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Chromium(V) Oxide Trichloride, and some Pentachlorido‐oxido‐chromate(V) Salts: Structures and Spectroscopic Characterization
Author(s) -
Hector Andrew L.,
Levason William,
Light Mark E.,
Reid Gillian,
Sardar Kripasindhu,
Zhang Wenjian
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300084
Subject(s) - monoclinic crystal system , orthorhombic crystal system , octahedron , crystallography , chromium , crystal structure , chemistry , molecule , chromate conversion coating , rubidium , potassium , organic chemistry
Crystalline CrOCl 3 contains [Cl 2 OCr(μ‐Cl) 2 CrOCl 2 ] molecules with two square pyramidal CrOCl 4 units sharing a common edge and with the Cr–O arranged anti , a new structure type for transition metal M O X 3 compounds. Crystals are monoclinic with space group P 2 1 / c , Z = 4, with a = 5.735(5), b = 13.738(7), c = 11.318(4) Å, α = 90°, β = 98.346(6)°, γ = 90°. Its IR and UV/Vis spectra are reported and compared with those of the C 3 v monomer found in the gas phase. Structures are also reported for M 2 [CrOCl 5 ] ( M = Cs or Rb) and show a pseudo‐octahedral anion. Cs 2 [CrOCl 5 ] adopts a K 2 PtCl 6 ‐type structure with [CrOCl 5 ] 2– ions randomly orientated, but Rb 2 [CrOCl 5 ] 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–Cl transO = 2.652(7), Cr–Cl transCl = 2.239(8)–2.342(3) Å. Corresponding Cr V oxide bromide species do not form.