Synthesis, Spectroscopic Properties and Hirshfeld Surface Analysis of 3,14-Dimethyl-2,6,13,17-tetraazoniatricyclo(16.4.0.07,12)docosane Tetrachloride Tetrahydrate

Single crystals of 3,14-dimethyl-2,6,13,17-tetraazoniatricyclo(16.4.0.07,12)docosane tetrachloride tetrahydrate compound, [C20H44N4]Cl4·4H2O (1), were obtained by a novel synthetic route and characterized by elemental analysis and X-ray diffraction. The synthesized compound crystallized in the monoclinic space group P21/n with two molecules of compound 1 in the unit cell [a = 7.5548(3) Å, b = 23.1838(8) Å, c = 8.3101(4) Å; β = 103.390(3)º]. The asymmetric unit contains half a centrosymmetric macrocyclic cation, two chloride anions and two water molecules. The organic [C20H44N4]4+ fragment of 1 adopts an exodentate [3,4,3,4]-D conformation. The C–C and N–C bond lengths of the macrocyclic tetracation range 1.525(3)-1.540(3) Å and 1.505(3)-1.519(3) Å, respectively. A three-dimensional hydrogen bonding network provides crystal cohesion through O–H···Cl, N–H···Cl and N–H···O interactions between organic cations, chloride anions and water molecules. The functional groups present in the crystal were studied by Fourier-transform infrared spectroscopy and Raman spectroscopy. The Hirshfeld surface analysis and 2D fingerprint plots revealed that the crystal packing in 1 is dominated by H···H, Cl···H/H···Cl and O···H/H···O contacts.