Chromium(V) Oxide Trichloride, and some Pentachlorido‐­oxido‐chromate(V) Salts: Structures and Spectroscopic ­Characterization. Issue 6 (14th March 2013)

• Record Type: Journal Article
• Authors: Hector, Andrew L.; Levason, William; Light, Mark E.; Reid, Gillian; Sardar, Kripasindhu; Zhang, Wenjian
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 639:Issue 6(2013)
• Page Start: 906
• Page End: 910
• Publication Date: 2013-03-14
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201300084
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Crystalline CrOCl<sub>3</sub> contains [Cl<sub>2</sub>OCr(μ‐Cl)<sub>2</sub>CrOCl<sub>2</sub>] molecules with two square pyramidal CrOCl<sub>4</sub> units sharing a common edge and with the Cr–O arranged <italic>anti</italic>, a new structure type for transition metal <italic>M</italic>O<italic>X</italic><sub>3</sub> compounds. Crystals are monoclinic with space group <italic>P</italic>2<sub>1</sub>/<italic>c</italic>, <italic>Z</italic> = 4, with <italic>a</italic> = 5.735(5), <italic>b</italic> = 13.738(7), <italic>c</italic> = 11.318(4) Å, <italic>α</italic> = 90°, <italic>β</italic> = 98.346(6)°, <italic>γ</italic> = 90°. Its IR and UV/Vis spectra are reported and compared with those of the <italic>C</italic><sub>3<italic>v</italic></sub> monomer found in the gas phase. Structures are also reported for <italic>M</italic><sub>2</sub>[CrOCl<sub>5</sub>] (<italic>M</italic> = Cs or Rb) and show a pseudo‐octahedral anion. Cs<sub>2</sub>[CrOCl<sub>5</sub>] adopts a K<sub>2</sub>PtCl<sub>6</sub>‐type structure with [CrOCl<sub>5</sub>]<sup>2–</sup> ions randomly orientated, but Rb<sub>2</sub>[CrOCl<sub>5</sub>] is orthorhombic with space group <italic>Pnma</italic> with <italic>a</italic> = 13.6471(7), <italic>b</italic> = 9.9175(5), and <italic>c</italic> = 6.9562(4) Å. Rietveld refinement of the data on the rubidium salt gave Cr–O = 1.628(1), Cr–Cl<sub>transO</sub> = 2.652(7), Cr–Cl<sub>transCl</sub> = 2.239(8)–2.342(3) Å. Corresponding Cr<sup>V</sup> oxide bromide species do not form.</p> </abstract>