Crystal structure of 2-pyridiniumferrocene tetrafluoroborate Fe(η5-C5H5)[(η5-C5H4)(2-C5H4NH+)](BF 4 − )

Protonation of Fe( ⁵-C₅H₅)[( ⁵-C₅H₄)(2-C₅H₄N)]1 in 98% H₂SO₄ followed by dilution with water and addition of NaBF₄ yields Fe( ⁵-C₅H₅)[( ⁵-C₅H₄)(2-C₅H₄NH⁺)](BF ₄ ^– )2 instead of a ferrocinium derivative. Complex2 crystallizes in the monoclinic system, P2₁ /a:a=7.984(1),b=9.981(2),c=18.220(4) Å,=102.31 (1)°,V=1418.5 ų,Z=4. The pyridinium ring makes a dihedral angle of 21.0(2)° with the cyclopentadienyl ring to which it is bound. One F atom of BF ₄ ^– is involved in short van der Walls contacts with the N (2.764(5) Å) and the H (2.08(6) Å) atoms of the NH⁺ moiety.     

Synthesis and crystal structure of (η5-C5H5)2Ti(NH(2,4-(C$${equiv}$$CSiMe3)2C6H3))2

The crystal structure of the bis-amido complex of Ti(IV) (η⁵-C₅H₅)₂Ti(NH(2,4-(CCSiMe₃)₂C₆H₃))₂ is reported. This complex was prepared in 52% yield from the reaction of (η⁵-C₅H₅)₂TiCl₂ with two equivalents of LiNH(2,4-(CCSiMe₃)₂C₆H₃) (prepared in situ in THF at −78^∘C). The substituted aniline H₂N(2,4-(CCSiMe₃)₂C₆H₃) was prepared in 70% yield from the reaction of 2,4-dibromoaniline with Me₃SiCCH using conventional Pd/Cu coupling methodology. The molecular structure of (η⁵-C₅H₅)₂Ti(NH(2,4-(CCSiMe₃)₂C₆H₃))₂ (monoclinic, space group C2/c, Z = 4, a = 29.7523(5) Å, b = 9.5339(2) Å, c = 15.8864(3) Å, β = 93.022(1)^∘ features a titanium (IV) center with a distorted tetrahedral geometry which lies on a crystallographic twofold axis. The amido units are arranged so that steric interactions are minimized. The Ti– N distance is 2.016(2) Å.     

X-ray structural and molecular mechanics investigation of cyclopentadienyl-carbonyl-triphenylophosphine-phenylacetyliron, (η5-C5H5)Fe(CO)(PPh3)(COCH2C6H5)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-phenylacetyl-iron (1) has been determined on the basis of X-ray data. The crystals are triclinic, space groupP¯1 (Z=2) with cell dimensions:a=9.546(1),b=10.233(1),c=5.012(2) Å,=93.70(1),=101.12(1), =112.58(1)°. The structure was solved by direct methods and refined anisotropically by a full-matrix, least-squares procedure against 4964 independent reflections, givingR=0.0416. The MM calculations done for a model of1 reproduced satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

Synthesis,crystal structure and spectral studies of the complex [Ni(C3H4N2)4(H2O)2]·(C6H4COSO2N)2

The title compound has been synthesized and its crystal structure determined at room temperature.M _r =731.39, triclinic, space groupP¯1,a=9.020(3),b=11.280(7),c=7.784(2)Å,=97.05(4),=97.08(2), =105.32(4)°, U=748(1)ų,Z=1,D _calc.=1.624 g/cm³. The finalR is 0.030 for 3095 independent observed reflections withI3(I). The crystal structure consists of repeated [Ni(im)₄(H₂O)₂]²⁺ cations and noncoordinated saccharin anions. In the complex cation [Ni(im)₄(H₂O)₂]²⁺, Ni² is bonded to four N atoms from four imidazole molecules and two O atoms from two water molecules forming an approximately square octahedral stereochemistry. The d-d transition spectrum of the title compound is also reported and is explained perfectly with the scaling radial theory which was proposed by us.     

Synthesis, X-ray and neutron diffraction and Mössbauer studies of SrFeOx crystals

Tetragonal single crystals of the nonstoichiometric strontium ferrate with the lattice parameters a = 3.8525(3) and c = 3.8781 (3) Å have been synthesized for the first time by the method of floating-zone melting in the SrFeO_x system. The neutron diffraction patterns of the crystals showed weak additional reflections indicating the formation of the superstructure with double spacing along the [hh0] direction. The Mössbauer spectra of the crystals were obtained and measured in the temperature range 80–300 K. It was established that below the temperature T _N = 232(1) K, the crystals are in the magnetically ordered state with 3/5 of iron ions being in the trivalent state and all the remaining iron ions in the tetravalent state. This leads to the crystal composition SrFeO_2.71. The electric resistivity of the crystals equal to 100 ω cm at room temperature drastically decreases at temperatures exceeding 470 K.     

Synthesis and crystal structure of a dinuclear organometallic phosphonium ylid complex, [(η5-C5H5(CO)C2(ε-CO)(ε-CHP(C6H5)3)+][PF – 6 ]

The title compound crystallizes in the centrosymmetric monoclinic space group P2₁/n withZ=4. The cation consists of two (⁵-C⁵h⁵)Fe(CO) units which are linked via a metal-metal bond (Fe(1)–Fe(2)=2.530(1) Å), a bridging carbonyl ligand (Fe(1)–C(4)=1.912(8) Å. Fe(2)–C(4)=1.940(9) Å) and a bridging phosphonium ylid ligand (Fe(1)–C(1)=1.991(6) Å, Fe(2)–C(1)=1.985(6) Å and C(1)–P(1)=1.781(6) Å).     

X-ray structural and molecular mechanics investigations of cyclopentadienyl-carbonyl-triphenylphosphine-methoxyacetyl-iron (η5-C5H5)Fe(CO)(PPh3)(COCH2OMe)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-methoxy-acetyl-iron (2) has been determined by X-ray. The crystals are monoclinic:P2₁/n,Z=4,=7.881(1),b=19.111(3),c=15.271(2) Å and=93.44(1)°. The structure was solved by direct methods, and refined anisotropically by full-matrix least-squares against 3419 independent reflections, givingR=0.0446. Molecular mechanics calculations reproduce satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

Synthesis,infrared and Mössbauer characterization and X-ray crystal structure of 1,10-phenanthrolinium tetrachloromethoxy phenylantimonate(V)

The compound has been characterized by X-ray crystal structure determination, Mössbauer and i.r. spectroscopy. It crystallizes in the monoclinic space groupP2 ₁ /c (No. 14) witha=24.228(4),b=8.335(2),c=23.975(4) Å,=117.83(3)° andZ=8. Least-squares refinement on 3749 observed reflections gave finalR=0.034 (R _w=0.037). The compound is constituted by [(C₆H₅)SbCl₄OMe]^– anions andphenH⁺cations. The coordination polyhedron about Sb is an octahedron (Sb-Cl 2.416(3), Sb-O 1.962(7) and Sb-C 2.138(9) Å). The whole structure is characterized by two short contacts (O(1)N(2) 2.76(1) O(2)N(4) 2.75(1) Å) involving the methoxy oxygens of the two independent anionic units [(C₆H₅)SbCl₄OMe]^– and two nitrogens of the two independent phenanthrolinium moieties.     

Synthesis and X-ray crystal structure of an organometallic phosphonate [η6-1,2-C6H4(OCH3)(P(O)(OCH2CH3)2)]Cr(CO)3

The chiral, racemic, arene phosphonate complex, [t⁶-1,2-C₆H₄(OCH₃t)(P(O)(OCH²CH₃t)²)t] Cr(CO)₃ (1), was prepared via the reaction of 1,2-C₆H₄(OCH₃)(P(O)(OCH²CH₃)²) with Cr(CO)₆ in refluxing dioxane/THF. The title complex crystallized in P1 with the cell dimensions: a = 8.4893(4) Å, b = 11.0638(9) Å, c = 11.2135(8) Å, and = 62.151(8), = 105.154(5), = 112.426(6), giving a volume of 856.34(10) ų. The conformation of 1 is described as eclipsed (E) in which the methoxy substituent eclipses a carbonyl ligand of the tripod, and the phosphonate substituent is staggered.     

Synthesis,spectroscopic studies,and crystal structure of the first monopyridinium salt of 1,1′-bis-(2-naphthol) sulfone,C25H19NO4S

The crystal and molecular structure of 1,1-bis-(2-naphthol) sulfone monopyridine (3) determined by single-crystal X-ray diffraction is reported. C₂₅H₁₉NO₄S crystallizes in the monoclinic space groupC2/c (No. 15) witha=17.095(4),b=14.574(2),c=18.731(2) Å,=116.29(2)°,Z=8,D _x =1.364 Mg m^–3,D _m =1.353(8) Mg m^–3. The phase problem was solved by direct methods and the final reliability factor obtained from full-matrix least-squares refinement of 2306 independent reflections is 0.067. The unit cell contains eight molecules with intramolecular hydrogen bonding and the molecules in the crystal lattice are held together by van der Waals forces. Conoscopic, infrared, and¹H and C¹³ NMR analyses have been performed. Details of the structural content and selected bond lengths and angles are discussed.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

Crystal and molecular structures of 1,1′-di-tert-butylnickelocene (η5-C5H4C4H 9 t )2Ni in the temperature range 143–243 K: Thermal motion in the crystal

The crystal structure of 1,1′-di-tert-butylnickelocene is studied by the X-ray diffraction technique in the temperature range 143–243 K. The crystals are monoclinic, space group P2₁/n, Z = 2. The molecule is centrosymmetric. The cyclic ligands are parallel and adopt a staggered conformation. At 143 K, the mean bond lengths are as follows: Ni-C, 2.194(6); C-C (in the ring), 1.421(6); and C-C (Me), 1.538(2) Å. Analysis of the thermal motion of the molecule is performed within the single-parameter model, which allows for the independent motion of the cyclopentadienyl ring with the tert-butyl group as a whole and the motion of the tert-butyl group. It is shown that the molecule is structurally nonrigid and the tert-butyl group executes librational motion. The B ₅ heights of the rotation barriers are estimated from the rms libration amplitudes: 〈?²〉 are equal to 40(5) and 34(4) kJ/mol at 143 and 243 K, respectively.     

Synthesis and structural analysis of (μ-SCH2CH2CH2S-μ)Fe2(CO)5(2-C5H4NPPh2)

Treatment of (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₆ with equimolar 2-C₅H₄NPPh₂ in the presence of Me₃NO·2H₂O in CH₂Cl₂/MeCN solutions gave the title complex (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₅(2-C₅H₄NPPh₂) in 76% yield. The title complex was characterized by spectroscopy as well as by single crystal X-ray diffraction analysis. The molecular structure consists of a butterfly [Fe₂S₂] cluster with propane, five carbonyls, and 2-C₅H₄NPPh₂. In the crystal packing diagram, intermolecular C–H···O hydrogen bonds between phenyl and carbonyl groups stabilize the solid state.     

Synthesis and molecular structure of the organometallic zwitterion (η5-C5H3MeBCl3)Fe(CO)3: evidence for alternative sites of nucleophilicity within the [(η5-C5R5)Fe(CO)2 − anion

The organometallic zwitterion (⁵-C₅H₃MeBCl₃)Fe(CO)₃ (2) is isolated as a minor product from the reaction between the sodium salt of the anion [(⁵-C₅H₄Me)Fe(CO)₂]^– and boron trichloride. The crystal structure of 2 [P2₁/n, a = 7.3927(5) Å, b = 13.8027(9) Å, c = 12.2759(9) Å, = = 90°, = 92.517(3)°] features discrete molecules in which the coordination sphere of the iron center comprises three carbonyls and a novel ( ⁵-C₅H₃MeBCl₃) ligand, derived from attack of BCl₃ on the ( ⁵-C₅H₄Me) moiety of the parent compound. The isolation of 2 confirms that the nucleophilic properties of organometallic anions of the type [( ⁵-C₅R₅)M(CO) _n ]^– (M = Fe, Ru, n = 2; M = Mo, W, n = 3) are not confined to the metal center, or to the carbonyl oxygens (examples of which have previously been reported) but also encompass the cyclopentadienyl ligand.     

The importance of inter-molecular forces in crystal structure analysis: Solid state study of the diag-to-lat isomerization of (η5-C5H4Me)Re(CO)2Br2

Single crystal X-ray structures of diag and lat-(⁵-C₅H₄Me)Re(CO)₂Br₂ have been determined. The diag form crystallizes in the triclinic space group , a = 6.751(2), b = 8.537(1), c = 9.758(1) Å = 96.70(1), = 93.15(2), = 104.96(2)°, V = 534.8(2) ų, Z = 2. The lat form is monoclinic, P2₁/c, a = 11.820(1), b = 7.133(1), c = 12.924(1) Å = 98.278(8)°, V = 1078.2(2) ų, Z = 4. The unit cell volumes (per Z) of the two isomers differ by ca 1%. Molecular modelling reveals an energy difference between the two isomers of 1 kJ mol^–1 or less. The XRD powder diffraction patterns for the lat isomer produced by crystallization from solution or prepared by thermal isomerization are identical. The evidence thus suggests that the solid state isomerization reaction is a novel example of a reaction which yields a molecular structure determined by crystal packing forces.     

Crystal structures of (η5-C5H4COMe)M(CO)3Me (M=Mo,W)

The crystal structures of ( ⁵-C₅H₄COMe)M(CO)₃Me (M=Mo,W) have been determined. They are not isostructural. M=Mo isP2₁/c,a=10.205(6),b=14.192(8),c=8.135(6) Å,=93.43(4)° andD(calc)=1.71 g cm^–3 forZ=4. M=WisP2₁/c,a=12.580(7),b=6.830(5),c=13.750(7) Å,=93.72(4)° andD(calc)=2.20 g cm^–3 forZ=4. Both have a four-legged piano stool geometry with the substituted carbon making the closest M-C( ⁵) approach. The methyl group in the M=W derivative is disordered between twotrans-ligand positions. The average bonding parameters for the more accurately determined Mo analog are: Mo-C()⁵)=2.34(3) Å, Mo-CO=1.98(2) Å, Mo-Me=2.304(4) Å.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.