Tetrakis(chloromethyl)phosphonium chloride monohydrate

Tetrakis­(chloro­methyl)­phospho­nium chloride monohydrate, C₄H₈Cl₄P⁺·Cl^?·H₂O or P(CH₂Cl)₄⁺·Cl^?·H₂O, is the first crystal structure determination of a tetrakis­(halogeno­methyl)­phospho­nium compound to date. The only comparable structures known so far are of phospho­nium ions containing just one halogeno­methyl group. The solvent water mol­ecule interacts with the Cl^? anion via hydrogen bonds, with O?Cl distances of 3.230 (2) and 3.309 (2) Å. The structure also contains several C—H?Cl^? and C—H?O contacts, though with longer D?A distances [D?A 3.286 (3)–3.662 (2) Å] or bent D—H?A angles. For these reasons, the C—H?Cl^? and C—H?O interactions should not be considered as strong hydrogen bonds.     

Multicentre hydrogen bonds in a 2:1 aryl­sulfonyl­imidazol­one ­hydro­chloride salt

The title compound, (S)‐(+)‐4‐[5‐(2‐oxo‐4,5‐di­hydro­imidazol‐1‐yl­sulfonyl)­indolin‐1‐yl­carbonyl]­anilinium chloride (S)‐(+)‐1‐[1‐(4‐amino­benzoyl)­indoline‐5‐sulfonyl]‐4‐phenyl‐4,5‐di­hydro­imidazol‐2‐one, C₂₄H₂₃N₄O₄S⁺·Cl^?·C₂₄H₂₂N₄O₄S, crystallizes in space group C2 from a CH₃OH/CH₂Cl₂ solution. In the crystal structure, there are two different conformers with their terminal C₆ aromatic rings mutually oriented at angles of 67.69 (14) and 61.16 (15)°. The distances of the terminal N atoms (of the two conformers) from the chloride ion are 3.110 (4) and 3.502 (4) Å. There are eight distinct hydrogen bonds, i.e. four N—H?Cl, three N—H?O and one N—H?N, with one N—H group involved in a bifurcated hydrogen bond with two acceptors sharing the H atom. C—H?O contacts assist in the overall hydrogen‐bonding process.     

2,2′‐(Iminodimethylene)bis(1H‐benzimidazolium)(1+) chloride

The title compound, C₁₆H₁₆N₅⁺·Cl⁻ (nbbH⁺·Cl⁻), displays N—H⋯N, N—H⋯Cl and π–π inter­actions in the crystal packing. The Cl⁻ anion is chelated by the nbbH⁺ cation via two N—H⋯Cl hydrogen bonds. Inter‐ion N—H⋯N and N—H⋯Cl hydrogen bonds link ions related by 2₁ screw axes into chains along the c axis. These chains are further linked by glide‐plane operations to generate a three‐dimensional network, which is additionally stabilized by inter­chain π–π inter­actions.     

Hydrogen‐bonded bilayers in ­piperazinium(2+) bis(mandelate) bis(methanol) solvate

In the title compound, C₄H₁₂N₂²⁺·2C₈H₇O₃^?·2CH₄O, the cations lie across centres of inversion and are disordered over two orientations with equal occupancy; there are equal numbers of (R)‐ and (S)‐mandelate anions present (mandelate is α‐hydroxy­benzene­acetate). The anions and the neutral water mol­ecules are linked by O—H?O hydrogen bonds [O?O 2.658 (3) and 2.682 (3) Å, and O—H?O 176 and 166°] into deeply folded zigzag chains. Each orientation of the cation forms two symmetry‐related two‐centre N—H?O hydrogen bonds [N?O 2.588 (4) and 2.678 (4) Å, and N—H?O 177 and 171°] and two asymmetric, but planar, three‐centre N—H?(O)₂ hydrogen bonds [N?O 2.686 (4)–3.137 (4) Å and N—H?O 137–147°], and by means of these the cations link the anion/water chains into bilayers.     

(2‐Hydroxy­ethyl)­hydrazinium(2+) dichloride

The crystal structure of the title compound, C₂H₁₀N₂O²⁺·2Cl⁻, is built up from one 2‐hydroxy­ethyl­hydrazinium(2+) cation and two Cl⁻ anions. The mol­ecular structure is stabilized by O—H⋯Cl and N—H⋯Cl hydrogen bonds. The crystal structure is stabilized by one N—H⋯O and three N—H⋯Cl inter­actions, and the three‐dimensional network of hydrogen bonds stabilizes the crystal packing. All five hydrazinium H atoms are involved in hydrogen bonds to Cl⁻ anions. The Cl⋯H contact distances range from 2.122 (15) to 2.809 (14) Å.     

(–)‐(S)‐2‐(Fluoro­di­phenyl­methyl)­pyrrolidinium chloride

The title compound, C₁₇H₁₉FN⁺·Cl^?, has an ionic structure, and cations and anions are linked into infinite chains by Cl?H—N—H?Cl hydrogen bonds. The absolute configuration (S) was confirmed.     

N,N′‐Bis(2‐hydroxycyclohexyl)‐N,N′‐bis(2‐hydroxyethyl)ethane‐1,2‐diaminium dichloride

The achiral meso form of the title compound, C₁₈H₃₈N₂O₄²⁺·2Cl⁻, crystallizes to form undulating layers consisting of chains linked via weak hydroxyalkyl C—H...Cl contacts. The chains are characterized by centrosymmetric hydrogen‐bonded dimers generated via N—H...Cl and hydroxycycloalkyl O—H...Cl interactions. trans‐N‐Alkyl bridges subdivide the chains into hydrophilic segments flanked by hydrophobic cycloalkyl stacks along [001].     

N6‐Furfuryladenine (kinetin) hydrochloride

In the title compound, N⁶‐furfuryl­adenin‐3‐ium chloride, C₁₀H₁₀N₅O⁺·Cl⁻, the adenine moiety exists as the N3‐protonated N7–H tautomer. The orientation of the N6 substituent (furfuryl moiety) is distal to the imidazole ring of the adenine base. The dihedral angle between the adenine plane and the furfuryl ring plane is 76.1 (2)°. Three N—H⋯Cl hydrogen bonds are responsible for the formation of a supramolecular chain‐like pattern. These supramolecular chains are interconnected by C—H⋯Cl hydrogen bonds to form a hydrogen‐bonded sheet and a three‐dimensional hydrogen‐bonded network.     

Secondary inter­actions in gold(I) complexes with thione ligands. 5. Two ionic compounds of the form bis­(thione)gold(I) bis(4‐halobenzene­sulfon­yl)amide

Bis(1,3‐thia­zolidine‐2‐thione‐κS²)gold(I) bis­(4‐chloro­benzene­sulfonyl)amide, [Au(C₃H₅NS₂)₂](C₁₂H₈Cl₂NS₂O₄), has no imposed symmetry. Classical N—H⋯N and N—H⋯O hydrogen bonds link the residues to form chains parallel to the b axis. Weaker inter­actions involve C—H⋯O, C—H⋯Au and a number of X⋯Cl contacts (X = Cl, S or Au) clustered in the region y ≃ . In bis­(1‐methyl­imidazolidine‐2‐thione‐κS²)gold(I) bis­(4‐iodo­benzene­sulfonyl)amide, [Au(C₄H₈N₂S)₂](C₁₂H₈I₂NS₂O₄), the Au atom of the cation and the N atom of the anion lie on the twofold axis (0, y, ) in the space group C2/c. The formula unit forms a self‐contained ring with two symmetry‐equivalent N—H⋯O hydrogen bonds, and weak C—H⋯X (X = O, I or S), Au⋯I and I⋯I contacts are observed. In both compounds, the anions display extended conformations.     

Three isomeric bis(methoxycarbonyl)[2.2]paracyclophanes

The title isomers 4,16‐ (pseudo‐ortho), 4,15‐ (pseudo‐gem) and 4,12‐bis­(methoxy­carbonyl)[2.2]­para­cyclo­phane (pseudo‐para), C₂₀H₂₀O₄, all show the typical structural features of [2.2]­para­cyclo­phanes (flattened boat conformation of the rings, lengthened single bonds in the bridges and narrow ring angles at the bridgehead atoms). The 4,12‐isomer displays crystallographic inversion symmetry. The carbonyl groups adopt a conformation in which they are directed away from the ring systems towards the nearest bridge; the corresponding angle at the ring substituent atom is widened. Crystal packing involves C—H?π interactions for the 4,15‐isomer and weak C—H?O hydrogen bonds for the other two isomers.     

trans‐Di­chloro­tetrakis(4‐methylpyrimidine‐N1)­ruthenium(II)

The title compound, trans‐[Ru^IICl₂(N¹‐mepym)₄] (mepym is 4‐methylpyrimidine, C₅H₆N₂), obtained from the reaction of trans,cis,cis‐[Ru^IICl₂(N¹‐mepym)₂(SbPh₃)₂] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N¹ and arranged in a propeller‐like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N³ and Cl atoms are involved in intermolecular C—H?N and C—­H?Cl hydrogen‐bond interactions.     

Antidiarrhetic loperamide hydrochloride

Single crystals of the anhydrous form of the title compound {systematic name: 1‐[3‐(dimethylcarbamoyl)‐3,3‐diphenylpropyl]‐4‐hydroxy‐4‐(4‐chlorophenyl)piperidin‐1‐ium chloride}, C₂₉H₃₄ClN₂O₂⁺·Cl⁻, were obtained by diffusion of acetone into a solution in 2‐propanol. In the structure, N—H...Cl⁻ and O—H...Cl⁻ hydrogen bonds connect neighbouring molecules and chloride anions to form chains along the c‐axis direction. Neighbouring chains along the b‐axis direction are connected by intermolecular C—H...Cl⁻ contacts, defining layers parallel to the (100) planes. The layers are connected by weak intermolecular C—H...Cl interactions only, which may account for the plate‐like shape of the crystals.     

Supramolecular structures of three isomeric 4‐(methyl­phenylamino)­pyridine‐3‐sulfonamides

The structures of the three title isomers, namely 4‐(2‐methyl­anilino)pyridine‐3‐sulfonamide, (I), 4‐(3‐methyl­anilino)pyridine‐3‐sulfonamide, (II), and 4‐(4‐methyl­anilino)pyridine‐3‐sulfonamide, (III), all C₁₂H₁₃N₃O₂S, differ in their hydrogen‐bonding arrangements. In all three mol­ecules, the conformation of the 4‐amino­pyridine‐3‐sulfon­amide moiety is conserved by an intra­molecular N—H⋯O hydrogen bond and a C—H⋯O inter­action. In the supra­mol­ecular structures of all three isomers, similar C(6) chains are formed via inter­molecular N—H⋯N hydrogen bonds. N—H⋯O hydrogen bonds lead to C(4) chains in (I), and to R₂²(8) centrosymmetric dimers in (II) and (III). In each isomer, the overall effect of all hydrogen bonds is to form layer structures.     

Constructor graph description of the hydrogen‐bonding supramolecular assembly in two ionic compounds: 2‐(pyrazol‐1‐yl)ethylammonium chloride and diaquadichloridobis(2‐hydroxyethylammonium)cobalt(II) dichloride

Covalent bond tables are used to generate hydrogen‐bond pattern designator symbols for the crystallographically characterized title compounds. 2‐(Pyrazol‐1‐yl)ethylammonium chloride, C₅H₁₀N₃⁺·Cl⁻, (I), has three unique, strong, charge‐assisted hydrogen bonds of the types N—H...Cl and N—H...N that form unary through ternary levels of graph‐set interactions. Diaquadichloridobis(2‐hydroxyethylammonium)cobalt(II) dichloride, [CoCl₂(C₂H₈NO)₂(H₂O)₂]Cl₂, (II), forms five unique charge‐assisted hydrogen bonds of the types O—H...Cl and N—H...Cl. These form graph‐set patterns up to the quinary level. The Co complex in (II) resides at a crystallographic inversion center; thus the number of hydrogen bonds to consider doubles due to their G‐equivalence, and the handling of such a case is demonstrated.     

Different supramolecular architectures mediated by different weak interactions in the crystals of three N‐aryl‐2,5‐dimethoxybenzenesulfonamides

The synthesis and evaluation of the pharmacological activities of molecules containing the sulfonamide moiety have attracted interest as these compounds are important pharmacophores. The crystal structures of three closely related N‐aryl‐2,5‐dimethoxybenzenesulfonamides, namely N‐(2,3‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (I), N‐(2,4‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (II), and N‐(2,4‐dimethylphenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₆H₁₉NO₄S, (III), are described. The asymmetric unit of (I) consists of two symmetry‐independent molecules, while those of (II) and (III) contain one molecule each. The molecular conformations are stabilized by different intramolecular interactions, viz. C—H…O interactions in (I), N—H…Cl and C—H…O interactions in (II), and C—H…O interactions in (III). The crystals of the three compounds display different supramolecular architectures built by various weak intermolecular interactions of the types C—H…O, C—H…Cl, C—H…π(aryl), π(aryl)–π(aryl) and Cl…Cl. A detailed Hirshfeld surface analysis of these compounds has also been conducted in order to understand the relationship between the crystal structures. The d _norm and shape‐index surfaces of (I)–(III) support the presence of various intermolecular interactions in the three structures. Analysis of the fingerprint plots reveals that the greatest contribution to the Hirshfeld surfaces is from H…H contacts, followed by H…O/O…H contacts. In addition, comparisons are made with the structures of some related compounds. Putative N—H…O hydrogen bonds are observed in 29 of the 30 reported structures, wherein the N—H…O hydrogen bonds form either C (4) chain motifs or R ₂²(8) rings. Further comparison reveals that the characteristics of the N—H…O hydrogen‐bond motifs, the presence of other interactions and the resultant supramolecular architecture is largely decided by the position of the substituents on the benzenesulfonyl ring, with the nature and position of the substituents on the aniline ring exerting little effect. On the other hand, the crystal structures of (I)–(III) display several weak interactions other than the common N—H…O hydrogen bonds, resulting in supramolecular architectures varying from one‐ to three‐dimensional depending on the nature and position of the substituents on the aniline ring.     

Protonation products of pentaaminopentane as novel building blocks for hydrogen‐bonded networks

The structures of 3‐amino‐1,2R,4S,5‐tetra­ammoniopentane tetrachloride monohydrate, C₅H₂₁N₅⁴⁺·4Cl^?·H₂O, and 1,2R,3,4S,5‐penta­ammoniopentane tetra­chloro­zincate tri­chlor­ide monohydrate, (C₅H₂₂N₅)[ZnCl₄]Cl₃·H₂O, have been determined from single‐crystal X‐ray diffraction data. Both compounds show a complex network of N—H?O, O—H?Cl and N—H?Cl hydrogen bonds. There are a total of 14 H atoms of the tetra‐cation and 15 H atoms of the penta‐cation available for hydrogen bonding. However, due to the particular shape of the primary linear poly­ammonium cations, only a certain number of H atoms can be involved in hydrogen‐bond formation. It is further shown that hydrogen bonding has an influence on the conformation of such alkyl­ammonium cations.     

The hydrochloride and hydrobromide salt forms of (S)‐amphetamine

Despite the high profile of amphetamine, there have been relatively few structural studies of its salt forms. The lack of any halide salt forms is surprising as the typical synthetic route for amphetamine initially produces the chloride salt. (S)‐Amphetamine hydrochloride [systematic name: (2S)‐1‐phenylpropan‐2‐aminium chloride], C₉H₁₄N⁺·Cl⁻, has a Z′ = 6 structure with six independent cation–anion pairs. That these are indeed crystallographically independent is supported by different packing orientations of the cations and by the observation of a wide range of cation conformations generated by rotation about the phenyl–CH₂ bond. The supramolecular contacts about the anions also differ, such that both a wide variation in the geometry of the three N—H...Cl hydrogen bonds formed by each chloride anion and differences in C—H...Cl contacts are apparent. (S)‐Amphetamine hydrobromide [systematic name: (2S)‐1‐phenylpropan‐2‐aminium bromide], C₉H₁₄N⁺·Br⁻, is broadly similar to the hydrochloride in terms of cation conformation, the existence of three N—H...X hydrogen‐bond contacts per anion and the overall two‐dimensional hydrogen‐bonded sheet motif. However, only the chloride structure features organic bilayers and Z′ > 1.     

Comparison of the methyl ester of l‐tyrosine hydrochloride and its methanol monosolvate

Solvent‐free (2S)‐methyl 2‐ammonio‐3‐(4‐hydroxy­phenyl)­propionate chloride, C₁₀H₁₄NO₃⁺·Cl⁻, (I), and its methanol solvate, C₁₀H₁₄NO₃⁺·Cl⁻·CH₃OH, (II), are obtained from different solvents: crystallization from ethanol or propan‐2‐ol gives the same solvent‐free crystals of (I) in both cases, while crystals of (II) were obtained by crystallization from methanol. The structure of (I) is characterized by the presence of two‐dimensional layers linked together by N—H⋯Cl and O—H⋯Cl hydrogen bonds and also by C—H⋯O contacts. Incorporation of the methanol solvent mol­ecule in (II) introduces additional O—H⋯O hydrogen bonds linking the two‐dimensional layers, resulting in the formation of a three‐dimensional network.     

Hydro­gen‐bonding patterns in two structural isomers of 3,6‐bis(2‐chloro­phenyl)‐1,4‐di­hydro‐1,2,4,5‐tetrazine

Two structural isomers, 3,6‐bis(2‐chloro­phenyl)‐1,4‐di­hydro‐1,2,4,5‐tetrazine, (I), and 3,5‐bis(2‐chloro­phenyl)‐4‐amino‐1H‐1,2,4‐triazole, (II), both C₁₄H₁₀Cl₂N₄, form chain‐like structures in the solid state, stabilized by N—H⋯N and N—H⋯Cl hydrogen bonds. A contribution from weak interactions to the strong hydrogen‐bond network is observed in both structures. The secondary graph sets for intermolecular hydrogen bonds [(11) for (I) and (12) for (II)] indicate the similarity between the networks.     

Two‐component molecular crystals composed of chloronitrobenzoic acids and 4‐aminopyridine

The crystal structures of the four isomeric organic salts 4‐amino­pyridinium 2‐chloro‐4‐nitro­benzoate, (I), 4‐amino­pyridinium 2‐chloro‐5‐nitro­benzoate, (II), 4‐amino­pyridinium 5‐chloro‐2‐nitro­benzoate, (III), and 4‐amino­pyridinium 4‐chloro‐2‐nitro­benzoate, (IV), all C₅H₇N₂⁺·C₇H₃ClNO₄^?, are presented. Compound (I) has one intramolecular hydrogen bond, one intermolecular C—H?O hydrogen bond and π–π‐stacking interactions. Compound (II) has N—H?O, C—H?O and C—H?Cl hydrogen bonds, and Cl?O—C electrostatic interactions. Compound (III) has N—H?O and C—H?O hydrogen bonds. Compound (IV) has a π–π‐stacking interaction, but no C—H?O hydrogen bonds.