Structural Measures of Element-Oxygen Bond Covalency from the · 2005-01-18 · 1 Structural...

1

Structural Measures of Element-Oxygen Bond Covalency from the

Changes to the Delocalisation of the Carboxylate Ligand.1

Rosalie K. Hocking and Trevor W. Hambley

SUPPORTING INFORMATION

Figures 6, 7 and 9 given in text in colour:

Figure 6

1 A preliminary account of this work has been reported: Inorg. Chem. 2003, 42, 2833-2835.

SrCa

Mg

Be

Ga

Al

B

In

Tl

C

Si Ge

Sn

Pb

Li

Na

H

ionic limit

*O

Te

*N

P

As

Sb

Bi

I *S

*Se

1.21

1.23

1.25

1.27

1.29

1.31

1.33

1.35

1.37

1.39

0 1 2 3 4 5 6 7Periodic Group Number

C-O

A(…

X)

Bon

d-Le

ngth

(Å

)

-19.00

1.00

21.00

41.00

61.00

81.00

101.00

11

Na

3

Li

19

K37

Rb

1 1413 15 16 172

1.00

1.33

1.50

1

H

5

B

13

Al

31

Ga

49

In

81

T l

14

Si32

Ge50

Sn82

Pb

6

C15

P33

As31

Sb83

Bi

7

N

12

Mg20

Ca38

Sr56

Ba

4

Be

17

Cl

9

F

35

Br53

I85

At

indicates insufficient data for that element.

1.13

1.21

1.70

16

S34

Se54

Te84

Po

8

O16

S34

Se54

Te84

Po

8

O

S16

Se34

Bond O

rder C-O

A

-%

Covalent X-C

arboxylate Bond0

100

60

30

90

80

5040

1020

70

(X-OA Interaction exhibiting some double-bond character)

2

NiII 4c, sq plPtII 4c, sq plRuIII Os(all)

RuII

FeII ls

RhIIIIrIII

CoIII

PtIVMnIV

FeIII hsMnIII lsCrIII

CdII

ZnIINiII hs

CoII hsFeII hsMnII hs

ionic limit

CuII long

CuII short ZnII 4c

ZnII 5c

PdII 4c, sq pl

1.24

1.25

1.26

1.27

1.28

1.29

1.30

1.31

5 6 7 8 9 10 11 12 13Periodic Group Number

C-O

A (…

M)

Bon

d-Le

ngth

(Å)

-10

0

10

20

30

40

50%

Covalent

Metal-C

arboxylate Bond

Figure 7

Figure 9

CuII longMnII hs

CoII

NiII

CuII 5c.

CuII short

NiII sq pl.

CoIII

CuII 4c.

PtIV

PtII sq pl.

MnIIICrIII

FeIII

ZnII 4c.

ZnII 5c.

ZnII

FeII ls

FeII hs

GdIII 9c.

carboxylic acid (H)

ionic limit

1.248

1.258

1.268

1.278

1.288

1.298

1.308

1.85 1.95 2.05 2.15 2.25 2.35

Metal-Carboxylate Bond-Length (Å)

C-O

A (…

M)

Bon

d-Le

ngth

(Å)

1.28

1.33

1.38

1.43

1.48

Bond-O

rder

1.35

1.30

1.24

1.41

1.48

% C

ovalent M

etal-Carboxylate B

ond10

50

20

40

30

0

3

A comment on statistics in this work

Statistical Example: The three scatter-plots representing the two bonds of the carboxylate

group OA-C and OB-C in the carboxylate ion, CoIII-carboxylate interactions and esters.

Figure S.1 represents the scatter plots of three sets of data, that representing the carboxylate group, free (the carboxylate anion), bound to CoIII and to C(ester). It is clear from a cursory examination that the three scatter-plots represent different distributions of data, despite the fact that they have large standard deviations relative to the differences between the distributions. Statisticians approach such situations by looking at the certainty on the mean, and not the distribution of the dataset. Clearly, the larger a data-set is the more certain you are of its mean. Thus if we had only two structures from each group to compare we could not clearly distinguish CoIII carboxylate from that of free carboxylate of the esters. However as the data-set gets larger we are more certain of its mean. The technique used to quantify such phenomena generally involves assuming a distribution, usually a normal distribution, then hypothesis testing of the certainty of the average based on the variation in the sample and its size. A simple way to do this is through the application of confidence intervals (CI). CIs are calculated using the formula, CI = ασN-½ where σ is the standard deviation and N is the number of structures in the sample. The α-value reflects the size of the confidence interval; in this work 95% confidence intervals are quoted on the mean, which corresponds to an α-value of 1.96.16,17

1.15

1.17

1.19

1.21

1.23

1.25

1.27

1.29

1.31

1.15 1.18 1.21 1.24 1.27 1.30 1.33 1.36 1.39 1.42

C-OA Bond-Length (Å)

C-O

B B

ond-

Leng

th (Å

)

Carboxylate Anion

Cobalt(III)

EstersCoIII-Carboxylate

4

Supplementary Figures

N

P

As

Sb

Bi

C

Si

Ge

Sn

Pb

B

AlGa

In

Tl

O

S

Se

Te

SrCa

Mg

Be

1.24

1.26

1.28

1.30

1.32

1.34

1.36

1.38

1.40 1.60 1.80 2.00 2.20 2.40 2.60

C-OA Bond Length (Å)

Elem

ent-O

xyge

n B

ond

Leng

th (Å

) Group 2Group 3Group 4Group 5Group 6

ionic limit

Figure S1. A plot element-oxygen bond length vs OA-C bond length

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.75 0.85 0.95 1.05 1.15 1.25 1.35 1.45 1.55 1.65 1.75C-O Bond-Length (Å)

Ener

gy (

Arb

.)

r = 1.196r = 1.368average

50% double, 50% single

resultant bond-length 1.250 Å

double bond limitr0 = 1.196 Å

single bond limitr0 = 1.368 Å

Figure S2. A plot of the functions representing the two contributions to the carboxylate

anion, a double bond form (blue) and a single bond(pink) form and their average(black).

5

Figure S3. Relationship between bond order, bond length and % ionic character.

Figure S4. Average bond lengths of the bound arm of the carboxylate group (OA-C) for a

series of elements which exhibit have data sets with different coordination numbers.

1.00

1.05

1.10

1.15

1.20

1.25

1.30

1.35

1.40

1.45

1.50

1.24 1.26 1.28 1.30 1.32 1.34 1.36 1.38Bond-Length (Å)

Bon

d-O

rder

C-O

A(…

M)

0

10

20

30

40

50

60

70

80

90

100%

Ionic Character

Poorly defined region

ZnII 6c.

ZnII 5c.

ZnII 4c.CuII 5c.

CuII 4c.

CuII 6c, short

CuII 6c, long

ionic limit

SnII/IV 5c.

SnII/IV 4c.

PbII 6c.

PbII 5c.

PbII 4c.CoII 4c.

CoII 6c.

1.24

1.25

1.26

1.27

1.28

1.29

1.30

0 1 2 3 4 5 6

Metal Centre

C-O

A(...

M)

Bon

d-Le

ngth

(Å

)

-10

0

10

20

30

40

50

% C

ovalent Character

in Metal C

arboxylate Bond

Zn(II)Cu(II) Sn(II/IV) Pb(II)Co(II)

6

Figure S5. A scatter plot of the CoIII-carboxylate bond length vs. the C-OA bond length.

Figure S6. A scatter plot of the NiII-carboxylate bond length vs. the C-OA bond length

for the subsets of all 6-coordinate NiII complexes.

y = -0.1608x + 1.5923R2 = 0.046

1.20

1.22

1.24

1.26

1.28

1.30

1.32

1.34

1.8 1.85 1.9 1.95 2 2.05

CoIII-Carboxylate Bond Length (Å)

C-O

A(..

.M)

Bon

d Le

ngth

(Å)

y = 0.0072x + 1.2519R2 = 0.0004

1.20

1.22

1.24

1.26

1.28

1.30

1.32

1.34

1.95 2.00 2.05 2.10 2.15 2.20

NiII-Carboxylate Bond Length (Å)

C-O

A(..

.M)

Bon

d Le

ngth

(Å)

7

Figure S7. The effect of trans-donors on palladium-carboxylate bonds.

Figure S8. The effect of trans-donors on platinum-carboxylate bonds.

1.26

1.27

1.28

1.29

1.30

C Cl N O Ptrans -donor

C-O

A B

ond-

Leng

th

13

18

23

28

33

38

43

48

53

% C

ovalent Character

1.27

1.28

1.29

1.30

1.31

1.32

C Cl N O P Strans -donor

C-O

A B

ond-

Leng

th (Å

)

25

30

35

40

45

50

55

60

65

70

% C

ovalent Character

8

Figure S9. Periodic trends in first ionization energies, the trends for the first 3 rows and

the most covalent elements follow those of our measure.45

SrCa

Mg

Be

Ga

Al

B

In

Tl

C

Si Ge

Sn

Pb

Li

Na

H

ionic limit

*O

Te

*N

P

As

Sb

Bi

I *S

*Se

1.21

1.23

1.25

1.27

1.29

1.31

1.33

1.35

1.37

1.39

0 1 2 3 4 5 6 7Periodic Group Number

C-O

A(…

X)

Bon

d-Le

ngth

(Å

)

-19.00

1.00

21.00

41.00

61.00

81.00

101.00

1 1413 15 16 172

1.00

1.33

1.50

1.13

1.21

1.70

Figure S10. Repeat of Figure 6 for comparison to the trends in ionisation energies.45

H

LiNa

Be

Mg

CaSr

B

TlAl &Ga

In

C

NO

I

GeSi

BiPb

Sn

PAs

SbTe

2.652.702.752.802.852.902.953.003.053.103.153.20

0 1 2 3 4 5 6 7 8Periodic Group Number

log(

1st I

onis

atio

n En

ergy

(kJ.

moL

-1))

131 1514 1716 182

9

In Figures S8 and S9 we have plotted the C-OA bond length and the 1st ionisation

energies of the main-group elements as a function of group number. There are two clear

correlations between the two measures. Firstly, the sequence B < C < N > O is observed

in both ionisation energies and the variation in bond length. The first ionisation energy of

oxygen is lower than that of nitrogen because its electron configuration requires the

pairing of electrons in the 2p orbitals resulting in a repulsion term not present in boron,

carbon and nitrogen.37 Secondly, the trends going down groups 13-15 are replicated,

particularly those for the elements (Al~Ga), (Si~Ge) and (P~As) which are more similar

than the other member of each group. The similarity of the second and 3rd row

covalence’s is attributable to the change in the spatial and shielding properties of the ns,

np and (n-1)d orbitals.

CoII hs

MnII hs

FeII hs

NiII hs

ZnII

CdII

CrIII

CoIII

Ionic Limit

1.245

1.250

1.255

1.260

1.265

1.270

1.275

1.280

5 6 7 8 9 10 11 12 13Group Number

Ave

rage

C-O

Bon

d Le

ngth

(Å)

for b

iden

tate

car

boxy

late

s

-5

0

5

10

15

20

25

% C

ovalent Character

in Metal-C

arboxylate Bond

FigureS11. Average of C-Obond length vs. group number for the some bidentate

carboxylate groups.

10

Table S1. Data for free carboxylate anions.

Average Median Number Standard

Deviation

Confidence

Interval

1.2505 1.2500 5033 0.0186 0.0005

11

Data for main-group elements

Table S2. Element-carboxylate distances for main-group elements (Å).

MEAN MEDIAN COUNT STDEV CONFIDENCE Li 1.914 1.901 11 0.086 0.051 Na 2.394 2.412 37 0.052 0.017 Ca 2.390 2.387 56 0.053 0.014 Pb 2.469 2.455 27 0.072 0.027 Th 2.529 2.399 28 0.277 0.103 Sr 2.557 2.559 24 0.039 0.015 Mg 2.088 2.075 94 0.067 0.013 Pb 2.542 2.560 120 0.116 0.021 Pb 2.546 2.543 45 0.108 0.032 Bi 2.425 2.410 309 0.143 0.016

Pb 4c 2.409 2.355 12 0.105 0.059 InIII 2.203 2.198 206 0.066 0.009

Sn 5c 2.187 2.172 289 0.083 0.010 Sn 2.163 2.150 610 0.084 0.007

AlIII 1.891 1.888 126 0.030 0.005 Sb 2.202 2.175 462 0.114 0.010 Be 1.623 1.613 50 0.024 0.007 Te 2.222 2.179 20 0.120 0.052

Sn 4c 2.116 2.095 74 0.072 0.016 Ge 5c 1.946 1.918 26 0.065 0.025

Ge 1.905 1.889 97 0.056 0.011 Ge 4c 1.906 1.866 12 0.104 0.059 Ge 6c 1.886 1.885 59 0.012 0.003

H 0.937 0.932 4585 0.127 0.004 Sn 6c 2.168 2.124 62 0.106 0.026 Si 5c 1.794 1.799 217 0.033 0.004

Si 1.789 1.798 233 0.039 0.005 Si 4c 1.680 1.693 9 0.024 0.015

B 1.485 1.487 159 0.034 0.005 GaIII 1.878 1.833 48 0.082 0.023 As 1.878 1.833 48 0.082 0.023 P 1.737 1.749 97 0.049 0.010 C 1.452 1.451 7276 0.018 0.000

N 3c 1.443 1.459 105 0.037 0.007 N 1.435 1.438 209 0.034 0.005

N 2c 1.428 1.433 104 0.029 0.006

12

Table S3. Distance of the element bound carboxylate arm (C-OA) for main-group

elements, (Å)

MEAN MEDIAN COUNT STDEV CONFIDENCE

Li 1.244 1.246 11 0.056 0.010 Na 1.249 1.248 37 0.058 0.002 Ca 1.251 1.252 56 0.009 0.002 Pb 1.251 1.260 27 0.021 0.008 Th 1.251 1.254 28 0.018 0.007 Sr 1.253 1.254 24 0.009 0.004 Mg 1.257 1.256 94 0.009 0.002 Pb 1.257 1.260 120 0.020 0.004 Pb 1.260 1.259 45 0.014 0.004 Bi 1.267 1.271 309 0.035 0.004

Pb 4c 1.267 1.269 12 0.014 0.008 InIII 1.270 1.271 206 0.014 0.002

Sn 5c 1.277 1.279 289 0.021 0.002 Tin 1.283 1.283 610 0.034 0.003 AlIII 1.285 1.284 126 0.013 0.002 Sb 1.285 1.285 462 0.018 0.002 Be 1.285 1.283 50 0.010 0.003 Te 1.287 1.295 20 0.023 0.010

Sn4c 1.291 1.294 74 0.021 0.005 Ge5c 1.292 1.297 26 0.019 0.007 GeIV 1.302 1.306 97 0.018 0.004 Ge 4c 1.305 1.303 12 0.031 0.018 Ge 6c 1.307 1.307 59 0.012 0.003

H 1.307 1.310 4585 0.019 0.001 Sn 6c 1.308 1.293 62 0.057 0.014 Si 5c 1.310 1.309 217 0.012 0.002 Si IV/II 1.310 1.309 233 0.012 0.002 Si 4c 1.316 1.312 9 0.015 0.010

B 1.321 1.323 159 0.013 0.002 GaIII 1.327 1.334 48 0.023 0.006 As 1.327 1.334 48 0.023 0.006 P 1.338 1.329 97 0.026 0.005 C 1.338 1.338 7276 0.018 0.000

N 3c 1.369 1.366 105 0.025 0.005 N 1.371 1.368 209 0.023 0.003

N 2c 1.373 1.369 104 0.022 0.004

13

Table S4. Distance of the unbound carboxylate arm (C-OB) for main-group elements,

(Å)

MEAN MEDIAN COUNT STDEV CONFIDENCE

Li 1.253 1.259 11 0.008 0.0048 Na 1.258 1.256 37 0.011 0.0035 Ca 1.246 1.246 56 0.013 0.0033 Pb 1.235 1.25 27 0.032 0.0122 Th 1.235 1.237 28 0.017 0.0063 Sr 1.257 1.261 24 0.009 0.0038 Mg 1.254 1.251 94 0.012 0.0025 Pb 1.248 1.249 120 0.017 0.0031 Pb 1.243 1.244 45 0.021 0.0061 Bi 1.240 1.236 309 0.027 0.0030

Pb 4c 1.244 1.248 12 0.008 0.0047 InIII 1.236 1.235 206 0.014 0.0019

Sn 5c 1.220 1.220 289 0.019 0.0022 Sn 1.224 1.221 610 0.028 0.0022

Al III 1.225 1.225 126 0.009 0.0015 Sb 1.227 1.226 462 0.016 0.0014 Be 1.233 1.232 50 0.011 0.0030 Te 1.216 1.22 20 0.013 0.0059

Sn 4c 1.220 1.219 74 0.017 0.0039 Ge 5c 1.223 1.219 26 0.017 0.0066

Ge 1.215 1.214 97 0.022 0.0043 Ge 4c 1.198 1.216 12 0.031 0.0173 Ge 6c 1.215 1.211 59 0.019 0.0050

H 1.211 1.208 4585 0.018 0.0005 Sn 6c 1.230 1.225 62 0.039 0.0097 Si 5c 1.215 1.216 217 0.010 0.0013 SiII/IV 1.215 1.215 233 0.010 0.0013 Si 4c 1.204 1.201 9 0.014 0.0094

B 1.210 1.209 159 0.008 0.0012 GaIII 1.214 1.216 48 0.016 0.0047 As 1.214 1.216 48 0.016 0.0047 P 1.199 1.199 97 0.016 0.0032 C 1.197 1.197 7276 0.072 0.0017

N 3c 1.196 1.195 105 0.015 0.0029 N 1.197 1.195 209 0.015 0.0020

N 2c 1.197 1.196 104 0.014 0.0027

14

Table S5. The distance of the adjoining Carbon-Carbon bond, Figure 3 , for main group

elements (Å)

MEAN MEDIAN COUNT STDEV CONFIDENCE Li 1.521 1.515 11 0.008 0.0047 Na 1.527 1.530 37 0.012 0.0040 Ca 1.529 1.526 56 0.025 0.0066 Pb 1.505 1.509 27 0.017 0.0065 Th 1.520 1.521 28 0.015 0.0056 Sr 1.517 1.515 24 0.01 0.0058 Mg 1.516 1.518 94 0.019 0.0038 Pb 1.520 1.522 120 0.015 0.0026 Pb 1.530 1.525 45 0.020 0.0060 Bi 1.520 1.517 309 0.033 0.0037

Pb 4c 1.507 1.508 12 0.013 0.0073 InIII 1.516 1.518 206 0.014 0.0018

Sn 5c 1.521 1.520 289 0.02 0.0026 Tin all 1.518 1.516 610 0.03 0.0025

AlIII 1.526 1.524 126 0.018 0.0032 Sb 1.522 1.518 462 0.022 0.0020 Be 1.512 1.510 50 0.022 0.0061 Te 1.517 1.517 20 0.023 0.0100

Sn 4c 1.508 1.507 74 0.02 0.0048 Ge 5c 1.523 1.524 26 0.014 0.0053

Ge 1.521 1.521 97 0.025 0.0050 Ge 4c 1.532 1.550 12 0.029 0.0506 Ge 6c 1.517 1.515 59 0.021 0.0053

H 1.509 1.508 4585 0.020 0.0006 Sn 6c 1.511 1.519 62 0.05 0.0130 Si 5c 1.523 1.524 217 0.014 0.0019 SiII/IV 1.522 1.523 233 0.015 0.0019 Si 4c 1.501 1.517 9 0.021 0.0135

B 1.514 1.515 159 0.015 0.0023 GaIII 1.509 1.515 48 0.021 0.0058 As 1.509 1.515 48 0.021 0.0058 P 1.501 1.500 97 0.020 0.0040 C 1.501 1.500 7276 0.153 0.0035

N 3c 1.488 1.499 105 0.037 0.0071 N 1.483 1.494 209 0.040 0.0055

N 2c 1.477 1.490 104 0.043 0.0082

15

Data for transition metals

Table S6. Metal-carboxylate distances for main-group elements, (Å).

AVERAGE MEDIAN STDEV CONFIDENCE COUNT Cu(II) Long 6 Coordinate

2.39 2.36 0.143 0.026 119

Cu(II) Short 6 Coordinate

1.96 1.96 0.030 0.003 308

Cu(II) 5 Coordinate

2.00 1.96 0.133 0.009 921

Cu(II) 4 Coordinate

1.95 1.95 0.029 0.003 433

Co(III) octahedral

1.91 1.91 0.025 0.001 1143

Co(II) octahedral

2.09 2.08 0.052 0.006 278

Ni(II) octahedral high spin

2.07 2.06 0.054 0.005 527

Ni(II) Low Spin 4 coordinate

1.87 1.87 0.023 0.007 48

Platinum(II) 4 Coordinate

2.03 2.02 0.032 0.004 249

Platinum(IV) 4 Coordinate

2.01 2.01 0.025 0.005 96

Manganese(II) 6 Coordinate

2.15 2.15 0.054 0.007 215

Manganese(III) 6 Coordinate

1.99 1.95 0.101 0.021 68

Chromium(III) 6 Coordinate

1.97 1.96 0.041 0.004 330

Fe(III) 6 Coordinate

2.00 1.99 0.037 0.001 561

Fe(II) high-spin 6-coordinate

2.10 2.10 0.022 0.005 68

Fe(II) low spin 6-coordinate

2.01 2.02 0.018 0.006 39

Zn(II) 4 coordinate

1.96 1.96 0.038 0.005 181

Zn(II) 5 coordinate

2.03 2.02 0.063 0.011 121

Zn(II) 6 coordinate

2.09 2.09 0.057 0.009 144

Gd(III) 9 coordinate

2.38 2.37 0.045 0.007 150

16

Table S7. Length of the element-bound carboxylate arm (C-OA) for transition metals (Å).

AVERAGE COUNT MEDIAN STDEV CONFIDENCE

Cu(II) Long 6 Coordinate

1.252 119 1.250 0.019 0.003


1.272 308 1.272 0.016 0.002

Cu(II) 5 Coordinate

1.272 921 1.272 0.021 0.001

Cu(II) 4 Coordinate

1.277 433 1.278 0.017 0.002

Co(III) octahedral

1.285 1143 1.286 0.019 0.001

Co(II) octahedral

1.263 278 1.262 0.016 0.002

Ni(II) octahedral high spin

1.267 527 1.266 0.020 0.002


1.290 48 1.291 0.015 0.004


1.292 249 1.294 0.033 0.004


1.301 96 1.298 0.030 0.006


1.265 215 1.264 0.020 0.003


1.286 68 1.285 0.025 0.006


1.288 330 1.290 0.013 0.001


1.284 561 1.28 0.020 0.001


1.259 68 1.261 0.013 0.003


1.278 39 1.279 0.014 0.004

Zn(II) 4 coordinate

1.272 181 1.276 0.025 0.004

Zn(II) 5 coordinate

1.268 121 1.268 0.020 0.004

Zn(II) 6 coordinate

1.262 144 1.262 0.017 0.003


1.266 150 1.266 0.016 0.003

17

Table S8. Length of the unbound carboxylate arm (C-OB) for transition metals, (Å).

AVERAGE

COUNT MEDIAN STDEV CONFIDENCE

Cu(II) Long 6 Coordinate

1.248 1.250 0.022 0.004 119


1.237 1.237 0.016 0.002 308

Cu(II) 5 Coordinate

1.234 1.233 0.016 0.001 921

Cu(II) 4 Coordinate

1.232 1.232 0.017 0.002 433

Co(III) octahedral 1.228 1.227 0.017 0.001 1143 Co(II) octahedral 1.246 1.243 0.030 0.004 278 Ni(II) octahedral high spin

1.246 1.245 0.028 0.002 527


1.227 1.225 0.012 0.003 48


1.227 1.228 0.031 0.004 249


1.216 1.218 0.025 0.005 96


1.242 1.242 0.020 0.003 215


1.230 1.229 0.023 0.005 68


1.223 1.223 0.013 0.001 330


1.228 1.227 0.012 0.001 561


1.223 1.219 0.008 0.002 68


1.246 1.246 0.013 0.003 39

Zn(II) 4 coordinate 1.231 1.229 0.018 0.003 181 Zn(II) 5 coordinate 1.236 1.236 0.015 0.003 121 Zn(II) 6 coordinate 1.243 1.244 0.015 0.002 144 Gd(III) 9 coordinate

1.243 1.242 0.014 0.004 150

18

Table S9. Length of the adjoining carbon-carbon bond, for the transition metals (Å).

AVERAGE MEDIAN STDEV CONFIDENCE COUNT

Cu(II) Long 6-Coordinate

1.520 1.520 0.018 0.003 119

Cu(II) Short 6-Coordinate

1.518 1.518 0.020 0.002 308

Cu(II) 5-Coordinate

1.518 1.519 0.023 0.001 921

Cu(II) 4-Coordinate

1.523 1.522 0.025 0.002 433

Co(III) octahedral

1.522 1.519 0.024 0.001 1143

Co(II) octahedral

1.513 1.515 0.032 0.004 278

Ni(II) octahedral (high spin)

1.521 1.519 0.020 0.002 527


1.516 1.512 0.021 0.006 48


1.522 1.519 0.037 0.005 249


1.525 1.525 0.038 0.008 96


1.516 1.516 0.025 0.003 215


1.516 1.513 0.039 0.009 68


1.527 1.525 0.021 0.002 330


1.523 1.52 0.017 0.001 561

Fe(II) highspin 6-coordinate

1.523 1.523 0.016 0.005 68


1.527 1.524 0.020 0.005 39

Zn(II) 4 coordinate

1.507 1.507 0.023 0.003 181

Zn(II) 5 coordinate

1.517 1.514 0.022 0.004 121

Zn(II) 6 coordinate

1.522 1.523 0.020 0.003 144


1.523 1.519 0.017 0.005 150

19

Data for the lanthanoids and actinoids

Table S10. Metal-carboxylate distances for 9c lanthanoids (Å).

MEAN MEDIAN STDEV CONFIDENCE COUNT

Yb(III) 2.306 2.301 0.024 0.014 12

Tb(III) 2.387 2.386 0.032 0.013 23

Sm(III) 2.410 2.414 0.027 0.011 23

Nd(III) 2.462 2.448 0.081 0.018 75

Lu(III) 2.314 2.303 0.049 0.026 14

La(III) 2.507 2.486 0.058 0.015 61

Gd(III) 2.378 2.370 0.045 0.007 150

Eu(III) 2.422 2.418 0.063 0.013 88

Dy(III) 2.368 2.362 0.047 0.021 19

Ce(III) 2.459 2.479 0.085 0.029 32

Table S11. Distance of the bound carboxylate arm (C-OA) for 9c lanthanoids, (Å).


Yb(III) 1.270 1.272 0.013 0.007 12

Tb(III) 1.269 1.268 0.022 0.009 23

Sm(III) 1.262 1.264 0.015 0.006 23

Nd(III) 1.260 1.259 0.020 0.005 75

Lu(III) 1.259 1.262 0.011 0.006 14

La(III) 1.263 1.262 0.027 0.007 61

Gd(III) 1.266 1.266 0.016 0.003 150

Eu(III) 1.270 1.266 0.028 0.006 88

Dy(III) 1.263 1.264 0.016 0.007 19

Ce(III) 1.268 1.270 0.016 0.006 32

20

Table S12. Distance of the bound carboxylate arm (C-OB) for 9c lanthanoids, Å.


Yb(III) 1.240 1.240 0.004 0.004 12

Tb(III) 1.241 1.239 0.026 0.011 23

Sm(III) 1.242 1.246 0.012 0.005 23

Nd(III) 1.242 1.241 0.003 0.014 75

Lu(III) 1.241 1.245 0.016 0.008 14

La(III) 1.242 1.236 0.028 0.007 61

Gd(III) 1.243 1.241 0.017 0.003 150

Eu(III) 1.245 1.244 0.025 0.005 88

Dy(III) 1.248 1.246 0.018 0.008 19

Ce(III) 1.234 1.232 0.009 0.003 32

Table S13. The distance of the adjoining Carbon-Carbon for the 9c lanthanoids Å.


Yb(III) 1.515 1.513 0.012 0.007 12

Tb(III) 1.512 1.512 0.012 0.005 23

Sm(III) 1.521 1.520 0.026 0.010 23

Nd(III) 1.514 1.509 0.024 0.005 75

Lu(III) 1.517 1.514 0.013 0.007 14

La(III) 1.517 1.517 0.035 0.009 61

Gd(III) 1.518 1.518 0.021 0.003 150

Eu(III) 1.511 1.516 0.028 0.006 88

Dy(III) 1.516 1.522 0.022 0.010 19

Ce(III) 1.511 1.513 0.016 0.006 32

21

Table S14. Metal-carboxylate distances for Actinoids, (Å).


U(III,IV,VI) 2.422 2.416 0.038 0.015 25

Th(IV) 2.379 2.366 0.059 0.028 17

Table S15. Distance of the bound carboxylate arm (C-OA) for 9c actinoids, (Å).


U(III,IV,VI) 1.280 1.276 0.024 0.009 25

Th(IV) 1.272 1.271 0.048 0.023 17

Table S16. Distance of the bound carboxylate arm (C-OB) for 9c actinoids, (Å).


U(III,IV,VI) 1.244 1.238 0.029 0.012 25

Th(IV) 1.243 1.228 0.036 0.017 17

Table S17. The distance of the adjoining carbon-carbon bond, (Å).


U(III,IV,VI) 1.511 1.516 0.031 0.012 25

Th(IV) 1.523 1.515 0.027 0.013 17

22

Data for electronegativity differences Table S18a Table of elements with C-OA bond-length, %covalent character and

electronegativity

Atomic

Number

Element C-OA Bond

Length (Å)

% Covalent Character Electronegativity

(Pauling Scale)

C-OA �(C-OA) % Cov �(%Cov.

)

Electro �(Electro

)

1 H 1.307 0.001 59.9 0.5 2.78 0.01

3 Li 1.250 0.010 0.7 12.4 1.27 0.81

4 Be 1.285 0.003 40.1 2.7 2.54 0.03

5 B 1.321 0.002 70.7 1.5 2.91 0.02

6 C 1.338 0.000 82.4 0.3 3.06 0.00

7 N 1.371 0.003 102 1.7 N/A N/A

7 N 2c 1.373 0.004 103 2.2 N/A N/A

7 N 3c 1.369 0.005 101 2.5 N/A N/A

8 O 1.368 100 0.0 3.47 0.00

8 O 1.352 0.007 91 4.0 3.19 0.08

11 Na 1.250 0.002 1 3.2 1.27 0.43

12 Mg 1.257 0.002 9 2.3 1.94 0.08

13 Al 1.285 0.002 40 2.2 2.55 0.03

14 Si 1.321 0.002 71 1.1 2.91 0.01

14 Si 4c 1.316 0.010 67 7.5 2.87 0.09

14 Si (II/IV) 1.310 0.002 63 1.2 2.82 0.01

15 P 1.338 0.005 82 3.4 3.06 0.05

16 S 1.316 0.014 67 10.8 2.87 0.13

20 Ca 1.251 0.002 1 3.0 1.44 0.30

21 Sc 1.278 0.005 33 5.5 2.45 0.07

22 Ti 1.288 0.003 43 3.3 2.58 0.04

23 V 1.283 0.002 39 1.8 2.53 0.02

24 Cr(III) 1.288 0.001 43 1.3 2.58 0.02

24

Table S20 b. Table of elements with C-OA bond-length, % covalent character and electronegativity

Atomic Number

Element C-OA Bond Length (Å)


(Pauling Scale) C-OA �(C-OA) % Cov �(%Cov.

) Electro �(Electro

) 25 MnII 1.260 0.003 13 3.2 2.07 0.08 25 MnIII 1.286 0.006 41 5.7 2.56 0.07 25 MnIV 1.300 0.009 54 7.8 2.72 0.09 26 FeII hs 1.262 0.003 16 3.6 2.15 0.08 26 FeIII 1.284 0.001 39 1.0 2.53 0.01 26 FeII ls 1.278 0.004 33 4.6 2.45 0.06 27 CoIII 6c 1.285 0.001 41 1.1 2.55 0.01 27 CoII 6c 1.263 0.002 16 2.3 2.16 0.05 28 NiII ls 1.290 0.004 45 3.9 2.61 0.05 28 NiII 6c

hs 1.267 0.002 21 1.9 2.25 0.04

29 CuII 6c Short

1.272 0.003 27 3.8 2.35 0.06

29 CuII Long

1.252 0.002 3 2.3 1.64 0.16

29 CuII 5c 1.272 0.001 27 1.5 2.36 0.02 29 CuII 4c

(as reported)

1.277 0.002 33 1.6 2.44 0.02

30 ZnII 4c 1.276 0.004 31 3.9 2.42 0.06 30 ZnII 5c 1.268 0.004 22 4.0 2.28 0.07 30 ZnII 6c 1.262 0.003 16 3.2 2.15 0.07 31 GaIII 1.327 0.023 75 16.3 2.97 0.23 32 Ge 6c 1.307 0.011 60 9.1 2.78 0.11

25

Table S20 c. Table of elements with C-OA bond-length, % covalent character and

electronegativity

Atomic

Number

Element C-OA Bond

Length (Å)

% Covalent Character Electronegativty

C-OA ∆(C-OA) % Cov ∆

(%Cov.)

Electro ∆

(Electro)

32 Ge 6c 1.307 0.011 60 9.1 2.78 0.11

32 Ge all 1.302 0.003 56 2.6 2.74 0.03

32 Ge 5c 1.292 0.025 47 23.2 2.63 0.27

33 As 1.327 0.023 75 16.3 2.97 0.23

38 Sr 1.253 0.015 5 19.7 1.75 0.56

39 Y 1.268 0.005 22 5.4 2.28 0.09

40 Zr 1.290 0.004 45 3.9 2.60 0.05

41 Nb 1.299 0.015 53 13.5 2.70 0.16

42 Mo 1.284 0.003 39 3.1 2.54 0.04

43 Tc 1.292 0.014 47 12.7 2.63 0.15

44 RuIII 1.293 0.003 48 2.9 2.64 0.04

44 RuII 1.277 0.003 32 2.9 2.43 0.04

45 RhIII 1.291 0.008 46 7.1 2.62 0.09

48 CdII 6c 1.252 0.006 3 7.6 1.63 0.37

49 InIII 1.270 0.002 25 2.0 2.32 0.03

50 Sn 4c 1.291 0.005 46 4.6 2.61 0.06

50 Sn 1.283 0.003 38 2.7 2.51 0.04

50 Sn 5c 1.277 0.002 32 2.5 2.44 0.04

51 Sb 1.285 0.002 40 1.6 2.54 0.02

52 Te 1.287 0.010 43 9.9 2.58 0.12

53 I 1.302 0.005 56 4.1 2.74 0.05

57 LaIII 9c 1.263 0.007 17 8.0 2.17 0.15

58 CeIII 9c 1.268 0.006 22 6.4 2.28 0.11

26

60 NdIII 9c 1.260 0.005 13 5.4 2.08 0.13

27

Table S20 d. Table of elements with C-OA bond-length, % covalent character and electronegativity.

Atomic

Number

Element C-OA Bond

Length (Å)


C-OA ∆ (C-OA) % Cov ∆ (%Cov.) Electro ∆ (Electro)

62 SmIII 9c 1.262 0.006 16 7.0 2.14 0.14

63 EuIII 9c 1.270 0.006 25 6.4 2.32 0.10

64 GdIII 1.266 0.003 20 3.0 2.23 0.06

65 TbIII 9c 1.269 0.009 23 9.9 2.23 0.06

66 DyIII 9c 1.263 0.007 16 8.2 2.15 0.16

70 YbIII 9c 1.270 0.007 24 8.1 2.31 0.13

71 LuIII 9c 1.259 0.006 12 7.2 2.04 0.17

72 Hf 1.296 0.005 50 4.5 2.67 0.05

73 Ta 1.329 0.023 77 16.0 2.98 0.24

74 W 1.291 0.008 46 7.8 2.61 0.09

75 Re 1.298 0.008 52 7.3 2.69 0.09

76 Os(all) 1.292 0.008 47 7.0 2.63 0.08

77 IrIII 1.291 0.006 46 6.0 2.62 0.07

78 PtIV 1.301 0.006 55 5.2 2.73 0.06

78 PtII 1.292 0.004 47 3.8 2.64 0.05

81 Th 1.251 0.007 2 8.8 1.46 0.53

82 Pb 4c 1.267 0.004 22 4.1 2.26 0.07

82 Pb 1.257 0.008 9 9.9 1.96 0.26

83 Bi 1.267 0.004 21 4.5 2.25 0.08

Excel spread-sheets containing full sets of data, including CSD codes are available

by writing to the authors rkh [email protected] and twh

[email protected],

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