(2E,25E)-11,14,17,33,36,39,42-Hepta­oxa­penta­cyclo­[41.4.0.05,10.018,23.027,32]hepta­tetra­conta-1(43),2,5(10),6,8,18,20,22,25,27,29,31,44,46-tetra­decaene-4,24-dione

Le Tuan Anh; Truong Hong Hieu; Anatoly T Soldatenkov; Svetlana A Soldatova; Victor N Khrustalev

doi:10.1107/S1600536811013201

. 2011 Apr 13;67(Pt 5):o1128–o1129. doi: 10.1107/S1600536811013201

(2E,25E)-11,14,17,33,36,39,42-Heptaoxapentacyclo[41.4.0.0^5,10.0^18,23.0^27,32]heptatetraconta-1(43),2,5(10),6,8,18,20,22,25,27,29,31,44,46-tetradecaene-4,24-dione

Le Tuan Anh ^a,^*, Truong Hong Hieu ^a, Anatoly T Soldatenkov ^b, Svetlana A Soldatova ^b, Victor N Khrustalev ^c

PMCID: PMC3089172 PMID: 21754440

Abstract

The title compound, C₄₀H₄₀O₉, is a product of the double crotonic condensation of bis(2-acetylphenoxy)-3-oxapentane with bis(2-formylphenoxy)-3,6-dioxaoctane. The title macromolecule includes the 31-crown-7-ether skeletal unit and adopts a saddle-like conformation. The two ethylene fragments have E configurations. The volume of the internal cavity of the macrocycle is approximately 125 Å³. In the crystal, the molecules are arranged at van der Waals distances.

Related literature

For general background to the design, synthesis and applications of macrocyclic ligands for coordination and supramolecular chemistry, see: Hiraoka (1978 ▶); Pedersen (1988 ▶); Bradshaw & Izatt (1997) ▶; Gokel & Murillo (1996 ▶). For related compounds, see: Levov et al. (2006 ▶, 2008 ▶); Anh et al. (2008 ▶)

Experimental

Crystal data

C₄₀H₄₀O₉
M _r = 664.72
Monoclinic,
a = 12.3268 (6) Å
b = 11.0271 (6) Å
c = 13.1142 (7) Å
β = 106.933 (1)°
V = 1705.32 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.973, T _max = 0.982
19455 measured reflections
5222 independent reflections
4511 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.128
S = 1.01
5222 reflections
442 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013201/rk2273sup1.cif

e-67-o1128-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013201/rk2273Isup2.hkl

e-67-o1128-Isup2.hkl^{(255.7KB, hkl)}

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

supplementary crystallographic information

Comment

Design, synthesis and applications of macrocyclic ligands for coordination and supramolecular chemistry draw very great attention of investigators during the last forty years (Hiraoka, 1978; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently, we have developed an effective method of synthesis of 14- and 17-membered azacrown (Levov et al., 2006; 2008) and crown (Anh et al., 2008) ethers. This method is based on domino reaction of three components - dialkyl ketone, bis(2-formylphenoxy)-3-oxapentane and ammonium acetate, i.e., the modified Petrenko–Kritchenko reaction (Levov, 2008).

In attempts to apply this chemistry for obtaining of a ditopic ligand, in which two azacrown units are connected to each other by polyether chain, we studied the similar condensation of bis(2-formylphenoxy)-3,6-dioxaoctane with bis(2-acetylphenoxy)-3-oxapentane and ammonium acetate, the latter being both a source of nitrogen and a template agent. However, instead of the expected azacrown system, tetrakis(benzo)-31-crown-7-ether (I) was formed.

The obtained compound I, C₄₀H₄₀O₉, includes the 31–crown–7–ether skeletal moiety and adopts a saddle-like conformation (Fig. 1). The two ethylene fragments have Econfigurations. The dihedral angles between the benzene planes of C1,C43–C47/C5–C10, C5–C10/C18–C23, C18–C23/C27–C32 and C27–C32/C1,C43–C47 are 64.91 (8), 65.14 (8), 61.64 (8) and 56.67 (9)°, respectively. The volume of the internal cavity of macrocycle I is approximately equal to 125 Å³. The distances from the center of macrocycle cavity, defined as centroid of O11/O14/O17/O33/O36/O39/O42 oxygen donor atoms, to the O11, O14, O17, O33, O36, O39 and O42 oxygen atoms are 3.286 (3), 3.638 (3), 3.460 (3), 3.308 (3), 3.486 (3), 3.524 (3) and 2.533 (3) Å, respectively.

In the crystal, the molecules of I are arranged at van der Waals distances.

Experimental

Ammonium acetate (2.0 g, 26 mmol) was added to a solution of bis(2-formylphenoxy)-3,6-dioxaoctane (1.38 g, 4.40 mmol) with bis(2-acetylphenoxy)-3-oxapentane (1.50 g, 4.40 mmol) in ethanol (50 ml). The reaction mixture was stirred at 323 K for 2 h (monitoring by TLC until disappearance of the starting organic compounds spots). At the end of the reaction, the formed wax-like precipitate was separated, washed with cold ethanol (50 ml) and re-crystallized from ethanol to give 0.82 g of light-yellow crystals of I (Fig. 2). Yield is 28%. M.p. = 400–402 K. IR (KBr), ν/cm^-1: 1618, 1682. ¹H NMR (CDCl₃ , 400 MHz, 300 K): δ = 3.54, 3.62, 3.85 and 4.11 (all m, 6H, 5H, 5H and 4H, respectively, OCH₂CH₂O), 6.70–7.23 and 7.28–7.55 (both m, 10H and 6H, respectively, H_arom), 7.27 and 7.87 (both d, 2H each, O═C—CH_trans═CH, J = 16.0). Anal. Calcd for C₄₀H₄₀O₉: C, 72.29; H, 6.03. Found: C, 72.31; H, 6.12.