3-(4-Bromo-benzyl-idene)-1,5-dioxaspiro-[5.5]undecane-2,4-dione.

The title mol-ecule, C(16)H(15)BrO(4), was prepared by the reaction of (R)-2,4-dioxo-1,5-dioxaspiro-[5.5]undecane and 4-bromo-benzaldehyde with ethanol. The 1,3-dioxane ring exhibits a distorted boat and the fused cyclo-hexane ring exhibits a chair conformation.

Related literature

For puckering parameters, see: Cremer & Pople (1975 ▶). For background information and related structures, see: Zeng & Jian (2009 ▶); Zeng et al. (2009 ▶).

Experimental

Crystal data

C16H15BrO4

M = 351.18

Orthorhombic,

a = 6.6008 (13) Å

b = 16.784 (3) Å

c = 13.424 (3) Å

V = 1487.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.78 mm−1

T = 293 K

0.18 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

12420 measured reflections

3243 independent reflections

2042 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.124

S = 0.93

3243 reflections

191 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.34 e Å−3

Absolute structure: Flack (1983 ▶), 1459 Friedel pairs

Flack parameter: −0.033 (13)

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001516/si2324sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001516/si2324Isup2.hkl

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

C16H15BrO4	F(000) = 712
Mr = 351.18	Dx = 1.568 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2042 reflections
a = 6.6008 (13) Å	θ = 3.0–27.5°
b = 16.784 (3) Å	µ = 2.78 mm−1
c = 13.424 (3) Å	T = 293 K
V = 1487.2 (5) Å3	Block, yellow
Z = 4	0.18 × 0.12 × 0.10 mm

Bruker SMART CCD area-detector diffractometer	2042 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.065
graphite	θmax = 27.5°, θmin = 3.0°
φ and ω scans	h = −8→8
12420 measured reflections	k = −21→21
3243 independent reflections	l = −17→17

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0603P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124	(Δ/σ)max < 0.001
S = 0.93	Δρmax = 0.31 e Å−3
3243 reflections	Δρmin = −0.34 e Å−3
191 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.0088 (18)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1459 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.033 (13)

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
Br1	−0.30705 (7)	0.16937 (3)	0.44191 (6)	0.0845 (2)
O4	0.3239 (4)	0.18964 (18)	−0.1213 (2)	0.0495 (7)
C8	0.2952 (5)	0.1895 (3)	−0.0213 (4)	0.0474 (9)
C10	0.5373 (7)	0.0731 (3)	−0.0208 (4)	0.0683 (13)
O3	0.5363 (4)	0.07733 (19)	−0.1204 (2)	0.0628 (8)
O2	0.2192 (4)	0.24707 (17)	0.0163 (3)	0.0565 (7)
C7	0.3358 (7)	0.0974 (3)	0.1252 (4)	0.0625 (11)
H7A	0.4214	0.0577	0.1490	0.075*
C4	0.1814 (6)	0.1207 (3)	0.1977 (4)	0.0562 (11)
C9	0.3812 (7)	0.1202 (3)	0.0332 (4)	0.0574 (11)
C12	0.3662 (6)	0.1150 (2)	−0.1684 (4)	0.0504 (10)
C6	−0.1475 (7)	0.1696 (3)	0.2454 (5)	0.0654 (13)
H6A	−0.2712	0.1920	0.2277	0.079*
C5	−0.0046 (7)	0.1545 (2)	0.1731 (4)	0.0626 (11)
H5A	−0.0327	0.1670	0.1071	0.075*
C1	−0.1088 (7)	0.1517 (2)	0.3444 (3)	0.0569 (10)
C13	0.4385 (7)	0.1343 (3)	−0.2731 (4)	0.0669 (13)
H13A	0.5485	0.1725	−0.2697	0.080*
H13B	0.4898	0.0862	−0.3043	0.080*
C11	0.1829 (5)	0.0624 (2)	−0.1692 (3)	0.0540 (10)
H11A	0.1366	0.0539	−0.1015	0.065*
H11B	0.2182	0.0110	−0.1973	0.065*
O1	0.6638 (6)	0.0322 (3)	0.0197 (3)	0.0997 (14)
C3	0.2160 (7)	0.1015 (3)	0.2968 (4)	0.0635 (12)
H3A	0.3378	0.0775	0.3143	0.076*
C2	0.0755 (7)	0.1171 (3)	0.3698 (4)	0.0690 (12)
H2A	0.1036	0.1046	0.4358	0.083*
C16	0.0131 (6)	0.0998 (3)	−0.2304 (4)	0.0694 (13)
H16A	−0.1028	0.0643	−0.2316	0.083*
H16B	−0.0287	0.1495	−0.1997	0.083*
C14	0.2691 (10)	0.1683 (3)	−0.3360 (5)	0.0853 (18)
H14A	0.3159	0.1742	−0.4041	0.102*
H14B	0.2334	0.2207	−0.3112	0.102*
C15	0.0829 (9)	0.1154 (4)	−0.3347 (4)	0.0873 (17)
H15A	−0.0252	0.1409	−0.3719	0.105*
H15B	0.1140	0.0651	−0.3670	0.105*

	U11	U22	U33	U12	U13	U23
Br1	0.0827 (3)	0.0985 (4)	0.0723 (4)	0.0064 (2)	−0.0037 (3)	−0.0060 (3)
O4	0.0564 (16)	0.0396 (14)	0.0526 (15)	0.0002 (11)	−0.0015 (12)	0.0001 (14)
C8	0.046 (2)	0.043 (2)	0.0540 (17)	0.0020 (15)	−0.0062 (16)	−0.0023 (18)
C10	0.062 (2)	0.057 (3)	0.086 (4)	0.020 (2)	−0.009 (2)	−0.007 (2)
O3	0.0540 (16)	0.0653 (19)	0.069 (2)	0.0174 (14)	−0.0026 (15)	0.0004 (17)
O2	0.0606 (15)	0.0474 (16)	0.0615 (17)	0.0070 (12)	−0.0094 (14)	−0.0046 (14)
C7	0.069 (3)	0.055 (3)	0.064 (3)	0.0137 (19)	−0.015 (2)	0.001 (2)
C4	0.064 (3)	0.049 (2)	0.056 (3)	0.0003 (18)	−0.015 (2)	0.0050 (19)
C9	0.052 (2)	0.049 (2)	0.072 (3)	0.006 (2)	−0.014 (2)	0.001 (2)
C12	0.0482 (18)	0.040 (2)	0.063 (3)	0.0070 (16)	−0.0009 (19)	−0.005 (2)
C6	0.058 (2)	0.056 (3)	0.083 (4)	−0.0011 (18)	−0.019 (3)	0.010 (2)
C5	0.063 (2)	0.065 (3)	0.060 (3)	−0.0008 (19)	−0.013 (2)	0.016 (2)
C1	0.070 (2)	0.052 (2)	0.049 (2)	−0.0062 (18)	−0.011 (2)	0.0021 (19)
C13	0.075 (3)	0.059 (3)	0.067 (3)	0.010 (2)	0.019 (2)	0.007 (2)
C11	0.057 (2)	0.045 (2)	0.060 (3)	−0.0001 (15)	−0.0026 (18)	−0.004 (2)
O1	0.095 (2)	0.111 (3)	0.093 (3)	0.059 (2)	−0.022 (2)	0.002 (2)
C3	0.070 (3)	0.063 (3)	0.057 (3)	0.012 (2)	−0.017 (2)	0.002 (2)
C2	0.083 (3)	0.061 (3)	0.063 (3)	0.002 (2)	−0.029 (3)	−0.002 (2)
C16	0.058 (2)	0.074 (3)	0.076 (4)	0.005 (2)	−0.009 (2)	−0.016 (3)
C14	0.111 (4)	0.091 (4)	0.054 (3)	0.040 (3)	0.020 (3)	0.016 (3)
C15	0.091 (4)	0.112 (4)	0.059 (3)	0.031 (3)	−0.014 (3)	−0.017 (3)

Br1—C1	1.875 (5)	C5—H5A	0.9300
O4—C8	1.355 (5)	C1—C2	1.391 (6)
O4—C12	1.431 (5)	C13—C14	1.513 (8)
C8—O2	1.201 (5)	C13—H13A	0.9700
C8—C9	1.487 (6)	C13—H13B	0.9700
C10—O1	1.210 (6)	C11—C16	1.525 (6)
C10—O3	1.338 (6)	C11—H11A	0.9700
C10—C9	1.487 (7)	C11—H11B	0.9700
O3—C12	1.441 (5)	C3—C2	1.374 (7)
C7—C9	1.328 (7)	C3—H3A	0.9300
C7—C4	1.462 (7)	C2—H2A	0.9300
C7—H7A	0.9300	C16—C15	1.497 (7)
C4—C3	1.387 (6)	C16—H16A	0.9700
C4—C5	1.392 (6)	C16—H16B	0.9700
C12—C11	1.498 (6)	C14—C15	1.517 (9)
C12—C13	1.520 (6)	C14—H14A	0.9700
C6—C5	1.377 (8)	C14—H14B	0.9700
C6—C1	1.385 (7)	C15—H15A	0.9700
C6—H6A	0.9300	C15—H15B	0.9700
C8—O4—C12	117.6 (4)	C12—C13—H13A	109.3
O2—C8—O4	118.3 (4)	C14—C13—H13B	109.3
O2—C8—C9	125.6 (5)	C12—C13—H13B	109.3
O4—C8—C9	115.8 (4)	H13A—C13—H13B	108.0
O1—C10—O3	118.8 (5)	C12—C11—C16	110.8 (4)
O1—C10—C9	124.1 (5)	C12—C11—H11A	109.5
O3—C10—C9	117.1 (4)	C16—C11—H11A	109.5
C10—O3—C12	118.3 (4)	C12—C11—H11B	109.5
C9—C7—C4	134.4 (4)	C16—C11—H11B	109.5
C9—C7—H7A	112.8	H11A—C11—H11B	108.1
C4—C7—H7A	112.8	C2—C3—C4	121.9 (4)
C3—C4—C5	117.8 (5)	C2—C3—H3A	119.0
C3—C4—C7	117.5 (4)	C4—C3—H3A	119.0
C5—C4—C7	124.5 (5)	C3—C2—C1	119.7 (5)
C7—C9—C10	117.2 (4)	C3—C2—H2A	120.2
C7—C9—C8	126.7 (4)	C1—C2—H2A	120.2
C10—C9—C8	116.1 (5)	C15—C16—C11	110.4 (4)
O4—C12—O3	109.8 (3)	C15—C16—H16A	109.6
O4—C12—C11	111.2 (3)	C11—C16—H16A	109.6
O3—C12—C11	112.0 (3)	C15—C16—H16B	109.6
O4—C12—C13	106.5 (3)	C11—C16—H16B	109.6
O3—C12—C13	105.2 (3)	H16A—C16—H16B	108.1
C11—C12—C13	111.8 (4)	C13—C14—C15	111.8 (4)
C5—C6—C1	120.6 (4)	C13—C14—H14A	109.3
C5—C6—H6A	119.7	C15—C14—H14A	109.3
C1—C6—H6A	119.7	C13—C14—H14B	109.3
C6—C5—C4	120.8 (5)	C15—C14—H14B	109.3
C6—C5—H5A	119.6	H14A—C14—H14B	107.9
C4—C5—H5A	119.6	C16—C15—C14	111.3 (4)
C6—C1—C2	119.1 (5)	C16—C15—H15A	109.4
C6—C1—Br1	120.4 (4)	C14—C15—H15A	109.4
C2—C1—Br1	120.4 (4)	C16—C15—H15B	109.4
C14—C13—C12	111.4 (4)	C14—C15—H15B	109.4
C14—C13—H13A	109.3	H15A—C15—H15B	108.0

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O2	0.93	2.45	3.004 (2)	117
C7—H7A···O1	0.93	2.40	2.812 (2)	106