2-Amino-4-(4-fluoro-phen-yl)-6-meth-oxy-4H-benzo[h]chromene-3-carbonitrile.

In the title mol-ecule, C(21)H(15)FN(2)O(2), the dihedral angle between the fluoro-substituted benzene ring and the mean plane of the 4H-benzo[h]chromene ring system [maximum deviation = 0.109 (2) Å] is 83.35 (7)°. The pyran ring adopts a slight sofa conformation with the tertiary C(H) atom forming the flap. The meth-oxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C-O-C-C = -4.3 (3)°]. In the crystal, mol-ecules are linked by inter-molecular N-H⋯N hydrogen bonds into infinite wave-like chains along the b axis. The crystal packing is further stabilized by π-π inter-actions [centroid-centroid distance = 3.7713 (9) Å].

Related literature

For the synthesis of 4H-chromene derivatives, see: Sayed et al. (2000 ▶); Bedair et al. (2001 ▶); El-Agrody et al. (2000 ▶, 2002 ▶). For the chemical and pharmacological properties of 4H-chromene and fused 4H-chromene derivatives, see: El-Agrody et al. (2000 ▶); Abd-El-Aziz et al. (2004 ▶, 2007 ▶); Sabry et al. (2011 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C21H15FN2O2

M = 346.35

Monoclinic,

a = 12.6336 (4) Å

b = 11.9333 (3) Å

c = 12.0471 (4) Å

β = 113.581 (2)°

V = 1664.56 (9) Å3

Z = 4

Cu Kα radiation

μ = 0.81 mm−1

T = 296 K

0.88 × 0.68 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.537, T max = 0.953

11390 measured reflections

3199 independent reflections

2770 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.132

S = 1.05

3199 reflections

245 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.21 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/S1600536812023021/lh5476sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023021/lh5476Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023021/lh5476Isup3.cml

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

C21H15FN2O2	F(000) = 720
Mr = 346.35	Dx = 1.382 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 3014 reflections
a = 12.6336 (4) Å	θ = 3.8–71.5°
b = 11.9333 (3) Å	µ = 0.81 mm−1
c = 12.0471 (4) Å	T = 296 K
β = 113.581 (2)°	Plate, yellow
V = 1664.56 (9) Å3	0.88 × 0.68 × 0.06 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2770 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω scans	θmax = 71.9°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→15
Tmin = 0.537, Tmax = 0.953	k = −12→14
11390 measured reflections	l = −12→14

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 atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.132	w = 1/[σ2(Fo2) + (0.0702P)2 + 0.3162P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3199 reflections	Δρmax = 0.22 e Å−3
245 parameters	Δρmin = −0.21 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: 0.0030 (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	1.08340 (11)	0.92571 (13)	0.19221 (15)	0.0946 (5)
O1	0.59888 (10)	0.46944 (9)	0.14761 (10)	0.0507 (3)
O2	0.85128 (13)	0.37355 (11)	−0.12356 (13)	0.0677 (4)
N1	0.52279 (14)	0.57508 (14)	0.24812 (14)	0.0569 (4)
N2	0.58458 (15)	0.85793 (13)	0.21110 (16)	0.0666 (4)
C1	0.58225 (13)	0.57477 (13)	0.17674 (13)	0.0442 (3)
C2	0.62297 (13)	0.66625 (13)	0.13969 (13)	0.0439 (3)
C3	0.68193 (12)	0.66037 (12)	0.05215 (13)	0.0416 (3)
H3A	0.6274	0.6888	−0.0262	0.050*
C4	0.70666 (12)	0.53883 (12)	0.03481 (12)	0.0412 (3)
C5	0.66493 (12)	0.45325 (12)	0.07952 (13)	0.0422 (3)
C6	0.68132 (12)	0.33927 (13)	0.05802 (13)	0.0437 (3)
C7	0.63629 (15)	0.24988 (14)	0.10278 (16)	0.0541 (4)
H7A	0.5972	0.2650	0.1522	0.065*
C8	0.64953 (19)	0.14210 (15)	0.07431 (19)	0.0656 (5)
H8A	0.6191	0.0841	0.1040	0.079*
C9	0.70845 (18)	0.11761 (15)	0.00090 (19)	0.0683 (5)
H9A	0.7161	0.0435	−0.0187	0.082*
C10	0.75491 (17)	0.20137 (15)	−0.04230 (17)	0.0592 (4)
H10A	0.7947	0.1839	−0.0904	0.071*
C11	0.74309 (13)	0.31434 (13)	−0.01470 (14)	0.0466 (4)
C12	0.78985 (14)	0.40492 (14)	−0.05799 (14)	0.0490 (4)
C13	0.77181 (13)	0.51312 (13)	−0.03431 (14)	0.0469 (4)
H13A	0.8026	0.5710	−0.0638	0.056*
C14	0.79036 (13)	0.73268 (12)	0.09176 (13)	0.0433 (3)
C15	0.80585 (16)	0.80610 (15)	0.01145 (16)	0.0573 (4)
H15A	0.7487	0.8125	−0.0664	0.069*
C16	0.90543 (18)	0.87111 (17)	0.04453 (19)	0.0682 (5)
H16A	0.9157	0.9203	−0.0102	0.082*
C17	0.98691 (16)	0.86051 (16)	0.15903 (19)	0.0629 (5)
C18	0.97531 (16)	0.78960 (18)	0.24158 (19)	0.0675 (5)
H18A	1.0327	0.7844	0.3194	0.081*
C19	0.87556 (15)	0.72490 (15)	0.20702 (16)	0.0567 (4)
H19A	0.8663	0.6758	0.2624	0.068*
C20	0.8921 (2)	0.46109 (19)	−0.1767 (2)	0.0726 (6)
H20A	0.9294	0.4291	−0.2248	0.109*
H20B	0.9463	0.5066	−0.1139	0.109*
H20C	0.8282	0.5064	−0.2271	0.109*
C21	0.60126 (14)	0.77220 (13)	0.17819 (14)	0.0479 (4)
H2N1	0.4932 (18)	0.510 (2)	0.2566 (19)	0.065 (6)*
H1N1	0.4912 (19)	0.642 (2)	0.251 (2)	0.073 (6)*

	U11	U22	U33	U12	U13	U23
F1	0.0660 (7)	0.0911 (9)	0.1290 (11)	−0.0335 (7)	0.0416 (7)	−0.0317 (8)
O1	0.0622 (7)	0.0378 (6)	0.0650 (7)	−0.0010 (5)	0.0391 (5)	−0.0020 (5)
O2	0.0845 (9)	0.0567 (8)	0.0838 (9)	0.0070 (6)	0.0566 (7)	−0.0061 (6)
N1	0.0703 (9)	0.0447 (8)	0.0724 (9)	−0.0022 (7)	0.0461 (8)	−0.0035 (7)
N2	0.0771 (10)	0.0491 (9)	0.0787 (10)	0.0032 (7)	0.0364 (8)	−0.0149 (7)
C1	0.0464 (7)	0.0404 (8)	0.0472 (8)	0.0021 (6)	0.0202 (6)	−0.0029 (6)
C2	0.0450 (7)	0.0399 (8)	0.0486 (8)	0.0018 (6)	0.0206 (6)	−0.0025 (6)
C3	0.0441 (7)	0.0378 (7)	0.0420 (7)	0.0014 (6)	0.0162 (6)	0.0007 (6)
C4	0.0429 (7)	0.0383 (7)	0.0411 (7)	0.0010 (5)	0.0155 (6)	−0.0019 (6)
C5	0.0444 (7)	0.0390 (7)	0.0440 (7)	0.0017 (6)	0.0185 (6)	−0.0025 (6)
C6	0.0433 (7)	0.0392 (8)	0.0443 (7)	0.0030 (6)	0.0131 (6)	−0.0014 (6)
C7	0.0605 (9)	0.0427 (8)	0.0615 (9)	0.0019 (7)	0.0269 (8)	0.0031 (7)
C8	0.0794 (12)	0.0396 (9)	0.0821 (12)	0.0006 (8)	0.0366 (10)	0.0040 (8)
C9	0.0804 (13)	0.0379 (9)	0.0857 (13)	0.0083 (8)	0.0322 (10)	−0.0052 (9)
C10	0.0653 (10)	0.0477 (9)	0.0664 (10)	0.0085 (8)	0.0283 (8)	−0.0084 (8)
C11	0.0460 (8)	0.0428 (8)	0.0471 (8)	0.0058 (6)	0.0146 (6)	−0.0042 (6)
C12	0.0494 (8)	0.0503 (9)	0.0499 (8)	0.0046 (7)	0.0227 (6)	−0.0053 (7)
C13	0.0506 (8)	0.0447 (8)	0.0488 (8)	−0.0014 (6)	0.0234 (6)	−0.0021 (6)
C14	0.0455 (7)	0.0367 (7)	0.0509 (8)	0.0004 (6)	0.0227 (6)	−0.0051 (6)
C15	0.0639 (10)	0.0539 (10)	0.0538 (9)	−0.0093 (8)	0.0232 (8)	0.0002 (7)
C16	0.0781 (13)	0.0595 (11)	0.0786 (12)	−0.0178 (9)	0.0434 (11)	−0.0029 (9)
C17	0.0534 (9)	0.0539 (10)	0.0883 (13)	−0.0127 (8)	0.0357 (9)	−0.0207 (9)
C18	0.0507 (10)	0.0709 (12)	0.0684 (11)	−0.0004 (8)	0.0107 (8)	−0.0124 (9)
C19	0.0566 (9)	0.0543 (10)	0.0550 (9)	−0.0006 (7)	0.0180 (7)	0.0028 (7)
C20	0.0858 (14)	0.0711 (13)	0.0848 (13)	−0.0002 (10)	0.0591 (12)	−0.0052 (10)
C21	0.0510 (8)	0.0442 (9)	0.0516 (8)	−0.0004 (6)	0.0237 (7)	−0.0039 (7)

F1—C17	1.364 (2)	C8—C9	1.396 (3)
O1—C1	1.3440 (18)	C8—H8A	0.9300
O1—C5	1.3979 (18)	C9—C10	1.364 (3)
O2—C12	1.3627 (19)	C9—H9A	0.9300
O2—C20	1.425 (2)	C10—C11	1.411 (2)
N1—C1	1.349 (2)	C10—H10A	0.9300
N1—H2N1	0.89 (2)	C11—C12	1.427 (2)
N1—H1N1	0.90 (2)	C12—C13	1.361 (2)
N2—C21	1.147 (2)	C13—H13A	0.9300
C1—C2	1.356 (2)	C14—C15	1.376 (2)
C2—C21	1.411 (2)	C14—C19	1.378 (2)
C2—C3	1.517 (2)	C15—C16	1.394 (3)
C3—C4	1.516 (2)	C15—H15A	0.9300
C3—C14	1.525 (2)	C16—C17	1.357 (3)
C3—H3A	0.9800	C16—H16A	0.9300
C4—C5	1.356 (2)	C17—C18	1.358 (3)
C4—C13	1.419 (2)	C18—C19	1.392 (3)
C5—C6	1.415 (2)	C18—H18A	0.9300
C6—C7	1.413 (2)	C19—H19A	0.9300
C6—C11	1.418 (2)	C20—H20A	0.9600
C7—C8	1.359 (3)	C20—H20B	0.9600
C7—H7A	0.9300	C20—H20C	0.9600
C1—O1—C5	118.35 (12)	C9—C10—H10A	119.7
C12—O2—C20	116.83 (14)	C11—C10—H10A	119.7
C1—N1—H2N1	115.9 (14)	C10—C11—C6	118.83 (15)
C1—N1—H1N1	113.3 (15)	C10—C11—C12	122.65 (15)
H2N1—N1—H1N1	124.2 (19)	C6—C11—C12	118.51 (14)
O1—C1—N1	110.73 (14)	C13—C12—O2	124.33 (15)
O1—C1—C2	123.18 (13)	C13—C12—C11	120.91 (14)
N1—C1—C2	126.07 (15)	O2—C12—C11	114.76 (14)
C1—C2—C21	117.63 (13)	C12—C13—C4	120.87 (15)
C1—C2—C3	123.24 (13)	C12—C13—H13A	119.6
C21—C2—C3	118.96 (13)	C4—C13—H13A	119.6
C4—C3—C2	109.01 (12)	C15—C14—C19	118.55 (15)
C4—C3—C14	112.07 (12)	C15—C14—C3	120.19 (14)
C2—C3—C14	112.70 (12)	C19—C14—C3	121.25 (14)
C4—C3—H3A	107.6	C14—C15—C16	121.29 (17)
C2—C3—H3A	107.6	C14—C15—H15A	119.4
C14—C3—H3A	107.6	C16—C15—H15A	119.4
C5—C4—C13	118.64 (14)	C17—C16—C15	118.01 (18)
C5—C4—C3	122.12 (13)	C17—C16—H16A	121.0
C13—C4—C3	119.19 (13)	C15—C16—H16A	121.0
C4—C5—O1	123.18 (13)	C16—C17—C18	122.84 (17)
C4—C5—C6	122.86 (14)	C16—C17—F1	118.04 (19)
O1—C5—C6	113.93 (13)	C18—C17—F1	119.11 (19)
C7—C6—C5	123.01 (14)	C17—C18—C19	118.47 (17)
C7—C6—C11	118.83 (14)	C17—C18—H18A	120.8
C5—C6—C11	118.13 (14)	C19—C18—H18A	120.8
C8—C7—C6	120.61 (17)	C14—C19—C18	120.84 (17)
C8—C7—H7A	119.7	C14—C19—H19A	119.6
C6—C7—H7A	119.7	C18—C19—H19A	119.6
C7—C8—C9	120.59 (18)	O2—C20—H20A	109.5
C7—C8—H8A	119.7	O2—C20—H20B	109.5
C9—C8—H8A	119.7	H20A—C20—H20B	109.5
C10—C9—C8	120.56 (16)	O2—C20—H20C	109.5
C10—C9—H9A	119.7	H20A—C20—H20C	109.5
C8—C9—H9A	119.7	H20B—C20—H20C	109.5
C9—C10—C11	120.55 (17)	N2—C21—C2	179.06 (19)
C5—O1—C1—N1	−176.40 (13)	C9—C10—C11—C12	−179.82 (17)
C5—O1—C1—C2	2.4 (2)	C7—C6—C11—C10	1.6 (2)
O1—C1—C2—C21	−178.96 (14)	C5—C6—C11—C10	−176.68 (14)
N1—C1—C2—C21	−0.3 (2)	C7—C6—C11—C12	−179.03 (14)
O1—C1—C2—C3	5.8 (2)	C5—C6—C11—C12	2.7 (2)
N1—C1—C2—C3	−175.55 (15)	C20—O2—C12—C13	−4.3 (3)
C1—C2—C3—C4	−10.64 (19)	C20—O2—C12—C11	175.28 (16)
C21—C2—C3—C4	174.21 (13)	C10—C11—C12—C13	176.76 (16)
C1—C2—C3—C14	−135.72 (15)	C6—C11—C12—C13	−2.6 (2)
C21—C2—C3—C14	49.13 (18)	C10—C11—C12—O2	−2.8 (2)
C2—C3—C4—C5	8.57 (19)	C6—C11—C12—O2	177.82 (14)
C14—C3—C4—C5	134.03 (14)	O2—C12—C13—C4	179.97 (14)
C2—C3—C4—C13	−173.90 (12)	C11—C12—C13—C4	0.4 (2)
C14—C3—C4—C13	−48.44 (17)	C5—C4—C13—C12	1.6 (2)
C13—C4—C5—O1	−179.35 (13)	C3—C4—C13—C12	−176.02 (14)
C3—C4—C5—O1	−1.8 (2)	C4—C3—C14—C15	106.56 (16)
C13—C4—C5—C6	−1.4 (2)	C2—C3—C14—C15	−130.03 (15)
C3—C4—C5—C6	176.10 (13)	C4—C3—C14—C19	−72.26 (18)
C1—O1—C5—C4	−4.4 (2)	C2—C3—C14—C19	51.14 (19)
C1—O1—C5—C6	177.49 (12)	C19—C14—C15—C16	0.4 (3)
C4—C5—C6—C7	−178.91 (15)	C3—C14—C15—C16	−178.43 (16)
O1—C5—C6—C7	−0.8 (2)	C14—C15—C16—C17	−0.4 (3)
C4—C5—C6—C11	−0.7 (2)	C15—C16—C17—C18	0.1 (3)
O1—C5—C6—C11	177.36 (12)	C15—C16—C17—F1	−178.75 (17)
C5—C6—C7—C8	176.61 (16)	C16—C17—C18—C19	0.1 (3)
C11—C6—C7—C8	−1.6 (2)	F1—C17—C18—C19	178.99 (16)
C6—C7—C8—C9	0.4 (3)	C15—C14—C19—C18	−0.2 (3)
C7—C8—C9—C10	0.8 (3)	C3—C14—C19—C18	178.68 (15)
C8—C9—C10—C11	−0.7 (3)	C17—C18—C19—C14	−0.1 (3)
C9—C10—C11—C6	−0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N1···N2i	0.89 (2)	2.17 (2)	3.054 (2)	175 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N1⋯N2i	0.89 (2)	2.17 (2)	3.054 (2)	175 (2)

Symmetry code: (i) .