Bis(η2‐cyclo­octene)(N,N‐di­methyl­dithiocarbamato‐S,S′)­iridium(I), the first example of a tetracoordinate IrI complex containing two π‐bonded monoolefin ligands

The title compound consists of [Ir(C₃H₆NS₂)(C₈H₁₄)₂] mol­ecules lying on positions with site symmetry 2. Both the coordination plane, defined by the metal, S atoms and the two midpoints of the olefinic bonds, and the di­thio­carbamate chelate system are essentially planar. The orientation of the coordinated C=C bonds with respect to the coordination plane is close to perpendicular [(C=C,Ir)/(Ir,S,S) interplanar angle: 79.4 (2)°]. The Ir—C distances are 2.144 (3) and 2.155 (3) Å, and the Ir—S bond length is 2.3661 (8) Å. Due to π‐coordination, the olefinic bonds are elongated to 1.424 (5) Å. The cyclo­octene ligands adopt a crown conformation.     

Strukturbestimmungen an nichtlinearen Metallocenen. II. Die Molekül- und KristallStruktur von Benzol-1,2-Dithiolato-di(π-Cyclopentadienyl)-Titan (IV)

The chelate complex (C₅H₅)₂TiS₂C₆H₄ crystallizes in the centrosymmetric monoclinic soace group P2¹/c with the cell dimensions a = 14.366 Å, b = 15.380 Å, c = 12.736 Å, β = 90.2° and Z = 8. The S₂C₆H₄ plane of the molecule is folded out of the TiS₂ plane by an angle of 46°. The coordination polyhedron around the titanium atom defined by the cyclopentadienyl ring centroids and the sulfur atoms is a distorted tetrahedron of nearly mm2? C2v symmetry. The distances Ti? S and S? C are shorter, then those of single bonds of these atoms. The cyclopentadienyl rings are in staggered or eclipsed arrangement with respect to each another.     

Crystal structure of Fe2P2O7

Fe₂P₂O₇ crystallizes in the $\text{C}\text{1}$ space group with lattice parameters a = 6.649(2)Å, b = 8.484(2)Å, c = 4.488(1)Å, α = 90.04°, β = 103.89(3)°, γ = 92.82(3)°, and ?_cal = 3.86 g/cc. It is essentially isostructural with β-Zn₂P₂O₇. As in the Zn compound, the bridging oxygen atom in the P₂O₇ group shows a high anisotropic thermal motion. It appears that the P-O-P bond angle is linear as a result of extensive π bonding with the p orbitals on the bridging oxygen atom. The high thermal motion is vibration of the atom into cavities in the structure.     

Crystal structure of a new modification of the cyanide-bridged copper(I) coordination compound [CuCN(bpy)] n

The hydrothermal reaction of CuCN and bpy in the presence of an octahedral cluster complex K_2.75Cs_1.25[Re₆Se₈(CN)₄(OH)₂]·H₂O affords a cyanide-bridged chain coordination polymer [CuCN(bpy)] _n (bpy — 2,2′-bipyridyl) (1). The structure is monoclinic, space group C2/c, a = 22.848(2) Å, b = 7.7182(8) Å, c = 14.4331(13) Å, β = 127.805(2)°, V = 2010.9(3) ų, Z = 8, d _x = 1.623 g/cm³. Copper atoms have a tetrahedral coordination environment formed by N atoms of the bpy molecule as well as N and C atoms of ambidentate bridging CN ligands.     

Coordination polymer of uranyl nitrate with 4,4,10,10-Tetramethyl-1,3,7,9-Tetraazaspiro[5.5]undecane-2,8-dione (Spirocarbone, Sk): Synthesis and study of molecular and crystal structures

The coordination polymer {[UO₂(NO₃)₂(C₁₁H₂₀N₄O₂)] · 2H₂O} _n (I) was obtained and examined by X-ray diffraction. The crystals are monoclinic, space group C2/c; a = 23.1386(13), b = 5.41575(15), c = 19.7769(11) Å, β = 125.285(8)°, V = 2023.01(17) ų, ρ_calcd = 2.20 g/cm³, Z = 4. The U atom occupies a special position in the center of inversion. Its coordination polyhedron is a distorted hexagonal bipyramid with axial oxo ligands. In the equatorial plane, the U(1) atom is coordinated by four O atoms of two bidentate nitrate anions and two O atoms of two carbonyl groups of organic spirocarbone (Sk) molecules, which are related by the symmetry operation (0.5 ? x, 0.5 ? y, ?z). In the crystal, polymer chains are parallel to the direction (101). Water molecules are hydrogen-bonded to the N(1) atom of ligand Sk; in addition, they are linked together by the intermolecular hydrogen bonds O(6)-H(6d)…O(6)ⁱ(ⁱ1/2 ? x, ?1/2 + y, 1/2 ? z); H…O 2.11 Å angle O-H…O 160°) and to the nitrate anions by the hydrogen bonds O(6)-H(6e)…O(3)ⁱ; H…O 2.29 Å; the angle O-H…O 149°). In the crystal, hydrogen-bonded water molecules form chains along the axis y that are perpendicular to the coordination polymers. To verify the purity of complex I, the Rietveld refinement of its X-ray powder diffraction pattern was performed. At room temperature, the unit cell parameters are a = 23.2965(6), b = 5.51225(15), c = 19.8588(6) Å, β = 125.6063(17)°, V = 2073.40(10) ų.     

The Crystal Structure of (1, 1′-ferrocenediyl)diphenylsilane

The crystal structure of (1,1′-ferrocenediyl)diphenylsilane has been determined from analysis of photographic X-ray data. The crystal system is orthorhombic, a = 14.18(2), b = 12.54(2), c = 9.28(1) Å, space group Pnma with four formula units. The molecule has crystallographic m (C_s) symmetry with atoms Fe and Si lying in the mirror plane, which bisects the two phenyl groups. The planar cyclopentadienyl rings are bridged by a single silicon atom, and are tilted 19.2° with respect to one another. The Fe—C(Cp) distances vary from 2.01(1) to 2.11(1) Å. The bridging angle C(1)—Si—C(1′) is 99.1°, while the Si—C(sp²) bond lengths range from 1.86 to 1.88 Å. The exocyclic C(1)—Si bond makes an angle of 40° with respect to the plane of the cyclopentadienyl ring.     

Electron diffraction investigation of the molecular structure of cyclopropyl silane

The molecular structure of cyclopropyl silane (CPS) has been determined by gas phase electron diffraction. Among other parameters the bond distances (r_a) are: C₁C₂ = 1.528(2) Å, C₂C₃ = 1.490(4) Å, SiC = 1.840(2) Å, CH = 1.095(3) Å. The angle between the ring plane and the bond SiC is 55.9(3)°. The introduction of a tilt of the silyl group is in agreement with the secondary effect of substituents. The role of the silicon 3d orbitals in the interpretation of the structural data of CPS is discussed. Our results support the interpretation of the SiC bond to silicon in terms of dπ conjugation. This causes an asymmetry in the structure of the ring. The (pd)_π bonding concept is considered to be the sum of three different contributions: ionic, steric and dπ conjugation.     

Crystal structure of barium (cyclohexane-1,2-diaminetetraacetato)cobaltate(III) nonahydrate Ba[Co(Cdta)]2 · 9H2O

The crystal structure of Ba[Co(Cdta)]₂ · 9H₂O has been determined by X-ray diffraction. The crystals are monoclinic, a = 15.9415(10) Å, b = 7.8449(6) Å, c = 32.230(2) Å, β = 100.387(8)°, Z = 4, space group C2/c)). The cyclohexane-1,2-diaminetetraacetate ion forms the octahedral [Co(Cdta)]^? complex through two donor nitrogen atoms and four oxygen atoms and is also connected to two barium atoms through oxygens. The Ba atoms are on a twofold axis. Its nearest environment comprises five O atoms of water molecules, one also being located on a twofold axis, and four O atoms of the four neighboring complex ions. This gives infinite layers parallel to the ab plane. All water molecules form hydrogen bonds within one layer.     

Etude spectroscopique de derives mercuriques d'amidesthiols: Partie II. Structure cristalline et spectres de vibration du bis(méthylcarbamoyléthanethiolato)mercure(II)

In the solid state, the compound [Hg(SCH₂CH₂CONHCH₃)₂] is characterized by mercury-sulphur bonds with no interaction between mercury and the amide group. The two Hg-S bonds are almost co-linear (S(1)-Hg-S(2) = 177.6(4)°). The vHgS stretching vibrations (382 and 340 cm^?1) are consistent with the short Hg-S distance (2.35(1) Å). Four additional sulphur atoms at distances from mercury ranging from 3.25 to 3.60 Å complete a distorted octahedron. These octahedra are joined by edges and form infinite sheets parallel to the xOz plane. Molecules are linked along the a axis by N-H?O hydrogen bonds. The average N?O distance is 2.78 Å and vNH and vCO appear at 3286 and 1640 cm^?1, respectively.     

Coordination polymer of cadmium(II) iodide with tetramethylpyrazine

Compound [CdI₂(Me₄Pyz)] is synthesized by the reaction of CdI₂ with tetramethylpyrazine (Me₄Pyz, C₈H₁₂N₂), and its structure is determined (CIF file CCDC 1538646). The crystals are monoclinic, space group C2/c, a = 14.732(3), b = 11.084(2), c = 7.792(2) Å, ß = 95.27(3)°, V = 1267.0(4) Å, ?_calcd = 2.634 g/cm³, Z = 4. Polymer chains [CdI₂(Me₄Pyz)]_221e extended along the direction [001] are formed in the structure of the complex due to the bridging iodine atoms. The coordination polyhedron of the Cd²⁺ ion is a trigonal bipyramid with four bridging iodine atoms and one nitrogen atom of the organic ligand lying in the equatorial plane along with two iodine atoms. The distance between the cadmium atoms in the chain is 4.155 Å.     

Crystal Structure of μ‐Oxo‐bis[9,22‐(bisbutyloxy)hemiporphyrazinato]iron(III)

The crystal structure of the title compound, C₆₈H₆₀N₁₆O₅Fe₂, shows a dinuclear complex of two crystallographically independent, distorted hemiporphrazinato iron complexes with five‐coordinate iron and oxygen as bridging ligand. The Fe1‐O1‐Fe2 angle is 151.16°, the Fe‐O bond lengths are Fe1‐O1 [1.771(2) Å] and Fe2‐O1 [1.773(2) Å]. The dinuclear complexes have a staggered conformation with a dihedral angle of 26.2°, but coaxially to form tetrameric units is not observed. The molecule is characterized by short Fe‐N (isoindole) bonds [1.998(3) Å] and long Fe‐N (pyridine) bonds, values range from [2.175(3) Å] to [2.245(3) Å].     

[Cu3(C11H12N3OS)3(C11H10N3OS)]SO4 · 3H2O, a trinuclear heteroleptic copper(II) complex with N-allyl-N′-salicylidenethiosemicarbazone and its cyclization product: Synthesis and X-ray diffraction study

Single crystals of a trinuclear copper(II) complex with N-allyl-N′-salicylidenethiosemicarbazone and its cyclization product were obtained and examined by X-ray diffraction. Prolonged keeping of the reaction mixture in aqueous ethanol at room temperature resulted in partial cyclization of the starting ligand into 2-(4-allyl-5-mercapto-4H-1,2,4-triazol-3-yl)phenol followed by coordination of both ligands to copper ions, giving a cluster-type trinuclear complex of the empirical formula C₄₄H₅₀N₁₂O₁₁S₅Cu₃. The crystals are monoclinic, space group P2₁/n, a = 14.1169(4) Å, b = 20.1006(5) Å, c = 19.6852(5) 0A, β = 107.065(2)°, Z = 4, R ₁ = 0.0586 (I > 4σ(I)). The structure of the complex consists of three square fragments; in each fragment, the Cu atom is coordinated in a tridentate fashion by the starting organic ligand in the thione form. The cyclization product of this ligand is coordinated through two triazole N atoms and the thiol S atom, thus extending the square environment of copper. The cluster structure of the complex is formed by the bridging bonds Cu-O-Cu between the Cu(1) and Cu(2) atoms and by the bridging bonds Cu-S-Cu between the Cu(2) and Cu(3) atoms.     

Die konformation des μ-bis[tetracarbonylrhenium(I)]-bis-[tetracarbonyl(trithiocarbonato)rhenium(I)], eines überraschenden reaktionsproduktes bei der umsetzung von CF3Re(CO)5 mit CS2

The molecular structure of [(C₆H₅)₃P]₂Pd(C₃H₄) has been determined from three-dimensional X-ray diffraction data. The crystal belongs to the triclinic system, space group P$\text{1}$, with two formula units in a cell of dimensions: a = 19.475(2), b = 10.204(2), c = 18.341(2) Å, α = 108.46(2), β = 85.46(1), and γ = 118.80(1)°.One of the olefinic bonds of allene is coordinated to the palladium atom: PdC(1) = 2.118(9) and PdC(2) = 2.067(8) Å. The coordinated allene is no longer linear, the C(1)C(2)C(3) angle being 148.3(8)°. The C(1)C(2) distance is 1.401(11) Å, whereas the uncoordinated bond remains unchanged [C(2)C(3) = 1.304(12) Å]. The Pd, P(1), P(2), C(1) and C(2) atoms lie almost in the same plane.     

A complex of cadmium(II) iodide with 4-cyanopyridine: Synthesis,crystal structure,and luminescent properties

The complex [CdI₂(4-CNPy)₂] (I) was obtained by a reaction of CdI₂ with 4-cyanopyridine (4-CNPy, C₆H₄N₂) and structurally characterized (CIF file CCDC no. 983377). The crystals of complex I are monoclinic, space group C2, a = 24.698(5) Å, b = 4.127(1) Å, c = 7.597(2) Å, β = 96.05(1)°, V = 770.0(3) ų, ρ_calcd = 2.477 g/cm³, Z = 2. In structure I, iodine atoms serve to unite complex molecules into the polymer chains [CdI₂(4-CNPy)₂]_∞ along the direction [010]. The Cd(1) atom lying on a twofold axis has a slightly distorted octahedral environment made up of four bridging iodine atoms and two nitrogen atoms of two ligands 4-CNPy (Cd-I_av, 2.947(2) and Cd-N(1), 2.410(6) Å). Within each chain, cadmium atoms are spaced apart at 4.13 Å. Complex I exhibits photoluminescence.     

Specific features of the reaction between tris(5-bromo-2-methoxyphenyl)antimony and 2-oxybenzaldoxime: Structure of bis(μ3-2-oxybenzaldoximato-O,O′,N)-(μ2-oxo)-bis(5-bromo-2-methoxyphenyl)antimony

Bis(μ₃-2-oxybenzaldoximato-O,O′,N)-(μ₂-oxo)-bis(5-bromo-2-methoxyphenyl)antimony, which crystallizes from toluene in the form of a solvate, has been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)antimony and 2-oxybenzaldoxime in the presence of hydrogen peroxide. According to X-ray diffraction data, the structurally equivalent antimony atoms in a binuclear complex molecule are linked via two tridentate bridging ligands and an oxygen atom and have a distorted octahedral coordination to the C₂O₃N surrounding The trans-angles of the octahedron are CSbO (168.7(1)°), CSbN (164.1(1)°), and OSbO (159.3(1)°), and the bond lengths are Sb-C (2.127(4), 2.159(3) Å) and Sb-N (2.238(3) Å). A molecule contains the three types of Sb-O distances with a bridging oxygen atom (1.950(1) Å), the oxygen atoms of oxy groups (2.002(2) Å), and the oxygen atoms of oxime groups (2.091(2) Å). Sb?OCH₃ intramolecular contacts (3.097, 3.290 Å) also exist.     

2-Nitro-N,N-bis(2-nitro­phenyl­thio)­benzenesulfon­amide

The central N atom of C₁₈H₁₂N₄O₈S is essentially planar, lying 0.071 (2) Å out of the plane defined by the three S atoms. N—S distances are 1.712 (2) and 1.721 (2) Å to S—Ar, and 1.681 (2) Å to SO₂—Ar. The nitro group on the phenyl ring carrying the SO₂ group lies out of plane, with C—C—N—O– torsion angle 69.8 (3)°, while the other two nitro groups are near coplanarity, with torsion angle magnitudes 10.4 (3) and 14.0 (3)°.     

The crystal structure of ammonium β-octamolybdate pentahydrate

X-ray structure analysis (film data, R = 0.080 for 1568 reflections) has confirmed the structure of the anion in (NH₄)₄[Mo₈O₂₆], 5H₂O, deduced by Lindqvist in 1950 from the Mo coordinates alone. The compound is triclinic, P$\text{1}$, a = 9.769(16), b = 9.832(13), c = 7.848(11) Å, α = 99.11(4), β = 101.03(11), γ = 97.40(4)°, Z = 1. Eight MoO₆ octahedra share edges in a compact grouping, with short terminal MoO bonds (1.69 to 1.75 Å), longer bonds (1.88–2.00 Å) to bicoordinate O atoms, and long bonds (2.18–2.39 Å) to multiply-shared interior atoms.     

catena‐Poly­[[bis­(nitrato)(pyrimidine)­copper(II)]‐μ‐pyrimidine‐N:N′]

The title compound, [Cu(NO₃)₂(C₄H₄N₂)₂]_n, crystallizes as a linear polymeric compound with one pyrimidine ligand bridging between two Cu^II atoms and a second pyrimidine ligand coordinated in a monodentate manner. The distorted octahedral geometry around the Cu^II atom consists of two pyrimidine N atoms at distances of 2.033 (4) and 2.025 (4) Å, and two nitrate O atoms at distances at 1.987 (3) and 1.973 (3) Å. The apical positions are occupied by an N atom of a bridging pyrimidine ligand [2.291 (4) Å] and a nitrate O atom at a long distance of 2.781 (3) Å. The basal plane is almost planar, with trans angles of 176.23 (14) and 165.34 (15)°.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.