Propellane, 8. Mitt.: Eine neue Synthese von Bis-Propellanen. 1,2,4,5-Bis{8′,11′-dioxa[4.3.3]propella(3′,4′)}benzol

Structural and theoretical study on the 1:2 addition complex of 1,2,4,5-bis{8′,11′-dithia[4.3.3]propella(3′,4′)}benzene with I2

“…The results of calculations performed using CRYSTAL09 with 6-31G(d,p) basis set on C, H, S, and LANL2DZ effective core potential on I, indicated the increase of the unit-cell volume by almost 30% when compared with the experimental value. Inclusion of the empirical dispersion correction to the calculations gave a fairly satisfactory result concerning the unit-cell volume: the volume increased by 2.2% only, however, the calculated I 2 bond length increased to 3.055 Å and S(12)Á Á ÁI (14) to 2.815 Å when compared to the experimental values. The use of MIDI!…”

“…method showed that the geometrical parameters of 3 molecule are comparable to those found for the experimental data from X-ray diffraction and those calculated with CRYSTAL09. However, there are significant differences for S(12)Á Á ÁI (14) and I(14)-I(15) distances ( Table 2). The elongation of S(12)Á Á ÁI (14) distance in the case of isolated complex 3ÁI 2 is due to lack of intermolecular interactions present in the crystalline state.…”

“…The unit-cell volume at this level of approximation grew up by 4%. Inclusion of Grimme correction deteriorated both the volume, which diminished by 7.1%, and S(12)Á Á ÁI (14) bond length (2.727 Å). In conclusion, the correct reproduction of the geometry in the studied case requires an all-electron good-quality basis set on all atoms rather than effective core-potential approach corrected with dispersion corrections.…”

“…The use of MIDI! basis set gave much better description of I 2 and S(12)Á Á ÁI (14) distances (optimised lengths 2.923 and 2.754 Å, respectively). The unit-cell volume at this level of approximation grew up by 4%.…”

“…For the minor component there are no obvious interactions between S(12) and I (16), and between S(9) and I(17), so the distance I(16)-I(17) = 2.74(2) Å is in agreement with the value of 2.715(6) Å within the limit of error. Additionally, I (14) and I (16) can be considered as acceptors in weak C(10)-H(10A)Á Á ÁI interactions ( Table 3).…”