1-Benzyl­sulfanyl-2-[(2-chloro­phen­yl)diazen­yl]benzene

The title compound, C19H15ClN2S, a divalent organosulfur compound belonging to the class of ortho-mercaptoazo compounds, is non-ionic in nature. The azo group in the mol­ecule is moved away from the S atom to attain the stable trans-azo configuration. Here the S atom is not electron deficient, so no intra­molecular N⋯S inter­action exists. Due to steric reasons, the mol­ecule is non-planar: the chlorophenyl and benzyl rings are oriented at dihedral angles of 3.21 (8) and 78.18 (5)°, respectively, with respect to the thiophenyl ring. There are no hydrogen bonds and the crystal structure is stabilized by van der Waals inter­actions

Synthesis and structural studies of cobalt complexes of tridentate ligands incorporating azo, oxime and carboxylate functions

335-338The tridentate ligands H2ArL ( where Ar = Ph, p-tolyl, -naphthyl) react with cobalt(II) acetate tetrahydrate, affording the dark green Et4N[CoIII(ArL)2] complex. The two quasireversible couples (in the range -0.65 to -1.20 V) in the cyclic voltammogram represent azo reduction. The X-ray structure of Et4N[Co(PhL)2] has been determined, revealing the meridional binding of the two ligands affording cis-CoN4O2 <span style="font-size:14.0pt;font-family:&quot;Times New Roman&quot;; mso-fareast-font-family:&quot;Times New Roman&quot;;mso-ansi-language:EN-US;mso-fareast-language: EN-US;mso-bidi-language:AR-SA">geometry.</span

First examples of carboxyl-bonded low-spin manganese(III) complexes

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Synthesis, structure and reactivity of palladated azo-oxime-carboxylates

90-94The bidentate ligands H2L(1) react with sodium tetrachloropalladate to form a presumably dimeric species [PdL]2 which on further treatment with triphenyl phosphine or n-butyl amine furnishes adducts of types [PdL(PPh3)] or [PdL(nBuNH2)] respectively. The X-ray structure of [PdL2(PPh3)] has been determined, revealing the square planar PdN2OP geo metry

<smarttagtype namespaceuri="urn:schemas-microsoft-com:office:smarttags" name="City"><smarttagtype namespaceuri="urn:schemas-microsoft-com:office:smarttags" name="place"> Crystal and molecular structure of <i style="">o</i>-thiobenzyl-N,N-dibenzylaniline (C₂₇H₂₅NS) </smarttagtype></smarttagtype>

172-174In crystals of o-thiobenzyl N,N-dibenzylaniline (I) (C27H25NS), there are three benzyl groups. N atom is two covalent with the C atoms of the two benzyl groups and the S atom is covalent with the C atom of the other benzyl group. The distances N1-C21, N1-C14 and S1-C7 have been found to be 1.489(4), 1.488(9) and 1.832(8)Å, respectively. The molecule is as a whole non-planar. The S1 and the N1 atoms make intramolecular hydrogen bonding. No intermolecular hydrogen bonding has been found and the molecules are stabilised by the network of Van der Waals interaction in their crystalline assembly

<span style="font-size:14.0pt;line-height:115%;font-family:"Times New Roman"; mso-fareast-font-family:"Times New Roman";color:black;mso-ansi-language:EN-IN; mso-fareast-language:EN-IN;mso-bidi-language:HI" lang="EN-IN">Crystal<span style="font-size:14.0pt;line-height:115%;font-family:"Times New Roman"; mso-fareast-font-family:"Times New Roman";color:black;mso-ansi-language:EN-IN; mso-fareast-language:EN-IN;mso-bidi-language:HI" lang="EN-IN"> and molecular structure of 2<span style="font-size:14.0pt;line-height:115%;font-family:"Times New Roman"; mso-fareast-font-family:HiddenHorzOCR;color:black;mso-ansi-language:EN-IN; mso-fareast-language:EN-IN;mso-bidi-language:HI" lang="EN-IN">-chloroazobenzene-2-sulphenylbromide <span style="font-size:14.0pt;line-height:115%;font-family: "Times New Roman";mso-fareast-font-family:"Times New Roman";color:black; mso-ansi-language:EN-IN;mso-fareast-language:EN-IN;mso-bidi-language:HI" lang="EN-IN">(C₁₂H₈BrC1N₂S)</span></span></span></span>

357-360The title compound 2-chloroazobenzene-2-sulphenylbromide (I) (C12H8BrClN2S) is ionic in nature. The electronegativity difference between S and Br atoms makes S atom electrophilic in nature and the presence of intramolecular interaction between the S atom and the azo group has been established by the formation of bond between S and N5 atom and increase in the bond distance between S and Br atoms to 3.23 1 (7)Å in the compound, which is greater than any known covalent length between them. The dihedral angle between the phenyl rings A and C is 46.13(0.13)0. The molecules are stabilised by the network of intermolecular hydrogen bonds and van der Waals contacts.</span

Azooximates of bi- and tri-valent nickel

The reaction of arylazooximes, RC(NOH)NNPh (HL^R, R = Me or Ph), with nickel(II) acetate tetrahydrate in methanol under anaerobic conditions afforded [NiL^R₃]^- isolated as the NEt₄⁺ salt. One (L^Ph)^- ligand in [NiL^Ph₃]^- underwent facile displacement by L–L ligands like 2,2′-bipyridine (bipy) furnishing [NiL^Ph₂ (bipy)]. The Ni^III–Ni^II reduction potential of [NiL^R₃]^- in acetonitrile is ≈ 0.1 V vs. saturated calomel electrode. The trivalent complex [NiL^R₃] was quantitatively isolated via constant-potential electrolysis at 0.3 V. The Ni^IV–Ni^III couple of the tris chelate was observed near 0.9 V, but the nickel(IV) complex could not be isolated in the solid state. The relatively low metal reduction potential allowing facile preparation of the stable [NiL^R₃] system is attributed to the strong-field nature of the oximato-N atom. In going from [NiL^Ph₃]^- to [NiL^Ph₂ (bipy)] the Ni^III–Ni^II reduction potential increases by ≈ 0.3 V showing that (L^Ph)^- is a much better stabiliser of Ni^III than is bipy. The crystal structures of [NEt₄][NiL^Ph₃] and [NiL^Ph₂ (bipy)] have been determined. The geometry of [NiL^R₃] (S = ½) was studied with the help of its EPR spectrum (d_z2 ground state) in the [CoL^R₃] lattice. Both [NiL^R₃]^- and [NiL^R₃] have exclusive meridional geometry consistent with steric and angular-overlap considerations. In [NiL^Ph₂ (bipy)] the two anionic oximato functions are placed in mutually trans positions. The oximato-N ligand displays substantial trans influence. Thus in [NiL^Ph₃]^- the Ni–N (azo) bond lying trans to Ni–N (oxime) is ≈ 0.05 Å longer than the other two mutually trans Ni–N (azo) bonds. The average Ni–N (azo) distance in [NiL^Ph₂ (bipy)] is ≈ 0.04 Å shorter than that in [NiL^Ph₃]^- because none of the Ni–N (azo) bonds in the former complex is subject to the trans influence of Ni–N (oxime). In both complexes the Ni–N (oxime) lengths are significantly shorter than the Ni–N (azo) lengths, consistent with stronger Ni–N (oxime) σ bonding which is also a reason behind the strong-field nature of the oximate ligand

<smarttagtype namespaceuri="urn:schemas-microsoft-com:office:smarttags" name="place" downloadurl="http://www.5iantlavalamp.com/"><smarttagtype namespaceuri="urn:schemas-microsoft-com:office:smarttags" name="City" downloadurl="http://www.5iamas-microsoft-com:office:smarttags"> Crystal and molecular structure of 2-thiobenzylazobenzene (C₁₉H₁₆N₂S) </smarttagtype></smarttagtype>

863-866The title compound (I, W=X=Y=H, Z = CH2Ph) is a divalent organosulphur compound of the type Ar-S-Z belonging to the class of ortho mercaptoazo compounds. The azo group is moved away from the sulphenyl sulphur atom to attain the stable trans azo configuration. The sulphur atom has used hybrid orbitals (sp3) and not pure p-orbitals for the bond formation. The benzyl units attached to the sulphenyl sulphur and the 2-benylazo unit are moved away from each other for steric reason. The molecule is as a whole non-planar but N1 and N2 atoms are coplanar with the respective phenyl rings to which they are attached. The S1 atom is coplanar with the phenyl group to which it is attached. The dihedral angle between the mean planes passing through the atoms of the thiophenyl group and the benzyl group is 75(1)°. There is no intermolecular hydrogen bond and the molecule is stabilised by the network of Van der Waal's interaction in their crystalline assembly