Synthesis and Structures of Polymeric Mn, Co, Cu, and Zn Complexes of 3-Diphenylamino-4-hydroxycyclobut-3-ene-1,2-dione (Diphenylaminosquarate) and of the Salt [Ni(H2O)6][(C
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- 作者：Avril R. Williams ; Bert D. Alleyne ; Lincoln A. Hall ; Andrew J. P. White ; David J. Williams ; and Laurence K. Thompson
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：November 13, 2000
- 年：2000
- 卷：39
- 期：23
- 页码：5265 - 5270
- 全文大小：125K
- 年卷期：v.39,no.23(November 13, 2000)
- ISSN：1520-510X
文摘
Reaction of M(NO3)2·xH2O (M = Mn, Co, Ni, Cu, Zn) with 3-diphenylamino-4-hydroxycyclobut-3-ene-1,2-dione (diphenylaminosquarate) produces the neutral polymeric species {M[G SRC="/images/entities/mgr.gif">-(C6H5)2NC4O3]2[H2O]2}n [M = Mn(1), Cu (2)]; {M[
ges/entities/mgr.gif">-(C6H5)2NC4O3][(C6H5)2NC4O3][H2O]3}n [M = Co (3), Zn (4)]; and in the case of Ni, the salt[Ni(H2O)6][(C6H5)2NC4O3]2·2H2O (5). Complexes 1 and 2 are isomorphous and crystallize in the monoclinicspace group P21/c with, for 1, a = 13.138(1) Å, b = 10.900(2) Å, c = 9.269(2) Å, ges/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 96.07(1)ges/entities/deg.gif">, and Z = 2.Complexes 3 and 4 are also isomorphous and crystallize in the space group P21/c with, for 3, a = 13.211(1) Å,b = 11.038(1) Å, c = 18.748(1) Å, ges/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 97.75(1)ges/entities/deg.gif">, and Z = 4. The nickel salt, 5, crystallizes in the triclinic spacegroup P
gif"> with a = 6.181(1) Å, b = 9.417(1) Å, c = 15.486(1) Å, ges/gifchars/alpha.gif" BORDER=0> = 101.37(1)ges/entities/deg.gif">, ges/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 95.51(1)ges/entities/deg.gif">, ges/gifchars/gamma.gif" BORDER=0 > = 107.57(1)ges/entities/deg.gif">, and Z = 1. In 1 and 2, the metal coordination is octahedral, comprising four ges/entities/mgr.gif">-1,3-bridging diphenylaminosquarate ligands and two trans aqua ligands. In 3 and 4, the metal coordination is again octahedral, comprisingtwo ges/entities/mgr.gif">-1,3-bridging and one pendant diphenylaminosquarate ligands, the octahedron being completed by threeaqua ligands in a meridional configuration. In 5, the hexaaquanickel(II) ion is linked by O-H···O hydrogenbonds to a pair of diphenylaminosquarate anions. These anion-cation units are linked via included water moleculesto form hydrogen-bonded chains. The diphenylaminosquarate ligands in the polymeric complexes 1-4 displaymultiple-bond localization, a feature which is absent in 5. Complex 1 exhibits weak antiferromagnetic coupling,whereas 2 shows no significant magnetic interactions.