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Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters
Inorganic Chemistry Communications 9 (2006) 1315–1318 www.elsevier.com/locate/inoche
Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters Zhen-He Xu, Yang-Guang Li, En-Bo Wang *, Chao Qin, Xin-Long Wang Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jinlin 130024, PR China Received 20 July 2006; accepted 10 August 2006 Available online 1 September 2006
Abstract Two new polyoxomolybdates Na5(NH4)16[Mo57Mn6(NO)6O174 (OH)3(H2O)24] Æ 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3 (H2O)24] Æ 53H2O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure. Ó 2006 Elsevier B.V. All rights reserved. Keywords: Polyoxometalates; Transition metal; Crystal structure; Magnetic
Polyoxometalates (POMs), in addition to their importance in catalysis, biochemical separation, and medicinal chemistry, play an important role in the design of new materials with novel electronic, magnetic, and topological properties [1–3]. The evolution of polyoxometalate chemistry depends on the synthesis of new compounds possessing unique structures and properties. They can be tuned at the molecular level and exhibit fascinating structures and properties [4]. A new area of interest is the construction of larger nanoscaled cluster containing polyoxoanions because of the potential application of these POMs-based clusters sparked by many applications found and proposed [5]. Therefore, the self-assembly process of nanoscale polyoxometalates has attracted the attentions of many groups, and a series of attractive giant polyoxometalates with nanoscale dimensions have been reported. Pope [6], Mu¨ller [7], Se´cheresse [8], Yamase [9], Kortz [10], Lu [11] and Zhang [12] and their co-workers also reported a series of nanoscale polyoxometalates. It is noteworthy that one part of challenging work in this field is the preparation of novel wheel-shape polyoxometa*
Corresponding author. Tel./fax: +86 431 5098787. E-mail address: [email protected] (E.-B. Wang).
1387-7003/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.08.013
lates. Mu¨ller’s group has reported several inorganic superfullerenes and giant ring shaped, electron-rich, mixedvalence polyoxomolybdate clusters which have been synthesized from an acidified aqueous molybdate solution reduced by reducing agents [13]. Within the class of large polyoxomolybdate (POMo) cluster, two predominant structural types can be considered: cyclic, or ring-shaped structure (Mo154, Mo176, Mo128Eu4) and hollow, spherical structures (Mo102, Mo132, Mo72V30, Mo214V30) [14]. In the vast amount of reported work, the rapid progress in the synthesis and characterization of new transition-metalsubstituted polyoxomolybdate (POMo) cluster is driven by interest in their structural diversity and fascinating properties [15]. Meanwhile, the metal oxide-based nanoobjects have a multitude of functions, e.g. potential ‘‘receptors’’ for anions and cations [16]. Therefore, it is still a matter of close attention to prepare wheel-shape polyoxometalates with novel structures and desirable properties. Our group has been devoting a lot of research time to the synthese of POMs with various structures [17]. So, it is also highly interesting to synthesize such polyoxoanions with nanoscaled. Inspired by the aforementioned considerations, we attempt to study the systematic synthesis of multi-metalsubstituted polyoxomolybdate (POMo) clusters. In this
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paper, we reported two mixed-valence nanoscale polyoxomolybdate-based cluster compounds: Na5(NH4)16[Mo57Mn6(NO)6O174(OH)3(H2O)24] Æ 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] Æ 53H2O (2). As far as we know, only two polyoxomolybdate (POMo) clusters with similar wheel-shape structures have been documented prior to this work [18]. Compounds 1 and 2 were synthesized from aqueous media and isolated as deep-red columnar crystals [19]. X-ray diffraction analysis [20] reveals that the two compounds have similar structure, and the structure of 1 is described here representatively. The structure of compound 1 consists of a discrete 57-membered cage-shaped [Mo57Mn6(NO)6- O174(OH)3(H2O)24]21 nanoanion that is made up of 51 MoO6 octahedra and 6 pentagonal {Mo(NO)O6} bipyramids. As shown in Figs. 1 and 2, four different but related building blocks have been found in compound 1. The first building block is the symmetric fMo17 gðBfMoVI 15 ðMoNOÞ2 20 O58 ðH2 OÞ2 g Þ moiety that is built by two {Mo8} units and one {Mo1} unit which symmetrically linked by sharing edges. Each of the basic {Mo8} units possesses a sevencoordinate {Mo(NO)O6} pentagonal bipyramid, which is symmetrically connected to five {Mo6} octahedra via edge-sharing mode. Four of the {Mo6} octahedra are further linked to another four {Mo6} octahedra by sharing corners to form the {Mo8} units. The structure of this octamolybdate building block is found in many other large polyoxometalate structures, with {Mo8}-type building block even very large and unusual clusters can be built up [21]. In addition, {MoV(l-H2O)2(l-OH)MoV}9+ subunits are also found in this structure. This building block is constructed from two edge-sharing molybdenum-oxygen
Fig. 1. Ball-and-stick representation of 1. (The color code is as follows: Mo, purple; O, red; N, green; Mn yellow). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. Polyhedral representation of 1. (The color code is as follows: Mo, purple; O, red; N, green; Mn yellow). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
octahedra. This cationic centers link the three {Mo17} moieties through corner-shared, leading to a six-cavity anionic {MO57(NO)6O174(OH)3(H2O)6}33 frame. Three of the six cavities ,which are positioned at the inner part of the anionic frame, are blocked by six coordinated {MnII(H2O)2}2+ units which is the third building block (Fig. 3). Each {Mo17} units links to two {MnII(H2O)2}2+ units through two terminal oxo groups of octahedral molybdenum sites ˚ . The structure with average Mn–O distance of 2.071 A analysis suggests that compound 2 is similar to 1, but Cu2+ is five-coordinate (Figure S1). In the IR spectrum of compound 1, the feature at 1619, 1404 cm1 can be regarded as H2O and NHþ 4 , respectively. The peaks at 942, 873, 804, 697, 607, 592 cm1 are attributed to m(Mo=O) and m(Mo–O–Mo) vibrations. The IR spectrum of compound 2 is similar to that of 1. The thermal gravimetric (TG) curve of 1 is shown in Figure S2. The weight loss of 17.60% in the range of 30– 310 °C corresponds to the loss of all noncoordinated and partly coordinated water molecules and NHþ 4 . The weight loss of 2.52% in the range of 321–355 °C corresponds to the loss of the remaining coordinated water molecules. The TG curve gives a total weight loss of 25.75% in the range of 30–550 °C, which agrees with the calculated value of 25.90%. In summary, two new polyoxomolybdate (POMo) clusters, Na5(NH4)16[Mo57Mn6(NO)6O174(OH)3(H2O)24] Æ 44H2O and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] Æ 53H2O , have been synthesized and characterized by singlecrystal X-ray analysis. The success in synthesizing compounds 1 and 2 might provide useful information for the design and synthesis of transition-metal oxide-based material and enlarge MO57M6 cluster-type polyoxomolybdates.
Z.-H. Xu et al. / Inorganic Chemistry Communications 9 (2006) 1315–1318
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Fig. 3. Combined polyhedra/ball and stick representation of 1. The yellow octahedral represent MnO6 and the balls represent Mo (purple) and O (red). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Under similar conditions, some extended experiments can be done: if employ other transition metal ions or rare earth ions to replace Mn or Cu ions, or block the three cavities located on the outer sphere by some suitable metal-oxygen fragment such as {MoO}4+,{VO}3+[22] step by step, many possible novel species are very likely to be obtained. Now, we are exploring this avenue. Acknowledgement This work was supported by the National Science Foundation of China (No. 20371011). Appendix A. Supplementary materials Crystal data and structure refinement, atomic coordinates, bond lengths and angles, anisotropic displacement parameters, the TG curve and IR spectra of compounds 1 and 2 are available from the authors on request. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2006.08.013. References [1] M.T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin, 1983. [2] (a) C.L. Hill, Chem. Rev. 98 (1998) 1–2; (b) E. Coronado, Carlos J. Go´mez-Garcı´a, Chem. Rev. 98 (1998) 273–296; (c) J.T. Rhule, C.L. Hill, D.A. Judd, R.F. Schinazi, Chem. Rev. 98 (1998) 327–357; (d) T. Yamase, Chem. Rev. 98 (1998) 307–325; (e) L.C. Baker, D.C. Glick, Chem. Rev. 98 (1998) 3–49; (f) D. Hagrman, R.C. Haushalter, J. Zubieta, Chem. Mater. 10 (1998) 361.
[3] M.T. Pope, A. Mu¨ller (Eds.), Polyoxometalates: From Platonic Solids to Anti-retroviral Activity, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1994. [4] (a) L.H. Bi, E.B. Wang, J. Peng, R.D. Huang, L. Xu, C.W. Hu, Inorg. Chem. 39 (2000) 671–679; (b) W.S. You, E.B. Wang, Y. Xu, Y.G. Li, C.W. Hu, Inorg. Chem. 40 (2001) 5468–5473; (c) J.Y. Niu, Q. Wu, J.P. Wang, J. Chem. Soc., Dalton Trans. (2002) 2512; (d) Y. Xia, P.F. Wu, Y.G. Wei, Y . Wang, H.Y. Guo, Cryst. Growth Des. 6 (2006) 253; (e) X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, Inorg. Chem. 43 (2004) 8005. [5] A. Mu¨ller, C. Serain, Acc. Chem. Res. 33 (2000) 2–10. [6] K. Wassermann, M.H. Dickman, M.T. Pope, Angew. Chem., Int. Ed. Engl. 36 (1997) 1445–1448. [7] (a) A. Mu¨ller, S.Q.N. Shah, H. Bo¨gge, M. Schmidtmann, Nature 397 (1999) 48–50; (b) L. Cronin, C. Beugholt, E. Krickemeyer, M. Schmidtmann, H. Bo¨gge, P. Ko¨gerler, T.K.K. Luong, A. Mu¨ller, Angew. Chem., Int. Ed. 41 (2002) 1162–1167. [8] C.D. Peloux, A. Dolbecq, P. Mialane, J. Marrot, E. Rivie`re, Francis Se´cheresse, Angew. Chem., Int. Ed. 40 (2001) 2455–2457. [9] K. Fukaya, T. Yamase, Angew. Chem., Int. Ed. 42 (2003) 654–658. [10] S.S. Mal, U. Kortz, Angew. Chem., Int. Ed. 44 (2005) 3777–3780. [11] W.B. Yang, C.Z. Lu, X. Lin, H.H. Zhuang, J. Chem. Soc., Chem. Commun. (2000) 1623. [12] S.W. Zhang, D.Q. Liao, M.C. Shao, Y.Q. Tang, J. Chem. Soc., Chem. Commun (1986) 835. [13] (a) A. Mu¨ller, F. Peters, M.T. Pope, D. Gatteschi, Chem. Rev. 98 (1998) 239–271; (b) A. Mu¨ller, S. Roy, Coord. Chem. Rev. 245 (2003) 153–166. [14] B. Botar, P. Ko¨gerler, C.L. Hill, J. Am. Chem. Soc. 128 (2006) 5336– 5337. [15] (a) B. Botar, P. Ko¨gerler, C.L. Hill, Chem. Commun. (2005) 3138– 3140; (b) M.T. Pope, A. Mu¨ller, Angew. Chem., Int. Ed. Engl. 30 (1991) 34; (c) M.I. Khan, A. Mu¨ller, S. Dillinger, H. Bo¨gge, Q. Chen, J. Zubieta, Angew. Chem., Int. Ed. 32 (1993) 1780.
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[16] (a) A. Mu¨ller, M. Luban, C. Schro¨der, R. Modler, P. Ko¨gerler, M. Axenovich, J. Schnack, P. Canfield, S. Bud’ko, N. Harrison, Chem. Phys. Chem. 2 (2001) 517–521; (b) B. Botar, P. Ko¨gerler, A. Mu¨ller, R. Garcia-Serres, C.L. Hill, Chem. Commun. (2005) 5621–5623; (c) A. Mu¨ller, L. Toma, H. Bo¨gge, M. Schmidtmann, P. Ko¨gerler, J. Chem. Soc., Chem. Commun. 16 (2003) 2000. [17] (a) H.Y. An, E.B. Wang, D.R. Xiao, Y.G. Ling, Z.M. Su, L. Xu, Angew. Chem., Int. Ed. 44 (2005) 904–908; (b) H.Y. An, D.R. Xiao, E.B. Wang, Y.G. Li, L. Xu, New J. Chem. 29 (2005) 854; (c) M. Yuan, Y.G. Li, E.B. Wang, Y. Lu, C.W. Hu, N.H. Hu, H.Q. Jia, J. Chem. Soc., Dalton Trans. (2002) 2916–2920. [18] (a) S.W. Zhang, G.Q. Huang, M.C. Shao, Y.Q. Tang, J. Chem. Soc., Chem. Commun. (1993) 37–38; (b) G.Q. Huang, S.W. Zhang, M.C. Shao, Polyhedron 12 (1993) 2067–2068; (c) G.Q. Huang, S.W. Zhang, M.C. Shao, Chin. Sci. Bull. 40 (1995) 1438–1441; (d) A. Mu¨ller, W. Plass, E. Krickemeyer, S. Dillinger, H. Bo¨gge, A. Armatage, A. Proust, C. Beugholt, U. Bergmann, Angew. Chem., Int. Ed. Engl. 33 (1994) 849; (e) A. Mu¨ller, E. Krickemeyer, S. Dillinger, H. Bo¨gge, W. Plass, A. Proust, L. Dloczik, C. Menke, J. Meyer, R. Rohlfing, Z. Anorg. Allg. Chem. 620 (1994) 599; (f) P. Ko¨gerler, A. Mu¨ller, J. Appl. Phys. 93 (2003) 7101–7102. [19] In a typical synthesis procedure for 1, first Na2MoO4 Æ H2O (2.425 g) and Mn(CH3COO)2 Æ 4H2O (3.675 g) were dissolved in water (50 ml). Then the solution was acidified with hydrochloric acid (2.0 ml, 17%). After addition of NH2OH Æ HCl (0.347 g), the resulting solution was stirred at room temperature for ca. 3–4 h. The reaction mixture was filtrated the next day, and the filtrate was kept in a wide-necked
Erlenmeyer flask without further disturbance for two weeks. The mainly precipitated deep-red columnar crystals of 1 were filtered, washed with cooled water, and finally dried in air (yield about: 15% based on Mo). Anal. Calc. for H203Mn6Mo57N22Na5O251: H, 1.94%; Mn, 3.16%; Mo, 52.4%; N, 2.95%; Na, 1.34%; found: H, 1.93% Mn, 3.15%; Mo, 52.5%; N, 2.96%; Na, 1.33%; selected FTIR data (cm1): 1619(m), 1404(s), 942(s), 873(vs), 804(vs), 697(s), 607(vs), 562(s). In a typical synthesis procedure for 2, first (NH4)6Mo7O24 Æ 4H2O (1.460 g) and Cu(CH3COO)2 Æ H2O (2.500 g) were dissolved in water (50 ml). Then the solution was acidified with hydrochloric acid (2.0 ml, 17%). After addition of NH2OH Æ HCl (0.347 g), the resulting solution was stirred at room temperature for ca. 3–4 h. The reaction mixture was filtrated the next day, and the filtrate was kept in a widenecked Erlenmeyer flask without further disturbance for two weeks. The mainly precipitated deep-red columnar crystals of 2 were filtered, washed with cooled water, and finally dried in air (yield about: 10% based on Mo). Anal. Calc. for H241Cu6Mo57N27O254: H, 2.28%, Cu, 3.64%, Mo, 51.79%, N, 3.59%; found: H, 2.29%, Cu, 3.65%, Mo, 51.78%, N, 3.58%; selected FTIR data (cm1): 1612(m), 1402(s), 940(s), 876(vs), 803(vs), 709(vs), 667(s), 608(vs), 574(s). ˚, b= [20] Crystal data for 1: orthorhombic, Cmcm, a = 23.650(5) A ˚ , c = 26.708(5) A ˚ , a = 90°, b = 90°, c = 90°, V = 41.196(8) A ˚ 3, Z = 4, R1(wR2) = 0.1266 (0.3291), S = CSD: 416,825. 26022(9) A ˚, Crystal data for 2: hexagonal, P6(3)/mmc, a = 23.459(3) A ˚ , c = 26.028(5) A ˚ , a = 90°, b = 90°, c = 120°, b = 23.459(3) A ˚ 3, Z = 2, R1(wR2) = 0.0501 (0.1456), S = CSD: V = 12,404(3) A 416,824. [21] (a) A. Mu¨ller, F. Peters, M.T. Pope, D. Gatteschi, Chem. Rev. 98 (1998) 239; (b) A. Mu¨ller, C. Beugholt, Nature 383 (1996) 296. [22] W.B. Yang, X. Lin, C.Z. Lu, H.H. Zhuang, J.S. Huang, Inorg. Chem. 39 (2000) 2706–2707.
Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters Zhen-He Xu, Yang-Guang Li, En-Bo Wang *, Chao Qin, Xin-Long Wang Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jinlin 130024, PR China Received 20 July 2006; accepted 10 August 2006 Available online 1 September 2006
Abstract Two new polyoxomolybdates Na5(NH4)16[Mo57Mn6(NO)6O174 (OH)3(H2O)24] Æ 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3 (H2O)24] Æ 53H2O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure. Ó 2006 Elsevier B.V. All rights reserved. Keywords: Polyoxometalates; Transition metal; Crystal structure; Magnetic
Polyoxometalates (POMs), in addition to their importance in catalysis, biochemical separation, and medicinal chemistry, play an important role in the design of new materials with novel electronic, magnetic, and topological properties [1–3]. The evolution of polyoxometalate chemistry depends on the synthesis of new compounds possessing unique structures and properties. They can be tuned at the molecular level and exhibit fascinating structures and properties [4]. A new area of interest is the construction of larger nanoscaled cluster containing polyoxoanions because of the potential application of these POMs-based clusters sparked by many applications found and proposed [5]. Therefore, the self-assembly process of nanoscale polyoxometalates has attracted the attentions of many groups, and a series of attractive giant polyoxometalates with nanoscale dimensions have been reported. Pope [6], Mu¨ller [7], Se´cheresse [8], Yamase [9], Kortz [10], Lu [11] and Zhang [12] and their co-workers also reported a series of nanoscale polyoxometalates. It is noteworthy that one part of challenging work in this field is the preparation of novel wheel-shape polyoxometa*
Corresponding author. Tel./fax: +86 431 5098787. E-mail address: [email protected] (E.-B. Wang).
1387-7003/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.08.013
lates. Mu¨ller’s group has reported several inorganic superfullerenes and giant ring shaped, electron-rich, mixedvalence polyoxomolybdate clusters which have been synthesized from an acidified aqueous molybdate solution reduced by reducing agents [13]. Within the class of large polyoxomolybdate (POMo) cluster, two predominant structural types can be considered: cyclic, or ring-shaped structure (Mo154, Mo176, Mo128Eu4) and hollow, spherical structures (Mo102, Mo132, Mo72V30, Mo214V30) [14]. In the vast amount of reported work, the rapid progress in the synthesis and characterization of new transition-metalsubstituted polyoxomolybdate (POMo) cluster is driven by interest in their structural diversity and fascinating properties [15]. Meanwhile, the metal oxide-based nanoobjects have a multitude of functions, e.g. potential ‘‘receptors’’ for anions and cations [16]. Therefore, it is still a matter of close attention to prepare wheel-shape polyoxometalates with novel structures and desirable properties. Our group has been devoting a lot of research time to the synthese of POMs with various structures [17]. So, it is also highly interesting to synthesize such polyoxoanions with nanoscaled. Inspired by the aforementioned considerations, we attempt to study the systematic synthesis of multi-metalsubstituted polyoxomolybdate (POMo) clusters. In this
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paper, we reported two mixed-valence nanoscale polyoxomolybdate-based cluster compounds: Na5(NH4)16[Mo57Mn6(NO)6O174(OH)3(H2O)24] Æ 44H2O (1) and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] Æ 53H2O (2). As far as we know, only two polyoxomolybdate (POMo) clusters with similar wheel-shape structures have been documented prior to this work [18]. Compounds 1 and 2 were synthesized from aqueous media and isolated as deep-red columnar crystals [19]. X-ray diffraction analysis [20] reveals that the two compounds have similar structure, and the structure of 1 is described here representatively. The structure of compound 1 consists of a discrete 57-membered cage-shaped [Mo57Mn6(NO)6- O174(OH)3(H2O)24]21 nanoanion that is made up of 51 MoO6 octahedra and 6 pentagonal {Mo(NO)O6} bipyramids. As shown in Figs. 1 and 2, four different but related building blocks have been found in compound 1. The first building block is the symmetric fMo17 gðBfMoVI 15 ðMoNOÞ2 20 O58 ðH2 OÞ2 g Þ moiety that is built by two {Mo8} units and one {Mo1} unit which symmetrically linked by sharing edges. Each of the basic {Mo8} units possesses a sevencoordinate {Mo(NO)O6} pentagonal bipyramid, which is symmetrically connected to five {Mo6} octahedra via edge-sharing mode. Four of the {Mo6} octahedra are further linked to another four {Mo6} octahedra by sharing corners to form the {Mo8} units. The structure of this octamolybdate building block is found in many other large polyoxometalate structures, with {Mo8}-type building block even very large and unusual clusters can be built up [21]. In addition, {MoV(l-H2O)2(l-OH)MoV}9+ subunits are also found in this structure. This building block is constructed from two edge-sharing molybdenum-oxygen
Fig. 1. Ball-and-stick representation of 1. (The color code is as follows: Mo, purple; O, red; N, green; Mn yellow). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. Polyhedral representation of 1. (The color code is as follows: Mo, purple; O, red; N, green; Mn yellow). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
octahedra. This cationic centers link the three {Mo17} moieties through corner-shared, leading to a six-cavity anionic {MO57(NO)6O174(OH)3(H2O)6}33 frame. Three of the six cavities ,which are positioned at the inner part of the anionic frame, are blocked by six coordinated {MnII(H2O)2}2+ units which is the third building block (Fig. 3). Each {Mo17} units links to two {MnII(H2O)2}2+ units through two terminal oxo groups of octahedral molybdenum sites ˚ . The structure with average Mn–O distance of 2.071 A analysis suggests that compound 2 is similar to 1, but Cu2+ is five-coordinate (Figure S1). In the IR spectrum of compound 1, the feature at 1619, 1404 cm1 can be regarded as H2O and NHþ 4 , respectively. The peaks at 942, 873, 804, 697, 607, 592 cm1 are attributed to m(Mo=O) and m(Mo–O–Mo) vibrations. The IR spectrum of compound 2 is similar to that of 1. The thermal gravimetric (TG) curve of 1 is shown in Figure S2. The weight loss of 17.60% in the range of 30– 310 °C corresponds to the loss of all noncoordinated and partly coordinated water molecules and NHþ 4 . The weight loss of 2.52% in the range of 321–355 °C corresponds to the loss of the remaining coordinated water molecules. The TG curve gives a total weight loss of 25.75% in the range of 30–550 °C, which agrees with the calculated value of 25.90%. In summary, two new polyoxomolybdate (POMo) clusters, Na5(NH4)16[Mo57Mn6(NO)6O174(OH)3(H2O)24] Æ 44H2O and (NH4)21[Mo57Cu6(NO)6O168(OH)3(H2O)24] Æ 53H2O , have been synthesized and characterized by singlecrystal X-ray analysis. The success in synthesizing compounds 1 and 2 might provide useful information for the design and synthesis of transition-metal oxide-based material and enlarge MO57M6 cluster-type polyoxomolybdates.
Z.-H. Xu et al. / Inorganic Chemistry Communications 9 (2006) 1315–1318
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Fig. 3. Combined polyhedra/ball and stick representation of 1. The yellow octahedral represent MnO6 and the balls represent Mo (purple) and O (red). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Under similar conditions, some extended experiments can be done: if employ other transition metal ions or rare earth ions to replace Mn or Cu ions, or block the three cavities located on the outer sphere by some suitable metal-oxygen fragment such as {MoO}4+,{VO}3+[22] step by step, many possible novel species are very likely to be obtained. Now, we are exploring this avenue. Acknowledgement This work was supported by the National Science Foundation of China (No. 20371011). Appendix A. Supplementary materials Crystal data and structure refinement, atomic coordinates, bond lengths and angles, anisotropic displacement parameters, the TG curve and IR spectra of compounds 1 and 2 are available from the authors on request. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2006.08.013. References [1] M.T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin, 1983. [2] (a) C.L. Hill, Chem. Rev. 98 (1998) 1–2; (b) E. Coronado, Carlos J. Go´mez-Garcı´a, Chem. Rev. 98 (1998) 273–296; (c) J.T. Rhule, C.L. Hill, D.A. Judd, R.F. Schinazi, Chem. Rev. 98 (1998) 327–357; (d) T. Yamase, Chem. Rev. 98 (1998) 307–325; (e) L.C. Baker, D.C. Glick, Chem. Rev. 98 (1998) 3–49; (f) D. Hagrman, R.C. Haushalter, J. Zubieta, Chem. Mater. 10 (1998) 361.
[3] M.T. Pope, A. Mu¨ller (Eds.), Polyoxometalates: From Platonic Solids to Anti-retroviral Activity, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1994. [4] (a) L.H. Bi, E.B. Wang, J. Peng, R.D. Huang, L. Xu, C.W. Hu, Inorg. Chem. 39 (2000) 671–679; (b) W.S. You, E.B. Wang, Y. Xu, Y.G. Li, C.W. Hu, Inorg. Chem. 40 (2001) 5468–5473; (c) J.Y. Niu, Q. Wu, J.P. Wang, J. Chem. Soc., Dalton Trans. (2002) 2512; (d) Y. Xia, P.F. Wu, Y.G. Wei, Y . Wang, H.Y. Guo, Cryst. Growth Des. 6 (2006) 253; (e) X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, Inorg. Chem. 43 (2004) 8005. [5] A. Mu¨ller, C. Serain, Acc. Chem. Res. 33 (2000) 2–10. [6] K. Wassermann, M.H. Dickman, M.T. Pope, Angew. Chem., Int. Ed. Engl. 36 (1997) 1445–1448. [7] (a) A. Mu¨ller, S.Q.N. Shah, H. Bo¨gge, M. Schmidtmann, Nature 397 (1999) 48–50; (b) L. Cronin, C. Beugholt, E. Krickemeyer, M. Schmidtmann, H. Bo¨gge, P. Ko¨gerler, T.K.K. Luong, A. Mu¨ller, Angew. Chem., Int. Ed. 41 (2002) 1162–1167. [8] C.D. Peloux, A. Dolbecq, P. Mialane, J. Marrot, E. Rivie`re, Francis Se´cheresse, Angew. Chem., Int. Ed. 40 (2001) 2455–2457. [9] K. Fukaya, T. Yamase, Angew. Chem., Int. Ed. 42 (2003) 654–658. [10] S.S. Mal, U. Kortz, Angew. Chem., Int. Ed. 44 (2005) 3777–3780. [11] W.B. Yang, C.Z. Lu, X. Lin, H.H. Zhuang, J. Chem. Soc., Chem. Commun. (2000) 1623. [12] S.W. Zhang, D.Q. Liao, M.C. Shao, Y.Q. Tang, J. Chem. Soc., Chem. Commun (1986) 835. [13] (a) A. Mu¨ller, F. Peters, M.T. Pope, D. Gatteschi, Chem. Rev. 98 (1998) 239–271; (b) A. Mu¨ller, S. Roy, Coord. Chem. Rev. 245 (2003) 153–166. [14] B. Botar, P. Ko¨gerler, C.L. Hill, J. Am. Chem. Soc. 128 (2006) 5336– 5337. [15] (a) B. Botar, P. Ko¨gerler, C.L. Hill, Chem. Commun. (2005) 3138– 3140; (b) M.T. Pope, A. Mu¨ller, Angew. Chem., Int. Ed. Engl. 30 (1991) 34; (c) M.I. Khan, A. Mu¨ller, S. Dillinger, H. Bo¨gge, Q. Chen, J. Zubieta, Angew. Chem., Int. Ed. 32 (1993) 1780.
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[16] (a) A. Mu¨ller, M. Luban, C. Schro¨der, R. Modler, P. Ko¨gerler, M. Axenovich, J. Schnack, P. Canfield, S. Bud’ko, N. Harrison, Chem. Phys. Chem. 2 (2001) 517–521; (b) B. Botar, P. Ko¨gerler, A. Mu¨ller, R. Garcia-Serres, C.L. Hill, Chem. Commun. (2005) 5621–5623; (c) A. Mu¨ller, L. Toma, H. Bo¨gge, M. Schmidtmann, P. Ko¨gerler, J. Chem. Soc., Chem. Commun. 16 (2003) 2000. [17] (a) H.Y. An, E.B. Wang, D.R. Xiao, Y.G. Ling, Z.M. Su, L. Xu, Angew. Chem., Int. Ed. 44 (2005) 904–908; (b) H.Y. An, D.R. Xiao, E.B. Wang, Y.G. Li, L. Xu, New J. Chem. 29 (2005) 854; (c) M. Yuan, Y.G. Li, E.B. Wang, Y. Lu, C.W. Hu, N.H. Hu, H.Q. Jia, J. Chem. Soc., Dalton Trans. (2002) 2916–2920. [18] (a) S.W. Zhang, G.Q. Huang, M.C. Shao, Y.Q. Tang, J. Chem. Soc., Chem. Commun. (1993) 37–38; (b) G.Q. Huang, S.W. Zhang, M.C. Shao, Polyhedron 12 (1993) 2067–2068; (c) G.Q. Huang, S.W. Zhang, M.C. Shao, Chin. Sci. Bull. 40 (1995) 1438–1441; (d) A. Mu¨ller, W. Plass, E. Krickemeyer, S. Dillinger, H. Bo¨gge, A. Armatage, A. Proust, C. Beugholt, U. Bergmann, Angew. Chem., Int. Ed. Engl. 33 (1994) 849; (e) A. Mu¨ller, E. Krickemeyer, S. Dillinger, H. Bo¨gge, W. Plass, A. Proust, L. Dloczik, C. Menke, J. Meyer, R. Rohlfing, Z. Anorg. Allg. Chem. 620 (1994) 599; (f) P. Ko¨gerler, A. Mu¨ller, J. Appl. Phys. 93 (2003) 7101–7102. [19] In a typical synthesis procedure for 1, first Na2MoO4 Æ H2O (2.425 g) and Mn(CH3COO)2 Æ 4H2O (3.675 g) were dissolved in water (50 ml). Then the solution was acidified with hydrochloric acid (2.0 ml, 17%). After addition of NH2OH Æ HCl (0.347 g), the resulting solution was stirred at room temperature for ca. 3–4 h. The reaction mixture was filtrated the next day, and the filtrate was kept in a wide-necked
Erlenmeyer flask without further disturbance for two weeks. The mainly precipitated deep-red columnar crystals of 1 were filtered, washed with cooled water, and finally dried in air (yield about: 15% based on Mo). Anal. Calc. for H203Mn6Mo57N22Na5O251: H, 1.94%; Mn, 3.16%; Mo, 52.4%; N, 2.95%; Na, 1.34%; found: H, 1.93% Mn, 3.15%; Mo, 52.5%; N, 2.96%; Na, 1.33%; selected FTIR data (cm1): 1619(m), 1404(s), 942(s), 873(vs), 804(vs), 697(s), 607(vs), 562(s). In a typical synthesis procedure for 2, first (NH4)6Mo7O24 Æ 4H2O (1.460 g) and Cu(CH3COO)2 Æ H2O (2.500 g) were dissolved in water (50 ml). Then the solution was acidified with hydrochloric acid (2.0 ml, 17%). After addition of NH2OH Æ HCl (0.347 g), the resulting solution was stirred at room temperature for ca. 3–4 h. The reaction mixture was filtrated the next day, and the filtrate was kept in a widenecked Erlenmeyer flask without further disturbance for two weeks. The mainly precipitated deep-red columnar crystals of 2 were filtered, washed with cooled water, and finally dried in air (yield about: 10% based on Mo). Anal. Calc. for H241Cu6Mo57N27O254: H, 2.28%, Cu, 3.64%, Mo, 51.79%, N, 3.59%; found: H, 2.29%, Cu, 3.65%, Mo, 51.78%, N, 3.58%; selected FTIR data (cm1): 1612(m), 1402(s), 940(s), 876(vs), 803(vs), 709(vs), 667(s), 608(vs), 574(s). ˚, b= [20] Crystal data for 1: orthorhombic, Cmcm, a = 23.650(5) A ˚ , c = 26.708(5) A ˚ , a = 90°, b = 90°, c = 90°, V = 41.196(8) A ˚ 3, Z = 4, R1(wR2) = 0.1266 (0.3291), S = CSD: 416,825. 26022(9) A ˚, Crystal data for 2: hexagonal, P6(3)/mmc, a = 23.459(3) A ˚ , c = 26.028(5) A ˚ , a = 90°, b = 90°, c = 120°, b = 23.459(3) A ˚ 3, Z = 2, R1(wR2) = 0.0501 (0.1456), S = CSD: V = 12,404(3) A 416,824. [21] (a) A. Mu¨ller, F. Peters, M.T. Pope, D. Gatteschi, Chem. Rev. 98 (1998) 239; (b) A. Mu¨ller, C. Beugholt, Nature 383 (1996) 296. [22] W.B. Yang, X. Lin, C.Z. Lu, H.H. Zhuang, J.S. Huang, Inorg. Chem. 39 (2000) 2706–2707.