Solvent roles in metal ion coordination: the NiCl2O-solvates, NiCl2 · 4MeOH, NiCl2 · 2MeOH · 0.5dioxan and NiCl2 · 2H2O · 2dioxan

Low-temperature, single crystal X-ray structural characterisations of trans-[NiCl₂(HOMe)₄], trans-O-[Ni(MeOH)₂(μ-Cl)_(2/2)2]_(∞∣∞) · 0.5dioxan and trans-trans-[Ni(H₂O)₂Cl₂(O-dioxan-O)_(2/2)]_(∞∣∞) · dioxan are recorded, offering intriguing insights into O-donor/Ni(II) relativities. All nickel atoms in all structures are located on crystallographic inversion centres, the last two compounds being one-dimensional polymers.     

Syntheses and crystal structures of cyano-bridged cluster-metal layered coordination polymers [Cu(dien)]3[W4Te4(CN)12] · 9H2O and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O

Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]₃[W₄Te₄(CN)₁₂] · 9H₂O (1) (dien=diethylenetriamine) and [Ni(en)(NH₃)]₃[W₄Se₄(CN)₁₂] · 7.5H₂O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K₆[W₄Te₄(CN)₁₂] · 5H₂O/K₆[W₄Se₄(CN)₁₂] · 6H₂O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P2₁ for 1; trigonal, space group for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W₄Te₄(CN)₁₂}/{W₄Se₄(CN)₁₂} connected, one another by {Cu(dien)} or {Ni(en)(NH₃)} fragments, respectively.     

BEDT-TTF salts of the unsymmetrical [M(tfadt)2] dithiolene complexes (M = Ni, Au; tfadt = S2C2(CN)(CF3))

Two closely related 1:1 salts are obtained upon electrocrystallization of BEDT-TTF (BEDT-TTF: bis(ethylenedithio)tetrathiafulvalene) in the presence of the isosteric [M(tfadt)₂]⁻ dithiolene complexes (tfadt: 1-trifluoromethyl-2-cyano-1,2-dithiolato), which essentially differ by their spin state, S = 0 in [Au(tfadt)₂]⁻, S = 1/2 in [Ni(tfadt)₂]⁻. In both [BEDT-TTF][M(tfadt)₂] salts, the BEDT-TTF radical cations form chains with a strong lateral overlap and strong antiferromagnetic interactions while the paramagnetic anions in the nickel-containing salt [BEDT-TTF][Ni(tfadt)₂] are essentially non-interacting. The structural differences between the nickel and gold complexes are analyzed and discussed.     

Syntheses, characterizations and crystal structures of two lead(II) diphosphonates: Pb2[NH(CH2PO3)2] · 2H2O and Pb3[HO2C(CH2)3NH(CH2PO3)2]2 · 2H2O

Hydrothermal reactions of lead(II) acetate and HO₂C(CH₂)₃N(CH₂PO₃H₂)₂ at 170 and 140 °C, respectively, resulted in two different lead diphosphonates, namely, Pb₂[NH(CH₂PO₃)₂] · 2H₂O (1), in which the butyric acid moiety of the HO₂C(CH₂)₃N(CH₂PO₃H₂)₂ has been cleaved and a novel layered compound, Pb₃[HO₂C(CH₂)₃NH(CH₂PO₃)₂]₂ · 2H₂O (2). Their crystal structures have been determined by single crystal X-ray diffraction. In compound 1, the interconnection of the lead(II) ions by bridging amino-diphosphonate ligands leads to the formation of a 3D network. Compound 2 features an unusual triple-layer structure with the non-coordinated butyric acid moieties as pendant groups between the layers.     

Synthesis and characterization of new AMTTO-imine-ligands and their silver(I) complexes: crystal structures of TAMTTO, [Ag2(TAMMTO)4](NO3)2 · 4MeOH, [Ag(TAMTTO)(PPh3)2]NO3 · 1.5THF, [Ag(FAMTTO)(PPh3)2]NO3

Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treatment of 2 with AgNO₃ gave the complex [Ag₂(TAMMTO)₄](NO₃)₂ · 4MeOH (4) and of 2 and 3 with [Ag(PPh₃)₂]NO₃ gave the complexes [Ag(TAMTTO)(PPh₃)₂]NO₃ · 1.5THF (5) and [Ag(FAMTTO)(PPh₃)₂]NO₃ (6), respectively. All the compounds have been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by ³¹P NMR spectroscopy. Crystal data for 2 at −80 °C: monoclinic, space group C2/c, a=2319.6(2), b=609.8(1), c=1673.6(2) pm, β=106.14(1)°, Z=8, R₁=0.0523; for 4 at −80 °C: triclinic, space group , a=877.6(1), b=1085.2(1), c=1557.7(2) pm, α=77.14(1)°, β=80.87(1)°, γ=78.18(1)°, Z=1, R₁=0.0407; for 5 at 20 °C: triclinic, space group , a=1151.1(2), b=1225.1(2), c=1887.4(3) pm, α=78.04(1)°, β=86.20(1)°, γ=76.03(1)°, Z=2, R₁=0.0662; for 6 at −80 °C: triclinic, space group , a=1189.7(2), b=1387.8(2), c=1410.9(2) pm, α=94.74(2)°, β=95.12(2)°, γ=112.41(2)°, Z=2, R₁=0.0511.     

Hydrothermal synthesis and crystal structure of a novel one-dimensional arsenic vanadate decorated with organonitrogen ligand: [H3V3O26(AsO4)4(phen)8(H2O)2] · 2H2O (phen=phenanthroline)

A novel organic-inorganic hybrid vanadium arsenate [H₃V₃O₂₆(AsO₄)₄(phen)₈(H₂O)₂] · 2H₂O 1 (phen=phenanthroline) was synthesized by the hydrothermal reaction of V₂O₅, VOSO₄, Na₂HAsO₄ · 7H₂O, phen and water. Its structure was determined by elemental analyses, XPS spectra, EPR spectrum, TG analysis, IR spectrum and single-crystal X-ray diffraction.     

Crystal structure and thermal characterization of cadmium oxalate [CdC2O4 · 3H2O] and barium-doped cadmium oxalate [Ba0.5Cd0.5(C2O4)2 · 5H2O] single crystals grown in silica gel

Pure cadmium oxalate trihydrate (COT) and barium added cadmium oxalate (BCO) single crystals were grown by controlled diffusion of Cd²⁺ and Ba²⁺ ions in silica gel at ambient temperature. A single test tube technique coupled with gel aging conferred maximum size crystals by controlling the nucleation rate. It was found that the pH and age of the gel greatly influenced the crystal quality, their size and transparency. Grown crystals CdC₂O₄ · 3H₂O and Ba_0.5Cd_0.5(C₂O₄)₂ · 5H₂O were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and thermal analysis. Effect of barium dopant on the growth and morphology of cadmium oxalate was studied. Pure cadmium oxalate crystallized in triclinic system and the barium-doped cadmium oxalate crystallized in hexagonal system with massive changes in their unit cell parameters. The infrared spectrum revealed the presence of oxalate ligands and water of hydration in both the pure and barium-doped crystals. Thermal analysis showed that the grown crystals were dehydrated thermally even from lower temperatures and the doped crystals were found more stable.     

Hydrothermal synthesis and characterization of a zinc-substituted gallium phosphite, [H3N(CH2)2NH3]1/2 · [GaZn(HPO3)3(H2O)2]

An organically templated zinc-substituted gallium phosphite, [H₃N(CH₂)₂NH₃]_1/2 · [GaZn(HPO₃)₃(H₂O)₂] was synthesized under mild hydrothermal conditions in the presence of ethylenediamine (en) as structure-directing agent and characterized by single-crystal X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pbcn with unit cell parameters: a = 18.6146(10) Å, b = 11.0454(6) Å, c = 10.9074(4) Å, V = 2242.62(19) Å³ and Z = 8. This compound has a three-dimensional framework built up from secondary building units (SBU) of Ga(III) (or Zn(II)) and HPO₃ pseudopyramid by sharing vertices. The structure displays a two-dimensional channel system running along the [0 0 1] and [0 1 0] direction with 5-, 8- and 10-membered rings. The diprotonated ethylenediamine template molecules are located in the channels. In this structure, some of the Ga(III) sites are occupied by Zn(II) atoms. The compound was also characterized by IR spectroscopy, inductively coupled plasma (ICP), X-ray photoelectron spectra (XPS), differential thermal and thermogravimetric analyses.     

Synthesis and structure of two polymeric barium-oxydiacetates: [Ba(oda) · H2O]n and [Ba(Hoda)2]n (H2oda: oxydiacetic acid)

The reaction of barium carbonate or hydroxide with oxydiacetic acid leads to the self-assembly of two barium oxydiacetate polymers in good yield: [Ba(oda) · H₂O]_n (1) and [Ba(Hoda)₂]_n (2). The products have been characterized by elemental analysis, IR, TGA and single crystal X-ray diffraction studies. The central barium atom in each mononuclear fragment is nine-coordinate in 1 and 10-coordinate in 2. These fragments are bridged by carboxylato groups in anti-anti conformation and through H-bonds bonding interactions forming complex 3D networks.     

Polymorphism in [(polyamine)Co(NO2)x]Y crystals caused by changes in torsional angles of the (amine)N-Co-N-O fragments (x = 2, Y = NO3: x = 3, Y = 0)

Herein, we report the synthesis and characterization of a third polymorph of trans-[Co(2,3,2-tet)(NO₂)₂]NO₃, III, crystallizing in space group (No. 2) obtained during an attempt to reproduce the synthesis of a previously reported polymorph, I (for more details of polymorphs I and II, see Introduction and references cited therein). The cations of polymorphs I and II differ primarily by the angles that the planes of the two -NO₂ ligands make with one another; the former being considerably larger than that in II. Polymorph III resembles II in that the torsional angular differences between the trans-nitro ligands are also small, but differ notably from that in I.The structure of the compound [(5-Me-(dpt)Co(NO₂)₃], was determined also. The space group is P2₁/n, with two molecules in the asymmetric unit, whose occupancies are 65% and 35% for molecules IVa and IVb, respectively. Again, the two differ by the torsional angles of the nitro ligands, specially two of them whose angular orientations are vastly different. Molecules IVa and IVb are compared with a previously obtained polymorph V of this same compound reported earlier. Once more, V is closely related in stereochemistry to IVb, but differs markedly from IVa in nitro torsional angles.In all cases, the Co(amine) fragments are closely super-imposable and the differences in nitro torsional angles are the result of the availability of several amine hydrogens of the basal plane with which to make intra-molecular hydrogen bonds. Clearly, these hydrogen bonds must be of very similar strength and the barriers to rotation of the -NO₂ ligands must have energies similar to the energetics of the hydrogen bonds causing the torsional motions.     

Homoleptic platinum(II) and palladium(II) complexes of 1,5,9-trithiacyclododecane: the crystal structures of [Pt(12S3)2](PF6)2 · 2CH3NO2 and [Pd(12S3)2](BF4)2 · 0.5H2O

The synthesis, spectroscopy, electrochemistry, and crystal structures of two new mononuclear homoleptic Pt(II) and Pd(II) complexes with the crown trithioether 1,5,9-trithiacyclododecane (12S3) are reported. In contrast to behavior with analogous smaller ring trithiacrowns, both metal complexes exhibit exodentate axial sulfur donors, a consequence of the preferred conformation of the 12S3 ligand. The lack of two axial metal-sulfur interactions correlates with the observed electronic spectroscopy and oxidative electrochemistry displayed by the complexes and contrasts with properties exhibited by complexes containing smaller polythioether macrocycles. The two complexes have electronic spectra dominated by charge transfer, not d-d bands and show no M²⁺/M³⁺ couples. Both complexes show a fluxional 12S3 ligand in solution due to a 1,5-metallotropic shift, an uncommon observation of this particular type of intramolecular ligand exchange. The ¹⁹⁵Pt NMR chemical shift of −4201 ppm for [Pt(12S3)₂]²⁺ is consistent with an alternating positioning of the four sulfur lone pairs on the coordinated thioethers. Although 12S3 is poorly pre-organized for facial complexation, its flexibility to position a sulfur in an exodentate fashion enables it to form stable complexes with d⁸ metal ions such as Pt(II) and Pd(II).     

Investigation of the MSO4 · xH2O (M = Zn, x = 7; M = Cd, x = 8/3)/methyl 2-pyridyl ketone oxime reaction system: A novel Cd(II) coordination polymer versus mononuclear and dinuclear Zn(II) complexes

The reactions of methyl 2-pyridyl ketone oxime, (py)C(Me)NOH, with MSO₄ · xH₂O (M = Zn, x = 7; M = Cd, x = 8/3), in the absence of an external base, have been investigated. The synthetic study has led to the two new complexes [Zn(SO₄){(py)C(Me)NOH}(H₂O)₃] · H₂O (1 · H₂O) and [Zn₂(SO₄)₂{(py)C(Me)NOH}₄] · (py)C(Me)NOH [2 · (py)C(Me)NOH], and the coordination polymer [Cd(SO₄){(py)C(Me)NOH}(H₂O)]_n · [Cd(SO₄){(py)C(Me)NOH}(H₂O)₂]_n (3). In the three complexes the organic ligand chelates through its nitrogen atoms. The sulfate anion in 1 · H₂O is monodentate; the complex molecule is the mer isomer considering the positions of the aqua ligands. The Zn^II centers in 2 · (py)C(Me)NOH are bridged by two syn, anti η¹:η¹:μ₂ ligands; each metal ion has the cis-cis-trans disposition of the coordinated sulfate oxygen, pyridyl nitrogen and oxime nitrogens, respectively. The molecular structure of 3 is unique consisting of two different linear and ladder - type chains. π-π stacking interactions and/or hydrogen bonds lead to the formation of interesting supramolecular architectures in the three complexes. The thermal decomposition of complex 3 has been studied. Characteristic vibrational (IR, Raman) bands are discussed in terms of the nature of bonding and the structures of the three complexes.     

One-pot synthesis of the decaniobate salt [N(CH3)4]6[Nb10O28] · 6H2O from hydrous niobium oxide

A robust and easily reproducible one-pot synthetic method for the preparation of [N(CH₃)₄]₆[Nb₁₀O₂₈] · 6H₂O is introduced.     

Octahedral rhenium cluster complexes with organic ligands: Synthesis, structure and properties of [Re6Q8(3,5-Me2PzH)6]Br2 · 2(3,5-Me2PzH) (Q = S, Se)

Two new octahedral cluster complexes - [Re₆S₈(3,5-Me₂PzH)₆]Br₂ · 2(3,5-Me₂PzH) (1) and [Re₆Se₈(3,5-Me₂PzH)₆]Br₂ · 2(3,5-Me₂PzH) (2), where 3,5-Me₂PzH is 3,5-dimethylpyrazole, have been synthesized using reaction of rhenium chalcobromide complexes Cs₄[Re₆S₈Br₆] · 2H₂O and Cs₃[Re₆Se₈Br₆] · H₂O, respectively, with molten 3,5-dimethylpyrazole. Both compounds synthesized were characterized by X-ray single-crystal diffraction and chemical analysis, IR and luminescent spectra.     

Hydrogen bond supramolecular self-assembly in nickel(II) dithiophosphates, Ni[S2P(OR)2]2, R = sec-Bu, iso-Bu, and their bis(pyrazole) adducts

The reaction between nickel(II) nitrate and potassium phosphorus-1,1-dithiolates (di-sec-butyl and di-iso-butyl) in methanol yields 2:1 complexes which were characterized by FT-IR and NMR spectroscopy. 2:1 pyrazole adducts of both compounds were also obtained.The X-ray diffraction analysis of the compounds reveals square planar, four-coordination geometry for the homoleptic compounds and a six-coordinated distorted octahedral geometry for the adducts. In Ni[S₂P(OBu^s)₂]₂ the molecules are associated through C-H?O hydrogen bonds (2.652 Å), and in Ni[S₂P(OBuⁱ)₂]₂ the molecules are associated through C-H?S hydrogen bonds (2.948 Å). The pyrazole adducts are associated through N-H?O bonds and N-H?S bonds from the pyrazole nitrogen atoms, to form supramolecular assemblies. Thus, Ni[S₂P(OBu^s)₂(Pz)₂]₂ (Pz = pyrazole) forms bi-dimensional layers through N-H?O and N-H?S bonds (2.502 and 2.965 Å, respectively), whereas Ni[S₂P(OBuⁱ)₂(Pz)₂]₂ forms linear chains with N-H?S bonds 2.728 Å. The dithiophosphato groups behave as isobidentate chelating ligands.     

Synthesis and crystal structures of [K(18-crown-6)][Rb(18-crown-6)]2Ge9 · 6NH3, [Rb(18-crown-6)]3Ge9 · 9NH3 and [Cs(18-crown-6)]3Ge9 · 6NH3

The new compounds [K(C₁₂H₂₄O₆)][Rb(C₁₂H₂₄O₆)]₂Ge₉ · 6NH₃, [Rb(C₁₂H₂₄O₆)]₃Ge₉ · 9NH₃ and [Cs(C₁₂H₂₄O₆)]₃Ge₉ · 6NH₃ were prepared by the extraction of binary and ternary phases of the nominal composition K₂Rb₂Ge₉, Rb₄Ge₉ and K₂Cs₂Ge₉ with liquid ammonia in the presence of 18-crown-6. The resulting crystals were characterized by low temperature X-ray structure analysis. All of them contain the 21 electron cluster , which is coordinated by alkali metal cations in ion-paired arrangements. The cages were assigned their specific point group symmetry and were compared with hitherto known structures.     

[Hg(9-methyl-1-deazapurine)2](NO3)2 · H2O: a complex with a distorted hexagonal bipyramidal metal ion coordination sphere

Reaction of 9-methyl-1-deazapurine (9-MeDP) with Hg(CF₃COO)₂ in the presence of NaNO₃ yields the title compound [Hg(9-MeDP)₂](NO₃)₂ · H₂O with the two 9-MeDP ligands bound to the metal ion via their N7 positions. The X-ray structure is reported: monoclinic, P2₁/c (no. 14), a = 5.4015(11), b = 20.467(4), c = 17.775(4) Å, β = 97.00(3)°, V = 1950.4(7) ų, Z = 4. Hg is eight-coordinate with two trans-oriented Hg-N bonds (2.073(3) and 2.075(3) Å) and three nearly coplanar, bidentate nitrate moieties (Hg-O: 2.716(3)-2.985(4) Å), leading to a distorted hexagonal bipyramidal environment of the metal ion. Within this structure, the nitrate ions form a honeycomb-like chain structure with Hg^II being positioned inside the combs. This work represents the first report of such geometry for a transition metal ion surrounded by symmetrically bidentate nitrate ions. The corresponding nucleoside, 1-deazapurine 2′-deoxyribonucleoside, also forms a stable 2:1 complex with Hg^II, as was shown by ¹H NMR spectroscopy, making it a potential candidate for incorporation into nucleic acids based on metal-mediated base pairs.     

The cyanocarbanion (C[C(CN)2]3) as monodentate ligand: Synthesis, structure and magnetic properties of [Mn2(bpym)3(tcpd)2(H2O)2] (tcpd = (C[C(CN)2]3) and bpym = 2,2′-bipyrimidine)

One-pot reaction between MnCl₂·4H₂O, K₂tcpd (tcpd²⁻ = [C₁₀N₆]²⁻ = (C[C(CN)₂]₃)²⁻ = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion) and 2,2′-bipyrimidine (bpym = C₈H₆N₄) in aqueous solution yields the new compound [Mn₂(bpym)₃(tcpd)₂(H₂O)₂] (1). The molecular structure of 1 consists of a centrosymmetrical binuclear complex which includes unprecedented unidentate tcpd ligands with two bidentate and a bis-chelate bpym units. Examination of the intermolecular distances reveals that the dinuclear units are held together by hydrogen bonds involving coordinated water molecules and two nitrile groups of the tcpd ligand, giving rise to a 2D structure overall. Variable-temperature magnetic susceptibility data show the occurrence of slight antiferromagnetic coupling (J = −0.58 cm⁻¹) between the Mn(II) ions through bridging bpym (the exchange Hamiltonian being defined as ).     

Hydrolytic stability of SnCl4 and GaCl3 in the formation of [cis-SnCl4(H2O)2] · 18-crown-6 · 2H2O and [[2,2,2]cryptand + 2H][GaCl4]2

The combination of anhydrous SnCl₄ with 18-crown-6 in aqueous conditions results in formation of the non-hydrolysed product [cis-SnCl₄(H₂O)₂] · 18-crown-6 · 2H₂O. The X-ray crystal structure shows extensive intermolecular hydrogen bonding involving the cis-octahedral SnCl₄(H₂O)₂ units, the uncoordinated water molecules and the crown ether. Similarly, [2,2,2]cryptand reacts with an aqueous solution formed by adding anhydrous GaCl₃ to slightly acidic water, affording [[2,2,2]cryptand + 2H⁺][GaCl₄]₂.     

The structural definition of adducts of stoichiometry MX:dpex (2:3)(∞), M = Cu, Ag, X = simple anion, dpex = Ph2E(CH2)xEPh2, E = P, As

Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph₂E(CH₂)_xEPh₂ (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe-P,P′)CuX(P-dppe-P′)CuX(P,P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph₂As(CH₂)₂AsPh₂), X = Br, F₃CCO₂ (= ‘tfa’), F₃CSO₃ (≡ ‘tfs’); dpex = ‘dpape’ (Ph₂As(CH₂)₂PPh₂), X = CN, SCN, OClO₃) are one-dimensional polymers ?-E′)₁AgX(E-dpex-E′)₂-AgX(E-dpex-E′)₁AgX?, P, As sites scrambled in the latter. AgNO₃:dpam (2:3) is also a one-dimensional polymer, ?AgO·NO·OAg(As-dpam-As)AgO·NO·OAg? (‘dpam’ ≡ Ph₂As(CH₂)₂AsPh₂). AgX:dpae (2:3) (X = I, CN, ClO₄, NO₃) and AgX:dpape (2:3) (X = Br, I, NO₃) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph₂P(CH₂)₂AsPh₂)₃] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (¹H, ³¹P NMR, ESI MS) and in the solid state (IR).