Each CrIII cation in the title compound is coordinated by the six N atoms from two 1,4,7-triazacyclononane (tacn) ligands, displaying a distorted octahedral environment. The crystal packing is stabilized by extensive hydrogen-bonding interactions involving the N—H groups of the tacn ligands, O—H groups or O atoms of the water molecules and Cl atoms of the [ZnCl4]2− anions.
Keywords: crystal structure; 1,4,7-triazacyclononane; tetrachloridozincate; chromium(III) complex; hydrogen bonding; synchrotron radiation
Abstract
The structure of the title compound, [Cr(tacn)2]2[ZnCl4]3·H2O (tacn is 1,4,7-triazacyclononane; C6H15N3), has been determined from synchrotron X-ray data. Each CrIII cation is coordinated by the six N atoms from the two tacn ligands, displaying a distorted octahedral geometry. Three distorted tetrahedral [ZnCl4]2− anions and one lattice water molecule lie outside this coordination sphere. The Cr—N bond lengths are in the range 2.0621 (11) to 2.0851 (12) Å, while the mean inner N—Cr—N bond angle is 82.51 (5)°. The crystal packing is stabilized by hydrogen-bonding interactions with the N—H groups of the tacn ligands and the water O—H groups acting as donors, and the O atoms of the water molecules and Cl atoms of the [ZnCl4]2− anions as acceptors. Overall these contacts lead to the formation of a three-dimensional network.
Chemical context
The 1,4,7-triazacyclononane (tacn, C6H15N3) ligand can coordinate facially to many transition metal ions in various oxidation states (Chaudhuri & Wieghardt, 1987 ▸). The macrocycle tacn is tridentate, a pure σ-donor with no π-acceptor capability. In particular, the preparation, spectroscopic properties and ligand field analysis of a [Cr(tacn)2]3+ complex with a chloride anion have been described (Wieghardt et al., 1983 ▸; Lee & Hoggard, 1991 ▸). Counter-anionic species play very important roles in the coordination chemistry and supramolecular chemistry of such complexes (Fabbrizzi & Poggi, 2013 ▸; Santos-Figueroa et al., 2013 ▸). The crystal structure of [Cr(tacn)2]Br5·5H2O (Scarborough et al., 2011 ▸) has been reported, but a [Cr(tacn)2]3+ complex with a [ZnCl4]2− counter-anion is not known.
The title compound is another example of a [Cr(tacn)2]3+ complex but with a different counter-anion. In order to confirm that the crystal is a salt of the [ZnCl4]2− anion, we report here the molecular and crystal structure of the new complex [Cr(tacn)2]2[ZnCl4]3·H2O, (I) determined from synchrotron X-ray data.
Structural commentary
The X-ray structural determination of (I) was carried out at 100 (2) K with synchrotron radiation to confirm its exact geometry and composition. The structure consists of two independent [Cr(tacn)2]3+ cations, three [ZnCl4]2− anions and one lattice water molecule. Fig. 1 ▸ shows an ellipsoid plot of the asymmetric unit of compound (I) with the atomic labelling scheme. The CrIII cation in both [Cr1A(tacn)2]3+ and [Cr2B(tacn)2]3+ is coordinated by the six N atoms from the two tacn ligands, displaying a distorted octahedral geometry. The Cr—N(tacn) bond distances for [Cr1A(tacn)2]3+ and [Cr2B(tacn)2]3+ are in the ranges 2.0709 (11) to 2.0828 (11) Å and 2.0621 (11) to 2.0851 (11) Å, respectively, in good agreement with the observed values in [Cr(tacn)2]Br3·5H2O [2.073 (1) Å; Scarborough et al., 2011 ▸] and [Cr(chxn)3][ZnCl4]Cl·3H2O [2.0737 (12)–2.0928 (12) Å; chxn = trans-1,2-cyclohexanediamine, C6H14N2; Moon & Choi, 2016 ▸]. However, the bond lengths and bond angles of the two discrete [Cr(tacn)2]3+ cations are slightly different from each other. In general, three metrics of the bond angles for [M(tacn)2]n+ cations are used. The angles are N—M—Nintra for the intraligand angles, and N—M—Ntrans and N—M—Ninter for trans and cis interligand angles, respectively (Lord et al., 2009 ▸). The mean N—M—Nintra, N—M—Ntrans and N—M—Ninter for [Cr1A(tacn)2]3+ are 82.35 (5), 178.60 (5) and 97.64 (5)° while the three corresponding angles for [Cr2B(tacn)2]3+ are 82.66 (5), 177.13 (5) and 97.36 (5)°, respectively. These values for each of the three types of angles may be compared with the literature values for [M(tacn)2]n+ (M = Mn2+, Fe2+, Fe3+, Co2+, Co3+ and Ni2+; Lord et al., 2009 ▸). All five-membered chelate rings of the tacn ligands have the stable gauche conformations. Three tetrahedral [ZnCl4]2− anions and an additional water molecule remain outside the coordination sphere of Cr3+. Each ZnCl4 2− anion has a slightly distorted tetrahedral coordination geometry because of the influence of hydrogen bonding on the Zn—Cl lengths and the Cl—Zn–Cl angles. The Zn—Cl bond lengths involved in hydrogen bonds were all found to have longer bonds than those not involved.
Figure 1.
The structures of the molecular components in the asymmetric unit of the title complex (I), drawn with displacement ellipsoids at the 70% probability level. Dashed lines represent hydrogen-bonding interactions. The H atoms on the C atoms have been omitted for clarity.
Supramolecular features
Extensive hydrogen-bonding interactions occur in the crystal structure (Table 1 ▸). The supramolecular architecture involves hydrogen-bonding interactions with the N—H groups from each of the tacn ligands, the O—H groups of the lattice water molecules acting as donors, and Cl atoms of the [ZnCl4]2− anions and the O atoms of the water molecules acting as acceptors, giving rise to a three-dimensional network structure. The network comprises columns of molecules that form along the a-axis direction (Fig. 2 ▸). These hydrogen-bonded networks help to stabilize the crystal structure.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N5A—H5A⋯O1W | 1.00 | 2.46 | 3.1535 (19) | 126 |
| N2B—H2B⋯Cl1E | 1.00 | 2.25 | 3.1608 (12) | 151 |
| N4B—H4B⋯Cl2D | 1.00 | 2.24 | 3.1179 (12) | 146 |
| O1W—H2OW⋯Cl3D | 0.96 (1) | 2.44 (1) | 3.3163 (16) | 152 (2) |
| N1A—H1A⋯Cl4C i | 1.00 | 2.23 | 3.2091 (13) | 167 |
| N4A—H4A⋯Cl1C i | 1.00 | 2.29 | 3.2377 (12) | 158 |
| N2A—H2A⋯Cl2C ii | 1.00 | 2.42 | 3.2981 (13) | 146 |
| N6A—H6A⋯Cl4C ii | 1.00 | 2.23 | 3.1811 (13) | 159 |
| N3A—H3A⋯Cl1C iii | 1.00 | 2.62 | 3.4416 (13) | 140 |
| N5A—H5A⋯Cl1C iii | 1.00 | 2.50 | 3.2875 (13) | 136 |
| N1B—H1B⋯Cl2D iv | 1.00 | 2.42 | 3.2707 (12) | 143 |
| N3B—H3B⋯Cl4E iv | 1.00 | 2.36 | 3.2884 (12) | 154 |
| N5B—H5B⋯Cl1E iv | 1.00 | 2.46 | 3.2932 (12) | 141 |
| N6B—H6B⋯Cl4D iv | 1.00 | 2.35 | 3.2935 (12) | 157 |
| O1W—H1OW⋯Cl2C v | 0.95 (1) | 2.32 (1) | 3.2520 (15) | 166 (2) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
.
Figure 2.
The crystal packing of complex (I) viewed perpendicular to the ac plane. Dashed lines represent O—H⋯Cl (purple), N—H⋯O (blue) and N—H⋯Cl (cyan) hydrogen-bonding interactions.
Database survey
A search of the Cambridge Structural Database (Version 5.39, Aug 2018 with four updates; Groom et al., 2016 ▸) gave 11 hits for trivalent metal complexes containing two tacn (C6H15N3) ligands. The structures of [Ni(tacn)2](NO3)Cl·H2O (Zompa & Margulis, 1978 ▸), [Fe(tacn)2]Cl3·5H2O (Boeyens et al., 1985 ▸), [Pd(tacn)2](PF6)3 (Blake et al., 1988 ▸) and [Co(tacn)2](ClO4)3 (Wang et al., 2002 ▸) have been published previously. However, only one structure containing the [Cr(tacn)3]3+ form is present (Scarborough et al., 2011 ▸). Each metal ion in all of these complexes is sandwiched between two tridentate tacn macrocycles. Until now, no structure of any salt of [Cr(tacn)2]3+ with the [ZnCl4]2− anion has been deposited.
Synthesis and crystallization
Commercially available (Sigma–Aldrich) 1,4,7-triazacyclononane was used as provided. All other chemicals were the best AR grade available. The starting material [Cr(tacn)2]Cl3 was prepared according to the literature (Wieghardt et al., 1983 ▸). The crude trichloride salt (0.10 g) was dissolved in 7 mL of 0.5 M HCl at 313 K. 5 mL of a 1 M HCl solution containing 0.25 g of solid ZnCl2 were added to this solution. The resulting mixture was filtered, and allowed to stand at room temperature for two days to give plate-like yellow crystals of the title tetrachloridozincate(II) salt suitable for single-crystal X-ray diffraction.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Non-hydrogen atoms were refined anisotropically. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.99 Å and N—H = 1.00 Å, and with U iso(H) values of 1.2U eq of the parent atoms. The O-bound H atoms of the water molecules were assigned based on a difference-Fourier map, and were refined with distance restraints of 0.95 (10) Å (using the DFIX and DANG commands), and U iso(H) values of 1.5U eq of the oxygen atom.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Cr(C6H15N3)2]2[ZnCl4]3·H2O |
| M r | 1260.36 |
| Crystal system, space group | Orthorhombic, P b c a |
| Temperature (K) | 100 |
| a, b, c (Å) | 17.281 (4), 16.753 (3), 33.405 (7) |
| V (Å3) | 9671 (3) |
| Z | 8 |
| Radiation type | Synchrotron, λ = 0.62998 Å |
| μ (mm−1) | 1.86 |
| Crystal size (mm) | 0.15 × 0.10 × 0.08 |
| Data collection | |
| Diffractometer | ADSC Q210 CCD area detector |
| Absorption correction | Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski et al., 1997 ▸) |
| T min, T max | 0.768, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 95478, 13601, 12445 |
| R int | 0.050 |
| (sin θ/λ)max (Å−1) | 0.696 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.025, 0.071, 1.06 |
| No. of reflections | 13601 |
| No. of parameters | 493 |
| No. of restraints | 3 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 1.01, −0.96 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019003086/sj5569sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019003086/sj5569Isup2.hkl
CCDC reference: 1900397
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| [Cr(C6H15N3)2]2[ZnCl4]3·H2O | Dx = 1.731 Mg m−3 |
| Mr = 1260.36 | Synchrotron radiation, λ = 0.62998 Å |
| Orthorhombic, Pbca | Cell parameters from 295495 reflections |
| a = 17.281 (4) Å | θ = 0.4–33.6° |
| b = 16.753 (3) Å | µ = 1.86 mm−1 |
| c = 33.405 (7) Å | T = 100 K |
| V = 9671 (3) Å3 | Plate, yellow |
| Z = 8 | 0.15 × 0.10 × 0.08 mm |
| F(000) = 5120 |
Data collection
| ADSC Q210 CCD area detector diffractometer | 12445 reflections with I > 2σ(I) |
| Radiation source: PLSII 2D bending magnet | Rint = 0.050 |
| ω scan | θmax = 26.0°, θmin = 1.6° |
| Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski et al., 1997) | h = −24→24 |
| Tmin = 0.768, Tmax = 1.000 | k = −23→23 |
| 95478 measured reflections | l = −46→46 |
| 13601 independent reflections |
Refinement
| Refinement on F2 | 3 restraints |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0409P)2 + 5.110P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.006 |
| 13601 reflections | Δρmax = 1.01 e Å−3 |
| 493 parameters | Δρmin = −0.96 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 | ||
| Cr1A | 0.82954 (2) | 0.48430 (2) | 0.74710 (2) | 0.00703 (4) | |
| N1A | 0.73238 (6) | 0.48954 (7) | 0.78330 (3) | 0.0113 (2) | |
| H1A | 0.687279 | 0.506644 | 0.766621 | 0.014* | |
| N2A | 0.87599 (6) | 0.55581 (6) | 0.79209 (3) | 0.0112 (2) | |
| H2A | 0.915224 | 0.592659 | 0.780136 | 0.013* | |
| N3A | 0.86016 (7) | 0.39319 (6) | 0.78636 (3) | 0.0116 (2) | |
| H3A | 0.874864 | 0.344914 | 0.770486 | 0.014* | |
| N4A | 0.79614 (7) | 0.57390 (6) | 0.70780 (3) | 0.01109 (19) | |
| H4A | 0.764457 | 0.614134 | 0.722638 | 0.013* | |
| N5A | 0.78444 (7) | 0.41078 (7) | 0.70289 (3) | 0.0131 (2) | |
| H5A | 0.761936 | 0.362150 | 0.715765 | 0.016* | |
| N6A | 0.92602 (6) | 0.48125 (7) | 0.70986 (3) | 0.0126 (2) | |
| H6A | 0.973683 | 0.486302 | 0.726647 | 0.015* | |
| C1A | 0.74241 (8) | 0.54831 (8) | 0.81699 (4) | 0.0149 (2) | |
| H1A1 | 0.752269 | 0.519256 | 0.842286 | 0.018* | |
| H1A2 | 0.694404 | 0.579882 | 0.820294 | 0.018* | |
| C2A | 0.80979 (8) | 0.60390 (8) | 0.80808 (4) | 0.0152 (2) | |
| H2A1 | 0.793951 | 0.644436 | 0.788136 | 0.018* | |
| H2A2 | 0.825747 | 0.631907 | 0.832836 | 0.018* | |
| C3A | 0.91411 (8) | 0.50600 (8) | 0.82401 (4) | 0.0153 (2) | |
| H3A1 | 0.880148 | 0.503350 | 0.847837 | 0.018* | |
| H3A2 | 0.963528 | 0.531163 | 0.832107 | 0.018* | |
| C4A | 0.92954 (8) | 0.42221 (9) | 0.80863 (4) | 0.0161 (3) | |
| H4A1 | 0.975126 | 0.422542 | 0.790678 | 0.019* | |
| H4A2 | 0.940669 | 0.386092 | 0.831365 | 0.019* | |
| C5A | 0.79365 (8) | 0.37205 (8) | 0.81358 (4) | 0.0141 (2) | |
| H5A1 | 0.803434 | 0.393743 | 0.840678 | 0.017* | |
| H5A2 | 0.789349 | 0.313284 | 0.815748 | 0.017* | |
| C6A | 0.71858 (8) | 0.40602 (8) | 0.79736 (4) | 0.0147 (2) | |
| H6A1 | 0.699861 | 0.372786 | 0.774846 | 0.018* | |
| H6A2 | 0.678589 | 0.405796 | 0.818579 | 0.018* | |
| C7A | 0.74887 (8) | 0.54068 (8) | 0.67381 (4) | 0.0159 (2) | |
| H7A1 | 0.780731 | 0.539014 | 0.649191 | 0.019* | |
| H7A2 | 0.703905 | 0.575871 | 0.668727 | 0.019* | |
| C8A | 0.72081 (8) | 0.45739 (9) | 0.68380 (4) | 0.0171 (3) | |
| H8A1 | 0.676127 | 0.460616 | 0.702275 | 0.021* | |
| H8A2 | 0.703626 | 0.430144 | 0.659046 | 0.021* | |
| C9A | 0.84575 (9) | 0.38539 (8) | 0.67355 (4) | 0.0170 (3) | |
| H9A1 | 0.839435 | 0.415422 | 0.648233 | 0.020* | |
| H9A2 | 0.839895 | 0.327834 | 0.667553 | 0.020* | |
| C10A | 0.92552 (9) | 0.40078 (8) | 0.69058 (4) | 0.0173 (3) | |
| H10C | 0.938524 | 0.359294 | 0.710587 | 0.021* | |
| H10D | 0.964601 | 0.398797 | 0.668937 | 0.021* | |
| C11A | 0.92473 (8) | 0.54815 (8) | 0.67986 (4) | 0.0150 (2) | |
| H11A | 0.908068 | 0.527532 | 0.653463 | 0.018* | |
| H11B | 0.977349 | 0.570786 | 0.676931 | 0.018* | |
| C12A | 0.86932 (9) | 0.61256 (8) | 0.69379 (4) | 0.0149 (2) | |
| H12C | 0.892906 | 0.643434 | 0.715918 | 0.018* | |
| H12D | 0.858029 | 0.649697 | 0.671493 | 0.018* | |
| Cr2B | 0.37785 (2) | 0.24725 (2) | 0.50148 (2) | 0.00596 (4) | |
| N1B | 0.30089 (6) | 0.15782 (6) | 0.51771 (3) | 0.00828 (18) | |
| H1B | 0.262173 | 0.150115 | 0.495797 | 0.010* | |
| N2B | 0.45967 (6) | 0.16291 (7) | 0.51723 (3) | 0.01044 (19) | |
| H2B | 0.505894 | 0.169844 | 0.499566 | 0.013* | |
| N3B | 0.37847 (6) | 0.26919 (7) | 0.56267 (3) | 0.00966 (19) | |
| H3B | 0.365415 | 0.326551 | 0.567453 | 0.012* | |
| N4B | 0.45940 (6) | 0.33063 (7) | 0.48468 (3) | 0.01023 (19) | |
| H4B | 0.506540 | 0.322634 | 0.501568 | 0.012* | |
| N5B | 0.30051 (6) | 0.33765 (6) | 0.48693 (3) | 0.00844 (18) | |
| H5B | 0.262920 | 0.344899 | 0.509396 | 0.010* | |
| N6B | 0.37491 (6) | 0.22685 (7) | 0.43992 (3) | 0.00947 (19) | |
| H6B | 0.360772 | 0.169847 | 0.434887 | 0.011* | |
| C1B | 0.34251 (7) | 0.08032 (7) | 0.52523 (4) | 0.0118 (2) | |
| H1B1 | 0.313751 | 0.036070 | 0.512406 | 0.014* | |
| H1B2 | 0.344478 | 0.069835 | 0.554383 | 0.014* | |
| C2B | 0.42428 (8) | 0.08337 (8) | 0.50860 (4) | 0.0136 (2) | |
| H2B1 | 0.455922 | 0.040725 | 0.520962 | 0.016* | |
| H2B2 | 0.423093 | 0.074245 | 0.479324 | 0.016* | |
| C3B | 0.48497 (8) | 0.17292 (8) | 0.56018 (4) | 0.0137 (2) | |
| H3B1 | 0.541986 | 0.168265 | 0.561918 | 0.016* | |
| H3B2 | 0.461894 | 0.130150 | 0.576784 | 0.016* | |
| C4B | 0.45967 (7) | 0.25416 (8) | 0.57609 (4) | 0.0130 (2) | |
| H4B1 | 0.462384 | 0.254683 | 0.605687 | 0.016* | |
| H4B2 | 0.494325 | 0.296402 | 0.565691 | 0.016* | |
| C5B | 0.32037 (7) | 0.21759 (8) | 0.58400 (4) | 0.0116 (2) | |
| H5B1 | 0.294559 | 0.248872 | 0.605307 | 0.014* | |
| H5B2 | 0.347052 | 0.171820 | 0.596692 | 0.014* | |
| C6B | 0.26045 (7) | 0.18728 (8) | 0.55445 (4) | 0.0103 (2) | |
| H6B1 | 0.230193 | 0.143422 | 0.566681 | 0.012* | |
| H6B2 | 0.224320 | 0.230879 | 0.547310 | 0.012* | |
| C7B | 0.42574 (8) | 0.41035 (8) | 0.49455 (4) | 0.0132 (2) | |
| H7B1 | 0.456972 | 0.452904 | 0.481828 | 0.016* | |
| H7B2 | 0.426943 | 0.418697 | 0.523886 | 0.016* | |
| C8B | 0.34263 (7) | 0.41501 (7) | 0.47962 (4) | 0.0118 (2) | |
| H8B1 | 0.315365 | 0.458898 | 0.493589 | 0.014* | |
| H8B2 | 0.342533 | 0.427027 | 0.450607 | 0.014* | |
| C9B | 0.25820 (7) | 0.30974 (8) | 0.45055 (4) | 0.0111 (2) | |
| H9B1 | 0.227682 | 0.354205 | 0.439070 | 0.013* | |
| H9B2 | 0.222138 | 0.266153 | 0.457783 | 0.013* | |
| C10B | 0.31657 (7) | 0.28003 (8) | 0.42001 (4) | 0.0118 (2) | |
| H10A | 0.289480 | 0.250080 | 0.398651 | 0.014* | |
| H10B | 0.343222 | 0.326058 | 0.407548 | 0.014* | |
| C11B | 0.45521 (7) | 0.24149 (8) | 0.42513 (4) | 0.0124 (2) | |
| H11C | 0.455822 | 0.242191 | 0.395500 | 0.015* | |
| H11D | 0.490099 | 0.198424 | 0.434418 | 0.015* | |
| C12B | 0.48249 (8) | 0.32173 (8) | 0.44140 (4) | 0.0130 (2) | |
| H12A | 0.539462 | 0.325548 | 0.438979 | 0.016* | |
| H12B | 0.459285 | 0.365434 | 0.425469 | 0.016* | |
| Zn1C | 0.07329 (2) | 0.67835 (2) | 0.74676 (2) | 0.01331 (4) | |
| Cl1C | 0.19073 (2) | 0.72564 (2) | 0.76712 (2) | 0.01642 (7) | |
| Cl2C | −0.02687 (2) | 0.72432 (2) | 0.78306 (2) | 0.02366 (8) | |
| Cl3C | 0.06377 (3) | 0.71107 (2) | 0.68204 (2) | 0.02680 (9) | |
| Cl4C | 0.07302 (2) | 0.54414 (2) | 0.75772 (2) | 0.01610 (7) | |
| Zn2D | 0.65175 (2) | 0.39591 (2) | 0.58225 (2) | 0.01018 (4) | |
| Cl1D | 0.57342 (2) | 0.49024 (2) | 0.60669 (2) | 0.02659 (9) | |
| Cl2D | 0.62528 (2) | 0.36622 (2) | 0.51676 (2) | 0.01529 (6) | |
| Cl3D | 0.64207 (2) | 0.28477 (2) | 0.62022 (2) | 0.01465 (6) | |
| Cl4D | 0.77816 (2) | 0.43965 (2) | 0.57568 (2) | 0.01200 (6) | |
| Zn3E | 0.65313 (2) | 0.10971 (2) | 0.41217 (2) | 0.00947 (4) | |
| Cl1E | 0.62418 (2) | 0.13302 (2) | 0.47869 (2) | 0.01281 (6) | |
| Cl2E | 0.64032 (2) | 0.22326 (2) | 0.37751 (2) | 0.01410 (6) | |
| Cl3E | 0.57773 (2) | 0.01372 (2) | 0.38615 (2) | 0.02218 (8) | |
| Cl4E | 0.78037 (2) | 0.06714 (2) | 0.41790 (2) | 0.01168 (6) | |
| O1W | 0.62401 (9) | 0.32554 (8) | 0.71692 (4) | 0.0364 (3) | |
| H1OW | 0.5882 (13) | 0.2988 (15) | 0.7337 (6) | 0.055* | |
| H2OW | 0.6101 (14) | 0.3130 (15) | 0.6899 (3) | 0.055* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cr1A | 0.00877 (10) | 0.00634 (9) | 0.00597 (9) | 0.00020 (7) | 0.00093 (6) | 0.00002 (6) |
| N1A | 0.0098 (5) | 0.0151 (5) | 0.0089 (5) | 0.0009 (4) | 0.0007 (4) | −0.0011 (4) |
| N2A | 0.0135 (5) | 0.0105 (5) | 0.0097 (5) | −0.0015 (4) | −0.0022 (4) | 0.0003 (4) |
| N3A | 0.0149 (5) | 0.0089 (5) | 0.0110 (5) | 0.0010 (4) | 0.0036 (4) | 0.0025 (4) |
| N4A | 0.0155 (5) | 0.0095 (4) | 0.0083 (4) | 0.0034 (4) | 0.0001 (4) | −0.0006 (4) |
| N5A | 0.0183 (5) | 0.0110 (5) | 0.0101 (5) | −0.0032 (4) | 0.0027 (4) | −0.0027 (4) |
| N6A | 0.0128 (5) | 0.0115 (5) | 0.0134 (5) | 0.0017 (4) | 0.0041 (4) | 0.0023 (4) |
| C1A | 0.0173 (6) | 0.0166 (6) | 0.0107 (5) | 0.0043 (5) | 0.0018 (5) | −0.0042 (5) |
| C2A | 0.0230 (7) | 0.0109 (5) | 0.0117 (6) | 0.0031 (5) | −0.0009 (5) | −0.0039 (4) |
| C3A | 0.0154 (6) | 0.0177 (6) | 0.0128 (6) | −0.0013 (5) | −0.0054 (5) | 0.0037 (5) |
| C4A | 0.0134 (6) | 0.0174 (6) | 0.0174 (6) | 0.0024 (5) | −0.0020 (5) | 0.0075 (5) |
| C5A | 0.0178 (6) | 0.0129 (5) | 0.0115 (5) | −0.0023 (5) | 0.0044 (5) | 0.0030 (4) |
| C6A | 0.0141 (6) | 0.0174 (6) | 0.0126 (6) | −0.0050 (5) | 0.0030 (5) | 0.0006 (5) |
| C7A | 0.0186 (6) | 0.0189 (6) | 0.0104 (5) | 0.0028 (5) | −0.0037 (5) | −0.0008 (5) |
| C8A | 0.0166 (6) | 0.0227 (7) | 0.0120 (6) | −0.0034 (5) | −0.0017 (5) | −0.0036 (5) |
| C9A | 0.0284 (7) | 0.0103 (5) | 0.0124 (6) | 0.0005 (5) | 0.0074 (5) | −0.0030 (4) |
| C10A | 0.0231 (7) | 0.0117 (6) | 0.0171 (6) | 0.0074 (5) | 0.0089 (5) | 0.0015 (5) |
| C11A | 0.0180 (6) | 0.0119 (6) | 0.0152 (6) | −0.0019 (5) | 0.0062 (5) | 0.0038 (5) |
| C12A | 0.0237 (7) | 0.0076 (5) | 0.0134 (6) | −0.0016 (5) | 0.0017 (5) | 0.0023 (4) |
| Cr2B | 0.00346 (9) | 0.00755 (9) | 0.00689 (9) | 0.00014 (6) | 0.00000 (6) | 0.00075 (6) |
| N1B | 0.0063 (4) | 0.0082 (4) | 0.0103 (4) | 0.0000 (4) | 0.0001 (4) | 0.0014 (3) |
| N2B | 0.0066 (5) | 0.0135 (5) | 0.0112 (5) | 0.0028 (4) | 0.0004 (4) | 0.0017 (4) |
| N3B | 0.0070 (5) | 0.0129 (5) | 0.0090 (5) | −0.0008 (4) | −0.0002 (4) | −0.0006 (4) |
| N4B | 0.0062 (4) | 0.0137 (5) | 0.0107 (5) | −0.0031 (4) | −0.0007 (4) | 0.0018 (4) |
| N5B | 0.0063 (4) | 0.0089 (4) | 0.0101 (4) | 0.0007 (4) | 0.0005 (4) | 0.0011 (4) |
| N6B | 0.0075 (5) | 0.0118 (5) | 0.0091 (4) | 0.0003 (4) | 0.0003 (4) | −0.0012 (4) |
| C1B | 0.0117 (6) | 0.0086 (5) | 0.0151 (6) | 0.0019 (4) | −0.0007 (4) | 0.0020 (4) |
| C2B | 0.0128 (6) | 0.0106 (5) | 0.0173 (6) | 0.0048 (5) | 0.0017 (5) | 0.0002 (5) |
| C3B | 0.0085 (5) | 0.0204 (6) | 0.0121 (5) | 0.0021 (5) | −0.0017 (4) | 0.0036 (5) |
| C4B | 0.0078 (5) | 0.0199 (6) | 0.0112 (5) | −0.0031 (5) | −0.0022 (4) | 0.0015 (5) |
| C5B | 0.0085 (5) | 0.0169 (6) | 0.0093 (5) | −0.0017 (4) | 0.0019 (4) | 0.0014 (4) |
| C6B | 0.0055 (5) | 0.0139 (5) | 0.0116 (5) | −0.0002 (4) | 0.0019 (4) | 0.0008 (4) |
| C7B | 0.0137 (6) | 0.0107 (5) | 0.0153 (6) | −0.0050 (5) | −0.0002 (5) | −0.0006 (4) |
| C8B | 0.0123 (6) | 0.0082 (5) | 0.0151 (6) | −0.0011 (4) | 0.0010 (4) | 0.0021 (4) |
| C9B | 0.0058 (5) | 0.0152 (5) | 0.0121 (5) | 0.0004 (4) | −0.0019 (4) | 0.0008 (4) |
| C10B | 0.0086 (5) | 0.0168 (6) | 0.0100 (5) | 0.0015 (4) | −0.0016 (4) | 0.0009 (4) |
| C11B | 0.0077 (5) | 0.0176 (6) | 0.0119 (5) | 0.0019 (5) | 0.0029 (4) | 0.0001 (4) |
| C12B | 0.0089 (5) | 0.0185 (6) | 0.0116 (5) | −0.0023 (4) | 0.0019 (4) | 0.0021 (4) |
| Zn1C | 0.01218 (8) | 0.00967 (8) | 0.01807 (8) | 0.00023 (6) | 0.00177 (5) | 0.00160 (5) |
| Cl1C | 0.01393 (14) | 0.00883 (13) | 0.02650 (17) | 0.00090 (10) | −0.00337 (12) | 0.00088 (11) |
| Cl2C | 0.01734 (16) | 0.01496 (15) | 0.0387 (2) | −0.00191 (12) | 0.00984 (14) | −0.00832 (14) |
| Cl3C | 0.0391 (2) | 0.02137 (17) | 0.01994 (17) | −0.01329 (15) | −0.00752 (15) | 0.00866 (13) |
| Cl4C | 0.01283 (15) | 0.01041 (14) | 0.02507 (16) | 0.00074 (11) | 0.00208 (12) | 0.00425 (11) |
| Zn2D | 0.00835 (7) | 0.01209 (7) | 0.01009 (7) | 0.00124 (5) | 0.00181 (5) | 0.00072 (5) |
| Cl1D | 0.0306 (2) | 0.02487 (18) | 0.02429 (18) | 0.01727 (15) | 0.01784 (15) | 0.01057 (14) |
| Cl2D | 0.00648 (13) | 0.02672 (17) | 0.01266 (14) | −0.00212 (11) | −0.00121 (10) | −0.00219 (11) |
| Cl3D | 0.01435 (14) | 0.01330 (14) | 0.01629 (14) | −0.00026 (11) | 0.00357 (11) | 0.00350 (11) |
| Cl4D | 0.01005 (13) | 0.01445 (13) | 0.01150 (13) | −0.00155 (10) | 0.00138 (10) | −0.00169 (10) |
| Zn3E | 0.00872 (7) | 0.01067 (7) | 0.00903 (7) | −0.00129 (5) | −0.00122 (5) | 0.00038 (5) |
| Cl1E | 0.00677 (13) | 0.02058 (15) | 0.01107 (13) | 0.00090 (11) | 0.00149 (10) | −0.00140 (11) |
| Cl2E | 0.01364 (13) | 0.01323 (13) | 0.01543 (14) | 0.00019 (11) | −0.00224 (11) | 0.00407 (10) |
| Cl3E | 0.02649 (18) | 0.01875 (16) | 0.02131 (16) | −0.01179 (13) | −0.01415 (14) | 0.00553 (12) |
| Cl4E | 0.00968 (13) | 0.01421 (13) | 0.01113 (12) | 0.00120 (10) | 0.00010 (10) | −0.00091 (10) |
| O1W | 0.0434 (8) | 0.0350 (7) | 0.0307 (7) | −0.0181 (6) | −0.0078 (6) | −0.0003 (6) |
Geometric parameters (Å, º)
| Cr1A—N1A | 2.0709 (11) | N1B—C1B | 1.5053 (16) |
| Cr1A—N5A | 2.0750 (11) | N1B—H1B | 1.0000 |
| Cr1A—N4A | 2.0761 (11) | N2B—C2B | 1.4942 (17) |
| Cr1A—N6A | 2.0807 (11) | N2B—C3B | 1.5092 (17) |
| Cr1A—N3A | 2.0808 (11) | N2B—H2B | 1.0000 |
| Cr1A—N2A | 2.0828 (11) | N3B—C4B | 1.4943 (16) |
| N1A—C6A | 1.4951 (17) | N3B—C5B | 1.5043 (16) |
| N1A—C1A | 1.5053 (17) | N3B—H3B | 1.0000 |
| N1A—H1A | 1.0000 | N4B—C7B | 1.4936 (17) |
| N2A—C2A | 1.4977 (17) | N4B—C12B | 1.5070 (17) |
| N2A—C3A | 1.5058 (17) | N4B—H4B | 1.0000 |
| N2A—H2A | 1.0000 | N5B—C9B | 1.4933 (16) |
| N3A—C4A | 1.4923 (18) | N5B—C8B | 1.5064 (16) |
| N3A—C5A | 1.5076 (17) | N5B—H5B | 1.0000 |
| N3A—H3A | 1.0000 | N6B—C11B | 1.4933 (16) |
| N4A—C12A | 1.4958 (18) | N6B—C10B | 1.5008 (16) |
| N4A—C7A | 1.5053 (17) | N6B—H6B | 1.0000 |
| N4A—H4A | 1.0000 | C1B—C2B | 1.5193 (18) |
| N5A—C8A | 1.4919 (18) | C1B—H1B1 | 0.9900 |
| N5A—C9A | 1.5048 (17) | C1B—H1B2 | 0.9900 |
| N5A—H5A | 1.0000 | C2B—H2B1 | 0.9900 |
| N6A—C10A | 1.4942 (18) | C2B—H2B2 | 0.9900 |
| N6A—C11A | 1.5036 (17) | C3B—C4B | 1.525 (2) |
| N6A—H6A | 1.0000 | C3B—H3B1 | 0.9900 |
| C1A—C2A | 1.520 (2) | C3B—H3B2 | 0.9900 |
| C1A—H1A1 | 0.9900 | C4B—H4B1 | 0.9900 |
| C1A—H1A2 | 0.9900 | C4B—H4B2 | 0.9900 |
| C2A—H2A1 | 0.9900 | C5B—C6B | 1.5181 (18) |
| C2A—H2A2 | 0.9900 | C5B—H5B1 | 0.9900 |
| C3A—C4A | 1.518 (2) | C5B—H5B2 | 0.9900 |
| C3A—H3A1 | 0.9900 | C6B—H6B1 | 0.9900 |
| C3A—H3A2 | 0.9900 | C6B—H6B2 | 0.9900 |
| C4A—H4A1 | 0.9900 | C7B—C8B | 1.5224 (19) |
| C4A—H4A2 | 0.9900 | C7B—H7B1 | 0.9900 |
| C5A—C6A | 1.5168 (19) | C7B—H7B2 | 0.9900 |
| C5A—H5A1 | 0.9900 | C8B—H8B1 | 0.9900 |
| C5A—H5A2 | 0.9900 | C8B—H8B2 | 0.9900 |
| C6A—H6A1 | 0.9900 | C9B—C10B | 1.5184 (18) |
| C6A—H6A2 | 0.9900 | C9B—H9B1 | 0.9900 |
| C7A—C8A | 1.514 (2) | C9B—H9B2 | 0.9900 |
| C7A—H7A1 | 0.9900 | C10B—H10A | 0.9900 |
| C7A—H7A2 | 0.9900 | C10B—H10B | 0.9900 |
| C8A—H8A1 | 0.9900 | C11B—C12B | 1.5247 (19) |
| C8A—H8A2 | 0.9900 | C11B—H11C | 0.9900 |
| C9A—C10A | 1.513 (2) | C11B—H11D | 0.9900 |
| C9A—H9A1 | 0.9900 | C12B—H12A | 0.9900 |
| C9A—H9A2 | 0.9900 | C12B—H12B | 0.9900 |
| C10A—H10C | 0.9900 | Zn1C—Cl3C | 2.2365 (6) |
| C10A—H10D | 0.9900 | Zn1C—Cl2C | 2.2492 (5) |
| C11A—C12A | 1.5159 (19) | Zn1C—Cl4C | 2.2780 (6) |
| C11A—H11A | 0.9900 | Zn1C—Cl1C | 2.2825 (5) |
| C11A—H11B | 0.9900 | Zn2D—Cl1D | 2.2353 (5) |
| C12A—H12C | 0.9900 | Zn2D—Cl3D | 2.2592 (5) |
| C12A—H12D | 0.9900 | Zn2D—Cl2D | 2.2896 (6) |
| Cr2B—N4B | 2.0621 (11) | Zn2D—Cl4D | 2.3145 (5) |
| Cr2B—N2B | 2.0670 (11) | Zn3E—Cl2E | 2.2379 (5) |
| Cr2B—N1B | 2.0755 (11) | Zn3E—Cl3E | 2.2447 (5) |
| Cr2B—N3B | 2.0772 (12) | Zn3E—Cl1E | 2.3112 (6) |
| Cr2B—N5B | 2.0776 (11) | Zn3E—Cl4E | 2.3195 (5) |
| Cr2B—N6B | 2.0851 (11) | O1W—H1OW | 0.947 (9) |
| N1B—C6B | 1.4962 (16) | O1W—H2OW | 0.956 (9) |
| N1A—Cr1A—N5A | 97.83 (5) | N4B—Cr2B—N6B | 81.91 (4) |
| N1A—Cr1A—N4A | 96.50 (5) | N2B—Cr2B—N6B | 98.96 (4) |
| N5A—Cr1A—N4A | 82.79 (5) | N1B—Cr2B—N6B | 97.11 (4) |
| N1A—Cr1A—N6A | 178.59 (5) | N3B—Cr2B—N6B | 178.66 (4) |
| N5A—Cr1A—N6A | 82.00 (5) | N5B—Cr2B—N6B | 82.71 (4) |
| N4A—Cr1A—N6A | 82.09 (5) | C6B—N1B—C1B | 111.76 (10) |
| N1A—Cr1A—N3A | 82.49 (4) | C6B—N1B—Cr2B | 105.99 (7) |
| N5A—Cr1A—N3A | 96.24 (5) | C1B—N1B—Cr2B | 111.10 (8) |
| N4A—Cr1A—N3A | 178.51 (5) | C6B—N1B—H1B | 109.3 |
| N6A—Cr1A—N3A | 98.92 (5) | C1B—N1B—H1B | 109.3 |
| N1A—Cr1A—N2A | 82.35 (5) | Cr2B—N1B—H1B | 109.3 |
| N5A—Cr1A—N2A | 178.68 (5) | C2B—N2B—C3B | 113.66 (10) |
| N4A—Cr1A—N2A | 98.49 (5) | C2B—N2B—Cr2B | 106.28 (8) |
| N6A—Cr1A—N2A | 97.85 (5) | C3B—N2B—Cr2B | 111.36 (8) |
| N3A—Cr1A—N2A | 82.48 (5) | C2B—N2B—H2B | 108.5 |
| C6A—N1A—C1A | 113.31 (10) | C3B—N2B—H2B | 108.5 |
| C6A—N1A—Cr1A | 105.85 (8) | Cr2B—N2B—H2B | 108.5 |
| C1A—N1A—Cr1A | 111.77 (8) | C4B—N3B—C5B | 112.82 (10) |
| C6A—N1A—H1A | 108.6 | C4B—N3B—Cr2B | 105.67 (8) |
| C1A—N1A—H1A | 108.6 | C5B—N3B—Cr2B | 111.16 (8) |
| Cr1A—N1A—H1A | 108.6 | C4B—N3B—H3B | 109.0 |
| C2A—N2A—C3A | 112.31 (10) | C5B—N3B—H3B | 109.0 |
| C2A—N2A—Cr1A | 105.80 (8) | Cr2B—N3B—H3B | 109.0 |
| C3A—N2A—Cr1A | 111.14 (8) | C7B—N4B—C12B | 113.80 (10) |
| C2A—N2A—H2A | 109.2 | C7B—N4B—Cr2B | 106.23 (8) |
| C3A—N2A—H2A | 109.2 | C12B—N4B—Cr2B | 112.02 (8) |
| Cr1A—N2A—H2A | 109.2 | C7B—N4B—H4B | 108.2 |
| C4A—N3A—C5A | 112.86 (11) | C12B—N4B—H4B | 108.2 |
| C4A—N3A—Cr1A | 106.23 (8) | Cr2B—N4B—H4B | 108.2 |
| C5A—N3A—Cr1A | 111.01 (8) | C9B—N5B—C8B | 111.97 (10) |
| C4A—N3A—H3A | 108.9 | C9B—N5B—Cr2B | 106.09 (8) |
| C5A—N3A—H3A | 108.9 | C8B—N5B—Cr2B | 110.75 (8) |
| Cr1A—N3A—H3A | 108.9 | C9B—N5B—H5B | 109.3 |
| C12A—N4A—C7A | 112.51 (10) | C8B—N5B—H5B | 109.3 |
| C12A—N4A—Cr1A | 106.01 (8) | Cr2B—N5B—H5B | 109.3 |
| C7A—N4A—Cr1A | 111.14 (8) | C11B—N6B—C10B | 112.35 (10) |
| C12A—N4A—H4A | 109.0 | C11B—N6B—Cr2B | 106.06 (8) |
| C7A—N4A—H4A | 109.0 | C10B—N6B—Cr2B | 110.86 (8) |
| Cr1A—N4A—H4A | 109.0 | C11B—N6B—H6B | 109.2 |
| C8A—N5A—C9A | 112.86 (11) | C10B—N6B—H6B | 109.2 |
| C8A—N5A—Cr1A | 105.70 (8) | Cr2B—N6B—H6B | 109.2 |
| C9A—N5A—Cr1A | 111.53 (9) | N1B—C1B—C2B | 110.75 (10) |
| C8A—N5A—H5A | 108.9 | N1B—C1B—H1B1 | 109.5 |
| C9A—N5A—H5A | 108.9 | C2B—C1B—H1B1 | 109.5 |
| Cr1A—N5A—H5A | 108.9 | N1B—C1B—H1B2 | 109.5 |
| C10A—N6A—C11A | 112.65 (11) | C2B—C1B—H1B2 | 109.5 |
| C10A—N6A—Cr1A | 105.97 (8) | H1B1—C1B—H1B2 | 108.1 |
| C11A—N6A—Cr1A | 111.62 (8) | N2B—C2B—C1B | 109.88 (10) |
| C10A—N6A—H6A | 108.8 | N2B—C2B—H2B1 | 109.7 |
| C11A—N6A—H6A | 108.8 | C1B—C2B—H2B1 | 109.7 |
| Cr1A—N6A—H6A | 108.8 | N2B—C2B—H2B2 | 109.7 |
| N1A—C1A—C2A | 110.02 (10) | C1B—C2B—H2B2 | 109.7 |
| N1A—C1A—H1A1 | 109.7 | H2B1—C2B—H2B2 | 108.2 |
| C2A—C1A—H1A1 | 109.7 | N2B—C3B—C4B | 110.32 (10) |
| N1A—C1A—H1A2 | 109.7 | N2B—C3B—H3B1 | 109.6 |
| C2A—C1A—H1A2 | 109.7 | C4B—C3B—H3B1 | 109.6 |
| H1A1—C1A—H1A2 | 108.2 | N2B—C3B—H3B2 | 109.6 |
| N2A—C2A—C1A | 108.99 (10) | C4B—C3B—H3B2 | 109.6 |
| N2A—C2A—H2A1 | 109.9 | H3B1—C3B—H3B2 | 108.1 |
| C1A—C2A—H2A1 | 109.9 | N3B—C4B—C3B | 108.37 (10) |
| N2A—C2A—H2A2 | 109.9 | N3B—C4B—H4B1 | 110.0 |
| C1A—C2A—H2A2 | 109.9 | C3B—C4B—H4B1 | 110.0 |
| H2A1—C2A—H2A2 | 108.3 | N3B—C4B—H4B2 | 110.0 |
| N2A—C3A—C4A | 110.46 (11) | C3B—C4B—H4B2 | 110.0 |
| N2A—C3A—H3A1 | 109.6 | H4B1—C4B—H4B2 | 108.4 |
| C4A—C3A—H3A1 | 109.6 | N3B—C5B—C6B | 109.85 (10) |
| N2A—C3A—H3A2 | 109.6 | N3B—C5B—H5B1 | 109.7 |
| C4A—C3A—H3A2 | 109.6 | C6B—C5B—H5B1 | 109.7 |
| H3A1—C3A—H3A2 | 108.1 | N3B—C5B—H5B2 | 109.7 |
| N3A—C4A—C3A | 109.19 (11) | C6B—C5B—H5B2 | 109.7 |
| N3A—C4A—H4A1 | 109.8 | H5B1—C5B—H5B2 | 108.2 |
| C3A—C4A—H4A1 | 109.8 | N1B—C6B—C5B | 108.97 (10) |
| N3A—C4A—H4A2 | 109.8 | N1B—C6B—H6B1 | 109.9 |
| C3A—C4A—H4A2 | 109.8 | C5B—C6B—H6B1 | 109.9 |
| H4A1—C4A—H4A2 | 108.3 | N1B—C6B—H6B2 | 109.9 |
| N3A—C5A—C6A | 110.40 (10) | C5B—C6B—H6B2 | 109.9 |
| N3A—C5A—H5A1 | 109.6 | H6B1—C6B—H6B2 | 108.3 |
| C6A—C5A—H5A1 | 109.6 | N4B—C7B—C8B | 109.93 (10) |
| N3A—C5A—H5A2 | 109.6 | N4B—C7B—H7B1 | 109.7 |
| C6A—C5A—H5A2 | 109.6 | C8B—C7B—H7B1 | 109.7 |
| H5A1—C5A—H5A2 | 108.1 | N4B—C7B—H7B2 | 109.7 |
| N1A—C6A—C5A | 109.08 (11) | C8B—C7B—H7B2 | 109.7 |
| N1A—C6A—H6A1 | 109.9 | H7B1—C7B—H7B2 | 108.2 |
| C5A—C6A—H6A1 | 109.9 | N5B—C8B—C7B | 111.02 (10) |
| N1A—C6A—H6A2 | 109.9 | N5B—C8B—H8B1 | 109.4 |
| C5A—C6A—H6A2 | 109.9 | C7B—C8B—H8B1 | 109.4 |
| H6A1—C6A—H6A2 | 108.3 | N5B—C8B—H8B2 | 109.4 |
| N4A—C7A—C8A | 110.37 (11) | C7B—C8B—H8B2 | 109.4 |
| N4A—C7A—H7A1 | 109.6 | H8B1—C8B—H8B2 | 108.0 |
| C8A—C7A—H7A1 | 109.6 | N5B—C9B—C10B | 108.91 (10) |
| N4A—C7A—H7A2 | 109.6 | N5B—C9B—H9B1 | 109.9 |
| C8A—C7A—H7A2 | 109.6 | C10B—C9B—H9B1 | 109.9 |
| H7A1—C7A—H7A2 | 108.1 | N5B—C9B—H9B2 | 109.9 |
| N5A—C8A—C7A | 109.90 (11) | C10B—C9B—H9B2 | 109.9 |
| N5A—C8A—H8A1 | 109.7 | H9B1—C9B—H9B2 | 108.3 |
| C7A—C8A—H8A1 | 109.7 | N6B—C10B—C9B | 110.07 (10) |
| N5A—C8A—H8A2 | 109.7 | N6B—C10B—H10A | 109.6 |
| C7A—C8A—H8A2 | 109.7 | C9B—C10B—H10A | 109.6 |
| H8A1—C8A—H8A2 | 108.2 | N6B—C10B—H10B | 109.6 |
| N5A—C9A—C10A | 110.38 (11) | C9B—C10B—H10B | 109.6 |
| N5A—C9A—H9A1 | 109.6 | H10A—C10B—H10B | 108.2 |
| C10A—C9A—H9A1 | 109.6 | N6B—C11B—C12B | 108.31 (10) |
| N5A—C9A—H9A2 | 109.6 | N6B—C11B—H11C | 110.0 |
| C10A—C9A—H9A2 | 109.6 | C12B—C11B—H11C | 110.0 |
| H9A1—C9A—H9A2 | 108.1 | N6B—C11B—H11D | 110.0 |
| N6A—C10A—C9A | 108.73 (11) | C12B—C11B—H11D | 110.0 |
| N6A—C10A—H10C | 109.9 | H11C—C11B—H11D | 108.4 |
| C9A—C10A—H10C | 109.9 | N4B—C12B—C11B | 110.32 (10) |
| N6A—C10A—H10D | 109.9 | N4B—C12B—H12A | 109.6 |
| C9A—C10A—H10D | 109.9 | C11B—C12B—H12A | 109.6 |
| H10C—C10A—H10D | 108.3 | N4B—C12B—H12B | 109.6 |
| N6A—C11A—C12A | 109.59 (10) | C11B—C12B—H12B | 109.6 |
| N6A—C11A—H11A | 109.8 | H12A—C12B—H12B | 108.1 |
| C12A—C11A—H11A | 109.8 | Cl3C—Zn1C—Cl2C | 112.37 (2) |
| N6A—C11A—H11B | 109.8 | Cl3C—Zn1C—Cl4C | 113.395 (16) |
| C12A—C11A—H11B | 109.8 | Cl2C—Zn1C—Cl4C | 104.464 (16) |
| H11A—C11A—H11B | 108.2 | Cl3C—Zn1C—Cl1C | 105.567 (16) |
| N4A—C12A—C11A | 108.78 (10) | Cl2C—Zn1C—Cl1C | 113.879 (19) |
| N4A—C12A—H12C | 109.9 | Cl4C—Zn1C—Cl1C | 107.248 (14) |
| C11A—C12A—H12C | 109.9 | Cl1D—Zn2D—Cl3D | 109.431 (19) |
| N4A—C12A—H12D | 109.9 | Cl1D—Zn2D—Cl2D | 112.432 (17) |
| C11A—C12A—H12D | 109.9 | Cl3D—Zn2D—Cl2D | 110.039 (18) |
| H12C—C12A—H12D | 108.3 | Cl1D—Zn2D—Cl4D | 112.48 (2) |
| N4B—Cr2B—N2B | 93.72 (5) | Cl3D—Zn2D—Cl4D | 112.585 (14) |
| N4B—Cr2B—N1B | 176.42 (4) | Cl2D—Zn2D—Cl4D | 99.600 (13) |
| N2B—Cr2B—N1B | 83.01 (5) | Cl2E—Zn3E—Cl3E | 110.568 (18) |
| N4B—Cr2B—N3B | 98.30 (4) | Cl2E—Zn3E—Cl1E | 109.412 (16) |
| N2B—Cr2B—N3B | 82.34 (4) | Cl3E—Zn3E—Cl1E | 111.573 (16) |
| N1B—Cr2B—N3B | 82.76 (4) | Cl2E—Zn3E—Cl4E | 113.441 (14) |
| N4B—Cr2B—N5B | 83.23 (5) | Cl3E—Zn3E—Cl4E | 111.220 (19) |
| N2B—Cr2B—N5B | 176.31 (4) | Cl1E—Zn3E—Cl4E | 100.238 (13) |
| N1B—Cr2B—N5B | 100.08 (5) | H1OW—O1W—H2OW | 106.9 (17) |
| N3B—Cr2B—N5B | 96.00 (4) | ||
| C6A—N1A—C1A—C2A | 136.07 (11) | C6B—N1B—C1B—C2B | −132.97 (11) |
| Cr1A—N1A—C1A—C2A | 16.58 (13) | Cr2B—N1B—C1B—C2B | −14.81 (13) |
| C3A—N2A—C2A—C1A | −72.26 (13) | C3B—N2B—C2B—C1B | 75.82 (13) |
| Cr1A—N2A—C2A—C1A | 49.17 (11) | Cr2B—N2B—C2B—C1B | −47.02 (12) |
| N1A—C1A—C2A—N2A | −43.73 (14) | N1B—C1B—C2B—N2B | 41.19 (14) |
| C2A—N2A—C3A—C4A | 135.60 (12) | C2B—N2B—C3B—C4B | −134.90 (11) |
| Cr1A—N2A—C3A—C4A | 17.29 (13) | Cr2B—N2B—C3B—C4B | −14.90 (12) |
| C5A—N3A—C4A—C3A | −73.41 (13) | C5B—N3B—C4B—C3B | 71.42 (13) |
| Cr1A—N3A—C4A—C3A | 48.46 (12) | Cr2B—N3B—C4B—C3B | −50.24 (11) |
| N2A—C3A—C4A—N3A | −43.79 (14) | N2B—C3B—C4B—N3B | 43.29 (14) |
| C4A—N3A—C5A—C6A | 134.71 (11) | C4B—N3B—C5B—C6B | −138.31 (11) |
| Cr1A—N3A—C5A—C6A | 15.58 (13) | Cr2B—N3B—C5B—C6B | −19.81 (12) |
| C1A—N1A—C6A—C5A | −73.30 (13) | C1B—N1B—C6B—C5B | 72.33 (13) |
| Cr1A—N1A—C6A—C5A | 49.53 (11) | Cr2B—N1B—C6B—C5B | −48.85 (11) |
| N3A—C5A—C6A—N1A | −43.29 (14) | N3B—C5B—C6B—N1B | 45.71 (13) |
| C12A—N4A—C7A—C8A | 134.34 (12) | C12B—N4B—C7B—C8B | 76.77 (13) |
| Cr1A—N4A—C7A—C8A | 15.63 (13) | Cr2B—N4B—C7B—C8B | −46.95 (11) |
| C9A—N5A—C8A—C7A | −73.87 (13) | C9B—N5B—C8B—C7B | −131.91 (11) |
| Cr1A—N5A—C8A—C7A | 48.28 (12) | Cr2B—N5B—C8B—C7B | −13.72 (12) |
| N4A—C7A—C8A—N5A | −42.73 (15) | N4B—C7B—C8B—N5B | 40.46 (14) |
| C8A—N5A—C9A—C10A | 134.71 (12) | C8B—N5B—C9B—C10B | 72.14 (13) |
| Cr1A—N5A—C9A—C10A | 15.90 (13) | Cr2B—N5B—C9B—C10B | −48.78 (11) |
| C11A—N6A—C10A—C9A | −72.64 (13) | C11B—N6B—C10B—C9B | −138.96 (11) |
| Cr1A—N6A—C10A—C9A | 49.68 (12) | Cr2B—N6B—C10B—C9B | −20.48 (12) |
| N5A—C9A—C10A—N6A | −43.54 (14) | N5B—C9B—C10B—N6B | 46.21 (13) |
| C10A—N6A—C11A—C12A | 137.57 (12) | C10B—N6B—C11B—C12B | 71.60 (13) |
| Cr1A—N6A—C11A—C12A | 18.49 (13) | Cr2B—N6B—C11B—C12B | −49.67 (11) |
| C7A—N4A—C12A—C11A | −71.67 (13) | C7B—N4B—C12B—C11B | −134.99 (11) |
| Cr1A—N4A—C12A—C11A | 50.00 (11) | Cr2B—N4B—C12B—C11B | −14.47 (13) |
| N6A—C11A—C12A—N4A | −45.37 (14) | N6B—C11B—C12B—N4B | 42.52 (14) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5A—H5A···O1W | 1.00 | 2.46 | 3.1535 (19) | 126 |
| N2B—H2B···Cl1E | 1.00 | 2.25 | 3.1608 (12) | 151 |
| N4B—H4B···Cl2D | 1.00 | 2.24 | 3.1179 (12) | 146 |
| O1W—H2OW···Cl3D | 0.96 (1) | 2.44 (1) | 3.3163 (16) | 152 (2) |
| N1A—H1A···Cl4Ci | 1.00 | 2.23 | 3.2091 (13) | 167 |
| N4A—H4A···Cl1Ci | 1.00 | 2.29 | 3.2377 (12) | 158 |
| N2A—H2A···Cl2Cii | 1.00 | 2.42 | 3.2981 (13) | 146 |
| N6A—H6A···Cl4Cii | 1.00 | 2.23 | 3.1811 (13) | 159 |
| N3A—H3A···Cl1Ciii | 1.00 | 2.62 | 3.4416 (13) | 140 |
| N5A—H5A···Cl1Ciii | 1.00 | 2.50 | 3.2875 (13) | 136 |
| N1B—H1B···Cl2Div | 1.00 | 2.42 | 3.2707 (12) | 143 |
| N3B—H3B···Cl4Eiv | 1.00 | 2.36 | 3.2884 (12) | 154 |
| N5B—H5B···Cl1Eiv | 1.00 | 2.46 | 3.2932 (12) | 141 |
| N6B—H6B···Cl4Div | 1.00 | 2.35 | 3.2935 (12) | 157 |
| O1W—H1OW···Cl2Cv | 0.95 (1) | 2.32 (1) | 3.2520 (15) | 166 (2) |
Symmetry codes: (i) x+1/2, y, −z+3/2; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, y−1/2, z.
Funding Statement
This work was funded by Andong National University grant 2018 Research Fund. Ministry of Science ICT and Future Planning grant . Pohang University of Science and Technology grant .
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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/S2056989019003086/sj5569sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019003086/sj5569Isup2.hkl
CCDC reference: 1900397
Additional supporting information: crystallographic information; 3D view; checkCIF report