Ethyl 2-amino-4-(4-fluoro­phen­yl)-6-meth­oxy-4H-benzo[h]chromene-3-carboxyl­ate

El-Agrody, A.M.; Al-Omar, M.A.; Amr, A.-G.E.; Chia, T.S.; Fun, H.-K.

doi:10.1107/S1600536812021939

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1803-o1804

doi:10.1107/S1600536812021939

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Ethyl 2-amino-4-(4-fluorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate

Ahmed M. El-Agrody,^a Mohamed A. Al-Omar,^b,^c Abdel-Galil E. Amr,^c,^d Tze Shyang Chia ^e and Hoong-Kun Fun ^e ^*‡

^aChemistry Department, Faculty of Science, King Khalid University, 9004, Abha, Saudi Arabia, ^bPharmaceutical Chemistry Department, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^cDrug Exploration & Development Chair (DEDC), College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^dApplied Organic Chemistry Department, National Research Center, Dokki 12622, Cairo, Egypt, and ^eX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 13 May 2012; accepted 15 May 2012; online 19 May 2012)

In the title compound, C₂₃H₂₀FNO₄, 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 methoxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C—O—C—C = −2.1 (2)°]. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules 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 interactions.

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_r = 393.40
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.117
S = 1.08
3657 reflections
273 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

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⋯Cg2^iv	0.93	2.94	3.7003 (17)	140
C20—H20C⋯Cg3^iv	0.96	2.74	3.5896 (17)	148
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021939/is5141sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536812021939/is5141Isup3.cml

checkCIF report

Comment top

The 4H-chromene nucleus is frequently found in bioactive compounds and plays an important role in biochemical processes (Jeso & Nicolaou, 2009; Alvey et al., 2008, 2009; Symeonidis et al., 2009). In addition, 4H-chromenes and fused 4H-chromenes nuclei are used in treatment of Alzheimer's disease and Schizophrenia disorder (Brühlmann et al., 2001). In view of the above observations and in continuation of our program on the chemistry of 4H-pyran derivatives (Bedair et al., 2001; El-Agrody et al., 2002, 2011; Abd-El-Aziz et al., 2004; Sabry et al., 2011), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The fluoro-substituted benzene ring (C14–C19) is approximately perpendicular to the 4H-benzo[h]chromene ring system [O1/C1–C13, maximum deviation = 0.264 (1) Å at atom C2] as indicated by the dihedral angle of 83.79 (6)°. The pyran ring (O1/C1–C5) adopts a flattened boat conformation [puckering parameters (Cremer & Pople, 1975), Q = 0.2599 (13) Å, θ = 79.3 (3)° and ϕ = 170.9 (3)°]. The atoms O1 and C3 are deviating from the mean plane of C1/C2/C4/C5 by 0.1589 (18) and 0.2820 (21) Å, respectively. The methoxy group (C20/O2) is slightly twisted from the attached benzene ring (C4–C6/C11–C13) of the 4H-benzo[h]chromene moiety with the torsion angle C20—O2—C12—C13 of -2.1 (2)°. An intramolecular N1—H1N1···O3 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) in the molecule.

In the crystal (Fig. 2), molecules are linked by intermolecular N1—H2N1···O3 and N1—H1N1···F1 hydrogen bonds (Table 1) into a layer parallel to the bc plane. The crystal packing is further stabilized by C—H···π interactions (Table 1), involving Cg1, Cg2 and Cg3 which are the centroids of C4–C6/C11–C13, C14–C19 and C6–C11 rings, respectively.

Related literature top

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 top

A solution of 4-methoxy-1-naphthol (0.01 mol) in EtOH (30 ml) was treated with ethyl α-cyano-p-fluorocinnamate (0.01 mol) and piperidine (0.5 ml). The reaction mixture was heated under reflux for 2 h. The obtained solid product was collected by filtration, dried and crystallized from ethanol to give the title compound. M.p.: 435–436 K.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. A packing view of the title compound along the a axis. The dashed lines represent the hydrogen bonds. For clarity sake, hydrogen atoms not involved in hydrogen bonding have been omitted.

Ethyl 2-amino-4-(4-fluorophenyl)-6-methoxy-4H- benzo[h]chromene-3-carboxylate top

Crystal data top

C₂₃H₂₀FNO₄	F(000) = 824
M_r = 393.40	D_x = 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

Data collection top

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

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0641P)² + 0.2106P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3657 reflections	Δρ_max = 0.19 e Å⁻³
273 parameters	Δρ_min = −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)

Crystal data top

C₂₃H₂₀FNO₄	V = 1937.24 (8) Å³
M_r = 393.40	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.6844 (3) Å	µ = 0.82 mm⁻¹
b = 16.1933 (4) Å	T = 296 K
c = 9.4579 (2) Å	0.81 × 0.74 × 0.04 mm
β = 94.288 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3657 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3009 reflections with I > 2σ(I)
T_min = 0.556, T_max = 0.972	R_int = 0.034
13713 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.19 e Å⁻³
3657 reflections	Δρ_min = −0.19 e Å⁻³
273 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg2^iv	0.93	2.94	3.7003 (17)	140
C20—H20C···Cg3^iv	0.96	2.74	3.5896 (17)	148

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+3/2; (iii) x, −y−1/2, z−3/2; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀FNO₄
M_r	393.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.6844 (3), 16.1933 (4), 9.4579 (2)
β (°)	94.288 (2)
V (Å³)	1937.24 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.81 × 0.74 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.556, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	13713, 3657, 3009
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.117, 1.08
No. of reflections	3657
No. of parameters	273
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···Cg2^iv	0.93	2.94	3.7003 (17)	140
C20—H20C···Cg3^iv	0.96	2.74	3.5896 (17)	148

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+3/2; (iii) x, −y−1/2, z−3/2; (iv) −x+1, −y+1, −z+1.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009

Acknowledgements

HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC also thanks the Malaysian Government and USM for the award of a research fellowship. The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding the work through the research group project No. RGP-VPP-099.

References

Abd-El-Aziz, A. S., El-Agrody, A. M., Bedair, A. H., Corkery, T. C. & Ata, A. (2004). Heterocycles, 63, 1793–1812. CAS Google Scholar
Alvey, L., Prado, S., Huteau, V., Saint-Joanis, B., Michel, S., Koch, M., Cole, S. T., Tillequin, F. & Janin, Y. L. (2008). Bioorg. Med. Chem. 16, 8264–8272. Web of Science CrossRef PubMed CAS Google Scholar
Alvey, L., Prado, S., Saint-Joanis, B., Michel, S., Koch, M., Cole, S. T., Tillequin, F. & Janin, Y. L. (2009). Eur. J. Med. Chem. 44, 2497–2505. Web of Science CrossRef PubMed CAS Google Scholar
Bedair, A. H., Emam, H. A., El-Hady, N. A., Ahmed, K. A. R. & El-Agrody, A. M. (2001). Farmaco, 56, 965–973. Web of Science CrossRef PubMed CAS 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
Brühlmann, C., Ooms, F., Carrupt, P.-A., Testa, B., Catto, M., Leonetti, F., Altomare, C. & Carotti, A. (2001). J. Med. Chem. 44, 3195–3198. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2009). SADABS, 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
El-Agrody, A. M., Eid, F. A., Emam, H. A., Mohamed, H. M. & Bedair, A. H. (2002). Z. Naturforsch. Teil B, 57, 579–585. CAS Google Scholar
El-Agrody, A. M., Sabry, N. M. & Motlaq, S. S. (2011). J. Chem. Res. 35, 77–83. CAS Google Scholar
Jeso, V. & Nicolaou, K. C. (2009). Tetrahedron Lett. 50, 1161–1163. Web of Science CrossRef CAS PubMed Google Scholar
Sabry, N. M., Mohamed, H. M., Khattab, E. S. A. E. H., Motlaq, S. S. & El-Agrody, A. M. (2011). Eur. J. Med. Chem. 46, 765–772. Web of Science CrossRef CAS PubMed 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
Symeonidis, T., Chamilos, M., Hadjipavlou-Litina, D. J., Kallitsakis, M. & Litinas, K. E. (2009). Bioorg. Med. Chem. Lett. 19, 1139–1142. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 68| Part 6| June 2012| Pages o1803-o1804

doi:10.1107/S1600536812021939

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 2-amino-4-(4-fluoro­phen­yl)-6-meth­­oxy-4H-benzo[h]chromene-3-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

Ethyl 2-amino-4-(4-fluorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate