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

The title compound, C₂₂H₁₈FNO₃, was synthesized by the reaction of 1-naphthol with eth­yl cyano­caetate and 3-fluoro­benzaldehyde in ethanol under microwave irradiation. In the crystal structure, there are intra­molecular N—H...O hydrogen bonds and inter­molecular N—H...O and N—H...F hydrogen bonds. An intra­molecular C—H...π inter­action is also present.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.084
• wR factor = 0.289
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.289
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.120
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.12
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 Perc.
PLAT084_ALERT_2_C High R2 Value ..................................       0.29
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           25.97
           From the CIF: _reflns_number_total               3509
           From the CIF: _diffrn_reflns_limit_ max hkl   10.    7.   38.
           From the CIF: _diffrn_reflns_limit_ min hkl    0.    0.  -38.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   11.    7.   40.
           Calculated minimum hkl  -11.   -7.  -40.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97.

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

Crystal data

C22H18FNO3	F(000) = 760
Mr = 363.37	Dx = 1.343 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.069 (2) Å	Cell parameters from 25 reflections
b = 6.136 (1) Å	θ = 10–13°
c = 32.537 (7) Å	µ = 0.10 mm^−1
β = 96.87 (3)°	T = 293 K
V = 1797.6 (6) Å^3	Block, colourless
Z = 4	0.4 × 0.3 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.120
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 1.3°
Graphite monochromator	h = 0→10
ω/2θ scans	k = 0→7
3741 measured reflections	l = −38→38
3509 independent reflections	3 standard reflections every 200 reflections
1679 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.084	H-atom parameters constrained
wR(F^2) = 0.289	w = 1/[σ^2(Fo^2) + (0.08P)^2 + 6.8P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3509 reflections	Δρmax = 0.33 e Å^−3
245 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (17)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
F	1.2082 (4)	0.1597 (8)	0.10104 (15)	0.0996 (15)
O1	0.6146 (5)	0.7810 (8)	0.00781 (13)	0.0745 (14)
O2	0.7413 (4)	0.4730 (8)	0.02520 (11)	0.0607 (12)
O3	0.5441 (4)	0.8428 (7)	0.13299 (11)	0.0550 (11)
N	0.5103 (6)	0.9974 (9)	0.07181 (15)	0.0634 (14)
H0A	0.5180	1.0137	0.0459	0.076*
H0B	0.4622	1.0916	0.0846	0.076*
C1	0.8548 (9)	0.2435 (14)	−0.0199 (2)	0.087 (2)
H1A	0.8688	0.2154	−0.0482	0.131*
H1B	0.8078	0.1200	−0.0089	0.131*
H1C	0.9493	0.2687	−0.0040	0.131*
C2	0.7590 (8)	0.4396 (13)	−0.01787 (18)	0.0682 (19)
H2A	0.8054	0.5659	−0.0288	0.082*
H2B	0.6631	0.4165	−0.0339	0.082*
C3	0.6643 (6)	0.6496 (11)	0.03450 (17)	0.0520 (15)
C4	0.6515 (6)	0.6628 (10)	0.07833 (15)	0.0465 (14)
C5	0.5723 (6)	0.8276 (10)	0.09204 (16)	0.0472 (14)
C6	0.7208 (6)	0.4859 (10)	0.10656 (16)	0.0472 (13)
H6A	0.6920	0.3449	0.0939	0.057*
C7	0.8909 (6)	0.4960 (10)	0.11317 (15)	0.0446 (13)
C8	0.9745 (6)	0.3210 (11)	0.10331 (17)	0.0525 (15)
H8A	0.9291	0.1972	0.0911	0.063*
C9	1.1263 (7)	0.3325 (12)	0.11181 (19)	0.0604 (17)
C10	1.1987 (7)	0.5058 (14)	0.1304 (2)	0.0679 (19)
H10A	1.3016	0.5067	0.1361	0.081*
C11	1.1159 (7)	0.6788 (14)	0.1403 (2)	0.073 (2)
H11A	1.1627	0.8005	0.1529	0.087*
C12	0.9627 (6)	0.6755 (11)	0.13183 (18)	0.0591 (16)
H12A	0.9077	0.7950	0.1387	0.071*
C13	0.6616 (5)	0.4966 (10)	0.14768 (16)	0.0460 (13)
C14	0.6927 (6)	0.3249 (11)	0.17630 (18)	0.0568 (16)
H14A	0.7466	0.2050	0.1690	0.068*
C15	0.6445 (7)	0.3323 (12)	0.21466 (19)	0.0651 (18)
H15A	0.6669	0.2178	0.2331	0.078*
C16	0.5617 (6)	0.5111 (12)	0.22652 (17)	0.0545 (16)
C17	0.5099 (7)	0.5236 (14)	0.2659 (2)	0.072 (2)
H17A	0.5293	0.4092	0.2845	0.087*
C18	0.4339 (8)	0.6959 (15)	0.2767 (2)	0.076 (2)
H18A	0.4027	0.7014	0.3029	0.091*
C19	0.4010 (7)	0.8681 (15)	0.2492 (2)	0.078 (2)
H19A	0.3472	0.9866	0.2572	0.094*
C20	0.4468 (6)	0.8664 (12)	0.20984 (18)	0.0610 (17)
H20A	0.4241	0.9813	0.1915	0.073*
C21	0.5282 (6)	0.6864 (11)	0.19866 (17)	0.0507 (15)
C22	0.5814 (6)	0.6669 (10)	0.15884 (16)	0.0458 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F	0.072 (3)	0.111 (4)	0.120 (4)	0.031 (3)	0.026 (2)	0.002 (3)
O1	0.085 (3)	0.095 (4)	0.042 (2)	0.014 (3)	0.003 (2)	0.025 (3)
O2	0.070 (3)	0.080 (3)	0.033 (2)	0.007 (3)	0.0082 (18)	−0.003 (2)
O3	0.068 (3)	0.058 (3)	0.039 (2)	0.005 (2)	0.0054 (17)	0.000 (2)
N	0.079 (4)	0.067 (3)	0.044 (3)	0.011 (3)	0.006 (2)	0.003 (3)
C1	0.102 (6)	0.106 (6)	0.056 (4)	−0.002 (5)	0.021 (4)	−0.018 (4)
C2	0.074 (4)	0.094 (5)	0.037 (3)	−0.002 (4)	0.013 (3)	−0.006 (3)
C3	0.046 (3)	0.069 (4)	0.040 (3)	−0.007 (3)	0.002 (2)	0.001 (3)
C4	0.048 (3)	0.060 (4)	0.031 (3)	0.002 (3)	0.001 (2)	0.003 (3)
C5	0.051 (3)	0.058 (4)	0.032 (3)	−0.001 (3)	0.003 (2)	0.003 (3)
C6	0.047 (3)	0.049 (3)	0.044 (3)	−0.005 (3)	0.002 (2)	−0.004 (3)
C7	0.043 (3)	0.056 (3)	0.036 (3)	−0.003 (3)	0.005 (2)	0.002 (3)
C8	0.056 (3)	0.059 (4)	0.043 (3)	−0.004 (3)	0.010 (3)	0.000 (3)
C9	0.053 (4)	0.082 (5)	0.050 (4)	0.016 (4)	0.019 (3)	0.006 (4)
C10	0.043 (3)	0.106 (6)	0.056 (4)	−0.008 (4)	0.010 (3)	0.001 (4)
C11	0.061 (4)	0.096 (6)	0.060 (4)	−0.030 (4)	0.001 (3)	−0.007 (4)
C12	0.053 (4)	0.070 (4)	0.055 (4)	−0.008 (3)	0.011 (3)	−0.009 (3)
C13	0.037 (3)	0.058 (4)	0.042 (3)	−0.005 (3)	0.001 (2)	0.001 (3)
C14	0.058 (4)	0.065 (4)	0.048 (3)	0.005 (3)	0.009 (3)	0.004 (3)
C15	0.064 (4)	0.081 (5)	0.050 (4)	−0.007 (4)	0.006 (3)	0.022 (4)
C16	0.047 (3)	0.078 (4)	0.038 (3)	−0.013 (3)	0.007 (2)	−0.002 (3)
C17	0.063 (4)	0.104 (6)	0.052 (4)	−0.018 (4)	0.016 (3)	0.010 (4)
C18	0.067 (4)	0.126 (7)	0.038 (3)	−0.016 (5)	0.019 (3)	0.000 (5)
C19	0.056 (4)	0.112 (6)	0.068 (5)	−0.007 (4)	0.014 (3)	−0.032 (5)
C20	0.057 (4)	0.082 (5)	0.044 (3)	−0.005 (4)	0.006 (3)	−0.016 (3)
C21	0.039 (3)	0.069 (4)	0.044 (3)	−0.012 (3)	0.005 (2)	−0.005 (3)
C22	0.043 (3)	0.054 (3)	0.040 (3)	−0.001 (3)	0.003 (2)	−0.001 (3)

Geometric parameters (Å, º)

F—C9	1.364 (7)	C8—H8A	0.9300
O1—C3	1.230 (7)	C9—C10	1.353 (9)
O2—C3	1.343 (7)	C10—C11	1.361 (10)
O2—C2	1.444 (7)	C10—H10A	0.9300
O3—C22	1.385 (7)	C11—C12	1.383 (8)
O3—C5	1.389 (6)	C11—H11A	0.9300
N—C5	1.322 (7)	C12—H12A	0.9300
N—H0A	0.8600	C13—C22	1.347 (8)
N—H0B	0.8600	C13—C14	1.412 (8)
C1—C2	1.490 (10)	C14—C15	1.372 (8)
C1—H1A	0.9600	C14—H14A	0.9300
C1—H1B	0.9600	C15—C16	1.409 (9)
C1—H1C	0.9600	C15—H15A	0.9300
C2—H2A	0.9700	C16—C21	1.416 (9)
C2—H2B	0.9700	C16—C17	1.418 (8)
C3—C4	1.447 (7)	C17—C18	1.332 (10)
C4—C5	1.347 (8)	C17—H17A	0.9300
C4—C6	1.510 (8)	C18—C19	1.395 (10)
C6—C13	1.502 (7)	C18—H18A	0.9300
C6—C7	1.533 (7)	C19—C20	1.392 (9)
C6—H6A	0.9800	C19—H19A	0.9300
C7—C8	1.374 (8)	C20—C21	1.400 (8)
C7—C12	1.382 (8)	C20—H20A	0.9300
C8—C9	1.373 (8)	C21—C22	1.441 (7)
C3—O2—C2	117.0 (5)	F—C9—C8	118.2 (7)
C22—O3—C5	118.1 (4)	C9—C10—C11	117.8 (6)
C5—N—H0A	120.0	C9—C10—H10A	121.1
C5—N—H0B	120.0	C11—C10—H10A	121.1
H0A—N—H0B	120.0	C10—C11—C12	120.7 (7)
C2—C1—H1A	109.5	C10—C11—H11A	119.6
C2—C1—H1B	109.5	C12—C11—H11A	119.6
H1A—C1—H1B	109.5	C7—C12—C11	120.5 (6)
C2—C1—H1C	109.5	C7—C12—H12A	119.7
H1A—C1—H1C	109.5	C11—C12—H12A	119.7
H1B—C1—H1C	109.5	C22—C13—C14	118.2 (5)
O2—C2—C1	107.0 (6)	C22—C13—C6	122.4 (5)
O2—C2—H2A	110.3	C14—C13—C6	119.4 (5)
C1—C2—H2A	110.3	C15—C14—C13	121.0 (6)
O2—C2—H2B	110.3	C15—C14—H14A	119.5
C1—C2—H2B	110.3	C13—C14—H14A	119.5
H2A—C2—H2B	108.6	C14—C15—C16	120.9 (6)
O1—C3—O2	121.7 (5)	C14—C15—H15A	119.6
O1—C3—C4	126.4 (6)	C16—C15—H15A	119.6
O2—C3—C4	111.9 (5)	C15—C16—C21	119.8 (5)
C5—C4—C3	118.5 (5)	C15—C16—C17	122.3 (6)
C5—C4—C6	122.5 (5)	C21—C16—C17	117.9 (7)
C3—C4—C6	118.9 (5)	C18—C17—C16	121.3 (7)
N—C5—C4	129.7 (5)	C18—C17—H17A	119.3
N—C5—O3	108.0 (5)	C16—C17—H17A	119.3
C4—C5—O3	122.3 (5)	C17—C18—C19	120.6 (6)
C13—C6—C4	110.1 (5)	C17—C18—H18A	119.7
C13—C6—C7	109.5 (4)	C19—C18—H18A	119.7
C4—C6—C7	113.3 (5)	C20—C19—C18	121.3 (7)
C13—C6—H6A	107.9	C20—C19—H19A	119.3
C4—C6—H6A	107.9	C18—C19—H19A	119.3
C7—C6—H6A	107.9	C19—C20—C21	118.0 (7)
C8—C7—C12	118.7 (5)	C19—C20—H20A	121.0
C8—C7—C6	120.6 (5)	C21—C20—H20A	121.0
C12—C7—C6	120.5 (5)	C20—C21—C16	120.8 (5)
C7—C8—C9	118.7 (6)	C20—C21—C22	122.9 (6)
C7—C8—H8A	120.6	C16—C21—C22	116.3 (6)
C9—C8—H8A	120.6	C13—C22—O3	122.8 (5)
C10—C9—F	118.4 (6)	C13—C22—C21	123.8 (5)
C10—C9—C8	123.5 (6)	O3—C22—C21	113.4 (5)
C3—O2—C2—C1	176.7 (5)	C4—C6—C13—C22	−11.6 (7)
C2—O2—C3—O1	−2.1 (8)	C7—C6—C13—C22	113.6 (6)
C2—O2—C3—C4	178.8 (5)	C4—C6—C13—C14	169.6 (5)
O1—C3—C4—C5	3.3 (9)	C7—C6—C13—C14	−65.2 (7)
O2—C3—C4—C5	−177.6 (5)	C22—C13—C14—C15	−0.9 (9)
O1—C3—C4—C6	−179.6 (6)	C6—C13—C14—C15	177.9 (5)
O2—C3—C4—C6	−0.5 (7)	C13—C14—C15—C16	0.4 (9)
C3—C4—C5—N	−6.0 (9)	C14—C15—C16—C21	−0.4 (9)
C6—C4—C5—N	177.0 (5)	C14—C15—C16—C17	179.8 (6)
C3—C4—C5—O3	174.6 (5)	C15—C16—C17—C18	178.8 (6)
C6—C4—C5—O3	−2.3 (8)	C21—C16—C17—C18	−1.0 (9)
C22—O3—C5—N	171.4 (5)	C16—C17—C18—C19	1.1 (11)
C22—O3—C5—C4	−9.1 (8)	C17—C18—C19—C20	−0.4 (11)
C5—C4—C6—C13	12.0 (7)	C18—C19—C20—C21	−0.3 (9)
C3—C4—C6—C13	−165.0 (5)	C19—C20—C21—C16	0.4 (8)
C5—C4—C6—C7	−111.0 (6)	C19—C20—C21—C22	−180.0 (5)
C3—C4—C6—C7	72.0 (6)	C15—C16—C21—C20	−179.6 (5)
C13—C6—C7—C8	114.6 (6)	C17—C16—C21—C20	0.2 (8)
C4—C6—C7—C8	−122.1 (6)	C15—C16—C21—C22	0.8 (8)
C13—C6—C7—C12	−60.8 (7)	C17—C16—C21—C22	−179.4 (5)
C4—C6—C7—C12	62.5 (6)	C14—C13—C22—O3	−179.6 (5)
C12—C7—C8—C9	−1.0 (8)	C6—C13—C22—O3	1.6 (8)
C6—C7—C8—C9	−176.5 (5)	C14—C13—C22—C21	1.4 (8)
C7—C8—C9—C10	1.6 (9)	C6—C13—C22—C21	−177.4 (5)
C7—C8—C9—F	−178.6 (5)	C5—O3—C22—C13	9.5 (7)
F—C9—C10—C11	178.8 (6)	C5—O3—C22—C21	−171.4 (5)
C8—C9—C10—C11	−1.3 (10)	C20—C21—C22—C13	179.0 (5)
C9—C10—C11—C12	0.5 (10)	C16—C21—C22—C13	−1.4 (8)
C8—C7—C12—C11	0.2 (9)	C20—C21—C22—O3	0.0 (7)
C6—C7—C12—C11	175.7 (5)	C16—C21—C22—O3	179.6 (5)
C10—C11—C12—C7	0.1 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1	0.86	2.15	2.732 (7)	125
N—H0A···O1^i	0.86	2.36	3.023 (7)	134
N—H0B···F^ii	0.86	2.46	3.166 (7)	140
C12—H12A···Cg1	0.93	2.72	3.069	103

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