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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): m447.
Published online 2008 February 6. doi:  10.1107/S1600536808003152
PMCID: PMC2960827

Diaqua­bis(4-formyl­benzoato-κO)zinc(II)

Abstract

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.

Related literature

A pseudo-polymorph of the title compound containing a solvent water mol­ecule exists in a P2/c modification, which features zinc in an unambiguous tetra­hedral coordination geometry; see Deng et al. (2006 [triangle]).

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Object name is e-64-0m447-scheme1.jpg

Experimental

Crystal data

  • [Zn(C8H5O3)2(H2O)2]
  • M r = 399.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m447-efi1.jpg
  • a = 27.537 (1) Å
  • b = 5.0039 (2) Å
  • c = 12.0930 (6) Å
  • β = 110.039 (2)°
  • V = 1565.4 (1) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.61 mm−1
  • T = 295 (2) K
  • 0.34 × 0.26 × 0.18 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.532, T max = 0.760
  • 7203 measured reflections
  • 1785 independent reflections
  • 1448 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.082
  • S = 1.09
  • 1785 reflections
  • 132 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808003152/bt2669sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003152/bt2669Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054G036), Heilongjiang University and the University of Malaya for supporting this work.

supplementary crystallographic information

Comment

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.

Experimental

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%.

Refinement

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.

Figures

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.

Crystal data

[Zn(C8H5O3)2(H2O)2]F000 = 816
Mr = 399.64Dx = 1.696 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5776 reflections
a = 27.537 (1) Åθ = 3.2–27.5º
b = 5.0039 (2) ŵ = 1.61 mm1
c = 12.0930 (6) ÅT = 295 (2) K
β = 110.039 (2)ºBlock, colorless
V = 1565.4 (1) Å30.34 × 0.26 × 0.18 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer1785 independent reflections
Radiation source: fine-focus sealed tube1448 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
Detector resolution: 10.000 pixels mm-1θmax = 27.5º
T = 295(2) Kθmin = 3.2º
ω scansh = −35→35
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)k = −6→6
Tmin = 0.532, Tmax = 0.760l = −15→15
7203 measured reflections

Refinement

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 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 reflectionsΔρmax = 0.59 e Å3
132 parametersΔρmin = −0.38 e Å3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Zn10.50000.07300 (7)0.75000.03500 (15)
O1W0.52887 (7)−0.2045 (3)0.67306 (15)0.0420 (4)
O10.44080 (6)0.3312 (3)0.69827 (13)0.0347 (4)
O20.46297 (6)0.2522 (3)0.54394 (14)0.0396 (4)
O30.28940 (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)
H1W10.5398 (10)−0.346 (3)0.7104 (19)0.051 (8)*
H1W20.5313 (11)−0.208 (5)0.6055 (12)0.062 (9)*
C10.43534 (8)0.3714 (4)0.59025 (19)0.0299 (5)
C20.39595 (8)0.5736 (4)0.52428 (18)0.0283 (4)
C30.35743 (9)0.6552 (5)0.5675 (2)0.0396 (5)
H30.35540.58090.63630.048*
C40.32199 (9)0.8489 (6)0.5070 (2)0.0444 (6)
H40.29630.90460.53570.053*
C50.32469 (8)0.9588 (4)0.4047 (2)0.0348 (5)
C60.36283 (9)0.8759 (5)0.3612 (2)0.0373 (5)
H60.36450.94850.29190.045*
C70.39830 (9)0.6846 (5)0.4219 (2)0.0358 (5)
H70.42400.63030.39320.043*
C80.28767 (9)1.1697 (5)0.3399 (2)0.0460 (6)
H80.26211.22330.36910.055*0.508 (5)
H8'0.29241.25510.27600.055*0.492 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0384 (2)0.02089 (19)0.0487 (3)0.0000.01878 (17)0.000
O1W0.0676 (11)0.0278 (8)0.0359 (10)0.0119 (8)0.0247 (8)0.0052 (7)
O10.0445 (9)0.0313 (8)0.0266 (8)−0.0005 (7)0.0101 (6)0.0054 (6)
O20.0460 (9)0.0351 (8)0.0355 (9)0.0121 (7)0.0111 (7)−0.0003 (7)
O30.051 (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)
C10.0335 (11)0.0244 (10)0.0276 (11)−0.0051 (8)0.0051 (8)−0.0011 (8)
C20.0318 (10)0.0251 (10)0.0264 (10)−0.0022 (8)0.0078 (8)−0.0022 (9)
C30.0413 (12)0.0478 (13)0.0338 (13)0.0033 (11)0.0180 (10)0.0055 (10)
C40.0356 (12)0.0557 (15)0.0458 (15)0.0093 (11)0.0190 (10)−0.0025 (12)
C50.0314 (11)0.0341 (12)0.0337 (12)0.0016 (9)0.0044 (9)−0.0032 (10)
C60.0418 (12)0.0386 (12)0.0322 (12)0.0061 (10)0.0135 (9)0.0093 (10)
C70.0417 (12)0.0366 (11)0.0342 (12)0.0106 (10)0.0196 (10)0.0037 (10)
C80.0368 (13)0.0432 (13)0.0497 (16)0.0091 (11)0.0043 (11)−0.0036 (12)

Geometric parameters (Å, °)

Zn1—O1w1.983 (2)C2—C31.395 (3)
Zn1—O1wi1.983 (2)C3—C41.392 (4)
Zn1—O1i2.005 (2)C3—H30.9300
Zn1—O12.005 (2)C4—C51.379 (4)
Zn1—O22.512 (2)C4—H40.9300
O1W—H1W10.84 (1)C5—C61.389 (3)
O1W—H1W20.84 (1)C5—C81.490 (3)
O1—C11.279 (3)C6—C71.385 (3)
O2—C11.241 (3)C6—H60.9300
O3—C81.251 (4)C7—H70.9300
O3'—C81.240 (5)C8—H80.9300
C1—C21.498 (3)C8—H8'0.9300
C2—C71.379 (3)
O1W—Zn1—O1Wi91.11 (10)C5—C4—H4119.8
O1W—Zn1—O1i100.59 (7)C3—C4—H4119.8
O1Wi—Zn1—O1i135.95 (7)C4—C5—C6120.0 (2)
O1W—Zn1—O1135.95 (7)C4—C5—C8121.1 (2)
O1Wi—Zn1—O1100.59 (7)C6—C5—C8118.9 (2)
O1i—Zn1—O199.75 (9)C7—C6—C5119.6 (2)
Zn1—O1W—H1W1117.8 (17)C7—C6—H6120.2
Zn1—O1W—H1W2130.4 (17)C5—C6—H6120.2
H1W1—O1W—H1W2111.8 (16)C2—C7—C6120.8 (2)
C1—O1—Zn1102.62 (13)C2—C7—H7119.6
O2—C1—O1120.65 (19)C6—C7—H7119.6
O2—C1—C2121.9 (2)O3—C8—O3'116.3 (3)
O1—C1—C2117.42 (19)O3—C8—C5123.1 (3)
C7—C2—C3119.6 (2)O3'—C8—C5120.4 (3)
C7—C2—C1120.14 (19)O3—C8—H8118.4
C3—C2—C1120.2 (2)C5—C8—H8118.4
C4—C3—C2119.5 (2)O3'—C8—H8'119.8
C4—C3—H3120.2C5—C8—H8'119.8
C2—C3—H3120.2H8—C8—H8'121.5
C5—C4—C3120.4 (2)
O1W—Zn1—O1—C1−27.75 (17)C3—C4—C5—C60.1 (4)
O1Wi—Zn1—O1—C1−130.56 (13)C3—C4—C5—C8−178.9 (2)
O1i—Zn1—O1—C188.73 (13)C4—C5—C6—C7−0.6 (4)
Zn1—O1—C1—O22.0 (2)C8—C5—C6—C7178.5 (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—C7160.7 (2)C5—C6—C7—C20.6 (4)
O2—C1—C2—C3164.4 (2)C4—C5—C8—O3178.6 (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—C4178.2 (2)C6—C5—C8—O3'173.9 (3)
C2—C3—C4—C50.3 (4)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O1ii0.84 (1)1.93 (1)2.761 (2)174 (3)
O1W—H1W2···O2iii0.84 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2669).

References

  • 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. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography