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J. CHEM. SOC. DALTON TRANS. 1992 2987Thallium Macrocyclic Chemistry: Synthesis and CrystalStructures of [TI( ['18]aneN2S,)]PF6 and [TI( ['18]aneS,)]PF6( [ I 8]aneN,S, = I ,4,10,13-tetrathia-7,16-diazacyclooctadecane,[ I 8]aneS, = I .4,7,10,13,16-hexathiacyclooctadecane) tAlexander J. Blake, Gillian Reid and Martin SchroderDepartment of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, UKReaction of TIPF, with 1 molar equivalent of L (L = [18]aneN,S, or [18]aneS,) in refluxing MeCNfollowed by addition of diethyl ether affords the 1 :1 complex [TILIPF, in high yield. The complex[TI([18]aneN2S )]PF, crystallises in the triclinic space group Pi with a = 9.733(6), b = 9.775(6),c = 11.370(8) A, a = 102.68(4), p = 92.35(4), y = 95.05(5)' and Z = 2.The structure shows thethallium(i) ion occupying the 'cradle' formed by the macrocycle and bound via an [N,S, + S,] donorset, TLS(4) 3.1 299(13), TI-S(13) 3.1445(13), TLN(7) 2.834(4), TI-N(16) 2.992(4), TI S ( l )3.4778(15) and TI 0 . S(10) 3.4739(14) A. This leaves the top face of the metal centre exposed,except for long-range interactions with two further thioether donor atoms from adjacent[T1([18]aneN,S,)lf cations, TI 0 . S(1') 3.643(1) (related by 1 - x, 1 - y, 1 - z ) , TI S(10")3.676(1) A (related by 1 - x, 1 - y, - z ) , and one F atom of the PF,- counter-ion, TI F(l)3.326(4) A. The complex [TI( [I 8]aneS,)] PF, crystallises in the monoclinic space group P2,/c witha = 11.0279(13), b = 18.61 7(5), c =10.8568(13) A, p = 96.876(13)" and Z = 4.The structure showsTI' interacting with all six macrocyclic thioether donors; two of those interactions, TI-S(l ) 3.1 64(5)and TI-S(13) 3.205(7) A, being considerably shorter than the other four, TI S(4) 3.370(5),TI S(7) 3.31 5(6), TI S(10) 3.347(7) and TI S(16) 3.356(6) A. There are additional long-range interactions with two further thioether donors from adjacent [TI( [l 8]aneS,)] + cations,TI ... S(7') 3.689(6) (related by - x , 1 - y, 1 - z ) and TI ... S(16") 3.688(6) A (related by 1 - x ,1 - y, 1 - z ) . There is also a long-range contact with one F atom of the PF,- counter-ion, TI F(6)3.052(24) A.We have been studying the co-ordination chemistry of thethioether macrocyclic ligands [9]aneS, (1,4,7-trithiacyclo-nonane), [ 14]aneS4 (1,4,8,1l-tetrathiacyclotetradecane),[ 15]aneS, (1,4,7,10,13-pentacyclopentadecane), [ 18]aneS,(1,4,7,10,13,16-hexathiacyclooctadecane) and the mixed thia-aza macrocycles [ 18]aneN2S, (1,4,10,13-tetrathia-7,16-diaza-cyclooctadecane) and Me2[18]aneN2S4 (7,16-dimethyl-1,4,10,1 3-tetrathia-7,16-diazacyclooctadecane)2 with transition-metal ions.These studies were initiated in an attempt tounderstand the relationships between the stereochemical andredox characteristics of these systems. As a result, we haveshown that macrocyclic ligands are very efficient at stabilisingdiscrete one-electron transfers. Thus, for example, mononuclearpalladium-(I) and -(HI) species are stabilised by co-ordination toMe2[ 1 8]aneN2S4 and [ 18]aneN,S4 re~pectively,~ while thecomplexes [Rh([9]aneS,),13 + and [Rh([ 18]aneS,)13 + bothexhibit chemically reversible Rh"'-Rh" and Rh"-Rh' redoxc o ~ p l e s .~ More recently, we have extended these studies toinclude d'' metal ions such as Cu',' Ad6 and and, forexample, we are now able to prepare the unique series[Au([9]aneS3),]"+ (n = 1-3).'-' In contrast, there have beenvery few reports on complexation of main-group elements withthese ligands8-' Wieghardt and co-workers have reportedthe structure of [Pb([9]aneS3),(OClO,),1 which shows adistorted square-antiprismatic geometry involving two faciallybound [9]aneS3 ligands, Pb-S 3.01 5(5), 3.084(4) and 3.129(5) A,with monodentate perchlorate ions completing the co-ordin-+ Supplementary data available: see Instructions for Authors, J.Chem.SOC., Dalton Trans., 1992, Issue 1, pp. xx-xxv.HN lJ J U[ 1 8]aneN2S4jl8JaneS~ation sphere, Pb-0 2.719(15) and 2.720(15) A. The structures of[(A1Me3),([14]aneS4)] and [AlMe3([12]aneS4)J ([ 12]aneS, =1,4,7,1O-tetrathiacyclododecane) have been reported:' theformer shows an exocyclic geometry in which one AlMe,fragment is bound to each S-donor, A1-S 2.512(2)- 2.531(2) A,generating a tetrahedral stereochemistry at each All" centre; incontrast the geometry at Al"' in [A1Me3([12]aneS,)] is trigonalbipyramidal with [12]aneS4 bridging AlMe, units, Al-S2.718(3) and 3.052(3) A. We have reported the structure of[Tl([9]aneS,)]PF,,'o while more recently Willey et al.' havedescribed the first examples of thioether crown complexation toBiCl, and SbCI, fragments.Izatt et al.' have studied the effectswhich partial substitution of S for 0 have upon binding of alkal2988 J. CHEM. SOC. DALTON TRANS. 1992Table 1 Bond lengths (A), angles and torsion angles (") with estimated standard deviations (e.s.d.s) for [Tl([18]aneN2S,)]+T1- - S( 1) 3.4778( 15) S( ljC(2) 1.837(6) C(6)-N(7) 1.481(7) C(12)-S(13) 1.81 5(5)1.8 17(6) TLS(4) 3.1299( 13) S( 1)-C( 18) 1.825(6) N(7)-C(8) 1.461 (7) S( 13)-C( 14)TI-N( 7) 2.834(4) C(2)-C(3) 1.528(8) C(8)-C(9) 1.543(8) C( 14)-C( 1 5 ) 1.523(8)T1- - S( 10) 3.4739(14) C(3)-S(4) 1.804(6) C(9 jS(10) 1.823(5) C(15 jN(16) 1.459(7)TI-S( 13) 3.1445( 13) S(4)-C(5) 1.8 16(6) S( 10)-C( 1 1 ) 1.8 18(6) N( 16)-C( 17) 1.465(7)1.529( 8) C( 1 7 W ( 18) 1.521(8) TI-N( 16) 2.992(4) C(5)-C(6) 1.512(8) C(l1)-C(12)S( 1 )-Tl-S(4)S( I )-TI-N( 7)S( 1)-Tl-S( 10)S( 1)-Tl-S( 13)S( 1 )-TI-N( 16)S(4)-TI-N( 7)S(4)-TI-S( 10)S(4)-Tl-S( 13)S(4)-TI-N( 16)N(7)-TI-S( 10)N(7)-Tl-S( 13)N(7)-Tl-N( 16)62.78(4)116.83(9)172.43(3)1 10.22(4)60.02(9)66.74( 9)11 1.30(3)65.90(4)62.1 5(9)79.30(9)137.22( 12)77.1 l(9)S( 10)-TI-S( 13)S( 1 0)-TI-N( 16)S( 13)-TI-N( 16)TI-S( 1)-C(2)TI-S( 1 j C ( 18)C(2kS(1 FC( 18)S(lW(2)-C(3)C( 2)-C( 3)-S(4)Tl-S(4)-C( 3)Tl-S(4)-C(5)C(3)-S(4FC(5)62.28(3)1 15.04(9)65.15(9)105.61(19)101.62( 19)101.6(3)112.4(4)1 1 1.8(4)104.1 1( 19)1OO.79( 19)99.0(3)1 15.0(4)1 12.6( 5 )110.5(3)119.3(3)112.9(4)1 12.8(4)1 15.0(4)97.9 1 (1 8)105.79( 18)103.29(25)1 12.9(4)C(ll)-C(l2)-S(13)Tl-S(13)-C(l2)TI-S( 13)-C( 14)C( 12)-S( 13)-C( 14)S( 13)-C( 14)-C( 15)C( 14)-C( 15)-N( 16)TI-N( 16)-C( 15)TI-N( 16)-C( 17)C( 15)-N( 16)-C( 17)N(16)-C( 17)-C( 18)S( 1 )-C( 18)-C( 17)110.7(4)102.73(17)102.92( 18)1oO.7 l(25)114.3(4)112.7(5)110.5(3)120.7(3)114.1(4)113.1(5)113.7(4)C( 18)-S( 1)-€(2)-C(3) - 129.6(4) C(5)-C(6)-N(7)-C(8) 71.2(6) C(ll)-C(12)-S(13)-C(14) 176.7(4)C(2)-S(1)-C(18jC(17) 74.2(5) C(6)-N(7)-C(8jC(9) 161.8(4) C(12)-S(13)-C(l4)-C(15) 72.3(4)S( 1 )-C(2)-C( 3)-S(4) 67.8(5) N(7)-C(8)-C(9)-S( 10) 64.4(5) S(13)-C(14)-(15)-N(16) 68.2(5)C(2)-C(3)-S(4)-C(5) - 179.2(4) C(S)-C(9)-S(lO)-C(ll) 77.8(4) C( 14)-C( 15)-N( 16)-C( 17) 77.6(6)S(4)-C(5)-C(6)-N(7) 65.3(6) S(10)-C(l l)-C(l2)-S(13) 67.5(4) N(l6)-C(l7)-C(lS)-S(l) 64.1(6)C( 3)-S(4)-C( 5)-C( 6) 78.1(4) C(9)-S( lO)-C( 1 1)-C( 12) - 124.2(4) C( 15)-N( 16)-C( 17)-C( 18) 163.5(5)Table 2 Atomic coordinates with e.s.d.s for [TI([l 8]aneN2S,)]PF,Y0.384 560(20)0.375 21(14)0.249 l(6)0.231 2(6)0.15003(14)0.149 4( 6)0.286 5(6)0.330 9(5)0.247 8(6)0.319 2(5)0.346 61(14)0.176 8(6)0.123 4( 5)0.087 85( 14)0.01 7 9(6)0.124 8(6)0.166 8(6)0.278 4(6)0.622 22( 15)0.622 4(4)0.561 9(4)0.621 9(4) -0.774 3 4 )0.683 5(4)0.469 O(4)0.222 3(5)1,0.415 130(20)0.363 ll(15)0.477 7(6)0.543 65( 13)0.713 6(5)0.771 8(5)0.684 9(4)0.695 8(5)0.645 9(5)0.459 56( 14)0.373 l(5)0.262 7(5)0.345 73( 13)0.193 5(5)0.096 O ( 5 )0.160 3(4)0.162 3(6)0.189 6(5)0.026 49( 14)0.191 3(3)0.044 2(4)0.050 6(4)0.009 3(4)0.002 4(4)0.601 4(5)-0.139 8(3)Z0.237 070(20)0.529 68(14)0.603 l(5)0.543 6(5)0.393 15( 12)0.353 2(5)0.3 17 O( 5)0.203 9(4)0.097 O(5)-0.021 4(5)-0.056 99(12)-0.115 7(5)-0.047 6(5)0.105 69(12)0.182 l(5)0.284 2(4)0.402 4( 5)0.504 6( 5)0.230 77( 14)0.240 1 (3)0.360 8(3)0.221 2(4)0.293 4(4)0.101 l(3)0.169 6(4)0.159 4(5)metals and Tl', Pb", Ag' and Hg" in a range of mixed thia-oxacrowns.The results show that such macrocycles form muchmore stable complexes with Ag' and Hg" than with TI' and Pb".However, no structural data are as yet available for thesecomplexes.We report herein the synthesis and single-crystal X-rayStructures Of [TI([ 1 8]aneN2S4)]PF6 and [TI([ 18]aneS6)]PF6,which incorporate potentially hexadentate ligands.Results and DiscussionTreatment of TlPF, with I molar equivalent of L (L =[18]aneN2S4 or [18]aneS,) in refluxing MeCN for 30 minaffords a colourless solution from which a white solid can beobtained upon addition of diethyl ether.Infrared spectroscopyand microanalytical data are consistent with the formulation ofthe products as [TIL]PF6. Fast atom bombardment massspectrometry of the complexes shows molecular ion peaks (M')at m/z 531 and 565 assigned to [T1([18]aneN2S4)]+ and[TI([ 18]aneS,)] + respectively. In order to define the nature ofthe interaction between the macrocyclic ligand and the metalion, and the conformation adopted by the macrocycle, single-crystal X-ray structure determinations were undertaken forboth complexes.Colourless crystals of [TI([ 18]aneN,S4)]PF, were grown byslow evaporation from a solution of the complex in MeCN.Asingle-crystal structure determination shows (Fig. 1, Tables 1and 2) the thallium(1) ion occupying a 'cradle' formed by the[ 1 8]aneN2S4 ligand. The metal ion appears to be bound via an[N2S2 + S,] donorset,Tl-S(4) 3.1299(13),Tl-S(13) 3.1445(13),and T1 S(10) 3.4739(14) A. The shorter TI-S and TI-N bondlengths are less than the sum of the formal ionic radii(1.50 + 1.84 = 3.34 8, for TI-S, 1.12 + 1.84 = 2.96 A forTl-N),14 consistent with a significant degree of covalency in thebonding for the primary co-ordination sphere.Furthermore, thelone pairs on all six macrocyclic donor atoms are clearlydirected towards the central metal ion, with the methylenechains of the macrocycle all directed towards one side of themetal ion. The top face of the thallium(1) ion is therefore exposedexcept for two further, long-range interactions with thioetherdonors from adjacent [TI([18]aneN2S4)]+ cations, T1 S(1')3.643(1) (related by 1 - x, 1 - y , 1 - z ) and T1 S ( l 0 )3.676(1) 8, (related by 1 - x, 1 - y , -2). This cation-cationcross-linking results in infinite double columns of cationsrunning along the c axis. There is also a very long-rangeinteraction of the thallium(1) centre with one F atom of thePF6- counter ion, T1 F 3.326(4) A.The packing diagramfor the complex is shown in Fig. 2. The unusual 'cradle'-likeconformation adopted by the macrocycle in this complexprobably reflects the considerable size mismatch between[18]aneN,S, and the large thallium(1) ion, and the stereo-chemical preferences of TI' for relatively high co-ordinationnumbers. The bond angles around T1' are extremely acute asa consequence of the long thallium-donor bond lengths.TI-N(7) 2.834(4), TI-N(16) 2.992(4) A, TI S(l) 3.4778(15J. CHEM. SOC. DALTON TRANS. 1992 2989Fig. 1 (a) View of the structure of [Tl([18]aneN2S,)]+ with number-ing scheme adopted. (b) Orthogonal view of ~l([18]aneN2S4)]+showing the conformation of the macrocycle‘\Fig. 2 Packing diagram of [Tl([18]aneN2S,)]PF6Previously, we have shown that, upon co-ordination to alarge metal ion such as AgI6 and Hgl,lS [18]aneN,S4 tends tobind through all six donor atoms, but distorts tetrahedrally inorder to accommodate the inherent stereochemical and sizemismatch between the metal ion and the ligand cavity.Thus,structural studies show that for the octahedral complexes rac-[M([ 1 8]aneN2S4)]”+ there is a direct correlation between thedegree of tetrahedral distortion and the ionic radius of the metalcentre.’ It appears however that in [T1([18]aneN,S4)]+ themetal ion is too large even for this, and we observe a newconformation for co-ordinated [l8 ]aneN,S,. Significantly,the 3C DEPT (distortionless enhancement of polarisationtransfer) NMR spectrum (CD,CN) of [TI([18]aneN2S4)]PF,exhibits only three carbon resonances at 298 K, 6 51.66, 36.05and 35.89, consistent with a time-averaged or fluxional speciesin solution.We wished t o compare the above structure of [T1([18]aneN2-S,)] + with its homoleptic thioether analogue. Slow evaporation..WFig. 3 (a) View of the structure of [Tl([18]aneS6)]PF6 withnumbering scheme adopted. (b) Orthogonal view of [T1([ 18]aneS,)]PF,showing the conformation of the macrocycleFig. 4 Packing diagram of [TI([ i8]aneS6)]PF6from a solution of [T1([18]aneS6)]PF, in MeCN gave crystalsof suitable quality for X-ray analysis. The structure shows(Fig. 3, Tables 3 and 4) the [T1([18]aneS6)]+ cation adoptinga very similar stereochemistry to that observed for [Tl([18]2990 J. CHEM. SOC.DALTON TRANS. 1992Table 3 Bond lengths (A), angles and torsion angles (”) with e.s.d.s for [T1([18]aneS6)]+TI-S( I ) 3.164(5) TI-S( 13) 3.205(7) C(5)-C(6)TI * S(4) 3.370(5) T1 9 S(16) 3.356(6) C(6)-S(7)TI - S(7) 3.315(6) S(l)-C(18) 1.789(19) C(12)-S(13)T1 - S( 10) 3.347(7) S(4)-C(5) I .802(23) S( 13)-C( 14)S( I)-Tl-S(4)S( 1 )-TI-S( 7)S( 1 )-TI-S( 10)S( 1 )-TI-S( 13)S( 1 )-TI-S( 16)S(4)-Tl-S(7)S(4)-Tl-S( 10)S(4)-TI-S( 13)S(4)-TI-S( 16)S( 7)-Tl-S( 10)S( 7)-Tl-S( 13)S(7)-TI-S( 16)S( 10)-TI-S( 13)S( 1 0)-TI-S( 1 6)S( 13)-TI-S( 16)63.27( 12)82.8 I( 13)105.72( 15)66.34( 15)65.65( 13)61.59( 13)12 1.16( 15)1 28.47( 16)105.76( 13)59.66( 16)102.55( 16)147.93( 14)63.88(18)12 1.96( 16)60.51(16)- 1 7 1.9(24)60.9( 17)82.2( 17)36(3)89.2(20)87.8(23)65.5(20)- 155.4(27)- 106.1(23)- 1 20( 3)102.6(9)110.2(6)114.8(8)8 9 3 11)105.6( 10)1 17.5(22)106.8( 10)107.7(7)114.6( 15)106.8( 13)80.6( 16)119.7(16)107.2( 16)121.1(21)Tl-S(7)-C(6)Tl-S(7)-C(8)Tl-S(7)-C(8’)C(6kS(7)-C@)C(6)-S(7)-C(8’)S(7)-CW-C(9)C(8)-C(9)-S( 10)n-s( lO)-C( 1 1)C(9)-S( 1 OW( 1 1)S( 10)-C( 1 l)-c( 12)C(12)-C( 1 l)-S(lO’)C( 1 1)-C( 12)-S( 13)TI-S( 13)-C( 12)TI-S( 13)-C( 14)TI-S( 10)-C(9)- 1 69.4( 17)170(3)- 176.6( 18)W6)- 69x421)- 85.3(20)-75.4(19)160.7( 18)7.8(21)176(3)1.50(3) C( 14)-C( 1 5 ) 1.52(4)1.796(24) C(15)-S(16) 1.790(25)1.82(3) S(16)-C(17) 1.806( 19)1.78(3) C(17)-C(18) 1.47(3)104.4( 8)100.0(9)11 1.9(25)94.0( 12)1 12.4(26)103.6( 18)1 14.9( 19)109.6(9)105.3(7)94.3( 1 1)113.2(16)101.9(18)107.2( 18)109.2(9)1 02.7(9)C( 12)-S( 13)-C( 14)S( 13)-C( 14)-C( 15)C( 14)-C( 15)-S( 16)Tl-S( 16)-C( 15)TI-S( 16)-C( 17)C( 15)-S( 16)-C( 17)S( 16)-C( 17)-C( 18)S(1 FC(18)-C(17)S( 1 )-C(2’)-C(3’)S(4)-C(3’)-C(2’)S(7)-C(8’)-C(9’)C(8’)-C(9’)-S( 10)C( ll)-S( lO)-C(9’)93.2( 13)108.0( 18)116.2(17)108.4(8)103.5(6)102.9(10)116.6(13)1 16.9( 14)124.4(24)115(3)119(6)114(6)95(3)C( 1 1bC( 12)-S( 13)-C( 14)C( 12)-S( 13)-C( 14)-C( 15)S( 13)-C( 14)-C( 15)-S( 16)C(14)-C(15)-S(16)-C(17) -C( 15)-S( 16)-C( 17)-C( 18)S( 16)-C( 17)-c(1 8kS( 1)S(1 )--C(2’)-C(3‘)-S(4)S(7)-C(8’)-C(9’)-S( 10)C(8’)-C(9’)-S( lO)-C( 1 1)163.7( 18)174.6( 18)123.2( 18)65.4( 16)65.3( 17)60.2(21)33(4)40(8)99(6)Table 4 Atomic coordinates with e.s.d.s for [TI([ 18]aneS,)]PF6Y0.234 1 l(6)0.332 9(4)0.199 6(5)0.013 2(6)0.306 5(5)0.530 O(4)0.399 6(24)0.323( 3)0.058 8(19)0.009 l(21)-0.031 l(5)-0.055(3)-0.099 5(24)0.074 2(21)0.201 3(20)0.427 O(20)0.541 O(19)0.568 l(16)0.482 9( 16)0.346( 3)0.26 1 (5)- 0.1 1 7( 6)- 0.053(4)0.106( 3)0.279 l(4)0.333 5(11)0.227 O( 12)0.409 4( 16)0.258 2( 17)0.153 4(23)0.327 8(20)0.230(3)0.143 6( 14)Y0.522 83(4)0.678 4(3)0.579 9(3)0.594 5(3)0.546 3(5)0.614 6(5)0.548 2(3)0.666 6(2 1)0.643 4( 19)0.629 8( 14)0.665 O( 13)0.655 l(16)0.605 9( 15)0.611 8(11)0.593 4( 18)0.563 O( 17)0.574 4( 16)0.629 9( 1 1)0.690 2( 1 1)0.698 2( 17)0.669 4( 17)0.628(6)0.679( 5 )0.656 8( 19)0.343 l(3)0.276 4(8)0.409 5(8)0.356 9( 10)0.294 O( 10)0.329 6( 17)0.400 4( 15)0.357 4(20)0.315 3(18)z0.396 93(5)0.470 6(4)0.685 2(4)0.445 9(5)0.160 8(5)0.166 8(4)0.364 7(5)0.631 7(13)0.730( 3)0.676 l(19)0.556 2(19)0.3 14 7(23)0.206 9(22)0.059 l(19)0.029 8(23)0.1 15 8(22)0.207 8( 18)0.450 5( 15)0.426 6( 16)0.635 4( 1 1)0.723(4)0.302( 5 )0.222(8)0.209 8(23)0.145 5(4)0.219 9(10)0.069 4( 16)0.103 l(21)0.029 O( 1 3)0.192( 3)0.247 O( 19)0.272 7( 16)0.1 18(3)aneN,S,)] +, with the macrocycle in a ‘cradle’-like conformation.In [T1([18)aneS6)]+ the metal ion interacts with all sixmacrocyclic donor atoms, with two TI-S bond lengths muchshorter, TI-S(l) 3.164(5) and TI-S(13) 3.205(7) A, than the otherfour, T1 S(4) 3.370(5), TI S(7) 3.315(6), TI S(10)3.347(7) and T1- - S(16) 3.356(6) A.These six macrocyclicdonors all lie on one side of the thallium(1) ion, with two muchlonger intermolecular T1 S interactions on the other side,T1 S(7’) 3.689(6) (related by -x, 1 - y, 1 - z) andTI S(16”) 3.688(6) A (related by 1 - x, 1 - y, 1 - z). OneF atom of the PF6- counter-ion also interacts at long rangewith the Tl’, T1. . F(6) 3.052(24) A. The packing diagram forthe complex is shown in Fig. 4.We have observed similar long TI-S bond distances and acuteS-TI-S angles (ca. 68”) for the complex [T1([9]aneS3)] + inwhich the trithia macrocycle is bound facially to the metal ion,TI-S 3.1 14(3), 3.092(3) and 3.1 1q3) A.Additonally, a thioetherdonor of an adjacent cation makes a long contact, T1 S’3.431(3), linking [T1([9]aneS3)] + cations to form infinitehelices.’O Wieghardt et all6 have reported the structure of therelated complex [T1(Me3[9]aneN3)] + (Me3[9]aneN3 = 1,4,7-trimethyl- 1,4,7-triazacyclonane), which shows the triaza macro-cycle binding facially to the thallium centre, T1-N 2.59(2),2.60(1) and 2.63(1) A, with PF6- counter ions bridging betweenthe cations, Tl...F 3.23(1)-3.54(2) A. These TI-N bonddistances are considerably shorter than those in [TI([18]-aneN,S,)] +, suggesting that the macrocyclic configurationplays a significant role in determining the stereochemistry andmetal-donor distances in the complex.The results described herein reveal that the intra- and inter-molecular contacts present in [TI([ 1 8]aneN2S4)]PF6 and[TI([ 18]aneS6)]PF6 lead to very similar overall geometries forthe two complexes.The very long metal-donor bond lengthsand acute angles at TI’ illustrate the severity of the sizemismatch between the metal-ion radius and the macrocycliccavity size in these systems.ExperimentalInfrared spectra were measured as KBr and CsI discs using aPerkin Elmer 598 spectrometer over the range 200-4000 cm-’J. CHEM. SOC. DALTON TRANS. 1992 299 1electronic spectra in quartz cells using a Perkin Elmer Lambda9 spectrophotometer and electron-impact mass spectra on aKratos MS902 spectrometer.Fast-atom bombardment (FAB)mass spectra in a 3-nitrobenzyl alcohol matrix, were recordedon a Kratos MS 50TC spectrometer. Microanalyses werecarried out by the University of Edinburgh ChemistryDepartment microanalytical service. Proton and ' 3C NMRspectra were run on Bruker WP200 (operating at 200.13 and50.32 MHz respectively) and JEOL FX90Q (operating at 89.55and 22.49 MHz respectively) spectrometers.Synthesis of' [TI([ 1 8]aneN2S4)]PF6.-The salt TlPF6 (40mg, 0.123 mmol) was added to a solution of [18]aneN2S,(43 mg, 0.123 mmol) in MeCN (10 cm3). The reaction mixturewas refluxed for 30 min to give a colourless solution. Thevolume of solvent was reduced to 5 cm3 and diethyl ether wasadded to afford a white precipitate which was recrystallisedfrom MeCN-Et20 and dried in uacuo.Yield 79% (Found:C, 21.3; H, 3.95; N,4.10; S, 18.6. Calc. for Cl,H26F,N,PS,Tl: C,21.3; H, 3.90; N, 4.15; S, 19.0%). FAB mass spectrum: m/z 531;calc. for [205TI([18]aneN2S4)]+ (M') m/z 531. NMR(CD,CN. 298 K): 'H (200.13 MHz), 6 2.96 (s, 8 H), 2.91 (m, 8 H)and 2.81 (m, 8 H); I3C DEPT (50.32 MHz), 6 51.66 (NCH2, 4C),36.05 (SCH,, 4C) and 35.89 (SCH,, 4C). IR (KBr disc): 3260m,2940w, 2910m, 2865w, 2820m, 2740w, 1480w, 1470m, 1445vs,1420m, 1380w, 1340w, 1295m, 1210m, 1175w, 1130m, 1000m,940m, 840vs, 780m, 760w, 710w, 640m and 555vs cm-'.Structure Determination of[Tl([ 1 8]aneN2S4)]PF6.-crystaldata. C, ,Hz6N2S4TlfPF,-, M = 675.87, triclinic, space groupp = 92.35(4), y = 95.05(5)", U = 1049 A3 [from 20 values of 30reflections measured at +o (29 = 3&32", x = 0.710 73 A)],Z = 2, D, = 2.139 g cm-,, T = 150 K, colourless block,0.39 x 0.39 x 0.58 mm, p = 8.285 mm-', F(0oO) = 652.Data collection and processing.Stoe STADI-4 four-circlediffractometer, graphite-monochromated Mo-Ka X-radiation,T = 150 K, w 2 9 scans using the learnt-profile method,' 2692unique data (Rin, = 0.0156), (28,,, 45", h - 10 to 10, k - 10 to10, 1 &l2), semiempirical absorption correcton applied, giving2633 reflections with F 2 6a(F) for use in all calculations. Nosignificant crystal decay or movement was observed.Structure solurion and rejinement. The T1 atom was located bya Patterson synthesis. Iterative cycles of least-squares refine-ment and Fourier difference syntheses located all non-Hatoms.' At isotropic convergence, final corrections (minimum0.864, maximum 1.188) for absorption effects were applied usingDIFABS. ' Non-H atoms were then refined (by least squares onF) l 8 with anisotropic thermal parameters, with H atomsincluded at fixed, calculated positions. At final convergenceR, R' = 0.0278, 0.0396 respectively, S = 0.981 for 237 refinedparameters and the final AF synthesis showed no peak above1.15 e k". The weighting scheme w' = a2(F) + O.OO0 358F2gave satisfactory agreement analyses and in the final cycle(A/C),,,~~ was 0.05. Selected bond lengths, angles and torsionangles are given in Table 1. Fractional atomic coordinates arelisted in Table 2.Pi, u = 9.733(6), b = 9.775(6), c = ii.370(8) A, = io2.68(4),Synthesis u# [TI( [ 1 8]aneS6)]PF,.--Procedure as for [Tl-([18]aneN2S4)]PF,, using TlPF6 (39 mg, 0.112 mmol) and[18]aneS, (40 mg, 0.111 mmol).Yield 72% (Found: C, 20.1;S, 27.1%). FAB mass spectrum: m/z 565; calc. for ["05T1([18]-aneS,)]+ ( M ' ) m/z 565. NMR (CD,CN, 298 K): 'H (89.55MHz), 6 2.96 (CH,, 24 H); 13C (22.49 MHz), 6 31.65 (SCH2).IR (KBr disc): 2920m, 2900m, 1415vs, 1400(sh), 1290w, 1255m,1215w, 1190m, 1150w, 1020w, 925w, 840vs(br), 740m, 710w,695w, 680m, 660w, 620w, 555vs and 480m cm-'.H, 3.45; s. 26.8. Cak. for C12H,,F6PS6Tl]: c , 20.3; H, 3.40;Structurc Determination of' [Tl([1 8]aneS6)]PF6.-Crystalduru. C , H 24S6T1 + PF, -, M = 709.96, monoclinic, spacegroup P2,/c, a = 11.0279(13), b = 18.617(5), c = 10.8568(13)A, p = 96.876(13)", U = 2213 A3 [from 28 values of 18reflections measured at fo (28 = 22-24", x = 0.710 73 A )],2 = 4, D, = 2.131 g ~ m - ~ , T = 150 K, colourless triangularplate,0.35 x 0.31 x 0.04mm,p = 8.035mm-', F(0oO) = 1368.Data collection and processing.The above procedure yielded4302 data of which 2678 were unique (Rint = 0.0529), 28,,, 45",h - 11 to 11, k - 6 to 20, l 0-1 l), semiempirical absorptioncorrection applied, giving 2297 reflections with F 2 k(F) foruse in all calculations. No significant crystal decay or movementwas observed.Structure solution and refinements. The above procedure wasemployed. At isotropic convergence, final corrections (minimum0.845, maximum 1.276) for absorption effects were applied usingDIFABS.During refinement, some disorder was identified inthe macrocycle and in the PF,- anion. The macrocyclicdisorder was modelled partially by constraining the C-C(1.52 A) and C-S (1.83 A) bond lengths in the disorderedregions S( 1) to S(4), S(7) to C( 1 1) and C( 14) to C( 15). This gaverise to two alternative, equally likely, sites for C(2) and C(3) andtwo alternative conformations for the linkage from S(7) to C( 11)in the ratio 0.837( 1) : 0.163(1). All subsequent discussion willrefer to the major [0.837(1)] component. Partial F atomoccupancies were also employed for the PF6- counter ion, suchthat there was a total of six F atoms around the P atom.Anisotropic thermal parameters were refined for T1, S, P and allfully occupied F atoms, with H atoms included at fixed,calculated positions.At final convergence R, R' = 0.0670,0.0880 respectively, S = 1.163 for 193 refined parameters andin the final AFsynthesis the largest peak of 1.82 e A-3 lay close toTI. The weighting scheme w-' = 02(F) + 0.000265F' gavesatisfactory agreement analyses and in the final cycle (A/omaX)was 0.06. Atomic scattering factors were inlaid,'* or taken fromref. 20. Molecular geometry calculations utilised CALC 21 andthe Figures were produced by ORTEP II.22 Selected bondlengths, angles and torsion angles are given in Table 3,fractional atomic coordinates in Table 4.Additional material available from the Cambridge Crystallo-graphic Data Centre comprises H-atom coordinates, thermalparameters and remaining bond lengths and angles.AcknowledgementsWe thank the SERC for support and the Royal Society ofEdinburgh and the Scottish Office Education Department for aSupport Research Fellowship (to M.S.).References1 M. Schroder, Pure Appl. Chem., 1988, 60, 517; A. J. Blake and2 G . Reid and M. Schroder, Chem. SOC. Rev., 1990,19,239.3 G. Reid, A. J. Blake, T. I. Hyde and M. Schroder, J. Chem. SOC.,Chem. Commun., 1988, 1397; A. J. Blake, G. Reid and M. Schroder,J. Chem. SOC., Dalton Trans., 1990,3363.4 A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde and M. Schroder,J. Chem. SOC., Dalton Trans., 1988, 1861; G. Reid and M. Schroder,unpublished work.5 N. Atkinson, A. J. Blake, M. G. B. Drew, G. Forsyth, A. J.Lavery,G. Reid and M. Schroder, f. Chem. SOC., Chem. Commun., 1989,984;A. J. Blake, A. J. Holder and M. Schroder, Polyhedron, 1990,9,2919;A. J. Blake, G. Reid and M. Schroder, unpublished work.6 A. J. Blake, G. Reid and M. Schroder, J. Chem. SOC., Dalton Trans.,1991, 615; A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde andM. Schroder, Polyhedron, 1989, 8, 513; A. J. Blake, R. 0. Gould,G. Reid and M. Schroder, f. Chem. SOC., Chem. Commun., 1990,974.7 A. J. Blake, R. 0. Gould, J. A. Greig, A. J. Holder, T. I. Hyde andM. Schroder, J. Chem. SOC., Chem. Commun., 1989,876; A. J. Blake,J. A. Greig, A. J. Holder, T. I. Hyde and M. Schroder, Angew. Chem.,1990, 102,203; Angew. Chem., Int. Ed. Engl., 1990,29, 197.8 H.-J. Kuppers, K. Wieghardt, B. Nuber and J. Weiss, 2. Anorg. Allg.Chem., 1989,577,155.M. Schroder, Adv. Inorg. Chem., 1990,35,129929 G. H. Robinson and S. A. Sangokoya, J. Am. Chem. SOC., 1988,110,1494; G. H. Robinson, H. Zhang and J. L. Atwood, Organometallics,1987,6,887.10 A. J. Blake, J. A. Greig and M. Schroder, J. Chem. SOC., DaltonTruns., 199 I , 529.1 1 K. Wieghardt, M. Kleine-Boymann, B. Nuber and J. Weiss, Inorg.Chem., 1986,25,1654.12 G. R. Willey, M. T. Lakin, M. Ravindran and N. W. Alcock, J. Chem.Soc., Chem. Commun., 1991, 271; G. R. Willey, M. T. Lakin andN. W. Alcock, J. Chem. SOC., Dalton Trans., 1992, 591.13 R. M. Izatt, R. E. Terry, L. D. Hansen, A. G. Avondet, J. S. Bradshaw,N. K. Dalley, T. E. Jensen and B. L. Haymore, Inorg. Chim. Acta,1978,30, 1 and refs. therein.14 R. D. Shannon, Acta Crystallogr., Sect. A, 1976,32, 751.15 A. J. Blake, G. Reid and M. Schroder, Polyhedron, 1990,9,2931.J. CHEM. SOC. DALTON TRANS. 199216 K. Wieghardt, M. Kleine-Boymann, B. Nuber and J. Weiss, Inorg.17 W. Clegg, Acta Crystallogr., Sect. A, 1981,37,22.18 G. M. Sheldrick, SHELX 76, program for crystal structurerefinement, University of Cambridge, 1976.19 N. Walker and D. Stuart, DIFABS, program for empiricalabsorption corrections, Acta Crystallogr., Sect. A, 1983,39, 158.20 D. T. Cromer and J. B. Mann, Acta Crystallogr., Secf. A, 1968,24,321.21 R. 0. Gould and P. Taylor, CALC, program for molecular geometry22 P. D. Mallinson and K. W. Muir, ORTEP 11, interactive version,Chem., 1986,25,1309.calculations, University of Edinburgh, 1985.J . Appl. Crystallogr., 1985, 18, 51.Received 28th April 1992; Paper 2/02184

ISSN:1477-9226    

DOI:10.1039/DT9920002987

出版商:RSC    

年代:1992

数据来源: RSC