Treatment of [ZrCI,( N Me,),] with boiling methanol provided colourless needle crystals which were identified by X-ray crystallography as the 'mixed' alcohol-alkoxide derivative [NHMe,],[ZrCI,(OMe)(MeOH)]CI.Crystals are orthorhombic, space group P2,2,2,, Z = 4, with a = 7.1 92( 8), b = 14.578( 11), c = 19.343(21) A. 1 71 7 Above-background reflections were collected on a diffractometer and the structure was refined to R = 0.065. In the [ZrCI,(OMe) (MeOH)] -anion, the zirconium atom is octahedral being bonded to four chlorine atoms [2.480(4)-2.496( 4) A] in the equatorial plane and t o t w o oxygen atoms in axial positions at distances of 1.847(10) and 2.264(9) A, identified with the O M e -and MeOH ligands respectively. The Zr-0-Me angle to the alcohol ligand is 128.6( 10) and to the alkoxide 171.4( 13)". This is the first k n o w n example of a linear zirconium-methoxide bond. The structural and bonding

Abstract. [InCla(C3HgN)

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