4-(4-Fluoro­phen­yl)-6-methyl­amino-5-nitro-2-phenyl-4H-pyran-3-carbo­nitrile

Vishnupriya, R.; Suresh, J.; Sivakumar, S.; Kumar, R.R.; Lakshman, P.L.N.

doi:10.1107/S1600536813009008

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages o687-o688

https://doi.org/10.1107/S1600536813009008

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4-(4-Fluorophenyl)-6-methylamino-5-nitro-2-phenyl-4H-pyran-3-carbonitrile

R. Vishnupriya,^a J. Suresh,^a S. Sivakumar,^b R. Ranjith Kumar ^b and P. L. Nilantha Lakshman ^c ^*

^aDepartment of Physics, The Madura College, Madurai 625 011, India, ^bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and ^cDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
^*Correspondence e-mail: plakshmannilantha@ymail.com

(Received 28 February 2013; accepted 2 April 2013; online 10 April 2013)

In the title compound, C₁₉H₁₄FN₃O₃, the central pyran ring adopts a boat conformation with the O atom and the quaternary C atom diagonally opposite displaced by 0.068 (1) and 0.075 (1) Å, respectively, above the mean plane defined by the other four ring atoms. The co-planar atoms of the pyran ring and the fluorophenyl ring are nearly perpendicular, as evidenced by the dihedral angle of 87.11 (1)°. The amine group forms an intramolecular N—H⋯O(nitro) hydrogen bond. In the crystal, molecules are linked into parallel chains along [100] by weak N—H⋯N and C—H⋯N(nitro) hydrogen bonds, generating C(8) and C(9) graph-set motifs, respectively.

Related literature

For the biological activity of substituted pyran derivatives, see: Lokaj et al. (1990 ); Marco et al. (1993 ). Some 4H-pyran derivatives are potential bioactive compounds and can be used as calcium antagonists, see: Suárez et al. (2002 ). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995 ). For ring conformation analysis, see: Cremer & Pople (1975 ). The title compound and some related compounds are widely used as organic intermediates in organic chemistry (Liang et al., 2009 ). For related structures, see: Nesterov et al. (2004 ); Nesterov & Viltchinskaia (2001 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₉H₁₄FN₃O₃
M_r = 351.33
Triclinic, $[P \overline 1]$
a = 9.3898 (3) Å
b = 9.9752 (3) Å
c = 11.1324 (3) Å
α = 98.765 (1)°
β = 113.991 (1)°
γ = 109.520 (1)°
V = 846.09 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.19 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.967, T_max = 0.974
16948 measured reflections
3680 independent reflections
2993 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.118
S = 1.06
3680 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	1.99	2.6089 (16)	128
N2—H2⋯N3ⁱ	0.86	2.30	2.9811 (17)	136
C6—H6A⋯N3ⁱ	0.96	2.60	3.222 (2)	123
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813009008/bh2475sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009008/bh2475Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009008/bh2475Isup3.cml

checkCIF report

Comment top

The title compound and some related compounds are widely used as organic intermediates in organic chemistry (Liang et al., 2009). Much interest has recently been paid to the design of polyfunctionalized substituted pyran derivatives, owing to their wide range of biological activities (Lokaj et al., 1990; Marco et al., 1993). Some 4H-pyran derivatives are potential bioactive compounds and can be used as calcium antagonists (Suárez et al., 2002). Thus, there has been a growing interest in the structures of 4H-pyran derivatives. The high biologically active value of these compounds in conjunction with our research interests prompted us to synthesize and report the X-ray study of the title compound.

In the title compound (C₁₉H₁₄FN₃O₃, Fig. 1) the six-membered central pyran ring adopts a boat conformation as evidenced by the puckering parameters q₂ = 0.0826 (12) Å, θ = 88.18 (4)°, φ = 127.06 (4)° (Cremer & Pople, 1975). The dihedral angle between the pseudo-axial aryl substituent and the flat part of the pyran ring is 87.11 (1)°. There is conjugation between the donor (NH) and the acceptor (CN) groups via the C4═C5 double bond, as found in other related compounds (Nesterov et al., 2001, 2004). Thus, the C5—N2 distance is 1.3130 (17) Å, which is shorter than the average conjugated C—N single bond, 1.370 (1) Å, found in the Cambridge Structural Database (Allen, 2002). In contrast, the C4═C5 bond is elongated in comparison with the C1═C2 bond and the standard value (Allen et al., 1987). The C4—N1 distance, 1.3855 (17) Å, is considerably shorter than usual C—NO₂ distance (1.468 Å, Allen et al., 1987) and the N1—O2 distance, 1.2558 (16) Å, is longer than the standard value (Allen et al., 1987). The dihedral angle between the flat part of the pyran ring and the phneyl ring at C1 is 49.22 (2)°. The phenyl and the fluorophenyl rings are substituting the pyran ring in a (–)-syn-clinal conformation, with torsion angles C2—C1—C11—C12 and C4—C3—C31—C32 of -51.4 (2)° and -60.76 (17)° respectively. The nitro group is bonded to the pyran ring at C4 with the torsion angle C5—C4—N1—O2 of -7.09 (3)°, indicating a (–)-syn-periplanar conformation for this group.

In the crystal structure, the molecules are linked together, to form an infinite one dimensional chain along [100], through intermolecular N2—H2···N3 and C6—H6A···N3 hydrogen bonds, generating graph set motifs C(8) and C(9) respectively (Fig. 2; Bernstein et al., 1995). In addition, there is a N—H···O intramolecular interaction which stabilizes the molecular conformation.

Related literature top

For the biological activity of substituted pyran derivatives, see: Lokaj et al. (1990); Marco et al. (1993). Some 4H-pyran derivatives are potential bioactive compounds and can be used as calcium antagonists, see: Suárez et al. (2002). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995). For ring conformation analysis, see: Cremer & Pople (1975). The title compound and some related compounds are widely used as organic intermediates in organic chemistry (Liang et al., 2009). For related structures, see: Nesterov et al. (2004); Nesterov & Viltchinskaia (2001). For a description of the Cambridge Structural Database, see: Allen (2002). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A mixture of benzoylacetonitrile (1.0 mmol), 4-fluoroaldehyde (1.0 mmol), Et₃N (1.0 mmol) and 10 ml EtOH were taken in 50 ml round bottom flask. The reaction mixture was stirred at room temperature for 5–10 min. Then N-methyl-1-(methylthio)-2-nitroethenamine was added into the reaction mixture and the system refluxed at 80°C. The consumption of starting material was monitored by TLC. After 90 min., the solid product was filtered and washed with diethyl ether (5 ml) and dried under vacuum condition to afford the pure product. Melting point: 210°C; Yield: 94%

Structure description top

For the biological activity of substituted pyran derivatives, see: Lokaj et al. (1990); Marco et al. (1993). Some 4H-pyran derivatives are potential bioactive compounds and can be used as calcium antagonists, see: Suárez et al. (2002). For hydrogen-bonding graph-set motifs, see: Bernstein et al. (1995). For ring conformation analysis, see: Cremer & Pople (1975). The title compound and some related compounds are widely used as organic intermediates in organic chemistry (Liang et al., 2009). For related structures, see: Nesterov et al. (2004); Nesterov & Viltchinskaia (2001). For a description of the Cambridge Structural Database, see: Allen (2002). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, showing 40% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Packing diagram showing the chain motifs C(8) and C(9) along the [100] direction.

4-(4-Fluorophenyl)-6-methylamino-5-nitro-2-phenyl-4H-pyran-3-carbonitrile top

Crystal data top

C₁₉H₁₄FN₃O₃	Z = 2
M_r = 351.33	F(000) = 364
Triclinic, P1	D_x = 1.379 Mg m⁻³
Hall symbol: -P 1	Melting point: 483 K
a = 9.3898 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9752 (3) Å	Cell parameters from 2000 reflections
c = 11.1324 (3) Å	θ = 2–27°
α = 98.765 (1)°	µ = 0.10 mm⁻¹
β = 113.991 (1)°	T = 293 K
γ = 109.520 (1)°	Block, colourless
V = 846.09 (4) Å³	0.23 × 0.20 × 0.19 mm

Data collection top

Bruker Kappa APEXII diffractometer	3680 independent reflections
Radiation source: fine-focus sealed tube	2993 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 0 pixels mm^-1	θ_max = 27.0°, θ_min = 2.1°
ω and φ scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→12
T_min = 0.967, T_max = 0.974	l = −14→14
16948 measured reflections

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.054P)² + 0.2234P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3680 reflections	Δρ_max = 0.24 e Å⁻³
236 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.047 (4)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₉H₁₄FN₃O₃	γ = 109.520 (1)°
M_r = 351.33	V = 846.09 (4) Å³
Triclinic, P1	Z = 2
a = 9.3898 (3) Å	Mo Kα radiation
b = 9.9752 (3) Å	µ = 0.10 mm⁻¹
c = 11.1324 (3) Å	T = 293 K
α = 98.765 (1)°	0.23 × 0.20 × 0.19 mm
β = 113.991 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	3680 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2993 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.974	R_int = 0.026
16948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
3680 reflections	Δρ_min = −0.22 e Å⁻³
236 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.90505 (16)	0.73779 (15)	0.01317 (13)	0.0338 (3)
C2	0.99879 (16)	0.69360 (14)	0.11020 (13)	0.0332 (3)
C3	0.96024 (16)	0.65343 (14)	0.22245 (13)	0.0331 (3)
H3	0.9429	0.5490	0.2121	0.040*
C4	0.79214 (17)	0.65768 (15)	0.19639 (13)	0.0350 (3)
C5	0.70197 (17)	0.70668 (15)	0.09468 (13)	0.0345 (3)
C6	0.4686 (2)	0.7677 (2)	−0.04503 (17)	0.0510 (4)
H6A	0.3650	0.7650	−0.0459	0.076*
H6B	0.4388	0.7028	−0.1331	0.076*
H6C	0.5440	0.8691	−0.0293	0.076*
C11	0.92473 (17)	0.76501 (15)	−0.10669 (14)	0.0359 (3)
C12	1.0837 (2)	0.85749 (18)	−0.08937 (16)	0.0461 (4)
H12	1.1788	0.9101	−0.0002	0.055*
C13	1.1012 (2)	0.8717 (2)	−0.20466 (17)	0.0538 (4)
H13	1.2085	0.9336	−0.1929	0.065*
C14	0.9618 (2)	0.79536 (19)	−0.33610 (17)	0.0535 (4)
H14	0.9749	0.8041	−0.4134	0.064*
C15	0.8026 (2)	0.7059 (2)	−0.35402 (16)	0.0561 (4)
H15	0.7076	0.6555	−0.4434	0.067*
C16	0.7828 (2)	0.69049 (19)	−0.23976 (15)	0.0479 (4)
H16	0.6746	0.6303	−0.2521	0.057*
C21	1.13736 (18)	0.66852 (16)	0.10462 (14)	0.0384 (3)
C31	1.11327 (17)	0.75233 (15)	0.36706 (13)	0.0352 (3)
C32	1.1702 (2)	0.90599 (18)	0.41307 (17)	0.0535 (4)
H32	1.1129	0.9507	0.3556	0.064*
C33	1.3112 (3)	0.9951 (2)	0.54360 (19)	0.0682 (5)
H33	1.3490	1.0989	0.5750	0.082*
C34	1.3930 (2)	0.9269 (2)	0.62448 (17)	0.0636 (5)
C35	1.3422 (2)	0.7764 (2)	0.58302 (18)	0.0657 (5)
H35	1.4015	0.7332	0.6409	0.079*
C36	1.2002 (2)	0.68821 (19)	0.45290 (16)	0.0515 (4)
H36	1.1630	0.5843	0.4230	0.062*
N1	0.72180 (15)	0.59726 (14)	0.27462 (12)	0.0421 (3)
N2	0.55637 (15)	0.71659 (15)	0.06560 (12)	0.0433 (3)
H2	0.5096	0.6909	0.1159	0.052*
N3	1.24589 (17)	0.64228 (17)	0.10373 (16)	0.0549 (4)
O1	0.76236 (12)	0.75260 (11)	0.00900 (10)	0.0393 (2)
O2	0.58447 (15)	0.60002 (16)	0.26385 (13)	0.0625 (3)
O3	0.79677 (15)	0.53945 (13)	0.35412 (11)	0.0523 (3)
F	1.53011 (18)	1.01296 (16)	0.75406 (12)	0.1082 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0310 (6)	0.0395 (7)	0.0353 (7)	0.0147 (5)	0.0211 (6)	0.0115 (5)
C2	0.0314 (6)	0.0383 (7)	0.0328 (6)	0.0150 (5)	0.0190 (5)	0.0104 (5)
C3	0.0350 (7)	0.0355 (6)	0.0338 (6)	0.0166 (5)	0.0197 (6)	0.0137 (5)
C4	0.0338 (7)	0.0421 (7)	0.0334 (6)	0.0147 (6)	0.0212 (6)	0.0140 (5)
C5	0.0318 (7)	0.0405 (7)	0.0341 (6)	0.0142 (6)	0.0205 (5)	0.0112 (5)
C6	0.0396 (8)	0.0696 (10)	0.0509 (9)	0.0300 (8)	0.0219 (7)	0.0255 (8)
C11	0.0388 (7)	0.0423 (7)	0.0354 (7)	0.0199 (6)	0.0231 (6)	0.0163 (6)
C12	0.0416 (8)	0.0537 (9)	0.0415 (8)	0.0146 (7)	0.0239 (7)	0.0173 (7)
C13	0.0538 (9)	0.0618 (10)	0.0579 (10)	0.0201 (8)	0.0396 (8)	0.0275 (8)
C14	0.0731 (11)	0.0616 (10)	0.0465 (9)	0.0319 (9)	0.0425 (9)	0.0265 (8)
C15	0.0614 (10)	0.0669 (11)	0.0342 (8)	0.0229 (8)	0.0225 (7)	0.0167 (7)
C16	0.0410 (8)	0.0590 (9)	0.0407 (8)	0.0158 (7)	0.0218 (7)	0.0186 (7)
C21	0.0354 (7)	0.0435 (7)	0.0385 (7)	0.0164 (6)	0.0208 (6)	0.0139 (6)
C31	0.0355 (7)	0.0410 (7)	0.0337 (7)	0.0170 (6)	0.0201 (6)	0.0148 (5)
C32	0.0596 (10)	0.0441 (8)	0.0478 (9)	0.0218 (7)	0.0186 (8)	0.0168 (7)
C33	0.0755 (13)	0.0427 (9)	0.0531 (10)	0.0088 (9)	0.0198 (9)	0.0062 (8)
C34	0.0530 (10)	0.0673 (11)	0.0362 (8)	0.0059 (9)	0.0102 (7)	0.0117 (8)
C35	0.0593 (11)	0.0757 (12)	0.0454 (9)	0.0271 (9)	0.0106 (8)	0.0284 (9)
C36	0.0544 (9)	0.0491 (9)	0.0445 (8)	0.0236 (7)	0.0164 (7)	0.0198 (7)
N1	0.0393 (7)	0.0504 (7)	0.0388 (6)	0.0150 (5)	0.0241 (5)	0.0170 (5)
N2	0.0362 (6)	0.0633 (8)	0.0435 (7)	0.0258 (6)	0.0260 (5)	0.0237 (6)
N3	0.0446 (8)	0.0647 (9)	0.0710 (9)	0.0295 (7)	0.0370 (7)	0.0240 (7)
O1	0.0381 (5)	0.0574 (6)	0.0411 (5)	0.0273 (5)	0.0273 (4)	0.0259 (5)
O2	0.0495 (7)	0.0981 (9)	0.0680 (8)	0.0353 (7)	0.0449 (6)	0.0453 (7)
O3	0.0570 (7)	0.0622 (7)	0.0492 (6)	0.0258 (6)	0.0314 (5)	0.0328 (5)
F	0.0874 (9)	0.0959 (10)	0.0492 (7)	−0.0025 (7)	−0.0066 (6)	0.0070 (6)

Geometric parameters (Å, º) top

C1—C2	1.3293 (18)	C13—H13	0.9300
C1—O1	1.3795 (15)	C14—C15	1.372 (2)
C1—C11	1.4717 (17)	C14—H14	0.9300
C2—C21	1.4276 (18)	C15—C16	1.382 (2)
C2—C3	1.5089 (17)	C15—H15	0.9300
C3—C4	1.5012 (18)	C16—H16	0.9300
C3—C31	1.5222 (18)	C21—N3	1.1369 (18)
C3—H3	0.9800	C31—C32	1.374 (2)
C4—C5	1.3796 (19)	C31—C36	1.374 (2)
C4—N1	1.3855 (17)	C32—C33	1.382 (2)
C5—N2	1.3130 (17)	C32—H32	0.9300
C5—O1	1.3566 (15)	C33—C34	1.354 (3)
C6—N2	1.4498 (19)	C33—H33	0.9300
C6—H6A	0.9600	C34—C35	1.351 (3)
C6—H6B	0.9600	C34—F	1.3599 (19)
C6—H6C	0.9600	C35—C36	1.381 (2)
C11—C12	1.382 (2)	C35—H35	0.9300
C11—C16	1.386 (2)	C36—H36	0.9300
C12—C13	1.380 (2)	N1—O3	1.2375 (16)
C12—H12	0.9300	N1—O2	1.2558 (16)
C13—C14	1.368 (2)	N2—H2	0.8600

C2—C1—O1	121.49 (11)	C13—C14—H14	120.0
C2—C1—C11	127.43 (12)	C15—C14—H14	120.0
O1—C1—C11	110.91 (11)	C14—C15—C16	120.27 (15)
C1—C2—C21	119.74 (12)	C14—C15—H15	119.9
C1—C2—C3	124.43 (11)	C16—C15—H15	119.9
C21—C2—C3	115.60 (11)	C15—C16—C11	119.75 (14)
C4—C3—C2	108.51 (10)	C15—C16—H16	120.1
C4—C3—C31	114.77 (10)	C11—C16—H16	120.1
C2—C3—C31	111.06 (10)	N3—C21—C2	175.98 (15)
C4—C3—H3	107.4	C32—C31—C36	118.79 (14)
C2—C3—H3	107.4	C32—C31—C3	121.42 (12)
C31—C3—H3	107.4	C36—C31—C3	119.77 (12)
C5—C4—N1	120.05 (12)	C31—C32—C33	120.93 (15)
C5—C4—C3	123.99 (11)	C31—C32—H32	119.5
N1—C4—C3	115.78 (11)	C33—C32—H32	119.5
N2—C5—O1	111.37 (11)	C34—C33—C32	118.19 (16)
N2—C5—C4	128.35 (12)	C34—C33—H33	120.9
O1—C5—C4	120.27 (11)	C32—C33—H33	120.9
N2—C6—H6A	109.5	C35—C34—C33	122.83 (16)
N2—C6—H6B	109.5	C35—C34—F	118.40 (17)
H6A—C6—H6B	109.5	C33—C34—F	118.76 (18)
N2—C6—H6C	109.5	C34—C35—C36	118.57 (16)
H6A—C6—H6C	109.5	C34—C35—H35	120.7
H6B—C6—H6C	109.5	C36—C35—H35	120.7
C12—C11—C16	119.61 (13)	C31—C36—C35	120.69 (15)
C12—C11—C1	121.15 (12)	C31—C36—H36	119.7
C16—C11—C1	119.16 (12)	C35—C36—H36	119.7
C13—C12—C11	119.86 (14)	O3—N1—O2	121.01 (11)
C13—C12—H12	120.1	O3—N1—C4	118.35 (12)
C11—C12—H12	120.1	O2—N1—C4	120.64 (12)
C14—C13—C12	120.41 (15)	C5—N2—C6	124.79 (12)
C14—C13—H13	119.8	C5—N2—H2	117.6
C12—C13—H13	119.8	C6—N2—H2	117.6
C13—C14—C15	120.07 (14)	C5—O1—C1	120.68 (10)

O1—C1—C2—C21	175.21 (12)	C1—C11—C16—C15	−175.02 (14)
C11—C1—C2—C21	0.5 (2)	C1—C2—C21—N3	−149 (2)
O1—C1—C2—C3	0.9 (2)	C3—C2—C21—N3	25 (2)
C11—C1—C2—C3	−173.81 (12)	C4—C3—C31—C32	−60.76 (17)
C1—C2—C3—C4	5.36 (18)	C2—C3—C31—C32	62.76 (17)
C21—C2—C3—C4	−169.14 (11)	C4—C3—C31—C36	120.98 (14)
C1—C2—C3—C31	−121.67 (14)	C2—C3—C31—C36	−115.50 (14)
C21—C2—C3—C31	63.83 (14)	C36—C31—C32—C33	−0.5 (3)
C2—C3—C4—C5	−6.35 (18)	C3—C31—C32—C33	−178.80 (15)
C31—C3—C4—C5	118.52 (14)	C31—C32—C33—C34	0.6 (3)
C2—C3—C4—N1	168.72 (11)	C32—C33—C34—C35	−0.2 (3)
C31—C3—C4—N1	−66.41 (15)	C32—C33—C34—F	−178.89 (18)
N1—C4—C5—N2	6.2 (2)	C33—C34—C35—C36	−0.4 (3)
C3—C4—C5—N2	−178.88 (13)	F—C34—C35—C36	178.36 (17)
N1—C4—C5—O1	−173.76 (12)	C32—C31—C36—C35	0.0 (2)
C3—C4—C5—O1	1.1 (2)	C3—C31—C36—C35	178.28 (15)
C2—C1—C11—C12	−51.4 (2)	C34—C35—C36—C31	0.5 (3)
O1—C1—C11—C12	133.39 (14)	C5—C4—N1—O3	172.24 (12)
C2—C1—C11—C16	125.37 (16)	C3—C4—N1—O3	−3.05 (18)
O1—C1—C11—C16	−49.82 (17)	C5—C4—N1—O2	−7.1 (2)
C16—C11—C12—C13	−1.8 (2)	C3—C4—N1—O2	177.62 (12)
C1—C11—C12—C13	174.97 (14)	O1—C5—N2—C6	0.9 (2)
C11—C12—C13—C14	0.3 (3)	C4—C5—N2—C6	−179.11 (14)
C12—C13—C14—C15	1.1 (3)	N2—C5—O1—C1	−173.84 (11)
C13—C14—C15—C16	−1.1 (3)	C4—C5—O1—C1	6.16 (19)
C14—C15—C16—C11	−0.4 (3)	C2—C1—O1—C5	−7.26 (19)
C12—C11—C16—C15	1.8 (2)	C11—C1—O1—C5	168.27 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.99	2.6089 (16)	128
N2—H2···N3ⁱ	0.86	2.30	2.9811 (17)	136
C6—H6A···N3ⁱ	0.96	2.60	3.222 (2)	123

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₄FN₃O₃
M_r	351.33
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.3898 (3), 9.9752 (3), 11.1324 (3)
α, β, γ (°)	98.765 (1), 113.991 (1), 109.520 (1)
V (Å³)	846.09 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.23 × 0.20 × 0.19

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	16948, 3680, 2993
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.06
No. of reflections	3680
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.99	2.6089 (16)	127.7
N2—H2···N3ⁱ	0.86	2.30	2.9811 (17)	136.2
C6—H6A···N3ⁱ	0.96	2.60	3.222 (2)	122.9

Symmetry code: (i) x−1, y, z.

Acknowledgements

JS thanks the UGC for the FIST support. JS and RV thank the management of the Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under the fast-track scheme (No. SR/FT/CS-073/2009).

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Liang, F., Cheng, X., Liu, J. & Liu, Q. (2009). Chem. Commun. pp. 3636–3638. Web of Science CSD CrossRef Google Scholar
Lokaj, J., Kettmann, V., Pavelčík, F., Ilavský, D. & Marchalín, Š. (1990). Acta Cryst. C46, 788–791. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Marco, J. L., Martín, G., Martín, N., Martínez-Grau, A., Seoane, C., Albert, A. & Cano, F. H. (1993). Tetrahedron, 49, 7133–7144. CSD CrossRef CAS Web of Science Google Scholar
Nesterov, V. N. & Viltchinskaia, E. A. (2001). Acta Cryst. C57, 616–618. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nesterov, V. N., Wiedenfeld, D. J., Nesterova, S. V. & Minton, M. A. (2004). Acta Cryst. C60, o334–o337. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. 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
Suárez, M., Salfrán, E., Verdecia, Y., Ochoa, E., Alba, L., Martín, N., Martínez, R., Quinteiro, M., Seoane, C., Novoa, H., Blaton, N., Peeters, O. M. & De Ranter, C. (2002). Tetrahedron, 58, 953–960. Google Scholar