metal-organic compounds
Bis(N-benzyl-N-methyldithiocarbamato-κ2S,S′)(pyridine-κN)cadmium(II)
aCenter of Research Excellence in Nanotechnology (CENT), King Fahd University of Petrolium & Minerals, Dhahran 31261, Saudia Arabia, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cCentre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The title compound, [Cd(C9H10NS2)2(C5H5N)], features a five-coordinate CdII atom, being coordinated by two nearly symmetrically chelating dithiocarbamate ligands and a pyridine N atom. The resulting NS4 donor set defines a distorted coordination geometry tending toward square pyramidal. In the molecular packing, centrosymmetric ten-membered {⋯HCNCS}2 synthons arise as a result of methylene-C—H⋯S interactions. These are connected into layers parallel to (10-2) via weak methyl-C—H⋯π(phenyl) interactions.
Keywords: crystal structure; cadmium; dithiocarbamate.
CCDC reference: 851623
Structure description
Binary cadmium dithiocarbamates self-assemble via secondary Cd⋯S interactions in their crystal structures (Tiekink, 2003) but, the addition of base can disrupt these arrangements. A practical application of this is that the compounds become more suitable as synthetic precursors for the generation of CdS nanoparticles (Ehsan et al., 2012; Tan et al. 2013; Mlowe et al., 2014). It was in this connection that the title compound was synthesized.
The cadmium atom in Cd[S2CNMe(CH2Ph)]2(NC5H5), Fig. 1, is chelated by two almost symmetrically chelating dithiocarbamate ligands and the pyridine-N atom. The near equivalence in the Cd—S bond lengths [i.e. Cd—S1–S4 = 2.5868 (5), 2.6421 (5), 2.5908 (4) and 2.6473 (5) Å, respectively] is reflected in the experimental equivalence in the associated C—S bond lengths that span the narrow range 1.7191 (17) −1.7284 (16) Å. The dihedral angle between the chelate rings is 43.36 (3)°, and the dihedral angles formed between the S1- and S3-chelate rings and the least-squares plane through the pyridine ring are 75.55 (6) and 75.99 (6)°, indicating that the pyridine molecule is symmetrically disposed with respect to each chelate ring. An indicator of coordination geometry in five-coordinate structures is the value of τ (Addison et al., 1984). In the present structure τ computes to 0.41 which is nearer to an ideal square pyramidal geometry (τ = 0) than to an ideal trigonal bipyramidal geometry with τ = 1.0. The presence acute ligand bite angles [i.e. S1—Cd—S2 is 69.295 (13)° and S3—Cd—S4 is 69.094 (13)°] is partially responsible for the observed distortion. The gross structural features just described, match literature precedents (Wei et al. 2005; Ehsan et al., 2012; Mlowe et al., 2014).
The most prominent feature of the molecular packing is the formation of supramolecular layers parallel to (10), Fig. 2. Thus, centrosymmetrically related molecules are connected via methylene-C—H⋯S interactions (Table 1) resulting in ten-membered {⋯HCNCS}2 synthons. The dimers are connected into a two-dimensional array via methyl-C—H⋯π(phenyl) interactions.
|
| Figure 2 of the title compound. The layers are sustained by C—H⋯S and C—H⋯ |
Synthesis and crystallization
Sodium N-benzyl, N-methyldithiocarbamate (2.00 g, 9.13 mmol) was dissolved in acetone (25 mL) and placed in a 250 mL round-bottom flask fitted with a dropping funnel, reflux condenser and an line. Cd(NO3)2·3H2O (1.32 g, 4.54 mmol) was added, and the milky-white solution was stirred for 30 min. At this point, pyridine (30 mL) was added to give a clear and colourless solution, and stirring was continued for a further 1 h. Filtration and slow evaporation of the reaction mixture afforded the title compound, Cd[S2CNMe(CH2Ph)]2(NC5H5), as colourless crystals. Yield 87%, M.p. 135°C. Anal. calc. for C23H25CdN3S4 (MW 584.10): C 47.25, H 4.28, N 7.19, S 21.91; found C 46.54, H 5.25, N 7.74, S 23.31%. 1H NMR (400 MHz, CDCl3): δ = 3.40 [s, 6H, 2(CH3)], 5.19 [s, 4H, 2(CH2)], 7.25–7.37 p.p.m. [complex pattern, 10H, aromatic 2(C6H5)], 7.48–9.03 [complex pattern, 5H, C5H5N]. TGA: 84–138°C (5.2% wt. loss); 138–156°C (2.9%); 146–210°C (5.5%); 210–260°C (1.1%); 260–400°C (59.1%) 26.2% residue. calc. for CdS, 24.7%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 851623
10.1107/S2414314615024293/sj4002sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314615024293/sj4002Isup2.hkl
Sodium N-benzyl, N-methyldithiocarbamate (2.00 g, 9.13 mmol) was dissolved in acetone (25 mL) and placed in a 250 mL round bottom flask fitted with a dropping funnel, reflux condenser and an δ = 3.40 [s, 6H, 2(CH3)], 5.19 [s, 4H, 2(CH2)], 7.25–7.37 ppm [complex pattern, 10H, aromatic 2(C6H5)], 7.48-9.03 [complex pattern, 5H, C5H5N]. TGA: 84–138°C (5.2% wt. loss); 138–156°C (2.9%); 146–210°C (5.5%); 210–260°C (1.1%); 260–400°C (59.1%) 26.2% residue. Calc. for CdS, 24.7%.
line. Cd(NO3)2·3H2O (1.32 g, 4.54 mmol) was added, and the milky white solution was stirred for 30 min. At this point, pyridine (30 mL) was added to give a clear and colourless solution, and stirring was continued for a further 1 h. Filtration and slow evaporation of the reaction mixture afforded the title compound, Cd[S2CNMe(CH2Ph)]2(NC5H5), as colourless crystals. Yield 87%, M.pt: 135 °C. Anal. Calc. for C23H25CdN3S4 (MW 584.10): C 47.25, H 4.28, N 7.19, S 21.91; Found C 46.54, H 5.25, N 7.74, S 23.31 %. 1H NMR (400 MHz, CDCl3):Sodium N-benzyl, N-methyldithiocarbamate (2.00 g, 9.13 mmol) was dissolved in acetone (25 mL) and placed in a 250 mL round-bottom flask fitted with a dropping funnel, reflux condenser and an δ = 3.40 [s, 6H, 2(CH3)], 5.19 [s, 4H, 2(CH2)], 7.25–7.37 p.p.m. [complex pattern, 10H, aromatic 2(C6H5)], 7.48–9.03 [complex pattern, 5H, C5H5N]. TGA: 84–138°C (5.2% wt. loss); 138–156°C (2.9%); 146–210°C (5.5%); 210–260°C (1.1%); 260–400°C (59.1%) 26.2% residue. calc. for CdS, 24.7%.
line. Cd(NO3)2·3H2O (1.32 g, 4.54 mmol) was added, and the milky white solution was stirred for 30 min. At this point, pyridine (30 mL) was added to give a clear and colourless solution, and stirring was continued for a further 1 h. Filtration and slow evaporation of the reaction mixture afforded the title compound, Cd[S2CNMe(CH2Ph)]2(NC5H5), as colourless crystals. Yield 87%, M.p. 135°C. Anal. calc. for C23H25CdN3S4 (MW 584.10): C 47.25, H 4.28, N 7.19, S 21.91; found C 46.54, H 5.25, N 7.74, S 23.31 %. 1H NMR (400 MHz, CDCl3):Binary cadmium dithiocarbamates self-assemble via secondary Cd···S interactions in their crystal structures (Tiekink, 2003) but, the addition of base can disrupt these networks. A practical application of this is that the compounds become more suitable as synthetic precursors for the generation of CdS nanoparticles (Ehsan et al., 2012; Tan et al. 2013; Mlowe et al., 2014). It was in this connection that the title compound was synthesized.
The cadmium atom in Cd[S2CNMe(CH2Ph)]2(NC5H5), Fig. 1, is chelated by two almost symmetrically chelating dithiocarbamate ligands and the pyridine-N atom. The near equivalence in the Cd—S bond lengths [i.e. Cd—S1–S4 = 2.5868 (5), 2.6421 (5), 2.5908 (4) and 2.6473 (5) Å, respectively] is reflected in the experimental equivalence in the associated C—S bond lengths that span the narrow range 1.7191 (17) –1.7284 (16) Å. The dihedral angle between the chelate rings is 43.36 (3)°, and the dihedral angles formed between the S1- and S3-chelate rings and the least-squares plane through the pyridine ring are 75.55 (6) and 75.99 (6)°, indicating that the pyridine molecule is symmetrically disposed with respect to each chelate ring. An indicator of coordination geometry in five-coordinate structures is the value of τ (Addison et al., 1984). In the present structure τ computes to 0.41 which is nearer to an ideal square pyramidal geometry (τ = 0) than to an ideal trigonal bipyramidal geometry with τ = 1.0. The presence acute ligand bite angles [i.e. S1—Cd—S2 is 69.295 (13)° and S3—Cd—S4 is 69.094 (13)°] is partially responsible for the observed distortion. The gross structural features just described, match literature precedents (Wei et al. 2005; Ehsan et al., 2012; Mlowe et al., 2014).
The most prominent feature of the molecular packing is the formation of supramolecular layers parallel to (102), Fig. 2. Thus, centrosymmetrically related molecules are connected via methylene-C—H···S interactions (Table 1) resulting in 10-membered {···HCNCS}2 synthons. The dimers are connected into a two-dimensional array via methyl-C—H···π(phenyl) interactions.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of Cd[S2CNMe(CH2Ph)]2(NC5H5) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. | |
Fig. 2. A view of the supramolecular layer parallel to (102) in the crystal structure of the title compound. The layers are sustained by C—H···S and C—H···π interactions, shown as orange and purple dashed lines, respectively. |
[Cd(C9H10NS2)2(C5H5N)] | F(000) = 1184 |
Mr = 584.10 | Dx = 1.575 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9361 (6) Å | Cell parameters from 9940 reflections |
b = 14.832 (1) Å | θ = 4.7–56.6° |
c = 18.9680 (13) Å | µ = 1.24 mm−1 |
β = 101.613 (1)° | T = 100 K |
V = 2462.6 (3) Å3 | Block, yellow |
Z = 4 | 0.40 × 0.40 × 0.40 mm |
Bruker SMART APEX diffractometer | 5650 independent reflections |
Radiation source: fine-focus sealed tube | 5201 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.636, Tmax = 0.636 | k = −19→19 |
30058 measured reflections | l = −24→24 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0237P)2 + 1.412P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
5650 reflections | Δρmax = 0.41 e Å−3 |
282 parameters | Δρmin = −0.31 e Å−3 |
[Cd(C9H10NS2)2(C5H5N)] | V = 2462.6 (3) Å3 |
Mr = 584.10 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.9361 (6) Å | µ = 1.24 mm−1 |
b = 14.832 (1) Å | T = 100 K |
c = 18.9680 (13) Å | 0.40 × 0.40 × 0.40 mm |
β = 101.613 (1)° |
Bruker SMART APEX diffractometer | 5650 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5201 reflections with I > 2σ(I) |
Tmin = 0.636, Tmax = 0.636 | Rint = 0.026 |
30058 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.41 e Å−3 |
5650 reflections | Δρmin = −0.31 e Å−3 |
282 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd | 0.22879 (2) | 0.27114 (2) | 0.48001 (2) | 0.01746 (4) | |
S1 | 0.11972 (5) | 0.22882 (3) | 0.34732 (2) | 0.01997 (9) | |
S2 | 0.11154 (5) | 0.10701 (3) | 0.47097 (2) | 0.02111 (9) | |
S3 | 0.12935 (5) | 0.33548 (3) | 0.58899 (2) | 0.01989 (9) | |
S4 | 0.25719 (4) | 0.44878 (3) | 0.48621 (2) | 0.01675 (8) | |
N1 | −0.01535 (16) | 0.06902 (9) | 0.33438 (7) | 0.0186 (3) | |
N2 | 0.14132 (15) | 0.51358 (9) | 0.59553 (7) | 0.0156 (3) | |
N3 | 0.48097 (16) | 0.23716 (9) | 0.51799 (8) | 0.0183 (3) | |
C1 | 0.06310 (17) | 0.12864 (11) | 0.38019 (9) | 0.0166 (3) | |
C2 | −0.0497 (2) | 0.08587 (13) | 0.25657 (9) | 0.0251 (4) | |
H2A | −0.1229 | 0.1356 | 0.2458 | 0.038* | |
H2B | −0.0938 | 0.0314 | 0.2313 | 0.038* | |
H2C | 0.0445 | 0.1018 | 0.2406 | 0.038* | |
C3 | −0.07418 (19) | −0.01537 (11) | 0.35810 (9) | 0.0213 (3) | |
H3A | −0.0305 | −0.0243 | 0.4099 | 0.026* | |
H3B | −0.0398 | −0.0661 | 0.3314 | 0.026* | |
C4 | −0.24685 (19) | −0.01729 (11) | 0.34673 (8) | 0.0192 (3) | |
C5 | −0.3330 (2) | 0.06057 (12) | 0.34563 (9) | 0.0222 (3) | |
H5 | −0.2831 | 0.1174 | 0.3523 | 0.027* | |
C6 | −0.4916 (2) | 0.05665 (13) | 0.33482 (10) | 0.0269 (4) | |
H6 | −0.5495 | 0.1106 | 0.3335 | 0.032* | |
C7 | −0.5647 (2) | −0.02603 (15) | 0.32604 (10) | 0.0301 (4) | |
H7 | −0.6730 | −0.0290 | 0.3186 | 0.036* | |
C8 | −0.4798 (2) | −0.10468 (13) | 0.32808 (10) | 0.0281 (4) | |
H8 | −0.5298 | −0.1615 | 0.3225 | 0.034* | |
C9 | −0.3221 (2) | −0.10036 (12) | 0.33824 (9) | 0.0232 (4) | |
H9 | −0.2646 | −0.1544 | 0.3395 | 0.028* | |
C10 | 0.17278 (17) | 0.44101 (11) | 0.56036 (8) | 0.0151 (3) | |
C11 | 0.06478 (19) | 0.50691 (12) | 0.65699 (9) | 0.0208 (3) | |
H11A | −0.0390 | 0.4836 | 0.6406 | 0.031* | |
H11B | 0.0599 | 0.5667 | 0.6783 | 0.031* | |
H11C | 0.1224 | 0.4660 | 0.6931 | 0.031* | |
C12 | 0.18704 (19) | 0.60540 (11) | 0.57864 (9) | 0.0187 (3) | |
H12A | 0.1029 | 0.6481 | 0.5808 | 0.022* | |
H12B | 0.2070 | 0.6067 | 0.5292 | 0.022* | |
C13 | 0.32917 (18) | 0.63419 (11) | 0.63151 (9) | 0.0168 (3) | |
C14 | 0.47127 (19) | 0.59832 (11) | 0.62688 (9) | 0.0199 (3) | |
H14 | 0.4793 | 0.5574 | 0.5893 | 0.024* | |
C15 | 0.60061 (19) | 0.62210 (12) | 0.67682 (9) | 0.0221 (3) | |
H15 | 0.6968 | 0.5972 | 0.6734 | 0.026* | |
C16 | 0.5905 (2) | 0.68217 (12) | 0.73185 (9) | 0.0235 (4) | |
H16 | 0.6795 | 0.6983 | 0.7660 | 0.028* | |
C17 | 0.4501 (2) | 0.71837 (12) | 0.73662 (10) | 0.0241 (4) | |
H17 | 0.4427 | 0.7598 | 0.7740 | 0.029* | |
C18 | 0.3198 (2) | 0.69417 (11) | 0.68669 (9) | 0.0206 (3) | |
H18 | 0.2237 | 0.7189 | 0.6904 | 0.025* | |
C19 | 0.5383 (2) | 0.15745 (12) | 0.50318 (9) | 0.0223 (3) | |
H19 | 0.4710 | 0.1136 | 0.4776 | 0.027* | |
C20 | 0.6921 (2) | 0.13664 (13) | 0.52385 (10) | 0.0255 (4) | |
H20 | 0.7297 | 0.0799 | 0.5121 | 0.031* | |
C21 | 0.7892 (2) | 0.19962 (13) | 0.56167 (10) | 0.0255 (4) | |
H21 | 0.8952 | 0.1872 | 0.5761 | 0.031* | |
C22 | 0.7303 (2) | 0.28154 (12) | 0.57855 (10) | 0.0240 (4) | |
H22 | 0.7949 | 0.3255 | 0.6056 | 0.029* | |
C23 | 0.57606 (19) | 0.29799 (12) | 0.55539 (9) | 0.0211 (3) | |
H23 | 0.5360 | 0.3544 | 0.5664 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.01342 (6) | 0.01678 (7) | 0.02104 (7) | −0.00078 (4) | 0.00073 (4) | −0.00360 (4) |
S1 | 0.0214 (2) | 0.0189 (2) | 0.01913 (19) | −0.00597 (16) | 0.00304 (15) | 0.00025 (15) |
S2 | 0.0254 (2) | 0.01795 (19) | 0.01831 (19) | −0.00568 (16) | 0.00052 (16) | 0.00007 (15) |
S3 | 0.02097 (19) | 0.01831 (19) | 0.0215 (2) | −0.00438 (15) | 0.00700 (16) | 0.00030 (16) |
S4 | 0.01800 (18) | 0.01699 (19) | 0.01633 (18) | 0.00039 (14) | 0.00602 (14) | −0.00006 (14) |
N1 | 0.0186 (7) | 0.0169 (7) | 0.0195 (7) | −0.0030 (5) | 0.0019 (5) | −0.0024 (5) |
N2 | 0.0136 (6) | 0.0177 (7) | 0.0157 (6) | −0.0006 (5) | 0.0035 (5) | −0.0013 (5) |
N3 | 0.0158 (7) | 0.0186 (7) | 0.0201 (7) | 0.0001 (5) | 0.0024 (5) | 0.0002 (5) |
C1 | 0.0129 (7) | 0.0167 (8) | 0.0203 (8) | 0.0011 (6) | 0.0036 (6) | −0.0021 (6) |
C2 | 0.0276 (9) | 0.0283 (9) | 0.0188 (8) | −0.0064 (7) | 0.0033 (7) | −0.0054 (7) |
C3 | 0.0225 (8) | 0.0141 (8) | 0.0253 (9) | −0.0027 (6) | 0.0000 (7) | −0.0022 (6) |
C4 | 0.0229 (8) | 0.0193 (8) | 0.0145 (7) | −0.0036 (6) | 0.0017 (6) | 0.0003 (6) |
C5 | 0.0255 (9) | 0.0206 (8) | 0.0206 (8) | −0.0025 (7) | 0.0047 (7) | −0.0014 (7) |
C6 | 0.0276 (9) | 0.0312 (10) | 0.0230 (9) | 0.0029 (8) | 0.0081 (7) | 0.0012 (7) |
C7 | 0.0228 (9) | 0.0444 (12) | 0.0239 (9) | −0.0064 (8) | 0.0063 (7) | 0.0046 (8) |
C8 | 0.0310 (10) | 0.0298 (10) | 0.0229 (9) | −0.0140 (8) | 0.0038 (7) | 0.0033 (7) |
C9 | 0.0294 (9) | 0.0193 (8) | 0.0197 (8) | −0.0039 (7) | 0.0021 (7) | 0.0015 (7) |
C10 | 0.0101 (7) | 0.0186 (8) | 0.0153 (7) | −0.0003 (6) | −0.0002 (5) | −0.0006 (6) |
C11 | 0.0196 (8) | 0.0266 (9) | 0.0175 (8) | −0.0003 (7) | 0.0070 (6) | −0.0047 (7) |
C12 | 0.0197 (8) | 0.0162 (8) | 0.0197 (8) | 0.0026 (6) | 0.0024 (6) | 0.0005 (6) |
C13 | 0.0192 (8) | 0.0134 (7) | 0.0180 (7) | −0.0003 (6) | 0.0046 (6) | 0.0022 (6) |
C14 | 0.0215 (8) | 0.0182 (8) | 0.0214 (8) | −0.0018 (6) | 0.0076 (6) | −0.0013 (6) |
C15 | 0.0176 (8) | 0.0242 (9) | 0.0255 (9) | −0.0019 (7) | 0.0070 (7) | 0.0022 (7) |
C16 | 0.0231 (8) | 0.0259 (9) | 0.0213 (8) | −0.0089 (7) | 0.0038 (7) | 0.0002 (7) |
C17 | 0.0308 (9) | 0.0206 (8) | 0.0219 (8) | −0.0052 (7) | 0.0079 (7) | −0.0058 (7) |
C18 | 0.0222 (8) | 0.0164 (8) | 0.0243 (8) | 0.0010 (6) | 0.0075 (7) | −0.0009 (7) |
C19 | 0.0214 (8) | 0.0219 (9) | 0.0240 (8) | 0.0012 (7) | 0.0053 (7) | −0.0027 (7) |
C20 | 0.0243 (9) | 0.0246 (9) | 0.0293 (9) | 0.0081 (7) | 0.0096 (7) | 0.0019 (7) |
C21 | 0.0155 (8) | 0.0308 (9) | 0.0304 (10) | 0.0036 (7) | 0.0054 (7) | 0.0094 (8) |
C22 | 0.0174 (8) | 0.0233 (9) | 0.0294 (9) | −0.0040 (7) | 0.0000 (7) | 0.0042 (7) |
C23 | 0.0183 (8) | 0.0186 (8) | 0.0254 (9) | 0.0004 (6) | 0.0023 (7) | 0.0008 (7) |
Cd—N3 | 2.2799 (14) | C7—H7 | 0.9500 |
Cd—S1 | 2.5868 (5) | C8—C9 | 1.384 (3) |
Cd—S3 | 2.5908 (4) | C8—H8 | 0.9500 |
Cd—S2 | 2.6421 (5) | C9—H9 | 0.9500 |
Cd—S4 | 2.6473 (5) | C11—H11A | 0.9800 |
S1—C1 | 1.7262 (17) | C11—H11B | 0.9800 |
S2—C1 | 1.7191 (17) | C11—H11C | 0.9800 |
S3—C10 | 1.7264 (17) | C12—C13 | 1.513 (2) |
S4—C10 | 1.7284 (16) | C12—H12A | 0.9900 |
N1—C1 | 1.335 (2) | C12—H12B | 0.9900 |
N1—C3 | 1.463 (2) | C13—C18 | 1.389 (2) |
N1—C2 | 1.467 (2) | C13—C14 | 1.396 (2) |
N2—C10 | 1.326 (2) | C14—C15 | 1.385 (2) |
N2—C11 | 1.469 (2) | C14—H14 | 0.9500 |
N2—C12 | 1.475 (2) | C15—C16 | 1.389 (2) |
N3—C23 | 1.340 (2) | C15—H15 | 0.9500 |
N3—C19 | 1.340 (2) | C16—C17 | 1.384 (3) |
C2—H2A | 0.9800 | C16—H16 | 0.9500 |
C2—H2B | 0.9800 | C17—C18 | 1.392 (2) |
C2—H2C | 0.9800 | C17—H17 | 0.9500 |
C3—C4 | 1.515 (2) | C18—H18 | 0.9500 |
C3—H3A | 0.9900 | C19—C20 | 1.386 (2) |
C3—H3B | 0.9900 | C19—H19 | 0.9500 |
C4—C5 | 1.386 (2) | C20—C21 | 1.375 (3) |
C4—C9 | 1.397 (2) | C20—H20 | 0.9500 |
C5—C6 | 1.392 (3) | C21—C22 | 1.387 (3) |
C5—H5 | 0.9500 | C21—H21 | 0.9500 |
C6—C7 | 1.384 (3) | C22—C23 | 1.381 (2) |
C6—H6 | 0.9500 | C22—H22 | 0.9500 |
C7—C8 | 1.388 (3) | C23—H23 | 0.9500 |
N3—Cd—S1 | 114.12 (4) | C7—C8—H8 | 120.0 |
N3—Cd—S3 | 107.77 (4) | C8—C9—C4 | 120.63 (17) |
S1—Cd—S3 | 137.998 (15) | C8—C9—H9 | 119.7 |
N3—Cd—S2 | 99.83 (4) | C4—C9—H9 | 119.7 |
S1—Cd—S2 | 69.295 (13) | N2—C10—S3 | 119.60 (12) |
S3—Cd—S2 | 101.303 (14) | N2—C10—S4 | 121.79 (12) |
N3—Cd—S4 | 97.24 (4) | S3—C10—S4 | 118.61 (9) |
S1—Cd—S4 | 107.379 (13) | N2—C11—H11A | 109.5 |
S3—Cd—S4 | 69.094 (13) | N2—C11—H11B | 109.5 |
S2—Cd—S4 | 162.384 (14) | H11A—C11—H11B | 109.5 |
C1—S1—Cd | 86.44 (6) | N2—C11—H11C | 109.5 |
C1—S2—Cd | 84.82 (6) | H11A—C11—H11C | 109.5 |
C10—S3—Cd | 87.02 (5) | H11B—C11—H11C | 109.5 |
C10—S4—Cd | 85.19 (6) | N2—C12—C13 | 110.41 (13) |
C1—N1—C3 | 122.72 (14) | N2—C12—H12A | 109.6 |
C1—N1—C2 | 121.19 (14) | C13—C12—H12A | 109.6 |
C3—N1—C2 | 116.08 (13) | N2—C12—H12B | 109.6 |
C10—N2—C11 | 121.63 (14) | C13—C12—H12B | 109.6 |
C10—N2—C12 | 122.96 (13) | H12A—C12—H12B | 108.1 |
C11—N2—C12 | 115.34 (13) | C18—C13—C14 | 119.01 (15) |
C23—N3—C19 | 118.46 (15) | C18—C13—C12 | 120.71 (15) |
C23—N3—Cd | 119.97 (11) | C14—C13—C12 | 120.24 (15) |
C19—N3—Cd | 121.57 (11) | C15—C14—C13 | 120.30 (16) |
N1—C1—S2 | 121.43 (12) | C15—C14—H14 | 119.8 |
N1—C1—S1 | 119.26 (12) | C13—C14—H14 | 119.8 |
S2—C1—S1 | 119.30 (9) | C14—C15—C16 | 120.40 (16) |
N1—C2—H2A | 109.5 | C14—C15—H15 | 119.8 |
N1—C2—H2B | 109.5 | C16—C15—H15 | 119.8 |
H2A—C2—H2B | 109.5 | C17—C16—C15 | 119.65 (16) |
N1—C2—H2C | 109.5 | C17—C16—H16 | 120.2 |
H2A—C2—H2C | 109.5 | C15—C16—H16 | 120.2 |
H2B—C2—H2C | 109.5 | C16—C17—C18 | 120.03 (16) |
N1—C3—C4 | 113.03 (14) | C16—C17—H17 | 120.0 |
N1—C3—H3A | 109.0 | C18—C17—H17 | 120.0 |
C4—C3—H3A | 109.0 | C13—C18—C17 | 120.60 (16) |
N1—C3—H3B | 109.0 | C13—C18—H18 | 119.7 |
C4—C3—H3B | 109.0 | C17—C18—H18 | 119.7 |
H3A—C3—H3B | 107.8 | N3—C19—C20 | 122.40 (16) |
C5—C4—C9 | 118.70 (16) | N3—C19—H19 | 118.8 |
C5—C4—C3 | 122.22 (15) | C20—C19—H19 | 118.8 |
C9—C4—C3 | 119.08 (15) | C21—C20—C19 | 118.82 (17) |
C4—C5—C6 | 120.89 (16) | C21—C20—H20 | 120.6 |
C4—C5—H5 | 119.6 | C19—C20—H20 | 120.6 |
C6—C5—H5 | 119.6 | C20—C21—C22 | 119.14 (16) |
C7—C6—C5 | 119.79 (18) | C20—C21—H21 | 120.4 |
C7—C6—H6 | 120.1 | C22—C21—H21 | 120.4 |
C5—C6—H6 | 120.1 | C23—C22—C21 | 118.80 (17) |
C6—C7—C8 | 119.95 (18) | C23—C22—H22 | 120.6 |
C6—C7—H7 | 120.0 | C21—C22—H22 | 120.6 |
C8—C7—H7 | 120.0 | N3—C23—C22 | 122.35 (16) |
C9—C8—C7 | 120.04 (17) | N3—C23—H23 | 118.8 |
C9—C8—H8 | 120.0 | C22—C23—H23 | 118.8 |
C3—N1—C1—S2 | 4.2 (2) | Cd—S3—C10—N2 | 177.56 (12) |
C2—N1—C1—S2 | −176.90 (12) | Cd—S3—C10—S4 | −2.63 (8) |
C3—N1—C1—S1 | −176.86 (12) | Cd—S4—C10—N2 | −177.61 (13) |
C2—N1—C1—S1 | 2.0 (2) | Cd—S4—C10—S3 | 2.58 (8) |
Cd—S2—C1—N1 | −177.38 (13) | C10—N2—C12—C13 | −100.13 (17) |
Cd—S2—C1—S1 | 3.67 (9) | C11—N2—C12—C13 | 76.79 (17) |
Cd—S1—C1—N1 | 177.29 (13) | N2—C12—C13—C18 | −103.51 (17) |
Cd—S1—C1—S2 | −3.74 (9) | N2—C12—C13—C14 | 74.33 (19) |
C1—N1—C3—C4 | 111.20 (17) | C18—C13—C14—C15 | 0.2 (2) |
C2—N1—C3—C4 | −67.76 (19) | C12—C13—C14—C15 | −177.64 (15) |
N1—C3—C4—C5 | −27.0 (2) | C13—C14—C15—C16 | −0.3 (3) |
N1—C3—C4—C9 | 154.03 (15) | C14—C15—C16—C17 | 0.0 (3) |
C9—C4—C5—C6 | −1.3 (3) | C15—C16—C17—C18 | 0.4 (3) |
C3—C4—C5—C6 | 179.78 (16) | C14—C13—C18—C17 | 0.1 (2) |
C4—C5—C6—C7 | 0.9 (3) | C12—C13—C18—C17 | 177.98 (15) |
C5—C6—C7—C8 | 0.0 (3) | C16—C17—C18—C13 | −0.4 (3) |
C6—C7—C8—C9 | −0.6 (3) | C23—N3—C19—C20 | −1.3 (3) |
C7—C8—C9—C4 | 0.2 (3) | Cd—N3—C19—C20 | 177.92 (13) |
C5—C4—C9—C8 | 0.7 (3) | N3—C19—C20—C21 | 0.8 (3) |
C3—C4—C9—C8 | 179.71 (16) | C19—C20—C21—C22 | 0.6 (3) |
C11—N2—C10—S3 | −2.3 (2) | C20—C21—C22—C23 | −1.4 (3) |
C12—N2—C10—S3 | 174.39 (11) | C19—N3—C23—C22 | 0.5 (3) |
C11—N2—C10—S4 | 177.86 (11) | Cd—N3—C23—C22 | −178.80 (13) |
C12—N2—C10—S4 | −5.4 (2) | C21—C22—C23—N3 | 0.9 (3) |
Cg1 is the centroid of the C4–C9 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···S2i | 0.99 | 2.79 | 3.5926 (17) | 138 |
C11—H11C···Cg1ii | 0.98 | 2.91 | 3.3715 (18) | 110 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1/2, −y−1/2, z−1/2. |
Cg1 is the centroid of the C4–C9 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···S2i | 0.99 | 2.79 | 3.5926 (17) | 138 |
C11—H11C···Cg1ii | 0.98 | 2.91 | 3.3715 (18) | 110 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1/2, −y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C9H10NS2)2(C5H5N)] |
Mr | 584.10 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 8.9361 (6), 14.832 (1), 18.9680 (13) |
β (°) | 101.613 (1) |
V (Å3) | 2462.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.24 |
Crystal size (mm) | 0.40 × 0.40 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.636, 0.636 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30058, 5650, 5201 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.051, 1.04 |
No. of reflections | 5650 |
No. of parameters | 282 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.31 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Footnotes
‡Additional correspondence author, e-mail: mazhar42pk@yahoo.com.
Acknowledgements
The authors acknowledge funding from the UMRG (RP007A-13AET) and the High-Impact Research Scheme (UM·C/625/1/HIR/242).
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ehsan, M. A., Ming, H. N., Misran, M., Arifin, Z., Tiekink, E. R. T., Safwan, A. P., Ebadi, M., Basirun, W. J. & Mazhar, M. (2012). Chem. Vapor Dep. 18, 191–200. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mlowe, S., Lewis, D. J., Azad Malik, M., Raftery, J., Mubofu, E. B., O'Brien, P. & Revaprasadu, N. (2014). New J. Chem. 38, 6073–6080. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tan, Y. S., Sudlow, A. L., Molloy, K. C., Morishima, Y., Fujisawa, K., Jackson, W. J., Henderson, W., Halim, S. N. B. A., Ng, S. W. & Tiekink, E. R. T. (2013). Cryst. Growth Des. 13, 3046–3056. Web of Science CSD CrossRef CAS Google Scholar
Tiekink, E. R. T. (2003). CrystEngComm, 5, 101–113. Web of Science CrossRef CAS Google Scholar
Wei, F.-X., Yin, X., Zhang, W.-G., Fan, J., Jiang, X.-H. & Wang, S.-L. (2005). Z. Kristallogr. New Cryst. Struct. 220, 417–419. CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.