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

Ismail, N.H.; Osman, C.P.; Awang, K.; Abdul Malek, S.N.; Ng, S.W.

doi:10.1107/S1600536808032224

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2164

doi:10.1107/S1600536808032224

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

Nor Hadiani Ismail,^a Che Puteh Osman,^a Khalijah Awang,^b Sri Nurestri Abdul Malek ^c and Seik Weng Ng ^b ^*

^aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cInstitute of Biological Sciences, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 23 September 2008; accepted 6 October 2008; online 22 October 2008)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.087
wR(F²) = 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

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

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808032224/ci2681sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032224/ci2681Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. The molecular structure of the title compound, showing 70% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.

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

Crystal data top

C₁₅H₈O₄	Z = 2
M_r = 252.21	F(000) = 260
Triclinic, P1	D_x = 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 top

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

Refinement top

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(F_o²) + (0.1778P)² + 2.2381P] where P = (F_o² + 2F_c²)/3
2419 reflections	(Δ/σ)_max = 0.001
173 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₅H₈O₄	γ = 64.692 (2)°
M_r = 252.21	V = 538.96 (3) Å³
Triclinic, P1	Z = 2
a = 6.9194 (2) Å	Mo Kα radiation
b = 8.0650 (2) Å	µ = 0.11 mm⁻¹
c = 10.7601 (3) Å	T = 100 K
α = 86.250 (2)°	0.22 × 0.04 × 0.04 mm
β = 83.214 (2)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	1880 reflections with I > 2σ(I)
4946 measured reflections	R_int = 0.024
2419 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.087	0 restraints
wR(F²) = 0.343	H-atom parameters constrained
S = 1.11	Δρ_max = 0.49 e Å⁻³
2419 reflections	Δρ_min = −0.44 e Å⁻³
173 parameters

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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₅H₈O₄
M_r	252.21
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.9194 (2), 8.0650 (2), 10.7601 (3)
α, β, γ (°)	86.250 (2), 83.214 (2), 64.692 (2)
V (Å³)	538.96 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.22 × 0.04 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4946, 2419, 1880
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.087, 0.343, 1.11
No. of reflections	2419
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.44

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

The authors thank the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sittie, A. A., Lemnmich, E., Olsen, C. E., Hviid, L., Kharazmi, A., Nkrumah, F. K. & Christensen, S. B. (1999). Planta Med. 65, 259–261. Web of Science CrossRef PubMed CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar