π-complexes of copper(I) ionic salts:: Synthesis and crystal structure of (4-allylthiosemicarbazide) (sulfamato)copper(I) and bis(4-allylthiosemicarbazide) (sulfato-O)dicopper(I)

被引:0
作者
Mel'nyk, OP
Filinchuk, YE
Schollmeyer, D
Mys'kiv, MG
机构
[1] Ivan Franko Natl Univ, Dept Chem, UA-79005 Lviv, Ukraine
[2] Univ Mainz, Inst Organ Chem, D-6500 Mainz, Germany
来源
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2001年 / 627卷 / 02期
关键词
copper(I) sulfamate; copper(I) sulfate; pi-complexes; crystal structure;
D O I
10.1002/1521-3749(200102)627:2<287::AID-ZAAC287>3.0.CO;2-P
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Single crystals of [Cu(ATSC)]NH2SO3, (1) (ATSC 4-allylthiosemicarbazide) were obtained by electrochemical synthesis using alternating current. Compound (1) crystallizes in P2(1)2(1)2(1) sp. gr., a=6.8284(2), b=9.3054(3), c= 16.1576(11) Angstrom, Z = 4. ATSC moiety acts as tetradentate ligand, chelating two symmetrically related copper atoms. The Cu atom possesses trigonal pyramidal coordination, formed by two sulphur atoms tone of them at the apical position), nitrogen atom and C=C bond. Sulfamate anion is associated via hydrogen bonds. By slow hydrolysis of 1 crystals of [Cu-2(ATSC)(2)]SO4 (2) were obtained: P (1) over bar sp, gr., a = 9.526(2), b = 12.687(2), c = 14.7340(10) Angstrom, alpha = 95.119(10), beta = 89.903(12), gamma = 109.113(14)degrees, Z = 4. The asymmetric unit of 2 contains two formula units, which are related by pseudosymmetry via a glide plane a. One half of four ATSC molecules act as in 1, the rest as tridentate ligands, which coordinate the two copper atoms in apical positions with sulfate anions. This Cu-S coordination was to date unknown. The structure of the ATSC ligands contributes to the unexpected competitiveness of C=bond in the coordination sphere of Cu-I inspite of strong donor atoms.
引用
收藏
页码:287 / 293
页数:7
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