On the Crystal Structure of Nitritopentamminechromium(III) Chloride.

Hansson, Margareta; Börtin, Olle; Glehn, Marianne von; Tolboe, O.; Paasiv́irta, Jaakko

doi:10.3891/acta.chem.scand.22-1689

Cited by 5 publications

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“…-28 (10) 190 ( 21) -92 ( 9) N(2) 0.2522 (11) 0.1993 (3) -0.0384 ( 6) 104 ( 7) 45 (3) 111 ( 8) 35 ( 7) 32 ( 12) 27 (4) N(3) 0.2527 (11) 0.2255 (3) 0.3600 ( 6) 58 ( 5) 36 (2) 140 ( 8) 15…”

Section: Table III Positional and Thermalmentioning

confidence: 99%

Nitrito-nitro linkage isomerization in the solid state. 2. A comparative study of the structures of nitrito- and nitropentaaminecobalt(III) dichloride

Grenthe¹,

Nordin²

1979

Inorg. Chem.

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The mechanism of the isomerization in the solid state of nitritopentaamminecobalt(III) dichloride to the thermodynamically more stable nitro compound and of the reverse photochemical nitro -* nitrito reaction have been investigated. Freshly synthesized crystals of [Co(NH3)5ONO]Cl2 and crystals of the same compound aged for 1 half-life have been used for structure determinations. The intensity data were collected by a computer-controlled diffractometer. The two structures are orthorhombic, space group P2,«6, with Z = 4. Monomeric cobalt complexes and chloride ions are linked by electrostatic forces and by a network of hydrogen bonds. The coordination around cobalt is close to octahedral, A comparison of the X-ray structures of the nitrito and nitro compounds and the changes in the powder diffractograms with time indicate that the thermal nitritonitro isomerization consists of two consecutive steps. The first step involves an intramolecular change of the coordination mode, most likely via a seven-coordinated transition state. The second step consists of a slow rearrangement which can be interpreted as a cooperative ~90°rotation of half of the number of the coordination polyhedra, or as a pseudo-C3-rotation or an intramolecular twist. The nitro -»• nitrito photoisomerization gives a nitrito compound with a structure different from the one originally synthesized. The photoreaction is probably also intramolecular, proceeding via a seven-coordinated transition state.

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“…-28 (10) 190 ( 21) -92 ( 9) N(2) 0.2522 (11) 0.1993 (3) -0.0384 ( 6) 104 ( 7) 45 (3) 111 ( 8) 35 ( 7) 32 ( 12) 27 (4) N(3) 0.2527 (11) 0.2255 (3) 0.3600 ( 6) 58 ( 5) 36 (2) 140 ( 8) 15…”

Section: Table III Positional and Thermalmentioning

confidence: 99%