3-(4-Bromo­benzyl­idene)-1,5-dioxaspiro­[5.5]undecane-2,4-dione

Zeng, W.-L.

doi:10.1107/S1600536811001516

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o426

doi:10.1107/S1600536811001516

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3-(4-Bromobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione

Wu-Lan Zeng ^a ^*

^aMicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: wulanzeng@163.com

(Received 30 December 2010; accepted 11 January 2011; online 15 January 2011)

The title molecule, C₁₆H₁₅BrO₄, was prepared by the reaction of (R)-2,4-dioxo-1,5-dioxaspiro[5.5]undecane and 4-bromobenzaldehyde with ethanol. The 1,3-dioxane ring exhibits a distorted boat and the fused cyclohexane 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_r = 351.18
Orthorhombic, P n a 2₁
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.124
S = 0.93
3243 reflections
191 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −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 ).

Supporting information

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

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

checkCIF report

Comment top

We have recently reported the crystal structure of 3-(2-Furylmethylene)-1,5-dioxaspiro[5.5]undecane-2,4-dione (Zeng & Jian, 2009) and 3-[(5-Methylfuran-2-yl)methylene]-1,5-dioxaspiro- [5.5]undecane-2,4-dione (Zeng et al. 2009). As part of our ongoing studies on new spiro compounds with potentially higher bioactivity, the title compound, (I) (Fig. 1), has been synthesized and its structure is determined here. The crystal structure analysis confirms the title compound with atom C7 connected by the 1,3-dioxane ring via C4-C7 single bond [1.462 (7)Å] and the phenyl ring via C7═C9 double bond [1.328 (7)Å]. In (I) (Fig. 1), the 1,3-dioxane ring has a distorted boat conformation. The four atoms (O3/C10/C8/O4)are approximately planar with an rms deviation of 0.0279 Å. The max. deviation from the mean plane is 0.029 (1) Å, and atoms C9 and C12 deviate -0.245 (2)Å and -0.567 (2) Å, respectively. Thus, the cyclohexane ring exists in a chair comformation (Cremer & Pople, 1975) with the puckering parameters Q =0.560 (5)Å, θ =3.9 (5)°, ϕ = 312 (10)°.

Related literature top

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

Experimental top

The mixture of malonic acid (6.24 g, 0.06 mol) and acetic anhydride(9 ml) in strong sulfuric acid (0.25 ml) was stirred with water at 303 K. After dissolving, cyclohexanone (5.88 g, 0.06 mol) was added dropwise into the solution for 1 h. The reaction was allowed to proceed for 4 h. The mixture was cooled and filtered, and then an ethanol solution of 4-bromobenzaldehyde (11.04 g,0.06 mol) was added. The solution was then filtered and concentrated. Single crystals were obtained by evaporation of an ethanol solution of (I) at room temperature over a period of one week.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.

3-(4-Bromobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione top

Crystal data top

C₁₆H₁₅BrO₄	F(000) = 712
M_r = 351.18	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0603P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.124	(Δ/σ)_max < 0.001
S = 0.93	Δρ_max = 0.31 e Å⁻³
3243 reflections	Δρ_min = −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	Absolute structure parameter: −0.033 (13)

Crystal data top

C₁₆H₁₅BrO₄	V = 1487.2 (5) Å³
M_r = 351.18	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 6.6008 (13) Å	µ = 2.78 mm⁻¹
b = 16.784 (3) Å	T = 293 K
c = 13.424 (3) Å	0.18 × 0.12 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2042 reflections with I > 2σ(I)
12420 measured reflections	R_int = 0.065
3243 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.124	Δρ_max = 0.31 e Å⁻³
S = 0.93	Δρ_min = −0.34 e Å⁻³
3243 reflections	Absolute structure: Flack (1983), 1459 Friedel pairs
191 parameters	Absolute structure parameter: −0.033 (13)
2 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrO₄
M_r	351.18
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	6.6008 (13), 16.784 (3), 13.424 (3)
V (Å³)	1487.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.78
Crystal size (mm)	0.18 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12420, 3243, 2042
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.124, 0.93
No. of reflections	3243
No. of parameters	191
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.34
Absolute structure	Flack (1983), 1459 Friedel pairs
Absolute structure parameter	−0.033 (13)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeng, W.-L. & Jian, F. (2009). Acta Cryst. E65, o1875. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zeng, W.-L., Zhang, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2035. Web of Science CSD CrossRef IUCr Journals Google Scholar