Poly[μ2-chlorido-dichlorido[μ2-4′-(4-pyrid­yl)-2,2′:6′,2′′-terpyridine]­copper(I)copper(II)]

Chao-Ying Zhu

doi:10.1107/S1600536811014759

. 2011 Apr 29;67(Pt 5):m639. doi: 10.1107/S1600536811014759

Poly[μ₂-chlorido-dichlorido[μ₂-4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine]copper(I)copper(II)]

Chao-Ying Zhu ^a,^*

PMCID: PMC3089113 PMID: 21754347

Abstract

In the mixed-valence Cu^I/Cu^II coordination polymer, [Cu₂Cl₃(C₂₀H₁₄N₄)]_n, the two Cu atoms are bridged to a pair of Cl atoms across a centre of inversion. The monovalent metal atoms is coordinated by a pyridine N atom as well as by three Cl atoms in a tetrahedral CuNCl₃ geometry. The divalent metal atom is N,N′,N′′-chelated by the heterocycle, and it exists in a square-pyramidal CuN₃Cl₂ geometry; the apical site is occupied by the second bridging Cl atom. The bridging modes of the Cl atoms and the heterocycle give rise to the formation of a layered arrangement parallel to (001).

Related literature

For related structures, see: Hou et al. (2005 ▶); Zhang et al. (2007 ▶)

Experimental

Crystal data

[Cu₂Cl₃(C₂₀H₁₄N₄)]
M _r = 543.78
Triclinic,
a = 8.1389 (8) Å
b = 9.8161 (10) Å
c = 12.4823 (13) Å
α = 79.512 (2)°
β = 85.036 (2)°
γ = 88.202 (2)°
V = 976.78 (17) Å³
Z = 2
Mo Kα radiation
μ = 2.60 mm⁻¹
T = 294 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.694, T _max = 0.771
7840 measured reflections
3778 independent reflections
3391 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.072
S = 1.06
3778 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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/S1600536811014759/ng5143sup1.cif

e-67-0m639-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014759/ng5143Isup2.hkl

e-67-0m639-Isup2.hkl^{(185.2KB, hkl)}

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

supplementary crystallographic information

Comment

Terpyridine and its derivatives have been receiving rapidly increasing attention recently not only because of their versatility as building blocks in supramolecular assembles, but also due to the interesting electronic, photonic and magnetic properties of their transition metal complexes.

4'-(4-Pyridyl)-2,2':6'2''-terpyridine(pyterpy) belongs to this group of ligands and has usually been used to construct a great variety of structurally interesting entities, such as ribbon-type coordination polymers (Hou et al., 2005) and self-catenated networks (Zhang et al., 2007).

The structure of the title compound (I) is shown in Fig. 1. Single-crystal X-ray diffraction shows that the asymmetric unit contains two Cu crystallographically nonequivalent atoms. The Cu1 atom has a distorted square-pyramidal coordination formed by three N atoms of tridentate 4'-(4-pyridyl)-2,2':6'2''-terpyridine (pyterpy) ligand and two Cl atoms. The Cu2 atom is coordinated by one N atom from the pendent monodentate pyridine of pyterpy as well as by three Cl atoms, conferring a tetrahedral coordination geometry. The two terpy ligands in a transoid arrangement link Cu1 and Cu2 atoms, to form a mixed-valence tetrameric M₄L₄ rectangular unit with a separation of 11.017 Å, which is smaller than those in reported ribbon-type compounds, and then linked by a Cu₂Cl₂ cluster, leading to the formation of an infinite 1-D coordination polymer (Fig. 2).

Experimental

The mixture of CuCl (0.020 g, 0.2 mmol), 4'-(4-pyridyl)-2,2':6'2''-terpyridine (pyterpy) (0.062 g, 0.1 mmol), and acetonitrile (6 ml) were placed and sealed in a 15 ml Teflon-lined stainless steel reactor and heated to 180 °C for 72 h, then cooled down to room temperature at a rate of 2 °C/ 20 min. Single crystals suitable for X-ray diffraction were obtained in the form of black bars in ca 20% yield.