catena-Poly[[[iodidocopper(I)]-{μ-N-[(pyridin-2-yl-κN)methyl­idene]pyridin-3-amine-κ2 N 3:N 1}] acetonitrile hemisolvate]

Ali Mahmoudi; Saeed Dehghanpour; Mojtaba Babakhodaverdi

doi:10.1107/S1600536812037270

. 2012 Sep 19;68(Pt 10):m1277–m1278. doi: 10.1107/S1600536812037270

catena-Poly[[[iodidocopper(I)]-{μ-N-[(pyridin-2-yl-κN)methylidene]pyridin-3-amine-κ² N ³:N ¹}] acetonitrile hemisolvate]

Ali Mahmoudi ^a,^*, Saeed Dehghanpour ^b, Mojtaba Babakhodaverdi ^a

PMCID: PMC3470156 PMID: 23125600

Abstract

In the asymmetric unit of the title polymeric complex, {[CuI(C₁₁H₉N₃)]·0.5CH₃CN}_n, there are two Cu^I atoms, two N-[(pyridin-2-yl-κN)methylidene]pyridin-3-amine (PyPy) ligands and two I atoms. Both Cu^I atoms have a distorted tetrahedral geometry, each being coordinated by one I atom, two N atoms of one PyPy ligand and one N atom from an adjacent PyPy ligand. In the crystal, infinite helical chains of [Cu₂(PyPy)₂]_n are formed propagating along the b axis. These chains are linked via weak C—H⋯I hydrogen bonds and π–π stacking interactions [shortest centroid–centroid distance = 3.2727 (14) Å]. During the refinement, electron-density peaks were located that were believed to be highly disordered solvent molecules (possibly acetonitrile). The SQUEEZE option in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155] indicated there were solvent cavities with a total volume of 196 Å³ containing approximately 60 electrons per unit cell, which equated to one molecule of acetonitrile per asymmetric unit.

Related literature

For related structures and applications of coordination polymers, see: Moulton & Zaworotko (2001 ▶); Fei et al. (2000 ▶). For the synthesis of the title ligand, see: Dehghanpour et al. (2009 ▶).

Experimental

Crystal data

[CuI(C₁₁H₉N₃)]·0.5C₂H₃N
M _r = 394.18
Monoclinic,
a = 7.1800 (2) Å
b = 13.2303 (7) Å
c = 27.9383 (13) Å
β = 90.741 (3)°
V = 2653.7 (2) Å³
Z = 8
Mo Kα radiation
μ = 3.96 mm⁻¹
T = 150 K
0.17 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.569, T _max = 0.733
19063 measured reflections
4676 independent reflections
2627 reflections with I > 2σ(I)
R _int = 0.104

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.178
S = 1.02
4676 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 1.39 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812037270/su2480sup1.cif

e-68-m1277-sup1.cif^{(28.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812037270/su2480Isup2.hkl

e-68-m1277-Isup2.hkl^{(270.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22A⋯I1ⁱ	0.95	3.03	3.789 (12)	138
C20—H20A⋯I1ⁱⁱ	0.95	3.14	4.025 (12)	156
C17—H17A⋯I2ⁱⁱⁱ	0.95	3.16	4.011 (11)	149

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

Acknowledgments

The authors are grateful to the Islamic Azad University, University Research Councils for partial support of this work. The crystal structure analysis was carried out by Dr A. J. Lough of the Department of Chemistry of the University of Toronto, Canada.

supplementary crystallographic information

Comment

In recent years, coordination polymers have received much attention due to their variety of architectures and the potential applications as functional materials (Moulton & Zaworotko, 2001). Early reports have shown that nitrogen heterocyclic ligands have been employed in the synthesis of many novel structures (Fei et al., 2000). Here, we report on the synthetic and crystal structure of a novel copper iodide complex based on the ligand pyridin-3-ylpyridin-2-ylmethyleneamine (PyPy).

The asymmetric unit of the title compound, Fig. 1, contains two Cu^I atoms, two pyridin-3-ylpyridin-2-ylmethyleneamine (Dehghanpour et al., 2009) ligands, and two I atoms, Each Cu⁺ atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from one PyPy ligand, one N atom from an adjacent PyPy ligand and one I atom. Each PyPy ligand chelates the Cu atom (via N, N' atoms) and also bridges to another Cu atom (with N" atom), resulting in the formation of chains propagating along the b axis.

The two ligands in the asymmetric unit are nearly planar. In ligand A the interplanar angles between chelate ring (N2/C6/C7/N3) and pyridine ring (lN3/C7-C11) is 2.11 (3)°, while for ligand B [chelate ring N5/C17/C18/N6 and pyridine ring N6/C18-C22] the same angle is 5.82 (4)°. In ligand A the two pyridine rings (N1/C1-C5 and N3/C7-C11) are inclined to one another by 12.11 (4)°. In ligand B the two pyridine rings (N6/C18-C22 and N4/C12-5C16) are inclined to one another by 7.49 (3)°. However, the interplanar angle between two ligand mean planes (A and B) is 52.82 (1)°.

In the crystal, these chains interact viaπ–π interactions between adjacent, inversion replated PyPy ligands The shortest distance of 3.2727 (14) Å [C15-C19 ring, symmetry code: (iii) = -x + 3, -y - 1, -z + 1] is observed between two inversion related ligands. These chains are further connected through C—H···I interactions (Table 1 and Fig 2.).

Experimental

The title complex was prepared by the reaction of CuI (19.1 mg, 0.1 mmol) and pyridin-3-ylpyridin-2-ylmethyleneamine (18.3 mg, 0.1 mmol) in 20 ml of acetonitrile at room temperature. Crystals of the title compound, suitable for X-ray analysis, were obtained by slow evaporation of the solvent at rt.