Versatile coordination patterns in the reaction system of N-benzoyl-N′-(2-pyridyl)thiourea with CuCl2. Their reaction conditions, systematic isolation and crystal structures

A versatile reaction system; N-benzoyl-N′-(2-pyridyl)thiourea (L) with CuCl2, has been studied under conditions of control of the relative concentration of the components (L or CuCl2). Therefore, both converse approaches were employed: one is dropwise addition of L to CuCl2 in ethanol solution, from which a dark-brown needle-like crystal, ∞1{[CuClL′][Cl]} 1, was obtained, which is a chloride-bridged one-dimensional Cu(II) polynuclear complex coordinated by the oxidative cyclization product L′ generated from L (L′ = 2-benzoylimino-[1,2,4]thiadiazolo-[2,3-a]pyridine), and the second approach is conversely dropping CuCl2 into L in acetone solution; at first, a pale-yellow reduced copper(I) mononuclear complex, [CuL2Cl] 2, was formed, which exhibits a planar molecular configuration with a regular three coordination geometry, and then a red bis-sulfur-bridged copper(II) dinuclear complex, {[CuLCl2]2} 3, appeared subsequently. The crystal structures of these three products have been determined by X-ray diffraction. From the presented results the coordination and redox reaction pathways in the L–CuCl2 system have been clearly revealed.

[1]  Gang Li,et al.  Oxidative cyclization and coordinate polymerization of N-benzoyl-N′-(2-pyridyl)thiourea with copper(II) chloride , 2000 .

[2]  Jin‐Pei Cheng,et al.  Electrochemical behaviour of ferrocenyl-containing acyl thiourea derivatives , 1997 .

[3]  Yu-Ming Xu,et al.  Studies on intramolecular hydrogen bonding of 1,1′-bis[N-formyl-N′-p-chlorophenylthiourea]ferrocene , 1997 .

[4]  T. Rojo,et al.  Synthesis and spectroscopic properties of two pyridine-2-carbaldehyde thiosemicarbazonecopper(II) compounds: [CuX2(C7H8N4S)]·H2O (X = Br, Cl). Crystal structure of the bromo complex , 1996 .

[5]  C. Doona,et al.  Equilibrium and Redox Kinetics of Copper(II)-Thiourea Complexes. , 1996, Inorganic chemistry.

[6]  M. Troester,et al.  Crystal Structures of a Family of New Copper(I) Cyanide Complexes of Thiourea and Substituted Thioureas. , 1996, Inorganic chemistry.

[7]  Yaofeng Yuan,et al.  Crystal and molecular structure of N-(ferrocenylcarbonyl)-N'-naphthyl thiourea , 1994 .

[8]  R. Zanoni,et al.  Formation of an anchored copper(II) complex on a thiourea-functionalized silica gel by in situ modification of the tethered ligating function , 1994 .

[9]  G. Kanagaraj,et al.  Synthesis and characterization of complexes of cobalt(II), nickel(II), zinc(II), cadmium(II) and mercury(II) with p-acetamidobenzaldehyde thiosemicarbazone , 1993 .

[10]  R. Willett.  Multiple Stereochemistry in Copper(II) Halides , 1991 .

[11]  K. Murray,et al.  Synthesis, reactions and copper(II), nickel(II), and zinc(II) complexes of N-(2-pyridinyl)ketothioacetamides , 1988 .

[12]  Olga Kennard,et al.  Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds , 1987 .

[13]  C. Bell,et al.  Copper complexes of pyridine 2-aldehyde and 2-acetylpyridine thiosemicarbazones , 1987 .

[14]  K. Murray,et al.  Copper, Thioamide Complexes. Syntheses and Structures of Di-m-chloro-bis[N-(pyridin-2-yl)benzenecarbothioamide-S,N']dicopper(I) and of Bis[N-(pyridin-2-yl)benzenecarbothioamide-S,N']copper(I) Chloride, Complxes Containing Tetrahedrally Coordinated Copper Centres , 1985 .

[15]  P. J. Taylor,et al.  The reversible cation-anion isomerisation of 2-imino-2H-pyrido [1,2-b][1,2,4]thia(oxa)diazole hydrobromide , 1982 .

[16]  E. Ainscough,et al.  Oxidation and other products from the reaction of thiones and phosphine sulphides with metal salts and halogens , 1978 .

[17]  E. L. Amma,et al.  Crystal and molecular structure of a colored intermediate from the reaction of tetramethylthiourea and copper(2+) (dichlorobis(tetramethylthiourea)copper(II)) , 1978 .

[18]  Rln Harris.  The oxidation of N-(2-Pyridyl)thioureas. The synthesis of [1,2,4]Thiadiazolo-[2,3-a]pyridinium salts , 1972 .

[19]  E. L. Amma,et al.  Crystal and molecular structure of chlorotris(N,N'-dimethylthiourea)copper(I) , 1971 .