The structure of carbodiimide, HNCNH

Abstract

An experimentally determined r _s -type structure of HNCNH is reported: r _NH = 1.0074 Å, r _CN = 1.2242 Å, ∠HNC = 118.63°, ∠NCN = 170.63°, ∠HN ··· NH = 88.99°. The number of digits quoted allow for errors with two significant figures. In order to obtain these values we recorded rotational—torsional spectra of HN¹³CNH, H¹⁵NC¹⁵NH and DNCND, by using isotopically enriched cyanamide. A chemical equilibrium exists between carbodiimide, HNCNH, and the more stable isomer cyanamide, H₂NCN, which strongly favours cyanamide (approximately 1:115 at 110 °C). The expensive C- and N-substituted isotopomers could only be investigated in the millimetre wave region, while for DNCND the far infrared spectrum between 10–350 cm⁻¹ was also recorded. Rotational constants of the three isotopomers, as well as of the parent species, were determined by fitting the assigned spectral transitions to the Watson Hamiltonian in S reduction. Using fitting programs written by Schwendeman and Rudolph, r _o, r_s and r^ρ _m structures of HNCNH were derived. The experimentally determined structural parameters are compared with an ab initio r_e structure.