Stabilization of the New Antimonide Zr2V6Sb9 by V–V and Sb–Sb Bonding

Sb−Sb Interactions in the Hafnium-Rich Antimonide Hf6TiSb4

“…Net small, but positive overlap populations are calculated as the result of the sums of filled bonding and antibonding states for both interactions, namely 0.053 electron per bond for the shorter and 0.023 for the longer one. Similar values were obtained for the bonds between 336 and 343 pm in Zr 2 V 6 Sb 9 (from 0.048 to 0.025) and for the longer bond of 336 pm in elemental antimony (0.077), using the same Hückel parameters for the Sb atoms . Marginal differences in the Mulliken charges show that Sb atoms with stronger or more Sb−Sb interactions are less reduced: these charges increase by going from Sb1 (charge −0.32, two Sb−Sb bonds) to Sb4 (−0.34, one bond, the weaker one) and Sb3 (−0.35, one bond, the stronger one) to Sb2 (−0.42, no Sb−Sb distance < 370 pm), while the same trend was observed in the case of Zr 2 V 6 Sb 9 ; i.e., the most reduced Sb atom takes part in the fewest and/or weakest Sb−Sb bonds.…”

Zr1-xTixSb: A Novel Antimonide on the Quasibinary Section ZrSb−TiSb with a Complex Crystal Structure Exhibiting Linear Sb Chains and Fragments of the TiSb Structure

“…Values similar to the latter are calculated for the Sb−Sb interactions in ZrSb (324 pm, 0.06; 325 pm, 0.09) and for the distances in (Zr,Ti)Sb between 329 and 348 pm (0.07−0.03), indicating weak bonding interactions in every case. Comparable values were also found for the interactions between 328 and 350 pm in the structures of (Zr,V) 11 Sb 8 (averaged 0.02), Zr 2 V 6 Sb 9 (0.04), (Hf,Ti) 7 Sb 4 (0.04), and Zr 3 Ni 3 Sb 4 (0.03) . The small positive values suggest weak bonding character, which was also obtained using quasirelativistic pseudopotential ab initio calculations at the second-order Moller−Plesset level (MP2) for even longer distances; also an Sb−Sb attraction was calculated for the Sb−Sb interaction of 378.5 pm in the dipnicogen hydride model dimer (H 2 Sb−SbH 2 ) 2 due to correlation effects .…”

A Three-Dimensional Extended Sb Network in the Metallic Antimonides (M‘,Ti)5Sb8 (M‘ = Zr, Hf, Nb, Mo)

“…The cumulated Sb−Sb MOPs per Sb atom follow the same trend as the PBOs, i.e., MOP(Sb1) = 0.59 > MOP(Sb2) = 0.43 > MOP(Sb3) = 0.28. The fact that stronger Sb−Sb interactions occur with a smaller reduction of the Sb atoms and therefore smaller Mulliken gross populations was shown earlier in the reports dealing with Zr 2 V 6 Sb 9 , (Hf,Ti) 7 Sb 4 , (Zr,Ti)Sb, (Zr,V) 11 Sb 8 , and (Zr,V) 13 Sb 10 and is also reflected in the electronic structure of Ti 5 Sb 8 : the Mulliken populations increase from Sb1 (5.12) over Sb2 (5.27) to Sb3 (5.40).…”