Supporting Information

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1 Supporting Information Halogen Bonding Synthon Modularity in Coordination Compounds Hamid Reza Khavasi *, Fataneh Norouzi and Alireza Azhdari Tehrani Faculty of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran , Iran. Experimental section page 2 Figure S1. The ORTEP diagram of asymmetric unit of compounds 2 and 3. page 4 Figure S2. Fragments selected for calculation of dimer binding energies in page 5 compounds 1-3. Table S1. Crystallographic data Page 6 Table S2. Selected bond distances and bond angles page 6 Table S3. Intermolecular interaction parameters page 6 References Page 7 1

2 Experimental Part Chemicals and instrumentation: All starting materials and solvents were purchased from commercial suppliers (Sigma-Aldrich and Merck) and used as received.the FT-IR spectra were recorded on a BOMEM - MB102 spectrometer in the range cm -1 using the KBr disk technique. Elemental analyses (carbon, hydrogen, and nitrogen) were performed using a Heraeus CHN-O Rapid analyzer. 1 H NMR spectra were recorded on a Bruker AC- 300 MHz spectrometer at ambient temperature in CD 3 OD and DMSO. All chemical shifts are quoted in part per million (ppm) relative to tetramethylsilane. Melting points were measured by a Bamstead Electrothermal type 9200 melting point apparatus and corrected. Synthesis The N-(3-chlorophenyl)-pyrazine-2-carboxamide (L 3-Cl ), N-(4-chlorophenyl)-pyrazine-2-carboxamide (L 4- Cl ) and [HgBr 2 (L 3-Cl )] were reported previously by some of us. S1 Synthesis of N-(3,4-dichlorophenyl)-pyrazine-2-carboxamide: A solution of 3,4-dichloroaniline (5mmol, 0.81g) in pyridine (10 ml) was added to a solution of pyrazine- 2-carboxylic acid (5mmol, 0.62g) in pyridine (10 ml). The resulting solution was stirred at 313 K for 20 min, and then triphenyl phosphite(5mmol, 1.3 ml) was added dropwise, and the reaction mixture was stirred 5 h at 373 K and 24 h at ambient temperature. The mixture was added to 100 ml distilled water. Precipitation of a white solid resulted with a yield of 85%, which was filtered off and dried under reduced pressure. (Melting point = C) Anal. Calcd for C 11 H 7 Cl 2 N 3 O: C, 49.28; H, 2.63; N, Found: C, 49.18; H, 2.56; N, FT-IR (KBr pellet, cm -1 ): 3221, 1674, 1512, 1377, 1114, 1014, 813, H NMR (CD 3 OD, δ from TMS): 9.38 (d,1h-pyrazine), 9.30 (amidic H), 8.87 (d,1h-pyrazine), 8.78 (d,1h-pyrazine), 8.21 (S, 1H-phenyl), (d, 1H-phenyl), (d, 1H-phenyl). Synthesis of [HgBr 2 (L 4-Cl )]: To a solution of HgBr 2 (0.036 g, 0.1 mmol), in 3 ml methanol, a solution of L 4-Cl (0.023 g, 0.1 mmol) in 3 ml methanol was added with stirring. The mixture was heated at 50 C for about 30 min and then filtered. Upon slow evaporation of the filtrate at room temperature, suitable crystals of complex [HgBr 2 (L 4-Cl )] for X-ray analysis were obtained after 10 days (yield 40%). Anal. Calcd for C 11 H 8 Br 2 HgClN 3 O 1 : C, 22.24; H, 1.36; N, Found: C, 22.20; H, 1.35; N, FT-IR (KBr pellet, cm -1 ): 3345, 1687, 1593, 1532, 1392,1040, 891, 824, 655, H NMR (DMSO, δ from TMS): (1H-pyrazine), 9.28 (amidic H), 8.92 (1H-pyrazine), 8.81 (1H-pyrazine), (2H-phenyl) and (2H-phenyl). Synthesis of [HgBr 2 (L 3,4-diCl )]: To a solution of HgBr 2 (0.028 g, 0.08 mmol), in 3 ml methanol, a solution of L 3,4-diCl (0.022 g, 0.08 mmol) in 3 ml methanol was added with stirring. The mixture was heated at 50 C for about 30 min and then filtered. Upon slow evaporation of the filtrate at room temperature, suitable crystals of complex [HgBr 2 (L 3,4-diCl )] for X-ray analysis were obtained after 7 days (yield 65%). Anal. Calcd for C 11 H 7 Br 2 Cl 2 HgN 3 O 1 : C, 21.02; H, 1.12; N, Found: C, 20.92; H, 1.03; N, FT-IR (KBr pellet, cm -1 ): 3579, 1681, 1608, 1515, 1380, 1014, 860, 651, H NMR (CD 3 OD, δ from TMS): 9.35 (d,1h-pyrazine), 8.84 (amidic H), 8.76 (d,1h-pyrazine), 8.16 (d,1h-pyrazine), 7.72 (d, 1H-phenyl), (d, 2H-phenyl). Single crystal data collection and refinement: For X-ray diffraction analysis, the intensity data were collected on a Bruker SMART APEX-II CCD diffractometer for 2 and a STOE IPDS-II diffractometer for compound 3, with graphite monochromated Mo- Kα radiation, Å. Cell parameters were retrieved using APEX II software S2 and refined using SAINT S3 for compound 2 and using the Stöe X-AREA S4 software package for 3, on all observed reflections. Absorption corrections were applied using SADABS S5 and X-RED S6 and X-SHAPE S7 software s for 2 and 3, 2

3 respectively. Both structures were solved by direct methods using SHELXS-97 S8 and refined with fullmatrix least-squares on F 2 using the SHELXL-97 S8 with X-STEP32 S9 crystallographic software package. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were added at ideal positions and constrained to ride on their parent atoms, with U iso (H) = 1.2U eq. Computational details for calculating halogen bonding binding energies: DFT calculations were conducted using the ORCA quantum chemistry package. S10 The local spin density approximation (LSD) exchange correlation potential was used with the local density approximation of the correlation energy. S11 Gradient-corrected geometry optimizations S12-13 were performed by using the generalized gradient approximation (Perdew Wang non-local exchange and correlation corrections PW91). S14 The selected two fragments were cut out directly from the CIF data without optimization. All C-H, O-H and N-H distances were normalized to neutron values and thus these values were retained for the energy calculations. An all-electron triple-zeta basis-set with a polarization function, TZP, has been used to ascribe all the atoms. Frozen core approximation was used to treat the core electrons. Scalar relativistic effects were account for by using the zeroth-order regular approximation (ZORA). S15-17 Hirshfeld Surface Analysis: The intermolecular interactions in the crystal structures of compounds 1, 2 and 3 are quantified via Hirshfeld surface analysis1 using CrystalExplorer 3.0. S18,19 Computational details for generating molecular electrostatic potential surface: Electrostatic potential surfaces were generated for compounds 1, 2 and 3 from DFT calculations performed at the B3LYP/6-311G (d,p) basis set for all atoms. Potential surfaces were mapped by conventional molecular electron density (0.008 electron/ Bohr 3 ) and color-coding. 3

4 (a) (b) Figure S1. The ORTEP diagram of asymmetric unit of compounds 2, (a) and 3, (b). Ellipsoids are drawn at 30% probability level. 4

5 (a) (b) (c) Figure S2. Fragments selected for calculation of dimer binding energies in compounds 1, (a), 2, (b) and 3, (c). 5

6 Table S1. Structural data and refinement for complexes 2 and 3. Complex 2 Complex 3 formula C 11H 8Br 2ClHgN 3O C 11H 7Br 2Cl 2HgN 3O fw λ/å T/K 298(2) 298(2) crystal.system Orthorhombic Orthorhombic space group Pbca Cmca a/å (8) (4) b/å (11) (7) c/å (3) (2) V/Å (5) (3) D calc/mg m Z 8 8 μ/mm F(000) θ/ R(int) GOOF R a 1 (I > 2σ(I)) wr b 2 (I > 2σ(I)) CCDC No a R 1 =Σ F o - F c /Σ F o. b wr 2 = [Σ(w(F 2 o - F 2 c ) 2 )/Σw(F 2 o )2] ½. Table S2. Selected bond length (Å) and angles ( ) around mercury (II) for complexes 1-3. Complex 1 a 2 3 Bond distance Hg1-N (10) 2.526(12) 2.552(14) Hg1-Br (12) (14) (18) Hg1-Br (14) (14) (16) Bond Angle N2-Hg1-Br1 98.3(3) 96.7(3) 95.9(3) N2-Hg1-Br (2) 95.1(3) 98.2(3) Br1-Hg1-Br (5) (6) (7) a From reference [S21] Table S3. Geometrical parameters of hydrogen bonding, π phen -NHCO- interaction and Hg Br contacts in complexes 1-3. D-H A d(d-h) (Å) d(h A) (Å) d(d A) (Å) D H...A / symmetry Complex 1 a C10-H10 O1-C (5) x, -1/2+y, 1/2-z π phen(c6-c11) Cg (-NHCO-) (6) - 1/2-x, y, 1/2-z Hg1 Br (1) -1/2+x, 1/2-y, -z Complex 2 C1-H1 Cl (1) 153 -x, -1/2-y, 1/2-z π phen(c6-c11) Cg (-NHCO-) (7) - ½+x, y, 1/2-z Cg (-NHCO-) π phen(c6-c11) (8) - ½+x, y, 1/2-z Hg1 Br (5) - -1/2+x, 1/2-y, 1-z Complex 3 C10-H10 O1-C (7) x, -1/2+y, 1/2-z N3-H3A Cl (7) x, -1/2+y, 1/2-z π phen(c6-c11) Cg (-NHCO-) (6) - 1/2-x, y, 1/2-z Hg1 Br (6) -1/2+x, 1/2-y, -z a From reference [S21] 6

7 References: [S1] Sasan, K.; Khavasi, H. R.; Davari, M. D. Monatsh. Chem. 2008, 139, [S2] APEX2 V Software for the CCD Detector System; Bruker Analytical X-ray Systems, Madison, WI, [S3] SAINT V 7.34 Software for the Integration of CCD Detector System Bruker Analytical X-ray Systems, Madison, WI, [S4] Stoe & Cie, X AREA, vesion 1.30: Program for the acquisition and analysis of data; Stoe & Cie GmbH: Darmatadt, Germany, [S5] SADABS V2.008/2 Program for absorption corrections using Bruker-AXS CCD based on the method of Robert Blessing; Blessing, R.H. Acta Cryst. A51, 1995, 33. [S6] Stoe & Cie, X RED, vesion 1.28b: Program for data reduction and absorption correction; Stoe & Cie GmbH: Darmatadt, Germany, [S7] Stoe & Cie, X SHAPE, vesion 2.05: Program for crystal optimization for numerical absorption correction; Stoe & Cie GmbH: Darmatadt, Germany, [S8] Sheldrick, G. M. SHELX97. Program for crystal structure solution and refinement. University of Göttingen, Germany, [S9] Stoe & Cie, X-STEP32, Version 1.07b: Crystallographic package; Stoe & Cie GmbH: Darmstadt, Germany, [S10] Neese, F.; Becker, U.; Ganyushin, D.; Liakos, D. G.; Kossmann, S.; Petrenko, T.; Riplinger, C.; Wennmohs, F. ORCA, 2.7.0, University of Bonn, Bonn, [S11] Vosko, S. H.; Wilk L.; Nusair, M. Can. J. Phys. 1980, 58, [S12] Versluis, L.; Ziegler, T.; J. Chem. Phys. 1988, 88, [S13] Fan, L.; Ziegler, T. J. Chem.Phys. 1991, 95, [S14] Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. 1992, 46, [S15] van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, [S16] van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1994, 101, [S17] van Lenthe, E.; Baerends, E. J.; Snijders, J. G. Int. J. Quantum Chem. 1996, 57, [S18] McKinnon, J. J.; Spackman, M. A.; Mitchell, A. S. Acta Crystallogr., 2004, B60, [S19] Spackman, M. A.; McKinnon, J. J. CrystEngComm, 2002, 4, [S20] Wolff, S. K.; Grimwood, D. J.; McKinnon, J. J.; Turner, M. J.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer 3.0, University of Western Australia, Perth, Australia, [S21] Khavasi, H. R.; Azhdari Tehrani, A. Inorg. Chem. 2013, 52,