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The centrosymmetric O—H...O-bonded head-to-head dimers of the title compound, C21H22O6, are linked together via bifurcated C—H...O inter­actions along the a axis and via favourable C—H...π inter­actions along the b axis in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105029422/av1256sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105029422/av1256Isup2.hkl
Contains datablock I

CCDC reference: 290567

Comment top

Protected myo-inositol derivatives are important precursors for the synthesis of phosphorylated myo-inositol derivatives (Sureshan et al., 2003), which play a significant role in cellular signal transduction (Potter & Lampe, 1995). myo-Inositol 1,3,5-orthoformate is a key intermediate for the synthesis of several myo-inositol phosphates and other cyclitols (Sarmah, Shashidhar et al., 2005). Encouraged by frequently encountered polymorphic (Gonnade et al., 2004, Bhosekar et al., 2005) and pseudopolymorphic (Manoj et al., 2005) behaviour of myo-inositol derivatives, 4,6-di-O-benzyl-myo inositol 1,3,5-orthoformate, (I), was also screened for the same property by varying crystallization conditions. However, compound (I) yielded only solvent free crystals of triclinic form from most of the common organic solvents, such as dichloromethane, ethyl acetate, chloroform, dioxane and acetonitrile.

Three axial positions at C1, C3 and C5 constitute the orthoformate bridge (Fig. 1). The conformation of the molecule as observed in the crystal shows three rather weak intramolecular interactions. The equatorial hydroxy group O2—H2A makes bifurcated O—H···O contacts with the orthoformate bridge atoms O1 and O3. Another bifurcated contact of C—H···O type is made by C2/H2 with ether O atoms O4 and O6 (Table 1). An almost perpendicular orientation of the phenyl rings [the dihedral angle between the rings is 83.35 (15)°] facilitates the somewhat off-centered C21—H21···π interaction (H21···C9 = 2.85 Å and H21···C14 = 2.83 Å).

Molecules of compound (I) form centrosymmetric dimers through conventional intermolecular O2—H2A···O1 bonds, bringing the orthoformate bridge heads closer but causing the two benzyloxy groups to point away (Fig. 2). These dimers also make centrosymmetric bifurcated C—H···O contacts with O3 (C15—H15B···O3 and C4—H4···O3) extended along the a axis, forming two-dimensional ribbon-like patterns with the hydrophilic groups clustered together and the hydrophobic phenyl rings protruding out (Fig. 2 and Table 1).

Both the phenyl rings make intermolecular C—H···π contacts; the C15/H15A group interacts with the C16–C21 aromatic ring (Table 1) to form layers normal to the [101] direction (Fig. 3) with a very favourable geometry, whereas the C9–C14 phenyl ring is held by C6—H6···C9 and C1—H1···C10 contacts (H6···C9 = 2.99 Å and H1···C10 = 2.94 Å, respectively) from one side and the above-mentioned intramolecular contact involving the C21/H21 group from the other side (Fig. 3). It is noteworthy that the phenyl rings are involved only in C—H···π contacts and not in any ππ stacking interactions in the structure. The significance of C—H···π interactions is well established in various fields of chemistry, including self-assembly (Xie et al., 2005), crystal packing (Suezawa et al., 2001), inclusion complexes (Kobayashi et al., 1993) and solid-state reactions (Sarmah, Gonnade et al., 2005). An extensive search (Takahashi et al., 2000) of the Cambridge Structural Database (CSD; Allen, 2002) for the existence of C—H···π interactions strongly suggests the weak hydrogen-bond character of these interactions (Nishio et al., 1998).

The packing of O—H···O bonded dimers down the c axis is shown in Fig. 4. The organization of molecules shows some voids (~3.5 × 5.0 Å), marked as A, that are too small for the inclusion of any organic solvent or even a water molecule.

Experimental top

2-O-Tosyl myo-inositol orthoformate (Sureshan et al., 2002) (0.177 g, 0.5 mmol) was dissolved in dimethylformamide (4 ml), and stirred for 2 min after the addition of sodium hydride (0.024 g, 1 mmol). Benzyl bromide (0.15 ml, 1 mmol) was then added and the mixture was stirred at room temperature for 5 min. The solvents were evaporated under reduced pressure and the residue obtained was worked up with ethyl acetate to obtain 2-O-tosyl 4,6-di-O-benzyl myo-inositol orthoformate. The tosyl group was cleaved by refluxing with sodium methoxide (0.270 g, 5 mmol) in methanol (5 ml) for 12 h. The reaction mixture was then quenched with ice and extracted with ethyl acetate. The extract then washed with dilute HCl, saturated Na2CO3 solution and brine, and dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure and the solid obtained was dissolved in dichloromethane, diluted with petroleum ether and stored at ambient temperature. Good quality colorless crystals were obtained after 4 h (0.188 g, 99%). M.p. 401–403 K (literature m.p. 393–396 K; Devaraj et al., 2005).

Refinement top

The hydroxy H atom was constrained to an ideal geometry [O—H = 0.82 Å and Uiso(H) = 1.5Ueq(C)]. Other H atoms were placed in idealized positions ((C—H = 0.98 Å for the cyclohexane ring H atoms and atom H7, C—H = 0.93 Å for phenyl H atoms, and C—H = 0.97 Å for methylene H atoms) and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL or SHELXL97? and PLATON.

Figures top
[Figure 1] Fig. 1. ORTEPIII (Burnett & Johnson, 1996) diagram of (I), drawn with 30% ellipsoidal probability. The broken lines show O—H···O, C—H···O and C—H···π intramolecular interactions.
[Figure 2] Fig. 2. Dimers linked by bifurcated C—H···O interactions viewed down b axis. The broken lines show O—H···O and C—H···O intermolecular hydrogen bonds. [Symmetry codes: (i) −x, 2 − y, 1 − z; (ii) 1 − x, 2 − y, 1 - z.]
[Figure 3] Fig. 3. Involvement of C—H···π contacts of both the phenyl rings. [Symmetry code: (i) −x, 1 − y, 2 − z; (ii) 1 − x, 2 − y, 2 - z.]
[Figure 4] Fig. 4. Molecular packing viewed down the c axis with voids marked as A.
4,6-di-O-benzyl-myo-inositol 1,3,5-orthoformate top
Crystal data top
C21H22O6Z = 2
Mr = 370.39F(000) = 392
Triclinic, P1Dx = 1.370 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0511 (11) ÅCell parameters from 4418 reflections
b = 10.0953 (12) Åθ = 2.4–25.0°
c = 10.6586 (13) ŵ = 0.10 mm1
α = 68.849 (2)°T = 298 K
β = 81.453 (2)°Plate, colourless
γ = 87.433 (2)°0.29 × 0.22 × 0.13 mm
V = 898.18 (19) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3328 independent reflections
Radiation source: fine-focus sealed tube2911 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ϕ and ω scansθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.972, Tmax = 0.987k = 1212
13398 measured reflectionsl = 1212
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0492P)2 + 0.1889P]
where P = (Fo2 + 2Fc2)/3
3328 reflections(Δ/σ)max < 0.001
245 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C21H22O6γ = 87.433 (2)°
Mr = 370.39V = 898.18 (19) Å3
Triclinic, P1Z = 2
a = 9.0511 (11) ÅMo Kα radiation
b = 10.0953 (12) ŵ = 0.10 mm1
c = 10.6586 (13) ÅT = 298 K
α = 68.849 (2)°0.29 × 0.22 × 0.13 mm
β = 81.453 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3328 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2911 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.987Rint = 0.025
13398 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.09Δρmax = 0.19 e Å3
3328 reflectionsΔρmin = 0.18 e Å3
245 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
O10.08346 (13)0.82091 (13)0.56489 (11)0.0548 (3)
O20.05322 (15)1.05070 (13)0.67506 (12)0.0610 (3)
H2A0.04881.07180.59390.091*
O30.29271 (14)0.96560 (12)0.50180 (11)0.0548 (3)
O40.43134 (11)0.80447 (11)0.83176 (10)0.0456 (3)
O50.31956 (14)0.72249 (13)0.55383 (11)0.0541 (3)
O60.15616 (12)0.64614 (11)0.91057 (10)0.0481 (3)
C10.07916 (18)0.79865 (18)0.70736 (16)0.0481 (4)
H10.02440.78380.75260.058*
C20.14470 (18)0.92921 (17)0.71997 (16)0.0465 (4)
H20.15260.90840.81590.056*
C30.30119 (18)0.95300 (17)0.64071 (15)0.0471 (4)
H30.34431.04010.64120.056*
C40.40363 (17)0.82758 (17)0.69805 (15)0.0432 (4)
H40.49940.84440.63800.052*
C50.33030 (18)0.69580 (17)0.69527 (15)0.0445 (4)
H50.39230.61240.73140.053*
C60.17021 (18)0.66758 (16)0.77084 (15)0.0455 (4)
H60.12820.58550.75950.055*
C70.2317 (2)0.84144 (19)0.49922 (17)0.0548 (4)
H70.22980.85450.40380.066*
C80.2177 (2)0.51857 (17)0.99283 (16)0.0519 (4)
H8A0.32250.51350.95850.062*
H8B0.16610.43770.99020.062*
C90.20203 (17)0.51446 (16)1.13636 (15)0.0420 (4)
C100.2683 (2)0.40657 (18)1.23196 (17)0.0549 (4)
H100.32000.33611.20700.066*
C110.2590 (2)0.4018 (2)1.36406 (19)0.0680 (5)
H110.30350.32801.42750.082*
C120.1838 (2)0.5060 (2)1.40202 (19)0.0665 (5)
H120.17830.50351.49070.080*
C130.1175 (2)0.6130 (2)1.30843 (19)0.0626 (5)
H130.06610.68331.33380.075*
C140.12607 (19)0.61784 (18)1.17634 (18)0.0535 (4)
H140.08030.69131.11370.064*
C150.5328 (2)0.90548 (17)0.83732 (17)0.0522 (4)
H15A0.48120.99390.82910.063*
H15B0.61340.92440.76200.063*
C160.59578 (17)0.85005 (16)0.96902 (16)0.0431 (4)
C170.73766 (19)0.89361 (19)0.97369 (19)0.0533 (4)
H170.79330.95420.89490.064*
C180.7966 (2)0.8478 (2)1.0941 (2)0.0651 (5)
H180.89100.87901.09640.078*
C190.7171 (3)0.7567 (2)1.2102 (2)0.0690 (6)
H190.75790.72471.29100.083*
C200.5772 (3)0.71263 (19)1.20726 (19)0.0665 (5)
H200.52280.65121.28640.080*
C210.5162 (2)0.75925 (18)1.08676 (18)0.0540 (4)
H210.42100.72901.08560.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0550 (7)0.0654 (7)0.0472 (6)0.0053 (6)0.0228 (5)0.0172 (5)
O20.0726 (8)0.0594 (7)0.0566 (7)0.0237 (6)0.0315 (6)0.0216 (6)
O30.0658 (8)0.0576 (7)0.0388 (6)0.0117 (6)0.0158 (5)0.0099 (5)
O40.0443 (6)0.0546 (6)0.0430 (6)0.0016 (5)0.0159 (5)0.0197 (5)
O50.0639 (8)0.0640 (7)0.0429 (6)0.0005 (6)0.0128 (5)0.0273 (5)
O60.0541 (7)0.0459 (6)0.0408 (6)0.0057 (5)0.0090 (5)0.0110 (5)
C10.0420 (9)0.0578 (10)0.0439 (8)0.0009 (7)0.0136 (7)0.0144 (7)
C20.0525 (10)0.0475 (9)0.0421 (8)0.0101 (7)0.0211 (7)0.0149 (7)
C30.0557 (10)0.0460 (9)0.0427 (8)0.0047 (7)0.0189 (7)0.0146 (7)
C40.0408 (8)0.0527 (9)0.0398 (8)0.0004 (7)0.0099 (6)0.0193 (7)
C50.0499 (9)0.0487 (9)0.0400 (8)0.0025 (7)0.0126 (7)0.0197 (7)
C60.0500 (9)0.0452 (9)0.0433 (8)0.0060 (7)0.0118 (7)0.0156 (7)
C70.0639 (11)0.0650 (11)0.0390 (8)0.0085 (9)0.0157 (8)0.0184 (8)
C80.0636 (11)0.0436 (9)0.0474 (9)0.0092 (8)0.0113 (8)0.0146 (7)
C90.0393 (8)0.0404 (8)0.0443 (8)0.0021 (6)0.0044 (6)0.0131 (6)
C100.0619 (11)0.0514 (9)0.0504 (9)0.0137 (8)0.0110 (8)0.0173 (8)
C110.0770 (13)0.0720 (13)0.0494 (10)0.0170 (10)0.0180 (9)0.0135 (9)
C120.0689 (13)0.0859 (14)0.0481 (10)0.0024 (11)0.0060 (9)0.0292 (10)
C130.0619 (12)0.0674 (12)0.0649 (12)0.0082 (9)0.0031 (9)0.0346 (10)
C140.0529 (10)0.0517 (9)0.0563 (10)0.0101 (8)0.0103 (8)0.0199 (8)
C150.0641 (11)0.0442 (9)0.0548 (10)0.0000 (8)0.0249 (8)0.0192 (7)
C160.0463 (9)0.0412 (8)0.0509 (9)0.0072 (7)0.0178 (7)0.0237 (7)
C170.0468 (9)0.0577 (10)0.0638 (11)0.0036 (8)0.0129 (8)0.0302 (8)
C180.0542 (11)0.0719 (12)0.0897 (15)0.0168 (10)0.0377 (11)0.0446 (12)
C190.0920 (16)0.0621 (12)0.0701 (13)0.0241 (11)0.0484 (12)0.0327 (10)
C200.0977 (16)0.0514 (10)0.0508 (10)0.0018 (10)0.0169 (10)0.0166 (8)
C210.0575 (10)0.0519 (10)0.0573 (10)0.0047 (8)0.0151 (8)0.0220 (8)
Geometric parameters (Å, º) top
O1—C71.405 (2)C8—H8B0.9700
O1—C11.4474 (19)C9—C101.381 (2)
O2—C21.4219 (18)C9—C141.383 (2)
O2—H2A0.8200C10—C111.381 (2)
O3—C71.403 (2)C10—H100.9300
O3—C31.4530 (18)C11—C121.376 (3)
O4—C41.4175 (17)C11—H110.9300
O4—C151.4246 (19)C12—C131.366 (3)
O5—C71.400 (2)C12—H120.9300
O5—C51.4502 (17)C13—C141.382 (2)
O6—C61.4124 (18)C13—H130.9300
O6—C81.4156 (18)C14—H140.9300
C1—C61.520 (2)C15—C161.501 (2)
C1—C21.526 (2)C15—H15A0.9700
C1—H10.9800C15—H15B0.9700
C2—C31.519 (2)C16—C211.376 (2)
C2—H20.9800C16—C171.389 (2)
C3—C41.530 (2)C17—C181.378 (3)
C3—H30.9800C17—H170.9300
C4—C51.525 (2)C18—C191.367 (3)
C4—H40.9800C18—H180.9300
C5—C61.534 (2)C19—C201.369 (3)
C5—H50.9800C19—H190.9300
C6—H60.9800C20—C211.388 (2)
C7—H70.9800C20—H200.9300
C8—C91.501 (2)C21—H210.9300
C8—H8A0.9700
C7—O1—C1110.08 (11)O6—C8—C9109.43 (13)
C2—O2—H2A109.5O6—C8—H8A109.8
C7—O3—C3110.53 (11)C9—C8—H8A109.8
C4—O4—C15113.17 (12)O6—C8—H8B109.8
C7—O5—C5111.38 (12)C9—C8—H8B109.8
C6—O6—C8115.54 (12)H8A—C8—H8B108.2
O1—C1—C6108.25 (13)C10—C9—C14118.23 (15)
O1—C1—C2109.05 (13)C10—C9—C8119.58 (14)
C6—C1—C2110.63 (12)C14—C9—C8122.17 (14)
O1—C1—H1109.6C9—C10—C11120.95 (17)
C6—C1—H1109.6C9—C10—H10119.5
C2—C1—H1109.6C11—C10—H10119.5
O2—C2—C3112.23 (13)C12—C11—C10120.12 (18)
O2—C2—C1112.14 (13)C12—C11—H11119.9
C3—C2—C1107.50 (13)C10—C11—H11119.9
O2—C2—H2108.3C13—C12—C11119.45 (18)
C3—C2—H2108.3C13—C12—H12120.3
C1—C2—H2108.3C11—C12—H12120.3
O3—C3—C2108.79 (12)C12—C13—C14120.60 (18)
O3—C3—C4106.57 (13)C12—C13—H13119.7
C2—C3—C4112.09 (13)C14—C13—H13119.7
O3—C3—H3109.8C13—C14—C9120.65 (16)
C2—C3—H3109.8C13—C14—H14119.7
C4—C3—H3109.8C9—C14—H14119.7
O4—C4—C5109.73 (12)O4—C15—C16110.26 (13)
O4—C4—C3114.27 (12)O4—C15—H15A109.6
C5—C4—C3107.18 (12)C16—C15—H15A109.6
O4—C4—H4108.5O4—C15—H15B109.6
C5—C4—H4108.5C16—C15—H15B109.6
C3—C4—H4108.5H15A—C15—H15B108.1
O5—C5—C4106.25 (12)C21—C16—C17118.63 (15)
O5—C5—C6106.18 (12)C21—C16—C15122.06 (15)
C4—C5—C6114.10 (13)C17—C16—C15119.30 (15)
O5—C5—H5110.0C18—C17—C16120.57 (18)
C4—C5—H5110.0C18—C17—H17119.7
C6—C5—H5110.0C16—C17—H17119.7
O6—C6—C1106.08 (13)C19—C18—C17120.31 (18)
O6—C6—C5114.81 (12)C19—C18—H18119.8
C1—C6—C5107.42 (13)C17—C18—H18119.8
O6—C6—H6109.5C18—C19—C20119.82 (17)
C1—C6—H6109.5C18—C19—H19120.1
C5—C6—H6109.5C20—C19—H19120.1
O5—C7—O3111.92 (13)C19—C20—C21120.32 (19)
O5—C7—O1111.65 (13)C19—C20—H20119.8
O3—C7—O1110.65 (14)C21—C20—H20119.8
O5—C7—H7107.5C16—C21—C20120.34 (17)
O3—C7—H7107.5C16—C21—H21119.8
O1—C7—H7107.5C20—C21—H21119.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O60.982.472.8550 (19)103
C2—H2···O40.982.693.0463 (18)102
O2—H2A···O30.822.632.9385 (18)104
O2—H2A···O10.822.662.9408 (18)102
C10—H10···O4i0.932.673.517 (2)152
C15—H15B···O3ii0.972.643.514 (2)150
C4—H4···O3ii0.982.623.466 (2)145
O2—H2A···O1iii0.822.152.8558 (16)144
C15—H15A···Cg1iv0.972.693.602158
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+2, z+1; (iii) x, y+2, z+1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC21H22O6
Mr370.39
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)9.0511 (11), 10.0953 (12), 10.6586 (13)
α, β, γ (°)68.849 (2), 81.453 (2), 87.433 (2)
V3)898.18 (19)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.29 × 0.22 × 0.13
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.972, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
13398, 3328, 2911
Rint0.025
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.113, 1.09
No. of reflections3328
No. of parameters245
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.18

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003), SHELXTL or SHELXL97? and PLATON.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O60.982.472.8550 (19)103
C2—H2···O40.982.693.0463 (18)102
O2—H2A···O30.822.632.9385 (18)104
O2—H2A···O10.822.662.9408 (18)102
C10—H10···O4i0.932.673.517 (2)152
C15—H15B···O3ii0.972.643.514 (2)150
C4—H4···O3ii0.982.623.466 (2)145
O2—H2A···O1iii0.822.152.8558 (16)144
C15—H15A···Cg1iv0.972.693.602158
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+2, z+1; (iii) x, y+2, z+1; (iv) x+1, y, z.
 

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