organic compounds
3,5,7-Triacetoxy-2-(3,4-diacetoxyphenyl)-4H-1-benzopyran-4-one
aDepartment of Applied Chemistry, Graduate School of Engineering, Kyushu, Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan, bDepartment of Biochemical Science and Technology, Faculty of Agriculture, Kagoshima University, Korimoto 1-21-24, Kasoshima, 890-0065, Japan, and cJapan Bruker AXS K.K.3-9, Moriya-cho Kanagawaku Yokohama 221-0022, Japan
*Correspondence e-mail: moriguch@che.kyutech.ac.jp
In the title compound, C25H20O12, commonly known as pentaacetylated quercetin, the benzene ring and one of its methoxy substituent groups is disordered (site occupancy ratio 0.523:0.427), with a dihedral angle between the major-disorder component and the benzene ring of the benzopyranone moiety of 10.8 (6)°. In the crystal, C—H⋯O hydrogen-bonding interactions give chains which extend along b.
Keywords: crystal structure; pentaacetylated quercetin; hydrogen bonding.
CCDC reference: 1445627
Structure description
Quercetin is the most studied and an important class of flavonoid found in vegetables, fruits and grains. Quercitin and its derivatives are valuable due to their important properties as anti-oxidative (Chopra et al., 2000), anticarcinogenic (Pereira et al., 1996), anti-inflammatory (Ferry et al., 1996) and anti-aggregatory agents (Pignatelli et al., 2000) and their vasodilating effects (Perez-Vizcaino et al., 2002). Acetylated quercetin derivatives have been used as HIV-1 integrase inhibitors for the treatment of HIV-1 infection (Li et al., 2014) as well as to evaluate the cell proliferation inhibition and apoptosis in HL-60 cells (Sakao et al., 2009). Thus, the elucidation of the crystal structures of quercetin derivatives has attracted much attention. Here,we report the of the title compound, the pentaacetyl-substituted quercitin derivative, C25H20O12.
In the title compound (Fig. 1), the benzene ring and one of its methoxy substituent groups, defined by C1A—C14A⋯C2A— O1A—C6AA—O2A is disordered, giving the alternative component C1B—C14B⋯C2B—O1B—C6B— O2B with a site occupancy ratio of 0.523:0.477. The dihedral angle between the major component (A) and the benzene ring of the benzopyranone moiety (defined by C2—C3⋯C12) is 10.8 (6)°. The conformations of the two acetyl groups A and B are very different [torsion angles C1A/B —C2A/B—O1A/B—C6A/B are 67.6 (12) and −106.1 (11)°, respectively]. In the crystal (Fig. 2), only weak C—H⋯O hydrogen-bonding interactions are present (Table 1), giving chains extending along b.
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For background and medical applications of quercitin derivatives, see: Chopra et al. (2000); Pereira et al. (1996); Ferry et al. (1996); Pignatelli et al. (2000); Perez-Vizcaino et al. (2002); Li et al. (2014); Sakao et al. (2009).
Synthesis and crystallization
The title compound was synthesized as follows (Fig. 3). Acetic anhydride (1 ml) was added to a solution of quercetin (2 mmol) in anhydrous pyridine (8 ml) at room temperature. The reaction mixture was stirred for 10 h at 343 K. After completion of reaction, the resultant mixture was cooled to room temperature, then poured into ice-cold water. The precipitate was separated by filtration and then washed with ice-cold water. The resulting precipitate was filtered and finally recrystallized from methanol. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanolic solution at room temperature.
m.p. 465–467 K; δH (400 MHz CDCl3) 7.75–7.67 (2H, m), 7.36 (1H, s), 7.33 (1H, J = 1.8 Hz, d), 6.87 (1H, J = 2.1 Hz, d), 2.42 (3H, s), 2.37–2.31 (12H, m). FABMS: MH+, 511.
Refinement
Crystal data, data collection and structure . Disorder was identified in the benzene ring and one of its acetyl substituent groups and the major and minor components A and B were included with refined occupancy factors of 0.523 (5) and 0.477 (5), respectively. Two low-angle reflections were considered to be affected by the beamstop during data collection, prompting a B-Alert in the checkCIF report.
details are summarized in Table 2Structural data
CCDC reference: 1445627
10.1107/S2414314616000286/zs2360sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616000286/zs2360Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616000286/zs2360Isup3.pdf
Supporting information file. DOI: 10.1107/S2414314616000286/zs2360Isup4.cml
The title compound was synthesized as follows (Fig. 3). Acetic anhydride (1 ml) was added to a solution of quercetin (2 mmol) in anhydrous pyridine (8 ml) at room temperature. The reaction mixture was stirred for 10 h at 343 K. After completion of reaction, the resultant mixture was cooled to room temperature, then poured into ice-cold water. The precipitate was separated by filtration and then washed with ice-cold water. The resulting precipitate was filtered and finally recrystallized from methanol. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanolic solution at room temperature.
m.p. 465–467 K; δH (400 MHz CDCl3) 7.75–7.67 (2H, m), 7.36 (1H, s), 7.33 (1H, J = 1.8 Hz, d), 6.87 (1H, J = 2.1 Hz, d), 2.42 (3H, s), 2.37–2.31 (12H, m). FABMS: MH+, 511.
Crystal data, data collection and structure
details are summarized in Table 2. Disorder was identified in the benzene ring and one of its acetyl substituent groups and the major and minor components A and B were included with refined occupancy factors of 0.523 (5) and 0.477 (5), respectively. Two low-angle reflections were considered to be affected by the beamstop during data collection, prompting a B-Alert in the checkCIF report.Quercetin is the most studied and an important class of flavonoid found in vegetables, fruits and grains. Quercitin and its derivatives are valuable due to their important properties as anti-oxidative (Chopra et al., 2000), anticarcinogenic (Pereira et al., 1996), anti-inflammatory (Ferry et al., 1996) and anti-aggregatory agents (Pignatelli et al., 2000) and their vasodilating effects (Perez-Vizcaino et al., 2002). Acetylated quercetin derivatives have been used as HIV-1 integrase inhibitors for the treatment of HIV-1 infection (Li et al., 2014) as well as to evaluate the cell proliferation inhibition and apoptosis in HL-60 cells (Sakao et al., 2009). Thus, the elucidation of the crystal structures of quercetin derivatives has attracted much attention. Here,we report the
of the title compound, the pentaacetyl-substituted quercitin derivative, C25H20O12.In the title compound (Fig. 1), the benzene ring and one of its methoxy substituent groups, defined by C1A—C14A···C2A— O1A—C6AA—O2A is disordered, giving the alternative component C1B—C14B···C2B—O1B—C6B— O2B with a site occupancy ratio of 0.523/0.477. The dihedral angle between the major component (A) and the benzene ring of the benzopyranone moiety (defined by C2—C3···C12) is 10.8 (6)°. The conformations of the two acetyl groups A and B are very different [torsion angles C1A/B —C2A/B—O1A/B—C6A/B are 67.6 (12) and −106.1 (11)°, respectively]. In the crystal (Fig. 2), only weak C—H···O hydrogen-bonding interactions are present (Table 1), giving chains extending along b.
For background and medical applications of quercitin derivatives, see: Chopra et al. (2000); Pereira et al. (1996); Ferry et al. (1996); Pignatelli et al. (2000); Perez-Vizcaino et al. (2002); Li et al. (2014); Sakao et al. (2009).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. Molecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 40% probability level. The bonds in the minor disordered B portion of the molecule are shown as dashed lines. | |
Fig. 2. Crystal packing diagram of the title compound, viewed along the b axis, with hydrogen atoms and the disordered portion omitted for clarity. | |
Fig. 3. Reaction scheme for the synthesis of the title compound. |
C25H20O12 | Dx = 1.435 Mg m−3 |
Mr = 512.41 | Melting point = 465–467 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25664 reflections |
a = 20.944 (6) Å | θ = 1.7–19.9° |
b = 9.316 (3) Å | µ = 0.12 mm−1 |
c = 24.309 (7) Å | T = 90 K |
V = 4743 (2) Å3 | Prism, yellow |
Z = 8 | 0.30 × 0.20 × 0.15 mm |
F(000) = 2128 |
Bruker APEXII CCD diffractometer | 4165 independent reflections |
Radiation source: fine-focus sealed tube | 3329 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 8.333 pixels mm-1 | θmax = 25.0°, θmin = 1.7° |
ω scans | h = −24→24 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −11→11 |
Tmin = 0.805, Tmax = 0.983 | l = −28→28 |
42484 measured reflections |
Refinement on F2 | 775 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
wR(F2) = 0.179 | w = 1/[σ2(Fo2) + (0.0743P)2 + 6.2477P] where P = (Fo2 + 2Fc2)/3 |
S = 1.21 | (Δ/σ)max = 0.003 |
4145 reflections | Δρmax = 0.34 e Å−3 |
429 parameters | Δρmin = −0.39 e Å−3 |
C25H20O12 | V = 4743 (2) Å3 |
Mr = 512.41 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 20.944 (6) Å | µ = 0.12 mm−1 |
b = 9.316 (3) Å | T = 90 K |
c = 24.309 (7) Å | 0.30 × 0.20 × 0.15 mm |
Bruker APEXII CCD diffractometer | 4165 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3329 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 0.983 | Rint = 0.065 |
42484 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 775 restraints |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 1.21 | Δρmax = 0.34 e Å−3 |
4145 reflections | Δρmin = −0.39 e Å−3 |
429 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.06601 (18) | 1.1281 (4) | 0.11576 (17) | 0.0369 (9) | |
C2 | 0.15863 (14) | 0.9957 (3) | 0.09647 (13) | 0.0200 (7) | |
C3 | 0.16239 (14) | 0.8854 (3) | 0.13579 (12) | 0.0177 (6) | |
C4 | 0.22412 (14) | 0.8435 (3) | 0.15093 (12) | 0.0181 (6) | |
C5 | 0.18454 (15) | 0.6718 (3) | 0.21506 (12) | 0.0199 (7) | |
C9 | 0.29542 (18) | 0.3080 (4) | 0.42104 (14) | 0.0307 (8) | |
C10 | 0.0014 (2) | 1.1652 (5) | 0.0935 (2) | 0.0582 (13) | |
H10A | −0.0287 | 1.0927 | 0.1042 | 0.087* | |
H10B | 0.0034 | 1.1704 | 0.0541 | 0.087* | |
H10C | −0.0118 | 1.2564 | 0.1080 | 0.087* | |
C11 | 0.21171 (15) | 1.0560 (3) | 0.07290 (12) | 0.0195 (7) | |
H11 | 0.2080 | 1.1275 | 0.0464 | 0.023* | |
C12 | 0.27162 (14) | 1.0068 (3) | 0.08978 (12) | 0.0172 (6) | |
C13 | 0.37350 (15) | 1.0017 (4) | 0.04557 (13) | 0.0226 (7) | |
C14 | 0.42571 (16) | 1.1000 (4) | 0.02728 (14) | 0.0309 (8) | |
H14A | 0.4663 | 1.0584 | 0.0362 | 0.046* | |
H14B | 0.4214 | 1.1908 | 0.0456 | 0.046* | |
H14C | 0.4229 | 1.1140 | −0.0118 | 0.046* | |
C15 | 0.27911 (14) | 0.9016 (3) | 0.12845 (12) | 0.0178 (6) | |
H15 | 0.3194 | 0.8703 | 0.1392 | 0.021* | |
C16 | 0.12419 (14) | 0.7042 (3) | 0.20045 (12) | 0.0199 (7) | |
C17 | 0.03850 (16) | 0.5420 (4) | 0.19534 (14) | 0.0286 (8) | |
C18 | −0.0154 (2) | 0.4829 (5) | 0.22801 (18) | 0.0556 (12) | |
H18A | −0.0424 | 0.5600 | 0.2401 | 0.083* | |
H18B | 0.0010 | 0.4325 | 0.2594 | 0.083* | |
H18C | −0.0397 | 0.4179 | 0.2056 | 0.083* | |
C19 | 0.10733 (14) | 0.8136 (3) | 0.16025 (12) | 0.0186 (7) | |
C20 | 0.3000 (2) | 0.1807 (4) | 0.45795 (15) | 0.0466 (11) | |
H20A | 0.3303 | 0.1138 | 0.4431 | 0.070* | |
H20B | 0.2590 | 0.1355 | 0.4608 | 0.070* | |
H20C | 0.3138 | 0.2109 | 0.4938 | 0.070* | |
C1A | 0.2481 (7) | 0.371 (2) | 0.3341 (8) | 0.0212 (19) | 0.523 (5) |
C2A | 0.1875 (3) | 0.3714 (7) | 0.3196 (3) | 0.0214 (13) | 0.523 (5) |
C3A | 0.1651 (3) | 0.4643 (8) | 0.2808 (3) | 0.0210 (14) | 0.523 (5) |
H3AA | 0.1221 | 0.4626 | 0.2716 | 0.025* | 0.523 (5) |
C4A | 0.2058 (14) | 0.562 (3) | 0.2545 (12) | 0.021 (2) | 0.523 (5) |
C5A | 0.2722 (12) | 0.5569 (19) | 0.2685 (7) | 0.021 (2) | 0.523 (5) |
H5AA | 0.3009 | 0.6171 | 0.2506 | 0.025* | 0.523 (5) |
C6A | 0.1296 (3) | 0.2842 (7) | 0.3962 (3) | 0.0299 (15) | 0.523 (5) |
C7A | 0.0733 (8) | 0.2110 (15) | 0.4167 (7) | 0.035 (3) | 0.523 (5) |
H7AA | 0.0580 | 0.1453 | 0.3893 | 0.053* | 0.523 (5) |
H7AB | 0.0840 | 0.1589 | 0.4495 | 0.053* | 0.523 (5) |
H7AC | 0.0407 | 0.2801 | 0.4249 | 0.053* | 0.523 (5) |
C1B | 0.2584 (8) | 0.380 (2) | 0.3359 (9) | 0.021 (2) | 0.477 (5) |
C2B | 0.1922 (4) | 0.4237 (9) | 0.3362 (3) | 0.0271 (15) | 0.477 (5) |
C3B | 0.1683 (4) | 0.5189 (9) | 0.2988 (3) | 0.0247 (16) | 0.477 (5) |
H3BA | 0.1256 | 0.5462 | 0.2998 | 0.030* | 0.477 (5) |
C4B | 0.2102 (16) | 0.575 (3) | 0.2584 (13) | 0.020 (2) | 0.477 (5) |
C5B | 0.2721 (13) | 0.538 (2) | 0.2600 (8) | 0.021 (2) | 0.477 (5) |
H5BA | 0.3003 | 0.5804 | 0.2352 | 0.025* | 0.477 (5) |
C6B | 0.1097 (4) | 0.2669 (7) | 0.3641 (3) | 0.0257 (15) | 0.477 (5) |
C7B | 0.0828 (9) | 0.1796 (16) | 0.4078 (7) | 0.034 (4) | 0.477 (5) |
H7BA | 0.0908 | 0.2246 | 0.4426 | 0.051* | 0.477 (5) |
H7BB | 0.0376 | 0.1702 | 0.4023 | 0.051* | 0.477 (5) |
H7BC | 0.1022 | 0.0862 | 0.4072 | 0.051* | 0.477 (5) |
O1 | 0.08826 (13) | 1.1645 (3) | 0.15904 (12) | 0.0444 (7) | |
O2 | 0.09928 (10) | 1.0439 (2) | 0.07868 (9) | 0.0276 (6) | |
O3 | 0.23438 (9) | 0.7396 (2) | 0.19011 (8) | 0.0198 (5) | |
O5 | 0.27204 (11) | 0.2696 (2) | 0.37146 (9) | 0.0297 (6) | |
O6 | 0.30964 (17) | 0.4278 (3) | 0.43146 (12) | 0.0604 (10) | |
O7 | 0.32388 (10) | 1.0796 (2) | 0.06773 (9) | 0.0204 (5) | |
O8 | 0.37262 (11) | 0.8752 (3) | 0.04125 (10) | 0.0323 (6) | |
O9 | 0.07285 (10) | 0.6385 (2) | 0.22703 (9) | 0.0234 (5) | |
O10 | 0.05366 (12) | 0.5113 (3) | 0.14961 (10) | 0.0360 (6) | |
O11 | 0.05105 (10) | 0.8403 (2) | 0.14948 (9) | 0.0257 (5) | |
O1A | 0.1440 (2) | 0.2725 (5) | 0.34135 (18) | 0.0257 (11) | 0.523 (5) |
O2A | 0.1551 (3) | 0.3705 (6) | 0.4252 (2) | 0.0500 (17) | 0.523 (5) |
C14A | 0.2939 (9) | 0.4632 (14) | 0.3083 (5) | 0.022 (2) | 0.523 (5) |
H14D | 0.3368 | 0.4602 | 0.3181 | 0.027* | 0.523 (5) |
O1B | 0.1528 (3) | 0.3714 (6) | 0.3783 (2) | 0.0365 (13) | 0.477 (5) |
O2B | 0.1042 (2) | 0.2270 (6) | 0.3176 (2) | 0.0369 (15) | 0.477 (5) |
C14B | 0.2953 (10) | 0.4398 (16) | 0.2979 (6) | 0.021 (2) | 0.477 (5) |
H14E | 0.3383 | 0.4148 | 0.2966 | 0.026* | 0.477 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.034 (2) | 0.032 (2) | 0.045 (2) | 0.0022 (16) | 0.0031 (17) | 0.0078 (17) |
C2 | 0.0195 (15) | 0.0191 (15) | 0.0214 (16) | 0.0019 (12) | −0.0029 (13) | −0.0015 (12) |
C3 | 0.0219 (15) | 0.0173 (15) | 0.0140 (14) | 0.0006 (12) | 0.0012 (12) | −0.0021 (12) |
C4 | 0.0248 (16) | 0.0150 (15) | 0.0146 (14) | 0.0011 (12) | 0.0008 (12) | −0.0009 (12) |
C5 | 0.0223 (16) | 0.0197 (15) | 0.0177 (15) | −0.0027 (13) | 0.0044 (12) | 0.0013 (12) |
C9 | 0.046 (2) | 0.0201 (18) | 0.0264 (17) | −0.0003 (15) | −0.0106 (15) | 0.0016 (14) |
C10 | 0.037 (2) | 0.062 (3) | 0.076 (3) | 0.017 (2) | 0.003 (2) | 0.018 (3) |
C11 | 0.0264 (16) | 0.0138 (15) | 0.0181 (15) | −0.0002 (12) | −0.0015 (13) | 0.0023 (12) |
C12 | 0.0228 (16) | 0.0127 (14) | 0.0160 (14) | −0.0040 (12) | 0.0019 (12) | −0.0034 (12) |
C13 | 0.0247 (17) | 0.0286 (19) | 0.0145 (15) | −0.0010 (14) | 0.0018 (13) | 0.0011 (13) |
C14 | 0.0236 (18) | 0.044 (2) | 0.0255 (18) | −0.0108 (16) | 0.0051 (14) | −0.0027 (16) |
C15 | 0.0185 (15) | 0.0166 (15) | 0.0184 (15) | 0.0011 (12) | −0.0002 (12) | −0.0024 (12) |
C16 | 0.0213 (16) | 0.0193 (15) | 0.0190 (15) | −0.0036 (12) | 0.0044 (12) | 0.0010 (12) |
C17 | 0.0312 (18) | 0.0279 (18) | 0.0267 (18) | −0.0060 (15) | −0.0012 (15) | 0.0064 (15) |
C18 | 0.055 (3) | 0.069 (3) | 0.043 (2) | −0.033 (2) | 0.005 (2) | 0.007 (2) |
C19 | 0.0195 (16) | 0.0186 (15) | 0.0178 (15) | −0.0004 (12) | −0.0004 (12) | −0.0040 (12) |
C20 | 0.091 (3) | 0.0222 (19) | 0.0269 (19) | −0.004 (2) | −0.018 (2) | 0.0061 (16) |
C1A | 0.033 (4) | 0.015 (3) | 0.016 (3) | −0.004 (3) | −0.005 (3) | 0.000 (3) |
C2A | 0.026 (3) | 0.018 (3) | 0.020 (3) | −0.004 (2) | 0.000 (2) | −0.001 (2) |
C3A | 0.023 (3) | 0.018 (3) | 0.022 (3) | −0.004 (3) | 0.000 (3) | 0.000 (2) |
C4A | 0.024 (4) | 0.019 (4) | 0.019 (4) | −0.003 (3) | 0.000 (3) | −0.001 (3) |
C5A | 0.028 (3) | 0.016 (4) | 0.018 (4) | −0.005 (3) | −0.002 (4) | −0.003 (3) |
C6A | 0.034 (3) | 0.029 (3) | 0.027 (3) | −0.003 (3) | 0.005 (3) | 0.001 (3) |
C7A | 0.028 (6) | 0.058 (7) | 0.020 (5) | −0.014 (5) | 0.014 (3) | 0.002 (5) |
C1B | 0.031 (4) | 0.015 (3) | 0.017 (3) | −0.001 (3) | −0.006 (3) | −0.004 (3) |
C2B | 0.038 (3) | 0.024 (3) | 0.019 (3) | −0.011 (3) | −0.001 (3) | 0.002 (3) |
C3B | 0.030 (3) | 0.024 (3) | 0.020 (3) | −0.008 (3) | 0.001 (3) | −0.001 (3) |
C4B | 0.026 (4) | 0.017 (4) | 0.018 (4) | −0.007 (3) | 0.001 (3) | 0.001 (3) |
C5B | 0.029 (3) | 0.015 (4) | 0.018 (4) | −0.006 (3) | −0.001 (4) | −0.004 (3) |
C6B | 0.026 (3) | 0.029 (3) | 0.023 (3) | 0.002 (3) | −0.001 (3) | 0.005 (3) |
C7B | 0.025 (6) | 0.050 (6) | 0.026 (6) | −0.008 (5) | 0.003 (4) | −0.006 (5) |
O1 | 0.0471 (16) | 0.0365 (16) | 0.0497 (18) | 0.0059 (13) | 0.0068 (14) | −0.0009 (13) |
O2 | 0.0228 (12) | 0.0310 (13) | 0.0290 (13) | 0.0044 (10) | −0.0031 (10) | 0.0084 (10) |
O3 | 0.0189 (11) | 0.0204 (11) | 0.0200 (11) | 0.0001 (9) | 0.0016 (8) | 0.0067 (9) |
O5 | 0.0512 (15) | 0.0180 (12) | 0.0199 (11) | 0.0003 (10) | −0.0083 (10) | 0.0009 (9) |
O6 | 0.112 (3) | 0.0216 (15) | 0.0476 (17) | −0.0083 (15) | −0.0493 (18) | 0.0033 (13) |
O7 | 0.0214 (11) | 0.0161 (11) | 0.0238 (11) | −0.0030 (9) | 0.0033 (9) | 0.0017 (9) |
O8 | 0.0392 (14) | 0.0251 (14) | 0.0326 (14) | 0.0042 (11) | 0.0131 (11) | 0.0013 (11) |
O9 | 0.0208 (11) | 0.0291 (12) | 0.0205 (11) | −0.0060 (9) | 0.0045 (9) | 0.0025 (9) |
O10 | 0.0475 (16) | 0.0306 (14) | 0.0299 (14) | −0.0111 (12) | 0.0027 (12) | −0.0028 (11) |
O11 | 0.0201 (12) | 0.0267 (13) | 0.0303 (13) | −0.0006 (9) | −0.0004 (10) | 0.0032 (10) |
O1A | 0.030 (2) | 0.024 (2) | 0.024 (2) | −0.006 (2) | −0.002 (2) | 0.0069 (18) |
O2A | 0.070 (4) | 0.044 (3) | 0.037 (3) | −0.029 (3) | 0.023 (3) | −0.014 (3) |
C14A | 0.029 (3) | 0.018 (4) | 0.020 (4) | 0.001 (3) | −0.007 (3) | −0.006 (3) |
O1B | 0.048 (3) | 0.038 (3) | 0.023 (3) | −0.018 (2) | 0.000 (2) | 0.009 (2) |
O2B | 0.029 (3) | 0.037 (3) | 0.045 (3) | −0.007 (2) | 0.006 (3) | −0.005 (3) |
C14B | 0.029 (3) | 0.017 (4) | 0.018 (4) | 0.002 (3) | −0.007 (3) | −0.005 (3) |
C1—O1 | 1.200 (5) | C19—O11 | 1.233 (4) |
C1—O2 | 1.383 (5) | C20—H20A | 0.9600 |
C1—C10 | 1.497 (6) | C20—H20B | 0.9600 |
C2—C11 | 1.371 (4) | C20—H20C | 0.9600 |
C2—O2 | 1.391 (4) | C1A—O5 | 1.40 (2) |
C2—C3 | 1.406 (4) | C1A—C2A | 1.315 (18) |
C3—C4 | 1.400 (4) | C1A—C14A | 1.43 (3) |
C3—C19 | 1.459 (4) | C2A—C3A | 1.363 (9) |
C4—O3 | 1.375 (4) | C2A—O1A | 1.400 (7) |
C4—C15 | 1.385 (4) | C3A—C4A | 1.40 (3) |
C5—C16 | 1.347 (4) | C3A—H3AA | 0.9300 |
C5—O3 | 1.362 (4) | C4A—C5A | 1.43 (4) |
C5—C4B | 1.49 (3) | C5A—C14A | 1.38 (2) |
C5—C4A | 1.47 (3) | C5A—H5AA | 0.9300 |
C9—O6 | 1.183 (4) | C6A—O2A | 1.194 (7) |
C9—O5 | 1.349 (4) | C6A—O1A | 1.373 (7) |
C9—C20 | 1.490 (5) | C6A—C7A | 1.449 (10) |
C10—H10A | 0.9600 | C7A—H7AA | 0.9600 |
C10—H10B | 0.9600 | C7A—H7AB | 0.9600 |
C10—H10C | 0.9600 | C7A—H7AC | 0.9600 |
C11—C12 | 1.397 (4) | C1B—C14B | 1.33 (3) |
C11—H11 | 0.9300 | C1B—C2B | 1.44 (2) |
C12—C15 | 1.368 (4) | C1B—O5 | 1.37 (3) |
C12—O7 | 1.394 (4) | C2B—C3B | 1.365 (11) |
C13—O8 | 1.184 (4) | C2B—O1B | 1.402 (7) |
C13—O7 | 1.377 (4) | C3B—C4B | 1.42 (3) |
C13—C14 | 1.494 (4) | C3B—H3BA | 0.9300 |
C14—H14A | 0.9600 | C4B—C5B | 1.34 (5) |
C14—H14B | 0.9600 | C5B—C14B | 1.39 (2) |
C14—H14C | 0.9600 | C5B—H5BA | 0.9300 |
C15—H15 | 0.9300 | C6B—O2B | 1.197 (7) |
C16—O9 | 1.395 (4) | C6B—O1B | 1.371 (7) |
C16—C19 | 1.456 (4) | C6B—C7B | 1.450 (11) |
C17—O10 | 1.191 (4) | C7B—H7BA | 0.9600 |
C17—O9 | 1.386 (4) | C7B—H7BB | 0.9600 |
C17—C18 | 1.486 (5) | C7B—H7BC | 0.9600 |
C18—H18A | 0.9600 | C14A—H14D | 0.9300 |
C18—H18B | 0.9600 | C14B—H14E | 0.9300 |
C18—H18C | 0.9600 | ||
O1—C1—O2 | 122.4 (3) | H20B—C20—H20C | 109.5 |
O1—C1—C10 | 127.0 (4) | O5—C1A—C2A | 121.5 (15) |
O2—C1—C10 | 110.6 (4) | O5—C1A—C14A | 116.5 (14) |
C11—C2—O2 | 117.6 (3) | C2A—C1A—C14A | 122 (2) |
C11—C2—C3 | 122.6 (3) | C3A—C2A—C1A | 121.3 (11) |
O2—C2—C3 | 119.9 (3) | C3A—C2A—O1A | 117.1 (6) |
C4—C3—C2 | 115.7 (3) | C1A—C2A—O1A | 121.5 (11) |
C4—C3—C19 | 119.7 (3) | C2A—C3A—C4A | 121.3 (13) |
C2—C3—C19 | 124.6 (3) | C2A—C3A—H3AA | 119.4 |
O3—C4—C15 | 114.7 (3) | C4A—C3A—H3AA | 119.4 |
O3—C4—C3 | 121.5 (3) | C5A—C4A—C3A | 117 (2) |
C15—C4—C3 | 123.8 (3) | C5A—C4A—C5 | 118 (2) |
C16—C5—O3 | 119.9 (3) | C3A—C4A—C5 | 124 (2) |
C16—C5—C4B | 131.4 (13) | C14A—C5A—C4A | 121 (2) |
O3—C5—C4B | 108.7 (12) | C14A—C5A—H5AA | 119.7 |
C16—C5—C4A | 127.8 (12) | C4A—C5A—H5AA | 119.7 |
O3—C5—C4A | 112.3 (12) | O2A—C6A—O1A | 121.8 (6) |
O6—C9—O5 | 122.2 (3) | O2A—C6A—C7A | 118.6 (9) |
O6—C9—C20 | 127.3 (3) | O1A—C6A—C7A | 118.4 (9) |
O5—C9—C20 | 110.5 (3) | C6A—C7A—H7AA | 109.5 |
C1—C10—H10A | 109.5 | C6A—C7A—H7AB | 109.5 |
C1—C10—H10B | 109.5 | H7AA—C7A—H7AB | 109.5 |
H10A—C10—H10B | 109.5 | C6A—C7A—H7AC | 109.5 |
C1—C10—H10C | 109.5 | H7AA—C7A—H7AC | 109.5 |
H10A—C10—H10C | 109.5 | H7AB—C7A—H7AC | 109.5 |
H10B—C10—H10C | 109.5 | C14B—C1B—C2B | 116 (2) |
C2—C11—C12 | 118.1 (3) | C14B—C1B—O5 | 129.2 (16) |
C2—C11—H11 | 120.9 | C2B—C1B—O5 | 114.0 (16) |
C12—C11—H11 | 120.9 | C3B—C2B—C1B | 122.1 (12) |
C15—C12—O7 | 121.5 (3) | C3B—C2B—O1B | 119.7 (7) |
C15—C12—C11 | 122.7 (3) | C1B—C2B—O1B | 118.1 (12) |
O7—C12—C11 | 115.6 (3) | C2B—C3B—C4B | 118.3 (15) |
O8—C13—O7 | 123.2 (3) | C2B—C3B—H3BA | 120.8 |
O8—C13—C14 | 126.5 (3) | C4B—C3B—H3BA | 120.8 |
O7—C13—C14 | 110.3 (3) | C5B—C4B—C3B | 119 (3) |
C13—C14—H14A | 109.5 | C5B—C4B—C5 | 122 (3) |
C13—C14—H14B | 109.5 | C3B—C4B—C5 | 119 (2) |
H14A—C14—H14B | 109.5 | C4B—C5B—C14B | 122 (2) |
C13—C14—H14C | 109.5 | C4B—C5B—H5BA | 119.2 |
H14A—C14—H14C | 109.5 | C14B—C5B—H5BA | 119.2 |
H14B—C14—H14C | 109.5 | O2B—C6B—O1B | 121.4 (7) |
C12—C15—C4 | 117.1 (3) | O2B—C6B—C7B | 118.7 (9) |
C12—C15—H15 | 121.4 | O1B—C6B—C7B | 118.0 (10) |
C4—C15—H15 | 121.4 | C6B—C7B—H7BA | 109.5 |
C5—C16—O9 | 120.2 (3) | C6B—C7B—H7BB | 109.5 |
C5—C16—C19 | 124.1 (3) | H7BA—C7B—H7BB | 109.5 |
O9—C16—C19 | 115.5 (3) | C6B—C7B—H7BC | 109.5 |
O10—C17—O9 | 122.4 (3) | H7BA—C7B—H7BC | 109.5 |
O10—C17—C18 | 127.8 (3) | H7BB—C7B—H7BC | 109.5 |
O9—C17—C18 | 109.7 (3) | C1—O2—C2 | 115.5 (3) |
C17—C18—H18A | 109.5 | C5—O3—C4 | 121.0 (2) |
C17—C18—H18B | 109.5 | C9—O5—C1A | 122.1 (6) |
H18A—C18—H18B | 109.5 | C9—O5—C1B | 116.0 (6) |
C17—C18—H18C | 109.5 | C13—O7—C12 | 119.1 (2) |
H18A—C18—H18C | 109.5 | C17—O9—C16 | 115.3 (2) |
H18B—C18—H18C | 109.5 | C6A—O1A—C2A | 117.3 (5) |
O11—C19—C16 | 121.0 (3) | C5A—C14A—C1A | 117.7 (17) |
O11—C19—C3 | 125.2 (3) | C5A—C14A—H14D | 121.1 |
C16—C19—C3 | 113.7 (3) | C1A—C14A—H14D | 121.1 |
C9—C20—H20A | 109.5 | C6B—O1B—C2B | 116.8 (6) |
C9—C20—H20B | 109.5 | C1B—C14B—C5B | 122.4 (19) |
H20A—C20—H20B | 109.5 | C1B—C14B—H14E | 118.8 |
C9—C20—H20C | 109.5 | C5B—C14B—H14E | 118.8 |
H20A—C20—H20C | 109.5 | ||
C6A—O1A—C2A—C1A | 67.6 (12) | O2—C2—C11—C12 | −179.0 (3) |
C6A—O1A—C2A—C3A | −115.3 (7) | O2—C2—C3—C19 | 0.5 (4) |
C2A—O1A—C6A—C7A | 163.8 (8) | O2—C2—C3—C4 | 179.7 (3) |
C2A—O1A—C6A—O2A | −3.5 (9) | C1A—C2A—C3A—C4A | 1 (2) |
C6B—O1B—C2B—C1B | −106.1 (11) | O1A—C2A—C3A—C4A | −176.5 (15) |
C6B—O1B—C2B—C3B | 77.2 (9) | C2—C3—C19—O11 | 0.2 (5) |
C2B—O1B—C6B—C7B | 161.1 (10) | C4—C3—C19—C16 | 1.6 (4) |
C2B—O1B—C6B—O2B | −3.1 (11) | C2—C3—C19—C16 | −179.3 (3) |
C2—O2—C1—C10 | −176.3 (3) | C19—C3—C4—C15 | 177.5 (3) |
C1—O2—C2—C11 | −108.2 (3) | C2—C3—C4—O3 | 178.2 (3) |
C2—O2—C1—O1 | 4.3 (5) | C19—C3—C4—O3 | −2.6 (4) |
C1—O2—C2—C3 | 74.1 (3) | C2—C3—C4—C15 | −1.7 (4) |
C5—O3—C4—C15 | −179.0 (2) | C4—C3—C19—O11 | −179.0 (3) |
C4—O3—C5—C4A | 178.5 (12) | C2A—C3A—C4A—C5A | 2 (3) |
C4—O3—C5—C16 | 1.5 (4) | C2A—C3A—C4A—C5 | −175.7 (15) |
C5—O3—C4—C3 | 1.1 (4) | O3—C4—C15—C12 | −179.2 (2) |
C9—O5—C1A—C14A | 70.9 (16) | C3—C4—C15—C12 | 0.7 (4) |
C1A—O5—C9—C20 | 163.8 (8) | C5A—C4A—C5—C16 | −173.0 (13) |
C1A—O5—C9—O6 | −16.3 (9) | C3A—C4A—C5A—C14A | −3 (3) |
C9—O5—C1A—C2A | −115.6 (14) | C5A—C4A—C5—O3 | 10 (2) |
C13—O7—C12—C11 | −131.8 (3) | C3A—C4A—C5—C16 | 5 (3) |
C12—O7—C13—C14 | −176.9 (3) | C3A—C4A—C5—O3 | −171.8 (18) |
C12—O7—C13—O8 | 4.6 (4) | C5—C4A—C5A—C14A | 175.2 (16) |
C13—O7—C12—C15 | 52.9 (4) | C4A—C5—C16—C19 | −179.0 (14) |
C17—O9—C16—C5 | −110.5 (3) | C4A—C5—C16—O9 | 5.6 (15) |
C17—O9—C16—C19 | 73.7 (3) | O3—C5—C16—C19 | −2.6 (4) |
C16—O9—C17—C18 | −178.6 (3) | O3—C5—C16—O9 | −178.0 (2) |
C16—O9—C17—O10 | 3.9 (5) | C4A—C5A—C14A—C1A | 1 (3) |
O5—C1A—C14A—C5A | 175.5 (13) | C2—C11—C12—C15 | 0.2 (4) |
C14A—C1A—C2A—C3A | −3 (2) | C2—C11—C12—O7 | −175.1 (3) |
O5—C1A—C2A—O1A | 1 (2) | O7—C12—C15—C4 | 175.1 (3) |
C2A—C1A—C14A—C5A | 2 (2) | C11—C12—C15—C4 | 0.1 (4) |
O5—C1A—C2A—C3A | −176.0 (10) | O9—C16—C19—O11 | −2.9 (4) |
C14A—C1A—C2A—O1A | 174.2 (12) | C5—C16—C19—C3 | 1.0 (4) |
C11—C2—C3—C19 | −177.2 (3) | O9—C16—C19—C3 | 176.6 (2) |
C11—C2—C3—C4 | 2.0 (4) | C5—C16—C19—O11 | −178.5 (3) |
C3—C2—C11—C12 | −1.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3A—H3AA···O9 | 0.93 | 2.22 | 2.842 (7) | 124 |
C5A—H5AA···O3 | 0.93 | 2.32 | 2.675 (18) | 102 |
C7A—H7AB···O8i | 0.96 | 2.43 | 3.331 (17) | 156 |
C20—H20A···O2Aii | 0.96 | 2.33 | 3.142 (7) | 142 |
C20—H20B···O6ii | 0.96 | 2.51 | 3.352 (5) | 146 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+1/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7A—H7AB···O8i | 0.96 | 2.43 | 3.331 (17) | 156 |
C20—H20A···O2Aii | 0.96 | 2.33 | 3.142 (7) | 142 |
C20—H20B···O6ii | 0.96 | 2.51 | 3.352 (5) | 146 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C25H20O12 |
Mr | 512.41 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 90 |
a, b, c (Å) | 20.944 (6), 9.316 (3), 24.309 (7) |
V (Å3) | 4743 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.805, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42484, 4165, 3329 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.179, 1.21 |
No. of reflections | 4145 |
No. of parameters | 429 |
No. of restraints | 775 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.39 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009).
Acknowledgements
We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA) for the X-ray analysis. This research was financially supported by JSPS KAKENH Grant No. 15 K05611.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Quercetin is the most studied and an important class of flavonoid found in vegetables, fruits and grains. Quercitin and its derivatives have been valuable due to their important properties as antioxidative (Chopra et al., 2000), anticarcinogenic (Pereira et al., 1996), anti-inflammatory (Ferry et al., 1996) and anti-aggregatory agents (Pignatelli et al., 2000) and their vasodilating effects (Pérez-Vizcaíno et al., 2002). Acetylated quercetin derivatives were used as HIV-1 integrase inhibitors for the treatment of HIV-1 infection (Li et al., 2014). They were also used to evaluate the cell proliferation inhibition and apoptosis in HL-60 cells (Sakao et al., 2009). Thus, the elucidation of the crystal structures of quercetin derivatives has attracted much attention. Here,we report the crystal structure of the title compound, the pentaacetyl- substituted quercitin derivative, C25H20O12.
In the title compound (Fig. 1), the benzene ring and one of its methoxy substituent groups, defined by C1A—C14A···C2A— O1A—C6AA—O2A is disordered, giving the alternative component C1B—C14B···C2B—O1B—C6B— O2B with a site occupancy factor of 0.523/0.477. The dihedral angle between the major component (A) and the benzene ring of the benzopyranone moiety (defined by C2—C3···C12) is 10.8 (6)°. The conformations of the two acetyl groups A and B are very different [torsion angles C1A/B —C2A/B—O1A/B—C6A/B are 67.6 (12) and −106.1 (11)°, respectively]. In the crystal (Fig. 2), only weak intermolecular C—H···O hydrogen-bonding interactions are present (Table 1), giving chains extending along b.