(μ-2-Pyridine­aldazine-κ4N,N′:N′′,N′′′)bis­[bis­(N,N-di-n-propyl­dithio­carbamato-κ2S,S′)cadmium(II)]

Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S1600536808025889

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page m1176

doi:10.1107/S1600536808025889

Open

access

(μ-2-Pyridinealdazine-κ⁴N,N′:N′′,N′′′)bis[bis(N,N-di-n-propyldithiocarbamato-κ²S,S′)cadmium(II)]

Pavel Poplaukhin ^a and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249-0698, USA
^*Correspondence e-mail: edward.tiekink@utsa.edu

(Received 10 August 2008; accepted 11 August 2008; online 16 August 2008)

The dinuclear centrosymmetric title compound, [Cd₂(C₇H₁₄NS₂)₄(C₁₂H₁₀N₄)], features a tetradentate 2-pyridinealdazine ligand that chelates two Cd centres. The coordination geometry for Cd is distorted octahedral based on a cis-N₂S₄ donor set. In the crystal structure, molecules are connected into a supramolecular chain aligned along the a direction via C—H⋯S and C—H⋯π contacts, and by π–π contacts [centroid-to-centroid distance 3.5708 (15) Å]. The n-propyl groups are each disordered, one equally over two sites and the other with a site-occupancy factor of 0.618 (8) for the major component.

Related literature

For background literature, see: Tiekink (2006 ); Benson et al. (2007 ). For a related structure, see: Lai & Tiekink (2006 ).

Experimental

Crystal data

[Cd₂(C₇H₁₄NS₂)₄(C₁₂H₁₀N₄)]
M_r = 1140.39
Monoclinic, P 2₁ /c
a = 9.0768 (16) Å
b = 11.137 (2) Å
c = 25.389 (5) Å
β = 92.216 (3)°
V = 2564.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 98 (2) K
0.35 × 0.12 × 0.10 mm

Data collection

Rigaku AFC12κ/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.656, T_max = 1 (expected range = 0.582–0.888)
20914 measured reflections
5861 independent reflections
5539 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.077
S = 1.08
5861 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N3/C15–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯S4ⁱ	0.99	2.83	3.815 (3)	171
C16—H16⋯S3ⁱⁱ	0.95	2.82	3.674 (3)	150
C3—H3B⋯Cgⁱⁱⁱ	0.95	2.99	3.853 (5)	147
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x+1, y, z; (iii) x, y-1, z.

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025889/ng2485sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025889/ng2485Isup2.hkl

checkCIF report

Comment top

Metal dithiocarbamates have recently been applied in crystal engineering studies (e.g. Tiekink, 2006; Benson et al., 2007). The title compound, {[(nPr)₂NCS₂]₂Cd(2-C₅H₄N—C(H)═N—N═C(H)C₅H₄N-2)- Cd[S₂CN(nPr)₂]₂} (I), features a centrosymmetric tetradentate 2-pyridinealdazine ligand coordinating to two Cd centres each of which is chelated by two dithiocarbamate ligands, Fig. 1. The molecule is centrosymmetric about the central N—N bond. The range of Cd—S bond distances is relatively narrow at 2.6124 (8) to 2.7165 (7) Å, but the Cd—N bond formed by the pyridine-N of 2.377 (2) Å is significantly shorter than the Cd—N bond distance of 2.6211 (19) Å formed with the azo-N atom. The coordination geometry is based on an octahedron within a cis-N₂S₄ donor set. The structure reported here for (I) resembles closely the dithiophosphate analogue (Lai & Tiekink, 2006). In the crystal structure, molecules are connected into a supramolecular chain, aligned along the a-direction and illustrated in Fig. 2, via C—H···S3 and π–π contacts. The latter occur between centrosymmetically related N3,C15—C19 rings with Cg···Cg = 3.5708 (15) Å. These are consolidated into the crystal structure via additional C—H···S4 contacts and C—H···π interactions, Table 1 and Fig. 3.

Related literature top

For background literature, see: Tiekink (2006); Benson et al. (2007). For a related structure, see: Lai & Tiekink (2006).

Experimental top

Compound (I) was prepared by standard methods (Benson et al., 2007) and red crystals were grown by the slow evaporation of a methanol–ethanol (1/1) solution of (I), m.p. 441-443 K. IR (cm^-1): 1474 (s, C═N), 1171 (s, C—S). TGA: One broad step with onset = 625 K, midpoint = 662 K, and endset = 711 K which corresponds to decomposition leading to CdS (mass loss 79.4% cf. theoretical mass loss = 74.4%).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) showing the crystallographic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. Unlabelled atoms are related by the symmetry operation i: -x, 1 - y, 1 - z. The minor components of the disordered n-propyl groups omitted for clarity.
	Fig. 2. View of a supramolecular chain in (I) highlighting the overlap of the aromatic rings to allow the formation of the π–π interactions. The C—H···S3 interactions are shown as orange dashed lines. Colour code: Cd (orange), S (yellow), O (red), N (blue), C (grey) & H (green).
	Fig. 3. View in projection of the crystal packing in (I). Colour code as for Fig. 2.

(µ-2-Pyridinealdazine- κ⁴N,N':N'',N''')bis[bis(N,N-di-n- propyldithiocarbamato-κ²S,S')cadmium(II)] top

Crystal data top

[Cd₂(C₇H₁₄NS₂)₄(C₁₂H₁₀N₄)]	F(000) = 1172
M_r = 1140.39	D_x = 1.477 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 16020 reflections
a = 9.0768 (16) Å	θ = 1.8–40.5°
b = 11.137 (2) Å	µ = 1.19 mm⁻¹
c = 25.389 (5) Å	T = 98 K
β = 92.216 (3)°	Prism, red
V = 2564.7 (8) Å³	0.35 × 0.12 × 0.10 mm
Z = 2

Data collection top

Rigaku AFC12κ/SATURN724 diffractometer	5861 independent reflections
Radiation source: fine-focus sealed tube	5539 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.656, T_max = 1	k = −14→14
20914 measured reflections	l = −32→31

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0362P)² + 2.6654P] where P = (F_o² + 2F_c²)/3
5861 reflections	(Δ/σ)_max = 0.001
299 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[Cd₂(C₇H₁₄NS₂)₄(C₁₂H₁₀N₄)]	V = 2564.7 (8) Å³
M_r = 1140.39	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0768 (16) Å	µ = 1.19 mm⁻¹
b = 11.137 (2) Å	T = 98 K
c = 25.389 (5) Å	0.35 × 0.12 × 0.10 mm
β = 92.216 (3)°

Data collection top

Rigaku AFC12κ/SATURN724 diffractometer	5861 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5539 reflections with I > 2σ(I)
T_min = 0.656, T_max = 1	R_int = 0.031
20914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.08	Δρ_max = 0.71 e Å⁻³
5861 reflections	Δρ_min = −0.72 e Å⁻³
299 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd	0.153452 (17)	0.407355 (14)	0.605114 (6)	0.01585 (6)
S1	0.07349 (7)	0.19908 (6)	0.56627 (3)	0.03080 (16)
S2	0.37230 (6)	0.24128 (5)	0.61348 (3)	0.02499 (14)
S3	−0.06899 (6)	0.53972 (6)	0.63409 (2)	0.02094 (12)
S4	0.19579 (6)	0.48599 (5)	0.70265 (2)	0.01910 (12)
N2	−0.0279 (2)	0.6233 (2)	0.73187 (8)	0.0204 (4)
N3	0.3282 (2)	0.53991 (17)	0.56901 (8)	0.0170 (4)
N4	0.06743 (19)	0.50248 (18)	0.51464 (7)	0.0162 (4)
C1	0.2466 (2)	0.1454 (2)	0.58446 (9)	0.0181 (4)
C2	0.1771 (3)	−0.0570 (2)	0.55108 (11)	0.0278 (5)	0.618 (8)
H2A	0.2185	−0.0870	0.5181	0.033*	0.618 (8)
H2B	0.0832	−0.0156	0.5417	0.033*	0.618 (8)
C3	0.1459 (5)	−0.1621 (4)	0.5862 (2)	0.0325 (13)	0.618 (8)
H3A	0.0719	−0.2141	0.5678	0.039*	0.618 (8)
H3B	0.2376	−0.2096	0.5912	0.039*	0.618 (8)
C4	0.0910 (4)	−0.1317 (4)	0.63923 (14)	0.0540 (10)	0.618 (8)
H4A	0.0742	−0.2057	0.6590	0.081*	0.618 (8)
H4B	−0.0017	−0.0869	0.6351	0.081*	0.618 (8)
H4C	0.1644	−0.0823	0.6585	0.081*	0.618 (8)
C80	0.1771 (3)	−0.0570 (2)	0.55108 (11)	0.0278 (5)	0.382 (8)
H80A	0.2327	−0.1285	0.5399	0.033*	0.382 (8)
H80B	0.1301	−0.0204	0.5191	0.033*	0.382 (8)
C30	0.0531 (8)	−0.0980 (6)	0.5891 (3)	0.031 (2)	0.382 (8)
H30A	−0.0184	−0.0312	0.5912	0.037*	0.382 (8)
H30B	0.0002	−0.1663	0.5720	0.037*	0.382 (8)
C40	0.0910 (4)	−0.1317 (4)	0.63923 (14)	0.0540 (10)	0.382 (8)
H40A	0.0021	−0.1544	0.6576	0.081*	0.382 (8)
H40B	0.1398	−0.0645	0.6578	0.081*	0.382 (8)
H40C	0.1584	−0.2003	0.6385	0.081*	0.382 (8)
N1	0.2807 (2)	0.0299 (2)	0.57585 (10)	0.0293 (5)	0.50
C5	0.4367 (6)	−0.0111 (5)	0.5768 (3)	0.0210 (11)	0.50
H5A	0.5005	0.0539	0.5641	0.025*	0.50
H5B	0.4462	−0.0812	0.5532	0.025*	0.50
C6	0.4858 (5)	−0.0460 (5)	0.6335 (2)	0.0235 (10)	0.50
H6A	0.4651	0.0209	0.6578	0.028*	0.50
H6B	0.4298	−0.1173	0.6447	0.028*	0.50
C7	0.6503 (6)	−0.0740 (5)	0.6360 (3)	0.0325 (13)	0.50
H7A	0.6809	−0.0963	0.6721	0.049*	0.50
H7B	0.7054	−0.0029	0.6254	0.049*	0.50
H7C	0.6702	−0.1407	0.6122	0.049*	0.50
N10	0.2807 (2)	0.0299 (2)	0.57585 (10)	0.0293 (5)	0.50
C50	0.4217 (7)	−0.0203 (5)	0.6042 (3)	0.0279 (13)	0.50
H50A	0.4466	0.0270	0.6363	0.033*	0.50
H50B	0.4068	−0.1051	0.6144	0.033*	0.50
C60	0.5433 (7)	−0.0108 (5)	0.5656 (3)	0.0360 (13)	0.50
H60A	0.5545	0.0740	0.5547	0.043*	0.50
H60B	0.5169	−0.0586	0.5337	0.043*	0.50
C70	0.6906 (7)	−0.0567 (6)	0.5903 (3)	0.0447 (16)	0.50
H70A	0.7677	−0.0504	0.5645	0.067*	0.50
H70B	0.6797	−0.1408	0.6009	0.067*	0.50
H70C	0.7180	−0.0081	0.6214	0.067*	0.50
C8	0.0275 (2)	0.5569 (2)	0.69392 (9)	0.0178 (4)
C9	−0.1698 (3)	0.6864 (2)	0.72549 (11)	0.0263 (5)
H9A	−0.1865	0.7086	0.6880	0.032*
H9B	−0.1652	0.7615	0.7464	0.032*
C10	−0.2992 (3)	0.6109 (3)	0.74297 (12)	0.0355 (7)
H10A	−0.2835	0.5887	0.7805	0.043*
H10B	−0.3050	0.5360	0.7220	0.043*
C11	−0.4437 (3)	0.6802 (4)	0.73570 (13)	0.0472 (9)
H11A	−0.5253	0.6304	0.7473	0.071*
H11B	−0.4602	0.7007	0.6984	0.071*
H11C	−0.4383	0.7540	0.7567	0.071*
C12	0.0537 (3)	0.6428 (2)	0.78277 (9)	0.0234 (5)
H12A	0.1123	0.5701	0.7918	0.028*
H12B	−0.0177	0.6551	0.8108	0.028*
C13	0.1564 (3)	0.7511 (2)	0.78105 (10)	0.0242 (5)
H13A	0.0972	0.8253	0.7767	0.029*
H13B	0.2198	0.7439	0.7503	0.029*
C14	0.2533 (3)	0.7595 (3)	0.83168 (11)	0.0304 (6)
H14A	0.3183	0.8295	0.8297	0.046*
H14B	0.3131	0.6865	0.8357	0.046*
H14C	0.1906	0.7678	0.8620	0.046*
C15	0.4586 (3)	0.5575 (2)	0.59424 (10)	0.0202 (5)
H15	0.4744	0.5230	0.6282	0.024*
C16	0.5719 (3)	0.6238 (2)	0.57324 (10)	0.0215 (5)
H16	0.6628	0.6342	0.5925	0.026*
C17	0.5501 (3)	0.6745 (2)	0.52364 (10)	0.0227 (5)
H17	0.6262	0.7192	0.5080	0.027*
C18	0.4137 (3)	0.6584 (2)	0.49713 (9)	0.0193 (4)
H18	0.3948	0.6930	0.4633	0.023*
C19	0.3063 (2)	0.59112 (19)	0.52103 (9)	0.0161 (4)
C20	0.1614 (2)	0.5730 (2)	0.49415 (9)	0.0169 (4)
H20	0.1376	0.6131	0.4619	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.01450 (9)	0.01688 (9)	0.01615 (10)	0.00097 (6)	0.00017 (6)	−0.00067 (6)
S1	0.0254 (3)	0.0220 (3)	0.0437 (4)	0.0073 (2)	−0.0170 (3)	−0.0097 (3)
S2	0.0160 (3)	0.0172 (3)	0.0413 (4)	−0.0007 (2)	−0.0038 (2)	0.0019 (2)
S3	0.0162 (3)	0.0263 (3)	0.0201 (3)	0.0040 (2)	−0.0029 (2)	−0.0056 (2)
S4	0.0159 (3)	0.0221 (3)	0.0192 (3)	0.0031 (2)	−0.0004 (2)	−0.0007 (2)
N2	0.0146 (9)	0.0258 (10)	0.0207 (10)	0.0011 (8)	0.0002 (7)	−0.0066 (8)
N3	0.0169 (9)	0.0166 (9)	0.0172 (9)	0.0019 (7)	−0.0018 (7)	−0.0009 (7)
N4	0.0135 (9)	0.0192 (9)	0.0156 (9)	−0.0008 (7)	−0.0038 (7)	−0.0006 (7)
C1	0.0185 (10)	0.0167 (10)	0.0193 (11)	0.0003 (8)	0.0025 (8)	0.0035 (9)
C2	0.0275 (13)	0.0207 (12)	0.0348 (14)	−0.0004 (10)	−0.0021 (10)	−0.0054 (11)
C3	0.031 (2)	0.022 (2)	0.045 (3)	−0.0029 (18)	−0.0006 (19)	−0.0092 (19)
C4	0.046 (2)	0.075 (3)	0.0421 (19)	−0.0291 (19)	0.0068 (15)	−0.0073 (18)
C80	0.0275 (13)	0.0207 (12)	0.0348 (14)	−0.0004 (10)	−0.0021 (10)	−0.0054 (11)
C30	0.026 (4)	0.022 (4)	0.043 (4)	−0.006 (3)	−0.003 (3)	−0.005 (3)
C40	0.046 (2)	0.075 (3)	0.0421 (19)	−0.0291 (19)	0.0068 (15)	−0.0073 (18)
N1	0.0196 (10)	0.0189 (10)	0.0493 (14)	0.0004 (8)	−0.0019 (9)	−0.0003 (10)
C5	0.014 (3)	0.023 (3)	0.026 (3)	0.0064 (18)	0.008 (2)	−0.008 (3)
C6	0.013 (2)	0.022 (2)	0.034 (3)	0.0030 (18)	−0.011 (2)	0.005 (2)
C7	0.019 (2)	0.022 (2)	0.056 (4)	0.0074 (19)	−0.011 (2)	−0.012 (2)
N10	0.0196 (10)	0.0189 (10)	0.0493 (14)	0.0004 (8)	−0.0019 (9)	−0.0003 (10)
C50	0.029 (3)	0.020 (3)	0.035 (4)	0.004 (2)	0.004 (3)	−0.003 (3)
C60	0.037 (4)	0.027 (3)	0.044 (3)	0.007 (2)	−0.003 (3)	0.002 (2)
C70	0.028 (3)	0.037 (3)	0.070 (5)	0.006 (3)	−0.001 (3)	−0.006 (3)
C8	0.0148 (10)	0.0182 (10)	0.0206 (11)	−0.0026 (8)	0.0029 (8)	−0.0004 (9)
C9	0.0171 (11)	0.0322 (13)	0.0294 (13)	0.0073 (10)	0.0000 (9)	−0.0119 (11)
C10	0.0184 (12)	0.0529 (18)	0.0356 (15)	0.0001 (12)	0.0065 (10)	−0.0130 (14)
C11	0.0168 (13)	0.082 (3)	0.0430 (17)	0.0039 (14)	0.0017 (11)	−0.0247 (18)
C12	0.0218 (11)	0.0296 (13)	0.0188 (11)	0.0009 (10)	0.0001 (9)	−0.0060 (10)
C13	0.0192 (11)	0.0249 (12)	0.0279 (13)	0.0031 (9)	−0.0042 (9)	−0.0050 (10)
C14	0.0236 (12)	0.0339 (14)	0.0329 (14)	0.0053 (11)	−0.0082 (10)	−0.0069 (11)
C15	0.0184 (11)	0.0198 (11)	0.0221 (11)	0.0017 (9)	−0.0051 (8)	0.0007 (9)
C16	0.0154 (10)	0.0198 (11)	0.0288 (12)	0.0000 (9)	−0.0046 (9)	−0.0037 (10)
C17	0.0180 (11)	0.0181 (11)	0.0319 (13)	−0.0008 (9)	0.0013 (9)	−0.0005 (10)
C18	0.0191 (11)	0.0177 (11)	0.0212 (11)	−0.0008 (8)	0.0013 (8)	0.0001 (9)
C19	0.0169 (10)	0.0141 (10)	0.0173 (11)	0.0016 (8)	0.0007 (8)	−0.0030 (8)
C20	0.0164 (10)	0.0187 (10)	0.0156 (10)	0.0022 (8)	0.0002 (8)	−0.0017 (8)

Geometric parameters (Å, º) top

Cd—N3	2.377 (2)	C6—H6A	0.9900
Cd—S1	2.6124 (8)	C6—H6B	0.9900
Cd—N4	2.6211 (19)	C7—H7A	0.9800
Cd—S3	2.6279 (7)	C7—H7B	0.9800
Cd—S4	2.6407 (7)	C7—H7C	0.9800
Cd—S2	2.7165 (7)	N10—C50	1.548 (7)
S1—C1	1.727 (2)	C50—C60	1.508 (9)
S2—C1	1.709 (2)	C50—H50A	0.9900
S3—C8	1.735 (2)	C50—H50B	0.9900
S4—C8	1.726 (2)	C60—C70	1.543 (8)
N2—C8	1.329 (3)	C60—H60A	0.9900
N2—C9	1.470 (3)	C60—H60B	0.9900
N2—C12	1.480 (3)	C70—H70A	0.9800
N3—C15	1.338 (3)	C70—H70B	0.9800
N3—C19	1.353 (3)	C70—H70C	0.9800
N4—C20	1.284 (3)	C9—C10	1.525 (4)
N4—N4ⁱ	1.409 (3)	C9—H9A	0.9900
C1—N10	1.342 (3)	C9—H9B	0.9900
C1—N1	1.342 (3)	C10—C11	1.527 (4)
C2—N1	1.474 (3)	C10—H10A	0.9900
C2—C3	1.505 (5)	C10—H10B	0.9900
C2—H2A	0.9900	C11—H11A	0.9800
C2—H2B	0.9900	C11—H11B	0.9800
C3—C4	1.493 (6)	C11—H11C	0.9800
C3—H3A	0.9900	C12—C13	1.526 (4)
C3—H3B	0.9900	C12—H12A	0.9900
C4—H4A	0.9800	C12—H12B	0.9900
C4—H4B	0.9800	C13—C14	1.532 (3)
C4—H4C	0.9800	C13—H13A	0.9900
C80—N10	1.474 (3)	C13—H13B	0.9900
C80—C30	1.578 (8)	C14—H14A	0.9800
C80—H80A	0.9900	C14—H14B	0.9800
C80—H80B	0.9900	C14—H14C	0.9800
C30—C40	1.358 (9)	C15—C16	1.389 (3)
C30—H30A	0.9900	C15—H15	0.9500
C30—H30B	0.9900	C16—C17	1.387 (4)
C40—H40A	0.9800	C16—H16	0.9500
C40—H40B	0.9800	C17—C18	1.398 (3)
C40—H40C	0.9800	C17—H17	0.9500
N1—C5	1.487 (5)	C18—C19	1.388 (3)
C5—C6	1.539 (8)	C18—H18	0.9500
C5—H5A	0.9900	C19—C20	1.472 (3)
C5—H5B	0.9900	C20—H20	0.9500
C6—C7	1.524 (7)

N3—Cd—S1	125.86 (5)	C6—C7—H7A	109.5
N3—Cd—N4	65.89 (6)	C6—C7—H7B	109.5
S1—Cd—N4	87.65 (5)	H7A—C7—H7B	109.5
N3—Cd—S3	106.92 (5)	C6—C7—H7C	109.5
S1—Cd—S3	113.49 (2)	H7A—C7—H7C	109.5
N4—Cd—S3	79.19 (4)	H7B—C7—H7C	109.5
N3—Cd—S4	94.63 (5)	C1—N10—C80	123.5 (2)
S1—Cd—S4	132.59 (2)	C1—N10—C50	117.5 (3)
N4—Cd—S4	135.68 (5)	C80—N10—C50	117.6 (3)
S3—Cd—S4	68.714 (18)	C60—C50—N10	106.6 (6)
N3—Cd—S2	87.49 (5)	C60—C50—H50A	110.4
S1—Cd—S2	67.45 (2)	N10—C50—H50A	110.4
N4—Cd—S2	122.40 (5)	C60—C50—H50B	110.4
S3—Cd—S2	158.05 (2)	N10—C50—H50B	110.4
S4—Cd—S2	94.19 (2)	H50A—C50—H50B	108.6
C1—S1—Cd	88.28 (8)	C50—C60—C70	110.9 (5)
C1—S2—Cd	85.28 (8)	C50—C60—H60A	109.5
C8—S3—Cd	86.54 (8)	C70—C60—H60A	109.5
C8—S4—Cd	86.30 (8)	C50—C60—H60B	109.5
C8—N2—C9	122.7 (2)	C70—C60—H60B	109.5
C8—N2—C12	121.6 (2)	H60A—C60—H60B	108.1
C9—N2—C12	115.64 (19)	C60—C70—H70A	109.5
C15—N3—C19	117.8 (2)	C60—C70—H70B	109.5
C15—N3—Cd	119.82 (16)	H70A—C70—H70B	109.5
C19—N3—Cd	122.14 (15)	C60—C70—H70C	109.5
C20—N4—N4ⁱ	112.8 (2)	H70A—C70—H70C	109.5
C20—N4—Cd	114.97 (14)	H70B—C70—H70C	109.5
N4ⁱ—N4—Cd	132.07 (19)	N2—C8—S4	121.29 (18)
N10—C1—N1	0.0 (2)	N2—C8—S3	120.26 (17)
N10—C1—S2	120.96 (18)	S4—C8—S3	118.45 (13)
N1—C1—S2	120.96 (18)	N2—C9—C10	112.7 (2)
N10—C1—S1	120.08 (18)	N2—C9—H9A	109.1
N1—C1—S1	120.08 (18)	C10—C9—H9A	109.1
S2—C1—S1	118.96 (14)	N2—C9—H9B	109.1
N1—C2—C3	112.9 (3)	C10—C9—H9B	109.1
N1—C2—H2A	109.0	H9A—C9—H9B	107.8
C3—C2—H2A	109.0	C9—C10—C11	110.7 (3)
N1—C2—H2B	109.0	C9—C10—H10A	109.5
C3—C2—H2B	109.0	C11—C10—H10A	109.5
H2A—C2—H2B	107.8	C9—C10—H10B	109.5
C4—C3—C2	115.8 (3)	C11—C10—H10B	109.5
C4—C3—H3A	108.3	H10A—C10—H10B	108.1
C2—C3—H3A	108.3	C10—C11—H11A	109.5
C4—C3—H3B	108.3	C10—C11—H11B	109.5
C2—C3—H3B	108.3	H11A—C11—H11B	109.5
H3A—C3—H3B	107.4	C10—C11—H11C	109.5
C3—C4—H4A	109.5	H11A—C11—H11C	109.5
C3—C4—H4B	109.5	H11B—C11—H11C	109.5
H4A—C4—H4B	109.5	N2—C12—C13	112.1 (2)
C3—C4—H4C	109.5	N2—C12—H12A	109.2
H4A—C4—H4C	109.5	C13—C12—H12A	109.2
H4B—C4—H4C	109.5	N2—C12—H12B	109.2
N10—C80—C30	112.8 (3)	C13—C12—H12B	109.2
N10—C80—H80A	109.0	H12A—C12—H12B	107.9
C30—C80—H80A	109.0	C12—C13—C14	110.9 (2)
N10—C80—H80B	109.0	C12—C13—H13A	109.5
C30—C80—H80B	109.0	C14—C13—H13A	109.5
H80A—C80—H80B	107.8	C12—C13—H13B	109.5
C40—C30—C80	119.5 (5)	C14—C13—H13B	109.5
C40—C30—H30A	107.4	H13A—C13—H13B	108.1
C80—C30—H30A	107.4	C13—C14—H14A	109.5
C40—C30—H30B	107.4	C13—C14—H14B	109.5
C80—C30—H30B	107.4	H14A—C14—H14B	109.5
H30A—C30—H30B	107.0	C13—C14—H14C	109.5
C30—C40—H40A	109.5	H14A—C14—H14C	109.5
C30—C40—H40B	109.5	H14B—C14—H14C	109.5
H40A—C40—H40B	109.5	N3—C15—C16	123.3 (2)
C30—C40—H40C	109.5	N3—C15—H15	118.4
H40A—C40—H40C	109.5	C16—C15—H15	118.4
H40B—C40—H40C	109.5	C17—C16—C15	118.9 (2)
C1—N1—C2	123.5 (2)	C17—C16—H16	120.6
C1—N1—C5	121.2 (3)	C15—C16—H16	120.6
C2—N1—C5	113.4 (3)	C16—C17—C18	118.5 (2)
N1—C5—C6	109.6 (5)	C16—C17—H17	120.7
N1—C5—H5A	109.8	C18—C17—H17	120.7
C6—C5—H5A	109.8	C19—C18—C17	118.9 (2)
N1—C5—H5B	109.8	C19—C18—H18	120.6
C6—C5—H5B	109.8	C17—C18—H18	120.6
H5A—C5—H5B	108.2	N3—C19—C18	122.7 (2)
C7—C6—C5	109.8 (5)	N3—C19—C20	117.2 (2)
C7—C6—H6A	109.7	C18—C19—C20	120.1 (2)
C5—C6—H6A	109.7	N4—C20—C19	119.5 (2)
C7—C6—H6B	109.7	N4—C20—H20	120.3
C5—C6—H6B	109.7	C19—C20—H20	120.3
H6A—C6—H6B	108.2

N3—Cd—S1—C1	69.94 (10)	S1—C1—N1—C2	0.0 (4)
N4—Cd—S1—C1	127.66 (9)	N10—C1—N1—C5	0 (100)
S3—Cd—S1—C1	−155.19 (8)	S2—C1—N1—C5	−17.3 (5)
S4—Cd—S1—C1	−73.14 (8)	S1—C1—N1—C5	162.8 (4)
S2—Cd—S1—C1	0.95 (8)	C3—C2—N1—C1	−120.0 (3)
N3—Cd—S2—C1	−131.74 (9)	C3—C2—N1—C5	76.1 (4)
S1—Cd—S2—C1	−0.97 (8)	C1—N1—C5—C6	88.3 (5)
N4—Cd—S2—C1	−72.54 (9)	C2—N1—C5—C6	−107.3 (4)
S3—Cd—S2—C1	96.17 (9)	N1—C5—C6—C7	−173.3 (4)
S4—Cd—S2—C1	133.80 (8)	N1—C1—N10—C80	0 (40)
N3—Cd—S3—C8	−87.89 (9)	S2—C1—N10—C80	179.9 (2)
S1—Cd—S3—C8	129.01 (8)	S1—C1—N10—C80	0.0 (4)
N4—Cd—S3—C8	−148.37 (9)	N1—C1—N10—C50	0 (100)
S4—Cd—S3—C8	0.51 (8)	S2—C1—N10—C50	13.8 (5)
S2—Cd—S3—C8	41.31 (10)	S1—C1—N10—C50	−166.1 (4)
N3—Cd—S4—C8	105.86 (9)	C30—C80—N10—C1	−74.1 (4)
S1—Cd—S4—C8	−103.38 (8)	C30—C80—N10—C50	92.0 (5)
N4—Cd—S4—C8	46.11 (10)	C1—N10—C50—C60	−95.8 (5)
S3—Cd—S4—C8	−0.51 (8)	C80—N10—C50—C60	97.3 (5)
S2—Cd—S4—C8	−166.33 (8)	N10—C50—C60—C70	179.0 (5)
S1—Cd—N3—C15	−110.58 (17)	C9—N2—C8—S4	179.07 (19)
N4—Cd—N3—C15	−178.32 (19)	C12—N2—C8—S4	1.9 (3)
S3—Cd—N3—C15	112.22 (17)	C9—N2—C8—S3	−0.9 (3)
S4—Cd—N3—C15	43.08 (17)	C12—N2—C8—S3	−178.15 (18)
S2—Cd—N3—C15	−50.92 (17)	Cd—S4—C8—N2	−179.2 (2)
S1—Cd—N3—C19	63.49 (18)	Cd—S4—C8—S3	0.82 (13)
N4—Cd—N3—C19	−4.25 (16)	Cd—S3—C8—N2	179.2 (2)
S3—Cd—N3—C19	−73.71 (17)	Cd—S3—C8—S4	−0.82 (13)
S4—Cd—N3—C19	−142.85 (16)	C8—N2—C9—C10	90.9 (3)
S2—Cd—N3—C19	123.15 (17)	C12—N2—C9—C10	−91.7 (3)
N3—Cd—N4—C20	1.00 (15)	N2—C9—C10—C11	179.9 (2)
S1—Cd—N4—C20	−130.34 (16)	C8—N2—C12—C13	88.1 (3)
S3—Cd—N4—C20	115.21 (16)	C9—N2—C12—C13	−89.3 (3)
S4—Cd—N4—C20	71.62 (17)	N2—C12—C13—C14	−172.8 (2)
S2—Cd—N4—C20	−69.06 (17)	C19—N3—C15—C16	−1.0 (3)
N3—Cd—N4—N4ⁱ	−174.1 (3)	Cd—N3—C15—C16	173.34 (18)
S1—Cd—N4—N4ⁱ	54.6 (3)	N3—C15—C16—C17	−0.1 (4)
S3—Cd—N4—N4ⁱ	−59.9 (2)	C15—C16—C17—C18	1.1 (4)
S4—Cd—N4—N4ⁱ	−103.4 (2)	C16—C17—C18—C19	−0.9 (4)
S2—Cd—N4—N4ⁱ	115.9 (2)	C15—N3—C19—C18	1.1 (3)
Cd—S2—C1—N10	−178.4 (2)	Cd—N3—C19—C18	−173.05 (17)
Cd—S2—C1—N1	−178.4 (2)	C15—N3—C19—C20	−178.9 (2)
Cd—S2—C1—S1	1.54 (13)	Cd—N3—C19—C20	6.9 (3)
Cd—S1—C1—N10	178.3 (2)	C17—C18—C19—N3	−0.2 (3)
Cd—S1—C1—N1	178.3 (2)	C17—C18—C19—C20	179.8 (2)
Cd—S1—C1—S2	−1.60 (13)	N4ⁱ—N4—C20—C19	178.0 (2)
N1—C2—C3—C4	55.2 (4)	Cd—N4—C20—C19	1.9 (3)
N10—C80—C30—C40	−47.3 (7)	N3—C19—C20—N4	−5.7 (3)
S2—C1—N1—C2	179.9 (2)	C18—C19—C20—N4	174.3 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···S4ⁱⁱ	0.99	2.83	3.815 (3)	171
C16—H16···S3ⁱⁱⁱ	0.95	2.82	3.674 (3)	150
C3—H3B···Cg^iv	0.95	2.99	3.853 (5)	147

Symmetry codes: (ii) −x, y+1/2, −z+3/2; (iii) x+1, y, z; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cd₂(C₇H₁₄NS₂)₄(C₁₂H₁₀N₄)]
M_r	1140.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	98
a, b, c (Å)	9.0768 (16), 11.137 (2), 25.389 (5)
β (°)	92.216 (3)
V (Å³)	2564.7 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.35 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku AFC12κ/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.656, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	20914, 5861, 5539
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.077, 1.08
No. of reflections	5861
No. of parameters	299
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.72

Computer programs: CrystalClear (Rigaku/MSC, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···S4ⁱ	0.99	2.83	3.815 (3)	171
C16—H16···S3ⁱⁱ	0.95	2.82	3.674 (3)	150
C3—H3B···Cgⁱⁱⁱ	0.95	2.99	3.853 (5)	147

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) x, y−1, z.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Benson, R. E., Ellis, C. A., Lewis, C. E. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 930–940. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Lai, C. S. & Tiekink, E. R. T. (2006). Z. Kristallogr. 221, 288–293. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiekink, E. R. T. (2006). CrystEngComm, 6, 104–118. Web of Science CrossRef 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.