Ranunculin.

In the title mol-ecule {systematic name: (5S)-5-[(β-d-gluco-pyranos-yloxy)meth-yl]furan-2(5H)-one}, C(11)H(16)O(8), the five-membered ring is essentially planar, the maximum deviation being 0.0151 (13) Å for the O atom. The six-membered ring adopts a chair conformation with puckering parameters Q = 0.581 (2) Å, θ = 9.0 (2)° and ϕ = 39.7 (13)°, and with all of the substituents of the glucoside unit having normal equatorial orientations. The crystal structure is stabilized by extensive O-H⋯O and C-H⋯O hydrogen bonding, resulting in a three-dimensional network.

Related literature

For background to ranunculin, see: Hill & van Heyningen (1951 ▶); Bai et al. (1996 ▶); Benn & Yelland (1968 ▶); Boll (1968 ▶); Camps et al. (1982 ▶); Fang et al. (1989 ▶). For chemical and spectrometric data for closely related, simple butenolides, see: Perry et al. (1996 ▶). For comparison bond distances, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C11H16O8

M = 276.24

Monoclinic,

a = 5.7944 (4) Å

b = 6.9359 (3) Å

c = 15.0491 (10) Å

β = 97.895 (2)°

V = 599.08 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 173 K

0.30 × 0.24 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer with APEXII CCD

Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T min = 0.961, T max = 0.997

1926 measured reflections

1133 independent reflections

1112 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.069

S = 1.04

1133 reflections

184 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.16 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034847/fl2315sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034847/fl2315Isup2.hkl

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

C11H16O8	F(000) = 292
Mr = 276.24	Dx = 1.531 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1560 reflections
a = 5.7944 (4) Å	θ = 1.0–30.0°
b = 6.9359 (3) Å	µ = 0.13 mm−1
c = 15.0491 (10) Å	T = 173 K
β = 97.895 (2)°	Plate, colorless
V = 599.08 (6) Å3	0.30 × 0.24 × 0.02 mm
Z = 2

Nonius APEXII CCD [APEXII is a Bruker machine - is this a KappaCCD upgraded with an APEXII CCD?]diffractometer	1133 independent reflections
Radiation source: fine-focus sealed tube	1112 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ & ω scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −6→6
Tmin = 0.961, Tmax = 0.997	k = −6→8
1926 measured reflections	l = −17→17

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)] = 0.026	Hydrogen site location: difference Fourier map
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.040P)2 + 0.1617P] where P = (Fo2 + 2Fc2)/3
1133 reflections	(Δ/σ)max = 0.002
184 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.16 e Å−3

Experimental. NMR data (400 MHz, 1H; 100 MHz 13C) for a solution in D2O containing sodium 3-trimethylsilylpropionate-2,3 - d4 as reference: δH (400 MHz) 7.77 (1H, dd, J = 1.5 and 5.8 Hz, H-4), 6.3 (1H, dd, J = 2.1 and 5.8 Hz, H-3), 5.47 (1H, m), 4.48 (1H, d, J = 7.9 Hz, H-1'), 4.30 (1H, dd, J = 3.2 and 12.2 Hz, H-6 A), 3.95 (1H, dd, J = 5.8 and 12.2 Hz, H-6B), 3.91 (1H, dd, J = 2.1 and 12.5 Hz, H-6A'), 3.72 (1H, dd, J = 5.8 and 12.5 Hz, H-6B'), 3.48 (1H, dd, dd, J = ca 9 Hz H-3'), 3.43 (1H, m, H-5'), 3.37 (1H, dd, J = ca 9 Hz, H=4'), and 3.25 (1H, dd, J = 7.9 and 9.2 Hz, H-2'); δC 179.2 s (C-2), 158.5 d (C-4), 124.7 d (C-3), 105.6 d (C-1'), 86.9 d (C-5), 78.7 d (C-5'), 78.3 d (C-3'), 75.6 d (C-2'), 72.2 d (C-4'), 71.7 t (C-6), 63.3 t (C-6').

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
O1	0.9146 (3)	−0.1112 (2)	0.96815 (9)	0.0225 (4)
O2	1.0618 (3)	−0.0493 (3)	1.11025 (10)	0.0309 (4)
O3	0.4499 (2)	0.0377 (2)	0.79524 (9)	0.0200 (3)
O4	0.5209 (2)	0.3269 (2)	0.73224 (9)	0.0188 (3)
O5	0.1227 (3)	−0.0568 (2)	0.63887 (10)	0.0241 (4)
H5O	0.085 (5)	−0.121 (5)	0.6833 (19)	0.036*
O6	−0.0241 (2)	0.2692 (2)	0.53178 (10)	0.0208 (4)
H6O	−0.025 (5)	0.336 (5)	0.479 (2)	0.031*
O7	0.3667 (3)	0.5126 (3)	0.50561 (9)	0.0215 (3)
H7O	0.259 (5)	0.591 (5)	0.4895 (18)	0.032*
O8	0.8805 (3)	0.6376 (3)	0.72096 (10)	0.0277 (4)
H8O	0.893 (5)	0.563 (5)	0.769 (2)	0.042*
C1	0.6798 (3)	0.0332 (4)	0.84401 (13)	0.0216 (5)
H1A	0.7191	0.1601	0.8721	0.026*
H1B	0.7947	0.0036	0.8030	0.026*
C2	0.8918 (4)	−0.0724 (3)	1.05518 (13)	0.0225 (5)
C3	0.6434 (4)	−0.0666 (4)	1.06406 (14)	0.0252 (5)
H3	0.5794	−0.0486	1.1183	0.030*
C4	0.5229 (4)	−0.0912 (3)	0.98301 (14)	0.0243 (5)
H4	0.3578	−0.0895	0.9699	0.029*
C5	0.6862 (4)	−0.1216 (3)	0.91570 (13)	0.0204 (5)
H5	0.6609	−0.2517	0.8874	0.025*
C6	0.4469 (4)	0.1343 (3)	0.71336 (13)	0.0178 (4)
H6	0.5552	0.0694	0.6765	0.021*
C7	0.2004 (3)	0.1338 (3)	0.66293 (13)	0.0176 (4)
H7	0.0906	0.1980	0.6994	0.021*
C8	0.2093 (3)	0.2433 (3)	0.57590 (13)	0.0167 (4)
H8	0.2985	0.1652	0.5363	0.020*
C9	0.3238 (3)	0.4413 (3)	0.59065 (13)	0.0172 (4)
H9	0.2164	0.5310	0.6170	0.021*
C10	0.5559 (3)	0.4305 (3)	0.65204 (13)	0.0180 (4)
H10	0.6738	0.3622	0.6208	0.022*
C11	0.6423 (4)	0.6302 (3)	0.67948 (14)	0.0218 (5)
H11A	0.6248	0.7137	0.6256	0.026*
H11B	0.5424	0.6840	0.7217	0.026*

	U11	U22	U33	U12	U13	U23
O1	0.0203 (7)	0.0294 (9)	0.0169 (7)	0.0038 (6)	−0.0002 (5)	0.0024 (6)
O2	0.0327 (8)	0.0329 (10)	0.0233 (8)	0.0036 (8)	−0.0095 (7)	−0.0014 (8)
O3	0.0212 (7)	0.0242 (8)	0.0137 (7)	−0.0011 (7)	−0.0005 (5)	0.0038 (6)
O4	0.0226 (7)	0.0190 (8)	0.0143 (7)	−0.0026 (6)	0.0005 (5)	−0.0001 (6)
O5	0.0317 (8)	0.0223 (8)	0.0172 (7)	−0.0077 (7)	−0.0007 (6)	0.0020 (7)
O6	0.0177 (7)	0.0259 (8)	0.0174 (7)	−0.0007 (6)	−0.0027 (6)	0.0030 (7)
O7	0.0218 (7)	0.0257 (8)	0.0172 (7)	0.0016 (7)	0.0036 (6)	0.0063 (7)
O8	0.0262 (8)	0.0330 (9)	0.0227 (8)	−0.0102 (8)	−0.0010 (6)	0.0034 (8)
C1	0.0200 (10)	0.0262 (12)	0.0175 (10)	−0.0020 (10)	−0.0010 (8)	0.0041 (9)
C2	0.0302 (11)	0.0188 (10)	0.0175 (9)	0.0063 (10)	0.0000 (9)	0.0026 (9)
C3	0.0306 (11)	0.0257 (11)	0.0201 (10)	0.0037 (10)	0.0064 (8)	0.0025 (10)
C4	0.0235 (10)	0.0234 (12)	0.0264 (12)	0.0004 (10)	0.0044 (9)	0.0071 (10)
C5	0.0217 (10)	0.0214 (11)	0.0168 (10)	−0.0001 (9)	−0.0023 (8)	0.0016 (9)
C6	0.0216 (10)	0.0179 (10)	0.0138 (9)	−0.0003 (9)	0.0020 (7)	0.0016 (9)
C7	0.0190 (10)	0.0188 (10)	0.0151 (9)	−0.0014 (9)	0.0025 (7)	0.0003 (9)
C8	0.0152 (10)	0.0207 (10)	0.0135 (9)	0.0003 (9)	−0.0001 (8)	−0.0008 (8)
C9	0.0185 (10)	0.0191 (10)	0.0143 (9)	0.0010 (9)	0.0038 (7)	0.0010 (9)
C10	0.0180 (10)	0.0216 (10)	0.0147 (9)	−0.0004 (10)	0.0038 (8)	0.0017 (9)
C11	0.0253 (11)	0.0206 (11)	0.0189 (10)	−0.0016 (9)	0.0004 (8)	0.0006 (10)

O1—C2	1.361 (2)	C2—C3	1.464 (3)
O1—C5	1.447 (2)	C3—C4	1.331 (3)
O2—C2	1.208 (3)	C3—H3	0.9500
O3—C6	1.401 (2)	C4—C5	1.493 (3)
O3—C1	1.430 (2)	C4—H4	0.9500
O4—C6	1.419 (3)	C5—H5	1.0000
O4—C10	1.443 (2)	C6—C7	1.523 (3)
O5—C7	1.427 (3)	C6—H6	1.0000
O5—H5O	0.86 (3)	C7—C8	1.521 (3)
O6—C8	1.434 (2)	C7—H7	1.0000
O6—H6O	0.92 (3)	C8—C9	1.528 (3)
O7—C9	1.425 (2)	C8—H8	1.0000
O7—H7O	0.84 (3)	C9—C10	1.525 (2)
O8—C11	1.435 (3)	C9—H9	1.0000
O8—H8O	0.88 (3)	C10—C11	1.511 (3)
C1—C5	1.519 (3)	C10—H10	1.0000
C1—H1A	0.9900	C11—H11A	0.9900
C1—H1B	0.9900	C11—H11B	0.9900
C2—O1—C5	109.40 (15)	O4—C6—H6	109.9
C6—O3—C1	111.09 (15)	C7—C6—H6	109.9
C6—O4—C10	112.00 (15)	O5—C7—C8	106.92 (16)
C7—O5—H5O	113 (2)	O5—C7—C6	111.72 (17)
C8—O6—H6O	110.7 (18)	C8—C7—C6	106.69 (16)
C9—O7—H7O	105.7 (19)	O5—C7—H7	110.5
C11—O8—H8O	107 (2)	C8—C7—H7	110.5
O3—C1—C5	108.08 (17)	C6—C7—H7	110.5
O3—C1—H1A	110.1	O6—C8—C7	108.63 (16)
C5—C1—H1A	110.1	O6—C8—C9	108.56 (17)
O3—C1—H1B	110.1	C7—C8—C9	112.90 (16)
C5—C1—H1B	110.1	O6—C8—H8	108.9
H1A—C1—H1B	108.4	C7—C8—H8	108.9
O2—C2—O1	120.56 (19)	C9—C8—H8	108.9
O2—C2—C3	130.8 (2)	O7—C9—C10	108.24 (15)
O1—C2—C3	108.66 (17)	O7—C9—C8	107.89 (16)
C4—C3—C2	108.1 (2)	C10—C9—C8	111.93 (17)
C4—C3—H3	125.9	O7—C9—H9	109.6
C2—C3—H3	125.9	C10—C9—H9	109.6
C3—C4—C5	109.8 (2)	C8—C9—H9	109.6
C3—C4—H4	125.1	O4—C10—C11	107.91 (16)
C5—C4—H4	125.1	O4—C10—C9	108.49 (15)
O1—C5—C4	103.91 (16)	C11—C10—C9	110.63 (17)
O1—C5—C1	106.48 (16)	O4—C10—H10	109.9
C4—C5—C1	115.19 (19)	C11—C10—H10	109.9
O1—C5—H5	110.3	C9—C10—H10	109.9
C4—C5—H5	110.3	O8—C11—C10	114.47 (18)
C1—C5—H5	110.3	O8—C11—H11A	108.6
O3—C6—O4	107.90 (15)	C10—C11—H11A	108.6
O3—C6—C7	109.54 (16)	O8—C11—H11B	108.6
O4—C6—C7	109.80 (16)	C10—C11—H11B	108.6
O3—C6—H6	109.9	H11A—C11—H11B	107.6
C6—O3—C1—C5	−162.86 (17)	O3—C6—C7—C8	179.11 (17)
C5—O1—C2—O2	−176.8 (2)	O4—C6—C7—C8	60.8 (2)
C5—O1—C2—C3	3.2 (2)	O5—C7—C8—O6	68.0 (2)
O2—C2—C3—C4	176.8 (3)	C6—C7—C8—O6	−172.30 (16)
O1—C2—C3—C4	−3.3 (3)	O5—C7—C8—C9	−171.50 (16)
C2—C3—C4—C5	2.0 (3)	C6—C7—C8—C9	−51.8 (2)
C2—O1—C5—C4	−2.0 (2)	O6—C8—C9—O7	−71.42 (19)
C2—O1—C5—C1	120.06 (19)	C7—C8—C9—O7	168.07 (16)
C3—C4—C5—O1	−0.1 (3)	O6—C8—C9—C10	169.60 (14)
C3—C4—C5—C1	−116.2 (2)	C7—C8—C9—C10	49.1 (2)
O3—C1—C5—O1	−175.41 (16)	C6—O4—C10—C11	−177.97 (16)
O3—C1—C5—C4	−60.8 (2)	C6—O4—C10—C9	62.1 (2)
C1—O3—C6—O4	−61.2 (2)	O7—C9—C10—O4	−169.84 (18)
C1—O3—C6—C7	179.26 (17)	C8—C9—C10—O4	−51.1 (2)
C10—O4—C6—O3	171.64 (15)	O7—C9—C10—C11	72.0 (2)
C10—O4—C6—C7	−69.02 (19)	C8—C9—C10—C11	−169.25 (17)
O3—C6—C7—O5	−64.4 (2)	O4—C10—C11—O8	74.2 (2)
O4—C6—C7—O5	177.31 (17)	C9—C10—C11—O8	−167.27 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O8i	0.86 (3)	2.17 (3)	2.910 (2)	144 (3)
O6—H6O···O5ii	0.92 (3)	1.94 (3)	2.824 (2)	162 (3)
O7—H7O···O6ii	0.84 (3)	1.84 (3)	2.668 (2)	173 (3)
O8—H8O···O2iii	0.88 (3)	1.96 (3)	2.830 (2)	167 (3)
C3—H3···O4iv	0.95	2.55	3.413 (3)	151
C4—H4···O1v	0.95	2.57	3.504 (3)	168
C8—H8···O7vi	1.00	2.37	3.306 (3)	155
C1—H1A···O2iii	0.99	2.38	3.289 (3)	153
C10—H10···O6vii	1.00	2.43	3.415 (3)	167
O6—H6O···O7	0.92 (3)	2.56 (3)	2.894 (2)	102 (2)
C11—H11A···O7	0.99	2.59	2.986 (3)	104

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5O⋯O8i	0.86 (3)	2.17 (3)	2.910 (2)	144 (3)
O6—H6O⋯O5ii	0.92 (3)	1.94 (3)	2.824 (2)	162 (3)
O7—H7O⋯O6ii	0.84 (3)	1.84 (3)	2.668 (2)	173 (3)
O8—H8O⋯O2iii	0.88 (3)	1.96 (3)	2.830 (2)	167 (3)
O6—H6O⋯O7	0.92 (3)	2.56 (3)	2.894 (2)	102 (2)

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