Tetra-μ-benzoato-bis­[(6-methyl­quino­line)­copper(II)]

Seung Man Yu; Chi-Ho Park; Pan-Gi Kim; Cheal Kim; Youngmee Kim

doi:10.1107/S1600536808016516

. 2008 Jun 7;64(Pt 7):m881–m882. doi: 10.1107/S1600536808016516

Tetra-μ-benzoato-bis[(6-methylquinoline)copper(II)]

Seung Man Yu ^a, Chi-Ho Park ^b, Pan-Gi Kim ^c, Cheal Kim ^a,^*, Youngmee Kim ^d,^*

PMCID: PMC2961840 PMID: 21202752

Abstract

In the title compound, [Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂], the paddle-wheel-type dinuclear complex is constructed by four bridging benzoate groups and two terminal 6-methylquinoline ligands. The asymmetric unit contains one-half of the whole molecule, and there is an inversion center at the mid-point of the Cu⋯Cu bond. The octahedral coordination of each Cu atom, with four O atoms in the equatorial plane, is completed by the N atom of the 6-methylquinoline molecule [Cu—N = 2.212 (2) Å] and by another Cu atom [Cu⋯Cu = 2.6939 (13) Å]. The Cu atom lies 0.234 Å out of the plane of the four O atoms. The molecular packing is stabilized by one intramolecular C—H⋯O as well as C—H⋯π and π–π interactions.

Related literature

For related literature, see: Batten & Robson (1998 ▶); Chun et al. (2005 ▶); Cotton & Walton (1993 ▶); Janiak (2003 ▶); Lee et al. (2008 ▶); Mines et al. (2002 ▶); Pichon et al. (2007 ▶); Yoo et al. (2003 ▶).

Experimental

Crystal data

[Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂]
M _r = 897.88
Triclinic,
a = 10.420 (7) Å
b = 10.590 (7) Å
c = 10.751 (6) Å
α = 70.399 (11)°
β = 64.234 (10)°
γ = 81.107 (10)°
V = 1006.5 (11) Å³
Z = 1
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 288 (2) K
0.10 × 0.08 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS: Bruker, 1997 ▶) T _min = 0.898, T _max = 0.915
5579 measured reflections
3848 independent reflections
3001 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.100
S = 1.04
3848 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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, New_Global_Publ_Block. DOI: 10.1107/S1600536808016516/bx2146sup1.cif

e-64-0m881-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016516/bx2146Isup2.hkl

e-64-0m881-Isup2.hkl^{(188.6KB, hkl)}

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

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

Cg1 is the centroid of the C22–C27 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O11	0.93	2.50	3.047 (4)	118
C2—H2⋯Cg1ⁱ	0.93	2.82	3.734 (3)	168

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Symmetry code: (i) Inline graphic .

Table 2. π–π interactions (Å, °).

Cg2 is the centroid of ring C22–C27. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI	CgJ	CgI⋯CgJ	Dihedral angle	Interplanar distance	Offset
Cg2	Cg2i	3.967 (4)		3.39	2.06

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Environmental Technology Educational Innovation Program (2006) of the Ministry of Environment, the Cooperative Research Program for Agricultural Science and Technology Development (20070301–036-019–02), and the Seoul R&BD Program is gratefully acknowledged.

supplementary crystallographic information

Comment

Coordination polymers comprised of metal ions and bridging ligands represent one of the most active areas of material science and chemical research due to their potential applications as functional materials ranging from catalysis, gas absorption, molecular recognition, optics, and so on (Batten & Robson, 1998; Chun et al., 2005; Mines et al., 2002; Janiak, 2003; Yoo et al., 2003). The continuing interest in this area is also due to their intriguing variety of architectures and topologies through the variation of building blocks and reaction conditions. The dinuclear metal carboxylates, M₂(O₂CR)₄, are one of the important building blocks for the study of structures of coordination polymers (Cotton & Walton, 1993) and copper(II) carboxylates among them are often used as building blocks to form a pillard-grid MOF with large pores (Pichon et al., 2007). We have also used copper(II) benzoate as a building block and reported the structure of copper(II) benzoate with quinoxaline (Lee, et al., 2008). In this work, we have employed 6-methylquinoline to investigate the substituent effect of an organic ligand on the structure of copper-benzoate containing coordination complexes.We report here on the structure of new copper(II) benzoate with 6-methylquinoline.

Asymmetric unit contains half of whole molecule, and there is an inversion center in the middle of Cu—Cu bond. Symmetric operation (-x + 1,-y + 2,-z + 1) produces a paddle-wheel type dinuclear copper-benzoate complex (Fig. 1). The paddle-wheel type dinuclear complex is constructed by four bridging benzoate groups and two terminal 6-methylquinoline ligands. The octahedral coordination of each Cu atom, with four oxygen atoms in the equatorial plane, is completed by nitrogen atom of 6-methylquinoline molecule (Cu—N 2.212 (2) Å) and by another copper atom (Cu···Cu 2.6939 (13) Å). The copper atom is 0.234 Å out of the plane of the four oxygen atoms.In the crystal structure the molecular packing is stabilized by one intramolecular C—H···O as well as C—H···π and π ···π interactions, Table, 1 and 2.

Experimental

19.0 mg (0.1 mmol) of Cu(NO₃)₂^.2.5H₂O and 28.0 mg (0.2 mmol) of C₆H₅COONH₄ were dissolved in 4 ml me thanol and carefully layered by 4 ml acetone solution of 6-methylquinoline ligand (29.0 mg, 0.2 mmol). Suitable crystals of the title compound for X-ray analysis were obtained in a few weeks.