5,11,17,23,29,35-Hexa-tert-butyl-37,38,39,40,41,42-hexa­kis­(eth­oxy­carbonyl­meth­oxy)calix[6]arene acetonitrile disolvate

Michaela Pojarová; Michal Dušek; Jan Budka; Ivana Císařová; Emanuel Makrlík

doi:10.1107/S1600536812015735

. 2012 Apr 18;68(Pt 5):o1418–o1419. doi: 10.1107/S1600536812015735

5,11,17,23,29,35-Hexa-tert-butyl-37,38,39,40,41,42-hexakis(ethoxycarbonylmethoxy)calix[6]arene acetonitrile disolvate

Michaela Pojarová ^a,^*, Michal Dušek ^a, Jan Budka ^b, Ivana Císařová ^c, Emanuel Makrlík ^d

PMCID: PMC3344542 PMID: 22590304

Abstract

In the title compound, C₉₀H₁₂₀O₁₈·2CH₃CN, the calix[6]arene has a 1,2,3-alternate conformation and possesses inversion symmetry. It crystallizes as an acetonitrile disolvate, with a half-molecule of calix[6]arene and one molecule of solvent in the asymmetric unit. In the crystal, the two solvent molecules are enclosed in voids between the calix[6]arene molecules. They form weak C—H⋯O hydrogen bonds involving an O atom of the lower rim substituent. The cavity of the calix[6]arene itself is enclosed by two opposite phenol rings, which are turned into the cavity due to the presence of a C—H⋯π interaction. The calix[6]arene molecule exhibits disorder of one substituent on its lower rim [occupancy ratio 0.897 (3):0.103 (3)].

Related literature

For general information about calixarenes, see: Gutsche (2008 ▶). For their applications in coordination chemistry, see: Homden & Redshaw (2008 ▶); Gibson et al. (1998 ▶), in supramolecular chemistry, see: Atwood et al. (2002 ▶) and in polymerization, see: Ling et al. (2003 ▶). For the synthesis of the title compound, see: McKervey et al. (1985 ▶).

Experimental

Crystal data

C₉₀H₁₂₀O₁₈·2C₂H₃N
M _r = 1571.97
Triclinic,
a = 12.6190 (2) Å
b = 13.1500 (3) Å
c = 14.8990 (4) Å
α = 75.9037 (11)°
β = 67.7646 (11)°
γ = 74.5815 (19)°
V = 2177.67 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.3 × 0.3 × 0.25 mm

Data collection

Nonius KappaCCD area-detector diffractometer
19018 measured reflections
9990 independent reflections
7277 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.183
S = 1.03
9990 reflections
538 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: COLLECT; data reduction: COLLECT and DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015735/su2398sup1.cif

e-68-o1418-sup1.cif^{(48.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015735/su2398Isup2.hkl

e-68-o1418-Isup2.hkl^{(488.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1C–C6C ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3E⋯O1C	0.96	2.47	3.250 (4)	139
C7C—H7C2⋯O3B	0.97	2.38	3.312 (3)	160
C12B—H12D⋯O2A	0.97	2.57	3.526 (3)	169
C15B—H15G⋯O3Aⁱ	0.96	2.48	3.398	160
C5C—H5C⋯O1Aⁱⁱ	0.93	2.44	3.190 (2)	138
C11C—H11G⋯O1Bⁱⁱ	0.96	2.56	3.477 (3)	159
C10C—H10I⋯Cg1ⁱⁱ	0.96	2.73	3.588 (3)	148

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This project was supported by the Praemium Academiae of the Academy of Science of the Czech Republic, by the Grant Agency of the Academy of Sciences of the CR (project No. IAAX08240901) and by the Grant Agency of the Faculty of Environmental Sciences, Czech University of Life Sciences, Prague (project No. 42900/1312/3114 "Environmental Aspects of Sustainable Development of Society").

supplementary crystallographic information

Comment

Calixarenes (Gutsche, 2008) have received considerable interest over the past four decades for their ability to entrap guest molecules. They have found applications in coordination (Homden & Redshaw, 2008; Gibson et al., 1998) and supramolecular chemistry (Atwood et al., 2002). They have also been investigated for their possible industrial applications such as, the catalysis of polymerization (Ling et al., 2003), or metal ion receptors (Homden & Redshaw, 2008).

The title compound crystallizes as a diacetonotrile solvate, with half a molecule of calix[6]arene and one molecule of acetonitrile in the asymmetric unit (Fig. 1). The molecular structure of the title compound is illustrated in Fig. 2. The acetonitrile molecule is bound to the calix[6]arene via a weak C-H···O hydrogen bond involving an O atom of a lower rim substituent (Table 1). Due to the presence of the oxygen atoms, the lower rim substituents are suitable acceptors of weak C-H···O hydrogen bonds (intra- and intermolecular) from surrounding bridging methylene (C7) and methyl (C15) groups (Table 1). The shape of the calix[6]arene cavity is influenced by the presence of C—H···π interactions between the methyl group of the tert-butyl group and the aromatic ring C1c-C6c (Table 1 and Fig. 3).

The lower-rim substituent atoms (O3a,C14a,C15a) of ring C1a-C6a, are disordered over two position with an occupancy ratio of 0.897 (3) : 0.103 (3).

Experimental

The title compound was prepared following a previously published procedure (McKervey et al. 1985).