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Synthesis, crystal and molecular structures of an isomorphic N, S-bridged [Cu2(μ2-I)2(PPh3)2(μ2-N, S-pymSH)] dimer and S-bonded [CuX(η1-S-pymSH)(PPh3)2] monomers (X = Cl, Br)

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Abstract

Monoclinic crystals of [Cu2(μ-I)2(PPh3)2(μ-N, S-pymSH)] · CH3CN) (1), were obtained by equimolar reaction of copper(I) iodide with pyrimidine-2-thione (pymSH), followed by the addition of triphenylphosphine (PPh3) in acetonitrile. Crystal data for 1: space group P21, Z = 2, a = 9.896, b = 18.378, c = 11.703 Å, β = 101.73°. It has an iodo-bridged Cu(μ-I)2Cu core and the pyrimdine-2-thione binds to both Cu centers via N, S-bridging across the Cu(μ-I)2Cu core. This N, S-bridging, a rare coordination mode for pyrimidine-2-thione, leads to a short Cu···Cu separation of 2.675(2) Å (sum of van der Waals radius of Cu atoms, 2.80 Å). The geometry around each Cu center is distorted tetrahedral with angles varying in the range, ca. 102–119°. Copper(I) chloride and bromide also yielded monoclinic crystals of S-bonded tetrahedral monomers, [CuBr(pymSH)(PPh3)2] 2 and [CuCl(pymSH)(PPh3)2] 3. Crystal data for 2: space group P21/n, Z = 8, a = 12.825, b = 43.122, c = 13.396 Å, β = 90.79°. Crystal data for 3: space group P21/c, Z = 4, a = 14.340, b = 10.111, c = 24.200 Å, β = 94.36°. Compound 2 has two crystallographically independent molecules in crystal lattice. The 31P NMR spectrum of 1 showed two signals for PPh3 ligands bonded to two Cu centers with different coordination cores: CuI2PN and CuI2PS. Both 2 and 3 showed one signal each for PPh3 in their 31P NMR spectra.

Graphical abstract

Reaction of copper(I) iodide with pyrimidine-2-thione and triphenylphosphine formed monoclinic crystals of dimer 1 with unusual N, S-bridging across Cu(μ2-I)2Cu core.

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Acknowledgments

One of us (PJK) is thankful to the University for research facilities. Financial support from Council of Scientific and Industrial Research, New Delhi, is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Guru Nanak Dev University, Amritsar, 143 005, India

    Tarlok S. Lobana & Parminderjit Kaur

  2. Departamento de Quimica Inorganica, Facultad de Farmacia, Universidad de Santiago, 15782, Santiago, Spain

    Alfonso Castineiras

  3. School of Chemistry, Crystal Structure Analysis Facility, The University of Sydney, Lidcombe, N.S.W., 2006, Australia

    Peter Turner & Timothy W. Failes

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  1. Tarlok S. Lobana
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  2. Parminderjit Kaur
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  3. Alfonso Castineiras
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  5. Timothy W. Failes
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Correspondence to Tarlok S. Lobana.

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Lobana, T.S., Kaur, P., Castineiras, A. et al. Synthesis, crystal and molecular structures of an isomorphic N, S-bridged [Cu2(μ2-I)2(PPh3)2(μ2-N, S-pymSH)] dimer and S-bonded [CuX(η1-S-pymSH)(PPh3)2] monomers (X = Cl, Br). Struct Chem 19, 727–733 (2008). https://doi.org/10.1007/s11224-008-9345-4

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