Hierarchical Ordering in Ternary Co-Crystals of C60, N-Benzyl

Communication pubs.acs.org/crystal

Hierarchical Ordering in Ternary Co-Crystals of C60, N‑Benzyl Ammonium Resorcinarene Bromide and Solvent Molecules N. Kodiah Beyeh, Fangfang Pan, and Kari Rissanen* Department of Chemistry, NanoScience Centre, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland S Supporting Information *

ABSTRACT: Co-crystallization of C60 together with an N-benzyl ammonium resorcinarene bromide from toluene:1,2-dichloroethane mixture results in ternary co-crystals where the modulated C60 lattice entraps dimeric resorcinarene assemblies, which, in turn, have 149 and 280 Å3 cavities filled with 1,2-dichloroethane molecules.

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INTRODUCTION The quest for complex self-assembling multicomponent architectures and nanostructures with potentially useful applications makes the use of weak noncovalent intermolecular interactions, viz., supramolecular interactions, an important area in contemporary chemistry.1,2 Resorcinarenes, with their ease in preparation and versatile host−guest properties, play an important role as very useful construction units in supramolecular chemistry.3 Resorcinarenes in C4v conformation possess a concave cavity that can bind a variety of guests leading to 1:1 open inclusion complexes,4 dimeric5,6 and hexameric7−10 capsular assemblies, and nanotubes.11 The electron-rich 2-position of the resorcinarene benzene ring is particularly suitable for electrophilic substitutions.3 Mannich condensation reaction with primary amines results in resorcinarene tetrabenzoxazines.12−14 Subsequently the sixmembered tetrabenzoxazine ring can be opened in the presence of mineral acids resulting in N-alkyl ammonium resorcinarene salts.13−15 In these inner salts the hydrogen bonds between the ammonium moieties and the anions (especially halides) form a strong circular (···H−(R′)N+(R″)−H···X−···H−(R′)N+(R″)− H···X−)2 hydrogen bond seam leading to compounds that can be regarded as hydrogen bonded analogues of cavitands13 since they possess a similar shape and cavity size as their covalent cavitand counterparts. Recently, these resorcinarene salts have been shown to act also as halogen bond16 acceptors with a striking similarity to deep-cavity cavitands.17 The nature of the groups attached to the upper-rim ammonium moieties in these resorcinarene salts has a direct effect on both the cavity size and its complexation ability toward guests. Short aliphatic chains such as propyl result in self-included pseudocapsular assemblies in the solid state.14,15 Slightly larger or longer substituents usually lead to 1:1 host− guest complexes since self-inclusion cannot happen.14 Obtaining © 2014 American Chemical Society

capsular assemblies, either dimeric or multimeric of these salts in the solid state, has so far not been successful. Unsubstituted fullerenes, C60, C70, and so forth, are a very interesting family of novel compounds, first as a guest in host−guest chemistry, but also for their interesting solid state properties.18 Crystal engineering19 provides a method for preparing crystal lattices, co-crystals, or hierarchical solid state structures which can manifest unprecedented physical or photophysical properties. The size and shape of fullerene C60 makes it a proper component for co-crystallization with a potential macrocyclic host compound, e.g., to trap fullerene inside the host cavity. There are several reports of multicomponent architectures involving fullerene C60 with several host molecules such as calix[n]arenes,20−28 nitrogen and oxygen bridged calixaromatics, 29 cyclotriveratrylene,30 azacrown ether,31,32 and other macrocycles33−39 in the solid state. The hydroxyl groups of calix[4]arenes and resorcinarenes are responsible for their C4v cone conformation. The inclusion of C60 is usually observed with larger calix[n]arenes (n > 4) due to their larger internal cavities. The internal cavity alone in calix[4]arene and resorcinarenes is too small to accommodate C60. Despite this, several co-crystallized complexes with interesting arrangements involving calix[4]arenes and C60 have been reported.22 Structures containing both resorcinarenes and fullerenes are sparse. One of the very few examples is the isopropyl alcohol mediated dimeric capsule of unsubstituted resorcinarene co-crystallized with C60 reported by Atwood et al.40 In this Communication, we report the hierarchical ordering of the components in a ternary co-crystal of C60, N-benzyl ammonium resorcinarene bromide and solvent molecules. Received: September 26, 2014 Revised: October 30, 2014 Published: October 31, 2014 6161

dx.doi.org/10.1021/cg5014413 | Cryst. Growth Des. 2014, 14, 6161−6165

Crystal Growth & Design

Communication

Figure 1. N-Benzyl ammonium resorcinarene bromide 1, fullerene C60, toluene, and 1,2-dichloroethane.

The N-benzyl ammonium resorcinarene bromide 1 (Figure 1) arranges into dimeric capsular entities inside the C60 lattice in a head-to-head, tail-to-tail fashion resulting in two differently sized cavities filled with solvent molecules.

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EXPERIMENTAL SECTION

Synthesis. The N-benzyl ammonium resorcinarene bromide 1, was synthesized according to reported procedures.13,14 Fullerene C60 and all solvents were commercially available. Single-Crystal Structure. Suitable single crystals for the solvate of N-benzyl ammonium resorcinarene bromide [1•(CH3OH)•(CHCl3)2] were obtained by slow evaporation from the solution mixture of methanol and chloroform containing resorcinarene bromide 1. Crystals of the ternary co-crystal [12•(C60)4•(C7H8)8•(C2H4Cl2)] were grown from the combination of the resorcinarene bromide 1 and fullerene C60 in a mixture of toluene and 1,2-dichloroethane. Chlorobenzene would have been an alternative to toluene as the crystallization solvent.41 The data for [1•(CH3OH)•(CHCl3)2] was collected at 120 K with an Agilent Super-Nova diffractometer using mirror-monochromatized Cu Kα (λ = 1.54184 Å) radiation and for [12•(C60)4•(C7H8)8•(C2H4Cl2)] at 170 K on an Agilent SuperNova diffractometer using mirror-monochromatized Mo Kα (λ = 0.71073 Å) radiation. CrysAlisPro42 program was used for the data collection and processing. The intensities were corrected for absorption using the Gaussian face index absorption correction method43 for [1•(CH3OH)•(CHCl3)2], and analytical face index absorption correction method44 for [12•(C60)4•(C7H8)8•(C2H4Cl2)]. The structures were solved by Direct method with SHELXS45 and refined by full-matrix least-squares methods using the OLEX2,46 which utilizes the SHELXL-97 module.45 All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms were introduced in proper positions with isotropic thermal parameters using the “riding model”. Crystal data, information regarding the data collection, reduction, and convergence results were documented in Table 1. Squeeze47 was applied to the structure refinement for [12•(C60)4•(C7H8)8•(C2H4Cl2)] due to the serious disorder of the guest molecules in the cavity of the capsule. The count of electron removed in total is 290 per cell, among which 225 are in the cavity. They can be accounted for by two C2H4Cl2 molecules in each cavity (200 electrons in total). The fullerene and toluene molecules in structure [12•(C60)4•(C7H8)8•(C2H4Cl2)] are ordered but with large thermal vibration; therefore, the anisotropic displacement parameters for the C atoms were restrained to approximately isotropic model.

Figure 2. Selected packing plots for the structure: (a) C60 packing (all other molecules removed for clarity), (b) resorcinarene bromide (green for the cation and brown for the anions) situated inside the lattice with two independent toluene molecules (blue and light blue), and (c) assembly of the resorcinarene bromide into the lattice of the hierarchical assembly.

resorcinarene bromide, four toluene, and one 1,2-dichloroethane solvent molecules. In addition, some electron density was observed in the cavity I of the resorcinarene dimer (Figure 3a), yet these solvent molecules were so badly disordered that they could not be located. However, combining the SQUEEZE47 estimated electron count in the voids and the solvent used for crystallization indicates that there are two additional, heavily disordered 1,2-dichloroethane in the cavity I. Four C60 molecules are packed tetrahedrally around the fourfold rotoinversion axis and create bilayered C60 lattice (Figure 2a) with a pore diameter of 12.08 Å. The C60 “tetrahedra” are slightly distorted with center-to-center distances of 10.012 and 10.17 Å to the neigboring C60 molecule (Figure 2b). The distance between the adjacent C60 “tetrahedra” is 10.204 Å (C60 center-to-center distance, Figure 2b). All these distances are in line with the reported contacts in the pure C60 crystals48,49

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RESULTS AND DISCUSSION Co-crystallization of the resorcinarene salt 1 and slight excess of C60 in a mixture of toluene and 1,2-dichloroethane resulted in single crystals of the assembly [1 2 •(C 60 ) 4 •(C 7 H 8 ) 8 • (C2H4Cl2)], Figure 2) analyzed by X-ray crystallography. The complex supramolecular assembly consisting of the fullerene C60, the resorcinarene bromide, and the solvent molecules crystallizes in tetragonal space group P4/n. The highly symmetrically packed lattice consists of four C60, two 6162



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Table 1. Information about Data Collection, and Structure Refinement Details Chemical formula Mr Crystal system, space group Temperature (K) a, b, c (Å) α, β, γ (deg) V (Å3) Z Radiation type μ (mm−1) Crystal size (mm) Tmin, Tmax No. of measured, independent and observed [I > 2σ(I)] reflections Rint (sin θ/λ)max (Å−1) R[F2 > 2σ(F2)], wR(F2), S No. of reflections No. of parameters No. of restraints Δρmax, Δρmin (e Å−3)

[1•(CH3OH)•(CHCl3)2]

[12•(C60)4•(C7H8)8•(C2H4Cl2)]

C72H88N4O8·4(Br)·2(CHCl3)·C2H6O 1741.91 Triclinic, Pi ̅ 120 13.3944 (3), 15.7651 (4), 20.8205 (4) 81.3104 (19), 77.788 (2), 66.947 (2) 3942.50 (16) 2 Cu Ka 4.82 0.38 × 0.17 × 0.11 0.090, 0.391 28078, 13954, 12382 0.034 0.596 0.038, 0.101, 1.01 13954 955 25 1.04, −0.76

2(C72H88N4O8)·8(Br)·4(C60)·8(C7H8)·C2H4Cl2 3316.31 Tetragonal, P4/n 170 24.9287 (16), 90, 24.746 (2) 90, 90, 90 15378 (2) 2 Mo Ka 1.14 0.16 × 0.12 × 0.06 0.647, 0.826 35918, 13552, 4463 0.072 0.595 0.129, 0.403, 0.95 13552 1104 672 1.17, −0.51

Figure 3. (a) Space-filling model highlighting the cavities I and II in the packed resorcinarenes, (b) a ball-and-stick model showing the encapsulated 1,2-dichloroethane (CPK) in the cavity II, (c) a ball-and-stick model of the face-to-tail arrangement of resorcinarene bromide 1 MeOH−CHCl3 (CPK) solvate.

molecules act as a glue between each C60 tetrahedron and resorcinarene molecules completing the assembly. From a topdown view, the 1-D lattice channels are filled with self-assembled resorcinarenes salts in a head-to-head and tail-to-tail alignment with two differently sized cavities (I and II, Figure 3a) filled with smaller molecules. To inspect the importance of C60 as the key element for the assembly and lattice formation, single crystals of the resorcinarene bromide 1 without C60 were obtained via slow evaporation from a mixture of methanol and chloroform. In the structure, the resorcinarene bromides stack in a head-to-tail

and comparable to those expected for the van der Waals interactions. In each C60 layer, two resorcinarene bromides are aligned in a tail-to-tail fashion creating a cavity (cavity II, Figure 3a) with size of 149 Å3 hosting a disordered 1,2-dichloroethane molecule. Considering the separation between the C60 layers and the dimension of the cavity in the C60 bilayer, a space of 12.08 × 24.15 Å is available (Figures 2c, 3a,b). The space is just big enough to host a dimeric head-to-head assembly forming a cavity with size of 280 Å3 (cavity I, Figure 3a) with heavily disordered 1,2-dichloroethane (Figure 3a). The two toluene 6163



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motif with a single cavity (235 Å3) that is filled with ordered MeOH and CHCl3 molecules (Figure 3c). Though it is a different solvent environment, these results confirm that the C60 molecules are crucial for the hierarchical ordering in the ternary structure. This is also supported by the unsuccessful attempts to crystallize the resorcinarene bromide 1 under the same condition as that with C60 thus underlining the necessity of C60. Hirshfeld surfaces50,51 can be used to analyze the nature of intermolecular interactions between C60, 1, and toluene. Although disordered solvents exist in this structure, the resorcinarene and C60 molecules are ordered, which provides accurate information about the weak van der Waals interactions between C60 molecules and resorcinarene salts (Figure 4).

absence of C60, the N-benzyl ammonium resorcinarene bromide forms head-to-tail assemblies with solvent filled cavities. These results provide further insights into the supramolecular assembly of fullerenes and their role in forming novel porous-like lattices. Such modulation of the native C60 packing is quite intriguing and can, when larger shape-persistent macrocycles are used, form very interesting solid state properties.

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ASSOCIATED CONTENT

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AUTHOR INFORMATION

* Supporting Information S

Crystallographic data (CIF) and figures concerning thermal ellipsoid plots for 12•(CH3OH)•(CHCl3)2 and 12•(C60)4• (C7H8)8•(C2H4Cl2), as well as the hydrogen bonded 1-D chain in 12•(CH3OH)•(CHCl3)2, and Hirshfeld surface analysis to show the packing environment in [12•(C60)4•(C7H8)8•(C2H4Cl2)] are available. This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author

*E-mail: kari.t.rissanen@jyu.fi. Tel.: +358 50 562 3721. Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors kindly acknowledged the Academy of Finland (KR.: no. 265328 and 263256, NKB: no. 258653) and the University of Jyväskylä for financial support.

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Figure 4. Hirshfeld surface50,51 showing the intermolecular interaction between the C60 lattice and the guests. The red color indicates strong interaction and the blue color the weakest interactions within the supramolecular aggregate.

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Based on this analysis, the toluene molecules act as adhesive to glue the C60 bilayers and resorcinarene bromide strands together via π···π and CH···π interactions (Figure 4). Structures of C60 with calix[4]arenes have been reported, among them fullerenes feature either as 1-D strands,52,53 flat sheets25 or discrete void-filling moieties,40 however, the fullerenes acting as two-layer-sheets with channels directing strand-shaped resorcinarene multimers as in [12•(C60)4•(C7H8)8•(C2H4Cl2)] is unprecedented.

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CONCLUSIONS In conclusion, we presented the first example of a hierarchical ordering in a ternary co-crystal of C60, N-benzyl ammonium resorcinarene bromide and solvent molecules. The N-benzyl ammonium resorcinarene bromide forms head-to-head and tailto-tail dimeric assemblies with two differently sized cavities filled with smaller molecules. The [12•(C60)4•(C7H8)8•(C2H4Cl2)], assembly crystallized from a mixture of toluene and 1,2dichloroethane. The toluene molecules assisted the selfassembly process acting as adhesives to glue the C60 molecules through multiple π···π and C−H···π interactions while the 1,2dichloroethane molecules are trapped in small cavities formed from the resorcinarenes during the lattice assembly. In the 6164



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Hierarchical Ordering in Ternary Co-Crystals of C60, N-Benzyl

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