A supramolecular carpet formed via self-assembly of bis(4,4′-dihydroxyphenyl) sulfone

Article abstract of DOI:10.1039/a700363c

Bis(4,4′-dihydroxyphenyl) sulfone 1 exploits its tetrahedrally disposed complementary hydrogen bonding sites to generate a unique doubly interwoven molecular carpet architecture in the solid state.

Full text of DOI:10.1039/a700363c

View Article Online / Journal Homepage / Table of Contents for this issue
A supramolecular carpet formed via self-assembly of bis(4,4A-dihydroxyphenyl)
sulfone†
Caitlin Davies,a Richard F. Langler,*a C. V. Krishnamohan Sharmab and Michael J. Zaworotko*b
a Department of Chemistry, Mount Allison University, Sackville, New Brunswick, Canada E0A 3C0
b Department of Chemistry, Saint Mary’s University, Halifax, Nova Scotia, Canada B3H 3C3
Bis(4,4A-dihydroxyphenyl) sulfone 1 exploits its tetrahed-
rally disposed complementary hydrogen bonding sites to
generate a unique doubly interwoven molecular carpet
architecture in the solid state.
The molecular carpet architecture of 1 demonstrates how
molecules with flexible hydrogen bonding sites can self-
assemble to yield 2D interwoven networks as an alternative to
3D diamondoid architectures. Such networks would be ex-
pected to have clay-like intercalation properties and, if
appropriate guests can be used to eschew interpenetration, large
cavities within the grid.9 The critical importance of com-
plementarity amongst the hydrogen bonding sites is illustrated
by what happens if one hydroxy substituent of 1 is replaced by
a chloro substituent. 4-chlorophenyl (4A-hydroxyphenyl) sul-
fone 2 exhibits a less predictable but nonetheless intriguing
crystal structure.§ Compound 2 crystallizes from CHCl3 (mp
150–151 °C) in the non-centrosymmetric space group P1 with,
remarkably, four molecules in the asymmetric unit. There are
two discrete hydrogen bonding motifs: i, simple linear hydrogen
bonding between sulfone and hydroxy groups [2.898(6) Å]; ii,
cyclic hydrogen bonding involving two of the sulfone O atoms
and three hydroxy groups, possibly with two of the hydroxy
groups being disordered [Scheme 1, O···O: 2.838(6), 2.881(6),
The concept of rational design of 2D and 3D frameworks has
evoked considerable interest in recent years as many functional
properties of solids are dependent on crystal packing.1,2
A
particularly interesting and relevant problem that has been
addressed by several groups concerns the preparation of open
cage and/or interwoven networks.3–5 While the former is
desired in the context of porous solids, the latter is an associated
phenomenon which invariably occurs if > 50% of a solid would
otherwise be empty. Such interpenetration (or catenation) is
appreciated for its aesthetic appeal and offers potential host
materials if guest molecules can be exploited to prevent
interpenetration.6 Understanding and predicting interpenetra-
tion patterns therefore constitutes an important aspect of crystal
engineering.
Self-assembly can be an effective strategy for crystal
engineering but it requires careful control over molecular
symmetry and functionality.3 In general, tetrahedral molecules
with rigid complementary hydrogen bonding sites adapt
diamondoid architecture with levels of interpenetration based
on the relative size of superdiamondoid cage and the volume of
the tecton.7 We report herein an alternate motif for such
compounds which occurs if there is flexibility present in the
tecton: interwoven 2D square grids.8
A solution of bis(4-chlorophenyl) sulfone (4.0 g) and sodium
hydroxide (4.0 g) in Me2SO (160 ml) and water (40 ml) was
maintained at 100 °C for two months. Extractive workup with
diethyl ether furnished a mixture of unchanged chloro sulfone,
bis(4-hydroxyphenyl) sulfone
1
and 4-chlorophenyl
(4A-hydroxyphenyl) sulfone 2. Chloroform elution on silica gel
furnished pure 1 (2%) and 2 (50%).
Fig. 1 ORTEP diagram of 1 illustrating a single hydrogen bonded
network
OH
R
S
O
O
1 R = OH
2 R = Cl
Non-centrosymmetric crystals of 1 were obtained from
acetone–CHCl3 (mp 247–249 °C). The crystal structure‡
reveals an infinite 2D hydrogen bonded network sustained by
interaction between hydroxy and sulfone groups (O···O
2.705(7), 2.800(3) Å, Fig. 1). The network generates square
cavities with ca. 8 3 10 Å dimensions, large enough to facilitate
generation of a 2-fold interwoven molecular carpet (Fig. 2). The
entangled 2D grids are stabilized by van der Waals and
herringbone interactions. A 3D diamondoid architecture is also
feasible but presumably packs less efficiently in the absence of
an appropriate guest.
Fig. 2 A space filling diagram of the interwoven supramolecular carpet
architecture of 1. The two independent grids are colour coded for clarity.
Chem. Commun., 1997
567

View Article Online
Since submission of this article an account of the structure of 1 has been
published. See G. Ferguson and C. Glidewell, Acta Crystallogr., Sect. C,
1996, 52, 2528.
§ Crystal Data for 2: As for 1 but 4-hydroxyphenyl, 4A-chlorophenyl
sulfone, M = 267.96, triclinic, P1, a = 7.6401(11), b = 9.2850(11),
S
O
O
O
O
c
= 17.6630(13) Å, a = 93.04(2), b = 91.51(3), g = 108.64(2),
O
V = 1184.35(24) Å3, Z = 4, Dcalc = 1.503 Mg m23, l = 0.70930 Å,
F(000) = 552. 3591 reflections with Inet > 3s (Inet) out of 4149 unique
reflections measured at 290 K for a crystal of dimensions 0.4 3 0.2 3 0.2
mm afforded values of Rf = 0.042 and Rw = 0.047.
Scheme 1
References
1 G. R. Desiraju, Crystal Engineering: The Design of Organic Solids,
Elsevier, Amsterdam, 1989.
2 B. F. Abrahams, B. F. Hoskins and R. Robson, J. Am. Chem. Soc., 1991,
113, 3603.
3.019(6), 2.913(6) Å]. Furthermore, there are two different
kinds of aryl–aryl stacking interactions: between chlorophenyl
and hydroxyphenyl groups and between adjacent chlorophenyl
groups. The mean interplanar distances and dihedral angles of
these two stacking interactions are 3.74 and 3.60 Å, 2.9 and 3.4°
respectively.
Compounds 1 and 2 illustrate clearly the importance of self-
assembly to crystal engineering. Compound 1 demonstrates
how tetrahedral moieties with complementary hydrogen bond-
ing sites are capable of self-assembling into a predictable 2D
motif if the hydrogen bonding sites are robust and flexible.
However, 2 demonstrates how even minor changes in func-
tionality can lead to unusual and unpredictable crystal pack-
ing.
3 M. J. Zaworotko, Chem. Soc. Rev., 1994, 283.
4 G. B. Gardner, D. Venkataraman, J. S. Moore and S. Lee, Nature, 1995,
374, 792; O. M. Yaghi, G. Li and H. Li, Nature, 1995, 378, 703;
M. E. Brown and M. D. Hollingsworth, Nature, 1995, 376, 323;
S. V. Kolotuchin, E. E. Fenlon, S. R. Wilson, C. J. Loweth and
S. C. Zimmerman, Angew. Chem., Int. Ed. Engl., 1995, 34, 2654;
S. Subramanian and M. J. Zaworotko, Angew. Chem., Int. Ed. Engl.,
1995, 34, 2127; M. Munakata, L. P. Wu, M. Yamamoto, T. Kuroda-Sowa
and M. Maekawa, J. Am. Chem. Soc., 1996, 118, 3117.
5 D. B. Amabilino and J. F. Stoddart, Chem. Rev., 1995, 95, 2725;
D. S. Reddy, D. C. Craig, A. D. Rae and G. R. Desiraju, J. Chem. Soc.,
Chem. Commun., 1994, 1457; D. M. Goodgame, S. Menzer, A. M. Smith
and D. J. Williams, J. Chem. Soc., Chem. Commun., 1995, 1975;
L. Carlucci, G. Ciani, D. M. Proserpio and A. Sironi, J. Chem. Soc.,
Chem. Commun., 1994, 2755; P. M. V. Calcar, M. M. Olmstead and
A. Balch, J. Chem. Soc., Chem. Commun., 1995, 1723; L. R.
MacGillivray, S. Subramanian and M. J. Zaworotko, J. Chem. Soc.,
Chem. Commun., 1994, 1325.
6 F. H. Herbstein, M. Kapon and G. M. Reisner, J. Inclusion Phenom.,
1987, 5, 211.
7 O. Ermer, J. Am. Chem. Soc., 1988, 110, 3747; O. Ermer, Angew. Chem.,
Int. Ed. Engl., 1988, 27, 829; X. Wang, M. Simard and J. D. Wuest, J. Am.
Chem. Soc., 1994, 116, 12119.
8 Supramolecular carpets from multiple components were reported by us
earlier: S. B. Copp, S. Subramanian and M. J. Zaworotko, Angew. Chem.,
Int. Ed. Engl., 1993, 32, 706; C. V. K. Sharma and M. J. Zaworotko,
Chem. Commun., 1996, 2655. Related coordination polymers have also
been encountered: D. M. L. Goodgame, S. Menzer, A. M. Smith and
D. J. Williams, Angew. Chem., Int. Ed. Engl., 1995, 34, 574.
9 A. Muller, H. Reuter and S. Dillinger, Angew. Chem., Int. Ed. Engl.,
1995, 34, 2328; S. B. Copp and M. J. Zaworotko, unpublished results.
Footnotes
† This ChemComm is also available in enhanced multi-media format via the
World Wide Web: http://chemistry.rsc.org/rsc/cccenha.htm
‡ Crystal Data for 1: 4,4A-Dihydroxyphenyl sulfone, M
= 249.26,
orthorhombic, C2cb, a = 8.1572(10), b = 19.2757(21), c = 15.0471(20)
Å, V = 2365.9(5) Å3, Z = 8, Dcalc = 1.40 Mg m23, l = 0.70930 Å,
F(000) = 1032.921 reflections with Inet > 3s (Inet) out of 1121 unique
reflections measured at 290 K for a crystal of dimensions 0.3 3 0.2 3 0.4
mm on an Enraf-Nonius CAD4 diffractometer using the w scan mode (4 <
2q < 50°) afforded, on convergence, final values of Rf = 0.077 and
Rw = 0.089. The H atom of one of the two OH groups was found via
difference Fourier map inspection. Other H atoms were placed in calculated
positions (C–H = 1.0 Å). All non-hydrogen atoms were anisotropically
refined. The crystallographic calculations were carried out using NRCVAX
program package. Atomic coordinates, bond lengths and angles, and
thermal parameters for both 1 and 2 (see below) have been deposited at the
Camrbidge Crystallograpic Centre (CCDC). See Information for Authors,
Issue No. 1. Any request to the CCDC for this material should quote the full
literature citation and the reference number 182/360.
Received, 17th May 1996; Revised manuscript received, 15th
January 1997; Com. 7/00363C
568
Chem. Commun., 1997