硫酸钒氧酰与1—(2—吡啶偶氮)—2—萘酚在硫醇体系中的反应及配合物晶体结构研究

STUDIES ON REACTION AND CRYSTAL STRUCTURE OF THE COMPLEX FORMED IN THE SYSTEM OF 2-HYDROSULFOBENZOTHIAZOL, VOSO_4 AND 1-(2-PYRIDYLAZO)-2-NAPHTHOL

VCSO_4在碱性条件下被2-硫醇基苯并噻唑还原为V(Ⅱ)离子。1-(2-吡啶偶氦)-2萘酚(PAN)与V(Ⅱ)离子配位成为二个五员环的三齿螯合物。巯基上的硫原予以S^(2-)的形式与V(Ⅱ)离子配位,构成一个四方锥型结构。PAN分子的三齿配位原子与硫原子构成四方锥的底平面。两个单核配合物的钒原子以硫原子为桥,二聚为双核配合物。两个硫原子互为二个四方锥的锥顶。两个四方锥的底平面平行;平面间垂直距离2.6(?)。两个单核物的钒硫原子构成的的桥原子平面,将两个底平面连接起来,相交91.8°。位于底平面上的V—S键长(2.27(?))比位于锥顶的V—S,键(2.76(?))短。可以认为,V—S键的电子在底平面上有一定离域;而锥顶的硫原子(S′)是另一个四方锥底平面上的原子,V—S′键是σ配键。

VOSO_4 is reduced to Ⅴ(Ⅱ) ion with 2-hydrosulfobenzothiazol in alkaline solution of C_2H_5OH/H_2O including alkaline. 1-(2-pyridylazo)-2naphthol (PAN) is coordinated to Ⅴ(Ⅱ) and form a terdentate chelate with both of five-membered rings. Two S atom from -SH group are connected also with Ⅴ(Ⅱ). And thus so, five atoms surrouding Ⅴ(Ⅱ) forming a structure of square prism. Fig. 1 show that atoms O(1), N(1), N(3) come from PAN molecule and S atom form the equatorial plane of the square prism. Dipolymer from two square-prisms is formed with two atoms of sulfur bridging two atoms of vanadium. Two atoms of surfur locate on the top in two square-prisms. Two equatorial planes in two of square prism are parallel and the vertical distance between them is 2.6(?). These equatorial planes are linked witn the plane of bridge (?) The angles between the bridging plane and two equatorial-planes are 91.8° The bond length of V-S (2.27(?)) is shorter than V-S' which locates on the top of the square prism. It is pertinent to consider that electrons on V-S bond are able to delocallize on the equ atorial plane. The atom of S' on the top of the prism is the atom on equatorial-plane of another square prism. The bond of V-S' is a bond only and it is different from the bond of V-O in VP^(2+). Crystal parameters: P2_1/c; a=10.404(1), b=8.272(2), c=15.819(4)(?), β=103.43(1)° z=4; R=0.064.