catena-Poly[[di-μ-chlorido-dicopper(I)]bis­[μ-η2,σ1-4-(2-allyl-2H-tetra­zol-5-yl)pyridine]]

Wei Wang

doi:10.1107/S1600536808017820

. 2008 Jun 19;64(Pt 7):m930. doi: 10.1107/S1600536808017820

catena-Poly[[di-μ-chlorido-dicopper(I)]bis[μ-η²,σ¹-4-(2-allyl-2H-tetrazol-5-yl)pyridine]]

Wei Wang ^a,^*

PMCID: PMC2961636 PMID: 21202785

Abstract

The title polymer, [Cu₂Cl₂(C₉H₉N₅)₂]_n, has been prepared by the solvothermal treatment of CuCl with 4-(2-allyl-2H-tetrazol-5-yl)pyridine. The crystal structure shows that the title compound is a homometallic Cu^I–olefin coordination polymer, in which the Cu₂Cl₂ nodes are bridged by two olefin ligands. The asymmetric unit contains one-half of the monomer, the complete monomer having twofold rotation symmetry. The coordination environment of Cu^I is slightly distorted tetrahedral, with coordination sites being two μ₂-Cl atoms, one pyridine N atom of an organic ligand and one allylic double bond of a symmetry-related ligand. Each organic molecule behaves as a bidentate ligand, connecting two neighboring Cu₂Cl₂ dimers in the polymeric chain, which runs along [010].

Related literature

For the solvothermal synthesis and for related structures, see: Ye et al. (2005 ▶, 2007 ▶). For related structures, see: Wang (2008a,b,c).

Experimental

Crystal data

[Cu₂Cl₂(C₉H₉N₅)₂]
M _r = 286.21
Monoclinic,
a = 17.270 (3) Å
b = 12.040 (2) Å
c = 13.064 (3) Å
β = 127.94 (3)°
V = 2142.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 293 (2) K
0.2 × 0.15 × 0.1 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.643, T _max = 0.800
10753 measured reflections
2451 independent reflections
1814 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.100
S = 1.06
2451 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶) and XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017820/bh2171sup1.cif

e-64-0m930-sup1.cif^{(14.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017820/bh2171Isup2.hkl

e-64-0m930-Isup2.hkl^{(120.5KB, hkl)}

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

Acknowledgments

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

Under hydrothermal or solvothermal conditions, some interesting reactions and compounds can be obtained, while these products could not be synthesized using conventional solution techniques. In sealed tubes, unstable Cu^I salts can exist under reduced pressure, and then interesting Cu^I coordination compounds can be obtained. The title compound is obtained through solvothermal treatment of CuCl and 4-(2-allyl-2H-tetrazol-5-yl)pyridine in methanol solvent at 348 K. Colourless block crystals suitable for X-ray diffractions have been isolated.

The Cu^I ion is coordinated to two olefin ligands and two bridging Cl atoms in a tetrahedral environment (Fig. 1). Two olefin ligands related by a twofold axis link the neighbouring Cu₂Cl₂ dimers to form an homometallic Cu^I olefin coordination polymer, developing along the [010] axis, with the Cu₂Cl₂ dimers acting as nodes. The allyl groups coordinate to Cu^I centers through N atoms of pyridine rings and double bonds of allyl groups. Unfortunately, the N atoms of tetrazole rings fail to coordinate Cu^I ions (Fig. 2).

Experimental

A mixture of 4-(2-allyl-2H-tetrazol-5-yl)pyridine (20 mg, 0.2 mmol), CuCl (36 mg, 0.4 mmol), and methanol (2 ml) sealed in a glass tube were maintained at 348 K. Crystals suitable for X-ray analysis were obtained after 5 days.