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3031081 
Journal Article 
Pr3S2Cl2[AsS3]: A Praseodymium(III) Sulfide Chloride Thioarsenate(III) with Double Chains of Condensed [SPr4](10+) Tetrahedra 
Kang, DHee; Ledderboge, F; Kleinke, H; Schleid, T 
2015 
1 
Zeitschrift fuer Anorganische und Allgemeine Chemie
ISSN: 0044-2313 
641 
2 
322-326 
WOS:000351444500030 
Single crystals of Pr3S2Cl2[AsS3] were obtained by reacting praseodymium sesquisulfide and trichloride with arsenic and sulfur (molar ratio: 7: 4: 6: 9) in torch- sealed evacuated silica ampoules at 850 degrees C for a week and subsequent slow cooling to room temperature. The transparent, pale yellowish green platelets crystallize monoclinically (Pr3S2Cl2[AsS3]: a = 2190.96(9) pm, b = 685.49(3) pm, c = 701.87(3) pm, beta = 98.752(3)degrees) in the non- centrosymmetric space group Cc with Z = 4. The crystal structure of Pr3S2Cl2[AsS3] comprises three crystallographically different Pr3+ cations. (Pr1)(3+) and (Pr2)(3+) exhibit bicapped trigonal prismatic environments of five sulfur and three chlorine atoms (C. N. = 8) each, whereas only seven sulfur atoms arranged as capped trigonal prism (C. N. = 7) are present in the case of (Pr3)(3+). Two of the five crystallographically different sulfur atoms (S1 and S2) are coordinated by four Pr3+ cations, each in the shape of slightly distorted [SPr4] 10+ tetrahedra (d(S- Pr) = 278- 294 pm). Hence, the crystal structure of Pr3S2Cl2[AsS3] contains double chains with the composition (1)(infinity){[S2Pr3](5+)}, consisting of two parallel edge-fused chains of anti-SiS2-analogous single strands (1)(infinity){[SPr2](4+)}, formed by transedge sharing [SPr4](10+) tetrahedra. The arrangement of the (1)(infinity){[S2Pr3](5+)} double chains running along [001] can be described as a hexagonal rod- packing. Chloride anions (Cl1 and Cl2) as well as the isolated, psi(1)-tetrahedral thioarsenate(III) groups [AsS3](3-) (d(As- S) = 228- 229 pm) consisting of three sulfur atoms (S3, S4, and S5) and an As3+ cation carrying a stereochemically active non- bonding electron pair take care of the three-dimensional interconnection and the charge balance of the (1)(infinity)[S2Pr3](5+)} double chains. All lone pairs at the As3+ cations of the [AsS3](3-) pyramids point in the same direction parallel to the c axis of the acentric crystal structure of Pr3S2Cl2[AsS3]. 
Sulfides; Praseodymium; Chlorides; Thioarsenates; Crystal structure