Crystal structure of 3-bromo-acetyl-6-chloro-2H-1-benzo-pyran-2-one.

In the title compound, C11H6BrClO3, the benzo-pyran ring system is essentially planar, with a maximum deviation of 0.036 (2) Å for the O atom. The Cl and Br atoms are displaced by -0.0526 (8) and 0.6698 (3) Å, respectively, from the mean plane of this ring system. In the crystal, two pairs of weak C-H⋯O hydrogen bonds to the same acceptor O atom link mol-ecules into inversion dimers.

Related literature

For applications of coumarins, see: Kale & Patwardhan (2014 ▸); Eid et al. (1994 ▸); Hsieh (2015 ▸); Ballazhi et al. (2015 ▸); Wang (2015 ▸); Lanoot et al. (2002 ▸); Morris & Russell (1971 ▸); Hooper et al. (1982 ▸); Khalfan et al. (1987 ▸). For related structures, see: Munshi et al. (2004 ▸); Munshi & Guru Row (2006 ▸); Chopra et al. (2006 ▸, 2007a ▸,b ▸).

Experimental

Crystal data

C11H6BrClO3

M = 301.51

Monoclinic,

a = 12.5770 (2) Å

b = 5.7977 (1) Å

c = 14.8390 (3) Å

β = 94.679 (2)°

V = 1078.42 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.05 mm−1

T = 293 K

0.40 × 0.10 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T min = 0.295, T max = 0.712

20627 measured reflections

2113 independent reflections

1532 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.076

S = 0.95

2113 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 1998 ▸); cell refinement: SAINT (Bruker, 1998 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Window (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012955/lh5773sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012955/lh5773Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012955/lh5773Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015012955/lh5773fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015012955/lh5773fig2.tif

The reaction scheme.

CCDC reference: 739322

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H6BrClO3	F(000) = 592
Mr = 301.51	Dx = 1.857 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2113 reflections
a = 12.5770 (2) Å	θ = 3.1–26.0°
b = 5.7977 (1) Å	µ = 4.05 mm−1
c = 14.8390 (3) Å	T = 293 K
β = 94.679 (2)°	Needle, yellow
V = 1078.42 (3) Å3	0.40 × 0.10 × 0.09 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2113 independent reflections
Radiation source: fine-focus sealed tube	1532 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.295, Tmax = 0.712	k = −7→7
20627 measured reflections	l = −18→18

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0424P)2 + 0.3438P] where P = (Fo2 + 2Fc2)/3
2113 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.82908 (2)	0.43513 (6)	0.08551 (2)	0.0724 (1)
Cl1	0.03785 (6)	−0.08546 (14)	0.11305 (5)	0.0667 (3)
O1	0.36571 (16)	0.6170 (3)	0.19323 (11)	0.0522 (6)
O2	0.52243 (17)	0.7733 (3)	0.18198 (12)	0.0592 (7)
O3	0.62089 (15)	0.2132 (3)	0.03489 (14)	0.0665 (7)
C1	0.4668 (2)	0.6090 (4)	0.16473 (15)	0.0450 (9)
C2	0.4945 (2)	0.4025 (4)	0.11494 (14)	0.0380 (8)
C3	0.4205 (2)	0.2395 (4)	0.09438 (15)	0.0396 (8)
C4	0.3152 (2)	0.2556 (4)	0.12289 (15)	0.0403 (8)
C5	0.2359 (2)	0.0892 (4)	0.10347 (16)	0.0453 (8)
C6	0.1383 (2)	0.1173 (5)	0.13694 (17)	0.0507 (9)
C7	0.1178 (3)	0.3055 (6)	0.19074 (19)	0.0624 (10)
C8	0.1941 (3)	0.4691 (6)	0.21009 (19)	0.0616 (11)
C9	0.2920 (2)	0.4454 (4)	0.17544 (16)	0.0476 (8)
C10	0.6045 (2)	0.3676 (4)	0.08674 (15)	0.0422 (8)
C11	0.6926 (2)	0.5239 (5)	0.12365 (18)	0.0546 (9)
H3	0.43848	0.11242	0.06054	0.0475*
H5	0.24924	−0.03874	0.06832	0.0543*
H7	0.05146	0.32003	0.21373	0.0747*
H8	0.18033	0.59506	0.24616	0.0741*
H11A	0.67683	0.68051	0.10379	0.0655*
H11B	0.69582	0.52191	0.18918	0.0655*

	U11	U22	U33	U12	U13	U23
Br1	0.0534 (2)	0.0854 (3)	0.0780 (2)	−0.0081 (2)	0.0030 (2)	−0.0066 (2)
Cl1	0.0485 (4)	0.0861 (6)	0.0667 (4)	0.0015 (4)	0.0129 (3)	0.0141 (4)
O1	0.0676 (13)	0.0426 (10)	0.0454 (10)	0.0208 (9)	−0.0008 (9)	−0.0103 (8)
O2	0.0855 (15)	0.0367 (10)	0.0539 (11)	0.0024 (10)	−0.0027 (10)	−0.0138 (9)
O3	0.0569 (12)	0.0673 (13)	0.0782 (13)	−0.0123 (10)	0.0231 (10)	−0.0361 (12)
C1	0.0644 (18)	0.0372 (15)	0.0318 (12)	0.0127 (13)	−0.0050 (12)	0.0010 (11)
C2	0.0543 (15)	0.0308 (13)	0.0285 (11)	0.0060 (11)	0.0008 (10)	−0.0006 (10)
C3	0.0543 (15)	0.0338 (13)	0.0313 (12)	0.0110 (12)	0.0075 (11)	−0.0007 (10)
C4	0.0516 (15)	0.0379 (14)	0.0315 (12)	0.0154 (12)	0.0049 (10)	0.0030 (10)
C5	0.0509 (15)	0.0454 (15)	0.0405 (13)	0.0126 (13)	0.0096 (11)	0.0052 (11)
C6	0.0472 (16)	0.0639 (18)	0.0411 (14)	0.0130 (13)	0.0050 (12)	0.0120 (13)
C7	0.0523 (18)	0.083 (2)	0.0535 (16)	0.0289 (17)	0.0142 (14)	0.0042 (16)
C8	0.065 (2)	0.069 (2)	0.0515 (16)	0.0325 (17)	0.0086 (14)	−0.0107 (14)
C9	0.0573 (16)	0.0468 (15)	0.0383 (12)	0.0195 (14)	0.0013 (11)	0.0005 (12)
C10	0.0558 (16)	0.0361 (13)	0.0348 (12)	−0.0014 (11)	0.0036 (11)	−0.0017 (11)
C11	0.0595 (18)	0.0532 (16)	0.0497 (15)	−0.0032 (13)	−0.0034 (13)	−0.0071 (13)

Br1—C11	1.921 (3)	C5—C6	1.371 (4)
Cl1—C6	1.741 (3)	C6—C7	1.389 (4)
O1—C1	1.373 (3)	C7—C8	1.363 (5)
O1—C9	1.371 (3)	C8—C9	1.379 (4)
O2—C1	1.197 (3)	C10—C11	1.500 (4)
O3—C10	1.209 (3)	C3—H3	0.9300
C1—C2	1.464 (3)	C5—H5	0.9300
C2—C3	1.344 (3)	C7—H7	0.9300
C2—C10	1.492 (4)	C8—H8	0.9300
C3—C4	1.426 (4)	C11—H11A	0.9700
C4—C5	1.401 (3)	C11—H11B	0.9700
C4—C9	1.393 (3)
Br1···O3	2.9589 (19)	C2···C10viii	3.417 (3)
Br1···H8i	3.1900	C2···O3viii	3.389 (3)
Cl1···C8ii	3.485 (4)	C3···O2i	3.343 (3)
Cl1···Cl1iii	3.5530 (11)	C3···O2ii	3.220 (3)
Cl1···H7iv	2.9400	C3···C10viii	3.518 (3)
O1···C5v	3.403 (3)	C3···O3vii	3.268 (3)
O1···O2i	2.992 (3)	C4···O2i	3.406 (3)
O2···C3v	3.220 (3)	C5···O3vii	3.337 (3)
O2···C11	2.779 (3)	C5···O1ii	3.403 (3)
O2···C4vi	3.406 (3)	C8···Cl1v	3.485 (4)
O2···C9vi	3.180 (3)	C9···O2i	3.180 (3)
O2···C2vi	3.129 (3)	C10···C2viii	3.417 (3)
O2···O1vi	2.992 (3)	C10···C3viii	3.518 (3)
O2···C1vi	2.988 (3)	C11···O2	2.779 (3)
O2···C3vi	3.343 (3)	C1···H11B	2.9200
O3···Br1	2.9589 (19)	C1···H11A	2.8900
O3···C5vii	3.337 (3)	H3···O2ii	2.8100
O3···C1viii	3.244 (3)	H3···O3	2.4300
O3···C2viii	3.389 (3)	H3···H5	2.5500
O3···C3vii	3.268 (3)	H3···O3vii	2.4400
O2···H11A	2.4000	H5···H3	2.5500
O2···H11B	2.6200	H5···O3vii	2.5400
O2···H3v	2.8100	H7···Cl1ix	2.9400
O3···H3	2.4300	H8···Br1vi	3.1900
O3···H3vii	2.4400	H11A···O2	2.4000
O3···H5vii	2.5400	H11A···C1	2.8900
C1···O3viii	3.244 (3)	H11B···O2	2.6200
C1···O2i	2.988 (3)	H11B···C1	2.9200
C2···O2i	3.129 (3)
C1—O1—C9	123.02 (19)	C4—C9—C8	121.4 (2)
O1—C1—O2	116.6 (2)	O3—C10—C2	119.3 (2)
O1—C1—C2	116.6 (2)	O3—C10—C11	121.4 (2)
O2—C1—C2	126.9 (2)	C2—C10—C11	119.4 (2)
C1—C2—C3	120.1 (2)	Br1—C11—C10	112.44 (18)
C1—C2—C10	121.1 (2)	C2—C3—H3	119.00
C3—C2—C10	118.8 (2)	C4—C3—H3	119.00
C2—C3—C4	122.0 (2)	C4—C5—H5	120.00
C3—C4—C5	123.8 (2)	C6—C5—H5	120.00
C3—C4—C9	117.4 (2)	C6—C7—H7	120.00
C5—C4—C9	118.8 (2)	C8—C7—H7	120.00
C4—C5—C6	119.2 (2)	C7—C8—H8	120.00
Cl1—C6—C5	120.2 (2)	C9—C8—H8	120.00
Cl1—C6—C7	118.8 (2)	Br1—C11—H11A	109.00
C5—C6—C7	121.0 (3)	Br1—C11—H11B	109.00
C6—C7—C8	120.5 (3)	C10—C11—H11A	109.00
C7—C8—C9	119.1 (3)	C10—C11—H11B	109.00
O1—C9—C4	120.8 (2)	H11A—C11—H11B	108.00
O1—C9—C8	117.8 (2)
C9—O1—C1—O2	177.6 (2)	C3—C4—C5—C6	177.6 (2)
C9—O1—C1—C2	−1.3 (3)	C9—C4—C5—C6	−0.3 (3)
C1—O1—C9—C4	−3.0 (3)	C3—C4—C9—O1	4.5 (3)
C1—O1—C9—C8	177.9 (2)	C3—C4—C9—C8	−176.5 (2)
O1—C1—C2—C3	4.1 (3)	C5—C4—C9—O1	−177.5 (2)
O1—C1—C2—C10	−175.44 (19)	C5—C4—C9—C8	1.6 (4)
O2—C1—C2—C3	−174.6 (2)	C4—C5—C6—Cl1	179.43 (19)
O2—C1—C2—C10	5.9 (4)	C4—C5—C6—C7	−1.1 (4)
C1—C2—C3—C4	−2.7 (3)	Cl1—C6—C7—C8	−179.3 (2)
C10—C2—C3—C4	176.9 (2)	C5—C6—C7—C8	1.2 (4)
C1—C2—C10—O3	−169.4 (2)	C6—C7—C8—C9	0.1 (4)
C1—C2—C10—C11	10.9 (3)	C7—C8—C9—O1	177.6 (3)
C3—C2—C10—O3	11.0 (3)	C7—C8—C9—C4	−1.4 (4)
C3—C2—C10—C11	−168.7 (2)	O3—C10—C11—Br1	−3.9 (3)
C2—C3—C4—C5	−179.6 (2)	C2—C10—C11—Br1	175.83 (17)
C2—C3—C4—C9	−1.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3vii	0.9300	2.4400	3.268 (3)	148.00
C5—H5···O3vii	0.9300	2.5400	3.337 (3)	144.00

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C3H3O3i	0.93	2.44	3.268(3)	148
C5H5O3i	0.93	2.54	3.337(3)	144

Symmetry code: (i) .