CRYSTAL GROWTH & DESIGN
Triangular Halogen-Halogen-Halogen Interactions as a Cohesive Force in the Structures of Trihalomesitylenes
2002 VOL. 2, NO. 4 299-302
Eric Bosch* Department of Chemistry, Southwest Missouri State University, Springfield, Missouri 65804
Charles L. Barnes Department of Chemistry, University of Missouri, Columbia, Missouri 65211 Received April 7, 2002;
Revised Manuscript Received May 20, 2002
ABSTRACT: The structures and molecular packing of tribromo- and triiodomesitylene are reported and compared to that of trichloromesitylene. Attractive triangular X3 interactions dominate the molecular packing in all three structures. The nonspherical atomic charge distribution on the halogens results in the formation donor-acceptor interactions in which each halogen atom is simultaneously a donor and an acceptor. These triangular X3 (X ) Br or I) interactions result in the formation of 2-dimensional sheetlike structures. Introduction The field of crystal engineering has been driven by the desire to rationally design technologically useful materials.1 As this area has developed, certain strategies have been widely exploited, most notably hydrogenbonding2 and metal coordination,3 although other, somewhat weaker, interactions are also recognized as useful tools.4 These weaker interactions include nitrogenhalogen donor-acceptor interactions5-8 as well as the donor-acceptor π-stacking of electron-rich and electronpoor planar aromatics.9 The role of chlorine-chlorine interactions in crystal engineering was recognized and exploited in the seminal studies of photodimerization begun by Schmidt and co-workers at the Weizmann Institute several decades ago.10 Those studies were related to the packing of alkenes in such a way that photoinduced cycloaddition reactions could take place in the solid state. In recent years, Desiraju has convincingly argued that the halogen-halogen interaction is an attractive force that can be used to manipulate and organize supermolecular structure within a crystal.11 Recently, Price12 and Murray13 have demonstrated that the nonspherical atomic charge distribution on the halogens is important in directing halogen-halogen interactions. In this paper, we focus on the role of triangular halogen-halogen-halogen interactions in controlling the crystal packing of the trihalomesitylenes 1, 2, and 3 (Chart 1). Experimental Section Synthesis. Triiodomesitylene was prepared according to the procedure of Merkusev et al.14 and recrystallized from dichloromethane. Tribromomesitylene was prepared by bromination of mesitylene with bromine in the dark in dichloromethane solution and recrystallized from dichloromethane. X-ray Crystallography. The X-ray data for triiodomesitylene and tribromomesitylene were collected on a Siemens CCD area detector-equipped diffractometer with MoKR radiation. The structures were solved using SHELXS-9715 and refined using SHELXL-97.16 Hydrogen atoms were included in the calculated positions. The crystallographic data are collected in Table 1.
Table 1. Crystallographic Data CCDC deposit no. formula fw cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, A3 Z µ, mm-1 R (F0) RW (F0)
1
2
CCDC-186932 C9H9I3 497.86 triclinic P-1 7.982(4) 9.587(4) 9.627(6) 120.010(7) 108.548(8) 94.437(8) 579.2(5) 2 8.045 0.0449 0.1216
CCDC-186931 C9H9Br3 356.89 triclinic P-1 7.6920(7) 9.0616(8) 9.0813(8) 119.8336(10) 106.877(2) 95.091(2) 504.30(8) 2 11.941 0.0432 0.1135
Chart 1
Results The structures of 1 and 2 are isostructural with space group P1 and Z ) 2. In each structure, the molecules are arranged as layers of two-dimensional sheets. The packing within each layer of 1 and 2 is dominated by halogen-halogen interactions that are emphasized in Figure 1 showing part of a two-dimensional sheet of 1. Indeed the space-filling model in Figure 1B emphasizes the halogen-halogen contacts. Each halogen atom is part of a triangular trihalogen interaction that is shown in Figure 2. This interaction can be described in terms of nonbonding interatomic distances, dij, and angles, θ1 and θ2, defined in Figure 2. The halogen-halogen distances, dij, collected in Table 2 are significantly lower than twice the van der Waals radii for 1 and 2. For comparison, the data from the published structure of
10.1021/cg025517w CCC: $22.00 © 2002 American Chemical Society Published on Web 06/12/2002
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Figure 1. (A) View of a portion of a sheet of triiodomesitylene molecules with thermal ellipsoids drawn at 50% probability.36 Iodine-iodine contacts shown with dashed lines. (B) Space filling representation of the same sheet. Table 2. Halogen-Halogen Contacts in Trihalomesitylenes. 2 × vdW a
halogen
d12
d13
d23
Ib
I Br Cl
3.851 3.596 3.662
3.897 3.626 3.651
3.933 3.658 3.594
3.96 3.70 3.52
Ic 4.30 3.90 3.60
a Where d represents the distance between halogen atoms ij labeled i and j, respectively (see Figure 3). b Taken from ref 25. c Taken from ref 26.
Chart 2
Figure 2. View of three triiodomesitylene molecules showing the relationship between adjacent molecules and defining the distances and angles reported in Tables 2 and 3.
trichloromesitylene is included in the table.17 The carbon-halogen-halogen angles, θ1 and θ2, tabulated in Table 2 are similar for each of 1, 2, and 3. One interaction is almost linear with θ1 ) 170.4° (( 5°), and the other is oblique with θ2 approximately 124.2° (( 6°). Discussion The triangular trihalogen nonbonding interaction shown in Figure 2 is made up of three cooperative halogen-halogen interactions with an orientation that Desiraju defined as type II (Chart 2).4,18 The type II interaction was considered to result from polarization of adjacent halogen atoms for a donor-acceptor interaction19 and has recently been understood in terms of the nonspherical atomic charge distribution on the halogen atoms.12,13 Indeed, the electrostatic potential calculated using MacSpartan Plus clearly shows the positive cap
on the iodine atom in iodobenzene as depicted in Figure 3. The halogen-halogen interaction in the series of trihalomesitylenes thus involves multiple Coulombic “donoracceptor” attractions as shown in Figure 4. This rationalization is consistent with Allen’s conclusions that halogens interact with nucleophiles “head-on” and electrophiles “side-on”.20 Desiraju reported this trimeric alignment of interhalogen interactions in his review 1998,21 and shortly thereafter Mak and Nangia reported the interaction for a series of tris(bromoaryl)triazines and reported bromine-bromine distances in the range 3.505-3.787 Å and angles θ1 and θ2 of approximately 165° and 106°.22 They also noted that there were only five other instances of this Br-Br-Br interaction reported in the Cambridge Database with Br-Br distances in the range 3.45-3.95 Å and angles θ1 and θ2 in the range 142-174° and 96-114°. Pennington et al. also noted this interaction in the structure of tetraiodoethylene and defined the iodine atom in each interaction as donor, ID, or acceptor, IA, and the interaction as a donor-acceptor interaction with I-I distances and
Figure 3. (A) Plot showing electrostatic potential about iodobenzene with maxima of negative and positive electrostatic potential indicated. Calculated with MacSpartan Plus. (B) Simplified representation of the electrostatic potential on the iodine atom.
Triangular Halogen-Halogen-Halogen Interactions
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synthon in crystal engineering, although many other factors must also be included in potential crystal engineering application. Figure 4. Interaction of areas of negative and positive electrostatic potential in the structures of the trihalomesitylenes. Table 3. Carbon-Halogen-Halogen Angles in Trihalomesitylenesa X1
X2
X3
halogen
θ1
θ2
θ1
θ2
θ1
θ2
I Br Cl
172.98 170.72 167.30
119.81 124.60 128.75
173.52 174.61 168.75
118.58 124.36 129.44
165.71 169.85 170.24
119.74 124.90 128.01
a
See Figure 2 for definition of θ1 and θ2. Table 4. Iodine-Iodine Distances and Carbon-Iodine-Iodine Angles in I3 Trimeric Interactions compound
distance
θ1
θ2
tetraiodoethylene5
3.837-3.960 175.1-177.1 102.0-103.2 hexaiodobenzene23 3.742-4.022 173.47-176.94 114.76-125.37 iodoform24 3.977 152.45 99.47 Table 5. Chlorine-Chlorine Distances and Carbon-Chlorine-Chlorine Angles in Cl3 Trimeric Interactions compound
1,3,5-trichloro-2,4,6trifluorobenzene27 N-trichloroacetylimino-1,2,3,4,5trithiadiazole28 1-(carboxymethyl)pyridinium bis(pentachlorophenol)29 O-methyl neopyrrolomycin30 4,5,6-trichlorocyclopenta-1,2-dithiole3-carbonitrile31 2,4,6-tris(4-chlorophenoxy) 1,3,5triazine21,32 3,5-dichloro-1H-1,2,4triazole33 4-N,N-dimethylaminopyridinium pentachlorophenolate34
distance 3.651
θ1 171.37
θ2 111.37
3.536-3.674 148.68-166.83 92.7-105.77 3.546-3.633 170.58-171.79 125.57-128.74 3.374-3.647 156.88-170.05 115.38-135.13 3.935
171.73
111.73
3.467
170.96
110.96
3.518
172.87
112.87
3.438-3.692 152.84-172.87 120.83-127.16
C-I- - -I angles similar to those reported here.5 We found two other clear examples of this I3 interaction in the Cambridge Structural Database: hexaiodobenzene23 and iodoform.24 The I-I distances and angles θ1 and θ2 are collected in Table 4. With respect to the trimeric chlorine-chlorine interaction, we found eight structures that included the trimeric Cl3 interaction as noted for trichloromesitylene. The defining angles θ1 and θ2 and Cl-Cl distances are collected in Table 5. The observation that the X3 synthon is rare is most likely because the geometry of molecules often precludes its formation as a repetitive entity. Clearly, the planar trihalomesitylenes have the perfect arrangement of methyl and halogen substituents that facilitate this interaction allowing it to dominate the crystal packing and form layered sheets within the crystal. Many related, but geometrically less restrictive, “donor-acceptor” halogenhalogen interactions have been observed including dimeric units and infinite ribbons.5,35 In conclusion, we note that the donor-acceptor halogen-halogen interactions must be considered as a viable
Acknowledgment. E.B. acknowledges a Faculty Research Grant from the Graduate College at Southwest Missouri State University. Supporting Information Available: X-ray crystallographic information files (CIF) are available for compounds 1 and 2. This material is available free of charge via the Internet at http://pubs.acs.org.
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CG025517W
