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[Zn(H{sub 2}PO{sub 4}){sub 4}]{sup 2-} clusters and {sub {infinity}}[Zn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}PO{sub 4}){sub 2}]{sup 4-} layers in two new zinc phosphates templated by [H{sub 2}(4-amino-2.2.6.6-tetramethylpiperidine)]{sup 2+} cations

Journal Article · · Journal of Solid State Chemistry
 [1];  [2];  [2];  [1]
  1. Unite de recherche 99/UR12-30, Departement de Chimie, Faculte des Sciences de Bizerte, 7021 Jarzouna (Tunisia)
  2. Laboratoire des Oxydes et Fluorures, UMR CNRS 6010, Faculte des Sciences et Techniques, Universite du Maine, 72085 Le Mans Cedex 9 (France)
+ Show Author Affiliations

Two zinc phosphates (ZnPO), [H{sub 2}(N{sub 2}C{sub 9}H{sub 20})].[Zn(H{sub 2}PO{sub 4}){sub 4}] (I) and [H{sub 2}(N{sub 2}C{sub 9}H{sub 20})]{sub 2}.[Zn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}PO{sub 4}){sub 2}].H{sub 2}O (II), are synthesized under hydrothermal conditions using 4-amino-2.2.6.6-tetramethylpiperidine as organic template. I crystallizes in P1-bar space group with a=8.7398(3)A, b=9.0417(3)A, c=15.3822(1)A, {alpha}=92.57(1){sup o}, {beta}=89.76(1){sup o}, {gamma}=102.16(2){sup o}, V=1187.1(1)A{sup 3} and Z=2. Its structure, refined to R=0.029 and R{sub w}=0.076 for 4279 independent reflections, consists of [Zn(H{sub 2}PO{sub 4}){sub 4}]{sup 2-} clusters held together through strong hydrogen bonds to form pseudo-layers between which the doubly protonated amine molecules are inserted. II is monoclinic, C2, with a=27.57(2)A, b=9.745(5)A, c=14.08(1)A, {beta}=103.72(5){sup o}, V=3675(4)A{sup 3} and Z=4 (R=0.079, R{sub w}=0.268, 2477 independent reflections). The structure of II consists of {sub {infinity}}[Zn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}PO{sub 4}){sub 2}]{sup 4-} inorganic (2D) layers built up from vertex-sharing [ZnO{sub 4}] and [(H{sub 2}/H)PO{sub 4}] tetrahedra. Organic cations and water molecules ensure the connection between these layers via hydrogen bonds. It is shown that numerous (1D) (2D), e.g., [H{sub 2}(N{sub 2}C{sub 9}H{sub 20})]{sub 2}.[Zn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}PO{sub 4}){sub 2}].H{sub 2}O, and (3D) (ZnPO) result from the condensation of the [Zn(H{sub 2}PO{sub 4}){sub 4}]{sup 2-} clusters.

OSTI ID:
20725974
Journal Information:
Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 6 Vol. 178; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AMINES
HYDROTHERMAL SYNTHESIS
LAYERS
MONOCLINIC LATTICES
SPACE GROUPS
TRICLINIC LATTICES
ZINC PHOSPHATES