The synthesis and crystal structure of a copper-sulfur cluster [Cu4(S5)2(C5H5N)4]·S8

The cluster [Cu₄(S₅)₂(C₅H₅N)₄]·S₈ with cage structure has been obtained by reaction of copper powder with sulfur and K₂S _x in pyridine, and its structure was determined by X-ray crystallography. The crystal data for the title compound: triclinic, P (No. 2),Z = 2,a = 11.818(4) Å,b = 13.155(3) Å,c = 14.177(4) Å, = 93.79(2)°, = 96.68(2)°, = 115.76(2)°,V = 1954.52(1) ų. The structure was refined toR = 0.038R _w = 0.053) for 6444 data withI > 3.0(I).Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.     

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster [V5O9(PhPO3)3(PhPO3H)2]2− and a comparison to the structure of the fully oxidized parent cluster [V5O7(OCH3)2(PhPO3)5]1−

The room temperature reaction of (Bu₄N)₃V₅O₁₄ with PhPO₃H₂ in methanol yields the pentanuclear V(V) cluster (Bu₄N)[V₅O₇(OCH₃)₂(PhPO₃)₅]·CH₃OH (1·CH₃OH). In contrast, the hydrothermal reaction of (Ph₄P) [VO₂Cl₂], PhPO₃H₂ and (NH₄)H₂PO₄ at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph₄P)₂[V₅O₉(PhPO₃)₃(PhPO₃H)₂] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P2₁/n,a=12.167(2) Å,b=23.348(5) Å,c=22.508(5) Å,β=98.49(2)°,V=6323.9(19) ų,Z=4,D _calc=1.558 g cm^?3; 3, triclinic, $P\bar 1$ ,a=13.478(3) Å,b=14.399(3) Å,c=23.638(5) Å,α=72.53(2)°,β=85.58(2)°,γ=69.88(4)°,V=4107.0(16) ų,Z=2, D_calc=1.479 g cm^?3.     

Hydrothermal synthesis,crystal structure and thermal stability of a new 2D layered metal(II) phosphonate: [NH3CH2CH2NH3][Fe2(O3PCH(OH)CO2)2(H2O)2]·2H2O

In the presence of ethylenediamine template agents, a metal(II) phosphonate, [NH₃CH₂CH₂NH₃][Fe₂(O₃PCH(OH)CO₂)₂(H₂O)₂]?·?2H₂O (1) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction as well as infrared spectroscopy, elemental analysis and thermogravimetric analysis. The compound crystallines in the monoclinic space group P2₁/n: Crystal data for 1: a?=?8.4523(8)?Å, b?=?9.8196(9)?Å, c?=?10.9217(10)?Å, β?=?105.9500(10)°, V?=?871.58(14)?Å, Z?=?2, D _c?=?2.103?g?cm^?3, R ₁?=?0.0290, wR ₂?=?0.0811. The Fe (II) cation is octahedrally coordinated by six oxygen atoms from the three ligands and one coordinated water molecule to form a 2D layered structure with a one-dimensional channel system in the a-axis direction.     

Synthesis,characterization, and crystal structure of a 2-D metal diphosphonate: Cu3(H2O)2[HO3PCH2N(CH3)CH2PO3]2 · 2H2O

Hydrothermal reaction of N-methyl-iminobis(methylenephosphonic acid), CH₃N(CH₂PO₃H₂)₂, (H₄L) with copper(II) acetate afforded a new layered Cu(II) amino diphosphonate, Cu₃(H₂O)₂(HL)₂?·?2H₂O (1). Compound 1 was studied by IR spectroscopy, TGA/DTA data, and X-ray diffraction (XRD) techniques. The XRD patterns are the same for the hydrated and the dehydrated complexes. A single-crystal X-ray crystallographic determination reveals copper in two different coordination environments. Cu1 has a distorted elongated tetragonal octahedral geometry, whereas Cu2 has a square-pyramidal distorted geometry. The HL trianion is a pentadentate ligand with a deprotonated nitrogen atom and two oxygen atoms of each phosphonate binding to copper. Hydrogen bonds between lattice water molecules in interlayer spaces and the non-coordinated phosphonate oxygen atoms as well as water ligands leads to a 3-D supramolecular network structure.     

Platinum-silver clusters: synthesis and crystal structure of [Pt3Ag(μ-CO)3(PPh3)5]ClO4 · 2H2O

Reaction of [NBu₄]₂[Pt₁₂(CO)₂₄] with [Ag(PPh₃)₄]ClO₄ and PPh₃ leads to two isolable platinum-silver clusters; the title complex was characterised by single crystal X-ray diffraction. the Pt₃Ag core is tetrahedral; one Pt atom is seven-coordinated, the other two are six-coordinate.     

N,N′-methylenedipyridinium Pt(II) and Pt(IV) hybrid salts: synthesis, crystal and molecular structures of [(C5H5N)2CH2] · [PtCl4] and [(C5H5N)2CH2] · [PtCl6]

The highly insoluble organic-inorganic hybrid ionic compounds N,N??-methylenedipyridinium tetrachloroplatinate(II) [(C₅H₅N)₂CH₂] · [PtCl₄] and N,N??-methylenedipyridinium hexachloroplatinate(IV) [(C₅H₅N)₂CH₂] · [PtCl₆] were obtained by the treatment of N,N??-methylenedipyridinium dichloride monohydrate [(C₅H₅N)₂CH₂]Cl₂ · H₂O with K₂[PtCl₄] or (NH₄)₂[PtCl₆], respectively, in an aqueous solution. Both complexes were isolated, purified, characterised by elemental analysis, and their molecular structures were confirmed by powder X-ray diffraction. The crystal structure of both compounds consists of separated discrete dications [(C₅H₅N)₂CH₂]²⁺ and anions [PtCl _n ]^2? (n = 4 or 6). As anticipated, the dications formed a butterfly shape consisting of two pyridine rings bound to the methylene group via their N atoms, while the Pt centre had a square planar geometry in [(C₅H₅N)₂CH₂] · [PtCl₄] and an octahedral coordination in [(C₅H₅N)₂CH₂] · [PtCl₆]. Interestingly, both crystal structures are stabilised by intermolecular C-H??Cl non-standard hydrogen bonds, ??-?? ring interactions between two pyridine rings of adjacent dications, and also by Cl-?? interactions.     

Synthesis and crystal structure of ((NH3CH2CH2)3N)2P6O18·6H2O

Chemical preparation and crystal structure are given for a new cyclohexaphosphate: ((NH₃CH₂CH₂)₃N)₂P₆O₁₈·6H₂O. This compound is triclinic P¯1 with the following unit-cell parameters: a = 10,281(1)Å, b = 11.083(1)Å, c = 9.307(2)Å, α = 103.83(1) °, β = 108.56(1) °, γ = 68.11(1) °, Z = 1, V = 924.2(3)ų and pcal. = 1.582 g.cm⁻³. Its atomic arrangements contain layers built by P₆O₁₈ ring anions spreading in the plans (001). Between these layers are located the organic groups which form hydrogen bonds with oxygen atoms of P₆O₁₈ rings and water molecules. Crystal structure has been solved and refined to R = 0.028 using 4540 independent reflections. The thermal behavior has been investigated and interpreted by comparison with IR absorption spectroscopy and X-ray diffraction experiments.     

The first decaruthenium hydrido cluster: synthesis and crystal structure of [N(PPh3)2]2[Ru10C(CO)24]·C6H14 and [N(PPh3)2][HRu10C(CO)24]

X-ray structural studies of new thermolysis products from the reaction of Ru₃(CO)₁₂ in heptane in the presence of 1,3,5-trimethylbenzene (mesitylene) confirm that they are the decaruthenium carbido-cluster dianion [Ru₁₀C(CO)₂₄]²⁻ (I) and the hydrido decaruthenium carbido-cluster monoanion [HRu₁₀C(CO)₂₄]⁻ (II). Both anions have the giant tetrahedron Ru₁₀ metal framework, and the monohydride provides the first example of a hydrido ligand in a tetrahedral Ru₄ cavity.     

Synthesis and structure of [Cr3O(CH3COO)6(H2O)3][UO2 (CH3COO)3] · 3H2O

Crystals of [Cr₃O(CH₃COO)₆(H₂O)₃][UO₂(CH₃COO)₃]·3H₂O (I) were synthesized for the first time and studied by X-ray crystallography. The crystals of I are orthorhombic: a = 8.3561(3) ?, b = 16.8421(5) ?, c = 25.7448(9) ?, V = 3623.2(2) ?³, space group P2₁2₁2₁, Z = 4, R = 0.0409. The structure is composed of trinuclear [Cr₃O(CH₃COO)₆(H₂O)₃]⁺ complexes and mononuclear [UO₂(CH₃COO)₃]^? complexes classified with crystal-chemical groups A₃M³B ₆ ² M ₃ ¹ (A = Cr³⁺, M³ = O^2?, B² = CH₃COO^?, M¹ = H₂O) and AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?), respectively. The complexes are bound to each other by electrostatic interactions and hydrogen bonds involving outer-sphere water molecules. The results of IR spectroscopic study of I are in good agreement with the structural data for the crystal.     

A cobalt molybdenum phosphate with a tunnel: Hydrothermal synthesisand structure of (NH3CH2CH2NH3)4·(NH3CH2CH2NH2)·Na·[Co2Mo12O30(PO4)(HPO4)4(H2PO4)3]·5H2O

Transition Metal Chemistry -     

The synthesis and crystal structure of novel Mo-Sn tetranuclear cubane-like cluster [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2)

The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo₃(SnBr₃)(μ ₃-O)(μ ₃-S)₃(dtp)₃(py)₃]·(CH₂Cl₂) (A) (dtp=S₂P(OC₂H₅)₂) are reported. The compound is prepared by the reaction of [Mo₃(μ ₃-O)(μ-S)₃(dtp)₄·(H₂O)] with SnBr ₃ ^? . The molecular structure of the cluster can be described as a [Mo₃OS₃] core with the SnBr ₃ ^? fragment linked to {Mo₃} triangle by three (μ ₃-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C_3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr ₃ ^? may cause electron transfer from Sn²⁺ to [Mo₃OS₃] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P2₁/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)ų, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,R _w=0.064.     

Reaction of chlorine with platinum(IV) triamine containing N,N-dimethylethylenediamine. The crystal structure of [Pt{(CH3)2N(CH2)2NH2}PyCl3]Cl·H2O[Pt{(CH3)2N(CH2)2NCl}PyCl3], and [Pt{(CH3)2N(CH2)2NH2}PyCl4]

The Platinum(II) diamine with N,N-dimethylethylenediamine (N,N-dimeEn) [Pt{(CH₃)₂N(CH₂)₂NH₂}Cl₂] (I) was synthesized. The reaction of the diamine with pyridine gave Pt(II) tetramine [Pt{(CH₃)₂N(CH₂)₂NH₂}Py₂]Cl₂ (II), which was oxidized with chlorine to give Pt(IV) triamine Pt{[(CH₃)₂N(CH₂)₂}PyCl₃]Cl · H₂O (III). The reaction of III with chlorine (chloroamidation) yielded chloroimide [Pt{(CH₃)₂N(CH₂)₂NCl}PyCl₃] (IV). The IR spectra of complexes I–IV and UV/Vis spectra of III and IV were studied. X-Ray diffraction analysis was performed for III (monoclinic crystals, space group P2₁/c, a = 7.7437(6), b = 8.1100(7), c = 28.52992(2) Å, β = 93.7280(10)°, Z = 4, R _hkl = 0.0420) and IV (orthorhombic crystals, space group Pna2₁, a = 15.7825(12), b = 7.4447(6), c = 12.3099(6) Å, Z = 4, R _hkl = 0.0539). During oxidation of Pt(II) tetramine with chlorine, the pyridine molecule is removed from the cis position relative to the (CH₃)₂N group (trans position relative to the NH₂ group) of N,N-dimethylethylenediamine. The reaction of chloroimide complex IV with concentrated HCl (dechloroamidation) at 20°C afforded the initial complex III; that at 100°C, gave triamine III together with Pt(IV) diamine [Pt(N,N-dimeEn)Cl₄] (V) (monoclinic crystals, space group P2₁/n, a = 7.1278(5), b = 11.5384(8), c = 12.7501(9) Å, β = 93.23(10)°, Z = 4, R _hkl = 0.0239).     

Hydrothermal synthesis and crystal structure of a heteropolyoxotungstate formed by sandwich-type heteropolyanion [Gd(PW11O39)2]11− and reduced [Cu(en)2] + cations

A heteropolyoxotungstate, [Cu(en)₂]₂H₈[Gd(PW₁₁O₃₉)₂] ·?(H₂en)_0.5 ·?3H₂O (1), has been hydrothermally synthesized and characterized by IR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a =?12.651(2) ų, b =?20.559(3) ų, c =?21.729(3) ų, α =?71.379(2), β =?82.829(2), γ =?75.532(2)°, V =?5179.5(14) ų, Z =?2, R ₁ =?0.0702 and ωR ₂ =?0.1479. The heteropolyanion is composed of two monovacant [α-PW₁₁O₃₉]^7? Keggin moieties linked via a Gd atom leading to a sandwich-type structure. The Gd center is in a distorted square antiprismatic coordination environment with eight oxygen atoms, four from each of the two [α-PW₁₁O₃₉]^7?moieties.     

Synthesis,crystal structure,and magnetism of a dinuclear nickel(II) complex [Ni2(MOBPT)2(N3)4] · 2H2O

A dinuclear nickel(II) complex, [Ni₂(MOBPT)₂(N₃)₄] · 2H₂O (MOBPT = 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, UV, IR, ESI-MS, and single crystal X-ray crystallography. The complex crystallizes in triclinic system, space group P 1 with a = 9.877(2) Å, b = 10.396(2) Å, c = 11.975(3) Å, α = 71.638(3)°, β = 74.968(3)°, γ = 64.747(3)°, V = 1044.2(4) ų, Z = 1, R = 0.0371 for 5774 observed reflections. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planar with each Ni²⁺ coordinated by four nitrogens from two MOBPT ligands and two axial azides in a distorted octahedral geometry. Magnetic measurements reveal weak antiferromagnetic exchange in the complex.     

Chlorine reaction with platinum triamine [Pt(N,N-DimeTm)PyCl3]Cl (N,N-DimeTm = (CH3)2N(CH2)3NH2). Crystal structure of [Pt(N,N-DimeTm)Cl2], [Pt(N,N-DimeTm(Py)Cl3]Cl · H2O and [Pt{(CH3)2N(CH2)2C(O)NH}(Py)Cl3]

Treatment of platinum(II) diamine [Pt(N,N-DimeTm)Cl₂] (I) with pyridine gave tetramine [Pt(N,N-DimeTm)Py₂]Cl₂ (II); by oxidation with chlorine this was converted to Pt(IV) triamine, [Pt“(N,N-DimeTm(Py)Cl₃]Cl (III) with a six-membered chelate ring. According to X-ray diffraction data, the reaction of complex II with chlorine is accompanied by removal of the pyridine molecule from the trans-position to the NH₂ group of N,N-dimethyltrimethylenediamine. The reaction of complex III with chlorine at 20°C afforded a mixture of compounds (IV) and the complex [Pt“(CH₃)₂N(CH₂)₂C(O)NH”(Py)Cl₃] (V) with an amidate six-membered metal ring, dimethylpropioamide, which was also isolated upon refluxing a mixture of IV in an aqueous solution. The UV/Vis and IR spectra of the obtained complexes were studied, and X-ray diffraction analysis of I, III, and V was performed. The crystals of I are triclinic, space group P $ \bar 1 $ ; a = 7.6526(4) Å, b = 11.5571(6) Å, c = 12.4432(7) Å, α = 113.85(1)°, β = 96.54(2)°, γ = 106.78(2)°; Z = 4; R _hkl = 0.051. The crystals of III are monoclinic, space group C2/c; a = 36.715(2) Å, b = 7.8179(4) Å, c = 29.721(16) Å, β = 127.80(1)°; Z = 16; R _hkl = 0.036. The crystals of V are monoclinic, space group P2₁/n; a = 7.0398(6) Å, b = 27.458(2) Å, c = 7.687(6) Å, β = 106.270(1)°; Z = 4; R _hkl = 0.052.     

A dinuclear molybdenum cluster containing i-mnt ligand: synthesis and crystal structure of [Mo_2S_4(i-mnt)_2] (Et_4N)_2

A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.