Synthesis and characterization of new oxidopolysulfidovanadates.
The alkali-metal oxidopolysulfidovanadates Cs(4)[(VO)(2)(eta(2)-S(2))(4)(mu-S(2))] (I), Cs(5)[(VO)(3)(eta(2)-S(2))(6)(mu-S(4))] (II), and K(6)[(VO)(4)(eta(2)-S(2))(8)(mu-S(3))].2CH(3)OH.0.6H(2)O (III) have been synthesized by means of methanothermal methods at 170 degrees C or 175 degrees C. These compounds each contain a V(5+) ion coordinated by an oxo ligand and two eta(2)-S(2)(2-) groups. In I, two such [VO(eta(2)-S(2))(2)](-) units are bridged by an S(2)(2)(-) unit. In II and III, two such [VO(eta(2)-S(2))(2)](-) units are joined by a V-S-V bond to form [(VO(eta(2)-S(2))(2))(2)](2-) units; in II, such a [(VO(eta(2)-S(2))(2))(2)](2-) unit is bridged to a [VO(eta(2)-S(2))(2)](-) unit by an S(4)(2-) group; in III, two such [(VO(eta(2)-S(2))(2))(2)](2-) units are bridged by an S(3)(2-) group. Crystallographic data at T = 153 K (compound, space group, Z, a, b, c, beta): I, P2(1)/n, 2, 7.4366(3), 10.3743(5), 13.1151(6) A, 101.097(1) degrees; II, P2(1)/c, 4, 8.4451(6), 24.5144(18), 14.0995(10) A, 101.325(1) degrees; III, C2/c, 4, 31.037(3), 12.5355(11), 8.7822(8) A, 93.127(2) degrees.
Emirdag-Eanes
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Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA.
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