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Acta Cryst. (2007). E63, m1560    [ doi:10.1107/S160053680702065X ]

catena-Poly[[diaquabis[(4-chlorophenylsulfinyl)acetato-[kappa]O]cobalt(II)]-[mu]-4,4'-bipyridine-[kappa]2N:N']

Y.-J. Hou, Y.-H. Yu, Z.-Z. Sun, B.-Y. Li and G.-F. Hou

Abstract top

In the title coordination polymer, [Co(C8H6ClO3S)2(C10H8N2)(H2O)2]n, the CoII atom exists in an octahedral coordination environment formed by two carboxylate O atoms from two (4-chlorophenylsulfinyl)acetate ligands, two N atoms from bipyridine ligands and two water molecules. The CoII atom lies on a twofold rotation axis. Bridging by the bipyridine ligand leads to a linear chain structure, and intermolecular O-H...O hydrogen bonds link the chains into a three-dimensional network.

Comment top

4,4'-Bipyridine and organic aromatic carboxylic acid ligands are often used to bridge metal atoms and these compounds can demonstrate various network topologies (Ghosh et al., 2005). The title compound, (I), is a cobalt(II) 4-chlorophenylsulfinylacetate that is bridged by 4,4'-bipyridine into a linear chain. The CoII atom shows an all-trans octahedral coordination. The chains are connected into a three-dimensional network via intermolecular O—H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For related literature, see: Ghosh et al. (2005); Nobles & Thompson (1965).

Experimental top

(4-Chlorophenylsulfanyl)acetic acid was prepared by nucleophilic reaction of chloroacetic acid and 4-chlorothiophenol under basic conditions. It was then oxidized using 30% aqueous hydrogen peroxide in acetic anhydride solution to produce 4-chlorophenylsulfinyl acetic acid (Nobles & Thompson, 1965). Cobalt nitrate hexahydrate (0.582 g, 2 mmol), 4,4'-bipyridine (0.312 g, 2 mmol) and 4-chlorophenylsulfinyl acetic acid (0.437 g, 2 mmol) were dissolved in water and the pH was adjusted to 6 with 0.01 M sodium hydroxide. Pink crystals separated from the filtered solution after several days.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic C) or C—H = 0.97 Å (methylene C), and with Uiso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H = 0.85 Å and with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Part of the polymeric structure of the title complex, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as spheres of arbitrary radii. [Symmetry codes: (I) -x, -y + 2, z; (II) x, y,z - 1; (III) -x, -y + 2, z - 1; (IV) x, y, z + 1].
[Figure 2] Fig. 2. A partial packing plot of (I). Dashed lines indicate the hydrogen-bonding interactions. H atoms not involved in hydrogen bonds have been omitted.
catena-Poly[[[diaquabis[(4-chlorophenylsulfinyl)acetato-\ κO]cobalt(II)]-µ-4,4'-bipyridine-κ2N:N'] top
Crystal data top
[Co(C8H6ClO3S)2(C10H8N2)(H2O)2]F(000) = 2808
Mr = 686.42Dx = 1.559 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 10618 reflections
a = 20.129 (4) Åθ = 6.3–54.9°
b = 25.466 (5) ŵ = 0.96 mm−1
c = 11.413 (2) ÅT = 293 K
V = 5850 (2) Å3Block, brown
Z = 80.27 × 0.25 × 0.19 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3237 independent reflections
Radiation source: fine-focus sealed tube2728 reflections with I > 2σ(I)
graphiteRint = 0.064
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −26→26
Tmin = 0.782, Tmax = 0.839k = −32→32
14081 measured reflectionsl = −14→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.081 w = 1/[σ2(Fo2) + (0.0254P)2 + 12.1874P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3237 reflectionsΔρmax = 0.35 e Å−3
188 parametersΔρmin = −0.33 e Å−3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.021 (18)
Crystal data top
[Co(C8H6ClO3S)2(C10H8N2)(H2O)2]V = 5850 (2) Å3
Mr = 686.42Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 20.129 (4) ŵ = 0.96 mm−1
b = 25.466 (5) ÅT = 293 K
c = 11.413 (2) Å0.27 × 0.25 × 0.19 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3237 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2728 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.839Rint = 0.064
14081 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.081 w = 1/[σ2(Fo2) + (0.0254P)2 + 12.1874P]
where P = (Fo2 + 2Fc2)/3
S = 1.04Δρmax = 0.35 e Å−3
3237 reflectionsΔρmin = −0.33 e Å−3
188 parametersAbsolute structure: Flack (1983), with how many Friedel pairs?
1 restraintFlack parameter: −0.021 (18)
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.02753 (18)0.72535 (12)0.2402 (3)0.0328 (8)
C20.06450 (19)0.70613 (13)0.1485 (3)0.0388 (8)
H10.06060.72140.07470.047*
C30.1071 (2)0.66474 (13)0.1647 (4)0.0479 (10)
H20.13320.65230.10350.058*
C40.1099 (2)0.64239 (14)0.2734 (4)0.0496 (10)
C50.0737 (2)0.66005 (17)0.3665 (4)0.0541 (11)
H30.07680.64400.43950.065*
C60.0322 (2)0.70276 (15)0.3487 (3)0.0469 (10)
H40.00740.71610.41070.056*
C70.02917 (17)0.82876 (11)0.1972 (3)0.0367 (8)
H50.05730.83070.26610.044*
H60.05720.82140.13000.044*
C8−0.00637 (19)0.88119 (11)0.1794 (3)0.0329 (8)
C90.0204 (2)1.04139 (13)0.4480 (3)0.0408 (9)
H70.03581.07060.40720.049*
C100.0198 (2)1.04325 (15)0.5685 (4)0.0463 (10)
H80.03291.07370.60710.056*
C110.00001.00000.6319 (4)0.0331 (13)
C120.00001.00000.7620 (5)0.0362 (14)
C130.0337 (2)0.96238 (15)0.8246 (3)0.0403 (9)
H90.05670.93590.78580.048*
C140.03323 (19)0.96414 (13)0.9455 (3)0.0391 (9)
H100.05740.93890.98630.047*
Cl10.16178 (8)0.58814 (6)0.29368 (16)0.0944 (5)
N10.00001.00000.3873 (3)0.0291 (10)
N20.00001.00001.0066 (3)0.0330 (11)
O1−0.06217 (15)0.78760 (10)0.3313 (3)0.0570 (8)
O2−0.06390 (14)0.88010 (10)0.1425 (3)0.0515 (7)
O30.02768 (11)0.92078 (8)0.2029 (2)0.0332 (5)
O40.10051 (11)1.02305 (8)0.19801 (19)0.0357 (5)
H120.12381.00580.14930.054*
H110.09921.05550.18080.054*
S2−0.03025 (5)0.77720 (3)0.21482 (9)0.0379 (2)
Co10.00001.00000.19793 (4)0.02525 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0347 (19)0.0281 (15)0.035 (2)−0.0017 (14)0.0055 (15)−0.0014 (15)
C20.045 (2)0.0334 (17)0.0378 (18)0.0034 (16)0.0094 (17)0.0062 (16)
C30.051 (3)0.0378 (19)0.055 (2)0.0070 (17)0.0152 (19)−0.0029 (19)
C40.043 (2)0.0368 (19)0.068 (3)0.0051 (18)−0.006 (2)0.0122 (19)
C50.060 (3)0.060 (3)0.042 (2)0.004 (2)0.001 (2)0.025 (2)
C60.057 (3)0.048 (2)0.036 (2)0.0026 (19)0.0103 (18)0.0008 (18)
C70.0383 (18)0.0291 (15)0.0428 (19)0.0013 (13)0.0046 (18)0.0000 (16)
C80.043 (2)0.0268 (14)0.028 (2)−0.0018 (15)0.0017 (16)0.0010 (14)
C90.065 (3)0.0351 (18)0.0219 (18)−0.0124 (17)−0.0059 (17)0.0031 (15)
C100.073 (3)0.036 (2)0.030 (2)−0.0120 (19)−0.0086 (19)−0.0009 (16)
C110.042 (4)0.045 (3)0.012 (3)−0.003 (2)0.0000.000
C120.051 (4)0.033 (3)0.025 (3)−0.006 (2)0.0000.000
C130.055 (3)0.045 (2)0.0208 (18)0.0106 (18)0.0064 (17)−0.0022 (16)
C140.049 (2)0.0390 (19)0.029 (2)0.0093 (16)0.0014 (18)0.0023 (16)
Cl10.0814 (11)0.0679 (8)0.1339 (14)0.0381 (7)−0.0058 (9)0.0272 (9)
N10.036 (3)0.036 (2)0.015 (2)0.0017 (17)0.0000.000
N20.043 (3)0.037 (2)0.019 (2)0.0003 (19)0.0000.000
O10.0551 (19)0.0439 (15)0.072 (2)0.0013 (13)0.0340 (16)−0.0001 (15)
O20.0508 (18)0.0356 (13)0.0683 (18)0.0025 (12)−0.0212 (15)−0.0091 (12)
O30.0443 (13)0.0252 (10)0.0300 (11)−0.0013 (9)−0.0008 (12)0.0005 (10)
O40.0400 (13)0.0332 (10)0.0338 (11)0.0043 (9)0.0046 (11)0.0019 (12)
S20.0343 (5)0.0284 (4)0.0511 (5)−0.0009 (3)0.0013 (4)−0.0024 (4)
Co10.0340 (3)0.0249 (3)0.0169 (2)0.0013 (3)0.0000.000
Geometric parameters (Å, °) top
C1—C61.369 (5)C10—H80.9300
C1—C21.374 (5)C11—C10i1.377 (5)
C1—S21.783 (3)C11—C121.484 (5)
C2—C31.371 (5)C12—C131.375 (4)
C2—H10.9300C12—C13i1.375 (4)
C3—C41.366 (6)C13—C141.381 (5)
C3—H20.9300C13—H90.9300
C4—C51.364 (6)C14—N21.330 (4)
C4—Cl11.747 (4)C14—H100.9300
C5—C61.387 (6)N1—C9i1.326 (4)
C5—H30.9300N1—Co12.161 (4)
C6—H40.9300N2—C14i1.330 (4)
C7—C81.528 (4)N2—Co1ii2.183 (4)
C7—S21.787 (3)O1—S21.500 (3)
C7—H50.9700O3—Co12.094 (2)
C7—H60.9700O4—Co12.107 (2)
C8—O21.232 (4)O4—H120.8498
C8—O31.248 (4)O4—H110.8502
C9—N11.326 (4)Co1—O3i2.094 (2)
C9—C101.376 (6)Co1—O4i2.107 (2)
C9—H70.9300Co1—N2iii2.183 (4)
C10—C111.377 (5)
C6—C1—C2120.1 (3)C13—C12—C11121.3 (2)
C6—C1—S2120.2 (3)C13i—C12—C11121.3 (2)
C2—C1—S2119.6 (3)C12—C13—C14119.6 (4)
C3—C2—C1120.6 (3)C12—C13—H9120.2
C3—C2—H1119.7C14—C13—H9120.2
C1—C2—H1119.7N2—C14—C13123.4 (3)
C4—C3—C2118.0 (4)N2—C14—H10118.3
C4—C3—H2121.0C13—C14—H10118.3
C2—C3—H2121.0C9—N1—C9i117.0 (4)
C5—C4—C3123.2 (4)C9—N1—Co1121.5 (2)
C5—C4—Cl1118.5 (3)C9i—N1—Co1121.5 (2)
C3—C4—Cl1118.3 (3)C14i—N2—C14116.7 (4)
C4—C5—C6117.8 (4)C14i—N2—Co1ii121.6 (2)
C4—C5—H3121.1C14—N2—Co1ii121.6 (2)
C6—C5—H3121.1C8—O3—Co1128.8 (2)
C1—C6—C5120.2 (4)Co1—O4—H12112.6
C1—C6—H4119.9Co1—O4—H11103.9
C5—C6—H4119.9H12—O4—H11111.7
C8—C7—S2110.1 (2)O1—S2—C1105.45 (17)
C8—C7—H5109.6O1—S2—C7104.87 (16)
S2—C7—H5109.6C1—S2—C797.23 (16)
C8—C7—H6109.6O3i—Co1—O3176.87 (13)
S2—C7—H6109.6O3i—Co1—O4i90.73 (8)
H5—C7—H6108.2O3—Co1—O4i89.26 (8)
O2—C8—O3127.4 (3)O3i—Co1—O489.26 (8)
O2—C8—C7117.8 (3)O3—Co1—O490.73 (8)
O3—C8—C7114.8 (3)O4i—Co1—O4179.95 (15)
N1—C9—C10123.2 (3)O3i—Co1—N188.43 (6)
N1—C9—H7118.4O3—Co1—N188.43 (6)
C10—C9—H7118.4O4i—Co1—N189.98 (6)
C9—C10—C11120.0 (4)O4—Co1—N189.98 (6)
C9—C10—H8120.0O3i—Co1—N2iii91.57 (6)
C11—C10—H8120.0O3—Co1—N2iii91.57 (6)
C10—C11—C10i116.6 (5)O4i—Co1—N2iii90.02 (6)
C10—C11—C12121.7 (2)O4—Co1—N2iii90.02 (6)
C10i—C11—C12121.7 (2)N1—Co1—N2iii180.000 (2)
C13—C12—C13i117.3 (5)
Symmetry codes: (i) −x, −y+2, z; (ii) x, y, z+1; (iii) x, y, z−1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H12···O1iv0.851.872.692 (3)164
O4—H12···S2iv0.852.983.806 (2)165
O4—H11···O2i0.851.842.651 (3)159
Symmetry codes: (iv) x+1/4, −y+7/4, z−1/4; (i) −x, −y+2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H12···O1i0.851.872.692 (3)164
O4—H12···S2i0.852.983.806 (2)165
O4—H11···O2ii0.851.842.651 (3)159
Symmetry codes: (i) x+1/4, −y+7/4, z−1/4; (ii) −x, −y+2, z.
references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Ghosh, S. K., Ribas, J. & Bharadwaj, P. K. (2005). Cryst. Growth Des. 5, 623–629.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Nobles, W. L. & Thompson, B. B. (1965). J. Pharm. Sci. 54, 709–713.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.