catena-Poly[[bis-(thio-cyanato-κN)cobalt(II)]-di-μ-thio-urea-κ(4)S:S].

In the title polymeric complex, [Co(NCS)(2){SC(NH(2))(2)}(2)](n), the asymmetric unit comprises a Co(II) ion, which is situated on an inversion centre, an N-bound thio-cyanate anion and a μ(2)-bridging thio-urea mol-ecule. The Co(II) atom is coordinated in a distorted octa-hedral fashion within an N(2)S(4) donor set. The bridging thio-urea ligands link Co(II) ions into a polymeric chain extending along [100]. The mol-ecular conformation is stabilized by intra-molecular N-H⋯N hydrogen bonds, which generate S(6) ring motifs. The crystal packing is stabilized by N-H⋯S inter-actions, which connect the chains into a three-dimensional architecture.

Related literature

For a general introduction to thio­cyanato complexes, see: Nardelli et al. (1957 ▶). For the crystal structure of the analogous CdII complex, see: Wang et al. (2002 ▶). For information on the properties of complexes incorporating these ligands, see: Yuan et al. (1997 ▶); Yu et al. (2001 ▶); Machura et al. (2011 ▶). For the use of CoII complexes with mixed S-donor ligands as precursors to CoS, see: Kropidłowska et al. (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Co(NCS)2(CH4N2S)2]

M = 327.33

Triclinic,

a = 3.855 (3) Å

b = 7.585 (2) Å

c = 10.094 (2) Å

α = 92.424 (3)°

β = 98.172 (2)°

γ = 104.166 (2)°

V = 282.4 (2) Å3

Z = 1

Mo Kα radiation

μ = 2.23 mm−1

T = 293 K

0.24 × 0.22 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.591, T max = 0.699

6452 measured reflections

1844 independent reflections

1764 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.052

S = 1.07

1844 reflections

71 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia (1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033193/tk5133sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033193/tk5133Isup2.hkl

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

[Co(NCS)2(CH4N2S)2]	Z = 1
Mr = 327.33	F(000) = 165
Triclinic, P1	Dx = 1.925 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.855 (3) Å	Cell parameters from 2298 reflections
b = 7.585 (2) Å	θ = 2.0–34.1°
c = 10.094 (2) Å	µ = 2.23 mm−1
α = 92.424 (3)°	T = 293 K
β = 98.172 (2)°	Block, brown
γ = 104.166 (2)°	0.24 × 0.22 × 0.16 mm
V = 282.4 (2) Å3

Bruker APEXII CCD diffractometer	1844 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.0 pixels mm-1	θmax = 34.1°, θmin = 2.0°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→10
Tmin = 0.591, Tmax = 0.699	l = −14→15
6452 measured reflections

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)] = 0.019	H-atom parameters constrained
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.0264P)2 + 0.0757P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1844 reflections	Δρmax = 0.61 e Å−3
71 parameters	Δρmin = −0.33 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: 0.203 (7)

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
C1	0.5577 (3)	0.18192 (15)	0.78972 (10)	0.01952 (19)
C2	0.9805 (3)	−0.29358 (15)	0.69572 (11)	0.02016 (19)
N1	0.5889 (3)	0.10262 (13)	0.69282 (9)	0.02280 (18)
N2	0.9447 (3)	−0.19551 (16)	0.80075 (10)	0.0295 (2)
H2A	0.9899	−0.2301	0.8800	0.035*
H2B	0.8759	−0.0966	0.7903	0.035*
N3	1.0858 (3)	−0.44519 (15)	0.71126 (11)	0.0324 (2)
H3A	1.1313	−0.4801	0.7904	0.039*
H3B	1.1091	−0.5092	0.6423	0.039*
S1	0.51233 (9)	0.29477 (5)	0.92362 (3)	0.03241 (9)
S2	0.89332 (7)	−0.22779 (3)	0.53449 (2)	0.01878 (8)
Co	0.5000	0.0000	0.5000	0.01874 (8)

	U11	U22	U33	U12	U13	U23
C1	0.0193 (4)	0.0231 (5)	0.0165 (4)	0.0073 (4)	0.0011 (3)	0.0004 (3)
C2	0.0189 (4)	0.0209 (5)	0.0200 (4)	0.0033 (4)	0.0031 (3)	0.0046 (4)
N1	0.0259 (4)	0.0256 (4)	0.0169 (4)	0.0078 (4)	0.0022 (3)	−0.0016 (3)
N2	0.0430 (6)	0.0313 (5)	0.0173 (4)	0.0147 (4)	0.0056 (4)	0.0040 (4)
N3	0.0484 (6)	0.0269 (5)	0.0256 (5)	0.0173 (5)	0.0027 (4)	0.0072 (4)
S1	0.03586 (17)	0.0469 (2)	0.01841 (14)	0.02104 (14)	0.00223 (11)	−0.00877 (12)
S2	0.02254 (13)	0.01991 (13)	0.01566 (12)	0.00861 (9)	0.00307 (9)	0.00202 (8)
Co	0.02202 (11)	0.02291 (12)	0.01230 (10)	0.00862 (8)	0.00200 (7)	−0.00215 (7)

C1—N1	1.1627 (14)	N3—H3A	0.8600
C1—S1	1.6226 (11)	N3—H3B	0.8600
C2—N2	1.3121 (15)	S2—Co	2.5668 (10)
C2—N3	1.3182 (15)	S2—Coi	2.6231 (14)
C2—S2	1.7338 (11)	Co—N1ii	2.0158 (10)
N1—Co	2.0158 (10)	Co—S2ii	2.5668 (10)
N2—H2A	0.8600	Co—S2iii	2.6231 (14)
N2—H2B	0.8600	Co—S2iv	2.6231 (14)
N1—C1—S1	179.17 (10)	N1—Co—S2ii	83.37 (3)
N2—C2—N3	120.18 (11)	N1ii—Co—S2ii	96.63 (3)
N2—C2—S2	121.31 (9)	N1—Co—S2	96.63 (3)
N3—C2—S2	118.50 (9)	N1ii—Co—S2	83.37 (3)
C1—N1—Co	160.34 (9)	S2ii—Co—S2	180.000 (11)
C2—N2—H2A	120.0	N1—Co—S2iii	88.73 (3)
C2—N2—H2B	120.0	N1ii—Co—S2iii	91.27 (3)
H2A—N2—H2B	120.0	S2ii—Co—S2iii	95.93 (5)
C2—N3—H3A	120.0	S2—Co—S2iii	84.07 (5)
C2—N3—H3B	120.0	N1—Co—S2iv	91.27 (3)
H3A—N3—H3B	120.0	N1ii—Co—S2iv	88.73 (3)
C2—S2—Co	117.06 (4)	S2ii—Co—S2iv	84.07 (5)
C2—S2—Coi	104.64 (4)	S2—Co—S2iv	95.93 (5)
Co—S2—Coi	95.93 (5)	S2iii—Co—S2iv	180.000 (11)
N1—Co—N1ii	180.0
S1—C1—N1—Co	−33 (7)	C2—S2—Co—N1	21.76 (5)
N2—C2—S2—Co	−19.76 (11)	Coi—S2—Co—N1	−88.02 (3)
N3—C2—S2—Co	160.47 (8)	C2—S2—Co—N1ii	−158.24 (5)
N2—C2—S2—Coi	84.92 (10)	Coi—S2—Co—N1ii	91.98 (3)
N3—C2—S2—Coi	−94.85 (10)	C2—S2—Co—S2ii	−117 (100)
C1—N1—Co—N1ii	−140 (100)	Coi—S2—Co—S2ii	133 (100)
C1—N1—Co—S2ii	12.8 (3)	C2—S2—Co—S2iii	109.79 (4)
C1—N1—Co—S2	−167.2 (3)	Coi—S2—Co—S2iii	0.0
C1—N1—Co—S2iii	108.9 (3)	C2—S2—Co—S2iv	−70.21 (4)
C1—N1—Co—S2iv	−71.1 (3)	Coi—S2—Co—S2iv	180.0

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1	0.86	2.26	3.079 (3)	159
N2—H2A···S1v	0.86	2.70	3.461 (3)	148
N3—H3A···S1vi	0.86	2.78	3.483 (3)	140
N3—H3B···S2vii	0.86	2.62	3.456 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1	0.86	2.26	3.079 (3)	159
N2—H2A⋯S1i	0.86	2.70	3.461 (3)	148
N3—H3A⋯S1ii	0.86	2.78	3.483 (3)	140
N3—H3B⋯S2iii	0.86	2.62	3.456 (3)	166

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