Hydro­gen‐bonded assemblages in 2,6‐bis­(hydroxy­methyl)‐4‐R‐phenol,with R = methyl,methoxy, phenoxy and 1‐(4‐methoxy­phenyl)‐1‐methyl­ethyl

Four derivatives of 2,6‐bis­(hydroxy­methyl)­phenol, with various para substituents, have been investigated; these are 2,6‐bis­(hydroxy­methyl)‐4‐methyl­phenol, C₉H₁₂O₃, (I), 2,6‐bis­(hydroxy­methyl)‐4‐methoxy­phenol, C₉H₁₂O₄, (II), 2,6‐bis­(hydroxy­methyl)‐4‐phenoxy­phenol, C₁₄H₁₄O₄, (III), and 2,6‐bis­(hydroxy­methyl)‐4‐[1‐(4‐methoxy­phenyl)‐1‐methyl­ethyl]­phenol, C₁₈H₂₂O₄, (IV). All four structures display hydrogen‐bonding networks resulting in sheets, with possible weak inter‐sheet π–π interactions in one case. In all the structures but one, the mol­ecules form centrosymmetric dimeric subunits held together by two hydrogen bonds between the hydroxy­methyl groups and, in two cases, by probable π–π interactions.     

Polymeric μ‐cyano‐di­cyano­nickelate(II)‐μ‐cyano‐trans‐bis­[N‐(2‐hydroxyethyl)ethyl­enedi­amine]­cadmium(II)

The title compound, catena‐poly­[[μ‐cyano‐1:2κ²C:N‐di­cyano‐1κ²C‐trans‐bis­[N‐(2‐hydroxy­ethyl)­ethane‐1,2‐di­amine‐2κ²N,N′]­cadmium(II)­nickel(II)]‐μ‐cyano‐1:2′κ²C:N], [CdNi(CN)₄(C₄H₁₂N₂O)₂], consists of alternating square‐planar Ni(CN)₄ fragments, formally dianionic, and Cd(hydet‐en)₂ moieties [hydet‐en is N‐(2‐hydroxy­ethyl)­ethyl­ene­di­amine], with the two bridging cyanide ligands in a mutually trans disposition at the Ni atom and cis at the Cd atom. The resulting one‐dimensional zigzag chain structure has the Ni atom on an inversion center, while the distorted octahedron centered on the Cd atom lies on a twofold axis. The polymer chains are connected into undulating sheets by weak interchain N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds, which are also present between successive sheets.     

1:1 Adduct of (S,S)‐4‐amino‐3,5‐bis­(1‐hydroxy­ethyl)‐1,2,4‐triazole with (S,S)‐1,2‐bis­(2‐hydroxy­propionyl)­hydrazine stabilized by eight hydrogen bonds

The structure of the cocrystallized 1:1 adduct of (S,S)‐4‐amino‐3,5‐bis­(1‐hydroxy­ethyl)‐1,2,4‐triazole and (S,S)‐1,2‐bis­(2‐hydroxy­propionyl)­hydrazine, C₆H₁₂N₄O₂·C₆H₁₂N₂O₄, has tetra­gonal symmetry. All eight O‐ and N‐bound H atoms are involved in inter­molecular hydrogen bonds, resulting in infinite zigzag chains of the triazole mol­ecules, with the hydrazine mol­ecules filling the gaps between the chains and completing a three‐dimensional hydrogen‐bonded array.     

Unexpected oxidation of a diphos­phine by bis­(1,3‐diphenylpropane‐1,3‐dionato)­cobalt(II), [Co(dbm)2]

The reaction of bis­(1,3‐diphenylpropane‐1,3‐dionato)cobalt(II), [Co(dbm)₂], with bis­(diphenyl­phosphino)ethane (dppe) affords the coordination polymer catena‐poly[[bis­(1,3‐diphenyl­propane‐1,3‐dionato‐κ²O,O′)cobalt(II)]‐μ‐ethyl­enebis(diphenyl­phosphine oxide)‐κ²O:O′], trans‐[Co(C₁₅H₁₁O₂)₂(C₂₆H₂₄O₂P₂)]_n, as a result of oxidation of the diphos­phine. The Co atom is octa­hedral, with a CoO₆ coordination sphere, and the chelating dbm ligands adopt a trans configuration. The Co atom also lies on a centre of inversion, with a further symmetry centre bis­ecting the bridging ethyl­enebis(diphenyl­phosphine oxide) ligand.     

A dinuclear uranium(IV) complex of the chelating ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene

The ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene (cp*py) forms a dinuclear complex with U^IV, i.e. di‐μ‐oxo‐bis­{chloro­(diethyl ether‐κO)[(η⁵,κN)‐1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­dienyl]uranium(IV)}, [U₂Cl₂O₂(C₁₄H₁₆N)₂(C₄H₁₀O)₂], in which cp*py acts as a chelating ligand, being bound to the metal atom by the cyclo­penta­dienyl unit and also by the N atom of the pyridyl ring.     

Bis­(di‐μ‐acetato‐aqua{2‐[N‐ethyl‐N‐(2‐hydroxy‐4‐methyl­benzyl)­amino­methyl]‐1‐methyl­benz­imid­az­ole}­nickel)­nickel(II) tetra­hy­drate

The previously unknown title compound, tetra‐μ‐ace­tato‐1:2κ²O;1:2κ²O:O′;­2:3κ²O;­2:3κ²O:O′‐di­aqua‐1κO,3κO‐bis­(μ‐2‐{[N‐ethyl‐N‐(2‐hy­droxy‐5‐methylbenzyl)­am­ino]­methyl}‐1‐methyl‐1H‐benz­imid­az­ole)‐1κ³N³,N,O:2κO;3κ³N³,N,O:2κO‐tri­nickel(II) tetra­hy­drate, [Ni₃(C₁₈H₂₂N₃O)₂(C₂H₃O₂)₄(H₂O)₂]·­4H₂O, (I), is a centrosymmetric linear trinuclear nickel(II) complex, where the Ni atoms are in an octahedral coordination and the ligand heteroatoms act so as to model amino acid residues.     

Redetermination of hexa­carbonyl­(η5‐cyclo­penta­dienyl)­bis(μ3‐selenido)­diiron(II)­cobalt(II)

The structure of the title compound, hexa­carbonyl‐1κ³C,2κ³C‐[3(η⁵)‐cyclo­penta­dienyl]­bis(μ₃‐selenido)­diiron(II)­cobalt(II),[CoFe₂(μ₃‐Se)₂(C₅H₅)(CO)₆], was redetermined at room temperature and the correct C2/c space group was assumed instead of the previously reported P space group [Mathur et al. (1995). Organometallics, 14 , 2115–2118]. Analysis of the literature data showed that the previously reported triclinic parameters correspond to a primitive subcell of the actual monoclinic C‐centred cell with cell dimensions close to those found by us. The title compound appeared to be isostructural with the sulfur–selenium analogue.     

Hexakis­(antipyrine‐O)­terbium(III) triperchlorate

In the title compound, hexakis(1,2‐di­hydro‐1,5‐di­methyl‐2‐phenyl‐3H‐pyrazol‐3‐one‐O)­terbium(III) triperchlorate, [Tb(C₁₁H₁₂N₂O)₆](ClO₄)₃, the Tb atom lies on a site of crystallographic symmetry and the unique Tb—O distance is 2.278 (2) Å. One of the perchlorate anions has threefold crystallographic symmetry, while the other is disordered about a site.     

Secondary inter­actions in gold(I) complexes with thione ligands. 5. Two ionic compounds of the form bis­(thione)gold(I) bis(4‐halobenzene­sulfon­yl)amide

Bis(1,3‐thia­zolidine‐2‐thione‐κS²)gold(I) bis­(4‐chloro­benzene­sulfonyl)amide, [Au(C₃H₅NS₂)₂](C₁₂H₈Cl₂NS₂O₄), has no imposed symmetry. Classical N—H⋯N and N—H⋯O hydrogen bonds link the residues to form chains parallel to the b axis. Weaker inter­actions involve C—H⋯O, C—H⋯Au and a number of X⋯Cl contacts (X = Cl, S or Au) clustered in the region y ≃ . In bis­(1‐methyl­imidazolidine‐2‐thione‐κS²)gold(I) bis­(4‐iodo­benzene­sulfonyl)amide, [Au(C₄H₈N₂S)₂](C₁₂H₈I₂NS₂O₄), the Au atom of the cation and the N atom of the anion lie on the twofold axis (0, y, ) in the space group C2/c. The formula unit forms a self‐contained ring with two symmetry‐equivalent N—H⋯O hydrogen bonds, and weak C—H⋯X (X = O, I or S), Au⋯I and I⋯I contacts are observed. In both compounds, the anions display extended conformations.     

First‐ and second‐ sphere coordination of the uranyl ion by bis­[2‐(2‐hydroxy­phenoxy)­ethoxy]­ethane

Uranyl nitrate hexahydrate reacts with bis­[2‐(2‐hydroxy­phenoxy)­ethoxy]­ethane (C₁₈H₂₂O₆), denoted LH₂ hereafter, in the presence of triethylamine to give ­triethylammonium aqua[2,2′‐(3,6‐dioxaoctane‐1,8‐diyldioxy)diphenolato‐κ²O,O′](nitrato‐κ²O,O′)dioxouranium(VI), (Et₃NH)[UO₂(H₂O)L(NO₃)], which possesses a symmetry plane. The uranyl ion is coordinated to the two phenoxide O atoms, a nitrate ion and a water mol­ecule (first sphere); the water mol­ecule is itself held in the crown ether chain by hydrogen‐bonding interactions, thus ensuring second‐sphere coordination by the ligand L.     

A novel Na–O–Ni–O–Ni bridging complex of Cl‐HXTA,where Cl‐HXTA is 2,6‐bis{[bis­(carboxyl­ato­methyl)­amino]­methyl}‐4‐chloro­phenolate

In the structure of the title compound, hepta­aqua‐1κ³O,2κ²O,3κ²O‐(μ₃‐2,6‐bis{[bis­(carboxyl­ato­methyl)­amino]methyl}‐4‐chloro­phenolato‐1κO;2κ⁴O,O′,N,O¹;3κ⁴O¹N′,O′′,O′′′)dinickel(II)­sodium(I) pentahydrate, [NaNi₂(C₁₆H₁₄ClN₂O₉)(H₂O)₇]·5H₂O or [Ni₂(Cl‐HXTA)(H₂O)₄{Na(H₂O)₃}]·5H₂O, the trinuclear complex unit consists of two distorted NiNO₅ octahedra bridged by a phenolate O atom and an NaO₄ tetrahedron bridged to one of the Ni octahedra by a carboxylate O atom. There are four intramolecular hydrogen bonds forming four six‐membered rings in the complex and the complex mol­ecules are connected to each other by a very complicated hydrogen‐bond network.     

Azido­[1,1′‐bis­(di­phenyl­phosphino)­ferrocene](penta­methyl­cyclo­penta­dienyl)­rhodium(III) hexa­fluoro­phosphate

In the title compound, azido‐2κN‐bis­[μ‐(1η⁵:2κP)‐di­phenyl­phosphino­cyclo­penta­dienyl][2(η⁵)‐penta­methyl­cyclo­penta­di­enyl]­iron(III)­rhodium(III) hexa­fluoro­phosphate, [{Rh(C₁₀H₁₅)(N₃)}{Fe(μ‐C₁₇H₁₄P)₂}]PF₆ or [FeRh(C₁₀H₁₅)(μ‐C₁₇H₁₄P)₂(N₃)]PF₆, the coordination sphere of Rh^III can be described as pseudo‐tetrahedral, composed of two P atoms from a 1,1′‐bis­(di­phenyl­phosphino)­ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C₅Me₅ (Cp*) ligand. The two cyclo­penta­dienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh⋯Fe distance is 4.340 (2) Å.     

Layered structures in proton‐transfer compounds of 5‐sulfosalicylic acid with the aromatic polyamines 2,6‐diamino­pyridine and 1,4‐phenyl­ene­diamine

The crystal structures of two proton‐transfer compounds of 3‐carb­oxy‐4‐hydroxy­benzene­sulfonic acid (5‐sulfosalicylic acid) with the aromatic polyamines 2,6‐diamino­pyridine [namely 2,6‐diamino­pyridinium 3‐carb­oxy‐4‐hydroxy­benzene­sulfonate monohydrate, C₅H₈N₃⁺·C₇H₅O₆S⁻·H₂O, (I)] and 1,4‐phenyl­ene­diamine [namely 1,4‐phenyl­ene­diaminium 3‐carboxyl­ato‐4‐hydroxy­benzene­sulfonate, C₆H₁₀N₂²⁺·C₇H₄O₆S²⁻, (II)] have been determined. Both compounds feature extensively hydrogen‐bonded three‐dimensional layered polymer structures having significant inter­layer π–π inter­actions between the cation and anion species. In (I), the pyridine N atom of the Lewis base is protonated and forms a direct hydrogen‐bonding inter­action with the water mol­ecule, which together with the two amine groups of the cation and the carboxylic acid group of the anion also give additional inter­actions with O‐atom acceptors of the sulfonate group. In (II), a dianionic species results from deprotonation of both the sulfonic and the carboxylic acid groups, and all available O‐atom acceptors inter­act with all dication donors, which lie about inversion centres.     

{2,5‐Bis[3‐(tert‐butyl­aminoxyl)­phenyl]‐1,1‐dimethyl‐3,4‐diphenyl­silole‐κO}bis­(1,1,1,5,5,5‐hexa­fluoro­pentane‐2,4‐dionato)­manganese(II)

In the structure of the first bis‐adduct of 2,5‐bis­[3‐(tert‐butyl­aminoxyl)­phenyl]‐1,1‐dimethyl‐3,4‐diphenyl­silole with bis­(hexa­fluoro­acetyl­acetonato)­manganese(II), [Mn(C₅HF₆O₂)₂(C₃₈H₄₂N₂O₂Si)₂], the Mn atom lies on a crystallographic inversion centre and is bound to two chelating hexafluoro­acetylacetonate ligands and two monodentate nitroxide groups in a distorted octa­hedral configuration. The silole ligands present a propeller‐like arrangement of the benzene rings around the Si‐containing five‐membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand.     

Hydro­gen bonding in proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases

The crystal structures of quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate trihydrate, C₉H₈N⁺·C₇H₅O₆S⁻·3H₂O, (I), 8‐hydroxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate monohydrate, C₉H₈NO⁺·C₇H₅O₆S⁻·H₂O, (II), 8‐amino­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate dihydrate, C₉H₉N₂⁺·C₇H₅O₆S⁻·2H₂O, (III), and 2‐carboxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate quinolinium‐2‐carboxylate, C₁₀H₈NO₂⁺·C₇H₅O₆S⁻·C₁₀H₇NO₂, (IV), four proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases, reveal in each the presence of variously hydrogen‐bonded polymers. In only one of these compounds, viz. (II), is the protonated quinolinium group involved in a direct primary N⁺—H⋯O(sulfonate) hydrogen‐bonding interaction, while in the other hydrates, viz. (I) and (III), the water mol­ecules participate in the primary intermediate interaction. The quinaldic acid (quinoline‐2‐carboxylic acid) adduct, (IV), exhibits cation–cation and anion–adduct hydrogen bonding but no direct formal heteromolecular interaction other than a number of weak cation–anion and cation–adduct π–π stacking associations. In all other compounds, secondary interactions give rise to network polymer structures.     

A one‐dimensional zigzag coordination polymer of di­aqua­(pyridine‐2,3‐di­carboxyl­ato)­cobalt(II)

The asymmetric unit of the title one‐dimensional coordination polymer, catena‐poly­[[μ‐pyridine‐2,3‐di­carb­oxyl­ato‐1κO:2κ²N,O′‐bis­[di­aqua­cobalt(II)]]‐μ‐pyridine‐2,3‐di­carboxyl­ato‐1κ²N,O:2κO′:1′κO′], [Co(C₇H₃NO₄)(H₂O)₂]_n, is composed of a cobalt(II) ion, a pyridine‐2,3‐di­carboxyl­ate dianion and two water mol­ecules. The polymer has a zigzag structure consisting of a chain of edge‐fused rings, and the polymer chains are linked by O—H⃛O hydrogen bonds into a three‐dimensional framework.     

trans‐Bis­(diethano­lamine)­bis­(iso­thio­cyanato)­nickel(II)

In the neutral title complex, trans‐bis(2,2′‐imino­di­ethanol‐N,O)­bis­(iso­thio­cyanato)­nickel(II), [Ni(NCS)₂(C₄H₁₁NO₂)₂], the iso­thio­cyanate ions and the di­ethanol­amine mol­ecules act as mono­dentate and bi­dentate ligands, respectively. The Ni^II ion exhibits a distorted octahedral configuration with crystallographically imposed inversion symmetry and N_NCS—Ni—N_amine and N_NCS—Ni—O_amine bond angles of 88.78 (10) and 89.44 (10)°, respectively. The Ni—N bond distances are in the range 2.069 (3)–2.096 (2) Å. The mol­ecules are linked by hydrogen bonds to form a three‐dimensional infinite lattice.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

{Bis­[2‐(2‐oxido‐1‐naphthylmethylidene­amino)­phenyl] disulfide}chloroiron(III)

The crystal structure of the title compound, {bis­[2‐(2‐oxido‐2‐naphthyl­idene­amino)­phenyl] di­sulfide‐κ⁵O,N,S,N′,O′}chloroiron(III), [FeCl(C₃₄H₂₂N₂O₂S₂)], has been determined. The structure consists of monomeric iron(III) complexes with distorted octahedral coordination. The di­sulfide functions as a pentadentate ligand and the Fe^III atom is coordinated through two N, two O and one S atom, and one chloride ion. The distance between the second S atom and the Fe^III atom is a non‐bonding 3.8473 (14) Å.     

Di­aqua­bis(4,5‐di­hydro‐1,2,4‐triazolo[1,5‐a]­pyrimidin‐5‐one‐N3)bis­(thiocyanato‐N)­nickel(II)

The title compound, [Ni(NCS)₂(C₅H₄N₄O)₂(H₂O)₂], crystallizes in the triclinic space group P. The molecular unit contains two neutral mol­ecules of 4,5‐di­hydro‐1,2,4‐triazolo[1,5‐a]­pyrimidin‐5‐one (5HtpO) coordinated through the N atom in position 3, two thio­cyanate ligands coordinated through their N atoms and two water mol­ecules completing an octahedral environment around the Ni^II ion, which lies on a centre of inversion. The structure is stabilized by hydrogen bonding. Distances in the coordination sphere are Ni—N3(5HtpO) 2.132 (2), Ni—O(water) 2.085 (2) and Ni—N(thio­cyanato) 2.040 (2) Å.