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Issue 47, 2020
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Crystal structure and thermodynamic properties of dinickel diphosphate dihydrate Ni2(H2O)2[P2O7]

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Abstract

Single crystals of dinickel diphosphate dihydrate, Ni2(H2O)2[P2O7], have been synthesized by a hydrothermal method. Its structure was refined in the monoclinic P21/n space group (unit cell parameters a = 6.2517(1) Å, b = 13.7892(3) Å, c = 7.2894(2) Å, β = 94.507(2)°, V = 626.45(2) Å3, and Z = 4) based on low-temperature X-ray diffraction data until R – 0.016. Corrugated chains of NiO5(H2O) octahedra sharing edges are aligned in the [10[1 with combining macron]] direction. They are linked into a three-dimensional framework through diphosphate groups and hydrogen bonds. A detailed crystal chemical analysis of the family Me2(H2O)2[X2O7] revealed correlations between the unit-cell parameters of the isotypic transition metal phosphates and arsenates, their structural features and the sizes of structure forming cations. Despite the isolation of the cis and trans edge-sharing infinite zigzag chains of Ni-centered octahedra from each other no pronounced low dimensionality is seen in the magnetic response of Ni2(H2O)2[P2O7]. The magnetic susceptibility χ evidences a short range correlation maximum at Tmax = 11.9 K accompanied by the onset of long-range magnetic order at TN = 9.4 K. Below TN, the title compound exhibits the features of an archetype three-dimensional easy-axis antiferromagnet which experiences a sequence of spin–flop and spin–flip phase transitions. Basing on specific heat Cp and magnetization M studies, the magnetic phase diagram of Ni2(H2O)2[P2O7] has been established.

Graphical abstract: Crystal structure and thermodynamic properties of dinickel diphosphate dihydrate Ni2(H2O)2[P2O7]

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Article information


Submitted
09 Oct 2020
Accepted
06 Nov 2020
First published
09 Nov 2020

Dalton Trans., 2020,49, 17368-17374
Article type
Paper

Crystal structure and thermodynamic properties of dinickel diphosphate dihydrate Ni2(H2O)2[P2O7]

G. V. Kiriukhina, O. V. Yakubovich, L. V. Shvanskaya, Y. A. Ovchenkov, A. S. Volkov, O. V. Dimitrova, S. V. Simonov and A. N. Vasiliev, Dalton Trans., 2020, 49, 17368
DOI: 10.1039/D0DT03505J

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