Syntheses, Structures, and Characterizations of Four New Silver(I) Sulfonate Coordination Polymers with Neutral Ligands Fang-Fang Li, Jian-Fang Ma,* Shu-Yan Song, and Jin Yang Department of Chemistry, Northeast Normal UniVersity, Changchun 130024, People’s Republic of China
CRYSTAL GROWTH & DESIGN 2006 VOL. 6, NO. 1 209-215
Heng-Qing Jia and Ning-Hai Hu Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People’s Republic of China ReceiVed June 27, 2005; ReVised Manuscript ReceiVed October 25, 2005
ABSTRACT: In this paper, four novel silver(I) sulfonate coordination polymers containing neutral ligands, namely, [Ag2L1(biim)2]‚ 2H2O (1), AgL2(biim) (2), [Ag(HL3)(Pic)2]‚H2O (3), and [Ag3(L3)(HL3)(4,4′-bipy)3(H2O)2]‚4H2O (4), have been synthesized [L1 ) 3-carboxy-4-hydroxybenzenesulfonate, L2 ) p-aminobenzenesulfonate, H2L3 ) p-hydroxybenzenesulfonic acid, biim ) 1,1′-(1,4-butanediyl)-bis(imidazole), Pic ) β-picoline, 4,4′-bipy ) 4,4′-bipyridine]. For compounds 1 and 2, Ag(I) cations are bridged by biim ligands to form a one-dimensional (1D) “zigzag” chain, and L1 and L2 sulfonate ligands are not coordinated to the silver cation. Compound 3 has a dimeric structure in which two silver cations are bridged by two HL3 ligands. For compound 4, L3 ligand coordinates to a silver cation as a monodentate ligand, and Ag(I) cations are bridged by 4,4′-bipy ligands to form a 1D chain. Compound 1 contains water dimers, while compound 4 contains water trimers. Compounds 1-3 display room-temperature photoluminescence. Introduction To design and synthesize metal-organic coordination networks (MOCNs) based on coordination bonds and noncovalent interactions (such as hydrogen-bonding interactions), the interactive information stored in the ligand, as well as the coordination geometry of the metal ions, should be taken into account. Careful selection of a suitable organic ligand containing the ability to form hydrogen bonding is helpful for constructing novel MOCNs. The -SO3- group can adopt many bridging coordination modes, and Ag, a d10 metal, has no crystal field stabilization energy and hence no dominant geometrical preferences.1b Therefore, interest has recently been focused on silver(I) sulfonates by reason of their abilities to form various structures and their properties.1l-1n On the basis of previous reports, the structure motif of most silver(I) sulfonates observed is a two-dimensional (2D) sheet, which is similar to that of metal phosphonates.2 In addition, the study of the effect of an organic group on the structures of silver(I) sulfonates has been explored by Shimizu.1b Some silver(I) sulfonate compounds modified by nitrogen-based ligands that display different structure motifs depending upon the presence of secondary ligands have been reported.2e-2k It has also been demonstrated that existence and changes of the neutral ligands in silver(I) sulfonates can result in surprising results. However, the information on silver sulfonate coordination polymers are not yet well understood, and investigations of silver(I) sulfonates with neutral ligands are rather insufficient. In this paper, four compounds, namely, [Ag2L1(biim)2]‚2H2O (1), AgL2(biim) (2), [Ag(HL3)(Pic)2]‚H2O (3), and [Ag3(L3)(HL3)(4,4′-bipy)3(H2O)2]‚4H2O (4) [L1 ) 3-carboxy-4-hydroxybenzenesulfonate, L2 ) p-aminobenzenesulfonate, H2L3 ) p-hydroxybenzenesulfonic acid, biim ) 1,1′-(1,4-butanediyl)bis(imidazole), Pic ) β-picoline, 4,4′-bipy ) 4,4′-bipyridine], were synthesized with two aims: one is to construct novel * Corresponding author. E-mail:
[email protected]. Fax: 86431-5684009.
Scheme 1.
Structures of the Sulfonate Ligands in This Work
MOCNs and the other is to explore the effect of the neutral ligands on silver sulfonates. The chosen sulfonate ligands containing -OH and -NH2 groups have a potential for hydrogenbonding interactions to construct new MOCNs and enhance crystal stability. The selected aromatic nitrogen bases are good neutral ligands for silver cations. Biim is a divergent bidentate ligand and commonly acts as a flexible bridging ligand. In our previous work, some coordination polymers containing biim ligand with different topologies have been reported.3 Therefore, biim was selected as a neutral ligand to construct novel silver sufonate coordination polymers and explore its effect on different silver sulfonate compounds. At the same time, Pic (a monodentate ligand) and 4,4′-bipy (a divergent bidentate ligand) were employed to synthesize new silver sulfonates and study the influence of the number of coordinating atoms of the neutral ligand on the silver sulfonate compound. Compounds 1 and 2 containing the same neutral ligand show a one-dimensional (1D) polymeric structure. Although compounds 3 and 4 contain the same sulfonate anion, 3 shows a discrete dimeric structure, while 4 displays a 1D chain structure. The structures of the sulfonate anions and neutral ligands used in this work are shown in Schemes 1 and 2. The work in this paper extends the previous work on silver(I) sulfonate coordination chemistry. All crystal structures have been determined by single-crystal X-ray diffraction, and the compounds are also characterized by IR and
10.1021/cg050293d CCC: $33.50 © 2006 American Chemical Society Published on Web 11/24/2005
210 Crystal Growth & Design, Vol. 6, No. 1, 2006
Li et al.
Table 1. Summary of X-ray Crystallographic Data for Compounds 1-4 compound
1
2
3
4
chem formula fw color, habit crystal size (mm3) cryst syst space group a (Å) b (Å) c (Å) R/° β/° γ/° V (Å3) Z µ (Mo KR, mm-1) F(000) θ range (deg) h range k range l range reflns collected/unique reflns obsd [I > 2σ(I)] GOF R1, wR2 (obsd) (∆/σ) max, mean max, min peaks (e Å-3)
C27H35Ag2N8O8S 847.43 colorless, platelet 0.182 × 0.112 × 0.068 triclinic P1h 10.174(5) 12.353(5) 14.723(5) 102.609(5) 107.015(5) 103.530(5) 1636(1) 2 1.320 854 1.78-26.04 -7 to 12 -15 to 14 -18 to 17 9291/6303 4409 0.930 0.0360, 0.0807 0.001, 0.000 0.415, -0.672
C16H20AgN5O3S 470.30 colorless, platelet 0.243 × 0.171 × 0.069 orthorhombic Pnma 14.125(5) 15.722(6) 8.510(3) 90.00 90.00 90.00 1890(1) 4 1.203 952 2.59-26.43 -17 to 14 -17 to 19 -10 to 10 10151/2006 1496 1.042 0.0455, 0.1116 0.000, 0.000 0.513, -0.567
C18H21AgN2O5S 485.30 colorless, platelet 0.230 × 0.116 × 0.065 triclinic P1h 9.725(3) 10.165(3) 10.444(3) 98.447(4) 94.940(5) 92.882(4) 1015.4(5) 2 1.125 492 1.98-28.26 -12 to 12 -11 to 13 -9 to 13 6434/4534 2954 0.893 0.0374, 0.0795 0.001, 0.000 0.482, -0.289
C42H45Ag3N6O14S2 1245.57 yellow, platelet 0.286 × 0.133 × 0.076 monoclinic C2/c 25.227(3) 11.430(1) 18.886(2) 90.00 125.869(2) 90.00 4413.1(9) 4 1.489 2496 1.99-26.07 -31 to 31 -13 to 14 -23 to 22 12165/4329 3293 0.943 0.0332, 0.0726 0.001, 0.000 0.864, -0.399
Scheme 2.
Structures of Three Neutral Ligands
elemental analyses. Moreover, compounds 1-3 exhibit photoluminescent properties at room temperature. Experimental Section Materials. 1,1′-(1,4-Butanediyl)bis(imidazole) was synthesized in accordance with the procedure reported.3c Other reagents and solvents employed were commercially available and used as received without further purification. Physical Methods. Elemental analyses were carried out with a Carlo Erba 1106 elemental analyzer, and the FT-IR spectra were recorded from KBr pellets in the range 4000-400 cm-1 on a Mattson AlphaCentauri spectrometer. The emission/excitation spectra were recorded on a Varian Cary Eclipse spectrometer. Synthesis of [Ag2L1(biim)2]‚2H2O (1). To a mixture of H2L1 (0.127 g, 0.5 mmol) and NaOH (0.04 g, 1.0 mmol) in water was added AgNO3 (0.170 g, 1.0 mmol) with constant stirring, to which was added biim (0.096 g, 0.5 mmol) in water. After the sample was stirred for 10 min, the precipitate was dissolved by dropwise addition of aqueous NH3 solution. Colorless crystals were obtained from the filtrate by slow evaporation after standing in the dark for several days (75% yield). Anal. Calcd for C27H35Ag2N8O8S: C 38.27, H 4.16, N 13.22. found: C 38.21, H 4.13, N 13.27. IR (KBr, cm-1) 3859(w), 3741(ms), 3443(ms), 2361(vs), 2336(vs), 1700(ms), 1645(ms), 1560(ms), 1515(ms), 1467(w), 1197(w), 673(ms), 565(w), 432(w), 406(ms). Synthesis of AgL2(biim) (2). To a mixture of HL2 (0.173 g, 1 mmol) and NaOH (0.040 g, 1 mmol) in water was added AgNO3 (0.255 g, 1.5 mmol) with constant stirring, and a white precipitate formed. The precipitate was dissolved by dropwise addition of aqueous NH3
solution, to which was added biim (0.288 g, 1.5 mmol) in 10 mL of ethanol. Colorless crystals were obtained from the filtrate by slow evaporation after standing in the dark room for several days (78% yield). Anal. Calcd for C16H20AgN5O3S: C 40.86, H 4.29, N 14.89. found: C 40.75, H 4.23, N 14.96. IR (KBr, cm-1) 3859(w), 3741(ms), 3439(s), 3343(s), 3227(ms), 3119(s), 2930(w), 2361(vs), 2336(vs), 1643(s), 1600(s), 1560(s), 1465(ms), 1340(w), 1187(vs), 1117(s), 1028(s), 1004(ms), 949(w), 830(ms), 788(w), 692(s), 662(ms), 569(s), 417(ms). Synthesis of [Ag(HL3)(Pic)2]‚H2O (3). A mixture of NaHL3 (0.098 g, 0.5 mmol) and AgNO3 (0.085 g, 0.5 mmol) in water was stirred for 5 min, to which was added an aqueous solution of β-Pic (0.093 g, 1 mmol). After the sample was stirred for 10 min, the precipitate was dissolved by dropwise addition of ethanol. Colorless crystals were obtained from the filtrate by slow evaporation after standing in the dark for several days (80% yield). Anal. Calcd for C18H21AgN2O5S: C 44.55, H 4.36, N 5.77. found: C 44.63, H 4.41, N 5.65. IR (KBr, cm-1) 3737(w), 3673(w), 3279(ms), 2360(vs), 2339(vs), 1700(w), 1650(ms), 1212(vs), 1180(vs), 1037(s), 1010(ms), 835(ms), 790(w), 703(s), 653(ms), 572(s), 421(ms). Synthesis of [Ag3(L3)(HL3)(4,4′-bipy)3(H2O)2]‚4H2O (4). A mixture of NaHL3 (0.098 g, 0.5 mmol) and AgNO3 (0.085 g, 0.5 mmol) in methanol was stirred for 5 min, to which was added 4,4′-bipy (0.039 g, 0.25 mmol) in methanol. After the mixture was stirred for 10 min, the precipitate was dissolved by dropwise addition of aqueous solution of NH3. Yellow crystals were obtained from the filtrate by slow evaporation after standing in the dark for several days (70% yield). Anal. Calcd for C42H45Ag3N6O14S2 : C 40.50, H 3.64, N 6.75. found: C 40.58, H 3.61, N 6.79. IR (KBr, cm-1) 3859(w), 3741(ms), 3673(ms), 3425(ms), 2361(vs), 2336(vs), 1652(ms), 1601(ms), 1455(ms), 1186(ms), 1119(w), 1024(w), 811(ms), 674(ms), 574(ms), 406(w). X-ray Crystallography. Experimental details of the X-ray analyses are provided in Table 1. Diffraction intensities for compounds 1-4 were collected on a Bruker Apex CCD diffractometer with graphitemonochromated MoKR radiation (λ ) 0.71069Å). The structures were solved with the direct method of SHELXS-974 and refined with fullmatrix least-squares techniques using the SHELXL-97 program5 within WINGX.6 Non-hydrogen atoms were refined anisotropically. Analytical expression of neutral-atom scattering factors were employed, and anomalous dispersion corrections were incorporated.7 Further details are provided in Supporting Information.
Results and Discussion Selected bond distances and angles for compounds 1-4 are listed in Table 2. As shown in Figure 1, the L1 ligand in compound 1 does not show any bonding actions with silver
Four New Silver(I) Sulfonate Coordination Polymers
Crystal Growth & Design, Vol. 6, No. 1, 2006 211
Table 2. Selected Bond Distances (Å) and Angles (°) for Compounds 1-4a Compound 1 Ag(1)-N(2)ii 2.114(3) Ag(1)-N(3) 2.113(3) Ag(2)-N(6) 2.102(3) Ag(2)-N(7)i 2.102(3) Ag(2)-Ag(2)iii 3.3399(11) N(3)-Ag(1)-N(2)ii 166.59(11) N(6)-Ag(2)-N(7)i 168.46(11) N(6)-Ag(2)-Ag(2)iii 118.86(8) N(7)i-Ag(2)-Ag(2)iii 72.65(8) Compound 2 Ag(1)-N(2) N(2)-Ag(1)-N(2)i
2.082(11) 180.0(2)
Ag(1)-N(1) Ag(1)-Ag(1)i N(2)-Ag(1)-N(1) N(1)-Ag(1)-Ag(1)i
Compound 3 2.168(3) Ag(1)-N(2) 3.1080(8) 167.00(9) N(2)-Ag(1)-Ag(1)i 92.04(7)
Ag(1)-N(1) Ag(2)-N(3) N(2)i-Ag(1)-N(1)
Compound 4 2.182(3) Ag(1)-N(2)i 2.173(3) Ag(2)-N(4)i 173.22(10) N(4)i-Ag(2)-N(3)
2.163(3) 96.80(7)
Figure 3. Hydrogen-bonding motif in 1. Hydrogen bonds: dashed lines. Table 3. Hydrogen-Bond Geometries for Compound 1, 3, and 4 (Å, °)a
2.166(3) 2.160(4) 180.000(2)
Symmetry codes for 1: i x - 1, y - 1, z; ii x + 1, y + 1, z; iii -x, -y, -z + 1. 2: i -x + 1, -y, -z + 2. 3: i -x, -y + 1, -z. 4: i x, y - 1, z. a
D-H‚‚‚A
d(D-H) [Å]
d(H‚‚‚A) [Å]
d(D‚‚‚A) [Å]
