The Carbon‐Centeredtriprismo‐Hexatungsten Chlorides C@W6Cl16and C@W6Cl18

A mixture of polymeric CW6Cl16(1)and molecular CW6Cl18(2)is formed in a reproducible reaction by heating purchased WCl4(contaminated by e.g. C6H2Cl4) in closed silica tubes at 925 K / 915 K. The direct synthesis of1from W, WCl5and CCl4succeeds at 1030 K / 870 K, but an optimized way to2was not yet found (low yield e.g. from W, WCl6and graphite or from W, WCl6and C6Cl6; 975 K / 965 K). The black crystals of1and2become greenish‐gray after grinding and they are not sensitive to hydrolysis and oxidation.1is diamagnetic with χmol= —865·10—6cm3mol—1and shows numerous FIR bands.1decomposes thermally (870—1060 K) to W and W2C. The13C NMR chemical shift of solid1is observed at +264 ppm. Compound2is soluble in DMSO and the green solution shows characteristic absorptions at 12900, 16500 and 24400 cm—1(13C NMR: δ = 279.9). The crystal structure of2represents ahcparrangement of isolatedtriprismo‐hexatungsten clusters [(CW Cl )Cl ] with 6¯m2 symmetry (d(W—W) = 2.743Å (6×), 2.930Å (3×); d¯(W—Cli) = 2.361Å, 2.434Å; d(W—Cla) = 2.377Å; d(W—C) = 2.157Å). In the structure of1the same central units are interconnected via four Cla—abridging ligands to form 2D puckered layers [(CW Cl )Cl )Cl ]; (d¯(W—W) = 2.658Å (6×), 3.020Å (3×); d¯(W—Cli) = 2.389Å, 2.456Å; d¯(W—Cla) = 2.389Å; d¯(W—Cla—a) = 2.548Å; d¯(W—C) = 2.15Å).Crystal data:1, CW6Cl16, orthorhombic,Pnma(62),oP92;a= 16.637Å,b= 12.958Å,c= 9.797Å,Z= 4; 2094 hkl,R(F) = 0.036. —2, CW6Cl18, hexagonal,P6¯2c(190),hP50;a= 8.923Å,c= 17.503Å,c/a= 1.962,Z= 2; 942 hkl,R(F) = 0.048.