Synthesis and characterization of bis(<Emphasis Type="Italic">O,O</Emphasis>′-diisopropylmonothiophosphato)nickel(II) adducts and molecular structures of bis(pyridine)bis(<Emphasis Type="Italic">O,O</Emphasis>′-diisopropylmonothiophosphato)nickel(II) complex

The present work demonstrates the synthesis and characterization of adducts with bis(O,O′-diisopropylmonothiophosphato)nickel(II) complex, Ni{S(O)P(OⁱPr)₂}₂(L) _n (n = 2, L = pyridine, 2-picoline, 3-picoline; n = 1, L = 2,2′-bipyridyl and 1,10-phenanthroline). The crystallographic investigation of Ni{S(O)P(OⁱPr)₂}₂(C₅H₅N)₂ reveals distorted octahedral geometry around the central nickel(II) atom. The monothiophosphate moieties show anisobidentate coordination to the central metal, while the pyridine ligands are in cis positions. These nickel(II) adducts were characterized by elemental analysis, a range of spectroscopic techniques, and magnetic susceptibility measurement.     

Nitrogen-donor base adducts of bis(O,O′-di-isoamyldithiophosphato)nickel(II)

A series of Ni^II complexes with the O,O-di-isoamylester of dithiophosphoric acid and nitrogen-donor ligands of composition [Ni(i-Am₂dtp)₂(L)]; [dtp = O₂PS₂ ^–; L = 2,2-bipyridine (bpy); 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (nphen); 4,7-diphenyl-1,10-phenanthroline (baphen); 2,9-dimethyl-1,10-phenanthroline (neo), 2-aminomethylpyridine (amp), 2-(2-aminoethyl)pyridine (aep), 2,2-dipiridylamine (dpa), 1,2-diaminopropane (1,2-dap) or trans 1,2-diaminocyclohexane (dch)] have been prepared. The compounds have been characterized by elemental analyses (C,H,N,S), electronic and i.r. spectroscopy, magnetic and conductivity measurements and by cyclic voltammetry. The results show that all complexes behave as non-electrolytes in acetone. Electronic spectra and magnetic moments suggest a distorted cis-octahedral geometry around the Ni^II atom [_eff/_B <3.10, 3.40 >], except for [Ni(i-Am₂dtp)₂(aep)], where the measured temperature dependence of the magnetic susceptibility proved the tetrahedrally coordinated nickel [4.06 _eff/_B (298 K) – 3.20 _eff/_B (80 K)]. In the [Ni(i-Am₂dtp)₂(neo)] complex, the nickel atom is penta-coordinated. The X-ray crystal and molecular structure of [Ni(i-Am₂dtp)₂(1,2-dap)] has been determined.     

Syntheses and crystal structures of (18-crown-6)bis(perchlorato-O,O′)strontium and (18-crown-6)bis(perchlorato-O,O′)barium

Two complexes, namely, (18-crown-6)bis(perchlorato-O,O′)strontium (I) and (18-crown-6)bis(perchlorato-O,O′)barium (II), are synthesized. Their crystal structures are determined by X-ray diffraction analysis. The structures of I (space group P2₁/c, a = 15.266 Å, b = 11.080 Å, c = 13.235 Å, β = 109.20°, Z = 4) and II (space group P2₁/n, a = 8.330 Å, b = 11.202 Å, c = 11.752 Å, β = 98.38°, Z = 2) are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.077 (I) and 0.041 (II) against 3714 (I) and 2478 (II) independent reflections (CAD-4 diffractometer, λMoK _α radiation). Complex molecules [Sr(18C6)(ClO₄)₂] in the structure of I and [Ba(18C6)(ClO₄)₂] in II (in the inversion center)—are of the host-guest type. The Sr²⁺ or Ba²⁺ cation is localized in the center of a cavity of the 18-crown-6 ligand and coordinated by its all six O atoms. In compounds I and II, the coordination polyhedron of the Sr²⁺ and Ba²⁺ cations (coordination number 10) can be described as a distorted hexagonal bipyramid with two bifurcated vertices at two O atoms of two ClO ₄ ^? ligands, which are disordered in I and II and each of them has two orientations.     

Crystal structure of bis[Ba(Aet)(OH2)5]bis(Aet)·4H2O

An X-ray crystallographic study is conducted of single crystals with the composition [Ba₂(Aet^?)₂·10(H₂O)]²⁺·2(Aet^?)·4H₂O, where Aet^? = (C₁₀H₁₁N₄O₂S₂)^? is the ethazole (2-(para-aminobenzenesulfamido)-5-ethyl-1,3,4-tiadiazole) anion. The crystals are monoclinic; the space group is P2₁/c, Z = 2; a = 9.793(2) Å, b = 15.408(4) Å, and c = 22.553(6) Å; β = 94.98(2)°; and R = 0.047. The independent part of the compound’s structural formula, [Ba(Aet)(OH₂)₅](Aet)·2H₂O, is isostructural with the analogous compound with the Sr atom. The ethazole anion is coordinated to the complexing metal atom by oxygen and nitrogen atoms to form a four-membered ring.     

Preparation and crystal structure of bis[(dibenzo-18-crown-6)potassium]bis(μ<Subscript>2</Subscript>-chloro)-tetrachlorodicuprate(II)

A new complex compound bis[(dibenzo-18-crown-6)potassium]bis(μ₂-chloro)-tetrachlorodicuprate( II), {[K(Db18c6)]₂Cu₂Cl₆} (I) was prepared and its crystal structure was investigated by XRD analysis. Complex molecule I consist of anion [Cu₂Cl₆]²⁻ located in a crystallographic center of inversion, and two centrosymmetrical to each other complex cations [K(Db18c6)]⁺ of “guest-host” type: the cation K⁺ is located in the cavity of the crown-ligand Db18c6 and is coordinated by all its six O atoms, and also by one Cl atom of anion [Cu₂Cl₆]²⁻. The coordination of this cation K⁺ is enlarged up to hexagonal-bipyramidal due to the formation of unusual coordination bond K⁺ → π(      

Gas-phase electronic absorption spectroscopy of substituted bis(η<Superscript>6</Superscript>-benzene)chromium derivatives: Rydberg transitions in bis(η<Superscript>6</Superscript>-anisole)chromium and bis(η<Superscript>6</Superscript>-2,6-dimethylpyridine)chromium

Gas-phase electronic absorption spectra of chromium bisarene complexes with oxygen- and nitrogen-containing ligands, (⁶-PhOMe)₂Cr (1) and (⁶-2,6-Me₂C₅H₃N)₂Cr (2), were first measured. Rydberg bands disappearing on going to the condensed-phase spectra were revealed. The first ionization potentials of complexes 1 and 2 (5.30 and 5.40 eV, respectively) were determined from the Rydberg frequencies. The Rydberg transitions were assigned and the corresponding Rydberg term values and quantum defects were determined. The effect of heteroatoms on the Rydberg structure parameters was revealed by comparing the spectra of complexes 1 and 2 with those of unsubstituted analogs. The appearance, in the ligand side chain, of an oxygen atom capable of being involved in conjugation with the -electron system of the aromatic ring results in substantial broadening of the observed Rydberg bands. This can be associated with an increased ligand contribution to the HOMO of the sandwich compound. The influence of the oxygen atom on the ionization energy of the molecule is insignificant. In contrast to this, introduction of a nitrogen atom into the carbocycle leads to a noticeable increase in the ionization potential of the molecule, while the ligand contribution to the HOMO of the complex remains practically unchanged.Based on materials of a lecture presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1854–1859, September, 2004.     

Synthesis and structure of (C=O→Si←O′=C′)bis(2-methyl-4-oxopyran-3-yloxy)difluoro-(λ<Superscript>6</Superscript>)siliconium

A new six-coordinate silicon compound, (C=O→Si←O′=C′)bis(2-methyl-4-oxopyran-3-yloxy)-difluoro(λ⁶)siliconium, containing two five-membered rings closed by C=O→Si coordination bonds, forms o protodesilylation trifluoro(phenyl)silane with 3-hydroxy-2-methylpyran-4-one (maltol). According to multinuclear NMR and IR spectral data and quantum-chemical calculations, the silicon atom in this compound has an octahedral environment with two cis-arranged C=O→Si bonds     

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) bis -( O,O ′-alkylene dithiophosphates): synthesis and characterization

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) alkylene dithiophosphates, (M = Nb(V) or Ta(V); G =–CHMeCHMe–,–CMe₂CMe₂–,–CH₂CMe₂CH₂–,–CH₂CEt₂CH₂–or–CMe₂CH₂CHMe–and X = Cl or OPrⁱ) have been synthesized by reaction of metal(V) chloride, MCl₅, or triisopropoxymetal(V) dichloride, (PrⁱO)₃MCl₂, with the sodium salts of O,O′-alkylene dithiophosphoric acids, in 1 : 2 molar ratio in THF under anhydrous conditions. These pink-purple or light-yellow compounds are viscous, semi-solid or solid, hydrolyzable and soluble in common organic solvents. These compounds have been characterized by elemental analyses, molecular weight determinations and spectral studies like IR and heteronuclear NMR (¹H, ¹³C and ³¹P), which indicated a bidentate mode of chelation of dithio ligands, leading to a pentagonal bipyramidal geometry around the niobium(V) or tantalum(V) centers.     

Synthesis and characterization of nitrogen-containing Lewis base adducts of bis(O,O′-dialkylmonoselenophosphato)cobalt(II) complexes

The adducts of bis(O,O′-dialkylmonoselenophosphato)cobalt(II) complexes, Co{O(Se)P(OR)₂}₂(L)₄ (where R?=?n-Pr, i-Pr; L?=?C₅H₅N, NC₅H₄Me-2, NC₅H₄Me-3), were synthesized by in situ reactions of CoCl₂?·?6H₂O, Lewis base, and NaO(Se)P(OR)₂. The single crystal structure of Co{O(Se)P(OⁱPr)₂}₂(C₅H₅N)₄ shows distorted octahedral geometry around cobalt(II) and monoselenophosphates are trans. The CoN₄ forms a square plane. These bis(O,O′-dialkylmonoselenophosphato)cobalt(II) adducts were characterized by elemental analyses, spectroscopic techniques (UV-Vis, infrared, ¹H and ³¹P), and magnetic moment measurements.     

Structure and Properties Characteristic of Dimeric Silver(I) Complex: Dinuclear Bis(O,O′-Diphenyldithiophosphato)bis(1,10-phenanthroline) Ag(I)

The complex bis(O,O-diphenyldithiophosphato)bis(1,10-phenanthroline) silver(I), Ag₂[(PhO)₂PS₂]₂(Phen)₂, has been synthesized and structurally characterized. Its crystal structure has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with unit cell parameters a = 11.140(2) Å, b = 10.044(2) Å, c = 23.006(6) Å, = 113.36(3)° V = 2363.1(9) ų, _calcd = 1.600 g/cm³, and Z = 4 for R ₁ = 0.0961. The coordination geometry of each Ag atom, by two N atoms from 1,10-phenanthroline ligand and by two S atoms from two O,O-diphenyldithio phosphate anions, is that of a tetrahedron. The two diphenyldithiophosphato ligands each bridge two silver atoms to form an eight-membered Ag₂S₄P₂ ring, while the 1,10-phenanthroline molecule coordinates to a silver atom to complete the local tetrahedral geometry. The Ag···Ag separation is 3.185(2) Å. The data of elemental analysis, IR and UV-vis spectroscopies are in good agreement with the crystal structure. The thermal gravimetry data indicate that there are two decomposition steps with one intense endothermical peak and one weak exothermical peak. The final product of the thermal decomposition is AgS.     

Cyclic bis(β-diketonate)- and bis(β-ketoesterate)-bridged titanium and zirconium alkoxide derivatives

Reaction of Ti(OiPr)(4) with various bis(β-diketones) and bis(β-ketoesters) (LH(2)) results in the formation of dimeric complexes [Ti(OiPr)(2)L](2), where each metal centre is coordinated by two terminal OiPr ligands and two bridging β-diketonate or β-ketoesterate groups (L). Macrocycles containing two M(OiPr)(2) moieties are thus formed. Reaction of Zr(OiPr)(4) with the same bis(β-diketones) and bis(β-ketoesters) results in different compounds, depending on the organic spacer connecting the two functional groups. With shorter spacers, the compounds [ZrL(OiPr)(2)](2)·2iPrOH are obtained, with the same structures as the corresponding titanium complexes. With longer spacers, however, complexes with a higher degree of substitution are formed, such as (ZrL(2))(2) and Zr(2)L(3)(OiPr)(2)·2iPrOH. The molecular weight and structure of all compounds was elucidated by ESI-MS. MS/MS of the corresponding [M+Na](+) precursor ions confirmed the proposed structures based on structure-specific product ions. Solution NMR experiments and DFT calculations additionally supported the proposed structures.     

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I) and bis(4‐picoline‐κN)gold(I) dichloridoaurate(I): space‐group ambiguity?

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I), [Au(C₆H₇N)₂][AuBr₂], (I), crystallizes in the monoclinic space group P2₁/n, with two half cations and one general anion in the asymmetric unit. The cations, located on centres of inversion, assemble to form chains parallel to the a axis, but there are no significant contacts between the cations. Cohesion is provided by flanking anions, which are connected to the cations by short Au...Au contacts and C—H...Br hydrogen bonds, and to each other by Br...Br contacts. The corresponding chloride derivative, [Au(C₆H₇N)₂][AuCl₂], (II), is isotypic. A previous structure determination of (II), reported in the space group P with very similar axis lengths to those of (I) [Lin et al. (2008). Inorg. Chem. 47 , 2543–2551], might be identical to the structure presented here, except that its γ angle of 88.79 (7)° seems to rule out a monoclinic cell. No phase transformation of (II) could be detected on the basis of data sets recorded at 100, 200 and 295 K.     

Synthesis and structure of diamine bis(phenolate) complexes containing the Ti(OEt)–O–Ti(OEt) function

Reaction of diamine-bis(phenol) ligands containing a mixture of N-methyl and N,N′-dimethyl-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine, H₂L¹ and H₂L³, with [Ti(OCHMe₂)₄ in absolute ethanol under reflux without exclusion of air and moisture gives [(L¹)Ti (OEt–O–Ti(OEt)(L¹)] (1). [(L³)Ti(OEt)–O–Ti(OEt)(L³)] (2) forms when the remaining solution containing [(L³)Ti(OEt)₂] (3) (characterised by X-ray crystallography) is hydrolysed with H₂O. For the N-methyl and N,N′-dimethyl ligand mixture H₂L² and H₂L⁴, which contain tert-butyl groups on the ortho-positions of the aryl rings, [(L²)Ti(OEt)–O–Ti(OEt)(L²)] (4) forms much more slowly and [(L⁴)Ti(OEt)₂] (5) does not hydrolyse when H₂O is added. When the N-protonated ligand N,N-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁵, is used, rapid hydrolysis to two isomers of [(L⁵)Ti(OEt–O–Ti(OEt)(L⁵)] (6) occurs without addition of water. For N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethylenediamine, H₂L⁶, hydrolysis to [(L⁶)Ti(OEt)–O–Ti(OEt)(L⁶)] (7) occurs slowly when H₂O is added. For pendant NMe₂ ligand N,N-dimethyl-N′,N′-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁷, the hydrolysis reaction readily gives [(L⁷)Ti(OEt)–O–Ti(OEt)(L⁷)] (8) for which an X-ray crystal structure was obtained. The ortho-tert-butyl ligand derivative H₂L⁸ formed a complex analysing as [(L⁸)Ti(OEt)–O–Ti(OEt)(L⁸)] (9) which could not be studied further due to insolubility. Pendant pyridine ligand N-(2-pyridylmethyl)-N,N-bis(2′-hydroxy-3′-methyl-5′-tert-butylbenzyl)amine, H₂L⁹, apparently forms isomers of [(L⁹)Ti(OEt)–O–Ti(OEt)(L⁹)] and possibly [{(L⁹)Ti(O)}₂] from [(L⁹)Ti(OEt)₂] (10). The ortho-tert-butyl ligand derivative H₂L¹⁰ formed [(L¹⁰)Ti(OEt)–O–Ti(OEt)(L¹⁰)] (11) for which an X-ray crystal structure was obtained.     

Structures of bis(2-thiobarbiturato-O)tetraaquamagnesium and catena-[(μ2-2-thiobarbiturato-O,O)(2-thiobarbiturato-O) bis(μ2-aqua)diaquastrontium] monohydrate

The crystal structures of bis(2-thiobarbiturato-O)tetraaquamagnesium Mg(H₂O)₄(HTBA-O)₂ I and catena-[(μ₂-2-thiobarbiturato-O,O)(2-thiobarbiturato-O)bis(μ₂-aqua)diaquastrontium] monohydrate catena-[Sr(μ₂-H₂O)₂(H₂O)₂(μ₂-HTBA-O,O)(HBTA-O)] _n · nH₂O (II), where H₂TBA is 2-thiobarbituric acid C₄H₄N₂O₂S, have been determined. Crystal data for a=6.7598(2) Å, b = 7.6060(2) Å, c = 8.5797(2) Å, α = 79.822(2)°, β = 76.622(1)°, γ = 69.124(1)°, V = 398.82(2) ų, space group P $\bar 1$ , Z = 1; for II: a = 20.8499(4) Å, b = 19.2649(5) Å, c = 4.14007(9) Å, β = 92.023(2)°, V = 1661.91(7) ų, space group P2₁/n, Z = 4. The Mg²⁺ ion in I is bonded to six O atoms of two HTBA^? ions and four water molecules that form a nearly regular octahedron. Each Sr²⁺ ion in II is coordinated to three oxygen atoms of three HTBA^? ions and six water molecules that form an almost ideal tricapped trigonal prism. These polyhedra share edges to form infinite chains. Intermolecular hydrogen bonds create layered structures of I and II.     

Crystal structure of bis(α,α′-dithio-bis(formamidinium)) bis(μ2-chloro)hexachlorodimercurate(II)

The crystal and molecular structure of bis(α,α′-dithio-bis(formamidinium)) bis(μ₂-chloro)hexachlorodimercurate(II) C₄H₁₆Hg₂Cl₈N₈S₄ (I), where α,α′-dithio-bis(formamidine) is C₂H₆N₄S₂, was solved. Crystals are monoclinic, a = 8.6417(6) Å, b = 14.648(1) Å, c = 10.2111(8) Å, β = 104.949(1)°, V = 1248.8(2) ų, space group P2₁/n, Z = 4. The crystal structure is built of HgCl ₄ ^2? ions linked via inversion centers into [Hg₂Cl₈]^4? pairs and C₂H₈N₄S ₂ ²⁺ cations. [Hg₂Cl₈]^4? anions and C₂H₈N₄S ₂ ²⁺ cations form alternating layers linked by N-H…Cl hydrogen bonds into a framework structure.     

Synthesis,spectral characterization,and evaluation of antimicrobial activity of O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and zinc bis(O,O′-alkanediyl) dithiophosphates

The synthesis of novel dithiophosphate derivatives has been achieved. Two O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and two Zinc bis(O,O′-alkanediyl) dithiophosphates are synthesized by an easy and facile chemical synthetic route. Zinc bis[O,O′-(2-methylpentane-2,4-diyl) dithiophosphate] L¹, Zinc bis[O,O′-(2-ethylhexane-1,3-diyl) dithiophosphate] L², O,O′-(2-methylpentane-2,4-diyl) S-(N-phthalimidomethyl) dithiophosphate L³ and O,O′-(2-ethylhexane-1,3-diyl) S-(N-phthalimidomethyl) dithiophosphate L⁴ are synthesized from the respective ammonium salts. Compounds L¹, L², L³, and L⁴ are characterized by (CHN) elemental analysis, ESI mass, FT-IR, ¹H, ¹³C, and ³¹P NMR techniques. The crystal structure of ammonium O,O′-(2-methylpentane-2,4-diyl) dithiophosphate is discussed. L¹, L², L³, and L⁴ were evaluated for antimicrobial activity. It was found that the phthalimide derivatives L³ and L⁴ showed much better antifungal potential against some species of fungus. The Zinc dithiophosphates L¹ and L² showed good antibacterial activity against Bacillus cereus and Escherichia coli.     

Synthesis,properties, and crystal structure of diphenylguanidinium bis(citrato)germanate hydrate (HDphg)<Subscript>2</Subscript>[Ge(HCit)<Subscript>2</Subscript>] · 1.08H<Subscript>2</Subscript>O

Diphenylguanidinium bis(citrato)germanate hydrate (HDphg)₂[Ge(HCit)₂] · 1.08H₂O (I) was prepared for the first time (H₄Cit is citric acid, Dphg is diphenylguanidine). The composition of I was determined using elemental analysis and thermogravimetry; the coordination sites of H₄Cit and the protonation sites of Dphg were identified by IR spectroscopy. Compound I was studied by X-ray diffraction. The crystals are monoclinic, a = 11.179(2) Å, b = 7.6081(15) Å, c = 23.529(5) Å, β = 95.38(3)°, V = 1992.3(7) ų, Z = 2, space group P2₁/c, R = 0.0339 for 2498 reflections with I>2σ(I). In the [Ge(HCit)₂]^2? complex anion, the Ge atom is bond to a distorted octahedral array of six O atoms of the two tridentate chelating HCit^3? ligands (Ge-O, 1.8045–1.9555 Å). In the crystal of I, the anions and cations are combined into layers by a system of hydrogen bonds.     

Bis(1,8-naphthylimides) and bis(1′,8′-naphthoylene-1,2-benzimidazoles) based on new bis(naphthalic anhydrides)

The reaction of bis(naphthalic anhydrides) with aniline and o-phenylenediamine under conditions of hightemperature cyclocondensation in m-cresol in the presence of a catalyst (benzoic acid) gives bis(1,8-naphthylimides) and bis(1,8-naphthoylene-1,2-benzimidazoles) which model the elementary units of polyimides and polynaphthoylenebenzimidazoles, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 649–652, May, 1991.     

Synthesis,Crystal, and Molecular Structure of bis(Thiosemicarbazide)Nickel(II) 1,5-Naphthalene Disulfonate Dihydrate Complex [Ni(Tsc)<Subscript>2</Subscript>](1,5-Nds) · 2H<Subscript>2</Subscript>O

Complex [Ni(Tsc)₂](1.5-Nds) · 2H₂O (I), where Tsc = thiosemicarbazide, NH₂NHC(=S)NH₂; 1,5-Nds^2– is double deprotonated anion of 1,5-naphthalene disulfonic acid \(\rm{CH_{10}H_6(SO_3)_2^{2-}}\) was synthesized, characterized by IR spectroscopy, and studied by thermogravimetry and X-ray diffraction. Crystal I is built of complex cations [Ni(Tsc)₂]²⁺, anions (Nds)^2–, and crystallization water molecules. The Ni atom is coordinated along the vertices of the trans-square by two sulfur atoms and two nitrogen atoms of two bidentate chelating ligands Tsc. The structural units of crystal I are joined by a branched network of N–H···O and O–H···O hydrogen bonds with the participation of donors, namely, the hydrogen atoms of two NH₂ groups and the NH group of complex cation [Cu(Tsc)]²⁺ and the H atoms of water molecules, and acceptors, namely, oxygen atoms of the sulfate group of anion 1,5-Nds^2– and solvate water molecules.