The crystal structures of three clozapinium salts: Different molecular configurations, and supramolecular assembly in one, two and three dimensions

Manpreet Kaur, Jerry P. Jasinski*, Hemmige S. Yathirajan, Channappa N. Kavitha, Christopher Glidewell, W. T A Harrison (Editor)

*Corresponding author for this work

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Abstract

The structures of three salts derived from clozapine, 8-chloro-11-(4-methyl-piperazin-1-yl)-5H-dibenzo[b,e][1,4]diazepine, are reported, namely, clozapinium 3,5-dinitrobenzoate dimethyl sulfoxide monosolvate, C18H20ClN4+-C7H3N2O6-·C2H6OS, (I), where the dimethyl sulfoxide component is disordered over two sets of atomic sites having occupancies 0.627 (2) and 0.373 (2); clozapinium hydrogen maleate 0.21-hydrate, C18H20ClN4+·C4H3O4-·0.21H2O, (II), and clozapinium 2-hydroxybenzoate, C18H20ClN4+·C7H5O3-, (III). In all three salts, the protonation site is the methylated N atom of the piperazine ring, and the dimensions and conformations of the fused tricyclic system are very similar. However, differences are apparent in the piperazine component: in both compounds (II) and (III), the unprotonated N atom of this ring has a pyramidal geometry, but in compound (I) this atom has a planar geometry. In compound (III), both N-substituents in this ring occupy equatorial sites, but in compound (II) the fused tricyclic system occupies an axial site of the piperazine ring. The independent components of compound (I) are linked within the selected asymmetric unit by a combination of N - H⋯O and C - H⋯O hydrogen bonds, and these hydrogen-bonded aggregates are linked into chains by an aromatic π- π stacking interaction. In compound (II), the components are linked into sheets by a combination of O - H⋯O, N - H⋯O and C - H⋯O hydrogen bonds, and in compound (III), a combination of N - H⋯O, C - H⋯O and C - H⋯N hydrogen bonds links the components into a three-dimensional framework structure. Comparisons are made with some similar compounds.

Original languageEnglish
Pages (from-to)406-413
Number of pages8
JournalActa Crystallographica Section E: Structure Reports Online
Volume71
Issue number4
Early online date25 Mar 2015
DOIs
Publication statusPublished - 1 Apr 2015

Fingerprint

Hydrogen bonds
Dimethyl sulfoxide
Salts
assembly
Crystal structure
Dimethyl Sulfoxide
salts
Atoms
crystal structure
configurations
rings
Hydroxybenzoates
Hydrogen
hydrogen bonds
Geometry
Clozapine
Protonation
Hydrates
Conformations
maleates

Keywords

  • Clozapinium
  • Crystal structure
  • Hydrogen bonding
  • Molecular configuration
  • Supramolecular assembly

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Materials Science(all)
  • Chemistry(all)

Cite this

The crystal structures of three clozapinium salts : Different molecular configurations, and supramolecular assembly in one, two and three dimensions. / Kaur, Manpreet; Jasinski, Jerry P.; Yathirajan, Hemmige S.; Kavitha, Channappa N.; Glidewell, Christopher; Harrison, W. T A (Editor).

In: Acta Crystallographica Section E: Structure Reports Online, Vol. 71, No. 4, 01.04.2015, p. 406-413.

Research output: Contribution to journalArticle

Kaur, Manpreet ; Jasinski, Jerry P. ; Yathirajan, Hemmige S. ; Kavitha, Channappa N. ; Glidewell, Christopher ; Harrison, W. T A (Editor). / The crystal structures of three clozapinium salts : Different molecular configurations, and supramolecular assembly in one, two and three dimensions. In: Acta Crystallographica Section E: Structure Reports Online. 2015 ; Vol. 71, No. 4. pp. 406-413.
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abstract = "The structures of three salts derived from clozapine, 8-chloro-11-(4-methyl-piperazin-1-yl)-5H-dibenzo[b,e][1,4]diazepine, are reported, namely, clozapinium 3,5-dinitrobenzoate dimethyl sulfoxide monosolvate, C18H20ClN4+-C7H3N2O6-·C2H6OS, (I), where the dimethyl sulfoxide component is disordered over two sets of atomic sites having occupancies 0.627 (2) and 0.373 (2); clozapinium hydrogen maleate 0.21-hydrate, C18H20ClN4+·C4H3O4-·0.21H2O, (II), and clozapinium 2-hydroxybenzoate, C18H20ClN4+·C7H5O3-, (III). In all three salts, the protonation site is the methylated N atom of the piperazine ring, and the dimensions and conformations of the fused tricyclic system are very similar. However, differences are apparent in the piperazine component: in both compounds (II) and (III), the unprotonated N atom of this ring has a pyramidal geometry, but in compound (I) this atom has a planar geometry. In compound (III), both N-substituents in this ring occupy equatorial sites, but in compound (II) the fused tricyclic system occupies an axial site of the piperazine ring. The independent components of compound (I) are linked within the selected asymmetric unit by a combination of N - H⋯O and C - H⋯O hydrogen bonds, and these hydrogen-bonded aggregates are linked into chains by an aromatic π- π stacking interaction. In compound (II), the components are linked into sheets by a combination of O - H⋯O, N - H⋯O and C - H⋯O hydrogen bonds, and in compound (III), a combination of N - H⋯O, C - H⋯O and C - H⋯N hydrogen bonds links the components into a three-dimensional framework structure. Comparisons are made with some similar compounds.",
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AU - Kaur, Manpreet

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AU - Yathirajan, Hemmige S.

AU - Kavitha, Channappa N.

AU - Glidewell, Christopher

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N2 - The structures of three salts derived from clozapine, 8-chloro-11-(4-methyl-piperazin-1-yl)-5H-dibenzo[b,e][1,4]diazepine, are reported, namely, clozapinium 3,5-dinitrobenzoate dimethyl sulfoxide monosolvate, C18H20ClN4+-C7H3N2O6-·C2H6OS, (I), where the dimethyl sulfoxide component is disordered over two sets of atomic sites having occupancies 0.627 (2) and 0.373 (2); clozapinium hydrogen maleate 0.21-hydrate, C18H20ClN4+·C4H3O4-·0.21H2O, (II), and clozapinium 2-hydroxybenzoate, C18H20ClN4+·C7H5O3-, (III). In all three salts, the protonation site is the methylated N atom of the piperazine ring, and the dimensions and conformations of the fused tricyclic system are very similar. However, differences are apparent in the piperazine component: in both compounds (II) and (III), the unprotonated N atom of this ring has a pyramidal geometry, but in compound (I) this atom has a planar geometry. In compound (III), both N-substituents in this ring occupy equatorial sites, but in compound (II) the fused tricyclic system occupies an axial site of the piperazine ring. The independent components of compound (I) are linked within the selected asymmetric unit by a combination of N - H⋯O and C - H⋯O hydrogen bonds, and these hydrogen-bonded aggregates are linked into chains by an aromatic π- π stacking interaction. In compound (II), the components are linked into sheets by a combination of O - H⋯O, N - H⋯O and C - H⋯O hydrogen bonds, and in compound (III), a combination of N - H⋯O, C - H⋯O and C - H⋯N hydrogen bonds links the components into a three-dimensional framework structure. Comparisons are made with some similar compounds.

AB - The structures of three salts derived from clozapine, 8-chloro-11-(4-methyl-piperazin-1-yl)-5H-dibenzo[b,e][1,4]diazepine, are reported, namely, clozapinium 3,5-dinitrobenzoate dimethyl sulfoxide monosolvate, C18H20ClN4+-C7H3N2O6-·C2H6OS, (I), where the dimethyl sulfoxide component is disordered over two sets of atomic sites having occupancies 0.627 (2) and 0.373 (2); clozapinium hydrogen maleate 0.21-hydrate, C18H20ClN4+·C4H3O4-·0.21H2O, (II), and clozapinium 2-hydroxybenzoate, C18H20ClN4+·C7H5O3-, (III). In all three salts, the protonation site is the methylated N atom of the piperazine ring, and the dimensions and conformations of the fused tricyclic system are very similar. However, differences are apparent in the piperazine component: in both compounds (II) and (III), the unprotonated N atom of this ring has a pyramidal geometry, but in compound (I) this atom has a planar geometry. In compound (III), both N-substituents in this ring occupy equatorial sites, but in compound (II) the fused tricyclic system occupies an axial site of the piperazine ring. The independent components of compound (I) are linked within the selected asymmetric unit by a combination of N - H⋯O and C - H⋯O hydrogen bonds, and these hydrogen-bonded aggregates are linked into chains by an aromatic π- π stacking interaction. In compound (II), the components are linked into sheets by a combination of O - H⋯O, N - H⋯O and C - H⋯O hydrogen bonds, and in compound (III), a combination of N - H⋯O, C - H⋯O and C - H⋯N hydrogen bonds links the components into a three-dimensional framework structure. Comparisons are made with some similar compounds.

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