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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3020.
Published online 2009 November 7. doi:  10.1107/S1600536809046157
PMCID: PMC2971999

9,9-Dimethyl-12-phenyl-8,9-dihydro-12H-benzo[a]xanthen-11(10H)-one

Abstract

The title compound, C25H22O2, was synthesized via the three-component coupling of benzaldehyde, 2-naphthol and 5,5-dimethyl­cyclo­hexane-1,3-dione. In the crystal structure, centrosymmetrically related mol­ecules are linked into dimers by pairs of inter­molecular C—H(...)O hydrogen bonds. The dimers are further connected into a three-dimensional network by π–π aromatic stacking inter­actions involving the naphthalene ring system, with centroid–centroid separations of 3.695 (7) Å.

Related literature

For the biological and pharmacological activity of xanthenes and benzoxanthenes, see: Ion et al. (1998 [triangle]); Lambert et al. (1997 [triangle]); Poupelin et al. (1978 [triangle]); Saint-Ruf et al. (1975 [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3020-scheme1.jpg

Experimental

Crystal data

  • C25H22O2
  • M r = 354.43
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3020-efi1.jpg
  • a = 9.1881 (18) Å
  • b = 9.2317 (18) Å
  • c = 12.866 (3) Å
  • α = 72.78 (3)°
  • β = 80.82 (3)°
  • γ = 62.17 (2)°
  • V = 921.6 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 113 K
  • 0.20 × 0.18 × 0.14 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.984, T max = 0.989
  • 8318 measured reflections
  • 4294 independent reflections
  • 2797 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.114
  • S = 0.97
  • 4294 reflections
  • 246 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.26 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/S1600536809046157/rz2384sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046157/rz2384Isup2.hkl

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

Acknowledgments

The authors thank the Tianjin Natural Science Foundation (07JCYBJC02200) 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 and are utilized as antagonists for paralyzing action of zoxazolamine (Saint-Ruf et al., 1975) and in photodynamic therapy (Ion et al., 1998). So far, no crystallographic studies have been performed on benzoxanthenes. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), bond lengths (Allen et al., 1987) and angles are within normal ranges. The pyran ring adopts a boat conformation, with atoms O1 and C11 displaced by 0.1568 (9) and 0.3301 (12) Å from the C1/C10/C12/C17 plane, while the cyclohexene ring displays an envelope conformation, with atom C15 displaced by 0.6705 (13) Å from the C12/C13/C14/C16/C17 plane. In the crystal packing (Fig. 2), centrosymmetrically related molecules are connected into dimers by intermolecular C—H···O hydrogen bonds (Table 1). The dimers are further linked into a three-dimensional network by π···π aromatic stacking interactions involving the naphthalene ring system, with centroid-to-centroid separations of 3.695 (7) Å.

Experimental

NaHSO4 (0.2 mmol) was added to benzaldehyde (1 mmol), 2-naphthol (1 mmol), 5,5 -dimethylcyclohexane-1,3-dione (1.1 mmol) and [BMIM]BF4 (1 ml; BMIM+ is 1-n-butyl-3-methylimidazolium), and the mixture was stirred at 80 °C for 1 h. After completion of the reaction as indicated by TLC, the system was cooled to room temperature. The mixture was washed with water (10 ml) and extracted with ethyl acetate (3×15 ml). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness. The product was purified by column chromatography on silica gel. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

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.
The molecular structure of the title compound, showing the atom-numbering scheme. Dispacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Packing diagram of the title compound, showing hydrogen-bonding interactions as dashed lines, H atoms are shown as small spheres of arbitary radii.

Crystal data

C25H22O2Z = 2
Mr = 354.43F(000) = 376
Triclinic, P1Dx = 1.277 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1881 (18) ÅCell parameters from 2907 reflections
b = 9.2317 (18) Åθ = 2.5–27.9°
c = 12.866 (3) ŵ = 0.08 mm1
α = 72.78 (3)°T = 113 K
β = 80.82 (3)°Prism, colourless
γ = 62.17 (2)°0.20 × 0.18 × 0.14 mm
V = 921.6 (3) Å3

Data collection

Rigaku Saturn CCD area-detector diffractometer4294 independent reflections
Radiation source: rotating anode2797 reflections with I > 2σ(I)
confocalRint = 0.027
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.5°
ω and [var phi] scansh = −12→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −12→12
Tmin = 0.984, Tmax = 0.989l = −16→13
8318 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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 0.97w = 1/[σ2(Fo2) + (0.0691P)2] where P = (Fo2 + 2Fc2)/3
4294 reflections(Δ/σ)max < 0.001
246 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.26 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
O10.80464 (10)0.56824 (10)0.17827 (6)0.0210 (2)
O21.16069 (10)0.04959 (11)0.40301 (7)0.0304 (3)
C10.66568 (14)0.56096 (15)0.23792 (9)0.0183 (3)
C20.51931 (15)0.71327 (15)0.21330 (10)0.0233 (3)
H20.51950.80810.15820.028*
C30.37777 (14)0.72247 (16)0.26954 (10)0.0248 (3)
H30.27860.82420.25300.030*
C40.37678 (14)0.58228 (16)0.35227 (10)0.0210 (3)
C50.23201 (15)0.59156 (17)0.41469 (10)0.0258 (3)
H50.13280.69380.40030.031*
C60.23318 (15)0.45569 (18)0.49505 (10)0.0268 (3)
H60.13520.46390.53610.032*
C70.37922 (15)0.30371 (17)0.51717 (10)0.0240 (3)
H70.37920.20960.57310.029*
C80.52136 (14)0.28998 (16)0.45884 (9)0.0203 (3)
H80.61880.18620.47480.024*
C90.52538 (14)0.42815 (15)0.37510 (9)0.0175 (3)
C100.67273 (13)0.41870 (14)0.31377 (9)0.0165 (2)
C110.83294 (13)0.25608 (14)0.32854 (9)0.0165 (3)
H110.84520.19390.40730.020*
C120.97420 (13)0.30107 (15)0.29088 (9)0.0171 (3)
C131.13999 (14)0.17861 (16)0.33168 (9)0.0193 (3)
C141.28077 (15)0.22110 (17)0.28404 (10)0.0244 (3)
H14A1.38360.11440.28880.029*
H14B1.29380.28530.32840.029*
C151.25745 (14)0.32512 (16)0.16526 (9)0.0205 (3)
C161.09217 (14)0.48479 (15)0.15974 (10)0.0221 (3)
H16A1.10300.56200.19410.027*
H16B1.06460.54450.08250.027*
C170.95571 (14)0.44364 (15)0.21571 (9)0.0183 (3)
C180.83235 (13)0.14387 (14)0.26191 (9)0.0167 (3)
C190.82901 (15)−0.01023 (15)0.31132 (10)0.0225 (3)
H190.8283−0.04850.38850.027*
C200.82669 (16)−0.10895 (16)0.24890 (11)0.0283 (3)
H200.8240−0.21390.28380.034*
C210.82820 (15)−0.05570 (17)0.13675 (11)0.0263 (3)
H210.8265−0.12350.09440.032*
C220.83223 (15)0.09814 (16)0.08610 (10)0.0233 (3)
H220.83350.13580.00890.028*
C230.83433 (14)0.19590 (15)0.14836 (9)0.0197 (3)
H230.83720.30070.11320.024*
C241.25856 (16)0.21964 (16)0.09293 (10)0.0247 (3)
H24A1.23940.28810.01750.037*
H24B1.17140.18340.11790.037*
H24C1.36550.11980.09710.037*
C251.39520 (16)0.37858 (19)0.12682 (11)0.0319 (3)
H25A1.50170.27760.13410.048*
H25B1.39280.44950.17130.048*
H25C1.37960.44300.05040.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0171 (4)0.0158 (4)0.0237 (5)−0.0045 (3)−0.0001 (3)−0.0013 (3)
O20.0233 (5)0.0274 (5)0.0263 (5)−0.0047 (4)−0.0044 (4)0.0036 (4)
C10.0162 (6)0.0188 (6)0.0185 (6)−0.0062 (5)0.0009 (5)−0.0064 (5)
C20.0242 (6)0.0158 (6)0.0233 (7)−0.0037 (5)−0.0038 (5)−0.0030 (5)
C30.0182 (6)0.0192 (6)0.0289 (7)0.0009 (5)−0.0049 (5)−0.0085 (5)
C40.0170 (6)0.0229 (6)0.0214 (6)−0.0044 (5)−0.0020 (5)−0.0100 (5)
C50.0158 (6)0.0306 (7)0.0279 (7)−0.0033 (5)−0.0016 (5)−0.0143 (6)
C60.0182 (6)0.0419 (8)0.0238 (7)−0.0136 (6)0.0041 (5)−0.0150 (6)
C70.0244 (6)0.0313 (7)0.0197 (6)−0.0144 (6)0.0003 (5)−0.0081 (5)
C80.0186 (6)0.0233 (6)0.0190 (6)−0.0076 (5)−0.0012 (5)−0.0081 (5)
C90.0157 (5)0.0200 (6)0.0162 (6)−0.0051 (5)−0.0014 (4)−0.0079 (5)
C100.0159 (5)0.0159 (5)0.0167 (6)−0.0043 (5)−0.0021 (4)−0.0067 (5)
C110.0161 (5)0.0141 (5)0.0160 (6)−0.0040 (4)−0.0015 (4)−0.0033 (4)
C120.0151 (5)0.0180 (6)0.0171 (6)−0.0053 (5)−0.0008 (4)−0.0065 (5)
C130.0181 (6)0.0227 (6)0.0148 (6)−0.0058 (5)−0.0019 (5)−0.0064 (5)
C140.0181 (6)0.0323 (7)0.0221 (7)−0.0098 (5)−0.0034 (5)−0.0070 (5)
C150.0173 (6)0.0239 (6)0.0207 (7)−0.0090 (5)0.0001 (5)−0.0069 (5)
C160.0223 (6)0.0199 (6)0.0255 (7)−0.0108 (5)0.0012 (5)−0.0062 (5)
C170.0166 (6)0.0184 (6)0.0194 (6)−0.0057 (5)−0.0012 (4)−0.0073 (5)
C180.0123 (5)0.0163 (5)0.0195 (6)−0.0042 (4)0.0009 (4)−0.0060 (5)
C190.0248 (6)0.0190 (6)0.0205 (6)−0.0087 (5)0.0036 (5)−0.0044 (5)
C200.0333 (7)0.0208 (6)0.0329 (8)−0.0146 (6)0.0086 (6)−0.0105 (6)
C210.0259 (7)0.0263 (7)0.0317 (8)−0.0119 (5)0.0041 (5)−0.0164 (6)
C220.0226 (6)0.0264 (7)0.0208 (6)−0.0098 (5)0.0001 (5)−0.0081 (5)
C230.0196 (6)0.0181 (6)0.0207 (6)−0.0083 (5)0.0003 (5)−0.0044 (5)
C240.0261 (6)0.0259 (7)0.0205 (7)−0.0100 (5)0.0017 (5)−0.0079 (5)
C250.0240 (7)0.0409 (8)0.0344 (8)−0.0176 (6)0.0018 (6)−0.0104 (7)

Geometric parameters (Å, °)

O1—C171.3697 (15)C14—C151.5321 (17)
O1—C11.4002 (14)C14—H14A0.9900
O2—C131.2224 (15)C14—H14B0.9900
C1—C101.3651 (16)C15—C251.5262 (17)
C1—C21.4116 (17)C15—C241.5293 (18)
C2—C31.3620 (17)C15—C161.5382 (17)
C2—H20.9500C16—C171.4932 (17)
C3—C41.4144 (18)C16—H16A0.9900
C3—H30.9500C16—H16B0.9900
C4—C51.4195 (17)C18—C191.3886 (17)
C4—C91.4287 (17)C18—C231.3964 (17)
C5—C61.3659 (19)C19—C201.3902 (19)
C5—H50.9500C19—H190.9500
C6—C71.4062 (19)C20—C211.3800 (19)
C6—H60.9500C20—H200.9500
C7—C81.3689 (17)C21—C221.3916 (18)
C7—H70.9500C21—H210.9500
C8—C91.4167 (17)C22—C231.3805 (18)
C8—H80.9500C22—H220.9500
C9—C101.4328 (16)C23—H230.9500
C10—C111.5210 (16)C24—H24A0.9800
C11—C121.5084 (16)C24—H24B0.9800
C11—C181.5298 (17)C24—H24C0.9800
C11—H111.0000C25—H25A0.9800
C12—C171.3367 (16)C25—H25B0.9800
C12—C131.4730 (17)C25—H25C0.9800
C13—C141.5104 (17)
C17—O1—C1117.38 (9)C15—C14—H14B108.8
C10—C1—O1122.50 (10)H14A—C14—H14B107.7
C10—C1—C2123.34 (11)C25—C15—C24109.07 (11)
O1—C1—C2114.16 (10)C25—C15—C14110.56 (11)
C3—C2—C1119.12 (11)C24—C15—C14109.76 (11)
C3—C2—H2120.4C25—C15—C16108.86 (11)
C1—C2—H2120.4C24—C15—C16111.11 (10)
C2—C3—C4120.76 (11)C14—C15—C16107.46 (10)
C2—C3—H3119.6C17—C16—C15112.02 (10)
C4—C3—H3119.6C17—C16—H16A109.2
C3—C4—C5121.59 (11)C15—C16—H16A109.2
C3—C4—C9119.45 (11)C17—C16—H16B109.2
C5—C4—C9118.96 (11)C15—C16—H16B109.2
C6—C5—C4120.98 (12)H16A—C16—H16B107.9
C6—C5—H5119.5C12—C17—O1122.42 (11)
C4—C5—H5119.5C12—C17—C16125.56 (11)
C5—C6—C7120.07 (12)O1—C17—C16111.98 (10)
C5—C6—H6120.0C19—C18—C23118.23 (12)
C7—C6—H6120.0C19—C18—C11121.73 (10)
C8—C7—C6120.65 (12)C23—C18—C11120.04 (11)
C8—C7—H7119.7C18—C19—C20120.59 (12)
C6—C7—H7119.7C18—C19—H19119.7
C7—C8—C9121.00 (11)C20—C19—H19119.7
C7—C8—H8119.5C21—C20—C19120.56 (12)
C9—C8—H8119.5C21—C20—H20119.7
C8—C9—C4118.34 (11)C19—C20—H20119.7
C8—C9—C10122.35 (10)C20—C21—C22119.49 (13)
C4—C9—C10119.31 (11)C20—C21—H21120.3
C1—C10—C9117.94 (10)C22—C21—H21120.3
C1—C10—C11119.67 (10)C23—C22—C21119.78 (12)
C9—C10—C11122.36 (10)C23—C22—H22120.1
C12—C11—C10108.68 (9)C21—C22—H22120.1
C12—C11—C18109.88 (10)C22—C23—C18121.36 (11)
C10—C11—C18110.04 (10)C22—C23—H23119.3
C12—C11—H11109.4C18—C23—H23119.3
C10—C11—H11109.4C15—C24—H24A109.5
C18—C11—H11109.4C15—C24—H24B109.5
C17—C12—C13118.84 (11)H24A—C24—H24B109.5
C17—C12—C11121.87 (10)C15—C24—H24C109.5
C13—C12—C11119.12 (10)H24A—C24—H24C109.5
O2—C13—C12120.62 (11)H24B—C24—H24C109.5
O2—C13—C14121.87 (11)C15—C25—H25A109.5
C12—C13—C14117.49 (10)C15—C25—H25B109.5
C13—C14—C15113.72 (10)H25A—C25—H25B109.5
C13—C14—H14A108.8C15—C25—H25C109.5
C15—C14—H14A108.8H25A—C25—H25C109.5
C13—C14—H14B108.8H25B—C25—H25C109.5
C17—O1—C1—C10−15.68 (17)C18—C11—C12—C13−81.65 (13)
C17—O1—C1—C2163.81 (11)C17—C12—C13—O2177.56 (12)
C10—C1—C2—C32.0 (2)C11—C12—C13—O2−7.11 (18)
O1—C1—C2—C3−177.51 (11)C17—C12—C13—C14−0.99 (17)
C1—C2—C3—C40.5 (2)C11—C12—C13—C14174.34 (11)
C2—C3—C4—C5177.48 (13)O2—C13—C14—C15150.16 (12)
C2—C3—C4—C9−1.5 (2)C12—C13—C14—C15−31.31 (16)
C3—C4—C5—C6−179.36 (13)C13—C14—C15—C25174.07 (11)
C9—C4—C5—C6−0.4 (2)C13—C14—C15—C24−65.56 (14)
C4—C5—C6—C70.1 (2)C13—C14—C15—C1655.38 (14)
C5—C6—C7—C80.0 (2)C25—C15—C16—C17−169.02 (10)
C6—C7—C8—C90.19 (19)C24—C15—C16—C1770.84 (13)
C7—C8—C9—C4−0.50 (18)C14—C15—C16—C17−49.25 (14)
C7—C8—C9—C10178.98 (12)C13—C12—C17—O1−176.11 (11)
C3—C4—C9—C8179.59 (11)C11—C12—C17—O18.69 (19)
C5—C4—C9—C80.59 (18)C13—C12—C17—C166.36 (19)
C3—C4—C9—C100.09 (18)C11—C12—C17—C16−168.84 (11)
C5—C4—C9—C10−178.91 (12)C1—O1—C17—C1214.15 (18)
O1—C1—C10—C9176.12 (11)C1—O1—C17—C16−168.01 (10)
C2—C1—C10—C9−3.32 (19)C15—C16—C17—C1220.60 (18)
O1—C1—C10—C11−5.42 (18)C15—C16—C17—O1−157.15 (10)
C2—C1—C10—C11175.13 (11)C12—C11—C18—C19127.33 (11)
C8—C9—C10—C1−177.25 (11)C10—C11—C18—C19−113.03 (12)
C4—C9—C10—C12.23 (18)C12—C11—C18—C23−53.01 (13)
C8—C9—C10—C114.34 (18)C10—C11—C18—C2366.63 (13)
C4—C9—C10—C11−176.19 (11)C23—C18—C19—C20−0.39 (17)
C1—C10—C11—C1224.78 (15)C11—C18—C19—C20179.28 (11)
C9—C10—C11—C12−156.83 (11)C18—C19—C20—C210.21 (19)
C1—C10—C11—C18−95.58 (13)C19—C20—C21—C220.06 (18)
C9—C10—C11—C1882.81 (14)C20—C21—C22—C23−0.13 (18)
C10—C11—C12—C17−26.92 (16)C21—C22—C23—C18−0.05 (18)
C18—C11—C12—C1793.53 (13)C19—C18—C23—C220.31 (16)
C10—C11—C12—C13157.90 (11)C11—C18—C23—C22−179.36 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8···O2i0.952.493.366 (2)154

Symmetry codes: (i) −x+2, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2384).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography