The synthesis and characterization of six new substituted guanidium tetrahydroxidohexaoxidopentaborate(1-) salts are reported: [C(NH2)2(NHMe)][B5O6(OH)4]·H2O (1), [C(NH2)2(NH{NH2})][B5O6(OH)4] (2), [C(NH2)2(NMe2)][B5O6(OH)4] (3), [C(NH2)(NMe2)2][B5O6(OH)4] (4), [C(NHMe)(NMe2)2][B5O6(OH)4]·B(OH)3 (5), and [TBDH][B5O6(OH)4] (6) (TBD = 1,5,7-triazabicyclo [4.4.0]dec-5-ene). Compounds 1-6 were prepared as crystalline salts from basic aqueous solution via self-assembly processes from B(OH)3 and the appropriate substituted cation. Compounds 1-6 were characterized by spectroscopic (NMR and IR) and by single-crystal XRD studies. A thermal (TGA) analysis on compounds 1-3 and 6 demonstrated that they thermally decomposed via a multistage process to B2O3 at >650 °C. The low temperature stage (<250 °C) was endothermic and corresponded to a loss of H2O. Reactant stoichiometry, solid-state packing, and H-bonding interactions are all important in assembling these structures. An analysis of H-bonding motifs in known unsubstituted guanidinium salts [C(NH2)3]2[B4O5(OH)4]·2H2O, [C(NH2)3][B5O6(OH)4]·H2O, and [C(NH2)3]3[B9O12(OH)6] and in compounds 1-6 revealed that two important H-bonding R22(8) motifs competed to stabilize the observed structures. The guanidinium cation formed charge-assisted pincer cation-anion H-bonded rings as a major motif in [C(NH2)3]2[B4O5(OH)4]·2H2O and [C(NH2)3]3[B9O12(OH)6], whereas the anion-anion ring motif was dominant in [C(NH2)3][B5O6(OH)4]·H2O and in compounds 1-6. This behaviour was consistent with the stoichiometry of the salt and packing effects also strongly influencing their solid-state structures.
Keywords: H-bonding; R22(8) motifs; XRD; borate; guanidinium salts; oxidoborate; pentaborate(1-); tetrahydroxidohexaoxidopentaborate(1-) salts.