(IUCr) Crystallography Journals Online

Abstract top

In the title complex, {[CaZn(C₁₀H₂O₈)(H₂O)₂]·H₂O}_n, the Zn^II ion is coordinated by four O atoms from four benzene-1,2,4,5-tetracarboxylate anions in a distorted tetrahedral geometry. The Ca^II 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 Ca^II and Zn^II 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 [mu] ₈-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-HO 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.

Comment top

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 Zn^II 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 Ca^II 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).

Poly[[diaqua(µ₈-benzene-1,2,4,5-tetracarboxylato)calciumzinc] monohydrate] top

Crystal data top

[CaZn(C₁₀H₂O₈)(H₂O)₂]·H₂O	F(000) = 412
M_r = 409.61	D_x = 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

Data collection top

Rigaku Saturn CCD diffractometer	1447 independent reflections
Radiation source: fine-focus sealed tube	1360 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.9°, θ_min = 2.1°
ω scans	h = −8→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −12→12
T_min = 0.651, T_max = 0.723	l = −14→9
3849 measured reflections

Refinement top

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(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
1447 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[CaZn(C₁₀H₂O₈)(H₂O)₂]·H₂O	V = 616.5 (2) Å³
M_r = 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)°

Data collection top

Rigaku Saturn CCD diffractometer	1447 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	1360 reflections with I > 2σ(I)
T_min = 0.651, T_max = 0.723	R_int = 0.027
3849 measured reflections	θ_max = 27.9°

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.099	Δρ_max = 0.38 e Å⁻³
S = 0.84	Δρ_min = −0.56 e Å⁻³
1447 reflections	Absolute structure: ?
106 parameters	Flack parameter: ?
0 restraints	Rogers parameter: ?

Special details top

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.

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

Zn1—O4ⁱ	1.9701 (15)	O3—C2	1.243 (3)
Zn1—O4ⁱⁱ	1.9701 (15)	O3—Ca1^v	2.3618 (17)
Zn1—O1ⁱⁱⁱ	1.9754 (15)	O4—C2	1.273 (3)
Zn1—O1	1.9754 (15)	O4—Zn1^vii	1.9701 (15)
Ca1—O2^iv	2.3571 (17)	O5—H5A	0.8500
Ca1—O2	2.3571 (17)	O5—H5B	0.8500
Ca1—O3^v	2.3618 (17)	C1—C3	1.517 (3)
Ca1—O3^vi	2.3618 (17)	C2—C4	1.497 (3)
Ca1—O5^iv	2.4003 (19)	C3—C5	1.391 (3)
Ca1—O5	2.4003 (19)	C3—C4	1.403 (3)
Ca1—O1^v	2.9172 (16)	C4—C5^viii	1.392 (3)
Ca1—O1^vi	2.9172 (16)	C5—C4^viii	1.392 (3)
O1—C1	1.280 (2)	C5—H5	0.9300
O1—Ca1^v	2.9172 (16)	O6—H6	0.8500
O2—C1	1.231 (3)

O4ⁱ—Zn1—O4ⁱⁱ	101.57 (9)	O3^v—Ca1—O1^vi	72.21 (5)
O4ⁱ—Zn1—O1ⁱⁱⁱ	109.22 (7)	O3^vi—Ca1—O1^vi	66.20 (5)
O4ⁱⁱ—Zn1—O1ⁱⁱⁱ	110.65 (7)	O5^iv—Ca1—O1^vi	123.51 (6)
O4ⁱ—Zn1—O1	110.65 (7)	O5—Ca1—O1^vi	75.32 (6)
O4ⁱⁱ—Zn1—O1	109.22 (7)	O1^v—Ca1—O1^vi	124.96 (6)
O1ⁱⁱⁱ—Zn1—O1	114.72 (9)	C1—O1—Zn1	123.33 (14)
O2^iv—Ca1—O2	98.59 (9)	C1—O1—Ca1^v	108.26 (12)
O2^iv—Ca1—O3^v	140.78 (6)	Zn1—O1—Ca1^v	105.21 (6)
O2—Ca1—O3^v	103.07 (6)	C1—O2—Ca1	149.04 (15)
O2^iv—Ca1—O3^vi	103.07 (6)	C2—O3—Ca1^v	141.97 (13)
O2—Ca1—O3^vi	140.78 (6)	C2—O4—Zn1^vii	111.98 (13)
O3^v—Ca1—O3^vi	79.77 (9)	Ca1—O5—H5A	123.2
O2^iv—Ca1—O5^iv	77.30 (6)	Ca1—O5—H5B	125.0
O2—Ca1—O5^iv	78.37 (7)	H5A—O5—H5B	109.3
O3^v—Ca1—O5^iv	138.88 (7)	O2—C1—O1	124.0 (2)
O3^vi—Ca1—O5^iv	75.09 (7)	O2—C1—C3	117.63 (18)
O2^iv—Ca1—O5	78.37 (7)	O1—C1—C3	118.31 (17)
O2—Ca1—O5	77.30 (6)	O3—C2—O4	123.82 (17)
O3^v—Ca1—O5	75.09 (7)	O3—C2—C4	119.71 (17)
O3^vi—Ca1—O5	138.88 (7)	O4—C2—C4	116.47 (18)
O5^iv—Ca1—O5	142.29 (10)	C5—C3—C4	118.95 (18)
O2^iv—Ca1—O1^v	152.50 (5)	C5—C3—C1	116.74 (18)
O2—Ca1—O1^v	73.48 (5)	C4—C3—C1	124.31 (17)
O3^v—Ca1—O1^v	66.20 (5)	C5^viii—C4—C3	119.66 (18)
O3^vi—Ca1—O1^v	72.21 (5)	C5^viii—C4—C2	119.30 (18)
O5^iv—Ca1—O1^v	75.32 (6)	C3—C4—C2	121.03 (18)
O5—Ca1—O1^v	123.51 (6)	C3—C5—C4^viii	121.39 (18)
O2^iv—Ca1—O1^vi	73.48 (5)	C3—C5—H5	119.3
O2—Ca1—O1^vi	152.50 (5)	C4^viii—C5—H5	119.3

O4ⁱ—Zn1—O1—C1	−44.54 (17)	Ca1^v—O3—C2—O4	−82.2 (3)
O4ⁱⁱ—Zn1—O1—C1	66.46 (16)	Ca1^v—O3—C2—C4	97.8 (2)
O1ⁱⁱⁱ—Zn1—O1—C1	−168.66 (17)	Zn1^vii—O4—C2—O3	1.6 (2)
O4ⁱ—Zn1—O1—Ca1^v	−169.11 (6)	Zn1^vii—O4—C2—C4	−178.32 (13)
O4ⁱⁱ—Zn1—O1—Ca1^v	−58.11 (7)	O2—C1—C3—C5	−77.1 (2)
O1ⁱⁱⁱ—Zn1—O1—Ca1^v	66.77 (4)	O1—C1—C3—C5	100.1 (2)
O2^iv—Ca1—O2—C1	−96.5 (3)	O2—C1—C3—C4	103.6 (2)
O3^v—Ca1—O2—C1	50.6 (3)	O1—C1—C3—C4	−79.2 (2)
O3^vi—Ca1—O2—C1	140.4 (3)	C5—C3—C4—C5^viii	−0.6 (3)
O5^iv—Ca1—O2—C1	−171.5 (3)	C1—C3—C4—C5^viii	178.61 (17)
O5—Ca1—O2—C1	−20.5 (3)	C5—C3—C4—C2	178.36 (17)
O1^v—Ca1—O2—C1	110.5 (3)	C1—C3—C4—C2	−2.4 (3)
O1^vi—Ca1—O2—C1	−25.9 (4)	O3—C2—C4—C5^viii	176.38 (17)
Ca1—O2—C1—O1	−45.2 (4)	O4—C2—C4—C5^viii	−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)
Ca1^v—O1—C1—O2	−82.4 (2)	C4—C3—C5—C4^viii	0.6 (3)
Zn1—O1—C1—C3	−22.6 (2)	C1—C3—C5—C4^viii	−178.66 (17)
Ca1^v—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.

Hydrogen-bond geometry (Å, º) top

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···O6^viii	0.85	2.11	2.914 (4)	157
O5—H5B···O1^ix	0.85	2.16	2.951 (2)	156

Symmetry codes: (viii) −x+1, −y, −z; (ix) −x, −y−1, −z.

Hydrogen-bond geometry (Å, º) top

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.

supplementary materials

Poly[[diaqua(₈-benzene-1,2,4,5-tetracarboxylato)calciumzinc] monohydrate]

Y.-Y. Jia, B. Chen and Y.-X. Yuan

	Fig. 1. View of the building units of the title compound showing the coordination environment around the metal ions. The displacement parameters of the atoms are displayed at the 30% probability level. [Symmetry code A: -x, y, -z - 1/2; B: x - 1, y, z; C: -x + 1, y, -z - 1/2; D: -x + 1, -y, -z - 1; E: x, -y - 1, z + 1/2; F: -x + 1, y, 1/2 - z; G: -x + 1, -y, -z.].
	Fig. 2. Packing plot of the title complex with O—H···O hydrogen bonds indicated by dashed lines.

supplementary materials

Poly[[diaqua(8-benzene-1,2,4,5-tetracarboxylato)calciumzinc] monohydrate]

Y.-Y. Jia, B. Chen and Y.-X. Yuan

Poly[[diaqua(₈-benzene-1,2,4,5-tetracarboxylato)calciumzinc] monohydrate]