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The crystal structure of solvent-free diphenylzinc has been determined. Crystals of [Ph2Zn] are triclinic, space group P1, with unit cell dimensions a = 9.956 (1) A, b = 10.024 (2) A, c = 12.011 (2) b, a = 113.74(2)O, / 3 = 108.79 (1)O, y = 97.68 (2)O, and Z = 2. The structure refinement converged at RF = 0.042. A remarkable PhZn(p-Ph)zZnPh dimeric structure is found, in which the zinc atoms are tricoordinated. The structure confirms the ability of Zn to take part in multicenter bonding to carbon. It is unique not only in the sense that it is the first example of an arylzinc derivative but also because of the unsymmetrical orientation of the p-phenyl groups: they retain the predominant bonding relation to one zinc atom, as the association of the two monomeric PhzZn units only partially disturbs their original, linear geometry: the average Zn-C bond distances within one PhzZn unit are 1.946 (5) A (terminal) and 2.011 (5) A (bridging), whereas the bridging Zn-C bond to the second PhzZn unit is 2.403 (5) A. In the crystal packing, two dimeric residues are weakly associated by interactions (3.0-3.7 A) between the two zinc atoms of one dimer and one of the terminal phenyl groups of the other.

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