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Syntheses, and Crystal and Molecular Structures of Tetraethylammonium, and Tetrapropylammonium Tris(thiocyanato)cadmates(II), [R 4 N][Cd(SCN) 3 ], (R=C 2 H 5 , C 3 H 7 )

1989; Oxford University Press; Volume: 62; Issue: 2 Linguagem: Inglês

10.1246/bcsj.62.424

1348-0634

Masahiro Taniguchi, Akira Ouchi,

Lanthanide and Transition Metal Complexes

Abstract The title complexes have been synthesized and their crystal and molecular structures determined by a single crystal X-ray diffraction technique. [(C2H5)4N][Cd(SCN)3] (1) is orthorhombic with a space group of A21am; a=10.773(2), b=16.574(4), c=9.871(2) Å, and Z=4, while [(C3H7)4N][Cd(SCN)3] (2) is triclinic with a space group of P\bar1; a=10.297(5), b=11.542(5), c=9.374(3) Å, α=90.10(3), β=91.61(4), γ=80.94(4)°, and Z=2. In 1, the metal atom has a 3N,3S-hexa-coordinated octahedral geometry, and three ligated N atoms take fac-configuration. Each pair of a metal atoms are bridged by three thiocyanate (SCN) ions, where two SCN ions are S-coordinated, while the other is N-coordinated to the same side metal atom, forming a linear polymeric form. In 2, the metal atom is in a 3N,2S-penta-coordinated trigonal-bipyramidal geometry, where one non-bridging SCN ion is N-coordinated equatorially, while four bridging SCN ions are ligated with two N (axially), and two S atoms (equatorially), respectively. Each pair of metal atoms is bridged by two SCN ions, forming a linear polymeric form. The respective tetraalkylammonium ions in 1 and 2 are not bridged to the complex anions, but are bonded only electrostatically. The final R values obtained are: 1, 0.042 and 2, 0.052.