2-Bromo-2-methyl-N-(4-methyl-2-oxo-2H-chromen-7-yl)propanamide.

In the title compound C(14)H(14)BrNO(3), the coumarin ring system is almost planar (r.m.s. deviation = 0.008 Å) and an intra-molecular C-H⋯O inter-action generates an S(6) ring. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, with the C=O unit of the coumarin ring system acting as the acceptor group, generating [010] C(8) chains. The chain connectivity is reinforced by two C-H⋯O inter-actions.

Related literature

For backgound to the properties of coumarin derivatives, see: Sinkel et al. (2008 ▶); Matyjaszewski et al. (2008 ▶); Stenzel-Rosenbaum et al. (2001 ▶); Thaisrivongs et al. (1994 ▶). For a related structure, see: Haridharan et al. (2010 ▶)

Experimental

Crystal data

C14H14BrNO3

M = 324.17

Triclinic,

a = 6.7054 (8) Å

b = 9.2415 (11) Å

c = 11.7612 (15) Å

α = 105.255 (5)°

β = 100.630 (5)°

γ = 93.572 (5)°

V = 686.33 (15) Å3

Z = 2

Mo Kα radiation

μ = 3.00 mm−1

T = 298 K

0.42 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.366, T max = 0.662

4624 measured reflections

2511 independent reflections

1716 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.174

S = 1.09

2511 reflections

179 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.16 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026802/hb5522sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026802/hb5522Isup2.hkl

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

C14H14BrNO3	Z = 2
Mr = 324.17	F(000) = 328
Triclinic, P1	Dx = 1.569 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7054 (8) Å	Cell parameters from 1785 reflections
b = 9.2415 (11) Å	θ = 2.5–24.5°
c = 11.7612 (15) Å	µ = 3.00 mm−1
α = 105.255 (5)°	T = 298 K
β = 100.630 (5)°	Slab, light-yellow
γ = 93.572 (5)°	0.42 × 0.20 × 0.15 mm
V = 686.33 (15) Å3

Bruker APEXII CCD diffractometer	2511 independent reflections
Radiation source: fine-focus sealed tube	1716 reflections with I > 2σ(I)
graphite	Rint = 0.020
phi and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→5
Tmin = 0.366, Tmax = 0.662	k = −11→10
4624 measured reflections	l = −11→14

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.1P)2 + 0.350P] where P = (Fo2 + 2Fc2)/3
2511 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 1.16 e Å−3
1 restraint	Δρmin = −0.53 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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	0.34908 (9)	0.90419 (7)	0.61854 (6)	0.0714 (3)
C1	0.2652 (7)	0.2486 (5)	1.0477 (4)	0.0377 (11)
C2	0.3283 (7)	0.3307 (5)	1.1731 (4)	0.0388 (11)
H2	0.3551	0.2772	1.2299	0.047*
C3	0.3497 (6)	0.4824 (5)	1.2107 (4)	0.0352 (10)
C4	0.3086 (6)	0.5641 (5)	1.1221 (4)	0.0291 (10)
C5	0.3260 (7)	0.7225 (5)	1.1480 (4)	0.0362 (11)
H5	0.3639	0.7807	1.2279	0.043*
C6	0.2890 (7)	0.7927 (5)	1.0596 (4)	0.0347 (10)
H6	0.3042	0.8976	1.0795	0.042*
C7	0.2285 (6)	0.7087 (5)	0.9391 (4)	0.0291 (9)
C8	0.2092 (6)	0.5511 (4)	0.9098 (4)	0.0282 (9)
H8	0.1700	0.4926	0.8301	0.034*
C9	0.2497 (6)	0.4850 (4)	1.0021 (4)	0.0267 (9)
C10	0.4152 (10)	0.5641 (7)	1.3424 (5)	0.0616 (15)
H10A	0.3063	0.6170	1.3694	0.092*
H10B	0.5336	0.6349	1.3549	0.092*
H10C	0.4477	0.4925	1.3872	0.092*
C11	0.1328 (7)	0.7309 (5)	0.7300 (4)	0.0394 (11)
C12	0.0809 (8)	0.8434 (6)	0.6573 (4)	0.0464 (12)
C13	−0.0004 (12)	0.9843 (7)	0.7192 (6)	0.0723 (18)
H13A	−0.1170	0.9573	0.7491	0.108*
H13B	−0.0397	1.0413	0.6629	0.108*
H13C	0.1037	1.0443	0.7851	0.108*
C14	−0.0590 (10)	0.7627 (8)	0.5376 (5)	0.0688 (17)
H14A	−0.1897	0.7310	0.5509	0.103*
H14B	−0.0003	0.6760	0.4984	0.103*
H14C	−0.0757	0.8300	0.4876	0.103*
N1	0.1878 (5)	0.7900 (4)	0.8526 (3)	0.0344 (9)
O1	0.2284 (4)	0.3286 (3)	0.9663 (3)	0.0340 (7)
O2	0.2428 (6)	0.1122 (4)	1.0081 (3)	0.0560 (10)
O3	0.1211 (7)	0.5975 (4)	0.6804 (3)	0.0650 (12)
H1N	0.196 (7)	0.891 (3)	0.889 (4)	0.048 (14)*

	U11	U22	U33	U12	U13	U23
Br1	0.0746 (4)	0.0678 (5)	0.0796 (6)	0.0004 (3)	0.0157 (3)	0.0365 (4)
C1	0.044 (2)	0.024 (3)	0.050 (3)	0.0048 (18)	0.007 (2)	0.020 (2)
C2	0.048 (2)	0.035 (3)	0.039 (3)	0.0044 (19)	0.0067 (19)	0.022 (2)
C3	0.041 (2)	0.034 (3)	0.032 (2)	0.0017 (18)	0.0041 (18)	0.014 (2)
C4	0.035 (2)	0.026 (2)	0.029 (2)	0.0043 (16)	0.0071 (16)	0.012 (2)
C5	0.049 (2)	0.026 (2)	0.028 (2)	0.0052 (18)	0.0016 (18)	0.002 (2)
C6	0.059 (3)	0.012 (2)	0.030 (3)	0.0029 (17)	0.0056 (19)	0.0035 (19)
C7	0.036 (2)	0.024 (2)	0.030 (2)	0.0050 (16)	0.0076 (16)	0.011 (2)
C8	0.038 (2)	0.018 (2)	0.026 (2)	0.0024 (16)	0.0035 (16)	0.0037 (19)
C9	0.0311 (18)	0.017 (2)	0.032 (2)	0.0040 (14)	0.0046 (16)	0.0070 (19)
C10	0.091 (4)	0.055 (4)	0.037 (3)	0.006 (3)	0.001 (3)	0.020 (3)
C11	0.055 (3)	0.035 (3)	0.031 (3)	0.009 (2)	0.0075 (19)	0.015 (2)
C12	0.060 (3)	0.041 (3)	0.042 (3)	0.008 (2)	0.008 (2)	0.018 (2)
C13	0.112 (5)	0.063 (4)	0.062 (4)	0.045 (4)	0.028 (3)	0.037 (3)
C14	0.080 (4)	0.074 (4)	0.051 (4)	−0.003 (3)	−0.012 (3)	0.036 (3)
N1	0.053 (2)	0.020 (2)	0.031 (2)	0.0074 (15)	0.0043 (16)	0.0105 (18)
O1	0.0520 (17)	0.0136 (15)	0.0361 (18)	0.0024 (12)	0.0046 (13)	0.0098 (14)
O2	0.088 (3)	0.0186 (18)	0.061 (2)	0.0042 (16)	0.0067 (19)	0.0166 (17)
O3	0.129 (4)	0.031 (2)	0.0283 (19)	0.016 (2)	0.0016 (19)	0.0069 (16)

Br1—C12	2.017 (5)	C8—H8	0.9300
C1—O2	1.213 (5)	C9—O1	1.385 (5)
C1—O1	1.353 (6)	C10—H10A	0.9600
C1—C2	1.439 (7)	C10—H10B	0.9600
C2—C3	1.344 (6)	C10—H10C	0.9600
C2—H2	0.9300	C11—O3	1.208 (6)
C3—C4	1.438 (7)	C11—N1	1.370 (6)
C3—C10	1.502 (7)	C11—C12	1.529 (7)
C4—C9	1.377 (6)	C12—C13	1.503 (8)
C4—C5	1.407 (6)	C12—C14	1.514 (7)
C5—C6	1.358 (7)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—C7	1.395 (6)	C13—H13C	0.9600
C6—H6	0.9300	C14—H14A	0.9600
C7—C8	1.397 (6)	C14—H14B	0.9600
C7—N1	1.414 (6)	C14—H14C	0.9600
C8—C9	1.373 (6)	N1—H1N	0.91 (2)
O2—C1—O1	116.6 (4)	H10A—C10—H10B	109.5
O2—C1—C2	125.3 (4)	C3—C10—H10C	109.5
O1—C1—C2	118.1 (4)	H10A—C10—H10C	109.5
C3—C2—C1	122.1 (4)	H10B—C10—H10C	109.5
C3—C2—H2	119.0	O3—C11—N1	123.0 (4)
C1—C2—H2	119.0	O3—C11—C12	120.7 (4)
C2—C3—C4	118.5 (4)	N1—C11—C12	116.2 (4)
C2—C3—C10	120.5 (4)	C13—C12—C14	111.2 (5)
C4—C3—C10	121.0 (4)	C13—C12—C11	116.9 (4)
C9—C4—C5	116.0 (4)	C14—C12—C11	109.7 (4)
C9—C4—C3	119.2 (4)	C13—C12—Br1	108.2 (4)
C5—C4—C3	124.8 (4)	C14—C12—Br1	106.0 (4)
C6—C5—C4	121.8 (4)	C11—C12—Br1	104.1 (3)
C6—C5—H5	119.1	C12—C13—H13A	109.5
C4—C5—H5	119.1	C12—C13—H13B	109.5
C5—C6—C7	120.5 (4)	H13A—C13—H13B	109.5
C5—C6—H6	119.7	C12—C13—H13C	109.5
C7—C6—H6	119.7	H13A—C13—H13C	109.5
C6—C7—C8	119.3 (4)	H13B—C13—H13C	109.5
C6—C7—N1	117.1 (4)	C12—C14—H14A	109.5
C8—C7—N1	123.5 (4)	C12—C14—H14B	109.5
C9—C8—C7	118.1 (4)	H14A—C14—H14B	109.5
C9—C8—H8	120.9	C12—C14—H14C	109.5
C7—C8—H8	120.9	H14A—C14—H14C	109.5
C8—C9—C4	124.2 (4)	H14B—C14—H14C	109.5
C8—C9—O1	114.9 (3)	C11—N1—C7	126.8 (4)
C4—C9—O1	120.9 (4)	C11—N1—H1N	122 (3)
C3—C10—H10A	109.5	C7—N1—H1N	111 (3)
C3—C10—H10B	109.5	C1—O1—C9	121.2 (3)
O2—C1—C2—C3	−179.9 (5)	C3—C4—C9—C8	−179.1 (4)
O1—C1—C2—C3	0.5 (6)	C5—C4—C9—O1	179.8 (3)
C1—C2—C3—C4	−0.2 (6)	C3—C4—C9—O1	0.5 (6)
C1—C2—C3—C10	179.8 (4)	O3—C11—C12—C13	150.9 (6)
C2—C3—C4—C9	−0.3 (6)	N1—C11—C12—C13	−27.8 (7)
C10—C3—C4—C9	179.7 (4)	O3—C11—C12—C14	23.1 (7)
C2—C3—C4—C5	−179.5 (4)	N1—C11—C12—C14	−155.6 (5)
C10—C3—C4—C5	0.5 (7)	O3—C11—C12—Br1	−89.9 (5)
C9—C4—C5—C6	−0.7 (6)	N1—C11—C12—Br1	91.4 (4)
C3—C4—C5—C6	178.6 (4)	O3—C11—N1—C7	−3.3 (7)
C4—C5—C6—C7	1.1 (7)	C12—C11—N1—C7	175.3 (4)
C5—C6—C7—C8	−1.0 (6)	C6—C7—N1—C11	177.9 (4)
C5—C6—C7—N1	178.4 (4)	C8—C7—N1—C11	−2.8 (6)
C6—C7—C8—C9	0.5 (6)	O2—C1—O1—C9	−180.0 (4)
N1—C7—C8—C9	−178.9 (4)	C2—C1—O1—C9	−0.3 (6)
C7—C8—C9—C4	−0.1 (6)	C8—C9—O1—C1	179.4 (4)
C7—C8—C9—O1	−179.7 (3)	C4—C9—O1—C1	−0.2 (5)
C5—C4—C9—C8	0.2 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O3	0.93	2.21	2.804 (6)	121
N1—H1N···O2i	0.91 (2)	2.12 (2)	3.016 (5)	168 (5)
C6—H6···O2i	0.93	2.38	3.189 (6)	145
C13—H13C···O2i	0.96	2.51	3.347 (8)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O3	0.93	2.21	2.804 (6)	121
N1—H1N⋯O2i	0.91 (2)	2.12 (2)	3.016 (5)	168 (5)
C6—H6⋯O2i	0.93	2.38	3.189 (6)	145
C13—H13C⋯O2i	0.96	2.51	3.347 (8)	146

Symmetry code: (i) .