Bis(N,N‐diethyl‐1,1‐di­seleno­carbam­ato‐Se)­selenium, [(Se2CNEt2)2Se]

The poly­seleno title compound, bis(N,N‐diethyl­seleno­carbamoyl) tri­selenide, [(Se₂CNEt₂)₂Se] or C₁₀H₂₀N₂Se₅, is obtained from the disproportion of sodium N,N‐diethyl‐1,1‐di­seleno­carbamate. An Se atom connects two N,N‐diethyl‐1,1‐di­seleno­carbamate groups with Se—Se distances in the range 2.4500 (11)–2.8601 (12) Å     

Bis(2,6‐di­amino‐3,5‐di­bromo­pyridinium) tetra­bromo­cuprate(II)

The title compound, (C₅H₆Br₂N₃)₂[CuBr₄], contains isolated substituted pyridinium cations and [CuBr₄]^2? anions. The di­amino­di­bromo­pyridinium ions are planar, while the Cu^II ions have a distorted compressed tetrahedral coordination with C₂ symmetry. The two independent trans‐Br—Cu—Br angles are 128.9 (1) and 136.0 (1)°, with Cu—Br distances of 2.3939 (15) and 2.3790 (16) Å.     

Molecular building blocks for solid‐state chalcogenides: solvothermal synthesis of [Mn(en)3]Te4 and [Fe(en)3]2(Sb2Se5)

Two new molecular metal chalcogenides, tris­(ethyl­enedi­amine‐N,N′)­manganese(II) tetratelluride, [Mn(C₂H₈N₂)₃]Te₄, (I), and bis­[tris­(ethyl­enedi­amine‐N,N′)­iron(II)] penta­seleno­diantimonate(III), [Fe(C₂H₈N₂)₃]₂(Sb₂Se₅), (II), containing the isolated molecular building blocks Te₄^2? and Sb₂Se₅^4?, have been synthesized by solvothermal reactions in an ethyl­enedi­amine solution at 433 K. The anion Te₄^2? in (I) is a zigzag oligometric chain with Te—Te bond lengths in the range 2.709–2.751 Å. There is a very short contact [3.329 (1) Å] between a pair of neighboring Te₄^2? anions. In (II), each Sb atom is surrounded by three Se atoms to give a tripodal coordination. One of the three independent Se atoms is a μ₂‐bridging ligand between two Sb atoms; the other two are terminal.     

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].     

The one‐dimensional structure of Cu(dmen)2Pd(CN)4 (dmen is N,N‐di­methyl­ethyl­enedi­amine)

The title compound, catena‐poly­[[μ‐cyano‐1:2κ²C:N‐dicyano‐1κ²C‐bis(N,N‐di­methyl­ethyl­enedi­amine‐2κ²N,N′)­pallad­ium(II)­copper(II)]‐μ‐cyano‐1:2′κ²C:N], [CuPd(CN)₄(C₄H₁₂N₂)₂]_n, consists of infinite quasi‐linear chains with all metal positions on centers of symmetry. The paramagnetic [Cu(dmen)₂]²⁺ cations are linked by diamagnetic [Pd(CN)₄]²⁻ anions via bridging cyano groups, which occupy trans positions in both cation and anion, giving rise to 2,2‐TT‐type chains. The coordination polyhedron of the paramagnetic Cu atom is an octahedron exhibiting typical elongation due to the Jahn–Teller effect, with two longer Cu—N([triple‐bond]C) bonds in the axial positions [2.5528 (13) Å] and four shorter Cu—N_dmen bonds (dmen is N,N‐dimethylethylenediamine) in the equatorial plane [1.9926 (11) and 2.1149 (12) Å]. The Cu—N[triple‐bond]C angle is 138.03 (12)°. Neighboring chains form weak N—H⋯NC hydrogen bonds.     

Cu2(dien)2Ag5(CN)9 containing the one‐dimensional polymeric cation [Cu(dien)Ag(CN)2]nn+ and the unusual [Ag2(CN)3]− anion (dien is diethylenetriamine)

From the 1:1 system of [Cu(dien)₂](NO₃)₂ and K[Ag(CN)₂] in water (dien is diethyl­enetri­amine, C₄H₁₃N₃), the novel compound catena‐poly­[bis­[[μ‐cyano‐1:2κ²C:N‐diethyl­enetri­amine‐2κ³N‐copper(II)silver(I)]‐μ‐cyano‐1:2′κ²C:N] di­cyano­silver(I) tri­cyanodisilver(I)], [CuAg(CN)₂(dien)]₂[Ag(CN)₂][Ag₂(CN)₃], has been isolated. The structure is formed from positively charged [–Cu(dien)–NC–Ag–CN–]_nⁿ⁺ chains and two isolated centrosymmetric [Ag(CN)₂]^? and [Ag₂(CN)₃]^? anions. In the cationic chains, the Cu atoms are linked by bridging di­cyano­argentate groups, and the deformed square‐pyramidal coordination polyhedron of the Cu^II cation is formed from a tridentate chelate‐like bonded dien ligand and two N‐bonded bridging cyano groups. One of the bridging cyano groups occupies the apical (ap) position [mean Cu—­N_eq = 2.02 (2) Å, and Cu—N_ap = 2.170 (3) Å; eq is equatorial]. Short argentophilic interactions in the range 3.16–­3.30 Å are present in the crystal structure.     

Three different bonding modes of cyano groups in the coordination polymer [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O (en is 1,2‐diaminoethane)

Partial reduction of the Cu^II ions in the aqueous system Cu^II–en–[Ni(CN)₄]^2? (1/1/1) (en is 1,2‐di­amino­ethane) yields a novel heterobimetallic mixed‐valence compound, poly­[[aqua­bis(1,2‐di­amino­ethane)copper(II)] [hexa‐μ‐cyano‐tetra­cyano­bis(1,2‐di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C₂H₈N₂)₂(H₂O)][Ni₂Cu₃(CN)₁₀(C₂H₈N₂)₂]·2H₂O or [Cu(en)₂(H₂O)][Cu(en)₂Ni₂Cu₂(CN)₁₀]·2H₂O. The structure is formed by a negatively charged two‐dimensional array of the cyano complex [Cu(en)₂Ni₂Cu₂(CN)₁₀]_n^2n?, [Cu(en)₂(H₂O)]²⁺ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen‐bonding system. The cyano groups act as terminal, μ₂‐bridging or μ₃‐bridging ligands.     

Two 2,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le–metal complexes (M = Cu and Ni)

The reaction of the diazine ligand 3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole (pod, C₁₂H₈N₄O), with Cu(CF₃SO₃)₂ or Ni(ClO₄)₂ afforded the title complexes di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole‐N²,N³]copper(II) bis­(tri­fluoro­methane­sul­fon­ate), [Cu(pod)₂(H₂O)₂](CF₃SO₃)₂, and di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le‐N²,N³]­nickel(II) diperchlorate, [Ni(pod)₂(H₂O)₂](ClO₄)₂. Both complexes present a crystallographically centrosymmetric mononuclear cation structure which consists of a six‐coordinated Cu^II or Ni^II ion with two pod mol­ecules acting as bidentate ligands and two axially coordinated water mol­ecules.     

Bis[N‐(2‐hydroxy­ethyl)‐β‐alaninato]copper(II)

The Cu^II ion in the title complex, [Cu(C₅H₁₀NO₃)₂] or [Cu(He‐ala)₂] [He‐ala = N‐(2‐hydroxy­ethyl)‐β‐alaninate], resides at the inversion centre of a square bipyramid comprised of two facially arranged tridentate He‐ala ligands. Each He‐ala ligand binds to a Cu^II ion by forming one six‐membered β‐alaninate chelate ring in a twist conformation and one five‐membered ethanol­amine ring in an envelope conformation, with Cu—N = 2.017 (2) Å, Cu—O_COO = 1.968 (1) Å and Cu—O_OH = 2.473 (2) Å. The [Cu(He‐ala)₂] mol­ecules are involved in a network of O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to the (10) plane. The layers are connected into a three‐dimensional structure by van der Waals inter­actions, so that the mol­ecular centres form pseudo‐face‐centered close packing.     

Di‐μ‐iodo‐bis{[1,1′‐methyl­enebis(3,5‐dimethyl‐1H‐pyrazole‐κN2)]copper(I)}

In the title compound, [Cu₂I₂(C₁₁H₁₆N₄)₂], each of the two crystallographically equivalent Cu atoms is tetrahedrally coordinated by two N atoms from one 1,1′‐methyl­ene­bis(3,5‐di­methyl‐1H‐pyrazole) ligand and two bridging iodide anions. The mol­ecule has a crystallographic center of symmetry located at the mid‐point of the Cu·Cu line. One H atom of the CH₂ group of the 1,1′‐methyl­ene­bis(3,5‐di­methyl‐1H‐pyrazole) ligand interacts with an iodide ion in an adjacent mol­ecule to afford pairwise intermolecular C—H·I contacts, thereby forming chains of mol­ecules running along the [101] direction.     

The diselanylbis(1,3‐dimethyl‐1H‐imidazol‐3‐ium) dication stabilized by the polymeric catena‐pentachloridotricuprate(I) anion

In the title compound, catena‐poly[diselanylbis(1,3‐dimethyl‐1H‐imidazol‐3‐ium) [μ₃‐chlorido‐tetra‐μ₂‐chlorido‐tricuprate(I)]], {(C₁₀H₁₆N₄Se₂)[Cu₃Cl₅]}_n, the diselenide dication is stabilized by catena‐[Cu₃Cl₅]²⁻ anions which associate through strong Cu—Cl bonds [average length = 2.3525 (13) Å] to form polymeric chains. The polymeric [Cu₃Cl₅]²⁻ anion contains crystallographically imposed twofold rotation symmetry, with distorted trigonal‐planar and tetrahedral geometries around the two symmetry‐independent Cu atoms. Likewise, the Se—Se bond of the cation is centered on a twofold rotation axis.     

Low‐dimensional compounds containing cyano groups. VI.

The title compound, [Cu₂(C₄H₁₂N₂)₂{Ag(CN)₂}₄(NH₃)]·2H₂O or [Ag₄Cu₂(CN)₈(C₄H₁₂N₂)₂(NH₃)]·2H₂O, contains two crystallographically different Cu^II atoms lying on twofold axes. The first Cu atom is hexacoordinated in the form of an elongated tetragonal bipyramid and is part of a plane in which Cu atoms are connected by two bridging di­amino­butane mol­ecules [Cu—N = 2.033 (4) Å] and two di­cyano­argentate anions [Cu—N = 2.622 (6) Å]. The ammine ligand stands perpendicular to this plane [Cu—N = 2.011 (6) Å] in a trans position to it. Another [Ag(CN)₂]⁻ anion connects the hexacoordinated Cu atom [Cu—N = 1.997 (8) Å] with the second Cu atom [Cu—N = 2.026 (7) Å], which is pentacoordinated in the form of a slightly distorted trigonal bipyramid by two monodentate di­cyano­argetate anions [Cu—N = 2.040 (5) Å]. The axial positions are occupied by two bridging di­amino­butane mol­ecules [Cu—N = 2.011 (4) Å] that connect the Cu atoms into chains parallel to the above plane. The water mol­ecules remain uncoordinated and thus a unique combination of two‐ and one‐dimensional structures is formed.     

Bis(3,5‐di­methyl­pyrazole‐κN2)silver(I) nitrate

The two independent bis(3,5‐di­methyl­pyrazole)silver(I) cations in crystalline [Ag(C₅H₇N₂)₂]NO₃ display N—Ag—N angles of 175.51 (14) and 174.44 (13)°, and an average Ag—N distance of 2.124 (5) Å. The nitrate anion is situated between [Ag(C₅H₇N₂)₂]⁺ units and interacts via hydrogen bonds with the NH groups. The two 3,5‐di­methyl­pyrazole ligands are trans about the silver center. Only a small deviation from linearity is observed in the coordination around silver.     

Two tetrahydrofuran solvates of HN(SePPh2)2

The X‐ray crystal structures of P,P′‐imino­bis­(di­phenyl­seleno­phosphine) tetra­hydro­furan solvate, C₂₄H₂₁NP₂Se₂·C₄H₈O, (I), and bis­(tetra­hydro­furan) solvate, C₂₄H₂₁NP₂Se₂·2C₄H₈O, (II), have been determined; (I) has twofold crystallographic symmetry. In each compound, the O atom of one mol­ecule of tetra­hydro­furan is hydrogen bonded to the amide‐H atom of HN(SePPh₂)₂. The conformation of the Se—P—N—P—Se chains in (I), (II), and the crystal structure of the unsolvated HN(SePPh₂)₂ are different.     

Bis­[N,N′‐bis­(di­phenyl­methyl­ene)ethyl­enedi­amine‐κ2N,N′]copper(I) di­chloro­cuprate(I)

The 1:1 adduct of N,N′‐bis­(di­phenyl­methyl­ene)­ethyl­enedi­amine (bz₂en) with copper(I) chloride, viz. [Cu(C₂₈H₂₄N₂)₂][CuCl₂], has been synthesized. The structure contains cationic moieties of Cu^I ions (Cu on a twofold axis) coordinated to four N atoms of two bz₂en mol­ecules (in a distorted tetrahedron) and linear di­chloro­cuprate(I) anions (with Cu on an inversion centre). These cations and anions are packed in columns along b. The packing of the cation and anion columns involves a significant C—H⋯Cl interaction and four short intermolecular C—H⋯π contacts, two of which are between cation columns.     

[N,N′‐Bis(5‐bromo­salicyl­idene)‐o‐phenylene­diaminato]copper(II)

In the title compound, {4,4′‐di­bromo‐2,2′‐[o‐phenyl­ene­bis­(nitrilo­methyl­idene)]­di­phen­ol­ato‐O,N,N′,O′}copper(II), [Cu(C₂₀H₁₂Br₂N₂O₂], the Cu^II ion shows a slightly distorted square‐planar geometry with the N₂O₂ atoms of the Schiff base imine–phenol tetradentate ligand.     

[N,N′‐Bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]­nickel(II) and [N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]copper(II)

In the title compounds, {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}nickel(II), [Ni(C₁₉H₂₀N₂O₂)], and {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}copper(II), [Cu(C₁₉H₂₀N₂O₂)], the Ni^II and Cu^II atoms are coordinated by two iminic N and two phenolic O atoms of the N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminate (SALPD^2?, C₁₇H₁₆N₂O₂^2?) ligand. The geometry of the coordination sphere is planar in the case of the Ni^II complex and distorted towards tetrahedral for the Cu^II complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20 (6) and 35.13 (7)°, respectively.     

Copper(I) and copper(II) complexes of an ethylene cross‐bridged cyclam

The preparation and crystal structures of (4,11‐di­benzyl‐1,4,8,11‐tetra­aza­bi­cyclo­[6.6.2]­hexa­decane‐κ⁴N)copper(I) hexa‐fluorophosphate, [Cu(C₂₆H₃₈N₄)]PF₆, and acetonitrile(4,11‐dibenzyl‐1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐κ⁴N)‐copper(II) bis(hexafluorophosphate), [Cu(C₂H₃N)(C₂₆H₃₈‐N₄)](PF₆)₂, are described. The Cu^I ion is tetracoordinated in a very distorted tetrahedron, while the Cu^II analogue is pentacoordinated in a square pyramid.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.