Packing incentives and a reliable N–H⋯N–pyridine synthon in co-crystallization of bipyridines with two agrochemical actives

Nauha, Elisa; Kolehmainen, Erkki; Nissinen, Maija

doi:10.1039/c1ce05730h

Cited by 38 publications

(28 citation statements)

References 24 publications

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“…Hydrogen bonding is one of the key interactions in the field of crystal engineering; the directional and predictable nature of the formation of hydrogen bonds has allowed the controlled growth of supramolecular assemblies in a range of areas, including pharmaceuticals (Schultheiss & Newman, 2009), porosity (Bojdys et al, 2011) and agrochemicals (Nauha et al, 2011). While salt formation is a well-established route for developing new solid forms of, for example, pharmaceuticals, with modified physical properties (Childs et al, 2007), the charge-assisted hydrogen bond is a much less studied interaction as a tool in crystal engineering (Ward, 2005).…”

Section: Introductionmentioning

confidence: 99%

Utilizing proton transfer to produce molecular salts in bromanilic acid substituted-pyridine molecular complexes – predictable synthons?

et al. 2013

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Controlled introduction of proton transfer into the design of a series of molecular complexes is described, delivering the systematic production of ionic molecular complexes (molecular salts). The controlled production of molecular salts has relevance as a potential strategy in the design of pharmaceutical materials. In nine molecular complexes consisting of bromanilic acid with the N-heterocyclic compounds 2-, 3- and 4-picoline [bis(2/3/4-methylpyridinium) 2,5-dibromo-3,6-dioxocyclohexa-1,4-diene-1,4-diolate, 2C6H8N(+)·C6Br2O4(2-)], 2,3-, 2,4-, 2,5- and 3,5-lutidine [2,3/2,4/2,5/3,5-dimethylpyridinium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate, C7H10N(+)·C6HBr2O4(-)], and 3-bromo-4-methylpyridine [3-bromo-4-methylpyridinium 2,5-dibromo-4-hydroxy-3,6-dioxocyclohexa-1,4-dien-1-olate, C6H7BrN(+)·C6HBr2O4(-)] and 2-bromo-3-methylpyridine [2-bromo-3-methylpyridine-2,5-dibromo-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione (1/1), C6H6BrN·C6H2Br2O4], proton transfer occurs readily between the bromanilic acid molecule and the N heteroatom of the pyridine ring, in all cases producing a charge-assisted bifurcated N-H...O hydrogen bond. This reinforces the value of this motif as a design tool in the crystal engineering of such complexes. The protonation state (and stoichiometry) significantly affect the supramolecular synthons obtained, but 1:2 stoichiometries reliably give rise to PBP synthons and 1:1 stoichiometries to PBBP synthons (where P indicates a methylpyridine co-molecule and B a bromanilic acid molecule). The influence of halogen interactions on the wider crystal packing is also discussed, with C-H...Br and Br...O interactions the most prevalent; only one Br...Br interaction is found.

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Section: Introductionmentioning

confidence: 99%

Utilizing proton transfer to produce molecular salts in bromanilic acid substituted-pyridine molecular complexes – predictable synthons?

et al. 2013

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“…The N-H···O and N-H···S intermolecular hydrogen bond interactions form among the CBT molecules. These interactions cause the formation of molecular dimers, generating R2 2 (12) and R2 2 (14) homosynthons. The N-H···O interactions occur between the tiyoamide hydrogen of CBT atom and the oxygen atom of carbonyl group, while N-H···S interactions form between the pyrrole amine of CBT and sulphur atom of the thiocarbonyl group.…”

Section: Ilkay Gumusmentioning

confidence: 99%

“…Co-crystal of carbazole-based thiourea derivative compound with acetic acid: Crystallography and Hirs... Figure 6. The formation of R 2 2(12) and R 2 2 (14) synthon generated through N-H···S and N-H···O hydrogen bonds. Figure 7.…”

Section: Ilkay Gumusmentioning

confidence: 99%

Co-crystal of carbazole-based thiourea derivative compound with acetic acid: Crystallography and Hirshfeld surface analysis

Gümüş

2019

Sakarya University Journal of Science

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Co-crystal of the N,N´-(((3,6-dichloro-9H-carbazole-1,8-diyl)bis(azanediyl))bis(carbonothioyl))bis(2,2dimethylpropanamide) as a carbazole-based thiourea derivative (CBT) with acetic acid (AcOH) was prepared and its molecular structure examined using the single crystal X-ray diffraction study and the Hirshfeld surface analysis. The co-crystal was designed to explore the supramolecular synthons and intermolecular interactions diversity between the components of co-crystal. The analysis of the crystal structure and packing revealed that the CBT:AcOH cocrystal are formed by a strong O-H⋯S and C-H•••O hydrogen bonding interactions between components of cocrystal. In addition, its' structure is further stabilized by strong C-H•••π stacking interactions and N-H•••O and N-H•••S homosynthons between CBT molecules. The Hirshfeld surfaces and associated two-dimensional fingerprint plots of the co-crystal were also analyzed to clarify the nature of the hydrogen bond interactions and close intermolecular interactions in the crystal structure. The Hirshfeld surfaces and the associated two-dimensional fingerprint plots analysis revealed that the majority of close contacts forming supramolecular structure were associated with relatively weak interactions such as H•••H, C•••H and N•••H. So, it can be said that these interactions play a major role in molecular crystal packing.

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“…In recent years, the crystal engineering of pharmaceutical solids has achieved considerable development in the pharmaceutical industry . The design of new multicomponent solid‐state assemblies, with improved properties, based on supramolecular synthons is the main goal in this area.…”

Section: Introductionmentioning

confidence: 99%

Solid-State Supramolecular Synthesis Based on the N–H…O Heterosynthon: An Approach to Solve the Polymorphism Problem in Famotidine

Russo

Brusau

Ellena

et al. 2014

Journal of Pharmaceutical Sciences

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Packing incentives and a reliable N–H⋯N–pyridine synthon in co-crystallization of bipyridines with two agrochemical actives

Cited by 38 publications

References 24 publications

Utilizing proton transfer to produce molecular salts in bromanilic acid substituted-pyridine molecular complexes – predictable synthons?

Utilizing proton transfer to produce molecular salts in bromanilic acid substituted-pyridine molecular complexes – predictable synthons?

Co-crystal of carbazole-based thiourea derivative compound with acetic acid: Crystallography and Hirshfeld surface analysis

Solid-State Supramolecular Synthesis Based on the N–H…O Heterosynthon: An Approach to Solve the Polymorphism Problem in Famotidine

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