The typical crystal structures of a few representative α-aryl-α-hydroxyphosphonates

The crystal structures of seven α-aryl-α-hydroxyphosphonates synthesized by the Pudovik reaction of substituted benzaldehydes and dialkyl phosphites, namely dimethyl [(hydroxy)(phenyl)methyl]phosphonate, C9H13O4P, dimethyl [(3,4-dimethoxyphenyl)(hydroxy)methyl]phosphonate, C11H17O6P, dimethyl (1-hydroxy-1-phenylethyl)phosphonate, C10H15O4P, dimethyl [1-hydroxy-1-(4-nitrophenyl)ethyl]phosphonate, C10H14NO6P, dibenzyl [hydroxy(2-nitrophenyl)methyl]phosphonate, C21H20NO6P, dibenzyl [(3-chlorophenyl)(hydroxy)methyl]phosphonate, C21H20ClO4P, and dibenzyl [hydroxy(4-methylphenyl)methyl]phosphonate, C22H23O4P, were studied to gain a better understanding of the organization in this type of molecule in the solid state. The crystals obtained for this series of compounds show a balance between C—OH...O=P chain-linked packing and the dimeric types of hydrogen-bond bridges of intermolecular pairs of such functions. The description is based on primary graph-set descriptors. Using graph-set descriptors one level deeper (i.e. secondary graph sets of the C—H...O type) revealed a similarity in the graph-set descriptors, suggesting a fine interplay of substituent- and shape-dependent effects on strong–weak interactions. It seems that the formation of chains or dimers is governed not only by the presence of a tertiary Cα atom, but also by the nature and crowding of the ortho substituents of the α-aryl group.

Hydrogen-bonded networks in oxygen-coordinated monoamide complexes of zinc(II)

The preparation of the bulky secondary amide N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamide and the determination of its crystal structure at 173(2) K are reported. The structure displays disorder of the tBu methyl groups due to thermal motion and an infinite N–H····O=C hydrogen-bonded chain described by a [Formula: see text] graph set. Reaction of this amide with ZnCl2 or ZnBr2 in tetrahydrofuran (THF) results in dihalo-(tetrahydrofurano)-(N-(2,6-diisopropylphenyl)–2,2-dimethylpropanamido)-zinc(II) complexes (Cl, Br) for which the crystal structures have also been determined. These complexes, as well as a chloroform solvate of the dichloro-complex, contain N–H····X–Zn hydrogen-bonded chains described by [Formula: see text] graph sets. Evaporative crystallization results in the loss of both chloroform and THF to afford crystals determined to be bis(μ2-chloro)-dichloro-bis(N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamido)-dizinc(II) by single crystal X-ray diffraction. This dimeric complex shows a complex network of N–H····Cl–Zn hydrogen bonds describable by [Formula: see text], [Formula: see text], and [Formula: see text] chains, small [Formula: see text] molecular “squares”, and larger [Formula: see text] rings.

Crystal structure of 3,6,6-trimethyl-4-oxo-1-(pyridin-2-yl)-4,5,6,7-tetrahydro-1H-indazol-7-aminium chloride and its monohydrate

The title compounds, C15H19N4O+·Cl−and C15H19N4O+·Cl−·H2O, obtained in attempts to synthesize metal complexes using tetrahydroindazole as a ligand, were characterized by NMR, IR and X-ray diffraction techniques. The partially saturated ring in the tetrahydroindazole core adopts a sofa conformation. An intramolecular N—H...N hydrogen bond formed by the protonated amino group and the N atom of the pyridyl substituent is found in the first structure. In the hydrochloride, the organic moieties are linked by two N—H...Cl−hydrogen bonds, forming aC(4) graph-set. In the hydrate crystal, a Cl−anion and a water molecule assemble the moieties into infinite bands showing hydrogen-bond patterns with graph setsC(6),R64(12) andR42(8). Organic moieties form π–π stacked supramolecular structures running along thebaxis in both structures.

Trimethyl 3,3′,3′′-(benzene-1,3,5-triyl)tripropynoate

In the title compound, C18H12O6, the alkyne bonds are distorted, featuring bond angles around the C—C[triple-bond]C—C group of 173.6 (1)/179.0 (1), 178.1 (1)/178.4 (1) and 174.9 (1)/175.9 (1)°, and the ester groups make angles of 3.5 (1), 13.8 (1) and 14.5 (1)° with the central benzene ring. In the crystal, molecules are connected in layers parallel to (131) by weak C—H...O hydrogen bonds, giving rise to a system of hydrogen-bonded ring motifs with graph setsR22(14) andR44(22). The layers are linked by C—H...O and C—H...π contacts.

Crystal structure of bis-p-anizidinegossypol with an unknown solvate

The title compound, C44H44N2O8, (systematic name: 1,1′,6,6′-tetrahydroxy-5,5′-diisopropyl-8,8′-bis{[(4-methoxyphenyl)iminiumyl]methyl}-3,3′-dimethyl-2,2′-binaphthalene-7,7′-diolate) has been obtained by the addition ofp-anizidine to gossypol dissolved in dichloromethane. In the solid state, the title compound exists in the enamine or quinoid form. The two naphthyl moieties are inclined to one another by 72.08 (5)°. The pendant phenyl rings are inclined at 22.26 (14) and 23.86 (13)° to the corresponding naphthyl rings. In the crystal, molecules are incorporated into layers through inversion-related pairs of O—H...O interactions [graph setsR22(20) andR22(10)] and translation-related O—H...O interactions [graph setC(15)]. The packing of these layers in the crystal structure gives rise to channels in the [011] direction, with hydrophobic interactions occurring between adjacent layers. The channels are 5–7 Å wide, and the void volume of each cell is 655 Å3, corresponding to 26.6% of the cell volume. Disordered guest molecules, probably solvent and water molecules, occupy these voids of the crystal; their contribution to the scattering was removed with the SQUEEZE routine [Spek (2015).Acta Cryst. C71, 9–18] ofPLATON[Spek (2009).Acta Cryst.D65, 148–155].

Crystal structure of fingolimod hydrochloride, C19H34ClNO2

The crystal structure of fingolimod hydrochloride (C19H34ClNO2) has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Fingolimod hydrochloride crystallizes in space group P21/n (#14) with a = 7.137 53(5), b = 5.957 98(4), c = 49.5196(4) Å, β = 91.0808(7)°, V = 2105.46(2) Å3, and Z = 4. The structure consists of a “lipid bilayer” packing. The polar ends of the molecules make O–H···Cl and N–H···Cl hydrogen bonds to the chloride anion, and the octyl side chains pack adjacent to each other. The hydrogen bonds form three types of chains with graph sets C1,2(7), C1,2(7), and C1,2(8). The result is a complex chain of hydrogen bonds parallel to the b-axis. The powder pattern has been submitted to ICDD for inclusion in future releases of the Powder Diffraction File™.