4-(4-Fluoro-phen-yl)-6-methyl-amino-5-nitro-2-phenyl-4H-pyran-3-carbo-nitrile.

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 fluoro-phenyl ring are nearly perpendicular, as evidenced by the dihedral angle of 87.11 (1)°. The amine group forms an intra-molecular N-H⋯O(nitro) hydrogen bond. In the crystal, mol-ecules 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 = 351.33

Triclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.118

S = 1.06

3680 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.22 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009008/bh2475sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009008/bh2475Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009008/bh2475Isup3.cml

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

C19H14FN3O3	Z = 2
Mr = 351.33	F(000) = 364
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.054P)2 + 0.2234P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3680 reflections	Δρmax = 0.24 e Å−3
236 parameters	Δρmin = −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

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) .