[MoOS3Cu3]-Based Coordination Polymers from the Same

Formation of Four Different [MoOS3Cu3]-Based Coordination Polymers from the Same Components via Four Synthetic Routes Jin-Xiang Chen,†,‡ Xiao-Yan Tang,† Yang Chen,† Wen-Hua Zhang,† Ling-Ling Li,† Rong-Xin Yuan,§ Yong Zhang,† and Jian-Ping Lang*,†

CRYSTAL GROWTH & DESIGN 2009 VOL. 9, NO. 3 1461–1469

College of Chemistry, Chemical Engineering and Materials Science, Suzhou UniVersity, Suzhou 215123, People’s Republic of China, School of Pharmaceutical Science, Southern Medical UniVersity, Guangzhou, 510515, People’s Republic of China, and Jiangsu Laboratory of AdVanced Functional Materials, Changshu Institute of Technology, Changshu 215500, People’s Republic of China ReceiVed August 15, 2008; ReVised Manuscript ReceiVed NoVember 23, 2008

ABSTRACT: Assembly of different [MoOS3Cu3]-based coordination polymers from the same components ([(n-Bu)4N]2[MoOS3Cu3(NCS)3] (1) and 4,4′-bypyridine (4,4′-bipy)) via different synthetic approaches has been investigated. Treatment of 1 with 4,4′-bipy (molar ratio ) 1:1) in aniline afforded {[{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)3] · 6(ani)}n (ani ) aniline) (2), while solid state reaction of 1 with equimolar 4,4′-bipy at ambient temperature followed by extraction with aniline yielded {[(n-Bu)4N]2[{MoOS3Cu3(NCS)2}2(4,4′-bipy)3] · 2(ani)}n (3). Diffusion reactions of an aniline solution of 1 with an aniline solution of 4,4′-bipy in a straight or zigzag glass tube resulted in the formation of {[MoOS3Cu3(NCS)(4,4′-bipy)2.5] · 3(ani)}n (4) and {[(MoOS3Cu3)2(NCS)(µ-NCS)(4,4′-bipy)4.5] · 7(ani)}n (5), respectively. Compounds 2-5 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compounds 2 consists of a 1D zigzag chain in which the dimeric [{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)2] units are linked by single 4,4′-bipy bridges, while 3 possesses a one-dimensional spiral chain built of the dimeric [{MoOS3Cu3(NCS)2}2(4,4′-bipy)2] units bridged by 4,4′-bipy ligands. Compound 4 contains a three-dimensional (3D) 3-fold interpenetrated network in which each [MoOS3Cu3] core acts as a tetrahedral four-connecting node to interconnect four other equivalent ones via single and double 4,4′-bipy bridges. Compound 5 has a unique 3D 2-fold interpenetrated network in which the [MoOS3Cu3] cores work as trigonal-pyramidal four- and tetragonal-pyramidal five-connecting nodes to link other equivalent cores through single thiocyanate bridges and single and double 4,4′-bipy bridges. The results may provide interesting insights into effects of synthetic approaches on the construction of cluster-based coordination polymers. Introduction Construction of cluster-based coordination polymers from the cluster precursors has recently received much attention not only due to their aesthetically appealing topological structures but also due to their potential applications in advanced materials.1-9 Among them, one interesting category is those of Mo(W)/Cu/S cluster-based compounds9 that are derived from the preformed Mo(W)/Cu/S clusters.10-12 Such compounds are usually prepared through the routine solution reactions of certain cluster precursors with various multitopic ligands in common organic solvents. It is noted that these reactions sometimes suffer from the instant and heavy precipitation of the products due to their low solubilities in solvents. This makes further structural characterization of the products quite difficult and thus limits the understanding and development of the chemistry of this type of cluster-based compounds. Fortunately, several other synthetic approaches for these cluster-based species, including solid state reactions at low-heating temperatures,12a,b,13 diffusion reactions in a glass tube (straight or zigzag),9b,e-g,i,k and solvothermal reactions,14,12h have been developed. However, each of the aforementioned methods is always employed for special cluster-based assemblies, and no reports have been devoted to explore the construction of cluster-based arrays from the same components via more than three different synthetic routes. * To whom correspondence should be addressed. Fax & Tel: Int. code +86 512 65880089; e-mail: [email protected]. † Suzhou University. ‡ Southern Medical University. § Changshu Institute of Technology.

On the other hand, we have been engaged in the assembly of Mo(W)/Cu/S-based coordination polymers from the preformed Mo(W)/Cu/S clusters.9 In our previous reports, we explored how the factors such as the geometry of the precursor clusters,9b,c,e,f solvents,9j,k ligand symmetry,9g molar ratios of the components,9k etc., affect the construction of cluster-based arrays. In several cases, the same components were found to produce the different products via two different synthetic methods. For example, reactions of [PPh4][Cp*MoS3(CuNCS)3] (Cp* ) pentamethylcyclopentadienyl) in aniline with a suspension of 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) in CH2Cl2 at ambient temperature for three days afforded a discrete tetranuclear cluster [PPh4]2[Cp*MoS3(CuNCS)3(µ3-Cl)]. However, solid state reactions of the same components at 100 °C for 12 h followed by extraction with aniline yielded one polymeric cluster {[Cp*MoS3Cu3(tpt)(ani)(NCS)2] · 0.75ani · 0.5H2O}n (ani ) aniline).9g This result encouraged us to consider the following question: what would be produced if each of the aforementioned methods (routine solution reaction, solid state reaction at lowheating temperatures, and diffusion reaction in a straight or zigzag glass tube) is employed for the same reaction? Therefore we carefully chose a known cluster [(n-Bu)4N]2[MoOS3Cu3(NCS)3] (1)15as a precursor and 4,4′-bipyridine (4,4′-bipy) as a ditopic ligand and aniline as a solvent, and carried out their reactions via these approaches, and isolated four Mo/Cu/S cluster-based polymers {[{MoOS3Cu3(NCS)(ani)2}2(4,4′bipy)3] · 6(ani)}n (2), {[(n-Bu)4N]2[{MoOS3Cu3(NCS)2}2(4,4′bipy)3] · 2(ani)}n (3), {[MoOS3Cu3(NCS)(4,4′-bipy)2.5] · 3(ani)}n (4), and {[(MoOS3Cu3)2(NCS)(µ-NCS)(4,4′bipy)4.5] · 7(ani)}n (5). The results represent a first example in which the same components produced four different cluster-based species through four different synthetic routes.

10.1021/cg800896k CCC: $40.75  2009 American Chemical Society Published on Web 01/12/2009

1462 Crystal Growth & Design, Vol. 9, No. 3, 2009

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Table 1. Summary of Crystallographic Data for 2-5 compounds

2

3

4

5

formula fw crystal system space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) Z T (K) Dcalc (g · cm-3) F(000) µ (Mo KR, mm-1) total no. of reflns no. of unique reflns no. of obsd reflns Ra (I > 2.00σ(I)) wRb GOFc ∆Fmax/∆Fmin (e/Å3)

C92H94Cu6Mo2N18O2S10 2313.45 triclinic P1j 15.7872(2) 17.1818(3) 19.9734(4) 64.672(8) 85.659(1) 89.496(3) 4881.3(4) 2 193(2) 1.574 2348 1.757 47033 17646 12838 0.0795 0.1959 1.115 1.245/-1.318

C78H110Cu6Mo2N14O2S10 2169.68 monolinic P21 9.901(2) 25.752(5) 18.883(4)

C44H41Cu3MoN9OS4 1126.66 monolinic P21/c 9.9998(17) 27.294(3) 17.664(3) 75.305(11) 100.510(9) 67.409(8) 4740.3(12) 4 193(2) 1.579 2276 1.807 43916 10189 9726 0.0947 0.1976 1.127 1.086/-1.353

C89H85Cu6Mo2N18O2S8 2268.49 triclinic P1j 17.1042(16) 18.3052(10) 20.336(2)

a R ) |Fo| - |Fc||Fo|. b wR ) {w(Fo2 - Fc2)2/w(Fo2)2}1/2. numbers of parameters refined.

97.90(3) 4769.0(17) 2 193(2) 1.511 2220 1.833 22810 13785 8161 0.0953 0.1547 1.139 1.005/-1.016 c

86.882(12) 5651.7(8) 2 193(2) 1.333 2294 1.516 55016 20583 13781 0.0997 0.1790 1.056 1.203/-1.108

GOF ) {w((Fo2 - Fc2)2)/(n - p)}1/2, where n ) number of reflections and p ) total

Herein we report their synthesis and structural characterization of 2-5. Materials and Methods Compound 1 was prepared according to the literature method.15 Other chemicals and reagents were obtained from commercial sources and used as received. Aniline was freshly distilled under reduced pressure, while other solvents were predried over activated molecular sieves and refluxed over the appropriate drying agents under argon. The elemental analyses for C, H, and N were performed on an EA1110 CHNS elemental analyzer. The IR spectra were recorded on a Nicolet MagNa-IR 550 as KBr disk (4000-400 cm-1). Powder X-ray diffraction (PXRD) patterns were collected on a Rigaku D/MAX-IIIC powder diffractometer with Cu KR radiation) (1.54956 Å). {[(MoOS3Cu3(NCS)(ani)2)2(4,4′-bipy)3] · 6(ani)}n (2). To a solution containing 1 (0.526 g, 0.5 mmol) in aniline (4 mL) was added a solution of 4,4′-bipy (0.088 g, 0.5 mmol) in aniline (2 mL). Some dark red precipitate was developed immediately. The resulting mixture was stirred at ambient temperature for 10 min and then filtered. Dark red crystals of 2 were isolated by layering Et2O (5 mL) onto the filtrate for one week, which were collected by filtration and washed with aniline/ Et2O (v/v ) 1: 4) and dried in vacuo. Yield: 0.247 g (43% based on Mo). Anal. Calcd. for C92H92Cu6Mo2N18O2S8: C, 47.81; H, 4.02; N, 10.91. Found: C, 48.03; H, 3.96; N, 11.18. IR (KBr disk, cm-1): 2088s, 1601s, 1411s, 1217s, 1066w, 904s, 807s, 631s, 441m. {[(n-Bu)4N]2[(MoOS3Cu3(NCS)2)2(4,4′-bipy)3] · 2(ani)}n (3). A red fine powder of 1 (0.526 g, 0.5 mmol) and a white fine powder of 4,4′bipy (0.088 g, 0.5 mmol) was mixed in an agate mortar, and then firmly ground at room temperature for 10 min. During this time, the mixture became slightly moistened and then was extracted by aniline (5 mL). After filtration, layering Et2O (6 mL) onto the filtrate for one week formed dark red crystals of 3, which were collected by filtration and washed with aniline/Et2O (v/v ) 1: 2) and dried in vacuo. Yield: 0.45 g (83% based on Mo). Anal. Calcd. for C78H110Cu6Mo2N14O2S10: C, 43.18; H, 5.11; N, 9.04. Found: C, 43.32; H, 5.18; N, 9.30. IR (KBr disk, cm-1): 2087s, 1601s, 1410s, 1218s, 1065w, 904s, 806s, 628s, 441m. {[MoOS3Cu3(NCS)(4,4′-bipy)2.5] · 3(ani)}n (4). A solution of 1 (0.526 g, 0.5 mmol) in aniline (2 mL) was placed in a straight glass tube (30 cm in length, 7 mm in inner diameter) followed by slow addition of 3 mL of aniline serving as a buffer band. A solution containing 4,4′-bipy (0.088 g, 0.5 mmol) in aniline (1 mL) was slowly layered onto the buffer band. Finally, diethyl ether (5 mL) was carefully layered onto the top solution and then the glass tube was capped with a rubber plug, which was further sealed with parafilm. The glass tube was left to stand at ambient temperature for five days, forming dark

red blocks of 4, which were collected by filtration and washed with aniline and Et2O (v/v ) 1:2) and dried in vacuo. Yield: 0.522 g (93% based on Mo). Anal. Calcd. for C44H41Cu3MoN9OS4: C, 46.90; H, 3.67; N, 11.19. Found: C, 46.67; H, 3.63; N, 11.33. IR (KBr disk, cm-1): 2088s, 1601s, 1410s, 1216s, 1066w, 903s, 806s, 627s, 443m. {[(MoOS3Cu3)2(NCS)(µ-NCS)(4,4′-bipy)4.5] · 7(ani)}n (5). Compound 5 was prepared in a manner similar to that described for 4, using the same amount of components that were loaded in a zigzag tube (30 cm in length, 7 mm in inner diameter). Dark red blocks of 5, which were collected by filtration and washed with cold aniline and Et2O (v/v ) 1:2) and dried in vacuo. Yield: 0.483 g (85% based on Mo). Anal. Calcd. for C89H85Cu6Mo2N18O2S8: C, 47.12; H, 3.78; N, 11.11. Found: C, 47.44; H, 3.89; N, 11.32. IR (KBr disk, cm-1): 2115s, 2081s, 1601s, 1410s, 1216s, 1066w, 901s, 806s, 628s, 440m. X-ray Structure Determination. Crystals of 2-5 suitable for single crystal X-ray analysis were obtained directly from the above preparations. All measurements were made on a Rigaku Mercury CCD X-ray diffractometer by using graphite monochromated Mo KR (λ ) 0.71070 Å). Single crystals of 2-5 were mounted with grease at the top of a glass fiber, and cooled to 193 K in a liquid-nitrogen stream. Cell parameters were refined on all observed reflections by using the program Crystalclear (Rigaku and MSc, Ver. 1.3, 2001). The collected data were reduced by the program CrystalClear, and an absorption correction (multiscan) was applied. The reflection data for 2-5 were also corrected for Lorentz and polarization effects. The crystal structures of 2-5 were solved by direct methods and refined on F2 by full-matrix least-squares methods using the SHELXTL software package.16 All non-hydrogen atoms were refined anisotropically. For 2, each of the four aniline solvent molecules lies on a center of inversion and the two nitrogen atoms were refined with occupancy factor of 0.5 each. Hydrogen atoms of the amine groups of the solvated or coordinated aniline molecules were located from Fourier maps. All other hydrogen atoms were placed in geometrically idealized positions (C-H ) 0.98 Å, with Uiso(H) ) 1.5Ueq(C) for methyl groups; C-H ) 0.99 Å, with Uiso(H) ) 1.2Ueq(C) for methylene groups; C-H ) 0.95 Å, with Uiso(H) ) 1.2Ueq(C) for aromatic rings) and constrained to ride on their parent atoms. The high R values for 3-5 are attributed to the relatively high anisotropic temperature factors for the N and C atoms of some pyridyl groups. A summary of the key crystallographic information and their selected bond lengths for 2-5 were listed in Tables 1 and 2, respectively.

Results and Discussion Synthetic and Spectral Aspects. In our previous papers, we reported employment of aniline as a good solvent for the

[MoOS3Cu3]-Based Coordination Polymers

Crystal Growth & Design, Vol. 9, No. 3, 2009 1463

Table 2. Selected Bond Distances (Å) of 2-5 Compound 2 Mo(1) · · · Cu(1) Mo(1) · · · Cu(3) Mo(2) · · · Cu(5) Mo(1)-O(1) Mo(1)-S(1) Mo(1)-S(3) Mo(2)-S(6) Cu(1)-S(1) Cu(2)-S(1) Cu(3)-S(2) Cu(4)-S(5) Cu(5)-S(5) Cu(6)-S(6) Cu(1)-N(1) Cu(2)-N(3) Cu(3)-N(5) Cu(4)-N(8) Cu(5)-N(9) Cu(6)-N(11)

2.6771(11) 2.7019(11) 2.7073(11) 1.700(5) 2.269(2) 2.265(2) 2.2726(19) 2.259(4) 2.264(2) 2.290(2) 2.274(2) 2.285(2) 2.250(2) 2.125(8) 2.126(7) 2.119(7) 2.067(6) 2.124(7) 2.156(7)

Mo(1) · · · Cu(1) Mo(1) · · · Cu(3) Mo(2) · · · Cu(5) Mo(1)-O(1) Mo(1)-S(1) Mo(1)-S(3) Mo(2)-S(5) Cu(1)-S(1) Cu(2)-S(1) Cu(3)-S(2) Cu(4)-S(4) Cu(5)-S(4) Cu(6)-S(5) Cu(1)-N(1) Cu(2)-N(5) Cu(3)-N(9) Cu(4)-N(10A) Cu(5)-N(8)

2.647(3) 2.657(3) 2.699(3) 1.684(10) 2.280(5) 2.259(6) 2.269(6) 2.246(6) 2.253(6) 2.286(6) 2.231(6) 2.317(6) 2.224(6) 2.028(13) 2.113(15) 2.144(15) 2.088(16) 2.120(14)

Mo(1) · · · Cu(1) Mo(1) · · · Cu(3) Mo(1)-S(1) Mo(1)-S(3) Cu(1)-S(3) Cu(2)-S(3) Cu(3)-S(1) Cu(1)-N(3C) Cu(2)-N(4) Cu(3)-N(5A)

2.7103(11) 2.6772(11) 2.2651(18) 2.2736(18) 2.2945(19) 2.2831(19) 2.277(2) 2.134(6) 2.038(6) 2.075(6)

Mo(1) · · · Cu(1) Mo(1) · · · Cu(3) Mo(2) · · · Cu(5) Mo(1)-O(1) Mo(1)-S(1) Mo(1)-S(3) Mo(2)-S(5) Cu(1)-S(1) Cu(2)-S(1) Cu(3)-S(2) Cu(4)-S(4) Cu(5)-S(4) Cu(6)-S(5) Cu(6)-S(7) Cu(1)-N(5A) Cu(2)-N(9A) Cu(3)-N(3D) Cu(4)-N(2) Cu(5)-N(6)

2.670(3) 2.697(3) 2.666(3) 1.749(16) 2.268(5) 2.276(6) 2.243(7) 2.230(6) 2.270(6) 2.302(6) 2.280(6) 2.240(6) 2.277(5) 2.353(6) 2.11(2) 2.066(19) 2.121(15) 2.086(17) 2.047(18)

Mo(1) · · · Cu(2) Mo(2) · · · Cu(4) Mo(2) · · · Cu(6) Mo(2)-O(2) Mo(1)-S(2) Mo(2)-S(5) Mo(2)-S(7) Cu(1)-S(2) Cu(2)-S(3) Cu(3)-S(3) Cu(4)-S(6) Cu(5)-S(7) Cu(6)-S(7) Cu(1)-N(2) Cu(2)-N(4) C u(3)-N(6) Cu(4)-N(7) Cu(5)-N(10) Cu(6)-N(12)

2.6560(12) 2.6665(11) 2.6751(12) 1.710(5) 2.2666(19) 2.2728(19) 2.257(2) 2.281(2) 2.272(2) 2.281(4) 2.274(4) 2.293(4) 2.290(2) 2.059(6) 2.058(6) 1.979(8) 2.101(7) 1.972(8) 2.038(6)

Compound 3 Mo(1) · · · Cu(2) Mo(2) · · · Cu(4) Mo(2) · · · Cu(6) Mo(2)-O(2) Mo(1)-S(2) Mo(2)-S(4) Mo(2)-S(6) Cu(1)-S(2) Cu(2)-S(3) Cu(3)-S(3) Cu(4)-S(5) Cu(5)-S(6) Cu(6)-S(6) Cu(2)-N(2) Cu(3)-N(7) Cu(4)-N(6) Cu(5)-N(3) Cu(6)-N(4)

2.689(3) 2.662(3) 2.635(3) 1.702(12) 2.260(6) 2.244(6) 2.253(5) 2.236(6) 2.309(6) 2.258(6) 2.295(6) 2.273(6) 2.229(6) 2.139(14) 1.998(15) 1.982(13) 2.085(13) 1.990(12)

Figure 1. (a) Perspective view of the repeating unit of 2 with 50% thermal ellipsoids. Symmetry codes: A, x + 1, y + 1, z; B, x - 1, y - 1, z. (b) Perspective view of the repeating unit of 3 with 50% thermal ellipsoids. Symmetry code: A, x, y, z - 1. All hydrogen atoms are omitted for clarity.

Compound 4 Mo(1) · · · Cu(2) Mo(1)-O(1) Mo(1)-S(2) Cu(1)-S(1) Cu(2)-S(2) Cu(3)-S(2) Cu(1)-N(6) Cu(2)-N(1) Cu(3)-N(2)

2.6972(11) 1.715(5) 2.2645(19) 2.314(2) 2.276(2) 2.2719(19) 1.953(7) 2.053(6) 2.070(6)

Compound 5 Mo(1) · · · Cu(2) Mo(2) · · · Cu(4) Mo(2) · · · Cu(6) Mo(2)-O(2) Mo(1)-S(2) Mo(2)-S(4) Mo(2)-S(6) Cu(1)-S(2) Cu(2)-S(3) Cu(3)-S(3) Cu(4)-S(5) Cu(5)-S(6) Cu(6)-S(6) Cu(1)-N(1) Cu(2)-N(7C) Cu(3)-N(10) Cu(4)-N(11) Cu(5)-N(4) Cu(6)-N(8)

2.664(3) 2.695(3) 2.686(3) 1.767(18) 2.263(5) 2.274(5) 2.261(5) 2.266(7) 2.259(5) 2.286(5) 2.266(6) 2.277(6) 2.275(6) 2.06(3) 2.012(15) 1.965(18) 1.96(3) 2.069(19) 2.017(14)

reactions of [PPh4][Cp*MoS3(CuNCS)3]9g,k with different Ndonor ligands due to its good capability for dissolving the

Figure 2. (a) View of a section of the 1D zigzag chain of 2 (extending along the [100] direction). (b) View of a section of the 1D spiral chain of 3 (extending along the c axis).


Chen et al.

Scheme 1. Reactions of 1 with 4,4′-bipy Using Four Different Synthetic Methods

Mo(W)/Cu/S clusters. Thus we again used aniline as a solvent for the reactions of 1 with equimolar 4,4′-bipy. Some dark red solid was thrown out of the solution within seconds. The solid was insoluble in aniline, MeCN, DMF, DMSO, CH2Cl2, and benzene, and seemed quite messy when we tried to characterize it by elemental analysis, IR spectroscopy and X-ray fluorescence analysis. After filtration, a standard workup resulted in the formation of dark red crystals of 2 in 43% yield (Scheme 1). In this case, aniline worked as a solvent and a ligand. As discussed later in this paper, the resulting product 2 includes aniline as lattice molecules in its crystal and as ligands coordinated to two copper(I) centers in each [MoOS3Cu3] core. On the other hand, in the past two decades, we have developed another synthetic approach, the so-called solid state reactions at low heating temperatures,9b,e-g,i,k,17 to create several dozens of Mo(W)/Cu(Ag)/S clusters and other coordination compounds. In some cases, this technique did generate products in relatively high yields that were remarkably different from those formed in normal solution reactions.9g,13d In this respect, we decided to attempt this type of solid state reaction to see whether it could produce different compounds. Compound 1 and 4,4′-bipy were ground finely in two separate agate mortars, and then they were mixed together and firmly ground at room temperature for 10 min. The resulting dark red solid was extracted by aniline and filtered. Diffusion of Et2O into the

filtrate did not form the previous product 2, but a different product 3 as dark red crystals in 83% yield (Scheme 1). After the structures of 1-3 were examined, one counter [(n-Bu)4N]+ cation and two terminal NCS groups in 1 were retained during this reaction, while all counter cations and two terminal NCS groups in 1 were lost in the case of 2. In the above two cases, we isolated the crystalline products using a straight slender glass tube that contained the aniline solution of the products. Diethyl ether was carefully layered onto the surface of the solution to grow crystals of good quality within one week. Employment of such a slender tube is assumed to be able to avoid the direct and fast mixing of the starting materials, and is sometimes effective for the growth of crystals which otherwise would be insoluble materials in the larger vessels such as beakers and flasks. Then what would happen if the reactions of 1 and 4,4′-bipy were carried out in such a tube? We employed a straight glass tube (30 cm in length, 7 mm in inner diameter) and loaded an aniline solution (2 mL) of 1 into it (see Figure S1, Supporting Information). Careful addition of pure aniline (3 mL) onto the solution followed by addition of an aniline solution (1 mL) of 4,4′-bipy did not cause the instant and thick precipitate. Further addition of Et2O onto the top solution followed by capping the tube by a rubber plug resulted in the formation of 4 as dark red crystals in 93% yield (Scheme 1). The solutions of 1 and 4,4′-bipy automatically diffused up



Figure 3. (a) Perspective view of the repeating unit of 4 with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry codes: A, -x, -y + 1, -z + 1; B, -x - 1, -y + 1, -z + 2; C, x + 1, -y + 1/2, z + 1/2. (b) View of the interactions of a [MoOS3Cu3(NCS)] core via a double 4,4′-bipy bridge and three single 4,4′-bipy bridges in 4. (c) View of a very distorted adamantane-shaped unit within the network of 4. (d) A ball-stick view showing the interpentration of three adamantine units. Color balls and sticks represent [MoOS3Cu3(NCS)] cores and 4,4′-bipy bridges. (e) A space-filling representation of the side-view of the triply interpenetrating frameworks in red, green, and blue. (f) View of the 3D structure formed from the interpenetration of the three diamond networks. The channels that result from the interpenetration extending along the a axis.


Figure 4. Perspective view of the repeating unit of 5 with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry codes: A, -x - 1, -y + 2, -z + 6; B, -x - 2, -y + 2, -z +5; C, -x 2, -y + 3, -z + 6; D, -x - 1, -y + 3, -z + 5.

and down into the solution of this band, respectively. When they finally met each other somewhere in the buffer band within two days, the reaction was observed to gradually take place to form a dark red solution without any precipitates. At the same time, Et2O in the upper level of the tube also gradually diffused into the resulting solution in the buffer band to make the product 4 crystallized. It took about another three days to form crystals of 4 on the surface of the tube. Compound 4 is remarkably different from 2 and 3, suggesting that the formation of other products from this reaction may be anticipated if such a diffusion reaction could be controlled. Therefore we designed to make a zigzag tube (see Figure S2, Supporting Information). The presence of several turns of this tube was believed to be able to more efficiently slow down the diffusion of the components. Compound 5 as dark red crystals (85% yield) was finally obtained in a manner similar to that described for 4, using the same amount of components that were loaded in a zigzag tube (30 cm in length, 7 mm in inner diameter) (Scheme 1). It took over three days for the two solutions to meet in the buffer band, and took another four days to form crystals of 5. The different diffusion times in the two cases may be ascribed to the different outcomes between the reactions in a straight tube or in a zigzag tube. In addition, we attempted the solvothermal reactions of 1 with 4,4′-bipy (molar ratio ) 1:1) by heating them in aniline in a sealed Pyrex tube at 70-100 °C for 1-2 days followed by slowly cooling of the solution to ambient temperature and failed to isolate any Mo/Cu/S clusters. Solids 2-5 are relatively stable toward oxygen and moisture and slightly soluble in DMSO and DMF. The elemental analyses of 2-5 were consistent with their chemical formula. We also examined the structural homogeneity of bulk samples of 2-5 through a comparison of experimental and simulated PXRD patterns. As shown in Figure S3, the experimental pattern for each title compound correlates well with the simulated one generated from single-crystal X-ray diffraction data. In the IR spectra of 2-5, peaks at ca. 903 cm-1 and 441 cm-1 were assigned to be the terminal ModO and bridging Mo-S stretching vibrations, respectively.9f The bands at 2088 (2), 2087 (3), 2088 (4), and 2081 (5) cm-1 were assigned to be the C≡N stretching vibrations of the terminal thiocyanate groups, while that at 2115 cm-1 in 5 was assumed to be that of the bridging NCS- ligands.9i,k The identities of 2-5 were confirmed by X-ray diffraction analysis.

Chen et al.

Crystal Structures of {[{MoOS3Cu3(NCS)(ani)2}2(4,4′bipy)3] · 6(ani)}n (2) and {[(n-Bu)4N]2[{MoOS3Cu3(NCS)2}2(4,4′bipy)3] · 2(ani)}n (3). Compound 2 crystallizes in the triclinic space group P1j and the asymmetric unit contains one [(MoOS3Cu3(SCN)(ani)2)2(4,4′-bipy)3] molecule, four aniline molecules, and four halves of aniline solvent molecules, while 3 crystallizes in the monoclinic space group P21 and the asymmetric unit consists of one [(MoOS3Cu3(SCN)2)2(4,4′bipy)3]2- dianion, two Bu4N+ cations, and two aniline solvent molecules. In 2 and 3, the oxidation states for Mo and Cu are +6 and +1, respectively. The neutral repeating unit of 2 and the anionic repeating unit of 3 have a double incomplete cubanelike structure, in which two incomplete cubane-like [MoOS3Cu3(NCS)(ani)2(4,4′-bipy)0.5] (2) or [MoOS3Cu3(NCS)2(4,4′bipy)0.5] (3) fragments are linked by two 4,4′-bipy ligands. Although the core structure of each fragment of 2 or 3 is similar to that of the cluster dianion of 1, the three Cu centers in each fragment adopt different coordination geometries. For 2, Cu1 and Cu2 (or Cu4 and Cu6) are coordinated by two µ3-S atoms and two N atoms from aniline and 4,4′-bipy ligands while Cu3 (or Cu5) by two µ3-S atoms, one N atom from one terminal NCS- and one N atom from 4,4′-bipy. For 3, one Cu atom is trigonally coordinated to two µ3-S atoms and one N atom from NCS- (Cu1 or Cu6), while the other two Cu are tetrahedrally coordinated either by two µ3-S atoms, one N from NCS-, and one N from 4,4′-bipy (Cu2 or Cu5) or by two µ3-S and two N atoms from two 4,4′-bipy (Cu3 or Cu4). As shown in Table 2, for the tetrahedrally coordinated Cu, the mean Mo · · · Cu contact for 2 (2.6783(11) Å) or 3 (2.681(3) Å) is almost the same as that observed in {[MoOS3Cu3I(dpds)2] · 0.5DMF · 2(MeCN)0.5}n (2.6820(15) Å, dpds ) dipyridyl disulfide).9f For the trigonally coordinated Cu1 and Cu6 in 3, the mean Mo · · · Cu contact (2.678(3) Å) is slightly longer than that of 1 (2.647(2) Å). It is noted that the aniline molecules in 2 act as a ligand to coordinate at Cu1, Cu2, Cu4 or Cu6. The mean Cu-N(aniline) bond length (2.127(8) Å) is longer than those of Cu-N(4′-bipy) (2.077(8) Å) and Cu-N(NCS) (1.976(8) Å). The terminal Mo-O, Mo-µ3-S, Cu-µ3-S bond lengths in 2 or 3 are normal relative to those of the corresponding ones of 1. Topologically, the dimeric repeating unit [{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)2] (2) or [{MoOS3Cu3(NCS)2}2(4,4′-bipy)2] (3) works as a Z-shaped two-connecting node, which is interconnected to two equivalent ones via a pair of 4,4′-bipy ligands to form a one-dimensional (1D) zigzag chain extending along the [110] direction (2) (Figure 2a) or a 1D spiral chain extending along the c axis (3) (Figure 2b). The two chains may also be viewed as being built of the incomplete cubane-like [MoOS3Cu3(NCS)(ani)2] (2) or [MoOS3Cu3(NCS)2] (3) fragments (as an angular two-connecting node) linked alternatively through single and double 4,4′-bipy bridges. It should be noted that relative to the known compound {[(n-Bu)4N]2[(WOS3Cu3Br2)2(4,4′-bipy)3]}n (a 1D zigzag anionic chain),18 3 has a similar formula but holds a 1D spiral chain, while 2 has a different formula but possesses an analogous 1D zigzag chain. For 2, the separation between the neighboring parallel chains is ca. 11 Å. Between the chains are squeezed aniline solvent molecules (see Figure S4, Supporting Information). For 3, the separation between the neighboring parallel chains is 9.9 Å. The aniline solvent molecules and the [(n-Bu)4N]+ cations are located between the 1D chains (see Figure S5, Supporting Information). Crystal Structure of {[MoOS3Cu3(NCS)(4,4′-bipy)2.5] · 3(ani)}n (4). Compound 4 crystallizes in the monoclinic space group P21/c, and the asymmetric unit contains one [MoOS3Cu3-



Figure 5. (a) View of the interactions of a [MoOS3Cu3(NCS)] core via a single NCS bridge, a double 4,4′-bipy bridge and two single 4,4′-bipy bridges in 5. (b) View of the interactions of a [MoOS3Cu3(NCS)] core via a single NCS bridge, a double 4,4′-bipy bridge and three single 4,4′-bipy bridges. (c) View of a hexagonal prismatic [(MoOS3Cu3)6(NCS)6(µ-NCS)6(4,4′-bipy)16] unit. Color balls and sticks represent [MoOS3Cu3(NCS)] cores and 4,4′-bipy bridges. (d) View of a double layered 2D honeycomb-like network extending along the [111] plane. (e) View of an adamantine type unit formed between two 2D layers. (f) View of a single 3D diamondoid network of 5. (g) View of the 2-fold interpenetration of two single 3D networks in red and blue. (h) View of the 3D 2-fold interpenetrated structure of 5 with the channels extending along the a axis.


(NCS)(4,4′-bipy)2.5] molecule and three aniline solvent molecules. Although the incomplete cubane-like [MoOS3Cu3] core in the repeating unit [MoOS3Cu3(NCS)(4,4′-bipy)2.5] (Figure 3a) also keeps the core structure of the dianion of 1, all the Cu atoms also adopt a distorted tetrahedral coordination geometry. Apart from the coordination of two µ3-S atoms, Cu1 is coordinated by one N atom from 4,4′-bipy and one N atom from a terminal NCS-, while Cu2 and Cu3 by two N atoms from two 4,4′-bipy. The mean Mo · · · Cu contact and the terminal Mo-O, Mo-µ3-S, Cu-µ3-S, Cu-N(4,4′-bipy), and Cu-N(NCS) bond lengths (Table 2) are quite similar to those of the corresponding ones in 2 and 3. In 4, each cluster core serves as a tetrahedral four-connecting node and is coordinated by five bridging 4,4′-bipy ligands, which link four equivalent cluster cores that lie at the corners of a slightly distorted tetrahedron (Figure 3b), forming a single adamantine type unit (Figure 3c). This unit is further interconnected by 4,4′-bipy bridges to form a unique 3D diamondoid net. Each single net interpenetrates two other identical ones (Figure 3d,e), resulting a triply interpenetrated net (Figure 3f). Such 3D nets stack along the a axis to give 1D irregular channels in the unit cell of the crystal. Although such 3-fold interpenetration significantly reduces the solvent-accessible void, a total channel volume of 2142.8 Å3 (45.2% of the total cell volume calculated by Platon program19) in each unit cell is still revealed. These channels are filled by aniline solvent molecules (see Figure S6, Supporting Information). The occurrence of such a 3-fold interpenetrated 3D net is uncommon in the cluster-based supramolecular chemistry. To our knowledge, only one example {[(WOS3Cu3)2Cu6Cl(4,4′-bipy)6]Cl · 2H2O}n was reported.18 This latter compound holds a 3-fold interpenetrated 3D net in which each cluster [WOS3Cu3] core also works as a tetrahedral 4-connecting node and is coordinated by a chloride and four bridging 4,4′-bipy ligands. Within the voids of the unit cell occupied the free chlorides and the disordered H2O solvent molecules. Crystal Structure of {[(MoOS3Cu3)2(NCS)(µ-NCS)(4,4′bipy)4.5] · 7(ani)}n (5). Compound 5 crystallizes in the triclinic space group P1j and the asymmetric unit contains one discrete [(MoOS3Cu3)2(NCS)(µ-NCS)(4,4′-bipy)4.5] molecule and seven aniline solvent molecules. The cluster molecule may be viewed as a double incomplete cubane-like structure in which two incomplete cubane-like [MoOS3Cu3(4,4′-bipy)2.5] and [MoOS3Cu3(NCS)(4,4′-bipy)2] fragments are linked by one single thiocyanate bridge (Figure 4). Each [MoOS3Cu3] core structure in these two cubane-like fragments is similar to that found in 1-4, but the Cu centers show different coordination environments. All the Cu atoms in 5 possess a distorted tetrahedral coordination geometry. Apart from the coordination of two µ3-S atoms, Cu1, Cu2, and Cu5 are coordinated by two N atom from two 4,4′-bipy, while Cu3 or Cu6 by one N or S from a bridging NCS- and one N atom from 4,4′-bipy, and Cu4 atom by one N atom from a terminal NCS- and one N atom from 4,4′-bipy. For the single Cu-µ-NCS-Cu bridge, the Cu6-µ-S7(NCS) bond length (Table 2) is slightly longer than that of the corresponding ones observed in {[{(η5-C5Me5)MoS3Cu3}2(NCS)3(µNCS)(bpe)3] · 3(ani)}n (2.339(3) Å),9g but the Cu3-µ-N10(NCS) bond length is shorter than that of the corresponding ones in the latter compound. The Mo · · · Cu contacts and all other bond lengths related to the terminal Mo-O, Mo-µ3-S, Cu-µ3-S, Cu-N(4,4′-bipy) and Cu-N(NCS) are quite similar to those of the corresponding ones in 2-4. From a topological view, the two [MoOS3Cu3] cores in the dimeric unit of 5 show remarkably different multiconnecting

Chen et al.

nodes. The core in [MoOS3Cu3(NCS)(4,4′-bipy)2] works as a rare trigonal-pyramidal four-connecting node (Figure 5a) while that in [MoOS3Cu3(4,4′-bipy)2.5] acts as a unique tetragonalpyramidal five-connecting node (Figure 5b). The coexistence of such 4- and 5-connecting nodes in one structure is unprecedented in the cluster-based supramolecular chemistry. Six couples of such 4- and 5-connecting nodes interconnect each other via six NCS bridges, eight single 4,4′-bipy bridges and four double 4,4′-bipy bridges to give a hexagonal prismatic [(MoOS3Cu3)6(NCS)6(µ-NCS)6(4,4′-bipy)16] unit (Figure 5c). Such units further fuse into a double layered 2D honeycomblike network extending along the [111] plane (Figure 5d). Interestingly, the six cores in the face of a hexagonal prismatic unit, together with four cores that belong to three corner sharing hexagonal faces from the adjacent layers, form an adamantine type unit (Figure 5e), which is further linked by 4,4′-bipy ligands to adjacent ones to form a 3D diamondoid net (Figure 5f). The large void generated in this net is partly reduced by the formation of a 2-fold interpenetration (Figure 5g). The two independent 3D networks stack along the a direction to give 1D rectangular channels (Figure 5h). The cross-section has an approximate area of 15.27 × 19.88 Å2. The channels occupy a total volume of 3260.1 Å3 (57.7% of the total cell volume calculated by the Platon program) and are filled with aniline solvents (see Figure S7, Supporting Information). Conclusions In this paper, we demonstrated our efforts to explore the effects of synthetic approaches on the assembly of [MoOS3Cu3]based coordination polymers. Compounds 2-5 were prepared from 1 and 4,4′-bipy using four different synthetic routes, that is, routine solution reaction, solid state reaction at ambient temperature, diffusion reaction in a straight or zigzag glass tube. These four compounds are structurally different: the former two have a 1D zigzag chain (2) or a 1D spiral chain structure (3), while the latter two have a rare 3D 3-fold interpenetrated network (4) or an unprecedented 3D 2-fold interpenetrated network (5). It is suggested that the products generated from solid state reactions at room temperature could be different from those derived from the routine solution reactions. The formation of different products in a straight or zigzag glass tube may be due to the different diffusion times of the components in these tubes. These results showed that the synthetic methodologies could place great impact on the construction of [MoOS3Cu3]based coordination polymers. Further studies on reactions of other cluster precursors such as [Et4N]4[WS4Cu4I6]9c and [PPh4][Cp*MoS3(CuNCS)3]9g with multitopic ligands (4,4-bipy, 1,2-bis(4-pyridyl)ethane, 1,3-bis(4-pyridyl)propane, etc.) using the above four methods are underway in this laboratory. Acknowledgment. This work was supported by the National Natural Science Foundation of China (20525101 and 20871088), the Specialized Research Fund for the Doctoral Program of Higher Education (20050285004), “SooChow Scholar” Program and Program for Innovative Research Team of Suzhou University, and the Nature Science Foundation of Guangdong Province (7300449). We are grateful to the editor and the reviewers for their helpful suggestions. Supporting Information Available: Crystal structural data for 2-5 in CIF format and the PXRD patterns and the crystal packing diagrams of 2-5. This material is available free of charge via the Internet at http://pubs.acs.org.



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[MoOS3Cu3]-Based Coordination Polymers from the Same

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