catena-Poly[[[bis­(methyl­amine)zinc(II)]-μ-4,4′-oxydibenzoato] N,N-dimethyl­acetamide solvate]

Xianzhu Xu; Peng Wang; Shujie Shi

doi:10.1107/S1600536807063155

. 2007 Dec 6;64(Pt 1):m90. doi: 10.1107/S1600536807063155

catena-Poly[[[bis(methylamine)zinc(II)]-μ-4,4′-oxydibenzoato] N,N-dimethylacetamide solvate]

Xianzhu Xu ^a,^*, Peng Wang ^a, Shujie Shi ^a

PMCID: PMC2914964 PMID: 21200657

Abstract

In the title zinc(II) coordination polymer, {[Zn(C₁₄H₈O₅)(CH₅N)₂]·C₄H₉NO}_n, each Zn(II) cation is tetrahedrally coordinated by two carboxylato O atoms of two oba anions (H₂oba is 4,4′-oxydibenzoic acid), and two N atoms from two methylamine molecules. Each oba anion bridges two Zn(II) cations through the two carboxylate groups in a monodentate fashion, forming one-dimensional polymeric chains. These chains are linked via N–H⋯O hydrogen bonds, forming a two-dimensional supramolecular network.

Related literature

For related literature, see: Kondo et al. (2004 ▶); Luo et al. (2003 ▶); Sun et al. (2005 ▶); Yaghi et al. (1998 ▶).

Experimental

Crystal data

[Zn(C₁₄H₈O₅)(CH₅N)₂]·C₄H₉NO
M _r = 470.82
Monoclinic,
a = 27.617 (6) Å
b = 8.9276 (18) Å
c = 21.212 (4) Å
β = 122.46 (3)°
V = 4413 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 293 (2) K
0.35 × 0.34 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (Higashi, 1995 ▶) T _min = 0.690, T _max = 0.850
20180 measured reflections
4942 independent reflections
2843 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.149
S = 1.04
4942 reflections
276 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2000 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063155/fj2083sup1.cif

e-64-00m90-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063155/fj2083Isup2.hkl

e-64-00m90-Isup2.hkl^{(242.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O4ⁱ	0.90	2.21	2.991 (5)	145
N2—H2A⋯O2ⁱⁱ	0.90	2.11	2.966 (4)	159
N2—H2B⋯O6ⁱⁱⁱ	0.90	2.40	3.276 (6)	164

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

Acknowledgments

This work was supported by the National Science Foundation of China (50678045), the Science Foundation of Heilongjiang Province (E200519), the China Postdoctoral Science Foundation and Heilongjiang Postdoctoral Financial Assistance.

supplementary crystallographic information

Comment

Recently, great interest has been focused on the design and synthesis of coordination polymers because of their intriguing network topologies and promising applications (Yaghi et al., 1998). It is well known that the selection of appropriate organic ligands is crucial to the design and synthesis of the supramolecular architectures. In preparing target metal complexes, carboxylate and organic amine ligands have been frequently employed (Luo et al., 2003). More and more interest has focused on long flexible ligands recently, and how to avoid, or make use of, their interpenetration to construct novel coordination polymers is an interesting challenge. 4,4'-oxybis(benzoic acid) (H₂oba) ligand, in which two benzene moieties are linked together by a µ₂-O bridge, is the typical example of flexible ligand and may offer more possibilities in geometry configuration and coordination modes towards the metal ions. As far as we know, several coordination polymers based on 4,4'-oxybis(benzoic acid) have been obtained (Kondo et al., 2004; Sun et al., 2005). We present here the solvothermal synthesis and crystal structure of title coordination polymer, [Zn(C₁₄H₈O₅)(CNH₅)₂^.(C₄NOH₉)]_n, (I).

The asymmetric unit of (I) consists of one crystallogaphically independent Zn(II) cation, one oba ligand, two methylamine and one dimethylacetamide molecule. Fig.1 shows the molecular structure of (I) with the atom-labelling scheme. The Zn(II) cation has a slightly distorted tetrahedral coordination geometry and formed by two carboxy oxygen atoms (O1 and O5A) from two oba ligands and two nitrogen atoms (N1 and N2) from two methylamine molecule, with Zn—O distances of 1.949 (3)–1.952 (3) Å and Zn—N distances in the range of 1.996 (4)–2.047 (4) Å. These values are in good agreement with those found in other extended structures (Kondo et al., 2004). The O—Zn—O and N—Zn—N bond angles are 106.28 (11)° and 106.15 (19)°, respectively. The N—Zn—O angles are in the range from 98.65 (12) to 115.75 (14)°. In (I), two carboxylate groups of each oba exhibit bis-monodentate coordination modes, namely oba anion acts as µ₂-bridging ligand to connect with two Zn(II) centers and each Zn(II) center connects with two oba anions to form the chain arrangement with Zn^···Zn distance of 14.512 (4) Å (Fig. 2). It is found that there are hydrogen bonding interactions between adjacent chains. The N—H^···O hydrogen bonds involve the uncoordinated carboxylic oxygen atoms of oba and N—H groups of methylamine molecules from adjacent chains (Table 2). In addition, dimethylacetamide molecules located in the crystal lattice with N—H^···O hydrogen bonding interactions involving the oxygen atoms of dimethylacetamide molecules and N—H groups of methylamine molecules (Table 2). Finally, the chains are linked together by hydrogen bonds to form two-dimensional supramolecular network (Fig. 2).

Experimental

(I) was solvothermally prepared from a mixture of Zn(NO₃)₂^.6H₂O (0.044 g, 0.2 mmol), 4,4'-oxybis(benzoic acid) (0.051 g, 0.2 mmol), methylamine (0.05 ml) and dimethylacetamide (10 ml). The slurry was stirred for 30 min and heated at 120 °C for 72 h in a Teflon-lined stainless steel autoclave (25 ml) under autogenous pressure. After cooling to room temperature, the block-shaped crystals were washed with water and dried in air.