Molecular Structures of RN(H)Py (R?=?2,4,6-Me3C6H2, 2,6-Et2C6H3, Ph3C), and the Copper Complex [Cu{(2,4,6-Me3C6H2)N(H)Py}2]BF4

Abstract  The molecular structures of RN(H)Py [R = 2,4,6-Me₃C₆H₂ (1), 2,6-Et₂C₆H₃ (2), -CPh₃ (3)] have been determined along with the copper(I) complex [Cu{(2,4,6-Me₃C₆H₂)N(H)Py}₂]BF₄ (4). Each of the amines exists as a hydrogen-bonded head-to-tail dimer. Compound 3 has four independent molecules in the asymmetric unit as a consequence of changes in the relative orientation of the pyridyl and phenyl rings. The copper in 4 is two-coordinate with the conformation of the aryl rings being dominated by inter-cation packing. Crystal data: 1 space group P2₁/c, a = 14.047(3), b = 7.154(1), c = 13.890(3) ?, β = 116.45(3)°; V = 1,249.7(4) ?³, Z = 4, R = 0.0547, wR ₂ = 0.1397; 2 space group P2₁/n, a = 13.035(3), b = 8.120(1), c = 13.562(3) ?, β = 111.87(3)°; V = 1,345.2(5) ?³, Z = 4, R = 0.0669, wR ₂ = 0.1512; 3 space group P2₁/c, a = 26.729(5), b = 17.008(3), c = 18.903(4) ?, β = 92.42(3)°; V = 8,586(3) ?³, Z = 8, R = 0.0911, wR ₂ = 0.163; 4 space group P2₁/c, a = 9.149(1), b = 15.901(3), c = 19.703(4) ?, β = 102.89(3)°; V = 2,794(1) ?³, Z = 4, R = 0.0504, wR ₂ = 0.1291. Graphical Abstract  The hydrogen-bonded head-to-tail dimer structures of RN(H)Py [R = 2,4,6-Me₃C₆H₂, 2,6-Et₂C₆H₃, -CPh₃] have been determined along with the two-coordinate copper complex [Cu{(2,4,6-Me₃C₆H₂)N(H)Py}₂]BF₄      

Structural Studies of the Coupling Products Between (C6H5)CH=NR (R?=?C6H5, i-C3H7) and the Ti(C5H5)(2,4-C7H11) Fragment (C7H11?=?dimethylpentadienyl)

Abstract  

The reactions of imines of the formula (C₆H₅)CH=NR (R = C₆H₅, i-C₃H₇) with Ti(C₅H₅)(2,4-C₇H₁₁)(PMe₃) (C₇H₁₁ = dimethylpentadienyl) lead to expulsion of the PMe₃ and coupling between the imine’s carbon atom and a single terminus of the 2,4-C₇H₁₁ ligand, resulting in C₅H₅, “diene,” and π-amide coordination in the 16 electron products. Examination of the Ti–C and C–C bonding parameters for the “diene” ligands reveals that they may be more appropriately regarded as enediyl ligands, leading to a formal +4 oxidation state for titanium. Both complexes crystallize in the triclinic space group P[`1] P\overline{1} . For the R = C₆H₅ coupling product, a = 10.4590(2) ?, b = 11.6407(2) ?, c = 17.3729(3) ?, α = 74.7610(7)°, β = 79.8600(6)°, γ = 82.2895(11)°, V = 2000.28(6) ?³, D _calc = 1.293 g/cm³ at 150(1) K. For the R = i-C₃H₇ coupling product, a = 8.1039(2) ?, b = 9.4115(2) ?, c = 13.0116(4) ?, α = 88.9906(18)°, β = 73.2780(15)°, γ = 83.3088(16)°, V = 943.82(4) ?³, D _calc = 1.250 g/cm³ at 150(1) K.     

Investigations of 2-Thiazoline-2-thiol as a Ligand: Synthesis and X-ray Structures of [Mn2(CO)7(μ-NS2C3H4)2] and [Mn(CO)3(PPh3)(κ2-NS2C3H4)]

Abstract  Treatment of Mn₂(CO)₁₀ with 2-thiazoline-2-thiol in the presence of Me₃NO at room temperature afforded the dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) in 51 and 34% yields, respectively. Compound 1 was quantitatively converted into 2 when reacted with one equiv of Me₃NO. Reaction of 1 with triphenylphosphine at room temperature furnished the mononuclear complex [Mn(CO)₃(PPh₃)(κ ²-NS₂C₃H₄)] (3) in 66% yield. All three new complexes have been characterized by elemental analyzes and spectroscopic data together with single crystal X-ray diffraction studies for 1 and 3. Compound 1 crystallizes in the orthorhombic space group Pbca with a = 12.4147(2), b = 16.2416(3), c = 19.0841(4) ?, β = 90°, Z = 8 and V = 3848.01(12) ?³ and 3 crystallizes in the monoclinic space group P 2₁/n with a = 10.41730(10), b = 14.7710(2), c = 14.9209(2) ?, β = 91.1760(10)°, Z = 4 and V = 2295.45(5) ?³. Graphical Abstract  Two new dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) were formed when [Mn₂(CO)₁₀] was treated with 2-thiazoline-2-thiol in the presence of Me₃NO. Compound 2 reacts with PPh₃ to give the monomeric complex [Mn(CO)₃(PPh₃ )(κ ²-NS₂C₃H₄)]. The structures of 1 and 3 were established by crystallography. Shishir Ghosh, Faruque Ahmed, Rafique Al-Mamun, Daniel T. Haworth, Sergey V. Lindeman, Tasneem A. Siddiquee, Dennis W. Bennett, Shariff E. Kabir Investigations of 2-thiazoline-2-thiol as a ligand: Synthesis and X-ray structures of [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] and [Mn(CO)₃ (PPh3)(κ ²-NS₂C₃H₄)].      

Diphosphine ring expansion and π-bond reduction in the reaction between 1,2-bis(diphenylphosphino) cyclobutenedione (bpcbd) and Ru3(CO)10(MeCN)2: X-ray diffraction structures of Ru3(CO)10[2,3- bis(diphenylphosphino)succinic anhydride] and Ru2(CO)6(bma)

Replacement of the acetonitrile ligands in Ru₃(CO)₁₀(MeCN)₂ by the diphosphine ligand 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) initially gives the unstable bpcbd-bridged cluster Ru₃(CO)₁₀(bpcbd) (1), followed by its subsequent transformation to the triruthenium cluster Ru₃(CO)₁₀(bma) (2). The decomposition of cluster 2 serves to produce the ruthenium compounds Ru₃(CO)₁₀[2,3-bis(diphenylphosphino)succinic anhydride] (3) and Ru₂(CO)₆(bma) (4). Compounds 2–4 provide the experimental evidence for the ring expansion of the cyclobutenedione ring via the formal insertion of an oxygen atom into the four-membered ring and hydrogen addition to the bond upon exposure to the atmosphere and/or moisture. Both 3 and 4 have been isolated and characterized in solution by IR and ³1P NMR spectroscopies, and the molecular structure of each product has been verified by X-ray crystallography. Ru₃(CO)₁₀[2,3-bis(diphenylphosphino)succinic anhydride] crystallizes, as the CH₂Cl₂ solvate, in the monoclinic space group P2₁/c, a = 12.178(2)Å, b = 15.988(2)Å, c = 22.472(3)Å, = 95.115(2)°, V = 4358(1)ų, Z = 4, and d_calc = 1.732 Mg/m³; R = 0.0344, R_w = 0.0931 for 5683 reflections with I > 2(I). The dinuclear compound Ru₂(CO)₆(bma) crystallizes in the triclinic space group P-1, a = 9.298(3)Å, b = 12.020(3)Å, c = 30.858(8)Å, = 81.774(5)°, = 89.276(5)°, = 83.545(4)°, V = 3391(1)ų, Z = 4, and d_calc = 1.730 Mg/m³; R = 0.0670, R_w = 0.1444 for 8766 reflections with I > 2a(I).     

Spectroscopic and X-ray Diffraction Data on Three Novel Trimetallic Clusters from Thermally Promoted Ligand Substitution in the Tetrahedrane Clusters MeCCo2MoCp(CO)8 and PhCCo2Mo(η5-C5H4CHO)(CO)8

Abstract  

The reaction between the ethylidyne-substituted cluster MeCCo₂MoCp(CO)₈ (1) and the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in refluxing CH₂Cl₂ has been investigated and found to afford the new mixed-metal clusters MeCCo₂MoCp(CO)₆[trans-2,3-bis(diphenylphosphino)succinic anhydride] (2) and Co₂MoCp(CO)₅[μ-C(Me)C=C(PPh₂)C(O)OC(O)](μ-PPh₂) (3), with the latter cluster representing the principal reaction product. Refluxing 1 with bma in either 1,2-dichloroethane or toluene yields only 3. The tetrahedrane cluster PhCCo₂Mo(η⁵-C₅H₄CHO)(CO)₈ (4), which contains a formyl-substituted cyclopentadienyl ring, has also been examined with added bma in refluxing CH₂Cl₂ and found to give only Co₂Mo(η⁵-C₅H₄CHO)(CO)₅[μ-C(Ph)C=C(PPh₂)C(O)OC(O)](μ-PPh₂) (5). All three products have been isolated and characterized spectroscopically in solution, and each molecular structure has been determined by X-ray crystallography. Cluster 2 contains a bridging diphosphine ligand with a succinic anhydride ring that results from the formal reduction of the maleic anhydride platform of the bma ligand, while clusters 3 and 5 each exhibit triangular Co₂Mo cores, whose one face is capped by a 6e- C(R)C=C(PPh₂)C(O)OC(O) [where R = Me (3), Ph (5)] ligand. The observed substitution products are discussed as a function of the capping carbyne group, ancillary polyene ligand, and related derivatives prepared by our groups.     

Syntheses, Spectroscopic Data, and X-ray Diffraction Structures of the Heterometallic RuRe Face-shared Bioctahedral (η6-cymene)Ru(μ-Cl)3Re(CO)3 and MnRu2 Edge-shared Trioctahedral [fac-ClRu(CO)3]2(μ-Cl)4Mn(H2O)2 Complexes

Abstract  Thermolysis of the diruthenium compound [(η⁶-cymene)RuCl₂]₂ (1) with ClRe(CO)₅ (2) leads to the formation of the new confacial bioctahedral compound (η⁶-cymene)Ru(μ-Cl)₃Re(CO)₃ (3) in good yields; the same product has also been isolated when a mixture of 1 and 2 is irradiated with near UV–vis light for an extended period of time. Heating 1 and ClMn(CO)₅ (4) does not furnish the corresponding manganese analogue of 3 but rather the trioctahedral halide-bridged product [fac-ClRu(CO)₃]₂(μ-Cl)₄Mn(H₂O)₂ (5). 3 and 5 have been fully characterized in solution and their molecular structures established by X-ray crystallography. Graphical Abstract  Thermolysis of [(η⁶-cymene)RuCl₂]₂ (1) with the respective pentacarbonyl ClM(CO)₅ [where M = Re (2); Mn(4)] affords the halide-bridged compounds (η⁶-cymene)Ru(μ-Cl)₃Re(CO)₃ (3) and [fac-ClRu(CO)₃]₂(μ-Cl)₄Mn(H₂O)₂ (5). 3 and 5 have been isolated and characterized spectroscopically in solution and their molecular structures established by X-ray crystallography.      

Structures and Characterization of [Zn(n-chlorosalicylato)2(N-methylnicotinamide)2(H2O)2] (n?=?4 or 5) Ligand Isomers

Abstract  

Two ligand isomers [Zn{4-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (I) and [Zn{5-ClC₆H₃-2-(OH)COO}₂(Menia)₂(H₂O)₂] (II) (Menia = N-methylnicotinamide) were prepared and characterized by elemental analysis, IR spectroscopy and thermal analysis. The X-ray crystal structures of complexes (I) and (II) were determined. Compound (I) crystallizes in the triclinic space group P[`1] P\bar{1} with a = 8.105(1) ?, b = 10.036(2) ?, c = 10.545(2) ?, α = 109.088(9)°, β = 91.416(8)°, γ = 102.757(9)°, V = 786.2(2) ?<sup>3</sup>, Z = 1. Compound (II) crystallizes in the triclinic space group P[`1] P\bar{1} . Its cell parameters are: a = 8.133(1) ?, b = 10.119(2) ?, c = 10.428(1) ?, α = 66.44(1)°, β = 74.32(1)°, γ = 80.16(1)°, V = 755.5(2) ?³, Z = 1. The molecular structure of both isomers is monomeric. Each Zn(II) atom is hexacoordinated by three pairs of unidentate ligands in trans-positions (ZnO₄N₂). The 5-Clsal complex is somewhat less distorted than 4-Clsal complex (Cl-sal = chlorosalicylate). The structural data are compared with those found in similar [Zn(RCOO)₂(NL)₂(H₂O)₂].     

Synthesis and Crystal Structure of MnII(OAc)2[15-MC MnIII(N)shi-5](Im)3(EtOH)3 (shi3??=?salicylhydroximate, ?OAc?=?acetate, Im?=?imidazole, and EtOH?=?ethanol)

Abstract  

The metallacrown complex Mn^II(OAc)₂[15-MC_Mn^III _(N)shi-5](Im)₃(EtOH)₃ has been synthesized and characterized by single-crystal X-ray diffraction and infrared spectroscopy. The compound crystallizes in the monoclinic space group P2₁/c with a = 24.3326(15) ?, b = 24.0354(15) ?, c = 27.0531(17) ?, α = 90.00°, β = 100.3883(11)°, γ = 90.00°, V = 15562.5(17) ?³, Z = 4, and Z′ = 2. Four of the five manganese(III) ions of the metallacrown ring adopt a distorted octahedral coordination geometry, and the fifth manganese(III) ion is five coordinate and exhibits a distorted square pyramidal environment. The configuration of the manganese(III) ions about the ring follows a pattern of ΔΛΔPP, with P representing planar. In addition, the imidazole units are bound to three separate ring manganese(III) ions, and the imidazole units are directed to the outside of the molecule. A manganese(II) ion is encapsulated in the central core of the molecule, and the central ion is seven coordinate with a face-capped trigonal prismatic geometry.     

Crystal Structure and Magnetic Properties of the Dinuclear MnII Compound [Mn2(bpy)4(2-ClC6H4COO)2](ClO4)2·2EtOH

Abstract  

The synthesis and crystal structure of the dinuclear manganese (II) compound [Mn₂(bpy)₄(2-ClC₆H₄COO)₂](ClO₄)₂·2EtOH is described. The complex crystallizes in the monoclinic system, space group P2₁/n with a = 12.2067(18), b = 17.335(3), c = 13.706(3) ? and β = 92.606(8)°. In this structure, two manganese ions are bridged by two 2-chlorobenzoate ligands in a syn–anti mode. The hexa-coordination of each manganese is completed by two 2,2′-bipyridine ligands. Two perchlorate anions and two molecules of ethanol complete the packing. In order to check the magnetic properties previously reported from a powder sample, new magnetic studies have been carried out from a crystal sample, obtaining J = −1.79 cm⁻¹ and g = 2.00 (H = −JS ₁ ·S ₂ ).     

Reactivity of [Re2(CO)8(MeCN)2] With 1-vinylimidazole: X-ray Structures of [Re2(CO)8{η1-NC3H3N(CH=CH2)}2] and [ReCl2(CO)2{η1-NC3H3N(CH=CH2)}2]

Abstract  Treatment of [Re₂(CO)₈(MeCN)₂] with excess 1-vinylimidazole in refluxing benzene gives three new compounds [Re₂(CO)₉{η ¹-NC₃H₃N(CH=CH₂)}] (1), [Re₂(CO)₈{η ¹-NC₃H₃N(CH=CH₂)}₂] (2) and [ReCl₂(CO)₂{η ¹-NC₃H₃N(CH=CH₂)}₂] (3) in 11, 32 and 2% yields, respectively. The solid-state structures of complexes 2 and 3 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the monoclinic space group C2/c, with lattice parameters a = 13.8378(5) ?, b = 11.8909(5) ?, c = 14.4591(6) ?, β = 116.6470(10)°, Z = 4 and V = 2131.99(15) ?³. Compound 3 crystallizes in the monoclinic space group C2/c, with lattice parameters a = 10.1028(3) ?, b = 13.5640(5) ?, c = 12.5398(4) ?, β = 109.637(2)°, Z = 4 and V = 1618.4(9) ?³. The disubstituted dinuclear compound 2 contains two 1-vinylimidazole ligands coordinated through the imino nitrogen atoms at the equatorial sites, whereas the mononuclear compound 3 contains two carbonyl ligands, two N coordinated η ¹-1-vinylimidazole ligands and two terminal Cl ligands. Graphical Abstract  Two dinuclear complesxes [Re₂(CO)₉{η ¹-NC₃H₃N(CH=CH₂)}] (1) and [Re₂(CO)₈{η ¹-NC₃H₃N(CH=CH₂)}₂] (2) and the mononuclear [ReCl₂(CO)₂{η ¹-NC₃H₃N(CH=CH₂)}₂] (3) were obtained from the reaction of [Re₂(CO)₈(MeCN)₂] with excess 1-vinylimidazole at 80 °C. The X-ray structrures of 2 and 3 are described.      

Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI?=?2,4-Dinitroimidazolate)

Abstract  

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)₂(H₂O)₃][Ni(DNI)₂(H₂O)₄]}·6H₂O, 1, and Pb(DNI)₂(H₂O)₄, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) ?, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) ?, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon.     

Synthesis and X-ray structural investigation of (C3N6H7)4(CN3H6)2[UO2(CrO4)4] · 4H2O and (H3O)6[UO2(CrO4)4]

Single crystals of the compounds (C₃N₆ H₇)₄(CN₃H₆)₂[UO₂(CrO₄)₄] · 4H₂O (I) and (H₃O)₆[UO₂(CrO₄)₄] (II) are synthesized, and their structures are investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 6.3951(8) ?, b = 10.8187(16) ?, c = 16.9709(18) ?, α = 93.674(4)°, β = 97.127(4)°, γ = 92.020(4)°, space group, P Z = 1, V = 1161.6(3) ?³, and R = 0.0470. Crystals of compound II belong to the monoclinic system with the unit cell parameters a = 14.3158(4) ?, b = 11.7477(3) ?, c = 13.1351(4) ?, β= 105.836(1)°, space group C2/c, Z = 4, V = 2125.2(1) ?³, and R = 0.0213. The uranium-containing structural units of crystals I and II are mononuclear anionic complexes of the composition [UO₂(CrO₄)₄]⁶⁻ with an island structure, which belong to the crystal-chemical group Am ₁⁴ (A = UO₂₊², M ¹ = CrO₂₋⁴) of the uranyl complexes. The [UO₂(CrO₄)₄]⁶⁻ anionic complexes are joined into a three-dimensional framework through the electrostatic interactions with outer-sphere cations and a system of hydrogen bonds. Original Russian Text ? L.B. Serezhkina, E.V. Peresypkina, A.V. Virovets, A.G. Verevkin, D.V. Pushkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 284–290.     

On the Two Closely Related Phases of [Ru(C5Me5)(η6-1,3-(Me2NCH2)2C6H4)](BF4) and the Reversible Solid–Solid Order–Disorder Phase Transition

Abstract  

Crystals of the complex [Ru(C₅Me₅)(η⁶-1,3-(Me₂NCH₂)₂C₆H₄)](BF₄) have been examined over the temperature range 150–300 K via X-ray diffraction measurements. This study shows that the Ru complex is a two-phase system in this T-range and the solid–solid transition is reversible. At 150 K, phase II (P2₁/c, Z′ = 4) is ordered and non-merohedrally twinned, a = 16.4396 (9) ?, b = 17.3226 (4) ?, c = 32.1874 (11) ?, β = 91.375 (2)°. At 295 K, phase I (Pbca, Z′ = 1) is disordered, a = 8.5071 (3) ?, b = 17.1567 (3) ?, c = 32.8250 (8) ?. The relationship between the two phases is obvious because the packing remains similar in the two phases. The greatest structural changes between the two phases are found in the rows of adjacent cations [Ru(C₅Me₅)(η⁶-1,3-(Me₂NCH₂)₂C₆H₄)]⁺ packed along the a direction. These rows are ordered in phase II but are disordered in phase I. The phase transition is first order. Significant changes in thermal motion for the cations are considered as being the driving force for the occurrence of this phase transition.     

Synthesis and Structure of a Silver(I) Complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n [L?=?2,3-bis(pyrimidine-2-thiomethyl)quinoxaline]

Abstract  The reaction of the dithioether ligand, 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline (L) with AgNO₃, leads to the formation of a novel complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}n 1, which has been characterized by single-crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 34.741(7), b = 9.930(2), c = 17.004(4) ?, β = 106.497(6)° and V = 5625(2) ?³.Complex 1 consists of 2D {[Ag₅(L)₂(NO₃)₄]⁺}n cations, uncoordinated anions and CHCl₃ solvent molecules. In 1, there exist three crystallographic independent Ag^I centers, which adopt different coordination geometries. There exist π–π stacking interactions in the complex and these weak interactions further stabilize the crystal structure in the solid state. The coordination feature of the ligand has been investigated by DFT calculations. Index Abstract  Synthesis and Structure of a Silver(I) Complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}_n [L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline] Chao-Yan Zhang, Qian Gao, Ya-Bo Xie*, and Jian-Bo Feng The crystal structure of complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}n (L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline) consists of 2D {[Ag₅(L)₂(NO₃)₄]⁺}n cations, uncoordinated anions and CHCl₃ solvent molecules. There exist three crystallographic independent Ag^I centers, which adopt different coordination geometries. The coordination feature of the ligand has been investigated by DFT calculations.      

Structural Studies of Coupling Products Formed Between (C6H5)CH=N(C6H5) and the M(C5H5)(6,6-dmch) Fragments (M?=?Ti, Zr; dmch?=?dimethylcyclohexadienyl)

Abstract  

The reactions of Ti(C₅H₅)(6,6-dmch)(PMe₃) and Zr(C₅H₅)(6,6-dmch)(PMe₃)₂ with two equivalents of C₆H₅C(H)=N(C₆H₅) have led to couplings of the imines to the 1,5 (terminal) positions of the 6,6-dmch ligands. In both cases the PMe₃ ligands are lost, and the metal complexes each attain 18 electron configurations via η⁵-(C₅H₅), η³-allyl, and bis(π-amide) coordination. The complexes each crystallize in the monoclinic space group P2₁/c. For the titanium complex, a = 10.4336(1) ?, b = 9.0407(1) ?, c = 32.5547(6) ?, β = 94.2939(5)°, V = 3062.17(7) ?³, D_calc = 1.264 at 200(1) K. For the zirconium complex, a = 13.8900(3) ?, b = 10.0873(2) ?, c = 22.4543(6) ?, β = 90.7638(7)°, V = 3145.85(12) ?³, D_calc = 1.322 at 150(1) K.     

Synthesis, Crystal Structure and Fluorescence Property of a Binuclear Zn(II) Complex: [Zn2(μ-N3)2(N3)2(L)2] [L?=?1-(1,10-phenanthrolin-2-yl)-2-pyridone]

Abstract  Hydrated zinc perchlorate reacted with sodium azide and 1-(1,10-phenanthrolin-2-yl)-2-pyridone (L) in methanol solution and resulted in the formation of a new binuclear complex: [Zn₂(μ-N₃)₂(N₃)₂(L)₂]. The complex has been characterized by elemental analysis and IR spectrum, and its crystal structure determined by X-ray crystallography and the complex crystallizes in the monoclinic system with space group P2₁/c and a = 11.409(2), b = 8.0733(15), c = 18.163(3) Ǻ, β = 99.095(3)°. In the complex two azide anions act as bridge ligand and another two azide anion and two 1-(1,10-phenanthrolin-2-yl)-2-pyridone function as terminal ligands, and Zn(II) ion lies in a distorted triangle bipyramid geometry. Index Abstract  The title binuclear Zn(II) complex was synthesized by zinc perchlorate, sodium azide and 1-(1,10-phenanthrolin-2-yl)-2-pyridone and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that azide anion function as both bridge ligand and terminal ligand, and 1-(1,10-phenanthrolin-2-yl)-2-pyridone only acts as a terminal ligand.      

Synthesis and Structure of a Novel Polyoxomolybdate Lanthanide Complex: [Er2(H2O)14Cr(OH)6Mo6O18][Cr(OH)6Mo6O18]?·?14H2O

Abstract  A novel polyoxometalate compound consisting of Anderson-type anions and trivalent lanthanide cations, [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈][Cr(OH)₆Mo₆O₁₈]·14H₂O (1), has been synthesized in aqueous solution and characterized by single crystal X-ray diffraction, elemental analyses, IR spectrum and TG analyses. Single crystal X-ray diffraction reveals that compound 1 crystallizes in the triclinic space group P-1 with a = 11.046 (5) ?, b = 11.653 (5) ?, c = 13.935 (5) ?, α = 75.006 (5)°, β = 84.497(5)°, γ = 89.515(5)°. The bulk ions of compound 1 in the cell unit exhibit orthorhombic C-centered packing mode, the eight [Cr(2)(OH)₆Mo₆O₁₈]³⁻ anions occupy the eight corners and the two [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈]³⁺ cations occupy the centres of two opposite faces, whereas anions and cations are linked together via hydrogen bonding interactions tightly forming a three-dimensional supramolecular architecture, which contains one-dimensional channels occupied by free water molecules. Index Abstract  The bulk ions of compound 1 in the cell unit exhibit orthorhombic C-centered packing mode, the eight [Cr(2)(OH)₆Mo₆O₁₈]³⁻ anions occupy the eight corners and the two [Er₂(H₂O)₁₄Cr(OH)₆Mo₆O₁₈]³⁺ cations occupy the centres of two opposite faces, whereas anions and cations are linked together via hydrogen bonding interactions tightly forming a three-dimensional supramolecular architecture, which contains one-dimensional channels occupied by free water molecules. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A Novel Keggin-Type Aluminotungstate Dimeric Compound: H3.5[Ni(2,2′-bipy)3]3{[AlW 10VI W 2V O40Ni(2,2′-bipy)2(H2O)]2Na0.5}

Abstract  A novel dimeric compound H_3.5[Ni(2,2′-bipy)₃]₃{[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5} prepared by the hydrothermal method consists of a {[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5}^9.5− heteropolyanion, and in the anion, two reduced Keggin heteropolyanions [AlW^VI ₁₀W₂^VO₄₀]⁷⁻ are bridged via Na coordination ion by means of an O–Na1–O linkage (O atoms from the surface bridging oxygen atoms of [AlW^VI ₁₀W₂^VO₄₀]⁷⁻) and two Ni coordination ions are linked to the Na1 square planar moiety by making use of Ni–Ow–Na1–Ow–Ni bridges. The crystal belongs to the monoclinic-space group C2/c, a = 46.592(9), b = 14.306(3), c = 25.967(5) ?, β = 90.14(3)°, V = 17308(6) ?³, Z = 4, D _c  = 3.116 Mg/m³. Index Abstract  A novel dimeric compound H_3.5[Ni(2,2′-bipy)₃]₃{[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5} prepared by the hydrothermal method consists of a {[AlW₁₂O₄₀Ni(2,2′-bipy)₂(H₂O)]₂Na_0.5}^9.5− heteropolyanion, and in the anion, two reduced Keggin heterpolyanions [AlW^VI ₁₀W^V ₂O₄₀]⁷⁻ are bridged via Na coordination ion by means of an O–Na1–O linkage (O atoms from the surface bridging oxygen atoms of [AlW^VI ₁₀W^V ₂O₄₀]⁷⁻) and two Ni coordination ions are linked to the Na1 square planar moiety by making use of Ni7–Ow7–Na17–Ow7–Ni bridges.      

Crystal Structures of the 1,2-Dihydroquinazolinium-4-yl Pd(II) Complexes [PdI{C=N(Xy)CH(R)NHC6H4-2}(CNXy)2]OTf (R?=?Me, CH?=?CH2, C6H4Me-4) and of the 2-Iminoaryl Pd(II) Complex [PdI(C6H4{N=C(H)C6H4Me-4}-2)(2,2′-bipyridine)]

Abstract  

The crystal structures of trans-[PdI{C=N(Xy)CH(R)NHC₆H₄-2}(CNXy)₂]OTf (R = Me (1·CHCl₃) space group P-1, a = 8.7665(4) ?, b = 15.5346(8) ?, c = 16.2415(8) ?, α = 72.698(2)o, β = 78.310(3)o, γ = 88.310(2)o, CH = CH₂ (2·0.5Et₂O) space group P2₁/c, a = 15.7868(6) ?, b = 14.5066(6) ?, c = 18.5814(7) ?, β = 106.707(2)o, C₆H₄Me-4 (Tol) (3) space group P-1, a = 11.96075(5) ?, b = 12.9452(51) ?, c = 13.1263(5) ?, α = 93.306o, β = 95.822(2)o, γ = 94.572(2)o) have been measured. The structural data suggest the existence of some electron delocalization over the heterocyclic ring, the extension of which seems to depend on the R substituent. The complex [PdI{C₆H₄(N=CHTol)-2}(bpy)] (Tol = C₆H₄Me-4, bpy = 2,2′-bipyridine, 4) is the fourth imino-substituted aryl palladium complex. Complex 4 crystallizes in triclinic P-1 with a = 8.7873(5) ?, b = 8.8936(5) ?, c = 13.8375(8) ?, α = 90.116(2)o, β = 92.760(2)o, γ = 106.243(2)o.     

Polyene ring attack in diag-CpRe(CO)2Br2 by hydride and cyclopentadiene displacement to furnish trans(Br)-[Re(CO)4Br2]? under CO: X-ray diffraction structure of trans(Br)-[Re(CO)4Br2][PPh4]

The reducing agent [Et₃BH][Li] reacts with diag-CpRe(CO)₂Br₂ in THF at –78C by polyene ring attack to give the anionic rhenium(I) compound [(⁴-C₅H₆)Re(CO)₂Br₂]^–. Monitoring the reaction by low-temperature IR spectroscopy has revealed that the reaction between diag-CpRe(CO)₂Br₂ and hydride is instantaneous and that the known compounds CpRe(CO)₂Br^– and CpRe(CO)₂Br(H) are not formed as the principal reduction products. The reduced compound [(⁴-C₅H₆)Re(CO)₂Br₂]^– is extremely temperature sensitive and decomposes upon warming to afford low yields of CpRe(CO)₃. We have explored the reactivity of the hydride reduction product with added CO and have isolated and structurally characterized the anionic tetracarbonyl compound trans(Br)-[Re(CO)₄Br₂]^– as the tetraphenylphosphonium salt. trans(Br)-[Re(CO)₄Br₂][PPh₄] crystallizes in the monoclinic space group C2/c, a = 16.908(2) Å, b = 7.1579(7) Å, c = 23.543(2) Å, = 96.144(9), V = 2832.9(5) ų, Z = 4, D_cacl = 1.870 g/cm³; R = 0.0419, R_w = 0.0450 for 1629 observed reflections with I > 3(I). The reaction between the product of hydride reduction and dppe is shown by IR and ³¹P NMR spectroscopies to produce mer-cis-BrRe(CO)₂(²-dppe)(¹-dppe).