Investigations on solid chlorine dioxide: temperature-dependent crystal structure, IR spectrum, and magnetic susceptibility

Abstract

Single crystals of chlorine dioxide were grown in situ on a four-circle diffractometer, and the crystal structures were solved at five different temperatures (-75, -90, -110, -130, and -150 °C). At -150 °C, the crystal system, space group, unit cell parameters, and R factor are as follows: orthorhombic, Pbca, a -10.767 (12) k,b = 6.654 (3) Á, c = 5.518 (1) Á, V = 395.29 (48) Á3, Z = 8, R = 0.024. In the solid state, the C102 molecules associate to form weakly bonded dimers which are "head to tail" with respect to one Cl-O bond. The intermolecular interaction was confirmed by magnetic measurements, which show a steep decrease to negative values below -93 °C, and by IR spectroscopy.

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…The Cl−O bond lengths of the investigated salts range from 1.384(4) to 1.418(4) Å (Table 2) and are comparable to the Cl−O bond length of 1.418(2) Å determined from the microwave spectrum of gaseous ClO 2 F [128–130] . They are much shorter than in solid ClO 2 (1.471(1) and 1.476(1) Å at 123 K) [131] . The observed O−Cl−O angles range from 117.37(10) to 119.65(10)°, which is to be expected from the VSEPR model, which predicts an angle below 120° for such a species.…”

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“…The IR spectrum of the (OClO) 2 dimer : In the solid state, OClO forms weakly bound dimers as depicted of C i symmetry with the following structural parameters 13. These dimers partially survive sublimation at −120 °C and can be trapped in a matrix within a few milliseconds.…”

“…11 °C) crystallizes at −59 °C and the yellow solid becomes diamagnetic at −84 °C 13. The weakly bound dimers in the solid state have been structurally characterized,13, 14 studied in the matrix by IR spectroscopy5 and are the subject of theoretical calculations 15. Scrambling of oxygen atoms between the isotopomers Cl 16 O 2 and Cl 18 O 2 occurs in the liquid state, presumably by dimer formation 16…”

Increased-Valence Structures for Qualitative Valence-Bond Representations of Electronic Structure for Electron-Rich Molecules

“…(a) OClOClO 2 , to demonstrate that the existence of long intermolecular OϪCl bonds between the two ClO 2 moieties [58] is associated [55] with the presence of a ClϪO threeelectron bond in each of these moieties.…”