3,6-Dibromo-7-ethyl-amino-4-methyl-2H-chromen-2-one.

In title compound, C(12)H(11)Br(2)NO(2), the coumarin ring system is almost planar, the two rings being inclined to one another by 1.40 (15)°. There are two short intra-molecular inter-actions (N-H⋯Br and C-H⋯Br) involving the Br atoms. In the crystal, mol-ecules stack along the a-axis direction via π-π inter-actions; the centroid-centroid distances vary from 3.6484 (19) to 3.7942 (19) Å.

Related literature

For the synthesis of the title compound, see: Belluti et al. (2010 ▶). For geometrical details of a coumarin compound, see: Kruszynski et al. (2005 ▶).

Experimental

Crystal data

C12H11Br2NO2

M = 361.04

Triclinic,

a = 7.5795 (9) Å

b = 7.6839 (9) Å

c = 11.2610 (14) Å

α = 93.628 (2)°

β = 98.288 (3)°

γ = 102.626 (3)°

V = 630.24 (13) Å3

Z = 2

Mo Kα radiation

μ = 6.42 mm−1

T = 293 K

0.20 × 0.18 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.360, T max = 0.446

3658 measured reflections

2314 independent reflections

1928 reflections with I > 2σ(I)

R int = 0.023

3 standard reflections every 200 reflections intensity decay 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.097

S = 1.00

2314 reflections

160 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201077X/su2385sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201077X/su2385Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681201077X/su2385Isup3.cml

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

C12H11Br2NO2	Z = 2
Mr = 361.04	F(000) = 352
Triclinic, P1	Dx = 1.903 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5795 (9) Å	Cell parameters from 1771 reflections
b = 7.6839 (9) Å	θ = 2.7–26.5°
c = 11.2610 (14) Å	µ = 6.42 mm−1
α = 93.628 (2)°	T = 293 K
β = 98.288 (3)°	Block, colourless
γ = 102.626 (3)°	0.20 × 0.18 × 0.15 mm
V = 630.24 (13) Å3

Enraf–Nonius CAD-4 diffractometer	1928 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 25.5°, θmin = 1.8°
ω/2θ scans	h = −9→8
Absorption correction: ψ scan (North et al., 1968)	k = −8→9
Tmin = 0.360, Tmax = 0.446	l = −11→13
3658 measured reflections	3 standard reflections every 200 reflections
2314 independent reflections	intensity decay: 1%

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0633P)2 + 0.0665P] where P = (Fo2 + 2Fc2)/3
2314 reflections	(Δ/σ)max = 0.001
160 parameters	Δρmax = 0.51 e Å−3
1 restraint	Δρmin = −0.42 e Å−3

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
Br1	0.93608 (5)	0.72412 (5)	0.21480 (3)	0.05088 (16)
Br2	0.64459 (6)	0.54212 (6)	0.87739 (3)	0.05501 (16)
O1	0.5330 (4)	0.1746 (4)	0.7375 (2)	0.0561 (7)
O2	0.6172 (3)	0.2336 (3)	0.5627 (2)	0.0410 (6)
N1	0.7998 (4)	0.3167 (4)	0.1806 (3)	0.0403 (7)
C1	0.6005 (5)	0.2886 (5)	0.6787 (3)	0.0414 (8)
C2	0.6637 (5)	0.4800 (5)	0.7146 (3)	0.0388 (7)
C3	0.7310 (4)	0.6008 (4)	0.6420 (3)	0.0358 (7)
C4	0.7489 (4)	0.5355 (4)	0.5224 (3)	0.0335 (7)
C5	0.6917 (4)	0.3514 (4)	0.4864 (3)	0.0334 (7)
C6	0.7056 (4)	0.2766 (4)	0.3743 (3)	0.0352 (7)
H6	0.6655	0.1534	0.3547	0.042*
C7	0.7792 (4)	0.3845 (4)	0.2908 (3)	0.0331 (7)
C8	0.8355 (4)	0.5712 (4)	0.3261 (3)	0.0355 (7)
C9	0.8197 (4)	0.6442 (4)	0.4371 (3)	0.0358 (7)
H9	0.8565	0.7677	0.4561	0.043*
C10	0.7902 (5)	0.7994 (5)	0.6800 (3)	0.0480 (9)
H10A	0.7510	0.8247	0.7552	0.072*
H10B	0.7361	0.8632	0.6195	0.072*
H10C	0.9213	0.8366	0.6894	0.072*
C11	0.7252 (5)	0.1281 (5)	0.1345 (3)	0.0442 (8)
H11A	0.5925	0.1010	0.1252	0.053*
H11B	0.7695	0.0515	0.1913	0.053*
C12	0.7831 (6)	0.0925 (6)	0.0148 (4)	0.0589 (10)
H12A	0.9142	0.1137	0.0251	0.088*
H12B	0.7420	0.1709	−0.0405	0.088*
H12C	0.7300	−0.0298	−0.0166	0.088*
H1	0.848 (4)	0.380 (4)	0.128 (2)	0.036 (9)*

	U11	U22	U33	U12	U13	U23
Br1	0.0641 (3)	0.0348 (2)	0.0574 (3)	0.00657 (16)	0.02514 (19)	0.01385 (16)
Br2	0.0732 (3)	0.0580 (3)	0.0363 (2)	0.0195 (2)	0.01301 (18)	−0.00175 (17)
O1	0.0735 (18)	0.0491 (16)	0.0446 (15)	0.0014 (13)	0.0231 (13)	0.0100 (12)
O2	0.0551 (14)	0.0292 (11)	0.0361 (13)	0.0006 (10)	0.0133 (11)	0.0011 (9)
N1	0.0510 (17)	0.0316 (14)	0.0416 (16)	0.0079 (12)	0.0197 (14)	0.0049 (12)
C1	0.0445 (18)	0.0410 (19)	0.0381 (19)	0.0082 (15)	0.0064 (15)	0.0061 (15)
C2	0.0437 (18)	0.0423 (18)	0.0297 (17)	0.0106 (14)	0.0041 (14)	−0.0011 (14)
C3	0.0338 (16)	0.0327 (16)	0.0396 (18)	0.0092 (13)	0.0017 (14)	−0.0031 (13)
C4	0.0334 (15)	0.0308 (16)	0.0348 (17)	0.0063 (12)	0.0039 (13)	0.0004 (13)
C5	0.0351 (16)	0.0281 (15)	0.0368 (17)	0.0067 (12)	0.0048 (13)	0.0057 (13)
C6	0.0406 (17)	0.0258 (15)	0.0386 (18)	0.0070 (12)	0.0067 (14)	0.0013 (13)
C7	0.0320 (15)	0.0285 (15)	0.0394 (18)	0.0078 (12)	0.0072 (13)	0.0014 (13)
C8	0.0366 (16)	0.0303 (16)	0.0389 (18)	0.0045 (12)	0.0067 (14)	0.0089 (13)
C9	0.0365 (16)	0.0230 (14)	0.0457 (19)	0.0050 (12)	0.0028 (14)	0.0016 (13)
C10	0.056 (2)	0.0335 (18)	0.050 (2)	0.0035 (16)	0.0098 (17)	−0.0084 (16)
C11	0.051 (2)	0.0350 (18)	0.045 (2)	0.0058 (15)	0.0098 (16)	−0.0020 (15)
C12	0.077 (3)	0.052 (2)	0.047 (2)	0.013 (2)	0.015 (2)	−0.0055 (18)

Br1—C8	1.899 (3)	C6—C7	1.390 (5)
Br2—C2	1.899 (3)	C6—H6	0.9300
O1—C1	1.200 (4)	C7—C8	1.418 (4)
O2—C5	1.375 (4)	C8—C9	1.369 (5)
O2—C1	1.379 (4)	C9—H9	0.9300
N1—C7	1.358 (4)	C10—H10A	0.9600
N1—C11	1.467 (4)	C10—H10B	0.9600
N1—H1	0.857 (5)	C10—H10C	0.9600
C1—C2	1.455 (5)	C11—C12	1.503 (5)
C2—C3	1.342 (5)	C11—H11A	0.9700
C3—C4	1.443 (5)	C11—H11B	0.9700
C3—C10	1.508 (4)	C12—H12A	0.9600
C4—C9	1.401 (5)	C12—H12B	0.9600
C4—C5	1.401 (4)	C12—H12C	0.9600
C5—C6	1.381 (5)
C5—O2—C1	122.3 (3)	C9—C8—C7	122.4 (3)
C7—N1—C11	122.7 (3)	C9—C8—Br1	119.2 (2)
C7—N1—H1	124 (2)	C7—C8—Br1	118.4 (2)
C11—N1—H1	113 (2)	C8—C9—C4	120.9 (3)
O1—C1—O2	116.8 (3)	C8—C9—H9	119.5
O1—C1—C2	127.6 (3)	C4—C9—H9	119.5
O2—C1—C2	115.7 (3)	C3—C10—H10A	109.5
C3—C2—C1	124.2 (3)	C3—C10—H10B	109.5
C3—C2—Br2	123.0 (3)	H10A—C10—H10B	109.5
C1—C2—Br2	112.8 (2)	C3—C10—H10C	109.5
C2—C3—C4	117.8 (3)	H10A—C10—H10C	109.5
C2—C3—C10	123.2 (3)	H10B—C10—H10C	109.5
C4—C3—C10	119.0 (3)	N1—C11—C12	109.7 (3)
C9—C4—C5	116.4 (3)	N1—C11—H11A	109.7
C9—C4—C3	124.5 (3)	C12—C11—H11A	109.7
C5—C4—C3	119.0 (3)	N1—C11—H11B	109.7
O2—C5—C6	115.9 (3)	C12—C11—H11B	109.7
O2—C5—C4	121.0 (3)	H11A—C11—H11B	108.2
C6—C5—C4	123.1 (3)	C11—C12—H12A	109.5
C5—C6—C7	120.3 (3)	C11—C12—H12B	109.5
C5—C6—H6	119.9	H12A—C12—H12B	109.5
C7—C6—H6	119.9	C11—C12—H12C	109.5
N1—C7—C6	122.4 (3)	H12A—C12—H12C	109.5
N1—C7—C8	120.7 (3)	H12B—C12—H12C	109.5
C6—C7—C8	116.9 (3)
C5—O2—C1—O1	179.8 (3)	C9—C4—C5—C6	1.1 (5)
C5—O2—C1—C2	1.1 (4)	C3—C4—C5—C6	−179.2 (3)
O1—C1—C2—C3	−177.1 (4)	O2—C5—C6—C7	−179.9 (3)
O2—C1—C2—C3	1.5 (5)	C4—C5—C6—C7	0.1 (5)
O1—C1—C2—Br2	3.8 (5)	C11—N1—C7—C6	8.0 (5)
O2—C1—C2—Br2	−177.6 (2)	C11—N1—C7—C8	−172.8 (3)
C1—C2—C3—C4	−2.8 (5)	C5—C6—C7—N1	178.4 (3)
Br2—C2—C3—C4	176.3 (2)	C5—C6—C7—C8	−0.8 (5)
C1—C2—C3—C10	178.0 (3)	N1—C7—C8—C9	−178.9 (3)
Br2—C2—C3—C10	−3.0 (5)	C6—C7—C8—C9	0.2 (5)
C2—C3—C4—C9	−178.8 (3)	N1—C7—C8—Br1	1.1 (4)
C10—C3—C4—C9	0.5 (5)	C6—C7—C8—Br1	−179.8 (2)
C2—C3—C4—C5	1.6 (5)	C7—C8—C9—C4	1.0 (5)
C10—C3—C4—C5	−179.2 (3)	Br1—C8—C9—C4	−179.0 (2)
C1—O2—C5—C6	177.8 (3)	C5—C4—C9—C8	−1.7 (5)
C1—O2—C5—C4	−2.2 (5)	C3—C4—C9—C8	178.7 (3)
C9—C4—C5—O2	−178.8 (3)	C7—N1—C11—C12	−175.8 (3)
C3—C4—C5—O2	0.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.86 (3)	2.67 (3)	3.055 (3)	109 (2)
C10—H10A···Br2	0.96	2.68	3.221 (4)	116

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.86 (3)	2.67 (3)	3.055 (3)	109 (2)
C10—H10A⋯Br2	0.96	2.68	3.221 (4)	116