The red-purple[Nb(pyc)4]·2C2H5OHcomplex is obtained by reaction of zinc-reduced ethanolic solutions ofniobium pentachloride with 2-pyridinecarboxylic acid. TheNb(IV) atom is octacoordinate, with four 2-pyridinecarboxylateligands spanning the Hoard−Silverton designated m edges ofa dodecahedron (D2d).The π-donor oxygen atoms of the ligand (Nb−Oav =2.009 Å) occupy the A sites, while the π-acceptor nitrogen atoms(Nb−Nav = 2.302 Å) reside at the B sites. This isthe first experimental evidence for Orgel's postulate regardingoctacoordinate d1 M(A-B)4stereochemistry.