The Inclusion of Carbon Disulfide in p-tert-Butylcalix[4]-and [6 ]arene - A Combined Crystallographic and Vibrational Spectroscopic Study

Abstract

Jürgen Schatz3, Frank Schildbacha, Axel L en tzb, Sylvia R a stä tte rb, Joachim Schilling5, Jö rg D o rm an n c, A n d reas R uoffc, and Tony D eb ae rd em ae k erd The inclusion complexes formed from carbon disulfide and /?-r£7-r-butylcalix[4]arene ( 1 C S 2) or /?-rm-butylcalix[6]arene (2-C S2) were investigated by X-ray crystal structure analysis, infrared (IR) and Raman spectroscopy. The complex 1 C S 2 crystallises in the space group P4/n, 2 C S 2 in the space group P2xln. In case of /?-rm-butylcalix[4]arene as host the carbon disulfide molecule is included in the cavity. In the crystal structure of p-rm -butylcalix[6]arene clathrate, self-com plexation o f one rm-butyl group in the cavity o f another calix[6]arene can be observed. Due to inclusion, the symmetry of CS2 is lowered both in the prm -butylcalix[4]arene and p-rm-butylcalix[6]arene case causing significant shifts in the fully assigned infrared and Raman spectra.

Vibrational analysis ofp-tert-butyl-calix[4]arene conformers byab initiocalculations

“…The calculated geometric parameters of calix [4]arene are in good accordance with X-ray experiments [14]. Computation reveals that the cone conformer is observed for isolated calix [4]arene molecules (table 1).…”

“…Partial cone 1,3-alternate 1,2-alternate IR spectroscopy is used generally for characterization of host-guest interactions [11][12][13] in calixarenes [14]. For a reliable explanation of IR spectra an analysis of normal vibrations must be platformed.…”

Insights into molecular recognition from the crystal structures of p-tert-butylcalix[6]arene complexed with different solvents

“…The CSD was queried for error-free organic crystal structures determined at room temperature or below. A total of ten different crystal structures were found: KAHJUY (benzene 1:3; Halit et al, 1988), KENBUA (tetrachloroethene 1:1; Andreetti et al, 1989), LODNIB (carbon disulfide 1:1; Schatz, Schildbach et al, 2000), TECDUB (DCM 1:2; Felsmann et al, 2006), UWIVUS (chlorobenzene 1:1; Ramon et al, 2011), UWIWAZ (bromobenzene 1:1; Ramon et al, 2011), VARGOL (acetonitrile 2:3; Dale et al, 2003), VARGUR (acetonitrile 1:2; Dale et al, 2003), WORMEV (toluene 1:1; Lu et al, 1999) and ZIPYOM (acetonitrile 2:3; Thue ´ry et al, 1994).…”

para-Acylcalix[n]arenes: from molecular to macroscopic assemblies

“…This structure can be called an open-container or head-to-tail complex and it is typical of para-butanoyl (C 4 ), para-hexanoyl (C 6 ) and para-octanoyl (C 8 ) calix [4]arenes with such guests as THF (in C 4 72 and C 8 71 ), DMSO, DMF, nitrobenzene, 68 hydroxylamine TEMPO-H, 67 (in C 6 ), and acetone (in C 8 ), 76 as well as for some other calix[n]arenes. [1][2][3]7,29,[50][51][52][53][54][55][56][57][58][59][60][77][78][79][80][81][82][83][84][85][86] In the case of the molecule with long alkanoyl arms (C 8 ) the cavity of the para-acylcalixarene becomes large enough to accommodate two molecules of the guest (THF, 71 acetone, or possibly others); however, these structures are not stable upon long storage at room temperature and easily transform to interdigitated guest-free form. The third type is the nanocapsular complex, 7,27,29,[51][52][53][54][55]70,72,[87][88]…”