Crystal and molecular structure of a chlorosulfonate of a novel cage chlorocarbon, C₁₀Cl₁₁SO₃Cl, determined by the symbolic addition method

Abstract

Hexachlorocyclopentadiene C5C16 dimerizes by catalytic action of aluminum chloride into an unusually stable chlorocarbon, C10Cl12. The configuration of the molecule has been studied by various physicochemical methods such as thermal and dielectric studies on crystals, nuclear magnetic resonance, infrared spectroscopic and dipole moment measurements of solutions. The results indicate that the molecule possesses a cage structure which consists of two cyclopentane rings connected by four single bonds. Since Cx0Cll2 exhibits a disordered structure in the room temperature phase, a chlorosulfonate group was introduced onto one of the apex carbon atoms. The material crystallizes in the monoclinic system with a= 16"758+0.003, b=8"753+0"002, c= 14"459+0"003, t= 112.0°+0.1; the space group is P21/a. The crystal structure was determined by the symbolic addition method and refined by the least-squares method. The basic cage structure is trans consisting of four cyclopentane and two cyclobutane rings, all of which are puckered. The chlorocarbon chlorosulfonate may then be called undecachloropentacyclo [5.3.0.02,6.03,9.04,8]decan-5-chlorosulfonate. The bond distances and angles in this fused ring system are discussed in detail.

The structure of C9Cl7(COOH).(O2C2H4), a condensed cage pentacyclononane compound, determined by the symbolic addition method

“…One notices obvious systematic variations in the bond angles. Similar variations have been observed in the decane compound (Okaya & Bednowitz, 1967).…”

“…As shown in Fig. 6(b) the bond angles show tendencies similar to those in the pentacyclodecane system [ Fig.3(c)] (Okaya & Bednowitz, 1967). The results well established that, for cyclopentane rings in such a condensed system, the least-constrained apex carbon atoms undergo the largest deviations from the normal valence angles.…”

“…3(c)]; e.g. the configuration of the cage was determined by a crystal structure analysis of its undecachlorochlorosulfonate derivative, C10CI~OSOzCI (Okaya & Bednowitz, 1967). The bond distances are shown in Fig.4.…”

Crystal and molecular structure of 14c-hydro-5a-phenylbenz[a]indeno[2,1-c]fluorene-5,10-dione

“…The mean of 18 C-H bond lengths is 0.98 A with a mean deviation of 0.05 A. The only anomalous deviation from the average (-0.2 A) was for the C( 19)-H- (19) bond in the phenyl group. This is not unexpected in view of the highly anisotropic thermal correction applied to C(19).…”