4-Bromo-methyl-7,8-dimethyl-coumarin.

In the title mol-ecule, C(12)H(11)BrO(2), all non-H atoms with the exception of the Br atom are essentially coplanar (r.m.s. deviation = 0.018 Å). The C-Br bond is inclined by 80.17 (12)° to this plane. The crystal structure is stabilized by weak C-H⋯O hydrogen bonds.

Related literature

For potential synthetic applications of the title compound, see: Cui et al. (2007 ▶); Zhao et al. (2008 ▶). For related structures, see: Gowda et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

C12H11BrO2

M = 267.12

Monoclinic,

a = 18.5025 (14) Å

b = 9.8785 (7) Å

c = 13.1639 (10) Å

β = 118.908 (2)°

V = 2106.3 (3) Å3

Z = 8

Mo Kα radiation

μ = 3.88 mm−1

T = 292 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2004 ▶) T min = 0.432, T max = 0.571

14710 measured reflections

3610 independent reflections

2516 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.05

3610 reflections

138 parameters

H-atom parameters constrained

Δρmax = 1.78 e Å−3

Δρmin = −0.73 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049135/lh5165sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049135/lh5165Isup2.hkl

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

C12H11BrO2	F(000) = 1072
Mr = 267.12	Dx = 1.685 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5018 reflections
a = 18.5025 (14) Å	θ = 2.4–28.6°
b = 9.8785 (7) Å	µ = 3.88 mm−1
c = 13.1639 (10) Å	T = 292 K
β = 118.908 (2)°	Block, colourless
V = 2106.3 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 8

Bruker Kappa APEXII CCD diffractometer	3610 independent reflections
Radiation source: fine-focus sealed tube	2516 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω and φ scans	θmax = 31.9°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker 2004)	h = −27→27
Tmin = 0.432, Tmax = 0.571	k = −14→14
14710 measured reflections	l = −19→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0574P)2 + 1.9612P] where P = (Fo2 + 2Fc2)/3
3610 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 1.78 e Å−3
0 restraints	Δρmin = −0.73 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.36207 (15)	0.1296 (2)	0.0849 (2)	0.0332 (5)
C2	0.39174 (15)	0.1512 (2)	0.2032 (2)	0.0363 (5)
C3	0.40658 (16)	0.2836 (3)	0.24674 (19)	0.0398 (5)
H3	0.4263	0.2974	0.3257	0.048*
C4	0.39291 (16)	0.3930 (3)	0.17644 (19)	0.0366 (5)
H4	0.4033	0.4797	0.2079	0.044*
C5	0.36354 (14)	0.3756 (2)	0.05795 (17)	0.0289 (4)
C6	0.34902 (13)	0.2433 (2)	0.01547 (17)	0.0292 (4)
C7	0.34654 (14)	0.4850 (2)	−0.02371 (18)	0.0303 (4)
C8	0.31617 (15)	0.4562 (2)	−0.13705 (19)	0.0354 (5)
H8	0.3025	0.5272	−0.1896	0.043*
C9	0.30411 (16)	0.3200 (2)	−0.1796 (2)	0.0371 (5)
C10	0.34498 (19)	−0.0090 (2)	0.0328 (3)	0.0460 (6)
H10A	0.3014	−0.0043	−0.0461	0.069*
H10B	0.3287	−0.0674	0.0764	0.069*
H10C	0.3939	−0.0443	0.0346	0.069*
C11	0.4099 (2)	0.0349 (3)	0.2855 (3)	0.0530 (7)
H11A	0.3594	−0.0110	0.2678	0.079*
H11B	0.4350	0.0684	0.3637	0.079*
H11C	0.4469	−0.0271	0.2778	0.079*
C12	0.36044 (16)	0.6286 (2)	0.0163 (2)	0.0383 (5)
H12A	0.3423	0.6421	0.0734	0.046*
H12B	0.3287	0.6883	−0.0489	0.046*
O1	0.32072 (11)	0.21805 (17)	−0.10098 (13)	0.0360 (4)
O2	0.28162 (15)	0.2864 (2)	−0.27881 (15)	0.0554 (5)
Br1	0.478174 (17)	0.67133 (3)	0.08473 (2)	0.04795 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0327 (11)	0.0270 (10)	0.0415 (11)	0.0027 (9)	0.0190 (9)	0.0012 (9)
C2	0.0344 (12)	0.0387 (13)	0.0398 (11)	0.0035 (10)	0.0211 (10)	0.0077 (9)
C3	0.0438 (13)	0.0458 (13)	0.0298 (10)	−0.0008 (11)	0.0178 (9)	−0.0007 (9)
C4	0.0432 (13)	0.0338 (12)	0.0336 (10)	−0.0029 (10)	0.0192 (9)	−0.0068 (9)
C5	0.0311 (11)	0.0248 (9)	0.0302 (9)	0.0002 (8)	0.0143 (8)	−0.0018 (7)
C6	0.0300 (10)	0.0285 (10)	0.0293 (9)	0.0007 (8)	0.0144 (8)	−0.0022 (7)
C7	0.0296 (10)	0.0252 (10)	0.0348 (9)	0.0003 (8)	0.0145 (8)	−0.0006 (8)
C8	0.0386 (12)	0.0317 (11)	0.0333 (9)	−0.0003 (9)	0.0153 (9)	0.0036 (8)
C9	0.0383 (12)	0.0369 (12)	0.0323 (9)	−0.0018 (10)	0.0140 (9)	−0.0019 (9)
C10	0.0564 (16)	0.0264 (11)	0.0576 (14)	0.0007 (11)	0.0295 (13)	−0.0007 (10)
C11	0.0552 (17)	0.0542 (17)	0.0511 (14)	0.0062 (14)	0.0269 (13)	0.0211 (13)
C12	0.0402 (13)	0.0256 (10)	0.0434 (12)	0.0017 (10)	0.0158 (10)	−0.0003 (9)
O1	0.0464 (10)	0.0278 (8)	0.0312 (7)	−0.0013 (7)	0.0169 (7)	−0.0053 (6)
O2	0.0764 (15)	0.0524 (11)	0.0310 (8)	−0.0053 (11)	0.0208 (9)	−0.0057 (8)
Br1	0.04529 (18)	0.04007 (16)	0.04762 (16)	−0.00806 (11)	0.01383 (12)	0.00024 (10)

C1—C6	1.393 (3)	C8—C9	1.433 (3)
C1—C2	1.394 (3)	C8—H8	0.9300
C1—C10	1.495 (3)	C9—O2	1.210 (3)
C2—C3	1.401 (4)	C9—O1	1.368 (3)
C2—C11	1.502 (3)	C10—H10A	0.9600
C3—C4	1.364 (4)	C10—H10B	0.9600
C3—H3	0.9300	C10—H10C	0.9600
C4—C5	1.392 (3)	C11—H11A	0.9600
C4—H4	0.9300	C11—H11B	0.9600
C5—C6	1.396 (3)	C11—H11C	0.9600
C5—C7	1.447 (3)	C12—Br1	1.959 (3)
C6—O1	1.382 (2)	C12—H12A	0.9700
C7—C8	1.346 (3)	C12—H12B	0.9700
C7—C12	1.492 (3)
C6—C1—C2	117.3 (2)	C9—C8—H8	118.9
C6—C1—C10	120.4 (2)	O2—C9—O1	116.7 (2)
C2—C1—C10	122.3 (2)	O2—C9—C8	125.9 (2)
C1—C2—C3	119.6 (2)	O1—C9—C8	117.38 (19)
C1—C2—C11	121.2 (2)	C1—C10—H10A	109.5
C3—C2—C11	119.2 (2)	C1—C10—H10B	109.5
C4—C3—C2	121.7 (2)	H10A—C10—H10B	109.5
C4—C3—H3	119.1	C1—C10—H10C	109.5
C2—C3—H3	119.1	H10A—C10—H10C	109.5
C3—C4—C5	120.4 (2)	H10B—C10—H10C	109.5
C3—C4—H4	119.8	C2—C11—H11A	109.5
C5—C4—H4	119.8	C2—C11—H11B	109.5
C4—C5—C6	117.4 (2)	H11A—C11—H11B	109.5
C4—C5—C7	124.5 (2)	C2—C11—H11C	109.5
C6—C5—C7	118.09 (18)	H11A—C11—H11C	109.5
O1—C6—C1	115.77 (19)	H11B—C11—H11C	109.5
O1—C6—C5	120.65 (19)	C7—C12—Br1	109.33 (17)
C1—C6—C5	123.6 (2)	C7—C12—H12A	109.8
C8—C7—C5	119.4 (2)	Br1—C12—H12A	109.8
C8—C7—C12	120.0 (2)	C7—C12—H12B	109.8
C5—C7—C12	120.64 (19)	Br1—C12—H12B	109.8
C7—C8—C9	122.3 (2)	H12A—C12—H12B	108.3
C7—C8—H8	118.9	C9—O1—C6	122.16 (18)
C6—C1—C2—C3	0.3 (4)	C7—C5—C6—C1	−179.3 (2)
C10—C1—C2—C3	180.0 (2)	C4—C5—C7—C8	−178.3 (2)
C6—C1—C2—C11	−178.3 (2)	C6—C5—C7—C8	1.2 (3)
C10—C1—C2—C11	1.3 (4)	C4—C5—C7—C12	0.3 (4)
C1—C2—C3—C4	−0.1 (4)	C6—C5—C7—C12	179.7 (2)
C11—C2—C3—C4	178.6 (3)	C5—C7—C8—C9	−3.5 (4)
C2—C3—C4—C5	−0.1 (4)	C12—C7—C8—C9	178.0 (2)
C3—C4—C5—C6	0.0 (4)	C7—C8—C9—O2	−175.6 (3)
C3—C4—C5—C7	179.5 (2)	C7—C8—C9—O1	3.3 (4)
C2—C1—C6—O1	179.1 (2)	C8—C7—C12—Br1	−101.7 (2)
C10—C1—C6—O1	−0.5 (3)	C5—C7—C12—Br1	79.8 (2)
C2—C1—C6—C5	−0.4 (4)	O2—C9—O1—C6	178.2 (2)
C10—C1—C6—C5	180.0 (2)	C8—C9—O1—C6	−0.8 (4)
C4—C5—C6—O1	−179.3 (2)	C1—C6—O1—C9	179.1 (2)
C7—C5—C6—O1	1.2 (3)	C5—C6—O1—C9	−1.4 (3)
C4—C5—C6—C1	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O2i	0.97	2.40	3.342 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O2i	0.97	2.40	3.342 (3)	163

Symmetry code: (i) .