catena-Poly[[(1,10-phenanthroline)copper(II)]-μ-oxalato]

Jun Wang; Yong Hou; Zhi-li Fang

doi:10.1107/S1600536810035440

. 2010 Sep 8;66(Pt 10):m1229. doi: 10.1107/S1600536810035440

catena-Poly[[(1,10-phenanthroline)copper(II)]-μ-oxalato]

Jun Wang ^a,^*, Yong Hou ^a, Zhi-li Fang ^b

PMCID: PMC2983185 PMID: 21587384

Abstract

In the title coordination polymer, [Cu(C₂O₄)(C₁₂H₈N₂)]_n, the Cu^II atom is six-coordinated by four O atoms from two oxalate ligands and two N atoms from one 1,10-phenanthroline (phen) ligand in a distorted octahedral coordination geometry. The oxalate anions act as bis-bidentate ligands, bridging the Cu–phen units in zigzag chains extending parallel to [100]. Interchain C—H⋯O hydrogen bonding and π–π stacking interactions [centroid–centroid distance = 3.7439 (17) Å] assemble neighboring chains, forming a three-dimensional supramolecular network.

Related literature

For the topologies and potential applications as functional materials of metal coordination polymers, see: Benneli & Gatteschi (2002 ▶); Qin et al. (2005 ▶); Qiu et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₂O₄)(C₁₂H₈N₂)]
M _r = 331.76
Orthorhombic,
a = 9.1445 (8) Å
b = 10.1443 (9) Å
c = 13.3294 (11) Å
V = 1236.50 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 298 K
0.42 × 0.35 × 0.29 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.544, T _max = 0.612
6811 measured reflections
2618 independent reflections
2373 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.059
S = 1.04
2618 reflections
190 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ▶), 1217 Friedel pairs
Flack parameter: 0.019 (14)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035440/zl2304sup1.cif

e-66-m1229-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035440/zl2304Isup2.hkl

e-66-m1229-Isup2.hkl^{(128.6KB, 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
C11—H11⋯O4ⁱ	0.93	2.51	3.416 (4)	166
C9—H9⋯O1ⁱⁱ	0.93	2.49	3.160 (3)	129
C2—H2⋯O2ⁱⁱⁱ	0.93	2.52	3.136 (3)	124
C1—H1⋯O4^iv	0.93	2.56	3.072 (3)	115

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

Acknowledgments

This work was supported financially by Zhongshan Polytechnic.

supplementary crystallographic information

Comment

The design and construction of metal coordination polymers based on metal ions and multifunctional bridging ligands is of great interest due to their intriguing topologies and potential applications as functional materials (Benneli & Gatteschi, 2002; Qiu et al., 2007). Copper, with its variable coordination numbers and flexible coordination geometry, provides unique opportunities for the discovery of unusual networks in this interesting and challenging field (Qin et al., 2005). We chose oxalate ligands as organic spacers since this rigid molecule has proven to be able to establish a bridge between metal centers. Herein, we present the structure of the title compound, [Cu(C₂O₄)(C₁₂H₈N₂)]_n.

The Cu^II atom exhibits a distorted octahedral configuration coordinated by four oxygen atoms from two oxalate ligands (Cu—O = 1.9753 (18)-2.3135 (18) Å) and two nitrogen atoms from one 1,10-phenanthroline ligand (Cu—N = 2.024 (2) and 2.049 (2) Å) (Fig. 1). The oxalate ligands bridge adjacent Cu-phen units to form a one-dimensional zigzag chain along the a-axis of the unit cell. The Cu—Cu separation is 5.529 (2) Å. Interchain π-π stacking interactions between phen ligands in neighboring chainslead to the formation of sheets of connected chains in the ab-plane. The centroid to centroid distances between neighboring 1,10-phenanthroline ligands is 3.7439 (17) Å [ring (C4-C9) to ring (N2, C1 to C5) (symmetry code: –1/2+x, 3/2–y, z)]. C–H···O hydrogen bonds interconnect these sheets to extend to a three-dimensional supramolecular network motif (Table 1; Fig. 2).

Experimental

A sample of cupric acetate (0.0399 g, 0.20 mmol), oxalic acid (0.1015 g, 0.50 mmol), 1,10-phenanthroline (0.2523 g, 0.50 mmol), were added to water (10 ml). The resultant mixture was sealed in a 25 ml stainless steel reactor with a Teflon liner and kept under autogenous pressure at 413 K for 78 h, and then cooled to room temperature at a rate of 0.5 K/min. Colorless blocky crystals of the title compound suitable for single-crystal X-ray diffraction analyses formed in a yield of approximately 65%.