Dibromidobis(N,N,N',N'-tetra-methyl-thio-urea-κS)cadmium(II).

In the title compound, [CdBr(2)(C(5)H(12)N(2)S)(2)], the Cd(II) atom lies on a twofold rotation axis. It exhibits a distorted tetra-hedral coordination environment defined by two S atoms of two tetra-methyl-thio-urea (tmtu) ligands and two bromide ions. The crystal structure is consolidated by C-H⋯N and C-H⋯S hydrogen bonds.

Related literature

For crystallographic and spectroscopic studies of thio­urea complexes, see: Al-Arfaj et al. (1998 ▶); Ali et al. (2009 ▶); Isab et al. (2009 ▶); Lobana et al. (2008 ▶); Marcos et al. (1998 ▶); Moloto et al. (2003 ▶). The structure of the title compound is isotypic with [Cd(tmtu)2I2] (Nawaz et al., 2010a ▶) and [Hg(tmtu)2Cl2] (Nawaz et al., 2010b ▶).

Experimental

Crystal data

[CdBr2(C5H12N2S)2]

M = 536.67

Monoclinic,

a = 18.6133 (17) Å

b = 10.0690 (9) Å

c = 13.4600 (12) Å

β = 130.834 (1)°

V = 1908.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 5.54 mm−1

T = 292 K

0.24 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.350, T max = 0.404

12678 measured reflections

2379 independent reflections

2114 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.052

S = 1.05

2379 reflections

92 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.45 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028102/wm2371sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028102/wm2371Isup2.hkl

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

[CdBr2(C5H12N2S)2]	F(000) = 1048
Mr = 536.67	Dx = 1.868 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 12678 reflections
a = 18.6133 (17) Å	θ = 2.5–28.3°
b = 10.0690 (9) Å	µ = 5.54 mm−1
c = 13.4600 (12) Å	T = 292 K
β = 130.834 (1)°	Block, colorless
V = 1908.6 (3) Å3	0.24 × 0.23 × 0.20 mm
Z = 4

Bruker SMART APEX area-detector diffractometer	2379 independent reflections
Radiation source: normal-focus sealed tube	2114 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.350, Tmax = 0.404	k = −13→13
12678 measured reflections	l = −17→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021	H-atom parameters constrained
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.025P)2 + 1.3001P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
2379 reflections	Δρmax = 0.44 e Å−3
92 parameters	Δρmin = −0.45 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0068 (2)

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.

	x	y	z	Uiso*/Ueq
Cd1	1.0000	0.70441 (2)	0.2500	0.03969 (8)
Br1	1.149352 (17)	0.56647 (3)	0.34643 (3)	0.05549 (9)
S1	1.03619 (4)	0.83583 (7)	0.44089 (5)	0.04794 (14)
N1	0.91758 (14)	0.76405 (19)	0.4771 (2)	0.0474 (4)
N2	0.85096 (13)	0.8900 (2)	0.29223 (18)	0.0471 (4)
C1	0.92634 (14)	0.82923 (19)	0.39910 (19)	0.0366 (4)
C2	0.8527 (2)	0.8077 (3)	0.4968 (3)	0.0672 (7)
H2A	0.8267	0.8928	0.4562	0.101*
H2B	0.8867	0.8145	0.5891	0.101*
H2C	0.8022	0.7444	0.4580	0.101*
C3	0.9861 (2)	0.6637 (3)	0.5706 (3)	0.0724 (8)
H3A	1.0111	0.6189	0.5359	0.109*
H3B	0.9552	0.6004	0.5851	0.109*
H3C	1.0369	0.7056	0.6522	0.109*
C4	0.75337 (18)	0.8418 (3)	0.2186 (3)	0.0694 (8)
H4A	0.7550	0.7542	0.2480	0.104*
H4B	0.7211	0.8394	0.1266	0.104*
H4C	0.7203	0.9005	0.2330	0.104*
C5	0.8609 (2)	0.9921 (3)	0.2254 (3)	0.0697 (8)
H5A	0.9218	1.0340	0.2870	0.105*
H5B	0.8118	1.0573	0.1892	0.105*
H5C	0.8557	0.9524	0.1561	0.105*

	U11	U22	U33	U12	U13	U23
Cd1	0.04286 (13)	0.04283 (13)	0.04311 (13)	0.000	0.03237 (11)	0.000
Br1	0.05068 (15)	0.05784 (16)	0.05843 (16)	0.01407 (10)	0.03588 (13)	0.00638 (11)
S1	0.0391 (3)	0.0665 (4)	0.0425 (3)	−0.0082 (2)	0.0286 (2)	−0.0132 (2)
N1	0.0572 (11)	0.0471 (10)	0.0559 (11)	0.0041 (9)	0.0448 (10)	0.0036 (8)
N2	0.0448 (10)	0.0540 (11)	0.0427 (10)	0.0038 (8)	0.0287 (9)	−0.0020 (8)
C1	0.0406 (10)	0.0363 (10)	0.0371 (10)	−0.0014 (8)	0.0272 (9)	−0.0061 (8)
C2	0.0799 (19)	0.0800 (19)	0.0815 (19)	−0.0012 (15)	0.0702 (18)	−0.0047 (15)
C3	0.090 (2)	0.0600 (16)	0.082 (2)	0.0174 (15)	0.0627 (19)	0.0238 (15)
C4	0.0393 (13)	0.101 (2)	0.0573 (16)	0.0026 (14)	0.0268 (12)	−0.0123 (15)
C5	0.0804 (19)	0.0721 (18)	0.0571 (15)	0.0165 (15)	0.0451 (15)	0.0201 (14)

Cd1—S1	2.5580 (6)	C2—H2B	0.9600
Cd1—S1i	2.5580 (6)	C2—H2C	0.9600
Cd1—Br1i	2.5735 (3)	C3—H3A	0.9600
Cd1—Br1	2.5735 (3)	C3—H3B	0.9600
S1—C1	1.731 (2)	C3—H3C	0.9600
N1—C1	1.335 (3)	C4—H4A	0.9600
N1—C3	1.460 (3)	C4—H4B	0.9600
N1—C2	1.463 (3)	C4—H4C	0.9600
N2—C1	1.331 (3)	C5—H5A	0.9600
N2—C5	1.455 (3)	C5—H5B	0.9600
N2—C4	1.471 (3)	C5—H5C	0.9600
C2—H2A	0.9600
S1—Cd1—S1i	117.70 (3)	H2A—C2—H2C	109.5
S1—Cd1—Br1i	105.899 (14)	H2B—C2—H2C	109.5
S1i—Cd1—Br1i	106.524 (15)	N1—C3—H3A	109.5
S1—Cd1—Br1	106.524 (15)	N1—C3—H3B	109.5
S1i—Cd1—Br1	105.899 (14)	H3A—C3—H3B	109.5
Br1i—Cd1—Br1	114.676 (17)	N1—C3—H3C	109.5
C1—S1—Cd1	100.04 (7)	H3A—C3—H3C	109.5
C1—N1—C3	122.1 (2)	H3B—C3—H3C	109.5
C1—N1—C2	122.3 (2)	N2—C4—H4A	109.5
C3—N1—C2	114.2 (2)	N2—C4—H4B	109.5
C1—N2—C5	121.5 (2)	H4A—C4—H4B	109.5
C1—N2—C4	122.8 (2)	N2—C4—H4C	109.5
C5—N2—C4	114.6 (2)	H4A—C4—H4C	109.5
N2—C1—N1	119.41 (19)	H4B—C4—H4C	109.5
N2—C1—S1	121.32 (16)	N2—C5—H5A	109.5
N1—C1—S1	119.26 (16)	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

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2	0.96	2.53	2.855 (4)	100
C5—H5A···S1	0.96	2.65	3.026 (3)	104

Table 1

Selected bond lengths (Å)

Cd1—S1	2.5580 (6)
Cd1—Br1	2.5735 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N2	0.96	2.53	2.855 (4)	100
C5—H5A⋯S1	0.96	2.65	3.026 (3)	104