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Sardar, K.
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article
Chromium(V) oxide trichloride, and some pentachlorido-oxido-chromate(V) salts: structures and spectroscopic characterization
Abstract
Crystalline CrOCl3 contains [Cl2OCr(?-Cl)2CrOCl2] molecules with two square pyramidal CrOCl4 units sharing a common edge and with the Cr–O arranged anti, a new structure type for transition metal MOX3 compounds. Crystals are monoclinic with space group P21/c, Z = 4, with a = 5.735(5), b = 13.738(7), c = 11.318(4) Å, ? = 90°, ? = 98.346(6)°, ? = 90°. Its IR and UV/Vis spectra are reported and compared with those of the C3v monomer found in the gas phase. Structures are also reported for M2[CrOCl5] (M = Cs or Rb) and show a pseudo-octahedral anion. Cs2[CrOCl5] adopts a K2PtCl6-type structure with [CrOCl5]2– ions randomly orientated, but Rb2[CrOCl5] is orthorhombic with space group Pnma with a = 13.6471(7), b = 9.9175(5), and c = 6.9562(4) Å. Rietveld refinement of the data on the rubidium salt gave Cr–O = 1.628(1), Cr–CltransO = 2.652(7), Cr–CltransCl = 2.239(8)–2.342(3) Å. Corresponding CrV oxide bromide species do not form