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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o547.
Published online 2010 February 6. doi:  10.1107/S1600536810004125
PMCID: PMC2983494

12-(4-Chloro­phen­yl)-9,9-dimethyl-9,10-dihydro-8H-benzo[a]xanthen-11(12H)-one

Abstract

The title compound, C25H21ClO2, was synthesized via the three-component coupling of 4-chloro­benzaldehyde, 2-naphthol and 5,5-dimethyl­cyclo­hexane-1,3-dione. The pyran ring adopts a boat conformation, while the cyclo­hexenone ring is in an envelope conformation. The 4-chloro­phenyl ring is almost perpendicular to the pyran ring [dihedral angle = 87.39 (1)°]. In the crystal, mol­ecules are connected by inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the biological activity of xanthenes and benzoxanthenes, see: Poupelin et al. (1978 [triangle]); Lambert et al. (1997 [triangle]) and for their applications see: Ion et al. (1998 [triangle]); Saint-Ruf et al. (1975 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o547-scheme1.jpg

Experimental

Crystal data

  • C25H21ClO2
  • M r = 388.87
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o547-efi1.jpg
  • a = 10.293 (2) Å
  • b = 11.621 (2) Å
  • c = 16.447 (3) Å
  • β = 90.04 (3)°
  • V = 1967.3 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 113 K
  • 0.16 × 0.14 × 0.08 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.967, T max = 0.983
  • 15871 measured reflections
  • 4667 independent reflections
  • 2863 reflections with I > 2σ(I)
  • R int = 0.079

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.136
  • S = 0.91
  • 4667 reflections
  • 255 parameters
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004125/bv2134sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004125/bv2134Isup2.hkl

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

Acknowledgments

The authors thank the Tangshan Municipal Science and Technology Commission (No. 07160213B) and Tangshan Normal College (No. 07 A02) for financial support.

supplementary crystallographic information

Comment

Xanthenes and benzoxanthenes are important biologically active heterocycles. They possess anti-inflammatory (Poupelin et al., 1978) and antiviral (Lambert et al., 1997) activities. These compounds are utilized as antagonists for paralyzing action of zoxazolamine (Saint-Ruf et al.,1975) and in photodynamic therapy (Ion et al.,1998). We report herein the crystal structure of the title compound.

The pyran ring of the title molecule (Fig.1) adopts a boat conformation. The cyclohexenone ring is in an envelope conformation with atom C15 at the flap. The 4-chloropheny ring and the planar part of the pyran ring (C1/C10/C12/C17) are nearly perpendicular to each other, with a dihedral angle of 87.39 (1)°. In the crystal, the molecules are connected by C—H···O hydrogen bonds.

Experimental

To a mixture of 2-naphthol (1.0 mmol), 4-chlorobenzaldehyde (1.0 mmol), and 5,5-dimethylcyclohexane-1,3-dione (1.1 mmol) was added strontium trifluoromethanesulfonate (0.1 mmol) in 1,2-dichloroethane (2 ml). The mixture was stirred at 80 °C for 5 h. The progress of the reaction was monitored by TLC. After completion of the reaction, water was added and the product was extracted with ethyl acetate (3 x 10 ml). The organic layer was dried (MgSO4)and evaporated, and the crude product was purified by flash chromatography on silica gel. Pure product crystallized slowly at room temperature in ethanol. A single-crystal was obtained by slow evaporation of a solution in ethanol.

Refinement

All H atoms were included in the refinement in the riding model approximation, with C–H = 0.95–1.00 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Figures

Fig. 1.
A view of the molecular structure of (I), showing the atom-numbering scheme. Dispacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The packing, showing hydrogen-bond interactions as dashed lines, H atoms are shown as small spheres of arbitary radii.

Crystal data

C25H21ClO2F(000) = 816
Mr = 388.87Dx = 1.313 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.293 (2) ÅCell parameters from 5755 reflections
b = 11.621 (2) Åθ = 2.2–27.8°
c = 16.447 (3) ŵ = 0.21 mm1
β = 90.04 (3)°T = 113 K
V = 1967.3 (7) Å3Prism, colourless
Z = 40.16 × 0.14 × 0.08 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer4667 independent reflections
Radiation source: rotating anode2863 reflections with I > 2σ(I)
confocalRint = 0.079
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.2°
ω and [var phi] scansh = −12→13
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −15→15
Tmin = 0.967, Tmax = 0.983l = −16→21
15871 measured reflections

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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 0.91w = 1/[σ2(Fo2) + (0.0704P)2] where P = (Fo2 + 2Fc2)/3
4667 reflections(Δ/σ)max = 0.001
255 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = −0.50 e Å3

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 (Å2)

xyzUiso*/Ueq
Cl10.73445 (5)0.84810 (5)1.12407 (3)0.03409 (17)
O10.32484 (13)0.87906 (11)0.73299 (7)0.0238 (3)
O20.25555 (13)0.57878 (11)0.92168 (7)0.0263 (3)
C10.44337 (19)0.83375 (16)0.70869 (10)0.0209 (4)
C20.4964 (2)0.88806 (17)0.63881 (10)0.0245 (4)
H20.44970.94730.61170.029*
C30.6149 (2)0.85411 (17)0.61122 (11)0.0257 (5)
H30.65170.89170.56540.031*
C40.68478 (19)0.76365 (17)0.64948 (10)0.0241 (4)
C50.8075 (2)0.72738 (18)0.62115 (11)0.0290 (5)
H50.84630.76590.57640.035*
C60.8714 (2)0.63750 (19)0.65724 (11)0.0302 (5)
H60.95440.61460.63780.036*
C70.8141 (2)0.57895 (18)0.72317 (11)0.0287 (5)
H70.85770.51530.74710.034*
C80.6959 (2)0.61332 (17)0.75303 (11)0.0244 (4)
H80.65960.57390.79820.029*
C90.62679 (18)0.70654 (16)0.71777 (10)0.0215 (4)
C100.50399 (18)0.74502 (16)0.74811 (10)0.0199 (4)
C110.44318 (18)0.69161 (16)0.82395 (10)0.0202 (4)
H110.44780.60590.81940.024*
C120.30257 (18)0.72721 (16)0.82882 (10)0.0202 (4)
C130.21423 (19)0.66017 (16)0.88135 (10)0.0211 (4)
C140.07188 (19)0.69208 (17)0.88032 (11)0.0261 (4)
H14A0.03090.66430.93110.031*
H14B0.02920.65240.83420.031*
C150.0482 (2)0.82193 (17)0.87251 (11)0.0260 (5)
C160.11871 (19)0.86281 (17)0.79483 (11)0.0248 (4)
H16A0.06840.83770.74670.030*
H16B0.12150.94800.79450.030*
C170.25322 (19)0.81783 (16)0.78815 (10)0.0216 (4)
C18−0.0967 (2)0.8461 (2)0.86518 (14)0.0378 (6)
H18A−0.11100.92940.86220.057*
H18B−0.14180.81490.91280.057*
H18C−0.13050.80950.81580.057*
C190.1024 (2)0.88391 (19)0.94769 (12)0.0323 (5)
H19A0.08910.96700.94190.048*
H19B0.19550.86770.95280.048*
H19C0.05710.85650.99640.048*
C200.51814 (18)0.72951 (16)0.90026 (10)0.0196 (4)
C210.53737 (19)0.84537 (16)0.91539 (10)0.0217 (4)
H210.50330.90070.87850.026*
C220.60548 (19)0.88237 (17)0.98344 (10)0.0227 (4)
H220.61930.96200.99300.027*
C230.65267 (18)0.80068 (18)1.03694 (10)0.0235 (4)
C240.63531 (19)0.68441 (18)1.02455 (11)0.0261 (4)
H240.66840.62981.06220.031*
C250.5679 (2)0.64900 (17)0.95526 (11)0.0245 (4)
H250.55560.56920.94540.029*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0361 (4)0.0441 (4)0.0221 (3)−0.0042 (2)−0.0111 (2)0.0026 (2)
O10.0252 (8)0.0268 (8)0.0194 (7)0.0030 (6)0.0051 (5)0.0050 (5)
O20.0293 (9)0.0257 (8)0.0239 (7)0.0018 (6)0.0032 (6)0.0039 (5)
C10.0202 (11)0.0275 (11)0.0148 (9)−0.0006 (8)0.0025 (7)−0.0025 (7)
C20.0312 (12)0.0260 (11)0.0163 (9)−0.0007 (9)0.0001 (8)0.0023 (7)
C30.0294 (12)0.0331 (12)0.0146 (9)−0.0039 (9)0.0043 (8)0.0002 (7)
C40.0267 (11)0.0302 (11)0.0154 (9)−0.0041 (9)0.0030 (7)−0.0036 (7)
C50.0263 (12)0.0398 (13)0.0208 (10)−0.0025 (9)0.0071 (8)−0.0026 (8)
C60.0235 (12)0.0424 (13)0.0248 (10)0.0021 (9)0.0051 (8)−0.0052 (9)
C70.0280 (12)0.0350 (13)0.0231 (10)0.0047 (9)0.0001 (8)−0.0011 (8)
C80.0241 (11)0.0320 (12)0.0172 (9)0.0012 (9)0.0014 (7)−0.0014 (7)
C90.0219 (11)0.0279 (11)0.0147 (8)−0.0027 (8)0.0008 (7)−0.0039 (7)
C100.0224 (11)0.0234 (11)0.0138 (8)−0.0028 (8)0.0002 (7)−0.0025 (7)
C110.0228 (11)0.0225 (10)0.0152 (8)0.0026 (8)0.0002 (7)−0.0007 (7)
C120.0222 (11)0.0242 (10)0.0143 (8)−0.0007 (8)0.0002 (7)−0.0023 (7)
C130.0231 (11)0.0204 (10)0.0197 (9)−0.0007 (8)−0.0002 (7)−0.0035 (7)
C140.0231 (12)0.0303 (12)0.0250 (10)−0.0031 (9)0.0033 (8)0.0015 (8)
C150.0243 (12)0.0297 (12)0.0240 (10)0.0035 (9)0.0039 (8)0.0020 (8)
C160.0235 (12)0.0300 (11)0.0210 (9)0.0035 (9)−0.0007 (7)0.0009 (8)
C170.0242 (11)0.0265 (11)0.0140 (8)−0.0012 (8)0.0026 (7)−0.0023 (7)
C180.0275 (13)0.0428 (15)0.0432 (13)0.0074 (10)0.0068 (10)0.0099 (10)
C190.0425 (15)0.0304 (12)0.0240 (10)0.0051 (10)0.0072 (9)−0.0021 (8)
C200.0183 (10)0.0262 (11)0.0143 (8)0.0020 (8)0.0034 (7)0.0016 (7)
C210.0238 (11)0.0254 (11)0.0158 (9)0.0030 (8)0.0000 (7)0.0029 (7)
C220.0240 (11)0.0250 (11)0.0192 (9)0.0012 (8)−0.0002 (7)0.0002 (7)
C230.0206 (11)0.0347 (12)0.0152 (9)0.0015 (9)0.0008 (7)0.0003 (8)
C240.0261 (12)0.0335 (12)0.0188 (9)0.0023 (9)−0.0012 (8)0.0070 (8)
C250.0293 (12)0.0242 (11)0.0199 (9)0.0015 (9)0.0019 (8)0.0026 (7)

Geometric parameters (Å, °)

Cl1—C231.7504 (19)C13—C141.511 (3)
O1—C171.369 (2)C14—C151.534 (3)
O1—C11.388 (2)C14—H14A0.9900
O2—C131.231 (2)C14—H14B0.9900
C1—C101.368 (3)C15—C181.523 (3)
C1—C21.420 (3)C15—C191.536 (3)
C2—C31.361 (3)C15—C161.545 (3)
C2—H20.9500C16—C171.484 (3)
C3—C41.420 (3)C16—H16A0.9900
C3—H30.9500C16—H16B0.9900
C4—C51.411 (3)C18—H18A0.9800
C4—C91.435 (2)C18—H18B0.9800
C5—C61.370 (3)C18—H18C0.9800
C5—H50.9500C19—H19A0.9800
C6—C71.410 (3)C19—H19B0.9800
C6—H60.9500C19—H19C0.9800
C7—C81.372 (3)C20—C211.383 (3)
C7—H70.9500C20—C251.398 (2)
C8—C91.420 (3)C21—C221.389 (3)
C8—H80.9500C21—H210.9500
C9—C101.431 (3)C22—C231.382 (3)
C10—C111.528 (2)C22—H220.9500
C11—C121.507 (3)C23—C241.378 (3)
C11—C201.537 (2)C24—C251.396 (3)
C11—H111.0000C24—H240.9500
C12—C171.347 (3)C25—H250.9500
C12—C131.477 (3)
C17—O1—C1117.88 (15)C15—C14—H14B108.9
C10—C1—O1123.37 (16)H14A—C14—H14B107.7
C10—C1—C2122.89 (18)C18—C15—C14110.08 (17)
O1—C1—C2113.74 (17)C18—C15—C19109.41 (17)
C3—C2—C1119.07 (18)C14—C15—C19109.66 (16)
C3—C2—H2120.5C18—C15—C16109.79 (17)
C1—C2—H2120.5C14—C15—C16107.30 (16)
C2—C3—C4121.38 (17)C19—C15—C16110.58 (17)
C2—C3—H3119.3C17—C16—C15113.05 (16)
C4—C3—H3119.3C17—C16—H16A109.0
C5—C4—C3121.86 (17)C15—C16—H16A109.0
C5—C4—C9119.55 (19)C17—C16—H16B109.0
C3—C4—C9118.58 (18)C15—C16—H16B109.0
C6—C5—C4120.98 (18)H16A—C16—H16B107.8
C6—C5—H5119.5C12—C17—O1122.17 (17)
C4—C5—H5119.5C12—C17—C16126.17 (17)
C5—C6—C7120.03 (19)O1—C17—C16111.65 (16)
C5—C6—H6120.0C15—C18—H18A109.5
C7—C6—H6120.0C15—C18—H18B109.5
C8—C7—C6120.4 (2)H18A—C18—H18B109.5
C8—C7—H7119.8C15—C18—H18C109.5
C6—C7—H7119.8H18A—C18—H18C109.5
C7—C8—C9121.35 (18)H18B—C18—H18C109.5
C7—C8—H8119.3C15—C19—H19A109.5
C9—C8—H8119.3C15—C19—H19B109.5
C8—C9—C10122.59 (16)H19A—C19—H19B109.5
C8—C9—C4117.64 (17)C15—C19—H19C109.5
C10—C9—C4119.76 (18)H19A—C19—H19C109.5
C1—C10—C9118.22 (16)H19B—C19—H19C109.5
C1—C10—C11120.41 (16)C21—C20—C25118.86 (17)
C9—C10—C11121.34 (16)C21—C20—C11119.82 (16)
C12—C11—C10109.01 (15)C25—C20—C11121.32 (17)
C12—C11—C20111.06 (14)C20—C21—C22121.22 (17)
C10—C11—C20110.16 (15)C20—C21—H21119.4
C12—C11—H11108.9C22—C21—H21119.4
C10—C11—H11108.9C23—C22—C21118.53 (18)
C20—C11—H11108.9C23—C22—H22120.7
C17—C12—C13118.09 (17)C21—C22—H22120.7
C17—C12—C11123.37 (17)C24—C23—C22122.26 (18)
C13—C12—C11118.54 (16)C24—C23—Cl1119.47 (14)
O2—C13—C12120.53 (18)C22—C23—Cl1118.26 (16)
O2—C13—C14121.94 (17)C23—C24—C25118.30 (17)
C12—C13—C14117.47 (16)C23—C24—H24120.8
C13—C14—C15113.33 (16)C25—C24—H24120.8
C13—C14—H14A108.9C24—C25—C20120.83 (19)
C15—C14—H14A108.9C24—C25—H25119.6
C13—C14—H14B108.9C20—C25—H25119.6
C17—O1—C1—C10−13.7 (3)C17—C12—C13—O2−177.76 (17)
C17—O1—C1—C2166.34 (15)C11—C12—C13—O21.7 (2)
C10—C1—C2—C3−2.7 (3)C17—C12—C13—C145.0 (2)
O1—C1—C2—C3177.34 (17)C11—C12—C13—C14−175.55 (15)
C1—C2—C3—C41.7 (3)O2—C13—C14—C15146.05 (17)
C2—C3—C4—C5179.68 (18)C12—C13—C14—C15−36.7 (2)
C2—C3—C4—C91.0 (3)C13—C14—C15—C18175.54 (16)
C3—C4—C5—C6−177.85 (18)C13—C14—C15—C19−64.0 (2)
C9—C4—C5—C60.8 (3)C13—C14—C15—C1656.1 (2)
C4—C5—C6—C70.7 (3)C18—C15—C16—C17−166.12 (17)
C5—C6—C7—C8−1.7 (3)C14—C15—C16—C17−46.5 (2)
C6—C7—C8—C91.3 (3)C19—C15—C16—C1773.1 (2)
C7—C8—C9—C10−179.36 (18)C13—C12—C17—O1−174.47 (15)
C7—C8—C9—C40.1 (3)C11—C12—C17—O16.1 (3)
C5—C4—C9—C8−1.2 (3)C13—C12—C17—C164.3 (3)
C3—C4—C9—C8177.50 (17)C11—C12—C17—C16−175.15 (16)
C5—C4—C9—C10178.32 (17)C1—O1—C17—C1211.2 (3)
C3—C4—C9—C10−3.0 (3)C1—O1—C17—C16−167.72 (15)
O1—C1—C10—C9−179.32 (16)C15—C16—C17—C1218.3 (3)
C2—C1—C10—C90.7 (3)C15—C16—C17—O1−162.83 (15)
O1—C1—C10—C11−1.1 (3)C12—C11—C20—C21−66.9 (2)
C2—C1—C10—C11178.86 (17)C10—C11—C20—C2154.0 (2)
C8—C9—C10—C1−178.37 (17)C12—C11—C20—C25113.16 (19)
C4—C9—C10—C12.1 (3)C10—C11—C20—C25−125.96 (18)
C8—C9—C10—C113.5 (3)C25—C20—C21—C220.5 (3)
C4—C9—C10—C11−176.02 (16)C11—C20—C21—C22−179.52 (16)
C1—C10—C11—C1216.0 (2)C20—C21—C22—C23−0.9 (3)
C9—C10—C11—C12−165.92 (16)C21—C22—C23—C240.6 (3)
C1—C10—C11—C20−106.13 (19)C21—C22—C23—Cl1−178.22 (14)
C9—C10—C11—C2072.0 (2)C22—C23—C24—C250.2 (3)
C10—C11—C12—C17−18.8 (2)Cl1—C23—C24—C25178.95 (15)
C20—C11—C12—C17102.80 (19)C23—C24—C25—C20−0.6 (3)
C10—C11—C12—C13161.81 (15)C21—C20—C25—C240.3 (3)
C20—C11—C12—C13−76.6 (2)C11—C20—C25—C24−179.72 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C24—H24···O2i0.952.563.376 (2)144

Symmetry codes: (i) −x+1, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2134).

References

  • Ion, R. M., Planner, A., Wiktorowicz, K. & Frackowiak, D. (1998). Acta Biochim. Pol.45, 833–845. [PubMed]
  • Lambert, R. W., Martin, J. A., Merrett, J. H., Parkes, K. E. B. & Thomas, G. J. (1997). PCT Int. Appl. WO 9706178, 1–80.
  • Poupelin, J. P., Saint-Ruf, G. Foussard-Blanpin, G. O., Narcisse, G., Uchida-Ernouf, G. & Lacroix, R. (1978). Eur. J. Med. Chem.13, 67–71.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Saint-Ruf, G., Hieu, H. T. & Poupelin, J. P. (1975). Naturwissenschaften, 62, 584–585. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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