In dichloridobis(1,3-diazinane-2-thione-κS)cadmium(II), the CdII atom is bound to two chloride anions and two thione ligands via their S atoms. The geometry around the CdII atom is distorted tetrahedral, with the bond angles in the range 101.61 (3)–118.00 (3)°. Intramolecular N—H⋯Cl hydrogen-bonding interactions stabilize a butterfly syn molecular conformation.
Keywords: crystal structure; cadmium chloride; 1,3-diazinane-2-thione
Abstract
In the structure of the title compound, [CdCl2(C4H8N2S)2], the CdII atom is coordinated by two chloride ions and two 1,3-diazinane-2-thione (Diaz) molecules through their S atoms. The geometry around the CdII atom is distorted tetrahedral, with bond angles in the range 101.55 (7)–117.91 (8)°. The CH2 groups of one Diaz ligand are disordered over two sets of sites with an occupancy ratio of 0.711 (12):0.289 (12). The molecular structure is stabilized by intramolecular N—H⋯Cl hydrogen-bonding interactions, generating a butterfly syn conformation. Intermolecular N—H⋯Cl and N—H⋯S interactions lead to the formation of a three-dimensional network structure. The structure has been determined from a crystal twinned by nonmerohedry, by a 180° rotation around the reciprocal c axis. The twin ratio refined to 0.8866 (6):0.1134 (6).
Chemical context
Cadmium is considered to be a soft Lewis acid and possesses high affininty towards sulfur donor ligands such as thiones. Upon exposure to living systems, it preferablly interacts with sulfur-containing biomoleules. Therefore, complexes of cadmium with thiones are important as structural models to understand metal–sulfur interactions in biological systems (Akrivos, 2001 ▸; Bell et al., 2004 ▸). In view of this, the crystal structures of several cadmium complexes of thiones, such as imidazolidine-2-thione (Imt) and 1,3-diazinane-2-thione (Diaz), have been reported (Ahmad et al., 2012 ▸; Al-Arfaj et al., 1998 ▸; Bell et al., 2004 ▸; Lobana et al., 2008 ▸; Malik et al., 2010 ▸; Mahmood et al., 2012 ▸, 2015 ▸; Wazeer et al., 2007 ▸). The complexity of structures of the L 2CdX 2 type (where L is a thione and X is a halide or pseudohalide) ranges from mononuclear tetrahedral complexes to polymeric octahedral species. We have reported recently the crystal structures of three cadmium complexes of Diaz, namely, [CdI2(Diaz)2], [Cd(CH3COO)2(Diaz)2] and [Cd(Diaz)4]SO4 (Ahmad et al., 2012 ▸; Mahmood et al., 2012 ▸, 2015 ▸). To learn more about the structural aspects of cadmium complexes, we report here the crystal structure of a cadmium chloride complex of 1,3-diazinane-2-thione, i.e. [CdCl2(Diaz)2], (I). The spectroscopic properties of the compound have been reported previously (Wazeer et al., 2007 ▸).
Structural commentary
In the molecular structure of (I) (Fig. 1 ▸), the CdII atom is bonded to two S atoms, each belonging to a Diaz molecule, and two chloride ions. The coordination geometry at the CdII atom is distorted tetrahedral, with the following bond angles: S—Cd—S = 105.08 (3)°, Cl—Cd—Cl = 101.61 (3)° and S—Cd—Cl in the range 108.91 (2)–118.00 (3)°. The Cl—Cd—Cl bond angle is significantly smaller than the other bond angles, which could be due to the involvement of Cl in intramolecular (N—H⋯Cl) hydrogen bonding. The Cd—S and Cd—Cl bond lengths are in agreement with those reported for related compounds (Ahmad et al., 2011 ▸, 2012 ▸; Al-Arfaj et al., 1998 ▸; Bell et al., 2004 ▸; Lobana et al., 2008 ▸; Malik et al., 2010 ▸; Mahmood et al., 2012 ▸, 2015 ▸; Wazeer et al., 2007 ▸). The two Diaz six-membered rings adopt half-chair conformations. In one of the two rings (the one involving atom S2), two of the methylene C atoms (C7 and C8) are disordered over two positions. The SCN2 moieties of the Diaz ligands are essentially planar and the corresponding C—S and C—N bond lengths are in the ranges 1.730 (3)–1.731 (3) and 1.318 (3)–1.327 (3) Å, respectively. The C—S bond length is slightly longer than in the free ligand [1.720 (2) Å [Popovic et al., 2001 ▸]. The shorter N—C(S) bond length compared to N—C(C) [1.456 (4) Å] is consistent with a significant N—C(S) double-bond character associated with an electronic delocalization towards the metal ion upon coordination. Compound (I) is related to that of the reported complexes [ZnCl2(Diaz)2] (Malik et al., 2011 ▸) and [CdI2(Diaz)2] (Ahmad et al., 2012 ▸) that both crystallize in space group C2/c. They show an equivalent degree of distortion from tetrahedral configuration as in (I). However, in [CdCl2(Dmtu)2] and [CdBr2(Dmtu)2] (Dmtu = N,N′-dimethylthiourea), the coordination geometry at the CdII atom is almost perfectly tetrahedral (Ahmad et al., 2011 ▸; Malik et al., 2010 ▸).
Figure 1.
A view of the molecular structure of the title compound, showing the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. The minor-occupancy C atoms are connected by dashed lines.
Supramolecular features
Compound (I) shows both intra- and intermolecular hydrogen-bonding interactions. One chloride anion (Cl2) is engaged in intramolecular N—H⋯Cl hydrogen-bonding interactions with one N—H group of each of the two Diaz ligands (Table 1 ▸). This results in a butterfly syn conformation, where the two Diaz six-membered rings reside on the same side of the CdS2 plane. When such interactions are not effective, an anti conformation may be observed, where the two Diaz rings are located anti relative to the CdS2 plane. This situation is observed in [CdI2(Diaz)2] (Ahmad et al., 2012 ▸). The second chloride (Cl1) anion undergoes intermolecular hydrogen-bonding interactions with one N—H group of a Diaz ligand belonging to an adjacent complex molecule, hence generating a chain structure along the a axis (Fig. 2 ▸). Furthermore, zigzag interchain N—H⋯S interactions take place, giving rise to a three-dimensional hydrogen-bonding network.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1—H1⋯Cl2 | 0.86 | 2.46 | 3.230 (3) | 149 |
| N2—H2⋯S2i | 0.86 | 2.55 | 3.363 (2) | 159 |
| N3A—H3C⋯Cl2 | 0.86 | 2.46 | 3.196 (3) | 144 |
| N3B—H3D⋯Cl2 | 0.86 | 2.48 | 3.196 (3) | 141 |
| N4A—H4C⋯Cl1ii | 0.86 | 2.44 | 3.270 (3) | 162 |
| N4B—H4D⋯Cl1ii | 0.86 | 2.46 | 3.270 (3) | 157 |
Symmetry codes: (i) 
; (ii) 
.
Figure 2.
The packing diagram for (I), showing the hydrogen-bonding interactions. The minor-occupancy disordered atoms have been omitted for clarity.
Database survey
A search of the Cambridge Structural Database (Groom & Allen, 2014 ▸) for cadmium complexes of 1,3-diazinane-2-thione yielded three structures including the above mentioned [CdI2(Diaz)2] (Ahmad et al., 2012 ▸). Although the structure of [ZnCl2(Diaz)2] (Malik et al., 2011 ▸) is similar to (I), the structure of a related mercury(II) complex is significantly different. It crystallizes in an ionic form, with {[Hg(Diaz)2]2+}2 cations and {[HgCl4]2−}2 anions (Popovic et al., 2001 ▸).
Synthesis and crystallization
1,3-Diazinane-2-thione (Diaz) was prepared according to the literature procedure of Ahmad et al. (2012 ▸). The complex was prepared by adding a solution of Diaz (0.24 g, 2.0 mmol) in methanol (15 ml) to an aqueous solution (5 ml) of cadmium chloride (1.0 mmol, 0.21 g) and stirring the resulting mixture for 30 min. The colourless solution was filtered and the filtrate was kept at room temperature for crystallization. After 48 h, light-yellow crystals were obtained. The crystals were washed with methanol and dried in air (yield: 0.25 g, 0.60 mmol, 60%). The spectroscopic data of compound (I) have been reported previously (Wazeer et al., 2007 ▸).
Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The crystal under investigation was found to be twinned by non-merohedry. The orientation matrices for the two components were identified using the program CELL NOW (Sheldrick, 2005 ▸), with the two components being related by a 180° rotation around the real/reciprocal axis [104]/(001). The two components were integrated using SAINT resulting in the following statistics: 7087 reflections (2024 unique) involved domain 1 only (mean I/σ = 23.7), 6799 reflections (1938 unique) involved domain 2 only (mean I/σ = 8.6) and 6567 reflections (1969 unique) the two domains (mean I/σ = 23.2).
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [CdCl2(C4H8N2S)2] |
| M r | 415.67 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 296 |
| a, b, c (Å) | 8.5078 (8), 14.7201 (13), 12.0019 (10) |
| β (°) | 101.016 (4) |
| V (Å3) | 1475.4 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 2.11 |
| Crystal size (mm) | 0.40 × 0.30 × 0.28 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (TWINABS; Sheldrick, 2009 ▸) |
| T min, T max | 0.487, 0.589 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3512, 3512, 3110 |
| R int | 0.037 |
| (sin θ/λ)max (Å−1) | 0.657 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.029, 0.077, 1.05 |
| No. of reflections | 3512 |
| No. of parameters | 184 |
| No. of restraints | 50 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.56, −1.18 |
The exact twin matrix identified by the integration program was found to be 1.00176 −0.00043 0.00606, −0.00069 −1.00042 0.00237, −0.52475 −0.00141 −1.00198. The structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of component 1 (including the overlapping ones) resulting in a BASF value of 0.1134 (6).
The C atoms of one Diaz moiety (C6/C7/C8) are disordered over two sets of sites, with an occupancy ratio of 0.715 (11):0.285 (11). Atoms N3A and N4A were constrained to have identical positions and displacement parameters as their equivalent partners in the major moiety, but their H atoms were included in the disorder model. Major and minor moieties were restrained to have similar geometries [SAME command in SHELX2014 (Sheldrick, 2015 ▸)], and their atoms were subjected to a rigid-bond restraint (RIGU command in SHELX2014). The anisotropic displacement parameters of these C atoms were also subjected to a rigid-bond restraint (RIGU).
H atoms were placed at calculated positions and allowed to ride, with C—H and N—H distances of 0.97 and 0.86 Å, respectively, and with U iso(H) = 1.2U eq(C,N).
Supplementary Material
Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901502109X/zl2641sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901502109X/zl2641Isup2.hkl
CCDC reference: 1435435
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by the Vice Chancellor, University of Sargodha, Pakistan.
supplementary crystallographic information
Crystal data
| [CdCl2(C4H8N2S)2] | F(000) = 824 |
| Mr = 415.67 | Dx = 1.871 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.5078 (8) Å | Cell parameters from 3110 reflections |
| b = 14.7201 (13) Å | θ = 2.2–27.9° |
| c = 12.0019 (10) Å | µ = 2.11 mm−1 |
| β = 101.016 (4)° | T = 296 K |
| V = 1475.4 (2) Å3 | Block, light yellow |
| Z = 4 | 0.40 × 0.30 × 0.28 mm |
Data collection
| Bruker APEXII CCD diffractometer | 3512 independent reflections |
| Radiation source: fine-focus sealed tube | 3110 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.037 |
| Detector resolution: 7.6 pixels mm-1 | θmax = 27.9°, θmin = 2.2° |
| φ and ω scans | h = −11→10 |
| Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | k = 0→19 |
| Tmin = 0.487, Tmax = 0.589 | l = 0→15 |
| 3512 measured reflections |
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)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.727P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 3512 reflections | Δρmax = 0.56 e Å−3 |
| 184 parameters | Δρmin = −1.18 e Å−3 |
| 50 restraints | Extinction correction: SHELXL2014 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0020 (4) |
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. |
| Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Cd1 | 0.24350 (2) | 0.25053 (2) | −0.17323 (2) | 0.03632 (9) | |
| Cl1 | 0.00058 (10) | 0.33253 (7) | −0.25626 (7) | 0.0599 (2) | |
| Cl2 | 0.24104 (10) | 0.26375 (5) | 0.03652 (7) | 0.04534 (18) | |
| S1 | 0.26254 (11) | 0.08460 (5) | −0.22331 (6) | 0.04513 (19) | |
| S2 | 0.50720 (10) | 0.32086 (6) | −0.20300 (6) | 0.0462 (2) | |
| N1 | 0.2258 (3) | 0.04740 (16) | −0.0092 (2) | 0.0449 (6) | |
| H1 | 0.1902 | 0.1020 | −0.0077 | 0.054* | |
| N2 | 0.3317 (3) | −0.06371 (16) | −0.1046 (2) | 0.0388 (5) | |
| H2 | 0.3724 | −0.0789 | −0.1622 | 0.047* | |
| C1 | 0.2737 (3) | 0.01920 (18) | −0.1023 (2) | 0.0330 (5) | |
| C2 | 0.2306 (5) | −0.0096 (2) | 0.0905 (2) | 0.0524 (8) | |
| H2A | 0.1458 | 0.0081 | 0.1298 | 0.063* | |
| H2B | 0.3322 | −0.0017 | 0.1422 | 0.063* | |
| C3 | 0.2098 (4) | −0.1080 (2) | 0.0549 (3) | 0.0486 (8) | |
| H3A | 0.2239 | −0.1466 | 0.1215 | 0.058* | |
| H3B | 0.1028 | −0.1176 | 0.0113 | 0.058* | |
| C4 | 0.3314 (4) | −0.1317 (2) | −0.0156 (3) | 0.0458 (7) | |
| H4A | 0.4368 | −0.1347 | 0.0324 | 0.055* | |
| H4B | 0.3070 | −0.1909 | −0.0500 | 0.055* | |
| C5 | 0.6195 (3) | 0.35738 (18) | −0.0751 (2) | 0.0355 (6) | |
| N3A | 0.5543 (3) | 0.37659 (18) | 0.0138 (2) | 0.0446 (6) | 0.715 (11) |
| H3C | 0.4526 | 0.3700 | 0.0077 | 0.053* | 0.715 (11) |
| C6A | 0.6473 (10) | 0.4084 (17) | 0.1216 (8) | 0.058 (4) | 0.715 (11) |
| H6A | 0.6716 | 0.3575 | 0.1733 | 0.069* | 0.715 (11) |
| H6B | 0.5846 | 0.4519 | 0.1553 | 0.069* | 0.715 (11) |
| C7A | 0.7995 (6) | 0.4519 (5) | 0.1047 (5) | 0.0599 (18) | 0.715 (11) |
| H7A | 0.8663 | 0.4651 | 0.1778 | 0.072* | 0.715 (11) |
| H7B | 0.7759 | 0.5086 | 0.0639 | 0.072* | 0.715 (11) |
| C8A | 0.8876 (8) | 0.3891 (5) | 0.0382 (5) | 0.0501 (17) | 0.715 (11) |
| H8A | 0.9821 | 0.4188 | 0.0214 | 0.060* | 0.715 (11) |
| H8B | 0.9206 | 0.3344 | 0.0815 | 0.060* | 0.715 (11) |
| N4A | 0.7753 (3) | 0.3665 (2) | −0.0678 (2) | 0.0503 (7) | 0.715 (11) |
| H4C | 0.8138 | 0.3587 | −0.1284 | 0.060* | 0.715 (11) |
| N3B | 0.5543 (3) | 0.37659 (18) | 0.0138 (2) | 0.0446 (6) | 0.285 (11) |
| H3D | 0.4519 | 0.3718 | 0.0043 | 0.053* | 0.285 (11) |
| C6B | 0.637 (2) | 0.405 (4) | 0.126 (2) | 0.054 (9) | 0.285 (11) |
| H6C | 0.5985 | 0.3701 | 0.1837 | 0.065* | 0.285 (11) |
| H6D | 0.6163 | 0.4686 | 0.1374 | 0.065* | 0.285 (11) |
| C7B | 0.8121 (14) | 0.3903 (11) | 0.1362 (9) | 0.051 (4) | 0.285 (11) |
| H7C | 0.8369 | 0.3264 | 0.1489 | 0.062* | 0.285 (11) |
| H7D | 0.8698 | 0.4242 | 0.2005 | 0.062* | 0.285 (11) |
| C8B | 0.864 (2) | 0.4215 (12) | 0.0283 (11) | 0.055 (5) | 0.285 (11) |
| H8C | 0.8404 | 0.4855 | 0.0154 | 0.066* | 0.285 (11) |
| H8D | 0.9787 | 0.4129 | 0.0348 | 0.066* | 0.285 (11) |
| N4B | 0.7753 (3) | 0.3665 (2) | −0.0678 (2) | 0.0503 (7) | 0.285 (11) |
| H4D | 0.8239 | 0.3416 | −0.1166 | 0.060* | 0.285 (11) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.03251 (13) | 0.03676 (13) | 0.03966 (13) | 0.00136 (8) | 0.00685 (9) | 0.00459 (8) |
| Cl1 | 0.0476 (4) | 0.0886 (6) | 0.0445 (4) | 0.0300 (4) | 0.0115 (3) | 0.0120 (4) |
| Cl2 | 0.0537 (5) | 0.0469 (4) | 0.0391 (3) | −0.0049 (3) | 0.0180 (3) | −0.0017 (3) |
| S1 | 0.0669 (5) | 0.0369 (4) | 0.0326 (3) | −0.0009 (3) | 0.0120 (3) | 0.0021 (3) |
| S2 | 0.0460 (4) | 0.0624 (5) | 0.0318 (3) | −0.0169 (4) | 0.0118 (3) | 0.0020 (3) |
| N1 | 0.0633 (17) | 0.0344 (12) | 0.0418 (12) | 0.0098 (12) | 0.0219 (12) | 0.0036 (10) |
| N2 | 0.0451 (14) | 0.0345 (12) | 0.0377 (11) | 0.0040 (10) | 0.0103 (10) | −0.0032 (10) |
| C1 | 0.0331 (14) | 0.0331 (13) | 0.0325 (11) | −0.0029 (11) | 0.0055 (10) | −0.0001 (10) |
| C2 | 0.076 (2) | 0.0485 (18) | 0.0372 (14) | 0.0022 (16) | 0.0223 (15) | 0.0047 (13) |
| C3 | 0.059 (2) | 0.0433 (17) | 0.0426 (15) | −0.0060 (15) | 0.0084 (14) | 0.0090 (13) |
| C4 | 0.0532 (19) | 0.0357 (15) | 0.0456 (15) | 0.0055 (14) | 0.0024 (14) | 0.0042 (12) |
| C5 | 0.0371 (15) | 0.0351 (14) | 0.0354 (12) | −0.0034 (11) | 0.0093 (11) | 0.0050 (10) |
| N3A | 0.0331 (13) | 0.0609 (16) | 0.0413 (12) | −0.0057 (11) | 0.0113 (10) | −0.0080 (11) |
| C6A | 0.055 (4) | 0.078 (9) | 0.042 (3) | −0.014 (4) | 0.011 (3) | −0.015 (4) |
| C7A | 0.049 (3) | 0.066 (4) | 0.064 (3) | −0.009 (3) | 0.010 (2) | −0.021 (3) |
| C8A | 0.032 (3) | 0.057 (4) | 0.059 (3) | 0.000 (3) | 0.004 (2) | −0.006 (3) |
| N4A | 0.0349 (14) | 0.0725 (19) | 0.0463 (13) | −0.0056 (12) | 0.0151 (11) | −0.0070 (12) |
| N3B | 0.0331 (13) | 0.0609 (16) | 0.0413 (12) | −0.0057 (11) | 0.0113 (10) | −0.0080 (11) |
| C6B | 0.042 (7) | 0.07 (2) | 0.046 (8) | −0.008 (7) | 0.008 (5) | −0.015 (9) |
| C7B | 0.044 (6) | 0.058 (9) | 0.050 (5) | −0.005 (5) | 0.005 (4) | −0.015 (5) |
| C8B | 0.036 (7) | 0.067 (10) | 0.060 (6) | −0.007 (7) | 0.004 (5) | −0.008 (6) |
| N4B | 0.0349 (14) | 0.0725 (19) | 0.0463 (13) | −0.0056 (12) | 0.0151 (11) | −0.0070 (12) |
Geometric parameters (Å, º)
| Cd1—Cl1 | 2.4361 (8) | N3A—C6A | 1.458 (7) |
| Cd1—S1 | 2.5280 (8) | N3A—H3C | 0.8600 |
| Cd1—Cl2 | 2.5290 (8) | C6A—C7A | 1.493 (12) |
| Cd1—S2 | 2.5571 (8) | C6A—H6A | 0.9700 |
| S1—C1 | 1.730 (3) | C6A—H6B | 0.9700 |
| S2—C5 | 1.731 (3) | C7A—C8A | 1.510 (8) |
| N1—C1 | 1.327 (3) | C7A—H7A | 0.9700 |
| N1—C2 | 1.456 (4) | C7A—H7B | 0.9700 |
| N1—H1 | 0.8600 | C8A—N4A | 1.476 (6) |
| N2—C1 | 1.319 (3) | C8A—H8A | 0.9700 |
| N2—C4 | 1.464 (4) | C8A—H8B | 0.9700 |
| N2—H2 | 0.8600 | N4A—H4C | 0.8600 |
| C2—C3 | 1.511 (5) | N3B—C6B | 1.456 (15) |
| C2—H2A | 0.9700 | N3B—H3D | 0.8600 |
| C2—H2B | 0.9700 | C6B—C7B | 1.484 (19) |
| C3—C4 | 1.497 (4) | C6B—H6C | 0.9700 |
| C3—H3A | 0.9700 | C6B—H6D | 0.9700 |
| C3—H3B | 0.9700 | C7B—C8B | 1.518 (15) |
| C4—H4A | 0.9700 | C7B—H7C | 0.9700 |
| C4—H4B | 0.9700 | C7B—H7D | 0.9700 |
| C5—N4B | 1.318 (4) | C8B—N4B | 1.492 (13) |
| C5—N4A | 1.318 (4) | C8B—H8C | 0.9700 |
| C5—N3B | 1.324 (3) | C8B—H8D | 0.9700 |
| C5—N3A | 1.324 (3) | N4B—H4D | 0.8600 |
| Cl1—Cd1—S1 | 118.00 (3) | N3A—C6A—H6A | 109.5 |
| Cl1—Cd1—Cl2 | 101.61 (3) | C7A—C6A—H6A | 109.5 |
| S1—Cd1—Cl2 | 108.91 (2) | N3A—C6A—H6B | 109.5 |
| Cl1—Cd1—S2 | 116.15 (3) | C7A—C6A—H6B | 109.5 |
| S1—Cd1—S2 | 105.08 (3) | H6A—C6A—H6B | 108.1 |
| Cl2—Cd1—S2 | 106.39 (3) | C6A—C7A—C8A | 109.9 (8) |
| C1—S1—Cd1 | 109.50 (9) | C6A—C7A—H7A | 109.7 |
| C5—S2—Cd1 | 110.63 (9) | C8A—C7A—H7A | 109.7 |
| C1—N1—C2 | 123.1 (2) | C6A—C7A—H7B | 109.7 |
| C1—N1—H1 | 118.4 | C8A—C7A—H7B | 109.7 |
| C2—N1—H1 | 118.4 | H7A—C7A—H7B | 108.2 |
| C1—N2—C4 | 124.4 (2) | N4A—C8A—C7A | 106.8 (5) |
| C1—N2—H2 | 117.8 | N4A—C8A—H8A | 110.4 |
| C4—N2—H2 | 117.8 | C7A—C8A—H8A | 110.4 |
| N2—C1—N1 | 118.9 (2) | N4A—C8A—H8B | 110.4 |
| N2—C1—S1 | 117.3 (2) | C7A—C8A—H8B | 110.4 |
| N1—C1—S1 | 123.8 (2) | H8A—C8A—H8B | 108.6 |
| N1—C2—C3 | 109.7 (2) | C5—N4A—C8A | 123.9 (3) |
| N1—C2—H2A | 109.7 | C5—N4A—H4C | 118.1 |
| C3—C2—H2A | 109.7 | C8A—N4A—H4C | 118.1 |
| N1—C2—H2B | 109.7 | C5—N3B—C6B | 127.0 (7) |
| C3—C2—H2B | 109.7 | C5—N3B—H3D | 116.5 |
| H2A—C2—H2B | 108.2 | C6B—N3B—H3D | 116.5 |
| C4—C3—C2 | 109.1 (3) | N3B—C6B—C7B | 109.7 (14) |
| C4—C3—H3A | 109.9 | N3B—C6B—H6C | 109.7 |
| C2—C3—H3A | 109.9 | C7B—C6B—H6C | 109.7 |
| C4—C3—H3B | 109.9 | N3B—C6B—H6D | 109.7 |
| C2—C3—H3B | 109.9 | C7B—C6B—H6D | 109.7 |
| H3A—C3—H3B | 108.3 | H6C—C6B—H6D | 108.2 |
| N2—C4—C3 | 110.5 (2) | C6B—C7B—C8B | 109.7 (18) |
| N2—C4—H4A | 109.5 | C6B—C7B—H7C | 109.7 |
| C3—C4—H4A | 109.5 | C8B—C7B—H7C | 109.7 |
| N2—C4—H4B | 109.5 | C6B—C7B—H7D | 109.7 |
| C3—C4—H4B | 109.5 | C8B—C7B—H7D | 109.7 |
| H4A—C4—H4B | 108.1 | H7C—C7B—H7D | 108.2 |
| N4B—C5—N3B | 119.7 (3) | N4B—C8B—C7B | 107.9 (11) |
| N4A—C5—N3A | 119.7 (3) | N4B—C8B—H8C | 110.1 |
| N4B—C5—S2 | 117.9 (2) | C7B—C8B—H8C | 110.1 |
| N4A—C5—S2 | 117.9 (2) | N4B—C8B—H8D | 110.1 |
| N3B—C5—S2 | 122.4 (2) | C7B—C8B—H8D | 110.1 |
| N3A—C5—S2 | 122.4 (2) | H8C—C8B—H8D | 108.4 |
| C5—N3A—C6A | 122.9 (4) | C5—N4B—C8B | 117.5 (7) |
| C5—N3A—H3C | 118.5 | C5—N4B—H4D | 121.3 |
| C6A—N3A—H3C | 118.5 | C8B—N4B—H4D | 121.3 |
| N3A—C6A—C7A | 110.8 (7) | ||
| C4—N2—C1—N1 | 7.1 (4) | S2—C5—N3A—C6A | −179.3 (12) |
| C4—N2—C1—S1 | −172.2 (2) | C5—N3A—C6A—C7A | 24 (2) |
| C2—N1—C1—N2 | −1.5 (4) | N3A—C6A—C7A—C8A | −51.6 (17) |
| C2—N1—C1—S1 | 177.7 (3) | C6A—C7A—C8A—N4A | 55.3 (10) |
| Cd1—S1—C1—N2 | −160.02 (19) | N3A—C5—N4A—C8A | 5.9 (6) |
| Cd1—S1—C1—N1 | 20.8 (3) | S2—C5—N4A—C8A | −174.4 (4) |
| C1—N1—C2—C3 | −29.8 (4) | C7A—C8A—N4A—C5 | −34.2 (8) |
| N1—C2—C3—C4 | 53.7 (4) | N4B—C5—N3B—C6B | −2 (3) |
| C1—N2—C4—C3 | 19.8 (4) | S2—C5—N3B—C6B | 178 (3) |
| C2—C3—C4—N2 | −49.1 (3) | C5—N3B—C6B—C7B | −12 (5) |
| Cd1—S2—C5—N4B | 157.6 (2) | N3B—C6B—C7B—C8B | 43 (4) |
| Cd1—S2—C5—N4A | 157.6 (2) | C6B—C7B—C8B—N4B | −61 (3) |
| Cd1—S2—C5—N3B | −22.8 (3) | N3B—C5—N4B—C8B | −16.5 (9) |
| Cd1—S2—C5—N3A | −22.8 (3) | S2—C5—N4B—C8B | 163.2 (8) |
| N4A—C5—N3A—C6A | 0.4 (12) | C7B—C8B—N4B—C5 | 47.6 (16) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl2 | 0.86 | 2.46 | 3.230 (3) | 149 |
| N2—H2···S2i | 0.86 | 2.55 | 3.363 (2) | 159 |
| N3A—H3C···Cl2 | 0.86 | 2.46 | 3.196 (3) | 144 |
| N3B—H3D···Cl2 | 0.86 | 2.48 | 3.196 (3) | 141 |
| N4A—H4C···Cl1ii | 0.86 | 2.44 | 3.270 (3) | 162 |
| N4B—H4D···Cl1ii | 0.86 | 2.46 | 3.270 (3) | 157 |
| C7B—H7C···Cl1iii | 0.97 | 2.85 | 3.769 (16) | 159 |
Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) x+1, y, z; (iii) x+1, −y+1/2, 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, New_Global_Publ_Block. DOI: 10.1107/S205698901502109X/zl2641sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901502109X/zl2641Isup2.hkl
CCDC reference: 1435435
Additional supporting information: crystallographic information; 3D view; checkCIF report