Synthesis and structure of zinc iodide complex with thiocarbamide, [Zn(CH4N2S)2I2]

A complex compound of zinc iodide with thiocarbamide [Zn(CH₄N₂S)₂I₂] is obtained and its structure is studied by X-ray diffraction. Crystals are monoclinic, a = 10.494(2) Å, b = 7.473(2) Å, c = 14.871(4) Å, β = 91.354(18)°, V = 1165.9(5) ų, space group P2₁/c, Z = 4. The structural unit of the crystal is molecular complex [Zn(CH₄N₂S)₂I₂], in which the zinc atom is coordinated by sulfur atoms of two thiocarbamide molecules and two iodine atoms.     

Crystal structure of samarium hexamolybdoaluminate Sm[Al(OH)6Mo6O18] · 11H2O

The structure of a new complex of samarium(III) with a hexamolybdoaluminate ion, Sm[Al(OH)₆Mo₆O₁₈] · 11H₂O, was established by the methods of X-ray diffraction analysis. The crystallographic data are as follows: sp. gr. Pbc2₁, a = 10.927(4) Å, b = 11.757(5) Å, c = 22.327(9) Å, V = 2868(1) ų, Z = 4, ρ _calcd = 3.040 g/cm³, R = 0.084, R _W = 0.198. In the [Al(OH)₆Mo₆O₁₈ ^3? anion, an Al atom is surrounded by six Mo atoms with distorted octahedral coordination. The anions are linked into chains via Sm atoms. The coordination polyhedron of a Sm atom is a tricapped trigonal prism with the vertices being occupied by two terminal oxygen atoms of two adjacent anions and seven water molecules.     

Crystal structure and vibrational spectra of two cadmium halide complexes with 1,2-Bis[2-(Diphenylphosphinylmethyl)phenoxy]ethane (L 1) and 1,3-bis[2-diphenylphosphinylmethyl)phenoxy]propane (L), CdBr2 ⋅ L 1 and CdI2 ⋅ L

Two cadmium halide complexes with 1,2-bis[2-(diphenylphosphinylmethyl)phenoxy]ethane (L ¹) and 1,3-bis[2-(diphenylphosphinylmethyl)phenoxy]propane (L), namely, CdBr₂ ? L ¹ (I) and CdI₂ ? L(II), have been synthesized. An analysis of their vibrational spectra is carried out. The structures of I and II are determined by X-ray diffraction. Crystals I are monoclinic, a = 31.562(6) Å, b = 13.548(3) Å, c = 18.733(4) Å, β = 91.28(3)°, space group C2/c, Z = 8, and R = 0.051 for 3776 reflections. Crystals II are triclinic, a = 11.803(2) Å, b = 12.554(3) Å, c = 14.686(3) Å, α = 90.30(3)°, β = 90.29(3)°, γ = 106.08(3)°, space group $P\bar 1$ , Z = 2, and R = 0.043 for 4916 reflections. Compounds I and II exhibit a polymeric chain structure. The potentially tetradentate ligands L ¹ and L are coordinated to the metal atoms only through two phosphoryl oxygen atoms and fulfill the bidentate bridging function. The environment of the Cd atom is completed to the tetrahedral coordination by two Br atoms in complex I and two I atoms in complex II. The mean distances are as follows: Cd-Br, 2.526(2) Å; Cd-I, 2.695 Å; and Cd-O, 2.243(8) Å in I and 2.210(4) Å in II. The L ¹ and L ligands in complexes I and II adopt an S-shaped conformation.     

Molecular interactions in substituted 2,2′-bipyridines: crystal structures of 2,2′-bipyridine-3,3′-dicarboxylic acid monohydrate and (2,2′-bipyridine-3,3′-dicarboxylic acid)dichlorocopper(II) dihydrate

In the monohydrate structurea=8.315(1),b=8.578(1),c=16.952(2)Å, Orthorhombic,P2₁2₁2₁, there are intramolecular interactions between the O atoms of the carboxyl groups and the C2 atoms of the opposite rings. The water molecule present in the structure is involved in an extensive network of hydrogen bonds. In the dichlorocopper(II) dihydrate complex structurea=12.442(1),b=19.614(1),c=14.481(1)Å, β=94.38(1)°, Monoclinic,C2/c, the Cu(II) is coordinated to two Cl atoms, two N atoms of the bipyridyle ligand and a water molecule. There are possible Cl ion bridges between the two Cu atoms to form pseudo-discrete dimers. The uncoordinated carboxylic acid groups and the water molecules, present in the complex, form an interesting network of hydrogen bonds.     

Synthesis and crystal structure of the [Co<Subscript>2</Subscript>(Nicotinamide)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>9</Subscript>COO)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)] complex

The [Co₂ L ₄(C₄H₉COO)₄(H₂O)] coordination compound of cobalt(II) valerate with nicotinamide (L) is synthesized and studied by IR spectroscopy. The crystal structure of the synthesized compound is determined. The crystals are triclinic, and the unit cell parameters are as follows: a = 10.2759(10) Å, b = 16.3858(10) Å, c = 16.4262(10) Å, α = 100.538(10)°, β = 101.199(10)°, γ = 90.813 (10)°, Z = 2, and space group P \(\bar 1\). The structural units of the crystal are dimeric molecular complexes in which pairs of cobalt atoms are linked by triple bridges formed by oxygen atoms of two bidentately coordinated valerate anions and a water molecule. The octahedral coordination of each cobalt atom is complemented by the pyridine nitrogen atoms of two nicotinamide ligands and the oxygen atom of the monodentate valerate group. The hydrocarbon chains of the valerate anions are disordered over two or three positions each.     

Synthesis and crystal structure of <Emphasis Type="Italic">catena</Emphasis>-bis(nicotinamide)aqua(μ-phthalato)copper(II) hemihydrate

The copper(II) phthalate complex with nicotinamide [CuL ₂(μ-Pht)(H₂O)] · 0.5H₂O(I) (where L is nicotinamide and Pht ^2? is an anion of phthalic acid) is synthesized and investigated using IR spectroscopy and X-ray diffraction. The crystals of compound I are monoclinic, a = 13.368(2) Å, b = 7.891(3) Å, c = 20.480(2) Å, β = 108.69(2)°, Z = 4, and space group P2₁/c. The structural units of crystal I are linear chains formed by bridging phthalate anions and crystallization water molecules. The copper atom is coordinated by two pyridine nitrogen atoms of two nicotinamide ligands (Cu-N, 2.001 and 2.045 Å), two oxygen atoms of different phthalate anions (Cu-O, 1.964 and 2.235 Å), and the oxygen atom of the H₂ O molecule (Cu-O, 2.014 Å). The coordination polyhedron of the copper atom is completed to an elongated (4 + 1 + 1) tetragonal bipyramid by the second (chelating) oxygen atom of the carboxyl group (Cu-O, 2.587 Å), which is one of the anions of phthalic acid. The linear polymer molecules are joined into complex macromolecular dimers with the closest internal contacts of the specific type. The macromolecular dimers are the main supramolecular ensembles of the crystal structure.     

Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

The new compound [Pd(NH₂CH₂CH₂OH)₄][Pd₆(NH₂CH₂CH₂S)₈]Cl₆ · 5H₂O (I) is synthesized and its crystal structure is determined. The crystals are monoclinic, a = 25.625(6) Å, b = 9.633(5) Å, c = 24.847(7) Å, β = 91.47(2)°, Z = 4, and space group C2/c. The structural units of crystals I are the centrosymmetric hexanuclear [Pd₆(NH₂CH₂CH₂S)₈]⁴⁺ cations, the mononuclear [Pd(NH₂CH₂CH₂OH)4]²⁺ cations with C ₂ symmetry, the Cl^? anions, and crystallization water molecules. In the hexanuclear cation, the interaction between the Pd atoms occurs through the S atoms of the mercaptoethylaminate ligands. The Pd(2) and Pd(3) atoms and the ligands form two metallochelate fragments in which the N and S atoms are located in cis positions. The average lengths of the Pd-S and Pd-N bonds are equal to 2.274(1) and 2.074(6) Å, respectively. The metallochelate fragments are joined to each other and to their centrosymmetric analogues through the Pd(1) atom, which coordinates four S atoms [the average Pd-S_av bond length is 2.332(1) Å]. In the mononuclear cation, the Pd(4) atom coordinates four N atoms of the monoethylaminate ligands [the Pd-N bond lengths are 2.045(6) and 2.056(6) Å]. The shortest Pd?Pd distance is equal to 3.207(1) Å. The bonding in the structure is provided by numerous hydrogen bonds with the participation of all the H₂O molecules, NH₂ groups, and Cl^? anions.     

Crystal structures and properties of isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide

The para and ortho isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide (I and II, respectively) are synthesized, and their physicochemical properties and structure are investigated. The para isomer I has a higher melting temperature and is less soluble in organic solvents as compared to the ortho isomer II. The electronic absorption spectra indicate that absorption for molecule I occurs at longer wavelengths than for molecule II. A correlation between the physicochemical properties and the crystal structures of compounds I and II is revealed. Crystals I · 0.5C₆H₆ are triclinic; the unit cell parameters are a = 11.760(2) Å, b = 13.958(3) Å, c = 15.012(3) Å, α = 108.01(2)°, β = 103.95(1)°, γ = 92.00(2)°, V = 2258.3(8) ų, space group $P\bar 1$ , and Z = 4. Crystals II are monoclinic; the unit cell parameters are a = 9.302(2) Å, b = 16.380(3) Å, c = 13.480(3) Å, β = 100.09(3)°, V = 2022.1(7) ų, space group P2₁/c, and Z = 4. Structures I · 0.5C₆H₆ and II are characterized by intramolecular and intermolecular hydrogen bonds.     

Synthesis, crystal structure, and thermal properties of {[Cd2(L1)3(sac)4]⋅2CH2Cl2}∞: A coordination polymer with non-interpenetrating ladders containing cadmium in a rare, trigonal bipyramidal coordination environment (L1 = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, sac = saccharinate)

The new coordination polymer, {[Cd₂(L1)₃(sac)₄]?2CH₂Cl₂}_∞:, has been prepared from the reaction of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L1) with [Cd(sac)₂(H₂O)₄].2H₂O(sac = saccharinate) in a methylene chloride/ethanol solvent mixture. The compound features a non-interpenetrating ladder motif constructed from Cd(L1)3 T-shaped units. The Cd atoms are coordinated to three nitrogen donor atoms from three L1 ligands and two nitrogen donor atoms from two saccharinate ligands in a rare, trigonal bipyramidal coordination environment. The compoundwas further characterized by IR spectroscopy and DTA/TGA. {[Cd₂(L1)₃(sac)₄]?2CH₂Cl₂}_∞: crystallizes in the triclinic space group P-1 with a = 10.8747(19)Å, b = 12.626(2)Å, c = 15.749(3)Å, α = 111.839(3)^°, β = 97.442(3)., and γ = 106.239(3)^°     

Synthesis and the crystal structure of aqua-dioxo-nitrato-(2,2′,6′,2″-terpyridine)-neptunium(V) [NpO2(NO3)(terpy)(H2O)]

The crystal structure of the [NpO₂(NO₃)(Terpy)(H₂O)] complex between pentavalent neptunium and 2,2′,6′,2″-terpyridine is determined. The crystal data are as follows: a = 11.130(3) Å, b = 7.916(2) Å, c = 18.324(5) Å, β = 100.873(6)°, V = 1585.5(8) ų, Z = 4, space group is P2₁/n, R = 0.044, and wR(F ²) = 0.092. The coordination polyhedron of the Np atom is a pentagonal bipyramid whose equatorial plane includes three nitrogen atoms of the Terpy molecule and two oxygen atoms of the nitrate ion and the water molecule.     

Crystal structure of calcium trans-N-(nitrilotriacetato)(pyridine-2-carboxylato)cobaltate(III) hexahydrate, Ca[Co(Nta)(Pic)]2] · 6H2O

Crystals of Ca[Co^III (Nta)(Pic)]₂ · 6H₂O (I) (where Nta ^3? and Pic ^? are the nitrilotriacetate and picolinate ions, respectively) are prepared and characterized by the X-ray diffraction technique. Crystals I are monoclinic, a = 18.599(4) Å, b = 12.556(3) Å, c = 14.042(3) Å, β = 102.90(3)°, V = 3196(1) ų, Z = 4, space group P2₁/c, R1 = 0.0278, wR2 = 0.0716, and Goof = 1.054 for 4982 reflections with I > 2σ(I). Structure I is built of the { Ca(H₂O)₄[Co(Nta)(Pic)]₂{ _1∞ polymer ribbons and molecules of crystallization water. One of the two symmetrically independent anionic complexes (B) is included in the chain and alternates with cationic units, whereas the other anionic complex (A) forms a branch of this chain. The cationic and anionic units are interlinked via the interactions of the Ca²⁺ cations with the carbonyl atoms of the main (Nta ^3?) and additional (Pic ^?1) ligands. The octahedral environment of the Co(III) atoms consists of donor atoms of the Nta ^3? (N + 3O) and Pic ^? (N + O) ligands. The coordination polyhedron of the Ca atom (pentagonal bipyramid) includes two carbonyl O atoms of two Nta ^3? ligands, one O_Pic atom, and four O_w atoms of water molecules.     

Crystal structure of zinc iodide complex with carbamide, ZnI2 · 2CO(NH2)2

The structure of ZnI₂ · 2CO(NH₂)₂ is determined by single-crystal X-ray diffraction. The crystals are monoclinic, a = 12.694(3) Å, b = 6.886(2) Å, c = 13.161(3) Å, β = 110.58(2)°, Z = 4, space group P2₁/a, and R = 0.0337 for 2481 reflections. Similar to the chloride analogue, the structure consists of discrete molecules with tetrahedrally coordinated Zn atoms. The bond lengths and angles are as follows: Zn-I, 2.5749(8) and 2.5473(8) Å; Zn-O, 1.954(3) and 1.985(4) Å; IZnI, 113.74(3)°; OZnO, 100.5(2)°; and IZnO, 108.5°–113.1(1)°. The crystal structure agrees with the IR and electronic absorption spectra of the crystals.     

Crystal structures of complexes of the <Emphasis Type="Italic">cys-syn-cys</Emphasis> isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][TaF₆] and [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) Å, b = 11.947(5) Å, c = 27.392(12) Å, β = 93.11(1)°, Z = 4, and space group P2₁/n for modification I; and a = 10.828(1) Å, b = 11.204(1) Å, c = 12.378(1) Å, α = 72.12(1)°, β = 79.40(1)°, γ = 73.70(1)°, Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] (III) with the unit cell parameters a = 10.796(3) Å, b = 11.183(3) Å, c = 12.352(3) Å, α = 72.364(5)°, β = 79.577(5)°, γ = 73.773(4)°, Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I–III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48–2.58 Å). The conformation of the macrocycle in complex I differs substantially from that in complex II (III).     

Synthesis and Crystal Structure of Di-μ-chlorido-bis{chlorido[4-ethyl-<Emphasis Type="Italic">N</Emphasis>-(pyridin-2-ylmethylidene-κ<Emphasis Type="Italic">N</Emphasis>)aniline-κ<Emphasis Type="Italic">N</Emphasis>]mercury(II)}

The centrosymmetric dinuclear title complex [Hg₂Cl₄(dip)₂] was synthesized using the Schiff base bidentate ligand (E)-4-ethyl-N-(pyridine-2-ylmethylene)benzeneamine (dip) and mercury(II) chloride salts. It has been characterized by elemental analysis, X-ray diffraction, and UV-Visible and infrared spectroscopic techniques. The X-ray analysis shows that the title compound crystallizes in the monoclinic sp. gr. P2₁/n, Z = 2 with a = 7.8233(17) Å, b = 15.178(3) Å, c = 12.559(3) Å, β = 97.021(3)°. The Hg(II) ion has a distorted trigonal–bipyramidal coordination environment formed by the bischelating N-heterocyclic ligands, two bridging Cl atoms and one terminal Cl atom.     

Synthesis and crystal structure of bis(carbamide)chromatoneptunyl NpO2CrO4 · 2[OC(NH2)2]

The crystal structure of the hexavalent neptunium complex NpO₂CrO₄ · 2[OC(NH₂)₂] is determined. The crystal data are a = 7.192(2) Å, b = 12.902(4) Å, c = 11.226(3) Å, β = 92.19(2)°, V = 1040.9(4) ų, space group P2₁/n, Z = 4, d _calcd = 3.223 g/cm³, R = 0.045, and R _w = 0.130. The coordination polyhedron of the Np atom is the pentagonal bipyramid whose equatorial plane is formed by the oxygen atoms of the chromate ions and carbamide molecules.     

Crystal structure of an yttrium nitrate complex with tetramethylurea

An X-ray diffraction study of Y(NO₃)₃ · 3TMU crystals is performed (heavy-atom method, difference electron-density maps, H atoms in calculated positions, full-matrix anisotropic-isotropic (H) least-squares refinement). The crystals are monoclinic, a = 9.353(1) Å, b = 15.966(3) Å, c = 18.805(8) Å, β = 95.41(2)°, Z = 4, and space group P2₁/c. The structural units of the crystals are molecular complexes. The coordination number of the Y atom is nine due to three bidentate NO₃ groups and three monodentate tetramethylurea molecules. The mean Y-O bond lengths are 2.464 and 2.274 Å for NO₃ and tetramethylurea, respectively.     

Crystal structures of benzo-18-crown-6 complexes with oxonium hexafluorotantalate and oxonium hexafluoroniobate

The crystal structures of [(benzo-18-crown-6) · H₃O]TaF₆ and [(benzo-18-crown-6) · H₃O]NbF₆ complex compounds are determined by X-ray diffraction. It is revealed that the tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and orthorhombic (II) modifications. The unit cell parameters of these compounds are as follows: a = 14.784(2) Å, b = 8.390(4) Å, c = 18.005(6) Å, β = 95.78(2)°, Z = 4, and space group P2₁/n for modification I; and a = 8.456(2) Å, b = 21.967(5) Å, c = 24.122(5) Å, Z = 8, and space group Pbca for modification II. The orthorhombic niobium complex [(benzo-18-crown-6) · H₃O]NbF₆ with the unit cell parameters a = 8.454(1) Å, b = 21.943(3) Å, c = 24.127(4) Å, Z = 8, and space group Pbca (III) is isostructural with tantalum complex II. The oxonium cation in complexes I–III is encapsulated by the crown ether and thus forms one ordinary and two bifurcate hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H ...F contacts (H...F, 2.48–2.58 Å).     

X-ray investigations of sulfur-containing fungicide: Structure of the benzoylphenyl(4-tolylazo)methyl 4-tolyl sulfone

Crystal and molecular structure of the of benzoylphenyl(4-tolylazo)methyl 4-tolyl sulfone was determined by x-ray analysis; crystal system, monoclinic; space group P2 ₁/c; a = 12.807(1) Å, b = 17.512(1) Å, c = 11.879(1) Å, β = 111.23(1)°. Conformation of the title compound is constrained by attraction of the positively charged sulfur and β-carbon atoms to the negatively charged oxygen atoms. Characteristic distribution of bond lengths in the central part of a molecule suggests that electrostatic interactions are strengthened by the stereoelectronic donation of electron density from the α-azo N2 towards the sulfonyl S and β-carbonyl C2 atoms.     

Crystal structure of SrFe(<Emphasis Type="Italic">EDTA</Emphasis>)Cl · 5H<Subscript>2</Subscript>O

The crystal structure of the SrFe(Edta)Cl · 5H₂O (I) complex is determined. The crystals are monoclinic, a = 7.530(4) Å, b = 10.575(3) Å, c = 23.308(10) Å, β = 95.75(4)°, Z = 4, and space group P2₁/c. The structural units of I are infinite ribbons of the molecular type that are formed by tetranuclear fragments. A tetranuclear fragment involves the centrosymmetric positively charged dimer group [Sr(H₂O)₄Cl] ₂ ²⁺ at the center and the [Fe(Edta)(H₂O)]_? anionic complexes, which compensate for the positive charge of the dimer group, at the periphery. These constituents are bound via bridging oxygen atoms of the Edta ligands. The coordination number of the Sr atom is nine. The Sr-O bond lengths lie in the range between 2.552 and 2.766 Å, the Sr-Cl bond length is 3.216(3) Å, and the Sr?Sr distance is 4.371(1) Å. The parameters of the [Fe(Edta)(H₂O)]^? group are within the range of values observed in such complexes: Fe-O, 1.996–2.086(3) Å; Fe-O(w), 2.110(4) Å; and Fe-N, 2.289(4) and 2.327(4) Å. Separate ribbons are linked by hydrogen bonds involving all H₂O molecules and terminal oxygen atoms of the Edta ligand.     

The Crystal and Molecular Structure of the Complex Diaquatetrakis(imidazole)copper(II) Terephthalate Crystal Structure Containing Cu(II) Him and TA

The title compound has been synthesized and its crystals structure determined at room temperature. MW = 536.01, monoclinic, space group C2/c, Z = 4, a = 22.193(5) Å, b = 8.038(2) Å, c = 15.699(4) Å, β = 119.64(2)°. The crystal structure consists of repeated [Cu(Him)₄(H₂O)₂] (Him = imidazole) cations and non-coordinated terephthalato dianions. The copper(II) ion displays an elongated octahedral coordination being linked to the four nitrogen atoms of the four imidazole ligands and to the two oxygen atoms of the two water molecules. The terephthalato dianions are hydrogen bonded to the four water molecules and four imidazole groups.