Solvent Dependence of the Structure and Magnetic Ordering of Ferrimagnetic Manganese(III) meso-Tetraphenylporphyrin Tetracyanoethenide, [MnTPP]+[TCNE]•-·x(solvent). Evidence for Orientationally Disordered [TCNE]•

Tetraphenylporphinatomanganate(III) tetracyanoethenide, [MnTPP][TCNE], is the prototype of a growing family of linear chain (1-D) coordination polymers that magnetically order as ferrimagnets. [MnTPP][TCNE]·xS [S = PhMe (x = 2), 1,2-C6H4Me2 (x = 1), 1,2-C6H4Cl2 (x = 3), 1,2,4-C6H3Cl3 (x = 2), and 1,3-C6H4Cl2 (x = 2)] have been prepared and structurally and magnetically characterized. All form 1-D chain structures with intrachain Mn···Mn separations ranging from 9.202 to 10.218 A. The 173 K crystal structure of [MnTPP][TCNE]·2PhMe has been rerefined, revealing that the [TCNE]•- is 2-fold-disordered and coordinated to MnIII by a pair of trans cyano nitrogen atoms to form parallel one-dimensional chains. The two orientations of [TCNE]•- are related by a 180° rotation about the diagonal axis joining the trans nitrogen atoms bound to MnIII. The major form has an occupancy of 83.3(4)% with a Mn−NTCNE distance of 2.328(3) A and a MnNC angle of 146.8(8)°. The minor form, with 16.7(4)% occupancy, has a Mn−NTCNE di...