2‐(Hydro­xy­methyl)­pyridinium di­hydrogenphosphate

The title compound, C₆H₈NO⁺·H₂PO₄⁻, consists of 2‐(hy­droxy­methyl)­pyridinium and di­hydrogen­phosphate ions. The di­hydrogen­phosphate moieties are linked into chains by pairs of P—O—H⃛O—P hydrogen bonds. The 2‐(hydroxy­methyl)­pyridinium cations are connected to the di­hydrogen­phosphate units by O—H⃛O and N—H⃛O hydrogen bonds. Weak π–π interactions help to determine the interchain packing.     

Charge‐transfer complexes of 4‐(di­methyl­amino)­pyridine with 2,4‐, 3,4‐ and 3,5‐di­nitro­benzoic acid

In the three title crystal structures 4‐(di­methyl­amino)­pyridinium 2,4‐di­nitro­benzoate, (I), 4‐(di­methyl­amino)­pyri­dinium 3,4‐di­nitro­benzo­ate, (II), and 4‐(di­methyl­amino)pyri­din­ium 3,5‐di­nitro­benzo­ate, (III), all C₇H₁₁N₂⁺·C₇H₃N₂O₆^?, the ions are connected by an N—H?O hydrogen bond. Dihedral angles between the pyridine and phenyl rings are 69.9 (1), 26.7 (1) and 56.2 (1)° in (I), (II) and (III), respectively. Donor–acceptor π–π stacking is observed in (II) and (III), but not in (I).     

Two polymorphs of bis(2‐bromophenyl) di­sulfide

Colourless crystals of the title compound, bis(2‐bromo­phenyl) di­sulfide, C₁₂H₈Br₂S₂, are obtained from the reaction of 2‐bromo­phenyl­mercaptan with metallic sodium and either zinc chloride or cadmium chloride in methanol. In the presence of Zn^II ions, the crystals are orthorhombic (space group Pbca, with Z′ = 1); with Cd^II ions present, the product is triclinic (space group , with Z′ = 4). Both polymorphs exhibit significant intramolecular C—H⋯S hydrogen bonds. In the ortho­rhombic form, mol­ecules are linked by intermolecular C—H⋯Br hydrogen bonds, while in the triclinic form, mol­ecules exhibit Br⋯Br contacts.     

Intramolecular cyclization of 4,7‐bis(2‐bromo­acetyl)‐1‐thia‐4,7‐di­azacyclo­nonane

The reaction of 1‐thia‐4,7‐di­azacyclo­nonane with bromo­acetyl bromide in CHCl₃ affords the unexpected salt 4‐(2‐bromo­acetyl)‐8‐oxo‐1‐thionia‐4,7‐di­aza­bi­cyclo­[5.2.2]­un­decane bromide, C₁₀H₁₆BrN₂O₂S⁺·Br⁻. Two units of the salt are linked by S⋯Br contacts about a crystallographic inversion centre, thus forming dimers that are linked by Br⋯Br contacts into extended ribbons. S⋯O contacts between these ribbons generate a two‐dimensional sheet.     

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].     

[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.     

Bis(μ‐hexa­methyl­enetetr­amine)­bis(aqua­di­bromo­cadmium)­di­aqua­di­bromo­cadmium dihydrate

The title compound, poly­[[di­aqua­di­bromo­cadmium‐μ‐(1,3,5,7‐tetra­aza­tri­cyclo[3.3.1.1^3,7]decane‐N¹:N⁵)‐aqua­cad­mium‐di‐μ‐bromo‐aqua­cadmium‐μ‐(1,3,5,7‐tetra­aza­tri­cyclo[3.3.1.1^3,7]decane‐N¹:N⁵)‐di‐μ‐bromo] dihydrate], [Cd₃­Br₆­(C₆­H₁₂­N₄)₂­(H₂O)₄]·­2H₂O, is made up of two‐dimensional neutral rectangular coordination layers. Each rectangular subunit is enclosed by a pair of Cd₃(μ₂‐Br)₆(H₂O)₃ fragments and a pair of (μ₂‐hmt)Cd(H₂O)₂Br₂(μ₂‐hmt) fragments as sides (hmt is hexa­methyl­enetetr­amine). The unique Cd^II atom in the Cd₂Br₂ ring in the Cd₃(μ₂‐Br)₆(H₂O)₃ fragment is in a slightly distorted octahedral CdNOBr₄ geometry, surrounded by one hmt ligand [2.433 (5) Å], one aqua ligand [2.273 (4) Å] and four Br atoms [2.6409 (11)–3.0270 (14) Å]. The Cd^II atom in the (μ₂‐hmt)Cd(H₂O)₂Br₂(μ₂‐hmt) fragment lies on an inversion center and is in a highly distorted octahedral CdN₂O₂Br₂ geometry, surrounded by two trans‐related N atoms of two hmt ligands [2.479 (5) Å], two trans‐related aqua ligands [2.294 (4) Å] and two trans‐related Br atoms [2.6755 (12) Å]. Adjacent two‐dimensional coordination sheets are connected into a three‐dimensional network by hydrogen bonds involving lattice water mol­ecules, and the aqua, bromo and hmt ligands belonging to different layers.     

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.     

Dibromo(pyridoxal semicarbazone‐κ3N1,O3,O3′)copper(II)

The title compound, di­bromo(3‐hydroxy‐5‐hydroxy­methyl‐2‐methyl‐4‐pyridine­carbox­aldehyde semicarbazone‐κ³N¹,O³,O^3′)copper(II), [CuBr₂(C₉H₁₂N₄O₃)], consists of discrete complex units with the tridentate pyridoxal semicarbazone ligand as a zwitterion in an almost planar configuration. The Cu^II ions are in a distorted square‐pyramidal coordination, with the equatorial Br atom at a distance of 2.4017 (6) Å and the apical Br atom at a distance of 2.6860 (6) Å.     

Di­bromo­[(–)‐sparteine‐κ2N,N′]­zinc(II)

In the title compound, di­bromo­[(6R,7S,8S,14S)‐1,3,4,7,7a,8,9,10,11,13,14,14a‐dodeca­hydro‐7,14‐methano‐2H,6H‐dipyrido­[1,2‐a:1′,2′‐e][1,5]­diazo­cine‐κ²N,N′]­zinc(II), [ZnBr₂(C₁₅H₂₆N₂)], the chiral nitro­gen‐chelating alkaloid (?)‐l ‐sparteine acts as a bidentate ligand, with two bromide ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedral structure. The dihedral angle between the N—Zn—N and Br—Zn—Br planes is 82.4 (1)°. The distortion of the tetrahedral coordination is demonstrated by the fact that the midpoint of the N?N line does not lie in the Br—Zn—Br plane, but is tilted towards one of the N atoms by 0.164 Å. Similarly, the midpoint of the Br?Br line is tilted towards one of the Br atoms by 0.117 Å.     

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.     

β‐Pyridinium di­chloro­iodide

The β modification of pyridinium di­chloro­iodide, C₅H₆N⁺·Cl₂I^?, was obtained as yellow crystals by the reaction of (C₅NH₅)AuCl₃, C₅H₆N⁺·Cl^? and I₂ in a vacuum‐sealed ampoule. The di­chloro­iodide ion is nearly symmetric and linear with I—Cl bond lengths of 2.544 (3) and 2.550 (3) Å and a Cl—I—Cl angle of 179.68 (12)°.     

The ternary complex 4‐(2‐pyridyl)pyridinium–3,5‐di­nitro­benzoate–3,5‐di­nitro­benzoic acid (1/1/1)

In the title ternary complex, C₁₀H₉N₂⁺·C₇H₃N₂O₆^?·C₇H₄N₂O₆, the pyridinium cation adopts the role of the donor in an intermolecular N—H?O hydrogen‐bonding interaction with the carboxyl­ate group of the 3,5‐di­nitro­benzoate anion. The mol­ecules of the ternary complex form molecular ribbons perpendicular to the b direction, which are stabilized by one N—H?O, one O—H?O and five C—H?O intermolecular hydrogen bonds. The ribbons are further interconnected by three intermolecular C—H?O hydrogen bonds into a three‐dimensional network.     

NiII and ZnII complexes of the hexadentate macrocyclic ligand cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine

The title pendent‐arm macrocyclic hexa­amine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni^II and Zn^II complexes (both as perchlorate salts), namely (cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­nickel(II) di­per­chlorate, [Ni(C₁₂H₃₀N₆)]­­(ClO₄)₂, and (cis‐6,13‐di­methyl‐1,4,8,11‐tetraaza‐cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­zinc(II) di­per­chlorate, [Zn(C₁₂H₃₀N₆)]­(ClO₄)₂. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal‐ion size and the present results are compared with other structures of this ligand.     

1,3‐Propane­di­ammonium bis(3′‐nitro‐trans‐cinnamate) and trans‐1,2‐cyclo­hexane­di­ammonium bis(3′‐nitro‐trans‐cinnamate)

In the title two adducts, C₃H₁₂N₂²⁺·2C₉H₆NO₄^?, (I), and C₆H₁₆N₂²⁺·2C₉H₆NO₄^?, (II), hydrogen bonds between the di­ammonium and carboxyl­ate ions form a two‐dimensional network parallel to the ab plane in (I) and one‐dimensional chains along the c axis in (II). The cyclo­hexane­di­ammonium ion in (II) has a crystallographic twofold axis.     

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.     

1,2‐Di­cyano‐1,2‐bis­(imidazolidine‐2‐thione)­digold(I) and 2,2‐di­cyano‐1,1‐bis­(di­methyl­thio­urea)­digold(I)

Gold(I) cyanide forms complexes with imidazolidine‐2‐thione (etu) and di­methyl­thio­urea (dmtu) with the formula [Au₂(CN)₂L₂], i.e. the title complexes di­cyano‐1κC,2κC‐bis(imidazolidine‐2‐thione)‐1κS,2κS‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₆N₂S)₂], and di­cyano‐1κ²C‐bis(N,N′‐di­methyl­thio­urea)‐2κ²S‐digold(I)(Au—Au), [Au₂(CN)₂(C₃H₈N₂S)₂]. In the etu complex, two approximately linear (etu)AuCN groups are held together by a weak homopolar Au—Au bond [3.117 (1) Å], with a torsion angle of 61 (3)° between the two groups. In the dmtu complex, an approximately linear Au(dmtu)₂ group is bound to an approximately linear Au(CN)₂ group by a weak heteropolar Au—Au bond [3.091 (1) Å], with a torsion angle of 83 (5)° between the two groups.     

Diphenyl(2‐thioxo‐1,3‐dithiole‐4,5‐di­thiolato‐S,S′)plumbane at 295 K and diphenyl(2‐thioxo‐1,3‐dithiole‐4,5‐di­thiolato‐S,S′)stannane at 150 K

Molecules of di­phenyl(2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ato‐S,S′)­plumbane, [Pb(C₃S₅)(C₆H₅)₂], are linked into sheets via two intermolecular Pb?S_thione interactions of 3.322 (4) and 3.827 (4) Å; the Pb centre has a distorted octahedral geometry. In contrast, mol­ecules of ­di­phenyl(2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ato‐S,S′)­stannane, [Sn(C₃S₅)(C₆H₅)₂], are linked into chains via a single intermolecular Sn—S_thione interaction of 2.8174 (9) Å; the Sn centre has a distorted trigonal‐bipy­ramidal geometry.     

[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.