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376

Lang et al.

Transition Met. Chem., 20, 376-379 (1995)

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-

[WS4Cu3C13Br] and [Et4N]4[WS4Cu416]
Jian-Ping Lang* and Guo-Qing Bian Department of Chemistry, Suzhou University, PO Box 174, Suzhou 215006, Jiangsu, P. R. China Jin-Hua Cai and Bei-ShengKang Fuzhou Laboratory of Structural Chemistry and Fujian Institute of Research on the Structure of Matter, Academia Sinica, Fuzhou 350002, Fufian, P. R. China Xin-Quan Xin Department of Chemistry, Nanjing University, Nanjing 210008, Jiangsu, P. R. China

Summary Reaction of [NH4]E[WS4] with CuX (X--C1 or I) and R4NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)4N]3[WS4Cu3ClaBr], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5)/~, V = 9661.8 ~3, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WSaCu3Br] of C a symmetry with a C1 atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et4N]4[WS4Cu416], crystallizes in the monoclinic space group C2/m with a=29.702(6), b=12.7887(5), c = 15.327(3)A, fl = 99.69(2)~ V = 5738.1/~3, Z = 4. In the cluster anion of (2), four edges of the WS 4 core are coordinated by four Cu atoms, giving a WS4Cu 4 aggregate of approximate CEv symmetry.

Preparation of [ (n-Bu)4N]3[WS4Cu3ClaBr] (1)
A well-ground mixture of [NH4]2[WS4] (0.35g, 1.0 mmol), CuC1 (0.10 g, 1.0 mmol) and n-Bu4NBr (0.64 g, 2.0mmol) was put into a reaction tube which was then sealed. A red-orange solid was obtained by heating the mixture in the solid state at 125 ~ for 15 h. After extracting the product with CH2C12 (40cm 3) and filtering the red-orange extract, the filtrate, on slow evaporation by standing in air at room temperature, deposited red-orange cubic crystals of (1). Yield: 0.21 g (22%). (Found: C, 40.5; H, 7.7; N, 3.1; W, 12.7; Cu, 13.3; C48HlosBrC13Cu3NaS4W calcd.: C, 40.7; H, 7.7; N, 3.0; W, 13.0; Cu, 13.5%). I.r. (cm-1): v(W--St), 482.9s; v(W--Sbr), 431.6s.

Preparation of [Et4N]4[WS4Cu416] (2)
Compound (2) was prepared in the same manner as (1) using CuI (0.38 g, 2.0 mmol), EtaNI (0.26 g, 1.0 mmol) and [(n-Bu)4N]I (0.37g, 1.0mmol) at ll0~ Yield: 0.08g (8.65%) of red-orange plate-like crystals of (2). (Found: C, 20.7; H, 4.3; N, 3.3;W, 9.4; Cu, 13.6; C32H8oCu416N4S4W calcd.: C, 20.8; H, 4.4; N, 3.0; W, 10.0; Cu, 13.8%). I.r. (cm- 1): v(W__Sbr)' 432S.

Introduction
It is well known that the tetrathiometallates MS~(M = Mo or W) bind as multidentate ligands to a wide variety of metal ions(1) and particularly to copper. The reaction of copper(I) with MS4 has led to a large number 2of heteronuclear compounds (2-12). So far, most of these MCuS cluster compounds reported in the literature have been prepared in solution. Recently, we have undertaken investigations on cluster compounds formed by reaction of [NH4]2[MS4] with CuX (X = C1, Br, I or CN) in the solid state and have prepared and structurally characterized a number of interesting mixed-metal cluster compounds t~3-~9). As an extension of this research, we now report the solid state synthesis and structural characterization of two new bimetallic cluster compounds [(n-Bu)4N]3[WS4Cu3C13Br] [(I)] and [Et4N]4[WS4Cu416] [(2)].

Measurements
I.r. spectra (KBr discs) were recorded with a Nicolet Fourier FT-170SX spectrophotometer. C, H, N analyses were performed on a Perkin-Elmer 240C elemental analyer. W and Cu analyses were performed on a JA-1100 ICP spectrophotometer. All solid state reactions were carried out under an Ar atmosphere.

Crystal structure determinations of (I) and (2)
A single crystal of 0.45 x 0.40 x 0.35mm for (1) or 0.40 x0.40 x 0.30mm for (2) was mounted on an MSC/Rigaku four-circle diffractometer. Cell constants were derived from indexing of 25 reflections in the 20 interval of 10-25 ~for (1) or 15-30 ~for (2). Intensity data were corrected for LP factors and for absorption empirically. There was no evidence of crystal decay from three representative reflections measured every 300 reflections. The structures of (I) and (2) were solved by direct

Experimental Materials
[NH4.]2[WS4] was prepared according to the literature (2~ Other reactants and solvents were used as purchased.
* Author to whom all correspondence should be directed.

0340-4285 O 1995 Chapman & Hall

. In the cation containing the N(3) atom. selected bond distances and angles are presented in Table 2. Three CuC1 groups are symmetrically bound to the WS 4 tetrahedron across three edges to form an incomplete WS4Cu 3 cube. Summary of crystal data for Copper(I) thiotungstate clusters 377 [(n-Bu)4N]3[WSaCu3C13Br](1) and [Et4N]4[WS~Cu4I 6] (2) (i) (2) Formula Formula weight Space group Crystal system a (]k) b (~) c (~) fl(~ V(~ 3) Z Dcalc (g cm.40 x 0.40 x 0.trianion and three n-Bu4N § cations..Transition Met. Cations containing the N(3). the remaining atoms were found during iterations of leastsquares refinement cycles and difference Fourier maps. S(3) ?C1(1) . H atoms were not included in the refinements. The coordination geometry of the W atom is a distorted tetrahedron [ S . the summation of the cations was four as cations containing N(4) and N(5) atoms both have site occupancy factors of 0. atoms C(31)-C(38) were disordered.2 4368 0. 20.40 x 0.W 1416.50 + 0..Br lengths of 2.075 0. N(4) and N(5) were-disordered.45 x 0. of variables R~ C48H losBrC13Cu3NS0.8 6 1.67 R3c Hexagonal 17.1 4 2.69(2) 5738.S angles varying from 100.5.71069 0. The geometry of the three equivalent copper atoms is distorted from the ideal tetrahedron with the angles at Cu in the range of 104.372(5) 90.W .39 0.051(5) 38.0.00 9661. The refinements of the occupancy factors converged in both cases to 0. Supplementary data. The anion is situated on a special position and has strict C a symmetry.45 + 0.9(1) to 117. The W. All calculations were performed on a VAX computer using the SDP/VAX program package (~2).073 0.x) 20 range (~ Unique data Observed data No.0a(I) 305 0.9(1)-114.35 tan 0 16 0 50 5432 3118. In (2).43 ~ shorter than the corre- Results and discussion Crystal structure of [n-Bu)4NJ[WS4Cu3CI3BrJ (1) The crystal structure of (I) consists of one [WS4C%C13Br] 3.42 0.327(3) 99.787(5) 15.S b r lengths.626/. 376-379 (1995) Table 1. The structure of the anion with its atomic numbering scheme is shown in Figure 1.062 1.0a(I) 189 0.35 tan 0 1-7 0-50 2103 t050. which is completed by a bromine bridging three Cu atoms.28 C32HsoCu416N484 w 1848.3) Crystal size (ram) /~(MoK~) (cm.30 68.079 1.995 298 __+1 co .anion with its 3 numbering scheme.336(3) ~ a r e 0. s(1) S(2)x: Br % e l Figure 1.0.1) F (0 0 0) Radiation Transmission factors Temperature (K) Scan mode Scan width (~ Scan rate (~min. Crystallographic data for (1) and (2) are summarized in Table 1. (21).702(6) 12. thermal parameters.35 31. including final atomic coordinates. Atomic scattering factors were taken from Ref. I > 3.598 RW b GOF Largest/smallest peaks in final difference map (e/~-3) methods. and structure factors for (I) and (2).7 3488 0.5. threefold axis. Br and S(3) atoms lie on the . Anisotropic thermal factors were introduced for all atoms of the anions and cations of (1) and (2).S t bond length is 0.710-0.99~) 298 ___1 co-20 0.71069 0.654-0.7(2) ~ The C u .20 0. The structure of the [WS4Cu3C13Br] .1(2)~ The W . Several atoms were located from an E map.06~ shorter than the W .94 C2/m Monoclinic 29.14 0.19 0. atoms C(41)-C(45) and C(51)-C(55) were also disordered. have been deposited with the Editor. bond lengths and angles.32/. Chem.. In the cations containing N(4) and N(5) atoms. I > 4.

these cluster compounds with higher nuclearity become unstable at higher temperatures and partly collapse to form a more stable cubane compound like (I).Cua(PPh3)3Br] {19) [2.405(2) 72. The structure closely resembles that of the recently studied molybdenum analogue [Et4N]4 [MoS4CugI6] (ts) with a WSgCu.1(3) 72.9(4) 119. thus (1) crystallizes in the trigonal space group R3c. 9 ) Cu(2) 'b 1(3a) 1(3) Figure 2.7(4) 72.C u lengths [2. 125~ a product similar to (1).770(7)-2. the shortest I(3)--Cu(1) or I(3a)--Cu(3a) contact of 3.487(3) 2.~ longer than the terminal chloro-copper bonds in [Pr4N]3[WS4Cu3C14] (23). W--S0) W S(3) W--Cu(2) S(2)--Cu(1) S(3)--Cu(2) Cu(1)--I(3) Cu(2)--I(3) S(1)--W--S(2) S(2)--W--S(3) W--S(2)--Cu(1) W--S(3)--Cu(2) S(2)--Cu(1)--S(3) s(z)--Cu(1)--I(3) S(3)--Cu(1)--I(3) S(1)--Cu(2) S(3) S(1)--Cu(2) I(3) S(3)--Cu(2)--I(3) Cu(1)--I(3)--Cu(2) 2.CuaC14] (W--Cu.816(3) 109. However.26/~ precludes any ~2-I bridges. The structure of the anion with its atomic numbering scheme is shown in Figure 2. is obtained.9(5) 125. The copper atoms are bound to the WS 4 core.540(3) 110.0(3) 98.6(4) 102. Chem. Complex (1) is similar to the known compounds [Pr4N]a[WS 4Cu3C14] (23) and [(n-Bu)4N]3EWS4Ag3CI4](24).7(2) 117.8(4) 106.6(5) 109.283(4) 2.234(6) 2. The anion of (I) has C3 symmetry while the latter two have 74symmetry.675(3) 2.] (23) in the tetragonal PT~2tc space group and [(n-Bu)4N]3[WSgAg3C14] (24) in the cubic P43m space group. When the right amount of triphenylphosphine was used.337(4) 2.260(3) 2. Ag--S or Ag--Clbr.. Selectedbond lengths (/~) and angles (~ in 1(2a) 1(2) Br--Cu Cu--C1 W--S(3) Cu--Br Cu(1) Br--Cu--C1 S--W--S(1) S--W--S(2) Cu--S--Cu(1) Cu--S(1)--W S--Cu--S(1) 2.8(2) Table 2. It is worth noting that some bonds in [Pr4N]3EWS.720(2) 104..733(2)A].378 Lang et al.0(3) Crystal structure of [Et4NJ4[WS4Cu416] (2) The crystal structure of (2) consists of one crystallographically independent [WS4Cu416] 4. another one or two copper atoms may attach to them and form WS4Cu s or W S 4 C u 6 aggregates as the temperature is raised. 376-379 (1995) (1) 2.7(2) 114.709(3) 2.6(4) 72. aggregate showing almost D2o symmetry.9(2) 71.C I ) (23) and in [(n-Bu)4N]3[WS4Ag3C14] (W--Ag.233(7) 2.434(3) 2.466(2) 2. Selectedbond lengths (~) and angles (~ in (2) 2. The Cu(1) and Cu(1 a) atoms possess trigonal planar coordination while the Cu(2) and Cu(2a) atoms have a tetrahedral geometry.351(5) 3.2(4) 118..tetraanion and four Et4N + cations.2(4) 96.8(1) 114. when excess phosphine was used. When triphenylphosphine was . It is noted that (2) contains no [(n-Bu)gN] + but rather [Et4N ] + cations.anion with its numbering scheme.2(3) 73.1(1) 107.5(3) 103. Because of the more strained framework of the cluster cores.9(2) 100.5(1) 104. The W .Cu416]*. Transition Met. except for the cell packing and the symmetry of the framework of the anions. The Cu--S lengths [2.N]4[MoSgCu416] (18). selected bond lengths and angles are listed in Table 3.7(1) 106. The tungsten atom has an essentially tetrahedral coordination geometry (angles close to 109~) with the tungsten and two sulphur atoms lying in a crystallographic mirror plane. whereas those in (1) have no statistical disorder.0(3) 106.I bonds do not serve as bridging ligands with Cu(1) and Cu(la). [EtgN]3[WS4CuaI4]..257(5) 2. whilst the three Cu--C1 lengths of 2.833(6)A] and [WS4.1(5) 95. The salt [(n-Bu)4N]I is used to decrease the melting point of the solid mixture in the synthesis of (2).1(3) 72. each being attached to one edge of the WS 4 tetrahedron. Table 3. In the cluster anions of (1) or (2).to the neutral cluster [WS4Cu3(PPh3)aBr] (19) was retained.9(3) 115.395(4) 2. Ag--C1 t or W--St) (24) are averaged because of the statistical distribution observed in the fragments of the two compounds.336(3) 2.294(6) 2.395(4)/~] are close to the values observed in compounds containing tetrahedrally-coordinated copper. Cu--S or C u .6(3) 70. possibly due to the solubility difference in dichloromethane.26. forming the linear cluster compound [WS4CuE(PPha)3] t25).715(2)-2.4(3) 86.720(2)A] are comparable to those observed in [Pr4N-]3[WS4Cu3C14] (23) [2.8(3) Cu--S W--S W--Cu Br--Cu--S S--Cu--C1 S--W--S(3) C1--Cu--S(1) Cu--S--W Br--Cu--S(1) Br--Cu(1)--S(2) I(la) C u ~ M) sponding Cu--Br lengths in [WS4Cu3(PPha)3Br](19). The I(3) and I(3a) atoms involved in the longer C u . [Pr4N]a[WSgCuaC1.1(3) 100.the bridging bromide in the substituted product [WS4Cu3(PPha)3Br] u 9) was replaced. This may be explained as follows: as the fifth and sixth edges of the WS 4 tetrahedron in the anion of (2) are uncoordinated.434(3) ~ are 0. respectively.0(3) 74.2(1) W--S(2) W Cu(1) S(1)--Cu(1) S(3)--Cu(1) Cu(1)--I(1) Cu(2)--I(2) S(1)--W--S(3) W--S(1)--Cu(2) W--S(3)--Cu(1) Cu(1)--s(a)--Cu(2) S(2)--Cu(1)--I(1) S(3)--Cu(1)--I(1) I(1)--Cu(1)--I(3) S(1)--Cu(2)--I(2) S(3)--Cu(2)--I(2) I(2)--Cu(2)--I(3) When the heating temperature in the synthesis of (2) is elevated to ca. the three terminal chloride ligands of (1) were replaced by the phosphine and the structure skeleton from the cluster anion [WS4Cu3C13Br] 3. the terminal halide ligands can be readily replaced by stronger ligands such as triphenylphosphine.1(2) 116.8(3) 117. 20. as observed in EEt. The structure of the [-WS.

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