4-Hy-droxy-1,1'-bis-[(S)-1-phenyl-eth-yl]-5,5',6,6'-tetra-hydro-3,4'-bipyridine-2,2'(1H,1'H)-dione.

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 enanti-omerically pure starting material. In the mol-ecule, 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 inter-mediate 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 inter-molecular O-H⋯O=C hydrogen bonds. The resulting one-dimensional supra-molecular 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 = 416.50

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 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

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813004017/nr2039sup1.cif

Click here for additional data file.

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813004017/nr2039Isup3.cml

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

C26H28N2O3	Dx = 1.242 Mg m−3
Mr = 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

Bruker P4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 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 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(Fo2) + (0.0483P)2 + 0.2404P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2250 reflections	Δρmax = 0.19 e Å−3
286 parameters	Δρmin = −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

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) .