Di-μ-iodido-bis­[(dimethyl 2,2′-biquinoline-4,4′-dicarboxyl­ate-κ2 N,N′)copper(I)]

Radosław Starosta; Urszula K Komarnicka; Justyna Nagaj; Kamila Stokowa-Sołtys; Aleksandra Bykowska

doi:10.1107/S1600536812020843

. 2012 May 12;68(Pt 6):m756–m757. doi: 10.1107/S1600536812020843

Di-μ-iodido-bis[(dimethyl 2,2′-biquinoline-4,4′-dicarboxylate-κ² N,N′)copper(I)]

Radosław Starosta ^a,^*, Urszula K Komarnicka ^a, Justyna Nagaj ^a, Kamila Stokowa-Sołtys ^a, Aleksandra Bykowska ^a

PMCID: PMC3379095 PMID: 22719316

Abstract

In the centrosymmetric dinuclear title complex, [Cu₂I₂(C₂₂H₁₆N₂O₄)₂], the Cu^I atom is coordinated in a distorted tetrahedral geometry by an N,N′-bidentate dimethyl 2,2′-biquinoline-4,4′-dicarboxylate ligand and two symmetry-related I atoms, which act as bridges to a symmetry-related Cu^I atom. The distance between the Cu^I atoms within the dinuclear unit is 2.6723 (11) Å.

Related literature

Copper(I) complexes are a subject of high interest and have been extensively studied during the past two decades because of their diversified photo-physical properties (Lavie-Cambot et al., 2008 ▶; Vorontsov et al., 2009 ▶; Hashimoto et al., 2011 ▶). The title complex is similar to other copper(I) complexes with halides and aromatic diimines: [Cu₂I₂(1,10-phenanthroline)₂] and Cu₂ X ₂(2,9-dimethyl-1,10-phenanthroline)₂], where X = I, Br, Cl (Healy et al., 1985 ▶); [Cu₂ X ₂(1,10-phenanthroline)₂], where X = Cl and I (Yu et al., 2004 ▶); [Cu₂ X ₂(NN)₂], where X = Br, I and NN = bidentate imino nitroxides (Oshio et al., 1996 ▶); [Cu₂Cl₂(dihexsyl-2,2′-biquinoline-4,4′-dicarboxylate)₂] [Cu₂Cl₂(2,2′-biquinoline-4,4′-dicarboxylic acid)₂] (Vatsadze et al., 2010 ▶). For the preparation of the dimethyl-2,2′-biquinoline-4,4′-dicarboxylate ligand, see: Pucci et al. (2011 ▶) and of the P(CH₂N(CH₂CH₂)₂O)₃ phosphane ligand, see: Starosta et al. (2010 ▶). graphic file with name e-68-0m756-scheme1.jpg

Experimental

Crystal data

[Cu₂I₂(C₂₂H₁₆N₂O₄)₂]
M _r = 1125.62
Triclinic,
a = 8.792 (3) Å
b = 9.157 (3) Å
c = 12.865 (4) Å
α = 96.59 (3)°
β = 102.49 (3)°
γ = 103.51 (3)°
V = 968.2 (5) Å³
Z = 1
Mo Kα radiation
μ = 2.76 mm⁻¹
T = 100 K
0.15 × 0.10 × 0.10 mm

Data collection

Kuma KM-4-CCD κ-geometry diffractometer
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2006 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.466, T _max = 0.912
15308 measured reflections
5471 independent reflections
4606 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.065
S = 1.02
5471 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020843/kp2406sup1.cif

e-68-0m756-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020843/kp2406Isup2.hkl

e-68-0m756-Isup2.hkl^{(267.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1A	2.088 (2)
Cu1—N1B	2.092 (2)
Cu1—I1	2.5473 (10)
Cu1—I1ⁱ	2.6996 (9)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to Dr Miłosz Siczek for the crystal measurements and help with the preparation of this manuscript.

supplementary crystallographic information

Comment

The asymmetric unit of the studied bis((µ-iodo)-(dimethyl-2,2'-biquinoline-4,4'-dicarboxylate))-di-copper(I) complex consist of the [(dimethyl-2,2'-biquinoline-4,4'-dicarboxylate)Cu(I)] moiety (Fig. 1, Table 1). Cu^I atoms are bridged by two iodide ions forming the planar rhombic Cu₂(µ-I)₂ core. Additionally coordinated by the imine nitrogen atoms of the dimethyl-2,2'-biquinoline-4,4'-dicarboxylate ligand, each Cu^I atom reveals a distorted tetrahedral geometry. Connected quinoline rings of the coordinated molecule of dimethyl-2,2'-biquinoline-4,4'-dicarboxylate are not coplanar, the angle between their planes is 5.40 (7)°.

Experimental

Crystals of the title complex were grown in the mixture of dichloromethane and acetone in an attempt to obtain crystals of [Cu(I)(dimethyl-2,2'-biquinoline-4,4'-dicarboxylate) P(CH₂N(CH₂CH₂)₂O)₃] complex. Cu^I was purchased from Aldrich. Dimethyl-2,2'-biquinoline-4,4'- dicarboxylate ligand was prepared from 2,2'-biquinoline-4,4'-dicarboxylic acid (Aldrich) according to the literature method (Pucci et al., 2011). P(CH₂N(CH₂CH₂)₂O)₃ phosphane ligand was synthesized as described previously (Starosta et al., 2010).