The CrIII atoms in the title compound show a distorted octahedral coordination with four N atoms of two ethane-1,2-diamine ligands (en) in the equatorial plane and two N-coordinated NCS− groups in axial positions. The [ZnCl4]2− anion has a slightly distorted tetrahedral geometry.
Keywords: Crystal structure; ethane-1,2-diamine; thiocyanate; trans isomer; chromium(III) complex; synchrotron data; hydrogen bonds
Abstract
The structure of the title compound, [Cr(NCS)2(C2H8N2)2]2[ZnCl4], has been determined from synchrotron data. In the asymmetric unit, there are four independent halves of the CrIII complex cations, each of which lies on an inversion centre, and one tetrachloridozincate anion in a general position. The CrIII atoms are coordinated by the four N atoms of two ethane-1,2-diamine (en) ligands in the equatorial plane and two N-bound NCS− anions in a trans arrangement, displaying a slightly distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(en) and Cr—N(NCS) bond lengths range from 2.0653 (10) to 2.0837 (10) Å and from 1.9811 (10) to 1.9890 (10) Å, respectively. The five-membered metalla-rings are in stable gauche conformations. The [ZnCl4]2− anion has a distorted tetrahedral geometry. The crystal structure is stabilized by intermolecular hydrogen bonds involving the en NH2 or CH2 groups as donors and chloride ligands of the anion and S atoms of NCS− ligands as acceptors.
Chemical context
The study of geometrical isomers in octahedral transition metal complexes with bidentate amines has been an area of intense activity and has provided much basic structural information and insights into their spectroscopic properties. Ethane-1,2-diamine (en) can act as a bidentate ligand to a central metal ion through its two nitrogen atoms, forming a five-membered ring. The [Cr(en)2 L 2]+ (where L is a monodentate ligand) cation can form either trans or cis geometric isomers. Infrared, electronic absorption and emission spectral properties are useful in determining the geometric isomers of chromium(III) complexes with mixed ligands (Choi, 2000a ▸,b ▸; Choi et al., 2002 ▸, 2004a ▸,b ▸; Choi & Moon, 2014 ▸). However, it should be noted that the geometric assignments based on spectroscopic studies are much less conclusive. In addition, NCS− is an ambidentate ligand because it can coordinate to a transition metal through the nitrogen (M—NCS), or the sulfur (M—SCN), or both (M–-NCS—M). In general, hard metals such as chromium, nickel and cobalt tend to form metal–NCS bonds, whereas the soft metals such as mercury, rhodium, iridium, palladium and platinum tend to bind through the S atom. The oxidation state of the metal, the nature of other ligands and steric factors also influence the mode of coordination.
Here, we report on the synthesis and structure of [Cr(en)2(NCS)2]2[ZnCl4] in order to determine the bonding mode of the thiocyanate group and the geometric features of the two en ligands, the two NCS groups and the [ZnCl4]2− anion. 
Structural commentary
Structural analysis shows that there are four crystallographically independent CrIII complex cations in which the four nitrogen atoms of the two en ligands occupy the equatorial sites and the two thiocyanate anions coordinate to the CrIII atom through their N atoms in a trans configuration. Fig. 1 ▸ shows an ellipsoid plot of two independent complex cations and one anion in trans-[Cr(en)2(NCS)2]2[ZnCl4], with the atom-numbering scheme.
Figure 1.
A perspective view (60% probability ellipsoids) of two independent chromium(III) complex cations and the unique tetrachloridozincate anion in trans-[Cr(en)2(NCS)2]2[ZnCl4]. The symmetry code for A′ atoms is −x + 2, −y, −z + 1 and for B′ atoms, the symmetry code is −x + 1, −y + 1, −z + 1.
The asymmetric unit contains four halves of the [Cr(en)2(NCS)2]+ complex cations and one [ZnCl4]2− anion. The four CrIII atoms are located on crystallographic centers of symmetry, so these complex cations have molecular Ci symmetry. The spatial configuration of the bidentate en ring is a stable gauche form, which has been observed in other compounds (Brencic & Leban, 1981 ▸; Choi et al., 2010 ▸). The carbon atoms in the en ring are arranged symmetrically above and below the plane defined by the chromium and the en nitrogen atoms. The two Cr–en rings are in δ and λ conformations as the CrIII atom occupies a special position with inversion symmetry. The Cr—N bond lengths for the en ligand range from 2.0653 (10) to 2.0837 (10) Å, in good agreement with those observed in trans-[Cr(en)2F2]ClO4 (Brencic & Leban, 1981 ▸), trans-[Cr(en)2Br2]ClO4 (Choi et al., 2010 ▸), trans-[Cr(Me2tn)2Cl2]2ZnCl4 (Me2tn = 2,2-dimethylpropane-1,3-diamine) (Choi et al., 2011 ▸) and trans-[Cr(2,2,3-tet)F2]ClO4 (2,2,3-tet = 1,4,7,11-tetraazaundecane) (Choi & Moon, 2014 ▸). The Cr—N(CS) distances lie in the range 1.9811 (10) to 1.9890 (10) Å and are similar to the average values of 1.9826 (15) and 1.996 (15) Å found in trans-[Cr(Me2tn)2(NCS)2]NCS (Choi & Lee, 2009 ▸) and cis-[Cr(cyclam)(NCS)2]NCS (cyclam = 1,4,8,11-tetraazacyclotetradecane) (Moon et al., 2013 ▸), respectively. The N-coordinating thiocyanato groups are almost linear with N—C—S angles ranging from 177.11 (8) to 179.15 (9)°. The [ZnCl4]2− counter-anion has a distorted tetrahedral geometry due to the influence of hydrogen bonding on the Zn—Cl bond lengths and the Cl—Zn—Cl angles. Zn—Cl bond lengths range from 2.2518 (8) to 2.2923 (8) Å and the Cl—Zn—Cl angles are in the range 106.71 (2)–112.49 (2)°.
Supramolecular features
In the asymmetric unit, a series of N—H⋯Cl and C—H⋯Cl hydrogen bonds link each anion to the four neighbouring cations, while N—H⋯S and C—H⋯S contacts interconnect the complex cations (Fig. 2 ▸, Table 1 ▸). An extensive array of additional, similar contacts generate a three-dimensional network of molecules stacked along the a-axis direction.
Figure 2.
The molecular packing for trans-[Cr(en)2(NCS)2]2[ZnCl4], viewed along the a axis. Hydrogen bonding is denoted by dashed liness, N—H⋯S (purple), C—H⋯S (grey), N—H⋯Cl (red), and C—H⋯Cl (blue).
Table 1. Hydrogen-bond geometry (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1AH1A1Cl3E i | 0.91 | 2.48 | 3.3700(13) | 165 |
| N2AH2A1Cl1E ii | 0.91 | 2.50 | 3.3483(13) | 155 |
| N2AH2A2Cl3E | 0.91 | 2.90 | 3.5797(12) | 133 |
| C1AH1A3S1A iii | 0.99 | 2.91 | 3.5983(15) | 127 |
| C2AH2A3Cl3E | 0.99 | 2.91 | 3.5533(15) | 123 |
| C2AH2A4S1B iv | 0.99 | 2.94 | 3.6270(15) | 128 |
| N1BH1B1Cl1E | 0.91 | 2.45 | 3.2813(13) | 152 |
| N1BH1B2S1A iii | 0.91 | 2.81 | 3.5401(13) | 138 |
| N2BH2B1Cl4E iv | 0.91 | 2.49 | 3.3532(13) | 159 |
| N2BH2B2Cl1E v | 0.91 | 2.77 | 3.4934(12) | 138 |
| C1BH1B3S1A iii | 0.99 | 2.98 | 3.5910(14) | 121 |
| C1BH1B3S1B v | 0.99 | 2.87 | 3.6440(14) | 136 |
| C2BH2B3Cl1E v | 0.99 | 2.93 | 3.5309(14) | 120 |
| N1CH1C1Cl4E | 0.91 | 2.40 | 3.3058(12) | 171 |
| N1CH1C2S1B | 0.91 | 2.73 | 3.4473(14) | 137 |
| N2CH2C1S1C iii | 0.91 | 2.50 | 3.2836(12) | 144 |
| N2CH2C2S1B vi | 0.91 | 2.75 | 3.4063(11) | 130 |
| N2CH2C2S1D iii | 0.91 | 2.88 | 3.5893(13) | 135 |
| C1CH1C4Cl1E | 0.99 | 2.86 | 3.7421(13) | 149 |
| N1DH1D1S1C | 0.91 | 2.61 | 3.4937(13) | 164 |
| N1DH1D2Cl2E | 0.91 | 2.49 | 3.3919(12) | 172 |
| N2DH2D1S1C vii | 0.91 | 2.78 | 3.6225(12) | 155 |
| N2DH2D2S1D viii | 0.91 | 2.67 | 3.3564(12) | 133 |
| C1DH1D3Cl3E | 0.99 | 2.88 | 3.7357(14) | 145 |
| C1DH1D4Cl2E ii | 0.99 | 2.98 | 3.7397(12) | 135 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
; (viii) 
.
Database survey
A search of the Cambridge Structural Database (Version 5.35, May 2014 with one update; Groom & Allen, 2014 ▸) indicates a total of 13 hits for CrIII complexes with a [Cr(en)2 L 2]+ unit. The crystal structures of trans-[Cr(en)2Cl2]Cl·HCl·2H2O (Ooi et al., 1960 ▸), trans-[Cr(en)2F2]X (X = ClO4, Cl, Br) (Brencic & Leban, 1981 ▸), cis-[Cr(en)2F2]ClO4 (Brencic et al., 1987 ▸), trans-[Cr(en)2Br2]ClO4 (Choi et al., 2010 ▸) have been reported previously. However, no structures of salts of [Cr(en)2(NCS)2]+ with any anions were found.
Synthesis and crystallization
All chemicals were reagent-grade materials and were used without further purification. The starting material, trans-[Cr(en)2(NCS)2]ClO4 was prepared according to the literature (Sandrini et al., 1978 ▸). The crude perchlorate salt (0.10 g) was dissolved in 5 mL of 0.1 M HCl at 333 K and added to 2 mL of 6 M HCl containing 0.3 g of solid ZnCl2. The resulting solution was filtered and allowed to stand at room temperature for two days to give red crystals of the tetrachloridozincate salt suitable for X-ray structural analysis.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Hydrogen atoms bound to carbon or nitrogen were placed in calculated positions (C—H = 0.95, N—H = 0.91 Å), and were included in the refinement using the riding-model approximation with U iso(H) set to 1.2U eq(C, N).
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Cr(NCS)2(C2H8N2)2]2[ZnCl4] |
| M r | 783.90 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 100 |
| a, b, c () | 7.6870(15), 13.853(3), 14.560(3) |
| , , () | 92.74(3), 92.76(3), 90.21(3) |
| V (3) | 1546.9(5) |
| Z | 2 |
| Radiation type | Synchrotron, = 0.62998 |
| (mm1) | 1.50 |
| Crystal size (mm) | 0.10 0.03 0.03 |
| Data collection | |
| Diffractometer | ADSC Q210 CCD area detector |
| Absorption correction | Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski Minor, 1997 ▸) |
| T min, T max | 0.865, 0.956 |
| No. of measured, independent and observed [I > 2(I)] reflections | 17036, 8546, 8434 |
| R int | 0.014 |
| (sin /)max (1) | 0.696 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.018, 0.049, 1.03 |
| No. of reflections | 8546 |
| No. of parameters | 322 |
| H-atom treatment | H-atom parameters constrained |
| max, min (e 3) | 0.48, 0.60 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014027479/sj5433sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027479/sj5433Isup2.hkl
CCDC reference: 1039747
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The X-ray crystallography experiment at PLS-II 2D-SMC beamline was supported in part by MISP and POSTECH.
supplementary crystallographic information
Crystal data
| [Cr(NCS)2(C2H8N2)2]2[ZnCl4] | Z = 2 |
| Mr = 783.90 | F(000) = 796 |
| Triclinic, P1 | Dx = 1.683 Mg m−3 |
| a = 7.6870 (15) Å | Synchrotron radiation, λ = 0.62998 Å |
| b = 13.853 (3) Å | Cell parameters from 94806 reflections |
| c = 14.560 (3) Å | θ = 0.4–33.6° |
| α = 92.74 (3)° | µ = 1.50 mm−1 |
| β = 92.76 (3)° | T = 100 K |
| γ = 90.21 (3)° | Needle, red |
| V = 1546.9 (5) Å3 | 0.10 × 0.03 × 0.03 mm |
Data collection
| ADSC Q210 CCD area-detector diffractometer | 8434 reflections with I > 2σ(I) |
| Radiation source: PLSII 2D bending magnet | Rint = 0.014 |
| ω scans | θmax = 26.0°, θmin = 2.4° |
| Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997) | h = −10→10 |
| Tmin = 0.865, Tmax = 0.956 | k = −19→19 |
| 17036 measured reflections | l = −20→20 |
| 8546 independent reflections |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
| wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.027P)2 + 0.6367P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 8546 reflections | Δρmax = 0.48 e Å−3 |
| 322 parameters | Δρmin = −0.60 e Å−3 |
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 | ||
| Cr1A | 1.0000 | 0.0000 | 0.5000 | 0.00585 (4) | |
| S1A | 1.34965 (3) | 0.21259 (2) | 0.69613 (2) | 0.01282 (5) | |
| N1A | 0.83989 (11) | 0.00710 (6) | 0.61105 (6) | 0.01133 (14) | |
| H1A1 | 0.7841 | −0.0505 | 0.6151 | 0.014* | |
| H1A2 | 0.9052 | 0.0192 | 0.6642 | 0.014* | |
| N2A | 0.86680 (11) | 0.12458 (6) | 0.46494 (6) | 0.01130 (14) | |
| H2A1 | 0.9409 | 0.1676 | 0.4417 | 0.014* | |
| H2A2 | 0.7803 | 0.1099 | 0.4216 | 0.014* | |
| N3A | 1.17486 (11) | 0.08052 (6) | 0.57360 (6) | 0.01110 (14) | |
| C1A | 0.70956 (13) | 0.08539 (8) | 0.59868 (7) | 0.01647 (18) | |
| H1A3 | 0.6706 | 0.1094 | 0.6594 | 0.020* | |
| H1A4 | 0.6066 | 0.0600 | 0.5616 | 0.020* | |
| C2A | 0.79203 (13) | 0.16675 (7) | 0.55045 (7) | 0.01477 (18) | |
| H2A3 | 0.7036 | 0.2159 | 0.5349 | 0.018* | |
| H2A4 | 0.8849 | 0.1982 | 0.5909 | 0.018* | |
| C3A | 1.24862 (12) | 0.13654 (6) | 0.62427 (6) | 0.00895 (15) | |
| Cr2B | 0.5000 | 0.5000 | 0.5000 | 0.00494 (4) | |
| S1B | 0.15226 (4) | 0.64435 (2) | 0.26918 (2) | 0.01492 (5) | |
| N1B | 0.33365 (10) | 0.38801 (6) | 0.52696 (5) | 0.00894 (13) | |
| H1B1 | 0.2819 | 0.3630 | 0.4735 | 0.011* | |
| H1B2 | 0.3944 | 0.3402 | 0.5545 | 0.011* | |
| N2B | 0.38490 (10) | 0.56908 (6) | 0.61174 (5) | 0.00906 (13) | |
| H2B1 | 0.4679 | 0.5980 | 0.6505 | 0.011* | |
| H2B2 | 0.3100 | 0.6152 | 0.5919 | 0.011* | |
| N3B | 0.32168 (11) | 0.55205 (6) | 0.41316 (6) | 0.01046 (14) | |
| C1B | 0.19944 (12) | 0.42703 (7) | 0.58878 (7) | 0.01159 (16) | |
| H1B3 | 0.1421 | 0.3736 | 0.6188 | 0.014* | |
| H1B4 | 0.1094 | 0.4622 | 0.5529 | 0.014* | |
| C2B | 0.28916 (13) | 0.49470 (7) | 0.66051 (6) | 0.01178 (16) | |
| H2B3 | 0.2022 | 0.5261 | 0.6999 | 0.014* | |
| H2B4 | 0.3714 | 0.4584 | 0.7001 | 0.014* | |
| C3B | 0.24999 (11) | 0.58858 (6) | 0.35161 (6) | 0.00807 (15) | |
| Cr3C | 0.0000 | 0.5000 | 0.0000 | 0.00436 (4) | |
| S1C | 0.47203 (3) | 0.29853 (2) | −0.07639 (2) | 0.01296 (5) | |
| N1C | 0.00397 (10) | 0.44890 (5) | 0.13158 (5) | 0.00792 (13) | |
| H1C1 | 0.1118 | 0.4263 | 0.1474 | 0.010* | |
| H1C2 | −0.0225 | 0.4973 | 0.1729 | 0.010* | |
| N2C | −0.12263 (11) | 0.36953 (6) | −0.03474 (5) | 0.00961 (14) | |
| H2C1 | −0.2372 | 0.3795 | −0.0499 | 0.012* | |
| H2C2 | −0.0729 | 0.3404 | −0.0842 | 0.012* | |
| N3C | 0.22291 (11) | 0.43406 (6) | −0.02527 (6) | 0.01166 (14) | |
| C1C | −0.12726 (13) | 0.36960 (7) | 0.13185 (6) | 0.01083 (16) | |
| H1C3 | −0.2464 | 0.3965 | 0.1322 | 0.013* | |
| H1C4 | −0.1076 | 0.3314 | 0.1871 | 0.013* | |
| C2C | −0.10560 (14) | 0.30666 (7) | 0.04542 (6) | 0.01285 (17) | |
| H2C3 | 0.0102 | 0.2756 | 0.0476 | 0.015* | |
| H2C4 | −0.1961 | 0.2554 | 0.0399 | 0.015* | |
| C3C | 0.32768 (12) | 0.37725 (7) | −0.04576 (6) | 0.00935 (15) | |
| Cr4D | 0.5000 | 0.0000 | 0.0000 | 0.00523 (4) | |
| S1D | 0.95604 (3) | 0.14416 (2) | −0.15730 (2) | 0.01195 (5) | |
| N1D | 0.46882 (10) | 0.12154 (5) | 0.08662 (5) | 0.00860 (13) | |
| H1D1 | 0.4761 | 0.1760 | 0.0545 | 0.010* | |
| H1D2 | 0.3627 | 0.1200 | 0.1116 | 0.010* | |
| N2D | 0.65239 (10) | −0.04648 (6) | 0.11111 (6) | 0.01038 (14) | |
| H2D1 | 0.6223 | −0.1080 | 0.1232 | 0.012* | |
| H2D2 | 0.7668 | −0.0458 | 0.0976 | 0.012* | |
| N3D | 0.70324 (10) | 0.06281 (6) | −0.05272 (6) | 0.01025 (14) | |
| C1D | 0.60962 (13) | 0.12127 (7) | 0.16052 (6) | 0.01106 (16) | |
| H1D3 | 0.5810 | 0.1665 | 0.2123 | 0.013* | |
| H1D4 | 0.7213 | 0.1420 | 0.1364 | 0.013* | |
| C2D | 0.62447 (13) | 0.01935 (7) | 0.19298 (6) | 0.01289 (17) | |
| H2D3 | 0.7235 | 0.0150 | 0.2386 | 0.015* | |
| H2D4 | 0.5166 | 0.0009 | 0.2225 | 0.015* | |
| C3D | 0.80965 (12) | 0.09622 (6) | −0.09656 (6) | 0.00862 (15) | |
| Zn1E | 0.22955 (2) | 0.24635 (2) | 0.28844 (2) | 0.00695 (3) | |
| Cl1E | 0.02321 (3) | 0.32263 (2) | 0.37380 (2) | 0.01053 (4) | |
| Cl2E | 0.09386 (3) | 0.12821 (2) | 0.20032 (2) | 0.01134 (4) | |
| Cl3E | 0.43186 (3) | 0.18443 (2) | 0.38989 (2) | 0.01078 (4) | |
| Cl4E | 0.37370 (3) | 0.34934 (2) | 0.20252 (2) | 0.01048 (4) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cr1A | 0.00661 (9) | 0.00475 (8) | 0.00601 (8) | −0.00088 (6) | −0.00137 (6) | 0.00022 (6) |
| S1A | 0.01664 (11) | 0.00822 (9) | 0.01275 (10) | −0.00177 (8) | −0.00551 (8) | −0.00184 (7) |
| N1A | 0.0113 (3) | 0.0130 (4) | 0.0098 (3) | −0.0010 (3) | 0.0011 (3) | 0.0008 (3) |
| N2A | 0.0132 (4) | 0.0082 (3) | 0.0123 (3) | 0.0008 (3) | −0.0029 (3) | 0.0013 (3) |
| N3A | 0.0104 (3) | 0.0111 (3) | 0.0116 (3) | −0.0023 (3) | −0.0021 (3) | 0.0001 (3) |
| C1A | 0.0114 (4) | 0.0213 (5) | 0.0167 (4) | 0.0046 (4) | 0.0025 (3) | −0.0014 (4) |
| C2A | 0.0159 (4) | 0.0108 (4) | 0.0168 (4) | 0.0051 (3) | −0.0028 (3) | −0.0038 (3) |
| C3A | 0.0089 (4) | 0.0083 (4) | 0.0098 (4) | 0.0012 (3) | 0.0002 (3) | 0.0031 (3) |
| Cr2B | 0.00588 (8) | 0.00513 (8) | 0.00366 (8) | 0.00158 (6) | −0.00107 (6) | −0.00018 (6) |
| S1B | 0.02450 (12) | 0.01331 (10) | 0.00660 (9) | 0.00362 (9) | −0.00526 (8) | 0.00280 (8) |
| N1B | 0.0101 (3) | 0.0080 (3) | 0.0085 (3) | 0.0000 (3) | 0.0000 (3) | −0.0010 (3) |
| N2B | 0.0108 (3) | 0.0089 (3) | 0.0073 (3) | 0.0019 (3) | 0.0004 (3) | −0.0017 (2) |
| N3B | 0.0097 (3) | 0.0120 (3) | 0.0096 (3) | 0.0020 (3) | −0.0020 (3) | 0.0010 (3) |
| C1B | 0.0096 (4) | 0.0123 (4) | 0.0131 (4) | 0.0000 (3) | 0.0029 (3) | 0.0006 (3) |
| C2B | 0.0149 (4) | 0.0130 (4) | 0.0078 (4) | 0.0015 (3) | 0.0036 (3) | 0.0005 (3) |
| C3B | 0.0088 (4) | 0.0081 (3) | 0.0072 (3) | −0.0002 (3) | 0.0009 (3) | −0.0011 (3) |
| Cr3C | 0.00541 (8) | 0.00389 (8) | 0.00375 (8) | 0.00058 (6) | −0.00073 (6) | 0.00083 (6) |
| S1C | 0.01002 (10) | 0.01022 (10) | 0.01841 (11) | 0.00200 (7) | 0.00200 (8) | −0.00320 (8) |
| N1C | 0.0104 (3) | 0.0082 (3) | 0.0051 (3) | −0.0003 (3) | −0.0013 (2) | 0.0009 (2) |
| N2C | 0.0148 (4) | 0.0081 (3) | 0.0059 (3) | −0.0035 (3) | −0.0017 (3) | 0.0012 (2) |
| N3C | 0.0102 (3) | 0.0136 (4) | 0.0116 (3) | 0.0033 (3) | 0.0015 (3) | 0.0032 (3) |
| C1C | 0.0145 (4) | 0.0110 (4) | 0.0071 (4) | −0.0040 (3) | 0.0001 (3) | 0.0028 (3) |
| C2C | 0.0226 (5) | 0.0071 (4) | 0.0088 (4) | −0.0038 (3) | −0.0014 (3) | 0.0024 (3) |
| C3C | 0.0092 (4) | 0.0105 (4) | 0.0085 (4) | −0.0013 (3) | −0.0004 (3) | 0.0023 (3) |
| Cr4D | 0.00413 (8) | 0.00421 (8) | 0.00761 (8) | 0.00135 (6) | 0.00197 (6) | 0.00099 (6) |
| S1D | 0.01028 (10) | 0.00953 (10) | 0.01695 (11) | 0.00014 (7) | 0.00598 (8) | 0.00466 (8) |
| N1D | 0.0086 (3) | 0.0064 (3) | 0.0109 (3) | 0.0017 (2) | 0.0022 (3) | 0.0002 (3) |
| N2D | 0.0099 (3) | 0.0084 (3) | 0.0129 (3) | 0.0023 (3) | −0.0004 (3) | 0.0025 (3) |
| N3D | 0.0084 (3) | 0.0091 (3) | 0.0134 (3) | −0.0004 (3) | 0.0031 (3) | −0.0002 (3) |
| C1D | 0.0138 (4) | 0.0092 (4) | 0.0101 (4) | −0.0006 (3) | −0.0003 (3) | 0.0002 (3) |
| C2D | 0.0175 (4) | 0.0120 (4) | 0.0094 (4) | 0.0001 (3) | 0.0001 (3) | 0.0029 (3) |
| C3D | 0.0081 (4) | 0.0063 (3) | 0.0114 (4) | 0.0018 (3) | −0.0001 (3) | −0.0002 (3) |
| Zn1E | 0.00724 (5) | 0.00672 (5) | 0.00674 (5) | 0.00094 (3) | −0.00074 (3) | −0.00012 (3) |
| Cl1E | 0.00871 (9) | 0.01205 (9) | 0.01064 (9) | 0.00290 (7) | 0.00053 (7) | −0.00174 (7) |
| Cl2E | 0.01069 (9) | 0.00975 (9) | 0.01296 (9) | −0.00072 (7) | −0.00204 (7) | −0.00320 (7) |
| Cl3E | 0.00939 (9) | 0.01256 (9) | 0.01027 (9) | 0.00166 (7) | −0.00291 (7) | 0.00272 (7) |
| Cl4E | 0.01084 (9) | 0.01095 (9) | 0.00978 (9) | −0.00068 (7) | −0.00084 (7) | 0.00329 (7) |
Geometric parameters (Å, º)
| Cr1A—N3Ai | 1.9838 (11) | Cr3C—N2C | 2.0653 (10) |
| Cr1A—N3A | 1.9838 (11) | Cr3C—N2Ciii | 2.0653 (10) |
| Cr1A—N1Ai | 2.0775 (10) | Cr3C—N1Ciii | 2.0727 (9) |
| Cr1A—N1A | 2.0776 (10) | Cr3C—N1C | 2.0727 (9) |
| Cr1A—N2A | 2.0818 (10) | S1C—C3C | 1.6215 (11) |
| Cr1A—N2Ai | 2.0818 (10) | N1C—C1C | 1.4891 (12) |
| S1A—C3A | 1.6181 (11) | N1C—H1C1 | 0.9100 |
| N1A—C1A | 1.4905 (14) | N1C—H1C2 | 0.9100 |
| N1A—H1A1 | 0.9100 | N2C—C2C | 1.4903 (12) |
| N1A—H1A2 | 0.9100 | N2C—H2C1 | 0.9100 |
| N2A—C2A | 1.4912 (13) | N2C—H2C2 | 0.9100 |
| N2A—H2A1 | 0.9100 | N3C—C3C | 1.1672 (13) |
| N2A—H2A2 | 0.9100 | C1C—C2C | 1.5125 (14) |
| N3A—C3A | 1.1704 (13) | C1C—H1C3 | 0.9900 |
| C1A—C2A | 1.5094 (16) | C1C—H1C4 | 0.9900 |
| C1A—H1A3 | 0.9900 | C2C—H2C3 | 0.9900 |
| C1A—H1A4 | 0.9900 | C2C—H2C4 | 0.9900 |
| C2A—H2A3 | 0.9900 | Cr4D—N3Div | 1.9890 (10) |
| C2A—H2A4 | 0.9900 | Cr4D—N3D | 1.9890 (10) |
| Cr2B—N3B | 1.9811 (10) | Cr4D—N1Div | 2.0765 (10) |
| Cr2B—N3Bii | 1.9811 (10) | Cr4D—N1D | 2.0766 (10) |
| Cr2B—N1Bii | 2.0707 (10) | Cr4D—N2D | 2.0799 (10) |
| Cr2B—N1B | 2.0708 (10) | Cr4D—N2Div | 2.0799 (10) |
| Cr2B—N2B | 2.0837 (10) | S1D—C3D | 1.6237 (11) |
| Cr2B—N2Bii | 2.0837 (10) | N1D—C1D | 1.4891 (13) |
| S1B—C3B | 1.6148 (10) | N1D—H1D1 | 0.9100 |
| N1B—C1B | 1.4879 (13) | N1D—H1D2 | 0.9100 |
| N1B—H1B1 | 0.9100 | N2D—C2D | 1.4903 (13) |
| N1B—H1B2 | 0.9100 | N2D—H2D1 | 0.9100 |
| N2B—C2B | 1.4907 (13) | N2D—H2D2 | 0.9100 |
| N2B—H2B1 | 0.9100 | N3D—C3D | 1.1690 (13) |
| N2B—H2B2 | 0.9100 | C1D—C2D | 1.5131 (13) |
| N3B—C3B | 1.1665 (13) | C1D—H1D3 | 0.9900 |
| C1B—C2B | 1.5092 (14) | C1D—H1D4 | 0.9900 |
| C1B—H1B3 | 0.9900 | C2D—H2D3 | 0.9900 |
| C1B—H1B4 | 0.9900 | C2D—H2D4 | 0.9900 |
| C2B—H2B3 | 0.9900 | Zn1E—Cl2E | 2.2518 (8) |
| C2B—H2B4 | 0.9900 | Zn1E—Cl4E | 2.2630 (7) |
| Cr3C—N3C | 1.9864 (10) | Zn1E—Cl3E | 2.2903 (8) |
| Cr3C—N3Ciii | 1.9864 (10) | Zn1E—Cl1E | 2.2923 (8) |
| N3Ai—Cr1A—N3A | 180.0 | N3C—Cr3C—N2Ciii | 92.81 (4) |
| N3Ai—Cr1A—N1Ai | 89.16 (4) | N3Ciii—Cr3C—N2Ciii | 87.19 (4) |
| N3A—Cr1A—N1Ai | 90.84 (4) | N2C—Cr3C—N2Ciii | 180.0 |
| N3Ai—Cr1A—N1A | 90.84 (4) | N3C—Cr3C—N1Ciii | 88.78 (4) |
| N3A—Cr1A—N1A | 89.16 (4) | N3Ciii—Cr3C—N1Ciii | 91.22 (4) |
| N1Ai—Cr1A—N1A | 180.0 | N2C—Cr3C—N1Ciii | 96.91 (4) |
| N3Ai—Cr1A—N2A | 90.31 (4) | N2Ciii—Cr3C—N1Ciii | 83.09 (4) |
| N3A—Cr1A—N2A | 89.69 (4) | N3C—Cr3C—N1C | 91.22 (4) |
| N1Ai—Cr1A—N2A | 97.06 (4) | N3Ciii—Cr3C—N1C | 88.78 (4) |
| N1A—Cr1A—N2A | 82.94 (4) | N2C—Cr3C—N1C | 83.09 (4) |
| N3Ai—Cr1A—N2Ai | 89.69 (4) | N2Ciii—Cr3C—N1C | 96.91 (4) |
| N3A—Cr1A—N2Ai | 90.31 (4) | N1Ciii—Cr3C—N1C | 180.0 |
| N1Ai—Cr1A—N2Ai | 82.94 (4) | C1C—N1C—Cr3C | 107.84 (6) |
| N1A—Cr1A—N2Ai | 97.06 (4) | C1C—N1C—H1C1 | 110.1 |
| N2A—Cr1A—N2Ai | 180.0 | Cr3C—N1C—H1C1 | 110.1 |
| C1A—N1A—Cr1A | 109.59 (6) | C1C—N1C—H1C2 | 110.1 |
| C1A—N1A—H1A1 | 109.8 | Cr3C—N1C—H1C2 | 110.1 |
| Cr1A—N1A—H1A1 | 109.8 | H1C1—N1C—H1C2 | 108.5 |
| C1A—N1A—H1A2 | 109.8 | C2C—N2C—Cr3C | 108.84 (6) |
| Cr1A—N1A—H1A2 | 109.8 | C2C—N2C—H2C1 | 109.9 |
| H1A1—N1A—H1A2 | 108.2 | Cr3C—N2C—H2C1 | 109.9 |
| C2A—N2A—Cr1A | 107.35 (6) | C2C—N2C—H2C2 | 109.9 |
| C2A—N2A—H2A1 | 110.2 | Cr3C—N2C—H2C2 | 109.9 |
| Cr1A—N2A—H2A1 | 110.2 | H2C1—N2C—H2C2 | 108.3 |
| C2A—N2A—H2A2 | 110.2 | C3C—N3C—Cr3C | 163.96 (8) |
| Cr1A—N2A—H2A2 | 110.2 | N1C—C1C—C2C | 106.92 (8) |
| H2A1—N2A—H2A2 | 108.5 | N1C—C1C—H1C3 | 110.3 |
| C3A—N3A—Cr1A | 166.35 (8) | C2C—C1C—H1C3 | 110.3 |
| N1A—C1A—C2A | 109.01 (8) | N1C—C1C—H1C4 | 110.3 |
| N1A—C1A—H1A3 | 109.9 | C2C—C1C—H1C4 | 110.3 |
| C2A—C1A—H1A3 | 109.9 | H1C3—C1C—H1C4 | 108.6 |
| N1A—C1A—H1A4 | 109.9 | N2C—C2C—C1C | 107.87 (7) |
| C2A—C1A—H1A4 | 109.9 | N2C—C2C—H2C3 | 110.1 |
| H1A3—C1A—H1A4 | 108.3 | C1C—C2C—H2C3 | 110.1 |
| N2A—C2A—C1A | 107.69 (8) | N2C—C2C—H2C4 | 110.1 |
| N2A—C2A—H2A3 | 110.2 | C1C—C2C—H2C4 | 110.1 |
| C1A—C2A—H2A3 | 110.2 | H2C3—C2C—H2C4 | 108.4 |
| N2A—C2A—H2A4 | 110.2 | N3C—C3C—S1C | 178.85 (9) |
| C1A—C2A—H2A4 | 110.2 | N3Div—Cr4D—N3D | 180.0 |
| H2A3—C2A—H2A4 | 108.5 | N3Div—Cr4D—N1Div | 89.74 (4) |
| N3A—C3A—S1A | 178.78 (9) | N3D—Cr4D—N1Div | 90.26 (4) |
| N3B—Cr2B—N3Bii | 180.0 | N3Div—Cr4D—N1D | 90.26 (4) |
| N3B—Cr2B—N1Bii | 89.64 (4) | N3D—Cr4D—N1D | 89.74 (4) |
| N3Bii—Cr2B—N1Bii | 90.36 (4) | N1Div—Cr4D—N1D | 180.00 (3) |
| N3B—Cr2B—N1B | 90.36 (4) | N3Div—Cr4D—N2D | 88.05 (4) |
| N3Bii—Cr2B—N1B | 89.64 (4) | N3D—Cr4D—N2D | 91.95 (4) |
| N1Bii—Cr2B—N1B | 180.0 | N1Div—Cr4D—N2D | 96.97 (4) |
| N3B—Cr2B—N2B | 91.27 (4) | N1D—Cr4D—N2D | 83.03 (4) |
| N3Bii—Cr2B—N2B | 88.73 (4) | N3Div—Cr4D—N2Div | 91.95 (4) |
| N1Bii—Cr2B—N2B | 96.72 (4) | N3D—Cr4D—N2Div | 88.05 (4) |
| N1B—Cr2B—N2B | 83.28 (4) | N1Div—Cr4D—N2Div | 83.03 (4) |
| N3B—Cr2B—N2Bii | 88.73 (4) | N1D—Cr4D—N2Div | 96.97 (4) |
| N3Bii—Cr2B—N2Bii | 91.27 (4) | N2D—Cr4D—N2Div | 180.0 |
| N1Bii—Cr2B—N2Bii | 83.28 (4) | C1D—N1D—Cr4D | 107.80 (6) |
| N1B—Cr2B—N2Bii | 96.72 (4) | C1D—N1D—H1D1 | 110.1 |
| N2B—Cr2B—N2Bii | 180.0 | Cr4D—N1D—H1D1 | 110.1 |
| C1B—N1B—Cr2B | 108.20 (6) | C1D—N1D—H1D2 | 110.1 |
| C1B—N1B—H1B1 | 110.1 | Cr4D—N1D—H1D2 | 110.1 |
| Cr2B—N1B—H1B1 | 110.1 | H1D1—N1D—H1D2 | 108.5 |
| C1B—N1B—H1B2 | 110.1 | C2D—N2D—Cr4D | 108.84 (6) |
| Cr2B—N1B—H1B2 | 110.1 | C2D—N2D—H2D1 | 109.9 |
| H1B1—N1B—H1B2 | 108.4 | Cr4D—N2D—H2D1 | 109.9 |
| C2B—N2B—Cr2B | 107.91 (6) | C2D—N2D—H2D2 | 109.9 |
| C2B—N2B—H2B1 | 110.1 | Cr4D—N2D—H2D2 | 109.9 |
| Cr2B—N2B—H2B1 | 110.1 | H2D1—N2D—H2D2 | 108.3 |
| C2B—N2B—H2B2 | 110.1 | C3D—N3D—Cr4D | 169.62 (8) |
| Cr2B—N2B—H2B2 | 110.1 | N1D—C1D—C2D | 107.70 (8) |
| H2B1—N2B—H2B2 | 108.4 | N1D—C1D—H1D3 | 110.2 |
| C3B—N3B—Cr2B | 164.42 (8) | C2D—C1D—H1D3 | 110.2 |
| N1B—C1B—C2B | 107.95 (8) | N1D—C1D—H1D4 | 110.2 |
| N1B—C1B—H1B3 | 110.1 | C2D—C1D—H1D4 | 110.2 |
| C2B—C1B—H1B3 | 110.1 | H1D3—C1D—H1D4 | 108.5 |
| N1B—C1B—H1B4 | 110.1 | N2D—C2D—C1D | 107.87 (8) |
| C2B—C1B—H1B4 | 110.1 | N2D—C2D—H2D3 | 110.1 |
| H1B3—C1B—H1B4 | 108.4 | C1D—C2D—H2D3 | 110.1 |
| N2B—C2B—C1B | 107.96 (7) | N2D—C2D—H2D4 | 110.1 |
| N2B—C2B—H2B3 | 110.1 | C1D—C2D—H2D4 | 110.1 |
| C1B—C2B—H2B3 | 110.1 | H2D3—C2D—H2D4 | 108.4 |
| N2B—C2B—H2B4 | 110.1 | N3D—C3D—S1D | 179.15 (9) |
| C1B—C2B—H2B4 | 110.1 | Cl2E—Zn1E—Cl4E | 111.63 (2) |
| H2B3—C2B—H2B4 | 108.4 | Cl2E—Zn1E—Cl3E | 111.31 (2) |
| N3B—C3B—S1B | 177.11 (8) | Cl4E—Zn1E—Cl3E | 106.71 (2) |
| N3C—Cr3C—N3Ciii | 180.0 | Cl2E—Zn1E—Cl1E | 107.46 (2) |
| N3C—Cr3C—N2C | 87.19 (4) | Cl4E—Zn1E—Cl1E | 112.49 (2) |
| N3Ciii—Cr3C—N2C | 92.81 (4) | Cl3E—Zn1E—Cl1E | 107.20 (2) |
| Cr1A—N1A—C1A—C2A | −33.94 (9) | Cr3C—N1C—C1C—C2C | 44.29 (8) |
| Cr1A—N2A—C2A—C1A | −45.42 (9) | Cr3C—N2C—C2C—C1C | 39.21 (9) |
| N1A—C1A—C2A—N2A | 52.98 (10) | N1C—C1C—C2C—N2C | −55.56 (10) |
| Cr2B—N1B—C1B—C2B | −41.73 (8) | Cr4D—N1D—C1D—C2D | −43.80 (8) |
| Cr2B—N2B—C2B—C1B | −40.80 (8) | Cr4D—N2D—C2D—C1D | −38.66 (9) |
| N1B—C1B—C2B—N2B | 55.28 (10) | N1D—C1D—C2D—N2D | 55.05 (10) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x+1, −y, −z.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1A—H1A1···Cl3Ev | 0.91 | 2.48 | 3.3700 (13) | 165 |
| N2A—H2A1···Cl1Evi | 0.91 | 2.50 | 3.3483 (13) | 155 |
| N2A—H2A2···Cl3E | 0.91 | 2.90 | 3.5797 (12) | 133 |
| C1A—H1A3···S1Avii | 0.99 | 2.91 | 3.5983 (15) | 127 |
| C2A—H2A3···Cl3E | 0.99 | 2.91 | 3.5533 (15) | 123 |
| C2A—H2A4···S1Bii | 0.99 | 2.94 | 3.6270 (15) | 128 |
| N1B—H1B1···Cl1E | 0.91 | 2.45 | 3.2813 (13) | 152 |
| N1B—H1B2···S1Avii | 0.91 | 2.81 | 3.5401 (13) | 138 |
| N2B—H2B1···Cl4Eii | 0.91 | 2.49 | 3.3532 (13) | 159 |
| N2B—H2B2···Cl1Eviii | 0.91 | 2.77 | 3.4934 (12) | 138 |
| C1B—H1B3···S1Avii | 0.99 | 2.98 | 3.5910 (14) | 121 |
| C1B—H1B3···S1Bviii | 0.99 | 2.87 | 3.6440 (14) | 136 |
| C2B—H2B3···Cl1Eviii | 0.99 | 2.93 | 3.5309 (14) | 120 |
| N1C—H1C1···Cl4E | 0.91 | 2.40 | 3.3058 (12) | 171 |
| N1C—H1C2···S1B | 0.91 | 2.73 | 3.4473 (14) | 137 |
| N2C—H2C1···S1Cvii | 0.91 | 2.50 | 3.2836 (12) | 144 |
| N2C—H2C2···S1Biii | 0.91 | 2.75 | 3.4063 (11) | 130 |
| N2C—H2C2···S1Dvii | 0.91 | 2.88 | 3.5893 (13) | 135 |
| C1C—H1C4···Cl1E | 0.99 | 2.86 | 3.7421 (13) | 149 |
| N1D—H1D1···S1C | 0.91 | 2.61 | 3.4937 (13) | 164 |
| N1D—H1D2···Cl2E | 0.91 | 2.49 | 3.3919 (12) | 172 |
| N2D—H2D1···S1Civ | 0.91 | 2.78 | 3.6225 (12) | 155 |
| N2D—H2D2···S1Dix | 0.91 | 2.67 | 3.3564 (12) | 133 |
| C1D—H1D3···Cl3E | 0.99 | 2.88 | 3.7357 (14) | 145 |
| C1D—H1D4···Cl2Evi | 0.99 | 2.98 | 3.7397 (12) | 135 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x+1, −y, −z; (v) −x+1, −y, −z+1; (vi) x+1, y, z; (vii) x−1, y, z; (viii) −x, −y+1, −z+1; (ix) −x+2, −y, −z.
References
- Arvai, A. J. & Nielsen, C. (1983). ADSC Quantum-210 ADX. Area Detector System Corporation, Poway, CA, USA.
- Brandenburg, K. (2007). DIAMOND. Crystal Impact GbR, Bonn, Germany.
- Brencic, J. V. & Leban, I. (1981). Z. Anorg. Allg. Chem. 480, 213–219.
- Brenčič, J. V., Leban, I. & Polanc, I. (1987). Acta Cryst. C43, 885–887.
- Choi, J.-H. (2000a). Chem. Phys. 256, 29–35.
- Choi, J.-H. (2000b). Spectrochim. Acta Part A, 58, 1599–1606. [DOI] [PubMed]
- Choi, J.-H., Hong, Y. P. & Park, Y. C. (2002). Spectrochim. Acta Part A, 56, 1653–1660.
- Choi, J.-H., Clegg, W., Harrington, R. W. & Lee, S. H. (2010). J. Chem. Crystallogr. 40, 567–571.
- Choi, J.-H., Joshi, T. & Spiccia, L. (2011). Z. Anorg. Allg. Chem. 637, 1194–1198.
- Choi, J.-H. & Lee, S. H. (2009). J. Mol. Struct. 932, 84–89.
- Choi, J.-H. & Moon, D. (2014). J. Mol. Struct. 1059, 325–331.
- Choi, J.-H., Oh, I.-G., Linder, R. & Schönherr, T. (2004a). Chem. Phys. 297, 7–12.
- Choi, J.-H., Oh, I. G., Suzuki, T. & Kaizaki, S. (2004b). J. Mol. Struct 694, 39–44.
- Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
- Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. [DOI] [PubMed]
- Moon, D., Choi, J.-H., Ryoo, K. S. & Hong, Y. P. (2013). Acta Cryst. E69, m376–m377. [DOI] [PMC free article] [PubMed]
- Ooi, S., Komiyama, Y. & Kuroya, H. (1960). Bull. Chem. Soc. Jpn, 33, 354–357.
- Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
- Sandrini, D., Gandolfi, M. T., Moggi, L. & Balzani, V. (1978). J. Am. Chem. Soc. 100, 1463–1468.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
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/S2056989014027479/sj5433sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027479/sj5433Isup2.hkl
CCDC reference: 1039747
Additional supporting information: crystallographic information; 3D view; checkCIF report