Novel Noninterpenetrating (3,6) Topological Coordination Networks Assembled from Flexible meso-Bis(Sulfinyl) Bridging Ligands Jian-Rong Li,† Ruo-Hua Zhang,† and Xian-He Bu*,†,‡ Department of Chemistry, Nankai University, Tianjin 300071, P. R. China, and State Key Lab of Structural Chemistry, Fuzhou 350002, P. R. China
CRYSTAL GROWTH & DESIGN 2004 VOL. 4, NO. 2 219-221
Received July 24, 2003
ABSTRACT: Two novel coordination polymers exhibiting an unusual noninterpenetrating six-connected 2D (3,6) topological network with triangular microporous grids assembled from ZnII and two structurally related flexible meso-bis(sulfinyl) ligands, {[Zn(L1)3](ClO4)2}∞ 1 and {[Zn(L2)3](ClO4)2‚CHCl3}∞ 2 (L1 ) meso-1,4-bis(ethylsulfinyl)butane; L2 ) meso-1,4-bis(butylsulfinyl)butane) have been synthesized and characterized by X-ray diffraction. Crystal data for 1: rhombohedral, space group R3 h c, a ) b ) 10.301(3), c ) 65.44(3) Å, V ) 6014(4) Å3, and Z ) 6. Crystal data for 2: rhombohedral, space group R3 h , a ) b ) 10.593(2), c ) 49.319(9) Å, V ) 4793(2) Å3, and Z ) 3. Construction of coordination networks with fascinating structural topologies has spawned an explosion of coordination compounds in recent years due to their potentials as functional materials.1 Concurrent with this has been the development of multidimensional frameworks based primarily upon linking metal centers with rigid linear ligands,2 of which the structures could be predicted in great degree based on the coordination geometry of metal ions and the conformation of ligands. However, less effort has been focused on the use of flexible ligands,3 which, with inconstant space conformations, are prone to change their conformations in different conditions. Our previous studies4 have shown that bis(sulfinyl) compounds are good bridging ligands for the construction of coordination polymers with both lanthanide and transitional metals, and these studies have resulted in many extended assemblies including four-,4b five-,4c and sixconnected4a topological networks. We have further substantiated that the network topology and the cavities of the coordination networks can be controlled by varying the chain length of the ligands.4a Herein, we report two novel 2D coordination networks, {[Zn(L1)3](ClO4)2}∞ 1 and {[Zn(L2)3](ClO4)2‚CHCl3}∞ 2, exhibiting rare six-connected 2D (3,6) topology5 with triangular grids, constructed from ZnII and two flexible structurally related bis(sulfinyl) ligands L1 and L2 (Chart 1). Chart 1
L1
L2
The ligands and were synthesized by adaptation of a literature procedure.6 The colorless crystals of 1 and 2 suitable for X-ray diffraction were obtained by diffusing an acetone solution of Zn(ClO4)2 to a chloroform solution of L (L1 or L2). Both crystals are air stable at room temperature, and decomposition of 1 occurs at above 233 °C, while 2 loses 10.5% total weight in 112 °C for the removal of a CHCl3 molecule per formula unit (calculated: 10.1%), and decomposition occurs at 227 °C. The IR spectra of 1 and 2 indicate the presence of strong SdO stretching vibrations at 989 and 980 cm-1, respectively, suggesting the coordination of the bis(sulfinyl) oxygen atoms to ZnII.7 * Corresponding author. E-mail:
[email protected]. Fax: +86-2223502458. † Nankai University. ‡ State Key Laboratory of Structural Chemistry.
Figure 1. Structures of 2D (3,6) topology networks in 1 and 2 with hydrogen atoms, perchlorate ions, and terminal groups of ligands omitted for clarity: (a) ball-and-stick mode; (b) space-filling mode.
Single-crystal X-ray diffraction analyses8 reveal that 1 and 2 have the similar noninterpenetrating 2D (3,6) topological networks consisting of six-coordinated ZnII nodes (Figure 1). The asymmetric unit of 1 consists of 1/6 unit of ZnII, 1/2 L1 coordinated to ZnII and 1/3 ClO4- to balance the charge. For 2, the only difference with 1 is that there is 1/6 unit of CHCl3 molecule in its asymmetric unit. Each ZnII center coordinates to six O donors of six independent ligands in regular octahedral geometry with six equal Zn-O bond lengths of 2.094(4) and 2.099(3) Å in 1 and 2, respectively. It should be noted that six-coordinated ZnII complexes with octahedral geometry are common, but regular octahedral geometry is rare.9 Each ZnII in 1 and 2
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Communications and the conformations of ligands. Further studies on the complexes of other structurally related flexible bis(sulfinyl) ligands are in progress in our lab. Acknowledgment. The work was financially supported by the Outstanding Youth Foundation of NSFC (No. 20225101). We thank Dr. Ming-Liang Tong and Prof. Susumu Kitagawa for very helpful discussions. Supporting Information Available: The synthesis and characterization of ligands L1 and L2, complexes 1 and 2, the luminescence emission spectra of the two complexes, and crystallographic data in CIF. This material is available free of charge via the Internet at http://pubs.acs.org.
Figure 2. Interlayer stacking form in 1 and 2.
References is linked to six other ZnII by the bis(sulfinyl) ligands to generate unique six-connected 2D (3,6) coordination networks containing 27-membered macrometallacycles with regular trigonal microporous grids formed by three metal centers and three L ligands. The distances of Zn-Zn in the trigonal grid are 10.301 Å for 1 and 10.593 Å for 2. In 1 and 2, all ligands are crystallographically identical showing a meso configuration and trans conformation with i symmetry located at the center of the butylenes. In addition, perchlorate anions have been partially infixed into the triangular grids with an up-and-down manner in the same layer in 1 and 2, which may be regarded as a template, and chloroform molecules are located between layers in 2. It is interesting and noteworthy that the octahedrally coordinated metal ions usually yield a cubic lattice related to R-polonium.1f,10 However, the present case exhibits a 2D six-connected (3,6) topology in good contrast to the wellknown three-connected (6,3) networks.3a,11 The flexible ligands used here take an up-and-down linkage form (or trans-trans form based on one ligand bridging two metal ions) and stretch out to generate such layer structure. The high symmetry with such close arrangement of molecules may effectively prevent interpenetrating. In the two complexes, face-to-face stacking of such layers does not afford a triangular channel or other substantial channels because adjacent layers move each other by 1/2 triangular unit in the a or b direction sequentially (Figure 2). The comparison of the structures of 1 and 2 gives insight into the influence of the terminal groups to the crystal structures. In 2, the larger butyl group of L2 sustains wider separation between layers (16.439(7) Å), which allows the inclusion of guest molecules, while in 1 the distance between adjacent layers (10.906(7) Å) is much shorter than that in 2, and no solvent molecule can be included. Some other topology networks, such as (4,4),4a,b (3/4,5)4c with this kind of ligand have been reported by us; these structural differences may be attributed to the differences of metal coordination geometry, or the spacers and terminal groups of the ligands. The luminescent properties of 1 and 2 were measured in the solid state (see Supporting Information). For 1, an emission at 512 nm was observed, but for 2 the emission appeared at 467 nm. The differences of the emission for 1 and 2 and the origin of these emissions are still under investigation in our lab. In conclusion, two novel coordination networks exhibiting rare noninterpenetrating 2D (3,6) networks with triangular grids have been constructed by two structurally related flexible bis(sulfinyl) ligands and ZnII. Such a structural type is the first example in bis(sulfinyl) complexes. The bulkiness of the terminal groups of ligands was found to change the distance between layers of the complexes, and the structure of the complexes is evidently controlled by the coordination geometry of the metal ions
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