A robust two-dimensional hydrogen-bonded network: The sulfamide moiety as a new building block for the design of molecular solids [7]

Full text of DOI:10.1021/ja981707c

11194
J. Am. Chem. Soc. 1998, 120, 11194-11195
A Robust Two-Dimensional Hydrogen-Bonded
Network: The Sulfamide Moiety as a New Building
Block for the Design of Molecular Solids
Bing Gong,*,† Chong Zheng,*,‡ Ewa Skrzypczak-Jankun,†
Yinfa Yan,† and Jianhua Zhang‡
Departments of Chemistry
The UniVersity of Toledo, Toledo, Ohio 43606
Northern Illinois UniVersity, DeKalb, Illinois 60115-2862
ReceiVed May 18, 1998
A principal goal of crystal engineering is the ability to
manipulate solid-state properties by systematic variations of the
molecular structure through alteration of the constituent mol-
ecules.1 Molecular solids with predefined solid-state structures
can find many important applications for developing new materi-
als. Current efforts in assembling molecular solids focus mainly
on one-dimensional aggregates such as chains, tapes, and
columns.2 Many examples of two-dimensional networks have
also been reported.2h,3 Except for the tetrahedron-centered
hydrogen-bonding topology that produces three-dimensional dia-
mondoid networks,4 little or no control over the assembly in the
third dimension has been realized. A recently reported system,5
based on a 2D network of guanidinium cations and sulfonate
anions, offered a very elaborate and advanced example of crystal
engineering. Here we report a previously unrecognized 2D
structural motif for the design and self-assembly of 3D molecular
arrays. This system makes use of the sulfamide functionality of
the N,N′-disubstituted sulfamide, as shown by general structure
1.
Figure 1. Packing of 1a. (a) One molecular layer held together by the
2D hydrogen-bonded sulfamide network. The viewing direction is
perpendicular to the plane of the 2D network. The isobutyl groups pack
above and below the 2D network. All six compounds pack similarly to
form layers based on the sulfamide network. (b) Packing of the molecular
layers along the third direction. Two layers are shown here. The planes
of two 2D sulfamide networks are perpendicular to that of the paper.
solid design,2b,h the tetrahedral-shaped sulfamide group, surpris-
ingly, has not been employed.6 For this reason, we have
synthesized sulfamides 1a-f and examined their solid-state
structures. Compounds 1a-f were prepared by treating the
corresponding amines or amino acid esters with sulfuryl chloride.7
X-ray crystallography (Supporting Information) showed a previ-
ously unknown 2D H-bonded network in the crystalline state of
all six compounds.8 As illustrated in Figure 1a, using 1a as an
example, one sulfamide group forms four hydrogen bonds with
those of four adjacent molecules. As a result, a rhombic 2D
network composed of the sulfamide groups is formed. Despite
the significant difference in size and properties of their substit-
uents, these sulfamides assemble in essentially the same way as
that shown in Figure 1a. The hydrogen bonds (Table 1) formed
by the sulfamide groups of these compounds vary to some extent
in their lengths and bond angles. However, all of the S atoms of
Compared to planar H-bonding functionalities such as amide
and carboxyl groups that have been extensively used in molecular
† The University of Toledo.
‡ Northern Illinois University.
(1) (a) Desiraju, G. R. Crystal Engineering: The Design of Organic Solids;
Elsevier: New York, 1989. (b) Moor, J. S.; Lee, S. Chem. Ind. 1994, 556.
(2) (a) Addadi, L.; Berkovitch-Yellin, A.; Weissbuch, I.; Mil, J. V.; Shimon,
L. J.; Lahav, M.; Leiserowitz, L. Angew. Chem., Int. Ed. Engl. 1985, 24, 466.
(b) Etter, M. C.; Urbanczyk-Lipkowska, Z.; Zia-Ebrahimi, M.; Panunyo, T.
W. J. Am. Chem. Soc. 1990, 112, 8415. (c) Lehn, J.-M.; Mascal, M.; DeCian,
A.; Fisher, J. J. J. Chem. Soc., Perkin Trans. 2 1992, 461. (d) Hosseini, M.
W.; Ruppert, T.; Schaeffer, P.; Decian, A.; Kyritsakas, N.; Fisher, J. J. Chem.
Soc., Chem. Commun. 1994, 2135. (e) Zerkowski, J. A.; MacDonald, J. C.;
Seto, C. T.; Wierda, D. A.; Whitesides, G. M. J. Am. Chem. Soc. 1994, 116,
4305. (f) Fan, E.; Yang, L.; Geib, S. J.; Stoner, T. C.; Hopkins, M. D.;
Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1995, 1251.
(3) (a) Chang, Y.-L.; West, M.-A.; Fowler, F. W.; Lauher, J. W. J. Am.
Chem. Soc. 1993, 115, 5991. (b) Reddy, D. S.; Goud, B. S.; Panneerselvam,
K.; Desiraju, G. R. J. Chem. Soc., Chem. Commun. 1993, 663. (c) Hollings-
worth, M. D.; Brown, M. E.; Santarsiero, B. D.; Huffman, J. C.; Goss, C. R.
Chem. Mater. 1994, 6, 1227. (d) Venkataraman, D.; Lee, S.; Zhang, J.; Moore,
J. S. Nature 1994, 371, 591. (e) Kolotuchin, S. V.; Fenlon, E. E.; Wilson, S.
R.; Loweth, C. J.; Zimmerman, S. C. Angew. Chem., Int. Ed. Engl. 1995, 34,
2654. (f) Bhyrappa, P.; Wilson, S. R.; Suslick, K. S. J. Am. Chem. Soc. 1997,
119, 8492.
(6) For an example using tertrahedral S atom (sulfone) in solid design,
see: Glidewell, C.; Ferguson, G. Acta Crystallogr. 1996, C52, 2528.
(7) Typically, the reaction is carried out by dropwise addition of a solution
of sulfuryl chloride in chloroform to a solution of the corresponding amine in
chloroform at 0 °C. The reaction mixture was warmed to room temperature,
stirred for 3-12 h, and washed with acidic and basic aqueous solutions.
Evaporation of chloroform results in a pure product. In the case where the
product was insoluble in the reaction medium, the pure product was obtained
by simple filtration. 1c,d were prepared by reacting sulfuryl chloride with
â-alanine ethyl ester and γ-aminobutyric acid methyl ester, respectively,
leading to the corresponding sulfamide dicarboxylic ethyl esters that were
then converted into the sulfamide dicarboxamides (1c,d) by aminolysis (30%
NH3 in water).
(8) (a) A search of the Cambridge Structural Database for structures
containing the disubstituted sulfamide substructure yielded only one relevant
example. The crystal structure of N,N′-di-tert-butylsulfamide8b shows that the
constituent molecules assemble into a hydrogen-bonded, one-dimensional
network. (b) Atwood, J. L.; Cowly, A. H.; Hunter, W. E.; Mehrotra, S. K.
Inorg. Chem. 1982, 21, 435.
(4) (a) Ermer, O.; Lindenberg, L. A. HelV. Chim. Acta 1991, 74, 825. (b)
Simard, M.; Su, D.; Wuest, J. D. J. Am. Chem. Soc. 1991, 113, 4696. (c)
Wang, X.; Simard, M.; Wuest, J. D. J. Am. Chem. Soc. 1994, 116, 12119. (d)
Zaworotko, M. J. Chem. Soc. ReV. 1994, 283. (e) Brunet, P.; Simard, M.;
Wuest, J. D. J. Am. Chem. Soc. 1997, 119, 2737.
(5) (a) Russell, V. A.; Etter, M. C.; Ward, M. D. J. Am. Chem. Soc. 1994,
116, 1941. (b) Russell, V. A.; Evans, C. C.; Li, W.; Ward, M. D. Science
1997, 276, 575. (c) Russell, V. A.; Ward, M. D. J. Mater. Chem. 1997, 7,
1123.
10.1021/ja981707c CCC: $15.00 © 1998 American Chemical Society
Published on Web 10/20/1998

Communications to the Editor
J. Am. Chem. Soc., Vol. 120, No. 43, 1998 11195
Table 1. Selected Structural Parameters for the 2D
Hydrogen-Bonded Network Composed of the Sulfamide Group and
Thickness of Individual Layers
d (S‚‚‚S) r (N-H‚‚‚O) r (N‚‚‚O) R (N-H‚‚‚O) thickness
structure
(Å)
(Å)
(Å)
(deg)
(Å)
1a
5.281
2.388
2.545
2.431
2.287
2.246
2.436
2.284
2.506
2.325
2.099
2.897
3.058
2.939
2.881
2.905
2.909
2.867
3.073
3.038
2.953
118.3
119.1
118.4
126.3
133.4
115.2
125.2
124.2
140.4
174.4
9.812
1b
4.909
5.229
5.153
4.962
5.187
5.286
5.341
5.139
13.345
1c
1d
9.665
17.367
1e
1f
13.993
11.732
Figure 2. Layered packing of 1c. A 3D hydrogen-bonded network is
observed in the solid-state structure of 1c, which is based on the 2D
sulfamide networks (perpendicular to the plane of the paper) and the 1D
hydrogen-bonded network involving the terminal primary amide groups.
The packing of 1f shows the same pattern.
the 2D networks lie in the same plane, resulting in the formation
of a sheet of sulfamide moieties.
Based on this 2D network and the tetrahedral shape of the
sulfamide groups, the sulfamide molecules pack with their long
axes parallel to each other and their substituents tilted relative to
the plane of the 2D H-bonded network (Figure 1a). This
arrangement facilitates the formation of the 2D molecular layers.9
The 2D layers formed by 1a,b,d,e assemble in the third dimension
in an organized way through van der Waals interaction between
terminal groups of the substituents R of adjacent layers. For 1d,
a weak C-H‚‚‚O interaction between methoxy O and aromatic
H atoms is also responsible for interlayer packing in the third
dimension. Due to the dense packing of constituent molecules
within a layer, penetration (interdigitation) of R groups into the
adjacent layer is not observed. Figure 1b shows the layered
packing of 1a. 1b,d,e show the same layered packing as that in
Figure 1b. Structural variation involving either terminal (1b vs
1d) or middle positions (1b vs 1e, introduction of chiral groups)
of substituents does not interfere with assembly of the sulfamide
sheets. Chiral 1e, as expected, crystallizes in the noncentro-
symmetric space group P2(1). Achiral 1d, surprisingly, also packs
in this space group. This class of compounds may thus offer a
new approach for designing noncentrosymmetric crystals. Vary-
ing the thickness of each layer (Table 1), as defined by the length
of its constituent molecules, is a way to adjust intersheet distances.
The robustness of the sulfamide sheet is further desmonstrated
with 1c,f. The expectation was that the primary amide groups
of 1c,f might interrupt the 2D sheets by forming unwanted
hydrogen bonds with the sulfamide moiety. Large single crystals
of 1c,f were obtained from a water solution by slow evaporation
of solvent at 30 °C. X-ray diffraction10 revealed again the
existence of a 2D H-bonded sulfamide sheet in the crystals of
1c,f. Instead of disrupting the 2D H-bonded network, the primary
amide groups form eight-membered cyclic dimer hydrogen
bonds11 that assemble the layers in the third dimension.12 Thus,
in 1c,f, a 3D H-bonded network is formed. Figure 2 show the
3D network formed by 1c. This implies that assembly of
analogues of 1c,f is very likely to offer a general strategy for
constructing hierarchical, 3D H-bonded structures. This approach
should simplify the study of molecular assmbly in the solid state
by fixing the first two dimensions and focusing on the last
remaining dimension.
Compared to planar amide and carboxyl groups, the sulfamide
moiety introduces features for crystal engineering: (1) Because
of its tetrahedral geometry, the sulfamide moiety offers an
additional dimension to the H-bonded network. (2) The constitu-
ent molecules assemble with their substituents extending above
and below the planes of the H-bonded 2D networks. This not
only helps the self-assembly of the 2D molecular layers with
adjustable thickness but also introduces systematically the ancil-
lary molecular functionality along the third dimension. (3) Since
each 2D layer provides two faces of well-ordered terminal groups,
stacking of the layers in the third dimension is reinforced by the
noncovalent interaction between the individual terminal groups.
Such 2D layers may serve as templates for designing solid-state
structures with sandwiched guest layers.
We have demonstrated a novel 2D H-bonded network com-
posed of the sulfamide moiety of N,N′-disubstituted sulfamide.
The 2D H-bonding motif is retained despite changes in the
substituents of the sulfamide molecules. Therefore, formation
of molecular layers is tunable by changing the substituents of
the sulfamide molecules. Assembly of 2D layers in the third
dimension, through either H-bonding or van der Waals interaction,
has been achieved. Efforts to designed layered materials based
on N,N′-dialkyl- or N,N′-diarylsulfamides and 3D molecular
arrays, based on sulfamide dicarboxamides and sulfamide dicar-
boxylic acids, are being made. N,N′-Disubstituted sulfamides
with two different substituents are also being designed and
synthesized. These unsymmetrical sulfamides may assemble into
molecular layers with two different surfaces. Polar-organized
crystals may result from the assembly of these 2D layers.
Incorporation of the 2D sulfamide network into self-assembled
monolayers should significantly enhance the stability of the
monolayers. The corresponding results will be reported later.
(9) The layered structures formed by 1b,d,e are to some extent similar to
previously reported 2D layered crystal structures of 4,4′-disubstituted meso-
hydrobenzoin: (a) Pennington, W. T.; Chakraborty, S.; Paul, I. C.; Curtin, D.
Y. J. Am. Chem. Soc. 1988, 110, 6498. (b) Swift, J. A.; Pal, R.; McBride, J.
M. J. Am. Chem. Soc. 1998, 120, 96.
(10) The X-ray data of 1a-e are given in the Supporting Information. The
X-ray data of 1f will be published as a separate paper: Gong, B.; Zheng, C.;
Zhang, J. Acta Crystallogr., in press.
Acknowledgment. We thank NIH (CA74402), NSF (DMR-9704048),
and the University of Toledo for support of this work, and Professor
Max O. Funk for helpful comments.
(11) (a) Leiserowitz, L.; Schmidt, G. M. J. J. Chem. Soc. A 1969, 2372.
(b) Leiserowitz, L.; Hagler, A. T. Proc. R. Soc. London, A 1983, 133.
(12) (a) The eight-membered cyclic dimer hydrogen bonds form via the
amide syn-H atoms. N‚‚‚O, N-H‚‚‚O observed: 1c, 2.963 Å, 169.3°; 1f, 2.946
Å, 175.4°. (b) The amide anti-H atoms form additional hydrogen bonds to
amide carbonyl O atoms of the neighboring cyclic hydrogen bond dimers,
which links the cyclic dimer hydrogen bonds into a ribbonlike network. N‚‚‚O,
N-H‚‚‚O observed: 1c, 2.960 Å, 156.3°; 1f, 2.981 Å, 152.1°.
Supporting Information Available: X-ray, atomic, and thermal data
for 1a-e (31 pages, print/PDF). X-ray crystallographic data, in CIF
format, for 1a-e, are available on the Web only. See any current
masthead page for ordering information and Web access instructions.
JA981707C