3-(2,4-Dichloro­phen­yl)-2-oxo-1-oxaspiro­[4.5]dec-3-en-4-yl acetate

In the title compound, C₁₇H₁₆Cl₂O₄, the cyclo­hexyl ring displays a chair conformation [the four C atoms are planar with a mean deviation of 0.001 (2) Å and the two C atoms at the flap positions deviate by 0.625 (2) and -0.680 (2) Å from the plane]. The furan ring is planar with a mean deviation of 0.004 (2) Å and forms a dihedral angle of 46.73 (2)° with the benzene ring.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.098
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  C8      ..       5.17 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          7

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The chemistry of tetronic acid compounds has being receiving increasing attention in recent years, and references cited therein (Fischer et al.,1993; Benson et al., 2000). Bayer company have developed three tetronic acids pesticides-spirodiclofen, spiromesifen and spirotetramat(BAYER Aktiengesellschaft, 1995). The cyclohexyl chair is linked by the spiro carbon atom to the five membered furan ring and the dichlorophenyl group to form the basic structure of the spirodiclofen derivative (Zhao et al., 2009) resulting in the title compound (I), (Fig. 1) by addition of the acetate group. The furan ring is planar with a mean deviation of 0.004 (2) Å. The dihedral angle between benzene and furan rings is 46.73 (2) °. The cyclohexyl ring displays a chair conformation with the deviations of C9 and C12 being 0.625 (2) and -0.680 (2) Å, respectively. Similar distortions were observed in the structure of a spirodiclofen derivative. (Zhou et al., (2009)). As expected, C7=C15, C8=O1 and C16=O4 are typically double bonds with bond distances of 1.336 (2), 1.201 (2) and 1.183 (2) Å, respectively. In the crystal, the molecules are linked through weak intermolecular contacts of C17—H17B···O1, forming chains running along the c axis.

Related literature

For tetronic acid, see: Fischer et al. (1993); Benson et al. (2000). For the chemistry of tetronic acid pesticides, see: BAYER Aktiengesellschaft (1995). For the synthesis and basic structure of the spirodiclofen derivative, see: Zhao et al. (2009); Zhou et al. (2009).

S2. Experimental

4-hydroxyl-3-(2,4-dichlorophenyl)-1-oxaspiro[4,5]dec- 3-en-2-one(10 mmol 3.12 g) was added to acetic anhydride (35 ml) and the mixture was stirred at reflux for 5 h. Then water (70 ml) was added and the solution was extracted with dichloromethane. The organic layer was dried over Na₂SO₄. After filtered and concentrated, the organic residue was purified by silica gel column chromatography, eluted with ethyl acetate-petroleum(1:30,v/v) to give a white solid, which was then recrystallized from 95% ethanol to give colourless blocks.

S3. Refinement

H atoms were included in calculated positions and refined using a rinding model, with C—H distances constrained to 0.96 Å for methyl H atoms, 0.93Å for aryl H atoms and 0.97 for the cyclopentane,with O—H distances constrained to 0.820 Å, and with U_iso(H) = 1.2Ueq(C,O).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

3-(2,4-Dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl acetate

Crystal data

C17H16Cl2O4	F(000) = 736
Mr = 355.20	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11608 reflections
a = 14.0705 (5) Å	θ = 3.1–27.4°
b = 12.9731 (4) Å	µ = 0.40 mm^−1
c = 9.2400 (3) Å	T = 296 K
β = 90.892 (1)°	Chunk, colorless
V = 1686.45 (10) Å^3	0.47 × 0.45 × 0.29 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	3835 independent reflections
Radiation source: rotating anode	2866 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10.00 pixels mm^-1	θmax = 27.4°, θmin = 3.1°
ω scans	h = −17→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.834, Tmax = 0.893	l = −11→11
16146 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.650P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3835 reflections	Δρmax = 0.22 e Å^−3
210 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0064 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl2	0.54892 (4)	0.47091 (4)	0.18788 (5)	0.06065 (17)
Cl1	0.38311 (4)	0.75742 (4)	0.51693 (6)	0.06588 (18)
O2	0.84926 (8)	0.39184 (10)	0.46610 (12)	0.0476 (3)
O1	0.75521 (9)	0.45025 (11)	0.64035 (13)	0.0536 (3)
C4	0.64126 (12)	0.56385 (12)	0.41374 (17)	0.0392 (3)
O3	0.76541 (10)	0.49671 (10)	0.13019 (13)	0.0549 (3)
C16	0.74521 (13)	0.59698 (16)	0.08843 (19)	0.0490 (4)
C7	0.72584 (12)	0.49944 (13)	0.39001 (17)	0.0401 (4)
C6	0.56414 (13)	0.69385 (14)	0.5600 (2)	0.0500 (4)
H6	0.5665	0.7404	0.6365	0.060*
C15	0.77593 (13)	0.47332 (13)	0.27392 (18)	0.0437 (4)
C3	0.55724 (12)	0.55682 (13)	0.33197 (17)	0.0417 (4)
C1	0.48284 (12)	0.68374 (13)	0.4763 (2)	0.0462 (4)
C9	0.85752 (12)	0.40299 (14)	0.30992 (18)	0.0445 (4)
C2	0.47789 (12)	0.61566 (14)	0.36203 (18)	0.0460 (4)
H2	0.4225	0.6094	0.3064	0.055*
O4	0.74584 (11)	0.66581 (11)	0.17247 (15)	0.0626 (4)
C5	0.64214 (13)	0.63370 (14)	0.52862 (19)	0.0467 (4)
H5	0.6969	0.6399	0.5857	0.056*
C8	0.77430 (12)	0.44761 (13)	0.51412 (18)	0.0424 (4)
C14	0.84764 (13)	0.29681 (15)	0.2402 (2)	0.0522 (4)
H14A	0.7892	0.2649	0.2718	0.063*
H14B	0.8438	0.3044	0.1358	0.063*
C13	0.93139 (16)	0.22725 (18)	0.2799 (3)	0.0715 (6)
H13A	0.9306	0.2126	0.3829	0.086*
H13B	0.9252	0.1624	0.2284	0.086*
C10	0.95350 (14)	0.45228 (17)	0.2795 (2)	0.0620 (5)
H10A	0.9596	0.5155	0.3348	0.074*
H10B	0.9564	0.4699	0.1776	0.074*
C11	1.03604 (15)	0.3808 (2)	0.3184 (3)	0.0772 (7)
H11A	1.0954	0.4127	0.2907	0.093*
H11B	1.0382	0.3700	0.4223	0.093*
C17	0.72453 (19)	0.6010 (2)	−0.0704 (2)	0.0764 (7)
H17A	0.6580	0.5890	−0.0877	0.092*
H17B	0.7608	0.5488	−0.1184	0.092*
H17C	0.7415	0.6676	−0.1071	0.092*
C12	1.02541 (16)	0.2775 (2)	0.2422 (3)	0.0867 (8)
H12A	1.0774	0.2326	0.2710	0.104*
H12B	1.0282	0.2876	0.1383	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl2	0.0609 (3)	0.0749 (3)	0.0461 (3)	−0.0062 (2)	−0.0021 (2)	−0.0182 (2)
Cl1	0.0520 (3)	0.0588 (3)	0.0873 (4)	0.0111 (2)	0.0151 (2)	−0.0012 (3)
O2	0.0461 (6)	0.0517 (7)	0.0450 (6)	0.0078 (6)	−0.0016 (5)	−0.0027 (5)
O1	0.0572 (8)	0.0654 (8)	0.0381 (6)	0.0063 (6)	−0.0007 (5)	−0.0010 (6)
C4	0.0433 (8)	0.0371 (8)	0.0374 (8)	−0.0017 (7)	0.0032 (7)	0.0010 (6)
O3	0.0725 (9)	0.0540 (7)	0.0385 (6)	0.0110 (7)	0.0104 (6)	−0.0009 (5)
C16	0.0452 (9)	0.0568 (11)	0.0450 (9)	0.0032 (8)	0.0047 (7)	0.0058 (9)
C7	0.0452 (9)	0.0375 (8)	0.0374 (8)	−0.0028 (7)	0.0015 (7)	−0.0027 (7)
C6	0.0523 (10)	0.0443 (9)	0.0535 (10)	−0.0017 (8)	0.0075 (8)	−0.0110 (8)
C15	0.0502 (9)	0.0409 (9)	0.0401 (8)	0.0013 (7)	0.0035 (7)	−0.0017 (7)
C3	0.0483 (9)	0.0428 (9)	0.0341 (8)	−0.0050 (7)	0.0027 (7)	0.0017 (7)
C1	0.0441 (9)	0.0409 (9)	0.0540 (10)	0.0017 (7)	0.0110 (8)	0.0058 (8)
C9	0.0434 (9)	0.0462 (9)	0.0439 (9)	0.0007 (7)	0.0021 (7)	−0.0073 (7)
C2	0.0423 (9)	0.0514 (10)	0.0444 (9)	−0.0025 (8)	0.0017 (7)	0.0078 (8)
O4	0.0823 (10)	0.0506 (8)	0.0545 (8)	0.0025 (7)	−0.0065 (7)	0.0040 (7)
C5	0.0449 (9)	0.0472 (10)	0.0478 (9)	−0.0006 (8)	−0.0014 (7)	−0.0085 (8)
C8	0.0417 (8)	0.0409 (9)	0.0445 (9)	−0.0021 (7)	−0.0019 (7)	−0.0037 (7)
C14	0.0444 (9)	0.0498 (10)	0.0621 (11)	0.0047 (8)	−0.0058 (8)	−0.0140 (9)
C13	0.0658 (13)	0.0610 (13)	0.0869 (16)	0.0216 (11)	−0.0206 (12)	−0.0258 (12)
C10	0.0538 (11)	0.0662 (13)	0.0662 (12)	−0.0137 (10)	0.0109 (10)	−0.0151 (10)
C11	0.0405 (10)	0.1057 (19)	0.0856 (16)	−0.0067 (11)	0.0009 (10)	−0.0284 (14)
C17	0.0956 (17)	0.0911 (17)	0.0426 (10)	0.0107 (14)	0.0081 (11)	0.0080 (11)
C12	0.0493 (12)	0.112 (2)	0.0985 (18)	0.0272 (13)	−0.0115 (12)	−0.0418 (16)

Geometric parameters (Å, º)

Cl2—C3	1.7388 (17)	C9—C14	1.526 (2)
Cl1—C1	1.7437 (17)	C2—H2	0.9300
O2—C8	1.359 (2)	C5—H5	0.9300
O2—C9	1.457 (2)	C14—C13	1.525 (3)
O1—C8	1.201 (2)	C14—H14A	0.9700
C4—C5	1.395 (2)	C14—H14B	0.9700
C4—C3	1.396 (2)	C13—C12	1.520 (4)
C4—C7	1.473 (2)	C13—H13A	0.9700
O3—C15	1.368 (2)	C13—H13B	0.9700
O3—C16	1.385 (2)	C10—C11	1.525 (3)
C16—O4	1.183 (2)	C10—H10A	0.9700
C16—C17	1.492 (3)	C10—H10B	0.9700
C7—C15	1.336 (2)	C11—C12	1.520 (3)
C7—C8	1.486 (2)	C11—H11A	0.9700
C6—C1	1.377 (3)	C11—H11B	0.9700
C6—C5	1.381 (2)	C17—H17A	0.9600
C6—H6	0.9300	C17—H17B	0.9600
C15—C9	1.500 (2)	C17—H17C	0.9600
C3—C2	1.384 (2)	C12—H12A	0.9700
C1—C2	1.377 (3)	C12—H12B	0.9700
C9—C10	1.524 (3)
C8—O2—C9	110.17 (12)	O2—C8—C7	109.76 (14)
C5—C4—C3	116.84 (15)	C13—C14—C9	111.57 (15)
C5—C4—C7	118.94 (14)	C13—C14—H14A	109.3
C3—C4—C7	124.16 (15)	C9—C14—H14A	109.3
C15—O3—C16	119.83 (14)	C13—C14—H14B	109.3
O4—C16—O3	121.77 (16)	C9—C14—H14B	109.3
O4—C16—C17	128.21 (19)	H14A—C14—H14B	108.0
O3—C16—C17	110.02 (18)	C12—C13—C14	111.3 (2)
C15—C7—C4	134.48 (15)	C12—C13—H13A	109.4
C15—C7—C8	105.27 (15)	C14—C13—H13A	109.4
C4—C7—C8	120.25 (14)	C12—C13—H13B	109.4
C1—C6—C5	118.93 (16)	C14—C13—H13B	109.4
C1—C6—H6	120.5	H13A—C13—H13B	108.0
C5—C6—H6	120.5	C9—C10—C11	112.02 (18)
C7—C15—O3	132.27 (16)	C9—C10—H10A	109.2
C7—C15—C9	112.81 (15)	C11—C10—H10A	109.2
O3—C15—C9	114.90 (14)	C9—C10—H10B	109.2
C2—C3—C4	122.29 (15)	C11—C10—H10B	109.2
C2—C3—Cl2	117.53 (13)	H10A—C10—H10B	107.9
C4—C3—Cl2	120.18 (13)	C12—C11—C10	110.95 (17)
C6—C1—C2	121.56 (16)	C12—C11—H11A	109.4
C6—C1—Cl1	119.41 (14)	C10—C11—H11A	109.4
C2—C1—Cl1	119.02 (14)	C12—C11—H11B	109.4
O2—C9—C15	101.97 (13)	C10—C11—H11B	109.4
O2—C9—C10	108.00 (14)	H11A—C11—H11B	108.0
C15—C9—C10	112.41 (16)	C16—C17—H17A	109.5
O2—C9—C14	108.69 (15)	C16—C17—H17B	109.5
C15—C9—C14	113.02 (14)	H17A—C17—H17B	109.5
C10—C9—C14	112.08 (15)	C16—C17—H17C	109.5
C1—C2—C3	118.43 (16)	H17A—C17—H17C	109.5
C1—C2—H2	120.8	H17B—C17—H17C	109.5
C3—C2—H2	120.8	C11—C12—C13	110.58 (18)
C6—C5—C4	121.95 (16)	C11—C12—H12A	109.5
C6—C5—H5	119.0	C13—C12—H12A	109.5
C4—C5—H5	119.0	C11—C12—H12B	109.5
O1—C8—O2	121.23 (15)	C13—C12—H12B	109.5
O1—C8—C7	129.01 (16)	H12A—C12—H12B	108.1
C15—O3—C16—O4	7.6 (3)	C7—C15—C9—C14	115.89 (18)
C15—O3—C16—C17	−172.61 (17)	O3—C15—C9—C14	−62.8 (2)
C5—C4—C7—C15	−134.5 (2)	C6—C1—C2—C3	−0.2 (3)
C3—C4—C7—C15	48.4 (3)	Cl1—C1—C2—C3	−179.30 (13)
C5—C4—C7—C8	44.9 (2)	C4—C3—C2—C1	0.4 (3)
C3—C4—C7—C8	−132.16 (17)	Cl2—C3—C2—C1	179.61 (13)
C4—C7—C15—O3	−1.1 (3)	C1—C6—C5—C4	0.7 (3)
C8—C7—C15—O3	179.42 (18)	C3—C4—C5—C6	−0.5 (3)
C4—C7—C15—C9	−179.47 (17)	C7—C4—C5—C6	−177.72 (16)
C8—C7—C15—C9	1.07 (19)	C9—O2—C8—O1	−179.13 (16)
C16—O3—C15—C7	44.5 (3)	C9—O2—C8—C7	0.84 (18)
C16—O3—C15—C9	−137.13 (16)	C15—C7—C8—O1	178.78 (18)
C5—C4—C3—C2	−0.1 (2)	C4—C7—C8—O1	−0.8 (3)
C7—C4—C3—C2	177.04 (15)	C15—C7—C8—O2	−1.19 (19)
C5—C4—C3—Cl2	−179.29 (13)	C4—C7—C8—O2	179.26 (14)
C7—C4—C3—Cl2	−2.2 (2)	O2—C9—C14—C13	−67.2 (2)
C5—C6—C1—C2	−0.3 (3)	C15—C9—C14—C13	−179.60 (18)
C5—C6—C1—Cl1	178.78 (14)	C10—C9—C14—C13	52.1 (2)
C8—O2—C9—C15	−0.20 (17)	C9—C14—C13—C12	−55.0 (2)
C8—O2—C9—C10	118.41 (16)	O2—C9—C10—C11	67.5 (2)
C8—O2—C9—C14	−119.78 (15)	C15—C9—C10—C11	179.18 (16)
C7—C15—C9—O2	−0.60 (19)	C14—C9—C10—C11	−52.2 (2)
O3—C15—C9—O2	−179.25 (14)	C9—C10—C11—C12	54.8 (3)
C7—C15—C9—C10	−116.02 (17)	C10—C11—C12—C13	−57.3 (3)
O3—C15—C9—C10	65.3 (2)	C14—C13—C12—C11	57.6 (3)