2-Formyl-3-hydr­oxy-9,10-anthroquinone

Abstract

The mol­ecule of the title compound, C₁₅H₈O₄, is approximately planar. An intra­molecular O—H⋯O hydrogen bond is observed between the hydr­oxy and formyl groups. The crystal used was a nonmerohedral twin, with a minor twin component of 15.9%.

Related literature

For anti­leshmanial and anti­plasmodial activities, see: Sittie et al. (1999 ▶). For the treatment of twinned diffraction data, see: Spek (2003 ▶).

Experimental

Crystal data

• C₁₅H₈O₄

• M _r = 252.21

• Triclinic,

• a = 6.9194 (2) Å

• b = 8.0650 (2) Å

• c = 10.7601 (3) Å

• α = 86.250 (2)°

• β = 83.214 (2)°

• γ = 64.692 (2)°

• V = 538.96 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 100 (2) K

• 0.22 × 0.04 × 0.04 mm

Data collection

• Bruker SMART APEXII area-detector diffractometer

• Absorption correction: none

• 4946 measured reflections

• 2419 independent reflections

• 1880 reflections with I > 2σ(I)

• R _int = 0.024

Refinement

• R[F ² > 2σ(F ²)] = 0.087

• wR(F ²) = 0.343

• S = 1.11

• 2419 reflections

• 173 parameters

• H-atom parameters constrained

• Δρ_max = 0.49 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.84	2.00	2.635 (5)	132

supplementary crystallographic information

Experimental

Rennellia elliptica Korth from the Rubiaceae family was collected from Kuala Keniam, Pahang, Malaysia. The root was chopped into small pieces and dried. The dried sample (1 kg) was ground and then extracted successively with hexane, dichloromethane and methanol. The dichloromethane extract was concentrated in vacuo to give 27 g crude extract. The crude extract was fractionated by column chromatography. The column (60 cm X 5 cm) was packed with acid-washed silica gel and eluted with hexane, dichloromethane and methanol. Nine fractions were obtained, and 3-hydroxy-2-formyl-9,10-anthraquinone (41.5 mg) was isolated from the third fraction (hexane:dichloromethane, 30:70) by slow evaporation of the solvent mixture. The yellow crystals obtained were washed with acetone.

Refinement

Carbon- and oxygen-bound H-atoms were placed in calculated positions (C—H = 0.95 Å and O—H = 0.84 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U_eq(C,O). The crystal studied was a non-merohedral twin. The TwinRotMat in PLATON (Spek, 2003) gave the twin law as (-1 0 0, 0 - 1 0, -0.343 - 0.049 1), whose inclusion in the refinement lowered the R index from 11.3 to 8.7%. The twin component refined to 18.9%. The refinement is deemed satisfactory although the wR₂ value for all reflections is somewhat high. The structure has a long C5–C14 bond; as the anisotropic displacement parameters are normal, the likely reason is localization of the double bonds in the ring. On the other hand, the C13–C14 bond is somewhat short.

Figures

Fig. 1.

The molecular structure of the title compound, showing 70% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.

Crystal data

C15H8O4	Z = 2
Mr = 252.21	F(000) = 260
Triclinic, P1	Dx = 1.554 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9194 (2) Å	Cell parameters from 1888 reflections
b = 8.0650 (2) Å	θ = 3.3–28.3°
c = 10.7601 (3) Å	µ = 0.11 mm−1
α = 86.250 (2)°	T = 100 K
β = 83.214 (2)°	Block, yellow
γ = 64.692 (2)°	0.22 × 0.04 × 0.04 mm
V = 538.96 (3) Å3

Data collection

Bruker SMART APEXII area-detector diffractometer	1880 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
graphite	θmax = 27.5°, θmin = 2.8°
ω scans	h = −8→8
4946 measured reflections	k = −10→10
2419 independent reflections	l = −13→13

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.343	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.1778P)2 + 2.2381P] where P = (Fo2 + 2Fc2)/3
2419 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

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

	x	y	z	Uiso*/Ueq
O1	0.3155 (6)	0.6486 (5)	0.0888 (3)	0.0251 (8)
O2	0.2501 (6)	0.3493 (5)	0.0941 (3)	0.0242 (8)
H2	0.2611	0.4345	0.0490	0.029*
O3	0.2366 (5)	−0.0898 (4)	0.4383 (3)	0.0153 (7)
O4	0.2779 (5)	0.4648 (4)	0.6688 (3)	0.0172 (7)
C1	0.3060 (7)	0.6395 (6)	0.2041 (4)	0.0178 (9)
H1	0.3171	0.7336	0.2474	0.021*
C2	0.2786 (7)	0.4901 (6)	0.2772 (4)	0.0143 (9)
C3	0.2544 (7)	0.3500 (6)	0.2187 (4)	0.0161 (9)
C4	0.2356 (7)	0.2059 (6)	0.2894 (4)	0.0152 (9)
H4	0.2187	0.1116	0.2500	0.018*
C5	0.2419 (6)	0.2016 (5)	0.4183 (4)	0.0123 (8)
C6	0.2335 (6)	0.0406 (5)	0.4916 (4)	0.0112 (8)
C7	0.2285 (6)	0.0417 (5)	0.6299 (4)	0.0112 (8)
C8	0.2117 (7)	−0.1043 (6)	0.7003 (4)	0.0139 (8)
H8	0.1986	−0.1999	0.6601	0.017*
C9	0.2144 (7)	−0.1091 (6)	0.8286 (4)	0.0179 (9)
H9	0.2031	−0.2083	0.8766	0.021*
C10	0.2336 (7)	0.0310 (6)	0.8883 (4)	0.0188 (9)
H10	0.2353	0.0269	0.9767	0.023*
C11	0.2503 (7)	0.1762 (6)	0.8187 (4)	0.0173 (9)
H11	0.2645	0.2709	0.8594	0.021*
C12	0.2462 (6)	0.1835 (5)	0.6895 (4)	0.0113 (8)
C13	0.2641 (6)	0.3403 (6)	0.6165 (4)	0.0126 (8)
C14	0.2621 (6)	0.3426 (5)	0.4787 (4)	0.0120 (8)
C15	0.2815 (7)	0.4851 (6)	0.4072 (4)	0.0133 (8)
H15	0.2968	0.5801	0.4468	0.016*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.038 (2)	0.0258 (18)	0.0125 (16)	−0.0155 (16)	−0.0033 (13)	0.0054 (13)
O2	0.046 (2)	0.0283 (18)	0.0063 (15)	−0.0226 (17)	−0.0062 (13)	0.0020 (12)
O3	0.0194 (15)	0.0131 (14)	0.0147 (15)	−0.0079 (12)	−0.0028 (11)	−0.0009 (11)
O4	0.0228 (16)	0.0148 (15)	0.0165 (15)	−0.0103 (13)	−0.0003 (12)	−0.0039 (11)
C1	0.021 (2)	0.017 (2)	0.016 (2)	−0.0078 (17)	−0.0040 (16)	0.0035 (16)
C2	0.0146 (19)	0.0149 (19)	0.0119 (19)	−0.0053 (16)	−0.0011 (14)	0.0030 (15)
C3	0.017 (2)	0.021 (2)	0.0103 (19)	−0.0080 (17)	−0.0030 (15)	0.0010 (15)
C4	0.016 (2)	0.016 (2)	0.014 (2)	−0.0074 (16)	−0.0007 (15)	−0.0025 (15)
C5	0.0106 (18)	0.0107 (18)	0.0135 (19)	−0.0032 (14)	0.0010 (14)	0.0003 (14)
C6	0.0099 (17)	0.0105 (18)	0.0121 (19)	−0.0036 (14)	−0.0001 (14)	−0.0004 (14)
C7	0.0109 (18)	0.0114 (18)	0.0103 (18)	−0.0038 (14)	−0.0025 (13)	0.0011 (14)
C8	0.0145 (19)	0.0118 (18)	0.015 (2)	−0.0053 (15)	−0.0023 (15)	0.0013 (14)
C9	0.019 (2)	0.017 (2)	0.017 (2)	−0.0081 (17)	−0.0012 (16)	0.0055 (16)
C10	0.024 (2)	0.022 (2)	0.0110 (19)	−0.0100 (18)	−0.0009 (16)	0.0026 (16)
C11	0.021 (2)	0.018 (2)	0.013 (2)	−0.0084 (17)	−0.0008 (16)	−0.0009 (15)
C12	0.0108 (18)	0.0112 (18)	0.0109 (18)	−0.0039 (14)	−0.0002 (14)	−0.0005 (14)
C13	0.0112 (18)	0.0125 (19)	0.0139 (19)	−0.0046 (15)	−0.0015 (14)	−0.0010 (14)
C14	0.0116 (18)	0.0112 (18)	0.0127 (19)	−0.0044 (14)	0.0001 (14)	−0.0002 (14)
C15	0.0138 (19)	0.0112 (18)	0.014 (2)	−0.0049 (15)	0.0006 (14)	−0.0017 (14)

Geometric parameters (Å, °)

O1—C1	1.234 (5)	C7—C8	1.398 (5)
O2—C3	1.345 (5)	C7—C12	1.403 (5)
O2—H2	0.84	C8—C9	1.380 (6)
O3—C6	1.222 (5)	C8—H8	0.95
O4—C13	1.226 (5)	C9—C10	1.397 (6)
C1—C2	1.464 (6)	C9—H9	0.95
C1—H1	0.95	C10—C11	1.388 (6)
C2—C15	1.400 (6)	C10—H10	0.95
C2—C3	1.407 (6)	C11—C12	1.391 (6)
C3—C4	1.391 (6)	C11—H11	0.95
C4—C5	1.390 (6)	C12—C13	1.487 (5)
C4—H4	0.95	C13—C14	1.483 (6)
C5—C14	1.410 (6)	C14—C15	1.387 (6)
C5—C6	1.494 (5)	C15—H15	0.95
C6—C7	1.485 (5)
C3—O2—H2	120.0	C9—C8—H8	120.1
O1—C1—C2	122.8 (4)	C7—C8—H8	120.1
O1—C1—H1	118.6	C8—C9—C10	120.4 (4)
C2—C1—H1	118.6	C8—C9—H9	119.8
C15—C2—C3	119.7 (4)	C10—C9—H9	119.8
C15—C2—C1	119.1 (4)	C11—C10—C9	120.0 (4)
C3—C2—C1	121.2 (4)	C11—C10—H10	120.0
O2—C3—C4	117.9 (4)	C9—C10—H10	120.0
O2—C3—C2	121.8 (4)	C10—C11—C12	120.2 (4)
C4—C3—C2	120.3 (4)	C10—C11—H11	119.9
C5—C4—C3	119.2 (4)	C12—C11—H11	119.9
C5—C4—H4	120.4	C11—C12—C7	119.6 (4)
C3—C4—H4	120.4	C11—C12—C13	119.4 (4)
C4—C5—C14	121.2 (4)	C7—C12—C13	121.1 (3)
C4—C5—C6	118.4 (4)	O4—C13—C14	121.0 (4)
C14—C5—C6	120.3 (4)	O4—C13—C12	121.0 (4)
O3—C6—C7	121.3 (4)	C14—C13—C12	118.0 (3)
O3—C6—C5	120.5 (4)	C15—C14—C5	119.0 (4)
C7—C6—C5	118.1 (3)	C15—C14—C13	119.7 (4)
C8—C7—C12	120.1 (4)	C5—C14—C13	121.3 (4)
C8—C7—C6	118.9 (4)	C14—C15—C2	120.5 (4)
C12—C7—C6	121.0 (3)	C14—C15—H15	119.8
C9—C8—C7	119.7 (4)	C2—C15—H15	119.8
O1—C1—C2—C15	176.5 (4)	C10—C11—C12—C7	−1.0 (6)
O1—C1—C2—C3	−2.1 (7)	C10—C11—C12—C13	180.0 (4)
C15—C2—C3—O2	179.8 (4)	C8—C7—C12—C11	1.0 (6)
C1—C2—C3—O2	−1.7 (7)	C6—C7—C12—C11	−177.2 (4)
C15—C2—C3—C4	−0.7 (7)	C8—C7—C12—C13	−180.0 (3)
C1—C2—C3—C4	177.9 (4)	C6—C7—C12—C13	1.8 (6)
O2—C3—C4—C5	179.3 (4)	C11—C12—C13—O4	−1.5 (6)
C2—C3—C4—C5	−0.3 (7)	C7—C12—C13—O4	179.4 (4)
C3—C4—C5—C14	1.4 (6)	C11—C12—C13—C14	179.2 (4)
C3—C4—C5—C6	−176.7 (4)	C7—C12—C13—C14	0.2 (6)
C4—C5—C6—O3	5.1 (6)	C4—C5—C14—C15	−1.6 (6)
C14—C5—C6—O3	−173.0 (4)	C6—C5—C14—C15	176.4 (3)
C4—C5—C6—C7	−176.8 (4)	C4—C5—C14—C13	178.7 (4)
C14—C5—C6—C7	5.1 (6)	C6—C5—C14—C13	−3.2 (6)
O3—C6—C7—C8	−4.6 (6)	O4—C13—C14—C15	1.6 (6)
C5—C6—C7—C8	177.4 (4)	C12—C13—C14—C15	−179.1 (4)
O3—C6—C7—C12	173.7 (4)	O4—C13—C14—C5	−178.7 (4)
C5—C6—C7—C12	−4.4 (6)	C12—C13—C14—C5	0.6 (6)
C12—C7—C8—C9	−0.5 (6)	C5—C14—C15—C2	0.7 (6)
C6—C7—C8—C9	177.7 (4)	C13—C14—C15—C2	−179.6 (4)
C7—C8—C9—C10	0.0 (7)	C3—C2—C15—C14	0.4 (6)
C8—C9—C10—C11	0.0 (7)	C1—C2—C15—C14	−178.1 (4)
C9—C10—C11—C12	0.5 (7)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.84	2.00	2.635 (5)	132