Crystal structure and magnetic properties of a new layered sodium nickel hydroxide phosphate, Na sub(2)Ni sub(3)(OH) sub( 2)(PO sub(4)) sub(2)

Mixed sodium nickel hydroxide phosphate, Na sub(2)Ni sub(3)(OH) sub( 2)(PO sub(4)) sub(2), has been synthesized hydrothermally from the system NiCO sub(3)-Na sub(4)P sub(2)O sub(7)-NaCl-H sub(2)O. Its monoclinic crystal structure has been determined by single crystal X-ray diffraction: a= 14.259(5),...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2013-10, Vol.42 (41), p.14718-14725
Main Authors: Yakubovich, Olga, Kiriukhina, Galina, Dimitrova, Olga, Volkov, Anatoly, Golovanov, Alexey, Volkova, Olga, Zvereva, Elena, Baidya, Santu, Saha-Dasgupta, Tanusri, Vasiliev, Alexander
Format: Article
Language:English
Subjects:
Cationic
Crystal structure
Honeycomb
Hydroxides
Nickel
Phosphates
Polyhedrons
Sodium
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Summary:Mixed sodium nickel hydroxide phosphate, Na sub(2)Ni sub(3)(OH) sub( 2)(PO sub(4)) sub(2), has been synthesized hydrothermally from the system NiCO sub(3)-Na sub(4)P sub(2)O sub(7)-NaCl-H sub(2)O. Its monoclinic crystal structure has been determined by single crystal X-ray diffraction: a= 14.259(5), b= 5.695(2), c= 4.933(1) Aa, beta = 104.28(3) degree , space group C2/m, Z= 2, rho sub(c) = 3.816 g cm super(-3), R= 0.026. The underlying spin model has been characterized in terms of first-principles electronic structure calculations. The compound is formed by alternating layers of [NiO sub(6)] octahedra and [NaO sub(7)] polyhedra, combined in the [100] direction with tetrahedral [PO sub(4)] oxocomplexes and hydrogen bonds. The novel phase is treated as an isostructural variant of the two-dimensional potassium manganese hydroxide vanadate, K sub(2)Mn sub(3)(OH) sub(2 )(VO sub(4)) sub(2), which can be formally obtained by morphotropic substitutions of all positions in the cationic sublattice. The stripe arrangement of Ni super(2+) ions (S= 1) within [NiO sub(4)(OH) sub(2)] layers of Na sub(2)Ni sub(3)(OH) sub( 2)(PO sub(4)) sub(2) is unique in the sense that its magnetic topology places it in between widely discussed honeycomb and kagome lattices. The Na sub(2)Ni sub(3)(OH) sub( 2)(PO sub(4)) sub(2) is a low-dimensional magnet, which reaches the short-range correlation regime at T sub(max) = 38.4 K and orders antiferromagnetically at T sub(N) = 33.4 K.
ISSN:1477-9226
1477-9234
DOI:10.1039/c3dt51657a