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

Zeng, W.-L.

doi:10.1107/S1600536811016813

organic compounds

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Volume 67| Part 6| June 2011| Page o1362

doi:10.1107/S1600536811016813

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3-(2,4-Dichlorobenzylidene)-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 21 April 2011; accepted 4 May 2011; online 7 May 2011)

In the title molecule, C₁₆H₁₄Cl₂O₄, the 1,3-dioxane and cyclohexane rings exhibit distorted boat and chair conformations, respectively. In the crystal, a pair of weak intermolecular C—H⋯O hydrogen bonds link the molecules into an inversion dimer.

Related literature

For ring puckering parameters, see: Cremer & Pople (1975 ). For related structures, see: Zeng (2011a ,b ).

Experimental

Crystal data

C₁₆H₁₄Cl₂O₄
M_r = 341.17
Triclinic, $[P \overline 1]$
a = 7.2378 (6) Å
b = 7.6496 (7) Å
c = 14.8099 (13) Å
α = 100.569 (2)°
β = 100.870 (2)°
γ = 99.050 (1)°
V = 775.80 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 K
0.24 × 0.22 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.903, T_max = 0.934
4085 measured reflections
2697 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.073
S = 1.01
2697 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.19 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
C13—H13⋯O3ⁱ	0.93	2.50	3.286 (3)	143
Symmetry code: (i) -x, -y+2, -z+1.

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/S1600536811016813/is2706sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016813/is2706Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016813/is2706Isup3.cml

checkCIF report

Comment top

We have recently reported the crystal structures of 3-(4-bromobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione and 3-(4-fluorobenzylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione (Zeng, 2011a,b). As part of our ongoing studies on new spiro compounds with potentially higher bioactivity, the title compound, (I), has been synthesized.

The crystal structure analysis (Fig. 1) confirms that the 1,3-dioxane ring and the benzene ring are connected via C10-C11 single bond [1.462 (3) Å] and C2═C10 double bond [1.346 (3) Å]. The 1,3-dioxane ring has a distorted boat conformation with C4 atom common to the cyclohexane forming the flap. The cyclohexane ring exists in a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.552 Å, θ = 0.7°, ϕ = 242.54°.

Related literature top

For ring puckering parameters, see: Cremer & Pople (1975). For related structures, see: Zeng (2011a,b).

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 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 2,4-dichlorobenzaldehyde (10.44 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, drawn with 30% probability ellipsoids and spheres of arbitrary size for the H atoms.

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

Crystal data top

C₁₆H₁₄Cl₂O₄	Z = 2
M_r = 341.17	F(000) = 352
Triclinic, P1	D_x = 1.461 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2378 (6) Å	Cell parameters from 1133 reflections
b = 7.6496 (7) Å	θ = 3.0–26.3°
c = 14.8099 (13) Å	µ = 0.43 mm⁻¹
α = 100.569 (2)°	T = 298 K
β = 100.870 (2)°	Block, colorless
γ = 99.050 (1)°	0.24 × 0.22 × 0.16 mm
V = 775.80 (12) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2697 independent reflections
Radiation source: fine-focus sealed tube	1596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
T_min = 0.903, T_max = 0.934	k = −9→8
4085 measured reflections	l = −15→17

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0188P)²] where P = (F_o² + 2F_c²)/3
2697 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₆H₁₄Cl₂O₄	γ = 99.050 (1)°
M_r = 341.17	V = 775.80 (12) Å³
Triclinic, P1	Z = 2
a = 7.2378 (6) Å	Mo Kα radiation
b = 7.6496 (7) Å	µ = 0.43 mm⁻¹
c = 14.8099 (13) Å	T = 298 K
α = 100.569 (2)°	0.24 × 0.22 × 0.16 mm
β = 100.870 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2697 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1596 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.934	R_int = 0.023
4085 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.01	Δρ_max = 0.19 e Å⁻³
2697 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
Cl1	0.24503 (11)	1.26534 (9)	0.42676 (5)	0.0765 (3)
Cl2	0.26105 (12)	1.05072 (12)	0.75170 (5)	0.0981 (3)
O1	0.0537 (2)	0.4031 (2)	0.21259 (10)	0.0524 (4)
O2	0.1859 (2)	0.5715 (2)	0.11368 (10)	0.0544 (4)
O3	−0.0445 (2)	0.5412 (2)	0.33392 (12)	0.0641 (5)
O4	0.2444 (3)	0.8711 (2)	0.14747 (12)	0.0737 (6)
C1	0.0566 (4)	0.5535 (3)	0.27859 (17)	0.0477 (6)
C2	0.1771 (3)	0.7246 (3)	0.27024 (16)	0.0446 (6)
C3	0.2092 (4)	0.7332 (4)	0.17488 (18)	0.0542 (7)
C4	0.1872 (3)	0.4094 (3)	0.15131 (15)	0.0475 (6)
C5	0.1083 (4)	0.2509 (3)	0.06858 (15)	0.0590 (7)
H5A	−0.0152	0.2648	0.0348	0.071*
H5B	0.0890	0.1396	0.0911	0.071*
C6	0.2453 (5)	0.2383 (4)	0.00165 (18)	0.0758 (9)
H6A	0.1968	0.1292	−0.0477	0.091*
H6B	0.2497	0.3416	−0.0278	0.091*
C7	0.4462 (5)	0.2341 (4)	0.0524 (2)	0.0789 (9)
H7A	0.5305	0.2360	0.0087	0.095*
H7B	0.4447	0.1222	0.0745	0.095*
C8	0.5242 (4)	0.3952 (4)	0.13604 (18)	0.0693 (8)
H8A	0.5420	0.5064	0.1133	0.083*
H8B	0.6483	0.3829	0.1699	0.083*
C9	0.3869 (3)	0.4063 (3)	0.20302 (16)	0.0540 (7)
H9A	0.3826	0.3025	0.2322	0.065*
H9B	0.4343	0.5152	0.2525	0.065*
C10	0.2437 (3)	0.8767 (3)	0.33824 (16)	0.0504 (6)
H10	0.2987	0.9759	0.3175	0.060*
C11	0.2451 (3)	0.9140 (3)	0.43884 (16)	0.0466 (6)
C12	0.2502 (3)	1.0907 (3)	0.48706 (18)	0.0499 (6)
C13	0.2546 (3)	1.1339 (3)	0.58226 (18)	0.0583 (7)
H13	0.2557	1.2523	0.6122	0.070*
C14	0.2571 (4)	0.9983 (4)	0.63227 (17)	0.0614 (7)
C15	0.2579 (4)	0.8223 (4)	0.58863 (18)	0.0626 (7)
H15	0.2625	0.7323	0.6231	0.075*
C16	0.2516 (3)	0.7824 (3)	0.49329 (17)	0.0556 (7)
H16	0.2518	0.6639	0.4641	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0930 (6)	0.0474 (4)	0.0950 (5)	0.0228 (4)	0.0231 (4)	0.0214 (4)
Cl2	0.1014 (7)	0.1296 (8)	0.0606 (5)	0.0288 (6)	0.0176 (4)	0.0099 (5)
O1	0.0548 (12)	0.0464 (10)	0.0572 (10)	0.0053 (8)	0.0212 (9)	0.0094 (8)
O2	0.0702 (13)	0.0456 (10)	0.0496 (9)	0.0117 (9)	0.0128 (9)	0.0161 (9)
O3	0.0681 (13)	0.0590 (12)	0.0697 (12)	0.0082 (10)	0.0341 (11)	0.0100 (10)
O4	0.1040 (17)	0.0512 (12)	0.0730 (13)	0.0128 (11)	0.0244 (11)	0.0288 (10)
C1	0.0491 (17)	0.0479 (16)	0.0474 (15)	0.0122 (13)	0.0102 (13)	0.0121 (13)
C2	0.0489 (16)	0.0360 (14)	0.0520 (15)	0.0104 (12)	0.0141 (13)	0.0126 (12)
C3	0.0559 (18)	0.0515 (17)	0.0574 (17)	0.0132 (14)	0.0092 (14)	0.0189 (15)
C4	0.0528 (17)	0.0466 (15)	0.0479 (14)	0.0090 (13)	0.0178 (13)	0.0166 (12)
C5	0.070 (2)	0.0499 (16)	0.0520 (15)	0.0002 (14)	0.0152 (14)	0.0059 (13)
C6	0.103 (3)	0.0626 (19)	0.0573 (17)	−0.0016 (18)	0.0341 (18)	0.0017 (15)
C7	0.088 (3)	0.072 (2)	0.090 (2)	0.0206 (18)	0.051 (2)	0.0148 (18)
C8	0.059 (2)	0.0699 (19)	0.0822 (19)	0.0148 (16)	0.0238 (16)	0.0149 (17)
C9	0.0538 (18)	0.0544 (16)	0.0552 (15)	0.0125 (13)	0.0128 (14)	0.0135 (13)
C10	0.0478 (17)	0.0459 (16)	0.0642 (17)	0.0165 (13)	0.0163 (13)	0.0191 (14)
C11	0.0400 (16)	0.0424 (15)	0.0575 (16)	0.0100 (12)	0.0089 (12)	0.0117 (13)
C12	0.0423 (16)	0.0448 (15)	0.0614 (16)	0.0100 (12)	0.0090 (12)	0.0103 (13)
C13	0.0466 (17)	0.0541 (17)	0.0687 (18)	0.0129 (13)	0.0097 (14)	0.0008 (15)
C14	0.0440 (18)	0.076 (2)	0.0596 (17)	0.0110 (15)	0.0103 (13)	0.0060 (16)
C15	0.0577 (19)	0.070 (2)	0.0611 (18)	0.0108 (15)	0.0078 (15)	0.0236 (16)
C16	0.0557 (18)	0.0443 (15)	0.0623 (17)	0.0084 (13)	0.0069 (14)	0.0086 (14)

Geometric parameters (Å, º) top

Cl1—C12	1.739 (2)	C7—C8	1.526 (3)
Cl2—C14	1.734 (2)	C7—H7A	0.9700
O1—C1	1.361 (3)	C7—H7B	0.9700
O1—C4	1.446 (2)	C8—C9	1.532 (3)
O2—C3	1.358 (3)	C8—H8A	0.9700
O2—C4	1.450 (2)	C8—H8B	0.9700
O3—C1	1.203 (2)	C9—H9A	0.9700
O4—C3	1.206 (3)	C9—H9B	0.9700
C1—C2	1.493 (3)	C10—C11	1.462 (3)
C2—C10	1.346 (3)	C10—H10	0.9300
C2—C3	1.485 (3)	C11—C12	1.400 (3)
C4—C5	1.507 (3)	C11—C16	1.402 (3)
C4—C9	1.509 (3)	C12—C13	1.381 (3)
C5—C6	1.530 (3)	C13—C14	1.382 (3)
C5—H5A	0.9700	C13—H13	0.9300
C5—H5B	0.9700	C14—C15	1.383 (3)
C6—C7	1.514 (4)	C15—C16	1.379 (3)
C6—H6A	0.9700	C15—H15	0.9300
C6—H6B	0.9700	C16—H16	0.9300

C1—O1—C4	119.82 (19)	H7A—C7—H7B	108.0
C3—O2—C4	118.34 (17)	C7—C8—C9	111.0 (2)
O3—C1—O1	118.7 (2)	C7—C8—H8A	109.4
O3—C1—C2	125.7 (2)	C9—C8—H8A	109.4
O1—C1—C2	115.4 (2)	C7—C8—H8B	109.4
C10—C2—C3	117.0 (2)	C9—C8—H8B	109.4
C10—C2—C1	126.3 (2)	H8A—C8—H8B	108.0
C3—C2—C1	116.4 (2)	C4—C9—C8	111.23 (19)
O4—C3—O2	118.8 (2)	C4—C9—H9A	109.4
O4—C3—C2	124.9 (2)	C8—C9—H9A	109.4
O2—C3—C2	116.2 (2)	C4—C9—H9B	109.4
O1—C4—O2	108.91 (17)	C8—C9—H9B	109.4
O1—C4—C5	106.67 (19)	H9A—C9—H9B	108.0
O2—C4—C5	106.30 (18)	C2—C10—C11	131.6 (2)
O1—C4—C9	111.22 (17)	C2—C10—H10	114.2
O2—C4—C9	110.75 (19)	C11—C10—H10	114.2
C5—C4—C9	112.76 (19)	C12—C11—C16	116.3 (2)
C4—C5—C6	111.0 (2)	C12—C11—C10	120.1 (2)
C4—C5—H5A	109.4	C16—C11—C10	123.5 (2)
C6—C5—H5A	109.4	C13—C12—C11	122.5 (2)
C4—C5—H5B	109.4	C13—C12—Cl1	117.25 (19)
C6—C5—H5B	109.4	C11—C12—Cl1	120.21 (19)
H5A—C5—H5B	108.0	C12—C13—C14	118.8 (2)
C7—C6—C5	111.9 (2)	C12—C13—H13	120.6
C7—C6—H6A	109.2	C14—C13—H13	120.6
C5—C6—H6A	109.2	C13—C14—C15	121.0 (2)
C7—C6—H6B	109.2	C13—C14—Cl2	119.2 (2)
C5—C6—H6B	109.2	C15—C14—Cl2	119.8 (2)
H6A—C6—H6B	107.9	C16—C15—C14	119.0 (2)
C6—C7—C8	111.6 (2)	C16—C15—H15	120.5
C6—C7—H7A	109.3	C14—C15—H15	120.5
C8—C7—H7A	109.3	C15—C16—C11	122.3 (2)
C6—C7—H7B	109.3	C15—C16—H16	118.8
C8—C7—H7B	109.3	C11—C16—H16	118.8

C4—O1—C1—O3	−173.9 (2)	C6—C7—C8—C9	54.4 (3)
C4—O1—C1—C2	10.6 (3)	O1—C4—C9—C8	174.74 (18)
O3—C1—C2—C10	23.5 (4)	O2—C4—C9—C8	−64.0 (2)
O1—C1—C2—C10	−161.3 (2)	C5—C4—C9—C8	55.0 (3)
O3—C1—C2—C3	−149.8 (2)	C7—C8—C9—C4	−54.3 (3)
O1—C1—C2—C3	25.3 (3)	C3—C2—C10—C11	−176.9 (2)
C4—O2—C3—O4	166.2 (2)	C1—C2—C10—C11	9.8 (4)
C4—O2—C3—C2	−17.3 (3)	C2—C10—C11—C12	−154.4 (2)
C10—C2—C3—O4	−19.7 (4)	C2—C10—C11—C16	29.0 (4)
C1—C2—C3—O4	154.3 (2)	C16—C11—C12—C13	−2.2 (4)
C10—C2—C3—O2	164.1 (2)	C10—C11—C12—C13	−179.0 (2)
C1—C2—C3—O2	−21.9 (3)	C16—C11—C12—Cl1	179.42 (17)
C1—O1—C4—O2	−47.4 (2)	C10—C11—C12—Cl1	2.6 (3)
C1—O1—C4—C5	−161.76 (18)	C11—C12—C13—C14	1.1 (4)
C1—O1—C4—C9	74.9 (2)	Cl1—C12—C13—C14	179.48 (19)
C3—O2—C4—O1	51.0 (3)	C12—C13—C14—C15	0.8 (4)
C3—O2—C4—C5	165.5 (2)	C12—C13—C14—Cl2	−179.59 (19)
C3—O2—C4—C9	−71.6 (2)	C13—C14—C15—C16	−1.4 (4)
O1—C4—C5—C6	−176.71 (19)	Cl2—C14—C15—C16	178.97 (19)
O2—C4—C5—C6	67.2 (3)	C14—C15—C16—C11	0.2 (4)
C9—C4—C5—C6	−54.3 (3)	C12—C11—C16—C15	1.6 (4)
C4—C5—C6—C7	53.8 (3)	C10—C11—C16—C15	178.3 (2)
C5—C6—C7—C8	−54.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3ⁱ	0.93	2.50	3.286 (3)	143

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Cl₂O₄
M_r	341.17
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.2378 (6), 7.6496 (7), 14.8099 (13)
α, β, γ (°)	100.569 (2), 100.870 (2), 99.050 (1)
V (Å³)	775.80 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.24 × 0.22 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.903, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	4085, 2697, 1596
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.073, 1.01
No. of reflections	2697
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −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
C13—H13···O3ⁱ	0.93	2.50	3.286 (3)	143

Symmetry code: (i) −x, −y+2, −z+1.

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
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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Volume 67| Part 6| June 2011| Page o1362

doi:10.1107/S1600536811016813

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