Dicyanidobis(thio-urea-κS)cadmium(II) monohydrate.

In the title compound, [Cd(CN)(2)(CH(4)N(2)S)(2)]·H(2)O, the Cd atom lies on a twofold rotation axis and is bonded to two S atoms of thio-urea and two C atoms of the cyanide anions in a distorted tetra-hedral environment. The crystal structure is stabilized by N-H⋯N(CN), N-H⋯O, O-H⋯N and N-H⋯S hydrogen bonds.

Related literature

For background to cadmium(II) complexes of thio­urea-type ligands, see: Corao & Baggio (1969 ▶); Malik et al. (2010 ▶); Marcos et al. (1998 ▶); Nawaz et al. (2010a ▶,b ▶); Wang et al. (2002 ▶). For the non-linear optical properties and semi-conducting applications of Cd–thio­urea complexes, see: Rajesh et al. (2004 ▶); Stoev & Ruseva (1994 ▶). For the structures of cyanido complexes of d 10 metal ions, see: Ahmad et al. (2009 ▶); Hanif et al. (2007 ▶); Yoshikawa et al. (2003 ▶).

Experimental

Crystal data

[Cd(CN)2(CH4N2S)2]·H2O

M = 334.70

Monoclinic,

a = 10.5955 (6) Å

b = 4.0782 (3) Å

c = 13.4127 (8) Å

β = 98.738 (1)°

V = 572.84 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.25 mm−1

T = 294 K

0.29 × 0.28 × 0.24 mm

Data collection

Bruker SMART APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.561, T max = 0.614

7211 measured reflections

1430 independent reflections

1376 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.043

S = 1.10

1430 reflections

86 parameters

All H-atom parameters refined

Δρmax = 0.73 e Å−3

Δρmin = −0.74 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: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028710/zl2290sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028710/zl2290Isup2.hkl

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

[Cd(CN)2(CH4N2S)2]·H2O	F(000) = 328
Mr = 334.70	Dx = 1.940 Mg m−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 7211 reflections
a = 10.5955 (6) Å	θ = 2.3–28.3°
b = 4.0782 (3) Å	µ = 2.25 mm−1
c = 13.4127 (8) Å	T = 294 K
β = 98.738 (1)°	Parallelepiped, yellow
V = 572.84 (6) Å3	0.29 × 0.28 × 0.24 mm
Z = 2

Bruker SMART APEX area-detector diffractometer	1430 independent reflections
Radiation source: normal-focus sealed tube	1376 reflections with I > 2σ(I)
graphite	Rint = 0.017
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.561, Tmax = 0.614	k = −5→5
7211 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)] = 0.018	All H-atom parameters refined
wR(F2) = 0.043	w = 1/[σ2(Fo2) + (0.0181P)2 + 0.3434P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
1430 reflections	Δρmax = 0.73 e Å−3
86 parameters	Δρmin = −0.73 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.072 (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	0.2500	−0.06581 (5)	0.2500	0.03756 (9)
S1	0.35766 (4)	0.31297 (11)	0.39821 (3)	0.03220 (11)
C1	0.06927 (16)	−0.2357 (5)	0.29604 (12)	0.0340 (3)
C2	0.28176 (16)	0.2070 (4)	0.49904 (12)	0.0322 (3)
N1	−0.02293 (17)	−0.3264 (6)	0.31974 (14)	0.0499 (4)
N2	0.16014 (18)	0.2695 (6)	0.49815 (14)	0.0535 (5)
N3	0.3466 (2)	0.0687 (6)	0.57851 (14)	0.0518 (5)
O1	0.7500	0.2524 (6)	0.2500	0.0451 (5)
H1	0.811 (3)	0.376 (7)	0.267 (2)	0.059 (8)*
H2	0.121 (3)	0.355 (8)	0.451 (2)	0.068 (9)*
H3	0.127 (3)	0.243 (7)	0.551 (2)	0.056 (7)*
H4	0.429 (4)	0.021 (8)	0.578 (3)	0.078 (10)*
H5	0.313 (3)	0.013 (7)	0.619 (3)	0.064 (9)*

	U11	U22	U33	U12	U13	U23
Cd1	0.02792 (11)	0.05064 (14)	0.03652 (12)	0.000	0.01265 (7)	0.000
S1	0.0315 (2)	0.0395 (2)	0.02651 (18)	−0.00063 (16)	0.00713 (14)	0.00102 (16)
C1	0.0321 (8)	0.0416 (9)	0.0291 (7)	0.0028 (7)	0.0072 (6)	0.0029 (7)
C2	0.0352 (8)	0.0371 (8)	0.0249 (7)	−0.0004 (7)	0.0063 (6)	−0.0031 (6)
N1	0.0367 (8)	0.0677 (12)	0.0477 (9)	−0.0040 (8)	0.0145 (7)	0.0077 (9)
N2	0.0403 (9)	0.0892 (16)	0.0338 (8)	0.0155 (10)	0.0148 (7)	0.0124 (9)
N3	0.0417 (9)	0.0832 (15)	0.0319 (8)	0.0100 (9)	0.0099 (7)	0.0164 (9)
O1	0.0373 (10)	0.0563 (13)	0.0423 (10)	0.000	0.0076 (8)	0.000

Cd1—C1i	2.2108 (17)	C2—N2	1.312 (2)
Cd1—C1	2.2108 (17)	N2—H2	0.78 (3)
Cd1—S1	2.6363 (5)	N2—H3	0.84 (3)
Cd1—S1i	2.6363 (5)	N3—H4	0.90 (4)
S1—C2	1.7300 (17)	N3—H5	0.72 (4)
C1—N1	1.134 (2)	O1—H1	0.83 (3)
C2—N3	1.305 (2)
C1i—Cd1—C1	143.47 (10)	N3—C2—S1	119.80 (15)
C1i—Cd1—S1	95.76 (4)	N2—C2—S1	121.13 (14)
C1—Cd1—S1	105.48 (5)	C2—N2—H2	120 (2)
C1i—Cd1—S1i	105.48 (5)	C2—N2—H3	120.4 (19)
C1—Cd1—S1i	95.76 (4)	H2—N2—H3	119 (3)
S1—Cd1—S1i	108.26 (2)	C2—N3—H4	119 (2)
C2—S1—Cd1	104.11 (6)	C2—N3—H5	119 (3)
N1—C1—Cd1	179.22 (18)	H4—N3—H5	122 (3)
N3—C2—N2	119.05 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H5···O1ii	0.72 (4)	2.26 (4)	2.961 (2)	166 (3)
N3—H4···S1ii	0.90 (4)	2.61 (4)	3.470 (2)	159 (3)
N2—H3···N1iii	0.84 (3)	2.22 (3)	3.035 (2)	163 (3)
N2—H2···N1iv	0.78 (3)	2.51 (3)	3.286 (3)	171 (3)
O1—H1···N1v	0.83 (3)	2.16 (3)	2.988 (2)	176 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H5⋯O1i	0.72 (4)	2.26 (4)	2.961 (2)	166 (3)
N3—H4⋯S1i	0.90 (4)	2.61 (4)	3.470 (2)	159 (3)
N2—H3⋯N1ii	0.84 (3)	2.22 (3)	3.035 (2)	163 (3)
N2—H2⋯N1iii	0.78 (3)	2.51 (3)	3.286 (3)	171 (3)
O1—H1⋯N1iv	0.83 (3)	2.16 (3)	2.988 (2)	176 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .