organic papers 7,8-Dihydroxy-3-methyl-10-oxo-1H,10Hpyrano[4,3-b]chromene-9-carboxylic

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1 organic papers Acta Crystallographica Section E Structure Reports Online ISSN ,8-Dihydroxy-3-methyl-10-oxo-1H,10Hpyrano[4,3-b]chromene-9-carboxylic acid Jian-Feng Wang, a * Yong-Jie Zhang, b Mei-Juan Fang, a Yao-Jian Huang, b Zan-Bin Wei, a Zhong-Hui Zheng, b Wen-Jin Su b and Yu-Fen Zhao a a Department of Chemistry, Xiamen University, Xiamen , People's Republic of China, and b Department of Biology, Xiamen University, Xiamen , People's Republic of China Correspondence jfwang@yanan.xmu.edu.cn Key indicators Single-crystal X-ray study T = 296 K Mean (C±C) = AÊ R factor = wr factor = Data-to-parameter ratio = 13.0 The structure of the title compound, anhydrofulvic acid, C 14 H 10 O 7, a yellow acidic metabolite isolated from Paecilomyces sp. was determined by X-ray analysis. The chromone ring system is essentially planar, with the carboxylic acid group coplanar with the ring. Comment The title compound, (I), had been prepared by dehydration of a natural product, fulvic acid [3,7,8-trihydroxy-3-methyl-10- oxo-4,10-dihydro-1h,3h-pyrano[4,3-b]chromene-9-carboxylic acid, (II)], isolated from several fungi (Dean et al., 1957). In this study, (I) was isolated from the fermentation broth of Paecilomyces sp., an endophytic fungus of Cephalataxus fortunei, and its structure was determined by X-ray analysis. Received 9 July 2003 Accepted 28 July 2003 Online 8 August 2003 For details of how these key indicators were automatically derived from the article, see The chromone ring system of (I) is essentially planar, with the hydroxyl and carboxylic acid groups coplanar with the benzene ring. There is one intermolecular hydrogen bond and three intramolecular hydrogen bonds in the crystal structure (Table 2), rendering the crystal very stable (m.p. 516±518 K). Experimental The title compound, (I), was isolated from the organic extract of the liquid culture of Paecilomyces sp. Recrystallization from ethyl acetate afforded green crystals suitable for X-ray analysis. The molecular formula of (I) was deduced from the high resolution ESI±MS spectrum as C 14 H 10 O 7, showing an accurate mass at m/z [M + H] +.The 13 C NMR analysis revealed 14 C atoms: (p.p.m.) = 20.0 (C13), 64.3(C12), 94.5 (C10), (C4), (C8), (C6), (C1), (C2), (C3), (C5), (C9), (C11), (C14) and (C7). # 2003 International Union of Crystallography Printed in Great Britain ± all rights reserved Crystal data C 14 H 10 O 7 M r = Monoclinic, P2 1 =c a = (5) A Ê b = (5) A Ê c = (5) A Ê = (5) V = (10) A Ê 3 Z =4 D x = Mg m 3 Mo K radiation Cell parameters from 2225 re ections = 2.4±27.5 = 0.13 mm 1 T = 296 (2) K Chunk, green mm o1244 Jian-Feng Wang et al. C 14 H 10 O 7 DOI: /S Acta Cryst. (2003). E59, o1244±o1245

2 organic papers Data collection Bruker AXS SMART area-detector diffractometer ' and! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.974, T max = measured re ections Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 201 parameters H atoms treated by a mixture of independent and constrained re nement Table 1 Selected geometric parameters (A Ê, ) independent re ections 2225 re ections with I > 2(I) R int = max = 27.5 h = 10! 10 k =0! 13 l =0! 19 w = 1/[ 2 (F o 2 ) + (0.0758P) P] where P =(F o 2 +2F c 2 )/3 (/) max < max = 0.24 e A Ê 3 min = 0.20 e A Ê 3 Extinction correction: SHELXL97 Extinction coef cient: (3) Figure 1 ORTEP3 (Farrugia, 1997) plot of the structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. O1ÐC (16) O1ÐC (14) C1ÐC (18) C1ÐC (15) C1ÐC (16) O2ÐC (18) O2ÐC (16) C2ÐO (14) C2ÐC (18) O3ÐC (15) C3ÐO (16) C3ÐC (16) C9ÐO1ÐC (9) C2ÐC1ÐC (10) O6ÐC2ÐC (11) O6ÐC2ÐC (11) C1ÐC2ÐC (10) O7ÐC3ÐC (11) O7ÐC3ÐC (11) C4ÐC3ÐC (11) C3ÐC4ÐC (11) O1ÐC5ÐC (10) O1ÐC5ÐC (10) C4ÐC5ÐC (10) C5ÐC6ÐC (11) C5ÐC6ÐC (10) C1ÐC6ÐC (10) O3ÐC7ÐC (11) O3ÐC7ÐC (11) C8ÐC7ÐC (10) O4ÐC (16) C4ÐC (18) O5ÐC (18) C5ÐC (16) C6ÐC (17) C7ÐC (16) C8ÐC (18) C8ÐC (18) C9ÐC (16) C10ÐC (2) C11ÐC (17) C9ÐC8ÐC (11) C9ÐC8ÐC (11) C7ÐC8ÐC (11) O1ÐC9ÐC (11) O1ÐC9ÐC (11) C8ÐC9ÐC (11) C2ÐC1ÐC (10) C6ÐC1ÐC (11) C11ÐO2ÐC (10) C11ÐC10ÐC (12) C10ÐC11ÐO (11) C10ÐC11ÐC (13) O2ÐC11ÐC (12) O2ÐC12ÐC (11) O4ÐC14ÐO (11) O4ÐC14ÐC (13) O5ÐC14ÐC (11) O-bound H atoms were located in a difference Fourier synthesis, and their coordinates were re ned. C-bound H atoms were placed at calculated positions (CÐH = 0.93, 0.96 or 0.97 A Ê ) and were included in the re nement in the riding-model approximation. Their displacement parameters were set at 1.2 or 1.5 times U eq of the parent C or O atoms, respectively. Data collection: SMART (Bruker, 2001); cell re nement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97. The authors thank the Natural Science Foundation of Fujian Province, China (No. C ), the Key Foundation of Science & Technology Project of Fujian Province, China (No H011) and the National High Technology Research and Development Program of China (863 Program, No AA620401) for supporting this work. Table 2 Hydrogen-bonding geometry (A Ê, ). DÐHA DÐH HA DA DÐHA O5ÐH5O (1) 1.19 (1) (15) 177 (2) O6ÐH6O (2) 1.56 (2) (18) (18) O7ÐH7O (2) 2.17 (2) (16) (19) O7ÐH7O4 i 0.84 (2) 1.94 (2) (15) 147 (2) Symmetry code: (i) 2 x; 1 2 y; 1 2 z. References Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115±119. Bruker (2001). SAINT (Version 6.22) and SMART (Version 5.625). Bruker AXS Inc., Madison, Wisconsin, USA. Dean, F. M., Eade, R. A., Moubasher, R. & Robertson, A. (1957). Nature (London), 157, 366. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Acta Cryst. (2003). E59, o1244±o1245 Jian-Feng Wang et al. C 14 H 10 O 7 o1245

3 supporting information [doi: /s ] 7,8-Dihydroxy-3-methyl-10-oxo-1H,10H-pyrano[4,3-b]chromene-9-carboxylic acid Jian-Feng Wang, Yong-Jie Zhang, Mei-Juan Fang, Yao-Jian Huang, Zan-Bin Wei, Zhong-Hui Zheng, Wen-Jin Su and Yu-Fen Zhao S1. Comment The title compound, (I), had been prepared by dehydration of a natural product, fulvic acid [3,7,8-trihydroxy-3- methyl-10-oxo-4,10-dihydro-1h,3h-pyrano[4,3-b]chromene- 9-carboxylic acid, (II)], isolated from several fungi (Dean, 1957). In this study, (I) was isolated from the fermentation broth of Paecilomyces sp., an endophytic fungi of Cephalataxus fortunei, and its structure was determined by X-ray analysis. The chromone ring system of (I) is essentially planar, with the hydroxyl and carboxylic acid groups coplanar with the ring. There is one intermolecular hydrogen bond and three intramolecular hydrogen bonds in the crystal structure (Table 2), which make the crystal very stable (m.p K). S2. Experimental The title compound, (I) was isolated from the organic extract of the liquid culture of the Paecilomyces sp. Recrystallization from ethyl acetate afforded green crystals suitable for X-ray analysis. The molecular formula of (I) was deduced from the high resolution ESI MS spectrum as C 14 H 10 O 7, showing an accurate mass at m/z [M + H] +. The 13 C NMR analysis revealed 14 carbons: δ (p.p.m.) = 20.0 (C13), 64.3(C12), 94.5 (C10), (C4), (C8), (C6), (C1), (C2), (C3), (C5), (C9), (C11), (C14) and (C7). S3. Refinement Molecule (I) crystallized in the monoclinic, space group P2 1 /c. H atoms on O atoms were located in difference Fourier syntheses and the C-bound H atoms were placed at calculated positions (C H = 0.93, 0.96 or 0.97 Å) and were included in the refinement in the riding-model approximation. Their displacement parameters were set at 1.2 and or 1.5 times U eq of the equivalent isotropic displacement parameters of the parent C or O atoms, respectively. sup-1

4 Figure 1 ORTEP-3 (Farrugia, 1997) plot of the structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. 7,8-Dihydroxy-3-methyl-10-oxo-1H,10H-pyrano[4,3-b]chromene-9-carboxylic acid Crystal data C 14 H 10 O 7 M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (5) Å b = (5) Å c = (5) Å β = (5) V = (10) Å 3 Z = 4 Data collection Bruker AXS area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.974, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections F(000) = 600 D x = Mg m 3 Melting point = K Mo Kα radiation, λ = Å Cell parameters from 2225 reflections θ = µ = 0.13 mm 1 T = 296 K Chunk, green mm 2615 measured reflections 2615 independent reflections 2225 reflections with I > 2σ(I) R int = θ max = 27.5, θ min = 2.4 h = k = 0 13 l = parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map sup-2

5 Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0758P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.24 e Å 3 Δρ min = 0.20 e Å 3 Extinction correction: SHELXL97, Fc * =kfc[ xfc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: (3) Special details Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq O (13) (9) (5) (2) C (14) (12) (7) (3) O (13) (10) (6) (3) C (15) (13) (7) (3) O (14) (10) (6) (3) C (16) (12) (8) (3) O (14) (10) (6) (3) C (17) (13) (8) (3) O (16) (11) (7) (3) C (16) (12) (7) (3) O (13) (10) (6) (3) C (14) (12) (7) (3) O (15) (10) (6) (3) C (15) (12) (8) (3) C (15) (12) (7) (3) C (16) (13) (8) (3) C (18) (14) (8) (3) C (17) (13) (8) (3) C (18) (13) (8) (3) C (2) (16) (9) (4) C (17) (14) (8) (3) H4A * H (3) (2) (8) 0.086* H (2) (2) (12) 0.066* H (3) (2) (15) 0.077* H10A * H12A * H12B * H13A * H13B * H13C * sup-3

6 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (5) (5) (4) (4) (3) (3) C (6) (6) (5) (5) (4) (4) O (5) (5) (5) (4) (4) (4) C (6) (6) (5) (5) (4) (4) O (6) (5) (5) (5) (4) (4) C (7) (6) (6) (5) (5) (4) O (7) (6) (4) (5) (4) (4) C (7) (6) (6) (6) (5) (4) O (8) (7) (5) (6) (5) (4) C (6) (6) (5) (5) (4) (4) O (6) (5) (4) (5) (4) (4) C (5) (6) (5) (5) (4) (4) O (7) (5) (4) (5) (5) (4) C (6) (6) (6) (5) (4) (4) C (6) (6) (6) (5) (4) (4) C (6) (6) (5) (5) (4) (4) C (7) (7) (6) (6) (5) (5) C (7) (7) (6) (5) (5) (5) C (7) (6) (6) (6) (5) (5) C (9) (8) (7) (7) (6) (6) C (6) (7) (6) (6) (5) (5) Geometric parameters (Å, º) O1 C (16) C7 C (16) O1 C (14) C8 C (18) C1 C (18) C8 C (18) C1 C (15) C9 C (16) C1 C (16) C10 C (2) O2 C (18) C11 C (17) O2 C (16) O3 H (10) C2 O (14) C4 H4A C2 C (18) O5 H (9) O3 C (15) O6 H (2) C3 O (16) O7 H (2) C3 C (16) C10 H10A O4 C (16) C12 H12A C4 C (18) C12 H12B O5 C (18) C13 H13A C5 C (16) C13 H13B C6 C (17) C13 H13C C9 O1 C (9) C11 C10 C (12) C2 C1 C (10) C10 C11 O (11) O6 C2 C (11) C10 C11 C (13) sup-4

7 O6 C2 C (11) O2 C11 C (12) C1 C2 C (10) O2 C12 C (11) O7 C3 C (11) O4 C14 O (11) O7 C3 C (11) O4 C14 C (13) C4 C3 C (11) O5 C14 C (11) C3 C4 C (11) C3 C4 H4A O1 C5 C (10) C5 C4 H4A O1 C5 C (10) C7 O3 H (11) C4 C5 C (10) C14 O5 H (11) C5 C6 C (11) C2 O6 H (12) C5 C6 C (10) C3 O7 H (16) C1 C6 C (10) C11 C10 H10A O3 C7 C (11) C9 C10 H10A O3 C7 C (11) O2 C12 H12A C8 C7 C (10) C8 C12 H12A C9 C8 C (11) O2 C12 H12B C9 C8 C (11) C8 C12 H12B C7 C8 C (11) H12A C12 H12B O1 C9 C (11) C11 C13 H13A O1 C9 C (11) C11 C13 H13B C8 C9 C (11) H13A C13 H13B C2 C1 C (10) C11 C13 H13C C6 C1 C (11) H13A C13 H13C C11 O2 C (10) H13B C13 H13C C6 C1 C2 O (11) C1 C6 C7 C (11) C14 C1 C2 O (18) O3 C7 C8 C (11) C6 C1 C2 C (18) C6 C7 C8 C (18) C14 C1 C2 C (11) O3 C7 C8 C (18) O6 C2 C3 O (18) C6 C7 C8 C (10) C1 C2 C3 O (11) C5 O1 C9 C (18) O6 C2 C3 C (11) C5 O1 C9 C (11) C1 C2 C3 C (19) C7 C8 C9 O (19) O7 C3 C4 C (12) C12 C8 C9 O (11) C2 C3 C4 C (19) C7 C8 C9 C (12) C9 O1 C5 C (11) C12 C8 C9 C (18) C9 O1 C5 C (18) O1 C9 C10 C (12) C3 C4 C5 O (11) C8 C9 C10 C (2) C3 C4 C5 C6 0.6 (2) C9 C10 C11 O2 3.4 (2) O1 C5 C6 C (10) C9 C10 C11 C (13) C4 C5 C6 C (18) C12 O2 C11 C (18) O1 C5 C6 C (17) C12 O2 C11 C (12) C4 C5 C6 C (12) C11 O2 C12 C (15) C2 C1 C6 C (16) C9 C8 C12 O (16) C14 C1 C6 C (11) C7 C8 C12 O (12) C2 C1 C6 C (11) C2 C1 C14 O (17) C14 C1 C6 C7 2.1 (2) C6 C1 C14 O (11) C5 C6 C7 O (11) C2 C1 C14 O (12) sup-5

8 C1 C6 C7 O3 2.1 (2) C6 C1 C14 O5 3.1 (2) C5 C6 C7 C (16) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O5 H5 O (1) 1.19 (1) (15) 177 (2) O6 H6 O (2) 1.56 (2) (18) (18) O7 H7 O (2) 2.17 (2) (16) (19) O7 H7 O4 i 0.84 (2) 1.94 (2) (15) 147 (2) Symmetry code: (i) x+2, y+1/2, z+1/2. sup-6