Structure of the hexafluorophosphate salts of [mu]-([eta superscript 6]:[eta superscript 6]-phenoxazine)bis[[eta superscript 5]-cyclopentadienyliron(lI)] (1) and ([eta superscript 5]-cyclopentadienyl)([eta superscript 6]-phenoxathiin)iron(II) (2)

Abstract

(1): [C[subscript 22]H[subscript 19]Fe[subscript 2]NO](PF[subscript 6])[subscript 2], M[subscript r] = 715.05, monoclinic, P2[subscript 1]/n, a = 10.635 (2), b = 9.928 (1), c = 22.562(7) [Angstrom], [beta] = 92.41 (1) °, V = 2380.1 (9) [Angstrom][superscript 3], Z = 4, D[subscript x] = 2.00 g cm [superscript -3] (163 K), Mo Ka radiation, [lambda] = 0.71069 [Angstrom], [mu] = 14.63 cm [superscript-1], F(000) = 1424, T = 163K, final R = 0.045 for 4787 reflections. (2): [C[subscript 17]H[subscript 13]FeOS]PF[subscript 6], M[subscript r] = 466.18, triclinic, P1, a = 8.461 (2), b = 10.273 (2), c = 10.562 (2) [Angstrom], [alpha] = 93.75 (2), [beta]= 110.41 (2), [gamma] = 102.84 (2) °, V = 828.6 (3) [Angstrom][superscript 3], Z = 2, D[subscript x] = 1.87g cm[superscript -3] (163K), MoK[alpha] radiation, [lambda] = 0.71069 [Angstrom], [mu] = 11.95 cm[superscript -1], F(000) = 468, T = 163 K, final R = 0.046 for 3031 reflections. The cyclopentadienyliron(II) moieties, ([eta superscript 5]- Cp)Fe[superscript II], in (1) are trans. Coordination is to the terminal phenyl ring(s) in both complexes and results in a flattening of phenoxathiin in (2), while phenoxazine in (1) remains essentially unchanged. The heterocycles are nearly planar, with (1) having a dihedral angle between planes through the phenyl rings of 176.9 (1) ° while (2) has a dihedral angle of 178.7 (1) °. Asymmetric C-O bond lengths are observed in (2) with the shorter bond being to the C atom of the coordinated ring, 1.387 (4) [Angstrom] versus 1.419 (5) [Angstrom], which is apparently due to the inductive effect of the coordinated ([eta subscript 5]-Cp)Fe[superscript II] group.