Heterometallic Copper(II)–Potassium 3D Coordination Polymers

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Heterometallic Copper(II) Potassium 3D Coordination Polymers Driven by Multifunctionalized Azo Derivatives of β-Diketones Maximilian N. Kopylovich,† Yauhen Yu. Karabach,† Kamran T. Mahmudov,† Matti Haukka,‡ Alexander M. Kirillov,† Pawez J. Figiel,† and Armando J. L. Pombeiro*,† †

Centro de Química Estrutural, Complexo I, Instituto Superior T
ecnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal ‡ Department of Chemistry, University of Eastern Finland, P.O. Box 111, FIN-80101, Joensuu, Finland

bS Supporting Information ABSTRACT: New 3D Cu(II)-K coordination polymers (CPs), [CuK(μ7-L1)(H2O)]n 3 nH2O (1), and [CuK(μ5-L2)(H2O)]n 3 2nH2O (2), were easily generated by self-assembly from copper(II) nitrate, potassium hydroxide, and azo derivatives of β-diketones, namely 3-(2-hydroxy-3-sulfo-5-chlorophenylhydrazo)pentane-2,4dione (H3L1) or 3-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)pentane-2,4-dione (H3L2). The single-crystal structures of 1 and 2 disclose similar 3D metal organic networks, driven by the 5-connected potassium, 6-connected L1, or 5-connected L2 nodes. The topological analysis of 1 reveals a rare binodal 5,6-connected underlying net with an unprecedented topology defined by the point (Schl€afli) symbol of (3 3 45 3 53 3 6)(32 3 46 3 53 3 64), while 2 features a uninodal 5-connected net with the bnn (hexagonal boron nitride) topology and the point symbol of (46 3 64). Both networks possess voids filled by crystallization water molecules, the reversible escape and binding of which was studied by thermal analyses. Upon a dehydration adsorption cycle, 1 undergoes structural changes, although without loss of crystallinity, while 2 basically preserves its initial structure, as confirmed by X-ray powder diffraction analyses. Besides, 1 and 2 act as catalyst precursors for the aerobic TEMPOmediated selective oxidation of benzyl alcohol to benzaldehyde in aqueous medium.

T

he design of new copper(II) CPs with attractive functional properties is an increasingly growing field of research.1,2 This fact can be related to the redox, magnetic, and coordinative versatilities of the copper ions within the metal organic frameworks. Often in the synthesis of copper containing CPs, the utilization of various polydentate N- and/or O-chelating terminal and bridging ligands (e.g., aminoalcohols, polycarboxylates, polynitriles, pyridyls, etc.), as well as of alkali metal ions, allows creation of polymeric architectures of diverse geometries and properties.1,2 Many ligands, used for the synthesis of copper CPs, contain either diketo- or azo-fragments, but not both of them.3,4 Azo derivatives of β-diketones (ADBs) are potentially versatile building blocks having, in one molecule, diketo- and azo-moieties and thus combining the coordination abilities of both these functional groups.5 In particular, ADBs bearing various functional groups (e.g., SO3H, OH, Cl, NO2, etc.) can coordinate copper and other metals in both terminal chelating and bridging modes, thus expanding the possibility for creating new polynuclear architectures. However, the number of copper(II) ADB polynuclear complexes is still rather scant,5 whereas the metal organic networks derived from ADBs are limited thus far to single examples.6 Hence, in pursuit of our recent studies on the synthesis of (i) copper organic networks7 and (ii) various copper ADB r 2011 American Chemical Society

derivatives,5,6a the main aim of the present work consists in the exploration of the yet unrealized potential of multifunctionalized ADB ligands as versatile building blocks for the design of 3D coordination networks. Thus, we now report the application of functionalized ADB ligands, 3-(2-hydroxy-3-sulfo-5-chlorophenylhydrazo)pentane-2, 4-dione (H3L1) and 3-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)pentane-2,4-dione (H3L2), for the synthesis of two new copper(II) potassium 3D coordination polymers, [CuK(μ7-L1)(H2O)]n 3 nH2O (1) and [CuK(μ5-L2)(H2O)]n 3 2nH2O (2) (Scheme 1). These compounds were generated by simple one-pot self-assembly procedures8 and isolated in good yields (51 68%) as brown (1) or dark-green (2) crystals upon slow evaporation at 25 °C of the reaction mixtures. The latter were obtained after stirring for a short time (5 min) the ethanol/acetone (1:1, v/v) or water solutions of H3L1 or H3L2, respectively, copper(II) nitrate, and potassium hydroxide.8 It should be mentioned that similar reactions and crystallization attempts using other alkali metal hydroxides (e.g., LiOH or NaOH) instead of KOH were not successful, thus pointing out the importance of K+ ions in the formation of Received: May 16, 2011 Revised: July 22, 2011 Published: August 17, 2011 4247

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Scheme 1. Simplified Structural Formulas of 1 (a) and 2 (b)a

a

The numbers indicate the corresponding extensions of polymeric motifs.

the present types of coordination polymers. The molecular structures of 1 and 2 were determined by single-crystal X-ray crystallography9 and supported by IR spectroscopy and elemental and differential thermal analyses. The crystal structures of 1 and 2 (Figure 1a,b) are constructed from copper(II) and potassium ions coupled via chelating anionic ADB ligands that act in overall μ7- or μ5-bridging modes, respectively. They equalize the charges of metal ions and provide further interconnection of the [CuK(μ-L1,2)(H2O)] units into infinite 3D metal organic frameworks (Figure 1c,d). In 1, the coordination sphere of the five-coordinate Cu1 atom is filled by the O5, O7, and N1 donor atoms [Cu1 O5 1.909(5), Cu1 O7 1.925(5), Cu1 N1 1.900(6) Å] of μ7-L1 that occupy basal positions and lie in plane with the parent atom [mean deviation of 0.003 Å], while the water oxygen O6 [Cu1 O6 1.935(6) Å] occupies a fourth basal position and deviates from the plane by 0.270 Å. The apical site is taken by the carbonyl oxygen O4 of an adjacent μ7-L1 moiety with a rather long Cu1 O4 bond distance of 2.760(12) Å (Figure 1a). Consequently, the Cu1 atoms exhibit a distorted square-pyramidal coordination geometry characterized by the τ parameter of ca. 0.033.10 Although in 2 the Cu1 atom and L2 are ligated in a manner similar to that of 1 (Figure 1a,b), the main distinctive feature of 2 consists in the absence of a coordination bond between the Cu1 center and the O4* atom from an adjacent ADB moiety [for all the symmetry operators, see Table S1; for simplicity, hereinafter asterisks correspond to symmetry generated atoms]. In fact, the Cu1 3 3 3 O4* separation [2.956(2) Å] is above the sum of the van der Waals radii of the Cu and O atoms [2.92 Å].11 Hence, the four-coordinate Cu1 atoms in 2 adopt a distorted square planar geometry [mean deviation from the plane of 0.06 Å] filled by the O5, O6, and N1 atoms of L2 and the O7 atom of the aqua ligand, with the bonding distances similar to those of 1 (Table S1). Owing to the chelating behavior of L1 and L2, the Cu1 atoms in 1 and 2 participate in two penta- and hexaorganometallacycles [e.g., Cu1 N1 C6 C1 O7 and Cu1 N1 C5 C6 O7 in 1], where the Cu1 and the corresponding ligand atoms lie in the same plane with a mean deviation of 0.013/0.022 and 0.044/0.035 Å, respectively. The bonding parameters within these organometallacycles (Table S1) are comparable to those of other Cu-ADB derivatives,5,6a also suggesting an electron density delocalization.

In both 1 and 2, the potassium atoms K1 adopt eightcoordinate {KO7Cl} or {KO8} environments, respectively (for bonding parameters, see Table S1 of the Supporting Information). The K1 centers bind five symmetry generated ADB moieties, thus acting as 5-connected nodes and providing the interlinkage of the [CuK(μ-L1,2)(H2O)] units in three directions (Figures 1 and 2). Hence, the ∼[K O2SO(O) L1,2 CdO]∼ 1D motifs are formed via coordination of the sulfo O1* and O2*, alkoxy O7* (or O6* in 2), and carbonyl O4* oxygen atoms of the neighboring ADB ligands to the potassium atoms (Figure 2a,b; blue arrows). These 1D motifs are further assembled into square grid layers via linkages of the K1 atoms with the Cl1* atoms of L1 [K1 Cl1* 3.390(3) Å] in 1 or the O8* and O9* atoms of nitro groups of L2 [K1 O8* 2.8812(17), K1 O9* 3.2732(16) Å] in 2 (Figure 2a, b; orange arrows). The interconnection of these layers into the overall 3D networks is provided by the sulfo oxygen atoms O1 and O2, which also act as bridges between the K1* atoms of the neighboring layers (Figure 2c,d; blue and orange planes correspond to the alternatively oriented collateral CP layers). The separation between the layers interconnected via the O1 atoms is shorter than that between the layers formed through bonds with the O2 atoms [3.009 vs 3.541 Å and 3.277 vs 3.392 Å for 1 and 2, correspondingly]. Besides, the sewing of the layers in 1 is further supported by the coordination of alkoxy oxygen atoms to the K1 atoms [K1 O7* 3.111(5) Å] and by the Cu1 O4 bond (Figure 2c, Table S1 of the Supporting Information). Furthermore, the 3D networks of 1 and 2 are additionally strengthened by multiple hydrogen bonds (Table S2 of the Supporting Information) involving crystallization and coordinated water molecules and by π 3 3 3 π stacking interactions between adjacent [CuK(μ-L1,2)(H2O)] units. A noteworthy feature of 2 also consists in the repeating H-bonding interactions of the coordinated O7 and crystallization O1S and O2S water molecules (also including their symmetry equivalents), thus giving rise to the branched infinite 1D {(H2O)6}n chains that run along the b axis (Figure S2 of the Supporting Information). These 1D water chains can be classified as C4A2 according to the systematization introduced by Infanes et al.12 For a better understanding of the intricate metal organic network of 1, we have carried out its topological analysis using TOPOS software13 and following the concept of the simplified underlying net.14 Thus, after reducing the organic building blocks 4248

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Figure 1. Structural fragments of 1 (a, c) and 2 (b, d) showing (a, b) ellipsoid plots (50% probability) with atom numbering scheme and (c, d) infinite 3D metal organic frameworks viewed along the a axis, with crystallization water molecules represented by a “space fill” model. H atoms (apart from those of H2O molecules) are omitted for clarity; intramolecular H-bonds are shown as gray dashed lines. Color codes: Cu (green), K (pink), C (gray), O (red), Cl (light green), N (blue), H (pale gray).

L1 to their centroids and omitting terminal H2O ligands (O6), the structure of 1 can be described as an underlying net constructed from the 5-connected K1 and the 6-connected L1 nodes, as well as the 2-connected Cu1 linkers. The topological analysis of this net discloses a binodal 5,6-connected framework (Figure 3a) with the new topology described by the point (Schl€afli) symbol of (3 3 45 3 53 3 6)(32 3 46 3 53 3 64), wherein the notations (3 3 45 3 53 3 6) and (32 3 46 3 53 3 64) correspond to the K1 and L1 nodes, respectively. The unprecedented character of this topology has been confirmed by the search over various databases.3,13,15 In spite of being still not very common, other examples of binodal 5,6-connected networks have been reported in recent years.16 From a topological point of view, the main difference of the metal organic network of 2 in comparison with that of 1 arises from the absence of the coordination bond between the Cu1 center and the O4* atom from the adjacent L2 moiety. As a result, the Cu1 atoms in 2 do not act as linkers between the L2 nodes. After contracting the CuL2 moieties to their centroids and eliminating terminal H2O ligands (O7), the resulting underlying net of 2 is composed of the 5-connected K1 and CuL2 nodes that are topologically equivalent, thus forming a uninodal 5-connected framework (Figure 3b) with the point symbol (46 3 64). This simplified net features the bnn (hexagonal boron nitride) topology according to the RCSR classification.15 However, if the intermolecular

Cu1 3 3 3 O4* interaction is taken into consideration, the topology of the resulting supramolecular net in 2 is similar to that of the valence-bonded underlying net 1. Although CPs with the bnn topology occur rather frequently,13,14c,17 compound 2 represents the first potassium containing net that adopts this type of topology. The differential thermal analysis of 1 and 2 reveals three and five thermal effects, respectively, over the 30 750 °C temperature range (Figure S7 and Table S4 of the Supporting Information). In the case of 1, the endothermic process in the 25 250 °C range with a maximum at 97 °C and overall mass loss of ca. 7.5% (calculated 7.7%) corresponds to elimination of two coordinated and crystallization water molecules. In the case of 2, two crystallization and one coordinated water molecules are released stepwise in the 25 70, 70 120, and 120 150 °C ranges (maxima at 50, 118, and 127 °C), corresponding to the mass loss of, on average, 3.5% per each step (calculated 3.6%). Further exothermic processes in the 150 350 (1) and 150 366 °C (2) temperature intervals are presumably associated to the multistep decomposition of the ligands. The X-ray powder diffraction analysis of 1 performed after its heating to 145 °C demonstrates some structural changes, although the thus formed product does not lose crystallinity (Figure S9a of the Supporting Information) and exhibits the ability of reversible adsorption from air of two water molecules per formula unit (Figure S8a,b of the Supporting Information). 4249

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Figure 2. Structural fragments of 1 (a, c) and 2 (b, d) showing (a, b) formation of the square-grid layers and (c, d) their interconnection into 3D networks; blue and pink planes correspond to the alternatively oriented layers and are drawn through the Cu1 atoms. The H atoms and crystallization water molecules are omitted for clarity; ellipsoids are drawn at the 50% probability level. Color codes: Cu (green), K (pink), C (gray), O (red), Cl (light green), N (blue).

Figure 3. Topological representations of the simplified underlying 3D nets showing (a) the binodal 5,6-connected network of 1 with the unprecedented topology and (b) the uninodal 5-connected network of 2 with the bnn topology. Further details: rotated views along the a (a) and b (b) axes. Color codes: 5-connected K1 nodes (pink), centroids of 6-connected L1 (a) or 5-connected CuL2 nodes (b) (yellow), Cu1 linkers (a) (green).

In contrast, after its dehydration at 85 °C, compound 2 reversibly adsorbs from air, in ca. 13 h, only one water molecule (Figure 3c,d). Moreover, the X-ray powder diffraction analysis of the compound after two dehydration adsorption cycles indicates that 2 basically preserves its initial structure (Figure S9b of the Supporting Information).

Owing to the presence of sulfo groups and potassium ions, both CPs display some solubility in water [S25°C = 0.5 (1) or 0.6 (2) g L 1] due to their partial dissociation, which can be important for potential biological18 or catalytic5a,6a,7b,7e applications in aqueous media. In fact, the preliminary studies show that 4250

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Crystal Growth & Design 1 and 2 act as catalyst precursors for the benzyl alcohol oxidation in alkaline (0.1 M K2CO3) aqueous solution, by O2/air in the presence of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) (Scheme S2),19 providing 60 (1) and 28% (2) yields of benzaldehyde after 6 h, and with a high selectivity (>99%) (Scheme S2, Table S5, runs 1 and 3). These yields are superior to that of 20% achieved in the oxidation catalyzed by a simple Cu(II) salt, Cu(NO3)2 (run 5). Extension of the reaction time to 18 h increases the yield of benzaldehyde up to 67 and 54% when using 1 and 2, respectively (Table S5, runs 2 and 4). As previously reported,5a,6a,20 we have also found that the presence of base (K2CO3), as well as of the TEMPO radical, is crucial to obtain high yields. We expect that our current catalytic system follows the previously proposed5a,6a mechanism, which involves coordination of the alcohol (alcoholate) and TEMPO to the copper center and β-hydrogen abstraction from the former by the latter ligand to form TEMPOH and a ligated alkoxyl radical which converts to the aldehyde. In summary, we have synthesized and fully characterized two novel heterometallic copper(II) potassium 3D coordination polymers, thus showing that the still underexplored multifunctionalized azo derivatives of β-diketones can act as versatile building blocks for the engineering of 3D metal organic networks. The study also contributes to the identification and classification of metal organic materials with new topologies.14 In particular, compound 1 reveals a rare binodal 5,6-connected net with the unprecedented topology, whereas 2 is a uninodal 5-connected net with the bnn topology. Besides, infinite 1D {(H2O)6}n chains have been identified in the structure of 2, thus widening the family of metal organic materials that host water clusters or polymeric water assemblies.21,22 Efficient reversible water sorption desorption and selective benzyl alcohol oxidation in water were achieved for the synthesized CPs. These results are of significance in designing new coordination networks driven by various ADB building blocks with desired useful properties, namely concerning gas sorption and oxidation catalysis.

’ ASSOCIATED CONTENT

bS

Supporting Information. Materials and instrumentation, synthesis and characterization of H3L1 and H3L2, refinement details of X-ray analyses, selected bonding parameters (Tables S1 S3), additional structural (Figures S1 S4) and topological (Figures S5 and S6) representations of 1 and 2, results of thermal (Figures S7 and S8; Table 4) and X-ray powder diffraction (Figure S9) analyses, procedure and additional discussion of catalytic studies, and crystallographic files in CIF format. This material is available free of charge via the Internet at http:// pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected] (A.J.L.P.). Phone: +351 218419237. Fax: +351 218464455.

’ ACKNOWLEDGMENT This work was supported by the Foundation for Science and Technology (FCT), Portugal, Pest-OE/QUI/UI0100/2011 and PTDC/QUI-QUI/102150/2008 projects, and “Science 2007” program. Y.Yu.K., K.T.M., and P.J.F. express gratitude to the

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FCT for their postdoc fellowships. We thank the Portuguese NMR Network (IST-UTL Center) for providing access to the NMR facility.

’ REFERENCES (1) (a) Batten, S. R.; Turner, D. R.; Neville, S. M. Coordination Polymers: Design, Analysis and Application; Royal Society of Chemistry: London, 2009. (b) Design and Construction of Coordination Polymers; Hong, M.-C., Chen, L., Eds.; Wiley: 2009. (c) Metal-Organic Frameworks: Design and Application; MacGillivray, L. R., Ed.; Wiley-Interscience: 2010. (d) Functional Metal-Organic Frameworks: Gas Storage, Separation and Catalysis; Schroder, M., Ed.; Springer: 2010. (2) For selected reviews on CPs, see: (a) Janiak, C.; Vieth, J. K. New J. Chem. 2010, 34, 2366. (b) Aaker€oy, C. B.; Champness, N. R.; Janiak, C. CrystEngComm 2010, 12, 22. (c) Adhikary, C.; Koner, S. Coord. Chem. Rev. 2010, 254, 2933. (d) Punniyamurthy, T.; Rout, L. Coord. Chem. Rev. 2008, 252, 134. (e) Robin, A. Y.; Fromm, K. M. Coord. Chem. Rev. 2006, 250, 2127. (f) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334. (3) See the Cambridge Structural Database (CSD, version 5.32, Feb. 2011): Allen, F. H. Acta Crystallogr. 2002, B58, 380. (4) (a) Aromi, G.; Gamez, P.; Reedijk, J. Coord. Chem. Rev. 2008, 252, 964. (b) Vigato, P. A.; Peruzzo, V.; Tamburini, S. Coord. Chem. Rev. 2009, 253, 1099. (c) Iskander, M. F.; Khalil, T. E.; Haase, W.; Werner, R.; Svoboda, I.; Fuess, H. Polyhedron 2001, 20, 2787. (d) Abrahams, B. F.; Egan, S. J.; Robson, R. J. Am. Chem. Soc. 1999, 121, 3535. (5) (a) Kopylovich, M. N.; Mahmudov, K. T.; Guedes da Silva, M. F. C.; Figiel, P. J.; Karabach, Y. Y.; Kuznetsov, M. L.; Luzyanin, K. V.; Pombeiro, A. J. L. Inorg. Chem. 2011, 50, 918. (b) Kopylovich, M. N.; Mahmudov, K. T.; Haukka, M.; Luzyanin, K. V.; Pombeiro, A. J. L. Inorg. Chim. Acta 2011, 374, 175. (c) Maharramov, A. M.; Alieva, R. A.; Mahmudov, K. T.; Kurbanov, A. V.; Askerov, R. K. Russ. J. Coord. Chem. 2009, 35, 704. (6) (a) Kopylovich, M. N.; Nunes, A. C. C.; Mahmudov, K. T.; Haukka, M.; Mac Leod, T. C. O.; Martins, L. M. D. R. S.; Kuznetsov, M. L.; Pombeiro, A. J. L. Dalton Trans. 2011, 40, 2822. (b) Hao, L.; Mu, C.; Wang, R. Acta Crystallogr. 2008, E64, m929. (7) (a) Karabach, Y. Y.; Guedes da Silva, M. F. C.; Kopylovich, M. N.; Gil-Hern
andez, B.; Sanchiz, J.; Kirillov, A. M.; Pombeiro, A. J. L. Inorg. Chem. 2010, 49, 11096. (b) Kirillov, A. M.; Coelho, J. A. S.; Kirillova, M. V.; Guedes da Silva, M. F. C.; Nesterov, D. S.; Gruenwald, K. R.; Haukka, M.; Pombeiro, A. J. L. Inorg. Chem. 2010, 49, 6390. (c) Karabach, Y. Y.; Kirillov, A. M.; Haukka, M.; Sanchiz, J.; Kopylovich, M. N.; Pombeiro, A. J. L. Cryst. Growth Des. 2008, 8, 4100. (d) Kirillov, A. M.; Karabach, Y. Y.; Haukka, M.; Guedes da Silva, M. F. C.; Sanchiz, J.; Kopylovich, M. N.; Pombeiro, A. J. L. Inorg. Chem. 2008, 47, 162. (e) Kirillova, M. V.; Kirillov, A. M.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2008, 3423. (f) Karabach, Y. Y.; Kirillov, A. M.; Haukka, M.; Kopylovich, M. N.; Pombeiro, A. J. L. J. Inorg. Biochem. 2008, 102, 1190. (8) Synthesis and analytical data of 1 and 2: In the case of 1, to an ethanol acetone solution (1/1, v/v, 100 mL) of H3L1 (335 mg, 1.0 mmol) [or, in the case of 2, to the aqueous solution (100 mL) of H3L2 (345 mg, 1.0 mmol)] were added KOH (56 mg, 1.0 mmol) and Cu(NO3)2 3 2.5H2O (233 mg, 1.0 mmol) in this order. The obtained mixture was stirred for 5 min and left for slow evaporation at room temperature (rt, ca. 20 °C). Brown crystals of 1 or dark green crystals of 2 were formed in 5 or 3 days, respectively, whereafter they were filtered off and dried in air. Analytical data for 1: Yield 51%, based on copper(II) nitrate. S25°C (in H2O) = 0.5 g L 1. Calcd for C11H12ClCuKN2O8S (M = 470.4): C, 28.09; H, 2.57; N, 5.96. Found: C, 27.92; H, 2.60; N, 5.64. IR, cm 1: 3437 (s br) ν(H2O), 3002 (w), 2925 (w), 2854 (w), 1654 (s br) ν(CdO), 1548 (w), 1522 (w), 1508 (m), 1455 (s), 1407 (m), 1375 (s), 1341 (w), 1317 (w), 1317 (w), 1264 (s), 1219 (m), 1172 (s br), 1090 (w), 1070 (w), 1040 (w), 992 (w), 974 (w), 937 (s), 870 (m), 799 (w), 761 (m), 663 (m), 637 (s), 586 (m), 544 (w), 514 (w), and 422 (w). Analytical data for 2: Yield 68%, based on copper(II) nitrate. S25°C 4251

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Crystal Growth & Design (in H2O) = 0.6 g L 1. Calcd for C11H14CuKN3O11S (M = 499.0): C, 26.48; H, 2.83; N, 8.42. Found: C, 26.60; H, 2.62; N, 8.29. IR, cm 1: 3543 (m br), 3435 (m br), and 3222 (m br) ν(H2O), 1808 (w), 1645 (vs br) ν(CdO), 1579 (s) ν(CdN), 1528 (m), 1502 (m), 1459 (s), 1427 (m), 1371 (s), 1331 (s), 1305 (w), 1279 (s), 1240 (m), 1217 (s), 1176 (s), 1089 (m), 1064 (w), 1041 (s), 994 (m), 945 (s), 909 (m), 898 (m), 835 (w), 818 (w), 776 (w), 738 (s), 662 (m), 629 (s), 589 (s), 557 (s), 523 (m), and 423 (w). (9) Crystal data: 1: C11H12ClCuKN2O8S, M = 470.38, λ = 0.71073 Å (Mo KR), T = 100(2) K, triclinic, space group P1, a = 7.1364(5), b = 11.4297(9), c = 11.7485(10) Å, R = 62.658(4), β = 75.568(5), γ = 88.560(5)°, V = 819.91(11) Å3, Z = 2, Dc = 1.905 g/cm3, F000 = 474, μ = 1.920 mm 1, 6049 reflections collected, 2920 unique (Rint = 0.0409), R1 = 0.0697, wR2 = 0.1726 (I > 2σ). 2: C11H14CuKN3O11S, M = 498.95, λ = 0.71073 Å (Mo KR), T = 100(2) K, monoclinic, space group P21n, a = 12.6476(2), b = 6.6691(1), c = 20.3388(3) Å, β = 96.917(1)°, V = 1703.05(4) Å3, Z = 4, Dc = 1.946 g/cm3, F000 = 1012, μ = 1.718 mm 1, 16423 reflections collected, 3921 unique (Rint = 0.0254), R1 = 0.0288, wR2 = 0.0714 (I > 2σ). (10) Addison, A. W.; Rao, T. N.; Reedijk, J.; Vanrijn, J.; Verschoor, G. C. J. Chem. Soc., Dalton Trans. 1984, 1349. (11) Bondi, A. J. Phys. Chem. 1964, 68, 441. (12) Infantes, L.; Motherwell, S. CrystEngComm 2002, 4, 454. (13) Blatov, V. A. IUCr CompComm Newsl. 2006, 7, 4. (14) (a) Blatov, V. A.; Proserpio, D. M. In Modern Methods of Crystal Structure Prediction; Oganov, A. R., Ed.; Wiley: 2010; pp 1 28. (b) Blatov, V. A.; O’Keeffe, M.; Proserpio, D. M. CrystEngComm 2010, 12, 44. (c) Alexandrov, E. V.; Blatov, V. A.; Kochetkova, A. V.; Proserpio, D. M. CrystEngComm 2011, 13, 3947. (15) The Reticular Chemistry Structure Resource (RCSR) Database. See also http://rcsr.anu.edu.au/. O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem. Res. 2008, 41, 1782. (16) (a) Zhang, L.-P.; Ma, J.-F.; Pang, Y.-Y.; Ma, J.-C.; Yang, J. CrystEngComm 2010, 12, 4433. (b) Liu, D.; Huang, G.; Huang, C.; Huang, X.; Chen, J.; You, X. Z. Cryst. Growth Des. 2009, 9, 5117. (c) Wang, X.; Liu, G.; Zhang, J.; Chen, Y.; Lin, H.; Zheng, W. Dalton Trans. 2009, 7347. (d) Jin, Y.; Qi, Y.; Batten, S. R.; Cao, P.; Chen, W.; Che, Y.; Zheng, J. Inorg. Chim. Acta 2009, 362, 3395. (e) Shyu, E.; LaDuca, R. L. Polyhedron 2009, 28, 826. (f) Kelly, N. R.; Goetz, S.; Batten, S. R.; Kruger, P. E. CrystEngComm 2008, 10, 68. (g) Cheng, J.-W.; Zheng, S.-T.; Ma, E.; Yang, G.-Y. Inorg. Chem. 2007, 46, 10534. (17) For selected examples, see:(a) Wen, L.-L.; Wang, F.; Leng, X.-K.; Wang, C.-G.; Wang, L.-Y.; Gong, J.-M.; Li, D.-F. Cryst. Growth Des. 2010, 10, 2835. (b) Dai, J.-C.; Wu, X.-T.; Hu, S.-M.; Fu, Z.-Y.; Zhang, J.-J.; Du, W.-X.; Zhang, H.-H.; Sun, R.-Q. Eur. J. Inorg. Chem. 2004, 2096. (c) Huang, Y.-G.; Wang, X.-T.; Jiang, F.-L.; Gao, S.; Wu, M.-Y.; Gao, Q.; Wei, W.; Hong, M.-C. Chem.—Eur. J. 2008, 14, 10340. (d) Martin, D. P.; Montney, M. R.; Supkowski, R. M.; LaDuca, R. L. Cryst. Growth Des. 2008, 8, 3091. (18) For a recent review, see: McKinlay, A. C.; Morris, R. E.; Horcajada, P.; F
erey, G.; Gref, R.; Couvreur, P.; Serre, C. Angew. Chem., Int. Ed. 2010, 49, 6260. (19) (a) Figiel, P. J.; Kopylovich, M. N.; Lasri, J.; Guedes da Silva, M. F. C.; da Silva, J. J. R. F.; Pombeiro, A. J. L. Chem. Commun. 2010, 46, 2766. (b) Figiel, P. J.; Kirillov, A. M.; Karabach, Y. Y.; Kopylovich, M. N.; Pombeiro, A. J. L. J. Mol. Catal. A 2009, 305, 178. (c) Figiel, P. J.; Kirillov, A. M.; Guedes da Silva, M. F. C.; Lasri, J.; Pombeiro, A. J. L. Dalton Trans. 2010, 39, 9879. (20) Gamez, P.; Arends, I. W. C. E.; Sheldon, R. A.; Reedijk, J. Adv. Synth. Catal. 2004, 346, 805. (21) For selected examples, see:(a) Kopylovich, M. N.; Tronova, E. A.; Haukka, M.; Kirillov, A. M.; Kukushkin, V. Y.; Frausto da Silva, J. J. R.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2007, 4621. (b) Fernandes, R. R.; Kirillov, A. M.; Guedes da Silva, M. F. C.; Ma, Z.; da Silva, J. A. L.; Frausto da Silva, J. J. R.; Pombeiro, A. J. L. Cryst. Growth Des. 2008, 8, 782. (c) Kirillova, M. V.; Kirillov, A. M.; Guedes da Silva, M. F. C.; Kopylovich, M. N.; Frausto da Silva, J. J. R.; Pombeiro, A. J. L. Inorg. Chim. Acta 2008, 361, 1728. (d) Karabach, Y. Y.; Kirillov, A. M.; Guedes

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da Silva, M. F. C.; Kopylovich, M. N.; Pombeiro, A. J. L. Cryst. Growth Des. 2006, 6, 2200. (22) For reviews on water clusters and assemblies, see: (a) Nangia, A. In Encyclopedia of Supramolecular Chemistry—Update; Atwood, J. L., Steed, J. W., Eds.; Taylor & Francis: London, 2007; Vol. 1.1, pp 1 9. (b) Infantes, L.; F
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