
TY  - JOUR
A1  - Turner, Peter 
A1  - Gunter, Maxwell J. 
A1  - Skelton, Brian W. 
A1  - White, Allan H. 
T1  - Crystal Structures of the Pentacoordinate Bromo, Isocyanato, Iodo, Acetato and Isothiocyanato Complexes of the <emph type="2">meso</emph>-Tetraphenylporphyrinatomanganese Cation
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1998
VL  - 51
IS  - 9
SP  - 835
EP  - 852
KW  - 
UR  - https://doi.org/10.1071/C97150 
N2  - 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&#183;5C7H8, and Mn(tpp)(NCS).0&#183;5C7H8 complexs are described. The monoclinic P21/c unit cell of Mn(tpp)(NCO) has a 14&#183;82(1), b 17&#183;136(5), c 14&#183;576(5) &#197;, &#946; 111&#183;41(5)&#176;, V 3446(3) &#197;3, Z 4. The refinement converged with conventional R(&#124;F&#124;) 0&#183;053 for No 3199 (I &#62; 3&#183;0&#963;(I)) &#8216;observed&#8217; reflections. The monoclinic P 21/m unit cell of Mn(tpp)Br.C7H8 has a 9&#183;984(1), b 15&#183;453(6), c 13&#183;583(3) &#197;, &#946; 103&#183;99(2)&#176;, V 2033(1) &#197;3, Z 2, R 0&#183;039 for No 2668. The Mn(tpp)I.C7H8 structure is triclinic, P-1, with a 22&#183;28(1), b 14&#183;466(4), c 13&#183;555(6) &#197;, &#945; 76&#183;32(3), &#946; 81&#183;74(4), &#947; 74&#183;75(3)&#176;, V 4079(3) &#197;3, Z 4, R 0&#183;050 for No 9039. The triclinic P-1 crystal structures of the Mn(tpp)(CO2CH3).0&#183;5C7H8 and Mn(tpp)(NCS).0&#183;5C7H8 complexes are isomorphous. The Mn(tpp)(CO2CH3).0&#183;5C7H8 structure has a 26&#183;18(1), b 13&#183;503(3), c 12&#183;074(6) &#197;, &#945; 66&#183;08(4), &#946; 81&#183;36(4), &#947; 86&#183;71(5)&#176;, V 3858(3) &#197;3, Z 4, R 0&#183;075 for No 6388. Solvate disorder, requiring a rigid body model, islargely responsible for the relatively high residuals. The Mn(tpp)(NCS).0&#183;5C7H8 structure has a 25&#183;442(6), b 13&#183;746(3), c 12&#183;182(5) &#197;, &#945; 66&#183;97(3), &#946; 78&#183;59(3), &#947; 87&#183;90(2)&#176;, V 3839(2) &#197;3, Z 4, R 0&#183;061 for No 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&#183;299(1) and 0&#183;274(1) &#197; for the Mn(tpp)(NCO) and Mn(tpp)Br.C7H8complexes, and 0&#183;240(1) and 0&#183;252(1), 0&#183;281(1) and 0&#183;278(1), and 0&#183;243(1) and 0&#183;244(1) &#197; for the independent (a) and (b) complex molecules of Mn(tpp)I.C7H8, Mn(tpp)(CO2CH3).0&#183;5C7H8, and Mn(tpp)(NCS).0&#183;5C7H8 respectively. The axial Mn&#8211;X bond lengths are 2&#183;029(5) and 2&#183;490(1) &#197; for the Mn(tpp)(NCO) and Mn(tpp)Br.C7H8 complexes, and 2&#183;767(1) and 2&#183;730(1), 2&#183;028(5) and 2&#183;010(5), and 2&#183;067(6) and 2&#183;072(5) &#197; for the (a) and (b) complex molecules of Mn(tpp)I.C7H8, Mn(tpp)(CO2CH3).0&#183;5C7H8, and Mn(tpp)(NCS).0&#183;5C7H8. One of the independent complex molecules in the Mn(tpp)(CO2CH3).0&#183;5C7H8 structure appears to exhibit acetate coordination through a carbonyl oxygen. 
ER  -

