(4aR,9R,9aR)-7-Bromo-9-nitro-methyl-2,3,4,4a,9,9a-hexa-hydro-1H-xanthen-1-one.

The title compound, C14H14BrNO4, contains a tricyclic ring system including three contiguous stereocenters all of which exhibit an R configuration. The cyclo-hexa-none ring adopts a chair conformation. The central oxane ring assumes a strained envelope conformation, with five of the ring atoms being nearly coplanar with the bromo-phenyl group and with the C atom adjacent to the O atom and fused with the cyclo-hexa-none ring as the flap. In the crystal, mol-ecules are linked into a three-dimensional network by C-H⋯O inter-actions.

Related literature

For related structures, see: Shi et al. (2004 ▶); Xia et al. (2009 ▶); Ndjakou Lenta et al. (2007 ▶). For background information on domino reactions, see Enders et al. (2007 ▶); Yu & Wang (2002 ▶).

Experimental

Crystal data

C14H14BrNO4

M = 340.17

Monoclinic,

a = 10.3457 (7) Å

b = 5.4662 (5) Å

c = 13.2446 (12) Å

β = 102.849 (2)°

V = 730.25 (11) Å3

Z = 2

Mo Kα radiation

μ = 2.83 mm−1

T = 296 K

0.53 × 0.47 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.224, T max = 0.673

6335 measured reflections

2655 independent reflections

1537 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.137

S = 1.00

2655 reflections

181 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.46 e Å−3

Absolute structure: Flack (1983 ▶), 1058 Friedel pairs

Flack parameter: 0.021 (17)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008659/fy2090sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008659/fy2090Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008659/fy2090Isup3.cml

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

C14H14BrNO4	F(000) = 344
Mr = 340.17	Dx = 1.547 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4391 reflections
a = 10.3457 (7) Å	θ = 3.2–27.4°
b = 5.4662 (5) Å	µ = 2.83 mm−1
c = 13.2446 (12) Å	T = 296 K
β = 102.849 (2)°	Platelet, colorless
V = 730.25 (11) Å3	0.53 × 0.47 × 0.14 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	2655 independent reflections
Radiation source: rotating anode	1537 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
Detector resolution: 10.00 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −6→6
Tmin = 0.224, Tmax = 0.673	l = −16→16
6335 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.137	w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2655 reflections	Δρmax = 0.36 e Å−3
181 parameters	Δρmin = −0.46 e Å−3
1 restraint	Absolute structure: Flack (1983), 1058 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.021 (17)

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.

	x	y	z	Uiso*/Ueq
C1	0.1121 (7)	0.9599 (12)	0.3568 (5)	0.0740 (18)
C2	0.2242 (7)	0.9776 (13)	0.4388 (6)	0.084 (2)
H2	0.2201	1.0658	0.4980	0.101*
C3	0.3408 (7)	0.8631 (13)	0.4308 (5)	0.079 (2)
H3	0.4154	0.8757	0.4847	0.095*
C4	0.3469 (5)	0.7291 (10)	0.3426 (5)	0.0575 (14)
C5	0.4665 (5)	0.4397 (10)	0.2629 (5)	0.0594 (15)
H5	0.4212	0.2917	0.2785	0.071*
C6	0.6112 (5)	0.3829 (12)	0.2656 (6)	0.074 (2)
H6A	0.6535	0.3222	0.3337	0.089*
H6B	0.6160	0.2555	0.2156	0.089*
C7	0.6840 (5)	0.6043 (15)	0.2415 (5)	0.0816 (19)
H7A	0.7741	0.5588	0.2397	0.098*
H7B	0.6882	0.7244	0.2960	0.098*
C8	0.6170 (5)	0.7183 (13)	0.1378 (6)	0.077 (2)
H8A	0.6599	0.8722	0.1292	0.092*
H8B	0.6273	0.6101	0.0820	0.092*
C9	0.4716 (5)	0.7627 (10)	0.1311 (4)	0.0553 (14)
C10	0.3944 (4)	0.5445 (8)	0.1576 (4)	0.0461 (12)
H10	0.3945	0.4183	0.1050	0.055*
C11	0.2504 (4)	0.6049 (10)	0.1573 (4)	0.0487 (12)
H11	0.2196	0.7266	0.1029	0.058*
C12	0.2391 (5)	0.7152 (9)	0.2586 (5)	0.0518 (14)
C13	0.1217 (6)	0.8341 (11)	0.2703 (5)	0.0650 (16)
H13	0.0473	0.8255	0.2160	0.078*
C14	0.1623 (5)	0.3767 (10)	0.1314 (5)	0.0572 (15)
H14A	0.2038	0.2403	0.1732	0.069*
H14B	0.0773	0.4073	0.1485	0.069*
N1	0.1410 (4)	0.3111 (10)	0.0188 (5)	0.0621 (14)
O1	0.4667 (3)	0.6210 (10)	0.3413 (3)	0.0647 (10)
O2	0.4213 (4)	0.9576 (7)	0.1075 (4)	0.0745 (13)
O3	0.1104 (4)	0.0988 (9)	−0.0041 (4)	0.1026 (17)
O4	0.1497 (5)	0.4689 (10)	−0.0439 (4)	0.0874 (14)
Br1	−0.04348 (7)	1.1196 (2)	0.36550 (7)	0.1208 (5)

	U11	U22	U33	U12	U13	U23
C1	0.094 (4)	0.080 (4)	0.048 (5)	0.010 (3)	0.015 (4)	−0.003 (4)
C2	0.096 (5)	0.101 (5)	0.057 (5)	0.017 (4)	0.022 (4)	−0.021 (4)
C3	0.091 (5)	0.100 (5)	0.042 (4)	0.014 (4)	0.003 (3)	−0.012 (4)
C4	0.064 (3)	0.065 (3)	0.044 (4)	0.008 (3)	0.015 (3)	0.007 (3)
C5	0.063 (3)	0.065 (3)	0.050 (4)	0.008 (3)	0.011 (3)	0.009 (3)
C6	0.045 (3)	0.093 (4)	0.078 (5)	0.008 (3)	−0.002 (3)	−0.024 (4)
C7	0.046 (3)	0.098 (5)	0.096 (5)	0.001 (4)	0.004 (3)	−0.019 (5)
C8	0.069 (4)	0.080 (4)	0.087 (6)	0.000 (3)	0.029 (4)	−0.008 (4)
C9	0.066 (3)	0.061 (4)	0.037 (4)	−0.004 (3)	0.008 (3)	−0.005 (3)
C10	0.053 (2)	0.047 (3)	0.039 (3)	0.000 (2)	0.011 (2)	−0.009 (2)
C11	0.057 (2)	0.044 (2)	0.044 (3)	−0.002 (3)	0.009 (2)	0.005 (3)
C12	0.053 (3)	0.054 (3)	0.050 (4)	0.003 (2)	0.013 (2)	0.006 (2)
C13	0.070 (3)	0.066 (4)	0.059 (5)	−0.001 (3)	0.013 (3)	0.010 (3)
C14	0.047 (3)	0.056 (3)	0.069 (5)	−0.006 (2)	0.013 (3)	0.001 (3)
N1	0.037 (2)	0.072 (3)	0.073 (4)	0.011 (2)	0.002 (2)	−0.010 (3)
O1	0.063 (2)	0.086 (2)	0.040 (2)	0.016 (2)	0.0012 (16)	−0.008 (2)
O2	0.084 (3)	0.056 (2)	0.083 (4)	−0.013 (2)	0.017 (2)	0.011 (2)
O3	0.097 (3)	0.070 (3)	0.123 (4)	−0.004 (3)	−0.015 (3)	−0.040 (3)
O4	0.104 (3)	0.105 (4)	0.052 (3)	−0.013 (3)	0.013 (3)	−0.012 (3)
Br1	0.1011 (5)	0.1479 (8)	0.1168 (8)	0.0504 (6)	0.0314 (5)	−0.0231 (7)

C1—C13	1.359 (9)	C7—H7B	0.9700
C1—C2	1.405 (9)	C8—C9	1.506 (8)
C1—Br1	1.857 (6)	C8—H8A	0.9700
C2—C3	1.383 (8)	C8—H8B	0.9700
C2—H2	0.9300	C9—O2	1.196 (6)
C3—C4	1.393 (8)	C9—C10	1.519 (7)
C3—H3	0.9300	C10—C11	1.525 (6)
C4—O1	1.376 (6)	C10—H10	0.9800
C4—C12	1.391 (7)	C11—C12	1.499 (7)
C5—O1	1.435 (8)	C11—C14	1.538 (7)
C5—C6	1.521 (7)	C11—H11	0.9800
C5—C10	1.538 (8)	C12—C13	1.417 (7)
C5—H5	0.9800	C13—H13	0.9300
C6—C7	1.497 (10)	C14—N1	1.502 (8)
C6—H6A	0.9700	C14—H14A	0.9700
C6—H6B	0.9700	C14—H14B	0.9700
C7—C8	1.527 (9)	N1—O4	1.214 (6)
C7—H7A	0.9700	N1—O3	1.223 (7)
C13—C1—C2	119.0 (6)	C7—C8—H8B	109.3
C13—C1—Br1	121.1 (5)	H8A—C8—H8B	108.0
C2—C1—Br1	119.8 (5)	O2—C9—C8	122.0 (5)
C3—C2—C1	119.6 (6)	O2—C9—C10	122.6 (5)
C3—C2—H2	120.2	C8—C9—C10	115.4 (5)
C1—C2—H2	120.2	C9—C10—C11	113.1 (4)
C2—C3—C4	120.3 (6)	C9—C10—C5	109.1 (4)
C2—C3—H3	119.8	C11—C10—C5	111.1 (4)
C4—C3—H3	119.8	C9—C10—H10	107.8
O1—C4—C3	116.4 (5)	C11—C10—H10	107.8
O1—C4—C12	122.0 (5)	C5—C10—H10	107.8
C3—C4—C12	121.5 (5)	C12—C11—C10	110.8 (4)
O1—C5—C6	106.3 (5)	C12—C11—C14	111.4 (4)
O1—C5—C10	108.8 (4)	C10—C11—C14	110.8 (4)
C6—C5—C10	111.9 (5)	C12—C11—H11	107.9
O1—C5—H5	109.9	C10—C11—H11	107.9
C6—C5—H5	109.9	C14—C11—H11	107.9
C10—C5—H5	109.9	C4—C12—C13	116.2 (5)
C7—C6—C5	111.7 (5)	C4—C12—C11	122.0 (5)
C7—C6—H6A	109.3	C13—C12—C11	121.5 (5)
C5—C6—H6A	109.3	C1—C13—C12	123.3 (6)
C7—C6—H6B	109.3	C1—C13—H13	118.3
C5—C6—H6B	109.3	C12—C13—H13	118.3
H6A—C6—H6B	107.9	N1—C14—C11	111.3 (5)
C6—C7—C8	111.8 (5)	N1—C14—H14A	109.4
C6—C7—H7A	109.2	C11—C14—H14A	109.4
C8—C7—H7A	109.2	N1—C14—H14B	109.4
C6—C7—H7B	109.2	C11—C14—H14B	109.4
C8—C7—H7B	109.2	H14A—C14—H14B	108.0
H7A—C7—H7B	107.9	O4—N1—O3	124.0 (6)
C9—C8—C7	111.5 (6)	O4—N1—C14	119.5 (5)
C9—C8—H8A	109.3	O3—N1—C14	116.4 (6)
C7—C8—H8A	109.3	C4—O1—C5	116.7 (4)
C9—C8—H8B	109.3
C13—C1—C2—C3	−1.3 (11)	C5—C10—C11—C14	−84.5 (5)
Br1—C1—C2—C3	−178.5 (6)	O1—C4—C12—C13	179.8 (5)
C1—C2—C3—C4	−0.6 (11)	C3—C4—C12—C13	−3.2 (9)
C2—C3—C4—O1	−179.9 (6)	O1—C4—C12—C11	−6.6 (8)
C2—C3—C4—C12	2.9 (11)	C3—C4—C12—C11	170.4 (6)
O1—C5—C6—C7	−61.4 (7)	C10—C11—C12—C4	−6.8 (7)
C10—C5—C6—C7	57.2 (7)	C14—C11—C12—C4	117.0 (5)
C5—C6—C7—C8	−55.4 (7)	C10—C11—C12—C13	166.4 (4)
C6—C7—C8—C9	51.6 (7)	C14—C11—C12—C13	−69.8 (6)
C7—C8—C9—O2	128.3 (7)	C2—C1—C13—C12	1.0 (10)
C7—C8—C9—C10	−51.1 (7)	Br1—C1—C13—C12	178.1 (4)
O2—C9—C10—C11	−3.6 (8)	C4—C12—C13—C1	1.2 (9)
C8—C9—C10—C11	175.8 (5)	C11—C12—C13—C1	−172.4 (6)
O2—C9—C10—C5	−127.8 (6)	C12—C11—C14—N1	162.8 (4)
C8—C9—C10—C5	51.6 (6)	C10—C11—C14—N1	−73.3 (5)
O1—C5—C10—C9	63.7 (5)	C11—C14—N1—O4	−25.2 (6)
C6—C5—C10—C9	−53.5 (6)	C11—C14—N1—O3	157.5 (4)
O1—C5—C10—C11	−61.7 (5)	C3—C4—O1—C5	166.4 (6)
C6—C5—C10—C11	−178.9 (5)	C12—C4—O1—C5	−16.5 (8)
C9—C10—C11—C12	−83.4 (6)	C6—C5—O1—C4	170.2 (5)
C5—C10—C11—C12	39.7 (6)	C10—C5—O1—C4	49.5 (7)
C9—C10—C11—C14	152.4 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1i	0.93	2.71	3.520 (9)	146
C8—H8B···O2ii	0.97	2.59	3.489 (6)	155
C8—H8A···O4iii	0.97	2.54	3.253 (4)	131
C10—H10···O2iv	0.98	2.53	3.300 (8)	135
C11—H11···O3v	0.98	2.59	3.547 (8)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1i	0.93	2.71	3.520 (9)	146
C8—H8B⋯O2ii	0.97	2.59	3.489 (6)	155
C8—H8A⋯O4iii	0.97	2.54	3.253 (4)	131
C10—H10⋯O2iv	0.98	2.53	3.300 (8)	135
C11—H11⋯O3v	0.98	2.59	3.547 (8)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .