Inhibition of a palladium(II) catalyst upon formation of a di‐μ‐chloro complex: di‐μ‐chloro‐bis­[1,2‐bis­(di­phenyl­phosphino)­ethane‐P,P′]dipalladium(II) bis­(tetra­fluoro­borate) bis­(deutero­chloro­form) solvate

The title compound was formed upon slow evaporation of a solution of the solvated dicationic complex bis­(aceto­nitrile)­bis­[1,2‐bis­(di­phenyl‐phosphino)­ethane]­palladium(II) bis(tetra­fluoro­borate) in deuterated chloro­form. The dinucleur palladium complex forms triclinic crystals and there is an inversion center between the Pd atoms. Compared to the corresponding monomeric compound, the Cl—Pd—Cl angles decrease upon briding from 94.19 (7) to 86.96 (4)°.     

Bis[2‐(3‐pyridinio)benzimidazolium] di‐μ‐chloro‐bis­[trichloro­cadmium(II)]

The title compound, (C₁₂H₁₁N₃)₂[Cd₂Cl₈], consists of two discrete 2‐(3‐pyridinio)benzimidazolium cations and one [Cd₂Cl₈]⁴⁻ anion. The dimeric [Cd₂Cl₈]⁴⁻ anion lies about an inversion centre and consists of two distorted [CdCl₅] trigonal bipyramids which share a common edge. The two Cd atoms are each coordinated by two μ‐Cl atoms and three terminal Cl atoms, with a Cd·Cd separation of 3.9853 (6) Å. The packing displays two‐dimensional hydrogen‐bonded sheets, which are further linked by C—H·Cl contacts and π–π stacking inter­actions to yield a three‐dimensional network.     

Bis­[N,N′‐diiso­propyl‐N‐(tri­methyl­silyl)­benzamidinium] di‐μ‐chloro‐bis­[tetra­chloro­zirconate(IV)] di­chloro­methane disolvate

The structure of the salt of the di‐μ‐chloro‐bis­[tetra­chloro­zirconate(IV)] anion and the N,N′‐iso­propyl‐N‐(tri­methyl­silyl)benzamidinium cation, (C₁₆H₂₉N₂Si)₂[Zr₂Cl₁₀]·2CH₂Cl₂, is reported. The anion lies about an inversion centre and shows a substantially octahedral coordination around Zr, while the structure of the cation is unequivocally assigned as that of a benzamidinium ion.     

Di‐μ‐benzoato‐bis­[di­carbonyl­(pyri­dine)­ruthenium(I)] (new polymorph) and di‐μ‐tri­fluoro­acetato‐bis­[di­carbonyl­(pyridine)­ruthenium(I)]

The syntheses and crystal structure determinations of a pair of `sawhorse' dimers are reported, viz. [Ru₂(C₆H₅CO₂)₂(C₅H₅N)₂(CO)₄] [a new polymorph, cf. Kepert, Deacon, Spiccia, Fallon, Skelton & White (2000). J. Chem. Soc. Dalton Trans. pp. 2867–2874] and [Ru₂(CF₃CO₂)₂(C₅H₅N)₂(CO)₄]. The Ru⋯Ru distances are 2.6724 (2) and 2.7122 (5) Å, respectively.     

Bis(μ‐ethyl pyridine‐2,6‐di­carboxyl­ato)­bis­[di­aqua­chloro­cadmium(II)] dihydrate

The reaction of cadmium chloride with pyridine‐2,6‐di­carboxylic acid (PDA) and 98% H₂SO₄ in ethanol led to the formation of the title compound, bis­[μ‐6‐(ethoxy­carbonyl)­pyridine‐2‐carboxyl­ato]‐1:2κ⁴O⁶,N,O²:O²;1:2κ⁴O²:O²,N,O⁶‐bis­[di­aqua­chloro­cadmium(II)] dihydrate, [Cd₂(C₉H₈NO₄)₂Cl₂(H₂O)₄]·2H₂O. PDA is esterified to monoethyl ­pyridine‐2,6‐di­carboxyl­ate (MEPD) by the catalysis of H₂SO₄ during the reaction. The dinuclear Cd^II complex lies about an inversion centre and the unique Cd atom has a pentagonal–bipyramidal geometry. The two Cd atoms are bridged by two carboxyl­ate O atoms, forming a planar Cd₂O₂ unit. Stair‐like chains are formed via O—H⋯Cl hydrogen bonds and these are further arranged into two‐dimensional layers via hydrogen bonds involving solvate water mol­ecules.     

Bis{μ‐2‐[3‐(cyclo­hexyl­ammonio)­propyl­imino­methyl]­phenolato}bis­[di­chloro­copper(II)]

The title compound, [Cu₂(C₁₆H₂₄N₂O)₂Cl₄], is a dinuclear copper(II) complex with inversion symmetry. Each Cu^II atom is five‐coordinated by two O and one N atom from two Schiff base ligands, and by two Cl atoms, giving an approximately trigonal–bipyramidal coordination environment.     

Poly[bis­[2‐(1‐cyclo­hexen­yl)ethyl­ammonium] di‐μ‐iodo‐diodo­plumbate(II)]

The title compound, (C₈H₁₆N)₂[PbI₄], crystallizes as an inorganic–organic hybrid perovskite, adopting the unusual 2a_p× 2a_p superstructure. As such, the structure consists of two‐dimensional sheets of corner‐sharing PbI₆ octa­hedra in the ab plane, separated by bilayers of 2‐(1‐cyclo­hexen­yl)ethyl­ammonium cations. The ethyl­ammonium groups are not in the plane of the cyclo­hexenyl rings.     

Aqua­di­chloro­(di‐2‐pyridyl­di­azene)copper(II) monohydrate

The crystal structure of the mononuclear title complex, [CuCl₂(C₁₀H₈N₄)(H₂O)]·H₂O, shows an s‐cis/E/s‐trans‐configured di‐2‐pyridyl­diazene ligand, with the square‐pyramidal Cu^II ion coordinated to one pyridyl and one diazene N atom together with two Cl atoms and one aqua ligand. The crystal packing involves both hydrogen‐bonding and π–π interactions. The solvent water mol­ecule links three monomers to one another through hydrogen‐bonding interactions in which two monomers are linked via chloro ligands and the third via the aqua ligand. Face‐to‐face and weak slipped π–π interactions also occur between di‐2‐pyridyl­diazene moieties, and these interactions are responsible for the interchain packing.     

A mixed‐valence CuII/CuI anion–cation complex: bis­[μ‐5‐sulfosali­cylato(3–)]bis­[(di‐2‐pyridylamine)­copper(II)] bis­[bis­(di‐2‐pyridyl­amine)copper(I)] dihydrate

The title compound, [Cu(C₇H₃O₆S)₂(C₁₀H₉N₃)₂][Cu^I(C₁₀H₉N₃)₂]₂·2H₂O, consists of anionic Cu^II moieties, cationic Cu^I species and uncoordinated water mol­ecules. The anionic dimeric unit consists of one crystallographically independent fully deprotonated 5‐sulfosalicylate (2‐oxido‐5‐sulfonatobenzoate) anion, a di‐2‐pyridylamine group and a Cu^II atom. Each Cu^II atom is five‐coordinate within a square‐pyramidal geometry. The anion lies on a special position of site symmetry. In the cationic monomer, the Cu^I atom adopts tetra­hedral geometry. The cations and anions are connected by O—H·O and N—H·O hydrogen bonds.     

cis‐Di­chloro­bis­(triphenyphosphite‐P)palladium(II)

In the title compound, [PdCl₂{P(OPh)₃}₂], the Pd^II centre shows slightly distorted square‐planar geometry, with the two chloro ligands in cis positions.     

A chloro‐bridged dinuclear phosphinitopalladium complex,di‐μ‐chloro‐bis­[(diphenoxy­phosphinite‐κP)(diphenoxy­phosphinito‐κP)palladium(II)]

The title compound, [Pd₂(C₁₂H₁₀O₃P)₂Cl₂(C₁₂H₁₁O₃P)₂], consists of a dinuclear μ‐chloro‐bridged palladium unit with two diphenoxy­phosphinite groups per Pd atom, linked together by a hydrogen bond. The asymmetric unit contains one half of the mol­ecule, with the other half generated by an inversion centre. The geometry around the P atoms may be described as distorted tetra­hedral. Adjacent mol­ecules of the complex are linked by weak C—H⋯O and C—H⋯Cl hydrogen bonds. The structure is additionally stabilized by π–π stacking inter­actions between the aryl rings. These inter­actions form a herring‐bone pattern in the crystal structure.     

Bis­[tris­(ethyl­enedi­amine)­cobalt(III)] di­chloro­bis­[μ‐(1‐hydroxy­ethyl­idene)­di­phospho­nato(4–)]­di­ruthenium(II,­III)­(Ru–Ru) chloride trihydrate

In the title compound, [Co(C₂H₈N₂)₃]₂[Ru₂(C₂H₄O₇P₂)₂Cl₂]Cl·3H₂O, the building unit contains two crystallographically independent dinuclear [Ru₂(hedp)₂Cl₂]⁵⁻ anions, where hedp [viz. (1‐hydroxy­ethyl­idene)­di­phospho­nate] serves as a bis‐chelating bridging ligand, two types of [Co(en)₃]³⁺ cations, one uncoordinated Cl⁻ anion and five water mol­ecules of crystallization. The [Ru₂(hedp)₂Cl₂]⁵⁻ anions are connected to one another, forming one‐dimensional chains along the a axis. The [Co(en)₃]³⁺ cations are located between these chains and lie across inversion centres. An extensive series of hydrogen bonds lead to the formation of a three‐dimensional supramol­ecular network structure, with channels generated along the [100] direction. The uncoordinated water mol­ecules and Cl⁻ anions reside in these channels.     

Hemi[hexa­aqua­magnesium(II)] (μ‐2,6‐bis{[bis­(carboxyl­ato­methyl)­amino]­methyl}‐4‐chloro­phenolato)­bis­[di­aqua­magnesium(II)] decahydrate

The crystal structure of the title compound, [Mg(H₂O)₆]_0.5[Mg₂(C₁₆H₁₄ClN₂O₉)(H₂O)₄]·10H₂O, shows that this bi­nuclear complex consists of two Mg centres in distorted octahedral geometry, joined by an oxo bridge which is a derivative of the deprotoned hydroxy group of the phenolate in the ligand mol­ecule. In the anion, the coordination sphere of each Mg^II ion is completed by two carboxyl­ates, a tertiary N atom and two water mol­ecules. The inner coordination spheres for the Mg^II ions are very similar, both in ligand sets and in geometry. Each unit of the binuclear complex has one negative charge neutralized by a neighbouring hydrated cation, [Mg(H₂O)₆]²⁺, in which the Mg atom lies on an inversion centre. In each cell, there are 34 water mol­ecules and most of them participate in the formation of hydrogen bonds, which contribute greatly to the stability of the whole structure.     

Bis­[bis­(di­phenyl­phosphino­methyl)­phenyl­phosphine]­di­chloro­tetra­gold(I) bis­[chloro­tris­(penta­fluoro­phenyl)­aurate(III)]

The cation of the title compound, [Au₄(PPh₂CH₂PPhCH₂PPh₂)₂Cl₂][Au(C₆F₅)₃Cl]₂ or [Au₄Cl₂(C₃₂H₂₉P₃)₂][AuCl(C₆F₅)₃]₂, displays a rhomboidal geometry for the Au atoms, with short Au?Au distances of 3.104 (2) and 3.185 (1) Å; the linear coordination at the Au^I atoms is distorted: P—Au—P 164.7 (2)° and P—Au—Cl 170.67 (11)°. The anion shows the expected square‐planar geometry at Au^III, with the Au atom 0.022 (5) Å out of the plane of the four donor atoms.     

Poly­[di­aqua­cobalt(II)‐di‐μ4‐benzene‐1,2,4‐tri­carboxyl­ato‐bis­[1,10‐phenanthrolinecobalt(II)]]

In the polymeric title compound, [Co₃(btc)₂(phen)₂(H₂O)₂]_n [btc is the benzene‐1,2,4‐tri­carboxyl­ate trianion (C₉H₃O₆) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], there are two different Co centres, Co1 and Co2. The Co1 centre has a deformed trigonal–bipyramidal geometry, while the Co2 centre lies on an inversion centre and has distorted octahedral geometry. Moreover, the 1,2‐di­carboxyl­ate groups of one btc ligand bridge the two adjacent Co2 centres, and each Co2 centre is coordinated by four carboxyl­ate O atoms from four different btc ligands, forming a novel kind of intersecting double‐chain structure, with a Co⋯Co separation of 7.755 Å, along the a axis. On the other hand, the two Co1 centres are bridged by two btc ligands and chelated by phen mol­ecules, respectively, producing a binuclear unit with a Co⋯Co separation of 8.406 Å, and these binuclear units are linked by btc bridges and Co2 centres to extend hybrid chains of Co1 and Co2 along the [101] direction. Furthermore, each btc ligand acts as a pentadentate bridge, linking the Co2 double‐chain structures and the hybrid chains of Co1 and Co2 to yield a two‐dimensional network, and this leads to the formation of very different kinds of voids.     

cis‐μ‐Chloro‐μ‐p‐toluene­thiol­ato‐bis­[chloro­(triethyl­phos­phine)­palladium]

The title compound, cis‐[Pd₂Cl₃(C₇H₇S)(C₆H₁₅P)₂], has bridging chloro and aryl­thiol­ato groups, with the phosphines being trans to the bridging chloro group. The four‐membered metallocyclic Pd₂ClS ring is unexpectedly non‐planar, with a dihedral angle of 133.8 (1)° between the PdCl₂SP coordination planes. Principal dimensions include Pd—Cl_t 2.316 (3) and 2.329 (3), Pd—Cl_b 2.442 (3) and 2.432 (3), Pd—S 2.280 (3) and 2.282 (3), and Pd—P 2.233 (3) and 2.236 (3) Å (where Cl_t and Cl_b are terminal and bridging chloro ligands, respectively).     

Bis(μ‐6‐hydroxy­picolinato)‐μ‐oxo‐bis­[di­pyridine­manganese(III)] monohydrate

The title compound, [Mn₂(μ‐O)(C₆H₃NO₃)₂(C₅H₅N)₄]·H₂O, was isolated from the reaction of 2,6‐pyridine­di­carboxylic acid with [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄] in pyridine. The dimanganese complex has twofold symmetry; the Mn^III atoms are bridged by one oxo and two amidate ligands and show compressed octahedral Jahn–Teller distortion. The molecular packing comprises a three‐dimensional structure constructed by means of extensive intermolecular interactions, including three kinds of hydrogen bonds and π–π interactions.     

μ‐Oxo‐bis­[(2,3,12,13‐tetra­bromo‐5,10,15,20‐tetra­phenyl­porphyrinato)­iron(III)] bis­(di­chloro­methane) solvate

The precise structure of the title compound, [Fe₂O(C₄₄H₂₄Br₄N₄)₂]·2CH₂Cl₂, is reported. The Fe—N distances are non‐equivalent in pairs because of the asymmetric peripheral substitution; the values are 2.098 Å to the brominated rings and 2.041 Å to the other two rings. The Fe—O bond distance is 1.7583 (4) Å. The mol­ecule has required twofold symmetry so that there is one unique porphyrin macrocycle and one Fe—O bond length in contrast to a previous report on the same species.     

The allyl complex di‐μ‐chloro‐bis­{[(1,2,3‐η)‐4‐oxo‐5,5‐di­methyl‐1‐(ethoxy­carbonyl)­hexenyl]palladium(II)}

The title compound, di‐μ‐chloro‐bis{[(2,3,4‐η)‐ethyl 6,6‐di­methyl‐5‐oxohept‐2‐enoato]­palladium(II)}, [Pd₂Cl₂(C₁₁­H₁₇­O₃)₂], is a binuclear chloro‐bridged palladium allyl complex that was obtained serendipitously From the reaction of 6,6‐di­methyl‐2‐hepten‐4‐ynoate with Na₂PdCl₄ in water‐containing alcohol. The allyl group is substituted with an ester and a tert‐butyl­carboxy group. The dimeric mol­ecules link via C—H?O contacts into a two‐dimensional network parallel to the bc plane.     

A linear Fe–O–Fe unit in bis­(dibenzyl­dimethyl­ammonium) μ‐oxo‐bis­[tribromo­ferrate(III)]

The title compound, (C₁₆H₂₀N)₂[Fe₂Br₆O], crystallizes with one dibenzyl­dimethylammonium cation and one half of a μ‐oxo‐bis­[tribromo­ferrate(III)] anion in the asymmetric unit. The bridging oxo group is situated on an inversion centre, resulting in a linear conformation for the Fe—O—Fe unit. The iron(III) cations have tetra­hedral geometry, with bond angles in the range 106.8 (1)–112.2 (1)°. The ion pairs are held together by Coulombic forces and C—H⋯Br hydrogen bonds. Each Br⁻ anion forms one hydrogen bond. No C—H⋯O hydrogen bonds are found between the O atom in the Fe—O—Fe unit and surrounding counter‐cations, consistent with the linear configuration of the Fe—O—Fe unit.