Novel disubstituted 5,5 0 -bi-1,2,4-triazines bearing pyridine (1), furan (2) and thiophene (3) rings at 6 and 6 0 -positions of the parent bitriazine were prepared as potential extractants of nuclear waste. The compounds were easily obtained by Stille coupling starting from 6,6 0 -bisbromo-3,3 0 -bis(N,N-dimethylamine)-5,5 0 -bi-1,2,4-triazine and the corresponding tin reagents. The molecular and crystal structures of the ligands 1-3 were determined by the X-ray analysis. The X-ray investigations show different conformations of the molecules described as gauche-gauche-gauche for 1 and gauche-cis-cis for 2 and 3. Each of the molecules resides on a twofold axis that passes through the middle of the central C5-C5 0 bond. The molecular packing in 1 is influenced by the pÁ Á Áp and weak C-HÁ Á Áp interactions. The crystal structures of 2 and 3 are governed by a combination of a weak C-HÁ Á ÁN hydrogen bonds and C-HÁ Á Áp interactions. Theoretical calculations using semi-empirical AM1 and DFT/B3LYP/6-311++G(d,p) ab initio methods were carried out to find correlation between conformational and electronic parameters of the molecules and their preferences to metal ions complexations.