We have synthesized by solid state chemistry and structurally characterized by single-crystal X-ray diffraction two new cluster compounds based on Nb 6 L i 12 L a 6 units (L=Br and/or F), namely, Nb 6 Br 8 F 7 and Na 2 NbF 6 –(Nb 6 Br 4 F 11 ). Nb 6 Br 8 F 7 crystallizes in the trigonal system (space group, R3c; Z=6; a=9.6373 (6) Å; c=35.415 (2) Å; R=0.0359) while Na 2 NbF 6 –(Nb 6 Br 4 F 11 ) (space group, Pm3m; Z=1; a=8.1765 (6) Å; R=0.0325) crystallizes in the cubic system. In both structures, fluorine and bromine are randomly distributed on the inner ligand positions (L i ) that edge bridge the octahedral Nb 6 cluster. In Nb 6 Br 8 F 7 , bromine fully occupies the apical ligand positions (L a ) whereas these positions are fully occupied by fluorine in Na 2 NbF 6 –(Nb 6 Br 4 F 11 ). The structural correlation between both compounds is discussed as well as the specificity of fluorine in the niobium cluster chemistry.