(R)-7-Bromo-2,3,4,4a-tetra-hydro-1H-xanthen-1-one.

The title compound, C(13)H(11)BrO(2), contains a tricyclic ring system with one chiral center which exhibits an R configuration. The crystal structure is devoid of any classical hydrogen bonding.

Related literature

For related structures, see: Shi et al. (2004 ▶); Ndjakou Lenta et al. (2007 ▶). Domino or cascade reactions allow, in principle, the formation of multiple new bonds and stereocenters in a one-pot system, see: Enders et al. (2007 ▶); Yu & Wang (2002 ▶).

Experimental

Crystal data

C13H11BrO2

M = 279.13

Monoclinic,

a = 7.5419 (4) Å

b = 6.9039 (3) Å

c = 10.7634 (5) Å

β = 93.7110 (12)°

V = 559.26 (5) Å3

Z = 2

Mo Kα radiation

μ = 3.67 mm−1

T = 296 K

0.40 × 0.37 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.252, T max = 0.386

5496 measured reflections

2525 independent reflections

1772 reflections with F 2 > 2σ(F 2)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.102

S = 1.00

2525 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.88 e Å−3

Absolute structure: Flack (1983 ▶), 1145 Friedel pairs

Flack parameter: 0.01 (2)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030244/pv2187sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030244/pv2187Isup2.hkl

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

C13H11BrO2	F(000) = 280.00
Mr = 279.13	Dx = 1.657 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2yb	Cell parameters from 4299 reflections
a = 7.5419 (4) Å	θ = 3.2–27.4°
b = 6.9039 (3) Å	µ = 3.67 mm−1
c = 10.7634 (5) Å	T = 296 K
β = 93.7110 (12)°	Chunk, yellow
V = 559.26 (5) Å3	0.40 × 0.37 × 0.26 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	1772 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1	Rint = 0.036
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.252, Tmax = 0.386	k = −8→8
5496 measured reflections	l = −12→13
2525 independent reflections

Refinement on F2	(Δ/σ)max = 0.001
R[F2 > 2σ(F2)] = 0.033	Δρmax = 0.64 e Å−3
wR(F2) = 0.102	Δρmin = −0.88 e Å−3
S = 1.00	Extinction correction: SHELXL97 (Sheldrick, 2008)
2525 reflections	Extinction coefficient: 0.035 (3)
147 parameters	Absolute structure: Flack (1983), 1145 Friedel pairs
H-atom parameters constrained	Flack parameter: 0.01 (2)
w = 1/[σ2(Fo2) + (0.02P)2 + P] where P = (Fo2 + 2Fc2)/3

Experimental. The structure of the title compound was confirmed by NMR and HRMS methods: 1HNMR (500 MHz, CDCl3): 7.33–7.31(m, 3H), 6.77–6.75(d, J=9.5 Hz,1H),5.00–4.97(m, 1H),2.62–2.58 (m, 1H), 2.51–2.46(m, 1H),2.42–2.35(m, 1H),2.13–2.07(m, 1H),2.04–1.96 (m, 1H), 1.75–1.65(m, 1H) p.p.m.; 13CNMR (125 MHz, CDCl3): 197.1, 154.8, 134.4, 131.8, 131.4, 129.9, 123.9, 117.8, 114.0, 74.8, 38.8, 29.6, 17.9 p.p.m.. HRMS: (EI+) m/z calcd for (C13H11BrO2)+ 277.9942, found 277.9949.

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

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 > 2σ(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	0.96613 (6)	0.67049 (12)	0.66752 (4)	0.0633 (2)
O1	0.5964 (5)	0.6274 (8)	−0.0423 (3)	0.0656 (16)
O2	0.2944 (3)	0.6625 (11)	0.3348 (2)	0.0473 (7)
C1	0.4600 (6)	0.6384 (11)	0.0116 (4)	0.0505 (16)
C2	0.2803 (7)	0.6187 (12)	−0.0570 (4)	0.063 (2)
C3	0.1314 (6)	0.7222 (8)	0.0028 (4)	0.0557 (18)
C4	0.1286 (5)	0.6734 (16)	0.1395 (3)	0.0519 (11)
C5	0.2999 (6)	0.7335 (7)	0.2089 (4)	0.0440 (13)
C6	0.4495 (4)	0.6742 (14)	0.4075 (3)	0.0401 (8)
C7	0.4396 (5)	0.6820 (14)	0.5352 (3)	0.0434 (10)
C8	0.5937 (5)	0.6827 (14)	0.6123 (3)	0.0454 (11)
C9	0.7562 (5)	0.6759 (14)	0.5602 (3)	0.0412 (9)
C10	0.7694 (5)	0.6637 (16)	0.4334 (3)	0.0425 (9)
C11	0.6136 (4)	0.6623 (14)	0.3548 (3)	0.0393 (8)
C12	0.6132 (5)	0.6402 (11)	0.2208 (4)	0.0447 (15)
C13	0.4640 (4)	0.6636 (15)	0.1494 (3)	0.0413 (9)
H5	0.3034	0.8753	0.2117	0.053*
H7	0.3294	0.6868	0.5692	0.052*
H8	0.5879	0.6877	0.6983	0.054*
H10	0.8801	0.6564	0.4004	0.051*
H12	0.7181	0.6095	0.1844	0.054*
H21	0.2509	0.4820	−0.0622	0.075*
H22	0.2883	0.6705	−0.1402	0.075*
H31	0.0191	0.6841	−0.0391	0.067*
H32	0.1475	0.8609	−0.0060	0.067*
H41	0.0304	0.7408	0.1742	0.062*
H42	0.1129	0.5347	0.1486	0.062*

	U11	U22	U33	U12	U13	U23
Br1	0.0439 (2)	0.0990 (4)	0.0455 (2)	−0.0020 (5)	−0.00874 (17)	0.0000 (5)
O1	0.062 (2)	0.095 (5)	0.0402 (16)	0.016 (2)	0.0060 (15)	−0.009 (2)
O2	0.0289 (13)	0.070 (2)	0.0433 (14)	0.006 (3)	0.0015 (10)	0.005 (3)
C1	0.053 (2)	0.056 (4)	0.042 (2)	0.012 (3)	−0.0026 (19)	−0.005 (2)
C2	0.063 (3)	0.079 (7)	0.043 (2)	0.004 (3)	−0.015 (2)	−0.003 (3)
C3	0.044 (2)	0.073 (5)	0.048 (2)	0.003 (2)	−0.012 (2)	0.009 (2)
C4	0.035 (2)	0.065 (3)	0.056 (2)	−0.011 (5)	−0.0060 (17)	0.009 (5)
C5	0.038 (2)	0.054 (3)	0.039 (2)	0.000 (2)	−0.0029 (18)	0.004 (2)
C6	0.0311 (18)	0.045 (2)	0.0437 (19)	−0.001 (3)	0.0006 (14)	0.007 (4)
C7	0.037 (2)	0.053 (2)	0.041 (2)	0.000 (3)	0.0100 (15)	0.006 (3)
C8	0.047 (2)	0.053 (3)	0.0361 (19)	−0.002 (3)	0.0038 (16)	−0.005 (3)
C9	0.0362 (19)	0.047 (2)	0.0400 (19)	−0.003 (4)	−0.0060 (14)	0.005 (4)
C10	0.0340 (19)	0.056 (2)	0.0378 (18)	0.001 (4)	0.0050 (14)	0.000 (4)
C11	0.0359 (19)	0.044 (2)	0.0376 (18)	−0.002 (3)	0.0014 (14)	−0.005 (4)
C12	0.034 (2)	0.058 (4)	0.042 (2)	0.006 (2)	0.0051 (15)	0.005 (3)
C13	0.040 (2)	0.045 (2)	0.0385 (19)	0.001 (4)	0.0004 (15)	0.001 (4)

Br1—C9	1.899 (3)	C10—C11	1.403 (5)
O1—C1	1.215 (6)	C11—C12	1.450 (5)
O2—C5	1.444 (5)	C12—C13	1.330 (5)
O2—C6	1.367 (4)	C2—H21	0.970
C1—C2	1.507 (7)	C2—H22	0.970
C1—C13	1.492 (6)	C3—H31	0.970
C2—C3	1.510 (8)	C3—H32	0.970
C3—C4	1.511 (6)	C4—H41	0.970
C4—C5	1.508 (6)	C4—H42	0.970
C5—C13	1.509 (6)	C5—H5	0.980
C6—C7	1.382 (5)	C7—H7	0.930
C6—C11	1.397 (5)	C8—H8	0.930
C7—C8	1.384 (5)	C10—H10	0.930
C8—C9	1.381 (5)	C12—H12	0.930
C9—C10	1.377 (5)
C5—O2—C6	116.2 (3)	C1—C2—H21	108.1
O1—C1—C2	121.5 (4)	C1—C2—H22	108.1
O1—C1—C13	121.2 (4)	C3—C2—H21	108.1
C2—C1—C13	117.2 (4)	C3—C2—H22	108.1
C1—C2—C3	114.7 (4)	H21—C2—H22	109.5
C2—C3—C4	111.5 (5)	C2—C3—H31	109.0
C3—C4—C5	110.8 (4)	C2—C3—H32	109.0
O2—C5—C4	107.2 (4)	C4—C3—H31	109.0
O2—C5—C13	111.3 (4)	C4—C3—H32	109.0
C4—C5—C13	113.7 (4)	H31—C3—H32	109.5
O2—C6—C7	118.2 (3)	C3—C4—H41	109.1
O2—C6—C11	120.8 (3)	C3—C4—H42	109.1
C7—C6—C11	120.8 (3)	C5—C4—H41	109.1
C6—C7—C8	120.0 (3)	C5—C4—H42	109.1
C7—C8—C9	119.2 (3)	H41—C4—H42	109.5
Br1—C9—C8	118.7 (2)	O2—C5—H5	108.1
Br1—C9—C10	119.4 (2)	C4—C5—H5	108.1
C8—C9—C10	121.8 (3)	C13—C5—H5	108.1
C9—C10—C11	119.1 (3)	C6—C7—H7	120.0
C6—C11—C10	119.0 (3)	C8—C7—H7	120.0
C6—C11—C12	117.7 (3)	C7—C8—H8	120.4
C10—C11—C12	123.3 (3)	C9—C8—H8	120.4
C11—C12—C13	120.6 (4)	C9—C10—H10	120.4
C1—C13—C5	119.6 (3)	C11—C10—H10	120.4
C1—C13—C12	121.5 (4)	C11—C12—H12	119.7
C5—C13—C12	118.7 (3)	C13—C12—H12	119.7
C5—O2—C6—C7	155.2 (7)	O2—C6—C7—C8	176.3 (8)
C5—O2—C6—C11	−30.1 (12)	O2—C6—C11—C10	−176.4 (9)
C6—O2—C5—C4	169.6 (7)	O2—C6—C11—C12	1.0 (13)
C6—O2—C5—C13	44.7 (8)	C7—C6—C11—C10	−1.8 (14)
O1—C1—C2—C3	−153.0 (6)	C7—C6—C11—C12	175.6 (8)
O1—C1—C13—C5	162.5 (7)	C11—C6—C7—C8	1.6 (14)
O1—C1—C13—C12	−12.2 (13)	C6—C7—C8—C9	0.1 (12)
C2—C1—C13—C5	−20.1 (11)	C7—C8—C9—Br1	−178.5 (7)
C2—C1—C13—C12	165.2 (8)	C7—C8—C9—C10	−1.6 (15)
C13—C1—C2—C3	29.6 (9)	Br1—C9—C10—C11	178.2 (7)
C1—C2—C3—C4	−50.2 (8)	C8—C9—C10—C11	1.4 (15)
C2—C3—C4—C5	60.7 (8)	C9—C10—C11—C6	0.3 (11)
C3—C4—C5—O2	−173.7 (6)	C9—C10—C11—C12	−176.9 (9)
C3—C4—C5—C13	−50.2 (9)	C6—C11—C12—C13	11.1 (13)
O2—C5—C13—C1	151.9 (7)	C10—C11—C12—C13	−171.7 (9)
O2—C5—C13—C12	−33.3 (10)	C11—C12—C13—C1	−179.0 (8)
C4—C5—C13—C1	30.7 (10)	C11—C12—C13—C5	6.3 (12)
C4—C5—C13—C12	−154.5 (8)