Step-wise dis-assembly of trimesic acid: mono- and bis(methanol) solvates

Abstract

Single crystal X-ray structures of methanol solvates of trimesic acid provide an insight into the step-wise dis-assembly of this strongly hydrogen-bonded acid through the disruption of acidacid head-to-tail dimer motifs by alcohols.Trimesic acid (benzene-1,3,5-tricarboxylic acid, H 3 TMA) is amongst the most used members of the benzenepolycarboxylic acid family, favoured by the supramolecular chemist for their numerous divergent carboxyl groups, useful in the creation of extensive arrays through hydrogen bonding 1 and metal-coordination bonds. 2 The inclusion of solvent molecules into the "chicken wire" solid state structure of H 3 TMA 1a,3 received interest, notably from Herbstein, in the 1970s and 1980s, 1a,1c,4 with more recent work investigating the formation of channels in H 3 TMA solvates utilising polyaromatic compounds as templates. 5 While the crystallographic study of solvates was initially hindered by rapid desolvation at room temperature, 6 the advent of low temperature systems for Xray data collection now allows for more precise structural determinations. 4e The crystallisation of a methanolic solution of H 3 TMA over a period of seven days at 218 °C resulted in a mixture of colourless blocks H 3 TMA·MeOH, 1, and colourless needles H 3 TMA·2MeOH, 2, the latter being the major component. Both 1 and 2 were analysed using single-crystal X-ray diffraction † and were found to possess tape structures, maintained by strong O-H…O hydrogen bonding interactions. 7

Supramolecular hydrogen bonding of [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]palladium(II) in the presence of competing solvents

“…In the presence of alcohols (although they represent relatively weak hydrogen-bond donors and acceptors), the supramolecular hydrogen bonding of organic carboxylic acids does not always preserve the (COOH) 2 intermolecular synthon. On some occasions, incorporation of the hydroxy group into the intermolecular hydrogen-bonding scheme has been observed (Dale et al, 2004). Not surprisingly, the same phenomenon characterizes the hydrogen-bonded assembly in (I).…”

Fluorine determines the aggregation of pyridines. Experimentversustheory

“…We have previously reported 1:1 and 1:2 TMA:MeOH solvates that demonstrated the stepwise dissolution of TMA via disruption by methanol of the R 2 2 (8) head-to-tail carboxylic acid dimer H-bonding pattern. This common pattern is seen in many pure carboxylic acids including the three-fold interpenetrated honeycomb lattice of pure TMA [1]. The disruption occurs via the insertion of an alcohol OH group into the R 2 2 (8) ring to generate an expanded R 3 3 (10) motif.…”

Benzene-1,3,5-tricarboxylic acid–1,2-bis(1,2,4-triazol-4-yl)ethane–water (4/1/2)

“…For related literature, see: Althoff et al (2006); Dale & Elsegood (2004); Dale et al (2004); Dorn et al (2005Dorn et al ( , 2006; Du et al (2005); Etter et al (1990); Fan et al (2005); Goldberg & Bernstein (2007); Janiak (2000); Shattock et al (2005); Turner et al (2008); ; Wisser & Janiak (2007a,b).…”

“…Hydrogen bonding within crystalline systems is of timely interest for the rational design of organized solids (Althoff et al, 2006;Dorn et al, 2005;Dorn et al 2006;Wisser & Janiak, 2007a,b). Co-crystallization of benzene-di, -tri-andtetra-carboxylic acids, like trimesic acid or hemimellitic acid with solvent molecules or nitrogen bases is the focus of permanent and recent research activities (Dale & Elsegood, 2004;Dale et al, 2004;Du et al, 2005;Fan et al, 2005;Goldberg & Bernstein, 2007;Shattock et al, 2005;Turner et al, 2008;. Co-crystal structures of trimesic acid (benzene-1,3,5-tricarboxylic acid) have been reported with 2,5-bis(3-and 4-pyridyl)-1,3,4-oxadiazole (twodimensional sheet, Du et al, 2005), 3,6-bis(3′-pyridyl)-1,2,4,5-tetrazine (one-dimensional ribbon, , 1,2-bis(4-pyridyl)ethane (two-dimensional 6,3-and 10,3-network with interpenetration, Shattock et al, 2005), mono-and bis(methanol) (one-dimensional tape, Dale et al, 2004), acetic acid (Goldberg & Bernstein, 2007) and dihydrate (threedimensional network, Fan et al, 2005).…”