Die Kristallstrukturen der Cyclothiazenokomplexe [MoCl₃(N₃S₂)(Pyridin)] und [MoCl₃(N₃S₂)(Tetrahydrofuran)] / The Crystal Structures of the Cyclothiazeno-Complexes [MoCl₃(N₃S₂)(Pyridine)] and [MoCl₃(N₃S₂)(Tetrahydrofurane)]

Abstract

<jats:p>An improved method of synthesis for MoCl<jats:sub>3</jats:sub>(N<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub>) from molybdenum pentachloride and trithiazylchloride is given. Its reaction with pyridine and tetrahydrofuran in a CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> suspension yields the donor-acceptor complexes [MoCl<jats:sub>3</jats:sub>(N<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub>)(C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>N)] and [MoCl<jats:sub>3</jats:sub>(N<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub>)(C<jats:sub>4</jats:sub>H<jats:sub>8</jats:sub>O)], respectively. Both are soluble in CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> and can be obtained in form of black, moisture sensitive crystals. Their IR spectra are reported and their crystal structures were determined by X-ray diffraction. Both compounds have nearly the same structure (monoclinic, space group P2<jats:sub>1</jats:sub>/c, Z = 4). Lattice constants: [MoCl<jats:sub>3</jats:sub>(N<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub>)(C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>N)], a = 1102.2, b = 997.7, c = 1134.9 pm, α = 94.19° (1582 observed, independent reflexions, R = 0.023); [MoCl<jats:sub>3</jats:sub>(N<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub>)(C<jats:sub>4</jats:sub>H<jats:sub>8</jats:sub>O)], a = 1069.7, b = 1002.5, c = 1122.0 pm, β = 93.77° (1440 reflexions, R = 0.024). In the molecules, the Mo atoms are members of nearly planar MoN<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub> rings with MoN bond distances between 178 and 185 pm , which correspond to double bonds. The sixfold coordination of the Mo atoms is completed by three chlorine atoms and the N or O atom of the pyridine or tetrahydrofuran ligand, respectively. The solvate molecules are in trans positions to one of the N atoms and form dihedral angles of 34.0° and 41.4° with the M oN<jats:sub>3</jats:sub>S<jats:sub>2</jats:sub> rings, respectively.</jats:p>

Donor-Akzeptor-Komplexe von WCl3(N3S2) und WBr3(N3S2). Die Kristallstruktur von WCl3(N3S2) ·THF/ Donor Acceptor Complexes of WCl3(N3S2) and WBr3 (N3S2).The Crystal Structure of WCl3(N3S2)·THF

“…V erzerrt oktaedrische A n o rd n u n g erreich en die M etallatom e durch D im erisie rung m ittels je eines a-N -A to m s der W N 3 S2-E inheit o d e r d urch A usbildung von C hlorobrücken des Typs MoC12M o [1], D urch R e ak tio n mit D onorm olekülen w erden diese B rücken gelöst und m onom ere K om plexe erh a lten . K ristallographisch charakterisierte B eispiele sind WC13 (N 3 S2)(C H 3 CN ) [2], MoC13 (N 3 S2)-T H F , MoC13 (N 3 S2) • Pyridin [3] und W C l3(N 3 S2) • Pyridin [4]. L etzteren K om plexerhielten w ir durch U m setzung von S5N 5 [WC14 (N 3 S2)] mit Pyri din [4], Im folgenden berichten wir vor allem über einige D o n o r-A k zep to r-K o m p lex e des WC13(N 3 S2), die w ir d urch d irek te E inw irkung der D onorm oleküle erh ielten [4], T ab .…”