2,4-Di­bromo-1,3-dihy­droxy-9H-xanthen-9-one

Huang, S.-W.; Yang, Z.-M.; Huang, F.-P.; Qin, J.-K.

doi:10.1107/S1600536813019296

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1361

doi:10.1107/S1600536813019296

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2,4-Dibromo-1,3-dihydroxy-9H-xanthen-9-one

Shi-Wen Huang,^a,^b Zheng-Min Yang,^a Fu-Ping Huang ^a and Jiang-Ke Qin ^a ^*

^aKey Laboratory for the Chemistry & Molecular Engineering of Medicinal Resources, Ministry of Education of China, School of Chemistry & Chemical Engineering, Guangxi Normal University, Guilin, 541004, People's Republic of China, and ^bDepartment of Pharmacy, Youjiang Medical University for Nationalities, Baise 533000, People's Republic of China
^*Correspondence e-mail: jiangkeq@163.com

(Received 26 May 2013; accepted 12 July 2013; online 31 July 2013)

The title compound, C₁₃H₆Br₂O₄, derived from xanthone, a fundamental structural framework of active ingredients in many medicinal plants, and was synthesized by bromination of 1,3-dihydroxyxanthen-9-one with N-bromosuccinimide. The molecular conformation is essentially planar, the dihedral angle between the benzene rings being 1.1 (4)°. This conformation is favorable for the formation of an intramolecular O—H⋯O hydrogen bond between a hydroxy group and the xanthone carbonyl group. In the crystal, molecules are associated into chains along the b-axis direction via C=O⋯H—O hydrogen bonds involving the other hydroxy group.

Related literature

For the pharmacological activity of xanthone derivatives, see: Cheng et al. (2011 ); Dao et al. (2012 ); Sousa et al. (2009 ); Szkaradek et al. (2013 ). For the synthesis of the xanthone used as a starting material, see: Liu et al. (2006 ). For related xanthone structures, see: Corrêa et al. (2010 ).

Experimental

Crystal data

C₁₃H₆Br₂O₄
M_r = 386.00
Orthorhombic, P n a 2₁
a = 18.4489 (15) Å
b = 16.9049 (13) Å
c = 3.8564 (3) Å
V = 1202.72 (16) Å³
Z = 4
Mo Kα radiation
μ = 6.75 mm⁻¹
T = 298 K
0.28 × 0.09 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.254, T_max = 0.688
6188 measured reflections
2120 independent reflections
1830 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.070
S = 1.04
2120 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 881 Friedel pairs
Absolute structure parameter: −0.008 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2	0.82	1.81	2.555 (7)	149
O3—H3⋯O2ⁱ	0.82	2.02	2.741 (7)	147
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813019296/bh2480sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019296/bh2480Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019296/bh2480Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536813019296/bh2480Isup4.cml

checkCIF report

Comment top

Xanthone, also named as dibenzo-γ-pyrone, is a fundamental structural framework of active ingredients in many medicinal plants, which derivatives have broad pharmacological activities, such as antioxidant (Cheng et al., 2011), antitumor (Sousa et al., 2009), anticonvulsant (Szkaradek et al., 2013) and inhibition of neuraminidase activity (Dao et al., 2012). The title compound in this study is a new xanthone derivative, which was synthesized by bromination of 1,3-dihydroxy-xanthen-9-one (Liu et al., 2006) with NBS.

We report here the synthesis and crystal structure of 2,4-dibromo-1,3-dihydroxy-xanthen-9-one (C₁₃H₆Br₂O₄, Fig. 1). The molecule of the title compound has a planar conformation, with characteristic bond lengths C2—Br1 = 1.893 (5) Å and C4—Br2 = 1.902 (5) Å. The molecular conformation is mainly controlled by the O4—H4···O2 intramolecular hydrogen bond between the hydroxy OH group and the carbonyl O atom. Molecules are further connected into a one-dimensional supramolecular architecture via O3—H3···O2 intermolecular hydrogen bonds (Fig. 2). The title compound has the same planar molecular conformation as that reported for other 1-hydroxy-9H-xanthen-9-one derivatives (Corrêa et al., 2010), while the carbonyl bond length C7═O2, 1.262 (7) Å, is slightly larger than the corresponding carbonyl bond lengths in these derivatives.

Related literature top

For the pharmacological activity of xanthone derivatives, see: Cheng et al. (2011); Dao et al. (2012); Sousa et al. (2009); Szkaradek et al. (2013). For the synthesis of the xanthone used as a starting material, see: Liu et al. (2006). For related xanthone structures, see: Corrêa et al. (2010).

Experimental top

The title compound was synthesized using the following procedure: in a 50 ml flask, 1,3-dihydroxy-xanthen-9-one (1010 mg, 4.43 mmol; Liu et al., 2006) was dissolved in CCl₄ (15 ml), then NBS (500 mg, 2.83 mmol) was added. The mixture was stirred at room temperature for 24 h. The residue was washed with acetone and then filtered. The yellow solid was collected and dried. Recrystallization from methanol solution afforded 2,4-dibromo-1,3-dihydroxy-xanthen-9-one as yellow crystals. The compound identity was confirmed by NMR spectroscopy. ¹H NMR (500 MHz, DMSO-d₆): 13.63 (s, 1H), 8.09 (dd, J = 7.9, 1.6 Hz, 1H), 7.87 (td, J = 7.8, 1.5 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.48 (t, J = 7.5 Hz, 1H).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound and the atom-numbering scheme.
	Fig. 2. The packing diagram of the title compound.

2,4-Dibromo-1,3-dihydroxy-9H-xanthen-9-one top

Crystal data top

C₁₃H₆Br₂O₄	F(000) = 744
M_r = 386.00	D_x = 2.132 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2778 reflections
a = 18.4489 (15) Å	θ = 3.3–26.2°
b = 16.9049 (13) Å	µ = 6.75 mm⁻¹
c = 3.8564 (3) Å	T = 298 K
V = 1202.72 (16) Å³	Block, yellow
Z = 4	0.28 × 0.09 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	2120 independent reflections
Radiation source: fine-focus sealed tube	1830 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −21→21
T_min = 0.254, T_max = 0.688	k = −20→15
6188 measured reflections	l = −4→4

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0232P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
2120 reflections	Δρ_max = 0.43 e Å⁻³
172 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 881 Friedel pairs
0 constraints	Absolute structure parameter: −0.008 (16)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₃H₆Br₂O₄	V = 1202.72 (16) Å³
M_r = 386.00	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 18.4489 (15) Å	µ = 6.75 mm⁻¹
b = 16.9049 (13) Å	T = 298 K
c = 3.8564 (3) Å	0.28 × 0.09 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	2120 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1830 reflections with I > 2σ(I)
T_min = 0.254, T_max = 0.688	R_int = 0.076
6188 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.43 e Å⁻³
S = 1.04	Δρ_min = −0.33 e Å⁻³
2120 reflections	Absolute structure: Flack (1983), 881 Friedel pairs
172 parameters	Absolute structure parameter: −0.008 (16)
1 restraint

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

	x	y	z	U_iso*/U_eq
Br1	0.65912 (3)	1.09241 (3)	−0.07056 (16)	0.03711 (16)
Br2	0.91885 (3)	0.97740 (3)	0.54899 (17)	0.03972 (17)
O1	0.61335 (17)	0.9267 (2)	0.0466 (12)	0.0366 (9)
O2	0.72160 (18)	0.7368 (2)	0.4658 (13)	0.0483 (11)
O3	0.8177 (2)	1.0920 (2)	0.2248 (11)	0.0408 (11)
H3	0.7904	1.1248	0.1377	0.061*
O4	0.83232 (18)	0.8253 (2)	0.5513 (13)	0.0452 (11)
H4	0.8074	0.7851	0.5521	0.068*
C1	0.6824 (3)	0.9348 (3)	0.1582 (13)	0.0262 (13)
C2	0.7137 (3)	1.0086 (3)	0.1241 (13)	0.0277 (13)
C3	0.7844 (3)	1.0223 (3)	0.2401 (14)	0.0293 (13)
C4	0.8233 (3)	0.9589 (3)	0.3828 (15)	0.0310 (14)
C5	0.7941 (3)	0.8853 (3)	0.4141 (16)	0.0323 (13)
C6	0.7210 (3)	0.8704 (3)	0.2998 (14)	0.0305 (14)
C7	0.6879 (3)	0.7943 (4)	0.3340 (15)	0.0351 (15)
C8	0.6131 (3)	0.7875 (3)	0.2015 (14)	0.0337 (14)
C9	0.5753 (3)	0.7164 (4)	0.2048 (17)	0.0400 (15)
H9	0.5977	0.6707	0.2858	0.048*
C10	0.5053 (3)	0.7135 (4)	0.0887 (19)	0.0479 (16)
H10	0.4797	0.6661	0.0978	0.057*
C11	0.4724 (3)	0.7802 (4)	−0.0412 (18)	0.0458 (15)
H11	0.4251	0.7770	−0.1236	0.055*
C12	0.5080 (3)	0.8511 (3)	−0.0515 (17)	0.0410 (14)
H12	0.4853	0.8965	−0.1333	0.049*
C13	0.5793 (3)	0.8533 (3)	0.0642 (17)	0.0314 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0367 (3)	0.0309 (3)	0.0438 (3)	0.0061 (2)	−0.0024 (3)	0.0080 (3)
Br2	0.0277 (3)	0.0461 (4)	0.0454 (3)	−0.0007 (2)	−0.0040 (3)	0.0016 (3)
O1	0.0249 (19)	0.033 (2)	0.052 (2)	0.0044 (15)	−0.007 (2)	0.008 (2)
O2	0.037 (2)	0.027 (2)	0.081 (3)	0.0009 (17)	−0.006 (3)	0.015 (2)
O3	0.040 (2)	0.025 (2)	0.058 (3)	−0.0020 (19)	−0.005 (2)	0.012 (2)
O4	0.032 (2)	0.037 (2)	0.067 (3)	0.0062 (16)	−0.010 (3)	0.015 (2)
C1	0.025 (3)	0.026 (3)	0.027 (3)	0.006 (2)	0.000 (2)	−0.002 (2)
C2	0.028 (3)	0.028 (3)	0.026 (4)	0.012 (2)	−0.002 (2)	0.001 (2)
C3	0.028 (3)	0.028 (3)	0.032 (3)	0.003 (3)	0.005 (2)	0.003 (3)
C4	0.022 (3)	0.036 (3)	0.034 (3)	0.000 (2)	0.006 (3)	−0.002 (3)
C5	0.027 (3)	0.036 (3)	0.034 (3)	0.006 (2)	0.005 (3)	0.008 (3)
C6	0.033 (3)	0.023 (3)	0.036 (3)	0.008 (2)	0.003 (2)	0.005 (2)
C7	0.028 (3)	0.037 (4)	0.041 (4)	0.001 (3)	0.008 (3)	0.003 (3)
C8	0.037 (4)	0.034 (4)	0.031 (3)	0.002 (3)	−0.001 (3)	−0.003 (3)
C9	0.038 (4)	0.028 (3)	0.054 (4)	−0.004 (3)	0.002 (3)	0.001 (3)
C10	0.040 (4)	0.048 (4)	0.056 (4)	−0.008 (3)	−0.003 (3)	0.003 (3)
C11	0.030 (3)	0.056 (4)	0.051 (4)	−0.007 (3)	−0.004 (3)	0.001 (4)
C12	0.028 (3)	0.048 (4)	0.048 (4)	0.006 (3)	−0.008 (3)	−0.001 (3)
C13	0.034 (3)	0.032 (3)	0.029 (3)	−0.001 (2)	0.010 (3)	0.001 (3)

Geometric parameters (Å, º) top

Br1—C2	1.893 (5)	C5—C6	1.442 (7)
Br2—C4	1.902 (5)	C6—C7	1.429 (8)
O1—C1	1.351 (6)	C7—C8	1.476 (8)
O1—C13	1.393 (6)	C8—C13	1.379 (7)
O2—C7	1.262 (7)	C8—C9	1.390 (8)
O3—C3	1.331 (7)	C9—C10	1.368 (8)
O3—H3	0.8200	C9—H9	0.9300
O4—C5	1.343 (6)	C10—C11	1.374 (8)
O4—H4	0.8200	C10—H10	0.9300
C1—C2	1.381 (7)	C11—C12	1.368 (8)
C1—C6	1.411 (7)	C11—H11	0.9300
C2—C3	1.398 (7)	C12—C13	1.389 (7)
C3—C4	1.402 (7)	C12—H12	0.9300
C4—C5	1.361 (7)

C1—O1—C13	119.9 (4)	O2—C7—C6	121.3 (5)
C3—O3—H3	109.5	O2—C7—C8	122.7 (5)
C5—O4—H4	109.5	C6—C7—C8	115.9 (5)
O1—C1—C2	117.1 (4)	C13—C8—C9	118.4 (5)
O1—C1—C6	121.4 (5)	C13—C8—C7	119.5 (5)
C2—C1—C6	121.5 (5)	C9—C8—C7	122.2 (5)
C1—C2—C3	120.6 (5)	C10—C9—C8	120.0 (6)
C1—C2—Br1	119.4 (4)	C10—C9—H9	120.0
C3—C2—Br1	120.0 (4)	C8—C9—H9	120.0
O3—C3—C2	124.2 (5)	C9—C10—C11	120.5 (6)
O3—C3—C4	117.3 (5)	C9—C10—H10	119.8
C2—C3—C4	118.5 (5)	C11—C10—H10	119.8
C5—C4—C3	122.1 (5)	C12—C11—C10	121.2 (5)
C5—C4—Br2	119.1 (4)	C12—C11—H11	119.4
C3—C4—Br2	118.8 (4)	C10—C11—H11	119.4
O4—C5—C4	121.2 (5)	C11—C12—C13	117.9 (5)
O4—C5—C6	118.6 (5)	C11—C12—H12	121.1
C4—C5—C6	120.2 (5)	C13—C12—H12	121.1
C1—C6—C7	121.0 (5)	C8—C13—C12	122.0 (5)
C1—C6—C5	117.1 (5)	C8—C13—O1	122.3 (5)
C7—C6—C5	121.9 (5)	C12—C13—O1	115.7 (5)

C13—O1—C1—C2	178.1 (5)	O4—C5—C6—C7	1.1 (9)
C13—O1—C1—C6	−1.2 (8)	C4—C5—C6—C7	−178.8 (5)
O1—C1—C2—C3	178.6 (5)	C1—C6—C7—O2	−178.7 (5)
C6—C1—C2—C3	−2.1 (8)	C5—C6—C7—O2	−0.1 (9)
O1—C1—C2—Br1	0.3 (6)	C1—C6—C7—C8	2.1 (8)
C6—C1—C2—Br1	179.6 (4)	C5—C6—C7—C8	−179.2 (5)
C1—C2—C3—O3	−178.2 (5)	O2—C7—C8—C13	179.3 (6)
Br1—C2—C3—O3	0.1 (8)	C6—C7—C8—C13	−1.6 (8)
C1—C2—C3—C4	1.7 (8)	O2—C7—C8—C9	−1.8 (9)
Br1—C2—C3—C4	−180.0 (4)	C6—C7—C8—C9	177.3 (5)
O3—C3—C4—C5	179.3 (5)	C13—C8—C9—C10	−3.0 (9)
C2—C3—C4—C5	−0.6 (9)	C7—C8—C9—C10	178.0 (6)
O3—C3—C4—Br2	1.0 (7)	C8—C9—C10—C11	1.9 (11)
C2—C3—C4—Br2	−178.9 (4)	C9—C10—C11—C12	−1.3 (12)
C3—C4—C5—O4	179.9 (6)	C10—C11—C12—C13	1.9 (10)
Br2—C4—C5—O4	−1.8 (8)	C9—C8—C13—C12	3.7 (9)
C3—C4—C5—C6	−0.2 (9)	C7—C8—C13—C12	−177.4 (6)
Br2—C4—C5—C6	178.1 (4)	C9—C8—C13—O1	−179.2 (6)
O1—C1—C6—C7	−0.8 (8)	C7—C8—C13—O1	−0.3 (9)
C2—C1—C6—C7	179.9 (5)	C11—C12—C13—C8	−3.1 (10)
O1—C1—C6—C5	−179.5 (5)	C11—C12—C13—O1	179.6 (6)
C2—C1—C6—C5	1.2 (8)	C1—O1—C13—C8	1.7 (9)
O4—C5—C6—C1	179.8 (5)	C1—O1—C13—C12	179.0 (5)
C4—C5—C6—C1	−0.1 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···Br1	0.82	2.61	3.139 (5)	124
O4—H4···O2	0.82	1.81	2.555 (7)	149
O3—H3···O2ⁱ	0.82	2.02	2.741 (7)	147

Symmetry code: (i) −x+3/2, y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2	0.82	1.81	2.555 (7)	149.4
O3—H3···O2ⁱ	0.82	2.02	2.741 (7)	146.7

Symmetry code: (i) −x+3/2, y+1/2, z−1/2.

Acknowledgements

This work was supported financially by grants from the National Natural Science Foundation of PRC (21002015) and the Natural Science Foundation of Guangxi (2010GXNSFB013013).

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