Synthesis and X-ray structure of [(μ-H)Os3(CO)10(μ-η2-N=CCH=CHCH=CC2H5)]

The reaction of [Os₃(CO)₁₀(MeCN)₂] with 2-ethylpyridine at ambient temperature leads to the isolation of the cluster [(-H)Os₃(CO)₁₀(-²-N=CCH=CHCH=CC₂H₅)][3 (65% yield) which has been structurally characterized by crystallographic methods. The compound crystallizes in the triclinic space group with a = 9.334(2), b = 9.918(2), c = 11.767(1) Å, = 92.13(2), = 99.93(1), = 99.88(2)°, V = 1054.7(3) ų and Z = 2. The same edge of the osmium triangle in the cluster is bridged by both the hydrido and the heterocyclic ligands, the latter through the nitrogen and the carbon atoms of the C=N bond.     

Comparison of the X-ray crystal structures of four closely related Mo(CO)5(R2PXR′) (R2 = OCH2CMe2CH2O, XR′ = S-2-Pr, NHC6H4-4-Me; R2 = Ph2, XR′ = NHC6H4-2-Me, OC6H4-4-SMe) complexes

The X-ray crystal structures of four closely related Mo(CO)₅(R₂PXR) (R₂ = OCH₂CMe₂CH₂O, XR = S-2-Pr, NHC₆H₄-4-Me; R₂ = Ph₂, XR = NHC₆H₄-2-Me, OC₆H₄-4-SMe) complexes have been determined. The R₂PXR ligands are oriented so that the P—X bond and one of the Mo—C bonds are nearly eclipsed. This results in the distortion of the octahedral coordination geometry via tilting of the Mo(CO)₅ group away from the XR group. As observed in related complexes, the Mo—C bond of the carbonyl trans to the phosphorus-donor group is shorter than are the Mo—C bonds of the carbonyls trans to carbonyls. In contrast, no significant differences were observed between the Mo—C bonds of carbonyls trans to phosphites and the Mo—C bonds of carbonyls trans to phosphinites. The conformations of the 1,3,2-dioxaphosphorinanes were distorted chairs with the P end of the chair significantly flattened relative to the seat of the chair. This conformation is similar to that which has been observed for 1,3,2-dioxaphosphorinanes in other transition metal complexes.     

Synthesis and crystal structure of [Y(NO3)3(OH2)3]·(Me2-16-crown-5)·H2O

The complex [Y(NO₃)₃(OH₂)₃]·(Me₂-16-crown-5)·H₂O has been prepared and its crystal and molecular structure determined using single crystal X-ray diffraction. The colorless crystals belong to the monoclinic space group P2₁/n with Z = 4. Lattice parameters are a = 10.420(1), b = 17.257(3), c = 14.646(2) Å, = 96.79(1)°, V = 2615.1(6) ų. The yttrium(III) ion is nine-coordinate, bonded to three bidentate nitrate groups and three water molecules. The average Y–O(nitrate) and Y–O(water) distances are 2.42(3) and 2.33(1) Å, respectively. The average HO–H···O hydrogen bonded separation is 2.767Å.     

Reinvestigation of the reaction of [Ru3(CO)12] with 2-mercaptobenzothiazole: X-ray structure of [(μ-H)2Ru3 (μ-η2-C7H4NS2)(μ3-η2-C7H4NS2)(CO)7]

Treatment of Ru₃(CO)₁₂ with 2-mercaptobenzothiazole at 68°C gave the known compound [(-H)Ru₃(₃-²-C₇H₄NS₂)(CO)₉] 1 and the new compound [(-H)₂Ru₃(-²-C ₇H₄NS₂) (₃-²-C₇H₄NS₂)(CO)₇] 2 in 15 and 10% yields respectively. Compound 2 has been characterized by elemental analysis, infrared, ¹H NMR and mass spectroscopic data together with single crystal X-ray crystallography. It crystallizes in the monoclinic space group C2/c with a = 31.662(6), b = 14.577(3), c = 11.602(2) Å, = 104.15(3)°, Z = 8, and V = 5192.4(2) ų. The compound consists of a Ru₃ triangle with three different Ru-Ru bond lengths [2.75264, 2.79084, 2.97604 Å] and the two 2-mercaptobenzothiazole ligands are differently attached to the metal atoms. Compound 2 is also obtained by the reaction of 1 with excess 2-mercaptobenzothiazole at 68°C.     

The properties,crystal, and molecular structure of catena-[(μ-acetato-) (μ-phthalazine)silver(I)dihydrate]: {[Ag(μ-O2CCH3) (μ-PHZ) (H2O)2]2}n

The crystal and molecular structure of catena-[(-acetato) (-phthalazine)-silver(I)dihydrate], {[Ag(O₂CCH₃) (C₈H₆N₂)(H₂O)₂]₂}_n, has been determined by single crystal X-ray analysis: the space group is P2₁/n,a=16.150(8) Å,b=3.886(5) Å,c=18.716(9) Å, =96.02(5)°,V=1168 ų. Phthalazine (PHZ) bridges the silver atoms to form {Ag--PHZ]₂ dimeric subunits. These dimeric subunits are planar and stack by bridging acetates to form a polymeric lattice. The acetates also form an asymrnetric chelate ring with the silver atoms which result in a distorted, square pyramidal configuration. The complex is further characterized by its IR and thermal properties.     

Synthesis and X-ray structure of [(μ-H)Ru3(CO)8(μ-Cl)(μ-dppm)] [dppm = bis(diphenylphosphino)methane]

The reaction of [Ru₃(CO)₁₀(-dppm)] 1 with PPhCl₂ in refluxing CHCl₃ results in the isolation of [(-H)Ru₃(CO)₈(-Cl)(-dppm)] 3 in 10% yield. Compound 3, which has been structurally characterized by crystallographic methods, is also formed from the reaction of 1 with H₂ in refluxing CCl₄. The compound crystallizes in the monoclinic space group P2₁/c with a = 16.814(2), b = 18.7590(12), c = 11.486(2) Å, = 97.745(11)°, V = 3589.8(8) ų, and Z = 4. The hydride and chloride ligands bridge the same edge of the triruthenium cluster as the dppm ligand.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

Synthesis and crystal structure of (CN3H6)2[UO2(OH)2(NCS)]NO3 and β-Cs3[UO2(NCS)5]

Compounds (CN₃H₆)₂[UO₂(OH)₂(NCS)]NO₃ (I) and β-Cs₃[UO₂(NCS)₅] (II) are synthesized and studied by IR spectroscopy and single-crystal X-ray diffraction. I and II crystallize in the orthorhombic system. For I, a = 12.2015(13) Å, b = 7.3295(8) Å, c = 16.310(2) Å, space group Pnma, Z = 4, and R = 0.0327; for II, a = 21.7891(6) Å, b = 13.5120(3) Å, c = 6.8522(2) Å, space group Pnma, Z = 4, and R = 0.0268. In structure I, complex groups form infinite chains [UO₂(OH)₂(NCS)] _n ^n? belonging to the AM ₂ ² M ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , M ² = OH^?, and M ¹ = NCS^?). The main structural elements of crystals II are mononuclear [UO₂(NCS)₅]^3? groups belonging to the AM ₅ ¹ group of uranyl complexes (A = UO ₂ ²⁺ and M ¹ = NCS^?). In I and II, uranium-containing complexes are connected with outer-sphere cations by electrostatic interactions, and in I a system of hydrogen bonds also contributes to their binding. Specific features of the packing of complex [UO₂(NCS)₅]^3? groups in the structures of two modifications of Cs₃[UO₂(NCS)₅] are discussed.     

Synthesis, spectroscopy, and X-ray structure of the polymer catena-[bis(azido-N)-copper(II)-μ-bis(2-benzimidazolyl)butane]

The title compound, catena-[bis(azido-N)-copper(II)-(bis(2-benzimidazolyl)butane), [Cu(C₁₈H₁₈N₄)(N₃)₂]_n, was obtained from the reaction of the ligand bis(2-benzimidazolyl)butane and Cu(N₃)₂. The x-ray crystal structure is reported. The compound crystallizes in the monoclinic space group P2₁/c with a = 8.2524(10), b = 12.765(5), c = 9.1125(15) Å, = 106.423(12)°, Z = 2. The Cu(II) ions are square-planar coordinated with trans-oriented end-on binding azido ligands. The structure is a polynuclear chain with the benzimidazole bridging at each end. In addition a N_(ligand)-H···N_(azido) H-bridge [N_(ligand)···N_(azido) = 2.994(7) Å] is present, resulting in a pseudo 2-dimensional lattice. The characteristic azido infrared vibrations are found at 2060 and 2077 cm^–1 (_as(N₃)) and 1284 and 1297 cm^–1 ((N₃)).     

Formation of a samarium alkoxide–aryloxide complex containing a novel butterfly framework: X-ray crystal structures of Sm4(μ3-O-i-Pr)3(μ2-O-i-Pr)4(O-i-Pr)2(O-2,6-i-Pr2C6H3)3(THF) and [Ti(O-i-Pr)2(O-2,6-i-Pr2C6H3) (μ-O-i-Pr)]2

Reaction of a 1:1 mixture of Sm[N(SiMe₃)₂]₃ and Ti(O-i-Pr)₄ with three equivalents of 2,6-di-iso-propylphenol, followed by crystallization from hexane/THF, leads to isolation of the tetranuclear samarium alkoxide Sm₄(₃-O-i-Pr)₃(₂-O-i-Pr)₄(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)₃(THF) (1), in addition to the dimeric titanium alkoxide [Ti(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)(-O-i-Pr)]₂ (2). 1 crystallizes in the space group while 2 crystallizes in space group P2₁/c. Cell parameters for 1: a = 15.928(6), b = 17.677(7), c = 18.99(1) Å, = 113.24(3), = 94.99(4), = 109.59(2)°, V = 4477(4) ų, D _calc = 1.350 Mg/m³, and Z = 2. Cell parameters for 2: a = 25.336(2), b = 12.082(1), c = 15.570(2) Å, = 96.510(8)°, V = 4735.4(8) ų, D _calc = 1.129 mg/m³, and Z = 4.     

Characterization of an asymmetric M(chelate)2(μ-Cl)2MCl2 dimer and isolation of corresponding DMSO adducts: X-ray crystal structures of Co(phen)2(μ-Cl)2CoCl2⋅C4H8O and M(chelate)Cl2(DMSO) x (Co, x = 1; Ni, x = 2) complexes

In aqueous solution, [M(chelate)Cl₂]x (chelate = 2,2-bipyridine, 1,10-phenanthroline) complexes can disproportionate to produce M(chelate)₂ ⁿ⁺ species that contain two chelating ligands. After extraction with organic solvent,Co(phen)₂(-Cl)₂CoCl₂(1) has been characterized by X-ray diffraction (monoclinic, C2/c, a = 10.278(2)Å, b = 22.026(5)Å, c = 12.941(3)Å, = 103.959(4)°, Z = 4, 2414 reflections [I 2 (I)], R ₁ = 0.0321, wR ₂ = 0.0864). However, addition of [M(chelate)Cl₂]x starting materials to dimethyl sulfoxide produces complexes that retain a single chelate ligand. The pentacoordinate complex Co(bpy)Cl₂DMSO (2) has been structurally characterized (triclinic, P , a = 7.824(2)Å, b = 9.570(4)Å, c = 10.025(2)Å, = 83.24(3)°, = 87.14(2)°, = 83.35(3)°, Z = 2, 2455 reflections [I 2 (I)], R ₁ = 0.0278, wR ₂ = 0.0747). In the case of nickel, two different geometric isomers are observed, depending on the chelate identity: trans-(DMSO)₂Ni(bpy)Cl₂ DMSO (3) (monoclinic, P21/c, a = 10.9149(8)Å, b = 12.1287(9)Å, c = 17.0044(13)Å, = 98.610(1)°, Z = 4,3519 reflections [I 2 (I)], R ₁ = 0.0209, wR ₂ = 0.0560) and cis-(DMSO)₂Ni(phen)Cl₂ (4) (monoclinic, P21/c, a = 8.404(2)Å, b = 14.051(4)Å, c = 16.710(4)Å, = 92.44(3)°, Z = 4, 3069 reflections [I 2 (I)], R ₁ = 0.0691, wR ₂ = 0.1782).     

Reactions of [Mn2(μ-pyS)2(CO)6] (pySH=pyridine-2-thiol) with triphenylphosphine (PPh3), diphenylphosphine (PHPh2) and bis(diphenylphosphino)methane (dppm): X-ray crystal structure of [Mn(pyS)(η1-dppm)2(CO)2]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 M equivalents of both PPh₃ and PHPh₂ to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)₃][L = PPh₃ (2) and PHPh₂ (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(¹-dppm)₂(CO)₂](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P2₁/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, = 99.870(8)°, V = 4988(2) ų, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.     

Molecular structures of [CpRu(PPh3)(dtoxa-H2O)]BF4 and {[CpRu(PPh3)2]2(μ-dtoxa)}(BF4)2, dtoxa=dithiooxamide

The reaction of [CpRu(PPh₃)₂(n-C₃H₇SH)]BF₄ with dithiooxamide (dtoxa) gave two products: {[CpRu(PPh₃)₂]₂(-dtoxa)} (BF₄)₂,1, and [CpRu(PPh₃)(dtoxa-H₂O)]BF₄,2. The structures of both complexes were determined by X-ray diffraction techniques. Compound1 crystallized in the triclinic space groupP _¯1,a=12.822(4),b=14.16(1),c=23.631(8) Å,=84.57(4),=83.64(3), =83.57(4)°,Z=2,R=0.069,R _w =0.084. The structure of1 shows two CpRu(PPh₃)₂ ⁺ units bridged through the S atoms of the dtoxa ligand. Ru-S distances are 2.377(6)Å for Ru1-S1 and 2.368(6) Å for Ru2-S2. Compound2 crystallized in the monoclinic space groupP2₁/c,a=13.446(3),b=13.461(7),c=31.214(7) Å,=100.78(3)°,Z=8,R=0.054,R _w =0.055. The structure of2 has two molecules in the asymmetric unit. The Ru is chelated to the dtoxa through the S atoms: Ru1-S1, 2.307(4); Ru1-S2, 2.300(4); Ru2-S3, 2.295(4); Ru2-S4, 2.287(4) Å. The coordination sphere of the Ru in2 is completed by a cyclopentadienyl ligand and a triphenylphosphine.     

Reaction of ethyl diazoacetate with Co3(CO)9(μ3-CCl): Isolation and X-ray structures of Co3(CO)9(μ3-CCO2Et), Co3(CO)9(μ3-CCH2CO2Et), and [Co3(CO)9(μ3-CCHCO2Et)]2

The reaction between the tricobalt cluster Co₃(CO)₉(₃-CCl) (1) and AlCl₃, followed by treatment with ethyl diazoacetate, N₂CHCO₂Et, affords a complex mixture of products in low yields. Column chromatography has allowed the isolation of the four cluster compounds Co₃(CO)₉(₃-CH) (2), Co₃(CO)₉(₃-CCO₂Et) (3), Co₃(CO)₉(₃-CCH₂CO₂Et) (4), and [Co₃(CO)₉(₃-CCHCO₂Et)]₂ (5). Clusters 4 and 5 are new and have been fully characterized in solution by IR and ¹H NMR spectroscopy. The molecular structures of clusters 3–5 have also been determined by single-crystal X-ray diffraction analysis. Co₃(CO)₉(₃-CCO₂Et) crystallizes in the triclinic space group P , a = 8.8393(5), b = 14.727(1), c = 15.272(1) Å, = 93.361(6), = 105.509(5)°, = 100.336(6)°, V = 1872.6(2) ų, Z = 4, and d _calc = 1.823 g/cm³. Co₃(CO)₉(₃-CCH₂CO₂Et) crystallizes in the monoclinic space group P2₁/n, a = 9.3806(7), b = 9.2617(8), c = 22.455(2) Å, = 94.483(7)°, V = 1944.9(3) ų, Z = 4, and d _calc = 1.803 g/cm³. [Co₃(CO)₉(₃-CCHCO₂Et)]₂ crystallizes in the monoclinic space group C2/c, a = 21.585(2), b = 8.7977(7), c = 20.784(1) Å, = 104.807(6)°, V = 3815.8(5) ų, Z = 4, and d _calc = 1.835 g/cm³. Plausible pathways leading to the formation of clusters 2, 4, and 5 are discussed.     

The crystal and molecular structure of trans-dimethyl 2α-methyl(3αH) perhydro [1,2]oxazolo-[2,3-a]azepine-2α,3α-dicarboxylate: A 7/5-fused ring system

The title compound crystallizes in the monoclinic space group P2₁/n, with a = 6.225(1), b = 14.612 (1), c = 15.520 (1) Å, = 96.6(3)°, Z = 4 and V = 1402.4ų. The stereochemistry of the 7/5-fused ring system is trans, the 7-membered and the 5-membered rings are found to be in the chair and envelope conformations, respectively. This represents the first study of a compound containing the 7/5-ring skeleton shown in (3) below.     

Reaction between [Ru3(CO)10(μ-dppm)] (dppm = Ph2PCH2PPh2) and Te2(C6H4OEt-4)2: X-ray crystal structure of [Ru2(CO)6{μ-C6H4PPh(CH2)PPh}]

Treatment of [Ru₃(CO)₁₀(-dppm)] (1) with the ditelluride Te₂(C₆H₄OEt-4)₂ in refluxing toluene afforded the new aryltellurol bridged complex [Ru₂(CO)₄(-TeC₆H₄OEt-4)₂ (-dppm)] (2) together with three known complexes [Ru₄(CO)₈(-CO)(₄-Te)₂(-dppm)] (3), [Ru₂(CO)₆{-CH₂PPh(C₆H₄)PPh}] (4), and [Ru₂(CO)₆{-C₆H₄PPh(CH₂)PPh}] (5). All the four complexes were characterized by spectroscopic methods, including an X-ray structure determination for 5. Complex 5 crystallizes in the monoclinic space group P2₁/c with a = 13.650(2), b = 9.995(2), c = 18.929(3) Å, = 97.49(2)°, V = 2560.4(8) ų, and Z = 4. In this complex the two ruthenium atoms are bridged by the phosphino-phosphide ligand C₆H₄PPh(CH₂)PPh which is attached to one Ru by the C₆H₄ group and a P atom while to the other Ru by both the two P atoms. Both the ruthenium atoms show distorted octahedral geometry. The Ru—Ru bond length is 2.8719(7) Å.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Synthesis and crystal structure of manganese(III) hydroxyl-containing Schiff base complexes: [Mn(III)(Hvanpa)2]N3 (H2vanpa = 1−(3-hydroxysalicylaldeneamino)-3-hydroxypropane)

The manganese complex, [Mn(III)(Hvanpa)₂]N₃ has been prepared and the crystal structure determined using x-ray crystallography. The mononuclear complex has a six-coordinate octahedral geometry. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.867(1), b = 13.316(2), c = 9.0110(1) Å, = 107.870(1)°, V = 1126.8(2) ų, and Z = 2. The Mn-O and Mn-N distances in the equatorial plane are in good agreement with those found for other manganese(III) Schiff base complexes. In the axial direction, the Mn-O distances of 2.274(2) Å is about 0.3 Å longer than those in the equatorial plane due to a Jahn-Teller distortion at the d⁴ manganese(III) center. In the crystal, each azido ion is linked through hydrogen bonding with two hydrogen atoms from the coordinate hydroxyl groups at the apical site.     

Synthesis and crystal structure of trans-[PdCl2(EtMeIm)2] (EtMeIm = N-ethyl-N′-methylimidazol-2-ylidene)

The palladium–carbene complex, trans-[Pd(EtMeIm)₂Cl₂] was prepared by carbene transfer via the Ag carbene species. The structure was determined by X-ray crystallography. It crystallizes in the monoclinic unit cell of dimensions of a = 8.0243(9), b = 8.5320(9), c = 11.7473(13) Å, = 100.151(2)° with space group of P2₁/n and Z = 2. The palladium atom is tetracoordinated by two chloride ions and two carbon atoms in a square planar geometry.