Lewis-Base Adducts of Groups 11 Metal(I) Compounds. LXII. The Crystal Structures of the 1 : 1 Adducts of Copper(I) Chloride, Bromide and Thiocyanate With Quinoline

Abstract

Adducts (1 : 1) of copper(I) chloride, bromide and thiocyanate with quinoline have been synthesized and have been the subject of single-crystal X-ray structure determinations at 295 K. Crystals of the chloride are orthorhombic, P 212121, a 15.358(7), b 14.309(6), c 3.801(2)Ǻ, Z 4; R was 0.055 for 541 'observed' reflections. Crystals of the bromide are monoclinic, C2/c, a 19.417(5), b 14.048(4), c 15.753(6) Ǻ, β 125.31(2)°, Z 4 tetramers; R was 0.049 for 1138 'observed' reflections. Crystals of the thiocyanate are monoclinic, P 21/c, a 5.682(1), b 10.412(2), c 16.838(5)Ǻ, β 97.48(2)°, Z 4 f.u .; R was 0.045 for 914 'observed' reflections. The chloride takes the form of the common 'stair' polymer, unexpectedly, while the thiocyanate is an expanded version of the same. The bromide provides a second example of a novel tetrameric 'basket' structure exemplified previously by the iodide analogue.

Two- and three-dimensional CuSCN co-ordination networks including new CuSCN structural motifs

“…12,21, 22 The stair-polymer arrangement observed in this complex has been observed before for [Cu(SCN)(NC 5 H 4 Me-2)] ∞ 14 and [Cu(SCN)(NC 9 H 7 )] ∞ (NC 9 H 7 = quinoline). 15 The bond lengths and angles at the copper() centre in 3 are typical of the values expected for a stair-polymer 14,15 but it can be seen that there are slight differences to those observed for 1 and 2. In particular there is a significant lengthening of the Cu-S bond lengths from 2.338(2), 2.349(2) Å in 1, 2.3549(13) Å in 2, to 2.4203(8), 2.5172(8) Å in 3.…”

“…12 It has been previously noted that the balance between the different forms of copper() pseudo-halide or halide is extremely subtle. 23 Although steric arguments have been used to explain the variation between the forms of Cu I SCN observed in previously reported complexes 15 this cannot be the reason for the differences observed in the structures of 1-3 as all the ligands have similar steric properties. Therefore, we can only attribute the variations in structures to the packing effects within the crystal lattice.…”

Assembly of Chiral Two- and Three-dimensional Copper(I) Pseudohalide Based Coordination Polymers with Asymmetrically Substituted Pyrazine and Pyrimidine Ligands

“…In a manner similar to 2, the Cu1±N3 bond adjacent to the methyl substituent of the heterocyclic diazine is markedly longer (2.259 (8) (X = Cl, Br, I) both to extend their coordination number to 3 and to adopt Cu±X±Cu values within a wide angular range is reflected in the much greater variety of CuX structural motifs (e.g.s rhomboid dimers, cubane-like tetramers, single and double chains, sheets) that have been found in their coordination polymers [14,15,17]. The thiocyanate anion can likewise exhibit both twofold and threefold bridging modes and structural motifs such as chains [18,19], staircase double chains [15,18,20] and sheets [15,19,21] have been reported.…”

A Polymeric Structure Containing Cu2Cl2 Units Bridged by 4,4‘-Bipyridine: (PPh3)2Cu2(μ-Cl)2(μ-4,4‘-bipyridine)

“…A series of Cu(I) compounds with chain structures containing Cu 2 Cl 2 dimers and with the general composition CuCl·L (where L = CH 3 CN, C 6 H 5 CN, quinoline C 9 H 7 N, pyridine) have also been reported. Each of these compounds contains Cu 2 Cl 2 dimers that are linked into an infinite chain by sharing the Cl atoms between dimers.…”