Poly[[aqua-μ6-benzene-1,2,3-tricarboxyl­ato-μ3-hydroxido-dizinc] hemihydrate]

Ma, C.-H.; Liu, Q.; Wang, X.-Y.; Dong, X.-W.; Li, Y.-J.

doi:10.1107/S1600536811055358

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m103-m104

doi:10.1107/S1600536811055358

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Poly[[aqua-μ₆-benzene-1,2,3-tricarboxylato-μ₃-hydroxido-dizinc] hemihydrate]

Chao-Hong Ma,^a Qiang Liu,^a Xiu-Yan Wang,^a Xian-Wu Dong ^a and Yu-Jie Li ^a ^*

^aJilin Agricultural Science and Technology College, Jilin 132101, People's Republic of China
^*Correspondence e-mail: jilindxw@yahoo.com.cn

(Received 7 December 2011; accepted 23 December 2011; online 7 January 2012)

In the title compound, {[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O}_n, there are three independent Zn^II atoms present; two are located on special positions, viz a twofold rotation axis and an inversion centre, and the third is located in a general position. The Zn^II atom on the inversion centre is six-coordinated by four O atoms from four different benzene-1,2,3-tricarboxylate anions and two OH⁻ anions. The Zn^II atom located on a twofold axis is four coordinated by two O atoms from two different benzene-1,2,3-tricarboxylate anions and two OH⁻ anions. The third Zn^II atom, located in a general position, is five coordinated by three O atoms from three different benzene-1,2,3-tricarboxylate anions, one OH⁻ anion and one water molecule. Each benzene-1,2,3-tricarboxylate anion bridges six Zn^II atoms, and the OH⁻ anion bridges three Zn^II atoms, resulting in the formation of a three-dimensional framework. A series of O—H⋯O hydrogen bonds involving the benzene-1,2,3-tricarboxylate anions, the OH⁻ anion and the coordinating and the two water solvent molecules further stablize the crystal structure. The two solvent water molecules show occupancies of 0.5 and 0.25.

Related literature

For complexes of benzene tricarboxylic acids, see: Chui et al. (1999 ); Majumder et al. (2005 ). For related structures, see: Wu et al. (2009 ).

Experimental

Crystal data

[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O
M_r = 381.89
Tetragonal, I 4₁ /a
a = 12.8412 (2) Å
c = 27.2647 (7) Å
V = 4495.85 (15) Å³
Z = 16
Mo Kα radiation
μ = 4.31 mm⁻¹
T = 293 K
0.28 × 0.23 × 0.21 mm

Data collection

Oxford Diffraction Gemini R Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.312, T_max = 0.399
9288 measured reflections
2048 independent reflections
1402 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 0.94
2048 reflections
198 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2W	0.86 (2)	2.37 (4)	3.121 (7)	146 (6)
O1W—H1WB⋯O2ⁱ	0.86 (2)	2.28 (5)	2.981 (6)	139 (6)
O1W—H1WB⋯O5ⁱⁱ	0.86 (2)	2.40 (4)	3.084 (6)	137 (5)
O7—H7O⋯O3ⁱⁱⁱ	0.79 (2)	2.38 (2)	3.174 (5)	179 (5)
O2W—H2WA⋯O3W^iv	0.64	2.30	2.776 (18)	134
O3W—H3WA⋯O2W^v	0.86	1.94	2.776 (18)	164
O3W—H3WB⋯O4^vi	0.90	2.24	2.811 (15)	121
Symmetry codes: (i) $[-y+{\script{3\over 4}}, x-{\script{3\over 4}}, z+{\script{1\over 4}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[y+{\script{1\over 4}}, -x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iv) $[-y+{\script{3\over 4}}, x-{\script{1\over 4}}, -z+{\script{3\over 4}}]$ ; (v) $[y+{\script{1\over 4}}, -x+{\script{3\over 4}}, -z+{\script{3\over 4}}]$ ; (vi) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055358/su2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055358/su2346Isup2.hkl

checkCIF report

Comment top

The title compound consists of three crystallographically unique Zn^II cations, two of which are located on special positions, one benzene-1,2,3-tricarboxylate anion, an OH^- anion (O7), a coordinated water molecule (O1W), and two disordered solvent water molecules (Fig. 1).

Atom Zn1 is located on an inversion center and is six coordinated by four oxygen atoms from four symmetry related 1,2,3-tricarboxybenzene anions and two symmetry related OH^- anions. The Zn1—O(carboxylate) distances are 2.022 (4) and 2.199 (3) Å. The Zn1—O7(OH^-) distance is 2.089 (3) Å. Atom Zn2, also located on a 2-fold axis, is four coordinated by two oxygen atoms from two symmetry related 1,2,3-tricarboxybenzene anions and two symmetry related OH^- anions. The Zn2—O (carboxylate) and Zn2—O7 distances are 1.943 (4) Å and 1.948 (3) Å, respectively. Atom Zn3, locate in a general position, is five coordinated by three oxygen atoms from three different 1,2,3-tricarboxybenzene anions, one OH^- anion and one water molecule (O1W). The Zn3—O(carboxylate) distances are 1.935 (4), 1.984 (3) and 2.008 (4) Å. The Zn3—O7 distance is 2.069 (4) Å, and the Zn3—O1W distance is 2.136 (5) Å. The Zn—O (carboxylate) distances are similar to those observed in related structures (Wu et al., 2009).

Each benzene-1,2,3-tricarboxylate anion bridges six Zn^II centers, and the OH^- anion bridges three Zn^II centers, leading to the formation of an infinite three-dimensional framework (Fig. 2). A series of O—H···O hydrogen bonds (Table 1) involving the tricarboxybenzene anions, the OH^- anion and the coordinating and two solvent water molecules (both of which are only partially occupied), further stabilize the crystal structure (Table 1).

Related literature top

For complexes of benzene tricarboxylic acids, see: Chui et al. (1999); Majumder et al. (2005). For related structures, see: Wu et al. (2009).

Experimental top

A mixture of benzene-1,2,3-tricarboxylic acid (0.063 g, 0.3 mmol), NaOH (0.036 g, 0.9 mmol), and Zn(Ac)₂ (0.066 g, 0.3 mmol), in 10 ml H₂O was sealed in 18 ml Teflon-lined stainless steel container. The container was heated to 433 K and held at that temperature for 72 h. It was then cooled to room temperature at a rate of 10 K per hour and block-like colourless crystals of the title compound were isolated.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and Westrip (2010).

Figures top

	Fig. 1. A view of the asymmetric unit of the title compound, showing the coordination environments of the three Zn^II centers and the 30% probability displacement ellipsoids [symmetry codes: (i) y + 1/4, -x + 1/4, z + 1/4; (ii) -y + 3/4, x - 1/4,- z + 3/4; (iii) -x + 1, -y, -z + 1; (iv) -x + 1, -y - 1/2, z; (v) -y + 3/4, x - 3/4, z + 1/4].
	Fig. 2. A view along the b axis of the three-dimensional structure of the title compound [the solvent water molecules and the H atoms have been omitted for clarity].

Poly[[aqua-µ₆-benzene-1,2,3-tricarboxylato-µ₃-hydroxido-dizinc] hemihydrate] top

Crystal data top

[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O	D_x = 2.257 Mg m⁻³
M_r = 381.89	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 2048 reflections
Hall symbol: -I 4ad	θ = 2.8–25.3°
a = 12.8412 (2) Å	µ = 4.31 mm⁻¹
c = 27.2647 (7) Å	T = 293 K
V = 4495.85 (15) Å³	Block, colourless
Z = 16	0.28 × 0.23 × 0.21 mm
F(000) = 3024

Data collection top

Oxford Diffraction Gemini R Ultra diffractometer	2048 independent reflections
Radiation source: fine-focus sealed tube	1402 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.3°, θ_min = 2.8°
ω scan	h = −15→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −15→15
T_min = 0.312, T_max = 0.399	l = −22→32
9288 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0506P)²] where P = (F_o² + 2F_c²)/3
2048 reflections	(Δ/σ)_max < 0.001
198 parameters	Δρ_max = 0.80 e Å⁻³
8 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O	Z = 16
M_r = 381.89	Mo Kα radiation
Tetragonal, I4₁/a	µ = 4.31 mm⁻¹
a = 12.8412 (2) Å	T = 293 K
c = 27.2647 (7) Å	0.28 × 0.23 × 0.21 mm
V = 4495.85 (15) Å³

Data collection top

Oxford Diffraction Gemini R Ultra diffractometer	2048 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1402 reflections with I > 2σ(I)
T_min = 0.312, T_max = 0.399	R_int = 0.051
9288 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	8 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.80 e Å⁻³
2048 reflections	Δρ_min = −0.53 e Å⁻³
198 parameters

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.5000	0.0000	0.5000	0.0208 (2)
Zn2	0.5000	−0.2500	0.49263 (3)	0.0250 (3)
Zn3	0.68168 (5)	−0.13663 (5)	0.57097 (2)	0.0274 (2)
O1	0.3829 (3)	−0.2239 (3)	0.44919 (13)	0.0350 (10)
O1W	0.8258 (4)	−0.1142 (4)	0.61415 (16)	0.0569 (13)
O2	0.4505 (3)	−0.0690 (3)	0.42997 (12)	0.0275 (9)
O3	0.3919 (3)	0.1070 (3)	0.36657 (11)	0.0224 (8)
O4	0.4706 (3)	0.0068 (3)	0.31306 (13)	0.0326 (10)
O5	0.2600 (3)	0.1066 (3)	0.28024 (12)	0.0312 (9)
O6	0.1945 (3)	−0.0076 (3)	0.22700 (13)	0.0411 (11)
O7	0.5375 (3)	−0.1373 (3)	0.53706 (12)	0.0209 (8)
C1	0.3132 (4)	−0.1383 (4)	0.38044 (18)	0.0250 (13)
C2	0.3150 (4)	−0.0597 (4)	0.34414 (17)	0.0201 (12)
C3	0.2429 (4)	−0.0677 (4)	0.30533 (19)	0.0273 (13)
C4	0.1747 (5)	−0.1498 (5)	0.3023 (2)	0.0485 (18)
H4	0.1296	−0.1543	0.2757	0.058*
C5	0.1720 (6)	−0.2254 (5)	0.3380 (3)	0.061 (2)
H5	0.1251	−0.2803	0.3357	0.074*
C6	0.2400 (5)	−0.2187 (5)	0.3774 (2)	0.0439 (17)
H6	0.2370	−0.2685	0.4022	0.053*
C7	0.3880 (4)	−0.1430 (4)	0.42282 (17)	0.0239 (12)
C8	0.3973 (4)	0.0242 (4)	0.34212 (17)	0.0197 (12)
C9	0.2329 (4)	0.0172 (4)	0.26799 (19)	0.0246 (12)
O2W	1.0000	−0.2500	0.5664 (4)	0.038 (3)	0.50
H2WA	0.9977	−0.2203	0.5475	0.057*	0.50
O3W	0.0743 (12)	−0.3649 (12)	0.2625 (5)	0.038 (4)	0.25
H3WA	0.0608	−0.3205	0.2396	0.057*	0.25
H3WB	0.0318	−0.4194	0.2582	0.057*	0.25
H1WA	0.885 (3)	−0.124 (5)	0.6006 (18)	0.057*
H1WB	0.825 (4)	−0.141 (5)	0.6431 (11)	0.057*
H7O	0.493 (3)	−0.139 (4)	0.5572 (14)	0.019 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0265 (5)	0.0185 (5)	0.0174 (4)	−0.0003 (4)	0.0020 (4)	0.0024 (3)
Zn2	0.0434 (6)	0.0173 (5)	0.0143 (4)	−0.0014 (4)	0.000	0.000
Zn3	0.0421 (5)	0.0242 (4)	0.0159 (3)	−0.0009 (3)	0.0057 (3)	0.0027 (3)
O1	0.047 (3)	0.030 (2)	0.028 (2)	−0.007 (2)	−0.0119 (19)	0.0136 (18)
O1W	0.054 (3)	0.073 (4)	0.043 (3)	0.000 (3)	−0.003 (2)	0.007 (3)
O2	0.040 (2)	0.028 (2)	0.0146 (18)	−0.0088 (19)	−0.0061 (16)	0.0001 (15)
O3	0.031 (2)	0.021 (2)	0.0149 (18)	−0.0029 (17)	−0.0013 (15)	0.0002 (15)
O4	0.036 (2)	0.037 (2)	0.024 (2)	−0.0105 (19)	0.0064 (18)	−0.0061 (17)
O5	0.047 (3)	0.024 (2)	0.0218 (19)	−0.0069 (19)	−0.0138 (18)	0.0090 (16)
O6	0.062 (3)	0.033 (2)	0.028 (2)	0.010 (2)	−0.025 (2)	−0.0059 (18)
O7	0.034 (2)	0.018 (2)	0.0101 (18)	−0.0017 (17)	0.0051 (17)	0.0005 (15)
C1	0.029 (3)	0.021 (3)	0.025 (3)	0.003 (3)	−0.006 (2)	0.000 (2)
C2	0.028 (3)	0.016 (3)	0.016 (3)	0.001 (2)	−0.002 (2)	−0.005 (2)
C3	0.033 (3)	0.021 (3)	0.028 (3)	0.002 (3)	−0.009 (3)	−0.002 (2)
C4	0.059 (5)	0.035 (4)	0.052 (4)	−0.009 (3)	−0.035 (4)	0.008 (3)
C5	0.065 (5)	0.041 (4)	0.078 (5)	−0.029 (4)	−0.037 (4)	0.020 (4)
C6	0.051 (4)	0.032 (4)	0.049 (4)	−0.009 (3)	−0.024 (3)	0.016 (3)
C7	0.025 (3)	0.033 (3)	0.013 (3)	0.005 (3)	0.003 (2)	0.000 (2)
C8	0.027 (3)	0.021 (3)	0.011 (2)	−0.001 (2)	−0.003 (2)	0.004 (2)
C9	0.023 (3)	0.026 (3)	0.025 (3)	0.001 (3)	−0.008 (2)	−0.001 (2)
O2W	0.039 (7)	0.030 (7)	0.044 (7)	−0.018 (5)	0.000	0.000
O3W	0.044 (11)	0.037 (10)	0.033 (9)	0.004 (8)	0.010 (8)	−0.014 (7)

Geometric parameters (Å, º) top

Zn1—O5ⁱ	2.022 (4)	O4—Zn3^vi	2.008 (4)
Zn1—O5ⁱⁱ	2.022 (4)	O5—C9	1.245 (6)
Zn1—O7ⁱⁱⁱ	2.089 (3)	O5—Zn1^vii	2.022 (3)
Zn1—O7	2.089 (3)	O6—C9	1.263 (6)
Zn1—O2	2.199 (3)	O6—Zn3^viii	1.935 (4)
Zn1—O2ⁱⁱⁱ	2.199 (3)	O7—H7O	0.79 (2)
Zn2—O1^iv	1.943 (4)	C1—C6	1.399 (8)
Zn2—O1	1.943 (4)	C1—C2	1.413 (7)
Zn2—O7	1.948 (3)	C1—C7	1.504 (7)
Zn2—O7^iv	1.948 (3)	C2—C3	1.410 (7)
Zn3—O6ⁱ	1.935 (4)	C2—C8	1.511 (7)
Zn3—O3ⁱⁱⁱ	1.984 (3)	C3—C4	1.373 (8)
Zn3—O4^v	2.008 (4)	C3—C9	1.497 (7)
Zn3—O7	2.069 (4)	C4—C5	1.374 (9)
Zn3—O1W	2.213 (5)	C4—H4	0.9300
O1—C7	1.265 (6)	C5—C6	1.388 (9)
O1W—H1WA	0.86 (2)	C5—H5	0.9300
O1W—H1WB	0.86 (2)	C6—H6	0.9300
O2—C7	1.259 (6)	O2W—H2WA	0.6405
O3—C8	1.257 (6)	O3W—H3WA	0.8614
O3—Zn3ⁱⁱⁱ	1.984 (3)	O3W—H3WB	0.8960
O4—C8	1.250 (6)

O5ⁱ—Zn1—O5ⁱⁱ	180.000 (1)	C8—O4—Zn3^vi	123.3 (3)
O5ⁱ—Zn1—O7ⁱⁱⁱ	87.68 (15)	C9—O5—Zn1^vii	135.5 (3)
O5ⁱⁱ—Zn1—O7ⁱⁱⁱ	92.32 (14)	C9—O6—Zn3^viii	133.0 (4)
O5ⁱ—Zn1—O7	92.32 (14)	Zn2—O7—Zn3	120.15 (18)
O5ⁱⁱ—Zn1—O7	87.68 (15)	Zn2—O7—Zn1	105.62 (15)
O7ⁱⁱⁱ—Zn1—O7	180.00 (15)	Zn3—O7—Zn1	114.77 (16)
O5ⁱ—Zn1—O2	86.24 (15)	Zn2—O7—H7O	104 (4)
O5ⁱⁱ—Zn1—O2	93.76 (15)	Zn3—O7—H7O	110 (4)
O7ⁱⁱⁱ—Zn1—O2	81.58 (13)	Zn1—O7—H7O	101 (4)
O7—Zn1—O2	98.42 (13)	C6—C1—C2	119.8 (5)
O5ⁱ—Zn1—O2ⁱⁱⁱ	93.76 (15)	C6—C1—C7	116.4 (5)
O5ⁱⁱ—Zn1—O2ⁱⁱⁱ	86.24 (15)	C2—C1—C7	123.8 (5)
O7ⁱⁱⁱ—Zn1—O2ⁱⁱⁱ	98.42 (13)	C3—C2—C1	117.6 (5)
O7—Zn1—O2ⁱⁱⁱ	81.58 (13)	C3—C2—C8	118.9 (4)
O2—Zn1—O2ⁱⁱⁱ	180.000 (1)	C1—C2—C8	123.1 (4)
O1^iv—Zn2—O1	104.9 (2)	C4—C3—C2	121.3 (5)
O1^iv—Zn2—O7	108.41 (15)	C4—C3—C9	117.7 (5)
O1—Zn2—O7	116.25 (16)	C2—C3—C9	120.9 (5)
O1^iv—Zn2—O7^iv	116.25 (16)	C3—C4—C5	121.1 (6)
O1—Zn2—O7^iv	108.41 (15)	C3—C4—H4	119.5
O7—Zn2—O7^iv	103.1 (2)	C5—C4—H4	119.5
O6ⁱ—Zn3—O3ⁱⁱⁱ	135.77 (17)	C4—C5—C6	119.3 (6)
O6ⁱ—Zn3—O4^v	102.75 (17)	C4—C5—H5	120.4
O3ⁱⁱⁱ—Zn3—O4^v	117.03 (14)	C6—C5—H5	120.4
O6ⁱ—Zn3—O7	98.68 (14)	C5—C6—C1	120.9 (6)
O3ⁱⁱⁱ—Zn3—O7	87.62 (14)	C5—C6—H6	119.5
O4^v—Zn3—O7	107.46 (15)	C1—C6—H6	119.5
O6ⁱ—Zn3—O1W	82.42 (17)	O2—C7—O1	124.3 (5)
O3ⁱⁱⁱ—Zn3—O1W	85.21 (16)	O2—C7—C1	119.8 (5)
O4^v—Zn3—O1W	81.20 (18)	O1—C7—C1	115.9 (5)
O7—Zn3—O1W	170.65 (17)	O4—C8—O3	122.0 (5)
C7—O1—Zn2	116.6 (3)	O4—C8—C2	115.0 (4)
Zn3—O1W—H1WA	120 (4)	O3—C8—C2	123.0 (5)
Zn3—O1W—H1WB	116 (4)	O5—C9—O6	125.4 (5)
H1WA—O1W—H1WB	110 (3)	O5—C9—C3	117.7 (4)
C7—O2—Zn1	128.5 (3)	O6—C9—C3	116.8 (5)
C8—O3—Zn3ⁱⁱⁱ	130.1 (3)	H3WA—O3W—H3WB	107.3

O1^iv—Zn2—O1—C7	−65.4 (4)	C7—C1—C2—C8	4.3 (8)
O7—Zn2—O1—C7	54.3 (4)	C1—C2—C3—C4	−1.2 (9)
O7^iv—Zn2—O1—C7	169.8 (4)	C8—C2—C3—C4	172.1 (6)
O5ⁱ—Zn1—O2—C7	141.0 (4)	C1—C2—C3—C9	174.2 (5)
O5ⁱⁱ—Zn1—O2—C7	−39.0 (4)	C8—C2—C3—C9	−12.5 (8)
O7ⁱⁱⁱ—Zn1—O2—C7	−130.8 (5)	C2—C3—C4—C5	2.2 (11)
O7—Zn1—O2—C7	49.2 (5)	C9—C3—C4—C5	−173.4 (7)
O2ⁱⁱⁱ—Zn1—O2—C7	−117 (100)	C3—C4—C5—C6	−0.5 (12)
O1^iv—Zn2—O7—Zn3	−45.2 (2)	C4—C5—C6—C1	−2.0 (12)
O1—Zn2—O7—Zn3	−163.02 (17)	C2—C1—C6—C5	2.9 (10)
O7^iv—Zn2—O7—Zn3	78.55 (17)	C7—C1—C6—C5	−175.8 (6)
O1^iv—Zn2—O7—Zn1	86.51 (19)	Zn1—O2—C7—O1	−39.5 (7)
O1—Zn2—O7—Zn1	−31.3 (2)	Zn1—O2—C7—C1	140.8 (4)
O7^iv—Zn2—O7—Zn1	−149.7 (2)	Zn2—O1—C7—O2	−15.6 (7)
O6ⁱ—Zn3—O7—Zn2	91.9 (2)	Zn2—O1—C7—C1	164.2 (3)
O3ⁱⁱⁱ—Zn3—O7—Zn2	−132.1 (2)	C6—C1—C7—O2	−174.5 (5)
O4^v—Zn3—O7—Zn2	−14.5 (2)	C2—C1—C7—O2	6.8 (8)
O1W—Zn3—O7—Zn2	−172.0 (9)	C6—C1—C7—O1	5.7 (8)
O6ⁱ—Zn3—O7—Zn1	−35.8 (2)	C2—C1—C7—O1	−172.9 (5)
O3ⁱⁱⁱ—Zn3—O7—Zn1	100.22 (18)	Zn3^vi—O4—C8—O3	27.5 (7)
O4^v—Zn3—O7—Zn1	−142.15 (16)	Zn3^vi—O4—C8—C2	−154.5 (3)
O1W—Zn3—O7—Zn1	60.3 (10)	Zn3ⁱⁱⁱ—O3—C8—O4	−156.6 (4)
O5ⁱ—Zn1—O7—Zn2	−90.46 (18)	Zn3ⁱⁱⁱ—O3—C8—C2	25.5 (7)
O5ⁱⁱ—Zn1—O7—Zn2	89.54 (18)	C3—C2—C8—O4	−75.5 (6)
O7ⁱⁱⁱ—Zn1—O7—Zn2	118.7 (5)	C1—C2—C8—O4	97.4 (6)
O2—Zn1—O7—Zn2	−3.92 (19)	C3—C2—C8—O3	102.5 (6)
O2ⁱⁱⁱ—Zn1—O7—Zn2	176.08 (19)	C1—C2—C8—O3	−84.5 (7)
O5ⁱ—Zn1—O7—Zn3	44.24 (18)	Zn1^vii—O5—C9—O6	5.9 (9)
O5ⁱⁱ—Zn1—O7—Zn3	−135.76 (18)	Zn1^vii—O5—C9—C3	−171.8 (4)
O7ⁱⁱⁱ—Zn1—O7—Zn3	−106.6 (3)	Zn3^viii—O6—C9—O5	−27.8 (9)
O2—Zn1—O7—Zn3	130.78 (17)	Zn3^viii—O6—C9—C3	149.8 (4)
O2ⁱⁱⁱ—Zn1—O7—Zn3	−49.22 (17)	C4—C3—C9—O5	151.0 (6)
C6—C1—C2—C3	−1.3 (8)	C2—C3—C9—O5	−24.6 (8)
C7—C1—C2—C3	177.3 (5)	C4—C3—C9—O6	−26.8 (8)
C6—C1—C2—C8	−174.3 (5)	C2—C3—C9—O6	157.6 (5)

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+1/4, z+1/4; (iii) −x+1, −y, −z+1; (iv) −x+1, −y−1/2, z; (v) −y+3/4, x−3/4, z+1/4; (vi) y+3/4, −x+3/4, z−1/4; (vii) −y+1/4, x−1/4, z−1/4; (viii) y+1/4, −x+3/4, −z+3/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2W	0.86 (2)	2.37 (4)	3.121 (7)	146 (6)
O1W—H1WB···O2^v	0.86 (2)	2.28 (5)	2.981 (6)	139 (6)
O1W—H1WB···O5ⁱⁱⁱ	0.86 (2)	2.40 (4)	3.084 (6)	137 (5)
O7—H7O···O3ⁱⁱ	0.79 (2)	2.38 (2)	3.174 (5)	179 (5)
O2W—H2WA···O3Wⁱ	0.64	2.30	2.776 (18)	134
O3W—H3WA···O2W^viii	0.86	1.94	2.776 (18)	164
O3W—H3WB···O4^ix	0.90	2.24	2.811 (15)	121

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+1/4, z+1/4; (iii) −x+1, −y, −z+1; (v) −y+3/4, x−3/4, z+1/4; (viii) y+1/4, −x+3/4, −z+3/4; (ix) −x+1/2, −y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O
M_r	381.89
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	12.8412 (2), 27.2647 (7)
V (Å³)	4495.85 (15)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	4.31
Crystal size (mm)	0.28 × 0.23 × 0.21

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.312, 0.399
No. of measured, independent and observed [I > 2σ(I)] reflections	9288, 2048, 1402
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 0.94
No. of reflections	2048
No. of parameters	198
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.53

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008) and Westrip (2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2W	0.86 (2)	2.37 (4)	3.121 (7)	146 (6)
O1W—H1WB···O2ⁱ	0.86 (2)	2.28 (5)	2.981 (6)	139 (6)
O1W—H1WB···O5ⁱⁱ	0.86 (2)	2.40 (4)	3.084 (6)	137 (5)
O7—H7O···O3ⁱⁱⁱ	0.79 (2)	2.38 (2)	3.174 (5)	179 (5)
O2W—H2WA···O3W^iv	0.64	2.30	2.776 (18)	134
O3W—H3WA···O2W^v	0.86	1.94	2.776 (18)	164
O3W—H3WB···O4^vi	0.90	2.24	2.811 (15)	121

Symmetry codes: (i) −y+3/4, x−3/4, z+1/4; (ii) −x+1, −y, −z+1; (iii) y+1/4, −x+1/4, z+1/4; (iv) −y+3/4, x−1/4, −z+3/4; (v) y+1/4, −x+3/4, −z+3/4; (vi) −x+1/2, −y−1/2, −z+1/2.

Acknowledgements

We thank Jilin Agricultural Science and Technology College for support.

References

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