J O U R N A L O F C H E M I S T R Y Materials Synthesis, structure and properties of new dithiolene complexes containing a 1,3,5-trithiepin ring Masaki Takahashi,*a† Neil Robertson,a‡ Akiko Kobayashi,b Hermut Becker,c Richard H. Friendc and Allan E. Underhilla aDepartment of Chemistry, University of Wales, Bangor, Bangor, Gwynedd, UK L L 57 2UW bDepartment of Chemistry, School of Science, the University of T okyo, Hongo, T okyo 113, Japan cDepartment of Physics, University of Cambridge, Cavendish L aboratory,Madingley Road, Cambridge, UK CB3 0HE Mono-tetrabutylammonium salts of nickel, copper, and gold 1,3,5-trithiepin-6,7-dithiolato (ttdt) complexes 1a–c have been prepared and the structures of 1b and 1c determined by X-ray crystallography.Cyclic voltammograms of these complexes showed oxidation peaks in the range 0.23–0.46 V (vs.SCE). Partially oxidised salts of these complexes were obtained either as amorphous or polycrystalline solids. The electrical conduction properties are reported. The crystal structure of (TTF)[Au(ttdt)2] obtained from the reaction of 1c and TTF3(BF4)2 was determined by X-ray crystallography. Bis(dithiolene) transition metal complexes have been investi- Preparation of (R4N)[M(ttdt)2] gated extensively during the last two decades, because of their (R=Bun, Me; M=Ni, Cu, Au) potential for the preparation of molecular conductors or superconductors.1 Recently, large third order non-linear optical (Bun4N)[Ni(ttdt)2] was prepared starting from 1,3-dithiolo[4,5- f ][1,3,5]trithiepin-2-thione 2 by the reported method.4 K2(ttdt) properties have been found in some of these complexes, and some of these complexes are also of interest because of their 3 was prepared by the hydrolysis of thione 2 with an excess of potassium hydroxide in ethanol and isolated by filtration under unique magnetic behaviour.The crystal structures of these complexes which contain columnar stacks of anions and their nitrogen. K2(ttdt) was allowed to react with NiCl2·6H2O in methanol.Addition of tetrabutylammonium bromide to the associated cations play an important role in determining their solid state properties. reaction mixture followed by filtration and recrystallisation yielded the green–black solid product (Scheme 1). One area of current interest in the field of molecular conductors is to construct molecular systems in which either (Bun4N)[M(ttdt)2] (M=Cu 1b, Au 1c) were prepared similarly by using copper(II) chloride or potassium tetrachloroaurate.The donors and acceptors (or ions) or donors and donors are interlinked. This can be achieved for example, by introducing corresponding tetramethylammonium salts of 1a–c were prepared using a similar procedure with tetramethylammonium bromide. a hydrogen bonding network.2 From this point of view, the study of compounds which include non-conjugated group 16 All these complexes gave satisfactory analytical data.The IR spectra contain absorption bands corresponding to elements at the periphery of donors (or acceptors) are important. Studies of TTF derivatives which have peripheral seven- the weakened CNC bond at around 1380 cm-1 for all the complexes and the absorption band corresponding to the CMS membered rings including SCH2OCH2S and SCH2SCH2S group have been reported recently.3 The radical cation salts bond appeared around 850 cm-1.Complexes 1b and 1c exhibited a singlet in 1H NMR spectra due to the SCH2 group at d ca. 4.0. of these donors showed relatively high room temperature conductivities (10-1–102 S cm-1) and also exhibited metal-like electrical conduction properties down to 4.2 K.Crystal structure of (Bun 4N)[M(ttdt)2] In contrast to these cationic salts, metal dithiolene complexes (M=Au, Cu) containing these moieties will give rise to anionic partially oxidised salts and therefore the lone pairs of electrons on the The crystal structures of the copper and gold complexes (1b, peripheral heteroatoms could interact favourably with counter- 1c) were determined by X-ray crystallography.The crystal cations in charge transfer salts. Kato et al. reported the preparation and the structure of the nickel bis(dithiolate) 1a.4 Although the platinum and palladium complexes of this ligand were prepared by Faulmann et al., the preparation of partially oxidised salts of these complexes was unsuccessful.5 Therefore, we have studied the preparation and the properties of bis(dithiolene) complexes 1a–c (Scheme 1) in which the metals (nickel, copper and gold) are coordinated by the 1,3,5-trithiepin-6,7- dithiolato ligand (ttdt) having the 1,3,5-trithiodimethyl group in the periphery of the molecule [M(ttdt)2]x-.† Present address; Centre for Instrumental Analysis, Ibaraki University, 2–1-1, Bunkyo, Mito 310, Japan. ‡ Present address; Department of Chemistry, University of Edinburgh, King’s Buildings, West Main Road, Edinburgh, Scotland, UK S M S S S S S S S S S S S S S S S SK SK S S S 1 2 2 3 2 K2(ttdt) KOH EtOH 2 3 1) metal salt* / MeOH 2) Bun 4NBr (a: M = Ni, b: M = Cu, c: M = Au) c: KAuCl4 b: CuCl2 (Bun 4N) * a: NiCl2 .6H2O Scheme 1 EH9 3JJ. J.Mater. Chem., 1998, 8(2), 319–324 319S M S S2 C2 C1 S1 NC NC CN CN S M S S2 C2 C1 S1 S4 C3 S3 S S S S S M S S2 C2 C1 S1 S S S4 S3 C4 C3 S M S S2 C2 C1 S1 S S S S5 C4 S4 C3 S3 S M S S S S S S S S M S S S S O S S O S [M(mnt)2] [M(dmit)2] [M(dddt)2] [M(ttdt)2] [M(ddtdt)2] [M(diod)2] Fig. 1 Compounds under study structures of these complexes are shown in Fig. 2 and 3. The bond lengths and SMMMS angles found in 1a–c and related complexes are summarized in Table 1. The crystal structures of 1a–c are similar and the structural Fig. 3 Molecular structure of [Au(ttdt)]- in the crystal of parameters of outer trithiepin rings are nearly the same. The (Bun4N)[Au(ttdt)2] 1c diVerences observed between the structures of these complexes are associated with the structural parameters of the inner but slightly shorter than that found for [Cu(dddt)2]- (1.39 A ° ) metallocycles because of the diVerent central metal atoms.The or [Cu(dmit)2]2- (1.36 A ° ). The exo-CMS bond lengths of the structures of these complexes are nearly planar about the metal ligand at 1.753–1.764 A ° , are close to the CMS bond lengths of atom and the outer trithiepin rings take up a chair-like the metallocycle (1.743–1.764 A ° ) and similar to the correspond- conformation. ing distances in related copper complexes (1.75–1.76 A ° ).These The copper complex 1b has basically a planar metallocycle values are in between the usual CNS bond length (1.71 A ° ) and with a slight twist associated with the two dithiolene planes CMS bond length (1.81 A ° ), suggesting that the CMS bonds (four sulfur atoms around the copper atom are deviated from on the dithiolene planes are delocalized.The CuMS bond their mean plane by 0.09–0.17 A ° ). This basically planar struclengths of between 2.181 and 2.190 A° , resemble those in ture is also observed for [Cu(mnt)2]- (the deviations of sulfur [Cu(mnt)2]- (2.170 A ° ) and [Cu(dddt)2]- (2.181 A ° ).The CMS atoms from the mean plane were 0.05–0.11 A ° )6a but is in sharp bond length present in the peripheral trithiepin ring is ca. contrast with the fact that the dithiolene planes in the crystal 1.80 A° , slightly longer than the CMS bonds of [Cu(dddt)2]- of [Cu(dddt)2]- (Bun4 salt) and [Cu(dmit)2]2- are twisted to (1.75 and 1.77 A ° ). 29° 6b and 57°,6c respectively. The CNC bond length of the The structure of the gold complex 1c is similar to those of metallocycle, 1.325 A ° , is a little longer than that of a usual the nickel and copper complexes (1a, 1b), having basically a CNC bond and similar to the value in [Cu(mnt)2]- (1.32 A ° ) planar structure around the gold atom with a chair-like bent peripheral trithiepin rings.The bond lengths and SMAuMS angle are close to the corresponding values of other gold complexes of related ligands (Tables 1 and 2). Redox potentials of (Bun 4N)[M(ttdt)2] (M=Ni, Cu, Au) Cyclic voltammetry measurements were carried out on 1a–c in acetonitrile using a standard calomel electrode with 0.1 M tetrabutylammonium hexafluorophosphate as the electrolyte.The redox potential of these complexes and other complexes are shown in Table 3. The nickel and gold complexes (1a, 1c) showed reversible oxidation peaks at +0.21 and +0.46 V (vs. SCE) respectively, whereas the copper complex 1b showed an irreversible oxidation peak at +0.45 V. The reversible oxidation waves observed for 1a and 1c disappeared on repetitive scans when the potential was increased to >1.5 V.Reversible reduction waves were observed for 1a–c (-0.59, -0.63, -0.91 V, respectively). The oxidation potential of the nickel complex 1a is 0.61 V lower than that of [Ni(mnt)2]-, 0.15 V higher than that of [Ni(dddt)2]- and is close to those of [Ni(dmit)2]- and [Ni(ddtdt)2]-. It therefore appears that nickel complexes of ligands containing seven-membered outer rings are slightly Fig. 2 Molecular structure of [Cu(ttdt)]- in the crystal of (Bun4N)[Cu(ttdt)2] 1b more diYcult to oxidise to the neutral complex than the 320 J. Mater. Chem., 1998, 8(2), 319–324Table 1 Bond distances (A° ) and bond angles (degrees) of some ammonium salts of nickel, copper and gold bis(dithiolene) complexes complex MMS1 C1MS1 C1NC2 S1MMMS2 C1MS3 S3MC3 C3MS4 [Ni(mnt)2]- a 2.149 1.72 1.37 92.5 [Ni(dmit)2]- b 2.156 1.72 1.35 93.2 [Ni(dddt)2]- c 2.132 1.75 1.28 91.1 1.77 1.81, 1.89 [Ni(ttdt)2]- d 2.141 1.72 1.37 91.3 1.76 1.81 1.81, 1.82 [Cu(mnt)2]- e 2.170 1.72 1.32 92.4 [Cu(dmit)2]2- f 2.272 1.73 1.36 94.0 1.75 [Cu(dddt)2]- g 2.181 1.73 1.39 91.5 1.76 1.75, 1.77 [Cu(ttdt)2]- 2.183(1) 1.752(5) 1.332(6) 91.68(6) 1.758(5) 1.805(5) 1.799(5) [Au(mnt)2]- h 2.317 1.75 1.33 90.5 [Au(dmit)2]- i 2.323 1.75 1.31 91.5 1.75 [Au(dddt)2] c 2.304 1.70 1.39 89.2 1.77 1.78, 1.88 [Au(ttdt)2]- 2.312(1) 1.750(5) 1.334(7) 89.35(6) 1.766(4) 1.810(5) 1.780(6) 1.809(6) The numbering of the atoms is as shown in the compounds.References: aA. Kobayashi and Y. Sasaki, Bull. Chem. Soc. Jpn., 1977, 50, 2650.bC. T. Vance, R. D. Bereman, J. Bordner, W. E. Hatfield and J. H. Helms, Inorg. Chem., 1985, 24, 2905. cA. J. Schultz, H. H. Wang, L. C. Soderholm, T. L. Sifter, J. M. Williams, K. Beckgaard and M.-H. Whangbo, Inorg. Chem., 1987, 26, 3757. dRef. 4. eRef. 6(a). fRef. 6(c). gRef 6(b). hP. Kuppusamy, N. Venkatalakshmi and P. T. Manoharan, J. Cryst. Spectrosc. Res., 1985, 15, 629. iG.Matsubayashi and A. Yokozawa, J. Chem. Soc., Dalton T rans., 1990, 3535. Table 2 Bond distances (A ° ) and bond angles (degrees) of [Au(ttdt)2]x- and [Au(dddt)2]x- complexes complex MMS1 C1MS1 C1NC2 S1MMMS2 C1MS3 S3MC3 C3MS4 (Bun4N)[Au(ttdt)2] 2.312(1) 1.750(5) 1.334(7) 89.35(6) 1.766(4) 1.810(5) 1.780(6) 1.809(6) TTF[Au(ttdt)2] 2.318(2) 1.754(5) 1.340(10) 90.78(6) 1.768(5) 1.810(5) 1.805(6) TTF[Au(dddt)2]a 2.304 1.78 1.29 89.8 1.77 1.77, 1.93 TTF[Au(dddt)2]a 2.303 1.76 1.37 89.8 1.76 1.68, 1.81 Reference: aU.Geiser, A. J. Schultz, H. H. Wang, M. A. Beno and J. M. Williams, Acta Crystallogr., Sect. C, 1988, 44, 259. Table 3 Redox potentials of nickel, copper and gold bis(dithiolene) Electrochemical oxidation of (R4N)[M(ttdt)2] complexes The electrochemical oxidation of 1a–c in the presence of alkali E1/V E2/V DE/V metal salts or TTF derivatives was investigated.A variety of complex -1P0 -2P-1 (E1-E2) solvent, electrode solvent systems and current densities were investigated. No crystals were obtained in the electrochemical crystallisation of [Ni(mnt)2]- a +0.82 (irr.) -0.14 0.96 MeCN, Ag/Ag+ the nickel complex 1a but an amorphous solid was obtained [Ni(dmit)2]- b +0.22 (irr.) -0.13 0.37 MeCN, SCE [Ni(dddt)2]- b +0.06 -0.69 0.75 MeCN, SCE on the anode in every experiment.Electrochemical oxidation [Ni(ddtdt)2]- b +0.16 -0.71 0.87 MeCN, SCE of the copper complex 1b aVorded only a small amount of a [Ni(ttdt)2]- +0.21 -0.59 0.80 MeCN, SCE mixture of products on the anode. Experiments involving the gold complex 1c resulted in the production of a polycrystalline [Cu(mnt)2]- a +0.96 (irr.) -0.03 0.99 MeCN, Ag/Ag+ product on the anode.The analytical results obtained for the [Cu(dddt)2]- c +0.38 (irr.) -0.49 0.87 DMF, Ag/Ag+ products obtained from (R4N)[Ni (ttdt)2] suggested a stoichi- [Cu(ttdt)2]- +0.45 (irr.) -0.63 1.08 MeCN, SCE ometry close to that of the neutral [Ni (ttdt)2] complex but [Au(mnt)2]- d +1.15 -0.88 2.03 CH2Cl2, Ag/Ag+ containing a small quantity of the counter-cation.From the [Au(dmit)2]- +0.35 -0.60 0.95 MeCN, SCE analytical data it was very diYcult to determine whether or [Au(dddt)2]- e +0.41 -1.32 1.73 CH2Cl2, SCE not partially oxidised products were obtained. For the nickel [Au(ttdt)2]- +0.46 -0.91 1.37 MeCN, SCE complexes, room temperature conductivities in the range 10-4–10-5 S cm-1 were obtained for products produced by Irr.=irreversible.References: aL. Persaud and C. H. Langford, Inorg. Chem., 1985, 24, 3562. bRef. 4. cRef. g in Table 1. dJ. C. Fitzmaurice, electrocrystallisation in the presence of alkali metal cations. A A. M. Z. Slawin, D. J. Williams, J. D. Woollins and A. J. Lindsay, higher conductivity of 10-1 S cm-1 was observed for the Polyhedron, 1990, 9, 1561.eRef. c in Table 1. product obtained in the presence of Me4N+ ions and whose composition was close to (Me4N)0.5[Ni(ttdt)2] from elemental analysis. These results are somewhat diVerent from those complexes of ligands containing six-membered outer rings. The reported by Cassoux who obtained the neutral nickel complex potentials are rather close to those of [Ni(dmit)2]- which directly from electrochemical and chemical oxidation of 1a.5 contains a conjugated CNS bond.The diVerence between the For the gold complexes, conductivities of around 10-3 S cm-1 oxidation and reduction potentials (DE) of 1a is 0.80 V, which were obtained for products obtained in the presence of alkali is considerably larger than DE of [Ni(dmit)2]-, but is close metal, Bun4N+, Me4N+ cations and BEDT-TTF.to the values of [Ni(dddt)2]- and [Ni(ddtdt)2]- and smaller Partially oxidised salts of [M(dmit)2]- (M=Ni, Au) than that of [Ni(mnt)2]-. The gold complex 1c is more have been shown to exhibit high room temperature conducdi Ycult to oxidise than [Au(dmit)2]- by 0.11 V and has a tivities {room temperature conductivity=101 S cm-1 for larger DE value than [Au(dmit)2]-. The copper complex 1b (Bun4N)0.29[Ni(dmit)2],7 102 S cm-1 for K0.5[Au(dmit)2],8 can be oxidised at a potential lower by 0.51 V compared with 10-1 S cm-1 for TTF0.67[Au(dmit)2]9} whereas the partially oxidised salts of [M(diod)2]- and [M(ttdt)2]- 1 complexes [Cu(mnt)2]-, but DE of 1b is similar to that of [Cu(mnt)2]-. J.Mater. Chem., 1998, 8(2), 319–324 321show relatively lower conductivities {room temperature con- dipotassium salt was added a methanolic solution (10 ml ) of NiCl2 6H2O (133 mg, 0.85 mmol). After stirring the reaction ductivity=10-2 S cm-1 for BEDT-TTF0.17[Ni(diod)2] (compressed pellets)10}. It seems that the bulk or the flip motion of mixture overnight at room temperature, air was bubbled through it for 15 min.The precipitate formed in the reaction the peripheral chair-like seven-membered rings on these ligands interferes with the packing of the anions and makes the was filtered oV and the filtrate was added to a methanolic solution (20 ml ) of tetrabutylammonium bromide (0.90 g, formation of partially oxidised products less likely. 2.8 mmol).The precipitate of 1a was collected by filtration (190 mg, 31%). Dark green crystals of 1a were obtained by Metathesis experiments recrystallisation from acetone and propan-2-ol under vacuum (mp 176.0–176.5 °C). DiVusion controlled metathesis experiments involving (TTF)3(BF4)2 and 1a–c in acetonitrile were carried out. Anal. Calc. for C24H44NS10Ni: C, 39.90; H, 6.11; N, 1.94; S, 44.17.Found: C, 40.28; H, 6.67; N, 1.92; S, 44.99%. IR (KBr Fine needle-shaped crystals were obtained for the nickel and gold complexes (1a, 1c), but no crystals were obtained using disk): 1479, 1453, 1385, 1212, 1164, 1120, 886, 850, 719 cm-1. UV–VIS (CH2Cl2): 395 nm (e=14 300 dm3 mol-1 cm-1), 340 the copper complex 1b. The structure of the gold complex was successfully determined by X-ray crystallography and revealed (e=28 200).near-IR (CH2Cl2): 911 (e=8200). that the product obtained was the 151 salt, TTF[Au(ttdt)2]. Some of the structural parameters are shown in Tables 2 and Preparation of (Bun 4N)[Cu(ttdt)2] 1b 4. In the crystal, a pair of TTF molecules are surrounded by a pair of gold complexes (Fig. 4), an arrangement also seen in A procedure similar to that used in the preparation of 1a the crystal packing of TTF[Au(dddt)2].The structure of was adopted using CuCl2 (130 mg, 1.0 mmol) instead of [Au(ttdt)2]- is very similar to that in (Bun4N)[Au(ttdt)2] and NiCl2 6H2O. The reddish black powder of 1b was obtained the structure of the TTF molecule is similar to that found in (508 mg, yield 72%). Deep red crystals were obtained by TTF[Au(dddt)2] (Tables 2 and 4). recrystallisation from acetone and propan-2-ol under vacuum Too little product was obtained from the experiment involv- (mp 140.5–141.0 °C).ing 1a for elemental analysis and the crystals were too thin for Anal. Calc. for C24H44NS10Cu: C, 39.44; H, 6.07; N, 1.92; S, an X-ray structure determination. 43.87. Found: C, 38.69; H, 6.12; N, 1.82; S, 42.98%.IR (KBr The electrical conductivity of the crystals of TTFx[Ni (ttdt)2] disk): 1481, 1452, 1373, 1213, 1164, 1120, 881, 850, 718 cm-1. obtained from the metathesis experiment of 1a was measured. 1H NMR (CDCl3): d 1.05(12 H, t), 1.45(16 H, m), 3.13(8 H, The room temperature conductivity was ca. 4.7×10-4 S cm-1 t), 4.01(8 H, s, SCH2). UV–VIS (CH2Cl2): 441 nm (e= and the band gap was 0.19 eV over the temperature range 22 200 dm3 mol-1 cm-1). 295–210 K. Preparation of (Bun 4N)[Au(ttdt)2] 1c Conclusion A procedure similar to that used in the preparation of 1a was The preparation, redox electrical properties of [M(ttdt)2]x- adopted using potassium tetrachloroaurate(III) (320 mg, complexes (M=Ni, Cu, or Au) have been described. The 0.85 mmol) instead of NiCl2 6H2O.Air was not bubbled crystal structure of the Cu and Au complexes have been through the solution. A black powder of 1c was obtained determined. Attempts to prepare partially oxidised products (115 mg, yield 16%). Yellow crystals were obtained by recrysby electrocrystallisation resulted in products which behaved tallisation of the product from acetone and propan-2-ol under as semiconductors from room temperature down to 200 K.vacuum (mp 197.0–198.5 °C). The yield of 1c was improved to The compound TTF[Au(ttdt)2] was prepared by metathesis. 35% when the reaction of K2(ttdt) with KAuCl4 was carried out at 50 °C over 2 days. Anal. Calc. for C24H44NS10Au: C, 33.36; H, 5.13; N, 1.62; S, Experimental 37.10. Found: C, 33.14; H, 4.88; N, 1.62; S, 38.46%. IR (KBr All the reaction were carried out under nitrogen.All the disk): 1482, 1374, 1213, 1164, 1120, 951, 872, 850, 719 cm-1. solvents used in the experiments were purified by published 1H NMR (CDCl3): d 1.03(12 H, t), 1.45(16 H, m), 3.12(8 H, methods. Melting points were uncorrected. A Perkin Elmer t), 3.95(8 H, s, SCH2). UV–VIS (CH2Cl2): 345 nm (e= 1600 series FTIR spectrophotometer was used for IR measure- 27 000 dm3 mol-1 cm-1).ment, a Carlo Erba elemental analyser 1106 was used for elemental analysis and a Bruker AC250 instrument was used Preparation of (Me4N)[M(ttdt)2] (M=Ni, Cu, Au) for 1H NMR measurements. UV–VIS spectra were recorded on Hitachi 200–10 spectrophotometer and near-IR spectra The tetramethylammonium salts were prepared by using was recorded on a Perkin Elmer Lambda 9 spectrophotometer.a similar procedure to that used in the preparation of Cyclic voltammograms was performed using a Polarographic corresponding tetrabutylammonium salts 1a–c. Tetramethyl- Analyser Model 264A. ammonium bromide was used instead of tetrabutylammonium bromide [yield: 49% (M=Ni), 36% (M=Cu), 50% Preparation of (Bun 4N)[Ni(ttdt)2] 1a (M=Au)]. Thione 2 (0.51 g, 2 mmol) was allowed to react with potassium hydroxide (0.90 g, 16 mmol) in 10 ml ethanol for 1.5 h at (Me4N)[Ni(ttdt)2].mp: 182.5–184.0 °C. Anal. Calc. for C12H20NS10Ni: C, 25.85; H, 3.62; N, 2.51; S, 57.50. Found: C, 40–60 °C. The resulting gray precipitate of K2(ttdt) was isolated by filtration under nitrogen. To a methanolic solution of the 26.68; H, 3.63; N, 2.30; S, 52.08%.Table 4 Bond distances (A ° ) and bond angles (degrees) of TTF in TTF[Au(ttdt)2] and TTF[Au(dddt)2] complex C5NC5 S6MC5MS7 C5MS6 S6MC6 C6NC7 TTF[Au(ttdt)2] 1.40(1) 115.3(4) 1.705(8), 1.725 (8) 1.716(7) 1.33(2) TTF[Au(dddt)2]a 1.51 115 1.63, 1.73 1.74 1.36 The numbering of the atoms is as shown in Fig. 4. Reference: aRef. a in Table 2. 322 J. Mater. Chem., 1998, 8(2), 319–324Fig. 4 Crystal structure of TTF[Au(ttdt)2]: (a) molecular structure of [Au(ttdt)2]x- in TTF[Au(ttdt)2]; (b) molecular structure of TTFx+ in TTF[Au(ttdt)2]; (c) crystal packing of TTF[Au(ttdt)2] (Me4N)[Cu(ttdt)2].mp: 152.0–153.0 °C. Anal. Calc. for 0.710 69 A ° ) and 12 kW rotating anode generator. Azimuthal scans of several reflections indicated no need for an absorption C12H20NS10Cu: C, 25.62; H, 3.58; N, 2.49; S, 56.99.Found: C, 24.65; H, 3.45; N, 2.34; S, 55.23%. correction. The data were corrected for Lorenz and polarization eVects. The structure was solved by heavy atom Patterson methods (PATTY) and expanded using Fourier techniques. (Me4N)[Au(ttdt)2]. mp: 145.0–146.0 °C. Anal. Calc. for C12H20NS10Au: C, 20.71; H, 2.90; N, 2.01; S, 46.08.Found: C, The refinement was carried out against F. The non-hydrogen atoms were refined anisotopically. The final cycle of full-matrix 21.40; H, 2.96; N, 1.90; S, 47.85%. least squares refinement was based on 3141 observed reflections [I>3.00s(I)] and 325 variable parameters with R(Rw)=0.052 X-Ray crystallography (0.037). All calculations were performed using teXsan crys- Crystal data for 1b.C24H36NS10Cu, M=722.70, primitive tallographic software package of Molecular Structure monoclinic cell, space group P21/n (no. 14), a=12.108(2), b= Corporation.11 17.141(1), c=16.813(2) A ° , b=102.16(1)°, V=3411.1(8) A ° 3, Z=4, Dc=1.407 g cm-3, m=12.68 cm-1. The intensity data (2h<55°) were collected on a Rigaku AFC5R diVractometer Crystal data for 1c.C24H44NS10Au, M=864.18, primitive monoclinic cell, space group P21/n (no. 14), a=12.155(4), with graphite monochromated Mo-Ka radiation (l= J. Mater. Chem., 1998, 8(2), 319–324 323b=17.230(4), c=16.974(3) A° , b=102.51(2)°, V=3470(1) A° 3, We thank the Ramsay Memorials Fellowships Trust and the Ministry of Education, Science and Culture in Japan for the Z=4, Dc=1.654 g cm-3, m=48.72 cm-1.The intensity data (2h<55°) were collected on a Rigaku AFC7R diVractometer support towards M. T. We also thank the British Council (to A. E. U.) and the EPSRC (to N. R.) for support. with graphite monochromated Mo-Ka radiation (l=0.710 69 A ° ). An empirical absorption correction based on azimuthal scans of several reflections was applied which resulted in References transmission factors ranging from 0.6145 to 1.0000. The data were corrected for Lorentz and polarization eVects.The struc- 1 P. Cassoux and L. Valade, Inorganic Materials, ed. D. W. Bruce ture was solved by heavy-atom Patterson methods (SAPI91) and D. O’Hare, John Wiley and Sons Inc., Chichester, 1992, ch. 1, pp. 1–58. and expanded using Fourier techniques. The refinement was 2 For example; (a) T.K. Hansen, T. Jørgensen, P. C. Stein and carried out against F. The non-hydrogen atoms were refined J. Becher, J. Org. Chem., 1992, 57, 6403; (b) T. K. Hansen, anisotopically. The final cycle of full-matrix least squares T. Jørgensen, F. Jensen, P. H. Thygesen, K. Christiansen, refinement was based on 3813 observed reflections M. B. Hursthouse, M. E.Harman, M. A. Malik, B. Girmay, [I>3.00s(I)] and 325 variable parameters with R(Rw)=0.046 A. E. Underhill, M. Begtrup, J. D. Kilburn, K. Belmore, (0.036). All calculations were performed using teXsan crys- P. RoepstorV and J. Becher, J. Org. Chem., 1993, 58, 1359. 3 (a) H. Mu� ller and Y. Ueba, Bull. Chem. Soc. Jpn., 1993, 66, 1773; tallographic software package of Molecular Structure (b) T.Mori, H. Inochi, A. M. Kini and J. M. Williams, Chem. Corporation.11 L ett., 1990, 1279; (c) H. Nakano, K. Yamada, T. Nogami, Y. Shirota, A. Miyamoto and H. Kobayashi, Chem. L ett., 1990, 2129; (d) H. Mu� ller and Y. Ueba, Synth. Met., 1995, 70, 1181; Crystal data for TTF[Au(ttdt)2]. C14H12S14Au, M=826.06, (e) H. Nakano, S. Ikegawa, K. Miyawaki, K. Yamada, T. Nogami primitive triclinic cell, space group P19 (no. 2), a=12.349(3), and Y. Shirota, Synth.Met., 1991, 41–43, 2409. b=13.438(3), c=7.387(2) A ° , a=124.54(2), b=120.88(2), c= 4 R. Kato, H. Kobayashi, A. Kobayashi and Y. Sasaki, Bull. Chem. 101.24(1)°, V=629(1) A ° 3, Z=1, Dc=2.179 g cm-3, m= Soc. Jpn., 1986, 59, 627. 70.27 cm-1. The intensity data (2h<55°) were collected on a 5 (a) C.Faulmann, A. Errami, B. Donnadieu, I. Malfant, J.-P. Legros, P. Cassoux, C. Rovira and E. Canadell, Inorg. Chem., 1996, 35, Rigaku AFC7R diVractometer with graphite monochromated 3856; (b) P. Cassoux, L. Brossard, M. Tokumoto, H. Kobayashi, Mo-Ka radiation (l=0.710 69 A ° ) and 18 kW rotating anode A. Moradpour, D. Zhu, M. Mizuno and E. Yagubskii, Synth. Met., generator. The linear absorption coeYcient, m, for Mo-Ka is 1995, 71, 1845. 70.3 cm-1. An empirical absorption correction based on azi- 6 (a) J. D. Forrester, A. Zalkin and D. H. Templeton, Inorg. Chem., muthal scans of several reflections was applied which resulted 1964, 3, 1507; (b) C. T. Vance, J. H. Welch and R. D. Bereman, in transmission factors ranging from 0.8003 to 0.9995. The Inorg. Chim. Acta, 1989, 164, 191; (c) G. Matsubayashi, K.Takahashi and T. Tanaka, J. Chem. Soc., Dalton T rans., 1988, data were corrected for Lorentz and polarization eVects. The 967. structure was solved by direct methods (SHELX86) and 7 P. Cassoux, L. Valade, H. Kobayashi, A. Kobayashi, R. A. Clark expanded using Fourier techniques. The refinement was carried and A. E. Underhill, Coord. Chem. Rev., 1991, 110, 115. out against F. The non-hydrogen atoms were refined anisotop- 8 L. Valade, J. P. Legros, C. Tejel, B. Pomarede, B. Garreau, ically. The final cycle of full-matrix least squares refinement M. F. Bruniquel, P. Cassoux, J. P. Ulmet, A. Audouard and was based on 2723 observed reflections [I>3.00s(I)] and L. Brossard, Synth. Met., 1991, 41–43, 2268. 9 C. E. A. Wainwright and A. E. Underhill, Mol. Cryst. L iq. Cryst., 128 variable parameters with R(Rw)=0.063 (0.077). All calcula- 1993, 234, 193. tions were performed using teXsan crystallographic software 10 (a) A. E. Underhill, N. Robertson and D. L. Parkin, Synth. Met., package of Molecular Structure Corporation.11 1995, 71, 1955; (b) C. F. Cleary, N. Robertson, M. Takahashi, Full crystallographic details, excluding structure factors, A. E. Underhill, D. E. Hibbs, M. B. Hursthouse and have been deposited at the Cambridge Crystallographic Data K. M. A. Malik, Polyhedron, 1997, 16, 1111. Centre (CCDC). See Information for Authors, J. Mater. Chem., 11 teXsan, Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TN, 1985 & 1992. 1998, Issue 1. Any request to the CCDC for this material should quote the full literature citation and the reference number 1145/73. Paper 7/05966C; Received 14th August, 1997 324 J. Mater. Chem., 1998, 8(2), 319–3