Gas phase electron diffraction study of 1-chloro-2,4-dimethyl-1,2-dihydro-1,5,2,3-phosphaoxadiazole

• Published in: Journal of molecular structure 1982, Vol.82 (1), p.115-131
• Main Authors: Khaikin, L.S., Grikina, O.E., Vilkov, L.V.
• Format: Article
• Language: English
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/0022-2860(82)85239-3

Earlier gas phase electron diffraction data on 1-chloro-2,4-dimethyl-1,2-dihydro-1,5,2,3-phosphaoxadiazole (I) obtained by these authors are treated using up-to-date developments in structure analysis and the conclusion of a considerable elongation of the P-Cl bond in chlorinated aminophosphines is subst antiated. This bond length ( r a) is found to be 2.168(4) Å in I, i.e. far larger than the sum of the covalent radii (2.09 Å). The r a parameters of the oxadiazaphospholene ring containing the NC double bond refine to the following values (bond lengths in Å, angles in degrees): ▪1.699(6); PO, 1.628(5); weighted average ▪, 1.403(9); NC, 1.277(8); NPO, 91.1(0.6); PNN, 108.7(1.0); POC, 109.3(1.0); NNC, 112.0(1.8); NCO, 114.0(2.0). The ring has an envelope-like nonplanar conformation with the P atom in the flap position. The dihedral angle between the NPO plane and the least-squares plane of the O-CN-N fragment is 20.0(2.5)°. The P–Cl bond is in the axial position. The amine nitrogen linked with phosphorus has a practically planar bond configuration (the sum of the valence angles at N is 357.7°).