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

• Published in: Journal of solid state chemistry Vol. 184; no. 9; pp. 2506 - 2515
• Main Authors: Karanović, Ljiljana, Poleti, Dejan, Đorđević, Tamara, Šutović, Sabina
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 01-09-2011; Elsevier
• Subjects: Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Hydrogen bonding; Hydrothermal synthesis; Inorganic–organic hybrid; Materials science; Open framework structure; Organic compounds; Other materials; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Zincophosphate; Zincophosphate; Inorganic–organic hybrid; Hydrothermal synthesis; Open framework structure; Hydrogen bonding; Raman spectra; Vertex; Hybrid material; XRD; Ammonia; Monocrystals; Organic-inorganic hybrid materials; Open framework; Hydrogen bonds; Inorganic-organic hybrid; Crystal growth from solutions; Aluminophosphates; X-ray diffraction analysis; Crystal structure
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2011.07.030

Two new zincophosphates, bis(ethylenediammonim)
catena-bis(μ-phosphato)zincate, (H
3NCH
2CH
2NH
3)
2[Zn(μ-PO
4)
2] (
1), and ammonium ammine-tris(μ-phosphato)tetrazincate, (NH
4)[(H
3N)Zn{(μ-PO
4)Zn}
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
2O
8
4− chains, running along the [0
0
1] direction, and diprotonated ethylenediammonium cations, H
2en
2+. The crystal structure of
2 is built up from ZnO
4, Zn(NH
3)O
3 and PO
4 vertex-sharing tetrahedra connected to form an open 3D framework. The ammonium groups, NH
4
+, are located in the channels formed by 8M-rings extending along [1
0
0]. In order to study vibrational behavior of H
2en
2+ and NH
4
+ cations, NH
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.
Structure of
1 (left): polyhedral (a) and ORTEP-like (b) representation of the ZnP
2O
8
4− chain with two H
2en
2+ cations. Structure of
2 (right): polyhedral structure of the layers I and II seen along [1
0
0] (
c-axis is vertical).
[Display omitted]
► 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
2O
8
4− chains and H
2en
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
3 molecule and NH
4
+ cations.