catena‐Poly[[dicyanamido(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)copper(II)]‐μ‐dicyanamido‐κ2N1:N5]

In the crystal structure of the title compound, [Cu(C₂N₃)₂(C₁₂H₁₂N₂)]_n, the Cu^II atom adopts a distorted square‐pyramidal geometry, the basal plane of which is formed by two N atoms of the bi­pyridine ligand, one N atom of a bidentate dicyan­amide anion and one N atom of a monodentate dicyan­amide anion [Cu—N = 1.9760 (15)–2.0157 (15) Å]. The apical position is occupied by an N atom of a bidentate dicyan­amide anion, located 2.2468 (16) Å from the Cu atom, thus forming a one‐dimensional polymeric chain.     

Hydrogen‐bonded sheets in 2‐(2‐aminophenyl)‐1H‐benzimidazol‐3‐ium dihydrogen phosphate

The title salt, C₁₃H₁₂N₃⁺·H₂PO₄⁻, contains a nonplanar 2‐(2‐aminophenyl)‐1H‐benzimidazol‐3‐ium cation and two different dihydrogen phosphate anions, both situated on twofold rotation axes in the space group C2. The anions are linked by O—H...O hydrogen bonds into chains of R₂²(8) rings. The anion chains are linked by the cations, via hydrogen‐bonding complementarities and electrostatic interactions, giving rise to a sheet structure with alternating rows of organic cations and inorganic anions. Comparison of this structure with that of the pure amine reveals that the two compounds generate characteristically different sheet structures. The anion–anion chain serves as a template for the assembly of the cations, suggesting a possible application in the design of solid‐state materials.     

Polysulfonylamines. CXCI. The `almost' polymorphs rac‐trans‐2‐aminocyclohexan‐1‐aminium di(methanesulfonyl)azanide and its 0.11‐hydrate

The title compound, C₆H₁₅N₂⁺·C₂H₆NO₄S₂⁻, crystallizes as a 0.11‐hydrate, (I), in the space group C2; the asymmetric unit consists of two cations (one of each enantiomer), one anion on a general position, two half anions, each with the N atom on a twofold axis, and approximately one fifth of a water molecule. The general anion departs significantly from the usual conformation: it lacks one of the typical `W'‐shaped sequence of O—S—N—S—O atoms. The compound also crystallizes in the solvent‐free form, (II), in the space group P2₁/c, with one formula unit in the asymmetric unit. Both compounds form ribbons of hydrogen‐bonded cation dimers parallel to the b axis. In (I), there are two independent ribbons of opposite chirality, each involving one anion on a special position, and these ribbons are connected by hydrogen bonds to the anion on a general position, resulting in a layer structure parallel to (100). In (II), the chains are connected by hydrogen bonds, and again a layer structure parallel to (100) results.     

1,1′‐Diethyl‐4,4′‐bipyridine‐1,1′‐diium bis(1,1,3,3‐tetracyano‐2‐ethoxypropenide): multiple C—H...N hydrogen bonds form a complex sheet structure

In the title salt, C₁₄H₁₈N₂²⁺·2C₉H₅N₄O⁻, the 1,1′‐diethyl‐4,4′‐bipyridine‐1,1′‐diium dication lies across a centre of inversion in the space group P2₁/c. In the 1,1,3,3‐tetracyano‐2‐ethoxypropenide anion, the two independent –C(CN)₂ units are rotated, in conrotatory fashion, out of the plane of the central propenide unit, making dihedral angles with the central unit of 16.0 (2) and 23.0 (2)°. The ionic components are linked by C—H...N hydrogen bonds to form a complex sheet structure, within which each cation acts as a sixfold donor of hydrogen bonds and each anion acts as a threefold acceptor of hydrogen bonds.     

Tris(1,10‐phenanthroline)sodium 2,4,6‐trimercapto‐1,3,5‐triazin‐1‐ide

The title compound, [Na(C₁₂H₈N₂)₃](C₃H₂N₃S₃), contains an Na⁺ centre which is ionicly bonded to three 1,10‐phenanthroline (phen) ligands and one tri­thio­cyanurate(1−) (ttcH₂) anion. In the crystal structure, the anions are linked via hydrogen bonds to form linear chains. The S and H atoms of the ttcH₂ anion participate in intermolecular N—H⋯S hydrogen bonding, with N⋯S distances of 3.298 (2) and 3.336 (2) Å. The phen ligands are almost parallel, with dihedral angles of 3.92 (5), 11.75 (5) and 15.45 (5)°; moreover, they are nearly perpendicular to the ttcH₂ chains, with angles of 81.94 (7), 85.86 (7) and 85.96 (7)°.     

2‐Ethyl‐6‐methylpyridin‐3‐ol and its salt bis(2‐ethyl‐3‐hydroxy‐6‐methylpyridinium) succinate

The title compounds, C₈H₁₁NO, (I), and 2C₈H₁₂NO⁺·C₄H₄O₄²⁻, (II), both crystallize in the monoclinic space group P2₁/c. In the crystal structure of (I), intermolecular O—H...N hydrogen bonds combine the molecules into polymeric chains extending along the c axis. The chains are linked by C—H...π interactions between the methylene H atoms and the pyridine rings into polymeric layers parallel to the ac plane. In the crystal structure of (II), the succinate anion lies on an inversion centre. Its carboxylate groups interact with the 2‐ethyl‐3‐hydroxy‐6‐methylpyridinium cations via intermolecular N—H...O hydrogen bonds with the pyridine ring H atoms and O—H...O hydrogen bonds with the hydroxy H atoms to form polymeric chains, which extend along the [01] direction and comprise R₄⁴(18) hydrogen‐bonded ring motifs. These chains are linked to form a three‐dimensional network through nonclassical C—H...O hydrogen bonds between the pyridine ring H atoms and the hydroxy‐group O atoms of neighbouring cations. π–π interactions between the pyridine rings and C—H...π interactions between the methylene H atoms of the succinate anion and the pyridine rings are also present in this network.     

Bis(tetra‐n‐butylammonium) bis(μ‐1,2‐dicyanoethene‐1,2‐dithiolato‐κ3S,S′:S′)bis[(1,2‐dicyanoethene‐1,2‐dithiolato‐κ2S,S′)cobalt(III)]

In the title compound, (C₁₆H₃₆N)₂[Co(C₄N₂S₂)₂]₂, pairs of [Co(C₄N₂S₂)₂]^? anions combine to form discrete crystallographically centrosymmetric dimers, which stack along the c axis, surrounded by the counter‐cations. The metal atom in the anion has a five‐coordinate distorted square‐pyramidal geometry.     

Di‐μ‐hydroxo‐bis­[aqua(1,10‐phenanthroline‐κ2N,N′)copper(II)] trans‐bis(2‐{[(E)‐5‐formyl‐2‐oxido‐κO‐benzyl­idene]­amino‐κN}ethanesulfonato(2–))copper(II) hexahydrate

The title compound, [Cu₂(OH)₂(C₁₂H₈N₂)₂(H₂O)₂][Cu(C₁₀H₉NO₅S)₂]·6H₂O, is comprised of a copper‐centred complex cation and a copper‐centred complex anion; the cation lies about an inversion centre and in the anion the Cu atom lies on an inversion centre. In the doubly charged bridged dicopper cation, each Cu centre has distorted square‐pyramidal geometry. In the square‐planar dianion, two sulfonate ligands are trans coordinated to the Cu atom via a deprotonated hydroxyl O atom and an imine N atom, forming two six‐membered chelate rings. The structure is stabilized by an extensive hydrogen‐bond system and aromatic‐ring stacking interactions.     

An optically resolved crystal of thiomalate: (S)‐1‐phenylethanaminium (R)‐thiomalate

The asymmetric unit of the optically resolved title salt, C₈H₁₂N⁺·C₄H₅O₄S⁻, contains a 1‐phenylethanaminium monocation and a thiomalate (3‐carboxy‐2‐sulfanylpropanoate) monoanion. The absolute configurations of the cation and the anion are determined to be S and R, respectively. In the crystal, cation–anion N—H...O hydrogen bonds, together with anion–anion O—H...O and S—H...O hydrogen bonds, construct a two‐dimensional supramolecular sheet parallel to the ab plane. The two‐dimensional sheet is linked with the upper and lower sheets through C—H...π interactions to stack along the c axis.     

Poly[bis[aquaneodymium(III)]‐μ2‐oxalato‐di‐μ4‐succinato]

In the title compound, [Nd₂(C₄H₄O₄)₂(C₂O₄)(H₂O)₂]_n, the flexible succinate anion assumes the gauche conformation and bridges the nine‐coordinate Nd atoms to generate two‐dimensional layers parallel to (010). The coordination polymer layers are linked into a three‐dimensional framework by the rigid oxalate ligands. The oxalate ions are located on a center of inversion.     

A novel heterocyclic compound: catena‐poly[[[diaquasodium(I)]‐di‐μ‐aqua] hemi(1,5‐dihydroxy‐4,8,9‐trioxa‐2,6‐diazabicyclo[3.3.1]nona‐2,6‐diene‐3,7‐diolate)]

In the title compound, {[Na(H₂O)₄]₂(C₄H₂N₂O₇)}_n, the 1,5‐dihydroxy‐4,8,9‐trioxa‐2,6‐diazabicyclo[3.3.1]nona‐2,6‐diene‐3,7‐diolate anion lies across a twofold axis in the space group C2/c; there are two independent Na sites, one on a twofold axis and the other on a centre of inversion. Hydrogen bonds link the {[Na(H₂O)₄]⁺}_n chains and diolate anions into a three‐dimensional framework.     

Crystallographic characterization of the first reported crystalline form of the potent hallucinogen (R)‐2‐amino‐1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propane or `bromodragonfly': the 1:1 anhydrous proton‐transfer compound with 3,5‐dinitrosalicylic acid

The 1:1 proton‐transfer compound of the potent substituted amphetamine hallucinogen (R)‐2‐amino‐1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propane (common trivial name `bromodragonfly') with 3,5‐dinitrosalicylic acid, namely 1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propan‐2‐aminium 2‐carboxy‐4,6‐dinitrophenolate, C₁₃H₁₃BrNO₂⁺·C₇H₃N₂O₇⁻, forms hydrogen‐bonded cation–anion chain substructures comprising undulating head‐to‐tail anion chains formed through C(8) carboxyl–nitro O—H...O associations and incorporating the aminium groups of the cations. The intrachain cation–anion hydrogen‐bonding associations feature proximal cyclic R₃³(8) interactions involving both an N⁺—H...O_phenolate and the carboxyl–nitro O—H...O associations and aromatic π–π ring interactions [minimum ring centroid separation = 3.566 (2) Å]. A lateral hydrogen‐bonding interaction between the third aminium H atom and a carboxyl O‐atom acceptor links the chain substructures, giving a two‐dimensional sheet structure. This determination represents the first of any form of this compound and is in the (R) absolute configuration. The atypical crystal stability is attributed both to the hydrogen‐bonded chain substructures provided by the anions, which accommodate the aminium proton‐donor groups of the cations and give crosslinking, and to the presence of the cation–anion aromatic ring π–π interactions.     

catena‐Poly[bis­[(1,10‐phenanthro­line)nickel(II)]‐μ‐3,6‐dicarboxy­cyclo­hexane‐1,2,4,5‐tetra­carboxyl­ato]

In the title compound, [Ni₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]_n, the 3,6‐dicarboxy­cyclo­hexane‐1,2,4,5‐tetra­carboxyl­ate (H₂chhc⁴⁻) anion has crystallographically imposed C₂ symmetry and bridges the six‐coordinate Ni atoms to generate polymeric [Ni₂(H₂chhc)_2/2(C₁₂H₈N₂)₂] chains extending in the [010] direction. The coordination polymer chains are linked into a three‐dimensional framework by O—H⋯O and C—H⋯O hydrogen bonds.     

N‐Methyl­pyridinium 3‐cyano‐4‐(di­cyano­methyl­ene)‐5‐oxo‐4,5‐di­hydro‐1H‐pyrrol‐2‐olate

The crystal structure of the title compound, C₆H₈N⁺·C₈HN₄O₂⁻, is characterized by three independent ion pairs (A, B and C) in the asymmetric unit. Each ion pair consists of an anion and a cation, and the three ion pairs have similar geometric parameters. All the anions are arranged as dianion dimers via two N—H⋯O hydrogen bonds and the dimers form one‐dimensional columns parallel to the b axis as a result of π–π interactions. The cations are also stacked, in two different ways: one type of stacking consists of alternating A and B cations, while the other type consists of C cations only. Each dianion dimer stack is surrounded by eight stacks of cations and is not connected directly to other dianion stacks.     

Poly­[[bis­[aqua(1,10‐phenanthroline)­lanthanum(III)]‐μ‐aqua‐di‐μ‐5‐sulfonatoisophthalato] monohydrate] and poly­[[[tri­aqua­lanthanum(III)]‐μ‐5‐sulfonatoisophthalato] monohydrate]

In the two related polymeric title compounds, {[La₂(sip)₂(phen)₂(H₂O)₃]·H₂O}_n [sip is the 5‐sulfonatoisophthalate trianion (C₈H₃O₇S³⁻) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], (I), and {[La(sip)(H₂O)₃]·H₂O}_n, (II), the lanthanum(III) ions are nine‐coordinate, with similar distorted monocapped square‐antiprism coordination geometry. The two crystal structures are very different. In (I), the sip anion acts as a pentadentate ligand, one of the coordinated water mol­ecules lies on a twofold axis and further inversion, n‐glide and translation operations generate a two‐dimensional framework. In (II), the sip anion functions as a hexadentate ligand and a three‐dimensional network with trinuclear 24‐membered rings is developed via inversion, n‐glide, twofold‐screw and translation operations. Both structures also have extensive O—H⋯O hydrogen‐bonded networks and π–π interactions.     

Ammonium 3‐cyano‐4‐(dicyano­methyl­ene)‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate monohydrate

Each anion of the title salt, NH₄⁺·C₈HN₄O₂⁻·H₂O, is linked by two N—H⋯O hydrogen bonds to another anion, thus forming an essentially planar centrosymmetric dimer. The dimers are considered to be mol­ecular building blocks of an anionic wall. The building blocks form infinite ribbons via–C—N⋯N—C– dipole–dipole and π–π inter­actions. Adjacent ribbons are stacked by means of π–π inter­actions, thus forming an anionic wall. Neighbouring walls are connected by (NH₄⁺…H₂O)_n chains running along the b axis.     

Λ‐{1,4,7,10‐Tetrakis­[(S)‐2‐hydroxy­propyl‐κO]‐1,4,7,10‐tetra­aza­cyclo­do­decane‐κ4N}cadmium(II) bis(2,4,6‐tri­nitro­phenolate) aceto­nitrile solvate

Crystallization of [Cd(S‐thpc12)](ClO₄)₂·H₂O {S‐thpc12 is 1,4,7,10‐tetrakis­[(S)‐2‐hydroxy­propyl]‐1,4,7,10‐tetra­aza­cyclo­do­decane} in the presence of two equivalents of sodium picrate monohydrate (sodium 2,4,6‐tri­nitro­phenolate monohydrate) diastereoselectively produces a neutral receptor complex, viz. the title compound, Λ‐[Cd(C₂₀H₄₄N₄O₄)](C₆H₂N₃O₇)₂·CH₃CN. In this complex, two picrate anions hydrogen bond, via their phenolate moieties, to the pendant hydroxyl groups of the receptor which, together with the four N atoms, themselves bond to Cd^II in an approximately cubic arrangement. One picrate anion hydrogen bonds to all four hydroxyl groups, one of which also acts as the sole hydrogen‐bond donor to the second picrate anion.     

(4,6‐Dimethyl‐2‐sulfanylidenepyrimidin‐1‐ium) trichlorido(thiourea‐κS)zinc(II)

The title compound, (C₆H₉N₂S)[ZnCl₃{SC(NH₂)₂}], exists as a zincate where the zinc(II) centre is coordinated by three chloride ligands and a thiourea ligand to form the anion. The organic cation adopts the protonated 4,6‐dimethyl‐2‐sulfanylidenepyrimidin‐1‐ium (L) form of 4,6‐dimethylpyrimidine‐2(1H)‐thione. Two short N—H...Cl hydrogen bonds involving the pyrimidine H atoms and the [ZnCl₃L]⁻ anion form a crystallographically centrosymmetric dimeric unit consisting of two anions and two cations. The packing structure is completed by longer‐range hydrogen bonds donated by the thiourea NH₂ groups to chloride ligand hydrogen‐bond acceptors.     

Poly[[[diaqua­zinc(II)]‐bis(μ2‐3‐cyano‐4‐dicyano­methyl­ene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ2N3:N3′)] dihydrate]

The coordination of the 3‐cyano‐4‐dicyano­methyl­ene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate anion to Zn^II, the apical sites of which are occupied by two water mol­ecules, results in the formation of two‐dimensional layers of the title coordination polymer, {[Zn(C₈HN₄O₂)₂(H₂O)₂]·2H₂O}_n, in which the Zn^II cations lie on inversion centres in space group C2/c, with water ligands in the apical sites of octa­hedral geometry. Hydrogen bonds between coordinated and lattice water mol­ecules, and π–π stacking inter­actions between the anions link adjacent layers into a continuous framework.     

catena‐Poly­[[(benzoato‐κO)silver(I)]‐μ‐2‐amino­pyrimidine‐κ2N1:N3]

The title complex, [Ag(C₇H₅O₂)(C₄H₅N₃)]_n, is a polymer based on a mononuclear silver(I)‐centered fragment. The Ag^I atom is trigonally coordinated by two N atoms from two 2‐­amino­pyrimidine ligands and one O atom from one benzoate anion, giving zigzag polymeric chains with an [–Ag—N—C—N–]_n backbone running along the a axis. It is proposed that intermolecular hydrogen bonding drives the formation of the chain polymer.