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Published on: December 29, 2016
The first lead cobalt phosphite, PbCo2(HPO3)3
Vadim M Kovrugin1, Marie Colmont2, Oleg I Siidra3
1Unité de Catalyse et Chimie du Solide (UCCS), UMR 8181 CNRS, Université Lille 1 Sciences et Technologies, 59655 Villeneuve d'ASCQ, France. kovrugin_vm@hotmail.com olivier.mentre@ensc-lille.fr and Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, 199034 St. Petersburg, Russian Federation and Laboratoire de Réactivité et Chimie des Solides (LRCS), UMR 7314 CNRS, Université de Picardie Jules Verne, 80039 Amiens Cedex, France.
Abstract:
Single crystals of a new lead cobalt phosphite, PbCo2(HPO3)3, have been synthesized using mild hydrothermal techniques and characterized by X-ray diffraction analysis, SQUID magnetic measurements, IR spectroscopy, UV/vis spectroscopy, thermogravimetric analysis, and scanning electron microscopy. PbCo2(HPO3)3 crystallizes in the non-centrosymmetric (NCS) R3m space group, a = 5.3145(15) Å, c = 25.494(7) Å, V = 623.6(4) Å3. The crystal structure of PbCo2(HPO3)3 is based upon 2D heteropolyhedral blocks built up from Co2O9 octahedral dimers and HPO3 pseudo-tetrahedra. Lead cations reside in the interlayer space of the structure. Here, the NCS character results reasonably from the cooperative Pb2+ lone electron pair arrangements, by analogy to the centrosymmetric compound (NH4)2Co2(HPO3)3 with similar but disordered blocks. A local twisting of specific HPO3 groups arises due to unreasonably short HH contacts between two phosphite oxoanions. In terms of the magnetic behavior, the new PbCo2(HPO3)3 phase demonstrates weak antiferromagnetic interactions inside the Co2O9 dimers between cobalt ions as expected from the phosphite μ-O bridges.
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