Synthesis, structure, and thermal stability of silver(I) coordination polymers with bis(pyridyl) ligands linked by an aromatic sulfonamide: One-dimensional-straight chain, one-dimensional-columnar with helical components, and two-dimensional-layer network structures

Article abstract of DOI:10.1021/cg4013944

Three different types of coordination polymers, one-dimensional (1D) straight chain, 1D-columnar structure, and two-dimensional (2D) layer structure, have been prepared by the complexation of Ag(I) ions with bis(pyridyl) ligands linked by an aromatic sulfonamides and structurally characterized by single-crystal X-ray diffraction and thermogravimetric analysis. Structural analyses showed that the complexation of the 3-pyridyl ligand with AgOTf and the complexation of the 4-pyridyl ligand with AgBF₄ in CHCl ₃/CH₃CN resulted in the formation of 1D straight-chain polymers. In the complexation of the 3-pyridyl ligand with AgBF₄ in CHCl₃/CH₃CN, the resulting continuous 1D columnar coordination polymers were formed containing a racemic mixture of left- and right-handed helices. Furthermore, the 2D-layer structure was constructed by the complexation of a 4-pyridyl ligand with AgSbF₆ in CHCl ₃/MeOH.

Full text of DOI:10.1021/cg4013944

Article
pubs.acs.org/crystal
Synthesis, Structure, and Thermal Stability of Silver(I) Coordination
Polymers with Bis(pyridyl) Ligands Linked by an Aromatic Sulfonamide:
One-Dimensional-Straight Chain, One-Dimensional-Columnar with
Helical Components, and Two-Dimensional-Layer Network Structures
Kosuke Katagiri,*,† Takahiro Sakai,† Maiko Hishikawa,† Hyuma Masu,‡ Masahide Tominaga,†
Kentaro Yamaguchi,† and Isao Azumaya*,§
†Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan
‡Center for Analytical Instrumentation, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
§Graduate School of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
S
* Supporting Information
ABSTRACT: Three different types of coordination polymers,
one-dimensional (1D) straight chain, 1D-columnar structure, and
two-dimensional (2D) layer structure, have been prepared by the
complexation of Ag(I) ions with bis(pyridyl) ligands linked by an
aromatic sulfonamides and structurally characterized by single-crystal
X-ray diffraction and thermogravimetric analysis. Structural analyses
showed that the complexation of the 3-pyridyl ligand with AgOTf
and the complexation of the 4-pyridyl ligand with AgBF4 in CHCl3/
CH3CN resulted in the formation of 1D straight-chain polymers. In
the complexation of the 3-pyridyl ligand with AgBF4 in CHCl3/
CH3CN, the resulting continuous 1D columnar coordination polymers were formed containing a racemic mixture of left- and right-handed
helices. Furthermore, the 2D-layer structure was constructed by the complexation of a 4-pyridyl ligand with AgSbF6 in CHCl3/MeOH.
rings at both ends of the linker in the same direction with a twist.
Previously, we revealed that the complexation of bis(pyridyl)
bidentate ligands linked by an aromatic sulfonamide with Ag(I)
ions resulted in the formation of infinite one-dimensional (1D)
straight and helical chains.10c Bis(pyridyl) ligands linked by an
aromatic sulfonamide are unique ligands because of the flexibility
of the S−N bond and the twisted synclinal conformation of the
sulfonamide. On the basis of these factors and as an extension of
our previous work, herein we focus on the elongation of the
sulfonamide linker to construct columnar or layer complexes. In
this paper, we report the synthesis of the elongated bis(pyridyl)
ligands 1 and 2, and the complexation of these ligands with Ag(I)
salts, as well as the crystal structures and thermal stability
properties of the resulting complexes. The bis(pyridyl) ligands
were elongated using a Suzuki-Miyaura coupling reaction. The
complexes 1a, 1b, 2a, and 2b were formulated as [Ag(1)OTf]n
(1a), [Ag(1)]n·nBF4 (1b), [Ag(2)CH3CN]n·nBF4·nCHCl3 (2a),
and [Ag(2)]n·nSbF6·nCH4O (2b). In complexes 1a and 2a,
infinite 1D straight chains with a T-shaped coordination geometry
about the Ag(I) centers were formed by the reaction of ligand 1 or
2 with Ag(I) salts in CHCl3/CH3CN. A continuous 1D columnar
coordination polymer composed of a racemic mixture of left- and
INTRODUCTION
■
Coordination polymers (CPs) and metal−organic frameworks
(MOFs) have attracted considerable attention because of their
potential applications in gas storage,1 selective heterogeneous
catalysis,2 sensing,3 molecular electronics,4 and magnetic
devices.5 The preparation of CPs or MOFs can be controlled
by many factors, including the metal/ligand stoichiometry, as
well as the temperature, concentration, and the type of
counterion used during their preparation process. The metal
ions used for the construction of these materials have also
received considerable attention in relation to their coordination
geometry.6 For example, CPs employing Ag(I) ions have been
widely used because of their variable coordination number and
flexible geometry and properties.7 Numerous multidentate
organic ligands have been designed to vary a range of different
factors, including the number and direction of the coordination
sites, the incorporation of N- or O-donor groups, and the size,
shape, and rigidity of the linker units.8 A variety of multidentate
organic ligands have been used for the construction of CPs and
MOFs,9 and simple bidentate ligands have been prepared
through the formation of connections between metal-coordination
sites and a linker. Linker units play a crucial role in the rational
design of coordination networks and frameworks within specific
structures. For example, aromatic sulfonamides represent good
building blocks for the construction of helical structures10 because
they exist in a synclinal conformation that orientates the aromatic
Received: September 18, 2013
Revised: November 24, 2013
Published: December 3, 2013
© 2013 American Chemical Society
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Article
C24H21N3O2S·0.80AgBF4·0.20CHCl3: C, 48.84; H, 3.59; N, 7.06.
Found: C, 48.54; H, 3.61; N, 6.76.
right-handed helices was formed by the reaction of ligand 1 with
AgBF4 in CHCl3/CH3CN. Layered coordination polymers were
constructed by the complexation of ligand 2 with AgSbF6 in
CHCl3/MeOH. The Ag(I) centers in these polymers possessed
two different types of coordination geometries, with each ion
coordinated to two or four pyridyl groups of the ligand 2. The
pairs of homochiral coordination polymers were associated
through π/π and CH/O interactions to form racemic two-
dimensional (2D) layer structures, and the 2D layer structures
associated to form a three-dimensional (3D) network.
Synthesis of N-Ethyl-N-(4-(4-pyridyl)phenyl)-4-(4-pyridyl)-
benzenesulfonamide·AgBF4 (2a). This material was prepared in
a similar manner to that described above for 1a using AgBF4 and 2 in
CHCl3/CH3CN. Elemental Analysis Calcd. for C24H21N3O2S·
0.75AgBF4·0.25CHCl3: C, 49.25; H, 3.62; N, 7.11. Found: C, 49.17;
H, 3.58; N, 6.82.
Synthesis of N-Ethyl-N-(4-(4-pyridyl)phenyl)-4-(4-pyridyl)-
benzenesulfonamide·AgSbF6 (2b). This material was prepared in
a similar manner to that described above for 1a using AgSbF6 and 2 in
CHCl3/MeOH (1:1 − v/v). Elemental Analysis Calcd. for
C24H21N3O2S·AgSbF6: C, 37.97; H, 2.79; N, 5.54. Found: C, 38.20;
H, 2.84; N, 5.40.
EXPERIMENTAL SECTION
■
Crystallization. Crystals of the complexes 1a, 1b, 2a, and 2b were
obtained from each reaction solution. The slow evaporation of the
solvents afforded diffraction quality crystals.
Synthesis of N-Ethyl-N-(4-(3-pyridyl)phenyl)-4-(3-pyridyl)-
benzenesulfonamide (1). Tetrakis(triphenylphosphine)palladium
(0) (0.23 g, 0.2 mmol) and Cs2CO3 (1.63 g, 5 mmol) were added
to a solution of N-(4-bromophenyl)-N-ethyl-bromobenzenesulfona-
mide (0.42 g, 1 mmol) and 3-pyridineboronic acid (0.59 g, 4.78
mmol) in toluene (7.5 mL) and methanol (2.5 mL), and the resulting
mixture was heated at 100 °C for 6 h. The mixture was cooled to room
temperature and filtered through Celite. The filtrate was then collected
and distilled to dryness under reduced pressure to give the crude
product, which was purified by silica gel column chromatography
(eluent CHCl3/MeOH = 20:1 − v/v) to give 1 in 94% yield as white
Measurement. X-ray data of the crystals were collected on a CCD
diffractometer using graphite monochromated Mo Kα (λ = 0.71073 Å)
radiation. Data collections for the crystals were carried out at low
temperature using liquid nitrogen. The crystal structures were solved
by direct methods SHELXS-97 and refined by full-matrix least-squares
SHELXL-97.11 All of the non-hydrogen atoms were refined
anisotropically, and the hydrogen atoms were included at their
calculated positions. Thermogravimetric analyses of the coordination
polymers were performed on a Rigaku Thermo plus TG8120
apparatus. Powder samples of the complexes were loaded into alumina
pans and heated at a ramp rate of 10 °C min−1 from room temperature
to 500 °C under a N2 atmosphere (20 mL min−1).
1
powder (0.39 g, 0.94 mmol): mp 133−135 °C H NMR (400 MHz,
CDCl3): δ (ppm) 8.86 (dd, J = 16.4, 2.4 Hz, 2H), 8.63 (td, J = 1.6, 4.7,
22.4 Hz, 2H), 7.89 (m, 2H), 7.76 (d, J = 8.8 Hz, 2H), 7.70 (d, J = 8.8 Hz,
2H), 7.57 (d, J = 8.4 Hz, 2H), 7.41 (m, 2H), 7.23 (d, J = 8.4 Hz, 2H), 3.70
(q, J = 7.2 Hz, 2H), 1.16 (t, J = 6.8 Hz, 3H); 13C NMR (125 MHz,
CDCl3): δ (ppm) 149.6 (CH), 148.8 (CH), 148.3 (CH), 148.2 (CH),
142.1 (Cq), 138.6 (Cq), 137.9 (Cq), 137.4 (Cq), 135.5 (Cq), 134.8 (Cq),
134.5 (CH), 134.3 (CH), 129.4 (CH), 128.4 (CH), 127.7 (CH), 123.7
(CH), 123.6 (CH), 45.60 (CH2), 14.02 (CH3); IR (solid state, ATR): ν
(cm−1) 3028 (w), 1600 (m), 1517 (m), 1347 (s), 1163 (s); FAB-MS: m/z
416.1 [M + H]+; Elemental Analysis Calc. for C24H21N3O2S: C, 69.37; H,
5.09; N, 10.11. Found: C, 69.21; H, 4.85; N, 9.94.
RESULTS AND DISCUSSION
■
The bis(pyridyl) ligands containing a sulfonamide (1 and 2)
were prepared by the Suzuki-Miyaura coupling reaction of a
bisbromobenzene sulfonamide 3 with a pyridine boronic acid
(Scheme 1). The crystal data and conformational parameters of
Synthesis of N-Ethyl-N-(4-(4-pyridyl)phenyl)-4-(4-pyridyl)-
benzenesulfonamide (2). Tetrakis(triphenylphosphine)palladium
(0) (0.46 g, 0.4 mmol) and Cs2CO3 (3.26 g, 10 mmol) were added
to a solution of N-(4-bromophenyl)-N-ethyl-bromobenzenesulfona-
mide (1.00 g, 2.39 mmol) and 4-pyridineboronic acid (1.30 g, 10
mmol) in toluene (15 mL) and methanol (5 mL), and the resulting
mixture was heated at 100 °C for 6 h. The mixture was cooled to room
temperature and filtered through Celite. The filtrate was then collected
and distilled to dryness under reduced pressure to give the crude
product, which was purified by silica gel column chromatography
(eluent CHCl3/MeOH = 20:1) to give 2 in 95% yield as white powder
(0.945 g, 2.27 mmol): mp 171−173 °C; 1H NMR (400 MHz,
CDCl3): δ (ppm) 8.69 (dd, J = 6.0, 20.4 Hz, 2H), 7.75 (s, 4H), 7.63
(d, J = 8.4 Hz, 2H), 7.53 (dd, J = 1.6, 4.8 Hz, 2H), 7.50 (dd, J = 1.6,
4.8 Hz, 2H), 7.24 (d, J = 8.8 Hz, 2H), 3.71 (q, J = 7.2 Hz, 2H), 1.15 (t,
J = 7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3): δ (ppm) 150.5 (CH),
150.3 (CH), 147.0 (Cq), 146.3 (Cq), 142.3 (Cq), 139.4 (Cq), 138.7 (Cq),
137.6(Cq), 129.3 (CH), 128.3 (CH), 127.6 (CH), 127.4 (CH), 121.6
(CH), 121.4 (CH), 45.55 (CH2), 13.98 (CH3) ppm; IR (solid state, ATR):
ν (cm−1) 3020 (w), 1595 (m), 1486 (m), 1348 (s), 1172 (s); FAB-MS:
m/z 416.2 [M + H]+; Elemental Analysis Calc. for C24H21N3O2S: C,
69.37; H, 5.09; N, 10.11. Found: C, 69.08; H, 4.95; N, 9.99.
Synthesis of N-Ethyl-N-(4-(3-pyridyl)phenyl)-4-(3-pyridyl)-
benzenesulfonamide·AgOTf (1a). AgOTf was added to a solution
of 1 in CHCl3/CH3CN (1:1 − v/v). After several minutes of stirring,
the desired complex precipitated as a white solid, which was collected
by filtration and dried under vacuum at 80 °C. Elemental Analysis
Calcd. for C24H21N3O2S·CF3O2SAg·0.40CHCl3·0.20CH3CN: C,
42.54; H, 3.04; N, 6.15. Found: C, 42.82; H, 2.90; N, 5.95.
Synthesis of N-Ethyl-N-(4-(3-pyridyl)phenyl)-4-(3-pyridyl)-
benzenesulfonamide·AgBF4 (1b). This material was prepared in
a similar manner to that described above for 1a using AgBF4 and 1 in
CHCl3/CH3CN (1:1 − v/v). Elemental Analysis Calcd. for
Scheme 1. Synthesis of the Bidentate Ligands 1 and 2
1 and 2 are shown in Tables 1 and 2, respectively. The torsion
angles of the sulfonamide moiety [C(Ph)−S−N−C(Ph)] are
81.3(2) and 75.9(2)°, respectively (Table 2), and therefore the
sulfonamide bonds of both of the sulfonamides were synclinal
(Figure 1).
The reaction of equimolar amounts of the sulfonamide
ligands (1 and 2) with Ag(I) salts gave the corresponding
complexes [AgLOTf]n (L = 1 (1a)), [AgL]n·nBF4 (L = 1 (1b)),
[AgLCH3CN]n·nBF4·nCHCl3 (L = 2 (2a)), and [AgL]n·nSbF6
nCH4O (L = 2 (2b)) (Figure 1). Complex 1a was obtained
from the reaction of ligand 1 with AgOTf in a mixture of CH3CN
and CHCl3, whereas complexes 1b and 2a were obtained by the
reaction of ligands 1 and 2 with AgBF4 in a mixture of CH3CN
and CHCl3. Complex 2b was obtained by the reaction of ligand 2
with AgSbF6 in a mixture of CHCl3 and MeOH. The crystals of
the complexes were obtained from each reaction solution directly.
The crystal data and conformational parameters of 1a, 1b, 2a, and
2b are shown in Tables 1 and 2, respectively. The sulfonamide
bonds of 1a and 2b were found to be synclinal, and the torsion
angles of the sulfonamide moiety were 75.5(8) and 62.4(8)°,
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Table 1. Crystallographic Data for Ligands 1 and 2 and Complexes 1a, 1b, 2a, and 2b
1
2
formula
formula weight
crystal system
space group
a (Å)
C24H21N3O2S
415.50
C24H21N3O2S
415.50
monoclinic
P21/c
monoclinic
C2/c
20.743(3)
5.7353(7)
18.342(2)
90
18.845(3)
18.777(3)
12.610(2)
90
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
112.779(1)
90
115.589(2)
90
2011.9(4)
4
4024.6(11)
8
Z
Dcalc (Mg/m3)
1.372
1.371
T (K)
μ (mm−1
120
120
)
0.188
0.188
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
CCDC number
0.0448, 0.0959
0.0691, 0.1068
959267
1b
0.0465, 0.1071
0.0746, 0.1211
959270
1a
2a
2b
formula
C25H21N3O5S2F3Ag
672.44
C24H21N3O2BF4SAg
572.18
C27H25N4O2SBF4Cl3Ag
770.60
C49H42N6O6S2SbF6Ag
1272.56
orthorhombic
Ibam
formula weight
crystal system
space group
a (Å)
triclinic
monoclinic
C2/c
monoclinic
P21/c
P1
̅
11.094(8)
11.531(8)
11.635(8)
87.702(10)
63.717(8)
79.934(9)
1312.8(16)
2
34.543(9)
8.342(2)
15.572(4)
90
21.370(4)
19.497(4)
7.470(1)
90
12.277(4)
22.291(7)
45.968(14)
90
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
92.096(4)
90
91.055(3)
90
90
90
4474(2)
8
3111.9(10)
4
12580(7)
8
Z
Dcalc (Mg/m3)
1.701
1.699
1.645
1.344
T (K)
μ (mm−1
120
120
150
120
)
0.990
1.040
1.029
1.020
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
CCDC number
0.0857, 0.2112
01327, 0.2429
959268
0.0535, 0.0956
0.1074, 0.1143
959269
0.0931, 0.2614
0.1609, 0.3469
959271
0.1116, 0.3032
0.2131, 0.3412
959272
Table 2. Conformational Parameters of the Sulfonamides 1 and 2, and the Complexes 1a, 1b, 2a, and 2b
1
2
torsion angle (deg) C1−N1−S1−C12
torsion angle (deg) C1−N1−S1−C12
81.3(2)
75.9(2)
1a
1b
2a
2b
75.5(8)
92.9(6)
152.0(5)
62.4(8)
respectively. In contrast, the sulfonamide bonds of 1b and 2a were
determined to be anticlinal and antiperiplanar, respectively, and
the torsion angles of the sulfonamide moieties in these complexes
were 92.9(6) and 152.0(5)°, respectively.
ligand 1 was connected by Ag(I) ions. The Ag(I) centers had a
T-shaped coordination geometry, with each of the ions
coordinated to two pyridyl groups of ligand 1 as well as a
trifluoromethanesulfonate anion (Figure 2a). Both enantiomers
of the 1D chain associated to form a racemic 1D chain through
a Ag/Ag interaction (Figure 2b). The Ag···Ag distance of
3.38(1) Å is longer than those of other complexes12 but still
The crystals of complex 1a crystallized in a triclinic system
with space group P1. The structure of complex 1a was shown to
̅
be an enantiopure infinite 1D coordination polymer, where
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Figure 1. Thermal ellipsoid models of the crystal structures of the sulfonamide ligands 1 and 2, and those of the corresponding Ag(I) complexes 1a,
1b, 2a, and 2b. The ellipsoids of all non-hydrogen atoms are drawn at the 50% probability level while isotropic hydrogen atoms are represented by
spheres of arbitrary size. The counteranions and solvent molecules are omitted for clarity.
The crystals of complex 1b crystallized in a monoclinic
system with space group C2/c. The structure of complex 1b
was shown to be a 1D columnar coordination polymer, where
the ligand 1 molecules were connected by Ag(I) ions. The
columnar structure was composed of a racemic mixture of
left- and right-handed helical chain. Both of the enantiomers of
the sulfonamide ligands 1 coordinated to the same Ag(I) ion
centers to form a racemic complex. The Ag(I) centers
possessed a four coordinate geometry (Figure 3a). The inner
space of the columnar structure contained BF4 anions, which
were connected to the ligand through CH/F interactions with a
C···F distance of 3.41(1) Å (Figure 3b). The racemic columns
were further associated through Ag/F interactions between the
fluorine atoms of the tetrafluoroborate and the Ag(I) ions of
the neighboring columns (with a Ag···F distance of 3.152(6) Å,
Figure 3c), as well as intermolecular multiple CH/O interactions
(with a C···O distance in the range of 3.196(9)−3.323(9) Å,
Figure 3c) to form a 3D network.
The crystals of complex 2a crystallized in a monoclinic
system with space group P21/c. The structure of complex 2a
was shown to be an infinite 1D coordination polymer, where
the ligand 2 molecules were connected by Ag(I) ions in an
antiperiplanar conformation. The Ag(I) centers had a T-shaped
coordination geometry, with each ion coordinated to the two
pyridyl groups of ligand 1 as well as an acetonitrile molecule. In
this coordination polymer, both of the enantiomers of ligand 2
constructed a 1D coordination polymer (Figure 4a). The racemic
1D polymers extended along the b axis through CH/O inter-
actions to form a 2D layer with a C···O distance of 3.43(1) Å
(Figure 4b). Furthermore, the 2D layers stacked to form a 3D
network through intermolecular CH/O interactions with C···O
distances of 3.32(1) and 3.40(1) Å (Figure 4c).
The crystals of complex 2b crystallized in an orthorhombic
system with space group Ibam. The structure of complex 2b
was shown to be a homochiral infinite coordination polymer,
where the ligand 2 molecules were connected by Ag(I) ions
with two coordination geometries. One of the Ag(I) centers
had a tetrahedral coordination geometry, where the ions were
coordinated to the four pyridyl groups of two ligand 2
molecules. The other coordination geometry had a linear
coordination geometry, where the ions were coordinated to the
two pyridyl groups of a ligand 2 molecule (Figure 5a). An
interesting feature of the structure of 2b was that pairs of
homochiral coordination polymers were associated through
Figure 2. Crystal structure of the Ag(I) complexes of 1a as ball and
stick models. (a) Homochiral 1D chain. (b) The pair of enantiomeric
1D chains. (c) 3D network structure accomplished though CH/O and
Ag/O interactions. The different enantiomeric chains are shown in
cyan and magenta. The red-dotted lines represent the Ag/O
interactions.
within the summed van der Waals radii of two Ag atoms
(3.44 Å),12e and this indicates the Ag···Ag interaction in 1a is
very weak. The racemic 1D chains extended along the b axis
through hydrogen-bonding interactions to form 2D layers with
a C···O distance of 3.41(2) Å (Figure 2c). Furthermore, the 2D
layers stacked to form a three-dimensional (3D) network
through intermolecular Ag/O interactions between Ag(I) ions
and the oxygen atom of the sulfonamides in 1a with a Ag···O
distance of 2.901(9) Å (Figure 2c).
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Figure 4. Crystal structures of the Ag(I) complexes of 2a as ball and
stick models. (a) Racemic 1D chain with the chloroform molecules
omitted for clarity. (b) 2D layer structure accomplished through CH/O
interactions. (c) 3D network structure accomplished through CH/O
interactions. The different enantiomeric chains are shown in cyan and
magenta. The red-dotted lines represent the CH/O interactions.
range of 50−260 °C, corresponding to the loss of free water
molecules per formula unit (exptl. 5.5%; calcd. 5.5%). The
TGA curve of complex 2b also contained only one distinct
weight loss event, which corresponded to the loss of one lattice
methanol molecule (exptl. 14.8%; calcd, 15.0%) in the range of
50−100 °C. This complex then decomposed at 300 °C.
Taken together, these results show that ligands 1 and 2,
which can be considered as flexible building blocks with the
sulfonamide moiety, can combine as Ag(I) complexes to form
coordination polymers (i.e., 1a, 1b, 2a, and 2b) through self-
assembly. In these complexes, the ligands have flexibility arising
from the twisting about the C−S−N−C units, and the Ag(I)
centers have several different stereochemistries. A comparison
of some of the structural features is given in Table 3. The
reaction of the ligand 1 with AgOTf gave the 1D straight chain
complex 1a, whereas its reaction with AgBF4 gave the 1D
columnar complex 1b. The major difference between
complexes 1a and 1b was the Ag(I) coordination geometry.
In general, it has been reported that out of about 3300 solid-
state structure of Ag(I) complexes, 24% are two-coordinate,
23% are three-coordinate, and 44% are four-coordinate.7a When
a strongly coordinating TfO− anion is used,7b the anions
coordinate to Ag(I) ions through one of the oxygen atoms, and
the Ag(I) center of 1a forms a three-coordinated T-shaped
geometry. In contrast, the BF4− anion is a weaker coordinating
anion, and the Ag(I) atoms of 1b, which are all connected to
four ligands, can then also be described as adopting a four-
coordinated square planar geometry.7h,j The sulfonamide bonds
of 1a and 1b were synclinal and anticlinal, and the torsion angles
of the C−S−N−C bonds were 75.5(8) and 92.9(6) °, respectively
(Table 2). The reaction of the ligand 2 with AgBF4 gave the 1D
straight chain complex 2a, whereas its reaction with AgSbF6 gave
the 2D layer complex 2b. The sulfonamide bonds of 2a and 2b
Figure 3. Crystal structure of the Ag(I) complexes of 1b as ball and
stick models. (a) Racemic helical 1D chain, with the counteranions
omitted for clarity. (b) Columnar structure containing BF4 anions. (c)
3D network structure accomplished through CH/O interactions. The
different enantiomeric chains are shown in cyan and magenta.
π/π and CH/O interactions to form a 2D layer structure, which
resulted in the crystal possessing no optical activity (Figure 5b).
Furthermore, the 2D layer structures associated to form a 3D
network (Figure 5c). The SbF6 anions occupied the space
between the 2D columnar structures.
To evaluate the thermal stability properties of complexes 1a,
1b, 2a, and 2b, their thermal behaviors were investigated under
a nitrogen atmosphere by thermogravimetric analysis (TGA)
(Figure 6). The TGA curves of infinite 1D coordination
polymers 1a and 2a showed that their frameworks were stable
up to 258 and 250 °C, respectively. Beyond these temperatures,
the framework began to decompose. The TGA curve for
complex 1b contained one distinct weight loss event in the
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Figure 6. Thermogravimetric analysis curves for complexes 1a
(green), 1b (blue), 2a (cyan), and 2b (red).
CONCLUSION
■
We have demonstrated that bidentate ligands containing tertiary
sulfonamides represent a versatile building block for the
construction of coordination polymers. The sulfonamides used in
the current study were essentially synclinal in terms of their
conformation, except when the counteranion was replaced by BF4
and the sulfonamides then existed in an anticlinal or antiperiplanar
conformation. The mixing of the ligands 1 or 2 with different Ag(I)
salts yields the corresponding complexes [AgLOTf]n (L = 1 (1a)),
[AgL]n·nBF4 (L = 1 (1b)), [AgLCH3CN]n·nBF4·nCHCl3 (L = 2
(2a)), and [AgL]n·nSbF6·nCH4O (L = 2 (2b)). In the crystals
of complexes 1a and 2a, infinite 1D straight chains with a
T-shaped coordination geometry about the Ag(I) centers were
formed by the reaction of ligands 1 or 2 with Ag(I) salts
in CH3CN/CHCl3. A continuous 1D columnar coordination
polymer containing a racemic mixture of left- and right-handed
helices was formed from the crystals of complex 1b.
Furthermore, the formation of a layered coordination polymer
consisting of a racemic mixture of left- and right-handed
polymers was observed from the crystals of complex 2b. The
self-assembly of sulfonamide ligands by metal coordination is
a suitable approach not only for the development of helical
metal−organic frameworks but also for the organization of
ordered arrangements into interesting 2D/3D networks. The
construction of optically pure left- or right-handed 1D helical
polymers via the introduction of chiral functional groups on
the nitrogen atom of the sulfonamide ligand is currently under
investigation in our laboratory.
Figure 5. Crystal structures of the Ag(I) complexes of 2b. (a)
Homochiral infinite coordination polymer shown as a ball and stick
model with the counteranions and solvent molecules omitted for clarity.
(b) 2D layer structure as a space-filling model with the counteranions
and solvent molecules omitted for clarity. (c) 3D network structure as a
ball and stick model with the solvent molecules omitted for clarity. The
different enantiomeric chains are shown in cyan and magenta.
were antiperiplanar and synclinal, and the torsion angles of their
C−S−N−C bonds were 152.0(5) and 62.4(8)°, respectively
(Table 2). In the 1D straight chain of 2a, the Ag(I) had a
T-shaped coordination geometry. The two pyridyl groups of the
ligand as well as an acetonitrile molecule were coordinated to the
Ag(I) center. In the 2D layer structure of 2b, the noncoordinating
SbF6− anions not only acted as the counteranions to balance the
charge but also had a spatial templating effect in building up the
network.7c Moreover, there were two different Ag(I) centers in
complex 2b. One of these centers had an essentially linear
N−Ag−N bond angle (N−Ag−N = 178.8(5)°) and was two-
coordinate, whereas the other center had a tetrahedral geometry
(N−Ag−N = 100.7(2), 107.7(8), and 120.8(14)°).
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectroscopic data and all crystallographic
data and crystallographic information files (CIF). This
material is available free of charge via the Internet at http://
pubs.acs.org.
Table 3. Comparison of Some of the Structural Features of Complexes 1a, 1b, 2a, and 2b
1a
1b
2a
2b
shape of CPs
1D-straight
synclinal
T-shape
OTf
1D-columnar
anticlinal
1D-straight
antiperiplanar
T-shape
2D-layer
conformation of ligand
coordination geometry (Ag(I))
counteranion
synclinal
square planar
BF4
tetrahedral, straight
BF4
SbF6
N(Py)−Ag−N(Py)/°
N(Py)−Ag−N(CN)/°
N(Py)−Ag−O(OTf)/°
162.5(3)
143.8(2), 174.2(2)
173.2(3)
100.7(2), 107.7(8), 120.8(14), 178.8(5)
90.5(3), 94.5(3)
91.5(4), 101.9(4)
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Article
M.; Yaghi, O. M. Science 2002, 295, 469−472. (e) Seo, J. S.; Whang,
D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404,
982−986. (f) Nakai, H.; Morita, H.; Tomasello, P.; Nakatsuji, H. J.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: katagirik@kph.bunri-u.ac.jp (K.K.).
*E-mail: isao.azumaya@phar.toho-u.ac.jp (I.A.).
Notes
■
́
Phys. Chem. A 1998, 102, 2033−2043. (g) Corma, A.; Fornes, V.;
García, H.; Miranda, M. A.; Sabater, M. J. J. Am. Chem. Soc. 1994, 116,
9767−9768.
(5) (a) Coronado, E.; Espallargas, G. M. Chem. Soc. Rev. 2013, 42,
1525−1539. (b) Sibille, R.; Mazet, T.; Malaman, B.; Francois, M.
Chem.Eur. J. 2012, 18, 12970−12973. (c) Bureekaew, S.; Horike, S.;
Higuchi, M.; Mizuno, M.; Kawamura, T.; Tanaka, D.; Yanai, N.;
Kitagawa, S. Nat. Mat. 2009, 8, 831−836. (d) Kurmoo, M. Chem. Soc.
Rev. 2009, 38, 1353−1379. (e) Wang, Y.-Q.; Wang, K.; Sun, Q.; Tian,
H.; Gao, E.-Q.; Song, Y. Dalton. Trans. 2009, 9854−9859. (f) Kutasi,
A. M.; Turner, D. R.; Jensen, P.; Moubaraki, B.; Batten, S. R.; Murray,
K. S. CrystEngComm 2009, 11, 2089−2095. (g) Meng, W.-L.; Liu, G.-
X.; Okamura, T.; Kawaguchi, H.; Zhang, Z.-H.; Sun, W. -Y.; Ueyama,
N. Cryst. Growth. Des. 2006, 6, 2092−2102.
(6) (a) Bo, Q.-B.; Wang, H.-Y.; Wang, D.-Q. New. J. Chem. 2013, 37,
380−390. (b) Zhang, W. H.; Dong, Z.; Wang, Y. Y.; Hou, L.; Jin, J. C.;
Huang, W. H.; Shi, Q. Z. Dalton. Trans. 2011, 40, 2509−2521. (c) Ma,
L.; Lin, W. J. Am. Chem. Soc. 2008, 130, 13834−13835. (d) Suslick, K.
S.; Bhyrappa, P.; Chou, J.-H.; Kosal, M. E.; Nakagaki, S.; Smithenry, D.
W.; Wilson, S. R. Acc. Chem. Res. 2005, 38, 283−291. (e) Kitaura, R.;
Onoyama, G.; Sakamoto, H.; Matsuda, R.; Noro, S.; Kitagawa, S.
Angew. Chem., Int. Ed. 2004, 43, 2684−2687. (f) Chen, B.; Fronczek,
F. R.; Maverick, A. W. Inorg. Chem. 2004, 43, 8209−8211.
(g) Smithenry, D. W.; Wilson, S. R.; Suslick, K. S. Inorg. Chem.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported in part by Senryaku, 2008−2012 from
the Ministry of Education, Culture, Sports, Science and
Technology of Japan.
REFERENCES
■
(1) (a) Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.;
DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P.
C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T. J. Am. Chem. Soc. 2013, 135,
10294−10297. (b) Park, J.; Wang, Z. U.; Sun, L.-B.; Chen, Y.-P.;
Zhou, H.-C. J. Am. Chem. Soc. 2012, 134, 20110−20116. (c) Bae, Y.
-S.; Lee, C. Y.; Kim, K. C.; Farha, O. K.; Nickias, P.; Hupp, J. T.;
Nguyen, S. T.; Snurr, R. Q. Angew. Chem., Int. Ed. 2012, 51, 1857−
1860. (d) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W. Chem. Rev.
2012, 112, 782−835. (e) Sumida, K.; Rogow, D. L.; Mason, J. A.;
McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R.
Chem. Rev. 2012, 112, 724−781. (f) Getman, R. B.; Bae, Y.-S.; Wilmer,
C. E.; Snurr, R. Q. Chem. Rev. 2012, 112, 703−723. (g) Guo, Z.; Wu,
H.; Srinivas, G.; Zhou, Y.; Xiang, S.; Chen, Z.; Yang, Y.; Zhou, W.;
O’Keeffe, M.; Chen, B. Angew. Chem., Int. Ed. 2011, 50, 3178−3181.
2003, 42, 7719−7721. (h) Nattinen, K. I.; Linnanto, J.; Rissanen, K.
̈
Eur. J. Inorg. Chem. 2003, 4078−4086. (i) Stang, P. J.; Olenyuk, B. Acc.
Chem. Res. 1997, 30, 502−518.
̂
(h) Murray, L. J.; Dinca, M.; Long, J. R. Chem. Soc. Rev. 2009, 38,
1294−1314. (i) Li, J.-R.; Kuppler, R. J.; Zhou, H. -C. Chem. Soc. Rev.
2009, 38, 1477−1504. (j) Rowsell, J. L. C.; Yaghi, O. M. Angew. Chem.,
Int. Ed. 2005, 44, 4670−4679. (k) Noro, S.-i.; Kitagawa, S.; Kondo, M.;
Seki, K. Angew. Chem., Int. Ed. 2000, 39, 2082−2084. (l) Kondo, M.;
Yoshitomi, T.; Seki, K.; Matsuzaka, H.; Kitagawa, S. Angew. Chem., Int.
Ed. 1997, 36, 1725−1727.
(7) (a) Haj, M. A.; Aakeroy, C. B.; Desper, J. New J. Chem. 2013, 37,
̈
204−211. (b) Hollis, C. A.; Batten, S. R.; Sumby, C. J. Cryst. Growth
Des. 2013, 13, 2350−2361. (c) Wu, J.-Y.; Chao, T.-C.; Zhong, M.-S.
́
Cryst. Growth Des. 2013, 13, 2953−2964. (d) Beziau, A.; Baudron, S.
A.; Hosseini, M. W. Dalton Trans. 2012, 41, 7227−7234. (e) Park, S.;
Lindoy, L. F.; Lee, S. S. Cryst. Growth Des. 2012, 12, 1320−1329.
(f) Chainok, K.; Neville, S. M.; Forsyth, C. M.; Gee, W. J.; Murray, K.
S.; Batten, S. R. CrystEngComm 2012, 14, 3717−3726. (g) Bloch, W.
M.; Sumby, C. J. Chem. Commun. 2012, 48, 2534−2536. (h) Leong,
W. L.; Vittal, J. J. Chem. Rev. 2011, 111, 688−764. (i) Steel, P. J.;
Fitchett, C. M. Coord. Chem. Rev. 2008, 252, 990−1006. (j) Young, A.
G.; Hanton, L. R. Coord. Chem. Rev. 2008, 252, 1346−1386.
(k) Burchell, T. J.; Eisler, D. J.; Puddephatt, R. J. Cryst. Growth Des.
2006, 6, 974−982. (l) Chen, C.-L.; Kang, B.-S.; Su, C.-Y. Aust. J. Chem.
2006, 59, 3−18. (m) Sarkar, M.; Biradha, K. CrystEngComm 2004, 6,
310−314. (n) Brammer, L.; Rodger, C. S.; Blake, A. J.; Brooks, N. R.;
Champness, N. R.; Cunningham, J. W.; Hubberstey, P.; Teat, S. J.;
(2) (a) Genna, D. T.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S.
J. Am. Chem. Soc. 2013, 135, 10586−10589. (b) Yoon, M.;
Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112, 1196−1231.
(c) Tanabe, K. K.; Cohen, S. M. Angew. Chem., Int. Ed. 2009, 48,
7424−7427. (d) Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.;
Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450−1459.
(e) Hasegawa, S.; Horike, S.; Matsuda, R.; Furukawa, S.; Mochizuki,
K.; Kinoshita, Y.; Kitagawa, S. J. Am. Chem. Soc. 2007, 129, 2607−
2614. (f) Cho, S.-H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht-
Schmitt, T. E. Chem. Commun. 2006, 2563−2565. (g) Wu, C.-D.; Hu,
A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940−8941.
(h) Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, A. G.;
Williams, I. D. Science 1999, 283, 1148−1150. (i) Davis, M. E. Acc.
Chem. Res. 1993, 26, 111−115.
Wilson, C.; Schroder, M. J. Chem. Soc., Dalton Trans. 2002, 31, 4134−
̈
4142. (o) Brooks, N. R.; Blake, A. J.; Champness, N. R.; Cunningham,
J. W.; Hubberstey, P.; Teat, S. J.; Wilson, C.; Schroder, M. J. Chem.
̈
(3) (a) Jia, J.; Xu, F.; Long, Z.; Hou, X.; Sepaniak, M. J. Chem.
Commun. 2013, 49, 4670−4672. (b) Zhu, X.; Zheng, H.; Wei, X.; Lin,
Z.; Guo, L.; Qiu, B.; Chen, G. Chem. Commun. 2013, 49, 1276−1278.
(c) Ferrando-Soria, J.; Serra-Crespo, P.; de Lange, M.; Gascon, J.;
Soc., Dalton Trans. 2001, 30, 2530−2538. (p) Blake, A. J.; Brooks, N.
R.; Champness, N. R.; Cunningham, J. W.; Hubberstey, P.; Schroder,
̈
M. CrystEngComm 2000, 2, 41−45. (q) Khlobystov, A. N.; Blake, A. J.;
Champness, N. R.; Lemenovskii, D. A.; Majouga, A. G.; Zyk, N. V.;
́ ́
Kapteijn, F.; Julve, M.; Cano, J.; Lloret, F.; Pasan, J.; Ruiz-Perez, C.;
Schroder, M. Coord. Chem. Rev. 2001, 222, 155−192.
̈
Journaux, Y.; Pardo, E. J. Am. Chem. Soc. 2012, 134, 15301−15304.
(d) Feng, P. L.; Leong, K.; Allendorf, M. D. Dalton. Trans. 2012, 41,
8869−8877. (e) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.;
Duyne, R. P. V.; Hupp, J. H. Chem. Rev. 2012, 112, 1105−1125.
(f) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem.
Soc. Rev. 2009, 38, 1330−1352. (g) Bae, Y. -S.; Farha, O. K.;
Spokoyny, A. M.; Mirkin, C. A.; Hupp, J. T.; Snurr, R. Q. Chem.
Commun. 2008, 4135−4137.
(8) (a) Cook, T. R.; Zheng, Y.-R.; Stang, P. J. Chem. Rev. 2013, 113,
734−777. (b) Allen, C. A.; Boissonnault, J. A.; Cirera, J.; Gulland, R.;
Paesani, F.; Cohen, S. M. Chem. Commun. 2013, 49, 3200−3202.
(c) Meng, L.; Cheng, Q.; Kim, C.; Gao, W.-Y.; Wojtas, L.; Chen, Y.-S.;
Zaworotko, M. J.; Zhang, X. P.; Ma, S. Angew. Chem., Int. Ed. 2012, 51,
10082−10085. (d) Li, S.-L.; Lan, Y.-Q.; Sakurai, H.; Xu, Q. Chem.
Eur. J. 2012, 18, 16302−16309. (e) Zhao, D.; Timmons, D. J.; Yuan,
D.; Zhou, H. -C. Acc. Chem. Res. 2011, 44, 123−133. (f) Adarsh, N. N.;
Kumar, D. K.; Dastidar, P. CrystEngComm 2009, 11, 796−802.
(g) Halder, P.; Zangrando, E.; Paine, T. K. Dalton. Trans. 2009, 5386−
5394. (h) Li, P.; Lou, J.; Zhou, Y.; Liu, X.; Chen, Z.; Weng, L. Dalton.
Trans. 2009, 4847−4849. (i) Kumar, D. K.; Das, A.; Dastidar, P. Cryst.
Growth. Des. 2007, 7, 205−207. (j) Kim, J.; Chen, B.; Reineke, T. M.;
(4) (a) Zeng, Y.; Fu, Z.; Chen, H.; Liu, C.; Liao, S.; Dai, J. Chem.
Commun. 2012, 48, 8114−8116. (b) Vitillo, J. G.; Groppo, E.; Bordiga,
S.; Chavan, S.; Ricchiardi, G.; Zecchina, A. Inorg. Chem. 2009, 48,
5439−5448. (c) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.;
Kim, J.; O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127−1129.
(d) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe,
205
dx.doi.org/10.1021/cg4013944 | Cryst. Growth Des. 2014, 14, 199−206

Crystal Growth & Design
Article
Li, H.; Eddaoudi, M.; Moler, D. B.; O’Keeffe, M.; Yaghi, O. M. J. Am.
Chem. Soc. 2001, 123, 8239−8247.
(9) (a) Keene, T. D.; Rankine, D.; Evans, J. D.; Southon, P. D.;
Kepert, C. J.; Aitken, J. B.; Sumby, C. J.; Doonan, C. J. Dalton. Trans.
2013, 42, 7871−7879. (b) Fang, Q.-R.; Yuan, D.-Q.; Sculley, J.; Lu,
W.-G.; Zhou, H.-C. Chem. Commun. 2012, 48, 254−256. (c) Rocca, J.
D.; Liu, D.; Lin, W. Acc. Chem. Res. 2011, 44, 957−968. (d) Ma, L.;
Mihalcik, D. J.; Lin, W. J. Am. Chem. Soc. 2009, 131, 4610−4612.
(10) (a) Iida, H.; Tang, Z.; Yashima, E. J. Polym. Sci., Part A: Polym.
Chem. 2013, 51, 2869−2879. (b) Ramesh, V. V. E.; Kale, S. S.;
Kotmale, A. S.; Gawade, R. L.; Puranik, V. G.; Rajamohanan, P. R.;
Sanjayan, G. J. Org. Lett. 2013, 15, 1504−1507. (c) Katagiri, K.; Ikeda,
T.; Tominaga, M.; Masu, H.; Azumaya, I. Cryst. Growth. Des. 2010, 10,
2291−2297. (d) Azumaya, I.; Kato, T.; Okamoto, I.; Yamasaki, R.;
Tanatani, A.; Yamaguchi, K.; Kagechika, H.; Takayanagi, H. Org. Lett.
2003, 5, 3939−3942.
(11) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112−122.
(12) (a) Carranza, M. P.; Manzano, B. P.; Jalon, F. A.; Rodríguez, A.
́
M.; Santos, L.; Moreno, M. New. J. Chem. 2013, 37, 3183−3194.
(b) Xiao, S. L.; Li, G. Y.; Qin, L.; Cui, G. H. Transition Met. Chem.
2013, 38, 779−785. (c) Song, R.-F. S.; Xie, Y.-B.; Li, J.-R.; Bu, X.-H.
Dalton Trans. 2003, 4742−4748. (d) Singh, K.; Long, J. R.;
Stavropoulos, P. J. Am. Chem. Soc. 1997, 119, 2942−2943.
(e) Bondi, A. J. Phys. Chem. 1964, 68, 441−451.
206
dx.doi.org/10.1021/cg4013944 | Cryst. Growth Des. 2014, 14, 199−206