Crystal and molecular structure of bis(tetraphenylphosphonium) bis(1,2-dicyanoethylene-1,2-dithiolato)oxovanadate(IV): its single-crystal electron spin resonance as a pure compound and diluted in the isomorphous molybdenum(IV) compound
Crystal and molecular structure of bis(tetraphenylphosphonium) bis(1,2-dicyanoethylene-1,2-dithiolato)oxovanadate(IV): its single-crystal electron spin resonance as a pure compound and diluted in the isomorphous molybdenum(IV) compound
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双(四苯基鏻)双(1,2-二氰基乙烯-1,2-二硫醇)氧钒酸盐(IV)的晶体和分子结构：其纯化合物的单晶电子自旋共振和稀释在同晶钼(IV)化合物中
DOI：
10.1039/dt9880000309
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发表时间：
1988
期刊：
影响因子：
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通讯作者：
J. Huffman
中科院分区：
文献类型：
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作者：
D. Collison;F. Mabbs;J. Temperley;G. Christou;J. Huffman
[PPh4]2[VO(mnt)2](mnt = 1,2-二氰基乙烯-1,2-二硫醇盐)的晶体结构已在 –154 °C 下通过 X 射线晶体学方法测定。该化合物在单斜空间群 P21/n 中结晶，a= 11.176(3)、b= 15.254(5)、c= 14.319(4)A、β= 97.62(1)°、Z= 2。阴离子围绕反转中心无序，每个位点占据 50%。阴离子具有近似四角锥体的几何形状，尺寸为：V–O 1.579(10)、V–S(3′) 2.356(4)、V–S(3) 2.372(3)、V–S(4) 2.360(3) 和 V–S(4′) 2.407(3)A。单晶 E.S.R.室温下的光谱和 Q 带频率给出了自旋哈密尔顿参数； g1= 1.970±0.002，g2=1.987±0.002，g3=1.988±0.002，A1=(–42.5±1.0)×10–4，A2=(–45.5±1.0)×10–4，A3=(–136.6±1.0)× 10–4 厘米–1； g1 和 A3 重合，但 g2 和 g3 分别相对 A1 和 A2 旋转 6°。类似地，对于 [PPh4]2[(Mo, V)O(mnt)2]：g1= 1.971 ± 0.001，g2= 1.986 ± 0.001，g3= 1.989 ± 0.001，A1=(–40.3 ± 0.3)× 10–4，A2=(–47.4 ± 0.3)× 10–4， A3=(–136.3±0.3)×10–4cm–1，Q′=3e2qQ/4I(2I–1)=–(0.09±0.05)×10–4cm–1； g1 和 A3 重合，g2 和 g3 分别从 A1 和 A2 旋转 5.5°。通过角度重叠和自旋哈密尔顿参数表达式的复合函数的约束最小化来分析 g 和 A 张量，以估计复合体中的 d 轨道混合。
The crystal structure of [PPh4]2[VO(mnt)2](mnt = 1,2-dicyanoethylene-1,2-dithiolate) has been determined at –154 °C by X-ray crystallographic methods. The compound crystallises in the monoclinic space group P21/n with a= 11.176(3), b= 15.254(5), c= 14.319(4)A, β= 97.62(1)°, and Z= 2. The anion is disordered about the inversion centre with 50% occupancy of each site. The anion has approximately square-pyramidal geometry with dimensions: V–O 1.579(10), V–S(3′) 2.356(4), V–S(3) 2.372(3), V–S(4) 2.360(3), and V–S(4′) 2.407(3)A. Single-crystal e.s.r. spectra at room temperature and Q-band frequencies gave the spin-Hamiltonian parameters; g1= 1.970 ± 0.002, g2= 1.987 ± 0.002, g3= 1.988 ± 0.002, A1=(–42.5 ± 1.0)× 10–4, A2=(–45.5 ± 1.0)× 10–4, and A3=(–136.6 ± 1.0)× 10–4 cm–1; g1 and A3 are coincident but g2 and g3 rotate by 6° from A1 and A2 respectively. Similarly for [PPh4]2[(Mo, V)O(mnt)2]: g1= 1.971 ± 0.001, g2= 1.986 ± 0.001, g3= 1.989 ± 0.001, A1=(–40.3 ± 0.3)× 10–4, A2=(–47.4 ± 0.3)× 10–4, A3=(–136.3 ± 0.3)× 10–4 cm–1, and Q′= 3e2qQ/4I(2I– 1)=–(0.09 ± 0.05)× 10–4 cm–1; g1 and A3 are coincident and g2 and g3 rotated 5.5° from A1 and A2 respectively. The g and A tensors have been analysed via both angular overlap and by constrained minimisation of a composite function of the expressions for the spin-Hamiltonian parameters to estimate the d-orbital mixing in the complex.