3-(2,4-Difluoro-anilino)-9-nitro-dibenzo[b,e]oxepin-11(6H)-one.

In the title compound, C(20)H(12)F(2)N(2)O(4), the two benzene rings of the tricyclic unit are oriented at a dihedral angle of 30.6 (1)°. The 2,4-difluoro-anilino residue is oriented at a dihedral angle of 68.2 (1)° with respect to the phen-oxy ring. In the crystal, N-H⋯O hydrogen bonds between the amino group and the carbonyl O atom of the oxepinone ring link the mol-ecules into infinte chains along the c axis.

Related literature

For palladium-catalysed amination reactions of n class="Chemical">aryl halides with anilines, see: Jensen et al. (2004 ▶). For p38 MAP kinase inhibitors based on dibenzo[b,e]oxepin-11(6H)-one, see: Laufer et al. (2006 ▶).

Experimental

Crystal data

C20H12F2N2O4

M = 382.32

Orthorhombic,

a = 27.0813 (15) Å

b = 13.0411 (8) Å

c = 4.5998 (2) Å

V = 1624.51 (15) Å3

Z = 4

Cu Kα radiation

μ = 1.08 mm−1

T = 193 K

0.47 × 0.24 × 0.12 mm

Data collection

Enraf–Nonius n class="Gene">CAD-4 diffractometer

Absorption correction: numerical (CORINC; Dräger & Gattow, 1971 ▶) T min = 0.721, T max = 0.882

3417 measured reflections

3010 independent reflections

2924 reflections with I > 2σ(I)

R int = 0.051

3 standard reflections every 60 min intensity decay: 3%

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.127

S = 1.03

3010 reflections

253 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack, (1983 ▶), 1270 Friedel pairs

Flack parameter: −0.22 (18)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002881/im2261sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002881/im2261Isup2.hkl

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

C20H12F2N2O4	F(000) = 784
Mr = 382.32	Dx = 1.563 Mg m−3
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 27.0813 (15) Å	θ = 65–69°
b = 13.0411 (8) Å	µ = 1.08 mm−1
c = 4.5998 (2) Å	T = 193 K
V = 1624.51 (15) Å3	Needle, yellow
Z = 4	0.47 × 0.24 × 0.12 mm

Enraf–Nonius CAD-4 diffractometer	2924 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.051
graphite	θmax = 69.8°, θmin = 3.3°
ω/2θ scans	h = −33→33
Absorption correction: numerical (CORINC; Dräger & Gattow, 1971)	k = −15→15
Tmin = 0.721, Tmax = 0.882	l = −5→5
3417 measured reflections	3 standard reflections every 60 min
3010 independent reflections	intensity decay: 3%

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)] = 0.047	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0989P)2 + 0.3414P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.023
3010 reflections	Δρmax = 0.17 e Å−3
253 parameters	Δρmin = −0.20 e Å−3
1 restraint	Absolute structure: Flack, (1983), 1270 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.22 (18)

Experimental. 1H NMR (200 MHz, DMSO-d~6~) δ in p.p.m. 5.32 (s, 2 H), 6.26 (m, 1 H), 6.65 (dd, J=8.65, 1.96 Hz, 1 H), 7.11 (m, 1 H), 7.39 (m, 2 H), 7.82 (m, 1 H), 8.02 (d, J=8.97 Hz, 1 H), 8.41 (dd, J=8.21, 2.53 Hz, 1 H), 8.52 (d, J=2.40 Hz, 1 H), 8.85 (s, NH,1 H).13C NMR (50 MHz, DMSO-d~6~) δ in p.p.m. 72.5, 102.1, 110.5, 116.5, 124.3, 127.0, 130.4, 134.1, 141.1, 142.9, 148.3, 152.9, 163.4, 185.1, C—F not detected.GC/MS, m/z (%) 382 (100, M+), 308 (12), 152 (9), 98 (7), 63 (1).

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.

	x	y	z	Uiso*/Ueq
O1	0.58864 (5)	0.24963 (11)	0.3890 (3)	0.0240 (3)
C2	0.56177 (7)	0.30020 (15)	0.5965 (4)	0.0215 (4)
C3	0.51656 (8)	0.25513 (16)	0.6587 (5)	0.0242 (4)
H3	0.5068	0.1947	0.5587	0.029*
C4	0.48548 (8)	0.29789 (17)	0.8665 (5)	0.0245 (4)
C5	0.50161 (8)	0.38484 (16)	1.0212 (5)	0.0242 (4)
H5	0.4818	0.4123	1.1728	0.029*
C6	0.54556 (8)	0.42947 (15)	0.9536 (5)	0.0234 (4)
H6	0.5556	0.4882	1.0605	0.028*
C7	0.57698 (7)	0.39218 (15)	0.7306 (4)	0.0216 (4)
C8	0.61655 (7)	0.46277 (15)	0.6377 (4)	0.0222 (4)
C9	0.65513 (7)	0.43587 (15)	0.4150 (5)	0.0215 (4)
C10	0.68194 (8)	0.51865 (17)	0.3032 (5)	0.0248 (4)
H10	0.6752	0.5865	0.3670	0.030*
C11	0.71823 (7)	0.50081 (16)	0.0997 (5)	0.0262 (5)
C12	0.73012 (8)	0.40368 (18)	0.0000 (5)	0.0275 (5)
H12	0.7551	0.3936	−0.1423	0.033*
C13	0.70420 (7)	0.32175 (17)	0.1161 (5)	0.0253 (5)
H13	0.7120	0.2541	0.0550	0.030*
C14	0.66696 (7)	0.33663 (16)	0.3204 (5)	0.0223 (4)
C15	0.64067 (7)	0.24498 (15)	0.4420 (5)	0.0253 (5)
H15A	0.6542	0.1820	0.3525	0.030*
H15B	0.6466	0.2412	0.6541	0.030*
N16	0.43947 (7)	0.25975 (16)	0.9317 (5)	0.0341 (5)
H16	0.4191	0.3040	1.0435	0.041*
C17	0.41597 (8)	0.18098 (18)	0.7713 (5)	0.0287 (5)
C18	0.37502 (8)	0.20134 (19)	0.5998 (6)	0.0352 (5)
H18	0.3631	0.2697	0.5860	0.042*
C19	0.35112 (10)	0.1240 (2)	0.4481 (7)	0.0434 (6)
H19	0.3226	0.1381	0.3345	0.052*
C20	0.36991 (10)	0.0266 (2)	0.4670 (6)	0.0407 (6)
C21	0.41046 (10)	0.00166 (19)	0.6308 (7)	0.0409 (6)
H21	0.4229	−0.0664	0.6384	0.049*
C22	0.43238 (9)	0.0805 (2)	0.7842 (6)	0.0355 (6)
F23	0.34769 (7)	−0.04940 (15)	0.3148 (5)	0.0629 (6)
F24	0.47133 (6)	0.05902 (13)	0.9539 (5)	0.0558 (5)
O25	0.61751 (6)	0.55042 (11)	0.7364 (4)	0.0302 (4)
N26	0.74461 (7)	0.58919 (15)	−0.0221 (5)	0.0315 (4)
O27	0.73855 (7)	0.67347 (14)	0.0898 (5)	0.0476 (5)
O28	0.77170 (7)	0.57374 (15)	−0.2321 (5)	0.0434 (5)

	U11	U22	U33	U12	U13	U23
O1	0.0251 (7)	0.0263 (7)	0.0205 (8)	−0.0019 (5)	0.0021 (6)	−0.0047 (6)
C2	0.0275 (9)	0.0227 (10)	0.0143 (9)	0.0030 (7)	−0.0011 (8)	0.0020 (8)
C3	0.0306 (10)	0.0249 (10)	0.0171 (10)	−0.0024 (8)	−0.0015 (9)	−0.0011 (8)
C4	0.0270 (10)	0.0287 (10)	0.0179 (11)	−0.0006 (8)	0.0009 (8)	0.0029 (8)
C5	0.0303 (10)	0.0286 (11)	0.0137 (10)	0.0044 (8)	0.0011 (8)	0.0012 (8)
C6	0.0327 (10)	0.0243 (9)	0.0132 (10)	0.0013 (8)	−0.0043 (8)	0.0005 (8)
C7	0.0253 (9)	0.0251 (10)	0.0142 (10)	0.0013 (8)	−0.0036 (8)	0.0021 (8)
C8	0.0271 (9)	0.0210 (9)	0.0184 (10)	0.0019 (7)	−0.0060 (8)	0.0015 (8)
C9	0.0230 (9)	0.0245 (9)	0.0170 (10)	−0.0001 (8)	−0.0063 (8)	0.0033 (8)
C10	0.0283 (10)	0.0227 (9)	0.0234 (11)	−0.0015 (8)	−0.0083 (9)	0.0037 (8)
C11	0.0246 (9)	0.0300 (11)	0.0239 (11)	−0.0059 (8)	−0.0052 (8)	0.0067 (9)
C12	0.0252 (9)	0.0333 (11)	0.0239 (11)	−0.0003 (8)	−0.0023 (9)	0.0038 (9)
C13	0.0256 (9)	0.0261 (10)	0.0241 (11)	0.0017 (8)	−0.0032 (9)	0.0014 (8)
C14	0.0218 (9)	0.0249 (10)	0.0201 (10)	0.0013 (7)	−0.0055 (8)	0.0019 (8)
C15	0.0266 (10)	0.0220 (10)	0.0275 (11)	0.0005 (7)	0.0022 (9)	0.0028 (9)
N16	0.0318 (9)	0.0404 (11)	0.0301 (11)	−0.0050 (8)	0.0088 (9)	−0.0101 (9)
C17	0.0274 (10)	0.0336 (11)	0.0250 (12)	−0.0039 (8)	0.0078 (9)	−0.0015 (9)
C18	0.0338 (11)	0.0355 (13)	0.0363 (14)	0.0036 (9)	0.0046 (10)	−0.0016 (11)
C19	0.0371 (12)	0.0532 (15)	0.0400 (16)	−0.0028 (11)	−0.0025 (12)	−0.0075 (13)
C20	0.0447 (14)	0.0424 (13)	0.0349 (15)	−0.0147 (11)	0.0132 (11)	−0.0110 (11)
C21	0.0444 (12)	0.0287 (12)	0.0495 (16)	−0.0035 (10)	0.0142 (12)	0.0015 (12)
C22	0.0309 (11)	0.0381 (12)	0.0373 (14)	−0.0009 (9)	0.0052 (11)	0.0077 (11)
F23	0.0677 (11)	0.0604 (11)	0.0606 (12)	−0.0257 (9)	0.0120 (10)	−0.0305 (10)
F24	0.0483 (9)	0.0541 (10)	0.0649 (12)	0.0051 (7)	−0.0134 (9)	0.0171 (9)
O25	0.0352 (8)	0.0244 (8)	0.0311 (9)	−0.0034 (6)	0.0017 (7)	−0.0047 (7)
N26	0.0312 (9)	0.0318 (10)	0.0314 (11)	−0.0070 (8)	−0.0010 (9)	0.0060 (9)
O27	0.0584 (11)	0.0300 (9)	0.0545 (13)	−0.0103 (8)	0.0147 (10)	0.0022 (8)
O28	0.0460 (9)	0.0441 (10)	0.0402 (11)	−0.0120 (8)	0.0137 (9)	0.0031 (9)

O1—C2	1.370 (2)	C12—H12	0.9500
O1—C15	1.431 (3)	C13—C14	1.392 (3)
C2—C3	1.388 (3)	C13—H13	0.9500
C2—C7	1.410 (3)	C14—C15	1.499 (3)
C3—C4	1.390 (3)	C15—H15A	0.9900
C3—H3	0.9500	C15—H15B	0.9900
C4—N16	1.375 (3)	N16—C17	1.416 (3)
C4—C5	1.408 (3)	N16—H16	0.9504
C5—C6	1.361 (3)	C17—C18	1.387 (3)
C5—H5	0.9500	C17—C22	1.385 (3)
C6—C7	1.419 (3)	C18—C19	1.387 (4)
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.476 (3)	C19—C20	1.371 (4)
C8—O25	1.230 (3)	C19—H19	0.9500
C8—C9	1.504 (3)	C20—F23	1.355 (3)
C9—C10	1.399 (3)	C20—C21	1.371 (4)
C9—C14	1.403 (3)	C21—C22	1.381 (4)
C10—C11	1.377 (3)	C21—H21	0.9500
C10—H10	0.9500	C22—F24	1.341 (3)
C11—C12	1.385 (3)	N26—O27	1.225 (3)
C11—N26	1.467 (3)	N26—O28	1.230 (3)
C12—C13	1.385 (3)
C2—O1—C15	115.13 (16)	C12—C13—H13	119.3
O1—C2—C3	114.11 (19)	C14—C13—H13	119.3
O1—C2—C7	123.99 (18)	C13—C14—C9	120.24 (19)
C3—C2—C7	121.85 (19)	C13—C14—C15	119.00 (19)
C2—C3—C4	120.4 (2)	C9—C14—C15	120.75 (19)
C2—C3—H3	119.8	O1—C15—C14	111.72 (16)
C4—C3—H3	119.8	O1—C15—H15A	109.3
N16—C4—C3	123.6 (2)	C14—C15—H15A	109.3
N16—C4—C5	117.53 (19)	O1—C15—H15B	109.3
C3—C4—C5	118.85 (19)	C14—C15—H15B	109.3
C6—C5—C4	120.02 (19)	H15A—C15—H15B	107.9
C6—C5—H5	120.0	C4—N16—C17	123.8 (2)
C4—C5—H5	120.0	C4—N16—H16	115.2
C5—C6—C7	122.89 (19)	C17—N16—H16	117.5
C5—C6—H6	118.6	C18—C17—C22	117.5 (2)
C7—C6—H6	118.6	C18—C17—N16	121.1 (2)
C2—C7—C6	115.63 (18)	C22—C17—N16	121.3 (2)
C2—C7—C8	128.01 (18)	C17—C18—C19	121.4 (2)
C6—C7—C8	115.54 (18)	C17—C18—H18	119.3
O25—C8—C7	119.20 (19)	C19—C18—H18	119.3
O25—C8—C9	116.95 (18)	C20—C19—C18	117.9 (2)
C7—C8—C9	123.78 (18)	C20—C19—H19	121.0
C10—C9—C14	118.6 (2)	C18—C19—H19	121.0
C10—C9—C8	115.52 (18)	F23—C20—C19	118.7 (3)
C14—C9—C8	125.81 (18)	F23—C20—C21	117.8 (3)
C11—C10—C9	119.3 (2)	C19—C20—C21	123.5 (2)
C11—C10—H10	120.3	C20—C21—C22	116.6 (2)
C9—C10—H10	120.3	C20—C21—H21	121.7
C10—C11—C12	123.1 (2)	C22—C21—H21	121.7
C10—C11—N26	118.3 (2)	F24—C22—C21	118.7 (2)
C12—C11—N26	118.6 (2)	F24—C22—C17	118.3 (2)
C11—C12—C13	117.4 (2)	C21—C22—C17	123.0 (2)
C11—C12—H12	121.3	O27—N26—O28	123.8 (2)
C13—C12—H12	121.3	O27—N26—C11	118.7 (2)
C12—C13—C14	121.3 (2)	O28—N26—C11	117.5 (2)
C15—O1—C2—C3	−140.97 (18)	C12—C13—C14—C9	−0.5 (3)
C15—O1—C2—C7	41.3 (3)	C12—C13—C14—C15	−179.1 (2)
O1—C2—C3—C4	179.62 (18)	C10—C9—C14—C13	−0.9 (3)
C7—C2—C3—C4	−2.6 (3)	C8—C9—C14—C13	−178.83 (19)
C2—C3—C4—N16	177.5 (2)	C10—C9—C14—C15	177.64 (19)
C2—C3—C4—C5	−2.8 (3)	C8—C9—C14—C15	−0.3 (3)
N16—C4—C5—C6	−176.1 (2)	C2—O1—C15—C14	−88.1 (2)
C3—C4—C5—C6	4.2 (3)	C13—C14—C15—O1	−121.5 (2)
C4—C5—C6—C7	−0.2 (3)	C9—C14—C15—O1	59.9 (3)
O1—C2—C7—C6	−176.19 (18)	C3—C4—N16—C17	−8.2 (4)
C3—C2—C7—C6	6.3 (3)	C5—C4—N16—C17	172.1 (2)
O1—C2—C7—C8	14.7 (3)	C4—N16—C17—C18	−110.1 (3)
C3—C2—C7—C8	−162.8 (2)	C4—N16—C17—C22	71.2 (3)
C5—C6—C7—C2	−4.9 (3)	C22—C17—C18—C19	0.4 (4)
C5—C6—C7—C8	165.57 (19)	N16—C17—C18—C19	−178.4 (2)
C2—C7—C8—O25	162.9 (2)	C17—C18—C19—C20	−1.5 (4)
C6—C7—C8—O25	−6.2 (3)	C18—C19—C20—F23	−178.5 (2)
C2—C7—C8—C9	−14.0 (3)	C18—C19—C20—C21	1.0 (4)
C6—C7—C8—C9	176.95 (17)	F23—C20—C21—C22	−179.9 (2)
O25—C8—C9—C10	−11.8 (3)	C19—C20—C21—C22	0.6 (4)
C7—C8—C9—C10	165.16 (18)	C20—C21—C22—F24	178.1 (2)
O25—C8—C9—C14	166.2 (2)	C20—C21—C22—C17	−1.8 (4)
C7—C8—C9—C14	−16.9 (3)	C18—C17—C22—F24	−178.6 (2)
C14—C9—C10—C11	1.4 (3)	N16—C17—C22—F24	0.1 (3)
C8—C9—C10—C11	179.54 (17)	C18—C17—C22—C21	1.3 (4)
C9—C10—C11—C12	−0.6 (3)	N16—C17—C22—C21	−179.9 (2)
C9—C10—C11—N26	177.82 (18)	C10—C11—N26—O27	10.3 (3)
C10—C11—C12—C13	−0.8 (3)	C12—C11—N26—O27	−171.3 (2)
N26—C11—C12—C13	−179.2 (2)	C10—C11—N26—O28	−169.8 (2)
C11—C12—C13—C14	1.3 (3)	C12—C11—N26—O28	8.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N16—H16···O25i	0.95	2.32	3.236 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N16—H16⋯O25i	0.95	2.32	3.236 (3)	162

Symmetry code: (i) .