24-Acetyl-8,11,14-trioxa-24,27-diaza­penta­cyclo­[19.5.1.122,26.02,7.015,20]octa­cosa-2,4,6,15(20),16,18-hexaen-28-one

Le Tuan Anh; Truong Hong Hieu; Anatoly T Soldatenkov; Nadezhda M Kolyadina; Victor N Khrustalev

doi:10.1107/S1600536812027274

. 2012 Jun 23;68(Pt 7):o2165–o2166. doi: 10.1107/S1600536812027274

24-Acetyl-8,11,14-trioxa-24,27-diazapentacyclo[19.5.1.1^22,26.0^2,7.0^15,20]octacosa-2,4,6,15(20),16,18-hexaen-28-one

Le Tuan Anh ^a,^*, Truong Hong Hieu ^a, Anatoly T Soldatenkov ^b, Nadezhda M Kolyadina ^b, Victor N Khrustalev ^c

PMCID: PMC3393972 PMID: 22798837

Abstract

The title compound, C₂₅H₂₈N₂O₅, is a product of the Petrenko–Kritchenko condensation of N-acetylpiperidone with 1,5-bis(2-formylphenoxy)-3-oxapentane and ammonium acetate. The molecule comprises a fused pentacyclic system containing an aza-14-crown-3-ether macrocycle, two piperidone and two benzene rings. The aza-14-crown-3-ether ring adopts a bowl conformation. The dihedral angle between the benzene rings fused to the aza-14-crown-4-ether unit is 70.18 (4)°. The central piperidone ring has a boat conformation, whereas the terminal piperidone ring adopts a chair conformation. The conformation of the central piperidone ring is determined by two intramolecular N—H⋯O hydrogen bonds. In the crystal, molecules are linked by weak C—H⋯O interactions into chains along [010].

Related literature

For general background to the design, synthesis and applications of macrocyclic ligands for coordination and supramolecular chemistry, see: Hiraoka (1978 ▶); Pedersen (1988 ▶); Gokel & Murillo (1996 ▶); Bradshaw & Izatt (1997 ▶). For related compounds, see: Levov et al. (2006 ▶, 2008 ▶); Komarova et al. (2008 ▶); Anh et al. (2008 ▶, 2012a ▶,b ▶); Hieu et al. (2011 ▶); Khieu et al. (2011 ▶); Sokol et al. (2011 ▶).

Experimental

Crystal data

C₂₅H₂₈N₂O₅
M _r = 436.49
Orthorhombic,
a = 17.1756 (6) Å
b = 11.1724 (4) Å
c = 22.6546 (8) Å
V = 4347.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.973, T _max = 0.977
54466 measured reflections
6326 independent reflections
4682 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.106
S = 1.00
6326 reflections
293 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 datablock(s) global, I. DOI: 10.1107/S1600536812027274/aa2068sup1.cif

e-68-o2165-sup1.cif^{(32.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027274/aa2068Isup2.hkl

e-68-o2165-Isup2.hkl^{(309.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027274/aa2068Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N27—H27⋯O8	0.90 (2)	2.49 (2)	3.0337 (13)	119 (1)
N27—H27⋯O14	0.90 (2)	2.44 (1)	3.0193 (13)	122 (1)
C21—H21⋯O28ⁱ	1.00	2.48	3.4683 (14)	168
C30—H30B⋯O28ⁱ	0.98	2.51	3.0556 (16)	115

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the Vietnam National University, Hanoi, (grant No. QG.11.09) for the financial support of this work.

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 several decades (Hiraoka, 1978; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently we have developed the effective methods of synthesis of azacrown ethers containing piperidine (Levov et al., 2006, 2008; Anh et al., 2008, 2012a, 2012b), perhydropyrimidine (Hieu et al., 2011), perhydrotriazine (Khieu et al., 2011) and bispidine (Komarova et al., 2008; Sokol et al., 2011) subunits.

In attempts to apply this chemistry for obtaining of a macrocyclic ligand containing N-acylsubstituted bispidine moiety, we studied the Petrenko-Kritchenko condensation of the N-acetylpiperidone with 1,5-bis(2-formylphenoxy)-3-oxapentane and ammonium acetate. The reaction have proceeded smoothly to give the expected azacrown system with a good yield (Fig. 1).

The molecule of the title compound, C₂₅H₂₈ N₂O₅, comprises a fused pentacyclic system containing the aza-14-crown-3-ether macrocycle, two piperidone and two benzene rings (Fig. 2). The aza-14-crown-3-ether ring adopts a bowl conformation. The configuration of the C7—O8—C9—C10—O11—C12—C13—O14—C15 polyether chain is t–g(-)–t–t–g(+)–t (t = trans, 180°; g = gauche, ±60°). The dihedral angle between the planes of the benzene rings fused to the aza-14-crown-4-ether moiety is 70.18 (4)°. The central piperidone ring has a boat conformation, whereas the terminal piperidone ring adopts a chair conformation. Apparently, the conformation of the central piperidone ring is determined by the two intramolecular N–H···O hydrogen bonds (Table 1). The nitrogen N24 atom has a trigonal-planar geometry (sum of the bond angles is 359.8°), while the nitrogen N27 atom adopts a trigonal-pyramidal geometry (sum of the bond angles is 326.7°).

The molecule of the title compound possesses four asymmetric centers at the C1, C21, C22 and C26 carbon atoms and can have potentially numerous diastereomers. The crystal of the title compound is racemic and consists of enantiomeric pairs with the following relative configuration of the centers: rac-1R*, 21S*,22R*,26S*.

In the crystal, the molecules are bound by the weak intermolecular C–H···O hydrogen bonding interactions into the chains along [010] (Fig. 3, Table 1). The crystal packing of the chains is stacking along the a axis (Fig. 3).

Experimental

Ammonium acetate (3.0 g, 39.0 mmol) was added to a solution of 1,5-bis(2-formylphenoxy)-3-oxapentane (3.14 g, 10.0 mmol) and N-acetylpiperidone (1.41 g, 10.0 mmol) in ethanol-acetic acid mixture (30 ml 1 ml). The reaction mixture was stirred at 293 K for 3 days (monitoring by TLC until disappearance of the starting heterocyclic ketone spot). At the end of the reaction, the formed precipitate was filtered off, washed with ethanol and re-crystallized from ethanol to give 2.54 g of white crystals of the title compound. Yield is 58%. M.p.= 500–502 K. IR (KBr), ν/cm^-1: 1603, 1649, 1713, 3405, 3460. ¹H NMR (CDCl₃, 400 MHz, 300 K): δ = 2.37 (s, 3H, CH₃C=O), 2.91 (m, 3H, H22, H26 and H27), 3.47 and 4.98 (both dd, 1H each, H1 and H21, J = 7.3 and 1.1), 3.92–4.10 (m, 12H, OCH₂CH₂OCH₂CH₂O, 2H23 and 2H25), 6.75–6.95 (m, 3H, H_arom), 7.21–7.36 (m, 5H, H_arom). Anal. Calcd. for C₂₅H₂₈N₂O₅: C, 68.79; H, 6.47; N, 6.42. Found: C, 69.03; H, 6.52; N, 6.43.