Hydrogen-bond networks in tris(4-hydroxyphenyl)methane and its 1:1 Molecular complex with 4,4′-bipyridine

Article abstract of DOI:10.1107/S0108270103014288

In tris(4-hydroxyphenyl)methane (or 4,4′,4″-methanetriyltriphenol), C₁₉H₁₆O ₃, molecules are connected by O - H...O hydrogen bonds [O...O = 2.662 (2) and 2.648 (2) A] into two-dimensional square networks that are twofold interpenetrated. In tris(4-hydroxyphenyl)methane-4,4′-bipyridine (1/1), C₁₉H ₁₆O₃·C₁₀H₈N₂, trisphenol molecules form rectangular networks via O - H...O [O...O = 2.694 (3) A] and C - H... O [C...O = 3.384 (3) A] hydrogen bonds. Bipyridine molecules hydrogen bonded to phenol moieties [O...N = 2.622 (3) and 2.764 (3) A] fill the voids to complete the structure.

Full text of DOI:10.1107/S0108270103014288

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
HÁ Á ÁO hydrogen bonds (Table 2). Hydroxy atom O1 acts as a
1
2
1
2
hydrogen-bond donor to atom O2 at (x � , y � , z), thus
generating chains of molecules running parallel to [110], and
atom O3 acts as a hydrogen-bond donor to atom O1 at (1 + x,
y, 1 + z), thus generating chains of molecules parallel to [101].
The intersection of these two linear motifs generates two-
dimensional square networks parallel to the (111) plane
ISSN 0108-2701
Hydrogen-bond networks in
tris(4-hydroxyphenyl)methane
and its 1:1 molecular complex
(
Fig. 2), which are identical to the square nets observed in
the crystal structure of 1,1,1-tris(4-hydroxyphenyl)ethane
Ferguson et al., 1997), with which the present compound is
isomorphous [after appropriate cell transformation of the
,1,1-tris(4-hydroxyphenyl)ethane cell from Ia to Cc]. The
third hydroxy group (O2) acts as a hydrogen-bond donor to
(
0
with 4,4 -bipyridine
1
a
a
Srinivasulu Aitipamula, Ashwini Nangia, *
1
1
3
atom O3 at (x � , � y, z � ), thus generating an identical
b
b
2
2
2
Ram Thaimattam and Mariusz Jask o lski
square network parallel to the (111) plane. These two square
ꢁ
networks interpenetrate in the structure at an angle of ꢀ160 ,
a
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India, and
b
being connected via the O2ÐH2Á Á ÁO3 hydrogen bond (Fig. 3).
Centre for Biocrystallographic Research, IBCh, Polish Academy of Sciences, and
Department of Crystallography, Mickiewicz University, Grunwaldzka 6, 60-780
Poznan, Poland
Correspondence e-mail: ansc@uohyd.ernet.in
Received 18 June 2003
Accepted 25 June 2003
Online 31 July 2003
0
00
In tris(4-hydroxyphenyl)methane (or 4,4 ,4 -methanetriyltri-
phenol), C H O , molecules are connected by OÐHÁ Á ÁO
1
9
16
3
Ê
hydrogen bonds [OÁ Á ÁO = 2.662 (2) and 2.648 (2) A] into two-
dimensional square networks that are twofold interpene-
0
trated. In tris(4-hydroxyphenyl)methane±4,4 -bipyridine (1/1),
C H O ÁC H N , trisphenol molecules form rectangular
1
9
16
3
10
8
2
Ê
The crystal structure of (II) contains one molecule of (I)
0
networks via OÐHÁ Á ÁO [OÁ Á ÁO = 2.694 (3) A] and CÐHÁ Á Á
Ê
and one molecule of 4,4 -bipyridine in the asymmetric unit
(Fig. 4). One of the hydroxy groups of the molecule of (I) acts
as a hydrogen-bond donor to a d-glide-related O atom, and
O [CÁ Á ÁO = 3.384 (3) A] hydrogen bonds. Bipyridine mol-
ecules hydrogen bonded to phenol moieties [OÁ Á ÁN =
Ê
.622 (3) and 2.764 (3) A] ®ll the voids to complete the
2
structure.
the other two hydroxy groups act as hydrogen-bond donors to
0
4
,4 -bipyridine molecules. Each molecule of (I) is connected to
Comment
The crystal structures of 1,1,1-tris(4-hydroxyphenyl)ethane
and its adducts with many nitrogen bases have been reported
(
2
Ferguson et al., 1997; B e nyei et al., 1998; Zakaria et al.,
002a,b). These structures contain sheets and open networks
+
�
of OÐHÁ Á ÁO, OÐHÁ Á ÁN and N ÐHÁ Á ÁO hydrogen bonds,
with up to tenfold interpenetration of giant hexagons in 1,1,1-
0
tris(4-hydroxyphenyl)ethane±4,4 -bipyridine (2/3) (B e nyei et
al., 1998). Molecules with C symmetry are important in the
3
crystal engineering (Desiraju, 1989; Moberg, 1998) of
supramolecular architectures, in host±guest systems and in the
design of non-linear optical materials. In this context, we have
determined the crystal structure of tris(4-hydroxyphenyl)-
0
methane, (I). Cocrystallization of (I) with 4,4 -bipyridine in a
2
:3 stoichiometry gave the 1:1 adduct, (II).
The crystal structure of (I) contains one molecule of tris(4-
hydroxyphenyl)methane in the asymmetric unit (Fig. 1). The
phenol groups act as donors and acceptors of hydrogen bonds,
such that each molecule is bonded to six others through OÐ
Figure 1
A view of the molecule of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level for non-H
atoms.
Acta Cryst. (2003). C59, o481±o484
DOI: 10.1107/S0108270103014288
# 2003 International Union of Crystallography o481

organic compounds
Figure 2
Aview of the crystal structure of (I), showing the two-dimensional square
network.
two others, thus forming zigzag chains via OÐHÁ Á ÁO
Figure 5
hydrogen bonds (Table 4). Atom O2 acts as a hydrogen-bond
3
1
1
Aview of the crystal structure of (II), showing the rectangular voids in the
ab plane. H atoms bonded to C atoms, except that involved in hydrogen
bonding (C15), have been omitted for clarity.
donor to atom O1 in the molecule at ( � x, + y, � + z), thus
4
4
4
generating a zigzag chain parallel to [011] and produced by the
d-glide plane. The zigzag chain related by the twofold rotation
axis runs parallel to [011]. Atom C15 acts as a hydrogen-bond
1
4
donor to atom O2 of the d-glide-related molecule at (� + x,
5
4
1
4
�
y, � + z), resulting in a zigzag chain parallel to [101]. The
net result of the OÐHÁ Á ÁO and CÐHÁ Á ÁO hydrogen-bonded
chains is a rectangular grid parallel to the ab plane, with voids
Ê
of 9.6 Â 12.5 A (Fig. 5). This two-dimensional network is not
¯
at but has undulated layers, with molecules of (I) occupying a
thickness approximately equal to the length of the c axis.
Atoms O1 and O3 act as hydrogen-bond donors to atoms N1
and N2, respectively. Thus, each rectangular network is
connected to two others by a bipyridine molecule parallel to
[
001]. The threading of two bipyridine molecules through a
rectangular void is shown as a stereoview in Fig. 6. The crystal
structure of (II) can be compared with the 2:1 adduct of
1,1,1-tris(4-hydroxyphenyl)ethane and bis(4-pyridyl)ethane
(Zakaria et al., 2002a), in which the supramolecular structure
consists of continuously interwoven bilayers.
Figure 3
A stereoview of (I), showing the concatenation of two square nets. H
atoms bonded to C atoms have been omitted for clarity.
Figure 6
A stereoview of the crystal structure of (II), showing two bipyridine
linkers connecting the hydrogen-bonded networks of (I) and passing
through the rectangular void of a third network. H atoms bonded to C
atoms, except that involved in hydrogen bonding (C15), have been
omitted for clarity.
Figure 4
A view of the molecular components of (II), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level
for non-H atoms.
ꢂ
o482 Srinivasulu Aitipamula et al.
19 16
C H O
3
and C19H
16
O ÁC10H N
3 8 2
Acta Cryst. (2003). C59, o481±o484

organic compounds
The conformations of the trisphenol molecules in the two
crystal structures are different (Tables 1 and 3); the torsion
angles about the C1ÐCaryl bond are similar in (II), whereas
they are very different in (I). In (II), the dihedral angle
between the planes of the bipyridine rings is � 32.2 (3)ꢁ.
Compound (II)
Crystal data
C
19
H
16
O
3
ÁC10
H
8
N
2
Mo Kꢁ radiation
Cell parameters from 2377
re¯ections
M
r
= 448.50
Orthorhombic, Fdd2
Ê
Ê
Ê
3
ꢁ
a = 26.483 (5) A
b = 34.102 (7) A
c = 10.483 (2) A
Ê
V = 9468 (3) A
ꢂ = 3.5±29.9
ꢃ = 0.08 mm
T = 100 (1) K
� 1
Experimental
Needle, brown
0.45 Â 0.40 Â 0.25 mm
Tris(4-hydroxyphenyl)methane was prepared according to the
procedure of Kolasa et al. (2000). A mixture of 4-hydroxybenz-
aldehyde (1.0 g, 8 mmol) and phenol (2.6 g, 28 mmol) in 1,4-dioxane
Z = 16
D = 1.259 Mg m
�
3
x
Data collection
(
15 ml) and water (15 ml) at 273 K was treated dropwise with
concentrated H SO (10 ml). The reaction mixture was allowed to
warm to room temperature and was stirred for 6 h before being
neutralized with NaHCO solution and extracted with ether. The
ether layer was washed with water and brine, dried with MgSO , and
Kuma KM-4 CCD diffractometer
scans
Rint = 0.043
2
4
ꢁ
!
ꢂmax = 29.9
2
3
2 391 measured re¯ections
352 independent re¯ections
h = � 36 ! 34
k = � 46 ! 45
l = � 14 ! 11
3
2951 re¯ections with I > 2ꢄ(I)
4
concentrated in vacuo to yield (I). The product was puri®ed by
column chromatography to yield pure (I), which was crystallized from
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢄ (F ) + (0.0517P) ]
o
methanol (m.p. 513 K). Crystals of the 1:1 molecular complex, (II)
0
2
2
2
R[F > 2ꢄ(F )] = 0.043
wR(F ) = 0.095
S = 1.12
where P = (F + 2F )/3
o c
(m.p. 470 K), of (I) and 4,4 -bipyridine were obtained upon cocrys-
tallization of the components in a 2:3 ratio from acetonitrile.
2
(Á/ꢄ)max = 0.069
Áꢅmax = 0.18 e AÊ
�
Ê
3
� 3
3
4
352 re¯ections
04 parameters
Áꢅmin = � 0.18 e A
Extinction correction: SHELXL97
Extinction coef®cient: 0.00029 (7)
Compound (I)
All H-atom parameters re®ned
Crystal data
�
3
C
19
H
16
O
3
D
x
= 1.242 Mg m
Table 3
Selected torsion angles ( ) for (II).
ꢁ
M
r
= 292.32
Monoclinic, Cc
Mo Kꢁ radiation
Cell parameters from 1475
re¯ections
Ê
a = 12.326 (3) A
C23ÐC22ÐC25ÐC29
H1AÐC1ÐC2ÐC7
� 32.2 (3)
H1AÐC1ÐC14ÐC15
H1AÐC1ÐC8ÐC9
� 34.6 (12)
� 40.7 (14)
Ê
b = 18.573 (4) A
ꢁ
ꢂ = 3.7±29.7
ꢃ = 0.08 mm
T = 100 (1) K
� 33.0 (14)
Ê
c = 7.4961 (15) A
� 1
ꢁ
ꢀ
= 114.36 (3)
Ê
3
V = 1563.4 (7) A
Z = 4
Needle, brown
0.40 Â 0.35 Â 0.20 mm
Table 4
Hydrogen-bonding geometry (A, ) for (II).
Ê
ꢁ
Data collection
Kuma KM-4 CCD diffractometer
!
R
int = 0.031
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
ꢁ
scans
459 measured re¯ections
ꢂmax = 29.7
iv
7
2
1
h = � 16 ! 16
k = � 25 ! 14
l = � 10 ! 10
C15ÐH15AÁ Á ÁO2
0.97 (3)
0.92 (4)
1.04 (3)
0.97 (3)
2.42 (3)
1.78 (4)
1.60 (3)
1.80 (3)
3.384 (3)
2.694 (3)
2.622 (3)
2.764 (3)
175 (2)
174 (3)
169 (3)
174 (3)
v
O2ÐH2Á Á ÁO1
056 independent re¯ections
844 re¯ections with I > 2ꢄ(I)
O1ÐH1Á Á ÁN1
vi
O3ÐH3Á Á ÁN2
Re®nement
1
4
5
4
1
4
3
1
1
4
1
3
4
5
4
Symmetry codes: (iv) x � ; � y; z � ; (v) � x; ‡ y; z � ; (vi) x � 4; � y; ‡ z.
2
2
2
o
2
4
4
Re®nement on F
2
w = 1/[ꢄ (F ) + (0.0573P)
2
R[F > 2ꢄ(F )] = 0.039
wR(F ) = 0.101
S = 1.22
+ 0.0272P]
where P = (Fo + 2F )/3
2
2
2
c
(Á/ꢄ)max < 0.001
Ê
� 3
� 3
Both structures are non-centrosymmetric. However, because the
anomalous dispersion effects were insigni®cant, Friedel opposite
re¯ections were merged. The Flack (1983) parameters are thus
2
2
056 re¯ections
63 parameters
Áꢅmax = 0.18 e A
Áꢅmin = � 0.20 e AÊ
All H-atom parameters re®ned
indeterminate. Re®ned CÐH distances of 0.93 (3)±1.02 (3) and
Ê
0.94 (2)±1.03 (3) A, and OÐH distances of 0.84 (3)±0.90 (3) and
0.92 (4)±1.04 (3) A were obtained for (I) and (II), respectively.
Table 1
Selected torsion angles ( ) for (I).
ꢁ
Ê
For both compounds, data collection: KM-4 Software (Kuma,
999); cell re®nement: KM-4 Software; data reduction: CrysAlis
H1AÐC1ÐC2ÐC3
H1AÐC1ÐC14ÐC19
26.9 (13)
16.9 (14)
H1AÐC1ÐC8ÐC9
61.2 (14)
1
(
(
(
Kuma, 1999); program(s) used to solve structure: SHELXS97
Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97
Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software
Table 2
Hydrogen-bonding geometry (A, ) for (I).
Ê
ꢁ
used to prepare material for publication: SHELXL97.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
The authors thank the DST and KBN for the award of an
Indo-Polish exchange programme (INT/POL/008/00), the
Mianowski Fund for the award of a fellowship to RT, and the
CSIR for the award of a fellowship to SA. The UPE
programme of UGC supports the University of Hyderabad.
i
O1ÐH1Á Á ÁO2
O2ÐH2Á Á ÁO3
O3ÐH3Á Á ÁO1
0.87 (2)
0.88 (2)
0.86 (3)
1.81 (3)
1.81 (2)
1.81 (3)
2.662 (2)
2.662 (2)
2.648 (2)
168 (3)
163 (2)
166 (3)
ii
iii
1
1
1
1
3
2
Symmetry codes: (i) x � 2; y � ; z; (ii) x � ; � y; z � ; (iii) 1 ‡ x; y; 1 ‡ z.
2
2
2
ꢂ
Acta Cryst. (2003). C59, o481±o484
Srinivasulu Aitipamula et al.
19 16
C H O
3
16
and C19H O
3
ÁC10H N
8 2
o483

organic compounds
Kolasa, T., Gunn, D. E., Bhatia, P., Basha, A., Craig, R. A., Stewart, A. O.,
Bouska, J. B., Harris, R. R., Hulkower, K. I., Malo, P. E., Bell, R. L., Carter,
G. W. & Brooks, C. D. (2000). J. Med. Chem. 43, 3322±3334.
Kuma (1999). KM-4 Software (Version 161) and CrysAlis (Version 162). Kuma
Diffraction, Wrocøaw, Poland.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: JZ1567). Services for accessing these data are
described at the back of the journal.
Moberg, C. (1998). Angew. Chem. Int. Ed. 37, 248±268.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of
G oÈ ttingen, Germany.
Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison,
Wisconsin, USA.
References
B e nyei, A. C., Couper, P. I., Ferguson, G., Glidewell, C., Lough, A. J. &
Meehan, P. R. (1998). Acta Cryst. C54, 1515±1519.
Desiraju, G. R. (1989). In Crystal Engineering: The Design of Organic Solids.
Amsterdam: Elsevier.
Ferguson, G., Bell, W., Couper, P. I. & Glidewell, C. (1997). Acta Cryst. B53,
Zakaria, C. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002a). Acta Cryst.
C58, o1±o5.
534±543.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
Zakaria, C. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002b). Acta Cryst.
C58, o204±o208.
ꢂ
o484 Srinivasulu Aitipamula et al.
19 16
C H O
3
and C19H
16
O ÁC10H N
3 8 2
Acta Cryst. (2003). C59, o481±o484