One-pot polymorphism of nonlinear optical materials. First example of organic polytypes

Timofeeva, Tatiana V.; Нестеров, В. Н.; Dolgushin, Fedor M.; Zubavichus, Yan V.; Goldshtein, James T.; Sammeth, David M.; Clark, Ronald D.; Penn, Benjamin G.; Antipin, M. Yu.

doi:10.1016/s1463-0184(00)00046-0

Cited by 29 publications

(29 citation statements)

References 27 publications

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“…The centrosymmetric triclinic (denoted 1t) and noncentrosymmetric orthorhombic crystals (denoted 1r) were found to be in an equal ratio. The concomitant crystallization of centrosymmetric and noncentrosymmetric polymorphs is a rare phenomenon and has been studied with respect to organic nonlinear optical (NLO) materials (Timofeeva et al, 2000(Timofeeva et al, , 2003Jha et al, 2018) and 3-(3-phenyl-1H-1,2,4-triazol-5yl)-2H-1-benzopyran-2-one (Shishkina et al, 2019).…”

Section: Crystallizationmentioning

confidence: 99%

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Shishkina

Konovalova

Karpina

et al. 2020

Acta Crystallogr C Struct Chem

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The dipharmacophore compound 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole, C10H11N5O, was studied on the assumption of its potential biological activity. Two concomitant polymorphs were obtained on crystallization from isopropanol solution and these were thoroughly studied. Identical conformations of the molecules are found in both structures despite the low difference in energy between the four possible conformers. The two polymorphs differ crucially with respect to their crystal structures. A centrosymmetric dimer formed due to both stacking interactions of the `head-to-tail' type and N—H...N(π) hydrogen bonds is the building unit in the triclinic structure. The dimeric building units form an isotropic packing. In the orthorhombic polymorphic structure, the molecules form stacking interactions of the `head-to-head' type, which results in their organization in a column as the primary basic structural motif. The formation of N—H...N(lone pair) hydrogen bonds between two neighbouring columns allows the formation of a double column as the main structural motif. The correct packing motifs in the two polymorphs could not be identified without calculations of the pairwise interaction energies. The triclinic structure has a higher density and a lower (by 0.60 kcal mol−1) lattice energy according to periodic calculations compared to the orthorhombic structure. This allows us to presume that the triclinic form of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole is the more stable.

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Section: Crystallizationmentioning

confidence: 99%

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Shishkina

Konovalova

Karpina

et al. 2020

Acta Crystallogr C Struct Chem

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“…The average distance between the molecular planes and the overlapping atoms are: 4/5, 3.51 (2) Å ; 3/5, 3.23 (7) Å . (Verma & Krishna, 1966), but recently Timofeeva et al (2000Timofeeva et al ( , 2003 reported two examples of organic polytypes, 1,1dicyano-4-(4-dimethylaminophenyl)-1,3-butadiene and 3methoxydicyanovinylbenzene, the first of which has two polytypic forms and the second of which has three polymorphic forms, two of which are polytypic. More recently, Parrish et al (2008) have reported five polymorphs of picryl bromide which are all polytypes of each other.…”

Section: Related Workmentioning

confidence: 99%

Four polymorphs (polytypes) of 5,6-dimethylbenzofurazan 1-oxide

Britton

Young

Noland

et al. 2012

Acta Crystallogr Sect B

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5,6-Dimethylbenzofurazan 1-oxide (Me2BF), C(8)H(8)N(2)O(2), occurs in four polymorphic forms that are polytypes of each other. Each polymorph of Me2BF contains molecules disordered about pseudo-twofold axes and arranged head-to-tail in ribbons, with the ribbons forming approximately planar layers held together by weak C-H···N and C-H···O interactions. Adjacent layers interact in different ways in the different polymorphs. In addition to twinning in the individual polymorphs, four examples of allotwining, that is, oriented overgrowths between different polymorphs, were found.

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“…Having come across some fundamentally different systems where allotwinning is realised in the infinite molecular chains of Sb 3 O 4 I (Hugonin et al, 2009) and the 1:1 co-crystals of sulfadimidine and 4-amino salicylic acid (Christensen, 2013), we infer that this phenomenon may be more common than the number of reported examples would suggest. Examples of organic polytype structures have been reported (Timofeeva et al, 2000(Timofeeva et al, , 2003Parrish et al, 2008;Britton et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Allotwinning in a molecular crystal: (1R,3S)-dimethyl 2-oxocyclohexane-1,3-dicarboxylate

Jahangiri

Fleckhaus

Lidin

et al. 2013

Acta Crystallogr Sect B

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Two polytypic modifications of (1R,3S)-dimethyl 2-oxocyclohexane-1,3-dicarboxylate intergrow to form allotwins. One phase shows monoclinic symmetry, Cc, while the other is orthorhombic Pmc21. The structures may be considered as two different modes of superstructure ordering of an underlying, disordered structure. Considered in the same metrically orthorhombic unit cell a = 37.8883, b = 4.7233, c = 11.6835 Å, the two can be conveniently distinguished by their non-standard centering, Cc being represented as Xc with the centering vectors (0 0 0); (½ 0 ½); (¼ ½ ¾); (¾ ½ ¼); and Pmc21 as Xmc21 with the centering vectors (0 0 0); (½ 0 0). The difference between the allotwin domains lies only in the relationship between next-nearest neighbors along the stacking direction 100 and hence the conformations and packing efficiencies are identical for both phases and all three domains. The stacking sequences for the two phases correspond to ABAB for the orthorhombic stacking and ABA'B'/AB'A'B for the two (equivalent) monoclinic stackings. The monoclinic phase dominates comprising ca 80% of the total volume. Within the monoclinic phase, the ratio between the two possible orientations is highly unbalanced (6:1) indicating relatively large domains. The allotwinning detected in this sample may appear exotic in molecular compounds, but we suggest that the rarity of such examples in the literature is a reflection of the paucity of software that can identify and handle such cases. It is easy to overlook the possibility that a complex diffraction pattern originates from allotwinning and assume that normal mono-component twinning is the cause. The underlying mechanism in this case is the formation of two-dimensional layers of molecules that allow for two equivalent, but in terms of absolute geometry, different, ways of stacking.

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One-pot polymorphism of nonlinear optical materials. First example of organic polytypes

Cited by 29 publications

References 27 publications

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Four polymorphs (polytypes) of 5,6-dimethylbenzofurazan 1-oxide

Allotwinning in a molecular crystal: (1R,3S)-dimethyl 2-oxocyclohexane-1,3-dicarboxylate

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