C14H12N2•½H2O, Mr = 217•27, tetragonal I41/a, a = 14•258 (3), c = 22•286 (4) Å, V = 4531 (3) Å3, Z = 16, Dx = 1•274 (1) g cm-3, Mo Kα radiation λ = 0•71073 Å, µ = 0•74 cm-1, F(000) = 1840, T = 297 K, R = 0•041 for 1196 unique observed reflections with I > 2σ(I). Pairs of dimethylphenanthroline molecules related by a twofold axis are bridged by water molecules lying on the twofold axis and H bonded to one of the N atoms in each molecule. The H bonds are long and far from linear: O—H 1•06 (4), H•••N 154 (3)°. This is presumably a consequence of the approximately parallel arrangement of the two phenanthroline molecules in the (phen)2.H2O complex, which are tilted 4•7 (1)° with respect to each other; the atoms in one molecule are 3•50 to 3•81 Å from the plane of the other molecule. On the other side of the phenanthroline is another phenanthroline related by a center of symmetry with the atoms of one molecule 3•41 to 3•45 Å from the plane of the other molecule. The phenanthroline molecule has close to 2mm symmetry, but the individual C6 rings are tilted about 1° with respect to each other.