catena-Poly[[bis­(μ-3-carboxy­benzoato)bis­(1,10-phenanthroline)tricopper(II)]-di-μ3-isophthalato]

Yan An; Xiao-Feng Li; Li-Hua Dong; Yan-Sheng Yin

doi:10.1107/S1600536808036908

. 2008 Nov 20;64(Pt 12):m1574–m1575. doi: 10.1107/S1600536808036908

catena-Poly[[bis(μ-3-carboxybenzoato)bis(1,10-phenanthroline)tricopper(II)]-di-μ₃-isophthalato]

Yan An ^a, Xiao-Feng Li ^a,^*, Li-Hua Dong ^a, Yan-Sheng Yin ^a

PMCID: PMC2959876 PMID: 21581177

Abstract

The title copper coordination polymer, [Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]_n, was synthesized by reacting Cu(NO₃)₂, isophthalic acid and 1,10-phenanthroline under hydrothermal conditions. The trinuclear unit presents a central almost planar CuO₄ chromophore with the cation on a symmetry center, and two symmetry-related CuN₂O₃ groups with the metal centre in a distorted square-pyramidal environment. These units are bridged by isophthalate ligands into one-dimensional double-chain coordination polymers which are, in turn, connected by various π–π stacking interactions (face-to-face distance ca 3.45 Å) and O—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network.

Related literature

For related literature on the design and construction of coordination polymers, see: Amabilino & Stoddart (1995 ▶); Han et al. (2005 ▶, 2007 ▶, 2008 ▶); He & Han (2007 ▶); Ma et al. (2007 ▶).

Experimental

Crystal data

[Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]
M _r = 1209.5
Triclinic,
a = 10.383 (1) Å
b = 10.659 (1) Å
c = 11.754 (1) Å
α = 83.147 (1)°
β = 86.191 (1)°
γ = 71.134 (1)°
V = 1221.6 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 293 (2) K
0.37 × 0.32 × 0.23 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.631, T _max = 0.738
9575 measured reflections
4741 independent reflections
4241 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.089
S = 1.09
4741 reflections
358 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036908/bg2210sup1.cif

e-64-m1574-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036908/bg2210Isup2.hkl

e-64-m1574-Isup2.hkl^{(232.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O6	1.923 (1)
Cu1—O2	2.010 (1)
Cu2—O3ⁱ	1.935 (1)
Cu2—O1	1.951 (1)
Cu2—N2	2.008 (2)
Cu2—N1	2.014 (2)
Cu2—O5	2.278 (1)

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O6—Cu1—O2ⁱⁱ	92.30 (6)
O6—Cu1—O2	87.70 (6)
O3ⁱ—Cu2—O1	92.66 (6)
O1—Cu2—N2	168.29 (7)
N2—Cu2—N1	81.94 (7)
O1—Cu2—O5	91.79 (6)
N1—Cu2—O5	98.46 (6)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4ⁱⁱⁱ	0.82	1.73	2.539 (2)	170

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Symmetry code: (iii) Inline graphic .

Acknowledgments

This work was supported by the Shanghai Municipal Education Commission, Project Nos. 2008068, 2008080.

supplementary crystallographic information

Comment

The design and construction of coordination polymers has attracted much attention owing to their intriguing topologies and potential applications as functional materials (Han et al., 2008, Ma et al., 2007). Many networks with various structural motifs have been documented in the past decade (Amabilino et al., 1995). Unlike pyridine 2,4-, 3,4- 2,5- and 2,6-dicarboxylic acids which were widely reported as bridging ligands to assemble various coordination polymers, isophthalic acid (H₂ip) has been reported only scarcely in the role of multicarboxylate ligand (Han et al., 2007). We report here the synthesis and structure of the title copper(II) coordination polymer [Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)]_n,assembled from isophthalic acid, 1,10-phenanthroline(phen) and copper(II), (I).

In I, there is one and a half Cu(II) ions (Cu1 lies on center of symmetry), one ip, one Hip and one phen ligand in each independent crystallographic unit. Each Cu2 ion is coordinated by three oxygen atoms from two ip ligands and one Hip ligand in a mono-bidentate and bidentate coordination modes and two nitrogen atoms from a chelate phen ligand to furnish a distorted square pyramidal geometry. On the other hand, each Cu1 atom is four-coordinated by four oxygen atoms, forming a slightly distorted square geometry. (Fig.1 and Table 1).

The carboxylate oxygen atoms bridge three copper atoms (Cu2, Cu1 and Cu2ⁱ) via the syn–anti O,O-bridges to form a trinuclear [Cu₃(ip)₂(Hip)₂(phen)₂] subunit (Fig. 1), which are interconnected through the bridging ip groups to form an infinite one-dimensional double chain with Cu···Cu distances of 3.755 (3) and 9.994 (3) Å (Fig. 2). The lateral phen ligands from adjacent double-chains are paired to furnish moderately strong π—π stacking interactions (face-face distance ca 3.45 (1) Å) (He et al.,2007, Han et al., 2005), which extend the double-chains into two-dimensional wavelike layers parallel to the ab plane in the lattice. These layers are further linked via strong hydrogen bonds between uncoordinated carboxylate oxygen atoms of ip ligands (Table 2), forming a three-dimensional supramolecular network.

Experimental

A mixture of Cu(NO₃)₂.2H₂O (0.5 mmol, 0.120 g), isophthalic acid (0.5 mmol, 0.084 g), NaOH (1 mmol, 0.04 g), and water (10 ml) was mixed in a 23 ml Teflon reactor, which was heated at 453 K for six days and then cooled to room temperature at a rate of 5 K h^-1. Yield: 48%. CH&N analysis for C₂₀H₁₇N₂O₈Cu_1.5 (found/calc): C, 47.05(47.22), H, 2.64(3.37), N, 5.73%(5.51%).