Chloridobis(1,10-phenanthroline-κ2 N,N′)copper(I) dichloridocopper(II)

Qingfen Meng; Yanmei Chen; Bing Li; Sanping Chen; Shengli Gao

doi:10.1107/S1600536810054073

. 2011 Jan 22;67(Pt 2):m226. doi: 10.1107/S1600536810054073

Chloridobis(1,10-phenanthroline-κ² N,N′)copper(I) dichloridocopper(II)

Qingfen Meng ^a,^b, Yanmei Chen ^b, Bing Li ^a, Sanping Chen ^a, Shengli Gao ^a,^*

PMCID: PMC3051778 PMID: 21522885

Abstract

The asymmetric unit of the title compound, [CuCl(C₁₂H₈N₂)₂]·[CuCl₂], contains two complex Cu(II) cations and two cuprate(I) anions. The Cu(II) atom is coordinated by two phenanthroline (phen) molecules and one chloride anion in a distorted trigonal–bipyramidal geometry. The Cu(II) complex cations form layers through π–π stacking [interplanar distance = 3.481 (2) Å]. The dichloridocuprate(I) anions are located between the layers, forming a sandwich-like structure.

Related literature

For the use of 1,10-phenanthroline (phen) in copper complexes, see: Wang et al. (2002 ▶, 2003 ▶); Lan et al. (2007 ▶). For complexes involving five-coordinated copper atoms with 1,10-phen ligands, see: Gkioni et al. (2008 ▶); Mao et al. (2004 ▶); Ma et al. (2000 ▶); Hu et al. (2006 ▶). For mixed-valence copper complexes with 1,10-phen, see: Xu et al. (2007 ▶).

Experimental

Crystal data

[CuCl(C₁₂H₈N₂)₂]·[CuCl₂]
M _r = 593.84
Monoclinic,
a = 9.8137 (3) Å
b = 17.8813 (6) Å
c = 26.2679 (7) Å
β = 90.535 (1)°
V = 4609.3 (2) Å³
Z = 8
Mo Kα radiation
μ = 2.21 mm⁻¹
T = 296 K
0.18 × 0.15 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.691, T _max = 0.957
35792 measured reflections
9043 independent reflections
6276 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.090
S = 1.01
9043 reflections
595 parameters
16 restraints
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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, global. DOI: 10.1107/S1600536810054073/jh2249sup1.cif

e-67-0m226-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054073/jh2249Isup2.hkl

e-67-0m226-Isup2.hkl^{(442.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N3	1.992 (3)
Cu1—N2	1.999 (3)
Cu1—N4	2.104 (3)
Cu1—N1	2.115 (3)
Cu1—Cl1	2.2721 (9)
Cu2—N5	1.983 (3)
Cu2—N8	1.992 (3)
Cu2—N7	2.125 (2)
Cu2—N6	2.162 (3)
Cu2—Cl2	2.2306 (10)
Cu3—Cl3	2.0813 (12)
Cu3—Cl4	2.0936 (11)
Cu4—Cl6	2.0669 (13)
Cu4—Cl5	2.0706 (11)

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Acknowledgments

We are grateful for financial support from the National Science Foundation of China (Nos. 20771089, 20873100).

supplementary crystallographic information

Comment

As bidentate diimine ligand, 1,10-phenanthroline (phen), has been widely used as the second ligand in prepare many kinds of metal-coordination complexes, especially in copper(II) complexes (Wang et al. 2003, Wang et al. 2002, Lan et al. 2007). Although many five-coordinated copper(II) complexes are well documented (Gkioni et al. 2008, Mao et al. 2004, Ma et al. 2000, Hu et al. 2006), the presence mixed-charge complexes have been rarely observed (Xu et al. 2007). Here we report a mixed-charge copper complex with 1,10-phenanthroline as coordinate ligand, this complex was constituted through π-π interactions. The Molecular structure of 1 showing 50% probability displacement ellipsoids was shown in Fig. 1. The coordinate environment of complex 1 shown in figure 2. The Packing diagram of 1 viewed down the a-axis was presented in Fig. 3. Selected band length and angle see table 1.

Experimental

The complex 1 was synthesized by solvothermal reaction. A mixture of 1,10-Phenanthroline monohydrate(0.0198 g, 0.1 mmol), CuCl₂.2H₂O (0.0170 g, 0.1 mmol), L1 (L1 = HO-(Ph)—CH=N—Ph—O—Ph—N=CH-(Ph)—OH (0.0204 g, 0.05 mmol) and CH₃CH₂OH (3 ml) was sealed in a 6 ml glass tube and heated to 393 K for 72 h. After cooling to room temperature, green crystals were obtained concomitanted with a lot of brown precipitation. The color of solution is light-brown. The ligand of L1 could't coordinate with Cu.