A decanuclear oxomolybdenum(V,VI) cluster with 4-isopropylpyridine

The title centrosymmetric cluster octakis(4-iso­propyl­pyridine-N)-di-μ₄-oxo-hexa-μ₃-oxo-octa-μ₂-oxo-deca­oxo­octa­molyb­denum(V)­dimolybdenum(VI), [Mo₁₀O₂₆(C₈H₁₁N)₈], consists of ten Mo atoms connected together by bridging oxo groups. Pentavalent Mo atoms are linked into four Mo₂^V pairs by metal–metal single bonds with lengths of 2.5637 (6) and 2.6132 (6) Å.     

Tetrapotassium nonastannide,K4Sn9

In K₄Sn₉, which crystallizes with a new structure type, the Sn atoms form isolated Wade nido‐[Sn₉]^4? clusters of approxi­mate C_4v symmetry (monocapped square antiprisms), with Sn—Sn distances ranging from 2.9264 (9) to 3.348 (1) Å. The cluster anions are separated by K⁺ cations and are in a hexagonal close‐packed arrangement.     

Bis(iminodiethylenedi­ammonium) di‐μ5‐hydrogen­phosphato‐penta­molybdate(VI) tetra­hydrate

The crystal structure of the title compound, (C₄H₁₅N₃)₂[Mo₅O₁₅(HPO₄)₂]·4H₂O, is made up of [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters, iminodiethylenediammonium cations and solvent water mol­ecules. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster, with approximate C₂ symmetry, can be considered as a ring formed by five distorted edge‐ and corner‐sharing MoO₆ octa­hedra, capped on both poles by a hydro­phosphate tetra­hedron. There exist N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds between the organic ammonium groups and the clusters, with inter­atomic N⋯O distances ranging from 2.675 (3) to 2.999 (3) Å, and C⋯O distances ranging from 3.139 (5) to 3.460 (5) Å.     

Tetra­butyl­bis(N‐phthaloyl­glycinato)­distannoxane dimer

The crystal structure of the title compound, [Sn₄(C₄H₉)₈(C₁₀H₆NO₄)₄O₂], contains centrosymmetric dimers. It contains a central Sn₂O₂ core with the O atoms bonded to two di­butyl­bis(N‐phthaloyl­glycinato)­tin units. The Sn atoms of the core are six‐coordinate in a skew trapezoidal bipyramidal geometry, while the exocyclic Sn atoms are essentially five‐coordinate in a distorted trigonal geometry. The Sn—C distances lie in a narrow range of 2.120 (5)–2.138 (4) Å.     

Di­chloro­bis(1,2‐phenyl­enedi­amine)­nickel(II)

The title compound, [NiCl₂(C₆H₈N₂)₂], contains centrosymmetric mol­ecules with two phenyl­ene­di­amine ligands coordinated in a bidentate fashion. The Ni—N distances are 2.088 (1) and 2.096 (1) Å, and the Ni—Cl distance of 2.4635 (4) Å. The plane of each phenyl­enedi­amine mol­ecule makes a dihedral angle of 26.53 (7)° with the NiN₄ plane. Extensive hydrogen bonding leads to distinct cleavage in the bc plane.     

Bis(4‐hydroxy­benzoato‐O)(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)nickel(II): a three‐dimensional framework built from O—H⋯O and N—H⋯O hydrogen bonds

The title compound, [Ni(C₇H₅O₃)₂(C₁₀H₂₄N₄)], contains octahedral Ni^II in a centrosymmetric trans configuration with Ni—N distances of 2.0637 (17) and 2.0699 (16) Å and an Ni—O distance of 2.1100 (14) Å. The mol­ecules are linked by a single type of O—H?O hydrogen bond [O?O 2.618 (2) Å and O—H?O 161°] into two‐dimensional sheets; a singletype of N—H?O hydrogen bond [N?O 2.991 (2) Å and N—H?O 139°] links these sheets into a three‐dimensional framework.     

Bis{μ‐2‐[(2,3‐dichloro­phenyl)­amino]­benzoato‐κO}di‐μ2‐ethoxo‐octa­methyl­di‐μ3‐oxo‐tetra­tin(IV)

The title compound, [Sn₄(CH₃)₈(C₁₃H₈Cl₂NO₂)₂(C₂H₅O)₂O₂], is a centrosymmetric dimer, with three linearly fused four‐membered Sn—O—Sn—O rings. The coordination poly­hedron of the Sn atom bonded to the carboxyl­ate can be described as trigonal–bipyramidal distorted toward square‐pyramidal. That of the second Sn atom is similar, but the distortion towards square‐pyramidal geometry is greater. The Sn—O and Sn—C distances are 2.020 (2)–2.226 (2) and 2.096 (4)–2.114 (4) Å, respectively. The benzene rings of the 2‐[(2,3‐dichloro­phenyl)­amino]benzoate ligand subtend an angle of 50.49 (17)°; the conformation of the ligand is stabilized by intra­molecular N—H⋯Cl and N—H⋯O hydrogen bonds. The structure is assembled viaπ–π stacking inter­actions to form chains parallel to [10].     

2,5‐Bis(methylthio)‐1,4‐benzo­quinone and 2‐methyl‐3‐(methylsulfonyl)benzo[b]thiophene

The structure of 2,5‐bis­(methyl­thio)‐1,4‐benzo­quinone, C₈H₈O₂S₂, is composed of an essentially planar centrosymmetric benzo­quinone substituted with two methyl­thio groups. The important bond distances are S—Csp³ 1.788 (2) and S—Csp² 1.724 (2) Å, and the two Csp²—Csp² distances are 1.447 (3) and 1.504 (3) Å, which differ significantly. There are short S?S interactions of 3.430 (1) Å and Csp²—H?O‐type contacts forming a dimeric motif with graph set R₂²(8). The structure of 2‐methyl‐3‐(methyl­sulfonyl)­benzo­[b]­thio­phene, C₁₀H₁₀O₂S₂, is composed of an essentially planar benzo­thio­phene moiety substituted with methyl and methyl­sulfonyl groups. The mean values of the important bond distances are endocyclic S—Csp² 1.734 (3), S=O 1.434 (4) and C—C_aromatic 1.389 (10) Å. The exocyclic S—Csp² and S—Csp³ distances are 1.759 (4) and 1.763 (5) Å, respectively.     

Dichloro­(O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid‐κ2N,N′)copper(II)

In the title compound, [CuCl₂(C₉H₁₂N₂O)], the Cu^II atom is coordinated by two Cl⁻ anions and two N atoms of one O‐ethyl 3‐methyl­pyridine‐2‐carboximidic acid mol­ecule in a slightly distorted square‐planar geometry, with Cu—N distances of 2.0483 (17) and 1.9404 (18) Å, and Cu—Cl distances of 2.2805 (10) and 2.2275 (14) Å. In addition, each Cu^II atom is connected by one Cl⁻ anion and the Cu^II atom from a neighbouring mol­ecule, with Cu⋯Cl and Cu⋯Cu distances of 2.9098 (13) and 3.4022 (12) Å, respectively, and, therefore, a centrosymmetric dimer is formed. Adjacent mol­ecular dimers are connected by π–π stacking inter­actions between pyridine rings to form a zigzag mol­ecular chain. The mol­ecular chains are also enforced by N—H⋯Cl and C—H⋯Cl inter­actions.     

Research on in part “loosely” coordinated trinuclear molybdenum cluster compounds — the synthesis and crystal structure of {Mo3(μ3-S)(μ-S)3[S2P(OEt)2]4 ṁ P(C6H5)3} (0.86CH2Cl2)

The synthesis and crystal structure of novel trinuclear molybdenum cluster compound with somewhat “loose” coordination site {Mo₃(μ₃-S)(μ-S)₃[S₂P(OEt)₂l₄ ? P(C₆H₅)₃} ? (0.86 CH₂C1₂) have been reported. The cluster crystallizes in the space group with two molecules in a unit cell whose parameters are a=10.472(4), b=14.375(2), c=21.695(3)Å; α=74.04(1)°, β=76.50(2)°, γ=72.22 (2)°, V=2950ų and D_o=1.693 g ? cm^?3. On the basis of 4840 independent reflections with I≥2σ(I), the structure was solved by heavy atom method and Fourier method and refined by full-matrix least-squares techniques to a final R=0.058. The distances between Mo atoms in this cluster are 2.731(1), 2.748(1) and 2.753(1)Å respectively. The meat value of Mo—Mo bond lengths is slightly shorter than those in other trinuclear Mo clusters with “loosely coordinated” site. In addition, the PPh₃ ligand is loosely coordinated to one Mo atom in direction opposite to the μ₃-S with Mo—P bond length of 2.647(3)Å. This is different from the other structurally analogous clusters, in which the loosely coordinated ligand is trans to μ₂-S. A summary of Mo—Mo and Mo—L bonding for such clusters is given.     

Di‐μ‐methoxy‐bis[(η5‐cyclopentadienyl)(nitrosyl‐κN)(trimethylsilylmethyl)molybdenum(II)]

The title complex, [Mo₂(C₅H₅)₂(CH₃O)₂(C₄H₁₁Si)₂(NO)₂], is formed in high yield by treating [CpMo(NO)(CH₂SiMe₃)₂] (Cp is cyclo­penta­dienyl) with methanol. The nitro­syl ligands are nearly linear [O—N—Mo 170.1 (4) and 170.1 (5)°], with short Mo—N bonds [1.769 (4) and 1.776 (4) Å] and long N—O bonds [1.216 (5) and 1.201 (4) Å]. The central four‐membered Mo₂O₂ ring exhibits an average Mo—O bond length of 2.15 Å.     

[μ-6,9-Cl-8-(OMe)-6,9-(η5-C5Me5)2-arachno-6,9,5-Rh2SB7H7]

The title compound, μ-6,9-chloro-8-methoxy-6,9-bis­(η⁵-penta­methyl­cyclo­penta­dienyl)-6,9-dirhoda-5-thia-arachno-decaborane(7), [Rh₂(CH₁₀B₇OS)(C₁₀H₁₅)₂Cl], has a single Cl atom bridging the two remote rhodium `prow' vertices of an arachno ten-vertex dirhoda­thia­decaborane cluster, with Rh—­Cl distances of 2.3475 (11) and 2.3536 (11) Å, and an Rh—Cl—Rh angle of 106.82 (4)°.     

[5‐Bromo‐N‐(2‐carboxylatophenyl)salicylideniminato]dimethyltin(IV)

The structure of the title di­methyl­tin(IV) complex, [2‐(5‐bromo‐2‐oxido­benzyl­idene­amino)­benzoato‐κ³O,N,O′]di­methyl­tin(IV), [Sn(CH₃)₂(C₁₄H₈BrNO₃)], features centrosymmetric dimers disposed about a central Sn₂O₂ core. Each Sn centre has seven‐coordinate pentagonal–bipyramidal geometry, taking into account two moderately long Sn—O contacts about an inversion centre [2.679 (4) and 2.981 (4) Å]. The methyl groups are in an axial orientation.     

Hydrogen bonding in C‐substituted nitroanilines: sheets built from alternating R(12) and R(36) rings in 2‐bromo‐6‐cyano‐4‐nitroaniline

Molecules of the title compound (systematic name: 2‐amino‐3‐bromo‐5‐nitro­benzo­nitrile), C₇H₄BrN₃O₂, are linked by N—H?N and N—H?O hydrogen bonds [H?N 2.19 Å, N?N 3.019 (4) Å and N—H?N 157°, and H?O 2.17 Å, N?O 2.854 (3) Å and N—H?O 134°] to form (10) sheets built from alternating R(12) and R(36) rings, both of which are centrosymmetric.     

Synthesis,Crystal Structure,and Bonding of (PCl4)2[Mo2Cl10], the First Compound in Mo–P–Cl System

An ampule reaction between Mo and PCl₅ at 200 °C yielded (PCl₄)₂[Mo₂Cl₁₀], the first ternary compound in Mo–P–Cl system. Single crystal X-ray diffraction gave a triclinic unit cell: a = 6.870(1), b = 8.892(2), c = 9.423(2) Å, α = 100.24(2), β = 95.55(2), γ = 96.12(2)° (V = 559.3(2) ų, Z = 1, sp. gr. P1, wR₂ = 0.0575 and R₁ = 0.0279. The ionic compound is built from edge sharing bioctahedra [Mo₂Cl₁₀]^2– and two tetrahedra PCl₄⁺. The averaged Mo–Cl_b distance, 2.503(1) Å, is longer than the Mo–Cl_t distance, 2.33(2) Å. The Mo … Mo distance, 3.77 Å, indicates the absence of a direct Mo–Mo interaction. Semiempirical and ab initio calculations showed the possibility for [Mo₂Cl₁₀]^2– to exist with long and short Mo to Mo distances, the letter corresponding to the Mo–Mo bond.     

Chloro{2,2′‐[(1S,2S)‐1,2‐di­phenyl‐1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}(ethanol‐κO)­manganese(III)

The crystal structure of the title compound, [MnCl(C₂₈H₂₂N₂O₂)(C₂H₆O)], has been determined at 173 (2) K in the non‐centrosymmetric space group P2₁2₁2₁. The asymmetric unit contains two molecular units. An intermolecular O—H⋯Cl hydrogen bond is formed between the OH group of an ethanol mol­ecule coordinated to the Mn atom and the coordinated Cl⁻ anion, and so polymeric chains of Mn‐containing fragments are formed [O—H⋯Cl = 3.1281 (16) and 3.1282 (15) Å]. The Mn atoms have a pseudo‐octahedral coordination sphere, with the four donor atoms of the Schiff base forming an equatorial plane [Mn—O distances are 1.8740 (13), 1.8717 (13), 1.8749 (13) and 1.8823 (13) Å, and Mn—N distances are 1.9868 (15), 1.9910 (14), 1.9828 (15) and 1.9979 (14) Å]. The axial positions are occupied by an ethanol mol­ecule [Mn—O distances of 2.3069 (15) and 2.3130 (15) Å] and a Cl⁻ ligand [Mn—Cl distances of 2.5732 (6) and 2.5509 (6) Å].     

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.     

1,2:1,3‐Bis(μ‐p‐toluato‐O:O′)‐1‐(triphenylphosphine‐P)‐1‐ruthena‐closo‐undecaborane

The title compound, [(PPh₃)(p‐MeC₆H₄COO)₂RuB₁₀H₈], contains an 11‐vertex closo‐type RuB₁₀ cluster fused to two symmetric exo­poly­hedral Ru—O—C—O—B five‐membered rings. Principal distances include Ru—B 2.010 (5)–2.392 (4) Å and Ru—O 2.218 (5) and 2.222 (2) Å.     

(η5‐Cyclo­penta­dienyl)(p‐fluoro­phenoxo)(nitro­syl)(tri­methyl­silyl­methyl)­molybdenum(II)

The title complex, [Mo(C₅H₅)(C₆H₄FO)(C₄H₁₁Si)(NO)], is formed by reacting CpMo(NO)(CH₂SiMe₃)₂, where Cp is cyclo­penta­dienyl, with one equivalent of p‐FC₆H₄OH. The complex exhibits the expected piano‐stool molecular structure, with a linear nitro­syl ligand [Mo—N—O 168.2 (2)°] having Mo—N and N—O distances of 1.764 (2) and 1.207 (3) Å, respectively. The phenoxo Mo—O distance of 1.945 (2) Å is suggestive of some multiple‐bond character.     

The dimeric mixed‐ligand titana­carborane sandwich [1‐(Cp)‐1‐Ti‐2‐(Me)‐3‐(SiMe3)‐2,3‐C2B4H4]2

The title dimer, bis­[1‐cyclo­penta­dienyl‐2‐methyl‐1‐titana‐3‐tri­methylsilyl‐2,3‐dicarba‐closo‐hexaborane(6)], [Ti(C₅H₅)(C₆­H₁₆­B₄Si)]₂, reveals that the centrosymmetric mol­ecule consists of two bent‐sandwich titanacarboranes bridged by the B—H—Ti bonds. The average bond distances are Ti—B 2.445 (3), Ti—C(cage) 2.334 (2) and Ti—C(Cp) 2.376 (3) Å, and the corresponding bond angles are Cp—Ti—Cp 163.2 (1) and Cp—Ti—Cb (Cb = C₂B₃ face) 139.9 (1)°; the Ti—H separations are 2.10 (2) and 2.19 (2) Å.