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Acta Cryst. (2007). E63, m2986    [ doi:10.1107/S1600536807056164 ]

Poly[[mu]6-benzene-1,2,4,5-tetracarboxylato-[kappa]6O1:O2:O2':O4:O5:O5'-bis[diaquazinc(II)]]

J. Wang, L. Lu, B. Yang, B.-Z. Zhao and S. W. Ng

Abstract top

The benzenetetracarboxylate tetraanion in the title compound, [Zn2(C8H2O8)(H2O)4]n, lies on a center of inversion. Two delocalized carboxylate -CO2 groups are each connected to two different diaquazinc units, whereas the other two localized carboxylate -CO2 are each bonded to one different diaquazinc unit. The metal atom is five-coordinate as a consequence of such [mu]6-bridging; the water molecules occupy an axial and an equatorial site of the trigonal bipyramid in the three-dimensional network. The architecture is further consolidated by extensive hydrogen bonding in which one water molecule serves as a donor and the other as both a donor and an acceptor.

Comment top

The are many crystallographic studies of coordination compounds of 1,2,4,5-benzenetetracarboxylic acid (Cambridge Structural Database, Version 5.28, Nov. 2006); a water-coordinated zinc derivative with zinc in both tetrahedral and octahedral geometries has been reported (Robl, 1987; Wei et al., 1991). A slight variation of the synthesis has yielded the title diaquazinc compound, which features a trigonal-bipyramidal zinc coordination environment (Scheme I; Fig. 1).

Related literature top

For the structure of catena-poly[µ5-1,2,4,5-benzenetetracarboxylato-pentaaquadizinc], which has one Zn atom in a tetrahedral and the other in an octahedral coordination geometry, see: Robl (1987); Wei et al. (1991).

Experimental top

Benzene-1,2,4,5-tetracarboxylic acid (0.05 g, 0.22 mmol), zinc acetate (0.062 g, 0.20 mmol) and sodium hydroxide (0.08 g, 0.20 mmol) were heated in acetonitrile (25 ml) until the reagents dissolved completely. The solution was filtered; diethyl ether was layered over the solution, which was kept in a closed container. Crystals were obtained after a week.

Refinement top

All hydrogen atoms were located in difference Fourier maps, and were refined with distance restraints of C–H 0.95±0.01 Å and O–H 0.85±0.01 Å. Their temperature factors were freely refined.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of a portion of the polymeric structure. Displacement ellipsoids are drawn at the 70% probabability level, and H atoms as spheres of arbitrary radii. [Symmetry codes (i): 1/2 + x, 3/2 - y, 1/2 + z; (ii) x - 1/2, 3/2 - y, 1/2 + z.]
Poly[µ6-benzene-1,2,4,5-tetracarboxylato- κ6O1:O2:O2':O4:O5:O5'-bis[diaquazinc(II)]] top
Crystal data top
[Zn2(C8H2O8)(H2O)4]F(000) = 452
Mr = 452.92Dx = 2.170 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2515 reflections
a = 5.259 (1) Åθ = 2.5–26.1°
b = 16.342 (1) ŵ = 3.53 mm−1
c = 8.143 (1) ÅT = 295 K
β = 97.939 (1)°Block, colorless
V = 693.1 (2) Å30.29 × 0.25 × 0.21 mm
Z = 2
Data collection top
Bruker APEX area-detector
diffractometer		1362 independent reflections
Radiation source: fine-focus sealed tube1284 reflections with I > 2σ(I)
graphiteRint = 0.028
φ and ω scansθmax = 26.1°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→5
Tmin = 0.428, Tmax = 0.524k = −19→16
3774 measured reflectionsl = −9→10
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)] = 0.024All H-atom parameters refined
wR(F2) = 0.066 w = 1/[σ2(Fo2) + (0.0414P)2 + 0.1318P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1362 reflectionsΔρmax = 0.41 e Å−3
130 parametersΔρmin = −0.46 e Å−3
5 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.030 (2)
Crystal data top
[Zn2(C8H2O8)(H2O)4]V = 693.1 (2) Å3
Mr = 452.92Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.259 (1) ŵ = 3.53 mm−1
b = 16.342 (1) ÅT = 295 K
c = 8.143 (1) Å0.29 × 0.25 × 0.21 mm
β = 97.939 (1)°
Data collection top
Bruker APEX area-detector
diffractometer		1362 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1284 reflections with I > 2σ(I)
Tmin = 0.428, Tmax = 0.524Rint = 0.028
3774 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.024All H-atom parameters refined
wR(F2) = 0.066Δρmax = 0.41 e Å−3
S = 1.06Δρmin = −0.46 e Å−3
1362 reflectionsAbsolute structure: ?
130 parametersFlack parameter: ?
5 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.64624 (4)0.66722 (1)0.6294 (1)0.0154 (1)
O10.6293 (3)0.78505 (9)0.57696 (18)0.0215 (3)
O20.4252 (3)0.79266 (9)0.31917 (17)0.0190 (3)
O30.9206 (3)0.87008 (9)0.28756 (18)0.0199 (3)
O40.9313 (3)0.99480 (9)0.18210 (18)0.0230 (3)
O1w0.3378 (3)0.6354 (1)0.4158 (2)0.0230 (3)
O2w0.8804 (3)0.5957 (1)0.5220 (2)0.0271 (4)
C10.5300 (4)0.8244 (1)0.4509 (3)0.0145 (4)
C20.5241 (4)0.9156 (1)0.4733 (2)0.0132 (4)
C30.6670 (4)0.9715 (1)0.3922 (2)0.0142 (4)
C40.8534 (4)0.9442 (1)0.2782 (2)0.0148 (4)
C50.6398 (4)1.0548 (1)0.4197 (2)0.0155 (4)
H10.308 (11)0.672 (3)0.341 (5)0.15 (3)*
H20.372 (5)0.591 (1)0.370 (3)0.04 (1)*
H31.008 (4)0.612 (2)0.478 (3)0.04 (1)*
H40.795 (5)0.564 (2)0.452 (3)0.04 (1)*
H50.748 (4)1.091 (1)0.371 (3)0.03 (1)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0175 (2)0.0122 (2)0.0172 (2)−0.0011 (1)0.0051 (1)0.0004 (1)
O10.033 (1)0.012 (1)0.018 (1)−0.001 (1)−0.004 (1)0.001 (1)
O20.024 (1)0.014 (1)0.018 (1)0.001 (1)−0.003 (1)−0.003 (1)
O30.024 (1)0.016 (1)0.022 (1)0.006 (1)0.010 (1)0.000 (1)
O40.028 (1)0.020 (1)0.024 (1)0.001 (1)0.014 (1)0.004 (1)
O1w0.026 (1)0.019 (1)0.025 (1)0.002 (1)0.006 (1)0.003 (1)
O2w0.019 (1)0.031 (1)0.033 (1)−0.004 (1)0.009 (1)−0.014 (1)
C10.014 (1)0.014 (1)0.017 (1)0.001 (1)0.004 (1)0.000 (1)
C20.015 (1)0.012 (1)0.013 (1)0.002 (1)0.000 (1)0.000 (1)
C30.016 (1)0.013 (1)0.014 (1)0.002 (1)0.003 (1)0.001 (1)
C40.014 (1)0.016 (1)0.015 (1)0.000 (1)0.001 (1)−0.002 (1)
C50.019 (1)0.014 (1)0.015 (1)−0.001 (1)0.004 (1)0.001 (1)
Geometric parameters (Å, °) top
Zn1—O11.972 (2)O1w—H20.85 (1)
Zn1—O2i2.084 (1)O2w—H30.85 (1)
Zn1—O3ii1.965 (1)O2w—H40.85 (1)
Zn1—O1w2.269 (2)C1—C21.502 (3)
Zn1—O2w1.986 (2)C2—C5iii1.394 (3)
O1—C11.262 (3)C2—C31.404 (3)
O2—C11.249 (3)C3—C51.390 (3)
O3—C41.261 (2)C3—C41.508 (2)
O4—C41.246 (2)C5—C2iii1.394 (3)
O1w—H10.85 (1)C5—H50.94 (1)
O3ii—Zn1—O1115.55 (6)Zn1—O2w—H4110 (2)
O3ii—Zn1—O2w125.00 (7)H3—O2w—H4106 (3)
O1—Zn1—O2w119.44 (7)O2—C1—O1124.8 (2)
O3ii—Zn1—O2i92.21 (6)O2—C1—C2120.2 (2)
O1—Zn1—O2i81.92 (6)O1—C1—C2114.9 (2)
O2w—Zn1—O2i95.49 (6)C5iii—C2—C3119.0 (2)
O3ii—Zn1—O1w89.93 (6)C5iii—C2—C1116.5 (2)
O1—Zn1—O1w92.96 (6)C3—C2—C1124.5 (2)
O2w—Zn1—O1w87.07 (6)C5—C3—C2119.2 (2)
O2i—Zn1—O1w174.88 (6)C5—C3—C4118.6 (2)
C1—O1—Zn1132.5 (1)C2—C3—C4122.2 (2)
C1—O2—Zn1iv133.5 (1)O4—C4—O3124.2 (2)
C4—O3—Zn1v116.6 (1)O4—C4—C3119.3 (2)
Zn1—O1w—H1116 (4)O3—C4—C3116.5 (2)
Zn1—O1w—H2111 (2)C3—C5—C2iii121.8 (2)
H1—O1w—H2109 (4)C3—C5—H5118 (2)
Zn1—O2w—H3126 (2)C2iii—C5—H5120 (2)
O3ii—Zn1—O1—C1−105.7 (2)C5iii—C2—C3—C5−0.6 (3)
O2w—Zn1—O1—C173.9 (2)C1—C2—C3—C5178.2 (2)
O2i—Zn1—O1—C1165.7 (2)C5iii—C2—C3—C4178.4 (2)
O1w—Zn1—O1—C1−14.4 (2)C1—C2—C3—C4−2.9 (3)
Zn1iv—O2—C1—O1155.2 (2)Zn1v—O3—C4—O4−3.8 (3)
Zn1iv—O2—C1—C2−19.4 (3)Zn1v—O3—C4—C3176.3 (1)
Zn1—O1—C1—O2−4.4 (3)C5—C3—C4—O4−16.9 (3)
Zn1—O1—C1—C2170.4 (1)C2—C3—C4—O4164.1 (2)
O2—C1—C2—C5iii106.5 (2)C5—C3—C4—O3163.0 (2)
O1—C1—C2—C5iii−68.6 (2)C2—C3—C4—O3−15.9 (3)
O2—C1—C2—C3−72.3 (3)C2—C3—C5—C2iii0.6 (3)
O1—C1—C2—C3112.6 (2)C4—C3—C5—C2iii−178.4 (2)
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) x+1/2, −y+3/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1···O1iv0.85 (1)2.33 (3)3.109 (2)152 (6)
O1w—H1···O20.85 (1)2.08 (4)2.745 (2)134 (5)
O1w—H2···O4vi0.85 (1)1.96 (1)2.767 (2)159 (3)
O2w—H3···O1wvii0.85 (1)1.91 (1)2.744 (2)168 (3)
O2w—H4···O4vi0.85 (1)1.89 (1)2.724 (2)172 (3)
Symmetry codes: (iv) x−1/2, −y+3/2, z−1/2; (vi) −x+3/2, y−1/2, −z+1/2; (vii) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1···O20.85 (1)2.08 (4)2.745 (2)134 (5)
O1w—H2···O4i0.85 (1)1.96 (1)2.767 (2)159 (3)
O2w—H3···O1wii0.85 (1)1.91 (1)2.744 (2)168 (3)
O2w—H4···O4i0.85 (1)1.89 (1)2.724 (2)172 (3)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z.
Acknowledgements top

The authors thank Sichuan University of Science and Technology and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2004). SMART (Version 6.36A) and SAINT (Version 6.36A). Bruker AXS Inc., Madison, Winconsin, USA.

Robl, C. (1987). Z. Anorg. Allg. Chem. 554, 79–86.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Wei, G.-C., Jin, Z.-S., Duan, Z.-B., Yang, K.-Y. & Ni, J.-Z. (1991). Chin. J. Struct. Chem. 10, 106–109.

Westrip, S. P. (2007). publCIF. In preparation.