Synthesis and unusual crystal structure of the Eu(III) complex with 1-(1,5-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione

The reaction of Eu(NO₃)₃ · 6H₂O with 1-(1,5-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione (HL) in the presence of NaOH in aqueous ethanol gave neutral complex [EuL₃(H₂O)] (I). The unstable adduct [EuL₃(H₂O)] · 1.3MeCN (Ia) was obtained from an acetonitrile solution and studied by X-ray diffraction. The crystals of Ia at 100 K are monoclinic, a = 17.551(3) Å, b = 11.532(2) Å, c = 20.371(3) Å, β = 110.886(3)°, V = 3852(1) ų, space group P2₁/c, Z = 4, R = 0.0505. The molecules are connected into chains by strong interactions between the europium atom of one molecule and the pyrazole N(2) atom of another molecule and additionally stabilized by strong hydrogen bonds O(1w)-H(1w1)…N(4)*. The chains are combined into layers by the hydrogen bonds (1w)-H(2w1)…N(2)*.     

Further studies on the taumerization of the hydrido (alkynyl) cluster Ru3Pt(μ-H) {μ4-ν2-C ≡ C1Bu} (CO)9(L2) to the vinylidene cluster Ru3Pt{μ4-ν2-C ≡ C(H)tBu} (CO)9(L2): X-ray structures of Ru3Pt(μ-H){μ4-ν2-C = C(H)tBu} (CO)9(L2); L2 = dppet,dppp, andS,S-dppb

The first order rate constants for the tautomerization of the hydrio(alkynyl) clusters Ru₃Pt(μ-H){μ₄-ν²-C ≡ C¹Bu}(CO)₉(L₂);1a: L₂ = dppe,1b; L₂ = dppet,1c; L₂ = dppp and1d; L₂ =S,S-dppb to the corresponding vinylidene clusters Ru₃Pt{μ₄-ν²-C = C(H)^tBu}(CO)₉(L₂)2 have been measured, and they follow the orser1d <1a <1b ～1c. The reactions involving1a and1d exhibit an inverse kinetic deuterium isotope effect. The structures of1b, 2b, 2c, and2d were determined by X-ray crystallography, and are compared with those of1a and2a which have been previously reported. Crystal data for1b, space groupPbca,a = 13.338(4) Å,b = 17.771(6) Å,c = 36.092(8) Å,Z = 8,R(R _w) = 0.059(0.058) for 2342 absorption corrected, observed data; for2b, space group P2₁/n,a = 10.566(2) Å,b = 20.234(5) Å,c = 20.270(3) Å,β = 96.11(1)°,Z = 4,R(R _w) = 0.043(0.053) for 5865 absorption corrected, observed data; for2c, space group P2₁/n,a = 14.211(5) Å,b = 19.534(2) Å,c = 15.870(2) Å,β = 100.81(2)°,Z = 4,R(R _w) = 0.055(0.031) for 6566 absorption corrected, observed data: for2d, space group P2₁2₁2₁,a = 12.309(4) Å,b = 19.047(6) Å,c = 19.206(4) Å,Z = 4,R(R _w) = 0.055(0.053) fpr 2151 absorption corrected, observed data. The fluxional behavior of1d and1e (which consists of two interconverting isomers) has been examined by variable temperature¹³C NMR spectroscopy and by³¹P EXSY.     

Thiourea-halide lattices. Part 1. Crystal structures of (n-C4H9)4N+F−·3(NH2)2CS, (n-C4H9)3(CH3) N+X−·2(NH2)2CS (X = Cl,Br), and (n-C3H7)4N+I−·(NH2)2CS

The title complexes (1, X = F;2, X = C 1; 3, X = Br and isomorphous with2; 4, X = I) have been prepared and characterized by X-ray crystallography. Crystal data, MoKα radiation:1, space groupCc,Z =4,a = 12.017(3),b = 14.263(5),c = 17.210(7) Å,β = 103.06(2)°, andR _F =0.053 for 2044 observed data;2, space groupCc,Z = 4,a = 12.817(3),b = 11.072(2),c = 16.781(5) Å,β =90.74(2)°,R _F = 0.044 for 2249 data;3,a = 12.873(4),b = 11. 119(2),c = 16.957(2) Å,β = 89.11(2)°,R _F = 0.049 for 2059 data;4, space groupP2₁/n,Z = 4,a = 8.858(2),b = 14.358(3),c = 15.379(3) Å,β = 93.88(1)°,R _F = 0.068 for 3119 data. In all four structures each thiourea molecule interacts with adjacent thiourea molecules via N-H ... S hydrogen bonds to give a ribbon-like arrangement, and also forms a pair of ‘chelating’ N-H ... X hydrogen bonds with a halide ion, resulting in an anionic framework (in1–3) or composite ribbon (in4) as a component in the crystal packing. The measured ranges of N... X distances are: 2.819(5)-2.994(7) Å for1, 3.252(3)-3.291(3)Å for 2, 3.353(6)-3.459(6)Å for3, and 3.564(5)-3.680(5) Å for 4.     

Chelating diamide complexes of titanium: new catalyst precursors for the highly active and living polymerization of α-olefins

The reaction of RHN(CH₂)₃NHR (1a,b) (a, R=2,6-ⁱPr₂C₆H₃; b, R=2,6-Me₂C₆H₃) with 2 equiv of BuLi followed by 2 equiv of ClSiMe₃ yields the silylated diamines R(Me₃Si)N(CH₂)₃N(SiMe₃)R (3a,b). The reaction of 3a,b with TiCl₄ yields the dichloride complexes [RN(CH₂)₃NR]TiCl₂ (4a,b) and two equiv of ClSiMe₃. An X-ray study of 4a (P2₁/n, a=9.771(1) Å, b=14.189(1) Å, c=21.081(2) Å, β=96.27(1)°, V=2905.2(5) ų, Z=4, T=25°C, R=0.0701, R_w=0.1495) revealed a distorted tetrahedral geometry about titanium with the aryl groups lying perpendicular to the TiN₂-plane. Compounds 4a,b react with 2 equiv of MeMgBr to give the dimethyl derivatives [RN(CH₂)₃NR]TiMe₂ (5a,b). An X-ray study of 5b (P2₁2₁2₁, a=8.0955(10) Å, b=15.288(4) Å, c=16.909(3) Å, V=2092.8(7) ų, Z=4, T=23°C, R=0.0759, R_w=0.1458) again revealed a distorted tetrahedral geometry about titanium with titanium–methyl bond lengths of 2.100(9) Å and 2.077(9) Å. These titanium dimethyl complexes are active catalysts for the polymerization of 1-hexene, when activated with methylaluminoxane (MAO). Activities up to 350,000 g of poly(1-hexene)/mmol catalyst·h were obtained in neat 1-hexene. These systems actively engage in chain transfer to aluminum. Equimolar amounts of 5a or 5b and B(C₆F₅)₃ catalyze the living aspecific polymerization 1-hexene. Polydispersities (M_w/M_n) as low as 1.05 were measured. Highly active living systems are obtained when 5a is activated with {Ph₃C}⁺[B(C₆F₅)₄]⁻. A primary insertion mode (1,2 insertion) has been assigned based on both the initiation of the polymer chain and its purposeful termination with iodine.     

An X-ray and 13C CP/MAS NMR study of C,C-linked bipyrazoles and bispyrazolylmethanes

4,4′-Methylene-bispyrazole (1) crystallizes in the P2₁/n space group with Z = 4, a = 5.4199(8) Å, b = 16.194(6) Å, c = 8.381(5) Å, β = 98.18(5)°. 4,4′-Methylene-bis (3,5-dimethylpyrazole) (2) crystallizes in the Pbca space group with Z = 8, a = 8.350(3) Å, b = 16.078(3) Å and c = 17.154(5) Å. Finally, 3,3′-bipyrazole (4) crystallizes in the P2₁/n space group with Z = 2, a = 5.465(2) Å, b = 5.491(3) Å, c = 10.058(4) Å and sol; = 92.88(2)°. The packing adopted by molecules 1 and 2 is related to the disposition of the pyrazole rings. In compound 4, all the molecules are joined to their neighbors by two double hydrogen bond systems forming zigzag chains. Using solid state ¹³C NMR spectroscopy, no dynamic proton transfer was observed in these crystals, and not on those of 3,5,3′,5′-tetramethyl-4,4′-bipyrazole (3) either.     

Ground state conformation of diphenylvinylphosphine sulfide and selenide

Single-crystal X-ray diffraction experiments have been performed on diphenylvinylphosphine sulfide ( 1 ): C₁₄H₁₃PS, space group P 2₁/c, a = 10.186(1) Ǎ, b = 11.918(1) Å, c = 11.426 Å, β = 112.22(2)°, V = 1284.1(2) ų, Z = 4, and diphenylvinylphosphine selenide ( 2 ): C₁₄H₁₃PSe, space group Pbca, a = 9.141 (3) Å, b = 16.458 (1) Å, c = 17.451 (1) Å, V = 2625.4 (9) ų, Z = 8. The structures were solved by direct methods and were refined by full matrix least-squares calculations to R = 0.046 and R_w = 0.058 using 2554 unique reflections with I > 3σ(I) in the case of 1 , and to R = 0.052 and R_w = 0.065 using 1953 unique reflections with I > 3σ(I) in the case of 2 . In close analogy to the previously studied vinyl phosphine oxides both 1 and 2 were found to exist in the s-cis conformation with the pertinent CC PX dihedral angles equal to 12.5° and 2.9° for 1 and 2 , respectively.     

The Role of Chloro Substituents in Solid Inclusion Formation. Crystal Structures Formed by a Bulky Hydroxy Host with Ethyl Acetate (2:1) and Cyclohexylamine (1:2) as Guest

Abstract

Two inclusion compounds of the 11-[bis(p‐chlorophenyl)hydroxymethyl]-9,10-dihydro-9,10-ethanoanthracene host (1) have been studied by X-ray diffraction in order to find an explanation of the exceptional clathrate formation ability of the present chloro-containing host as compared with that of closely related chlorine-free host analogues. Crystal data: 1·ethyl acetate (2:1), C₂₇H₂₂OCl₂·½(C₄H₈O₂), M_w = 501.45, P2_1/c, a = 8.9060(5), b = 11.1109(6), c = 25.642(1) Å, β = 99.03(1)°, Z = 4, R = 0.047 for 2029 F values with I>2σ(I); 1·cyclohexylamine (1:2), 2[C₂₉H₂₂OCI₂·2(C₆H₁₃N)], M_w = 1311.50, Pc, a = 12.144(2), b = 12.689(3), c =23.119(8) Å, β = 91.68(1)°, Z = 2, R = 0.054 for 3073 F values with I>2σ(I). Although the two solid inclusion compounds differ in host‐guest stoichiometry, space group symmetry and also in host‐guest recognition mode, both co-crystals are held together by numerous C?H…X (X = O, N or Cl) interactions, in which the chloro-substituents of 1 play a very active role. The observed frequent participation of chlorine in intermolecular interactions in these compounds suggests an ability of the (C?)Cl substituents to effectively enhance the crystal formation in the absence of more dominant forces.     

Structural Studies on Dimethyltin(IV) Carboxylates

In order to correlate ¹¹⁹Sn Mössbauer parameters and structural data for dimethyltin(IV) derivatives, the molecular structures of bis(acetato)dimethyltin(IV) and bis(trifluoroacetato)dimethyltin(IV) were determined by single crystal X-ray diffration. Crystals of Me₂Sn(OOCCH₃)₂ are monoclinic, a = 26.282(4), b = 5.282(1), c = 14.434(3) Å, β = 101.17(2)°, Z = 8, space group C2/c, and those of [Me₂Sn(OOCCF₃)₂]_n are monoclinic, a = 8.444(1), b = 17.689(1), c = 15.368(1) Å, β = 93.013(9)°, Z = 8, space group Cc. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.025 and 0.027 (R_w = 0.023 and 0.030) for 2 298 and 4 182 reflections with I ≥ 3σ(F²), respectively.     

Synthesis and crystal structure of the π copper(I) cyanide complex with N,N′-diallyl thiocarbamide 2CuCN · (C<Subscript>3</Subscript>H<Subscript>5</Subscript>NH)<Subscript>2</Subscript>CS

Crystals of the π copper(I) cyanide complex with N,N′-diallyl thiocarbamide, 2CuCN · (C₃H₅NH)₂CS (I), are synthesized from an aqueous-methanol solution of potassium nitroprusside, diallyl thiocarbamide on a copper electrode using the method of alternating-current electrochemical synthesis. The crystals are monoclinic: space group P2₁/n, a = 6.9440(5) Å, b = 13.760(1)) Å, c = 12.733(1) Å, β = 97.280(9)°, V = 1206.8(2) ų, Z = 4, R = 0.0361, R _w = 0.0362 for 2836 independent reflections with F ≥ 4σ(F). A unique polymeric structure is built due to the Cu(I)-(C=C) π bond and the bridging function of the thioamide S atom of the ligand molecule and one of the two independent cyano groups.     

X-RAY CRYSTAL STRUCTURE OF AN ORGANOINDIUM ALKOXIDE DIMER, (Ph2InOSiMe3)2

Abstract

The solid-state structure of (Ph₂InOSiMe₃)₂, 1, has been established by single-crystal X-ray analysis. Monoclinic crystals of 1 belong to space group P2₁/c, with a = 9.136(1), b = 15.503(2), c = 11.836(1) Å, β=102.46(1)°, Z = 2. Refinement of atomic parameters converged at R = 0.050 (R _w = 0.063) over 1718 observed reflections with I > 3.0σ(I). The dimeric molecule lies on a crystallographic centre of symmetry with In-O = 2.159(7) and 2.149(8) Å, O-In-O = 78.9(3)°, and In-O-In = 101.1(3)°. Compound 1 is only the second example of a simple dimeric organoindium alkoxide to be structurally characterized in this manner.     

CRYSTAL STRUCTURES AND TRIBOLUMINESCENT ACTIVITIES OF SAMARIUM(III) COMPLEXES

Abstract

The triboluminescence spectra and crystal structures of 1,2-dimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (1) and 1,2,6-trimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (2) were determined. The triboluminescent maximums are similar to those of the photoluminescence. Complex 1 is centrosymmetric and the triboluminescent emission may correlate with the disorder of all S atoms, all CF₃ groups and the cation. The triboluminescent activity of complex 2 may correlate with its noncentrosymmetric space group. Complex 1 crystallizes in the monoclinic space group P2₁/a with cell parameters a = 19.874(2) Å, b = 22.922(2)Å, c = 21.188(1)Å, β = 108.126(6)°, V = 9173(1)ų; Z = 8; R = 0.0758 and R_w = 0.1315. Complex 2 crystallizes in the monoclinic space group Pn with cell parameters a = 11.2808(6)Å, b = 11.0199(5)Å c c = 18.4336(9)Å, β = 108.126(6)° V = 2285.28(19)ų; Z = 4; R = 0.0347 and R_w = 0.0900. All the structures were refined by full-matrix least squares methods.     

Synthesis and structures of two hydrazone compounds derived from 4-methylbenzohydrazide

Two hydrazone compounds N′-(2,4-dichlorobenzylidene)-4-methylbenzohydrazide monohydrate (1) and 2-chloro-5-nitro-N′-(4-methylbenzylidene)benzohydrazide (2) derived from 4-methylbenzohydrazide with different benzaldehydes are synthesized and characterized by physicochemical methods and single crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group P2₁2₁2₁ with unit cell parameters a = 4.714(2) Å, b = 13.093(3) Å, c = 24.754(3) Å, V = 1527.9(8) ų, Z = 4, R ₁ = 0.0812, and wR ₂ = 0.1623. Compound 2 crystallizes in the monoclinic space group Cc with unit cell parameters a = 11.564(2) Å, b = 13.271(2) Å, c = 9.462(2) Å, β = 96.860(2)°, V = 1441.7(4) ų, Z = 4, R ₁ = 0.0461, and wR ₂ = 0.0896. The crystals of the compounds are stabilized by intermolecular hydrogen bonds as well as π…π stacking interactions.     

Syntheses and structures of mononuclear eight-coordinate Na[ErIII(Cydta)(H2O2]·5H2O (Cydta = trans-1,2-cyclohexanediaminetetraacetic acid) and binuclear nine-coordinate Na2[SmIII(Cydta)][SmIII(Cydta)(H2O)3] · 11H2O

The title complexes, Na[Er^III(Cydta)(H₂O)₂] · 5H₂O (I) and Na₂[Sm^III(Cydta)][Sm^III(Cydta)(H₂O)₃] · 11H₂O (II) (Cydta is trans-1,2-cyclohexanediaminetetraacetic acid), are prepared and characterized using IR, elemental analyses, and single-crystal X-ray diffraction techniques. Crystal I belongs to triclinic system (space group P1), which has a mononuclear eight-coordinate slightly distorted square antiprismatic conformation. The crystal data are as follows: a = 8.371(12) Å, b = 9.952(14) Å, c = 14.74(2) Å, α = 88.32(2)°, β = 76.30(2)°, γ = 87.87(2)°, V = 1192(3) ų, Z = 1, ρ = 1.835 g/cm³, μ = 3.612 mm^?1, F(000) = 658, R = 0.0194, and wR = 0.0520 for 4130 observed reflections with I≥2σ(I). Crystal II belongs to monoclinic system (space group P2₁/n), which has the binuclear nine-coordinate structure with tricapped trigonal prismatic conformation for Sm(1) and the pseudomonocapped square antiprismatic conformation for Sm(2). The crystal data are as follows: a = 12.283(6) Å, b = 15.626(7) Å, c = 25.875(12) Å, β = 97.962(7)°, V = 4919(4) ų, Z = 4, ρ = 1.717 g/cm³, μ = 2.476 mm^?1, F(000) = 2536, R = 0.0781, and wR = 0.1745 for 8554 observed reflections with I ≥ 2σ(I).     

Crystal structures and antibacterial activity of hydrazone derivatives from 1H-indol-3-acetohydrazide

A series of three new hydrazone derivatives C₂₂H₁₉N₃O₂ (1), C₁₇H₁₃ClN₄O₃ (2), and C₂₁H₂₄N₄O₂·CH₄O (3) obtained by the condensation of ¹H-indol-3-acetohydrazide with 2-methoxynaphthaldehyde, 2-chloro-5-nitrobenzaldehyde, and 4-diethylaminosalicylaldehyde, respectively, in methanol, ia prepared. The compounds are characterized by elemental analysis, IR spectra, ¹H NMR spectra, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P2₁/n with unit cell dimensions a = 17.740(2) Å, b = 5.621(1) Å, c = 18.573(3) Å, β = 92.659(2)°, V = 1850.0(6) ų, Z = 4, R ₁ = 0.0610 and wR ₂ = 0.1155. Compound 2 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 29.178(2) Å, b = 8.195(1) Å, c = 14.372(1) Å, β = 109.446(2)°, V = 3240.5(5) ų, Z = 8, R ₁ = 0.0452 and wR ₂ = 0.1028. Compound 3 crystallizes in the monoclinic space group Pc with unit cell dimensions a = 6.579(1) Å, b = 15.112(2) Å, c = 10.676(2) Å, β = 90.030(2)°, V = 1061.4(3) ų, Z = 2, R ₁ = 0.0535 and wR ₂ = 0.1123. The single crystal X-ray structural determination reveals that the molecules of the compounds are much twisted due to the lack of efficient conjugation. Preliminary biological tests indicate that the compounds are effective antibacterial material.     

Synthesis and Structures of [Mo12E16(PEt3)10] (E = S,Se)

Dodecanuclcar cluster complexes [Mo₁₂S₁₆(PEt₃)₁₀] 1 and [Mo₁₂Se₁₆(PEt₃)₁₀] 2 have been prepared by the reactions of [Mo₆S₈(PEt₃)₆] with sulfur or [Mo₆Se₈(PEt₃)₆] with Cp₂TiSe₅, respectively, in toluene at refluxing temperature. The structures have been determined at 173 K by X-ray crystallography. The compound 1 ·3CHCl₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 14.859(5) Å, b = 15.868(4) Å, c = 14.200(7) Å, α = 100.58(3)°, β = 117.58(3)°, γ = 79.53(2)°, V = 2899(1) ų, and Z = 1. Full-matrix least-squares refinement using 9016 observed reflections (I_o > 2σ(I_o)) gave R = 0.056, and R_w = 0.045. The data for 2 ·2CHCl₃ are: triclinic, $ {\rm P}\bar 1 $, a = 15.737(4) Å, b = 18.763(9) Å, c = 13.062(4) Å, α = 102.45(3)°, β = 128.54(2)°, γ = 69.49(3)°, V = 2825 ų, Z = 1, R = 0.096, and R_w = 0.120 for 5922 reflections (I_o > 2σ(I_o)). The cluster complexes 1 and 2 have two octahedral molybdenum cluster units linked by the rhomboidal intercluster Mo₂(μ₄-E)₂ bonding. The intercluster Mo—Mo distances in 1 are 3.419 Å and 2 3.551 Å. The cyclic voltammetry of 1 and 2 shows two oxidation and two reduction steps separated as large as 380–490 mV. The UV-Vis spectra of the dodecanuclear cluster complexes 1 and 2 have an extra weak band at around 744 nm which is absent in the starting octahedral cluster complexes.     

Two fumarato-bridged Co(II) coordination polymers: syntheses,crystal structures and properties of Co(H2O)4L and [Co3(H2O)4(OH)2L2]·2H2O with H2LHOOCCHCHCOOH

Two fumarato-bridged Co(II) coordination polymers Co(H₂O)₄L 1 and [Co₃(H₂O)₄(OH)₂L₂]·2H₂O 2 with H₂LHOOCCH CHCOOH were prepared. Complex 1 consists of polymeric chains _∞¹[Co(H₂O)₄(C₄H₂O₄)_2/2], which result from octahedrally coordinated Co atoms bridged by bis-monodentate fumarate anions and are assembled by interchain hydrogen bonds. Within 2, the edge-shared Co₂O₁₀ bi-octahedra are connected to the CoO₆ octahedra to form 1D cobalt oxide chains and 3D open framework generated from the chains inter-linked by bis-bidentate fumarate anions displays rhombic tunnels, which are filled with the lattice H₂O molecules. Thermal and magnetic behaviors of both the title coordination polymers are discussed. Crystal data: (1) monoclinic, P2₁/c, Z=4, a=7.493(1) Å, b=14.377(1) Å, c=7.708(1) Å, β=99.54(1)°, V=818.9(2) Å³, R₁=0.0304, and wR₂=0.0669 for 1487 observed reflections (I⩾2σ(I)) out of 1877 unique reflections; (2) monoclinic, P2₁/c, Z=2, a=6.618(1) Å, b=8.172(2) Å, c=15.578(3) Å, β=96.30(3)°, V=837.4(3) Å³, R₁=0.0360 and wR₂=0.0663 for 1442 observed reflections (I⩾2σ(I)) out of 1927 unique reflections.     

Synthes and crystal structure of chiral amin alcohol-nickel complexes

Two novel chiral amino alcohol-nickel complexes (I) and (II) have been first reported from the direct reaction of L-plenylglycinol with Ni(OAc)₂ · 4H₂O in anhydrous ethanol and L-phenylalaninol with NiCl₂ · 6H₂O in anhydrous methanol. The crystal structures of I and II were determined by X-ray diffraction and further characterized by elemental analysis and IR. For I: C₂₄H₃₁N₃NiO₃, monoclinic, P2₁, a = 5.2581(12), b = 23.683(5), c = 13.744(3) Å, β = 97.939(6)°, V = 1695.1(7) ų, Z = 2, ρ_calcd = 0.917 g/cm³, the final R factor was R ₁ = 0.0897, 5315 for reflections were observed with I ₀ > 2σ(I ₀); for II: C₂₇H₄₃Cl₂N₃NiO₅, orthorhombic, P2₁2₁2₁, a = 9.844(3), b = 12.373(3), c = 26.158(7) Å, V = 3186.3(14) ų, Z = 4, ρ_calcd = 1.291 g/cm³, the final R factor was R ₁ = 0.0371, 6265 for reflections were observed with I > 2σ(I).     

Crystal structures of new isostructural oxovanadium(V) complexes with hydrazone ligands

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L¹)(OMe)]₂ (1) and [VO(L²)(OMe)]₂ (2), where L¹ and L² are the deprotonated forms of 3-bromo-N′-[1-(2-hydroxyphenyl)×ethylidene]benzohydrazide (H₂L¹) and 3-chloro-N′-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L²) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3)°, γ = 77.869(3)°, V = 849.9(4) ų, Z = 1, R ₁ = 0.0634, wR ₂ = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2)°, β = 71.783(2)°, γ = 79.822(2)°, V = 835.0(4) ų, Z = 1, R ₁ = 0.0511, wR ₂ = 0.1076. Each V atom in the complexes is octahedrally coordinated.     

Metal thiolate compounds: Processable ceramic precursors

Full crystallographic characterization has been obtained for [Hg(SBz)₂]_∞ (9), ClHgSBz · TMEDA (10), [ClHgS-i-Pr]_∞ (11), [ClHg(S-neo-Pent)·0.5Py]_∞ (12), In[S-2,4,6-(i-Pr)₃C₆H₂]₃·2MeCN (13), [In(S-2-MeO,5-Me, C₆H₃)₃]₂ (14) and In(S-o-C₆H₄CH₂N(CH₃)₂)₃ (15). Relevent metal thiolate interactions, terminal and bridging, are highlighted within the realm of thermolytic conversion of these species into binary metal thiolates. Pertinent crystallographic data for these compounds include:9: C2/c,a=22.599(4)Å,b=4.334(1)Å,c=29.596(5)Å,β=106.76(1)°,V=2775.6ų,Z=8,R=3.6%;10: P $\bar 1$ ,a=8.136(2)Å,b=9.958(7)Å,c=11.834(3)Å,α=108.71(2)°,β=92.93(2)°,γ=109.05(2)°,V=845.3ų,Z=2,R=5.0%;11: C2,a=21.430(7)Å,b=4.678(2)Å,c=6.724(2)Å,β=90.43°,V=674.0ų,Z=2,R=3.9%;12: C2,a=16.732(2)Å,b=11.200(1)Å,c=11.929(2)Å,β=104.21(1)°,V=2167.1ų,Z=4,R=3.5%;13: P $\bar 1$ ,a=13.680(8)Å,b=13.815(6)Å,c=15.155(9)Å,α=77.77(4)°,β=72.57(4)°,γ=88.18(4)°,V=2669.1ų,Z=8,R=12.0%;14: C2,a=8.323(2)Å,b=24.970(4)Å,c=12.466(2)Å,β=104.32(2)°,V=2510.1ų,Z=4,R=8.2%;15: P2₁/c,a=17.587(5)Å,b=11.786(2)Å,c=13.865(2)Å,β=101.66(2)°,V=2814.6ų,Z=4,R=3.2%. The molecules-to-materials transition, from a relatively simple divalent system, to the more mechanistically complex trivalent metal system is outlined.