Oxomolybdenum phthalocyanine (MoOPc) and tin phthalocyanine (SnPc), which both have a pyramidal molecular shape, were deposited onto sapphire by organic molecular beam deposition. The crystalline phase of these films was determined to be triclinic by X-ray diffraction and absorption spectra with reference to previously formed titanylphthalocyanine (TiOPc) and vanadylphthalocyanine (VOPc) films. Values for the third-order nonlinear optical susceptibility chi((3)) Of the triclinic MoOPc and SnPc films were slightly smaller than those of TiOPc and VOPc but still much larger than those of planar metallophthalocyanines such as copper phthalocyanine and zinc phthalocyanine. Molecular shape is an important factor determining the nonlinear optical properties of metallophthalocyanines.