Can methanol act as a ligand?
There are several complexes where methanol acts as ligand. Some examples are:


methanol coordinated vanadium(V) chalcogenido complexes: $\ce{V(Chal)Cl2(OMe)(HOMe)2}$ where $\ce{Chal = O, S, Se}$
bis(μ-methoxo)dichromium(III) complexes, $\ce{[(L^{Se})2Cr2(μ-OCH3)2(CH3OH)2]}$ and $\ce{[(L^{Se})2Cr2(μ-OCH3)2(CH3OH)(CH3O)]}$, where $\ce{L^{Se}}$ represents the dianion of 2,2‘-selenobis(4,6-di-tert-butylphenol)
di-µ-chlorido-bis[dichloridobis(methanol-κO)iridium(III)] dihydrate  $\ce{[Ir2Cl6(CH3OH)4]2H2O}$
$\ce{M(CH3OH)3SO4}$ where $\ce{M = Ni, Co, Zn}$ 


Reference

Google: Methanol ligand complex. First 4 search results.