Supramolecular Architecture in Some 4-Halophenylboronic Acids

CRYSTAL GROWTH & DESIGN

Supramolecular Architecture in Some 4-Halophenylboronic Acids

2007 VOL. 7, NO. 10 1958-1963

Manishkumar R. Shimpi, Nanappan SeethaLekshmi, and Venkateswara Rao Pedireddi* Solid State & Supramolecular Structural Chemistry Unit, DiVision of Organic Chemistry, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008, India ReceiVed NoVember 29, 2006; ReVised Manuscript ReceiVed July 7, 2007

ABSTRACT: Crystal structures of 4-chloro- and 4-bromophenylboronic acids (1 and 2) and hydrates of 2 and 4-iodophenylboronic acid in two different forms (2a, 3a, and 3b), which were characterized by single-crystal X-ray diffraction methods, are reported. In structures 1 and 2, -B(OH)2 forms a syn-anti conformation, but it exists in syn-syn as well as anti-anti conformations in the hydrated structures 2a, 3a, and 3b. In all the structures, the molecules are held together by O-H‚‚‚O interactions formed by -B(OH)2 groups. The C-H‚‚‚X (X ) Cl, Br, and I) interactions play an important role in crystal packing. In 2, Br‚‚‚Br interactions are also observed. Interestingly, all the three hydrates form similar types of three-dimensional structures with the formation of channels, which are occupied by water molecules. The two hydrates of 4-iodophenylboronic acid (3a and 3b) are distinguishable on the basis of O‚‚‚O short contacts, with an identical host lattice of the boronic acid. Introduction

Chart 1

Crystal engineering and supramolecular chemistry1,2 are based on prior knowledge of the characteristics of noncovalent bonds, such as geometrical features, energy, etc., which are very much dependent on the nature of atoms in a given molecular entity, that are involved in the formation of the bonds.3-5 In this respect, elegancy and robustness of hydrogen bonds formed by various functional groups such as -COOH, -CONH2, etc. were demonstrated both experimentally and theoretically and also have been successfully employed for the preparation of numerous molecular adducts of targeted assemblies with distinct architectures.6-8 However, boronic acids with a general representation of -B(OH)2, which are also potential entities to form hydrogen bonds, have not been well explored for supramolecular synthesis,9 except for a few examples that appeared in the literature recently10 including our report on the synthesis of supramolecular assemblies of some boronic acids with aza-donor compounds.11 It is surprising to note that attention toward the determination of three-dimensional (3D) structures of boronic acids has increased only in recent times (see Supporting Information) as evident from a search performed on the Cambridge Structural Database (CSD).9a This is due to the utility of boronic acids in Suzuki coupling and many other organic transformations, bioactivity studies, etc.12-14 Apart from conventional hydrogen bonds, hydrogen bonds involving halogen atoms as acceptors are of current interest to structural and supramolecular chemists.15-17 However, the reports on the utility of halo compounds especially haloboronic acids in supramolecular synthesis are scarce. Thus, we are interested in exploring different types of noncovalent interactions in various halogen substituted phenylboronic acids, as a forerunner to explore new avenues in materials science and biological studies, in particular, 4-halophenylboronic acids, due to their antibacterial properties.19 As a result, we have synthesized various halogenated boronic acids following the reported procedures.20 Herein, we discuss the structural features of 4-chlorophenylboronic acid (1), 4-bromophenylboronic acid (2), and its monohydrate (2a), and two hydrates of 4-iodophenylboronic acid (3a and 3b), as shown in Chart 1. * To whom correspondence [email protected].

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Results and Discussion Solid-State Structure of 4-Chlorophenylboronic Acid (1). 1 gave good quality single crystals during crystallization from H2O that were suitable for analysis by X-ray diffractions methods. The obtained data revealed that 1 crystallizes in P21/c space group (Table 1). It is known from the literature that the -B(OH)2 functional group shows mainly three types of conformations, as shown below, with syn-anti conformation, the most commonly observed one (see Supporting Information).

In the crystal structure of 1, the -B(OH)2 moiety adopted the most preferred syn-anti conformation, as shown in the ORTEP structure (Figure 1a). In the crystal lattice, the adjacent entities are held together by O-H‚‚‚O interactions forming R22(8) and R22(18) motifs (Figure 1b). The geometrical parameters of hydrogen bonds are given in Table 2. In the crystal structure of 1, molecular chains are formed by the interplay of C-H‚‚‚Cl interactions (Figure 1b). It is worth noting the absence of Cl‚‚‚Cl interactions. Such one-dimensional chains are arranged in a perpendicular manner and are held together by O-H‚‚‚O hydrogen bonds (H‚‚‚O, 1.75 Å) formed by the anti H-atom of the -B(OH)2

10.1021/cg060863p CCC: $37.00 © 2007 American Chemical Society Published on Web 08/29/2007

Architecture of 4-Halophenylboronic Acids

Crystal Growth & Design, Vol. 7, No. 10, 2007 1959

Table 1. Selected Crystal Data, Data Collection, and Refinement Parameters of Boronic Acids 1, 2, 2a, 3a, and 3b

formula formula wt. crystal habit crystal color crystal system space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å 3) Z Dcalc (g cm-3) T (K) Mo KR µ (mm-1) 2θ range (deg) limiting indices F(000) reflns measured unique reflns. reflns used no. of parameters GOF on F2 R1 [I > 2σ(I)] wR2

1

2

2a

3a

3b

C6H6BClO2 156.37 blocks colorless monoclinic P21/c 14.678(4) 5.951 9.030(2) 90 105.72(4) 90 759.3(3) 4 1.368 133(2) 0.71073 0.433 46.58 -16 e h g 16 -6 e k g 6 -9 e l g 10 320 4363 1085 881 115 1.104 0.0385 0.1115

C6H6BBrO2 200.83 blocks colorless triclinic P1h 5.010(3) 7.241(4) 10.989(6) 103.30(8) 97.06(9) 100.52(9) 375.7(4) 2 1.775 133(2) 0.71073 5.400 46.60 -5 e h g 5 -7 e k g 8 -12 e l g 9 196 1607 1069 867 115 0.970 0.0622 0.1607

2(C6H6BBrO2): 1.5(H2O) 425.66 blocks colorless orthorhombic Ibam 14.427(9) 24.973(1) 9.901(6) 90 90 90 3567.0(4) 8 1.585 133(2) 0.71073 4.561 46.56 -16 e h g 2 -24 e k g 25 -10 e l g 11 1664 3585 1286 707 112 1.011 0.0728 0.2058

2(C6H6BIO2): (H2O) 511.64 plates colorless orthorhombic Ibam 15.157(8) 24.837(1) 9.872(5) 90 90 90 3716.0(3) 8 1.829 133(2) 0.71073 3.397 46.66 -16 e h g 16 -22 e k g 27 -10 e l g 10 1920 7780 1432 968 116 1.021 0.0563 0.1554

2(C6H6BIO2): (H2O) 511.64 blocks colorless orthorhombic Ibam 19.280(6) 18.881(6) 9.854(3) 90 90 90 3587.1(2) 8 1.895 133(2) 0.71073 3.520 46.52 -21 e h g 18 -20 e k g 20 -10 e l g 10 1920 7507 1377 1128 108 1.088 0.0525 0.1794

moiety as shown in Figure 1b. In fact, this resembles one of the rare arrangements of structural packing of the amide compounds, in particular, one having features identical to 3,5dinitrobenzamide.8a Structures of 4-Bromophenylboronic Acid (2) and Its Hydrate (2a). The solid-state structure of 2 reported in the literature,18a in a P6/mcc space group, with an R-factor of 0.24, is not so reliable to validate the structural features of a compound. Another structure known for this compound is an ethanol solvate.18c Hence, we attempted the crystallization of 2 and noted that it crystallizes from H2O or a mixture of H2O and CH3OH, in the P1h space group. The analysis of molecular geometry reveals that, in 2 also, the -B(OH)2 group is in the

syn-anti conformation (see Figure 2a), suggesting the packing of molecules in the crystal lattice mimicking the amide functionality. In fact, the arrangement observed is as anticipated, and the interaction between the molecules is shown in Figure 2b. As observed in 1, the -B(OH)2 moieties on the adjacent molecules are held together by O-H‚‚‚O hydrogen bonds with a H‚‚‚O distance of 1.78 Å (Table 2). However, these dimers, unlike in 1, are held together by Br‚‚‚Br rather than C-H‚‚‚Br interactions. The Br‚‚‚Br interaction distance is 3.57 Å and belongs to the type I halogen‚‚‚halogen interactions with the C-Br‚‚‚Br angle of 165°. Thus, the molecules of 2 formed infinite chains, and these in turn are held together by O-H‚‚‚O hydrogen bonds (H‚‚‚O, 1.94 Å) formed by the anti-H atom of the -B(OH)2 moiety. However, the interaction between the chains is quite different than observed in 1 as molecules related by translation-symmetry participated in the establishment of the interaction. As a result, the structure of 2 is similar to the general class of amide structures. The 3D stacking of these sheets is depicted in Figure 2c. However, crystallization of 2 from CH3OH solution gave crystals 2a, with unit cell parameters different than those mentioned above. However, the structure determination revealed that 2a is a hydrate of 2. The contents of the asymmetric unit are shown in Figure 3a. Nevertheless, the structural arrangement of molecules in 2a and furthermore the crystal packing in a 3D arrangement are quite intriguing with the formation of the channel structure.

Figure 1. (a) ORTEP of 4-chlorophenylboronic acid (1). (b) View along the b-axis showing the two-dimensional network of O-H‚‚‚O and C-H‚‚‚Cl interactions.

In the crystal lattice of 2a, there are two molecules of boronic acid in the asymmetric unit with a different conformation of the -B(OH)2 moiety. It is interesting that neither of them has the conformation discussed in the structures of 1 and 2 but rather adopted syn-syn and anti-anti orientations (see Figure 3a). These differently oriented acids interact through O-H‚‚‚O hydrogen bonds (H‚‚‚O, 1.78 Å) yielding dimers. Further, these dimers interact with each other through -H atoms in anti

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Table 2. Geometrical Features of Hydrogen Bonds and van Der Waals Contacts in the Structures 1, 2, 2a, 3a, and 3a compound 1 2 2a

O-H‚‚‚O 1.75 1.75 1.78 1.94 1.78 1.91

3a

1.78 1.91

3b

1.77 1.88

2.72 2.73 2.75 2.80 2.73 2.79 1.94 2.65 2.66 2.79 2.74 2.78 2.18 2.64 2.76 2.78 2.73 2.74 2.63 2.74

C-H‚‚‚O

C-H‚‚‚Cl 3.00

4.07

C-H‚‚‚Br

C-H‚‚‚I

168 175 172 144 164 147

2.77

3.57

131

170

2.67 2.74 2.54

3.58 3.75 3.57

143 155 158

163 146

2.55

3.58

158

3.35 3.38

4.12 4.26

129 140

163 144

2.48 2.79

3.51 3.79

160 155

3.35 3.48

4.16 4.21

133 126

3.15

4.09

147

3.26 3.28

4.07 4.13

133 136

a In each row for every interactions the three numbers correspond to distances H‚‚‚A (A ) O/Cl/Br/I), D‚‚‚A (DdO/C) in Å and the angle D-H‚‚‚A (°), respectively; in the column corresponding to O-H‚‚‚O interaction, the single value represents the O‚‚‚O contacts.

Figure 2. (a) ORTEP of 4-bromophenylboronic acid, 2. (b) Twodimensional arrangement of molecules (view along the c-axis) in the crystal structure of 2 with Br‚‚‚Br interactions and O-H‚‚‚O hydrogen bonds. (c) Packing of sheets (along the a-axis) in the three-dimensional arrangement.

positions as observed in the structure of 1 (chloro analogue) rather than that observed in 2. The hydrogen-bonding network is shown in Figure 3b. The analysis of C-H‚‚‚Br interactions also show the resemblance of 2a to that of 1 with the formation of C-H‚‚‚Br interactions (H‚‚‚Br, 3.26, 3.28 Å) and no Br‚‚‚Br interactions. In addition,

the molecular tapes resulting from the C-H‚‚‚Br interactions are further held together by C-H‚‚‚O hydrogen bonds (H‚‚‚O, 2.54 Å) as shown in Figure 3c. Such networks in the 3D arrangement gave a channel structure along the c-axis, which is occupied by two water molecules and one of them is disordered. The channels are shown in Figure 3d without water molecules for the purpose of clarity. In fact, this structure has a topological arrangement close to that observed in the ethanol solvate of 2, reported recently.18c In our continued efforts, however, we were not yet successful in obtaining any new forms or solvates. However, our experiments with 4-iodophenylboronic acid gave different hydrated forms as described below. Two Hydrates of 4-Iodophenylboronic Acid, 3a and 3b. Crystallization of 4-iodophenylboronic acid from acetone gave single crystals 3a in its hydrated form as determined from X-ray diffraction methods. Interestingly, the analysis of the molecular packing in the crystal lattice shows that 3a is isostructural to that of 2a in all aspects except for the intra- and intermolecular distances. Thus, in the structure of 3a the two molecules in the asymmetric unit also form dimers through O-H‚‚‚O hydrogen bonds (H‚‚‚O, 1.78 Å, see Table 2), which in turn are held together by a series of C-H‚‚‚I (H‚‚‚I, 3.35, 3.38 Å) and C-H‚ ‚‚O (H‚‚‚O, 2.55 Å) interactions (Table 2). The packing of the molecules is shown in Figure 4. However, the water molecules in the channels are arranged in a manner different from that of 2a. In the present case, the water molecules constituted a linear chain, while the molecules formed a corner-shared square network in 2a (compare Figures 4d and 3e). The linear chains of water molecules have lot of importance in biological systems and account for the properties of proteins,21 and since several boronic acids have been found to be bioactive reagents, the observed water channels in the crystal structure of 3a are of great significance for further studies. Indeed, boric acid, an inorganic equivalent of boronic acid, had been shown to form elegant water channels in its adduct with a polyimidazole tripod, which has been reported recently;22 this further supports the importance of the water channels in boronic acids. In our efforts to obtain an anhydrous form of 4-iodophenylboronic acid, crystallization reactions were carried out from different solvents. Thus, 3b crystals, obtained from CH3OH with a morphology different from that of 3a, examined under the optical microscope, have been characterized by single-crystal

Architecture of 4-Halophenylboronic Acids

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Figure 3. (a) Composition of the asymmetric unit contents in the hydrate of 4-bromophenylboronic acid (2a). (b) Interaction between the molecules that are held together through O-H‚‚‚O hydrogen bonds. (c) Molecular tapes observed in 2a. (d) Channel structure formed by the boronic acid molecules as host (view along the c-axis). (e) Arrangement of water molecules in the channels.

X-ray diffraction methods. Although the unit cell parameters obtained were considerably different from 3a, the structure determination revealed that it is identical to 3a in all aspects and furthermore is isostructural and isomorphic with 2a. However, structures 3a and 3b show a difference in the arrangement of water molecules as well as the dimension of the channel. In the channels of 3b, the water molecules exist in a linear chain mode, but they remain discrete without any interactions with the neighboring molecules. The distance between the adjacent water molecules is 4.93 Å (O‚‚‚O distance), while it is 2.18 and 2.76 Å in 3a (see Table 2). In the case of 3a, the dimension of the channel is 11 × 11 Å2 and in 3b it is 9 × 12 Å.2 Comparison of Crystal Structures of 1, 2, 2a, 3a, and 3b. It is apparent from the structural studies that halogen substitution did not affect the conformation of -B(OH)2 as both 1 and 2 adopted a syn-anti orientation, which was observed predominantly in the other boronic acids. In addition, the hydrogenbonding patterns formed by the -B(OH)2 moieties in both of the above cases are similar to the general patterns observed for this class of compounds. Nevertheless, in the hydrate structures 2a, 3a, and 3b, syn-syn and anti-anti conformations were preferred. Also, different types of interactions mediated by halogen atoms were observed, perhaps due to the size and electronic factors. The trend appears to be following the general features known for other related compounds possessing different

functional groups. For example, the -Cl atom being small and with high electronegativity shows a tendency to form C-H‚‚‚ Cl rather than Cl‚‚‚Cl interactions, whereas the -Br atom yields Br‚‚‚Br more readily than C-H‚‚‚Br. Thus, the absence of Cl‚ ‚‚Cl interactions in 1 and the appearance of Br‚‚‚Br is quite obvious, and it can be concluded that in the crystal structure of anhydrous 4-iodophenylboronic acid, the I‚‚‚I interactions may play a more significant role. Conclusions In conclusion, we have studied the solid-state structures of 4-chloro and 4-bromo derivatives of phenylboronic acid and hydrates of bromo and iodo derivatives. The general nature of intermolecular interactions formed by the -B(OH)2 moiety, and rationalization of different types of C-H‚‚‚X (X ) Cl, Br and I) in the boronic acid series has been demonstrated in a systematic manner. We believe that this is first of its kind of analysis of the halogen derivatives of boronic acids. Furthermore, two hydrate structures of 4-iodophenylboronic acid, which are differentiated by the arrangement of the guest species (water molecules) perhaps may lead to the further exploration of these type of forms, as such examples deviate from the other classes of polymorphssstructural, conformational, concomitant, configurational, etc.sappearing in the literature. We are of the opinion that this study further leads to the systematic investiga-

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Figure 4. Arrangements of molecules (view along the b-axis) of 4-iodophenylboronic acid in its water adduct 3a. Compare it with Figures 1b and 3b to appreciate the similarity. (b) Molecular tapes observed along the a-axis in the structures of 3a, formed due to the C-H‚‚‚I and C-H‚‚‚O interaction. (c) Channel structure in 3a along the crystallographic c-axis with water molecules in the channels. Interaction between the water molecules observed in channels 3a and 3b, respectively, is shown in panels (d) and (e).

tion of numerous halogen derivatives, such as di-, tri-, and polysubstituted boronic acids, and we are forwarding in those directions to explore and unveil the unusual properties of those compounds for applications in various disciplines viz., functional group interconversions in organic synthesis, biology, and materials science. Experimental Procedures Preparation of Single Crystals of 1, 2, 2a, 3a, and 3b. 4-Chloro-, 4-bromo-, and 4-iodophenylboronic acids were prepared following the standard procedures described in the literature.20 Single crystals of the corresponding compounds and the hydrates were prepared by crystallization of the compounds from an appropriate solvent. The crystals of 4-chloro- and 4-bromophenylboronic acids were obtained as pure forms (1 and 2) upon crystallization from water. However, the latter gave a hydrate form (2a) when the crystallization was carried out using CH3OH. 4-Iodophenylboronic acid gave hydrates only but in two different forms (3a and 3b). These crystals were obtained from acetone and CH3OH. Crystal Structure Determination. The single crystals thus obtained as described above were used for structure determination by X-ray diffraction methods. Good quality single crystals, chosen with the aid of a Polaroid optical microscope having a CCD camera device attachment, were glued to a glass fiber using an adhesive and mounted on the goniometer of the X-ray diffractometer equipped with APEX area detector. The intensity data were collected at 133 K, as boronic acids are known for instability upon exposure to the X-rays at room temperature. The obtained data were processed using SAINT software,23 and structure determination and refinement were carried out using SHELXTL suite of programs.23 All the non-hydrogen atoms were refined anisotropically, and hydrogen atoms were refined isotropically. The crystallographic details of the structures are given in Table 1. The

analysis of intermolecular interactions and calculation of hydrogen bond parameters were performed using PLATON software.24 The characteristics of the hydrogen bonds are given in Table 2. Supporting Information Available: Crystallographic information files (cif) of the compounds and refcodes from a CSD search for boronic acid. This material is available free of charge via the Internet at http:// pubs.acs.org.

References (1) (a) Lehn, J.-M. Supramolecular Chemistry: Concepts and PerspectiVes; VCH: New York, 1995. (b) Atwood, J. L.; Davies, J. E. D.; MacNicol, D. D.; Vogtle, F. In ComprehensiVe Supramolecular Chemistry; Pergamon, Oxford, UK, 1996; Vols. 1-11. (c) Jeffrey, G. A.; Saenger, W. Hydrogen Bonding in Biologcal Structures; Springer: Berlin, 1991. (d) Desiraju, G. R. Crystal Engineering: The Design of Organic Solids; Elsevier: Amsterdam, 1989. (e) MacDonald, J. C.; Whitesides, G. M. Chem. ReV. 1994, 94, 2383-2420. (2) (a) Kolotuchin, S. V.; Fenlon, E. E.; Wilson, S. R.; Loweth, C. J.; Zimmerman, S. C. Angew. Chem., Int. Ed. 1996, 34, 2654-2657. (b) Braga, D.; Grepioni, F. Angew. Chem., Int. Ed. 2004, 43, 40024011. (c) Almarsson, O.; Zaworotko, M. J. Chem. Commun. 2004, 10, 1889-1896. (d) Hofmann, D. W. M.; Kuleshova, L. N.; Antipin, M. Y. Cryst. Growth Des. 2004, 4, 1395-1402. (3) (a) Etter, M. C. Acc. Chem. Res. 1990, 23, 120-126. (b) Desiraju, G. R. Acc. Chem. Res. 1996, 29, 441-449. (c) Desiraju, G. R. Nature 2001, 412, 397-400. (d) Desiraju, G. R. Angew. Chem., Int. Ed. 1995, 34, 2311-2327. (4) (a) Bernstein, J.; Davis, R. E.; Shimoni, L.; Chang, N.-L. Angew. Chem., Int. Ed. 1995, 34, 1555-1573. (b) Biradha, K.; Mahata, G. Cryst. Growth Des. 2005, 5, 61-63. (c) Dunitz, J. D.; Gavezzotti, A. Angew. Chem., Int. Ed. 2005, 44, 1766-1787.

Architecture of 4-Halophenylboronic Acids (5) (a) Frisˇcic´, T.; Drab, D. M.; MacGillivray, L. R. Org. Lett. 2004, 6, 4647-4650. (b) MacGillivray, L. R.; Reid, J. L.; Ripmeester, J. A.; Papaefstathiou, G. S. Ind. Eng. Chem. Res. 2002, 41, 4494-4497. (c) Thalladi, V. R.; Goud, B. S.; Hoy, V. J.; Allen, F. H.; Howard, J. A. K.; Desiraju, G. R. Chem. Commun. 1996, 401-402. (6) (a) Price, S. L. CrystEngComm 2004, 6, 344-353. (b) Dunitz, J. D.; Gavezzotti, A. Angew. Chem., Int. Ed. 2005, 44, 1766-1787. (c) Dunitz, J. D. Chem. Commun. 2003, 9, 545-548. (d) Dunitz, J. D.; Gavezzotti, A. HelV. Chim. Acta 2002, 85, 3949-3964. (7) (a) Varughese, S.; Pedireddi, V. R. Tetrahedron Lett. 2005, 46, 24112415. (b) Arora, K. K.; Pedireddi, V. R. J. Org. Chem. 2003, 68, 9177-9185. (c) Pedireddi, V. R.; PrakashaReddy, J. Tetrahedron Lett. 2002, 43, 4927-4930. (d) Pedireddi, V. R. Cryst. Growth Des. 2001, 1, 383-385. (e) Chatterjee, S.; Pedireddi, V. R.; Ranganathan, A.; Rao, C. N. R. J. Mol. Struct. 2000, 520, 107-115. (8) (a) Prakashareddy, J.; Pedireddi, V. R. Tetrahedron 2004, 60, 88178827. (b) Arora, K. K.; Pedireddi, V. R. Tetrahedron 2004, 60, 919925. (c) Pedireddi, V. R.; Prakashareddy, J. Tetrahedron Lett. 2003, 44, 6679-6681. (d) Pedireddi, V. R.; Prakashareddy, J.; Arora, K. K. Tetrahedron Lett. 2003, 44, 4857-4860. (e) Ranganathan, A.; Pedireddi, V. R.; Rao, C. N. R. J. Am. Chem. Soc. 1999, 121, 17521753. (9) (a) Allen, F. H.; Kennard, O. Chem. Des. Automat. News 1993, 8, 31-37. (b) Rettig, S. J.; Trotter, J. Can. J. Chem. 1997, 55, 30713075. (c) Rodrı´guez-Cuamatzi, P.; Vargas-DIÄaz, G.; Maris, T.; Wuest, J. D.; Ho¨pfl, H. Acta Crystallogr. Sect. E 2004, E60, o1315-o1317. (d) Shull, B. K.; Spielvogel, D. E.; Gopalaswamy, R.; Sankar, S.; Boyle, P. D.; Head, G.; Devito, K. J. J. Chem. Soc., Perkin Trans. 2000, 2, 557-561. (e) Zarychta, B.; Zaleski, J.; Sporzyn˜ski, A.; Dabrowski, M.; Serwatowski, J. Acta Crystallogr. 2004, C60, o344o345. (10) (a) Bradley, D. C.; Harding, K. S.; Keefe, A. D.; Motevalli, M.; Zheng, D. H. J. Chem. Soc., Dalton Trans. 1996, 3931-3936. (b) Gainsford, G. J.; Meinhold, R. H.; Woolhouse, A. D. Acta Crystallogr. 1995, C51, 2694-2696. (c) Soundararajan, S.; Duesler, E. N.; Hageman, J. H. Acta Crystallogr. 1993, C49, 690-693. (d) Aakero¨y, C. B.; Desper, J.; Levin, B. CrystEngComm 2005, 7, 102-107. (e) Rodrı´guez-Cuamatzi, P.; Vargas-DIÄaz, G.; Ho¨pfl, H. Angew. Chem., Int. Ed. 2004, 43, 3041-3044. (f) Fournier, J. H.; Maris, T.; Wuest, J. D.; Guo, W.; Galoppini, E. J. Am. Chem. Soc. 2003, 125, 10021006. (g) Rodrı´guez-Cuamatzi, P.; Arillo-Flores, O. I.; BernalUruchurtu, M. I.; Ho¨pfl, H. Cryst. Growth Des. 2005, 5, 167-175. (11) Pedireddi, V. R.; SeethaLekshmi, N. Tetrahedron Lett. 2004, 45, 1903-1906. (12) (a) Miyaura, N.; Suzuki, A. Chem. ReV. 1995, 95, 2457-2483. (b) Suzuki, A. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds. Wiley-VCH: Weinheim, Germany, 1998. (c) Ahn, Y. H.; Chang, Y. T. J. Comb. Chem. 2004, 6, 293-296. (d) Arvela, R. K.; Leadbeater, N. E. Org. Lett. 2005, 7, 2101-2104. (e) Dvorak, C. A.; Rudolph, D. A.; Ma, S.; Carruthers, N. I. J. Org. Chem. 2005, 70, 4188-4190. (f) Miao, G.; Ye, P.; Yu, L.; Baldino, C. M. J. Org. Chem. 2005, 70, 2332-2334. (13) (a) Archer, S. J.; Camac, D. M.; Wu, Z. J.; Farrow, N. A.; Domaille, P. J.; Wasserman, Z. R.; Bukhtiyarova, M.; Rizzo, C.; Jagannathan, S.; Mersinger, L. J.; Kettner, C. A. Chem. Biol. 2002, 9, 79-92. (b) Kinder, D. H.; Frank, S. K.; Ames, M. M. J. Med. Chem. 1990, 33, 819-823. (c) Lebarbier, C.; Carreaux, F.; Carboni, B.; Boucher, J. L. Bioorg. Med. Chem. Lett. 1998, 8, 2573-2576. (d) Yang, W.; Gao, X.; Wang, B. Med. Res. ReV. 2003, 23, 346-368. (e) Fabre, B.; Taillebois, L. Chem. Commun. 2003, 2982-2983. (f) Friggeri, A.; Kobayashi, H.; Shinkai, S.; Reinhoudt, D. N. Angew. Chem., Int. Ed. Engl. 2001, 40, 4729-4731. (g) Koyama, T.; Terauchi, K. J. Chromatogr. B Biomed. Appl. 1996, 679, 31-40.

Crystal Growth & Design, Vol. 7, No. 10, 2007 1963 (14) (a) Ivanov, D.; Bachovchin, W. W.; Redfield, A. G. Biochemistry 2002, 41, 1587-1590. (b) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Nature 1995, 374, 345-347. (c) James, T. D.; Shinkai, S. Top. Curr. Chem. 2002, 218, 159-200. (d) Pargellis, C. A.; Campbell, S. J.; Pav, S.; Graham, E. T.; Pitner, T. P. J. Enzyme Inhib. 1997, 11, 151-169. (e) Priestley, E. S.; De, L. I.; Ghavimi, B.; Erickson-Viitanen, S.; Decicco, C. P. Bioorg. Med. Chem. Lett. 2002, 12, 3199-3202. (f) Saitoh, H.; Aungst, B. J. Pharm. Res. 1999, 16, 1786-1789. (g) Zhao, J.; Fyles, T. M.; James, T. D. Angew. Chem., Int. Ed. Engl. 2004, 43, 3461-3464. (15) Metrangolo, P.; Neukirch, H.; Pilati, T.; Resnati, G. Acc. Chem. Res. 2005, 38, 386-395. (16) (a) Pedireddi, V. R.; Reddy, D. S.; Goud, B. S.; Craig, D. C.; Rae, A. D.; Desiraju, G. R. J. Chem. Soc. Perkin Trans. 2 1994, 23532360. (b) Desiraju, G. R. in Organic Solid State Chemistry, ed. G. R. Desiraju, Elsevier, Amsterdam, 1987, pp. 519-546. (c) Schmidt, G. M. J. Pure Appl. Chem. 1971, 27, 647. (d) Lahav, M.; Schmidt, G. M. J. J. Chem. Soc. B 1967, 239. (17) (a) Metrangolo, P.; Resnati, G. Chem. Eur. J. 2001, 7, 2511-2519. (b) Sarma, J. A. R. P.; Desiraju, G. R. Acc. Chem. Res. 1986, 19, 222-228. (c) Caronna, T.; Liantonio, R.; Logothetis, T. A.; Metrangolo, P.; Pilati, T.; Resnati, G. J. Am. Chem. Soc. 2004, 126, 4500-4501. (d) Corradi, E.; Meille, S. V.; Messina, M. T.; Metrangolo, P.; Resnati, G. Angew. Chem., Int. Ed. Engl. 2000, 39, 1782-1786. (e) Goroff, N. S.; Curtis, S. M.; Webb, J. A.; Fowler, F. W.; Lauher, J. W. Org. Lett. 2005, 7, 1891-1893. (f) Ouvrard, C.; Le Questel, J. Y.; Berthelot, M.; Laurence, C. Acta Crystallogr. Sect. B 2003, 59, 512-526. (18) (a) Zvonkova, Z. V.; Gluskova, V. P. Kristallografiya (Russ.)(Crystallogr. Rep.), 1958, 3, 559-561. (b) Horton, P. N.; Hursthouse, M. B.; Beckett, M. A.; Rugen-Hankey, M. P. Acta Crystallogr. Sect. E 2004, E60, o2204-2206. (c) Bhuvanesh, N. S. P.; Reibenspies, J. H. Acta Crystallogr. Sect. E 2005, E61, o362-o364. (19) (a) Martin, R.; Gold, M.; Jones, J. B. Bioorg. Med. Chem. Lett. 1994, 4, 1229-1234. (b) Beesley, T.; Gascoyne, N.; Knott-Hunziker, V.; Petursson, S.; Waley, S. G.; Jaurin, B.; Gundstrom, T. Biochem. J 1983, 209, 229-233. (c) Crompton, I. E.; Cuthbert, B. K.; Lowe, G.; Waley, S. G. Biochem. J 1988, 251, 453-459. (20) (a) Breuer, S. W.; Thorpe, F. G. Tetrahedron Lett. 1974, 42, 37193720. (b) Kricka, L. J.; Cooper, M.; Ji, X. Anal. Biochem. 1996, 240, 119-125. (c) Bouillon, A.; Lancelot, J. C.; Collot, V.; Bovy, P. R.; Rault, S. Tetrahedron 2002, 58, 2885-2890. (d) Parry, P. R.; Wang, C.; Batsanov, A. S.; Bryce, M. R.; Tarbit, B. J. Org. Chem. 2002, 67, 7541-7543. (21) (a) Agre, P.; Bonhievers, M.; Borgnia, M. J. J. Biol. Chem. 1998, 273, 14659-14662. (b) Williams, K. A.; Nature, 2000, 403, 112115. (c) Zhang, P. J.; Toyoshima, C.; Yonekuri, K.; Green, N. M.; Stoks, D. L. Nature 1998, 392, 835-839. (22) Cheruzel, L. E.; Mashuta, M. S.; Buchanan, R. M. Chem. Commun. 2005, 2223-2225. (23) (a) Siemens, SMART-Version 5.611, Siemens Analytical X-ray Instruments Inc., Madison, WI, U.S.A., 1995. (b) Sheldrick, G. M. SADABS Siemens Area Detector Absorption Correction Program, University of Gottingen, Gottingen, Germany, 1994. (c) Sheldrick, G. M. SHELXTL-Version 5.10, Program for Crystal Structure Solution and Refinement, University of Gottingen, Gottingen, Germany. (24) Hydrogen bond calculations were carried out by using the HBOND NORM option of A. L. Spek, PLATON, Molecular Geometry Program, University of Utrecht, The Netherlands 1995.

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