Diiodidobis(N,N,N′,N′-tetra­methyl­thio­urea-κS)cadmium(II)

Nawaz, S.; Sadaf, S.; Fettouhi, M.; Fazal, A.; Ahmad, S.

doi:10.1107/S1600536810028114

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m951

https://doi.org/10.1107/S1600536810028114

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Diiodidobis(N,N,N′,N′-tetramethylthiourea-κS)cadmium(II)

Sidra Nawaz,^a Sana Sadaf,^a Mohammed Fettouhi,^b Atif Fazal ^b and Saeed Ahmad ^a ^*

^aDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan, and ^bDepartment of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
^*Correspondence e-mail: saeed_a786@hotmail.com

(Received 5 July 2010; accepted 14 July 2010; online 17 July 2010)

In the title compound, [CdI₂(C₅H₁₂N₂S)₂], the Cd^II ion is located on a twofold rotation axis and is coordinated in a distorted tetrahedral mode by two iodide ions and by two tetramethylthiourea (tmtu) ligands through their S atoms. The crystal structure is stabilized by C—H⋯N and C—H⋯S hydrogen bonds.

Related literature

For background to thiourea complexes of group 12 elements, see: Ahmad et al. (2009 ); Bell et al. (2001 , 2004 ); Lobana et al. (2008 ); Marcos et al. (1998 ); Matsunaga et al. (2005 ); Moloto et al. (2003 ); Wazeer et al. (2007 ). The structure of the title compound is isotypic with [Cd(tmtu)₂Br₂] (Nawaz et al., 2010a ) and [Hg(tmtu)₂Cl₂] (Nawaz et al., 2010b ).

Experimental

Crystal data

[CdI₂(C₅H₁₂N₂S)₂]
M_r = 630.65
Monoclinic, C 2/c
a = 18.985 (5) Å
b = 10.395 (3) Å
c = 13.719 (4) Å
β = 130.740 (4)°
V = 2051.4 (9) Å³
Z = 4
Mo Kα radiation
μ = 4.27 mm⁻¹
T = 294 K
0.33 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.333, T_max = 0.482
13642 measured reflections
2557 independent reflections
2235 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.04
2557 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N2	0.96	2.51	2.859 (6)	101
C4—H4A⋯N1	0.96	2.52	2.853 (5)	100
C5—H5A⋯S1	0.96	2.66	3.026 (5)	103

Data collection: SMART (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028114/wm2373sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028114/wm2373Isup2.hkl

checkCIF report

Comment top

A considerable amount of work has been done in recent years on the synthesis and characterization of cadmium(II) and mercury(II) complexes of thiourea type ligands due to their variable binding modes and because of the their importance in biological systems (Ahmad et al., 2009; Bell et al., 2001, 2004; Lobana et al., 2008; Marcos et al., 1998; Matsunaga et al., 2005; Moloto et al., 2003; Wazeer et al., 2007). Cadmium(II) complexes with thiones possess a variety of structures ranging from four- to six-coordinate species with tetrahedral and octahedral environments for the Cd^II atom, respectively. In some cases, these units further aggregate to form polymeric structures (Bell et al., 2001, 2004; Lobana et al., 2008; Matsunaga et al., 2005; Moloto, et al., 2003; Wazeer et al., 2007). We report here the crystal structure of a cadmium(II) iodide complex with tetramethylthiourea (tmtu).

In the title complex, the cadmium atom is bonded to two I^- ions and to two tetramethylthiourea ligands through the sulfur atoms in a distorted tetrahedral mode (Fig. 1). The compound is isotypic with [Cd(tmtu)₂Br₂] (Nawaz et al., 2010a) and [Hg(tmtu)₂Cl₂] (Nawaz et al., 2010b).

For a more detailed description of the structure, see: Nawaz et al. (2010a).

Related literature top

For background to thiourea complexes of group 12 elements, see: Ahmad et al. (2009); Bell et al. (2001, 2004); Lobana et al. (2008); Marcos et al. (1998); Matsunaga et al. (2005); Moloto et al. (2003); Wazeer et al. (2007). The structure of the title compound is isotypic with [Cd(tmtu)₂Br₂] (Nawaz et al., 2010a) and [Hg(tmtu)₂Cl₂] (Nawaz et al., 2010b).

Experimental top

To 0.37 g (1.0 mmol) cadmium(II) iodide in 10 ml water was added to two equivalents of tetramethylthiourea in 15 ml methanol. A clear solution was obtained that was stirred for 30 minutes. The colorless solution was filtered and the filtrate was kept at room temperature for crystallization. As a result, a white crystalline product was obtained, that was washed with methanol and dried.

Structure description top

For a more detailed description of the structure, see: Nawaz et al. (2010a).

For background to thiourea complexes of group 12 elements, see: Ahmad et al. (2009); Bell et al. (2001, 2004); Lobana et al. (2008); Marcos et al. (1998); Matsunaga et al. (2005); Moloto et al. (2003); Wazeer et al. (2007). The structure of the title compound is isotypic with [Cd(tmtu)₂Br₂] (Nawaz et al., 2010a) and [Hg(tmtu)₂Cl₂] (Nawaz et al., 2010b).

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of title compound with atomic numbering scheme. Displacement ellipsoids drawn at the 30% probability level. H-atoms were omitted for clarity.

Diiodidobis(N,N,N',N'-tetramethylthiourea- κS)cadmium(II) top

Crystal data top

[CdI₂(C₅H₁₂N₂S)₂]	F(000) = 1192
M_r = 630.65	D_x = 2.042 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 13642 reflections
a = 18.985 (5) Å	θ = 2.4–28.3°
b = 10.395 (3) Å	µ = 4.27 mm⁻¹
c = 13.719 (4) Å	T = 294 K
β = 130.740 (4)°	Block, colorless
V = 2051.4 (9) Å³	0.33 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX area-detector diffractometer	2557 independent reflections
Radiation source: normal-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.333, T_max = 0.482	k = −13→13
13642 measured reflections	l = −18→18

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0229P)² + 2.9795P] where P = (F_o² + 2F_c²)/3
2557 reflections	(Δ/σ)_max = 0.002
91 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[CdI₂(C₅H₁₂N₂S)₂]	V = 2051.4 (9) Å³
M_r = 630.65	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.985 (5) Å	µ = 4.27 mm⁻¹
b = 10.395 (3) Å	T = 294 K
c = 13.719 (4) Å	0.33 × 0.22 × 0.20 mm
β = 130.740 (4)°

Data collection top

Bruker SMART APEX area-detector diffractometer	2557 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2235 reflections with I > 2σ(I)
T_min = 0.333, T_max = 0.482	R_int = 0.022
13642 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.054	H-atom parameters constrained
S = 1.04	Δρ_max = 0.67 e Å⁻³
2557 reflections	Δρ_min = −0.58 e Å⁻³
91 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	1.0000	0.71325 (3)	0.2500	0.04562 (8)
I1	1.155686 (14)	0.56794 (2)	0.35345 (2)	0.06074 (8)
S1	1.03756 (5)	0.84000 (9)	0.43960 (7)	0.05829 (19)
N1	0.92464 (19)	0.7668 (2)	0.4801 (3)	0.0568 (6)
N2	0.85712 (18)	0.8932 (3)	0.3011 (2)	0.0569 (6)
C1	0.93150 (19)	0.8328 (3)	0.4031 (3)	0.0462 (6)
C2	0.8634 (3)	0.8067 (4)	0.5045 (4)	0.0777 (10)
H2A	0.8343	0.8869	0.4619	0.116*
H2B	0.8992	0.8168	0.5954	0.116*
H2C	0.8165	0.7423	0.4722	0.116*
C3	0.9920 (3)	0.6671 (4)	0.5676 (4)	0.0870 (12)
H3A	1.0154	0.6268	0.5308	0.130*
H3B	0.9622	0.6037	0.5808	0.130*
H3C	1.0425	0.7054	0.6486	0.130*
C4	0.7619 (2)	0.8470 (4)	0.2310 (4)	0.0808 (11)
H4A	0.7637	0.7632	0.2621	0.121*
H4B	0.7299	0.8422	0.1408	0.121*
H4C	0.7297	0.9054	0.2444	0.121*
C5	0.8660 (3)	0.9963 (4)	0.2369 (4)	0.0840 (11)
H5A	0.9259	1.0360	0.2972	0.126*
H5B	0.8184	1.0594	0.2048	0.126*
H5C	0.8594	0.9610	0.1666	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.04989 (15)	0.04876 (16)	0.04920 (15)	0.000	0.03717 (13)	0.000
I1	0.05619 (12)	0.06315 (14)	0.06036 (13)	0.01437 (9)	0.03692 (11)	0.00562 (9)
S1	0.0509 (4)	0.0769 (5)	0.0529 (4)	−0.0122 (4)	0.0365 (3)	−0.0185 (4)
N1	0.0677 (15)	0.0552 (14)	0.0648 (15)	0.0083 (12)	0.0508 (14)	0.0065 (12)
N2	0.0576 (14)	0.0651 (15)	0.0490 (13)	0.0072 (12)	0.0352 (12)	−0.0014 (11)
C1	0.0517 (14)	0.0473 (14)	0.0470 (13)	−0.0003 (11)	0.0355 (12)	−0.0087 (11)
C2	0.092 (3)	0.090 (3)	0.091 (3)	0.005 (2)	0.077 (2)	0.003 (2)
C3	0.109 (3)	0.067 (2)	0.103 (3)	0.025 (2)	0.077 (3)	0.030 (2)
C4	0.0502 (17)	0.118 (3)	0.068 (2)	0.0085 (19)	0.0360 (17)	−0.014 (2)
C5	0.102 (3)	0.081 (3)	0.064 (2)	0.019 (2)	0.052 (2)	0.0211 (19)

Geometric parameters (Å, º) top

Cd1—S1	2.5670 (9)	C2—H2B	0.9600
Cd1—S1ⁱ	2.5670 (10)	C2—H2C	0.9600
Cd1—I1ⁱ	2.7489 (7)	C3—H3A	0.9600
Cd1—I1	2.7489 (7)	C3—H3B	0.9600
S1—C1	1.731 (3)	C3—H3C	0.9600
N1—C1	1.335 (4)	C4—H4A	0.9600
N1—C2	1.465 (4)	C4—H4B	0.9600
N1—C3	1.466 (4)	C4—H4C	0.9600
N2—C1	1.330 (4)	C5—H5A	0.9600
N2—C5	1.464 (5)	C5—H5B	0.9600
N2—C4	1.468 (4)	C5—H5C	0.9600
C2—H2A	0.9600

S1—Cd1—S1ⁱ	118.23 (5)	H2A—C2—H2C	109.5
S1—Cd1—I1ⁱ	107.41 (2)	H2B—C2—H2C	109.5
S1ⁱ—Cd1—I1ⁱ	105.36 (2)	N1—C3—H3A	109.5
S1—Cd1—I1	105.36 (2)	N1—C3—H3B	109.5
S1ⁱ—Cd1—I1	107.41 (2)	H3A—C3—H3B	109.5
I1ⁱ—Cd1—I1	113.34 (3)	N1—C3—H3C	109.5
C1—S1—Cd1	100.59 (9)	H3A—C3—H3C	109.5
C1—N1—C2	122.5 (3)	H3B—C3—H3C	109.5
C1—N1—C3	121.9 (3)	N2—C4—H4A	109.5
C2—N1—C3	114.3 (3)	N2—C4—H4B	109.5
C1—N2—C5	121.3 (3)	H4A—C4—H4B	109.5
C1—N2—C4	122.9 (3)	N2—C4—H4C	109.5
C5—N2—C4	114.9 (3)	H4A—C4—H4C	109.5
N2—C1—N1	119.4 (3)	H4B—C4—H4C	109.5
N2—C1—S1	121.3 (2)	N2—C5—H5A	109.5
N1—C1—S1	119.3 (2)	N2—C5—H5B	109.5
N1—C2—H2A	109.5	H5A—C5—H5B	109.5
N1—C2—H2B	109.5	N2—C5—H5C	109.5
H2A—C2—H2B	109.5	H5A—C5—H5C	109.5
N1—C2—H2C	109.5	H5B—C5—H5C	109.5

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2	0.96	2.51	2.859 (6)	101
C4—H4A···N1	0.96	2.52	2.853 (5)	100
C5—H5A···S1	0.96	2.66	3.026 (5)	103

Experimental details

Crystal data
Chemical formula	[CdI₂(C₅H₁₂N₂S)₂]
M_r	630.65
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	18.985 (5), 10.395 (3), 13.719 (4)
β (°)	130.740 (4)
V (Å³)	2051.4 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.27
Crystal size (mm)	0.33 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.333, 0.482
No. of measured, independent and observed [I > 2σ(I)] reflections	13642, 2557, 2235
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.04
No. of reflections	2557
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.58

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2	0.96	2.51	2.859 (6)	101
C4—H4A···N1	0.96	2.52	2.853 (5)	100
C5—H5A···S1	0.96	2.66	3.026 (5)	103

Acknowledgements

We gratefully acknowledge King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, for providing the X-ray facility.

References

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