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

Zeng, W.-L.; Zhang, H.-X.; Jian, F.-F.

doi:10.1107/S1600536809038781

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2586

doi:10.1107/S1600536809038781

Open

access

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

Wu-Lan Zeng,^a Hua-Xiang Zhang ^a and Fang-Fang Jian ^b ^*

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

(Received 18 September 2009; accepted 24 September 2009; online 30 September 2009)

In the title compound, C₁₈H₁₈O₄, the 1,3-dioxane ring adopts a distorted envelope conformation with the C atom common to the cyclohexane ring forming the flap. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds occur.

Related literature

For background information on spiro-compounds, see: Jiang et al. (1998 ); Lian et al. (2008 ); Wei et al. (2008 ).

Experimental

Crystal data

C₁₈H₁₈O₄
M_r = 298.32
Triclinic, $[P \overline 1]$
a = 7.1177 (14) Å
b = 9.5506 (19) Å
c = 11.734 (2) Å
α = 106.82 (3)°
β = 100.14 (3)°
γ = 93.35 (3)°
V = 746.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
7448 measured reflections
3401 independent reflections
2309 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.130
S = 1.17
3401 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O2ⁱ	0.97	2.52	3.440 (2)	158
Symmetry code: (i) -x, -y+1, -z.

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809038781/hb5108sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038781/hb5108Isup2.hkl

checkCIF report

Comment top

Spiro compounds are widely used in medicine, catalysis and optical materials (Lian et al., 2008; Jiang et al., 1998; Wei et al., 2008) owing to their interesting conformational features. We report here the synthesis and structure of the title compound, (I) (Fig. 1), as part of our ongoing studies on new spiro compounds with potentially higher bioactivity.

The 1,3-dioxane ring is in a distored envelope conformation with atom C11 atom common to the cyclohexane forming the flap. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background information on spiro-compounds, see: Jiang et al. (1998); Lian et al. (2008); Wei et al. (2008).

Experimental top

A 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 303K, After dissolving, cyclohexanone (5.88 g, 0.06 mol) was added dropwise into 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 (Z)-3-phenylacrylaldehyde (7.92g, 0.06 mol) was added. The solution was then filtered and concentrated. Yellow blocks of (I) were obtained by evaporation of a petroleum ether–ethylacetate (3:1 v/v) solution 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: SHELXTL (Sheldrick, 2008).

Figures top

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

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

Crystal data top

C₁₈H₁₈O₄	Z = 2
M_r = 298.32	F(000) = 316
Triclinic, P1	D_x = 1.327 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1177 (14) Å	Cell parameters from 3401 reflections
b = 9.5506 (19) Å	θ = 3.1–27.5°
c = 11.734 (2) Å	µ = 0.09 mm⁻¹
α = 106.82 (3)°	T = 293 K
β = 100.14 (3)°	Block, yellow
γ = 93.35 (3)°	0.22 × 0.18 × 0.10 mm
V = 746.6 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	2309 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −8→9
7448 measured reflections	k = −12→12
3401 independent reflections	l = −15→15

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0724P)²] where P = (F_o² + 2F_c²)/3
3401 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₈O₄	γ = 93.35 (3)°
M_r = 298.32	V = 746.6 (3) Å³
Triclinic, P1	Z = 2
a = 7.1177 (14) Å	Mo Kα radiation
b = 9.5506 (19) Å	µ = 0.09 mm⁻¹
c = 11.734 (2) Å	T = 293 K
α = 106.82 (3)°	0.22 × 0.18 × 0.10 mm
β = 100.14 (3)°

Data collection top

Bruker SMART CCD diffractometer	2309 reflections with I > 2σ(I)
7448 measured reflections	R_int = 0.016
3401 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.17	Δρ_max = 0.30 e Å⁻³
3401 reflections	Δρ_min = −0.21 e Å⁻³
199 parameters

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
O4	0.07551 (13)	0.64682 (9)	0.13593 (9)	0.0440 (3)
O3	0.27862 (12)	0.86963 (9)	0.18966 (9)	0.0435 (3)
C18	−0.01600 (18)	0.86915 (14)	0.26210 (12)	0.0386 (3)
O2	−0.18747 (14)	0.63080 (11)	0.20875 (11)	0.0555 (3)
C17	−0.05451 (19)	0.70896 (14)	0.20042 (13)	0.0408 (3)
C11	0.19207 (18)	0.73899 (13)	0.09196 (12)	0.0375 (3)
C12	0.07076 (19)	0.77924 (15)	−0.01133 (13)	0.0443 (3)
H12A	−0.0251	0.8396	0.0195	0.053*
H12B	0.0042	0.6902	−0.0723	0.053*
C10	0.35558 (19)	0.65608 (14)	0.05319 (14)	0.0440 (3)
H10A	0.3043	0.5604	−0.0042	0.053*
H10B	0.4353	0.6405	0.1235	0.053*
C16	0.16915 (19)	0.94609 (15)	0.26336 (13)	0.0443 (3)
C4	−0.2995 (2)	1.28109 (15)	0.52506 (13)	0.0430 (3)
C14	−0.1418 (2)	1.08555 (15)	0.39392 (13)	0.0450 (3)
H14A	−0.0315	1.1500	0.4069	0.054*
C15	−0.15033 (19)	0.93622 (15)	0.32054 (13)	0.0426 (3)
H15A	−0.2635	0.8767	0.3116	0.051*
O1	0.23340 (15)	1.06908 (12)	0.32633 (13)	0.0728 (4)
C13	−0.2902 (2)	1.13463 (16)	0.44451 (13)	0.0453 (3)
H13A	−0.3994	1.0674	0.4260	0.054*
C5	−0.4695 (2)	1.31394 (17)	0.56535 (14)	0.0511 (4)
H5A	−0.5745	1.2418	0.5408	0.061*
C9	0.4779 (2)	0.74002 (16)	−0.00542 (15)	0.0520 (4)
H9A	0.5422	0.8302	0.0551	0.062*
H9B	0.5757	0.6807	−0.0346	0.062*
C3	−0.1442 (2)	1.39115 (17)	0.56447 (14)	0.0505 (4)
H3A	−0.0287	1.3716	0.5399	0.061*
C6	−0.4845 (2)	1.45175 (18)	0.64115 (15)	0.0576 (4)
H6A	−0.5987	1.4717	0.6676	0.069*
C8	0.3571 (2)	0.77756 (18)	−0.11085 (16)	0.0584 (4)
H8A	0.3042	0.6875	−0.1755	0.070*
H8B	0.4376	0.8363	−0.1426	0.070*
C2	−0.1606 (2)	1.52867 (18)	0.63955 (15)	0.0585 (4)
H2A	−0.0563	1.6015	0.6649	0.070*
C7	0.1938 (2)	0.86284 (17)	−0.06957 (15)	0.0551 (4)
H7A	0.2471	0.9577	−0.0115	0.066*
H7B	0.1140	0.8803	−0.1390	0.066*
C1	−0.3313 (3)	1.55903 (18)	0.67735 (15)	0.0590 (4)
H1A	−0.3420	1.6523	0.7274	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0515 (5)	0.0329 (5)	0.0487 (6)	0.0045 (4)	0.0164 (4)	0.0102 (4)
O3	0.0393 (5)	0.0384 (5)	0.0451 (6)	0.0004 (4)	0.0101 (4)	0.0006 (4)
C18	0.0396 (6)	0.0387 (7)	0.0341 (7)	0.0034 (5)	0.0056 (5)	0.0072 (6)
O2	0.0517 (6)	0.0479 (6)	0.0653 (8)	−0.0055 (5)	0.0172 (5)	0.0136 (5)
C17	0.0412 (7)	0.0411 (7)	0.0386 (7)	0.0026 (6)	0.0063 (6)	0.0112 (6)
C11	0.0407 (6)	0.0300 (6)	0.0389 (7)	0.0024 (5)	0.0092 (5)	0.0059 (5)
C12	0.0454 (7)	0.0429 (7)	0.0438 (8)	0.0112 (6)	0.0078 (6)	0.0113 (6)
C10	0.0470 (7)	0.0359 (6)	0.0493 (8)	0.0123 (6)	0.0113 (6)	0.0110 (6)
C16	0.0415 (7)	0.0416 (7)	0.0428 (8)	0.0034 (6)	0.0089 (6)	0.0024 (6)
C4	0.0470 (7)	0.0489 (7)	0.0366 (7)	0.0114 (6)	0.0134 (6)	0.0144 (6)
C14	0.0458 (7)	0.0465 (7)	0.0407 (8)	0.0060 (6)	0.0115 (6)	0.0082 (6)
C15	0.0420 (7)	0.0462 (7)	0.0384 (7)	0.0034 (6)	0.0086 (6)	0.0112 (6)
O1	0.0542 (6)	0.0493 (6)	0.0873 (9)	−0.0122 (5)	0.0238 (6)	−0.0238 (6)
C13	0.0448 (7)	0.0481 (7)	0.0426 (8)	0.0063 (6)	0.0109 (6)	0.0118 (6)
C5	0.0522 (8)	0.0555 (8)	0.0493 (9)	0.0097 (7)	0.0199 (7)	0.0151 (7)
C9	0.0492 (8)	0.0500 (8)	0.0612 (10)	0.0158 (7)	0.0235 (7)	0.0145 (7)
C3	0.0492 (8)	0.0571 (9)	0.0440 (9)	0.0071 (7)	0.0147 (6)	0.0104 (7)
C6	0.0644 (10)	0.0632 (9)	0.0533 (10)	0.0229 (8)	0.0298 (8)	0.0165 (8)
C8	0.0696 (10)	0.0579 (9)	0.0577 (10)	0.0154 (8)	0.0298 (8)	0.0216 (8)
C2	0.0685 (10)	0.0551 (9)	0.0474 (9)	0.0000 (8)	0.0143 (8)	0.0086 (8)
C7	0.0685 (10)	0.0530 (8)	0.0541 (10)	0.0214 (7)	0.0191 (8)	0.0253 (8)
C1	0.0802 (11)	0.0530 (9)	0.0458 (9)	0.0170 (8)	0.0236 (8)	0.0099 (7)

Geometric parameters (Å, º) top

O4—C17	1.3536 (17)	C14—C15	1.428 (2)
O4—C11	1.4344 (16)	C14—H14A	0.9300
O3—C16	1.3515 (17)	C15—H15A	0.9300
O3—C11	1.4437 (16)	C13—H13A	0.9300
C18—C15	1.3575 (19)	C5—C6	1.381 (2)
C18—C16	1.4665 (19)	C5—H5A	0.9300
C18—C17	1.4765 (19)	C9—C8	1.522 (2)
O2—C17	1.2062 (17)	C9—H9A	0.9700
C11—C10	1.5080 (18)	C9—H9B	0.9700
C11—C12	1.5174 (18)	C3—C2	1.378 (2)
C12—C7	1.522 (2)	C3—H3A	0.9300
C12—H12A	0.9700	C6—C1	1.369 (2)
C12—H12B	0.9700	C6—H6A	0.9300
C10—C9	1.524 (2)	C8—C7	1.526 (2)
C10—H10A	0.9700	C8—H8A	0.9700
C10—H10B	0.9700	C8—H8B	0.9700
C16—O1	1.2045 (17)	C2—C1	1.384 (2)
C4—C3	1.394 (2)	C2—H2A	0.9300
C4—C5	1.395 (2)	C7—H7A	0.9700
C4—C13	1.457 (2)	C7—H7B	0.9700
C14—C13	1.344 (2)	C1—H1A	0.9300

C17—O4—C11	118.14 (10)	C14—C15—H15A	115.5
C16—O3—C11	119.54 (10)	C14—C13—C4	127.39 (14)
C15—C18—C16	123.28 (12)	C14—C13—H13A	116.3
C15—C18—C17	117.99 (12)	C4—C13—H13A	116.3
C16—C18—C17	118.63 (12)	C6—C5—C4	121.11 (15)
O2—C17—O4	118.86 (12)	C6—C5—H5A	119.4
O2—C17—C18	124.36 (14)	C4—C5—H5A	119.4
O4—C17—C18	116.68 (12)	C8—C9—C10	111.66 (12)
O4—C11—O3	110.01 (11)	C8—C9—H9A	109.3
O4—C11—C10	107.54 (10)	C10—C9—H9A	109.3
O3—C11—C10	106.20 (10)	C8—C9—H9B	109.3
O4—C11—C12	109.82 (10)	C10—C9—H9B	109.3
O3—C11—C12	110.77 (10)	H9A—C9—H9B	107.9
C10—C11—C12	112.40 (12)	C2—C3—C4	120.55 (15)
C11—C12—C7	111.29 (12)	C2—C3—H3A	119.7
C11—C12—H12A	109.4	C4—C3—H3A	119.7
C7—C12—H12A	109.4	C1—C6—C5	119.95 (15)
C11—C12—H12B	109.4	C1—C6—H6A	120.0
C7—C12—H12B	109.4	C5—C6—H6A	120.0
H12A—C12—H12B	108.0	C9—C8—C7	110.64 (13)
C11—C10—C9	111.33 (10)	C9—C8—H8A	109.5
C11—C10—H10A	109.4	C7—C8—H8A	109.5
C9—C10—H10A	109.4	C9—C8—H8B	109.5
C11—C10—H10B	109.4	C7—C8—H8B	109.5
C9—C10—H10B	109.4	H8A—C8—H8B	108.1
H10A—C10—H10B	108.0	C3—C2—C1	120.34 (16)
O1—C16—O3	117.67 (13)	C3—C2—H2A	119.8
O1—C16—C18	125.75 (14)	C1—C2—H2A	119.8
O3—C16—C18	116.55 (12)	C12—C7—C8	111.50 (12)
C3—C4—C5	118.04 (14)	C12—C7—H7A	109.3
C3—C4—C13	122.64 (13)	C8—C7—H7A	109.3
C5—C4—C13	119.32 (14)	C12—C7—H7B	109.3
C13—C14—C15	121.18 (14)	C8—C7—H7B	109.3
C13—C14—H14A	119.4	H7A—C7—H7B	108.0
C15—C14—H14A	119.4	C6—C1—C2	120.00 (16)
C18—C15—C14	128.93 (13)	C6—C1—H1A	120.0
C18—C15—H15A	115.5	C2—C1—H1A	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O2ⁱ	0.97	2.52	3.440 (2)	158

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈O₄
M_r	298.32
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1177 (14), 9.5506 (19), 11.734 (2)
α, β, γ (°)	106.82 (3), 100.14 (3), 93.35 (3)
V (Å³)	746.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.18 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7448, 3401, 2309
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.130, 1.17
No. of reflections	3401
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O2ⁱ	0.97	2.52	3.440 (2)	158

Symmetry code: (i) −x, −y+1, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jiang, Y. Z., Xue, S., Li, Z., Deng, J. G., Mi, A. Q. & Albert, S. C. C. (1998). Tetrahedron, 9, 3185–3189. CrossRef CAS Google Scholar
Lian, Y., Guo, J. J., Liu, X. M. & Wei, R. B. (2008). Chem. Res. Chin. Univ. 24, 441–444. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wei, R. B., Liu, B., Liu, Y., Guo, J. J. & Zhang, D. W. (2008). Chin. J. Or. C. 28, 1501–1514. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2586

doi:10.1107/S1600536809038781

Open

access