Hydrogen-bonding networks of adamantane-based bisphenol molecules: Toward the preparation of molecular crystals with channels

Article abstract of DOI:10.1021/cg101427k

A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual molecules in crystalline

Full text of DOI:10.1021/cg101427k

DOI: 10.1021/cg101427k
Hydrogen-Bonding Networks of Adamantane-Based Bisphenol
Molecules: Toward the Preparation of Molecular Crystals with Channels
2011, Vol. 11
542–546
Masahide Tominaga,* Hyuma Masu, and Isao Azumaya*
Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido,
Sanuki, Kagawa 769-2193, Japan
Received October 26, 2010; Revised Manuscript Received December 13, 2010
ABSTRACT: A series of adamantane-based bisphenol molecules with structurally related V-shaped skeletons were designed to
examine the influence of molecular shapes and steric hindrances for the molecular association and packing of individual
molecules in crystalline lattices. Single crystal X-ray analysis revealed that multiple intermolecular hydrogen bonds were formed
between the hydroxyl groups of the phenol moieties. Crystallographic analysis of 1,3-bis(4-hydroxy-3,5-dimethylphenyl)-
adamantane (1) indicated the creation of a one-dimensional (1D) zigzag polymer through hydrogen bonds. In the crystals of 1,3-
bis(3-bromo-4-hydroxyphenyl)adamantane (2), infinite 1D polymers composed of cyclic frameworks were sustained by
intermolecular hydrogen bonds. 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3) and 1,3-bis(4-hydroxyphenyl)adamantane
(4) formed frameworks with channels containing chloroform molecules in the solid state. Continuous 1D polymers consisting of
cyclic frameworks were generated in crystals 3a and 4a, and these 1D polymers packed into two-dimensional (2D) layers with
channel structures.
Introduction
bisphenol can provide two V-directional hydrogen-bonding
sites for the formation of a predictable network with large
cavities based on cooperative interactions. Thus, we have
planned to introduce various types of substitution groups
on the o-position of the phenol ring for the generation of novel
molecular architectures and to explore zeolite-like crystalline
materials with channels. Here we report on the syntheses and
structures of a series of adamantane-based bisphenol mole-
cules with structurally related V-shaped skeletons: 1,3-bis(4-
hydroxy-3,5-dimethylphenyl)adamantane (1), 1,3-bis(3-bromo-
4-hydroxyphenyl)adamantane (2), 1,3-bis(3-chloro-4-hydroxy-
phenyl)adamantane (3), and 1,3-bis(4-hydroxyphenyl)adaman-
tane (4).19 These compounds are directed to forming host
molecules for guest-inclusion networks in crystalline lattices.
Single crystals suitable for diffraction analysis were obtained
as crystals by the slowevaporation of a chloroform solution of
1 (crystal 1a), 2 (crystal 2a), 3 (crystal 3a), and 4 (crystal 4a).
X-ray diffraction experiments revealed the formation of 1D
zigzag polymers for crystal 1a, 1D polymers composed of
cyclic structures for crystal 2a, and zeolite-like frameworks
with channels comprised of 1D polymers bearing cyclic
structures for crystals 3a and 4a. Such crystal arrangements
were formed through multiple hydrogen bonds between the
hydroxyl groups of phenol moieties.
The rational design of molecular solids and materials has
attracted considerable interest in the area of crystal engineer-
ing and supramolecular chemistry for last three decades.1,2 In
particular, the developments of microporous materials with
channels and cavities are important as molecular analogues of
zeolites, which have practical applications such as gas absorp-
tion, size selective separation, and heterogeneous catalysis.3,4
A number of two- and three-dimensional frameworks includ-
ing small organic molecules were constructed by spontaneous
self-aggregation through hydrogen bonds in crystal engineer-
ing, which is a valuable noncovalent interaction with direc-
tionality and moderate bond strength.5-9 Bisphenols and
related simple building block compounds are known to afford
organic solids that adopt a variety of supramolecular net-
works,10 where phenolic hydroxyl groups play a crucial role in
the formation of characteristic hydrogen-bonded motifs such
as cyclic oligomers, linear chains, and other assemblies.11
Various bisphenol molecules have been designed and pre-
pared, which are composed of adequate linkers and two phenol
units. As a linker unit, methylene, cyclohexane, and phenylene
spacers have been utilized to connect two phenol rings to each
other. Examples are bisphenol A,12 bisphenol F,13 1,1-bis(4-
hydroxyphenyl)cyclohexane,14 and bisphenol 4,40-terphenyl-
diol15 (see ref 16 for further examples); these crystalline solids
yield diverse molecular architectures through multiple hydro-
gen bonds. In addition, a series of bis-catechol and -resorcinol
compounds crystallized as hydrogen-bonded networks with
channels via molecular self-assembly.17 Recently, we have
demonstrated the creation of unique hydrogen-bonded
networks with guest-inclusion ability that are built from an
adamantane-based bisphenol compound in the solid state, in
which two molecules of 2,6-dimethoxyphenol are linked
by a bulky adamantane spacer.18 This adamantane-based
Experimental Section
Synthesis of 1,3-Bis(4-hydroxy-3,5-dimethylphenyl)adamantane
(1). A mixture of 1,3-adamantanediol (1.68 g, 0.01 mol) and 2,6-
dimethylphenol (24.4 g, 0.20 mol) in trifluoroacetic acid (75 mL)
and 1,2-dichloroethane (75 mL) in the presence of catalytic amounts
of trifluoromethanesulfonic acid was stirred at 90 °C for 8 h under
an argon atmosphere. The solvents were removed under reduced
pressure, and the reaction mixture was washed with H2O, saturated
aqueous NaHCO3, H2O, and brine and dried over Na2SO4. Eva-
poration of the solvent followed by silica gel column chromatogra-
phy (eluent: chloroform/hexane = 1/2) and gel permeation chro-
matography (JAIGEL 1Hþ2H, chloroform) afforded the title
compound as a white solid (2.22 g, 5.90 mmol) in 59% yield. mp
195-196 °C. FT-IR (ATR, cm-1): 3365, 2901, 1558, 1506, 1490,
*Corresponding authors. Telephone: þ81-87-894-5111, ext 6308.
Fax: þ81-87-894-0181. E-mail: tominagam@kph.bunri-u.ac.jp (M.T.);
azumayai@kph.bunri-u.ac.jp (I.A.).
r
pubs.acs.org/crystal
Published on Web 01/12/2011
2011 American Chemical Society

Article
Crystal Growth & Design, Vol. 11, No. 2, 2011 543
Table 1. Crystal Data of Crystals 1a-4a
crystal
1a
2a
3a
4a
formula
fw
C26H32O2
376.52
monoclinic
C2/c
8.136(2)
11.986(2)
21.178(4)
90
98.029(2)
90
C22H22Br2O2
478.22
triclinic
P1
6.909(1)
10.591(2)
14.238(4)
108.020(3)
97.455(3)
102.059(2)
947.5(4)
2
C22H22Cl2O2 0.5CHCl3
3
C22H24O2 0.5CHCl3
3
448.48
monoclinic
C2/c
380.10
triclinic
P1
crystal system
space group
˚
a (A)
26.384(2)
6.4107(5)
27.200(3)
90
117.200(1)
90
4091.9(7)
8
1.458
6.354(1)
12.695(2)
13.196(3)
117.671(2)
90.941(2)
99.691(2)
923.8(3)
2
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
˚
V (A )
Z
2044.9(7)
4
1.223
Dcalc (Mg/m3)
T (K)
1.676
150
1.366
120
150
120
R1, wR2 [I > 2σ(I )]
R1, wR2 (all data)
CCDC number
0.0406, 0.1047
0.0504, 0.1118
796676
0.0351, 0.0959
0.0429, 0.0996
796677
0.0405, 0.0985
0.0554, 0.1087
796678
0.0453, 0.1077
0.0511, 0.1116
796679
Figure 1. Thermal ellipsoidal models of the crystal structures of adamantane-based bisphenol molecules 1-4. (a) crystal 1a, (b) crystal 2a,
(c) crystal 3a, and (d) crystal 4a. Only representative atoms are indicated for the disordered atoms in which unique positions were not clearly
defined (i.e., hydrogen atoms of the hydroxyl groups of 4a, chloroform molecules of 3a and 4a).
1
1219, 1187, 937, 772. H NMR (400 MHz, CDCl3, 27 °C) δ 6.99
(s, 4H), 4.49 (s, 2H), 2.27 (s, 2H), 2.24 (s, 12H), 1.94-1.75 (m, 12H).
13C NMR (100 MHz, CDCl3, 27 °C) δ 150.03 (Cq), 142.67 (Cq),
125.10 (CH and Cq), 122.41 (CH), 49.58 (CH2), 42.52 (CH2), 36.51
(Cq), 35.94 (CH2), 29.96 (CH), 16.16 (CH3). MS (FAB, m/z) calcd
for C26H33O2 (M þ Hþ) 377.24, found 377.0. Elemental analysis.
Calcd for C26H32O2: C, 82.94; H, 8.57. Found: C, 82.67; H, 8.66.
Synthesis of 1,3-Bis(3-bromo-4-hydroxyphenyl)adamantane (2).
The title compound was synthesized in 55% yield as a white solid
in a manner similar to that described for the preparation of 1. mp
140-141 °C. FT-IR (ATR, cm-1): 3363, 2901, 1558, 1507, 1496,
1221, 1171, 816, 773. 1H NMR (400 MHz, CDCl3, 27 °C) δ 7.42 (d,
2H, J = 2.0 Hz), 7.20 (dd, 2H, J = 8.4, 2.4 Hz), 6.96 (d, 2H, J = 8.4
Hz), 5.49 (s, 2H), 2.26 (s, 2H), 1.86-1.72 (m, 12H). 13C NMR (100
MHz, CDCl3, 27 °C) δ 150.01 (Cq), 144.38 (Cq), 128.49 (CH), 125.67
(CH), 115.64 (CH), 110.06 (Cq), 49.13 (CH2), 42.08 (CH2), 36.70
5.45 (s, 2H), 2.28 (s, 2H), 1.89-1.74 (m, 12H). 13C NMR (100 MHz,
CDCl3, 27 °C) δ 149.15 (Cq), 144.05 (Cq), 125.56 (CH), 124.91 (CH),
119.57 (Cq), 115.81 (CH), 49.16 (CH2), 42.17 (CH2), 36.79 (Cq),
35.57 (CH2), 29.39 (CH). MS (FAB, m/z) calcd for C22H23Cl2O2
(M þ Hþ) 389.10, found 389.7. Elemental analysis. Calcd for
C
22H22Cl2O2 0.25H2O: C, 67.10; H, 5.76. Found: C, 67.09; H, 5.62.
3
Crystallization. Different types of single crystals of a series of
adamantane-based bisphenol derivatives 1-4 were obtained by the
slow evaporation of a chloroform solution of 1 (crystal 1a), 2
(crystal 2a), 3 (crystal 3a), and 4 (crystal 4a).
Measurement. X-ray data for the crystals were collected on a
CCD diffractometer with graphite monochromated Mo KR (λ =
0.71073 A) radiation. Data collection was carried out at 150 K (for
˚
crystals 1a and 2a) or 120 K (for crystals 3a and 4a) using liquid
nitrogen. The crystal structures were solved by direct methods
SHELXS-9720 and refined by full-matrix least-squares. All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms were
included at their calculated positions, except that of the hydroxyl
group of 4a.
(Cq), 35.48 (CH2), 29.32 (CH). MS (FAB, m/z) calcd for C22
H
for C22H22Br2O2: C, 55.25; H, 4.64. Found: C, 55.25; H, 4.44.
-
23Br2O2 (M þ Hþ) 477.00, found 477.4. Elemental analysis. Calcd
Synthesis of 1,3-Bis(3-chloro-4-hydroxyphenyl)adamantane (3).
The title compound was synthesized in 70% yield as a white solid
in a manner similar to that described for the preparation of 1. mp
134-135 °C. FT-IR (ATR, cm-1): 3364, 2898, 1559, 1502, 1207, 1175,
1054, and 808. 1H NMR (400 MHz, CDCl3, 27 °C) δ 7.29 (d, 2H,
J = 2.0 Hz), 7.18 (dd, 2H, J = 8.8, 2.4 Hz), 6.96 (d, 2H, J = 8.8 Hz),
Results and Discussion
Three types of adamantane-based bisphenol molecules 1-3
were newly prepared by a coupling reaction of o-substituted
phenol derivatives and 1,3-adamantanediol in a mixture of

544 Crystal Growth & Design, Vol. 11, No. 2, 2011
Tominaga et al.
Table 2. Conformational Parameters of Adamantane-Based Bisphenols
1-4
crystal
˚
1a
2a
3a
4a
bond length (A)
C2-C3
1.528 1.538 1.523 1.530
1.528 1.535 1.535 1.527
C5-C6
torsion angle (deg)
P1-adamantane (C1-C2-C3-C4) 58.38 86.88 51.65 73.97
64.95 58.04
P2-adamantane (C4-C5-C6-C7) 58.38 1.14
Chart 1. Adamantane-Based Bisphenols 1-4
Figure 2. Crystal structure of 1a. (a) A hydrogen-bonded infinite
1D zigzag chain from the front view (along the a axis). (b) Top view
(along the b axis) of the packing structure. The molecules are
colored in cyan except the representative molecules for clarity.
Hydrogen bonds are indicated by black dotted lines.
intermolecular hydrogen bonds between the hydroxyl groups
of the o-bromophenol moieties (the distance of the O
trifluoroacetic acid and 1,2-dichloroethane (v/v = 1/1) in the
presence of catalytic amounts of trifluoromethanesulfonic
acid to give 55-70% yield. The resulting disubstituted ada-
mantanes 1-3 were characterized by 1H and 13C NMR spec-
troscopy, elemental analysis, and FAB mass spectroscopy.
The analysis data were in full agreement with the structures
presented. Crystal data of all crystals are shown in Table 1. A
series of adamantane-based bisphenol molecules 1-4 dis-
played C1 symmetry (Figure 1). X-ray analysis revealed the
bond lengths and torsion angles (CHPh-CPh-Cad-CH2ad) of
the two single-bonds between the adamantane skeleton and
thephenyl ring of1-4, and the valuesarepresented in Table 2.
The dihedral angle of the cofacial pair of aromatic rings was
88.93° (1a), 89.67° (2a), 89.80° (3a), and 87.55° (4a).
O
atoms is 2.85 A), which assembled into an infinite 1D polymer
3 3 3
˚
via hydrogen bonding between hydroxyl groups of the o-
bromophenol parts (the distance of the O O atoms is 2.77
3 3 3
˚
A) directly along the c axis (Figure 3). Therefore, discrete
rhombic cyclic hydrogen-bonded networks were constructed
fromfour hydroxyl groups of2 inthe 1D polymers. Individual
1D polymers pack together to generate a 3D network struc-
ture, where cyclic frameworks built from two molecules of
2 were stacked with a shift by one-half of a molecule along the
b axis and directly along the a axis of a unit cell, resulting in the
formation of cylinder-shaped arrangements that filled the
cavity of neighboring cyclic frameworks. The plane distance
˚
between 1D polymers was 4.39 A (measured between the
The crystal 1a crystallized in the monoclinic system and the
space group C2/c. Crystal packing examination revealed that
the crystal 1a consists of infinite 1D zigzag chains with lengths
plane composed of two pairs of C2 and C6 in Table 2).
The crystal 3a crystallized in the monoclinic system and the
space group C2/c, and it included one molecule of 3 and one-
half moleculeof chloroform in the asymmetric unit. In crystals
˚
of 16.6 A (measured from the center of the adamantane to the
center of the adamantane) through intermolecular hydrogen
bonds between hydroxyl groups of dimethylphenol moieties
˚
3a, cyclic structures with sizes of 11.2 A (measured from the
center of the adamantane to the center of the adamantane)
were constructed from two molecules of 3 by intermolecular
hydrogen bonds between hydroxyl groups of the o-chloro-
˚
in 1 (the distance of the O O atoms is 2.85 A) along the ac
3 3 3
plane (Figure 2). Individual 1D zigzag chains associated into
3D architectures with a shift by one molecule along the a axis
and directly along the b axis of a unit cell.
˚
phenol moieties (the distance of the O O atoms is 2.89 A),
3 3 3
which assembled into an infinite 1D polymer via hydrogen
bonding between hydroxyl groups of theo-chlorophenol parts
The crystal 2a crystallized in the triclinic system and the
˚
space group P1. The cyclic structure with sizes of 10.9 A
(measured from the center of the adamantane to the center of
the adamantane) was formed from two molecules of 2 by
˚
(the distance of the O O atoms is 2.80 A) directly along the
3 3 3
a axis (Figure 4). Individual 1D polymers composed of cyclic
frameworks stack to create 2D layers with channel structures

Article
Crystal Growth & Design, Vol. 11, No. 2, 2011 545
Figure 3. Crystal structure of 2a. (a) A hydrogen-bonded infinite
1D chain composed of cyclic frameworks from the front view (along
the b axis). (b) Space-filling model of the packing structure from the
front view. (c) Top view (along the a axis) of the packing structure.
The molecules are colored in cyan and aqua blue except the
representative molecules for clarity. Hydrogen bonds are indicated
by black dotted lines.
Figure 4. Crystal structure of 3a. (a) A hydrogen-bonded infinite
1D chain and channel-shaped network structure from the top view
(along the b axis). (b) Space-filling model of the network structure
from the front view. (c) Side view of the packing structure. The
molecules are colored in cyan and aqua blue except the representa-
tive molecules for clarity. Hydrogen bonds are indicated by black
dotted lines. Solvent molecules (chloroform) are omitted for clarity.
via hydrogen bonds between hydroxyl groups of the o-chlor-
layers with channel structures through hydrogen bonding
between hydroxyl groups of the phenol units (the distance
˚
ophenol parts (the distance of the O O atoms is 2.80 A) that
align with the b axis (Figure 4). The distance between 1D
3 3 3
˚
of the O O atoms is 2.62 A) that are aligned with the a axis.
3 3 3
˚
˚
polymers is 6.41 A (measured between the plane composed of
The distance between the 1D polymers is 5.43 A (measured
two pairs of C2 and C6 in Table 2). Chloroform molecules
were trapped inside the center of a sizable rhombic cavity in
the channels. Furthermore, packing of the 2D layered aggre-
gates in the crystal is realized along the c axis. Therefore, the
channel, which was similar to that in zeolite-like organic
solids, remained.
between the plane composed of two pairs of C2 and C6 in
Table 2). Chloroform molecules were trapped in the rhombic
cavity of the channels. Furthermore, packing of the 2D
layered aggregates in the crystal is realized along the b and c
axes.
Insummary, four types of newhydrogen-bondedmolecular
networks including guest molecules based on four structurally
related adamantane-based bisphenol molecules 1-4 with
different substituent groups in the ortho position on the phe-
nol ring have been designed and characterized. From X-ray
diffraction analysis of each organic solid, the phenolic hydro-
xyl groups were observed to be crucial in generating diverse
supramolecular architectures in the crystalline lattice. In
particular, the substituent groups in the ortho position on
the phenol ring influence the molecular packing due to steric
hindrance and hydrogen-bonding potential. As a result, ada-
mantane-based bisphenol 3 and 4 were valuable building blo-
cks for designing a zeolite-like host framework in the solid
The crystal 4a crystallized in the triclinic system and the
space group P1, and it includedone moleculeof4 and one-half
molecule of chloroform in the asymmetric unit. In the crystals
˚
4a, cyclic structures with sizes of 11.4 A (measured from the
center of the adamantane to the center of the adamantane)
were built from two molecules of 4 by intermolecular hydro-
gen bonds between the hydroxyl groups of the phenol moieties
˚
(the distance of the O O atoms is 2.82 A), which associated
3 3 3
into infinite 1D polymers via hydrogen bonds between the
hydroxyl groups of phenol parts (the distance of the O
O
atoms is 2.85 A) directly along the bc plane (Figure 5). 1D
3 3 3
˚
polymers bearing cyclic frameworks stacked to construct 2D

546 Crystal Growth & Design, Vol. 11, No. 2, 2011
Tominaga et al.
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state. Studies on the formation of 3D frameworks with guest-
inclusion capacities from tri- and tetra-substituted adaman-
tane molecules bearing functionalized phenol parts are under
investigation.
Acknowledgment. This research was supported by a Grant-
in-Aid for Young Scientists (B) from the Ministry of Educa-
tion, Science, Sports and Culture of Japan (No. 22750113).
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