Dataset Information

Syntheses, crystal structures and Hirshfeld surface analyses of four mol-ecular salts of amitriptynol.

ABSTRACT: The syntheses and crystal structures of four salts of amitriptynol (C₂₀H₂₅NO) with different carb-oxy-lic acids are described. The salts formed directly from solutions of amitriptyline (which first hydrolysed to amitriptynol) and the cor-responding acid in aceto-nitrile to form amitriptynolium [sys-tem-atic name: (3-{2-hy-droxy-tri-cy-clo[9.4.0.0^3,8]penta-deca-1(11),3,5,7,12,14-hexa-en-2-yl}pro-pyl)di-methyl-az-an-ium] 4-meth-oxy-benzoate monohydrate, C₂₀H₂₆NO⁺·C₈H₇O₃ ^-·H₂O, (I), ami-triptynolium 3,4-di-meth-oxy-benzoate trihydrate, C₂₀H₂₆NO⁺·C₉H₉O₄ ^-·3H₂O, (II), amitriptynolium 2-chloro-benzoate, C₂₀H₂₆NO⁺·C₇H₄ClO₂ ^-, (III), and amitriptynolium thio-phene-2-carboxyl-ate monohydrate, C₂₀H₂₆NO⁺·C₅H₃O₂S^-·H₂O, (IV). Compound (III) crystallizes with two cations, two anions and six water mol-ecules in the asymmetric unit. The different conformations of the amitriptynolium cations are determined by the torsion angles in the di-methyl-amino-propyl chains and the -CH₂-CH₂- bridge between the benzene rings in the tricyclic ring system, and are complicated by disorder of the bridging unit in II and III. The packing in all four salts is dominated by N-H⋯O and O-H⋯O hydrogen bonds. Hirshfeld surface analyses show that the amitriptynolium cations make similar inter-species contacts, despite the distinctly different packing in each salt.

SUBMITTER: Vinaya

PROVIDER: S-EPMC10162082 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Syntheses, crystal structures and Hirshfeld surface analyses of four mol-ecular salts of amitriptynol.

Vinaya Anil Kumar Haleyur G HG Mohan Kumar Thaluru M TM Lakshmana Beliyaiah B Basavaraju Yeriyur B YB Yathirajan Hemmige S HS Parkin Sean S

Acta crystallographica. Section E, Crystallographic communications 20230414 Pt 5

The syntheses and crystal structures of four salts of amitriptynol (C20H25NO) with different carb-oxy-lic acids are described. The salts formed directly from solutions of amitriptyline (which first hydrolysed to amitriptynol) and the cor-responding acid in aceto-nitrile to form amitriptynolium [sys-tem-atic name: (3-{2-hy-droxy-tri-cy-clo[9.4.0.03,8]penta-deca-1(11),3,5,7,12,14-hexa-en-2-yl}pro-pyl)di-methyl-az-an-ium] 4-meth-oxy-benzoate monohydrate, C20</s ...[more]

PMID: 37151840

Similar Datasets

Project description:The structures and Hirshfeld surface analysis of three salts of 1-(4-nitro-phenyl)-piperazine are discussed. In 4-(4-nitro-phen-yl)piperazin-1-ium salicylate (C10H14N3O2 +·C7H5O3 -), there are strong hydrogen bonds between cation and anion and the 4-nitro-phenyl substituent occupies an equatorial position in the piperazinium ring. The cation and anion are linked together by supra-molecular inter-actions [graph-set notation of hydrogen bonding (6) propagating in the a-axis direction]. Additionally, there is π-π stacking involving the salicylate anion and the piperazinium cation in adjacent asymmetric units as well as a C-H⋯π inter-action between a hydrogen atom on the piperazine ring and the phenyl ring within the salicyclate anion. In bis-[4-(4-nitro-phen-yl)piperazin-1-ium] bis-(4-fluoro-benzoate) trihydrate (2C10H14N3O2 +·2C7H4FO2 -·3H2O), there are two cations, two anions, and three water mol-ecules of solvation in the asymmetric unit, all linked by hydrogen bonds [graph-set notation of hydrogen bonding R 2 2(20) between adjacent cations and R 3 3(9) between a cation and its adjacent anion]. In the anion, the 4-nitro-phenyl ring occupies an axial substitution position in the piperazinium ring, which is relatively rare. Within the asymmetric unit, the phenyl groups in the cations show an offset π-π inter-action. Additionally, there is a C-H⋯π inter-action between a hydrogen atom on the phenyl ring within a cation and the phenyl ring within an anion. In 4-(4-nitro-phen-yl)piperazin-1-ium 3,5-di-nitro-benzoate (C10H14N3O2 +·C7H4N2O6 -), there is a strong N-H⋯O hydrogen bond linking the cation and anion and the 4-nitro-phenyl ring occupies an axial substitution position in the piperazinium ring, as seen in the previous structure. In the crystal, the cation and the anion form a complex three-dimensional hydrogen-bonded array involving R 2 2(8), R 4 4(12) and R 4 4(20) rings propogating in the a-axis direction. The nitro-phenyl group is disordered with occupancies of 0.806 (10) and 0.194 (10).

Project description:The crystal structures of two ammonium salts of 2-amino-4-nitro-benzoic acid are described, namely di-methyl-aza-nium 2-amino-4-nitro-benzoate, C2H8N+·C7H5N2O4-, (I), and di-butyl-aza-nium 2-amino-4-nitro-benzoate, C8H20N+·C7H5N2O4-, (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl-ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti-periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl-ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra-molecular chain by charge-assisted amine-N-H⋯O(carboxyl-ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N-O⋯π(arene) and methyl-C-H⋯O(nitro) inter-actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N-H⋯O(carboxyl-ate) hydrogen bonding. The formation of ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds, involving all ammonium-N-H and carboxyl-ate O atoms leads to a three-dimensional architecture; additional C-H⋯O(nitro) inter-actions contribute to the packing. The Hirshfeld surface analysis confirms the importance of the hydrogen bonding in both crystal structures. Indeed, O⋯H/H⋯O inter-actions contribute nearly 50% to the entire Hirshfeld surface in (I).

Dataset Information

Syntheses, crystal structures and Hirshfeld surface analyses of four mol-ecular salts of amitriptynol.

Publications

Syntheses, crystal structures and Hirshfeld surface analyses of four mol-ecular salts of amitriptynol.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets