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Acta Cryst. (2007). E63, m1838    [ doi:10.1107/S1600536807025299 ]

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

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

Abstract top

In the title coordination polymer, [Zn(C8H6ClO3S)2(C10H8N2)(H2O)2]n, the ZnII atom exists in an octahedral coordination environment that is formed by two carboxylate O atoms from two (4-chlorophenylsulfinyl)acetate ligands, two N atoms from two bipyridine ligands and two water molecules. The ZnII atom lies on a twofold 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

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

The title compound has the zinc bis(4-chlorophenylsulfinylacetate) bridged by 4,4'-bipyridine into a linear chain (Fig. 1). The ZnII 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 the isostructural cobalt compound, see (Hou et al. 2007b). For related literature, see: Hou et al. (2007a); Rigaku (1998); Molecular Structure Corporation & Rigaku (2002); Sheldrick (1997a, 1997b); Nobles & Thompson (1965).

Experimental top

(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 (Nobles & Thompson, 1965). Zinc nitrate hexahydrate (0.592 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.

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).

The Flack parameter was refined from 1371 Friedel pairs.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation &Rigaku, 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 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].
[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]\ zinc(II)]-µ-4,4'-bipyridine-κ2N:N'] top
Crystal data top
[Zn(C8H6ClO3S)2(C10H8N2)(H2O)2]F000 = 2832
Mr = 692.86Dx = 1.558 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation
λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 12841 reflections
a = 20.194 (5) Åθ = 6.3–54.9º
b = 25.528 (8) ŵ = 1.20 mm−1
c = 11.458 (6) ÅT = 293 (2) K
V = 5907 (4) Å3Block, colorless
Z = 80.27 × 0.25 × 0.19 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3142 independent reflections
Radiation source: fine-focus sealed tube2962 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 293(2) Kθmax = 27.5º
ω scansθmin = 3.2º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −26→26
Tmin = 0.738, Tmax = 0.804k = −33→31
14000 measured reflectionsl = −14→12
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.0385P)2 + 0.7396P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.062(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.28 e Å−3
3142 reflectionsΔρmin = −0.17 e Å−3
188 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), from 1371 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.017 (8)
Secondary atom site location: difference Fourier map
Crystal data top
[Zn(C8H6ClO3S)2(C10H8N2)(H2O)2]V = 5907 (4) Å3
Mr = 692.86Z = 8
Orthorhombic, Fdd2Mo Kα
a = 20.194 (5) ŵ = 1.20 mm−1
b = 25.528 (8) ÅT = 293 (2) K
c = 11.458 (6) Å0.27 × 0.25 × 0.19 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3142 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2962 reflections with I > 2σ(I)
Tmin = 0.738, Tmax = 0.804Rint = 0.024
14000 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.062Δρmax = 0.28 e Å−3
S = 1.06Δρmin = −0.17 e Å−3
3142 reflectionsAbsolute structure: Flack (1983), from 1371 Friedel pairs
188 parametersFlack parameter: 0.017 (8)
1 restraint
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
C10.02754 (11)0.72498 (7)0.2397 (2)0.0334 (5)
C20.06452 (12)0.70605 (8)0.1464 (2)0.0413 (5)
H10.06060.72110.07290.050*
C30.10706 (13)0.66457 (8)0.1647 (2)0.0487 (6)
H20.13360.65210.10450.058*
C40.10952 (13)0.64206 (9)0.2733 (3)0.0505 (6)
C50.07313 (15)0.66025 (11)0.3662 (3)0.0561 (7)
H30.07600.64440.43910.067*
C60.03208 (14)0.70286 (10)0.3482 (2)0.0485 (6)
H40.00760.71650.40990.058*
C70.02983 (10)0.82874 (7)0.1969 (2)0.0374 (4)
H50.05760.83060.26580.045*
H60.05790.82130.13020.045*
C8−0.00572 (11)0.88119 (7)0.17876 (17)0.0337 (5)
C90.01985 (13)1.04164 (8)0.4480 (2)0.0437 (5)
H70.03471.07080.40710.052*
C100.01934 (16)1.04353 (10)0.5687 (2)0.0489 (6)
H80.03191.07390.60750.059*
C110.00001.00000.6309 (3)0.0347 (8)
C120.00001.00000.7607 (3)0.0380 (8)
C130.03379 (13)0.96210 (9)0.8246 (2)0.0416 (5)
H90.05670.93570.78610.050*
C140.03333 (11)0.96369 (8)0.9447 (2)0.0405 (5)
H100.05720.93840.98520.049*
Cl10.16118 (5)0.58797 (3)0.29340 (12)0.0958 (3)
N10.00001.00000.3880 (2)0.0313 (6)
N20.00001.00001.0064 (2)0.0342 (6)
O1−0.06247 (10)0.78794 (6)0.32997 (18)0.0598 (5)
O2−0.06317 (9)0.88029 (6)0.14055 (18)0.0539 (5)
O30.02837 (7)0.92075 (5)0.20348 (13)0.0352 (3)
O40.10101 (7)1.02337 (5)0.19763 (13)0.0378 (3)
H120.12421.00610.14910.057*
H110.09971.05580.18050.057*
S1−0.03021 (3)0.777363 (17)0.21386 (5)0.03840 (13)
Zn10.00001.00000.198249 (18)0.02787 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0359 (11)0.0260 (8)0.0384 (13)−0.0028 (7)0.0043 (8)0.0004 (8)
C20.0475 (13)0.0375 (10)0.0390 (11)0.0028 (9)0.0112 (9)0.0060 (9)
C30.0496 (14)0.0409 (11)0.0557 (14)0.0050 (10)0.0141 (11)−0.0017 (11)
C40.0435 (13)0.0381 (11)0.0700 (17)0.0048 (10)−0.0043 (11)0.0100 (11)
C50.0664 (18)0.0572 (14)0.0446 (14)0.0015 (13)0.0001 (12)0.0200 (12)
C60.0589 (15)0.0509 (13)0.0359 (12)0.0054 (11)0.0088 (10)0.0043 (11)
C70.0373 (10)0.0271 (8)0.0478 (12)−0.0029 (7)0.0039 (10)−0.0011 (9)
C80.0440 (12)0.0287 (8)0.0282 (14)0.0033 (8)0.0010 (9)−0.0018 (8)
C90.0696 (15)0.0359 (10)0.0255 (11)−0.0108 (10)−0.0049 (10)0.0047 (9)
C100.0792 (18)0.0401 (12)0.0274 (12)−0.0121 (12)−0.0103 (11)−0.0014 (10)
C110.046 (2)0.0390 (19)0.0190 (18)0.0008 (12)0.0000.000
C120.045 (2)0.043 (2)0.027 (2)−0.0058 (13)0.0000.000
C130.0551 (14)0.0442 (12)0.0255 (11)0.0101 (10)0.0047 (9)−0.0012 (9)
C140.0498 (13)0.0422 (11)0.0295 (12)0.0099 (9)0.0011 (10)0.0037 (9)
Cl10.0835 (6)0.0675 (5)0.1364 (9)0.0378 (5)−0.0058 (6)0.0273 (5)
N10.0389 (16)0.0346 (14)0.0204 (15)0.0012 (9)0.0000.000
N20.0429 (17)0.0363 (15)0.0233 (15)−0.0023 (10)0.0000.000
O10.0569 (11)0.0459 (9)0.0766 (13)0.0038 (8)0.0336 (10)−0.0001 (9)
O20.0546 (11)0.0341 (7)0.0729 (12)0.0044 (7)−0.0229 (9)−0.0095 (8)
O30.0453 (8)0.0272 (6)0.0333 (8)0.0002 (5)−0.0010 (7)−0.0007 (6)
O40.0391 (8)0.0364 (6)0.0380 (8)0.0041 (6)0.0044 (6)0.0040 (6)
S10.0353 (3)0.0278 (2)0.0521 (3)−0.00156 (18)0.0019 (2)−0.0024 (2)
Zn10.03723 (16)0.02579 (13)0.02058 (13)0.00031 (13)0.0000.000
Geometric parameters (Å, °) top
C1—C61.369 (3)C10—H80.9300
C1—C21.390 (3)C11—C10i1.376 (3)
C1—S11.799 (2)C11—C121.487 (3)
C2—C31.380 (3)C12—C13i1.392 (3)
C2—H10.9300C12—C131.392 (3)
C3—C41.371 (4)C13—C141.377 (3)
C3—H20.9300C13—H90.9300
C4—C51.374 (4)C14—N21.346 (3)
C4—Cl11.746 (2)C14—H100.9300
C5—C61.383 (4)N1—C9i1.328 (3)
C5—H30.9300N1—Zn12.174 (3)
C6—H40.9300N2—C14i1.346 (3)
C7—C81.533 (3)N2—Zn1ii2.198 (3)
C7—S11.797 (2)O1—S11.5057 (19)
C7—H50.9700O3—Zn12.1036 (14)
C7—H60.9700O4—Zn12.1254 (15)
C8—O21.240 (3)O4—H120.8499
C8—O31.255 (2)O4—H110.8500
C9—N11.328 (3)Zn1—O3i2.1036 (14)
C9—C101.385 (4)Zn1—O4i2.1254 (15)
C9—H70.9300Zn1—N2iii2.198 (3)
C10—C111.376 (3)
C6—C1—C2121.2 (2)C13i—C12—C11121.74 (16)
C6—C1—S1119.95 (18)C13—C12—C11121.74 (16)
C2—C1—S1118.72 (18)C14—C13—C12120.1 (2)
C3—C2—C1119.0 (2)C14—C13—H9119.9
C3—C2—H1120.5C12—C13—H9119.9
C1—C2—H1120.5N2—C14—C13123.3 (2)
C4—C3—C2118.8 (2)N2—C14—H10118.4
C4—C3—H2120.6C13—C14—H10118.4
C2—C3—H2120.6C9—N1—C9i117.6 (3)
C3—C4—C5122.8 (2)C9—N1—Zn1121.18 (14)
C3—C4—Cl1118.2 (2)C9i—N1—Zn1121.18 (14)
C5—C4—Cl1119.0 (2)C14i—N2—C14116.6 (3)
C4—C5—C6118.1 (2)C14i—N2—Zn1ii121.68 (14)
C4—C5—H3121.0C14—N2—Zn1ii121.68 (14)
C6—C5—H3121.0C8—O3—Zn1128.19 (13)
C1—C6—C5120.0 (2)Zn1—O4—H12112.7
C1—C6—H4120.0Zn1—O4—H11104.1
C5—C6—H4120.0H12—O4—H11111.7
C8—C7—S1109.64 (15)O1—S1—C7104.88 (11)
C8—C7—H5109.7O1—S1—C1105.59 (11)
S1—C7—H5109.7C7—S1—C197.06 (10)
C8—C7—H6109.7O3i—Zn1—O3176.74 (8)
S1—C7—H6109.7O3i—Zn1—O489.52 (6)
H5—C7—H6108.2O3—Zn1—O490.50 (6)
O2—C8—O3127.44 (18)O3i—Zn1—O4i90.50 (6)
O2—C8—C7118.01 (18)O3—Zn1—O4i89.52 (6)
O3—C8—C7114.54 (18)O4—Zn1—O4i179.62 (8)
N1—C9—C10122.9 (2)O3i—Zn1—N188.37 (4)
N1—C9—H7118.6O3—Zn1—N188.37 (4)
C10—C9—H7118.6O4—Zn1—N190.19 (4)
C11—C10—C9119.4 (2)O4i—Zn1—N190.19 (4)
C11—C10—H8120.3O3i—Zn1—N2iii91.63 (4)
C9—C10—H8120.3O3—Zn1—N2iii91.63 (4)
C10—C11—C10i117.7 (3)O4—Zn1—N2iii89.81 (4)
C10—C11—C12121.16 (16)O4i—Zn1—N2iii89.81 (4)
C10i—C11—C12121.16 (16)N1—Zn1—N2iii180.000 (1)
C13i—C12—C13116.5 (3)
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···O1iv0.851.882.706 (2)164
O4—H12···S1iv0.852.993.8217 (18)165
O4—H11···O2i0.851.852.657 (2)158
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···O1i0.851.882.706 (2)164
O4—H12···S1i0.852.993.8217 (18)165
O4—H11···O2ii0.851.852.657 (2)158
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.

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

Hou, Y.-J., Yu, Y.-H., Sun, Z.-Z., Li, B.-Y. & Hou, G.-F. (2007a). Acta Cryst. E63, m1530–?.

Hou, Y.-J., Yu, Y.-H., Sun, Z.-Z., Li, B.-Y. & Hou, G.-F. (2007b). Acta Cryst. E63, m1560–?.

Molecular Structure Corporation & Rigaku (2002). CrystalStructure. Version 3.10. MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA, and Rigaku Corporation, 3-9-12 Akishima, Tokyo, Japan.

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

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

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

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