Crystal structure and computational study of 3,4-dihy­droxy-3-hy­droxy­methyl-9-methyl-6-methyl­idene-3a,4,5,6,6a,9,9a,9b-octa­hydro­azuleno[4,5-b]furan-2,8(3H,7H)-dione

The cyclo­pentane ring displays a twist conformation and the γ-lactone ring has an envelope conformation while the cyclo­heptane ring adopts a twist-chair conformation. O—H...O hydrogen bonds link the mol­ecules, forming a three-dimensional network. A comparison between the structural parameters obtained by X-ray structure analysis and theoretical calculations give a satisfactory agreement.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.096
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.65 mm
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT791_ALERT_4_G The Model has Chirality at C1      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C4      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C5      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C6      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C7      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C8      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C10     (Chiral SPGR)          S Verify
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

3,4-Dihydroxy-3-hydroxymethyl-9-methyl-6-methylidene-3a,4,5,6,6a,9,9a,9b-octahydroazuleno[4,5-b]furan-2,8(3H,7H)-dione

Crystal data

C15H20O6	F(000) = 632
Mr = 296.31	Dx = 1.427 Mg m^−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7099 reflections
a = 8.1980 (1) Å	θ = 4.4–70.5°
b = 10.0290 (2) Å	µ = 0.92 mm^−1
c = 16.7720 (3) Å	T = 293 K
V = 1378.96 (4) Å^3	Prism, colourless
Z = 4	0.65 × 0.47 × 0.30 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	2623 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2502 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 10.2673 pixels mm^-1	θmax = 70.9°, θmin = 5.1°
ω scans	h = −10→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −12→12
Tmin = 0.773, Tmax = 1.000	l = −20→20
12778 measured reflections

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0594P)^2 + 0.2045P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max < 0.001
R[F^2 > 2σ(F^2)] = 0.035	Δρmax = 0.27 e Å^−3
wR(F^2) = 0.096	Δρmin = −0.17 e Å^−3
S = 1.05	Extinction correction: SHELXL97 (Sheldrick, 2008), FC^*=KFC[1+0.001XFC^2Λ^3/SIN(2Θ)]^-1/4
2623 reflections	Extinction coefficient: 0.0184 (14)
200 parameters	Absolute structure: Flack (1983), 1073 Friedel pairs
0 restraints	Absolute structure parameter: −0.09 (9)
Hydrogen site location: mixed

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2767 (2)	0.42340 (18)	0.94867 (10)	0.0363 (5)
O2	0.5458 (2)	0.3191 (2)	1.23883 (10)	0.0417 (6)
O3	0.6704 (3)	0.7021 (2)	0.83279 (12)	0.0430 (6)
O4	0.4798 (3)	0.3608 (2)	0.79632 (13)	0.0583 (8)
O5	0.2968 (2)	0.68723 (17)	0.81640 (11)	0.0385 (5)
O6	0.0874 (2)	0.4674 (2)	0.85721 (12)	0.0526 (7)
C1	0.6584 (3)	0.5976 (2)	0.89063 (13)	0.0298 (7)
C2	0.7676 (3)	0.6329 (3)	0.96189 (15)	0.0371 (7)
C3	0.7539 (3)	0.5438 (2)	1.03466 (14)	0.0324 (7)
C4	0.6038 (3)	0.5670 (2)	1.08525 (13)	0.0294 (7)
C5	0.4523 (3)	0.4859 (2)	1.05600 (13)	0.0259 (6)
C6	0.4448 (3)	0.4643 (2)	0.96656 (13)	0.0266 (6)
C7	0.4782 (3)	0.5846 (2)	0.91215 (13)	0.0255 (6)
C8	0.3588 (3)	0.5632 (2)	0.84275 (13)	0.0284 (6)
C9	0.2237 (3)	0.4813 (2)	0.88134 (14)	0.0331 (7)
C10	0.4595 (3)	0.3538 (2)	1.10233 (13)	0.0280 (6)
C11	0.5437 (3)	0.3898 (2)	1.17991 (13)	0.0301 (7)
C12	0.6183 (3)	0.5262 (3)	1.17351 (14)	0.0347 (7)
C13	0.8685 (3)	0.4549 (3)	1.05183 (18)	0.0476 (9)
C14	0.4213 (4)	0.4848 (3)	0.77071 (15)	0.0384 (8)
C15	0.3005 (3)	0.2790 (3)	1.11343 (15)	0.0389 (8)
H1	0.69630	0.51390	0.86680	0.0360*
H2A	0.88010	0.63170	0.94400	0.0450*
H2B	0.74270	0.72350	0.97810	0.0450*
H3O	0.755 (6)	0.703 (4)	0.812 (2)	0.0650*
H4	0.57660	0.66200	1.08300	0.0350*
H4O	0.480 (6)	0.298 (5)	0.754 (3)	0.0880*
H5	0.35370	0.53380	1.07230	0.0310*
H5O	0.200 (5)	0.668 (4)	0.794 (2)	0.0580*
H6	0.51910	0.39170	0.95210	0.0320*
H7	0.44530	0.66550	0.94070	0.0310*
H10	0.53330	0.29460	1.07310	0.0340*
H12A	0.73190	0.52400	1.18980	0.0420*
H12B	0.56050	0.58900	1.20720	0.0420*
H13A	0.85900	0.40230	1.09730	0.0570*
H13B	0.95820	0.44510	1.01840	0.0570*
H14A	0.33360	0.47210	0.73260	0.0460*
H14B	0.50810	0.53410	0.74470	0.0460*
H15A	0.25390	0.25940	1.06220	0.0580*
H15B	0.32090	0.19720	1.14150	0.0580*
H15C	0.22600	0.33280	1.14360	0.0580*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0354 (9)	0.0441 (9)	0.0295 (8)	−0.0134 (7)	−0.0076 (7)	0.0066 (8)
O2	0.0504 (11)	0.0463 (10)	0.0285 (9)	−0.0056 (9)	−0.0076 (8)	0.0089 (8)
O3	0.0399 (10)	0.0489 (11)	0.0403 (10)	−0.0025 (9)	0.0115 (8)	0.0163 (9)
O4	0.0839 (17)	0.0463 (12)	0.0448 (11)	0.0247 (12)	−0.0133 (11)	−0.0176 (9)
O5	0.0447 (10)	0.0302 (8)	0.0407 (9)	0.0053 (8)	−0.0094 (8)	0.0039 (8)
O6	0.0391 (11)	0.0711 (15)	0.0477 (11)	−0.0126 (10)	−0.0136 (9)	0.0099 (10)
C1	0.0314 (12)	0.0314 (12)	0.0266 (10)	−0.0001 (10)	0.0055 (9)	0.0032 (10)
C2	0.0306 (12)	0.0426 (13)	0.0380 (13)	−0.0097 (11)	0.0022 (10)	0.0041 (11)
C3	0.0280 (12)	0.0377 (12)	0.0316 (12)	−0.0081 (10)	−0.0029 (9)	0.0002 (10)
C4	0.0336 (12)	0.0265 (11)	0.0280 (11)	−0.0041 (9)	−0.0003 (10)	−0.0019 (9)
C5	0.0263 (10)	0.0268 (10)	0.0245 (10)	−0.0014 (8)	0.0010 (9)	−0.0005 (8)
C6	0.0271 (11)	0.0273 (11)	0.0254 (11)	−0.0027 (9)	−0.0011 (8)	0.0001 (8)
C7	0.0294 (11)	0.0239 (10)	0.0232 (10)	0.0018 (9)	0.0020 (9)	−0.0017 (8)
C8	0.0341 (12)	0.0255 (11)	0.0256 (10)	0.0043 (9)	−0.0024 (9)	−0.0004 (9)
C9	0.0339 (13)	0.0363 (12)	0.0290 (11)	−0.0009 (10)	−0.0050 (10)	−0.0016 (10)
C10	0.0322 (11)	0.0280 (11)	0.0239 (10)	−0.0019 (9)	0.0002 (9)	−0.0003 (8)
C11	0.0285 (11)	0.0360 (12)	0.0257 (11)	0.0012 (10)	−0.0001 (10)	−0.0007 (9)
C12	0.0390 (13)	0.0385 (13)	0.0266 (11)	−0.0052 (11)	−0.0022 (10)	−0.0040 (10)
C13	0.0364 (14)	0.0650 (19)	0.0413 (14)	0.0038 (13)	−0.0002 (12)	0.0033 (14)
C14	0.0478 (15)	0.0404 (14)	0.0269 (11)	0.0048 (12)	−0.0004 (11)	−0.0054 (10)
C15	0.0414 (14)	0.0425 (14)	0.0328 (12)	−0.0135 (12)	−0.0028 (11)	0.0052 (11)

Geometric parameters (Å, º)

O1—C6	1.469 (3)	C8—C9	1.523 (3)
O1—C9	1.342 (3)	C10—C11	1.517 (3)
O2—C11	1.216 (3)	C10—C15	1.515 (4)
O3—C1	1.432 (3)	C11—C12	1.502 (4)
O4—C14	1.400 (4)	C1—H1	0.9800
O5—C8	1.415 (3)	C2—H2A	0.9700
O6—C9	1.197 (3)	C2—H2B	0.9700
O3—H3O	0.78 (5)	C4—H4	0.9800
O4—H4O	0.95 (5)	C5—H5	0.9800
O5—H5O	0.90 (4)	C6—H6	0.9800
C1—C2	1.535 (3)	C7—H7	0.9800
C1—C7	1.526 (3)	C10—H10	0.9800
C2—C3	1.517 (4)	C12—H12A	0.9700
C3—C4	1.513 (3)	C12—H12B	0.9700
C3—C13	1.327 (4)	C13—H13A	0.9300
C4—C5	1.564 (3)	C13—H13B	0.9300
C4—C12	1.540 (3)	C14—H14A	0.9700
C5—C6	1.517 (3)	C14—H14B	0.9700
C5—C10	1.537 (3)	C15—H15A	0.9600
C6—C7	1.537 (3)	C15—H15B	0.9600
C7—C8	1.536 (3)	C15—H15C	0.9600
C8—C14	1.530 (3)
C6—O1—C9	110.78 (17)	C2—C1—H1	109.00
C1—O3—H3O	112 (3)	C7—C1—H1	109.00
C14—O4—H4O	111 (3)	C1—C2—H2A	108.00
C8—O5—H5O	105 (3)	C1—C2—H2B	108.00
O3—C1—C7	106.82 (19)	C3—C2—H2A	108.00
O3—C1—C2	108.59 (19)	C3—C2—H2B	108.00
C2—C1—C7	113.59 (19)	H2A—C2—H2B	107.00
C1—C2—C3	116.6 (2)	C3—C4—H4	108.00
C2—C3—C4	114.90 (19)	C5—C4—H4	108.00
C4—C3—C13	123.9 (2)	C12—C4—H4	108.00
C2—C3—C13	121.2 (2)	C4—C5—H5	108.00
C5—C4—C12	102.98 (18)	C6—C5—H5	108.00
C3—C4—C5	112.96 (18)	C10—C5—H5	108.00
C3—C4—C12	115.8 (2)	O1—C6—H6	109.00
C4—C5—C6	114.63 (19)	C5—C6—H6	109.00
C4—C5—C10	105.03 (18)	C7—C6—H6	109.00
C6—C5—C10	112.24 (17)	C1—C7—H7	108.00
O1—C6—C5	106.26 (18)	C6—C7—H7	108.00
O1—C6—C7	105.37 (18)	C8—C7—H7	108.00
C5—C6—C7	117.89 (17)	C5—C10—H10	107.00
C1—C7—C8	116.72 (19)	C11—C10—H10	107.00
C1—C7—C6	112.32 (18)	C15—C10—H10	107.00
C6—C7—C8	103.10 (17)	C4—C12—H12A	111.00
O5—C8—C7	110.05 (17)	C4—C12—H12B	110.00
O5—C8—C9	110.22 (19)	C11—C12—H12A	110.00
C9—C8—C14	107.58 (19)	C11—C12—H12B	111.00
C7—C8—C14	117.2 (2)	H12A—C12—H12B	109.00
O5—C8—C14	109.00 (19)	C3—C13—H13A	120.00
C7—C8—C9	102.52 (18)	C3—C13—H13B	120.00
O1—C9—O6	122.5 (2)	H13A—C13—H13B	120.00
O1—C9—C8	110.8 (2)	O4—C14—H14A	110.00
O6—C9—C8	126.7 (2)	O4—C14—H14B	110.00
C5—C10—C11	104.24 (17)	C8—C14—H14A	110.00
C5—C10—C15	117.1 (2)	C8—C14—H14B	110.00
C11—C10—C15	113.83 (19)	H14A—C14—H14B	108.00
O2—C11—C12	125.7 (2)	C10—C15—H15A	109.00
O2—C11—C10	124.4 (2)	C10—C15—H15B	109.00
C10—C11—C12	109.92 (18)	C10—C15—H15C	110.00
C4—C12—C11	106.21 (19)	H15A—C15—H15B	109.00
O4—C14—C8	109.2 (2)	H15A—C15—H15C	109.00
O3—C1—H1	109.00	H15B—C15—H15C	109.00
C6—O1—C9—O6	−176.4 (2)	C6—C5—C10—C15	−79.1 (3)
C6—O1—C9—C8	3.7 (2)	C4—C5—C6—O1	−163.79 (17)
C9—O1—C6—C5	139.66 (18)	O1—C6—C7—C1	−151.38 (17)
C9—O1—C6—C7	13.8 (2)	C5—C6—C7—C8	−143.2 (2)
O3—C1—C2—C3	171.8 (2)	O1—C6—C7—C8	−24.9 (2)
O3—C1—C7—C8	54.4 (2)	C5—C6—C7—C1	90.3 (2)
C7—C1—C2—C3	53.2 (3)	C1—C7—C8—C14	32.2 (3)
O3—C1—C7—C6	173.17 (17)	C6—C7—C8—O5	143.33 (18)
C2—C1—C7—C6	−67.1 (2)	C6—C7—C8—C9	26.1 (2)
C2—C1—C7—C8	174.11 (19)	C6—C7—C8—C14	−91.4 (2)
C1—C2—C3—C13	104.8 (3)	C1—C7—C8—C9	149.70 (18)
C1—C2—C3—C4	−76.4 (3)	C1—C7—C8—O5	−93.1 (2)
C2—C3—C4—C5	86.5 (2)	O5—C8—C9—O6	43.5 (3)
C2—C3—C4—C12	−155.1 (2)	O5—C8—C9—O1	−136.56 (19)
C13—C3—C4—C5	−94.8 (3)	C14—C8—C9—O1	104.7 (2)
C13—C3—C4—C12	23.7 (3)	C14—C8—C9—O6	−75.2 (3)
C12—C4—C5—C10	−34.5 (2)	O5—C8—C14—O4	−178.8 (2)
C12—C4—C5—C6	−158.11 (19)	C7—C8—C14—O4	55.4 (3)
C5—C4—C12—C11	26.5 (2)	C9—C8—C14—O4	−59.3 (3)
C3—C4—C5—C10	91.2 (2)	C7—C8—C9—O1	−19.4 (2)
C3—C4—C5—C6	−32.5 (2)	C7—C8—C9—O6	160.6 (2)
C3—C4—C12—C11	−97.3 (2)	C5—C10—C11—O2	165.6 (2)
C10—C5—C6—C7	−165.7 (2)	C5—C10—C11—C12	−12.6 (3)
C4—C5—C10—C15	155.79 (19)	C15—C10—C11—O2	36.8 (3)
C6—C5—C10—C11	154.2 (2)	C15—C10—C11—C12	−141.4 (2)
C4—C5—C10—C11	29.1 (2)	O2—C11—C12—C4	172.8 (2)
C4—C5—C6—C7	−46.0 (3)	C10—C11—C12—C4	−9.1 (3)
C10—C5—C6—O1	76.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^i	0.78 (5)	2.06 (4)	2.818 (3)	168 (4)
O4—H4O···O3^ii	0.95 (5)	2.14 (5)	2.956 (3)	144 (4)
O4—H4O···O5^ii	0.95 (5)	2.45 (5)	3.156 (3)	132 (4)
O5—H5O···O6	0.90 (4)	2.45 (4)	2.877 (3)	109 (3)
O5—H5O···O2^iii	0.90 (4)	2.22 (4)	3.096 (2)	164 (4)

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, −y+1, z−1/2.