Solution and Solid-State Preparation of 18-Crown-6 and 15-Crown-5 Adducts of Hydrogen Sulfate Salts and an Investigation of the Reversible

Dehydration Processes
Dario Braga,* Massimo Gandolfi, Matteo Lusi, Marco Polito,* Katia Rubini, and Fabrizia Grepioni*
Dipartimento di Chimica G. Ciamician, UniVersita di Bologna, Via Selmi 2, 40126 Bologna, Italy ` ReceiVed October 27, 2006; ReVised Manuscript ReceiVed February 20, 2007

CRYSTAL GROWTH & DESIGN

2007 VOL. 7, NO. 5 919-924

ABSTRACT: A new class of organic-inorganic complexes has been prepared by reaction in solution or by mechanical mixing of 15-Crown-5 or 18-Crown-6 ethers with MSO4 (M ) Mn2+, Cd2+, Pb2+) and/or H2SO4 in stoichiometric amount. The complexes (15-Crown-5)[Mn(H2O)2(HSO4)2] (1), (15-Crown-5)[Cd(H2O)2(HSO4)2] (2), (15-Crown-5)[(H7O3)(HSO4)2]H2O (3), (18-Crown6)[Pb(HSO4)2] (4), and (18-Crown-6)[(H5O2)(HSO4)] (5) have been characterized by single-crystal X-ray diffraction. Compounds 1 and 2 undergo reversible water release-uptake processes, accompanied by a change in coordination at the metal centers; the dehydration and phase-transition processes have been investigated by DSC, TGA, and variable-temperature X-ray powder diffraction. Introduction After the pioneering work of Pedersen,1 crown ethers and their complexes with metal cations have attracted much attention. This is partly due to the fact that crown ethers are able to form stable complexes with alkali and transition-metal atoms and hydrogen-bonding cations and present unusual coordination numbers and arrangements with various metal ions,2 but also to their utilization in supramolecular chemistry and crystal engineering as modules for the construction of complex superstructures.3 We have recently communicated4 that crown ethers can also be used in solid-solid and solid-liquid processes to capture alkali metal cations and the ammonium cation in extended hydrogen-bonded networks formed by inorganic acid anions, such as the hydrogensulphate. We have shown that manual grinding of solid 18-Crown-6 and solid [NH4][HSO4] in the air leads to formation of the crown ether complex 18-Crown-6 [NH4][HSO4]2H2O, the water molecules being taken up from ambient humidity during grinding. The crown ether 15-Crown5, which is a liquid at room temperature, has been otherwise kneaded with solid ammonium hydrate sulfate to produce the complex (15-Crown-5)3[NH4]2[HSO4]3H2O.4 In this paper, we extend our strategy to the complexation (either in solution or by solid-state methods)5 of metal cations, namely Mn2+, Cd2+, and Pb2+. The motivation for this study is manifold: (i) hydrogen sulfate salts are of interest because of the presence of hydrogen bonds between ions, a relevant supramolecular chemistry and crystal engineering issue;6 (ii) crown ether complexes have been used in ion recognition, complexation, and in self-assembly processes;7 (iii) hydrogen sulfate salts, in particular those based on solid acid salts such as CsHSO4, Rb3H(SeO4)2, etc., have found applications in a number of devices such as H2 and H2O sensors, fuel and steam cells, and high-energy-density batteries.8 Herein, we report the synthesis and characterization of five novel compounds containing either the 15-Crown-5 or the 18Crown-6 ether, namely (15-Crown-5)[Mn(H2O)2(HSO4)2] (1), (15-Crown-5)[Cd(H2O)2(HSO4)2] (2), (15-Crown-5)[(H7O3) (HSO4)2]H2O (3), (18-Crown-6)[Pb(HSO4)2] (4), and (18Crown-6)[(H5O2)(HSO4)2] (5). These complexes have all been
* E-mail: dario.braga@unibo.it (D.B.); fabrizia.grepioni@unibo.it (F.G.).

obtained by direct reaction in solution, with the exception of compound, 4, which has been obtained by mechanical mixing of the reactants in the solid state. Because complexes 1 and 2 are obtained in the form of hydrates, we have also investigated their thermal behavior via DSC, TGA, and variable-temperature X-ray diffraction experiments. In particular, we have investigated the release-uptake of water of crystallization and the stability of the anhydrous phases as well as the existence of order-disorder phase transitions. These issues are relevant for a potential exploitation of these salts in fuel-cell applications and are of interest in the investigation of crystal polymorphism9 and crystal design.10 Experimental Section
Synthesis. All starting materials were purchased from Aldrich. Reagent grade solvents and bi-distilled water were used. (15-Crown-5)[Mn(H2O)2(HSO4)2] (1). 15-Crown-5 (0.220 g, 1 mmol), MnSO4H2O (0.169 g, 1 mmol), and H2SO4 (0.100 g, 1 mmol) were dissolved in 4 mL of water. The solution was refluxed for 1 h. Single crystals of 1 were obtained by slow evaporation of the solution. (15-Crown-5)[Cd(H2O)2(HSO4)2] (2). 15-Crown-5 (0.220 g, 1 mmol), CdSO4H2O (0.226 g, 1 mmol), and H2SO4 (0.098 g, 1 mmol) were dissolved in 4 mL of water. The solution was refluxed for 1 h. Single crystals of 2 were obtained by slow evaporation of the solution. (15-Crown-5)[(H7O3)(HSO4)2]H2O (3). 15-Crown-5 (0.220 g, 1 mmol) and H2SO4 (0.100 g, 1 mmol) were dissolved in 2 mL of water. Single crystals of 3 were obtained by slow evaporation of the solution. (18-Crown-6)[Pb(HSO4)2] (4). 18-Crown-6 (0.264 g, 1 mmol), PbSO4 (0.303 g 1 mmol), and H2SO4 (0.100 g, 1 mmol) were stirred in 2 mL of water for 1 h. The solution was then filtered, and single crystals of 4 were obtained by slow evaporation of the solvent. The obtained product was not pure: the presence of undefined substance was detected by comparison of calculated and measured X-ray powder diffractograms. A faster and more quantitative reaction was performed grinding the same reagents in a mortar in the absence of water: the reaction mixture was left in a desiccator for 48 h; after this time, only compound 4 was present. Synthesis of (18-Crown-6)[(H5O2)(HSO4)] (5). 18-Crown-6 (0.264 g, 1 mmol) and H2SO4 (0.100 g, 1 mmol) were dissolved in 2 mL of water. Single crystals of 5 were obtained by slow evaporation of the solution. Thermogravimetric Analysis (TGA). TGA analysis was performed with a Perkin-Elmer TGA-7. Each sample, contained in a platinum crucible, was heated in a nitrogen flow (20 cm3 min-1) at a rate of 5 C min-1, up to decomposition. The samples weights were in the range 5-10 mg.

10.1021/cg0607598 CCC: $37.00 2007 American Chemical Society Published on Web 03/31/2007

920 Crystal Growth & Design, Vol. 7, No. 5, 2007

Table 1. Crystallographic Data and Details of Measurements for Compounds 1-5 1 chemical formula fw cryst syst space group a () b () c () R (deg) (deg) (deg) V (3) Z Dcalcd (g cm-3) (mm-1) no. of measured reflns R1 (on Fo2, I > 2(I)) wR2 (all data) C10H26MnO15S2 505.37 orthorhombic Ccm21 7.418(3) 18.016(5) 14.851(3) 90 90 90 1985(1) 4 1.691 0.948 1537 0.0540 0.1546 2 C10H26CdO15S2 562.83 orthorhombic Ccm21 7.511(3) 18.212(6) 14.920(6) 90 90 90 2041(1) 4 1.832 1.345 1855 0.0541 0.1310 3 C10H30O13S 390.40 triclinic P1 h 7.6336(4) 10.5457(5) 12.9774(6) 103.899(1) 105.679(1) 96.469(1) 958.59(8) 2 1.353 0.227 11088 0.0615 0.2019 4 C12H26O14PbS2 665.64 triclinic P1 h 10.336(5) 10.418(6) 10.648(3) 76.58(4) 77.71(3) 76.96(4) 1070.8(9) 2 2.064 8.138 3973 0.0348 0.0927

Braga et al.

5 C12H30O12S 398.42 monoclinic P21 11.079(4) 8.220(4) 11.525(5) 90 112.95(5) 90 966.5(7) 2 1.369 0.223 3111 0.0883 0.3356

Differential Scanning Calorimetry (DSC). Calorimetric measurements were performed with a Perkin-Elmer DSC-7 equipped with a PII intracooler. Temperature and enthalpy calibrations were performed using high-purity standards (n-decane, benzene, and indium). Heating of the aluminum open pans containing the samples (3-5 mg) was carried out at 5 C min-1 in the temperature range 40-180 C. X-ray Diffraction. Single-crystal data for compounds 1, 2, 4, and 5 were collected on a NONIUS CAD-4 diffractometer; for compound 3, data were collected on a Bruker Smart CCD diffractometer. Both instruments were equipped with a graphite monochromator (Mo-Ka radiation, ) 0.71073 ) and operated at room temperature. Data collection and refinement details are listed in Table 1. The hydrogensulphate anion in both 1 and 2 was found to be disordered (50:50 occupancy) around one of the S-O axes. A small amount of disorder (90:10 occupancy) was detected for two of the five crown ether oxygen atoms in 3. All non-H atoms were refined anisotropically. HOH atoms were directly located only in compounds 3 and 4 and were not refined. HCH atoms for all compounds were added in calculated positions and refined riding on their respective C atoms. SHELXL9711a was used for structure solution and refinement on F2, and PLATON11b and SCHAKAL11c were used for the hydrogen bonding analyses and molecular graphics, respectively. The identity between the bulk material obtained via the solid-state processes and the structures obtained by single crystals was verified by comparing calculated and observed powder diffraction patterns (see the Supporting Information). Powder data were collected on a Philips XPert automated diffractometer with Cu-KR radiation, graphite monochromator. The program PowderCell 2.211d was used for calculation of X-ray powder patterns.

An important aspect of compound 1 is that the water removal does not cause decomposition, but leads to formation of an anhydrous crystalline phase. The thermogravimetric analysis (TGA, Figure 2a) shows a weight loss in the range 70-120 C, corresponding to the loss of two water molecules. The differential scanning calorimetry diagram (DSC, Figure 2b) shows a broad endothermic peak approximately in the same temperature range, corresponding to the removal of the metalcoordinated water molecules. A more detailed insight of the thermal behavior of 1 is obtained by variable-temperature X-ray powder diffraction experiments (VT-XRPD, see the Experimental Section).l Figure 3 provides a clear indication that the transition of 1 to 1-anhydrous leads from one crystalline phase to another. Compound 1-anhydrous is hygroscopic and when left in air at room temperature for a few hours slowly reconverts to the hydrated complex 1, as can be seen in Figure 4, which shows the comparison between the experimental XRPD pattern and

Results and Discussion We will describe separately the preparation and characterization of the complexes obtained with 15-Crown-5 and of those obtained with 18-Crown-6. Compound (15-Crown-5)[Mn(H2O)2(HSO4)2], 1, has been prepared by boiling a water solution of MnSO4, 15-Crown-5 ,and H2SO4 in a 1:1:1 molar ratio. Single crystals of 1 have been obtained by slow evaporation of the solution in the air (see Experimental Section). In crystalline 1, the Mn2+ cation is coordinated to five oxygen atoms of the crown ether (Mn Ocrown ) 2.173(3)-2.248(5) ) and two water molecules (Mn Owater ) 2.149(6) and 2.154(5) ). The oxygen atoms constitute the vertices of a pentagonal bipyramid around the metal center, as shown in Figure 1a. The structure of 1 is characterized by the presence of hydrogen-bonded dimers of HSO4- anions (OanionOanion ) 2.65(1)-2.74(1) ) linked by hydrogen bonds via the coordination water molecules (OwaterOanion ) 2.50(1) and 2.62(1) ; see Figure 1b). The hydrogensulphate anions are disordered over two positions around one of the S-O bonds (see the Experimental Section).

Figure 1. (a) Coordination geometry of the crown ether and the water molecules (light blue spheres) around the Mn2+ ion; (b) dimers of HSO4- anions (oxygens in blue) are linked together via hydrogen bonds with the metal-coordinated water molecules (OanionOanion ) 2.65(1)2.74(1) ; OwaterOanion ) 2.50(1) and 2.62(1) ). Only one image of the disordered HSO4- anion is shown for clarity. No HOH atoms were observed. HCH atoms omitted for clarity.

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Crystal Growth & Design, Vol. 7, No. 5, 2007 921

Figure 4. Comparison between the XRPD pattern measured on compound 1-anhydrous left in the air after dehydration of 1 (top) and that computed on the basis of the single-crystal structure of 1 (bottom).

Figure 2. TGA (a) and DSC (b) diagrams, showing (a) a weight loss between 70 and 120 C corresponding to the loss of two water molecules and (b) endothermic peak associated with the water-removal process.

Figure 5. Comparison between the XRPD patterns of compound 2 (top) and that of 2-anhydrous (bottom), obtained by heating the sample at 100 C. Figure 3. Variable-temperature powder diffraction experiments: compound 1 converts to the anhydrous crystalline form 1-anhydrous between 85 and 105 C. The transformation is reversible if the anhydrous compound is then exposed to water.

that computed on the basis of the single-crystal structure. No single-crystal X-ray data are available for 1-anhydrous. Diffraction, thermogravimetric, and calorimetric measurements are all consistent with a reversible release-uptake of water from 1, with a change in the crystal structure. It is worth stressing that we are observing a transition from a water complex, whereby the metal cation bears two water ligands and the crown ether and is linked to the hydrogen sulfate via hydrogen bonds, to a new complex, which very likely fulfills the coordination requirement of the metal center by establishing MnO coordination bonds with the anions. Compound (15-Crown-5)[Cd(H2O)2(HSO4)2], 2, has been prepared in manner similar to that of 1 by boiling a water solution of CdSO4, 15-Crown-5, and H2SO4 in a 1:1:1 molar ratio. Crystals of 2 have been obtained by slow evaporation of

the solution (see the Experimental Section) and used for singlecrystal X-ray diffraction experiments. Compound 2 is isomorphous with compound 1. As in the case of 1, the hydrogensulphate anion is disordered in the crystal structure. The CdO distances are slightly longer with respect to the MnO distances in compound 1 (CdOwater ) 2.34(1) and 2.24(1) , Cd Ocrown ) 2.239(8)-2.334(10) ), probably reflecting the difference in the ionic radii. The TGA of compound 2 shows a loss of weight between 50 and 100 C, corresponding to the loss of two water molecules. As demonstrated by a VT-XRPD experiment, the loss of water is again accompanied by a phase transition to an anhydrous crystalline form (see Figure 5). If the anhydrous form thus obtained is left in air at room temperature, it slowly reconverts to 2. Despite compound 2 and compound 1 being isomorphous, the two anhydrous crystalline forms 1-anhydrous and 2-anhydrous are different. This difference may indicate the possibility of crystal polymorphism for these phases. In the course of the same study, we have also attempted preparation of the hydrogen sulfate complex of 15-Crown-5.

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Complexes with hydronium and metals cations of crown ethers are well-known and have been extensively studied by Steed and others.12 Compound (15-Crown-5)[H7O3][HSO4]H2O, 3, has been prepared by slow evaporation of a water solution containing 15-Crown-5 ether and sulfuric acid in a stoichiometric ratio (see the Experimental Section). The complex is characterized by the presence of the cluster H7O3+ (OO distances ) 2.439(4) and 2.483(3) ). The tri-oxygen cation H7O3+ has been observed in a few cases, with geometrical parameters in agreement with those of compound 3.12 The oxygen atoms of the crown ether are hydrogen bonded to a water molecule on one side of the ring (OO distances of 2.775(3) and 2.751(3) ) and an oxygen atom of the H7O3+ cluster on the opposite side (OO distances of 2.775(3) and 2.792(3) ; Figure 6a). The hydrogensulphate anions interact with both the water molecules attached to the crown ether and the H7O3+ cluster, as shown in Figure 6b. All oxygen atoms of the hydrogen sulfate anions are involved in hydrogen-bonding interactions, with formation of ribbons extending along the crystallographic a-axis direction. Solid 18-Crown-6 has been reacted with PbSO4, because initial attempts with the smaller 15-Crown-5 had failed to give new compounds. The compound (18-Crown-6)[Pb(HSO4)2], 4, has been synthesized by grinding a 1:2:1 molar ratio of PbSO4, H2SO4, and 18-Crown-6 in a mortar. Mechanical mixing of reactants has been used before in the preparation of potassium salts.4 The polycrystalline product was dissolved in water, and slow evaporation of the water solution afforded single crystals suitable for X-ray diffraction. Complex 4 crystallizes as an anhydrous form, with the lead ion coordinated to the six oxygen atoms of the ether and two oxygens of different hydrogensulphate units (PbOanion ) 2.509(6) and 2.605(6) ). The structure of 4 is characterized by the presence of dimers of HSO4- anions linked by hydrogen bonds (OO ) 2.60(1) and 2.61(1) ), as shown in Figure 7. Heating of complex 4 does not lead to any crystal transformation; decomposition takes place at 140 C. In the course of the same investigation, we have attempted isolation of a hydrogen sulfate water complex analogous to that obtained with the 15-Crown-5. Indeed, slow evaporation (see Experimental Section) of a water solution containing 18Crown-6 and sulfuric acid in a stoichiometric ratio yielded single crystals of (18-Crown-6)[(H5O2)(HSO4)], 5. The structure of 5 is characterized by the presence of the cation H5O2+ (OO ) 2.41(1) ), linked by hydrogen bonds to four oxygen atoms of the crown ether (OO ) 2.71(1), 2.74(1), 2.92(1), and 2.62(1) ). The hydrogensulphate anions form a chain (OO distance of 2.65(1) ), which is hydrogen-bonded on opposite sides to one of the two oxygen atoms of the H5O2+ cation (OanionOcation ) 2.52(1) ; Figure 8). The thermal behavior of 3 and 5 could not be investigated, as both compounds melt at low temperature (ca. 40 C) and readily decompose upon heating. Conclusions In this paper, we have reported the preparation and characterization of three novel metal complexes containing the crown ethers 15-Crown-5 and 18-Crown-6 with the cations Mn2+, Cd2+, and Pb2+ as well as the identification of two hydrogen sulfate salts, in which the crown ethers are linked to hydronium ions. It is interesting to speculate on the different behavior of the crystals of the Mn2+ and Cd2+ complexes with respect to that of Pb2+. On heating, the former hydrated compounds release

Figure 6. Structural and packing features of crystalline (15-Crown5)[H7O3][HSO4]H2O, 3. (a) Each crown ether coordinates one water molecule on one side of the ring (OO distances of 2.775(3) and 2.751(3) ) andan oxygen atom of the H7O3+ cluster (violet spheres) on the opposite side (OO distances of 2.775(3) and 2.792(3) ). (b) The hydrogensulphate anions interact both with the water molecules attached to the crown ether and with the H7O3+ cluster (OO distances in the range 2.531(3)-2.692(3) ). (c) All oxygen atoms of the hydrogen sulfate anions are involved in hydrogen-bonding interactions, with formation of ribbons that extend along the a-axis direction in the crystal.

water molecules that are directly coordinated to the metal centers; therefore, the reversible water release-uptake process can be seen as a complexation equilibrium, by which the water molecules are removed from the metal cation coordination sphere and are, very likely, replaced by direct MO(hydrogen sulfate) interactions of the kind observed in compound 3. The

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Crystal Growth & Design, Vol. 7, No. 5, 2007 923

Figure 7. The basic packing motif in crystalline (18-Crown-6)[Pb(HSO4)2], 4: dimers of hydrogen-bonded HSO4- anions (OO ) 2.60(1) and 2.61(1) ) are coordinated to the lead atoms bound to the crown ethers (PbOanion ) 2.509(6) and 2.605(6) ), thus forming a supramolecular chain extending along the (111) direction in the crystal.

References
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Figure 8. The basic packing motif in crystalline (18-Crown-6)[(H5O2)(HSO4)], 5. The H5O2+ cations (violet spheres, OO distance ) 2.41(1) ) are linked by hydrogen bonds to four oxygen atoms of the crown ether (OO ) 2.71(1), 2.74(1), 2.92(1), and 2.62(1) ). The hydrogensulphate anions form a chain (OO distance of 2.65(1) ), which is hydrogen-bonded on opposite sides to one of the two oxygen atoms of the H5O2+ cation (OanionOcation ) 2.52(1) ). No HOH atoms were observed.

new structures, however, are unstable with respect to hydration and easily revert to the more stable water complexes upon exposure to atmospheric humidity. The diffractograms of the two anhydrous phases, 1-anhydrous and 2-anhydrous, are indicative of crystalline nature of the materials; considering the high temperatures at which they are obtained, it is also very likely that the high-temperature phases are in a dynamical state with reorientational motions of the crown ethers and/or the hydrogen sulfate anions. Besides the heterogeneous complexation phenomena shown by 1 and 2, we have also provided, with compound 4, another example of successful mechanical preparation of a supramolecular complex by solid-state grinding of the reactants. Both the possibility of preparing new complexes by removal of water (or other solvents) from aquo-complexes in an heterogeneous solid-vapor processes and the possibility of using solvent-free methods to prepare otherwise elusive materials are notions of interest in crystal engineering and solidstate supramolecular chemistry. Acknowledgment. We thank MiUR (PRIN2004 and FIRB2001) and the University of Bologna for financial support.
Supporting Information Available: Crystallographic data in CIF format, ORTEP diagrams and calculated plus experimental X-ray powder diffractograms for compounds 1-5. This material is available free of charge via the Internet at http://pubs.acs.org.

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