Diaqua­(5-carb­oxy­benzene-1,3-di­carboxyl­ato-κO1)(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′)zinc

Mei, C.-Z.; Li, K.-H.; Shan, W.-W.

doi:10.1107/S1600536811019519

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m804

doi:10.1107/S1600536811019519

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Diaqua(5-carboxybenzene-1,3-dicarboxylato-κO¹)(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)zinc

Chong-Zhen Mei,^a Kai-Hui Li ^a and Wen-Wen Shan ^a ^*

^aInstitute of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: hbsysww@163.com

(Received 15 May 2011; accepted 23 May 2011; online 28 May 2011)

In the title compound, [Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂], the Zn^II atom is five-coordinated by two N atoms from a 4,4′-dimethyl-2,2′-bipyridine ligand, one O atom from a 5-carboxybenzene-1,3-dicarboxylate ligand and two water molecules in a distorted trigonal–bipyramidal geometry. The complex molecules are linked by intermolecular O—H⋯O hydrogen bonds and partly overlapping π–π interactions [centroid–centroid distance = 4.017 (2) Å] into a three-dimensional supramolecular network.

Related literature

For background to the network topologies and applications of coordination polymers, see: Maspoch et al. (2007 ); Ockwig et al. (2005 ); Zang et al. (2006 ). For O—H⋯O hydrogen bonds, see: Desiraju et al. (2004 ). For π–π interactions, see: Zang et al. (2010 ).

Experimental

Crystal data

[Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂]
M_r = 493.76
Triclinic, $[P \overline 1]$
a = 9.1938 (9) Å
b = 10.7978 (8) Å
c = 11.5842 (7) Å
α = 85.238 (6)°
β = 72.960 (7)°
γ = 69.760 (8)°
V = 1031.40 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.780, T_max = 0.798
7701 measured reflections
3607 independent reflections
3246 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.05
3607 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6ⁱ	0.82	1.79	2.603 (2)	171
O1W—H1WA⋯O1ⁱⁱ	0.84	1.81	2.635 (2)	165
O1W—H1WB⋯O2ⁱⁱⁱ	0.84	1.75	2.593 (2)	171
O2W—H2WA⋯O2^iv	0.85	1.86	2.688 (2)	166
O2W—H2WB⋯O4^v	0.84	1.79	2.633 (2)	176
Symmetry codes: (i) -x-1, -y+1, -z+2; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z; (iv) -x, -y+1, -z+1; (v) -x, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019519/hy2433sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019519/hy2433Isup2.hkl

checkCIF report

Comment top

Supramolecular coordination assemblies have received much attention not only for their variety of architectures but also for the potential applications as functional materials (Maspoch et al., 2007; Ockwig et al., 2005). A great number of multidentate organic ligands such as organic aromatic polycarboxylate ligands and N-donor building blocks have been successfully employed in the generation of many interesting systems (Zang et al., 2006). To further explore the influence of multicarboxylate and N-donor ligands on the properties and construction of coordination compounds, we undertake the synthetic and structural studies on a Zn(II) complex based on benzene-1,3,5-tricarboxylic acid (H₃btc) and 4,4'-dimethyl-2,2'-bipyridine (dmbpy), Zn(Hbtc)(bmbpy)(H₂O)₂.

As shown in Fig. 1, the asymmetric unit consists of one Zn^II atom, one Hbtc ligand, one dmbpy ligand and two coordinated water molecules. The Hbtc ligand occurs in a form with an intact COOH group. The metal ion is coordinated by one O atom from the Hbtc ligand, two O atoms of water molecules and two N atoms from the chelating dmbpy ligand, completing a distorted trigonal bipyramidal geometry. N1, O1W and O2W comprise the equatorial plane, while O3 and N2 occupy the axial positions. A pair of symmetry-related complex molecules are associated together through O1W—H1WA···O1ⁱ hydrogen bonds (Table 1) [symmetry code: (i) 1-x, 1-y, 1-z], forming a dimeric unit, in which π–π stacking interaction occurs with a centroid–centroid distance of 4.017 (2)Å between two face-to-face aromatic rings (phenyl ring and pyridine ring bearing the N1 atom). Adjacent dimeric units are connected by O2W—H2WA···O2ⁱⁱ hydrogen bonds [symmetry code: (ii) -x, 1-y, 1-z], resulting in a one-dimensional supramolecular chain running along the a-axis (Fig. 2). As depicted in Fig. 3, the chains are extended to a two-dimensional supramolecular structure through O1W—H1WB···O2ⁱⁱⁱ and O2W—H2WB···O4^iv hydrogen bonds [symmetry codes: (iii) x, 1+y, z; (iv) -x, 2-y, 1-z]. The hydroxyl group and the uncoordinated O atom of the intact COOH group serve as donor and accepter, respectively. Neighboring such carboxylic groups are linked together through O5—H5A···O6^v hydrogen bonds [symmetry code: (v) -1-x, 1-y, 2-z]. Thus, the layers are interconnected into a three-dimensional supramolecular structure (Fig. 4).

Related literature top

For background to the network topologies and applications of coordination polymers, see: Maspoch et al. (2007); Ockwig et al. (2005); Zang et al. (2006). For O—H···O hydrogen bonds, see: Desiraju et al. (2004). For π–π interactions, see: Zang et al. (2010).

Experimental top

The title compound was synthesized hydrothermally in a Teflon-lined stainless steel container by heating a mixture of benzene-1,3,5-tricarboxylic acid (0.011 g, 0.05 mmol), 4,4'-dimethyl-2,2'-bipyridine (0.009 g, 0.05 mmol), Zn(NO₃)₂.6H₂O (0.015 g, 0.05 mmol) and NaOH (0.004 g, 0.1 mmol) in 7 ml of distilled water at 120°C for 3 d, and then cooled to room temperature. Colorless block crystals of the title compound were obtained in 68% yield based on zinc.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Irrespective H atoms are omitted for clarity.
	Fig. 2. A view of the supramolecular chain in the title compound. Dashed lines represent hydrogen bonds and π–π interactions. [Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 1+x, y, z.]
	Fig. 3. A view of the two-dimensional supramolecular structure in the title compound. Dashed lines represent hydrogen bonds. [Symmetry codes: (iii) x, 1+y, z; (iv) -x, 2-y, 1-z.]
	Fig. 4. The three-dimensional supramolecular structure connected by interlayer hydrogen bonds (dashed lines).

Diaqua(5-carboxybenzene-1,3-dicarboxylato-κO¹)(4,4'-dimethyl-2,2'- bipyridine-κ²N,N')zinc top

Crystal data top

[Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂]	Z = 2
M_r = 493.76	F(000) = 508
Triclinic, P1	D_x = 1.590 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1938 (9) Å	Cell parameters from 4795 reflections
b = 10.7978 (8) Å	θ = 3.5–29.1°
c = 11.5842 (7) Å	µ = 1.24 mm⁻¹
α = 85.238 (6)°	T = 296 K
β = 72.960 (7)°	Block, colorless
γ = 69.760 (8)°	0.21 × 0.20 × 0.19 mm
V = 1031.40 (16) Å³

Data collection top

Bruker APEXII CCD diffractometer	3607 independent reflections
Radiation source: fine-focus sealed tube	3246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.780, T_max = 0.798	k = −12→12
7701 measured reflections	l = −13→13

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0516P)²] where P = (F_o² + 2F_c²)/3
3607 reflections	(Δ/σ)_max = 0.009
292 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂]	γ = 69.760 (8)°
M_r = 493.76	V = 1031.40 (16) Å³
Triclinic, P1	Z = 2
a = 9.1938 (9) Å	Mo Kα radiation
b = 10.7978 (8) Å	µ = 1.24 mm⁻¹
c = 11.5842 (7) Å	T = 296 K
α = 85.238 (6)°	0.21 × 0.20 × 0.19 mm
β = 72.960 (7)°

Data collection top

Bruker APEXII CCD diffractometer	3607 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3246 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.798	R_int = 0.032
7701 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	Δρ_max = 0.34 e Å⁻³
3607 reflections	Δρ_min = −0.28 e Å⁻³
292 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.29959 (3)	0.80971 (2)	0.41463 (2)	0.02705 (12)
O1	0.3344 (2)	0.21247 (17)	0.51057 (18)	0.0451 (5)
O2	0.1654 (2)	0.11417 (16)	0.62226 (18)	0.0417 (5)
O3	0.1815 (2)	0.68960 (16)	0.50550 (15)	0.0353 (4)
O4	−0.0341 (2)	0.81358 (16)	0.64551 (17)	0.0442 (5)
O5	−0.4023 (2)	0.60517 (15)	0.91517 (15)	0.0378 (4)
H5A	−0.4810	0.5991	0.9684	0.057*
O6	−0.3417 (2)	0.38720 (15)	0.90916 (15)	0.0377 (4)
O1W	0.34722 (19)	0.87467 (15)	0.55069 (14)	0.0310 (4)
H1WA	0.4474	0.8605	0.5349	0.046*
H1WB	0.2920	0.9551	0.5668	0.046*
O2W	0.1124 (2)	0.92769 (15)	0.35858 (16)	0.0380 (4)
H2WA	0.0254	0.9106	0.3765	0.057*
H2WB	0.0912	1.0101	0.3581	0.057*
N1	0.4831 (2)	0.64334 (18)	0.31684 (17)	0.0294 (4)
N2	0.4584 (2)	0.89292 (18)	0.27789 (18)	0.0313 (5)
C1	0.2061 (3)	0.2140 (2)	0.5853 (2)	0.0295 (5)
C2	0.0560 (3)	0.7072 (2)	0.5941 (2)	0.0277 (5)
C3	−0.3103 (3)	0.4905 (2)	0.8723 (2)	0.0257 (5)
C4	0.0878 (3)	0.3468 (2)	0.6388 (2)	0.0244 (5)
C5	−0.0533 (3)	0.3572 (2)	0.7292 (2)	0.0261 (5)
H5	−0.0770	0.2816	0.7590	0.031*
C6	−0.1601 (3)	0.4811 (2)	0.7756 (2)	0.0254 (5)
C7	−0.1244 (3)	0.5936 (2)	0.73168 (19)	0.0246 (5)
H7	−0.1955	0.6759	0.7635	0.030*
C8	0.0167 (3)	0.5847 (2)	0.6404 (2)	0.0241 (5)
C9	0.1210 (3)	0.4604 (2)	0.5950 (2)	0.0256 (5)
H9	0.2154	0.4532	0.5337	0.031*
C10	0.4961 (3)	0.5176 (2)	0.3444 (2)	0.0352 (6)
H10	0.4184	0.5014	0.4101	0.042*
C11	0.6183 (3)	0.4113 (2)	0.2805 (2)	0.0378 (6)
H11	0.6214	0.3259	0.3027	0.045*
C12	0.7357 (3)	0.4315 (2)	0.1840 (2)	0.0341 (6)
C13	0.8735 (4)	0.3183 (3)	0.1126 (3)	0.0495 (7)
H13A	0.9377	0.2685	0.1638	0.074*
H13B	0.9394	0.3519	0.0463	0.074*
H13C	0.8313	0.2621	0.0821	0.074*
C14	0.7234 (3)	0.5617 (2)	0.1547 (2)	0.0319 (6)
H14	0.8002	0.5794	0.0894	0.038*
C15	0.5972 (3)	0.6652 (2)	0.2222 (2)	0.0269 (5)
C16	0.5789 (3)	0.8062 (2)	0.1965 (2)	0.0278 (5)
C17	0.6761 (3)	0.8476 (2)	0.0971 (2)	0.0374 (6)
H17	0.7560	0.7855	0.0409	0.045*
C18	0.6557 (3)	0.9805 (2)	0.0801 (2)	0.0384 (6)
C19	0.7596 (4)	1.0268 (3)	−0.0278 (3)	0.0604 (9)
H19A	0.8531	1.0303	−0.0091	0.091*
H19B	0.6990	1.1132	−0.0489	0.091*
H19C	0.7930	0.9666	−0.0946	0.091*
C20	0.5346 (3)	1.0673 (3)	0.1677 (3)	0.0436 (7)
H20	0.5178	1.1574	0.1616	0.052*
C21	0.4393 (3)	1.0211 (2)	0.2634 (2)	0.0398 (6)
H21	0.3581	1.0815	0.3204	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02375 (18)	0.02181 (17)	0.03013 (18)	−0.00935 (12)	0.00191 (12)	0.00227 (11)
O1	0.0236 (10)	0.0374 (10)	0.0601 (12)	−0.0075 (8)	0.0085 (9)	−0.0093 (9)
O2	0.0267 (9)	0.0214 (8)	0.0687 (13)	−0.0072 (7)	−0.0004 (9)	−0.0071 (8)
O3	0.0319 (10)	0.0301 (9)	0.0400 (10)	−0.0185 (7)	0.0036 (8)	0.0062 (7)
O4	0.0418 (11)	0.0204 (8)	0.0559 (12)	−0.0106 (8)	0.0066 (9)	0.0036 (8)
O5	0.0326 (10)	0.0273 (9)	0.0371 (10)	−0.0088 (8)	0.0132 (8)	−0.0019 (7)
O6	0.0350 (10)	0.0280 (9)	0.0419 (10)	−0.0160 (8)	0.0064 (8)	0.0056 (8)
O1W	0.0220 (9)	0.0236 (8)	0.0419 (10)	−0.0063 (7)	−0.0016 (8)	−0.0038 (7)
O2W	0.0299 (10)	0.0224 (8)	0.0614 (12)	−0.0118 (7)	−0.0109 (9)	0.0087 (8)
N1	0.0298 (11)	0.0249 (10)	0.0308 (10)	−0.0114 (8)	−0.0025 (9)	0.0018 (8)
N2	0.0269 (11)	0.0269 (10)	0.0334 (11)	−0.0088 (9)	0.0008 (9)	0.0014 (9)
C1	0.0227 (13)	0.0257 (12)	0.0387 (14)	−0.0066 (10)	−0.0073 (11)	−0.0044 (10)
C2	0.0272 (13)	0.0243 (12)	0.0321 (13)	−0.0128 (10)	−0.0062 (11)	0.0086 (10)
C3	0.0262 (12)	0.0240 (12)	0.0236 (11)	−0.0099 (10)	−0.0011 (10)	0.0021 (9)
C4	0.0211 (12)	0.0230 (11)	0.0294 (12)	−0.0099 (9)	−0.0048 (10)	0.0009 (9)
C5	0.0281 (13)	0.0202 (11)	0.0304 (12)	−0.0121 (10)	−0.0052 (10)	0.0046 (9)
C6	0.0237 (12)	0.0256 (11)	0.0258 (11)	−0.0107 (10)	−0.0033 (10)	0.0029 (9)
C7	0.0232 (12)	0.0196 (11)	0.0270 (12)	−0.0075 (9)	−0.0008 (10)	0.0003 (9)
C8	0.0220 (12)	0.0240 (11)	0.0256 (11)	−0.0099 (9)	−0.0040 (10)	0.0037 (9)
C9	0.0198 (12)	0.0273 (12)	0.0286 (12)	−0.0122 (9)	−0.0004 (10)	0.0016 (10)
C10	0.0410 (15)	0.0290 (13)	0.0341 (13)	−0.0167 (11)	−0.0040 (12)	0.0064 (11)
C11	0.0471 (17)	0.0233 (12)	0.0422 (15)	−0.0103 (11)	−0.0149 (13)	0.0060 (11)
C12	0.0369 (15)	0.0291 (13)	0.0359 (14)	−0.0065 (11)	−0.0144 (12)	−0.0011 (11)
C13	0.0533 (19)	0.0326 (14)	0.0516 (17)	−0.0004 (13)	−0.0134 (15)	−0.0062 (13)
C14	0.0288 (14)	0.0317 (13)	0.0305 (13)	−0.0088 (10)	−0.0033 (11)	0.0012 (10)
C15	0.0244 (12)	0.0296 (12)	0.0249 (12)	−0.0096 (10)	−0.0043 (10)	0.0030 (10)
C16	0.0250 (13)	0.0258 (12)	0.0303 (12)	−0.0090 (10)	−0.0050 (10)	0.0033 (10)
C17	0.0323 (14)	0.0343 (13)	0.0343 (14)	−0.0098 (11)	0.0054 (12)	0.0006 (11)
C18	0.0371 (15)	0.0327 (13)	0.0425 (15)	−0.0160 (12)	−0.0046 (12)	0.0101 (12)
C19	0.063 (2)	0.0489 (18)	0.062 (2)	−0.0310 (16)	0.0061 (17)	0.0128 (16)
C20	0.0425 (16)	0.0268 (13)	0.0559 (17)	−0.0132 (12)	−0.0060 (14)	0.0082 (12)
C21	0.0383 (15)	0.0256 (12)	0.0456 (15)	−0.0087 (11)	0.0008 (13)	−0.0008 (11)

Geometric parameters (Å, º) top

Zn1—O1W	1.9922 (16)	C7—C8	1.392 (3)
Zn1—O2W	2.0018 (16)	C7—H7	0.9300
Zn1—O3	2.0115 (16)	C8—C9	1.389 (3)
Zn1—N1	2.1159 (19)	C9—H9	0.9300
Zn1—N2	2.1826 (19)	C10—C11	1.374 (4)
O1—C1	1.238 (3)	C10—H10	0.9300
O2—C1	1.262 (3)	C11—C12	1.370 (4)
O3—C2	1.268 (3)	C11—H11	0.9300
O4—C2	1.235 (3)	C12—C14	1.391 (3)
O5—C3	1.275 (3)	C12—C13	1.506 (4)
O5—H5A	0.8200	C13—H13A	0.9600
O6—C3	1.257 (3)	C13—H13B	0.9600
O1W—H1WA	0.8444	C13—H13C	0.9600
O1W—H1WB	0.8446	C14—C15	1.387 (3)
O2W—H2WA	0.8460	C14—H14	0.9300
O2W—H2WB	0.8421	C15—C16	1.487 (3)
N1—C10	1.341 (3)	C16—C17	1.382 (3)
N1—C15	1.346 (3)	C17—C18	1.386 (3)
N2—C21	1.336 (3)	C17—H17	0.9300
N2—C16	1.346 (3)	C18—C20	1.386 (4)
C1—C4	1.516 (3)	C18—C19	1.501 (4)
C2—C8	1.505 (3)	C19—H19A	0.9600
C3—C6	1.480 (3)	C19—H19B	0.9600
C4—C5	1.384 (3)	C19—H19C	0.9600
C4—C9	1.386 (3)	C20—C21	1.374 (4)
C5—C6	1.394 (3)	C20—H20	0.9300
C5—H5	0.9300	C21—H21	0.9300
C6—C7	1.384 (3)

O1W—Zn1—O2W	117.76 (7)	C7—C8—C2	120.5 (2)
O1W—Zn1—O3	99.49 (7)	C4—C9—C8	121.6 (2)
O2W—Zn1—O3	94.51 (7)	C4—C9—H9	119.2
O1W—Zn1—N1	115.84 (7)	C8—C9—H9	119.2
O2W—Zn1—N1	124.77 (8)	N1—C10—C11	123.3 (2)
O3—Zn1—N1	89.06 (7)	N1—C10—H10	118.3
O1W—Zn1—N2	93.17 (7)	C11—C10—H10	118.3
O2W—Zn1—N2	89.03 (7)	C12—C11—C10	119.9 (2)
O3—Zn1—N2	163.37 (7)	C12—C11—H11	120.1
N1—Zn1—N2	75.66 (7)	C10—C11—H11	120.1
C2—O3—Zn1	133.53 (15)	C11—C12—C14	117.2 (2)
C3—O5—H5A	109.5	C11—C12—C13	121.7 (2)
Zn1—O1W—H1WA	110.1	C14—C12—C13	121.0 (2)
Zn1—O1W—H1WB	111.0	C12—C13—H13A	109.5
H1WA—O1W—H1WB	112.2	C12—C13—H13B	109.5
Zn1—O2W—H2WA	119.9	H13A—C13—H13B	109.5
Zn1—O2W—H2WB	120.2	C12—C13—H13C	109.5
H2WA—O2W—H2WB	109.6	H13A—C13—H13C	109.5
C10—N1—C15	117.7 (2)	H13B—C13—H13C	109.5
C10—N1—Zn1	124.60 (16)	C15—C14—C12	120.5 (2)
C15—N1—Zn1	117.70 (14)	C15—C14—H14	119.7
C21—N2—C16	118.1 (2)	C12—C14—H14	119.7
C21—N2—Zn1	125.98 (17)	N1—C15—C14	121.4 (2)
C16—N2—Zn1	115.76 (15)	N1—C15—C16	115.7 (2)
O1—C1—O2	125.7 (2)	C14—C15—C16	123.0 (2)
O1—C1—C4	117.5 (2)	N2—C16—C17	121.5 (2)
O2—C1—C4	116.8 (2)	N2—C16—C15	114.79 (19)
O4—C2—O3	126.4 (2)	C17—C16—C15	123.7 (2)
O4—C2—C8	118.0 (2)	C16—C17—C18	120.8 (2)
O3—C2—C8	115.6 (2)	C16—C17—H17	119.6
O6—C3—O5	123.0 (2)	C18—C17—H17	119.6
O6—C3—C6	119.6 (2)	C17—C18—C20	116.4 (2)
O5—C3—C6	117.45 (19)	C17—C18—C19	121.4 (2)
C5—C4—C9	119.4 (2)	C20—C18—C19	122.2 (2)
C5—C4—C1	121.50 (19)	C18—C19—H19A	109.5
C9—C4—C1	119.1 (2)	C18—C19—H19B	109.5
C4—C5—C6	119.9 (2)	H19A—C19—H19B	109.5
C4—C5—H5	120.0	C18—C19—H19C	109.5
C6—C5—H5	120.0	H19A—C19—H19C	109.5
C7—C6—C5	120.0 (2)	H19B—C19—H19C	109.5
C7—C6—C3	120.7 (2)	C21—C20—C18	120.3 (2)
C5—C6—C3	119.27 (19)	C21—C20—H20	119.8
C6—C7—C8	120.7 (2)	C18—C20—H20	119.8
C6—C7—H7	119.6	N2—C21—C20	122.7 (2)
C8—C7—H7	119.6	N2—C21—H21	118.6
C9—C8—C7	118.4 (2)	C20—C21—H21	118.6
C9—C8—C2	121.1 (2)

O1W—Zn1—O3—C2	57.8 (2)	O4—C2—C8—C9	−173.5 (2)
O2W—Zn1—O3—C2	−61.4 (2)	O3—C2—C8—C9	5.7 (3)
N1—Zn1—O3—C2	173.8 (2)	O4—C2—C8—C7	5.3 (3)
N2—Zn1—O3—C2	−163.2 (2)	O3—C2—C8—C7	−175.5 (2)
O1W—Zn1—N1—C10	89.3 (2)	C5—C4—C9—C8	0.6 (3)
O2W—Zn1—N1—C10	−105.6 (2)	C1—C4—C9—C8	179.8 (2)
O3—Zn1—N1—C10	−10.8 (2)	C7—C8—C9—C4	−0.3 (3)
N2—Zn1—N1—C10	175.8 (2)	C2—C8—C9—C4	178.6 (2)
O1W—Zn1—N1—C15	−88.84 (17)	C15—N1—C10—C11	−0.6 (4)
O2W—Zn1—N1—C15	76.23 (18)	Zn1—N1—C10—C11	−178.77 (19)
O3—Zn1—N1—C15	171.07 (17)	N1—C10—C11—C12	0.7 (4)
N2—Zn1—N1—C15	−2.30 (16)	C10—C11—C12—C14	−0.6 (4)
O1W—Zn1—N2—C21	−63.8 (2)	C10—C11—C12—C13	179.0 (2)
O2W—Zn1—N2—C21	54.0 (2)	C11—C12—C14—C15	0.5 (4)
O3—Zn1—N2—C21	156.6 (2)	C13—C12—C14—C15	−179.0 (2)
N1—Zn1—N2—C21	−179.6 (2)	C10—N1—C15—C14	0.5 (3)
O1W—Zn1—N2—C16	121.32 (17)	Zn1—N1—C15—C14	178.81 (18)
O2W—Zn1—N2—C16	−120.94 (18)	C10—N1—C15—C16	−179.1 (2)
O3—Zn1—N2—C16	−18.3 (4)	Zn1—N1—C15—C16	−0.8 (3)
N1—Zn1—N2—C16	5.44 (17)	C12—C14—C15—N1	−0.5 (4)
Zn1—O3—C2—O4	3.8 (4)	C12—C14—C15—C16	179.1 (2)
Zn1—O3—C2—C8	−175.34 (15)	C21—N2—C16—C17	−3.1 (4)
O1—C1—C4—C5	−175.4 (2)	Zn1—N2—C16—C17	172.22 (19)
O2—C1—C4—C5	3.9 (3)	C21—N2—C16—C15	177.2 (2)
O1—C1—C4—C9	5.5 (3)	Zn1—N2—C16—C15	−7.5 (3)
O2—C1—C4—C9	−175.3 (2)	N1—C15—C16—N2	5.6 (3)
C9—C4—C5—C6	−0.3 (3)	C14—C15—C16—N2	−174.0 (2)
C1—C4—C5—C6	−179.5 (2)	N1—C15—C16—C17	−174.1 (2)
C4—C5—C6—C7	−0.3 (3)	C14—C15—C16—C17	6.2 (4)
C4—C5—C6—C3	−179.9 (2)	N2—C16—C17—C18	2.2 (4)
O6—C3—C6—C7	178.6 (2)	C15—C16—C17—C18	−178.1 (2)
O5—C3—C6—C7	−1.8 (3)	C16—C17—C18—C20	0.2 (4)
O6—C3—C6—C5	−1.8 (3)	C16—C17—C18—C19	−179.6 (3)
O5—C3—C6—C5	177.8 (2)	C17—C18—C20—C21	−1.6 (4)
C5—C6—C7—C8	0.7 (3)	C19—C18—C20—C21	178.2 (3)
C3—C6—C7—C8	−179.8 (2)	C16—N2—C21—C20	1.7 (4)
C6—C7—C8—C9	−0.3 (3)	Zn1—N2—C21—C20	−173.1 (2)
C6—C7—C8—C2	−179.2 (2)	C18—C20—C21—N2	0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱ	0.82	1.79	2.603 (2)	171
O1W—H1WA···O1ⁱⁱ	0.84	1.81	2.635 (2)	165
O1W—H1WB···O2ⁱⁱⁱ	0.84	1.75	2.593 (2)	171
O2W—H2WA···O2^iv	0.85	1.86	2.688 (2)	166
O2W—H2WB···O4^v	0.84	1.79	2.633 (2)	176

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₄O₆)(C₁₂H₁₂N₂)(H₂O)₂]
M_r	493.76
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.1938 (9), 10.7978 (8), 11.5842 (7)
α, β, γ (°)	85.238 (6), 72.960 (7), 69.760 (8)
V (Å³)	1031.40 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.21 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.780, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	7701, 3607, 3246
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.05
No. of reflections	3607
No. of parameters	292
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱ	0.82	1.79	2.603 (2)	171
O1W—H1WA···O1ⁱⁱ	0.84	1.81	2.635 (2)	165
O1W—H1WB···O2ⁱⁱⁱ	0.84	1.75	2.593 (2)	171
O2W—H2WA···O2^iv	0.85	1.86	2.688 (2)	166
O2W—H2WB···O4^v	0.84	1.79	2.633 (2)	176

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

Acknowledgements

This work was supported financially by the Natural Science Foundation of Henan Province (No. 2010 A140009) and the International Technology Cooperation Project of Science and Technology Department of Henan Province of China (No. 104300510044).

References

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