The complex [Ni(L-H)2] • CHCl3 (I), where L-H is the (9E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H) -ylidene]hydrazone anion (L), was synthesized for the first time. The crystal structure of I was solved. The L-H and L-H′ anions exist as cis- and trans-isomers and are linked to the central Ni2+ atom in a tridentate chelating mode giving rise to two conjugated five-membered metal rings of different composition (NiN3C and NiONC2) at each anion. The Ni2+ coordination polyhedron is a highly distorted octahedron whose axial positions are occupied by N(3) and N(3)′ atoms. The vertices of the tetrahedrally distorted equatorial base of the octahedron are occupied by the N(1) and N(1)′ atoms of the dihydroisoquinoline fragment (A) and the O(1) and O(1)′ atoms of the phenanthrenequinone fragment (B). Complex I occurs as the cis-isomer. The conformations of the L-H anions in I and the L molecules in L • H2O do not differ much. The randomly disordered CHCl3 solvent molecules in I occupy crystal voids between the centrosymmetric dimeric associates. Spectroscopic (IR and UV-Vis) characteristics of I were obtained. © 2011 Pleiades Publishing, Ltd.