catena-Poly[[diaqua­bis[(4-chloro­phenyl­sulfin­yl)acetato-κO]cobalt(II)]-μ-4,4′-bipyridine-κ²N:N′]

In the title coordination polymer, [Co(C₈H₆ClO₃S)₂(C₁₀H₈N₂)(H₂O)₂]_n, the Co^II 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 Co^II 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.

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

No syntax errors found



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

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S1. Comment

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 Co^II 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

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

S2. Experimental

(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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.5U_eq(O).

Computing details

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

	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].
	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']

Crystal data

[Co(C8H6ClO3S)2(C10H8N2)(H2O)2]	F(000) = 2808
Mr = 686.42	Dx = 1.559 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 10618 reflections
a = 20.129 (4) Å	θ = 6.3–54.9°
b = 25.466 (5) Å	µ = 0.96 mm^−1
c = 11.413 (2) Å	T = 293 K
V = 5850 (2) Å^3	Block, brown
Z = 8	0.27 × 0.25 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3237 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −26→26
Tmin = 0.782, Tmax = 0.839	k = −32→32
14081 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0254P)^2 + 12.1874P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3237 reflections	Δρmax = 0.35 e Å^−3
188 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.021 (18)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.02753 (18)	0.72535 (12)	0.2402 (3)	0.0328 (8)
C2	0.06450 (19)	0.70613 (13)	0.1485 (3)	0.0388 (8)
H1	0.0606	0.7214	0.0747	0.047*
C3	0.1071 (2)	0.66474 (13)	0.1647 (4)	0.0479 (10)
H2	0.1332	0.6523	0.1035	0.058*
C4	0.1099 (2)	0.64239 (14)	0.2734 (4)	0.0496 (10)
C5	0.0737 (2)	0.66005 (17)	0.3665 (4)	0.0541 (11)
H3	0.0768	0.6440	0.4395	0.065*
C6	0.0322 (2)	0.70276 (15)	0.3487 (3)	0.0469 (10)
H4	0.0074	0.7161	0.4107	0.056*
C7	0.02917 (17)	0.82876 (11)	0.1972 (3)	0.0367 (8)
H5	0.0573	0.8307	0.2661	0.044*
H6	0.0572	0.8214	0.1300	0.044*
C8	−0.00637 (19)	0.88119 (11)	0.1794 (3)	0.0329 (8)
C9	0.0204 (2)	1.04139 (13)	0.4480 (3)	0.0408 (9)
H7	0.0358	1.0706	0.4072	0.049*
C10	0.0198 (2)	1.04325 (15)	0.5685 (4)	0.0463 (10)
H8	0.0329	1.0737	0.6071	0.056*
C11	0.0000	1.0000	0.6319 (4)	0.0331 (13)
C12	0.0000	1.0000	0.7620 (5)	0.0362 (14)
C13	0.0337 (2)	0.96238 (15)	0.8246 (3)	0.0403 (9)
H9	0.0567	0.9359	0.7858	0.048*
C14	0.03323 (19)	0.96414 (13)	0.9455 (3)	0.0391 (9)
H10	0.0574	0.9389	0.9863	0.047*
Cl1	0.16178 (8)	0.58814 (6)	0.29368 (16)	0.0944 (5)
N1	0.0000	1.0000	0.3873 (3)	0.0291 (10)
N2	0.0000	1.0000	1.0066 (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)
O3	0.02768 (11)	0.92078 (8)	0.2029 (2)	0.0332 (5)
O4	0.10051 (11)	1.02305 (8)	0.19801 (19)	0.0357 (5)
H12	0.1238	1.0058	0.1493	0.054*
H11	0.0992	1.0555	0.1808	0.054*
S2	−0.03025 (5)	0.77720 (3)	0.21482 (9)	0.0379 (2)
Co1	0.0000	1.0000	0.19793 (4)	0.02525 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0347 (19)	0.0281 (15)	0.035 (2)	−0.0017 (14)	0.0055 (15)	−0.0014 (15)
C2	0.045 (2)	0.0334 (17)	0.0378 (18)	0.0034 (16)	0.0094 (17)	0.0062 (16)
C3	0.051 (3)	0.0378 (19)	0.055 (2)	0.0070 (17)	0.0152 (19)	−0.0029 (19)
C4	0.043 (2)	0.0368 (19)	0.068 (3)	0.0051 (18)	−0.006 (2)	0.0122 (19)
C5	0.060 (3)	0.060 (3)	0.042 (2)	0.004 (2)	0.001 (2)	0.025 (2)
C6	0.057 (3)	0.048 (2)	0.036 (2)	0.0026 (19)	0.0103 (18)	0.0008 (18)
C7	0.0383 (18)	0.0291 (15)	0.0428 (19)	0.0013 (13)	0.0046 (18)	0.0000 (16)
C8	0.043 (2)	0.0268 (14)	0.028 (2)	−0.0018 (15)	0.0017 (16)	0.0010 (14)
C9	0.065 (3)	0.0351 (18)	0.0219 (18)	−0.0124 (17)	−0.0059 (17)	0.0031 (15)
C10	0.073 (3)	0.036 (2)	0.030 (2)	−0.0120 (19)	−0.0086 (19)	−0.0009 (16)
C11	0.042 (4)	0.045 (3)	0.012 (3)	−0.003 (2)	0.000	0.000
C12	0.051 (4)	0.033 (3)	0.025 (3)	−0.006 (2)	0.000	0.000
C13	0.055 (3)	0.045 (2)	0.0208 (18)	0.0106 (18)	0.0064 (17)	−0.0022 (16)
C14	0.049 (2)	0.0390 (19)	0.029 (2)	0.0093 (16)	0.0014 (18)	0.0023 (16)
Cl1	0.0814 (11)	0.0679 (8)	0.1339 (14)	0.0381 (7)	−0.0058 (9)	0.0272 (9)
N1	0.036 (3)	0.036 (2)	0.015 (2)	0.0017 (17)	0.000	0.000
N2	0.043 (3)	0.037 (2)	0.019 (2)	0.0003 (19)	0.000	0.000
O1	0.0551 (19)	0.0439 (15)	0.072 (2)	0.0013 (13)	0.0340 (16)	−0.0001 (15)
O2	0.0508 (18)	0.0356 (13)	0.0683 (18)	0.0025 (12)	−0.0212 (15)	−0.0091 (12)
O3	0.0443 (13)	0.0252 (10)	0.0300 (11)	−0.0013 (9)	−0.0008 (12)	0.0005 (10)
O4	0.0400 (13)	0.0332 (10)	0.0338 (11)	0.0043 (9)	0.0046 (11)	0.0019 (12)
S2	0.0343 (5)	0.0284 (4)	0.0511 (5)	−0.0009 (3)	0.0013 (4)	−0.0024 (4)
Co1	0.0340 (3)	0.0249 (3)	0.0169 (2)	0.0013 (3)	0.000	0.000

Geometric parameters (Å, º)

C1—C6	1.369 (5)	C10—H8	0.9300
C1—C2	1.374 (5)	C11—C10^i	1.377 (5)
C1—S2	1.783 (3)	C11—C12	1.484 (5)
C2—C3	1.371 (5)	C12—C13	1.375 (4)
C2—H1	0.9300	C12—C13^i	1.375 (4)
C3—C4	1.366 (6)	C13—C14	1.381 (5)
C3—H2	0.9300	C13—H9	0.9300
C4—C5	1.364 (6)	C14—N2	1.330 (4)
C4—Cl1	1.747 (4)	C14—H10	0.9300
C5—C6	1.387 (6)	N1—C9^i	1.326 (4)
C5—H3	0.9300	N1—Co1	2.161 (4)
C6—H4	0.9300	N2—C14^i	1.330 (4)
C7—C8	1.528 (4)	N2—Co1^ii	2.183 (4)
C7—S2	1.787 (3)	O1—S2	1.500 (3)
C7—H5	0.9700	O3—Co1	2.094 (2)
C7—H6	0.9700	O4—Co1	2.107 (2)
C8—O2	1.232 (4)	O4—H12	0.8498
C8—O3	1.248 (4)	O4—H11	0.8502
C9—N1	1.326 (4)	Co1—O3^i	2.094 (2)
C9—C10	1.376 (6)	Co1—O4^i	2.107 (2)
C9—H7	0.9300	Co1—N2^iii	2.183 (4)
C10—C11	1.377 (5)
C6—C1—C2	120.1 (3)	C13—C12—C11	121.3 (2)
C6—C1—S2	120.2 (3)	C13^i—C12—C11	121.3 (2)
C2—C1—S2	119.6 (3)	C12—C13—C14	119.6 (4)
C3—C2—C1	120.6 (3)	C12—C13—H9	120.2
C3—C2—H1	119.7	C14—C13—H9	120.2
C1—C2—H1	119.7	N2—C14—C13	123.4 (3)
C4—C3—C2	118.0 (4)	N2—C14—H10	118.3
C4—C3—H2	121.0	C13—C14—H10	118.3
C2—C3—H2	121.0	C9—N1—C9^i	117.0 (4)
C5—C4—C3	123.2 (4)	C9—N1—Co1	121.5 (2)
C5—C4—Cl1	118.5 (3)	C9^i—N1—Co1	121.5 (2)
C3—C4—Cl1	118.3 (3)	C14^i—N2—C14	116.7 (4)
C4—C5—C6	117.8 (4)	C14^i—N2—Co1^ii	121.6 (2)
C4—C5—H3	121.1	C14—N2—Co1^ii	121.6 (2)
C6—C5—H3	121.1	C8—O3—Co1	128.8 (2)
C1—C6—C5	120.2 (4)	Co1—O4—H12	112.6
C1—C6—H4	119.9	Co1—O4—H11	103.9
C5—C6—H4	119.9	H12—O4—H11	111.7
C8—C7—S2	110.1 (2)	O1—S2—C1	105.45 (17)
C8—C7—H5	109.6	O1—S2—C7	104.87 (16)
S2—C7—H5	109.6	C1—S2—C7	97.23 (16)
C8—C7—H6	109.6	O3^i—Co1—O3	176.87 (13)
S2—C7—H6	109.6	O3^i—Co1—O4^i	90.73 (8)
H5—C7—H6	108.2	O3—Co1—O4^i	89.26 (8)
O2—C8—O3	127.4 (3)	O3^i—Co1—O4	89.26 (8)
O2—C8—C7	117.8 (3)	O3—Co1—O4	90.73 (8)
O3—C8—C7	114.8 (3)	O4^i—Co1—O4	179.95 (15)
N1—C9—C10	123.2 (3)	O3^i—Co1—N1	88.43 (6)
N1—C9—H7	118.4	O3—Co1—N1	88.43 (6)
C10—C9—H7	118.4	O4^i—Co1—N1	89.98 (6)
C9—C10—C11	120.0 (4)	O4—Co1—N1	89.98 (6)
C9—C10—H8	120.0	O3^i—Co1—N2^iii	91.57 (6)
C11—C10—H8	120.0	O3—Co1—N2^iii	91.57 (6)
C10—C11—C10^i	116.6 (5)	O4^i—Co1—N2^iii	90.02 (6)
C10—C11—C12	121.7 (2)	O4—Co1—N2^iii	90.02 (6)
C10^i—C11—C12	121.7 (2)	N1—Co1—N2^iii	180.000 (2)
C13—C12—C13^i	117.3 (5)

Symmetry codes: (i) −x, −y+2, z; (ii) x, y, z+1; (iii) x, y, z−1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H12···O1^iv	0.85	1.87	2.692 (3)	164
O4—H12···S2^iv	0.85	2.98	3.806 (2)	165
O4—H11···O2^i	0.85	1.84	2.651 (3)	159

Symmetry codes: (i) −x, −y+2, z; (iv) x+1/4, −y+7/4, z−1/4.