Hydrogen-bond networks in the mono- and diprotonated cyclic diamine [9]aneN2S

Abstract

The hydrogen-bond networks in the mono- and diprotonated cyclic diamine, 1-thia-4,7-diazacyclononane, [9]aneN2S, have been examined. Crystals of the monoprotonated, form [9]aneN2S ⋅ HCl, contain a ribbon-like network of alternating strong and weak intermolecular N\(---\)H ⋅⋅⋅ Cl hydrogen bonds and weak intramolecular N\(---\)H ⋅⋅⋅ N hydrogen bonds. Crystal data for [9]aneN2S ⋅ HCl: monoclinic, a = 6.6640(6) A, b = 10.3493(9) A, c = 6.9807(6) A, β = 108.847(1)°, V = 455.63(7) A3, space group P21, Z = 2. In the di-protonated form, [9]aneN2S ⋅ 2HBr, the ribbon-like network comprises strong intermolecular and weak intramolecular N\(---\)H ⋅⋅⋅ Br hydrogen bonds. Crystal data for [9]aneN2S ⋅ 2HBr: orthorhombic, a = 12.5918(13) A, b = 8.0753(9) A, c = 10.6856(11) A, V = 1086.5(2) A3, space group Pnma, Z = 4. The chloride anions of [9]aneN2S ⋅ HCl align in interlocking columns in the a- and c-direction whereas the bromide anions in [9]aneN2S ⋅ 2HBr occupy channels in the b-direction.