Two thiolate-ligated zinc complexes, ZnL(S3(Me)N3)(Pr)(.-)MeOH (1) and hydride-reduced ZnL(S2(Me)N3(Pr)H4)(.-)MeOH (2), are reported, each containing a cocrystallized MeOH molecule H-bonded to a zinc-bound sulfur. IR and X-ray structural data indicate that the S ... H-OMe interaction in 2 is comparable to the interaction between Et(3)N and H-OMe. These data suggest that, in liver alcohol dehydrogenase, alcohols may be activated in a similar manner, without requiring prior coordination to the metal.