Morpholinium 2,4-dinitrophenolate Aqua Salt and Ethylenediammonium 2,4-dinitrophenolate Aqua Salt

Abstract The structures of the aqua salts of 2,4-dinitrophenolate (2,4-DNP⁻) with ethylenediammonium (EDA²⁺) and morpholinium (MP⁺) have been determined by X-ray diffraction, the first with 2:1 stoichiometry. The EDA²⁺ salt crystallizes in P_21/c space group, with a = 5.887; b = 23.441; c = 7.075, β = 96.61, R1 = 0.0365 for reflections with Fo > 4sig(Fo). MP⁺ salt crystallizes as P_–1 space group; a = 6.655; b = 9.388 c = 11.452; α = 104.82 β = 102.31 γ = 105.24, with R₁ = 0.0334. Phenolates and ammonium groups interact through hydrogen bonds and the N+···O distances for MP⁺ and EDA²⁺ salts are 2.783 ? and 2.812 ?, respectively. There is one water molecule by asymmetric unit, interacting with phenolate and ammonium ions. The arrays of hydrogen bonds are cyclic, with six and four members alternated and the position of the units is dependent on the ability to form hydrogen bonds. The Job’s plot for ethylenediamine and 2,4 dinitrophenol shows the same 2:1 stoichiometry in ethanol for EDA²⁺-2,4-DNP⁻ salt. Graphical abstract Structures of the dinitrophenolate aqua salts of morpholinium and ethylenediammonium are described with cyclic networks of hydrogen bonds between the species.      

Crystal structure of 2,4-di-para-methoxyphenylcyclobutadiene-1,3-quinone

The crystal structure of 2,4-di-p-methoxyphenylcyclobutadiene-1,3-quinone has been been determined using three-dimensional X-ray data collected by means of a Picker FACS-1 four-circle diffractometer. The crystal used was one of four modifications of this compound, two low density (1.38 g cm^?3) and two high density (1.54 g cm^?3) forms, obtained by us, depending on crystallization conditions. The space group isP¯1, with unit cell dimensionsa = 3.89,b = 10.80,c = 9.03 Å, α = 77.88, β = 74.12, γ = 85.15 °D _m = 1.38 g cm^?3 andZ = 1. A least-squares refinement of the positional and anisotropic thermal parameters gave a finalR-value of 6.0% for 364 reflections and 121 variables. The zwitter-ionic nature of the molecule can be seen in both the partial delocalization of the bonds in the 4-membered ring (which is square-planar) and the bonds joining thep-phenylene and 4-membered rings. The nearly planarp-phenylene rings themselves are quinone-like in structure and are parallel, but not coplanar. The columnar packing of the molecules resembles that of graphite, and observed interplanar spacing is 3.64 Å.     

Crystal structure of 4-methylpyridinium 2,4-dinitrophenolate

A crystalline salt of 4-methylpyridinium 2,4-dinitrophenolate has been prepared and characterized by X-ray crystallography. The salt crystallizes in the monoclinic space group P2_1/c with a = 9.105(2), b = 7.617(2), c = 18.424(3) Å, = 90.00, = 101.19(1), = 90.00°, V = 1253.5(5) ų, and Z = 4. In the title salt, the phenolate and pyridinium ion are held by bifurcated hydrogen bonds of N–H···O, and are arranged in an almost coplanar manner to each other due to two sets of CHO hydrogen bonds. The geometrical arrangement in the title salt is characterized by the formation of herringbone motif of 4-methylpyridinium 2,4-dinitrophenolate. The herringbone motif is stablized by CHO hydrogen bonds. The face-to-face interval between the phenolate and pyridinium ring is 3.3094 Å, in a range governed by – interaction.     

Electrical conductivity of 2,4-dinitrosoresorcinol and its complexes

Electrical conductivity measurements of 2,4-dinitrosoresorcinol (DNR) and its complexes were measured in the temperature range 20–115°C to give faint semiconducting behaviour for these systems. The conductivity values of the bis Co, Ni, Cu and Zn systems indicated that the metal ion forms a bridge between the two ligands facilitating the transfer of current carriers with some degree of delocalization in the excited state. As the iron content in the complexes increased, a gradual increase of electrical conductivity occurred, that might be due to lattice imperfections.     

Structure and IR spectroscopic behavior of 2,4-dimethylpyridinium pentachlorophenolate

The structure of 2,4-dimethylpyridinium pentachlorophenolate (DMP PCP) has been determined by X-ray diffraction. The crystals are monoclinic, space groupP2₁,/n, witha=8.729(7),b=13.72(1),c=12.82(1) Å,=91.39(8)° andZ=4. The structure was solved by the direct methods, and refined toR=0.040 for 2375 non-zero independent reflections. The N⁺-HO^– hydrogen bond is of length 2.604(3) Å. The ionic character of the hydrogen bond has been confirmed by the IR spectra.     

Crystal structure of 2,4-dinitroimidazole (24DNI)

A single-crystal X-ray diffraction study verified that the target oxidizer molecule 2,4-dinitroimidazole (24DNI) had been synthesized by thermal rearrangement of 1,4-dinitroimidazole. 24DNI crystallizes in the orthorhombic space group Pbca with unit-cell dimensionsa=10.127(2),b=18.497(2),c=6.333(2) Å, andZ=8 and has a density of 1.770 g/cm³. The molecular packing consists of hydrogen-bonded chains of 24DNI molecules [N(1)–H(1)...N(3)] in thea direction which are held together in the lateral direction by molecular forces. Some structural features of 24DNI·are compared with those of 1,4-dinitroimidazole.     

X-ray structural and spectroscopic investigation of 1-piperidine-2,4-dinitrobenzene

The crystal structure of the title compound (C₁₁H₁₃N₃O₄) has been determined by single-crystal X-ray diffraction. The compound is monoclinic, space group P2₁/n, witha=9.968(2),b=9.156(2),c=13.249(2)Å, =102.05(2)°, andD _x=1.563 gcm^–3 forZ=4. The aromatic ring shows a slight boat deformation. Theo- andp-NO₂ groups are twisted out of the plane of the phenyl ring by 39.0(2)° and 4.4(1)°, respectively. The piperidine ring exhibits a slightly deformed chair conformation. Short C–H...O intermolecular contacts stabilize the three dimensional structure. UV and NMR data indicate that the molecule in solution presents a conformation similar to that of the the solid state.     

Intramolecular interactions in ethyl bis-(2,4-dinitrophenyl)acetate

The crystal structure of ethyl bis(2,4-dinitrophenyl)acetate, determined by room temperature X-ray diffraction, shows that this crowded molecule contains two short intramolecular interactions between nitro oxygen atoms and electron deficient carbon atoms. One mimics an early stage of the nucleophilic addition to a carbonyl group (O...C, 2.730 Å), and the other mimics an early stage of a Michael reaction (O...C, 2.854 Å). Crystal data: C₁₆H₁₂N₄O₁₀, M _r = 420.29, a = 10.079(1), b = 11.139(1), c = 16.162(1) Å, = 91.319(7)°, monoclinic, P2₁/c, Z = 4.     

Crystal and molecular structure of 5-benzylidene-3-acetyl-2,4-oxolandione

The title compound crystallizes in the monoclinic space groupP2₁/n (No. 14),a=14.923(2),b=4.165(2),c=18.097(2) Å,=106.40(1)°,Z=4. The structure was solved by direct methods, and refined by full-matrix least squares toR=0.048 for 1313 observed reflections. Inter- and intramolecular hydrogen bonding is observed, the latter resulting in the formation of dimers.     

Structure ofcis-2,4-bis (trichloromethyl)-1,3,5,-trioxane

cis-2,4-Bis(trichloromethyl)-1,3,5-trioxane is monoclinic,C2/c, a=19.432(4),b=5.895(1),c=20.721(6) Å,=100.66(2)°,Z=8. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least-squares to a finalR value of 0.034 using 1786 reflections. The molecule is in the chair conformation with the –CCl₃ groups located equatorially [at C(2) and C(6) in the numbering scheme used in the paper]. Endocyclic parameters quoted cyclically are O(1)-C(2) 1.418(3), C(2)-O(3) 1.387(3), O(3)-C(4) 1.419(3), C(4)-O(5) 1.416(3), O(5)-C(6) 1.391(4), C(6)-O(1) 1.415(3) Å; and angles at O(1) 108.7(2), C(2) 110.5(2), O(3) 110.1(2), C(4) 109.5(2), O(5) 109.9(2), C(6) 110.5(2)°. The average endocyclic torsion angle is 59.1(5)°.     

Crystal structure of bis(2,4-pentanedionato)copper(II)

The structure of bis(acetylacetonato)copper(II) has been redetermined from single crystal X-ray diffraction data. The unit cell parameters area=11.331(9),b=4.697(3),c=10.290(9) Å, and=91.84(7)dg. A finalR=0.056 for 727 observed reflections was obtained. The O-Cu-O chelate (bite) angle is 93.2(2)°. The two Cu-O bond lengths are 1.914(4) and 1.912(4) Å. The complex has a slight chair structure and a step angle of 7.05°.     

The (−)-gossypol-2,4-pentanedione (1:2) inclusion complex

(–)-Gossypol and 2,4-pentanedione form an inclusion complex in a one-to-two molar ratio. The compound crystallizes in the tetragonal P4₁2₁2 space group and has unit cell dimensions of a=b = 10.9966(7) Å and c = 60.213(4) Å. Both solvent molecules are in the enol form and occupy two distinct cavities within the structure. The first cavity is formed between pairs of gossypol naphthalene rings and contains a pair of symmetry-related solvent molecules that each accept a hydrogen bond from one of the surrounding gossypol molecules. The four molecules together form a wedge-shaped assembly that is repeated throughout the cell. The assemblies stack to form columns, and adjacent columns are aligned parallel to form layers. Neighboring layers are oriented at 90° angles, which accounts for the fourfold symmetry of the space group. The second solvent cavity is located in isolated pockets that form between the layers. These solvent molecules also accept hydrogen bonds from the surrounding gossypol molecules. Although many gossypol solvates have been reported, this structure is unusual in a number of features. It is the first report of a chiral non-conglomerate gossypol solvate. It is also the only known chiral gossypol inclusion complex to not lose appreciable amounts of solvent when removed from its mother liquor.     

Crystal and molecular structure of 6-nitro-1,3-benzdioxin: Comparison with the molecular structures of the 2,4-bis(dichloromethyl) and 2,4-bis(trichloromethyl) derivatives

6-Nitro-1,3-benzdioxin is orthorhombic,Pbca,a=7.278(4),b=19.292(3),c=10.978(1) Å,Z=8. The structure was solved by direct methods from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer and refined by least squares to a finalR value of 0.041 using 725 reflections. Some parameters associated with the heterocycle are torsion angle (C_Ar)O-C-O-C(C_Ar) 69.1(4)°; bond lengths C_Ar-O 1.362(3), (C_Ar)O-C 1.434(5), (C_Ar.O)C-O 1.377(5), O-C(C_Ar) 1.431(5), C-C_Ar 1.501(5) Å; bond angles C_Ar-O-C 113.5(3), O-C-O 111.5(3), C-O-C(C_Ar) 110.3(3), O-C-C_Ar 109.9(3)°;H_axH_ax 2.52(5) Å.     

Crystal structure of two lipophilic antifolates: 2,4-diamino-5-(n-hexyl)-6-methylpyrimidine and 2,4-diamino-5-(n-heptyl)-6-methylpyrimidine ethanesulfonate

The 5-hexyl (I) and the 5-heptyl (II) analogs of 2,4-diamino-6-methylpyrimidine both crystallize in the space groupP2₁/c withZ=4. Unit cell parameters of I are C₁₁H₂₀N₄·H₂O,a=17.204(3),b=4.609(9),c=16.765(2)Å,= 91.53(2)°; those of II are C₁₂H₂₃N₄ ⁺·C₂H₅SO₃ ^–,a=12.489(1),b=16.702(2),c=8.9558(7)Å,=99.208(8)°. The molecular packing of I contains one water, while II forms a salt with ethanesulfonic acid. The alkyl chain of I adopts an alltrans conformation; in contrast, II has onegauche orientation between carbons 2 and 3 of heptyl. These are the first structural data on two alkyl lipophilic antifolates with antineoplastic activity.     

Synthesis and crystal structure of 7,7-dimethyl-2,4-diphenyl-5-oxo-1,4,5,6,7,8-hexahydroquinolin

The 7,7-dimethyl-2,4-diphenyl-5-oxo-1,4,5,6,7,8-hexahydroquinolin was synthesized and the compound was identified by IR, ¹H NMR, elemental analysis and X-ray crystallography. It crystallized in the triclinic space group , with a = 7.129(2) Å, b = 10.514(3) Å, c = 13.040(3) Å, =76.58(2)°, =88.97(2)°, =79.24(2)°, and D _calc = 1.172 g cm^–3 for Z = 2. X-ray analysis revealed that the atoms C(2), C(3), C(4), C(10), C(9), and N form a six-membered ring that adopts a boat conformation, and another six-membered ring (C(10)–C(9)–C(8)–C(7)–C(6)–C(5)) adopts a half-chair conformation. In addition, there is an intermolecular hydrogen bond (N–H0O) in the product molecule.     

X-ray and infrared spectroscopic studies of potassium hydrogen bis-(2,4-dichlorophenoxyisobutyrylglycinate)

Crystals of the title compound belong to space groupP¯1, withZ=1. TheK ⁺ ions and the acidic protons occupy centers of symmetry. This and the very short OO distance of 2.430 (9) Å classify the compound as a typeA acid salt. The infrared spectrum shows the _s OHO band near 800 cm^–1 with remarkably good definition at –170°C.     

Structure and conformation of 6-nitro-2,4-bis(dichloromethyl)-1,3-benzdioxin

6-Nitro-2,4-bis(dichloromethyl)-1,3-benzdioxin is monoclinic,P2₁/c, witha=8.514(1),b=22.187(3),c=7.931(1) Å,=117.96(1)°,Z=4. The structure was solved, from data collected with MoK radiation on an Enraf-Nonius CAD4 diffractometer, by direct methods and refined by full-matrix least squares using 2170 unique reflections to give a finalR factor of 0.032. The heterocyclic ring in the title compound has an envelope conformation with thecis-dichloromethyl groups in pseudoequatorial positions. The average C-C(HCl₂) distance is 1.516(4) Å. A comparison is given with the structure of the analogous compound 6-nitro-2,4-bis(trichloromethyl)-1,3-benzdioxin (Irving, A., and Irving, H. M. N. H. (1986)J. Crystallogr. Spectrosc. Res. 16, 703) which also containscis-halogenoalkyl groups but in which the –CCl₃ group at the 4-position occupies a pseudoaxial position.