Monoclinic polymorph of trans-tetra-aquabis-[(4-pyridylsulfanyl)-acetato-κN]cobalt(II).

The crystal structure of the title compound, [Co(C(7)H(6)NO(2)S)(2)(H(2)O)(4)], is a polymorph of the structure first reported by Du, Zhao & Wang [(2004). Dalton Trans, pp. 2065-2072]. The asymmetric unit of the title compound contains one half-mol-ecule; the Co(II) atom lies on an inversion centre in a distorted octa-hedral geometry coordinated by two N atoms of the pyridine rings of the 4-pyridylthio-acetate anions and four O atoms of water mol-ecules. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules, forming a three-dimensional network.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Chiang et al. (1993 ▶); Du et al. (2004 ▶); Du & Li (2006 ▶); Kondo et al. (2002 ▶); For related structures, see: Fang et al. (2004 ▶); Zhang et al. (2004 ▶).

Experimental

Crystal data

[Co(n class="CellLine">C7H6NO2S)2(H2O)4]

M = 467.37

Monoclinic,

a = 12.173 (1) Å

b = 10.479 (1) Å

c = 7.523 (2) Å

β = 106.78 (3)°

V = 918.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.21 mm−1

T = 293 (2) K

0.45 × 0.40 × 0.30 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XEMP; Siemens, 1994 ▶) T min = 0.608, T max = 0.684

3491 measured reflections

2651 independent reflections

2283 reflections with I > 2σ(I)

R int = 0.024

3 standard reflections every 97 reflections intensity decay: 2.0%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.102

S = 1.37

2651 reflections

125 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.37 e Å−3

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCANS; data reduction: XSCANS; 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: enCIFer (Allen et al. 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023593/ez2135sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023593/ez2135Isup2.hkl

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

[Co(C7H6NO2S)2(H2O)4]	F000 = 482
Mr = 467.37	Dx = 1.689 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.173 (1) Å	θ = 1.7–7.9º
b = 10.479 (1) Å	µ = 1.21 mm−1
c = 7.523 (2) Å	T = 293 (2) K
β = 106.78 (3)º	Block, pink
V = 918.8 (3) Å3	0.45 × 0.40 × 0.30 mm
Z = 2

Siemens P4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 30.0º
Monochromator: graphite	θmin = 1.8º
T = 293(2) K	h = −17→16
2θ/ω scans	k = −14→1
Absorption correction: ψ scan(XEMP; Siemens, 1994)	l = −1→10
Tmin = 0.608, Tmax = 0.684	3 standard reflections
3491 measured reflections	every 97 reflections
2651 independent reflections	intensity decay: 2.0%
2283 reflections with I > 2σ(I)

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.0291P)2 + 0.3487P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max = 0.001
S = 1.37	Δρmax = 0.41 e Å−3
2651 reflections	Δρmin = −0.37 e Å−3
125 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.073 (6)
Secondary atom site location: difference Fourier map

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
Co1	0.5000	0.5000	0.0000	0.01988 (13)
S1	1.03489 (4)	0.69603 (5)	0.41990 (8)	0.03026 (16)
O1	1.27843 (14)	0.69566 (16)	0.5784 (2)	0.0379 (4)
O2	1.32163 (14)	0.52026 (19)	0.4432 (3)	0.0413 (4)
O1W	0.56051 (12)	0.31434 (14)	0.0783 (2)	0.0303 (3)
H1W	0.5952	0.2790	0.0135	0.046*
H2W	0.5996	0.3114	0.1871	0.046*
O2W	0.48936 (14)	0.5278 (2)	0.2660 (2)	0.0386 (4)
H3W	0.5470	0.5169	0.3536	0.058*
H4W	0.4300	0.5267	0.2967	0.058*
N1	0.67362 (13)	0.57244 (16)	0.0968 (2)	0.0246 (3)
C1	1.25327 (16)	0.6025 (2)	0.4709 (3)	0.0294 (4)
C2	1.12871 (16)	0.5827 (2)	0.3577 (3)	0.0296 (4)
H2A	1.1051	0.4969	0.3782	0.036*
H2B	1.1223	0.5915	0.2267	0.036*
C3	0.76428 (16)	0.50244 (19)	0.0894 (3)	0.0249 (4)
H3	0.7508	0.4274	0.0205	0.030*
C4	0.87692 (16)	0.5353 (2)	0.1785 (3)	0.0257 (4)
H4	0.9369	0.4834	0.1686	0.031*
C5	0.89935 (15)	0.64675 (19)	0.2828 (3)	0.0228 (4)
C6	0.80572 (17)	0.7236 (2)	0.2835 (3)	0.0305 (4)
H6	0.8171	0.8014	0.3458	0.037*
C7	0.69607 (17)	0.6831 (2)	0.1909 (3)	0.0314 (5)
H7	0.6346	0.7350	0.1938	0.038*

	U11	U22	U33	U12	U13	U23
Co1	0.01396 (18)	0.0244 (2)	0.02025 (19)	0.00132 (12)	0.00333 (12)	−0.00054 (13)
S1	0.0187 (2)	0.0350 (3)	0.0329 (3)	−0.00349 (18)	0.00085 (18)	−0.0080 (2)
O1	0.0261 (7)	0.0401 (9)	0.0392 (9)	−0.0061 (7)	−0.0036 (6)	0.0038 (7)
O2	0.0210 (7)	0.0621 (12)	0.0403 (9)	0.0061 (7)	0.0078 (6)	0.0027 (8)
O1W	0.0248 (7)	0.0294 (7)	0.0337 (8)	0.0049 (6)	0.0034 (6)	0.0022 (6)
O2W	0.0234 (7)	0.0702 (12)	0.0225 (7)	0.0067 (7)	0.0068 (6)	−0.0021 (7)
N1	0.0169 (7)	0.0273 (8)	0.0281 (8)	0.0001 (6)	0.0041 (6)	−0.0015 (6)
C1	0.0168 (8)	0.0434 (12)	0.0263 (9)	−0.0039 (8)	0.0034 (7)	0.0109 (9)
C2	0.0172 (8)	0.0392 (11)	0.0297 (10)	0.0010 (7)	0.0026 (7)	−0.0015 (8)
C3	0.0189 (8)	0.0261 (9)	0.0287 (9)	−0.0022 (7)	0.0049 (7)	−0.0042 (8)
C4	0.0169 (8)	0.0272 (9)	0.0317 (10)	0.0009 (7)	0.0050 (7)	−0.0023 (8)
C5	0.0173 (8)	0.0266 (9)	0.0230 (8)	−0.0013 (6)	0.0033 (6)	0.0005 (7)
C6	0.0226 (9)	0.0286 (10)	0.0382 (11)	−0.0003 (7)	0.0053 (8)	−0.0108 (8)
C7	0.0197 (9)	0.0307 (10)	0.0416 (12)	0.0037 (7)	0.0053 (8)	−0.0067 (9)

Co1—O2Wi	2.0632 (16)	N1—C3	1.340 (2)
Co1—O2W	2.0632 (16)	N1—C7	1.345 (3)
Co1—O1Wi	2.1034 (15)	C1—C2	1.524 (3)
Co1—O1W	2.1034 (15)	C2—H2A	0.9700
Co1—N1i	2.1644 (16)	C2—H2B	0.9700
Co1—N1	2.1644 (16)	C3—C4	1.385 (3)
S1—C5	1.7523 (19)	C3—H3	0.9300
S1—C2	1.800 (2)	C4—C5	1.389 (3)
O1—C1	1.248 (3)	C4—H4	0.9300
O2—C1	1.257 (3)	C5—C6	1.397 (3)
O1W—H1W	0.8200	C6—C7	1.382 (3)
O1W—H2W	0.8200	C6—H6	0.9300
O2W—H3W	0.8200	C7—H7	0.9300
O2W—H4W	0.8200
O2Wi—Co1—O2W	180.0	O1—C1—O2	126.42 (19)
O2Wi—Co1—O1Wi	88.52 (7)	O1—C1—C2	119.1 (2)
O2W—Co1—O1Wi	91.48 (7)	O2—C1—C2	114.4 (2)
O2Wi—Co1—O1W	91.48 (7)	C1—C2—S1	111.63 (16)
O2W—Co1—O1W	88.52 (7)	C1—C2—H2A	109.3
O1Wi—Co1—O1W	180.0	S1—C2—H2A	109.3
O2Wi—Co1—N1i	87.28 (7)	C1—C2—H2B	109.3
O2W—Co1—N1i	92.72 (7)	S1—C2—H2B	109.3
O1Wi—Co1—N1i	90.07 (6)	H2A—C2—H2B	108.0
O1W—Co1—N1i	89.93 (6)	N1—C3—C4	123.78 (18)
O2Wi—Co1—N1	92.72 (7)	N1—C3—H3	118.1
O2W—Co1—N1	87.28 (7)	C4—C3—H3	118.1
O1Wi—Co1—N1	89.93 (6)	C3—C4—C5	119.23 (18)
O1W—Co1—N1	90.07 (6)	C3—C4—H4	120.4
N1i—Co1—N1	180.0	C5—C4—H4	120.4
C5—S1—C2	102.29 (10)	C4—C5—C6	117.35 (17)
Co1—O1W—H1W	116.8	C4—C5—S1	125.34 (15)
Co1—O1W—H2W	111.7	C6—C5—S1	117.27 (15)
H1W—O1W—H2W	109.0	C7—C6—C5	119.40 (19)
Co1—O2W—H3W	118.7	C7—C6—H6	120.3
Co1—O2W—H4W	125.3	C5—C6—H6	120.3
H3W—O2W—H4W	113.0	N1—C7—C6	123.38 (18)
C3—N1—C7	116.71 (16)	N1—C7—H7	118.3
C3—N1—Co1	122.00 (13)	C6—C7—H7	118.3
C7—N1—Co1	120.65 (13)
O2Wi—Co1—N1—C3	−59.79 (17)	Co1—N1—C3—C4	−168.13 (16)
O2W—Co1—N1—C3	120.21 (17)	N1—C3—C4—C5	0.2 (3)
O1Wi—Co1—N1—C3	−148.31 (17)	C3—C4—C5—C6	−3.3 (3)
O1W—Co1—N1—C3	31.69 (17)	C3—C4—C5—S1	174.30 (16)
O2Wi—Co1—N1—C7	129.63 (17)	C2—S1—C5—C4	8.6 (2)
O2W—Co1—N1—C7	−50.37 (17)	C2—S1—C5—C6	−173.75 (17)
O1Wi—Co1—N1—C7	41.12 (17)	C4—C5—C6—C7	3.5 (3)
O1W—Co1—N1—C7	−138.88 (17)	S1—C5—C6—C7	−174.29 (18)
O1—C1—C2—S1	−5.4 (3)	C3—N1—C7—C6	−2.6 (3)
O2—C1—C2—S1	175.01 (16)	Co1—N1—C7—C6	168.50 (19)
C5—S1—C2—C1	−176.55 (15)	C5—C6—C7—N1	−0.6 (4)
C7—N1—C3—C4	2.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1ii	0.82	2.05	2.849 (2)	163
O1W—H2W···O1iii	0.82	1.95	2.757 (2)	167
O2W—H3W···O2iii	0.82	1.91	2.725 (2)	176
O2W—H4W···O2iv	0.82	1.95	2.743 (2)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O1i	0.82	2.05	2.849 (2)	163
O1W—H2W⋯O1ii	0.82	1.95	2.757 (2)	167
O2W—H3W⋯O2ii	0.82	1.91	2.725 (2)	176
O2W—H4W⋯O2iii	0.82	1.95	2.743 (2)	163

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