Synthesis and Characterization of New Oxidopolysulfidovanadates

The alkali-metal oxidopolysulfidovanadates Cs4[(VO)2(η2-S2)4(μ-S2)] (I), Cs5[(VO)3(η2-S2)6(μ-S4)] (II), and K6[(VO)4(η2-S2)8(μ-S3)]·2CH3OH·0.6H2O (III) have been synthesized by means of methanothermal methods at
170 °C or 175 °C. These compounds each contain a V5+ ion coordinated by an oxo ligand and two η2-S22-
groups. In I, two such [VO(η2-S2)2]- units are bridged by an S22- unit. In II and III, two such [VO(η2-S2)2]-
units are joined by a V−S−V bond to form [(VO(η2-S2)2)2]2- units; in II, such a [(VO(η2-S2)2)2]2- unit is bridged
to a [VO(η2-S2)2]- unit by an S42- group; in III, two such [(VO(η2-S2)2)2]2- units are bridged by an S32- group.
Crystallographic data at T = 153 K (compound, space group, Z, a, b, c, β):  I, P21/n, 2, 7.4366(3), 10.3743(5),
13.1151(6) Å, 101.097(1)°; II, P21/c, 4, 8.4451(6), 24.5144(18), 14.0995(10) Å, 101.325(1)°; III, C2/c, 4, 31.037(3), 12.5355(11), 8.7822(8) Å, 93.127(2)°.

本研究通过甲醇热法（methanothermal methods）于170 ℃或175 ℃下合成了三种碱金属氧化多硫钒酸盐：Cs₄[(VO)₂(η²-S₂)₄(μ-S₂)] (I)、Cs₅[(VO)₃(η²-S₂)₆(μ-S₄)] (II)以及K₆[(VO)₄(η²-S₂)₈(μ-S₃)]·2CH₃OH·0.6H₂O (III)。上述三类化合物均各含有一个被氧配体与两个η²-S₂²⁻基团配位的五价钒离子。在化合物I中，两个此类[VO(η²-S₂)₂]⁻单元通过一个S₂²⁻单元进行桥联。在化合物II与III中，两个此类[VO(η²-S₂)₂]⁻单元经由V−S−V键结合形成[(VO(η²-S₂)₂)₂]²⁻单元；其中，化合物II中的此类[(VO(η²-S₂)₂)₂]²⁻单元通过一个S₄²⁻基团桥联至一个[VO(η²-S₂)₂]⁻单元；化合物III中的两个此类[(VO(η²-S₂)₂)₂]²⁻单元则通过一个S₃²⁻基团进行桥联。于153 K下采集的晶体学数据（化合物、空间群、晶胞参数Z、a、b、c、β）如下：I：空间群P2₁/n，Z=2，a=7.4366(3) Å，b=10.3743(5) Å，c=13.1151(6) Å，β=101.097(1)°；II：空间群P2₁/c，Z=4，a=8.4451(6) Å，b=24.5144(18) Å，c=14.0995(10) Å，β=101.325(1)°；III：空间群C2/c，Z=4，a=31.037(3) Å，b=12.5355(11) Å，c=8.7822(8) Å，β=93.127(2)°。