Molecular and Supramolecular Structures of 1‐Phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H2L) and its Complexes with Diphenyllead(IV) Chloride and Acetate

Reaction of 1‐phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H₂L) with diphenyllead(IV) dichloride and acetate afforded the complexes [PbPh₂Cl₂(H₂L)₂] and [PbPh₂L]. The ligand and the complexes were characterized by elemental analyses, ¹H and ¹³C NMR spectroscopy and X‐ray crystallography. In the asymmetric unit of crystals of the ligand there are four independent molecules of H₂L and four molecules of water, which associate in the lattice as two independent sheets. The complex [PbPh₂Cl₂(H₂L)₂]·4MeOH has slightly distorted all‐trans octahedral geometry around the lead atom, and the fact that the ligand is S‐bound rather than O‐bound suggests that PbPh₂Cl₂ behaves as a “soft” Lewis acid. Hydrogen bonds involving NH groups, Cl atoms and MeOH molecules form a three‐dimensional supramolecular structure. In [PbPh₂L]·Me₂CO, the L^2? anion bridges between two metal centres, binding to one strongly via the N and S atoms and weakly via the O atom, and to the other via the O atom, thus creating polymeric chains along the b axis. The double deprotonation and metallation of H₂L induce significant changes in its configuration and lengthen the C‐S and C‐O bonds, suggesting an evolution of the dianion towards a thiol‐enol form.     

Di‐μ‐sulfido‐bis[diaqua(18‐crown‐6)­barium(II)]–saccharin (1/2)

The mol­ecule of the title compound {systematic name: di‐μ‐sulfido‐bis[di­aqua(1,4,7,10,13,16‐hexaoxa­cyclo­octade­cane‐κ⁶O)barium(II)] bis­[1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxide]}, [Ba₂S₂(C₁₂H₂₄O₆)₂(H₂O)₄](C₇H₅NO₃S)₂, lies on an inversion centre. The Ba^II atom encapsulated by the 18‐crown‐6 ring is coordinated by the six O atoms of the crown, two water O atoms and two bridging S atoms. The four‐membered ring composed of the Ba^II atoms and the bridging S atoms makes a dihedral angle of 67.1 (1)° with the crown‐ether ring. The aromatic ring system of the saccharin moiety is essentially planar. The packing is built up from layers of the mol­ecules and is stabilized by three intermolecular O—H?O hydrogen bonds.     

Metal Derivatives of Heterocyclic‐2‐thiones: Crystal Structures of [Bis(diphenylphosphanyl)propane][bis(pyrimidine‐2‐thiolato)]ruthenium(II) and [Bis(diphenylphosphanyl)methane][bis(pyridine‐2‐thiolato)]ruthenium(II)

Ruthenium(II) Complexes containing pyrimidine‐2‐thiolate (pymS^–) and bis(diphenylphosphanyl)alkanes [Ph₂P–(CH₂)_m–PPh₂, m = 1, dppm; m = 2, dppe; m = 3, dppp; m = 4, dppb] are described. Reactions of [RuCl₂L₂] (L = dppm, dppp) and [Ru₂Cl₄L₃] (L = dppb) with pyrimidine‐2‐thione (pymSH) in 1:2 molar ratio in dry benzene in the presence of Et₃N base yielded the [Ru(pymS)₂L] complexes (pymS^– = pyrimidine‐2‐thiolate; L = dppm ( 1 ); dppp ( 3 ); dppb ( 4 )). The complex [Ru(pymS)₂(dppe)] ( 2 ) was indirectly prepared by the reaction of [Ru(pymS)₂(PPh₃)₂] with dppe. These complexes were characterized using analytical data, IR, ¹H, ¹³C, ³¹P NMR spectroscopy, and X‐ray crystallography (complex 3 ). The crystal structure of the analogous complex [Ru(pyS)₂(dppm)] ( 5 ) with the ligand pyridine‐2‐thiolate (pyS^–) was also described. X‐ray crystallographic investigation of complex 3 has shown two four‐membered chelate rings (N, S donors) and one six‐membered ring (P, P donors) around the metal atom. Compound 5 provides the first example in which Ru^II has three four‐membered chelate rings: two made up by N, S donor ligands and one made up by P, P donor ligand. The arrangement around the metal atoms in each complex is distorted octahedral with cis:cis:trans:P, P:N, N:S, S dispositions of the donor atoms. The ³¹P NMR spectroscopic data revealed that the complexes are static in solution, except 2 , which showed the presence of more than one species.     

Polymeric (O‐ethyl di­thio­carbonato)silver(I)

The title compound, [Ag(C₃H₅OS₂)]_n, is polymeric in the solid state and adopts a layered structure in which each Ag atom is five‐coordinated in a distorted trigonal‐bipyramidal geometry defined by four S atoms belonging to four different xanthate groups and by a neigbouring Ag atom [Ag⃛Ag = 3.0540 (8) Å]. Each S atom is three‐coordinated to one C and two Ag atoms. The structure can be envisaged as being formed by Ag₂(S₂COEt)₂ units in which every S atom is bonded to another Ag atom from a different unit and the Ag atoms are also bonded to two different S atoms of two other units. The result is a two‐dimensional network of condensed metallacycles of six or eight atoms.     

Di­iodo­bis(1‐methyl‐1,3‐imidazolium‐2‐thiol­ato‐S)­mercury(II)

The reaction of 1‐methyl‐1,3‐imidazole‐2‐thione (meimtH) with mercury(II) iodide in methanol in a 2:1 molar ratio resulted in the formation of single crystals of the title compound, [HgI₂(C₄H₆N₂S)₂]. The Hg atom is coordinated by two I [2.7809 (9) and 2.7999 (8) Å] and two thione S atoms [2.520 (3) and 2.576 (3) Å] with irregular tetrahedral coordination geometry. The NH groups of the imidazole ring take part in intra‐ and intermolecular hydrogen bonds with I atoms [N?I 3.596 (8) and 3.611 (9) Å, respectively] joining mol­ecules into infinite chains parallel to the z axis.     

Two isomorphous ZnII/CoII complexes with tri‐tert‐butoxysilanethiol and histamine,and (4‐hydroxymethyl‐1H‐imidazole‐κN)bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II)

The complexes [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], and [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], are isomorphous. The central Zn^II/Co^II ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH₂ groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The Zn^II atom in [(1H‐imidazol‐4‐yl‐κN³)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ²O,S)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₄H₆N₂O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.     

Coordination Mode of the Nickel(II) Cation with N‐Diisopropoxyphosphinyl‐p‐bromothiobenzamide

Reaction of the potassium salt of N‐diisopropoxyphosphinyl‐p‐bromothiobenzamide p‐BrC₆H₄C(S)NHP(O)(OiPr)₂ ( HL ) with Ni(NO₃)₂ in aqueous EtOH leads to complex of formula [Ni(HL‐O)₂(L‐O,S)₂] ( 1 ). The structure of 1 was investigated by single crystal X‐ray diffraction analysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal‐bipyramidal environment, (O^ax)₂(O^eq)₂(S^eq)₂, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5‐O,S‐coordination mode. The chelating ligands are bound in trans configuration.     

2,5‐Bis(2‐(diphenylphosphino)phenyl)‐1,3,4‐oxadiazole ligands and their Cu(I) complexes for Sonogashira coupling reaction

Two diphosphane ligands – 2,5‐bis(2‐(diphenylphosphino)‐5‐R)phenyl)‐1,3,4‐oxadiazole ( L1 , R = H, L2 , R = OMe) and their binuclear complexes, L1Cu and L2Cu , were prepared and characterized. The molecular structures of L1Cu and L2Cu , as perchlorate salts, were established by X‐ray crystallography, which showed them to be binuclear complexes with each Cu atom tetrahedrally coordinated by two P atoms and two N atoms. The ligands and their Cu(I) complexes catalyzed Sonogashira coupling reactions of iodobenzene with phenylacetylene in the presence of K₂CO₃ under Pd‐free conditions. Coupling reactions catalyzed by L1 or L2 with Cu(MeCN)₄ClO₄ in situ exhibited better yields than those by the corresponding Cu(I) complexes L1Cu or L2Cu . Detailed studies showed L1 or L2 with Cu(MeCN)₄ClO₄ to be suitable catalysts for the coupling reaction of terminal alkynes and aryl halides. The coupling reactions of aryl iodides with electron‐withdrawing groups showed better results. Copyright © 2014 John Wiley & Sons, Ltd.     

(4,6‐Dimethyl‐2‐sulfanylidenepyrimidin‐1‐ium) trichlorido(thiourea‐κS)zinc(II)

The title compound, (C₆H₉N₂S)[ZnCl₃{SC(NH₂)₂}], exists as a zincate where the zinc(II) centre is coordinated by three chloride ligands and a thiourea ligand to form the anion. The organic cation adopts the protonated 4,6‐dimethyl‐2‐sulfanylidenepyrimidin‐1‐ium (L) form of 4,6‐dimethylpyrimidine‐2(1H)‐thione. Two short N—H...Cl hydrogen bonds involving the pyrimidine H atoms and the [ZnCl₃L]⁻ anion form a crystallographically centrosymmetric dimeric unit consisting of two anions and two cations. The packing structure is completed by longer‐range hydrogen bonds donated by the thiourea NH₂ groups to chloride ligand hydrogen‐bond acceptors.     

LSb(μ‐I)2(μ‐S)SbL: a Neutral Triply Bridged Complex obtained from Sb Powder and Diiodine activated by Tetraphenyldithioimidodiphosphine (HL)

The synthesis of the complex LSb(μ‐I)₂(μ‐S)SbL ( 1 ) was accomplished by reacting antimony powder with diiodine activated by tetraphenyldithioimidodiphosphine (SPPh₂NHPPh₂S) (H L ). X‐ray diffraction (tetragonal, M = 1426.30, space group I 4₁/a (No. 88), Z = 8, a = 18.020(2) Å, c = 33.037(4) Å) shows that ( 1 ) is a dinuclear Sb^III complex, in which the two metal ions are bridged by one sulphide and two iodide anions. An anionic bidentate L ligand completes the coordination sphere of each metal with its two sulphur atoms, leading to a slightly distorted pyramidal coordination geometry, since each metal ion shows the presence of a sterically active lone‐pair in trans position to the bridging sulphide. ³¹P CP‐MAS NMR and IR spectroscopies are in accordance with the structural features of the complex.     

Synthesis and characterization of crown ether–containing N‐phosphorylated thioureas RC(S)NHP(O)(OiPr)2 (R = 1‐aza‐15‐crown‐5, 1‐aza‐12‐crown‐4) and their Co(II) and Ni(II) complexes

The reaction of the lithium salts of N‐phosphorylated thioureas RC(S)NHP(O)(OiPr)₂ (R = 1‐aza‐15‐crown‐5, HL ^I ; 1‐aza‐12‐crown‐4, HL ^II ) with Co(II) or Ni(II) leads to the chelate complexes [ ML ^I,II ₂ ]. The metal center is found in a tetrahedral ([ CoL ^I,II ₂ ]) or square planar ([ NiL ^I,II ₂ ]) O₂S₂ environment formed by the CS sulfur atoms and the PO oxygen atoms of two deprotonated ligands L . The molecular structure of [ CoL ^I ₂ ] was elucidated by X‐ray diffraction and the extraction properties of HL ^I,II and [ ML ^I,II ₂ ] toward alkali metal and ammonium picrates were investigated. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:486–491, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20637     

N‐Methylimidazolkomplexe des Berylliums: [Be(Me‐Im)4]I2 und [Be3(μ‐OH)3(Me‐Im)6]Cl3

Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)₄]I₂ ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R₁ = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)₄]²⁺ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be₃(μ‐OH)₃(Me‐Im)₆]Cl₃ ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively [ 2a : Space group P2₁/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph₄P)₂[Be₂Cl₆] single crystals of (Ph₄P)Cl·CH₂Cl₂ ( 3 ) were identified crystallographically (P2₁/n, Z = 4) which are isotypical with the corresponding known bromide (Ph₄P)Br·CH₂Cl₂.     

Polymeric di­aqua­tetra‐μ‐thio­cyanato‐manganese(II)­mercury(II) bis(N,N‐di­methyl­acet­amide) solvate

In the title complex, {[MnHg(SCN)₄(H₂O)₂]·2C₄H₉NO}_n, each Mn atom is octahedrally coordinated to four equatorial thio­cyanate N atoms and two axial water O atoms. The Mn atom and two O atoms lie on a twofold axis. Two kinds of crystallographically independent Hg atoms (denoted Hg1 and Hg2) are tetrahedrally coordinated with four thiocyanate S atoms and each Hg atom lies on a axis. N,N‐Di­methyl­acet­amide mol­ecules are connected to coordinated water mol­ecules through hydrogen bonds. Each pair of Mn and Hg atoms is bridged via one thiocyanate ion. An Mn₂Hg1Hg2(SCN)₄ 16‐membered ring is formed as a unit and the four metal atoms are in a chair‐form tetrahedral arrangement. The units are linked with one another and form infinite two‐dimensional networks.     

Poly[bis(μ‐4‐benzoyl‐1‐isonicotinoylthiosemicarbazide‐κ2N:S)dichloridocadmium(II)]

The asymmetric unit of the title complex, [CdCl₂(C₁₄H₁₂N₄O₂S)₂]_n, consists of one Cd^II ion located on the crystallographic inversion centre, one 4‐benzoyl‐1‐isonicotinoylthiosemicarbazide ligand and one chloride ligand. The central Cd^II ion adopts a distorted octahedral coordination geometry formed by two pyridyl N atoms of two ligands, two S atoms of two other ligands and two chloride ligands. The thiosemicarbazide ligands act as bridges, linking the metal ions into a two‐dimensional layered structure parallel to the bc plane. Intermolecular N—H...O hydrogen bonds and C—H...π interactions exist between adjacent layers.     

Three‐dimensional networks in bis(imidazolium) 2,2′‐dithiodibenzoate and 4‐methylimidazolium 2‐[(2‐carboxyphenyl)disulfanyl]benzoate

Cocrystallization of imidazole or 4‐methylimidazole with 2,2′‐dithiodibenzoic acid from methanol solution yields the title 2:1 and 1:1 organic salts, 2C₃H₅N₂⁺·C₁₄H₁₀O₄S₂²⁻, (I), and C₄H₇N₂⁺·C₁₄H₁₀O₄S₂⁻, (II), respectively. Compound (I) crystallizes in the monoclinic C2/c space group with the mid‐point of the S—S bond lying on a twofold axis. The component ions in (I) are linked by intermolecular N—H...O hydrogen bonds to form a two‐dimensional network, which is further linked by C—H...O hydrogen bonds into a three‐dimensional network. In contrast, by means of N—H...O, N—H...S and O—H...O hydrogen bonds, the component ions in (II) are linked into a tape and adjacent tapes are further linked by π–π, C—H...O and C—H...π interactions, resulting in a three‐dimensional network.     

The novel chain‐like anion ∞1[NaMo8O26(mim)2]3− in (Hmim)3[NaMo8O26(mim)2] (mim is 1‐methylimidazole)

Tris(1‐methylimidazolium) bis(1‐methylimidazole)hexacosaoxidooctamolybdatesodium, (C₄H₇N₂)₃[NaMo₈O₂₆(C₄H₆N₂)₂], prepared from an aqueous solution containing Na₂MoO₄ and 1‐methylimidazole, contains the novel chain‐like anion _∞¹[NaMo₈O₂₆(mim)₂]^{3 −} (mim is 1‐methylimidazole). The [Mo₈O₂₆(mim)₂]⁴⁻ building unit, which lies across a center of inversion, is comprised of eight edge‐sharing MoO₆ and MoO₅(N_mim) octahedra. These molybdate units are interlinked by sodium, itself exhibiting a sixfold coordination with O atoms.     

Structural properties of trans‐cyclohexane‐1,2‐diamine complexes of copper(II) and zinc(II) acesulfamates

The title compounds, trans‐bis(trans‐cyclohexane‐1,2‐diamine)bis(6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ido)copper(II), [Cu(C₄H₄NO₄S)₂(C₆H₁₄N₂)₂], (I), and trans‐diaquabis(cyclohexane‐1,2‐diamine)zinc(II) 6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ide dihydrate, [Zn(C₆H₁₄N₂)₂(H₂O)₂](C₄H₄NO₄S)₂·2H₂O, (II), are two‐dimensional hydrogen‐bonded supramolecular complexes. In (I), the Cu^II ion resides on a centre of symmetry in a neutral complex, in a tetragonally distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two N atoms of two acesulfamate ligands. Intermolecular N—H...O and C—H...O hydrogen bonds produce R₂²(12) motif rings which lead to two‐dimensional polymeric networks. In contrast, the Zn^II ion in (II) resides on a centre of symmetry in a complex dication with a less distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two O atoms from aqua ligands. In (II), an extensive two‐dimensional network of N—H...O, O—H...O and C—H...O hydrogen bonds includes R₂¹(6) and R₄⁴(16) motif rings.     

Crystal structure and photoluminescence properties of a new monomeric copper(II) complex: bis(3‐{[(3‐hydroxypropyl)imino]methyl}‐4‐nitrophenolato‐κ3O,N,O′)copper(II)

Copper(II)–Schiff base complexes have attracted extensive interest due to their structural, electronic, magnetic and luminescence properties. The title novel monomeric Cu^II complex, [Cu(C₁₀H₁₁N₂O₄)₂], has been synthesized by the reaction of 3‐{[(3‐hydroxypropyl)imino]methyl}‐4‐nitrophenol (H₂L ) and copper(II) acetate monohydrate in methanol, and was characterized by elemental analysis, UV and IR spectroscopies, single‐crystal X‐ray diffraction analysis and a photoluminescence study. The Cu^II atom is located on a centre of inversion and is coordinated by two imine N atoms, two phenoxy O atoms in a mutual trans disposition and two hydroxy O atoms in axial positions, forming an elongated octahedral geometry. In the crystal, intermolecular O—H…O hydrogen bonds link the molecules to form a one‐dimensional chain structure and π–π contacts also connect the molecules to form a three‐dimensional structure. The solid‐state photoluminescence properties of the complex and free H₂L have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong green emission at 520 nm and H₂L displays a blue emission at 480 nm.     

A three‐dimensional cadmium(II) coordination polymer: poly[[[μ‐4,4′‐(propane‐1,3‐diyl)dipyridine‐κ2N:N](μ‐3,3′‐thiodipropionato‐κ3O,O′:O)cadmium(II)] monohydrate]

In the title coordination polymer, {[Cd(C₆H₈O₄S)(C₁₃H₁₄N₂)]·H₂O}_n, the Cd^II atom displays a distorted octahedral coordination, formed by three carboxylate O atoms and one S atom from three different 3,3′‐thiodipropionate ligands, and two N atoms from two different 4,4′‐(propane‐1,3‐diyl)dipyridine ligands. The Cd^II centres are bridged through carboxylate O atoms of 3,3′‐thiodipropionate ligands and through N atoms of 4,4′‐(propane‐1,3‐diyl)dipyridine ligands to form two different one‐dimensional chains, which intersect to form a two‐dimensional layer. These two‐dimensional layers are linked by S atoms of 3,3′‐thiodipropionate ligands from adjacent layers to form a three‐dimensional network.     

Tris(3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carboxamidato‐κ2N2,N)­cobalt(III)

In the crystal structure of the title complex, [Co(C₆H₈N₃S)₃], the Co^III atom is octahedrally coordinated by three monodeprotonated bidentate 3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carbox­amide ligands with two thio­carbox­amide N atoms in axial positions. The asymmetric unit contains two mol­ecules (A and B) and these mol­ecules are arranged in chains in an alternating fashion connected by N—H⋯S interactions.