Communication pubs.acs.org/crystal
Structural Diversity in the Complexes of Trimeric Perfluoro‑o‑phenylene Mercury with Tetrathia- and Tetramethyltetraselenafulvalene Published as part of the Crystal Growth & Design Mikhail Antipin Memorial virtual special issue Raúl Castañeda,† Andrey A. Yakovenko,‡ Sergiu Draguta,† Marina S. Fonari,†,§ Mikhail Yu. Antipin,†,∥ and Tatiana V. Timofeeva*,†,⊥ †
Department of Biology and Chemistry, New Mexico Highlands University, Las Vegas, New Mexico 87701, United States X-ray Science Division Argonne National Laboratory, 9700 South Cass Avenue, Building 401 MS-16, Argonne, Illinois 60439, United States § Institute of Applied Physics, Academy of Sciences of Moldova, Academy Str., 5 MD2028 Chisinau, Moldova ∥ A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., B-344, Moscow, 119991, Russia ⊥ ITMO University, St. Petersburg 197101, Russia ‡
S Supporting Information *
ABSTRACT: Five potential charge transfer complexes of trimeric perfluoro-o-phenylene mercury (I) with tetrathiafulvalene (TTF) and tetramethyltetraselenefulvalene (TMTSF) were grown from different solvent mixtures. The adducts (I)2· TTF (1) and I·TTF (2) were grown by slow evaporation from the 1:1 mixture of dichloromethane (CH2Cl2, DCM) and carbon disulfide (CS2). Use of the different 1:1 solvent mixtures of dichloromethane (CH2Cl2, DCM) and dichloroethane (C2H4Cl2, DCE) has led to the crystalline adducts I·TTF (3) and I·TTF·DCE (4). Adduct I.TMTSF (5) was grown by the interface crystallization on the border of two immiscible layers, ethyl acetate, and carbon disulfide. The cocrystals differ by the donor−acceptor ratio, molecular packing, and the solvent inclusion. The components in 1−5 form mixed donor−acceptor stacks. The stacks are stabilized by Hg···S and Hg···C short contacts, while the lateral interactions between stacks include F···F, CH···F, and S/Se···F short contacts.
A
used in the synthesis of other organometallic compounds like orthophenylene zinc.4 Complexation of electronegative molecules such as acetonitrile,5 dimethylformamide,6 and acetylacetone7 by the macrocycle I was reported. Since I possesses extremely strong electron acceptor properties primarily oxoand thiophilicity,8 this rationalizes its application as an acceptor component of CT materials. The examples of complexes between I and different planar molecules such as azulene,9 TTF,10 and carbazole,11 or nonplanar molecules such as corannulene12 and bycorannulenyl13 were reported. The complexes of I with TTF and TCNQ were first reported by Haneline and Gabbai.̈ 10 Having experience in the chemistry of this metallocycle14 and encouraged by that research, we aimed to reproduce the system I−TTF with an emphasis on possible different stoichiometry and polymorphic modifications in that system. The availability of a number of fluorine atoms in the
ctive investigations of charge-thansfer complexes were started in 1973 when the TTF (donor)−TCNQ (acceptor) charge-transfer (CT) complex was reported.1 Nowadays this area continues to attract attention covering organic salts with TTF or its derivatives in the form of neutral molecules or anions,2 along with some new acceptors. Trimeric perfluoro-ophenylene mercury (I) (Scheme 1) is a cyclic organometallic electron acceptor with three active sites. This planar molecule was first synthethized by Sartori et al. in 19683 and has been Scheme 1. Targeted Molecules with the Notations Used in This Study
Received: October 28, 2014 Revised: February 5, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/cg501594t Cryst. Growth Des. XXXX, XXX, XXX−XXX
Communication
Crystal Growth & Design
Figure 1. ADA arrangements in the stacks in 1 (a), 2 (b), 3 with two formula units (c), 4 (d), and 5 (e) showing Hg and S labels and 50% probability displacement ellipsoids. Dashed lines denote short contacts.
ment of the thermal and photostability of the materials.17 Furthemore, we compared the TTF complexes with its Secontaining analogue tetramethyltetraselenefulvalene (TMTSF), since the substitution of S in thiophene-comprising semiconductors with more polarizable heavy chalcogen atoms
molecule I should assist in the cocrystallization via meaningful F···F interactions,15 whose additional advantage is that they are predominantly realized in the form of planar association patterns thus governing the formation of extended planar arrays.16 Their contributions are reported impact into improveB
DOI: 10.1021/cg501594t Cryst. Growth Des. XXXX, XXX, XXX−XXX
Communication
Crystal Growth & Design
Figure 2. Fragments of crystal packing motifs in compounds 1 (a) along the (130) plane, 4 (b) along (303)̅ , and 5 (c) along the (111) plane sustained by interactions with participation of fluorine atoms.
resulted in the significant enchancement of mobility as it has been reported so far.18 Complex 1, including its crystal structure (CSD refcode: PAGLEP), was first reported by Haneline and Gabbai.̈ 10 Repeating the same procedure two CT polymorphs, 1 with a donor/acceptor ratio 1:2 identical to that reported earlier10 and
I·TTF(2) with a donor−acceptor ratio of 1:1, were found as major and minor components of the bulk crystalline material. Adducts 1 and 2 differ substantially in their crystal shape and color; 1 grows as orange needles, and 2 grows as brown prisms (see Figure 1S in the Supporting Information, SI). Until now we were unable to find an experimental procedure to obtain C
DOI: 10.1021/cg501594t Cryst. Growth Des. XXXX, XXX, XXX−XXX
Communication
Crystal Growth & Design
lateral interactions between stacks are most pronounced in the triclinic crystals 1, 4, and 5 where they include the interplay of F···F, CH···F, and S/Se···F short contacts (Figure 2) that combine the components from the adjacent stacks in the infinitive smoothen motifs with different degrees of corrugation. In 1 the components from the adjacent stacks are associated into planar layers extended parallel to the (130) plane (Figure 2a). Within the layer the self-association of molecules I via short F···F contacts occurs. The calculated F···F distances and C−F···F angles for the fluorine atoms depicted in Figure 2a are F(1)···F(11) = 2.777(5) Å, ∠C(2)F(1)F(11) = 127.5(4)°; F(1)···F(12) = 2.879(6) Å, ∠C(2)F(1)F(12) = 171.6(4)°; F(2)···F(10) = 2.875(5) Å, ∠C(3)F(2)F(10) = 172.7(4)°; F(7)···F(6)= 2.842(6) Å, ∠C(9)F(6)F(7) = 156.4(4)°. At least two of these contacts, F(1)···F(12) and F(2)···F(10) with the CFF angles close to 180° might be referred to the Type II in classification suggested by Ramasubbu et al.23 and considered as meaningful for stabilization of the crystal lattice. The TTF molecules are connected within this layer through the CH···F [H(21)···F(7) = 2.36(1) and H(20)···F(4) 2.41(1) Å] and S···F [ S(1)···F(5) = 3.178(5) and S(2)···F(5) = 3.189(5) Å] short contacts so that each TTF molecule is surrounded by four molecules of I. The layers stack along the b axis with the interlayer separation of 3.300 Å. It is appropriate to mention that I itself exhibits polymorphic diversity,24 and among its four currently known polymorph modifications (CSD refcodes: MOXMAN, MOXMAN01, MOXMAN02, MOXMAN03) only the monoclinic polymorph (MOXMAN01) that crystallizes in the space group C2/c packs in layers. Despite the DCE inclusion in the crystal lattice of pseudopolymorph 4 with the 1:1 donor/acceptor ratio, the triclinic crystal system is preserved that is accompanied by the increase in the unit cell dimensions and the unit cell volume compared with 1. The packing motifs in 4 somewhat differ from 1 due to the DCE inclusion that disrupts some of the intralayer short contacts. Nevertheless, in the infinite planar motifs extended parallel to the bc plane and shown in Figure 2b the acceptor molecules I are held together via two short F···F contacts, F(10)···F(6) = 2.80(1) Å, ∠C(15)F(10)F(6) = 155(1)° and F(5)···F(11) = 2.87(1) Å, ∠C(8)F(5)F(11) = 160(1)° giving rise to the homomolecular tapes, while donor− acceptor interactions cause S···F contacts S(3)···F(2) = 3.17(2) Å, S(3)···F(3) = 3.22(1) Å, and S(1)···F(8) = 3.180(9) Å, and short CH···F contacts that include H(26a)···F(4) = 2.21(3); H(26b)···F(12) = 2.45(3); H(24)···F(6) = 2.51(2), and H(19)···F(8) = 2.49(2) Å. The layers stack along the crystallographic a direction, the separation between the layers being 3.351 Å. No meaningful homomeric contacts have been found in 5, while the methyl groups of the TMTSF molecules provide the reliable H-donors for the CH···F interactions for fluorine atoms marked at Figure 2c with the CH···F distances in the range of 2.43(1)−2.61(1) Å. Thermogravimetic (TGA) and differential scanning calorimetry (DCS) profiles for complexes 1 and 5 are shown in Figure 2S in SI. TTF has a lower thermal stability with respect to its organoselenium counterpart TMTSF; it decomposes at 175.2 °C, while TMTSF decomposes at 237.5 °C. In complex 1 it was observed that the decomposition of TTF occurred first at 269.6 °C, and the decomposition of macrocycle I occurred at 308.0 °C; thus TTF molecule was stabilized by macrocycle I. On the other hand complex 5 with TMTSF decomposes as a whole at
complex 2 as a major component. Since it is known that different solvents can produce different polymorphs,19 several other conditions to obtain adducts of I with TTF were studied. Crystallization of equimolar amounts of I and TTF from a 1:1 mixture of DCE and diethyl ether gave no single crystals; crystallization from carbon disulfide gave the reported complex 1.10 Use of different 1:1 solvent mixtures, dichloromethane (CH2Cl2, DCM) and dichloroethane (C2H4Cl2, DCE), has led to the new crystalline polymorph I·TTF (3), solvatomorph I· TTF·DCE (4), and I·TTF observed before as adduct 2. It should be mentioned that only by X-ray single crystal analysis has the identity of 3 and 4 been proven. Crystals of I·TMTSF (5) grow very fast from different solvents such as DCM, DCE, ethyl acetate, carbon disulfide, acetylacetone, and the 1:1 mixture of DCM/CS2 giving very small crystals not suitable for X-ray diffraction. Complex 5 for X-ray study was grown by the interface crystallization on the border of two immiscible layers, ethyl acetate, and carbon disulfide (the details of the synthetic procedures for the five compounds are given in Supporting Information (SI)). X-ray analysis revealed that complexes differ by the donor− acceptor ratio, being 1:2 in 1, and 1:1 in 2−5, and the solvent inclusion in 4. Adducts 1, 4, and 5 crystallize in the triclinic space group P1̅, while adducts 2 and 3 crystallize in the monoclinic P21/c space group with the unit cell for 3 approximately twice larger than for 2 (Table 1S in SI). Only in complex 1 do the TTF molecules reside on inversion centers, and in the other compounds the components occupy general positions. In all materials the donor and acceptor components form stacks. The ADA (A − for acceptor, D − for donor) fragments of stacks for 1−5 are shown in Figure 1. The different molar ratio in 1 against 2−5 defines two different modes of the components’ alternation in the stacks: in 1 this is the ADAADAA sequence, while in 2−5 this is the ADADAD sequence. Everywhere further only the contacts Hg···S, Hg···C, F···F, CH···F, and S/Se···F shorter than the sum of van der Waals radii for the corresponding atoms (RHg = 1.73−2 Å, RS = 1.8−2.03 Å, RC = 1.7 Å, RF = 1.47 Å)20,21 are discussed unless otherwise specified. The mutual arrangement of the donor and acceptor molecules in stacks is asymmetric as it is dictated by the necessary compromise between the D2h and D3h symmetries of donor and acceptor, and the tendency to maximize the possible Hg···S contacts since the highly thiophilic nature of Hg(II) is well-known.22 The donor−acceptor ratio 1:1 makes possible interactions of one molecule of I with two donor molecules in 2−5. The shortest Hg···S and Hg···C contacts are shown in Figure 1 by dashed lines and are summarized in Table 2S in SI. Usually only two of three Hg atoms are involved into Hg···S contacts in the range of 3.281(7)−3.724(3) Å. In 5 seven Hg···Se contacts have been observed in the range of 3.351(4)−3.777(4) Å with the shortest one of 3.351(4) Å between the Hg(1) and Se(2) atoms located strictly one above the other. The molecules in stacks are arranged approximately in the parallel planes with the dihedral angles between the donor and acceptor mean planes of 6.76° in 1, 7.40° in 2, 2.54° and 7.85° in 3, 4.03° in 4, and 2.84° in 5. The TTF molecule, that is ideally planar in 1, adopts a concave shape in 3 and 4 (the dihedral angles between the five-membered rings in TTF are equal to 3.14° in 2, 7.97 and 16.58° in 3, and 11.58° in 4). Crystal packing motifs belong to the cofacial type of stacks aggregation in the triclinic crystals 1, 4, and 5, and the herringbone type for the monoclinic crystals 2 and 3. The D
DOI: 10.1021/cg501594t Cryst. Growth Des. XXXX, XXX, XXX−XXX
Communication
Crystal Growth & Design 249.2 °C suggesting stronger interactions of macrocycle I with TMTSF than with TTF. In summary, several solvent systems were explored for growing cocrystals of I with two electron donor molecules TTF and TMTSF. As a result only one type of cocrystal was obtained for the I−TMTSF system. On the contrary four complexes of I with TTF, presenting examples of polymorphism, solvatomorphism, and complexes with different stoichiometry, were obtained. That demonstrates that for TTF as well as for I structural deversity is quite common and might be used for tuning the electronic properties of TTF and trimeric perfluoro-o-phenylene mercury-based materials. It should be emphasized that all these materials form stacks with significant Hg···S(Se) nonbonded interactions and planar donor−acceptor fragments which are mostly identified by nonbonded interactions with the F atoms. These results are in line with the observations done before that demonstrated that TTF can produce CT materials with a different donor/acceptor ratio with iodine.25 Polymorphs are also common for TTF adducts. For instance, chloroanyl produces four CT polymorph adducts with TTF from different solvent systems.26 Recently mixed and/or segregated donor/acceptor stacks were observed in CT materials;27 nowadays synthesis of CT materials that differ from this traditional packing is attracting attention in the search for new properties such as ferroelectricity that these materials can have.28 In addition some nontraditional packing modes can produce higher ionic character as was found, for instance, in black crystalline adducts of chloranyl with TTF.26 We suggest that TTF complex 2 that has a dark brown color could be the one with the higher degree of charge transfer among others studied in this project.
■
(5) Yang, X.; Zheng, Z.; Knobler, C. B.; Hawthorne, M. F. J. Am. Chem. Soc. 1993, 115, 193−195. (6) Tsunoda, M.; Gabbaï, F. P. J. Am. Chem. Soc. 2003, 125, 10492− 10493. (7) Tikhonova, I. A.; Yakovenko, A. A.; Tugashov, K. I.; Dolgushin, F. M.; Novikov, V. V.; Antipin, M. Y.; Shur, V. B. Organometallics 2006, 25, 6155−6158. (8) (a) Tikhonova, I. A.; Dolgushin, F. M.; Tugashov, K. I.; Petrovskii, P. V.; Furin, G. G.; Shur, V. B. J. Organomet. Chem. 2002, 654, 123−131. (b) Tikhonova, I. A.; Tugashov, K. I.; Dolgushin, F. M.; Petrovskii, P. V.; Shur, V. B. Organometallics 2007, 26, 5193−5198. (9) Tikhonova, I. A.; Tugashov, K. I.; Dolgushin, F. M.; Yakovenko, A. A.; Strunin, B. N.; Petrovskii, P. V.; Furin, G. G.; Shur, V. B. Inorg. Chim. Acta 2006, 359, 2728−2735. (10) Haneline, M. R.; Gabbaï, F. P. C.R. Acad. Sci., Ser. IIc: Chim. 2004, 7, 871−876. (11) Burress, C. N.; Gabbaï, F. P. Heteroat. Chem. 2007, 18, 195− 201. (12) Filatov, A. S.; Jackson, E. A.; Scott, L. T.; Petrukhina, M. A. Angew. Chem., Int. Ed. 2009, 48, 8473−8476. (13) Filatov, A. S.; Greene, A. K.; Jackson, E. A.; Scott, L. T.; Petrukhina, M. A. J. Organomet. Chem. 2011, 696, 2877−2881. (14) (a) Tikhonova, I. A.; Yakovenko, A. A.; Tugashov, K. I.; Dolgushin, F. M.; Petrovskii, P. V.; Minacheva, M. K.; Strunin, B. N.; Shur, V. B. Russ. Chem. Bull. 2013, 62, 710−715. (b) Castañeda, R.; Draguta, S.; Yakovenko, A.; Fonari, M.; Timofeeva, T. Acta Crystallogr., Sect. E 2014, 70, m164−m165. (15) (a) Reichenbacher, K.; Suss, H. I.; Hulliger, J. Chem. Soc. Rev. 2005, 34, 22−30. (b) Chopra, D.; Row, T. N. G. CrystEngComm 2011, 13, 2175−2186. (c) Priimagi, A.; Cavallo, G.; Metrangolo, P.; Resnati, G. Acc. Chem. Res. 2013, 46, 2686−2695. (16) Awwadi, F. F.; Willett, R. D.; Peterson, K. A.; Twamley, B. J. Phys. Chem. A 2007, 111, 2319−2328. (17) Mas-Torrent, M.; Rovira, C. Chem. Rev. 2011, 111, 4833−4856. (18) Yamamoto, T.; Takimiya, K. J. Am. Chem. Soc. 2007, 129, 2224− 2225. (19) Bernstein, J. Polymorphism in Molecular Crystals; Clarendon Press/International Union of Crystallography: Gloucestershire, U.K., 2002. (20) Canty, A. J.; Deacon, G. B. Inorg. Chim. Acta 1980, 45, L225− L227. (21) Bondi, A. J. Phys. Chem. 1964, 68, 441−451. (22) Huang, W.; Zhu, X.; Wua, D.; He, C.; Hu, X.; Duan, C. Dalton Trans. 2009, 10457−10465. (23) Ramasubbu, N.; Parthasarathy, R.; Murray-Rust, P. J. Am. Chem. Soc. 1986, 108, 4308−4314. (24) Haneline, M. R.; Gabbai, F. P. Z. Naturforsch., B: Chem. Sci. 2004, 59, 1483−1487. (25) Lebedev, V.; Laukhina, E.; Moreno-Calvo, E.; Rovira, C.; Laukhin, V.; Ivanov, I.; Dolotov, S. M.; Traven, V. F.; Chernyshev, V. V.; Veciana, J. J. Mater. Chem. 2014, 2, 139−146. (26) Lapidus, S. H.; Naik, A.; Wixtrom, A.; Massa, N. E.; Ta Phuoc, V.; del Campo, L.; Lebègue, S.; Á ngyán, J. G.; Abdel-Fattah, T.; Pagola, S. Cryst. Growth Des. 2013, 14, 91−100. (27) Goetz, K. P.; Vermeulen, D.; Payne, M. E.; Kloc, C.; McNeil, L. E.; Jurchescu, O. D. J. Mater. Chem. 2014, 2, 3065−3076. (28) Chen, S.; Zeng, X. C. J. Am. Chem. Soc. 2014, 136, 6428−6436.
ASSOCIATED CONTENT
S Supporting Information *
Synthetic procedures, additional figures, tables with the selected crystallographic data and H-bonds, as well as the X-ray crystallographic files in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS The authors are grateful for NSF support via DMR-0934212 (PREM) and IIA-130134.
■
REFERENCES
(1) Anderson, P. W.; Lee, P. A.; Saitoh, M. Solid State Commun. 1973, 13, 595−598. (2) (a) Murata, T.; Morita, Y.; Yakiyama, Y.; Fukui, K.; Yamochi, H.; Saito, G.; Nakasuji, K. J. Am. Chem. Soc. 2007, 129, 10837−10846. (b) Kurmoo, M.; Graham, A. W.; Day, P.; Coles, S. J.; Hursthouse, M. B.; Caulfield, J. L.; Singleton, J.; Pratt, F. L.; Hayes, W. J. Am. Chem. Soc. 1995, 117, 12209−12217. (c) Huang, Y.-D.; Huo, P.; Shao, M.-Y.; Yin, J.-X.; Shen, W.-C.; Zhu, Q.-Y.; Dai, J. Inorg. Chem. 2014, 53, 3480−3487. (3) Sartori, P.; Golloch, A. Chem. Ber. 1968, 101, 2004−2009. (4) Goedheijt, M. S.; Nijbacker, T.; Akkerman, O. S.; Bickelhaupt, F.; Veldman, N.; Spek, A. L. Angew. Chem., Int. Ed. 1996, 35, 1550−1552. E
DOI: 10.1021/cg501594t Cryst. Growth Des. XXXX, XXX, XXX−XXX
