The crystal structures of trimesic acid, its hydrates and complexes. IV. Trimesic acid–dimethyl sulphoxide

Abstract

C9H6Os. C2HsSO iS monoclinic, with a = 8.743 (4), b = 6.803 (4), c = 10-677 (5) A, fl = 96.24 (4) °, z = 2, space group P2~ or P2~/m. The structure was refined to R = 8.4% (in space group P2 0 for 1751 counter reflections. There are hydrogen bonds both between pairs of TMA molecules (but carboxylic acid dimers are not formed) and between TMA and DMSO molecules. O atoms of the DMSO molecules are part of the walls of channels formed by the TMA molecules, while the methyl groups of the DMSO molecules lie within the channels; the lone pair of the DMSO S atom is stereochemically active in the sense that it appears to influence the intermolecular arrangement.1613

The Chemistry of Porous Organic Molecular Materials

“…However, TMA was recently revisited from a fresh perspective, after CSP calculations revealed an energetically stable, low-density polymorphic form, referred to as the δ-polymorph, which remained hidden, despite many groups studying the crystallization behavior of this molecule over the last 50 years. [285][286][287][288][289][290][291][292][293][294] In this study, a high throughput crystallization workflow was developed to screen 280 binary solvent crystallization conditions, of which less than 2% either yielded this δ-polymorph directly, or gave a structure that transformed to this form after activation of the crystal pores. [295] Unlike the nonporous α-polymorph reported by Duchamp et al, the computationally-identified δpolymorph of TMA had a SA BET 910 m 2 g -1 at 77.3 K. CSP was also used by Hisaki et al (Tp-apo, Figures 13 and 16) [296] to predict the structure of a carboxylic acid-based HOF material, that could not be determined directly from X-ray data alone.…”

“…The structure Duchamp reported is nonporous due to the nonplanar hydrogen‐bonded interactions between TMA molecules causing the hydrogen‐bonded networks to interlock. However, TMA was recently revisited from a fresh perspective, after CSP calculations revealed an energetically stable, low‐density polymorphic form, referred to as the δ−polymorph, which remained hidden, despite many groups studying the crystallization behavior of this molecule over the last 50 years 285–294. In this study, a high throughput crystallization workflow was developed to screen 280 binary solvent crystallization conditions, of which less than 2% either yielded this δ‐polymorph directly, or gave a structure that transformed to this form after activation of the crystal pores 295.…”

Trimesic acid dimethyl sulfoxide solvate: space group revision

“…For the first report on the title solvate structure, see: Herbstein et al (1978). For the use of trimesic acid as a building block for supramolecular networks, see: Almeida Paz & Klinowski (2004).…”

“…The clathration ability of TMA allowed to prepare a number of solvate structures, including hydrates, and consequently determination of these structures. Among them, the dimethylsulfoxide (DMSO) solvate has been reported already 30 years ago (Herbstein et al, 1978). The data were collected at room temperature with Mo-Kα radiation.…”

“…The structure of the title solvate, C 9 H 6 O 6 ÁC 2 H 6 OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978). Acta Cryst.…”