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

Hui-Feng Zhang; Yan Li; Wen-Xiu Zhao; Liang-Zhong Zhao; Duo Zhang

doi:10.1107/S1600536811018721

. 2011 May 25;67(Pt 6):m784–m785. doi: 10.1107/S1600536811018721

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, Duo Zhang ^c

PMCID: PMC3120526 PMID: 21754666

Abstract

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,
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[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 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

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.

Supplementary Material

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

e-67-0m784-sup1.cif^{(18.5KB, cif)}

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

e-67-0m784-Isup2.hkl^{(151.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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)

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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)

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Symmetry code: (i) Inline graphic .

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

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Symmetry codes: (ii) Inline graphic ; (iii) .

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.