catena-Poly[[(triphenyl­phosphane)copper(I)]-di-μ-iodido-[(triphenyl­phosphane)copper(I)]-μ-{1,2-bis­[1-(pyridin-4-yl)ethyl­idene]hydrazine}]

Hoong-Kun Fun; Wan-Sin Loh; Goutam K Patra; Anindita Mukherjee; Pankaj K Pal

doi:10.1107/S1600536811036555

. 2011 Sep 14;67(Pt 10):m1389. doi: 10.1107/S1600536811036555

catena-Poly[[(triphenylphosphane)copper(I)]-di-μ-iodido-[(triphenylphosphane)copper(I)]-μ-{1,2-bis[1-(pyridin-4-yl)ethylidene]hydrazine}]

Hoong-Kun Fun ^a,^*,^‡, Wan-Sin Loh ^a,^§, Goutam K Patra ^b, Anindita Mukherjee ^b, Pankaj K Pal ^b

PMCID: PMC3201507 PMID: 22058699

Abstract

In the title coordination polymer, [Cu₂I₂(C₁₄H₁₄N₄)(C₁₈H₁₅P)₂]_n, the Cu^I atom is coordinated by two I atoms, one P atom and one N atom in a fairly regular tetrahedral arrangement. A crystallographic inversion centre generates a Cu₂I₂ diamond with a Cu–Cu separation of 3.0120 (5) Å. The complete N,N′-(1-pyridin-4-yl-ethethylidene)-hydrazine molecule is also generated by inversion symmetry, and this bridging ligand leads to [011] polymeric chains in the crystal structure.

Related literature

For background to copper(I) iodide and triphenylphosphine networks, see: Siedel & Stang (2002 ▶); Fujita et al. (2005 ▶); Banerjee et al. (2008 ▶); Zhou et al. (2006 ▶); Yam & Lo (1999 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Cu₂I₂(C₁₄H₁₄N₄)(C₁₈H₁₅P)₂]
M _r = 1143.72
Triclinic,
a = 9.2788 (4) Å
b = 11.4322 (5) Å
c = 12.4204 (5) Å
α = 74.566 (2)°
β = 76.690 (2)°
γ = 72.067 (2)°
V = 1192.41 (9) Å³
Z = 1
Mo Kα radiation
μ = 2.29 mm⁻¹
T = 100 K
0.36 × 0.23 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.494, T _max = 0.724
33229 measured reflections
8881 independent reflections
7865 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.086
S = 1.05
8881 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 2.34 e Å⁻³
Δρ_min = −1.81 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036555/hb6379sup1.cif

e-67-m1389-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036555/hb6379Isup2.hkl

e-67-m1389-Isup2.hkl^{(434.4KB, hkl)}

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

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

Cu1—I1ⁱ	2.6417 (3)
Cu1—I1	2.6781 (3)
Cu1—N1	2.0586 (15)
Cu1—P1	2.2278 (5)

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Cu1ⁱ—I1—Cu1

68.967 (9)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of a research fellowship.

supplementary crystallographic information

Comment

Copper(I) iodides are interesting building blocks for the formation of extended solid-state coordination architectures (Siedel et al., 2002; Fujita et al., 2005; Banerjee et al., 2008). Copper(I) complexes with PPh₃ as a co-ligand are of rising importance owing to their diverse structures and photophysical and chemical properties (Zhou et al., 2006; Yam & Lo, 1999).

The asymmetric unit of the title polymeric compound (Fig. 1) contains one Cu^I cation, one iodine anion, one triphenylphosphane unit and one N,N'-(1-pyridin-4-yl-ethethylidene)-hydrazine unit. The other half being generated by an inversion center (symmetry code: -x + 2, -y, -z). Each Cu^I cation is tetracoordinated by one nitrogen, one phosphorus and two iodine atoms. The Cu–I distances are 2.6417 (3) and 2.6781 (3) Å. In the crystal (Fig. 2 & Fig. 3), the nitrogen atoms are bridged together, leading to the formation of polymeric chains along the [011].

Experimental

The N,N'-bis-(1-pyridin-4-yl-ethethylidene)-hydrazine component was prepared in good yield as a yellow solid by condensing hydrazine hydrate with 4-acetylpyridine in anhydrous methanol in 1:2 molar ratio. The Cu(I) complex was prepared in the following way: to a solution of PPh₃ (0.262 g, 1 mmol) in CH₃CN (50 ml), CuI (0.19 g, 1 mmol) was added. The reaction mixture was stirred for about 1 h to obtain a white turbid solution. Then N,N'-bis-(1-pyridin-4-yl-ethethylidene)-hydrazine (0.238 g, 1 mmol) in 20 ml CHCl₃ was added with constant stirring at room temperature to give a clear yellowish solution. Orange–red block-shaped crystals were obtained by slow evaporation of the solution after 2 days. Yield: 0.45 g (70%).