Synthesis and Crystal Structure of Bis-{N-[2-(6-ethylpyridyl)]-salicylideneiminato} Cobalt(Ⅱ)

1 INTRODUCTION The Schiff bases derived from salicylaldehyde and 2-aminopyridine derivatives have been used as potentially terdentate ligands[1]. Yamada and Yam- anouchi have synthesized the type of ML2nH2O complexes (M = CoⅡ, NiⅡ, CuⅡ, ZnⅡ or PdⅡ)[     

Direct Synthesis of a Dimeric Mixed-Anions Bismuth(III) Complex: Synthesis and Structural Characterization of [Bi2(Phen)4(No3)4.4I0.6]I3 (A New Dimeric Compound)

A direct synthetic method of mixing Bi(NO₃)₃ and NaI with 1,10-phenanthroline yielded red crystals of [Bi₂(phen)₄(NO₃)_4.4I_0.6]I₃. In this complex the cationic part is in fact binuclear and contains two [Bi(phen)(NO₃)_1.7I_0.3] groups linked via a bridging NO^? ₃ anion. The I^? ₃ anion was not coordinated to bismuth(III) and the lone pair of valence electrons of the bismuth(III) ions appears to be stereochemically inactive. There are two independent NO^? ₃ anions, one coordinated to bismuth but another shares a position with I^? anion. The final results of crystallography show that 40% of these positions are occupied by NO^? ₃ anions and 60% by I^? anions that are coordinated to bismuth atom in bidentate fashion (NO^? ₃) and in unidentate fashion (I^?). An interesting point is that the I^? ₃ anion was produced by direct synthetic method (Branched tube method). There is a π-π stacking interaction between the parallel aromatic rings around the Bi(III) ion.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-(PNP)[TcCl4(Py)2] und trans-(PNP)[TcBr4(Py)2]

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl₄(Py)₂] and trans-(PNP)[TcBr₄(Py)₂] By reaction of (PNP)₂[TcX₆] with pyridine in the presence of [BH₄]^? (PNP)[TcX₄(Py)₂], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic Tc^III complexes (monoclinic, space group P2₁/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D_2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants f_d(TcCl) = 1.45, f_d(TcBr) = 1.035, f_d(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse der bindungsisomeren Chlororhodanoiridate(III) trans-[IrCl2(SCN)4]3− und trans-[IrCl2(NCS)(SCN)3]3−

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? By treatment of Na₂[IrCl₆] with NaSCN in 2N HCl the linkage isomers trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu₄N)₃[IrCl₂(SCN)₄] ( 1 ) (monoclinic, space group P2₁/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me₄N)₃[IrCl₂(NCS)(SCN)₃] ( 2 ) (monoclinic, space group P2₁/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are f_d(IrS) = 1.52 and f_d(IrCl) = 1.72 mdyn/Å.     

High Intensity Trip-Multiplet Transitions,a Reality! Synthesis,Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Dibromophthalocyaninato(2–)molybdate(III)

Oxophthalocyaninato(2–)molybdenum(IV), activated by bromine oxidation prior to use, reacts with fused triphenylphosphine in the presence of bis(triphenylphosphine)iminium bromide to yield linear-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2–)molybdate(III), ^l(PNP)^trans[Mo(Br)₂pc^2?]. It crystallizes triclinic with crystal data: a = 10.506(1) Å, b = 12.436(2) Å, c = 12.918(2) Å, α = 76.186(1)°, β = 67.890(1)°, γ = 68.689(1)°; space group P1 (No. 2); Z = 1. Mo^III is in a pseudo-octahedral coordination geometry with the bromo ligands in trans-arrangement. The Mo? N_p and Mo? Br distance is 2.043(10) and 2.588(1) Å, respectively. The PNP cation adopts a linear conformation. In the IR spectrum v_as(Mo? Br) is observed at 218 cm^?1 and v_as(P? N) of the linear (P? N? P) core at 1406 cm^?1. Cyclic and differential-pulse voltammetry show two quasi-reversible cathodic processes at ?1.15 and ?0.53 V vs. Ag/AgCl. The first is assigned to a phthalocyaninate directed reduction (pc^2?/pc^3?), while the latter arises from a Mo directed reduction (Mo^III/Mo^II). Spectral monitoring confirms the reversible Mo^III/Mo^II reduction. Two quasi-reversible anodic processes at 0.60 and 1.27 V are assigned to the successive Mo directed oxidation with redox couples Mo^III/Mo^IV and Mo^IV/Mo^V. For the first time, three very intense spin-allowed trip-quartet transitions are observed in the electronic absorption spectra at 7140 (TQI), 16890 (TQ2) and 18700 cm^?1 (TQ3) together with a sing-quartet transition at 15850 cm^?1 and characteristic ?Q”? region with maximum at 28500 cm^?1 and ?N”? region at 37400 cm^?1. All electronic excitations are of comparable intensity. A prominent low temperature emission at 6690 cm^?1 is assigned to a spin-forbidden trip-sextet.     

Synthesis,Characterization and Crystal Structure of a Nickel(II) Schiff Base Complex Derived from Acetylacetone and Ethylenediamine

The square-planar nickel (II) complex of composition [Ni(bae)]·½H₂O (1) [where H₂bae is bis(acetylacetone)ethylenediamine] has been synthesized by [2 + 1] template condensation of acetylacetone and ethylenediamine in the presence of NiCl₂·6H₂O and characterized. An X-ray structure determination of the complex has been completed. Average Ni-N and Ni-O distances are, respectively, 1.86(2) Å and 1.849(14) Å. N···N bite distance and bite angle are 2.627(6) Å and 87.2(2)°, respectively, for the five-membered chelate ring. The water molecule forms hydrogen bonds with O atoms of two complex molecules.     

[Li(12-Krone-4){(Me3Si)2N}2TiCH2SiMe2NSiMe3] – ein Ionenpaar mit gestreckter Li–C–Ti-Achse

[Li(12-Crown-4){(Me₃Si)₂N}₂TiCH₂SiMe₂NSiMe₃] – an Ion-Pair with a Linear Li–C–Ti-Axis The title compound ( 1 ) has been prepared from Ti[N(SiMe₃)₂]₃ and n-butyllithium in OEt₂/n-hexane in the presence of 12-crown-4. Smaragd-green single crystals of 1 · C₇H₈ which were suitable for X-ray crystallography were formed from toluene solutions at –18 °C. According to the crystal structure determination 1 forms ion pairs between the lithium atom and the CH₂-carbon atom which is member of a planar Ti–C–Si–N heterocycle. The coordination geometry of the Li–C–Ti axis is linear (bond angle 172.8° in average of the two symmetry independent species) with coordination number five at the CH₂-carbon atom.     

Crystal Structure of [Et_4N][Sm(S_2CNEt_2)_4]

The crystal structure of .[Et4N][Sm(S2CNEt2)4] was determined by X-ray diffraction technique. The crystal crystallizes in monoclinic system, space group P21/n with a= 1. 1695(3), b=2.0821(6), c=1.7420(7) nm, β=99. 79(3)°? Z=4, Dc= 1. 39 g/ cm3, μ(Mo/KTσ) = 18. 4 cm-1, F(000) = 1812. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R of 0. 053 for 3116 (Ⅰ> 3σ- (Ⅰ)) reflections. Each asymmetric unit contains two ions [Sm (S2CNEt2)4]-1 and [Et4N] +1, having distance between central atoms N5 and Sm3+ to be 0. 6522 nm. The atom Sm is coordinated by eight sulphur atoms. The Sm-S distance lies in the range of 0. 285-0. 290 nm with an average of 0. 288 nm.     

Synthesis and Crystal Structure of a Dinuclear Cobalt(II) Complex [Co2(1H-benzimidazole)4(1,4-bdoa)2]

1 INTRODUCTION In the last decades, metal carboxylate complexes have become a particularly important subject in mo- dern coordination chemistry owing to their fascina- ting structural diversity and potential applications as functional materials[1～3]. The generation of supramo- lecular architectures relies on the combination of se- veral factors, such as the coordination geometry of metals, bonding of the ligands and reaction condi- tions[4, 5]. In relation to the ligands, the judicious c…     

Molecular Topology in Crystals of a Potassium(I) Complex with [Z-5-(2-Chlorobenzylidene)-4-Oxoimidazolin-2-YL]-3-Amino-Propanoate

In a complex with [ Z -5-(2-chlorobenzylidene)-4-oxoimidazolin-2-yl]-3-amino-propanoate acid (APAC), potassium ion adopts distorted square-bipyramidal (4 + 2) coordination. All donor atoms are oxygens; four of them originate from carboxylate groups of APAC, while the remaining ones are water oxygens. The equatorial plane of coordination polyhedron is composed of two carboxylate oxygens (with K-O distances of 2.769 and 2.806 Å) and two water oxygens (with K-O distances of 2.722 and 2.749 Å). Two axial K-O bonds (2.663 and 2.664 Å), involving the remaining carboxylate O atoms, complete the sixfold coordination of the K atom. Coordination polyhedra are condensed in two ways. The distance between two potassium pairs are significantly different, 4.224 and 3.801 Å. APAC molecules are held together by a network of hydrogen bonds and create a gap along the [ab] plane with molecular ribbons of potassium ions and water molecules inside. Due to the potassium alignment of aliphatic chains in two neighbouring, crystalgraphically independent APAC molecules, small cavities are created, which form small channels along the b axis with the remaining water molecule.     

Synthesis,Structure and Characterization of the Cyano-Bridged Heteropolymer Poly{[Bis(Trimethylenediamine)Copper(II)][Hexacyanocobalt(III)]} Perchlorate Dihydrate with a Two-Dimensional Framework

The complex [Cu(tn)₂]₂[Co(CN)₆](ClO₄)·2H₂O (tn = trimethylenediamine) has been prepared and characterized by elemental analysis, IR, electronic and electronic spin resonance spectra and magnetic properties. The x-ray structure analysis shows that each [Co(CN)₆]^3? ion coordinates to four [Cu(tn)₂]²⁺ cations through four cyano nitrogen atoms in the same plane, providing a two-dimensional square network structure, formed from Co-CN-Cu(tn)₂-NC-Co linkages.     

Synthesis and Crystal Structure of an Mn(II) Complex with Benzoylacetone

The complex (benzoato)benzoylacetonato(bipyridine)Mn(II) has been prepared and its crystal structure determined by X-ray diffraction methods. Benzoic acid, benzoylacetone (bzac) and 2,2'-bipyridine all chelate to Mn(II) to form a six coordinate complex. As bond angles around the Mn(II) atom greatly deviate from those expected for an octahedron, the coordination geometry may be described as distorted pyramidal with a bidentate carboxyl group occupying the apex of the pyramid. Although the Mn atom deviates by 0.550 Å from the enol ring plane of bzac, Mn-O distances [2.105(2) and 2.098(2) Å] are normal. This suggests the existence of electrostatic interactions between Mn(II) and the bzac ligand.     

Synthesis, Crystal Structure and Biological Activity of 2-Chloro-N-{2-fluoro-5-[N-(phenylsulfonyl) phenyl- sulfonamido] phenyl} benzamide

2-Chloro-N-{2-fluoro-5-[N-(phenylsulfonyl)phenylsulfonamido]phenyl}benzamide was synthesized and its crystal structure was also determined by X-ray single-crystal diffraction. The title compound(C25H18C1FN2O5S2) belongs to monoclinic, space group P21/n with a=0.7377(3) nm, b=1.2036(5) nm, c=2.6846(11) nm, β=90.895(9)°,V=2.3833(16) nm3, Mr=544.98, Z=4, Dc= 1.519 g/cm3, μ=0.385 mm-1, F(000)=1120, R1=0.0632, and wR2=0. 1438. Its crystal structure belongs to a novel class that has not been reported yet, and its preliminary herbicidal activity was also tested. Its inhibition rate to seedling growth of barnyard grass reaches 15.1% at 100 μg/mL.     

Sm2As4O9: Ein ungewöhnliches Samarium(III)‐Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]

Sm₂As₄O₉: An Unusual Samarium(III) Oxoarsenate(III) According to Sm₄[As₂O₅]₂[As₄O₈] Pale yellow single crystals of the new samarium(III) oxoarsenate(III) with the composition Sm₄As₈O₁₈ were obtained by a typical solid‐state reaction between Sm₂O₃ and As₂O₃ using CsCl and SmCl₃ as fluxing agents. The compound crystallizes in the triclinic crystal system with the space group (No. 2, Z = 2; a = 681.12(5), b = 757.59(6), c = 953.97(8) pm, α = 96.623(7), β = 103.751(7), γ = 104.400(7)°). The crystal structure of samarium(III) oxoarsenate(III) with the formula type Sm₄[As₂O₅]₂[As₄O₈] (≡ 2 × Sm₂As₄O₉) contains two crystallographically different Sm³⁺ cations, where (Sm1)³⁺ is coordinated by eight, but (Sm2)³⁺ by nine oxygen atoms. Two different discrete oxoarsenate(III) anions are present in the crystal structure, namely [As₂O₅]^4? and [As₄O₈]^4?. The [As₂O₅]^4? anion is built up of two Ψ¹‐tetrahedra [AsO₃]^3? with a common corner, whereas the [As₄O₈]^4? anion consists of four Ψ¹‐tetrahedra with ring‐shaped vertex‐connected [AsO₃]^3? pyramids. Thus at all four crystallographically different As³⁺ cations stereochemically active non‐binding electron pairs (“lone pairs”) are observed. These “lone pairs” direct towards the center of empty channels running parallel to [010] in the overall structure, where these “empty channels” being formed by the linkage of layers with the ecliptically conformed [As₂O₅]^4? anions and the stair‐like shaped [As₄O₈]^4? rings via common oxygen atoms (O1 – O6, O8 and O9). The oxygen‐atom type O7, however, belongs only to the cyclo‐[As₄O₈]^4? unit as one of the two different corner‐sharing oxygen atoms.     

Kristallstruktur von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Crystal Structure of (Me₄N)₃[Ir(SCN)₆], Vibrational Spectra and Normal Coordinate Analysis From a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Ir(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of (Me₄N)₃[Ir(SCN)₆] (trigonal, space group R3, a = 14.838(2), c = 23.827(1) Å, Z = 6) reveals the presence of two crystallographically independent complex anions which C_3i symmetry correlates with the cation/anion ratio 3 : 1. The thiocyanate ligands are exclusively S-coordinated with the average Ir–S distance of 2.384 Å and the Ir–S–C angle of 106.4°. The torsion angles S–Ir–S–C are 17.5 and 42.1°. The IR and Raman spectra of the (n-Bu₄N) salt are assigned by normal coordinate analysis based on the molecular parameters of the X-ray determination. The valence force constant f_d(IrS) is 1.57 mdyn/Å.     

Synthesis and Extended 3D Hydrogen-bonded Structure of Complex Tris(violurato-N,O) Cobalt(III) Hexahydrate

1 INTRODUCTION The study of cobalt complexes plays an important role in pharmacology, coordination chemistry and bio- inorganic chemistry. The recent work on organoco- baloximes shows that it has outgrown its initial rele- vance of Vitamin B12 model and acquired an indepen- dent research field because of its rich chemistry[1~4]. At the same time, research on the complexes with oxime ligands has considerable interest owning to their special catalytic, electric, magnetic properties and bio…     

AlIII-Phthalocyanine: Darstellung,Eigenschaften und Kristallstruktur von Tetra(n-butyl)ammonium-trans-di(nitrito(O))phthalocyaninato(2−)aluminat(III)

Al^III Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)-ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III) [Al(Cl)Pc^2?] reacts with excess (ⁿBu₄N)NO₂ in dimethylformamide yielding less soluble blue tetra(n-butyl)ammonium-trans-di(nitrito(O))phthalocyaninato(2?)aluminate(III), (ⁿBu₄N)^trans[Al(ONO)₂Pc^2?], which crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4. The Al atom is in the special position 4 d in the center of the Pc^2? ligand and the two nitrit ions are monodentate O-coordinated in a mutually trans arrangement to the Al atom. The Al? O and average Al? N_iso bond distances are 1.927(2) and 1.956 Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.277(4) Å; d(N? O) = 1.221(4) Å; ?(O? N? O) = 114.3(3)°; ?(Al? O? N) = 121.3(2)°. The non-bonded O atoms are trans to the Al atom. The Pc^2? ligand is slightly ruffled. The UV-VIS-NIR spectra and the vibrational spectra are discussed.     

Synthesis and crystal structure of [Co(mpt)_2{P(OCH_3)_3}_2]BF_4 (Hmpt = 2-mercaptothiazoline)

The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c with a= 0.8078(5), b=2.6020(18), c=1.2191(7) nm, β= 99.38 (1)°, V= 2.528(3) nm3, and Z = 4. The structure comprises discrete cations [Co(mpt)2{P(OCH3)3}2.] and anions BF4- , in which the cobalt (Ⅲ) atom is coordinated to two chelate mpt- and two as-oriented monodentate P(OCH3)3 ligands in a highly distorted octahedral geometry. The most distorted angles are S(2)-Co(1)-S(2a) of 162.23(10)° and N(1)-Co(1)-S(2) of 71. 47 (13)°, the latter is caused by the geometric constraint of the bidentate ligand mpt- . Cyclic voltammetry has been used to study the electrochemical behavior of the title complex on the R electrode in MeCN solution with 0.1 mol·L-1 of Bun4NBF4 as electrolyte. The results indicate that the title complex is unstable in MeCN.     

Synthesis,Crystal Structure and Fluorescence of A 1-D Polymeric Zinc(Ii) Complex with Pyrazine-2-Carboxylate as a Bridging Ligand

A one-dimensional chain complex {[Zn(pyz)(SCN)(H₂O)₂]·H₂O}_∞ (pyz = pyrazine-2-carboxylic anion) has been synthesized and its crystal structure determined by X-ray crystallography. The complex crystallizes in an orthorhombic system and the space group is P2 ₁2₁2₁ with a = 6.873(3), b = 9.847(4), c = 16.466(7) Å. The Zn(II) ion is located in a distorted octahedral environment with two oxygen atoms O(3) and O(4) from terminal ligands of two water molecules, another oxygen atom O(1) from the carboxylate group of pyz, and three nitrogen atoms, N(1), and N(2A) from two different pyz and N(3) from a terminal thiocyanate anion, in which a chelated five-membered ring is formed by coordination of O(1) and N(1) to the Zn(1) atom. Therefore, an infinite zigzag chain consisting of Zn(II) ions and pyz anions is constructed and the chains are linked together with hydrogen bonding from coordinated and uncoordinated water molecules. The fluorescence spectra for the bridging ligand Na(pyz) and the complex were measured at room temperature in aqueous solution and in the solid state.     

Synthesis and Crystal Structure of a Novel Co(II)-Nitronyl Complex [Co(IM2-Py)(PCA)(N_3)_2]

1 INTRODUCTION The design and synthesis of molecule-based mag-netic materials is one of the major subjects of mate-rials science. Nitronyl nitroxides acting as useful pa-ramagnetic building blocks have been extensively usedto assemble molecular magnetic materials in the pastfew years[1～5]. However, their weakly basic charac-ter strongly limits their coordination ability. Mean-while, the azide anion is a versatile ligand which canlink the transition metal atoms with different coor-dinatio…