catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethano­lato-κ4 N,O:O,N′)dicopper(II)(Cu—Cu)]-di-μ-bromido]

Matthias Zeller; Barry L Westcott; Kristin M Kopp-Vaughn; Allen D Hunter

doi:10.1107/S1600536808024197

. 2008 Aug 6;64(Pt 9):m1121. doi: 10.1107/S1600536808024197

catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethanolato-κ⁴ N,O:O,N′)dicopper(II)(Cu—Cu)]-di-μ-bromido]

Matthias Zeller ^a, Barry L Westcott ^b,^*, Kristin M Kopp-Vaughn ^b, Allen D Hunter ^a

PMCID: PMC2960673 PMID: 21201583

Abstract

The title complex, [Cu₂Br₃(C₁₁H₉N₂O₂)]_n, was one of three isolated by slow evaporation of an acetonitrile reaction mixture of CuBr₂ with di-2-pyridyl ketone (1:1 molar ratio). The title complex contains a 2:1 metal-to-ligand ratio of copper(II) with the hydrated form of the ligand, di-2-pyridylmethanediol. The two copper centers are bridged by a bromide ion and the alkoxy O atom, and the Cu—Cu distance is 2.9801 (5) Å. The dimeric units are further linked by bromide ions, leading to a two-dimensional extended bridged structure. O—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

Apart from the title complex, two others were isolated from the reaction mixture and structurally characterized. One was identical to that of Parker et al. (2000 ▶), the other is reported in the following paper by Westcott et al. (2008 ▶). For other related structures, see: Wang et al. (1986 ▶); Mariezcurrena et al. (1999 ▶).

Experimental

Crystal data

[Cu₂Br₃(C₁₁H₉N₂O₂)]
M _r = 568.01
Triclinic,
a = 8.7708 (7) Å
b = 9.6018 (8) Å
c = 10.1839 (8) Å
α = 73.7060 (10)°
β = 70.8520 (10)°
γ = 63.9280 (10)°
V = 718.28 (10) Å³
Z = 2
Mo Kα radiation
μ = 11.30 mm⁻¹
T = 100 (2) K
0.39 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003 ▶) T _min = 0.122, T _max = 0.424
7397 measured reflections
3537 independent reflections
3305 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.061
S = 1.09
3537 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024197/fj2131sup1.cif

e-64-m1121-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024197/fj2131Isup2.hkl

e-64-m1121-Isup2.hkl^{(173.4KB, 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
O1—H1⋯O2ⁱ	0.84	2.33	3.014 (2)	139

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr Guy Crundwell (CCSU) for helpful discussions. BLW acknowledges funding from the National Science Foundation (NSF # 0420322). MZ and ADH acknowledge funding from the National Science Foundation (NSF #0087210) and the Ohio Board of Regents (CAP-491).

supplementary crystallographic information

Comment

The structure of the title compound, is shown below. The complex was one of three Cu-dpkoh complexes isolated from the 1:1 molar mixture of copper(II)bromide and di-2-pyridyl ketone. The title complex was the second isolated from solution. One other complex had been reported previously by Parker, et al., another unique complex is described elsewhere: Westcott, et al.(2008).

The complex contains two copper centers that are 2.9801 (5) Å apart and are bridged by the hydrated form of the ligand di-2-pyridylketone. Each copper center is also coordinated to the ligand through one unique nitrogen atom and a by a µ-hydroxyl bridge. Additionally, each Cu center coordinates one bromide ion. The bromide ion then acts as a bridging ligand to the next di-copper unit, leading to a polymeric structure as shown in Figure 2.

Experimental

Di-2-pyridyl ketone (dpk) was purchased from Aldrich and used as received. Copper(II) bromide hexahydrate was dried in an oven at 110 C for 48 h before use. DPK (1 mmol) and copper(II) bromide (1 mmol) were combined in 40 ml of acetonitirle and stirred for 30 minutes. The resulting green crystals were isolated after 4 days by slow evaporation of the solution.