The compounds Co(OC(2)OPor). CH2Cl2 (1), Co(OC(2)OPor)(NO)(out).0.46CHCl(3) (2), Co(OC(3)OPor). CHCl3 (3), and Co(OC(3)OPor)(MeIm). 3C(7)H(8) (4) (OC(2)OPor = 5,10, 15,20-(benzene-1,2,4, 5-tetrakis(2-phenyloxy)ethoxy)-2',2 ", 2''',2''''-tetraylporphyrinato dianion; OC(3)OPor = 5,10,15,20-(benzene-1,2,4,5-tetrakis(2-phenyloxy)propoxy)-2',2 " ,2''',2''''-tetraylporphyrinato dianion; MeIm = 1-methylimidazole), have been synthesized, and their structures have been determined by single-crystal X-ray diffraction methods at T = -120 degreesC: 1, a = 8,824(1) Angstrom, b = 16.674(1) Angstrom, c = 16.836(1) Angstrom, alpha = 103.453(1)degrees, beta = 92.752(1)degrees, gamma = 90.983(1)degrees, P (1) over bar, Z = 2; 2, a = 9.019(1) Angstrom, b = 16.588(2) Angstrom, c = 16.909(2) Angstrom, alpha = 103.923(2)degrees, beta = 92.082(2)degrees, gamma = 93.583(2)degrees, P (1) over bar, Z = 2; 4, a = 13.484(3) Angstrom, b = 14.404(3) Angstrom, c = 14.570(3) Angstrom, alpha = 105.508(3)degrees, beta = 100.678(3)degrees, gamma = 93.509(4)degrees, P (1) over bar, Z = 2; 3, a = 16.490(1) Angstrom, b = 22.324(2) Angstrom, c = 17.257(1) Angstrom, b = 92.437(1)degrees, P2(1)/n, Z = 4, These compounds are the first structurally characterized Go-bound members of the OC(n)OPor ligand system. The NO ligand in 2 and the MeIm ligand in 4 bind asymmetrically and lead to several metrical changes in these porphyrins, e.g., variations in average porphryin deviations and Co atom displacements relative to the porphyrinato N atoms and the mean porphyrin planes.