Poly[{μ2-1,2-bis­[4-(3-pyrid­yl)pyrimidin-2-ylsulfan­yl]ethane}di-μ2-cyanido-dicopper(I)]

Ya-Wen Zhang; Hua-Ze Dong; Lin Cheng

doi:10.1107/S1600536808013172

. 2008 Jun 7;64(Pt 7):m868. doi: 10.1107/S1600536808013172

Poly[{μ₂-1,2-bis[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]ethane}di-μ₂-cyanido-dicopper(I)]

Ya-Wen Zhang ^a, Hua-Ze Dong ^b, Lin Cheng ^a,^*

PMCID: PMC2961664 PMID: 21202742

Abstract

The asymmetric unit of the title complex, [Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]_n, contains one Cu^I cation, one cyanide ligand and half of a centrosymmetric 1,2-bis[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]ethane (bppe) ligand. The Cu^I atom displays a trigonal coordination geometry, being surrounded by one C atom from one cyanide anion and two N atoms from one cyanide and one bppe ligand. In the complex, each cyanide anion links two Cu^I atoms in a bis-monodentate mode into a zigzag [–Cu—CN–]_n chain. Two parallel chains are linked by bppe ligands into a ladder chain.

Related literature

For related literature, see: Awaleh et al. (2005 ▶); Bu et al. (2003 ▶); Chen et al. (2003 ▶); Su et al. (2000 ▶); Xie et al. (2005 ▶).

Experimental

Crystal data

[Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]
M _r = 291.81
Monoclinic,
a = 16.025 (4) Å
b = 16.296 (7) Å
c = 9.3103 (17) Å
β = 105.660 (19)°
V = 2341.1 (12) Å³
Z = 8
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 153 (2) K
0.50 × 0.20 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.431, T _max = 0.823
6130 measured reflections
2290 independent reflections
1925 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.083
S = 1.09
2290 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2000 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013172/hg2393sup1.cif

e-64-0m868-sup1.cif^{(14.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013172/hg2393Isup2.hkl

e-64-0m868-Isup2.hkl^{(112.7KB, hkl)}

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

There has been current significant interest in the rational design and synthesis of metal-organic coordination architectures by using flexible bridging units due that the flexibility and conformational freedoms of such ligands offer the possibility for the construction of unprecedented frameworks (Su et al., 2000). Recently, flexible thioethers have been well established ligands in coordination and metallosupramolecular chemistry because of their rich structural information (Awaleh et al., 2005, Bu et al., 2003, Chen et al., 2003, Xie et al., 2005). Herein, we report the crystal structure of the title compound, [Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]_n, based on a pyridyl dithioether ligand–1,2-bis(4-(pyridinyl-4-)pyrimidin-2-ylthio)ethane. The asymmetric unit of the title complex, contains one Cu^I cation, one cyano and half a bppe (bppe = 1,2-bis(4-(pyridinyl-4-)pyrimidin -2-ylthio)ethane) ligand. The Cu^I atom displays a triangular geometry, being surrounded by one carbon atom (Cu1—C11a 1.873 (3) Å) from one cyano anion and two nitrogen atoms from one cyano (Cu1—N4 1.916 (2) Å) and one bppe ligand (Cu1—N3 1.873 (3) Å). In the complex, each cyano aion links two Cu^I atoms in a bis-monodentate mode into a zigzag (CuCN)_n chain. The shortest intrachain Cu—Cu distance is 4.894 (2) Å. Two parallel zigzag chains were linked by bppe ligands into a one-dimensional ladder chain, in which the Cu—Cu distance separated by bppe is 11.648 (3) Å. The ladder chain is stabilized by the intraladder C–H···N hydrogen bonds (C9—N1 2.810 (3) Å; C8—N2 3.398 (4) Å). Finally, the ladder chains were constructed into a three-dimensional supramolecular network by the interladder C10–H···N1c (c = -1/2 + x,1/2 - y,1/2 + z) hydrogen bond with the C···N distance 2.891 (4) Å.

Experimental

A mixture of bppe (0.040 g, 0.1 mmol), CuCN (0.018 g, 0.2 mmol), and water (6 ml) were heated in a 15-ml Teflon-lined vessel at 403 K for 3 days, followed by slow cooling (5 K/hr) to room temperature. After filtration and washing with H2O, colorless needle-like crystals were collected and dried in air (0.019 g, yield ca 32% based on bppe).