Crystal structure ofmer,trans-[Ru(NO2)(trpy) (PPh3) 2 + ][PF 6 − ]: a “problem structure”

The complexmer,trans-[Ru(NO₂)(trpy)(PPh₃) ₂ ⁺ ][PF ₆ ^– ] crystallizes in the centrosymmetric monoclinic space groupP2₁/n withZ=4; the ruthenium atom lies close toy=1/4 and all data withh+l=2n+1 are systematically weak. The trpy ligand is not strictly planar, but has a dish-like geometry. The nitro ligand is rotated from the plane of the Ru(trpy) moiety, the N₃Ru/NO₂ interplanar angle being 32.5^o. Ruthenium-ligand distances are: Ru–PPh₃=2.418(4) Å and 2.429(4) Å, Ru–NO₂=2.063(12) Å, Ru–N(trpy, outer)=2.100(12) Å and 2.116(12) Å and Ru–N(trpy, central)=2.004(11) Å.     

Crystal structure ofcis-[Ru(bpy)2(PPh3)Cl+][ClO 4 − ]·(toluene)·∼0.5(CH2Cl2), a species with two different disordered solvent molecules of crystallization

The complexcis-[Ru(bpy)₂(PPh₃)Cl⁺][ClO ₄ ^– ] (where bpy=2,2-bipyridyl) crystallizes from a solution in toluene/dichloromethane as the toluene-hemi(dichloromethane) solvate in the centrosymmetric space group witha=10.343(2)Å,b=11.823(3)Å,c=18.469(4)Å, =98.90(2)^o, =93.32(2)^o, =101.46(2)^o,V=2177.8(8)ų andZ=2. The structure was refined toR(F)=4.6% for those 4248 reflections above 6(F _o ). The octahedral Ru(II) cation is associated with the bond lengths Ru–Cl=2.424(2)Å, Ru–PPh₃=2.328(1) Å and Ru–N=2.045(5)–2.109(4)Å. Both the cation and the perchlorate anion are ordered. However, the unit cell also contains two disordered toluene molecules (centered about inversion centers at 1, 1/2, 0 and 1/2, 0, 1/2), and a disordered dichloromethane molecule of a partial occupancy (centered about 1/2, 0, 1).     

Crystal structure ofcis-[Ru(bpy)2{PPh2(o-tol)}Cl][ClO4]·1.5(CH2Cl2), a structure containing both ordered and disordered dichloromethane molecules of crystallization

The complexcis-[Ru(bpy)₂ {PPh₂(o-tol)}Cl][ClO₄] crystallizes from dichloromethane as the sesqui-dichloromethane solvate. The complex crystallizes in the monoclinic space group P2₁/n with Z=4. The structure was refined toR=5.50% for those 2552 independent reflections with |F ₀|>6(|F ₀|) The octahedral Ru(II) cation is associated with the following bond lengths: Ru-PPh₂(o-tol)=2.360(3)Å. Ru–Cl=2.433(2)Å and Ru–N(bpy)=2.041(8)–2.095(8)Å. Both the perchlorate anion and the dichloromethane molecules of solvation exhibit large amplitudes of vibration. One dichloromethane molecule lies in a general position, the other lies about an inversion center and suffers from disorder.     

Synthesis ofcis-[Ru{4,4′-(t-Bu)2bpy}2(PPh3)Cl+][ClO 4 − ] and the crystal structure of its disordered hemiacetonitrile,hemitoluene solvate

The complexcis-[Ru{4,4-(t-Bu)₂bpy}₂(PPh₃)Cl⁺][ClO ₄ ^– ·0.5(toluene)·0.5(MeCN), where 4,4-(t-Bu)₂bpy=4,4-di(t-butyl)-2,2-bipyridyl crystallizes with an ordered racemic mixture of the chiral cations in the centrosymmetric triclinic space group (No. 2). The structure was refined toR=4.42% for those 6426 reflections with 20=5–50^o and |F _o|>6(F). Ruthenium ligand distances are Ru–Cl=2.423(2)Å, Ru–PPh₃=2.346(2)Å and Ru–N=2.056(4)–2.098(4)Å. Both the Ru(II)-containing cation and the perchlorate anion are ordered, but the toluene and acetonitrile exhibit an interesting type of scrambled disorder about the inversion center atx=1,y=1/2,z=0.     

Crystal structure of [Co(Ox)(NH3)4][Bi(Edta)] ⋅ 3H2O

The crystal structure of [Co(Ox)(NH₃)₄][Bi(Edta)] ? 3H₂O is determined. The crystals are monoclinic, a = 9.291 Å, b = 22.275 Å, c = 11.402 Å, β = 105.79°, V = 2270.7 ų, Z = 4, and space group P2₁/c. The [Bi(Edta)]^? anionic complexes are linked into polymeric chains through two Bi-O bonds with the neighboring complexes.     

Synthesis and crystal structure of a palladium dimer containing ferrocenyldiphenylphosphine, trans-[Pd(μ-Cl)(CH3)(PPh2Fc)]2

The chloro-bridged dimeric complex, trans-[Pd(-Cl)(CH₃)(PPh₂Fc)]₂, was prepared by reaction of [Pd(Cl)(CH₃)(COD)] (COD = cis,cis-1,5-cyclooctadiene) with 1 equivalent of PPh₂Fc (PPh₂Fc = ferrocenyldiphenylphosphine) in acetone medium. The complex was characterized by ¹H and ³¹P NMR spectroscopy and a single crystal X-ray diffraction study revealed a trans geometry. The compound crystallizes in the triclinic space group P1, a = 11.476(2) Å, b = 14.059(3) Å, c = 14.658(3) Å and = 82.34(3)°, = 75.09(3)°, and = 68.48(3)° with Z = 2. Most important geometrical parameters include bond lengths Pd(1)–P(1) 2.2165(10), Pd(2)–P(2) 2.2290(10), Pd(1)–C(1) 2.157(3), Pd(2)–C(2) 2.079(4), Pd(1)–Cl(1) 2.4329(13), Pd(1)–Cl(2) 2.4106(11), Pd(2)–Cl(1) 2.4169(10), and Pd(2)–Cl(2) 2.4414(13) Å and bond angles P(1)–Pd(1)–C(1) 87.47(8), P(1)–Pd(1)–Cl(2) 176.88(4), C(1)–Pd(1)–Cl(1) 173.93(7), P(2)–Pd(2)–C(2) 89.03(11), P(2)–Pd(2)–Cl(1) 174.18(4), and C(2)–Pd(2)–Cl(2) 173.50(11)°. The effective and Tolman cone angles for P(1) were calculated as 170 and 167° and that for P(2) as 179 and 177°, respectively.     

Structures and crystallization behavior of cis-α-[Co(trien)(NO2)2]·ClO4 (I), cis-β-[Co(trien)(NO2)2]Br·2H2O (II), and cis-β-[Co(trien)(NO2)2]·ClO3 (III)

Structures, conformations, and crystallization behavior of compounds cis--[Co(trien)(NO₂)₂]·ClO₄ (I), cis--[Co(trien)(NO₂)₂]Br·2H₂O (II), and cis--[Co(trien)(NO₂)₂]·ClO₃ (III) are reported. Compound (I) crystallized in space group Pbca, with a = 12.3323(9), b = 13.0265(9) and c = 18.1597(13) Å; compound (II) crystallized in space group Pca2₁, with a = 8.1844(7), b = 14.7011(14) and c = 12.4875(12) Å, while compound (III) also crystallized in space group Pca2₁, with a = 12.4897(8), b = 8.8499(6) and c = 12.6500(8) Å. In all three cases, the Co(III) ions were six-coordinated with nitrogens from trien and two nitrates. Inter- and intramolecular hydrogen bonding interactions are discussed to explain the conglomerate versus racemate crystallization behavior adopted by these three compounds, with comparison of their known analogue compounds of cis-/-[Co(trien)(NO₂)₂]X, where X = halide and NO^– ₃. For the cis--[Co(trien)(NO₂)₂]⁺ cation, the conformation of the cation itself determines the intramolecular hydrogen bonding pattern, and the interaction of counteranions can be ignored, while in cis--[Co(trien)(NO₂)₂]·ClO₄, the perchlorate interrupts the intramolecular hydrogen bonding pattern observed in the halide analog.     

Crystal structure of [Mn(II)(phen)(ClCH2COO)2]n (phen = 1,10−phenanthroline)

A new polymeric manganese(II) complex, [Mn(II)(phen)(ClCH₂COO)₂]_n, was obtained from the reaction of Mn(ClCH₂COO)₂ with phen and its structure was determined by x-ray crystallography. The complex crystallizes in the monoclinic system, space group C2/c with a = 19.706(4), b = 11.381(3), c = 7.482(3) Å, = 94.01(3)°, V = 1674.0(8) ų, and Z = 4. The structure consists of an infinite chain. The manganese atom is located on a twofold axis and presents a distorted octahedral coordination sphere, which consists of the two N atoms of a phen ligand (Mn—N = 2.304(2) Å) and four carboxylato ligands. The Mn···Mn distance within the chain is 4.53 Å, and the carboxylato bridges present a syn-anti conformation.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

Crystal structure of [Mn(bpy)3](ClO4)2·0.5(bpy) (bpy=2,2′-bipyridine)

A new monomeric manganese(II) complex with 2,2′-bipyridine (bpy), [Mn(bpy)₃-] (ClO₄)₂·0.5(bpy), has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group $P\bar 1$ witha=9.535(2),b=13.194(3),c=14.854(3) Å, α=96.50(3), β=107.26(3), γ=91.19(3)°,V=1770.2(7) ų, andZ=2. The structure comprises discrete [Mn(bpy)₃]²⁺ cations in which the metal atom is coordinated in a highly distorted octahedral environment by three chelate bpy ligands [Mn?N=2.229(3)–2.289(2) Å]. The solvate bpy molecule and a pair of coordinated bpy ligands each from the adjacent cations are arranged in an off-set fashion, showing significant intermolecular stacking interaction with close interplanar contacts ofca. 3.47 Å.     

Crystal structure of [Yb(L(NO3)2(H2O)2](NO3), L = bromo-N,N,N′,N′-tetraethylmalonamide

[Yb(L(NO₃)₂(H₂O)₂](NO₃), L = bromo-N,N,N,N-tetraethylmalonamide crystallizes in the triclinic spacegroup P-1 with cell dimensions a = 9.030(9), b = 12.036(12), c = 12.392(13) Å, = 84.52(1), = 77.58(1), = 67.21(1)° , d_calc = 1.935 g cm^-3 for Z = 2. The ytterbium atom in the complex cation is nine-coordinate being bonded to two oxygen atoms from the malonamide ligand, two nitrate anions, and three water molecules.     

Crystal structure of tylophorine methiodide monohydrate,C25H30NO 4 + I−·H2O

The crystal structure of tylophorine (Chemical name 2,3,6,7 tetramethoxy phenanthro [9,10:6, 7] indolizidine. Contribution No. 0871.) methiodide monohydrate has been determined. C₂₅H₃₀NO ₄ ⁺ I^–·H₂0, triclinic, P,a=8.831(1)Å, b=10.842(2),c=13.902(2), =105.0(1)^o, =104.7(1), =97.3(1),V=1210.22ų, Z=2,D _x =1.428 g./cm^–3, (CuK)=1.54184Å, (CUK)=107.2 cm^–1, F(000)=544,T=295^oK,R=0.038,Rw=0.046, for 2331 observed reflections withI2(I). Apart from van der Waals forces, the structure is stabilized by two hydrogen bonds of the type Ow(H) ... O and Ow(H) ... I^– involving the water molecule as the donor and atom O4 of the methoxy group and I^– as acceptors.     

Thermal decomposition of energetic materials. 44. Rapid thermal decomposition of the propyl-1,3-diammonium salts of NO 3 − and ClO 4 − , and the crystal structure of the ClO 4 − salt

The temperature dependence of the IR spectra of the condensed phase (dT/dt=5°C min^–1) and the fast thermolysis (dT/dt100°C sec^–1) of propyl-1,3-diammonium dinitrate (PDD) and diperchlorate (PDP) are compared. Rapid-scan FTIR/temperature profiling shows that PDP explodes on heating while PDD decomposes with much less energy. HNO₃(g) is formed by deneutralization in the initial decomposition of PDD, but HClO₄(g) is not detected from PDP. PDP is unique among the compounds studied by this technique in that a solid-solid phase transition can be detected during rapid heating. The initial phase of PDP has been characterized by X-ray crystallography: monoclinic,P2₁/c,a=7.316(2),b=14.428(2),c=9.742(2) Å,=96.81°,V=1021.1(3) ų,Z=4,D=1.789 g cm^–3,R(F)=0.034,R(wF)=0.040.     

Crystal structure of cobalt(III) compound with ethylenediamine-N,N′-Di-3-propionic acid, [Co(H2 Eddp)(HEddp)]Br2 ⋅ 4H2O

The crystal structure of [Co(H₂ Eddp)(HEddp)]Br₂ ? 4H₂O is determined [R1 = 0.0551 and wR2 = 0.1298 for 2580 reflections with I > 2σ(I)]. The structure consists of the [Co(H₂ Eddp)(tHEddp)]²⁺ cationic complexes, Br^? anions, and molecules of crystallization water. Two tridentate ligands, which differ in the degree of protonation, coordinate the Co atom by two N atoms and one O atom, each forming a meridional isomer. In the complex, the configurations of the N(2) and N(4) atoms, which are included in two chelate rings each, differ from those of the N(1) and N(3) atoms, which are included only in the five-membered rings and bear uncoordinated propionate groups. The Co-N(1) and Co-N(3) bonds are longer than the Co-N(2) and Co-N(4) bonds (mean 1.987 and 1.957 Å, respectively). The Co-O(5) bond with the neutral ligand is longer than the Co-O(1) bond with the negatively charged carboxyl group (1.927 and 1.901 Å, respectively). The C(13)-O(5) carbonyl bond in the coordinated COOH group is elongated to 1.266 Å. The system of hydrogen bonds interlinks the cationic complexes, Br^? anions, and water molecules into a three-dimensional framework.     

Reaction of bis(dimethoxyphosphino)dimethylhydrazine (dmpdmh) with Ru3(CO)12: Evidence for facile ligand fragmentation in Ru3(CO)10(dmpdmh) to give Ru4(CO)12[μ-N(Me)N(Me)], Ru3(CO)11[P(OMe)3], and Ru3(CO)9[μ-P(OMe)3]

Thermolysis of the cluster Ru₃(CO)₁₂ with the bis(phosphanyl)hydrazine ligand (MeO)₂PN (Me)N(Me)P(OMe)₂ (dmpdmh) in toluene at 75°C furnishes the known clusters Ru₄(CO)₁₂ [-N(Me)N(Me)] (2) and Ru₃(CO)₁₁[P(OMe)₃] (3), in addition to the new cluster Ru₃ (CO)₁₀(dmpdmh) (1) and the phosphite-tethered cluster Ru₃(CO)₉[-P(OMe)₃] (4). The simple substitution product Ru₃(CO)₁₀(dmpdmh), a logical intermediate to clusters 2–4, was synthesized by treating Ru₃(CO)₁₂ with Me₃NO in CH₂Cl₂ at room temperature, and independent thermolysis reactions using cluster 1 was shown to yield clusters 2–4. The solid-state structure of clusters 2 and 4 were unequivocally established by X-ray diffraction analysis. Ru₄(CO)₁₂[-N(Me)N(Me)] crystallizes in the orthorhombic space group Pnna (#52), a = 12.913(1), b = 13.3238(6), c = 12.5690(8) Å, V = 2162.5(2) ų, Z = 4, and d _calc = 2.452 g/cm³. Ru₃(CO)₉[-P(OMe)₃] crystallizes in the triclinic space group P a = 9.586(1), b = 14.354(1), c = 14.997(2) Å, = 89.82(1)°, = 98.36(1)°, = 92.010(8)°, V = 2040.4(4) ų, Z = 4, and d _calc = 2.212 g/cm³. The coordination of the dimethylazo linkage to the four ruthenium atoms in 2 and the phosphorus atom and one of the oxygen atoms of the methoxy groups to the three ruthenium centers in 4 are confirmed by X-ray analysis.     

Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] · 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 · 8H2O, Ba[Cu(SS-HEdds)]ClO4 · 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 · 6H2O

Four Cu(II) complexes with the RR,SS-Edds ^4? and SS-HEdds ^3? anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] · 6H₂O (I) and Ba2[Cu(RR,SS-Edds)](ClO₄)₂ · 8H₂O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]^2? complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO₄ · 2H₂O (III) and Ba3[Cu2(RR,SS-Edds)₂](ClO₄)₂ · 6H₂O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I–IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970–2.014 and 1.921–1.970 Å, respectively. The axial Cu-O bonds with the acetate groups and ClO ₄ ^? anions are elongated to 2.293–2.500 and 2.727–2.992 Å, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II–IV, the Ba²⁺ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO ₄ ^? anions. The coordination number of the Ba cations is nine. The structural units in I–IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO ₄ ^? anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.     

Crystal growth,structure, crystalline perfection and characterization of zinc magnesium ammonium sulfate hexahydrate mixed crystals ZnxMg(1−x)(NH4)2(SO4)2·6H2O

Mixed crystals Zn_xMg_(1?x)(NH₄)₂(SO₄)₂·6H₂O of the two well-known Tutton's salts Zn(NH₄)₂(SO₄)₂·6H₂O and Mg(NH₄)₂(SO₄)₂·6H₂O were grown with varying molar proportions (x=0.10–0.90) by slow evaporation solution growth technique. The mixed crystal Zn_0.54Mg_0.46(NH₄)₂(SO₄)₂·6H₂O is crystallizing in monoclinic system with space group P2₁/c and cell parameters a=6.2217(4) Å, b=12.5343(7) Å, c=9.2557(6) Å, β=106.912(3)°. The coexistence of zinc and magnesium ions in the mixed crystal was confirmed by inductively coupled plasma (ICP), atomic absorption spectroscopy (AAS) and energy dispersive X-ray spectroscopy (EDS). Compositional dependence of lattice parameters follows Vegard's relations. Slight variations are observed in FT-IR and XRD of pure and mixed crystals. Comparison of crystalline perfection as evaluated by high-resolution X-ray diffraction (HRXRD) for mixed crystals of various proportions reveals a reasonably good crystalline perfection for the mixed crystal with nearly equimolar ratio of Zn and Mg. The surface morphology of the mixed crystals changing with composition was studied by scanning electron microscopy (SEM). UV–vis studies reveal that the transparency of the mixed crystals was not much affected.     

Six-coordinated zinc complexes: [Zn(H2O)4(phen)] (NO3)2·H2O and [ZnNO3(H2O)(bipy)(Him)]NO3 (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, and Him = imidazole)

Two novel six-coordinated zinc complexes, tetra-aqua(1,10-phenanthroline)zinc dinitrate monohydrate, [Zn(H₂O)₄(phen)](NO₃)₂·H₂O (1) and aqua(2,2-bipyridine)(imidazole)-nitratozinc nitrate, [ZnNO₃(H₂O)(bipy)(Him)]NO₃ (2) were prepared. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 8.780(4), b = 13.609(4), c = 15.368(5) Å, = 93.86(2)°C, V = 1832.1(12) ų. In 1, a phenanthroline molecule chelates the zinc atom and four water molecules complete the octahedral geometry around the metal. Compound 2 crystallizes in the monoclinic space group P2₁/n with a = 7.250(1), b = 24.554(4), c = 10.258(2) Å, = 107.880(10)°, V = 1737.9(5) ų. In 2, a bipyridine molecule and a nitrate anion chelate the zinc atom. An imidazole molecule and a water molecule then complete the six-coordinated geometry around zinc. The intermolecular packing is controlled by hydrogen bonding, especially in 1 and by stacking. The thermal stability of the compounds and the loss of water molecules and ligands was monitored by a thermogravimetric study.     

Crystal structure of a new mineral lahnsteinite Zn4(SO4)(OH)6 · 3H2O

A sample of a new mineral from the oxidation zone of the hydrothermal Pb, Zn, Ag Friedrichssegen deposit (Rhineland-Palatinate, Germany) was studied by single-crystal X-ray diffraction. The parameters of the triclinic (pseudoorthorhombic) unit cell are found to be a = 8.312(1) ?, b = 14.545(1) ?, c = 18.504(2) ?, ?? = 89.71 (1)°, ?? = 90.05(1)°, ?? = 90.13(1)°, and V = 2237.3(3) ?³. The structure is solved by direct methods into the sp. gr. P1 and refined to an R factor of 10.7% using 3788 reflections with |F| > 3??(F) in the isotropic-anisotropic approximation. The crystallochemical formula of lahnsteinite (Z = 8) is [(Zn_2.6Fe_0.3Cu_0.1)^VI(OH)₃][Zn^IV(OH)₃(H₂O)][SO₄] · 2H₂O, where the compositions of the layer composed of Zn octahedra and isolated Zn and S tetrahedra are given in square brackets. The mineral under study is chemically and structurally similar to namuwite and is a natural analog of synthetic zinc hydroxide sulfate trihydrate.     

X-ray diffraction studies oncis-[Ru(bpy)2(PMe3)Cl+][ClO4 −] andcis-[Ru(bpy)2{PMe2(o-tol)}Cl+][ClO4 −]; two ordered structures in thecis-bis(bipyridyl)chloro(phosphine)-ruthenium(II) series

The complexcis-[Ru(bpy)₂(PMe₃)Cl⁺][ClO₄ ^?] crystallizes in space group P2₁/c andcis-[Ru(bpy)₂{PMe₂(o-tol)]Cl⁺][ClO₄ ^?] crystallizes in space group $P\bar 1$ ; each is present as a racemate and neither structure suffers from disorder. The Ru?PMe₂(o-tol) bond length of 2.324(2)Å is slightly longer than the simple Ru?PMe₃ bond length of 2.310(2) Å.