Bis(N-benzyl-N-methyl­dithio­carbamato-κ2S,S′)(pyridine-κN)cadmium(II)

Ehsan, M.A.; Mazhar, M.; Tiekink, E.R.T.

doi:10.1107/S2414314615024293

metal-organic compounds

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ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152429

doi:10.1107/S2414314615024293

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Bis(N-benzyl-N-methyldithiocarbamato-κ²S,S′)(pyridine-κN)cadmium(II)

Muhammad Ali Ehsan,^a Muhammad Mazhar ^b ‡ and Edward R. T. Tiekink ^c ^*

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 16 December 2015; accepted 17 December 2015; online 12 January 2016)

The title compound, [Cd(C₉H₁₀NS₂)₂(C₅H₅N)], features a five-coordinate Cd^II 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

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Chemical scheme

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).

Figure 1
The molecular structure of Cd[S₂CNMe(CH₂Ph)]₂(NC₅H₅) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

The most prominent feature of the molecular packing is the formation of supramolecular layers parallel to (10 $[\overline{2}]$ ), 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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view of the supramolecular layer parallel to (10 $[\overline{2}]$ ) 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.

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 inert gas 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cd(C₉H₁₀NS₂)₂(C₅H₅N)]
M_r	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 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.636, 0.636
No. of measured, independent and observed [I > 2σ(I)] reflections	30058, 5650, 5201
R_int	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
Δρ_max, Δρ_min (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 ).

Structural data

CCDC reference: 851623

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314615024293/sj4002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314615024293/sj4002Isup2.hkl

checkCIF report

Synthesis and crystallization top

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 inert gas 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): 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%.

Refinement top

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C).

Experimental top

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 inert gas 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%.

Structure description top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	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.

Bis(N-benzyl-N-methyldithiocarbamato-κ²S,S')(pyridine-κN)cadmium(II) top

Crystal data top

[Cd(C₉H₁₀NS₂)₂(C₅H₅N)]	F(000) = 1184
M_r = 584.10	D_x = 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

Data collection top

Bruker SMART APEX diffractometer	5650 independent reflections
Radiation source: fine-focus sealed tube	5201 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.636, T_max = 0.636	k = −19→19
30058 measured reflections	l = −24→24

Refinement top

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(F_o²) + (0.0237P)² + 1.412P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
5650 reflections	Δρ_max = 0.41 e Å⁻³
282 parameters	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cd(C₉H₁₀NS₂)₂(C₅H₅N)]	V = 2462.6 (3) Å³
M_r = 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)°

Data collection top

Bruker SMART APEX diffractometer	5650 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5201 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.636	R_int = 0.026
30058 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.051	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
5650 reflections	Δρ_min = −0.31 e Å⁻³
282 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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)]
M_r	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)
T_min, T_max	0.636, 0.636
No. of measured, independent and observed [I > 2σ(I)] reflections	30058, 5650, 5201
R_int	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
Δρ_max, Δρ_min (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

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