Inorganic Chemistry, Vol.54, No.14, 7014-7020, 2015
Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba2M(VO4)(2)(OH), M = V3+, Mn3+, and Fe3+, with Interesting Jahn-Teller and Spin-Liquid Behavior
A new series of transition metal vanadates, namely, Ba2M(VO4)(2)(OH) (M = V3+, Mn3+, and Fe3+), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 degrees C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba2V(VO4)(2)(OH) is monoclinic in space group P2(1)/m, a = 7.8783(2) angstrom, b = 6.1369(1) angstrom, c = 9.1836(2) angstrom, beta = 113.07(3)degrees, V = 408.51(2) angstrom(3). The other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba2Mn(VO4)(2)(OH) analogue yielded a new understanding of the Jahn-Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Single-crystal temperature-dependent magnetic studies on Ba2V(VO4)(2)(OH) reveal a broad feature over a wide temperature range with maximum at similar to 100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.