language: en

DOI: 10.1002/zaac.200700523

Structural Investigations and Thermal Behavior of (NH 4 )[Cr(C 2 O 4 ) 2 ] · 2H 2 O

V. Kahlenberg a, *, W. Wertl a , A. Kremenovic ´ , P. Schuster c , and H. Schottenberger c
Innsbruck/Austria,
a Institute of Mineralogy and Petrography and c Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck
b Belgrade/Serbia,
Faculty of Mining and Geology, Laboratory of Crystallography, University of Belgrade

[Received November, 16 th 2007.]

Abstract. Single crystals of ammonium chromium(III) dioxalate dihydrate (or ammonium diaquo bis(μ-oxalato)chromate(III)) have been obtained from aqueous solution of oxalic acid and ammonium dichromate. A pale violet crystal of good optical quality was used for the structure determination at 񮽙100(2) and 25(2) °C, respectively. The basic crystallographic data for the low temperature data set are as follows: monoclinic, space group C2/m, a 񮽙 6.597(2) A b 񮽙 7.301(2) A c 񮽙 9.983(3) A β 񮽙 92.32(2)°, V 񮽙 480.5(2) A ˚ . The structure was solved by direct methods and refined (using anisotropic displacement parameters for all non-hydrogen atoms) to a final residual of R1 񮽙 0.032 for 503 independent observed reflections (I>2σ(I)). The compound is isotypic with the corresponding rubidium salt. The structure is built up from alternating layers parallel to (001) containing (NH 4 ) 񮽙 ions or Cr(C 2 O 4 ) 2 (H 2 O) 2 octahedra, respectively. The corners of the octahedra consist of four O atoms from two oxalate groups and two additional water molecules. The ammonium cations (occupying Wyckoff-site 2a) are disordered among two possible orientations. They provide linkage between different octahedral layers by hydrogen bridging. The water molecules in turn form hydrogen bridges with adjacent octahedra within the same layer. Further structural characterization included infrared spectroscopy. According to DTA/TG experiments the present compound shows several thermal processes in the range between room temperature and 900 °C.

Keywords: Chromium; Ammonium chromium(III) dioxalate dihy- drate; Crystal structures; Thermal analysis Introduction