Melemium Methylsulfonates HC6N7(NH2)3H2C6N7(NH2)3(SO3Me)3·H2O and H2C6N7(NH2)3(SO3Me)2·H2O 

Abstract Melem C 6 N 7 (NH 2 ) 3 was shown to form a variety of adduct phases and salts. Salts of melem can be yielded by reaction of melem with strong acids. We investigated the reaction of melem with methylsulfonic acid, thus identifying two new melemium salts with formulas HC 6 N 7 (NH 2 ) 3 H 2 C 6 N 7 (NH 2 ) 3 (SO 3 Me) 3 ·H 2 O ( 1 ) and H 2 C 6 N 7 (NH 2 ) 3 (SO 3 Me) 2 ·H 2 O ( 2 ), respectively. The structures of both compounds were elucidated using single‐crystal XRD compound 1 : ( P \bar{1} no. 2, Z = 2, a = 10.096(2), b = 12.865(3), c = 13.369(3) Å, α = 63.28(3), β = 81.19(3), γ = 72.92(3)°, V = 1461.4(7) Å 3 ) compound 2 : ( P 2 1 / n , no. 14, Z = 4, a = 8.0757(16), b = 7.6937(15), c = 27.540(6) Å, β = 92.03(3)°, V = 1710.6(6) Å 3 ). Both compounds are discussed in comparison to structural data from the literature of other melemium salts. We also present new synthetic approaches for the preparation of melem in larger quantities.