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.     

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).     

Structure of tetrakis-pivaloyltrifluoroacetonates of heavy rare earth elements and sodium. Crystal structure of NaEr(C8H10O2F3)4

The structure of a compound from an isostructural series of pivaloyltrifluoroacetonates of heavy rare- earth elements (REE) (Cd- Lu) and sodium, NaEr(C₈H₁₀O₂F₃)₄, was studied by X- ray diffractometry (“Syntex P2₁,” λMoK_α, 1891 reflections, R =0.0601);a =13.114(4), c =21.004(9) å, V =3128(2) å ³, Z =3,space group P3 ₁. The structures of this series are of ionic type and contain the [Ln(pta) ₄]^? complex anion and the Na⁺ cation. The coordination polyhedron of Ln is a tetragonal antiprism, an ssss stereoisomer. Na is surrounded by 4O +4F in the form of an octahedron with two centered faces. Both polyhedra are distorted (average Er- 0 distances are 2.325 å, Na- O 2.397 å, Na- F 2.682 å) and linked by common faces into polymeric helicoidal ribbons extended along the c axis and arranged according to the closest packing law. It is established that the Na cation affects the stereochemistry of the anion. A relationship between the structure of the compound and its volatility and crystal morphology is discussed.     

Crystal structure of lead(II) dipivaloylmethanate

The volatile complex of lead(II) with 2,2,6,6-tetramethylheptane-3,5-dione is investigated by X-ray diffractometry. Crystal data: a = 10.901(2), b = 21489(4), c = 10.203(2) å, space group Pccn (N 56), V = 2503.4(8) å³, M = 573.74, Z = 4, d_calc = 2.522 g/cm³. The crystal structure is of molecular type; the molecule of the complex has a nonplanar structure. The lead atom is coordinated by four oxygen atoms of the two bidentate ligands. Films of the complex on substrates of Si and SiO₂ single crystals, melted quartz, and glass were obtained by thermal evaporation in vacuum. X-Ray diffraction analysis of the polycrystals and films of the complex showed that the films are distinctly textured along the b axis.     

Redetermination of the crystal structure of potassium peroxodisulfate (K2S2O8)

The crystal structure of potassium peroxodisulfate was determined. The crystals are triclinic, a =5.115(1),b =7.034(2), c =5.505(1) å, α =106.32(2),gb =90.18(2), γ =106.12(2)?, V_cell = 181.90(7) å³, space group Pī, Z =1, d_calc =2.468 g/cm ³ [“Syntex P2₁,” λCuK_α, 994 reflections measured in a whole sphere to 2Τ_max =114?, including 496 independent reflections (R_int = 0.0571), R(F) = 0.0391, wR(F²) = 0.0933 for 486 F_hkl > 4Σ(F)]. An absorption correction (Μ = 171.37 cm^?1) was applied taking into account the shape and size of the crystal using data about face indices. The representative of the single crystal was proven by comparing the experimental and calculated diffractograms. The geometrical characteristics of S₂O ₈ ² : S-O 1.645(2), S = 0 1.421(3)-1.429(2), O-O 1.495(5) å, S-O-O 106.2(2)?.     

Crystal and molecular structure of chloro-bis(1,2-cyclohexanedione-dioxime)triphenylphosphinecobalt(III)

The structure of chloro-bis(1,2-cyclohexanedionediaxwte)triphenylphosphinecobalt(III) [Co(NioxH)₂PPh₃Cl] was determined by X-ray diffraction analysis. The crystal is monoclinic, a = 17.049(3), b = 15.223(3), c = 11.032(3) å, Β = 87.44(2)?, R(hkl) = 0.068 for 2739 reflections with I ≥2Σ(I). The structure is molecular. In the octahedral complex, the cobalt(III) atom is coordinated by two NioxH residues (av Co-N = 1.876 å), the phosphorus atom (Co-P = 2.307 å), and the Cl^- union (Co-Cl = 2.260 å). In the crystal, there are weak intermolecular interactions C-H…Cl and C-H…O.     

Specific nonbonding interactions in the structure of (N2H5)2[Mo3S7I6]·1.5H2O

The crystal structure of (N₂H₅)₂[Mo₃S₇I₆]· 1.5H₂O is investigated;triclinic crystals, a-10.029(2), b = 10.258(3), c =14.152(2) å, a =109.21(2), Β =106.14(1), γ =98.97(2)?, V _cell =1270.6(5) å ³, space group P1, Z =2, d _calc =3.572 g/cm ³, CAD-4 diffractometer, λMoK_α, 2θ_max =50?, N _tot =4118, R(F) = 0.0554, wR(F²) = 0.1365 for 3057 F_hkl 4Σ(F). The cluster onions are united into centrosymmetric dimers with distances 3S_ax...I 3.324(5)-3.473(4) å. The dimers, in turn, form a three-dimensional framework with cations and solvate water molecules in the cavities due to additional contacts S_eq...I and S_ax...I 3.624(4)-3.785(4) å. The hydrogen bonds formed in the structure are N(N₂H₅)...O(H₂O) and N(N₂H₅)...I 2.78(4)-2.96(8), 3.64(3)-3.75(3) å. The nonbonding interactions completely determine the crystal structure.     

Synthesis and crystal structure determination of iridium(III) acetylacetonate and its Br-and I-substituted analogs

γ-Halogen-substituted iridium(III) acetylacetonates of general formula Ir(acacX)₃,where acacX = CH₃ -CO-CX-CO- CH₃,X =Br, I, were synthesized. The compounds are characterized by melting points and chemical analysis data for C, H, Br, and I. An X-ray diffraction analysis was performed for iridium(III) acetylacetonate and its y-substituted analogs, crystal data were obtained, and crystal structures were determined. The crystals are monoclinic;the structures are molecular. Crystal data: Ir(acac)3 _- IrO₆C₁₅H₂₁,a = 13.900(2), b = 16.440(3), c = 7.494(2) å, γ =98.63(2)?, V= 1693.2 å³,space group P2₁/b,Z = 4, d_calc =1.92 g/cm³,sin θ/λ_max = 0.703, F_hkl = 2841, R = 0.044. Ir(acacBr)_3- IrBr₃O₆C₁₅H₁₈,a = 12.794(2), b = 15.753(2), c = 9.990(2) å Β = 105.76(2)?, V= 1937.6 å³,space group P2₁/n,Z =4, d_calc =2.49 g/cm³, sinθ/λ_max = 0.702, F_hkl = 1748, R = 0.048. Ir(acacI)3- M₃O₆C₁₅H₁₈,a = 12.855(2), b = 10.136(2), c =16.338(3)å, Β = 104.6(2)?, V=2059.8å³,space group P2₁/n, Z =4, d_calc = 2.79g/cm³, θ_max =25?, F_hkl = 2817, R =0.032. The Ir..Ir distances were estimated to be > 7.49 å for Ir(acac)3 and > 8.10 å for Ir(acacBr)3 and Ir(acacl)₃.If the estimate is limited to 10 å, the intermolecular coordination number (ICN) in the structures is 10.     

Crystal and molecular structures of bis-(5-methyl-5-butoxy-hexanedionato-2,4) Copper(II) and bis-(2,2-dimethyl-5-cyclohexyl-pentanedionato-3,5) Copper(II)

Two new volatile complexes of Cu(II) containing methoxy groups were studied in a combined X-ray diffraction investigation of the mono- (KUMA automatic diffractometer, MoK_α radiation) and polycrystals (DRON-3M, CuK_α radiation). The structures are molecular and consist of the trans-complexes of bis-(5-methyl-5-butoxy-hexanedionato-2,4)copper(II), C₂₂H₃₈CuO₆, and bis-(2,2-dimethyl-5-cyclohexyl-pentanedionato-3,5) Copper(II), C₂₈H₄₆CuO₆. The crystal data of C₂₂H₃₈CuO₆: a = 8.939(1), b = 8.887(2), c = 8.326(1) å, α = 107.92(2), Β = 108.15(1), γ = 85.52(2)?, space group P1,V= 597.9(2) å³, Z = 1, d_x = 1.283 g/cm³. The crystal data of C₂₈H₄₆CuO₆: a = 18.625(3), b = 16.126(2), c= 13.613(3) å, Β = 132.19?, space group P2₁/n, V= 3029.3(9) å³, Z = 4, d_x= 1.189 g/cm³. In both cases, the square planar environment of the Cu atom with Cu...O distances of 1.90 å is completed by interactions with two carbon atoms of the terminal groups of the two neighboring molecules at Cu...C distances of 3.66 å (average).     

A new type of mixed framework in the crystal structure of binary molybdate Nd2Zr3(MoO4)9

Single crystals of binary molybdate Nd₂ZrMoO₄)₉ were grown. The crystal structure of this compound was investigated by X-ray diffraction analysis (CAD-4 diffractometer, MoKα radiation, 2844 reflections. R = 0.0230), and a new type of structure was found. The crystals are trigonal with cell dimensions a = 9.804(1), c = 58.467(12) å, V= 4867(1) å³, Z = 6, d_calc = 4.098 g/cm₃, space group R ₃ ^? c. The structure involves polyhedra of three types: MoO₄ tetrahedra, ZrO₆ octahedra, and NdO₉ tricapped trigonal prisms linked by their common vertices into an original three-dimensional framework.     

Crystal structure of kuznetsovite Hg3(AsO4)Cl

The crystal structure of a rare supergene mineral kuznetsovite Hg₃(As0₄)Cl, previously determined from powder data, is refined (space group P2₁3, a = 8.379(3) å, V = 588.3(4) å⁰³, Z = 4, d_calc = 8.763 glcm³, 3.44 < θ < 24.96?, 563 I_hkl(msd)/211 I_hkl(indep), R₁ = 0.0997, wR₂ = 0.2515). It is formed from the Cl^? and (AsO₄)^3- anions (As-O 1.74(3) and 1.79(1) å) and the trigonal cations Hg ₃ ⁴⁺ (Hg-Hg 2.675(5) å, HgHgHg 60?). The coordination polyhedron around each mercury atom involves two mercury atoms, two oxygen atoms at short Hg-0 distances (2.17(3) and 2.28(3) å, < OHgO 94.3(13)?), and more remote oxygen and chlorine atoms (Hg-0 2.601(6) å, Hg-Cl 2.838(9) å). The polyhedron is irregular and close to a trigonal antiprism. The Hg₃ triangles alternate with AsO₄ tetrahedra along each coordinate axis. Taking into consideration only short Hg-0 bonds (2.17(3) and 2.28(3) å), one can isolate a framework with chlorine ions lying in the cavities.     

Polymorphous transformation of a clathrate in the pyridinecadmium nitrate system

The polymorphous transformation of the [CdPy ₄(NO₃)2]·2Py clathrate (Py is pyridine) at 221 K is investigated by analyzing the temperature dependences of the Raman spectra and the lattice parameters in the range 100–293 K The crystal structures of the high- and low-temperature modifications of the clathrate were determined. Above the transition point the clathrate crystallizes in space group Ccca (at 293 K: a = 12.360(4), b = 15.456(3), c = 16.931(3) å, V = 3234(1) å³, Z = 4, R = 0.050 for 879 reflections and 126 refined parameters). Below 221K the unit cell of the clathrate is transformed into the primitive cell, space group Pcca (at 215 K: a = 11.953(3), b = 15.129(3), c = 17.234(3) A, V = 3234(1) å³, Z =4, R = 0.057 for 1596 reflections and 210 refined parameters). In both modifications, the host complex involves four pyridine ligands and two monodentate trans-nitrato groups forming a distorted octahedron around the central atom. The guest pyridine molecules lie in the cavities of the molecular framework of the complex. As the clathrate is cooled, the a and b parameters decrease and the c parameter increases; at transition point, each of these parameters abruptly changes by about 0.2 A. The nitrate ligand undergoes ordering and inclination to the equatorial plane of the complex by 20?.     

Crystal and molecular structure of 5,5-BIS(hydroxymethyl)-2-OXO-2-[l-(2-trifluoromethyl-3,3,3-trifluoropropioneamido)-1-trifluoromethyl-2,2,2-trifluoroethyl]-1,3,2-dioxaphosphorinane

The crystal and molecular structure of 5,5-bis(hydroxymethyl)-2-oxo-2-[1-(2-trifluoromethyl-3,3,3-tri-fluoropropioneamido)-1-trifluoromethyl-2,2,2-trifluoroethyl]-1,3,2-dioxaphosphorinane (I) - an effective inhibitor of phosphorolytic enzymes - has been determined by X-ray diffractometry. Crystals I are monoclinic: space group P2₁/c, a = 9.962(3), b = 20.468(3), c = 9.527(3) å, Β = 108.04(2)?, Z = 4; R = 0.061 for 3065 independent reflections with I ≥ 3Σ. In a sterically strained molecule I, the coordination polyhedron of the P atom is a distorted tetrahedron with an elongated exocyclic P-C bond [1.906(2) å]. The six-membered heterocycle of I has a distorted chair conformation with a significantly flattened angle at the P atom. In the crystal structure, molecules I are linked into centrosymmetric H-dimers by a pair of strong H-bonds of O-H...O=P type and also into infinite (along the z axis) chains by H-bonds of N-H...O = C and C-H...O = C type.     

The chemistry and the stereochemistry of poly(N-alkyliminoalanes) : V. The preparation and crystal structure of the pentamer [(HalN-i-Pr)2(H2AlNH-i-Pr)3]

The compound [(HAlN-i-Pr)₂(H₂AlNH-i-Pr)₃] has been prepared and the crystal and molecular structure determined by an X-ray analysis, carried out with three-dimensional data collected on a diffractometer. The molecule is made up of a cyclohexane-type ring, [(HAlN-i-Pr)₂(H₂AlNH-i-Pr)], in skewboat conformation, on each side of which is bonded an -H₂AlNH-i-Pr- bridging unit between a nitrogen atom and an aluminum atom of the ring. The molecule lies on a binary axis of the crystal, but this symmetry is fulfilled only by a statistical orientation of the asymmetric molecular units (the statistical model is not however completely defined). The AlN bond lengths range from 1.901 to 1.985 Å; the average NC bond length is 1.527(9) Å. Main crystal data are: monoclinic space group C2/c; a = 10.15(2), b = 21.64(3), c = 12.84(2) Å, β = 111.9(5)°; Z = 4; calculated density 1.095 g/cm³. The structure was solved by direct methods and block-matrix least-squares converged to an R value of 5.6%.     

Crystal structure of (Et4N) [(µ-H)Fe3(µ3-Se)(CO)9]

The crystal structure of (Et₄N)[(μ-H)Fe₃(μ₃-Se)(CO)₉] is determined;the crystals are monoclinic, a = 11.172(2), b =32.332(5), c =13.552(3) ?, μ =91.86(2)‡, V _cell =4893(2) ? ³, space group P2₁/n, Z =8, d _calc =1.710 g/cm ³, CAD-4 diffractometer, MoK_α radiation;the total number of data collected 4395,including 4086 independent reflections(R_int =0.0701), R(F) =0.0566, wR(F ²) =0.1202 for 1963 F _hkl > 4Σ(F). The data were corrected for the 37.8% linear drop of intensities of the control reflections due to crystal decay. The Fe-H bond lengths are 1.5(1)-1.72(9) ?. As in the case of three-osmium clusters,the presence of the Μ-H ligand leads to a lengthening of the Fe-Fe bond by approximately 0.1 ? and to push-away of the equatorial carbonyl ligands leading to an increase in the FeFeC angle by approximately 5–10‡, whereas the axial CO and (Μ ₃-Se) remain unchanged.     

Crystal structure of sodium dichlorobis(acetylacetonato)rhodiate(iii) monohydrate Na[Rh(C5H7O2)2Cl2] · H2O. pseudoperiodicity as the consequence of the packing law of complexes in crystals

The crystal structure of Na[Rh(acac)₂Cl₂] · H₂O (acac) =C ₅H₇O ₂ ^? )is determined The crystals are triclinic, space group P1, with unit cell dimensions a =12.616(2), b =8.411(4), c =8.499(4) å,a =108.37(4), Β =95.47(4), γ =110.45(4)?, V =780.3(6) å ³, Z =2, d _calc =1.758 g/cm ³, R =0.0461. The strong pseudoperiodicity observed experimentally (no reflections with odd indices h) led to a set of experimental data obtained in the unit cell that is reduced along the a axis (“Syntex P2 ₁ ” automatic diffractometer, λMoK _α, graphite monochromator), 1466 measured and 1302 observed I_hkl included in the calculation. This is due to the alternation of the central atoms of octahedral complex onions at intervals of 1/2a. The Rh- 0 and Rh- Cl distances are, on the average, 2.001(3) and 2.325(2), respectively. The cis- angles of ClRhO type are close to 90?, and the average value of the ORhO chelate angle is 95.1? (within 3Σ with Σ ? 0.1?). The average interatomic distances and bond angles (according to types) in the acac ligand are as follows: O- C 1.274, (C- C)_ring 1.397, C_ring- C_sub 1.506 å with Σ not higher than 0.006 å,RhOC 122.2?, (OCC) _ring 126.4?, (OCC)_term 114.2?, (CCC)_ring 127.3?, (CC)_ringc_sub 119.3? (Σ within 0.2– 0.6?). The distorted octahedron around the Na ion consists of five O atoms (of the H₂O molecule and the neighboring acac ligands, distances within 2.364– 2.409 å) and one Cl ion lying at a distance of 2.970 å. The structure in general is of ribbon type: Rh_1,2 and Na octahedra are linked by a common edge O(2′)O(1) and common face O(3)O(4′)O(2′) into infinite ribbons, which are extended along the [100] axis and which are translationally identical in the [010] and [001] directions. The H ₂O molecule forms two Cl(l)...H₂O...Cl(2′) hydrogen bonds: 3.116 and 3.179 å, respectively, which link the Rh octahedra into infinite chains in the [120] direction.     

Crystal and molecular structure oftrans-bis-(1,1,1-trifluoro-5-methoxy-5-methyl-2,4-hexanedionato) copper(II)

A combined X-ray diffraction study of the single crystals (Enraf-Nonius CAD-4 automatic diffractometer, MoK_α radiation, graphite monochromator) and polycrystals (DRON-UM1, CuK_α radiation, Ni filter) of a new volatile complex of Cu(II) obtained from fluorinated alkoxy-Β-diketone, CF₃-CO-CH₂-CO-C(CH₃)₂OCH₃, is reported. The compound has a molecular structure; the crystals consist of trans-bis(1,1,1-trifluoro-5-methoxy-5-methyl-2,4-hexanedionato)copper(II) complexes. The structure was refined anisotropically for 2314 independent reflections with I > 2Σ(I) to R = 0.069. Crystal data: a = 24.469(3), c = 10.581(2) å, V = 5486.4 å³, space group R3, Z = 9, d_calc = 1.17 g/cm³. The complexes are packed to form through channels ≈5 å in diameter along the c axis, with terminal fluorine atoms facing the channels. The crystal-chemical data of the compound are compared with those of the nonfluorinated analog, trans-bis(2-methoxy-2,6,6-trimethylheptane-3,5-dionato)copper(II). The introduction of CF₃ groups into alkoxy-Β-diketone considerably decreases the sublimation temperature of the complex. The geometrical characteristics of chelate nodes in the complexes are almost equal: the Cu-0 distances are 1.92 å and the O-Cu-0 bond angles 92.1? (average). In both cases, the square planar environment of the Cu atom is completed to bipyramidal by interactions with the oxygen atoms of the methoxy groups of the neighboring molecules, with Cu...O distances being 2.8 å.     

Crystal Structure of a New Cation-ordered Fluorite-related Phase: Bi2Te2WO10

Bi₂Te₂WO₁₀ crystallises in the monoclinic system (space group C2/c, Z = 4) with a = 12.4972(7) Å, b = 5.6414(3) Å, c = 12.2705(6) Å and β = 91.38(3)°. The structure has been solved by means of single crystal X-ray diffraction data analysis. The reliability factors are R1 = 0.030 and wR2 = 0.065 for 1258 structure factors and 70 parameters. The Bi₂Te₂WO₁₀ crystal structure can be described as a regular stacking along the Ox axis of polyhedral layers with the stereochemically active lone pairs E of the Bi^III and Te^IV atoms all located between these layers. The cohesion of the three-dimensional network is therefore only ensured between succesive layers by weak Bi? O(5) bonds.     

Ion-selective and complexation properties, vibrational spectra, and crystal and molecular structure of 1,5-bis[2-(hydroxyethoxyphosphoryl)phenoxy]-3-oxapentane

The ion-selective properties of 1,5-bis[2-(hydroxyethoxyphosphoryl)phenoxy]-3-oxapentane H₂R² have been described. The molecular and crystal structure of H₂R² has been determined by powder X-ray crystallography and IR spectroscopy. The molecule has the twofold symmetry axis, orthorhombic crystal system, space group Pbcn, a = 16.830(2) ?, b = 8.866(15) ?, c = 15.7190(2) ?, V = 2346.1(6) ?³, Z = 4. A new CuR² · 2H₂O complex has been synthesized and characterized.     

X-ray diffraction study of the clathrate [MnPy4(NO3)2)]·2Py and complex [MnPy3(NO3)2] formed in the pyridine (Py)-manganese nitrate system

A clathrate compound [MnPy₄(NO₃)₂]·2Py was synthesized and studied by single-crystal X-ray diffraction analysis (KM-4 diffractometer, CuK_α,ω/2? scan mode,? _max=78°). The unit cell is base-centered orthorhombic, space group Ccca, a=12.097(4), b=15.197(4), c=17.213(4) Å, V=3164(2) ų, Z=4, R=0.072, for 632 reflections and 107 parameters in the least-squares analysis. The host molecule has 222 symmetry. Two monodentate nitrato groups and four pyridine ligands are coordinated to Mn(II) along the symmetry axes (the former via O). The pyridine guest molecules lie in the cavities of the crystal framework. For [MnPy₃(NO₃)₂)], only unit cell parameters were determined: a=12.467(5), b=9.514(2), c=16.383(5) Å,β=108.93(4), V=1838(1) ų space group C2/c or Cc (according to extinctions). The pyridine-manganese nitrate system is shown to be analogous to the previously investigated Co, Ni, Cu, Zn, and Cd systems.