Assessing the Orbital Contribution in the “Spodium Bond ...

doi.org/10.26434/chemrxiv.12936230.v5

Assessing the Orbital Contribution in the “Spodium Bond” by NaturalOrbital for Chemical Valence-Charge Displacement AnalysisGianluca Ciancaleoni, Luca Rocchigiani

Submitted date: 13/03/2021 • Posted date: 15/03/2021Licence: CC BY-NC-ND 4.0Citation information: Ciancaleoni, Gianluca; Rocchigiani, Luca (2020): Assessing the Orbital Contribution inthe “Spodium Bond” by Natural Orbital for Chemical Valence-Charge Displacement Analysis. ChemRxiv.Preprint. https://doi.org/10.26434/chemrxiv.12936230.v5

The term “spodium bond” (SpB) has been recently proposed for the non-coordinative interaction between apolarised group 12 metal and a mild Lewis base. In most of the systems showing short metal-donor distances,however, SpB coexists with other weak interactions, including hydrogen and halogen bonding. Here we showtheir mutual importance can be probed by dissecting the orbital component of the interaction through theNatural Orbital for Chemical Valence-Charge Displacement analysis. NOCV-CD gives us straightforwardsnapshots of relative energies and electrons involved, either for model and “real” adducts, allowing us todemonstrate the lack of a direct correlation between a favourable metal-base distance and the presence of anorbital contribution for the SpB.

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Assessing the Orbital Contribution in the “Spodium Bond” by

Natural Orbital for Chemical Valence-Charge Displacement

Analysis

Gianluca Ciancaleoni,a* Luca Rocchigianib*

a Università degli Studi di Pisa, Dipartimento di Chimica e Chimica Industriale, via Giuseppe Moruzzi

13, 56124 Pisa, Italy. E-mail: [email protected]

b School of Chemistry, University of East Anglia, Norwich Research Park, NR4 7TJ, Norwich, UK. E-

mail: [email protected]

Abstract

The term “spodium bond” (SpB) has been recently proposed to describe the non-coordinative

interaction that can be established between a polarized group 12 metal and a mild Lewis base (LB).

Most of the systems showing short metal-donor distances compatible with SpB are characterized by the

coexistence of multiple weak interactions, including hydrogen and halogen bonding, making the

assessment of real importance of SpB difficult. Here we show that the relative importance of each

contribution can be probed by dissecting the orbital component of the interaction through the Extended

Transition State-Natural Orbital for Chemical Valence-Charge Displacement analysis (ETS-NOCV-

CD). The latter gives useful information about relative energies and electrons involved, either for

model ([(thiourea)2MX2]…LB, M = Zn, Cd, Hg, X = Cl, I, LB = CH2S, CH2O, CH3CN and CO) and a

variety of structures extracted from experimentally characterized adducts, allowing us to demonstrate

the lack of a direct correlation between a favorable metal-base distance and the presence of an orbital

contribution for the SpB.

Introduction

σ-hole bonding,1 i.e. the attractive interaction between a polarized main group atom and a Lewis base

(LB), is gaining considerable importance within the family of “non-covalent” interactions. It arises

from an anisotropic charge distribution around the polarized atom, which creates a region of positive

electrostatic potential (σ-hole) interacting with electron-rich moieties. The most notable example is the

halogen bond (XB),2–4 which is increasingly establishing as a versatile tool in crystal engineering,

catalysis and photoluminescence.3 More recently, the family of σ-hole interactions has been expanding

throughout the periodic table to chalcogen (ChB),5–8 pnictogen (PB)9 and tetrel bond (TB).10 Along

with all these, π-hole interactions demonstrated to be worth of attention.11,12 Generally speaking, σ- and

π-hole interactions display a relevant orbital contribution to the bonding energy, which is, however,

smaller than the electrostatic one.

The latest addition to the group of σ-hole interactions is the metal bond, which entails systems where a

σ-hole is localized on a transition metal having a completely filled d shell. For instance, the existence

of a “coinage metal-bond” has been proposed to account for the mainly electrostatic interaction (in

some cases with non-negligible covalent character, especially for gold13,14) between a polarized group

11 metal (such as in AgCl or small metal clusters) and a LB.15,16 It is worth mentioning that some

authors propose a more concise and general nomenclature,17 recognizing the common nature of all

these weak interactions. Joy and Jemmis underlined that a LB → M polarization is possible only for

metals having a completely filled d shell, whereas for others, as rhodium and cobalt for instance, a M

→ LB polarization prevails, even if this depends also on the exact nature of the LB.18

An interesting case is that of group 12 metals, for which the capability of forming the so-called

“spodium bond” (SpB)19,20 has been proposed.21 In a recent contribution, Frontera et al. analyzed a

series of [(thiourea)2MX2] complexes (M = Zn, Cd, Hg; X = Cl, Br, I) and revealed that σ-holes located

along the bisector of the S–M–S bond can establish weak, non-coordinative interactions with mild LBs

such as CO, CH3CN or CH2O.22 Such model adducts generally show the concomitant presence of a

series of weak interactions, including hydrogen (HB) and chalcogen bonds, as evidenced by the

quantum theory of atoms in molecules (QTAIM). Since they all contribute to the overall fragment

interaction energy, it is important to disentangle these contributions to provide a precise assessment of

the importance of SpB.

A recent theoretical and detailed work used the Energy Decomposition Analysis (EDA)23,24 and other

tools on HgCl2...LB adducts, highlighting that these are held together by a composition of electrostatic

(Eelst) and orbital (Eorb) contributions.25 Despite the latter is found to account for 20-30% of the overall

attraction energy, it is still of interest to better understand what is the role of the SpB in the Eorb term,

which would correspond to a net charge transfer from the filled orbitals of the LB to the empty σ*(M-

X) orbital.

As previously noted, the inspection of the Cambridge Structural Database (CSD) reveals the existence

of a number of structures of group 12 compounds showing intermolecular M...LB distances shorter than

the sum of the corresponding van der Waals radii in the solid-state.22 In the large majority of the cases,

though, many interactions are potentially active. In a very simplistic approximation, one could group

them all under the SpB umbrella, but this is not obvious, especially from the orbital point of view.

In view of this, we took inspiration from the work by Frontera et al. and investigated the adducts

showed in Scheme 1 by Extended Transition State-Natural Orbital for Chemical Valence (ETS-

NOCV)26,27-Charge Displacement (CD)28–30 analysis, which recently proved to be a powerful tool for

the characterization of adducts held together by multiple interactions.31–35 With the results of the model

systems [(thiourea)2MX2]…LB in hand, we then selected some experimentally characterized structures,

where we isolated the adducts hypothetically involved in a SpB and we applied both EDA and ETS-

NOCV-CD analyses.

Our specific aim is to show that i) the ETS-NOCV-CD analysis can be used to separate and quantify

the different interactions between two fragments involved in SpB interactions, both in terms of energy

and amount of electron density involved, and ii) to look for a correlation between M–LB spatial

proximity and presence of an “orbital” SpB.

1: M = Cd, X1 = X2 = Cl, 2: M = Cd, X1 = X2 = I,

3: M = Zn, X1 = X2 = Cl, 4: M = Zn, X1 = F, X2 = Cl,

5: M = Hg, X1 = X2 = Cl, LB = CH2S, CH2O, CO, CH3CN

X1

M

SC(NH2)2(H2N)2CS

X2

LB

Scheme 1. Numbering of the model complexes studied and optimized structure of 1CH2S.

Results and discussion

Model systems: 1CH2S. ETS-NOCV-CD and EDA calculations on model complexes 1-5 (Scheme 1)

with different Lewis bases (CH2S, CH2O, CO and CH3CN) were performed at the M06-

D0/TZVP/ZORA level (if not otherwise specified, see Computational Details and Table 1). The choice

of the functional has been made to be consistent with a recent contribution by Joy and Jemmis on

similar systems.18 Starting with 1CH2S, we observed that the total interaction energy (Eint) between 1

and CH2S amounts to -10.5 kcal/mol and it is composed by a steric energy (Est = Pauli repulsive term

EPauli + electrostatic term Eelst) of 2.2 kcal/mol, a dispersion energy of -0.9 kcal/mol and a considerable

orbital contribution (Eorb) of -11.8 kcal/mol (Table 1). The latter shows to be quite stable towards

changing the functional at fixed geometry, oscillating between –11.7 and –13.4 kcal/mol (Table

1). As for the basis set, it is important to use an adequately large one, as Eorb is over-estimated

when a small basis set (sVP) is used. The discrepancies in the dispersion terms (Edisp) are due to

the different corrections used (in ORCA 4.1.0, M06 functional comes only with the D0

correction).

Table 1. Dependence of EDA results with functional/basis set for 1CH2S.

Functional/basis set Eint Eorb Est Edisp

M06-D0/ZORA-TZVP -10.5 -11.8 2.2 -0.9

B3LYP-D3/ZORA-TZVP -10.0 -11.7 9.4 -7.6

PBE0-D3/ZORA-TZVP -10.3 -11.7 5.6 -4.3

TPSSh-D3/ZORA-TZVP -10.8 -12.3 7.2 -5.7

TPSS-D3/ZORA-TZVP -10.8 -13.0 8.0 -5.8

BLYP-D3/ZORA-TZVP -10.1 -13.1 12.1 -9.1

BP86-D3/ZORA-TZVP -12.5 -13.4 9.3 -8.3

B3LYP-D3/ZORA-sVP -14.6 -15.8 8.9 -7.6

BP86-D3/ZORA-sVP -16.9 -17.8 9.3 -8.3

The decomposition of Est in EPauli and Eelst, which is not possible with ORCA 4.1.0, can be done

with ADF (B3LYP-D3, ZORA and TZ2P basis set), leading to the following results: Eint = -8.6,

Eorb = -12.3, EPauli = 39.0, Eelst = -27.7 and Edisp = -7.6 kcal/mol. Noteworthy, the value of Eorb is

similar to that obtained with ORCA, whereas Eint is smaller. The complete decomposition

shows that the electrostatic component is very relevant, as it happens with all the σ-hole

interactions. The orbital term is about 25% of all the attractive forces, similarly to what

observed by Cheng on HgCl2.25

A visual inspection of the geometry of 1CH2S shows clearly that many interactions concur in

the stabilization of the adduct. The same conclusion can be drawn by computing the

deformation map between the adduct and the sum of the isolated and frozen fragments, showing

how the electronic density changes upon the formation of the adduct (Δρtot, Figure 1). One set

of accumulation/depletion (blue/red coloured) regions can be observed on the Cd-S axis, while

another set lies on the Cl-H axis. This suggests that the metal center definitely interacts with the

Lewis base, but there is also a Cl–H hydrogen bond (HB). Disentangling these two interactions

would be desirable for a complete bond analysis.

While it is not possible to decompose Eelst in chemically meaningful contributions, this can be

done with Eorb. The stability of the latter towards the computational parameters (Table 1),

would suggest that the choice of the functional is not crucial. However, to be consistent with the

literature,18 the M06 functional was used throughout this study.

The decomposition of Eorb could be potentially done by taking advantage of the symmetry of

the system, at least in cases where different contributions belong to different irreducible

representations.36 Anyway, this approach often requires an in silico modification of the system

experimentally studied in order to achieve a perfect symmetry. The ETS-NOCV analysis allows

an alternative route to the decomposition of Δρtot and Eorb into chemically meaningful

contributions (Δρk and Ek) without passing through irreducible representations. The two

methodologies have been compared for halogen bonding and, when both are applicable, give

similar results.32

Figure 1. Isodensity surface plots (isodensity value 1 me a.u.-3 except for Δρ1, 0.7 me a.u.-3) for the

deformation maps relative to Δρtot and Δρk (k = 0, 1 and 2) of the [1]…[CH2S] interaction. The charge

flux is red → blue. Aside each Δρk map, the corresponding Charge Displacement function is shown.

Black dots indicate the position on the axis of the atomic nuclei. A yellow vertical band indicates the

boundary between the fragments.

In the case of 1CH2S, the application of ETS-NOCV analysis leads to the isolation of the main

components of the interaction (Figure 1), as described below.

- Δρ0 contains only the regions involved with the Cd...S interaction, with electron depletion

around the sulfur atom and accumulation located on both the interfragment space and

coordinated thioureas. The sulfur atom is donating electron density to the metal and at the same

time the electrons of the cadmium-thiourea bonds are repelled by the presence of the LB. This

term can be associated to the orbital equivalent of the “spodium bond” and accounts for -7.2

kcal/mol (eigenvalue υ0 = 0.30). It contains both interfragment charge transfer and

intrafragment polarization.

- Δρ1 describes a large polarization of the double bond of CH2S upon the formation of the

adduct, where the electron density moves from C (depletion) to S (accumulation). Smaller

details can be highlighted: the accumulation regions on the sulfur atom of the LB have a

noticeable pointed shape toward the sulfur atoms of the coordinated thiourea, whereas on the

latter small depletion regions are present. This pattern indicates a weak S-S interaction (ChB).

Δρ1 accounts for -0.9 kcal/mol (υ1 = 0.13).

- Δρ2 contains only the regions involved with the Cl…H interaction, with the typical pattern of a

HB: depletion on chloride, accumulation between the latter and hydrogen and polarization

pattern on H-C bond. Noteworthy, the charge flux is on the opposite direction with respect to

Δρ0. Δρ2 accounts for -1.7 kcal/mol (υ2 = 0.11).

- Δρk, with k > 2, contains only diffuse polarization regions that cannot be related to any

specific and relevant bond components (Supporting Information). The sum of all these

contributions accounts for the remaining -2.0 kcal/mol, with each contribution being smaller

than 0.5 kcal/mol (υk < 0.05).

While the analysis of the eigenvalues can be a useful criterion to decide whether the NOCV

components is relevant or not, it is not proportional to the energy contribution Ek or the value of

CTk (see later) and it will not be discussed in the detail.

Δρk can be separately integrated by the Charge Displacement analysis (CD) to have quantitative

information about the electron density involved in each single contribution (Δq, in

millielectrons, me). Each Δρk function has been integrated along the appropriate axis (Cd-S for

Δρ0, the bisector of the S–S–S angle for Δρ1 and Cl-H for Δρ2) to give 3 separate CD functions.

CD0 is found to be positive at any position, suggesting a net Cd←S charge transfer (Figure 1).

The value of Δq at the isoboundary, CT0 (CTSpB) is 125 me (Table 2). CD1 has a different

behaviour as it is negative at first (charge transfer from 1 to CH2S) and then it changes sign

because of the double bond polarization. At the isoboundary position, CT1 (CTChB) is equal to -

11 me. The latter is the sum of the projections of each single S→S CT on the chosen axis.

Considering that the S–S–S angle is 86.7°, each S→S charge transfer can be estimated as -7.6

me. The large polarization of the double bond interferes with this estimation, likely

underestimating it. The CD relative to the HB is negative, as the direction of the flux is Cl→H,

but there is no change of sign, as also the polarization is toward the same direction. CT2 (CTHB)

is -18 me.

Table 2. Orbital energies (in kcal/mol) and CT values (in me) relative to the different bond components

for the adducts between complexes 1-5 and CH3CN, CO, CH2O, CH2S.

Adduct Eorb ESpB (CTSpB) EHB (CTHB) EChB (CTChB)

1CH3CN -6.2 -2.5 (42) -1.4 (-17) -0.3 (5)

1CO -2.8 -0.7 (15) - -0.3 (-2)

1CH2O -8.2 -4.5 (65) -1.5 (-17) -0.5 (1)

1CH2S -11.8 -7.2 (125) -1.7 (-18) -0.9 (-11)

2CO -2.4 -0.6 (18) -1.0 (-16)a -0.5 (-6)

3CH3CN -3.8 -0.2 (1) -1.5 (-31) -0.6 (8)

3CO -1.5 -0.3 (9) - -0.7 (-3)

3CH2O -3.0 - -1.2 (-27) -0.7 (11)

3CH2S -3.6 - -1.2 (-12) -1.2 (-1)

4CH2O -4.5 -1.9 (31) -1.2 (-14) -

5CH3CN -4.8 -1.2 (18) -1.8 (-24) -0.2 (5)

5CO -2.1 -0.5 (16) -0.1 (-2)a -0.2 (-3)

5CH2O -4.6 -1.9 (27) -1.4 (-15) -0.2 (1)

5CH2S -6.1 -2.8 (54) -1.7 (-19) -0.4 (-3)

a Halogen → CO transfer

Model systems: other [(thiourea)2MX2]-LB. In analogy to 1CH2S, also the other Cd model

adducts are held together by more than one interaction. EDA data show that Eorb varies

significantly as a function of the Lewis base and this is reflected also in its composition in the

NOCV analysis. For example, replacing CH2S with CO in 1 lowers the total interaction energy

by over 6 kcal/mol (Eint = -4.4 kcal/mol), with an Eorb of only -2.8 kcal/mol (the list of NOCV

eigenvalues is reported in the Supporting Information). This clearly corresponds to the lack of

HB but, more importantly, to a much weaker SpB contribution (Table 2). Obviously, the two

things are not mutually independent, as the presence of an interaction can make the others

stronger. The other donors investigated in combination with 1 fall in between these two

extremes, in the order ESpB CH2S > CH2O > CH3CN > CO, with a clear correlation between

Eint, Eorb and ESpB.

Interestingly enough, when chlorides are replaced by iodides in the CO adduct (2CO), a small

I→CO contribution emerges, similar to what happens with coordinated triple bonds (see

Supporting Information).37,38 This contribution is larger, in energy, than SpB and S-S CT (Table

2).

When stronger Lewis bases such as ammonia are used, the interaction becomes stronger and the

distance shorter (length 2.4 Å) and the Cd-N bond possesses more than one component, as

expected from the Dewar-Chatt-Duncanson model. In fact, applying the ETS-NOCV-CD

analysis on 1NH3 Δρ0 describes the N→Cd σ donation (CT0 = 157 me, E0 = -13.5 kcal/mol),

Δρ1 and Δρ2 two different Cd→N small yet noticeable π back-donation components (CT1 = -5

me, CT2 = -11 me, E1 = E2 = -0.6 kcal/mol, Figure 2).

Figure 2. Isodensity surfaces (isodensity value 2 me a.u.-3 for Δρ0, 0.5 me a.u.-3 for Δρ1 and Δρ2)

for the deformation maps relative to Δρk (k = 1 and 2) of the 1NH3 adduct. The charge flux is

red → blue. Below each Δρk map, the corresponding Charge Displacement function is shown.

Black dots indicate the position on the axis of the atomic nuclei. A yellow vertical band

indicates the boundary between the fragments.

The total EDA results (performed with ADF) about the Cd-N interaction show that Eint, Eorb,

Eelst, EPauli and Edisp amount to -16.3, -18.2, -52.3, 59.0 and –4.9 kcal/mol, respectively. The

strength of the interaction is about double than that of 1CH2S, but the ratio between Eorb and the

sum of all the attractive terms is very similar: 24% for 1NH3 versus 26% for 1CH2S.

Therefore, it seems that the main differences between a coordinative and spodium bond, beside

the distance and the interaction energy (for which it is not easy to set a discriminating value), is

not in their energy composition, as the relative weights of the EDA terms are similar, but that in

the case of SpB any back-donation component already decayed and only the donation remains

active.39

Passing from Cd to Zn, the values of Eint drop considerably (Table 3) and the orbital

contribution of the SpB becomes almost negligible in the whole series, both in terms of energy

(maximum -0.3 kcal/mol, Table 2) and electrons involved (0-9 me), reasonably owing to the

lower polarizability of Zn. From the orbital point of view, the zinc adducts are essentially held

together by HB, with a small contribution from ChB (Figure 3 and Table 2). For example, for

the 3CH2S adduct, the interaction energy is -6.9 kcal/mol, of which -3.6 is the orbital term and -

2.5 kcal/mol is the steric one. The orbital term is decomposed mainly in Δρ0 (ChB component, -

1.2 kcal/mol, -1 me), Δρ1 (HB component, -1.2 kcal/mol, 12 me) and Δρ2 (double bond

polarization, -0.3 kcal/mol). All of the other contributions are energetically negligible and do

not show any sign of orbital SpB.

Anyway, Est values are slightly negative, indication that the electrostatic term is comparable to

the Pauli repulsion term, confirming the importance of electrostatics: the ratio Eorb/Eint is always

smaller for zinc adducts than for the corresponding cadmium counterparts (e.g. 0.66 for

1CH3CN and 0.50 for 3CH3CN). This indicates that for zinc adducts the global interaction is

less covalent than for cadmium adducts, and this is a first indication that the spatial proximity is

not enough to induce an orbital SpB. This does not exclude that there could be a contribution of

the polarized metal in the electrostatic term.

Figure 3. Isodensity surfaces (isodensity 0.5 me a.u.-3) for the deformation maps relative to Δρk (k = 0-

2) of the 3CH2S adduct. The charge flux is red → blue.

Anyway, this is notably affected by the nature of the halide: if the chloride trans to the LB is

swapped with a fluoride, the SpB returns to be relevant for Eorb (-1.9 kcal/mol and 31 me for

4H2CO).

Hg complexes have an intermediate behaviour between that of Cd and Zn ones, first of all in

terms of Eint, but also in terms of orbital spodium bond contribution. For example, 5CH2S

shows an ESpB of -2.8 kcal/mol, corresponding to a charge transfer of 54 me, 71 me lower than

that of 1CH2S (Table 2). This fits with the findings by Frontera et al., which showed that van

der Waals-corrected Cd...LB distances are generally shorter than Hg...LB ones and electrostatic

potentials are more positive on Cd than on Hg. This is likely due to the combination of the

smaller atomic radius of Hg and the steric congestion around the metal, which do not allow an

efficient approach by the LB. This is even more evident for the other donors in the series, where

the SpB is not the dominant term and has a similar or lower energy contribution than HB

contributions.

Table 3. EDA results (in kcal/mol) for the adducts between complexes 1-5 and CH3CN, CO,

CH2O, CH2S.

Adduct Eint Eorb Est Edisp

1CH3CN -9.4 -6.2 -2.2 -0.9

1CO -4.4 -2.8 -1.2 -0.4

1CH2O -9.0 -8.2 -0.1 -0.7

1CH2S -10.5 -11.8 2.2 -0.9

1NH3 -21.9 -16.9 -4.3 -0.7

2CO -3.4 -2.4 -0.4 -0.6

3CH3CN -7.6 -3.8 -2.8 -1.1

3CO -3.2 -1.5 -1.2 -0.5

3CH2O -6.1 -3.0 -2.5 -0.7

3CH2S -6.9 -3.6 -2.5 -0.8

4CH2O -7.5 -4.5 -2.4 -0.6

5CH3CN -8.3 -4.8 -2.4 -1.1

5CO -3.6 -2.1 -0.9 -0.6

5CH2O -6.9 -4.6 -1.6 -0.7

5CH2S -8.2 -6.1 -1.2 -0.9

Also for mercury, Est is slightly negative and generally the ratio Eorb/Eint is intermediate

between those of cadmium and zinc adducts.

Structure from Crystallographically characterized systems. From our analysis on model systems, it

clearly appears that the relative extent of the SpB orbital contribution strongly depends on the

system investigated, starting from the nature of the metal and its degree of polarization. Also,

while generally larger SpB contributions lead to shorter M…LB distances, there is no obvious

correlation between donor-acceptor distance and interaction energy in none of the compound

series. This is mostly a consequence of the coexistence of multiple interactions, which all

contribute to the final geometry.32 This is true even for simple biatomic molecules,40 but

becomes crucial for adducts held together by multiple weak interactions.

For this reason, it is of interest to extend ETS-NOCV-CD to experimentally characterised group

12 complexes showing short, but not coordinative X-M…LB arrangements. This allows to

assess whether they arise from a net SpB charge transfer and what is the role of the other

intermolecular interactions in determining such arrangements.

Scheme 2. Experimentally characterised structures selected for ETS-NOCV-CD analysis with

their respective CCDC code; dashed lines represent putative SpB interactions.

By analyzing the database of structures with reduced M...LB distances compatible with SpB,22

we have selected exemplificative adducts for each metal containing different ligands, charges

and donor types (Scheme 2). We deliberately chose fragments with a large span of interactions

energies, ranging from very positive (OTOFOU) to very negative (DUKTAF) values of Eint, to

check how the latter impacts on Eorb and its decomposition into contributions.

EDA results (Table 4) clearly show that all the structures have a favourable orbital contribution

to Eint (Eorb <0), even when the two fragments would repel each other when taken out of the

crystal lattice, as in OTOFOU, where two [CdCl4]2- anions are close each other. As only the

orbital term is important in the ETS-NOCV-CD analysis, the intrinsic instability of the isolated

adduct is not an issue, here. And, indeed, the decomposition of Eorb for such structures by

NOCV (Table 4) offers interesting details about the impact of the different intermolecular

interactions.

Starting with zinc systems, two different adducts can be isolated from the ASEZIJ lattice (-a and -b in

Table 4), the former of which has an Eint much smaller than the latter. In both cases, the bromine atom,

although it is spatially close to the zinc and laying approximately on the prolongation of the Br-Zn

bond (Br-Zn...Br angles = 163.9 and 143.9°, respectively), does not show any SpB orbital contribution.

The only orbital interaction is a halogen bond (XB) between the σ hole on the Br2 moiety and the lone

pairs of the bromine atoms coordinated to the zinc. As before, it cannot be excluded that the presence

of the metal could be important in the electrostatic term in determining the adduct geometry.

Table 4. EDA results (in kcal/mol) and CT values (in me) relative to the different bond

components for experimental solid-state dimers from CSD.

Adduct Eint Eorb Est Edisp ESpB (CTSpB) EHB (CTHB) EChB (CTChB) EXB (CTXB) ref

M = Zn

ASEZIJ-a -8.8 -6.1 -2.3 -0.4 - - - -4.5 (-77) 41

ASEZIJ-b -15.2 -14.8 0.0 -0.5 - - - -12.9 (-136) 41

YAGGET -17.4 -3.2 -13.5 -0.7 -1.8 (25) - - - 42

GOVLAE -21.6 -6.6 -12.8 -2.2 -1.1 (a) -2.4 (-45) - - 43

VARCEY 1.1 -3.8 6.9 -2.0 - -1.3 (24) - - 44

M = Cd

PEKSUT -1.6 -6.5 6.9 -2.0 -2.7 (56)b - -1.1 (1) - 45

CTURCD -2.9 -6.1 5.3 -2.1 -2.3 (46)b - - - 46

OTOFOU 206.5 -14.1 221.2 -0.7 -3.1 (c) - - - 47

HUWYON -25.6 -10.4 -13.0 -2.2 - -2.5 (c)

-1.6 (c)

- - 48

M = Hg

DUKTAF -133.4 -19.7 -112.5 -1.1 - -3.2 (-52) - -5.7 (-64) 49

KUSMAM -117.5 -23.5 -91.7 -2.4 -5.4 (-79)

-2.4 (4)

- -3.7 (-45) - 50

BEJGOM -76.3 -14.2 -60.7 -1.5 -5.2 (58) -1.3 (-33) - - 51

DEZGEV -17.7 -6.2 -9.5 -2.0 -2.8 (33) - - - 52

a: mixed with HB, see ESI; b: mixed with ChB, see ESI; c: integration unfeasible due to the

symmetry of the adduct.

On the contrary, in the dimer extracted from YAGGET, the oxygen of water prefers to establish an

orbital SpB with zinc rather than a selective HB with the ammonia protons (Figure 4a). In this way, it

can electrostatically interact with all the amino protons. The integration of the corresponding function,

Δρ0, leads to a CT0 of 25 me (-1.8 kcal/mol), which is the sum of the water polarization under the

electrostatic effect of the amino protons and the orbital SpB, the presence of which is confirmed by the

presence of a second maximum in the integrated function (Figure 4a).

a) b) c)

d) e) f)

Figure 4. Isodensity surface plots for the deformation maps relative to a) Δρ0 of the YAGGET adduct

(isodensity value 0.5 me a.u.-3) and, aside, the corresponding Charge Displacement function; b) Δρ0 of

the VARCEY adduct (isodensity value 0.3 me a.u.-3); c) Δρ0 of the PEKSUT adduct (isodensity value

0.6 me a.u.-3); d) Δρ0 of the OTOFOU adduct (isodensity value 0.5 me a.u.-3); e) Δρ1 of the DUKTAF

adduct (isodensity value 1.0 me a.u.-3); f) Δρ2 of the DUKTAF adduct (isodensity value 0.8 me a.u.-3).

The charge flux is red → blue.

In the case of GOVLAE, the adduct is mainly held together by HBs between the amino protons and the

sulfur atoms, but minor polarization regions on the metal in Δρ1 does not allow to completely exclude

the presence of a small SpB.

In VARCEY (Figure 4b), no SpB can be found in the NOCV terms. In fact, it is true that an

accumulation region is present between the chlorine and the zinc, but there is no

depletion/accumulation pattern on the metal. On the other hand, such a pattern is on the coordinated

thioureas, suggesting that this term refers only to the ChB between the lone pairs of chloride and the σ-

holes of the sulfur atoms.

The comparison with PEKSUT and CTURCD, which are very similar to VARCEY but with cadmium

instead of zinc (and bromine instead of chlorine for CTURCD), reveals how SpB is sensitive to the

details of the structure. In fact, in PEKSUT and CTURCD, accumulation regions are clearly visible on

the metal (Δρ0, Figure 4c and Supporting Information) and on the thiourea ligands, indication that SpB

and ChB in this case are not perfectly separated. Noteworthy, also Δρ1 refers the ChB (see Supporting

Information).

HUWYON is held together only by HBs, with no involvement of the metal (see Supporting

Information), whereas about OTOFOU we already mentioned that it has a relevant orbital contribution,

even if it is a stable adduct only if placed in its crystal lattice. In this case, the analysis of Est is not very

informative, while the analysis of Eorb is still greatly useful, as it is not important here why the two

fragments are positioned at that distance (lattice stabilization), but what happens to the orbital mixing

when they assume that peculiar position. In the case of OTOFOU, both Δρ0 and Δρ1 contains orbital

SpB contributions associated with large polarization effects (Figure 4d), which are unavoidable when

two anions are close each other. Unfortunately, the integration of the Δρ functions is not informative, as

the adduct is so symmetrical that any flux from one fragment to the other is counterbalanced by a

similar one with opposite sign, making the sum null.

Finally, for mercury adducts, the fragment isolated from the DUKTAF lattice contains three moieties

and has been separated into two fragments, [HgBr4]2- and [(H2O)(BrPyH)]+. The fragmentation could

have been [(HgBr4)(H2O)]2- and [BrPyH]+ with no substantial differences. Despite the spatial proximity

of the bromine to the mercury, the only intermolecular interactions here are a XB between the

coordinated bromine (LB) and the bromine on the pyridinium (LA) and a HB between another

coordinated bromine and the water (Figure 4e and f). The very large value of Eint obviously depends on

the electrostatic cation/anion attraction, but this contribution is mainly in Est and does not affect much

Eorb.

KUSMAM is interesting, too, because the adduct contains two different mercury atoms, one belonging

to the anion and the second to the cation, and both of them are bound to chlorine ligands. The ETS-

NOCV-CD analysis reveals not only that a chlorine on the anion establishes a SpB with the mercury on

the cation (79 me, see Table 4), but also, less obvious, viceversa: the chlorine on the cation donates a

very small amount of charge (5 me) to the mercury on the anion (see Supporting Information).

In BEJGOM the nitrate anion establishes either a SpB with the mercury (58 me), but also a HB with a

hydrogen of the complex (-33 me), whereas in DEZGEV the nitrogen of the acetonitrile shows a N →

Hg charge transfer of 33 me (see Supporting Information).

It is interesting to note that for each metal, both examples with and without an orbital SpB can be found

and quantified, making difficult to give a general rule for the occurrence of SpB. Of course, a polarized

metal is needed, but this is not uncommon: in many cases the metal is bound to electronegative atoms

and therefore a σ-hole can likely be present. For lighter and less polarizable metals, as zinc, the

polarization, and hence SpB, is more difficult to achieve, but if electrostatics keep the LB in the right

position, as in YAGGET, the SpB can be induced. Secondly, the LB should be not too strong to

coordinate and not too weak to not interact. Anyway, a pure SpB is difficult to obtain, as the ancillary

ligands around the metal very likely establish other weak interactions with the LB, in some cases

favouring the occurrence of SpB, as the HB in the model systems.

From the methodological point of view, the separation of the contributions is often perfect, with some

exceptions. In addition, it should be highlighted that the ETS-NOCV-CD analysis is quite fast (three

single point calculations, generally taking from 0.5 to 10 h depending on the size of the system), robust

with respect to the choice of the computational details and greatly informative.

Conclusions

The application of ETS-NOCV-CD analysis allows the disentanglement of the complex network of

weak interactions that drives the non-coordinative attraction between group 12 complexes and Lewis

bases.

By assessing the orbital contribution to the interaction energy, we could characterize each component

separately and observe that a net LB→M charge transfer, compatible with the establishment of the so-

called Spodium Bond (SpB), can occur. The extent of such contribution is strongly affected by the

metal, ligands and bases involved and generally, when the same ligand set is investigated, it seems to

be more important for Cd complexes than for Hg and Zn.

The application of this method to “real-life” structures revealed that there is no direct correlation

between short M...LB distances and LB→M charge transfer, as other intermolecular forces such as

hydrogen, chalcogen or halogen bond can intervene in determining the structural features of that

particular molecular network. Therefore, while it can be used as a screening parameter while looking

for potential SpB interactions, a M...LB distance shorter than the sum of the van der Waals radii does

not guarantee that a net SpB will be present, so each structure needs to be evaluated individually. ETS-

NOCV-CD, at this point, can be used to quickly visualize whether the bond has an orbital contribution

or not.

Computational Details

All the geometries were optimized with ORCA 4.1.0,53,54 using the M06 functional. Dispersion forces

were taken into account by using the D3 correction with zero damping (Becke-Johnson damping is not

available for M06).55 Relativistic effects were treated with the scalar zeroth-order regular

approximation (ZORA).56,57 The basis set was ZORA-TZVP for all the atoms except for iodine,

cadmium and tellurium, for which OLD-ZORA-TZVP was used, and mercury, for which SARC-

ZORA-TZVP was used. Coulomb-fitting auxiliary basis sets SARC/J have been used.58 The grid was

set to 5, the SCF requirements were set to “very tight” and the number of radial points was set to 6. No

negative frequencies were found.

Geometries taken from literature (ref. 22 and CSD) have not been re-optimized.

Energy decomposition analysis (EDA).23

The EDA has been performed with a large variety of functional/basis sets combinations, either using

ORCA 4.1.0 or ADF (development version r47686).59 The EDA allows the decomposition of the bond

energy into physically meaningful contributions. The interaction energy (Eint) is the difference of

energy between the adduct and the unrelaxed fragments. It can be divided into contributions associated

with the orbital, steric and dispersion interactions, as shown in eqn (1)

Eint = Est + Eorb + Edisp (1)

Est is usually called the steric interaction energy and it is the sum of Eelst, the classical electrostatic

interaction between the unperturbed charge distributions of the fragments (ρA and ρB) at their final

positions in the adduct, and the Pauli repulsion (EPauli) that is the energy change associated with going

from ρA + ρB to the antisymmetrized and renormalized wave function. The decomposition of Est is not

possible with ORCA 4.1.0, while it is with ADF. Est comprises the destabilizing interactions between

the occupied orbitals and is responsible for any steric repulsion. Eorb is the contribution arising from

allowing the wave function to relax to the fully converged one, accounting for electron pair bonding,

charge transfer and polarization, while Edisp is the contribution of the dispersion forces.

Extended Transition State-Natural Orbital for Chemical Valence theory (ETS-NOCV) and

Charge Displacement function analysis.

In the NOCV approach, the electron density rearrangement taking place upon formation of AB from

fragments A and B is defined with respect to a reference system made up of the occupied ψiA and ψi

B

orbitals of A and B orthonormalized with respect to each other (ψi0). In other words, rather than two

separate A and B determinants, their antisymmetrized product is taken as the fragment–fragment non-

interacting reference (the so-called “promolecule”). The resulting electron density rearrangement,

(2)

where ψi(AB) is the set of occupied orbitals of the adduct, can be brought into diagonal form in terms of

NOCVs. These are defined as the eigenfunctions, ϕ±k, of the so-called “valence operator” 60–62

(3)

The fragmentation depends on the interaction under examination and is generally indicated in each

case. The NOCVs can be grouped in pairs of complementary orbitals (ϕk, ϕ−k) corresponding to

eigenvalues with same absolute value but opposite sign (Eq. 4).

(4)

where k numbers the NOCV pairs (k = 0 for the largest value of |νk|). In this framework, Δρtot can be

defined as in Eq. 5.

(5)

Hence, on formation of AB from the promolecule, a fraction νk of electrons is transferred from the ϕ–k

to the ϕk orbital. Only some NOCVs pairs have νk significantly different from zero and this subgroup is

generally enough to describe the A…B interaction. For each value of k, an energy contribution

associated with the k-th NOCV pair is given.

The NOCV analysis has been performed with ORCA 4.1.0.

The Charge Displacement function analysis is based on Eq. (6). The function Δq(z’) defines, at each

point along a chosen axis, the amount of electron charge that, upon formation of the bond between the

fragments, moves across a plane perpendicular to the axis through the point z’. A positive (negative)

value corresponds to electrons flowing in the direction of decreasing (increasing) z. Charge

accumulates where the slope of Δq is positive and decreases where it is negative.

(6)

In order to extract a CT value from the Δq curve, it is useful to fix a plausible boundary separating the

fragments in the adducts (isoboundary). Unless otherwise specified, we chose the point on the z axis at

which equal-valued isodensity surfaces of the isolated fragments are tangent.36 At this point, the value

of Δqk is represented by CTk.

The cubes have been created with ORCA 4.1.0 and manipulated with a Python software developed in

the group of Dr. Leonardo Belpassi. Electronic deformation maps have been created with Molekel.

Acknowledgements

This work was supported by the University of Pisa (PRA_2018_36 grant). LR is thankful to the

University of East Anglia for support.

Conflicts of interest

There are no conflicts to declare.

Supporting Information

Additional tables and figure, XYZ coordinates for all the system studied, including our selection from

X-ray crystallographic data.

References

(1) Politzer, P.; Murray, J. S.; Clark, T. Halogen Bonding and Other σ-Hole Interactions: A

Perspective. Physical Chemistry Chemical Physics. The Royal Society of Chemistry June 18,

2013, pp 11178–11189.

(2) Wang, H.; Bisoyi, H. K.; Urbas, A. M.; Bunning, T. J.; Li, Q. The Halogen Bond: An Emerging

Supramolecular Tool in the Design of Functional Mesomorphic Materials. Chem. - A Eur. J.

2019, 25 (6), 1369–1378.

(3) Cavallo, G.; Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.; Terraneo, G. The

Halogen Bond. Chem. Rev. 2016, 116 (4), 2478–2601.

(4) Desiraju, G. R.; Ho, P. S.; Kloo, L.; Legon, A. C.; Marquardt, R.; Metrangolo, P.; Politzer, P.;

Resnati, G.; Rissanen, K. Definition of the Halogen Bond (IUPAC Recommendations 2013).

Pure Appl. Chem. 2013, 85 (8), 1711–1713.

(5) Pascoe, D. J.; Ling, K. B.; Cockroft, S. L. The Origin of Chalcogen-Bonding Interactions. J. Am.

Chem. Soc. 2017, 139 (42), 15160–15167.

(6) Scilabra, P.; Terraneo, G.; Resnati, G. The Chalcogen Bond in Crystalline Solids: A World

Parallel to Halogen Bond. Acc. Chem. Res. 2019, 52, 1313–1324.

(7) Garrett, G. E.; Gibson, G. L.; Straus, R. N.; Seferos, D. S.; Taylor, M. S. Chalcogen Bonding in

Solution: Interactions of Benzotelluradiazoles with Anionic and Uncharged Lewis Bases. J. Am.

Chem. Soc. 2015, 137 (12), 4126–4133.

(8) Aakeroy, C. B.; Bryce, D. L.; Desiraju, G. R.; Frontera, A.; Legon, A. C.; Nicotra, F.; Rissanen,

K.; Scheiner, S.; Terraneo, G.; Metrangolo, P.; et al. Definition of the Chalcogen Bond (IUPAC

Recommendations 2019). Pure Appl. Chem. 2019, 91 (11), 1889–1892.

(9) Scilabra, P.; Terraneo, G.; Resnati, G. Fluorinated Elements of Group 15 as Pnictogen Bond

Donor Sites. Journal of Fluorine Chemistry. Elsevier B.V. November 1, 2017, pp 62–74.

(10) Bauzá, A.; Seth, S. K.; Frontera, A. Tetrel Bonding Interactions at Work: Impact on Tin and

Lead Coordination Compounds. Coordination Chemistry Reviews. Elsevier B.V. April 1, 2019,

pp 107–125.

(11) Bauzá, A.; Mooibroek, T. J.; Frontera, A. The Bright Future of Unconventional σ/π-Hole

Interactions. ChemPhysChem. Wiley-VCH Verlag August 1, 2015, pp 2496–2517.

(12) Politzer, P.; Murray, J. S. Electrostatics and Polarization in σ- and π-Hole Noncovalent

Interactions: An Overview. ChemPhysChem. Wiley-VCH Verlag April 2, 2020, pp 579–588.

(13) Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. Microwave Spectra and Structures

of KrAuF, KrAgF, and KrAgBr; 83Kr Nuclear Quadrupole Coupling and the Nature of Noble

Gas-Noble Metal Halide Bonding. J. Am. Chem. Soc. 2004, 126 (4), 1235–1246.

(14) Evans, C. J.; Lesarri, A.; Gerry, M. C. L. Noble Gas-Metal Chemical Bonds. Microwave

Spectra, Geometries, and Nuclear Quadrupole Coupling Constants of Ar-AuCl and Kr-AuCl. J.

Am. Chem. Soc. 2000, 122 (25), 6100–6105.

(15) Zierkiewicz, W.; Michalczyk, M.; Scheiner, S. Regium Bonds between Mn Clusters (M = Cu,

Ag, Au and n = 2-6) and Nucleophiles NH3 and HCN. Phys. Chem. Chem. Phys. 2018, 20 (35),

22498–22509.

(16) Wang, R.; Yang, S.; Li, Q. Coinage-Metal Bond between [1.1.1]Propellane and M2/Mcl/MCH3

(M = Cu, Ag, and Au): Cooperativity and Substituents. Molecules 2019, 24 (14).

(17) Legon, A. C.; Walker, N. R. What’s in a Name? “Coinage-Metal” Non-Covalent Bonds and

Their Definition. Physical Chemistry Chemical Physics. Royal Society of Chemistry July 25,

2018, pp 19332–19338.

(18) Joy, J.; Jemmis, E. D. Contrasting Behavior of the Z Bonds in X-Z···Y Weak Interactions: Z =

Main Group Elements Versus the Transition Metals. Inorg. Chem. 2017, 56 (3), 1132–1143.

(19) Karmakar, M.; Frontera, A.; Chattopadhyay, S.; Mooibroek, T. J.; Bauzá, A. Intramolecular

Spodium Bonds in Zn(II) Complexes: Insights from Theory and Experiment. Int. J. Mol. Sci.

2020, 21 (19), 1–14.

(20) Mahmoudi, G.; Lawrence, S. E.; Cisterna, J.; Cárdenas, A.; Brito, I.; Frontera, A.; Safin, D. A. A

New Spodium Bond Driven Coordination Polymer Constructed from Mercury( Ii ) Azide and

1,2-Bis(Pyridin-2-Ylmethylene)Hydrazine. New J. Chem. 2020.

(21) Alkorta, I.; Elguero, J.; Frontera, A. Not Only Hydrogen Bonds: Other Noncovalent Interactions.

Crystals. MDPI AG March 6, 2020, p 180.

(22) Bauzá, A.; Alkorta, I.; Elguero, J.; Mooibroek, T. J.; Frontera, A. Spodium Bonds: Noncovalent

Interactions Involving Group 12 of Elements. Angew. Chemie Int. Ed. 2020, anie.202007814.

(23) Hopffgarten, M. von; Frenking, G. Energy Decomposition Analysis. Wiley Interdiscip. Rev.

Comput. Mol. Sci. 2012, 2 (1), 43–62.

(24) Frenking, G.; Krapp, A. Unicorns in the World of Chemical Bonding Models. J. Comput. Chem.

2007, 28 (1), 15–24.

(25) Xia, T.; Li, D.; Cheng, L. Theoretical Analysis of the Spodium Bonds in HgCl2⋯L (L = ClR,

SR2, and PR3) Dimers. Chem. Phys. 2020, 539, 110978.

(26) Mitoraj, M. P.; Michalak, A.; Ziegler, T. A Combined Charge and Energy Decomposition

Scheme for Bond Analysis. J. Chem. Theory Comput. 2009, 5 (4), 962–975.

(27) Radoń, M. On the Properties of Natural Orbitals for Chemical Valence. Theor. Chem. Acc. 2008,

120 (4–6), 337–339.

(28) Ciancaleoni, G.; Nunzi, F.; Belpassi, L. Charge Displacement Analysis—A Tool to

Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds. Molecules 2020,

25 (2), 300.

(29) Ciancaleoni, G. Lewis Base Activation of Lewis Acid: A Detailed Bond Analysis. ACS Omega

2018, 3 (11), 16292–16300.

(30) Bistoni, G.; Rampino, S.; Tarantelli, F.; Belpassi, L. Charge-Displacement Analysis via Natural

Orbitals for Chemical Valence: Charge Transfer Effects in Coordination Chemistry. J. Chem.

Phys. 2015, 142 (8), 084112.

(31) Buttarazzi, E.; Rosi, F.; Ciancaleoni, G. Influence of Halogen Bonding on Gold(i)-Ligand Bond

Components and DFT Characterization of a Gold-Iodine Halogen Bond. Phys. Chem. Chem.

Phys. 2019, 21 (36), 20478–20485.

(32) Ciancaleoni, G.; Belpassi, L. Disentanglement of Orthogonal Hydrogen and Halogen Bonds via

Natural Orbital for Chemical Valence: A Charge Displacement Analysis. J. Comput. Chem.

2020, 41 (12), 1185–1193.

(33) Novák, M.; Foroutan-Nejad, C.; Marek, R. Asymmetric Bifurcated Halogen Bonds. Phys. Chem.

Chem. Phys. 2015, 17 (9), 6440–6450.

(34) Bora, P. L.; Novák, M.; Novotný, J.; Foroutan-Nejad, C.; Marek, R. Supramolecular Covalence

in Bifurcated Chalcogen Bonding. Chem. - A Eur. J. 2017, 23 (30), 7315–7323.

(35) Mitoraj, M. P.; Michalak, A. Theoretical Description of Halogen Bonding - An Insight Based on

the Natural Orbitals for Chemical Valence Combined with the Extended-Transition- State

Method (ETS-NOCV). J. Mol. Model. 2013, 19 (11), 4681–4688.

(36) Salvi, N.; Belpassi, L.; Tarantelli, F. On the Dewar-Chatt-Duncanson Model for Catalytic

Gold(I) Complexes. Chem. - A Eur. J. 2010, 16 (24), 7231–7240.

(37) Bartalucci, N.; Belpassi, L.; Marchetti, F.; Pampaloni, G.; Zacchini, S.; Ciancaleoni, G. Ubiquity

of Cis-Halide → Isocyanide Direct Interligand Interaction in Organometallic Complexes.

Inorganic Chemistry. American Chemical Society December 3, 2018, pp 14554–14563.

(38) Ciancaleoni, G.; Belpassi, L.; Marchetti, F. Back-Donation in High-Valent D0 Metal

Complexes: Does It Exist? The Case of NbV. Inorg. Chem. 2017, 56 (18), 11266–11274.

(39) Bistoni, G.; Belpassi, L.; Tarantelli, F. Disentanglement of Donation and Back-Donation Effects

on Experimental Observables: A Case Study of Gold-Ethyne Complexes. Angew. Chemie - Int.

Ed. 2013, 52 (44), 11599–11602.

(40) Krapp, A.; Bickelhaupt, F. M.; Frenking, G. Orbital Overlap and Chemical Bonding. Chem. - A

Eur. J. 2006, 12 (36), 9196–9216.

(41) Hausmann, D.; Feldmann, C. Bromine-Rich Zinc Bromides: Zn6Br12(18-Crown-6)2×(Br2)5,

Zn4Br8(18-Crown-6)2×(Br2)3, and Zn6Br12(18-Crown-6)2×(Br2)2. Inorg. Chem. 2016, 55

(12), 6141–6147.

(42) Qu, Y.; Liu, Z. Di; Tan, M. Y.; Zhu, H. L. Bis[Tetraamminezinc(II)] Tetrapicrate Trihydrate.

Acta Crystallogr. Sect. E Struct. Reports Online 2004, 60 (9), m1343–m1345.

(43) Cameron, E. M.; Louch, W. E.; Cameron, T. S.; Knop, O. Thiocyanates. 1: N-H(N)...S Bonding

in Tetrahedral [Zn(NCS)2L]0 Complexes (L = MexH2-XN(CH2)2NH 2-YMey, x, y = 0-2).

Zeitschrift fur Anorg. und Allg. Chemie 1998, 624 (10), 1629–1641.

(44) Nithya, K.; Karthikeyan, B.; Ramasamy, G.; Muthu, K.; Meenakshisundaram, S. P. Growth and

Characterization of Fe3+-Doped Bis(Thiourea)Zinc(II) Chloride Crystals. Spectrochim. Acta -

Part A Mol. Biomol. Spectrosc. 2011, 79 (5), 1648–1653.

(45) Marcos, C.; Alía, J. M.; Adovasio, V.; Prieto, M.; García-Granda, S. Bis(Thiourea)Cadmium

Halides. Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1998, 54 (9), 1225–1229.

(46) Nardelli, M.; Cavalca, L.; Braibanti, A. The Structure of Rhombic Thallous Nitrate. Gazz. Chim.

Ital. 1957, 87, 137.

(47) Li, Q.; Qiu, S. C.; Zhang, J.; Chen, K.; Huang, Y.; Xiao, X.; Zhang, Y.; Li, F.; Zhang, Y. Q.;

Xue, S. F.; et al. Twisted Cucurbit[n]Urils. Org. Lett. 2016, 18 (16), 4020–4023.

(48) Moloto, M. J.; Malik, M. A.; O’Brien, P.; Motevalli, M.; Kolawole, G. A. Synthesis and

Characterisation of Some N-Alkyl/Aryl and N,N′-Dialkyl/Aryl Thiourea Cadmium(II)

Complexes: The Single Crystal X-Ray Structures of [CdCl2(CS(NH2) NHCH3)2]n and

[CdCl2(CS(NH2)NHCH2 CH3)2]. Polyhedron 2003, 22 (4), 595–603.

(49) Al-Far, R. H.; Haddad, S. F.; Ali, B. F. Three Isomorphous 2,6-Dibromo-Pyridinium Tetra-

Bromidometallates: (C 5H4Br2N)2[MBr4] ·2H2O (M = Cu, Cd and Hg). Acta Crystallogr. Sect.

C Cryst. Struct. Commun. 2009, 65 (11), m451–m454.

(50) Sobhia, M. E.; Panneerselvam, K.; Chacko, K. K.; Suh, I. H.; Weber, E.; Reutel, C. Crystal

Structure of the 2:1 Complex of Mercury(II) Chloride with Trithiapyridino-12-Crown-4 Having

Unusual Mercury Coordination. Inorganica Chim. Acta 1992, 194 (1), 93–97.

(51) Canty, A. J.; Chaichit, N.; Gatehouse, B. M.; George, E. E. Coordination Chemistry of

Methylmercury (II). Complexes of Aromatic Nitrogen Donor Tripod Ligands Involving New

Coordination Geometries for MeHgII. Inorg. Chem. 1981, 20 (12), 4293–4300.

(52) Lee, K. M.; Chen, J. C. C.; Huang, C. J.; Lin, I. J. B. Rectangular Architectures Formed by

Acyclic Diamido-Metal-N-Heterocyclic Carbenes with Skewed Conformation. CrystEngComm

2007, 9 (4), 278–281.

(53) Neese, F. The ORCA Program System. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2012, 2 (1),

73–78.

(54) Neese, F. Software Update: The ORCA Program System, Version 4.0. Wiley Interdiscip. Rev.

Comput. Mol. Sci. 2017, 8 (1), e1327.

(55) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio

Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-

Pu. J. Chem. Phys. 2010, 132 (15), 154104.

(56) van Lenthe, E.; Baerends, E. J.; Snijders, J. G. Relativistic Regular Two Component

Hamiltonians. J. Chem. Phys. 1993, 99 (6), 4597–4610.

(57) Van Lenthe, E. Geometry Optimizations in the Zero Order Regular Approximation for

Relativistic Effects. J. Chem. Phys. 1999, 110 (18), 8943–8953.

(58) Weigend, F. Accurate Coulomb-Fitting Basis Sets for H to Rn. Phys. Chem. Chem. Phys. 2006,

8 (9), 1057–1065.

(59) te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; van Gisbergen, S. J. A.;

Snijders, J. G.; Ziegler, T. Chemistry with ADF. J. Comput. Chem. 2001, 22 (9), 931–967.

(60) Nalewajski, R. F.; Mrozek, J.; Michalak, A. Two-Electron Valence Indices from the Kohn-Sham

Orbitals. Int. J. Quantum Chem. 1997, 61 (3), 589–601.

(61) Nalewajski, R. F.; Ozek, J. Modified Valence Indices from the Two‐particle Density Matrix. Int.

J. Quantum Chem. 1994, 51 (4), 187–200.

(62) Nalewajski, R. F.; Köster, A. M.; Jug, K. Chemical Valence from the Two-Particle Density

Matrix. Theor. Chim. Acta 1993, 85 (6), 463–484.

FOR TABLE OF CONTENTS ONLY

A series of adducts between polarized group 12 metal and a mild Lewis Base has been studied,

resulting to be held together by a combination of weak interactions: spodium bond, hydrogen bond,

halogen bond and chalcogen bond. The ETS-NOCV-CD analysis allowed the decomposition of the

interaction into chemically meaningful contributions, allowing a complete quantification of each

component.

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S1

ELECTRONIC SUPPORTING INFORMATION

Assessing the Orbital Contribution in the “Spodium Bond” by

Natural Orbital for Chemical Valence-Charge Displacement

Analysis

Gianluca Ciancaleoni,a,* Luca Rocchigianib,*

a Università degli Studi di Pisa, Dipartimento di Chimica e Chimica Industriale, via Giuseppe Moruzzi

13, 56124 Pisa, Italy. E-mail: [email protected]

b School of Chemistry, University of East Anglia, Norwich Research Park, NR4 7TJ, Norwich, UK. E-

mail: [email protected]

Electronic deformation maps for all the relevant NOCV contributions of all the considered

systems……………………………………………………………………………………………S2-S15

EDA results, in kcal/mol, for all the adducts considered here……………………………………….S16

NOCV eigenvalues υk for all the adducts considered here………………………………………...…S17

DFT coordinates of all the system considered, including our selection from X-ray crystallographic

data……………………………………………………………………………………………….S18-S34

Bibliography…………………………………………………………………………………..………S35

S2

Electronic deformation maps for all the relevant NOCV contributions of all the considered

systems.

Figure S1. Isodensity surfaces (isodensity value 0.3 me a.u.−3) for the deformation maps relative to Δρk

(k = 3-5) of the 1CH3CN adduct. The charge flux is red → blue. E3 = -0.5 kcal/mol, E4 = -0.3 kcal/mol,

E5 = -0.2 kcal/mol.

Δρ0 (1.4 me a.u.−3) Δρ1 (1.0 me a.u.−3) Δρ2 (0.2 me a.u.−3)

Figure S2. Isodensity surfaces (isodensity values given for each contribution) for the deformation maps

relative to Δρk (k = 0-2) of the 1CH2O adduct. The charge flux is red → blue.


S3


relative to Δρk (k = 0-2) of the 1CO adduct. The charge flux is red → blue.







S4

Δρ0 (0.9 me a.u.−3) Δρ1 (0.2 me a.u.−3) Δρ2 (0.2 me a.u.−3) Δρ3(0.3 me a.u.−3)


relative to Δρk (k = 0-2) of the 3CH3CN adduct. The charge flux is red → blue.

S5

Δρ0 (0.6 me a.u.−3) Δρ1 (0.6 me a.u.−3)


relative to Δρk (k = 0 and 1) of the 3CH2CO adduct. The charge flux is red → blue.

Δρ0 (0.5 me a.u.−3) Δρ1 (0.7 me a.u.−3)


relative to Δρk (k = 0-2) of the 3CH2S adduct. The charge flux is red → blue.


Figure S9. Isodensity surfaces (isodensity values given for each contribution) for the deformation

maps relative to Δρk (k = 0-2) of the 4CH2O adduct. The charge flux is red → blue.

S6



maps relative to Δρk (k = 0-2) of the 5CH3CN adduct. The charge flux is red → blue.



maps relative to Δρk (k = 0-2) of the 5CO adduct. The charge flux is red → blue.



maps relative to Δρk (k = 0-2) of the 5CH2O adduct. The charge flux is red → blue.

S7



maps relative to Δρk (k = 0-2) of the 5CH2S adduct. The charge flux is red → blue.

Δρ0 (2 me a.u.−3) Δρ1 (0.5 me a.u.−3) Δρ3 (0.5 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the 1NH3 adduct. The charge flux is red → blue. For a

coordinated LB, beyond the smaller Cd-LB distance (here it is 2.4 Å), it is evident, in Δρ1 and Δρ2 the

presence of a small back-donation contribution (red-colored regions on the metal). In particular, E0 = -

13.5, E1 = E2 = -0.6 kcal/mol and CT0 = 157, CT1 = -5 and CT2 = -11 me.

S8

Δρ0 (0.6 me a.u.−3) Δρ1 (0.3 me a.u.−3)

Δρ0 (1.5 me a.u.−3) Δρ1 (0.5 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the ASEZIJ adduct (top: dimer a; bottom: dimer b).1 The charge

flux is red → blue. In this structure, two different Zn2Br6 moieties coexist in the crystalline cell. Both

of them interacts with the Br2, but with a different geometry. In both dimers, Δρ0 describes a halogen

bond and Δρ1 a polarization, in both cases with negligible contributions on the metal. No evidence of a

direct Br2 → Zn charge transfer.

S9

Δρ0 (0.3 me a.u.−3) Δρ1 (0.3 me a.u.−3)


maps relative to Δρk (k = 0 and 1) of the VARCEY adduct.2 The charge flux is red → blue. In this

system, Δρ0 describes two chalcogen bond between the chloride and the two sulfur ligands. This is

demonstrated by the absence of any contribution on the metal. Δρ1 is a polarization with no net charge

transfer between the two fragments.

Δρ0 (0.5 me a.u.−3) Δρ1 (0.5 me a.u.−3)


maps relative to Δρk (k = 0 and 1) of the YAGGET adduct.3 The charge flux is red → blue. In this

system, Δρ0 shows a direct O → Zn charge transfer, as demonstrated by the depletion/accumulation

regions on the metal. Δρ1 involves only the molecule of water, which is polarized by the presence of the

cation.

S10

Δρ0 (0.9 me a.u.−3) Δρ1 (0.3 me a.u.−3)


maps relative to Δρk (k = 0 and 1) of the GOVLAE adduct.4 The charge flux is red → blue. In this

structure, both Δρ0 and Δρ1 describe hydrogen bonds between the amino protons on one fragment and

the sulfur atom of the other fragment. Only very small polarization regions are present on the metal.

Δρ0 (0.6 me a.u.−3) Δρ1 (0.2 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the PEKSUT adduct.5 The charge flux is red → blue.

S11

Δρ0 (0.5 me a.u.−3) Δρ1 (0.2 me a.u.−3)


maps relative to Δρk (k = 0 and 1) of the CTURCD adduct.6 The charge flux is red → blue. In this

system, Δρ0 describe a charge shift from the chlorine to the cadmium, as demonstrated by the

accumulation regions on the metal, but also a component of the Cl → S chalcogen bond is present

(accumulation regions also on the thiourea ligands). Δρ1 is only polarization, as no accumulation region

is present between the two fragments.



maps relative to Δρk (k =0, 1 and 2) of the OTOFOU adduct.7 The charge flux is red → blue. In this

system, both Δρ0 and Δρ1 show two Cl → Cd spodium bonds, in a symmetrical way. Their further

disentanglement is not possible. The other contribution, as Δρ2, are only due to polarization. Being an

adduct made by two anions, the electronic repulsion is very marked.

S12

Δρ0 (0.6 me a.u.−3) Δρ1 (0.6 me a.u.−3)

Δρ2 (0.3 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the HUWYON adduct.8 The charge flux is red → blue. In this

system, all of the deformation maps describe hydrogen bond components between the amino protons

and the sulfur atoms. The metal is practically not involved.

S13

Δρ0 (0.8 me a.u.−3) Δρ1 (1.0 me a.u.−3)

Δρ2 (0.8 me a.u.−3)


maps relative to Δρk (k = 0-2) of the DUKTAF adduct.9 The charge flux is red → blue. In this three-

component system, the two fragments (arbitrarily chosen) are HgBr42- and [H2O

…C5H4NBr2]+. A

different choice could have been [HgBr42-… H2O] and [C5H4NBr2]

+, but for the search of the spodium

bond, the results would be likely similar. Δρ0 is just polarization, in particular due to the repulsion

between the lone pairs of two iodine atoms, Δρ1 is a halogen bond and Δρ2 a hydrogen bond between

the anion and the water. Also in this case, the metal is never involved.

S14

Δρ0 (1.0 me a.u.−3) Δρ1 (1.0 me a.u.−3)


maps relative to Δρk (k = 0 and 1) of the KUSMAM adduct.10 The charge flux is red → blue. In this

system there are a cationic mercury moiety and an anionic one, both of which with chlorine atoms

coordinated. In this context, the chloride of the anionic moiety establishes a “spodium bond” with the

cationic metal (Δρ0), whereas another chlorine bound to the anionic moiety establishes a chalcogen

bond with one of the sulfur atoms bound the cationic fragment.

S15

Δρ0 (1.0 me a.u.−3) Δρ1 (0.6 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the BEJGOM adduct.11 The charge flux is red → blue. The

nitrate establishes a spodium bond with the mercury (Δρ0) and a hydrogen bond with a CH of the

ligand (Δρ1).

Δρ0 (0.7 me a.u.−3) Δρ1 (0.3 me a.u.−3)


maps relative to Δρk (k = 1 and 2) of the DEZGEV adduct.12 The charge flux is red → blue. The

acetonitrile establishes a spodium bond with the mercury (Δρ0), whereas Δρ1 is only a polarization

contribution. Generally, the acetonitrile coordinates a metal with a M-N-C angle of 180°, while here

the Hg-N-C angle is 115°, therefore also in this case it is not a standard coordination bond.

S16

Table S1. EDA results, in kcal/mol, for all the adducts considered here.

Adduct Eint Eorb Est Edisp

1CH3CN -9.4 -6.2 -2.2 -0.9

1CO -4.4 -2.8 -1.2 -0.4

1CH2O -9.0 -8.2 -0.1 -0.7

1CH2S -10.5 -11.8 2.2 -0.9

1NH3 -21.9 -16.9 -4.3 -0.7

2CO -3.4 -2.4 -0.4 -0.6

3CH3CN -7.6 -3.8 -2.8 -1.1

3CO -3.2 -1.5 -1.2 -0.5

3CH2O -6.1 -3.0 -2.5 -0.7

3CH2S -6.9 -3.6 -2.5 -0.8

4CH2O -7.5 -4.5 -2.4 -0.6

5CH3CN -8.3 -4.8 -2.4 -1.1

5CO -3.6 -2.1 -0.9 -0.6

5CH2O -6.9 -4.6 -1.6 -0.7

5CH2S -8.2 -6.1 -1.2 -0.9

ASEZIJ-a -8.8 -6.1 -2.3 -0.4

ASEZIJ-b -15.2 -14.8 0.0 -0.5

YAGGET -17.4 -3.2 -13.5 -0.7

VARCEY 1.1 -3.8 6.9 -2.0

GOVLAE -21.6 -6.6 -12.8 -2.2

PEKSUT -1.6 -6.5 6.9 -2.0

CTURCD -2.9 -6.1 5.3 -2.1

OTOFOU 206.5 -14.1 221.2 -0.7

HUWYON -25.6 -10.4 -13.0 -2.2

DUKTAF -133.4 -19.7 -112.5 -1.1

KUSMAM -117.5 -23.5 -91.7 -2.4

BEJGOM -76.3 -14.2 -60.7 -1.5

DEZGEV -17.7 -6.2 -9.5 -2.0

S17

Table S2. NOCV eigenvalues υk for all the adducts considered here.

υ0 υ1 υ3 υ4 υ5

1CH3CN 0.14 0.10 0.06 0.05 0.04

1CO 0.12 0.08 0.06 0.02 0.02

1CH2O 0.20 0.11 0.07 0.05 0.03

1CH2S 0.30 0.13 0.11 0.05 0.03

1NH3 0.35 0.08 0.07 0.06 0.04

2CO 0.11 0.08 0.07 0.02 0.02

3CH3CN 0.11 0.06 0.04 0.03 0.03

3CO 0.09 0.05 0.04 0.02 0.01

3CH2O 0.10 0.07 0.04 0.03 0.03

3CH2S 0.11 0.09 0.05 0.03 0.03

4CH2O 0.13 0.10 0.05 0.04 0.03

5CH3CN 0.12 0.10 0.04 0.04 0.04

5CO 0.10 0.06 0.05 0.03 0.02

5CH2O 0.14 0.10 0.04 0.04 0.03

5CH2S 0.20 0.11 0.07 0.04 0.03

ASEZIJ-a 0.30 0.05 0.03 0.03 0.02

ASEZIJ-b 0.46 0.05 0.04 0.04 0.03

YAGGET 0.11 0.05 0.04 0.02 0.02

VARCEY 0.11 0.07 0.05 0.04 0.04

GOVLAE 0.15 0.10 0.07 0.05 0.04

PEKSUT 0.17 0.10 0.07 0.06 0.05

CTURCD 0.16 0.09 0.08 0.06 0.06

OTOFOU 0.16 0.15 0.10 0.09 0.09

HUWYON 0.15 0.12 0.12 0.09 0.06

DUKTAF 0.33 0.30 0.16 0.11 0.07

KUSMAM 0.26 0.21 0.16 0.11 0.10

BEJGOM 0.22 0.11 0.09 0.07 0.07

DEZGEV 0.16 0.07 0.07 0.05 0.04

S18

DFT-optimized coordinates

21 1CO Cd -0.8503358 0.3477284 0.0000000 S 0.6248150 0.9803771 -2.0013229 C 0.3905361 -0.2072297 -3.1898518 N 0.6966292 0.1018251 -4.4652231 H 0.7240333 -0.5949072 -5.1894430 H 1.0527610 1.0209826 -4.6566746 N -0.0687883 -1.4304731 -2.9470044 H -0.2740215 -2.0640687 -3.7019642 H -0.3030002 -1.7176225 -1.9945550 S 0.6248150 0.9803771 2.0013229 C 0.3905361 -0.2072297 3.1898518 N 0.6966292 0.1018251 4.4652231 H 0.7240333 -0.5949072 5.1894430 H 1.0527610 1.0209826 4.6566746 N -0.0687883 -1.4304731 2.9470044 H -0.2740215 -2.0640687 3.7019642 H -0.3030002 -1.7176225 1.9945550 C -0.2684705 3.5716883 0.0000000 O -0.7325420 4.6117002 0.0000000 Cl -2.9440858 1.4323074 0.0000000 Cl -0.8904952 -2.1411914 0.0000000 25 1CH3CN S 1.4186331 -0.1190058 -2.2600110 C 0.3129630 -0.9048271 -3.2837723 N 0.2030015 -0.4651654 -4.5548279 H -0.2503260 -1.0183262 -5.2619383 H 0.8013555 0.2892045 -4.8407631 N -0.4526328 -1.9262144 -2.9201652 H -1.1848485 -2.2604507 -3.5250643 H -0.3737025 -2.3266048 -1.9813301 S 1.4186331 -0.1190058 2.2600110 C 0.3129630 -0.9048271 3.2837723 N 0.2030015 -0.4651654 4.5548279 H -0.2503260 -1.0183262 5.2619383 H 0.8013555 0.2892045 4.8407631 N -0.4526328 -1.9262144 2.9201652 H -1.1848485 -2.2604507 3.5250643 H -0.3737025 -2.3266048 1.9813301 N 1.7995749 2.1268125 0.0000000 C 0.8748358 2.8463377 0.0000000 C -0.3054573 3.6946649 0.0000000

S19

H -0.3105326 4.3231856 -0.8876941 H -1.1802954 3.0433921 0.0000000 H -0.3105326 4.3231856 0.8876941 Cd 0.3392578 -0.4658222 0.0000000 Cl -1.8460287 0.5395105 0.0000000 Cl -0.0097085 -2.9684868 0.0000000 23 1CH2O S -0.3073834 1.5088618 -2.3400684 C 0.4918221 0.2820962 -3.2086779 N -0.0277669 -0.1065231 -4.3885682 H 0.4860910 -0.6894637 -5.0267605 H -0.8755813 0.3328829 -4.6984440 N 1.6116498 -0.3025680 -2.8034157 H 1.9384375 -1.1438938 -3.2504945 H 2.0361423 -0.0325046 -1.9101795 S -0.3073834 1.5088618 2.3400684 C 0.4918221 0.2820962 3.2086779 N -0.0277669 -0.1065231 4.3885682 H 0.4860910 -0.6894637 5.0267605 H -0.8755813 0.3328829 4.6984440 N 1.6116498 -0.3025680 2.8034157 H 1.9384375 -1.1438938 3.2504945 H 2.0361423 -0.0325046 1.9101795 O -2.4928959 1.1446069 0.0000000 Cl -0.4443231 -1.7771128 0.0000000 Cl 2.6181593 0.6497352 0.0000000 C -3.2533640 0.1898027 0.0000000 H -4.3404715 0.3491102 0.0000000 H -2.8677720 -0.8363786 0.0000000 Cd 0.0738451 0.5824613 0.0000000 23 1CH2S S -0.0827006 1.7291071 -2.4317890 C 0.5393920 0.2686712 -3.0594208 N -0.1543730 -0.3702624 -4.0153217 H 0.1508085 -1.2523377 -4.3907967 H -1.0854634 -0.0497845 -4.2116181 N 1.7071787 -0.2392627 -2.6830060 H 1.9276222 -1.1997482 -2.8956430 H 2.1965938 0.1888753 -1.8904427 S -0.0827006 1.7291071 2.4317890 C 0.5393920 0.2686712 3.0594208 N -0.1543730 -0.3702624 4.0153217 H 0.1508085 -1.2523377 4.3907967 H -1.0854634 -0.0497845 4.2116181 N 1.7071787 -0.2392627 2.6830060 H 1.9276222 -1.1997482 2.8956430

S20

H 2.1965938 0.1888753 1.8904427 S -2.6601114 1.6969818 0.0000000 Cl -0.3011303 -1.4397684 0.0000000 Cl 2.7287941 1.0154471 0.0000000 C -3.3049712 0.2130919 0.0000000 H -4.3834076 0.0831451 0.0000000 H -2.6678844 -0.6689992 0.0000000 Cd 0.1905946 0.9495856 0.0000000 23 1nh3 Cd 1.75074171417487 -0.34499620384956 0.61972979654036 S 2.38693976089007 2.32020092280199 0.99315052784198 C 1.37528767969345 2.69781134847804 -0.34292143702461 N 0.28888489758096 3.46134836974005 -0.16604160966000 H -0.43464905248969 3.47028489014231 -0.86903652308861 H -0.01584116956664 3.58153595171730 0.78506215303234 N 1.66596552938858 2.29975756506253 -1.57701034939502 H 0.95979260219891 2.34089558075180 -2.29631018394208 H 2.38764538753477 1.58915275127563 -1.69577356102890 S 1.42394425853998 -3.07013972783836 0.96278082046443 C 0.36830249010397 -3.07983613614854 -0.39283987987891 N -0.90921505265737 -3.45185305552763 -0.24187619433201 H -1.58522033369031 -3.24150386581215 -0.96011338507132 H -1.25374267268339 -3.49292725204414 0.70202498048189 N 0.79360531413497 -2.78334993954142 -1.61600736343591 H 0.12573426769626 -2.59090415411026 -2.34708567726225 H 1.71083555995876 -2.34831503086354 -1.71741112386349 Cl -0.67308839947927 0.09187023973704 0.03348097189145 Cl 3.19706791355752 -0.58663675379595 -1.41762868064508 H 2.14801861361687 -0.39595227959865 3.60691439510320 N 1.37870398956192 -0.30068583076451 2.95627487153316 H 0.71241682279327 -1.04729274719650 3.12317491939421 H 0.92086987914155 0.58953535738453 3.11946253234517 21 2CO Cd 0.7944321 -0.4796226 0.0000000 S 1.8101975 0.0436643 -2.2671793 C 0.2733163 -0.2134045 -2.9748660 N -0.3050397 0.7812336 -3.6578824 H -1.2639341 0.7130257 -3.9596242 H 0.0934022 1.6982039 -3.5514528 N -0.3505307 -1.3877562 -2.9161873 H -1.3355785 -1.4451445 -3.1274181 H 0.0199375 -2.0996574 -2.2887196 S 1.8101975 0.0436643 2.2671793 C 0.2733163 -0.2134045 2.9748660 N -0.3050397 0.7812336 3.6578824 H -1.2639341 0.7130257 3.9596242 H 0.0934022 1.6982039 3.5514528

S21

N -0.3505307 -1.3877562 2.9161873 H -1.3355785 -1.4451445 3.1274181 H 0.0199375 -2.0996574 2.2887196 C 1.4341260 2.8679927 0.0000000 O 1.0325872 3.9352006 0.0000000 I -1.6609288 0.7298625 0.0000000 I 0.5162424 -3.2337632 0.0000000 21 3CO S 1.4788923 0.5038953 -1.9614695 C 0.3729415 -0.1796946 -3.0620419 N 0.1213895 0.4788292 -4.2052085 H -0.4616994 0.0934387 -4.9279537 H 0.5037697 1.4003337 -4.3173459 N -0.2280683 -1.3484639 -2.8697587 H -1.0092276 -1.6236821 -3.4426628 H -0.0561576 -1.8675646 -2.0069528 S 1.4788923 0.5038953 1.9614695 C 0.3729415 -0.1796946 3.0620419 N 0.1213895 0.4788292 4.2052085 H -0.4616994 0.0934387 4.9279537 H 0.5037697 1.4003337 4.3173459 N -0.2280683 -1.3484639 2.8697587 H -1.0092276 -1.6236821 3.4426628 H -0.0561576 -1.8675646 2.0069528 C 0.1615973 3.3415265 0.0000000 O -0.7365464 4.0432315 0.0000000 Cl -1.7265612 0.4342882 0.0000000 Cl 0.4692589 -2.5180361 0.0000000 Zn 0.3885715 -0.2151934 0.0000000 25 3CH3CN S 1.1760625 0.2570181 -1.9551357 C 0.3303319 -0.6760978 -3.1002416 N 0.0701351 -0.1231160 -4.2998436 H -0.2318957 -0.6783364 -5.0821176 H 0.3903583 0.8147809 -4.4636662 N -0.0761820 -1.9234099 -2.8945667 H -0.7061219 -2.3724167 -3.5389909 H 0.1236164 -2.3853938 -2.0065335 S 1.1760625 0.2570181 1.9551357 C 0.3303319 -0.6760978 3.1002416 N 0.0701351 -0.1231160 4.2998436 H -0.2318957 -0.6783364 5.0821176 H 0.3903583 0.8147809 4.4636662 N -0.0761820 -1.9234099 2.8945667 H -0.7061219 -2.3724167 3.5389909 H 0.1236164 -2.3853938 2.0065335

S22

N 1.9250329 2.9741071 0.0000000 C 0.7542713 3.0117946 0.0000000 C -0.7008945 3.0470382 0.0000000 H -1.0554617 3.5687622 -0.8865642 H -1.1016737 2.0317525 0.0000000 H -1.0554617 3.5687622 0.8865642 Zn 0.2723843 -0.6915090 0.0000000 Cl -1.9320964 -0.4013025 0.0000000 Cl 0.7412902 -2.9354622 0.0000000 23 3CH2O S -0.3988164 1.1499375 -1.9445374 C 0.4520061 0.2756608 -3.1277674 N -0.0901351 0.1790966 -4.3577558 H 0.4498045 -0.1305044 -5.1475919 H -0.9692942 0.6370047 -4.5198955 N 1.6235869 -0.3164194 -2.9246207 H 2.0073675 -0.9477625 -3.6083245 H 2.0864010 -0.2345639 -2.0184842 S -0.3988164 1.1499375 1.9445374 C 0.4520061 0.2756608 3.1277674 N -0.0901351 0.1790966 4.3577558 H 0.4498045 -0.1305044 5.1475919 H -0.9692942 0.6370047 4.5198955 N 1.6235869 -0.3164194 2.9246207 H 2.0073675 -0.9477625 3.6083245 H 2.0864010 -0.2345639 2.0184842 O -2.9897984 1.2891856 0.0000000 Cl -0.2249313 -2.0486804 0.0000000 Cl 2.6877502 0.2316377 0.0000000 C -3.2953368 0.1107631 0.0000000 H -4.3530151 -0.1987333 0.0000000 H -2.5396413 -0.6874337 0.0000000 Zn 0.3931318 0.0783623 0.0000000 23 3CH2S S -0.3080158 1.2506865 -1.9579546 C 0.4837090 0.2876121 -3.1158719 N -0.0879312 0.1556834 -4.3270882 H 0.4052558 -0.2454337 -5.1060531 H -0.9698677 0.6090657 -4.4857576 N 1.6384461 -0.3345447 -2.9067360 H 1.9780535 -1.0226345 -3.5584987 H 2.1167716 -0.2324712 -2.0106470 S -0.3080158 1.2506865 1.9579546 C 0.4837090 0.2876121 3.1158719 N -0.0879312 0.1556834 4.3270882

S23

H 0.4052558 -0.2454337 5.1060531 H -0.9698677 0.6090657 4.4857576 N 1.6384461 -0.3345447 2.9067360 H 1.9780535 -1.0226345 3.5584987 H 2.1167716 -0.2324712 2.0106470 S -3.2802922 1.6371554 0.0000000 Cl -0.2310171 -1.9354071 0.0000000 Cl 2.7405705 0.2575836 0.0000000 C -3.3699645 0.0218552 0.0000000 H -4.3324557 -0.4841313 0.0000000 H -2.4830492 -0.6099183 0.0000000 Zn 0.4433656 0.1769354 0.0000000 23 4CH2O S -1.94912098958993 -0.57837272316930 -0.70114957373374 C -2.74233134870818 0.66664786591978 0.18395185420413 N -4.04376286565034 0.88456968222457 -0.06280398783033 H -4.59190163330959 1.53017776559058 0.48023406314953 H -4.48670364618057 0.37760147393721 -0.80783130187716 N -2.14791608206820 1.39506823060903 1.11180128812911 H -2.59684315173387 2.21883842560647 1.47860568334733 H -1.14354073003173 1.24397039288287 1.31231528185913 S 2.02537871620469 -1.13170206158770 -1.13844495346292 C 2.92063338891517 -1.23373007265356 0.32897964985930 N 4.01998836556481 -2.00750675123610 0.31877502239041 H 4.61112106036095 -2.10818964144735 1.12605365622413 H 4.28694064264979 -2.46314670754318 -0.53546165086329 N 2.60236700120976 -0.61105556341171 1.44703079954432 H 3.17779595249886 -0.71021359028495 2.26754065214168 H 1.74594120552962 -0.02230220897879 1.49660308651668 Cl 0.21182725243605 2.36320472245855 -1.73356070540645 F 0.41204950726002 0.76420633610312 1.23085802371931 Zn 0.25947304306026 0.38541436103791 -0.72952876502115 O -0.03995493371654 -0.75949160065226 -3.40867661770142 C -0.54802752331517 0.04763572559461 -4.13334050099777 H -0.75090832449455 -0.18368065760033 -5.20152547081404 H -0.82959490689134 1.05777659660052 -3.77491553337674 21 5CO S 1.7626920 0.5205308 -2.3248543 C 0.3140913 -0.2019000 -2.9221474 N -0.4095301 0.4958646 -3.8055781 H -1.2926700 0.1506040 -4.1444445 H -0.2021633 1.4735403 -3.9093845 N -0.0602400 -1.4255652 -2.5972876 H -1.0096308 -1.7163103 -2.7775196 H 0.4314791 -1.9146838 -1.8359452 S 1.7626920 0.5205308 2.3248543

S24

C 0.3140913 -0.2019000 2.9221474 N -0.4095301 0.4958646 3.8055781 H -1.2926700 0.1506040 4.1444445 H -0.2021633 1.4735403 3.9093845 N -0.0602400 -1.4255652 2.5972876 H -1.0096308 -1.7163103 2.7775196 H 0.4314791 -1.9146838 1.8359452 C 0.3812315 3.3260353 0.0000000 O -0.5221909 4.0209486 0.0000000 Cl -1.3398610 0.3556463 0.0000000 Cl 1.2432259 -2.5570345 0.0000000 Hg 1.1695380 0.0902435 0.0000 25 5CH3CN S 1.4803429 -0.0144665 -2.2960632 C 0.1807630 -0.7848654 -3.1074729 N -0.2334755 -0.2345517 -4.2609287 H -0.8888264 -0.6988501 -4.8660831 H 0.1669648 0.6407954 -4.5463669 N -0.4008949 -1.8938024 -2.6894668 H -1.2701904 -2.1962685 -3.0999117 H -0.1022533 -2.3440723 -1.8137376 S 1.4803429 -0.0144665 2.2960632 C 0.1807630 -0.7848654 3.1074729 N -0.2334755 -0.2345517 4.2609287 H -0.8888264 -0.6988501 4.8660831 H 0.1669648 0.6407954 4.5463669 N -0.4008949 -1.8938024 2.6894668 H -1.2701904 -2.1962685 3.0999117 H -0.1022533 -2.3440723 1.8137376 N 2.4184665 2.4304775 0.0000000 C 1.3124652 2.8179078 0.0000000 C -0.0748041 3.2566632 0.0000000 H -0.2718087 3.8555108 -0.8867310 H -0.7278577 2.3799384 0.0000000 H -0.2718087 3.8555108 0.8867310 Hg 0.7977307 -0.4774574 0.0000000 Cl -1.6559630 0.0366642 0.0000000 Cl 0.6087197 -3.1030525 0.0000000 23 5CH2O S -0.2479848 1.5815594 -2.3128523 C 0.5129427 0.2464492 -3.0769270 N -0.0533760 -0.2219947 -4.2008022 H 0.3772193 -0.9451121 -4.7513770 H -0.9584016 0.1251682 -4.4621333 N 1.6350570 -0.3015973 -2.6513893

S25

H 1.9322765 -1.1935533 -3.0147519 H 2.0858927 0.0384123 -1.7888290 S -0.2479848 1.5815594 2.3128523 C 0.5129427 0.2464492 3.0769270 N -0.0533760 -0.2219947 4.2008022 H 0.3772193 -0.9451121 4.7513770 H -0.9584016 0.1251682 4.4621333 N 1.6350570 -0.3015973 2.6513893 H 1.9322765 -1.1935533 3.0147519 H 2.0858927 0.0384123 1.7888290 O -2.8314192 1.4034912 0.0000000 Cl -0.2666660 -1.5741968 0.0000000 Cl 2.8058111 0.7957730 0.0000000 C -3.3164352 0.2852206 0.0000000 H -4.4092080 0.1483728 0.0000000 H -2.6830515 -0.6121595 0.0000000 Hg 0.1337175 0.8948354 0.0000000 23 5CH2S S -0.1098234 1.6796995 -2.3309636 C 0.5498171 0.2569122 -3.0339058 N -0.0894423 -0.2596339 -4.0944557 H 0.2565774 -1.0722631 -4.5762531 H -1.0056260 0.0884036 -4.3134602 N 1.6689376 -0.3059032 -2.6201261 H 1.9005867 -1.2416454 -2.9157740 H 2.1505005 0.0610968 -1.7848513 S -0.1098234 1.6796995 2.3309636 C 0.5498171 0.2569122 3.0339058 N -0.0894423 -0.2596339 4.0944557 H 0.2565774 -1.0722631 4.5762531 H -1.0056260 0.0884036 4.3134602 N 1.6689376 -0.3059032 2.6201261 H 1.9005867 -1.2416454 2.9157740 H 2.1505005 0.0610968 1.7848513 S -3.0677501 1.7689569 0.0000000 Cl -0.2635046 -1.4586333 0.0000000 Cl 2.8736708 0.8212930 0.0000000 C -3.3850192 0.1816683 0.0000000 H -4.4109324 -0.1783228 0.0000000 H -2.5848543 -0.5575136 0.0000000 Hg 0.1953350 1.0092189 0.0000000 18 ASEZIJ Br -0.30335 -1.14091 5.71444 Br 0.00000 0.00000 3.75600 Zn -2.41208 -4.05292 7.54638 Br -4.48771 -3.09835 7.95457

S26

Br -0.56803 -2.78717 8.31961 Br -2.09503 -4.65850 5.17626 Zn -1.98453 -6.99982 6.00460 Br 0.09110 -7.95439 5.59641 Br -3.82855 -8.26553 5.23129 Br -2.30155 -6.39419 8.37463 Zn 0.00000 0.00000 0.00000 Br -2.07563 0.95457 0.40819 Br 1.84405 1.26575 0.77323 Br 0.31705 -0.60558 -2.37012 Zn 0.42755 -2.94690 -1.54178 Br 2.50318 -3.90147 -1.94997 Br -1.41647 -4.21260 -2.31509 Br 0.11053 -2.34127 0.82825 42 BEJGOM Hg 0.00000 0.00000 0.00000 C 1.28260 1.55620 -0.24013 C -3.19965 -1.09851 0.22058 C -4.51903 -1.18260 0.67789 C -4.97989 -0.13110 1.49393 C -4.15572 0.90939 1.77360 C -2.87184 0.93054 1.26219 C -2.60389 -2.28796 -0.58742 C -1.44136 -2.92489 0.25303 C -1.57468 -4.25142 0.64685 C -0.55931 -4.79039 1.42204 C 0.51454 -4.02830 1.79191 C 0.54694 -2.70378 1.35216 C -2.14527 -1.78885 -1.97876 C -2.89431 -2.09306 -3.12004 C -2.44452 -1.61180 -4.33944 C -1.27832 -0.90247 -4.41740 C -0.62854 -0.61477 -3.25965 N -2.39313 -0.07042 0.49252 N -0.39624 -2.17596 0.58822 N -1.03885 -1.06641 -2.04922 O -3.65233 -3.21958 -0.73086 H 1.78007 1.47171 -1.19976 H 2.01582 1.54243 0.54668 H 0.72805 2.48003 -0.20506 H -5.15161 -2.01380 0.41901 H -5.98658 -0.16073 1.90384 H -4.50546 1.72663 2.38736 H -2.23389 1.76769 1.48833 H -2.43612 -4.83370 0.36489 H -0.61156 -5.82091 1.73999 H 1.30328 -4.43379 2.39019 H 1.37712 -2.07041 1.64922 H -3.79542 -2.66977 -3.05169

S27

H -3.01734 -1.81966 -5.23165 H -0.89144 -0.57744 -5.37212 H 0.24817 0.00018 -3.30493 H -3.68059 -3.74546 -1.22621 O -0.00000 0.00000 2.97333 N -0.34602 1.00147 3.55349 O -0.19937 2.15489 3.04301 O -0.81565 0.93983 4.67431 38 CTURCD Cd 0.00000 0.00000 0.00000 Cl 0.00000 2.53421 -0.22970 Cl 0.00000 -0.81161 -2.38322 S -2.25636 -0.58256 0.93113 N -4.68840 -0.42805 0.02367 H -5.29854 -0.42416 -0.58243 H -4.90563 -0.35839 0.85291 N -3.14129 -0.64454 -1.59894 H -3.77162 -0.63781 -2.18401 H -2.32217 -0.71942 -1.85009 C -3.43115 -0.53994 -0.31531 S 2.25636 -0.58256 0.93113 C 3.43115 -0.53994 -0.31531 N 4.68840 -0.42805 0.02367 H 5.29854 -0.42416 -0.58243 H 4.90563 -0.35839 0.85291 N 3.14129 -0.64454 -1.59894 H 3.77162 -0.63781 -2.18401 H 2.32217 -0.71942 -1.85009 Cd 0.00000 0.81161 5.75606 Cl 0.00000 3.34583 5.52636 Cl -0.00000 0.00000 3.37284 S -2.25636 0.22905 6.68720 N -4.68840 0.38356 5.77973 H -5.29854 0.38746 5.17364 H -4.90563 0.45322 6.60898 N -3.14129 0.16708 4.15712 H -3.77162 0.17381 3.57206 H -2.32217 0.09219 3.90597 C -3.43115 0.27168 5.44075 S 2.25636 0.22905 6.68720 C 3.43115 0.27168 5.44075 N 4.68840 0.38356 5.77973 H 5.29854 0.38746 5.17364 H 4.90563 0.45322 6.60898 N 3.14129 0.16708 4.15712 H 3.77162 0.17381 3.57206 H 2.32217 0.09219 3.90597 55

S28

DEZGEV Hg 0.00000 0.00000 0.00000 O -1.53504 4.62527 0.80491 N -0.00186 -2.99195 0.49439 C -0.73150 -1.84751 0.56406 O -2.92228 -1.93044 3.55471 N -1.93236 -2.20099 1.02196 C -0.77966 -4.06539 0.90915 H -0.51842 -4.95676 0.95331 N 1.91969 -1.87711 -0.15912 C -1.97465 -3.57094 1.23280 H -2.70451 -4.05610 1.54369 N 3.27979 -4.24338 -0.53810 C 1.35412 -3.04173 0.05773 N -4.21687 -0.20084 2.97744 H -4.48440 -0.07002 3.78385 H -4.50215 0.30429 2.34297 C 3.18826 -1.89816 -0.58058 H 3.62911 -1.09733 -0.74938 N 1.11511 2.28536 -1.64507 C 3.85284 -3.08865 -0.76923 H 4.73324 -3.07180 -1.06881 N 0.63042 3.02717 0.30151 C 2.02451 -4.23776 -0.12888 H 1.58885 -5.04255 0.03544 N 1.04817 0.12376 -2.50025 C -3.04653 -1.28656 1.24843 H -3.82634 -1.60759 0.76941 H -2.81865 -0.41182 0.89851 N 1.63164 1.04737 -5.05453 C -3.37904 -1.16441 2.71658 N -0.95619 4.79579 2.97509 H -1.51236 5.43459 3.12633 H -0.45855 4.50027 3.61044 C 0.55669 1.92685 -0.45976 C 1.52776 3.60510 -1.60044 H 1.94141 4.08381 -2.28252 C 1.21262 4.05475 -0.37854 H 1.36324 4.91199 -0.05357 C 1.22022 1.40295 -2.76603 C 1.17016 -0.70847 -3.53057 H 1.03452 -1.61968 -3.40335 C 1.49624 -0.23761 -4.78732 H 1.62515 -0.85124 -5.47430 C 1.46786 1.88880 -4.03623 H 1.52185 2.80622 -4.17984 C 0.14205 3.15443 1.67272 H 0.88746 3.33580 2.26620 H -0.26901 2.32057 1.94977 C -0.86951 4.27397 1.77488 N 0.00000 -0.00000 3.11503

S29

C 0.86110 -0.55117 3.59104 C 1.98752 -1.22951 4.19738 H 1.98192 -1.07493 5.14491 H 1.92318 -2.17200 4.02675 H 2.80357 -0.89083 3.82328 20 DUKTAF N -2.31980 -0.96203 5.16962 H -2.33171 -1.44129 4.45644 C -3.29205 -1.10389 6.06848 C -3.30990 -0.35350 7.20530 H -3.98726 -0.45978 7.83437 Br -4.62246 -2.35320 5.68380 C -2.30578 0.56428 7.40306 H -2.30454 1.09156 8.16954 Br 0.00000 0.00000 4.03922 C -1.29786 0.71121 6.47127 H -0.62242 1.33699 6.59872 C -1.31416 -0.08088 5.36150 Br -2.21552 1.02156 0.95948 Hg 0.00000 0.00000 -0.00000 Br 0.25355 1.12269 -2.32331 Br -0.50234 -2.57162 0.08454 Br 2.17213 0.26072 1.39153 O -2.21736 -2.49777 3.03266 H -1.90015 -2.24982 2.23365 H -2.50279 -3.24931 3.12247 38 GOVLAE Zn 0.00000 0.00000 0.00000 N -0.03939 1.95432 0.05306 C -0.02857 3.11988 0.09789 S -0.05333 4.44877 0.18005 N -1.65316 -0.90882 0.43410 C -2.51646 -1.64227 0.69752 S -3.71393 -2.67014 1.03699 N 0.82651 -0.61243 -1.80521 H 0.25378 -1.22890 -2.22359 H 0.96083 0.14813 -2.37079 C 2.12478 -1.25357 -1.49450 C 2.74091 -0.63166 -0.25113 N 1.73717 -0.64291 0.84733 H 2.00777 -0.06221 1.53299 H 1.63770 -1.52287 1.17627 H 1.98924 -2.17119 -1.35374 H 2.72234 -1.10970 -2.21123 H 2.99126 0.25631 -0.42046 H 3.48472 -1.14236 0.03042 Zn -0.03210 -4.45254 3.59251

S30

N -0.00203 -2.49769 3.63007 C -0.01841 -1.33137 3.63929 S 0.00000 0.00000 3.61880 N 1.62533 -5.33237 3.11694 C 2.49209 -6.04871 2.81992 S 3.69440 -7.05402 2.43331 N -0.85548 -5.15190 5.36731 H -0.27978 -5.78435 5.75674 H -0.99336 -4.41901 5.96751 C -2.15071 -5.78413 5.02708 C -2.76994 -5.10822 3.81379 N -1.76628 -5.06378 2.71611 H -2.03972 -4.45322 2.05807 H -1.66265 -5.92706 2.34676 H -2.01082 -6.69358 4.84397 H -2.74887 -5.67647 5.74964 H -3.02450 -4.23025 4.02407 H -3.51134 -5.60887 3.50880 62 HUWYON Cd 0.00000 0.00000 -0.00000 Cl 1.73454 1.47183 0.92359 Cl 0.81871 -0.73762 -2.24401 S -0.41984 -2.04661 1.36718 S -2.14695 1.21745 -0.50626 N -2.66625 0.20996 -2.92299 H -3.14644 -0.34841 -2.47901 N -1.32781 2.08260 -2.94707 H -1.29355 2.03249 -3.80504 H -0.91252 2.71310 -2.53595 N -2.09712 -3.99597 0.97369 H -2.17286 -3.92875 1.82774 N -1.24791 -3.09548 -0.93670 H -1.70368 -3.65358 -1.40507 H -0.74084 -2.52029 -1.32609 C -2.04165 1.16391 -2.24003 C -2.60053 0.04691 -4.31401 H -1.66665 0.00987 -4.57521 H -2.98965 0.82887 -4.73421 C -3.28505 -1.16009 -4.84316 H -3.06771 -1.27006 -5.77144 H -4.23482 -1.05818 -4.74612 H -2.99478 -1.93347 -4.35327 C -1.32507 -3.12109 0.37362 C -2.83569 -5.06917 0.32846 H -2.23336 -5.60633 -0.20898 H -3.51410 -4.69524 -0.25604 C -3.48768 -5.93038 1.38147 H -4.02456 -6.60373 0.95694 H -4.04331 -5.38469 1.94274

S31

H -2.80946 -6.35140 1.91448 S 0.00000 -0.00000 3.85751 Cd -0.41984 -2.04661 5.22470 Cl -2.15438 -3.51844 4.30110 Cl -1.23855 -1.30899 7.46871 S 1.72711 -3.26406 5.73096 N 2.24641 -2.25656 8.14768 H 2.72660 -1.69820 7.70371 N 0.90797 -4.12921 8.17177 H 0.87371 -4.07910 9.02974 H 0.49268 -4.75971 7.76065 N 1.67729 1.94936 4.25101 H 1.75302 1.88214 3.39696 N 0.82807 1.04887 6.16140 H 1.28384 1.60697 6.62977 H 0.32100 0.47368 6.55079 C 1.62181 -3.21052 7.46473 C 2.18069 -2.09352 9.53871 H 1.24681 -2.05648 9.79991 H 2.56981 -2.87548 9.95891 C 2.86521 -0.88652 10.06786 H 2.64787 -0.77655 10.99614 H 3.81498 -0.98843 9.97082 H 2.57494 -0.11314 9.57797 C 0.90524 1.07448 4.85107 C 2.41585 3.02256 4.89624 H 1.81352 3.55972 5.43368 H 3.09426 2.64863 5.48074 C 3.06785 3.88377 3.84323 H 3.60473 4.55712 4.26776 H 3.62347 3.33808 3.28196 H 2.38962 4.30479 3.31022 40 KUSMAM C -0.02512 -6.29892 6.40493 H -0.10008 -7.08695 6.93161 C -1.14795 -5.71773 5.84385 H -2.00740 -6.09176 6.00087 C -1.01768 -4.59286 5.05709 C -2.24193 -3.97661 4.43388 H -2.55642 -3.25378 5.03269 H -2.95219 -4.66567 4.40892 C -1.79701 -4.73449 1.71751 H -2.50970 -5.39632 1.90347 H -1.89489 -4.45294 0.77250 C -0.44936 -5.42345 1.87477 H -0.42448 -6.23139 1.30229 H -0.33654 -5.71083 2.81502 C 2.32329 -5.09464 2.26683 H 1.99644 -5.53749 3.08919

S32

H 2.71164 -5.79120 1.68089 C 3.40409 -4.10373 2.63678 H 3.69405 -3.63994 1.81201 H 4.18210 -4.60951 2.98058 C 2.62407 -3.85269 5.33511 H 3.32632 -4.54743 5.38859 H 2.72677 -3.27252 6.12937 C 1.28035 -4.54816 5.44263 C 1.20415 -5.71557 6.18719 H 1.99331 -6.10971 6.54431 Cl 0.00000 0.00000 3.23900 Hg 0.46723 -2.35239 3.07246 N 0.18659 -3.99141 4.89195 S -2.07738 -3.28825 2.77054 S 0.91886 -4.31500 1.41457 S 2.95903 -2.84290 3.86901 Cl -0.64399 2.26493 0.29997 Cl 2.12680 -1.12777 0.39889 Cl -1.78877 -1.75798 -0.24684 Hg -0.00000 0.00000 0.00000 Cl -0.83678 -4.20528 -3.39020 Cl -3.60756 -0.81258 -3.48912 Cl 0.30801 -0.18237 -2.84340 Hg -1.48077 -1.94035 -3.09023 10 OTOFOU Cd -0.129825 12.514331 33.062348 Cl -0.685040 12.333910 35.395368 Cl -0.945463 14.453801 31.768444 Cl 2.284888 13.378429 33.242727 Cl 0.067638 10.549821 31.641534 Cd -3.133622 9.842669 31.359046 Cl -2.578407 10.023090 29.026025 Cl -2.317984 7.903199 32.652950 Cl -5.548335 8.978571 31.178666 Cl -3.331085 11.807179 32.779860 38 PEKSUT Cd 0.000000 0.000000 0.000000 Br -2.644420 0.344200 -0.201550 Br 0.766580 -0.099780 -2.521220 S 0.845520 2.173270 0.961670 C 0.943870 3.379970 -0.229090 N 1.114390 4.618240 0.134500 H 1.190250 5.285720 -0.509550 H 1.162040 4.833270 1.036350 N 0.885720 3.141720 -1.549250 H 0.961020 3.791520 -2.105500 H 0.773660 2.339670 -1.834710

S33

S 0.261020 -2.317300 0.961670 C 0.047190 -3.508970 -0.229090 N -0.104950 -4.749630 0.134500 H -0.202490 -5.414290 -0.509550 H -0.113930 -4.969700 1.036350 N 0.051960 -3.263780 -1.549250 H -0.041590 -3.911200 -2.105500 H 0.148960 -2.459760 -1.834710 Cd -0.766580 0.099780 5.939100 Br -3.411010 0.443980 5.737550 Br 0.000000 0.000000 3.417880 S 0.078940 2.273050 6.900770 C 0.177290 3.479750 5.710010 N 0.347810 4.718020 6.073600 H 0.423660 5.385500 5.429550 H 0.395460 4.933050 6.975450 N 0.119140 3.241500 4.389850 H 0.194430 3.891300 3.833600 H 0.007080 2.439450 4.104390 S -0.505560 -2.217520 6.900770 C -0.719390 -3.409190 5.710010 N -0.871530 -4.649850 6.073600 H -0.969080 -5.314510 5.429550 H -0.880510 -4.869920 6.975450 N -0.714620 -3.164000 4.389850 H -0.808170 -3.811420 3.833600 H -0.617630 -2.359980 4.104390 38 VARCEY C 0.64361 3.23340 -0.11319 N 0.76335 4.45352 0.34669 N 0.38450 3.08111 -1.37957 S 0.83429 1.93922 0.98954 Cl 0.42341 0.00000 -2.22655 Cl -2.29130 0.00000 0.21269 Zn 0.00000 0.00000 0.00000 H 0.36142 2.30921 -1.73645 H 0.33659 3.76089 -1.87962 H 0.89318 4.55480 1.18253 H 0.69287 5.11333 -0.19269 C 0.64361 -3.23340 -0.11319 N 0.76335 -4.45352 0.34669 N 0.38450 -3.08111 -1.37957 S 0.83429 -1.93922 0.98954 H 0.36142 -2.30921 -1.73645 H 0.33659 -3.76089 -1.87962 H 0.89318 -4.55480 1.18253 H 0.69287 -5.11333 -0.19269 Cl 0.00000 0.00000 3.63357 Cl -2.71472 0.00000 6.07281

S34

Zn -0.42341 0.00000 5.86012 C 0.22020 3.23340 5.74693 N 0.33993 4.45352 6.20681 N -0.03892 3.08111 4.48055 S 0.41088 1.93922 6.84966 H -0.06199 2.30921 4.12368 H -0.08683 3.76089 3.98050 H 0.46977 4.55480 7.04266 H 0.26946 5.11333 5.66743 C 0.22020 -3.23340 5.74693 N 0.33993 -4.45352 6.20681 N -0.03892 -3.08111 4.48055 S 0.41088 -1.93922 6.84966 H -0.06199 -2.30921 4.12368 H -0.08683 -3.76089 3.98050 H 0.46977 -4.55480 7.04266 H 0.26946 -5.11333 5.66743 20 YAGGET Zn 7.194042 2.377041 15.221184 N 6.170256 1.526231 13.718602 H 5.814189 2.159946 13.205885 H 5.521513 1.015493 14.052369 H 6.720545 1.025168 13.231874 N 8.987897 1.418732 15.304459 H 9.042828 0.834436 14.635254 H 9.059298 0.989717 16.081330 H 9.645798 2.013730 15.232991 N 6.281341 2.040382 16.990186 H 6.311100 2.779563 17.484711 H 6.698256 1.379590 17.417883 H 5.432814 1.812963 16.847992 N 7.422060 4.362591 15.142402 H 7.217520 4.653293 14.327105 H 8.266742 4.572075 15.327663 H 6.883829 4.746801 15.737911 H 4.027543 4.099210 15.620962 H 3.984097 3.739259 14.301116 O 4.303185 3.545667 15.045502

S35

References (1) Hausmann, D.; Feldmann, C. Bromine-Rich Zinc Bromides: Zn6Br12(18-Crown-6)2×(Br2)5,

Zn4Br8(18-Crown-6)2×(Br2)3, and Zn6Br12(18-Crown-6)2×(Br2)2. Inorg. Chem. 2016, 55

(12), 6141–6147.

(2) Nithya, K.; Karthikeyan, B.; Ramasamy, G.; Muthu, K.; Meenakshisundaram, S. P. Growth and

Characterization of Fe3+-Doped Bis(Thiourea)Zinc(II) Chloride Crystals. Spectrochim. Acta -

Part A Mol. Biomol. Spectrosc. 2011, 79 (5), 1648–1653.

(3) Qu, Y.; Liu, Z. Di; Tan, M. Y.; Zhu, H. L. Bis[Tetraamminezinc(II)] Tetrapicrate Trihydrate.

Acta Crystallogr. Sect. E Struct. Reports Online 2004, 60 (9), m1343–m1345.

(4) Cameron, E. M.; Louch, W. E.; Cameron, T. S.; Knop, O. Thiocyanates. 1: N-H(N)...S Bonding

in Tetrahedral [Zn(NCS)2L]0 Complexes (L = MexH2-XN(CH2)2NH 2-YMey, x, y = 0-2).

Zeitschrift fur Anorg. und Allg. Chemie 1998, 624 (10), 1629–1641.

(5) Marcos, C.; Alía, J. M.; Adovasio, V.; Prieto, M.; García-Granda, S. Bis(Thiourea)Cadmium

Halides. Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1998, 54 (9), 1225–1229.

(6) Nardelli, M.; Cavalca, L.; Braibanti, A. The Structure of Rhombic Thallous Nitrate. Gazz. Chim.

Ital. 1957, 87, 137.

(7) Li, Q.; Qiu, S. C.; Zhang, J.; Chen, K.; Huang, Y.; Xiao, X.; Zhang, Y.; Li, F.; Zhang, Y. Q.;

Xue, S. F.; et al. Twisted Cucurbit[n]Urils. Org. Lett. 2016, 18 (16), 4020–4023.

(8) Moloto, M. J.; Malik, M. A.; O’Brien, P.; Motevalli, M.; Kolawole, G. A. Synthesis and

Characterisation of Some N-Alkyl/Aryl and N,N′-Dialkyl/Aryl Thiourea Cadmium(II)

Complexes: The Single Crystal X-Ray Structures of [CdCl2(CS(NH2) NHCH3)2]n and

[CdCl2(CS(NH2)NHCH2 CH3)2]. Polyhedron 2003, 22 (4), 595–603.

(9) Al-Far, R. H.; Haddad, S. F.; Ali, B. F. Three Isomorphous 2,6-Dibromo-Pyridinium Tetra-

Bromidometallates: (C 5H4Br2N)2[MBr4] ·2H2O (M = Cu, Cd and Hg). Acta Crystallogr. Sect.

C Cryst. Struct. Commun. 2009, 65 (11), m451–m454.

(10) Sobhia, M. E.; Panneerselvam, K.; Chacko, K. K.; Suh, I. H.; Weber, E.; Reutel, C. Crystal

Structure of the 2:1 Complex of Mercury(II) Chloride with Trithiapyridino-12-Crown-4 Having

Unusual Mercury Coordination. Inorganica Chim. Acta 1992, 194 (1), 93–97.

(11) Canty, A. J.; Chaichit, N.; Gatehouse, B. M.; George, E. E. Coordination Chemistry of

Methylmercury (II). Complexes of Aromatic Nitrogen Donor Tripod Ligands Involving New

S36

Coordination Geometries for MeHgII. Inorg. Chem. 1981, 20 (12), 4293–4300.

(12) Lee, K. M.; Chen, J. C. C.; Huang, C. J.; Lin, I. J. B. Rectangular Architectures Formed by

Acyclic Diamido-Metal-N-Heterocyclic Carbenes with Skewed Conformation. CrystEngComm

2007, 9 (4), 278–281.

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