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

Zeng, W.-L.; Suo, J.-L.; Jian, F.

doi:10.1107/S1600536810040675

organic compounds

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Volume 66| Part 11| November 2010| Page o2837

https://doi.org/10.1107/S1600536810040675

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

Wu-Lan Zeng,^a Jin-Long Suo ^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 9 October 2010; accepted 11 October 2010; online 20 October 2010)

In the title molecule, C₁₇H₁₈O₅, which was prepared by the reaction of (R)-1,5-dioxaspiro[5.5]undecane-2,4-dione and 4-methoxybenzaldehyde with ethanol, the 1,3-dioxane ring is in a distorted envelope conformation with the spiro C atom forming the flap. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For background information on spiro-compounds, see: Jiang et al. (1998 ); Lian et al. (2008 ); Wei et al. (2008 ). For a related structure, see: Zeng et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₇H₁₈O₅
M_r = 302.31
Monoclinic, P 2₁ /c
a = 15.723 (3) Å
b = 10.531 (2) Å
c = 9.2029 (18) Å
β = 90.00 (3)°
V = 1523.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
14509 measured reflections
3493 independent reflections
2450 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.185
S = 1.11
3493 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O3ⁱ	0.93	2.58	3.405 (3)	149 (3)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810040675/hb5678sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040675/hb5678Isup2.hkl

checkCIF report

Comment top

Spiro compounds are widely used in medicine, catalysis and optical material (Lian et al., 2008; Jiang et al., 1998; Wei et al., 2008) owing to their interesting conformational features. We have recently reported the crystal structure of (Z)-3-(3-phenylallylidene)-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 reported here.

The 1,3-dioxane ring is in a distored envelope conformation with atom C11 atom common to the cyclohexane forming the flap. The cyclohexane exists in a distorted chair comformation, with the puckering parameters Q=0.552Å, theta=175.1°, Phi=39.2°; The crystal structure is stabilized by weak intra and 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). For a related structure, see: Zeng et al. (2009). For puckering parameters, see: Cremer & Pople (1975).

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 303 K. 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 4-methoxybenzaldehyde (8.16 g, 0.06 mol) was added. The solution was then filtered and concentrated. Colourless blocks of (I) were obtained by evaporation of an petroleum ether-ethylacetate (3:1 v/v) solution at room temperature over a period of one week.

Structure description top

For background information on spiro-compounds, see: Jiang et al. (1998); Lian et al. (2008); Wei et al. (2008). For a related structure, see: Zeng et al. (2009). For puckering parameters, see: Cremer & Pople (1975).

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.

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

Crystal data top

C₁₇H₁₈O₅	F(000) = 640
M_r = 302.31	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2450 reflections
a = 15.723 (3) Å	θ = 3.2–27.5°
b = 10.531 (2) Å	µ = 0.10 mm⁻¹
c = 9.2029 (18) Å	T = 293 K
β = 90.00 (3)°	Block, colorless
V = 1523.8 (5) Å³	0.25 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2450 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
phi and ω scans	h = −20→20
14509 measured reflections	k = −11→13
3493 independent reflections	l = −11→11

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0988P)² + 0.1666P] where P = (F_o² + 2F_c²)/3
3493 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₇H₁₈O₅	V = 1523.8 (5) Å³
M_r = 302.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.723 (3) Å	µ = 0.10 mm⁻¹
b = 10.531 (2) Å	T = 293 K
c = 9.2029 (18) Å	0.25 × 0.16 × 0.10 mm
β = 90.00 (3)°

Data collection top

Bruker SMART CCD diffractometer	2450 reflections with I > 2σ(I)
14509 measured reflections	R_int = 0.057
3493 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.11	Δρ_max = 0.34 e Å⁻³
3493 reflections	Δρ_min = −0.41 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
O5	0.35323 (7)	0.60512 (11)	0.18736 (14)	0.0621 (4)
O4	0.27576 (8)	0.50924 (12)	0.37464 (12)	0.0613 (4)
O3	0.14427 (8)	0.56348 (16)	0.42086 (13)	0.0767 (4)
C12	0.20204 (11)	0.56349 (17)	0.33460 (18)	0.0573 (4)
O1	−0.22145 (8)	0.60711 (16)	0.16227 (16)	0.0799 (5)
C9	0.20107 (11)	0.62557 (17)	0.1912 (2)	0.0591 (4)
C11	0.34102 (10)	0.49138 (15)	0.26925 (17)	0.0520 (4)
C5	0.04075 (11)	0.64170 (17)	0.13577 (19)	0.0596 (4)
O2	0.29512 (10)	0.73591 (18)	0.0312 (2)	0.1155 (7)
C2	−0.13524 (11)	0.61345 (19)	0.15722 (19)	0.0612 (4)
C17	0.31883 (13)	0.38211 (18)	0.1710 (2)	0.0663 (5)
H17A	0.2690	0.4036	0.1141	0.080*
H17B	0.3054	0.3080	0.2293	0.080*
C4	−0.01498 (12)	0.72360 (19)	0.0631 (2)	0.0696 (5)
H4A	0.0072	0.7881	0.0054	0.084*
C6	0.00472 (12)	0.54299 (19)	0.2157 (2)	0.0661 (5)
H6A	0.0402	0.4856	0.2628	0.079*
C13	0.42224 (12)	0.4727 (2)	0.3519 (2)	0.0744 (6)
H13A	0.4141	0.4065	0.4239	0.089*
H13B	0.4364	0.5505	0.4027	0.089*
C8	0.13114 (12)	0.66335 (18)	0.1175 (2)	0.0669 (5)
H8A	0.1438	0.7143	0.0378	0.080*
C7	−0.08152 (12)	0.5284 (2)	0.2265 (2)	0.0668 (5)
H7A	−0.1040	0.4617	0.2803	0.080*
C10	0.28435 (12)	0.66098 (19)	0.1279 (2)	0.0707 (5)
C3	−0.10110 (13)	0.7112 (2)	0.0747 (2)	0.0725 (5)
H3A	−0.1368	0.7681	0.0274	0.087*
C15	0.4723 (2)	0.3234 (3)	0.1548 (4)	0.1182 (11)
H15A	0.5187	0.3067	0.0880	0.142*
H15B	0.4637	0.2483	0.2139	0.142*
C14	0.49532 (14)	0.4363 (3)	0.2527 (3)	0.1001 (9)
H14A	0.5445	0.4144	0.3112	0.120*
H14B	0.5104	0.5085	0.1926	0.120*
C16	0.39229 (19)	0.3516 (3)	0.0700 (3)	0.1034 (9)
H16A	0.3777	0.2787	0.0107	0.124*
H16B	0.4023	0.4231	0.0058	0.124*
C1	−0.25940 (14)	0.5094 (3)	0.2471 (3)	0.1045 (9)
H1A	−0.3202	0.5159	0.2409	0.157*
H1B	−0.2420	0.5182	0.3466	0.157*
H1C	−0.2416	0.4280	0.2110	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.0527 (7)	0.0513 (7)	0.0822 (8)	−0.0017 (5)	0.0135 (6)	0.0140 (5)
O4	0.0618 (7)	0.0751 (8)	0.0470 (6)	−0.0023 (6)	0.0115 (5)	−0.0021 (5)
O3	0.0619 (8)	0.1095 (12)	0.0587 (7)	−0.0099 (7)	0.0195 (6)	−0.0150 (7)
C12	0.0573 (9)	0.0596 (10)	0.0549 (9)	−0.0089 (8)	0.0141 (7)	−0.0117 (7)
O1	0.0530 (8)	0.1061 (12)	0.0808 (9)	−0.0026 (7)	0.0057 (6)	0.0112 (8)
C9	0.0532 (9)	0.0508 (9)	0.0732 (11)	0.0017 (7)	0.0182 (8)	0.0042 (7)
C11	0.0554 (9)	0.0501 (9)	0.0506 (8)	−0.0030 (7)	0.0110 (7)	0.0037 (6)
C5	0.0575 (10)	0.0563 (10)	0.0650 (10)	0.0027 (8)	0.0121 (7)	0.0050 (7)
O2	0.0713 (10)	0.1084 (13)	0.1668 (16)	0.0208 (9)	0.0394 (10)	0.0879 (12)
C2	0.0524 (9)	0.0747 (12)	0.0563 (9)	0.0010 (8)	0.0056 (7)	−0.0017 (8)
C17	0.0790 (13)	0.0524 (10)	0.0675 (11)	0.0010 (8)	0.0074 (9)	−0.0063 (8)
C4	0.0639 (11)	0.0664 (12)	0.0787 (12)	0.0033 (9)	0.0108 (9)	0.0185 (9)
C6	0.0606 (11)	0.0611 (11)	0.0765 (12)	−0.0023 (8)	−0.0002 (8)	0.0152 (9)
C13	0.0626 (11)	0.0894 (15)	0.0710 (11)	−0.0060 (10)	−0.0017 (9)	0.0195 (10)
C8	0.0621 (11)	0.0569 (10)	0.0816 (12)	0.0061 (8)	0.0200 (9)	0.0130 (8)
C7	0.0622 (11)	0.0716 (12)	0.0666 (10)	−0.0104 (9)	0.0009 (8)	0.0157 (9)
C10	0.0582 (10)	0.0566 (11)	0.0972 (14)	0.0080 (8)	0.0229 (9)	0.0234 (9)
C3	0.0640 (12)	0.0718 (12)	0.0816 (12)	0.0103 (9)	0.0032 (9)	0.0159 (10)
C15	0.110 (2)	0.105 (2)	0.140 (2)	0.0499 (18)	0.0472 (19)	0.0149 (19)
C14	0.0599 (12)	0.129 (2)	0.1108 (18)	0.0150 (13)	0.0135 (12)	0.0447 (18)
C16	0.115 (2)	0.0978 (19)	0.0974 (16)	0.0332 (16)	0.0266 (15)	−0.0256 (14)
C1	0.0627 (13)	0.159 (3)	0.0916 (16)	−0.0262 (14)	0.0035 (11)	0.0349 (16)

Geometric parameters (Å, º) top

O5—C10	1.348 (2)	C4—C3	1.365 (3)
O5—C11	1.4281 (19)	C4—H4A	0.9300
O4—C12	1.344 (2)	C6—C7	1.368 (3)
O4—C11	1.4245 (19)	C6—H6A	0.9300
O3—C12	1.2064 (19)	C13—C14	1.516 (3)
C12—C9	1.473 (3)	C13—H13A	0.9700
O1—C2	1.358 (2)	C13—H13B	0.9700
O1—C1	1.423 (3)	C8—H8A	0.9300
C9—C8	1.352 (3)	C7—H7A	0.9300
C9—C10	1.481 (2)	C3—H3A	0.9300
C11—C13	1.499 (3)	C15—C16	1.509 (4)
C11—C17	1.504 (2)	C15—C14	1.535 (5)
C5—C6	1.394 (3)	C15—H15A	0.9700
C5—C4	1.400 (3)	C15—H15B	0.9700
C5—C8	1.449 (3)	C14—H14A	0.9700
O2—C10	1.201 (2)	C14—H14B	0.9700
C2—C7	1.386 (3)	C16—H16A	0.9700
C2—C3	1.387 (3)	C16—H16B	0.9700
C17—C16	1.517 (3)	C1—H1A	0.9600
C17—H17A	0.9700	C1—H1B	0.9600
C17—H17B	0.9700	C1—H1C	0.9600

C10—O5—C11	118.18 (13)	H13A—C13—H13B	107.9
C12—O4—C11	119.39 (13)	C9—C8—C5	133.89 (17)
O3—C12—O4	117.97 (17)	C9—C8—H8A	113.1
O3—C12—C9	125.58 (18)	C5—C8—H8A	113.1
O4—C12—C9	116.32 (14)	C6—C7—C2	119.86 (18)
C2—O1—C1	118.23 (18)	C6—C7—H7A	120.1
C8—C9—C12	126.06 (16)	C2—C7—H7A	120.1
C8—C9—C10	116.61 (16)	O2—C10—O5	118.29 (17)
C12—C9—C10	117.06 (16)	O2—C10—C9	125.55 (18)
O4—C11—O5	110.20 (13)	O5—C10—C9	116.15 (15)
O4—C11—C13	106.60 (14)	C4—C3—C2	119.86 (18)
O5—C11—C13	105.28 (14)	C4—C3—H3A	120.1
O4—C11—C17	110.06 (14)	C2—C3—H3A	120.1
O5—C11—C17	110.83 (14)	C16—C15—C14	110.4 (2)
C13—C11—C17	113.69 (16)	C16—C15—H15A	109.6
C6—C5—C4	117.22 (17)	C14—C15—H15A	109.6
C6—C5—C8	125.26 (17)	C16—C15—H15B	109.6
C4—C5—C8	117.48 (16)	C14—C15—H15B	109.6
O1—C2—C7	124.10 (17)	H15A—C15—H15B	108.1
O1—C2—C3	116.19 (17)	C13—C14—C15	111.7 (2)
C7—C2—C3	119.70 (17)	C13—C14—H14A	109.3
C11—C17—C16	110.71 (19)	C15—C14—H14A	109.3
C11—C17—H17A	109.5	C13—C14—H14B	109.3
C16—C17—H17A	109.5	C15—C14—H14B	109.3
C11—C17—H17B	109.5	H14A—C14—H14B	107.9
C16—C17—H17B	109.5	C15—C16—C17	111.1 (2)
H17A—C17—H17B	108.1	C15—C16—H16A	109.4
C3—C4—C5	121.64 (18)	C17—C16—H16A	109.4
C3—C4—H4A	119.2	C15—C16—H16B	109.4
C5—C4—H4A	119.2	C17—C16—H16B	109.4
C7—C6—C5	121.66 (18)	H16A—C16—H16B	108.0
C7—C6—H6A	119.2	O1—C1—H1A	109.5
C5—C6—H6A	119.2	O1—C1—H1B	109.5
C11—C13—C14	111.92 (18)	H1A—C1—H1B	109.5
C11—C13—H13A	109.2	O1—C1—H1C	109.5
C14—C13—H13A	109.2	H1A—C1—H1C	109.5
C11—C13—H13B	109.2	H1B—C1—H1C	109.5
C14—C13—H13B	109.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O3ⁱ	0.93	2.58	3.405 (3)	149 (3)

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈O₅
M_r	302.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.723 (3), 10.531 (2), 9.2029 (18)
β (°)	90, 90.00 (3), 90
V (Å³)	1523.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.16 × 0.10

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14509, 3493, 2450
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.185, 1.11
No. of reflections	3493
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.41

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
C8—H8A···O3ⁱ	0.93	2.5762	3.405 (3)	149 (3)

Symmetry code: (i) x, −y+3/2, z−1/2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 6, 1354–1358. CrossRef Web of Science 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. Org. Chem. 28, 1501–1514. CAS Google Scholar
Zeng, W.-L., Zhang, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2586. Web of Science CSD CrossRef IUCr Journals Google Scholar

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