- Email: [email protected]
pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers
Available online at www.sciencedirect.com
Inorganic Chemistry Communications 10 (2007) 1257–1261 www.elsevier.com/locate/inoche
pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers Rong-Guang Lin, La-Sheng Long *, Rong-Bin Huang, Lan-Sun Zheng State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China Received 31 March 2007; accepted 4 August 2007 Available online 10 August 2007
Abstract Three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ6nH2O (1), {NH4[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 5nH2O (2), [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O (3), have been synthesized under different pH conditions. Complex 1, which exhibits a one-dimensional (1D) structure, is formed at [H+] = 2.0 mol L1. Reaction at pH 4 leads to another one-dimensional (1D) coordination polymer of 2. At pH 5, a two-dimensional (2D) coordination polymer of complex 3 is formed, showing clearly structural effects on pH response. 2007 Elsevier B.V. All rights reserved. Keywords: 4-Sulfocalix[4]arene; Manganese; Coordination polymer; pH-Dependent
Crystal engineering and design of solid-state architectures of coordination polymers are currently of interest in the field of supramolecular chemistry and material science [1,2], due to their potential as functional materials as well as their interesting compositions and topologies [2–4]. Water-soluble calix[n]arenes, possessing strongly hydrophilic upper and lower rims and a strongly hydrophobic conelike cavity, have become increasingly important in the field of supramolecular chemistry and crystal engineering in recent decades [5,6]. As a multifunctional supramolecular synthon, 4-sulfocalixarene can form various kinds of supramolecular aggregations which include ‘Russion dolls’ or ‘molecular capsules’ [7], ‘Ferris wheels’ [8], hydrogen bonded polymers [9], 1D [10] and 2D [9–11] coordination polymers, water-filled channels [12], as well as nanometer scale spheres and tubules [13]. Owing to the assembly of supramolecular architectures easily affected by external physical or chemical stimuli, however, the reaction pathways frequently changed case by case, resulting in
*
Corresponding author. Tel.: +86 592 218 5191; fax: +86 592 218 3047. E-mail address: [email protected] (L.-S. Long).
1387-7003/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2007.08.003
poor selectivity [14]. pH value of the reaction, as one of the external stimuli, is especially important in the assembly of supramolecular architectures [15]. It affects not only the ligand coordination ability but also its charge and, therefore, the metal-to-ligand ratio and, consequently, the resulting topology [5,15,16]. However, systematic investigations focusing on the influence of pH value of the reaction, while keeping numerous other factors constant, are still very rare in this system [15i]. Here we report crystal structures of three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 6nH2O (1), {NH4[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 5nH2O (2), [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O (3), which are prepared under the different pH conditions [17]. Their structural diversities show clearly structural effects on pH response. Compound 1 [18] crystallizes in the monoclinic space group P21/n. Crystal structure analysis reveals that there are one and a half manganese ions (one of the manganese ions (Mn2) has a 50% site occupancy), one monoprotoned H4CAS4 ligand, six coordination water molecules, and six lattice water molecules in the asymmetric unit of 1. Of the two independent Mn2+ centers in the asymmetry unit, one
1258
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
(Mn1) is six-coordinated in an octahedral geometry by four water molecules, and two sulfonate groups belonging to two H5CAS3 ligands with their two conelike cavities pointing to the same direction in a cis arrangement, the other (Mn2) is six-coordinated by four water molecules and two monodentate sulfonato groups from two H5CAS3 ligands with their two conelike cavities pointing to the opposite direction in a trans arrangement as shown in Fig. 1. The 1D structure of 1 can be viewed as connection of adjacent mononuclear complexes of transMn(H2O)4(H5CAS3) by a pair of [Mn(H2O)4]2+ cations through the sulfonato group in the trans-Mn(H2O)4(H5CAS3) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 1. This linking mode results in each (H5CAS3) ligand coordinated with three [Mn(H2O)4]2+ cations and the fourth sulfonato group protonated and hydrogen-bonded to the lattice water (O5w) (O2SO– ˚ , O2SO(14) O(5w) = 2.601(4) A ˚, H O(5w) = 1.88 A
Compound 2 [18] crystallizes in the triclinic space group P 1. Crystal structure analysis reveals that there are one and a half manganese ions (one of the manganese ions (Mn2) has a 50% site occupancy), one H4CAS4 ligand, six coordination water molecules, five lattice water molecules and one NHþ 4 in the asymmetric unit of 2. In the two independent manganese centers in the asymmetry unit, Mn1 is sixcoordinated by four water molecules and two sulfonate oxygen atoms of two H4CAS4 ligands with their conelike cavities pointing to the same direction, Mn2 is six-coordinated by four water molecules and sulfonato oxygen atoms from two H4CAS4 ligands with their conelike cavities pointing to the opposite direction. The two sulfonato groups coordinated to Mn1 and Mn2 centers are in a trans arrangement as shown in Fig. 2. The 1D structure of 2 can be viewed as connection of adjacent mononuclear complexes of trans-Mn(H2O)4(H4CAS4) by a pair of [Mn(H2O)4]2+ cations through the sulfonato group in trans-Mn(H2O)4(H4CAS4) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 2. The NHþ 4 ion is hydrogen-bonded to the uncoordinated sulfonato group ˚ , N(1) O(15)SO2 = (H3N(1)–H O(15)SO2 = 1.96 A ˚, 2.860(7) A
Fig. 1. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 1. Lattice water and hydrogen atoms have been omitted for clarity.
Fig. 2. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 2. Lattice water and hydrogen atoms have been omitted for clarity.
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
˚ ,
Fig. 3. Ball and stick plot showing the 2D layer structure of 3. Lattice water and hydrogen atoms have been omitted for clarity (top layer, gray; bottom layer, black).
1259
Since the only difference in the synthesis condition among 1 to 3 is the pH value of the reaction, their structural differences clearly show that the pH value of the reaction is of key importance in the assembly of 4-sulfocalix[4]arene-based coordination polymers, and the higher the pH value of the reaction, the higher the dimension of the complex. For example, at 2.0 mol L1 HCl, one of sulfonato groups of the 4-sulfocalix[4]arene is protonated and each of the remaining sulfonato groups of the 4-sulfocalix[4]arene is respectively coordinated to one Mn2+ ion, 1D chain structure of 1 was formed; while at pH 5, no sulfonato groups of the 4-sulfocalix[4]arene are protonated and each sulfonato group of the 4-sulfocalix[4]arene coordinated with one Mn2+ ion, 2D layer structure of 3 was expected. Interestingly, in the complex 2, although no sulfonato groups of the 4-sulfocalix[4]arene are protonated at pH 4, the 4-sulfocalix[4]arene only coordinated with three Mn2+ ions, instead of four as observed in complex 3. Considered that the concentration of [NHþ 4 ] at pH 4 is by no means larger than that at pH 5 [20], that is, the concentration of [NHþ 4 ] is not key factor influencing on the structures of 2 and 3 at pH 4 and 5, respectively, it is reasonable to attribute the structural difference between 2 and 3 to their difference in the pH value of the reactions, since higher pH value of the reaction would favor the coordination of Mn2+ to the sulfonato group of 4-sulfocalix[4]arene. Although it is clear that the assembly of the complexes is pH-dependent, trying to obtain 2 through transformation of 1 was failure. In stead, we obtained a new 1D chain structure of {(NH4)2[(C28H20O16S4)Mn(H2O)4]}n Æ 6nH2O (4). Crystal analysis [21] reveals that there are two crystallographic independent manganese ions (each manganese ions (Mn2) has a 50% site occupancy), one H4CAS4 ligand, four coordination water molecules, six lattice water molecules and two NHþ 4 in the asymmetric unit of 4. In the two independent manganese centers in the asymmetry unit, both Mn1 and Mn2 are six-coordinated by four water molecules and two sulfonate oxygen atoms of two H4CAS4 ligands with their conelike cavities pointing to the opposite direction. The 1D structure of 4 can be viewed as connection of adjacent mononuclear complexes of transMn(H2O)4(H4CAS4) by a [Mn(H2O)4]2+ cation through the sulfonato group in trans-Mn(H2O)4(H4CAS4) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 4. Since the 1D structure of 4 is neither different from that of 1, nor that of 2, it is reasonable to deduce that 1 could not transform into 2. This is understandable from the difference in the ratio of Mn2+ to H4CAS4 ligand in the related reactions. In the reaction of 2, the ratio of Mn2+ to H4CAS4 ligand is about 9:1, while this in the reaction of 4 is 1.5:1. In summary, based on the same molecular building block, 4-sulfocalix[4]arene and MnCl2, we have synthesized three manganese/4-sulfocalix[4]arene complexes under the different pH conditions. Their structures range from onedimensional to two-dimensional coordination complexes, showing clearly the structural response on pH value of
1260
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
Fig. 4. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 4. Lattice water and hydrogen atoms have been omitted for clarity.
the reaction. Investigation on their structural difference reveals that high pH value of the reaction will favor the coordination of H4CAS4 ligand to Mn2+, and to the formation of high-dimensional coordination polymer. Acknowledgements We thank the NNSFC (Grant Nos. 20471050, 20271044 and 20423002) and the 973 project (Grant 2007CB815304) from MSTC for financial support. Appendix A. Supplementary material Crystallographic data for 1–3 have been deposited with the Cambridge Crystallographic Date CCDC 635453, 635454 and 635455 contain the supplementary crystallographic data for compounds 1, 2 and 3. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; [email protected]]. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2007.08.003. References [1] (a) J.M. Lehn, Supramolecular Chemistry, VCH, Weinheim, 1995; (b) D. Braga, F. Grepioni, G.R. Desiraju, Chem. Rev. 98 (1998) 1375; (c) A.J. Blake, N.R. Champness, P. Hubberstey, W.S. Li, M.A. Withersby, M. Schro¨der, Coordination Chemistry Reviews 183 (1999) 117; (d) P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem., Int. Ed. 38 (1999) 2639; (e) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; (f) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511; (g) G.R. Desiraju, Acc. Chem. Res. 35 (2002) 565; (h) C.N.R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem., Int. Ed. 43 (2004) 1466; (i) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334. [2] S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998) 1460. [3] (a) O.M. Yaghi, G. Li, H. Li, Nature 37 (1995) 703; (b) G.B. Carder, D. Venkataraman, J.S. Moore, S. Lee, Nature 374 (1995) 792.
[4] (a) O.M. Yaghi, H. Li, C. David, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474; (b) S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853. [5] (a) J.L. Atwood, L.J. Barbour, M.J. Hardie, C.L. Raston, Coordin. Chem. Rev. 222 (2001) 3; (b) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Chem. Commun. (2006) 4567. [6] (a) S.G. Bott, A.W. Coleman, J.L. Atwood, J. Am. Chem. Soc. 110 (1988) 610; (b) C.P. Johnson, J.L. Atwood, Inorg. Chem. 35 (1996) 2602; (c) J.L. Atwood, G.W. Orra, N.C. Means, F. Hamada, H.M. Zhang, S.G. Bott, K.D. Robinson, Inorg. Chem. 31 (1992) 603. [7] (a) A. Drljaca, M.J. Hardie, C.L. Raston, J. Chem. Soc., Dalton Trans. (1999) 3639; (b) A. Drljaca, M.J. Hardie, C.L. Raston, L. Spiccia, Chem. Eur. J. 5 (1999) 2295; (c) S. Airey, A. Drljaca, M.J. Hardie, C.L. Raston, Chem. Commun. (1999) 1137; (d) A. Drljaca, M.J. Hardie, T.J. Ness, C.L. Raston, Eur. J. Inorg. Chem. (2000) 2221; (e) M.J. Hardie, J.A. Johnson, C.L. Raston, H.R. Webb, Chem. Commun. (2000) 849; (f) S.J. Dalgarno, C.L. Raston, J. Chem. Soc., Dalton Trans. (2003) 287; (g) S.J. Dalgarno, J. Fisher, C.L. Raston, Chem. Eur. J. 12 (2006) 2772; (h) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Cryst. Growth Des. 6 (2006) 175. [8] A. Drljaca, M.J. Hardie, J.A. Johnson, C.L. Raston, H.R. Webb, Chem. Commun. (1999) 1135. [9] J.L. Atwood, L.J. Barbour, S. Dalgarno, C.L. Raston, H.R. Webb, J. Chem. Soc., Dalton Trans. (2002) 4351. [10] J.L. Atwood, T.N. Ness, P.J. Nichols, C.L. Raston, Cryst. Growth Des. 2 (2002) 171. [11] (a) H.R. Webb, M.J. Hardie, C.L. Raston, Chem. Eur. J. 7 (2001) 3616; (b) S.J. Dalgarno, C.L. Raston, Chem. Commun. (2002) 2216. [12] Y. Liu, D.S. Guo, H.Y. Zhang, S. Kang, H.B. Song, Cryst. Growth Des. 6 (2006) 1399. [13] G.W. Orr, L.J. Barbour, J.L. Atwood, Science 285 (1999) 1043. [14] (a) B.J. Holliday, C.A. Mirkin, Angew. Chem., Int. Ed. Engl. 40 (2001) 2022; (b) K. Maeda, H. Mochizuki, M. Watanabe, E. Yashima, J. Am. Chem. Soc. 128 (2006) 7639. [15] (a) R.D. Gautam, Angew. Chem., Int. Ed. Engl. 34 (1995) 2311; (b) N. Matsumoto, Y. Motoda, T. Matsuo, T. Nakashima, N. Re, F. Dahan, J.-P. Tuchagues, Inorg. Chem. 38 (1999) 1165; (c) J.W. Lee, K. Kim, K. Kim, Chem. Commun. (2001) 1042; (d) D. Braga, L. Maini, M. Polito, E. Tagliavini, F. Grepioni, Coordin. Chem. Rev. 246 (2003) 53;
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261 (e) N. Niklas, F. Hampelb, R. Alsfasser, Chem. Commun. (2003) 1586; (f) J.-H. Yang, S.-L. Zheng, X.-L. Yu, X.-M. Chen, Cryst. Growth Des. 4 (2004) 831; (g) P.-Q. Zheng, Y.-P. Ren, L.-S. Long, R.-B. Huang, L.-S. Zheng, Inorg. Chem. 44 (2005) 1190; (h) P.M. Forster, N. Stock, A.K. Cheetham, Angew. Chem., Int. Ed. 44 (2005) 7608; (i) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Cryst. Growth Des. 6 (2006) 174. [16] (a) M.P. Suh, B.Y. Shim, T.-S. Yoon, Inorg. Chem. 33 (1994) 5509; (b) G. Battistuzzi, M. Borsari, L. Menabue, M. Saladini, M. Sola, Inorg. Chem. 35 (1996) 4239; (c) S.J. Dalgarno, M.J. Hardie, C.L. Raston, Cryst. Growth Des. 4 (2004) 227; (d) Z.-H. Zhou, Y.-F. Deng, H.-L. Wan, Cryst. Growth Des. 5 (2005) 1109; (e) Y.B. Go, X. Wang, E.V. Anokhina, A.J. Jacobson, Inorg. Chem. 44 (2005) 8265; (f) G.Q. Zhang, G.Q. Yang, J.S. Ma, Cryst. Growth Des. 6 (2006) 375; (g) W.-G. Lu, L. Jiang, X.-L. Feng, T.-B. Lu, Cryst. Growth Des. 6 (2006) 564. [17] Preparation of 1: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) were dissolved in hydrochloric (1.5 mL, 2.0 mol L1). When the solution was allowed to stand in air for two weeks colorless plates crystals of 1 were obtained in 27% yield based on 4-sulfocalix[4]arene. Anal. Calcd (found) for {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 6nH2O: C, 32.30 (32.43); H, 4.33 (4.22). Characteristic IR absorption data, m/cm1 (KBr): 3392s, 1638m, 1472m, 1429w, 1374w, 1270m, 1168s, 1122m, 1105m, 1047s, 891w, 814w, 787m, 730w, 660m, 628m, 558m. Preparation of 2: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) was dissolved in water (1.5 mL) and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) was added to the solution. When the pH of the reaction mixture was carefully adjusted to 4.0 by adding ammonia water (0.50 mol L1), and the mixture was allowed to stand in air for three weeks. Pale brown plates crystals of 2 were obtained in 11% yield based on 4-sulfocalix[4]arene. When characteristic IR absorption data, m/cm1 (KBr): 3206s, 1624m, 1474w, 1446w, 1401m, 1276w, 1220m, 1160m, 1120m, 1041m, 891w, 797w, 734w, 661m, 622w, 566m. Preparation of 3: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) was dissolved in water (1.5 mL)
[18]
[19] [20]
[21]
1261
and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) was added to the solution, the pH of the reaction mixture was carefully adjusted to 5 by adding ammonia water (0.50 mol L1), and the mixture was allowed to stand in air for two months. Pale purple plates crystals of 3 were obtained in 7% yield based on 4-sulfocalix[4]arene. Anal. Calcd (found) for [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O: C, 30.47 (30.68); H, 4.352 (4.316); S, 11.63 (11.52). Characteristic IR absorption data, m/cm1 (KBr): 3207s, 2921m, 2851m, 1634m, 1597m, 1448m, 1276m, 1159s, 1121s, 1043s, 896w, 797w, 736w, 660m, 624m, 562m. (It was mentioned that, when the amount of starting materials of the reaction was amplified to four times, and the solution of the reaction was fully evaporated, the yield for complexes 1 to 3 is about 63.7%, 50.4% and 47.8%, respectively). Crystallographic data for (a) 1 (C28H44O28S4Mn1.5): Mr = 1039.28, ˚ , b = 28.589(5) A ˚, c= space group P21/n, a = 11.6842(19) A ˚ , b = 92.973(3),V = 4092.5(11) A ˚ 3, Z = 4, q = 1.687 12.268(2) A g cm3, l = 0.774 mm1, T = 123 K, R1 = 0.0469, wR2 = 0.1184. (b) Compound 2 (C28H45O27N1S4Mn1.5): Mr = 1038.30, space group P 1, ˚ , b = 12.694(4) A ˚ , c = 14.918(5) A ˚ , a = 79.087(6), a = 11.458(4) A ˚ 3, Z = 2, q = 1.715 b = 70.957(6), c = 89.248(6), V = 2011.2(11) A g cm3, l = 0.786 mm1, T = 298 K, R1 = 0.0714, wR2 = 0.1667. (c) Compound 3 (C28H48O30S4Mn2): Mr = 1102.80, space group P4/n, ˚ , c = 13.951(4) A ˚ , V = 1915.7(6) A ˚ 3, Z = 8, q = a = 11.7181(16) A 3 1 1.912 g cm , l = 0.991 mm , T = 123 K, R1 = 0.0796, wR2 = 2155. H. Iki, H. Kijima, I. Hamachi, S. Shinkai, Supramol. Chem. 4 (1995) 223. Considered the pH value in the system of 2 are þ pH ¼ pK a þ lg½NH3 =½NHþ 4 , i.e., lg½NH3 =½NH4 ¼ 5:25 (at pH 4, pKa = pKw pK(NH3) = 14 4.75, K(NH3) = 1.85 · 105) (where [NH3] and [NHþ 4 ] are the concentration at equilibrium at pH 4). Owing to [NH3] = [NHþ 4 ] = C0 (where C0 equals to total concentration of ammonia added in the reaction), we could obtain þ þ lg½NH3 =½NHþ thus lgfC 0 =½NHþ 4 ¼ lg½C 0 NH4 =½NH4 , 4 1g 5:25 þ , which could be simplified as ¼ 5:25, or C 0 =½NH4 1 ¼ 10 þ C 0 =½NHþ 4 ¼ 1. That is, the concentration of ½NH4 at pH 4 equals to the total concentration of ammonia added in the reaction. Similarly, we could also obtain the concentration of ½NHþ 4 at pH 5 equals to the total concentration of ammonia added in the reaction. Crystallographic data for (a) 4 (C28H48MnN2O26S4): Mr = 1011.86, ˚ , b = 12.596(3) A ˚ , c = 14.375(4) A ˚, space group P 1, a = 11.158(3) A ˚ 3, a = 93.055(5), b = 96.850(5), c = 91.026(5), V = 2002.4(9) A Z = 2, q = 1.678 g cm3, l = 0.638 mm1, T = 298 K, R1 = 0.0968. wR2 = 0.2424.
Inorganic Chemistry Communications 10 (2007) 1257–1261 www.elsevier.com/locate/inoche
pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers Rong-Guang Lin, La-Sheng Long *, Rong-Bin Huang, Lan-Sun Zheng State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China Received 31 March 2007; accepted 4 August 2007 Available online 10 August 2007
Abstract Three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ6nH2O (1), {NH4[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 5nH2O (2), [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O (3), have been synthesized under different pH conditions. Complex 1, which exhibits a one-dimensional (1D) structure, is formed at [H+] = 2.0 mol L1. Reaction at pH 4 leads to another one-dimensional (1D) coordination polymer of 2. At pH 5, a two-dimensional (2D) coordination polymer of complex 3 is formed, showing clearly structural effects on pH response. 2007 Elsevier B.V. All rights reserved. Keywords: 4-Sulfocalix[4]arene; Manganese; Coordination polymer; pH-Dependent
Crystal engineering and design of solid-state architectures of coordination polymers are currently of interest in the field of supramolecular chemistry and material science [1,2], due to their potential as functional materials as well as their interesting compositions and topologies [2–4]. Water-soluble calix[n]arenes, possessing strongly hydrophilic upper and lower rims and a strongly hydrophobic conelike cavity, have become increasingly important in the field of supramolecular chemistry and crystal engineering in recent decades [5,6]. As a multifunctional supramolecular synthon, 4-sulfocalixarene can form various kinds of supramolecular aggregations which include ‘Russion dolls’ or ‘molecular capsules’ [7], ‘Ferris wheels’ [8], hydrogen bonded polymers [9], 1D [10] and 2D [9–11] coordination polymers, water-filled channels [12], as well as nanometer scale spheres and tubules [13]. Owing to the assembly of supramolecular architectures easily affected by external physical or chemical stimuli, however, the reaction pathways frequently changed case by case, resulting in
*
Corresponding author. Tel.: +86 592 218 5191; fax: +86 592 218 3047. E-mail address: [email protected] (L.-S. Long).
1387-7003/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2007.08.003
poor selectivity [14]. pH value of the reaction, as one of the external stimuli, is especially important in the assembly of supramolecular architectures [15]. It affects not only the ligand coordination ability but also its charge and, therefore, the metal-to-ligand ratio and, consequently, the resulting topology [5,15,16]. However, systematic investigations focusing on the influence of pH value of the reaction, while keeping numerous other factors constant, are still very rare in this system [15i]. Here we report crystal structures of three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 6nH2O (1), {NH4[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 5nH2O (2), [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O (3), which are prepared under the different pH conditions [17]. Their structural diversities show clearly structural effects on pH response. Compound 1 [18] crystallizes in the monoclinic space group P21/n. Crystal structure analysis reveals that there are one and a half manganese ions (one of the manganese ions (Mn2) has a 50% site occupancy), one monoprotoned H4CAS4 ligand, six coordination water molecules, and six lattice water molecules in the asymmetric unit of 1. Of the two independent Mn2+ centers in the asymmetry unit, one
1258
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
(Mn1) is six-coordinated in an octahedral geometry by four water molecules, and two sulfonate groups belonging to two H5CAS3 ligands with their two conelike cavities pointing to the same direction in a cis arrangement, the other (Mn2) is six-coordinated by four water molecules and two monodentate sulfonato groups from two H5CAS3 ligands with their two conelike cavities pointing to the opposite direction in a trans arrangement as shown in Fig. 1. The 1D structure of 1 can be viewed as connection of adjacent mononuclear complexes of transMn(H2O)4(H5CAS3) by a pair of [Mn(H2O)4]2+ cations through the sulfonato group in the trans-Mn(H2O)4(H5CAS3) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 1. This linking mode results in each (H5CAS3) ligand coordinated with three [Mn(H2O)4]2+ cations and the fourth sulfonato group protonated and hydrogen-bonded to the lattice water (O5w) (O2SO– ˚ , O2SO(14) O(5w) = 2.601(4) A ˚, H O(5w) = 1.88 A
Compound 2 [18] crystallizes in the triclinic space group P 1. Crystal structure analysis reveals that there are one and a half manganese ions (one of the manganese ions (Mn2) has a 50% site occupancy), one H4CAS4 ligand, six coordination water molecules, five lattice water molecules and one NHþ 4 in the asymmetric unit of 2. In the two independent manganese centers in the asymmetry unit, Mn1 is sixcoordinated by four water molecules and two sulfonate oxygen atoms of two H4CAS4 ligands with their conelike cavities pointing to the same direction, Mn2 is six-coordinated by four water molecules and sulfonato oxygen atoms from two H4CAS4 ligands with their conelike cavities pointing to the opposite direction. The two sulfonato groups coordinated to Mn1 and Mn2 centers are in a trans arrangement as shown in Fig. 2. The 1D structure of 2 can be viewed as connection of adjacent mononuclear complexes of trans-Mn(H2O)4(H4CAS4) by a pair of [Mn(H2O)4]2+ cations through the sulfonato group in trans-Mn(H2O)4(H4CAS4) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 2. The NHþ 4 ion is hydrogen-bonded to the uncoordinated sulfonato group ˚ , N(1) O(15)SO2 = (H3N(1)–H O(15)SO2 = 1.96 A ˚, 2.860(7) A
Fig. 1. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 1. Lattice water and hydrogen atoms have been omitted for clarity.
Fig. 2. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 2. Lattice water and hydrogen atoms have been omitted for clarity.
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
˚ ,
Fig. 3. Ball and stick plot showing the 2D layer structure of 3. Lattice water and hydrogen atoms have been omitted for clarity (top layer, gray; bottom layer, black).
1259
Since the only difference in the synthesis condition among 1 to 3 is the pH value of the reaction, their structural differences clearly show that the pH value of the reaction is of key importance in the assembly of 4-sulfocalix[4]arene-based coordination polymers, and the higher the pH value of the reaction, the higher the dimension of the complex. For example, at 2.0 mol L1 HCl, one of sulfonato groups of the 4-sulfocalix[4]arene is protonated and each of the remaining sulfonato groups of the 4-sulfocalix[4]arene is respectively coordinated to one Mn2+ ion, 1D chain structure of 1 was formed; while at pH 5, no sulfonato groups of the 4-sulfocalix[4]arene are protonated and each sulfonato group of the 4-sulfocalix[4]arene coordinated with one Mn2+ ion, 2D layer structure of 3 was expected. Interestingly, in the complex 2, although no sulfonato groups of the 4-sulfocalix[4]arene are protonated at pH 4, the 4-sulfocalix[4]arene only coordinated with three Mn2+ ions, instead of four as observed in complex 3. Considered that the concentration of [NHþ 4 ] at pH 4 is by no means larger than that at pH 5 [20], that is, the concentration of [NHþ 4 ] is not key factor influencing on the structures of 2 and 3 at pH 4 and 5, respectively, it is reasonable to attribute the structural difference between 2 and 3 to their difference in the pH value of the reactions, since higher pH value of the reaction would favor the coordination of Mn2+ to the sulfonato group of 4-sulfocalix[4]arene. Although it is clear that the assembly of the complexes is pH-dependent, trying to obtain 2 through transformation of 1 was failure. In stead, we obtained a new 1D chain structure of {(NH4)2[(C28H20O16S4)Mn(H2O)4]}n Æ 6nH2O (4). Crystal analysis [21] reveals that there are two crystallographic independent manganese ions (each manganese ions (Mn2) has a 50% site occupancy), one H4CAS4 ligand, four coordination water molecules, six lattice water molecules and two NHþ 4 in the asymmetric unit of 4. In the two independent manganese centers in the asymmetry unit, both Mn1 and Mn2 are six-coordinated by four water molecules and two sulfonate oxygen atoms of two H4CAS4 ligands with their conelike cavities pointing to the opposite direction. The 1D structure of 4 can be viewed as connection of adjacent mononuclear complexes of transMn(H2O)4(H4CAS4) by a [Mn(H2O)4]2+ cation through the sulfonato group in trans-Mn(H2O)4(H4CAS4) complex coordinated to [Mn(H2O)4]2+ cations as shown in Fig. 4. Since the 1D structure of 4 is neither different from that of 1, nor that of 2, it is reasonable to deduce that 1 could not transform into 2. This is understandable from the difference in the ratio of Mn2+ to H4CAS4 ligand in the related reactions. In the reaction of 2, the ratio of Mn2+ to H4CAS4 ligand is about 9:1, while this in the reaction of 4 is 1.5:1. In summary, based on the same molecular building block, 4-sulfocalix[4]arene and MnCl2, we have synthesized three manganese/4-sulfocalix[4]arene complexes under the different pH conditions. Their structures range from onedimensional to two-dimensional coordination complexes, showing clearly the structural response on pH value of
1260
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261
Fig. 4. ORTEP plot showing the coordination environment of Mn2+ and the 1D structure of 4. Lattice water and hydrogen atoms have been omitted for clarity.
the reaction. Investigation on their structural difference reveals that high pH value of the reaction will favor the coordination of H4CAS4 ligand to Mn2+, and to the formation of high-dimensional coordination polymer. Acknowledgements We thank the NNSFC (Grant Nos. 20471050, 20271044 and 20423002) and the 973 project (Grant 2007CB815304) from MSTC for financial support. Appendix A. Supplementary material Crystallographic data for 1–3 have been deposited with the Cambridge Crystallographic Date CCDC 635453, 635454 and 635455 contain the supplementary crystallographic data for compounds 1, 2 and 3. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; [email protected]]. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2007.08.003. References [1] (a) J.M. Lehn, Supramolecular Chemistry, VCH, Weinheim, 1995; (b) D. Braga, F. Grepioni, G.R. Desiraju, Chem. Rev. 98 (1998) 1375; (c) A.J. Blake, N.R. Champness, P. Hubberstey, W.S. Li, M.A. Withersby, M. Schro¨der, Coordination Chemistry Reviews 183 (1999) 117; (d) P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem., Int. Ed. 38 (1999) 2639; (e) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; (f) O.R. Evans, W. Lin, Acc. Chem. Res. 35 (2002) 511; (g) G.R. Desiraju, Acc. Chem. Res. 35 (2002) 565; (h) C.N.R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem., Int. Ed. 43 (2004) 1466; (i) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334. [2] S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998) 1460. [3] (a) O.M. Yaghi, G. Li, H. Li, Nature 37 (1995) 703; (b) G.B. Carder, D. Venkataraman, J.S. Moore, S. Lee, Nature 374 (1995) 792.
[4] (a) O.M. Yaghi, H. Li, C. David, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474; (b) S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853. [5] (a) J.L. Atwood, L.J. Barbour, M.J. Hardie, C.L. Raston, Coordin. Chem. Rev. 222 (2001) 3; (b) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Chem. Commun. (2006) 4567. [6] (a) S.G. Bott, A.W. Coleman, J.L. Atwood, J. Am. Chem. Soc. 110 (1988) 610; (b) C.P. Johnson, J.L. Atwood, Inorg. Chem. 35 (1996) 2602; (c) J.L. Atwood, G.W. Orra, N.C. Means, F. Hamada, H.M. Zhang, S.G. Bott, K.D. Robinson, Inorg. Chem. 31 (1992) 603. [7] (a) A. Drljaca, M.J. Hardie, C.L. Raston, J. Chem. Soc., Dalton Trans. (1999) 3639; (b) A. Drljaca, M.J. Hardie, C.L. Raston, L. Spiccia, Chem. Eur. J. 5 (1999) 2295; (c) S. Airey, A. Drljaca, M.J. Hardie, C.L. Raston, Chem. Commun. (1999) 1137; (d) A. Drljaca, M.J. Hardie, T.J. Ness, C.L. Raston, Eur. J. Inorg. Chem. (2000) 2221; (e) M.J. Hardie, J.A. Johnson, C.L. Raston, H.R. Webb, Chem. Commun. (2000) 849; (f) S.J. Dalgarno, C.L. Raston, J. Chem. Soc., Dalton Trans. (2003) 287; (g) S.J. Dalgarno, J. Fisher, C.L. Raston, Chem. Eur. J. 12 (2006) 2772; (h) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Cryst. Growth Des. 6 (2006) 175. [8] A. Drljaca, M.J. Hardie, J.A. Johnson, C.L. Raston, H.R. Webb, Chem. Commun. (1999) 1135. [9] J.L. Atwood, L.J. Barbour, S. Dalgarno, C.L. Raston, H.R. Webb, J. Chem. Soc., Dalton Trans. (2002) 4351. [10] J.L. Atwood, T.N. Ness, P.J. Nichols, C.L. Raston, Cryst. Growth Des. 2 (2002) 171. [11] (a) H.R. Webb, M.J. Hardie, C.L. Raston, Chem. Eur. J. 7 (2001) 3616; (b) S.J. Dalgarno, C.L. Raston, Chem. Commun. (2002) 2216. [12] Y. Liu, D.S. Guo, H.Y. Zhang, S. Kang, H.B. Song, Cryst. Growth Des. 6 (2006) 1399. [13] G.W. Orr, L.J. Barbour, J.L. Atwood, Science 285 (1999) 1043. [14] (a) B.J. Holliday, C.A. Mirkin, Angew. Chem., Int. Ed. Engl. 40 (2001) 2022; (b) K. Maeda, H. Mochizuki, M. Watanabe, E. Yashima, J. Am. Chem. Soc. 128 (2006) 7639. [15] (a) R.D. Gautam, Angew. Chem., Int. Ed. Engl. 34 (1995) 2311; (b) N. Matsumoto, Y. Motoda, T. Matsuo, T. Nakashima, N. Re, F. Dahan, J.-P. Tuchagues, Inorg. Chem. 38 (1999) 1165; (c) J.W. Lee, K. Kim, K. Kim, Chem. Commun. (2001) 1042; (d) D. Braga, L. Maini, M. Polito, E. Tagliavini, F. Grepioni, Coordin. Chem. Rev. 246 (2003) 53;
R.-G. Lin et al. / Inorganic Chemistry Communications 10 (2007) 1257–1261 (e) N. Niklas, F. Hampelb, R. Alsfasser, Chem. Commun. (2003) 1586; (f) J.-H. Yang, S.-L. Zheng, X.-L. Yu, X.-M. Chen, Cryst. Growth Des. 4 (2004) 831; (g) P.-Q. Zheng, Y.-P. Ren, L.-S. Long, R.-B. Huang, L.-S. Zheng, Inorg. Chem. 44 (2005) 1190; (h) P.M. Forster, N. Stock, A.K. Cheetham, Angew. Chem., Int. Ed. 44 (2005) 7608; (i) S.J. Dalgarno, J.L. Atwood, C.L. Raston, Cryst. Growth Des. 6 (2006) 174. [16] (a) M.P. Suh, B.Y. Shim, T.-S. Yoon, Inorg. Chem. 33 (1994) 5509; (b) G. Battistuzzi, M. Borsari, L. Menabue, M. Saladini, M. Sola, Inorg. Chem. 35 (1996) 4239; (c) S.J. Dalgarno, M.J. Hardie, C.L. Raston, Cryst. Growth Des. 4 (2004) 227; (d) Z.-H. Zhou, Y.-F. Deng, H.-L. Wan, Cryst. Growth Des. 5 (2005) 1109; (e) Y.B. Go, X. Wang, E.V. Anokhina, A.J. Jacobson, Inorg. Chem. 44 (2005) 8265; (f) G.Q. Zhang, G.Q. Yang, J.S. Ma, Cryst. Growth Des. 6 (2006) 375; (g) W.-G. Lu, L. Jiang, X.-L. Feng, T.-B. Lu, Cryst. Growth Des. 6 (2006) 564. [17] Preparation of 1: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) were dissolved in hydrochloric (1.5 mL, 2.0 mol L1). When the solution was allowed to stand in air for two weeks colorless plates crystals of 1 were obtained in 27% yield based on 4-sulfocalix[4]arene. Anal. Calcd (found) for {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]}n Æ 6nH2O: C, 32.30 (32.43); H, 4.33 (4.22). Characteristic IR absorption data, m/cm1 (KBr): 3392s, 1638m, 1472m, 1429w, 1374w, 1270m, 1168s, 1122m, 1105m, 1047s, 891w, 814w, 787m, 730w, 660m, 628m, 558m. Preparation of 2: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) was dissolved in water (1.5 mL) and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) was added to the solution. When the pH of the reaction mixture was carefully adjusted to 4.0 by adding ammonia water (0.50 mol L1), and the mixture was allowed to stand in air for three weeks. Pale brown plates crystals of 2 were obtained in 11% yield based on 4-sulfocalix[4]arene. When characteristic IR absorption data, m/cm1 (KBr): 3206s, 1624m, 1474w, 1446w, 1401m, 1276w, 1220m, 1160m, 1120m, 1041m, 891w, 797w, 734w, 661m, 622w, 566m. Preparation of 3: MnCl2 Æ 6H2O (0.050 g, 0.25 mmol) was dissolved in water (1.5 mL)
[18]
[19] [20]
[21]
1261
and 4-sulfocalix[4]arene (0.022 g, 0.028 mmol) was added to the solution, the pH of the reaction mixture was carefully adjusted to 5 by adding ammonia water (0.50 mol L1), and the mixture was allowed to stand in air for two months. Pale purple plates crystals of 3 were obtained in 7% yield based on 4-sulfocalix[4]arene. Anal. Calcd (found) for [(C28H20O16S4)Mn2(H2O)8]n Æ 6nH2O: C, 30.47 (30.68); H, 4.352 (4.316); S, 11.63 (11.52). Characteristic IR absorption data, m/cm1 (KBr): 3207s, 2921m, 2851m, 1634m, 1597m, 1448m, 1276m, 1159s, 1121s, 1043s, 896w, 797w, 736w, 660m, 624m, 562m. (It was mentioned that, when the amount of starting materials of the reaction was amplified to four times, and the solution of the reaction was fully evaporated, the yield for complexes 1 to 3 is about 63.7%, 50.4% and 47.8%, respectively). Crystallographic data for (a) 1 (C28H44O28S4Mn1.5): Mr = 1039.28, ˚ , b = 28.589(5) A ˚, c= space group P21/n, a = 11.6842(19) A ˚ , b = 92.973(3),V = 4092.5(11) A ˚ 3, Z = 4, q = 1.687 12.268(2) A g cm3, l = 0.774 mm1, T = 123 K, R1 = 0.0469, wR2 = 0.1184. (b) Compound 2 (C28H45O27N1S4Mn1.5): Mr = 1038.30, space group P 1, ˚ , b = 12.694(4) A ˚ , c = 14.918(5) A ˚ , a = 79.087(6), a = 11.458(4) A ˚ 3, Z = 2, q = 1.715 b = 70.957(6), c = 89.248(6), V = 2011.2(11) A g cm3, l = 0.786 mm1, T = 298 K, R1 = 0.0714, wR2 = 0.1667. (c) Compound 3 (C28H48O30S4Mn2): Mr = 1102.80, space group P4/n, ˚ , c = 13.951(4) A ˚ , V = 1915.7(6) A ˚ 3, Z = 8, q = a = 11.7181(16) A 3 1 1.912 g cm , l = 0.991 mm , T = 123 K, R1 = 0.0796, wR2 = 2155. H. Iki, H. Kijima, I. Hamachi, S. Shinkai, Supramol. Chem. 4 (1995) 223. Considered the pH value in the system of 2 are þ pH ¼ pK a þ lg½NH3 =½NHþ 4 , i.e., lg½NH3 =½NH4 ¼ 5:25 (at pH 4, pKa = pKw pK(NH3) = 14 4.75, K(NH3) = 1.85 · 105) (where [NH3] and [NHþ 4 ] are the concentration at equilibrium at pH 4). Owing to [NH3] = [NHþ 4 ] = C0 (where C0 equals to total concentration of ammonia added in the reaction), we could obtain þ þ lg½NH3 =½NHþ thus lgfC 0 =½NHþ 4 ¼ lg½C 0 NH4 =½NH4 , 4 1g 5:25 þ , which could be simplified as ¼ 5:25, or C 0 =½NH4 1 ¼ 10 þ C 0 =½NHþ 4 ¼ 1. That is, the concentration of ½NH4 at pH 4 equals to the total concentration of ammonia added in the reaction. Similarly, we could also obtain the concentration of ½NHþ 4 at pH 5 equals to the total concentration of ammonia added in the reaction. Crystallographic data for (a) 4 (C28H48MnN2O26S4): Mr = 1011.86, ˚ , b = 12.596(3) A ˚ , c = 14.375(4) A ˚, space group P 1, a = 11.158(3) A ˚ 3, a = 93.055(5), b = 96.850(5), c = 91.026(5), V = 2002.4(9) A Z = 2, q = 1.678 g cm3, l = 0.638 mm1, T = 298 K, R1 = 0.0968. wR2 = 0.2424.