Iodido{4-phenyl-1-[1-(1,3-thia­zol-2-yl-κN)ethyl­idene]thio­semicarbazidato-κ2N′,S}{4-phenyl-1-[1-(1,3-thia­zol-2-yl)ethyl­idene]thio­semicarbazide-κS}cadmium(II)

Venkatraman, R.; Samuel, D.S.; Arslan, Z.; Hossain, M.A.; Fronczek, F.R.

doi:10.1107/S160053681300915X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m246-m247

https://doi.org/10.1107/S160053681300915X

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Iodido{4-phenyl-1-[1-(1,3-thiazol-2-yl-κN)ethylidene]thiosemicarbazidato-κ²N′,S}{4-phenyl-1-[1-(1,3-thiazol-2-yl)ethylidene]thiosemicarbazide-κS}cadmium(II)

Ramaiyer Venkatraman,^a ^* Dasary S. Samuel,^a Zikri Arslan,^a Md. Alamgir Hossain ^a and Frank R. Fronczek ^b

^aDepartment of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217-0510, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: ramaiyer.venkatraman@jsums.edu

(Received 13 February 2013; accepted 3 April 2013; online 10 April 2013)

In the title complex, [Cd(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)], the Cd^II ion is pentacoordinated by two thiosemicarbazone ligands (one neutral and the other anionic) and one iodide ion in a distorted square pyramidal (τ = 0.35) geometry. The central ion is coordinated by the thiazole N atom, the thioureido N and the S atom of the deprotonated thiosemicarbazone ligand. The other ligand is linked with the central ion through the C=S group. The deprotonated ligand intramolecularly hydrogen bonds to the thiazole ring N atom, while the ligand forms an intermolecular hydrogen bond to the thiolate S atom of the second ligand. The deprotonation of the tridentate ligand and its coordination to the Cd^II ion via the S atom strikingly affects the C—S bond lengths. The C—S bond lengths in the neutral and deprotonated ligands in the metal complex are 1.709 (3) and 1.748 (2) Å, respectively, whereas it is 1.671 (3) Å in the free ligand. In the metal complex, the Cd—S distances are 2.6449 (6) and 2.5510 (6) Å. The Cd—I bond length is 2.7860 (2) Å.

Related literature

For properties of thiosemicarbazones and Cd complexes, see: Casas et al. (2000 ); Milczarska et al. (1998 ); Venkatraman et al. (2009 ); Dasary et al. (2011 ); Viñuelas-Zahínos et al. (2011 ); Arumugam et al. (2011 ). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[Cd(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]
M_r = 791.04
Triclinic, $[P \overline 1]$
a = 8.6685 (4) Å
b = 10.1323 (5) Å
c = 16.7220 (8) Å
α = 76.607 (2)°
β = 79.481 (2)°
γ = 77.910 (2)°
V = 1383.15 (11) Å³
Z = 2
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 90 K
0.13 × 0.06 × 0.05 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.760, T_max = 0.896
14913 measured reflections
8142 independent reflections
6715 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.060
S = 1.02
8142 reflections
354 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯S2ⁱ	0.84 (2)	2.74 (2)	3.559 (2)	166 (2)
N7—H7N⋯N5	0.86 (2)	1.90 (2)	2.651 (3)	144 (3)
Symmetry code: (i) -x, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681300915X/bv2219sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681300915X/bv2219Isup2.hkl

checkCIF report

Comment top

Heterocyclic thiosemicarbazones are versatile ligands forming complexes with a variety of transition metal ions. These ligands and their metal complexes are found to exhibit cytotoxic effects (Casas et al., 2000, Milczarska et al., 1998). Among several metals ions that complex with thiosemicarbazones, cadmium (II) has received less attention (Viñuelas-Zahínos et al. 2011). In continuation of our structural studies of metal thiosemicarbazones (Venkatraman et al., 2009; Dasary et al., 2011; Arumugam et al. 2011), we herein report the Cd^II complex of 2- acetyl thiazole N(4) phenyl thiosemicarbazone. The title complex is obtained from the reaction of cadmium (II) iodide with two equivalents of neutral ligands in methanol. This complex is an isomorph of the Hg complex reported by us earlier (Dasary et al., 2011). In this complex, the Cd^II is tridentately attached to one of the deprotonated ligand through the donor groups of N1, N2 and S2, while the metal ion is singly coordinated to the other ligand via S4. As shown in Fig. 1, one iodide is found to coordinate with the central metal ion from other side forming a pentacoodinated complex (τ= 0.35) with a pyramidal square planar geometry (Addison et al., 1984). The deprotonated ligand is twisted due to intra-molecularly hydrogen bonds (N7H···N5), while the ligand forms an intermolecular hydrogen bond via S2 with NH group (N4) from the other ligand (Fig. 2). The deprotonation of the tridentate ligand and its coordination to the Cd via the S atom strikingly affects the C—S bond lengths. The C—S bond distances in the neutral and deprotonated ligands in the metal complex are 1.709 (3) Å and 1.748 (2) Å respectively whereas it is 1.671 (3) Å in the free ligand. In the metal complex, the Cd—S distances are 2.6449 (6) Å, 2.5510 (6) Å. The Cd—I bond distance is 2.7860 (2) Å. The torsion angles (N2—N3—C6—N4), and (N6—N7—C18—N8) for two ligands is 179.48 (8)° and 8.5 (3)° respectively. Hydrogen bonding details are given in Table 1.

Related literature top

For properties of thiosemicarbazones and Cd complexes, see: Casas et al. (2000); Milczarska et al. (1998); Venkatraman et al. (2009); Dasary et al. (2011); Viñuelas-Zahínos et al. (2011); Arumugam et al. (2011). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984);

Experimental top

To a boiling methanol solution (50 ml) containing 2-acetylthiazole phenylthiosemicarbazone (1.38 g, 5 mmol) was added an equimolar of cadmium (II) iodide (1.38 g, 5 mmol) in 20 ml of methanol solution (Venkatraman et al., 2009)). The mixture was refluxed for 3 to 4 h under stirring. The resulting bright yellow solid obtained was filtered and dried (65% yield). Crystals suitable for diffraction were obtained from the mother liquor at ambient temperature after two days in a methanol–DMF mixture (5:1 V/V).

Structure description top

For properties of thiosemicarbazones and Cd complexes, see: Casas et al. (2000); Milczarska et al. (1998); Venkatraman et al. (2009); Dasary et al. (2011); Viñuelas-Zahínos et al. (2011); Arumugam et al. (2011). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984);

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Intra- and inter-molecular H-hydrogen bonding of the compound (1) viewed along b axis.

Iodido{4-phenyl-1-[1-(1,3-thiazol-2-yl-κN)ethylidene]thiosemicarbazidato-κ²N',S}{4-phenyl-1-[1-(1,3-thiazol-2-yl)ethylidene]thiosemicarbazide-κS}cadmium(II) top

Crystal data top

[Cd(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]	Z = 2
M_r = 791.04	F(000) = 776
Triclinic, P1	D_x = 1.899 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6685 (4) Å	Cell parameters from 6604 reflections
b = 10.1323 (5) Å	θ = 2.5–30.9°
c = 16.7220 (8) Å	µ = 2.24 mm⁻¹
α = 76.607 (2)°	T = 90 K
β = 79.481 (2)°	Needle, yellow
γ = 77.910 (2)°	0.13 × 0.06 × 0.05 mm
V = 1383.15 (11) Å³

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	8142 independent reflections
Radiation source: fine-focus sealed tube	6715 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 31.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −12→12
T_min = 0.760, T_max = 0.896	k = −14→14
14913 measured reflections	l = −23→23

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0252P)² + 0.1767P] where P = (F_o² + 2F_c²)/3
8142 reflections	(Δ/σ)_max = 0.002
354 parameters	Δρ_max = 0.92 e Å⁻³
3 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Cd(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]	γ = 77.910 (2)°
M_r = 791.04	V = 1383.15 (11) Å³
Triclinic, P1	Z = 2
a = 8.6685 (4) Å	Mo Kα radiation
b = 10.1323 (5) Å	µ = 2.24 mm⁻¹
c = 16.7220 (8) Å	T = 90 K
α = 76.607 (2)°	0.13 × 0.06 × 0.05 mm
β = 79.481 (2)°

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	8142 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	6715 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.896	R_int = 0.024
14913 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	3 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.92 e Å⁻³
8142 reflections	Δρ_min = −0.60 e Å⁻³
354 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
Cd1	0.330279 (19)	0.896637 (16)	0.264500 (10)	0.01247 (4)
I1	0.213720 (18)	1.080081 (15)	0.128204 (9)	0.01602 (4)
S1	0.89644 (7)	0.80381 (6)	0.20293 (4)	0.01885 (12)
S2	0.16206 (7)	0.96342 (6)	0.39576 (4)	0.01535 (11)
S3	0.98373 (7)	0.36995 (6)	0.41505 (4)	0.01949 (12)
S4	0.27226 (7)	0.64947 (6)	0.26713 (4)	0.01495 (11)
N1	0.5972 (2)	0.86012 (19)	0.19861 (12)	0.0142 (4)
N2	0.5065 (2)	0.85083 (19)	0.36308 (12)	0.0128 (4)
N3	0.4565 (2)	0.84714 (19)	0.44586 (12)	0.0140 (4)
N4	0.2430 (2)	0.8941 (2)	0.54478 (12)	0.0133 (4)
H4N	0.144 (2)	0.921 (3)	0.5524 (17)	0.016*
N5	0.6877 (2)	0.4726 (2)	0.41015 (13)	0.0158 (4)
N6	0.7257 (2)	0.49547 (19)	0.22678 (13)	0.0151 (4)
N7	0.5761 (2)	0.5403 (2)	0.26598 (13)	0.0147 (4)
H7N	0.570 (3)	0.534 (3)	0.3188 (13)	0.018*
N8	0.4803 (2)	0.5489 (2)	0.14662 (13)	0.0174 (4)
H8N	0.571 (3)	0.504 (3)	0.1322 (18)	0.021*
C1	0.6688 (3)	0.8655 (2)	0.11853 (15)	0.0186 (5)
H1	0.6100	0.8870	0.0731	0.022*
C2	0.8309 (3)	0.8379 (3)	0.10863 (16)	0.0207 (5)
H2	0.8978	0.8375	0.0569	0.025*
C3	0.7028 (3)	0.8282 (2)	0.25083 (15)	0.0133 (4)
C4	0.6581 (3)	0.8217 (2)	0.34029 (15)	0.0136 (4)
C5	0.7822 (3)	0.7869 (2)	0.39688 (16)	0.0174 (5)
H5A	0.7525	0.8454	0.4384	0.026*
H5B	0.8853	0.8026	0.3644	0.026*
H5C	0.7902	0.6899	0.4249	0.026*
C6	0.3038 (3)	0.8948 (2)	0.46333 (14)	0.0136 (4)
C7	0.3157 (3)	0.8592 (2)	0.61768 (14)	0.0137 (4)
C8	0.4782 (3)	0.8135 (2)	0.62054 (15)	0.0175 (5)
H8	0.5490	0.7996	0.5715	0.021*
C9	0.5353 (3)	0.7884 (2)	0.69633 (16)	0.0208 (5)
H9	0.6462	0.7581	0.6983	0.025*
C10	0.4341 (3)	0.8066 (2)	0.76886 (16)	0.0201 (5)
H10	0.4751	0.7900	0.8199	0.024*
C11	0.2714 (3)	0.8496 (2)	0.76577 (15)	0.0175 (5)
H11	0.2004	0.8610	0.8151	0.021*
C12	0.2133 (3)	0.8755 (2)	0.69095 (15)	0.0154 (4)
H12	0.1022	0.9049	0.6893	0.018*
C13	0.7108 (3)	0.4442 (2)	0.49162 (15)	0.0181 (5)
H13	0.6268	0.4618	0.5351	0.022*
C14	0.8628 (3)	0.3890 (3)	0.50580 (16)	0.0200 (5)
H14	0.8969	0.3644	0.5590	0.024*
C15	0.8225 (3)	0.4389 (2)	0.36162 (15)	0.0152 (5)
C16	0.8407 (3)	0.4521 (2)	0.27193 (15)	0.0151 (4)
C17	1.0016 (3)	0.4115 (3)	0.22704 (16)	0.0172 (5)
H17A	0.9970	0.4318	0.1672	0.026*
H17B	1.0384	0.3126	0.2456	0.026*
H17C	1.0758	0.4633	0.2387	0.026*
C18	0.4532 (3)	0.5759 (2)	0.22228 (14)	0.0135 (4)
C19	0.3685 (3)	0.5824 (2)	0.08851 (15)	0.0163 (5)
C20	0.3172 (3)	0.7197 (2)	0.05317 (15)	0.0180 (5)
H20	0.3514	0.7913	0.0696	0.022*
C21	0.2159 (3)	0.7507 (3)	−0.00614 (15)	0.0186 (5)
H21	0.1800	0.8441	−0.0305	0.022*
C22	0.1664 (3)	0.6454 (3)	−0.03024 (15)	0.0186 (5)
H22	0.0967	0.6669	−0.0710	0.022*
C23	0.2185 (3)	0.5100 (3)	0.00503 (16)	0.0186 (5)
H23	0.1848	0.4383	−0.0116	0.022*
C24	0.3201 (3)	0.4775 (2)	0.06488 (15)	0.0166 (5)
H24	0.3559	0.3841	0.0892	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01077 (8)	0.01618 (8)	0.01024 (8)	−0.00112 (6)	−0.00187 (6)	−0.00305 (6)
I1	0.01858 (8)	0.01534 (7)	0.01276 (8)	0.00038 (6)	−0.00397 (6)	−0.00170 (6)
S1	0.0111 (3)	0.0200 (3)	0.0233 (3)	−0.0016 (2)	0.0015 (2)	−0.0041 (2)
S2	0.0130 (3)	0.0212 (3)	0.0106 (3)	0.0018 (2)	−0.0028 (2)	−0.0042 (2)
S3	0.0147 (3)	0.0227 (3)	0.0211 (3)	−0.0013 (2)	−0.0068 (2)	−0.0030 (2)
S4	0.0135 (3)	0.0173 (3)	0.0147 (3)	−0.0032 (2)	−0.0017 (2)	−0.0042 (2)
N1	0.0121 (9)	0.0148 (9)	0.0151 (10)	−0.0030 (7)	−0.0001 (7)	−0.0022 (7)
N2	0.0131 (9)	0.0128 (9)	0.0126 (9)	−0.0025 (7)	−0.0012 (7)	−0.0030 (7)
N3	0.0142 (9)	0.0157 (9)	0.0125 (9)	−0.0031 (7)	−0.0036 (7)	−0.0015 (7)
N4	0.0121 (9)	0.0188 (9)	0.0099 (9)	−0.0030 (7)	−0.0021 (7)	−0.0039 (7)
N5	0.0152 (10)	0.0151 (9)	0.0185 (10)	−0.0040 (7)	−0.0035 (8)	−0.0038 (8)
N6	0.0140 (9)	0.0147 (9)	0.0182 (10)	−0.0036 (7)	−0.0006 (8)	−0.0067 (8)
N7	0.0130 (9)	0.0180 (9)	0.0136 (10)	−0.0012 (7)	−0.0025 (8)	−0.0048 (8)
N8	0.0161 (10)	0.0201 (10)	0.0163 (10)	0.0027 (8)	−0.0053 (8)	−0.0072 (8)
C1	0.0194 (12)	0.0217 (12)	0.0143 (11)	−0.0045 (9)	0.0015 (9)	−0.0051 (9)
C2	0.0192 (12)	0.0238 (12)	0.0169 (12)	−0.0030 (10)	0.0041 (10)	−0.0053 (10)
C3	0.0104 (10)	0.0115 (10)	0.0182 (11)	−0.0035 (8)	0.0006 (9)	−0.0043 (9)
C4	0.0138 (11)	0.0101 (10)	0.0165 (11)	−0.0032 (8)	−0.0031 (9)	−0.0004 (8)
C5	0.0148 (11)	0.0185 (11)	0.0193 (12)	−0.0016 (9)	−0.0073 (9)	−0.0020 (9)
C6	0.0162 (11)	0.0143 (10)	0.0116 (10)	−0.0038 (8)	−0.0033 (9)	−0.0032 (8)
C7	0.0197 (11)	0.0106 (10)	0.0125 (11)	−0.0054 (8)	−0.0055 (9)	−0.0007 (8)
C8	0.0193 (12)	0.0186 (11)	0.0152 (11)	−0.0031 (9)	−0.0050 (9)	−0.0029 (9)
C9	0.0219 (13)	0.0197 (12)	0.0220 (13)	−0.0048 (10)	−0.0090 (10)	−0.0013 (10)
C10	0.0302 (14)	0.0158 (11)	0.0173 (12)	−0.0049 (10)	−0.0125 (10)	−0.0017 (9)
C11	0.0283 (13)	0.0129 (10)	0.0114 (11)	−0.0042 (9)	−0.0051 (10)	−0.0004 (9)
C12	0.0187 (12)	0.0130 (10)	0.0152 (11)	−0.0038 (9)	−0.0041 (9)	−0.0021 (9)
C13	0.0195 (12)	0.0203 (12)	0.0151 (12)	−0.0052 (9)	−0.0039 (9)	−0.0018 (9)
C14	0.0218 (13)	0.0222 (12)	0.0169 (12)	−0.0057 (10)	−0.0073 (10)	−0.0006 (10)
C15	0.0174 (11)	0.0111 (10)	0.0189 (12)	−0.0035 (8)	−0.0071 (9)	−0.0025 (9)
C16	0.0171 (11)	0.0125 (10)	0.0171 (12)	−0.0033 (8)	−0.0044 (9)	−0.0036 (9)
C17	0.0115 (11)	0.0228 (12)	0.0192 (12)	−0.0024 (9)	−0.0010 (9)	−0.0094 (10)
C18	0.0131 (10)	0.0132 (10)	0.0139 (11)	−0.0034 (8)	−0.0017 (8)	−0.0015 (8)
C19	0.0132 (11)	0.0214 (12)	0.0140 (11)	0.0000 (9)	−0.0042 (9)	−0.0039 (9)
C20	0.0197 (12)	0.0182 (11)	0.0174 (12)	−0.0034 (9)	−0.0033 (10)	−0.0055 (9)
C21	0.0207 (12)	0.0183 (11)	0.0144 (11)	−0.0007 (9)	−0.0015 (9)	−0.0014 (9)
C22	0.0146 (11)	0.0285 (13)	0.0128 (11)	−0.0033 (9)	−0.0038 (9)	−0.0035 (10)
C23	0.0200 (12)	0.0213 (12)	0.0170 (12)	−0.0070 (10)	−0.0010 (10)	−0.0070 (10)
C24	0.0176 (12)	0.0137 (10)	0.0175 (12)	−0.0028 (9)	−0.0022 (9)	−0.0012 (9)

Geometric parameters (Å, º) top

Cd1—N2	2.3524 (19)	C5—H5A	0.9800
Cd1—N1	2.3673 (19)	C5—H5B	0.9800
Cd1—S2	2.5510 (6)	C5—H5C	0.9800
Cd1—S4	2.6449 (6)	C7—C8	1.393 (3)
Cd1—I1	2.7860 (2)	C7—C12	1.397 (3)
S1—C2	1.709 (3)	C8—C9	1.394 (3)
S1—C3	1.716 (2)	C8—H8	0.9500
S2—C6	1.748 (2)	C9—C10	1.386 (4)
S3—C14	1.706 (3)	C9—H9	0.9500
S3—C15	1.731 (2)	C10—C11	1.393 (4)
S4—C18	1.708 (2)	C10—H10	0.9500
N1—C3	1.320 (3)	C11—C12	1.382 (3)
N1—C1	1.363 (3)	C11—H11	0.9500
N2—C4	1.291 (3)	C12—H12	0.9500
N2—N3	1.367 (3)	C13—C14	1.360 (3)
N3—C6	1.314 (3)	C13—H13	0.9500
N4—C6	1.367 (3)	C14—H14	0.9500
N4—C7	1.413 (3)	C15—C16	1.457 (3)
N4—H4N	0.842 (19)	C16—C17	1.483 (3)
N5—C15	1.325 (3)	C17—H17A	0.9800
N5—C13	1.368 (3)	C17—H17B	0.9800
N6—C16	1.302 (3)	C17—H17C	0.9800
N6—N7	1.378 (3)	C19—C24	1.379 (3)
N7—C18	1.342 (3)	C19—C20	1.392 (3)
N7—H7N	0.864 (19)	C20—C21	1.382 (3)
N8—C18	1.325 (3)	C20—H20	0.9500
N8—C19	1.432 (3)	C21—C22	1.393 (3)
N8—H8N	0.85 (2)	C21—H21	0.9500
C1—C2	1.360 (3)	C22—C23	1.377 (3)
C1—H1	0.9500	C22—H22	0.9500
C2—H2	0.9500	C23—C24	1.391 (3)
C3—C4	1.465 (3)	C23—H23	0.9500
C4—C5	1.495 (3)	C24—H24	0.9500

N2—Cd1—N1	69.91 (7)	C12—C7—N4	115.6 (2)
N2—Cd1—S2	74.23 (5)	C7—C8—C9	119.1 (2)
N1—Cd1—S2	141.74 (5)	C7—C8—H8	120.5
N2—Cd1—S4	102.87 (5)	C9—C8—H8	120.5
N1—Cd1—S4	96.47 (5)	C10—C9—C8	121.5 (2)
S2—Cd1—S4	104.16 (2)	C10—C9—H9	119.2
N2—Cd1—I1	146.34 (5)	C8—C9—H9	119.2
N1—Cd1—I1	94.99 (5)	C9—C10—C11	119.0 (2)
S2—Cd1—I1	107.969 (15)	C9—C10—H10	120.5
S4—Cd1—I1	108.767 (14)	C11—C10—H10	120.5
C2—S1—C3	90.02 (12)	C12—C11—C10	120.0 (2)
C6—S2—Cd1	97.99 (8)	C12—C11—H11	120.0
C14—S3—C15	89.54 (12)	C10—C11—H11	120.0
C18—S4—Cd1	100.32 (8)	C11—C12—C7	120.9 (2)
C3—N1—C1	111.6 (2)	C11—C12—H12	119.6
C3—N1—Cd1	113.40 (15)	C7—C12—H12	119.6
C1—N1—Cd1	134.96 (16)	C14—C13—N5	115.1 (2)
C4—N2—N3	116.89 (19)	C14—C13—H13	122.5
C4—N2—Cd1	119.85 (16)	N5—C13—H13	122.5
N3—N2—Cd1	123.19 (14)	C13—C14—S3	110.70 (19)
C6—N3—N2	113.65 (19)	C13—C14—H14	124.7
C6—N4—C7	132.1 (2)	S3—C14—H14	124.7
C6—N4—H4N	113.3 (19)	N5—C15—C16	125.7 (2)
C7—N4—H4N	114.6 (19)	N5—C15—S3	113.64 (18)
C15—N5—C13	111.0 (2)	C16—C15—S3	120.61 (18)
C16—N6—N7	117.6 (2)	N6—C16—C15	125.3 (2)
C18—N7—N6	118.8 (2)	N6—C16—C17	116.1 (2)
C18—N7—H7N	126.0 (19)	C15—C16—C17	118.5 (2)
N6—N7—H7N	114.9 (19)	C16—C17—H17A	109.5
C18—N8—C19	126.4 (2)	C16—C17—H17B	109.5
C18—N8—H8N	117 (2)	H17A—C17—H17B	109.5
C19—N8—H8N	117 (2)	C16—C17—H17C	109.5
C2—C1—N1	114.9 (2)	H17A—C17—H17C	109.5
C2—C1—H1	122.6	H17B—C17—H17C	109.5
N1—C1—H1	122.6	N8—C18—N7	117.1 (2)
C1—C2—S1	110.05 (19)	N8—C18—S4	124.02 (18)
C1—C2—H2	125.0	N7—C18—S4	118.89 (18)
S1—C2—H2	125.0	C24—C19—C20	120.9 (2)
N1—C3—C4	122.9 (2)	C24—C19—N8	119.3 (2)
N1—C3—S1	113.40 (18)	C20—C19—N8	119.7 (2)
C4—C3—S1	123.67 (17)	C21—C20—C19	119.3 (2)
N2—C4—C3	113.9 (2)	C21—C20—H20	120.4
N2—C4—C5	125.2 (2)	C19—C20—H20	120.4
C3—C4—C5	120.9 (2)	C20—C21—C22	120.2 (2)
C4—C5—H5A	109.5	C20—C21—H21	119.9
C4—C5—H5B	109.5	C22—C21—H21	119.9
H5A—C5—H5B	109.5	C23—C22—C21	119.9 (2)
C4—C5—H5C	109.5	C23—C22—H22	120.0
H5A—C5—H5C	109.5	C21—C22—H22	120.0
H5B—C5—H5C	109.5	C22—C23—C24	120.4 (2)
N3—C6—N4	117.7 (2)	C22—C23—H23	119.8
N3—C6—S2	128.92 (18)	C24—C23—H23	119.8
N4—C6—S2	113.34 (17)	C19—C24—C23	119.3 (2)
C8—C7—C12	119.4 (2)	C19—C24—H24	120.3
C8—C7—N4	125.0 (2)	C23—C24—H24	120.3

N2—Cd1—S2—C6	−9.65 (9)	N2—N3—C6—N4	179.49 (18)
N1—Cd1—S2—C6	−30.51 (11)	N2—N3—C6—S2	−1.4 (3)
S4—Cd1—S2—C6	89.99 (8)	C7—N4—C6—N3	5.1 (4)
I1—Cd1—S2—C6	−154.51 (7)	C7—N4—C6—S2	−174.19 (19)
N2—Cd1—S4—C18	−69.76 (10)	Cd1—S2—C6—N3	10.5 (2)
N1—Cd1—S4—C18	1.05 (10)	Cd1—S2—C6—N4	−170.29 (15)
S2—Cd1—S4—C18	−146.47 (8)	C6—N4—C7—C8	−0.7 (4)
I1—Cd1—S4—C18	98.58 (8)	C6—N4—C7—C12	178.1 (2)
N2—Cd1—N1—C3	2.61 (15)	C12—C7—C8—C9	−1.6 (3)
S2—Cd1—N1—C3	24.0 (2)	N4—C7—C8—C9	177.2 (2)
S4—Cd1—N1—C3	−98.76 (15)	C7—C8—C9—C10	0.7 (4)
I1—Cd1—N1—C3	151.67 (15)	C8—C9—C10—C11	0.7 (4)
N2—Cd1—N1—C1	−176.6 (2)	C9—C10—C11—C12	−1.0 (3)
S2—Cd1—N1—C1	−155.22 (18)	C10—C11—C12—C7	0.0 (3)
S4—Cd1—N1—C1	82.0 (2)	C8—C7—C12—C11	1.3 (3)
I1—Cd1—N1—C1	−27.6 (2)	N4—C7—C12—C11	−177.6 (2)
N1—Cd1—N2—C4	−3.14 (16)	C15—N5—C13—C14	0.1 (3)
S2—Cd1—N2—C4	−169.57 (17)	N5—C13—C14—S3	−0.3 (3)
S4—Cd1—N2—C4	89.12 (16)	C15—S3—C14—C13	0.33 (19)
I1—Cd1—N2—C4	−70.69 (19)	C13—N5—C15—C16	178.5 (2)
N1—Cd1—N2—N3	179.88 (17)	C13—N5—C15—S3	0.2 (2)
S2—Cd1—N2—N3	13.46 (14)	C14—S3—C15—N5	−0.31 (18)
S4—Cd1—N2—N3	−87.86 (15)	C14—S3—C15—C16	−178.66 (19)
I1—Cd1—N2—N3	112.34 (15)	N7—N6—C16—C15	4.1 (3)
C4—N2—N3—C6	171.65 (19)	N7—N6—C16—C17	−176.95 (18)
Cd1—N2—N3—C6	−11.3 (2)	N5—C15—C16—N6	−2.1 (4)
C16—N6—N7—C18	−175.2 (2)	S3—C15—C16—N6	176.07 (18)
C3—N1—C1—C2	−0.1 (3)	N5—C15—C16—C17	179.0 (2)
Cd1—N1—C1—C2	179.13 (16)	S3—C15—C16—C17	−2.9 (3)
N1—C1—C2—S1	0.0 (3)	C19—N8—C18—N7	−177.6 (2)
C3—S1—C2—C1	0.08 (19)	C19—N8—C18—S4	3.7 (3)
C1—N1—C3—C4	177.1 (2)	N6—N7—C18—N8	8.5 (3)
Cd1—N1—C3—C4	−2.3 (3)	N6—N7—C18—S4	−172.77 (15)
C1—N1—C3—S1	0.2 (2)	Cd1—S4—C18—N8	−108.70 (19)
Cd1—N1—C3—S1	−179.24 (9)	Cd1—S4—C18—N7	72.63 (18)
C2—S1—C3—N1	−0.15 (18)	C18—N8—C19—C24	−115.4 (3)
C2—S1—C3—C4	−177.1 (2)	C18—N8—C19—C20	68.2 (3)
N3—N2—C4—C3	−179.80 (18)	C24—C19—C20—C21	0.3 (4)
Cd1—N2—C4—C3	3.0 (2)	N8—C19—C20—C21	176.6 (2)
N3—N2—C4—C5	−1.1 (3)	C19—C20—C21—C22	−0.2 (4)
Cd1—N2—C4—C5	−178.23 (16)	C20—C21—C22—C23	−0.1 (4)
N1—C3—C4—N2	−0.4 (3)	C21—C22—C23—C24	0.2 (4)
S1—C3—C4—N2	176.24 (16)	C20—C19—C24—C23	−0.1 (4)
N1—C3—C4—C5	−179.2 (2)	N8—C19—C24—C23	−176.4 (2)
S1—C3—C4—C5	−2.6 (3)	C22—C23—C24—C19	−0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···S2ⁱ	0.84 (2)	2.74 (2)	3.559 (2)	166 (2)
N7—H7N···N5	0.86 (2)	1.90 (2)	2.651 (3)	144 (3)

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cd(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]
M_r	791.04
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	8.6685 (4), 10.1323 (5), 16.7220 (8)
α, β, γ (°)	76.607 (2), 79.481 (2), 77.910 (2)
V (Å³)	1383.15 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.24
Crystal size (mm)	0.13 × 0.06 × 0.05

Data collection
Diffractometer	Bruker Kappa APEXII DUO CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.760, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	14913, 8142, 6715
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.060, 1.02
No. of reflections	8142
No. of parameters	354
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.60

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···S2ⁱ	0.842 (19)	2.74 (2)	3.559 (2)	166 (2)
N7—H7N···N5	0.864 (19)	1.90 (2)	2.651 (3)	144 (3)

Symmetry code: (i) −x, −y+2, −z+1.

Acknowledgements

The National Science Foundation is acknowledged for a CAREER award (CHE-1056927) to MAH. Purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

References

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