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

In the title compound, C21H15BrN2O2, the 14 non-H atoms of the 4H-benzo[h]chromene fused-ring system are approximately coplanar (r.m.s. deviation = 0.129 Å). Within this system, the 4H-pyran ring adopts a flattened half-chair conformation with the methine C atom lying 0.281 (4) Å above the plane of the remaining atoms (r.m.s. deviation = 0.0446 Å). The bromo-benzene ring is almost perpendicular to the fused-ring system [dihedral angle = 85.34 (13)°]. In the crystal, supra-molecular layers parallel to (101) are sustained by amine-cyano N-H⋯N and amine-meth-oxy N-H⋯O hydrogen bonds. The layers stack with inter-actions of the type (bromo-benzene)C-H⋯π(outer-C6 ring of the fused-ring system) connecting them.

Related literature

For background to biologically active mol­ecules having the 4H-chromene or 4H-benzochromene residue, see: Sabry et al. (2011 ▶); Amin et al. (2010 ▶); Kidwai et al. (2010 ▶); Singh et al. (2010 ▶), For the structure of the fluoro derivative, see: Al-Dies et al. (2012 ▶).

Experimental

Crystal data

C21H15BrN2O2

M = 407.26

Monoclinic,

a = 6.0823 (7) Å

b = 16.6918 (18) Å

c = 17.7700 (16) Å

β = 93.646 (9)°

V = 1800.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.30 mm−1

T = 295 K

0.30 × 0.10 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.694, T max = 1.000

8976 measured reflections

4144 independent reflections

2250 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.150

S = 1.03

4144 reflections

243 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.78 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/S1600536813005461/hb7048sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813005461/hb7048Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813005461/hb7048Isup3.cml

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

C21H15BrN2O2	F(000) = 824
Mr = 407.26	Dx = 1.502 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1634 reflections
a = 6.0823 (7) Å	θ = 3.4–27.5°
b = 16.6918 (18) Å	µ = 2.30 mm−1
c = 17.7700 (16) Å	T = 295 K
β = 93.646 (9)°	Prism, yellow
V = 1800.4 (3) Å3	0.30 × 0.10 × 0.10 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	4144 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2250 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.041
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.4°
ω scan	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −15→21
Tmin = 0.694, Tmax = 1.000	l = −22→23
8976 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.057P)2 + 0.4428P] where P = (Fo2 + 2Fc2)/3
4144 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.71 e Å−3
2 restraints	Δρmin = −0.78 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br1	0.16537 (9)	0.98612 (4)	0.33868 (3)	0.0969 (3)
O1	0.0181 (4)	0.64654 (15)	0.64437 (13)	0.0504 (6)
O2	0.1773 (4)	0.92192 (15)	0.81237 (13)	0.0573 (7)
N1	0.1307 (6)	0.5382 (2)	0.5848 (2)	0.0582 (8)
H1	0.207 (7)	0.513 (3)	0.552 (2)	0.093 (17)*
H2	0.008 (4)	0.517 (3)	0.598 (3)	0.089 (17)*
N2	0.6286 (6)	0.5888 (2)	0.50299 (19)	0.0676 (9)
C1	0.0644 (5)	0.7191 (2)	0.68158 (16)	0.0393 (8)
C2	−0.0802 (5)	0.73721 (19)	0.73914 (16)	0.0375 (7)
C3	−0.2638 (6)	0.6894 (2)	0.75334 (18)	0.0453 (8)
H3	−0.2931	0.6437	0.7246	0.054*
C4	−0.3989 (6)	0.7094 (2)	0.80851 (19)	0.0520 (9)
H4	−0.5225	0.6783	0.8160	0.062*
C5	−0.3531 (6)	0.7762 (2)	0.8539 (2)	0.0547 (10)
H5	−0.4446	0.7887	0.8922	0.066*
C6	−0.1753 (6)	0.8235 (2)	0.84260 (18)	0.0500 (9)
H6	−0.1447	0.8672	0.8741	0.060*
C7	−0.0360 (5)	0.8068 (2)	0.78307 (17)	0.0405 (8)
C8	0.1447 (6)	0.8565 (2)	0.76620 (17)	0.0430 (8)
C9	0.2710 (5)	0.8382 (2)	0.70790 (18)	0.0446 (8)
H9	0.3847	0.8725	0.6964	0.054*
C10	0.2321 (5)	0.7680 (2)	0.66466 (16)	0.0390 (7)
C11	0.3774 (5)	0.7476 (2)	0.60075 (17)	0.0411 (8)
H11	0.5311	0.7556	0.6192	0.049*
C12	0.3481 (5)	0.6601 (2)	0.58086 (17)	0.0419 (8)
C13	0.1747 (6)	0.6157 (2)	0.60137 (18)	0.0455 (8)
C14	0.3613 (7)	0.9720 (2)	0.8004 (2)	0.0635 (11)
H14A	0.3620	1.0166	0.8345	0.095*
H14B	0.3509	0.9913	0.7494	0.095*
H14C	0.4949	0.9419	0.8092	0.095*
C15	0.5037 (6)	0.6215 (2)	0.53744 (19)	0.0479 (9)
C16	0.3287 (5)	0.8045 (2)	0.53448 (17)	0.0409 (8)
C17	0.1278 (6)	0.8030 (3)	0.4940 (2)	0.0577 (10)
H17	0.0232	0.7651	0.5058	0.069*
C18	0.0789 (6)	0.8566 (3)	0.4364 (2)	0.0627 (11)
H18	−0.0580	0.8551	0.4100	0.075*
C19	0.2331 (7)	0.9121 (2)	0.41810 (19)	0.0549 (10)
C20	0.4365 (6)	0.9136 (2)	0.4556 (2)	0.0581 (10)
H20	0.5421	0.9504	0.4423	0.070*
C21	0.4832 (6)	0.8596 (2)	0.51378 (19)	0.0505 (9)
H21	0.6214	0.8606	0.5394	0.061*

	U11	U22	U33	U12	U13	U23
Br1	0.1155 (5)	0.0841 (4)	0.0888 (4)	−0.0019 (3)	−0.0114 (3)	0.0431 (3)
O1	0.0523 (13)	0.0429 (15)	0.0572 (13)	−0.0032 (11)	0.0139 (11)	−0.0239 (12)
O2	0.0760 (17)	0.0383 (15)	0.0578 (14)	−0.0057 (13)	0.0074 (12)	−0.0170 (12)
N1	0.063 (2)	0.0407 (19)	0.073 (2)	−0.0020 (17)	0.0213 (18)	−0.0202 (17)
N2	0.079 (2)	0.054 (2)	0.073 (2)	0.0104 (19)	0.0324 (18)	0.0012 (18)
C1	0.0484 (19)	0.0320 (18)	0.0372 (16)	0.0036 (15)	0.0016 (15)	−0.0055 (14)
C2	0.0478 (18)	0.0313 (17)	0.0333 (15)	0.0080 (15)	0.0011 (14)	−0.0027 (14)
C3	0.056 (2)	0.0330 (19)	0.0466 (19)	0.0026 (16)	0.0040 (16)	0.0014 (16)
C4	0.056 (2)	0.049 (2)	0.053 (2)	0.0027 (18)	0.0115 (18)	0.0047 (18)
C5	0.066 (2)	0.050 (2)	0.050 (2)	0.008 (2)	0.0177 (18)	−0.0008 (18)
C6	0.070 (2)	0.039 (2)	0.0417 (18)	0.0098 (19)	0.0078 (17)	−0.0074 (16)
C7	0.0516 (19)	0.0335 (18)	0.0361 (16)	0.0076 (16)	−0.0003 (15)	0.0001 (14)
C8	0.057 (2)	0.0304 (18)	0.0404 (17)	0.0094 (16)	−0.0021 (16)	−0.0060 (15)
C9	0.0510 (19)	0.0344 (19)	0.0482 (19)	0.0006 (16)	0.0011 (16)	−0.0017 (15)
C10	0.0486 (18)	0.0333 (18)	0.0353 (16)	0.0043 (16)	0.0041 (14)	−0.0009 (14)
C11	0.0445 (18)	0.040 (2)	0.0390 (17)	0.0029 (16)	0.0023 (14)	−0.0008 (15)
C12	0.0511 (19)	0.0356 (19)	0.0397 (17)	0.0065 (16)	0.0087 (15)	0.0006 (15)
C13	0.056 (2)	0.041 (2)	0.0400 (17)	0.0097 (18)	0.0032 (16)	−0.0114 (16)
C14	0.066 (2)	0.041 (2)	0.083 (3)	−0.005 (2)	0.000 (2)	−0.016 (2)
C15	0.063 (2)	0.037 (2)	0.0444 (18)	0.0100 (18)	0.0124 (17)	0.0034 (16)
C16	0.0457 (18)	0.0371 (19)	0.0399 (17)	0.0018 (16)	0.0032 (15)	−0.0047 (15)
C17	0.052 (2)	0.062 (3)	0.059 (2)	−0.0083 (19)	−0.0018 (18)	0.013 (2)
C18	0.057 (2)	0.071 (3)	0.059 (2)	−0.005 (2)	−0.0058 (19)	0.015 (2)
C19	0.076 (3)	0.043 (2)	0.0458 (19)	0.004 (2)	−0.0022 (19)	0.0060 (17)
C20	0.066 (2)	0.047 (2)	0.062 (2)	−0.014 (2)	0.008 (2)	0.0042 (19)
C21	0.051 (2)	0.047 (2)	0.053 (2)	−0.0032 (18)	−0.0037 (17)	−0.0006 (18)

Br1—C19	1.901 (3)	C8—C9	1.363 (5)
O1—C13	1.360 (4)	C9—C10	1.413 (4)
O1—C1	1.399 (4)	C9—H9	0.9300
O2—C8	1.372 (4)	C10—C11	1.521 (4)
O2—C14	1.423 (5)	C11—C12	1.510 (5)
N1—C13	1.349 (5)	C11—C16	1.528 (4)
N1—H1	0.877 (10)	C11—H11	0.9800
N1—H2	0.874 (10)	C12—C13	1.357 (5)
N2—C15	1.144 (4)	C12—C15	1.414 (5)
C1—C10	1.355 (5)	C14—H14A	0.9600
C1—C2	1.423 (4)	C14—H14B	0.9600
C2—C3	1.408 (5)	C14—H14C	0.9600
C2—C7	1.416 (4)	C16—C17	1.378 (5)
C3—C4	1.360 (5)	C16—C21	1.382 (5)
C3—H3	0.9300	C17—C18	1.378 (5)
C4—C5	1.395 (5)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.372 (5)
C5—C6	1.364 (5)	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.368 (5)
C6—C7	1.424 (5)	C20—C21	1.387 (5)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.424 (5)	C21—H21	0.9300
C13—O1—C1	117.8 (3)	C12—C11—C16	114.0 (3)
C8—O2—C14	117.6 (3)	C10—C11—C16	110.1 (3)
C13—N1—H1	120 (3)	C12—C11—H11	107.8
C13—N1—H2	120 (3)	C10—C11—H11	107.8
H1—N1—H2	118 (5)	C16—C11—H11	107.8
C10—C1—O1	123.2 (3)	C13—C12—C15	117.1 (3)
C10—C1—C2	122.6 (3)	C13—C12—C11	123.2 (3)
O1—C1—C2	114.1 (3)	C15—C12—C11	119.7 (3)
C3—C2—C7	119.4 (3)	N1—C13—C12	127.7 (3)
C3—C2—C1	122.8 (3)	N1—C13—O1	110.5 (3)
C7—C2—C1	117.8 (3)	C12—C13—O1	121.9 (3)
C4—C3—C2	120.9 (3)	O2—C14—H14A	109.5
C4—C3—H3	119.6	O2—C14—H14B	109.5
C2—C3—H3	119.6	H14A—C14—H14B	109.5
C3—C4—C5	120.3 (4)	O2—C14—H14C	109.5
C3—C4—H4	119.8	H14A—C14—H14C	109.5
C5—C4—H4	119.8	H14B—C14—H14C	109.5
C6—C5—C4	120.6 (3)	N2—C15—C12	178.6 (4)
C6—C5—H5	119.7	C17—C16—C21	117.9 (3)
C4—C5—H5	119.7	C17—C16—C11	120.8 (3)
C5—C6—C7	120.7 (3)	C21—C16—C11	121.2 (3)
C5—C6—H6	119.7	C18—C17—C16	121.2 (4)
C7—C6—H6	119.7	C18—C17—H17	119.4
C2—C7—C8	119.0 (3)	C16—C17—H17	119.4
C2—C7—C6	118.0 (3)	C19—C18—C17	119.8 (3)
C8—C7—C6	123.1 (3)	C19—C18—H18	120.1
C9—C8—O2	124.5 (3)	C17—C18—H18	120.1
C9—C8—C7	120.6 (3)	C20—C19—C18	120.5 (3)
O2—C8—C7	114.9 (3)	C20—C19—Br1	119.7 (3)
C8—C9—C10	121.1 (3)	C18—C19—Br1	119.7 (3)
C8—C9—H9	119.5	C19—C20—C21	119.1 (4)
C10—C9—H9	119.5	C19—C20—H20	120.4
C1—C10—C9	118.8 (3)	C21—C20—H20	120.4
C1—C10—C11	120.8 (3)	C16—C21—C20	121.4 (3)
C9—C10—C11	120.4 (3)	C16—C21—H21	119.3
C12—C11—C10	109.0 (3)	C20—C21—H21	119.3
C13—O1—C1—C10	14.6 (4)	C8—C9—C10—C11	−178.8 (3)
C13—O1—C1—C2	−165.3 (3)	C1—C10—C11—C12	−17.0 (4)
C10—C1—C2—C3	175.4 (3)	C9—C10—C11—C12	162.5 (3)
O1—C1—C2—C3	−4.7 (4)	C1—C10—C11—C16	108.7 (3)
C10—C1—C2—C7	−4.1 (4)	C9—C10—C11—C16	−71.8 (4)
O1—C1—C2—C7	175.8 (3)	C10—C11—C12—C13	17.6 (4)
C7—C2—C3—C4	0.1 (5)	C16—C11—C12—C13	−105.8 (3)
C1—C2—C3—C4	−179.4 (3)	C10—C11—C12—C15	−163.8 (3)
C2—C3—C4—C5	−2.3 (5)	C16—C11—C12—C15	72.8 (4)
C3—C4—C5—C6	1.5 (5)	C15—C12—C13—N1	−0.6 (5)
C4—C5—C6—C7	1.6 (5)	C11—C12—C13—N1	178.1 (3)
C3—C2—C7—C8	−177.4 (3)	C15—C12—C13—O1	178.7 (3)
C1—C2—C7—C8	2.1 (4)	C11—C12—C13—O1	−2.7 (5)
C3—C2—C7—C6	2.8 (4)	C1—O1—C13—N1	165.0 (3)
C1—C2—C7—C6	−177.7 (3)	C1—O1—C13—C12	−14.4 (4)
C5—C6—C7—C2	−3.7 (5)	C12—C11—C16—C17	56.2 (4)
C5—C6—C7—C8	176.6 (3)	C10—C11—C16—C17	−66.6 (4)
C14—O2—C8—C9	−2.8 (5)	C12—C11—C16—C21	−124.5 (3)
C14—O2—C8—C7	177.4 (3)	C10—C11—C16—C21	112.6 (4)
C2—C7—C8—C9	1.1 (5)	C21—C16—C17—C18	−2.2 (6)
C6—C7—C8—C9	−179.1 (3)	C11—C16—C17—C18	177.0 (3)
C2—C7—C8—O2	−179.0 (3)	C16—C17—C18—C19	0.7 (6)
C6—C7—C8—O2	0.7 (4)	C17—C18—C19—C20	1.3 (6)
O2—C8—C9—C10	177.5 (3)	C17—C18—C19—Br1	−179.9 (3)
C7—C8—C9—C10	−2.6 (5)	C18—C19—C20—C21	−1.7 (6)
O1—C1—C10—C9	−177.2 (3)	Br1—C19—C20—C21	179.6 (3)
C2—C1—C10—C9	2.7 (5)	C17—C16—C21—C20	1.9 (5)
O1—C1—C10—C11	2.3 (5)	C11—C16—C21—C20	−177.3 (3)
C2—C1—C10—C11	−177.8 (3)	C19—C20—C21—C16	0.0 (6)
C8—C9—C10—C1	0.7 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2i	0.88 (1)	2.22 (2)	3.059 (5)	159 (4)
N1—H2···O2ii	0.87 (3)	2.56 (5)	3.324 (4)	147 (4)
C18—H18···Cg1iii	0.93	2.87	3.528 (4)	129

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2i	0.88 (1)	2.22 (2)	3.059 (5)	159 (4)
N1—H2⋯O2ii	0.87 (3)	2.56 (5)	3.324 (4)	147 (4)
C18—H18⋯Cg1iii	0.93	2.87	3.528 (4)	129

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