catena-Poly[[[bis-(thio-urea-κS)cadmium]-di-μ-thio-cyanato-κ(2)N:S;κ(2)S:N] dihydrate].

The title compound, {[Cd(NCS)(2)(CH(4)N(2)S)(2)]·2H(2)O}(n), forms a one-dimensional chain parallel to the a axis, caused by the presence of the bridging thio-cyanate groups. Two solvent mol-ecules per complex are present in the lattice. The Cd(II) ion is situated on an inversion centre and is coordinated in a distorted octa-hedral fashion by two N and two S atoms from four thio-cyanate ligands and by two S atoms from two thio-urea mol-ecules. Weak O-H⋯S, N-H⋯O and N-H⋯N inter-actions reinforce the structure.

Related literature

For a general introduction to thio­cyanato complexes, see: Nardelli et al. (1957 ▶). For the syntheses and structures of a series of cadmium complexes with thio­urea derivatives and thio­cyanato ligands, see: Wang et al. (2002 ▶); Cavalca et al. (1960 ▶); Zhu et al. (2000 ▶); Yang et al. (2001 ▶); Ahmad et al. (2008 ▶); Williams et al. (1992 ▶). For information on the properties of complexes incorporating these ligands, see: Yuan et al. (1997 ▶); Krunks et al. (1997 ▶); Amutha et al. (2011 ▶); Machura et al. (2011 ▶). For the use of CdII complexes with mixed S-donor ligands as precursors to CdS, see: Kropidłowska et al. (2008 ▶).

Experimental

Crystal data

[Cd(NCS)2(CH4N2S)2]·2H2O

M = 416.84

Triclinic,

a = 5.8533 (3) Å

b = 7.3527 (3) Å

c = 8.8630 (4) Å

α = 73.413 (4)°

β = 76.926 (4)°

γ = 88.856 (4)°

V = 355.69 (3) Å3

Z = 1

Mo Kα radiation

μ = 2.12 mm−1

T = 293 K

0.53 × 0.42 × 0.23 mm

Data collection

Oxford Diffraction KM-4-CCD diffractometer

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.558, T max = 0.725

7642 measured reflections

2268 independent reflections

1985 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.062

S = 1.05

2268 reflections

85 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030267/fj2575sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030267/fj2575Isup2.hkl

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

[Cd(NCS)2(CH4N2S)2]·2H2O	Z = 1
Mr = 416.84	F(000) = 206
Triclinic, P1	Dx = 1.946 Mg m−3
Hall symbol: -P 1	Melting point: 460 K
a = 5.8533 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3527 (3) Å	Cell parameters from 4676 reflections
c = 8.8630 (4) Å	θ = 2.9–33.8°
α = 73.413 (4)°	µ = 2.12 mm−1
β = 76.926 (4)°	T = 293 K
γ = 88.856 (4)°	Block, colourless
V = 355.69 (3) Å3	0.53 × 0.42 × 0.23 mm

Oxford Diffraction KM-4-CCD diffractometer	1985 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω–scan	θmax = 31°, θmin = 2.9°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2008), based on expressions derived by Clark & Reid (1995)]	h = −8→8
Tmin = 0.558, Tmax = 0.725	k = −10→10
7642 measured reflections	l = −12→12
2268 independent reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0266P)2] where P = (Fo2 + 2Fc2)/3
2268 reflections	(Δ/σ)max < 0.001
85 parameters	Δρmax = 0.47 e Å−3
3 restraints	Δρmin = −0.51 e Å−3

Experimental. CrysAlisPro, (Oxford Diffraction, 2008). Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by (Clark & Reid, 1995).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.5	0.5	0	0.03082 (8)
S1	0.24899 (10)	0.38566 (9)	0.30122 (7)	0.03890 (15)
S2	0.25651 (10)	0.82898 (8)	−0.03961 (7)	0.03377 (13)
N1	0.6502 (3)	0.3430 (3)	0.3988 (3)	0.0424 (5)
H1A	0.7326	0.2965	0.4686	0.051*
H1B	0.7155	0.4193	0.3061	0.051*
N2	0.3288 (4)	0.1803 (3)	0.5771 (3)	0.0481 (6)
H2A	0.4141	0.1352	0.6452	0.058*
H2B	0.1813	0.1488	0.6023	0.058*
N3	−0.1946 (3)	0.6528 (3)	0.0619 (3)	0.0391 (5)
C1	0.4240 (4)	0.2975 (3)	0.4340 (3)	0.0321 (5)
C2	−0.0091 (4)	0.7257 (3)	0.0194 (3)	0.0281 (4)
O1	0.1962 (4)	0.9249 (3)	0.3133 (2)	0.0524 (5)
H1C	0.216 (7)	0.902 (5)	0.229 (3)	0.079*
H1D	0.193 (7)	1.038 (3)	0.296 (4)	0.079*

	U11	U22	U33	U12	U13	U23
Cd1	0.02632 (12)	0.03241 (13)	0.03125 (13)	−0.00184 (9)	−0.00529 (9)	−0.00613 (10)
S1	0.0255 (3)	0.0545 (4)	0.0282 (3)	0.0010 (3)	−0.0048 (2)	0.0002 (3)
S2	0.0298 (3)	0.0265 (3)	0.0402 (3)	−0.0021 (2)	−0.0038 (2)	−0.0050 (2)
N1	0.0333 (10)	0.0557 (13)	0.0361 (11)	−0.0005 (10)	−0.0120 (9)	−0.0065 (10)
N2	0.0454 (12)	0.0560 (13)	0.0333 (11)	−0.0053 (11)	−0.0110 (10)	0.0044 (10)
N3	0.0330 (10)	0.0371 (11)	0.0500 (13)	−0.0009 (9)	−0.0106 (9)	−0.0158 (10)
C1	0.0357 (12)	0.0316 (11)	0.0295 (11)	0.0009 (9)	−0.0074 (9)	−0.0100 (9)
C2	0.0335 (11)	0.0264 (10)	0.0266 (10)	0.0050 (9)	−0.0101 (9)	−0.0088 (8)
O1	0.0662 (13)	0.0522 (11)	0.0412 (11)	−0.0028 (11)	−0.0197 (10)	−0.0113 (10)

Cd1—N3i	2.3734 (19)	N1—H1A	0.86
Cd1—N3ii	2.3734 (19)	N1—H1B	0.86
Cd1—S1	2.6431 (6)	N2—C1	1.318 (3)
Cd1—S1iii	2.6431 (6)	N2—H2A	0.86
Cd1—S2iii	2.7585 (6)	N2—H2B	0.86
Cd1—S2	2.7585 (6)	N3—C2	1.154 (3)
S1—C1	1.714 (2)	N3—Cd1iv	2.3734 (19)
S2—C2	1.649 (2)	O1—H1C	0.797 (17)
N1—C1	1.317 (3)	O1—H1D	0.805 (17)
N3i—Cd1—N3ii	180	C1—S1—Cd1	111.15 (8)
N3i—Cd1—S1	95.01 (6)	C2—S2—Cd1	96.75 (7)
N3ii—Cd1—S1	84.99 (6)	C1—N1—H1A	120
N3i—Cd1—S1iii	84.99 (6)	C1—N1—H1B	120
N3ii—Cd1—S1iii	95.01 (6)	H1A—N1—H1B	120
S1—Cd1—S1iii	180	C1—N2—H2A	120
N3i—Cd1—S2iii	89.81 (5)	C1—N2—H2B	120
N3ii—Cd1—S2iii	90.19 (5)	H2A—N2—H2B	120
S1—Cd1—S2iii	92.043 (19)	C2—N3—Cd1iv	148.15 (19)
S1iii—Cd1—S2iii	87.957 (19)	N1—C1—N2	118.6 (2)
N3i—Cd1—S2	90.19 (5)	N1—C1—S1	122.51 (18)
N3ii—Cd1—S2	89.81 (5)	N2—C1—S1	118.87 (18)
S1—Cd1—S2	87.957 (19)	N3—C2—S2	179.5 (2)
S1iii—Cd1—S2	92.043 (19)	H1C—O1—H1D	108 (3)
S2iii—Cd1—S2	180.00 (3)
N3i—Cd1—S1—C1	−43.20 (10)	N3ii—Cd1—S2—C2	30.81 (10)
N3ii—Cd1—S1—C1	136.80 (10)	S1—Cd1—S2—C2	−54.18 (8)
S2iii—Cd1—S1—C1	46.79 (9)	S1iii—Cd1—S2—C2	125.82 (8)
S2—Cd1—S1—C1	−133.21 (9)	Cd1—S1—C1—N1	22.3 (2)
N3i—Cd1—S2—C2	−149.19 (10)	Cd1—S1—C1—N2	−157.98 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1v	0.86	2.26	3.049 (3)	153
N1—H1B···N3i	0.86	2.3	3.147 (3)	167
N2—H2A···O1v	0.86	2.4	3.159 (3)	147
N2—H2B···O1vi	0.86	2.19	3.050 (3)	175
O1—H1C···S2	0.80 (2)	2.54 (2)	3.340 (2)	177 (4)
O1—H1D···S1vii	0.81 (2)	2.59 (2)	3.377 (2)	165 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86	2.26	3.049 (3)	153
N1—H1B⋯N3ii	0.86	2.3	3.147 (3)	167
N2—H2A⋯O1i	0.86	2.4	3.159 (3)	147
N2—H2B⋯O1iii	0.86	2.19	3.050 (3)	175
O1—H1C⋯S2	0.80 (2)	2.54 (2)	3.340 (2)	177 (4)
O1—H1D⋯S1iv	0.81 (2)	2.59 (2)	3.377 (2)	165 (3)

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