Dimethyl 2-[22,24-dimethyl-23-oxo-8,11,14-trioxa-25-aza­tetra­cyclo­[19.3.1.02,7.015,20]penta­cosa-2,4,6,15(20),16,18-hexaen-25-yl]but-2-enedioate

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

doi:10.1107/S1600536812018867

. 2012 May 2;68(Pt 6):o1588–o1589. doi: 10.1107/S1600536812018867

Dimethyl 2-[22,24-dimethyl-23-oxo-8,11,14-trioxa-25-azatetracyclo[19.3.1.0^2,7.0^15,20]pentacosa-2,4,6,15(20),16,18-hexaen-25-yl]but-2-enedioate

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

PMCID: PMC3379201 PMID: 22719399

Abstract

The title compound, C₂₉H₃₃NO₈, is a product of the Michael addition of the cyclic secondary amine subunit of the aza-14-crown-4 ether to dimethyl acetylenedicarboxylate. The piperidinone ring exhibits a distorted chair conformation, and the dimethyl ethylenedicarboxylate fragment has a cis configuration with a dihedral angle of 78.96 (5)° between the two carboxylate groups. The crystal packing is stabilized by weak C—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₂₉H₃₃NO₈
M _r = 523.56
Triclinic,
a = 8.8135 (4) Å
b = 8.9469 (4) Å
c = 18.3067 (9) Å
α = 79.077 (1)°
β = 78.218 (1)°
γ = 69.800 (1)°
V = 1315.05 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.10 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 = 0.972, T _max = 0.976
17255 measured reflections
7669 independent reflections
6322 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.117
S = 1.00
7669 reflections
347 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536812018867/cv5289sup1.cif

e-68-o1588-sup1.cif^{(35.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018867/cv5289Isup2.hkl

e-68-o1588-Isup2.hkl^{(375.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812018867/cv5289Isup3.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
C13—H13A⋯O1ⁱ	0.99	2.56	3.2877 (18)	130
C29—H29A⋯O3ⁱⁱ	0.98	2.44	3.2498 (18)	139
C33—H33A⋯O5ⁱⁱⁱ	0.98	2.56	3.4092 (16)	145

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

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 forty years (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, 2012), perhydropyrimidine (Hieu et al., 2011) and perhydrotriazine subunits (Khieu et al., 2011).

In attempts to apply this chemistry for obtaining of a macrocyclic ligand bringing the desirable functional groups, we studied the Michael addition of the cyclic secondary amine subunit of the crown ether to dimethyl ethylenedicarboxylate. The expected reaction is well known (Schwan & Warkentin, 1988), but might be highly hindered due to the steric reasons. We have found, however, that the expected N-vynilation proceeded smoothly with the formation of an N-maleinate derivative of the azacrown system.

The title compound I, C₂₉H₃₃NO₈, is a product of the Michael addition of the cyclic secondary amine subunit of the aza-14-crown-4 ether to dimethyl acetylenedicarboxylate (Figure 1). The title macromolecule includes the aza-14-crown-4-ether skeletal moiety and adopts a bowl conformation (Figure 2). 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 piperidinone ring of the bicyclic fragment have a slightly flattenned chair conformation. The dihedral angle between the planes of the benzene rings fused to the aza-14-crown-4-ether moiety is 56.33 (4)°. The methyl substituents at the C22 and C24 carbon atoms occupy the sterically favorable equatorial positions. The carboxylate substituents are rotated to each other by 78.96 (5)°. The volume of the internal cavity of macrocycle I is approximately equal to 57 Å³.

The molecule of I possesses four asymmetric centers at the C1, C21, C22 and C24 carbon atoms and can have potentially numerous diastereomers. The crystal of I is racemic and consists of enantiomeric pairs with the following relative configuration of the centers: rac-1R*,21S*,22R*,24S*.

In the crystal, the molecules of I are bound to each other by weak C—H···O hydrogen bonding interactions (Table 1) into three-dimensional framework.

Experimental

Dimethyl acetylenedicarboxylate (0.11 g, 0.79 mmol) was added to a solution of bis(benzo)-(β,β'-dimethyl-γ-piperidono)aza-14-crown-4 ether (0.30 g, 0.79 mmol) in chloroform (20 ml). The reaction mixture was stirred at 293 K for 3 days (monitoring by TLC until disappearance of the starting organic compounds spots). At the end of the reaction, the formed precipitate was separated, washed with cold chloroform (40 ml) and re-crystallized from ethanol to give 0.41 g of pale yellow crystals of I. Yield is 99%. M.p. = 506–508 K. IR (KBr), ν/cm^-1: 1599, 1643, 1710, 1729. ¹H NMR (CDCl₃, 400 MHz, 300 K): δ = 0.43 (d, 6H, C—CH₃, J = 7.0), 3.00 and 3.17 (both s, 3H each, CH₃), 3.46, 3.54, 3.60 and 3.68 (all m, 2H, 4H, 2H and 2H, respectively, H22, H24 and OCH₂CH₂OCH₂CH₂O), 3.76 and 3.83 (both d, 1H each, H1 and H21, J = 10.1), 6.39 and 6.43 (both m, 2H each, H_arom), 6.49(c, 1H, O₂C—CH=C—CO₂), 6.58 (dd, 2H, J = 7.2 and 2.0), 6.86 (tt, 2H, J = 8.4 and 2.0, H_arom). Anal. Calcd for C₂₉H₃₃NO₈: C, 66.53; H, 6.35; N, 2.68. Found: C, 66.81; H, 6.70; N, 2.75.