Synthesis, Crystal Structure, and Vibrational Spectra
of M₄V₂O₃(SO₄)₄ (M = K, Rb, Cs)

V. N. Krasil’nikov, A. P. Tyutyunnik, V. G. Zubkov, I. F. Berger,
L. Ya. Perelyaeva, and I. V. Baklanova

Institute of Solid-State Chemistry, Ural Branch, Russian Academy of Sciences,
ul. Pervomaiskaya 91, Yekaterinburg, 620219 Russia

Received July 15, 2009.

Abstract—Synthesis was performed and physicochemical properties were studied for the M₄V₂O₃(SO₄)₄ com-
plexes, where M = K, Rb, or Cs. Their crystal structures were determined using the set of data from X-ray dif-
fraction and neutron diffraction studies. All compounds crystallize in a triclinic lattice (space group Z = 2)
with the parameters: a = 7.7688(2), 7.8487(1), 8.1234(1) Å; b = 10.4918(3), 10.8750(2), 11.1065(1) Å; c =
11.9783(4), 12.1336(2), and 11.8039(1) Å; = 76.600(2), 77.910(1), 79.589(1); = 75.133(2), 75.718(1),
87.939(1); = 71.285(2), 72.189(1), 75.567(1); V = 881.78(5), 945.42(3), 1014.34(2) ų for K, Rb, Cs,
respectively. The structure of M₄V₂O₃(SO₄)₄ was found to be formed by discrete complex anions
incorporating two oxygen-bridged vanadium atoms in a distorted octahedral oxygen environment. The sulfate
groups are coordinated by the vanadium atoms in the chelating mode with a large scatter of S–O interatomic
distances and OSO angles. Every VO₆ octahedron has a short terminal vanadium–oxygen bond with a length of
about 1.6 Å. The complex anions in potassium and rubidium compounds differ from that in
Cs₄V₂O₃(SO₄)₄ in the type of symmetry and mutual spatial orientation. The vibrational spectra were presented
and interpreted in line with the structural analysis data.

DOI: 10.1134/S0036023611040152

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