Synthesis and X-ray Powder Structures of Two Lamellar Copper Arylenebis(phosphonates)

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• 作者：Damodara M. Poojary ; Baolong Zhang ; Paul Bellinghausen ; and Abraham Clearfield
• 刊名：Inorganic Chemistry
• 出版年：1996
• 出版时间：August 14, 1996
• 年：1996
• 卷：35
• 期：17
• 页码：4942 - 4949
• 全文大小：236K
• 年卷期：v.35,no.17(August 14, 1996)
• ISSN：1520-510X

文摘

Reaction of copper salts with1,4-phenylenebis(phosphonic acid) yielded a conventional layeredcompound,Cu₂[(O₃PC₆H₄PO₃)(H₂O)₂],while a similar reaction with 4,4'-biphenylenebis(phosphonic acid)resulted in a newlamellar structure with compositionCu[HO₃P(C₆H₄)₂PO₃H].The structures of these compounds were solvedabinitio by using X-ray powder diffraction data. The crystalsof the phenylenebis(phosphonate) compound aremonoclinic, space group C2/c, with a= 18.8892(4) Å, b = 7.6222(2) Å,c = 7.4641(2) Å, mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 90.402(2)mages/entities/deg.gif">,andZ = 4. The layer structure in this case is similar tothat in copper phenylphosphonate,Cu[O₃PC₆H₅]. Themetalatoms display a distorted square pyramidal geometry where four of thecoordination sites are occupied by thephosphonate oxygens. The remaining site is filled by an oxygenatom of the water molecule. Adjacent metal-O₃PC layers are covalently pillared by the phenyl groupof the phosphonates to create a 3-dimensional structure.Cu[HO₃P(C₆H₄)₂PO₃H]is triclinic, space group Pmages/entities/onemacr.gif">, with a =4.856(2) Å, b = 14.225(5) Å, c =4.788(2) Å, mages/gifchars/alpha.gif" BORDER=0>= 97.85(1)mages/entities/deg.gif">, mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 110.14(1)mages/entities/deg.gif">, mages/gifchars/gamma.gif" BORDER=0 > =89.38(1)mages/entities/deg.gif">, and Z = 1. The structure in thiscase, ideally consists of linearchains of copper atoms. The copper atoms are bridged bycentrosymmetrically related phosphonate groups utilizingtwo of their oxygen atoms. This binding mode leads to squareplanar geometry for the copper atoms. The thirdoxygen atom of the phosphonate is protonated and is involved in linkingadjacent linear chains through hydrogenbonds. At the same time, these hydroxyl oxygens interact weakly(Cu-O = 3.14 Å) with the copper atoms ofthe adjacent chain. Considering these long Cu-O interactions,the geometry of the copper atom may be describedas distorted square bipyramidal. As in the phenylphosphonatestructure, the biphenyl groups covalently link theCu-O₃PC networks in the perpendiculardirection.