A 1:2 co-crystal of 2,2′-thiodibenzoic acid and triphenylphosphane oxide: crystal structure, Hirshfeld surface analysis and computational study

The asymmetric unit of the title co-crystal, 2,20-thiodibenzoic acid–triphenylphosphane oxide (1/2), C14H10O4S2C18H15OP, comprises two molecules of 2,20 -thiodibenzoic acid [TDBA; systematic name: 2-[(2-carboxyphenyl)sulfanyl]benzoic acid] and four molecules of triphenylphosphane oxide [TPPO;systematic name: (diphenylphosphoryl)benzene]. The two TDBA molecules are twisted about their disulfide bonds and exhibit dihedral angles of 74.40 (5) and 72.58 (5) between the planes through the two SC6H4 residues. The carboxylic acid groups are tilted out of the planes of the rings to which they are attached forming a range of CO2/C6 dihedral angles of 19.87 (6)–60.43 (8). Minor conformational changes are exhibited in the TPPO molecules with the range of dihedral angles between phenyl rings being �2.1 (1) to �62.8 (1). In the molecular packing, each TDBA acid molecule bridges two TPPO molecules via hydroxy-O—HO(oxide) hydrogen bonds to form two three-molecule aggregates. These are connected into a three-dimensional architecture by TPPO-C—HO(oxide, carbonyl) and TDBA-C—H(oxide, carbonyl) interactions. The importance of HH, OH/HO and CH/HC contacts to the calculated Hirshfeld surfaces has been demonstrated. In terms of individual molecules, OH/HO contacts are more important for the TDBA (ca 28%) than for the TPPO molecules (ca 13%), as expected from the chemical composition of these species. Computational chemistry indicates the four independent hydroxy-O—HO(oxide) hydrogen bonds in the crystal impart about the same energy (ca 52 kJ mol-1), with DTBA-phenyl-C—HO(oxide) interactions being next most stabilizing (ca 40 kJ mol-1)

Crystal structure, Hirshfeld surface analysis and computational study of the 1:2 co-crystal formed between N,N′-bis(pyridin-4-ylmethyl)ethanediamide and 4-chlorobenzoic acid

The asymmetric unit of the title 1:2 co-crystal, C14H14N4O22C7H5ClO2,comprises two half molecules of oxalamide (4LH2), as each is disposed about a centre of inversion, and two molecules of 4-chlorobenzoic acid (CBA), each in general positions. Each 4LH2 molecule has a (+)antiperiplanar conformation with the pyridin-4-yl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angles between the respective central core and the pyridyl rings being 68.65 (3) and 86.25 (3), respectively, representing the major difference between the independent 4LH2 molecules. The anti conformation of the carbonyl groups enables the formation of intramolecular amide-N—HO(amide) hydrogen bonds, each completing an S(5) loop. The two independent CBA molecules are similar and exhibit C6/CO2 dihedral angles of 8.06 (10) and 17.24 (8), indicating twisted conformations. In the crystal, two independent, three-molecule aggregates are formed via carboxylic acid-O—HN(pyridyl) hydrogen bonding. These are connected into a supramolecular tape propagating parallel to [100] through amide-N—HO(amide) hydrogen bonding between the independent aggregates and ten-membered {HNC2O}2 synthons. The tapes assemble into a three-dimensional architecture through pyridyl- and methylene-C—HO(carbonyl) and CBA-C—HO(amide) interactions. As revealed by a more detailed analysis of the molecular packing by calculating the Hirshfeld surfaces and computational chemistry, are the presence of attractive and dispersive ClC O interactions which provide interaction energies approximately one-quarter of those provided by the amideN—HO(amide) hydrogen bonding sustaining the supramolecular tape

2-[Carbamothioyl(2-hydroxyethyl)amino]ethyl benzoate: crystal structure, Hirshfeld surface analysis and computational study

The title di-substituted thio­urea, C12H16N2O3S, has the hy­droxy­lethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine—C—C—O(hydroxyl, carbon­yl) torsion angles of 49.39 (13) and 59.09 (12)°, respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26 (4)°. In the crystal, supra­molecular layers propagating in the ac plane are formed via a combination of hydroxyl-O—H...S(thione), amine-N—H...O(hydroxyl, carbon­yl) hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of π–π stacking [inter-centroid separation = 3.8722 (7) Å] and parallel C=O...π inter­actions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the inter­actions involving the benzene residue

The 1:2 co-crystal formed between N,N′-bis(pyridin-4-ylmethyl)ethanediamide and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study

The crystal and molecular structures of the title 1:2 co-crystal, C14H14N4O2-2C7H6O2, are described. The oxalamide molecule has a (+)-antiperiplanar conformation with the 4-pyridyl residues lying to either side of the central, almost planar C2N2O2 chromophore (r.m.s. deviation = 0.0555 A˚ ). The benzoic acid molecules have equivalent, close to planar conformations [C6/CO2 dihedral angle = 6.33 (14) and 3.43 (10)]. The formation of hydroxy-O—HN(pyridyl) hydrogen bonds between the benzoic acid molecules and the pyridyl residues of the diamide leads to a three-molecule aggregate. Centrosymmetrically related aggregates assemble into a six-molecule aggregate via amide-N—HO(amide) hydrogen bonds through a 10-membered {HNC2O}2 synthon. These are linked into a supramolecular tape via amide-N—HO(carbonyl) hydrogen bonds and 22-membered {HOCONC4NH}2 synthons. The contacts between tapes to consolidate the three-dimensional architecture are of the type methylene-C—HO(amide) and pyridyl-C—HO(carbonyl). These interactions are largely electrostatic in nature. Additional non-covalent contacts are identified from an analysis of the calculated Hirshfeld surfaces