Alternariol 9-O-methyl ether dimethyl sulfoxide monosolvate.

THE TITLE COMPOUND (SYSTEMATIC NAME: 3,7-dihy-droxy-9-meth-oxy-1-methyl-6H-benzo[c]chromen-6-one dimethyl sulfoxide monosolvate), C15H12O5·C2H6OS, was isolated from an unidentified endophytic fungus (belonging to class Ascomycetes) of Taxus sp. In the crystal, both the alternariol 9-O-methyl ether (AME) and the dimethyl sulfoxide (DMSO) mol-ecules exhibit crystallographic mirror symmetry. One of the hy-droxy groups makes bifurcated hydrogen bonds, viz. an intra-molecular bond with the carbonyl group and an inter-molecular bond with the carbonyl group in an inversion-related AME mol-ecule. In the crystal, the AME mol-ecules are organized into stacks parallel with the b axis by π-π inter-actions between centrosymmetrically related mol-ecules [the distance between the centroid of the central ring and the centroid of the meth-oxy-substituted benzene ring in the next mol-ecule of the stack is 3.6184 (5) Å]. Pairs of DMSO mol-ecules, linked via centrosymmetric C-H⋯O contacts, are inserted into the voids created by the AME mol-ecules, making O-H⋯O and C-H⋯O contacts with the hosts.

Related literature

For the bioactivity of AME and its precursor alternariol, see: Aly et al. (2008 ▶); Brugger et al. (2006 ▶); Pfeiffer et al. (2007 ▶); Miller et al. (2012 ▶). For their occurrence as contaminants in food and beverages, see: Lau et al. (2003 ▶). For the related crystal strucutre of alternariol, see: Dasari et al. (2012 ▶).

Experimental

Crystal data

C15H12O5·C2H6OS

M = 350.37

Monoclinic,

a = 18.8906 (8) Å

b = 6.8391 (3) Å

c = 15.3542 (8) Å

β = 126.815 (3)°

V = 1588.08 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 150 K

0.38 × 0.09 × 0.05 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.916, T max = 0.988

7177 measured reflections

1524 independent reflections

1382 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.093

S = 1.10

1524 reflections

144 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.32 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: SHELXTL-Plus.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813012294/fy2088sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012294/fy2088Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012294/fy2088Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H12O5·C2H6OS	F(000) = 736
Mr = 350.37	Dx = 1.465 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 4872 reflections
a = 18.8906 (8) Å	θ = 2.7–30.6°
b = 6.8391 (3) Å	µ = 0.24 mm−1
c = 15.3542 (8) Å	T = 150 K
β = 126.815 (3)°	Plate, colourless
V = 1588.08 (13) Å3	0.38 × 0.09 × 0.05 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	1524 independent reflections
Radiation source: fine-focus sealed tube	1382 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ scans, and ω scans with κ offsets	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −21→22
Tmin = 0.916, Tmax = 0.988	k = −8→8
7177 measured reflections	l = −18→18

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.055P)2 + 0.9734P] where P = (Fo2 + 2Fc2)/3
1524 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.27 e Å−3
3 restraints	Δρmin = −0.32 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	Uiso*/Ueq	Occ. (<1)
O1	0.39016 (10)	0.0000	0.94667 (11)	0.0391 (4)
H1O1	0.3537	0.0000	0.9575	0.059*
O2	0.42281 (8)	0.0000	0.67046 (11)	0.0206 (3)
O3	0.45897 (9)	0.0000	0.55957 (11)	0.0265 (4)
O4	0.34069 (9)	0.0000	0.35176 (11)	0.0237 (3)
H1O4	0.3931	0.0000	0.4162	0.036*
O5	0.04062 (9)	0.0000	0.22240 (11)	0.0268 (4)
C1	0.21796 (12)	0.0000	0.64985 (15)	0.0174 (4)
C2	0.25831 (11)	0.0000	0.76077 (13)	0.0205 (4)
H2	0.2229	0.0000	0.7842	0.025*
C3	0.34992 (13)	0.0000	0.83847 (15)	0.0227 (5)
C4	0.40259 (13)	0.0000	0.80403 (15)	0.0209 (4)
H4C	0.4639	0.0000	0.8540	0.025*
C5	0.36216 (13)	0.0000	0.69341 (16)	0.0173 (4)
C6	0.39827 (13)	0.0000	0.56791 (16)	0.0190 (4)
C7	0.30546 (12)	0.0000	0.47951 (15)	0.0172 (4)
C8	0.28052 (13)	0.0000	0.37232 (16)	0.0185 (4)
C9	0.19222 (13)	0.0000	0.28315 (15)	0.0202 (4)
H9	0.1757	0.0000	0.2126	0.024*
C10	0.12935 (13)	0.0000	0.30239 (16)	0.0192 (4)
C11	0.15201 (12)	0.0000	0.40773 (13)	0.0194 (4)
H11	0.1077	0.0000	0.4170	0.023*
C12	0.24039 (13)	0.0000	0.49846 (16)	0.0161 (4)
C13	0.27066 (12)	0.0000	0.61190 (15)	0.0162 (4)
C14	0.11825 (10)	0.0000	0.57677 (11)	0.0218 (4)
H14A	0.0970	−0.1146	0.5317	0.033*	0.50
H14B	0.0970	0.1146	0.5317	0.033*	0.50
H14C	0.0974	0.0000	0.6204	0.033*
C15	0.01044 (14)	0.0000	0.11184 (16)	0.0292 (5)
H15A	−0.0530	0.0000	0.0641	0.044*
H15B	0.0320	−0.1146	0.0986	0.044*	0.50
H15C	0.0320	0.1146	0.0986	0.044*	0.50
S1D	0.30260 (3)	0.0000	0.10913 (4)	0.02538 (19)
O1D	0.27939 (9)	0.0000	−0.00407 (11)	0.0298 (4)
C1D	0.37818 (10)	0.1967 (2)	0.17933 (12)	0.0285 (4)
H4	0.3992	0.1972	0.2538	0.043*
H3	0.3489	0.3181	0.1455	0.043*
H5	0.4273	0.1808	0.1765	0.043*

	U11	U22	U33	U12	U13	U23
O1	0.0209 (8)	0.0812 (13)	0.0132 (7)	0.000	0.0091 (7)	0.000
O2	0.0136 (7)	0.0319 (7)	0.0157 (7)	0.000	0.0084 (6)	0.000
O3	0.0170 (7)	0.0435 (9)	0.0217 (8)	0.000	0.0131 (6)	0.000
O4	0.0209 (7)	0.0340 (8)	0.0190 (7)	0.000	0.0134 (6)	0.000
O5	0.0173 (7)	0.0422 (9)	0.0130 (7)	0.000	0.0048 (6)	0.000
C1	0.0179 (10)	0.0161 (9)	0.0162 (9)	0.000	0.0092 (8)	0.000
C2	0.0195 (10)	0.0265 (10)	0.0188 (10)	0.000	0.0132 (9)	0.000
C3	0.0221 (10)	0.0303 (11)	0.0142 (10)	0.000	0.0100 (9)	0.000
C4	0.0135 (9)	0.0284 (10)	0.0151 (10)	0.000	0.0054 (8)	0.000
C5	0.0166 (9)	0.0180 (9)	0.0180 (10)	0.000	0.0108 (8)	0.000
C6	0.0189 (10)	0.0190 (9)	0.0184 (10)	0.000	0.0108 (8)	0.000
C7	0.0181 (10)	0.0152 (9)	0.0176 (10)	0.000	0.0103 (9)	0.000
C8	0.0236 (10)	0.0152 (9)	0.0200 (10)	0.000	0.0150 (9)	0.000
C9	0.0257 (11)	0.0198 (9)	0.0140 (9)	0.000	0.0113 (9)	0.000
C10	0.0165 (9)	0.0190 (9)	0.0157 (10)	0.000	0.0062 (8)	0.000
C11	0.0164 (10)	0.0226 (9)	0.0176 (10)	0.000	0.0094 (9)	0.000
C12	0.0188 (9)	0.0118 (8)	0.0161 (9)	0.000	0.0097 (8)	0.000
C13	0.0163 (9)	0.0145 (9)	0.0165 (10)	0.000	0.0092 (8)	0.000
C14	0.0174 (10)	0.0307 (10)	0.0190 (10)	0.000	0.0119 (9)	0.000
C15	0.0266 (12)	0.0389 (12)	0.0132 (10)	0.000	0.0072 (9)	0.000
S1D	0.0166 (3)	0.0424 (3)	0.0167 (3)	0.000	0.0097 (2)	0.000
O1D	0.0221 (8)	0.0481 (9)	0.0152 (7)	0.000	0.0090 (6)	0.000
C1D	0.0306 (8)	0.0267 (8)	0.0234 (8)	0.0054 (6)	0.0136 (7)	0.0019 (6)

O1—C3	1.351 (2)	C7—C12	1.423 (3)
O1—H1O1	0.8003	C8—C9	1.386 (3)
O2—C6	1.349 (2)	C9—C10	1.385 (3)
O2—C5	1.386 (2)	C9—H9	0.9300
O3—C6	1.228 (2)	C10—C11	1.403 (2)
O4—C8	1.350 (2)	C11—C12	1.393 (3)
O4—H1O4	0.8859	C11—H11	0.9300
O5—C10	1.360 (2)	C12—C13	1.472 (3)
O5—C15	1.431 (2)	C14—H14A	0.9600
C1—C2	1.388 (2)	C14—H14B	0.9600
C1—C13	1.423 (3)	C14—H14C	0.9600
C1—C14	1.508 (2)	C15—H15A	0.9600
C2—C3	1.394 (3)	C15—H15B	0.9600
C2—H2	0.9300	C15—H15C	0.9600
C3—C4	1.378 (3)	S1D—O1D	1.5166 (15)
C4—C5	1.383 (3)	S1D—C1D	1.7790 (15)
C4—H4C	0.9300	S1D—C1Di	1.7790 (15)
C5—C13	1.401 (3)	C1D—H4	0.9600
C6—C7	1.437 (3)	C1D—H3	0.9600
C7—C8	1.415 (3)	C1D—H5	0.9600
C3—O1—H1O1	109.6	O5—C10—C11	113.60 (17)
C6—O2—C5	122.59 (15)	C9—C10—C11	122.51 (17)
C8—O4—H1O4	105.8	C12—C11—C10	120.51 (16)
C10—O5—C15	118.07 (16)	C12—C11—H11	119.7
C2—C1—C13	119.87 (17)	C10—C11—H11	119.7
C2—C1—C14	115.84 (16)	C11—C12—C7	117.39 (17)
C13—C1—C14	124.30 (16)	C11—C12—C13	124.49 (17)
C1—C2—C3	122.50 (18)	C7—C12—C13	118.13 (17)
C1—C2—H2	118.7	C5—C13—C1	115.19 (17)
C3—C2—H2	118.7	C5—C13—C12	116.97 (17)
O1—C3—C4	117.92 (18)	C1—C13—C12	127.83 (17)
O1—C3—C2	123.20 (18)	C1—C14—H14A	109.5
C4—C3—C2	118.88 (18)	C1—C14—H14B	109.5
C3—C4—C5	118.47 (18)	H14A—C14—H14B	109.5
C3—C4—H4C	120.8	C1—C14—H14C	109.5
C5—C4—H4C	120.8	H14A—C14—H14C	109.5
C4—C5—O2	112.33 (16)	H14B—C14—H14C	109.5
C4—C5—C13	125.09 (18)	O5—C15—H15A	109.5
O2—C5—C13	122.58 (17)	O5—C15—H15B	109.5
O3—C6—O2	115.63 (17)	H15A—C15—H15B	109.5
O3—C6—C7	126.07 (18)	O5—C15—H15C	109.5
O2—C6—C7	118.30 (17)	H15A—C15—H15C	109.5
C8—C7—C12	120.78 (17)	H15B—C15—H15C	109.5
C8—C7—C6	117.79 (17)	O1D—S1D—C1D	105.68 (6)
C12—C7—C6	121.43 (18)	O1D—S1D—C1Di	105.68 (6)
O4—C8—C9	116.93 (17)	C1D—S1D—C1Di	98.23 (10)
O4—C8—C7	122.14 (17)	S1D—C1D—H4	109.5
C9—C8—C7	120.93 (18)	S1D—C1D—H3	109.5
C10—C9—C8	117.89 (18)	H4—C1D—H3	109.5
C10—C9—H9	121.1	S1D—C1D—H5	109.5
C8—C9—H9	121.1	H4—C1D—H5	109.5
O5—C10—C9	123.89 (18)	H3—C1D—H5	109.5
C13—C1—C2—C3	0.000 (1)	C15—O5—C10—C11	180.0
C14—C1—C2—C3	180.0	C8—C9—C10—O5	180.0
C1—C2—C3—O1	180.0	C8—C9—C10—C11	0.0
C1—C2—C3—C4	0.000 (1)	O5—C10—C11—C12	180.0
O1—C3—C4—C5	180.000 (1)	C9—C10—C11—C12	0.0
C2—C3—C4—C5	0.000 (1)	C10—C11—C12—C7	0.0
C3—C4—C5—O2	180.0	C10—C11—C12—C13	180.0
C3—C4—C5—C13	0.0	C8—C7—C12—C11	0.0
C6—O2—C5—C4	180.0	C6—C7—C12—C11	180.0
C6—O2—C5—C13	0.0	C8—C7—C12—C13	180.0
C5—O2—C6—O3	180.0	C6—C7—C12—C13	0.0
C5—O2—C6—C7	0.0	C4—C5—C13—C1	0.0
O3—C6—C7—C8	0.0	O2—C5—C13—C1	180.0
O2—C6—C7—C8	180.0	C4—C5—C13—C12	180.0
O3—C6—C7—C12	180.0	O2—C5—C13—C12	0.000 (1)
O2—C6—C7—C12	0.0	C2—C1—C13—C5	0.000 (1)
C12—C7—C8—O4	180.0	C14—C1—C13—C5	180.0
C6—C7—C8—O4	0.0	C2—C1—C13—C12	180.0
C12—C7—C8—C9	0.0	C14—C1—C13—C12	0.0
C6—C7—C8—C9	180.0	C11—C12—C13—C5	180.0
O4—C8—C9—C10	180.0	C7—C12—C13—C5	0.0
C7—C8—C9—C10	0.0	C11—C12—C13—C1	0.0
C15—O5—C10—C9	0.0	C7—C12—C13—C1	180.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1Dii	0.80	1.82	2.617 (2)	175
O4—H1O4···O3	0.89	1.76	2.575 (2)	151
O4—H1O4···O3iii	0.89	2.59	3.162 (2)	123
C4—H4C···O1iv	0.93	2.62	3.467 (2)	152
C1D—H4···O4	0.96	2.70	3.401 (2)	130
C1D—H5···O2iii	0.96	2.66	3.2970 (19)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O1D i	0.80	1.82	2.617 (2)	175
O4—H1O4⋯O3	0.89	1.76	2.575 (2)	151
O4—H1O4⋯O3ii	0.89	2.59	3.162 (2)	123
C4—H4C⋯O1iii	0.93	2.62	3.467 (2)	152
C1D—H4⋯O4	0.96	2.70	3.401 (2)	130
C1D—H5⋯O2ii	0.96	2.66	3.2970 (19)	124

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