Poly[[hexa­aqua­bis­(μ3-benzene-1,3,5-tricarboxyl­ato-κ3O1:O3:O5)bis­(5,5′-dimethyl-2,2′-bipyridine-κ2N,N′)trizinc] hexa­hydrate]

Shan, W.-W.; Xiong, H.-L.; Mei, C.-Z.

doi:10.1107/S1600536811022173

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m921-m922

doi:10.1107/S1600536811022173

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Poly[[hexaaquabis(μ₃-benzene-1,3,5-tricarboxylato-κ³O¹:O³:O⁵)bis(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)trizinc] hexahydrate]

Wen-Wen Shan,^a ^* Han-Lin Xiong ^a and Chong-Zhen Mei ^a

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

(Received 1 June 2011; accepted 8 June 2011; online 18 June 2011)

In the title compound, {[Zn₃(C₉H₃O₆)₂(C₁₂H₁₂N₂)₂(H₂O)₆]·6H₂O}_n, one Zn^II atom, lying on an inversion center, is six-coordinated by two O atoms from two benzene-1,3,5-tricarboxylate (btc) ligands and four water molecules in a distorted octahedral geometry. The other Zn^II atom is five-coordinated by two N atoms from a 5,5′-dimethyl-2,2′-bipyridine (dmbpy) ligand, two O atoms from two btc ligands and one water molecule in a distorted trigonal–bipyramidal geometry. The compound features a one-dimensional ladder structure, with windows of ca 10.245 (1) × 15.446 (2) Å. The ladders are linked together by intermolecular O—H⋯O hydrogen bonds and π–π interactions between the benzene rings and between the pyridine rings [centroid-to-centroid distances 3.858 (2) and 3.911 (3) Å, respectively] to form a three-dimensional supramolecular structure. One of the lattice water molecules is disordered over two positions in a 0.592:0.408 ratio.

Related literature

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

Experimental

Crystal data

[Zn₃(C₉H₃O₆)₂(C₁₂H₁₂N₂)₂(H₂O)₆]·6H₂O
M_r = 1195.00
Triclinic, $[P \overline 1]$
a = 10.2454 (10) Å
b = 10.5799 (10) Å
c = 12.658 (1) Å
α = 68.910 (8)°
β = 74.848 (8)°
γ = 81.834 (8)°
V = 1233.90 (19) Å³
Z = 1
Mo Kα radiation
μ = 1.54 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 = 0.739, T_max = 0.759
9149 measured reflections
4330 independent reflections
3426 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.01
4330 reflections
336 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O5ⁱ	0.84	1.93	2.754 (4)	166
O1W—H1WB⋯O6Wⁱⁱ	0.84	1.96	2.805 (5)	176
O2W—H2WA⋯O2ⁱⁱⁱ	0.85	1.95	2.768 (4)	162
O2W—H2WB⋯O5Wⁱⁱⁱ	0.85	2.14	2.806 (6)	135
O3W—H3WB⋯O3ⁱⁱⁱ	0.85	2.16	2.740 (4)	125
O3W—H3WC⋯O5	0.85	2.26	2.705 (4)	113
O4W—H4WA⋯O5W	0.95	2.22	3.166 (19)	173
O4W′—H4WD⋯O2	0.87	2.63	3.499 (11)	177
O5W—H5WA⋯O6W	0.85	2.14	2.987 (9)	179
O5W—H5WC⋯O6^iv	0.90	2.28	3.151 (7)	164
O6W—H6WB⋯O1^iv	0.85	2.16	2.947 (5)	154
O6W—H6WD⋯O4^v	0.85	2.23	3.019 (6)	154
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+1, -z+1; (iii) x, y-1, z; (iv) x, y+1, z; (v) x-1, y+1, z.

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/S1600536811022173/hy2439sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022173/hy2439Isup2.hkl

checkCIF report

Comment top

In recent years, 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). According to literature, carboxylate-based ligands are good bridging ligands to construct coordination polymers, in which many supramolecular structures have been furnished (Zang et al., 2006, 2010). The rational assembly of target metal–organic networks depends on deliberate designs of the ligands with adjustable connectivity and a reasonable choice of metal ions with specific coordination nature. Additionally, the use of auxiliary ligands is also an effective method for the construction of coordination polymers (Du et al., 2007). To further explore the influence of multicarboxylates and N-donor ligands on the properties and construction of coordination compounds, we undertake synthetic and structural studies on the title compound, a Zn(II) complex based on benzene-1,3,5-tricarboxylic acid (H₃btc) and 5,5'-dimethyl-2,2'-bipyridine (dmbpy).

As shown in Fig. 1, the asymmetric unit of the title compound consists of one and a half Zn^II atoms, one btc ligand, one dmbpy ligand, three coordinated and three uncoordinated water molecules. Zn2 atom is located on an inversion center. Zn1 atom is coordinated by two O atoms from two btc ligands, one water molecule and two N atoms from one chelating dmbpy ligand, completing a distorted trigonal–bipyramidal geometry. N2, O1 and O4ⁱ [symmetry code: (i) x - 1, y, z] comprise the equatorial plane, while O1W and N1 occupy the axial positions. Zn2 atom is in a distorted octahedral coordination environment and coordinated by two O atoms from a pair of symmetry-related btc ligands and four O atoms from two pairs of coordinated water molecules. O2W, O2Wⁱⁱ, O3W and O3Wⁱⁱ [symmetry code: (ii) -x + 1, -y - 1, -z + 1] comprise the equatorial plane, while O6 and O6ⁱⁱ occupy the axial positions. As depicted in Fig. 2, adjacent Zn1 atoms are linked together through btc ligands, forming a chain running along the a axis with the dmbpy ligands hanging from the chain. A pair of symmetry-related chains are connected by Zn2 atoms, resulting in a one-dimensional ladder structure containing large windows [ca 10.245 (1) × 15.446 (2) Å²]. The ladders are extended into a three-dimensional supramolecular structure through hydrogen bonds (Table 1) (Desiraju, 2004) and π–π stacking interactions (Zang et al., 2010), with centroid–centroid distances of 3.858 (2) and 3.911 (3) between the benzene rings and between the pyridine rings (Fig. 3).

Related literature top

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

Experimental top

All starting materials used in the synthesis were of analytical grade and obtained from commercial sources without further purification. 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), 5,5'-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. Washed with deionized water and dried, colorless block crystals of the title compound were obtained in 72% 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. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x - 1, y, z; (ii) -x + 1, -y - 1, -z + 1.]
	Fig. 2. The one-dimensional ladder structure in the title compound.
	Fig. 3. A view of the three-dimensional supramolecular structure in the title compound. Dashed lines represent hydrogen bonds.

Poly[[hexaaquabis(µ₃-benzene-1,3,5-tricarboxylato- κ³O¹:O³:O⁵)bis(5,5'-dimethyl-2,2'-bipyridine- κ²N,N')trizinc] hexahydrate] top

Crystal data top

[Zn₃(C₉H₃O₆)₂(C₁₂H₁₂N₂)₂(H₂O)₆]·6H₂O	Z = 1
M_r = 1195.00	F(000) = 616
Triclinic, P1	D_x = 1.608 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2454 (10) Å	Cell parameters from 3902 reflections
b = 10.5799 (10) Å	θ = 3.0–29.2°
c = 12.658 (1) Å	µ = 1.54 mm⁻¹
α = 68.910 (8)°	T = 296 K
β = 74.848 (8)°	Block, colourless
γ = 81.834 (8)°	0.21 × 0.20 × 0.19 mm
V = 1233.90 (19) Å³

Data collection top

Bruker APEXII CCD diffractometer	4330 independent reflections
Radiation source: fine-focus sealed tube	3426 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→11
T_min = 0.739, T_max = 0.759	k = −12→12
9149 measured reflections	l = −14→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0713P)² + 0.3228P] where P = (F_o² + 2F_c²)/3
4330 reflections	(Δ/σ)_max < 0.001
336 parameters	Δρ_max = 0.74 e Å⁻³
12 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Zn₃(C₉H₃O₆)₂(C₁₂H₁₂N₂)₂(H₂O)₆]·6H₂O	γ = 81.834 (8)°
M_r = 1195.00	V = 1233.90 (19) Å³
Triclinic, P1	Z = 1
a = 10.2454 (10) Å	Mo Kα radiation
b = 10.5799 (10) Å	µ = 1.54 mm⁻¹
c = 12.658 (1) Å	T = 296 K
α = 68.910 (8)°	0.21 × 0.20 × 0.19 mm
β = 74.848 (8)°

Data collection top

Bruker APEXII CCD diffractometer	4330 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3426 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.759	R_int = 0.034
9149 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	12 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	Δρ_max = 0.74 e Å⁻³
4330 reflections	Δρ_min = −0.59 e Å⁻³
336 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.12533 (4)	0.26423 (4)	0.27950 (4)	0.02392 (16)
Zn2	0.5000	−0.5000	0.5000	0.0307 (2)
O1	0.2755 (2)	0.1223 (3)	0.3318 (2)	0.0318 (7)
O2	0.3634 (3)	0.3178 (3)	0.2870 (3)	0.0402 (7)
O3	0.8425 (3)	0.3214 (2)	0.3035 (2)	0.0308 (7)
O4	0.9762 (2)	0.1367 (2)	0.3164 (2)	0.0291 (6)
O5	0.7603 (3)	−0.3095 (2)	0.4380 (3)	0.0328 (7)
O6	0.5455 (3)	−0.3002 (3)	0.4271 (3)	0.0361 (7)
O1W	0.0603 (3)	0.3070 (3)	0.4344 (2)	0.0333 (7)
H1WA	0.1250	0.3022	0.4656	0.050*
H1WB	−0.0007	0.2560	0.4821	0.050*
O2W	0.4783 (3)	−0.4920 (3)	0.3334 (3)	0.0432 (8)
H2WA	0.4387	−0.5581	0.3356	0.065*
H2WB	0.4504	−0.4322	0.2770	0.065*
O3W	0.7074 (3)	−0.5649 (3)	0.4677 (3)	0.0408 (8)
H3WB	0.7155	−0.6398	0.4555	0.061*
H3WC	0.7508	−0.5056	0.4082	0.061*
O4W	0.4365 (14)	0.6435 (16)	0.0453 (12)	0.117 (3)	0.408 (9)
H4WA	0.4059	0.6795	0.1072	0.175*	0.408 (9)
H4WB	0.4578	0.5864	0.0534	0.175*	0.408 (9)
O4W'	0.4797 (10)	0.5541 (10)	0.0114 (9)	0.117 (3)	0.592 (9)
H4WD	0.4529	0.4924	0.0792	0.175*	0.592 (9)
H4WE	0.4258	0.6206	−0.0140	0.175*	0.592 (9)
O5W	0.3621 (5)	0.7702 (6)	0.2466 (6)	0.142 (2)
H5WA	0.2969	0.7985	0.2914	0.213*
H5WC	0.4226	0.7649	0.2885	0.213*
O6W	0.1335 (5)	0.8711 (5)	0.4028 (4)	0.1048 (18)
H6WB	0.1775	0.9325	0.4047	0.157*
H6WD	0.0961	0.9389	0.3584	0.157*
N1	0.1983 (3)	0.2550 (3)	0.1050 (3)	0.0302 (8)
N2	0.1122 (3)	0.4690 (3)	0.1716 (3)	0.0269 (7)
C1	0.3732 (4)	0.1913 (4)	0.3168 (3)	0.0247 (8)
C2	0.8611 (4)	0.1978 (4)	0.3186 (3)	0.0207 (8)
C3	0.6509 (4)	−0.2463 (4)	0.4204 (3)	0.0248 (8)
C4	0.5062 (3)	0.1165 (4)	0.3354 (3)	0.0216 (8)
C5	0.6183 (3)	0.1867 (4)	0.3203 (3)	0.0235 (8)
H5	0.6110	0.2808	0.2988	0.028*
C6	0.7415 (3)	0.1176 (3)	0.3371 (3)	0.0207 (8)
C7	0.7516 (3)	−0.0216 (3)	0.3692 (3)	0.0201 (8)
H7	0.8338	−0.0679	0.3806	0.024*
C8	0.6407 (4)	−0.0943 (3)	0.3851 (3)	0.0215 (8)
C9	0.5189 (4)	−0.0233 (4)	0.3676 (3)	0.0225 (8)
H9	0.4443	−0.0708	0.3777	0.027*
C10	0.2447 (4)	0.1427 (4)	0.0791 (4)	0.0375 (10)
H10	0.2463	0.0610	0.1400	0.045*
C11	0.2910 (4)	0.1418 (5)	−0.0342 (4)	0.0412 (11)
C12	0.3435 (6)	0.0116 (5)	−0.0579 (5)	0.0621 (15)
H12A	0.3412	−0.0615	0.0144	0.093*
H12B	0.4349	0.0210	−0.1032	0.093*
H12C	0.2876	−0.0075	−0.1000	0.093*
C13	0.2863 (5)	0.2651 (5)	−0.1217 (4)	0.0447 (11)
H13	0.3157	0.2694	−0.1988	0.054*
C14	0.2389 (5)	0.3818 (5)	−0.0967 (4)	0.0419 (11)
H14	0.2364	0.4645	−0.1564	0.050*
C15	0.1949 (4)	0.3746 (4)	0.0188 (3)	0.0304 (9)
C16	0.1458 (4)	0.4930 (4)	0.0569 (4)	0.0287 (9)
C17	0.1358 (4)	0.6233 (4)	−0.0215 (4)	0.0386 (11)
H17	0.1577	0.6387	−0.1010	0.046*
C18	0.0930 (5)	0.7297 (4)	0.0198 (4)	0.0443 (12)
H18	0.0871	0.8175	−0.0322	0.053*
C19	0.0590 (4)	0.7070 (4)	0.1378 (4)	0.0381 (11)
C20	0.0129 (5)	0.8197 (5)	0.1863 (5)	0.0533 (13)
H20A	0.0763	0.8258	0.2281	0.080*
H20B	−0.0747	0.8018	0.2381	0.080*
H20C	0.0073	0.9038	0.1240	0.080*
C21	0.0697 (4)	0.5739 (4)	0.2107 (4)	0.0341 (10)
H21	0.0465	0.5561	0.2906	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0188 (3)	0.0242 (3)	0.0267 (3)	−0.00367 (17)	−0.00609 (18)	−0.00453 (19)
Zn2	0.0273 (4)	0.0215 (3)	0.0435 (4)	−0.0059 (3)	−0.0063 (3)	−0.0107 (3)
O1	0.0175 (14)	0.0356 (15)	0.0417 (18)	−0.0021 (11)	−0.0126 (12)	−0.0080 (13)
O2	0.0321 (17)	0.0315 (16)	0.059 (2)	0.0060 (12)	−0.0200 (15)	−0.0145 (14)
O3	0.0290 (15)	0.0192 (14)	0.0441 (18)	−0.0061 (11)	−0.0087 (13)	−0.0086 (12)
O4	0.0138 (13)	0.0267 (14)	0.0460 (18)	−0.0001 (11)	−0.0073 (12)	−0.0112 (13)
O5	0.0298 (16)	0.0214 (14)	0.0508 (19)	0.0007 (11)	−0.0178 (14)	−0.0111 (13)
O6	0.0268 (15)	0.0224 (14)	0.062 (2)	−0.0077 (11)	−0.0145 (14)	−0.0120 (14)
O1W	0.0301 (15)	0.0433 (17)	0.0287 (16)	−0.0092 (12)	−0.0089 (12)	−0.0104 (13)
O2W	0.055 (2)	0.0332 (16)	0.046 (2)	−0.0066 (14)	−0.0158 (16)	−0.0136 (14)
O3W	0.0314 (16)	0.0288 (15)	0.062 (2)	−0.0021 (12)	−0.0040 (14)	−0.0191 (15)
O4W	0.113 (3)	0.119 (3)	0.118 (3)	−0.0102 (14)	−0.0282 (15)	−0.0372 (15)
O4W'	0.113 (3)	0.119 (3)	0.118 (3)	−0.0102 (14)	−0.0282 (15)	−0.0372 (15)
O5W	0.101 (4)	0.110 (4)	0.181 (6)	0.005 (3)	−0.051 (4)	0.001 (4)
O6W	0.134 (4)	0.123 (4)	0.060 (3)	−0.088 (3)	−0.015 (3)	−0.010 (3)
N1	0.0326 (19)	0.0304 (18)	0.0263 (19)	−0.0060 (14)	−0.0052 (15)	−0.0074 (15)
N2	0.0208 (17)	0.0305 (18)	0.028 (2)	−0.0039 (13)	−0.0064 (14)	−0.0063 (15)
C1	0.0166 (19)	0.034 (2)	0.024 (2)	0.0013 (16)	−0.0068 (15)	−0.0099 (17)
C2	0.021 (2)	0.0235 (19)	0.0158 (19)	−0.0072 (15)	−0.0019 (15)	−0.0034 (15)
C3	0.029 (2)	0.0240 (19)	0.023 (2)	−0.0083 (17)	−0.0042 (16)	−0.0090 (16)
C4	0.0177 (19)	0.029 (2)	0.018 (2)	−0.0007 (15)	−0.0030 (15)	−0.0088 (16)
C5	0.0210 (19)	0.0210 (18)	0.027 (2)	−0.0016 (15)	−0.0076 (16)	−0.0039 (16)
C6	0.0172 (18)	0.0230 (18)	0.023 (2)	−0.0042 (14)	−0.0044 (15)	−0.0075 (16)
C7	0.0162 (18)	0.0193 (17)	0.023 (2)	−0.0018 (14)	−0.0043 (15)	−0.0054 (15)
C8	0.024 (2)	0.0216 (18)	0.020 (2)	−0.0039 (15)	−0.0046 (15)	−0.0082 (16)
C9	0.0166 (19)	0.0274 (19)	0.024 (2)	−0.0048 (15)	−0.0049 (15)	−0.0085 (16)
C10	0.044 (3)	0.032 (2)	0.035 (3)	−0.0078 (19)	−0.009 (2)	−0.008 (2)
C11	0.040 (3)	0.051 (3)	0.039 (3)	−0.005 (2)	−0.007 (2)	−0.023 (2)
C12	0.077 (4)	0.057 (3)	0.058 (4)	0.001 (3)	−0.007 (3)	−0.034 (3)
C13	0.050 (3)	0.057 (3)	0.029 (3)	−0.008 (2)	−0.007 (2)	−0.017 (2)
C14	0.050 (3)	0.044 (3)	0.028 (3)	−0.008 (2)	−0.008 (2)	−0.006 (2)
C15	0.025 (2)	0.036 (2)	0.031 (2)	−0.0059 (17)	−0.0084 (18)	−0.0081 (19)
C16	0.025 (2)	0.029 (2)	0.033 (3)	−0.0058 (16)	−0.0085 (18)	−0.0090 (18)
C17	0.050 (3)	0.033 (2)	0.025 (2)	−0.005 (2)	−0.009 (2)	0.0014 (19)
C18	0.049 (3)	0.030 (2)	0.045 (3)	−0.003 (2)	−0.017 (2)	0.002 (2)
C19	0.031 (2)	0.031 (2)	0.050 (3)	0.0001 (18)	−0.012 (2)	−0.011 (2)
C20	0.056 (3)	0.040 (3)	0.063 (4)	0.001 (2)	−0.010 (3)	−0.020 (3)
C21	0.033 (2)	0.033 (2)	0.036 (3)	−0.0050 (18)	−0.0079 (19)	−0.0092 (19)

Geometric parameters (Å, º) top

Zn1—O4ⁱ	2.033 (2)	N2—C16	1.338 (5)
Zn1—O1	2.055 (3)	N2—C21	1.346 (5)
Zn1—O1W	2.089 (3)	C1—C4	1.505 (5)
Zn1—N2	2.112 (3)	C2—C6	1.509 (5)
Zn1—N1	2.172 (3)	C3—C8	1.502 (5)
Zn2—O6ⁱⁱ	2.047 (2)	C4—C9	1.382 (5)
Zn2—O6	2.047 (2)	C4—C5	1.390 (5)
Zn2—O3Wⁱⁱ	2.119 (3)	C5—C6	1.393 (5)
Zn2—O3W	2.119 (3)	C5—H5	0.9300
Zn2—O2W	2.148 (3)	C6—C7	1.375 (5)
Zn2—O2Wⁱⁱ	2.148 (3)	C7—C8	1.393 (5)
O1—C1	1.256 (4)	C7—H7	0.9300
O2—C1	1.250 (5)	C8—C9	1.389 (5)
O3—C2	1.246 (4)	C9—H9	0.9300
O4—C2	1.260 (4)	C10—C11	1.391 (6)
O4—Zn1ⁱⁱⁱ	2.033 (2)	C10—H10	0.9300
O5—C3	1.250 (4)	C11—C13	1.378 (6)
O6—C3	1.260 (4)	C11—C12	1.510 (7)
O1W—H1WA	0.8433	C12—H12A	0.9600
O1W—H1WB	0.8428	C12—H12B	0.9600
O2W—H2WA	0.8457	C12—H12C	0.9600
O2W—H2WB	0.8499	C13—C14	1.375 (7)
O3W—H3WB	0.8500	C13—H13	0.9300
O3W—H3WC	0.8500	C14—C15	1.390 (6)
O4W—H4WA	0.9537	C14—H14	0.9300
O4W—H4WB	0.5942	C15—C16	1.477 (6)
O4W—H4WE	0.9037	C16—C17	1.387 (5)
O4W'—O4W'^iv	1.27 (2)	C17—C18	1.377 (6)
O4W'—H4WB	0.7048	C17—H17	0.9300
O4W'—H4WD	0.8736	C18—C19	1.380 (6)
O4W'—H4WE	0.8501	C18—H18	0.9300
O5W—H5WA	0.8514	C19—C21	1.386 (6)
O5W—H5WC	0.9000	C19—C20	1.496 (6)
O6W—H6WB	0.8520	C20—H20A	0.9599
O6W—H6WD	0.8499	C20—H20B	0.9600
N1—C10	1.335 (5)	C20—H20C	0.9601
N1—C15	1.344 (5)	C21—H21	0.9300

O4ⁱ—Zn1—O1	98.75 (10)	O6—C3—C8	115.5 (3)
O4ⁱ—Zn1—O1W	95.22 (11)	C9—C4—C5	118.9 (3)
O1—Zn1—O1W	95.94 (11)	C9—C4—C1	120.4 (3)
O4ⁱ—Zn1—N2	121.50 (11)	C5—C4—C1	120.7 (3)
O1—Zn1—N2	137.13 (11)	C4—C5—C6	120.7 (3)
O1W—Zn1—N2	94.52 (12)	C4—C5—H5	119.7
O4ⁱ—Zn1—N1	91.75 (12)	C6—C5—H5	119.7
O1—Zn1—N1	89.17 (12)	C7—C6—C5	119.4 (3)
O1W—Zn1—N1	170.62 (11)	C7—C6—C2	121.7 (3)
N2—Zn1—N1	76.46 (13)	C5—C6—C2	119.0 (3)
O6ⁱⁱ—Zn2—O6	180.00 (15)	C6—C7—C8	121.1 (3)
O6ⁱⁱ—Zn2—O3Wⁱⁱ	91.78 (11)	C6—C7—H7	119.4
O6—Zn2—O3Wⁱⁱ	88.22 (11)	C8—C7—H7	119.4
O6ⁱⁱ—Zn2—O3W	88.22 (11)	C9—C8—C7	118.6 (3)
O6—Zn2—O3W	91.78 (11)	C9—C8—C3	120.0 (3)
O3Wⁱⁱ—Zn2—O3W	180.0	C7—C8—C3	121.4 (3)
O6ⁱⁱ—Zn2—O2W	91.61 (11)	C4—C9—C8	121.4 (3)
O6—Zn2—O2W	88.39 (11)	C4—C9—H9	119.3
O3Wⁱⁱ—Zn2—O2W	86.71 (12)	C8—C9—H9	119.3
O3W—Zn2—O2W	93.29 (12)	N1—C10—C11	123.4 (4)
O6ⁱⁱ—Zn2—O2Wⁱⁱ	88.39 (11)	N1—C10—H10	118.3
O6—Zn2—O2Wⁱⁱ	91.61 (11)	C11—C10—H10	118.3
O3Wⁱⁱ—Zn2—O2Wⁱⁱ	93.29 (12)	C13—C11—C10	116.4 (4)
O3W—Zn2—O2Wⁱⁱ	86.71 (12)	C13—C11—C12	122.7 (4)
O2W—Zn2—O2Wⁱⁱ	180.0	C10—C11—C12	120.9 (4)
C1—O1—Zn1	104.3 (2)	C11—C12—H12A	109.5
C2—O4—Zn1ⁱⁱⁱ	112.2 (2)	C11—C12—H12B	109.5
C3—O6—Zn2	129.0 (2)	H12A—C12—H12B	109.5
Zn1—O1W—H1WA	111.8	C11—C12—H12C	109.5
Zn1—O1W—H1WB	112.0	H12A—C12—H12C	109.5
H1WA—O1W—H1WB	110.0	H12B—C12—H12C	109.5
Zn2—O2W—H2WA	114.2	C14—C13—C11	121.1 (4)
Zn2—O2W—H2WB	135.2	C14—C13—H13	119.5
H2WA—O2W—H2WB	97.6	C11—C13—H13	119.5
Zn2—O3W—H3WB	109.3	C13—C14—C15	119.2 (4)
Zn2—O3W—H3WC	109.3	C13—C14—H14	120.4
H3WB—O3W—H3WC	109.5	C15—C14—H14	120.4
H4WA—O4W—H4WB	121.9	N1—C15—C14	120.4 (4)
H4WA—O4W—H4WE	153.9	N1—C15—C16	115.2 (4)
H4WB—O4W—H4WE	73.1	C14—C15—C16	124.3 (4)
O4W'^iv—O4W'—H4WB	148.4	N2—C16—C17	121.1 (4)
O4W'^iv—O4W'—H4WD	78.5	N2—C16—C15	116.7 (3)
H4WB—O4W'—H4WD	71.6	C17—C16—C15	122.3 (4)
O4W'^iv—O4W'—H4WE	133.7	C18—C17—C16	119.3 (4)
H4WB—O4W'—H4WE	72.4	C18—C17—H17	120.4
H4WD—O4W'—H4WE	119.7	C16—C17—H17	120.4
H5WA—O5W—H5WC	94.0	C17—C18—C19	120.5 (4)
H6WB—O6W—H6WD	82.4	C17—C18—H18	119.8
C10—N1—C15	119.6 (4)	C19—C18—H18	119.8
C10—N1—Zn1	125.4 (3)	C18—C19—C21	116.9 (4)
C15—N1—Zn1	115.0 (3)	C18—C19—C20	122.2 (4)
C16—N2—C21	119.0 (3)	C21—C19—C20	120.8 (4)
C16—N2—Zn1	116.5 (3)	C19—C20—H20A	109.5
C21—N2—Zn1	124.5 (3)	C19—C20—H20B	109.4
O2—C1—O1	122.5 (3)	H20A—C20—H20B	109.5
O2—C1—C4	119.7 (3)	C19—C20—H20C	109.5
O1—C1—C4	117.8 (3)	H20A—C20—H20C	109.5
O3—C2—O4	123.0 (3)	H20B—C20—H20C	109.5
O3—C2—C6	118.8 (3)	N2—C21—C19	123.2 (4)
O4—C2—C6	118.2 (3)	N2—C21—H21	118.4
O5—C3—O6	125.0 (3)	C19—C21—H21	118.4
O5—C3—C8	119.5 (3)

O4ⁱ—Zn1—O1—C1	−177.5 (2)	C2—C6—C7—C8	−179.4 (3)
O1W—Zn1—O1—C1	−81.3 (3)	C6—C7—C8—C9	0.1 (6)
N2—Zn1—O1—C1	22.0 (3)	C6—C7—C8—C3	−179.9 (3)
N1—Zn1—O1—C1	90.9 (3)	O5—C3—C8—C9	−178.7 (4)
O3Wⁱⁱ—Zn2—O6—C3	152.0 (4)	O6—C3—C8—C9	3.0 (5)
O3W—Zn2—O6—C3	−28.0 (4)	O5—C3—C8—C7	1.3 (6)
O2W—Zn2—O6—C3	−121.2 (4)	O6—C3—C8—C7	−177.1 (3)
O2Wⁱⁱ—Zn2—O6—C3	58.8 (4)	C5—C4—C9—C8	0.1 (6)
O4ⁱ—Zn1—N1—C10	−60.6 (3)	C1—C4—C9—C8	179.9 (3)
O1—Zn1—N1—C10	38.1 (3)	C7—C8—C9—C4	−0.2 (6)
N2—Zn1—N1—C10	177.4 (3)	C3—C8—C9—C4	179.8 (3)
O4ⁱ—Zn1—N1—C15	119.6 (3)	C15—N1—C10—C11	0.0 (6)
O1—Zn1—N1—C15	−141.7 (3)	Zn1—N1—C10—C11	−179.8 (3)
N2—Zn1—N1—C15	−2.4 (3)	N1—C10—C11—C13	−0.3 (7)
O4ⁱ—Zn1—N2—C16	−80.7 (3)	N1—C10—C11—C12	179.5 (4)
O1—Zn1—N2—C16	76.6 (3)	C10—C11—C13—C14	0.3 (7)
O1W—Zn1—N2—C16	−179.7 (3)	C12—C11—C13—C14	−179.4 (5)
N1—Zn1—N2—C16	2.9 (3)	C11—C13—C14—C15	−0.1 (7)
O4ⁱ—Zn1—N2—C21	97.6 (3)	C10—N1—C15—C14	0.2 (6)
O1—Zn1—N2—C21	−105.1 (3)	Zn1—N1—C15—C14	180.0 (3)
O1W—Zn1—N2—C21	−1.3 (3)	C10—N1—C15—C16	−178.1 (3)
N1—Zn1—N2—C21	−178.7 (3)	Zn1—N1—C15—C16	1.7 (4)
Zn1—O1—C1—O2	6.0 (5)	C13—C14—C15—N1	−0.1 (6)
Zn1—O1—C1—C4	−173.7 (3)	C13—C14—C15—C16	178.0 (4)
Zn1ⁱⁱⁱ—O4—C2—O3	−2.2 (5)	C21—N2—C16—C17	−0.9 (6)
Zn1ⁱⁱⁱ—O4—C2—C6	176.1 (2)	Zn1—N2—C16—C17	177.5 (3)
Zn2—O6—C3—O5	14.6 (6)	C21—N2—C16—C15	178.5 (3)
Zn2—O6—C3—C8	−167.1 (2)	Zn1—N2—C16—C15	−3.0 (4)
O2—C1—C4—C9	−179.5 (4)	N1—C15—C16—N2	0.8 (5)
O1—C1—C4—C9	0.1 (5)	C14—C15—C16—N2	−177.4 (4)
O2—C1—C4—C5	0.3 (6)	N1—C15—C16—C17	−179.7 (4)
O1—C1—C4—C5	180.0 (3)	C14—C15—C16—C17	2.0 (6)
C9—C4—C5—C6	0.1 (6)	N2—C16—C17—C18	1.3 (6)
C1—C4—C5—C6	−179.8 (3)	C15—C16—C17—C18	−178.1 (4)
C4—C5—C6—C7	−0.1 (6)	C16—C17—C18—C19	−0.8 (7)
C4—C5—C6—C2	179.3 (3)	C17—C18—C19—C21	−0.1 (6)
O3—C2—C6—C7	−171.4 (3)	C17—C18—C19—C20	179.6 (4)
O4—C2—C6—C7	10.2 (5)	C16—N2—C21—C19	0.0 (6)
O3—C2—C6—C5	9.1 (5)	Zn1—N2—C21—C19	−178.4 (3)
O4—C2—C6—C5	−169.2 (3)	C18—C19—C21—N2	0.6 (6)
C5—C6—C7—C8	0.0 (6)	C20—C19—C21—N2	−179.2 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O5^v	0.84	1.93	2.754 (4)	166
O1W—H1WB···O6W^vi	0.84	1.96	2.805 (5)	176
O2W—H2WA···O2^vii	0.85	1.95	2.768 (4)	162
O2W—H2WB···O5W^vii	0.85	2.14	2.806 (6)	135
O3W—H3WB···O3^vii	0.85	2.16	2.740 (4)	125
O3W—H3WC···O5	0.85	2.26	2.705 (4)	113
O4W—H4WA···O5W	0.95	2.22	3.166 (19)	173
O4W′—H4WD···O2	0.87	2.63	3.499 (11)	177
O5W—H5WA···O6W	0.85	2.14	2.987 (9)	179
O5W—H5WC···O6^viii	0.90	2.28	3.151 (7)	164
O6W—H6WB···O1^viii	0.85	2.16	2.947 (5)	154
O6W—H6WD···O4^ix	0.85	2.23	3.019 (6)	154

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

Experimental details

Crystal data
Chemical formula	[Zn₃(C₉H₃O₆)₂(C₁₂H₁₂N₂)₂(H₂O)₆]·6H₂O
M_r	1195.00
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	10.2454 (10), 10.5799 (10), 12.658 (1)
α, β, γ (°)	68.910 (8), 74.848 (8), 81.834 (8)
V (Å³)	1233.90 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.54
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	0.739, 0.759
No. of measured, independent and observed [I > 2σ(I)] reflections	9149, 4330, 3426
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.01
No. of reflections	4330
No. of parameters	336
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.59

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
O1W—H1WA···O5ⁱ	0.84	1.93	2.754 (4)	166
O1W—H1WB···O6Wⁱⁱ	0.84	1.96	2.805 (5)	176
O2W—H2WA···O2ⁱⁱⁱ	0.85	1.95	2.768 (4)	162
O2W—H2WB···O5Wⁱⁱⁱ	0.85	2.14	2.806 (6)	135
O3W—H3WB···O3ⁱⁱⁱ	0.85	2.16	2.740 (4)	125
O3W—H3WC···O5	0.85	2.26	2.705 (4)	113
O4W—H4WA···O5W	0.95	2.22	3.166 (19)	173
O4W'—H4WD···O2	0.87	2.63	3.499 (11)	177
O5W—H5WA···O6W	0.85	2.14	2.987 (9)	179
O5W—H5WC···O6^iv	0.90	2.28	3.151 (7)	164
O6W—H6WB···O1^iv	0.85	2.16	2.947 (5)	154
O6W—H6WD···O4^v	0.85	2.23	3.019 (6)	154

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

Acknowledgements

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

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