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The title compound, C17H22O4, is an oxabicyclo­[2.2.1]hept-5-ene with two exo-oriented hydroxy­methyl groups which are not parallel to each other. The mol­ecules are linked to each other by hydrogen bonds, resulting in a supra­molecular network. Inter­molecular O—H...O hydrogen bonding is observed between the hydroxyl groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050234/hg2310sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050234/hg2310Isup2.hkl
Contains datablock I

CCDC reference: 667382

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.032
  • wR factor = 0.083
  • Data-to-parameter ratio = 9.9

checkCIF/PLATON results

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Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.27 Ratio
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.38 Ratio PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.63 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C8
Alert level G REFLT03_ALERT_4_G 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. From the CIF: _diffrn_reflns_theta_max 27.62 From the CIF: _reflns_number_total 1915 Count of symmetry unique reflns 1927 Completeness (_total/calc) 99.38% 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 PLAT792_ALERT_1_G Check the Absolute Configuration of C11 = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C12 = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C13 = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C14 = ... R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Furans are generally much less reactive dienes in Diels-Alder cycloaddition reaction due to their inherent aromaticity (Balaban et al., 2004) and usually facile retro- Diels-Alder reaction of the resulting adducts (Woodward, 1940). In view of the importance and great potential of Diels-Alder cycloadducts of furano derivatives as key intermediates for synthesizing structurally complex targets (Hudlicky et al., 1996) or achieving highly region-stereocontrolled reactions via the corresponding oxabicyclic adducts (Chiu & Lautens, 1997), a great deal of effort has been devoted to the development of chemical and physical means to promote the frequently difficult [4 + 2] cycloaddition of cyclic furano dienes. For example, Ultrasonic irradiation effectively promoted the Diels-Alder reaction of substituted furans with dimethyl maleate in very high exo selectivity (Wei, 2004) and the resulting product stereochemistry was unambiguously confirmed a single-crystal X-ray diffraction analysis (Fig. 1) of the corresponding reduction derivative diol (I). The oxidol bridge is on the same side as two hydroxymethyls, which are not parallel each other.

The molecules are linked by O···O hydrogen bonds to form a two-dimensional supramolecular network structure (Fig. 2). Inter-molecular O—H···O hydrogen bonding is observed between the O(3) and O(2) hydroxyl groups.

Related literature top

For related literature, see: Balaban et al. (2004); Chiu & Lautens (1997); Hudlicky et al. (1996); Wei (2004); Woodward (1940); Buser & Vasella (2005).

Experimental top

The title compound was prepared according to literature method (Wei, 2004). Single crystals suitable for X-ray determination were obtained by slow evaporation of a AcOEt solution over a period of several days. IR (film): 3361, 2934, 2837, 1730, 1601, 1587, 1490, 1257, 1155, 1038 cm-1; 1H NMR (200 MHz, CDCl3) delta 2.14–2.47 (m, 2H), 2.67–2.90 (m, 2H), 3.25–3.40 (m, 2H), 3.61–3.79 (m, 2H), 3.78 (m, 2H), 3.81 (s, 3H), 4.86 (d, J = 4.4 Hz, 1H), 6.15 (d, J = 5.8 Hz, 1H), 6.29 (dd, J = 3.8, 5.8 Hz, 1H), 6.75–6.85 (m, 3H), 7.19 (dd, J = 7.4, 7.6 Hz, 1H) p.p.m.; 13C NMR (75 MHz, CDCl3) delta 31.0, 33.8, 46.9, 48.5, 55.1, 60.7, 61.0, 79.2, 90.5, 111.2, 114.0, 120.6, 129.3, 135.2, 136.6, 143.5, 159.6 p.p.m.; LRMS (EI) m/z 290 (M+, 0.04%), 272 (0.1), 254 (0.1), 202 (22), 121 (42), 81 (100).

Refinement top

All H atoms were placed geometrically (C—H values were set to 0.98, 0.97, 0.96, 0.93 and 0.82 A° for atoms CH, CH2, CH3, CH (phenyl) and OH, respectively) and refined with a riding model, with Uiso(H) = 1.2 or 1.5 times Ueq(C), or 1.5 Ueq(O). In the absence of significant anomalous dispersion effects, 1530 Freidel pairs were merged before refinement.

Structure description top

Furans are generally much less reactive dienes in Diels-Alder cycloaddition reaction due to their inherent aromaticity (Balaban et al., 2004) and usually facile retro- Diels-Alder reaction of the resulting adducts (Woodward, 1940). In view of the importance and great potential of Diels-Alder cycloadducts of furano derivatives as key intermediates for synthesizing structurally complex targets (Hudlicky et al., 1996) or achieving highly region-stereocontrolled reactions via the corresponding oxabicyclic adducts (Chiu & Lautens, 1997), a great deal of effort has been devoted to the development of chemical and physical means to promote the frequently difficult [4 + 2] cycloaddition of cyclic furano dienes. For example, Ultrasonic irradiation effectively promoted the Diels-Alder reaction of substituted furans with dimethyl maleate in very high exo selectivity (Wei, 2004) and the resulting product stereochemistry was unambiguously confirmed a single-crystal X-ray diffraction analysis (Fig. 1) of the corresponding reduction derivative diol (I). The oxidol bridge is on the same side as two hydroxymethyls, which are not parallel each other.

The molecules are linked by O···O hydrogen bonds to form a two-dimensional supramolecular network structure (Fig. 2). Inter-molecular O—H···O hydrogen bonding is observed between the O(3) and O(2) hydroxyl groups.

For related literature, see: Balaban et al. (2004); Chiu & Lautens (1997); Hudlicky et al. (1996); Wei (2004); Woodward (1940); Buser & Vasella (2005).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXL97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The 2-D network supramolecular structure of (I). H atoms and 2-(3- methoxy-phenyl)-ethyl have been omitted for clarity. Dashed lines indicate hydrogen-bonding interactions.
{3-Hydroxymethyl-1-[2-(3-methoxyphenyl)ethyl]-7-oxabicyclo[2.2.1]hept-5-en-2- yl}methanol top
Crystal data top
C17H22O4F(000) = 624
Mr = 290.35Dx = 1.245 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 3969 reflections
a = 11.8025 (4) Åθ = 2.7–26.5°
b = 14.9842 (4) ŵ = 0.09 mm1
c = 8.7569 (3) ÅT = 294 K
V = 1548.67 (9) Å3Block, colorless
Z = 40.43 × 0.27 × 0.24 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
1719 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
Graphite monochromatorθmax = 27.6°, θmin = 2.2°
φ and ω scansh = 1512
9219 measured reflectionsk = 1919
1915 independent reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0473P)2 + 0.1224P]
where P = (Fo2 + 2Fc2)/3
1915 reflections(Δ/σ)max < 0.001
193 parametersΔρmax = 0.15 e Å3
1 restraintΔρmin = 0.16 e Å3
Crystal data top
C17H22O4V = 1548.67 (9) Å3
Mr = 290.35Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 11.8025 (4) ŵ = 0.09 mm1
b = 14.9842 (4) ÅT = 294 K
c = 8.7569 (3) Å0.43 × 0.27 × 0.24 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
1719 reflections with I > 2σ(I)
9219 measured reflectionsRint = 0.019
1915 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0321 restraint
wR(F2) = 0.084H-atom parameters constrained
S = 1.08Δρmax = 0.15 e Å3
1915 reflectionsΔρmin = 0.16 e Å3
193 parameters
Special details top

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
xyzUiso*/Ueq
O11.09490 (11)0.61849 (8)0.76469 (15)0.0394 (3)
C161.06391 (15)0.44022 (12)0.5973 (2)0.0395 (4)
H16A1.00720.45060.67550.047*
H16B1.02620.41420.50950.047*
C20.93740 (19)0.87373 (13)0.8725 (3)0.0521 (5)
C121.02937 (13)0.60627 (11)0.5159 (2)0.0345 (4)
H121.04480.63060.41410.041*
C170.90595 (14)0.57645 (12)0.5238 (2)0.0399 (4)
H17A0.89700.52180.46580.048*
H17B0.88650.56370.62920.048*
C90.97705 (16)0.74553 (13)0.6911 (3)0.0469 (5)
H9A0.90980.71490.72710.056*
H9B0.95550.78220.60460.056*
C111.06362 (15)0.67730 (11)0.6400 (2)0.0371 (4)
C151.25209 (18)0.64819 (12)0.6179 (3)0.0510 (5)
H151.32980.64930.60040.061*
C141.18359 (14)0.57231 (12)0.6848 (2)0.0396 (4)
H141.22710.53010.74710.047*
C10.9513 (2)0.96320 (13)0.8366 (3)0.0540 (5)
H11.01230.98110.77670.065*
C101.17892 (15)0.71219 (13)0.5895 (3)0.0482 (5)
H101.19450.76780.54710.058*
C131.11664 (13)0.52951 (11)0.5509 (2)0.0347 (4)
H131.16690.52090.46310.042*
O40.8824 (2)1.11539 (11)0.8606 (3)0.1037 (8)
C81.0225 (2)0.80543 (15)0.8182 (4)0.0675 (7)
H8A1.04490.76850.90390.081*
H8B1.08950.83620.78150.081*
C60.8749 (2)1.02585 (14)0.8895 (3)0.0633 (6)
C50.7847 (2)1.00053 (18)0.9786 (4)0.0775 (8)
H50.73381.04291.01480.093*
C30.8458 (2)0.84890 (16)0.9595 (4)0.0721 (7)
H30.83430.78900.98240.087*
C40.7704 (3)0.91245 (18)1.0134 (4)0.0867 (9)
H40.70960.89491.07380.104*
C70.9686 (4)1.1454 (2)0.7638 (5)0.1168 (15)
H7A1.04081.12810.80460.175*
H7B0.96521.20920.75590.175*
H7C0.95901.11950.66440.175*
O31.14629 (12)0.37876 (8)0.65379 (16)0.0444 (3)
H3A1.19700.37280.59060.067*
O20.82975 (11)0.64249 (10)0.46535 (16)0.0453 (3)
H20.83670.64570.37230.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0426 (6)0.0421 (6)0.0334 (6)0.0039 (5)0.0046 (5)0.0004 (5)
C160.0389 (9)0.0394 (8)0.0401 (10)0.0001 (7)0.0008 (8)0.0001 (8)
C20.0563 (11)0.0425 (10)0.0576 (13)0.0038 (9)0.0086 (10)0.0140 (9)
C120.0327 (8)0.0400 (8)0.0309 (8)0.0024 (7)0.0001 (7)0.0031 (7)
C170.0344 (8)0.0467 (10)0.0387 (9)0.0008 (7)0.0029 (8)0.0012 (8)
C90.0439 (10)0.0438 (9)0.0529 (12)0.0080 (8)0.0075 (9)0.0081 (9)
C110.0369 (8)0.0365 (8)0.0380 (10)0.0006 (7)0.0036 (7)0.0011 (7)
C150.0333 (8)0.0505 (9)0.0692 (15)0.0072 (9)0.0008 (10)0.0006 (10)
C140.0320 (8)0.0411 (9)0.0456 (11)0.0032 (7)0.0063 (8)0.0016 (8)
C10.0625 (12)0.0495 (10)0.0498 (12)0.0005 (9)0.0107 (10)0.0126 (10)
C100.0426 (10)0.0398 (9)0.0621 (13)0.0073 (8)0.0022 (10)0.0062 (10)
C130.0316 (7)0.0397 (8)0.0328 (9)0.0014 (7)0.0041 (7)0.0017 (7)
O40.156 (2)0.0442 (9)0.1105 (19)0.0152 (11)0.0508 (17)0.0004 (11)
C80.0644 (14)0.0529 (12)0.0852 (18)0.0172 (11)0.0225 (14)0.0283 (13)
C60.0859 (16)0.0431 (10)0.0610 (14)0.0087 (11)0.0140 (14)0.0082 (10)
C50.0764 (16)0.0672 (14)0.089 (2)0.0094 (12)0.0282 (16)0.0190 (15)
C30.0869 (18)0.0480 (12)0.0814 (19)0.0108 (12)0.0080 (16)0.0010 (13)
C40.0826 (18)0.0800 (16)0.097 (2)0.0172 (15)0.0362 (19)0.0135 (18)
C70.196 (4)0.0599 (16)0.094 (3)0.013 (2)0.037 (3)0.0105 (18)
O30.0483 (7)0.0418 (7)0.0431 (7)0.0082 (6)0.0041 (6)0.0046 (6)
O20.0367 (6)0.0586 (8)0.0406 (7)0.0091 (6)0.0030 (6)0.0016 (7)
Geometric parameters (Å, º) top
O1—C141.437 (2)C15—H150.9300
O1—C111.451 (2)C14—C131.552 (3)
C16—O31.428 (2)C14—H140.9800
C16—C131.530 (2)C1—C61.382 (3)
C16—H16A0.9700C1—H10.9300
C16—H16B0.9700C10—H100.9300
C2—C31.373 (3)C13—H130.9800
C2—C11.387 (3)O4—C61.368 (3)
C2—C81.511 (3)O4—C71.399 (4)
C12—C171.525 (2)C8—H8A0.9700
C12—C111.574 (2)C8—H8B0.9700
C12—C131.574 (2)C6—C51.373 (4)
C12—H120.9800C5—C41.365 (4)
C17—O21.432 (2)C5—H50.9300
C17—H17A0.9700C3—C41.386 (4)
C17—H17B0.9700C3—H30.9300
C9—C111.513 (2)C4—H40.9300
C9—C81.527 (3)C7—H7A0.9600
C9—H9A0.9700C7—H7B0.9600
C9—H9B0.9700C7—H7C0.9600
C11—C101.523 (3)O3—H3A0.8200
C15—C101.314 (3)O2—H20.8200
C15—C141.513 (3)
C14—O1—C1196.39 (13)C15—C14—H14114.9
O3—C16—C13112.27 (14)C13—C14—H14114.9
O3—C16—H16A109.2C6—C1—C2120.2 (2)
C13—C16—H16A109.2C6—C1—H1119.9
O3—C16—H16B109.2C2—C1—H1119.9
C13—C16—H16B109.2C15—C10—C11106.37 (17)
H16A—C16—H16B107.9C15—C10—H10126.8
C3—C2—C1118.8 (2)C11—C10—H10126.8
C3—C2—C8120.9 (2)C16—C13—C14111.59 (15)
C1—C2—C8120.3 (2)C16—C13—C12115.11 (13)
C17—C12—C11114.31 (15)C14—C13—C12100.28 (13)
C17—C12—C13113.70 (14)C16—C13—H13109.8
C11—C12—C13101.03 (13)C14—C13—H13109.8
C17—C12—H12109.2C12—C13—H13109.8
C11—C12—H12109.2C6—O4—C7118.3 (2)
C13—C12—H12109.2C2—C8—C9113.20 (18)
O2—C17—C12112.39 (15)C2—C8—H8A108.9
O2—C17—H17A109.1C9—C8—H8A108.9
C12—C17—H17A109.1C2—C8—H8B108.9
O2—C17—H17B109.1C9—C8—H8B108.9
C12—C17—H17B109.1H8A—C8—H8B107.8
H17A—C17—H17B107.9O4—C6—C5115.2 (2)
C11—C9—C8112.05 (16)O4—C6—C1124.2 (2)
C11—C9—H9A109.2C5—C6—C1120.6 (2)
C8—C9—H9A109.2C4—C5—C6119.3 (2)
C11—C9—H9B109.2C4—C5—H5120.4
C8—C9—H9B109.2C6—C5—H5120.4
H9A—C9—H9B107.9C2—C3—C4120.5 (2)
O1—C11—C9111.07 (15)C2—C3—H3119.7
O1—C11—C10101.51 (14)C4—C3—H3119.7
C9—C11—C10117.20 (15)C5—C4—C3120.6 (3)
O1—C11—C12100.04 (12)C5—C4—H4119.7
C9—C11—C12119.19 (15)C3—C4—H4119.7
C10—C11—C12105.14 (15)O4—C7—H7A109.5
C10—C15—C14105.69 (18)O4—C7—H7B109.5
C10—C15—H15127.2H7A—C7—H7B109.5
C14—C15—H15127.2O4—C7—H7C109.5
O1—C14—C15102.48 (14)H7A—C7—H7C109.5
O1—C14—C13101.29 (13)H7B—C7—H7C109.5
C15—C14—C13106.85 (17)C16—O3—H3A109.5
O1—C14—H14114.9C17—O2—H2109.5
C11—C12—C17—O275.2 (2)O3—C16—C13—C1456.0 (2)
C13—C12—C17—O2169.53 (15)O3—C16—C13—C12169.41 (15)
C14—O1—C11—C9173.54 (15)O1—C14—C13—C1685.19 (15)
C14—O1—C11—C1048.20 (15)C15—C14—C13—C16167.91 (14)
C14—O1—C11—C1259.66 (14)O1—C14—C13—C1237.20 (15)
C8—C9—C11—O161.3 (2)C15—C14—C13—C1269.70 (16)
C8—C9—C11—C1054.7 (3)C17—C12—C13—C163.9 (2)
C8—C9—C11—C12176.68 (19)C11—C12—C13—C16119.04 (16)
C17—C12—C11—O187.36 (16)C17—C12—C13—C14123.77 (16)
C13—C12—C11—O135.14 (15)C11—C12—C13—C140.84 (16)
C17—C12—C11—C933.8 (2)C3—C2—C8—C972.7 (3)
C13—C12—C11—C9156.28 (16)C1—C2—C8—C9108.0 (3)
C17—C12—C11—C10167.70 (15)C11—C9—C8—C2179.5 (2)
C13—C12—C11—C1069.80 (16)C7—O4—C6—C5176.5 (3)
C11—O1—C14—C1549.05 (16)C7—O4—C6—C14.1 (5)
C11—O1—C14—C1361.25 (13)C2—C1—C6—O4179.6 (3)
C10—C15—C14—O132.1 (2)C2—C1—C6—C50.3 (4)
C10—C15—C14—C1374.0 (2)O4—C6—C5—C4180.0 (3)
C3—C2—C1—C60.8 (4)C1—C6—C5—C40.6 (5)
C8—C2—C1—C6178.4 (2)C1—C2—C3—C41.6 (4)
C14—C15—C10—C110.5 (2)C8—C2—C3—C4177.7 (3)
O1—C11—C10—C1530.7 (2)C6—C5—C4—C30.1 (5)
C9—C11—C10—C15151.8 (2)C2—C3—C4—C51.2 (5)
C12—C11—C10—C1573.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2i0.821.932.7409 (19)173
Symmetry code: (i) x+1/2, y+1, z.

Experimental details

Crystal data
Chemical formulaC17H22O4
Mr290.35
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)294
a, b, c (Å)11.8025 (4), 14.9842 (4), 8.7569 (3)
V3)1548.67 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.43 × 0.27 × 0.24
Data collection
DiffractometerBruker APEX CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9219, 1915, 1719
Rint0.019
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.084, 1.08
No. of reflections1915
No. of parameters193
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2i0.821.932.7409 (19)172.7
Symmetry code: (i) x+1/2, y+1, z.
 

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