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Results of single-crystal X-ray experiments performed for the title compounds, (1S,2R,3S,4R,5R)-4-benzyl­oxy-2-[1-(benzyl­oxy)­allyl]-5-hydroxy­methyl-2,3,4,5-tetra­hydro­furan-3-ol, C22H26O5, (I), and (3R,5S,6S,7S,8S)-3,6-bis­(benzyl­oxy)-5-iodo­methyl-2,3,4,5-tetra­hydro­furo­[3,2-b]­furan-2-one, C21H21IO5, (II), demonstrate that the tetra­hydro­furan ring that is common to both structures adopts a different conformation in each mol­ecule. Structural analyses of (I) and (II), which were prepared from the same precursor, indicate that their different conformations are caused by hydrogen-bonding interactions in the case of (I) and the presence of a fused bicyclic ring system in the case of (II). Density functional theory calculations on simplified analogs of (I) and (II) are also presented.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103025757/sq1137sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025757/sq1137Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025757/sq1137IIsup3.hkl
Contains datablock II

CCDC references: 229118; 229119

Comment top

The chiral molecules (1S,2R,3S,4R,5R)-4-Benzyloxy-2-[1-(benzyloxy)allyl]-5-hydroxymethyl- 2,3,4,5-tetrahydrofuran-3-ol, (I), and (3R,5S,6S,7S,8S)-3,6-bis(benzyloxy)-5-iodomethyl-2,3,4,5- tetrahydrofuro[3,2-b]furan-2-one, (II), have been prepared from the same precursor, namely (3S,4R,5R,6S)-3,6-bis(benzyloxy)-octa-1,7-diene-4,5-diol, (III), and structurally characterized during the course of our work toward the synthesis of natural products related to marine sponge extracts. Diene diol (III) was also used to prepare a Conduritol E derivative that we have reported previously (Clark et al., 2001). We compare here the conformational properties of these two tetrahydrofuran ring-bearing compounds, (I) and (II).

The absolute stereochemical assignment of (I) [R (C1), S (C2), R (C3), R (C4) and S (C5)] is based solely on knowledge of the synthesis, while the chiral centers in (II) were unequivocally assigned as S (C1), S (C2), S (C3), S (C4) and R (C5) from the crystallographic data. Crystallographic studies verify the expectation that the five-membered O1—C1–C4 heterocycles in both structures have the same relative stereochemistry, with all substituents in a cis arrangement with respect to one another. In the case of (II), this all-cis arrangement forces the substituents on atoms C3, C4 and C5 to be directed toward the concave face of the bicyclic ring system.

Although the bond distances in (I) and (II) are typical, several bond angles of the O1—C1—C2—C3—C4 ring system in (I) exhibit appreciable differences from the corresponding parameters in (II). The C3—C2—C1 [99.4 (2)°], O1—C4—C3 [105.25 (18)°], and C1—O1—C4 [108.91 (17)°] angles in (I) differ significantly from the related C3—C2—C1 [104.6 (4)°], O1—C4—C3 [107.0 (3)°], and C1—O1—C4 [110.1 (3)°] angles in (II). The presence of a second ring in (II), which is fused to the tetrahydrofuranyl ring of interest at the C1 and C2 positions, causes widening of these bond angles, with concomitant reduction of the C5—C1—C2 and C1—C2—O2 angles.

The stereochemical properties of the O1—C1–C4 heterocycles of (I) and (II) were further characterized by conformational analysis according to Cremer & Pople (1975) by using the program RING5 (Guzei, 2003). The conformation of the O1—C1–C4 ring system in (I) is characterized by the puckering amplitude, q2, of 0.410 Å and phase angle, ϕ2, of 63.36°. The latter value indicates that the ring conformation is intermediate between the twisted 3T2 and envelope 3E, in which atom C2 would be the flap atom. A similar conformation intermediate between twisted 4T3 and envelope 4E is observed for the O2—C6—C5—C1—C2 ring in (II), which is characterized by a q2 value of 0.296 Å and a phase angle of 279.61°. This ring does not deviate quite as much from planarity, as revealed by the puckering amplitude. The other five-membered ring in (II), O1—C1–C4, has an envelope conformation, E2, with atom C1 occupying the flap position [q2=0.295 Å and ϕ2=37.96°].

The primary contributors to the adopted conformations of the O1—C1–C4 rings of the two structures are the presence of hydrogen-bonding interactions in (I) and a bicyclic ring system in (II). In (I), an intramolecular O3—H3.·O5 hydrogen bond is observed Table 1. ?The corresponding values for 155 compounds with 192 similar hydrogen bonds reported to the Cambridge Structural Database (CSD; Allen, 2002) are 2.73 (8) Å and 161 (6)°? This distance is indicative of a reasonably strong hydrogen bond and could affect the bond angles and ring conformation mentioned earlier. In the lattice of (I), intermolecular O5—H5.·O1[x + 1/2, −y + 3/2, −z] hydrogen-bonding interactions form a series of one-dimensional chains in the a direction (Table 1). The relevant values for 398 compounds with 429 similar hydrogen bonds (CSD) are 2.82 (6) Å and 166 (8)°. Both types of hydrogen-bonding interactions may influence the positioning of the flap atom C2 in (I). In contrast, (II) does not contain hydrogen bonds but instead contains a bicyclic ring system. Steric repulsion and torsional strain of the adjoined rings in (II) are probably minimized when atom C1 is the flap atom of the O1—C1–C4 heterocycle.

In order to compare the observed ring conformations with theoretical data, density-functional theory calculations were performed on simplified analogs of (I) and (II), referred to as (Ia) and (IIa). In both molecules, the phenyl rings were replaced by methyl groups, and the I atom was replaced with an H in (IIa), in order to reduce computational time. The geometry optimizations were performed at the B3LYP/6–311++G** level (Gaussian98). The calculated C—O bond distances agree with experimental data within 0.006 Å in (I) and 0.01 Å in (II), while the calculated C—C distances for both molecules differ by up to 0.026 Å from the experimental parameters. The puckering coordinates for the O1—C1–C4 ring in (Ia) (q2=0.391 Å and ϕ2=66.14°) are in excellent agreement with the experimental data producing a similar conformation, i.e. intermediate between 2T3 and E3 with atom C2 in the flap position of the envelope configuration.

The results of conformational analysis of (IIa) differ considerably from those obtained for (II), apparently because of the influence of the I atom on the lattice packing. While the energy required to affect torsion angles in the lattice may not exceed several kcal mol−1 it is instructive to appreciate the changes that a large atom can introduce. Thus, ring O1—C1–C4 in (IIa) (q2=0.374 Å and ϕ2=345.84°) is in a twisted conformation, 1T5, and ring O2—C6—C5—C1—C2 (q2=0.203 Å and ϕ2=83.55°) adopts a conformation intermediate between 3E and 3T4, with atom C5 in the flap position. For the two rings, both the conformations and the amplitudes are very different from the corresponding values in the parent compound (III)? (see above), indicating that the lattice forces in the solid-state structure of (II) play a sinificant role and considerably affect the molecular configuration.

Experimental top

For the preparation of (I), diene diol (III) was treated with meta-chloroperoxybenzoic acid in CH2Cl2 at room temperature for 36 h, providing the monoepoxide (IV) in 43% yield as a ~1:1 mixture of stereoisomers, along with 40% of unreacted (III). Subjection of (IV) to MeONa in MeOH at reflux for 3 h then provided the crystalline alcohol (I) in 38% yield (m.p. 393–396 K). 1H NMR (CDCl3, 300 MHz): 3.68 (dd, J = 7.9, 2.8 Hz, 1H), 3.73 (AB*X, JAB = 12.6 Hz, JBX = 2.1 Hz, 1H), 3.78 (A*BX, JAB = 12.6 Hz, JAX = 8.1 Hz, 1H), 4.17 (ABX*, ddd, J = 8.1, 3.0, 2.1 Hz, 1H), 4.22 (br d, J = 7.2 Hz, 1H), 4.29 (dd, J = 8.2, 4.5 Hz, 1 H); 4.37 (dd, J = 4.5, 2.8 Hz, 1H), 4.49 (d, J = 11 Hz, 1H), 4.50 (d, J = 11 Hz, 1H), 4.64 (d, J = 11 Hz, 1H), 4.80 (d, J = 11 Hz, 1H), 5.41 (m, 2H), 5.92 (m, 1H). For the preparation of (II), diene diol (III) was treated with I2 and NaHCO3 in CH2Cl2 at 273 K for 1 h, providing the iodoetherification product (V) in 35% yield, along with 60% of unreacted (III). Ozonolysis of (V) at 195 K followed by oxidation of the resulting hemiacetal with tetra-n-propylammonium perruthenate and N-methylmorpholine N-oxide provided the crystalline lactone (II) in 53% yield over two steps (m.p. 389 K). 1H NMR (CDCl3, 300 MHz): 3.21 (dd, J = 10.2, 7.1 Hz, 1H), 3.45 (dd, J = 10.2, 6.4 Hz, 1H), 4.21 (d, J = 5.0 Hz, 1H), 4.22 (dd, J = 6.3, 4.8 Hz, 1H), 4.38 (aq, J = 6.9 Hz, 1H), 4.50 (dd, J = 5.0, 4.0 Hz, 1H), 4.54 (d, J = 11 Hz, 1H), 4.76 (d, J = 11 Hz, 1H), 4.85 (dd, J = 4.5, 4.0 Hz, 1H), 4.91 (ABq, J = 11 Hz, 2H).

Refinement top

Hydroxy H atoms were constrained to an ideal geometry [with Uiso(H) = 1.5Ueq(O)] and allowed to rotate freely about their C—O bonds. All other H atoms were constrained and allowed to ride on their parent C atoms [with Uiso(H) = 1.2Ueq(C)]. In (I), atoms C16, C17, C18, C19, C20 and C21 were fitted to a regular hexagon.

Computing details top

Data collection: SMART (Bruker, 2000–2003) for (I); SMART (Bruker, 2000-2003) for (II). For both compounds, cell refinement: SMART. Data reduction: SAINT? and SHELXTL (Bruker, 2000–2003) for (I); SHELXTL for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 30% probability level and the intramolecular hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. The molecular structure of (II). Displacement ellipsoids are shown at the 30% probability level.
(I) top
Crystal data top
C22H26O5Dx = 1.271 Mg m3
Mr = 370.43Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 3927 reflections
a = 5.5273 (5) Åθ = 2.0–50.0°
b = 13.4315 (13) ŵ = 0.09 mm1
c = 26.074 (2) ÅT = 173 K
V = 1935.7 (3) Å3Needle, colourless
Z = 40.50 × 0.30 × 0.30 mm
F(000) = 792
Data collection top
Bruker CCD 1000 area-detector
diffractometer
2262 independent reflections
Radiation source: fine-focus sealed tube1973 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ϕ and ω scansθmax = 26.4°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
h = 06
Tmin = 0.933, Tmax = 0.974k = 016
10541 measured reflectionsl = 031
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1041P)2]
where P = (Fo2 + 2Fc2)/3
2262 reflections(Δ/σ)max < 0.001
234 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C22H26O5V = 1935.7 (3) Å3
Mr = 370.43Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.5273 (5) ŵ = 0.09 mm1
b = 13.4315 (13) ÅT = 173 K
c = 26.074 (2) Å0.50 × 0.30 × 0.30 mm
Data collection top
Bruker CCD 1000 area-detector
diffractometer
2262 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
1973 reflections with I > 2σ(I)
Tmin = 0.933, Tmax = 0.974Rint = 0.045
10541 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.00Δρmax = 0.34 e Å3
2262 reflectionsΔρmin = 0.20 e Å3
234 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
xyzUiso*/Ueq
O10.1619 (4)0.65835 (12)0.04537 (7)0.0274 (4)
O20.0072 (4)0.40576 (12)0.07685 (7)0.0333 (5)
O30.2720 (3)0.61807 (14)0.10932 (8)0.0294 (5)
H30.28870.66880.09080.044*
O40.0294 (4)0.77535 (12)0.15874 (6)0.0280 (5)
O50.2313 (4)0.79140 (13)0.05448 (7)0.0295 (5)
H50.29100.81170.02680.044*
C10.1262 (5)0.57022 (17)0.07558 (10)0.0235 (6)
H10.28660.54590.08810.028*
C20.0238 (5)0.60492 (18)0.12125 (10)0.0241 (6)
H20.00490.55780.15070.029*
C30.1044 (5)0.70289 (17)0.13265 (10)0.0252 (6)
H3A0.25580.68870.15230.030*
C40.1730 (5)0.74323 (18)0.07905 (10)0.0241 (6)
H40.34330.76830.08010.029*
C50.0093 (6)0.48991 (18)0.04322 (10)0.0273 (6)
H5A0.16080.50960.03490.033*
C60.1432 (6)0.4688 (2)0.00512 (11)0.0338 (7)
H60.30480.44540.00240.041*
C70.0529 (7)0.4804 (2)0.05091 (11)0.0403 (8)
H7A0.10830.50370.05500.048*
H7B0.14830.46550.08020.048*
C80.1436 (7)0.3273 (2)0.05918 (13)0.0467 (9)
H8A0.31070.35180.05390.056*
H8B0.08230.30110.02610.056*
C90.1406 (6)0.2469 (2)0.09918 (11)0.0347 (7)
C100.0486 (6)0.1808 (2)0.10170 (12)0.0380 (7)
H100.17590.18490.07730.046*
C110.0556 (6)0.1090 (2)0.13904 (12)0.0396 (7)
H110.18720.06360.14020.048*
C120.1261 (6)0.1024 (2)0.17467 (12)0.0363 (7)
H120.12030.05290.20060.044*
C130.3157 (6)0.1676 (2)0.17254 (12)0.0387 (7)
H130.44230.16320.19710.046*
C140.3241 (6)0.2397 (2)0.13501 (13)0.0384 (7)
H140.45660.28470.13370.046*
C150.0770 (7)0.7492 (2)0.21063 (10)0.0374 (7)
H15A0.15300.68250.21230.045*
H15B0.07580.74730.23040.045*
C160.2433 (3)0.82546 (12)0.23249 (6)0.0277 (6)
C170.2034 (4)0.86255 (16)0.28153 (6)0.0397 (8)
H170.06710.84080.30070.048*
C180.3629 (5)0.93140 (16)0.30252 (7)0.0569 (12)
H180.33570.95670.33600.068*
C190.5623 (4)0.96315 (14)0.27446 (10)0.0636 (12)
H190.67141.01020.28880.076*
C200.6022 (3)0.92606 (16)0.22541 (9)0.0562 (10)
H200.73850.94780.20620.067*
C210.4427 (4)0.85722 (15)0.20443 (6)0.0377 (7)
H210.46990.83190.17090.045*
C220.0111 (5)0.82450 (18)0.05849 (10)0.0244 (6)
H22A0.06970.84550.02430.029*
H22B0.01840.88290.08160.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0346 (11)0.0227 (8)0.0250 (10)0.0001 (9)0.0071 (8)0.0014 (7)
O20.0394 (13)0.0241 (8)0.0364 (11)0.0065 (9)0.0076 (10)0.0032 (8)
O30.0206 (10)0.0301 (9)0.0374 (12)0.0013 (8)0.0053 (9)0.0062 (8)
O40.0371 (12)0.0267 (8)0.0202 (9)0.0063 (9)0.0032 (9)0.0015 (7)
O50.0252 (11)0.0334 (9)0.0298 (11)0.0030 (9)0.0050 (8)0.0096 (8)
C10.0240 (15)0.0240 (11)0.0224 (13)0.0019 (11)0.0042 (11)0.0008 (10)
C20.0225 (14)0.0249 (12)0.0249 (14)0.0023 (11)0.0019 (11)0.0041 (11)
C30.0258 (15)0.0255 (11)0.0244 (13)0.0030 (11)0.0009 (11)0.0034 (10)
C40.0227 (14)0.0234 (11)0.0263 (14)0.0043 (11)0.0012 (11)0.0003 (10)
C50.0289 (15)0.0249 (11)0.0280 (14)0.0019 (11)0.0002 (12)0.0012 (10)
C60.0357 (17)0.0274 (13)0.0382 (17)0.0057 (12)0.0040 (13)0.0067 (12)
C70.052 (2)0.0359 (14)0.0334 (16)0.0022 (15)0.0034 (15)0.0084 (13)
C80.053 (2)0.0347 (14)0.052 (2)0.0147 (16)0.0200 (18)0.0058 (15)
C90.0363 (17)0.0266 (13)0.0411 (17)0.0131 (13)0.0086 (14)0.0037 (12)
C100.0307 (16)0.0408 (15)0.0425 (17)0.0051 (14)0.0037 (14)0.0045 (14)
C110.0324 (17)0.0376 (15)0.0489 (19)0.0049 (14)0.0007 (15)0.0042 (14)
C120.0403 (19)0.0311 (13)0.0375 (17)0.0111 (14)0.0015 (14)0.0029 (13)
C130.0353 (17)0.0426 (15)0.0383 (17)0.0121 (15)0.0062 (14)0.0086 (14)
C140.0317 (17)0.0312 (13)0.0524 (19)0.0030 (14)0.0029 (15)0.0139 (14)
C150.049 (2)0.0372 (14)0.0261 (15)0.0117 (15)0.0039 (14)0.0084 (12)
C160.0317 (15)0.0252 (11)0.0262 (14)0.0050 (12)0.0034 (12)0.0019 (11)
C170.0367 (18)0.0530 (17)0.0293 (16)0.0143 (16)0.0067 (13)0.0071 (14)
C180.070 (3)0.0490 (18)0.052 (2)0.032 (2)0.030 (2)0.0263 (17)
C190.069 (3)0.0311 (15)0.090 (3)0.0069 (18)0.050 (3)0.0006 (19)
C200.041 (2)0.0542 (19)0.073 (3)0.0155 (19)0.017 (2)0.028 (2)
C210.0340 (17)0.0361 (14)0.0430 (17)0.0030 (14)0.0027 (15)0.0088 (13)
C220.0275 (15)0.0241 (11)0.0215 (13)0.0052 (11)0.0026 (11)0.0023 (10)
Geometric parameters (Å, º) top
O1—C11.435 (3)C9—C101.373 (4)
O1—C41.440 (3)C9—C141.382 (4)
O2—C81.421 (3)C10—C111.371 (4)
O2—C51.431 (3)C10—H100.9500
O3—C21.418 (3)C11—C121.371 (4)
O3—H30.8400C11—H110.9500
O4—C31.399 (3)C12—C131.366 (5)
O4—C151.423 (3)C12—H120.9500
O5—C221.416 (3)C13—C141.378 (4)
O5—H50.8400C13—H130.9500
C1—C51.514 (4)C14—H140.9500
C1—C21.524 (4)C15—C161.490 (3)
C1—H11.0000C15—H15A0.9900
C2—C31.524 (4)C15—H15B0.9900
C2—H21.0000C16—C171.3900
C3—C41.546 (4)C16—C211.3900
C3—H3A1.0000C17—C181.3900
C4—C221.510 (4)C17—H170.9500
C4—H41.0000C18—C191.3900
C5—C61.489 (4)C18—H180.9500
C5—H5A1.0000C19—C201.3900
C6—C71.303 (4)C19—H190.9500
C6—H60.9500C20—C211.3900
C7—H7A0.9500C20—H200.9500
C7—H7B0.9500C21—H210.9500
C8—C91.501 (4)C22—H22A0.9900
C8—H8A0.9900C22—H22B0.9900
C8—H8B0.9900
C1—O1—C4108.91 (17)C10—C9—C8120.4 (3)
C8—O2—C5113.1 (2)C14—C9—C8120.8 (3)
C2—O3—H3109.5C11—C10—C9120.7 (3)
C3—O4—C15112.85 (19)C11—C10—H10119.7
C22—O5—H5109.5C9—C10—H10119.7
O1—C1—C5109.9 (2)C10—C11—C12120.4 (3)
O1—C1—C2104.55 (19)C10—C11—H11119.8
C5—C1—C2114.9 (2)C12—C11—H11119.8
O1—C1—H1109.1C13—C12—C11119.5 (3)
C5—C1—H1109.1C13—C12—H12120.2
C2—C1—H1109.1C11—C12—H12120.2
O3—C2—C3112.7 (2)C12—C13—C14120.3 (3)
O3—C2—C1113.2 (2)C12—C13—H13119.8
C3—C2—C199.4 (2)C14—C13—H13119.8
O3—C2—H2110.4C13—C14—C9120.3 (3)
C3—C2—H2110.4C13—C14—H14119.9
C1—C2—H2110.4C9—C14—H14119.9
O4—C3—C2116.7 (2)O4—C15—C16107.9 (2)
O4—C3—C4109.00 (19)O4—C15—H15A110.1
C2—C3—C4103.9 (2)C16—C15—H15A110.1
O4—C3—H3A109.0O4—C15—H15B110.1
C2—C3—H3A109.0C16—C15—H15B110.1
C4—C3—H3A109.0H15A—C15—H15B108.4
O1—C4—C22109.3 (2)C17—C16—C21120.0
O1—C4—C3105.25 (18)C17—C16—C15120.05 (17)
C22—C4—C3115.4 (2)C21—C16—C15119.92 (17)
O1—C4—H4108.9C18—C17—C16120.0
C22—C4—H4108.9C18—C17—H17120.0
C3—C4—H4108.9C16—C17—H17120.0
O2—C5—C6111.9 (2)C17—C18—C19120.0
O2—C5—C1102.99 (19)C17—C18—H18120.0
C6—C5—C1113.3 (2)C19—C18—H18120.0
O2—C5—H5A109.5C20—C19—C18120.0
C6—C5—H5A109.5C20—C19—H19120.0
C1—C5—H5A109.5C18—C19—H19120.0
C7—C6—C5124.2 (3)C19—C20—C21120.0
C7—C6—H6117.9C19—C20—H20120.0
C5—C6—H6117.9C21—C20—H20120.0
C6—C7—H7A120.0C20—C21—C16120.0
C6—C7—H7B120.0C20—C21—H21120.0
H7A—C7—H7B120.0C16—C21—H21120.0
O2—C8—C9107.6 (2)O5—C22—C4111.1 (2)
O2—C8—H8A110.2O5—C22—H22A109.4
C9—C8—H8A110.2C4—C22—H22A109.4
O2—C8—H8B110.2O5—C22—H22B109.4
C9—C8—H8B110.2C4—C22—H22B109.4
H8A—C8—H8B108.5H22A—C22—H22B108.0
C10—C9—C14118.8 (3)
C4—O1—C1—C5155.8 (2)C1—C5—C6—C7118.9 (3)
C4—O1—C1—C232.0 (3)C5—O2—C8—C9176.8 (3)
O1—C1—C2—O377.7 (3)O2—C8—C9—C1080.5 (3)
C5—C1—C2—O342.8 (3)O2—C8—C9—C1497.6 (3)
O1—C1—C2—C342.0 (3)C14—C9—C10—C110.0 (4)
C5—C1—C2—C3162.5 (2)C8—C9—C10—C11178.2 (3)
C15—O4—C3—C269.5 (3)C9—C10—C11—C120.3 (5)
C15—O4—C3—C4173.3 (2)C10—C11—C12—C130.4 (5)
O3—C2—C3—O436.2 (3)C11—C12—C13—C140.2 (4)
C1—C2—C3—O4156.3 (2)C12—C13—C14—C90.1 (4)
O3—C2—C3—C483.8 (3)C10—C9—C14—C130.2 (4)
C1—C2—C3—C436.3 (2)C8—C9—C14—C13178.0 (3)
C1—O1—C4—C22132.4 (2)C3—O4—C15—C16173.5 (2)
C1—O1—C4—C37.9 (3)O4—C15—C16—C17137.1 (2)
O4—C3—C4—O1144.1 (2)O4—C15—C16—C2145.0 (3)
C2—C3—C4—O119.0 (3)C21—C16—C17—C180.0
O4—C3—C4—C2223.5 (3)C15—C16—C17—C18178.0 (2)
C2—C3—C4—C22101.6 (2)C16—C17—C18—C190.0
C8—O2—C5—C671.5 (3)C17—C18—C19—C200.0
C8—O2—C5—C1166.5 (2)C18—C19—C20—C210.0
O1—C1—C5—O2174.8 (2)C19—C20—C21—C160.0
C2—C1—C5—O267.6 (3)C17—C16—C21—C200.0
O1—C1—C5—C653.8 (3)C15—C16—C21—C20178.0 (2)
C2—C1—C5—C6171.3 (2)O1—C4—C22—O559.0 (3)
O2—C5—C6—C7125.3 (3)C3—C4—C22—O559.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O50.841.932.741 (3)163
O5—H5···O1i0.841.942.754 (3)162
Symmetry code: (i) x+1/2, y+3/2, z.
(II) top
Crystal data top
C21H21IO5F(000) = 480
Mr = 480.28Dx = 1.566 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 6.0077 (7) ÅCell parameters from 2146 reflections
b = 15.4106 (14) Åθ = 2.0–50.0°
c = 11.0654 (13) ŵ = 1.60 mm1
β = 96.066 (2)°T = 296 K
V = 1018.72 (19) Å3Needle, colourless
Z = 20.40 × 0.30 × 0.30 mm
Data collection top
Bruker CCD 1000 area-detector
diffractometer
2969 independent reflections
Radiation source: fine-focus sealed tube2480 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 26.3°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
h = 67
Tmin = 0.567, Tmax = 0.645k = 818
4977 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.065 w = 1/[σ2(Fo2) + (0.0326P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2969 reflectionsΔρmax = 0.52 e Å3
244 parametersΔρmin = 0.27 e Å3
1 restraintAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (2)
Crystal data top
C21H21IO5V = 1018.72 (19) Å3
Mr = 480.28Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.0077 (7) ŵ = 1.60 mm1
b = 15.4106 (14) ÅT = 296 K
c = 11.0654 (13) Å0.40 × 0.30 × 0.30 mm
β = 96.066 (2)°
Data collection top
Bruker CCD 1000 area-detector
diffractometer
2969 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Blessing, 1995)
2480 reflections with I > 2σ(I)
Tmin = 0.567, Tmax = 0.645Rint = 0.018
4977 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.065Δρmax = 0.52 e Å3
S = 1.03Δρmin = 0.27 e Å3
2969 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
244 parametersAbsolute structure parameter: 0.02 (2)
1 restraint
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
xyzUiso*/Ueq
I0.54530 (4)0.31222 (3)0.55513 (2)0.07157 (12)
O10.2583 (6)0.3727 (2)0.3021 (3)0.0676 (9)
O20.1573 (5)0.2594 (2)0.0896 (3)0.0550 (8)
O30.5039 (4)0.44003 (19)0.1315 (3)0.0554 (8)
O40.4830 (5)0.2770 (2)0.0138 (3)0.0675 (9)
O50.0054 (6)0.1788 (2)0.2772 (3)0.0653 (8)
C10.1356 (7)0.3935 (3)0.1900 (4)0.0508 (10)
H10.04000.44470.19440.061*
C20.0040 (5)0.3110 (5)0.1532 (3)0.0505 (8)
H20.13570.32350.10220.061*
C30.0375 (7)0.2688 (3)0.2726 (4)0.0557 (11)
H30.18900.28280.29180.067*
C40.1373 (5)0.3126 (5)0.3668 (3)0.0515 (8)
H40.05960.34360.42730.062*
C50.2970 (7)0.4013 (3)0.0947 (4)0.0488 (10)
H50.22430.43250.02410.059*
C60.3306 (6)0.3079 (5)0.0608 (3)0.0494 (9)
C70.4894 (8)0.5315 (3)0.1538 (5)0.0703 (14)
H7A0.35060.54470.18740.084*
H7B0.49180.56330.07830.084*
C80.6834 (7)0.5571 (3)0.2410 (4)0.0560 (12)
C90.7090 (9)0.5196 (4)0.3539 (5)0.0719 (14)
H90.60130.48070.37520.086*
C100.8901 (11)0.5381 (4)0.4361 (5)0.0846 (17)
H100.90680.51150.51200.102*
C111.0484 (11)0.5976 (4)0.4040 (6)0.0867 (18)
H111.17430.60970.45770.104*
C121.0192 (10)0.6379 (4)0.2947 (6)0.0794 (16)
H121.12220.67940.27530.095*
C130.8365 (11)0.6180 (4)0.2106 (6)0.0660 (16)
H130.81820.64540.13530.079*
C140.1731 (9)0.1296 (4)0.2050 (5)0.0721 (14)
H14A0.20680.15600.12550.086*
H14B0.30970.12690.24440.086*
C150.0774 (8)0.0407 (3)0.1932 (5)0.0551 (13)
C160.1154 (8)0.0289 (4)0.1351 (5)0.0685 (14)
H160.18410.07670.10370.082*
C170.2049 (8)0.0518 (4)0.1236 (5)0.0741 (15)
H170.33300.05810.08400.089*
C180.1094 (10)0.1235 (4)0.1692 (5)0.0732 (15)
H180.17190.17820.16170.088*
C190.0821 (9)0.1129 (4)0.2269 (5)0.0707 (14)
H190.15000.16120.25760.085*
C200.1733 (9)0.0324 (4)0.2394 (5)0.0618 (14)
H200.30110.02670.27940.074*
C210.3001 (9)0.2495 (4)0.4299 (5)0.0735 (14)
H21A0.37530.21840.36970.088*
H21B0.21880.20740.47350.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I0.06916 (17)0.0762 (2)0.06637 (17)0.0028 (3)0.00675 (11)0.0060 (3)
O10.081 (2)0.068 (2)0.0506 (18)0.0253 (18)0.0070 (16)0.0043 (17)
O20.0504 (18)0.055 (2)0.0604 (19)0.0089 (16)0.0076 (15)0.0097 (15)
O30.0429 (15)0.0475 (19)0.074 (2)0.0033 (13)0.0012 (14)0.0037 (15)
O40.0513 (17)0.067 (2)0.086 (2)0.0020 (14)0.0128 (15)0.0166 (17)
O50.079 (2)0.049 (2)0.065 (2)0.0107 (17)0.0048 (16)0.0003 (16)
C10.054 (2)0.039 (3)0.058 (3)0.005 (2)0.003 (2)0.002 (2)
C20.0370 (15)0.055 (2)0.058 (2)0.004 (4)0.0002 (14)0.002 (4)
C30.049 (2)0.058 (3)0.060 (3)0.002 (2)0.005 (2)0.002 (2)
C40.0517 (18)0.051 (2)0.0538 (19)0.003 (4)0.0135 (15)0.008 (4)
C50.038 (2)0.054 (3)0.053 (2)0.000 (2)0.0023 (18)0.004 (2)
C60.0440 (18)0.055 (3)0.0477 (18)0.006 (4)0.0026 (15)0.003 (4)
C70.062 (3)0.051 (3)0.094 (4)0.001 (2)0.011 (2)0.004 (3)
C80.060 (3)0.039 (3)0.070 (3)0.004 (2)0.005 (2)0.006 (2)
C90.081 (3)0.056 (3)0.080 (4)0.006 (3)0.013 (3)0.008 (3)
C100.120 (5)0.058 (4)0.073 (4)0.002 (3)0.005 (3)0.012 (3)
C110.099 (4)0.061 (4)0.094 (4)0.004 (3)0.023 (3)0.025 (3)
C120.083 (4)0.051 (3)0.103 (4)0.022 (3)0.004 (3)0.015 (3)
C130.086 (4)0.034 (3)0.077 (4)0.010 (3)0.004 (3)0.000 (3)
C140.066 (3)0.065 (4)0.084 (4)0.014 (3)0.005 (3)0.011 (3)
C150.056 (3)0.052 (3)0.054 (3)0.011 (2)0.006 (2)0.006 (2)
C160.059 (3)0.065 (4)0.083 (4)0.019 (3)0.012 (3)0.011 (3)
C170.058 (3)0.087 (5)0.076 (4)0.001 (3)0.001 (2)0.014 (3)
C180.089 (4)0.066 (4)0.060 (3)0.012 (3)0.016 (3)0.001 (3)
C190.082 (3)0.063 (4)0.065 (3)0.007 (3)0.004 (3)0.013 (3)
C200.067 (3)0.066 (4)0.053 (3)0.006 (3)0.008 (2)0.002 (3)
C210.075 (3)0.056 (3)0.088 (4)0.004 (3)0.001 (3)0.003 (3)
Geometric parameters (Å, º) top
I—C212.143 (5)C9—C101.373 (8)
O1—C11.412 (5)C9—H90.9300
O1—C41.417 (7)C10—C111.395 (9)
O2—C61.347 (6)C10—H100.9300
O2—C21.454 (6)C11—C121.354 (9)
O3—C51.400 (5)C11—H110.9300
O3—C71.434 (6)C12—C131.396 (8)
O4—C61.199 (5)C12—H120.9300
O5—C31.401 (6)C13—H130.9300
O5—C141.434 (6)C14—C151.497 (8)
C1—C51.510 (6)C14—H14A0.9700
C1—C21.529 (8)C14—H14B0.9700
C1—H10.9800C15—C201.388 (7)
C2—C31.517 (6)C15—C161.395 (7)
C2—H20.9800C16—C171.367 (8)
C3—C41.553 (6)C16—H160.9300
C3—H30.9800C17—C181.365 (8)
C4—C211.499 (8)C17—H170.9300
C4—H40.9800C18—C191.383 (7)
C5—C61.506 (9)C18—H180.9300
C5—H50.9800C19—C201.369 (8)
C7—C81.486 (6)C19—H190.9300
C7—H7A0.9700C20—H200.9300
C7—H7B0.9700C21—H21A0.9700
C8—C91.370 (7)C21—H21B0.9700
C8—C131.380 (7)
C1—O1—C4110.1 (3)C8—C9—C10121.4 (5)
C6—O2—C2110.8 (4)C8—C9—H9119.3
C5—O3—C7113.6 (3)C10—C9—H9119.3
C3—O5—C14114.7 (4)C9—C10—C11118.8 (6)
O1—C1—C5108.5 (3)C9—C10—H10120.6
O1—C1—C2104.6 (4)C11—C10—H10120.6
C5—C1—C2103.5 (3)C12—C11—C10120.1 (6)
O1—C1—H1113.2C12—C11—H11119.9
C5—C1—H1113.2C10—C11—H11119.9
C2—C1—H1113.2C11—C12—C13120.9 (6)
O2—C2—C3111.0 (5)C11—C12—H12119.6
O2—C2—C1104.3 (3)C13—C12—H12119.6
C3—C2—C1104.6 (3)C8—C13—C12119.0 (6)
O2—C2—H2112.1C8—C13—H13120.5
C3—C2—H2112.1C12—C13—H13120.5
C1—C2—H2112.1O5—C14—C15106.2 (4)
O5—C3—C2114.9 (5)O5—C14—H14A110.5
O5—C3—C4109.0 (4)C15—C14—H14A110.5
C2—C3—C4103.7 (4)O5—C14—H14B110.5
O5—C3—H3109.7C15—C14—H14B110.5
C2—C3—H3109.7H14A—C14—H14B108.7
C4—C3—H3109.7C20—C15—C16117.5 (5)
O1—C4—C21108.4 (3)C20—C15—C14122.2 (5)
O1—C4—C3107.0 (3)C16—C15—C14120.3 (5)
C21—C4—C3113.1 (6)C17—C16—C15121.0 (5)
O1—C4—H4109.4C17—C16—H16119.5
C21—C4—H4109.4C15—C16—H16119.5
C3—C4—H4109.4C18—C17—C16121.1 (5)
O3—C5—C6110.0 (3)C18—C17—H17119.4
O3—C5—C1116.5 (3)C16—C17—H17119.4
C6—C5—C1102.1 (4)C17—C18—C19118.5 (5)
O3—C5—H5109.3C17—C18—H18120.7
C6—C5—H5109.3C19—C18—H18120.7
C1—C5—H5109.3C20—C19—C18120.9 (5)
O4—C6—O2121.7 (6)C20—C19—H19119.5
O4—C6—C5128.1 (5)C18—C19—H19119.5
O2—C6—C5110.2 (4)C19—C20—C15120.8 (5)
O3—C7—C8108.4 (4)C19—C20—H20119.6
O3—C7—H7A110.0C15—C20—H20119.6
C8—C7—H7A110.0C4—C21—I112.2 (4)
O3—C7—H7B110.0C4—C21—H21A109.2
C8—C7—H7B110.0I—C21—H21A109.2
H7A—C7—H7B108.4C4—C21—H21B109.2
C9—C8—C13119.7 (5)I—C21—H21B109.2
C9—C8—C7119.0 (5)H21A—C21—H21B107.9
C13—C8—C7121.3 (5)

Experimental details

(I)(II)
Crystal data
Chemical formulaC22H26O5C21H21IO5
Mr370.43480.28
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21
Temperature (K)173296
a, b, c (Å)5.5273 (5), 13.4315 (13), 26.074 (2)6.0077 (7), 15.4106 (14), 11.0654 (13)
α, β, γ (°)90, 90, 9090, 96.066 (2), 90
V3)1935.7 (3)1018.72 (19)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.091.60
Crystal size (mm)0.50 × 0.30 × 0.300.40 × 0.30 × 0.30
Data collection
DiffractometerBruker CCD 1000 area-detector
diffractometer
Bruker CCD 1000 area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Blessing, 1995)
Empirical (using intensity measurements)
(SADABS; Blessing, 1995)
Tmin, Tmax0.933, 0.9740.567, 0.645
No. of measured, independent and
observed [I > 2σ(I)] reflections
10541, 2262, 1973 4977, 2969, 2480
Rint0.0450.018
(sin θ/λ)max1)0.6250.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.135, 1.00 0.028, 0.065, 1.03
No. of reflections22622969
No. of parameters234244
No. of restraints01
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.200.52, 0.27
Absolute structure?Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter?0.02 (2)

Computer programs: SMART (Bruker, 2000–2003), SMART (Bruker, 2000-2003), SMART, SAINT? and SHELXTL (Bruker, 2000–2003), SHELXTL, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O50.841.932.741 (3)163
O5—H5···O1i0.841.942.754 (3)162
Symmetry code: (i) x+1/2, y+3/2, z.
 

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