Bis{1-[(1H-benzimidazol-2-yl)meth­yl]-1H-imidazole-κN3}­bis­(3,5-dicarb­oxy­benzoato-κO1)zinc octa­hydrate

Zhao, L.; Liu, B.; Li, T.; Meng, X.

doi:10.1107/S160053681200147X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m162

doi:10.1107/S160053681200147X

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Bis{1-[(1H-benzimidazol-2-yl)methyl]-1H-imidazole-κN³}bis(3,5-dicarboxybenzoato-κO¹)zinc octahydrate

Lei Zhao,^a Bingtao Liu,^b Ting Li ^c and Xiangru Meng ^c ^*

^aSchool of Chemical and Engineering, Zhengzhou University, Zhengzhou 450001, People's Republic of China, ^bSchool of Environmental and Municipal Engineering, North China Institute of Water Conservancy and Hydroelectric Power, Zhengzhou 450011, People's Republic of China, and ^cDepartment of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: mxr@zzu.edu.cn

(Received 11 January 2012; accepted 12 January 2012; online 18 January 2012)

In the title complex, [Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O, the Zn^II ion exhibits site symmetry 2. It shows a distorted tetrahedral coordination defined by two N atoms from two symmetry-related 1-[(1H-benzimidazol-2-yl)methyl]-1H-imidazole ligands and by two O atoms from two symmetry-related monodeprotonated 3,5-dicarboxybenzoate anions. In the crystal, complex molecules and solvent water molecules are linked through intermolecular O—H⋯O, O—H⋯N, and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For background information on Zn^II complexes constructed from both aromatic carboxylates and N-heterocyclic ligands, see: Lin et al. (2008 ); Tian et al. (2010 ).

Experimental

Crystal data

[Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O
M_r = 1024.22
Monoclinic, C 2/c
a = 20.870 (4) Å
b = 15.008 (3) Å
c = 15.472 (3) Å
β = 109.51 (3)°
V = 4567.9 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 293 K
0.18 × 0.15 × 0.14 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004 ) T_min = 0.896, T_max = 0.917
15325 measured reflections
4127 independent reflections
3898 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.158
S = 1.07
4127 reflections
314 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O9	0.85	2.22	2.936 (8)	142
O9—H9A⋯O4	0.85	2.15	2.634 (7)	115
O9—H9B⋯O10	0.85	2.24	2.783 (12)	122
O10—H10A⋯O9	0.85	1.93	2.783 (12)	179
N4—H4⋯O7ⁱ	0.86	1.97	2.808 (4)	163
O3—H3⋯O10ⁱⁱ	0.82	2.56	3.341 (10)	159
O5—H5⋯N3ⁱⁱⁱ	0.82	1.77	2.577 (3)	165
O7—H7A⋯O2^iv	0.85	1.98	2.784 (4)	156
O7—H7B⋯O8^v	0.85	1.95	2.796 (5)	179
O8—H8B⋯O6^vi	0.85	2.02	2.799 (6)	152
O10—H10B⋯O6^vii	0.85	2.03	2.728 (9)	139
Symmetry codes: (i) x+1, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x-1, -y+1, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681200147X/ff2052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200147X/ff2052Isup2.hkl

checkCIF report

Comment top

It is well known that the Zn^II ion is able to coordinate simultaneously to both oxygen-containing and nitrogen-containing ligands and the final products can exhibit attractive structures and useful functional properties. A great number of Zn^II complexes containing both aromatic carboxylates and N-heterocyclic ligands have been reported (Lin et al., 2008; Tian et al., 2010). In order to further explore such compounds with new structures, we selected 1-((1H-benzimidazol-1-yl)methyl)-1H-imidazole and 1,3,5-benzenetricarboxylic acid as ligands to self-assemble with Zn(NO₃)₂ and obtained the title complex, {[Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂] (H₂O)₈}, the crystal structure of which is reported herein. As shown in Figure 1, two 1-((1H-benzimidazol-1-yl)methyl)-1H-imidazole ligands and two monodeprotonated 1,3,5-benzenetricarboxylic acid anions coordinate to the Zn^II ion which is located on a twofold rotation axis. The Zn—O bond length is slightly shorter than the Zn—N bond length. The environment around the Zn^II ion can be best described as distorted tetrahedral. O—H···O, O—H···N, and N—H···O hydrogen bonds between solvent water/water molecules, between solvent water molecules and carboxylate O atoms, between carboxyl groups and solvent water molecules, between carboxyl groups and benzimidazole N atoms, between benzimidazole units and solvent water molecules of adjacent molecules consolidate the crystal packing (Figure 2).

Related literature top

For background information on Zn^II complexes constructed from both aromatic carboxylates and N-heterocyclic ligands, see: Lin et al. (2008); Tian et al. (2010).

Experimental top

A mixture of Zn(NO₃)₂ (0.1 mmol), 1-((1H-benzimidazol-1-yl)methyl)-1H-imidazole (0.1 mmol), 1,3,5-benzenetricarboxylic acid (0.1 mmol) and water (10 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 120 °C for 72 h, then cooled to room temperature. Colourless crystals were obtained from the filtrate and dried in air.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: 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).

Figures top

	Fig. 1. View of the title complex showing labeling and 30% probability displacement ellipsolids. H atoms are omitted for clarity. [Symmetry code A: -x + 2, +y, -z + 1.5.]
	Fig. 2. View of the crystal packing of the title complex, showing the three-dimensional structure stabilized by hydrogen bonds.

Bis{1-[(1H-benzimidazol-2-yl)methyl]-1H-imidazole- κN³}bis(3,5-dicarboxybenzoato-κO¹)zinc octahydrate top

Crystal data top

[Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O	F(000) = 2128
M_r = 1024.22	D_x = 1.489 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6831 reflections
a = 20.870 (4) Å	θ = 1.7–27.9°
b = 15.008 (3) Å	µ = 0.63 mm⁻¹
c = 15.472 (3) Å	T = 293 K
β = 109.51 (3)°	Prism, colourless
V = 4567.9 (16) Å³	0.18 × 0.15 × 0.14 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	4127 independent reflections
Radiation source: fine-focus sealed tube	3898 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.3°, θ_min = 2.0°
ω scans	h = −25→25
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −17→18
T_min = 0.896, T_max = 0.917	l = −18→18
15325 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0953P)² + 7.0031P] where P = (F_o² + 2F_c²)/3
4127 reflections	(Δ/σ)_max < 0.001
314 parameters	Δρ_max = 1.08 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O	V = 4567.9 (16) Å³
M_r = 1024.22	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.870 (4) Å	µ = 0.63 mm⁻¹
b = 15.008 (3) Å	T = 293 K
c = 15.472 (3) Å	0.18 × 0.15 × 0.14 mm
β = 109.51 (3)°

Data collection top

Rigaku Saturn diffractometer	4127 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	3898 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.917	R_int = 0.031
15325 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.07	Δρ_max = 1.08 e Å⁻³
4127 reflections	Δρ_min = −0.45 e Å⁻³
314 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
Zn1	1.0000	0.47361 (3)	0.7500	0.02673 (18)
N1	1.00685 (12)	0.54973 (17)	0.85945 (17)	0.0303 (5)
N2	1.04718 (12)	0.60129 (16)	0.99936 (16)	0.0295 (5)
N3	1.20973 (13)	0.63838 (16)	1.09909 (17)	0.0323 (6)
N4	1.15439 (13)	0.75634 (17)	1.11874 (19)	0.0368 (6)
H4	1.1219	0.7891	1.1235	0.044*
O1	0.91112 (10)	0.41744 (14)	0.70946 (15)	0.0353 (5)
O2	0.95138 (12)	0.31291 (17)	0.64061 (18)	0.0486 (6)
O3	0.67237 (16)	0.42512 (17)	0.6806 (3)	0.0685 (9)
H3	0.6539	0.4603	0.6391	0.082*
O4	0.60726 (13)	0.3058 (2)	0.6317 (3)	0.0730 (10)
O5	0.70841 (13)	0.02986 (15)	0.5653 (3)	0.0604 (8)
H5	0.7129	−0.0244	0.5703	0.073*
O6	0.81799 (15)	0.02479 (16)	0.5819 (3)	0.0655 (9)
O7	0.03572 (17)	0.8297 (2)	0.1368 (3)	0.0841 (11)
H7A	0.0096	0.7939	0.1517	0.101*
H7B	0.0500	0.8761	0.1688	0.101*
O8	0.5834 (2)	0.5183 (3)	0.7433 (3)	0.1037 (14)
H8A	0.5724	0.4636	0.7401	0.124*
H8B	0.6017	0.5138	0.8011	0.124*
O9	0.4962 (3)	0.3677 (5)	0.6555 (6)	0.214 (4)
H9A	0.5130	0.3746	0.6129	0.256*
H9B	0.4592	0.3966	0.6428	0.256*
O10	0.4214 (6)	0.4833 (11)	0.5182 (7)	0.417 (11)
H10A	0.4442	0.4475	0.5597	0.501*
H10B	0.3822	0.4733	0.5214	0.501*
C1	1.05420 (15)	0.53995 (19)	0.9405 (2)	0.0303 (6)
H1A	1.0878	0.4964	0.9546	0.036*
C2	0.96815 (16)	0.6220 (2)	0.8680 (2)	0.0381 (7)
H2A	0.9311	0.6451	0.8215	0.046*
C3	0.99263 (16)	0.6536 (2)	0.9542 (2)	0.0396 (8)
H3A	0.9758	0.7015	0.9782	0.048*
C4	1.09106 (16)	0.6115 (2)	1.0948 (2)	0.0344 (7)
H4A	1.1063	0.5531	1.1204	0.041*
H4B	1.0650	0.6377	1.1298	0.041*
C5	1.15158 (15)	0.6686 (2)	1.10402 (19)	0.0302 (6)
C6	1.21887 (16)	0.7856 (2)	1.1250 (2)	0.0347 (7)
C7	1.24868 (19)	0.8692 (2)	1.1402 (3)	0.0483 (9)
H7C	1.2251	0.9194	1.1480	0.058*
C8	1.3160 (2)	0.8734 (3)	1.1431 (3)	0.0519 (9)
H8C	1.3381	0.9282	1.1529	0.062*
C9	1.35128 (18)	0.7980 (3)	1.1318 (3)	0.0506 (9)
H9C	1.3964	0.8037	1.1353	0.061*
C10	1.32114 (17)	0.7154 (2)	1.1157 (2)	0.0419 (8)
H10C	1.3446	0.6653	1.1074	0.050*
C11	1.25365 (15)	0.7105 (2)	1.1124 (2)	0.0327 (7)
C12	0.90560 (15)	0.3445 (2)	0.6650 (2)	0.0314 (6)
C13	0.83856 (15)	0.2976 (2)	0.64489 (19)	0.0297 (6)
C14	0.78386 (15)	0.3418 (2)	0.6558 (2)	0.0332 (7)
H14A	0.7884	0.4009	0.6749	0.040*
C15	0.72163 (16)	0.2984 (2)	0.6385 (2)	0.0357 (7)
C16	0.71589 (16)	0.2091 (2)	0.6120 (2)	0.0363 (7)
H16A	0.6747	0.1797	0.6007	0.044*
C17	0.77091 (16)	0.1639 (2)	0.6024 (2)	0.0346 (7)
C18	0.83224 (16)	0.2091 (2)	0.6178 (2)	0.0344 (7)
H18A	0.8691	0.1796	0.6098	0.041*
C19	0.66265 (17)	0.3463 (2)	0.6498 (3)	0.0439 (8)
C20	0.76632 (18)	0.0659 (2)	0.5806 (3)	0.0435 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0215 (3)	0.0258 (3)	0.0320 (3)	0.000	0.0078 (2)	0.000
N1	0.0237 (12)	0.0282 (12)	0.0380 (14)	−0.0005 (10)	0.0089 (10)	−0.0032 (11)
N2	0.0276 (12)	0.0287 (12)	0.0324 (13)	−0.0035 (10)	0.0104 (10)	−0.0038 (10)
N3	0.0291 (13)	0.0262 (12)	0.0383 (14)	−0.0012 (10)	0.0070 (11)	0.0028 (11)
N4	0.0317 (14)	0.0321 (14)	0.0479 (16)	−0.0030 (11)	0.0152 (12)	−0.0087 (12)
O1	0.0294 (11)	0.0326 (11)	0.0417 (12)	−0.0077 (9)	0.0090 (9)	−0.0042 (9)
O2	0.0372 (13)	0.0513 (15)	0.0651 (16)	−0.0110 (11)	0.0276 (12)	−0.0135 (12)
O3	0.0585 (18)	0.0375 (15)	0.119 (3)	−0.0020 (13)	0.0428 (18)	−0.0142 (16)
O4	0.0347 (14)	0.0558 (17)	0.129 (3)	−0.0097 (13)	0.0275 (16)	−0.0182 (18)
O5	0.0418 (15)	0.0241 (12)	0.111 (3)	−0.0081 (10)	0.0193 (15)	−0.0041 (13)
O6	0.0515 (17)	0.0367 (15)	0.115 (3)	−0.0043 (12)	0.0364 (17)	−0.0187 (14)
O7	0.078 (2)	0.065 (2)	0.129 (3)	−0.0150 (17)	0.060 (2)	−0.018 (2)
O8	0.100 (3)	0.089 (3)	0.111 (3)	0.001 (2)	0.020 (3)	0.001 (2)
O9	0.117 (5)	0.204 (7)	0.321 (10)	0.020 (5)	0.074 (6)	−0.060 (7)
O10	0.317 (14)	0.76 (3)	0.254 (12)	0.332 (17)	0.204 (12)	0.243 (16)
C1	0.0241 (14)	0.0280 (15)	0.0376 (16)	−0.0019 (11)	0.0087 (12)	−0.0011 (12)
C2	0.0307 (16)	0.0373 (17)	0.0415 (18)	0.0074 (13)	0.0055 (13)	−0.0038 (14)
C3	0.0378 (17)	0.0364 (17)	0.0443 (18)	0.0087 (14)	0.0135 (15)	−0.0062 (14)
C4	0.0345 (16)	0.0372 (16)	0.0318 (15)	−0.0090 (13)	0.0113 (13)	−0.0024 (13)
C5	0.0302 (15)	0.0292 (15)	0.0298 (15)	−0.0035 (12)	0.0083 (12)	−0.0002 (12)
C6	0.0341 (16)	0.0323 (16)	0.0349 (16)	−0.0050 (13)	0.0077 (13)	−0.0040 (13)
C7	0.053 (2)	0.0324 (18)	0.060 (2)	−0.0087 (16)	0.0192 (18)	−0.0079 (16)
C8	0.051 (2)	0.043 (2)	0.058 (2)	−0.0209 (18)	0.0141 (18)	−0.0030 (17)
C9	0.0346 (18)	0.061 (2)	0.053 (2)	−0.0129 (17)	0.0102 (16)	0.0041 (18)
C10	0.0336 (17)	0.0413 (19)	0.049 (2)	0.0004 (14)	0.0110 (15)	0.0042 (15)
C11	0.0312 (15)	0.0283 (15)	0.0347 (16)	−0.0033 (12)	0.0059 (12)	0.0020 (12)
C12	0.0313 (15)	0.0315 (15)	0.0306 (15)	−0.0058 (12)	0.0092 (12)	0.0026 (12)
C13	0.0292 (15)	0.0295 (15)	0.0282 (14)	−0.0068 (12)	0.0065 (12)	0.0010 (12)
C14	0.0341 (16)	0.0243 (14)	0.0388 (17)	−0.0066 (12)	0.0092 (13)	−0.0024 (12)
C15	0.0303 (16)	0.0310 (16)	0.0436 (18)	−0.0041 (13)	0.0093 (13)	−0.0014 (13)
C16	0.0304 (16)	0.0294 (16)	0.0460 (18)	−0.0070 (13)	0.0084 (13)	0.0007 (13)
C17	0.0315 (16)	0.0273 (15)	0.0429 (18)	−0.0067 (12)	0.0097 (13)	−0.0013 (13)
C18	0.0309 (16)	0.0330 (16)	0.0405 (17)	−0.0047 (13)	0.0137 (13)	−0.0020 (13)
C19	0.0345 (18)	0.0325 (17)	0.063 (2)	−0.0033 (14)	0.0139 (16)	−0.0040 (16)
C20	0.0409 (19)	0.0302 (17)	0.058 (2)	−0.0065 (15)	0.0153 (16)	−0.0036 (15)

Geometric parameters (Å, º) top

Zn1—O1	1.941 (2)	C1—H1A	0.9300
Zn1—O1ⁱ	1.941 (2)	C2—C3	1.344 (5)
Zn1—N1	2.008 (2)	C2—H2A	0.9300
Zn1—N1ⁱ	2.008 (2)	C3—H3A	0.9300
N1—C1	1.320 (4)	C4—C5	1.493 (4)
N1—C2	1.385 (4)	C4—H4A	0.9700
N2—C1	1.338 (4)	C4—H4B	0.9700
N2—C3	1.367 (4)	C6—C7	1.384 (5)
N2—C4	1.463 (4)	C6—C11	1.390 (4)
N3—C5	1.322 (4)	C7—C8	1.392 (5)
N3—C11	1.388 (4)	C7—H7C	0.9300
N4—C5	1.334 (4)	C8—C9	1.392 (6)
N4—C6	1.388 (4)	C8—H8C	0.9300
N4—H4	0.8600	C9—C10	1.375 (5)
O1—C12	1.278 (4)	C9—H9C	0.9300
O2—C12	1.233 (4)	C10—C11	1.394 (5)
O3—C19	1.266 (4)	C10—H10C	0.9300
O3—H3	0.8200	C12—C13	1.503 (4)
O4—C19	1.253 (4)	C13—C14	1.378 (4)
O5—C20	1.272 (4)	C13—C18	1.386 (4)
O5—H5	0.8200	C14—C15	1.396 (4)
O6—C20	1.236 (4)	C14—H14A	0.9300
O7—H7A	0.8500	C15—C16	1.395 (4)
O7—H7B	0.8492	C15—C19	1.485 (5)
O8—H8A	0.8501	C16—C17	1.384 (5)
O8—H8B	0.8502	C16—H16A	0.9300
O9—H9A	0.8500	C17—C18	1.397 (4)
O9—H9B	0.8501	C17—C20	1.505 (4)
O10—H10A	0.8502	C18—H18A	0.9300
O10—H10B	0.8498

O1—Zn1—O1ⁱ	128.52 (13)	N4—C6—C11	105.8 (3)
O1—Zn1—N1	108.11 (10)	C6—C7—C8	116.0 (3)
O1ⁱ—Zn1—N1	100.57 (10)	C6—C7—H7C	122.0
O1—Zn1—N1ⁱ	100.57 (10)	C8—C7—H7C	122.0
O1ⁱ—Zn1—N1ⁱ	108.11 (10)	C7—C8—C9	121.9 (3)
N1—Zn1—N1ⁱ	110.65 (15)	C7—C8—H8C	119.0
C1—N1—C2	105.8 (3)	C9—C8—H8C	119.0
C1—N1—Zn1	123.9 (2)	C10—C9—C8	121.8 (3)
C2—N1—Zn1	130.3 (2)	C10—C9—H9C	119.1
C1—N2—C3	108.0 (2)	C8—C9—H9C	119.1
C1—N2—C4	125.9 (3)	C9—C10—C11	116.7 (3)
C3—N2—C4	126.2 (3)	C9—C10—H10C	121.6
C5—N3—C11	107.3 (3)	C11—C10—H10C	121.6
C5—N4—C6	108.1 (3)	N3—C11—C6	107.7 (3)
C5—N4—H4	125.9	N3—C11—C10	131.0 (3)
C6—N4—H4	125.9	C6—C11—C10	121.3 (3)
C12—O1—Zn1	116.8 (2)	O2—C12—O1	123.7 (3)
C19—O3—H3	109.5	O2—C12—C13	121.3 (3)
C20—O5—H5	109.5	O1—C12—C13	115.0 (3)
H7A—O7—H7B	119.4	C14—C13—C18	119.9 (3)
H8A—O8—H8B	90.1	C14—C13—C12	120.1 (3)
H9A—O9—H9B	109.5	C18—C13—C12	119.9 (3)
H10A—O10—H10B	98.7	C13—C14—C15	120.5 (3)
N1—C1—N2	110.7 (3)	C13—C14—H14A	119.7
N1—C1—H1A	124.7	C15—C14—H14A	119.7
N2—C1—H1A	124.7	C16—C15—C14	119.2 (3)
C3—C2—N1	109.3 (3)	C16—C15—C19	120.4 (3)
C3—C2—H2A	125.4	C14—C15—C19	120.4 (3)
N1—C2—H2A	125.4	C17—C16—C15	120.6 (3)
C2—C3—N2	106.3 (3)	C17—C16—H16A	119.7
C2—C3—H3A	126.9	C15—C16—H16A	119.7
N2—C3—H3A	126.9	C16—C17—C18	119.3 (3)
N2—C4—C5	112.4 (2)	C16—C17—C20	120.7 (3)
N2—C4—H4A	109.1	C18—C17—C20	119.9 (3)
C5—C4—H4A	109.1	C13—C18—C17	120.4 (3)
N2—C4—H4B	109.1	C13—C18—H18A	119.8
C5—C4—H4B	109.1	C17—C18—H18A	119.8
H4A—C4—H4B	107.9	O4—C19—O3	123.9 (3)
N3—C5—N4	111.1 (3)	O4—C19—C15	118.6 (3)
N3—C5—C4	124.1 (3)	O3—C19—C15	117.5 (3)
N4—C5—C4	124.8 (3)	O6—C20—O5	124.1 (3)
C7—C6—N4	132.0 (3)	O6—C20—C17	119.6 (3)
C7—C6—C11	122.2 (3)	O5—C20—C17	116.3 (3)

O1—Zn1—N1—C1	121.9 (2)	C5—N3—C11—C10	178.6 (3)
O1ⁱ—Zn1—N1—C1	−14.8 (3)	C7—C6—C11—N3	179.9 (3)
N1ⁱ—Zn1—N1—C1	−128.9 (3)	N4—C6—C11—N3	0.0 (3)
O1—Zn1—N1—C2	−60.7 (3)	C7—C6—C11—C10	0.8 (5)
O1ⁱ—Zn1—N1—C2	162.6 (3)	N4—C6—C11—C10	−179.1 (3)
N1ⁱ—Zn1—N1—C2	48.5 (3)	C9—C10—C11—N3	−178.9 (3)
O1ⁱ—Zn1—O1—C12	−34.72 (19)	C9—C10—C11—C6	−0.1 (5)
N1—Zn1—O1—C12	−155.2 (2)	Zn1—O1—C12—O2	−6.1 (4)
N1ⁱ—Zn1—O1—C12	88.8 (2)	Zn1—O1—C12—C13	172.90 (18)
C2—N1—C1—N2	0.5 (3)	O2—C12—C13—C14	−166.9 (3)
Zn1—N1—C1—N2	178.40 (19)	O1—C12—C13—C14	14.1 (4)
C3—N2—C1—N1	−0.2 (3)	O2—C12—C13—C18	14.9 (4)
C4—N2—C1—N1	−179.1 (3)	O1—C12—C13—C18	−164.2 (3)
C1—N1—C2—C3	−0.6 (4)	C18—C13—C14—C15	−0.9 (5)
Zn1—N1—C2—C3	−178.3 (2)	C12—C13—C14—C15	−179.2 (3)
N1—C2—C3—N2	0.5 (4)	C13—C14—C15—C16	1.5 (5)
C1—N2—C3—C2	−0.2 (4)	C13—C14—C15—C19	−179.6 (3)
C4—N2—C3—C2	178.7 (3)	C14—C15—C16—C17	−0.4 (5)
C1—N2—C4—C5	86.6 (4)	C19—C15—C16—C17	−179.3 (3)
C3—N2—C4—C5	−92.1 (4)	C15—C16—C17—C18	−1.2 (5)
C11—N3—C5—N4	0.7 (3)	C15—C16—C17—C20	175.5 (3)
C11—N3—C5—C4	−178.9 (3)	C14—C13—C18—C17	−0.7 (5)
C6—N4—C5—N3	−0.8 (4)	C12—C13—C18—C17	177.5 (3)
C6—N4—C5—C4	178.9 (3)	C16—C17—C18—C13	1.8 (5)
N2—C4—C5—N3	−87.7 (4)	C20—C17—C18—C13	−175.0 (3)
N2—C4—C5—N4	92.7 (4)	C16—C15—C19—O4	−2.6 (5)
C5—N4—C6—C7	−179.5 (4)	C14—C15—C19—O4	178.5 (3)
C5—N4—C6—C11	0.5 (3)	C16—C15—C19—O3	174.8 (4)
N4—C6—C7—C8	179.3 (3)	C14—C15—C19—O3	−4.1 (5)
C11—C6—C7—C8	−0.6 (5)	C16—C17—C20—O6	−172.3 (4)
C6—C7—C8—C9	−0.3 (6)	C18—C17—C20—O6	4.4 (5)
C7—C8—C9—C10	1.0 (6)	C16—C17—C20—O5	4.9 (5)
C8—C9—C10—C11	−0.8 (5)	C18—C17—C20—O5	−178.4 (3)
C5—N3—C11—C6	−0.4 (3)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O9	0.85	2.22	2.936 (8)	142
O9—H9A···O4	0.85	2.15	2.634 (7)	115
O9—H9B···O10	0.85	2.24	2.783 (12)	122
O10—H10A···O9	0.85	1.93	2.783 (12)	179
N4—H4···O7ⁱⁱ	0.86	1.97	2.808 (4)	163
O3—H3···O10ⁱⁱⁱ	0.82	2.56	3.341 (10)	159
O5—H5···N3^iv	0.82	1.77	2.577 (3)	165
O7—H7A···O2^v	0.85	1.98	2.784 (4)	156
O7—H7B···O8^vi	0.85	1.95	2.796 (5)	179
O8—H8B···O6^vii	0.85	2.02	2.799 (6)	152
O10—H10B···O6^viii	0.85	2.03	2.728 (9)	139

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O
M_r	1024.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.870 (4), 15.008 (3), 15.472 (3)
β (°)	109.51 (3)
V (Å³)	4567.9 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.18 × 0.15 × 0.14

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2004)
T_min, T_max	0.896, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	15325, 4127, 3898
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.158, 1.07
No. of reflections	4127
No. of parameters	314
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.45

Computer programs: CrystalClear (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O9	0.85	2.22	2.936 (8)	142.0
O9—H9A···O4	0.85	2.15	2.634 (7)	115.4
O9—H9B···O10	0.85	2.24	2.783 (12)	121.9
O10—H10A···O9	0.85	1.93	2.783 (12)	179.1
N4—H4···O7ⁱ	0.86	1.97	2.808 (4)	163.2
O3—H3···O10ⁱⁱ	0.82	2.56	3.341 (10)	159.1
O5—H5···N3ⁱⁱⁱ	0.82	1.77	2.577 (3)	165.4
O7—H7A···O2^iv	0.85	1.98	2.784 (4)	156.4
O7—H7B···O8^v	0.85	1.95	2.796 (5)	179.4
O8—H8B···O6^vi	0.85	2.02	2.799 (6)	151.8
O10—H10B···O6^vii	0.85	2.03	2.728 (9)	139.3

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

Acknowledgements

We gratefully acknowledge financial support by the National Natural Science Foundation of China (No. J0830412).

References

Lin, J.-D., Cheng, J.-W. & Du, S.-W. (2008). Cryst. Growth Des. 9, 3345–3353. Web of Science CrossRef 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
Tian, L., Yang, N. & Zhao, G.-Y. (2010). Inorg. Chem. Commun. 13, 1497–1500. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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