Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group
Само за регистроване кориснике
2022
Аутори
Lazić, AnitaRadovanović, Lidija
Gak Simić, Kristina
Rogan, Jelena
Janjić, Goran
Trišović, Nemanja
Đorđević, Ivana
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Two spirohydantoin derivatives, 3-(4-chlorobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (1) and 3-(4-bromobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (2), were synthesized and analyzed by single crystal X-ray diffraction, DFT and QTAIM calculations. Simple substitution of the benzoyl unit gave rise to different crystal structures. In 1, a parallel stack along the b-axis with alternating perpendicular separation is formed, while in 2 the R46(32) nets are joined together to form stacks which enclose linear channels. Hierarchical development of these crystal structures was analyzed through dimeric motifs associated with the presence of intermolecular interactions. By including the previously reported structurally-related spirohydantoin derivatives, we created a set of structures which enabled us to evaluate substituent effects on their conformational preferences, i.e., widening of the dihedral angle between the hydantoin and substituted benzoyl unit when going from F to Br. A conformatio...nal search revealed that the value of the torsion angle N3-C11-C12-C13 can be regarded as a compromise between the extended conjugation between the carbonyl and phenyl group and intramolecular C-H⋯O interaction between these two groups. This intramolecular effect is more pronounced on the torsion angle C2-N3-C11-C12, which defines the relative orientation between the hydantoin ring and the carbonyl bridge. The present work may provide a basis for design of new cyclohexane-5-spirohydantoins with potential for pharmaceutical applications both at the molecular and supramolecular level.
Извор:
CrystEngComm, 2022, 24, 22, 4106-4119Издавач:
- Royal Society of Chemistry
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200026 (Универзитет у Београду, Институт за хемију, технологију и металургију - ИХТМ) (RS-MESTD-inst-2020-200026)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200135 (Универзитет у Београду, Технолошко-металуршки факултет) (RS-MESTD-inst-2020-200135)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200287 (Иновациони центар Технолошко-металуршког факултета у Београду доо) (RS-MESTD-inst-2020-200287)
DOI: 10.1039/d2ce00376g
ISSN: 1466-8033
WoS: 000797591300001
Scopus: 2-s2.0-85132794812
Колекције
Институција/група
Inovacioni centarTY - JOUR AU - Lazić, Anita AU - Radovanović, Lidija AU - Gak Simić, Kristina AU - Rogan, Jelena AU - Janjić, Goran AU - Trišović, Nemanja AU - Đorđević, Ivana PY - 2022 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/5169 AB - Two spirohydantoin derivatives, 3-(4-chlorobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (1) and 3-(4-bromobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (2), were synthesized and analyzed by single crystal X-ray diffraction, DFT and QTAIM calculations. Simple substitution of the benzoyl unit gave rise to different crystal structures. In 1, a parallel stack along the b-axis with alternating perpendicular separation is formed, while in 2 the R46(32) nets are joined together to form stacks which enclose linear channels. Hierarchical development of these crystal structures was analyzed through dimeric motifs associated with the presence of intermolecular interactions. By including the previously reported structurally-related spirohydantoin derivatives, we created a set of structures which enabled us to evaluate substituent effects on their conformational preferences, i.e., widening of the dihedral angle between the hydantoin and substituted benzoyl unit when going from F to Br. A conformational search revealed that the value of the torsion angle N3-C11-C12-C13 can be regarded as a compromise between the extended conjugation between the carbonyl and phenyl group and intramolecular C-H⋯O interaction between these two groups. This intramolecular effect is more pronounced on the torsion angle C2-N3-C11-C12, which defines the relative orientation between the hydantoin ring and the carbonyl bridge. The present work may provide a basis for design of new cyclohexane-5-spirohydantoins with potential for pharmaceutical applications both at the molecular and supramolecular level. PB - Royal Society of Chemistry T2 - CrystEngComm T1 - Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group EP - 4119 IS - 22 SP - 4106 VL - 24 DO - 10.1039/d2ce00376g ER -
@article{ author = "Lazić, Anita and Radovanović, Lidija and Gak Simić, Kristina and Rogan, Jelena and Janjić, Goran and Trišović, Nemanja and Đorđević, Ivana", year = "2022", abstract = "Two spirohydantoin derivatives, 3-(4-chlorobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (1) and 3-(4-bromobenzoyl)-1,3-diazaspiro[4.5]decane-2,4-dione (2), were synthesized and analyzed by single crystal X-ray diffraction, DFT and QTAIM calculations. Simple substitution of the benzoyl unit gave rise to different crystal structures. In 1, a parallel stack along the b-axis with alternating perpendicular separation is formed, while in 2 the R46(32) nets are joined together to form stacks which enclose linear channels. Hierarchical development of these crystal structures was analyzed through dimeric motifs associated with the presence of intermolecular interactions. By including the previously reported structurally-related spirohydantoin derivatives, we created a set of structures which enabled us to evaluate substituent effects on their conformational preferences, i.e., widening of the dihedral angle between the hydantoin and substituted benzoyl unit when going from F to Br. A conformational search revealed that the value of the torsion angle N3-C11-C12-C13 can be regarded as a compromise between the extended conjugation between the carbonyl and phenyl group and intramolecular C-H⋯O interaction between these two groups. This intramolecular effect is more pronounced on the torsion angle C2-N3-C11-C12, which defines the relative orientation between the hydantoin ring and the carbonyl bridge. The present work may provide a basis for design of new cyclohexane-5-spirohydantoins with potential for pharmaceutical applications both at the molecular and supramolecular level.", publisher = "Royal Society of Chemistry", journal = "CrystEngComm", title = "Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group", pages = "4119-4106", number = "22", volume = "24", doi = "10.1039/d2ce00376g" }
Lazić, A., Radovanović, L., Gak Simić, K., Rogan, J., Janjić, G., Trišović, N.,& Đorđević, I.. (2022). Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group. in CrystEngComm Royal Society of Chemistry., 24(22), 4106-4119. https://doi.org/10.1039/d2ce00376g
Lazić A, Radovanović L, Gak Simić K, Rogan J, Janjić G, Trišović N, Đorđević I. Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group. in CrystEngComm. 2022;24(22):4106-4119. doi:10.1039/d2ce00376g .
Lazić, Anita, Radovanović, Lidija, Gak Simić, Kristina, Rogan, Jelena, Janjić, Goran, Trišović, Nemanja, Đorđević, Ivana, "Unravelling conformational and crystal packing preferences of cyclohexane-5-spirohydantoin derivatives incorporating a halogenated benzoyl group" in CrystEngComm, 24, no. 22 (2022):4106-4119, https://doi.org/10.1039/d2ce00376g . .