STRUCTURES OF 5-COORDINATE DINITROSYLS OF MANGANESE .1. MONOCLINIC FORM OF DINITROSYL-BIS (DIMETHYL PHENYLPHOSPHONITE) MANGANESE(I) CHLORIDE, [MN(NO)2(P(OCH3)2C6H5)2CL]

The structure of dinitrosylbis(dimethyl phenylphosphonite)manganese(I) chloride, [Mn(NO)2{P(OCH3)2C6H5}2Cl], has been determined by X-ray diffraction. The compound crystallizes from benzene in the monoclinic space group C2/c with a=25.86 (1) Å, b=11.863 (5) Å, c=14.563 (5) Å, 13=90.96 (5)°, V=4467.5 Å3, p(obsd)=1.45 g cm-3, and Z=8. The structure was solved by conventional Patterson and Fourier methods and refined by block-diagonal least squares to a conventional R=0.041 for 2265 reflections with I>1.65σ(I). The coordination geometry about the manganese is trigonal bipyramidal with the phosphorate ligands trans. The two NO groups are ordered, and the atoms of the {Mn(NO)2Cl} group are coplanar with the NO groups bent in toward each other. Bond lengths and angles of interest are Mn-N=1.665, 1.650 (10) Å, N-O=1.18, 1.18 (1) Å, Mn-N-O=163, 166 (1)°, Mn-P=2.294, 2.291 (5) Å, Mn-Cl=2.351 (5) Å, N-Mn-N=111.5°, O-Mn-O=99.0°, and Cl-Mn-N=123.9, 124.6°. The phosphonite ligands bend toward the CI atom, away from the NO groups: P-Mn-P=166.9°, P-Mn-Cl=83.4, 83.5°, P-Mn-N angles are between 91.3 and 95.6°; P⋯Cl=3.09, 3.09 Å, and P⋯N distances are between 2.85 and 2.95 Å. © 1979, American Chemical Society. All rights reserved.