Halogen and Hydrogen Bond Architectures in Switchable Chains of Di

Article pubs.acs.org/crystal

Halogen and Hydrogen Bond Architectures in Switchable Chains of Di- and Trihaloimidazoles Michał Andrzejewski, Jędrzej Marciniak, Kacper W. Rajewski, and Andrzej Katrusiak* Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland S Supporting Information *

ABSTRACT: Halogen bonds have been employed for controlling the structure of NH···N hydrogen-bonded chains in halogenated imidazoles; the CH···halogen contacts stabilize the coplanar arrangement of molecules, whereas the halogen··· halogen contacts twist the molecules around the NH···N bonds and stretch their N··· N distances. The interplay of halogen···halogen and NH···N hydrogen bonds leads to isostructural relations of 4,5-dihaloimidazoles as well as between trichloro- and tribromoimidazole. However, the increasing steric hindrance excludes the triiodoimidazole from this isostructural series, and the triiodo derivative forms an unusual structure with three symmetry-independent molecules. All symmetrically substituted 4,5-dichloro-, dibromo-, and diiodoimidazoles as well as trichloro-, tribromo-, and triiodoimidazoles have been synthesized and crystallized and their structures determined. The derived rules also apply to the co-crystal structures of 4,5diiodoimidazole:2,4,5-triiodoimidazole as well as to 4-iodoimidazole:2,4-diiodoimidazole. The halogen interactions prove an efficient means for engineering and tuning new materials with desired dielectric properties relying on highly polarizable NH···N hydrogen bonds.

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molecules.6−8 It appears that parallel chains may be more favorable for ferroelectric structures, as was observed in 2methylbenzimidazole.4 Halogen bonds (X···X bonds, X = Cl, Br, and I) are generally defined as electrostatic interaction between a halogen atom, acting as a Lewis acid, and a neutral or anionic Lewis base.9 X···X bonds are classified into two types, according to the C−X···X angles,10,11 and they also form supramolecular X3 synthons.12 X···X bonds are selective and directional, and their energy can be comparable to that of hydrogen bonds.13 Therefore, X···X bonds have been used for designing molecular systems of desired properties,14 such as molecular conductors, optoelectronic materials,15 and other functional materials.16 Presently, we have used X···X bonds in conjunction with bistable NH···N bonds for designing crystals of halogenated imidazoles. The energy of X···X bonds between positive polar and negative equatorial regions of halogen atoms depends on their electronegativity and polarizability in the F < Cl < Br < I sequence. X···X bonds may also exhibit an amphoteric character because X atoms act as an electron donor and acceptor at the same time.17 X···X bonds are particularly important for molecular arrangement and as cohesion forces in the crystals without other strong interactions.18,19 In the series of haloimidazoles, we intended to employ the X···X bonds and H bonds in order to obtain structures with possibly small differences between H sites in the NH···N bond. In our search for the NH···N-bonded structures with reduced differences

INTRODUCTION Materials with high dielectric permittivity, hysteresis, piezoelectric, piroelectric, and ferroelectric properties are sought because of their possible applications in electronic, optoelectronic, detector, and electromechanic devices.1 Crystals with NH···N hydrogen bonds were shown to exhibit ferroelectric properties caused by the switchable bond polarization depending on the proton site.2,3 Recently, ferroelectric properties of NH···N hydrogen-bonded molecular crystals of 2-methylbenzimidazole and 5,6-dichloro-2-methyl-benzimidazole were reported.4 Also, pyrazole, 1,2-diazole, was shown to undergo pressure-induced phase transition analogous to those in KH 2PO 4 (KDP) type ferroelectrics.5 At high-pressure, imidazole, 1,3-diazole, centrosymmetric at ambient conditions, space group P21/c, crystallizes in a noncentrosymmetric form of polar space group Aba2.6 In the ambient-pressure phase α, the chains of NH···N-bonded mutually twisted imidazole molecules are arranged antiparallel, whereas in high-pressure phase β the NH···N-bonded planar chains run along diagonal directions [011] and [0−11] and, consequently, all chains contribute to the polarity of the crystal along [001]. This suggested that imidazole derivatives can exhibit ferroelectric properties associated with the bistable NH···N bonds in polar crystals. In our present study, we have synthesized a series of new imidazole derivatives by substituting the H atoms with halogen atoms. It was our intention to employ the interactions between halogen atoms for generating new arrangements and architectures of chains. The unsubstituted imidazole and benzimidazole form chains with molecules twisted around the NH···N bonds; however, moderate pressure changes this preference to chains with coplanar or nearly coplanar © 2015 American Chemical Society

Received: October 21, 2014 Revised: February 19, 2015 Published: February 20, 2015 1658

DOI: 10.1021/cg501561w Cryst. Growth Des. 2015, 15, 1658−1665

Article

Crystal Growth & Design

structures of 4,5-dichloroimidazole (dClIm, Figure 1d) and cocrystal of bis(4,5-diiodoimidazole)·triiodoimidazole (2dIIm·tII, Figure 1g) determined previously.20,21 In these symmetrically and asymmetrically halogenated imidazoles, the coupling of molecular orientation and favored H tautomers in conjunction with the X···X bonds has been investigated. Noteworthy is that imidazolium salts and organic−inorganic hybrid compounds exhibit the desired ferroelectric properties.22,23 Although the mechanism of ferroelectricity is different than in NH···Nbonded ferroelectrics, their other properties are related to the ionic liquid salts based on imidazolium derivatives.

induced by N protonation, we have chosen the 4,5-di- and 2,4,5-trihaloimidazoles (denoted dXIm and tXIm, respectively). Their molecular H tautomers are mutually symmetric with respect to the pseudo 2-fold axis of the molecular ring. Owing to this molecular pseudosymmetry, the NH···N bonds could switch more easily, and the crystal polarization could be reversed by the external field. The proton sites could be either disordered or correlated, and this in turn can generate polar nanoregions and crystal structures of high electric permittivity. The series of imidazole halo derivatives synthesized and determined in this study are shown in Figure 1.

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EXPERIMENTAL SECTION

Synthesis of Haloimidazoles. 2,4,5-Tribromo-1H-imidazole (tBrIm) was prepared by bromination of imidazole.24 2,4,5-Triiodo1H-imidazole (tIIm) was synthesized in the reaction of imidazole with iodine.25 4,5-Diiodo-1H-imidazole (dIIm) and the 4-iodo-1Himidazole·2,4-diiodo-1H-imidazole co-crystal (IIm·dIIm) were separated after partial iodination of imidazole. 2,4,5-Trichloro-1Himidazole (tClIm) was purchased from SynChem and recrystallized from isopropanol. 4,5-Dibromo-1H-imidazole (dBrIm) from SigmaAldrich was used as delivered. All halogenated imidazoles form nice crystals with well-developed faces (Figure S1 in Supporting Information) when recrystallized by evaporation from methanol and ethanol solutions. X-ray Diffraction Analyses. The diffraction data were collected on an Agilent Xcalibur four-circle CCD diffractometer with a Mo X-ray source. CrysAlis software was used for controlling the measurements and data reduction.26 Absorption corrections were calculated by Abspack.27 Program interface Olex228 was used. Structures were solved by direct methods of Shelxs and refined with anisotropic nonhydrogen atoms by full-matrix least-squares on F2s by Shelxl.29 Hydrogen atoms were located from the molecular geometry at distances NH 0.86 Å and CH 0.98 Å; the Uiso parameters of H atoms were constrained to 1.2Ueq of their carriers. The symmetry of structures tClIm, tBrIm, and tIIm·2dIIm21 requires that the azole hydrogen atoms are disordered at the half-occupied sites according to the space-group symmetry requirements (Figure S2 in Supporting Information). For other crystals, the amine H atoms were located either in the Fourier maps in correlation with the distances of conjugated HN−CN bonds system or we attempted to refine the site-occupancy factor (SOF) of the H atoms ideally located in its two sites as a free variable according to the formula SOF(N1) + SOF(N3) = 1. However, because of the dominating scattering of the halogen atoms, no conclusive information about the H site could be obtained. The strong scattering of halogen atoms dominates the diffraction of the crystal, and consequently the precision of positions of weakly scattering H, C, and N atoms as well as of the dimensions involving these atoms are relatively low. In the final models for all structures, the H atoms were arbitrally assigned to atom N1. Selected information about the determined structures has been listed in Table 1. Electrostatic potential of the halogenated imidazole molecules was computed at MP2/Def-2-qzupd level of theory30,31 using Gaussian09,

Figure 1. Haloimidazoles studied in this paper and their acronyms: (a) 4,5-dichloro-1H-imidazole (dClIm), (b) 4,5-dibromo-1H-imidazole (dBrIm), (c) 4,5-diiodo-1H-imidazole (dIIm), (d) 2,4,5-trichloro-1Himidazole (tClIm), (e) 2,4,5-tribromo-1H-imidazole (tBrIm), (f) 2,4,5-triiodo-1H-imidazole (tIIm), (g) co-crystalline 2,4,5-triiodo-1Himidazole·4,5-diiodo-1H-imidazole 1:2 complex (tIIm·2dIIm), and (h) co-crystalline 4-iodo-1H-imidazole·2,4-diiodo-1H-imidazole 1:1 complex (IIm·dIIm).

We have also obtained a 1:1 co-crystal of asymmetric molecules of 4-iodo- and 2,4-diiodoimidazoles, IIm:dIIm (Figure 1h). The asymmetric molecules in this co-crystal favor one polarity of chains, unlike in symmetric di- and trihaloimidazoles (Figure 1a−f). Along with the series of the crystal structures determined by us, we have analyzed the

Table 1. Selected Crystallographic Data of the Investigated Haloimidazolesa

a

name

dClIm20

dBrIm

dIIm

tClIm

tBrIm

tIIm

IIm·dIIm

tIIm·2dIIm21

formula space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z/Z′

C3H2N2Cl2 P41212 6.843(4) 6.843(4) 24.236(7) 90 1134.891 8/1

C3H2N2Br2 P41212 6.8566(4) 6.8566(4) 25.535(2) 90 1200.48(17) 8/1

C3H2N2I2 P41212 6.8867(4) 6.8867(4) 28.275(3) 90 1340.99(2) 8/1

C3H1N2Cl3 Ama2 9.9264(8) 16.0761(14) 3.8161(4) 90 608.965(13) 4/0.5

C3H1N2Br3 Ama2 10.1305(4) 16.7094(10) 4.0483(2) 90 685.27(7) 4/0.5

C3H1N2I3 P21/a 9.4587(4) 22.0806(7) 14.0805(5) 108.219(4) 2793.34(3) 12/3

C3H3N2I1·C3H2N2I2 P21/c 4.5050(3) 19.0373(7) 15.2402(8) 100.280(5) 1201.68(10) 4/1

C3H1N2I3·2(C3H2N2I2) P21/m 4.27080(10) 27.9241(6) 8.8926(2) 101.611(1) 1038.81(4) 2/0.5

See Table S1 in Supporting Information for detailed information. 1659


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Figure 2. (a−c)Space-filling drawings illustrating the planar arrangement of disubstituted imidazoles dClIm, dBrIm, and dIIm, respectively, and (d− f) steric hindrances twisting the molecules about the NH···N bonds in trihaloimidazoles tClIm, tBrIm, and tIIm, respectively. (g) In co-crystal tIId· 2dIIm, the steric hindrances twist the molecules around every second and third NH···N bonds. (h) In co-crystal IIm·dIIm, no steric hindrances are present, and the chains are nearly planar. rev. D.32 The electrostatic potential was mapped on the molecular surface defined as 0.001 au electron-density envelope33 (Figure S3).

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DISCUSSION The main structural feature of all investigated haloimidazoles are the chains of NH···N-bonded molecules (Figures 2, 3, and 4). In turn, these NH···N-bonded chains are arranged through X···X interactions into 3D patterns, except for dClIm, dBrIm, and IIm·dIIm where the chains are arranged into layers, but no

Figure 4. Intermolecular interactions in the studied co-crystals: (a) IIm:dIIm, with no X···X interactions, and (b) tIIm:2dIIm co-crystal, a chain of NH···N hydrogen bonds (highlighted blue) is supported by I···I bonds (purple).

X···X contacts shorter than the sum of van der Waals radii are present. The halogen substituents considerably affect the structure and interactions of the chains in several ways. The electronegative halogen atoms withdraw electrons of the imidazole ring and affect the strength of NH···N bonds. The X···X bonds and steric hindrances between voluminous halogen atoms are equally important for the structure of chains and their arrangement. The dXim crystals are isostructural in noncentrosymmetric space group P41212. Relative to dClIm, the unit-cell dimension a increases in dBrIm and dIIm by 2.0 and 6.4% and dimension c by 5.3 and 16.7%, respectively. tClIm and tBrIm are also isostructurally related; they both form polar crystals of spacegroup symmetry Ama2. The considerably different tIIm structure, of centrosymmetric space group P21/a and Z′ = 3 (Table 1), can be attributed to steric hindrances, as will be

Figure 3. . Halogen···halogen contacts around a single chain of NH··· N-bonded haloimidazole molecules in (a) dClIm, (b) dBrIm (no X···X contacts shorter than the sum of van der Waals radii), (c) dIIm, (d) tClIm, and (e) tBrIm. Contacts Cl···Cl, Br···Br and I···I are highlighted green, orange and purple, respectively. 1660


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Crystal Growth & Design discussed later. The effect of steric hindrance on molecular packing is also apparent in the structure of co-crystal tIIm· 2dIIm (Figure 5).21 The amphoteric character of iodine atom

Table 2. Dimensions of NH···N Bonds in Halogenated Imidazolesa compound dClImb dBrIm dIIm tClIm tBrIm tIImc

Figure 5. One translationally repeated interval of NH···N-bonded chain, including four symmetry-independent parts, each of one dIIm molecule and a half tIIm molecule in the tIIm·2dIIm co-crystal. The mirror planes perpendicular through tIIm molecules and the inversion centers between dIIm molecules imply the disorder of azole H atoms shown at their half-occupied sites in this drawing.

IIm·dIImd tIIm·2dIIme

D···H (Å)

H···A (Å)

D···A (Å)

DH···A (deg)

0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.879 0.879

2.020 1.957 1.950 2.021 2.105 1.875 1.930 1.915 2.021 1.948 1.875 1.921

2.799(2) 2.812(15) 2.805(19) 2.869(5) 2.952(12) 2.734(6) 2.789(5) 2.774(2) 2.872(11) 2.799(10) 2.754(9) 2.800(6)

166.0 173.2 172.7 168.64 168.01 176.2 177.3 176.6 170.1(6) 170.1(6) 177.74 178.4

a

Detailed information, including symmetry codes of the H-acceptor atoms, are given in Table S2 in Supporting Information. Three independent NH···N bonds are listed for tIIm, likewise two H-bonds for each co-crystal. The H atoms were fixed at ideal positions. b According to ref 20. cIndependent bonds N(1A)H···N(3B), N(1B)H···N(3C), and N(1C)H···N(3A); each is described on one line. d Two symmetry-independent H bonds: N11H···N3 and N1H···N13. e Two independent bonds: N2H···N2 and N1H···N3; according to ref 21.

I1 leads to trifurcated contacts in tIIm·2dIIm. The relation of unit-cell parameters between co-crystals tIIm·2dIIm and IIm· dIIm may be due to similar dimensions of molecules NH···Nbonded in chains, but no other apparent isostructural features between these crystals have been found. Conductive properties of the haloimidazoles are likely to occur along the NH···N hydrogen bonds.34−36 The proton transfers in H bonds of haloimidazoles may be hampered by a long N···N distance, for example, of 2.952(12) Å in tBrIm, but facilitated by identically oriented H-bonded molecules, favored by X···X bonds, and resulting from the crystal-symmetry requirements. It is remarkable that one of three symmetryindependent NH···N bonds in tIIm is shorter and more linear than that in imidazole high-pressure phase β (2.755 Å at 3.35 GPa).6 It illustrates that the H-bond dimensions are considerably affected by crystal packing and other intermolecular interactions, mainly halogen bonds within and without the chains. The NH···N hydrogen bonds are bent between 166.0° (dClIm) and 178.4° (tIIm·2dIIm), and their length significantly varies between 2.734(6) Å in tIIm and 2.952(12) Å in tBrIm (Table 2). Apart from tClIm, tBrIm, and IIm·dIIm, all compounds form NH···N bonds shorter than that in neat imidazole phase α (N···N = 2.861(1) Å at 296 K).6 The N···N distances in isostructural dihaloimidazoles are consistent within errors (Figure 6), whereas in trihaloimidazoles the NH···N distances can be related to the size of halogen substituents and lead to structural transformations, as will be discussed below. In dihaloimidazoles, the NH···N-bonded chains run along diagonal directions [110] and [1-10], and the unit-cell parameter a changes much less than parameter c in the dXIm series (Table 1, Figure 7). The shorter N···N distances are favorable for activating the proton transfer between H-bonded molecules. Unlike the nearly planar NH···N-bonded chains of dihaloimidazole molecules, the trihaloimidazole (tClIm, tBrIm, and tIIm) chains are twisted (Table S2 in Supporting Information). In tClIm and tBrIm, the departures of H-bonded molecules from the planar arrangement are due to the steric hindrances X···X between the halogen atoms across the H bonds (Figure 2d−g) and to the X···X interactions. The angle between best planes fitted to the H-bonded molecules are equal to 47.61(8)° in tClIm, 42.0(1)° in tBrIm, and 56.5(6), 102.5(5), and 105.1(5)° across three symmetry-independent H-bonds in tIIm (Table S2 in Supporting Information). The

Figure 6. Correlation between N···N distances and angles NHN of the H bonds in halogenated imidazoles (acronyms as in Figure 1; Im-α denotes the imidazole phase α under normal conditions). Im-α at 0.1 MPa/296 K (red hexagon) has been included for comparison. The highlighted points illustrate the spread of H-bond dimensions within one crystal. Arrows indicate the series of analogous dClIm → dBrIm → dIIm and tClIm → tBrIm → tIIm compounds.

tIIm structure shows that effects other than steric hindrances contribute to the position of H-bonded molecules. The Hbonded molecules in imidazole α6 and benzimidazole α7 are twisted, too. The halogen bonds affect the geometry of the NH···N bonds and are responsible for the arrangement of H-bonded chains (Figures 2−4). The dimensions of X···X halogen bonds investigated in the halogenated imidazoles, X···X distances, and CX···X angles are listed in Table 3. Halogen bonds are absent in the dClIm, dBrIm, and IIm·dIIm structures. It is apparent that within the NH···N-bonded chains the halogen bonds have been replaced by stacking interactions and X···π contacts in dClIm and dBrIm (Figure 8 and Table S3 in Supporting Information). In the series of investigated haloimidazoles, the structure of dIIm is the only one where 1661


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Figure 7. Unit-cell projections of haloimidazole structures. In(d) tClIm, (e) tBrIm, and (g) tIIm·2dIIm structures, crystal symmetry requires that protons and alternative NC−N bonds are disordered. The regions of Cl···Cl, Br···Br, and I···I interactions are highlighted green, orange, and pink, respectively.

was shown recently for the series of halomethanes CH3X and dihalomethanes CH2XY (X, Y = Cl, Br, and I) that the X···X halogen bonds and CH···X bonds compete in governing the molecular packing in crystals.37 However in the tXIm molecules, no CH groups are present, and we found that in the dXIm structures the C2H group is likewise not involved in CH···X contacts. Moreover, the halogen atoms at C2 in tXIm do not form any intermolecular X···X contacts. All such contacts exclusively involve the vicinal halogen atoms at C4 and C5. All but one X···X bond in tIIm significantly divert from the ideal types I and II and synthon X3. Molecules in tIIm are NH··· N-bonded into sinusoidal ribbons that are shifted in phase with respect to their neighbors (Figure 9). Every third triiodiimidazole molecule interconnects these ribbons into a layer via I···I contacts. Neighboring layers are shifted by a/2 along the x axis, which produces considerable voids of solvent-accessible volume (19 Å3, 0.7% of the unit-cell volume). Although there are no X···X contacts shorter than the sum of van der Waals radii in dClIm and dBrIm,38 in dIIm each

Table 3. Dimensions of X···X Contacts in Halogenated Imidazolesa compound dIIm tClIm tBrIm tIIm tIIm·2dIIm21

X1···X2 (Å)

Θ1 X1···X2 (deg)

Θ2 X1···X2 (deg)

3.910(4) 3.910(4) 3.4760(7) 3.4760(7) 3.6164(14) 3.6164(14) 3.805(4) 3.872 3.912 3.917 3.917

109.8(9) 109.8(9) 127.082(13) 127.082(13) 124.5(3) 124.5(3) 140.9(5) 124.12 117.93 112.62 112.62

177.7(4) 177.7(4) 162.36(7) 162.36(7) 161.6(3) 161.6(3) 140.9(5) 173.56 165.78 167.29 167.29

a No X···X bonds are formed in structures dClIm, dBrIm and IIm· dIIm.

all four intermolecular interactions types (NH···N, X···X, X···π, and π···π) are present (Table S4 in Supporting Information). It 1662


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Figure 8. (a) Shortest contacts X···π correlated with CX···π (C atom) angles and (b) the distances between stacked rings plotted versus their shifts.

Figure 10. Topology of halogen−halogen interactions: (a) sinusoidal shape in dIIm and (b and c) zigzag chains in tClIm and tBrIm, respectively.

longer than in the dihaloimidazoles, where no such steric hindrances are present. Thus, in trihaloimidazoles the NH···N bonds compete with the X···X steric hindrances within the chains. This competition can be responsible for the structure of tIIm, which is markedly different than those of isostructural tClIm and tBrIm. It can be estimated (Table 2 and Figures 6,7, and 9) that in this series the I···I repulsion would stretch the NH···N bond to more than 3 Å in a hypothetical tIIm structure that is isostructural to crystals tClIm and tBrIm. Instead, the tIIm structure is formed with three independent molecules linked by short H bonds, but without steric hindrances. In this highly unusual structure (Z′ = 3), the steric hindrances between iodine atoms in chains have been released, and consequently all three symmetry-independent NH···N bonds are significantly shorter than those in tClIm and tBrIm (Table 2, Figure 4). Although group C2H is not involved in any short contacts, it is characteristic that in all investigated structures with the C2H groups the NH···N-bonded molecules are coplanar. This orientation is consistent with electrostatic attraction between a positive net charge of the H atom and the negative rim of halogen atoms. Apart from tIIm, the stacking interactions

Figure 9. (a) A single layer of tIIm molecules in NH···N-bonded sinusoidal chains (highlighted blue), interconnected by iodine···iodine type-I bonds (purple), and (b) two such neighboring layers (marked green and red).

iodine atom forms one contact with a neighboring molecule (Figures 3 and 10). In isostructural tClIm and tBrIm, there are two bifurcated interactions involving C4 and C5 X atoms, and the X atom bonded to C2 does not interact with other halogen atoms (Figures 3 and 10). In summary, the steric hindrances are responsible for the twisted positions of molecules in NH···N-bonded chains (Figure 2) and also for stretching the H bonds in tClIm and tBrIm. Therefore, the bonds in these structures are significantly 1663


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between molecules are present in all crystal structures (Table S4 in Supporting Information).

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CONCLUSIONS The structure of halogenated imidazoles can be efficiently controlled by halogen···halogen interactions, but the main structural feature of halogenated imidazoles, the NH···Nbonded chains, is preserved. Within the chains, the coplanar arrangement of molecules is stabilized by CH−halogen interactions, whereas the steric hindrances between voluminous halogen atoms twist the NH···N-bonded molecules. For this reason, no planar chains could be obtained in trihaloimidazoles. Halogen···halogen interactions between chains are very important for the arrangement of chains, although in none of the structures investigated were the halogen atoms at C2 involved in X···X bonds. The series of isostructural crystals are formed for dichloro-, dibromo-, and diiodoimidazole (space group P412121) and for trichloro- and tribromoimidazole (space group Ama2); however, the structure of triiodoimidazole significantly diverges from the latter series (space group P21/ a, Z′ = 3). It is plausible that the different triiodoimidazole structure is due to considerable steric hindrances within the NH···N-bonded chains, as suggested by considerably increased NH···N bond length between trichloro- and tribromoimidazole. The NH···N bonds in halogenated imidazoles vary considerably in length; both much shorter and longer bonds are present than in imidazole phases α and β. For these reasons, the halogenations of NH···N-bonded compounds appears a useful means for engineering novel functional materials of ferroelectric and relaxor properties.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format, selected bond lengths and angles, electrostatic-potential surfaces, and electrostatic potential mapped on Hirschfeld surfaces.39 This material is available free of charge via the Internet at http://pubs.acs.org. Full crystal data have also been deposited in the Cambridge Crystallographic Database Centre as supplementary publication numbers CCDC 1030310, 1030311, 1030312, 1030313, 1030314, and 1030345. Their copies can be obtained free of charge from http://www.ccdc.cam.ac.uk.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +48 (61) 8291590. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This study was partly supported by the Foundation for Polish Science, Team program 2009-4/6. The theoretical computations were performed in the Poznań Supercomputing and Networking Center, and their grant is gratefully acknowledged.

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REFERENCES

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