Ethyl 2-amino-4-(4-fluoro-phen-yl)-6-meth-oxy-4H-benzo[h]chromene-3-carboxyl-ate.

In the title compound, C(23)H(20)FNO(4), the fluoro-substituted benzene ring is approximately perpendicular to the mean plane of the 4H-benzo[h]chromene ring system [maximum deviation = 0.264 (1) Å], with a dihedral angle of 83.79 (6)°. The pyran ring adopts a flattened boat conformation. The meth-oxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C-O-C-C = -2.1 (2)°]. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯F hydrogen bonds into a layer parallel to the bc plane. The crystal packing also features C-H⋯π inter-actions.

Related literature

For background to and applications of 4H-chromene and its derivatives, see: Jeso & Nicolaou (2009 ▶); Alvey et al. (2008 ▶, 2009 ▶); Symeonidis et al. (2009 ▶); Brühlmann et al. (2001 ▶); Bedair et al. (2001 ▶); El-Agrody et al. (2002 ▶, 2011 ▶); Abd-El-Aziz et al. (2004 ▶); Sabry et al. (2011 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H20FNO4

M = 393.40

Monoclinic,

a = 12.6844 (3) Å

b = 16.1933 (4) Å

c = 9.4579 (2) Å

β = 94.288 (2)°

V = 1937.24 (8) Å3

Z = 4

Cu Kα radiation

μ = 0.82 mm−1

T = 296 K

0.81 × 0.74 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.556, T max = 0.972

13713 measured reflections

3657 independent reflections

3009 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.117

S = 1.08

3657 reflections

273 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.19 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021939/is5141sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021939/is5141Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812021939/is5141Isup3.cml

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

C23H20FNO4	F(000) = 824
Mr = 393.40	Dx = 1.349 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 3029 reflections
a = 12.6844 (3) Å	θ = 3.5–66.5°
b = 16.1933 (4) Å	µ = 0.82 mm−1
c = 9.4579 (2) Å	T = 296 K
β = 94.288 (2)°	Plate, colourless
V = 1937.24 (8) Å3	0.81 × 0.74 × 0.04 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3657 independent reflections
Radiation source: fine-focus sealed tube	3009 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 70.1°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→15
Tmin = 0.556, Tmax = 0.972	k = −19→19
13713 measured reflections	l = −11→11

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.2106P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3657 reflections	Δρmax = 0.19 e Å−3
273 parameters	Δρmin = −0.19 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0059 (5)

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
F1	0.04716 (11)	0.70219 (9)	0.55146 (16)	0.1144 (5)
O1	0.28914 (8)	0.30595 (6)	0.72092 (10)	0.0487 (3)
O2	0.63332 (8)	0.50557 (7)	0.64293 (13)	0.0584 (3)
O3	0.10800 (9)	0.34723 (7)	1.07127 (11)	0.0559 (3)
O4	0.16230 (8)	0.47933 (6)	1.06692 (10)	0.0516 (3)
N1	0.16357 (11)	0.25396 (8)	0.84457 (17)	0.0554 (3)
C1	0.22572 (10)	0.31944 (8)	0.82843 (14)	0.0429 (3)
C2	0.22913 (10)	0.39123 (8)	0.90464 (13)	0.0416 (3)
C3	0.29340 (10)	0.46421 (8)	0.85933 (14)	0.0413 (3)
H3A	0.3264	0.4904	0.9450	0.050*
C4	0.38041 (10)	0.43437 (8)	0.77125 (13)	0.0408 (3)
C5	0.37413 (10)	0.35926 (8)	0.70758 (14)	0.0404 (3)
C6	0.45447 (10)	0.32854 (8)	0.62507 (13)	0.0405 (3)
C7	0.45043 (11)	0.24931 (9)	0.56213 (14)	0.0461 (3)
H7A	0.3928	0.2151	0.5737	0.055*
C8	0.53032 (12)	0.22258 (9)	0.48457 (16)	0.0525 (4)
H8A	0.5274	0.1699	0.4453	0.063*
C9	0.61650 (13)	0.27393 (10)	0.46379 (17)	0.0576 (4)
H9A	0.6700	0.2555	0.4095	0.069*
C10	0.62263 (11)	0.35095 (10)	0.52281 (17)	0.0524 (4)
H10A	0.6801	0.3846	0.5080	0.063*
C11	0.54257 (10)	0.37989 (9)	0.60603 (14)	0.0425 (3)
C12	0.54691 (10)	0.46009 (9)	0.67061 (15)	0.0442 (3)
C13	0.46888 (11)	0.48548 (8)	0.75189 (14)	0.0441 (3)
H13A	0.4737	0.5370	0.7953	0.053*
C14	0.22577 (11)	0.52880 (8)	0.77811 (14)	0.0437 (3)
C15	0.17007 (12)	0.50829 (10)	0.65164 (16)	0.0526 (4)
H15A	0.1735	0.4547	0.6170	0.063*
C16	0.10939 (14)	0.56660 (12)	0.57628 (19)	0.0671 (5)
H16A	0.0721	0.5526	0.4913	0.081*
C17	0.10514 (15)	0.64454 (13)	0.6283 (2)	0.0727 (6)
C18	0.15756 (18)	0.66735 (11)	0.7526 (2)	0.0810 (6)
H18A	0.1526	0.7210	0.7866	0.097*
C19	0.21853 (14)	0.60881 (10)	0.82764 (19)	0.0622 (4)
H19A	0.2552	0.6235	0.9127	0.075*
C20	0.64028 (13)	0.58658 (9)	0.69998 (18)	0.0575 (4)
H20A	0.7007	0.6141	0.6667	0.086*
H20B	0.6474	0.5836	0.8016	0.086*
H20C	0.5774	0.6168	0.6702	0.086*
C21	0.16104 (11)	0.40092 (9)	1.01911 (14)	0.0442 (3)
C22	0.09169 (15)	0.49981 (11)	1.17445 (17)	0.0610 (4)
H22A	0.1145	0.4732	1.2635	0.073*
H22C	0.0203	0.4818	1.1458	0.073*
C23	0.09548 (19)	0.59157 (12)	1.19019 (19)	0.0759 (5)
H23A	0.0444	0.6088	1.2541	0.114*
H23D	0.0797	0.6169	1.0993	0.114*
H23C	0.1648	0.6080	1.2273	0.114*
H2N1	0.1556 (15)	0.2184 (12)	0.773 (2)	0.068 (5)*
H1N1	0.1147 (16)	0.2602 (11)	0.906 (2)	0.072 (6)*

	U11	U22	U33	U12	U13	U23
F1	0.1074 (10)	0.1103 (10)	0.1298 (11)	0.0645 (8)	0.0372 (8)	0.0582 (9)
O1	0.0469 (5)	0.0443 (5)	0.0570 (6)	−0.0104 (4)	0.0167 (4)	−0.0092 (4)
O2	0.0475 (6)	0.0507 (6)	0.0788 (7)	−0.0143 (5)	0.0166 (5)	−0.0054 (5)
O3	0.0612 (6)	0.0524 (6)	0.0566 (6)	−0.0015 (5)	0.0200 (5)	0.0075 (5)
O4	0.0598 (6)	0.0483 (6)	0.0486 (5)	0.0028 (5)	0.0162 (4)	−0.0032 (4)
N1	0.0545 (7)	0.0450 (7)	0.0694 (8)	−0.0103 (6)	0.0231 (6)	−0.0064 (6)
C1	0.0402 (7)	0.0416 (7)	0.0478 (7)	−0.0003 (6)	0.0087 (5)	0.0035 (6)
C2	0.0423 (7)	0.0396 (7)	0.0434 (7)	0.0014 (5)	0.0067 (5)	0.0027 (5)
C3	0.0433 (7)	0.0377 (7)	0.0434 (7)	−0.0023 (5)	0.0058 (5)	−0.0030 (5)
C4	0.0392 (6)	0.0393 (7)	0.0441 (7)	−0.0001 (5)	0.0048 (5)	0.0020 (5)
C5	0.0372 (6)	0.0391 (7)	0.0454 (7)	−0.0051 (5)	0.0064 (5)	0.0029 (5)
C6	0.0416 (7)	0.0389 (7)	0.0411 (6)	0.0001 (5)	0.0039 (5)	0.0025 (5)
C7	0.0495 (8)	0.0424 (7)	0.0469 (7)	−0.0050 (6)	0.0066 (6)	−0.0001 (6)
C8	0.0584 (9)	0.0456 (8)	0.0543 (8)	0.0028 (7)	0.0090 (7)	−0.0080 (6)
C9	0.0524 (8)	0.0589 (9)	0.0635 (9)	0.0049 (7)	0.0184 (7)	−0.0057 (7)
C10	0.0439 (7)	0.0524 (9)	0.0623 (9)	−0.0034 (6)	0.0129 (6)	−0.0003 (7)
C11	0.0404 (7)	0.0426 (7)	0.0448 (7)	−0.0016 (6)	0.0054 (5)	0.0022 (5)
C12	0.0386 (7)	0.0424 (7)	0.0518 (7)	−0.0062 (6)	0.0044 (6)	0.0035 (6)
C13	0.0448 (7)	0.0370 (7)	0.0506 (7)	−0.0036 (6)	0.0037 (6)	−0.0016 (5)
C14	0.0434 (7)	0.0379 (7)	0.0515 (7)	−0.0014 (6)	0.0147 (6)	0.0025 (5)
C15	0.0534 (8)	0.0487 (8)	0.0560 (8)	0.0019 (7)	0.0069 (7)	0.0054 (6)
C16	0.0567 (9)	0.0809 (13)	0.0644 (10)	0.0084 (9)	0.0101 (8)	0.0218 (9)
C17	0.0642 (10)	0.0712 (12)	0.0866 (13)	0.0283 (9)	0.0316 (10)	0.0321 (10)
C18	0.1016 (16)	0.0440 (10)	0.1021 (15)	0.0229 (10)	0.0396 (13)	0.0101 (9)
C19	0.0748 (11)	0.0420 (8)	0.0715 (10)	0.0022 (7)	0.0179 (8)	−0.0034 (7)
C20	0.0520 (8)	0.0460 (8)	0.0738 (10)	−0.0141 (7)	0.0003 (7)	0.0007 (7)
C21	0.0447 (7)	0.0446 (8)	0.0433 (7)	0.0037 (6)	0.0043 (6)	0.0054 (6)
C22	0.0720 (10)	0.0627 (10)	0.0506 (8)	0.0126 (8)	0.0203 (7)	−0.0010 (7)
C23	0.1027 (15)	0.0662 (11)	0.0607 (10)	0.0248 (10)	0.0188 (9)	−0.0052 (8)

F1—C17	1.364 (2)	C9—C10	1.366 (2)
O1—C1	1.3606 (16)	C9—H9A	0.9300
O1—C5	1.3942 (15)	C10—C11	1.4106 (19)
O2—C12	1.3619 (16)	C10—H10A	0.9300
O2—C20	1.4188 (18)	C11—C12	1.4346 (19)
O3—C21	1.2254 (17)	C12—C13	1.3615 (19)
O4—C21	1.3475 (17)	C13—H13A	0.9300
O4—C22	1.4432 (17)	C14—C19	1.383 (2)
N1—C1	1.3367 (18)	C14—C15	1.383 (2)
N1—H2N1	0.89 (2)	C15—C16	1.382 (2)
N1—H1N1	0.88 (2)	C15—H15A	0.9300
C1—C2	1.3668 (19)	C16—C17	1.357 (3)
C2—C21	1.4431 (18)	C16—H16A	0.9300
C2—C3	1.5156 (18)	C17—C18	1.358 (3)
C3—C4	1.5109 (18)	C18—C19	1.385 (3)
C3—C14	1.5236 (19)	C18—H18A	0.9300
C3—H3A	0.9800	C19—H19A	0.9300
C4—C5	1.3568 (19)	C20—H20A	0.9600
C4—C13	1.4173 (18)	C20—H20B	0.9600
C5—C6	1.4191 (18)	C20—H20C	0.9600
C6—C7	1.4137 (18)	C22—C23	1.494 (2)
C6—C11	1.4151 (18)	C22—H22A	0.9700
C7—C8	1.365 (2)	C22—H22C	0.9700
C7—H7A	0.9300	C23—H23A	0.9600
C8—C9	1.399 (2)	C23—H23D	0.9600
C8—H8A	0.9300	C23—H23C	0.9600
C1—O1—C5	118.20 (10)	O2—C12—C11	114.43 (12)
C12—O2—C20	117.07 (12)	C12—C13—C4	120.84 (13)
C21—O4—C22	117.42 (12)	C12—C13—H13A	119.6
C1—N1—H2N1	117.5 (12)	C4—C13—H13A	119.6
C1—N1—H1N1	115.7 (13)	C19—C14—C15	118.37 (14)
H2N1—N1—H1N1	121.7 (17)	C19—C14—C3	121.43 (14)
N1—C1—O1	110.17 (12)	C15—C14—C3	120.20 (13)
N1—C1—C2	127.59 (13)	C16—C15—C14	120.71 (16)
O1—C1—C2	122.24 (12)	C16—C15—H15A	119.6
C1—C2—C21	119.41 (12)	C14—C15—H15A	119.6
C1—C2—C3	120.70 (11)	C17—C16—C15	118.97 (18)
C21—C2—C3	119.47 (12)	C17—C16—H16A	120.5
C4—C3—C2	109.69 (11)	C15—C16—H16A	120.5
C4—C3—C14	110.40 (11)	C16—C17—C18	122.44 (16)
C2—C3—C14	112.54 (11)	C16—C17—F1	118.6 (2)
C4—C3—H3A	108.0	C18—C17—F1	118.98 (19)
C2—C3—H3A	108.0	C17—C18—C19	118.42 (17)
C14—C3—H3A	108.0	C17—C18—H18A	120.8
C5—C4—C13	119.14 (12)	C19—C18—H18A	120.8
C5—C4—C3	120.69 (12)	C14—C19—C18	121.09 (18)
C13—C4—C3	120.16 (12)	C14—C19—H19A	119.5
C4—C5—O1	122.35 (11)	C18—C19—H19A	119.5
C4—C5—C6	122.52 (12)	O2—C20—H20A	109.5
O1—C5—C6	115.12 (11)	O2—C20—H20B	109.5
C7—C6—C11	118.93 (12)	H20A—C20—H20B	109.5
C7—C6—C5	123.01 (12)	O2—C20—H20C	109.5
C11—C6—C5	118.06 (12)	H20A—C20—H20C	109.5
C8—C7—C6	120.59 (13)	H20B—C20—H20C	109.5
C8—C7—H7A	119.7	O3—C21—O4	121.78 (12)
C6—C7—H7A	119.7	O3—C21—C2	127.02 (13)
C7—C8—C9	120.42 (14)	O4—C21—C2	111.19 (12)
C7—C8—H8A	119.8	O4—C22—C23	106.36 (14)
C9—C8—H8A	119.8	O4—C22—H22A	110.5
C10—C9—C8	120.42 (14)	C23—C22—H22A	110.5
C10—C9—H9A	119.8	O4—C22—H22C	110.5
C8—C9—H9A	119.8	C23—C22—H22C	110.5
C9—C10—C11	120.66 (14)	H22A—C22—H22C	108.6
C9—C10—H10A	119.7	C22—C23—H23A	109.5
C11—C10—H10A	119.7	C22—C23—H23D	109.5
C10—C11—C6	118.95 (13)	H23A—C23—H23D	109.5
C10—C11—C12	122.14 (13)	C22—C23—H23C	109.5
C6—C11—C12	118.90 (12)	H23A—C23—H23C	109.5
C13—C12—O2	125.08 (13)	H23D—C23—H23C	109.5
C13—C12—C11	120.49 (12)
C5—O1—C1—N1	−166.73 (12)	C7—C6—C11—C12	−179.64 (12)
C5—O1—C1—C2	13.33 (19)	C5—C6—C11—C12	0.08 (19)
N1—C1—C2—C21	1.2 (2)	C20—O2—C12—C13	−2.1 (2)
O1—C1—C2—C21	−178.85 (12)	C20—O2—C12—C11	177.94 (12)
N1—C1—C2—C3	−171.35 (14)	C10—C11—C12—C13	−179.08 (13)
O1—C1—C2—C3	8.6 (2)	C6—C11—C12—C13	1.7 (2)
C1—C2—C3—C4	−24.06 (17)	C10—C11—C12—O2	0.9 (2)
C21—C2—C3—C4	163.38 (11)	C6—C11—C12—O2	−178.31 (12)
C1—C2—C3—C14	99.26 (15)	O2—C12—C13—C4	178.23 (13)
C21—C2—C3—C14	−73.30 (15)	C11—C12—C13—C4	−1.8 (2)
C2—C3—C4—C5	20.10 (17)	C5—C4—C13—C12	0.0 (2)
C14—C3—C4—C5	−104.48 (14)	C3—C4—C13—C12	−178.74 (12)
C2—C3—C4—C13	−161.16 (12)	C4—C3—C14—C19	−117.90 (14)
C14—C3—C4—C13	74.27 (15)	C2—C3—C14—C19	119.17 (14)
C13—C4—C5—O1	−179.49 (12)	C4—C3—C14—C15	61.86 (16)
C3—C4—C5—O1	−0.7 (2)	C2—C3—C14—C15	−61.06 (16)
C13—C4—C5—C6	1.8 (2)	C19—C14—C15—C16	0.5 (2)
C3—C4—C5—C6	−179.41 (12)	C3—C14—C15—C16	−179.29 (13)
C1—O1—C5—C4	−17.49 (19)	C14—C15—C16—C17	0.0 (2)
C1—O1—C5—C6	161.27 (11)	C15—C16—C17—C18	−0.7 (3)
C4—C5—C6—C7	177.85 (12)	C15—C16—C17—F1	178.41 (15)
O1—C5—C6—C7	−0.91 (18)	C16—C17—C18—C19	0.8 (3)
C4—C5—C6—C11	−1.9 (2)	F1—C17—C18—C19	−178.22 (16)
O1—C5—C6—C11	179.37 (11)	C15—C14—C19—C18	−0.3 (2)
C11—C6—C7—C8	0.2 (2)	C3—C14—C19—C18	179.47 (15)
C5—C6—C7—C8	−179.52 (13)	C17—C18—C19—C14	−0.4 (3)
C6—C7—C8—C9	−1.3 (2)	C22—O4—C21—O3	−5.2 (2)
C7—C8—C9—C10	1.1 (2)	C22—O4—C21—C2	175.45 (12)
C8—C9—C10—C11	0.3 (2)	C1—C2—C21—O3	10.6 (2)
C9—C10—C11—C6	−1.3 (2)	C3—C2—C21—O3	−176.74 (13)
C9—C10—C11—C12	179.44 (14)	C1—C2—C21—O4	−170.03 (12)
C7—C6—C11—C10	1.11 (19)	C3—C2—C21—O4	2.62 (17)
C5—C6—C11—C10	−179.17 (12)	C21—O4—C22—C23	−170.70 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N1···O3i	0.89 (2)	2.23 (2)	3.0969 (19)	165.8 (17)
N1—H1N1···O3	0.89 (2)	2.111 (18)	2.7570 (18)	129.1 (16)
N1—H1N1···F1ii	0.89 (2)	2.32 (2)	3.034 (2)	137.6 (16)
C8—H8A···Cg1iii	0.93	2.81	3.5633 (16)	139
C10—H10A···Cg2iv	0.93	2.94	3.7003 (17)	140
C20—H20C···Cg3iv	0.96	2.74	3.5896 (17)	148

Table 1

Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of C4–C6/C11–C13, C14–C19 and C6–C11 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N1⋯O3i	0.89 (2)	2.23 (2)	3.0969 (19)	165.8 (17)
N1—H1N1⋯O3	0.89 (2)	2.111 (18)	2.7570 (18)	129.1 (16)
N1—H1N1⋯F1ii	0.89 (2)	2.32 (2)	3.034 (2)	137.6 (16)
C8—H8A⋯Cg1iii	0.93	2.81	3.5633 (16)	139
C10—H10A⋯Cg2iv	0.93	2.94	3.7003 (17)	140
C20—H20C⋯Cg3iv	0.96	2.74	3.5896 (17)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .