Synthesis and crystal structure of two novel nickel (imidazole) complexes having hydrogen-bonded networks

Two nickel (imidazole) complexes, Ni(im)₆Cl₂·4H₂O (1) and Ni(im)₆(NO₃)₂ (2) (im=imidazole) have been synthesized and characterized by elemental analysis, IR, UV, TG and single crystal X-ray diffraction. 1 crystallizes in the triclinic space group P-1 with a=8.800(6) Å, b=9.081(6) Å, c=10.565(7) Å, =75.058(9)°, β=83.143(8)°, γ=61.722(8)°, V=718.3(8) Å³, Z=1 and R₁ (wR₂)=0.0469 (0.1497). 2 crystallizes in the trigonal space group R-3 with a=12.370(6) Å, b=12.370(6) Å, c=14.782(14) Å, =90.00°, β=90.00°, γ=120.00°, V=1959(2) Å³, Z=3 and R₁ (wR₂)=0.0358 (0.0955). 1 and 2 exhibit different supramolecular network due to their different counter anions and different hydrogen bonding connection. In compound 1, [Ni(im)₆]²⁺ cation and counter anions Cl⁻ alternatively array in an ABAB fashion via N–HCl hydrogen bonding. In compound 2, the plane of each NO₃²⁻ is almost parallel and each NO₃²⁻ connect three different [Ni(im)₆]²⁺ cations via N–HO hydrogen bonding.     

Structural and spectroscopic properties of Hexamethylenetetramine cobalt(II) complex: [Co(NCS)2(hmt)2(H2O)2][Co(NCS)2(H2O)4] (H2O)

Synthesis, structure, spectroscopy and thermal properties of complex [Co(NCS)₂(hmt)₂(H₂O)₂][Co(NCS)₂(H₂O)₄] (H₂O) (I), assembled by hexamethylenetetramine and octahedral Co(II) metal ions, are reported. Crystal data for I: F_w 387.34, a=9.020(8), b=12.887(9), c=7.95(1) Å, =96.73(4), β=115.36(5), γ=94.16(4)°, V=820(1) Å³, Z=2, space group=P−1, T=173 K, λ(Mo-K)=0.71070 Å, ρ_calc=1.718567 g cm⁻³, μ=17.44 cm⁻¹, R=0.088, R_w=0.148. An interesting two-dimensional network is assembled via hydrogen bonds through coordinated and free water molecules. The d–d transition energy levels of Co(II) ion are determined by UV–vis spectroscopy and calculated by ligand field theory. The calculated results agree well with experiment ones.     

Structure and conformation of 2,3,4-triphenyl-1-oxa-4-azabutadiene

2,3,4-triphenyl-1-oxa-4-azabutadine (C20H15NO) has been studied by X-ray analysis and AM1 molecular orbital methods. It crystallises in the triclinic space group P-1 with a=9.414(3), b=10.479(3), c=8.385(2) Å, =103.31(3)°, β=97.10(3)°, γ=74.09(1)°, V=772.5(4) ų, Z=2, D_c=1.227 gcm⁻³, and μ(MoK)=0.075 mm⁻¹ and F₀₀₀=300. The structure was solved by direct methods and refined to R=0.043 for 2672 reflections [I>2σ(I)]. The conformational analysis of the title compound were investigated by semi-empirical quantum mechanical AM1 calculations. The minimum conformation energies were calculated as a function of the three torsion angles θ₁(O(1)C(7)C(8)N(1)), θ₂(C(8)N(1)C(15)C(16)) and θ₃(C(14)C(9)C(8)N(1)). The results are compared with the X-ray results. C=O and C=N groups are twisted about each other by 95.5(2)°.     

Tautomeric properties, conformations and structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine

The crystal structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine (C₁₃H₁₀NO₂Cl) was determined by X-ray analysis. It crystallizes orthorhombic space group P2₁2₁2₁ with a=12.967(2) Å, b=14.438(3) Å, c=6.231(3) Å, V=1166.5(6) Å³, Z=4, D_c=1.41 g cm⁻³ and μ(MoK)=0.315 mm⁻¹. The title compound is thermochromic and the molecule is nearly planar. Both tautomeric forms (keto and enol forms in 68(3) and 32(3)%, respectively) are present in the solid state. The molecules contain strong intramolecular hydrogen bonds, N1–H1O1/O2 (2.515(1) and 2.581(2) Å) for the keto form and O1–H01N1 for the enol one. There is also strong intermolecular O2–HO1 hydrogen bonding (2.599(2) Å) between neighbouring molecules. Minimum energy conformations AM1 were calculated as a function of the three torsion angles, θ₁(N1–C7–C6–C5), θ₂(C8–N1–C7–C6) and θ₃(C9–C8–N1–C7), varied every 10°. Although the molecule is nearly planar, the AM1 optimized geometry of the title compound is not planar. The non-planar conformation of the title compound corresponding to the optimized X-ray structure is the most stable conformation in all calculations.     

Comparison of optical properties and crystal structures of the praseodymium and europium chloroderivatives of acetates

The praseodymium and europium dichloroacetates were obtained in the form of monocrystals. Crystal structures of the Ln(HCl₂CCOO)₃·2H₂O (Ln=Pr, Eu) compounds were determined by X-ray analysis. Both crystals proved to be isomorphous. They are monoclinic, space group P2₁/n with: a=9.747(6), b=13.857(7), and c=23.595(9) Å, β=95.03(4)°, U=3175(3) Å³, Z=8 for C₆H₇Cl₆O₈Pr and a=9.634(7), b=13.757(11), and c=23.524(14) Å, β=94.84(4)°, U=3107(4) Å³, Z=8 for C₆H₇Cl₆O₈Eu. There are two symmetry independent lanthanide cations, which adopt a nine-coordinate geometry with seven oxygen atoms from carboxylate groups and two oxygen atoms from water molecules. Absorption (Pr³⁺, Eu³⁺), emission and emission excitation (Eu³⁺) spectra of single crystals of Ln(HCl₂CCOO)₃·2H₂O were recorded at room temperature and low temperatures down to 4.2 K. Spectral intensities of the investigated systems are parametrized in terms of the Judd–Ofelt theory and compared to those of lanthanide trichloroacetates and acetates crystals. The relationship between the hypersensitivity and covalency is discussed. The nephelauxetic ratio β and Sinha's parameter δ are calculated based on the absorption spectra. The variation of these parameters and their correlation with the nature of metal–ligand bond is discussed. The bond polarity and bond strength of coordination complex determine the activity and stereospecifity of the catalyst thus the study of these properties are very important because of the application of lanthanide carboxylates as precursors of catalysts. The spectroscopic results are correlated with those from the crystal structure studies, especially with Ln–O distances and the co-ordinating forms of the carboxylate ions. The vibronic coupling in the f–f transitions were analysed. In order to determine the vibronic coupling quantitatively, calculations of the R=I_VIB./I_0-phonon rates were performed from the low temperature absorption spectra. The correlation between the vibronic coupling and covalency is analysed.     

A triple helical calcium-based coordination polymer with strong blue fluorescent emission

A hydrothermal reaction of 1,3-dicyanobenzene and Ca(OH)₂ yielded a triple helical calcium-based coordination polymer of the formula, C₂₀H₂₅Ca_2.50O_18.50 (1). The 1,3-benzenecarboxylate anion, found in the final product was generated in situ during the synthesis by the hydrolysis of 1,3-dicyanobenzene. X-ray diffraction study shows that the complex 1 crystallizes in the monoclinic system, C2/c space group, a=15.5701(5), b=21.4445(7), c=17.1601(6) Å, β=111.7400(7)°, V=5322.1(3) Å³, Z=8, D_c=1.651 Mg/m³. The calcium atoms show differences in the coordination environments. Complex 1 emits strong blue fluorescent light (λ_em(max)=419 nm) when it is excited by UV light (λ_ex(max)=316 nm) in the solid state at room temperature.     

Synthesis, characterization and reactivity of tetracyclopentadienylniobium(IV), a precursor to organometallic derivatives of niobium(IV)

In toluene as medium, tetra(cyclopentadienyl)niobium(IV), NbCp₄, has been prepared in satisfactory yields from the reaction of NaCp with: (a) Nb₂C1₁₀, (b) NbCl₄(THF)₂, or (c) NbCp₂Cl₂. Tetracyclopentadienylniobium(IV) has been characterized by X-ray diffraction. Crystal data: C₂₀H₂₀Nb, M=353.29 g mol⁻¹, hexagonal, space group P6₅ (no. 170), a=b=9.396(2), c=31.23(3) Å, V=2388(2) ų, Z=6, d_calc=1.48 g cm⁻³, λ(Cu–K)=1.54184 Å, T=291 K, μ=62.04 cm⁻¹, F(000)=1686. Two of the four cyclopentadienyl ligands are bonded to niobium in a pentahapto fashion, the other two being monohapto. NbCp₄ undergoes cyclopentadiene elimination in the presence of species containing active protons such as Ph₃SiOH or strong acids, the products being tris- or biscyclopentadienyl compounds depending on the molar ratio of the reagents.     

Hydrogen bonds in the crystal packings of mesalazine and mesalazine hydrochloride

The crystal structures of pharmaceutical product mesalazine (marketed also under different proprietary names as Salofalk, Asacol, Asacolitin, and Claversal) and its hydrochloride are reported. In the crystal mesalazine is in zwitterion form as 5-ammoniosalicylate (1) whereas mesalazine hydrochloride crystallizes in an ionized form as 5-ammoniosalicylium chloride (2). Compound 1 (C₇H₇O₃N) crystallizes in the monoclinic space group P2₁/n with a = 3.769(1) Å, b = 7.353(2) Å, c = 23.475(5) Å, β = 94.38(2)°, V = 648.7(8) ų, Z = 4, D_c = 1.568 g cm⁻³ and μ(MoK) = 1.2 cm⁻¹. Compound 2 (C₇H₈O₃NCl) crystallizes in the triclinic space group P with a = 4.4839(2) Å, b = 5.7936(2) Å, c = 15.6819(5) Å, = 81.329(3)°, β = 88.026(3)°, γ = 79.317(4)°, V = 395.74(3) ų, Z = 2, D_c = 1.591 g cm⁻³ and μ(CuK) = 40.8 cm⁻¹. The crystal structures were solved by direct methods and refined to R = 0.041 for 1 and 0.028 for 2, using 607 and 1374 observed reflections, respectively. The configuration of both molecules, with the ortho hydroxyl to a carboxyl group, favours the intramolecular hydrogen bonds. Very complex systems of intermolecular hydrogen bonds were observed in both crystal packings. They are discussed in terms of graph-set notation. The mesalazine crystal structure is characterized by two-dimensional network of hydrogen bonds in the ab plane. The crystal structure pattern of mesalazine hydrochloride is a three-dimensional network significantly supported by N⁺---HCl⁻ interactions.     

Synthesis and structure of a novel three-dimensional metal selenite containing multidirectional intersecting double helical chains: [Fe2(H2O)4(SeO3)2]

A novel three-dimensional metal selenite [Fe₂(H₂O)₄(SeO₃)₂] (1) has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum, TG analysis and the single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a=6.5283(13) Å, b=8.8754(18) Å, c=7.6798(15) Å, (=98.82(3)β, V=439.71(15) Å3, and Z=2. Compounds 1 exhibits interesting three-dimensional structure constructed from {FeO₆} octahedra and {SeO₃} pyramids linked via the corner- and/or edge-sharing mode. The most interesting structural feature of compound 1 is that the existence of multidirectional intersecting double helical chains in one compound.     

Cation–anion interactions in triphenyl telluronium salts. The crystal structures of (Ph3Te)2[MCl6] (M=Pt, Ir), (Ph3Te)[AuCl4], and (Ph3Te)(NO3)·HNO3

Triphenyltelluronium hexachloroplatinate (1), hexachloroiridate (2), tetrachloroaurate (3), and tetrachloroplatinate (4) were prepared from Ph₃TeCl and potassium salts of the corresponding anions. Upon recrystallization of 4 from concentrated nitric acid, K₂[PtCl₆] and (Ph₃Te)(NO₃)·HNO₃ (5) were obtained. The crystal structures of 1–3 and 5 are reported. Compounds 1 and 2 are isostructural. They are triclinic, P , Z=2 (the asymmetric unit contains two formula units). Compound 1: a=10.7535(2), b=17.2060(1), c=21.4700(3) Å, =78.9731(7), β=77.8650(4), γ=78.8369(4)°. Compound 2: a=10.7484(2), b=17.1955(2), c=21.4744(2) Å, =78.834(1), β=77.649(1), γ=78.781(1)°. Compound 3 is monoclinic, P2₁/c, Z=4, a=8.432(2), b=14.037(3), c=17.306(3) Å, β=93.70(3)°. Compound 5 is monoclinic. P2₁/n, Z=4, a=9.572(2), b=14.050(3), c=13.556(3) Å, β=90.76(3)°. The primary bonding in the Ph₃Te⁺ cation in each salt is a trigonal AX₃E pyramid with Te---C bond lengths in the range 2.095(8)–2.14(2) Å and the bond angles 94.1(6)–100.9(5)°. The weak TeCl (1–3) and TeO (5) secondary interactions expand the coordination sphere. In 1 and 2 the cation shows a trigonal bipyramidal AX₃YE coordination with one primary Te---C bond and the shortest secondary TeCl contact in axial positions and the two other Te---C bonds and the lone-pair in equatorial positions. The cation in 3 shows a distorted octahedral AX₃Y₃E environment and that in 5 is a more complex AX₃Y₃Y′₂ arrangement. In both latter salts the structure is a complicated three-dimensional network of cations and anions.     

Conformational and structural analysis of N-N′-bis(4-methoxybenzylidene)ethylenediamine

The Schiff base compound, N-N′-bis(4-methoxybenzylidene)ethylenediamine (C₁₈H₂₀N₂O₂) has been synthesized and its crystal structure has been investigated by X-ray analysis and PM3 method. The compound crystallizes in monoclinic space group P2₁/n with a=10.190(1), b=7.954(1), c=10.636(1) Å, β=111.68(1)°, V=801.1(1) ų, Z=2 and D_cal=1.229 Mgm⁻³. The title structure was solved by direct methods and refined to R=0.056 for 2414 reflections [I>3.0σ(I)] by full-matrix anisotropic least-squares methods. The energy profile of the compound was calculated by PM3 method as a function of θ[N1′–C9′–C9–N1]. The most stable molecular structure of the title compound is the anti conformation, which is different in energy by 5.0 and 1.0 kcal mol⁻¹ from the eclipsed conformation I and gauche conformations, (III and V), respectively.     

Structure analysis and the standard molar enthalpy of formation of a coordination polymer [Co(TO)2Cl2]n (TO = 1,2,4-triazole-5-one)

A coordination polymer was synthesized by the reaction of CoCl₂ with 1,2,4-triazole-5-one (TO) and charaterized by means of IR and TG–DTG. Single-crystal structure analysis showed that the complex crystallized in the monoclinic space group C2/c: a = 23.105(9) Å, b = 3.5683(2) Å, c = 13.589(6) Å,  = 90°, β = 124.038(4)°, γ = 90°, V = 928.4(7) Å³, Z = 4. The standard molar enthalpy of formation of the complex was determined to be (−1034.28 ± 0.95) kJ mol⁻¹.     

Syntheses and crystal structures of 1,2:5,6:9,10:13,14:17,18:21,22-hexabenzo-3,7,11,15,19,23-hexadehydro[24]annulene (HBC), 1,2:5,6:9,10:13,14-tetrabenzo-3,7,11,15-tetradehydro[16]annulene (QBC) and a tetracobalt complex of QBC. The first example of a transition metal complex of QBC

1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15-tetradehydro[16]annulene, or tetrabenzocyclyne (QBC) and 1,2:5,6:9,10:13,14:17,18:21,22-hexabenzo-3,7,11,15,19,23-hexadehydro[24]annulene (HBC) have been structurally characterized by X-ray. crystallography. QBC crystallizes in two different space groups; P2₁/c with a = 10.652(3) Å, b = 10.624(2) Å, c = 19.549(4) Å, β = 93.83(2)°, V = 2207.4(8) ų, and Z = 4 and P4₁2₁2 with a = 9.330(1) Å, c = 25.497(8) Å, V = 2219.6(12) Å, and Z = 4. HBC crystallizes in monoclinic P2₁/n with a = 14.763(3) Å, b = 10.296(2) Å, c = 22.057(4) Å, β = 108.61(3), V = 3177.4(11) ų, T = 133 K, and Z = 4. Reaction of QBC with dicobaltoctacarbonyl has produced a tetracobalt complex which has been characterized by X-ray crystallography. This complex crystallizes in monoclinic P2₁/c with a = 14.699(3) Å, b = 17.188(3) Å, c = 17.254(3) Å, β = 112.63(3)°, V = 4023.5(13) ų, and Z = 4. Only two of the four C---C triple bonds of QBC bind to dicobalthexacarbonyl moieties even when excess dicobaltoctacarbonyl is used.     

Synthesis and structure of the iron-substituted silylacetylene [(η-C5H5)Fe(CO)2SiMe2C]2 and its cobalt hexacarbonyl derivative [(η-C5H5)Fe(CO)2SiMe2C]2 · Co2(CO)6

A transition metal-substituted silylacetylene [(η⁵-C₅H₅)Fe(CO)₂SiMe₂C]₂, [FpMe₂SiC]₂ (I) was synthesized and characterized spectroscopically and structurally. I crystallized in the monoclinic space group P2₁/n, A = 13.011(3) Å B = 12.912(3) Å, C = 13.175(5) Å, β = 94.95(2). The acetylene linkage is reactive toward Co₂(CO)₈ to form I. Co₂(CO)₆ (II) which was also characterized spectroscopically and by single crystal X-ray diffraction. II crystallized in the orthorhombic space group Pbca, A = 17.64(2) Å, B = 14.225(10) Å, C = 24.49(2) Å.     

Structures of propionaldehyde, butyraldehyde, and pivalaldehyde complexes of the chiral rhenium fragment [(η-C5H5)Re(NO)(PPh3)]

The crystal structures of propionaldehyde complex (RS,SR)-(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₃)]⁺ PF₆⁻ (1b⁺ PF₆^s−; monoclinic, P2₁/c (No. 14), a = 10.166 (1) Å, b = 18.316(1) Å, c = 14.872(2) Å, β = 100.51(1)°, Z = 4) and butyraldehyde complex (RS,SR)-[(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₂CH₃)]⁺ PF₆⁻ (1c⁺PF₆⁻; monoclinic, P2₁/a (No. 14), a = 14.851(1) Å, b = 18.623(3) Å, c = 10.026(2) Å, β = 102.95(1)°, Z = 4) have been determined at 22°C and −125°C, respectively. These exhibit C O bond lengths (1.35(1), 1.338(5) Å) that are intermediate between those of propionaldehyde (1.209(4) Å) and 1-propanol (1.41 Å). Other geometric features are analyzed. Reaction of [(η⁵-C₅H₅)Re(NO)(PPh₃)(ClCH₂Cl)]⁺ BF₄⁻ and pivalaldehyde gives [(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHC(CH₃)₃)]⁺BF₄⁻ (81%), the spectroscopic properties of which establish a π C O binding mode.     

Novel coordination of a hydroxamic acid : Crystal structures of bis(glycinohydroxamoto)nickel(II) and tris(glycinohydroxamoto)cobalt(III)

The structures of two glycinohydroxamoto (GHA) complexes of Ni(II) and Co(III) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(GHA)₂ are monoclinic with a = 5.360(1), b = 7.315(4), c = 10.194(4) Å, β = 96.57(3), Z = 2, and space group P2₁/c. The crystals of Co(GHA)₃•1/2 H₂O are monoclinic with a = 22.467(19), b = 8.041(4), c = 13.700(11) Å, β = 116.01(7), Z = 8, and space group C2/c. The values of the final residuals R for Ni(GHA)₂ and Co(GHA)₃•1/2 H₂O are 0.0275 and 0.032, respectvely. The molecular structures of Ni(GHA)₂ and Co(GHA)₃ consist of a square planar and an octahedral coordination, respectively, with the glycinohydroxamato (NH₂CH₂CONOH⁻) ligands coordinating to the metal ion via the N (amino) and the N (NOH⁻). These two complexes are the first well-established cases of coordination of the NHO⁻ group of a hydroxamic acid to a transition metal via the nitrogen atom.     

Structural features of dibromobis(nicotinamide)zinc(II) complex

A novel ligand complex of Zn(II) with nicotinamide (one form of niacine) and two bromine ions were synthesised and characterised on the basis of elemental analysis, FT-IR spectroscopy and X-ray crystallography. Crystal system is monoclinic, space group C2/c (no: 15), cell parameters are a=13.3535(9) Å, b=6.3859(7) Å, c=19.1940(19) Å, β=101.75(3)°, V=1602.5(3) Å³ and Z=4. It has been proven that the nicotinamide ligands in the structure of the Zn(II) complex are coordinated to the metal ion with N atoms ([ZnBr₂(na)₂] where na: nicotinamide).     

三环已基锡L-扁桃酸酯配合物的合成、结构及性质

三环己基氢氧化锡与L-扁桃酸(物质的量比1:1)在苯和乙醇混合溶剂中反应合成了三环己基锡L-扁桃酸酯。 经X射线衍射方法测定了其晶体结构,配合物属斜方晶系,空间群为P2₁2₁2₁,晶体学参数a=0.80825(4) nm,b=1.77151(8) nm,c=1.8385(2) nm,α=β=γ=90°,V=2.6324(2) nm³,Z=4,D_c=1.310 g/nm³,μ(MoKα)=9.92 cm^-1,F(000)=1080,R₁=0.0472,wR₂=0.1341。 中心锡原子与环己基碳原子和氧原子构成畸型四面体。 对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。 研究了配合物的热稳定性、电化学性能、圆二色谱和体外抗癌活性。     

Dynamic behaviour and X-ray analysis of chiral η-allylpalladium complexes. II

The DANTE technique and NOESY two-dimensional method have been employed to observe the isomerization of the chiral cationic complex [Pd(η³-CH₂CMeCH₂(P-P′)]⁺ (1a), where P-P′ = the chiral chelating ligand (S)(N-diphenylphosphino)(2-diphenylphosphinoxymethyl)pyrrolidine. The rate constant was found to be 0.5 s⁻¹ in CHCl₃ at 295 K and 1.50 s⁻¹ in the presence of added free ligand. In the latter case the epimerization proceeds by a π-σ-π mechanism via the intermediacy of a primary η¹-allylpalladium complex. Although the intermediate was not detected, the NMR findings reveal that it has the allylic terminus η¹-bonded to palladium. The structure of 1a in its PF₆⁻ salt has been determined. The compound crystallizes in the orthorhombic space group P2₁2₁2₁ with a 10.029(4) b 19.203(8) c 36.115(6) Å, Z = 8, R = 0.0572 and R_w = 0.0712 for 3716 observed reflections with I > 3σ(I).     

Hydrothermal synthesis and structure of one-dimensional Co(dien)2(VO3)3·(H2O) (dien=diethylenetriamine)

One-dimensional Co(dien)₂(VO₃)₃·(H₂O) was prepared from the hydrothermal reaction of NH₄VO₃, Co₂O₃, diethylenetriamine (dien) and H₂O at 130 °C. The compound crystallizes in the monoclinic system, space group P2₁/c with a=16.1581(6) Å, b=8.7006(3) Å, c=13.9893(4) Å, β=103.1483(11)°, V=1915.13(11) Å³, Z=4, and R₁=0.0268 for 3060 observed reflections. Single crystal X-ray diffraction revealed that the structure is composed of infinite one-dimensional chains formed by corner-sharing VO₄ tetrahedra with Co(dien)³⁺ complex cations and crystallization water molecules occupying the interchain positions, which are held together to a three-dimensional network via extensive hydrogen-bonding interactions. The compound, with a new zig-zag conformation of metavanadate chains, is the first example of vanadium oxides incorporating trivalent transition metal coordination groups. Other characterizations by elemental analysis, IR and thermal analysis are also described.