metal-organic compounds
Poly[[diaqua(μ8-benzene-1,2,4,5-tetracarboxylato)calciumzinc] monohydrate]
aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
*Correspondence e-mail: 13623712409@139.com
In the title complex, {[CaZn(C10H2O8)(H2O)2]·H2O}n, the ZnII ion is coordinated by four O atoms from four benzene-1,2,4,5-tetracarboxylate anions in a distorted tetrahedral geometry. The CaII ion is eight-coordinated by six O atoms from four benzene-1,2,4,5-tetracarboxylate anions and by two water molecules in a distorted square-antiprismatic geometry. The CaII and ZnII ions and the lattice water molecule are located on twofold rotation axes; the centroid of the benzene-1,2,4,5-tetracarboxylate anion is located on a centre of inversion. The μ8-bridging mode of the anion results in the formation of a three-dimensional structure with channels extending along [100] in which lattice water molecules are situated. Intermolecular O—H⋯O hydrogen bonds involving the coordinating and lattice water molecules as donors and the carboxylate O atoms and lattice water molecules as acceptors are present in the structure.
Related literature
For background to complexes based on benzene-1,2,4,5-tetracarboxylic acid and its anions, see: Prajapati et al. (2009); Xie et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku/MSC, 2004); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812034113/wm2661sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034113/wm2661Isup2.hkl
A mixture of ZnCl2 (0.05 mmol), CaCl2 (0.05 mmol), benzene-1,2,4,5-tetracarboxylic acid (0.05 mmol), water (4 ml) and methanol (4 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 393 K for 72 h, then cooled to room temperature. Colourless crystals were obtained from the filtrate and dried in air.
The H atom bound to C5 was positioned geometrically and refined as riding, with C—H = 0.93 Å. H atoms bound to water O atoms were found from difference maps and refined with distance restraints of O—H = 0.85 Å. All H atoms were refined with Uiso(H) = 1.2 Ueq(C,O).
Data collection: CrystalClear (Rigaku/MSC, 2004); cell
CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[CaZn(C10H2O8)(H2O)2]·H2O | F(000) = 412 |
Mr = 409.61 | Dx = 2.207 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2006 (12) Å | Cell parameters from 1852 reflections |
b = 9.770 (2) Å | θ = 2.1–27.9° |
c = 11.259 (3) Å | µ = 2.47 mm−1 |
β = 115.33 (2)° | T = 293 K |
V = 616.5 (2) Å3 | Prism, colourless |
Z = 2 | 0.19 × 0.17 × 0.14 mm |
Rigaku Saturn CCD diffractometer | 1447 independent reflections |
Radiation source: fine-focus sealed tube | 1360 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.9°, θmin = 2.1° |
ω scans | h = −8→7 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | k = −12→12 |
Tmin = 0.651, Tmax = 0.723 | l = −14→9 |
3849 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
1447 reflections | (Δ/σ)max < 0.001 |
106 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[CaZn(C10H2O8)(H2O)2]·H2O | V = 616.5 (2) Å3 |
Mr = 409.61 | Z = 2 |
Monoclinic, P2/c | Mo Kα radiation |
a = 6.2006 (12) Å | µ = 2.47 mm−1 |
b = 9.770 (2) Å | T = 293 K |
c = 11.259 (3) Å | 0.19 × 0.17 × 0.14 mm |
β = 115.33 (2)° |
Rigaku Saturn CCD diffractometer | 1447 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | 1360 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 0.723 | Rint = 0.027 |
3849 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.38 e Å−3 |
1447 reflections | Δρmin = −0.56 e Å−3 |
106 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.0000 | −0.23661 (3) | −0.2500 | 0.01455 (15) | |
Ca1 | 0.5000 | −0.51637 (6) | 0.2500 | 0.01865 (18) | |
O1 | 0.2538 (3) | −0.34567 (15) | −0.11362 (14) | 0.0200 (3) | |
O2 | 0.5157 (3) | −0.35902 (17) | 0.09520 (15) | 0.0244 (4) | |
O3 | 0.7153 (3) | −0.29814 (17) | −0.11799 (15) | 0.0221 (3) | |
O4 | 0.8547 (3) | −0.10913 (16) | −0.16958 (16) | 0.0209 (3) | |
O5 | 0.0955 (3) | −0.4370 (2) | 0.14219 (19) | 0.0345 (4) | |
H5A | 0.0534 | −0.3562 | 0.1510 | 0.041* | |
H5B | −0.0270 | −0.4882 | 0.1110 | 0.041* | |
C1 | 0.4111 (4) | −0.2941 (2) | −0.00731 (19) | 0.0144 (4) | |
C2 | 0.7341 (3) | −0.1716 (2) | −0.11904 (19) | 0.0156 (4) | |
C3 | 0.4642 (3) | −0.1423 (2) | −0.00489 (18) | 0.0138 (4) | |
C4 | 0.6098 (3) | −0.0840 (2) | −0.05841 (18) | 0.0139 (4) | |
C5 | 0.3573 (4) | −0.0571 (2) | 0.05340 (18) | 0.0160 (4) | |
H5 | 0.2618 | −0.0953 | 0.0898 | 0.019* | |
O6 | 1.0000 | 0.1852 (4) | −0.2500 | 0.0787 (13) | |
H6 | 0.9216 | 0.1282 | −0.2269 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0131 (2) | 0.0155 (2) | 0.0160 (2) | 0.000 | 0.00726 (16) | 0.000 |
Ca1 | 0.0200 (3) | 0.0125 (3) | 0.0166 (3) | 0.000 | 0.0012 (2) | 0.000 |
O1 | 0.0177 (7) | 0.0131 (7) | 0.0220 (7) | −0.0011 (5) | 0.0016 (6) | 0.0009 (5) |
O2 | 0.0274 (8) | 0.0226 (8) | 0.0185 (7) | 0.0040 (6) | 0.0054 (6) | 0.0062 (6) |
O3 | 0.0241 (8) | 0.0164 (7) | 0.0272 (8) | −0.0003 (7) | 0.0123 (7) | −0.0057 (6) |
O4 | 0.0220 (8) | 0.0206 (7) | 0.0271 (8) | −0.0008 (6) | 0.0171 (7) | −0.0036 (6) |
O5 | 0.0247 (8) | 0.0326 (9) | 0.0434 (11) | 0.0056 (8) | 0.0118 (8) | 0.0062 (8) |
C1 | 0.0128 (9) | 0.0134 (9) | 0.0171 (9) | 0.0011 (7) | 0.0063 (7) | −0.0012 (7) |
C2 | 0.0110 (8) | 0.0198 (10) | 0.0144 (9) | 0.0009 (8) | 0.0040 (7) | −0.0045 (7) |
C3 | 0.0118 (8) | 0.0148 (9) | 0.0136 (9) | −0.0016 (7) | 0.0043 (7) | −0.0032 (7) |
C4 | 0.0121 (8) | 0.0153 (10) | 0.0136 (9) | −0.0013 (7) | 0.0050 (7) | −0.0031 (7) |
C5 | 0.0156 (9) | 0.0174 (10) | 0.0160 (9) | −0.0031 (8) | 0.0077 (7) | −0.0023 (7) |
O6 | 0.071 (3) | 0.040 (2) | 0.085 (3) | 0.000 | −0.005 (2) | 0.000 |
Zn1—O4i | 1.9701 (15) | O3—C2 | 1.243 (3) |
Zn1—O4ii | 1.9701 (15) | O3—Ca1v | 2.3618 (17) |
Zn1—O1iii | 1.9754 (15) | O4—C2 | 1.273 (3) |
Zn1—O1 | 1.9754 (15) | O4—Zn1vii | 1.9701 (15) |
Ca1—O2iv | 2.3571 (17) | O5—H5A | 0.8500 |
Ca1—O2 | 2.3571 (17) | O5—H5B | 0.8500 |
Ca1—O3v | 2.3618 (17) | C1—C3 | 1.517 (3) |
Ca1—O3vi | 2.3618 (17) | C2—C4 | 1.497 (3) |
Ca1—O5iv | 2.4003 (19) | C3—C5 | 1.391 (3) |
Ca1—O5 | 2.4003 (19) | C3—C4 | 1.403 (3) |
Ca1—O1v | 2.9172 (16) | C4—C5viii | 1.392 (3) |
Ca1—O1vi | 2.9172 (16) | C5—C4viii | 1.392 (3) |
O1—C1 | 1.280 (2) | C5—H5 | 0.9300 |
O1—Ca1v | 2.9172 (16) | O6—H6 | 0.8500 |
O2—C1 | 1.231 (3) | ||
O4i—Zn1—O4ii | 101.57 (9) | O3v—Ca1—O1vi | 72.21 (5) |
O4i—Zn1—O1iii | 109.22 (7) | O3vi—Ca1—O1vi | 66.20 (5) |
O4ii—Zn1—O1iii | 110.65 (7) | O5iv—Ca1—O1vi | 123.51 (6) |
O4i—Zn1—O1 | 110.65 (7) | O5—Ca1—O1vi | 75.32 (6) |
O4ii—Zn1—O1 | 109.22 (7) | O1v—Ca1—O1vi | 124.96 (6) |
O1iii—Zn1—O1 | 114.72 (9) | C1—O1—Zn1 | 123.33 (14) |
O2iv—Ca1—O2 | 98.59 (9) | C1—O1—Ca1v | 108.26 (12) |
O2iv—Ca1—O3v | 140.78 (6) | Zn1—O1—Ca1v | 105.21 (6) |
O2—Ca1—O3v | 103.07 (6) | C1—O2—Ca1 | 149.04 (15) |
O2iv—Ca1—O3vi | 103.07 (6) | C2—O3—Ca1v | 141.97 (13) |
O2—Ca1—O3vi | 140.78 (6) | C2—O4—Zn1vii | 111.98 (13) |
O3v—Ca1—O3vi | 79.77 (9) | Ca1—O5—H5A | 123.2 |
O2iv—Ca1—O5iv | 77.30 (6) | Ca1—O5—H5B | 125.0 |
O2—Ca1—O5iv | 78.37 (7) | H5A—O5—H5B | 109.3 |
O3v—Ca1—O5iv | 138.88 (7) | O2—C1—O1 | 124.0 (2) |
O3vi—Ca1—O5iv | 75.09 (7) | O2—C1—C3 | 117.63 (18) |
O2iv—Ca1—O5 | 78.37 (7) | O1—C1—C3 | 118.31 (17) |
O2—Ca1—O5 | 77.30 (6) | O3—C2—O4 | 123.82 (17) |
O3v—Ca1—O5 | 75.09 (7) | O3—C2—C4 | 119.71 (17) |
O3vi—Ca1—O5 | 138.88 (7) | O4—C2—C4 | 116.47 (18) |
O5iv—Ca1—O5 | 142.29 (10) | C5—C3—C4 | 118.95 (18) |
O2iv—Ca1—O1v | 152.50 (5) | C5—C3—C1 | 116.74 (18) |
O2—Ca1—O1v | 73.48 (5) | C4—C3—C1 | 124.31 (17) |
O3v—Ca1—O1v | 66.20 (5) | C5viii—C4—C3 | 119.66 (18) |
O3vi—Ca1—O1v | 72.21 (5) | C5viii—C4—C2 | 119.30 (18) |
O5iv—Ca1—O1v | 75.32 (6) | C3—C4—C2 | 121.03 (18) |
O5—Ca1—O1v | 123.51 (6) | C3—C5—C4viii | 121.39 (18) |
O2iv—Ca1—O1vi | 73.48 (5) | C3—C5—H5 | 119.3 |
O2—Ca1—O1vi | 152.50 (5) | C4viii—C5—H5 | 119.3 |
O4i—Zn1—O1—C1 | −44.54 (17) | Ca1v—O3—C2—O4 | −82.2 (3) |
O4ii—Zn1—O1—C1 | 66.46 (16) | Ca1v—O3—C2—C4 | 97.8 (2) |
O1iii—Zn1—O1—C1 | −168.66 (17) | Zn1vii—O4—C2—O3 | 1.6 (2) |
O4i—Zn1—O1—Ca1v | −169.11 (6) | Zn1vii—O4—C2—C4 | −178.32 (13) |
O4ii—Zn1—O1—Ca1v | −58.11 (7) | O2—C1—C3—C5 | −77.1 (2) |
O1iii—Zn1—O1—Ca1v | 66.77 (4) | O1—C1—C3—C5 | 100.1 (2) |
O2iv—Ca1—O2—C1 | −96.5 (3) | O2—C1—C3—C4 | 103.6 (2) |
O3v—Ca1—O2—C1 | 50.6 (3) | O1—C1—C3—C4 | −79.2 (2) |
O3vi—Ca1—O2—C1 | 140.4 (3) | C5—C3—C4—C5viii | −0.6 (3) |
O5iv—Ca1—O2—C1 | −171.5 (3) | C1—C3—C4—C5viii | 178.61 (17) |
O5—Ca1—O2—C1 | −20.5 (3) | C5—C3—C4—C2 | 178.36 (17) |
O1v—Ca1—O2—C1 | 110.5 (3) | C1—C3—C4—C2 | −2.4 (3) |
O1vi—Ca1—O2—C1 | −25.9 (4) | O3—C2—C4—C5viii | 176.38 (17) |
Ca1—O2—C1—O1 | −45.2 (4) | O4—C2—C4—C5viii | −3.7 (3) |
Ca1—O2—C1—C3 | 131.8 (2) | O3—C2—C4—C3 | −2.6 (3) |
Zn1—O1—C1—O2 | 154.42 (16) | O4—C2—C4—C3 | 177.33 (17) |
Ca1v—O1—C1—O2 | −82.4 (2) | C4—C3—C5—C4viii | 0.6 (3) |
Zn1—O1—C1—C3 | −22.6 (2) | C1—C3—C5—C4viii | −178.66 (17) |
Ca1v—O1—C1—C3 | 100.63 (17) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y, −z−1/2; (iii) −x, y, −z−1/2; (iv) −x+1, y, −z+1/2; (v) −x+1, −y−1, −z; (vi) x, −y−1, z+1/2; (vii) x+1, y, z; (viii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O4 | 0.85 | 2.49 | 3.255 (4) | 151 |
O5—H5A···O6viii | 0.85 | 2.11 | 2.914 (4) | 157 |
O5—H5B···O1ix | 0.85 | 2.16 | 2.951 (2) | 156 |
Symmetry codes: (viii) −x+1, −y, −z; (ix) −x, −y−1, −z. |
Experimental details
Crystal data | |
Chemical formula | [CaZn(C10H2O8)(H2O)2]·H2O |
Mr | 409.61 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.2006 (12), 9.770 (2), 11.259 (3) |
β (°) | 115.33 (2) |
V (Å3) | 616.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.47 |
Crystal size (mm) | 0.19 × 0.17 × 0.14 |
Data collection | |
Diffractometer | Rigaku Saturn CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2004) |
Tmin, Tmax | 0.651, 0.723 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3849, 1447, 1360 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.099, 0.84 |
No. of reflections | 1447 |
No. of parameters | 106 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.56 |
Computer programs: CrystalClear (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O4 | 0.85 | 2.49 | 3.255 (4) | 150.5 |
O5—H5A···O6i | 0.85 | 2.11 | 2.914 (4) | 157.1 |
O5—H5B···O1ii | 0.85 | 2.16 | 2.951 (2) | 155.6 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y−1, −z. |
Acknowledgements
This study was supported by the Science and Technology Department of Henan Province (082102330003).
References
Prajapati, R., Mishra, L., Kimura, K. & Raghavaiah, P. (2009). Polyhedron, 28, 600–608. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2004). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, Z.-L., Feng, M.-L., Li, J.-R. & Huang, X.-Y. (2008). Inorg. Chem. Commun. 11, 1143–1146. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
A large number of complexes constructed from the multidentate aromatic ligand benzene-1,2,4,5-tetracarboxylic acid and its corresponding anions have been extensively studied due to the diversity of the coordination modes and sensitivity to pH values of the carboxylate anions. Some of the final products exhibit useful functional properties (Prajapati et al., 2009; Xie et al., 2008). In order to further explore complexes with new structures, we selected benzene-1,2,4,5-tetracarboxylic acid as precursor to self-assembly with ZnCl2 and CaCl2 simultaneously in solution and obtained the title complex, [CaZn(C10H2O8)(H2O)2].(H2O), the crystal structure of which is reported herein.
As shown in Figure 1, the ZnII ion displays a distorted tetrahedral coordination geometry defined by four oxygen atoms from four symmetry-related benzene-1,2,4,5-tetracarboxylate groups (O1, O1A, O4B and O4C). The CaII ion is bound to six oxygen atoms from four benzene-1,2,4,5-tetracarboxylate groups (O1E, O1D, O2, O2F, O3D, O3E) and two water molecules (O5, O5F) leading to a distorted square-antiprismatic geometry. The base plane of the square antiprism consists of atoms O1E, O2F, O3E, and O5F with a mean deviation of 0.1065 Å from the least-squares plane. The top plane of the square antiprism consists of symmetry-related atoms O1D, O2, O3D, and O5. The dihedral angle between the two planes is 3.9 °. The three-dimensional set-up of the structure leaves space for channels extending along [100] where the lattice water molecules are located.
Intermolecular O—H···O hydrogen bonds between coordinating water molecules and lattice water molecules, between coordinating water molecules and carboxylate groups, and between solvent water molecules and carboxylate groups consolidate the crystal packing (Table 1, Fig. 2).