Chlorobis[N′‐ethoxycarbonyl‐N‐(4‐methylphenyl)thiourea‐κS]copper(I)

The title complex, chloro­bis{ethyl N‐[(4‐methyl­anilino)­thio­carbonyl]­carbamate‐κS}copper(I), [CuCl(C₁₁H₁₄N₂O₂S)₂], was synthesized by the reaction of cupric chloride with the corresponding thio­urea derivative. The complex has imposed crystallographic m symmetry and the Cu^I coordination environment is trigonal planar, formed by two S atoms and one Cl atom. The formation of intramolecular hydrogen bonds promotes the stability of the complex.     

N‐Ethylpyridinium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)nickelate

The title compound, (C₇H₁₀N)[Ni(C₃S₅)₂] or (Etpy)[Ni(dmit)₂] (where Etpy is the N‐ethyl­pyridinium cation, C₇H₁₀N⁺, and dmit is the 2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ate dianion, C₃S₅²⁻), crystallizes in the P space group with two mol­ecules in the asymmetric unit. The [Ni(dmit)₂]⁻ monoanion has a planar D_2h conformation, with the central Ni atom and the four coordinated S atoms forming an NiS₄ square plane. The six‐membered ring of the Etpy cation also shows good planarity, as expected. There are two main types of disorder in the two Etpy cations. Several short intermolecular interactions are present, such as S⋯S, Ni⋯S and Ni⋯Ni, which help to form the enhanced three‐dimensional structure of the crystal.     

Supramolecular framework in catena‐poly[[(nitrato‐κO)silver(I)]‐μ‐(R,S)‐2‐(pyridin‐4‐ylsulfinyl)pyrimidine‐κ3N,O:N′]

In the title complex, [Ag(NO₃)(C₉H₇N₃OS)]_n, η¹:η¹:η¹:μ₂‐bridging 2‐(pyridin‐4‐ylsulfinyl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag^I cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [01] direction. An FT–IR spectroscopic study shows a decreased stretching frequency for the η¹‐O‐bonded S=O group compared with that of the free ligand. The parallel chains are arranged and interconnected via O(S=O)...π(pyridine/pyrimidine) and C—H(pyridine)...O(NO₃⁻) interactions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO₃⁻)...π(pyrimidine) interactions to form a three‐dimensional supramolecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)...π(pyridine/pyrimidine) and anion(NO₃⁻)...π(pyrimidine) interactions in the supramolecular assembly of the title complex are presented.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

N‐Benzoyl‐N′,N′‐dibutylselenourea and its palladium(II) complex

The crystal and molecular structures of N‐benzoyl‐N′,N′‐dibutylselenourea (HL), C₁₆H₂₄N₂OSe, and the corresponding complex bis(N‐benzoyl‐N′,N′‐dibutylselenoureato‐κ²Se,O)palladium(II), [Pd(C₁₆H₂₃N₂OSe)₂], are reported. The selenourea molecule is characterized by intermolecular hydrogen bonds between the selenoamidic H atom and the Se atom of a neighbouring molecule forming a dimer, presumably as a consequence of resonance‐assisted hydrogen bonding or π‐bonding co‐operativity. A second dimeric hydrogen bond is also described. In the palladium complex, the typical square‐planar coordination characteristic of such ligands results in a cis‐[Pd(L‐Se,O)₂] complex.     

(1R,2S)‐2‐[N‐Methyl‐N‐(4‐toluene­sulfonyl)amino]‐1‐phenylpropan‐1‐ol

In the title compound, C₁₇H₂₁NO₃S, the S atom is in a distorted tetrahedral geometry and the N atom exhibits sp² character. The antiperiplanar conformation is observed for the N and hydroxyl‐O atoms and the torsion angle around the N—C linkage is ?136.3 (2)°. The mol­ecules are linked by O—H?O intermolecular hydrogen bonds to form an infinite one‐dimensional chains along the c axis.     

Bis[μ3‐cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3–)]bis(2,2′‐bipyridine)dichloridotetracopper(II) dihydrate

The title complex, bis[μ₃‐cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3−)]‐1:2:4κ⁷N,N′,N′′,O:O′,O′′:O′′′;2:3:4κ⁷O′′′:N,N′,N′′,O:O′,O′′‐bis(2,2′‐bipyridine)‐2κ²N,N′;4κ²N,N′‐dichlorido‐1κCl,3κCl‐tetracopper(II) dihydrate, [Cu₄(C₁₂H₁₂N₃O₄)₂Cl₂(C₁₀H₈N₂)₂]·2H₂O, consists of a neutral cyclic tetracopper(II) system having an embedded centre of inversion and two solvent water molecules. The coordination of each Cu^II atom is square‐pyramidal. The separations of Cu^II atoms bridged by cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidate(3−) and carboxyl groups are 5.2096 (4) and 5.1961 (5) Å, respectively. A three‐dimensional supramolecular structure involving hydrogen bonding and aromatic stacking is observed.     

Syntheses,Structures, and Properties of the Complexes [Ag(N∧S)n](X), N∧S = 1‐Methyl‐2‐(alkylthiomethyl)‐1H‐benzimidazoles,X = PF6 (n = 2) or PO2F2 (n = 1)

The complexes [Ag(η²‐N∧S)₂](PF₆), N∧S = 1‐methyl‐2‐(methylthiomethyl)‐1H‐benzimidazole, mmb (complex 1 ) or 1‐methyl‐2‐(tert‐butylthiomethyl)‐1H‐benzimidazole, mtb (complex 2 ), and [Ag(μ,η²‐mmb)(μ,η²‐O₂PF₂)] (complex 3 ) were synthesized and characterized by X‐ray crystallography. Long Ag–S (ca. 2.70 Å) and shorter Ag–N bonds (ca. 2.23 Å) are part of characteristically distorted tetrahedral coordination arrangements at the silver(I) ions in 1 and 2 . Unexpectedly, the comparison with the copper analogue [Cu(η²‐mmb)₂](PF₆) reveals a more tetrahedral and less linear coordination arrangement for the corresponding silver species. Compound 3 as obtained by hydrolysis of the PF₆ ion or by the use of AgPO₂F₂ exhibits bridging mmb and η²‐difluorophosphate ligands in a chain‐type structure.     

Poly[bis(N‐methylformamide)tetra‐μ‐thiocyanato‐manganese(II)mercury(II)]

The title complex, [MnHg(NCS)₄(C₂H₅NO)₂]_n, consists of slightly distorted MnN₄O₂ octa­hedra and HgS₄ tetra­hedra. Each Mn^II cation is bound to four N atoms of the NCS groups and two O atoms of the N‐methyl­formamide (NMF) ligands in a cis configuration. Each Hg^II cation is coordinated to four S atoms of NCS groups. Each pair of Mn^II and Hg^II cations is connected by an –NCS– bridge, forming an infinite three‐dimensional –Mn—NCS—Hg– network.     

(N‐{[4‐(1,3‐Benzothiazol‐2‐yl)anilino]carbonylmethyl‐κO}iminodiacetato‐κ3O,N,O′)(1,10‐phenanthroline‐κ2N,N′)cobalt(II) pentahydrate

The title compound, [Co(C₁₉H₁₅N₃O₅S)(C₁₂H₈N₂)]·5H₂O, has a moderately distorted octahedral coordination environment composed of two N atoms of a 1,10‐phenanthroline ligand and one N and three O atoms of an N‐{[4‐(1,3‐benzothiazol‐2‐yl)anilino]carbonylmethyl}iminodiacetate (ZL‐5²⁻) ligand. The ring systems of the phenanthroline and ZL‐5²⁻ ligands are coplanar and the complexes pack in layers parallel to the ab plane with the rings of adjacent complexes facing one another. The layers stack along the c axis and are linked by hydrogen bonds involving the five water solvent molecules in the asymmetric unit and O atoms of the acetate groups of the ZL‐5²⁻ ligand. This is believed to be the first crystal structure of a complex of a 2‐(4‐aminophenyl)benzothiazole ligand.     

catena‐Poly[[[aqua[3‐(2‐pyridylsulfanyl)propionato N‐oxide‐κO1]copper(II)]‐μ‐[3‐(2‐pyridylsulfanyl)propionato N‐oxide‐κ3O3:O1,O1′] dihydrate]

In the title complex, {[Cu(C₈H₈NO₃S)₂(H₂O)]·2H₂O}_n, the Cu^II cation has a distorted square‐pyramidal coordination environment consisting of five O atoms, one from a water molecule, one from an N—O group and the other three from the carboxylate groups of two 3‐(2‐pyridylsulfanyl)propionate N‐oxide anions. The aqua[3‐(2‐pyridylsulfanyl)propionato N‐oxide]copper(II) moieties are bridged by 3‐(2‐pyridylsulfanyl)propionate N‐oxide anions to form an infinite three‐dimensional coordination polymer with a zigzag chain structure. The crystal structure is stabilized by hydrogen bonds.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

The Structure of Bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium in the Solid State and in Solution

The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]₂, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl₂ in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) ų, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc₁^≠) and the energy barrier (δGc₂^≠) were 11.5 ± 0.1 Kcal mol^?1 at 246 K and 9.8 ± 0.1 Kcal mol^?1 at 199 K, respectively, calculated by dynamic NMR data.     

catena‐Poly[tris(ethylenediamine‐κ2N,N′)nickel(II) [[trithiocyanato‐κ3N‐sodium(I)]‐μ‐aqua‐κ2O:O]]

The title complex, {[Ni(C₂H₈N₂)₃][Na(NCS)₃(H₂O)]}_n, con­sists of discrete [Ni(en)₃]²⁺ dications (en is ethyl­enedi­amine) and polymeric [(H₂O)_0.5Na(NCS)₃(H₂O)_0.5]_n^2n? anions. The compound crystallizes in space group Pc1. The Ni^II atom lies on a threefold axis and has a distorted octahedral coordination geometry. The Na⁺ cation also lies on a site with imposed crystallographic threefold symmetry and is coordinated by the thio­cyanate N atoms (the thio­cyanates are in general posi­tions), by one water mol­ecule with crystallographically imposed 32 symmetry and by a second water mol­ecule with crystallographically imposed symmetry. The unique Na atom thus has trigonal–bipyramidal coordination. The O atoms of the water mol­ecules bridge the Na⁺ cations to form one‐dimensional polymeric chains in the crystal structure. The [Ni(en)₃]²⁺ dications are distributed around and between the chains and are linked to them via N—H?S hydrogen bonds.     

Bis­(saccharinato‐κN)zinc(II) com­plexes with N,N′‐bidentate 2‐amino­methyl­pyridine and 2‐amino­ethylpyridine

The structures of trans‐bis[2‐(amino­methyl)­pyridine‐κ²N,N′]­bis­(saccharinato‐κN)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₆H₈N₂)₂], (I), and [2‐(amino­ethyl)­pyridine‐κ²N,N′]bis­(saccharinato‐κN)­zinc(II), [Zn(C₇H₄NO₃S)₂(C₇H₁₀N₂)], (II), exhibit octa‐ and tetrahedrally coordinated Zn^II atoms, respectively. The di­amine ligands behave as N,N′‐bidentate ligands, while saccharinate (sac) is coordinated through the N atom. In (I), the complex lies about an inversion centre with the Zn atom disordered and displaced by 0.256 (2) Å from a centre of symmetry towards a sac N atom. The crystal structure of (I) is stabilized by N—H⋯O hydrogen bonds and the crystal packing of (II) is determined by hydrogen bonding as well as weak π–π stacking interactions between the sac ligands.     

μ‐{N,N′‐Bis[2‐(dimethyl­amino)ethyl]oxamidato(2–)}‐1κ2O,O′:2κ4N,N′,N′′,N′′′‐bis­(4,4′‐dimethyl‐2,2′‐bipyridine‐1κ2N,N′)dinickel(II) bis­(perchlorate)

In the crystal structure of the title complex, [Ni₂(C₁₀H₂₀N₄O₂)(C₁₂H₁₂N₂)₂](ClO₄)₂ or [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ {H₂dmaeoxd is N,N′‐bis­[2‐(dimethyl­amino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd²⁻ ligand is in a cis conformation and bridges two Ni^II atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd²⁻ ligands inter­act with each other via C—H⋯O hydrogen bonds and π–π inter­actions, which results in an extended chain along the c axis.     

Cobalt(II) Complexes with N‐Thioacylamidophosphates and 2,2′‐Bipyridyl and 1,10‐Phenathroline. Crystal Structures,Solution 1H NMR Spectral and Magnetic Properties

Structure and magnetic properties of N‐diisopropoxyphosphorylthiobenzamide PhC(S)‐N(H)‐P(O)(OiPr)₂ ( HL^I ) and N‐diisopropoxyphosphoryl‐N′‐phenylthiocarbamide PhN(H)‐C(S)‐N(H)‐P(O)(OiPr)₂ ( HL^II ) complexes with the Co^II cation of formulas [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂] ( 1 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂] ( 2 ), [Co{PhC(S)‐N(H)‐P(O)(OiPr)₂}₂{PhC(S)‐N‐P(O)(OiPr)₂}₂] ( 1a ) and [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂}(2,2′‐bipy)] ( 3 ), [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂(1,10‐phen)] ( 4 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂(2,2′‐bipy)] ( 5 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂(1,10‐phen)] ( 6 ) were investigated. Paramagnetic shifts in the ¹H NMR spectrum were observed for high‐spin Co^II complexes with HL^I,II , incorporating the S‐C‐N‐P‐O chelate moiety and two aromatic chelate ligands. Investigation of the thermal dependence of the magnetic susceptibility has shown that the extended materials 1‐2 and 6 show ferromagnetic exchange between distorted tetrahedral ( 1 , 2 ) or octahedral ( 1a , 6 ) metal atoms whereas 3 and 5 show antiferromagnetic properties. Compound 4 behaves as a spin‐canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, T_c = 115 K. Complexes 1 and 1a were investigated by single crystal X‐ray diffraction. The cobalt(II) atom in complex 1 resides a distorted tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex 1a has a tetragonal‐bipyramidal structure, Co(O^ax)₂(O^eq)₂(S^eq)₂, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in the typical 1,5‐O,S coordination mode. The ligands are in a trans configuration.     

catena‐Poly[[(2,2′‐diamino‐4,4′‐bithiazole){μ3‐cis‐N‐(2‐carboxylatophenyl)‐N′‐[3‐(dimethylamino)propyl]oxamidato(3−)}dicopper(II)] nitrate 0.6‐hydrate]

The title complex, {[Cu₂(C₁₄H₁₆N₃O₄)(C₆H₆N₄S₂)]NO₃·0.6H₂O}_n, is a one‐dimensional copper(II) coordination polymer bridged by cis‐oxamide and carboxylate groups. The asymmetric unit is composed of a dinuclear copper(II) cation, [Cu₂(dmapob)(dabt)]⁺ {dmapob is N‐(2‐carboxylatophenyl)‐N′‐[3‐(dimethylamino)propyl]oxamidate and dabt is 2,2′‐diamino‐4,4′‐bithiazole}, one nitrate anion and one partially occupied site for a solvent water molecule. The two Cu^II ions are located in square‐planar and square‐pyramidal coordination environments, respectively. The separations of the Cu atoms bridged by oxamide and carboxylate groups are 5.2053 (3) and 5.0971 (4) Å, respectively. The complex chains are linked by classical hydrogen bonds to form a layer and then assembled by π–π stacking interactions into a three‐dimensional network. The influence of the terminal ligand on the structure of the complex is discussed.     

[μ3‐cis‐N‐(2‐Aminoethyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3−)]bis(2,2′‐diamino‐4,4′‐bi‐1,3‐thiazole)tetracopper(II) bis(2,4,6‐trinitrophenolate)

The title complex, [Cu₄(C₁₁H₁₀N₃O₄)₂(C₆H₆N₄S₂)₂](C₆H₂N₃O₇)₂, consists of a circular tetracopper(II) cation with an embedded inversion centre and two uncoordinated picrate (2,4,6‐trinitrophenolate) anions. The Cu^II cations at the inner sites of N‐(2‐aminoethyl)‐N′‐(2‐carboxylatophenyl)oxamidate(3−) (oxbe) have square‐planar environments and those at the outer sites are in square‐pyramidal geometries. The separations of pairs of Cu^II cations bridged by cis‐oxamide and carboxylate groups are 5.2217 (5) and 5.2871 (5) Å, respectively. The tetracopper(II) cations and picrate anions are connected by N—H...O hydrogen bonds into a two‐dimensional network parallel to the (010) plane, and these two‐dimensional networks are assembled by two types of π–π stacking interactions into a three‐dimensional supramolecular structure.     

[N,N′‐Bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]­nickel(II) and [N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]copper(II)

In the title compounds, {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}nickel(II), [Ni(C₁₉H₂₀N₂O₂)], and {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}copper(II), [Cu(C₁₉H₂₀N₂O₂)], the Ni^II and Cu^II atoms are coordinated by two iminic N and two phenolic O atoms of the N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminate (SALPD^2?, C₁₇H₁₆N₂O₂^2?) ligand. The geometry of the coordination sphere is planar in the case of the Ni^II complex and distorted towards tetrahedral for the Cu^II complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20 (6) and 35.13 (7)°, respectively.