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

In the title coordination polymer, [Cd(C₈H₆ClO₃S)₂(C₁₀H₈N₂)(H₂O)₂]_n, the Cd^II atom exists in an octa­hedral coordination environment formed by two carboxylate O atoms from two (4-chloro­phenyl­sulfin­yl)acetate ligands, two N atoms from two bipyridine ligands and two water mol­ecules. The Cd^II atom lies on a twofold rotation axis. Bridging by the bipyridine ligand leads to a linear chain structure, while 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) = 0.006 Å
• R factor = 0.025
• wR factor = 0.062
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.83
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12    ..  S1      ..       3.04 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported O4     ..  S1      ..       3.84 Ang.
PLAT731_ALERT_1_C Bond    Calc   1.475(11), Rep    1.475(5) ......       2.20 su-Ra
              C11  -C12     1.555   1.555

Alert level G
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           27.51
           From the CIF: _reflns_number_total               3370
           Count of symmetry unique reflns         1820
           Completeness (_total/calc)            185.16%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1550
           Fraction of Friedel pairs measured     0.852
           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 Cd1         (2)       2.28
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
   5 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Recently, we reported the crystal structure of diaquabis[(4-nitrophenylsulfinylacetato)(4,4'-bipyridine)zinc(II) (Hou et al. 2007a). We also reported that of diaquabis[(4-chlorophenylsulfinylacetato)(4,4'-bipyridine)cobalt(II) (Hou et al. 2007b); diaquabis[(4-chlorophenylsulfinylacetato)(4,4'-bipyridine)zinc(II) (Hou et al. 2007) and diaquabis[(4-chlorophenylsulfinylacetato)(4,4'-bipyridine)nickel(II) (Su et al. 2007); this paper reports the isostructural cadmium compound.

In the title compound the cadmium bis(4-chlorophenylsulfinylacetate) moiety is bridged by 4,4'-bipyridine into a linear chain (Fig. 1). The Cd^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 isostructural compounds, see: Hou et al. (2007, 2007a,b); Su et al. (2007).

S2. Experimental

(4-Chlorophenylsulfanyl)acetic acid was prepared by the 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. Cadmium nitrate hexahydrate (0.692 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; colorless 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) = 1.2Ueq(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 U_iso(H) = 1.5Ueq(O).

The Flack parameter was refined from 1550 Friedel pairs.

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 atomlabelling 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- κO]cadmium(II)]-µ-4,4'-bipyridine-κ²N:N']

Crystal data

[Cd(C8H6ClO3S)2(C10H8N2)(H2O)2]	F(000) = 2976
Mr = 739.89	Dx = 1.628 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 13606 reflections
a = 25.664 (5) Å	θ = 6.2–55.1°
b = 20.103 (7) Å	µ = 1.09 mm^−1
c = 11.705 (2) Å	T = 293 K
V = 6039 (3) Å^3	Block, colorless
Z = 8	0.22 × 0.21 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3370 independent reflections
Radiation source: fine-focus sealed tube	3214 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −33→33
Tmin = 0.793, Tmax = 0.823	k = −26→26
14361 measured reflections	l = −14→15

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)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 7.9326P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3370 reflections	Δρmax = 0.85 e Å^−3
188 parameters	Δρmin = −0.30 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1550 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

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	0.27829 (11)	0.97188 (15)	1.0099 (3)	0.0389 (7)
C2	0.29867 (13)	0.93630 (16)	0.9191 (3)	0.0469 (7)
H1	0.2841	0.9403	0.8467	0.056*
C3	0.34059 (13)	0.89508 (18)	0.9366 (3)	0.0573 (9)
H2	0.3539	0.8694	0.8773	0.069*
C4	0.36233 (14)	0.89255 (17)	1.0430 (4)	0.0572 (9)
C5	0.34323 (17)	0.9276 (2)	1.1350 (4)	0.0621 (10)
H3	0.3591	0.9249	1.2063	0.074*
C6	0.29992 (14)	0.96660 (19)	1.1179 (3)	0.0545 (8)
H4	0.2852	0.9895	1.1789	0.065*
C7	0.17595 (10)	0.96841 (14)	0.9710 (3)	0.0440 (6)
H5	0.1834	0.9395	0.9067	0.053*
H6	0.1746	0.9413	1.0395	0.053*
C8	0.12325 (12)	1.00291 (16)	0.9529 (2)	0.0380 (8)
C9	−0.03579 (12)	1.03376 (16)	0.7185 (3)	0.0424 (7)
H7	−0.0610	1.0576	0.7583	0.051*
C10	−0.03732 (13)	1.03504 (17)	0.6005 (3)	0.0428 (7)
H8	−0.0632	1.0592	0.5634	0.051*
C11	0.0000	1.0000	0.5360 (7)	0.0386 (15)
C12	0.0000	1.0000	0.4100 (6)	0.0365 (15)
C13	0.04492 (13)	1.0104 (2)	0.3517 (3)	0.0501 (9)
H9	0.0762	1.0168	0.3904	0.060*
C14	0.04330 (13)	1.01123 (18)	0.2342 (4)	0.0497 (8)
H10	0.0738	1.0200	0.1941	0.060*
Cd1	0.0000	1.0000	0.97656 (3)	0.03051 (7)
Cl1	0.41728 (5)	0.84252 (7)	1.06118 (18)	0.1051 (5)
N1	0.0000	1.0000	0.7792 (5)	0.0397 (13)
N2	0.0000	1.0000	0.1761 (5)	0.0363 (12)
O1	0.21608 (10)	1.06206 (14)	1.0980 (3)	0.0711 (8)
O2	0.12289 (9)	1.05949 (13)	0.9125 (3)	0.0610 (6)
O3	0.08505 (7)	0.96899 (10)	0.9828 (2)	0.0439 (4)
O4	−0.03001 (8)	0.88990 (9)	0.9748 (2)	0.0460 (4)
H12	−0.0111	0.8637	0.9356	0.069*
H11	−0.0602	0.8994	0.9497	0.069*
S1	0.22630 (3)	1.02914 (3)	0.98480 (9)	0.04591 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0287 (12)	0.0422 (14)	0.0458 (19)	−0.0016 (11)	−0.0039 (11)	−0.0056 (12)
C2	0.0417 (16)	0.0516 (17)	0.0473 (17)	0.0035 (13)	−0.0068 (13)	−0.0148 (14)
C3	0.0435 (18)	0.0535 (18)	0.075 (2)	0.0086 (15)	0.0005 (16)	−0.0196 (16)
C4	0.0440 (18)	0.0443 (17)	0.083 (3)	0.0054 (14)	−0.0152 (17)	−0.0022 (16)
C5	0.063 (2)	0.058 (2)	0.065 (2)	−0.0025 (18)	−0.0300 (19)	−0.0011 (19)
C6	0.055 (2)	0.062 (2)	0.0466 (19)	0.0023 (16)	−0.0026 (15)	−0.0106 (16)
C7	0.0303 (13)	0.0449 (13)	0.0567 (18)	−0.0001 (10)	0.0022 (14)	−0.0052 (15)
C8	0.0348 (13)	0.0526 (15)	0.027 (2)	0.0024 (12)	−0.0002 (9)	0.0003 (13)
C9	0.0467 (16)	0.0551 (16)	0.0255 (15)	0.0094 (13)	0.0051 (14)	0.0001 (15)
C10	0.0476 (18)	0.0549 (18)	0.0261 (15)	0.0102 (14)	−0.0004 (12)	0.0042 (13)
C11	0.038 (3)	0.051 (3)	0.027 (3)	−0.0046 (18)	0.000	0.000
C12	0.048 (4)	0.050 (3)	0.012 (3)	0.0037 (18)	0.000	0.000
C13	0.0365 (17)	0.089 (3)	0.0252 (16)	−0.0037 (16)	−0.0040 (12)	−0.0114 (15)
C14	0.0384 (16)	0.083 (2)	0.0276 (16)	−0.0046 (14)	0.0050 (13)	−0.0050 (19)
Cd1	0.02765 (11)	0.04510 (12)	0.01878 (10)	0.00082 (12)	0.000	0.000
Cl1	0.0695 (8)	0.0855 (8)	0.1602 (15)	0.0381 (7)	−0.0354 (9)	−0.0021 (9)
N1	0.041 (3)	0.052 (3)	0.026 (4)	−0.0011 (16)	0.000	0.000
N2	0.041 (3)	0.051 (3)	0.016 (3)	0.0030 (15)	0.000	0.000
O1	0.0513 (15)	0.0625 (15)	0.100 (2)	0.0063 (12)	−0.0047 (14)	−0.0428 (15)
O2	0.0376 (12)	0.0706 (15)	0.0746 (17)	0.0064 (11)	0.0094 (11)	0.0252 (13)
O3	0.0305 (9)	0.0614 (11)	0.0398 (11)	0.0023 (8)	0.0009 (10)	0.0052 (11)
O4	0.0456 (11)	0.0459 (10)	0.0464 (11)	0.0043 (8)	−0.0044 (10)	−0.0037 (10)
S1	0.0309 (3)	0.0403 (3)	0.0665 (5)	−0.0002 (3)	0.0026 (4)	−0.0005 (4)

Geometric parameters (Å, º)

C1—C6	1.384 (5)	C10—H8	0.9300
C1—C2	1.384 (4)	C11—C10^i	1.408 (5)
C1—S1	1.787 (3)	C11—C12	1.475 (5)
C2—C3	1.374 (5)	C12—C13^i	1.356 (5)
C2—H1	0.9300	C12—C13	1.356 (5)
C3—C4	1.366 (5)	C13—C14	1.377 (6)
C3—H2	0.9300	C13—H9	0.9300
C4—C5	1.376 (6)	C14—N2	1.322 (5)
C4—Cl1	1.745 (3)	C14—H10	0.9300
C5—C6	1.375 (5)	Cd1—O3^i	2.2712 (19)
C5—H3	0.9300	Cd1—O3	2.2712 (19)
C6—H4	0.9300	Cd1—N1	2.310 (6)
C7—C8	1.535 (4)	Cd1—N2^ii	2.336 (6)
C7—S1	1.785 (3)	Cd1—O4	2.344 (2)
C7—H5	0.9700	Cd1—O4^i	2.344 (2)
C7—H6	0.9700	N1—C9^i	1.345 (5)
C8—O2	1.232 (4)	N2—C14^i	1.322 (5)
C8—O3	1.244 (4)	N2—Cd1^iii	2.336 (6)
C9—N1	1.345 (5)	O1—S1	1.504 (3)
C9—C10	1.382 (5)	O4—H12	0.8500
C9—H7	0.9300	O4—H11	0.8500
C10—C11	1.408 (5)
C6—C1—C2	120.7 (3)	C13^i—C12—C11	120.2 (3)
C6—C1—S1	120.0 (2)	C13—C12—C11	120.2 (3)
C2—C1—S1	119.2 (2)	C12—C13—C14	118.6 (4)
C3—C2—C1	119.5 (3)	C12—C13—H9	120.7
C3—C2—H1	120.2	C14—C13—H9	120.7
C1—C2—H1	120.2	N2—C14—C13	122.5 (4)
C4—C3—C2	118.6 (3)	N2—C14—H10	118.8
C4—C3—H2	120.7	C13—C14—H10	118.8
C2—C3—H2	120.7	O3^i—Cd1—O3	176.31 (13)
C3—C4—C5	123.3 (3)	O3^i—Cd1—N1	91.84 (6)
C3—C4—Cl1	117.6 (3)	O3—Cd1—N1	91.84 (6)
C5—C4—Cl1	119.2 (3)	O3^i—Cd1—N2^ii	88.16 (6)
C6—C5—C4	117.8 (4)	O3—Cd1—N2^ii	88.16 (6)
C6—C5—H3	121.1	N1—Cd1—N2^ii	180.000 (4)
C4—C5—H3	121.1	O3^i—Cd1—O4	86.77 (7)
C5—C6—C1	120.1 (4)	O3—Cd1—O4	93.26 (7)
C5—C6—H4	120.0	N1—Cd1—O4	89.50 (6)
C1—C6—H4	120.0	N2^ii—Cd1—O4	90.50 (6)
C8—C7—S1	110.0 (2)	O3^i—Cd1—O4^i	93.26 (7)
C8—C7—H5	109.7	O3—Cd1—O4^i	86.77 (7)
S1—C7—H5	109.7	N1—Cd1—O4^i	89.50 (6)
C8—C7—H6	109.7	N2^ii—Cd1—O4^i	90.50 (6)
S1—C7—H6	109.7	O4—Cd1—O4^i	179.00 (12)
H5—C7—H6	108.2	C9—N1—C9^i	116.2 (6)
O2—C8—O3	127.4 (3)	C9—N1—Cd1	121.9 (3)
O2—C8—C7	118.5 (3)	C9^i—N1—Cd1	121.9 (3)
O3—C8—C7	114.1 (3)	C14^i—N2—C14	118.1 (6)
N1—C9—C10	123.8 (4)	C14^i—N2—Cd1^iii	120.9 (3)
N1—C9—H7	118.1	C14—N2—Cd1^iii	120.9 (3)
C10—C9—H7	118.1	C8—O3—Cd1	126.71 (19)
C9—C10—C11	120.5 (4)	Cd1—O4—H12	113.7
C9—C10—H8	119.8	Cd1—O4—H11	95.2
C11—C10—H8	119.8	H12—O4—H11	118.2
C10—C11—C10^i	115.2 (6)	O1—S1—C7	104.72 (17)
C10—C11—C12	122.4 (3)	O1—S1—C1	105.57 (16)
C10^i—C11—C12	122.4 (3)	C7—S1—C1	96.59 (14)
C13^i—C12—C13	119.6 (6)

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	1.86	2.710 (3)	175
O4—H12···S1^iv	0.85	3.04	3.841 (2)	159
O4—H11···O2^i	0.85	1.86	2.692 (3)	166

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