Methyl 4-(4-fluoro­anilino)-1,2,6-tris­(4-fluoro­phen­yl)-1,2,5,6-tetra­hydro­pyri­dine-3-carboxyl­ate

Anthal, S.; Brahmachari, G.; Das, S.; Kant, R.; Gupta, V.K.

doi:10.1107/S160053681300370X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages o373-o374

doi:10.1107/S160053681300370X

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Methyl 4-(4-fluoroanilino)-1,2,6-tris(4-fluorophenyl)-1,2,5,6-tetrahydropyridine-3-carboxylate

Sumati Anthal,^a Goutam Brahmachari,^b Suvankar Das,^b Rajni Kant ^a and Vivek K. Gupta ^a ^*

^aPost-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bLaboratory of Natural Products & Organic Synthesis, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, West Bengal, India
^*Correspondence e-mail: vivek_gupta2k2@hotmail.com

(Received 24 January 2013; accepted 6 February 2013; online 9 February 2013)

In the title molecule, C₃₁H₂₄F₄N₂O₂, the tetrahydropyridine ring adopts a distorted boat conformation. An intramolecular N—H⋯O hydrogen bond is formed by the amino group and ccarboxyl C=O atom. The crystal structure features weak C—H⋯F and C—H⋯O interactions.

Related literature

For biological activity of functionalized piperidine derivatives, see: Zhou et al. (2007 ); Misra et al. (2009 ); Bin et al. (2001 ); Agrawal & Somani (2009 ); Jaen et al. (1988 ). For general background to functionalized piperidines, see: Kamei et al. (2005 ). For related structures, see: Sambyal et al. (2011 ); Brahmachari & Das (2012 ); Khan et al. (2010 ); Anthal et al. (2013 ). For asymmetry parameters, see: Duax et al. (1975 ).

Experimental

Crystal data

C₃₁H₂₄F₄N₂O₂
M_r = 532.52
Triclinic, $[P \overline 1]$
a = 9.7990 (2) Å
b = 10.7316 (4) Å
c = 13.7395 (4) Å
α = 110.797 (3)°
β = 100.338 (2)°
γ = 96.323 (2)°
V = 1304.81 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.899, T_max = 1.000
42990 measured reflections
5413 independent reflections
3730 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.118
S = 1.05
5413 reflections
353 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O1	0.86	2.05	2.695 (2)	131
C20—H20⋯F2ⁱ	0.93	2.54	3.384 (2)	152
C32—H32⋯O1ⁱⁱ	0.93	2.47	3.311 (3)	151
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681300370X/gk2551sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300370X/gk2551Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300370X/gk2551Isup3.cml

checkCIF report

Comment top

Functionalized piperidines, very particularly 1,4-disubstituted piperidine scaffolds, are found to be useful in designing a variety of medicinal entities exhibiting a broad spectrum of pharmacological activities that include antibacterial (Zhou et al., 2007), antimalarial (Misra et al., 2009), anti-hypertensive, anticonvulsant, anti-inflammatory (Bin et al., 2001), and enzyme inhibitory activity (Agrawal & Somani, 2009; Jaen et al., 1988). Moreover, a large number of compounds bearing piperidine scaffold have already entered into preclinical and clinical trials over the last few years (Kamei et al., 2005). Hence, investigation of the structural features of biologically relevant piperidine derivatives is demanding. In continuation of our structural studies of densely functionalized piperidines (Sambyal et al., 2011; Brahmachari & Das, 2012) we present here the crystal structure of the title compound. The molecular structure of the title compound is illustrated in Fig.1. The bond lengths and angles of the title compound are normal and correspond to those observed in related structures (Khan et al., 2010; Anthal et al., 2013). In the title molecule, tetrahydropyridine ring adopts a distorted boat conformation with asymmetry parameters [ΔC_s(C2)=10.10] and [ΔC_s(C3-C4)=15.48] (Duax et al., 1975). In the crystal, an intramolecular hydrogen bond N9-H9···O1 is found. This intramolecular interaction leads to the formation of a pseudo-six membered ring comprising atoms O1, C7, C3, C4, N9 and H9. The molecular structure is stablized by N—H···O intramolecular interaction and crystal packing is stablized by C—H···F and C—H···O intermolecular interactions (Table 1). Molecules are linked via C—H···F and C—H···O hydrogen bonds to form chains along [010](Fig. 2).

Related literature top

For biological activity of functionalized piperidine derivatives, see: Zhou et al. (2007); Misra et al. (2009); Bin et al. (2001); Agrawal & Somani (2009); Jaen et al. (1988). For general background to functionalized piperidines, see: Kamei et al. (2005). For related structures, see: Sambyal et al. (2011); Brahmachari & Das, (2012); Khan et al. (2010); Anthal et al. (2013). For asymmetry parameters, see: Duax et al. (1975).

Experimental top

An oven-dried screw cap reaction tube was charged with a magnetic stir bar, 4-fluoroaniline (2 mmol), methyl acetoacetate (1 mmol) and Bi(NO₃)₃.5H₂O (10 mol%) in 4 ml ethanol; the mixture was stirred at room temperature for 20 min, and then 4-fluorobenzaldehyde (2 mmol) was added to the reaction mixture and stirring was continued up to 12 h to complete the reaction (monitored by TLC). On completion of the reaction, a thick white precipitate was obtained. The solid residue was filtered off and washed with cold ethanol–water. The solid mass was dissolved in hot ethyl acetate–ethanol mixture and filtered off when bismuth salt separated out; the filtrate on standing afforded white crystals of the title compound, characterized by elemental analyses and spectral studies including FT—IR, ¹H-NMR, and ¹³C-NMR. For X-ray study, single crystals were prepared by further recrystallization by slow evaporation from ethanol-ethyl acetate-water solution. Methyl 1,2,6-tris(4-fluorophenyl)-4-((4-fluorophenyl)amino)-1,2,5,6- tetrahydropyridine-3-carboxylate : white crystals; mp 452–454 K. Anal. Calcd for C₃₁H₂₄F₄N₂O₂: C 69.92, H 4.54, N 5.26; found: C 69.95, H 4.52, N 5.28.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the title molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing arrangement of molecules viewed down the a axis. Short contacts are shown with dashed lines.

Methyl 4-(4-fluoroanilino)-1,2,6-tris(4-fluorophenyl)-1,2,5,6-tetrahydropyridine-3-carboxylate top

Crystal data top

C₃₁H₂₄F₄N₂O₂	Z = 2
M_r = 532.52	F(000) = 552
Triclinic, P1	D_x = 1.355 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7990 (2) Å	Cell parameters from 14371 reflections
b = 10.7316 (4) Å	θ = 3.5–29.0°
c = 13.7395 (4) Å	µ = 0.10 mm⁻¹
α = 110.797 (3)°	T = 293 K
β = 100.338 (2)°	Block, white
γ = 96.323 (2)°	0.30 × 0.20 × 0.20 mm
V = 1304.81 (7) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5413 independent reflections
Radiation source: fine-focus sealed tube	3730 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.5°, θ_min = 3.5°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −13→13
T_min = 0.899, T_max = 1.000	l = −17→17
42990 measured reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0523P)² + 0.1709P] where P = (F_o² + 2F_c²)/3
5413 reflections	(Δ/σ)_max = 0.001
353 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₃₁H₂₄F₄N₂O₂	γ = 96.323 (2)°
M_r = 532.52	V = 1304.81 (7) Å³
Triclinic, P1	Z = 2
a = 9.7990 (2) Å	Mo Kα radiation
b = 10.7316 (4) Å	µ = 0.10 mm⁻¹
c = 13.7395 (4) Å	T = 293 K
α = 110.797 (3)°	0.30 × 0.20 × 0.20 mm
β = 100.338 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5413 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	3730 reflections with I > 2σ(I)
T_min = 0.899, T_max = 1.000	R_int = 0.044
42990 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.05	Δρ_max = 0.17 e Å⁻³
5413 reflections	Δρ_min = −0.20 e Å⁻³
353 parameters

Special details top

Experimental. 1H NMR (400 MHz, CDCl₃): δH 2.62 (dd, J = 2.4, 15.2 Hz, 1H), 2.78 (dd, J = 5.2, 15 Hz, 1H), 3.91 (s, 3H), 5.04 (br d, 1H), 6.27 (br s, 1H), 6.33–6.39(m, 4H), 6.78 (t, J = 8.8 Hz, 2H), 6.84 (t, J = 8.8 Hz, 2H), 6.93–6.99 (m, 4H), 7.07–7.11 (m, 2H), 7.19–7.25 (m, 2H), 10.17 (br s, 1H). ¹³C NMR (100 MHz, CDCl₃): δC 33.71, 51.19, 55.19, 57.45, 97.64, 113.88, 113.95, 114.98, 115.2, 115.30, 115.51, 115.73, 115.96, 127.88, 127.96, 128.12, 128.20, 133.62, 133.64, 138.05, 138.99, 143.06, 154.10, 156.03, 156.44, 159.67, 160.37, 160.83, 162.12, 162.80, 163.27, 168.38. IR ν_max (KBr): 3240, 3065, 2945, 2838, 1653, 1591, 1506, 1450, 1371, 1269, 1229, 1076, 812, 771, 685 cm^-1. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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.

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

	x	y	z	U_iso*/U_eq
O1	0.05599 (13)	0.35453 (13)	−0.02481 (9)	0.0522 (3)
O2	0.25451 (13)	0.51103 (13)	0.02833 (9)	0.0553 (3)
N1	0.38897 (13)	0.47214 (13)	0.29805 (10)	0.0384 (3)
F1	0.16292 (17)	1.01431 (15)	0.51876 (13)	0.1073 (5)
F2	0.97011 (11)	0.61739 (14)	0.44660 (11)	0.0792 (4)
F3	0.36636 (18)	−0.16496 (14)	0.06807 (15)	0.1252 (6)
F4	−0.31258 (16)	−0.11300 (15)	0.23046 (12)	0.1002 (5)
C2	0.30643 (16)	0.54303 (16)	0.24088 (12)	0.0360 (4)
H2	0.3679	0.5755	0.2025	0.043*
C3	0.18153 (16)	0.44415 (16)	0.15708 (12)	0.0367 (4)
C4	0.10236 (16)	0.35791 (16)	0.18759 (12)	0.0372 (4)
C5	0.15506 (16)	0.36802 (17)	0.30004 (12)	0.0395 (4)
H5A	0.1036	0.2934	0.3110	0.047*
H5B	0.1403	0.4525	0.3504	0.047*
C6	0.31341 (16)	0.36283 (16)	0.31870 (12)	0.0361 (4)
H6	0.3484	0.3785	0.3943	0.043*
C7	0.15522 (17)	0.43097 (17)	0.04696 (13)	0.0401 (4)
C8	0.2415 (3)	0.4972 (2)	−0.08105 (16)	0.0754 (7)
H8A	0.2506	0.4070	−0.1235	0.113*
H8B	0.3144	0.5618	−0.0846	0.113*
H8C	0.1507	0.5135	−0.1081	0.113*
N9	−0.01024 (14)	0.26238 (15)	0.12273 (11)	0.0476 (4)
H9	−0.0379	0.2597	0.0589	0.057*
C10	0.26522 (16)	0.66857 (16)	0.31793 (12)	0.0365 (4)
C11	0.15179 (18)	0.72134 (18)	0.28316 (14)	0.0467 (4)
H11	0.0984	0.6782	0.2131	0.056*
C12	0.1167 (2)	0.8370 (2)	0.35088 (17)	0.0586 (5)
H12	0.0396	0.8709	0.3271	0.070*
C13	0.1962 (2)	0.9001 (2)	0.45242 (17)	0.0618 (5)
C14	0.3100 (2)	0.8534 (2)	0.49011 (16)	0.0650 (6)
H14	0.3640	0.8990	0.5598	0.078*
C15	0.3432 (2)	0.73677 (19)	0.42233 (13)	0.0514 (5)
H15	0.4197	0.7033	0.4475	0.062*
C16	0.53521 (16)	0.50829 (16)	0.33293 (12)	0.0358 (4)
C17	0.61195 (17)	0.62124 (18)	0.32556 (14)	0.0461 (4)
H17	0.5643	0.6733	0.2947	0.055*
C18	0.75664 (18)	0.65696 (19)	0.36303 (15)	0.0520 (5)
H18	0.8059	0.7324	0.3575	0.062*
C19	0.82704 (17)	0.5806 (2)	0.40835 (14)	0.0495 (4)
C20	0.75808 (17)	0.46901 (18)	0.41701 (13)	0.0446 (4)
H20	0.8079	0.4179	0.4476	0.053*
C21	0.61273 (17)	0.43295 (17)	0.37959 (12)	0.0395 (4)
H21	0.5653	0.3570	0.3855	0.047*
C22	0.33464 (16)	0.22233 (16)	0.25164 (13)	0.0376 (4)
C23	0.35639 (18)	0.19043 (19)	0.14950 (13)	0.0484 (4)
H23	0.3650	0.2581	0.1223	0.058*
C24	0.3656 (2)	0.0598 (2)	0.08718 (16)	0.0664 (6)
H24	0.3781	0.0386	0.0180	0.080*
C25	0.3560 (2)	−0.0368 (2)	0.1291 (2)	0.0742 (7)
C26	0.3379 (2)	−0.0102 (2)	0.2300 (2)	0.0761 (7)
H26	0.3334	−0.0781	0.2572	0.091*
C27	0.3264 (2)	0.12074 (19)	0.29126 (17)	0.0576 (5)
H27	0.3128	0.1404	0.3601	0.069*
C28	−0.08772 (17)	0.16492 (17)	0.15122 (13)	0.0412 (4)
C29	−0.20066 (19)	0.19542 (19)	0.19642 (14)	0.0507 (4)
H29	−0.2260	0.2797	0.2086	0.061*
C30	−0.2760 (2)	0.1026 (2)	0.22363 (16)	0.0609 (5)
H30	−0.3518	0.1232	0.2547	0.073*
C31	−0.2376 (2)	−0.0200 (2)	0.20425 (16)	0.0609 (5)
C32	−0.1273 (2)	−0.0550 (2)	0.15877 (16)	0.0639 (6)
H32	−0.1042	−0.1403	0.1457	0.077*
C33	−0.0510 (2)	0.0396 (2)	0.13272 (15)	0.0544 (5)
H33	0.0254	0.0187	0.1026	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0623 (8)	0.0492 (8)	0.0333 (6)	0.0029 (6)	−0.0044 (6)	0.0117 (6)
O2	0.0675 (8)	0.0600 (8)	0.0367 (7)	0.0003 (7)	0.0078 (6)	0.0224 (6)
N1	0.0352 (7)	0.0357 (8)	0.0428 (8)	0.0036 (6)	0.0012 (6)	0.0178 (6)
F1	0.1155 (11)	0.0732 (9)	0.1012 (11)	0.0462 (8)	0.0230 (9)	−0.0112 (8)
F2	0.0355 (6)	0.0991 (10)	0.1020 (10)	0.0026 (6)	0.0006 (6)	0.0478 (8)
F3	0.1320 (14)	0.0455 (8)	0.1517 (15)	0.0252 (8)	0.0197 (11)	−0.0127 (9)
F4	0.1154 (11)	0.0859 (10)	0.1022 (11)	−0.0199 (8)	0.0182 (9)	0.0544 (9)
C2	0.0386 (8)	0.0365 (9)	0.0317 (8)	0.0047 (7)	0.0035 (6)	0.0146 (7)
C3	0.0381 (8)	0.0356 (9)	0.0314 (8)	0.0067 (7)	0.0031 (6)	0.0095 (7)
C4	0.0344 (8)	0.0385 (9)	0.0332 (8)	0.0084 (7)	0.0038 (6)	0.0088 (7)
C5	0.0388 (9)	0.0425 (10)	0.0326 (8)	0.0039 (7)	0.0067 (7)	0.0109 (7)
C6	0.0394 (9)	0.0383 (9)	0.0282 (8)	0.0049 (7)	0.0036 (6)	0.0128 (7)
C7	0.0483 (10)	0.0349 (9)	0.0352 (9)	0.0116 (8)	0.0060 (7)	0.0119 (7)
C8	0.1054 (18)	0.0825 (16)	0.0432 (11)	0.0043 (13)	0.0191 (11)	0.0329 (11)
N9	0.0469 (8)	0.0512 (9)	0.0350 (7)	−0.0055 (7)	−0.0031 (6)	0.0154 (7)
C10	0.0396 (9)	0.0344 (9)	0.0349 (8)	0.0029 (7)	0.0052 (7)	0.0156 (7)
C11	0.0471 (10)	0.0413 (10)	0.0466 (10)	0.0063 (8)	0.0006 (8)	0.0165 (8)
C12	0.0543 (11)	0.0463 (11)	0.0735 (14)	0.0167 (9)	0.0100 (10)	0.0214 (10)
C13	0.0688 (13)	0.0451 (12)	0.0626 (13)	0.0172 (10)	0.0195 (11)	0.0062 (10)
C14	0.0734 (14)	0.0617 (13)	0.0410 (11)	0.0175 (11)	0.0030 (9)	0.0010 (10)
C15	0.0565 (11)	0.0529 (11)	0.0383 (10)	0.0170 (9)	0.0025 (8)	0.0118 (9)
C16	0.0376 (9)	0.0346 (9)	0.0290 (8)	0.0054 (7)	0.0034 (6)	0.0075 (7)
C17	0.0432 (10)	0.0448 (10)	0.0502 (10)	0.0057 (8)	0.0044 (8)	0.0221 (9)
C18	0.0446 (10)	0.0494 (11)	0.0591 (12)	−0.0024 (8)	0.0094 (8)	0.0221 (9)
C19	0.0317 (9)	0.0610 (12)	0.0478 (10)	0.0051 (8)	0.0030 (7)	0.0155 (9)
C20	0.0433 (10)	0.0489 (11)	0.0362 (9)	0.0138 (8)	0.0034 (7)	0.0115 (8)
C21	0.0425 (9)	0.0366 (9)	0.0344 (8)	0.0052 (7)	0.0035 (7)	0.0111 (7)
C22	0.0336 (8)	0.0351 (9)	0.0393 (9)	0.0013 (7)	0.0024 (7)	0.0129 (7)
C23	0.0493 (10)	0.0511 (11)	0.0405 (10)	0.0146 (8)	0.0052 (8)	0.0136 (8)
C24	0.0613 (13)	0.0671 (15)	0.0492 (12)	0.0206 (11)	0.0031 (9)	−0.0010 (11)
C25	0.0605 (13)	0.0387 (12)	0.0953 (19)	0.0088 (10)	0.0072 (12)	−0.0018 (12)
C26	0.0708 (15)	0.0408 (12)	0.124 (2)	0.0070 (10)	0.0310 (14)	0.0373 (14)
C27	0.0602 (12)	0.0484 (12)	0.0743 (14)	0.0096 (9)	0.0254 (10)	0.0309 (11)
C28	0.0390 (9)	0.0409 (10)	0.0343 (9)	0.0006 (7)	0.0009 (7)	0.0094 (7)
C29	0.0530 (11)	0.0451 (11)	0.0495 (10)	0.0103 (8)	0.0117 (8)	0.0128 (9)
C30	0.0555 (12)	0.0673 (14)	0.0609 (12)	0.0068 (10)	0.0203 (10)	0.0239 (11)
C31	0.0667 (13)	0.0560 (13)	0.0542 (12)	−0.0094 (10)	0.0038 (10)	0.0256 (10)
C32	0.0830 (15)	0.0419 (12)	0.0604 (13)	0.0123 (10)	0.0023 (11)	0.0188 (10)
C33	0.0550 (11)	0.0527 (12)	0.0529 (11)	0.0169 (9)	0.0105 (9)	0.0164 (9)

Geometric parameters (Å, º) top

O1—C7	1.2234 (19)	C14—C15	1.382 (2)
O2—C7	1.346 (2)	C14—H14	0.9300
O2—C8	1.437 (2)	C15—H15	0.9300
N1—C16	1.3902 (19)	C16—C17	1.399 (2)
N1—C6	1.4578 (19)	C16—C21	1.404 (2)
N1—C2	1.4771 (19)	C17—C18	1.379 (2)
F1—C13	1.357 (2)	C17—H17	0.9300
F2—C19	1.3652 (19)	C18—C19	1.367 (3)
F3—C25	1.359 (2)	C18—H18	0.9300
F4—C31	1.362 (2)	C19—C20	1.363 (2)
C2—C3	1.513 (2)	C20—C21	1.385 (2)
C2—C10	1.536 (2)	C20—H20	0.9300
C2—H2	0.9800	C21—H21	0.9300
C3—C4	1.367 (2)	C22—C27	1.382 (2)
C3—C7	1.441 (2)	C22—C23	1.383 (2)
C4—N9	1.346 (2)	C23—C24	1.382 (3)
C4—C5	1.499 (2)	C23—H23	0.9300
C5—C6	1.537 (2)	C24—C25	1.355 (3)
C5—H5A	0.9700	C24—H24	0.9300
C5—H5B	0.9700	C25—C26	1.361 (3)
C6—C22	1.522 (2)	C26—C27	1.387 (3)
C6—H6	0.9800	C26—H26	0.9300
C8—H8A	0.9600	C27—H27	0.9300
C8—H8B	0.9600	C28—C29	1.378 (2)
C8—H8C	0.9600	C28—C33	1.378 (2)
N9—C28	1.430 (2)	C29—C30	1.371 (3)
N9—H9	0.8600	C29—H29	0.9300
C10—C15	1.384 (2)	C30—C31	1.357 (3)
C10—C11	1.387 (2)	C30—H30	0.9300
C11—C12	1.383 (3)	C31—C32	1.365 (3)
C11—H11	0.9300	C32—C33	1.380 (3)
C12—C13	1.355 (3)	C32—H32	0.9300
C12—H12	0.9300	C33—H33	0.9300
C13—C14	1.365 (3)

C7—O2—C8	116.47 (15)	C14—C15—H15	119.2
C16—N1—C6	119.96 (12)	C10—C15—H15	119.2
C16—N1—C2	121.58 (13)	N1—C16—C17	122.49 (14)
C6—N1—C2	118.45 (12)	N1—C16—C21	120.70 (14)
N1—C2—C3	110.16 (12)	C17—C16—C21	116.81 (14)
N1—C2—C10	112.28 (12)	C18—C17—C16	121.44 (16)
C3—C2—C10	113.35 (13)	C18—C17—H17	119.3
N1—C2—H2	106.9	C16—C17—H17	119.3
C3—C2—H2	106.9	C19—C18—C17	119.45 (17)
C10—C2—H2	106.9	C19—C18—H18	120.3
C4—C3—C7	120.82 (14)	C17—C18—H18	120.3
C4—C3—C2	117.19 (13)	C20—C19—F2	119.03 (16)
C7—C3—C2	121.68 (14)	C20—C19—C18	121.73 (16)
N9—C4—C3	124.80 (14)	F2—C19—C18	119.24 (17)
N9—C4—C5	119.74 (14)	C19—C20—C21	118.97 (16)
C3—C4—C5	115.31 (13)	C19—C20—H20	120.5
C4—C5—C6	108.80 (12)	C21—C20—H20	120.5
C4—C5—H5A	109.9	C20—C21—C16	121.61 (16)
C6—C5—H5A	109.9	C20—C21—H21	119.2
C4—C5—H5B	109.9	C16—C21—H21	119.2
C6—C5—H5B	109.9	C27—C22—C23	118.21 (17)
H5A—C5—H5B	108.3	C27—C22—C6	119.57 (15)
N1—C6—C22	113.71 (12)	C23—C22—C6	122.17 (15)
N1—C6—C5	109.48 (12)	C22—C23—C24	121.17 (19)
C22—C6—C5	109.88 (12)	C22—C23—H23	119.4
N1—C6—H6	107.9	C24—C23—H23	119.4
C22—C6—H6	107.9	C25—C24—C23	118.6 (2)
C5—C6—H6	107.9	C25—C24—H24	120.7
O1—C7—O2	121.68 (15)	C23—C24—H24	120.7
O1—C7—C3	125.38 (16)	C24—C25—F3	118.5 (3)
O2—C7—C3	112.93 (14)	C24—C25—C26	122.6 (2)
O2—C8—H8A	109.5	F3—C25—C26	118.9 (2)
O2—C8—H8B	109.5	C25—C26—C27	118.4 (2)
H8A—C8—H8B	109.5	C25—C26—H26	120.8
O2—C8—H8C	109.5	C27—C26—H26	120.8
H8A—C8—H8C	109.5	C22—C27—C26	121.0 (2)
H8B—C8—H8C	109.5	C22—C27—H27	119.5
C4—N9—C28	125.43 (14)	C26—C27—H27	119.5
C4—N9—H9	117.3	C29—C28—C33	119.57 (17)
C28—N9—H9	117.3	C29—C28—N9	120.08 (16)
C15—C10—C11	117.64 (15)	C33—C28—N9	120.34 (16)
C15—C10—C2	121.57 (14)	C30—C29—C28	120.60 (18)
C11—C10—C2	120.71 (14)	C30—C29—H29	119.7
C12—C11—C10	121.19 (16)	C28—C29—H29	119.7
C12—C11—H11	119.4	C31—C30—C29	118.48 (19)
C10—C11—H11	119.4	C31—C30—H30	120.8
C13—C12—C11	118.93 (18)	C29—C30—H30	120.8
C13—C12—H12	120.5	C30—C31—F4	118.8 (2)
C11—C12—H12	120.5	C30—C31—C32	122.91 (19)
F1—C13—C12	119.10 (19)	F4—C31—C32	118.3 (2)
F1—C13—C14	118.73 (19)	C31—C32—C33	118.21 (19)
C12—C13—C14	122.17 (18)	C31—C32—H32	120.9
C13—C14—C15	118.48 (18)	C33—C32—H32	120.9
C13—C14—H14	120.8	C28—C33—C32	120.22 (18)
C15—C14—H14	120.8	C28—C33—H33	119.9
C14—C15—C10	121.58 (17)	C32—C33—H33	119.9

C16—N1—C2—C3	144.95 (14)	C2—C10—C15—C14	176.90 (17)
C6—N1—C2—C3	−35.70 (18)	C6—N1—C16—C17	−173.09 (14)
C16—N1—C2—C10	−87.70 (17)	C2—N1—C16—C17	6.3 (2)
C6—N1—C2—C10	91.65 (16)	C6—N1—C16—C21	5.7 (2)
N1—C2—C3—C4	46.48 (19)	C2—N1—C16—C21	−174.97 (14)
C10—C2—C3—C4	−80.28 (17)	N1—C16—C17—C18	178.43 (16)
N1—C2—C3—C7	−127.14 (15)	C21—C16—C17—C18	−0.4 (2)
C10—C2—C3—C7	106.10 (16)	C16—C17—C18—C19	0.0 (3)
C7—C3—C4—N9	−5.0 (2)	C17—C18—C19—C20	0.4 (3)
C2—C3—C4—N9	−178.70 (14)	C17—C18—C19—F2	−179.16 (16)
C7—C3—C4—C5	170.58 (14)	F2—C19—C20—C21	179.08 (15)
C2—C3—C4—C5	−3.1 (2)	C18—C19—C20—C21	−0.5 (3)
N9—C4—C5—C6	126.42 (15)	C19—C20—C21—C16	0.1 (2)
C3—C4—C5—C6	−49.43 (19)	N1—C16—C21—C20	−178.54 (14)
C16—N1—C6—C22	−71.66 (17)	C17—C16—C21—C20	0.3 (2)
C2—N1—C6—C22	108.98 (15)	N1—C6—C22—C27	151.32 (15)
C16—N1—C6—C5	165.02 (13)	C5—C6—C22—C27	−85.58 (18)
C2—N1—C6—C5	−14.34 (17)	N1—C6—C22—C23	−31.4 (2)
C4—C5—C6—N1	57.41 (16)	C5—C6—C22—C23	91.67 (17)
C4—C5—C6—C22	−68.15 (16)	C27—C22—C23—C24	1.9 (3)
C8—O2—C7—O1	−2.9 (2)	C6—C22—C23—C24	−175.43 (16)
C8—O2—C7—C3	175.84 (16)	C22—C23—C24—C25	−1.5 (3)
C4—C3—C7—O1	7.4 (3)	C23—C24—C25—F3	−179.41 (17)
C2—C3—C7—O1	−179.21 (15)	C23—C24—C25—C26	−0.1 (3)
C4—C3—C7—O2	−171.29 (14)	C24—C25—C26—C27	1.2 (3)
C2—C3—C7—O2	2.1 (2)	F3—C25—C26—C27	−179.50 (19)
C3—C4—N9—C28	175.11 (15)	C23—C22—C27—C26	−0.7 (3)
C5—C4—N9—C28	−0.3 (2)	C6—C22—C27—C26	176.63 (17)
N1—C2—C10—C15	25.0 (2)	C25—C26—C27—C22	−0.7 (3)
C3—C2—C10—C15	150.68 (16)	C4—N9—C28—C29	89.3 (2)
N1—C2—C10—C11	−158.12 (14)	C4—N9—C28—C33	−91.4 (2)
C3—C2—C10—C11	−32.5 (2)	C33—C28—C29—C30	0.4 (3)
C15—C10—C11—C12	−0.9 (3)	N9—C28—C29—C30	179.73 (16)
C2—C10—C11—C12	−177.81 (16)	C28—C29—C30—C31	−0.5 (3)
C10—C11—C12—C13	0.9 (3)	C29—C30—C31—F4	−179.58 (17)
C11—C12—C13—F1	179.37 (18)	C29—C30—C31—C32	−0.1 (3)
C11—C12—C13—C14	0.0 (3)	C30—C31—C32—C33	0.8 (3)
F1—C13—C14—C15	179.77 (19)	F4—C31—C32—C33	−179.70 (17)
C12—C13—C14—C15	−0.9 (3)	C29—C28—C33—C32	0.3 (3)
C13—C14—C15—C10	0.9 (3)	N9—C28—C33—C32	−179.00 (16)
C11—C10—C15—C14	0.0 (3)	C31—C32—C33—C28	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1	0.86	2.05	2.695 (2)	131
C20—H20···F2ⁱ	0.93	2.54	3.384 (2)	152
C32—H32···O1ⁱⁱ	0.93	2.47	3.311 (3)	151

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₃₁H₂₄F₄N₂O₂
M_r	532.52
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.7990 (2), 10.7316 (4), 13.7395 (4)
α, β, γ (°)	110.797 (3), 100.338 (2), 96.323 (2)
V (Å³)	1304.81 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.899, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	42990, 5413, 3730
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.05
No. of reflections	5413
No. of parameters	353
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.20

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1	0.86	2.05	2.695 (2)	131
C20—H20···F2ⁱ	0.93	2.54	3.384 (2)	152
C32—H32···O1ⁱⁱ	0.93	2.47	3.311 (3)	151

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y, −z.

Acknowledgements

RK acknowledges the Department of Science & Technology for a single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. GB is thankful to the CSIR, New Delhi, for financial support [grant No. 02 (110)/12/EMR-II]. VKG thanks the University of Jammu for financial support.

References

Agrawal, A. G. & Somani, R. R. (2009). Mini Rev. Med. Chem. 9, 638–652. CrossRef PubMed CAS Google Scholar
Anthal, S., Brahmachari, G., Das, S., Kant, R. & Gupta, V. K. (2013). Acta Cryst. E69, o299–o300. CSD CrossRef IUCr Journals Google Scholar
Bin, H., Crider, A. M. & Stables, J. P. (2001). Eur. J. Med. Chem. 36, 265–286. Web of Science PubMed Google Scholar
Brahmachari, G. & Das, S. (2012). Tetrahedron Lett. 53, 1479–1484. Web of Science CSD CrossRef CAS Google Scholar
Duax, W. L. & Norton, D. A. (1975). In Atlas of Steroid Structures, Vol. 1. New York: Plenum Press. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Jaen, J. C., Wise, L. D., Heffner, T. G., Pugsley, T. A. & Meltzer, L. T. (1988). J. Med. Chem. 31, 1621–1625. CrossRef CAS PubMed Google Scholar
Kamei, K., Maeda, N., Katswagi-Ogino, R., Koyamaa, M., Nakajima, M., Tatsuoka, T., Ohno, T. & Inoue, T. (2005). Bioorg. Med. Chem. Lett. 15, 2990–2993. Web of Science CrossRef PubMed CAS Google Scholar
Khan, T. K., Khan, Md. M. & Bannuru, K. K. R. (2010). Tetrahedron, 66, 7762–7772. Web of Science CSD CrossRef CAS Google Scholar
Misra, M., Pandey, S. K., Pandey, V. P., Pandey, J., Tripathi, R. & Tripathi, R. P. (2009). Bioorg. Med. Chem. 17, 625–633. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sambyal, A., Bamezai, R. K., Razdan, T. K. & Gupta, V. K. (2011). J. Chem. Crystallogr. 41, 868–873. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, Y., Gregor, V. E., Ayida, B. K., Winters, G. C., Sun, Z., Murphy, D., Haley, G., Bailey, D., Froelich, J. M., Fish, S., Webber, S. E., Hermann, T. & Wall, D. (2007). Bioorg. Med. Chem. Lett. 17, 1206–1210. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 69| Part 3| March 2013| Pages o373-o374

doi:10.1107/S160053681300370X

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

Methyl 4-(4-fluoro­anilino)-1,2,6-tris­­(4-fluoro­phen­yl)-1,2,5,6-tetra­hydro­pyri­dine-3-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Methyl 4-(4-fluoroanilino)-1,2,6-tris(4-fluorophenyl)-1,2,5,6-tetrahydropyridine-3-carboxylate