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In the title compound, C14H12Cl2O4, the cyclo­butane ring is folded. There are inter­molecular Cl...O and C—H...O inter­actions in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040948/at6066sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040948/at6066Isup2.hkl
Contains datablock I

CCDC reference: 296516

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.046
  • wR factor = 0.140
  • Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C1 PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. O4 .. 3.08 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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

Comment top

We have investigated the photo-induced reaction of 3,4-dichlorocoumarin and 2,3-dimethoxy-1,3-butadiene and obtained the title compound, (I), as one of the products. As part of this study, we have undertaken the X-ray crystallographic analysis of (I) in order to elucidate the conformation and configuration of this cycloadduct product.

The bond lengths and angles in (I) are in good agreement with expected values, except for the C3—C14 [1.581 (4) Å] bond length. Owing to the presence of Cl atom and a methoxy group, this bond is longer than the mean Csp3—Csp3 distance [1.55 (2) Å] reported for cyclobutanes (Allen et al., 1987). The cyclobutane ring is folded. The dihedral angle between the C3/C5/C14 and C5/C6/C14 planes is 31.4 (4)°. The coumarin moiety is essentially planar, with C6 deviating from the mean plane by 0.405 (5) Å. The two Cl atoms lie on the same side of the coumarin plane.

In the crystal structure of (I), molecules are linked by intermolecular Cl1···O4(3/2 − x, y − 1/2, 3/2 − z) [3.080 (3) Å] interactions. Similar interactions are observed in the related compound 4a,4c,9 b,9c-tetrahydro-4 b,4c,9 b,9c-tetrachlorocyclobuta[1,2 − a:3,4 − a']diindene- 5,10-dione (Zhang et al., 2003). These short contacts, together with intermolecular C—H···O interactions (Table 2) and van der Waals forces, stabilize the crystal structure.

Experimental top

Compound (I) was prepared by the photo-induced reaction of a benzene solution of 3,4-dichlorocoumarin with an excess amount of 2,3-dimethoxy-1,3-butadiene, irradiated by light of wavelength longer than 300 nm for 7 h. It was isolated by column chromatography of the reaction mixture after evaporation of the solvent on silica gel. Single crystals of (I) were obtained by slow evaporation from a petroleum ether–ethyl acetate (1:3) solution (yield 23%).

Refinement top

The H atoms were included in the riding-model approximation, with C—H distances of 0.93, 0.96 and 0.97 Å for aromatic, methyl and methylene H atoms, respectively, and with Uiso(H) = 1.2Ueq(aromatic and methylene C) or 1.5Ueq(methyl C).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
1-Acetyl-2a,8 b-dichloro-1-methoxy-1,2,2a,8 b-tetrahydro-3H- cyclobuta[c]chromen-3-one top
Crystal data top
C14H12Cl2O4F(000) = 648
Mr = 315.14Dx = 1.500 Mg m3
Monoclinic, P21/nMelting point: 467.2 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 12.678 (3) ÅCell parameters from 25 reflections
b = 8.7360 (17) Åθ = 2.0–26.0°
c = 13.185 (3) ŵ = 0.47 mm1
β = 107.09 (3)°T = 293 K
V = 1395.8 (6) Å3Block, colorless
Z = 40.43 × 0.33 × 0.28 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1870 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.051
Graphite monochromatorθmax = 26.0°, θmin = 2.0°
ω/2θ scansh = 015
Absorption correction: ψ scan
(XCAD4; Harms & Wocadlo, 1995)
k = 010
Tmin = 0.813, Tmax = 0.876l = 1515
2851 measured reflections3 standard reflections every 200 reflections
2727 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0637P)2 + P]
where P = (Fo2 + 2Fc2)/3
2727 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C14H12Cl2O4V = 1395.8 (6) Å3
Mr = 315.14Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.678 (3) ŵ = 0.47 mm1
b = 8.7360 (17) ÅT = 293 K
c = 13.185 (3) Å0.43 × 0.33 × 0.28 mm
β = 107.09 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1870 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XCAD4; Harms & Wocadlo, 1995)
Rint = 0.051
Tmin = 0.813, Tmax = 0.8763 standard reflections every 200 reflections
2851 measured reflections intensity decay: none
2727 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.00Δρmax = 0.33 e Å3
2727 reflectionsΔρmin = 0.30 e Å3
181 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
xyzUiso*/Ueq
Cl10.74570 (8)0.19543 (11)0.72000 (7)0.0541 (3)
Cl20.61485 (7)0.08808 (10)0.48364 (7)0.0476 (3)
O10.8303 (3)0.0642 (3)0.3948 (2)0.0717 (8)
O20.86173 (17)0.3151 (2)0.43481 (17)0.0390 (5)
O30.9417 (2)0.4089 (3)0.7044 (2)0.0611 (7)
O40.80183 (17)0.5250 (3)0.59365 (16)0.0388 (5)
C10.7267 (3)0.1100 (5)0.2647 (3)0.0567 (10)
H1A0.71920.02500.21700.085*
H1B0.76400.19240.24130.085*
H1C0.65500.14360.26580.085*
C20.7925 (3)0.0617 (4)0.3741 (3)0.0415 (8)
C30.8132 (2)0.1812 (3)0.4620 (2)0.0338 (7)
C40.9707 (3)0.2937 (5)0.4253 (4)0.0628 (11)
H4A0.99790.38920.40710.094*
H4B0.96830.21970.37090.094*
H4C1.01880.25770.49160.094*
C50.8686 (3)0.1284 (4)0.5770 (3)0.0417 (8)
H5A0.85420.02240.59030.050*
H5B0.94670.15160.60300.050*
C60.7951 (2)0.2427 (4)0.6114 (2)0.0357 (7)
C70.8527 (3)0.3969 (4)0.6395 (2)0.0399 (7)
C80.7041 (2)0.5234 (3)0.5087 (2)0.0310 (6)
C90.6598 (3)0.6645 (4)0.4769 (3)0.0403 (7)
H90.69440.75230.51080.048*
C100.5633 (3)0.6762 (4)0.3939 (3)0.0462 (8)
H100.53210.77150.37210.055*
C110.5140 (3)0.5446 (4)0.3441 (3)0.0485 (9)
H110.44920.55160.28830.058*
C120.5594 (3)0.4026 (4)0.3760 (3)0.0422 (8)
H120.52490.31500.34180.051*
C130.6570 (2)0.3899 (3)0.4592 (2)0.0304 (6)
C140.7121 (2)0.2407 (3)0.4981 (2)0.0317 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0626 (6)0.0650 (6)0.0392 (5)0.0042 (5)0.0220 (4)0.0161 (4)
Cl20.0439 (5)0.0364 (4)0.0636 (6)0.0099 (4)0.0175 (4)0.0009 (4)
O10.094 (2)0.0428 (16)0.0707 (19)0.0205 (15)0.0122 (16)0.0073 (13)
O20.0359 (11)0.0371 (12)0.0462 (13)0.0001 (9)0.0157 (10)0.0047 (10)
O30.0425 (14)0.0682 (18)0.0548 (15)0.0048 (13)0.0131 (12)0.0078 (14)
O40.0369 (12)0.0372 (12)0.0356 (12)0.0012 (10)0.0001 (9)0.0027 (9)
C10.064 (2)0.063 (3)0.0398 (19)0.008 (2)0.0102 (17)0.0085 (18)
C20.0451 (18)0.0360 (18)0.0461 (19)0.0043 (14)0.0176 (15)0.0013 (15)
C30.0363 (16)0.0294 (16)0.0365 (16)0.0037 (13)0.0119 (13)0.0021 (13)
C40.042 (2)0.071 (3)0.082 (3)0.0002 (19)0.029 (2)0.009 (2)
C50.0394 (17)0.0413 (19)0.0423 (18)0.0072 (14)0.0087 (14)0.0044 (15)
C60.0367 (16)0.0399 (17)0.0298 (15)0.0014 (13)0.0086 (13)0.0063 (13)
C70.0352 (16)0.049 (2)0.0320 (16)0.0010 (15)0.0046 (14)0.0007 (15)
C80.0313 (15)0.0322 (15)0.0285 (14)0.0021 (13)0.0072 (12)0.0000 (12)
C90.0480 (19)0.0267 (16)0.0437 (18)0.0011 (14)0.0093 (15)0.0042 (14)
C100.053 (2)0.0386 (19)0.0426 (19)0.0131 (16)0.0075 (16)0.0032 (15)
C110.0409 (18)0.056 (2)0.0395 (18)0.0130 (16)0.0020 (15)0.0013 (16)
C120.0375 (17)0.0435 (19)0.0400 (18)0.0003 (15)0.0025 (14)0.0046 (15)
C130.0320 (15)0.0300 (16)0.0303 (15)0.0001 (12)0.0111 (12)0.0007 (12)
C140.0315 (15)0.0295 (15)0.0338 (15)0.0039 (12)0.0092 (13)0.0004 (12)
Geometric parameters (Å, º) top
Cl1—C61.772 (3)C4—H4C0.9600
Cl2—C141.787 (3)C5—C61.524 (4)
O1—C21.199 (4)C5—H5A0.9700
O2—C31.416 (4)C5—H5B0.9700
O2—C41.435 (4)C6—C71.525 (5)
O3—C71.203 (4)C6—C141.553 (4)
O4—C71.343 (4)C8—C91.369 (4)
O4—C81.405 (3)C8—C131.383 (4)
C1—C21.499 (5)C9—C101.385 (5)
C1—H1A0.9600C9—H90.9300
C1—H1B0.9600C10—C111.379 (5)
C1—H1C0.9600C10—H100.9300
C2—C31.525 (4)C11—C121.380 (5)
C3—C51.542 (4)C11—H110.9300
C3—C141.581 (4)C12—C131.397 (4)
C4—H4A0.9600C12—H120.9300
C4—H4B0.9600C13—C141.496 (4)
C3—O2—C4114.5 (3)C7—C6—C14112.6 (2)
C7—O4—C8123.0 (2)C5—C6—Cl1118.7 (2)
C2—C1—H1A109.5C7—C6—Cl1105.5 (2)
C2—C1—H1B109.5C14—C6—Cl1118.3 (2)
H1A—C1—H1B109.5O3—C7—O4118.2 (3)
C2—C1—H1C109.5O3—C7—C6122.2 (3)
H1A—C1—H1C109.5O4—C7—C6119.6 (2)
H1B—C1—H1C109.5C9—C8—C13122.3 (3)
O1—C2—C1123.4 (3)C9—C8—O4114.9 (3)
O1—C2—C3119.1 (3)C13—C8—O4122.8 (3)
C1—C2—C3117.5 (3)C8—C9—C10119.7 (3)
O2—C3—C2111.3 (2)C8—C9—H9120.1
O2—C3—C5113.0 (3)C10—C9—H9120.1
C2—C3—C5118.0 (3)C11—C10—C9119.1 (3)
O2—C3—C14104.8 (2)C11—C10—H10120.5
C2—C3—C14118.7 (3)C9—C10—H10120.5
C5—C3—C1488.7 (2)C10—C11—C12121.0 (3)
O2—C4—H4A109.5C10—C11—H11119.5
O2—C4—H4B109.5C12—C11—H11119.5
H4A—C4—H4B109.5C11—C12—C13120.3 (3)
O2—C4—H4C109.5C11—C12—H12119.8
H4A—C4—H4C109.5C13—C12—H12119.8
H4B—C4—H4C109.5C8—C13—C12117.6 (3)
C6—C5—C387.4 (2)C8—C13—C14118.7 (2)
C6—C5—H5A114.1C12—C13—C14123.7 (3)
C3—C5—H5A114.1C13—C14—C6115.8 (2)
C6—C5—H5B114.1C13—C14—C3121.4 (2)
C3—C5—H5B114.1C6—C14—C385.0 (2)
H5A—C5—H5B111.3C13—C14—Cl2112.0 (2)
C5—C6—C7111.1 (3)C6—C14—Cl2111.3 (2)
C5—C6—C1490.4 (2)C3—C14—Cl2108.5 (2)
C4—O2—C3—C265.5 (3)C9—C8—C13—C121.7 (4)
C4—O2—C3—C570.0 (3)O4—C8—C13—C12179.7 (3)
C4—O2—C3—C14164.9 (3)C9—C8—C13—C14179.0 (3)
O1—C2—C3—O2124.9 (3)O4—C8—C13—C140.4 (4)
C1—C2—C3—O254.1 (4)C11—C12—C13—C81.2 (5)
O1—C2—C3—C58.2 (5)C11—C12—C13—C14179.5 (3)
C1—C2—C3—C5172.9 (3)C8—C13—C14—C618.7 (4)
O1—C2—C3—C14113.4 (4)C12—C13—C14—C6160.6 (3)
C1—C2—C3—C1467.7 (4)C8—C13—C14—C381.8 (4)
O2—C3—C5—C683.8 (3)C12—C13—C14—C398.9 (3)
C2—C3—C5—C6143.9 (3)C8—C13—C14—Cl2147.7 (2)
C14—C3—C5—C621.8 (2)C12—C13—C14—Cl231.5 (4)
C3—C5—C6—C792.4 (3)C5—C6—C14—C13144.3 (3)
C3—C5—C6—C1422.2 (2)C7—C6—C14—C1331.1 (3)
C3—C5—C6—Cl1145.1 (2)Cl1—C6—C14—C1392.5 (3)
C8—O4—C7—O3172.6 (3)C5—C6—C14—C321.7 (2)
C8—O4—C7—C69.6 (4)C7—C6—C14—C391.5 (3)
C5—C6—C7—O355.2 (4)Cl1—C6—C14—C3144.9 (2)
C14—C6—C7—O3154.9 (3)C5—C6—C14—Cl286.3 (2)
Cl1—C6—C7—O374.6 (4)C7—C6—C14—Cl2160.6 (2)
C5—C6—C7—O4127.1 (3)Cl1—C6—C14—Cl237.0 (3)
C14—C6—C7—O427.4 (4)O2—C3—C14—C1325.3 (3)
Cl1—C6—C7—O4103.1 (3)C2—C3—C14—C1399.8 (3)
C7—O4—C8—C9175.7 (3)C5—C3—C14—C13138.7 (3)
C7—O4—C8—C135.6 (4)O2—C3—C14—C692.0 (2)
C13—C8—C9—C101.4 (5)C2—C3—C14—C6142.9 (3)
O4—C8—C9—C10179.8 (3)C5—C3—C14—C621.4 (2)
C8—C9—C10—C110.6 (5)O2—C3—C14—Cl2157.18 (19)
C9—C10—C11—C120.1 (5)C2—C3—C14—Cl232.2 (3)
C10—C11—C12—C130.4 (5)C5—C3—C14—Cl289.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O3i0.962.553.468 (5)159
Symmetry code: (i) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC14H12Cl2O4
Mr315.14
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)12.678 (3), 8.7360 (17), 13.185 (3)
β (°) 107.09 (3)
V3)1395.8 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.43 × 0.33 × 0.28
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(XCAD4; Harms & Wocadlo, 1995)
Tmin, Tmax0.813, 0.876
No. of measured, independent and
observed [I > 2σ(I)] reflections
2851, 2727, 1870
Rint0.051
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.140, 1.00
No. of reflections2727
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.30

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Cl1—C61.772 (3)C3—C141.581 (4)
Cl2—C141.787 (3)C5—C61.524 (4)
O3—C71.203 (4)
C3—O2—C4114.5 (3)C1—C2—C3117.5 (3)
C7—O4—C8123.0 (2)O2—C3—C2111.3 (2)
Cl1—C6—C7—O4103.1 (3)Cl1—C6—C14—Cl237.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O3i0.962.553.468 (5)159
Symmetry code: (i) x+2, y+1, z+1.
 

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