The structures of eleven (4-phenyl)piperazinium salts containing organic anions

Eleven (4-phenyl)piperazinium salts containing organic anions have been prepared and structurally characterized, namely, 4-phenylpiperazin-1-ium 4-fluorobenzoate monohydrate, C10H15N2+center dot C7H4FO2-center dot H2O, 1; 4-phenylpiperazin-1-ium 4-bromobenzoate monohydrate, C10H15N2+center dot C7H4BrO2-center dot H2O, 3; 4-phenylpiperazin-1-ium 4-iodobenzoate, C10H15N2+center dot C7H4IO2-, 4; 4-phenylpiperazin-1-ium 4-nitrobenzoate, C10H15N2+center dot C7H4NO4-, 5; 4-phenylpiperazin-1-ium 3,5-dinitrosalicylate, C10H15N2+center dot C7H3N2O7-, 6; 4-phenylpiperazin-1-ium 3,5-dinitrobenzoate, C10H15N2+center dot C7H3N2O6-, 7; 4-phenylpiperazin-1-ium picrate, C10H15N2+center dot C6H2N3O7-, 8; 4-phenylpiperazin-1-ium benzoate monohydrate, C10H15N2+center dot C7H5O2-center dot H2O, 9; 4-phenylpiperazin-1-ium p-toluenesulfonate, C10H15N2+center dot C7H7O3S-, 10; 4-phenylpiperazin-1-ium tartarate monohydrate, C10H15N2+center dot C4H5O6-center dot H2O, 11; and 4-phenylpiperazin-1-ium fumarate, C10H15N2+center dot C4H3O4-, 12. Compounds 1 and 3-12 are all 1:1 salts with the acid proton transferred to the phenylpiperaizine basic N atom (the secondary amine) with the exception of 3 where there is disorder in the proton position with it being 68% attached to the base and 32% attached to the acid. Of the structures with similar stoichiometries only 3 and 9 are isomorphous. The 4-phenyl substituent in all cases occupies an equatorial position except for 12 where it is in an axial position. The crystal chosen for structure 7 was refined as a nonmerohedral twin. There is disorder in 5, 6, 10 and 11. For both 5 and 6, a nitro group is disordered and was modeled with two equivalent orientations with occupancies of 0.62 (3)/0.38 (3) and 0.690 (11)/0.310 (11), respectively. For 6, 10 and 11, this disorder is associated with the phenyl ring of the phenylpiperazinium cation with occupancies of 0.687 (10)/0.313 (10), 0.51 (7)/0.49 (7) and 0.611 (13)/389 (13), respectively. For all salts, the packing is dominated by the N-H center dot center dot center dot O hydrogen bonds formed by the cation and anion. In addition, several structures contain C-H center dot center dot center dot pi (1, 3, 4, 8, 9, 10, and 12) and aromatic pi-pi stacking interactions (6 and 8) and one structure (5) contains a -NO2 center dot center dot center dot pi interaction. For all structures, the Hirshfeld surface fingerprint plots show the expected prominent spikes as a result of the N-H center dot center dot center dot O and O-H center dot center dot center dot O hydrogen bonds.