3-Amino-1-(4-fluoro-phen-yl)-8-meth-oxy-1H-benzo[f]chromene-2-carbonitrile.

The title compound, C21H15FN2O2, features an approximately planar 1H-benzo[f]chromene fused-ring system (r.m.s. deviation for the 14 non-H atoms = 0.052 Å), with the fluoro-benzene ring being almost perpendicular to this [dihedral angle = 85.30 (7) °]. The furan ring has a flattened half-chair conformation, with the methine C atom deviating by 0.132 (2) Å from the plane of the remaining atoms (r.m.s. deviation = 0.0107 Å). In the crystal, inversion dimers are formed via pairs of amine-cyano N-H⋯N hydrogen bonds. The dimers are connected into a three-dimensional architecture by C-H⋯N(cyano), C-H⋯π and π-π [inter-centroid distance = 3.6671 (10) Å] inter-actions.

Related literature

For background and various applications of benzo- and naphtho­pyran- derivatives, see: Bonsignore et al. (1993 ▶); Hafez et al. (1987 ▶). For background to the chemistry and biological activity of 4H-pyran derivatives, see: El-Agrody et al. (2011 ▶); Sabry et al. (2011 ▶). For related structures, see: Wang et al. (2008 ▶); Shekhar et al. (2012 ▶); Amr et al. (2013 ▶).

Experimental

Crystal data

C21H15FN2O2

M = 346.35

Triclinic,

a = 8.9672 (7) Å

b = 10.4365 (8) Å

c = 10.9058 (8) Å

α = 103.063 (7)°

β = 106.859 (7)°

γ = 111.399 (8)°

V = 844.01 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 295 K

0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.722, T max = 1.000

7109 measured reflections

3902 independent reflections

2716 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.138

S = 1.05

3902 reflections

244 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681300545X/hb7047sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300545X/hb7047Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300545X/hb7047Isup3.cml

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

C21H15FN2O2	Z = 2
Mr = 346.35	F(000) = 360
Triclinic, P1	Dx = 1.363 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9672 (7) Å	Cell parameters from 2078 reflections
b = 10.4365 (8) Å	θ = 3.2–27.5°
c = 10.9058 (8) Å	µ = 0.10 mm−1
α = 103.063 (7)°	T = 295 K
β = 106.859 (7)°	Prism, light-brown
γ = 111.399 (8)°	0.30 × 0.20 × 0.10 mm
V = 844.01 (11) Å3

Agilent SuperNova Dual diffractometer with an Atlas detector	3902 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2716 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.2°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→12
Tmin = 0.722, Tmax = 1.000	l = −14→13
7109 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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.0568P)2 + 0.1033P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3902 reflections	Δρmax = 0.20 e Å−3
244 parameters	Δρmin = −0.16 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: 0.031 (4)

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	0.65107 (18)	1.02622 (15)	1.19074 (13)	0.0888 (4)
O1	0.93475 (14)	0.70759 (13)	0.65915 (12)	0.0489 (3)
O2	0.08769 (17)	0.77609 (16)	0.33736 (14)	0.0685 (4)
N1	1.0769 (2)	0.62403 (19)	0.79544 (18)	0.0538 (4)
N2	0.8096 (2)	0.4809 (2)	0.97164 (18)	0.0655 (5)
C1	0.7901 (2)	0.72705 (17)	0.59527 (16)	0.0416 (4)
C2	0.8067 (2)	0.7931 (2)	0.49837 (18)	0.0511 (4)
H2A	0.9069	0.8184	0.4806	0.061*
C3	0.6756 (2)	0.8201 (2)	0.43063 (18)	0.0518 (4)
H3	0.6879	0.8664	0.3681	0.062*
C4	0.5202 (2)	0.77860 (17)	0.45373 (15)	0.0428 (4)
C5	0.3816 (2)	0.80453 (18)	0.38152 (17)	0.0489 (4)
H5	0.3935	0.8522	0.3199	0.059*
C6	0.2310 (2)	0.75979 (19)	0.40231 (17)	0.0493 (4)
C7	0.2135 (2)	0.6892 (2)	0.49622 (17)	0.0503 (4)
H7	0.1100	0.6585	0.5094	0.060*
C8	0.3452 (2)	0.66482 (18)	0.56843 (16)	0.0444 (4)
H8	0.3307	0.6182	0.6305	0.053*
C9	0.50492 (19)	0.70961 (16)	0.55037 (15)	0.0391 (4)
C10	0.64573 (19)	0.68629 (16)	0.62547 (15)	0.0370 (3)
C11	0.63936 (18)	0.62664 (16)	0.73856 (15)	0.0370 (3)
H11	0.5315	0.5327	0.7006	0.044*
C12	0.79503 (19)	0.59719 (16)	0.78873 (15)	0.0396 (4)
C13	0.93049 (19)	0.63973 (17)	0.75081 (16)	0.0411 (4)
C14	0.0952 (3)	0.8443 (3)	0.2389 (2)	0.0773 (6)
H14A	−0.0123	0.8498	0.2013	0.116*
H14B	0.1107	0.7867	0.1661	0.116*
H14C	0.1921	0.9424	0.2829	0.116*
C15	0.63823 (18)	0.73347 (16)	0.85967 (15)	0.0376 (3)
C16	0.7538 (2)	0.88289 (19)	0.91135 (18)	0.0509 (4)
H16	0.8299	0.9174	0.8704	0.061*
C17	0.7591 (3)	0.9820 (2)	1.0222 (2)	0.0614 (5)
H17	0.8370	1.0825	1.0558	0.074*
C18	0.6474 (2)	0.9291 (2)	1.08140 (18)	0.0567 (5)
C19	0.5336 (2)	0.7830 (2)	1.03607 (19)	0.0614 (5)
H19	0.4600	0.7495	1.0792	0.074*
C20	0.5293 (2)	0.6848 (2)	0.92405 (17)	0.0507 (4)
H20	0.4517	0.5844	0.8918	0.061*
C21	0.80450 (19)	0.53183 (18)	0.88874 (17)	0.0453 (4)
H1	1.096 (3)	0.588 (2)	0.861 (2)	0.065 (6)*
H2	1.158 (3)	0.672 (2)	0.772 (2)	0.063 (6)*

	U11	U22	U33	U12	U13	U23
F1	0.1109 (10)	0.0868 (9)	0.0662 (8)	0.0463 (7)	0.0490 (7)	0.0064 (7)
O1	0.0466 (6)	0.0623 (7)	0.0539 (7)	0.0294 (5)	0.0262 (5)	0.0343 (6)
O2	0.0705 (8)	0.0905 (10)	0.0680 (9)	0.0550 (8)	0.0249 (7)	0.0441 (8)
N1	0.0463 (9)	0.0631 (10)	0.0626 (10)	0.0293 (7)	0.0230 (7)	0.0338 (8)
N2	0.0573 (9)	0.0839 (12)	0.0741 (11)	0.0350 (8)	0.0293 (8)	0.0542 (10)
C1	0.0456 (8)	0.0443 (9)	0.0396 (8)	0.0234 (7)	0.0177 (7)	0.0188 (7)
C2	0.0538 (10)	0.0611 (11)	0.0502 (10)	0.0272 (8)	0.0289 (8)	0.0301 (9)
C3	0.0615 (10)	0.0584 (11)	0.0460 (9)	0.0287 (8)	0.0257 (8)	0.0306 (8)
C4	0.0527 (9)	0.0411 (9)	0.0357 (8)	0.0234 (7)	0.0165 (7)	0.0155 (7)
C5	0.0637 (11)	0.0474 (10)	0.0396 (9)	0.0299 (8)	0.0178 (8)	0.0203 (7)
C6	0.0575 (10)	0.0528 (10)	0.0426 (9)	0.0345 (8)	0.0152 (8)	0.0176 (8)
C7	0.0516 (9)	0.0617 (11)	0.0456 (9)	0.0328 (8)	0.0210 (8)	0.0210 (8)
C8	0.0515 (9)	0.0515 (10)	0.0376 (8)	0.0281 (7)	0.0201 (7)	0.0194 (7)
C9	0.0466 (8)	0.0376 (8)	0.0320 (8)	0.0205 (6)	0.0146 (6)	0.0115 (6)
C10	0.0445 (8)	0.0350 (8)	0.0318 (7)	0.0190 (6)	0.0153 (6)	0.0124 (6)
C11	0.0380 (8)	0.0355 (8)	0.0364 (8)	0.0154 (6)	0.0142 (6)	0.0157 (6)
C12	0.0442 (8)	0.0377 (8)	0.0383 (8)	0.0195 (6)	0.0159 (6)	0.0168 (7)
C13	0.0443 (8)	0.0390 (8)	0.0399 (8)	0.0205 (7)	0.0150 (7)	0.0156 (7)
C14	0.0899 (15)	0.0878 (16)	0.0666 (13)	0.0557 (13)	0.0184 (11)	0.0427 (12)
C15	0.0386 (8)	0.0412 (8)	0.0351 (8)	0.0187 (6)	0.0145 (6)	0.0181 (6)
C16	0.0589 (10)	0.0453 (10)	0.0502 (10)	0.0188 (8)	0.0305 (8)	0.0192 (8)
C17	0.0745 (12)	0.0440 (10)	0.0576 (11)	0.0199 (9)	0.0313 (10)	0.0123 (9)
C18	0.0660 (11)	0.0633 (12)	0.0422 (9)	0.0335 (9)	0.0254 (8)	0.0117 (9)
C19	0.0593 (11)	0.0734 (13)	0.0491 (10)	0.0220 (9)	0.0328 (9)	0.0195 (9)
C20	0.0501 (9)	0.0492 (10)	0.0450 (9)	0.0129 (7)	0.0224 (7)	0.0172 (8)
C21	0.0399 (8)	0.0488 (9)	0.0491 (9)	0.0212 (7)	0.0159 (7)	0.0234 (8)

F1—C18	1.362 (2)	C8—C9	1.423 (2)
O1—C13	1.3508 (19)	C8—H8	0.9300
O1—C1	1.3933 (18)	C9—C10	1.428 (2)
O2—C6	1.3665 (19)	C10—C11	1.508 (2)
O2—C14	1.419 (2)	C11—C12	1.513 (2)
N1—C13	1.345 (2)	C11—C15	1.529 (2)
N1—H1	0.89 (2)	C11—H11	0.9800
N1—H2	0.87 (2)	C12—C13	1.351 (2)
N2—C21	1.146 (2)	C12—C21	1.410 (2)
C1—C10	1.369 (2)	C14—H14A	0.9600
C1—C2	1.400 (2)	C14—H14B	0.9600
C2—C3	1.356 (2)	C14—H14C	0.9600
C2—H2A	0.9300	C15—C20	1.379 (2)
C3—C4	1.416 (2)	C15—C16	1.381 (2)
C3—H3	0.9300	C16—C17	1.379 (2)
C4—C9	1.415 (2)	C16—H16	0.9300
C4—C5	1.418 (2)	C17—C18	1.363 (3)
C5—C6	1.364 (2)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.357 (3)
C6—C7	1.402 (2)	C19—C20	1.387 (2)
C7—C8	1.361 (2)	C19—H19	0.9300
C7—H7	0.9300	C20—H20	0.9300
C13—O1—C1	118.99 (12)	C10—C11—C15	111.81 (12)
C6—O2—C14	117.43 (15)	C12—C11—C15	109.77 (12)
C13—N1—H1	120.1 (13)	C10—C11—H11	108.5
C13—N1—H2	114.8 (13)	C12—C11—H11	108.5
H1—N1—H2	123.1 (19)	C15—C11—H11	108.5
C10—C1—O1	122.98 (14)	C13—C12—C21	118.53 (14)
C10—C1—C2	123.20 (15)	C13—C12—C11	123.71 (14)
O1—C1—C2	113.82 (13)	C21—C12—C11	117.57 (13)
C3—C2—C1	119.46 (15)	N1—C13—O1	110.25 (14)
C3—C2—H2A	120.3	N1—C13—C12	127.35 (16)
C1—C2—H2A	120.3	O1—C13—C12	122.39 (14)
C2—C3—C4	120.94 (16)	O2—C14—H14A	109.5
C2—C3—H3	119.5	O2—C14—H14B	109.5
C4—C3—H3	119.5	H14A—C14—H14B	109.5
C9—C4—C5	120.25 (15)	O2—C14—H14C	109.5
C9—C4—C3	118.64 (15)	H14A—C14—H14C	109.5
C5—C4—C3	121.11 (16)	H14B—C14—H14C	109.5
C6—C5—C4	120.17 (16)	C20—C15—C16	118.03 (15)
C6—C5—H5	119.9	C20—C15—C11	121.98 (14)
C4—C5—H5	119.9	C16—C15—C11	119.93 (13)
O2—C6—C5	125.58 (17)	C17—C16—C15	121.56 (16)
O2—C6—C7	114.43 (15)	C17—C16—H16	119.2
C5—C6—C7	119.99 (15)	C15—C16—H16	119.2
C8—C7—C6	121.13 (16)	C18—C17—C16	118.34 (17)
C8—C7—H7	119.4	C18—C17—H17	120.8
C6—C7—H7	119.4	C16—C17—H17	120.8
C7—C8—C9	120.94 (16)	C19—C18—F1	118.80 (17)
C7—C8—H8	119.5	C19—C18—C17	122.38 (16)
C9—C8—H8	119.5	F1—C18—C17	118.82 (17)
C4—C9—C10	120.40 (14)	C18—C19—C20	118.59 (16)
C4—C9—C8	117.51 (14)	C18—C19—H19	120.7
C10—C9—C8	122.09 (15)	C20—C19—H19	120.7
C1—C10—C9	117.30 (14)	C15—C20—C19	121.09 (16)
C1—C10—C11	121.40 (14)	C15—C20—H20	119.5
C9—C10—C11	121.23 (13)	C19—C20—H20	119.5
C10—C11—C12	109.72 (12)	N2—C21—C12	177.89 (18)
C13—O1—C1—C10	3.0 (2)	C8—C9—C10—C11	−6.2 (2)
C13—O1—C1—C2	−177.54 (13)	C1—C10—C11—C12	−9.55 (19)
C10—C1—C2—C3	0.5 (3)	C9—C10—C11—C12	173.70 (12)
O1—C1—C2—C3	−179.02 (15)	C1—C10—C11—C15	112.49 (15)
C1—C2—C3—C4	−1.7 (3)	C9—C10—C11—C15	−64.26 (17)
C2—C3—C4—C9	0.7 (3)	C10—C11—C12—C13	9.0 (2)
C2—C3—C4—C5	−179.04 (16)	C15—C11—C12—C13	−114.21 (16)
C9—C4—C5—C6	−1.6 (2)	C10—C11—C12—C21	−176.02 (13)
C3—C4—C5—C6	178.06 (15)	C15—C11—C12—C21	60.74 (17)
C14—O2—C6—C5	0.5 (3)	C1—O1—C13—N1	176.64 (13)
C14—O2—C6—C7	−178.87 (16)	C1—O1—C13—C12	−3.7 (2)
C4—C5—C6—O2	−178.78 (15)	C21—C12—C13—N1	1.8 (3)
C4—C5—C6—C7	0.6 (3)	C11—C12—C13—N1	176.66 (15)
O2—C6—C7—C8	179.82 (15)	C21—C12—C13—O1	−177.78 (14)
C5—C6—C7—C8	0.4 (3)	C11—C12—C13—O1	−2.9 (2)
C6—C7—C8—C9	−0.3 (3)	C10—C11—C15—C20	137.00 (15)
C5—C4—C9—C10	−178.61 (13)	C12—C11—C15—C20	−100.99 (17)
C3—C4—C9—C10	1.7 (2)	C10—C11—C15—C16	−45.73 (19)
C5—C4—C9—C8	1.6 (2)	C12—C11—C15—C16	76.27 (18)
C3—C4—C9—C8	−178.05 (14)	C20—C15—C16—C17	−1.3 (3)
C7—C8—C9—C4	−0.7 (2)	C11—C15—C16—C17	−178.64 (16)
C7—C8—C9—C10	179.57 (14)	C15—C16—C17—C18	0.4 (3)
O1—C1—C10—C9	−178.74 (13)	C16—C17—C18—C19	0.8 (3)
C2—C1—C10—C9	1.8 (2)	C16—C17—C18—F1	−179.78 (17)
O1—C1—C10—C11	4.4 (2)	F1—C18—C19—C20	179.49 (17)
C2—C1—C10—C11	−175.07 (14)	C17—C18—C19—C20	−1.1 (3)
C4—C9—C10—C1	−2.9 (2)	C16—C15—C20—C19	1.0 (3)
C8—C9—C10—C1	176.87 (14)	C11—C15—C20—C19	178.28 (16)
C4—C9—C10—C11	174.03 (13)	C18—C19—C20—C15	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2i	0.89 (2)	2.16 (2)	3.043 (2)	170.0 (18)
C19—H19···N2ii	0.93	2.51	3.259 (3)	138
C11—H11···Cg1iii	0.98	2.90	3.7084 (17)	141
C14—H14C···Cg1iv	0.96	2.92	3.772 (3)	148

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C4,C9,C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2i	0.89 (2)	2.16 (2)	3.043 (2)	170.0 (18)
C19—H19⋯N2ii	0.93	2.51	3.259 (3)	138
C11—H11⋯Cg1iii	0.98	2.90	3.7084 (17)	141
C14—H14C⋯Cg1iv	0.96	2.92	3.772 (3)	148

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