Molecular geometry of substituted benzene derivatives. II. A bond angle versus electronegativity correlation for the phenyl derivatives of second-row elements

Abstract

The angular deformations induced in the carbon skeleton of the benzene ring by substitution of a hydrogen atom with a second-row element have been investigated, using the best structural data available in the literature. It is shown that a linear correlation exists between the internal bond angle at the carbon atom at which substitution takes place and Pauling's electronegativity of the substituent. From this correlation, the actual electronegativities of phosphorus and sulphur in several classes of related compounds and individual molecules are evaluated. Similar correlations are shown to exist for the phenyl derivatives of first-and third-row elements.

trans-Acetato(methoxycarbonyl)bis(triphenylphosphine)palladium(II)

“…The last two values are in good agreement with the molecular geometries of substituted benzene derivatives discussed by Domenicano, Vaciago & Coulson (1975).…”

6-N-Dimethylaminonaphthylsulphonylaziridine

“…The internal angle at the S-substituted C atom is 121.5 (3) ° in good agreement with values reported for phenyl sulphones (Domenicano, Vaciago & Coulson, 1975). The naphthalene system is not planar: the (4) 19078 (17) 84954 (50) C (5) 21036 (15) 90256 (45) C (6) 17108 (14) 93692 (47) C (7) 19295 (17) 97825 (51) C (8) 25457 (17) 98539 (52) C (9) 29353 (17) 95268 (47) C (10) 27345 (14) 91328 ( (12) 40017 (21) 106411 (70) C (13) 41714 (13) 77332 (90) S (14) 9247 (4) 91502 (14) O (15) 7712 (11) 75753 (38) O (16) 67642 (l 1) 93450 (40) N (17) 7465 (13) 108805 (45) C (18) 1233 (18) 115306 (63) C (19) 6182 (20) 125625 (66) x y H (102) 3195 (15) 7765 (46) H (103) 2142 (15) 7429 (49) n (104) 1457 (16) 8420 (44) n (107) 1671 (16) 10013 (49) H (108) 2733 (15) 9171 (46) H …”

Trichloro(2-phenylthiophenyl)tellurium

“…Also, there are large deviations in bond angles from 120 ° which do not seem to follow a simple pattern. The average C-S distance is 1.771 (7) [3] A, which is slightly shorter than that proposed by Domenicano, Vaciago & Coulson (1975), 1.781 (3)A. The distance Te-C = 2.…”