Solid-state chemistry of organic polyvalent iodine compounds. VI. The crystal structure and topotactic hydrolysis of 3-oxo-3H-2,1-benzoxiodol-1-yl o-fluorobenzoate
Abstract
3-Oxo-3H-2,1-benzoxiodol-1-yl o-fluorobenzoate (IIIc) is formed as a topotactically aligned crystal structure when single crystals of its dibenzoyl peroxide isomer thermally decompose at room temperature. Independently, it has been found that single crystals of IIIc grown from solvents are hydrolyzed to o-iodosobenzoic acid, II, and o-fluorobenzoic acid after ∼4 weeks in a moist atmosphere at ∼45°C. II is formed topotactically in a conservatively twinned arrangement in which the (100) planes of the equally present twin members are parallel to (001) of IIIc. In addition, the 4 Å b axes of the twin members align with the 4 Å a axis of IIIc. Other examples of topotactic hydrolyses resulting in twinned arrangements of II are cited in reference to the novel possibility that the favored mode of alignment (the specific topotaxy between the reactant and one twin member) is one which, when augmented by conservative twinning, results in a favorable interphase between the conservatively twinned members. The transformation IIIc → II and more than 20 other corroborating examples of topotaxy in our studies lead us to expect the alignment of 4 Å axes whenever they are present in both the reactant and product of topotactic transformations involving comparable aromatic molecules. The crystal structure of IIIc (C 14H 8IFO 4), a = 4.08, b = 12.00, c = 26.25 Å, β = 90.5°, Z = 4, {P2 1}/{c} (refined to R = 0.10 for 453 photographically recorded intensities) consists of chains of transoid "dimers" similar to those previously observed in structures of closely related derivatives.
- Publication:
-
Journal of Solid State Chemistry France
- Pub Date:
- January 1976
- DOI:
- 10.1016/0022-4596(76)90043-8
- Bibcode:
- 1976JSSCh..16..283G