Abstract
Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-di-thione (SNS), isoindoline-1,3-di-thione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis-[(aceto-nitrile-κN)(6-sulfanylidenepiperidin-2-one-κS)copper(I)], [Cu2I2(CH3CN)2(C5H7NOS)2] (I), bis-(aceto-nitrile-κN)tetra-μ3-iodido-bis-(6-sulfanylidenepiperidin-2-one-κS)-tetra-hedro-tetra-copper(I), [Cu4I4(CH3CN)4(C5H7NOS)4] (II), catena-poly[[(μ-6-sulfanylidenepiperidin-2-one-κ2 O:S)copper(I)]-μ3-iodido], [CuI(C5H7NOS)] n (III), poly[[(piperidine-2,6-di-thione-κS)copper(I)]-μ3-iodido], [CuI(C5H7NS2)] n (IV), and poly[[(μ-isoindoline-1,3-di-thione-κ2 S:S)copper(I)]-μ3-iodido], [CuI(C8H5NS2)] n (V). Compounds I and II crystallize as discrete dimeric and tetra-meric complexes, whereas III, IV, and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexa-gonal [Cu3I3] structure that is not supported by bridging ligands. Structures I, II, and IV display weak to moderately strong Cu⋯Cu cuprophilic inter-actions [Cu⋯Cu inter-nuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding inter-actions between the N-H of the ligand and the μ2 and μ3-I- atoms. Structure III contains classical N-H⋯O inter-actions between the SNO ligands that connect the mol-ecules in a three-dimensional framework. Complex V features π-π stacking inter-actions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV, there were three partially occupied solvent mol-ecules of di-chloro-methane and one partially occupied mol-ecule of aceto-nitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent mol-ecules. The given chemical formula and other crystal data do not take into account the solvent mol-ecules.
Highlights
Copper (I) iodide compounds have been of interest for the past 50 years because of their diverse structural (Peng et al, 2010) and spectroscopic properties (Ford et al, 1999; Hardt & Pierre, 1973)
We were interested in exploring the structures of CuI coordination complexes with three ligands, piperidine-2,6-dithione (SNS), isoindoline-1,3-dithione (SNS6), and 6-thioxopiperidin-2-one
Each Cu center is coordinated by two 2-IÀ atoms, one molecule of acetonitrile, and the thione moiety of the SNO ligand and has a slightly distorted tetrahedral geometry (I—Cu—I and I— Cu—L angles of 100.19 (3)–118.719 (16); L = SNO or acetonitrile)
Summary
Copper (I) iodide compounds have been of interest for the past 50 years because of their diverse structural (Peng et al, 2010) and spectroscopic properties (Ford et al, 1999; Hardt & Pierre, 1973). To III, IV crystallizes with layered two-dimensional polymeric sheets with the symmetry-independent unit formula [Cu(2-I)(2-SNS)]2 (Fig. 7); the Cu and 2-IÀ atoms form Cu2(2-I) rhombi where the center of each rhombus resides on a crystallographic inversion center. These values are consistent with little to no CuÁ Á ÁCu cuprophilic interaction in the Cu1 dimer while indicating that there is a weak CuÁ Á ÁCu cuprophilic interaction in the Cu2 dimer For both half dimers, the Cu atom’s distorted tetrahedral [I—Cu—I angles between 115.06 (3) and 117.46 (3) and S—Cu—I angles of 96.95 (4)–119.35 (6)] coordination sphere is filled by two thione moieties from the 2-SNS ligand; only one of these 2-SNS ligands per Cu atom is symmetry-independent (Fig. 8). This results in a packing motif with a polar arrangement of SNS6 ligands on one side of the inorganic sheets, which results in a smaller spacing between the inorganic layers [7.598 (3) A , see Fig. 12] in V than in III [14.134 (5) A , see Fig. 13]
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