Synthesis and absolute structure of (R)-2-(benzyl-selan-yl)-1-phenyl-ethanaminium hydrogen sulfate monohydrate: crystal structure and Hirshfeld surface analyses.

A hydrogen sulfate salt, C15H18NSe+·HSO4 -·H2O or [BnSeCH2CH(Ph)NH3 +](HSO4 -), of a chiral selenated amine (R)-2-(benzyl-selan-yl)-1-phenyl-ethan-amine (BnSeCH2CH(Ph)NH2) has been synthesized and characterized by elemental analysis,1H and 13C{1H} NMR, FT-IR analysis, and single-crystal X-ray diffraction studies. The title salt crystallizes in the monohydrate form in the non-centrosymmetric monoclinic P21 space group. The cation is somewhat W shaped with the dihedral angle between the two aromatic rings being 60.9 (4)°. The carbon atom attached to the amine nitro-gen atom is chiral and in the R configuration, and, the -C-C- bond of the -CH2-CH- fragment has a staggered conformation. In the crystal structure, two HSO4 - anions and two water mol-ecules form an R 4 4(12) tetra-meric type of assembly comprised of alternating HSO4 - anions and water mol-ecules via discrete D(2) O-H⋯O hydrogen bonds. This tetra-meric assembly aggregates along the b-axis direction as an infinite one-dimensional tape. Adjacent tapes are inter-connected via discrete D(2) N-H⋯O hydrogen bonds between the three amino hydrogen atoms of the cation sandwiched between the two tapes and the three HSO4 - anions of the nearest asymmetric units, resulting in a complex two-dimensional sheet along the ab plane. The pendant arrangement of the cations is stabilized by C-H⋯π inter-actions between adjacent cations running as chains down the [010] axis. Secondary Se⋯O [3.1474 (4) Å] inter-actions are also observed in the crystal structure. A Hirshfeld surface analysis, including d norm, shape-index and fingerprint plots of the cation, anion and solvent mol-ecule, was carried out to confirm the presence of various inter-actions in the crystal structure.

Crystal structure and photoluminescent properties of bis-(4'-chloro-2,2':6',2''-terpyrid-yl)cobalt(II) dichloride tetra-hydrate.

In the title hydrated complex, [Co(C15H10ClN3)2]Cl2·4H2O, the complete dication is generated by symmetry. The CoN6 moiety shows distortion from regular octa-hedral geometry with the trans bond angles of two N-Co-N units being 160.62 (9)°. In the crystal, O-H⋯Cl and C-H⋯O inter-actions link the components into (001) sheets. The title compound exhibits blue-light emission, as indicated by photoluminescence data, and a HOMO-LUMO energy separation of 2.23 eV was obtained from its diffuse reflectance spectrum.

N-[2-(Tri-fluoro-meth-yl)phen-yl]maleamic acid: crystal structure and Hirshfeld surface analysis.

The title mol-ecule, C11H8F3NO3, adopts a cis configuration across the -C=C- double bond in the side chain and the dihedral angle between the phenyl ring and side chain is 47.35 (1)°. The -COOH group adopts a syn conformation (O=C-O-H = 0°), unlike the anti conformation observed in related maleamic acids. In the crystal, inversion dimers linked by pairs of O-H⋯O hydrogen bonds are connected via N-H⋯O hydrogen bonds and C-H⋯O inter-actions into (100) sheets, which are cross-linked by another C-H⋯O inter-action to result in a three-dimensional network. The Hirshfeld surface fingerprint plots show that the highest contribution to surface contacts arises from O⋯H/H⋯O contacts (26.5%) followed by H⋯F/F⋯H (23.4%) and H⋯H (17.3%).

Crystal structures of 2-amino-pyridine citric acid salts: C5H7N2+·C6H7O7- and 3C5H7N2+·C6H5O73.

2-Amino-pyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-amino-pyridinium citrate salts, viz. C5H7N2+·C6H7O7- (I) (systematic name: 2-amino-pyridin-1-ium 3-carb-oxy-2-carb-oxy-methyl-2-hy-droxy-propano-ate), and 3C5H7N2+·C6H5O73- (II) [systematic name: tris-(2-amino-pyridin-1-ium) 2-hy-droxy-propane-1,2,3-tri-carboxyl-ate]. The supra-molecular synthons present are analysed and their effect upon the crystal packing is presented in the context of crystal engineering. Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carb-oxy-lic group of citric acid, while in II all three carb-oxy-lic groups of the acid are deprotonated and the charges are compensated for by three 2-amino-pyridinium cations. In both structures, a complex supra-molecular three-dimensional architecture is formed. In I, the supra-molecular aggregation results from Namino-H⋯Oacid, Oacid⋯H-Oacid, Oalcohol-H⋯Oacid, Namino-H⋯Oalcohol, Npy-H⋯Oalcohol and Car-H⋯Oacid inter-actions. The mol-ecular conformation of the citrate ion (CA3-) in II is stabilized by an intra-molecular Oalcohol-H⋯Oacid hydrogen bond that encloses an S(6) ring motif. The complex three-dimensional structure of II features Namino-H⋯Oacid, Npy-H⋯Oacid and several Car-H⋯Oacid hydrogen bonds. In the crystal of I, the common charge-assisted 2-amino-pyridinium-carboxyl-ate heterosynthon exhibited in many 2-amino-pyridinium carboxyl-ates is not observed, instead chains of N-H⋯O hydrogen bonds and hetero O-H⋯O dimers are formed. In the crystal of II, the 2-amino-pyridinium-carboxyl-ate heterosynthon is sustained, while hetero O-H⋯O dimers are not observed. The crystal structures of both salts display a variety of hydrogen bonds as almost all of the hydrogen-bond donors and acceptors present are involved in hydrogen bonding.

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 dnorm 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 R22(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.

Crystal structures of isomeric 3,5-di-chloro-N-(2,3-di-methyl-phen-yl)benzene-sulfonamide, 3,5-di-chloro-N-(2,6-di-methyl-phen-yl)benzene-sulfonamide and 3,5-di-chloro-N-(3,5-di-methyl-phen-yl)benzene-sulfonamide.

The crystal structures of three isomeric compounds of formula C14H13Cl2NO2S, namely 3,5-di-chloro-N-(2,3-di-methyl-phen-yl)-benzene-sulfonamide (I), 3,5-di-chloro-N-(2,6-di-methyl-phen-yl)benzene-sulfonamide (II) and 3,5-di-chloro-N-(3,5-di-methyl-phen-yl)benzene-sulfonamide (III) are described. The mol-ecules of all the three compounds are U-shaped with the two aromatic rings inclined at 41.3 (6)° in (I), 42.1 (2)° in (II) and 54.4 (3)° in (III). The mol-ecular conformation of (II) is stabilized by intra-molecular C-H⋯O hydrogen bonds and C-H⋯π inter-actions. The crystal structure of (I) features N-H⋯O hydrogen-bonded R22(8) loops inter-connected via C(7) chains of C-H⋯O inter-actions, forming a three-dimensional architecture. The structure also features π-π inter-actions [Cg⋯Cg = 3.6970 (14) Å]. In (II), N-H⋯O hydrogen-bonded R22(8) loops are inter-connected via π-π inter-actions [inter-centroid distance = 3.606 (3) Å] to form a one-dimensional architecture running parallel to the a axis. In (III), adjacent C(4) chains of N-H⋯O hydrogen-bonded mol-ecules running parallel to [010] are connected via C-H⋯π inter-actions, forming sheets parallel to the ab plane. Neighbouring sheets are linked via offset π-π inter-actions [inter-centroid distance = 3.8303 (16) Å] to form a three-dimensional architecture.

Crystal structures of isomeric 4-bromo-N-[(2-nitro-phen-yl)sulfon-yl]benzamide and 4-bromo-N-[(4-nitro-phen-yl)sulfon-yl]benzamide.

The syntheses and crystal structures of the isomeric 4-bromo-N-[(2-nitro-phen-yl)sulfon-yl]benzamide, (I), and 4-bromo-N-[(4-nitro-phen-yl)sulfon-yl]benzamide, (II), are described (mol-ecular formula = C13H9BrN2O5S in each case). The asymmetric unit of (I) contains two independent mol-ecules [(IA) and (IB)], while that of (II) contains one mol-ecule. The benzoic acid aromatic ring of mol-ecule (IA) is disordered due to rotation about the Car-C(=O) bond over two orientations in a 0.525 (9):0.475 (9) ratio. The dihedral angle between the benzene rings is 85.9 (3)° in (IA) and 65.22 (19)° in (IB), while in (II), the corresponding value is 56.7 (7)°. In the crystals of (I) and (II), N-H⋯O, C-H⋯O and C-H⋯π inter-actions generate three-dimensional networks.

Crystal structures of N-(3-fluoro-benzo-yl)benzene-sulfonamide and N-(3-fluoro-benzo-yl)-4-methyl-benzene-sulfonamide.

The crystal structures of two N-(aryl-sulfon-yl)aryl-amides, namely N-(3-fluoro-benzo-yl)benzene-sulfonamide, C13H10FNO3S, (I), and N-(3-fluoro-benzo-yl)-4-methyl-benzene-sulfonamide, C14H12FNO3S, (II), are described and compared with related structures. The dihedral angle between the benzene rings is 82.73 (10)° in (I) compared to 72.60 (12)° in (II). In the crystal of (I), the mol-ecules are linked by C-H⋯O and C-H⋯π inter-actions, resulting in a three-dimensional grid-like architecture, while C-H⋯O inter-actions lead to one-dimensional ribbons in (II). The crystals of both (I) and (II) feature strong but non-structure-directing N-H⋯O hydrogen bonds with R 2 (2)(8) ring motifs. The structure of (I) also features π-π stacking inter-actions.

Comparison of the crystal structures of methyl 4-bromo-2-(meth-oxy-meth-oxy)benzoate and 4-bromo-3-(meth-oxy-meth-oxy)benzoic acid.

The title compounds, C10H11BrO4, (I), and C9H9BrO4, (II), are derivatives of bromo-hy-droxy-benzoic acids. Compound (II) crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In both (I) and (II), the O-CH2-O-CH3 side chain is not in its fully extended conformation; the O-C-O-C torsion angle is 67.3 (3) ° in (I), and -65.8 (3) and -74.1 (3)° in mol-ecules A and B, respectively, in compound (II). In the crystal of (I), mol-ecules are linked by C-H⋯O hydrogen bonds, forming C(5) chains along [010]. The chains are linked by short Br⋯O contacts [3.047 (2) Å], forming sheets parallel to the bc plane. The sheets are linked via C-H⋯π inter-actions, forming a three-dimensional architecture. In the crystal of (II), mol-ecules A and B are linked to form R 2 (2)(8) dimers via two strong O-H⋯O hydrogen bonds. These dimers are linked into ⋯A-B⋯A-B⋯A-B⋯ [C 2 (2)(15)] chains along [011] by C-H⋯O hydrogen bonds. The chains are linked by slipped parallel π-π inter-actions [inter-centroid distances = 3.6787 (18) and 3.8431 (17) Å], leading to the formation of slabs parallel to the bc plane.

Crystal structures of three N-(aryl-sulfon-yl)-4-fluoro-benzamides.

The crystal structures of three N-aryl-sulfonyl-4-fluoro-benzamides, namely 4-fluoro-N-(2-methyl-phenyl-sulfon-yl)benzamide, C14H12FNO3S, (I), N-(2-chloro-phenyl-sulfon-yl)-4-fluorobenzamide, C13H9ClFNO3S, (II), and N-(4-chloro-phenyl-sulfon-yl)-4-fluoro-benzamide monohydrate, C13H9ClFNO3S·H2O, (III), are described and compared with related structures. The asymmetric unit of (I) contains two independent mol-ecules (A and B), while that of (II) contains just one mol-ecule, and that of (III) contains a mol-ecule of water in addition to one main mol-ecule. The dihedral angle between the benzene rings is 82.83 (11)° in mol-ecule A and 85.01 (10)° in mol-ecule B of (I), compared to 89.91 (10)° in (II) and 81.82 (11)° in (III). The crystal structure of (I) features strong N-H⋯O hydrogen bonds between the A and B mol-ecules, resulting in an R 4 (4)(16) tetra-meric unit. These tetra-meric units are connected into sheets in the bc plane by various C-H⋯O inter-actions, and adjacent sheets are further inter-linked via C-H⋯πar-yl inter-actions, forming a three-dimensional architecture. The crystal structure is further stabilized by πar-yl-πar-yl and S=O⋯πar-yl inter-actions. In the crystal of (II), mol-ecules are connected into R 2 (2)(8) and R 2 (2)(14) dimers via N-H⋯O hydrogen bonds and C-H⋯O inter-actions, respectively; the dimers are further inter-connected via a weak C=O⋯πar-yl inter-action, leading to the formation of chains along [1-10]. In the crystal of (III), N-H⋯O and O-H⋯O hydrogen bonds involving both the main mol-ecule and the solvent water mol-ecule results in the formation of sheets parallel to the bc plane. The sheets are further connected by C-H⋯O inter-actions and weak C-Cl⋯πar-yl, C-F⋯πar-yl and S=O⋯πar-yl inter-actions, forming a three-dimensional architecture.

Crystal structures of 3-fluoro-N-[2-(tri-fluoro-meth-yl)phen-yl]benzamide, 3-bromo-N-[2-(tri-fluoro-meth-yl)phen-yl]benzamide and 3-iodo-N-[2-(tri-fluoro-meth-yl)phen-yl]benzamide.

In the title compounds, C14H9F4NO, (I), C14H9BrF3NO, (II), and C14H9F3INO, (III), the two benzene rings are inclined to one another by 43.94 (8)° in mol-ecule A and 55.66 (7)° in mol-ecule B of compound (I), which crystallizes with two independent mol-ecules in the asymmetric unit, but by only 10.40 (12)° in compound (II) and 12.5 (2)° in compound (III). In the crystals of all three compounds, N-H⋯O hydrogen bonds link the mol-ecules to form chains propagating along the a-axis direction for (I), and along the b-axis direction for (II) and (III). In the crystal of (I), -A-B-A-B- chains are linked by C-H⋯O hydrogen bonds, forming layers parallel to (010). Within the layers there are weak offset π-π inter-actions present [inter-centroid distances = 3.868 (1) and 3.855 (1) Å]. In the crystals of (II) and (III), the chains are linked via short halogen-halogen contacts [Br⋯Br = 3.6141 (4) Šin (II) and I⋯I = 3.7797 (5) Šin (III)], resulting in the formation of ribbons propagating along the b-axis direction.

Crystal structure of 1-(5-bromo-1-benzo-furan-2-yl)ethanone oxime.

The title compound, C10H8BrNO2, is almost planar (r.m.s. deviation for the non-H atoms = 0.031 Å) and the conformation across the C=N bond is trans. Further, the O atom of the benzo-furan ring is syn to the N atom of the oxime group. In the crystal, inversion dimers linked by pairs of O-H⋯N hydrogen bonds generate R 2 (2)(6) loops. Very weak aromatic π-π stacking inter-actions [centroid-centroid separations = 3.9100 (12) and 3.9447 (12) Å] are also observed.

Crystal structures of 4-meth-oxy-N-(4-methyl-phenyl)benzene-sulfonamide and N-(4-fluoro-phenyl)-4-meth-oxy-benzene-sulfonamide.

Crystal structures of two N-(ar-yl)aryl-sulfonamides, namely, 4-meth-oxy-N-(4-methyl-phen-yl)benzene-sulfonamide, C14H15NO3S, (I), and N-(4-fluoro-phen-yl)-4-meth-oxy-benzene-sulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzene-sulfonamide ring is disordered over two orientations, in a 0.516 (7):0.484 (7) ratio, which are inclined to each other at 28.0 (1)°. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36 (19)°, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26 (13)°. In the crystal structure of (I), N-H⋯O hydrogen bonds form infinite C(4) chains extended in [010], and inter-molecular C-H⋯πar-yl inter-actions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N-H⋯O hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C-H⋯O inter-molecular inter-actions consolidate the crystal packing of (II) into a three-dimensional supra-molecular architecture.

Crystal structure of 2-(4-methyl-piperazin-1-yl)quinoline-3-carbaldehyde.

In the title compound, C15H17N3O, the aldehyde group is twisted relative to the quinoline group by17.6 (2)° due to the presence of a bulky piperazinyl group in the ortho position. The piperazine N atom attached to the aromatic ring is sp (3)-hybridized and the dihedral angle between the mean planes through the the six piperazine ring atoms and through the quinoline ring system is 40.59 (7)°. Both piperazine substituents are in equatorial positions.

Crystal structures of three N-ar-yl-2,2,2-tri-bromo-acetamides.

Three N-ar-yl-2,2,2-tri-bromo-acetamides, namely, 2,2,2-tri-bromo-N-(2-fluoro-phen-yl)-acetamide, C8H5Br3FNO, (I), 2,2,2-tri-bromo-N-[3-(tri-fluoro-methyl)-phen-yl]-acetamide, C9H5Br3F3NO, (II) and 2,2,2-tri-bromo-N-(4-fluoro-phen-yl)-acetamide, C8H5Br3FNO, (III) were synthesized and their crystal structures were analysed. In the crystal structure of (I), C-Br⋯πar-yl inter-actions connect the mol-ecules into dimers, which in turn are connected via Br⋯Br contacts [3.6519 (12) Å], leading to the formation of a one-dimensional ladder-type architecture. The crystal structure of (II) features chains linked by N-H⋯O and C-H⋯O hydrogen bonds. Two such chains are inter-linked to form ribbons through Br⋯Br [3.6589 (1) Å] and Br⋯F [3.0290 (1) Å] inter-actions. C-Br⋯πar-yl and C-F⋯πar-yl inter-actions between the ribbons extend the supra-molecular architecture of (II) from one dimension to two. In (III), the mol-ecules are connected into R 2 (2)(8) dimers via pairs of C-H⋯F inter-actions and these dimers form ribbons through Br⋯Br [3.5253 (1) Å] contacts. The ribbons are further inter-linked into columns via C-Br⋯O=C contacts, forming a two-dimensional architecture.

Crystal structure of 4-meth-oxy-phenyl 2-oxo-2H-chromene-3-carboxyl-ate.

In the title compound, C17H12O5, the dihedral angle between the planes of the coumarin ring system (r.m.s. deviation = 0.015 Å) and the benzene ring is 48.04 (10)°. The central CO2 group subtends a dihedral angle of 27.15 (11)° with the coumarin ring system and 74.86 (13)° with the benzene ring. In the crystal, mol-ecules are linked by C-H⋯O inter-actions, which generate a three-dimensional network. Very weak C-H⋯π inter-actions are also observed.

Crystal structure of 2-chloro-N-(3-fluoro-phen-yl)acetamide.

In the title compound, C8H7ClFNO, the F atom is disordred over the meta positions of the benzene ring in a 0.574 (4):0.426 (4) ratio and the Cl atom is syn to the O atom [O-C-C-Cl = 5.6 (3)°]. A short intra-molecular C-H⋯O contact occurs. In the crystal, mol-ecules are linked into amide C(4) chains propagating in [101] by N-H⋯O hydrogen bonds.

Crystal structure of 4-bromo-phenyl-2-oxo-2H-chromene-3-carboxyl-ate.

In the title compound, C16H9BrO4, the coumarin ring system is approximately planar, with an r.m.s deviation of the ten fitted non-H atoms of 0.031 Å, and forms a dihedral angle of 25.85 (10)° with the bromo-benzene ring. The carbonyl atoms are syn. In the crystal, mol-ecules are connected along [001] via C-H⋯O inter-actions, forming C(6) chains. Neighbouring C(6) chains are connected via several π-π inter-actions [range of centroid-centroid distances = 3.7254 (15)-3.7716 (16) Å], leading to sheets propagating in the bc plane.

Crystal structure of bis-(4-meth-oxy-phenyl) malonate.

The complete mol-ecule of the title compound, C17H16O6, is generated by crystallographic twofold symmetry, with the central methyl-ene C atom lying on the rotation axis. The carbonyl O atom is disordered over two adjacent positions in a 0.63 (3):0.37 (3) ratio and the dihedral angle between the benzene rings in the two halves of the mol-ecule is 79.31 (12)°. In the crystal, mol-ecules are connected by C-H⋯O hydrogen bonds, generating (110) sheets. Very weak intra-sheet C-H⋯π inter-actions are also observed.

Crystal structure of (R)-6'-bromo-3,3-dimethyl-3',4'-di-hydro-2'H-spiro-[cyclo-hexane-1,3'-1,2,4-benzo-thia-diazine] 1',1'-dioxide.

In the title compound, C14H19BrN2O2S, the 1,2,4-thia-diazinane ring adopts an envelope conformation with the N atom (attached to the sulfonyl group) as the flap, while the cyclo-hexane ring adopts a chair conformation. The mean plane of the cyclo-hexane ring is almost normal to the benzene ring and the mean plane of the 1,2,4-thia-diazinane ring, making dihedral angles of 70.4 (2) and 71.43 (19)°, respectively. Furthermore, the dihedral angle between the benzene ring and the mean plane of the 1,2,4-thia-diazinane ring is 4.91 (18)°. The mol-ecular structure is stabilized by an intra-molecular C-H⋯O hydrogen bond, which encloses an S(6) ring motif. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds into chains along [10-1], forming a C(6) graph-set motif. These chains are inter-connected via C-H⋯π inter-actions, leading to chains along [-101], so finally forming sheets parallel to (010).