Coordination polymers and networks constructed from bidentate ligands linked with sulfonamide and silver(I) ions

Article abstract of DOI:10.1021/cg100013g

Ligands that consist of pyridine rings linked by sulfonamide are simple and unique building blocks which form infinite polymers and networks via metal-coordination and hydrogen bonds (H-bonds). Single crystal X-ray analysis revealed that the complexation of bidentate ligands 1 and 2 bearing secondary sulfonamide with silver(I) ion results in the formation of [AgL ₂(OTf)] (1a), [Ag₂(μ-L)₂(OTf)₂] (2a), and [AgL(OTf)]_n (2b) complexes. The complex 1a assembled into extended one-dimensional (1D) chains through H-bonds between the N-H moieties of sulfonamide and nitrogen atom of pyridyl groups. These individual chains associated into a three-dimensional (3D) network structure via C...O interactions between pyridyl protons and the oxygen atom of sulfonamides. The complex 2a assembled into two-dimensional (2D) sheets through H-bonds between the N-H moieties of sulfonamide and H₂O molecules. In the complex 2b, enantiopure continuous 1D chain [AgL(OTf)]_n was formed. In these structures, the silver(I) centers have a T-shaped stereochemistry in which each ion is coordinated by two pyridyl groups of the ligand and a trifluoromethane sulfonate anion. In the complex of ligands 3 and 4 with an ethyl group on the nitrogen atom of sulfonamide and silver(I) ions, continuous 1D homochiral chains [AgL(OTf)]_n (3a) and helical polymers [AgL]_n(OTf) _n (4a) were formed. Both 1D homochiral polymers contained a racemic mixture of right-and left-handed coordination polymers, which assemble into 2D sheets and 3D networks via Ag...Ag, Ag...O, and C-H...O interactions.

Full text of DOI:10.1021/cg100013g

DOI: 10.1021/cg100013g
Coordination Polymers and Networks Constructed from
Bidentate Ligands Linked with Sulfonamide and Silver(I) Ions
2010, Vol. 10
2291–2297
Kosuke Katagiri, Takashi Ikeda, 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 January 4, 2010; Revised Manuscript Received March 15, 2010
ABSTRACT: Ligands that consist of pyridine rings linked by sulfonamide are simple and unique building blocks which form
infinite polymers and networks via metal-coordination and hydrogen bonds (H-bonds). Single crystal X-ray analysis revealed
that the complexation of bidentate ligands 1 and 2 bearing secondary sulfonamide with silver(I) ion results in the formation of
[AgL2(OTf)] (1a), [Ag2(μ-L)2(OTf)2] (2a), and [AgL(OTf)]n (2b) complexes. The complex 1a assembled into extended one-
dimensional (1D) chains through H-bonds between the N-H moieties of sulfonamide and nitrogen atom of pyridyl groups.
These individual chains associated into a three-dimensional (3D) network structure via C-H O interactions between pyridyl
3 3 3
protons and the oxygen atom of sulfonamides. The complex 2a assembled into two-dimensional (2D) sheets through H-bonds
between the N-H moieties of sulfonamide and H2O molecules. In the complex 2b, enantiopure continuous 1D chain
[AgL(OTf)]n was formed. In these structures, the silver(I) centers have a T-shaped stereochemistry in which each ion is
coordinated by two pyridyl groups of the ligand and a trifluoromethane sulfonate anion. In the complex of ligands 3 and 4 with
an ethyl group on the nitrogen atom of sulfonamide and silver(I) ions, continuous 1D homochiral chains [AgL(OTf)]n (3a)
and helical polymers [AgL]n(OTf)n (4a) were formed. Both 1D homochiral polymers contained a racemic mixture of right- and
left-handed coordination polymers, which assemble into 2D sheets and 3D networks via Ag Ag, Ag O, and C-H
3 3 3 3 3 3
O
3 3 3
interactions.
Introduction
represent valuable building blocks for the creation of solid-
state structures. N-Phenylbenzenesulfonamide derivatives exist
in a synclinal conformation which places the aromatic rings at
both ends in the same direction with a twist. Moreover, a
unique feature of sulfonamide is that a secondary sulfonamide
forms hydrogen bonds (H-bonds) because the preferable
synclinal conformation tends to place the sulfonyl oxygen
and sulfonamide proton on the same side of the molecule.
Thus, it is expected that the orientation of the hydroxyl,
carboxyl, and pyridyl groups as a coordination site connected
with sulfonamide leads to predictable and desired structural
aggregates. Herein the syntheses and structures of bis(pyridyl)
ligands linked with secondary and tertiary sulfonamide, and
their silver(I) complexes are reported. Single crystals suitable
for diffraction studies were obtained as crystals 1a-4a by the
slow evaporation of a CH3CN/CHCl3 solution of four types
ofbidentate ligands (1-4, Scheme1)and AgOTf, respectively.
X-ray diffraction experiments confirmed the formation of
H-bonded one-dimensional (1D) polymers for crystal 1a,
H-bonded two-dimensional (2D) sheets for crystal 2a, infinite
1D homochiral chains for crystals 2b, 3a, and continuous 1D
homochiral helical polymers for crystal 4a. All H-bonded and
metal-coordinated structures assemble into 2D sheets and
three-dimensional (3D) networks via Ag Ag, Ag O,
Over the last two decades, the construction of metal-organic
frameworks has attracted considerable recent interest toward
the development of new functional materials in the field of
materials and solids.1 This interest has been ascribed to their
potential applications such as gas adsorption,2 selective orga-
nic catalysis,3 sensing,4 molecular electronics,5 and magnetic
devices.6 A number of metal-organic architectures have been
successfully designed and synthesized by the selection of the
metal’s coordination preferences and ligand geometry. Such
selection has led to unique structures and useful properties.7
A variety of multidentate organic ligands for producing
metal-organic frameworks have been exploited,8 and simple
bidentate ligands were prepared by the connection between
metal-coordination sites and a linker.1g,i,9 Linker units of the
ligand often play a crucial role in crystal engineering because
of their directionality to control the design of various mole-
cular assemblies and have been extensively used to assemble
organic molecular building blocks into well-defined crystal-
line materials.10 Phenyl, acetylenic, and vinyl linker are used
as rigid spacers,11 and urea, amide, and hydrazine groups
provide secondary noncovalent interaction sites.12 The use of
such linkers leads to the creation of complex structures from
simple building blocks. However, other novel linker units that
can be incorporated into bis(pyridyl) ligands remain to be
exploited. We recently described pseudopolymorphs of aro-
matic bis-phenyl and macrocyclic derivatives with sulfon-
amide moieties.13 The crystals of these pseudopolymorphs
were found to exhibit diverse structures through noncovalent
interactions.13 These results showed that aromatic sulfonamides
3 3 3
3 3 3
and C-H O interactions.
3 3 3
Experimental Section
N-(2-Pyridyl)-3-pyridylsulfonamide (1). 2-Aminopyridine (0.941 g,
10 mmol) and pyridine (10 mL) were added to a solution of
3-pyridylsulfonyl chloride (1.78 g, 10 mmol) in dichloromethane
(100 mL) with stirring for 4 h at room temperature. The reaction
mixture was extracted with chloroform (600 mL). The organic layer
was washed with excess water (300 mLꢀ10) and brine (200 mL) and
dried over Na2SO4. After evaporation, the crude product was purified
*Corresponding author. Tel: 81-87-894-5111 ex. 6308. Fax: 81-87-894-
0181. E-mail: azumayai@kph.bunri-u.ac.jp.
r
2010 American Chemical Society
Published on Web 04/20/2010
pubs.acs.org/crystal

2292 Crystal Growth & Design, Vol. 10, No. 5, 2010
Scheme 1. Syntheses of Bidentate Ligands (1-4)
Katagiri et al.
ethyl acetate/hexane=1:1) to give 4 in 79% yield as a white powder
(1.01 g, 3.85 mmol): mp 88-89 °C; 1H NMR (400 MHz, CDCl3): δ
8.88 (d, J=1.6 Hz, 1H), 8.82 (dd, J=4.8, 1.6 Hz, 1H), 8.58 (dd, J=
4.4, 1.2 Hz, 1H), 8.28 (d, J=2 Hz, 1H), 7.84 (dt, J=8.8, 1.6 Hz, 1H),
7.50 (dt, J=8, 1.6 Hz, 1H), 7.43 (dd, J=8.8, 4.8 Hz, 1H), 7.33 (d,
J=4.8 Hz, 1H), 3.69 (q, J=7.2 Hz, 2H) and 1.14 (t, J=6.8 Hz, 3H)
ppm; 13C NMR (125 MHz, CDCl3): δ 153.51 (CH), 149.67 (CH),
149.26 (CH), 148.17 (CH), 136.59 (CH), 135.03 (CH), 134.96 (Cq),
134.85 (Cq), 123.89 (CH), 123.65 (CH), 45.92 (CH2) and 14.05
(CH3) ppm; FAB-MS m/z 264.2 [M þ H]þ; HRMS: m/z calcd for
C
12H14N3O2S: 264.0807. Found 264.0776; elemental analysis calc.
for C12H13N3O2S: C, 54.74; H, 4.98; N, 15.96. Found: C, 54.72; H,
4.80; N, 15.84.
2N-(2-Pyridyl)-3-pyridylsulfonamide AgOTf (1a). AgOTf was
3
added to a solution of 1 in CH3CN/CHCl3. After several minutes
of stirring, the complex precipitated as a white solid, which was
collected by filtration and dried under vacuum.
by silica gel column chromatography (eluent chloroform/methanol=
10:1) to give 1 in 92% yield as a white powder (2.16 g, 9.2 mmol): mp
186-188 °C; 1H NMR (400 MHz, DMSO-d6): δ 9.01 (d, J=2.0 Hz,
1H), 8.73 (dd, J=1.6, 4.8 Hz, 1H), 8.22 (dt, J=2.0, 8.0 Hz, 1H), 7.96
(d, J=4.8 Hz, 1H), 7.78 (dt, J=2.0, 6.8 Hz, 1H), 7.56 (dd, J=4.8, 8.0
2N-(3-Pyridyl)-3-pyridylsulfonamide AgOTf (2a, 2b). This was
prepared similarly from AgOTf and 2.
3
N-Ethyl-N-(2-pyridyl)-3-pyridylsulfonamide AgOTf (3a). This
was prepared similarly from AgOTf and 3.
3
Hz, 1H), 7.23 (d, J=8.8 Hz, 1H), and 6.87 (t, J=6.4 Hz, 1H) ppm; 13
C
N-Ethyl-N-(3-pyridyl)-3-pyridylsulfonamide AgOTf (4a). This
was prepared similarly from AgOTf and 4.
3
NMR (125 MHz, DMSO-d6): δ 154.32 (Cq), 152.87 (CH), 147.40
(CH), 142.35 (CH), 141.50 (CH), 139.44 (Cq), 134.75 (CH), 124.48
(CH), 115.27 (CH), and 114.94 (CH) ppm; FAB-MS: m/z 236.1 [Mþ
H]þ; HRMS: m/z calcd for C10H10N3O2S: 236.0494. Found 236.0522;
Elemental analysis calc. for C10H9N3O2S: C, 51.05; H, 3.86; N, 17.86.
Found: C, 51.18; H, 3.67; N, 17.48.
Measurement. X-ray data of the crystals were collected on a CCD
˚
diffractometer with graphite monochromated MoKR (λ=0.71073 A)
radiation. Data collections for crystals were carried out at low
temperature (150 K) using liquid nitrogen. The crystal structures
were solved by direct methods SHELXS-97 and refined by full-
matrix least-squares SHELXL-97.14 All non-hydrogen atoms were
refined anisotropically and hydrogen atoms were included as their
calculated positions.
N-(3-Pyridyl)-3-pyridylsulfonamide (2). 3-Aminopyridine (0.941 g,
10 mmol) and pyridine (10 mL) were added to a solution of 3-pyridyl-
sulfonyl chloride (1.78 g, 10 mmol) in dichloromethane (100 mL) with
stirring for 4 h at room temperature. The reaction mixture was
extracted with chloroform (600 mL). The organic layer was washed
with excess water (300 mL ꢀ 10) and brine (200 mL) and dried over
Na2SO4. After evaporation, the crude product was purified by silica gel
column chromatography (eluent chloroform/methanol=10:1) to give
2 in 83% yield as a white powder (1.95 g, 8.3 mmol): mp 184-186 °C;
1H NMR (400 MHz, DMSO-d6): δ 8.89 (dd, J=0.8, 2.4 Hz, 1H), 8.80
(dd, J=1.6, 4.8 Hz, 1H), 8.30-8.29 (m, 2H), 8.13 (dq, J=1.6, 8.4 Hz,
1H), 7.62 (ddd, J = 0.8, 4.8, 8.0 Hz, 1H), 7.53 (dq, J = 1.2, 8.0 Hz,
1H), and 7.31 (ddd, J=0.4, 4.4, 8.0 Hz, 1H) ppm; 13C NMR(125 MHz,
DMSO-d6): δ 153.68 (CH), 147.02 (CH), 145.80 (CH), 142.30 (CH),
135.60 (Cq), 134.66 (CH), 133.87 (Cq), 128.08 (CH), 124.39 (CH), and
124.04 (CH) ppm; FAB-MS: m/z 236.1 [M þ H]þ; HRMS: m/z calcd
for C10H10N3O2S: 236.0494. Found 236.0473; Elemental analysis calc.
for C10H9N3O2S: C, 51.05; H, 3.86; N, 17.86. Found: C, 51.04; H, 3.62;
N, 17.65.
Results and Discussion
Bis(pyridyl) ligands containing sulfonamides (1 and 2) were
prepared by the reaction of sulfonyl chloride and amino pyri-
dine. Crystal data and conformational parameters of 1 and 2
are shown in Tables 1 and 2, respectively. The sulfonamide
bonds of all sulfonamides are synclinal (Figure 1), and the
torsion angles of the sulfonamide moiety [C(Py)-S-N-C(Py)]
are 66.6(2), 71.2(2), and 86.0(2)° (Table 2).
Reaction of equimolar amounts of the sulfonamide ligands
(1, 2) with AgOTf gave the corresponding complexes [AgL2-
(OTf)] (L=1 (1a)), [Ag2(μ-L)2(OTf)2] 2H2O (L=2 (2a)), and
3
[AgL(OTf)]n nCHCl3 (L=2 (2b)). The crystals of complexes
3
1a, 2a, and 2b were isolated as analytically pure, air-stable,
white solids thatare slightly soluble in organic solvents such as
chloroform, dichloromethane, tetrahydrofuran, and metha-
nol. Crystal data and conformational parameters of 1a, 2a,
and 2b are shown in Tables 1 and 2, respectively. The sulfo-
namide bonds of 1a, 2a, and 2b are synclinal (Figure 2), and
the torsion angles of the sulfonamide moiety [C(Py)-S-
N-C(Py)] are 69.8(6), 77.8(6), 59.0(3), and 59.8(5)° (Table 2).
The silver(I) centers have a T-shaped stereochemistry, each
ion is coordinated to two pyridyl groups of the ligand 1, 2 and
a trifluoromethanesulfonate anion.
N-Ethyl-N-(2-pyridyl)-3-pyridylsulfonamide (3). 2-Ethylamino-
pyridine (0.562 g, 4.87 mmol) and pyridine (5 mL) was added to a
solution of 3-pyridylsulfonyl chloride (0.893 g, 5 mmol) in dichloro-
methane (50 mL) with stirring for 4 h at room temperature. The
reaction mixture was extracted with chloroform (300 mL). The orga-
nic layer was washed with excess water (150 mL ꢀ 10) and brine
(100 mL) and dried over Na2SO4. After evaporation, the crude pro-
duct was purified by silica gel column chromatography (eluent ethyl
acetate/hexane=1:4) to give 3 in 90% yield as a colorless oil (1.15 g,
4.38 mmol): 1H NMR (400 MHz, CDCl3): δ 8.84 (s, 1H), 8.77 (d, J=
4.8 Hz, 1H), 8.34 (d, J=4.8 Hz, 1H), 7.93 (d, J=8.4 Hz, 1H), 7.77
(t, J=6.4 Hz, 1H), 7.55 (d, J=8.0 Hz, 1H), 7.41 (t, J=6.6 Hz, 1H),
7.20 (t, J=6.0 Hz, 1H), 3.84 (q, J=7.2 Hz, 2H) and 1.13 (t, J=6.8 Hz,
3H) ppm; 13C NMR (125 MHz, CDCl3): δ 153.09 (CH), 151.64 (Cq),
148.43 (CH), 148.33 (CH), 137.96 (CH), 135.15 (CH), 135.12 (Cq),
123.37 (CH), 123.34 (CH), 122.16 (CH), 43.58 (CH2) and 13.94 (CH3)
The crystal of complex 1a crystallized in a triclinic system,
space group P1, and included four molecules of ligand 1, two
molecules of AgOTf, and two molecules of tetrahydrofuran in
the unit cell. Examination of the crystal packing showed that
the crystal of complex 1a consists of infinite 1D chains
through intermolecular H-bonds betweenthe pyridyl nitrogen
atom and the nitrogen atom of the sulfonamide in complex 1a
(the distances of N1 N6 and N3 N4 are 2.906(7) and
ppm; FAB-MS m/z 264.2 [MþH]þ; HRMS: m/z calcd for C12H14
-
N3O2S: 264.0807. Found 264.0847; elemental analysis calc. for C12H13-
N3O2S: C, 54.74; H, 4.98; N, 15.96. Found: C, 54.36; H, 4.86; N, 15.65.
N-Ethyl-N-(3-pyridyl)-3-pyridylsulfonamide (4). 3-Ethylamino-
pyridine (0.562 g, 4.87 mmol) and pyridine (5 mL) was added to a
solution of 3-pyridylsulfonyl chloride (0.893 g, 5 mmol) in dichloro-
methane (50 mL) with stirring for 4 h at room temperature.
The reaction mixture was extracted with chloroform (300 mL).
The organic layer was washed with excess water (150 mLꢀ10) and
brine (100 mL) and dried over Na2SO4. After evaporation, the crude
product was purified by silica gel column chromatography (eluent
3 3 3
3 3 3
˚
2.930(5) A, respectively) along the ac plane (Figure 3a). The
oxygen atoms of the sulfonamide are weakly coordinated
to the silver(I) of neighboring polymer chains (the Ag
˚
O
3 3 3
distance is 2.901(5) A). Furthermore, the 1D chain form a 3D
network by intermolecular multiple C-H O interactions
3 3 3

Article
Crystal Growth & Design, Vol. 10, No. 5, 2010 2293
Table 1. Crystallographic Data for Sulfonamide 1-4 and Complexes 1a-4a
1
2
3
4
a
;
formula
formula weight
space group
C10H9N3O2S
235.26
P1
5.853(1)
8.893(2)
10.734(2)
89.484(2)
84.630(2)
71.987(2)
150
C10H9N3O2S
235.26
P1
6.134 (2)
7.475(2)
11.245(3)
89.835(3)
84.335(3)
84.964(3)
150
C12H13N3O2S
263.31
P21
9.355(2)
5.578(1)
12.427(3)
90
105.339(3)
90
150
625.4(2)
2
1.398
˚
a (A)
˚
b (A)
˚
c (A)
R (°)
β (°)
γ (°)
T (K)
3
˚
V (A )
Z
528.9(2)
2
1.477
511.1(2)
2
1.529
Dcalc (Mg/m3)
μ (mm-1
)
0.294
0.304
0.256
R1, wR2 [I>2σ(I)]
R1, wR2 (all data)
CCDC number
0.0384, 0.1082
0.0418, 0.1116
759730
0.0369, 0.0888
0.0462, 0.0948
759732
0.0347, 0.0918
0.0384, 0.0936
759735
1a
2a
2b
3a
4a
formula
formula weight
space group
C25H26N6O8S3F3Ag
799.57
P1
8.167(2)
13.281(3)
15.470(4)
93.653(3)
104.099(3)
92.475(3)
150
C22H22N6O12S4F6Ag2
1020.44
P1
9.286(2)
9.546(1)
10.359(1)
112.859(2)
100.525(2)
95.132(2)
120
C12H10N3O5S2F3Cl3Ag
611.57
P21
8.419(2)
14.489(3)
9.108(2)
90
112.637(2)
90
120
1025.4(3)
2
1.981
C13H13N3O5S2F3Ag
520.25
P21/n
8.649(1)
15.158(2)
13.874(2)
90
100.356(2)
90
150
1789.3(4)
4
1.931
C13H13N3O5S2F3Ag
520.25
P21/c
11.4959(7)
11.1319(6)
14.4961(8)
90
106.451(1)
90
150
1779.1(2)
4
1.942
˚
a (A)
˚
b (A)
˚
c (A)
R (°)
β (°)
γ (°)
T (K)
3
˚
V (A )
Z
1621.1(7)
2
1.638
818.7(3)
1
2.070
Dcalc (Mg/m3)
μ (mm-1
)
0.887
1.555
1.634
1.421
1.429
R1, wR2 [I>2σ(I)]
R1, wR2 (all data)
CCDC number
0.0463, 0.1245
0.0636, 0.1335
759733
0.0317, 0.0441
0.0406, 0.0457
768083
0.0412, 0.0782
0.0515, 0.0818
768084
0.0317, 0.0731
0.0485, 0.0790
759734
0.0284, 0.0710
0.0334, 0.0740
759736
a Compound 3 was obtained as oil.
Table 2. Conformational Parameters of Sulfonamide 1-4 and
Complexes 1a-4a
Figure 1. Thermal ellipsoid models of the crystal structures of sulfon-
amide ligands 1, 2, and 4. Ellipsoids of all non-hydrogen atoms are
drawn at the 50% probability.
sulfonamide ligand and silver(I) ions self-assemble to form an
18-membered disilver macrocycle [Ag2(μ-2)2(OTf)2] in a chair
conformation (Figure 4a). The macrocycles associate through
intermolecular H-bonds between the nitrogen atom of the
sulfonamide and water molecules, intermolecular H-bonds
between the oxygen atom of the sulfonamide and water
1
2
3
4
torsion angle (deg)
C1-N1-S1-C6
66.6(2)
71.2(2)
86.0(2)
1aa
2a
2b
3a
4a
torsion angle (deg)
C1-N1-S1-C6
70.2(4), 78.0(4) 59.0(3) 59.8(5) 101.0(2) 77.2(2)
molecules (the distances of N1-H1 O6, O6-H6A O5,
3 3 3 3 3 3
O6-H6A O1, and O6-H6B O5 are 2.777(3), 3.036(4),
3 3 3
3 3 3
a Two conformers of ligands are included in the asymmetric unit of
the crystal (see Figure 2).
˚
2.977(4), and 2.815(4) A, respectively), to give infinite 2D
sheets (Figure 4b). Furthermore, the 2D sheets form a 3D
O
˚
(the C O distance ranged from 3.202(9) to 3.415(9) A)
between pyridyl protons and the oxygen atoms of sulfon-
amides in 1a along the a and b axis (Figure 3b).
The crystal of complex 2a crystallized in a triclinic system,
space group P1, and included a ligand 2, a silver trifluoro-
methanesulfonate and a water molecule in the unit cell. The
network by intermolecular Ag O interactions (the Ag
˚
is 2.804(4) A, Figure 4c).
3 3 3
3 3 3
3 3 3
The crystal of complex 2b crystallized in a monoclinic
system, space groupP21, andincluded twomolecules of ligand
2, two molecules of AgOTf and two molecules of chloroform
in the unit cell. The structure of complex 2b is shown to be

2294 Crystal Growth & Design, Vol. 10, No. 5, 2010
Katagiri et al.
Figure 2. Thermal ellipsoid models of the crystal structures of the
silver(I) complexes: [Ag(1)2(OTf)] THF (1a), [Ag2(μ-2)2(OTf)2]
3
þ3
2H2O (2a), [Ag(2)(OTf)] (2b), [Ag(3)(OTf)] (3a), and [Ag(4)] -
OTf- (4a). The solvent molecules are omitted for clarity. Ellipsoids
of all non-hydrogen atoms are drawn at the 50% probability.
Figure 4. Crystal structure of complex 2a as a ball and stick model.
(a) The disilver macrocycle. Solvent molecules (H2O) are omitted
for clarity. (b) H-bonded infinite 2D sheets. (c) 3D network struc-
ture via Ag O interactions. H-bonds are indicated by black dash
lines and Ag O interactions are indicated by red dash lines.
3 3 3
3 3 3
Thus, N-ethylated ligands (3, 4) of the sulfonamide moiety
were prepared to construct continuous 1D polymers. The
sulfonamide 4 was obtained as colorless crystal, whereas the
sulfonamide 3 was obtained as colorless oil. Crystal data and
conformational parameters of 4 are shown in Tables 1 and 2,
respectively. The sulfonamide bond of 4 is synclinal (Figure 1),
and the torsion angle of the sulfonamide moiety [C(Py)-S-
N-C(Py)] is 86.0(2)° (Table 2).
The reaction of equimolar amounts of the sulfonamide ligands
(3, 4) with the AgOTf gave the corresponding complexes
[AgL(OTf)]n (L=3 (3a)) and [AgL]n(OTf)n (L=4 (4a)). The
silver(I) complexes 3a and 4a were also isolated as analytically
pure, air-stable, white solids that are slightly soluble in organic
solvents such as chloroform, dichloromethane, tetrahydrofu-
ran, and methanol. Crystal data and conformational para-
meters of 3a and 4a are shown in Table 1 and 2, respectively.
The sulfonamide bond of 4a is synclinal (Figure 2) and the
torsion angle of the sulfonamide moiety [C(Py)-S-N-C(Py)]
is 77.2(2)° (Table 2). Interestingly, the sulfonamide bond of 3a is
anticlinal (Figure 2), and the torsion angle is 101.0(2)° (Table 2).
The crystal of complex 3a crystallized in a monoclinic
system, space group P21/n, and included four molecules of
ligand 3 and four molecules of AgOTf in the unit cell. X-ray
Figure 3. Crystal structure of silver(I) complex 1a as a ball and stick
model. (a) H-bonded infinite 1D chain and intermolecular multiple
Ag O interactions. (b) 3D network structure via C-H O inter-
actions. Solvent molecules (THF) are omitted for clarity. H-bonds
3 3 3
3 3 3
are indicated by black dash lines, and Ag O interactions and
C-H O interactions are indicated by red dash lines.
3 3 3
3 3 3
enantiopure 1D polymer, in which ligand 2 is connected by
silver(I) ions (Figure 5a). The homochiral polymers are
further associated through H-bond between N-H moieties
and oxygen atoms of trifluoromethanesulfonate ion (the
˚
N-H O is 2.318(3) A) to form 2D layers (Figure 5b).
3 3 3
Furthermore, the 2D layers stack to form a 3D network by
intermolecular Ag O interactions (the Ag O distance is
3 3 3 3 3 3
˚
2.836(5) A).
As shown in the crystals of complex 1a, 2a, and 2b, silver
complexes assembled into infinite 1D polymer and 2D layers
via H-bonding interactions, which pack into 3D networks.

Article
Crystal Growth & Design, Vol. 10, No. 5, 2010 2295
Figure 5. Crystal structure of complex 2b as a ball and stick model.
(a) Homochiral 1D chain. (b) The 2D layered structure through
H-bonds between 1D polymers. (c) 3D network structure via Ag
interactions. Solvent molecules (CHCl3) are omitted for clarity,
O
3 3 3
Figure 6. Crystal structure of complex 3a as a ball and stick model.
(a) Homochiral 1D chain. (b) 2D layered structure via intermole-
H-bonds are indicated by black dash lines and Ag O interactions
are indicated by red dash lines.
3 3 3
cular multiple Ag OandC-H O interactions between 1D chains.
3 3 3
3 3 3
(c) 3D network structure via C-H O interactions. The enantio-
meric chains are shown in cyan and magenta, respectively.
3 3 3
crystallographic analysis revealed that the product was an
infinite 1D polymeric structure formed by silver(I) atoms
alternating with ligand 3 that are mutually bridging and
contain a racemic mixture of both right- and left-handed
coordination chains per unit cell (Figure 6). Both enantiomers
of the 1D chain extend along the plane of the b and c axes. An
interesting feature of the structure of 3a is that pairs of homo-
of complex 4a was shown to be 1D homochiral helical
polymer, in which ligand 4 was connected by silver(I) ions
(Figure 7a). The crystals contain a racemic mixture of both
right- and left-handed helical coordination polymers. Both
enantiomers of the helical polymeric strand extend along the
plane of the a and c axes. The homochiral helical polymers are
further associated through Ag Ag bonding (the Ag Ag
chiral chains are further associated through weak Ag
˚
O
interaction (the Ag O distance is 2.723(2) A) and intermole-
3 3 3
3 3 3
3 3 3
3 3 3
˚
˚
cular C-H O interactions (the C O distance is 3.181(3) A)
distance is 3.116(5) A), to form racemic 2D layers along the
c axis (Figure 7b). Furthermore, the 2D layers stack to form a
3 3 3
3 3 3
between pyridyl protons and the oxygen atoms of coordinated
trifluoromethanesulfonate anion along thec axis toformrace-
mic 2D sheets of chains, resulting in the optical inactivity of
the crystal (Figure 6b). Furthermore, the 2D layer was found
to stack to yield a 3D network by intermolecular multiple
3D network by intermolecular C-H O interactions (the
3 3 3
˚
O distance is 3.293(3) A) between pyridyl protons and
the oxygen atom of the sulfonamides in 4a along the a axis
C
3 3 3
(Figure 7c). The counteranions (TfO-) are also coordinated
C-H O interactions (the C O distance ranged from
to the silver(I) centers (the distances of Ag O are 2.799(2),
3 3 3
3 3 3
3 3 3
˚
˚
3.138(3) and 2.909(3) A), and they form a bridge between the
3.108(3) to 3.617(4) A) between pyridyl protons and the
oxygen atoms of the sulfonamides along the b axis (Figure 6c).
The crystal of complex 4a crystallized in a monoclinic sys-
tem, space group P21/c, and included four molecules of ligand
4 and four molecules of AgOTf in the unit cell. The structure
silver ions. The fragment that determines the pitch of the
helix is composed of two atoms of silver(I) ions and two mole-
cules of ligand 4, where the distance between silver(I) atoms is
˚
11.132(1) A.

2296 Crystal Growth & Design, Vol. 10, No. 5, 2010
Katagiri et al.
complexes, 2D sheets and 3D network structures were formed
via Ag Ag, Ag O, and C-H O interactions. The self-
3 3 3 3 3 3 3 3 3
assembly of ligands with the sulfonamide moiety via metal-
coordination is a suitable approach not only for the develop-
ment of novel metal-organic frameworks but also ordered
arrangements into 1D arrays. The construction of optically
pure left- or right-handed 1D helical polymers by introducing
chiral functional groups on the nitrogen atom of the sulfon-
amide ligand is currently under investigation.
Supporting Information Available: 1H and 13C NMR spectro-
scopic data (PDF) and crystallographic analysis data are available
free of charge via the Internet at http://pubs.acs.org.
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