Inorg. Chem. 2000, 39, 5383-5389 5383 Heteroatomic Deltahedral Clusters of Main-Group Elements: Synthesis and Structure of 3- 2- 2- the Zintl Ions [In4Bi5] , [InBi3] , and [GaBi3] Li Xu and Slavi C. Sevov* Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 ReceiVed August 11, 2000 Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, 3- indium or gallium and bismuth. Nine-atom clusters [In4Bi5] are characterized in two different compounds, (Na-crypt)3[In4Bi5](4, P21/n, a ) 23.572(6) Å, b ) 15.042(4) Å, c ) 24.071(4) Å, â ) 106.00(3)°, Z ) 4) and (K-crypt)6[In4Bi5][In4Bi5]‚1.5en‚0.5tol (5, P21/c, a ) 28.532(2) Å, b ) 23.707(2) Å, c ) 28.021(2) Å, â ) 2- 2- 93.274(4)°, Z ) 4). Tetrahedra of [InBi3] or [GaBi3] are found in (K-crypt)2[InBi3]‚en (1, P21, a ) 12.347(4) Å, b ) 20.884(4) Å, c ) 12.619(7) Å, â ) 119.02(4)°, Z ) 2) and in the isostructural (Rb-crypt)2[InBi3]‚en (2, a ) 12.403(8) Å, b ) 20.99(1) Å, c ) 12.617(9) Å, â ) 118.83(4)°) and (K-crypt)2[GaBi3]‚en (3, a ) 12.324(5) Å, b ) 20.890(8) Å, c ) 12.629(5) Å, â ) 118.91(3)°). All compounds are crystallized from ethylenediamine/ crypt solutions of precursors with nominal composition “A5E2Bi4” where A ) Na, K, or Rb and E ) Ga or In. The cluster in 4 is a well-ordered monocapped square antiprism with the four indium atoms occupying the five- 3- bonded positions. Compound 5 contains two independent [In4Bi5] clusters; one is the same as the cluster in 4, while the other is a tricapped trigonal prism with two elongated prismatic edges. All compounds are EPR-silent and therefore diamagnetic. Introduction solid-state precursors.8-30 Until recently these precursors were thought to be alloys without structural features and definitely Zintl ions made from solutions have been known for more without clusters. Only recently it was discovered that some of than a century, since 1891 when Johannis reported the first the cluster ions found in solutions actually exist in the precursor 1 reduction of lead by sodium in liquid ammonia. Studies carried solids as well.31-35 They are characterized in the Zintl (valence) out in the following 40 years suggested that the green sodium- + lead solution contained polyanions of nine lead atoms, i.e., 4Na V + 4- 2,3 (8) Corbett, J. D. Chem. Re . 1985, 85, 383. [Pb9] . During that time anions of other groups such as (9) Corbett, J. D. Struct. Bonding 1977, 87, 157. 3- 2- 3 Sb7 and Te4 were also proposed. More systematic studies (10) Corbett, J. D Angew. Chem., Int. Ed. 2000, 39, 670. by E. Zintl in the 1930s suggested even more polyanions such (11) Fa¨ssler, T. F.; Schutz, U. Inorg. Chem. 1999, 38, 1866. 4- 3- 3- 2- (12) Campbell, J.; Schrobilgen, G. Inorg. Chem. 1997, 36, 4078. as Sn9 ,As7 ,Bi7 , and Se4 , all deduced from results of (13) Somer, M.; Carrillo-Cabrera, W.; Peters, E. M.; Peters, K.; von potentiometric titration of liquid ammonia solutions of the Schnering, H. G. Z. Anorg. Allg. Chem. 1998, 624, 1915. corresponding elements and alkali metals.4,5 Later, dissolution (14) Fa¨ssler, T. F.; Hoffmann, R. Angew. Chem., Int. Ed. Engl. 1999, 38, of precursor alloys of the latter was also employed. Also, 543. (15) Fa¨ssler, T. F.; Hoffmann, S. Z. Kristallogr. 1999, 214, 722. ethylenediamine (en) was often used as a solvent instead of (16) Campbell, J.; Dixon, D. A.; Helene, P. A. M.; Schrobilgen, G. J. Inorg. liquid ammonia. Thus, in 1970 using ethylenediamine, Kummer Chem. 1995, 34, 5798. and Diehl isolated and structurally characterized the first (17) Corbett, J. D.; Edwards, P. A. J. Am. Chem. Soc. 1977, 99, 3313. 4- ‚ 6 (18) Burns, R. C.; Corbett, J. D. Inorg. Chem. 1985, 24, 1489. example of a deltahedral Zintl ion, Sn9 in (Na4 7en)Sn9. (19) Critchlow, S. C.; Corbett, J. D. J. Am. Chem. Soc. 1983, 105, 5715. Several years later, a much better approach for the stabilization (20) Belin, C. H. E.; Corbett, J. D.; Cisar, A. J. Am. Chem. Soc. 1977, 99, of Zintl ions was developed by Corbett.7 It involves the use of 7163. the cagelike complexing reagent 4,7,13,16,21,24-hexaoxa-1,- (21) (a) Angillela, V.; Belin, C. J. Chem. Soc., Faraday Trans. 1991, 87, 203. (b) Belin, C.; Mercier, H.; Angillela, V. New J. Chem. 1991, 15, 10-diazabicyclo-[8,8,8]-hexacosane, abbreviated as crypt.It 931. effectively sequesters cations such as Na+,K+, and to some (22) Fa¨ssler, T. F.; Hunziker, M. A. Inorg. Chem. 1994, 33, 5380. extent Rb+ and therefore prevents back-donation of electrons (23) Edwards, P. A.; Corbett, J. D. Inorg. Chem. 1977, 16, 903. (24) (a) Critchlow, S. C.; Corbett, J. D. Inorg. Chem. 1984, 23, 770. (b) from the anion to the cation. A variety of homoatomic and a Corbett, J. D.; Cisar, A. Inorg. Chem. 1977, 16, 2482. few heteroatomic deltahedral Zintl ions have been synthesized (25) Fa¨ssler, T. F.; Hunziker, M. A. Z. Anorg. Allg. Chem. 1996, 622, 837. from such mixed ethylenediamine/crypt solutions of dissolved (26) Critchlow, S. C.; Corbett, J. D. Inorg. Chem. 1982, 21, 3286. (27) Critchlow, S. C.; Corbett, J. D. Inorg. Chem. 1985, 24, 979. (28) Burns, R. C.; Corbett, J. D. J. Am. Chem. Soc. 1982, 104, 2804. (1) Johannis, A. C. R. Hebd. Seances Acad Sci. 1891, 113, 795. (29) Burns, R. C.; Corbett, J. D. J. Am. Chem. Soc. 1981, 103, 2627. (2) Johannis, A. Ann. Chim. Phys. 1906, 7, 75. (30) Bormann, H.; Cambell, J.; Dixon, D. A.; Mercier, H. P. A.; Pirani, A. (3) Kraus, C. A. Trans. Am. Electrochem. 1924, 45, 175. M.; Schrobilgen, G. J. Inorg. Chem. 1998, 37, 1929. (4) Zintl, E.; Goubeau, J.; Dullenkopf, W. Z. Phys. Chem. A 1931, 154, (31) Queneau, V.; Sevov, S. C. Angew. Chem., Int. Ed. Engl. 1997, 36, 1. 1754. (5) Zintl, E.; Kaiser, H. Z. Anorg. Allg. Chem. 1933, 211, 113. (32) Queneau, V.; Sevov, S. C. Inorg. Chem. 1998, 37, 1358. (6) Kummer, D.; Diehl, L. Angew. Chem., Int. Ed. Engl. 1970, 9, 895. (33) Queneau, V.; Todorov, E.; Sevov, S. C. J. Am. Chem. Soc. 1998, 120, (7) Adolphson, D. G.; Corbett, J. D.; Merryman, D. J. J. Am. Chem. Soc. 3263. 1976, 98, 7234. (34) Todorov, E.; Sevov, S. C. Inorg. Chem. 1998, 37, 3889. 10.1021/ic000925f CCC: $19.00 © 2000 American Chemical Society Published on Web 10/26/2000 5384 Inorganic Chemistry, Vol. 39, No. 23, 2000 Xu and Sevov 3- 3- 5- 5- compounds Rb12Si17,K12Sn17,Cs4Ge9,K4Pb9,Cs4Pb9, etc. These synthesis: [In4Bi5] , [Tl4Sb5] , [In5Bi4] , and [Tl5Sb4] . 3- 5- compounds established, for the first time, relations between Zintl Furthermore, closo-clusters such as [In5Bi4] , [In6Bi3], 3- 5- 2- phases and Zintl ions. [Tl5Sb4] , and [Tl6Sb3] isoelectronic with closo-E9 are good Only four heteroatomic deltahedral Zintl ions have been candidates. We have explored these systems as well as the Ga/ 2- reported before. These include the tetrahedral [Sn2Bi2] and Bi system (electronegativities of 1.81 and 2.02 for Ga and Bi, 2- 26,27 [Pb2Sb2] and the mono- and bicapped square antiprismatic respectively). Our initial goal was the synthesis of these clusters 3- 3- 28 [TlSn8] and [TlSn9] , respectively, all refined with statisti- in the solid state, in compounds similar to the known A4E9 (A 2- 4- 31-35 cally disordered heteroatoms. The species [Tl2Te2] ,onthe ) alkali metal) with the E9 clusters. This, however, has other hand, has a butterfly shape despite being isoelectronic with not been achieved so far. All reactions resulted in Zintl phases the tetrahedral clusters (above).29,30 There are a number of with extended structures and with rather localized “normal” two- advantages that heteroatomic clusters with elements of different center-two-electron bonding between indium or gallium and the groups may have over homoatomic species. These possibilities bismuth. Nevertheless, using these and similar Zintl phases as are (a) different reactivity at different vertexes because of the precursors for solution studies, we were able to synthesize occupation by different elements, (b) ability to increase or reduce deltahedral clusters in solids crystallized from such solutions. the charge of the cluster by simply changing the ratio between Here we report the syntheses and structures of (K-crypt)2[InBi3]‚ the two elements, (c) better potential for interconnecting clusters en (1), (Rb-crypt)2[InBi3]‚en (2), and (K-crypt)2[GaBi3]‚en (3)) 2- 2- via bonds between two vertexes of different kinds from each with tetrahedra of [InBi3] or [GaBi3] , and (Na-crypt)3[In4- cluster, and (d) opportunity to study the cluster chemistry of Bi5](4) and (K-crypt)6[In4Bi5][In4Bi5]‚1.5en‚0.5tol (5) with nine- 3- elements that may not be able to form such deltahedral clusters atom deltahedral clusters of [In4Bi5] . Compound 1 is isos- 26,27 on their own. The difficulties associated with the formation of tructural with (K-crypt)2[Sn2Bi2] and (K-crypt)2[Pb2Sb2](6), heteroatomic deltahedral clusters stem from the fact that atoms compound 5 is isostructural with (K-crypt)6E9E9‚1.5en‚0.5tol of different groups have, of course, different sizes, electrone- (E ) Sn, Pb) (7),25 while 4 crystallizes in a new structural type. gativities, number of valence electrons, different stability of the The cluster in 4 and one of the clusters in 5 are the first examples s pair of electrons, etc.