NITROSYLMETALLOPORPHYRINS .5. MOLECULAR STEREOCHEMISTRY OF NITROSYL(5,10,15,20-TETRATOLYLPORPHINATO)MANGANESE(II) AND NITROSYL(4-METHYLPIPERIDINE)(5,10,15,20-TETRAPHENYLPORPHINATO)MANGANESE(II)

The molecular stereochemistries of five-coordinate nitrosyl(5,10,15,20-tetratolylporphinato)manganese(II) (I) and six-coordinate nitrosyl(4-methylpiperidine)(5,10,15,20-tetraphenylporphinato)manganese(II) (II) have been determined by X-ray diffraction methods. I crystallizes as the benzene solvate in the monoclinic system, space group P21/a. The unit cell has a = 15.755 (6) Å,b = 16.979 (4) Å, c = 17.389 (3) Å, β = 112.43 (2)°, and Z = 4. II crystallizes as a chloroform solvate in the orthorhombic system, space group P212121. The unit cell constants are a = 17.561 (6) Å, b = 25.580 (13) Å, and c = 10.175 (6) Å for Z = 4. Both complexes have essentially linear Mn-N-O groups. The Mn-N(NO) bond distances [1.641 (2) Å (I) and 1.644 (5) Å (II)] are not affected by the increase in coordination number, but the Mn-N(porphinato) bond distances [2.004 (5) Å (I) and 2.027 (3) Å (II)] are affected. The data for I along with the results for Fe(TPP)(NO) and Co(TPP)(NO) permit an assessment of the effects of nonbonded repulsion between the axial ligand and porphinato ligand on the displacements of the respective metal atoms. © 1979, American Chemical Society. All rights reserved.