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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m951.
Published online 2010 July 17. doi:  10.1107/S1600536810028114
PMCID: PMC3007464

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

Abstract

In the title compound, [CdI2(C5H12N2S)2], the CdII 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 [triangle]); Bell et al. (2001 [triangle], 2004 [triangle]); Lobana et al. (2008 [triangle]); Marcos et al. (1998 [triangle]); Matsunaga et al. (2005 [triangle]); Moloto et al. (2003 [triangle]); Wazeer et al. (2007 [triangle]). The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a [triangle]) and [Hg(tmtu)2Cl2] (Nawaz et al., 2010b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m951-scheme1.jpg

Experimental

Crystal data

  • [CdI2(C5H12N2S)2]
  • M r = 630.65
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m951-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.054
  • S = 1.04
  • 2557 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.67 e Å−3
  • Δρmin = −0.58 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028114/wm2373Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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 CdII 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).

Experimental

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.

Refinement

H atoms were placed in calculated positions with a C—H distance of 0.96 Å and Uiso(H) = 1.5 Ueq(C).

Figures

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.

Crystal data

[CdI2(C5H12N2S)2]F(000) = 1192
Mr = 630.65Dx = 2.042 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 13642 reflections
a = 18.985 (5) Åθ = 2.4–28.3°
b = 10.395 (3) ŵ = 4.27 mm1
c = 13.719 (4) ÅT = 294 K
β = 130.740 (4)°Block, colorless
V = 2051.4 (9) Å30.33 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEX area-detector diffractometer2557 independent reflections
Radiation source: normal-focus sealed tube2235 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −25→25
Tmin = 0.333, Tmax = 0.482k = −13→13
13642 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0229P)2 + 2.9795P] where P = (Fo2 + 2Fc2)/3
2557 reflections(Δ/σ)max = 0.002
91 parametersΔρmax = 0.67 e Å3
0 restraintsΔρmin = −0.58 e Å3

Special details

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)

xyzUiso*/Ueq
Cd11.00000.71325 (3)0.25000.04562 (8)
I11.155686 (14)0.56794 (2)0.35345 (2)0.06074 (8)
S11.03756 (5)0.84000 (9)0.43960 (7)0.05829 (19)
N10.92464 (19)0.7668 (2)0.4801 (3)0.0568 (6)
N20.85712 (18)0.8932 (3)0.3011 (2)0.0569 (6)
C10.93150 (19)0.8328 (3)0.4031 (3)0.0462 (6)
C20.8634 (3)0.8067 (4)0.5045 (4)0.0777 (10)
H2A0.83430.88690.46190.116*
H2B0.89920.81680.59540.116*
H2C0.81650.74230.47220.116*
C30.9920 (3)0.6671 (4)0.5676 (4)0.0870 (12)
H3A1.01540.62680.53080.130*
H3B0.96220.60370.58080.130*
H3C1.04250.70540.64860.130*
C40.7619 (2)0.8470 (4)0.2310 (4)0.0808 (11)
H4A0.76370.76320.26210.121*
H4B0.72990.84220.14080.121*
H4C0.72970.90540.24440.121*
C50.8660 (3)0.9963 (4)0.2369 (4)0.0840 (11)
H5A0.92591.03600.29720.126*
H5B0.81841.05940.20480.126*
H5C0.85940.96100.16660.126*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.04989 (15)0.04876 (16)0.04920 (15)0.0000.03717 (13)0.000
I10.05619 (12)0.06315 (14)0.06036 (13)0.01437 (9)0.03692 (11)0.00562 (9)
S10.0509 (4)0.0769 (5)0.0529 (4)−0.0122 (4)0.0365 (3)−0.0185 (4)
N10.0677 (15)0.0552 (14)0.0648 (15)0.0083 (12)0.0508 (14)0.0065 (12)
N20.0576 (14)0.0651 (15)0.0490 (13)0.0072 (12)0.0352 (12)−0.0014 (11)
C10.0517 (14)0.0473 (14)0.0470 (13)−0.0003 (11)0.0355 (12)−0.0087 (11)
C20.092 (3)0.090 (3)0.091 (3)0.005 (2)0.077 (2)0.003 (2)
C30.109 (3)0.067 (2)0.103 (3)0.025 (2)0.077 (3)0.030 (2)
C40.0502 (17)0.118 (3)0.068 (2)0.0085 (19)0.0360 (17)−0.014 (2)
C50.102 (3)0.081 (3)0.064 (2)0.019 (2)0.052 (2)0.0211 (19)

Geometric parameters (Å, °)

Cd1—S12.5670 (9)C2—H2B0.9600
Cd1—S1i2.5670 (10)C2—H2C0.9600
Cd1—I1i2.7489 (7)C3—H3A0.9600
Cd1—I12.7489 (7)C3—H3B0.9600
S1—C11.731 (3)C3—H3C0.9600
N1—C11.335 (4)C4—H4A0.9600
N1—C21.465 (4)C4—H4B0.9600
N1—C31.466 (4)C4—H4C0.9600
N2—C11.330 (4)C5—H5A0.9600
N2—C51.464 (5)C5—H5B0.9600
N2—C41.468 (4)C5—H5C0.9600
C2—H2A0.9600
S1—Cd1—S1i118.23 (5)H2A—C2—H2C109.5
S1—Cd1—I1i107.41 (2)H2B—C2—H2C109.5
S1i—Cd1—I1i105.36 (2)N1—C3—H3A109.5
S1—Cd1—I1105.36 (2)N1—C3—H3B109.5
S1i—Cd1—I1107.41 (2)H3A—C3—H3B109.5
I1i—Cd1—I1113.34 (3)N1—C3—H3C109.5
C1—S1—Cd1100.59 (9)H3A—C3—H3C109.5
C1—N1—C2122.5 (3)H3B—C3—H3C109.5
C1—N1—C3121.9 (3)N2—C4—H4A109.5
C2—N1—C3114.3 (3)N2—C4—H4B109.5
C1—N2—C5121.3 (3)H4A—C4—H4B109.5
C1—N2—C4122.9 (3)N2—C4—H4C109.5
C5—N2—C4114.9 (3)H4A—C4—H4C109.5
N2—C1—N1119.4 (3)H4B—C4—H4C109.5
N2—C1—S1121.3 (2)N2—C5—H5A109.5
N1—C1—S1119.3 (2)N2—C5—H5B109.5
N1—C2—H2A109.5H5A—C5—H5B109.5
N1—C2—H2B109.5N2—C5—H5C109.5
H2A—C2—H2B109.5H5A—C5—H5C109.5
N1—C2—H2C109.5H5B—C5—H5C109.5

Symmetry codes: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···N20.962.512.859 (6)101
C4—H4A···N10.962.522.853 (5)100
C5—H5A···S10.962.663.026 (5)103

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2373).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography