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

Romero, N.; Gnecco, D.; Terán, J.; Bernès, S.

doi:10.1107/S1600536813004017

organic compounds

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ISSN: 2056-9890

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

doi:10.1107/S1600536813004017

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

Nancy Romero,^a Dino Gnecco,^b Joel Terán ^b and Sylvain Bernès ^c ^*

^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 ); 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

Crystal data

C₂₆H₂₈N₂O₃
M_r = 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)
R_int = 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
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: XSCANS; data reduction: XSCANS; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813004017/nr2039sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004017/nr2039Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004017/nr2039Isup3.cml

checkCIF report

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···O═C 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]²⁰_D = -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.

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

	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).
	Fig. 2. Molecular structure of the title compound, with 50% probability level displacement ellipsoids for non-H atoms.
	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

C₂₆H₂₈N₂O₃	D_x = 1.242 Mg m⁻³
M_r = 416.50	Melting point: 444 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 62 reflections
a = 9.6647 (13) Å	θ = 4.7–12.0°
b = 9.7281 (10) Å	µ = 0.08 mm⁻¹
c = 23.684 (3) Å	T = 296 K
V = 2226.7 (5) Å³	Plate, colourless
Z = 4	0.60 × 0.60 × 0.08 mm
F(000) = 888

Data collection top

Bruker P4 diffractometer	R_int = 0.019
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.3°
Graphite monochromator	h = −11→2
ω scans	k = −11→1
3173 measured reflections	l = −1→28
2250 independent reflections	3 standard reflections every 97 reflections
1843 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0483P)² + 0.2404P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2250 reflections	Δρ_max = 0.19 e Å⁻³
286 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0098 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Assigned from synthesis. Friedel pairs (621) were merged

Crystal data top

C₂₆H₂₈N₂O₃	V = 2226.7 (5) Å³
M_r = 416.50	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.6647 (13) Å	µ = 0.08 mm⁻¹
b = 9.7281 (10) Å	T = 296 K
c = 23.684 (3) Å	0.60 × 0.60 × 0.08 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.019
3173 measured reflections	3 standard reflections every 97 reflections
2250 independent reflections	intensity decay: 1.5%
1843 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.19 e Å⁻³
2250 reflections	Δρ_min = −0.15 e Å⁻³
286 parameters	Absolute structure: Assigned from synthesis. Friedel pairs (621) were merged

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6918 (2)	0.2061 (2)	0.96330 (9)	0.0342 (5)
C2	0.7571 (3)	0.3060 (3)	0.93294 (10)	0.0324 (6)
O2	0.8401 (2)	0.27815 (18)	0.89463 (8)	0.0451 (5)
C3	0.7286 (3)	0.4508 (3)	0.94792 (10)	0.0330 (6)
C4	0.6613 (3)	0.4827 (3)	0.99592 (11)	0.0360 (6)
O4	0.6401 (2)	0.61396 (19)	1.01054 (8)	0.0515 (6)
H4	0.591 (4)	0.629 (4)	1.0457 (14)	0.077*
C5	0.6126 (3)	0.3712 (3)	1.03453 (11)	0.0397 (7)
H5A	0.5315	0.4021	1.0551	0.048*
H5B	0.6845	0.3498	1.0617	0.048*
C6	0.5774 (3)	0.2438 (3)	1.00066 (12)	0.0395 (6)
H6A	0.5579	0.1683	1.0262	0.047*
H6B	0.4950	0.2608	0.9783	0.047*
C7	0.7035 (3)	0.0612 (3)	0.94466 (11)	0.0364 (7)
H7A	0.7807	0.0575	0.9179	0.044*
C8	0.7425 (4)	−0.0316 (3)	0.99393 (13)	0.0523 (8)
H8A	0.8233	0.0043	1.0123	0.078*
H8B	0.7616	−0.1225	0.9802	0.078*
H8C	0.6673	−0.0352	1.0204	0.078*
C9	0.5745 (3)	0.0181 (3)	0.91220 (11)	0.0412 (7)
C10	0.5143 (4)	−0.1103 (4)	0.91817 (15)	0.0656 (10)
H10A	0.5525	−0.1738	0.9430	0.079*
C11	0.3974 (5)	−0.1450 (5)	0.8874 (2)	0.0934 (15)
H11A	0.3575	−0.2312	0.8920	0.112*
C12	0.3405 (5)	−0.0541 (6)	0.8505 (2)	0.0936 (15)
H12A	0.2614	−0.0779	0.8304	0.112*
C13	0.3993 (4)	0.0718 (5)	0.84287 (17)	0.0778 (12)
H13A	0.3616	0.1332	0.8170	0.093*
C14	0.5151 (3)	0.1078 (4)	0.87365 (12)	0.0557 (9)
H14A	0.5541	0.1942	0.8684	0.067*
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'A	0.9110	0.6518	0.9570	0.044*
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'A	0.7012	0.4593	0.8380	0.052*
H5'B	0.6462	0.6098	0.8461	0.052*
C6'	0.8320 (3)	0.6029 (3)	0.80695 (10)	0.0445 (7)
H6'A	0.9038	0.5341	0.8024	0.053*
H6'B	0.7879	0.6161	0.7706	0.053*
C7'	0.9595 (3)	0.8177 (3)	0.78050 (10)	0.0380 (7)
H7'A	0.9965	0.9002	0.7989	0.046*
C8'	1.0818 (3)	0.7410 (3)	0.75459 (13)	0.0517 (8)
H8'A	1.1431	0.7112	0.7841	0.078*
H8'B	1.1307	0.8011	0.7294	0.078*
H8'C	1.0486	0.6625	0.7341	0.078*
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)
H10B	0.9502	0.8189	0.6663	0.055*
C11'	0.7697 (4)	0.9065 (4)	0.64424 (13)	0.0623 (10)
H11B	0.7848	0.9015	0.6055	0.075*
C12'	0.6498 (4)	0.9619 (4)	0.66362 (14)	0.0677 (11)
H12B	0.5838	0.9950	0.6385	0.081*
C13'	0.6274 (4)	0.9684 (4)	0.72079 (15)	0.0694 (10)
H13B	0.5451	1.0050	0.7345	0.083*
C14'	0.7266 (3)	0.9210 (3)	0.75817 (12)	0.0540 (9)
H14B	0.7104	0.9267	0.7968	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0404 (13)	0.0275 (11)	0.0346 (11)	−0.0001 (11)	0.0091 (10)	−0.0041 (9)
C2	0.0325 (14)	0.0351 (14)	0.0297 (12)	−0.0011 (13)	0.0019 (12)	−0.0017 (12)
O2	0.0508 (12)	0.0422 (11)	0.0423 (10)	0.0002 (10)	0.0178 (10)	−0.0038 (9)
C3	0.0391 (15)	0.0313 (14)	0.0285 (13)	−0.0026 (13)	0.0019 (13)	0.0015 (11)
C4	0.0411 (15)	0.0299 (13)	0.0369 (14)	0.0002 (13)	0.0029 (14)	−0.0022 (12)
O4	0.0783 (15)	0.0321 (10)	0.0440 (11)	0.0044 (12)	0.0186 (12)	−0.0040 (9)
C5	0.0492 (17)	0.0355 (14)	0.0345 (13)	0.0030 (15)	0.0127 (13)	−0.0003 (12)
C6	0.0438 (15)	0.0335 (13)	0.0413 (13)	−0.0009 (15)	0.0131 (14)	0.0015 (12)
C7	0.0408 (16)	0.0304 (14)	0.0379 (15)	0.0023 (13)	0.0076 (13)	−0.0029 (12)
C8	0.069 (2)	0.0383 (16)	0.0498 (17)	0.0068 (17)	0.0001 (18)	0.0023 (14)
C9	0.0424 (16)	0.0387 (16)	0.0425 (15)	−0.0041 (15)	0.0104 (14)	−0.0084 (13)
C10	0.075 (2)	0.055 (2)	0.067 (2)	−0.022 (2)	0.007 (2)	−0.0112 (18)
C11	0.090 (3)	0.079 (3)	0.112 (3)	−0.046 (3)	0.012 (3)	−0.025 (3)
C12	0.061 (3)	0.115 (4)	0.105 (3)	−0.021 (3)	−0.015 (3)	−0.047 (3)
C13	0.064 (2)	0.100 (3)	0.069 (2)	0.016 (3)	−0.022 (2)	−0.023 (2)
C14	0.060 (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—C2	1.363 (3)	C14—H14A	0.9300
N1—C6	1.463 (3)	N1'—C2'	1.348 (3)
N1—C7	1.482 (3)	N1'—C6'	1.464 (3)
C2—O2	1.241 (3)	N1'—C7'	1.478 (3)
C2—C3	1.478 (4)	C2'—O2'	1.240 (3)
C3—C4	1.346 (4)	C2'—C3'	1.469 (4)
C3—C4'	1.488 (3)	C3'—C4'	1.334 (4)
C4—O4	1.339 (3)	C3'—H3'A	0.9300
C4—C5	1.495 (4)	C4'—C5'	1.501 (4)
O4—H4	0.97 (4)	C5'—C6'	1.482 (4)
C5—C6	1.515 (4)	C5'—H5'A	0.9700
C5—H5A	0.9700	C5'—H5'B	0.9700
C5—H5B	0.9700	C6'—H6'A	0.9700
C6—H6A	0.9700	C6'—H6'B	0.9700
C6—H6B	0.9700	C7'—C9'	1.517 (4)
C7—C8	1.523 (4)	C7'—C8'	1.527 (4)
C7—C9	1.524 (4)	C7'—H7'A	0.9800
C7—H7A	0.9800	C8'—H8'A	0.9600
C8—H8A	0.9600	C8'—H8'B	0.9600
C8—H8B	0.9600	C8'—H8'C	0.9600
C8—H8C	0.9600	C9'—C10'	1.390 (4)
C9—C10	1.385 (5)	C9'—C14'	1.392 (4)
C9—C14	1.388 (4)	C10'—C11'	1.380 (4)
C10—C11	1.386 (6)	C10'—H10B	0.9300
C10—H10A	0.9300	C11'—C12'	1.357 (5)
C11—C12	1.359 (6)	C11'—H11B	0.9300
C11—H11A	0.9300	C12'—C13'	1.373 (5)
C12—C13	1.362 (6)	C12'—H12B	0.9300
C12—H12A	0.9300	C13'—C14'	1.384 (5)
C13—C14	1.381 (5)	C13'—H13B	0.9300
C13—H13A	0.9300	C14'—H14B	0.9300

C2—N1—C6	119.3 (2)	C2'—N1'—C6'	119.8 (2)
C2—N1—C7	119.1 (2)	C2'—N1'—C7'	120.4 (2)
C6—N1—C7	118.4 (2)	C6'—N1'—C7'	116.79 (19)
O2—C2—N1	121.9 (2)	O2'—C2'—N1'	121.2 (2)
O2—C2—C3	120.3 (2)	O2'—C2'—C3'	121.7 (2)
N1—C2—C3	117.8 (2)	N1'—C2'—C3'	117.1 (2)
C4—C3—C2	120.8 (2)	C4'—C3'—C2'	123.3 (2)
C4—C3—C4'	124.5 (2)	C4'—C3'—H3'A	118.3
C2—C3—C4'	114.6 (2)	C2'—C3'—H3'A	118.3
O4—C4—C3	120.8 (2)	C3'—C4'—C3	124.0 (2)
O4—C4—C5	119.1 (2)	C3'—C4'—C5'	117.8 (2)
C3—C4—C5	120.1 (2)	C3—C4'—C5'	118.2 (2)
C4—O4—H4	116 (2)	C6'—C5'—C4'	111.5 (2)
C4—C5—C6	109.9 (2)	C6'—C5'—H5'A	109.3
C4—C5—H5A	109.7	C4'—C5'—H5'A	109.3
C6—C5—H5A	109.7	C6'—C5'—H5'B	109.3
C4—C5—H5B	109.7	C4'—C5'—H5'B	109.3
C6—C5—H5B	109.7	H5'A—C5'—H5'B	108.0
H5A—C5—H5B	108.2	N1'—C6'—C5'	112.2 (2)
N1—C6—C5	110.8 (2)	N1'—C6'—H6'A	109.2
N1—C6—H6A	109.5	C5'—C6'—H6'A	109.2
C5—C6—H6A	109.5	N1'—C6'—H6'B	109.2
N1—C6—H6B	109.5	C5'—C6'—H6'B	109.2
C5—C6—H6B	109.5	H6'A—C6'—H6'B	107.9
H6A—C6—H6B	108.1	N1'—C7'—C9'	110.0 (2)
N1—C7—C8	110.8 (2)	N1'—C7'—C8'	109.7 (2)
N1—C7—C9	110.5 (2)	C9'—C7'—C8'	115.1 (2)
C8—C7—C9	115.2 (2)	N1'—C7'—H7'A	107.2
N1—C7—H7A	106.6	C9'—C7'—H7'A	107.2
C8—C7—H7A	106.6	C8'—C7'—H7'A	107.2
C9—C7—H7A	106.6	C7'—C8'—H8'A	109.5
C7—C8—H8A	109.5	C7'—C8'—H8'B	109.5
C7—C8—H8B	109.5	H8'A—C8'—H8'B	109.5
H8A—C8—H8B	109.5	C7'—C8'—H8'C	109.5
C7—C8—H8C	109.5	H8'A—C8'—H8'C	109.5
H8A—C8—H8C	109.5	H8'B—C8'—H8'C	109.5
H8B—C8—H8C	109.5	C10'—C9'—C14'	117.5 (3)
C10—C9—C14	117.4 (3)	C10'—C9'—C7'	122.4 (3)
C10—C9—C7	122.7 (3)	C14'—C9'—C7'	120.1 (2)
C14—C9—C7	119.8 (3)	C11'—C10'—C9'	120.5 (3)
C9—C10—C11	120.5 (4)	C11'—C10'—H10B	119.8
C9—C10—H10A	119.7	C9'—C10'—H10B	119.8
C11—C10—H10A	119.7	C12'—C11'—C10'	121.5 (3)
C12—C11—C10	120.6 (4)	C12'—C11'—H11B	119.3
C12—C11—H11A	119.7	C10'—C11'—H11B	119.3
C10—C11—H11A	119.7	C11'—C12'—C13'	119.1 (3)
C11—C12—C13	120.1 (4)	C11'—C12'—H12B	120.4
C11—C12—H12A	120.0	C13'—C12'—H12B	120.4
C13—C12—H12A	120.0	C12'—C13'—C14'	120.4 (3)
C12—C13—C14	119.8 (4)	C12'—C13'—H13B	119.8
C12—C13—H13A	120.1	C14'—C13'—H13B	119.8
C14—C13—H13A	120.1	C13'—C14'—C9'	121.0 (3)
C13—C14—C9	121.5 (4)	C13'—C14'—H14B	119.5
C13—C14—H14A	119.2	C9'—C14'—H14B	119.5
C9—C14—H14A	119.2

C6—N1—C2—O2	−169.0 (2)	C6'—N1'—C2'—O2'	169.0 (3)
C7—N1—C2—O2	−9.4 (4)	C7'—N1'—C2'—O2'	9.0 (4)
C6—N1—C2—C3	12.4 (4)	C6'—N1'—C2'—C3'	−11.1 (4)
C7—N1—C2—C3	172.0 (2)	C7'—N1'—C2'—C3'	−171.1 (2)
O2—C2—C3—C4	−166.8 (3)	O2'—C2'—C3'—C4'	170.0 (3)
N1—C2—C3—C4	11.8 (4)	N1'—C2'—C3'—C4'	−10.0 (4)
O2—C2—C3—C4'	11.4 (4)	C2'—C3'—C4'—C3	−179.2 (3)
N1—C2—C3—C4'	−170.0 (2)	C2'—C3'—C4'—C5'	−1.1 (4)
C2—C3—C4—O4	177.4 (3)	C4—C3—C4'—C3'	59.3 (4)
C4'—C3—C4—O4	−0.5 (4)	C2—C3—C4'—C3'	−118.7 (3)
C2—C3—C4—C5	−0.8 (4)	C4—C3—C4'—C5'	−118.8 (3)
C4'—C3—C4—C5	−178.8 (3)	C2—C3—C4'—C5'	63.2 (3)
O4—C4—C5—C6	150.8 (3)	C3'—C4'—C5'—C6'	30.6 (4)
C3—C4—C5—C6	−30.9 (4)	C3—C4'—C5'—C6'	−151.1 (2)
C2—N1—C6—C5	−44.4 (3)	C2'—N1'—C6'—C5'	40.8 (4)
C7—N1—C6—C5	155.8 (2)	C7'—N1'—C6'—C5'	−158.4 (2)
C4—C5—C6—N1	51.5 (3)	C4'—C5'—C6'—N1'	−48.9 (3)
C2—N1—C7—C8	131.3 (3)	C2'—N1'—C7'—C9'	−135.9 (3)
C6—N1—C7—C8	−68.8 (3)	C6'—N1'—C7'—C9'	63.5 (3)
C2—N1—C7—C9	−99.8 (3)	C2'—N1'—C7'—C8'	96.5 (3)
C6—N1—C7—C9	60.1 (3)	C6'—N1'—C7'—C8'	−64.1 (3)
N1—C7—C9—C10	−140.3 (3)	N1'—C7'—C9'—C10'	−133.8 (3)
C8—C7—C9—C10	−13.8 (4)	C8'—C7'—C9'—C10'	−9.2 (4)
N1—C7—C9—C14	41.5 (3)	N1'—C7'—C9'—C14'	47.8 (3)
C8—C7—C9—C14	168.0 (3)	C8'—C7'—C9'—C14'	172.3 (3)
C14—C9—C10—C11	−1.3 (5)	C14'—C9'—C10'—C11'	1.1 (5)
C7—C9—C10—C11	−179.6 (3)	C7'—C9'—C10'—C11'	−177.3 (3)
C9—C10—C11—C12	0.5 (6)	C9'—C10'—C11'—C12'	−0.7 (5)
C10—C11—C12—C13	0.9 (7)	C10'—C11'—C12'—C13'	−0.3 (6)
C11—C12—C13—C14	−1.4 (7)	C11'—C12'—C13'—C14'	0.9 (6)
C12—C13—C14—C9	0.5 (5)	C12'—C13'—C14'—C9'	−0.5 (6)
C10—C9—C14—C13	0.8 (5)	C10'—C9'—C14'—C13'	−0.5 (5)
C7—C9—C14—C13	179.1 (3)	C7'—C9'—C14'—C13'	178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2′ⁱ	0.97 (4)	1.67 (4)	2.637 (3)	177 (4)

Symmetry code: (i) x−1/2, −y+3/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₈N₂O₃
M_r	416.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	9.6647 (13), 9.7281 (10), 23.684 (3)
V (Å³)	2226.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.60 × 0.60 × 0.08

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3173, 2250, 1843
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.095, 1.04
No. of reflections	2250
No. of parameters	286
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15
Absolute structure	Assigned 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···A	D—H	H···A	D···A	D—H···A
O4—H4···O2'ⁱ	0.97 (4)	1.67 (4)	2.637 (3)	177 (4)

Symmetry code: (i) x−1/2, −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

Didierjean, C., Marin, J., Wenger, E., Briand, J.-P., Aubry, A. & Guichard, G. (2004). Acta Cryst. C60, o200–o203. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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Volume 69| Part 3| March 2013| Pages o408-o409

doi:10.1107/S1600536813004017

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

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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