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Title: Two new zincophosphates, (H{sub 3}NCH{sub 2}CH{sub 2}NH{sub 3}){sub 2}[Zn({mu}-PO{sub 4}){sub 2}] and (NH{sub 4})[(H{sub 3}N)Zn{l_brace}({mu}-PO{sub 4})Zn{r_brace}{sub 3}]: Crystal structures and relationships to similar open framework zinco- and aluminophospates

Journal Article · · Journal of Solid State Chemistry
 [1];  [2];  [3];  [1]
  1. Laboratory of Crystallography, Faculty of Mining and Geology, University of Belgrade, Dusina 7, 11000 Belgrade (Serbia)
  2. Department of General and Inorganic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade (Serbia)
  3. Institut fuer Mineralogie und Kristallographie, Universitaet Wien-Geozentrum, Althanstrasse 14, A-1090 Vienna (Austria)

Two new zincophosphates, bis(ethylenediammonim) catena-bis({mu}-phosphato)zincate, (H{sub 3}NCH{sub 2}CH{sub 2}NH{sub 3}){sub 2}[Zn({mu}-PO{sub 4}){sub 2}] (1), and ammonium ammine-tris({mu}-phosphato)tetrazincate, (NH{sub 4})[(H{sub 3}N)Zn{l_brace}({mu}-PO{sub 4})Zn{r_brace}{sub 3}] (2), were synthesized under hydrothermal conditions and their crystal structures were determined by single-crystal X-ray diffraction analysis. The crystal structure of 1 consists of infinite macroanionic ZnP{sub 2}O{sub 8}{sup 4-} chains, running along the [0 0 1] direction, and diprotonated ethylenediammonium cations, H{sub 2}en{sup 2+}. The crystal structure of 2 is built up from ZnO{sub 4}, Zn(NH{sub 3})O{sub 3} and PO{sub 4} vertex-sharing tetrahedra connected to form an open 3D framework. The ammonium groups, NH{sub 4}{sup +}, are located in the channels formed by 8M-rings extending along [1 0 0]. In order to study vibrational behavior of H{sub 2}en{sup 2+} and NH{sub 4}{sup +} cations, NH{sub 3} molecules in 1 and 2, single-crystal Raman spectra were obtained. Structural, chemical and topological similarities to the other open framework zinco- and aluminophosphates incorporating different guest species are discussed. - Graphical Abstract: Structure of 1 (left): polyhedral (a) and ORTEP-like (b) representation of the ZnP{sub 2}O{sub 8}{sup 4-} chain with two H{sub 2}en{sup 2+} cations. Structure of 2 (right): polyhedral structure of the layers I and II seen along [1 0 0] (c-axis is vertical). Highlights: > Synthesis under hydrothermal conditions and the crystal structures of two new zincophosphates. > Compound 1 is a new inorganic-organic hybrid compound. > Structure of 1 consists of infinite macroanionic ZnP{sub 2}O{sub 8}{sup 4-} chains and H{sub 2}en{sup 2+} (en=ethylenediamine) cations. > Structure of 2 is a novel 3D open framework structure with 8M channels. > Structure of 2 is the first 3D zincophosphate which incorporates both, the coordinated NH{sub 3} molecule and NH{sub 4}{sup +} cations.

OSTI ID:
21580270
Journal Information:
Journal of Solid State Chemistry, Vol. 184, Issue 9; Other Information: DOI: 10.1016/j.jssc.2011.07.030; PII: S0022-4596(11)00409-9; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
Country of Publication:
United States
Language:
English