Crystal structures of [N(C4H9)4][NbCl4OAlCl3] and [N(C3H7)4][NbCl6]

[N(C 4 H 9 ) 4 ][NbCl 4 OAlCl 3 ] 1 crystallized after two months in form of yellow needles in a Schlenk-tube from a CH 2 Cl 2 /n-hexane solution containing equimolar amounts of [N(C 4 H 9 ) 4 ]Cl, NbCl 5 and AlCl 3 . Yellow crystals of [N(C 3 H 7 ) 4 ][NbCl 6 ] 2 yielded from the reaction of equimolar amounts of [N(C 3 H 7 ) 4 ]Cl and NbCl 5 in the same solvent. The oxygen in 1 indicates a reaction of the educts with traces of water. Both compounds crystallize in the space group P2 1 /n. ( 1 : a=10.664(1)Å, b=14.177(1)Å, c=19.429(3)Å, β=90.01(1)°, Z=4; 2 : a=11.678(2)Å, b=15.581(2)Å, c=11.769(1)Å, β=91.51(2)°, Z=4). 1 is characterized by [N(C 4 H 9 ) 4 ] + cations and [NbCl 4 OAlCl 3 ] units which are linked by chlorine bridges to dimeric anions. [NbCl 4 OAlCl 3 ] - has a nearly linear Nb-O-Al bridge (bond angles 178.9(3)°) with a Nb-O bond length of 1.769(4) Å and a Al-O bond length of 1.771(5) Å. The structure of 2 contains [N(C 3 H 7 ) 4 ] + cations and [NbCl 6 ] - anions.