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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m32.
Published online 2007 December 6. doi:  10.1107/S1600536807062460
PMCID: PMC2914921

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

Abstract

The Zn atom in the title mononuclear complex, [Zn(C8H7O2)2(H2O)2], lies on a special position of site symmetry 2. The carboxyl­ate group binds in a monodentate manner so that the geometry is best described as tetra­hedral. Adjacent mol­ecules are linked by O—H(...)O hydrogen bonds into a three-dimensional network.

Related literature

For related literature, see: Song et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m32-scheme1.jpg

Experimental

Crystal data

  • [Zn(C8H7O2)2(H2O)2]
  • M r = 371.70
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m32-efi1.jpg
  • a = 26.8432 (5) Å
  • b = 5.0600 (1) Å
  • c = 12.0609 (2) Å
  • β = 106.806 (1)°
  • V = 1568.22 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.59 mm−1
  • T = 273 (2) K
  • 0.32 × 0.29 × 0.26 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.605, T max = 0.660
  • 9051 measured reflections
  • 1784 independent reflections
  • 1566 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.076
  • S = 1.05
  • 1784 reflections
  • 112 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 2004 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062460/ng2397sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062460/ng2397Isup2.hkl

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

Acknowledgments

The authors acknowledge South China University of Technology and Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

In the structural investigation of 4-methylbenzate complexes, it has been found that the 4-methylbenzoic acid functions as a multidentate ligand [(Song et al. (2007)], with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Zn complex obtained by the reaction of 4-methylbenzoic acid with zinc chloride in alkaline aqueous solution.

As illustrated in Figure 1, the ZnII atom, possesses crystallogarphically imposed C2 symmetry, which is coordinated by two O atoms from two 4-methylbenzate ligands and two water molecules, and displays a tetrahedral geometry. Intermolecular O—H···O hydrogen bonding interactions (Table 1) between the coordinated water molecules and the carboxyl O atoms of 4-methylbenzate ligands stabilize the structural packing (Fig. 2).

Experimental

A mixture of zinc nitrate(1 mmol), 4-methylbenzoic acid (1 mmol) NaOH (1.5 mmol) and H2O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. The crystals obtained were washed with water and dryed in air.

Refinement

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 - 0.97 Å, and with Uiso(H) = 1.2 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å, and with Uiso(H) = 1.5 Ueq(O).

Figures

Fig. 1.
The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids. Unlabeled atoms are related to the labelled atoms by the symmetry operator (-x, y, 0.5 - z).
Fig. 2.
A packing view of the title compound. The intermolecluar hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(C8H7O2)2(H2O)2]F000 = 768
Mr = 371.70Dx = 1.574 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3600 reflections
a = 26.8432 (5) Åθ = 3.0–27.5º
b = 5.06000 (10) ŵ = 1.59 mm1
c = 12.0609 (2) ÅT = 273 (2) K
β = 106.8060 (10)ºBlock, colorless
V = 1568.22 (5) Å30.32 × 0.29 × 0.26 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer1784 independent reflections
Radiation source: fine-focus sealed tube1566 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 273(2) Kθmax = 27.5º
[var phi] and ω scanθmin = 3.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −34→34
Tmin = 0.605, Tmax = 0.660k = −6→6
9051 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0378P)2 + 0.8633P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1784 reflectionsΔρmax = 0.25 e Å3
112 parametersΔρmin = −0.42 e Å3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
C10.06512 (8)0.6273 (4)0.40073 (18)0.0311 (4)
C20.10484 (7)0.4299 (4)0.46142 (17)0.0300 (4)
C30.10475 (9)0.3264 (4)0.56687 (19)0.0409 (5)
H30.07950.38130.60090.049*
C40.14146 (9)0.1422 (5)0.6231 (2)0.0437 (5)
H40.14080.07710.69480.052*
C50.17921 (8)0.0533 (4)0.5741 (2)0.0384 (5)
C60.17872 (9)0.1556 (5)0.4675 (2)0.0463 (6)
H60.20360.09850.43290.056*
C70.14237 (8)0.3399 (5)0.4110 (2)0.0416 (5)
H70.14290.40440.33910.050*
C80.21820 (10)−0.1520 (5)0.6349 (2)0.0550 (6)
H8A0.2226−0.14450.71660.082*
H8B0.2510−0.11830.62040.082*
H8C0.2059−0.32430.60620.082*
O10.05926 (5)0.6655 (3)0.29258 (12)0.0356 (3)
O20.03766 (6)0.7481 (3)0.45086 (13)0.0415 (4)
O1W0.02917 (7)1.2004 (3)0.16969 (14)0.0450 (4)
H1W0.0402 (11)1.342 (3)0.199 (2)0.067*
H2W0.0326 (10)1.199 (5)0.1058 (12)0.067*
Zn10.00000.92389 (6)0.25000.03485 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0344 (10)0.0256 (9)0.0297 (11)−0.0033 (8)0.0038 (9)−0.0014 (7)
C20.0319 (9)0.0304 (9)0.0257 (10)0.0002 (8)0.0053 (8)−0.0020 (8)
C30.0470 (12)0.0430 (11)0.0362 (12)0.0136 (10)0.0177 (10)0.0066 (9)
C40.0527 (13)0.0423 (12)0.0365 (13)0.0112 (10)0.0135 (11)0.0113 (9)
C50.0369 (11)0.0322 (10)0.0392 (12)0.0039 (9)0.0000 (9)−0.0018 (9)
C60.0383 (11)0.0568 (13)0.0453 (14)0.0146 (11)0.0142 (11)−0.0009 (11)
C70.0425 (12)0.0514 (12)0.0328 (12)0.0069 (10)0.0139 (10)0.0041 (10)
C80.0494 (14)0.0459 (13)0.0588 (17)0.0159 (11)−0.0015 (12)−0.0005 (12)
O10.0428 (8)0.0325 (7)0.0296 (8)0.0029 (6)0.0074 (6)0.0073 (6)
O20.0459 (8)0.0389 (8)0.0379 (9)0.0135 (7)0.0094 (7)−0.0002 (7)
O1W0.0727 (11)0.0285 (7)0.0383 (9)−0.0127 (7)0.0232 (9)−0.0040 (6)
Zn10.0361 (2)0.02136 (17)0.0484 (2)0.0000.01423 (16)0.000

Geometric parameters (Å, °)

C1—O21.241 (2)C6—H60.9300
C1—O11.283 (2)C7—H70.9300
C1—C21.490 (3)C8—H8A0.9600
C2—C31.376 (3)C8—H8B0.9600
C2—C71.395 (3)C8—H8C0.9600
C3—C41.383 (3)O1—Zn12.0078 (14)
C3—H30.9300O1W—Zn11.9867 (14)
C4—C51.387 (3)O1W—H1W0.813 (9)
C4—H40.9300O1W—H2W0.803 (9)
C5—C61.383 (3)Zn1—O1Wi1.9867 (14)
C5—C81.506 (3)Zn1—O1i2.0078 (14)
C6—C71.379 (3)
O2—C1—O1120.38 (18)C6—C7—H7119.9
O2—C1—C2122.17 (19)C2—C7—H7119.9
O1—C1—C2117.43 (17)C5—C8—H8A109.5
C3—C2—C7118.26 (19)C5—C8—H8B109.5
C3—C2—C1121.13 (17)H8A—C8—H8B109.5
C7—C2—C1120.59 (18)C5—C8—H8C109.5
C2—C3—C4121.21 (19)H8A—C8—H8C109.5
C2—C3—H3119.4H8B—C8—H8C109.5
C4—C3—H3119.4C1—O1—Zn1102.32 (12)
C3—C4—C5121.0 (2)Zn1—O1W—H1W123.8 (18)
C3—C4—H4119.5Zn1—O1W—H2W129.3 (18)
C5—C4—H4119.5H1W—O1W—H2W106.9 (15)
C6—C5—C4117.58 (19)O1Wi—Zn1—O1W90.48 (9)
C6—C5—C8121.9 (2)O1Wi—Zn1—O1i100.86 (7)
C4—C5—C8120.5 (2)O1W—Zn1—O1i136.77 (7)
C7—C6—C5121.8 (2)O1Wi—Zn1—O1136.77 (7)
C7—C6—H6119.1O1W—Zn1—O1100.86 (6)
C5—C6—H6119.1O1i—Zn1—O198.74 (8)
C6—C7—C2120.1 (2)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1ii0.813 (9)1.973 (10)2.774 (2)168 (3)
O1W—H2W···O2iii0.803 (9)1.931 (11)2.726 (2)171 (3)

Symmetry codes: (ii) x, y+1, z; (iii) x, −y+2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2397).

References

  • Bruker (2004). APEX2, SAINT and SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023–m1024.

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