D Mannitol 1,2,6 tribenzoate

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organic papers

o1118

Jenny M. Carret al. C₂₇H₂₆O₉ DOI: 10.1107/S1600536801018074 Acta Cryst.(2001). E57, o1118±o1119 Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

D

-Mannitol-1,2,6-tribenzoate

Jenny M. Carr,a_{Scott P. Draffin,}b

Peter J. Duggan,c_{Gary D.}

Fallonc_{* and David G.}

Humphreya

a_{CSIRO Forestry and Forest Products, Private Bag}

10, Clayton South, Victoria 3169, Australia, b_{Centre of Green Chemistry, PO Box 23,}

Monash University, Victoria 3800, Australia, andc_{School of Chemistry, PO Box 23, Monash} University, Victoria 3800, Australia

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study T= 123 K

Mean(C±C) = 0.002 AÊ Rfactor = 0.036 wRfactor = 0.087

Data-to-parameter ratio = 10.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

d-Mannitol-1,2,6-tribenzoate, C27H26O9, was obtained as a

side product from the reaction of d-mannitol with benzoyl

chloride in hot pyridine. The major product of the reaction

wasd-mannitol-1,6-dibenzoate.

Comment

The application of boronic acids as labile protective agents in the selective functionalization of polyols is currently one of the focus areas of our research (Bhaskaret al., 2001). The title compound, (I), was obtained from a control experiment, which was performed in order to determine the yield and selectivity

of the reaction of d-mannitol with benzoyl chloride in the

absence of a boronic acid. It is interesting to note that the third

acylation ofd-mannitol occurs at 2-OH, rather than at 3-OH.

Experimental

d-Mannitol (20.03 g, 0.11 mol) was treated with benzoyl chloride (12.30 ml, 0.11 mol) in hot pyridine (75 ml), following the procedure of Morpain & Tisserand (1979). After the reaction mixture was cooled, a white precipitate was obtained, which was recrystallized from hot methanol to afford pured-mannitol-1,6-dibenzoate (4.29 g, 20%) (Bhaskar et al., 2001). The addition of water to the recrys-tallization ®ltrate, followed by prolonged cooling, produced a crop of colourless needles that were collected by ®ltration, washed with diethyl ether and dried in air. Spectroscopic and X-ray crystal-lographic characterization of the needles revealed the second product to be d-mannitol-1,2,6-tribenzoate (0.31 g, 2%); m.p. 438±441 K [literature 439±440 K (Hockett & Fletcher, 1944)].

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Crystal data

C27H26O9

Mr= 494.48

Orthorhombic,P212121

a= 5.572 (1) AÊ b= 15.530 (1) AÊ c= 27.221 (2) AÊ V= 2355.5 (5) AÊ3

Z= 4

Dx= 1.394 Mg mÿ3

MoKradiation

Cell parameters from 35667 re¯ections

= 2.6±28.3

= 0.11 mmÿ1

T= 123 (2) K Acicular, colourless 0.300.220.18 mm

Data collection

KappaCCD diffractometer CCD ('and!) scans 26379 measured re¯ections 3347 independent re¯ections 2894 re¯ections withI> 2(I)

Rint= 0.042

max= 28.3

h=ÿ7!7 k=ÿ20!17 l=ÿ36!36

Re®nement

Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.036}

wR(F2_{) = 0.087}

S= 1.08 3347 re¯ections 328 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2₍_F

o2) + (0.0433P)2

+ 0.3834P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.008

max= 0.24 e AÊÿ3

min=ÿ0.17 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O3ÐH1 O7i _0.84 _2.15 _{2.9641 (19)} ₁₆₃

O4ÐH2A O3ii _0.84 _2.15 _{2.9164 (18)} ₁₅₂

O4ÐH2A O3 0.84 2.43 2.8636 (18) 113 O5ÐH3A O9iii _0.84 _1.94 _{2.7668 (19)} ₁₆₉

Symmetry codes: (i)1

2x;32ÿy;2ÿz; (ii)xÿ12;32ÿy;2ÿz; (iii) 1x;y;z.

As the absolute structure cannot be reliably determined for this light-atom study, all Friedel pairs (2368) have been merged. The H light-atoms were included in the riding-model approximation. The torsion angles about the CÐO bonds of the hydroxyl groups have been re®ned.

Data collection: COLLECT (Nonius, 1997±2000); cell re®nement:

HKLandSCALEPACK(Otwinowski & Minor, 1997); data reduc-tion: HKL, DENZO (Otwinowski & Minor, 1997) and SCALE-PACK; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP3for Windows (Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

This work was supported by the Australian Research Council.

References

Bhaskar, V., Duggan, P. J., Humphrey, D. G., Krippner, G. Y., McCarl, V. & Offermann, D. A. (2001).J. Chem. Soc. Perkin Trans.1, pp. 1098±1102. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.

Hockett, R. C. & Fletcher, H. G. (1944).J. Am. Chem. Soc.66, 469±471, and references therein.

Morpain, C. & Tisserand, M. (1979).J. Chem. Soc. Perkin Trans.1, pp. 1379± 1383.

Nonius (1997±2000).COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter and R. M. Sweet, pp. 307±326. London: Academic Press.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.

Figure 1

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supporting information

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Acta Cryst. (2001). E57, o1118–o1119

supporting information

Acta Cryst. (2001). E57, o1118–o1119 [doi:10.1107/S1600536801018074]

D

-Mannitol-1,2,6-tribenzoate

Jenny M. Carr, Scott P. Draffin, Peter J. Duggan, Gary D. Fallon and David G. Humphrey

S1. Comment

The application of boronic acids as labile protective agents in the selective functionalization of poly-ols is currently one

of the focus areas of our research (Bhaskar et al., 2001). The title compound, (I), was obtained from a control experiment,

which was performed in order to determine the yield and selectivity of the reaction of D-mannitol with benzoyl chloride

in the absence of a boronic acid. It is interesting to note that the third acylation of D-mannitol occurs at 2-OH, rather than

3-OH.

S2. Experimental

D-Mannitol (20.03 g, 0.11 mol) was treated with benzoyl chloride (12.30 ml, 0.11 mol) in hot pyridine (75 ml), following

the procedure of Morpain & Tisserand (1979). After the reaction mixture was cooled, a white precipitate was obtained

which was recrystallized from hot methanol to afford pure D-mannitol-1,6-dibenzoate (4.29 g, 20%) (Bhaskar et al.,

2001). The addition of water to the recrystallization filtrate, followed by prolonged cooling, produced a crop of colourless

needles that were collected by filtration, washed with diethyl ether and dried in air. Spectroscopic and X-ray

crystallographic characterization of the needles revealed the second product to be D-mannitol-1,2,6-tribenzoate (0.31 g,

2%). m.p. 438–441 K [literature 439–440 K (Hockett & Fletcher, 1944)].

S3. Refinement

Because the absolute structure cannot be reliably determined for this light-atom study, all Friedel pairs (2368) have been

merged. The H atoms were included in the riding-model approximation. The torsion angles about the C—O bonds of the

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[image:4.610.124.483.71.253.2]

Figure 1

View of (I) (50% probability displacement ellipsoids).

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Crystal data

C27H26O9

Mr = 494.48

Orthorhombic, P212121

a = 5.572 (1) Å

b = 15.530 (1) Å

c = 27.221 (2) Å

V = 2355.5 (5) Å3

Z = 4

F(000) = 1040

Dx = 1.394 Mg m−3 Melting point = 165–168 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 35667 reflections

θ = 2.6–28.3°

µ = 0.11 mm−1

T = 123 K

Acicular, colourless 0.3 × 0.22 × 0.18 mm

Data collection

KappaCCD diffractometer CCD scans

26379 measured reflections 3347 independent reflections 2894 reflections with I > 2σ(I)

Rint = 0.042

θmax = 28.3°, θmin = 2.6°

h = −7→7

k = −20→17

l = −36→36

Refinement

Refinement on F2 Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.036}

wR(F2_{) = 0.087}

S = 1.08 3347 reflections 328 parameters 0 restraints

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2₍_F

o2) + (0.0433P)2 + 0.3834P] where P = (Fo2 + 2Fc2)/3

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Acta Cryst. (2001). E57, o1118–o1119

Special details

Experimental. IR (KBr): 3523 cm-1₍_s_{), 3464(}_s_{), 1721(}_s_{), 1702(}_s_{), 1698(}_s_{), 1693(}_s_{), 1602(w), 1585(w), 1492(w),} 1452(m), 1341(m), 1321(m), 1286(s), 1248(s), 1180(w), 1124(s), 1112(s), 1095(m), 1073(m), 1055(m), 1028(m), 973(w), 937(w), 914(w), 890(w), 876(w), 843(w), 817(w), 733(w), 710(s), 690(w), 676(w).

APCI MS (MeCN/H2O/MeOH): 517 (M+Na+).

1_{H n.m.r. (300 MHz, DMSO):}_δ_{3.63 (t, J8 Hz, 1H), 3.91 (m, 1H), 4.28 (m, 2H), 4.48 (dd, J1.2 Hz, 1H), 4.59 (dd, J6.6}

Hz, 1H), 4.93 (m, 2H), 5.16 (m, 2H), 5.43 (dt, J3.2 Hz, 1H), 7.41 (t, J8 Hz, 3H), 7.51 (q, J5.1 Hz, 4H), 7.64 (m, 3H), and 7.95 (m, 5H).

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

C1 0.6532 (3) 0.90581 (10) 1.02859 (5) 0.0257 (3)

H1A 0.6655 0.8453 1.0397 0.031*

H1B 0.8118 0.9236 1.0157 0.031*

C2 0.4672 (3) 0.91269 (9) 0.98835 (5) 0.0200 (3)

H2 0.3029 0.9055 1.0026 0.024*

C3 0.5040 (3) 0.84870 (9) 0.94622 (5) 0.0182 (3)

H3 0.6498 0.8649 0.9269 0.022*

C4 0.2836 (2) 0.84831 (10) 0.91264 (5) 0.0184 (3)

H4 0.2605 0.9086 0.9007 0.022*

C5 0.3221 (2) 0.79167 (10) 0.86725 (5) 0.0197 (3)

H5 0.3839 0.7339 0.8774 0.024*

C6 0.0906 (3) 0.78130 (10) 0.83890 (5) 0.0225 (3)

H6A −0.0383 0.7601 0.8608 0.027*

H6B 0.04 0.8372 0.8248 0.027*

C7 0.4023 (3) 0.93413 (10) 1.09772 (5) 0.0250 (3)

C8 0.3493 (3) 0.99616 (10) 1.13791 (5) 0.0257 (3)

C9 0.5071 (3) 1.06237 (11) 1.14897 (6) 0.0339 (4)

H9 0.6529 1.0679 1.1312 0.041*

C10 0.4529 (4) 1.12046 (12) 1.18587 (7) 0.0427 (5)

H10 0.562 1.1655 1.1935 0.051*

C11 0.2404 (4) 1.11297 (13) 1.21156 (6) 0.0425 (5)

H11 0.2029 1.153 1.2368 0.051*

C12 0.0832 (4) 1.04767 (13) 1.20063 (6) 0.0416 (5)

H12 −0.0638 1.0432 1.2181 0.05*

C13 0.1375 (3) 0.98793 (11) 1.16409 (6) 0.0338 (4)

H13 0.0302 0.942 1.1572 0.041*

C14 0.3296 (3) 1.05813 (10) 0.97932 (6) 0.0256 (3)

C15 0.3858 (3) 1.14201 (10) 0.95574 (6) 0.0249 (3)

C16 0.5947 (3) 1.15360 (11) 0.92828 (6) 0.0286 (4)

H16 0.7069 1.1079 0.9251 0.034*

C17 0.6380 (3) 1.23234 (11) 0.90562 (6) 0.0348 (4)

H17 0.7785 1.24 0.8864 0.042*

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H18 0.5087 1.3534 0.8959 0.043*

C19 0.2694 (3) 1.28784 (12) 0.93855 (6) 0.0344 (4)

H19 0.1585 1.3339 0.9421 0.041*

C20 0.2239 (3) 1.20951 (11) 0.96073 (6) 0.0289 (4)

H20 0.0816 1.2018 0.9795 0.035*

C21 −0.0454 (3) 0.70303 (10) 0.76941 (5) 0.0228 (3)

C22 0.0142 (3) 0.64023 (10) 0.73013 (5) 0.0226 (3)

C23 −0.1537 (3) 0.62648 (11) 0.69305 (6) 0.0288 (4)

H23 −0.2989 0.6586 0.6926 0.035*

C24 −0.1089 (3) 0.56595 (11) 0.65676 (6) 0.0326 (4)

H24 −0.2229 0.5568 0.6313 0.039*

C25 0.1006 (3) 0.51906 (10) 0.65753 (6) 0.0295 (4)

H25 0.1289 0.4767 0.633 0.035*

C26 0.2700 (3) 0.53307 (11) 0.69369 (6) 0.0329 (4)

H26 0.4151 0.5009 0.6938 0.04*

C27 0.2283 (3) 0.59416 (11) 0.72993 (6) 0.0306 (4)

H27 0.3457 0.6045 0.7545 0.037*

O1 0.58698 (19) 0.96051 (7) 1.06978 (4) 0.0265 (3)

O2 0.48923 (18) 0.99710 (6) 0.96617 (4) 0.0233 (2)

O3 0.53636 (17) 0.76484 (6) 0.96754 (4) 0.0206 (2)

H1 0.6303 0.7359 0.9499 0.031*

O4 0.07167 (17) 0.82501 (7) 0.93867 (4) 0.0247 (2)

H2A 0.1079 0.7928 0.9623 0.037*

O5 0.49849 (19) 0.83535 (7) 0.83905 (4) 0.0273 (2)

H3A 0.5638 0.8005 0.8196 0.041*

O6 0.13745 (18) 0.71908 (7) 0.79978 (4) 0.0235 (2)

O7 0.2927 (2) 0.86750 (7) 1.09080 (4) 0.0322 (3)

O8 0.1615 (2) 1.04522 (7) 1.00639 (5) 0.0404 (3)

O9 −0.24122 (19) 0.73684 (8) 0.77320 (4) 0.0320 (3)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0264 (7) 0.0291 (9) 0.0217 (7) 0.0052 (7) −0.0034 (6) −0.0100 (7)

C2 0.0198 (7) 0.0195 (8) 0.0207 (7) 0.0014 (6) −0.0005 (5) −0.0003 (6)

C3 0.0164 (6) 0.0205 (8) 0.0176 (6) 0.0002 (6) 0.0009 (5) 0.0008 (6)

C4 0.0173 (6) 0.0213 (8) 0.0167 (6) 0.0012 (6) 0.0006 (5) −0.0005 (6)

C5 0.0169 (7) 0.0237 (8) 0.0186 (7) 0.0004 (6) 0.0007 (6) 0.0000 (6)

C6 0.0204 (7) 0.0280 (9) 0.0191 (7) 0.0017 (6) 0.0007 (6) −0.0054 (6)

C7 0.0283 (8) 0.0265 (9) 0.0202 (7) 0.0010 (7) −0.0045 (6) 0.0012 (6)

C8 0.0335 (8) 0.0242 (8) 0.0194 (7) −0.0008 (7) −0.0014 (6) 0.0010 (6)

C9 0.0364 (9) 0.0351 (9) 0.0303 (8) −0.0049 (8) 0.0036 (8) −0.0064 (7)

C10 0.0510 (12) 0.0390 (11) 0.0381 (10) −0.0137 (9) 0.0025 (9) −0.0151 (8)

C11 0.0579 (12) 0.0434 (11) 0.0263 (8) −0.0032 (10) 0.0050 (8) −0.0122 (8)

C12 0.0457 (10) 0.0485 (12) 0.0306 (9) −0.0043 (9) 0.0115 (8) −0.0042 (8)

C13 0.0406 (10) 0.0320 (10) 0.0289 (8) −0.0086 (8) 0.0050 (7) −0.0033 (7)

C14 0.0227 (8) 0.0266 (9) 0.0274 (8) 0.0016 (6) −0.0007 (6) −0.0042 (7)

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Acta Cryst. (2001). E57, o1118–o1119

C16 0.0248 (8) 0.0281 (9) 0.0330 (8) 0.0009 (7) 0.0019 (7) −0.0004 (7)

C17 0.0262 (8) 0.0392 (11) 0.0391 (10) −0.0007 (8) 0.0048 (7) 0.0046 (8)

C18 0.0383 (10) 0.0309 (10) 0.0381 (9) −0.0012 (8) −0.0041 (8) 0.0093 (8)

C19 0.0348 (9) 0.0296 (10) 0.0387 (9) 0.0085 (7) −0.0019 (8) 0.0033 (8)

C20 0.0252 (8) 0.0312 (9) 0.0301 (8) 0.0030 (7) 0.0011 (7) −0.0011 (7)

C21 0.0215 (7) 0.0272 (8) 0.0198 (7) −0.0036 (6) 0.0001 (6) 0.0008 (6)

C22 0.0248 (7) 0.0247 (8) 0.0183 (7) −0.0029 (6) 0.0005 (6) −0.0006 (6)

C23 0.0266 (8) 0.0330 (10) 0.0267 (8) 0.0011 (7) −0.0044 (6) −0.0026 (7)

C24 0.0375 (9) 0.0368 (10) 0.0233 (8) −0.0041 (8) −0.0086 (7) −0.0055 (7)

C25 0.0374 (9) 0.0258 (9) 0.0254 (8) −0.0074 (7) 0.0043 (7) −0.0064 (7)

C26 0.0307 (8) 0.0336 (10) 0.0346 (9) 0.0042 (7) −0.0006 (7) −0.0084 (8)

C27 0.0274 (8) 0.0377 (10) 0.0268 (8) 0.0016 (7) −0.0058 (7) −0.0086 (7)

O1 0.0298 (6) 0.0271 (6) 0.0227 (5) −0.0015 (5) −0.0017 (5) −0.0064 (4)

O2 0.0243 (5) 0.0198 (6) 0.0258 (5) 0.0013 (5) 0.0031 (5) −0.0019 (4)

O3 0.0214 (5) 0.0208 (5) 0.0197 (5) 0.0039 (4) −0.0001 (4) −0.0004 (4)

O4 0.0165 (5) 0.0383 (7) 0.0193 (5) 0.0005 (4) 0.0016 (4) 0.0008 (5)

O5 0.0238 (5) 0.0348 (6) 0.0232 (5) −0.0039 (5) 0.0083 (5) −0.0053 (5)

O6 0.0214 (5) 0.0297 (6) 0.0195 (5) 0.0014 (4) −0.0015 (4) −0.0072 (4)

O7 0.0451 (7) 0.0245 (7) 0.0270 (6) −0.0085 (5) −0.0026 (5) −0.0014 (5)

O8 0.0347 (7) 0.0308 (7) 0.0556 (8) 0.0063 (5) 0.0203 (6) 0.0037 (6)

O9 0.0224 (5) 0.0461 (8) 0.0275 (6) 0.0040 (5) −0.0014 (5) −0.0110 (5)

Geometric parameters (Å, º)

C1—O1 1.4543 (17) C13—H13 0.95

C1—C2 1.5117 (19) C14—O8 1.2085 (19)

C1—H1A 0.99 C14—O2 1.3481 (18)

C1—H1B 0.99 C14—C15 1.485 (2)

C2—O2 1.4484 (17) C15—C20 1.390 (2)

C2—C3 1.5312 (19) C15—C16 1.395 (2)

C2—H2 1 C16—C17 1.391 (2)

C3—O3 1.4371 (17) C16—H16 0.95

C3—C4 1.5309 (18) C17—C18 1.381 (2)

C3—H3 1 C17—H17 0.95

C4—O4 1.4237 (16) C18—C19 1.392 (2)

C4—C5 1.5319 (19) C18—H18 0.95

C4—H4 1 C19—C20 1.382 (2)

C5—O5 1.4197 (17) C19—H19 0.95

C5—C6 1.512 (2) C20—H20 0.95

C5—H5 1 C21—O9 1.2155 (18)

C6—O6 1.4616 (17) C21—O6 1.3353 (17)

C6—H6A 0.99 C21—C22 1.485 (2)

C6—H6B 0.99 C22—C27 1.391 (2)

C7—O7 1.2162 (19) C22—C23 1.393 (2)

C7—O1 1.3434 (19) C23—C24 1.386 (2)

C7—C8 1.487 (2) C23—H23 0.95

C8—C13 1.384 (2) C24—C25 1.376 (2)

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C9—C10 1.383 (2) C25—C26 1.381 (2)

C9—H9 0.95 C25—H25 0.95

C10—C11 1.380 (3) C26—C27 1.388 (2)

C10—H10 0.95 C26—H26 0.95

C11—C12 1.372 (3) C27—H27 0.95

C11—H11 0.95 O3—H1 0.84

C12—C13 1.393 (2) O4—H2A 0.84

C12—H12 0.95 O5—H3A 0.84

O1—C1—C2 110.08 (12) C13—C12—H12 119.7

O1—C1—H1A 109.6 C8—C13—C12 119.42 (16)

C2—C1—H1A 109.6 C8—C13—H13 120.3

O1—C1—H1B 109.6 C12—C13—H13 120.3

C2—C1—H1B 109.6 O8—C14—O2 123.81 (14)

H1A—C1—H1B 108.2 O8—C14—C15 124.90 (14)

O2—C2—C1 107.93 (12) O2—C14—C15 111.28 (13)

O2—C2—C3 105.30 (11) C20—C15—C16 119.78 (15)

C1—C2—C3 113.89 (11) C20—C15—C14 118.86 (14)

O2—C2—H2 109.9 C16—C15—C14 121.36 (14)

C1—C2—H2 109.9 C17—C16—C15 119.73 (15)

C3—C2—H2 109.9 C17—C16—H16 120.1

O3—C3—C4 109.77 (11) C15—C16—H16 120.1

O3—C3—C2 107.61 (10) C18—C17—C16 120.25 (16)

C4—C3—C2 110.02 (11) C18—C17—H17 119.9

O3—C3—H3 109.8 C16—C17—H17 119.9

C4—C3—H3 109.8 C17—C18—C19 119.94 (16)

C2—C3—H3 109.8 C17—C18—H18 120

O4—C4—C3 111.66 (11) C19—C18—H18 120

O4—C4—C5 111.82 (11) C20—C19—C18 120.13 (16)

C3—C4—C5 111.80 (11) C20—C19—H19 119.9

O4—C4—H4 107.1 C18—C19—H19 119.9

C3—C4—H4 107.1 C19—C20—C15 120.16 (16)

C5—C4—H4 107.1 C19—C20—H20 119.9

O5—C5—C6 111.44 (11) C15—C20—H20 119.9

O5—C5—C4 105.01 (12) O9—C21—O6 123.48 (14)

C6—C5—C4 110.69 (11) O9—C21—C22 123.06 (13)

O5—C5—H5 109.9 O6—C21—C22 113.45 (12)

C6—C5—H5 109.9 C27—C22—C23 119.63 (14)

C4—C5—H5 109.9 C27—C22—C21 122.16 (14)

O6—C6—C5 106.87 (11) C23—C22—C21 118.19 (14)

O6—C6—H6A 110.3 C24—C23—C22 119.95 (15)

C5—C6—H6A 110.3 C24—C23—H23 120

O6—C6—H6B 110.3 C22—C23—H23 120

C5—C6—H6B 110.3 C25—C24—C23 120.06 (15)

H6A—C6—H6B 108.6 C25—C24—H24 120

O7—C7—O1 123.81 (14) C23—C24—H24 120

O7—C7—C8 124.41 (15) C24—C25—C26 120.49 (15)

(9)

supporting information

sup-7

Acta Cryst. (2001). E57, o1118–o1119

C13—C8—C9 119.82 (15) C26—C25—H25 119.8

C13—C8—C7 119.22 (14) C25—C26—C27 119.96 (16)

C9—C8—C7 120.96 (15) C25—C26—H26 120

C10—C9—C8 120.21 (17) C27—C26—H26 120

C10—C9—H9 119.9 C26—C27—C22 119.87 (15)

C8—C9—H9 119.9 C26—C27—H27 120.1

C11—C10—C9 120.01 (18) C22—C27—H27 120.1

C11—C10—H10 120 C3—O3—H1 109.5

C9—C10—H10 120 C4—O4—H2A 109.5

C12—C11—C10 119.98 (17) C5—O5—H3A 109.5

C12—C11—H11 120 C7—O1—C1 116.91 (12)

C10—C11—H11 120 C14—O2—C2 118.02 (11)

C11—C12—C13 120.55 (17) C21—O6—C6 116.00 (11)

C11—C12—H12 119.7

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H1···O7i _0.84 _2.15 _{2.9641 (19)} ₁₆₃

O4—H2A···O3ii _0.84 _2.15 _{2.9164 (18)} ₁₅₂

O4—H2A···O3 0.84 2.43 2.8636 (18) 113

O5—H3A···O9iii _0.84 _1.94 _{2.7668 (19)} ₁₆₉