NaSi reacts with MoCl5 and 15-crown-5 in toluene with reduction of Mo(V) to Mo(IV). Work-up in DME yields MoCl4(DME). 15-crown-5 (1). MoCl4(DME) (2) is prepared more conveniently from MoCl5/DME. 1 and 2 were characterized spectroscopically and by X-ray structure determination. Crystal data: 1, space group P2(1)2(1)2(1) (No. 19), Z = 4,2765 observed independent reflexions, R = 0.026, cell dimensions (110 K): a = 16.292(4), b = 12.884(3), c = 10.452(2)angstrom. 2, space group 142d (No. 122), Z = 8,558 observed independent reflexions, R = 0.037, cell dimensions (292 K): a = b = 9.56(2), c = 23.777(6) angstrom. The MoCl4(DME) molecule of 1 and 2 forms a distorted octahedron. There are four non-coordinating 15-crown-5 molecules present in the unit cell of 1. The UV/VIS spectrum and the magnetic properties of 2 are discussed.