3,6,8-Tribromo-7-ethyl­amino-4-methyl-2H-chromen-2-one

Zhang, T.; Xi, H.; Miao, C.; Chen, L.; Sun, X.

doi:10.1107/S1600536812009221

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1013

doi:10.1107/S1600536812009221

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3,6,8-Tribromo-7-ethylamino-4-methyl-2H-chromen-2-one

Ting Zhang,^a Hai-tao Xi,^a ^* Chun-bao Miao,^a Liang Chen ^a and Xiao-qiang Sun ^a

^aKey Laboratory of Fine Chemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China
^*Correspondence e-mail: xht@cczu.edu.cn

(Received 13 February 2012; accepted 1 March 2012; online 10 March 2012)

In the title molecule, C₁₂H₁₀Br₃NO₂, the 2H-chromen ring is essentially planar (r.m.s. deviation = 0.022 Å) with the ethylamino group oriented at 13.9 (5)° with respect to the ring. The molecular structure is stabilized by intramolecular N—H⋯Br and C—H⋯Br interactions.

Related literature

For the synthetic procedure, see: Belluti et al. (2010 ). For a related structure, see: Kruszynski et al. (2005 ).

Experimental

Crystal data

C₁₂H₁₀Br₃NO₂
M_r = 439.94
Monoclinic, P 2₁ /c
a = 8.5045 (9) Å
b = 7.2551 (8) Å
c = 21.556 (2) Å
β = 94.720 (2)°
V = 1325.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 9.12 mm⁻¹
T = 296 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 = 0.263, T_max = 0.342
7355 measured reflections
2457 independent reflections
2002 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.099
S = 1.01
2457 reflections
169 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.87 (1)	2.64 (4)	3.039 (4)	109 (3)
C10—H10A⋯Br2	0.96	2.60	3.176 (5)	118
C13—H13A⋯Br3	0.97	2.71	3.146 (7)	108

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009221/pv2515sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009221/pv2515Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009221/pv2515Isup3.cml

checkCIF report

Comment top

The title compound is used as an important intermediate in the synthesis of fluorescent tracers (Belluti et al., (2010). The 2H-chromen ring in the title molecule (Fig. 1) is essentially planar (rmsd 0.022) with ethylamino group oriented at 13.9 (5)° with respect to the ring. The molecular dimensions of the title compound are in agreement with the corresponding dimensions of the structure of a related compound (Kruszynski et al., 2005).

In the crystal of the title compound, there are only N—H···Br and C—H···Br intramolecular hydrogen bonds which stabilize the molecular structure.

Related literature top

For the synthetic procedure, see: Belluti et al. (2010). For a related structure, see: Kruszynski et al. (2005).

Experimental top

The title compound was prepared by a method reported in the literature (Belluti et al., (2010)). To a suspension of 4-methyl-7-N,N-diethylamino coumarin (10 mmol, 2.31 g) and bromosuccinimide (11 mmol, 1.95 g) in carbon tetrachloride (100 ml), a catalytic amount of benzoyl peroxide was added. The reaction mixture was refluxed for 8 h, the succinimide thus produced during the reaction was filtered off, and the solvent was washed with water, dried and removed under reduced pressure to afford the title compound as a pale yellow product. Colorless block of the title compound were grown in ethanol (20 ml) by evaporating the solvent slowly at room temperature for about 5 days.

Structure description top

In the crystal of the title compound, there are only N—H···Br and C—H···Br intramolecular hydrogen bonds which stabilize the molecular structure.

For the synthetic procedure, see: Belluti et al. (2010). For a related structure, see: Kruszynski et al. (2005).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); 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.

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I).

3,6,8-Tribromo-7-ethylamino-4-methyl-2H-chromen-2-one top

Crystal data top

C₁₂H₁₀Br₃NO₂	F(000) = 840
M_r = 439.94	D_x = 2.205 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2620 reflections
a = 8.5045 (9) Å	θ = 2.4–25.5°
b = 7.2551 (8) Å	µ = 9.12 mm⁻¹
c = 21.556 (2) Å	T = 296 K
β = 94.720 (2)°	BLOCK, colorless
V = 1325.5 (3) Å³	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2002 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 25.5°, θ_min = 1.9°
ω/2θ scans	h = −9→10
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.263, T_max = 0.342	l = −26→23
7355 measured reflections	3 standard reflections every 200 reflections
2457 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0605P)² + 0.6207P] where P = (F_o² + 2F_c²)/3
2457 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.63 e Å⁻³
1 restraint	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₂H₁₀Br₃NO₂	V = 1325.5 (3) Å³
M_r = 439.94	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5045 (9) Å	µ = 9.12 mm⁻¹
b = 7.2551 (8) Å	T = 296 K
c = 21.556 (2) Å	0.20 × 0.18 × 0.15 mm
β = 94.720 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2002 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.263, T_max = 0.342	3 standard reflections every 200 reflections
7355 measured reflections	intensity decay: 1%
2457 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	1 restraint
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.63 e Å⁻³
2457 reflections	Δρ_min = −0.56 e Å⁻³
169 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.35825 (6)	0.11548 (6)	0.05870 (2)	0.04316 (16)
Br2	0.41792 (7)	0.58281 (7)	−0.22380 (2)	0.05645 (19)
Br3	0.01975 (6)	0.79144 (7)	0.09690 (2)	0.05198 (18)
O1	0.3974 (3)	0.3023 (4)	−0.05962 (13)	0.0364 (7)
C8	0.1457 (5)	0.6305 (6)	0.0522 (2)	0.0354 (9)
C5	0.3144 (4)	0.4156 (5)	−0.02319 (19)	0.0313 (9)
C4	0.2630 (5)	0.5889 (5)	−0.0453 (2)	0.0335 (9)
C7	0.1975 (5)	0.4566 (6)	0.07545 (19)	0.0335 (9)
C2	0.3720 (5)	0.5264 (6)	−0.14159 (19)	0.0377 (10)
O2	0.5003 (4)	0.2360 (5)	−0.14659 (15)	0.0560 (9)
C9	0.1786 (5)	0.6931 (5)	−0.0049 (2)	0.0359 (9)
H9	0.1434	0.8097	−0.0174	0.043*
C1	0.4277 (5)	0.3477 (6)	−0.1195 (2)	0.0371 (10)
C3	0.2947 (5)	0.6444 (5)	−0.1069 (2)	0.0334 (9)
C6	0.2846 (5)	0.3532 (5)	0.03440 (19)	0.0314 (9)
N1	0.1665 (5)	0.3812 (6)	0.13117 (19)	0.0511 (11)
C10	0.2404 (6)	0.8311 (7)	−0.1302 (2)	0.0519 (12)
H10A	0.2757	0.8515	−0.1708	0.078*
H10B	0.2836	0.9243	−0.1021	0.078*
H10C	0.1273	0.8365	−0.1325	0.078*
C13	0.1232 (8)	0.4655 (9)	0.1875 (3)	0.0650 (15)
H13A	0.0167	0.5137	0.1812	0.078*
H13B	0.1938	0.5673	0.1986	0.078*
C14	0.1322 (8)	0.3266 (9)	0.2388 (2)	0.0668 (15)
H14A	0.0715	0.2198	0.2258	0.100*
H14B	0.0906	0.3791	0.2749	0.100*
H14C	0.2402	0.2916	0.2488	0.100*
H1	0.218 (6)	0.287 (5)	0.147 (2)	0.064 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0588 (3)	0.0282 (2)	0.0433 (3)	0.00216 (19)	0.0097 (2)	0.00324 (18)
Br2	0.0814 (4)	0.0539 (3)	0.0367 (3)	0.0003 (3)	0.0208 (3)	0.0071 (2)
Br3	0.0578 (3)	0.0458 (3)	0.0550 (3)	0.0094 (2)	0.0203 (2)	−0.0111 (2)
O1	0.0488 (17)	0.0293 (15)	0.0323 (16)	0.0073 (13)	0.0110 (13)	0.0001 (12)
C8	0.039 (2)	0.033 (2)	0.034 (2)	0.0012 (18)	0.0082 (19)	−0.0109 (17)
C5	0.033 (2)	0.0264 (19)	0.035 (2)	−0.0005 (16)	0.0062 (18)	−0.0065 (17)
C4	0.038 (2)	0.028 (2)	0.035 (2)	−0.0015 (17)	0.0053 (18)	−0.0023 (17)
C7	0.035 (2)	0.036 (2)	0.030 (2)	−0.0066 (18)	0.0046 (17)	−0.0056 (18)
C2	0.049 (2)	0.037 (2)	0.028 (2)	−0.005 (2)	0.0055 (19)	0.0018 (18)
O2	0.083 (3)	0.0467 (19)	0.041 (2)	0.0135 (19)	0.0224 (19)	−0.0055 (16)
C9	0.041 (2)	0.025 (2)	0.042 (3)	0.0028 (17)	0.0050 (19)	−0.0048 (18)
C1	0.048 (2)	0.032 (2)	0.032 (2)	−0.0022 (19)	0.009 (2)	−0.0029 (18)
C3	0.040 (2)	0.027 (2)	0.034 (2)	−0.0009 (17)	0.0014 (18)	0.0025 (17)
C6	0.039 (2)	0.0244 (19)	0.031 (2)	−0.0015 (17)	0.0038 (18)	−0.0006 (16)
N1	0.071 (3)	0.048 (3)	0.037 (2)	0.004 (2)	0.017 (2)	0.0048 (18)
C10	0.065 (3)	0.040 (2)	0.051 (3)	0.015 (2)	0.011 (3)	0.014 (2)
C13	0.086 (4)	0.068 (4)	0.043 (3)	−0.006 (3)	0.020 (3)	−0.009 (3)
C14	0.089 (4)	0.079 (4)	0.034 (3)	−0.011 (3)	0.014 (3)	0.005 (3)

Geometric parameters (Å, º) top

Br1—C6	1.894 (4)	O2—C1	1.200 (5)
Br2—C2	1.891 (4)	C9—H9	0.9300
Br3—C8	1.899 (4)	C3—C10	1.503 (6)
O1—C5	1.372 (5)	N1—C13	1.434 (6)
O1—C1	1.376 (5)	N1—H1	0.866 (10)
C8—C9	1.362 (6)	C10—H10A	0.9600
C8—C7	1.415 (6)	C10—H10B	0.9600
C5—C6	1.365 (6)	C10—H10C	0.9600
C5—C4	1.402 (6)	C13—C14	1.494 (8)
C4—C9	1.396 (6)	C13—H13A	0.9700
C4—C3	1.434 (6)	C13—H13B	0.9700
C7—N1	1.365 (6)	C14—H14A	0.9600
C7—C6	1.415 (6)	C14—H14B	0.9600
C2—C3	1.344 (6)	C14—H14C	0.9600
C2—C1	1.448 (6)

C5—O1—C1	122.5 (3)	C5—C6—C7	122.6 (4)
C9—C8—C7	122.4 (4)	C5—C6—Br1	118.1 (3)
C9—C8—Br3	114.8 (3)	C7—C6—Br1	119.2 (3)
C7—C8—Br3	122.8 (3)	C7—N1—C13	131.0 (4)
C6—C5—O1	117.7 (3)	C7—N1—H1	122 (4)
C6—C5—C4	122.0 (4)	C13—N1—H1	99 (4)
O1—C5—C4	120.3 (4)	C3—C10—H10A	109.5
C9—C4—C5	115.9 (4)	C3—C10—H10B	109.5
C9—C4—C3	124.8 (4)	H10A—C10—H10B	109.5
C5—C4—C3	119.3 (4)	C3—C10—H10C	109.5
N1—C7—C8	126.3 (4)	H10A—C10—H10C	109.5
N1—C7—C6	119.2 (4)	H10B—C10—H10C	109.5
C8—C7—C6	114.5 (4)	N1—C13—C14	109.8 (5)
C3—C2—C1	123.3 (4)	N1—C13—H13A	109.7
C3—C2—Br2	122.2 (3)	C14—C13—H13A	109.7
C1—C2—Br2	114.5 (3)	N1—C13—H13B	109.7
C8—C9—C4	122.5 (4)	C14—C13—H13B	109.7
C8—C9—H9	118.7	H13A—C13—H13B	108.2
C4—C9—H9	118.7	C13—C14—H14A	109.5
O2—C1—O1	116.0 (4)	C13—C14—H14B	109.5
O2—C1—C2	127.7 (4)	H14A—C14—H14B	109.5
O1—C1—C2	116.2 (4)	C13—C14—H14C	109.5
C2—C3—C4	118.3 (4)	H14A—C14—H14C	109.5
C2—C3—C10	122.6 (4)	H14B—C14—H14C	109.5
C4—C3—C10	119.1 (4)

C1—O1—C5—C6	176.9 (4)	C1—C2—C3—C4	−1.4 (6)
C1—O1—C5—C4	−3.0 (6)	Br2—C2—C3—C4	179.1 (3)
C6—C5—C4—C9	−0.4 (6)	C1—C2—C3—C10	178.8 (4)
O1—C5—C4—C9	179.6 (3)	Br2—C2—C3—C10	−0.7 (6)
C6—C5—C4—C3	−178.4 (4)	C9—C4—C3—C2	−177.2 (4)
O1—C5—C4—C3	1.5 (6)	C5—C4—C3—C2	0.6 (6)
C9—C8—C7—N1	−178.1 (4)	C9—C4—C3—C10	2.6 (7)
Br3—C8—C7—N1	−0.1 (6)	C5—C4—C3—C10	−179.5 (4)
C9—C8—C7—C6	−0.5 (6)	O1—C5—C6—C7	−178.7 (3)
Br3—C8—C7—C6	177.5 (3)	C4—C5—C6—C7	1.2 (6)
C7—C8—C9—C4	1.4 (7)	O1—C5—C6—Br1	−0.6 (5)
Br3—C8—C9—C4	−176.8 (3)	C4—C5—C6—Br1	179.3 (3)
C5—C4—C9—C8	−0.9 (6)	N1—C7—C6—C5	177.1 (4)
C3—C4—C9—C8	177.0 (4)	C8—C7—C6—C5	−0.7 (6)
C5—O1—C1—O2	−179.4 (4)	N1—C7—C6—Br1	−1.1 (5)
C5—O1—C1—C2	2.2 (6)	C8—C7—C6—Br1	−178.8 (3)
C3—C2—C1—O2	−178.2 (5)	C8—C7—N1—C13	−22.3 (9)
Br2—C2—C1—O2	1.4 (6)	C6—C7—N1—C13	160.2 (5)
C3—C2—C1—O1	0.0 (6)	C7—N1—C13—C14	−169.4 (5)
Br2—C2—C1—O1	179.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (1)	2.64 (4)	3.039 (4)	109 (3)
C10—H10A···Br2	0.96	2.60	3.176 (5)	118
C13—H13A···Br3	0.97	2.71	3.146 (7)	108

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀Br₃NO₂
M_r	439.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.5045 (9), 7.2551 (8), 21.556 (2)
β (°)	94.720 (2)
V (Å³)	1325.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.12
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.263, 0.342
No. of measured, independent and observed [I > 2σ(I)] reflections	7355, 2457, 2002
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.099, 1.01
No. of reflections	2457
No. of parameters	169
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.56

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (1)	2.64 (4)	3.039 (4)	109 (3)
C10—H10A···Br2	0.96	2.60	3.176 (5)	118
C13—H13A···Br3	0.97	2.71	3.146 (7)	108

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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