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Acta Cryst. (2008). E64, m276-m277    [ doi:10.1107/S1600536807064860 ]

catena-Poly[[tetraaquazinc(II)]-[mu]-2,2'-dihydroxy-5,5'-diazenediyldibenzoato]

Y.-H. Tan, Q.-S. Li, X.-P. Luo and X.-B. Xie

Abstract top

In the title compound, [Zn(C14H8N2O6)(H2O)4]n, the 2,2'-dihydroxy-5,5'-diazenediyldibenzoate ligand acts as a carboxylate bridge, leading to the formation of a polymeric chain running along the [1\overline{1}0] direction. The ZnII atom is hexa-coordinated in a distorted octahedral geometry by six O atoms [Zn-O = 2.055 (4)-2.132 (3) Å] from two carboxylate ligands and four water molecules. The crystal packing is stabilized by intermolecular O-H...O, O-H...N and C-H...O hydrogen bonds, and two [pi]-[pi] interactions. The centroid-centroid distances are 3.803 (16) and 3.804 (17) Å.

Comment top

Olsalazine, 2,2'-dihydroxy-5,5'-diazenediyldibenzoic acid, has been widely used to prevent and treat the inflammatory bowel diseases, such as ulcerative colitis (Klotz, 2005). In previous work, we have synthesized a serial of Zn (Tang, Tan, Chen & Cao, 2007), Cd and Co (Tang, Yang et al., 2007) complexes with phenanthroline as auxiliary ligand. We have also reported a Mn complex of olsalazine (Tang, Tan & Cao, 2007), but the zinc complex with single olsalazine as building block has not been reported yet. Here we reported the crystal structure of the title compound, (I), a new zinc complex of olsalazine.

In (I), the Zn atom is hexa-coordinated (Fig. 1) by two O atoms from two L ligands [H2L=3,3-azo-bis(6-hydroxybenzoic acid)] and four water molecules in a distorted octahedral geometry (Table 1). Two ligands are cis to each other in an octahedral environment. Each ligand L acts as a carboxylate bridge, which leads to formation of a polymeric chain running in the direction [110]. Two neighbouring polymeric chains are paired by π···π interactions between the aromatic rings; the distances Cg1···Cg1i and Cg2···Cg2i are 3.803 (16) and 3.804 (17) Å, respectively [Cg1 and Cg2 are centroids of C2—C7 and C8—C13 rings, respectively; symmetry code: (i) x - 1, y - 1, z]. The crystal packing is further stabilized by the intermolecular O—H···O, O—H···N and C—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Klotz (2005); Tang, Tan & Cao (2007); Tang, Tan, Chen & Cao (2007); Tang, Yang et al. (2007).

Refinement top

The hydroxy and C-bound H atoms were placed in calculated positions (C—H = 0.93 Å and O—H = 0.82 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C,O). The water H atoms were located in a difference Fourier map and refined isotropically.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. A part of the polymeric structure of (I), showing displacement ellipsoids drawn at the 30% probability level and the atomic labelling. Unlabelled atoms are related to labelled atoms by the symmetry code (x - 1, y + 1, z).
catena-Poly[[tetraaquazinc(II)]- µ-2,2'-dihydroxy-5,5'-diazenediyldibenzoato] top
Crystal data top
[Zn(C14H8N2O6)(H2O)4]F000 = 896
Mr = 437.66Dx = 1.752 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 935 reflections
a = 9.510 (2) Åθ = 1.8–26.0º
b = 11.255 (3) ŵ = 1.54 mm−1
c = 16.214 (4) ÅT = 296 (2) K
β = 107.019 (3)ºBlock, orange
V = 1659.5 (7) Å30.25 × 0.22 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3278 independent reflections
Radiation source: fine-focus sealed tube3036 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 296(2) Kθmax = 26.0º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −11→11
Tmin = 0.699, Tmax = 0.861k = −13→13
10784 measured reflectionsl = −19→19
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)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0307P)2 + 1.3308P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3278 reflectionsΔρmax = 0.39 e Å−3
277 parametersΔρmin = −0.70 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C14H8N2O6)(H2O)4]V = 1659.5 (7) Å3
Mr = 437.66Z = 4
Monoclinic, P21/cMo Kα
a = 9.510 (2) ŵ = 1.54 mm−1
b = 11.255 (3) ÅT = 296 (2) K
c = 16.214 (4) Å0.25 × 0.22 × 0.10 mm
β = 107.019 (3)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3278 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		3036 reflections with I > 2σ(I)
Tmin = 0.699, Tmax = 0.861Rint = 0.034
10784 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039277 parameters
wR(F2) = 0.098H atoms treated by a mixture of
independent and constrained refinement
S = 1.10Δρmax = 0.39 e Å−3
3278 reflectionsΔρmin = −0.70 e Å−3
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
Zn10.71408 (5)0.64023 (4)0.21196 (3)0.03166 (13)
O60.9487 (4)0.4284 (3)0.2011 (2)0.0620 (11)
O50.7705 (4)0.5388 (3)0.1179 (2)0.0434 (8)
O40.6849 (4)0.5057 (3)−0.0439 (2)0.0511 (9)
H4A0.68730.53590.00250.077*
O31.5187 (4)−0.2597 (3)−0.0536 (2)0.0570 (10)
H3A1.5603−0.2816−0.00420.085*
O21.5791 (3)−0.2637 (2)0.10891 (19)0.0375 (7)
O11.4725 (4)−0.1395 (3)0.17841 (18)0.0508 (8)
O4W0.5362 (4)0.5313 (3)0.2060 (3)0.0535 (9)
O3W0.8865 (4)0.7510 (3)0.2132 (3)0.0501 (8)
O2W0.6659 (4)0.7520 (3)0.3064 (2)0.0493 (9)
O1W0.8398 (4)0.5403 (3)0.3147 (2)0.0431 (8)
N21.0930 (4)0.1421 (3)0.0030 (2)0.0343 (7)
N11.1233 (4)0.1052 (3)−0.0637 (2)0.0334 (8)
C140.8672 (5)0.4557 (4)0.1291 (3)0.0402 (11)
C130.8783 (5)0.3916 (3)0.0511 (3)0.0335 (9)
C120.7874 (5)0.4192 (4)−0.0312 (3)0.0343 (9)
C110.7972 (5)0.3553 (4)−0.1026 (3)0.0414 (10)
H11A0.73670.3751−0.15710.050*
C100.8949 (5)0.2633 (4)−0.0935 (3)0.0372 (9)
H10A0.89890.2196−0.14140.045*
C90.9877 (5)0.2357 (3)−0.0127 (3)0.0316 (9)
C80.9781 (5)0.2998 (4)0.0582 (3)0.0370 (10)
H8A1.04060.28070.11230.044*
C71.2236 (4)0.0099 (3)−0.0537 (3)0.0322 (9)
C61.2416 (5)−0.0349 (4)−0.1298 (3)0.0396 (10)
H6A1.1871−0.0025−0.18220.048*
C51.3378 (6)−0.1259 (4)−0.1296 (3)0.0473 (12)
H5A1.3469−0.1558−0.18120.057*
C41.4210 (5)−0.1727 (4)−0.0517 (3)0.0372 (10)
C31.4032 (4)−0.1293 (4)0.0259 (2)0.0301 (8)
C21.3051 (5)−0.0383 (3)0.0244 (3)0.0316 (9)
H2A1.2936−0.00930.07580.038*
C11.4901 (5)−0.1794 (4)0.1108 (3)0.0321 (9)
H1WA0.872 (6)0.496 (5)0.283 (4)0.062 (18)*
H3WA0.872 (7)0.779 (5)0.170 (4)0.05 (2)*
H4WA0.507 (9)0.504 (6)0.159 (5)0.09 (3)*
H2WA0.597 (7)0.802 (5)0.260 (4)0.073 (19)*
H3WB0.921 (7)0.796 (6)0.250 (5)0.07 (2)*
H4WB0.545 (7)0.488 (5)0.253 (4)0.066 (19)*
H1WB0.895 (8)0.580 (6)0.359 (4)0.08 (2)*
H2WB0.619 (8)0.703 (6)0.330 (5)0.09 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0368 (2)0.0289 (2)0.0260 (2)0.0034 (2)0.00388 (19)0.0022 (2)
O60.076 (2)0.070 (2)0.0266 (18)0.045 (2)−0.0057 (17)−0.0064 (16)
O50.0494 (18)0.0396 (16)0.0341 (18)0.0196 (14)0.0009 (13)−0.0061 (13)
O40.056 (2)0.0503 (18)0.0372 (19)0.0296 (16)−0.0021 (15)−0.0070 (15)
O30.076 (2)0.062 (2)0.0339 (19)0.0451 (19)0.0164 (18)0.0057 (16)
O20.0453 (16)0.0341 (14)0.0297 (16)0.0143 (13)0.0057 (13)0.0039 (12)
O10.068 (2)0.0524 (16)0.0286 (15)0.0272 (18)0.0085 (16)0.0010 (16)
O4W0.051 (2)0.059 (2)0.039 (2)−0.0120 (16)−0.0032 (17)0.0131 (19)
O3W0.060 (2)0.055 (2)0.030 (2)−0.0195 (17)0.0066 (17)0.001 (2)
O2W0.061 (2)0.051 (2)0.034 (2)0.0169 (18)0.0105 (16)0.0009 (15)
O1W0.0504 (19)0.0440 (17)0.0321 (19)0.0105 (15)0.0077 (14)0.0042 (14)
N20.0380 (17)0.0340 (15)0.0279 (17)0.0107 (16)0.0052 (14)0.0014 (16)
N10.0393 (18)0.0326 (17)0.0265 (18)0.0100 (14)0.0070 (15)0.0019 (13)
C140.044 (2)0.037 (2)0.036 (3)0.0115 (19)0.0051 (19)−0.0071 (19)
C130.039 (2)0.0294 (19)0.026 (2)0.0077 (17)−0.0003 (18)−0.0018 (15)
C120.032 (2)0.034 (2)0.032 (2)0.0076 (18)0.0013 (16)0.0019 (18)
C110.042 (2)0.048 (2)0.027 (2)0.014 (2)−0.0004 (18)0.000 (2)
C100.047 (2)0.039 (2)0.023 (2)0.0071 (19)0.0049 (17)−0.0056 (17)
C90.035 (2)0.0302 (19)0.028 (2)0.0089 (16)0.0061 (17)−0.0002 (16)
C80.043 (2)0.037 (2)0.026 (2)0.0108 (19)0.0030 (18)−0.0017 (18)
C70.035 (2)0.0308 (19)0.029 (2)0.0071 (16)0.0067 (17)0.0030 (17)
C60.047 (3)0.040 (2)0.026 (2)0.015 (2)0.0027 (18)0.0056 (18)
C50.068 (3)0.049 (2)0.023 (2)0.020 (3)0.009 (2)−0.001 (2)
C40.046 (2)0.034 (2)0.031 (2)0.0162 (18)0.0108 (19)0.0018 (17)
C30.035 (2)0.0271 (17)0.0262 (19)0.0065 (17)0.0064 (16)0.0032 (17)
C20.035 (2)0.0306 (19)0.029 (2)0.0051 (17)0.0088 (17)−0.0001 (17)
C10.036 (2)0.0322 (19)0.026 (2)0.0039 (17)0.0059 (17)−0.0014 (16)
Geometric parameters (Å, °) top
Zn1—O3W2.055 (4)N2—N11.267 (5)
Zn1—O4W2.069 (4)N2—C91.425 (5)
Zn1—O1W2.075 (3)N1—C71.413 (5)
Zn1—O2i2.086 (3)C14—C131.487 (6)
Zn1—O52.097 (3)C13—C81.385 (6)
Zn1—O2W2.132 (3)C13—C121.396 (6)
O6—C141.236 (6)C12—C111.389 (6)
O5—C141.286 (5)C11—C101.370 (6)
O4—C121.350 (5)C11—H11A0.9300
O4—H4A0.8200C10—C91.383 (6)
O3—C41.356 (5)C10—H10A0.9300
O3—H3A0.8200C9—C81.383 (6)
O2—C11.278 (5)C8—H8A0.9300
O2—Zn1ii2.086 (3)C7—C21.387 (6)
O1—C11.240 (5)C7—C61.389 (6)
O4W—H4WA0.80 (8)C6—C51.372 (6)
O4W—H4WB0.88 (7)C6—H6A0.9300
O3W—H3WA0.74 (6)C5—C41.382 (6)
O3W—H3WB0.78 (7)C5—H5A0.9300
O2W—H2WA1.02 (7)C4—C31.406 (6)
O2W—H2WB0.87 (7)C3—C21.381 (5)
O1W—H1WA0.83 (6)C3—C11.493 (5)
O1W—H1WB0.88 (7)C2—H2A0.9300
O3W—Zn1—O4W177.75 (16)C12—C13—C14121.8 (4)
O3W—Zn1—O1W92.90 (16)O4—C12—C11117.9 (4)
O4W—Zn1—O1W89.28 (15)O4—C12—C13121.6 (4)
O3W—Zn1—O2i89.72 (15)C11—C12—C13120.5 (4)
O4W—Zn1—O2i88.10 (14)C10—C11—C12120.7 (4)
O1W—Zn1—O2i177.36 (13)C10—C11—H11A119.7
O3W—Zn1—O587.93 (16)C12—C11—H11A119.7
O4W—Zn1—O591.35 (16)C11—C10—C9119.8 (4)
O1W—Zn1—O594.52 (13)C11—C10—H10A120.1
O2i—Zn1—O585.89 (11)C9—C10—H10A120.1
O3W—Zn1—O2W88.49 (17)C8—C9—C10119.4 (4)
O4W—Zn1—O2W92.21 (18)C8—C9—N2116.8 (4)
O1W—Zn1—O2W86.44 (15)C10—C9—N2123.8 (4)
O2i—Zn1—O2W93.32 (13)C9—C8—C13122.0 (4)
O5—Zn1—O2W176.33 (15)C9—C8—H8A119.0
C14—O5—Zn1128.2 (3)C13—C8—H8A119.0
C12—O4—H4A109.5C2—C7—C6119.2 (4)
C4—O3—H3A109.5C2—C7—N1125.4 (4)
C1—O2—Zn1ii128.5 (3)C6—C7—N1115.4 (3)
Zn1—O4W—H4WA109 (6)C5—C6—C7121.6 (4)
Zn1—O4W—H4WB114 (4)C5—C6—H6A119.2
H4WA—O4W—H4WB122 (6)C7—C6—H6A119.2
Zn1—O3W—H3WA109 (5)C6—C5—C4119.3 (4)
Zn1—O3W—H3WB125 (5)C6—C5—H5A120.3
H3WA—O3W—H3WB111 (7)C4—C5—H5A120.3
Zn1—O2W—H2WA91 (3)O3—C4—C5117.9 (4)
Zn1—O2W—H2WB101 (5)O3—C4—C3122.2 (4)
H2WA—O2W—H2WB112 (5)C5—C4—C3119.9 (4)
Zn1—O1W—H1WA93 (4)C2—C3—C4120.0 (3)
Zn1—O1W—H1WB117 (4)C2—C3—C1119.0 (4)
H1WA—O1W—H1WB125 (6)C4—C3—C1121.0 (4)
N1—N2—C9114.4 (3)C3—C2—C7120.0 (4)
N2—N1—C7117.7 (3)C3—C2—H2A120.0
O6—C14—O5122.6 (4)C7—C2—H2A120.0
O6—C14—C13120.1 (4)O1—C1—O2123.5 (4)
O5—C14—C13117.3 (4)O1—C1—C3119.8 (4)
C8—C13—C12117.6 (4)O2—C1—C3116.7 (4)
C8—C13—C14120.6 (4)
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O60.84 (6)1.86 (6)2.677 (5)168 (6)
O1W—H1WB···N2iii0.88 (7)2.32 (6)3.058 (5)143 (6)
O2W—H2WA···O1i1.01 (6)1.63 (6)2.636 (5)170 (6)
O2W—H2WB···O3iv0.87 (7)2.44 (8)2.997 (5)123 (6)
O3W—H3WA···N1v0.74 (6)2.17 (6)2.893 (5)164 (5)
O3W—H3WB···O6iii0.78 (8)1.95 (7)2.664 (5)152 (7)
O4W—H4WA···O4vi0.79 (7)2.20 (8)2.875 (6)144 (8)
O4W—H4WB···O1iii0.89 (6)1.85 (6)2.703 (5)160 (6)
O3—H3A···O20.821.802.528 (4)147
O4—H4A···O50.821.812.537 (4)148
C2—H2A···O1Wvii0.932.533.405 (6)157
Symmetry codes: (iii) −x+2, y+1/2, −z+1/2; (i) x−1, y+1, z; (iv) x−1, −y+1/2, z+1/2; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z; (vii) −x+2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O3W2.055 (4)Zn1—O2i2.086 (3)
Zn1—O4W2.069 (4)Zn1—O52.097 (3)
Zn1—O1W2.075 (3)Zn1—O2W2.132 (3)
O3W—Zn1—O4W177.75 (16)O1W—Zn1—O594.52 (13)
O3W—Zn1—O1W92.90 (16)O2i—Zn1—O585.89 (11)
O4W—Zn1—O1W89.28 (15)O3W—Zn1—O2W88.49 (17)
O3W—Zn1—O2i89.72 (15)O4W—Zn1—O2W92.21 (18)
O4W—Zn1—O2i88.10 (14)O1W—Zn1—O2W86.44 (15)
O1W—Zn1—O2i177.36 (13)O2i—Zn1—O2W93.32 (13)
O3W—Zn1—O587.93 (16)O5—Zn1—O2W176.33 (15)
O4W—Zn1—O591.35 (16)
Symmetry codes: (i) x−1, y+1, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O60.84 (6)1.86 (6)2.677 (5)168 (6)
O1W—H1WB···N2ii0.88 (7)2.32 (6)3.058 (5)143 (6)
O2W—H2WA···O1i1.01 (6)1.63 (6)2.636 (5)170 (6)
O2W—H2WB···O3iii0.87 (7)2.44 (8)2.997 (5)123 (6)
O3W—H3WA···N1iv0.74 (6)2.17 (6)2.893 (5)164 (5)
O3W—H3WB···O6ii0.78 (8)1.95 (7)2.664 (5)152 (7)
O4W—H4WA···O4v0.79 (7)2.20 (8)2.875 (6)144 (8)
O4W—H4WB···O1ii0.89 (6)1.85 (6)2.703 (5)160 (6)
O3—H3A···O20.821.802.528 (4)147
O4—H4A···O50.821.812.537 (4)148
C2—H2A···O1Wvi0.932.533.405 (6)157
Symmetry codes: (ii) −x+2, y+1/2, −z+1/2; (i) x−1, y+1, z; (iii) x−1, −y+1/2, z+1/2; (iv) −x+2, −y+1, −z; (v) −x+1, −y+1, −z; (vi) −x+2, y−1/2, −z+1/2.
Acknowledgements top

This work was supported by the Gannan Medical University Master Development Foundation.

references
References top

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Tang, Y.-Z., Tan, Y.-H. & Cao, Y.-W. (2007). Acta Cryst. E63, m1175–m1176.

Tang, Y.-Z., Tan, Y.-H., Chen, S.-H. & Cao, Y.-W. (2007). Z. Anorg. Allg. Chem. 633, 332–335.

Tang, Y.-Z., Yang, S.-P., Tan, Y.-H., Chen, S.-H., Cao, Y.-W. & Wang, P. (2007). Wuji Huaxue Xuebao (Chin. J. Inorg. Chem.), 23, 70–74.