Ethyl 2-amino-4,6-bis-(4-fluoro-phen-yl)cyclo-hexa-1,3-diene-1-carboxyl-ate.

In the title compound, C(21)H(19)F(2)NO(2), the cyclo-hexa-1,3-diene ring is in a distorted envelope conformation. The dihedral angles between the mean planes of the diene moiety and the two fluoro-phenyl rings are 42.8 (2) and 75.0 (5)°. The two fluoro-phenyl rings are inclined to one another by 87.0 (3)°. In the crystal, intra-molecular N-H⋯O hydrogen bonds and weak N-H⋯O and N-H⋯F inter-molecular inter-actions are observed forming an infinite two-dimensional network along [011].

Related literature

For background to the applications of cyclo­hexenones, see: Padmavathi et al. (1999 ▶, 2000 ▶); Padmavathi, Sharmila, Balaiah et al. (2001 ▶); Padmavathi, Sharmila, Somashekara Reddy & Bhaskar Reddy (2001 ▶). For the structure of the precursor of the title compound, see: Dutkiewicz et al. (2011 ▶). For various derivatives of 4,4-difluoro­chalcone, see: Fun et al. (2010a ▶,b ▶); Jasinski et al. (2010a ▶,b ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C21H19F2NO2

M = 355.37

Orthorhombic,

a = 18.0199 (5) Å

b = 9.6391 (2) Å

c = 21.0754 (7) Å

V = 3660.70 (18) Å3

Z = 8

Cu Kα radiation

μ = 0.80 mm−1

T = 173 K

0.20 × 0.14 × 0.12 mm

Data collection

Oxford Xcalibur Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.856, T max = 0.910

10556 measured reflections

3461 independent reflections

2612 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.180

S = 1.04

3461 reflections

245 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681200373X/mw2046sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200373X/mw2046Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681200373X/mw2046Isup3.cml

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

C21H19F2NO2	F(000) = 1488
Mr = 355.37	Dx = 1.290 Mg m−3
Orthorhombic, Pbcn	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4418 reflections
a = 18.0199 (5) Å	θ = 3.2–71.3°
b = 9.6391 (2) Å	µ = 0.80 mm−1
c = 21.0754 (7) Å	T = 173 K
V = 3660.70 (18) Å3	Block, yellow
Z = 8	0.20 × 0.14 × 0.12 mm

Oxford Xcalibur Eos Gemini diffractometer	3461 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2612 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 16.1500 pixels mm-1	θmax = 71.4°, θmin = 4.2°
ω scans	h = −21→16
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.856, Tmax = 0.910	l = −22→25
10556 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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.180	w = 1/[σ2(Fo2) + (0.1072P)2 + 0.4506P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3461 reflections	Δρmax = 0.41 e Å−3
245 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (2)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
F1	0.28820 (7)	0.39132 (16)	0.58085 (8)	0.0963 (5)
F2	0.66890 (12)	0.94956 (19)	0.80642 (12)	0.1445 (8)
O1	0.57361 (8)	0.00028 (13)	0.57519 (7)	0.0679 (4)
O2	0.66652 (8)	0.05261 (14)	0.50837 (8)	0.0695 (4)
N1	0.72288 (11)	0.3120 (2)	0.51875 (9)	0.0692 (5)
H1B	0.7509 (15)	0.380 (3)	0.5083 (10)	0.076 (7)*
H1A	0.7197 (12)	0.239 (2)	0.4942 (11)	0.066 (6)*
C1	0.49783 (15)	−0.1988 (2)	0.57203 (16)	0.0931 (8)
H1C	0.4854	−0.2832	0.5484	0.140*
H1D	0.4545	−0.1375	0.5734	0.140*
H1E	0.5124	−0.2235	0.6154	0.140*
C2	0.56045 (13)	−0.12602 (19)	0.53997 (12)	0.0746 (6)
H2A	0.6054	−0.1850	0.5401	0.089*
H2B	0.5473	−0.1043	0.4954	0.089*
C3	0.62737 (10)	0.08577 (18)	0.55369 (10)	0.0578 (5)
C4	0.63143 (11)	0.21328 (19)	0.58891 (10)	0.0572 (5)
C5	0.67799 (11)	0.31852 (19)	0.56986 (10)	0.0572 (5)
C6	0.68054 (11)	0.44920 (19)	0.60540 (10)	0.0609 (5)
H6A	0.7040	0.5274	0.5867	0.073*
C7	0.65069 (11)	0.4618 (2)	0.66361 (10)	0.0600 (5)
C8	0.61518 (13)	0.3357 (2)	0.69326 (10)	0.0667 (5)
H8A	0.5763	0.3668	0.7232	0.080*
H8B	0.6532	0.2852	0.7181	0.080*
C9	0.58026 (11)	0.23520 (19)	0.64523 (10)	0.0592 (5)
H9A	0.5759	0.1435	0.6671	0.071*
C10	0.50212 (11)	0.27746 (17)	0.62632 (9)	0.0559 (5)
C11	0.44170 (12)	0.2002 (2)	0.64594 (11)	0.0684 (6)
H11A	0.4499	0.1195	0.6709	0.082*
C12	0.37006 (13)	0.2363 (2)	0.63060 (12)	0.0770 (6)
H12A	0.3293	0.1813	0.6443	0.092*
C13	0.35890 (12)	0.3530 (2)	0.59515 (11)	0.0690 (6)
C14	0.41611 (13)	0.4322 (2)	0.57387 (12)	0.0748 (6)
H14A	0.4070	0.5126	0.5490	0.090*
C15	0.48779 (12)	0.3937 (2)	0.58902 (11)	0.0715 (6)
H15A	0.5281	0.4476	0.5737	0.086*
C16	0.65610 (11)	0.5913 (2)	0.70079 (11)	0.0648 (5)
C17	0.66870 (14)	0.7180 (2)	0.67350 (13)	0.0781 (6)
H17A	0.6753	0.7226	0.6288	0.094*
C18	0.67220 (15)	0.8387 (3)	0.70790 (17)	0.0898 (8)
H18A	0.6790	0.9256	0.6874	0.108*
C19	0.66577 (16)	0.8309 (3)	0.77206 (18)	0.0979 (9)
C20	0.6589 (2)	0.7078 (3)	0.80307 (16)	0.1065 (10)
H20A	0.6580	0.7039	0.8481	0.128*
C21	0.65327 (18)	0.5888 (3)	0.76701 (13)	0.0934 (8)
H21A	0.6473	0.5023	0.7879	0.112*

	U11	U22	U33	U12	U13	U23
F1	0.0684 (8)	0.0980 (10)	0.1224 (13)	0.0017 (7)	−0.0188 (8)	−0.0061 (8)
F2	0.1599 (17)	0.0981 (12)	0.175 (2)	−0.0024 (11)	0.0216 (15)	−0.0716 (13)
O1	0.0700 (8)	0.0498 (7)	0.0838 (10)	−0.0096 (6)	0.0083 (7)	−0.0045 (6)
O2	0.0641 (8)	0.0553 (7)	0.0891 (11)	0.0019 (6)	0.0118 (8)	−0.0099 (7)
N1	0.0711 (11)	0.0588 (10)	0.0776 (13)	−0.0125 (8)	0.0186 (10)	−0.0101 (9)
C1	0.0954 (18)	0.0609 (12)	0.123 (2)	−0.0220 (12)	0.0001 (16)	0.0023 (13)
C2	0.0793 (14)	0.0475 (10)	0.0970 (17)	−0.0052 (9)	−0.0028 (12)	−0.0052 (10)
C3	0.0523 (9)	0.0474 (9)	0.0737 (13)	0.0016 (7)	−0.0012 (10)	0.0031 (8)
C4	0.0568 (10)	0.0500 (9)	0.0646 (12)	−0.0010 (8)	0.0013 (9)	0.0002 (8)
C5	0.0565 (10)	0.0524 (9)	0.0627 (12)	−0.0008 (8)	0.0039 (9)	−0.0009 (8)
C6	0.0622 (11)	0.0510 (9)	0.0696 (13)	−0.0085 (8)	0.0040 (10)	−0.0006 (8)
C7	0.0620 (11)	0.0568 (10)	0.0613 (12)	−0.0023 (8)	−0.0005 (9)	−0.0001 (8)
C8	0.0737 (13)	0.0658 (11)	0.0607 (12)	−0.0078 (9)	0.0050 (10)	0.0020 (9)
C9	0.0644 (11)	0.0490 (9)	0.0642 (12)	−0.0044 (8)	0.0068 (9)	0.0062 (8)
C10	0.0627 (11)	0.0452 (8)	0.0598 (11)	−0.0051 (8)	0.0086 (9)	−0.0033 (7)
C11	0.0690 (12)	0.0577 (11)	0.0784 (14)	−0.0072 (9)	0.0090 (11)	0.0090 (9)
C12	0.0653 (12)	0.0725 (13)	0.0932 (17)	−0.0160 (10)	0.0096 (12)	0.0049 (12)
C13	0.0622 (12)	0.0663 (12)	0.0786 (14)	0.0002 (9)	−0.0066 (11)	−0.0128 (10)
C14	0.0780 (14)	0.0578 (11)	0.0886 (16)	−0.0029 (10)	−0.0080 (12)	0.0086 (10)
C15	0.0680 (13)	0.0568 (11)	0.0897 (16)	−0.0090 (9)	0.0015 (11)	0.0141 (10)
C16	0.0651 (11)	0.0623 (11)	0.0671 (13)	0.0023 (9)	0.0036 (10)	−0.0047 (9)
C17	0.0852 (15)	0.0661 (13)	0.0831 (16)	−0.0069 (10)	0.0037 (12)	−0.0076 (11)
C18	0.0873 (17)	0.0642 (13)	0.118 (2)	−0.0003 (11)	0.0098 (16)	−0.0136 (14)
C19	0.0881 (18)	0.0780 (16)	0.128 (3)	0.0035 (13)	0.0108 (16)	−0.0422 (16)
C20	0.129 (3)	0.098 (2)	0.092 (2)	0.0000 (17)	0.0041 (18)	−0.0281 (16)
C21	0.119 (2)	0.0792 (15)	0.0816 (18)	−0.0014 (14)	0.0062 (15)	−0.0085 (13)

F1—C13	1.360 (2)	C8—H8B	0.9900
F2—C19	1.355 (3)	C9—C10	1.519 (3)
O1—C3	1.350 (2)	C9—H9A	1.0000
O1—C2	1.445 (2)	C10—C11	1.382 (3)
O2—C3	1.230 (2)	C10—C15	1.393 (3)
N1—C5	1.348 (3)	C11—C12	1.375 (3)
N1—H1B	0.86 (3)	C11—H11A	0.9500
N1—H1A	0.88 (2)	C12—C13	1.366 (3)
C1—C2	1.491 (3)	C12—H12A	0.9500
C1—H1C	0.9800	C13—C14	1.359 (3)
C1—H1D	0.9800	C14—C15	1.381 (3)
C1—H1E	0.9800	C14—H14A	0.9500
C2—H2A	0.9900	C15—H15A	0.9500
C2—H2B	0.9900	C16—C17	1.369 (3)
C3—C4	1.438 (3)	C16—C21	1.397 (4)
C4—C5	1.376 (3)	C17—C18	1.372 (3)
C4—C9	1.518 (3)	C17—H17A	0.9500
C5—C6	1.466 (3)	C18—C19	1.359 (5)
C6—C7	1.345 (3)	C18—H18A	0.9500
C6—H6A	0.9500	C19—C20	1.360 (4)
C7—C16	1.478 (3)	C20—C21	1.379 (4)
C7—C8	1.508 (3)	C20—H20A	0.9500
C8—C9	1.536 (3)	C21—H21A	0.9500
C8—H8A	0.9900
C3—O1—C2	117.35 (16)	C4—C9—H9A	106.6
C5—N1—H1B	121.5 (15)	C10—C9—H9A	106.6
C5—N1—H1A	118.0 (15)	C8—C9—H9A	106.6
H1B—N1—H1A	120 (2)	C11—C10—C15	117.13 (19)
C2—C1—H1C	109.5	C11—C10—C9	120.48 (17)
C2—C1—H1D	109.5	C15—C10—C9	122.39 (17)
H1C—C1—H1D	109.5	C12—C11—C10	122.20 (19)
C2—C1—H1E	109.5	C12—C11—H11A	118.9
H1C—C1—H1E	109.5	C10—C11—H11A	118.9
H1D—C1—H1E	109.5	C13—C12—C11	118.4 (2)
O1—C2—C1	106.7 (2)	C13—C12—H12A	120.8
O1—C2—H2A	110.4	C11—C12—H12A	120.8
C1—C2—H2A	110.4	C14—C13—F1	119.0 (2)
O1—C2—H2B	110.4	C14—C13—C12	122.1 (2)
C1—C2—H2B	110.4	F1—C13—C12	118.9 (2)
H2A—C2—H2B	108.6	C13—C14—C15	118.8 (2)
O2—C3—O1	120.91 (17)	C13—C14—H14A	120.6
O2—C3—C4	126.45 (17)	C15—C14—H14A	120.6
O1—C3—C4	112.64 (17)	C14—C15—C10	121.3 (2)
C5—C4—C3	120.69 (18)	C14—C15—H15A	119.3
C5—C4—C9	119.73 (17)	C10—C15—H15A	119.3
C3—C4—C9	119.46 (16)	C17—C16—C21	116.2 (2)
N1—C5—C4	124.37 (18)	C17—C16—C7	122.8 (2)
N1—C5—C6	115.42 (17)	C21—C16—C7	120.8 (2)
C4—C5—C6	120.21 (18)	C16—C17—C18	122.8 (3)
C7—C6—C5	122.06 (17)	C16—C17—H17A	118.6
C7—C6—H6A	119.0	C18—C17—H17A	118.6
C5—C6—H6A	119.0	C19—C18—C17	118.3 (3)
C6—C7—C16	122.23 (18)	C19—C18—H18A	120.8
C6—C7—C8	118.36 (18)	C17—C18—H18A	120.8
C16—C7—C8	119.27 (18)	F2—C19—C18	118.8 (3)
C7—C8—C9	114.13 (17)	F2—C19—C20	118.9 (3)
C7—C8—H8A	108.7	C18—C19—C20	122.3 (2)
C9—C8—H8A	108.7	C19—C20—C21	117.9 (3)
C7—C8—H8B	108.7	C19—C20—H20A	121.1
C9—C8—H8B	108.7	C21—C20—H20A	121.1
H8A—C8—H8B	107.6	C20—C21—C16	122.2 (3)
C4—C9—C10	113.29 (17)	C20—C21—H21A	118.9
C4—C9—C8	110.75 (16)	C16—C21—H21A	118.9
C10—C9—C8	112.54 (17)
C3—O1—C2—C1	−178.43 (19)	C8—C9—C10—C15	70.1 (2)
C2—O1—C3—O2	−4.5 (3)	C15—C10—C11—C12	−1.0 (3)
C2—O1—C3—C4	175.00 (17)	C9—C10—C11—C12	179.0 (2)
O2—C3—C4—C5	5.9 (3)	C10—C11—C12—C13	−0.5 (4)
O1—C3—C4—C5	−173.59 (18)	C11—C12—C13—C14	1.2 (4)
O2—C3—C4—C9	−177.93 (19)	C11—C12—C13—F1	−178.6 (2)
O1—C3—C4—C9	2.6 (3)	F1—C13—C14—C15	179.4 (2)
C3—C4—C5—N1	−0.6 (3)	C12—C13—C14—C15	−0.5 (4)
C9—C4—C5—N1	−176.69 (19)	C13—C14—C15—C10	−1.1 (4)
C3—C4—C5—C6	178.74 (18)	C11—C10—C15—C14	1.8 (3)
C9—C4—C5—C6	2.6 (3)	C9—C10—C15—C14	−178.2 (2)
N1—C5—C6—C7	−166.7 (2)	C6—C7—C16—C17	22.1 (3)
C4—C5—C6—C7	14.0 (3)	C8—C7—C16—C17	−162.2 (2)
C5—C6—C7—C16	177.17 (19)	C6—C7—C16—C21	−153.7 (2)
C5—C6—C7—C8	1.4 (3)	C8—C7—C16—C21	22.1 (3)
C6—C7—C8—C9	−31.0 (3)	C21—C16—C17—C18	−5.4 (4)
C16—C7—C8—C9	153.08 (18)	C7—C16—C17—C18	178.6 (2)
C5—C4—C9—C10	96.8 (2)	C16—C17—C18—C19	2.7 (4)
C3—C4—C9—C10	−79.4 (2)	C17—C18—C19—F2	−179.8 (2)
C5—C4—C9—C8	−30.7 (3)	C17—C18—C19—C20	2.6 (5)
C3—C4—C9—C8	153.10 (17)	F2—C19—C20—C21	177.8 (3)
C7—C8—C9—C4	43.9 (2)	C18—C19—C20—C21	−4.5 (5)
C7—C8—C9—C10	−84.0 (2)	C19—C20—C21—C16	1.5 (5)
C4—C9—C10—C11	123.5 (2)	C17—C16—C21—C20	3.3 (4)
C8—C9—C10—C11	−109.9 (2)	C7—C16—C21—C20	179.4 (3)
C4—C9—C10—C15	−56.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2i	0.86 (3)	2.23 (3)	3.066 (2)	165 (2)
N1—H1A···O2	0.88 (2)	2.06 (2)	2.708 (2)	130.3 (19)
N1—H1A···F1ii	0.88 (2)	2.37 (2)	3.104 (2)	141.9 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2i	0.86 (3)	2.23 (3)	3.066 (2)	165 (2)
N1—H1A⋯O2	0.88 (2)	2.06 (2)	2.708 (2)	130.3 (19)
N1—H1A⋯F1ii	0.88 (2)	2.37 (2)	3.104 (2)	141.9 (19)

Symmetry codes: (i) ; (ii) .