Bis(μ-N-benzyl-N-methyl­dithio­carbamato)-1:2κ3 S,S′:S′;1:2κ3 S:S,S′-bis­[bis­(N-benzyl-N-methyl­dithio­carbamato-κ2 S,S′)thallium(III)]

The molecule of the dinuclear title compound, [Tl2(C9H10NS2)6], possesses a crystallographically imposed centre of symmetry. Each TlIII atom is seven-coordinated by S atoms of four different dithio­carbamate anions in a distorted penta­gonal-bipyramidal coordination geometry. The crystal structure is stabilized by a C—H⋯S hydrogen-bond inter­action linking complex mol­ecules into chains running parallel to the b axis. Intramolecular C—H⋯S hydrogen bonds are also present

Metal dithiocarbamate precursors for the preparation of a binary sulfide and a pyrochlore: Synthesis, structure, continuous shape measure and bond valence sum analysis of antimony(III) dithiocarbamates

The antimony(III) complexes [Sb(chmdtc) 3 ] (1), [Sb(chedtc) 3 ] (2) and [Sb(dchdtc) 3 ] 0.5 C 7 H 8 (3) (where chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc = dicyclohexyldithiocarbamate) have been prepared and characterized by electronic, IR and NMR ( 1 H and 13 C) spectra and single crystal X-ray diffraction. Electronic spectra of the complexes show charge transfer transitions. The characteristic thioureide bands occur at 1468, 1479 and 1445 cm ?1 for (1), (2) and (3) respectively. The single crystal X-ray structures of (1), (2) and (3) reveal anisobidentate binding of the dithiocarbamates. Short CAH???S contacts are observed along the ‘a’ axis in (2) and (3). CShM calculations on the SbS 6 chromophores support the distorted octahedral geometry in (1) and (2), and the distorted pentagonal pyramidal geometry in (3), clearly quantifying the extent of deviation from the ideal geom- etries. The nature of the substituents and the lone pair of electrons present in antimony are responsible for the shift of the metal atom position from the geometrical center of the six sulfur atoms. BVS of the compounds show the highly covalent nature of the SbAS bonds. Nano Sb 2 S 3 and (Tl + 2/3?2d )[Tl 3+ 1?y Sb 3+ y ] Sb 2 O 6 O 0 1/3?d , a pyrochlore, have been prepared from the precursors and have been characterized by PXRD, FESEM, EDX, HRTEM and SAED

Synthesis and characterization of gallium(III) dithiocarbamates as suitable nano-gallium(III) sulfide precursors

Gallium(III) complexes [Ga(chmdtc) 3 ] (1) and [Ga(chedtc) 3 ] (2) (where chmdtc = cyclohexylmethyldithiocarbamate and chedtc = cyclohexylethyldithiocarbamate) have been prepared and characterized by infrared, nuclear magnetic resonance ( 1 H and 13 C) spectra, thermo- gravimetry, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction (XRD). The thermogravimetric curves obtained for both complexes are almost similar. The final residue corresponded to gallium sulfide (Ga 2 S 3 ) above 700°C for complexes (1) and (2). In the single crystal X-ray structure of [Ga(chedtc) 3 ] (2), Ga-S bonds, and the associated C-S bonds show asymmetry as a requirement of packing. The complex shows distorted octahedral geometry due to its bite angle variations. Nano-α-Ga 2 S 3 was prepared from single source precursors [Ga(chmdtc) 3 ] (1) and [Ga(chedtc) 3 ] (2). Prepared nano-Ga 2 S 3 have been characterized by powder XRD, energy-dispersive X-ray spectroscopy technique, and transmission electron microscopy (TEM)-selected area electron diffraction analysis showing the nano-sized nature of Ga 2 S 3 . TEM micrographs confirmed the size of the particles to be 50 nm

Continuous Shape Measure of electronic effect free steric distortions in tris(dithiocarbamato)indium(III): Synthesis, spectral, electrochemical, single crystal X-ray structural investigations and BVS calculations on tris(dithiocarbamato)indium(III) complexes

Geometrical distortions from an ideal octahedral geometry (iOh) towards an ideal trigonal prism (itp) in tris(dithiocarbamato)indium(III) complexes have been quantified by Continuous Shape Measure (CShM) analysis. Three tris(disubstituted dithiocarbamato)indium(III) complexes, cyclohexylmethyldithiocarbamate (chmdtc) (1), cyclohexylethyldithiocarbamate (chedtc) (2) and dicyclohexyldithiocarbamate (dchdtc) (3), have been prepared and characterized by spectral, cyclic voltammetric and single crystal X-ray structural techniques. The electronic effects are at a minimum for trivalent indium and the distortions follow the order: (3) > (1) > (2), as per the CShM values. The IR spectra indicate a contribution of the thioureide form of the dithiocarbamates to the stabilization of the compounds, with a characteristic C–N stretch in the range 1446–1475 cm?1.1H NMR spectra indicate that the protons in the vicinity of the thioureide nitrogen are the most affected on complexation.13C NMR spectra showed the characteristic thioureide carbon signals at 201.18, 200.98 and 200.94 ppm for complexes (1), (2) and (3) respectively. Cyclic voltammetric investigations revealed three single electron additions to the trivalent indium. The single crystal X-ray structures showed little change in the In–S and thioureide C–N bond distances or the S–In–S bite angles with changes in the steric demands, in the absence of any significant electronic effects. Bond Valence Sums (BVS) of the complexes identified the formal oxidation of indium to be +3 and the observed deviations show the increased covalent bonding. Nano indium sulfides have been prepared from the dithiocarbamates through a non-conventional solvothermal process. The nanosulfides have been characterized by SEM and EDX techniques. The ease and yield of formation follow the order: (3) > (1) > (2)

Mono and trivalent thallium-sulfur interactions and their influence on the formation of nano thallium sulphide: Single crystal X-ray structural and spectral studies on thallium(I)/(III)-cyclohexylpiperazine dithiocarbamates

Thallium(i) and thallium(iii)-cyclohexylpiperazine dithiocarbamates have been prepared with the same donor environment for the first time and analyzed by electronic, IR, 1H, 13C NMR spectral, CV and single crystal X-ray structural analyses. Solvothermal decomposition of the dithiocarbamates yielded nano Tl4S3 and were characterized. Bond parameters from single crystal X-ray structures have been used in continuous symmetry measure and bond valence sum analysis of the compounds to establish the octahedral geometry and formal oxidation numbers of thallium. [Tl(chpzdtc)]2 (1) shows extensive non covalent interactions and the hemidirected TlS2CSTl core is of distorted square pyramidal geometry with the stereo chemically active lone pair of thallium(I) occupying a vertex of the square pyramid. This is the first report which identifies the 4f7/2 and 4f5/2 electron binding energies of Tl(i) and Tl(III) dithiocarbamates unambiguously and the effect of Tl⋯action on XPS binding energies. [Tl(chpzdtc)3] (2), the trivalent analogue as a contrast is a typical holodirected TlS6 distorted octahedral core with no significant supramolecular interactions. Mean Tl-S bond distances in 1 and 2 are 2.985(7) and 2.6789(19) Å, respectively, which clearly support the higher ease of solvothermal decomposition of 1 to nano Tl4S3 than 2. A strong correlation exists between the bond strengths of Tl-S, the thioureide C-N and the ease of formation of Tl4S3 from the two dithiocarbamates 1 and 2

Synthesis, spectral and single crystal structure determination of [1,3-bis(diphenylphosphino-kP,P′)propane(4-morpholinecarbodithioato-S,S′) nickel(II) perchlorate and [1,4-bis(diphenylphosphino-kP,P′)butane (4-morpholinecarbodithioato-S,S′)nickel(II) perchlorate complexes

[Ni(mdtc)(1,3-dppp)]ClO4 (1), and [Ni(mdtc)(1,4-dppb))ClO4 (2) [(mdtc(-) = 4-morpholinecarbodithioato anion. 1,3-dppp = 1,3-bis(diphenylphosphino)propane, 1.4-dppb = 1.4-bis(diphenylphosphino)butane)] have been prepared from their parent dithiocarbamate. The planar complexes were characterized by electronic and IR spectra. Single crystal X-ray structures of compounds 1 and 2 were determined. Both the complexes have planar NiS2P2 chromophores in keeping with the observed diamagnetism. Ln complexes 1 and 2 the Ni-S and Ni-P distances are symmetric. The thioureide C-N distances of both the complexes show a decreasing trend compared to the C-N distance in the parent Ni(mdtc),. The resulting P-Ni-P angles are higher in both the complexes (96.5(1)degrees in 1. 101.4(8)degrees in 2) due to puckering of propane and the butyl alkyl chain associated with 1,3-dppp and 1,4-dpppb

Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds: Synthesis, spectral and single crystal X-ray structural studies on NiS2PN and NiS2PC chromophores

Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds of NiS2PN and NiS2PC chromophores has been investigated by synthesizing and characterizing them. The complexes show the characteristic thioureide IR band at similar to 1530 cm(-1). Electronic spectrum of the cyanide analogue shows a strong blue shift relative to others. X-ray structures of [Ni(pipdtc)(4-MP)(NCS)] (1), [Ni(pipdtc)(PPh3)(NCS)] (2) and [Ni(pipdtc)(PPh3)(CN)] (3) (pipdtc = piperidinecarbodithioate anion, 4-MP = tri(4-methylphenyl)phopshine) are reported. Ni-S bond distance trans to 4-MP(1) is longer than the distances in (2) and (3) and Ni-S bond distances trans to Ni-NCS/CN decrease as follows: (3) > (2) > (1). Particularly, 4-MP shows a highly significant trans influence than triphenylphosphine on Ni-S bond. Similarly, CN- exerts a marginally significant trans influence compared to NCS-. Thioureide C-N distances are relatively very short due to the drift of electron density towards the metal. The Ni-N-C angle (163.5(2)A degrees) observed in (2) indicates deviation from linearity to a larger extent compared to that in (1) (176.3(3)A degrees) due to the steric effect of the 4-methyl group. The reduction potentials (CV) for the mixed ligand complexes are much less compared to that of the parent NiS4 chromophore due to the pi-acidic phosphines

Synthesis, spectroscopic studies, and single crystal X-ray diffraction analysis of a lead(II) based hybrid perovskite: Morpholinium trichloroplumbate(II)

Morpholinium trichloroplumbate(II), [cyclo-O(CH2CH2)2NH]PbCl3 (1), has been synthesized and characterized by elemental analysis, FTIR and 1H and 13C NMR spectroscopy, thermogravimetric analysis (TGA), diffuse reflectance spectra, and single-crystal X-ray diffraction analysis. An FTIR spectrum showed a shift of 100 cm-1 in the NH2 stretching due to the protonated nitrogen of the morpholinium ion. 1H NMR spectrum of the compound showed significant high-frequency shift of the resonance for the CH2 protons due to the presence of cationic charge on the adjacent nitrogen and hydrogen bonded interactions. Contrary to 1H NMR, the 13C NMR signals showed a lowering of 'δ' in the hybrid material. A diffuse reflectance spectrum (DRS) illustrated intense charge transfer in the compound. The observed band gap value for the compound is 3.23 eV based on the DRS data. TG-DT analysis showed the compound to be stable up to 241°C. Single crystal X-ray diffraction analysis of the hybrid material showed the Pb2+ ion being surrounded by six chloride anions in a distorted octahedral geometry. In addition to the six chloride anions, the oxygen atom of the morpholinium cation is also in short contact with the lead cation. Bond valence sum (BVS) calculation confirmed the formal oxidation state of lead to be +2. Continuous symmetry measure (CSM) calculations indicated the PbCl6 to be a distorted octahedron with a magnitude of 5.246 clearly far away from the trigonal prismatic geometry

Synthesis, structural, Continuous Shape Measure and bond valence sum characterization of bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition

Bismuth(III) complexes, [Bi(chmdtc)3] (1) [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) (where chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc = dic- yclohexyldithiocarbamate) have been prepared and characterized by electronic, IR, NMR (1H and13C) spectra, and single crystal X-ray diffraction. Electronic spectra of the complexes show signature bands in the range 418–423 nm due to charge transfer transitions. The characteristic thioureide bands occur at 1474, 1467 and 1443 cm?1for (1), (2) and (3) respectively. Single crystal X-ray structures of [Bi(chmdtc)3] (1), [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) indicate that the short Bi–S interactions between the molecules lead to dimeric structures. CShM calculations on the chromophores clearly quantify the extent of deviation from the ideal geometry. BiS6chromophore in (1) is a distorted octahedron. The coor- dination geometry for both [Bi(chedtc)3] (2) and [Bi(dchdtc)3] (3) should be better described as distorted pentagonal pyramidal. The higher BVS values observed in the present set of compounds support the fact that the Bi–S bonds are more covalent