5H,10H-Dithiolo<2,3-b><2,5>benzodithiocine-2-thione | 107470-30-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5H,10H-Dithiolo<2,3-b><2,5>benzodithiocine-2-thione
• 英文别名: 5H,10H-dithiolo[2,3-b]-2,5-benzodithiocine-2-thione；S=C(oxddt)；S=C(o-xylenediyldithioethylene-1,2-dithiolate)；o-xylenediyldithioethylene-1,3-dithiol-2-thione；5H,10H-Dithiolo[2,3-b][2,5]benzodithiocine-2-thione (C-centred monoclinic form)；5,10-dihydro-[1,3]dithiolo[4,5-c][2,5]benzodithiocine-2-thione
• CAS: 107470-30-4
• 化学式: C₁₁H₈S₅
• 分子量: 300.515
• InChiKey: RSFWCSJMYBZTTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  133
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5H,10H-Dithiolo<2,3-b><2,5>benzodithiocine-2-thione 在 亚磷酸三乙酯 作用下， 反应 2.0h， 以61%的产率得到Bis(o-xylylenedithio)tetrathiafulvalene
  参考文献：
  名称：

  Kumar, S. Kalyan; Singh, Harkesh B.; Jasinski, Jerry P., Journal of the Chemical Society. Perkin transactions I, 1991, # 12, p. 3341 - 3348

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(tetraetylammonium) bis(thioxo-1,3-dithiole-4,5-dithiolato)zincate(II) 、 1,2-二(溴甲基)苯 以68%的产率得到5H,10H-Dithiolo<2,3-b><2,5>benzodithiocine-2-thione
  参考文献：
  名称：

  双（邻苯二甲撑二硫代）四硫富瓦烯的合成

  摘要：

  DOI：

  10.1007/bf00575258

文献信息

• Crystallographic and molecular mechanics investigation of an order–disorder transition and dimorphism in 5<i>H</i>,10<i>H</i>-dithiolo[2,3-<i>b</i>]-2,5-benzodithiocine-2-thione
  作者：Zahid H. Chohan、William T. A. Harrison、R. Alan Howie、Bruce F. Milne、James L. Wardell

  DOI：10.1107/s0108768100010636

  日期：2000.12.1

  Single-crystal X-ray structures are presented for three forms of 5H,10H-dithiolo[2,3-b]-2,5-benzodithiocine-2-thione. The α (at 150 K) and α′ (at ambient) forms are very similar and differ only in the presence of crystallographic m symmetry in the molecules of α′, which is absent in the case of α. This pair is related by an order–disorder transition. The β phase (also determined at 150 K) has a different structure in terms of the molecular packing from either of the other two and therefore constitutes a true polymorph. Molecular mechanics calculations indicated that the most stable CHCl₃-solvated conformations for the title compound were a pair of twisted U-shaped enantiomers, U_R and U_L , i.e. similar to the arrangements found in the α and β phases, with the low-lying saddle point between them corresponding to the situation in the α′ phase. These calculations also indicated that the most stable CHCl₃-solvated conformation for the related dibromo-5H,10H-dithiolo[2,3-b]-2,5-benzodithiocine-2-thione was Z-shaped, in agreement with the crystal structure determined earlier for its DMSO solvate [Wang et al. (1998). Synthesis, pp. 1615–1618].

  本文展示了 5H,10H-二硫环戊并[2,3-b]-2,5-苯并二硫杂-2-硫酮的三种单晶 X 射线结构。α（150 K 时）和 α′（常温下）非常相似，区别仅在于 α′分子中存在晶体学 m 对称性，而 α 不存在。β 相（也是在 150 K 下测定的）的分子堆积结构不同于其他两种，因此是一种真正的多晶体。分子力学计算表明，标题化合物在 CHCl3 溶液中最稳定的构象是一对扭曲的 U 型对映体，即 UR 和 UL 即类似于 α 和 β 相中的排列，它们之间的低洼鞍点与 α′ 相中的情况相对应。这些计算还表明，相关的二溴-5H,10H-二硫环戊并[2,3-b]-2,5-苯并二硫杂-2-硫酮在 溶液中最稳定的构象为 Z 形，这与早先确定的其 DMSO 溶剂的晶体结构一致[Wang 等人 (1998)。 合成》，第 1615-1618 页]。
• Square-planar metal dithiolene complexes (M=Ni, Au) exhibiting cis and trans forms based on structurally flexible o-xylylene backbone
  作者：Mitsushiro Nomura、Kazuto Harada、Toshinori Suzuki、Masatsugu Kajitani、Toru Sugiyama

  DOI：10.1016/j.poly.2012.08.026

  日期：2012.10

  The square-planar metal dithiolene complexes of o-xylenediyldithioethylene-1,2-dithiolate (oxddt) ligand, (Et4P)[Ni(oxddt)(2)] (1), (Ph4P)[Ni(oxddt)(2)] (2) and (Ph4P)[Au(oxddt)(2)] (3), were prepared and characterized. Among them, the Ni complexes 1 and 2 showed cis-anti-form structures, whose two benzene rings of the Ni(oxddt)(2) molecule are closely located to the dithiolene rings but located on the opposite side with respect to the dithiolene ring. In contrast to these Ni complexes, the Au complex 3 has a trans-anti form, suggesting that a Ni/Au substitution in the [M(oxddt)(2)] modifies those molecular structures in the crystals. An intramolecular pi orbital overlap at the alpha-LUMO + 5 level between benzene and dithiolene rings was observed in the [Ni(oxddt)(2)] complex with the cis-anti-form. Redox behavior of 1 and 3 were investigated by cyclic voltammetry measurements. (C) 2012 Elsevier Ltd. All rights reserved.
• CpCo(dithiolene) complexes of highly flexible oxddt ligand with two different Z-shaped and U-shaped structures
  作者：Mitsushiro Nomura、Daisuke Takeuchi、Yoshiko Toyota、Eriko Suzuki、Chikako Fujita-Takayama、Toru Sugiyama、Masatsugu Kajitani

  DOI：10.1016/j.jorganchem.2009.07.026

  日期：2009.12

  [CpCo(oxddt)] complex (2, oxddt = o-xylenediyldithioethylene-1,2-dithiolate, Cp = eta(5)-cyclopentadienyl) was obtained from o-xylenediyldithioethylene-1,3-dithiol-2-one (O=C(oxddt)) (1). 2 further reacted with diazoalkanes (N2CHR) to form some alkylidene-bridged adducts [CpCo(CHR)(oxddt)] (R = H (3a), SiMe3 (3b)). Adduct 3a further reacted with protic acids (HX) to give some S-methylated adducts [CpCo(X)(oxddt)(S-Me)] (X = Cl (4a), OCOCF3 (4c)), followed by the Co-C bond cleavage in the three-membered cobaltathiirane ring. Two different Z-shaped and U-shaped molecular structures were observed by X-ray diffraction studies. In the former structure (Z), the dithiolene and o-xylylene planes are located at almost parallel position each other, and in the latter structure (U), both planes are not parallel but the o-xylylene moiety is located closer to the dithiolene plane than the Z-shaped one. The Z-shaped structure involves 1 and 2. The U-shaped structure involves 3a, 3b, 4a and 4c. Complex 1 showed a one-dimensional chain through intermolecular pi-pi interaction in the crystal. Complex 2 had a dimeric interaction between dithioethylenedithiolate moieties (S2C2S2) in the oxddt. The SiMe3 group in 3b was placed at an exo-position with respect to the cobaltadithiolene ring due to a steric hindrance from the U-shaped oxddt ligand. In 4a, the X and Me groups are located at the opposite side of the dithiolene plane (anti-form) but in 4c, both groups are presented at the same side of the dithiolene plane (syn-form). The NMR analysis of 4a in solution indicated existence of both anti-and syn-isomers (7:1). (C) 2009 Elsevier B.V. All rights reserved.