Dibromidobis(1,10-phenanthroline-κ2 N,N′)cadmium(II)

Yu-Hui Sun; Shu-Fen Luo; Xiu-Zhi Zhang; Zi-Yi Du

doi:10.1107/S1600536809020352

. 2009 Jun 6;65(Pt 7):m708. doi: 10.1107/S1600536809020352

Dibromidobis(1,10-phenanthroline-κ² N,N′)cadmium(II)

Yu-Hui Sun ^a, Shu-Fen Luo ^a, Xiu-Zhi Zhang ^a, Zi-Yi Du ^a,^*

PMCID: PMC2969372 PMID: 21582654

Abstract

The title compound, [CdBr₂(C₁₂H₈N₂)₂], synthesized by the hydrothermal reaction of Cd(CH₃COO)₂·2H₂O with NaBr and 1,10-phenanthroline, has the Cd^II cation coordinated by two Br⁻ anions and four N atoms from two 1,10-phenanthroline ligands in a distorted octahedral geometry. The crystal packing is stabilized by intermolecular π–π interactions with centroid–centroid distances 3.572 (1) and 3.671 (1) Å together with C—H⋯Br hydrogen bonds.

Related literature

For other cadmium–halogen compounds with 1,10-phenanthroline (phen) as a coligand, see: Cao et al. (2007 ▶); Chen et al. (2003 ▶); Guo et al. (2006 ▶); He et al. (2005 ▶); Li et al. (2007 ▶); Wang et al. (1996 ▶); Zhang (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[CdBr₂(C₁₂H₈N₂)₂]
M _r = 632.63
Triclinic,
a = 9.3996 (2) Å
b = 10.1421 (3) Å
c = 12.8441 (3) Å
α = 78.927 (2)°
β = 81.303 (1)°
γ = 70.633 (1)°
V = 1128.58 (5) Å³
Z = 2
Mo Kα radiation
μ = 4.53 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.06 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.279, T _max = 0.762
15420 measured reflections
5656 independent reflections
4515 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.109
S = 1.03
5656 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020352/sj2628sup1.cif

e-65-0m708-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020352/sj2628Isup2.hkl

e-65-0m708-Isup2.hkl^{(273.3KB, hkl)}

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

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

Cd1—N3	2.359 (3)
Cd1—N2	2.367 (3)
Cd1—N1	2.442 (3)
Cd1—N4	2.471 (3)
Cd1—Br1	2.6249 (6)
Cd1—Br2	2.6913 (5)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Br2ⁱ	0.93	2.81	3.731 (5)	171
C20—H20A⋯Br2ⁱⁱ	0.93	2.88	3.776 (5)	162

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

Acknowledgments

This work was supported by the Natural Science Foundation (NSF) of Jiangxi Province (grant No. 2008GQH0013), the NSF of Jiangxi Provincial Education Department (grant No. GJJ09317), and the Key Laboratory of Jiangxi University for Functional Materials Chemistry.

supplementary crystallographic information

Comment

Recently, there have been a number of reports of cadmium-halogen complexes with 1,10-phenanthroline (phen) as a coligand (Cao et al., 2007; Chen et al., 2003; Guo et al., 2006; He et al., 2005; Li et al., 2007; Wang et al., 1996; Zhang, et al., 2007). We have synthesized the mononuclear title complex [CdBr₂(phen)₂], (I), Fig 1. The Cd^II cation is coordinated by two Br^- anions and four N atoms from two 1,10-phenanthroline ligands in a distorted octahedral geometry, Table 1. The Cd—Br and Cd—N bond lengths are in the expected ranges (Allen et al. 1987). It is worthy of note that compound I crystallizes in the triclinic space group P-1 , while the analogous mononuclear chlorido and iodido complexes [CdCl₂(phen)₂] (Wang et al., 1996) and [CdI₂(phen)₂] (Cao et al., 2007) crystallize in the monoclinic, P21/c, and orthorhombic, Pbcn, space groups respectively.

The crystal packing is stabilized by intermolecular π–π interactions between the phen rings, with centroid-centroid distances of 3.572 (1) Å (from two adjacent C13/C14/C15/C16/C24/N3 rings) and 3.671 (1) Å (from two adjacent C7/C8/C9/C10/N2/C11 rings), and C—H···Br hydrogen bonds, Table 2.

Experimental

A mixture of Cd(CH₃COO)₂.2(H₂O) (67 mg, 0.25 mmol), NaBr (36 mg, 0.35 mmol) and 1,10-phenanthroline (69 mg, 0.35 mmol) in 10 ml distilled water was put into a Parr Teflon-lined autoclave (23 ml) and heated at 413 K for 3 days. On cooling, yellow block-shaped crystals of compound I were collected in a ca 55% yield based on Cd.