The simple 1:1 reaction of naphthalene-2,3-diol (H2Np) with Ti(OiPr)(4) has a complicated outcome, one rich in diversity and elucidated in this paper by X-ray crystallography and NMR spectroscopy. The reaction in CDCl3 produces a crystalline precipitate, which was found to be the symmetrical dimer [TiNp((OPr)-Pr-i)(2)](2)((HOPr)-Pr-i)(2) whose coordinated HOiPr units are hydrogen bonded to OiPr groups (A). A second crystal was also harvested and found to be a partially hydrolyzed 6:6 assembly [Ti-3(mu(3)-O)(u-Np)(2)(Np)(u-(OPr)-Pr-i)((OPr)-Pr-i)((HOPr)-Pr-i)(2)(mu -O)](2) (B) constructed of mu-oxo-linked inverted halves, each a 3:3 assembly anchored by a mu(3)-oxo group. The supernatant was deduced to contain a soluble 3:3 product [TiNp((OPr)-Pr-i)(2)](3)((HOPr)-Pr-i) possessing the same stereochernistry as B and its likely hydrolysis precursor. When A was redissolved, it produced what appeared to be a 4:4 condensation product, which was also present in the supernatant when the reaction was conducted in the presence of HOPr-absorbing 13X molecular sieves, or when the reaction mixture was heated. In an analogous reaction, Ti((OBu)-Bu-i)(4) produced only an A-like dimeric product possessing pentacoordinate metal centers,