Crystal and molecular structure of the mixed-ligand complex Zn[S2CN(CH3)2]2Phen

The crystal and molecular structure of the mixed-ligand complex Zn[S₂CN(CH₃)₂]₂Phen is determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK_α radiation, 3347 F(hkl), R = 0.0385). The crystals are monoclinic, a =13.340(3), b =13.827(3), c =24.698(5) å, Β =102.58(3)? V = 4446(2) å ³, Z = 8, d_calc = 1.452 g/cm³ , space group C2/c. The structure consists of monomeric molecules in which the zinc atom has a distorted octahedral environment (4S+2N). The molecular packing in the crystal involves dimers related by the 2 rotation axis and forming continuous chains along the c axis.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Two Succinato‐bridged Zinc(II) Phenanthroline Complexes: [Zn(phen)L2/2](H2L) and [(phen)2Zn(μ‐L)Zn(phen)2]L � 11H2O with H2L = Succinic Acid

Two mixed ligand Zn^II complexes [Zn(phen)L_2/2](H₂L) ( 1 ) and [(phen)₂Zn(μ‐L)Zn(phen)₂]L � 11H₂O ( 2 ) with H₂L = suc‐cinic acid were prepared and crystallographically characterized. Complex 1 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.618(1) Å, b = 9.585(1) Å, c = 15.165(1) Å, β = 96.780(6)°, V = 1965.6(3)ų, Z = 4 and complex 2 in the triclinic space group P 1¯ (no. 2) with a = 12.989(2)Å, b = 14.464(2)Å, c = 18.025(3)Å, α = 90.01(1)°, β = 109.69(1)°, γ = 112.32(1)°, V = 2917.4(8) ų, Z = 2. 1 consists of succinic acid molecules and 1D zigzag [Zn(phen)(C₄H₄O₄)_2/2] polymeric chains, in which the tetrahedrally coordinated Zn atoms are bridged by bis ‐ monodentate succinato ligands. Succinic acid molecules play an important role in supramolecular assemblies of the polymeric chains into 2D layers as well as in the stacking of 2D layers. 2 is composed of [(phen)₂Zn(μ‐L)Zn(phen)₂]²⁺ complex cations, succinate anions and hydrogen bonded water molecules. Within the divalent cations, Zn atoms are octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis‐chelating succinato ligand. Through the intermolecular π—π stacking interactions, the complex cations form positively charged 2D layers, between which the noncoordinating succinate anions and water molecules are sandwiched.     

Crystal structure of a new molecular complex of fullerene with tetramethyltetraselenafulvalene: C60·TMTSF·2CS2

A new molecular complex of fullerene with tetramethyltetraselenafulvalene (TMTSF), C₆₀·TMTSF·2CS₂, (1) was synthesized. The structure and composition of the complex were established by X-ray diffraction analysis. The crystals of C₆₀·C₁₀H₁₂Se₄·2CS₂ are monoclinic:a=15.407(2),b=12.934(2),c=12.026(2) Å β=108.39(3)°,V=2274.1(6) ų, space groupCm, Z=2,d _calc=1.929 g cm^?3,R=0.047. The crystal structure of 1 consists of layers. Layers formed by fullerene and CS₂ molecules alternate with layers of TMTSF molecules. Peculiarities of the crystal structure of 1 are the nonplanar conformation of TMTSF molecules and the absence of shortened C…C contacts between adjacent fullerenes molecules. The energy of intermolecular TMTSF…C₆₀ interactions in the crystal was estimated.     

Synthesis and crystal and molecular structure of the mixed-ligand coordination compound ZnPhen(n-C4H9OCS2)2

A mixed-ligand complex ZnPhen(n-BuOCS₂)₂ has been synthesized. The structure of the compound was solved by X-ray diffractometry (X8 APEX diffractometer, MoK _α radiation, 4254 F _hkl , R = 0.0448). Triclinic crystals with the parameters a = 9.4464(3) Å, b = 11.0279(4) Å, c = 13.6528(6) Å;α = 106.940(1)°, β = 98.382(1)°, γ = 106.347(1)°; V = 1264.72(8) ų; Z = 2, space group 1. P1ˉ. The structure consists of discrete mononuclear molecules. The polyhedron of the Zn atom is a trigonal bipyramid N₂S₃ formed by coordination of the N atoms of the bidentate Phen molecules and the sulfur atoms of the monodentate and cyclic bidentate xanthate ligands. Dimer assemblies are formed in the structure due to π-π interactions of Phen molecules. Original Russian Text Copyright ? 2006 by R. F. Klevtsova, T. G. Leonova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 6, pp. 1189–1194, November–December, 2006.     

Structurally characterized dinuclear zinc(II) bis(salamo)‐type tetraoxime complex possessing square pyramidal and trigonal bipyramidal geometries

A novel dinuclear Zn(II) complex with the chemical formula [Zn₂(L)(OCH₃)] has been synthesized by a bis(salamo)‐type tetraoxime ligand based on 3‐bromo‐5‐chlorosalicylicaldehyde, and characterized by elemental analyses, IR, UV–vis, and fluorescent spectra, and single‐crystal X‐ray diffraction analysis. All the Zn(II) atoms are pentacoordinated by N₂O₂ donor atoms from the (L)³⁻ unit and one oxygen atom from one μ₂‐methoxyl group. The Zn(II) (Zn1 and Zn4) atoms have distorted square pyramidal geometries (τ₁ = 0.458, τ₄ = 0.388), whereas the Zn2 and Zn3 atoms adopt trigonal bipyramidal (τ₂ = 0.675, τ₃ = 0.550) geometries. The Zn(II) complex is self‐assembled by intermolecular C H···O interactions to form an infinite three‐dimensional supramolecular structure. Interestingly, the intermolecular C H···π interactions in the Zn(II) complex is involved not in the formation of three‐dimensional structures but rather in the formation of the 0D dimer structure. Meanwhile, the optical properties of the Zn(II) complex were also measured and are discussed.     

Crystal and molecular structure of the volatile mixed-ligand complex Zn(S2CN(i-C4H9)2)2Phen

The crystal and molecular structure of the mixed-ligand complex Zn(S₂CN(i-C₄H₉)₂)₂Phen was determined by single-crystal X-ray diffractometry (Syntex P2₁ diffractometer, CuK_α radiation, 1738 F(hkl),R = 0.036). The crystals are triclinic, a =18.564(4), b =10.487(1), c =17.505(4) å, α = 84.04(2), Β =94.88(2), γ =90.87(2)?;V =3377(1) å ³, Z = 4, d_calc = 1.287 g/cm³, space group C-1. The structure consists of monomeric molecules in which the zinc atom has a distorted octahedral environment (4S+2N).     

Synthesis and polymer structure of [Zn(4,4′-bipy){(i-PrO)2PS2}2]n and thermal properties of ZnL{(i-PrO)2PS2}2 (L = phen, 2,2′-bipy, 4,4′-bipy)

A new mixed-ligand complex, Zn(4,4′-bipy){(i-PrO)₂PS₂}₂, was synthesized. Single crystals were grown,and the structure of the complex was determined by X-ray diffraction (CAD-4 diffractometer, MoK_α radiation, 14807 F_hkl, R =0.0391. The crystals are monoclinic with unit cell dimensions a-17.569(2), b = 26.253(5), c = 27.915(3) Å, ß =100.70(1)°, V = 12652(3) ų, Z = 16, d_valc = 1.361 g/cm³, space group P2₁/n. The structure is formed from infinite zigzag polymer chains stretched along the a axis. The coordination polyhedron of the Zn atom is a distorted tetrahedron formed by two S atoms of two monodentate diisopropyldithiophosphate ligands and two N atoms of two bridging bidentate 4,4′-bipy molecules. When heated in vacuum, the compounds ZnL{(i-PrO)₂PS₂}₂ (L) =phen, 2,2′-bipy, 4,4′-bipy are volatile.     

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF A 4,4′-BIPY-BRIDGED BINUCLEAR ZINC(II) COMPLEX, 2[R2NCS2]2 · Zn(4,4′-BIPY) (R=PIPERIDYL)

Abstract

The crystal structure of the title complex 2[R₂NCS₂]₂ · Zn(4,4′-bipy) (R = Piperidyl), 1, revealed that it consists of dimers made up from two crystallographically independent molecules. Each zinc atom in 1 forms a 5-coordinate pseudo-square-based pyramidal arrangement (with four Zn-S and one Zn-N interactions). Bondlengths to Zn with the coordinating atoms are comparable to those in other Zn(II) dithiocarbamate complexes. The piperidine ring has a chair conformation. To allow improved packing, the title complex molecules form an approximately linear arrangement extending along both a and b. TGA showed that 1 is decomposed in two close steps to produce ZnS as identified by residual weight. The complex 1 crystallizes in the monoclinic space group C2/c with cell parameters: a = 22.021(5), b = 22.215(3), c = 17.537(2) Å, β = 93.49(2)°, V = 8563(3) ų and Z = 8. The structure was refined by full-matrix least-squares methods to R = 0.067, R_w = 0.114.     

Synthesis, Characterization and Crystal Structure of a One-dimensional Diamagnetic Metal-radical Complex: [Zn(NIT4py)2(DTB)2(H2O)2]

A novel one-dimensional complex [Zn(NIT4py)₂(DTB)₂(H₂O)₂] (1), with mixed ligands [where NIT4py is 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and DTB is 3,5-dinitrobenzoate] has been synthesized and characterized by elemental analyses, i.r., u.v.–vis spectra, thermogravimetric analysis, X-ray single crystal diffraction and magnetic measurements. The complex crystallizes in the triclinic crystal system and space group Pî. The Zn ^II ion is in a distorted octahedral environment: two nitrogen atoms from two NIT4py entities, two oxygen atoms from two DTB units in the basal plane; and two oxygen atoms from the two water molecules in the axial position. The [Zn(NIT4py)₂(DTB)₂(H₂O)₂] units are connected as a one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the two radicals.     

Three multinuclear Co(II), Zn(II) and Cd(II) complexes based on a single-armed salamo-type bisoxime: syntheses,structural characterizations and fluorescent properties

Three multinuclear complexes, [Co(L)(OAc)Co(CH₃CH₂OH)₂]·H₂O, [Zn(L)(OAc)Zn(CH₃OH)], and [{Cd(L)(OAc)Cd(CH₃OH)}₂], containing a single-armed salamo-type bisoxime H₃L have been synthesized and characterized structurally. The Co(II) complex forms a dimeric unit by intermolecular hydrogen bond interactions of neighboring dimeric molecules. The Zn(II) complex also forms a dimeric unit by intermolecular hydrogen bond interactions. Interesting features of the crystal structure include O?O short contacts. Meanwhile, self-assembling infinite 1-D, 2-D, and 3-D supramolecular structures are formed by intermolecular hydrogen bond and C–H?π interactions. The Cd(II) complex forms an infinite 2-D supramolecular structure by intermolecular hydrogen bond interactions. The photophysical properties of the Co(II), Zn(II), and Cd(II) complexes have also been discussed.     

Crystal structure and thermodecomposition kinetics of a three-dimensional supramolecular Mn complex with 8-hydroxyquinoline

A three-dimensional supramolecular complex, [Mn(8-OHQ)₃] · CH₃OH (8-OHQ is 8-hydroxyquinoline), C₂₈H₂₂MnN₃O₄, was synthesized in methanol, and its crystal structure was determined by X-ray crystallography. The crystals are triclinic, space group P $P\bar 1$ , a = 10.823(2) Å, b = 13.222(3) Å, c = 17.283(3) Å, α = 90.03(3)°, β = 93.15(3)°, γ = 92.58(3)°, V = 2467.0(8) ų, Z = 4, F(000) = 1072, ρ = 1.399 g/cm³, μ = 0.575 mm^?1. Hydrogen bonds and intermolecular interactions, which are observed in the complex, stabilize its structure. The thermal decomposition kinetics of the complex was investigated under nonisothermal conditions using the Achar differential method and the Coats-Redfern integral method.     

Synthesis,Structure, and Polarized Optical Spectra of a New Fluoromanganate(III): [(H3N(CH2)2)2NH2]2[MnF5(H2O)]3

The synthesis and crystal structure of a new fluoromanganate(III), [(H₃N(CH₂)₂)₂NH₂]₂[MnF₅(H₂O)]₃, is reported. The unit cell is unusually large: monoclinic, P2₁/c (no. 14), a = 41.0512(13) Å; b = 9.6469(4) Å; c = 12.8021(7) Å; β = 91.927(4)°; Z = 8, R = 0.0627 and wR₂ = 0.1347. The [MnF₅(H₂O)]^2– anions are octahedral with a strong distortion along the F–Mn OH₂ axes due to the Jahn-Teller effect. A very rich intermolecular hydrogen bond framework is present, leading to chains of octahedra linked by double-hydrogen bonds. The polarized optical spectra on single crystals are explained in terms of the intraconfigurational d⁴ transitions split by a ligand field of C_4v symmetry.     

Crystal Structure and Disorder Phenomena of the Adduct of Neutral C60 and the Ionic Gold Complex (Ptol3)2AuNO3

The adduct C₆₀·(Ptol₃)₂AuNO₃ has been crystallized from toluene solutions of C₆₀ and (Ptol₃)₂AuNO₃ as violet, trigonal plate‐shaped crystals. The compound was studied by single‐crystal x‐ray diffraction ( , a = 1278.17(3), c = 2282.92(6) pm). The gold complex is dissociated into [(Ptol₃)₂Au]⁺ cations, which encapsulate the neutral C₆₀ molecules, and nitrate anions. The intermolecular interactions between the fullerene molecules and the gold complex cations and the resulting disorder is investigated. The crystal structure of C₆₀·(Ptol₃)₂AuNO₃ is providing an instructive example, demonstrating that symmetry‐matching is not always sufficient for avoiding disorder.     

Crystal and molecular structure of the monoclinic modification of Mn(S2CO-i-C3H7)2(2,2’-bipy)

The crystal and molecular structure of modification II of the Mn(S₂CO-i-C₃H₇)₂(2,2’-Bipy) complex was determined from X-ray diffraction data (“Syntex P2₁” diffractometer, CuK_α radiation, 1603 F(hkl), R = 0.0446). The crystals are monoclinic,a = 23350(3),b = 9.325(1),c = 22.030(2) å, Β = 106.98(1)?,V = 4587.7 å³, Z =8, d _calc = 1.394 g/cm³, space group C2/c. The structure consists of monomeric molecules in which the manganese atom has a distorted octahedral environment (4S + 2N). The orthorhombic and monoclinic modifications of the complex are compared with respect to the molecular geometry and packing.     

Modified components of RNA. The molecular and crystal structure of 5-carboxymethylaminomethyl-2-thiouridine (S2cmnm5U)

The structure of the title compound 1 has been determined by X-ray analysis. The following crystal data were found: orthorhombic, P2₁2₁2₁, a = 5.243(2), b = 24.864(4), and c = 37.083(6) Å. Three molecules of the compound with four molecules of water are present in the independent part of the unit cell. The sugar ring puckering is ³E for the molecules A and C and ³T₂ for the molecule B. The conformation of the hydroxymethylene group is g⁺ and g⁻ for B and A, C, respectively. The torsion angles χ for all molecules are in the range of the anti conformation. In the crystal lattice of 1 both the intra-and intermolecular hydrogen bonding systems occur.     

Crystal and molecular structure of the [Zn(HL)Cl]·EtOH compound, (H2L = chiral bis(menthane)propylenediaminodioxime)

The crystal structure of a solvate [Zn(HL)Cl]·EtOH is determined by single crystal X-ray crystallography (150 K, Bruker X8 Apex CCD autodiffractometer, MoK _α radiation). The crystals are triclinic, unit cell parameters are: a = 7.4755(4) Å, b = 13.9701(11) Å, c = 14.4593(19) Å, α = 82.277(2)°, β = 75.410(2)°, γ = 75.356(1)°, space group P1. The structure of the solvate contains two crystallographically independent complex [Zn(HL)Cl] molecules and two non-coordinated ethanol molecules. In each of the molecules, Zn²⁺ ions coordinate N atoms of tetradentate chelating ligands HL^? and a Cl atom. ClN₄ polyhedra have a distorted tetragonal pyramidal geometry. EtOH molecules make H-bonds with the complex molecules, thus facilitating the formation of chains along the x axis.     

Volatile ZnPhen(S2CNEt2)2 and MnPhen(S2CNEt2)2 complexes and the MnZn2Phen3(S2CNEt2)6 phase: Thermal behavior and crystal and molecular structures of two modifications of ZnPhen(S2CNEt2)2

Two crystal modifications, I and II, of the ZnPhen(S₂CNEt₂)₂ complex have been isolated. According to XRD data, the single crystals of I are triclinic with a=9.745(2), b=10.252(2), c=14.331(3) Å, α=99.18(2), β=91.01(2), γ=113.28(2)°, V=1293.2(4) ų, space group P1, Z=2, d_calc=1.401 g/cm³. The crystals of II are monoclinic with a=7.220(6), b=18.095(2), c=19.050(4) Å, β=95.85(2)°, V=2475.8(7) ų, space group C2/c, Z=4, d_calc=1.461 g/cm³. In both modifications, the structure is formed by monomer molecules with a distorted octahedral environment of the zinc atom. All atoms in I are in the general position; in II, the atoms are linked by the twofold rotation axis. It is shown by X-ray phase analysis (XRPA) that the MnPhen(S₂CNEt₂)₂ complexes (III) are isostructural to modification I of the ZnPhen(S₂CNEt₂)₂ complex, which underlies the synthesis of a solid solution of these complexes, MnZn₂Phen₃(S₂CNEt₂)₆ (phase IV). It is found that MPhen(S₂CNEt₂)₂ (M=Zn²⁺, Mn²⁺) and phase IV quantitatively sublime when heated in vacuum. Thermolysis of III in argon yields manganese(II) sulfide of cubic modification; the main product of thermolysis of phase IV is a solid solution of Zn_xMn_1?xS of hexagonal modification.     

Lanthanide(III) (Eu,Gd, Tb,Dy) Complexes Derived from 4‐(Pyridin‐2‐yl)methyleneamino‐1,2,4‐triazole: Crystal Structure,Magnetic Properties,and Photoluminescence

The reaction of lanthanide(III) nitrates with 4‐(pyridin‐2‐yl)methyleneamino‐1,2,4‐triazole (L) was studied. The compounds [Ln(NO₃)₃(H₂O)₃] ? 2 L, in which Ln=Eu ( 1 ), Gd ( 2 ), Tb ( 3 ), or Dy ( 4 ), obtained in a mixture of MeCN/EtOH have the same structure, as shown by XRD. In the crystals of these compounds, the mononuclear complex units [Ln(NO₃)₃(H₂O)₃] are linked to L molecules through intermolecular hydrogen‐bonding interactions to form a 2D polymeric supramolecular architecture. An investigation into the optical characteristics of the Eu³⁺‐, Tb³⁺‐, and Dy³⁺‐containing compounds ( 1 , 3 , and 4 ) showed that these complexes displayed metal‐centered luminescence. According to magnetic measurements, compound 4 exhibits single‐ion magnet behavior, with ΔE_eff/k_B=86 K in a field of 1500 Oe.