organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 3| March 2013| Pages o408-o409

4-Hy­dr­oxy-1,1′-bis­­[(S)-1-phenyl­eth­yl]-5,5′,6,6′-tetra­hydro-3,4′-bi­pyridine-2,2′(1H,1′H)-dione

aUniversidad Juárez Autónoma de Tabasco, División Académica de Ciencias Básicas, Km. 1 carretera Cunduacán, Jalpa de Méndez AP 24, Cunduacán, Tabasco, Mexico, bCentro de Química, Benemerita Universidad Autónoma de Puebla, Edif. 103H Complejo de Ciencias, C.U., 72570 Puebla, Pue., Mexico, and cUniversidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Av. Universidad S/N, Ciudad Universitaria, San Nicolás de los Garza, Nuevo León CP 66451, Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com

(Received 11 January 2013; accepted 9 February 2013; online 20 February 2013)

The title bis-piperidine, C26H28N2O3, was unexpectedly obtained via a dimerization mechanism promoted by acetic acid when performing the Dieckmann cyclization of a chiral amido ester. The S,S configuration was assigned by reference to the enanti­omerically pure starting material. In the mol­ecule, two core heterocycles are linked by a σ bond. One ring includes a keto–enol group, while the other presents an enone functionality. Both rings present a conformation inter­mediate between envelope and screw-boat, and the dihedral angle between the mean planes passing through the rings [48.9 (1)°] is large enough to avoid hindrance between ring substituents. The enol tautomeric form in one ring favors the formation of strong inter­molecular O—H⋯O=C hydrogen bonds. The resulting one-dimensional supra­molecular structure features single-stranded helices running along the 21 screw axis parallel to [100].

Related literature

For natural products having a bis-piperidine substructure, see: Gil et al. (1995[Gil, L., Baucherel, X., Martin, M.-T., Marazano, C. & Das, B. C. (1995). Tetrahedron Lett. 36, 6231-6234.]); Torres et al. (2000[Torres, Y. R., Berlinck, R. G. S., Magalhães, A., Schefer, A. B., Ferreira, A. G., Hajdu, E. & Muricy, G. (2000). J. Nat. Prod. 63, 1098-1105.]); Matsunaga et al. (2004[Matsunaga, S., Miyata, Y., van Soest, R. W. M. & Fusetani, N. (2004). J. Nat. Prod. 67, 1758-1760.]); Smith & Sulikowski (2010[Smith, B. J. & Sulikowski, G. A. (2010). Angew. Chem. Int. Ed. 49, 1599-1602.]). For related structures of monocyclic piperidines, see: Didierjean et al. (2004[Didierjean, C., Marin, J., Wenger, E., Briand, J.-P., Aubry, A. & Guichard, G. (2004). Acta Cryst. C60, o200-o203.]); Romero et al. (2005[Romero, N., Terán, J. L., Gnecco, D. & Bernès, S. (2005). Acta Cryst. E61, o2924-o2926.]). For the application of Dieckmann condensation in organic synthesis, see: Scheiber & Nemes (2008[Scheiber, P. & Nemes, P. (2008). Arkivoc, iii, 194-199.]). For an example of self-condensation of a dione similar to that used for the synthesis of the title compound, see: Sugasawa & Oka (1954[Sugasawa, S. & Oka, K. (1954). Chem. Pharm. Bull. 2, 85-88.]).

[Scheme 1]

Experimental

Crystal data
  • C26H28N2O3

  • Mr = 416.50

  • Orthorhombic, P 21 21 21

  • a = 9.6647 (13) Å

  • b = 9.7281 (10) Å

  • c = 23.684 (3) Å

  • V = 2226.7 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 296 K

  • 0.60 × 0.60 × 0.08 mm

Data collection
  • Bruker P4 diffractometer

  • 3173 measured reflections

  • 2250 independent reflections

  • 1843 reflections with I > 2σ(I)

  • Rint = 0.019

  • 3 standard reflections every 97 reflections intensity decay: 1.5%

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.095

  • S = 1.04

  • 2250 reflections

  • 286 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O4—H4⋯O2′i 0.97 (4) 1.67 (4) 2.637 (3) 177 (4)
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2].

Data collection: XSCANS (Siemens, 1996[Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound is a byproduct of the Dieckmann cyclization carried on the chiral amido ester 3 (Fig. 1). When concentrated acetic acid is used in the fourth synthetic step, a dimerization occurs during the decarboxylation process, affording the title molecule I as the major product, while the expected piperidine-2,4-dione 5 is obtained in low yield. This synthetic route for the preparation of this kind of piperidone derivatives is known to be successful in many cases (e.g. Scheiber & Nemes, 2008). However, it seems that the possible interference of secondary reactions like dimerization is poorly commented in the literature, probably because these reactions are seen as a trouble for the intended synthetic target. To the best of our knowledge, a single article clearly commented on this problem (Sugasawa & Oka, 1954). In this report, the authors added a note in the galley proofs, which is worth to quote in full: "in the course of the present work, we prepared N-benzyl-2,4-dioxopiperidine [···]. Our attempt to condense this ketone with ethyl cyanoacetate under Cope condition was not effected because this compound was found to undergo bimolecular self-condensation fairly rapidly, at a room temperature [···]. This tendency of the easy intermolecular self-condensation [of N-benzyl-2,4-dioxopiperidine] is so remarkable when compared with the stability of the corresponding 5-ethyl derivatives, which suffer no change when kept in a stoppered bottle at room temperature for a long time".

The synthesis of the title compound in good yield now confirms the observations done by Sugasawa & Oka 59 years ago.

The molecular structure of I is built up from one ring including a keto-enol group (ring N1/C2···C6) bonded to a ring with the enone functionality (ring N1'/C2'···C6', see Fig. 2). Both rings present a conformation intermediate between envelope and screw-boat, with Cremer parameters being θ = 118.1° and ϕ = 101.0° for the keto-enol ring, and θ = 60.5° and ϕ = 278.5° for the enone ring. The dihedral angle between mean planes passing through these heterocycles, 48.9 (1)°, is large enough to avoid hindrance between atoms O2 and O4 in the first ring and H atoms at C3' and C5' in the other ring. Heterocycles in I have indeed conformations close to those observed in monocyclic related compounds which were X-ray characterized (e.g. Didierjean et al., 2004; Romero et al., 2005). In the solid state, the enolic tautomer of I seems to be favored over the di-ketone because the presence of a donor OH group allows the formation of stabilizing intermolecular O—H···OC hydrogen bonds in the crystal. These strong interactions generate a supramolecular structure based on single stranded helices running along the 21 crystallographic screw axis in the [100] direction (Fig. 3).

The reported structure may be of interest in the field of natural products. It has been reported that the biosynthesis of some bis-piperidine alkaloids isolated from marine sponges, like halicyclamine A (Gil et al., 1995) or haliclonacyclamine C (Smith & Sulikowski, 2010) could involve the dimerization of dihydropyridines. Other natural products of interest also share the title compound bis-piperidine scaffold, with additional points of cyclization between the piperidine rings (Torres et al., 2000; Matsunaga et al., 2004).

Related literature top

For natural products having a bis-piperidine substructure, see: Gil et al. (1995); Torres et al. (2000); Matsunaga et al. (2004); Smith & Sulikowski (2010). For related structures of monocyclic piperidines, see: Didierjean et al. (2004); Romero et al. (2005). For the application of Dieckmann condensation in organic synthesis, see: Scheiber & Nemes (2008). For an example of self-condensation of a dione similar to that used for the synthesis of the title compound, see: Sugasawa & Oka (1954).

Experimental top

The synthesis is described in Fig. 1. A solution of 1 (41.2 mmol, 1 eq.) and methyl acrylate (49.6 mmol, 1.2 eq.) was stirred overnight at 298 K. The reaction mixture was concentrated under reduced pressure, and the crude purified by column chromatography (SiO2, CH2Cl2:MeOH, 97:3), to afford 2 as a colourless oil (98%). An amount of 2 (40.6 mmol, 1 eq.) was dissolved in diethyl malonate (40 ml) and the mixture refluxed until the reaction was complete (6 h). After concentration, the crude was chromatographed (Al2O3, n-hexane:AcOEt, 1:1), to afford 3, as a colourless oil (75%). A suspension of NaH (34.2 mmol, 2.5 eq.) in cyclohexane (100 ml) was refluxed for 20 min, and then, a solution of 3 (13.7 mmol, 1.1 eq. in 30 ml of anhydrous toluene) was added dropwise. After refluxing the mixture for 5 h, a solid was obtained, 4, which was filtered and dried in air. This solid was treated with acetic acid:water (30%, v/v) for the decarboxylation process. The mixture was refluxed until gas evolution stopped. After cooling down to 298 K, pH was adjusted to 7 with NaHCO3, and the mixture was washed with CH2Cl2 (3 × 50 ml). The organic phase was dried over Na2SO4, and concentrated. Compounds 5 and I were separated by column chromatography, (SiO2, CH2Cl2:MeOH, 95:5). The title compound I was obtained in 80% yield, and was recrystallized from AcOEt:n-hexane (1:1). m.p. = 444 K, [α]20D = -172.5 (c=1, CH2Cl2). Compound 5, a colourless oil, was isolated in low yield (< 20%). Key NMR and IR data are given in the archived CIF.

Refinement top

All C-bound H atoms were placed in idealized positions and refined as riding to their carrier atoms, with bond lengths fixed to 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2) or 0.98 Å (methine CH). Isotropic displacement parameters were calculated as Uiso(H) = xUeq(carrier atom), with x = 1.5 (methyl groups) or x = 1.2 (other H atoms). H4 (hydroxyl group) was found in a difference map and refined with free coordinates and Uiso(H4) = 1.5Ueq(O4). The absolute configuration for C7 and C7' is based on the known configuration of the enantiomerically pure starting material, (S)-(–)-1-phenylethylamine, and 621 measured Friedel pairs were merged for refinement.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The synthesis of the title molecule, I. (i) Methyl acrylate, MeOH, 25 °C, 12 h. (ii) Diethyl malonate, reflux, 6 h. (iii) NaH, cyclohexane/toluene, reflux. (iv) AcOH/H2O (30%, v/v).
[Figure 2] Fig. 2. Molecular structure of the title compound, with 50% probability level displacement ellipsoids for non-H atoms.
[Figure 3] Fig. 3. A chain of hydrogen-bonded molecules, along the screw axis parallel to [100].
4-Hydroxy-1,1'-bis[(S)-1-phenylethyl]-5,5',6,6'-tetrahydro-3,4'-bipyridine-2,2'(1H,1'H)-dione top
Crystal data top
C26H28N2O3Dx = 1.242 Mg m3
Mr = 416.50Melting point: 444 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 62 reflections
a = 9.6647 (13) Åθ = 4.7–12.0°
b = 9.7281 (10) ŵ = 0.08 mm1
c = 23.684 (3) ÅT = 296 K
V = 2226.7 (5) Å3Plate, colourless
Z = 40.60 × 0.60 × 0.08 mm
F(000) = 888
Data collection top
Bruker P4
diffractometer
Rint = 0.019
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.3°
Graphite monochromatorh = 112
ω scansk = 111
3173 measured reflectionsl = 128
2250 independent reflections3 standard reflections every 97 reflections
1843 reflections with I > 2σ(I) intensity decay: 1.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095 w = 1/[σ2(Fo2) + (0.0483P)2 + 0.2404P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2250 reflectionsΔρmax = 0.19 e Å3
286 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.0098 (15)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Assigned from synthesis. Friedel pairs (621) were merged
Crystal data top
C26H28N2O3V = 2226.7 (5) Å3
Mr = 416.50Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.6647 (13) ŵ = 0.08 mm1
b = 9.7281 (10) ÅT = 296 K
c = 23.684 (3) Å0.60 × 0.60 × 0.08 mm
Data collection top
Bruker P4
diffractometer
Rint = 0.019
3173 measured reflections3 standard reflections every 97 reflections
2250 independent reflections intensity decay: 1.5%
1843 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.19 e Å3
2250 reflectionsΔρmin = 0.15 e Å3
286 parametersAbsolute structure: Assigned from synthesis. Friedel pairs (621) were merged
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.6918 (2)0.2061 (2)0.96330 (9)0.0342 (5)
C20.7571 (3)0.3060 (3)0.93294 (10)0.0324 (6)
O20.8401 (2)0.27815 (18)0.89463 (8)0.0451 (5)
C30.7286 (3)0.4508 (3)0.94792 (10)0.0330 (6)
C40.6613 (3)0.4827 (3)0.99592 (11)0.0360 (6)
O40.6401 (2)0.61396 (19)1.01054 (8)0.0515 (6)
H40.591 (4)0.629 (4)1.0457 (14)0.077*
C50.6126 (3)0.3712 (3)1.03453 (11)0.0397 (7)
H5A0.53150.40211.05510.048*
H5B0.68450.34981.06170.048*
C60.5774 (3)0.2438 (3)1.00066 (12)0.0395 (6)
H6A0.55790.16831.02620.047*
H6B0.49500.26080.97830.047*
C70.7035 (3)0.0612 (3)0.94466 (11)0.0364 (7)
H7A0.78070.05750.91790.044*
C80.7425 (4)0.0316 (3)0.99393 (13)0.0523 (8)
H8A0.82330.00431.01230.078*
H8B0.76160.12250.98020.078*
H8C0.66730.03521.02040.078*
C90.5745 (3)0.0181 (3)0.91220 (11)0.0412 (7)
C100.5143 (4)0.1103 (4)0.91817 (15)0.0656 (10)
H10A0.55250.17380.94300.079*
C110.3974 (5)0.1450 (5)0.8874 (2)0.0934 (15)
H11A0.35750.23120.89200.112*
C120.3405 (5)0.0541 (6)0.8505 (2)0.0936 (15)
H12A0.26140.07790.83040.112*
C130.3993 (4)0.0718 (5)0.84287 (17)0.0778 (12)
H13A0.36160.13320.81700.093*
C140.5151 (3)0.1078 (4)0.87365 (12)0.0557 (9)
H14A0.55410.19420.86840.067*
N1'0.8952 (2)0.7324 (2)0.82498 (8)0.0355 (5)
C2'0.9292 (3)0.7510 (3)0.87967 (10)0.0340 (6)
O2'1.0011 (2)0.8499 (2)0.89480 (8)0.0513 (6)
C3'0.8771 (3)0.6493 (3)0.92029 (10)0.0370 (7)
H3'A0.91100.65180.95700.044*
C4'0.7837 (3)0.5535 (3)0.90715 (10)0.0321 (6)
C5'0.7280 (3)0.5523 (3)0.84798 (11)0.0430 (7)
H5'A0.70120.45930.83800.052*
H5'B0.64620.60980.84610.052*
C6'0.8320 (3)0.6029 (3)0.80695 (10)0.0445 (7)
H6'A0.90380.53410.80240.053*
H6'B0.78790.61610.77060.053*
C7'0.9595 (3)0.8177 (3)0.78050 (10)0.0380 (7)
H7'A0.99650.90020.79890.046*
C8'1.0818 (3)0.7410 (3)0.75459 (13)0.0517 (8)
H8'A1.14310.71120.78410.078*
H8'B1.13070.80110.72940.078*
H8'C1.04860.66250.73410.078*
C9'0.8503 (3)0.8648 (3)0.73878 (11)0.0361 (6)
C10'0.8695 (3)0.8573 (3)0.68070 (11)0.0454 (7)
H10B0.95020.81890.66630.055*
C11'0.7697 (4)0.9065 (4)0.64424 (13)0.0623 (10)
H11B0.78480.90150.60550.075*
C12'0.6498 (4)0.9619 (4)0.66362 (14)0.0677 (11)
H12B0.58380.99500.63850.081*
C13'0.6274 (4)0.9684 (4)0.72079 (15)0.0694 (10)
H13B0.54511.00500.73450.083*
C14'0.7266 (3)0.9210 (3)0.75817 (12)0.0540 (9)
H14B0.71040.92670.79680.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0404 (13)0.0275 (11)0.0346 (11)0.0001 (11)0.0091 (10)0.0041 (9)
C20.0325 (14)0.0351 (14)0.0297 (12)0.0011 (13)0.0019 (12)0.0017 (12)
O20.0508 (12)0.0422 (11)0.0423 (10)0.0002 (10)0.0178 (10)0.0038 (9)
C30.0391 (15)0.0313 (14)0.0285 (13)0.0026 (13)0.0019 (13)0.0015 (11)
C40.0411 (15)0.0299 (13)0.0369 (14)0.0002 (13)0.0029 (14)0.0022 (12)
O40.0783 (15)0.0321 (10)0.0440 (11)0.0044 (12)0.0186 (12)0.0040 (9)
C50.0492 (17)0.0355 (14)0.0345 (13)0.0030 (15)0.0127 (13)0.0003 (12)
C60.0438 (15)0.0335 (13)0.0413 (13)0.0009 (15)0.0131 (14)0.0015 (12)
C70.0408 (16)0.0304 (14)0.0379 (15)0.0023 (13)0.0076 (13)0.0029 (12)
C80.069 (2)0.0383 (16)0.0498 (17)0.0068 (17)0.0001 (18)0.0023 (14)
C90.0424 (16)0.0387 (16)0.0425 (15)0.0041 (15)0.0104 (14)0.0084 (13)
C100.075 (2)0.055 (2)0.067 (2)0.022 (2)0.007 (2)0.0112 (18)
C110.090 (3)0.079 (3)0.112 (3)0.046 (3)0.012 (3)0.025 (3)
C120.061 (3)0.115 (4)0.105 (3)0.021 (3)0.015 (3)0.047 (3)
C130.064 (2)0.100 (3)0.069 (2)0.016 (3)0.022 (2)0.023 (2)
C140.060 (2)0.0543 (19)0.0529 (18)0.0013 (19)0.0122 (17)0.0087 (16)
N1'0.0458 (13)0.0324 (12)0.0283 (10)0.0111 (11)0.0044 (10)0.0032 (9)
C2'0.0389 (14)0.0290 (13)0.0341 (13)0.0029 (14)0.0037 (12)0.0004 (12)
O2'0.0703 (14)0.0451 (12)0.0385 (10)0.0271 (12)0.0081 (11)0.0027 (9)
C3'0.0493 (17)0.0367 (15)0.0251 (12)0.0032 (15)0.0030 (13)0.0004 (11)
C4'0.0361 (15)0.0295 (13)0.0308 (13)0.0006 (13)0.0040 (12)0.0010 (11)
C5'0.0483 (17)0.0441 (16)0.0364 (13)0.0171 (16)0.0055 (14)0.0013 (13)
C6'0.0631 (19)0.0415 (15)0.0290 (13)0.0164 (17)0.0049 (14)0.0005 (13)
C7'0.0437 (16)0.0348 (14)0.0354 (14)0.0078 (14)0.0014 (13)0.0067 (12)
C8'0.0450 (16)0.0530 (18)0.0570 (17)0.0050 (17)0.0057 (15)0.0153 (16)
C9'0.0420 (15)0.0326 (14)0.0336 (13)0.0035 (14)0.0037 (13)0.0026 (12)
C10'0.0488 (17)0.0521 (18)0.0354 (13)0.0087 (16)0.0085 (15)0.0035 (13)
C11'0.072 (2)0.080 (2)0.0351 (15)0.010 (2)0.0004 (17)0.0130 (17)
C12'0.066 (2)0.083 (3)0.054 (2)0.022 (2)0.007 (2)0.0172 (19)
C13'0.052 (2)0.086 (3)0.070 (2)0.023 (2)0.0059 (19)0.006 (2)
C14'0.0559 (19)0.066 (2)0.0401 (15)0.0104 (19)0.0106 (16)0.0035 (15)
Geometric parameters (Å, º) top
N1—C21.363 (3)C14—H14A0.9300
N1—C61.463 (3)N1'—C2'1.348 (3)
N1—C71.482 (3)N1'—C6'1.464 (3)
C2—O21.241 (3)N1'—C7'1.478 (3)
C2—C31.478 (4)C2'—O2'1.240 (3)
C3—C41.346 (4)C2'—C3'1.469 (4)
C3—C4'1.488 (3)C3'—C4'1.334 (4)
C4—O41.339 (3)C3'—H3'A0.9300
C4—C51.495 (4)C4'—C5'1.501 (4)
O4—H40.97 (4)C5'—C6'1.482 (4)
C5—C61.515 (4)C5'—H5'A0.9700
C5—H5A0.9700C5'—H5'B0.9700
C5—H5B0.9700C6'—H6'A0.9700
C6—H6A0.9700C6'—H6'B0.9700
C6—H6B0.9700C7'—C9'1.517 (4)
C7—C81.523 (4)C7'—C8'1.527 (4)
C7—C91.524 (4)C7'—H7'A0.9800
C7—H7A0.9800C8'—H8'A0.9600
C8—H8A0.9600C8'—H8'B0.9600
C8—H8B0.9600C8'—H8'C0.9600
C8—H8C0.9600C9'—C10'1.390 (4)
C9—C101.385 (5)C9'—C14'1.392 (4)
C9—C141.388 (4)C10'—C11'1.380 (4)
C10—C111.386 (6)C10'—H10B0.9300
C10—H10A0.9300C11'—C12'1.357 (5)
C11—C121.359 (6)C11'—H11B0.9300
C11—H11A0.9300C12'—C13'1.373 (5)
C12—C131.362 (6)C12'—H12B0.9300
C12—H12A0.9300C13'—C14'1.384 (5)
C13—C141.381 (5)C13'—H13B0.9300
C13—H13A0.9300C14'—H14B0.9300
C2—N1—C6119.3 (2)C2'—N1'—C6'119.8 (2)
C2—N1—C7119.1 (2)C2'—N1'—C7'120.4 (2)
C6—N1—C7118.4 (2)C6'—N1'—C7'116.79 (19)
O2—C2—N1121.9 (2)O2'—C2'—N1'121.2 (2)
O2—C2—C3120.3 (2)O2'—C2'—C3'121.7 (2)
N1—C2—C3117.8 (2)N1'—C2'—C3'117.1 (2)
C4—C3—C2120.8 (2)C4'—C3'—C2'123.3 (2)
C4—C3—C4'124.5 (2)C4'—C3'—H3'A118.3
C2—C3—C4'114.6 (2)C2'—C3'—H3'A118.3
O4—C4—C3120.8 (2)C3'—C4'—C3124.0 (2)
O4—C4—C5119.1 (2)C3'—C4'—C5'117.8 (2)
C3—C4—C5120.1 (2)C3—C4'—C5'118.2 (2)
C4—O4—H4116 (2)C6'—C5'—C4'111.5 (2)
C4—C5—C6109.9 (2)C6'—C5'—H5'A109.3
C4—C5—H5A109.7C4'—C5'—H5'A109.3
C6—C5—H5A109.7C6'—C5'—H5'B109.3
C4—C5—H5B109.7C4'—C5'—H5'B109.3
C6—C5—H5B109.7H5'A—C5'—H5'B108.0
H5A—C5—H5B108.2N1'—C6'—C5'112.2 (2)
N1—C6—C5110.8 (2)N1'—C6'—H6'A109.2
N1—C6—H6A109.5C5'—C6'—H6'A109.2
C5—C6—H6A109.5N1'—C6'—H6'B109.2
N1—C6—H6B109.5C5'—C6'—H6'B109.2
C5—C6—H6B109.5H6'A—C6'—H6'B107.9
H6A—C6—H6B108.1N1'—C7'—C9'110.0 (2)
N1—C7—C8110.8 (2)N1'—C7'—C8'109.7 (2)
N1—C7—C9110.5 (2)C9'—C7'—C8'115.1 (2)
C8—C7—C9115.2 (2)N1'—C7'—H7'A107.2
N1—C7—H7A106.6C9'—C7'—H7'A107.2
C8—C7—H7A106.6C8'—C7'—H7'A107.2
C9—C7—H7A106.6C7'—C8'—H8'A109.5
C7—C8—H8A109.5C7'—C8'—H8'B109.5
C7—C8—H8B109.5H8'A—C8'—H8'B109.5
H8A—C8—H8B109.5C7'—C8'—H8'C109.5
C7—C8—H8C109.5H8'A—C8'—H8'C109.5
H8A—C8—H8C109.5H8'B—C8'—H8'C109.5
H8B—C8—H8C109.5C10'—C9'—C14'117.5 (3)
C10—C9—C14117.4 (3)C10'—C9'—C7'122.4 (3)
C10—C9—C7122.7 (3)C14'—C9'—C7'120.1 (2)
C14—C9—C7119.8 (3)C11'—C10'—C9'120.5 (3)
C9—C10—C11120.5 (4)C11'—C10'—H10B119.8
C9—C10—H10A119.7C9'—C10'—H10B119.8
C11—C10—H10A119.7C12'—C11'—C10'121.5 (3)
C12—C11—C10120.6 (4)C12'—C11'—H11B119.3
C12—C11—H11A119.7C10'—C11'—H11B119.3
C10—C11—H11A119.7C11'—C12'—C13'119.1 (3)
C11—C12—C13120.1 (4)C11'—C12'—H12B120.4
C11—C12—H12A120.0C13'—C12'—H12B120.4
C13—C12—H12A120.0C12'—C13'—C14'120.4 (3)
C12—C13—C14119.8 (4)C12'—C13'—H13B119.8
C12—C13—H13A120.1C14'—C13'—H13B119.8
C14—C13—H13A120.1C13'—C14'—C9'121.0 (3)
C13—C14—C9121.5 (4)C13'—C14'—H14B119.5
C13—C14—H14A119.2C9'—C14'—H14B119.5
C9—C14—H14A119.2
C6—N1—C2—O2169.0 (2)C6'—N1'—C2'—O2'169.0 (3)
C7—N1—C2—O29.4 (4)C7'—N1'—C2'—O2'9.0 (4)
C6—N1—C2—C312.4 (4)C6'—N1'—C2'—C3'11.1 (4)
C7—N1—C2—C3172.0 (2)C7'—N1'—C2'—C3'171.1 (2)
O2—C2—C3—C4166.8 (3)O2'—C2'—C3'—C4'170.0 (3)
N1—C2—C3—C411.8 (4)N1'—C2'—C3'—C4'10.0 (4)
O2—C2—C3—C4'11.4 (4)C2'—C3'—C4'—C3179.2 (3)
N1—C2—C3—C4'170.0 (2)C2'—C3'—C4'—C5'1.1 (4)
C2—C3—C4—O4177.4 (3)C4—C3—C4'—C3'59.3 (4)
C4'—C3—C4—O40.5 (4)C2—C3—C4'—C3'118.7 (3)
C2—C3—C4—C50.8 (4)C4—C3—C4'—C5'118.8 (3)
C4'—C3—C4—C5178.8 (3)C2—C3—C4'—C5'63.2 (3)
O4—C4—C5—C6150.8 (3)C3'—C4'—C5'—C6'30.6 (4)
C3—C4—C5—C630.9 (4)C3—C4'—C5'—C6'151.1 (2)
C2—N1—C6—C544.4 (3)C2'—N1'—C6'—C5'40.8 (4)
C7—N1—C6—C5155.8 (2)C7'—N1'—C6'—C5'158.4 (2)
C4—C5—C6—N151.5 (3)C4'—C5'—C6'—N1'48.9 (3)
C2—N1—C7—C8131.3 (3)C2'—N1'—C7'—C9'135.9 (3)
C6—N1—C7—C868.8 (3)C6'—N1'—C7'—C9'63.5 (3)
C2—N1—C7—C999.8 (3)C2'—N1'—C7'—C8'96.5 (3)
C6—N1—C7—C960.1 (3)C6'—N1'—C7'—C8'64.1 (3)
N1—C7—C9—C10140.3 (3)N1'—C7'—C9'—C10'133.8 (3)
C8—C7—C9—C1013.8 (4)C8'—C7'—C9'—C10'9.2 (4)
N1—C7—C9—C1441.5 (3)N1'—C7'—C9'—C14'47.8 (3)
C8—C7—C9—C14168.0 (3)C8'—C7'—C9'—C14'172.3 (3)
C14—C9—C10—C111.3 (5)C14'—C9'—C10'—C11'1.1 (5)
C7—C9—C10—C11179.6 (3)C7'—C9'—C10'—C11'177.3 (3)
C9—C10—C11—C120.5 (6)C9'—C10'—C11'—C12'0.7 (5)
C10—C11—C12—C130.9 (7)C10'—C11'—C12'—C13'0.3 (6)
C11—C12—C13—C141.4 (7)C11'—C12'—C13'—C14'0.9 (6)
C12—C13—C14—C90.5 (5)C12'—C13'—C14'—C9'0.5 (6)
C10—C9—C14—C130.8 (5)C10'—C9'—C14'—C13'0.5 (5)
C7—C9—C14—C13179.1 (3)C7'—C9'—C14'—C13'178.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O2i0.97 (4)1.67 (4)2.637 (3)177 (4)
Symmetry code: (i) x1/2, y+3/2, z+2.

Experimental details

Crystal data
Chemical formulaC26H28N2O3
Mr416.50
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)9.6647 (13), 9.7281 (10), 23.684 (3)
V3)2226.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.60 × 0.60 × 0.08
Data collection
DiffractometerBruker P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3173, 2250, 1843
Rint0.019
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.095, 1.04
No. of reflections2250
No. of parameters286
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.15
Absolute structureAssigned from synthesis. Friedel pairs (621) were merged

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O2'i0.97 (4)1.67 (4)2.637 (3)177 (4)
Symmetry code: (i) x1/2, y+3/2, z+2.
 

Acknowledgements

The authors wish to acknowledge CONACyT–Gobierno del Estado Tabasco and the Universidad Juárez Autónoma de Tabasco for financial support via projects TAB-2009-C18–122141 and UJAT-2009-C05–02, respectively.

References

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Volume 69| Part 3| March 2013| Pages o408-o409
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