Structural Correlations in High-Spin Complexes of [Fe{HC(3,5-Me2pz)3}2]2+: Solid State Structure of [Fe{HC(3,5-Me2pz)3}2][Fe2OCl6]

Abstract  The cation in the solid state structure of [Fe{HC(3,5-Me₂pz)₃}₂][Fe₂OCl₆] (pz = pyrazolyl ring) contains an octahedral iron(II) center with an average Fe–N bond distance of 2.17 Å, indicating that the iron(II) is in the high-spin form. While M–N bond distances of this length with κ³-[HC(3,5-Me₂pz)₃] ligands generally cause tilting of pz to open up the “bite” angle, in this structure the average tilting angle is only 3.1°, a much lower value than observed in earlier structures of this same cation paired with different anions. The crystals are monoclinic, space group P2₁/n, with a = 11.1671(12) Å, b = 10.8091(11) Å, c = 17.4385(17) Å, α = γ = 90°, β = 95.685(2)°, and Z = 2. Graphical Abstract  The cation in the solid state structure of [Fe{HC(3,5-Me₂pz)₃}₂][Fe₂OCl₆] (pz = pyrazolyl ring) contains an octahedral iron(II) center in the high-spin form with unusual orientations of the pyrazolyl rings.      

Synthesis, Crystal Structure and Properties of the Binuclear Complex [Sm2(C10H9N2O4)2(C10H8N2O4)2(H2O)4]

Abstract  A novel binuclear Smarium (III) complex with N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) was prepared and characterized. The crystal structure of [Sm₂(H₂L)₂(HL)₂(H₂O)₄] (1) was determined by X-ray single crystal diffractometry. 1 crystallizes in the monoclinic systerm, space group P2(1)/c, with a = 0.10229(2), c = 31.549(7), b = 0.70599(15) nm, and Z = 4. In the structure, Sm(III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. H₂L and HL act as tridentate ligands which form two stable five-numbered chelating rings sharing one edge in the keto form for each ligand, and the carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure. The complex was researched the interaction with calf thymus DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation .The complex also shows good fluorescence property. Index Abstract  The title compound, [Sm₂(H₂L)₂(HL)₂(H₂O)₄] was synthesized by the treatment of N-(2-propionic acid)-salicyloyl hydrazone (C₁₀H₁₀N₂O₄, H₃L) and Sm(NO₃) · 4H₂O and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that Sm (III) is nine-coordinated by carboxyl O and acyl O atoms and imido N atoms of two ligands (H₂L and HL forms) and O atoms from two water molecules. The carboxyl groups of two ligands were coordinated via bidentated bridging form. The coordination polyhedron around Sm (III) was described as a monocapped square antiprism. The inter- and intramolecular hydrogen bonds resulted in a three-dimensional network and provided extra stability for the structure.      

Synthesis and Crystal Structure of Copper II and Silver I Complex with 1,4-diazabicyclo[2.2.2]octane[Cu(CBC)2(Dabco)(H2O)] n (1) and [Ag2(HBC)2(Dabco)] n (2)

Two 1D polymeric complex, [Cu(CBC)₂(Dabco)(H₂O)] _n (1) and [Ag₂(HBC)₂(Dabco)] _n (2) have been synthesized and characterized by X-ray single crystal analysis, where CBCH is p-chlorobenzoic acid, HBCH 2 is 2-hydroxybenzoic acid and Dabco is 1,4-diazabicyclo[2.2.2]octane. Complex 1 has been obtained in high yield by hydrothermal synthesis from CuO and CBCH and Dabco, and complex 2 has been obtain by evaporation of the solvent from silver salicylate and Dabco, 1 crystallizes in the orthorhombic space group Pmn2 ₁ with a = 24.3310(5) ?, b = 6.9050(6) ?, c = 5.9980(5) ?, Z = 2, V = 1007.70(4) ?³ and Dx = 1.657 g cm⁻³, 2 crystallizes in the monoclinic space group P2 ₁ /m with a = 10.292(3) ?, b = 6.913(2) ?, c = 14.417(4) ?, β = 95.660(5), Z = 2, V = 1020.8(5) ?³ and Dx = 1.959 g cm⁻³. The final R value is 0.0302 for 1323 measured reflections for 1 and the final R value is 0.0684 for 1545 measured reflections for 2. The atomic arrangement is built by infinite one-dimensional polymeric chain in both complexes. These chains are cross-linked by hydrogen bonds involving the coordinated water molecules to form a two-dimensional framework in complex 1.     

Synthesis and structural analysis of Bis(2-hydroxyphenyl) phenylamine, PhN(o-C6H4OH)2: Comparison with Tris(2-hydroxyphenyl)amine N(o-C6H4OH)3

The molecular structures of N(o-C₆H₄OH)₃, PhN(o-C₆H₄OH)₂, andp-TolN(o-C₆H₄OMe)₂ have been determined by X-ray diffraction, thereby indicating several structural differences. For example, whereas the nitrogen in N(o-C₆H₄OH)₃ is pyramidal with Σ_C–N–C = 348.3^∘, the nitrogen atoms in PhN(o-C₆H₄OH)₂ andp-TolN(o-C₆H₄OMe)₂ are trigonal planar with Σ_C–N–C = 359.9^∘ and Σ_C–N–C = 360.0^∘, respectively. The phenyl andp-tolyl groups of PhN(o-C₆H₄OH)₂ andp-TolN(o-C₆H₄OMe)₂ lie close to the trigonal plane, while theo-C₆H₄OH ando-C₆H₄OMe groups are almost orthogonal to this plane. The coplanar and orthogonal orientations of the aryl groups of PhN(o-C₆H₄OH)₂ andp-TolN(o-C₆H₄OMe)₂ are in marked contrast to those of the phenyl groups within Ph₃N, which exhibit dihedral angles in the range 38–52^∘ and approximateD₃ symmetry. The observed structures of PhN(o-C₆H₄OH)₂ andp-TolN(o-C₆H₄OMe)₂ may be rationalized in terms of maximizing delocalization of the nitrogen lone pair into the phenyl andp-tolyl groups, while minimizing unfavorable overlap with theo-C₆H₄OH ando-C₆H₄OMe groups due to the presence of π-donatingortho-substituents; the orthogonal orientation of theo-C₆H₄OH ando-C₆H₄OMe groups is also one that minimizes unfavorable steric interactions between theortho-substituents.     

Interaction of N-(4-methoxyphenyl)-2,4,6-trinitroaniline with tris(triphenylphosphinegold)oxonium tetrafluoroborate; X-ray structure of salt [O(AuPPh3)3]2 2{(4-MeO)C6H4-N-C6H2-[2,4,6-(NO2)3]}

The structure of the auration product of N-(5-methoxybenzene)-2,4,6-trinitroaniline is determined. The compound of composition C₆₇H₅₄Au₃N₄O₈P₃ (3) crystallizes in triclinic space group P with a = 13.8280(4), b = 14.7641(4), c = 17.4531(5) Å, α = 111.550(1), β = 102.779(1), γ = 103.040(1)^∘, Z = 2. The compound represents a salt tris(triphenylphosphinegold) oxonium N-(4-methoxyphenyl)-2,4,6-trinitroanilinate, with a hexanuclear dimeric structure of the cation and a para-quinoid form of the anion that is responsible for the dark-red color of the compound.     

Transfer of Amide and 2-Methoxyethoxy Groups and Sodium Encapsulation in the Reaction of TaCl3[N(TMS)2]2 with Sodium Bis(2-methoxyethoxy)aluminum Hydride: X-ray Structure of [NaAl{N(TMS)2}(OCH2CH2OMe)3]2

Abstract  The reaction between the tantalum compound TaCl₃[N(TMS)₂]₂ and the hydridic reducing agent sodium bis(2-methoxyethoxy)aluminum hydride (Vitride) has been investigated in toluene solution at room temperature and found to afford the dimeric aluminate complex [NaAl{N(TMS)₂}(OCH₂CH₂OMe)₃]₂ as the sole isolable product. The molecular structure of the product establishes the existence of a four-coordinate aluminum atom and the formal transfer of the 2-methoxyethoxy and bis(trimethylsilyl)amide groups to the aluminate product. The aggregation of two NaAl{N(TMS)₂}(OCH₂CH₂OMe)₃ units serves to bind the two sodium cations in a crown-ether fashion through six ancillary oxygen atoms. Index Abstract  The reaction between TaCl₃[N(TMS)₂]₂ and the reducing agent Vitride has been examined and found to furnish the dimeric aluminate complex [NaAl{N(TMS)₂}(OCH₂CH₂OMe)₃]₂ in low yields. X-ray diffraction analysis confirms the attendant transfer of the 2-methoxyethoxy and bis(trimethylsilyl)amide groups to the aluminate product, which exists as a dimer that encapsulates two sodium counter ions via the 2-methoxyethoxy appendages.

Crystal structure of bis[dihydrobis(3,5-dimethy-1-pyrazolyl)borato]cadmium(II)

The structure of [H₂B(3,5-Me₂pz)₂]₂Cd shows the four nitrogen donor atoms form a pseudotetrahedral arrangement about the cadmium(II). The intraligand N—Cd—N angles are restricted to an average of 91.4° by the chelate rings forcing the interligand N—Cd—N bond angles to average 119.4°. The Cd—N bond distances average 2.21 Å with a range of 0.04 Å. The crystal is in the triclinic space group, P with a = 7.6793(2) Å, b = 8.5992(2) Å, c = 25.0874(4) Å, = 91.0791(2)°, = 97.9769(4)°, = 110.2344(6)°, and Z = 2.     

X-ray Crystal Structure of Trans -UO2(N(SiMe3)2)2(THF)2: One in a Series of Uranyl(VI) Complexes Supported by Bis(trimethylsilyl)amido Ligands

Abstract The title compound trans-UO₂(N(SiMe₃)₂)₂(THF)₂ (1) was synthesized and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c (#15) with lattice parameters a = 16.0771(5) ?, b = 13.1196(4) ?, c = 16.9391(6) ?, β = 116.853(1)°, V = 3187.61(18) ?³, Z = 4, D _calc = 1.532 g cm^-3. The six-coordinate uranium(VI) center adopts an all-trans octahedral geometry consisting of mutually trans oxo groups, silylamido ligands, and neutral THF donors. Structural comparisons of this uranyl(VI) bis(amido) complex with a related tris(amido) derivative within the series are made based on symmetry, charge, and coordination number. Graphical Abstract The X-ray crystal structure of the title complex is reported, providing comparisons based on symmetry, charge, and coordination number with a related uranyl(VI) amido derivative within this series.      

Structural characterization of a zinc(II) complex of a tris(oxime)amine ligand

The ligand tris(1-propan-2-onyl oxime)amine (TRISOXH₃) binds to zinc(II) acetate as a tridentate N₃ donor, with a third oxime group remaining unbound and extending into the crystal lattice. The crystal structure shows a distorted trigonal bipyramidal geometry around the zinc center. An intramolecular hydrogen bonding interaction between a coordinated oxime donor and an oxygen of a bound acetate is observed. This structure is similar to that of a previously reported zinc(II) complex of a related bis(oxime)amine ligand. However, the structure of Zn(TRISOXH₃)(OAc)₂ is different in ligand coordination mode and metal coordination number from those of the previously reported complexes Ni(TRISOXH₃)Cl₂ or [Ni(TRISOXH₃)(NO₃)(H₂O)]NO₃.     

Crystal and Molecular Structures of C6H5CH2SOCH2CONHCH2C6H5 and C6H5SOCH2CON(iC3H7)2

Abstract  The crystal structures for two of the ligands C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) have been determined by X-ray diffraction. These compounds crystallize in orthorhombic system with space groups and cell parameters, Pca21(no. 29), a = 8.4600(5) ?, b = 5.3534(5) ?, c = 32.136(2) ?, V = 1455.42(15) ?³ and Pna21(no. 33) a = 17.5563(11) ?, b = 5.7902(4) ?, c = 14.2866(9) ?, V = 1452.30(16) ?³, respectively. These molecules are stabilized in solid state by various intra and intermolecular hydrogen bonding interactions to give polymeric structures. The reported IR spectra of these compounds in solid state could be explained on the basis of the observed intermolecular hydrogen bonding interactions. Index Abstract  The title compounds C₆H₅CH₂SOCH₂CONHCH₂C₆H₅ (1) and C₆H₅SOCH₂CON(ⁱC₃H₇)₂ (2) were prepared by the oxidation of corresponding sulfides with H₂O₂/SeO₂ in methanol and their structures were determined. The structures show that the SO and CO groups are having “anti” configuration in 1 and “syn” configuration in 2. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis, spectroscopic characterisation and X-ray structure of [trans-Co(en)2(NO2)2]2(Cr2O7)

Dark red crystals of bis[trans-dinitrobis(ethylenediamine)cobalt(III)] dichromate, [trans-Co(en)₂(NO₂)₂]₂(Cr₂O₇) have been obtained by slowly allowing to mix the solutions of potassium dichromate and trans-dinitrobis(ethylenediamine)cobalt(III) nitrate in 1:2 molar ratio in aqueous medium. Elemental analyses and spectroscopic techniques (IR, UV/visible, ¹H and ¹³C NMR) were used for characterizing the complex salt. The complex salt crystallizes in the orthorhombic space group Fdd2 with unit cell dimensions a = 24.778(2) ?, b = 30.457(2) ?, c = 6.5364(5) ?, Z = 8, V = 4932.8(7) ?³, R₁ = 0.0617 and wR₂ = 0.1518. X-ray structure determination revealed an ionic structure consisting of cationic cobaltammine [trans-Co(en)₂(NO₂)₂]NO₃ and dichromate anion. It is the first crystal structure of this cation with a dianion.     

Synthesis and crystal structure of Cu3(Bipy)2(L1)2(L2)2? 4H2O(Bipy = 2,2′-bipyridine, L1 =1-((2-sulfonateethylimino)methyl)-2-naphthol), L2 = 2-hydroxy-1-naphthaldehyde)

The title compound, Cu₃(Bipy)₂(L¹)₂(L²)₂⋅4H₂O, was synthesized in the methanol solution of Bipy and Cu(II) in the presence of 1-((2-sulfonate-ethylimino)-methyl)-2-naphthol (L¹), which was condensation compound of taurine and 2-hydroxy-1-naphthaldehyde. This complex crystallized in the space group P-1 with a = 9.825(2) ?, b = 12.626(2) ?, c = 14.342(3) ?, α = 90.29(1)^∘, β = 100.67(1)^∘, γ = 101.67(2)^∘, and Z = 2. In the trinuclear Cu(II) complex, there are two type Cu atoms which have square and square pyramid geometries, respectively. The Cu–N distances vary from 1.965(3) to 2.000(4) ?, while the Cu–O distances are between 1.896(3) and 2.337(4) ?.     

Structure of diaqua(itaconato) cadmium(II), [Cd(C5H4O4)(OH2)2]

[Cd(C₅H₄O₄)(OH₂)₂] (1), crystallizes in the monoclinic system, space groupP2₁/n, with lattice parametersa=7.323(2),b=16.028(6),c=7.202(2) Å, β=113.11(1)°, andZ=4. The Cd atom coordinates to seven oxygens in a monocapped trigonal antiprism fashion. The antiprisms share one vertex to form chains which run approximately parallel to thec axis. The itaconate ligands link the chains to form layers which stack along theb axis.     

Synthesis and structure of (NH4)4[(DMF)2Mo8O26]· 2CH3CH2OH·2H2O (DMF= N , N -dimethylformamide)

A new organic-inorganic hybrid γ-octamolybdate complex, (NH₄)₄[(C₃H₇NO)₂Mo₈O₂₆]·2CH₃CH₂OH·2H₂O was synthesized from the mixture of ethanol, DMF, 4-aminobenzoic acid, (NH₄)₆Mo₇O₂₄·4H₂O, HCl and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2₁/n space group with the crystal cell parameters of a = 8.8825(4), b = 21.1608(10), c = 11.1343(6) ?, β = 104.7720(10)°, V = 2023.64(17) ?³ and Z = 2. The crystal X-ray analysis shows that two DMF molecules are bound to γ-octamolybdate anion. The molecular structure is stabilized by the complex hydrogen bonding.     

Growth and characterization of KY(WO4)2 crystals

Single-crystal growth of KY(WO₄)₂ (KYW) by top-seeded solution growth technique has been investigated. The effects of seed orientation, temperature gradient experienced by the growing crystal and rate of crystallization on crystal quality are reported. The best results are obtained when the growth is seeded along the 0 1 0 direction. Minute deviations from this growth direction are found to be detrimental to crystal perfection. The differential thermal analysis shows that the amount of super-cooling required for dissolution and crystallization of KYW in the flux is only 5° and this promotes an easy formation of tiny crystallites in the solution. Consequently, the crystal rotation and the solution cooling rates are found to have pronounced effects on the growth of KYW crystal.     

Synthesis, characterization and crystal structure of [Ni(DACH)2](H2O)2(CH3COO)2 (DACH = 1,4-diazacycloheptane): a three-dimensional (3-D) hydrogen-bonded network embodying 1-D water chains

The mononuclear complex [Ni(DACH)₂](H₂O)₂(CH₃COO)₂ (DACH = 1,4-diazacyclo-heptane) has been synthesized and characterized by IR, UV-Vis, elemental analysis and single crystal X-ray diffraction. The complex crystallizes in monoclinic system, P2₁/n space group with a=7.500(3) ?, b=8.788(3) ?, c=16.429(6) ?, β=93.395(5)°, D _c =1.269 g cm⁻³, μ=0.930 mm⁻¹, V=1080.9(6) ?³, Z=2. The central Ni^II atom is in a square-planar coordination geometry formed by four N atoms of two DACH chelated ligands. The notable feature of the title compound resides in the formation of a three-dimensional network through hydrogen bonds between the [Ni(DACH)₂]²⁺ cations, the CH₃COO⁻ counter anions and the guest water molecules trapped in the crystal lattice.     

Synthesis and crystal structures of two copper(I) π-complexes with 1-allyloxybenzotriazole of CuBr?C6H4N3(OC3H5) and 2CuCl?C6H4N3(OC3H5) compositions

Both compounds of CuBr⋅C₆H₄N₃(OC₃H₅) (sp. gr. P1, a = 7.633(1) Å, b = 9.987(1) Å, c = 14.898(2) Å, α = 104.75(1)^∘, β = 94.76(1)^∘, γ = 106.90(1)^∘) (I) and 2CuCl⋅C₆H₄N₃(OC₃H₅) (sp. gr. Cc, a = 11.2483(4) Å, b = 16.7076(6) Å, c = 7.2948(3) Å, β = 118.612(2)^∘) (II) composition were prepared by alternating-current electrochemical synthesis. In I due to a bridging function of organic moieties 16-membered cycles appear which are combined into ribbons {Cu₂Br₂[(C₆H₄N₃(OC₃H₅)]₂}_n. Each of two crystallographically independent copper atom possesses a trigonal-pyramidal arrangement with different degree of tetrahedral distortion. Distinctive numbers of hydrogen bonds around Br1 and Br2 atoms cause rather appreciable distinctions in copper–olefinic bond interaction effectiveness for each metal atom. In II Cu₂Cl₂ rhombs are joined to infinite chains oriented along [010] direction. Each ligand molecule is also coordinated through the C=C—bond of the allylic group to copper atom of one inorganic chain and through the nitrogen atom to a metal atom belonging to another copper-halide chain. Cu1 atoms is tetrahedrally surrounded by three chlorine atoms and nitrogen one, whereas a trigonal-planar arrangement of Cu2 atom is formed by two halogen atoms and slightly disordered olefinic group.     

A new dabco templated metal sulfate, (C6H14N2)[Mn (H2O)6](SO4)2. Chemical preparation, hydrogen-bonded structure and thermal decomposition

The crystal structure of manganese sulfate templated by 1,4-diaza-bicyclo[2.2.2]octane (abbreviated dabco), (C₆H₁₄N₂)[Mn(H₂O)₆](SO₄)₂, was investigated using single crystal X-ray diffraction data. It crystallises in the monoclinic system (space group P2₁/c) with the following unit-cell parameters: a = 12.1392(2) ?, b = 12.3117(2) ?, c = 12.2765(2) ?, β = 104.607(1)°, V = 1775.47(5) ?³ and Z = 4. The structure has been solved using direct methods and refined by least-squares analysis [R ₁ = 0.0381, wR ₂ = 0.1082]. The crystal structure of the title compound is built from isolated [Mn(H₂O)₆]²⁺ octahedral cations, 1,4-diaza-bicyclo[2.2.2]octandiium cations (C₆H₁₄N₂)²⁺ and sulfate anions (SO₄)²⁻ connected by a three-dimensional hydrogen-bond network. The thermal decomposition of the precursor, studied by thermogravimetry and temperature-dependent X-ray powder diffraction, proceeds through four stages giving rise to the mixture of Mn₂O₃and Mn₃O₄. Supplementary Material CCDC 620298 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.     

Synthesis, structure and supramolecular assembly in the crystalline state of a bifunctionalized arylimido derivative of hexamolybdate [n-Bu4N]2[Mo6O17(o,p-(MeO)2C6H3N)2]

A novel bifunctionalized arylimido derivative of hexamolybdate [n-Bu₄N]₂[Mo₆O₁₇(o,p-(MeO)₂C₆H₃N)₂] (1) was synthesized by self-assembled metathesis of α-type octamolybdate ion and 2,4-dimethoxyaniline and structurally characterized by crystal X-ray diffraction. Crystallographic data for1: monoclinic system, space group:C2/c,a = 17.319(4),b = 18.087(4),c = 21.357(5) ?, β = 106.486(4),V = 6415(2) ?³, andZ = 4,D_c = 1.693 g/cm³,R₁ = 0.0439. The complex has a short Mo–N bond length of 1.735(5) ? and an imido (Mo–N–C) bond angle of 177.8(4)^∘. The complex has also been characterized by¹H NMR, IR, and UV–vis spectroscopy.     

Synthesis and Crystal Structures of Bromo(1,10-phenanthroline- N , N ′)tris(2-cyanoethyl)phosphinocopper(I) and Bromo(2,2′-bipyridine- N , N ′)tris(2-cyanoethyl)phosphinocopper(I)

The two new complexes bromo(1,10-phenanthroline-N,N′)tris(2-cyanoethyl)phosphinocopper(I) and bromo(2,2′-bipyridine-N,N′)tris(2-cyanoethyl)phosphinocopper(I) were synthesized and their X-ray crystal structures were determined. The first complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 7.7596(7) ?, b = 11.470(1) ?, c = 12.803(1) ?, α = 78.884(1)^°, β = 79.759(1)^°, γ = 86.867(1)^°, V = 1100.0(2) ?³ and Z = 2. The second complex crystallizes in the orthorhombic space group Pbca with the crystal cell parameters a = 10.614(1) ?, b = 12.345(1) ?, c = 31.903(3) ?, V = 4180.3(7) ?³ and Z = 8. In both compounds, the copper(I) ion is four-coordinate with a distorted tetrahedral geometry. In the 1,10-phenanthroline complex, an intermolecular dipole–dipole interaction between two cyano groups stabilizes an unfavorable synclinal conformation of one cyanoethyl group of the phosphine ligand.