In the title mercury complex, the HgII atom is coordinated by two Cl atoms and by two N atoms from two 2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole) ligands, which gives rise to a zigzag helical 1-D polymer propagating along the b-axis direction.
Keywords: crystal structure, mercury coordination polymer, (benzimidazol-2-yl)benzene ligands
Abstract
In the title mercury complex, catena-poly[[dichloridomercury(II)]-μ-2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole)-κ2 N 3:N 3′], [HgCl2(C26H25BrN4)]n, the HgII atom is coordinated by two Cl atoms and by two N atoms from two 2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole) ligands. The metal cation adopts a distorted tetrahedral coordination geometry with with bond angles around mercury of 100.59 (15)° [N—Hg—N] and 126.35 (7)° [Cl—Hg—Cl]. This arrangement gives rise to a zigzag helical 1-D polymer propagating along the b-axis direction.
Chemical context
In the last one decade, 1,3-bis(benzimidazol-2-yl)benzene-based ligands have been studied extensively due to the presence of active sites for binding of metal atoms (Yang et al., 2012 ▸; Tam et al., 2011 ▸; Dorazco-Gonzalez, 2014 ▸). Very recently, dinuclear zinc complexes containing (benzimidazol-2-yl)benzene-based ligands have shown remarkable anticancer activities (Xie et al., 2014 ▸). Helical and non-helical complexes with copper(I) have been reported by Ruettimann et al. (1992 ▸). Palladium complexes with bromo-functionalized benzimidazole derivatives have been utilized for Heck reactions (Reddy & Krishna, 2005 ▸).
A survey of the structural investigations of mercury halide complexes with benzimidazole derivatives have shown that they come in two main types, viz. polymeric, bridging either through the halide (Zhang et al., 2015 ▸; Li et al., 2007 ▸; Shen et al., 2005 ▸) or through alternative N atoms from the benzimidazole moieties (Xiao et al., 2009 ▸, 2011 ▸; Huang et al., 2006 ▸; Li et al., 2007 ▸, 2012a ▸,b ▸; Dey et al., 2013 ▸; Du et al., 2011 ▸; Chen et al., 2013 ▸; Su et al., 2003 ▸; Xu et al., 2011 ▸), or discrete molecules, i.e. non-polymeric (Xiao et al., 2011 ▸; Wu et al., 2009 ▸; Zhao et al., 2012 ▸; Lou et al., 2012 ▸; Zhu et al., 2009 ▸; Carballo et al., 1993 ▸; Yan et al., 2012 ▸; Hu et al., 2012 ▸, 2015 ▸; Ding et al., 2012 ▸; Matthews et al., 1998 ▸; Manjunatha et al., 2011 ▸; Wang et al., 2007 ▸, 2009 ▸, 2012 ▸, 2015 ▸; Chen et al., 2014 ▸; Su et al., 2003 ▸; Quiroz-Castro et al., 2000 ▸; Yang & Luo, 2012 ▸; He et al., 2012 ▸; Bouchouit et al., 2015 ▸).
In the present case, during the attempted synthesis of the C-2 mercurated derivative 3 from 2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole), 1, using n-BuLi and mercuric chloride, the mercury complex 2 was isolated unexpectedly (Fig. 1 ▸).
Figure 1.
Diagram showing the the starting compound, 1, the title compound, 2, and the expected product, 3.
Structural commentary
The structure of 2 with empirical formula, C26H25BrCl2HgN4, is reported in this paper. As a result of the presence of the Br and t-butyl substituents on the central ring, coordination of the HgII atom to this ring is prevented and thus a monomeric complex is formed, as has previously been observed for an HgCl2 complex with a similar ligand but with a central pyridine ring rather than a phenyl ring (Liu et al., 2007 ▸).
Another related structure has recently been reported of a dinuclear structure of HgCl2 with a similar ligand to 1 where there is a methyl substituent on the C1 atom of the imidazole ring (Hu et al., 2015 ▸). In the case of 2, however, a zigzag polymeric structure forms in the b-axis direction, in which the HgCl2 moiety is linked by atoms N1 from one ligand and N3 from an adjoining ligand. The coordination environment around the mercury atom is distorted tetrahedral with bond angles ranging from 100.6 (2) to 126.35 (7)° (Fig. 2 ▸). The two Hg—N bond lengths are equivalent at 2.333 (4) and 2.338 (4) Å. However, the metal–halogen bonds are not similar [Hg—Cl1 = 2.4424 (13) and Hg—Cl2 = 2.4020 (15) Å]. The ligand adopts a conformation whereby the two benzimidazole moieties are not coplanar with each other or the central phenyl ring. The dihedral angles between the benzimidazole moieties N1/N2/C1–C7 and N3/N4/C19–C24 are 60.9 (2)° while they make dihedral angles of 55.6 (2) and 84.2 (2)°, respectively, with the central ring.
Figure 2.
Diagram showing the three units which assemble to form a coordination polymer and illustrating its zigzag helical nature (with H atoms omitted for clarity). Displacement parameters are drawn at the 30% probability level. [Symmetry codes: (A) 1 − x, 
+ y, z − ; (B) 1 − x, y − , z − .]
Supramolecular features
The combination of HgCl2 with 2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole) results in a zigzag helical 1-D coordination polymer that propagates along the b-axis direction. This is mediated by the HgCl2 moiety, which is linked by atoms N1 from one ligand and N3 from an adjoining ligand (Fig. 2 ▸). Although helices are inherently chiral in nature, the overall structure is not chiral as the individual helices are related by a center of inversion. The internal structure of this polymer is stabilized by both C—H⋯Cl and C—H⋯N interactions (Table 1 ▸). In addition, there are both C—H⋯π (Table 1 ▸) and π–π interactions [Cg6⋯Cg6(1 − x, −y, −z) = 3.531 (2) Å, where Cg6 is the centroid of the benzimidazole ring system N3/N4/C19–C24 and C25]. There are no halogen bonds or C—H⋯Br interactions present. Apart from van der Waals interactions, there are no significant interactions between the zigzag chains of the coordination polymer (Fig. 3 ▸).
Table 1. Hydrogen-bond geometry (Å, °).
Cg1 is the centroid of the imidazole ring N1/N2/C1/C2/C7.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C3—H3A⋯N3i | 0.95 | 2.65 | 3.459 (7) | 144 |
| C8—H8A⋯Cl2ii | 0.98 | 2.71 | 3.643 (6) | 160 |
| C8—H8B⋯Cl1iii | 0.98 | 2.82 | 3.719 (6) | 152 |
| C21—H21B⋯Cl1ii | 0.95 | 2.77 | 3.616 (3) | 149 |
| C16—H16B⋯Cg1ii | 0.98 | 2.91 | 3.671 (8) | 135 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 3.
Packing diagram showing two units of the polymer, which repeat in the b-axis direction, viewed along the a axis.
Database survey
A search of the Cambridge Structural Database (Version 5.37 with updates May 2016; Groom et al., 2016 ▸) reveals that there is no report in the literature for a mercury complex with 2,2′-(2-bromo-5-tert-butyl-1,3-phenylene)bis(1-methyl-1H-benzimidazole) that has been structurally characterized. A cadmium complex, bis[1,3-bis(benzimidazol-2-yl)benzene]dichloridocadmium(II), in which the Cd is coordinated by two Cl atoms and two N atoms in a distorted tetrahedral configuration has been reported (Jiang et al., 2010 ▸). In the title complex 2, cadmium is replaced by an HgII atom along with a slight modification of the ligand.
Synthesis and crystallization
To a solution of 1 (0.2 g, 0.42 mmol) in THF (15 ml) was added dropwise a solution of n-BuLi (0.3 ml, 0.47 mmol) at 195 K. The synthesis of compound 1 will be published elsewhere. The reaction mixture turned blue after immediate addition of n-BuLi. The reaction mixture was stirred for 30 min at 195 K followed by the addition of HgCl2 (0.126 g, 0.466 mmol). The reaction mixture was warmed to room temperature and stirred for 16 h. The reaction mixture was then filtered through Whatman filter paper and the solvent was evaporated on a rotary evaporator. Colourless plate-shaped crystals were obtained by the slow evaporation of an ethyl acetate solution of the compound at room temperature.
Yield 44% (0.138 g), 1H NMR (400 MHz, CDCl3): δ 7.88–7.86 (m, 3H), 7.45–7.34 (m, 7H), 3.98 (s, 6H), 1.46 (s, 9H). 13C NMR (100 MHz, DMSO): 152.3, 151.2, 141.6, 135.2, 131.8, 131.4, 123.3, 122.7, 121.6, 119.1, 111.0, 34.9, 31.1, 30.8. Analysis calculated for C26H25N4Cl2BrHg: C, 41.92; H, 3.38; N, 7.52. Found C, 42.68; H, 4.14; N, 6.29.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with U iso(H) = 1.2U eq(C) or 1.5U eq(C) for methyl H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [HgCl2(C26H25BrN4)] |
| M r | 744.90 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 123 |
| a, b, c (Å) | 9.50481 (18), 13.3872 (2), 20.3322 (4) |
| β (°) | 93.0955 (19) |
| V (Å3) | 2583.36 (9) |
| Z | 4 |
| Radiation type | Cu Kα |
| μ (mm−1) | 14.57 |
| Crystal size (mm) | 0.37 × 0.09 × 0.03 |
| Data collection | |
| Diffractometer | Agilent Xcalibur, Ruby, Gemini |
| Absorption correction | Analytical [CrysAlis PRO (Agilent, 2012 ▸) based on expressions derived by Clark & Reid (1995 ▸)] |
| T min, T max | 0.331, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 9778, 5217, 4596 |
| R int | 0.034 |
| (sin θ/λ)max (Å−1) | 0.628 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.038, 0.104, 1.07 |
| No. of reflections | 5217 |
| No. of parameters | 300 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 1.34, −1.88 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017001888/zl2694sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017001888/zl2694Isup2.hkl
CCDC reference: 1530778
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
RJB is grateful for funding from NSF (award 1205608) and the Partnership for Reduced Dimensional Materials for partial funding of this research, to Howard University Nanoscience Facility for access to liquid nitrogen, and the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. HBS is grateful to the DST, New Delhi, for a J. C. Bose National Fellowship. VR gratefully acknowledges the Council of Scientific and Industrial Research (CSIR), New Delhi, for a Senior Research Fellowship.
supplementary crystallographic information
Crystal data
| [HgCl2(C26H25BrN4)] | F(000) = 1432 |
| Mr = 744.90 | Dx = 1.915 Mg m−3 |
| Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
| a = 9.50481 (18) Å | Cell parameters from 4457 reflections |
| b = 13.3872 (2) Å | θ = 3.9–74.8° |
| c = 20.3322 (4) Å | µ = 14.57 mm−1 |
| β = 93.0955 (19)° | T = 123 K |
| V = 2583.36 (9) Å3 | Plate, colorless |
| Z = 4 | 0.37 × 0.09 × 0.03 mm |
Data collection
| Agilent Xcalibur, Ruby, Gemini diffractometer | 5217 independent reflections |
| Radiation source: Enhance (Cu) X-ray Source | 4596 reflections with I > 2σ(I) |
| Detector resolution: 10.5081 pixels mm-1 | Rint = 0.034 |
| ω scans | θmax = 75.6°, θmin = 4.0° |
| Absorption correction: analytical [CrysAlis PRO (Agilent, 2012) based on expressions derived by Clark & Reid (1995)] | h = −11→11 |
| Tmin = 0.331, Tmax = 1.000 | k = −10→16 |
| 9778 measured reflections | l = −25→20 |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
| wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0583P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.001 |
| 5217 reflections | Δρmax = 1.34 e Å−3 |
| 300 parameters | Δρmin = −1.88 e Å−3 |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Hg | 0.26669 (2) | 0.15196 (2) | 0.17398 (2) | 0.03689 (9) | |
| Br1 | 0.78523 (7) | 0.01223 (6) | 0.26403 (4) | 0.05807 (19) | |
| Cl1 | 0.07681 (12) | 0.04507 (10) | 0.12894 (8) | 0.0455 (3) | |
| Cl2 | 0.3350 (3) | 0.17449 (13) | 0.28849 (7) | 0.0680 (5) | |
| N1 | 0.4632 (4) | 0.0840 (3) | 0.12648 (19) | 0.0297 (8) | |
| N2 | 0.6469 (4) | −0.0168 (3) | 0.1125 (2) | 0.0332 (8) | |
| C1 | 0.5402 (5) | 0.0084 (4) | 0.1512 (2) | 0.0290 (9) | |
| C2 | 0.5243 (5) | 0.1104 (4) | 0.0687 (2) | 0.0325 (10) | |
| C3 | 0.4867 (6) | 0.1831 (4) | 0.0214 (2) | 0.0380 (11) | |
| H3A | 0.407599 | 0.225411 | 0.026176 | 0.046* | |
| C4 | 0.5690 (7) | 0.1912 (5) | −0.0326 (3) | 0.0443 (13) | |
| H4A | 0.546152 | 0.239743 | −0.065535 | 0.053* | |
| C5 | 0.6869 (7) | 0.1279 (5) | −0.0392 (3) | 0.0462 (13) | |
| H5A | 0.742376 | 0.136244 | −0.076319 | 0.055* | |
| C6 | 0.7235 (6) | 0.0557 (4) | 0.0054 (3) | 0.0415 (12) | |
| H6A | 0.801480 | 0.012676 | −0.000153 | 0.050* | |
| C7 | 0.6402 (5) | 0.0478 (4) | 0.0599 (2) | 0.0336 (10) | |
| C8 | 0.7432 (5) | −0.1007 (4) | 0.1193 (3) | 0.0412 (11) | |
| H8A | 0.706934 | −0.149329 | 0.150248 | 0.062* | |
| H8B | 0.835960 | −0.077071 | 0.136067 | 0.062* | |
| H8C | 0.751825 | −0.132519 | 0.076325 | 0.062* | |
| C9 | 0.5103 (5) | −0.0449 (4) | 0.2128 (2) | 0.0295 (9) | |
| C10 | 0.6114 (5) | −0.0530 (4) | 0.2651 (2) | 0.0328 (9) | |
| C11 | 0.5801 (5) | −0.1064 (4) | 0.3208 (2) | 0.0347 (10) | |
| C12 | 0.4486 (6) | −0.1492 (4) | 0.3257 (2) | 0.0340 (10) | |
| H12A | 0.429536 | −0.186816 | 0.363769 | 0.041* | |
| C13 | 0.3436 (5) | −0.1382 (4) | 0.2757 (2) | 0.0326 (10) | |
| C14 | 0.3774 (5) | −0.0858 (4) | 0.2192 (2) | 0.0301 (9) | |
| H14A | 0.307701 | −0.078004 | 0.184253 | 0.036* | |
| C15 | 0.1946 (6) | −0.1774 (5) | 0.2844 (3) | 0.0446 (13) | |
| C16 | 0.1931 (7) | −0.2560 (6) | 0.3375 (3) | 0.0569 (16) | |
| H16A | 0.250243 | −0.313200 | 0.325066 | 0.085* | |
| H16B | 0.096006 | −0.277900 | 0.342884 | 0.085* | |
| H16C | 0.232117 | −0.227992 | 0.379161 | 0.085* | |
| C17 | 0.1086 (9) | −0.0864 (7) | 0.3074 (4) | 0.069 (2) | |
| H17A | 0.014973 | −0.108654 | 0.319073 | 0.103* | |
| H17B | 0.098912 | −0.037282 | 0.271679 | 0.103* | |
| H17C | 0.157701 | −0.055702 | 0.345930 | 0.103* | |
| C18 | 0.1272 (7) | −0.2131 (5) | 0.2188 (3) | 0.0504 (14) | |
| H18A | 0.189918 | −0.261007 | 0.198742 | 0.076* | |
| H18B | 0.111504 | −0.155783 | 0.189316 | 0.076* | |
| H18C | 0.036859 | −0.245312 | 0.226242 | 0.076* | |
| N3 | 0.7624 (4) | −0.2007 (3) | 0.3870 (2) | 0.0334 (8) | |
| N4 | 0.7052 (7) | −0.0512 (4) | 0.4249 (3) | 0.0574 (15) | |
| C19 | 0.6851 (6) | −0.1200 (4) | 0.3764 (3) | 0.0389 (11) | |
| C20 | 0.8389 (4) | −0.1846 (3) | 0.44605 (14) | 0.0393 (11) | |
| C21 | 0.9323 (4) | −0.2448 (2) | 0.48302 (18) | 0.0436 (12) | |
| H21B | 0.958442 | −0.308251 | 0.466606 | 0.052* | |
| C22 | 0.9875 (5) | −0.2123 (3) | 0.54401 (18) | 0.0604 (18) | |
| H22B | 1.051354 | −0.253523 | 0.569280 | 0.073* | |
| C23 | 0.9493 (6) | −0.1196 (4) | 0.56803 (19) | 0.085 (3) | |
| H23B | 0.987023 | −0.097343 | 0.609714 | 0.102* | |
| C24 | 0.8559 (6) | −0.0593 (3) | 0.5311 (2) | 0.092 (4) | |
| H24B | 0.829779 | 0.004111 | 0.547474 | 0.111* | |
| C25 | 0.8007 (5) | −0.0918 (3) | 0.4701 (2) | 0.0562 (17) | |
| C26 | 0.6419 (11) | 0.0482 (6) | 0.4279 (4) | 0.080 (3) | |
| H26D | 0.560680 | 0.052189 | 0.396154 | 0.121* | |
| H26E | 0.711628 | 0.098707 | 0.417059 | 0.121* | |
| H26F | 0.610913 | 0.060333 | 0.472366 | 0.121* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Hg | 0.03625 (13) | 0.03134 (14) | 0.04333 (13) | 0.00299 (7) | 0.00463 (8) | 0.00013 (8) |
| Br1 | 0.0463 (3) | 0.0589 (4) | 0.0671 (4) | −0.0147 (3) | −0.0146 (3) | 0.0142 (3) |
| Cl1 | 0.0290 (5) | 0.0381 (7) | 0.0696 (8) | −0.0006 (5) | 0.0036 (5) | 0.0048 (6) |
| Cl2 | 0.1242 (16) | 0.0414 (8) | 0.0383 (6) | 0.0101 (9) | 0.0035 (8) | −0.0041 (6) |
| N1 | 0.0269 (18) | 0.030 (2) | 0.0319 (17) | −0.0004 (15) | 0.0016 (14) | 0.0021 (15) |
| N2 | 0.0281 (18) | 0.034 (2) | 0.0383 (19) | −0.0019 (16) | 0.0042 (15) | −0.0003 (17) |
| C1 | 0.0243 (19) | 0.030 (2) | 0.033 (2) | −0.0040 (17) | 0.0014 (16) | −0.0013 (18) |
| C2 | 0.034 (2) | 0.034 (3) | 0.0289 (19) | −0.0077 (19) | −0.0034 (17) | −0.0009 (19) |
| C3 | 0.044 (3) | 0.034 (3) | 0.035 (2) | −0.010 (2) | −0.002 (2) | 0.005 (2) |
| C4 | 0.061 (3) | 0.039 (3) | 0.033 (2) | −0.018 (3) | −0.001 (2) | 0.003 (2) |
| C5 | 0.051 (3) | 0.053 (3) | 0.035 (2) | −0.023 (3) | 0.009 (2) | −0.006 (2) |
| C6 | 0.041 (3) | 0.042 (3) | 0.042 (2) | −0.011 (2) | 0.010 (2) | −0.008 (2) |
| C7 | 0.032 (2) | 0.032 (2) | 0.037 (2) | −0.0111 (19) | 0.0068 (18) | −0.0054 (19) |
| C8 | 0.030 (2) | 0.037 (3) | 0.057 (3) | 0.002 (2) | 0.008 (2) | −0.003 (2) |
| C9 | 0.030 (2) | 0.026 (2) | 0.032 (2) | 0.0013 (17) | −0.0007 (17) | 0.0030 (17) |
| C10 | 0.029 (2) | 0.026 (2) | 0.042 (2) | −0.0050 (18) | −0.0071 (18) | 0.0024 (19) |
| C11 | 0.039 (2) | 0.032 (3) | 0.032 (2) | 0.001 (2) | −0.0086 (18) | −0.0024 (19) |
| C12 | 0.039 (3) | 0.032 (3) | 0.030 (2) | 0.0009 (19) | 0.0011 (19) | 0.0045 (18) |
| C13 | 0.031 (2) | 0.036 (3) | 0.032 (2) | 0.0023 (19) | 0.0047 (18) | −0.0002 (18) |
| C14 | 0.027 (2) | 0.033 (2) | 0.0302 (19) | 0.0032 (18) | 0.0007 (16) | −0.0002 (17) |
| C15 | 0.032 (3) | 0.060 (4) | 0.042 (3) | −0.003 (2) | 0.006 (2) | 0.015 (3) |
| C16 | 0.057 (4) | 0.061 (4) | 0.053 (3) | −0.016 (3) | 0.005 (3) | 0.009 (3) |
| C17 | 0.060 (4) | 0.073 (5) | 0.075 (5) | 0.013 (4) | 0.027 (3) | 0.007 (4) |
| C18 | 0.047 (3) | 0.050 (4) | 0.054 (3) | −0.020 (3) | −0.004 (2) | 0.011 (3) |
| N3 | 0.0333 (19) | 0.027 (2) | 0.0393 (19) | −0.0024 (16) | −0.0082 (16) | 0.0031 (16) |
| N4 | 0.074 (4) | 0.044 (3) | 0.051 (3) | 0.019 (3) | −0.027 (3) | −0.016 (2) |
| C19 | 0.045 (3) | 0.034 (3) | 0.037 (2) | −0.001 (2) | −0.011 (2) | 0.003 (2) |
| C20 | 0.043 (3) | 0.039 (3) | 0.035 (2) | −0.001 (2) | −0.004 (2) | 0.002 (2) |
| C21 | 0.042 (3) | 0.042 (3) | 0.045 (3) | 0.004 (2) | −0.006 (2) | 0.007 (2) |
| C22 | 0.055 (4) | 0.077 (5) | 0.048 (3) | 0.012 (3) | −0.018 (3) | 0.002 (3) |
| C23 | 0.106 (7) | 0.090 (6) | 0.055 (4) | 0.031 (5) | −0.043 (5) | −0.027 (4) |
| C24 | 0.124 (8) | 0.075 (6) | 0.070 (5) | 0.039 (5) | −0.057 (5) | −0.037 (4) |
| C25 | 0.070 (4) | 0.049 (4) | 0.048 (3) | 0.013 (3) | −0.021 (3) | −0.005 (3) |
| C26 | 0.110 (7) | 0.047 (4) | 0.079 (5) | 0.035 (4) | −0.042 (5) | −0.021 (4) |
Geometric parameters (Å, º)
| Hg—N1 | 2.333 (4) | C13—C15 | 1.530 (7) |
| Hg—N3i | 2.338 (4) | C14—H14A | 0.9500 |
| Hg—Cl2 | 2.4020 (15) | C15—C16 | 1.508 (8) |
| Hg—Cl1 | 2.4424 (13) | C15—C18 | 1.525 (8) |
| Br1—C10 | 1.870 (5) | C15—C17 | 1.553 (10) |
| N1—C1 | 1.331 (6) | C16—H16A | 0.9800 |
| N1—C2 | 1.383 (6) | C16—H16B | 0.9800 |
| N2—C1 | 1.359 (6) | C16—H16C | 0.9800 |
| N2—C7 | 1.374 (7) | C17—H17A | 0.9800 |
| N2—C8 | 1.452 (7) | C17—H17B | 0.9800 |
| C1—C9 | 1.483 (6) | C17—H17C | 0.9800 |
| C2—C3 | 1.401 (7) | C18—H18A | 0.9800 |
| C2—C7 | 1.404 (7) | C18—H18B | 0.9800 |
| C3—C4 | 1.387 (8) | C18—H18C | 0.9800 |
| C3—H3A | 0.9500 | N3—C19 | 1.318 (7) |
| C4—C5 | 1.417 (10) | N3—C20 | 1.387 (4) |
| C4—H4A | 0.9500 | N4—C19 | 1.355 (7) |
| C5—C6 | 1.358 (9) | N4—C25 | 1.369 (6) |
| C5—H5A | 0.9500 | N4—C26 | 1.463 (9) |
| C6—C7 | 1.401 (7) | C20—C21 | 1.3900 |
| C6—H6A | 0.9500 | C20—C25 | 1.3900 |
| C8—H8A | 0.9800 | C21—C22 | 1.3900 |
| C8—H8B | 0.9800 | C21—H21B | 0.9500 |
| C8—H8C | 0.9800 | C22—C23 | 1.3900 |
| C9—C14 | 1.389 (7) | C22—H22B | 0.9500 |
| C9—C10 | 1.398 (6) | C23—C24 | 1.3900 |
| C10—C11 | 1.387 (7) | C23—H23B | 0.9500 |
| C11—C12 | 1.383 (8) | C24—C25 | 1.3900 |
| C11—C19 | 1.478 (6) | C24—H24B | 0.9500 |
| C12—C13 | 1.392 (7) | C26—H26D | 0.9800 |
| C12—H12A | 0.9500 | C26—H26E | 0.9800 |
| C13—C14 | 1.399 (7) | C26—H26F | 0.9800 |
| N1—Hg—N3i | 100.59 (15) | C16—C15—C18 | 112.8 (6) |
| N1—Hg—Cl2 | 105.64 (11) | C16—C15—C13 | 111.5 (5) |
| N3i—Hg—Cl2 | 115.22 (11) | C18—C15—C13 | 110.7 (5) |
| N1—Hg—Cl1 | 102.02 (10) | C16—C15—C17 | 107.9 (6) |
| N3i—Hg—Cl1 | 103.38 (10) | C18—C15—C17 | 107.8 (6) |
| Cl2—Hg—Cl1 | 126.35 (7) | C13—C15—C17 | 105.7 (6) |
| C1—N1—C2 | 105.5 (4) | C15—C16—H16A | 109.5 |
| C1—N1—Hg | 125.2 (3) | C15—C16—H16B | 109.5 |
| C2—N1—Hg | 129.3 (3) | H16A—C16—H16B | 109.5 |
| C1—N2—C7 | 106.8 (4) | C15—C16—H16C | 109.5 |
| C1—N2—C8 | 128.6 (4) | H16A—C16—H16C | 109.5 |
| C7—N2—C8 | 124.4 (4) | H16B—C16—H16C | 109.5 |
| N1—C1—N2 | 112.5 (4) | C15—C17—H17A | 109.5 |
| N1—C1—C9 | 123.9 (4) | C15—C17—H17B | 109.5 |
| N2—C1—C9 | 123.5 (4) | H17A—C17—H17B | 109.5 |
| N1—C2—C3 | 131.1 (5) | C15—C17—H17C | 109.5 |
| N1—C2—C7 | 108.9 (4) | H17A—C17—H17C | 109.5 |
| C3—C2—C7 | 120.0 (5) | H17B—C17—H17C | 109.5 |
| C4—C3—C2 | 117.6 (6) | C15—C18—H18A | 109.5 |
| C4—C3—H3A | 121.2 | C15—C18—H18B | 109.5 |
| C2—C3—H3A | 121.2 | H18A—C18—H18B | 109.5 |
| C3—C4—C5 | 120.8 (5) | C15—C18—H18C | 109.5 |
| C3—C4—H4A | 119.6 | H18A—C18—H18C | 109.5 |
| C5—C4—H4A | 119.6 | H18B—C18—H18C | 109.5 |
| C6—C5—C4 | 122.5 (5) | C19—N3—C20 | 106.0 (4) |
| C6—C5—H5A | 118.7 | C19—N3—Hgii | 123.8 (3) |
| C4—C5—H5A | 118.7 | C20—N3—Hgii | 129.2 (3) |
| C5—C6—C7 | 116.5 (6) | C19—N4—C25 | 106.3 (5) |
| C5—C6—H6A | 121.7 | C19—N4—C26 | 127.3 (5) |
| C7—C6—H6A | 121.7 | C25—N4—C26 | 126.4 (5) |
| N2—C7—C6 | 131.2 (5) | N3—C19—N4 | 112.5 (4) |
| N2—C7—C2 | 106.3 (4) | N3—C19—C11 | 125.0 (5) |
| C6—C7—C2 | 122.5 (5) | N4—C19—C11 | 122.4 (5) |
| N2—C8—H8A | 109.5 | N3—C20—C21 | 131.9 (3) |
| N2—C8—H8B | 109.5 | N3—C20—C25 | 108.0 (3) |
| H8A—C8—H8B | 109.5 | C21—C20—C25 | 120.0 |
| N2—C8—H8C | 109.5 | C20—C21—C22 | 120.0 |
| H8A—C8—H8C | 109.5 | C20—C21—H21B | 120.0 |
| H8B—C8—H8C | 109.5 | C22—C21—H21B | 120.0 |
| C14—C9—C10 | 119.3 (4) | C23—C22—C21 | 120.0 |
| C14—C9—C1 | 119.0 (4) | C23—C22—H22B | 120.0 |
| C10—C9—C1 | 121.6 (4) | C21—C22—H22B | 120.0 |
| C11—C10—C9 | 119.5 (4) | C22—C23—C24 | 120.0 |
| C11—C10—Br1 | 118.6 (3) | C22—C23—H23B | 120.0 |
| C9—C10—Br1 | 121.8 (4) | C24—C23—H23B | 120.0 |
| C12—C11—C10 | 120.4 (4) | C23—C24—C25 | 120.0 |
| C12—C11—C19 | 118.0 (5) | C23—C24—H24B | 120.0 |
| C10—C11—C19 | 121.6 (5) | C25—C24—H24B | 120.0 |
| C11—C12—C13 | 121.3 (5) | N4—C25—C24 | 132.8 (3) |
| C11—C12—H12A | 119.4 | N4—C25—C20 | 107.2 (3) |
| C13—C12—H12A | 119.4 | C24—C25—C20 | 120.0 |
| C12—C13—C14 | 117.7 (5) | N4—C26—H26D | 109.5 |
| C12—C13—C15 | 120.7 (5) | N4—C26—H26E | 109.5 |
| C14—C13—C15 | 121.5 (4) | H26D—C26—H26E | 109.5 |
| C9—C14—C13 | 121.6 (4) | N4—C26—H26F | 109.5 |
| C9—C14—H14A | 119.2 | H26D—C26—H26F | 109.5 |
| C13—C14—H14A | 119.2 | H26E—C26—H26F | 109.5 |
| C2—N1—C1—N2 | −0.7 (5) | C11—C12—C13—C15 | −174.2 (5) |
| Hg—N1—C1—N2 | 178.9 (3) | C10—C9—C14—C13 | −2.4 (8) |
| C2—N1—C1—C9 | −178.7 (4) | C1—C9—C14—C13 | 179.1 (5) |
| Hg—N1—C1—C9 | 0.8 (6) | C12—C13—C14—C9 | −0.7 (8) |
| C7—N2—C1—N1 | 1.1 (5) | C15—C13—C14—C9 | 176.1 (5) |
| C8—N2—C1—N1 | −173.1 (5) | C12—C13—C15—C16 | −20.5 (8) |
| C7—N2—C1—C9 | 179.1 (4) | C14—C13—C15—C16 | 162.8 (5) |
| C8—N2—C1—C9 | 4.9 (8) | C12—C13—C15—C18 | −147.0 (5) |
| C1—N1—C2—C3 | 178.3 (5) | C14—C13—C15—C18 | 36.3 (8) |
| Hg—N1—C2—C3 | −1.2 (8) | C12—C13—C15—C17 | 96.5 (6) |
| C1—N1—C2—C7 | 0.0 (5) | C14—C13—C15—C17 | −80.2 (7) |
| Hg—N1—C2—C7 | −179.5 (3) | C20—N3—C19—N4 | −0.1 (7) |
| N1—C2—C3—C4 | −179.2 (5) | Hgii—N3—C19—N4 | 169.2 (4) |
| C7—C2—C3—C4 | −1.1 (7) | C20—N3—C19—C11 | −176.2 (5) |
| C2—C3—C4—C5 | −0.1 (8) | Hgii—N3—C19—C11 | −6.9 (8) |
| C3—C4—C5—C6 | 1.4 (8) | C25—N4—C19—N3 | −1.0 (8) |
| C4—C5—C6—C7 | −1.4 (8) | C26—N4—C19—N3 | 177.1 (8) |
| C1—N2—C7—C6 | −179.8 (5) | C25—N4—C19—C11 | 175.2 (6) |
| C8—N2—C7—C6 | −5.3 (8) | C26—N4—C19—C11 | −6.6 (12) |
| C1—N2—C7—C2 | −1.0 (5) | C12—C11—C19—N3 | 80.3 (8) |
| C8—N2—C7—C2 | 173.5 (4) | C10—C11—C19—N3 | −99.4 (7) |
| C5—C6—C7—N2 | 178.9 (5) | C12—C11—C19—N4 | −95.5 (7) |
| C5—C6—C7—C2 | 0.2 (7) | C10—C11—C19—N4 | 84.8 (8) |
| N1—C2—C7—N2 | 0.6 (5) | C19—N3—C20—C21 | 176.7 (4) |
| C3—C2—C7—N2 | −177.9 (4) | Hgii—N3—C20—C21 | 8.2 (7) |
| N1—C2—C7—C6 | 179.5 (4) | C19—N3—C20—C25 | 1.1 (5) |
| C3—C2—C7—C6 | 1.0 (7) | Hgii—N3—C20—C25 | −167.4 (3) |
| N1—C1—C9—C14 | 54.6 (7) | N3—C20—C21—C22 | −175.2 (5) |
| N2—C1—C9—C14 | −123.2 (5) | C25—C20—C21—C22 | 0.0 |
| N1—C1—C9—C10 | −123.9 (5) | C20—C21—C22—C23 | 0.0 |
| N2—C1—C9—C10 | 58.3 (7) | C21—C22—C23—C24 | 0.0 |
| C14—C9—C10—C11 | 3.6 (8) | C22—C23—C24—C25 | 0.0 |
| C1—C9—C10—C11 | −177.8 (5) | C19—N4—C25—C24 | −175.9 (4) |
| C14—C9—C10—Br1 | −173.0 (4) | C26—N4—C25—C24 | 5.9 (12) |
| C1—C9—C10—Br1 | 5.5 (7) | C19—N4—C25—C20 | 1.7 (7) |
| C9—C10—C11—C12 | −1.8 (8) | C26—N4—C25—C20 | −176.5 (8) |
| Br1—C10—C11—C12 | 175.0 (4) | C23—C24—C25—N4 | 177.4 (7) |
| C9—C10—C11—C19 | 177.9 (5) | C23—C24—C25—C20 | 0.0 |
| Br1—C10—C11—C19 | −5.4 (7) | N3—C20—C25—N4 | −1.8 (5) |
| C10—C11—C12—C13 | −1.4 (8) | C21—C20—C25—N4 | −178.0 (5) |
| C19—C11—C12—C13 | 178.9 (5) | N3—C20—C25—C24 | 176.2 (4) |
| C11—C12—C13—C14 | 2.6 (8) | C21—C20—C25—C24 | 0.0 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the imidazole ring N1/N2/C1/C2/C7.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3A···N3i | 0.95 | 2.65 | 3.459 (7) | 144 |
| C8—H8A···Cl2ii | 0.98 | 2.71 | 3.643 (6) | 160 |
| C8—H8B···Cl1iii | 0.98 | 2.82 | 3.719 (6) | 152 |
| C21—H21B···Cl1ii | 0.95 | 2.77 | 3.616 (3) | 149 |
| C16—H16B···Cg1ii | 0.98 | 2.91 | 3.671 (8) | 135 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017001888/zl2694sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017001888/zl2694Isup2.hkl
CCDC reference: 1530778
Additional supporting information: crystallographic information; 3D view; checkCIF report