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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o56.
Published online 2009 December 4. doi:  10.1107/S1600536809051320
PMCID: PMC2980257

4-(4-Chloro­phen­yl)-7,7-dimethyl-7,8-dihydro-4H-1-benzopyran-2,5(3H,6H)-dione

Abstract

The title compound, C17H17ClO3, has been synthesized by the reaction of p-chloro­benzaldehyde, isopropyl­idene malonate and 5,5-dimethyl­cyclo­hexane-1,3-dione with triethyl­benzyl­ammonium chloride in water as a green solvent. The six membered pyran­one ring of the hexa­hydro­coumarin system has a screw-boat conformation while the dimethyl­cyclo­hexenone system has a distorted envelope conformation. The dihedral angle between the least-squares planes of the coumarin ring system and the benzene ring is 85.64 (9)°.

Related literature

For applications of coumarin derivatives, see: Wang et al. (1999 [triangle]); Yang (2001 [triangle]). For related structures, see: Itoh & Kanemasa (2003 [triangle]); Itoh et al. (2005 [triangle]). For ring puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-66-00o56-scheme1.jpg

Experimental

Crystal data

  • C17H17ClO3
  • M r = 304.76
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o56-efi1.jpg
  • a = 11.9005 (12) Å
  • b = 5.7971 (8) Å
  • c = 22.608 (2) Å
  • β = 93.972 (1)°
  • V = 1555.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 298 K
  • 0.48 × 0.39 × 0.34 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1999 [triangle]) T min = 0.889, T max = 0.919
  • 7519 measured reflections
  • 2789 independent reflections
  • 1585 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.186
  • S = 1.05
  • 2789 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 1999 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051320/bh2260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051320/bh2260Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The research was supported by the Open Foundation of Key Disciplines within the Zhejiang Provincial Key Disciplines.

supplementary crystallographic information

Comment

Coumarin is an important chemical having unique characteristics. It is widely used in hand soaps, detergents, lotions and laser dyes (Wang et al., 1999). Coumarin and some of its derivatives have been tested in pharmacology for treatment of HIV (Yang, 2001). To obtain coumarin in a more environment friendly way, water was used as a green solvent in the synthesis of the title compound (Fig.1 and Experimental).

In the molecule of the title compound (Fig. 2), the two six membered rings of the hexahydrocoumarin system are not planar, having screw-boat and envelope conformations respectively: the pyranone ring A (O1/C1···C4/C9) adopts the screw-boat conformation with puckering parameters (Cremer & Pople, 1975) Q= 0.430 (5) Å, θ= 61.8 (5)° and [var phi] = 134.7 (6)°; the ring B (C4···C9) exists in a distorted envelope conformation [Q = 0.408 (4) Å, θ= 127.0 (6)° and [var phi]= 343.4 (7)°)] with C7 displaced by 0.558 (5) Å from the plane of the other ring atoms. Ring C (C12···C17) is a benzene ring, which makes a dihedral angle of 85.64 (9)° with the least-squares plane of the coumarin ring. The analogue of the title compound including Br in place of Cl has been reported and an enantiomerically pure crystal characterized by X-ray diffraction (Itoh & Kanemasa, 2003; Itoh et al., 2005).

Experimental

A mixture of 4-chlorobenzaldehyde (100 mmol), 5,5-dimethyl-1,3-cyclohexanedione (100 mmol), isopropylidene malonate (100 mmol), triethylbenzylammonium chloride (TEBA) (15 mmol) and 400 mL of water was transferred into a flask connected with refluxing equipment (Fig. 1). After stirring at 345 K (72°C) for 5 h, the reaction mixture was cooled to room temperature, the precipitated product was filtered and recrystallized with ethanol to give the title compound. Crystals suitable for X-ray structure analysis were obtained by slow evaporation from a solution of isopropyl alcohol at room temperature.

Refinement

All H atoms were placed in geometrical positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.98 Å. They were treated as riding atoms, with Uiso(H) = 1.5Ueq(carrier C) for methyl groups and Uiso(H) = 1.2Ueq(carrier C) for other H atoms.

Figures

Fig. 1.
The preparation of the title compound.
Fig. 2.
Structure of the title compound, showing 30% probability displacement ellipsoids with atomic numbering scheme.

Crystal data

C17H17ClO3F(000) = 640
Mr = 304.76Dx = 1.301 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1909 reflections
a = 11.9005 (12) Åθ = 2.7–23.0°
b = 5.7971 (8) ŵ = 0.25 mm1
c = 22.608 (2) ÅT = 298 K
β = 93.972 (1)°Prism, colorless
V = 1555.9 (3) Å30.48 × 0.39 × 0.34 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2789 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
graphiteRint = 0.034
[var phi] and ω scansθmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1999)h = −12→14
Tmin = 0.889, Tmax = 0.919k = −6→6
7519 measured reflectionsl = −27→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0667P)2 + 1.4872P] where P = (Fo2 + 2Fc2)/3
2789 reflections(Δ/σ)max < 0.001
192 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = −0.51 e Å3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl1−0.43477 (9)0.5886 (3)0.12137 (6)0.1069 (6)
O10.1778 (2)0.6708 (5)0.18437 (12)0.0681 (8)
O20.1132 (3)0.5408 (7)0.26641 (15)0.1127 (13)
O30.0220 (3)1.3042 (5)0.07706 (14)0.0936 (10)
C10.1180 (4)0.7039 (10)0.2336 (2)0.0765 (13)
C20.0708 (4)0.9367 (9)0.24091 (17)0.0810 (14)
H2A0.13051.03950.25590.097*
H2B0.01490.93030.27010.097*
C30.0160 (3)1.0357 (7)0.18295 (16)0.0598 (10)
H30.00491.20170.18830.072*
C40.0969 (3)1.0017 (6)0.13547 (15)0.0505 (9)
C50.0888 (3)1.1459 (7)0.08223 (17)0.0602 (10)
C60.1584 (3)1.0799 (8)0.03203 (18)0.0751 (12)
H6A0.17201.21680.00890.090*
H6B0.11560.97270.00640.090*
C70.2710 (3)0.9703 (7)0.05132 (16)0.0580 (10)
C80.2544 (3)0.7783 (7)0.09489 (18)0.0631 (10)
H8A0.22910.64160.07310.076*
H8B0.32650.74240.11550.076*
C90.1725 (3)0.8325 (6)0.13923 (16)0.0518 (9)
C100.3488 (4)1.1568 (8)0.0813 (2)0.0812 (13)
H10A0.31371.22110.11450.122*
H10B0.36161.27670.05320.122*
H10C0.41951.08830.09470.122*
C110.3302 (4)0.8824 (9)−0.0017 (2)0.0955 (15)
H11A0.40200.81870.01150.143*
H11B0.34091.0077−0.02850.143*
H11C0.28490.7653−0.02170.143*
C12−0.0981 (3)0.9254 (6)0.16736 (15)0.0524 (9)
C13−0.1075 (3)0.7218 (7)0.13616 (17)0.0585 (10)
H13−0.04280.65310.12350.070*
C14−0.2100 (3)0.6170 (7)0.12320 (17)0.0636 (10)
H14−0.21410.47780.10270.076*
C15−0.3048 (3)0.7190 (8)0.14062 (17)0.0638 (11)
C16−0.3001 (3)0.9189 (9)0.17169 (18)0.0719 (12)
H16−0.36580.98540.18380.086*
C17−0.1966 (3)1.0245 (7)0.18543 (17)0.0666 (11)
H17−0.19321.16180.20680.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0534 (6)0.1496 (13)0.1172 (11)−0.0213 (7)0.0011 (6)0.0253 (9)
O10.0610 (16)0.0693 (18)0.0721 (18)−0.0014 (13)−0.0099 (14)0.0155 (15)
O20.128 (3)0.132 (3)0.075 (2)−0.020 (2)−0.0128 (19)0.040 (2)
O30.110 (2)0.074 (2)0.097 (2)0.0438 (19)0.0137 (19)0.0108 (18)
C10.072 (3)0.101 (4)0.054 (3)−0.020 (3)−0.017 (2)0.008 (3)
C20.081 (3)0.110 (4)0.050 (2)−0.024 (3)−0.004 (2)−0.018 (3)
C30.064 (2)0.057 (2)0.059 (2)−0.0037 (19)0.0033 (18)−0.0186 (19)
C40.0476 (18)0.048 (2)0.055 (2)−0.0025 (16)−0.0024 (15)−0.0082 (18)
C50.060 (2)0.053 (2)0.067 (3)0.0078 (19)−0.0015 (19)−0.001 (2)
C60.073 (3)0.091 (3)0.061 (2)0.014 (2)0.002 (2)0.007 (2)
C70.055 (2)0.062 (2)0.057 (2)0.0042 (18)0.0022 (17)−0.002 (2)
C80.051 (2)0.055 (2)0.084 (3)0.0043 (18)0.0070 (19)0.001 (2)
C90.0462 (19)0.051 (2)0.057 (2)−0.0052 (17)−0.0076 (16)0.0054 (19)
C100.073 (3)0.069 (3)0.101 (3)−0.013 (2)0.002 (2)0.005 (3)
C110.092 (3)0.110 (4)0.087 (3)0.014 (3)0.025 (3)−0.007 (3)
C120.056 (2)0.054 (2)0.047 (2)0.0089 (17)0.0058 (16)−0.0044 (18)
C130.0450 (19)0.062 (2)0.068 (2)0.0058 (17)0.0046 (17)−0.014 (2)
C140.053 (2)0.066 (3)0.071 (3)−0.0035 (19)−0.0004 (18)−0.002 (2)
C150.050 (2)0.081 (3)0.061 (2)−0.002 (2)0.0028 (18)0.018 (2)
C160.053 (2)0.094 (3)0.071 (3)0.020 (2)0.022 (2)0.018 (3)
C170.077 (3)0.064 (3)0.060 (2)0.015 (2)0.015 (2)−0.004 (2)

Geometric parameters (Å, °)

Cl1—C151.749 (4)C7—C101.549 (5)
O1—C11.374 (5)C8—C91.480 (5)
O1—C91.384 (4)C8—H8A0.9700
O2—C11.206 (5)C8—H8B0.9700
O3—C51.214 (4)C10—H10A0.9600
C1—C21.475 (7)C10—H10B0.9600
C2—C31.534 (6)C10—H10C0.9600
C2—H2A0.9700C11—H11A0.9600
C2—H2B0.9700C11—H11B0.9600
C3—C41.503 (5)C11—H11C0.9600
C3—C121.520 (5)C12—C131.376 (5)
C3—H30.9800C12—C171.392 (5)
C4—C91.330 (5)C13—C141.375 (5)
C4—C51.463 (5)C13—H130.9300
C5—C61.501 (5)C14—C151.357 (5)
C6—C71.519 (5)C14—H140.9300
C6—H6A0.9700C15—C161.354 (6)
C6—H6B0.9700C16—C171.391 (6)
C7—C81.509 (5)C16—H160.9300
C7—C111.520 (6)C17—H170.9300
C1—O1—C9120.2 (3)C9—C8—H8B108.7
O2—C1—O1116.0 (5)C7—C8—H8B108.7
O2—C1—C2127.8 (5)H8A—C8—H8B107.6
O1—C1—C2116.2 (4)C4—C9—O1122.9 (3)
C1—C2—C3112.9 (3)C4—C9—C8126.0 (3)
C1—C2—H2A109.0O1—C9—C8110.9 (3)
C3—C2—H2A109.0C7—C10—H10A109.5
C1—C2—H2B109.0C7—C10—H10B109.5
C3—C2—H2B109.0H10A—C10—H10B109.5
H2A—C2—H2B107.8C7—C10—H10C109.5
C4—C3—C12112.6 (3)H10A—C10—H10C109.5
C4—C3—C2107.8 (3)H10B—C10—H10C109.5
C12—C3—C2111.1 (3)C7—C11—H11A109.5
C4—C3—H3108.4C7—C11—H11B109.5
C12—C3—H3108.4H11A—C11—H11B109.5
C2—C3—H3108.4C7—C11—H11C109.5
C9—C4—C5118.7 (3)H11A—C11—H11C109.5
C9—C4—C3121.0 (3)H11B—C11—H11C109.5
C5—C4—C3120.2 (3)C13—C12—C17117.7 (3)
O3—C5—C4121.1 (4)C13—C12—C3121.3 (3)
O3—C5—C6120.8 (4)C17—C12—C3121.0 (3)
C4—C5—C6117.9 (3)C14—C13—C12121.9 (3)
C5—C6—C7114.3 (3)C14—C13—H13119.1
C5—C6—H6A108.7C12—C13—H13119.1
C7—C6—H6A108.7C15—C14—C13119.2 (4)
C5—C6—H6B108.7C15—C14—H14120.4
C7—C6—H6B108.7C13—C14—H14120.4
H6A—C6—H6B107.6C16—C15—C14121.2 (4)
C8—C7—C6110.1 (3)C16—C15—Cl1120.2 (3)
C8—C7—C11110.9 (3)C14—C15—Cl1118.6 (4)
C6—C7—C11111.2 (3)C15—C16—C17119.8 (4)
C8—C7—C10109.3 (3)C15—C16—H16120.1
C6—C7—C10108.8 (3)C17—C16—H16120.1
C11—C7—C10106.5 (3)C16—C17—C12120.2 (4)
C9—C8—C7114.1 (3)C16—C17—H17119.9
C9—C8—H8A108.7C12—C17—H17119.9
C7—C8—H8A108.7
C9—O1—C1—O2169.1 (3)C5—C4—C9—O1−172.3 (3)
C9—O1—C1—C2−12.9 (5)C3—C4—C9—O13.8 (5)
O2—C1—C2—C3−138.5 (4)C5—C4—C9—C82.4 (5)
O1—C1—C2—C343.7 (5)C3—C4—C9—C8178.5 (3)
C1—C2—C3—C4−48.0 (5)C1—O1—C9—C4−12.2 (5)
C1—C2—C3—C1275.9 (4)C1—O1—C9—C8172.4 (3)
C12—C3—C4—C9−97.0 (4)C7—C8—C9—C416.7 (5)
C2—C3—C4—C926.0 (5)C7—C8—C9—O1−168.1 (3)
C12—C3—C4—C579.1 (4)C4—C3—C12—C1335.1 (5)
C2—C3—C4—C5−157.9 (3)C2—C3—C12—C13−86.0 (4)
C9—C4—C5—O3−179.1 (4)C4—C3—C12—C17−146.4 (3)
C3—C4—C5—O34.7 (5)C2—C3—C12—C1792.5 (4)
C9—C4—C5—C66.0 (5)C17—C12—C13—C14−0.3 (5)
C3—C4—C5—C6−170.1 (3)C3—C12—C13—C14178.2 (4)
O3—C5—C6—C7152.0 (4)C12—C13—C14—C151.3 (6)
C4—C5—C6—C7−33.1 (5)C13—C14—C15—C16−1.6 (6)
C5—C6—C7—C849.9 (5)C13—C14—C15—Cl1177.7 (3)
C5—C6—C7—C11173.2 (4)C14—C15—C16—C170.9 (6)
C5—C6—C7—C10−69.9 (5)Cl1—C15—C16—C17−178.3 (3)
C6—C7—C8—C9−41.4 (4)C15—C16—C17—C120.0 (6)
C11—C7—C8—C9−164.8 (3)C13—C12—C17—C16−0.3 (5)
C10—C7—C8—C978.1 (4)C3—C12—C17—C16−178.8 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2260).

References

  • Bruker (1999). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Itoh, K., Hasegawa, M., Tanaka, J. & Kanemasa, S. (2005). Org. Lett.7, 979–981. [PubMed]
  • Itoh, K. & Kanemasa, S. (2003). Tetrahedron Lett.44, 1799–1802.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, X. F., Qu, Y. & Gu, F. (1999). Speciality Petrochemicals, 1, 49–52.
  • Yang, J. S. (2001). West China J. Pharm. Sci.16, 285–288.

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