5‐n‐Butylpyridine‐2‐carboxylate–copper(II) and –iron(III) complexes

In trans‐bis(5‐n‐butyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­bis­(methanol‐κO)copper(II), [Cu(C₁₀H₁₂NO₂)₂(CH₄O)₂], the Cu atom lies on a centre of symmetry and has a distorted octahedral coordination. The Cu—O(methanol) bond length in the axial direction is 2.596 (3) Å, which is much longer than the Cu—­O(carboxylate) and Cu—N distances in the equatorial plane [1.952 (2) and 1.977 (2) Å, respectively]. In mer‐tris(5‐n‐bu­tyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­iron(III), [Fe(C₁₀H₁₂NO₂)₃], the Fe atom also has a distorted octahedral geometry, with Fe—O and Fe—N bond‐length ranges of 1.949 (4)–1.970 (4) and 2.116 (5)–2.161 (5) Å, respectively. Both crystals are stabilized by stacking interactions of the 5‐n‐butyl­pyridine‐2‐carboxyl­ate ligand, although hydrogen bonds also contribute to the stabilization of the copper(II) complex.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

[N,N′‐Bis(5‐bromo­salicyl­idene)‐1,3‐di­amino­propane]­nickel(II) and [N,N′‐­bis(5‐chloro­salicyl­idene)‐1,3‐­di­amino­propane]copper(II)

The title compounds, {4,4′‐di­bromo‐2,2′‐[1,3‐propane­diyl­bis(nitrilo­methyl­idyne‐N)]­diphenolato‐O,O′}nickel(II), [Ni(C₁₇­H₁₄­Br₂­N₂O₂)], and {4,4′‐di­chloro‐2,2′‐[1,3‐pro­pane­diyl­bis­(ni­trilo­methyl­idyne‐N)]­di­phen­ol­ato‐O,O′}­copper(II), [Cu­(C₁₇­H₁₄­Cl₂­N₂O₂)], lie on crystallographic twofold axes. In both structures, the metal coordination sphere is a tetrahedrally distorted square plane formed by the four‐coordinate N₂O₂ donor set of the Schiff base imine–phenol ligands. In the Ni compound, the Ni—O and Ni—N distances are 1.908 (3) and 1.959 (4) Å, respectively, while in the Cu compound, the Cu—O and Cu—N distances are 1.907 (2) and 1.960 (2) Å, respectively. The two Schiff base moieties, which themselves are nearly planar, are inclined at an angle of 29.26 (7)° for the Ni compound and 29.26 (5)° for the Cu compound.     

catena‐Poly­[[[1,8‐bis(2‐hydroxy­ethyl)‐1,3,6,8,10,13‐hexa­aza­cyclo­tetra­decane]copper(II)]‐μ‐cyano‐[tri­cyano­nitro­soiron(III)]‐μ‐cyano]

The bimetallic title complex, [CuFe(CN)₅(C₁₂H₃₀N₆O₂)(NO)] or [Cu(L)Fe(CN)₅(NO)] [where L is 1,8‐bis(2‐hydroxy­ethyl)‐1,3,6,8,10,13‐hexa­aza­cyclo­tetra­decane], has a one‐dimensional zigzag polymeric –Cu(L)–NC–Fe(NO)(CN)₃–CN–Cu(L)– chain, in which the Cu^II and Fe^II centres are linked by two CN groups. In the complex, the Cu^II ion is coordinated by four N atoms from the L ligand [Cu—N(L) = 1.999 (2)–2.016 (2) Å] and two cyanide N atoms [Cu—N = 2.383 (2) and 2.902 (3) Å], and has an elongated octahedral geometry. The Fe^II centre is in a distorted octahedral environment, with Fe—N(nitroso) = 1.656 (2) Å and Fe—C(CN) = 1.938 (3)–1.948 (3) Å. The one‐dimensional zigzag chains are linked to form a three‐dimensional network via N—H⋯N and O—H⋯N hydrogen bonds.     

Dimeric copper(II) trimethylsilyl­acetate adducts with pyridine, 2‐­methylpyridine, 3‐methylpyridine and quinoline,and a polymeric copper(II) trimethylsilylacetate

In the crystals of bis(pyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₅H₅N)₂], (I), the dinuclear Cu^II complexes have cage structures with Cu?Cu distances of 2.632 (1) and 2.635 (1) Å. In the crystals of bis(2‐­methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₆H₇N)₂], (II), bis­(3‐methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₆H₇N)₂], (III), and bis(quinoline‐N)­tetrakis(μ‐­trimethylsilylacetato‐O:O′)dicopper(II), [Cu₂(C₅H₁₁O₂Si)₄(C₉H₇N)₂], (IV), the centrosymmetric dinuclear Cu^II complexes have a cage structure with Cu?Cu distances of 2.664 (1), 2.638 (3) and 2.665 (1) Å, respectively. In the crystals of catena‐poly­[tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II)], [Cu₂(C₅H₁₁O₂Si)₄]_n, (V), the dinuclear Cu^II units of a cage structure are linked by the cyclic Cu—O bonds at the apical positions to form a linear chain by use of a glide translation.     

Barium(II)–2,4‐dinitrophenolate–18‐crown‐6 at 183 K

The title compound, bis(2,4‐dinitrophenolato‐κ²O,O′)(1,4,7,10,13,16‐hexaoxadecane‐κ⁶O)barium(II), [Ba(C₆H₃N₂O₅)₂(C₁₂H₂₄O₆)], is a 1:1 complex of barium(II)–2,4‐di­nitro­phenolate and 1,4,7,10,13,16‐hexaoxa­cyclo­octa­decane (18‐crown‐6). Its structure is located on a crystallographic inversion centre. The temperature dependence of the crystal structure has been studied. The monoclinic β angle of the P2₁/­n space group increases with increasing temperature. The packing structure of the complex is stabilized by intermolecular C—H?O interactions.     

Adducts of 1,1,1‐tris(4‐hydroxy­phenyl)­ethane with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐bis(4‐pyridyl)­ethene: continuously interwoven structures in three dimensions

In the adduct 1,2‐bis(4‐pyridyl)­ethane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₂H₁₂N₂·2C₂₀H₁₈O₃, the bipyridyl component lies across an inversion centre in P. The tris‐phenol mol­ecules [systematic name: 4,4′,4′′‐(ethane‐1,1,1‐triyl)­triphenol] are linked by O—H?O hydrogen bonds to form sheets built from R(38) rings, and symmetry‐related pairs of sheets are linked by the bipyridyl mol­ecules via O—H?N hydrogen bonds to form open bilayers. Each bilayer is interwoven with two adjacent bilayers, forming a continuous three‐dimensional structure. In the adduct 1,2‐bis(4‐pyridyl)­ethene–1,1,1‐tris(4‐hydroxy­phenyl)­ethane–methanol (1/1/1), C₁₂H₁₀N₂·C₂₀H₁₈O₃·CH₄O, the mol­ecules are linked by O—H?O and O—H?N hydrogen bonds into three interwoven three‐dimensional frameworks, generated by single spiral chains along [010] and [001] and a triple‐helical spiral along [100].     

(1R,2R)‐1,2‐Di­phenyl‐1,2‐bis(8‐quinoline­sulfonyl­amino)ethyl­enedi­amine–acetone (1/1)

The crystal structure of the new chiral complex (1R,2R)‐1,2‐di­phenyl‐1,2‐bis(8‐quinoline­sulfonyl­amino)‐ ethyl­enedi­amine–acetone (1/1), C₃₂H₂₆N₄O₄S₂^.C₃H₆O, is reported. The conformation of the C₃₂H₂₆N₄O₄S₂ (BQSDA) mol­ecule is determined by a bifurcated N—H?N hydrogen‐bond system. The acetone of solvation is linked to the BQSDA mol­ecule by an N—H?O hydrogen bond.     

Three complexes of bis(N‐methyl­benzo­hydro­xamato‐O,O′)copper(II)

The first single‐crystal studies of three bis‐transoid Cu–hydrox­amate salts, bis(3‐methoxy‐4,N‐dimethyl­benzo­hydrox­amato‐O,O′)copper(II), [Cu(C₁₀H₁₂NO₃)₂], bis(4‐chloro‐N‐methyl­benzo­hydro­xamato‐O,O′)copper(II), [Cu­(C₈­H₇­Cl­NO₂)₂], bis(N‐methyl‐3,5‐di­nitro­benzo­hydro­xamato‐O,O′)copper(II)–chloro­form (1/2), [Cu­(C₈­H₆­N₃O₆)₂]·­2CHCl₃, are presented. The Cu atom in each of the title compounds sits at a center of inversion and displays a nearly square‐planar geometry with the hydro­xamate‐O atoms connected to it in a syn configuration. The N atoms are in a transoid configuration. Each five‐membered Cu–hydro­xamate ring is planar, thus providing evidence that a planar N atom is present in each ring. The phenyl groups are twisted with respect to the hydro­xamate group by ～40–54°. The angular strain of the sp² carbonyl oxy­gen is significant (～10° from ideal).     

Completing the bis[hydroxybis(pyridin‐2‐yl)methanesulfonato‐κ3N,O,N′]MII series (M = Mn to Zn) with the copper(II) and cobalt(II) structures

The Cu^II complex bis[hydroxybis(pyridin‐2‐yl)methanesulfonato‐κ³N,O,N′]copper(II) hexahydrate, [Cu(C₁₁H₉N₂O₄S)₂]·6H₂O, (I), crystallizes in the space group P, compared with P2₁/c for the anhydrous Co^II analogue bis[hydroxybis(pyridin‐2‐yl)methanesulfonato‐κ³N,O,N′]cobalt(II), [Co(C₁₁H₉N₂O₄S)₂], (II). However, both molecules sit on a crystallographic inversion centre and are thus very similar in appearance. Jahn–Teller elongation of the Cu—O bonds [2.347 (3) Å in (I) and 2.064 (2) Å in (II)] influences the S—O bond lengths, which are all around 1.455 (3) Å in (I) and 1.436 (2)–1.473 (2) Å in (II).     

Adducts of nickel(II) acetylacetonate chelating with heterocyclic bases: 3‐­cyanopyridine and 4‐cyanopyridine

In both title compounds, (acetyl­acetonato‐O,O′)­bis(3‐cyano­pyridine‐N)­nickel(II), (I), and (acetyl­acetonato‐O,O′)­bis(4‐cyanopyridine‐N)­nickel(II), (II), both [Ni(C₅­H₇O₂)₂(C₆H₄N₂)₂], the Ni^II atom, which is situated on a centre of symmetry, is octahedrally coordinated. Distances and angles for (I) and (II), respectively, are: Ni—O 2.009 (2)/2.016 (2) and 2.0110 (16)/2.0238 (18) Å, Ni—N 2.116 (3) and 2.179 (2) Å, O—Ni—O 91.86 (10) and 90.19 (7)°, and O—Ni—N 91.27 (11)/90.19 (11) and 89.65 (8)/90.79 (7)°.     

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°].     

Dimeric hexakis(4‐methyl­benzoato)­bis(1,10‐phenanthroline)didyspros­ium(III)

The title compound, [Dy₂(C₈H₇O₂)₆(C₁₂H₈N₂)₂], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ⁴O:O′‐bis[bis(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ⁸O:O′‐bis[(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the Dy^III ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the Dy^III ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.     

μ‐Aqua‐penta­aqua­[μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine]­chloro­dinickel(II) trichloride trihydrate

The title compound, μ‐aqua‐1:2κ²O‐penta­aqua‐1κ²O,2κ³O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ²N¹,N⁶:2κ²N²,N³‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni₂Cl(C₁₆H₁₄­N₄)(H₂O)₆]Cl₃·3H₂O, consists of two Ni^II atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

(2,2′‐Bi­pyridine‐κ2N,N′)(dichromato‐κO)copper(II)

The title compound, [Cu(Cr₂O₇)(C₁₀H₈N₂)₂], a new mixed‐metal molecular compound, contains isolated molecular units, each comprised of one Cu^II atom coordinated to two 2,2′‐bi­pyridine ligands and also to an oxy­gen vertex of a dichromate anion. The Cu^II atom has an approximate trigonal–bipyramidal geometry, which is consistent with previous studies. Both enantiomers of the chiral complex mol­ecule are present and are related by inversion centers. In a reported pyridine analogue, achiral [Cu(Cr₂O₇)(pyridine)₄] chains pack in the non‐centrosymmetric space group Pna2₁. Differences in the organic ligands influence the chirality and dimensionality of the Cu—Cr₂O₇ bonding.     

Hydrogen‐bonded 1,2‐bis(4‐pyridyl)ethylene and maleic acid

The title compound (systematic name: 4,4′‐ethyl­ene­dipyridinium dimaleate), C₁₂H₁₂N₂²⁺·2C₄H₃O₄^?, is a 1:2 adduct of 1,2‐bis(4‐pyridyl)­ethyl­ene (BPE) and maleic acid (MA). The interaction between the two components in the molecular complex is due to intermolecular hydrogen bonding via an N⁺—H?O^? hydrogen bond.     

catena‐Poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ2N,N′)copper(II)]‐μ‐di­thion­ato‐κ2O:O′] and trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ2N,N′)copper(II) di­thionate

In title an­hydro­us catena‐poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ²N,N′)copper(II)]‐μ‐di­thionato‐κ²O:O′], [Cu(S₂O₆)(C₂H₈N₂)₂]_n or [{H₂N(CH₂)₂NH₂}₂Cu(O·O₂SSO₂·O)]_∞, successive Cu atoms are bridged by a single doubly charged di­thionate group, forming a one‐dimensional polymer with inversion centres at the metal atoms and the mid‐point of the S—S bond [Cu—O = 2.5744 (15) Å]. In title (hydrated) trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ²N,N′)copper(II) di­thionate, [Cu(C₃H₁₀N₂)₂(H₂O)₂](S₂O₆) or [{H₂N(CH₂)₃NH₂}₂Cu(OH₂)₂](S₂O₆), both ions have imposed 2/m symmetry. The `axial' anion components are displaced by a pair of water ligands [Cu—O = 2.439 (3) Å], the shorter Cu—O distance being compensated by the lengthened Cu—N distance [2.0443 (18), cf. 2.0100 (13) and 2.0122 (16) Å].     

A bis­(acetyl­acetonato)­uranium(IV) complex of the Schiff base N,N′‐bis(3‐hydroxy­salicyl­idene)‐2‐methyl‐1,2‐propane­di­amine

The title complex, bis­(acetyl­acetonato‐κ²O,O′)[N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐propane­di­amine‐κ⁴N,O,O′,N′]­uranium(IV) tetra­hydro­furan solvate, [U(C₁₈H₁₈N₂O₄)(C₅H₇O₂)₂]·C₄H₈O, is a rare example of a uranium(IV) complex with a compartmental Schiff base. The U atom is located in the N₂O₂ inner site of the hexadentate N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐pro­pane­di­amine group and is bound also to the two O atoms of both acetyl­acetonate moieties, which results in a dodecahedral coordination environment. Centrosymmetric dimers are formed through intermolecular hydrogen bonds that link the terminal uncoordinated hydroxy groups to one another and to the O atoms of the acetyl­acetonate ligands.     

Bis­[bis(N,N‐diethyl‐1,1‐di­seleno­car­bam­ato)copper(II)], [Cu(Se2CNEt2)2]2

The title centrosymmetric Cu^II binuclear complex, bis(μ‐N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′:Se)­bis­[(N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′)copper(II)], [Cu(Se₂CNEt₂)₂]₂ or [Cu₂(C₅H₁₀NSe₂)₄], is built from two symmetry‐related [Cu{Se₂CN(Et)₂}₂] units by pairs of Cu—Se bonds. The coordination geometry at the unique Cu atom is distorted square pyramidal, with Cu—Se distances in the range 2.4091 (11)—2.9095 (10) Å.