organic compounds
Dimethyl 2-[24-acetyl-28-oxo-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-27-yl]but-2-enedioate
aDepartment of Chemistry, Vietnam National University, 144 Xuan Thuy, Cau Giay, Hanoi, Vietnam, bOrganic Chemistry Department, Russian People's Friendship University, Miklukho-Maklaya Street 6, Moscow, 117198, Russian Federation, and cX-ray Structural Centre, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, B-334, Moscow 119991, Russian Federation
*Correspondence e-mail: thh1101@yahoo.com
The title compound, C31H34N2O9, is a product of the Michael addition of the cyclic secondary amine subunit of the (bispidino)aza-14-crown-4 ether to dimethyl acetylenedicarboxylate. The molecule comprises a tricyclic system containing the aza-14-crown-3 ether macrocycle and two six-membered piperidinone rings. The aza-14-crown-3-ether ring adopts a bowl conformation with a dihedral angle between the planes of the fused benzene rings of 51.14 (5)°. The central piperidone ring has a boat conformation, whereas the terminal piperidone ring adopts a chair conformation. The dimethyl ethylenedicarboxylate fragment has a cis configuration with a dihedral angle of 56.56 (7)° between the two carboxylate groups. The crystal packing is stabilized by weak C—H⋯O hydrogen bonds.
Related literature
For general background, see: Hiraoka (1982); Pedersen (1988); Schwan & Warkentin (1988); Gokel & Murillo (1996); Bradshaw & Izatt (1997). For related compounds, see: Levov et al. (2006, 2008); Komarova et al. (2008); Anh et al. (2008); Anh, Hieu, Soldatenkov, Kolyadina & Khrustalev (2012a,b); Anh, Hieu, Soldatenkov, Soldatova & Khrustalev (2012); Hieu et al. (2011); Khieu et al. (2011); Sokol et al. (2011).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2005); cell 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.
Supporting information
https://doi.org/10.1107/S1600536812030644/rk2370sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030644/rk2370Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812030644/rk2370Isup3.cml
Dimethylacetylenedicarboxylate (0.24 g, 1.69 mmol) was added to a solution of (bispidino)aza-14-crown-4ether (0.25 g, 0.57 mmol) in chloroform (20 ml). The reaction mixture was stirred at 293 K for one day (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 (15 ml) and re-crystallized from ethanol to give 0.32 g of colourless crystals of I. Yield is 98%. M.p. = 522-524 K. IR (KBr), ν/cm-1: 1603, 1651, 1715. 1H NMR (CDCl3, 400 MHz, 300 K): δ = 2.33 (s, 3H, CH3C═O), 3.02 (m, 2H, H22 and H26), 3.28 and 3.43 (both s, 3H each, OCH3), 3.79-4.10 (m, 12H, OCH2CH2OCH2CH2O, 2H23 and 2H25), 4.4 and 4.56 (both d, 1H each, H1 and H21, J = 7.3), 6.56 (s, 1H, C═CHCOO), 6.70-6.78 (m, 4H, Harom), 7.05 (d, 2H, H3 and H19, J = 7.6), 7.21 (m, 2H, Harom). Anal. Calcd for C31H34 N2O9: C, 64.35; H, 5.92; N, 4.84. Found: C, 64.41; H, 6.07; N, 4.67.
The hydrogen atoms were placed in calculated positions with C–H = 0.95-1.00Å and refined in the riding model with fixed isotropic displacement parameters: Uiso(H) = 1.5Ueq(C) for the methyl group and 1.2Ueq(C) for the other groups.
Azacrown
draw very great attention of investigators over the last half century owing to their great potential for both theoretical and practical interest (Hiraoka, 1982; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently we have designed one more effective route to reach this fascinating region of macroheterocyclic compounds, namely, the effective method of synthesis of azacrown containing piperidine (Levov et al., 2006, 2008; Anh et al., 2008; Anh, Hieu, Soldatenkov, Kolyadina & Khrustalev, 2012a; Anh, Hieu, Soldatenkov, Soldatova & Khrustalev, 2012), perhydropyrimidine (Hieu et al., 2011), perhydrotriazine (Khieu et al., 2011) and bispidine (Komarova et al., 2008; Sokol et al., 2011; Anh, Hieu, Soldatenkov, Kolyadina & Khrustalev, 2012b) subunits.In attempts to develop the chemistry for new azacrown systems and to obtain macrocyclic ligands bringing the desirable functional groups, we studied the Michael addition of the cyclic secondary amine subunit of the (bispidino)aza-14-crown-4 ether to dimethyl acetylenedicarboxylate. The expected reaction is well known (Schwan & Warkentin, 1988), but might be highly hindered in the case of (bispidino)azacrown system due to the steric reasons. We have found that the expected N-vynilation reaction of the (bispidino)azacrown ether proceeded smoothly to give an N-maleinate derivative of the azacrown system with a good yield (Fig. 1).
The molecule of I, C31H34N2O9, comprises a tricyclic system containing the aza-14-crown-3-ether macrocycle and two six-membered piperidinone 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 51.14 (5)°. The central piperidone ring has a boat conformation, whereas the terminal piperidone ring adopts a chair conformation. The nitrogen N24 atom has a trigonal-planar geometry (sum of the bond angles is 360.0°), while the nitrogen N27 atom adopts a trigonal-pyramidal geometry (sum of the bond angles is 340.5°). The dimethyl ethylenedicarboxylate fragment has a cis configuration with a dihedral angle of 56.56 (7)° between the two carboxylate groups.
The molecule of I possesses four asymmetric centers at the C1, C21, C22 and C26 carbon atoms and can have potentially numerous
The crystal of I is racemic and consists of enantiomeric pairs with the following of the centers: rac-1R*, 21S*,22R*,26S*.In the crystal, the molecules of I are bound by the weak intermolecular C–H···O hydrogen bonding interactions into three-dimensional framework (Table 1).
For general background, see: Hiraoka (1982); Pedersen (1988); Schwan & Warkentin (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, 2012b); Anh et al., 2012; Hieu et al. (2011); Khieu et al. (2011); Sokol et al. (2011).
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C31H34N2O9 | F(000) = 1224 |
Mr = 578.60 | Dx = 1.337 Mg m−3 |
Monoclinic, P21/c | Melting point = 522–524 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6634 (6) Å | Cell parameters from 6686 reflections |
b = 26.3883 (18) Å | θ = 2.3–30.4° |
c = 11.4375 (8) Å | µ = 0.10 mm−1 |
β = 99.614 (1)° | T = 100 K |
V = 2875.6 (3) Å3 | Prism, light yellow |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Bruker APEXII CCD diffractometer | 8396 independent reflections |
Radiation source: fine-focus sealed tube | 6209 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
φ and ω scans | θmax = 30.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→13 |
Tmin = 0.971, Tmax = 0.981 | k = −37→36 |
36500 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.046P)2 + 1.09P] where P = (Fo2 + 2Fc2)/3 |
8396 reflections | (Δ/σ)max < 0.001 |
382 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C31H34N2O9 | V = 2875.6 (3) Å3 |
Mr = 578.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6634 (6) Å | µ = 0.10 mm−1 |
b = 26.3883 (18) Å | T = 100 K |
c = 11.4375 (8) Å | 0.30 × 0.20 × 0.20 mm |
β = 99.614 (1)° |
Bruker APEXII CCD diffractometer | 8396 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 6209 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.981 | Rint = 0.045 |
36500 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.40 e Å−3 |
8396 reflections | Δρmin = −0.26 e Å−3 |
382 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.11569 (13) | 0.11896 (5) | 0.20020 (11) | 0.0157 (2) | |
H1 | 0.0768 | 0.1525 | 0.2195 | 0.019* | |
C2 | 0.09245 (13) | 0.11385 (5) | 0.06665 (11) | 0.0179 (3) | |
C3 | 0.02840 (14) | 0.15322 (6) | −0.00310 (12) | 0.0216 (3) | |
H3 | 0.0081 | 0.1840 | 0.0335 | 0.026* | |
C4 | −0.00658 (16) | 0.14824 (6) | −0.12602 (13) | 0.0276 (3) | |
H4 | −0.0504 | 0.1754 | −0.1727 | 0.033* | |
C5 | 0.02316 (16) | 0.10347 (6) | −0.17898 (13) | 0.0287 (3) | |
H5 | −0.0025 | 0.0996 | −0.2624 | 0.034* | |
C6 | 0.08995 (15) | 0.06399 (6) | −0.11215 (12) | 0.0250 (3) | |
H6 | 0.1117 | 0.0336 | −0.1497 | 0.030* | |
C7 | 0.12495 (14) | 0.06917 (5) | 0.01056 (12) | 0.0200 (3) | |
O8 | 0.18727 (11) | 0.03213 (4) | 0.08372 (8) | 0.0225 (2) | |
C9 | 0.24451 (16) | −0.01130 (6) | 0.03346 (13) | 0.0250 (3) | |
H9A | 0.3061 | −0.0007 | −0.0232 | 0.030* | |
H9B | 0.1685 | −0.0329 | −0.0088 | 0.030* | |
C10 | 0.32707 (16) | −0.03936 (5) | 0.13614 (13) | 0.0250 (3) | |
H10A | 0.2677 | −0.0460 | 0.1972 | 0.030* | |
H10B | 0.3595 | −0.0723 | 0.1092 | 0.030* | |
O11 | 0.44422 (10) | −0.00887 (4) | 0.18432 (8) | 0.0223 (2) | |
C12 | 0.50802 (16) | −0.02495 (5) | 0.29917 (13) | 0.0250 (3) | |
H12A | 0.5739 | −0.0531 | 0.2926 | 0.030* | |
H12B | 0.4353 | −0.0373 | 0.3438 | 0.030* | |
C13 | 0.58570 (15) | 0.01879 (5) | 0.36341 (13) | 0.0220 (3) | |
H13A | 0.6447 | 0.0070 | 0.4376 | 0.026* | |
H13B | 0.6472 | 0.0350 | 0.3131 | 0.026* | |
O14 | 0.48284 (9) | 0.05405 (3) | 0.38952 (8) | 0.01810 (19) | |
C15 | 0.52964 (13) | 0.09761 (5) | 0.44734 (11) | 0.0154 (2) | |
C16 | 0.66552 (13) | 0.10392 (5) | 0.50956 (11) | 0.0175 (3) | |
H16 | 0.7331 | 0.0778 | 0.5094 | 0.021* | |
C17 | 0.70186 (14) | 0.14851 (5) | 0.57176 (12) | 0.0202 (3) | |
H17 | 0.7942 | 0.1525 | 0.6148 | 0.024* | |
C18 | 0.60535 (14) | 0.18708 (5) | 0.57162 (12) | 0.0202 (3) | |
H18 | 0.6306 | 0.2175 | 0.6143 | 0.024* | |
C19 | 0.47031 (14) | 0.18075 (5) | 0.50794 (11) | 0.0182 (3) | |
H19 | 0.4042 | 0.2075 | 0.5071 | 0.022* | |
C20 | 0.42963 (13) | 0.13655 (5) | 0.44570 (11) | 0.0147 (2) | |
C21 | 0.27882 (13) | 0.13019 (5) | 0.38529 (11) | 0.0144 (2) | |
H21 | 0.2286 | 0.1629 | 0.3921 | 0.017* | |
C22 | 0.20355 (13) | 0.08817 (5) | 0.44644 (11) | 0.0158 (2) | |
H22 | 0.2728 | 0.0704 | 0.5076 | 0.019* | |
C23 | 0.08405 (14) | 0.11077 (5) | 0.50463 (11) | 0.0191 (3) | |
H23A | 0.0399 | 0.0836 | 0.5455 | 0.023* | |
H23B | 0.1229 | 0.1364 | 0.5644 | 0.023* | |
N24 | −0.02109 (11) | 0.13426 (5) | 0.41473 (10) | 0.0192 (2) | |
C25 | −0.08063 (13) | 0.10019 (6) | 0.31856 (12) | 0.0207 (3) | |
H25A | −0.1472 | 0.1192 | 0.2591 | 0.025* | |
H25B | −0.1331 | 0.0727 | 0.3506 | 0.025* | |
C26 | 0.03642 (13) | 0.07711 (5) | 0.25846 (11) | 0.0168 (2) | |
H26 | −0.0050 | 0.0520 | 0.1970 | 0.020* | |
N27 | 0.26543 (11) | 0.11722 (4) | 0.25751 (9) | 0.0146 (2) | |
C28 | 0.13448 (13) | 0.05052 (5) | 0.35589 (11) | 0.0173 (3) | |
O28 | 0.14211 (11) | 0.00491 (4) | 0.36862 (9) | 0.0246 (2) | |
C29 | −0.05451 (14) | 0.18412 (6) | 0.42329 (13) | 0.0233 (3) | |
O29 | 0.00129 (12) | 0.21020 (4) | 0.50702 (10) | 0.0323 (3) | |
C30 | −0.16326 (16) | 0.20626 (6) | 0.32678 (15) | 0.0304 (3) | |
H30A | −0.1776 | 0.2421 | 0.3437 | 0.046* | |
H30B | −0.2519 | 0.1879 | 0.3236 | 0.046* | |
H30C | −0.1309 | 0.2032 | 0.2503 | 0.046* | |
C31 | 0.36237 (13) | 0.14313 (5) | 0.19759 (11) | 0.0149 (2) | |
C32 | 0.44149 (13) | 0.11639 (5) | 0.13532 (11) | 0.0162 (2) | |
H32 | 0.4245 | 0.0809 | 0.1296 | 0.019* | |
C33 | 0.55331 (14) | 0.13640 (5) | 0.07407 (11) | 0.0170 (2) | |
O33 | 0.67355 (10) | 0.12234 (4) | 0.09900 (9) | 0.0259 (2) | |
O34 | 0.50805 (10) | 0.16863 (4) | −0.01385 (9) | 0.0238 (2) | |
C34 | 0.61758 (16) | 0.18984 (6) | −0.07172 (14) | 0.0277 (3) | |
H34A | 0.5771 | 0.2155 | −0.1293 | 0.042* | |
H34B | 0.6600 | 0.1628 | −0.1127 | 0.042* | |
H34C | 0.6896 | 0.2055 | −0.0122 | 0.042* | |
C35 | 0.37909 (14) | 0.19960 (5) | 0.21065 (11) | 0.0172 (2) | |
O35 | 0.48639 (11) | 0.22224 (4) | 0.20779 (10) | 0.0258 (2) | |
O36 | 0.25872 (10) | 0.22096 (4) | 0.22817 (9) | 0.0209 (2) | |
C36 | 0.25952 (17) | 0.27511 (5) | 0.24882 (14) | 0.0266 (3) | |
H36A | 0.1657 | 0.2889 | 0.2206 | 0.040* | |
H36B | 0.3274 | 0.2913 | 0.2059 | 0.040* | |
H36C | 0.2859 | 0.2818 | 0.3339 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0137 (6) | 0.0194 (6) | 0.0137 (6) | −0.0016 (5) | 0.0010 (4) | −0.0006 (5) |
C2 | 0.0145 (6) | 0.0247 (7) | 0.0141 (6) | −0.0040 (5) | 0.0011 (4) | −0.0005 (5) |
C3 | 0.0203 (6) | 0.0263 (7) | 0.0179 (6) | −0.0004 (5) | 0.0025 (5) | 0.0014 (5) |
C4 | 0.0263 (7) | 0.0376 (9) | 0.0184 (7) | 0.0024 (6) | 0.0023 (6) | 0.0072 (6) |
C5 | 0.0285 (7) | 0.0429 (9) | 0.0142 (6) | −0.0008 (7) | 0.0026 (5) | 0.0000 (6) |
C6 | 0.0265 (7) | 0.0325 (8) | 0.0160 (6) | −0.0032 (6) | 0.0039 (5) | −0.0050 (6) |
C7 | 0.0178 (6) | 0.0250 (7) | 0.0171 (6) | −0.0034 (5) | 0.0023 (5) | −0.0011 (5) |
O8 | 0.0290 (5) | 0.0207 (5) | 0.0175 (5) | 0.0017 (4) | 0.0031 (4) | −0.0036 (4) |
C9 | 0.0301 (7) | 0.0218 (7) | 0.0223 (7) | −0.0007 (6) | 0.0019 (6) | −0.0092 (6) |
C10 | 0.0309 (7) | 0.0165 (7) | 0.0270 (7) | −0.0033 (6) | 0.0027 (6) | −0.0063 (5) |
O11 | 0.0263 (5) | 0.0194 (5) | 0.0201 (5) | −0.0024 (4) | 0.0011 (4) | −0.0001 (4) |
C12 | 0.0335 (8) | 0.0162 (7) | 0.0237 (7) | 0.0036 (6) | −0.0001 (6) | −0.0005 (5) |
C13 | 0.0219 (6) | 0.0188 (7) | 0.0245 (7) | 0.0055 (5) | 0.0012 (5) | −0.0030 (5) |
O14 | 0.0171 (4) | 0.0143 (4) | 0.0229 (5) | −0.0004 (3) | 0.0035 (4) | −0.0024 (4) |
C15 | 0.0180 (6) | 0.0154 (6) | 0.0132 (6) | −0.0016 (5) | 0.0039 (5) | 0.0008 (5) |
C16 | 0.0163 (6) | 0.0194 (6) | 0.0171 (6) | 0.0021 (5) | 0.0037 (5) | 0.0020 (5) |
C17 | 0.0158 (6) | 0.0269 (7) | 0.0168 (6) | −0.0025 (5) | −0.0003 (5) | −0.0002 (5) |
C18 | 0.0215 (6) | 0.0210 (7) | 0.0172 (6) | −0.0032 (5) | 0.0006 (5) | −0.0045 (5) |
C19 | 0.0204 (6) | 0.0176 (6) | 0.0166 (6) | 0.0010 (5) | 0.0029 (5) | −0.0008 (5) |
C20 | 0.0157 (6) | 0.0165 (6) | 0.0117 (5) | −0.0003 (5) | 0.0020 (4) | 0.0018 (5) |
C21 | 0.0145 (5) | 0.0168 (6) | 0.0116 (5) | −0.0002 (4) | 0.0015 (4) | −0.0003 (4) |
C22 | 0.0156 (6) | 0.0185 (6) | 0.0135 (6) | −0.0008 (5) | 0.0032 (4) | 0.0010 (5) |
C23 | 0.0178 (6) | 0.0250 (7) | 0.0148 (6) | −0.0015 (5) | 0.0041 (5) | −0.0014 (5) |
N24 | 0.0140 (5) | 0.0260 (6) | 0.0178 (5) | −0.0004 (4) | 0.0031 (4) | −0.0040 (5) |
C25 | 0.0143 (6) | 0.0285 (7) | 0.0195 (6) | −0.0041 (5) | 0.0034 (5) | −0.0038 (5) |
C26 | 0.0158 (6) | 0.0196 (6) | 0.0150 (6) | −0.0041 (5) | 0.0028 (5) | −0.0025 (5) |
N27 | 0.0133 (5) | 0.0186 (5) | 0.0119 (5) | −0.0020 (4) | 0.0018 (4) | −0.0004 (4) |
C28 | 0.0166 (6) | 0.0202 (6) | 0.0165 (6) | −0.0022 (5) | 0.0070 (5) | 0.0002 (5) |
O28 | 0.0298 (5) | 0.0182 (5) | 0.0266 (5) | −0.0019 (4) | 0.0068 (4) | 0.0005 (4) |
C29 | 0.0180 (6) | 0.0265 (7) | 0.0263 (7) | −0.0004 (5) | 0.0067 (5) | −0.0024 (6) |
O29 | 0.0315 (6) | 0.0279 (6) | 0.0356 (6) | −0.0008 (5) | 0.0003 (5) | −0.0092 (5) |
C30 | 0.0249 (7) | 0.0306 (8) | 0.0349 (8) | 0.0064 (6) | 0.0029 (6) | −0.0010 (7) |
C31 | 0.0155 (6) | 0.0165 (6) | 0.0121 (5) | −0.0008 (5) | 0.0006 (4) | 0.0014 (4) |
C32 | 0.0166 (6) | 0.0171 (6) | 0.0147 (6) | 0.0005 (5) | 0.0016 (5) | 0.0000 (5) |
C33 | 0.0192 (6) | 0.0182 (6) | 0.0137 (6) | 0.0004 (5) | 0.0034 (5) | −0.0027 (5) |
O33 | 0.0178 (5) | 0.0355 (6) | 0.0245 (5) | 0.0042 (4) | 0.0042 (4) | 0.0056 (4) |
O34 | 0.0209 (5) | 0.0289 (5) | 0.0231 (5) | 0.0031 (4) | 0.0082 (4) | 0.0099 (4) |
C34 | 0.0299 (8) | 0.0269 (8) | 0.0300 (8) | 0.0000 (6) | 0.0156 (6) | 0.0087 (6) |
C35 | 0.0192 (6) | 0.0186 (6) | 0.0137 (6) | 0.0010 (5) | 0.0028 (5) | 0.0007 (5) |
O35 | 0.0238 (5) | 0.0200 (5) | 0.0355 (6) | −0.0045 (4) | 0.0105 (4) | −0.0014 (4) |
O36 | 0.0199 (5) | 0.0163 (5) | 0.0266 (5) | 0.0025 (4) | 0.0044 (4) | −0.0001 (4) |
C36 | 0.0338 (8) | 0.0174 (7) | 0.0292 (8) | 0.0052 (6) | 0.0069 (6) | −0.0006 (6) |
C1—N27 | 1.4862 (16) | C20—C21 | 1.5143 (17) |
C1—C2 | 1.5124 (17) | C21—N27 | 1.4854 (16) |
C1—C26 | 1.5560 (18) | C21—C22 | 1.5548 (17) |
C1—H1 | 1.0000 | C21—H21 | 1.0000 |
C2—C3 | 1.3907 (19) | C22—C28 | 1.5081 (18) |
C2—C7 | 1.4025 (19) | C22—C23 | 1.5456 (18) |
C3—C4 | 1.3962 (19) | C22—H22 | 1.0000 |
C3—H3 | 0.9500 | C23—N24 | 1.4576 (17) |
C4—C5 | 1.380 (2) | C23—H23A | 0.9900 |
C4—H4 | 0.9500 | C23—H23B | 0.9900 |
C5—C6 | 1.386 (2) | N24—C29 | 1.3623 (19) |
C5—H5 | 0.9500 | N24—C25 | 1.4621 (17) |
C6—C7 | 1.3944 (19) | C25—C26 | 1.5435 (18) |
C6—H6 | 0.9500 | C25—H25A | 0.9900 |
C7—O8 | 1.3603 (17) | C25—H25B | 0.9900 |
O8—C9 | 1.4338 (17) | C26—C28 | 1.5097 (18) |
C9—C10 | 1.500 (2) | C26—H26 | 1.0000 |
C9—H9A | 0.9900 | N27—C31 | 1.4245 (16) |
C9—H9B | 0.9900 | C28—O28 | 1.2130 (16) |
C10—O11 | 1.4228 (17) | C29—O29 | 1.2283 (18) |
C10—H10A | 0.9900 | C29—C30 | 1.509 (2) |
C10—H10B | 0.9900 | C30—H30A | 0.9800 |
O11—C12 | 1.4196 (17) | C30—H30B | 0.9800 |
C12—C13 | 1.500 (2) | C30—H30C | 0.9800 |
C12—H12A | 0.9900 | C31—C32 | 1.3311 (18) |
C12—H12B | 0.9900 | C31—C35 | 1.5036 (18) |
C13—O14 | 1.4292 (16) | C32—C33 | 1.4799 (18) |
C13—H13A | 0.9900 | C32—H32 | 0.9500 |
C13—H13B | 0.9900 | C33—O33 | 1.2076 (16) |
O14—C15 | 1.3650 (15) | C33—O34 | 1.3337 (16) |
C15—C16 | 1.3950 (18) | O34—C34 | 1.4512 (16) |
C15—C20 | 1.4086 (18) | C34—H34A | 0.9800 |
C16—C17 | 1.3894 (19) | C34—H34B | 0.9800 |
C16—H16 | 0.9500 | C34—H34C | 0.9800 |
C17—C18 | 1.3804 (19) | C35—O35 | 1.2019 (16) |
C17—H17 | 0.9500 | C35—O36 | 1.3373 (16) |
C18—C19 | 1.3942 (18) | O36—C36 | 1.4481 (17) |
C18—H18 | 0.9500 | C36—H36A | 0.9800 |
C19—C20 | 1.3885 (18) | C36—H36B | 0.9800 |
C19—H19 | 0.9500 | C36—H36C | 0.9800 |
N27—C1—C2 | 114.34 (10) | N27—C21—H21 | 108.1 |
N27—C1—C26 | 107.57 (10) | C20—C21—H21 | 108.1 |
C2—C1—C26 | 111.62 (10) | C22—C21—H21 | 108.1 |
N27—C1—H1 | 107.7 | C28—C22—C23 | 105.85 (10) |
C2—C1—H1 | 107.7 | C28—C22—C21 | 110.33 (10) |
C26—C1—H1 | 107.7 | C23—C22—C21 | 110.96 (11) |
C3—C2—C7 | 118.54 (12) | C28—C22—H22 | 109.9 |
C3—C2—C1 | 119.31 (12) | C23—C22—H22 | 109.9 |
C7—C2—C1 | 122.01 (12) | C21—C22—H22 | 109.9 |
C2—C3—C4 | 121.13 (14) | N24—C23—C22 | 110.07 (10) |
C2—C3—H3 | 119.4 | N24—C23—H23A | 109.6 |
C4—C3—H3 | 119.4 | C22—C23—H23A | 109.6 |
C5—C4—C3 | 119.31 (14) | N24—C23—H23B | 109.6 |
C5—C4—H4 | 120.3 | C22—C23—H23B | 109.6 |
C3—C4—H4 | 120.3 | H23A—C23—H23B | 108.2 |
C4—C5—C6 | 120.89 (13) | C29—N24—C23 | 120.37 (11) |
C4—C5—H5 | 119.6 | C29—N24—C25 | 125.43 (12) |
C6—C5—H5 | 119.6 | C23—N24—C25 | 114.19 (11) |
C5—C6—C7 | 119.59 (14) | N24—C25—C26 | 110.62 (10) |
C5—C6—H6 | 120.2 | N24—C25—H25A | 109.5 |
C7—C6—H6 | 120.2 | C26—C25—H25A | 109.5 |
O8—C7—C6 | 123.83 (13) | N24—C25—H25B | 109.5 |
O8—C7—C2 | 115.64 (11) | C26—C25—H25B | 109.5 |
C6—C7—C2 | 120.50 (13) | H25A—C25—H25B | 108.1 |
C7—O8—C9 | 119.25 (11) | C28—C26—C25 | 105.72 (10) |
O8—C9—C10 | 105.72 (11) | C28—C26—C1 | 110.66 (10) |
O8—C9—H9A | 110.6 | C25—C26—C1 | 111.13 (11) |
C10—C9—H9A | 110.6 | C28—C26—H26 | 109.8 |
O8—C9—H9B | 110.6 | C25—C26—H26 | 109.8 |
C10—C9—H9B | 110.6 | C1—C26—H26 | 109.8 |
H9A—C9—H9B | 108.7 | C31—N27—C21 | 113.99 (10) |
O11—C10—C9 | 107.99 (12) | C31—N27—C1 | 116.30 (10) |
O11—C10—H10A | 110.1 | C21—N27—C1 | 110.20 (9) |
C9—C10—H10A | 110.1 | O28—C28—C22 | 124.07 (12) |
O11—C10—H10B | 110.1 | O28—C28—C26 | 124.59 (12) |
C9—C10—H10B | 110.1 | C22—C28—C26 | 110.61 (11) |
H10A—C10—H10B | 108.4 | O29—C29—N24 | 121.24 (13) |
C12—O11—C10 | 112.57 (11) | O29—C29—C30 | 120.99 (14) |
O11—C12—C13 | 109.13 (12) | N24—C29—C30 | 117.76 (13) |
O11—C12—H12A | 109.9 | C29—C30—H30A | 109.5 |
C13—C12—H12A | 109.9 | C29—C30—H30B | 109.5 |
O11—C12—H12B | 109.9 | H30A—C30—H30B | 109.5 |
C13—C12—H12B | 109.9 | C29—C30—H30C | 109.5 |
H12A—C12—H12B | 108.3 | H30A—C30—H30C | 109.5 |
O14—C13—C12 | 107.14 (11) | H30B—C30—H30C | 109.5 |
O14—C13—H13A | 110.3 | C32—C31—N27 | 119.05 (12) |
C12—C13—H13A | 110.3 | C32—C31—C35 | 121.12 (12) |
O14—C13—H13B | 110.3 | N27—C31—C35 | 119.75 (11) |
C12—C13—H13B | 110.3 | C31—C32—C33 | 126.45 (12) |
H13A—C13—H13B | 108.5 | C31—C32—H32 | 116.8 |
C15—O14—C13 | 117.64 (10) | C33—C32—H32 | 116.8 |
O14—C15—C16 | 123.71 (12) | O33—C33—O34 | 123.74 (12) |
O14—C15—C20 | 115.90 (11) | O33—C33—C32 | 121.90 (12) |
C16—C15—C20 | 120.33 (12) | O34—C33—C32 | 114.26 (11) |
C17—C16—C15 | 119.87 (12) | C33—O34—C34 | 114.68 (11) |
C17—C16—H16 | 120.1 | O34—C34—H34A | 109.5 |
C15—C16—H16 | 120.1 | O34—C34—H34B | 109.5 |
C18—C17—C16 | 120.73 (12) | H34A—C34—H34B | 109.5 |
C18—C17—H17 | 119.6 | O34—C34—H34C | 109.5 |
C16—C17—H17 | 119.6 | H34A—C34—H34C | 109.5 |
C17—C18—C19 | 119.04 (12) | H34B—C34—H34C | 109.5 |
C17—C18—H18 | 120.5 | O35—C35—O36 | 124.79 (12) |
C19—C18—H18 | 120.5 | O35—C35—C31 | 124.67 (12) |
C20—C19—C18 | 121.91 (12) | O36—C35—C31 | 110.53 (11) |
C20—C19—H19 | 119.0 | C35—O36—C36 | 117.33 (11) |
C18—C19—H19 | 119.0 | O36—C36—H36A | 109.5 |
C19—C20—C15 | 118.10 (11) | O36—C36—H36B | 109.5 |
C19—C20—C21 | 119.71 (11) | H36A—C36—H36B | 109.5 |
C15—C20—C21 | 122.07 (11) | O36—C36—H36C | 109.5 |
N27—C21—C20 | 113.17 (10) | H36A—C36—H36C | 109.5 |
N27—C21—C22 | 107.93 (10) | H36B—C36—H36C | 109.5 |
C20—C21—C22 | 111.15 (10) | ||
N27—C1—C2—C3 | −118.70 (13) | C22—C23—N24—C29 | −122.32 (13) |
C26—C1—C2—C3 | 118.90 (13) | C22—C23—N24—C25 | 56.46 (14) |
N27—C1—C2—C7 | 65.64 (16) | C29—N24—C25—C26 | 122.45 (14) |
C26—C1—C2—C7 | −56.75 (16) | C23—N24—C25—C26 | −56.26 (15) |
C7—C2—C3—C4 | 1.7 (2) | N24—C25—C26—C28 | 57.46 (14) |
C1—C2—C3—C4 | −174.11 (12) | N24—C25—C26—C1 | −62.65 (14) |
C2—C3—C4—C5 | −0.1 (2) | N27—C1—C26—C28 | 2.43 (14) |
C3—C4—C5—C6 | −1.5 (2) | C2—C1—C26—C28 | 128.63 (11) |
C4—C5—C6—C7 | 1.3 (2) | N27—C1—C26—C25 | 119.57 (11) |
C5—C6—C7—O8 | 178.27 (13) | C2—C1—C26—C25 | −114.23 (12) |
C5—C6—C7—C2 | 0.3 (2) | C20—C21—N27—C31 | −38.88 (14) |
C3—C2—C7—O8 | −179.92 (12) | C22—C21—N27—C31 | −162.31 (10) |
C1—C2—C7—O8 | −4.24 (18) | C20—C21—N27—C1 | −171.75 (10) |
C3—C2—C7—C6 | −1.8 (2) | C22—C21—N27—C1 | 64.81 (12) |
C1—C2—C7—C6 | 173.87 (12) | C2—C1—N27—C31 | 39.86 (16) |
C6—C7—O8—C9 | 12.0 (2) | C26—C1—N27—C31 | 164.43 (10) |
C2—C7—O8—C9 | −169.97 (12) | C2—C1—N27—C21 | 171.54 (11) |
C7—O8—C9—C10 | 169.85 (11) | C26—C1—N27—C21 | −63.88 (13) |
O8—C9—C10—O11 | −67.15 (14) | C23—C22—C28—O28 | −105.51 (14) |
C9—C10—O11—C12 | 164.25 (12) | C21—C22—C28—O28 | 134.37 (13) |
C10—O11—C12—C13 | −156.42 (12) | C23—C22—C28—C26 | 65.06 (13) |
O11—C12—C13—O14 | 70.09 (14) | C21—C22—C28—C26 | −55.06 (13) |
C12—C13—O14—C15 | −179.32 (11) | C25—C26—C28—O28 | 106.01 (14) |
C13—O14—C15—C16 | −17.86 (18) | C1—C26—C28—O28 | −133.57 (13) |
C13—O14—C15—C20 | 164.85 (11) | C25—C26—C28—C22 | −64.49 (13) |
O14—C15—C16—C17 | −176.19 (12) | C1—C26—C28—C22 | 55.92 (13) |
C20—C15—C16—C17 | 0.99 (19) | C23—N24—C29—O29 | −0.9 (2) |
C15—C16—C17—C18 | −0.8 (2) | C25—N24—C29—O29 | −179.56 (13) |
C16—C17—C18—C19 | 0.0 (2) | C23—N24—C29—C30 | 179.47 (12) |
C17—C18—C19—C20 | 0.7 (2) | C25—N24—C29—C30 | 0.8 (2) |
C18—C19—C20—C15 | −0.51 (19) | C21—N27—C31—C32 | 127.63 (12) |
C18—C19—C20—C21 | 175.64 (12) | C1—N27—C31—C32 | −102.47 (14) |
O14—C15—C20—C19 | 177.05 (11) | C21—N27—C31—C35 | −49.22 (15) |
C16—C15—C20—C19 | −0.34 (18) | C1—N27—C31—C35 | 80.68 (14) |
O14—C15—C20—C21 | 0.99 (17) | N27—C31—C32—C33 | −175.87 (11) |
C16—C15—C20—C21 | −176.40 (11) | C35—C31—C32—C33 | 0.9 (2) |
C19—C20—C21—N27 | 126.37 (12) | C31—C32—C33—O33 | 119.73 (16) |
C15—C20—C21—N27 | −57.63 (15) | C31—C32—C33—O34 | −63.77 (18) |
C19—C20—C21—C22 | −111.98 (13) | O33—C33—O34—C34 | −5.65 (19) |
C15—C20—C21—C22 | 64.01 (15) | C32—C33—O34—C34 | 177.93 (12) |
N27—C21—C22—C28 | −3.72 (14) | C32—C31—C35—O35 | −28.2 (2) |
C20—C21—C22—C28 | −128.38 (11) | N27—C31—C35—O35 | 148.54 (13) |
N27—C21—C22—C23 | −120.71 (11) | C32—C31—C35—O36 | 152.95 (12) |
C20—C21—C22—C23 | 114.63 (11) | N27—C31—C35—O36 | −30.27 (15) |
C28—C22—C23—N24 | −58.32 (14) | O35—C35—O36—C36 | −2.02 (19) |
C21—C22—C23—N24 | 61.39 (13) | C31—C35—O36—C36 | 176.78 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18···O35i | 0.95 | 2.47 | 3.1735 (17) | 131 |
C25—H25A···O33ii | 0.99 | 2.30 | 3.2091 (17) | 152 |
C34—H34A···O35iii | 0.98 | 2.53 | 3.5045 (19) | 174 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C31H34N2O9 |
Mr | 578.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 9.6634 (6), 26.3883 (18), 11.4375 (8) |
β (°) | 99.614 (1) |
V (Å3) | 2875.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.971, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36500, 8396, 6209 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 1.00 |
No. of reflections | 8396 |
No. of parameters | 382 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.26 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18···O35i | 0.95 | 2.47 | 3.1735 (17) | 131 |
C25—H25A···O33ii | 0.99 | 2.30 | 3.2091 (17) | 152 |
C34—H34A···O35iii | 0.98 | 2.53 | 3.5045 (19) | 174 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2. |
Acknowledgements
We thank the Vietnam National University, Hanoi (grant No. QG.11.09), for the financial support of this work.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Azacrown ethers draw very great attention of investigators over the last half century owing to their great potential for both theoretical and practical interest (Hiraoka, 1982; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently we have designed one more effective route to reach this fascinating region of macroheterocyclic compounds, namely, the effective method of synthesis of azacrown ethers containing piperidine (Levov et al., 2006, 2008; Anh et al., 2008; Anh, Hieu, Soldatenkov, Kolyadina & Khrustalev, 2012a; Anh, Hieu, Soldatenkov, Soldatova & Khrustalev, 2012), perhydropyrimidine (Hieu et al., 2011), perhydrotriazine (Khieu et al., 2011) and bispidine (Komarova et al., 2008; Sokol et al., 2011; Anh, Hieu, Soldatenkov, Kolyadina & Khrustalev, 2012b) subunits.
In attempts to develop the chemistry for new azacrown systems and to obtain macrocyclic ligands bringing the desirable functional groups, we studied the Michael addition of the cyclic secondary amine subunit of the (bispidino)aza-14-crown-4 ether to dimethyl acetylenedicarboxylate. The expected reaction is well known (Schwan & Warkentin, 1988), but might be highly hindered in the case of (bispidino)azacrown system due to the steric reasons. We have found that the expected N-vynilation reaction of the (bispidino)azacrown ether proceeded smoothly to give an N-maleinate derivative of the azacrown system with a good yield (Fig. 1).
The molecule of I, C31H34N2O9, comprises a tricyclic system containing the aza-14-crown-3-ether macrocycle and two six-membered piperidinone 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 51.14 (5)°. The central piperidone ring has a boat conformation, whereas the terminal piperidone ring adopts a chair conformation. The nitrogen N24 atom has a trigonal-planar geometry (sum of the bond angles is 360.0°), while the nitrogen N27 atom adopts a trigonal-pyramidal geometry (sum of the bond angles is 340.5°). The dimethyl ethylenedicarboxylate fragment has a cis configuration with a dihedral angle of 56.56 (7)° between the two carboxylate groups.
The molecule of I possesses four asymmetric centers at the C1, C21, C22 and C26 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*,26S*.
In the crystal, the molecules of I are bound by the weak intermolecular C–H···O hydrogen bonding interactions into three-dimensional framework (Table 1).