Soft scorpionate coordination at alkali metals

Three soft scorpionate coordination complexes of alkali metals are presented together with an overview of the structural preferences of alkali metal soft scorpionate complexes. This analysis suggests that these thione-based ligands will continue to be a rich source of inter­esting alkali metal motifs worthy of isolation and characterization.

A one-dimensional lead(II) coordination polymer with terminal and bridging 5-carb­oxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxyl­ate ligands

Hydro­thermal synthesis yields a one-dimensional lead(II) coordination polymer of 5-carb­oxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxyl­ate, in which aromatic stacking and hydrogen bonds lead to a three-dimensional supra­molecular architecture.

Low-dimensional compounds containing cyanide groups. XXV. Synthesis, spectroscopic properties and crystal structures of two ionic iron(II) complexes with tri­cyano­methanide: tris­(1,10-phenanthroline-κ²N,N′)iron(II) bis­(tri­cyano­methanide) and tris­(2,2′-bi­pyridine-κ²N,N′)iron(II) bis­(tri­cyano­methanide) sesquihydrate

Two new diamagnetic Fe^II coordination compounds are ionic, with distorted octa­hedral [Fe(phen)₃]²⁺ or [Fe(bpy)₃]²⁺ complex cations (phen is 1,10-phenanthroline and bpy is 2,2′-bi­pyridine) and two uncoordinated planar tri­cyano­methanide (tcm) counter-anions balancing the positive charges of the cations. The structures are stabilized by π–π inter­actions between stacked aromatic rings of adjacent phen mol­ecules and by O—H⋯N hydrogen bonds.

An iron(III) complex salt containing pyrazole as both ligand and counter-ion: bis­(1H-pyrazol-2-ium) penta­cyanido(1H-pyrazole-κN²)ferrate(III)

In a complex salt composed of an [Fe(CN)₅(pyrazole)]²⁻ dianion and two 1H-pyrazol-2-ium cations, the dianion is a mononuclear cluster in which the Fe^III cation is coordinated by five cyanide ligands and by one of the N atoms of a pyrazole ligand. A three-dimensional supra­molecular network is formed through a rich scheme of N—H⋯N hydrogen bonds and C—H⋯π inter­actions among the cations and anions.

The structure of {[Co(pht)(bpy)(H₂O)]·3H₂O}_n (pht is phthalate and bpy is 4,4′-bi­pyridine) and the role of solvent water clusters in structure stability

In a two-dimensional cobalt(II) coordination polymer of benzene-1,2-di­carboxyl­ate and 4,4′-bi­pyridine, inter­planar cohesion is achieved via oligomeric solvent water clusters.

A one-dimensional ladder-like six-coordinate cadmium polymer: catena-poly[bis­[(S)-2-methyl­piper­azine-1,4-diium] [bis­[tri­chlorido­cadmium(II)]-di-μ₃-chlorido]]

An organic–inorganic hybrid complex consists of hydrogen-bonded 2-methyl­piperazinediium cations in the presence of one-dimensional polymeric {[CdCl₃(μ₃-Cl)]²⁻}_n anions. The Cd^II centres are hexa­coordinated by three terminal chlorides and three bridging chlorides and have a slightly distorted octa­hedral arrangement.

The mol­ecular structure of high-spin (S = ) manganese(II) phthalocyanine in tetra­butyl­ammonium bromido(phthalocyaninato)manganese(II)

The molecular structure of high-spin (S = ) manganese(II) bromide phthalocyanine as the tetrabutylammonium salt has been determined. The geometry of the Mn^IIN₄ fragment in this salt is similar to that of the high-spin (S = ) manganese(II) tetra­phenyl­porphyrin complex with 1-methyimidazole.

Substitutional disorder in Sr_2−yEu_yB_2−2xSi_2+3xAl_2−xN_8+x (x ≃ 0.12, y ≃ 0.10)

A novel nitride was synthesized from Sr₃N₂, EuN, Si₃N₄, AlN and BN under nitro­gen gas pressure. The structure consists of a host framework with Sr/Eu atoms accommodated in the cavities. The host framework is constructed by the linkage of MN₄ tetra­hedra (M = Si, Al) and BN₃ triangles, and contains substitutional disorder described by the alternative occupation of B₂ or Si₂N on the (0, 0, z) axis.

Two crown-ether-coordinated caesium halogen salts

In the crystal structures of two crown-ether-coordinated caesium halogen salt hydrates, hydrogen bonds between bromide ligands and water mol­ecules lead to one-dimensional chains running along the b axis in one compound, whereas two-dimensional sheets of water mol­ecules and chloride ligands are formed which combine with the polymeric caesium–crown polymer to give a three-dimensional network in the other complex. Although both compounds have a similar composition, i.e. a Cs⁺ cation with a halogen, an 18-crown-6 ether and a water ligand, the crystal structures are rather different. [OK?]

A new P,S-coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with Pd^II and Pt^II

Fc(PSPh₂)(CH₂SPSPh₂), a new chiral ferrocenyl (Fc) compound, is the precursor to a new P,S-coordinating ferrocenyl ligand, [Fc(PPh₂)(CH₂S)]⁻, which reacts with Pd and Pt precursors giving dinuclear complexes displaying a butterfly geometry.

Tris(2,2′-bi­pyridine)­iron(II) bis­(1,1,3,3-tetra­cyano-2-eth­oxy­propenide) dihydrate: chiral hydrogen-bonded frameworks inter­penetrate in three dimensions

Multiple hydrogen bonds in tris­(2,2′-bi­pyridine)­iron(II) bis­(1,1,3,3-tetra­cyano-2-eth­oxy­propenide) link water mol­ecules, anions and chiral cations into two inter­penetrating chiral frameworks.

Phase transitions and twinned low-temperature structures of tetra­ethyl­ammonium tetra­chlorido­ferrate(III)

At room temperature, tetra­ethyl­ammonium tetra­chlorido­ferrate(III) has a disordered structure in the high-hexa­gonal space group P6₃mc. At 230 K, the structure is merohedrally twinned in the low-hexa­gonal space group P6₃. At 170 and 110 K, the structure is identical in the ortho­rhom­bic space group Pca2₁ and twinned by reticular pseudomerohedry. All three space groups are polar and the direction of the polar axis is not affected by the twinning.

Synthesis, characterization and crystal structure of the new penta­hydrate of bis­(2,2′-bi­pyridine-κ²N,N′)(oxalato-κ²O¹,O²)nickel(II)

The new penta­hydrate of bis­(2,2′-bi­pyridine)­oxalatonickel(II) was obtained from a reaction at 281 K, whereas the previously reported tetra­hydrate was obtained at room temperature. The complex mol­ecules are involved in an extended system of hydrogen bonds with solvent water mol­ecules. Additionally, π–π inter­actions also contribute to the stabilization of the extended structure.

Intra- and inter­molecular Se⋯X (X = Se, O) inter­actions in selenium-containing heterocycles: 3-benzoyl­imino-5-(morpholin-4-yl)-1,2,4-diselen­azole

The Se⋯O distance of 2.302 (3) Å in the title compound, combined with a longer than usual amide C=O bond of 2.252 (5) Å, suggest a significant inter­action between the amide O atom and its adjacent Se atom. An analysis of related structures containing an Se—Se⋯X unit (X = Se, S, O) shows a strong correlation between the Se—Se bond length and the strength of the Se⋯X inter­action.

Cd^II and Co^II coordination polymers constructed from benzene-1,4-di­car­boxy­lic acid and 2-(pyridin-3-yl)-1H-benzimidazole ligands

A novel infinite two-dimensional cadmium(II) polymer and a one-dimensional cobalt(II) polymer constructed by benzene-1,4-di­carboxyl­ate ligands are formed. The two complexes are finally assembled to form three-dimensional network structures.

syn and anti conformations in 2-hy­droxy-5-[(E)-(4-nitro­phen­yl)diazen­yl]benzoic acid and two related salts

The comparison of the crystal structures of 5-(4-nitro­phenyl­diazen­yl)salicylic acid and two related salts shows that the intra­molecular O—H⋯O hydrogen bonds in the anions are stronger than that in the neutral mol­ecule. The nitro­phenyl­diazenyl and carb­oxy­lic acid/carboxyl­ate groups in the neutral molecule and the sodium salt are located anti to each other, whereas in the ammonium salt, the anion adopts a syn conformation.

A twofold inter­penetrating three-dimensional zinc–organic framework built from naphthalene-1,4-di­carboxyl­ate and 4,4′-bi­pyridine ligands

In a novel three-dimensional Zn^II complex prepared by the solvothermal assembly of Zn(NO₃)·6H₂O, naphthalene-1,4-di­carb­oxy­lic acid (1,4-H₂ndc) and 4,4′-bi­pyridine (bpy), the two crystallographically independent Zn atoms adopt the same four-coordinated tetra­hedral ZnO₃N geometry. The supra­molecular secondary building unit (SBU) is a distorted paddle-wheel-like {Zn₂(COO)₂N₂O₂} unit and these units are linked by 1,4-ndc ligands within the layer to form a two-dimensional net parallel to the ab plane, which is further connected by bpy ligands to give rise to a three-dimensional framework.

Zn/Mn–MOFs with `S-shaped' packing modes

Two novel polymers exhibiting metal–organic frameworks (MOFs) have been synthesized by the combination of a metal ion with benzene-1,3,5-tri­carboxyl­ic acid and 1,10-phenanthroline under hydro­thermal conditions. The overall topology of the Zn^II MOF is that of a 6³ net and that of the Mn^II MOF is a rutile net.

Two molybdenum penta­carbonyl complexes with electro­neutral phos­phane ligands: [bis­(morpholin-4-yl)(penta­fluoro­ethyl)phosphane-κP]penta­carbonylmolybdenum(0) and penta­carbonyl[(penta­fluoro­ethyl)bis­(piperidin-1-yl)phosphane-κP]molybdenum(0)

The structures of two new electro­neutral (penta­fluoro­ethyl)phosphane-ligand-containing Mo complexes are reported. Key distance and angle values are compared with those of similar complexes.

(H₃O)₂NaAl₃F₁₂, isostructural with A₂NaAl₃F₁₂ (A = K⁺, Rb⁺, Cs⁺) fluorides having HTB-type sheets

In the crystal structure of (H₃O)₂NaAl₃F₁₂, the hydrogen bonding of H₃O⁺ cations with F⁻ anions implies a strong tilt of the AlF₆ octa­hedra from the normal to the plane of the corrugated [AlF₄⁻]_n HTB (hexa­gonal tungsten bronze) layers.

A two-dimensional Cd^II coordination polymer with 2,2′-(disulfane­diyl)dibenzoate and 1,10-phen­anthroline ligands

A new two-dimensional cadmium(II) coordination polymer containing 44-membered metallamacrocycles and helical chains has been prepared under solvo­thermal conditions using flexible 2,2′-(disulfane­diyl)di­benzoate and 1,10-phenanthroline ligands.

Two different one-dimensional supra­molecular chains formed from the reaction of 2-[1-(pyridin-4-ylmethyl)-1H-benzimidazol-2-yl]quinoline with two different precursors, Co(NO₃)₂ and CoCl₂

Two different one-dimensional supra­molecular chains with Co^II cations have been synthesized based on the semi-rigid ligand 2-[1-(pyridin-4-ylmethyl)-1H-benzimidazol-2-yl)quinoline (L), obtained by condensation of 2-(1H-benzimidazol-2-yl)quinoline and 4-(chloro­methyl)pyridine hydro­chloride, and the precursors Co(NO₃)₂ and CoCl₂.