The structure of a previously unknown form of dichlorido(4,4′-dimethyl-2,2′-bipyridine)copper(II) was obtained via a DMSO-mediated dehydration of Cu(4,4′-dimethyl-2,2′-bipyridine)copper(II)·0.25H2O. The crystal structure reveals chloride-bridged copper(II) chains connected via intermolecular C—H⋯Cl hydrogen bonds.
Keywords: crystal structure, copper bipyridine complex, dehydration, hydrogen bonding
Abstract
The title compound, [CuCl2(C12H12N2)]n, was obtained via a DMSO-mediated dehydration of Cu(4,4′-dimethyl-2,2′-bipyridine)copper(II)·0.25H2O. The central CuII atom is coordinated in a distorted trigonal–bipyramidal geometry by two N atoms of a chelating 4,4′-dimethyl-2,2′-bipyridine ligand [average Cu—N = 2.03 (3) Å] and three Cl atoms, one terminal with a short Cu—Cl bond of 2.2506 (10) Å, and two symmetry-equivalent and bridging bonds. The bridging Cl atom links the CuII ions into chains parallel to [001] via one medium and one long Cu—Cl bond [2.3320 (10) and 2.5623 (9) Å]. The structure displays both inter- and intramolecular C—H⋯Cl hydrogen bonding.
Chemical context
Bipyridine complexes of copper(II), [(2,2′-bipy)CuX
2] (X = Cl, Br) have been used in a number of important applications in recent years, most notably in the areas of catalysis for organic synthesis (Ricardo et al., 2008 ▸; Csonka et al., 2008 ▸; Thorpe et al., 2012 ▸), DNA cleavage (Jaividhya et al., 2012 ▸), degradation of pesticides (Knight et al., 2014 ▸) and water oxidation (Barnett et al., 2012 ▸). Such complexes are characterized by an extensive number of metal coordination geometries including square-planar/tetrahedral, square-pyramidal/trigonal–bipyramidal and distorted octahedral. The associated halide ligands (chloride, bromide) can adopt terminal or bridging bonding modes leading to monomeric, dimeric or polymeric chain structures which can influence complex solubility in organic solvents and consequently their possible application in homogeneous catalysis. A third factor which influences the structural forms of these complexes is the nature of the solvent, with strongly coordinating ligands forming solvent adducts. For example, the reaction of dimethyl-2,2′-bipyridine with CuI and/or CuII in DMSO or water led to the isolation of 10 different crystalline materials, suggesting that a large number of structural motifs are possible including five-coordinate monomers, distorted tetrahedral monomers, stacked planar monomers, stacked planar bibridged dimers and and five-coordinate bibridged dimers (Willett et al., 2001 ▸). A large number of ring-substituted 2,2′-bipyridine complexes have also been prepared and characterized including dichlorido(4,4′-dimethyl-2,2′-bipyridine) copper(II) hemihydate. In this paper we describe the synthesis and structural characterization of a previously unknown form of dichlorido(4,4′-dimethyl-2,2′-bipyridine)copper(II) via a DMSO-mediated dehydration of Cu(4,4′-dimethyl-2,2′-bipyridine)Cl2·0.25H2O. The crystal structure reveals single chlorido-bridged copper(II) chains with a distorted trigonal–bipyramidal geometry of the metal cations. We conclude that the presence of the 4,4′-dimethyl substituents does not prevent the formation of a catenated structure, which was previously suggested as an explanation for the dimeric arrangement in Cu(4,4′-dimethyl-2,2′-bipyridine)Cl2·0.5H2O (González et al., 1993 ▸).
Structural commentary
In the title complex (1), Fig. 1 ▸, the central CuII atom is coordinated by the two nitrogen atoms, N1 and N12 of the chelating 2,2′-bipyridine subunit and three chlorine atoms, one terminal (Cl1) with a short Cu—Cl bond, and two bridging chlorine atoms (Cl2), which are symmetry equivalent. The bridging chlorine ligand links Cu atoms into chains via one medium and one long Cu—Cl bond [2.3320 (10) and 2.5623 (9) Å]. The geometry around the Cu ion is best described as a distorted trigonal bipyramid with the coordination polyhedron defined by the two N atoms and three Cl atoms, one of which links the monomeric subunits into a chain, which contrasts with the four-coordinate square-planar geometry found in Cu(2,2′-bipyridine)Cl2 (Wang et al., 2004 ▸; Garland et al., 1988 ▸). The two axial sites are occupied by N1 and Cl1 [N1—Cu1—Cl1 = 172.93 (10)°] and the basal plane contains the N12 atom, the Cl2 atom and the bridging Cl2 atom. The terminal Cu1—Cl1 and medium-length bridging Cu1—Cl2 bond lengths in (1) are 2.2506 (10) and 2.3320 (10) Å which are comparable to those found in the related structure Cu(2,2′-bipyridine)Cl2 [2.254 (4) Å; Wang et al., 2004 ▸] and its polymorph [2.291 (3) Å; Hernández-Molina et al., 1999 ▸], and in dichlorido(4,4′-dimethyl)-2,2′-bipyridine)copper(II) hemihydrate [2.255 (2) and 2.274 (2) Å, respectively; González et al., 1993 ▸]. However, the longer bridging Cu—Cl bond has a length of 2.5623 (9) Å which is shorter than those found in the above comparison structures [3.047 (3), 2.674 (3) and 2.754 (2) Å]. The Cu—N1 and Cu—N12 bond lengths in (1) are 2.009 (3) and 2.047 (3) Å, similar to those found in the above structures [2.024 (6), 2.037 (8), and 2.001 (3) and 2.035 (4) Å, respectively]. These comparisons indicate that neither hydration nor 4,4′-dialkyl substitution significantly affects either the terminal Cu—Cl or Cu—N bond lengths. The bipyridine ring presents a bite angle of 79.25 (12)° to Cu, similar to that found in the above-mentioned structures, 80.5 (3), 79.6 (3) and 80.2 (1)° respectively, and forming a virtually planar five-membered ring. The C—C and C—N bond lengths and angles are within expected limits.
Figure 1.
ORTEP-style view of compound (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x − 1, −y + 2, z − 
.]
Supramolecular features
The crystal structure of (1) can best be described as a linear polymer consisting of monomeric units with chains extending parallel to [001]. The chains are connected via weak C—H⋯Cl hydrogen bonds (Table 1 ▸ and Fig. 2 ▸). Adjacent copper atoms are bridged via single chlorine atoms [Cu1—Cl2i = 2.5623 (9) Å; (i) = x, −y + 2, z − ). This contrasts with the structure found in Cu(2,2′-bipyridine)Cl2 in which two chlorine atoms link the monomeric substructures into a catenated complex. In (1) an intramolecular C—H⋯Cl hydrogen bond is also observed (Table 1 ▸).
Table 1. Hydrogen-bond geometry (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| C11H11ACl1 | 0.95 | 2.61 | 3.211(4) | 122 |
| C8H8ACl2i | 0.95 | 2.88 | 3.666(4) | 140 |
| C10H10ACl1ii | 0.95 | 2.88 | 3.733(4) | 149 |
Symmetry codes: (i) 
; (ii) 
.
Figure 2.
Selected portion of the crystal packing diagram of compound (1), showing interchain C—H⋯Cl hydrogen bonding (see Table 1 ▸ for details).
Database survey
A large number of unsubstituted and substituted bipyridine copper complexes with halide ligands can be found in the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2015 ▸). These structures have four-, five, and six-coordination. The related structure dichlorido(4,4′-dimethyl)-2,2′-bipyridine)copper(II) hemihydrate (González et al., 1993 ▸) crystallizes with a dimeric arrangement of subunits. The unsubstituted complex Cu(2,2′-bipyridine)Cl2 has been found to form both simple monomeric (Kostakis et al., 2006 ▸) and chain structures (Hernández-Molina et al., 1999 ▸; Wang et al., 2004 ▸), the latter bearing similarities to the structure of (1).
Synthesis and crystallization
Solvents and reagents were obtained and purified as follows: DMSO (Aldrich), dried over 4 Å molecular sieves, CuCl2·2H2O, 4,4′-dimethyl-2,2′-bipyridine (Sigma–Aldrich) used as received. Cu(4,4′-dimethyl-2,2′-bipyridine)Cl2·0.25 H2O was prepared according to the literature procedure (Moore et al., 2012 ▸). Cu(4,4′-dimethyl-2,2′-bipyridine)Cl2·0.25 H2O (0.4091 g, 1.266 mmol) was dissolved in anhydrous DMSO (500 ml) and stored at 277 K for 30 months (shorter periods of time, e.g. 7 days, did not result in dehydration). The DMSO was then removed under a stream of N2 and the resulting solid was further dried in vacuo at 313 K to give (1) as a green powder (0.386 g, 1.21 mmol, 96% yield). A portion of (1) was dissolved in DMSO and concentrated under a stream of N2 (flow rate = 12 l/min) over 7 days in an open vial to give green plates. Analysis calculated for CuC12H12N2Cl2: C, 45.23; H, 3.80; N, 8.79. Found: C, 44.69; H, 3.66; N, 8.20.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were included in calculated positions and refined as riding: C—H = 0.95–0.98 Å with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for other H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [CuCl2(C12H12N2)] |
| M r | 318.68 |
| Crystal system, space group | Monoclinic, C c |
| Temperature (K) | 150 |
| a, b, c () | 9.1101(6), 20.0087(12), 7.1231(4) |
| () | 110.491(2) |
| V (3) | 1216.25(13) |
| Z | 4 |
| Radiation type | Mo K |
| (mm1) | 2.21 |
| Crystal size (mm) | 0.27 0.12 0.07 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2002 ▸) |
| T min, T max | 0.646, 0.746 |
| No. of measured, independent and observed [I > 2(I)] reflections | 7099, 2945, 2829 |
| R int | 0.049 |
| (sin /)max (1) | 0.685 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.030, 0.072, 1.05 |
| No. of reflections | 2945 |
| No. of parameters | 156 |
| No. of restraints | 2 |
| H-atom treatment | H-atom parameters constrained |
| max, min (e 3) | 0.56, 0.48 |
| Absolute structure | Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983 ▸) |
| Absolute structure parameter | 0.011(15) |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015008944/zl2617sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008944/zl2617Isup2.hkl
CCDC reference: 1063931
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work received support from the Defense Threat Reduction Agency–Joint Science and Technology Office for Chemical and Biological Defense (MIPR #B102405M, B112542M and HDTRA136555). DAK is grateful to the American Society of Engineering Education and Office of Naval Research for a Distinguished Faculty Fellowship.
supplementary crystallographic information
Crystal data
| [CuCl2(C12H12N2)] | F(000) = 644 |
| Mr = 318.68 | Dx = 1.740 Mg m−3 |
| Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.1101 (6) Å | Cell parameters from 4788 reflections |
| b = 20.0087 (12) Å | θ = 2.6–29.1° |
| c = 7.1231 (4) Å | µ = 2.21 mm−1 |
| β = 110.491 (2)° | T = 150 K |
| V = 1216.25 (13) Å3 | Plate, green |
| Z = 4 | 0.27 × 0.12 × 0.07 mm |
Data collection
| Bruker APEXII CCD diffractometer | 2945 independent reflections |
| Radiation source: sealed tube | 2829 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.049 |
| ω scans | θmax = 29.1°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −12→12 |
| Tmin = 0.646, Tmax = 0.746 | k = −27→27 |
| 7099 measured reflections | l = −9→9 |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 2945 reflections | Δρmax = 0.56 e Å−3 |
| 156 parameters | Δρmin = −0.48 e Å−3 |
| 2 restraints | Absolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983). |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.011 (15) |
Special details
| Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.99673 (5) | 0.95231 (2) | 0.74601 (5) | 0.01585 (12) | |
| Cl1 | 1.12820 (11) | 0.85482 (5) | 0.80882 (16) | 0.0243 (2) | |
| Cl2 | 1.15771 (10) | 1.00184 (5) | 1.04309 (13) | 0.01687 (18) | |
| N1 | 0.8565 (4) | 1.03282 (16) | 0.6685 (5) | 0.0166 (6) | |
| C2 | 0.9078 (5) | 1.0962 (2) | 0.6952 (6) | 0.0217 (8) | |
| H2A | 1.0170 | 1.1044 | 0.7567 | 0.026* | |
| C3 | 0.8073 (5) | 1.14974 (19) | 0.6364 (6) | 0.0213 (8) | |
| H3A | 0.8479 | 1.1940 | 0.6576 | 0.026* | |
| C4 | 0.6467 (5) | 1.13963 (18) | 0.5460 (6) | 0.0164 (7) | |
| C4A | 0.5357 (5) | 1.19727 (19) | 0.4831 (7) | 0.0219 (8) | |
| H4AA | 0.4287 | 1.1817 | 0.4592 | 0.033* | |
| H4AB | 0.5414 | 1.2168 | 0.3597 | 0.033* | |
| H4AC | 0.5642 | 1.2311 | 0.5892 | 0.033* | |
| C5 | 0.5941 (5) | 1.07339 (18) | 0.5156 (6) | 0.0155 (6) | |
| H5A | 0.4856 | 1.0641 | 0.4530 | 0.019* | |
| C6 | 0.7009 (4) | 1.02135 (18) | 0.5771 (5) | 0.0136 (6) | |
| C7 | 0.6593 (4) | 0.94980 (17) | 0.5520 (5) | 0.0137 (7) | |
| C8 | 0.5058 (4) | 0.9266 (2) | 0.4740 (6) | 0.0167 (7) | |
| H8A | 0.4208 | 0.9573 | 0.4344 | 0.020* | |
| C9 | 0.4773 (5) | 0.85789 (19) | 0.4542 (6) | 0.0162 (7) | |
| C9A | 0.3132 (5) | 0.8319 (2) | 0.3748 (7) | 0.0225 (8) | |
| H9AA | 0.2582 | 0.8514 | 0.2425 | 0.034* | |
| H9AB | 0.2588 | 0.8441 | 0.4666 | 0.034* | |
| H9AC | 0.3151 | 0.7832 | 0.3630 | 0.034* | |
| C10 | 0.6064 (5) | 0.81541 (19) | 0.5120 (6) | 0.0192 (7) | |
| H10A | 0.5919 | 0.7684 | 0.4982 | 0.023* | |
| C11 | 0.7558 (5) | 0.84178 (19) | 0.5896 (6) | 0.0191 (7) | |
| H11A | 0.8425 | 0.8120 | 0.6290 | 0.023* | |
| N12 | 0.7834 (3) | 0.90766 (15) | 0.6114 (5) | 0.0153 (6) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.01070 (19) | 0.0139 (2) | 0.0205 (2) | 0.00155 (17) | 0.00239 (16) | 0.00001 (18) |
| Cl1 | 0.0162 (4) | 0.0162 (4) | 0.0347 (5) | 0.0053 (3) | 0.0016 (4) | 0.0024 (4) |
| Cl2 | 0.0135 (4) | 0.0235 (4) | 0.0134 (4) | −0.0012 (3) | 0.0044 (3) | −0.0025 (3) |
| N1 | 0.0131 (15) | 0.0153 (14) | 0.0203 (15) | 0.0005 (12) | 0.0046 (13) | −0.0014 (12) |
| C2 | 0.0144 (18) | 0.0188 (18) | 0.029 (2) | −0.0023 (14) | 0.0042 (16) | −0.0002 (15) |
| C3 | 0.0200 (19) | 0.0150 (17) | 0.026 (2) | −0.0012 (14) | 0.0050 (17) | −0.0016 (15) |
| C4 | 0.0171 (17) | 0.0148 (17) | 0.0170 (17) | 0.0004 (13) | 0.0057 (14) | −0.0009 (13) |
| C4A | 0.0179 (18) | 0.0161 (18) | 0.030 (2) | 0.0021 (15) | 0.0061 (16) | −0.0006 (16) |
| C5 | 0.0107 (15) | 0.0151 (16) | 0.0198 (18) | 0.0020 (14) | 0.0043 (14) | −0.0005 (14) |
| C6 | 0.0143 (16) | 0.0144 (16) | 0.0133 (16) | 0.0018 (13) | 0.0063 (13) | 0.0007 (13) |
| C7 | 0.0149 (17) | 0.0130 (16) | 0.0140 (17) | 0.0000 (13) | 0.0062 (15) | −0.0001 (12) |
| C8 | 0.0148 (19) | 0.0168 (18) | 0.0184 (17) | 0.0005 (13) | 0.0057 (15) | −0.0008 (14) |
| C9 | 0.0154 (17) | 0.0172 (17) | 0.0161 (17) | −0.0030 (13) | 0.0057 (14) | −0.0018 (14) |
| C9A | 0.017 (2) | 0.0190 (19) | 0.029 (2) | −0.0051 (15) | 0.0047 (17) | −0.0032 (16) |
| C10 | 0.0202 (18) | 0.0128 (16) | 0.0239 (19) | 0.0004 (14) | 0.0069 (16) | 0.0013 (14) |
| C11 | 0.0161 (18) | 0.0154 (17) | 0.025 (2) | 0.0028 (13) | 0.0062 (16) | −0.0002 (14) |
| N12 | 0.0123 (14) | 0.0136 (14) | 0.0191 (15) | 0.0022 (12) | 0.0044 (12) | 0.0000 (12) |
Geometric parameters (Å, º)
| Cu1—N1 | 2.009 (3) | C5—C6 | 1.387 (5) |
| Cu1—N12 | 2.047 (3) | C5—H5A | 0.9500 |
| Cu1—Cl1 | 2.2506 (10) | C6—C7 | 1.476 (5) |
| Cu1—Cl2 | 2.3320 (10) | C7—N12 | 1.354 (4) |
| Cu1—Cl2i | 2.5623 (9) | C7—C8 | 1.391 (5) |
| Cl2—Cu1ii | 2.5623 (9) | C8—C9 | 1.398 (5) |
| N1—C2 | 1.343 (5) | C8—H8A | 0.9500 |
| N1—C6 | 1.357 (5) | C9—C10 | 1.391 (5) |
| C2—C3 | 1.375 (6) | C9—C9A | 1.494 (5) |
| C2—H2A | 0.9500 | C9A—H9AA | 0.9800 |
| C3—C4 | 1.392 (5) | C9A—H9AB | 0.9800 |
| C3—H3A | 0.9500 | C9A—H9AC | 0.9800 |
| C4—C5 | 1.400 (5) | C10—C11 | 1.382 (6) |
| C4—C4A | 1.495 (5) | C10—H10A | 0.9500 |
| C4A—H4AA | 0.9800 | C11—N12 | 1.341 (5) |
| C4A—H4AB | 0.9800 | C11—H11A | 0.9500 |
| C4A—H4AC | 0.9800 | ||
| N1—Cu1—N12 | 79.25 (12) | C6—C5—H5A | 120.1 |
| N1—Cu1—Cl1 | 172.93 (10) | C4—C5—H5A | 120.1 |
| N12—Cu1—Cl1 | 93.82 (9) | N1—C6—C5 | 121.6 (4) |
| N1—Cu1—Cl2 | 92.64 (10) | N1—C6—C7 | 113.8 (3) |
| N12—Cu1—Cl2 | 143.41 (9) | C5—C6—C7 | 124.6 (4) |
| Cl1—Cu1—Cl2 | 93.79 (4) | N12—C7—C8 | 122.0 (3) |
| N1—Cu1—Cl2i | 89.55 (9) | N12—C7—C6 | 114.5 (3) |
| N12—Cu1—Cl2i | 121.94 (9) | C8—C7—C6 | 123.4 (3) |
| Cl1—Cu1—Cl2i | 93.01 (4) | C7—C8—C9 | 119.5 (4) |
| Cl2—Cu1—Cl2i | 93.29 (3) | C7—C8—H8A | 120.2 |
| Cu1—Cl2—Cu1ii | 111.20 (4) | C9—C8—H8A | 120.2 |
| C2—N1—C6 | 118.8 (3) | C10—C9—C8 | 117.6 (4) |
| C2—N1—Cu1 | 124.2 (3) | C10—C9—C9A | 122.0 (4) |
| C6—N1—Cu1 | 117.0 (2) | C8—C9—C9A | 120.4 (4) |
| N1—C2—C3 | 122.1 (4) | C9—C9A—H9AA | 109.5 |
| N1—C2—H2A | 119.0 | C9—C9A—H9AB | 109.5 |
| C3—C2—H2A | 119.0 | H9AA—C9A—H9AB | 109.5 |
| C2—C3—C4 | 120.5 (3) | C9—C9A—H9AC | 109.5 |
| C2—C3—H3A | 119.7 | H9AA—C9A—H9AC | 109.5 |
| C4—C3—H3A | 119.7 | H9AB—C9A—H9AC | 109.5 |
| C3—C4—C5 | 117.2 (3) | C11—C10—C9 | 119.8 (3) |
| C3—C4—C4A | 121.2 (3) | C11—C10—H10A | 120.1 |
| C5—C4—C4A | 121.7 (4) | C9—C10—H10A | 120.1 |
| C4—C4A—H4AA | 109.5 | N12—C11—C10 | 122.7 (3) |
| C4—C4A—H4AB | 109.5 | N12—C11—H11A | 118.6 |
| H4AA—C4A—H4AB | 109.5 | C10—C11—H11A | 118.6 |
| C4—C4A—H4AC | 109.5 | C11—N12—C7 | 118.3 (3) |
| H4AA—C4A—H4AC | 109.5 | C11—N12—Cu1 | 126.3 (3) |
| H4AB—C4A—H4AC | 109.5 | C7—N12—Cu1 | 115.3 (2) |
| C6—C5—C4 | 119.9 (4) | ||
| C6—N1—C2—C3 | 1.2 (6) | N1—C6—C7—C8 | 175.7 (3) |
| Cu1—N1—C2—C3 | 178.8 (3) | C5—C6—C7—C8 | −4.1 (6) |
| N1—C2—C3—C4 | 0.1 (6) | N12—C7—C8—C9 | −0.5 (6) |
| C2—C3—C4—C5 | −1.0 (6) | C6—C7—C8—C9 | 179.5 (3) |
| C2—C3—C4—C4A | 179.3 (4) | C7—C8—C9—C10 | −0.9 (6) |
| C3—C4—C5—C6 | 0.7 (5) | C7—C8—C9—C9A | 178.7 (3) |
| C4A—C4—C5—C6 | −179.7 (4) | C8—C9—C10—C11 | 1.3 (6) |
| C2—N1—C6—C5 | −1.6 (5) | C9A—C9—C10—C11 | −178.3 (4) |
| Cu1—N1—C6—C5 | −179.3 (3) | C9—C10—C11—N12 | −0.4 (6) |
| C2—N1—C6—C7 | 178.6 (3) | C10—C11—N12—C7 | −1.0 (6) |
| Cu1—N1—C6—C7 | 0.9 (4) | C10—C11—N12—Cu1 | 174.3 (3) |
| C4—C5—C6—N1 | 0.6 (6) | C8—C7—N12—C11 | 1.4 (6) |
| C4—C5—C6—C7 | −179.7 (3) | C6—C7—N12—C11 | −178.6 (3) |
| N1—C6—C7—N12 | −4.3 (4) | C8—C7—N12—Cu1 | −174.4 (3) |
| C5—C6—C7—N12 | 176.0 (4) | C6—C7—N12—Cu1 | 5.6 (4) |
Symmetry codes: (i) x, −y+2, z−1/2; (ii) x, −y+2, z+1/2.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C11—H11A···Cl1 | 0.95 | 2.61 | 3.211 (4) | 122 |
| C8—H8A···Cl2iii | 0.95 | 2.88 | 3.666 (4) | 140 |
| C10—H10A···Cl1iv | 0.95 | 2.88 | 3.733 (4) | 149 |
Symmetry codes: (iii) x−1, −y+2, z−1/2; (iv) x−1/2, −y+3/2, z−1/2.
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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/S2056989015008944/zl2617sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008944/zl2617Isup2.hkl
CCDC reference: 1063931
Additional supporting information: crystallographic information; 3D view; checkCIF report