Tuning the Framework Formation of Silver(I) Complexes with Flexible

the flexibility and conformation freedoms of such ligands offer the possibility for .... The 5-coordination geometry observed here is not very com...
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CRYSTAL GROWTH & DESIGN

Tuning the Framework Formation of Silver(I) Complexes with Flexible Bis(benzothiazol-2-ylsulfanyl)alkanes by Varying the Ligand Spacers and Counteranions

2004 VOL. 4, NO. 1 79-84

Ru-Qiang Zou,† Jian-Rong Li,† Ya-Bo Xie,† Ruo-Hua Zhang,† and Xian-He Bu*,†,‡ Department of Chemistry, Nankai University, Tianjin 300071, P. R. China, and The State Key Laboratory of Structural Chemistry, Fuzhou 350002, P. R. China Received July 3, 2003;

Revised Manuscript Received September 24, 2003

ABSTRACT: In our efforts to systematically investigate the influences of terminal groups, ligand spacers, and counteranions on the framework formations of the AgI complexes with thioether ligands, four structurally related flexible N-containing heterocyclic thioethers, bis(benzothiazol-2-ylsulfanyl)methane (L1), 1,3-bis(benzothiazol-2ylsulfanyl)propane (L2), 1,4-bis(benzothiazol-2-ylsulfanyl)butane (L3) and 1,5-bis(benzothiazol-2-ylsulfanyl)pentane (L4), and seven new AgI complexes of these ligands, [AgL1(NO3)]∞ 1, {[AgL1](ClO4)(H2O)}2 2, {[AgL2(NO3)](CHCl3)}2 3, {[AgL3](ClO4)}∞ 4, {[AgL3](BF4)}∞ 5, {[AgL4(NO3)]CHCl3}2 6, and {[AgL4(ClO4)]2}∞ 7, have been synthesized and characterized. The crystal structures of these complexes show that all the other complexes except 4 and 5 form ligand-supported dinuclear clusters, and in 1 and 7 the dinuclear cluster units are further linked by anions to form 1D chains, and complexes 4 and 5 exhibit 1D zigzag chain structures. Furthermore, these ligands coordinate to AgI ions in N,N-bidentate rather than N,N,S-tridentate or N,N,S,S-tetradentate modes, and the AgI centers adopt 2- to 5-coordination geometries with different coordination environments. In 1, 2, 3, 6, and 7, the coordination modes of the ligands are not sensitive to the changes of the spacers, and the terminal groups seem to be the determining factor in controlling the coordination modes of the ligands. However, the differences of the -(CH2)n- ligand spacers also contribute to the geometrical differences of the dinuclear units. The structural differences between 1 and 2, 6, and 7 show the influences of the counteranions on the coordination geometries of AgI ions and the structures of the complexes. Introduction In recent years, the rational design of coordination polymers based on multitopic bridging ligands and metal centers represents one of the most rapidly developing fields owing to their potential as functional materials,1,2 and the uses of flexible ligands in such studies have attracted increasing attention because the flexibility and conformation freedoms of such ligands offer the possibility for the construction of diverse frameworks with tailored properties and functions.3-9 However, the factors governing the formation of the complexes with such ligands are complicated, and include not only the inherent properties of metal ions and ligands but also anion-based interactions and solvent effects.10 We are currently engaged in a detailed study of the coordination chemistry of dithioether ligands, consisting of various terminal groups linked via flexible multimethylene chain spacers.11 As a continuation of our efforts to investigate the influences of terminal groups, ligand spacers, and counteranions on the framework formations of the AgI complexes with thioether ligands,11 four structurally related flexible N-containing heterocyclic thioethers, bis(benzothiazol-2-ylsulfanyl)methane (L1), 1,3-bis(benzothiazol-2-ylsulfanyl)propane (L2), 1,4bis(benzothiazol-2-ylsulfanyl)butane (L3) and 1,5-bis(benzothiazol-2-ylsulfanyl)pentane (L4) (Chart 1), and seven new AgI complexes of these ligands, [AgL1(NO3)]∞ * To whom correspondence should be addressed. Fax: +86-2223502458. E-mail: [email protected]. † Nankai University. ‡ The State Key Laboratory of Structural Chemistry.

Chart 1

1, {[AgL1](ClO4)(H2O)}2 2, {[AgL2(NO3)](CHCl3)}2 3, {[AgL3](ClO4)}∞ 4, {[AgL3](BF4)}∞ 5, {[AgL4(NO3)]CHCl3}2 6, and {[AgL4(ClO4)]2}∞ 7, have been synthesized and characterized. We report herein the syntheses and crystal structures of these complexes, as well as the influences of ligand spacers and counteranions on their framework formations. Crystallographic data and experimental details for structural analyses are summarized in Table 1. Results and Discussion (1) and {[AgL1](ClO4)(H2O)}2 (2). The formation of a 1D chain and a dinuclear AgI complex with L1 was achieved by varying counteranions in the preparation of complexes. Complex 1 has a onedimensional polymeric structure with the neutral [AgL1(NO3)]2 as repeating unit (Figure 1), which is a centrosymmetric 16-membered macrometallacycle formed by two L1 bridging two AgI ions through benzothiazole nitrogen donors in cis-form, and the Ag‚‚‚Ag nonbonding distance in the dinuclear unit is 8.621 Å. Each AgI is bonded to two N donors of two benzothiazole rings from two distinct L1 ligands and three O donors from two NO3- anions. The coordination geometry can be described as a distorted trigonal bipyramid. The Ag-N [AgL1(NO

3)]∞

10.1021/cg0341149 CCC: $27.50 © 2004 American Chemical Society Published on Web 11/05/2003

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Zou et al.

Table 1. Crystallographic Data and Structural Refinement Summary for Complexes 1-7 chem form form wt cryst syst space group a/Å b/Å c/Å R/° β/° γ/° V/Å3 T/K Dc/g cm-3 Z µ(Mo-KR)/ mm-1 no. unique data (Rint) no. measd reflns Ra/wRb a

1

2

3

4

5

6

7

C15H10AgN3O3S4 516.37 monoclinic C2/c

C30H24Ag2Cl2N4O10S8 1143.65 monoclinic P2(1)/n

C18H15AgCl3N3O3S4 663.79 triclinic P1 h

C18H16AgClN2O4S4 595.89 monoclinic C2/c

C18H16AgBF4N2S4 583.25 monoclinic C2/c

C20H19AgCl3N3O3 S4 691.84 triclinic P1 h

C38H36Ag2Cl2N4O8S8 1219.83 triclinic P1 h

15.611(6) 13.561(6) 16.790(7) 90 95.629(7) 90 3537(3) 293(2) 1.939 8 1.634

11.518(3) 14.148(4) 13.899(4) 90 112.123(4) 90 2098.2(10) 293(2) 1.810 2 1.515

9.786(4) 10.500(4) 13.263(5) 98.842(8) 92.006(7) 116.650(6) 1195.1(8) 293(2) 1.845 2 1.555

23.239(12) 6.001(3) 16.245(8) 90 109.009(9) 90 2142.0(19) 293(2) 1.848 4 1.485

23.233(12) 6.001(3) 16.228(9) 90 109.078(10) 90 2138.2(19) 293(2) 1.812 4 1.376

10.055(4) 10.369(4) 14.029(6) 80.831(7) 86.920(6) 65.435(6) 1313.1(9) 273(2) 1.750 2 1.420

12.094(5) 13.077(5) 16.097(6) 108.992(7) 94.586(7) 107.799(7) 2245.9(16) 293(2) 1.804 2 1.419

3531 (0.0428)

3657 (0.0214)

4203(0.0282)

1985 (0.0301)

1993 (0.0629)

4592(0.0176)

9098 (0.0296)

7762

8390

4910

5245

5258

5406

13117

0.0510/0.0953

0.0740/0.1841

0.0687/0.1528

0.0457/0.1124

0.0597/0.1480

0.0588/0.1187

0.0417/0.1117

R ) ∑(||Fo| - |Fc||)/∑|Fo|. wR ) b

[∑(|Fo|2

-

|Fc|2)2/∑(Fo2)]1/2.

Figure 1. View of the one-dimensional polymeric structure of 1.

bond distances are normal for the AgI complexes with aromatic nitrogen-donor ligands,12 and the Ag-O bond lengths (from 2.451 to 2.594 Å) are also in the normal range for analogous complexes11 (see Table 2). The 5-coordination geometry observed here is not very common for silver complexes.13 The two terminal benzothiazole rings of the same ligand are almost perpendicular to each other with a dihedral angle of ca. 87.9°. The adjacent dinuclear units are further linked by two NO3- bridges to form a 1D chain with the nearest Ag‚‚‚Ag separation of 3.919 Å. Interestingly, each NO3anion shows chelating and bridging coordination modes: two oxygen atoms of NO3- anion chelate one AgI and simultaneously one of the chelating oxygen atoms bridges another AgI of adjacent dinuclear units. The reaction of L1 with AgClO4‚H2O instead of AgNO3 gave rise to a dinuclear complex 2 consisting of a centrosymmetric [Ag2L12]2+ cation, two uncoordinated ClO4- anions, and two disordered water molecules (Figure 2a). Each Ag1 center shows slightly distorted linear coordination geometry composed of two benzothiazole nitrogens from two distinct L1 ligands. The Ag-N bond distances fall in the range of 2.136(4)∼ 2.147(4) Å, which are shorter than those found in other Ag-N complexes.12 Two AgI centers are bridged equivalently by two L1 ligands to form a 16-membered macrometallacycle in which the Ag‚‚‚Ag separation is 3.454 Å. Different from complex 1, the four benzothiazole rings in the dinuclear unit are all parallel to each other. The centroid-centroid distance of 3.48 Å between benzothiazole rings of adjacent ligands indicates significant

Figure 2. (a) The dinuclear structure of 2 and (b) the 2D network formed by the weak interactions of Ag‚‚‚O and S‚‚‚O.

intramolecular face-to-face π-π stacking interactions, which further stabilize the structure. Each uncoordinated ClO4- anion shows weak Ag‚‚‚O interaction with the AgI center of one dinuclear unit (the Ag‚‚‚O distance is ca. 2.792 Å) and S‚‚‚O interaction with a benzothiazole S atom from another dinuclear unit (the

Tuning the Framework Formation of Silver(I) Complexes

Figure 3. (a) The dinuclear structure of 3 and (b) the 2D network formed by the Ag‚‚‚S weak interactions and the faceto-face π-π stacking interactions.

S‚‚‚O distance is ca. 3.257 Å). These weak Ag‚‚‚O and S‚‚‚O interactions link these dinuclear units into a quasi 2D network (Figure 2b). In addition, two disordered water molecules fill in the cavity formed by four dinuclear units. {[AgL2(NO3)](CHCl3)}2 (3). The reaction of AgNO3 with L2 leads to the formation of a neutral dimeric complex {[AgL2(NO3)](CHCl3)}2 3, which consists of neutral binuclear unit [AgL2(NO3)] and two CHCl3 molecules (Figure 3a). Two AgI ions are bridged equivalently by two L2 ligands with N donors to form a 20membered macrometallacycle with a crystallographic center of symmetry. Each AgI center has a slightly distorted trigonal planar geometry coordinated by two benzothiazole N donors from two distinct L2 ligands and an O donor from nitrate. The Ag-N and Ag-O bond distances fall in the expected range.11,12 The AgI center deviates from the coordination plane by ca. 0.183 Å, and the bond angles around AgI center range from 118.27 to 103.05°. In the dinuclear unit, the ligand also adopts N,Nbidentate coordination mode, but the coordination mode of nitrate and the coordination geometry of AgI are different from those in complex 1. The AgI ions are 0.4 Å above and below the plane formed by four N donors, and the Ag‚‚‚Ag nonbonding distance in the dinuclear unit is 10.52 Å. The two terminal benzothiazole groups of each ligand are inclined to each other at an angle of 106.4°. It is noteworthy that there are weak Ag‚‚‚S interactions between adjacent binuclear units, and these weak interactions extend the dinuclear units into a quasi 1D chain. In addition, there are intermolecular π-π stacking interactions between adjacent 1D chains with the centroid-centroid distance of 3.48 Å between

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Figure 4. (a) The one-dimensional chain of 4 and (b) the 2D network formed by the Ag‚‚‚S weak interactions and the π-π stacking interactions.

benzothiazole rings (Figure 3b). The co-effects of the Ag‚‚‚S and π-π interactions further stabilize the structure. {[AgL3](ClO4)}∞ (4) and {[AgL3](BF4)}∞ (5). Complex 4 and 5 are isostructural, so we only describe the structure of 4. Complex 4 is composed of {[AgL3]+}∞ zigzag cation chains and ClO4- anions. Each AgI ion has a linear geometry comprised of two benzothiazole N donors from distinct L3 ligands. The Ag-N distance of 2.136(6) Å is shorter than those found in other AgI complexes with N-containing ligands.12 In 4, the AgI ions are bridged by L3 ligands with two N donors to form a 1D chain along the b direction (Figure 4a) with the adjacent Ag‚‚‚Ag nonbonding distance being ca. 12.001 Å. It is noteworthy that L3 adopts a N,N-bidentate bridging mode in trans-form, while in 1 and 2, L1 bridges the AgI ions in cis-form. Only the N atoms of the benzothiazole rings of L3 coordinate to AgI centers, which is similar to L1 in 1 and 2. Each AgI center in one chain shows weak interactions with two S atoms of the benzothiazole rings from two adjacent chains (the Ag‚‚‚S distance is 3.54 Å), and these weak interactions link the 1D chains into a quasi 2D network (Figure 4b). There are also face-to-face π-π stacking interactions between adjacent chains.14 {[AgL4(NO3)]CHCl3}2 (6) and {[AgL4(ClO4)]2}∞ (7). Complex 6 is also a centrosymmetric dinuclear structure (Figure 5a), and the coordination geometry of AgI is a distorted tetrahedron coordinated by two N donors of two benzothiazolyl groups from two distinct L4 ligands and two O atoms of NO3-. In the dinuclear unit, two AgI centers are bridged by two L4 to form a 24membered macrometallacycle with Ag‚‚‚Ag separation of ca. 10.523 Å. The two AgI ions are above or below the mean plane formed by four N donors by 0.414(4) Å.

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Figure 5. (a) The dinuclear structure of 6 and (b) the 1D chain formed by the S‚‚‚S weak interactions.

Zou et al.

are some solvent molecules encapsulated in the space among adjacent dinuclear units in 2, 3, and 6 (disordered water molecules in 2, CHCl3 molecules in 3 and 6). In 1∼3, 6, and 7, there exist some geometrical differences in the dinuclear units: (i) the coordination numbers of AgI ions are different (5 in 1, 2 in 2, 3 in 3, 4 in 6, and 4 in 7; (ii) the two benzothiazole rings coordinated to the same AgI in 1, 6, and 7 are declined to each other, while in 2 they are parallel to each other with stronger intramolecular π-π stacking. The structural differences of 1 and 2 may be due to the difference of counteranions. In general, the effect of anions can be explained from their differences in sizes and coordination ability.15 NO3- participates in the formation of 1, while in 2 ClO4- only acts as counterion, and consequently, the dinuclear units of 1 are further linked by NO3- to form a chain structure. Also, due to the different coordination modes of NO3- (chelating in 6) and ClO4- (bridging in 7), the complexes of L4 with AgNO3 and AgClO4 take different structures. However, since the size of BF4- is similar to that of ClO4- and they do not take part in the coordination to AgI ions in 4 and 5, the two complexes show similar structures. In summary, this work illustrates some useful results of ligand design for self-assembly of diverse coordination aggregates with AgI ions. Unlike our previous work,11 the differences of ligand spacers in L1, L2, and L4 do not greatly influence the structures of their complexes, but the terminal groups seem to be a determining factor to affect the frameworks of these complexes. However, the changes of the (CH2)n ligands spacers also cause subtle geometrical differences in the dinuclear units of these complexes. These results indicate that the changes of counteranions could adjust the framework formation of such complexes, and this may provide an effective method for controlling the structures of complexes with tailored properties. Experimental Procedures

Figure 6. View of the one-dimensional polymeric structure of 7.

There exist weak S‚‚‚S polarized interactions between adjacent dinuclear units with S‚‚‚S distance of 3.622 Å (Figure 5b), and these S‚‚‚S interactions extend the dinuclear units into a chain structure. Complex 7 consists of 1D chain formed via linking the [Ag2L42]2+ moieties by ClO4- ions (Figure 6), and each AgI center is tetrahedrally coordinated to two N donors of two distinct L4 ligands and two O donors from two ClO4-. Adjacent AgI centers bridged by ClO4- ions have slightly different coordination environments indicated by different bond lengths and angles around Ag(1) and Ag(2). Two ligands bridge two Ag1 ions with N donors in cis-form to form a 24-membered macromatallacycle with Ag‚‚‚Ag separation of 12.93 Å. Two ClO4- ions taking bidentate bridging mode bridge two AgI ions to form an eight-membered ring with Ag‚‚‚Ag separation of 5.516 Å. In general, all complexes except 4 and 5 form dinuclear units, among which 1 and 7 are linked by anions to form extended structures. It is noteworthy that there

Materials and General Methods. All the solvents and reagents for synthesis were commercially available and used as received. Elemental analyses were performed on a PerkinElmer 240C analyzer, and IR spectra on a 170SX (Nilolet) FTIR spectrometer. 1H NMR spectra were recorded on a Bruker AC-P500 spectrometer (300 MHz) at 25 °C using tetramethylsilane as internal reference. Thermal stability (DTA) studies were carried out on a NETZSCH TG 209 instrument. Synthesis of Ligands. Bis(benzothiazol-2-ylsulfanyl)methane (L1). Dibromomethane (1.74 g, 0.01 mol) was added dropwise to a hot solution (∼50 °C) of 2-sulfanylbenzothiazole sodium salt (3.78 g, 0.02 mol) in ethanol (30 mL), and the mixture was further stirred at 50 °C for 6 h. After cooling, the mixture was added additional water (30 mL) and left to stand for 5 h. The precipitate was filtered, washed with ethanol and water, and recrystallized from CHCl3/Et2O to obtain light yellow powder. Yield: 80%. 1H NMR (300 MHz, CDCl3): δ 5.34 (s, 2H), 7.32∼7.93 (m, 8H). IR (KBr, cm-1): 3048w, 2923w, 2874w, 1558w, 1456s, 1424vs, 1309m, 1237m, 1018m, 1003s, 753vs, 725s. L2, L3, and L4 were synthesized by the similar procedure as described above. 1,3-Bis(benzothiazol-2-ylsulfanyl)propane (L2). Yield: 80%. 1H NMR (CDCl3): δ 2.41 (t, 2H), 3.53 (t, 4H), 7.26∼7.84 (m, 8H). IR (KBr, cm-1): 3054w, 2960w, 2914w, 1555w, 1451s, 1419vs, 1307m, 1236m, 1006m, 991s, 764vs, 757vs, 726s. 1,4-Bis(benzothiazol-2-ylsulfanyl)butane (L3). Yield: 83%. 1 H NMR (CDCl3): δ 2.04 (t, 4H), 3.42 (t, 4H), 7.30∼7.87 (m,

Tuning the Framework Formation of Silver(I) Complexes

Crystal Growth & Design, Vol. 4, No. 1, 2004 83

8H). IR (KBr, cm-1): 3034w, 2956w, 2880w, 1559w, 1456s, 1426vs, 1305m, 1230m, 998s, 753vs, 721s. 1,5-Bis(benzothiazol-2-ylsulfanyl)pentane (L4). Yield: 85%. 1H NMR (CDCl3): δ 1.65 (t, 2H), 1.93 (m, 4H), 3.37 (m, 4H), 7.25∼7.87 (m, 8H). IR (KBr, cm-1): 3062w, 2940w, 2859w, 1560w, 1456s, 1423vs, 1309m, 1235m, 1010m, 1000s, 756vs, 726s, 704w. Preparation of Complexes. [AgL1(NO3)]∞ (1). The reaction of L1 (35 mg, 0.1 mmol) with AgNO3 (17 mg, 0.1 mmol) in MeOH (10 mL) for a few minutes afforded a light yellow solid, which was filtered, washed with acetone, and dried in air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et2O into the acetonitrile solution of the solid. Yield: 54%. Anal. Calcd for C15H10AgN3O3S4: C, 34.89; H, 1.95; N, 8.14. Found: C, 35.61; H, 2.21; N, 8.42. IR (KBr, cm-1): 3035w, 3017w, 2890w, 1630w, 1454s, 1418vs, 1285vs, 1033s, 1008s, 753s, 725m, 694m. DTA data (peak position): 172, 237, and 307 °C. {[AgL1](ClO4)(H2O)}2 (2). A solution of AgClO4‚H2O (23 mg, 0.1 mmol) in MeOH (10 mL) was added to a solution of L1 (35 mg, 0.1 mmol) in CHCl3 (20 mL) in a 50 mL beaker and the resulted solution was kept at room temperature in the dark. Light yellow crystals formed at the bottom of the beaker after 3 days. Yield: 53%. Anal. Calcd for C30H24Ag2Cl2N4O10S8: C, 31.51; H, 2.12; N, 4.90. Found: C, 31.78; H, 2.05; N, 4.61. IR (KBr, cm-1): 3440m, 3015w, 3020w, 2900w, 1561w, 1455s, 1085vs, 756s, 720s, 620s. DTA data (peak position): 103, 178, 231, and 320 °C. {[AgL2(NO3)](CHCl3)}2 (3). A solution of AgNO3 (17 mg, 0.1 mmol) in MeOH (10 mL) was added to a solution of L2 (38 mg, 0.1 mmol) in CHCl3 (20 mL), and light yellow power formed immediately. Yield: 65%. Single crystals suitable for X-ray analysis were obtained by recrystallization the powder from MeCN/Et2O. Anal. Calcd for C18H15AgCl3N3O3S4: C, 32.57; H, 2.28; N, 6.33. Found: C, 32.25; H, 2.02; N, 6.55. IR (KBr, cm-1): 3060w, 3022w, 2950w, 1630w, 1456s, 1426vs, 1375vs, 1310s, 996s, 754s, 726m, 685m, 666m. DTA data (peak position): 109, 197, and 334 °C. {[AgL3](ClO4)}∞ (4). A solution of AgClO4‚H2O (46 mg, 0.2 mmol) in CH3CN (10 mL) was added to a solution of L3 (81 mg, 0.2 mmol) in CHCl3 (10 mL). The reaction mixture was filtered to give a colorless solution. Slow diffusion of Et2O into the resulted solution yielded light yellow single crystals suitable for X-ray analysis in 50% yield. Anal. Calcd for C18H16AgClN2O4S4: C, 36.28; H, 2.71; N, 4.70. Found: C, 36.05; H, 2.48; N, 4.92. IR (KBr, cm-1): 3055w, 3037w, 2985w, 1617w, 1561w, 1452m, 1426m, 1416s, 1090vs, 1040s, 998m, 771m, 754m, 623m. DTA data (peak position): 135, 266, and 345 °C. {[AgL3](BF4)}∞ (5). A solution of AgBF4‚H2O (43 mg, 0.2 mmol) in CH3CN (10 mL) was added to a solution of L3 (81 mg, 0.2 mmol) in CHCl3 (10 mL). The reaction mixture was filtered to give a colorless solution. Slow diffusion of Et2O into the resulted solution yielded light yellow single crystals suitable for X-ray analysis in 50% yield. Anal. Calcd for C18H16AgBF4N2S4: C, 37.07; H, 2.77; N, 4.80. Found: C, 36.83; H, 2.53; N, 4.93. IR (KBr, cm-1): 3045w, 3025w, 2976w, 1627w, 1457w, 1427m, 1307s, 1062vs, 1034vs, 998m, 761s, 754m, 533w. DTA data (peak position): 167 and 366 °C. {[AgL4(NO3)](CHCl3)}2 (6). A solution of AgNO3 (17 mg, 0.1 mmol) in MeOH (5 mL) was added to a solution of L4 (40 mg, 0.1 mmol) in CHCl3 (5 mL), and light yellow power was formed immediately in 54% yield. Single crystals were obtained by recrystallization the powder from MeCN/Et2O. Anal. Calcd for C20H19AgCl3N3O3S4: C, 34.72; H, 2.77; N, 6.07. Found: C, 34.48; H, 2.51; N, 6.31. IR (KBr, cm-1): 3029w, 3013w, 2965w, 1561w, 1455s, 1423vs, 1368vs, 1309s, 1236m, 1219m, 1198m, 1093m, 1036s, 1015s, 771s, 755vs, 727s, 694m, 665m. DTA data (peak position): 94, 224, and 328 °C. {[AgL4(ClO4)]2}∞ (7). A solution of AgClO4‚H2O (46 mg, 0.2 mmol) in CH3CN (10 mL) was added to a solution of L4 (81 mg, 0.2 mmol) in CHCl3 (10 mL). The reaction mixture was filtered to give a colorless solution. Slow diffusion of Et2O into the resulted solution yielded light yellow single crystals suitable for X-ray analysis in 65% yield. Anal. Calcd for C38H36Ag2Cl2N4O8S8: C, 37.42; H, 2.97; N, 4.59. Found: C, 37.23; H,

2.64; N, 4.87. IR (KBr, cm-1): 3067w, 3023w, 2920w, 1624w, 1563w, 1454m, 1413s, 1089vs, 1035s, 941m, 766s, 726m, 695m, 625s. DTA data (peak position): 225 °C. Caution! Although we have met no problems in handling perchlorate salt during this work, these should be treated cautiously, owing to their potential explosive nature. X-ray Crystallography. Single-crystal X-ray diffraction measurements were carried out on a Bruker Smart 1000 CCD diffractometer equipped with a graphite crystal monochromator situated in the incident beam for data collection at room temperature. The determination of unit cell parameters and data collections was performed with Mo-KR radiation (λ ) 0.71073 Å). Unit cell dimensions were obtained with leastsquares refinements, and all structures were solved by direct methods. Silver atoms in each complex were located from E-maps. The non-hydrogen atoms were located in successive difference Fourier syntheses (in complex 1, the oxygen atoms of the nitrate anions are disordered and treated isotropically). The final refinement was performed by full matrix leastsquares methods with anisotropic thermal parameters for nonhydrogen atoms on F2. The hydrogen atoms were added theoretically and riding on the concerned atoms. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-211344 for 1, 211345 for 2, 211346 for 3, 211347 for 4, 211348 for 5, 211349 for 6 and 211350 for 7. Copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: int. code +44(1223)336-033; E-mail: [email protected]].

Acknowledgment. This work was supported by the Outstanding Youth Foundation of NSFC (No. 20225101). Supporting Information Available: Crystallographic information files (CIF) of compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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CG0341149