Crystalline inclusion compounds of new hydroxy hosts featuring a pentaaryl substituted cyclopentadienol framework

Article abstract of DOI:10.1007/s10847-010-9850-0

The new host compounds 2 and 3 containing a biphenyl or terphenyl moiety attached to the 1-position of a bulky 2,3,4,5-tetraphenylcyclopentadiene-1-ol building unit have been synthesized. Crystal structures of corresponding inclusion complexes with n-hexa

Full text of DOI:10.1007/s10847-010-9850-0

J Incl Phenom Macrocycl Chem (2011) 70:1–9
DOI 10.1007/s10847-010-9850-0
ORIGINAL ARTICLE
Crystalline inclusion compounds of new hydroxy hosts featuring
a pentaaryl substituted cyclopentadienol framework
•
Alexander Ruffani Wilhelm Seichter
•
Edwin Weber
Received: 27 May 2010 / Accepted: 25 August 2010 / Published online: 14 September 2010
ꢀ Springer Science+Business Media B.V. 2010
Abstract The new host compounds 2 and 3 containing a
biphenyl or terphenyl moiety attached to the 1-position of a
bulky 2,3,4,5-tetraphenylcyclopentadiene-1-ol building unit
have been synthesized. Crystal structures of corresponding
inclusion complexes with n-hexane (2a), DMSO (2b)
and THF (3a) are reported and comparatively discussed
involving known inclusion structures of 1, being the parent
of this particular class of host molecules. The structural
modification from 1 via 2–3 gives rise to distinct changes of
the inclusion property concerning molecular assembly and
stoichiometric ratio of the crystal components.
possible stronger binding of the guest molecule and
increase of the complexation selectivity [6]. Very often
these functional moieties are hydroxyl groups being
established by the particular class of hydroxy hosts [7–10].
An individual example of such a host compound is given
with formula 1 (Scheme 1) showing a bulky pentaphenyl
substituted cyclopentadien-1-ol structure.
Remarkably, although the crystal structures of 1 and of
its inclusion complexes with water, methanol, ethanol and
DMSO are known for a long time [11, 12], there is no
reference indicating further development of the topic.
This prompted to synthesize related compounds of this
structure type that are 2 [13, 14] and 3 (Scheme 1), i.e.
the biphenyl and terphenyl analogous compounds of 1,
and study potential formation of crystalline inclusion
complexes. In the present paper, we describe prepara-
tion of three inclusion complexes of 2 and 3, namely 2a
[2Án-hexane (2:1)], 2b [2ÁDMSO (1:2)] and 3a [3ÁTHF
(1:2)], and report on their crystal structures, including a
comparison with the existing structures of the parent
compound 1 [11, 12].
Keywords Hydroxy hosts Á Organic guests Á Crystalline
inclusion compounds Á X-ray crystal structures Á
Supramolecular interactions
Introduction
Compounds featuring molecular shape awkwardness
encounter difficulties with close-packing in the crystal
lattice [1]. Owing to this, they frequently use a secondary
molecule as a fill in to avoid the packing problem and
hence give rise to the formation of crystalline host–guest
inclusion compounds [2, 3]. The shape awkwardness of the
host molecule is mostly caused by the concurrence of bulky
residues attached to a rigid framework structure [4, 5]. In
many cases, functional groups are also present rendering
Results and discussion
Synthesis
The host compounds 2 and 3 were prepared from 2,3,4,
5-tetraphenylcyclopentadienone (tetracyclone) and 4-biphe-
nyllithium or 4-(p-terphenyl)lithium following a literature
procedure [13]. Crystals of the inclusion compounds 2a, 2b
and 3a were obtained by slow evaporation of a solution of
the respective host compound in the corresponding guest
solvent. Details are specified in the ‘‘Experimental’’
section.
A. Ruffani Á W. Seichter Á E. Weber (&)
Institut fu¨r Organische Chemie,
¨
Technische Universitat Bergakademie Freiberg,
Leipziger Str. 29, 09596 Freiberg, Sachs, Germany
e-mail: edwin.weber@chemie.tu-freiberg.de
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J Incl Phenom Macrocycl Chem (2011) 70:1–9
bonds between the cyclopentadiene and the phenyl rings
˚
which range from 1.475(2) to 1.487(2) A. These values
agree with those found in the reported inclusion structures of
the parent compound [11, 12].
Due to the steric crowding around the hydroxy sub-
stituent, crystals of this kind of compounds in general
require the presence of a second molecular species capable
to satisfy the hydrogen bond potential of the host [3, 6] or,
in an occasionally successful solvent-free crystal, the
molecules are associated only by weak hydrogen bonding
[15] such as represented with the crystal structures
involving the host compound 1 [11, 12]. Nevertheless, in
the case of the solvent free 1, the molecule can still use the
hydroxyl group for weak conventional hydrogen bonding
[11]. This, however, does not occur in the inclusion
structure of 2 with hexane (2:1) (2a), in which the hydroxy
hydrogen of the host is without an external strong hydrogen
bond acceptor. Instead, a strong intramolecular hydrogen
˚
bond [C(7)–H(7)ÁÁÁO(1) 2.32 A, 127.4ꢁ] dictates the posi-
tion of the hydroxy hydrogen and thus favours formation of
an intramolecular O–HÁÁÁp contact [16] with the phenyl
˚
ring E acting as an acceptor [O(1)–H(1)ÁÁÁC(29) 2.62 A,
Scheme 1 Compounds studied in this paper
129.6ꢁ] (Fig. 1). Although the parameters of the O–HÁÁÁp
interaction are not ideal, the IR analysis with v~=
3,540 cm-1 (KBr) for the hydroxyl stretching band pro-
vides further evidence of the O–HÁÁÁp contact in the crystal.
This behaviour corresponds with the structural and spec-
troscopic data found for the intramolecular O–HÁÁÁp inter-
actions of crystalline 2,6-diphenylphenol [17] and related
4-nitro-2,6-diarylphenols [18]. To achieve a reasonable
hydrogen bond geometry of this interaction in 2a, an
individual carbon atom [C(29)] instead the centre of the
aromatic ring was chosen as an acceptor site (cf. Fig. 1).
The aromatic rings of the biphenyl part in 2a are twisted at
an angle of 41.2(1)ꢁ.
In the crystal structure of 2a the hexane molecule is
located on a symmetry centre at ‘, ‘, ‘. Being unable to
form intermolecular contacts, the guest molecule is disor-
dered over three positions with relative site occupancies in
the ratio 2:2:1, which indicates a lack of spatial matching
between the crystal components. Thus, the structural
organization in the crystal of 2a is mediated by a variety of
weak CHÁÁÁp interactions [19] between the aromatic units
of the host molecules. As displayed in Fig. 2, the guest
molecules are accommodated in channel-like cavities
extending in direction of the crystallographic b-axis.
Crystallization of 2 from DMSO yields an inclusion
compound 2b of the stoichiometric host:guest ratio 1:2,
showing the monoclinic space group P21/n. The content of
the asymmetric cell unit is displayed in Fig. 3. The twist
angle between the rings of the biphenyl part is 23.0(1)ꢁ; the
phenylene ring of this unit is oriented nearly orthogonal with
respect to the cyclopentadiene moiety. The oxygen of the
X-ray structural study
The solid phase structures of the inclusion compounds 2a
[2Án-hexane (2:1)], 2b [2ÁDMSO (1:2)] and 3a [3ÁTHF
(1:2)] have been determined by X-ray diffraction. Crys-
tallographic data and selected refinement parameters are
presented in Table 1. Perspective views of the molecular
structures and illustrations of the crystal packings are dis-
played in Figs. 1, 2, 3, 4, 5, and 6. In order to simplify
structural characterization, ring fragments of the host
molecules are marked with capital letters in the illustrations
of the molecular structures. The conformation can be
described by a set of interplanar angles, which define the
inclination of the aromatic rings with respect to the plane
of the cyclopentadiene ring. These geometrical parameters
together with relevant bond distanced are presented in
Table 2. Information regarding hydrogen bonding in the
crystals are listed in Table 3.
The aromatic rings B–E of the molecules 2 and 3 (Figs. 1,
3, 5) are arranged in a propeller-like fashion around the
cyclopentadiene ring, which reduces intramolecular sterical
strain. Consequently, restricted conformational freedom is
found within these unit as follows from the geometric
parameters listed in Table 2. The cyclopentadienyl and the
aromatic rings hardly deviate from planarity. Taking into
account experimental error, the bond lengths within the C5
ring are similar for the hosts 2 and 3 and range between
˚
1.344(2) and 1.355(2) A for the double bonds and 1.529(2)–
˚
1.540(2) A for the single bonds. The C(1)–C(30) bond is
˚
significantly longer [1.521(2)–1.539(2) A] than the other
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3
Table 1 Crystallographic and structure refinement data of the compounds studied
Compound
2a
2b
3a
Empirical formula
C41H30OÁ
0.5 C6H14
581.74
C41H30OÁ
2 C2H6SO
694.91
C47H34OÁ
2 C2H8O
758.95
Formula weight
Crystal system
Space group
Triclinic
P - 1
Monoclinic
P21/n
Triclinic
P - 1
˚
a (A)
9.9643(3)
10.1346(3)
18.1430(5)
79.029(1)
75.200(1)
65.864(2)
1,608.84(8)
2
12.1417(7)
21.2276(12)
14.5344(8)
90.0
10.2718(3)
10.5248(3)
20.0114(5)
76.615(1)
85.409(1)
81.098(1)
2,077.09(10)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c(ꢁ)
97.877(3)
90.0
3
˚
V (A )
3,710.7(4)
4
Z
F(000)
Dc (Mg m-3
l (mm-1
618
1472
808
)
1.201
1.244
1.213
)
0.070
0.184
0.073
Data collection
Temperature (K)
153(2)
153(2)
153(2)
No. of collected reflections
Within the h-limit (ꢁ)
35,456
45,601
51,896
1.1–27.4
2.3–27.4
1.7–27.1
Index ranges h, k,
l
-12/12, -13/13, -23/22
-15/15, -27/25, -18/18
-13/13, -13/13, -25/25
No. of unique reflections
7,288
8,183
9,078
Rint
0.0243
0.0659
0.0257
Refinement calculations: full-matrix least- squares on all F2 values
Weighting expression wa
[r2(F2o) ? (0.0868P)2 ?
[r2(F2o) ? (0.0688P)2 ?
0.8589P)]-1
[r2(F2o) ? (0.0854P)2 ?
0.4874P)]-1
0.5278P)]-1
No. of refined parameters
No. of F values used [I [ 2r(I)]
Final R-Indices
429
455
528
5,932
6,088
7,220
wR on F2
0.1505
0.1264
0.1449
S (=Goodness of fit on F2)
1.024
1.022
1.050
-3
)
˚
Final Dqqmax/Dqmin (e A
0.38/-0.33
0.72/-0.62
0.33/-0.31
P = (F2o ? 2F2c)/3
a
disordered solvent molecule is associated to the hydroxy
dimer of guest molecules via C–HÁÁÁO hydrogen bonding.
The host lattice is dominated by aromatic edge-to-face
interactions[20]. A comparative examination of the inclusion
structure of 2b with the corresponding DMSO complex of
compound 1 [11], which crystallizes also in the space group
P21/n, reveals different host:guest stoichiometries. The
crystal structure of the latter complex is composed of discrete
O–HÁÁÁO bonded (1:1) host–guest pairs, i.e. the acidic
hydrogens of the solvent molecule are excluded from coor-
dination. The packing of the host in 1ÁDMSO is characterized
by stacking of aromatic building units along the b-axis.
Similar structural features are also found in the inclusion
compound of 3 with THF (1:2), although it crystallizes in
the triclinic space group P - 1 with the cell unit containing
one host molecule and two molecules of solvent. The
hydrogen of the host via O–HÁÁÁO bonding [d(OÁÁÁO)
˚
2.685(2), 2.747(2) A] and takes part in coordination to
an arene hydrogen of a second host molecule [C(21)–
˚
H(21)ÁÁÁO(1H)/O(1HA) 2.65/2.38 A, 168.9/169.8ꢁ]. In a
similar fashion, the oxygen atom of the second DMSO
molecule acts as bifurcated acceptor and is involved in host–
˚
guest interaction [C(15)–H(15)ÁÁÁO(1G) 2.58 A, 176.2ꢁ] as
well as in association to a symmetry related guest molecule
˚
[C(2G)–H(2G3)ÁÁÁO(1G) 2.61 A, 145.9ꢁ] thus forming a
centrosymmetric dimer.
According to the given pattern of hydrogen bonding, the
crystal structure of 2b (Fig. 4) can be regarded as being
composed of molecular associates consisting of two O–HÁÁÁO
bonded (1:1) host–guest units which are linked to a cyclic
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Fig. 1 ORTEP plot of
2Án-hexane (2:1) (2a), including
the atom numbering scheme of
non-hydrogen atoms. Thermal
ellipsoids are drawn at 40%
probability level. The hydrogen
bond interaction is marked as
broken line while the broken
double line represents the
intramolecular O–HÁÁÁp
C14
C15
C9
C13
C8
C16
C
C12
B
C7
C10
C17
C11
H7
C20
C21
C19
C3
O1
C6
hydrogen bond
AC2
C4
C5
D
C2G
C18
C1
C3G
C1G
H1
C22
C30
C23
C25
C31
C24
F
C35
C32
C26
E
C34
C29
C27
C33
C28
C36
C37
C41
G
C38
C40
C39
Fig. 2 Packing diagram of 2a
viewed down the
crystallographic b-axis. With
exception of the hydroxy
hydrogen all other hydrogen
atoms are omitted for clarity.
Oxygen atoms are shaded. Only
one position of the disordered
solvent molecule is displayed
stoichiometric unit of the complex is shown in Fig. 5. The
aromatic rings of the terphenyl part of the host are twisted
in the same direction at angles of 32.9(1) (rings F/G) and
43.4(1)ꢁ (rings G/H). Ring F of this unit is oriented nearly
orthogonal with respect to the plane of the C5 ring. One of
the solvent molecules is coordinated by its disordered
oxygen atom via O–HÁÁÁO bonding with the hydroxy
hydrogen of the host [O(1)–H(1)ÁÁÁO(1G)/O(1GA) 2.01,
by C–HÁÁÁO bonding to two neighbouring host molecules
˚
[d(HÁÁÁO) 2.53, 2.77 A], while one of the acidic hydrogens
of this guest is connected to the oxygen of a further host
˚
molecule [C(3H)–H(3H2)ÁÁÁO(1) 2.65 A, 135.9ꢁ].
The crystal structure of 3a is characterized by a stack-
ing-like arrangement of host molecules in direction of the
b-axis. As depicted in Fig. 6, the host lattice contains
cavities each occupied with a pair of guest molecules. The
environment of the first solvent component which is firmly
bound within the crystal lattice is given by the bulky parts
˚
1.98 A, 174.2, 151.3ꢁ]. The oxygen atom of the second
guest molecule is coordinated in an unsymmetric fashion
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J Incl Phenom Macrocycl Chem (2011) 70:1–9
5
Fig. 3 ORTEP plot of the
stoichiometric unit of 2ÁDMSO
(1:2) (2b), including the atom
numbering scheme of non-
hydrogen atoms. Broken lines
represent hydrogen bond type
interactions. The two disordered
positions of the coordinated
solvent molecule are marked by
different bond types. Thermal
ellipsoids are drawn at 40%
probability level
Fig. 4 Packing structure of 2b
viewed down the b-axis. Only
the host hydrogens involved in
H bonding are depicted for
clarity. Heteroatoms are shaded.
Broken lines represent hydrogen
bond type interactions
of four host molecules, while pairs of the second solvent
component are included in cavities defined by the terphenyl
fragments of six host molecules.
cylcopentadiene derivatives 1–3 are related to this type of
host structure as they comprise a variable narrow element
attached to a bulky pentacyclic fragment corresponding to
one half a of ‘wheel-and-axle’ molecule. According to this
structural relationship, compounds of this particular type are
expected to form crystalline inclusions, which has previ-
ously been shown with compound 1 as the parent of this
substance class [11, 12]. Modification of the phenyl group in
the 1-position of the compound 1 to give the biphenyl and
terphenyl analogous compounds 2 and 3, respectively,
Conclusion
Compounds featuring a ‘wheel-and-axle’ geometry [10, 21,
22] have proven efficient hosts for crystalline inclu-
sion formation. In a sense, the pentaaryl substituted
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Fig. 5 ORTEP plot of the
stoichiometric unit of 3ÁTHF
(1:2) 3a, including the atom
numbering scheme of non-
hydrogen atoms. Broken lines
represent hydrogen bond type
interactions. The two disordered
oxygen positions of the
coordinated solvent molecule
are marked by different bond
types. Thermal ellipsoids are
drawn at 40% probability level
Fig. 6 Packing structure of 3a
viewed down the a-axis. Only
the host hydrogens involved in
H bonding are depicted for
clarity. Heteroatoms are shaded.
Broken lines represent hydrogen
bond type interactions
causes an increase of the bulk in the molecule and thus gives
rise to distinct changes of the inclusion behaviour, involving
both the molecular assembly in the crystal and the stoichi-
ometric ratio of the crystal components.
creates an enlarged number of weak donor- and acceptor
sites which promote formation of multiple intermolecular
CHÁÁÁp contacts and/or arene stacking. Interactions of
this type as well as the irregular molecular geometry favour
a packing structure with an antiparallel arrangement of
neighbouring host molecules. This is realized in the pres-
ent inclusion structures of 2 and 3, most perceptible with the
2Án-hexane (2:1) inclusion compound 2a. Due to the
hydrophobic nature of the solvent molecule, the hydroxy
hydrogen of the alcoholic host is used for intramolecular
The reported inclusion structures of 1 exclusively contain
polar solvents, namely H2O, DMSO, MeOH and EtOH [11,
12]. Their crystals are composed of discrete O–HÁÁÁO bonded
1:1 host–guest units, showing poor association among one
another. Introduction of the more extended biphenyl and
terphenyl units attached to C1 of the five-membered ring
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J Incl Phenom Macrocycl Chem (2011) 70:1–9
7
Hence, it is shown that modification of 1 along the lines of
2 and 3, or potentially otherwise, is a promising approach
to open a new versatile class of inclusion hosts being easily
to vary in structure and producible at low cost.
Table 2 Selected structural parameters of the host molecules 2 and 3
in their inclusion structures
Compound
2a
2b
3a
Interplanar angles (ꢁ)a
A/B
A/C
A/D
A/E
A/F
F/G
G/H
37.9(1)
52.1(1)
51.8(1)
36.3(1)
83.3(1)
41.2(1)
63.0(1)
47.7(1)
48.6(1)
62.7(1)
89.7(1)
23.0(1)
33.7(1)
54.9(1)
59.8(1)
58.0(1)
89.2(1)
32.9(1)
43.4(1)
Experimental
General
Melting points (uncorrected) were determined using a
¨
microscope heating stage PHMK Rapido (Wagetechnik
˚
Bond lengths (A)
Dresden). IR spectra were measured on a Nicolet FT-IR 510
as KBr pellets. 1H and 13C NMR spectra were recorded on a
Bruker Avance DPX 400 at 400 and 100 MHz, respectively,
using TMS as reference. MS spectra were obtained from
Hewlett Packard 5890II/MS 5989A (GC MS) and Micro-
mass Zabspec (FAB MS) instruments. Elemental analyses
were performed on a Heraeus CHN rapid analyzer. All
solvents were purified by standard procedures [25].
C(1)–C(2)
C(1)–C(5)
1.531(2)
1.529(2)
1.539(2)
1.355(2)
1.482(2)
1.492(2)
1.481(2)
1.350(2)
1.481(2)
1.475(2)
1.493(2)
1.534(2)
1.533(2)
1.525(2)
1.349(2)
1.483(2)
1.501(2)
1.478(2)
1.344(2)
1.484(2)
1.487(2)
1.488(2)
1.540(2)
1.532(2)
1.521(2)
1.353(2)
1.472(2)
1.495(2)
1.480(2)
1.347(2)
1.483(2)
1.478(2)
1.484(2)
1.484(2)
C(1)–C(30)
C(2)–C(3)
C(2)–C(6)
C(3)–C(4)
C(3)–C(12)
C(4)–C(5)
4-Bromobiphenyl was purchased from Fluka, 4-bromo-
p-terphenyl was prepared as described in the literature [26].
C(4)–C(18)
C(5)–C(24)
C(33)–C(36)
C(39)–C(42)
Bond angles (ꢁ)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(1)
C(5)–C(1)–C(2)
a
Synthesis of host compounds 2 and 3: general
procedure
Tetracyclone (2.88 g, 7.50 mmol) was added (at the
beginning as a solid and after that as a solution in dry
toluene) to a stirred solution of the corresponding organ-
yllithium compound (8.65 mmol), prepared from the
respective aryl bromide (8.65 mmol) and n-BuLi (1.6 M in
hexane 6.25 mL, 10 mmol) in dry diethylether (10 mL), at
room temperature under argon. Stirring of the mixture was
continued until completeness of the reaction, which is indi-
cated by bleaching of the black–violet colour of the tetra-
cyclone, then quenched with water and acidified (diluted
hydrochloric acid). The organic layer was separated, filtered
and dried (Na2SO4). The layer was concentrated on evapo-
ration of solvent to about 10% of its volume. Petroleum ether
(90–100 ꢁC) was added to precipitate the crude product,
which was collected and recrystallized from petroleum ether.
Details for the individual compounds are given below.
108.5(1)
109.8(1)
109.2(1)
109.1(1)
103.1(1)
109.8(1)
108.8(1)
109.6(1)
109.6(1)
102.2(1)
109.1(1)
109.4(1)
109.6(1)
109.4(1)
102.5(1)
Means angle between the best plane through atoms of the rings.
Ring A: C(1)…C(5), ring B: C(6)…C(11), ring C: C(12)…C(17), ring
D: C(18)…C(23), ring E: C(24)…C(29), ring F: C(30)…C(35), ring
G: C(36)…C(41), and ring H: C(42)…C(47)
O–HÁÁÁp(arene) bonding, while the oxygen is involved in a
strong intramolecular C–HÁÁÁO hydrogen bond. This may
explain the high degree of dynamic disorder of the solvent
within the channel-like cavity structure of the host lattice.
The elongated geometry of 2 and 3 involves also a higher
ratio of crystal solvent, which is reflected by the 1:2 host–
guest stoichiometry of 2b and 3a. As expected, in each of the
structures one of the solvent molecules is tightly connected
to the host via O–HÁÁÁO bonding, whereas the second,
weakly bonded solvent component occupies the lattice voids
left by the 1:1 host–guest entities.
1-Biphenylyl-2,3,4,5-tetraphenylcyclopentadiene-
1-ol (2)
4-Bromobiphenyl (2.02 g, 8.65 mmol) was used to yield
2.4 g (52%) of a colourless powder. Mp: 212–215 ꢁC (lit.
[13] mp: 214–216 ꢁC). IR (KBr) v~, cm-1: 3,550 (O–H),
3,084, 3,053, 3,028 (Ar–H), 1,629, 1,600 (C=C), 1,486,
1,440, 1,078 (C–O), 809 (Ar, 1,4-disubst.), 757, 700 (Ar,
On general inspection of the new inclusion structures,
one may gain the impression that the host molecules
assemble to pairs via specific interaction of the modifying
aromatic moiety imitating a ‘wheel-and-axle’ host geom-
etry similar to the transition metal [23] and carboxylic
dimer [24] mediated mimicries of wheel-and-axle hosts.
1
monosubst.). H NMR ([D6] DMSO) d, ppm: 6.41 (s, 1 H,
OH), 6.97–7.18 (m, 20 H, Ar–H), 7.29–7.65 (m, 9 H,
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Table 3 Parameters of possible hydrogen-bond type interactions in 2a, 2b and 3a
˚
Distances (A)
Atoms involved
Symmetry
Angles (ꢁ)
D–HÁÁÁA
DÁÁÁA
HÁÁÁA
2a
O(1)–H(1)ÁÁÁC(29)a
x, y, z
3.223(3)
2.997(3)
3.620(3)
3.703(3)
3.699(3)
2.58
2.32
2.86
2.89
2.82
132.1
127.5
138.1
144.3
154.0
C(7)–H(7)ÁÁÁO(1)
x, y, z
C(7)–H(7)ÁÁÁC(22)a
C(13)–H(13)ÁÁÁC(27)a
C(19)–H(19)ÁÁÁC(27)a
2b
x, -1 ? y, z
-1 ? x, y, z
2 - x, 1 - y, -z
O(1)–H(1)ÁÁÁO(1H)
O(1)–H(1)ÁÁÁO(1HA)
C(1G)–H(1G2)ÁÁÁO(1)
C(14)–H(14)ÁÁÁO(1H)
C(21)–H(21)ÁÁÁO(1H)
C(21)–H(21)ÁÁÁO(1HA)
C(15)–H(15)ÁÁÁO(1G)
C(2G)–H(2G3)ÁÁÁO(1G)
C(10)–H(10)ÁÁÁC(27)a
C(13)–H(13)ÁÁÁC(39)a
C(32)–H(32)ÁÁÁC(20)a
C(34)–H(34)ÁÁÁC(34)a
3a
x, y, z
2.747(2)
2.685(2)
3.622(3)
3.525(3)
3.589(3)
3.321(3)
3.523(3)
3.470(3)
3.731(3)
3.693(3)
3.760(3)
3.398(3)
1.91
1.86
2.64
2.60
2.65
2.38
2.58
2.61
2.80
2.87
2.86
2.77
171.8
166.6
176.0
170.7
169.8
168.9
176.2
145.9
165.9
144.9
159.1
124.3
x, y, z
0.5 ? x, 0.5 - y, -0.5 ? z
-0.5 ? x, 0.5 - y, -0.5 ? z
0.5 ? x, 0.5 - y, -0.5 ? z
0.5 ? x, 0.5 - y, -0.5 ? z
-0.5 ? x, 0.5 - y, -0.5 ? z
2 - x, 1 - y, -z
-1 ? x, y, z
1.5 - x, 0.5 ? y, 0.5 - z
2 - x, -y, -z
2 - x, -y, 1 - z
O(1)–H(1)ÁÁÁO(1G)
O(1)–H(1)ÁÁÁO(1GA)
C(3H)–H(3H2)ÁÁÁO(1)
C(23)–H(23)ÁÁÁO(1H)
C(46)–H(46)ÁÁÁO(1H)
C(7)–H(7)ÁÁÁC(47)a
C(21)–H(21)ÁÁÁC(15)a
C(27)–H(27)ÁÁÁC(41)a
C(14)–H(14)ÁÁÁcentroid ring(B)b
C(32)–H(32)ÁÁÁcentroid ring(H)b
a
x, y, z
2.846(2)
2.751(2)
3.433(3)
3.267(3)
3.540(3)
3.545(3)
3.630(3)
3.810(3)
3.561(3)
3.505(3)
2.01
1.98
2.65
2.53
2.77
2.79
2.86
2.89
2.74
2.72
174.2
151.3
135.9
134.9
138.8
137.0
138.9
162.5
144.7
140.2
x, y, z
x, -1 ? y, z
-1 ? x, 1 ? y, z
1 - x, -y, -z
1 - x, 1 - y, -z
1 - x, 2 - y, 1 - z
x, 1 ? y, z
1 - x, 1 - y, 1 - z
-x, 1 - y, -z
In order to achieve reasonable hydrogen bond geometries, individual carbon atoms instead of ring entries were chosen as acceptors
b
Means centre of the aromatic ring. Ring A: C(1)…C(5), ring B: C(6)…C(11), ring C: (12)…C(17), ring D: C(18)…C(23), ring E:
C(24)…C(29), ring F: C(30)…C(35), ring G: C(36)…C(41), and ring H: C(42)…C(47)
Ar–H). 13C NMR ([D6] DMSO) d, ppm: 89.4 (C–O),
125.6–184.5 (C=C, Ar–C). MS (GC) m/z: 538 (M?). Anal,
calcd for C41H30O: C 91.42, H 5.61; found C 91.20,
H 5.73.
NMR ([D6] DMSO) d, ppm: 6.41 (s, 1 H, OH), 6.98–7.18
(m, 20 H, Ar–H), 7.35–7.77 (m, 13 H, Ar–H). 13C NMR
([D6] DMSO) d, ppm: 89.7 (C–O), 126.0–148.8 (C=C,
Ar–C). MS (FAB) m/z: 615 (M?). Anal calcd for C47H34O:
C 91.82, H 5.57; found C 91.68, H 5.45.
1-Terphenylyl-2,3,4,5-tetraphenylcyclopentadiene-
1-ol (3)
Preparation of inclusion compounds
4-Bromoterphenyl (2.67 g, 8.65 mmol) was used to yield
1.5 g (28%) of a colourless powder. Mp: 228–231 ꢁC. IR
(KBr) v~, cm-1: 3,550 (O–H), 3,084, 3,053, 3,033 (Ar–H),
1,631, 1,605 (C=C), 1,498, 1,484, 1,440, 1,078 (C–O), 832,
Single crystals of the inclusion compounds 2a, 2b and 3a
were obtained from solutions of the corresponding host
compounds (2 and 3) in the respective guest solvents
(n-hexane, DMSO, THF) and subsequent slow evaporation
at room temperature.
1
803 (Ar, 1,4-disubst.), 762, 747, 700 (Ar, monosubst.). H
123

J Incl Phenom Macrocycl Chem (2011) 70:1–9
X-ray crystallography
9
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