Crystal structure of 1,1′-biphenyl-2,2′,3,3′- tetracarboxylic and 1,1′-biphenyl-2,2′,3,3′,5,5′,6, 6′-octacarboxylic acids: Solid-state chiralization and dissociation

Article abstract of DOI:10.1016/j.tetasy.2004.10.016

X-ray diffraction analysis revealed unexpected stereochemical features accompanying crystal self-assembly of the two title oligocarboxylic acids.

Full text of DOI:10.1016/j.tetasy.2004.10.016

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 15 (2004) 3805–3810
Crystal structure of 1,10-biphenyl-2,20,3,30-tetracarboxylic and
1,10-biphenyl-2,20,3,30,5,50,6,60-octacarboxylic acids: solid-state
chiralization and dissociation
a
a
a
b
Petr Holy´,a, Petr Sehnal, Milos Tichy, Jirı Zavada and Ivana Cısarova
´
*
ˇ
ˇ´ ´
´ ˇ
´
a
´
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam.2,
166 10 Prague 6, Czech Republic
bDepartment of Inorganic Chemistry, Faculty of Natural Sciences, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
Received 29September 2004; accepted 19October 2004
Abstract—X-ray diffraction analysis revealed unexpected stereochemical features accompanying crystal self-assembly of the two title
oligocarboxylic acids.
ꢀ 2004 Elsevier Ltd. All rights reserved.
1. Introduction
via intermolecular double hydrogen bonds (Scheme 1a
and b).
Currently we are interested in the self-assembly of sym-
metrical 1,10-biphenyl oligocarboxylic acids. As part of a
more extensive study1 on porous architectures, we have
recently investigated the self-assembling behavior of two
isomeric tetracarboxylic acids, 1 and 2, which may be
viewed upon as the Siamese twins belonging, respec-
tively, to the terephthalic and isophthalic families. Self-
assembling patterns of the twin tectons have been corre-
lated with those established earlier for the parent benz-
ene dicarboxylic acids. Both terephthalic as well as
isophthalic tectons tend to form 1D ribbons organized
The Siamese twins 1 and 2 replicate this self-assembling
motif in two divergent directions giving rise to 2D
infinite grids set up from open cyclotetrameric
compartments.2
The isomeric Siamese twin 3 awaits analogous scrutiny.
The parent phthalic acid tecton is known3 to self-assem-
ble via intermolecular double hydrogen bonds under the
formation of zig-zag 1D ribbons (Scheme 1c). The twin
tecton 3, on replication with this motif in two divergent
H
O
O
O
H O
O
O
O H
O H
O
H
O
O
H
O
H
a
O
O
O
O
H
H
H
O
H
O
H
O
O
O
O
O
O
O
H
O
H
H
H
O
H
O
O
O
O
O
O
O
H
O
O
c
b
Scheme 1.
*
Corresponding author. Tel.: +420 220 183 382; fax: +420 220 183 560; e-mail: petrholy@uochb.cas.cz
0957-4166/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2004.10.016

´
P.Holy et al./ Tetrahedron: Asymmetry 15 (2004) 3805–3810
3806
(orthogonal) directions, would tend to yield nonporous
corrugated 2D layers or infinite helices.
COOCH3
I
COOCH3
COOCH3
i
ii, iii
COOCH3
COOCH3
3
More interesting, in this context, is the homologous octa-
carboxy-substituted twin tecton 4, which on replication
of the phthalic acid self-assembling motif in four ortho-
gonal directions might provide access to infinite aniso-
tropic open-pore 3D structures set up from coaxial
helices; we have recently discovered such patterns in
the cyclodextrin series.1f,g
COOCH3
Br
Br
H3C
H3C
CH3
CH3
ROOC
ROOC
COOR
COOR
iv
We herein report the X-ray structure of the two twin tec-
tons 3 and 4.
5: R = H
v, vi
6: R = CH3
COOH
vii, ii, iii
4
COOH
Scheme 2. Reagents and conditions: (i) Cu, 240ꢁC; (ii) NaOH, H2O,
EtOH; (iii) HCl; (iv) KMnO4, Py, 110ꢁC; (v) SOCl2; (vi) MeOH; (vii)
Cu, DMF, 150ꢁC.
HOOC
HOOC
HOOC
HOOC
COOH
COOH
1
2
COOH
HOOC
HOOC
HOOC
COOH
COOH
HOOC
HOOC
COOH
COOH
HOOC
COOH
3
4
2. Results and discussion
2.1. Synthesis
1,10-Biphenyl-2,20,3,30-tetracarboxylic acid 3 was pre-
pared by Ullmann coupling of dimethyl 3-iodophthal-
ate4 by modification of a known procedure.5 The
corresponding octacarboxylic acid 4 was prepared anal-
ogously (Scheme 2), starting from 3-bromo-1,2,4,5-benz-
enetetracarboxylic acid6
5
permanganate oxidation of bromodurene.
easily accessible by
Figure 1. Molecular structure of tetraacid 3 (only one enantiomer is
shown). Ellipsoids for 50% probability.
2.2. X-ray crystallographic analysis
2.2.1. Molecular structure of 1,10-biphenyl-2,20,3,30-tetra-
carboxylic acid 3. The investigated crystal of tecton 3
corresponds to the monohydrate. The molecular struc-
ture (Fig. 1) exhibits nearly orthogonal orientation of
the coupled phenyl groups (dihedral angle 88.69ꢁ). Phe-
nyl groups in the individual molecules are almost ideally
planar, the observed displacements of the individual ring
Planes of both carboxyl groups placed in the inner
(2,20-) positions of the twin molecule 3 are almost per-
pendicular with respect to the adjacent phenyl rings
(dihedral angle 75.36ꢁ and 82.86ꢁ, respectively).
Whereas planes of the outer carboxyls (3,30-) attached
to C3 and C30 are turned out much less, the correspond-
ing dihedral angles were only 15.08ꢁ and 9.32ꢁ, respec-
tively. Also these findings differ markedly from the
arrangement found7 in the parent phthalic acid, which
exhibits mild, and comparable, deviation of both the
neighboring carboxyls from the plane of the benzene
ring, the corresponding dihedral angles being 30.5ꢁ
and 32.0ꢁ, respectively.
˚
carbons being close to 0.013A (at C3) or less. Although
more significant displacements occur at the pivotal car-
bons of the adjacent carboxyls, as evident from the per-
tinent torsion angles C7–C2–C3–C8 (À8.78ꢁ) and C70–
C20–C30–C80 (À4.91ꢁ), the observed values are markedly
smaller than those reported by Ermer7 for the parent
phthalic acid (20.3ꢁ).

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P.Holy et al./ Tetrahedron: Asymmetry 15 (2004) 3805–3810
3807
Finally, the intramolecular single hydrogen bond be-
tween the inner carboxyls distinguishes the twin mole-
cule 3 (Fig. 1) from the parent phthalic acid. This
might suggest that the arrangement of carboxyl groups
in the two compared molecules depends on the absence
or presence of the intramolecular hydrogen bond. A
caveat against such a conclusion provides however the
known crystal structure of benzene-1,2,3-tricarboxylic,8
benzene-1,2,4-tricarboxylic,9 and benzene-1,2,4,5-tetra-
carboxylic10 acids. Notably, in all the three phthalic acid
homologues, which do not exhibit intramolecular
hydrogen bonds, values of the torsion angles about
carboxylic groups closely resemble the pattern found
in the biphthalic acid 3 rather than that in the parent
phthalic acid. According to Ermer,7 the distinct geome-
try in phthalic acid can be rationalized in terms of spe-
cific packing (intermolecular) forces accompanying the
crystal self-assembly.
2.2.2. Chiral aspects of the crystal self-assembly of the
tecton 3. Orthogonal arrangement of the coupled
phenyls accounts for the axial chirality of tecton 3 in
the investigated crystal. Both enantiomers with other-
wise identical geometries are present in the unit cell
and are held together by hydrogen bonds mediated by
water molecules (Fig. 2).
Figure 2. Perspective view on stacking of molecules of tetraacid 3 and
water. Scheme of stacks differing in chirality below.
Homochiral tectons are organized in stacks along axis b
via direct single hydrogen bonds connecting the carb-
oxyl at position 3 with the corresponding group placed
at position 2 in the neighboring molecule. Alternation
of the homochiral stacks with the antipode stacks along
axis c gives rise to zones of high and low polarity, in
which the water-mediated hydrogen bonds between car-
boxyls or the aromatic moieties, respectively, prevail.
The resulting architecture thus differs fundamentally
from the prediction based on the helical elaboration of
the phthalic acid motif (Scheme 1c).
inner 2,20-carboxyls can be found in both twin tectons
3 and 4.
A striking difference exists, however, concerning the nat-
ure of this particular bond in the two compared mole-
cules. While
a
simple uncharged intramolecular
hydrogen bond results in tetraacid 3, the corresponding
hydrogen bonding in octaacid 4 is accompanied by the
dissociation of the participating acceptor carboxyl
group in the 2-position. This is a surprising observation,
since carboxyl dissociation is very uncommon in the
crystallography of carboxylic acids.ꢀ Two water mole-
cules (from total four symmetrically independent ones)
bind the liberated proton in the complex H5Oþ2 ion
(Fig. 4) by a strong symmetrical hydrogen bond (the dis-
tances of hydrogen H1a to the both acceptor atoms O1w
and O2w are identical within the accuracy limits).
2.2.3. Molecular structure of 1,10-biphenyl-2,20,3,30,
5,50,6,60-octacarboxylic acid 4. The investigated crystal
corresponds to the tetrahydrate. The molecular struc-
ture of the twin tecton 4 (Fig. 3) resembles in most
respects that described above for the tetracarboxy-
substituted twin 3. Thus, the coupled phenyl groups
in 4 are nearly planar and mutually orthogonal,
with the dihedral angle between the planes of the
adjacent aromatic rings being 83.18ꢁ. The pivotal car-
bons of all the individual carboxyls are displaced only
mildly from the plane of the neighboring aromatic ring,
the pertinent values of the torsion angles C17–C12–
C13–C8 (3.94ꢁ), C19–C15–C16–C110 (À12.42ꢁ), C27–
C22–C23–C28 (7.98ꢁ), and C29–C25–C26–C210
(À12.09ꢁ) closely approaching those established for
tetraacid 3.
2.2.4. Chiral aspects of the crystal self-assembly of the
tecton 4. In contrast to the tetra-substituted twin tec-
ton 3, the orthogonal arrangement of the coupled phe-
nyl rings, alone, cannot promote axial chirality in the
octa-substituted homologue 4, owing to the persisting
planes of symmetry. In the investigated crystal of tecton
4, however, the introduction of an intramolecular
hydrogen bond (along with the accompanying deproto-
nization) chiralizes the intrinsically achiral molecule.
Also the dihedral angles between the planes of the indi-
vidual carboxyl groups and the corresponding aromatic
rings in the tecton 4 follow an analogous pattern as
found for the lower homologue 3, the inner 2,20,6,60-car-
boxyls being much more turned out (63.92–79.50ꢁ) than
those in the outer 3,30,5,50-positions (10–16ꢁ). Further-
more, the intramolecular hydrogen bond involving the
ꢀ We are aware of only one, a peculiar precedent concerning trifluoro-
acetic acid. For the tetrahydrate an ionic structure (H5O2)[(CF3-
COO)2H]Æ6H2O, which is analogous to the present case, was
confirmed by X-ray analysis, whereas the perdeuterated tetrahydrate
was found to be molecular (non-ionic); Ref. 11.

´
P.Holy et al./ Tetrahedron: Asymmetry 15 (2004) 3805–3810
3808
Figure 5. Perspective view on the unit cell in the crystal of the
tetrahydrate of octaacid 4. Scheme of chirality of individual molecules
of 4 below.
Figure 3. Molecular structure of octaacid 4 (only one enantiomer is
shown). Ellipsoids for 50% probability.
1c), as similarly observed above for the lower homo-
logue 3.
2.2.5. Concluding remarks on the predictability of the
crystal packing of the investigated twin tectons. The ob-
served discord between the actual crystal structure of the
twin tectons 3 and 4 and the prediction based on a
multidirectional replication of the self-assembling motif
outlined in Scheme 1c contrasts with the successful cor-
relations we attained previously with the akin tectons 1
and 2 on basis of the corresponding Scheme 1a and b.
Low stability of the key motif from Scheme 1c may be
responsible for this failure. As already noted by Ermer
in his analysis,7 expression of this motif in the crystal
of phthalic acid imposes a severe strain in the structure
of the parent molecule. Less strained alternatives, which
avoid the geometrically demanding double hydrogen
bonds can accordingly prevail in crystal packing of the
twins 3 and 4.
Figure 4. Hydrogen bonding of the complex H5Oþ2 ion in the crystal of
the tetrahydrate of octaacid 4.
Both enantiomers can be discerned in the elementary cell
containing eight molecules of tecton 4 (four enantio-
meric pairs) accompanied by 32 molecules of water
(Fig. 5).
3. Experimental
Melting points were determined on a Kofler apparatus
and are uncorrected. H NMR spectra were measured
1
Homochiral molecules are stacked along the b and c
axis, while along the a axis, chirality alternates. The
neighboring tectons are linked by single intermolecular
hydrogen bonds between the proximate carboxyls, each
molecule being interconnected with six surrounding
counterparts. The direct hydrogen bonds between prox-
imal carboxyls are complemented by indirect ones
involving water molecules. Also the complex ion H5O2þ
arising from the dissociation of the carboxylic group
(Fig. 4) participates in the 3D hydrogen bonded net-
work, which in turn results in very dense crystal packing
(dc = 1.7227gcmÀ3). In this way, the crystal architecture
differs fundamentally from the prediction based of the
helical elaboration of the phthalic acid motif (Scheme
on a Varian Unity XL-200 and a Bruker 400 spectro-
meter (200 and 400MHz, respectively, FT mode) in deu-
teriochloroform or in hexadeuteriodimethyl sulfoxide.
Mass spectra were recorded on a ZAB-EQ (VG-Analyt-
ical) instrument. Thioglycerol–glycerol and 2-hydroxy-
ethyl disulfide matrices were used for the FAB
technique.
3.1. Synthesis
3.1.1. 1,10-Biphenyl-2,20,3,30-tetracarboxylic acid 3. This
tetraacid was prepared5 by saponification of the tetra-
methyl ester, which was obtained by Ullmann coupling

´
P.Holy et al./ Tetrahedron: Asymmetry 15 (2004) 3805–3810
3809
of dimethyl 3-iodophthalate.4 Yield 76%, mp 274–275ꢁC,
lit.5 265ꢁC. 1H NMR (DMSO-d6): d 13.0 (s, 4H);
7.87 (dd, J = 7.7 and 1.3Hz, 2H); 7.53 (t, J = 7.7Hz,
2H); 7.44 (dd, J = 7.7 and 1.3Hz, 2H). Anal. Calcd
for C16H10O8ÆH2O: C, 55.18; H; 3.47. Found C, 54.99;
H, 3.36. The monocrystal (monohydrate) for X-ray
analysis was obtained by slow crystallization from
water.
acid was allowed to crystallize in a refrigerator over-
night, filtered off, washed with a small amount of
water, and dried in vacuo at 120ꢁC. Yield 338mg
(89%), mp >350ꢁC. FAB MS: m/z 573 [M+3Na]+; 551
[M+2Na]+; 529[M+Na] +; 507 [M+H]+. HR FAB MS:
m/z for C20H10O16+H calcd 507.0047; found 507.0031.
1H NMR (DMSO-d6): d 13.30 (s, 8H); 8.13 (s, 2H).
The monocrystal (tetrahydrate) for X-ray analysis was
obtained by slow cooling of hot aqueous solution.
3.1.2. 3-Bromo-1,2,4,5-benzenetetracarboxylic acid 5. To
a stirred solution of 3-bromo-1,2,4,5-tetramethyl-benzene
(25g; 117mmol, prepared in 77% yield by bromination12
of 1,2,4,5-tetramethylbenzene) in pyridine (200mL) was
added a hot solution of potassium permanganate (248g;
1.57mol) in water (1330mL) at 115ꢁC for 8h. After an
additional 5h heating, the deposited manganese dioxide
was filtered off, and washed with 0.3% aqueous KOH
(2 · 300mL). The combined filtrates were collected and
concentrated to 500mL. After acidification with concd
HCl to pH1, the precipitated tetraacid was filtered off,
washed with water, acetone, and dried. Yield 31.4g
(80%), mp >350ꢁC, lit.6 240–265ꢁC. 1H NMR (D2O/
NaOD): d 8.60 (s, 1H). Anal. Calcd for C10H5BrO8
(333.05): C, 36.06; H, 1.51; Br, 23.99. Found: C, 35.96;
H, 1.58; Br, 23.51.
3.2. X-ray diffraction analysis
X-ray data were collected on a Nonius Kappa CCD dif-
˚
fractometer, MoKa radiation (k = 0.71073A, graphite
monochromator) at 150(2) K. The structure was solved
by direct methods (SIR9214), full-matrix least-squares
refinements on F2 were carried out using the program
SHELXL9715. All nonhydrogen atoms were refined aniso-
tropically and converged ((D/r)max = 0.003). The posi-
tions of the hydrogen atoms bonded to oxygen were
found on a difference Fourier map and refined isotropi-
cally. Those in CH moieties were fixed into idealized
positions (riding model) and assigned temperature
factors Hiso (H) = 1.2 Ueq (pivot atom). Crystal data,
measurement and refinement details are summarized in
Table 1. Parameters of hydrogen bonds are collected in
Table 2.
3.1.3. Tetramethyl 3-bromo-1,2,4,5-benzenetetra-carb-
oxylate 6. A mixture of tetraacid 5 (3.33g; 10.0mmol),
thionyl chloride (40mL; 550mmol), and a drop of DMF
was heated at reflux for 8h. The excess of thionyl chlo-
ride was then removed in vacuo and the residue heated
to reflux with methanol (50mL) for 1h. After filtration,
the solvent was removed, and the crude tetraester crys-
tallized successively from methanol and toluene/petro-
All crystallographic data for the investigated structures
3 and 4 have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publication
numbers: 3-CCDC 250626, 4-CCDC 250625. Copies of
the data can be obtained, free of charge, on application
1
leum ether. Yield 73%, mp 135ꢁC. H NMR(CDCl3):
d 8.65 (s, 1H); 4.01 (s, 6H); 3,96 (s, 6H). FAB MS:
Table 1. Crystallographic data
m/z 389/391 [M+H]+; 357/359[M+H–CH OH]+. Anal.
3
Compound
3ÆH2O
4Æ4H2O
Calcd for C14H13O8Br (389.05): C, 43.21; H, 3.37; Br,
20.53. Found C, 43.40; H, 3.42; Br, 20.48.
Formula
Mr
C
16H12O8ÆH2O
C20H9O16ÆH3OÆ3H2O
578.34
348.26
3.1.4. Octamethyl 1,10-biphenyl-2,20,3,30,5,50,6,60-octa-
carboxylate 7. A mixture of bromotetraester 6 (2.5g;
6.42mmol) and activated13 copper bronze (2.5g;
39.3mmol) in DMF (7.5mL) was heated 3.5h at
150ꢁC. After dilution with water (50mL), the mixture
was extracted with ethyl acetate (3 · 50mL). The com-
bined extracts were washed with water (20mL), dried
over Na2SO4, and evaporated. The residue was sub-
jected to column chromatography (silica gel 250g; tolu-
ene/ethyl acetate/ethanol 90:8:2 to 90:8:4). After
separation of the side product (tetramethyl 1,2,4,5-benz-
enetetracarboxylate; 634mg; 2.04mmol; 32%), the de-
sired octaester was eluted (1.107g; 1.79mmol; 56%).
Mp after crystallization from toluene 174–176ꢁC. 1H
NMR (200MHz; CDCl3): d 8.41 (s, 2H); 3.91 (s, 12
H); 3.60 (s, 12 H). FAB MS: m/z 619[M+H] +; 587
[M+H–CH3OH]+. Anal. Calcd for C28H26O16 (618.12):
C, 54.38; H, 4.24. Found C, 54.36; H, 4.27.
Crystal system
Space group
Triclinic
P-1 (No. 2)
7.5640(4)
9.1680(4)
12.0240(7)
87.827(3)
76.165(3)
66.436(2)
2
Monoclinic
C2/c (No. 15)
20.8270(10)
12.9211(10)
19.3320(10)
˚
a, A
˚
b, A
˚
c, A
a, ꢁ
b, ꢁ
c, ꢁ
Z
121.007(2)
8
3
˚
V, A
Dc, gcmÀ3
740.56(7)
1.562
4459.0(4)
1.723
Crystal dimensions, mm 0.25 · 0.1 · 0.025 0.4 · 0.25 · 0.075
Appearance
l, mmÀ1
h Range
Colorless bar
0.131
Colorless plate
0.160
À9 , 9
À25, 25
À15, 15
À23, 19
24,721
k Range
l Range
À10, 11
À15, 15
12,956
Reflections measured
)
Independent (Rint
3333 (0.0310)
2532
250
4294 (0.0378)
3474
425
Observed [I > 2r(I)]
Parameters refined
3.1.5. 1,10-Biphenyl-2,20,3,30,5,50,6,60-octacarboxylic acid
4. A mixture of octaester 7 (500mg; 0.808mmol) and
aqueous 2.6M NaOH (5mL) was heated at reflux for
8h. After acidification with concd HCl to pH1, the octa-
S
1.011
0.0460
1.055
0.0443
0.1206
R
wR2
0.1172
0.460; À0.4090.317;
À3
˚
Dqmax; Dqmin, eA
À0.350

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P.Holy et al./ Tetrahedron: Asymmetry 15 (2004) 3805–3810
3810
Table 2. Parameters of hydrogen bonds in the investigated crystals
˚
Distances (A)
Compound
Specification
Bond angle (ꢁ)
O–Hꢀ ꢀ ꢀO
O–Hꢀ ꢀ ꢀO
O–H
Hꢀ ꢀ ꢀO
Oꢀ ꢀ ꢀO
3ÆH2O
O6–H60ꢀ ꢀ ꢀO1
0.92(2)
0.95(3)
0.99(3)
0.90(2)
0.91(4)
0.91(4)
0.91(4)
1.82(3)
1.73(3)
1.69(3)
1.85(3)
1.90(4)
2.13(4)
2.46(4)
2.7150(17)
2.6759(18)
2.6310(17)
2.7103(18)
2.797(2)
161(2)
174(2)
159(2)
158(2)
170(3)
138(3)
141(3)
O4–H40ꢀ ꢀ ꢀO5ai
O2–H20ꢀ ꢀ ꢀO1w
O8–H80ꢀ ꢀ ꢀO1waii
O1w–H1bꢀ ꢀ ꢀO1aiii
O1w–H1aꢀ ꢀ ꢀO7aiv
O1w–H1aꢀ ꢀ ꢀO3av
2.8703(17)
3.219(2)
4Æ4H2O
O1w–H1aꢀ ꢀ ꢀO2w
O1w–H1bꢀ ꢀ ꢀO15bi
O1w–H1bꢀ ꢀ ꢀO15bii
O1w–H1cꢀ ꢀ ꢀO23biii
O2w–H2aꢀ ꢀ ꢀO13biv
O2w–H2bꢀ ꢀ ꢀO22bii
O3w–H3aꢀ ꢀ ꢀO27bv
O3w–H3bꢀ ꢀ ꢀO25bvi
O4w–H4aꢀ ꢀ ꢀO17
1.21(3)
1.00(5)
1.00(7)
0.98(3)
0.98(4)
0.85(3)
0.99(3)
0.98(4)
1.01(4)
1.11(4)
1.00(3)
0.95(4)
0.97(4)
0.90(3)
0.90(3)
0.90(3)
0.96(3)
0.93(4)
1.21(3)
2.15(5)
2.05(5)
1.67(3)
1.70(5)
1.88(3)
1.79(3)
1.88(4)
1.81(4)
1.74(4)
1.52(3)
1.58(4)
1.63(4)
1.81(3)
2.52(3)
1.81(3)
1.63(3)
1.79(4)
2.412(2)
2.870(2)
2.816(2)
2.635(2)
2.665(2)
2.703(2)
2.707(2)
2.832(2)
2.793(2)
2.824(2)
2.5109(19)
2.523(2)
2.5823(19)
2.7081(19)
3.0460(19)
2.7086(19)
2.582(2)
2.693(2)
176(3)
128(4)
132(4)
166(3)
167(4)
162(3)
153(3)
165(4)
163(3)
164(3)
172(3)
173(3)
164(3)
175(3)
118(2)
171(3)
174(3)
165(3)
O4w–H4bꢀ ꢀ ꢀO3wbvii
O12–H12ꢀ ꢀ ꢀO21
O14–H14ꢀ ꢀ ꢀO4wbviii
O28–H15ꢀ ꢀ ꢀO22bii
O16–H16ꢀ ꢀ ꢀO11bix
O16–H16ꢀ ꢀ ꢀO12bix
O18–H18ꢀ ꢀ ꢀO11bv
O24–H24ꢀ ꢀ ꢀO3wbx
O26–H26ꢀ ꢀ ꢀO21bxi
Symmetry transformations used to generate equivalent atoms:
(ai): x, 1 + y, z; (aii): Àx, Ày, 1 À z; (aiii): Àx, 1 À y, 1 À z; (aiv): À1 + x, 1 + y, z; (av): À1 + x, y, z; (bi): x, Ày, À1/2 + z; (bii): 3/2 À x, À1/2 + y,
3/2 À z; (biii): 3/2 À x, 1/2 À y, 1 À z; (biv): À1/2 + x, À1/2 À y, À1/2 + z; (bv): 3/2 À x, 1/2 + y, 3/2 À z; (bvi): 1/2 + x, 1/2 À y, 1/2 + z; (bvii):
À1/2 + x, À1/2 + y, z; (bviii): 1/2 + x, À1/2 + y, z; (bix): x, Ày, 1/2 + z; (bx): 2 À x, y, 3/2 À z; (bxi): À1/2 + x, À1/2 + y, À1/2 + z.
´
´
´
ˇ
´
2. Holy´, P.; Sehnal, P.; Zavada, J.; Tichy, M.; Cısarova, I.
Tetrahedron: Asymmetry 2003, 14, 245–253.
3. Leiserowitz, L. Acta Crystallogr., Sect. B 1976, 32, 775–
802.
to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: +44(0)-1223-336033 or e-mail: deposit@
ccdc.cam.ac.uk).
4. Twiss, D.; Heinzelmann, R. V. J.Org.Chem. 1950, 15,
496–510.
5. Kenner, J.; Mathews, A. M. J.Am.Chem.Soc. 1914, 105,
2471–2482.
Acknowledgements
The financial support provided by the Grant Agency of
the Czech Republic to the authors (Grant No. 203/03/
0087) and to the Center for Molecular and Crystal
Structures (Grant No. 203/99/M037) is gratefully
acknowledged.
6. Bovonsombat, P.; McNelis, E. Synthesis 1993, 237–241.
7. Ermer, O. Helv.Chim.Acta 1981, 64, 1902–1909.
8. (a) Mo, F.; Adman, E. Acta Crystallogr., Sect. B 1975, 31,
192; (b) Fornies-Marquina, J. M.; Courseille, C.; Busetta,
B.; Hospital, M. Cryst.Struct.Commun. 1971, 1, 47; (c)
Takusagawa, F.; Hirotsu, K.; Shimada, A. Bull.Chem.
Soc.Jpn. 1973, 46, 2998–3004.
9. Takusagawa, F.; Hirotsu, K.; Shimada, A. Bull.Chem.
Soc.Jpn. 1973, 46, 2960.
References
10. Takusagawa, F.; Hirotsu, K.; Shimada, A. Bull.Chem.
Soc.Jpn. 1971, 44, 1274–1278.
11. Mootz, D.; Schilling, M. J. J.Am.Chem.Soc. 1992, 114,
7435–7439.
´
´
ˇ
´
1. (a) Holy´, P.; Zavada, J.; Cısarova, I.; Podlaha, J. Angew.
Chem., Int. Ed. 1999, 38, 381–383; (b) Holy´, P.; Zavada, J.;
´
´
Cısarova, I.; Podlaha, J. Tetrahedron: Asymmetry 2001,
12, 3035–3045; (c) Holy´, P.; Zavada, J.; Zezula, J.;
´
Cısarova, I.; Podlaha, J. Collect.Czech.Chem.Commun.
2001, 66, 820–832; (d) Holy´, P.; Podlaha, J.; Cısarova, I.;
´
Zavada, J. Collect.Czech.Chem.Commun. 2001, 66, 947–
958; (e) Tichy´, M.; Holy´, P.; Zavada, J.; Cısarova, I.;
Podlaha, J. Tetrahedron: Asymmetry 2001, 12, 2295–2300;
´
(f) Kraus, T.; Budesınsky, M.; Zavada, J.; Cısarova, I.
Angew.Chem., Int.Ed. 2002, 40, 1715–1717; (g) Kraus, T.;
´ ˇ ´
Zavada, J.; Cısarova, I. Eur.J.Org.Chem.
ˇ
´
´
12. Philippi, E.; Seka, R. Monatsh.Chem. 1924, 45, 273–279.
13. Vogelꢁs Textbook of Practical Organic Chemistry, 5th ed.;
Furniss, B. S., Hannaford, A. J., Tatchell, A. R., Eds.
John Wiley & Sons: New York, 1989; p 426.
14. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi,
A.; Burla, M. C.; Polidori, G.; Camalli, M. J.Appl.
Crystallogr. 1994, 27, 435.
15. Sheldrick, G. M. SHELXL-97 A Program for Crystal
Structure Refinement; University of Go¨ttingen: Germany,
1997.
ˇ
´
´
ˇ
´
´
´
ˇ
´
ˇˇ´
´
´
´
ˇ
´
2004, 4060–
4069.