Structural Diversities of Silver(I) Coordination Compounds with

(b) Batten, S. R.; Hoskins, B. F.; Moubaraki, B.; Murray, K. S.; Robson, R. J. Chem. Soc. ...... (a) Long, D.-L.; Blake, A. J.; Champness, N. R.; Wils...
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CRYSTAL GROWTH & DESIGN

Structural Diversities of Silver(I) Coordination Compounds with Flexible Dithioether Ligands Based upon Changing the Ligand Spacers

2003 VOL. 3, NO. 5 829-835

Jian-Rong Li,† Ruo-Hua Zhang,† and Xian-He Bu*,†,‡ Department of Chemistry, Nankai University, Tianjin 300071, People’s Republic of China, and The State Key Laboratory of Structural Chemistry, Fuzhou 350002, People’s Republic of China Received June 6, 2003;

Revised Manuscript Received June 27, 2003

ABSTRACT: To investigate the influences of ligand spacers of flexible bis(thioether) bridging ligands on the framework formations of their complexes, six new AgI coordination compounds with a series of structurally related bis(tert-butylthio)alkane ligands, Ln ) (CH3)3CS-(CH2)n-SC(CH3)3 where n ) 1-6, [(AgL1)ClO4]n (1), {[Ag(L2)1.5]ClO4}n (2), [(AgL3)ClO4]2 (3), {[Ag(L4)1.5]ClO4}n (4), [(AgL5)ClO4]2 (5), and {[Ag(L6)1.5]ClO4}n (6), have been synthesized and structurally characterized by elemental analysis, IR, 1H NMR spectra, and X-ray crystallography. In 1, the AgI centers are linked by bridging L1 to form a one-dimensional (1-D) zigzag chain, and complex 2 has an extended two-dimensional (2-D) (6,3) topologic array with hexagonal 30-membered macrometallacycles. Complexes 3 and 5 show similar discrete dinuclear structures. Complexes 4 and 6 consist of single-double bridging chains in which dinuclear macrometallacycles are further linked by single bridging L ligands. The differences among these structures indicate that the spacers of ligands have important effects on the framework formation of their AgI complexes, and this presents a feasible way for controlling the structures of such complexes by modifying the ligand spacers. Introduction There is still great current interest in the investigation of inorganic-organic supramolecular coordination architectures with useful properties.1-3 Considerable progress has been made on the theoretical forecast and network-based approaches aiming at controlling the topology structure and geometry of the networks to produce useful functional materials.4 However, the prediction of coordination frameworks is still subjective and cannot be generalized because the self-assembly progress is highly influenced by several factors such as the ligands’ nature,3a solvents,5,3d,f templates,6 counterions,7 and so on. Accordingly, to understand the intriguing connection between complex structures and factors affecting the framework formation is one of the key points for the rational design of crystalline materials and seems to be a long-range challenge. We are currently engaged in the synthesis and coordination chemistry studies on flexible linear dithioether ligands depicted by the generalized Scheme 1, in which two terminal groups are linked via spacer groups, X, with various space size and shapes. Some successful examples have shown that such ligands are able to generate unusual AgI coordination polymers with unique structures.8 In addition, an interesting feature of these complexes is that they prefer forming macrometallacycles, which act as structural units to construct multidimensional frameworks. In view of the diverse coordinating behaviors of these flexible S-donor ligands with AgI and the sensitivity of the structures of AgI complexes to the slight variations of ligands, we synthesized and characterized a new * To whom correspondence should be addressed. Fax: +86-2223502458. E-mail: [email protected]. † Nankai University. ‡ The State Key Laboratory of Structural Chemistry.

Scheme 1

series of the coordination compounds of AgClO4 with bis(tert-butylthio) ligands [Ln ) (CH3)3CS-(CH2)n-SC(CH3)3 where n ) 1-6]. In this paper, we report these results as well as a systematic structural comparison of relative AgI complexes of some flexible dithioether ligands. Experimental Procedures Materials and General Methods. All the reagents for syntheses were commercially available and employed without further purification or purified by standard methods prior to use. A series of dithioether ligands, Ln ) (CH3)3CS-(CH2)nSC(CH3)3 where n ) 1-6, were synthesized by the reaction of homologous bis(bromo)alkane with sodium tert-butylthiolate according to the similar literature method.11 Elemental analyses were performed on a Perkin-Elmer 240C analyzer. IR spectra (KBr pellets) were taken on a FT-IR 170SX (Nicolet) spectrometer. 1H NMR spectra were measured on a Bruker AC-P500 spectrometer (300 MHz) at 25 °C in CDCl3 with tetramethylsilane as the internal reference. Thermal analyses were performed in the temperature range of 25-400 °C on a NETZSCH TG209 instrument. Colorless single crystals suitable for X-ray analyses for the six complexes were obtained by the similar method as follows: to a solution of AgClO4‚H2O (0.1 mmol) in acetone (2 mL) was slowly added a CHCl3 solution (2 mL) of ligand (0.2 mmol). The mixture was stirred for 10 min and filtered. Colorless single crystals were obtained by slow diffusion of ether to above filtrate in the dark. [(AgL1)ClO4]n 1. Yield: 62%. Anal. Calcd. for C9H20S2AgClO4: C, 27.05; H, 5.04. Found: C, 27.21; H, 4.93. IR (KBr

10.1021/cg034092q CCC: $25.00 © 2003 American Chemical Society Published on Web 07/22/2003

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Table 1. Crystallographic Data and Structural Refinement Details for 1-6 formula Mr crystal size (mm) crystal system space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) Dc (Mg m-3) Z T (K) µ (mm-1) F(000) refl. collected unique refl. (Rint) parameters goodness of fit R1 [I > 2σ(I)] wR2 (all data) max. diff. peak (e Å-3)

1

2

3

4

5

6

C9H20S2AgClO4 399.69 0.32 × 0.26 × 0.20 monoclinic P21/c 8.774(5) 17.26(1) 10.025(5) 90 96.90(1) 90 1507(1) 1.761 4 293(2) 1.791 808 7279 2876 (0.0822) 161 1.005 0.0609 0.1271 0.520

C30H66S6Ag2Cl2O8 1033.83 0.26 × 0.22 × 0.16 trigonal R-3 11.735(2) 11.735(2) 28.352(6) 90 90 120 3382(1) 1.523 3 293(2) 1.305 1602 5377 1556 (0.0423) 77 1.033 0.0362 0.0864 0.470

C11H24S2AgClO4 427.74 0.30 × 0.25 × 0.20 monoclinic P21/n 8.973(2) 11.276(3) 17.260(5) 90 94.843(5) 90 1740.1(8) 1.633 4 293(2) 1.557 872 6480 3070 (0.0409) 178 1.023 0.0496 0.1402 0.973

C18H39S3AgClO4 558.99 0.24 × 0.20 × 0.18 monoclinic P21/n 10.971(9) 13.75(1) 17.29(2) 90 90.98(1) 90 2608(4) 1.424 4 293(2) 1.134 1164 9125 4594 (0.0638) 253 0.979 0.0477 0.0849 0.359

C13H28S2AgClO4 455.79 0.40 × 0.36 × 0.18 triclinic P-1 9.316(4) 9.699(5) 11.033(5) 72.942(7) 87.615(7) 85.065(7) 949.3(8) 1.595 2 293(2) 1.432 468 5465 3844 (0.0201) 197 1.040 0.0349 0.0844 0.397

C21H45S3AgClO4 601.07 0.30 × 0.28 × 0.26 monoclinic P21/n 10.378(2) 14.131(3) 20.043(4) 90 102.37(3) 90 2871(1) 1.391 4 293(2) 1.036 1260 11736 5058 (0.0533) 271 1.003 0.0765 0.2737 1.435

pellet, cm-1): 2965m, 1964w, 1461m, 1369m, 1089s, 752w, 620s. 1H NMR (CD3OD): δ 1.46 (s, 18H, -C(CH3)4), 3.30 (s, 2H, S-CH2-S). Decomposition temperature: 108 °C. {[Ag(L2)1.5]ClO4}n 2. Yield: 58%. Anal. Calcd. for C15H33S3AgClO4: C, 34.85; H, 6.39. Found: C, 34.74; H, 6.52. IR (KBr pellet, cm-1): 2964m, 2021w, 1684w, 1462m, 1372m, 1101s, 759w, 620m. 1H NMR (CD3OD): δ 1.46 (s, 18H, -C(CH3)4), 3.13 (t, 4H, S-CH2). Decomposition temperature: 161 °C. [(AgL3)ClO4]2 3. Yield: 67%. Anal. Calcd. for C11H24S2AgClO4: C, 30.89; H, 5.66. Found: C, 30.68; H, 5.79. IR (KBr pellet, cm-1): 2965m, 2018w, 1636w, 1466m, 1370m, 1098s, 726w, 620s. 1H NMR (CD3OD): δ 1.50 (s, 18H, -C(CH3)4), 2.31 (t, 2H, C-CH2-C), 3.08 (t, 4H, S-CH2). Decomposition temperature: 174 °C. {[Ag(L4)1.5]ClO4}n 4. Yield: 69%. Anal. Calcd. for C18H39S3AgClO4: C, 38.68; H, 7.03. Found: C, 38.51; H, 7.24. IR (KBr pellet, cm-1): 2960m, 2030w, 1630w, 1461m, 1372m, 1107s, 724w, 621m. 1H NMR (CD3OD): δ 1.44 (s, 18H, -C(CH3)4), 1.89 (t, 4H, C-CH2), 2.84 (t, 4H, S-CH2). Decomposition temperature: 169 °C. [(AgL5)ClO4]2 5. Yield: 64%. Anal. Calcd. for C13H28S2AgClO4: C, 34.26; H, 6.19. Found: C, 34.35; H, 6.08. IR (KBr pellet, cm-1): 2964m, 2023w, 1697m, 1463m, 1375m, 1098s, 753w, 621s. 1H NMR (CD3OD): δ 1.63 (s, 18H, -C(CH3)4), 1.66 (t, 2H, C-CH2-C), 1.76 (t, 4H, C-CH2), 2.87 (t, 2H, S-CH2). Decomposition temperature: 157 °C. {[Ag(L6)1.5]ClO4}n 6. Yield: 54%. Anal. Calcd. for C21H45S3AgClO4: C, 42.06; H, 7.57. Found: C, 42.20; H, 7.39. IR (KBr pellet, cm-1): 2939m, 2033w, 1633w, 1460m, 1367m, 1112s, 738w, 621m. 1H NMR (CD3OD): δ 1.49 (s, 18H, -C(CH3)4), 1.56 (t, 4H, C-CH2-C), 1.80 (t, 4H, C-CH2), 2.89 (t, 4H, S-CH2). Decomposition temperature: 178 °C. Safety Note. Although we experienced no problems with the compounds reported in this work, perchlorate salts of metal complexes with organic ligands are potentially explosive and should be handled with great caution. X-ray Structure Determination. Single-crystal X-ray diffraction measurements for 1-6 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 298(2) K. The determination of unit cell parameters and data collections was performed with MoKR radiation (λ ) 0.71073 Å). Unit cell dimensions were obtained with leastsquares refinements. The program SAINT12 was used for integration of the diffraction profiles. All the structures were solved by direct methods combining successive difference Fourier syntheses using the SHELXS program of the SHELXTL package and refined with SHELXL.13 The final refinement was performed by full matrix least-squares methods with

Table 2. Selected Bond Lengths (Å) and Angles (deg) for 1-6a 1 Ag(1)-S(1) Ag(1)-S(2)* S(1)-Ag(1)-S(2)* 2 Ag(1)-S(1) S(1)-Ag(1)-S(1)* 3 Ag(1)-S(1) Ag(1)-S(2) S(1)-Ag(1)-S(2) 4 Ag(1)-S(1) Ag(1)-S(3) S(1)-Ag(1)-S(3) S(3)-Ag(1)-S(2)* 5 Ag(1)-S(1) Ag(1)-S(2)* S(1)-Ag(1)-S(2)* 6 Ag(1)-S(1) Ag(1)-S(2) S(1)-Ag(1)-S(2) S(1)-Ag(1)-S(3) S(2)-Ag(1)-S(3)

2.432(2) 2.397(2) 160.7(9)

Ag(1)-O(1) Ag(1)-O(4)

2.662(2) 2.760(2)

2.410(2) 2.414(2) 162.4(5)

Ag(1)-O(1)

2.941(2)

2.577(2) 2.560(2) 115.2(4) 124.0(8)

Ag(1)-S(2)* Ag(1)-O(1) S(1)-Ag(1)-S(2)*

2.470(1) 2.464(1) 151.0(9)

Ag(1)-O(1) Ag(1)-O(4)

2.490(3) 2.530(3) 134.9(9) 118.4(1) 95.90(2)

Ag(1)-S(3) Ag(1)-O(1) O(1)-Ag(1)-S(1) O(1)-Ag(1)-S(2) O(1)-Ag(1)-S(3)

2.527(5) 119.6(1)

2.560(2) 2.711(2) 117.9(6) 2.638(1) 2.783(1) 2.573(3) 2.470(9) 97.2(3) 110.4(3) 92.5(4)

a Symmetry codes: 1, *: x, -y + 3/2, z - 1/2; 4, *: -x + 1, -y + 1, -z + 1; 5, *: -x + 1, -y, -z + 1.

anisotropic thermal parameters for non-hydrogen atoms on F2. The hydrogen atoms were added theoretically and riding on the concerned atoms and refined with fixed thermal factors. Crystallographic data and experimental details for structural analyses are summarized in Table 1. Selected bond lengths and angles are listed in Table 2.

Results and Discussion Syntheses and General Characterization. The six AgI complexes 1-6 were prepared by a similar reaction of AgClO4‚H2O with 2 equiv of related ligands L1-L6 in chloroform/acetone solution by the ether diffusion method. Elemental analyses reveal that the components of these complexes are [(AgL1)ClO4]n (1), {[Ag(L2)1.5]ClO4}n (2), [(AgL3)ClO4]2 (3), {[Ag(L4)1.5]ClO4}n (4), [(AgL5)ClO4]2 (5), and {[Ag(L6)1.5]ClO4}n (6), respec-

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Figure 1. (a) View of the l-D chain of 1 with the crystallographic asymmetric unit labeled and (b) the double chain structure of 1 linked by perchlorate.

tively, being consistent with the crystallographic results. IR spectra of the complexes are similar and show the characteristic vibration of S-C at 720-760 cm-1, and the existence of ClO4- is also confirmed. The 1H NMR spectra of the complexes show no signal of coupling to the AgI nuclei. All crystals of the complexes are airstable but are moderately sensitive to light, and complex 1 darkens rapidly in solution in daylight. The complexes are solvable in DMF, methanol, and acetonitrile, slightly soluble in acetone and ethanol but insoluble in water. Description of Crystal Structures. [(AgL1)ClO4]n 1. The structure of 1 consists of -L1-Ag-L1-Ag- polymeric cation chains running in the [001] direction and perchlorate anions that weakly coordinate to AgI ions. Each AgI center is coordinated to two sulfur atoms of two distinct L1 and a pair of oxygen atoms from two ClO4-. The Ag-S bond distances of 2.432(2) and 2.397(2) Å are in the normal range of such complexes,8a and the Ag-O bond lengths are 2.662(6) and 2.760(6) Å, respectively, indicating weak coordination of ClO4-. The S-Ag-S angle of 160.7(8)° deviates from 180° for linear twocoordinated AgI ion probably because of the weak coordination of ClO4-. The AgI centers are linked by a pair of sulfur atoms of L1 to form a 1-D zigzag chain running in the [001] direction (Figure 1a), with an intrachain Ag‚‚‚Ag separation of 5.356(6) Å. In addition, the ClO4- also acts as bridges to link adjacent AgI centers to form eight-membered macrometallacycles; thus, the structure can be considered as a double-bridge chain (Figure 1b). Two tert-butyl groups of each ligand and ClO4- are arranged alternately in two sides of the -L1-Ag-L1-Ag- chain probably because of steric crowding. {[Ag(L2)1.5]ClO4}n 2. Complex 2 is a 2-D (6,3) coordination network. The AgI center, with a 3-fold axis passing through it, is coordinated to three sulfur atoms

Figure 2. (a) View of the coordination environment of Ag in 2, (b) the 2-D (6,3) network along ab plane in 2, and (c) the stacking of layers in 2. The tert-butyl groups were omitted for clarity.

from different ligands (Figure 2a). Thus, AgI ion is in a trigonal coordination geometry with the Ag-S bond length of 2.527(5) Å and S-Ag-S bond angle of 119.6(1)°. Furthermore, one oxygen atom of ClO4- weakly coordinates to the AgI center in a 3-fold axis position with the Ag(1)-O(1) distance of 2.797(4) Å, which induces the AgI atom to deviate slightly from the S3 plane of 0.159(3) Å. In 2, each ligand binds to two AgI centers through the S atoms, and each AgI center is coordinated by three L2 to form centro-symmetric hexagonal 30-membered [Ag6L26] macrometallacyclic units, in which six AgI centers locate at two different planes, up and down alternately. The distance of adjacent Ag atoms is 7.022(4) Å, and the S‚‚‚S distance in L2 is 4.359(4) Å. Eventually, the macrometallacyclic

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Figure 3. (a) View of the dinuclear structure of 3 with the crystallographic asymmetry unit labeled and (b) view of the molecular structure of 3 showing the weak coordination of perchlorate.

unit extends out in the a and b directions to form a 2-D (6,3) network (Figure 2b,c). In addition, the tert-butyl groups of the ligand are located alternately up and down the sheet probably to reduce steric hindrance. Compound 2 has the similar structural features with the previously reported complex {[Ag(L8)1.5]ClO4}n (8) (L8 ) bis(phenylthio)ethane).8e Each complex comprises an infinite 2-D network with a (6,3) topology containing 1:1.5 of Ag/L, but there are a few differences in the coordination configuration around the AgI center and the shape of macrometallacycles because of the difference of terminal groups of the two ligands. It should also be noted that in 2, the 2-D layers stack in an ABAB sequence (Figure 2c) along the c axis, and the face-toface stacking of such sheets does not show substantial channels when viewed down the stacking direction because adjacent layers move each other a 1/2 macrometallacycle unit in the a or b direction sequentially. [(AgL3)ClO4]2 3. The structure of 3 consists of a dimeric cation and ClO4-. Each AgI center is coordinated to two sulfur atoms from two distinct L3 (Figure 3a). Both Ag-S bond lengths are almost equal [2.410(2) and 2.414(2) Å]. The S-Ag-S angle is 162.44(6)°, deviating from 180° of the linear two-coordinated geometry of the AgI ion because of the weak interaction between the oxygen atom of ClO4- and the AgI atom [the shortest

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Figure 4. (a) View of the dinuclear unit of 4 with the crystallographic asymmetry unit labeled and (b) the 1-D chain structure of 4 showing the packing in the unit cell (perchlorate and tert-butyl groups were omitted for clarity).

Ag‚‚‚O distance is 2.941(5) Å] (Figure 3b). In the dimeric cation, two AgI atoms are linked by two L3 to form a 12-membered macrometallacycle related by a crystallographic center of symmetry with a Ag‚‚‚Ag nonbonded distance of 4.818 Å. The macrometallacycle adopts a chairlike conformation with each pair of tert-butyl groups around one AgI center located at the same side of the mean plane of S(1), S(2), S(1)*, and S(2)* (symmetry code: * -x, -y + 1, -z + 1). The two AgI centers are almost coplanar with S(1)-S(2)-S(1)*-S(2)* (an av. deviation of 0.0009 Å), and two ClO4- attach very weakly to two AgI centers and are located up and down the mean plane of S(1)-S(2)-S(1)*-S(2)*. {[Ag(L4)1.5]ClO4}n 4. The structure of 4 has a 1-D arrangement of a single-double bridging chain. Each AgI center is trigonally coordinated to three sulfur atoms from three distinct L4 ligands with three Ag-S bond lengths of 2.560(2) Å [Ag(1)-S(3) and Ag(1)-S(2*)] for the dinuclear unit and 2.577(2) Å [Ag(1)-S(1)] for the single bridging unit. The sum of three S-Ag-S bond angles is 357.2(6)°, which is near 360° for the trigonal plane coordination geometry as one oxygen atom of ClO4- weakly coordinates to the AgI center [the Ag(1)O(1) distance is 2.711(5) Å]. Two AgI centers are bridged by two L4 to form a 14-membered macrometallacycle (Figure 4a), and each AgI center is further linked by the ligands to form a single-double bridging chain (Figure 4b). The Ag‚‚‚Ag distances within the ring and in single

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Figure 6. (a) View of the dinuclear unit of 6 with the crystallographic asymmetry unit labeled and (b) the 1-D chain structure of 6 showing the packing in the unit cell (perchlorate and tert-butyl groups were omitted for clarity).

Figure 5. (a) View of the dinuclear structure of 5 with the crystallographic asymmetry unit labeled and (b) view of the structure of 5 showing the weak coordination of perchlorate.

bridging units are 7.571(5) and 8.690(5) Å, respectively. In 4, the binuclear unit is similar to that of [Ag2L3]2, but the distances between the oxygen atoms of the ClO4- and AgI ions are different: a long-range interaction for 3, weak monodentate coordination for 4. [(AgL5)ClO4]2 5. The structure of 5 shows that it is also a dinuclear compound, in which two tetrahedrally coordinated AgI centers are linked by L5 ligands to form a 16-membered ring (Figure 5a). The bond angles

around the AgI center are in the range of 94.3(4)-151.0(9)°, and the Ag-S and Ag-O bond lengths are 2.464(5)-2.470(5) and 2.638(5)-2.783(5) Å, respectively. Each ClO4- weakly coordinates to metal center in a rare µ2 bridging mode through two oxygen atoms to form an eight-membered ring in which the mean plane of Cl(1)Ag(1)-Ag(1)*-Cl(1)* makes a 74.9(5)° dihedral angle with the mean plane formed by Ag(1), S(1), S(2), S(1)*, S(2)*, and Ag (2)* (symmetry code: * -x + 1, -y, -z + 1). As that in 3, the macrometallacycle of Ag2S4 adopts also chairlike shape with a pair of tert-butyl groups at the back of the chair and another pair at the feet. Both macrocycles of Ag2S4 and Ag2O4 make up a centralsymmetric binuclear cage (Figure 5b). In the cage, the

Table 3. Comparisons of the Structures of the AgI (Perchlorate or Tetrafluoroborate) Complexes with Some Structurally Related Dithioether Ligandsa compound 1 2 3 4 5 6 7 8 9 10 11 12 13

formula [(AgL1)ClO

4]n {[Ag(L2)1.5]ClO4}n [(AgL3)ClO4]2 {[Ag(L4)1.5]ClO4}n [(AgL5)ClO4]2 {[Ag(L6)1.5]ClO4}n {[Ag(L7)1.5]ClO4}n {[Ag(L8)1.5]ClO4}n {[Ag(L9)2]BF4}n9 {[Ag(L10)1.5]ClO4}n {[Ag(L11)2]ClO4}n [(AgL12)ClO4]2 [(AgL13)BF4]n

structural features

ref

1-D single-bridge zigzag chains 2-D (6,3) topology layers, hexagonal starlike, [30]-rings dinuclear, [12]-rings 1-D single, double-bridge chains, [14]-rings dinuclear, [16]-rings 1-D single, double-bridge chains, [18]-rings 3-D (10,3)-a net 2-D (6,3) topology layers, clover-like, [30]-rings 3-D net 2-D (6,3) topology layers, honeycomblike, [42]-rings 2-D (4,4) topology layers, [32]-rings dinuclear, [18]-rings 1-D (S, µ2-S), double-bridge chains

this paper this paper this paper this paper this paper this paper 8c 8e 8a 8b 8d 8f 8a

a Ligands: L7 ) bis(phenylthio)methane, L8 ) bis(phenylthio)ethane, L9 ) bis(phenylthio)propane, L10 ) bis(phenylthio)butane, L11 ) bis(phenylthio)pentane, L12 ) bis(phenylthio)hexane, and L13 ) bis(methylthio)butane.

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Ag‚‚‚Ag distance is 5.221(5) Å, which is shorter than that in 3 and 4 because of a pair of AgI centers in 5 being linked further by ClO4-. The structure of the complex is similar to that of 3 in the moiety of the dinuclear macrometallacycle, but the Ag-O bond length is shorter than that in 3. This indicates that the interaction of the metal center and perchlorate in 5 is stronger than that in 3 because L5 is more flexible than L3. The cage structure of 5 is also similar with the analogous complex {[Ag(L12)]ClO4}2 (12) (L12 ) bis(phenylthion)hexane),8f but in the latter the ClO4coordinates strongly to the AgI center. {[Ag(L6)1.5]ClO4}n 6. The structure of 6 is similar to that of 4. A view of the dinuclear unit is shown in Figure 6a. A pair of AgI atoms is linked by two bridging L6 ligands to form [Ag2L6]2 binuclear units with 18membered macrometallacycles. Adjacent [Ag2L6]2 units are further linked by other ligands to form a singledouble bridging chain (Figure 6b). The Ag‚‚‚Ag distances within the ring unit and in the single bridge are 9.287 and 9.803 Å, respectively. Each AgI center is coordinated to three sulfur atoms from three distinct ligands and an oxygen atom of ClO4- exhibiting a strongly distorted tetrahedral coordination geometry with the bond angles ranging from 92.5(4) to 134.90(9)°. It should be noted that in 6 the Ag-O bond distance of 2.470(9) Å lies in the range of the normal coordination bonds,10 which is different from those weak coordinations of oxygen atoms in other complexes. Comparing with 4, another difference is the packing model of 1-D chains; in 4 all 1-D chains are arranged in the same direction along the crystallographic a axis (Figure 4b), while in 6 those chains are disposed crossly in an interlaced pattern in the ab plane (Figure 6b). In summary, a series of novel AgClO4 complexes with flexible dithioether ligands with different spacers have been described. On the basis of this work and other reported AgI coordination compounds with bis(phenylthioether)alkane or bis(methylthioether)alkane ligands (Table 3), we may come to the following conclusions: (i) the ligand spacers have great influence on the structures of such complexes, (ii) the terminal groups of the ligands also play important roles in controlling the structures of such complexes, and (iii) the Ag-S bond distances are related to the number of S atoms around Ag and the coordination geometries of the metal centers. Acknowledgment. The work was financially supported by the Outstanding Youth Foundation of NSFC (No. 20225101).

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Supporting Information Available: Six X-ray crystallographic files in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

References (1) For recent reviews, see: (a) Hollingsworth, M. D. Science 2002, 29, 2410. (b) Evans, O. R.; Lin, W.-B. Acc. Chem. Res. 2002, 35, 511. (c) Gade, L. H. Acc. Chem. Res. 2002, 35, 575. (d) Seidel, S. R.; Stang, P. J. Acc. Chem. Res. 2002, 35, 972. (e) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629. (f) Eddaoudi, M. D.; Moler, B.; Li, H.-L.; Chen, B.-L.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319. (g) Fujita, M.; Umemoto, K.; Yoshizawa, M.; Fujita, N.; Kusukawa, T.; Biradha, K. Chem. Commun. 2001, 509. (h) Swiegers, G. F.; Malefetse, T. J. Chem. Rev. 2000, 100, 3483. (i) Braga, D. J. Chem. Soc., Dalton Trans.

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