Supporting Information for

A Dual Approach to Study the Synthesis, Crystal Structure and Nonlinear Optical

Properties of Binuclear Pd(II) Complex of 3-Methyl-5-(trifluoromethyl) pyrazole and its

Potential Quantum Chemical Analogues

Shabbir Muhammad,a* Sajjad Hussain*,b,c Xuenian Chen,b Abdullah G. Al-Sehemi,d Zi-Jian

Li,e Chin-Hung Lai,f Javed Iqbal,g

a Department of Physics, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabiab School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and

Advanced Energy Materials, Henan Normal University, Xinxiang 453007, Chinac Department of Chemistry, Mohi-ud-Din Islamic University, Nerian Sharif AJ&K, Pakistand Department of Chemistry, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi

Arabiae Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 2019 Jia Luo Road, Shanghai 201800,

Chinaf Department of Medical Applied Chemistry, Chung Shan Medical University, 402 Taichung, Taiwang Department of Chemistry, University of Agriculture Faisalabad, 38000, Faisalabad Pakistan.

E-mail of Corresponding author: mshabbir@kku.edu.sa

Figure S1. FTIR spectrum of [Pd2 (C5H5F3N2)2(C5H4F3N2)2Cl2].3(C2H6O), 1

Figure S2. The contents of unit cell and packing diagram by single-crystal X-ray diffraction analysis along the [c. o. b.] axis where hydrogen atoms are omitted for clarity

Figure S3. Molecular structure of complex 1 hydrogen atom and solvent molecules are

omitted for clarity

Table S1. The selected bond lengths (Å) and bond angles (deg) for complex 1 from it

experimentally determined single crystal. The numbering is according to Figure S3.

Bond length Bond angle

Pd(1)—Cl(1) 2.282(2) N (1)— Pd (1)— Cl(1) 177.9(2)

Pd(1)—N(1) 2.001(6) N (1)— Pd (1)— N(6) 91.2(3)

Pd(1)—N(2) 1.989(7) N (2)— Pd (1)— Cl(1) 91.14(19)

Pd(1)—N(6) 2.012(7) N (2)— Pd (1)— N(1) 87.6(3)

Pd(2)—Cl(2) 2.278(19) N (2)— Pd (1)— N(6) 178.7(3)

Pd(2)—N (3) 2.017(5) N (6)— Pd (1)— Cl(1) 90.0(2)

Pd(2)—N (4) 1.993(6 N (3)— Pd (2)— Cl(2) 177.9(2)

Pd(2)—N (5) 2.023(6) N (3)— Pd (2)— N(5) 91.6(3)

N(1)— N (4) 1.376(9) N (4)— Pd (2)— Cl(2) 91.05(18)

N(1)—C(1) 1.337(10) N (4)— Pd (2)— N(3) 87.6(2)

N(2)— N (3) 1.369(9) N (4)— Pd (2)— N(5) 177.8(3)

N(2)—C(5) 1.350(9) N (5)— Pd (2)— Cl(2) 89.81(19)

N(3)—C(2) 1.339(9 N (4)— N (1)— Pd(1) 118.2(5)

N(4)—C(8) 1.347(10) C (1)— N (1)— Pd(1) 135.6(6)

N(5)—N(7) 1.354(9) N (2)— N (3)— Pd(2) 117.3(5)

N(6)—N(8) 1.363(10) C (2)— N (3)— Pd(2) 136.7(6)

Symmetry code: (i) x, y, z (ii) –x, –y, –z.

Table S2. Some important geometrical parameters of complex 1 according to Figure 1(b) as

calculated for optimized geometry in gas phase (Cal.Gas) in solid-state optimized geometry

within PBC (Cal. PBC) and in experimental crystal (Exp.).

ParameterCal.Gas

(Å)

Cal. PBC

(Å)

Exp.(Å)Parameter

Cal.Gas

(Å)

Cal. PBC

(Å)

Exp.(Å)

Pd(1)-Cl(3) 2.335 2.315 2.284 N(9)-N(11) 1.337 1.364 1.376

Pd(1)-N(5) 2.059 2.069 2.011 N(5)-N(6) 1.337 1.364 1.369

Pd(1)-N(8) 2.069 2.046 2.013 C(34)-F(7) 1.342 1.378 1.325

Pd(1)-N(9) 2.032 2.029 1.987 Triangles (o)

N(5)-N(6) 1.337 1.364 1.369 N(5)-Pd(1)-N(9) 86.63 87.47 87.25

Pd(2)-Cl(4) 2.335 2.314 2.284 N(6)-Pd(2)-N(11) 86.63 87.44 87.25

Pd(2)-N(11) 2.059 2.053 2.021 N(8)-Pd(1)-Cl(3) 89.25 88.53 90.24

Pd(2)-N(10) 2.069 2.037 2.028 N(10)-Pd(2)-Cl(4) 89.24 87.68 89.33

Pd(2)-N(6) 2.032 2.011 1.988 N(5)-Pd(1)-N(8) 92.38 91.31 91.32

N(9)-C(39) 1.34239 1.359 1.380 N(10)-Pd(2)-N(11) 92.38 92.03 92.40

Figure S 4. The optimized structures of complexes 1, 2 and 3 as optimized at M06/6-311G*/LANL2TZ. The value in bracket is experimental from single crystal structure.