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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702065X/ng2260sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680702065X/ng2260Isup2.hkl
Contains datablock I

CCDC reference: 650519

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.040
  • wR factor = 0.081
  • Data-to-parameter ratio = 17.2

checkCIF/PLATON results

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Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4 PLAT480_ALERT_4_C Long H...A H-Bond Reported H12 .. S2 .. 2.98 Ang.
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C26 H24 Cl2 Co1 N2 O8 S2 Atom count from _chemical_formula_moiety: REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.49 From the CIF: _reflns_number_total 3237 Count of symmetry unique reflns 1757 Completeness (_total/calc) 184.23% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1480 Fraction of Friedel pairs measured 0.842 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (9) 0.81 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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).

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

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-\kO]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 m3
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 mm1
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)
Graphite monochromatorRint = 0.064
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 2626
Tmin = 0.782, Tmax = 0.839k = 3232
14081 measured reflectionsl = 1414
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 Å3
188 parametersΔρmin = 0.33 e Å3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
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 Å3
3237 reflectionsΔρmin = 0.33 e Å3
188 parametersAbsolute structure: Flack (1983), with how many Friedel pairs?
1 restraintAbsolute structure 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*
C80.00637 (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)
O10.06217 (15)0.78760 (10)0.3313 (3)0.0570 (8)
O20.06390 (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*
S20.03025 (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, º) 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, z1.
Hydrogen-bond geometry (Å, º) 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: (i) x, y+2, z; (iv) x+1/4, y+7/4, z1/4.

Experimental details

Crystal data
Chemical formula[Co(C8H6ClO3S)2(C10H8N2)(H2O)2]
Mr686.42
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)293
a, b, c (Å)20.129 (4), 25.466 (5), 11.413 (2)
V3)5850 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.96
Crystal size (mm)0.27 × 0.25 × 0.19
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.782, 0.839
No. of measured, independent and
observed [I > 2σ(I)] reflections
14081, 3237, 2728
Rint0.064
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.081, 1.04
No. of reflections3237
No. of parameters188
No. of restraints1
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0254P)2 + 12.1874P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.35, 0.33
Absolute structureFlack (1983), with how many Friedel pairs?
Absolute structure parameter0.021 (18)

Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H12···O1i0.851.872.692 (3)163.6
O4—H12···S2i0.852.983.806 (2)165.0
O4—H11···O2ii0.851.842.651 (3)159.0
Symmetry codes: (i) x+1/4, y+7/4, z1/4; (ii) x, y+2, z.
 

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