Alternariol 9-O-methyl ether dimethyl sulfoxide monosolvate

Dasari, S.; Miller, K.I.; Kalaitzis, J.A.; Bhadbhade, M.; Neilan, B.A.

doi:10.1107/S1600536813012294

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages o872-o873

doi:10.1107/S1600536813012294

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Alternariol 9-O-methyl ether dimethyl sulfoxide monosolvate

Sreekanth Dasari,^a Kristin I. Miller,^a John A. Kalaitzis,^a Mohan Bhadbhade ^b and Brett A. Neilan ^a ^*

^aSchool of Biotechnology and Biomolecular Sciences, University of New South Wales, Sydney, NSW 2052, Australia, and ^bMark Wainwright Analytical Centre, University of New South Wales, Sydney, NSW 2052, Australia
^*Correspondence e-mail: b.neilan@unsw.edu.au

(Received 14 January 2013; accepted 6 May 2013; online 11 May 2013)

The title compound (systematic name: 3,7-dihydroxy-9-methoxy-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) molecules exhibit crystallographic mirror symmetry. One of the hydroxy groups makes bifurcated hydrogen bonds, viz. an intramolecular bond with the carbonyl group and an intermolecular bond with the carbonyl group in an inversion-related AME molecule. In the crystal, the AME molecules are organized into stacks parallel with the b axis by π–π interactions between centrosymmetrically related molecules [the distance between the centroid of the central ring and the centroid of the methoxy-substituted benzene ring in the next molecule of the stack is 3.6184 (5) Å]. Pairs of DMSO molecules, linked via centrosymmetric C—H⋯O contacts, are inserted into the voids created by the AME molecules, 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_r = 350.37
Monoclinic, C 2/m
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.093
S = 1.10
1524 reflections
144 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O1Dⁱ	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) x, y, z+1; (ii) -x+1, y, -z+1; (iii) -x+1, y, -z+2.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813012294/fy2088sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813012294/fy2088Isup3.cml

checkCIF report

Comment top

Extracts of the fungal endophyte Ascomycete F53 have previously demonstrated promising anti-proliferative activity against multiple myeloma RPMI-8226 cells, and mild growth inhibitory activities against Staphylococcus aureus, Escherichia coli and Cryptococcus albidus (Miller et al., 2012). The mycotoxin alternariol 9-O-methyl ether (AME) was previously thought to be produced soley by the fungal genus Alternaria however, its production has recently been reported from other fungal genera including Phoma sp.. Chemical profiling and genetic analysis of the fungus demonstrated the potential of the fungus to biosynthesize the mycotoxins, AOH, AME and other related derivatized secondary metabolites (data not shown).

Alternariol 9-O-methyl ether (AME; C₁₅H₁₂O₅) and its precursor alternariol (AOH) are well known for their mammalian toxicity, mutagenic properties and mild antimicrobial properties.

Although AME has been well studied as a mycotoxin, the crystal structure was only recently reported by us (Dasari et al., 2012). Due to the title compound's demonstrated varied biological activities it is a suitable candidate molecule to study its molecular arrangement in different crystalline environments. In this report, we present the DMSO solvated form of this compound.

An ORTEP view of the molecule and the solvent, DMSO, (Fig. 1) shows two O—H···O hydrogen bonds; one within the AME molecule (O4—H1O4···O3) and the other one between AME and DMSO (O1—H1O1···O1d). The molecular association involving significant interactions (Fig. 2) shows that the two DMSO molecules are held between two pairs of AME molecules making a network of C—H···O hydrogen bonds (Table 1). The two DMSO molecules are associated via centrosymmetric C1D—H3···O1D contacts. Each of these is attached through their methyl groups to two AME molecules via C—H···O contacts (Fig. 2 and Table 1). The two views of molecular packing looking down b axis (Fig. 3) and down an arbitrary direction (Fig. 4) show stacking of molecules with the DMSO molecules inserted into the crystal lattice without disturbing the parallel layer arrangement that was observed in the unsolvated form.

Related literature top

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 top

The fungal endophyte Ascomycete F53 was isolated from the Chinese medicinal plant Taxus yunnanensis, which was collected from mountainious area of Yunnan province in the Peoples Republic of China. A seed culture of Ascomycete F53 was used to innoculate 1L malt extract broth which was incubated for 21 days for the production of fungal secondary metabolites. The culture broth and mycelium were extracted with ethyl acetate (1L) to yield crude extract which was then fractionated on silica gel using a stepwise gradient of hexane to ethyl acetate and then with methanol to yield 12 fractions. The ethyl acetate fraction was further separated using C18 Sep-pak soild phase extraction column and eluted with a stepwise gradient of water to methanol. The fraction which eluted with 2:1 water/methanol yielded the title compound. The compound was dissolved in DMSO, and on slow evaporation of the solvent, formed plate like crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound showing the intramolecular and intermolecular AME···DMSO hydrogen bonds. Thermal ellipsoids are drawn at 40% probability level.
	Fig. 2. Molecular association between AME molecules and solvent DMSO molecules depicting a network of interactions.
	Fig. 3. Packing of molecules viewed down the crystallographic b axis.
	Fig. 4. Packing of molecules along an arbitrary direction.

3,7-Dihydroxy-9-methoxy-1-methyl-6H-benzo[c]chromen-6-one dimethylsulfoxide monosolvate top

Crystal data top

C₁₅H₁₂O₅·C₂H₆OS	F(000) = 736
M_r = 350.37	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.055P)² + 0.9734P] where P = (F_o² + 2F_c²)/3
1524 reflections	(Δ/σ)_max < 0.001
144 parameters	Δρ_max = 0.27 e Å⁻³
3 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₅H₁₂O₅·C₂H₆OS	V = 1588.08 (13) Å³
M_r = 350.37	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 18.8906 (8) Å	µ = 0.24 mm⁻¹
b = 6.8391 (3) Å	T = 150 K
c = 15.3542 (8) Å	0.38 × 0.09 × 0.05 mm
β = 126.815 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1524 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1382 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.988	R_int = 0.029
7177 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.10	Δρ_max = 0.27 e Å⁻³
1524 reflections	Δρ_min = −0.32 e Å⁻³
144 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	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

Symmetry codes: (ii) x, y, z+1; (iii) −x+1, y, −z+1; (iv) −x+1, y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₅·C₂H₆OS
M_r	350.37
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	150
a, b, c (Å)	18.8906 (8), 6.8391 (3), 15.3542 (8)
β (°)	126.815 (3)
V (Å³)	1588.08 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.38 × 0.09 × 0.05

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.916, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7177, 1524, 1382
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.093, 1.10
No. of reflections	1524
No. of parameters	144
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1Dⁱ	0.80	1.82	2.617 (2)	174.6
O4—H1O4···O3	0.89	1.76	2.575 (2)	151.0
O4—H1O4···O3ⁱⁱ	0.89	2.59	3.162 (2)	123.2
C4—H4C···O1ⁱⁱⁱ	0.93	2.62	3.467 (2)	152.0
C1D—H4···O4	0.96	2.70	3.401 (2)	130.3
C1D—H5···O2ⁱⁱ	0.96	2.66	3.2970 (19)	123.9

Symmetry codes: (i) x, y, z+1; (ii) −x+1, y, −z+1; (iii) −x+1, y, −z+2.

Acknowledgements

Funding from the Australian Endeavour Fellowship Scheme (SD) and and the Australian Research Council (BAN) is gratefully acknowledged.

References

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