Crystal structure of tetra­ethyl 27,30-dioxo-7,12,20,25-tetra-tert-but­yl-3,16-dioxa-9,22,28,31-tetra­thia­hepta­cyclo­[21.3.1.11,5.14,8.110,14.114,18.117,21]dotriaconta-4,6,8(29),10,12,17,19,21(32),23,25-deca­ene-2,2,15,15-tetra­carboxyl­ate

Mehmet Akkurt; Jerry P Jasinski; Shaaban K Mohamed; Omran A Omran; Mustafa R Albayati

doi:10.1107/S205698901501748X

. 2015 Sep 26;71(Pt 10):o778–o779. doi: 10.1107/S205698901501748X

Crystal structure of tetraethyl 27,30-dioxo-7,12,20,25-tetra-tert-butyl-3,16-dioxa-9,22,28,31-tetrathiaheptacyclo[21.3.1.1^1,5.1^4,8.1^10,14.1^14,18.1^17,21]dotriaconta-4,6,8(29),10,12,17,19,21(32),23,25-decaene-2,2,15,15-tetracarboxylate

Mehmet Akkurt ^a, Jerry P Jasinski ^b, Shaaban K Mohamed ^c,^d, Omran A Omran ^e,^f, Mustafa R Albayati ^g,^*

PMCID: PMC4647429 PMID: 26594475

Abstract

The asymmetric unit of the title compound, C₅₄H₆₄O₁₂S₄, consists of one half of the molecule, which is located on an inversion centre. The heterocyclic six-membered ring adopts a distorted envelope conformation with the spiro C atom as the flap. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds with an R ² ₂(14) motif, forming a chain along the b-axis direction.

Keywords: crystal structure, calixarenes, macrocycles, hydrogen bonding

Related literature

For industrial application of calixarenes, see: Shokova & Kovalev (2003 ▸); Stoikov et al. (2003 ▸). For macrocyclic reactions of calixarenes, see: Agrawal & Pancholi (2007 ▸); Higuchi et al. (2000 ▸); Omran & Antipin (2014 ▸).

Experimental

Crystal data

C₅₄H₆₄O₁₂S₄
M _r = 1033.29
Triclinic,
a = 10.9366 (6) Å
b = 11.7386 (5) Å
c = 12.6262 (8) Å
α = 100.018 (4)°
β = 113.884 (6)°
γ = 105.884 (4)°
V = 1348.75 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.49 × 0.32 × 0.14 mm

Data collection

Agilent Xcalibur, Eos, Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▸) T _min = 0.715, T _max = 0.967
16365 measured reflections
8908 independent reflections
6481 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.169
S = 1.07
8908 reflections
324 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901501748X/is5424sup1.cif

e-71-0o778-sup1.cif^{(35KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901501748X/is5424Isup2.hkl

e-71-0o778-Isup2.hkl^{(487.8KB, hkl)}

Click here for additional data file.^{(2.7MB, tif)}

a x y z . DOI: 10.1107/S205698901501748X/is5424fig1.tif

View of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are omitted for clarity. [Symmetry code: (a) 1 − x, 1 − y, 1 − z.]

Click here for additional data file.^{(1.8MB, tif)}

a . DOI: 10.1107/S205698901501748X/is5424fig2.tif

The molecular packing of the title compound viewed down the a axis. H atoms not involved in the C—H⋯O hydrogen bonds are omitted for clarity.

CCDC reference: 1425819

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C26H26AO4ⁱ	0.97	2.35	3.298(5)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

OAO would like to acknowledge support from the Deanship of Scientific Research, Majmaah University, for funding this work under project No. 1. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

S1. Comment

The macrocyclic calixarenes have been considered to be not only as good substrats in industrial chemistry but also in research field of supramolecular chemistry (Agrawal & Pancholi, 2007; Higuchi et al., 2000; Omran & Antipin, 2014). They have also been used as sensors, catalysis and molecular recognition or ion separtion (Shokova & Kovalev, 2003; Stoikov et al., 2003). In this context and following to our on-going study we report in this study the synthesis and crystal structure of the title compound.

Figure 1 shows the title molecule which lies on a crystallographic inversion centre. The heterocyclic six-membered ring (S1/C2/C21/O2/C13/C14) adopts a distorted envelope conformation with the puckering parameters of Q_T = 0.547 (2) Å, θ = 50.6 (2)° and φ = 65.2 (3)°. In the crystal, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules, forming fourteen-membered rings with R₂²(14) ring motifs, into chains along the b axis (Fig. 2).

S2. Experimental

A mixture of 1.5 g (2.08 mmol) thiacalexarene (TCA), 10 g sodium carbonate, 0.5 g of tetraethylammonium bromide (TEAB) and diethyl bromomalonate 3 ml (8. 02 mmol) in 50 ml benzene was heated at 373 K with stirring for 6 days. The reaction mixture was filtered off and the benzene layer was evaporated under vacuum to dryness. The solid residue was washed by hydrochloric diluted solution and extracted by methylene chloride (3 times). The methylene chloride portions were concentrated and methanol was added. Yellow color of two solid mixture products were precipitated and filtered off. The mixture was separated by fractional crystallization by using a mixture of methylene chloride / methanol (1:1 v:v) to afford the title compound as yellow crystals in 85% yield.