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The central ring of the anthrone system in the title compound, C17H14O4, has a shallow envelope conformation, and each of the two outer rings is inclined at an angle of 17.41 (3)°. In the solid state, the mol­ecules exist as centrosymmetrically related O-H...O hydrogen-bonded dimers. Two intramolecular O-H...O hydrogen bonds, involving the central carbonyl O atom and having a graph-set motif of S(6), are observed. These intramolecular interactions lead co-operatively to an O-H...O...H-O pattern that has a binary graph-set motif of R^1_2(10).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103009223/sk1634sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103009223/sk1634Isup2.hkl
Contains datablock I

CCDC reference: 214410

Comment top

Anthracenones substituted at atom C10 have attained paramount significance because of their broad spectrum of biological activities, including antipsoriatic activity and leukotriene biosynthesis inhibition (Hayden et al., 1994; Muller & Prinz, 1997; Earl et al., 1998). The 5-LO (LO is lipoxygenase) pathway has been the major focus of study because of the pronounced pro-inflammatory role of leukotrienes and the approval of 5-LO inhibitors for the treatment of asthma (Young, 1999). Although less well characterized, the 12-LO pathway may also play an important role in the progression of human diseases such as cancer (Honn et al., 1994) and psoriasis (Ikai, 1999). In this paper, we report the crystal structure of the title compound, (I), and the interesting hydrogen-bond patterns observed in the solid state.

Fig. 1 shows a perspective view of (I), with the atom-numbering scheme. Most of the bond lengths and angles are unexceptional and comparable to those reported for related structures (Brown & Fullerton, 1980; Skrzat & Roszak, 1986; Roszak & Engelen, 1990). The anthrone carbonyl C9O9 distance [1.2603 (13) Å] is significantly longer than that usually observed for carbonyl bonds. This is probably a result of the involvement of atom O9 in two intramolecular hydrogen bonds. The anthracenone tricyclic ring system is nonplanar; the dihedral angle between the two halves of the system is 16.30 (3)° and that between the two outer planar rings is 17.41 (3)°. The central ring adopts a shallow envelope conformation [Cremer & Pople (1975) puckering parameters Q = 0.206 (1) Å, q2 = 0.189 (1) Å, q3 = −0.083 (1) Å, θ = 113.8 (4)° and ϕ2 = 357.4 (4)°] for the atoms sequence C9—C12—C11—C10—C14—C13. The envelope atom, C10, lies 0.291 (2) Å from the plane defined by the remaining five ring atoms. However, in related compounds, shallow boat-like (Brown & Fullerton, 1980; Roszak & Engelen, 1990) and chair-like conformations (Skrzat & Roszak, 1986) have been reported.

The propene and hydroxy substituents at atom C10 are nearly perpendicular to the least-squares plane of the anthracenone system, with dihedral angles of 86.47 (6) and 86.93 (1)°, respectively (the plane of the OH group is defined by atoms C10, O15 and H15). The hydroxy group is oriented roughly perpendicular to the central ring of the anthrone system in related compounds (Skrzat & Roszak, 1986; Roszak & Engelen, 1990).

There are two intramolecular hydrogen bonds between the 1,8-hydroxy groups and the carbonyl O atom of the central ring of (I) (Table 2), each generating an S(6) graph-set motif (Bernstein et al., 1995). Thus, the carbonyl O atom is an acceptor of two hydrogen bonds, and these intramolecular interactions lead cooperatively to an O—H···O···H—O pattern, which has a binary graph-set motif of R12(10). The hydroxy substituent at atom C10 forms an intermolecular hydrogen bond with the hydroxy O atom at atom C1 of a neighbouring centrosymmetrically related molecule. This interaction links the molecules into O—H···O hydrogen-bonded dimers that have a graph-set motif of R22(14).

Experimental top

1,8-Dihydroxyanthraquinone (750 mg, 3.1 mmol), allyl bromide (654 mg, 5.4 mmol) and indium metal (413 mg, 3.6 mmol) were added to? a mixture of THF (10 ml), CH3OH (10 ml) and water (5 ml), and the reaction mixture was stirred at 303–305 K for 4–6 h. The reaction mixture was then quenched with saturated brine solution and dilute HCl until the mixture became clear. The product was extracted (CHCl3), the extract was dried (Na2SO4) and the solvent was removed. Column chromatography (silica gel, 60–120 mesh) was used to isolate a pure yellow solid from the residue. The resulting yellow solid was recrystallized from a mixture of ethyl acetate and methanol to afford crystals of (I) (yield 90%, m.p. 394–396 K). MS (m/z, mass/relative intensity): 282 [M+]; 1H NMR (CDCl3): δ 2.56 (1H, s, OH), 2.59–2.62 (2H, m, CH2), 4.58–4.90 (2H, m, CH2), 5.10–5.24 (1H, m, CH), 6.83 (2H, d, Jo = 8.2, H–2,7), 7.32 (2H, d, Jo = 8.2, H–4,5), 7.51 (2H, t, Jo = 8.2, H–3,6), 12.04 (2H, s, 2 × OH); 13C NMR (normal/DEPT–135; CDCl3): 54.23 (-ve, CH2), 72.96 (ab, C), 114.32 (ab, C), 116.87 (+ve, CH), 119.87 (-ve, CH2), 130.84 (+ve, CH), 136.58 (+ve, CH), 148.58 (ab, C), 161.77 (ab, C), 192.13 (ab, C). UVmax (EtOH): 374 (8 × 102), 299 (7.4 × 102), 267 (6.2 × 102) nm. Analysis found: C 72.6, H 4.7%; C17H14O4 requires: C 72.34; H 4.96%.

Refinement top

Hydroxy H atoms were located from difference Fourier maps, and these atoms' positions and their individual isotropic displacement parameters were refined freely. The remaining H atoms were placed in idealized positions (C—H = 0.95–0.99 Å) and were constrained to ride on their parent atoms, with Uiso(H) equal to 1.5Ueq(C). Reflection 0 2 0 was partially obscured by the beam stop and hence was omitted.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids have been drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii.
[Figure 2] Fig. 2. The connection of molecules of (I) into dimers [symmetry code: (i) 1 − x,-y,-z]. H atoms bonded to C atoms have been omitted for clarity.
10-[1-(prop-2-enyl)]-1,8,10-trihydoxy-9(10H)-anthracenone top
Crystal data top
C17H14O4F(000) = 592
Mr = 282.28Dx = 1.427 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3936 reflections
a = 9.0267 (1) Åθ = 2.0–30.0°
b = 20.0965 (3) ŵ = 0.10 mm1
c = 8.0592 (1) ÅT = 160 K
β = 116.0327 (9)°Tablet, yellow
V = 1313.65 (3) Å30.30 × 0.25 × 0.18 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
2963 reflections with I > 2σ(I)
Radiation source: Nonius FR591 sealed tube generatorRint = 0.049
Horizontally mounted graphite crystal monochromatorθmax = 30.0°, θmin = 2.7°
Detector resolution: 9 pixels mm-1h = 1211
ϕ and ω scans with κ offsetsk = 280
34734 measured reflectionsl = 011
3832 independent reflections
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)] = 0.047Hydrogen site location: geom & difmap
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0739P)2 + 0.264P]
where P = (Fo2 + 2Fc2)/3
3832 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C17H14O4V = 1313.65 (3) Å3
Mr = 282.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.0267 (1) ŵ = 0.10 mm1
b = 20.0965 (3) ÅT = 160 K
c = 8.0592 (1) Å0.30 × 0.25 × 0.18 mm
β = 116.0327 (9)°
Data collection top
Nonius KappaCCD
diffractometer
2963 reflections with I > 2σ(I)
34734 measured reflectionsRint = 0.049
3832 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.33 e Å3
3832 reflectionsΔρmin = 0.24 e Å3
202 parameters
Special details top

Experimental. Solvent used: Ethyl acetate and MeOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.718 (1) Frames collected: 690 Seconds exposure per frame: 22 Degrees rotation per frame: 1.1 Crystal-Detector distance (mm): 30.20

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
O10.51224 (12)0.09385 (4)0.28402 (13)0.0326 (2)
H10.437 (2)0.0691 (10)0.307 (3)0.058 (5)*
O80.15891 (12)0.10467 (5)0.28243 (15)0.0407 (3)
H80.216 (3)0.0607 (12)0.318 (3)0.083 (7)*
O90.35688 (11)0.00909 (4)0.31614 (12)0.0311 (2)
O150.70088 (12)0.16817 (4)0.06173 (13)0.0303 (2)
H150.631 (2)0.1530 (9)0.045 (3)0.053 (5)*
C10.60757 (15)0.04985 (6)0.24571 (16)0.0269 (2)
C20.73263 (15)0.07554 (6)0.20827 (17)0.0306 (3)
H20.75210.12210.21470.037*
C30.82826 (15)0.03304 (6)0.16180 (17)0.0308 (3)
H30.91230.05090.13410.037*
C40.80403 (14)0.03550 (6)0.15466 (17)0.0282 (2)
H40.87130.06400.12260.034*
C50.45255 (16)0.22534 (6)0.13530 (18)0.0309 (3)
H50.51970.25460.10500.037*
C60.30254 (17)0.24741 (6)0.12428 (18)0.0344 (3)
H60.26640.29130.08190.041*
C70.20529 (16)0.20699 (7)0.17352 (19)0.0340 (3)
H70.10380.22310.16660.041*
C80.25679 (15)0.14231 (6)0.23360 (17)0.0300 (3)
C90.44482 (14)0.04697 (6)0.27165 (15)0.0251 (2)
C100.66851 (14)0.13730 (6)0.20255 (16)0.0252 (2)
C110.50429 (14)0.16046 (6)0.19067 (16)0.0253 (2)
C120.40543 (14)0.11781 (6)0.23839 (16)0.0251 (2)
C130.58036 (13)0.01977 (5)0.24000 (15)0.0241 (2)
C140.68139 (13)0.06203 (6)0.19455 (15)0.0241 (2)
C160.81159 (15)0.16202 (6)0.38569 (17)0.0285 (3)
H1610.91700.15490.37810.034*
H1620.79870.21060.39600.034*
C170.82346 (14)0.12965 (6)0.55763 (17)0.0297 (3)
H170.82540.08240.56250.036*
C180.83142 (17)0.16214 (7)0.70299 (19)0.0380 (3)
H1810.82980.20940.70280.046*
H1820.83880.13830.80820.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0396 (5)0.0233 (4)0.0360 (5)0.0038 (4)0.0177 (4)0.0021 (4)
O80.0308 (5)0.0431 (6)0.0546 (6)0.0001 (4)0.0246 (5)0.0032 (5)
O90.0319 (4)0.0297 (5)0.0349 (5)0.0049 (3)0.0177 (4)0.0016 (4)
O150.0354 (5)0.0280 (4)0.0308 (5)0.0047 (3)0.0176 (4)0.0016 (3)
C10.0315 (6)0.0233 (5)0.0231 (5)0.0022 (4)0.0094 (5)0.0014 (4)
C20.0338 (6)0.0248 (6)0.0293 (6)0.0044 (5)0.0102 (5)0.0008 (5)
C30.0279 (6)0.0326 (6)0.0300 (6)0.0057 (5)0.0110 (5)0.0005 (5)
C40.0244 (5)0.0306 (6)0.0293 (6)0.0009 (4)0.0115 (5)0.0005 (5)
C50.0365 (6)0.0246 (6)0.0316 (6)0.0016 (5)0.0148 (5)0.0012 (5)
C60.0410 (7)0.0266 (6)0.0329 (6)0.0070 (5)0.0138 (5)0.0008 (5)
C70.0308 (6)0.0352 (7)0.0342 (7)0.0075 (5)0.0127 (5)0.0031 (5)
C80.0268 (6)0.0337 (6)0.0292 (6)0.0010 (5)0.0121 (5)0.0031 (5)
C90.0250 (5)0.0269 (6)0.0218 (5)0.0038 (4)0.0089 (4)0.0004 (4)
C100.0278 (5)0.0231 (5)0.0260 (5)0.0037 (4)0.0131 (4)0.0006 (4)
C110.0267 (5)0.0242 (5)0.0235 (5)0.0010 (4)0.0097 (4)0.0017 (4)
C120.0247 (5)0.0251 (5)0.0246 (5)0.0009 (4)0.0101 (4)0.0021 (4)
C130.0255 (5)0.0227 (5)0.0228 (5)0.0007 (4)0.0094 (4)0.0001 (4)
C140.0227 (5)0.0238 (5)0.0235 (5)0.0017 (4)0.0080 (4)0.0004 (4)
C160.0265 (6)0.0266 (6)0.0308 (6)0.0050 (4)0.0109 (5)0.0026 (5)
C170.0275 (6)0.0249 (6)0.0303 (6)0.0007 (4)0.0068 (5)0.0002 (4)
C180.0399 (7)0.0399 (7)0.0366 (7)0.0043 (6)0.0190 (6)0.0000 (5)
Geometric parameters (Å, º) top
O1—C11.3605 (14)C6—H60.9500
O1—H10.925 (19)C7—C81.3937 (18)
O8—C81.3465 (15)C7—H70.9500
O8—H81.00 (2)C8—C121.4138 (16)
O9—C91.2603 (13)C9—C131.4610 (16)
O15—C101.4315 (14)C9—C121.4632 (17)
O15—H150.87 (2)C10—C111.5162 (16)
C1—C21.3896 (17)C10—C141.5206 (16)
C1—C131.4177 (16)C10—C161.5557 (16)
C2—C31.3779 (18)C11—C121.4072 (16)
C2—H20.9500C13—C141.4073 (15)
C3—C41.3919 (17)C16—C171.4914 (17)
C3—H30.9500C16—H1610.9900
C4—C141.3877 (16)C16—H1620.9900
C4—H40.9500C17—C181.3152 (18)
C5—C61.3902 (18)C17—H170.9500
C5—C111.3908 (17)C18—H1810.9500
C5—H50.9500C18—H1820.9500
C6—C71.3762 (19)
C1—O1—H1106.8 (12)O15—C10—C11110.55 (9)
C8—O8—H8104.7 (13)O15—C10—C14110.58 (9)
C10—O15—H15108.6 (12)C11—C10—C14113.17 (9)
O1—C1—C2117.56 (11)O15—C10—C16103.91 (9)
O1—C1—C13122.06 (11)C11—C10—C16110.09 (9)
C2—C1—C13120.36 (11)C14—C10—C16108.11 (9)
C3—C2—C1119.61 (11)C5—C11—C12119.66 (11)
C3—C2—H2120.2C5—C11—C10119.29 (10)
C1—C2—H2120.2C12—C11—C10121.03 (10)
C2—C3—C4121.25 (11)C11—C12—C8119.24 (11)
C2—C3—H3119.4C11—C12—C9120.69 (10)
C4—C3—H3119.4C8—C12—C9119.69 (11)
C14—C4—C3119.84 (11)C14—C13—C1118.76 (10)
C14—C4—H4120.1C14—C13—C9120.50 (10)
C3—C4—H4120.1C1—C13—C9120.67 (10)
C6—C5—C11120.00 (12)C4—C14—C13120.16 (11)
C6—C5—H5120.0C4—C14—C10118.40 (10)
C11—C5—H5120.0C13—C14—C10121.27 (10)
C7—C6—C5121.33 (12)C17—C16—C10115.68 (10)
C7—C6—H6119.3C17—C16—H161108.4
C5—C6—H6119.3C10—C16—H161108.4
C6—C7—C8119.53 (12)C17—C16—H162108.4
C6—C7—H7120.2C10—C16—H162108.4
C8—C7—H7120.2H161—C16—H162107.4
O8—C8—C7117.63 (11)C18—C17—C16124.38 (12)
O8—C8—C12122.21 (12)C18—C17—H17117.8
C7—C8—C12120.15 (12)C16—C17—H17117.8
O9—C9—C13120.26 (10)C17—C18—H181120.0
O9—C9—C12120.47 (10)C17—C18—H182120.0
C13—C9—C12119.13 (10)H181—C18—H182120.0
O1—C1—C2—C3177.53 (11)O9—C9—C12—C87.88 (17)
C13—C1—C2—C31.30 (18)C13—C9—C12—C8167.84 (10)
C1—C2—C3—C41.13 (19)O1—C1—C13—C14178.32 (10)
C2—C3—C4—C140.11 (19)C2—C1—C13—C140.45 (17)
C11—C5—C6—C72.33 (19)O1—C1—C13—C91.33 (17)
C5—C6—C7—C80.8 (2)C2—C1—C13—C9177.44 (10)
C6—C7—C8—O8179.26 (12)O9—C9—C13—C14178.49 (10)
C6—C7—C8—C121.95 (19)C12—C9—C13—C145.78 (16)
C6—C5—C11—C121.09 (18)O9—C9—C13—C14.56 (17)
C6—C5—C11—C10179.79 (11)C12—C9—C13—C1171.16 (10)
O15—C10—C11—C534.15 (14)C3—C4—C14—C130.75 (17)
C14—C10—C11—C5158.81 (11)C3—C4—C14—C10174.51 (11)
C16—C10—C11—C580.09 (13)C1—C13—C14—C40.58 (16)
O15—C10—C11—C12147.17 (10)C9—C13—C14—C4176.42 (10)
C14—C10—C11—C1222.51 (15)C1—C13—C14—C10174.55 (11)
C16—C10—C11—C1298.59 (12)C9—C13—C14—C108.45 (16)
C5—C11—C12—C81.59 (17)O15—C10—C14—C438.39 (14)
C10—C11—C12—C8177.09 (10)C11—C10—C14—C4163.04 (10)
C5—C11—C12—C9171.28 (11)C16—C10—C14—C474.75 (13)
C10—C11—C12—C910.05 (17)O15—C10—C14—C13146.40 (10)
O8—C8—C12—C11178.15 (11)C11—C10—C14—C1321.75 (15)
C7—C8—C12—C113.12 (18)C16—C10—C14—C13100.46 (12)
O8—C8—C12—C98.92 (18)O15—C10—C16—C17171.40 (10)
C7—C8—C12—C9169.82 (11)C11—C10—C16—C1770.20 (13)
O9—C9—C12—C11179.29 (10)C14—C10—C16—C1753.88 (13)
C13—C9—C12—C114.99 (16)C10—C16—C17—C18127.90 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O90.925 (19)1.74 (2)2.5753 (13)148.0 (17)
O8—H8···O91.00 (2)1.64 (2)2.5555 (14)149 (2)
O15—H15···O1i0.87 (2)2.15 (2)2.9985 (13)166.3 (17)
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC17H14O4
Mr282.28
Crystal system, space groupMonoclinic, P21/c
Temperature (K)160
a, b, c (Å)9.0267 (1), 20.0965 (3), 8.0592 (1)
β (°) 116.0327 (9)
V3)1313.65 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.25 × 0.18
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
34734, 3832, 2963
Rint0.049
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.135, 1.05
No. of reflections3832
No. of parameters202
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.24

Computer programs: COLLECT (Nonius, 2000), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).

Selected torsion angles (º) top
C14—C10—C11—C1222.51 (15)C12—C9—C13—C145.78 (16)
C10—C11—C12—C910.05 (17)C9—C13—C14—C108.45 (16)
C13—C9—C12—C114.99 (16)C11—C10—C14—C1321.75 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O90.925 (19)1.74 (2)2.5753 (13)148.0 (17)
O8—H8···O91.00 (2)1.64 (2)2.5555 (14)149 (2)
O15—H15···O1i0.87 (2)2.15 (2)2.9985 (13)166.3 (17)
Symmetry code: (i) x+1, y, z.
 

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