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Crystal structure of 1-[(2S*,4R*)-6-fluoro-2-methyl-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one

aDepartment of Chemistry, Kuvempu University, Jnanasahyadri, Shankaraghatta 577 451, India, bInstitution of Excellence, University of Mysore, Manasagangotri, Mysore 570 006, India, cDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysore 570 005, India, and dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India
*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 2 August 2014; accepted 26 August 2014; online 30 August 2014)

In the title compound, C14H17FN2O, the 1,2,3,4-tetra­hydro­pyridine ring of the quinoline moiety adopts a half-chair conformation, while the pyrrolidine ring has an envelope conformation with the central methyl­ene C atom as the flap. The pyrrolidine ring lies in the equatorial plane and its mean plane is normal to the mean plane of the quinoline ring system, with a dihedral angle value of 88.37 (9)°. The bridging N—C bond distance [1.349 (3) Å] is substanti­ally shorter than the sum of the covalent radii (dcov: C—N = 1.47 Å and C=N = 1.27 Å), which indicates partial double-bond character for this bond, resulting in a certain degree of charge delocalization. In the crystal, mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (10-1). These two-dimensional networks are linked via C—H⋯F hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional structure.

1. Chemical context

Tetra­hydro­quinolines have been significant synthetic targets due to their ubiquitous distribution in natural products and as medicinal agents (Trost et al., 1991[Trost, B. M. (1991). Science, 254, 1471-1477.]). They are potential anti­cancer agents and 2-aryl-4-(2-oxopyrrolidin-1-yl)-1,2,3,4-tetra­hydro­quinolines have been reported to be inhibitors of HIV transcription. Furthermore, 2-methyl tetra­hydro­quino­lines have also been found to exhibit high modulating activity in multidrug resistance (MDR) (Hiessbock et al., 1999[Hiessbock, R., Wolf, C., Richter, E., Hitzler, M., Chiba, P., Kratzel, M. & Ecker, G. (1999). J. Med. Chem. 42, 1921-1926.]). In view of their broad spectrum of medicinal properties and in continuation of our work on new quinoline-based therapeutic agents (Pradeep et al., 2014[Pradeep, P. S., Naveen, S., Kumara, M. N., Mahadevan, K. M. & Lokanath, N. K. (2014). Acta Cryst. E70, o981-o982.]), we have synthesized the title compound and report herein on its spectroscopic and crystallographic characterization.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title mol­ecule is shown in Fig. 1[link]. The relative configuration of the asymmetric centers is S for atom C2 and R for atom C4.

[Figure 1]
Figure 1
A view of the mol­ecular structure of the title mol­ecule, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The pyrrolidine ring adopts an envelope conformation with the flap atom C15 deviating by 0.197 (2) Å from the mean plane defined by the atoms N12/C13/C14/C16. The pyrrolidine ring lies in the equatorial plane and its mean plane is perpendicular to the mean plane of the quinoline ring system, as indicated by the dihedral angle of 88.37 (9)°. The N12—C13 distance [1.349 (3) Å] is substanti­ally shorter than the sum of the covalent radii [dcov: C—N = 1.47 Å and C=N = 1.27 Å; Holleman et al., 2007[Holleman, A. F. (2007). Lehrbuch der Anorganischen Chemie, p. 138. Berlin/New York: De Gruyter.]], which indicates partial double-bond character for this bond, resulting in a certain degree of charge delocalization. The C13=O1 bond length of 1.235 (3) Å confirms the presence of a keto group in the pyrrolidine moiety.

The tetra­hydro­pyridine ring of the quinoline system adopts a half-chair conformation with atom C10 deviating by 0.285 (2) Å from the mean plane defined by atoms N1/C2–C4/C9. This is confirmed by the puckering amplitude Q = 0.496 (2) Å. Although the quinoline ring system adopts a distorted half-chair conformation, the torsion angles C9—N1—C2—C3 and C2—C3—C4—C10 are −40.8 (2) and −53.0 (2)°, respectively. These differ from the corresponding angles [−47.8 (2) and −45.0 (2)°, respectively] in 6-eth­oxy-1,2,3,4-tetra­hydro-2,2,4-tri­methyl­quinoline (Rybakov et al., 2004[Rybakov, V. B., Alekseev, N. V., Sheludyakov, V. D., Ivanov, Y. A., Frolov, A. Y. & Aslanov, L. A. (2004). Acta Cryst. E60, o1145-o1146.]). This can be attributed to the steric hindrance caused by the change in the substituents on the quinoline ring system.

The conformation of the tetra­hydro­pyridine ring and that of the pyrrolidine ring are similar to those observed in, for example, 1-[2-(2-fur­yl)-6-methyl-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one (Vizcaya et al., 2012[Vizcaya, L. A., Mora, A. J., Delgado, G. E., Bahsas, A., Mora, U. & Kouznetsov, V. V. (2012). J. Chem. Crystallogr. 42, 267-270.]).

3. Supra­molecular features

In the crystal, mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (10[\overline{1}]); see Fig. 2[link] and Table 1[link]. These two-dimensional networks are linked via C—H⋯F hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional structure (Table 1[link] and Fig. 3[link]).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯O1i 0.84 (3) 2.46 (3) 3.273 (2) 162 (2)
C7—H7⋯O1ii 0.93 2.51 3.351 (3) 150
C15—H15B⋯F1iii 0.97 2.48 3.189 (3) 130
C11—H11CCg1iv 0.97 2.80 3.748 (3) 168
Symmetry codes: (i) [-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (iii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) -x+2, -y+1, -z.
[Figure 2]
Figure 2
A viewed along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1[link] for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
[Figure 3]
Figure 3
A viewed along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1[link] for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Allen et al., 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) for the substructure (1,2,3,4-tetra­hydro­quinolin-4-yl)pyrrolidin-2-one yielded seven hits. Two of these crystallized in a chiral space group; P212121 for the 2-(4-meth­oxy­phen­yl) derivative (refcode: HABXIT; Shen & Ji, 2008[Shen, S.-S. & Ji, S.-J. (2008). Chin. J. Chem. 26, 935-940.]), and P61 for the trans diastereomer of the 2-(4-nitro­phen­yl)-5-(5-phenyl-1,2-oxazol-3-yl) derivative (refcode: IKAZEA; Gutierrez et al., 2011a[Gutierrez, M., Vallejos, G., Fernández, C., Cárdenas, A. & Brito, I. (2011a). Acta Cryst. E67, o175-o176.]). The crystal structure of the racemic form of the latter has also been reported (refcode: QALCOX; Gutierrez et al., 2011b[Gutierrez, M., Astudillo, L., Quesada, L., Brito, I. & López-Rodríguez, M. (2011b). Acta Cryst. E67, o308-o309.]).

In all seven compounds, the tetra­hydro­pyridine ring has a half-chair conformation, while in three mol­ecules the pyrrolidine ring has an envelope conformation and in another three mol­ecules a twist conformation. The orientation of the pyrrolidine ring with respect to the quinoline ring is very similar if one excludes the two compounds that have a substituent in the 5-position of the quinoline ring (Gutierrez et al., 2011a[Gutierrez, M., Vallejos, G., Fernández, C., Cárdenas, A. & Brito, I. (2011a). Acta Cryst. E67, o175-o176.],b[Gutierrez, M., Astudillo, L., Quesada, L., Brito, I. & López-Rodríguez, M. (2011b). Acta Cryst. E67, o308-o309.]). The two mean planes are inclined to one another by dihedral angles varying from ca 79.98 to 89.59°, compared to 88.37 (9)° in the title compound.

5. Synthesis and crystallization

A catalytic amount of SbF3 (10 mol%) was added to a mixture of 4-flouroaniline (1 equivalent) and N-vinyl­pyrrolidone (2–3 equivalents) in aceto­nitrile (5–10 ml). The reaction mixture was stirred at ambient temperature (292 K) for 20–70 min. After completion of the reaction, as indicated by TLC using ethyl acetate/hexane as eluent, the solvent was removed under vacuo. The crude product was then quenched with water and the catalyst was decomposed by addition of the appropriate amount of sodium bicarbonate solution. It was then extracted with ethyl acetate (10 ml × 5 times), dried and purified by column chromatography using ethyl acetate/hexane as eluent (petroleum ether/ethyl acetate 80:20 v/v). White crystals were obtained by slow evaporation of the solvent.

In the 1H NMR spectrum of the title compound, the three quadrates at δ 1.60, 2.95 and 3.22 p.p.m. correspond to three protons at C3—H, C5′—H and C4′—H, respectively. A doublet at δ 5.24 p.p.m. corresponds to C4—H, a singlet at δ 5.62 p.p.m. corresponds to the –NH proton and the number of protons is in accordance with the obtained structure. Additional support to elucidate the structure was obtained from 13C NMR (see the archived CIF for more details). The mass spectrum was recorded as additional evidence for the proposed structure: M+1 peak at m/z = 250.1.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The NH H atom was located from a difference Fourier map and freely refined. The C-bound H atoms were fixed geometrically (C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula C14H17FN2O
Mr 248.30
Crystal system, space group Monoclinic, P21/n
Temperature (K) 100
a, b, c (Å) 11.3414 (3), 9.1909 (3), 12.6799 (4)
β (°) 111.569 (2)
V3) 1229.17 (7)
Z 4
Radiation type Cu Kα
μ (mm−1) 0.79
Crystal size (mm) 0.23 × 0.22 × 0.21
 
Data collection
Diffractometer Bruker X8 Proteum
Absorption correction Multi-scan (SADABS; Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.])
Tmin, Tmax 0.834, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections 8574, 2009, 1488
Rint 0.071
(sin θ/λ)max−1) 0.585
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.122, 1.00
No. of reflections 2009
No. of parameters 168
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.20, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2013[Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]), 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.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.])'.

Supporting information


Chemical context top

Tetra­hydro­quinolines have been significant synthetic targets due to their ubiquitous distribution in natural products and as medicinal agents (Trost et al., 1991). They are potential anti­cancer agents and 2-aryl-4-(2-oxopyrrolidin-1-yl)-1,2,3,4-tetra­hydro­quinolines have been reported to be inhibitors of HIV transcription. Furthermore, 2-methyl tetra­hydro­quinolines have also been found to exhibit high modulating activity in multidrug resistance (MDR) (Hiessbock et al., 1999). In view of their broad spectrum of medicinal properties and in continuation of our work on new quinoline-based therapeutic agents (Pradeep et al., 2014), we have synthesized the title compound and report herein on its spectroscopic and crystallographic characterization.

Structural commentary top

The molecular structure of the title molecule is shown in Fig. 1. The title compound is chiral, crystallizing in the orthorhombic space group P212121. Atom C4 has an R configuration while atom C2 has an S configuration.

The pyrrolidine ring adopts an envelope conformation with the flap atom C15 deviating by 0.197 (2) Å from the mean plane defined by the atoms N12/C13/C14/C16. The pyrrolidine ring lies in the equatorial plane and its mean plane is perpendicular to the mean plane of the quinoline ring system, as indicated by the dihedral angle of 88.37 (9)°. The N12—C13 distance [1.349 (3) Å] is substanti­ally shorter than the sum of the covalent radii [dcov: C—N = 1.47 Å and CN = 1.27 Å; Holleman et al., 2007], which indicates partial double-bond character for this bond, resulting in a certain degree of charge delocalization. The C13O1 bond length of 1.235 (3) Å confirms the presence of a keto group in the pyrrolidine moiety.

The tetra­hydro­pyridine ring of the quinoline system adopts a half-chair conformation with atom C10 deviating by 0.285 (2) Å from the mean plane defined by atoms N1/C2–C4/C10/C9. This is confirmed by the puckering amplitude Q = 0.496 (2) Å. Although the quinoline ring system adopts a distorted half-chair conformation, the torsion angles C9—N1—C2—C3 and C2—C3—C4—C10 are -40.8 (2) and -53.0 (2)°, respectively. These differ from the corresponding values [-47.8 (2) and -45.0 (2)°, respectively] reported for 6-eth­oxy-1,2,3,4-tetra­hydro-2,2,4-tri­methyl­quinoline by Rybakov et al. (2004). This can be attributed to the steric hindrance caused by the change in the substituents on the quinoline ring system.

The conformation of the tetra­hydra­pyridine ring and that of the pyrrolidine ring are similar to those observed in, for example, 1-[2-(2-furyl)-6-methyl-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one (Vizcaya et al., 2012).

Supra­molecular features top

In the crystal, molecules are linked by N—H···O and C—H···O hydrogen bonds, forming sheets lying parallel to (101); see Fig. 2 and Table 1. These two-dimensional networks are linked via C—H···F hydrogen bonds and C—H···π inter­actions, forming a three-dimensional structure (Table 1 and Fig. 3).

Database survey top

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Allen et al., 2002) for the substructure (1,2,3,4-tetra­hydro­quinolin-4-yl)pyrrolidin-2-one yielded seven hits. Two of these also crystallized in a chiral space group; P212121 for the 2-(4-meth­oxy­phenyl) derivative (refcode: HABXIT; Shen & Ji, 2008), and P61 for the trans diastereomer of the 2-(4-nitro­phenyl)-5-(5-phenyl-1,2-oxazol-3-yl) derivative (refcode: IKAZEA; Gutierrez et al., 2011a). The crystal structure of the racemic form of the latter has also been reported (refcode: QALCOX; Gutierrez et al., 2011b).

In all seven compounds, the tetra­hydro­pyridine ring has a half-chair conformation, while in three molecules the pyrrolidine ring has an envelope conformation and in another three molecules a twist conformation. The orientation of the pyrrolidine ring with respect to the quinoline ring is very similar if one excludes the two compounds that have a substituent in the 5-position of the quinoline ring (Gutierrez et al., 2011a,b). The two mean planes are inclined to one another by dihedral angles varying from ca 79.98 to 89.59°, compared to 88.37 (9) ° in the title compound.

Synthesis and crystallization top

A catalytic amount of SbF3 (10 mol%) was added to a mixture of 4-flouroaniline (1 equivalent) and N-vinyl­pyrrolidone (2–3 equivalents) in aceto­nitrile (5–10 ml). The reaction mixture was stirred at ambient temperature (~292 K) for 20–70 min. After completion of the reaction, as indicated by TLC using ethyl acetate/hexane as eluent, the solvent was removed under vacuo. The crude product was then quenched with water and the catalyst was decomposed by addition of the appropriate amount of sodium bicarbonate solution. It was then extracted with ethyl acetate (10 ml × 5 times), dried and purified by column chromatography using ethyl acetate/hexane as eluent (petroleum ether/ethyl acetate 80:20 v/v). White crystals were obtained by slow evaporation of the solvent.

In the 1H NMR spectrum of the title compound, the three quadrates at δ 1.60, 2.95 and 3.22 p.p.m. correspond to three protons at C3—H, C5'—H and C4'—H, respectively. A doublet at δ 5.24 p.p.m. corresponds to C4—H, a singlet at δ 5.62 p.p.m. corresponds to the –NH proton and the number of protons is in accordance with the obtained structure. Additional support to elucidate the structure was obtained from 13C NMR (see the archived CIF for more details). The mass spectrum was recorded as additional evidence for the proposed structure: M+1 peak at m/z = 250.1.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom was located from a difference Fourier map and freely refined. The C-bound H atoms were fixed geometrically (C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.

Related literature top

For related literature, see: Allen (2002); Gutierrez et al. (2011a, 2011b); Pradeep et al. (2014); Rybakov et al. (2004); Shen & Ji (2008); Trost (1991); Vizcaya et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); 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: PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010)'.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A viewed along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
[Figure 3] Fig. 3. A viewed along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
1-[(2S,4R)-6-Fluoro-2-methyl-1,2,3,4-tetrahydroquinolin-4-yl]pyrrolidin-2-one top
Crystal data top
C14H17FN2OF(000) = 528
Mr = 248.30Dx = 1.342 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 2009 reflections
a = 11.3414 (3) Åθ = 4.5–64.4°
b = 9.1909 (3) ŵ = 0.79 mm1
c = 12.6799 (4) ÅT = 100 K
β = 111.569 (2)°Block, white
V = 1229.17 (7) Å30.23 × 0.22 × 0.21 mm
Z = 4
Data collection top
Bruker X8 Proteum
diffractometer
2009 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode1488 reflections with I > 2σ(I)
Helios multilayer optics monochromatorRint = 0.071
Detector resolution: 18.4 pixels mm-1θmax = 64.4°, θmin = 4.5°
ϕ and ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
k = 1010
Tmin = 0.834, Tmax = 0.848l = 1414
8574 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0682P)2]
where P = (Fo2 + 2Fc2)/3
2009 reflections(Δ/σ)max = 0.049
168 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C14H17FN2OV = 1229.17 (7) Å3
Mr = 248.30Z = 4
Monoclinic, P21/nCu Kα radiation
a = 11.3414 (3) ŵ = 0.79 mm1
b = 9.1909 (3) ÅT = 100 K
c = 12.6799 (4) Å0.23 × 0.22 × 0.21 mm
β = 111.569 (2)°
Data collection top
Bruker X8 Proteum
diffractometer
2009 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1488 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.848Rint = 0.071
8574 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.20 e Å3
2009 reflectionsΔρmin = 0.22 e Å3
168 parameters
Special details top

Experimental. 1H NMR was recorded at 400 MHz in Dimethylsulfoxide (DMSO-d6). 13C NMR was recorded at 400 MHz in DMSO-d6. Mass spectra was recorded on a Jeol SX 102=DA-6000 (10 kV) fast atom bombardment (FAB) mass spectrometer. 1H NMR(400 MHz, DMSO-d6): δ = 1.12 (s, 3H), 1.60 (q, J = 12.00 Hz, 1H), 1.72–1.74 (m, 1H), 1.89–1.91 (m, 2H), 2.26–2.28 (m, 2H), 2.95 (q, J = 6.80 Hz, 1H), 3.22 (q, J = 7.20 Hz, 1H), 3.41–3.43 (m, 1H), 5.24 (d, J = 5.60 Hz, 1H), 5.62 (s, 1H), 6.40–6.41 (m, 1H), 6.49–6.50 (m, 1H), 6.74–6.75 (m, 1H) p.p.m..

13C NMR (400 MHz, DMSO-d6): δ = 17.6, 21.6, 30.6, 33.2, 41.6, 46.1, 47.2, 11.7, 114.4, 119.2, 142.9, 153.1, 155.4, 174.6 p.p.m..

MS (70 eV) m/z (%): 250.1 (M+, 99.63)

HPLC Purity = 97.9%.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
xyzUiso*/Ueq
F10.84526 (11)0.14151 (14)0.28243 (11)0.0311 (4)
O11.19100 (13)0.59593 (18)0.49292 (13)0.0316 (5)
N11.15416 (15)0.3610 (2)0.07073 (15)0.0220 (6)
N121.06638 (14)0.62374 (18)0.30482 (14)0.0181 (5)
C21.23865 (17)0.4842 (2)0.11812 (18)0.0208 (6)
C31.16936 (17)0.5931 (2)0.16463 (18)0.0217 (6)
C41.13482 (16)0.5243 (2)0.25882 (17)0.0191 (6)
C50.98300 (17)0.3254 (2)0.26777 (18)0.0201 (7)
C60.92150 (17)0.1966 (2)0.22961 (19)0.0226 (7)
C70.93354 (18)0.1203 (2)0.14035 (19)0.0236 (7)
C81.01288 (18)0.1756 (2)0.09018 (19)0.0224 (7)
C91.07908 (16)0.3066 (2)0.12729 (17)0.0188 (6)
C101.06312 (16)0.3830 (2)0.21747 (17)0.0177 (6)
C111.27895 (19)0.5500 (3)0.02753 (19)0.0280 (7)
C131.09465 (18)0.6419 (2)0.41705 (18)0.0217 (7)
C140.98829 (18)0.7274 (2)0.4329 (2)0.0252 (7)
C150.92345 (18)0.7996 (2)0.31843 (19)0.0246 (7)
C160.94501 (18)0.6917 (2)0.23558 (19)0.0242 (7)
H1N1.182 (2)0.296 (3)0.039 (2)0.033 (7)*
H21.314100.449400.180400.0250*
H3A1.092900.625500.104100.0260*
H3B1.222900.677300.194000.0260*
H41.214400.499600.320600.0230*
H50.971300.374400.327300.0240*
H70.889300.034100.114800.0280*
H81.022900.125200.030400.0270*
H11A1.317700.476400.002700.0420*
H11B1.338700.626800.059900.0420*
H11C1.206000.588500.032100.0420*
H14A1.021200.799300.492500.0300*
H14B0.930400.663500.451100.0300*
H15A0.961600.893100.315300.0300*
H15B0.833700.813200.302300.0300*
H16A0.877400.620300.210000.0290*
H16B0.951200.741200.170300.0290*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0307 (6)0.0272 (8)0.0426 (9)0.0022 (5)0.0220 (6)0.0062 (6)
O10.0320 (8)0.0396 (11)0.0193 (9)0.0119 (7)0.0048 (7)0.0021 (7)
N10.0231 (8)0.0223 (11)0.0230 (11)0.0002 (8)0.0113 (8)0.0032 (9)
N120.0185 (8)0.0178 (10)0.0172 (10)0.0019 (7)0.0055 (7)0.0011 (8)
C20.0169 (9)0.0252 (12)0.0189 (12)0.0030 (8)0.0048 (8)0.0023 (9)
C30.0197 (9)0.0230 (12)0.0216 (12)0.0038 (8)0.0066 (9)0.0035 (9)
C40.0159 (9)0.0208 (12)0.0187 (12)0.0019 (8)0.0042 (8)0.0025 (9)
C50.0223 (10)0.0180 (12)0.0210 (12)0.0035 (8)0.0090 (9)0.0017 (9)
C60.0206 (9)0.0211 (12)0.0279 (13)0.0013 (9)0.0112 (9)0.0085 (10)
C70.0225 (10)0.0161 (12)0.0281 (13)0.0008 (8)0.0046 (9)0.0019 (10)
C80.0254 (10)0.0178 (12)0.0226 (12)0.0018 (9)0.0073 (9)0.0021 (9)
C90.0159 (9)0.0185 (12)0.0194 (12)0.0051 (8)0.0035 (8)0.0040 (9)
C100.0157 (9)0.0163 (12)0.0190 (11)0.0034 (8)0.0040 (8)0.0020 (9)
C110.0244 (10)0.0359 (14)0.0254 (13)0.0044 (10)0.0112 (9)0.0019 (11)
C130.0256 (10)0.0194 (12)0.0213 (12)0.0030 (9)0.0099 (9)0.0008 (10)
C140.0281 (10)0.0227 (13)0.0290 (13)0.0002 (9)0.0156 (9)0.0012 (10)
C150.0221 (10)0.0215 (12)0.0298 (13)0.0024 (9)0.0090 (9)0.0007 (10)
C160.0194 (9)0.0266 (13)0.0232 (12)0.0066 (9)0.0038 (9)0.0000 (10)
Geometric parameters (Å, º) top
F1—C61.371 (2)C14—C151.518 (3)
O1—C131.235 (3)C15—C161.528 (3)
N1—C21.462 (3)C2—H20.9800
N1—C91.392 (3)C3—H3A0.9700
N12—C41.453 (3)C3—H3B0.9700
N12—C131.349 (3)C4—H40.9800
N12—C161.472 (3)C5—H50.9300
N1—H1N0.84 (3)C7—H70.9300
C2—C111.510 (3)C8—H80.9300
C2—C31.519 (3)C11—H11A0.9600
C3—C41.524 (3)C11—H11B0.9600
C4—C101.520 (3)C11—H11C0.9600
C5—C61.369 (3)C14—H14A0.9700
C5—C101.392 (3)C14—H14B0.9700
C6—C71.380 (3)C15—H15A0.9700
C7—C81.376 (3)C15—H15B0.9700
C8—C91.405 (3)C16—H16A0.9700
C9—C101.409 (3)C16—H16B0.9700
C13—C141.514 (3)
C2—N1—C9119.93 (17)C2—C3—H3B110.00
C4—N12—C13123.12 (17)C4—C3—H3A110.00
C4—N12—C16123.22 (16)C4—C3—H3B110.00
C13—N12—C16112.59 (17)H3A—C3—H3B108.00
C2—N1—H1N116.2 (17)N12—C4—H4107.00
C9—N1—H1N113.5 (18)C3—C4—H4107.00
C3—C2—C11112.08 (17)C10—C4—H4107.00
N1—C2—C3108.38 (17)C6—C5—H5120.00
N1—C2—C11109.48 (18)C10—C5—H5120.00
C2—C3—C4110.45 (15)C6—C7—H7121.00
N12—C4—C10112.27 (16)C8—C7—H7121.00
C3—C4—C10110.07 (16)C7—C8—H8119.00
N12—C4—C3112.50 (15)C9—C8—H8119.00
C6—C5—C10120.03 (19)C2—C11—H11A109.00
F1—C6—C7118.91 (17)C2—C11—H11B109.00
F1—C6—C5118.54 (18)C2—C11—H11C109.00
C5—C6—C7122.6 (2)H11A—C11—H11B110.00
C6—C7—C8118.04 (18)H11A—C11—H11C109.00
C7—C8—C9121.42 (19)H11B—C11—H11C110.00
N1—C9—C10121.63 (17)C13—C14—H14A111.00
N1—C9—C8119.20 (18)C13—C14—H14B111.00
C8—C9—C10119.11 (18)C15—C14—H14A111.00
C4—C10—C9119.59 (17)C15—C14—H14B111.00
C4—C10—C5121.56 (17)H14A—C14—H14B109.00
C5—C10—C9118.84 (17)C14—C15—H15A111.00
O1—C13—C14126.5 (2)C14—C15—H15B111.00
N12—C13—C14108.20 (18)C16—C15—H15A111.00
O1—C13—N12125.3 (2)C16—C15—H15B111.00
C13—C14—C15103.28 (18)H15A—C15—H15B109.00
C14—C15—C16103.30 (16)N12—C16—H16A111.00
N12—C16—C15102.49 (17)N12—C16—H16B111.00
N1—C2—H2109.00C15—C16—H16A111.00
C3—C2—H2109.00C15—C16—H16B111.00
C11—C2—H2109.00H16A—C16—H16B109.00
C2—C3—H3A110.00
C9—N1—C2—C340.8 (2)C3—C4—C10—C5156.85 (18)
C9—N1—C2—C11163.35 (18)C3—C4—C10—C924.2 (2)
C2—N1—C9—C8170.60 (18)C10—C5—C6—F1178.75 (18)
C2—N1—C9—C1012.4 (3)C10—C5—C6—C71.1 (3)
C13—N12—C4—C3133.86 (19)C6—C5—C10—C4178.91 (19)
C13—N12—C4—C10101.3 (2)C6—C5—C10—C90.1 (3)
C16—N12—C4—C358.9 (2)F1—C6—C7—C8178.47 (19)
C16—N12—C4—C1066.0 (2)C5—C6—C7—C81.4 (3)
C4—N12—C13—O111.8 (3)C6—C7—C8—C90.7 (3)
C4—N12—C13—C14168.15 (17)C7—C8—C9—N1177.40 (19)
C16—N12—C13—O1179.74 (19)C7—C8—C9—C100.3 (3)
C16—N12—C13—C140.4 (2)N1—C9—C10—C43.4 (3)
C4—N12—C16—C15172.51 (17)N1—C9—C10—C5177.61 (19)
C13—N12—C16—C1519.0 (2)C8—C9—C10—C4179.63 (18)
N1—C2—C3—C461.2 (2)C8—C9—C10—C50.6 (3)
C11—C2—C3—C4177.83 (17)O1—C13—C14—C15160.3 (2)
C2—C3—C4—N12179.05 (16)N12—C13—C14—C1519.8 (2)
C2—C3—C4—C1053.0 (2)C13—C14—C15—C1630.3 (2)
N12—C4—C10—C530.7 (3)C14—C15—C16—N1229.9 (2)
N12—C4—C10—C9150.31 (18)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C5–C10 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.84 (3)2.46 (3)3.273 (2)162 (2)
C7—H7···O1ii0.932.513.351 (3)150
C15—H15B···F1iii0.972.483.189 (3)130
C11—H11C···Cg1iv0.972.803.748 (3)168
Symmetry codes: (i) x+5/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iii) x+3/2, y+1/2, z+1/2; (iv) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C5–C10 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.84 (3)2.46 (3)3.273 (2)162 (2)
C7—H7···O1ii0.932.513.351 (3)150
C15—H15B···F1iii0.972.483.189 (3)130
C11—H11C···Cg1iv0.972.803.748 (3)168
Symmetry codes: (i) x+5/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z1/2; (iii) x+3/2, y+1/2, z+1/2; (iv) x+2, y+1, z.

Experimental details

Crystal data
Chemical formulaC14H17FN2O
Mr248.30
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)11.3414 (3), 9.1909 (3), 12.6799 (4)
β (°) 111.569 (2)
V3)1229.17 (7)
Z4
Radiation typeCu Kα
µ (mm1)0.79
Crystal size (mm)0.23 × 0.22 × 0.21
Data collection
DiffractometerBruker X8 Proteum
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2013)
Tmin, Tmax0.834, 0.848
No. of measured, independent and
observed [I > 2σ(I)] reflections
8574, 2009, 1488
Rint0.071
(sin θ/λ)max1)0.585
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.122, 1.00
No. of reflections2009
No. of parameters168
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.22

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010)'.

 

Acknowledgements

The authors are grateful to the IOE, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.  Google Scholar
First citationGutierrez, M., Astudillo, L., Quesada, L., Brito, I. & López-Rodríguez, M. (2011b). Acta Cryst. E67, o308–o309.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationGutierrez, M., Vallejos, G., Fernández, C., Cárdenas, A. & Brito, I. (2011a). Acta Cryst. E67, o175–o176.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationHiessbock, R., Wolf, C., Richter, E., Hitzler, M., Chiba, P., Kratzel, M. & Ecker, G. (1999). J. Med. Chem. 42, 1921–1926.  Web of Science PubMed CAS Google Scholar
First citationHolleman, A. F. (2007). Lehrbuch der Anorganischen Chemie, p. 138. Berlin/New York: De Gruyter.  Google Scholar
First citationMacrae, 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.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationPradeep, P. S., Naveen, S., Kumara, M. N., Mahadevan, K. M. & Lokanath, N. K. (2014). Acta Cryst. E70, o981–o982.  CSD CrossRef IUCr Journals Google Scholar
First citationRybakov, V. B., Alekseev, N. V., Sheludyakov, V. D., Ivanov, Y. A., Frolov, A. Y. & Aslanov, L. A. (2004). Acta Cryst. E60, o1145–o1146.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShen, S.-S. & Ji, S.-J. (2008). Chin. J. Chem. 26, 935–940.  Web of Science CSD CrossRef CAS Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTrost, B. M. (1991). Science, 254, 1471–1477.  CrossRef PubMed CAS Web of Science Google Scholar
First citationVizcaya, L. A., Mora, A. J., Delgado, G. E., Bahsas, A., Mora, U. & Kouznetsov, V. V. (2012). J. Chem. Crystallogr. 42, 267–270.  Web of Science CSD CrossRef CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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