Vier Natrium‐di(arensulfonyl)amide: Lamellare Schichten mit kurzen Zwischenschichtkontakten C–H…O(Nitro), C–H…F–C oder C–I…I–C

Structures of Ionic Di(arenesulfonyl)amides. 3. Four Sodium Di(arenesulfonyl)amides: Lamellar Layers Exhibiting Short C–H…O(nitro), C–H…F–C, or C–I…I–C Interlayer Contacts Low‐temperature X‐ray crystal structures are reported for NaN(SO₂C₆H₄‐4‐X)₂ · n H₂O, where X = NO₂ and n = 3 ( 1 , monoclinic, space group P2₁, Z = 2), X = F and n = 3 ( 2 , monoclinic, P2₁/c, Z = 4), X = F and n = 1 ( 3 , orthorhombic, Pccn, Z = 8), or X = I and n = 1 ( 4 , monoclinic, P2₁/c, Z = 4). The four compounds are examples of layered inorgano‐organic solids where the inorganic component is comprised of metal cations, N(SO₂)₂ groups and H₂O molecules and the outer regions are formed by the 4‐substituted phenyl rings of the folded anions. In the two‐dimensional coordination networks, the cations adopt either an octahedral [Na(O–S)₂(OH₂)₄] ( 1 , 2 ) or a distorted monocapped octahedral [NaN(O–S)₄(OH₂)₂] ( 3 , 4 ) environment. Taking into account the differing crystal symmetries within the two pairs of compounds, it is remarkable that the trihydrates 1 / 2 and the monohydrates 3 / 4 each display chemically identical and nearly isometric Na–O or Na–O/N networks. In the crystal packings, parallel layers are connected through weak hydrogen bonds C–H…O(nitro) ( 1 ) or C–H…F ( 2 , 3 ), or through short “type I” I…I contacts ( 4 ). There is good evidence that the strikingly distinct crystal symmetries in the halogenated homologues 3 / 4 are determined by the specific complementarity requirements of the interlayer binding centres.     

Crystal structures of sodium magnesium selenate decahydrate,Na2Mg(SeO4)2·10H2O,a new selenate salt,and sodium magnesium selenate dihydrate,Na2Mg(SeO4)2·2H2O

Metal selenates crystallize in many instances in isomorphic structures of the corresponding sulfates. Sodium magnesium selenate decahydrate, Na₂Mg(SeO₄)₂·10H₂O, and sodium magnesium selenate dihydrate, Na₂Mg(SeO₄)₂·2H₂O, were synthesized by preparing solutions of Na₂SeO₄ and MgSeO₄·6H₂O with different molar ratios. The structures contain different Mg octahedra, i.e. [Mg(H₂O)₆] octahedra in the decahydrate and [MgO₄(H₂O)₂] octahedra in the dihydrate. The sodium polyhedra are also different, i.e. [NaO₂(H₂O)₄] in the decahydrate and [NaO₆(H₂O)] in the dihydrate. The selenate tetrahedra are connected with the chains of Na polyhedra in the two structures. O—H…O hydrogen bonding is observed in both structures between the coordinating water molecules and selenate O atoms.     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.     

A whole zoo of hydrogen bonds in one crystal structure: tris(isonicotinium) hydrogensulfate sulfate monohydrate

Depending on the reaction partner, the organic ditopic molecule isonicotinic acid (Hina) can act either as a Brønsted acid or base. With sulfuric acid, the pyridine ring is protonated to become a pyridinium cation. Crystallization from ethanol affords the title compound tris(4‐carboxypyridinium) hydrogensulfate sulfate monohydrate, 3C₆H₆NO₂⁺·HSO₄⁻·SO₄²⁻·H₂O or [(H₂ina)₃(HSO₄)(SO₄)(H₂O)]. This solid contains 11 classical hydrogen bonds of very different flavour and nonclassical C—H…O contacts. All N—H and O—H donors find at least one acceptor within a suitable distance range, with one of the three pyridinium H atoms engaged in bifurcated N—H…O hydrogen bonds. The shortest hydrogen‐bonding O…O distance is subtended by hydrogensulfate and sulfate anions, viz. 2.4752 (19) Å, and represents one of the shortest hydrogen bonds ever reported between these residues.     

Lamellare Schichtstrukturen von M[N(SO2C6H4‐4‐COOCH3)2] · n H2O (M = Na,n = 1; M = K,n = 0): Gibt es schwache Wasserstoffbrücken CH2–H…O=C zwischen den Schichten?

Structures of Ionic Di(arenesulfonyl)amides. 5. Lamellar Layer Structures of M[N(SO₂C₆H₄‐4‐COOCH₃)₂] · n H₂O (M = Na, n = 1; M = K, n = 0): Are there Weak Hydrogen Bonds CH₂–H…O=C between the Layers? The new lamellar compounds NaN(SO₂C₆H₄‐4‐COOMe)₂ · H₂O ( 1 a ) and KN(SO₂C₆H₄‐4‐COOMe)₂ ( 2 a ), obtained by neutralizing the corresponding strong NH acid with aqueous NaOH or KOH, were characterized by low‐temperature X‐ray diffraction ( 1 a : orthorhombic, space group Pbca, Z = 8, Z′ = 1; 2 a : orthorhombic, P2₁2₁2₁, Z = 8, Z′ = 2). Both crystals are further examples of layered inorgano‐organic solids where the inorganic component is comprised of metal cations, coordinating N(SO₂)₂ groups and water molecules (in 1 a ) and the outer regions are formed by the 4‐substituted phenyl rings of the folded anions, which approximate to mirror symmetry. In the two‐dimensional networks, the cations adopt respectively a distorted octahedral [Na(O–S)₄(OH₂)₂], an irregular [K(1)O₆N₂], or an irregular [K(2)O₉] coordination. In contrast to the previously reported carboxylic congeners, where an extensive series of C–O–H…O=C hydrogen bonds is observed between layers, the esterified materials do not display any O–CH₂–H…O=C interlayer bonding, although such interactions and short C_ar–H…O=C/O=S contacts exist within the lamellae.     

Supramolecular interactions in salts/cocrystals involving pyrimidine derivatives of sulfonate/carboxylic acid

The crystal structures of three compounds involving aminopyrimidine derivatives are reported, namely, 5-fluorocytosinium sulfanilate–5-fluorocytosine–4-azaniumylbenzene-1-sulfonate (1/1/1), C₄H₅FN₃O⁺·C₆H₆NO₃S⁻·C₄H₄FN₃O·C₆H₇NO₃S, I , 5-fluorocytosine–indole-3-propionic acid (1/1), C₄H₄FN₃O·C₁₁H₁₁NO₂, II , and 2,4,6-triaminopyrimidinium 3-nitrobenzoate, C₄H₈N₅⁺·C₇H₄NO₄⁻, III , which have been synthesized and characterized by single-crystal X-ray diffraction. In I , there are two 5-fluorocytosine (5FC) molecules (5FC-A and 5FC-B) in the asymmetric unit, with one of the protons disordered between them. 5FC-A and 5FC-B are linked by triple hydrogen bonds, generating two fused rings [two R₂²(8) ring motifs]. The 5FC-A molecules form a self-complementary base pair [R₂²(8) ring motif] via a pair of N—H…O hydrogen bonds and the 5FC-B molecules form a similar complementary base pair [R₂²(8) ring motif]. The combination of these two types of pairing generates a supramolecular ribbon. The 5FC molecules are further hydrogen bonded to the sulfanilate anions and sulfanilic acid molecules via N—H…O hydrogen bonds, generating R₄⁴(22) and R⁶₆(36) ring motifs. In cocrystal II , two types of base pairs (homosynthons) are observed via a pair of N—H…O/N—H…N hydrogen bonds, generating R₂²(8) ring motifs. The first type of base pair is formed by the interaction of an N—H group and the carbonyl O atom of 5FC molecules through a couple of N—H…O hydrogen bonds. Another type of base pair is formed via the amino group and a pyrimidine ring N atom of the 5FC molecules through a pair of N—H…N hydrogen bonds. The base pairs (via N—H…N hydrogen bonds) are further bridged by the carboxyl OH group of indole-3-propionic acid and the O atom of 5FC through O—H…O hydrogen bonds on either side of the R₂²(8) motif. This leads to a DDAA array. In salt III , one of the N atoms of the pyrimidine ring is protonated and interacts with the carboxylate group of the anion through N—H…O hydrogen bonds, leading to the primary ring motif R₂²(8). Furthermore, the 2,4,6-triaminopyrimidinium (TAP) cations form base pairs [R₂²(8) homosynthon] via N—H…N hydrogen bonds. A carboxylate O atom of the 3-nitrobenzoate anion bridges two of the amino groups on either side of the paired TAP cations to form another ring [R₃²(8)]. This leads to the generation of a quadruple DADA array. The crystal structures are further stabilized by π–π stacking ( I and III ), C—H…π ( I and II ), C—F…π ( I ) and C—O…π ( II ) interactions.     

Cs2.91Na1.34Fe3+0.25[Fe3O(SO4)6(H2O)3]·5H2O,a member of the Maus's salt family

The title compound, tricaesium sodium iron(III) μ₃‐oxido‐hexa‐μ₂‐sulfato‐tris[aquairon(III)] pentahydrate, Cs_2.91Na_1.34Fe³⁺_0.25[Fe₃O(SO₄)₆(H₂O)₃]·5H₂O, belongs to the family of Maus's salts, K₅[Fe₃O(SO₄)₆(H₂O)₃]·6H₂O, which is based on the triaqua‐μ₃‐oxido‐hexa‐μ‐sulfato‐triferrate(III) anion, [Fe₃O(SO₄)₆(H₂O)₃]⁵⁻, with Fe in a characteristically distorted octahedral coordination environment, sharing a common corner via an oxide O atom. Cs in four different cation sites, Na in three different cation sites and five water molecules link the anions in three dimensions and set up a crystal structure in which those parts parallel to (001) and within 0.05 < z < 0.95 have a distinct trigonal pseudosymmetry, whereas the cation arrangement and bonding near z∼ 0 generate a clear‐cut noncentrosymmetric polar edifice with the monoclinic space group C2. The structure shows some cation disorder in the region near z ∼ , where one Na atom in octahedral coordination is partly substituted by Fe³⁺, and a Cs atom is substituted by small amounts of Na on a separate nearby site. One Na atom, located on a twofold axis at z = 0 and tetrahedrally coordinated by four sulfate O atoms of two [Fe₃O(SO₄)₆(H₂O)₃]⁵⁻ units, plays a key role in generating the noncentrosymmetric structure. Three of the seven different cation sites are on twofold axes (one Na⁺ site and two Cs⁺ sites), and all other atoms of the structure are in general positions.     

Planarity of heteroaryldithiocarbazic acid derivatives showing tuberculostatic activity: structure–activity relationships

The search for new tuberculostatics is an important issue due to the increasing resistance of Mycobacterium tuberculosis to existing agents and the resulting spread of the pathogen. Heteroaryldithiocarbazic acid derivatives have shown potential tuberculostatic activity and investigations of the structural aspects of these compounds are thus of interest. Three new examples have been synthesized. The structure of methyl 2‐[amino(pyridin‐3‐yl)methylidene]hydrazinecarbodithioate, C₈H₁₀N₄S₂, at 293 K has monoclinic (P2₁/n) symmetry. It is of interest with respect to antibacterial properties. The structure displays N—H…N and N—H…S hydrogen bonding. The structure of N′‐(pyrrolidine‐1‐carbonothioyl)picolinohydrazonamide, C₁₁H₁₅N₅S, at 100 K has monoclinic (P2₁/n) symmetry and is also of interest with respect to antibacterial properties. The structure displays N—H…S hydrogen bonding. The structure of (Z)‐methyl 2‐[amino(pyridin‐2‐yl)methylidene]‐1‐methylhydrazinecarbodithioate, C₉H₁₃N₄S₂, has triclinic (P) symmetry. The structure displays N—H…S hydrogen bonding.     

Lamellare Schichten auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstrukturen der Komplexe [Mg(H2O)6]Z2 und [Be(H2O)4]Z2�2 H2O mit Z‐ = C6H4(SO2)2N‐: Metallsalze des Benzol‐1, 2‐di(sulfonyl)amins. 8 [1, 2]

Metal Salts of Benzene‐1, 2‐di(sulfonyl)amine. 8. Lamellar Layers Based upon Hydrogen Bonding and π‐Stacking: Crystal Structures of the Complexes [Mg(H₂O)₆]Z₂ and [Be(H₂O)₄]Z₂�2 H₂O, where Z^‐ is C₆H₄(SO₂)₂N^‐ The crystal structures of the title complexes (both triclinic, space group P1¯, Z = 1 for M = Mg, Z = 2 for M = Be) have been determined by low‐temperature X‐ray diffraction. They consist of non‐coordinating ortho‐benzenedisulfonimide anions and, respectively, inversion‐symmetric octahedral [Mg(H₂O)₆]²⁺ cations or tetrahedral [Be(H₂O)₄]²⁺ cations and two non‐coordinating water molecules. In both structures, all O—H hydrogen bond donor groups are used to associate the components into two‐dimensional assemblies comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of vertically protruding benzo rings. Carbocycles drawn alternatingly from adjacent layers form π‐stacking arrays, whereby the aromatic rings display intercentroid distances in the range 340—370 pm. Several short C—H ⃜O contacts, which may be viewed as weak hydrogen bonds, occur within and between the layers.     

Supramolecular hydrogen‐bonding patterns in the organic–inorganic hybrid compound bis(4‐amino‐5‐chloro‐2,6‐dimethylpyrimidinium) tetrathiocyanatozinc(II)–4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine–water (1/2/2)

Zinc thiocyanate complexes have been found to be biologically active compounds. Zinc is also an essential element for the normal function of most organisms and is the main constituent in a number of metalloenzyme proteins. Pyrimidine and aminopyrimidine derivatives are biologically very important as they are components of nucleic acids. Thiocyanate ions can bridge metal ions by employing both their N and S atoms for coordination. They can play an important role in assembling different coordination structures and yield an interesting variety of one‐, two‐ and three‐dimensional polymeric metal–thiocyanate supramolecular frameworks. The structure of a new zinc thiocyanate–aminopyrimidine organic–inorganic compound, (C₆H₉ClN₃)₂[Zn(NCS)₄]·2C₆H₈ClN₃·2H₂O, is reported. The asymmetric unit consist of half a tetrathiocyanatozinc(II) dianion, an uncoordinated 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidinium cation, a 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine molecule and a water molecule. The Zn^II atom adopts a distorted tetrahedral coordination geometry and is coordinated by four N atoms from the thiocyanate anions. The Zn^II atom is located on a special position (twofold axis of symmetry). The pyrimidinium cation and the pyrimidine molecule are not coordinated to the Zn^II atom, but are hydrogen bonded to the uncoordinated water molecules and the metal‐coordinated thiocyanate ligands. The pyrimidine molecules and pyrimidinium cations also form base‐pair‐like structures with an R₂²(8) ring motif via N—H…N hydrogen bonds. The crystal structure is further stabilized by intermolecular N—H…O, O—H…S, N—H…S and O—H…N hydrogen bonds, by intramolecular N—H…Cl and C—H…Cl hydrogen bonds, and also by π–π stacking interactions.     

通过氢键构筑的含3-硝基邻苯二甲酸的层状超分子化合物

合成了含大量氢键的层状超分子化合物[C₄H₁₂N₂](HL)₂ (I)和[YL(HL)(H₂O)₃]₂•2H₂O (II) (H₂L＝O₂NC₆H₃- (CO₂H)₂, 3-硝基邻苯二甲酸), 并通过元素分析、红外分析和单晶X衍射表征了组成与结构. 化合物I为双质子化哌嗪阳离子和3-硝基邻苯二甲酸氢根阴离子组成的加合物, 阴离子之间靠强烈的O—H…O氢键形成无限链状结构, 同时阴离子链通过N—H…O氢键与阳离子扩展成网状结构, 相邻的网状结构再由分子间弱作用力构筑成层状超分子. 化合物II则是在双核稀土配合物结构单元通过O—H…O氢键构成的网状结构基础上再进一步由层间弱作用力构筑成的层状超分子化合物. 化合物II的网格结构中, 菱形单元空隙里填充的两个结晶水通过氢键将结点上的双核单元更牢固地结合在一起. 化合物I为单斜晶系, P2₁/c空间群, a＝1.3176(3) nm, b＝1.1096(2) nm, c＝0.75950(15) nm, b＝97.14(3)°, V＝1.1017(4) nm³, Z＝4, μ＝0.129 mm^－1, D_c＝1.533 Mg/m³. 化合物II为三斜晶系, P-1空间群, a＝0.81262(16) nm, b＝0.86942(18) nm, c＝1.5011(3) nm, α＝99.84(3)°, β＝91.26(3)°, γ＝104.55(3)°, V＝1.0091(4) nm³, Z＝1, μ＝2.983 mm^－1, D_c＝1.910 Mg/m³.     

A comparative study of two polymorphs of bis(1‐hydroxy‐2‐methylpropan‐2‐aminium) carbonate

Alkanolamines have been known for their high CO₂ absorption for over 60 years and are used widely in the natural gas industry for reversible CO₂ capture. In an attempt to crystallize a salt of (RS)‐2‐(3‐benzoylphenyl)propionic acid with 2‐amino‐2‐methylpropan‐1‐ol, we obtained instead a polymorph (denoted polymorph II) of bis(1‐hydroxy‐2‐methylpropan‐2‐aminium) carbonate, 2C₄H₁₂NO⁺·CO₃²⁻, (I), suggesting that the amine group of the former compound captured CO₂ from the atmosphere forming the aminium carbonate salt. This new polymorph was characterized by single‐crystal X‐ray diffraction analysis at low temperature (100 K). The salt crystallizes in the monoclinic system (space group C2/c, Z = 4), while a previously reported form of the same salt (denoted polymorph I) crystallizes in the triclinic system (space group P, Z = 2) [Barzagli et al. (2012). ChemSusChem, 5 , 1724–1731]. The asymmetric unit of polymorph II contains one 1‐hydroxy‐2‐methylpropan‐2‐aminium cation and half a carbonate anion, located on a twofold axis, while the asymmetric unit of polymorph I contains two cations and one anion. These polymorphs exhibit similar structural features in their three‐dimensional packing. Indeed, similar layers of an alternating cation–anion–cation neutral structure are observed in their molecular arrangements. Within each layer, carbonate anions and 1‐hydroxy‐2‐methylpropan‐2‐aminium cations form planes bound to each other through N—H…O and O—H…O hydrogen bonds. In both polymorphs, the layers are linked to each other via van der Waals interactions and C—H…O contacts. In polymorph II, a highly directional C—H…O contact (C—H…O = 156°) shows as a hydrogen‐bonding interaction. Periodic theoretical density functional theory (DFT) calculations indicate that both polymorphs present very similar stabilities.     

Complexes of nickel(II) and copper(II) with 1,2,4‐triazole‐3‐carboxylic acid and of cobalt(III) with 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid

Because of their versatile coordination modes and strong coordination ability for metals, triazole ligands can provide a wide range of possibilities for the construction of metal–organic frameworks. Three transition‐metal complexes, namely bis(μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato)‐κ³N ²,O :N ¹;κ³N ¹:N ²,O‐bis[triamminenickel(II)] tetrahydrate, [Ni₂(C₃HN₃O₂)₂(NH₃)₆]·4H₂O, (I), catena‐poly[[[diamminediaquacopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ¹:N ⁴,O‐[diamminecopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ⁴,O :N ¹] dihydrate], {[Cu₂(C₃HN₃O₂)₂(NH₃)₄(H₂O)₂]·2H₂O}_n , (II), (μ‐5‐amino‐1,2,4‐triazol‐1‐ide‐3‐carboxylato‐κ²N ¹:N ²)di‐μ‐hydroxido‐κ⁴O :O‐bis[triamminecobalt(III)] nitrate hydroxide trihydrate, [Co₂(C₃H₂N₄O₂)(OH)₂(NH₃)₆](NO₃)(OH)·3H₂O, (III), with different structural forms have been prepared by the reaction of transition metal salts, i.e. NiCl₂, CuCl₂ and Co(NO₃)₂, with 1,2,4‐triazole‐3‐carboxylic acid or 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid hemihydrate in aqueous ammonia at room temperature. Compound (I) is a dinuclear complex. Extensive O—H…O, O—H…N and N—H…O hydrogen bonds and π–π stacking interactions between the centroids of the triazole rings contribute to the formation of the three‐dimensional supramolecular structure. Compound (II) exhibits a one‐dimensional chain structure, with O—H…O hydrogen bonds and weak O—H…N, N—H…O and C—H…O hydrogen bonds linking anions and lattice water molecules into the three‐dimensional supramolecular structure. Compared with compound (I), compound (III) is a structurally different dinuclear complex. Extensive N—H…O, N—H…N, O—H…N and O—H…O hydrogen bonding occurs in the structure, leading to the formation of the three‐dimensional supramolecular structure.     

Supramolecular architectures in two 1:1 cocrystals of 5‐fluorouracil with 5‐bromothiophene‐2‐carboxylic acid and thiophene‐2‐carboxylic acid

In solid‐state engineering, cocrystallization is a strategy actively pursued for pharmaceuticals. Two 1:1 cocrystals of 5‐fluorouracil (5FU; systematic name: 5‐fluoro‐1,3‐dihydropyrimidine‐2,4‐dione), namely 5‐fluorouracil–5‐bromothiophene‐2‐carboxylic acid (1/1), C₅H₃BrO₂S·C₄H₃FN₂O₂, (I), and 5‐fluorouracil–thiophene‐2‐carboxylic acid (1/1), C₄H₃FN₂O₂·C₅H₄O₂S, (II), have been synthesized and characterized by single‐crystal X‐ray diffraction studies. In both cocrystals, carboxylic acid molecules are linked through an acid–acid R ₂²(8) homosynthon (O—H…O) to form a carboxylic acid dimer and 5FU molecules are connected through two types of base pairs [homosynthon, R ₂²(8) motif] via a pair of N—H…O hydrogen bonds. The crystal structures are further stabilized by C—H…O interactions in (II) and C—Br…O interactions in (I). In both crystal structures, π–π stacking and C—F…π interactions are also observed.     

Crystal structures,thermal stabilities,and dissolution behaviours of tinidazole and the tinidazole–vanillic acid cocrystal: insights from energy frameworks

The crystal structures of the antimicrobial drug tinidazole [ TNZ ; systematic name: 1‐(2‐ethylsulfonylethyl)‐2‐methyl‐5‐nitroimidazole, C₈H₁₃N₃O₄S] and the 1:1 cocrystal of TNZ with the naturally occurring compound vanillic acid ( VA ; systematic name: 4‐hydroxy‐3‐methoxybenzoic acid, C₈H₈O₄), namely, the TNZ – VA cocrystal, were determined by single‐crystal X‐ray analysis at 100 K. The supramolecular structure of the TNZ – VA cocrystal is composed of a carboxylic acid dimer and an O—H…N(heterocycle) synthon in the form of layers made up of O—H…N and O—H…O hydrogen bonds. The layers are joined via C—H…O hydrogen bonds, π–π stacking and C—H…π interactions. The energy framework analysis, together with interaction energy calculations using the DLPNO‐CCSD(T) method, indicates that the TNZ – VA cocrystal inherits strong interactions from the TNZ and VA crystals, which accounts for the enhanced thermal stability and reduced dissolution rate. To the best of our knowledge, this is the first example of a cocrystal containing TNZ .     

Sodium magnesium sulfate decahydrate,Na2Mg(SO4)2·10H2O,a new sulfate salt

The structure of synthetic disodium magnesium disulfate decahydrate at 180 K consists of alternating layers of water‐coordinated [Mg(H₂O)₆]²⁺ octahedra and [Na₂(SO₄)₂(H₂O)₄]²⁻ sheets, parallel to [100]. The [Mg(H₂O)₆]²⁺ octahedra are joined to one another by a single hydrogen bond, the other hydrogen bonds being involved in inter‐layer linkage. The Mg²⁺ cation occupies a crystallographic inversion centre. The sodium–sulfate sheets consist of chains of water‐sharing [Na(H₂O)₆]⁺ octahedra along b, which are then connected by sulfate tetrahedra through corner‐sharing. The associated hydrogen bonds are the result of water–sulfate interactions within the sheets themselves. This is believed to be the first structure of a mixed monovalent/divalent cation sulfate decahydrate salt.     

Unusual hydrogen bonding in L‐cysteine hydrogen fluoride

L‐Cysteine hydrogen fluoride, or bis(L‐cysteinium) difluoride–L‐cysteine–hydrogen fluoride (1/1/1), 2C₃H₈NO₂S⁺·2F⁻·C₃H₇NO₂S·HF or L‐Cys⁺(L‐Cys...L‐Cys⁺)F⁻(F⁻...H—F), provides the first example of a structure with cations of the `triglycine sulfate' type, i.e.A⁺(A...A⁺) (where A and A⁺ are the zwitterionic and cationic states of an amino acid, respectively), without a doubly charged counter‐ion. The salt crystallizes in the monoclinic system with the space group P2₁. The dimeric (L‐Cys...L‐Cys⁺) cation and the dimeric (F⁻...H—F) anion are formed via strong O—H...O or F—H...F hydrogen bonds, respectively, with very short O...O [2.4438 (19) Å] and F...F distances [2.2676 (17) Å]. The F...F distance is significantly shorter than in solid hydrogen fluoride. Additionally, there is another very short hydrogen bond, of O—H...F type, formed by a L‐cysteinium cation and a fluoride ion. The corresponding O...F distance of 2.3412 (19) Å seems to be the shortest among O—H...F and F—H...O hydrogen bonds known to date. The single‐crystal X‐ray diffraction study was complemented by IR spectroscopy. Of special interest was the spectral region of vibrations related to the above‐mentioned hydrogen bonds.     

Mechanochemical synthesis and X‐ray structural characterization of three 3‐nitrophenol cocrystals with three aminal cage azaadamantanes: the role of the stereoelectronic effect on intermolecular hydrogen‐bonding patterns

The structures of the cocrystalline adducts of 3‐nitrophenol (3‐NP) with 1,3,5,7‐tetraazatricyclo[3.3.1.1^3,7]decane [HMTA, ( 1 )] as the 2:1:1 hydrate, 2C₆H₅NO₃·C₆H₁₂N₄·H₂O, ( 1a ), with 1,3,6,8‐tetraazatricyclo[4.3.1.1^3,8]undecane [TATU ( 2 )] as the 2:1 cocrystal, 2C₆H₅NO₃·C₇H₁₄N₄, ( 2a ), and with 1,3,6,8‐tetraazatricyclo[4.4.1.1^3,8]dodecane [TATD, ( 3 )] as the 2:1 cocrystal, 2C₆H₅NO₃·C₈H₁₆N₄, ( 3a ), are reported. In the binary crystals ( 2a ) and ( 3a ), the 3‐nitrophenol molecules are linked via O—H…N hydrogen bonds into aminal cage azaadamantanes. In ( 1a ), the structure is stabilized by O—H…N and O—H…O hydrogen bonds, and generates ternary cocrystals. There are C—H…O hydrogen bonds present in all three cocrystals, and in ( 1a ), there are also C—H…O and C—H…π interactions present. The presence of an ethylene bridge in the structures of ( 2 ) and ( 3 ) defines the formation of a hydrogen‐bonded motif in the supramolecular architectures of ( 2a ) and ( 3a ). The differences in the C—N bond lengths of the aminal cage structures, as a result of hyperconjugative interactions and electron delocalization, were analysed. These three cocrystals were obtained by the solvent‐free assisted grinding method. Crystals suitable for single‐crystal X‐ray diffraction were grown by slow evaporation from a mixture of hexanes.     

Copper(II) bis(4,4,4‐trifluoro‐1‐phenylbutane‐1,3‐dionate) complexes with pyridin‐2‐one, 3‐hydroxypyridine and 3‐hydroxypyridin‐2‐one ligands: molecular structures and hydrogen‐bonded networks

Copper(II) bis(4,4,4‐trifluoro‐1‐phenylbutane‐1,3‐dionate) complexes with pyridin‐2‐one (pyon), 3‐hydroxypyridine (hpy) and 3‐hydroxypyridin‐2‐one (hpyon) were prepared and the solid‐state structures of (pyridin‐2‐one‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO)] or [Cu(tfpb‐κ²O ,O ′)₂(pyon‐κO )], (I), bis(pyridin‐3‐ol‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO)₂] or [Cu(tfpb‐κ²O ,O ′)₂(hpy‐κO )₂], (II), and bis(3‐hydroxypyridin‐2‐one‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO₂)₂] or [Cu(tfpb‐κ²O ,O ′)₂(hpyon‐κO )₂], (III), were determined by single‐crystal X‐ray analysis. The coordination of the metal centre is square pyramidal and displays a rare example of a mutual cis arrangement of the β‐diketonate ligands in (I) and a trans‐octahedral arrangement in (II) and (III). Complex (II) presents the first crystallographic evidence of κO‐monodentate hpy ligation to the transition metal enabling the pyridine N atom to participate in a two‐dimensional hydrogen‐bonded network through O—H…N interactions, forming a graph‐set motif R ₂²(7) through a C—H…O interaction. Complex (III) presents the first crystallographic evidence of monodentate coordination of the neutral hpyon ligand to a metal centre and a two‐dimensional hydrogen‐bonded network is formed through N—H…O interactions facilitated by C—H…O interactions, forming the graph‐set motifs R ₂²(8) and R ₂²(7).