Dipolar S=O...C=O and C—H...O interactions in the molecular organization of 4,6‐di‐O‐acetyl‐2‐O‐tosyl‐myo‐inositol 1,3,5‐orthoesters

In the absence of conventional hydrogen bonding, the molecules of 4,6‐di‐O‐acetyl‐2‐O‐tosyl‐myo‐inositol 1,3,5‐orthoformate, C₁₈H₂₀O₁₀S, (I), and 4,6‐di‐O‐acetyl‐2‐O‐tosyl‐myo‐inositol 1,3,5‐orthobenzoate, C₂₄H₂₄O₁₀S, (II), are associated via C—H...O interactions. Molecules of (II) are additionally linked via dipolar S=O...C=O contacts. It is interesting to note that the sulfonyl O atom involved in the dipolar S=O...C=O contacts does not take part in any other interaction, indicating the competitive nature of this contact relative to the weak hydrogen‐bonding interactions.     

A novel heterometallic dinuclear compound: rac‐pentaaqua‐1κ5O‐(μ‐2‐sulfidoacetato‐1:2κ3O:O′,S)bis(2‐sulfidoacetato‐2κ2O,S)manganese(II)tin(IV)

The title racemic heterometallic dinuclear compound, [MnSn(C₂H₂O₂S)₃(H₂O)₅], (I), contains one main group Sn^IV metal centre and one transition metal Mn^II centre, and, by design, links the Mn^II centre to the building unit of the (Δ/Λ) [SnL₃]²⁻ complex anion (L is the 2‐sulfidoacetate dianion). In this cluster, the Sn^IV centre of the (Δ/Λ) [SnL₃]²⁻ unit is coordinated by three O atoms and three S atoms from three L ligands to form an [SnO₃S₃] octahedral coordination environment. The Mn^II centre is in an [MnO₆] octahedral coordination environment, with five O atoms from five water molecules and the sixth from the μ₂‐L ligand of the (Δ/Λ) [SnL₃]²⁻ unit. Between adjacent dinuclear molecules, there are many hydrogen‐bond interactions of O—H...O, O—H...S, C—H...O and C—H...S types. Of these, eight pairs of O—H...O hydrogen bonds fuse all the dinuclear molecules into two‐dimensional supramolecular sheets along the bc plane. Adjacent supramolecular sheets are further connected through O—H...S hydrogen bonds to give a three‐dimensional supramolecular network.     

Intra‐ and intermolecular Se...X (X = Se,O) interactions in selenium‐containing heterocycles: 3‐benzoylimino‐5‐(morpholin‐4‐yl)‐1,2,4‐diselenazole

In the selenium‐containing heterocyclic title compound {systematic name: N‐[5‐(morpholin‐4‐yl)‐3H‐1,2,4‐diselenazol‐3‐ylidene]benzamide}, C₁₃H₁₃N₃O₂Se₂, the five‐membered 1,2,4‐diselenazole ring and the amide group form a planar unit, but the phenyl ring plane is twisted by 22.12 (19)° relative to this plane. The five consecutive N—C bond lengths are all of similar lengths [1.316 (6)–1.358 (6) Å], indicating substantial delocalization along these bonds. The Se...O distance of 2.302 (3) Å, combined with a longer than usual amide C=O bond of 2.252 (5) Å, suggest a significant interaction between the amide O atom and its adjacent Se atom. An analysis of related structures containing an Se—Se...X unit (X = Se, S, O) shows a strong correlation between the Se—Se bond length and the strength of the Se...X interaction. When X = O, the strength of the Se...O interaction also correlates with the carbonyl C=O bond length. Weak intermolecular Se...Se, Se...O, C—H...O, C—H...π and π–π interactions each serve to link the molecules into ribbons or chains, with the C—H...O motif being a double helix, while the combination of all interactions generates the overall three‐dimensional supramolecular framework.     

2,3:4,6‐Di‐O‐isopropylidene‐α‐l‐sorbofuranose and 2,3‐O‐isopropylidene‐α‐l‐sorbofuranose

In the title compounds, C₁₂H₂₀O₆, (I), and C₉H₁₆O₆, (II), the five‐membered furanose ring adopts a ⁴T₃ conformation and the five‐membered 1,3‐dioxolane ring adopts an E₃ conformation. The six‐membered 1,3‐dioxane ring in (I) adopts an almost ideal ^OC₃ conformation. The hydrogen‐bonding patterns for these compounds differ substantially: (I) features just one intramolecular O—H...O hydrogen bond [O...O = 2.933 (3) Å], whereas (II) exhibits, apart from the corresponding intramolecular O—H...O hydrogen bond [O...O = 2.7638 (13) Å], two intermolecular bonds of this type [O...O = 2.7708 (13) and 2.7730 (12) Å]. This study illustrates both the similarity between the conformations of furanose, 1,3‐dioxolane and 1,3‐dioxane rings in analogous isopropylidene‐substituted carbohydrate structures and the only negligible influence of the presence of a 1,3‐dioxane ring on the conformations of furanose and 1,3‐dioxolane rings. In addition, in comparison with reported analogs, replacement of the –CH₂OH group at the C1‐furanose position by another group can considerably affect the conformation of the 1,3‐dioxolane ring.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

catena‐Poly[[diaquazinc(II)]‐μ‐4,4′‐sulfonyldibenzoato‐κ2O:O′]

The title compound, [Zn(C₁₄H₈O₆S)(H₂O)₂]_n, is the first reported metal complex of the 4,4′‐sulfonyldibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H₂O)₂]²⁺ and sulfonyldibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The Zn^II centre occupies a strongly distorted tetrahedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxylate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxylates [Zn—O = 2.528 (2) Å]. Hydrogen bonds between carboxylate O atoms and coordinated water molecules in adjacent chains lead to the formation of a three‐dimensional network structure.     

Bis(dimethyl sulfoxide‐S)tetrakis(μ‐p‐hydroxybenzoato‐O:O′)dirhodium(II)–tetrakis(μ‐butyrato‐O:O′)bis(dimethyl sulfoxide‐S)dirhodium(II) cocrystal ethanol disolvate

The title structure, [Rh₂(C₇H₅O₃)₄(C₂H₆OS)₂]·[Rh₂(C₄H₇­O₂)₄(C₂H₆OS)₂]·2C₂H₆O, contains two discrete neutral Rh–Rh dimers cocrystallized as the ethanol disolvate. Each dimer is situated on an inversion center. The butyrate chain displays disorder in one C‐atom position. In each dimer, the di­methyl sulfoxide ligand (dmso) is bound via S, as expected. The ethanol is a hydrogen‐bond acceptor for one p‐hydroxy­benzoate hydroxyl group and acts as a hydrogen‐bond donor to the dmso O atom of a neighboring p‐hydroxy­benzoate dirhodium complex. A third hydrogen bond is formed from the other p‐hydroxy­benzoate hydroxyl group to the dmso O atom of a butyrate–dirhodium complex.     

Cocrystals of 6‐propyl‐2‐thiouracil: N—H...O versus N—H...S hydrogen bonds

In order to investigate the relative stability of N—H...O and N—H...S hydrogen bonds, we cocrystallized the antithyroid drug 6‐propyl‐2‐thiouracil with two complementary heterocycles. In the cocrystal pyrimidin‐2‐amine–6‐propyl‐2‐thiouracil (1/2), C₄H₅N₃·2C₇H₁₀N₂OS, (I), the `base pair' is connected by one N—H...S and one N—H...N hydrogen bond. Homodimers of 6‐propyl‐2‐thiouracil linked by two N—H...S hydrogen bonds are observed in the cocrystal N‐(6‐acetamidopyridin‐2‐yl)acetamide–6‐propyl‐2‐thiouracil (1/2), C₉H₁₁N₃O₂·2C₇H₁₀N₂OS, (II). The crystal structure of 6‐propyl‐2‐thiouracil itself, C₇H₁₀N₂OS, (III), is stabilized by pairwise N—H...O and N—H...S hydrogen bonds. In all three structures, N—H...S hydrogen bonds occur only within R₂²(8) patterns, whereas N—H...O hydrogen bonds tend to connect the homo‐ and heterodimers into extended networks. In agreement with related structures, the hydrogen‐bonding capability of C=O and C=S groups seems to be comparable.     

Bis(2‐amino‐1H‐benzimidazol‐3‐ium) tetrakis(μ‐but‐2‐enoato)‐κ4O:O′;κ3O,O′:O;κ3O:O,O′‐bis[bis(but‐2‐enoato‐κ2O,O′)holmium(III)]

The title ionic compound, (C₇H₈N₃)₂[Ho₂(C₄H₅O₂)₈], is constructed from two almost identical independent centrosymmetric anionic dimers balanced by two independent 2‐amino‐1H‐benzimidazol‐3‐ium (Habim⁺) cations. The asymmetric part of each dimer is made up of one Ho^III cation and four crotonate (crot or but‐2‐enoate) anions, two of them acting in a simple η²‐chelating mode and the remaining two acting in two different μ₂:η² fashions, viz. purely bridging and bridging–chelating. Symmetry‐related Ho^III cations are linked by two Ho—O—Ho and two Ho—O—C—O—Ho bridges which lead to rather short intracationic Ho...Ho distances [3.8418 (3) and 3.8246 (3) Å]. In addition to the obvious Coulombic interactions linking the cations and anions, the isolated [Ho₂(crot)₈]²⁻ and Habim⁺ ions are linked by a number of N—H...O hydrogen bonds, in which all N—H groups of the cation are involved as donors and all (simple chelating) crot O atoms are involved as acceptors. These interactions result in compact two‐dimensional structures parallel to (110), which are linked to each other by weaker π–π contacts between Habim⁺ benzene groups.     

[2‐(2‐Pyridyl)‐1H‐benzimidazole‐κ2N2,N3]bis(p‐toluato‐κ2O,O′)manganese(II)

In the title compound, [Mn(C₈H₇O₂)₂(C₁₂H₉N₃)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2‐(2‐pyridyl)benzimidazole ligand [Mn—N = 2.1954 (13) and 2.2595 (14) Å] and two p‐toluate ligands [Mn—O = 2.1559 (13)–2.2748 (14) Å]. It displays a severely distorted octahedral geometry, with cis angles ranging from 58.87 (4) to 106.49 (5)°. Intermolecular C—H...O hydrogen bonds between the p‐toluate ligands link the molecules into infinite chains, and every two neighbouring chains are further coupled by N—H...O and C—H...O hydrogen bonds between the 2‐(2‐pyridyl)benzimidazole and p‐toluate ligands, leading to an infinite ribbon‐like double‐chain packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and possible C—H...π interactions, as well as stacking interactions involving the 2‐(2‐pyridyl)benzimidazole ligands.     

1‐(Thiophen‐3‐yl)ethanone

The structure of the title compound, C₆H₆OS, exhibits a flip‐type disorder of the thiophene ring [occupancy ratio = 0.848 (3):0.152 (3)], which is typical for many thiophene derivatives. The puckered thiophene ring is essentially coplanar with the plane formed by the non‐H atoms of the acetyl substituent, similar to its simple analogues, i.e. 3‐acetyl‐2‐carboxythiophene, 4‐acetyl‐3‐carboxythiophene and 3,5‐diacetyl‐2‐ethylamino‐4‐methylthiophene. In the crystal structure, molecules are connected by C—H...π hydrogen bonds, forming a sheet parallel to the (001) plane. Moreover, an inspection of the crystal lattice reveals that there are short S...O contacts connecting the molecules of adjacent sheets. Comparison of the title crystal structure with its simple 3‐methoxythiophene analogue shows a close similarity in the herringbone arrangement of molecules and in the presence of C—H...π interactions and S...O contacts.     

Short intermolecular N—Br...O=C contacts in 1,3‐dibromo‐5,5‐dimethylimidazolidine‐2,4‐dione

In the title compound, C₅H₆Br₂N₂O₂, all atoms except for the methyl group lie on a mirror plane in the space group Pnma (No. 62). All bond lengths are normal and the five‐membered ring is planar by symmetry. Two short intermolecular N—Br...O=C contacts [Br...O = 2.787 (2) and 2.8431 (19) Å] are present, originating primarily from the O‐atom lone pairs donating electron density to the antibonding orbitals of the N—Br bonds (delocalization energy transfers 3.27 and 2.11 kcal mol⁻¹). The total stabilization energies of the Br...O interactions are 3.4828 and 2.3504 kcal mol⁻¹.     

Three sterically hindered 6‐amino‐5‐cyano‐2‐methyl‐4‐(1‐naphthyl)‐4H‐pyran‐3‐carboxylate derivatives

In the title compounds, 2‐methoxyethyl 6‐amino‐5‐cyano‐2‐methyl‐4‐(1‐naphthyl)‐4H‐pyran‐3‐carboxylate, C₂₁H₂₀N₂O₄, (II), isopropyl 6‐amino‐5‐cyano‐2‐methyl‐4‐(1‐naphthyl)‐4H‐pyran‐3‐carboxylate, C₂₁H₂₀N₂O₃, (III), and ethyl 6‐amino‐5‐cyano‐2‐methyl‐4‐(1‐naphthyl)‐4H‐pyran‐3‐carboxylate, C₂₀H₁₈N₂O₃, (IV), the heterocyclic pyran ring adopts a flattened boat conformation. In (II) and (III), the carbonyl group and a double bond of the heterocyclic ring are mutually anti, but in (IV) they are mutually syn. The ester O atoms in (II) and (III) and the carbonyl O atom in (IV) participate in intramolecular C—H...O contacts to form six‐membered rings. The dihedral angles between the naphthalene substituent and the closest four atoms of the heterocyclic ring are 73.3 (1), 71.0 (1) and 74.3 (1)° for (II)–(IV), respectively. In all three structures, only one H atom of the NH₂ group takes part in N—H...O [in (II) and (III)] or N—H...N [in (IV)] intermolecular hydrogen bonds, and chains [in (II) and (III)] or dimers [in (IV)] are formed. In (II), weak intermolecular C—H...O and C—H...N hydrogen bonds, and in (III) intermolecular C—H...O hydrogen bonds link the chains into ladders along the a axis.     

4,5‐Bis(furoylsulfanyl)‐1,3‐dithiole‐2‐thione

The title compound, C₁₃H₆O₄S₅, possesses crystallographically imposed mirror symmetry, with the atoms of the C=S group lying on the mirror plane. It is an example of the general formula [RCO]₂(dmit), where R is a furan ring and dmit is 2‐thioxo‐1,3‐dithiole‐4,5‐dithiol­ate. The components exhibit some polarization of their mol­ecular–electronic structure. The dmit and furan moieties exhibit a high degree of conjugation, as the introduction of C=O connecting the conjugated furan (donor) and dmit (acceptor) rings forms a good conjugated system with high delocalization. A polar three‐dimensional framework is built from a combination of inter­molecular contacts, namely S⋯S inter­actions and C—H⋯O hydrogen bonding. The structural characteristics lead to good second‐order non‐linear optical properties.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

Intermolecular O—H⃛O hydrogen bonding in the three independent molecules of (2S)‐3‐(4‐hydroxyphenyl)‐2‐(1‐oxoisoindolin‐2‐yl)­propanoic acid

The title compound, C₁₇H₁₅NO₄, derived from l ‐tyrosine, crystallizes with three independent mol­ecules which differ in the conformation of the asymmetric unit: the N—C—C—C_ipso torsion angles are ?71.7 (5), ?63.6 (6) and ?52.5 (5)°, respectively. Deformations in the phenol ring hydroxy O—C—C angles of 116.5 (4)/123.9 (4), 121.7 (5)/118.1 (4) and 122.4 (5)/118.6 (5)°, respectively, result from their respective intermolecular hydrogen‐bonding environments. Intermolecular O_acid—H?O=C_indole, O_phenol—H?O—H_phenol and O_phenol—H?O=C_indole hydrogen bonds, with O?O distances in the range 2.607 (4)–2.809 (4) Å, are present in combination with C—H?O and C—H?π_arene interactions. The primary hydrogen‐bonding systems assemble with graph sets R₃³(8) and R₃²(22).     

5‐[4‐(Diethoxyphosphoryl)‐2,3,5,6‐tetrafluorophenyl]‐10,15,20‐tris(pentafluorophenyl)porphyrin

The title compound, C₄₈H₂₀F₁₉N₄O₃P, prepared by the nucleophilic attack of triethyl phosphite on one of the 4‐fluoro atoms of 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin, contains a single molecule in the asymmetric unit. The porphyrin unit is almost planar [largest non‐H atom deviation = 0.174 (6) Å], and has the planes of the neighbouring benzene rings oriented at angles ranging from 64.3 (2) to 89.6 (3)° relative to the porphyrin core. The P=O group is almost coplanar with the attached benzene ring, subtending an angle of 4.0 (3)°. Several weak supramolecular interactions, namely C—H...π, C—F...π, P=O...π, C—H...(O,F) and F...F contacts, contribute to the crystal packing.     

mer‐Bis(1,4‐dibenzoylthiosemicarbazidato‐κ3O,N,O′)cobalt(II)

The title complex, [Co(C₁₅H₁₂N₃O₂S)₂], consists of an octahedrally coordinated Co^II ion, with two crystallographically independent 1,4‐dibenzoylthiosemicarbazidate ligands in a tridentate mer coordination [Co—O = 2.064 (3)–2.132 (3) Å and Co—N = 2.037 (3)–2.043 (3) Å]. There are intermolecular N—H...S hydrogen bonds involving one ligand and strong π–π stacking interactions involving the other ligand, resulting in a three‐dimensional supramolecular framework. The hydrogen bonds and π–π interactions, as well as different intramolecular aryl–benzamide H—C...H(—N) distances, give rise to a difference in conformation between the two ligands.     

Supramolecular structures of bis‐thionooxalamic acid esters derived from (±)‐cyclohexane‐1,2‐diamine and (±)‐1,2‐diphenylethylenediamine

The bis‐thionooxalamic acid esters trans‐(±)‐diethyl N,N′‐(cyclohexane‐1,2‐diyl)bis(2‐thiooxamate), C₁₄H₂₂N₂O₄S₂, and (±)‐N,N′‐diethyl (1,2‐diphenylethane‐1,2‐diyl)bis(2‐thiooxamate), C₂₂H₂₄N₂O₄S₂, both consist of conformationally flexible molecules which adopt similar conformations with approximate C₂ rotational symmetry. The thioamide and ester parts of the thiooxamate group are significantly twisted along the central C—C bond, with the S=C—C=O torsion angles in the range 30.94 (19)–44.77 (19)°. The twisted s‐cis conformation of the thionooxamide groups facilitates assembly of molecules into a one‐dimensional polymeric structure via intermolecular three‐center C=S...NH...O=C hydrogen bonds and C—H...O interactions formed between molecules of the opposite chirality.     

Polymorph of {2‐[(2‐hydroxyethyl)iminiomethyl]phenolato‐κO}dioxido{2‐[(2‐oxidoethyl)iminomethyl]phenolato‐κ3O,N,O′}molybdenum(VI)

A second polymorphic form (form I) of the previously reported compound {2‐[(2‐hydroxyethyl)iminiomethyl]phenolato‐κO}dioxido{2‐[(2‐oxidoethyl)iminomethyl]phenolato‐κ³O,N,O′}molybdenum(VI) (form II), [Mo(C₉H₉NO₂)O₂(C₉H₁₁NO₂)], is presented. The title structure differs from the previously reported polymorph [Głowiak, Jerzykiewicz, Sobczak & Ziółkowski (2003). Inorg. Chim. Acta, 356 , 387–392] by the fact that the asymmetric unit contains three molecules linked by O—H...O hydrogen bonds. These trimeric units are further linked through O—H...O hydrogen bonds to form a chain parallel to the [11] direction. As in the previous polymorph, each molecule is built up from an MoO₂²⁺ cation surrounded by an O,N,O′‐tridentate ligand (O⁻C₆H₄CH=NCH₂CH₂O⁻) and weakly coordinated by a second zwitterionic ligand (O⁻C₆H₄CH=N⁺HC₂H₄OH). All complexes are chiral with the absolute configuration at Mo being C or A. The main difference between the two polymorphs results from the alternation of the chirality at Mo within the chain.