Poly[diaqua­(μ4-benzene-1,2,4,5-tetra­carboxyl­ato)[μ2-1,4-bis­(3-pyridyl­meth­yl)piperazine]dizinc(II)]

Zhang, H.-F.; Li, Y.; Zhao, W.-X.; Zhao, L.-Z.; Zhang, D.

doi:10.1107/S1600536811018721

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m784-m785

doi:10.1107/S1600536811018721

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Poly[diaqua(μ₄-benzene-1,2,4,5-tetracarboxylato)[μ₂-1,4-bis(3-pyridylmethyl)piperazine]dizinc(II)]

Hui-Feng Zhang,^a,^b Yan Li,^c ^* Wen-Xiu Zhao,^b Liang-Zhong Zhao ^c and Duo Zhang ^c

^aCollege of Life Science, Jilin University, Changchun 130022, People's Republic of China, ^bFaculty of Pharmacy, Jilin Medical College, Jilin 132013, People's Republic of China, and ^cDepartment of Etiology, Jilin Medical College, Jilin 132013, People's Republic of China
^*Correspondence e-mail: leeyan201182@yahoo.cn

(Received 4 April 2011; accepted 17 May 2011; online 25 May 2011)

In the title compound, [Zn₂(C₁₀H₂O₈)(C₁₆H₂₀N₄)(H₂O)₂]_n, the Zn^II atom is in a distorted tetrahedral environment, being coordinated by one N atom from a 1,4-bis(3-pyridylmethyl)piperazine (3-bpmp) ligand, two O atoms from two carboxylate groups of the pyromellitate anion and one water molecule. The distortion of the tetrahedral coordination may be ascribed to the hydrogen bonds between the carboxylate groups and the adjacent water molecules. Each Zn^II atom links to three organic ligands and each pyromellitate ligand coordinates to four Zn^II atoms, forming a (3,4)-connected infinite three-dimensional framework. O—H⋯N interactions also occur.

Related literature

For a coordination polymer containing 3-bpmp, see: Martin et al. (2009 ). For the preparation of N,N-bis(3-pyridylmethyl)piperazine, see: Pocic et al. (2005 ). 3-bpmp and its derivatives are important heteroaromatic N-donor bridging ligands for the construction of coordination polymers, see: Farnum & LaDuca (2010 ).

Experimental

Crystal data

[Zn₂(C₁₀H₂O₈)(C₁₆H₂₀N₄)(H₂O)₂]
M_r = 685.24
Monoclinic, P 2₁ /c
a = 9.5630 (5) Å
b = 9.8747 (5) Å
c = 16.1808 (7) Å
β = 120.673 (2)°
V = 1314.20 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.89 mm⁻¹
T = 293 K
0.22 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.672, T_max = 0.767
7908 measured reflections
3096 independent reflections
2622 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.03
3096 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O5	1.9442 (16)
Zn1—O1	1.9762 (15)
Zn1—O3ⁱ	1.9795 (14)
Zn1—N1	2.0443 (18)

O5—Zn1—O1	121.11 (7)
O5—Zn1—O3ⁱ	106.68 (7)
O1—Zn1—O3ⁱ	103.27 (6)
O5—Zn1—N1	111.84 (8)
O1—Zn1—N1	104.45 (7)
O3ⁱ—Zn1—N1	108.74 (7)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O4ⁱⁱ	0.85	1.82	2.662 (2)	173
O5—H5B⋯N2ⁱⁱⁱ	0.85	1.91	2.751 (2)	169
Symmetry codes: (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018721/zk2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018721/zk2007Isup2.hkl

checkCIF report

Comment top

1,4-bis(3-pyridylmethyl)piperazine (3-bpmp) and its derivatives are important heteroaromatic N-donor bridging ligands for the construction of coordination polymers (Farnum & LaDuca, 2010). Whereas, only a handful of polymers based on 3-bpmp have been described (Martin et al., 2009). The title compound was prepared during an attempt to prepare a coordination polymer containing both pyromellitic acid and 3-bpmp ligands.

The asymmetric unit of the title compound (Fig. 1) contains a zinc^II ion, a half 3-bpmp ligand, a half pyromellitate anion on the crystallographic inversion centre, and one coordinated water molecule. the Zn1 atom is situated in a distorted tetrahedron center, coordinated by one N atoms (N1) from 3-bpmp, two O atoms (O1, O3i) from two carboxylate groups of pyromellitate and one water molecule (Table 1). The other two carboxylate O atoms (O2, O4i) are also close to the Zn1 center, however, the lengths of Zn1—O (2.730 (2) Å) and Zn1—O4i (2.884 (2) Å) are too long to be considered as bonding interactions, thus the Zn^II center can be best described as four rather than six coordinated, which may be ascribed to the hydrogen bonds between the carboxylate groups and the adjacent water molecules (Table 1).

In the crystal structure, each pyromellitate ligand coordinates to four Zn^II atoms in tetra-monodentate bridging mode, and each Zn^II atom is linked to two pyromellitate ligands to construct waved (4,4)-grid [Zn₂(pyromellitate)]_n layers that are oriented parallel to the (1 0 1) crystal planes (Fig. 2). The two Zn^II atoms between the adjacent layers are connected by 3-bpmp ligand thus a (3,4)-connected infinite three-dimensional framework are formed (Fig. 3). Withal, there are intralayer hydrogen bonding between the water molecule ligands and unligated pyromellitate O atoms provides additional stabilization of the layer motifs.

Related literature top

For a coordination polymer containing 3-bpmp, see: Martin et al. (2009). For the preparation of N,N-bis(3-pyridylmethyl)piperazine, see: Pocic et al. (2005). 1,4-bis(3-pyridylmethyl)piperazine (3-bpmp) and its derivatives are important heteroaromatic N-donor bridging ligands for the construction of coordination polymers, see: Farnum & LaDuca (2010).

Experimental top

Zinc nitrate hexahydrate and pyromellitic acid were obtained commercially. 1,4-bis(3-pyridylmethyl)piperazine was prepared via a published procedure (Pocic, et al., 2005). A mixture of zinc nitrate hexahydrate (135 mg, 0.50 mmol), pyromellitic acid (62 mg, 0.25 mmol), 1,4-bis(3-pyridylmethyl)piperazine (33 mg, 0.12 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr Acid Digestion bomb, which was then heated under autogenous pressure at 398 K for 72 h, then cooled to RT at a rate of 5 °c/h. The resulting yellowish crystals of the title compound were obtained. Elemental analysis (%) calcd for title compound: C, 45.57; H, 3.82; N, 8.18; found: 45.63; H, 3.87; N, 8.23.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. ORTEP drawing of the title components with thermal ellipsoids at the 50% probability level. Symmetry codes: (i) 2 - x, -1/2 + y, 1.5 - z
	Fig. 2. Face-on view of the (4,4)-grid layer motif in the title compound viewing along the c axis.
	Fig. 3. A packing view of three-dimensional network of the title compound nearly viewing along the a axis.

Poly[diaqua(µ₄-benzene-1,2,4,5-tetracarboxylato)[µ₂-1,4-bis(3- pyridylmethyl)piperazine]dizinc(II)] top

Crystal data top

[Zn₂(C₁₀H₂O₈)(C₁₆H₂₀N₄)(H₂O)₂]	F(000) = 700
M_r = 685.24	D_x = 1.732 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5630 (5) Å	Cell parameters from 2721 reflections
b = 9.8747 (5) Å	θ = 3.7–24.2°
c = 16.1808 (7) Å	µ = 1.89 mm⁻¹
β = 120.673 (2)°	T = 293 K
V = 1314.20 (11) Å³	Block, yellow
Z = 2	0.22 × 0.16 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3096 independent reflections
Radiation source: fine-focus sealed tube	2622 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 28.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
T_min = 0.672, T_max = 0.767	k = −12→6
7908 measured reflections	l = −20→20

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0309P)² + 0.7095P] where P = (F_o² + 2F_c²)/3
3096 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Zn₂(C₁₀H₂O₈)(C₁₆H₂₀N₄)(H₂O)₂]	V = 1314.20 (11) Å³
M_r = 685.24	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5630 (5) Å	µ = 1.89 mm⁻¹
b = 9.8747 (5) Å	T = 293 K
c = 16.1808 (7) Å	0.22 × 0.16 × 0.15 mm
β = 120.673 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3096 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2622 reflections with I > 2σ(I)
T_min = 0.672, T_max = 0.767	R_int = 0.027
7908 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.03	Δρ_max = 0.44 e Å⁻³
3096 reflections	Δρ_min = −0.44 e Å⁻³
190 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	0.86004 (3)	0.65356 (2)	0.795439 (16)	0.02201 (8)
O1	0.80856 (18)	0.79217 (16)	0.69580 (11)	0.0338 (4)
O2	0.6272 (2)	0.8500 (2)	0.73459 (13)	0.0557 (6)
O3	0.91934 (16)	1.09247 (16)	0.66965 (10)	0.0286 (3)
O4	0.92729 (17)	0.96053 (17)	0.56165 (11)	0.0324 (4)
O5	0.8690 (2)	0.69929 (17)	0.91493 (11)	0.0420 (4)
H5A	0.8933	0.6451	0.9611	0.063*
H5B	0.8548	0.7783	0.9303	0.063*
N1	0.6991 (2)	0.50031 (18)	0.72410 (12)	0.0259 (4)
N2	0.14900 (18)	0.44565 (17)	0.51164 (11)	0.0216 (3)
C1	0.6825 (2)	0.8567 (2)	0.68146 (14)	0.0258 (4)
C2	0.5924 (2)	0.93592 (19)	0.58884 (13)	0.0188 (4)
C3	0.6703 (2)	1.00226 (19)	0.54740 (13)	0.0185 (4)
C4	0.4233 (2)	0.9353 (2)	0.54138 (13)	0.0209 (4)
H4	0.3718	0.8921	0.5697	0.025*
C5	0.8530 (2)	1.0158 (2)	0.59632 (14)	0.0213 (4)
C6	0.7442 (3)	0.3710 (2)	0.74772 (17)	0.0337 (5)
H6	0.8454	0.3527	0.8014	0.040*
C7	0.6469 (3)	0.2646 (2)	0.69576 (17)	0.0372 (5)
H7	0.6810	0.1759	0.7146	0.045*
C8	0.4979 (3)	0.2906 (2)	0.61535 (16)	0.0320 (5)
H8	0.4308	0.2194	0.5792	0.038*
C9	0.4484 (2)	0.4234 (2)	0.58848 (14)	0.0240 (4)
C10	0.5518 (2)	0.5241 (2)	0.64550 (15)	0.0255 (4)
H10	0.5188	0.6136	0.6292	0.031*
C11	0.2899 (2)	0.4555 (2)	0.49833 (14)	0.0277 (5)
H11A	0.2952	0.5465	0.4775	0.033*
H11B	0.2747	0.3934	0.4479	0.033*
C12	0.1496 (2)	0.5559 (2)	0.57275 (14)	0.0259 (4)
H12A	0.1503	0.6424	0.5445	0.031*
H12B	0.2473	0.5503	0.6356	0.031*
C13	−0.0016 (2)	0.4524 (2)	0.41650 (14)	0.0268 (4)
H13A	−0.0033	0.3782	0.3767	0.032*
H13B	−0.0039	0.5366	0.3850	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01665 (12)	0.02323 (14)	0.01964 (12)	0.00100 (9)	0.00455 (9)	0.00333 (9)
O1	0.0293 (8)	0.0325 (9)	0.0299 (8)	0.0108 (7)	0.0080 (7)	0.0142 (7)
O2	0.0492 (11)	0.0897 (17)	0.0311 (9)	0.0197 (10)	0.0226 (9)	0.0280 (10)
O3	0.0168 (7)	0.0368 (9)	0.0263 (7)	−0.0055 (6)	0.0067 (6)	−0.0122 (6)
O4	0.0217 (7)	0.0422 (10)	0.0313 (8)	−0.0014 (7)	0.0122 (6)	−0.0115 (7)
O5	0.0718 (13)	0.0275 (9)	0.0280 (8)	0.0159 (8)	0.0264 (9)	0.0076 (7)
N1	0.0180 (8)	0.0266 (9)	0.0271 (9)	−0.0008 (7)	0.0072 (7)	0.0006 (7)
N2	0.0143 (7)	0.0277 (9)	0.0188 (8)	−0.0016 (7)	0.0056 (6)	−0.0025 (7)
C1	0.0219 (10)	0.0233 (11)	0.0195 (9)	−0.0036 (8)	0.0013 (8)	0.0034 (8)
C2	0.0170 (9)	0.0163 (9)	0.0162 (8)	0.0006 (7)	0.0034 (7)	0.0009 (7)
C3	0.0137 (8)	0.0167 (9)	0.0184 (9)	−0.0015 (7)	0.0033 (7)	−0.0032 (7)
C4	0.0186 (9)	0.0203 (10)	0.0205 (9)	−0.0038 (7)	0.0075 (8)	0.0028 (7)
C5	0.0156 (9)	0.0222 (10)	0.0205 (9)	−0.0010 (7)	0.0052 (7)	0.0013 (8)
C6	0.0241 (11)	0.0308 (12)	0.0320 (12)	0.0043 (9)	0.0040 (9)	0.0010 (9)
C7	0.0348 (13)	0.0230 (11)	0.0425 (13)	0.0040 (9)	0.0116 (11)	−0.0022 (10)
C8	0.0274 (11)	0.0287 (12)	0.0352 (12)	−0.0047 (9)	0.0125 (10)	−0.0094 (9)
C9	0.0167 (9)	0.0315 (11)	0.0242 (10)	−0.0006 (8)	0.0105 (8)	−0.0016 (8)
C10	0.0198 (10)	0.0245 (11)	0.0288 (10)	0.0000 (8)	0.0100 (8)	0.0020 (8)
C11	0.0176 (9)	0.0394 (13)	0.0238 (10)	−0.0038 (9)	0.0089 (8)	−0.0019 (9)
C12	0.0160 (9)	0.0323 (12)	0.0229 (10)	−0.0044 (8)	0.0052 (8)	−0.0075 (8)
C13	0.0189 (9)	0.0361 (12)	0.0189 (9)	−0.0002 (9)	0.0049 (8)	−0.0057 (8)

Geometric parameters (Å, º) top

Zn1—O5	1.9442 (16)	C3—C5	1.512 (2)
Zn1—O1	1.9762 (15)	C4—C3ⁱⁱⁱ	1.390 (3)
Zn1—O3ⁱ	1.9795 (14)	C4—H4	0.9300
Zn1—N1	2.0443 (18)	C6—C7	1.370 (3)
O1—C1	1.276 (3)	C6—H6	0.9300
O2—C1	1.220 (3)	C7—C8	1.377 (3)
O3—C5	1.271 (2)	C7—H7	0.9300
O3—Zn1ⁱⁱ	1.9795 (14)	C8—C9	1.387 (3)
O4—C5	1.235 (2)	C8—H8	0.9300
O5—H5A	0.8501	C9—C10	1.374 (3)
O5—H5B	0.8501	C9—C11	1.507 (3)
N1—C6	1.340 (3)	C10—H10	0.9300
N1—C10	1.352 (3)	C11—H11A	0.9700
N2—C12	1.469 (3)	C11—H11B	0.9700
N2—C11	1.472 (2)	C12—C13^iv	1.514 (3)
N2—C13	1.479 (2)	C12—H12A	0.9700
C1—C2	1.511 (3)	C12—H12B	0.9700
C2—C4	1.392 (3)	C13—C12^iv	1.514 (3)
C2—C3	1.394 (3)	C13—H13A	0.9700
C3—C4ⁱⁱⁱ	1.390 (3)	C13—H13B	0.9700

O5—Zn1—O1	121.11 (7)	N1—C6—H6	118.8
O5—Zn1—O3ⁱ	106.68 (7)	C7—C6—H6	118.8
O1—Zn1—O3ⁱ	103.27 (6)	C6—C7—C8	119.3 (2)
O5—Zn1—N1	111.84 (8)	C6—C7—H7	120.4
O1—Zn1—N1	104.45 (7)	C8—C7—H7	120.4
O3ⁱ—Zn1—N1	108.74 (7)	C7—C8—C9	119.7 (2)
C1—O1—Zn1	108.28 (14)	C7—C8—H8	120.2
C5—O3—Zn1ⁱⁱ	113.58 (13)	C9—C8—H8	120.2
Zn1—O5—H5A	125.6	C10—C9—C8	117.44 (19)
Zn1—O5—H5B	124.8	C10—C9—C11	121.47 (19)
H5A—O5—H5B	109.5	C8—C9—C11	121.07 (19)
C6—N1—C10	117.61 (18)	N1—C10—C9	123.6 (2)
C6—N1—Zn1	120.29 (14)	N1—C10—H10	118.2
C10—N1—Zn1	121.67 (14)	C9—C10—H10	118.2
C12—N2—C11	111.10 (16)	N2—C11—C9	112.87 (16)
C12—N2—C13	109.56 (15)	N2—C11—H11A	109.0
C11—N2—C13	108.82 (15)	C9—C11—H11A	109.0
O2—C1—O1	123.6 (2)	N2—C11—H11B	109.0
O2—C1—C2	119.6 (2)	C9—C11—H11B	109.0
O1—C1—C2	116.57 (19)	H11A—C11—H11B	107.8
C4—C2—C3	119.48 (17)	N2—C12—C13^iv	110.75 (16)
C4—C2—C1	117.36 (17)	N2—C12—H12A	109.5
C3—C2—C1	123.07 (17)	C13^iv—C12—H12A	109.5
C4ⁱⁱⁱ—C3—C2	119.02 (17)	N2—C12—H12B	109.5
C4ⁱⁱⁱ—C3—C5	117.67 (17)	C13^iv—C12—H12B	109.5
C2—C3—C5	123.24 (17)	H12A—C12—H12B	108.1
C3ⁱⁱⁱ—C4—C2	121.50 (18)	N2—C13—C12^iv	110.43 (16)
C3ⁱⁱⁱ—C4—H4	119.3	N2—C13—H13A	109.6
C2—C4—H4	119.3	C12^iv—C13—H13A	109.6
O4—C5—O3	123.94 (18)	N2—C13—H13B	109.6
O4—C5—C3	120.13 (17)	C12^iv—C13—H13B	109.6
O3—C5—C3	115.80 (17)	H13A—C13—H13B	108.1
N1—C6—C7	122.4 (2)

O5—Zn1—O1—C1	−48.49 (17)	C4ⁱⁱⁱ—C3—C5—O4	−67.8 (3)
O3ⁱ—Zn1—O1—C1	−167.62 (14)	C2—C3—C5—O4	115.2 (2)
N1—Zn1—O1—C1	78.70 (15)	C4ⁱⁱⁱ—C3—C5—O3	108.3 (2)
O5—Zn1—N1—C6	−83.24 (18)	C2—C3—C5—O3	−68.7 (3)
O1—Zn1—N1—C6	144.06 (17)	C10—N1—C6—C7	−0.3 (4)
O3ⁱ—Zn1—N1—C6	34.32 (19)	Zn1—N1—C6—C7	−173.04 (19)
O5—Zn1—N1—C10	104.37 (17)	N1—C6—C7—C8	1.0 (4)
O1—Zn1—N1—C10	−28.33 (18)	C6—C7—C8—C9	−0.3 (4)
O3ⁱ—Zn1—N1—C10	−138.07 (16)	C7—C8—C9—C10	−1.0 (3)
Zn1—O1—C1—O2	13.3 (3)	C7—C8—C9—C11	177.0 (2)
Zn1—O1—C1—C2	−161.64 (13)	C6—N1—C10—C9	−1.0 (3)
O2—C1—C2—C4	−34.3 (3)	Zn1—N1—C10—C9	171.57 (16)
O1—C1—C2—C4	140.9 (2)	C8—C9—C10—N1	1.7 (3)
O2—C1—C2—C3	149.1 (2)	C11—C9—C10—N1	−176.32 (19)
O1—C1—C2—C3	−35.7 (3)	C12—N2—C11—C9	70.1 (2)
C4—C2—C3—C4ⁱⁱⁱ	−0.9 (3)	C13—N2—C11—C9	−169.16 (18)
C1—C2—C3—C4ⁱⁱⁱ	175.55 (18)	C10—C9—C11—N2	−100.7 (2)
C4—C2—C3—C5	176.05 (18)	C8—C9—C11—N2	81.4 (2)
C1—C2—C3—C5	−7.5 (3)	C11—N2—C12—C13^iv	178.22 (17)
C3—C2—C4—C3ⁱⁱⁱ	1.0 (3)	C13—N2—C12—C13^iv	57.9 (2)
C1—C2—C4—C3ⁱⁱⁱ	−175.72 (18)	C12—N2—C13—C12^iv	−57.8 (2)
Zn1ⁱⁱ—O3—C5—O4	14.7 (3)	C11—N2—C13—C12^iv	−179.41 (18)
Zn1ⁱⁱ—O3—C5—C3	−161.19 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4^v	0.85	1.82	2.662 (2)	173
O5—H5B···N2^vi	0.85	1.91	2.751 (2)	169

Symmetry codes: (v) x, −y+3/2, z+1/2; (vi) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₁₀H₂O₈)(C₁₆H₂₀N₄)(H₂O)₂]
M_r	685.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.5630 (5), 9.8747 (5), 16.1808 (7)
β (°)	120.673 (2)
V (Å³)	1314.20 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.89
Crystal size (mm)	0.22 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.672, 0.767
No. of measured, independent and observed [I > 2σ(I)] reflections	7908, 3096, 2622
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.03
No. of reflections	3096
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.44

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008) and local programs.

Selected geometric parameters (Å, º) top

Zn1—O5	1.9442 (16)	Zn1—O3ⁱ	1.9795 (14)
Zn1—O1	1.9762 (15)	Zn1—N1	2.0443 (18)

O5—Zn1—O1	121.11 (7)	O5—Zn1—N1	111.84 (8)
O5—Zn1—O3ⁱ	106.68 (7)	O1—Zn1—N1	104.45 (7)
O1—Zn1—O3ⁱ	103.27 (6)	O3ⁱ—Zn1—N1	108.74 (7)

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱⁱ	0.85	1.82	2.662 (2)	173
O5—H5B···N2ⁱⁱⁱ	0.85	1.91	2.751 (2)	169

Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2.

Acknowledgements

This work was supported financially by the Education Committee of Jilin Province "12th Five-year Plan" Natural Science Foundation (No. 2011423).

References

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Pocic, D., Planeix, J.-M., Kyritsakas, N., Jouaiti, A., Abdelaziz, H. & Wais, M. (2005). CrystEngComm, 7, 624–628. Web of Science CSD CrossRef CAS Google Scholar
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