Pillared Layered Metal Phosphonates. Syntheses and X-ray Powder Structures of Copper and Zinc Alkylenebis(phosphonates)
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- 作者：Damodara M. Poojary ; Baolong Zhang ; and Abraham Clearfield
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：December 24, 1997
- 年：1997
- 卷：119
- 期：51
- 页码：12550 - 12559
- 全文大小：245K
- 年卷期：v.119,no.51(December 24, 1997)
- ISSN：1520-5126
文摘
Covalently pillared layered metal phosphonate compounds wereprepared by the reaction of divalent metalsalts with alkylenebis(phosphonic acids). Cu(II) yieldscompoundsCu2[(O3PC2H4PO3)(H2O)2](1) and Cu2[(O3PC3H6PO3)(H2O)2]·H2O(2) when copper sulfate was reacted withethylenebis(phosphonic acid) and propylenebis(phosphonic acid), respectively. The correspondingbis(phosphonates) obtained for the reaction with zincchlorideareZn2[(O3PC2H4PO3)(H2O)2](3) andZn2[(O3PC3H6PO3)](4). The structures of these four compoundsweredetermined ab initio from their X-ray powder diffractiondata and refined by Rietveld methods. Crystal dataforcompound 1: space groupP21/c, a =8.0756(1) Å, b = 7.5872(1) Å, c =7.4100(1) Å, 
LIGN="middle"> = 116.319(1)
, Z =2.Crystal data for compound 2: space groupPnc2, a = 4.3276(2) Å, b =17.3181(8) Å c = 6.7624(3) Å, Z =2.Crystal data for compound 3: space groupP21/n, a =5.6861(8) Å, b = 15.230(2) Å, c =4.7923(6) Å, = 91.936(2).Crystal data for compound 4: space groupPna21, a = 8.4886(6) Å,b = 5.2720(4) Å, c = 18.865(1) Å,Z = 4. Themetal-oxygen bridging interactions form two-dimensional layers in allfour compounds. The layers are connectedto each other by the alkylene groups leading to three-dimensionalstructures. In the copper compounds the metalatoms are five coordinate where four of the binding sites are from thephosphonate oxygens and one from the wateroxygen. The coordination geometry of the copper atoms in compounds1 and 2 may be described asdistortedsquare-pyramidal, but the distortion is severe in the case of compound2. The zinc atoms in zinc ethylenebis(phosphonate) have distorted octahedral geometry. The phosphonateoxygens provide five binding sites for themetal through chelation and bridging while the water oxygen occupiesthe sixth coordination site. The metal atomsin compound 4, on the other hand, are tetrahedrallycoordinated by the phosphonate oxygens. Unlikecompounds1-3, this compound does not contain any watermolecules. The interlamellar separation is 7.2 and 7.6 Å forcopperethylenebis(phosphonate) and zinc ethylenebis(phosphonate),respectively. The difference in the layer separation,however, is significant in the propylenebis(phosphonates).For copper and zinc compounds the values are 8.65 and9.4 Å, respectively. The layer-connecting alkyl chains createopen spaces whose sizes are determined by the lengthof the chain. Thus, a new class of pillared materials withdefinable cavity sizes may be prepared.
LIGN="middle"> = 116.319(1), Z =2.Crystal data for compound 2: space groupPnc2, a = 4.3276(2) Å, b =17.3181(8) Å c = 6.7624(3) Å, Z =2.Crystal data for compound 3: space groupP21/n, a =5.6861(8) Å, b = 15.230(2) Å, c =4.7923(6) Å, = 91.936(2).Crystal data for compound 4: space groupPna21, a = 8.4886(6) Å,b = 5.2720(4) Å, c = 18.865(1) Å,Z = 4. Themetal-oxygen bridging interactions form two-dimensional layers in allfour compounds. The layers are connectedto each other by the alkylene groups leading to three-dimensionalstructures. In the copper compounds the metalatoms are five coordinate where four of the binding sites are from thephosphonate oxygens and one from the wateroxygen. The coordination geometry of the copper atoms in compounds1 and 2 may be described asdistortedsquare-pyramidal, but the distortion is severe in the case of compound2. The zinc atoms in zinc ethylenebis(phosphonate) have distorted octahedral geometry. The phosphonateoxygens provide five binding sites for themetal through chelation and bridging while the water oxygen occupiesthe sixth coordination site. The metal atomsin compound 4, on the other hand, are tetrahedrallycoordinated by the phosphonate oxygens. Unlikecompounds1-3, this compound does not contain any watermolecules. The interlamellar separation is 7.2 and 7.6 Å forcopperethylenebis(phosphonate) and zinc ethylenebis(phosphonate),respectively. The difference in the layer separation,however, is significant in the propylenebis(phosphonates).For copper and zinc compounds the values are 8.65 and9.4 Å, respectively. The layer-connecting alkyl chains createopen spaces whose sizes are determined by the lengthof the chain. Thus, a new class of pillared materials withdefinable cavity sizes may be prepared.