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Acta Cryst. (2007). E63, m1530    [ doi:10.1107/S1600536807020260 ]

catena-Poly[[diaquabis[(4-nitrophenylsulfinyl)acetato-[kappa]O]zinc(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, [Zn(C8H6NO5S)2(C10H8N2)(H2O)2]n, each ZnII ion is in a slightly distorted octahedral coordination environment, formed by two carboxylate O atoms from two (4-nitrophenylsulfinyl)acetate ligands, two N atoms from bipyridine ligands and two water molecules. The ZnII ions and the bipryidine ligands lie on crystallographic twofold axes with the ZnII ions linked by bipyridine ligands into a one-dimensional chain structure. In the crystal structure, intermolecular O-H...O hydrogen bonds link one-dimensional chains into a three-dimensional network.

Comment top

4,4'-Bipyridine and organic aromatic carboxylic acid ligands are often used in syntheses to bridge metal atoms and these compound can demonstrate fascinating network topologies and potential application in the field of host–guest chemistry, ion exchange and catalysis (Ghosh et al., 2005). Simple carboxylic acids containing the 4-nitrophenyl group exhibit a variety of supramolecular aggregation patterns (Glidewell et al., 2002). Recently, our attention has been focused on 4-nitrophenylsulfinyl acetic acid, whose crystal structure has been reported previously (Glidewell et al., 2003).

Complex(I) consists of linear chains formed through 4,4'-bipy ligands linking six-coordinate ZnII ions (Fig. 1). The ZnII ion has slightly distorted octahedral geometry. Two N donors of two 4,4'-bipy ligands and two coordinated water molecules lie in the equatorial plane, while two O-atom donors of two (4-nitrophenylsulfinyl)acetate ligands are in the axial positions.

These one-dimensional chains are connected into a three dimensional network via intermolecular O—H···O hydrogen bonds(Table 1),(Fig. 2).

Related literature top

For synthetic background, see: Ghosh et al. (2005), and for previously published structures related to the topic, see: Glidewell et al. (2002, 2003). For preparation details, see: Nobles & Thompson (1965).

Experimental top

(4-Nitrophenylsulfanyl)acetic acid was prepared by a nucleophilic reaction of chloroacetic acid and 4-nitrothiophenol under basic conditions. (4-nitrophenylsulfanyl)acetic acid was then oxidized using 30% aqueous hydrogen peroxide in acetic anhydride solution, producing 4-nitrophenylsulfinyl acetic acid (Nobles & Thompson, 1965). Zinc nitrate hexahydrate (0.586 g, 2 mmol) and (4-nitrophenylsulfinyl)acetic acid (0.458 g, 2 mmol) and 4,4'-bipyridine (0.312 g, 2 mmol) were dissolved in water and the pH was adjusted to 6 with 0.01M 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, withwith 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 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 donor to acceptor non-bonded contacts invloved in hydrogen bonding. H atoms have been omitted.
catena-Poly[[diaquabis[(4-nitrophenylsulfinyl)acetato-κO]zinc(II)]- µ-4,4'-bipyridine-κ2N:N'] top
Crystal data top
[Zn(C8H6NO5S)2(C10H8N2)(H2O)2]F(000) = 2928
Mr = 713.98Dx = 1.604 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 12942 reflections
a = 20.079 (4) Åθ = 6.3–54.9°
b = 25.646 (5) ŵ = 1.04 mm−1
c = 11.485 (2) ÅT = 293 K
V = 5914 (2) Å3Block, colourless
Z = 80.28 × 0.23 × 0.20 mm
Data collection top
Rigaku RAXIS-RAPID
diffractometer		3335 independent reflections
Radiation source: fine-focus sealed tube3138 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −26→26
Tmin = 0.761, Tmax = 0.822k = −33→33
14073 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)] = 0.029H-atom parameters constrained
wR(F2) = 0.077 w = 1/[σ2(Fo2) + (0.047P)2 + 4.1913P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.005
3335 reflectionsΔρmax = 0.55 e Å−3
206 parametersΔρmin = −0.31 e Å−3
13 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.022 (14)
Crystal data top
[Zn(C8H6NO5S)2(C10H8N2)(H2O)2]V = 5914 (2) Å3
Mr = 713.98Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 20.079 (4) ŵ = 1.04 mm−1
b = 25.646 (5) ÅT = 293 K
c = 11.485 (2) Å0.28 × 0.23 × 0.20 mm
Data collection top
Rigaku RAXIS-RAPID
diffractometer		3335 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3138 reflections with I > 2σ(I)
Tmin = 0.761, Tmax = 0.822Rint = 0.027
14073 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.077Δρmax = 0.55 e Å−3
S = 1.07Δρmin = −0.31 e Å−3
3335 reflectionsAbsolute structure: Flack (1983)
206 parametersFlack parameter: 0.022 (14)
13 restraints
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
C10.02856 (17)0.72739 (13)0.5181 (3)0.0284 (7)
C20.0666 (2)0.70549 (15)0.4295 (3)0.0362 (8)
H10.06470.71890.35440.043*
C30.10728 (19)0.66355 (14)0.4545 (3)0.0374 (9)
H20.13340.64840.39690.045*
C40.1084 (2)0.64463 (14)0.5672 (3)0.0338 (8)
C50.0714 (2)0.66611 (15)0.6570 (3)0.0398 (9)
H30.07330.65240.73190.048*
C60.0315 (2)0.70887 (15)0.6312 (3)0.0364 (8)
H40.00690.72500.68970.044*
C70.03217 (17)0.83002 (12)0.4745 (4)0.0310 (7)
H50.05900.83100.54480.037*
H60.06140.82320.40910.037*
C8−0.00307 (18)0.88235 (12)0.4576 (3)0.0280 (7)
C90.0212 (2)1.04111 (14)0.7267 (4)0.0370 (8)
H70.03691.06990.68600.044*
C100.0210 (2)1.04293 (17)0.8483 (4)0.0414 (9)
H80.03491.07290.88690.050*
C110.00001.00000.9105 (5)0.0300 (13)
C120.00001.00001.0404 (5)0.0359 (14)
C130.0321 (2)0.96088 (16)1.1036 (4)0.0383 (9)
H90.05360.93381.06500.046*
C140.03179 (19)0.96264 (14)1.2234 (4)0.0355 (8)
H100.05450.93691.26430.043*
N10.1489 (2)0.59871 (17)0.5925 (4)0.0506 (9)
N20.00001.00000.6666 (4)0.0264 (10)
N30.00001.00001.2837 (4)0.0308 (11)
O1−0.06561 (15)0.78963 (11)0.5975 (3)0.0472 (7)
O2−0.06099 (15)0.88136 (10)0.4182 (3)0.0446 (7)
O30.03031 (12)0.92181 (8)0.4850 (2)0.0302 (5)
O40.1760 (2)0.57580 (17)0.5154 (4)0.0837 (12)
O50.1539 (2)0.58524 (18)0.6938 (4)0.0845 (12)
O60.10205 (11)1.02344 (9)0.4739 (2)0.0324 (5)
H120.12671.00440.43140.049*
H110.09761.05510.45370.049*
S2−0.02931 (4)0.77903 (3)0.48577 (9)0.0311 (2)
Zn10.00001.00000.47672 (3)0.02310 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0334 (17)0.0190 (14)0.0327 (19)−0.0014 (12)0.0014 (15)0.0027 (13)
C20.046 (2)0.0311 (17)0.0318 (18)0.0040 (16)0.0073 (17)0.0063 (15)
C30.0390 (19)0.0333 (18)0.040 (2)0.0061 (15)0.0095 (16)−0.0009 (15)
C40.0373 (18)0.0277 (17)0.0365 (19)0.0073 (15)−0.0023 (16)0.0044 (15)
C50.048 (2)0.039 (2)0.0323 (19)0.0122 (18)0.0004 (17)0.0072 (16)
C60.043 (2)0.0346 (19)0.032 (2)0.0091 (16)0.0062 (16)0.0000 (15)
C70.0333 (16)0.0209 (14)0.0387 (17)−0.0012 (12)0.0007 (16)−0.0004 (15)
C80.0412 (17)0.0217 (14)0.021 (2)0.0032 (14)0.0011 (14)−0.0002 (12)
C90.056 (2)0.0340 (18)0.0209 (16)−0.0072 (17)−0.0033 (18)0.0036 (15)
C100.065 (3)0.037 (2)0.0219 (19)−0.010 (2)−0.0070 (18)−0.0022 (16)
C110.034 (3)0.039 (3)0.017 (3)0.000 (2)0.0000.000
C120.046 (4)0.041 (4)0.020 (3)−0.004 (2)0.0000.000
C130.052 (2)0.039 (2)0.0238 (18)0.0089 (17)0.0028 (17)−0.0022 (16)
C140.0454 (19)0.0375 (18)0.0236 (17)0.0085 (15)0.0011 (18)0.0042 (15)
N10.058 (2)0.048 (2)0.046 (2)0.0266 (18)0.0021 (18)0.0042 (17)
N20.035 (3)0.027 (2)0.017 (2)0.0019 (16)0.0000.000
N30.038 (3)0.035 (3)0.019 (2)−0.0026 (17)0.0000.000
O10.0427 (15)0.0356 (15)0.063 (2)0.0060 (12)0.0208 (15)0.0064 (14)
O20.0513 (15)0.0249 (12)0.0578 (17)0.0043 (11)−0.0216 (14)−0.0069 (12)
O30.0410 (12)0.0197 (9)0.0299 (12)0.0006 (9)−0.0014 (12)−0.0005 (10)
O40.0909 (16)0.0800 (16)0.0802 (17)0.0424 (12)0.0035 (13)−0.0019 (12)
O50.0888 (16)0.0848 (16)0.0797 (17)0.0400 (12)0.0001 (13)0.0060 (13)
O60.0356 (12)0.0293 (11)0.0323 (12)0.0041 (9)0.0041 (12)0.0017 (11)
S20.0310 (4)0.0203 (3)0.0418 (5)−0.0003 (3)−0.0009 (4)0.0015 (4)
Zn10.0327 (3)0.0192 (2)0.0174 (2)−0.0002 (2)0.0000.000
Geometric parameters (Å, °) top
C1—C61.384 (5)C11—C10i1.379 (5)
C1—C21.391 (5)C11—C121.492 (6)
C1—S21.801 (3)C12—C13i1.396 (5)
C2—C31.381 (5)C12—C131.396 (5)
C2—H10.9300C13—C141.377 (6)
C3—C41.383 (5)C13—H90.9300
C3—H20.9300C14—N31.343 (5)
C4—C51.384 (6)C14—H100.9300
C4—N11.460 (5)N1—O41.194 (6)
C5—C61.390 (5)N1—O51.217 (6)
C5—H30.9300N2—C9i1.330 (4)
C6—H40.9300N2—Zn12.181 (4)
C7—C81.530 (4)N3—C14i1.343 (5)
C7—S21.803 (3)N3—Zn1ii2.217 (5)
C7—H50.9700O1—S21.500 (3)
C7—H60.9700O3—Zn12.098 (2)
C8—O21.248 (5)O6—Zn12.136 (2)
C8—O31.254 (4)O6—H120.8500
C9—N21.330 (4)O6—H110.8501
C9—C101.397 (6)Zn1—O3i2.098 (2)
C9—H70.9300Zn1—O6i2.136 (2)
C10—C111.379 (5)Zn1—N3iii2.217 (5)
C10—H80.9300
C6—C1—C2121.6 (3)C13—C12—C11121.3 (3)
C6—C1—S2118.3 (3)C14—C13—C12119.6 (4)
C2—C1—S2120.0 (3)C14—C13—H9120.2
C3—C2—C1119.2 (4)C12—C13—H9120.2
C3—C2—H1120.4N3—C14—C13122.7 (4)
C1—C2—H1120.4N3—C14—H10118.6
C2—C3—C4118.5 (3)C13—C14—H10118.6
C2—C3—H2120.7O4—N1—O5122.0 (4)
C4—C3—H2120.7O4—N1—C4120.3 (4)
C3—C4—C5123.3 (3)O5—N1—C4117.7 (4)
C3—C4—N1118.5 (4)C9—N2—C9i117.5 (5)
C5—C4—N1118.1 (3)C9—N2—Zn1121.3 (2)
C4—C5—C6117.7 (3)C9i—N2—Zn1121.3 (2)
C4—C5—H3121.1C14—N3—C14i117.9 (5)
C6—C5—H3121.1C14—N3—Zn1ii121.0 (3)
C1—C6—C5119.6 (4)C14i—N3—Zn1ii121.0 (3)
C1—C6—H4120.2C8—O3—Zn1127.2 (2)
C5—C6—H4120.2Zn1—O6—H12113.9
C8—C7—S2109.2 (2)Zn1—O6—H11100.0
C8—C7—H5109.8H12—O6—H11117.0
S2—C7—H5109.8O1—S2—C1105.68 (17)
C8—C7—H6109.8O1—S2—C7105.22 (18)
S2—C7—H6109.8C1—S2—C796.11 (15)
H5—C7—H6108.3O3—Zn1—O3i174.79 (15)
O2—C8—O3127.3 (3)O3—Zn1—O6i90.57 (9)
O2—C8—C7117.3 (3)O3i—Zn1—O6i89.50 (9)
O3—C8—C7115.4 (3)O3—Zn1—O689.50 (9)
N2—C9—C10122.9 (4)O3i—Zn1—O690.57 (9)
N2—C9—H7118.5O6i—Zn1—O6178.29 (15)
C10—C9—H7118.5O3—Zn1—N287.39 (7)
C11—C10—C9119.5 (4)O3i—Zn1—N287.39 (7)
C11—C10—H8120.3O6i—Zn1—N290.86 (7)
C9—C10—H8120.3O6—Zn1—N290.86 (7)
C10i—C11—C10117.6 (5)O3—Zn1—N3iii92.61 (7)
C10i—C11—C12121.2 (3)O3i—Zn1—N3iii92.61 (7)
C10—C11—C12121.2 (3)O6i—Zn1—N3iii89.14 (7)
C13i—C12—C13117.4 (5)O6—Zn1—N3iii89.14 (7)
C13i—C12—C11121.3 (3)N2—Zn1—N3iii180.000 (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
O6—H12···O1iv0.851.882.731 (4)176
O6—H11···O2i0.851.832.655 (4)162
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
O6—H12···O1i0.851.882.731 (4)176
O6—H11···O2ii0.851.832.655 (4)162
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.

Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2002). Acta Cryst. C58, o201–o203.

Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2003). Acta Cryst. C59, o124–o126.

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 Inc., The Woodlands, Texas, USA.

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.