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The coordination of heterocyclic thiourea ligands (L = N-(2-pyridyl)-N′-phenylthiourea (1), N-(2-pyridyl)-N′-methylthiourea (2), N-(3-pyridyl)-N′-phenylthiourea (3), N-(3-pyridyl)-N′-methylthiourea (4), N-(4-pyridyl)-N′-phenylthiourea (5), N-(2-pyrimidyl)-N′-phenylthiourea (6), N-(2-pyrimidyl)-N′-methylthiourea (7), N-(2-thiazolyl)-N′-methylthiourea (8), N-(2-benzothiazolyl)-N′-methylthiourea (9), N,N′-bis(2-pyridyl)thiourea (10) and N,N′-bis(3-pyridyl)thiourea (11)) with CuX (X = Cl, Br, I, NO3) has been investigated. CuX:L product stoichiometries of 1:1–1:5 were found, with 1:1 being most common. X-ray structures of four 3-coordinate mononuclear CuXL2 complexes (CuCl(6)2, CuCl(7)2, CuBr(6)2, and CuBr(9)2) are reported. In contrast, CuBr(1)2 is a 1D sulfur-bridged polymer. CuIL structures (L = 7, 8) are 1D chains with corner-sharing Cu2(μ-I)2 and Cu2(μ-S)2 units, and CuCl(10) is a 2D network having μ-Cl and N-/S-bridging L. Two [CuL2]NO3 structures are reported: a mononuclear 4-coordinate copper complex with chelating ligands (L = 10) and a 1D link-chain with N-/S-bridging L (L = 3). Two ligand oxidative cyclizations were encountered during crystallization. CuI crystallized with 6 to produce zigzag ladder polymer [(CuI)2(12)]·½CH3CN (12 = N-(pyrimidin-2-yl)benzo[d]thiazol-2-amine) and CuNO3 crystallized with 10 to form [Cu2(NO3)(13)2(MeCN)]NO3 (13 = dipyridyltetraazathiapentalene).
Saxena, Aakarsh; Dugan, Emily C.; Liaw, Jeffrey; Dembo, Matthew D.; and Pike, Robert D., Copper(I) Complexes of Heterocyclic Thiourea Ligands (2009). Polyhedron, 28(18), 4017-4031.