Literature DB >> 22590344

Alternariol 9-O-methyl ether.

Sreekanth Dasari, Mohan Bhadbhade, Brett A Neilan.

Abstract

The title compound (AME; systematic name: 3,7-dihy-droxy-9-meth-oxy-1-methyl-6H-benzo[c]chromen-6-one), C(15)H(12)O(5), was isolated from an endophytic fungi Alternaria sp., from Catharanthus roseus (common name: Madagascar periwinkle). There is an intramolecular O-H⋯O hydrogen bond in the essentially planar mol-ecule (r.m.s. deviation 0.02 Å). In the crystal, the molecule forms an O-H⋯O hydrogen bond with its centrosymmetric counterpart with four bridging inter-actions (two O-H⋯O and two C-H⋯O). The almost planar sheets of the dimeric units thus formed are stacked along b axis via C-H⋯π and π-π contacts [with C⋯C short contacts between aromatic moieties of 3.324 (3), 3.296 (3) and 3.374 (3) Å].

Entities: Chemical Disease Species

Year: 2012 PMID： 22590344 PMCID： PMC3344582 DOI： 10.1107/S1600536812015000

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

Species of the fungal genus Alternaria are known producers of mycotoxins and have previously been described as plant endophytes. For the isolation of Alternariol (AOH) and Alternariol 9-O-methyl ether (AME) see: An et al. (1989 ▶); Wen (2009 ▶); Ashour et al. (2011 ▶). For 1H, 13C and two-dimensional experimental data analysis see: Koch et al. (2005 ▶); Siegel et al. (2010 ▶). For the biological activity see: Aly et al. (2008 ▶).

Experimental

Crystal data

C15H12O5 M = 272.25 Triclinic, a = 7.1819 (7) Å b = 8.9393 (8) Å c = 10.2511 (10) Å α = 105.296 (5)° β = 105.174 (4)° γ = 101.430 (4)° V = 586.90 (10) Å3 Z = 2 Mo Kα radiation μ = 0.12 mm−1 T = 160 K 0.29 × 0.13 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.967, T max = 0.993 7824 measured reflections 2062 independent reflections 1718 reflections with I > 2σ(I) R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.033 wR(F 2) = 0.096 S = 1.05 2062 reflections 184 parameters H-atom parameters constrained Δρmax = 0.25 e Å−3 Δρmin = −0.20 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: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015000/hg5207sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015000/hg5207Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₅H₁₂O₅	Z = 2
M_r = 272.25	F(000) = 284
Triclinic, P1	D_x = 1.541 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1819 (7) Å	Cell parameters from 4112 reflections
b = 8.9393 (8) Å	θ = 2.7–29.6°
c = 10.2511 (10) Å	µ = 0.12 mm⁻¹
α = 105.296 (5)°	T = 160 K
β = 105.174 (4)°	Plates, colourless
γ = 101.430 (4)°	0.29 × 0.13 × 0.06 mm
V = 586.90 (10) Å³

Bruker Kappa APEXII CCD diffractometer	2062 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ scans, and ω scans with κ offsets	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.967, T_max = 0.993	k = −10→10
7824 measured reflections	l = −12→12

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0511P)² + 0.1544P] where P = (F_o² + 2F_c²)/3
2062 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

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	U_iso*/U_eq
O1	0.65936 (15)	−0.18780 (12)	0.08182 (10)	0.0292 (3)
H1	0.7594	−0.2138	0.1163	0.044*
O2	0.84646 (14)	0.13308 (12)	0.56397 (9)	0.0245 (3)
O3	0.96545 (14)	0.26527 (12)	0.79381 (10)	0.0267 (3)
O4	0.78595 (15)	0.45323 (13)	0.91399 (10)	0.0329 (3)
H4	0.8735	0.4077	0.9083	0.049*
O5	0.17885 (16)	0.48775 (13)	0.61731 (11)	0.0331 (3)
C1	0.4041 (2)	0.07774 (16)	0.25561 (14)	0.0202 (3)
C2	0.4514 (2)	−0.03110 (16)	0.15399 (14)	0.0225 (3)
H2	0.3642	−0.0722	0.0598	0.027*
C3	0.6240 (2)	−0.08085 (16)	0.18775 (14)	0.0219 (3)
C4	0.7533 (2)	−0.02073 (16)	0.32735 (14)	0.0223 (3)
H4A	0.8701	−0.0517	0.3529	0.027*
C5	0.7053 (2)	0.08647 (16)	0.42815 (14)	0.0201 (3)
C6	0.8305 (2)	0.23648 (16)	0.67963 (14)	0.0208 (3)
C7	0.66319 (19)	0.30221 (15)	0.66141 (14)	0.0200 (3)
C8	0.6471 (2)	0.41025 (16)	0.78306 (14)	0.0232 (3)
C9	0.4878 (2)	0.47638 (16)	0.77364 (14)	0.0244 (3)
H9	0.4787	0.5483	0.8542	0.029*
C10	0.3421 (2)	0.43228 (16)	0.64067 (15)	0.0241 (3)
C11	0.3534 (2)	0.32476 (17)	0.51851 (14)	0.0249 (3)
H11	0.2522	0.2980	0.4311	0.030*
C12	0.5112 (2)	0.25710 (15)	0.52416 (14)	0.0197 (3)
C13	0.5353 (2)	0.14195 (16)	0.40140 (14)	0.0197 (3)
C14	0.2119 (2)	0.11934 (18)	0.20211 (14)	0.0267 (3)
H14A	0.1482	0.0608	0.1014	0.040*
H14B	0.2416	0.2335	0.2180	0.040*
H14C	0.1232	0.0903	0.2528	0.040*
C15	0.1611 (2)	0.60559 (18)	0.73528 (16)	0.0309 (4)
H15A	0.1602	0.5618	0.8112	0.046*
H15B	0.0380	0.6330	0.7045	0.046*
H15C	0.2733	0.7010	0.7693	0.046*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0335 (6)	0.0342 (6)	0.0220 (5)	0.0176 (5)	0.0108 (4)	0.0050 (4)
O2	0.0216 (5)	0.0295 (5)	0.0189 (5)	0.0119 (4)	0.0028 (4)	0.0029 (4)
O3	0.0210 (5)	0.0307 (6)	0.0217 (5)	0.0091 (4)	0.0008 (4)	0.0033 (4)
O4	0.0267 (6)	0.0418 (6)	0.0203 (5)	0.0153 (5)	0.0002 (4)	−0.0020 (4)
O5	0.0346 (6)	0.0396 (6)	0.0266 (5)	0.0252 (5)	0.0080 (4)	0.0050 (5)
C1	0.0205 (7)	0.0210 (7)	0.0199 (7)	0.0052 (5)	0.0071 (5)	0.0084 (5)
C2	0.0224 (7)	0.0254 (7)	0.0178 (7)	0.0049 (6)	0.0046 (5)	0.0075 (6)
C3	0.0261 (7)	0.0211 (7)	0.0211 (7)	0.0070 (6)	0.0121 (6)	0.0071 (6)
C4	0.0204 (7)	0.0251 (7)	0.0245 (7)	0.0100 (6)	0.0086 (6)	0.0095 (6)
C5	0.0188 (7)	0.0223 (7)	0.0180 (7)	0.0049 (5)	0.0045 (5)	0.0069 (5)
C6	0.0188 (7)	0.0203 (7)	0.0204 (7)	0.0032 (5)	0.0055 (6)	0.0046 (6)
C7	0.0185 (7)	0.0194 (7)	0.0212 (7)	0.0041 (5)	0.0060 (6)	0.0067 (6)
C8	0.0216 (7)	0.0227 (7)	0.0203 (7)	0.0033 (6)	0.0039 (6)	0.0044 (6)
C9	0.0278 (8)	0.0215 (7)	0.0228 (7)	0.0090 (6)	0.0098 (6)	0.0031 (6)
C10	0.0239 (7)	0.0238 (7)	0.0278 (7)	0.0112 (6)	0.0090 (6)	0.0102 (6)
C11	0.0259 (7)	0.0282 (8)	0.0188 (7)	0.0123 (6)	0.0037 (6)	0.0055 (6)
C12	0.0198 (7)	0.0187 (7)	0.0205 (7)	0.0045 (5)	0.0064 (5)	0.0075 (6)
C13	0.0197 (7)	0.0200 (7)	0.0202 (7)	0.0054 (5)	0.0069 (5)	0.0080 (6)
C14	0.0243 (8)	0.0326 (8)	0.0191 (7)	0.0106 (6)	0.0037 (6)	0.0040 (6)
C15	0.0335 (8)	0.0301 (8)	0.0333 (8)	0.0185 (7)	0.0152 (7)	0.0065 (7)

O1—C3	1.3602 (16)	C5—C13	1.3958 (19)
O1—H1	0.8200	C6—C7	1.4299 (19)
O2—C6	1.3446 (16)	C7—C8	1.4090 (18)
O2—C5	1.3884 (15)	C7—C12	1.4338 (18)
O3—C6	1.2344 (16)	C8—C9	1.382 (2)
O4—C8	1.3486 (16)	C9—C10	1.3835 (19)
O4—H4	0.8200	C9—H9	0.9300
O5—C10	1.3508 (17)	C10—C11	1.3955 (19)
O5—C15	1.4317 (16)	C11—C12	1.3819 (19)
C1—C2	1.3889 (19)	C11—H11	0.9300
C1—C13	1.4305 (18)	C12—C13	1.4743 (18)
C1—C14	1.5031 (19)	C14—H14A	0.9600
C2—C3	1.3890 (19)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.3784 (18)	C15—H15A	0.9600
C4—C5	1.3785 (19)	C15—H15B	0.9600
C4—H4A	0.9300	C15—H15C	0.9600

C3—O1—H1	109.5	C8—C9—C10	117.96 (12)
C6—O2—C5	122.41 (10)	C8—C9—H9	121.0
C8—O4—H4	109.5	C10—C9—H9	121.0
C10—O5—C15	118.10 (11)	O5—C10—C9	123.74 (12)
C2—C1—C13	119.78 (12)	O5—C10—C11	114.42 (12)
C2—C1—C14	116.06 (11)	C9—C10—C11	121.84 (12)
C13—C1—C14	124.16 (12)	C12—C11—C10	121.63 (12)
C1—C2—C3	122.49 (12)	C12—C11—H11	119.2
C1—C2—H2	118.8	C10—C11—H11	119.2
C3—C2—H2	118.8	C11—C12—C7	116.99 (12)
O1—C3—C4	122.22 (12)	C11—C12—C13	125.49 (12)
O1—C3—C2	118.81 (12)	C7—C12—C13	117.51 (12)
C4—C3—C2	118.97 (12)	C5—C13—C1	114.81 (12)
C3—C4—C5	118.40 (12)	C5—C13—C12	117.24 (12)
C3—C4—H4A	120.8	C1—C13—C12	127.96 (12)
C5—C4—H4A	120.8	C1—C14—H14A	109.5
C4—C5—O2	111.77 (11)	C1—C14—H14B	109.5
C4—C5—C13	125.54 (12)	H14A—C14—H14B	109.5
O2—C5—C13	122.68 (12)	C1—C14—H14C	109.5
O3—C6—O2	115.38 (12)	H14A—C14—H14C	109.5
O3—C6—C7	125.97 (12)	H14B—C14—H14C	109.5
O2—C6—C7	118.65 (11)	O5—C15—H15A	109.5
C8—C7—C6	118.38 (11)	O5—C15—H15B	109.5
C8—C7—C12	120.11 (12)	H15A—C15—H15B	109.5
C6—C7—C12	121.49 (12)	O5—C15—H15C	109.5
O4—C8—C9	116.98 (12)	H15A—C15—H15C	109.5
O4—C8—C7	121.56 (12)	H15B—C15—H15C	109.5
C9—C8—C7	121.46 (12)

C13—C1—C2—C3	−0.4 (2)	C15—O5—C10—C11	−176.59 (12)
C14—C1—C2—C3	−179.96 (13)	C8—C9—C10—O5	179.73 (13)
C1—C2—C3—O1	−179.96 (12)	C8—C9—C10—C11	−0.1 (2)
C1—C2—C3—C4	0.3 (2)	O5—C10—C11—C12	179.96 (12)
O1—C3—C4—C5	−179.60 (12)	C9—C10—C11—C12	−0.2 (2)
C2—C3—C4—C5	0.2 (2)	C10—C11—C12—C7	0.1 (2)
C3—C4—C5—O2	178.48 (11)	C10—C11—C12—C13	179.58 (12)
C3—C4—C5—C13	−0.5 (2)	C8—C7—C12—C11	0.4 (2)
C6—O2—C5—C4	−179.66 (12)	C6—C7—C12—C11	178.63 (12)
C6—O2—C5—C13	−0.6 (2)	C8—C7—C12—C13	−179.21 (12)
C5—O2—C6—O3	179.01 (11)	C6—C7—C12—C13	−0.93 (19)
C5—O2—C6—C7	−0.80 (19)	C4—C5—C13—C1	0.4 (2)
O3—C6—C7—C8	0.1 (2)	O2—C5—C13—C1	−178.50 (11)
O2—C6—C7—C8	179.88 (12)	C4—C5—C13—C12	−179.87 (12)
O3—C6—C7—C12	−178.21 (13)	O2—C5—C13—C12	1.2 (2)
O2—C6—C7—C12	1.6 (2)	C2—C1—C13—C5	0.05 (19)
C6—C7—C8—O4	0.7 (2)	C14—C1—C13—C5	179.61 (12)
C12—C7—C8—O4	179.02 (12)	C2—C1—C13—C12	−179.65 (12)
C6—C7—C8—C9	−179.00 (13)	C14—C1—C13—C12	−0.1 (2)
C12—C7—C8—C9	−0.7 (2)	C11—C12—C13—C5	−179.96 (13)
O4—C8—C9—C10	−179.16 (12)	C7—C12—C13—C5	−0.44 (19)
C7—C8—C9—C10	0.5 (2)	C11—C12—C13—C1	−0.3 (2)
C15—O5—C10—C9	3.5 (2)	C7—C12—C13—C1	179.25 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O4ⁱ	0.82	2.47	2.9371 (19)	117
C9—H9···O1ⁱⁱ	0.93	2.64	3.4645 (16)	148
C4—H4A···O2ⁱⁱⁱ	0.93	2.32	3.2511 (16)	174
O4—H4···O3	0.82	1.84	2.5692 (13)	148
O1—H1···O3ⁱⁱⁱ	0.82	2.14	2.9619 (13)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O4ⁱ	0.82	2.47	2.9371 (19)	117
C9—H9⋯O1ⁱⁱ	0.93	2.64	3.4645 (16)	148
C4—H4A⋯O2ⁱⁱⁱ	0.93	2.32	3.2511 (16)	174
O4—H4⋯O3	0.82	1.84	2.5692 (13)	148
O1—H1⋯O3ⁱⁱⁱ	0.82	2.14	2.9619 (13)	176

Symmetry codes: (i) ; (ii) ; (iii) .

4 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Cytotoxic metabolites from the fungal endophyte Alternaria sp. and their subsequent detection in its host plant Polygonum senegalense.

Authors: Amal H Aly; RuAngelie Edrada-Ebel; Ine Dewi Indriani; Victor Wray; Werner E G Müller; Frank Totzke; Ute Zirrgiebel; Christoph Schächtele; Michael H G Kubbutat; W H Lin; Peter Proksch; Rainer Ebel
Journal: J Nat Prod Date: 2008-05-22 Impact factor: 4.050

3. Total synthesis of alternariol.

Authors: Karen Koch; Joachim Podlech; Erika Pfeiffer; Manfred Metzler
Journal: J Org Chem Date: 2005-04-15 Impact factor: 4.354

4. Alternariol.

Authors: David Siegel; Sergey Troyanov; Johannes Noack; Franziska Emmerling; Irene Nehls
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2010-05-15