The di­acetate of (+)-pinoresinol

The crystal structure of a monoclinic form of the di­acetate of (+)-pinoresinol, the di­acetate of 4,4'-[(1S,3aR,4S,6aR)-tetra­hydro-1H,3H-furo[3,4-c]­furan-1,4-diyl]bis[2-­methoxy­phen­ol], C₂₄H₂₆O₈, has been determined. Attempts to determine the crystal structure of a triclinic form of this compound did not give satisfactory results. One of the five-membered rings in the central dioxabi­cyclo­octane ring system adopts an envelope conform­ation, with a bridge C atom as `flap'. The other five-membered ring is twisted on the benzyl­ic C atom and the adjacent bridge C atom.

Key indicators

• Single-crystal X-ray study
• T = 183 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.149
• Data-to-parameter ratio = 10.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           30.51
         From the CIF: _reflns_number_total               3326
         Count of symmetry unique reflns         3330
         Completeness (_total/calc)             99.88%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2001); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL.

2,2'-dimethoxy-4,4'-(tetrahydro-1H,3H-furo[3,4-c]furan-1,4-diyl)diphenyl 1,1'-diacetate

Crystal data

C24H26O8	Dx = 1.397 Mg m^−3
Mr = 442.45	Melting point: 439 K K
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.9938 (1) Å	Cell parameters from 6622 reflections
b = 14.4485 (2) Å	θ = 2.2–30.5°
c = 9.8439 (1) Å	µ = 0.11 mm^−1
β = 112.278 (1)°	T = 183 K
V = 1052.09 (2) Å^3	Plate, colourless
Z = 2	0.20 × 0.14 × 0.06 mm
F(000) = 468

Data collection

Siemens SMART CCD diffractometer	3326 independent reflections
Radiation source: fine-focus sealed tube	2600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 30.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.979, Tmax = 0.994	k = −20→20
16818 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
3326 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.29 e Å^−3
1 restraint	Δρmin = −0.23 e Å^−3

Special details

Experimental. Data were collected at 183 K using a Siemens SMART CCD diffractometer equipped with a Siemens LT-2 A low temperature device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 6622 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2081 (3)	1.02708 (17)	0.1643 (2)	0.0338 (5)
O2	0.3322 (3)	0.87679 (17)	0.0771 (2)	0.0306 (5)
O3	0.5275 (4)	0.84512 (17)	0.7586 (3)	0.0401 (6)
O4	0.6064 (4)	1.11024 (17)	0.9068 (3)	0.0387 (6)
O5	0.9870 (3)	0.93916 (16)	1.4976 (2)	0.0321 (5)
O6	0.9017 (3)	1.09780 (17)	1.5954 (2)	0.0285 (5)
O7	0.0801 (3)	0.8029 (2)	0.0667 (3)	0.0387 (6)
O8	1.1669 (3)	1.13639 (18)	1.5810 (3)	0.0332 (5)
C1	0.4608 (4)	0.9171 (2)	0.5232 (3)	0.0256 (6)
C2	0.3561 (4)	0.9831 (2)	0.4219 (3)	0.0263 (6)
H2	0.3147	1.0368	0.4553	0.037 (10)*
C3	0.3136 (4)	0.9699 (2)	0.2733 (3)	0.0251 (6)
C4	0.3772 (4)	0.8902 (2)	0.2279 (3)	0.0267 (6)
C5	0.4848 (4)	0.8273 (2)	0.3267 (4)	0.0283 (6)
H5	0.5290	0.7746	0.2932	0.054 (13)*
C6	0.5291 (4)	0.8410 (2)	0.4758 (4)	0.0283 (6)
H6	0.6058	0.7984	0.5450	0.046 (12)*
C7	0.1631 (5)	1.1148 (3)	0.2076 (4)	0.0353 (7)
H7A	0.0955	1.1056	0.2713	0.019 (8)*
H7B	0.0888	1.1497	0.1202	0.059 (14)*
H7C	0.2742	1.1493	0.2610	0.038 (11)*
C8	0.4988 (4)	0.9329 (2)	0.6843 (3)	0.0263 (6)
H8	0.3916	0.9637	0.6935	0.036 (10)*
C9	0.6677 (4)	0.9902 (2)	0.7679 (3)	0.0230 (6)
H9	0.7672	0.9777	0.7322	0.023 (8)*
C10	0.6335 (5)	1.0930 (2)	0.7742 (3)	0.0299 (6)
H10A	0.7383	1.1289	0.7727	0.089 (19)*
H10B	0.5251	1.1117	0.6885	0.036 (10)*
C11	0.6879 (4)	1.0428 (2)	1.1465 (3)	0.0226 (6)
C12	0.8018 (4)	0.9790 (2)	1.2434 (3)	0.0250 (6)
H12	0.8309	0.9230	1.2067	0.030 (10)*
C13	0.8740 (4)	0.9962 (2)	1.3943 (3)	0.0247 (6)
C14	0.8297 (4)	1.0798 (2)	1.4442 (3)	0.0250 (6)
C15	0.7111 (4)	1.1407 (2)	1.3501 (3)	0.0271 (6)
H15	0.6784	1.1956	1.3870	0.035 (10)*
C16	0.6384 (4)	1.1224 (2)	1.2006 (3)	0.0255 (6)
H16	0.5547	1.1644	1.1354	0.041 (11)*
C17	1.0113 (5)	0.8484 (2)	1.4504 (4)	0.0344 (7)
H17A	0.8935	0.8180	1.4052	0.072 (16)*
H17B	1.0885	0.8122	1.5352	0.073 (17)*
H17C	1.0688	0.8528	1.3786	0.033 (10)*
C18	0.6113 (4)	1.0241 (2)	0.9835 (3)	0.0237 (6)
H18	0.4848	1.0008	0.9549	0.024 (9)*
C19	0.7163 (4)	0.9566 (2)	0.9258 (3)	0.0223 (5)
H19	0.8494	0.9598	0.9839	0.034 (10)*
C20	0.6465 (4)	0.8569 (2)	0.9081 (3)	0.0277 (6)
H20A	0.7487	0.8129	0.9333	0.040 (11)*
H20B	0.5812	0.8453	0.9741	0.038 (11)*
C21	0.1711 (4)	0.8337 (2)	0.0038 (4)	0.0270 (6)
C22	0.1270 (5)	0.8325 (3)	−0.1572 (4)	0.0353 (7)
H22A	0.0365	0.7844	−0.2029	0.072 (17)*
H22B	0.2367	0.8193	−0.1758	0.064 (15)*
H22C	0.0786	0.8929	−0.1990	0.11 (2)*
C23	1.0789 (4)	1.1229 (2)	1.6550 (3)	0.0262 (6)
C24	1.1414 (4)	1.1345 (3)	1.8166 (4)	0.0360 (8)
H24A	1.2698	1.1513	1.8564	0.087 (18)*
H24B	1.1247	1.0763	1.8610	0.076 (18)*
H24C	1.0711	1.1835	1.8389	0.042 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0434 (13)	0.0315 (13)	0.0239 (11)	0.0059 (10)	0.0101 (10)	0.0033 (9)
O2	0.0334 (12)	0.0348 (13)	0.0278 (11)	−0.0090 (10)	0.0162 (10)	−0.0081 (9)
O3	0.0588 (16)	0.0295 (13)	0.0239 (11)	−0.0183 (12)	0.0065 (11)	0.0021 (9)
O4	0.0641 (16)	0.0275 (12)	0.0315 (12)	0.0159 (11)	0.0260 (12)	0.0092 (10)
O5	0.0404 (13)	0.0253 (11)	0.0247 (10)	0.0051 (10)	0.0059 (9)	0.0017 (9)
O6	0.0290 (11)	0.0346 (12)	0.0246 (10)	−0.0036 (9)	0.0133 (9)	−0.0053 (9)
O7	0.0309 (12)	0.0484 (15)	0.0377 (14)	−0.0089 (11)	0.0141 (10)	0.0027 (11)
O8	0.0279 (10)	0.0361 (13)	0.0378 (12)	−0.0025 (10)	0.0151 (10)	−0.0075 (10)
C1	0.0260 (14)	0.0269 (15)	0.0239 (14)	−0.0063 (11)	0.0094 (12)	−0.0020 (12)
C2	0.0292 (15)	0.0255 (14)	0.0249 (14)	−0.0006 (12)	0.0109 (12)	−0.0027 (12)
C3	0.0269 (14)	0.0239 (15)	0.0257 (14)	−0.0021 (11)	0.0113 (12)	−0.0020 (11)
C4	0.0306 (15)	0.0264 (15)	0.0269 (15)	−0.0062 (12)	0.0150 (13)	−0.0046 (12)
C5	0.0319 (16)	0.0245 (15)	0.0324 (16)	−0.0011 (12)	0.0165 (13)	−0.0027 (12)
C6	0.0285 (15)	0.0245 (15)	0.0306 (16)	0.0001 (12)	0.0097 (12)	0.0018 (12)
C7	0.0442 (19)	0.0312 (17)	0.0325 (17)	0.0060 (14)	0.0169 (15)	0.0035 (13)
C8	0.0291 (15)	0.0264 (15)	0.0234 (14)	−0.0033 (12)	0.0098 (12)	0.0009 (11)
C9	0.0218 (13)	0.0259 (14)	0.0208 (13)	−0.0007 (11)	0.0073 (11)	−0.0012 (11)
C10	0.0385 (17)	0.0262 (15)	0.0280 (15)	−0.0032 (13)	0.0160 (13)	0.0004 (12)
C11	0.0237 (14)	0.0203 (13)	0.0233 (13)	−0.0030 (11)	0.0084 (11)	0.0004 (11)
C12	0.0297 (14)	0.0194 (13)	0.0253 (14)	0.0010 (11)	0.0096 (12)	−0.0015 (11)
C13	0.0268 (14)	0.0221 (14)	0.0259 (14)	−0.0027 (11)	0.0108 (12)	0.0010 (11)
C14	0.0265 (14)	0.0267 (15)	0.0224 (14)	−0.0042 (11)	0.0100 (12)	−0.0050 (11)
C15	0.0247 (13)	0.0260 (15)	0.0335 (16)	−0.0018 (11)	0.0144 (12)	−0.0069 (12)
C16	0.0225 (13)	0.0237 (14)	0.0288 (14)	0.0029 (11)	0.0079 (11)	0.0004 (12)
C17	0.0423 (18)	0.0251 (16)	0.0306 (16)	0.0044 (14)	0.0079 (14)	0.0005 (13)
C18	0.0218 (13)	0.0257 (15)	0.0226 (13)	0.0032 (11)	0.0071 (11)	0.0045 (11)
C19	0.0217 (12)	0.0208 (13)	0.0217 (13)	0.0022 (10)	0.0051 (11)	0.0007 (10)
C20	0.0312 (15)	0.0241 (15)	0.0287 (15)	0.0020 (12)	0.0125 (13)	0.0038 (12)
C21	0.0254 (14)	0.0250 (15)	0.0300 (15)	0.0024 (12)	0.0099 (12)	−0.0023 (12)
C22	0.0388 (18)	0.0388 (19)	0.0259 (16)	−0.0013 (15)	0.0096 (14)	−0.0045 (14)
C23	0.0277 (14)	0.0212 (14)	0.0293 (14)	0.0041 (12)	0.0104 (12)	−0.0047 (12)
C24	0.0311 (16)	0.045 (2)	0.0304 (16)	0.0021 (15)	0.0097 (13)	−0.0095 (15)

Geometric parameters (Å, º)

O1—C3	1.363 (4)	C9—H9	1.0000
O1—C7	1.426 (4)	C10—H10A	0.9900
O2—C21	1.365 (4)	C10—H10B	0.9900
O2—C4	1.402 (4)	C11—C12	1.389 (4)
O3—C20	1.428 (4)	C11—C16	1.387 (4)
O3—C8	1.439 (4)	C11—C18	1.509 (4)
O4—C18	1.448 (4)	C12—C13	1.397 (4)
O4—C10	1.424 (4)	C12—H12	0.9500
O5—C13	1.354 (4)	C13—C14	1.399 (4)
O5—C17	1.428 (4)	C14—C15	1.366 (5)
O6—C23	1.361 (4)	C15—C16	1.387 (4)
O6—C14	1.401 (4)	C15—H15	0.9500
O7—C21	1.205 (4)	C16—H16	0.9500
O8—C23	1.206 (4)	C17—H17A	0.9800
C1—C6	1.385 (4)	C17—H17B	0.9800
C1—C2	1.404 (5)	C17—H17C	0.9800
C1—C8	1.514 (4)	C18—C19	1.530 (4)
C2—C3	1.384 (4)	C18—H18	1.0000
C2—H2	0.9500	C19—C20	1.530 (4)
C3—C4	1.399 (4)	C19—H19	1.0000
C4—C5	1.370 (5)	C20—H20A	0.9900
C5—C6	1.388 (4)	C20—H20B	0.9900
C5—H5	0.9500	C21—C22	1.488 (4)
C6—H6	0.9500	C22—H22A	0.9800
C7—H7A	0.9800	C22—H22B	0.9800
C7—H7B	0.9800	C22—H22C	0.9800
C7—H7C	0.9800	C23—C24	1.484 (4)
C8—C9	1.531 (4)	C24—H24A	0.9800
C8—H8	1.0000	C24—H24B	0.9800
C9—C10	1.516 (4)	C24—H24C	0.9800
C9—C19	1.531 (4)
C3—O1—C7	117.0 (2)	O5—C13—C12	125.4 (3)
C21—O2—C4	115.8 (2)	O5—C13—C14	116.6 (3)
C20—O3—C8	109.5 (2)	C12—C13—C14	118.0 (3)
C18—O4—C10	110.1 (2)	C15—C14—C13	121.4 (3)
C13—O5—C17	116.7 (2)	C15—C14—O6	120.1 (3)
C23—O6—C14	116.7 (2)	C13—C14—O6	118.5 (3)
C6—C1—C2	120.3 (3)	C14—C15—C16	120.0 (3)
C6—C1—C8	121.6 (3)	C14—C15—H15	120.0
C2—C1—C8	118.1 (3)	C16—C15—H15	120.0
C3—C2—C1	119.9 (3)	C15—C16—C11	120.0 (3)
C3—C2—H2	120.1	C15—C16—H16	120.0
C1—C2—H2	120.1	C11—C16—H16	120.0
O1—C3—C2	125.4 (3)	O5—C17—H17A	109.5
O1—C3—C4	116.0 (3)	O5—C17—H17B	109.5
C2—C3—C4	118.6 (3)	H17A—C17—H17B	109.5
C5—C4—C3	121.7 (3)	O5—C17—H17C	109.5
C5—C4—O2	120.0 (3)	H17A—C17—H17C	109.5
C3—C4—O2	118.3 (3)	H17B—C17—H17C	109.5
C4—C5—C6	119.8 (3)	O4—C18—C11	108.7 (2)
C4—C5—H5	120.1	O4—C18—C19	105.3 (2)
C6—C5—H5	120.1	C11—C18—C19	116.8 (2)
C1—C6—C5	119.7 (3)	O4—C18—H18	108.6
C1—C6—H6	120.2	C11—C18—H18	108.6
C5—C6—H6	120.2	C19—C18—H18	108.6
O1—C7—H7A	109.5	C9—C19—C18	102.2 (2)
O1—C7—H7B	109.5	C9—C19—C20	104.0 (2)
H7A—C7—H7B	109.5	C18—C19—C20	114.5 (2)
O1—C7—H7C	109.5	C9—C19—H19	111.8
H7A—C7—H7C	109.5	C18—C19—H19	111.8
H7B—C7—H7C	109.5	C20—C19—H19	111.8
O3—C8—C1	109.2 (3)	O3—C20—C19	107.5 (2)
O3—C8—C9	105.4 (2)	O3—C20—H20A	110.2
C1—C8—C9	115.5 (2)	C19—C20—H20A	110.2
O3—C8—H8	108.8	O3—C20—H20B	110.2
C1—C8—H8	108.8	C19—C20—H20B	110.2
C9—C8—H8	108.8	H20A—C20—H20B	108.5
C8—C9—C10	114.6 (3)	O7—C21—O2	122.0 (3)
C8—C9—C19	101.9 (2)	O7—C21—C22	126.7 (3)
C10—C9—C19	104.5 (2)	O2—C21—C22	111.4 (3)
C8—C9—H9	111.7	C21—C22—H22A	109.5
C10—C9—H9	111.7	C21—C22—H22B	109.5
C19—C9—H9	111.7	H22A—C22—H22B	109.5
O4—C10—C9	107.5 (2)	C21—C22—H22C	109.5
O4—C10—H10A	110.2	H22A—C22—H22C	109.5
C9—C10—H10A	110.2	H22B—C22—H22C	109.5
O4—C10—H10B	110.2	O8—C23—O6	122.2 (3)
C9—C10—H10B	110.2	O8—C23—C24	126.3 (3)
H10A—C10—H10B	108.5	O6—C23—C24	111.4 (3)
C12—C11—C16	119.6 (3)	C23—C24—H24A	109.5
C12—C11—C18	120.5 (3)	C23—C24—H24B	109.5
C16—C11—C18	119.8 (3)	H24A—C24—H24B	109.5
C11—C12—C13	120.8 (3)	C23—C24—H24C	109.5
C11—C12—H12	119.6	H24A—C24—H24C	109.5
C13—C12—H12	119.6	H24B—C24—H24C	109.5
C6—C1—C2—C3	3.2 (4)	C11—C12—C13—O5	−179.4 (3)
C8—C1—C2—C3	−178.0 (3)	C11—C12—C13—C14	−0.7 (4)
C7—O1—C3—C2	11.0 (4)	O5—C13—C14—C15	−177.3 (3)
C7—O1—C3—C4	−171.2 (3)	C12—C13—C14—C15	3.8 (4)
C1—C2—C3—O1	177.5 (3)	O5—C13—C14—O6	−1.1 (4)
C1—C2—C3—C4	−0.1 (4)	C12—C13—C14—O6	−179.9 (3)
O1—C3—C4—C5	179.8 (3)	C23—O6—C14—C15	−107.9 (3)
C2—C3—C4—C5	−2.3 (5)	C23—O6—C14—C13	75.8 (4)
O1—C3—C4—O2	1.6 (4)	C13—C14—C15—C16	−3.1 (5)
C2—C3—C4—O2	179.4 (3)	O6—C14—C15—C16	−179.3 (3)
C21—O2—C4—C5	95.0 (4)	C14—C15—C16—C11	−0.8 (4)
C21—O2—C4—C3	−86.7 (3)	C12—C11—C16—C15	3.9 (4)
C3—C4—C5—C6	1.7 (5)	C18—C11—C16—C15	−178.8 (3)
O2—C4—C5—C6	179.9 (3)	C10—O4—C18—C11	148.0 (3)
C2—C1—C6—C5	−3.8 (4)	C10—O4—C18—C19	22.2 (3)
C8—C1—C6—C5	177.4 (3)	C12—C11—C18—O4	−142.4 (3)
C4—C5—C6—C1	1.4 (5)	C16—C11—C18—O4	40.3 (3)
C20—O3—C8—C1	151.0 (3)	C12—C11—C18—C19	−23.5 (4)
C20—O3—C8—C9	26.3 (3)	C16—C11—C18—C19	159.2 (3)
C6—C1—C8—O3	−28.2 (4)	C8—C9—C19—C18	−90.3 (3)
C2—C1—C8—O3	153.0 (3)	C10—C9—C19—C18	29.3 (3)
C6—C1—C8—C9	90.3 (3)	C8—C9—C19—C20	29.1 (3)
C2—C1—C8—C9	−88.4 (4)	C10—C9—C19—C20	148.7 (2)
O3—C8—C9—C10	−146.3 (3)	O4—C18—C19—C9	−31.5 (3)
C1—C8—C9—C10	93.0 (3)	C11—C18—C19—C9	−152.2 (2)
O3—C8—C9—C19	−34.1 (3)	O4—C18—C19—C20	−143.2 (3)
C1—C8—C9—C19	−154.8 (3)	C11—C18—C19—C20	96.1 (3)
C18—O4—C10—C9	−3.1 (4)	C8—O3—C20—C19	−7.1 (3)
C8—C9—C10—O4	93.5 (3)	C9—C19—C20—O3	−14.7 (3)
C19—C9—C10—O4	−17.2 (3)	C18—C19—C20—O3	95.9 (3)
C16—C11—C12—C13	−3.1 (4)	C4—O2—C21—O7	−5.5 (5)
C18—C11—C12—C13	179.6 (3)	C4—O2—C21—C22	173.6 (3)
C17—O5—C13—C12	−10.3 (4)	C14—O6—C23—O8	5.8 (4)
C17—O5—C13—C14	171.0 (3)	C14—O6—C23—C24	−176.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O8^i	0.95	2.47	3.382 (4)	161
C10—H10A···O6^ii	0.99	2.59	3.250 (4)	125
C20—H20A···O7^iii	0.99	2.47	3.310 (4)	142
C24—H24C···O7^iv	0.98	2.48	3.452 (4)	172

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