IDENTIFICATION OF A NOVEL TETRAGONALLY COMPRESSED 6-COORDINATE COPPER(II) COMPLEX - PREPARATION AND CHARACTERIZATION OF A 3-CHLOROANILINIUM COPPER CHLORIDE COMPLEX, (3-CHLOROANILINIUM)8[CUCL6]CL4

被引：64

作者：

TUCKER, DA ^{[1
]}

WHITE, PS ^{[1
]}

TROJAN, KL ^{[1
]}

KIRK, ML ^{[1
]}

HATFIELD, WE ^{[1
]}

机构：

[1] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599

来源：

INORGANIC CHEMISTRY | 1991年 / 30卷 / 04期

关键词：

D O I：

10.1021/ic00004a040

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A monmeric hexachlorocuprate(II) ion has been found in the compound (3-chloroanilinium)8[CuCl6]Cl4, CuC48H56Cl18N8. The compound crystallizes in the triclinic space group PlBAR, with unit cell dimensions a = 8.5488 (16) angstrom, b = 13.964 (6) angstrom, c = 14.273 (7) angstrom, alpha = 90.46 (4)-degrees, beta = 107.82 (3)-degrees, and gamma = 102.11 (3)-degrees with Z = 1. The coordination about the discrete [CuCl6]4- ion is that of a tetragonally compressed octahedron with bond distances Cu-Cl(1) = 2.2773 (11) angstrom, Cu-Cl(2) = 2.6061 (18) angstrom, and Cu-Cl(3) = 2.6086 (20) angstrom. The two short bond distances are of the order frequently seen for copper-chloride bonds, but the remaining four bond distances are remarkably long for in-plane 4 + 2 coordination. The Cl(1)-Cu-Cl(1a), Cl(2)-Cu-Cl(2a), and Cl(3)-Cu-Cl(3a) angles are strictly 180-degrees, and the 12 remaining Cl(i)-Cu-Cl(j) angles differ from 90-degrees by 0.4-1.0-degrees. The EPR spectrum of a powered sample is of the "reversed" nature indicative of a 2A ground state with g parallel-to = 2.06 and g perpendicular-to = 2.19. Magnetic susceptibility data provide evidence for antiferromagnetic interactions between the hexachlorocuprate cations, since there is a maximum in the magnetic susceptibility near 10 K. The data may be approximated by Heisenberg chain theory with J = -5.6 cm-1 and g = 2.00 and an interchain exchange parameter J'= -2.1 cm-1.

引用

页码：823 / 826

页数：4

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[2]

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