Temperature-induced first-order displacive phase transition of isonicotinamide-4-methoxybenzoic acid co-crystal

Chia, Tze Shyang; Quah, Ching Kheng

doi:10.1107/s2052520616019405

Cited by 3 publications

(1 citation statement)

References 46 publications

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“…Isonicotinamide is a heavily used ingredient in crystal engineering, whose multiple HB donor and acceptor sites make it an important motif in constructing a structural landscape of multicomponent cocrystals or salts. ,,,, XPS ,, spectra at the N 1s edge were used to characterize IN-based crystals. Structurally, it is an isomer of nicotinamide, with a primary amide (−CO–NH 2 ) group para substituted on the pyridine ring.…”

Section: Introductionmentioning

confidence: 99%

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

Zhang

Wang

et al. 2022

J. Phys. Chem. C

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Proton transfer (PT) in organic crystals creates localized charges and strong hydrogen bonding (HB), making the self-consistent field (SCF) calculation of core-ionized and core-excited states challenging. Today most corresponding X-ray spectral measurements are interpreted based on empirical fitting and/or chemical intuitions. Here we present a systematic quantum mechanical/molecular mechanical (QM/MM) study of N 1s X-ray photoelectron (XPS) and absorption (XAS) spectra of three isonicotinamide (IN)-based organic crystals with full (1), half (2), and no (3) protonations. A complete picture of the structure–spectroscopy relation in different crystal environments was provided, and assignments to three unprotonated (pyridinic, p; amide, a 1 and a 2) sites and one protonated (pyridinic, h) N site were clearly made. We found that including distant residues as natural population analysis (NPA) point charges can effectively enhance the SCF convergence of the core states. The size of the QM part was tuned, and with some 140–170 atoms we achieved spectral convergence that can represent the infinite crystal. At the crystal structures, simulated relative binding energies deviate ≤0.3 eV to experiments. Simulated XAS spectra agree well with experiments, and with molecular orbital analysis we interpreted the π* structures as hybrid local excitation and charge transfer states (πLE–CT *) or pure LE states (πLE *). Analyses on both spectra helped understand the PT and HB nature in such organic crystals, and a debate in XPS interpretation of 3 was resolved and its XAS assignment corrected. Further, to model the dynamical effect of the proton in 2, XPS/XAS spectra were evaluated at snapshots with varying N–H distances. A continuous picture illustrates the sensitive influence of proton position to both spectra. Reduction of the N–H distance by only 0.2 Å from the crystal structure (1.1 Å) excellently reproduced both spectra. This perturbation phenomenologically models effects of vibration from the equilibrium crystal structure and environmental temperature and pressure factors.

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Section: Introductionmentioning

confidence: 99%

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

Zhang

Wang

et al. 2022

J. Phys. Chem. C

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A positive to negative uniaxial thermal expansion crossover in an organic benzothienobenzothiophene structure

Dumitrescu

Roche

Moreau

et al. 2020

Acta Crystallogr Sect B

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Compound 6,6′-([1]benzothieno[3,2-b][1]benzothiophene-2,7-diyl)bis(butan-1-ol) (BTBT-C4OH) displays a continuous type 0 first-order isosymmetric phase transition at 200 K which is accompanied by a continuous change of the thermal expansion along the b axis from positive to negative. The equivalent isotropic atomic displacement parameters for all non-hydrogen atoms as well as all the eigenvalues of the anisotropic atomic displacement tensor show discontinuous behavior at the phase transition. The eigenvalues of the translational tensor in a rigid-body description of the molecule are all discontinuous at the phase transition, but the librational eigenvalues are discontinuous only in their temperature derivative. BTBT-C4OH displays a similar type of quasi-supercritical phase transition as bis(hydroxyhexyl)[1]benzothieno[3,2-b][1]benzothiophene (BTBT-C6OH), despite the difference in molecular packing and the very large difference in thermal expansion magnitudes.

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Temperature-induced phase transition of isonicotinamide-malonic acid (2/1) and supramolecular construct analysis of isonicotinamide structures

Chia

Quah

2018

Zeitschrift Für Kristallographie - Crystalline Materials

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The isonicotinamide-malonic acid (2/1) co-crystal salt (2IN·C3) exhibits a first-order displacive structural phase transition from low-temperature triclinic P1̅ crystal structure to high-temperature monoclinic C2/c crystal structure and vice versa at the transition temperatures of 298 (1) and 295 (1) K, respectively, as determined by variable-temperature SCXRD analysis and DSC measurements. The asymmetric unit of 2IN·C3 comprises three malonic acid molecules and six isonicotinamide molecules at the low-temperature phase, and this is reduced to a half-molecule of malonic acid and an isonicotinamide molecule in the high-temperature phase. The carboxyl and pyridinium H atoms are disordered at both phases. The observed phase transition near room temperature is triggered by the molecular displacement of the isonicotinamide molecule and the syn-anti conformational transformation of the malonic acid molecule with deviation angles of 10.4 and 11.7°, respectively, which induced an energy change of 19.1 kJ mol−1 in the molecular cluster comprising a central isonicotinamide molecule and eight neighboring molecules. However, the total interaction energy of the molecular cluster of a central malonic acid molecule and eight neighboring molecules does not change significantly upon the phase transition. The molecules of isonicotinamide structures except IN·IN+·triazole‒ form zero-dimensional finite arrays or one-dimensional chains as the primary supramolecular construct by carboxyl···pyridyl (−35.9 to −56.7 kJ mol−1) and carboxamide···carboxamide (−53.6 to −68.7 kJ mol−1) or carboxyl···carboxamide (−52.6 to −67.1 kJ mol−1) synthons.

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Temperature-induced first-order displacive phase transition of isonicotinamide-4-methoxybenzoic acid co-crystal

Cited by 3 publications

References 46 publications

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

A positive to negative uniaxial thermal expansion crossover in an organic benzothienobenzothiophene structure

Temperature-induced phase transition of isonicotinamide-malonic acid (2/1) and supramolecular construct analysis of isonicotinamide structures

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