Structure of [Ru(phen)3](ClO4)2.(C2H5)2O

The title solvated complex, in which phen denotes 1,10‐phenanthroline, crystallizes in the monoclinic space group P2₁/n with a = 13.313 (3), b = 15.980 (3), c = 18.392 (4) Å, α = 96.76 (3)°, Z = 4, V = 3885.4 (14) ų, D_cal = 1.564 Mg m^‐3. The crystal is composed of racemic layers of complex cations, with the ether solvents located near, and the perchlorate anions sandwiched between, indicating the hydrophobic environment in the complex layer and the stacking interaction between the enantiomeric cations. The average length of the Ru‐N bonds is 2.064 (2) Å and the average ligand bite angle is 80.00 (7)°.     

Crystal Structure Investigation of 2-Pheny limidazo [f]1,10-phenanthroline

The crystal structure of the title compound (PIP) has been determined by single crystal X-ray diffraction methods. C₁₉H₁₂N₄. C₂H₅OH crystallizes in the monoclinic space group P2₁/n with a = 11.4414(8), b = 12.6052(9), c = 12.4627(8) Å, β = 100.345(2)°, Z = 4, V = 1768.17 ų, D_cal = 1.286 Mg. m⁻³, μ (MoKα) = 0.80 cm^-1, F(000) = 720. The structure was solved by the direct methods and refined by full-matrix least-squares method to a final R = 0.0337 and R_w = 0.0332 for 2306 reflections with F₀ > 4σ(F₀). The phenl ring and the imidazo[f]1,10-phenanthroline moiety are coplanar in the crystal. The packing of the molecules involves hydrogen bonded association of the hydroxyl group of ethanol both with the N H of the imidazole moiety of one PIP and one nitrogen atom of the phenanthroline moiety of another PIP.     

Structural and spectroscopic study of tetrakis(N,N-diethyldithiocarbamato)molybdenum(V) triiodide,Mo[S2CN(C2H5)2]4 I3

Oxidation of Mo₂[S₂CN(C₂H₅)₂]₆ with iodine in a 12 molar ratio yielded the complex MO[S₂CN(C₂H₅)₂]₄ I₃, for which magnetic susceptibility, NMR, IR, UV/visible spectra, and single crystal X-ray structure are reported. Crystals of Mo[S₂CN(C₂H₅)₂]₄ I₃ are monoclinic, space groupC2/c (No. 15),a=26.242(7),b=7.003(1),c=20.447(3) Å,D _o =1.97,Z=4,D _c =1.890 g cm^–3. The structure was determined from 1909 observed reflections and refined by blocked cascade least squares to anR factor of 0.042. The core of the cation, Mo[S₂CN(C₂H₅)₂] ₄ ⁺ , is dodecahedral with approximate point symmetryD _2d (¯42m). The eight S atoms coordinated to the Mo center can be divided into two sets, each forming a distorted tetrahedron. The set constituting a flattened tetrahedron has a mean Mo-S distance of 2.545(2) Å, whereas the set that forms an elongated one has a mean value of 2.500(2) Å. The oxidation state of +5 for the molybdenum atom is supported by the thioureide band [v(RNC)] at 1507 cm^–1, which lies between those of similar Mo(IV) and Mo(VI) complexes.     

Crystal structure of Zn[Cl2Ti(C5H5)2]2·2C6H6

The structure of crystals of the composition Zn[Cl₂Ti(C₅H₅)₂]₂·2C₆H₆ has been determined from Patterson and Fourier syntheses of two projections, and refined toR = 0·117 by full-matrix three-dimensional least-squares methods. The crystals are orthorhombic:Pbcn,a = 18·45(5),b = 15·40(6),c = 11·35(3) Å,Z= 4. The complex consists of a central distorted ZnCl ₄ ^2– tetrahedron linked along the Cl—Cl edges to two distorted TiCl₂(C₅H₅)₂ ⁺ tetrahedra in such a way that their centres are nearly collinear The two C₆H₆ molecules in the formulae unit may be regarded as benzene of crystallization.     

Electronic Structure of [Cu(C7H4NO3S)2(H2O)4] · 2H2O Crystal

The electronic absorption spectrum and ESR spectrum of the crystal of the title compound [Cu(C₇H₄NO₃S)₂(H₂O)₄] · 2 H₂O, are measured. The experimental results are discussed quantitatively by using the ligand field theory and the radial wave function of non-free Cu(II). The electronic structure of the compound is in agreement with its crystal structure.     

Crystal structure of the orange isomer of [(C6H5)3P]2[C2S2(CF3)2]RuCO

The structure of the title compound has been determined by X-ray analysis. It is monoclinic:a = 10.147,b = 10.081,c = 38.627 Å, β = 102.27 °,Z = 4,P2₁/c. The structure was solved by standard methods and refined by least squares to a (conventional)R-factor of 4.7%. The Ru atom is in square-pyramidal configuration: the Ru-S distances (2.286, 2.336Å) are significantly different, but the Ru-P distances average to 2.389 Å. Comparisons are made with the violet isomer.     

Crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline)cobalt(III) chloride 3.5 hydrate

The crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline) cobalt(III) chloride 3.5 hydrate [Co(Ceida)(H₂O)(Phen)Cl · 3.5H₂O (I) has been determined by ¹H NMR technique and X-ray diffraction analysis. The crystals are triclinic, a = 10.352(2) Å, b = 12.534(3) Å, c = 20.665(4) Å, α = 107.02(3)°, β = 92.22(3)°, γ = 111.63(3)°, Z = 4, space group $P\bar 1$ , andR = 0.0438. The unit cell involves two crystallographically nonequivalent but virtually identical cationic complexes [Co(Ceida)(H₂O)(Phen)]⁺. The tridentate chelate ligand Ceida ^2? (N + 2O) occupies the face in the coordination octahedron of the Co atom, and the propionamide group remains free. The mean bond lengths are as follows: Co-O_Ceida, 1.876 Å; Co-N_Ceida, 1.981 Å; Co-N_Phen, 1.945 Å; and Co-O_w, 1.915 Å. In the structure, the arrangement of cationic complexes and certain water molecules exhibits a pseudosymmetry (the 2₁ axis). The cations and water molecules are located in the layers, and the anions are arranged between the layers. The structural elements are linked by hydrogen bonds and van der Waals interactions.     

Chiral bisphosphanes XII: Synthesis and molecular structure of cis-{rac,trans-1,2-bis[bis(morpholin-4-yl)-phosphino]cyclopentane}dimethylplatinum(II), cis-[C5H8{P[N(C2H4)2O-cyclo]2}2Pt(CH3)2]

Crystals of the title compound are monoclinic, space group P2₁/c, with a = 10.2621(8), b = 15.372(5), c = 17.612(2) Å, = 95.928(9)°, and Z = 4. Coordination about the central metal deviates slightly from ideal square-planar geometry. The five-membered chelate ring adopts an envelope conformation with one of the two P atoms (P1) deviating from the least-squares plane spanned by the central metal, the bridging CH carbons, and donor atom P2. While the morpholino substituents at the latter show little axial-equatorial discrimination for their orientation with respect to the coordination plane, the spatial alignments of the N(C₂H₄)₂O rings attached to P1 differ significantly between a more equatorial and a more axial disposition. The conformationally dissimilar arrangement of the two P donor groups within the envelope-like chelate ring manifests itself in unequal Pt–P bond lengths: d(Pt–P1) = 2.2677(16), d(Pt–P2) = 2.2825(16) Å. The Pt–CH₃ distances amount to 2.114(6) (trans to P2) and 2.141(6) Å (trans to P1), respectively.     

Structure of diaqua(itaconato) cadmium(II), [Cd(C5H4O4)(OH2)2]

[Cd(C₅H₄O₄)(OH₂)₂] (1), crystallizes in the monoclinic system, space groupP2₁/n, with lattice parametersa=7.323(2),b=16.028(6),c=7.202(2) Å, β=113.11(1)°, andZ=4. The Cd atom coordinates to seven oxygens in a monocapped trigonal antiprism fashion. The antiprisms share one vertex to form chains which run approximately parallel to thec axis. The itaconate ligands link the chains to form layers which stack along theb axis.     

Biscyclopentadienides with transition metal-mercury bonds. II: Dithiocarbamato derivatives of molybdenum and tungsten,and X-ray structure of (η5-C5H5)2Mo[HgS2CN(C2H5)2]2

The reactions in THF or benzene between Cp₂ M (HgX)₂ ·x HgX ₂ (M = Mo or W; O ?x ? 1;X ^? = Cl^?, Br^?, I^?, SCN^?, OAc^?) and sodium diethyl-dithiocarbamate $$\begin{gathered} Cp_2 M\left( {HgX} \right)_2 .xHgX_2 + \left( {2 + x} \right)Nadtc \rightleftharpoons Cp_2 M\left( {Hgdtc} \right)_2 \hfill \\ + xHg\left( {dtc} \right)_2 + \left( {2 + x} \right)NaX \hfill \\ \end{gathered} $$ as well as between Cp₂ MH₂ and mercury diethyldithiocarbamate $$x2Cp_2 MH_2 + 2Hg\left( {dtc} \right)_{2 - } Cp_2 M\left( {Hgdtc} \right)_2 + \left\{ {Cp_2 Mdtc} \right\}dtc + 2H_2 $$ give the compound Cp₂ M(Hgdtc)₂ (dtc is diethyldithiocarbamate anion). The structure of the molybdenum complex determined by the X-ray method (a = 12.776(4),b = 7.835(4),c = 27.397(7) Å β = 111.18(2) °; space groupC2/c (No. 15);Z = 4) consists of discrete molecules occupying special positions on two-fold axes. A short Mo-Hg distance of 2.643(8) Å and a rather long Hg-S one of 2.50(2) Å were found. The diethyldithiocarbamate anion behaves like a monodentate ligand. IR and¹H,¹³C NMR results agree with the molecular structure determination and confirm a weak bond between mercury and dithiocarbamate and strong molybdenum-mercury bond. A considerable solvent effect (C₆D₆ vs. CDCl₃ solutions) has been observed on the¹H chemical shifts of both dtc and Cp ligands. The {Cp₂Modtc}⁺ X ^? (X = dtc and PF₆) complexes, although not obtained in a pure form, were included in the discussion of the spectroscopic features of those with theM-Hg bonds.     

The crystal field theory for D2d symmetric complexes and the splitting of d-orbitals of Mo5+ in Mo[S2CN(C2H5)2]4I3

The energy order assignment of the d-orbitals of Mo⁵⁺ in Mo[S₂CN(C₂H₅)₂]₄I₃ given by Jasimet al. (1985) is restudied and corrected. It is indicated that, in general, the energy order of the d-orbitals of D_2d symmetric complexes is depending on the bond angles and bond lengths of the ligands, thus there cannot be any universal energy order.     

Synthesis and crystal structure of the thiophene-3-acetonitrile complex fac-[Mo(CO)3{NCCH2(C4 H 3S-3)}3]

Reaction of fac-[Mo(CO)₃(NCMe)₃] with three equivalents of NCCH₂(C₄ H ₃S-3) in acetonitrile gives the tris(thiophene-3-acetonitrile) complex, fac-[Mo(CO)₃{NCCH₂(C₄H₃S-3)}₃] (1) in 7% yield. Complex 1 crystallizes out in the orthorhombic space group Pnma with a = 12.714(17), b = 16.41(2), c = 11.304(16) Å, Z = 4. The structure has crystallographic m symmetry and the metal is in an almost perfect octahedral environment, with a facial arrangement of carbonyl and thiophene-3-acetonitrile groups. The thiophene rings are disordered.     

Structure of the [5S,15S] isomer of the macrocyclic complex, [La(NCS)3(C24H30N6)]

The crystal and molecular structure of the [5S,15S] isomer of the [LaL(NCS)₃] complex (L=C₂₆H₃₀N₆) was determined by single crystal X-ray diffraction analysis. The compound crystallizes in the orthorhombic space group P2₁2₁2₁ witha=13.647(4),b=19.504(4),c=11.606(4)Å. The 9-coordinate La(III) is bound to the N atoms of three monodentate isothiocyanates and to the six N atoms of the macrocycle ligand L, which has an 18-membered, six-nitrogen donor cavity and two peripheral –CH₃ substituents.