Crystal structures of the pentacoordinate bromo, isocyanato, iodo, acetato and isothiocyanato complexes of the meso-tetraphenylporphyrinatomanganese cation

The room-temperature single-crystal X-ray diffraction determined structures of the Mn(tpp)Br . C7H8, Mn(tpp) (NCO), Mn(tpp)I . C7H8, Mn(tpp)(CO2CH3). 0.5C(7)H(8), and Mn(tpp)(NCS). 0.5C(7)H(8) complexes are described. The monoclinic P2(1)/c unit cell of Mn(tpp)(NCO) has a 14.82(1), b 17.136(5), c 14.576(5)Angstrom, beta 111.41(5)degrees, V 3446(3)Angstrom(3), Z 4. The refinement converged with conventional R(\F\) 0.053 for N-o 3199 (I > 3.0 sigma(I)) 'observed' reflections. The monoclinic P2(1)/m unit cell of Mn(tpp)Br . C7H8 has a 9.984(1), b 15.453(6), c 13.583(3) Angstrom, beta 103.99(2)degrees, V 2033(1) Angstrom(3), Z 2, R 0.039 for N-o 2668. The Mn(tpp)I . C7H8 structure is triclinic, P (1) over bar, with a 22.28(1), b 14.466(4), c 13.555(6) Angstrom, alpha 76.32(3), beta 81.74(4), gamma 74.75(3)degrees, V 4079(3) Angstrom(3), Z 4, R 0.050 for N-o 9039. The triclinic P (1) over bar crystal structures of the Mn(tpp)(CO2CH3). 0.5C(7)H(8) and Mn(tpp)(NCS).0.5C(7)H(8) complexes are isomorphous. The Mn(tpp)(CO2CH3). 0.5C(7)H(8) structure has a 26.18(1), b 13.503(3), c 12.074(6) Angstrom, alpha 66.08(4), beta 81.36(4), gamma 86.71(5)degrees, V 3858(3) Angstrom(3), Z 4, R 0.075 for N-o 6388. Solvate disorder! requiring a rigid body model, is largely responsible for the relatively high residuals. The Mn(tpp)(NCS). 0.5C(7)H(8) structure has a 25.442(6), b 13.746(3), c 12.182(5) Angstrom, alpha 66.97(3), beta 78.59(3), gamma 87.90(2)degrees, V 3839(2) Angstrom(3), Z 4, R 0.061 for N-o 5506. The asymmetric units of the iodo, acetato and isothiocyanato structures each contain two crystallographically independent complex molecules that are sensitive to crystal packing forces. The metal ion displacements from the least-squares planes formed by the pyrrole nitrogen atoms are 0.299(1) and 0.274(1) Angstrom, for the Mn(tpp)(NCO) and Mn(tpp)Br . C7H8 complexes, and 0.240(1) and 0.252(1), 0.281(1) and 0.278(1), and 0.243(1) and 0.244(1) Angstrom for the independent (a) and (b) complex molecules of Mn(tpp)I . C7H8, Mn(tpp)(CO2CH3). 0.5C(7)H(8), and Mn(tpp)(NCS). 0.5C(7)H(8) respectively. The axial Mn-X bond lengths are 2.029(5) and 2.490(1) Angstrom for the Mn(tpp)(NCO) and Mn(tpp)Br . C7H8 complexes, and 2.767(1) and 2.730(1), 2.028(5) and 2.010(5), and 2.067(6) and 2.072(5) Angstrom for the (a) and (b) complex molecules of Mn(tpp)I . C7H8, Mn(tpp)(CO2CH3). 0.5C(7)H(8), and Mn(tpp)(NCS). 0.5C(7)H(8). One of the independent complex molecules in the Mn(tpp)(CO2CH3). 0.5C(7)H(8) structure appears to exhibit acetate coordination through a carbonyl oxygen.