7‐Carboxyl­ato‐8‐hydroxy‐2‐methyl­quinolinium monohydrate and 7‐carboxy‐8‐hydroxy‐2‐methyl­quinolinium chloride monohydrate at 100 K

Both 7‐carboxyl­ato‐8‐hydroxy‐2‐methyl­quinolinium monohydrate, C₁₁H₉NO₃·H₂O, (I), and 7‐carboxy‐8‐hydroxy‐2‐methyl­quinolinium chloride monohydrate, C₁₁H₁₀NO₃⁺·Cl⁻·H₂O, (II), crystallize in the centrosymmetric P space group. Both compounds display an intramolecular O—H⋯O hydrogen bond involving the hydroxy group; this hydrogen bond is stronger in (I) due to its zwitterionic character [O⋯O = 2.4449 (11) Å in (I) and 2.5881 (12) Å in (II)]. In both crystal structures, the HN⁺ group participates in the stabilization of the structure via intermolecular hydrogen bonds with water mol­ecules [N⋯O = 2.7450 (12) Å in (I) and 2.8025 (14) Å in (II)]. In compound (II), a hydrogen‐bond network connects the Cl⁻ anion to the carboxylic acid group [Cl⋯O = 2.9641 (11) Å] and to two water mol­ecules [Cl⋯O = 3.1485 (10) and 3.2744 (10) Å].     

3,5‐Bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone and 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidinium chloride: potential biophotonic materials

In the title compound 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone, C₂₂H₂₃NO₃, (I), the central heterocyclic ring adopts a flattened boat conformation, while in the related salt 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidin­ium chloride, C₂₂H₂₄NO₃⁺·Cl⁻, (II), the ring exhibits a `sofa' conformation in which the N atom deviates from the planar fragment. The pendant benzene rings are twisted from the heterocyclic ring planes in both mol­ecules in the same direction, the range of dihedral angles between the ring planes being 24.5 (2)–32.7 (2)°. The dominant packing motif in (I) involves centrosymmetric dimers bound by weak intermolecular C—H⋯O hydrogen bonds. In (II), cations and anions are linked by strong N—H⋯Cl hydrogen bonds, while weak C—H⋯O and C—H⋯Cl hydrogen bonds link the cations and anions into a three‐dimensional framework.     

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.     

Two rhod­amine derivatives: 9‐[2‐(ethoxycarbonyl)phenyl]‐3,6‐bis(ethyl­amino)‐2,7‐di­methyl­xanthyl­ium chloride monohydrate and 3,6‐di­amino‐9‐[2‐(methoxy­carbonyl)­phenyl]xanthyl­ium chloride trihydrate

The title compounds, C₂₈H₃₁N₂O₃⁺·Cl^?·H₂O (common name rhod­amine‐6g), (I), and C₂₁H₁₇N₂O₃⁺·Cl^?·3H₂O (common name rhod­amine‐123), (II), both have planar xanthene skeletons with a formal +1 charge on the amino N atoms delocalized through the π‐electron system so that the N—Csp² bond distances indicate significant double‐bond character. The substituted planar phenyl groups make angles of 63.29 (8) and 87.96 (11)° with the xanthene planes in (I) and (II), respectively. In both mol­ecules, the carbonyl bond vectors point toward the xanthene rings. The ethyl­amine groups in (I) are oriented similarly with their CH₂–CH₃ bond vectors pointing nearly perpendicular to the xanthene plane. The chloride ions and water mol­ecules are disordered in both structures. In (I), the chloride ion and water mol­ecule are disordered between two sites. One water and chloride alternately occupy the same site with occupancy factors of 0.5. The other 0.5‐chloride and 0.5‐water occupy two distinct positions separated by 0.747 (8) Å. In (II), the chloride ion is disordered between three sites and one of the waters is disordered about two other sites. Both crystal structures are stabilized by hydrogen bonds involving the chloride ions, amino groups and water mol­ecules, as well as by π–π stacking between xanthene planes.     

Neutral 4‐phenyl‐1‐[phenyl(pyridin‐2‐yl)methylidene]semicarbazide and its salt forms with inorganic anions

Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spectroscopic characterization (IR and NMR spectroscopy) of four such compounds, namely the neutral molecule 4‐phenyl‐1‐[phenyl(pyridin‐2‐yl)methylidene]semicarbazide, C₁₉H₁₆N₄O, (I), abbreviated as HBzPyS, and three different hydrated salts, namely the chloride dihydrate, C₁₉H₁₇N₄O⁺·Cl^?·2H₂O, (II), the nitrate dihydrate, C₁₉H₁₇N₄O⁺·NO₃^?·2H₂O, (III), and the thiocyanate 2.5‐hydrate, C₁₉H₁₇N₄O⁺·SCN^?·2.5H₂O, (IV), of 2‐[phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium, abbreviated as [H₂BzPyS]⁺·X^?·nH₂O, with X = Cl^? and n = 2 for (II), X = NO₃^? and n = 2 for (III), and X = SCN^? and n = 2.5 for (IV), showing the influence of the anionic form in the intermolecular interactions. Water molecules and counter‐ions (chloride or nitrate) are involved in the formation of a two‐dimensional arrangement by the establishment of hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in the solid state. The neutral HBzPyS molecule crystallized as the E isomer due to the existence of weak π–π interactions between pairs of molecules. The calculated IR spectrum of the hydrated [H₂BzPyS]⁺ cation is in good agreement with the experimental results.     

1‐(2‐{4‐[6‐Hydro­xy‐2‐(4‐hydroxy­phenyl)­benzo­[b]­thiol‐3‐yl­carbonyl]­phenoxy}ethyl)­piperidinium chloride

The title compound, raloxifene hydro­chloride, C₂₈H₂₈NO₄S⁺·Cl^?, belongs to the benzo­thio­phene class of antiosteoporotic drugs. In the molecular cation, the 2‐phenol ring sustains a dihedral angle of 45.3 (1)° relative to the benzo­[b]­thio­phene system. The benzo­[b]­thio­phene and phenyl ring planes are twisted with respect to the carbonyl plane, with the smallest twist component occurring between the phenyl and carbonyl planes. The N atom bears the positive charge in the molecular cation and the piperidine ring adopts an almost perfect chair conformation. The Cl^? anion is involved in the formation of N—H?Cl and O—H?Cl intermolecular hydrogen bonds, which lead to the formation of a layer of molecular cations.     

The salt‐type 1:2 adduct of meso‐5,5,7,12,12,14‐hexa‐C‐methyl‐1,4,8,11‐tetraazacyclotetradecane (tet‐a) and 5‐nitroisophthalic acid forms a hydrogen‐bonded sheet ­structure containing two configur­ational isomers of [(tet‐a)H2]2+

The title compound, meso‐5,7,7,12,14,14‐hexa­methyl‐4,11‐di­aza‐1,8‐diazo­nia­cyclo­tetra­decane bis(3‐carboxy‐5‐nitro­benz­oate), C₁₆H₃₈N₄²⁺·2C₈H₄NO₆^?, is a salt in which the cation is present as two configurational isomers, disordered across a common centre of inversion in P, with occupancies of 0.847 (3) and 0.153 (3). The anions are linked into chains by a single O—H?O hydrogen bond [H?O 1.71 Å, O?O 2.5063 (15) Å and O—H?O 156°] and the cations link these anion chains into sheets by means of a range of N—H?O hydrogen bonds [H?O 1.81–2.53 Å, N?O 2.718 (5)–3.3554 (19) Å and N—H?O 146–171°].     

Clarithromycin hydro­chloride 3.5‐hydrate

The absolute configuration was determined for the title compound, C₃₈H₇₀NO₁₃⁺·Cl^?·3.5H₂O. The cation contains a 14‐membered macrocyclic lactone and two sugars, namely cladinose and desos­amine. The six‐membered rings of the sugars adopt chair conformations. The structure is stabilized by strong hydrogen bonds, with O?O distances in the range 2.486 (9)–2.830 (5) Å; other distances are N?O = 2.860 (5), N?Cl = 3.134 (4) and O?Cl = 3.303 (4) Å.     

A novel bridged asymmetric binuclear manganese(II) complex with DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benz­imidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane]

The crystal structure of the title compound, tetra­chloro­[μ‐1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­azaheptane]­dimanganese(II) methanol pentasolvate tetrahydrate, [Mn₂Cl₄(C₄₄H₄₃N₁₃)]·5CH₄O·4H₂O, contains an ­asymmetric dinuclear Mn^II–DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane] complex with an intra‐ligand bridging group (–NCH₂CH₂N–), as well as several solvate mol­ecules (methanol and water). Both Mn^II cations have similar distorted octahedral coordination geometries. One Mn^II cation is coordinated by a Cl⁻ anion and five N atoms from the ligand, and the other is coordinated by three Cl⁻ anions and three N atoms of the same ligand. The Mn⋯Mn distance is 7.94 Å. A Cl⋯H—O⋯H—O⋯H—N hydrogen‐bond chain is also observed, connecting the two parts of the complex.     

l‐Methioninium chloride and l‐seleno­methioninium chloride at 103 K

The crystal structures of the title compounds, (S)‐1‐carboxy‐3‐(methyl­sulfanyl)­propanaminium chloride, C₅H₁₂NO₂S⁺·Cl⁻, and (S)‐1‐carboxy‐3‐(methyl­selanyl)­propanaminium chloride, C₅H₁₂NO₂Se⁺·Cl⁻, are isomorphous. The proton­ated l ‐methionine and l ‐seleno­methionine mol­ecules have almost identical conformations and create very similar contacts with the Cl⁻ anions in the crystal structures of both compounds. The amino acid cations and the Cl⁻ anions are linked viaN—H⋯Cl⁻ and O—H⋯Cl⁻ hydrogen bonds.     

Hydrogen bonding in two salts of 3‐methylthio‐4‐(propargylthio)quinoline

In 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium chloride monohydrate, C₁₃H₁₂NS₂⁺·Cl^?·H₂O, and 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium tri­chloro­acetate, C₁₃H₁₂­NS₂⁺·­C₂Cl₃O₂^?, the terminal alkyne group forms C[triple‐bond]C—H?O hydrogen bonds of favourable geometry. The conformation of the flexible propargyl­thio group is different in the two structures.     

2(S)‐Amino‐3‐[1H‐imidazol‐4(5)‐yl]­propyl cyclo­hexylmethyl ether di­hydro­chloride and 2(S)‐amino‐3‐[1H‐imidazol‐4(5)‐yl]­propyl 4‐bromo­benzyl ether di­hydro­chloride

(Cyclo­hexyl­methyl­oxy­methyl)(1H‐imidazol‐4‐io­methyl)‐(S)‐ammonium dichloride, C₁₃H₂₅N₃O⁺·2Cl^?, and (4‐bromo­benzyl)(1H‐imidazol‐4‐io­methyl)‐(S)‐ammonium dichloride, C₁₃H₁₈BrN₃O⁺·2Cl^?, are model compounds with different biological activities for evaluation of the hist­amine H3‐receptor activation mechanism. Both title compounds occur in almost similar extended conformations.     

Two‐component molecular crystals from N‐heteroaromatics and nitro­benzoic acids

Five two‐component molecular crystals, benzimidazolium 3‐nitro­benzoate, C₇H₇N₂⁺·C₇H₄NO₄^?, (I), benzimidazolium 4‐nitro­benzoate, C₇H₇N₂⁺·C₇H₄NO₄^?, (II), 1H‐benzotriazole–3‐nitro­benzoic acid (1/1), C₆H₅N₃·C₇H₅NO₄, (III), imidazol­ium 3‐nitro­benzoate, C₃H₅N₂⁺·C₇H₄NO₄^?, (IV), and imid­azolium 4‐nitro­benzoate, C₃H₅N₂⁺·C₇H₄NO₄^?, (V), were prepared with the aim of making chiral crystals. Only (I) crystallizes in a chiral space group. The mol­ecules of (I) and (II) are linked by hydrogen bonds to form 2₁ spiral chains. In (III), (IV) and (V), macrocyclic structures are formed from two acid and two base components, by an alternate arrangement of the acid and base moieties.     

The hydrogen‐bonded adduct 7,16‐diazonia‐18‐crown‐6–4‐aminobenzenesulfonate–water (1/2/2)

In the title hydrated adduct, 1,4,10,13‐tetraoxa‐7,16‐diazo­nia­cyclo­octa­decane bis(4‐amino­benzene­sulfonate) dihydrate, C₁₂H₂₈N₂O₄²⁺·2C₆H₆NO₃S⁻·2H₂O, formed between 7,16‐di­aza‐18‐crown‐6 and the dihydrate of 4‐amino­benzene­sulfonic acid, the macrocyclic cations lie across centres of inversion in the orthorhombic space group Pbca. The anions alone form zigzag chains, and the cations and anions together form sheets that are linked via water mol­ecules and anions to form a three‐dimensional grid.     

The antiestrogen [2‐(4‐benzyl­phenoxy)­ethyl]­diethyl­ammonium chloride

The crystal structure of the title compound, C₁₉H₂₆NO⁺·Cl^? (common name: N,N‐diethyl‐2‐[(4‐phenyl­methyl)phenoxy]‐ethan­amine hydro­chloride), contains one mol­ecule in the asymmetric unit. The planes through the two phenyl rings are roughly perpendicular. Protonation occurs at the N atom, to which the Cl^? ion is linked via an N—H?Cl hydrogen bond. The mol­ecule adopts an eclipsed rather than extended conformation.     

Absolute configuration of (−)‐4‐(3,4‐di­chloro­phenyl)‐4‐(2‐pyridyl)­butanoic acid: essential information to determine crucial steric features of ­arpromidine‐type hist­amine H2 receptor agonists

The structural information gained from the study of the chiral building block (R)‐(?)‐4‐(3,4‐di­chloro­phenyl)‐4‐(2‐pyridyl)­butanoic acid–l ‐(?)‐ephedrine [methyl(1‐hydroxy‐1‐phenyl­prop‐2‐yl)ammon­ium 4‐(3,4‐di­chloro­phenyl)‐4‐(2‐pyrid­yl)but­an­oate], C₁₀H₁₆NO⁺·C₁₅H₁₂Cl₂NO₂^?, can be used to deduce the absolute configuration of highly potent arpromidine‐type hist­amine H₂ receptor agonists, as the chiral butanoic acid can be converted to (R)‐(?)‐3‐(3,4‐di­chloro­phenyl)‐3‐(2‐pyridyl)­propyl­amine and to the corresponding R‐configured arpromidine analogue.     

2,4‐Diamino‐5‐(1‐naphthyl)‐3,5‐diaza‐1‐azoniaspiro[5.5]undeca‐1,3‐diene chloride

The title salt, C₁₈H₂₂N₅⁺·Cl^?, is a member of a new series of lipophilic 4,6‐di­amino spiro‐s‐triazines which are potent in­hib­itors of di­hydro­folate reductase. The protonated triazine ring deviates from planarity, whereas the cyclo­hexane ring adopts a chair conformation. A rather unusual hydrogen‐bonding scheme exists in the crystal. There is a centrosymmetric arrangement involving two amino groups and two triazine ring N atoms, with graph‐set R(8) and an N?N distance of 3.098 (3) Å, flanked by two additional R(8) systems, involving two amino groups, a triazine ring N atom and a Cl^? anion, with N?Cl distances in the range 3.179 (2)–3.278 (2) Å. Furthermore, the Cl^? anion, the protonated triazine ring N atom and an amino group form a hydrogen‐bonding system with graph‐set R(6).     

(Z)‐2‐Methylbuten‐1‐yl(aryl)iodonium trifluoromethanesulfonates containing electron‐withdrawing groups on the aryl moiety

The crystal structures of [(Z)‐2‐methyl­but‐1‐en‐1‐yl]­[4‐(tri­fluoro­methyl)­phenyl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₂H₁₃F₃I⁺·CF₃O₃S^?, (I), (3,5‐di­chloro­phenyl)­[(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₁H₁₂­Cl₂I⁺·CF₃O₃S^?, (II), and bis{[3,5‐bis­(tri­fluoro­methyl)­phenyl][(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium} bis­(tri­fluoro­methane­sulfonate) di­chloro­methane solvate, 2C₁₃H₁₂F₆I⁺·­2CF₃­O₃S^?·CH₂Cl₂, (III), are described. Neither simple acyclic β,β‐di­alkyl‐substituted alkenyl­(aryl)­idonium salts nor a series containing electron‐deficient aryl rings have been described prior to this work. Compounds (I)–(III) were found to have distorted square‐planar geometries, with each I atom interacting with two tri­fluoro­methane­sulfonate counter‐ions.     

Aqua(2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole‐κ2N,N′)(imino­diacetato‐κ3O,N,O′)­chromium(III) chloride mono­hydrate

Crystals of the title compound, [Cr(C₄H₅NO₄)(C₆H₆N₄S₂)(H₂O)]Cl·H₂O, consist of Cr^III complex cations, Cl⁻ counter‐ions and lattice water mol­ecules. The complex cation assumes an octahedral coordination geometry, formed by a tridentate imino­di­acetate dianion (IDA), a di­amino­bi­thia­zole (DABT) mol­ecule and a water mol­ecule. The planar DABT group chelates the Cr^III ion with normal Cr—N distances [2.0574 (17) and 2.0598 (17) Å], but the DABT mol­ecule is inclined to the coordination plane by a dihedral angle of 17.23 (7)°. In the monodentate carboxylate groups of the IDA ion, the coordinated C—O bonds [1.288 (3) and 1.284 (3) Å] are much longer than the uncoordinated C—O bonds [1.222 (3) and 1.225 (3) Å].     

The 2:1 complex of maleic acid and 1,4‐diazabicyclo[2.2.2]octane: hydrogen‐bonded sheets linked by C–H⋯O hydrogen bonds

In the title complex, 1,4‐diazo­niabi­cyclo­[2.2.2]­octane bis­(hy­drogen maleate), C₆H₁₄N₂²⁺·2C₄H₃O₄^?, the C₄H₃O₄^? and C₆H₁₄N₂²⁺ ions, derived from maleic acid and 1,4‐di­aza­bi­cyclo­[2.2.2]­octane, respectively, are disordered across a mirror plane in space group Cmc2₁, and they are linked by two nearly linear N—H?O hydrogen bonds, with N?O distances of 2.662 (3) and 2.614 (4) Å, and N—H?O angles of 173°. The crystal structure consists of sheets with reticulations of 3.3792 (4) Å in stratum and 7.3892 (8) Å in width. The sheets are linked by C—H?O hydrogen bonds.