2,6-Bis[(4R,5R)-4,5-diphenyl-4,5-di­hydro-1,3-oxazol-2-yl]pyridine

Lin, N.; Deng, Y.-Q.; Chen, M.-M.; Luo, R.-S.; Ng, S.W.

doi:10.1107/S1600536811014668

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1344

doi:10.1107/S1600536811014668

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2,6-Bis[(4R,5R)-4,5-diphenyl-4,5-dihydro-1,3-oxazol-2-yl]pyridine

Ning Lin,^a Yan-Qiu Deng,^a Miao-Miao Chen,^a Ren-Shi Luo ^a and Seik Weng Ng ^b ^*

^aInstitute of Drug Synthesis and Pharmaceutical Processes, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 April 2011; accepted 19 April 2011; online 7 May 2011)

The molecule of the title compound, C₃₅H₂₇N₃O₂, lies on a twofold rotation axis passing through the pyridine ring. The five-membered ring is approximately flat (r.m.s. deviation = 0.065 Å) and is essentially coplanar [dihedral angle = 4.2 (2)°] with the pyridine ring.

Related literature

For the synthesis of the precursor, see: Desimoni et al. (2001 ). For the structure of 2,6-bis(2-oxazolinyl)pyridine, see: Sada et al. (2003 ).

Experimental

Crystal data

C₃₅H₂₇N₃O₂
M_r = 521.60
Monoclinic, C 2
a = 19.035 (2) Å
b = 6.5908 (7) Å
c = 14.3001 (15) Å
β = 129.454 (1)°
V = 1385.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.38 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
3266 measured reflections
1299 independent reflections
1190 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.099
S = 1.05
1299 reflections
182 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.11 e Å⁻³
Absolute structure: 768 Friedel pairs merged

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014668/bt5522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014668/bt5522Isup2.hkl

checkCIF report

Comment top

We report here the cyclization of the two side arms of (2,6-bis[(1R,2S)N,N'-2-chloro-1,2-diphenylethyl]-pyridinedicarboxamide to form a di-substituted pyridine having two 1,3-oxazoline rings. The title compound is intended for an evaluation of its phamaceutical properties. It lies on a twofold rotation axis that passes through the pyridine ring (Fig. 1). The five-membered ring is approximately flat [r.m.s. deviation 0.065 Å] and is nearly coplanar [dihedral angle 4.2 (2)°] with the pyridine ring. In the parent compound, 2,6-bis(2-oxazolinyl)pyridine, the three rings are similarly nearly coplanar (Sada et al., 2003).

Related literature top

For the synthesis of the precursor, see: Desimoni et al. (2001). For the structure of 2,6-bis(2-oxazolinyl)pyridine, see: Sada et al. (2003).

Experimental top

To a suspension of 2,6-bis[(1R,2S)N,N'-2-chloro-1,2-diphenylethyl]-pyridinedicarboxamide (Desimoni et al., 2001) (0.89 g, 1.5 mmol) in ethanol (26 ml), an equeous solution of 2 N sodium hydroxide (13 ml) was added and the mixture was refluxed 8 h. The hot suspension was filtered and the white solid was washed with water (0.73 g, yield 90%). Crystals were obtained by recrystallization from ethyl acetate; m.p. 474–474 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₃₅H₃₇N₃O₂ at the 50% probability level; H atoms are drawn as arbitrary radius.

2,6-Bis[(4R,5R)-4,5-diphenyl-4,5-dihydro-1,3-oxazol-2-yl]pyridine top

Crystal data top

C₃₅H₂₇N₃O₂	F(000) = 548
M_r = 521.60	D_x = 1.251 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 1652 reflections
a = 19.035 (2) Å	θ = 2.8–26.1°
b = 6.5908 (7) Å	µ = 0.08 mm⁻¹
c = 14.3001 (15) Å	T = 293 K
β = 129.454 (1)°	Prism, colourless
V = 1385.2 (3) Å³	0.38 × 0.20 × 0.16 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 25.0°, θ_min = 2.9°
ϕ and ω scans	h = −22→22
3266 measured reflections	k = −7→7
1299 independent reflections	l = −17→15

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0722P)² + 0.0677P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1299 reflections	Δρ_max = 0.16 e Å⁻³
182 parameters	Δρ_min = −0.11 e Å⁻³
1 restraint	Absolute structure: 768 Friedel pairs merged
Primary atom site location: structure-invariant direct methods

Crystal data top

C₃₅H₂₇N₃O₂	V = 1385.2 (3) Å³
M_r = 521.60	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 19.035 (2) Å	µ = 0.08 mm⁻¹
b = 6.5908 (7) Å	T = 293 K
c = 14.3001 (15) Å	0.38 × 0.20 × 0.16 mm
β = 129.454 (1)°

Data collection top

Bruker SMART CCD diffractometer	1190 reflections with I > 2σ(I)
3266 measured reflections	R_int = 0.017
1299 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
1299 reflections	Δρ_min = −0.11 e Å⁻³
182 parameters	Absolute structure: 768 Friedel pairs merged

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

	x	y	z	U_iso*/U_eq
O1	−0.00290 (12)	0.4999 (2)	0.24429 (14)	0.0590 (5)
N1	0.0000	0.3969 (4)	0.0000	0.0453 (6)
N2	0.00872 (13)	0.1951 (3)	0.18302 (16)	0.0503 (5)
C1	0.0000	0.8221 (5)	0.0000	0.0582 (8)
H1	0.0000	0.9632	0.0000	0.070*
C2	−0.00113 (15)	0.7152 (4)	0.0817 (2)	0.0538 (6)
H2	−0.0023	0.7831	0.1377	0.065*
C3	−0.00049 (13)	0.5041 (3)	0.07933 (18)	0.0449 (5)
C4	0.00168 (14)	0.3864 (4)	0.16940 (19)	0.0472 (5)
C5	0.00709 (15)	0.1499 (4)	0.2830 (2)	0.0505 (5)
H5	0.0604	0.0679	0.3445	0.061*
C6	−0.07812 (16)	0.0392 (4)	0.2397 (2)	0.0522 (5)
C7	−0.16168 (18)	0.0935 (5)	0.1346 (2)	0.0769 (8)
H7	−0.1661	0.1950	0.0859	0.092*
C8	−0.2399 (2)	−0.0029 (6)	0.1005 (3)	0.0909 (10)
H8	−0.2964	0.0356	0.0294	0.109*
C9	−0.2346 (2)	−0.1521 (6)	0.1699 (4)	0.0887 (10)
H9	−0.2872	−0.2154	0.1468	0.106*
C10	−0.1519 (2)	−0.2093 (5)	0.2738 (3)	0.0833 (9)
H10	−0.1481	−0.3124	0.3212	0.100*
C11	−0.07370 (18)	−0.1150 (4)	0.3090 (2)	0.0648 (7)
H11	−0.0175	−0.1553	0.3800	0.078*
C12	0.01565 (15)	0.3640 (4)	0.33649 (19)	0.0498 (5)
H12	−0.0314	0.3795	0.3447	0.060*
C13	0.10798 (15)	0.4089 (4)	0.45661 (19)	0.0493 (5)
C14	0.14229 (19)	0.2821 (5)	0.5543 (2)	0.0654 (7)
H14	0.1074	0.1742	0.5463	0.078*
C15	0.2283 (2)	0.3148 (6)	0.6638 (3)	0.0788 (8)
H15	0.2515	0.2268	0.7284	0.095*
C16	0.27910 (19)	0.4766 (5)	0.6770 (3)	0.0738 (8)
H16	0.3367	0.4995	0.7506	0.089*
C17	0.24501 (16)	0.6032 (5)	0.5823 (3)	0.0712 (8)
H17	0.2794	0.7136	0.5916	0.085*
C18	0.16001 (17)	0.5710 (4)	0.4720 (2)	0.0600 (6)
H18	0.1378	0.6592	0.4079	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0850 (11)	0.0442 (10)	0.0564 (9)	0.0107 (8)	0.0489 (9)	0.0016 (8)
N1	0.0524 (14)	0.0389 (14)	0.0499 (14)	0.000	0.0350 (12)	0.000
N2	0.0666 (11)	0.0425 (12)	0.0597 (11)	−0.0016 (9)	0.0486 (10)	−0.0038 (9)
C1	0.070 (2)	0.0344 (17)	0.061 (2)	0.000	0.0377 (17)	0.000
C2	0.0642 (14)	0.0395 (13)	0.0570 (13)	0.0013 (11)	0.0381 (12)	−0.0048 (11)
C3	0.0466 (12)	0.0397 (13)	0.0473 (11)	0.0004 (9)	0.0294 (10)	−0.0013 (9)
C4	0.0525 (12)	0.0443 (13)	0.0496 (12)	0.0032 (10)	0.0347 (10)	−0.0006 (10)
C5	0.0618 (13)	0.0449 (13)	0.0549 (12)	−0.0013 (10)	0.0418 (11)	−0.0010 (11)
C6	0.0666 (13)	0.0445 (12)	0.0565 (12)	−0.0065 (11)	0.0442 (12)	−0.0076 (10)
C7	0.0767 (17)	0.079 (2)	0.0661 (15)	−0.0148 (16)	0.0411 (15)	0.0034 (15)
C8	0.0714 (18)	0.103 (3)	0.0825 (19)	−0.0200 (19)	0.0413 (16)	−0.010 (2)
C9	0.090 (2)	0.083 (2)	0.117 (2)	−0.0336 (19)	0.078 (2)	−0.029 (2)
C10	0.106 (2)	0.0622 (18)	0.122 (2)	−0.0105 (17)	0.092 (2)	0.0006 (19)
C11	0.0817 (16)	0.0521 (14)	0.0830 (17)	0.0032 (13)	0.0629 (15)	0.0058 (14)
C12	0.0648 (13)	0.0450 (13)	0.0543 (12)	0.0017 (11)	0.0448 (12)	−0.0005 (10)
C13	0.0642 (13)	0.0468 (13)	0.0546 (12)	−0.0019 (10)	0.0460 (11)	−0.0041 (10)
C14	0.0837 (17)	0.0614 (17)	0.0612 (14)	−0.0122 (14)	0.0507 (14)	−0.0017 (13)
C15	0.0943 (19)	0.080 (2)	0.0591 (15)	0.0159 (19)	0.0474 (15)	0.0108 (16)
C16	0.0644 (15)	0.078 (2)	0.0718 (16)	0.0007 (15)	0.0399 (14)	−0.0115 (16)
C17	0.0644 (16)	0.0689 (18)	0.0885 (18)	−0.0091 (14)	0.0523 (16)	−0.0086 (16)
C18	0.0687 (15)	0.0554 (15)	0.0696 (14)	−0.0040 (13)	0.0504 (13)	0.0000 (12)

Geometric parameters (Å, º) top

O1—C4	1.354 (3)	C8—H8	0.9300
O1—C12	1.440 (3)	C9—C10	1.362 (5)
N1—C3	1.341 (2)	C9—H9	0.9300
N1—C3ⁱ	1.341 (2)	C10—C11	1.379 (4)
N2—C4	1.270 (3)	C10—H10	0.9300
N2—C5	1.480 (3)	C11—H11	0.9300
C1—C2	1.376 (3)	C12—C13	1.513 (3)
C1—C2ⁱ	1.376 (3)	C12—H12	0.9800
C1—H1	0.9300	C13—C18	1.376 (3)
C2—C3	1.392 (3)	C13—C14	1.384 (3)
C2—H2	0.9300	C14—C15	1.386 (4)
C3—C4	1.481 (3)	C14—H14	0.9300
C5—C6	1.507 (3)	C15—C16	1.370 (5)
C5—C12	1.563 (3)	C15—H15	0.9300
C5—H5	0.9800	C16—C17	1.355 (4)
C6—C7	1.371 (4)	C16—H16	0.9300
C6—C11	1.384 (3)	C17—C18	1.381 (4)
C7—C8	1.392 (4)	C17—H17	0.9300
C7—H7	0.9300	C18—H18	0.9300
C8—C9	1.355 (5)

C4—O1—C12	106.19 (17)	C10—C9—H9	120.1
C3—N1—C3ⁱ	116.5 (2)	C9—C10—C11	120.4 (3)
C4—N2—C5	106.44 (19)	C9—C10—H10	119.8
C2—C1—C2ⁱ	118.4 (3)	C11—C10—H10	119.8
C2—C1—H1	120.8	C10—C11—C6	120.6 (3)
C2ⁱ—C1—H1	120.8	C10—C11—H11	119.7
C1—C2—C3	119.1 (2)	C6—C11—H11	119.7
C1—C2—H2	120.5	O1—C12—C13	110.46 (18)
C3—C2—H2	120.5	O1—C12—C5	103.00 (15)
N1—C3—C2	123.5 (2)	C13—C12—C5	114.64 (19)
N1—C3—C4	116.65 (18)	O1—C12—H12	109.5
C2—C3—C4	119.9 (2)	C13—C12—H12	109.5
N2—C4—O1	118.7 (2)	C5—C12—H12	109.5
N2—C4—C3	126.5 (2)	C18—C13—C14	118.5 (2)
O1—C4—C3	114.73 (18)	C18—C13—C12	122.2 (2)
N2—C5—C6	112.22 (19)	C14—C13—C12	119.3 (2)
N2—C5—C12	103.37 (18)	C13—C14—C15	120.5 (3)
C6—C5—C12	112.88 (18)	C13—C14—H14	119.7
N2—C5—H5	109.4	C15—C14—H14	119.7
C6—C5—H5	109.4	C16—C15—C14	120.0 (3)
C12—C5—H5	109.4	C16—C15—H15	120.0
C7—C6—C11	118.5 (2)	C14—C15—H15	120.0
C7—C6—C5	121.4 (2)	C17—C16—C15	119.6 (3)
C11—C6—C5	120.1 (2)	C17—C16—H16	120.2
C6—C7—C8	120.2 (3)	C15—C16—H16	120.2
C6—C7—H7	119.9	C16—C17—C18	121.1 (3)
C8—C7—H7	119.9	C16—C17—H17	119.5
C9—C8—C7	120.6 (3)	C18—C17—H17	119.5
C9—C8—H8	119.7	C13—C18—C17	120.3 (3)
C7—C8—H8	119.7	C13—C18—H18	119.9
C8—C9—C10	119.7 (3)	C17—C18—H18	119.9
C8—C9—H9	120.1

C2ⁱ—C1—C2—C3	0.42 (15)	C8—C9—C10—C11	0.5 (5)
C3ⁱ—N1—C3—C2	0.45 (17)	C9—C10—C11—C6	0.1 (5)
C3ⁱ—N1—C3—C4	−178.3 (2)	C7—C6—C11—C10	−1.0 (4)
C1—C2—C3—N1	−0.9 (3)	C5—C6—C11—C10	176.2 (3)
C1—C2—C3—C4	177.79 (15)	C4—O1—C12—C13	109.2 (2)
C5—N2—C4—O1	1.7 (3)	C4—O1—C12—C5	−13.6 (2)
C5—N2—C4—C3	−179.57 (19)	N2—C5—C12—O1	14.4 (2)
C12—O1—C4—N2	8.5 (3)	C6—C5—C12—O1	−107.09 (19)
C12—O1—C4—C3	−170.44 (17)	N2—C5—C12—C13	−105.65 (19)
N1—C3—C4—N2	3.9 (3)	C6—C5—C12—C13	132.9 (2)
C2—C3—C4—N2	−174.8 (2)	O1—C12—C13—C18	5.3 (3)
N1—C3—C4—O1	−177.25 (15)	C5—C12—C13—C18	121.1 (2)
C2—C3—C4—O1	4.0 (3)	O1—C12—C13—C14	−173.81 (18)
C4—N2—C5—C6	111.8 (2)	C5—C12—C13—C14	−58.0 (3)
C4—N2—C5—C12	−10.1 (3)	C18—C13—C14—C15	−1.9 (4)
N2—C5—C6—C7	−42.1 (3)	C12—C13—C14—C15	177.2 (2)
C12—C5—C6—C7	74.2 (3)	C13—C14—C15—C16	1.7 (4)
N2—C5—C6—C11	140.8 (2)	C14—C15—C16—C17	−0.4 (4)
C12—C5—C6—C11	−102.8 (2)	C15—C16—C17—C18	−0.5 (4)
C11—C6—C7—C8	1.1 (4)	C14—C13—C18—C17	1.0 (3)
C5—C6—C7—C8	−176.0 (3)	C12—C13—C18—C17	−178.2 (2)
C6—C7—C8—C9	−0.5 (5)	C16—C17—C18—C13	0.3 (4)
C7—C8—C9—C10	−0.3 (5)

Symmetry code: (i) −x, y, −z.

Experimental details

Crystal data
Chemical formula	C₃₅H₂₇N₃O₂
M_r	521.60
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	19.035 (2), 6.5908 (7), 14.3001 (15)
β (°)	129.454 (1)
V (Å³)	1385.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.38 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3266, 1299, 1190
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.05
No. of reflections	1299
No. of parameters	182
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.11
Absolute structure	768 Friedel pairs merged

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank the Scientific Research Foundation for Returned Overseas Chinese Scholars and the Programme for New Century Excellent Talents (both from the State Education Ministry of China), the Project of International Science and Technology Cooperation (from the Ministry of Science and Technology of China) and the University of Malaya for supporting this study.

References

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