CRYSTAL GROWTH & DESIGN
Supramolecular Solid-State Interactions between Helicene-like Terpyridinium Cation and Tris(tetrachloro-benzenediolato)phosphate(V) (TRISPHAT) Anion
2006 VOL. 6, NO. 6 1493-1496
Katell Se´ne´chal-David,† Loı¨c Toupet,‡ Olivier Maury,*,†,§ and Hubert Le Bozec*,† Laboratoire Sciences Chimiques, UMR 6226 CNRS-UniVersite´ de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France, Groupe de la Matie` re Condense´ e et Mate´ riau, UniVersite´ Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France, and Laboratoire de Chimie, UMR 5182 ENS-Lyon, 46 Alle´ e d’Italie, F-69364 Lyon Cedex 07, France ReceiVed March 17, 2006; ReVised Manuscript ReceiVed April 6, 2006
ABSTRACT: This article describes the supramolecular solid-state interactions between the racemic helicene-like terpyridium cation and the propeller-like tris(tetrachloro-benzenediolato)phosphate(V) (TRISPHAT) anion and gives valuable information concerning the different weak interactions types involving the TRISPHAT anion. Introduction The octahedral anion tris(tetrachloro-benzenediolato)phosphate(V) known as TRISPHAT, first described by Lacour in 1997,1 presents a helicoidal axis of chirality and can be prepared on a large scale under pure enantiomeric forms (Λ and ∆).2 This D3-symmetric anion has been widely used as an efficient NMR chiral shift reagent,3 as a chiral inducer onto labile cations,4 and for its ion-pair-mediated resolution properties.5,6 As a racemate, we have used this anion to strongly increase the solubility of cationic tris(bipyridyl) metal complexes, allowing the preparation and solution nonlinear optical studies of metallopolymers and metallo-dendrimers.7 By contrast, a limited number of supramolecular solid-state assemblies featuring the TRISPHAT anion have been described. Two examples of crystal structures between organometallic or metallo-organic cations and enantiopure TRISPHAT mainly interacting via π-π stacking have been recently reported.8,9 It is also interesting to note that the cocrystallization of TRISPHAT with D3-symmetric crystal violet gave a structure where no 3-fold embrace between anion and cation could be observed,10 whereas the association of a ruthenocene-like complex with TRISPHAT led to the formation of the first solid-state 1D supramolecular chains.11 In this article, we report the second example of such a supramolecular interaction between racemic TRISPHAT and a terpyridinium derivative. Results and Discussion
Figure 1. Two diastereoisomeric forms of L. Table 1. Crystal Data and Refinements Parameters formula M, g crystal size, mm3 color crystal system space group a, Å b, Å c, Å β, deg V, Å3 Z λ (Mo KR), Å µ, cm-1 F(000) T, K Dc, g‚cm-3 θ range, deg hkl ranges variables reflns measured reflns [I > 2σ(I)] R1 [I > 2σ(I)]/R1 (all data) wR2 [I > 2σ(I)]/wR2 (all data)
C43H44N4‚PO6C18Cl12‚2C2H5OH 1478.6 0.42 × 0.40 × 0.1 red monoclinic P21/c 11.0250(1) 25.8624(4) 24.5040(4) 99.042(1) 6900.1(2) 4 0.710 73 5.60 3028 293 1.463 1.57-26.74 0 < h < 13; 0 < k < 32; -31 < l < 31 779 14 454 8800 0.084/0.143 0.221/0.257
During the course of our studies aiming at the design of lanthanide complexes for nonlinear optical applications,12 we have prepared a dibutylaminophenyl-functionalized bis-annelated terpyridyl ligand, L (Figure 1). Depending of the relative conformation of the cyclohexyl fragments, this terpyridine derivative can exist as a pair of diastereoisomers, d,l and meso, having C2 and Cs symmetry, respectively.13 However, their too rapid interconversion in solution enables us to evidence this equilibrium by low temperature 1H NMR.13 Since the d,l isomer
presents a helicene-like structure (with Λ or ∆ enantiomers, Figure 2), we sought to associate the corresponding protonated terpyridinium cation with racemic TRISPHAT to displace the d,l T meso equilibrium toward the formation of the d,l isomer.14
* E-mail:
[email protected]. † Laboratoire Sciences Chimiques, UMR 6226 CNRS-Universite ´ de Rennes 1. ‡ Groupe de la Matie ` re Condense´e et Mate´riau, Universite´ Rennes 1. § UMR 5182 ENS-Lyon.
The pale yellow terpyridine ligand reacted instantaneously in dichloromethane with [HNBu3][TRISPHAT] yielding a violet solid (Scheme 1), which was fully characterized by 1H and 31P NMR spectroscopy and elemental analysis. The 1H NMR did not exhibit significant differences as compared to the unproto-
10.1021/cg060147n CCC: $33.50 © 2006 American Chemical Society Published on Web 05/10/2006
1494 Crystal Growth & Design, Vol. 6, No. 6, 2006
Se´ne´chal-David et al.
Figure 2. CPK representation of both Λ and ∆ enantiomers of the terpyridinium cation.
Scheme 1.
nated ligand (∆δ < 0.2 ppm) even at low temperature indicating a very weak cation-anion interaction in dichloromethane solution. By slow evaporation of an ethanolic solution of [LH][TRISPHAT], violet crystals suitable for X-ray diffraction analysis could be obtained. The salt crystallizes in a centrosymmetric space group as an ethanol solvate of general formula [LH(EtOH)][TRISPHAT]‚EtOH. Crystal data and refinement parameters are summerized in Table 1, and bond lengths and angles are described in Supporting Information. Interestingly, each terpyridinium cation displays exclusively the helicene-like conformation, which favors the interaction with the propellerlike anion. Both Λ,∆ isomers of the terpyridinium (Figure 2) and TRISPHAT are present in the elementary unit cell. The elemental molecular unit consists of a fully dissociated ion pair (Figure 3). The TRISPHAT anion exhibits a quasi-perfect
Figure 3. ORTEP drawing of the cation. The TRISPHAT anion and interstitial solvent molecules have been omitted for clarity.
Protonation of L
octahedral structure with the largest deviation from octahedral angles being 3.2° at the phosphorus atoms and average P-O distances of ca. 1.720 Å, in agreement with literature data.1 The terpyridinium cation depicted in Figure 3 is a ∆ isomer; it is
Figure 4. Crystallographic packing along the c axis to illustrate the polymeric chains: TRISPHAT and terpyridinium featuring the same handedness are colored in yellow and red (Λ isomers) and in sky blue and blue (∆ isomers), respectively.
Supramolecular Solid-State Interactions
Figure 5. Detail of the intermolecular interactions. TRISPHAT is colored in yellow with chlorine atoms in red; terpyridinium is colored in gray. Only the hydogen atoms of the terpyridinium involved in the packing interactions are represented in black.
stabilized by two hydrogen bonds with one ethanol molecule, namely, N2-H2-O7 and N3-H3-O7. The terpyridine adopts a forced cisoid conformation due to the annelation with dihedral angles between the two vicinal pyridinic rings of 11.5° and 15.3°. It is also interesting to note that the dialkylaminophenyl group forms a dihedral angle with the central pyridinic ring of 69.7° due to sterical repulsion between ortho-aromatic protons and aliphatic CH2 protons of the dimethylene bridge.15 The crystal packing (Figure 4) consists of polymeric chains along the c crystallographic axis built from alternation of the terpyridinium cation and the TRISPHAT anion with a Λ,Λ,∆,∆ isomer sequence. This sequence induces two different types of intrachain interactions between neighbors, namely, the homochiral and heterochiral ones, that are interactions between anions and cations featuring similar and opposite handedness, respectively. The heterochiral interactions are due to π-π stacking (d ) 3.4 Å) between the tetrachlorobenzene ring of TRISPHAT and the phenyl of the distal quinoline moieties of the terpyridinium, acting as π-acceptor and -donor, respectively (Figure 5). On the other hand, the homochiral interactions are ensured by strong CH-π hydrogen bonds between aromatic protons of the dialkylaminophenyl group and the catechol ring (d ) 2.8 Å)16 and also by additional CH-Cl hydrogen bonds.10 Finally, the interchain interactions result from π-π stacking between two pyridinic rings of two vicinal terpyridinium derivatives, with a plane to plane distance of 3.5 Å. Conclusions This article described the supramolecular solid-state interactions between the racemic helicene-like terpyridium cation and the propeller-like TRISPHAT anion. The crystal structure exhibits a complex packing ensured by CH-Cl, CH-π, and π-π stacking interactions between vicinal anion and cation and gives valuable information about the different weak interaction types involving the TRISPHAT anion. Experimental Section [LH][TRISPHAT]. To a dichloromethane solution of terpyridine was slowly added 1 equiv of [HNBu3][TRISPHAT] at room temperature. The initially yellow solution turned rapidly deep red and was stirred at room temperature for 2 h. The solvent was then removed under vacuum; the resulting solid was dissolved in the minimum amount of dichloromethane and precipitated upon addition of pentane. After filtration, the red solid was dried under vacuum. Crystallization in ethanol afforded red needles suitable for X-ray diffraction analysis. 1H NMR (CD2Cl2): δ ) 8.4 (d, J ) 8.4 Hz, 2H, H8′), 8.2 (d, J ) 8.4 Hz,
Crystal Growth & Design, Vol. 6, No. 6, 2006 1495 2H, H11′), 7.9 (ddd, 2H, H9′), 7.8 (ddd, 2H, H10′), 7.1 (d, J ) 8.8 Hz, 2H, H8), 6.8 (d, J ) 8.8 Hz, 2H, H9), 3.4 (t, J ) 7.6 Hz, 4H, H11), 3.3 (m, 4H, H16), 3.1 (m, 4H, H15), 2.8 (s, 6H, H7′), 1.7 (m, 4H, H12), 1.4 (m, 4H, H13), 1.0 (t, J ) 7.3 Hz, 6H, H14). 31P NMR (CD2Cl2): δ ) -81.0. UV-visible (CH2Cl2): λmax ) 516 nm (7400) λ ) 407 nm (22 400). Elemental analysis calcd for C61H45N4O6PCl12‚CH2Cl2 (found): wt % C 50.61 (50.77), wt % H 3.22 (3.64), wt % N 3.81 (3.72). X-ray Crystal Structure. The crystal (0.42 × 0.40 × 0.12 mm3) was studied on a NONIUS Kappa CCD with graphite monochromatized Mo KR radiation at 293 K. The data collection17 (Nonius, 1999) (2θmax ) 60°, 295 frames via 1.1° ω rotation and 55 s per frame) gives 70 851 reflections. The data reduction with Denzo and Scalepack18 leads to 14 454 independent reflections from which 8800 with I > 2.0σ(I). The structure was solved with SIR-2002,19 which reveals the non-hydrogen atoms of the structure. After anisotropic refinement, many hydrogen atoms may be found with a Fourier difference map. The whole structure was refined with SHELXH20 by the full-matrix least-squares techniques. The structure consists of one anion, one cation, one ethanol molecule, and two half ethanol molecules. The large absolute value of parameter shift to “su” ratio (4.2) is due to the large motion of the n-butyl groups. Crystallographic data for the structural analysis has been deposited with the Cambridge Crystallographic Data Centre, CCDC 296477. Supporting Information Available: Crystallographic data in CIF format. This material is available free of charge via the Internet at http:// pubs.acs.org.
References (1) Lacour, J.; Ginglinger, C.; Grivet, C.; Bernardinelli, G. Angew. Chem., Int. Ed. Engl. 1997, 36, 608-610. (2) Faverger, F.; Goujon-Ginglinger, C.; Monchaud, D.; Lacour, J. J. Org. Chem. 2004, 69, 8521-8524. (3) For selected examples, see: (a) Lacour, J.; Ginglinger, C.; Faverger, F.; Torche-Haldimann, S. Chem. Commun. 1997, 2285-2286. (b) Ratni, H.; Jodry, J. J.; Lacour, J.; Kundig, E. P. Organometallics 2000, 19, 3997-3999. (c) Planas, J. G.; Prim, D.; Rose, E.; RoseMunch, F.; Monchaud, D.; Lacour, J. Organometallics 2001, 20, 4107-4110. (d) Bruylants, G.; Bresson, C.; Boisdenghien, A.; Pierard, F.; Kirsch-De Mesmaeker, A.; Lacour, J.; Bartik, K. New J. Chem. 2003, 27, 748-751. (4) (a) Monchaud, D.; Jodry, J. J.; Pomeranc, D.; Heitz, V.; Chambron, J.-C.; Sauvage, J.-P.; Lacour, J. Angew. Chem., Int. Ed. 2002, 41, 2317-2318. (b) Jodry, J. J.; Frantz, R.; Lacour, J. Inorg. Chem. 2004, 43, 3329-3331. (5) (a) Lacour, J.; Torche-Haldimann, S.; Jodry, J. J.; Ginglinger, C.; Faverger, F. Chem. Commun. 1998, 1733-1734. (b) Jodry, J. J.; Lacour, J. Chem.sEur. J. 2000, 6, 4297-4304. (6) For a recent review, see: Lacour, J.; Hebbe-Viton, V. Chem. Soc. ReV. 2003, 32, 373-382 and references therein. (7) (a) Le Bozec, H.; Le Bouder, T.; Maury, O.; Bondon, A.; Zyss, J.; Ledoux, I. AdV. Mater. 2001, 13, 1677-1681. (b) Le Bouder, T.; Maury, O.; Le Bozec, H.; Bondon, A.; Costuas, K.; Amouyal, E.; Zyss, J.; Ledoux, I. J. Am. Chem. Soc. 2003, 125, 12884-12899. (c) Maury, O.; Le Bozec, H. Acc. Chem. Res. 2005, 39, 691-704. (8) Chavarot, M.; Me´nage, S.; Hamelin, O.; Charnay, F.; Pecaut, J.; Fontecave, M. Inorg. Chem. 2003, 42, 4810-4816. (9) Mimassi, L.; Guyard-Duhayon, C.; Rager, M. N.; Amouri, H. Inorg. Chem. 2004, 43, 6644-6649. (10) Lacour, J.; Bernardinelli, G.; Russell, V.; Dance, I. CrystEngComm 2002, 4, 165-170. (11) Amouri, H.; Caspar, R.; Gruselle, M.; Guyard-Duhayon, C.; Boubakeur, K.; Lev, D. A.; Collins, L. S. B.; Grotjahn, D. B. Organometallics 2004, 23, 4338-4341. (12) (a) Se´ne´chal, K.; Toupet, L.; Ledoux, I.; Zyss, J.; Le Bozec, H.; Maury, O. Chem. Commun. 2004, 2180-2181. (b) Tancrez, N.; Feuvrie, C.; Ledoux, I.; Zyss, J.; Toupet, L.; Le Bozec, H.; Maury, O. J. Am. Chem. Soc. 2005, 127, 13474-13475. (13) Similar equilibrium has already been evidenced: Thummel, R. P.; Jahng, Y. J. Org. Chem. 1985, 50, 2407-2412. (14) Maury, O.; Lacour, J.; Le Bozec H. Eur. J. Inorg. Chem. 2001, 201204 (15) (a) Keuper, R.; Risch, N.; Flo¨rke, U.; Haupt, H.-J. Liebigs Ann. 1996, 705-715. (b) Sielemann, D.; Winter, A.; Flo¨rke, U.; Risch, N. Org. Biomol. Chem. 2004, 2, 863-868.
1496 Crystal Growth & Design, Vol. 6, No. 6, 2006 (16) For a review on CH-π interactions, see: Nishio, M. CrystEngComm 2004, 6, 130-158. (17) Nonius, B.V. KappaCCD Software; Delft, The Netherlands, 1999. (18) Otwinowski, Z.; Minor, W. Processing of X-ray Diffraction Data Collected in Oscillation Mode. In Macromolecular Crystallography. Part A; Carter, C. W., Sweet, R. M., Eds.; Methods in Enzymology, Vol. 276; Academic Press: London, 1997; pp 307-326.
Se´ne´chal-David et al. (19) Burla, M. C.; Camalli, M.; Carrozzini, B.; Cascarano, G.; Giacovazzo, C.; Polidori, G.; Spagna, R. Acta Crystallogr., Sect. A 2000, 56, 451457. (20) Sheldrick, G. M. SHELX97. Program for the Refinement of Crystal Structures; University of Go¨ttingen: Germany, 1997.
CG060147N
