Procedures for the purification and subsequent crystallization of the slightly soluble four-coordinate metal-porphines, the simplest possible porphyrin derivatives, are described. Crystals of the porphine derivatives of cobalt(II), copper(II), platinum(II), and two polymorphs of zinc(II) were obtained. Analysis of the crystal and molecular structures shows that all except the platinum(II) derivative form an unusual trimeric species in the solid state. The isomorphous cobalt(II), copper(II), and one zinc(II) polymorph pack in the unit cell to form dimers as well as the trimers. Interplanar spacings between porphine rings are similar in both the dimers and trimers and range between 3.24 and 3.37 angstrom. Porphine rings are strongly overlapped with lateral shifts between ring centers in both the dimers and trimers with values between 1.52 and 1.70 angstrom or in Category S as originally defined by Scheidt and Lee. Periodic trends in the M-N-P bond distances parallel those observed previously for tetraphenyl- and ctaethylporphyrin derivatives.