Acta Cryst. (2008). E64, m447 [ doi:10.1107/S1600536808003152 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
O)zinc(II)The ZnII atom in the title compound, [Zn(C8H5O3)2(H2O)2], which lies on a twofold rotation axis, is coordinated by two monodentate carboxylate groups and two water molecules in a tetrahedral geometry; the geometry is distorted towards octahedral owing to two long Zn
Ocarbonyl contacts [2.512 (2) Å]. Hydrogen-bonding interactions give rise to a three-dimensional network. The formyl group is disordered approximately equally over two positions.
Zinc diacetate dihydrate (2.2 g, 10 mmol) was added to anaqueous solution of 4-formylbenzoic acid (3.0 g, 20 mmol) that has earlier been treated with 1 ml pyridine to give a pH of 6. The solution was allowed to evaporate at room temperature; colorless prismatic crystals separated from the filtered solution after several days. C&N elemental analysis. Calc. C16H14O8Zn: C 48.08, H3.53%. Found: C 48.06, H 3.56%.
The formyl group is disordered over two sites; the ratio of the site occupation factors refined to a 0.508 (5):0.492 (5) ratio.
The carbon-bound H atoms were placed in calculated positions [C–H 0.93 Å and Uiso(H) 1.2Ueq(C)], and were included in the refinement in the riding-model approximation. The water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.85±0.01 Å and H···H 1.39±0.01 Å; their displacement parameters were freely refined.
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
![[Figure 1]](./bt2669fig1thm.gif)
| Fig. 1. Anisotropic displacement parameter plot of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radius. |
| [Zn(C8H5O3)2(H2O)2] | F000 = 816 |
| Mr = 399.64 | Dx = 1.696 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 5776 reflections |
| a = 27.537 (1) Å | θ = 3.2–27.5º |
| b = 5.0039 (2) Å | µ = 1.61 mm−1 |
| c = 12.0930 (6) Å | T = 295 (2) K |
| β = 110.039 (2)º | Block, colorless |
| V = 1565.4 (1) Å3 | 0.34 × 0.26 × 0.18 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 1785 independent reflections |
| Radiation source: fine-focus sealed tube | 1448 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| Detector resolution: 10.000 pixels mm-1 | θmax = 27.5º |
| T = 295(2) K | θmin = 3.2º |
| ω scans | h = −35→35 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −6→6 |
| Tmin = 0.532, Tmax = 0.760 | l = −15→15 |
| 7203 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0444P)2 + 0.5739P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max = 0.001 |
| 1785 reflections | Δρmax = 0.59 e Å−3 |
| 132 parameters | Δρmin = −0.38 e Å−3 |
| 3 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Zn(C8H5O3)2(H2O)2] | V = 1565.4 (1) Å3 |
| Mr = 399.64 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 27.537 (1) Å | µ = 1.61 mm−1 |
| b = 5.0039 (2) Å | T = 295 (2) K |
| c = 12.0930 (6) Å | 0.34 × 0.26 × 0.18 mm |
| β = 110.039 (2)º |
| Rigaku R-AXIS RAPID diffractometer | 1785 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1448 reflections with I > 2σ(I) |
| Tmin = 0.532, Tmax = 0.760 | Rint = 0.034 |
| 7203 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 3 restraints |
| wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.09 | Δρmax = 0.59 e Å−3 |
| 1785 reflections | Δρmin = −0.38 e Å−3 |
| 132 parameters |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Zn1 | 0.5000 | 0.07300 (7) | 0.7500 | 0.03500 (15) | |
| O1W | 0.52887 (7) | −0.2045 (3) | 0.67306 (15) | 0.0420 (4) | |
| O1 | 0.44080 (6) | 0.3312 (3) | 0.69827 (13) | 0.0347 (4) | |
| O2 | 0.46297 (6) | 0.2522 (3) | 0.54394 (14) | 0.0396 (4) | |
| O3 | 0.28940 (13) | 1.2782 (7) | 0.2481 (3) | 0.0537 (13) | 0.508 (5) |
| O3' | 0.25060 (16) | 1.2320 (10) | 0.3707 (4) | 0.0757 (18) | 0.492 (5) |
| H1W1 | 0.5398 (10) | −0.346 (3) | 0.7104 (19) | 0.051 (8)* | |
| H1W2 | 0.5313 (11) | −0.208 (5) | 0.6055 (12) | 0.062 (9)* | |
| C1 | 0.43534 (8) | 0.3714 (4) | 0.59025 (19) | 0.0299 (5) | |
| C2 | 0.39595 (8) | 0.5736 (4) | 0.52428 (18) | 0.0283 (4) | |
| C3 | 0.35743 (9) | 0.6552 (5) | 0.5675 (2) | 0.0396 (5) | |
| H3 | 0.3554 | 0.5809 | 0.6363 | 0.048* | |
| C4 | 0.32199 (9) | 0.8489 (6) | 0.5070 (2) | 0.0444 (6) | |
| H4 | 0.2963 | 0.9046 | 0.5357 | 0.053* | |
| C5 | 0.32469 (8) | 0.9588 (4) | 0.4047 (2) | 0.0348 (5) | |
| C6 | 0.36283 (9) | 0.8759 (5) | 0.3612 (2) | 0.0373 (5) | |
| H6 | 0.3645 | 0.9485 | 0.2919 | 0.045* | |
| C7 | 0.39830 (9) | 0.6846 (5) | 0.4219 (2) | 0.0358 (5) | |
| H7 | 0.4240 | 0.6303 | 0.3932 | 0.043* | |
| C8 | 0.28767 (9) | 1.1697 (5) | 0.3399 (2) | 0.0460 (6) | |
| H8 | 0.2621 | 1.2233 | 0.3691 | 0.055* | 0.508 (5) |
| H8' | 0.2924 | 1.2551 | 0.2760 | 0.055* | 0.492 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0384 (2) | 0.02089 (19) | 0.0487 (3) | 0.000 | 0.01878 (17) | 0.000 |
| O1W | 0.0676 (11) | 0.0278 (8) | 0.0359 (10) | 0.0119 (8) | 0.0247 (8) | 0.0052 (7) |
| O1 | 0.0445 (9) | 0.0313 (8) | 0.0266 (8) | −0.0005 (7) | 0.0101 (6) | 0.0054 (6) |
| O2 | 0.0460 (9) | 0.0351 (8) | 0.0355 (9) | 0.0121 (7) | 0.0111 (7) | −0.0003 (7) |
| O3 | 0.051 (2) | 0.055 (2) | 0.052 (2) | 0.0156 (17) | 0.0141 (17) | 0.0215 (19) |
| O3' | 0.058 (3) | 0.086 (4) | 0.079 (3) | 0.036 (2) | 0.019 (2) | 0.008 (3) |
| C1 | 0.0335 (11) | 0.0244 (10) | 0.0276 (11) | −0.0051 (8) | 0.0051 (8) | −0.0011 (8) |
| C2 | 0.0318 (10) | 0.0251 (10) | 0.0264 (10) | −0.0022 (8) | 0.0078 (8) | −0.0022 (9) |
| C3 | 0.0413 (12) | 0.0478 (13) | 0.0338 (13) | 0.0033 (11) | 0.0180 (10) | 0.0055 (10) |
| C4 | 0.0356 (12) | 0.0557 (15) | 0.0458 (15) | 0.0093 (11) | 0.0190 (10) | −0.0025 (12) |
| C5 | 0.0314 (11) | 0.0341 (12) | 0.0337 (12) | 0.0016 (9) | 0.0044 (9) | −0.0032 (10) |
| C6 | 0.0418 (12) | 0.0386 (12) | 0.0322 (12) | 0.0061 (10) | 0.0135 (9) | 0.0093 (10) |
| C7 | 0.0417 (12) | 0.0366 (11) | 0.0342 (12) | 0.0106 (10) | 0.0196 (10) | 0.0037 (10) |
| C8 | 0.0368 (13) | 0.0432 (13) | 0.0497 (16) | 0.0091 (11) | 0.0043 (11) | −0.0036 (12) |
| Zn1—O1w | 1.983 (2) | C2—C3 | 1.395 (3) |
| Zn1—O1wi | 1.983 (2) | C3—C4 | 1.392 (4) |
| Zn1—O1i | 2.005 (2) | C3—H3 | 0.9300 |
| Zn1—O1 | 2.005 (2) | C4—C5 | 1.379 (4) |
| Zn1—O2 | 2.512 (2) | C4—H4 | 0.9300 |
| O1W—H1W1 | 0.84 (1) | C5—C6 | 1.389 (3) |
| O1W—H1W2 | 0.84 (1) | C5—C8 | 1.490 (3) |
| O1—C1 | 1.279 (3) | C6—C7 | 1.385 (3) |
| O2—C1 | 1.241 (3) | C6—H6 | 0.9300 |
| O3—C8 | 1.251 (4) | C7—H7 | 0.9300 |
| O3'—C8 | 1.240 (5) | C8—H8 | 0.9300 |
| C1—C2 | 1.498 (3) | C8—H8' | 0.9300 |
| C2—C7 | 1.379 (3) | ||
| O1W—Zn1—O1Wi | 91.11 (10) | C5—C4—H4 | 119.8 |
| O1W—Zn1—O1i | 100.59 (7) | C3—C4—H4 | 119.8 |
| O1Wi—Zn1—O1i | 135.95 (7) | C4—C5—C6 | 120.0 (2) |
| O1W—Zn1—O1 | 135.95 (7) | C4—C5—C8 | 121.1 (2) |
| O1Wi—Zn1—O1 | 100.59 (7) | C6—C5—C8 | 118.9 (2) |
| O1i—Zn1—O1 | 99.75 (9) | C7—C6—C5 | 119.6 (2) |
| Zn1—O1W—H1W1 | 117.8 (17) | C7—C6—H6 | 120.2 |
| Zn1—O1W—H1W2 | 130.4 (17) | C5—C6—H6 | 120.2 |
| H1W1—O1W—H1W2 | 111.8 (16) | C2—C7—C6 | 120.8 (2) |
| C1—O1—Zn1 | 102.62 (13) | C2—C7—H7 | 119.6 |
| O2—C1—O1 | 120.65 (19) | C6—C7—H7 | 119.6 |
| O2—C1—C2 | 121.9 (2) | O3—C8—O3' | 116.3 (3) |
| O1—C1—C2 | 117.42 (19) | O3—C8—C5 | 123.1 (3) |
| C7—C2—C3 | 119.6 (2) | O3'—C8—C5 | 120.4 (3) |
| C7—C2—C1 | 120.14 (19) | O3—C8—H8 | 118.4 |
| C3—C2—C1 | 120.2 (2) | C5—C8—H8 | 118.4 |
| C4—C3—C2 | 119.5 (2) | O3'—C8—H8' | 119.8 |
| C4—C3—H3 | 120.2 | C5—C8—H8' | 119.8 |
| C2—C3—H3 | 120.2 | H8—C8—H8' | 121.5 |
| C5—C4—C3 | 120.4 (2) | ||
| O1W—Zn1—O1—C1 | −27.75 (17) | C3—C4—C5—C6 | 0.1 (4) |
| O1Wi—Zn1—O1—C1 | −130.56 (13) | C3—C4—C5—C8 | −178.9 (2) |
| O1i—Zn1—O1—C1 | 88.73 (13) | C4—C5—C6—C7 | −0.6 (4) |
| Zn1—O1—C1—O2 | 2.0 (2) | C8—C5—C6—C7 | 178.5 (2) |
| Zn1—O1—C1—C2 | −175.83 (14) | C3—C2—C7—C6 | −0.1 (3) |
| O2—C1—C2—C7 | −17.2 (3) | C1—C2—C7—C6 | −178.6 (2) |
| O1—C1—C2—C7 | 160.7 (2) | C5—C6—C7—C2 | 0.6 (4) |
| O2—C1—C2—C3 | 164.4 (2) | C4—C5—C8—O3 | 178.6 (3) |
| O1—C1—C2—C3 | −17.8 (3) | C6—C5—C8—O3 | −0.5 (4) |
| C7—C2—C3—C4 | −0.3 (4) | C4—C5—C8—O3' | −7.0 (5) |
| C1—C2—C3—C4 | 178.2 (2) | C6—C5—C8—O3' | 173.9 (3) |
| C2—C3—C4—C5 | 0.3 (4) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W1···O1ii | 0.84 (1) | 1.93 (1) | 2.761 (2) | 174 (3) |
| O1W—H1W2···O2iii | 0.84 (1) | 1.88 (1) | 2.720 (2) | 174 (3) |
| Symmetry codes: (ii) −x+1, y−1, −z+3/2; (iii) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W1···O1i | 0.84 (1) | 1.93 (1) | 2.761 (2) | 174 (3) |
| O1W—H1W2···O2ii | 0.84 (1) | 1.88 (1) | 2.720 (2) | 174 (3) |
| Symmetry codes: (i) −x+1, y−1, −z+3/2; (ii) −x+1, −y, −z+1. |
We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this work.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2006). Acta Cryst. E62, m3524–m3526.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2008). publCIF. In preparation.
A pseuodpolymorph of the title compound containing a solvent water molecule was isolated from the reaction of zinc acetate and 4-formylbenzoic acid in the presence of sodium hydroxide (Deng et al., 2006). The reaction with pyridine in place of sodium hydroxide yielded the title polymorph.