The crystal and molecular structure of NPCl₂(NSOF)₂ at –160°C

Abstract

Cyclo-tri-#-nitrido-dichlorophosphorusbis(oxofluorosulphur), NPC12(NSOF)2, is monoclinic, space group P21/c, with a= 7.728 (3), b = 7.664 (3), c= 14"097 (4)/~,, fl= 96.01 (2) ° at -160°C. The structure was solved by conventional Patterson and Fourier techniques and refined by block-diagonal leastsquares analysis of 1624 counter intensities measured at -160°C to a final R of 0.107. Mean bond lengths are P-N 1.596 (8), P-C1 1.956 (4), S-F 1.570 (7) and S=O 1.420 (8) A. The N-S bonds in the S-N-S section of the ring have a mean value of 1.568 (9)/~. The mean length of the other N-S bonds is 1.527 (9)/~. The six-membered ring has a twisted chair conformation with the oxygen atoms cis with respect to the ring plane. The molecular dimensions are compared with those in related compounds.

Derivatives of cis-NPCl2(NSOCl)2 and (NPCl2)2NS0Cl, Part XIII [1] Methyl- and Ethylamino Derivatives of the Ring System cis-NPCl2(NSOX)2 with X = Chlorine and Fluorine

“…In view of the free space available at the oxygen atoms [7,8] we suppose that in the isomer formed in the highest yield the amino and oxygen ligands are in cis-position.…”

The crystal and molecular structure of (NPCl2)2NSOCl at –140°C

“…It is remarkable that the relatively low-melting compounds NPCI2(NSOF)2 (56.5-58.5°C; Baalmann & van de Grampel, 1973;Tucker & van de Grampel, 1974) and (NPCI2)2NSOC1 (60-62 °C; Baalmann et al, 1972) have short non-bonded contacts with two neighbouring molecules, whereas the relatively highmelting compound NPCI2(NSOC1)2 (94.9-95.9°C; van de Grampel & Vos, 1963) possesses short CI... O contacts (3.05, 3.09 ~) with four neighbours (van de Grampel & Vos, 1969). This suggests for this class of compounds a relationship between the number of intermolecular contacts and the melting point.…”

Structure of cis-5,5-dichloro-1,3-diphenyl-1λ6,3λ6,2,4,6,5λ5-dithiatriazaphosphorine 1,3-dioxide

“…P and S atoms show a distorted tetrahedral geometry. The observed P-C1 bond lengths [average value 1.981 (2)A] and C1-P-C1 bond angles [average value 101.5 (1) ° ] may be compared with those reported for related compounds (van de Grampel & Vos, 1969;Tucker & van de Grampel, 1974;Perales, Fayos, van de Grampel & de Ruiter, 1980;van Bolhuis et al, 1981). Short C-H...O bonds (Berkovitch-Yellin & Leiserowitz, 1984) are O(ll)...H(ll0) (x, y--l, z) =2.41(3)A and O(21)...H(29) (x, y-I, z)= 2.59 (3) A [sum of the van der Waals radii is 2.72 A (Bondi, 1964)] and O(11)...C1(21) (I-x, I-y,-z) =3.139 (2)A (sum of the van der Waals radii is * Throughout this paper the mean values and their standard errors have been calculated using the formulae given by Domenicano, Vaciago & Coulson (1979).…”