Hydrothermal synthesis and structural characterization of three reduced phosphomolybdates

Abstract

Three reduced molybdenum(V) phosphates, Na₂[H₂DaHex]_4.5[H₃O]{Mn[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·2H₂O (1), [H₂DaHex]₄[Zn(H₂O)]₂{Zn[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·6H₂O (2), and [H₂DaHex]_3.5[Cd(H₂O)₂]_1.5[Cd(H₂O)]{Cd[Mo₆O₁₂(OH)₃(HPO₄)₂(PO₄)₂]₂}·3.5H₂O (3) (DaHex = 1,6-diaminylhexane), were hydrothermally synthesized by using the same organic template (DaHex) and characterized by elemental analysis, IR, TGA, powder XRD, and single-crystal X-ray diffraction. Crystallographic analysis reveals that the compounds contain M[P₄Mo₆]₂ (M = Mn for 1, Zn for 2, Cd for 3) polyanions, which are further connected by various metal ions to form different topological structures. In 1, the cluster anion Mn[P₄Mo₆]₂ is discrete. For 2 and 3, M[P₄Mo₆]₂ (Zn for 2, Cd for 3) clusters are linked by transition metal ions to form different infinite chains. Then, all the 1-D chains are further packed into 3-D supramolecular structures via hydrogen-bonding interactions. The formations of 1, 2, and 3 demonstrate that not only organic templates, but transition metal ions also play very important roles in the M-P₄Mo₆ system.

Keywords:

• Hydrothermal synthesis
• Phosphomolybdates
• Crystal structure
• 1-D chain

Supplementary material

CCDC-922341, 922342, and 922343 contain the supplementary crystallographic data for 1, 2, and 3. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1E2, UK; Fax: [phone]; or E-mail: [email protected].

Acknowledgment

We thank the National Natural Science Foundation of China (20971068) and Jiangsu Province (Grant BK2012823) for financial support.