Coordination Polymers and Networks Constructed from Bidentate

Apr 20, 2010 - (k) Fujita , M.; Kwon , Y. J.; Washizu , S.; Ogura , K. J. Am. Chem. Soc. 1994, 116 ..... (e) Wu , C.-D.; Hu , A.; Zhang , L.; Lin , W...
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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 onedimensional (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 3 3 3 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 3 3 3 Ag, Ag 3 3 3 O, and C-H 3 3 3 O interactions.

Introduction 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 organic 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 molecular assemblies and have been extensively used to assemble organic molecular building blocks into well-defined crystalline 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 aromatic bis-phenyl and macrocyclic derivatives with sulfonamide moieties.13 The crystals of these pseudopolymorphs were found to exhibit diverse structures through noncovalent interactions.13 These results showed that aromatic sulfonamides

represent valuable building blocks for the creation of solidstate 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 of bidentate ligands (1-4, Scheme 1) 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 3 3 3 Ag, Ag 3 3 3 O, and C-H 3 3 3 O interactions. Experimental Section

*Corresponding author. Tel: 81-87-894-5111 ex. 6308. Fax: 81-87-8940181. E-mail: [email protected].

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 mL  10) and brine (200 mL) and dried over Na2SO4. After evaporation, the crude product was purified

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Crystal Growth & Design, Vol. 10, No. 5, 2010 Scheme 1. Syntheses of Bidentate Ligands (1-4)

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 Hz, 1H), 7.23 (d, J=8.8 Hz, 1H), and 6.87 (t, J=6.4 Hz, 1H) ppm; 13C 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 [M þ 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. N-(3-Pyridyl)-3-pyridylsulfonamide (2). 3-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 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; 1 H 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. N-Ethyl-N-(2-pyridyl)-3-pyridylsulfonamide (3). 2-Ethylaminopyridine (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 dichloromethane (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 mL  10) and brine (100 mL) and dried over Na2SO4. After evaporation, the crude product 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) ppm; FAB-MS m/z 264.2 [MþH]þ; HRMS: m/z calcd for C12H14N3O2S: 264.0807. Found 264.0847; elemental analysis calc. for C12H13N3O2S: 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-Ethylaminopyridine (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 dichloromethane (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 mL  10) and brine (100 mL) and dried over Na2SO4. After evaporation, the crude product was purified by silica gel column chromatography (eluent

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 C12H14N3O2S: 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 3 AgOTf (1a). AgOTf was 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. 2N-(3-Pyridyl)-3-pyridylsulfonamide 3 AgOTf (2a, 2b). This was prepared similarly from AgOTf and 2. N-Ethyl-N-(2-pyridyl)-3-pyridylsulfonamide 3 AgOTf (3a). This was prepared similarly from AgOTf and 3. N-Ethyl-N-(3-pyridyl)-3-pyridylsulfonamide 3 AgOTf (4a). This was prepared similarly from AgOTf and 4. 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 fullmatrix least-squares SHELXL-97.14 All non-hydrogen atoms were refined anisotropically and hydrogen atoms were included as their calculated positions.

Results and Discussion Bis(pyridyl) ligands containing sulfonamides (1 and 2) were prepared by the reaction of sulfonyl chloride and amino pyridine. 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] 3 2H2O (L=2 (2a)), and [AgL(OTf)]n 3 nCHCl3 (L = 2 (2b)). The crystals of complexes 1a, 2a, and 2b were isolated as analytically pure, air-stable, white solids that are slightly soluble in organic solvents such as chloroform, dichloromethane, tetrahydrofuran, and methanol. Crystal data and conformational parameters of 1a, 2a, and 2b are shown in Tables 1 and 2, respectively. The sulfonamide bonds of 1a, 2a, and 2b are synclinal (Figure 2), and the torsion angles of the sulfonamide moiety [C(Py)-SN-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. 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 between the pyridyl nitrogen atom and the nitrogen atom of the sulfonamide in complex 1a (the distances of N1 3 3 3 N6 and N3 3 3 3 N4 are 2.906(7) and 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 3 3 3 O distance is 2.901(5) A˚). Furthermore, the 1D chain form a 3D network by intermolecular multiple C-H 3 3 3 O interactions

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Table 1. Crystallographic Data for Sulfonamide 1-4 and Complexes 1a-4a formula formula weight space group a (A˚) b (A˚) c (A˚) R (°) β (°) γ (°) T (K) V (A˚3) Z Dcalc (Mg/m3) μ (mm-1) R1, wR2 [I >2σ(I )] R1, wR2 (all data) CCDC number

formula formula weight space group a (A˚) b (A˚) c (A˚) R (°) β (°) γ (°) T (K) V (A˚3) Z Dcalc (Mg/m3) μ (mm-1) R1, wR2 [I >2σ(I )] R1, wR2 (all data) CCDC number a

1

2

3

4

C10H9N3O2S 235.26 P1 5.853(1) 8.893(2) 10.734(2) 89.484(2) 84.630(2) 71.987(2) 150 528.9(2) 2 1.477 0.294 0.0384, 0.1082 0.0418, 0.1116 759730

C10H9N3O2S 235.26 P1 6.134 (2) 7.475(2) 11.245(3) 89.835(3) 84.335(3) 84.964(3) 150 511.1(2) 2 1.529 0.304 0.0369, 0.0888 0.0462, 0.0948 759732

;a

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 0.256 0.0347, 0.0918 0.0384, 0.0936 759735

1a

2a

2b

3a

4a

C25H26N6O8S3F3Ag 799.57 P1 8.167(2) 13.281(3) 15.470(4) 93.653(3) 104.099(3) 92.475(3) 150 1621.1(7) 2 1.638 0.887 0.0463, 0.1245 0.0636, 0.1335 759733

C22H22N6O12S4F6Ag2 1020.44 P1 9.286(2) 9.546(1) 10.359(1) 112.859(2) 100.525(2) 95.132(2) 120 818.7(3) 1 2.070 1.555 0.0317, 0.0441 0.0406, 0.0457 768083

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 1.634 0.0412, 0.0782 0.0515, 0.0818 768084

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 1.421 0.0317, 0.0731 0.0485, 0.0790 759734

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 1.429 0.0284, 0.0710 0.0334, 0.0740 759736

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 sulfonamide ligands 1, 2, and 4. Ellipsoids of all non-hydrogen atoms are drawn at the 50% probability.

torsion angle (deg) C1-N1-S1-C6

1

2

66.6(2)

71.2(2)

a

1a

2a

3

4 86.0(2)

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) a Two conformers of ligands are included in the asymmetric unit of the crystal (see Figure 2).

(the C 3 3 3 O distance ranged from 3.202(9) to 3.415(9) A˚) between pyridyl protons and the oxygen atoms of sulfonamides 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 trifluoromethanesulfonate and a water molecule in the unit cell. The

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 molecules (the distances of N1-H1 3 3 3 O6, O6-H6A 3 3 3 O5, O6-H6A 3 3 3 O1, and O6-H6B 3 3 3 O5 are 2.777(3), 3.036(4), 2.977(4), and 2.815(4) A˚, respectively), to give infinite 2D sheets (Figure 4b). Furthermore, the 2D sheets form a 3D network by intermolecular Ag 3 3 3 O interactions (the Ag 3 3 3 O is 2.804(4) A˚, Figure 4c). The crystal of complex 2b crystallized in a monoclinic system, space group P21, and included two molecules 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

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Figure 2. Thermal ellipsoid models of the crystal structures of the silver(I) complexes: [Ag(1)2(OTf)] 3 THF (1a), [Ag2(μ-2)2(OTf)2] 3 2H2O (2a), [Ag(2)(OTf)] (2b), [Ag(3)(OTf)] (3a), and [Ag(4)]þOTf- (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 structure via Ag 3 3 3 O interactions. H-bonds are indicated by black dash lines and Ag 3 3 3 O interactions are indicated by red dash lines.

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 3 3 3 O interactions. (b) 3D network structure via C-H 3 3 3 O interactions. Solvent molecules (THF) are omitted for clarity. H-bonds are indicated by black dash lines, and Ag 3 3 3 O interactions and C-H 3 3 3 O interactions are indicated by red dash lines.

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 3 3 3 O is 2.318(3) A˚) to form 2D layers (Figure 5b). Furthermore, the 2D layers stack to form a 3D network by intermolecular Ag 3 3 3 O interactions (the Ag 3 3 3 O distance is 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.

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)-SN-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, tetrahydrofuran, and methanol. Crystal data and conformational parameters 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

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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 3 3 3 O interactions. Solvent molecules (CHCl3) are omitted for clarity, H-bonds are indicated by black dash lines and Ag 3 3 3 O interactions are indicated by red dash lines.

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 homochiral chains are further associated through weak Ag 3 3 3 O interaction (the Ag 3 3 3 O distance is 2.723(2) A˚) and intermolecular C-H 3 3 3 O interactions (the C 3 3 3 O distance is 3.181(3) A˚) between pyridyl protons and the oxygen atoms of coordinated trifluoromethanesulfonate anion along the c axis to form racemic 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 C-H 3 3 3 O interactions (the C 3 3 3 O distance ranged from 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 system, space group P21/c, and included four molecules of ligand 4 and four molecules of AgOTf in the unit cell. The structure

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Figure 6. Crystal structure of complex 3a as a ball and stick model. (a) Homochiral 1D chain. (b) 2D layered structure via intermolecular multiple Ag 3 3 3 O and C-H 3 3 3 O interactions between 1D chains. (c) 3D network structure via C-H 3 3 3 O interactions. The enantiomeric chains are shown in cyan and magenta, respectively.

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 3 3 3 Ag bonding (the Ag 3 3 3 Ag 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 3D network by intermolecular C-H 3 3 3 O interactions (the C 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 (Figure 7c). The counteranions (TfO-) are also coordinated to the silver(I) centers (the distances of Ag 3 3 3 O are 2.799(2), 3.138(3) and 2.909(3) A˚), and they form a bridge between the silver ions. The fragment that determines the pitch of the helix is composed of two atoms of silver(I) ions and two molecules of ligand 4, where the distance between silver(I) atoms is 11.132(1) A˚.

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complexes, 2D sheets and 3D network structures were formed via Ag 3 3 3 Ag, Ag 3 3 3 O, and C-H 3 3 3 O interactions. The selfassembly of ligands with the sulfonamide moiety via metalcoordination is a suitable approach not only for the development 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 sulfonamide ligand is currently under investigation. Supporting Information Available: 1H and 13C NMR spectroscopic data (PDF) and crystallographic analysis data are available free of charge via the Internet at http://pubs.acs.org.

References

Figure 7. Crystal structure of complex 4a as a ball and stick model. (a) Homochiral helical 1D polymer. (b) 2D layered structure via Ag 3 3 3 Ag bondings between 1D polymers. (c) 3D network structure via C-H 3 3 3 O interactions. Trifluoromethanesulfonate anions are omitted for clarity and the enantiomeric polymers are shown in cyan and magenta, respectively.

In conclusion, we have demonstrated that bidentate ligands with secondary and tertiary sulfonamides represent a versatile building block of metal-organic frameworks. Single crystals of ligands 1, 2, and 4 revealed that all ligands exist in the synclinal conformation. The mixing of the ligands (1-4) with AgOTf yields the corresponding complexes [AgL2(OTf)] (1a), [Ag2(μ-L)2(OTf)2] (2a), [AgL(OTf)]n (2b, 3a), and [AgL]n(OTf)n (4a). In the crystals of complex 1a, silver complex units assembled to form 1D polymers through H-bonds. The disilver macrocycles associated through H-bonds between the sulfonamide moieties and water molecules to give 2D sheets in the crystals of complex 2a, whereas the homochiral coordination polymers were assembled in the crystals of complex 2b. Furthermore, the constructions of the coordination polymers (3a) and the helical coordination polymers (4a) as a racemic mixture of left- and right-handed polymers were observed in the crystals of complexes 3a and 4a, respectively. In all these

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