Synthesis and characterization of 9-(4-nitrophenyl)3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione and its methoxyphenyl derivative

9-(4-Nitrophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione (NTHA) crystallizes in orthorhombic space group P2₁2₁2₁ with a = 5.9716(1) Å, b = 18.0476(3) Å, c = 19.2445(2) Å, V = 2074.04(5) ų, Z = 4, D_cal = 1.263 Mg m^?3 and R = 0.0521 (wR = 0.1326) for 4078 observed reflections. 9-(4-Nitrophenyl)-10-(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H) acridinedione NMTHA, crystallizes in monoclinic space group P2₁/c with a = 15.669(5) Å, b = 10.652(4) Å, c = 18.337(6) Å, β = 108.25(1)^°, V = 2906.66(2) ų, Z = 4, D_cal = 1.245 Mg m^?3 and R = 0.0725 (wR = 0.1847) for 5105 observed reflections. The experimental values are compared with the theoretical values calculated based on the semiemperical methods. The structures are stabilized by N–H?sO and C–H?sO types of intermolecular interactions in addition to van der Waals forces.     

Crystal structure of the new radical cation salt (<Emphasis Type="Italic">DOET</Emphasis>)<Subscript>4</Subscript>[Fe(CN)<Subscript>5</Subscript>NO]<Subscript>1.25</Subscript>(C<Subscript>6</Subscript>H<Subscript>5</Subscript>Cl)<Subscript>0.75</Subscript>

A new radical cation salt based on 4,5-(1,4-dioxanediyl-2,3-dithio)-4′,5′-ethylenedithiotetrathiafulvalene (DOET) with the photochromic anion [Fe(CN)₅NO]^2?, namely, (DOET)₄[Fe(CN)₅ NO]_1.25(C₆H₅Cl)_0.75, is synthesized. Single crystals of this salt are studied using X-ray diffraction [a = 10.398(2) Å, b = 11.168(2) Å, c = 18.499(4) Å, α = 103.14(3)°, β = 92.80(3)°, γ = 106.02(3)°, V = 1996.3(7) ų, space group \(P\bar 1\), and Z = 1]. In the structure, radical cation layers alternate with anion layers along the c axis. The centrosymmetric dimers are formed by DOET radical cations in the donor layer with packing of the β type. Like the vast majority of DOET-based salts, the new salt possesses semiconductor properties.     

Crystal and molecular structures of [Co(<Emphasis Type="Italic">D</Emphasis>H)(<Emphasis Type="Italic">o-phen</Emphasis>)<Subscript>2</Subscript>][BF<Subscript>4</Subscript>]<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of a new mixed-ligand complex [Co(DH)(o-phen)₂][BF₄]₂ · 2H₂O is determined by X-ray diffraction. The crystal is monoclinic, a = 12.2081(11) Å, b = 14.3474(9) Å, c = 17.7393(16) Å, β = 104.95(1)°, and space group P2₁/c. The coordination octahedron of Co³⁺ is formed by two nitrogen atoms of the dimethylglyoxime molecule and four nitrogen atoms of o-phenanthroline molecules. The dimethylglyoxime molecule is singly deprotonated and acts as DH^?. The mean Co-N distances for dioxime and o-phenanthroline are 1.911 and 1.964 Å, respectively. The key role in the formation of the crystal structure is played by [BF₄]^? outer-sphere anions and crystallization water molecules, which form an extended hydrogen-bond system.     

Synthesis and an X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The synthesis and X-ray diffraction study of compound Rb₂[(UO₂)₂(C₂O₄)₃], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) Å, b = 8.8259(8) Å, c = 11.3220(7) Å, β = 105.394(2)°, and V = 770.7(1) ų; space group P2₁/n, Z = 2, and R ₁ = 0.0271. [(UO₂)₂(C₂O₄)₃]^2? layers belonging to the AK _0.5 ⁰² T ¹¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and T ¹¹ = C₂O ₄ ^2? ) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.     

Crystal structure of <Emphasis Type="Italic">p</Emphasis>-carboxyphenylhydrazone benzoylacetone

The crystal structure of p-carboxyphenylhydrazone benzoylacetone is determined. The crystals are monoclinic, a = 13.614(4) Å, b = 11.388(2) Å, c = 20.029(6) Å, β = 104.82(2)°, V = 2339(9) ų, Z = 8, space group C2/c, and R = 0.038 for 1622 reflections with I > 2σ(I). The crystal is built of C₁₇H₁₄N₂O₄ neutral molecules that are linked by O-H?O hydrogen bonds between the carboxyl groups into centrosymmetric pseudodimers. The effect of carboxylation of the phenylhydrazone fragment and the position of the carboxyl group on the molecular packing in the crystal is determined. The N(1)-H(1N)?O(1) intramolecular hydrogen bond (N-H, 0.94 Å; H?O, 1.87 Å; N?O, 2.59 Å; and the N-H?O angle, 133°) is formed in the molecule.     

X-ray mapping in heterocyclic design: 16. X-ray diffraction study of 1-(4-chlorophenacyl)-4-methyl-1,5,6,7-tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-cyclopenta[<Emphasis Type="Italic">b</Emphasis>]pyridin-2-one

The structure of 1-(4-chlorophenacyl)-4-methyl-1,5,6,7-tetrahydro-2H-cyclopenta[b]pyridin-2-one is studied using single-crystal X-ray diffraction. The structure (a = 37.006(8) Å, b = 8.967(3) Å, c = 27.911(3) Å, β = 96.52(2)°, Z = 24, space group P2₁/c) is solved by direct methods and refined to R₁ = 0.0608 and wR₂ = 0.1170. Six crystallographically independent molecules differ in the dihedral angle between the phenyl and heterocycle planes. The formation of Cl?Cl aggregates is discussed.     

X-ray mapping in heterocyclic design: XII. X-ray diffraction study of 2-pyridones containing cycloalkane fragments annelated to the C(5)-C(6) bond

The structures of 4,6-dimethyl-1H-pyridin-2-one [a = 6.125(2) Å, b = 15.153(4) Å, and c = 14.477(4) Å, Z = 8, space group Pbca], the 2: 1: 1 complex of 4-methyl-1,5,6,7-tetrahydro-2H-cyclopenta[b]pyridin-2-one with phosphoric acid and methanol [a = 11.181(2) Å, b = 14.059(6) Å, c = 13.593(4) Å, β = 97.78(2)°, Z = 8, space group P2₁/n], 4-methyl-1,5,6,7,8,9-hexahydro-2H-cyclohepta[b]pyridin-2-one [a = 12.565(6) Å, b = 5.836(6) Å, c = 13.007(3) Å, β = 93.10(3)°, Z = 4, space group P2₁/n], and 4-methyl-5,6,7,8,9,10-hexahydrocycloocta[b]pyridin-2(1H)-one [a = 12.955(3) Å, b = 6.1595(15) Å, c = 13.038(3) Å, β = 95.50(2)°, Z = 4, space group P2₁/n] are determined by single-crystal X-ray diffraction. The structures are solved by direct methods and refined by the full-matrix least-squares procedure in the anisotropic approximation to R = 0.0755, 0.0644, 0.0754, and 0.0569, respectively. The structures of 4-methyl-1,5,6,7-tetrahydro-2H-cyclopenta[b]pyridin-2-one [a = 7.353(4) Å, b = 8.176(4) Å, c = 13.00(1) Å, β = 105.64(2)°, Z = 4, space group P2₁/c] and 2-oxo-1,2,5,6,7,8-hexahydroquinoline-3-carbonitrile [a = 5.9870(2) Å, b = 16.5280(5) Å, c = 9.6540(3) Å, β = 111.52(4)°, Z = 4, space group P2₁/c] are studied by the powder diffraction technique. The structures are solved using the grid search procedure and refined by the Rietveld method to R _wp = 0.108 and 0.058, R_exp = 0.032 and 0.027, R _p = 0.076 and 0.043, R _b = 0.123 and 0.077, and χ² = 7.9 and 3.64, respectively. In all the structures, hydrogen bonds involving the N, H, and O atoms of the pyridone fragment are formed.     

Crystal structure of <Emphasis Type="Italic">L</Emphasis>-serine phosphate

The crystal structure of L-serine phosphate (C₃O₃NH₇ · H₃PO₄) is determined by single-crystal X-ray diffraction. The unit cell parameters are as follows: a = 9.134(5) Å, b = 9.489(5) Å, c = 4.615(5) Å, γ = 99.54(5)°, space group P2₁, and Z = 2. The amino group of serine is protonated by a hydrogen atom of the phosphoric acid. The H₂PO ₄ ^1? ions are linked by hydrogen bonds into infinite ribbons aligned along the twofold screw axes. The ribbons form layers alternating with layers of serine molecules, which are directly linked by hydrogen bonds.     

Coordination dimers constructed from metal(II) halides and the organic ligand 1,2-dimethoxy- 4,5-bis(2-pyridylethynyl)benzene

A series of new coordination compounds has been synthesized using the organic ligand 1,2-dimethoxy-4,5-bis(2-pyridylethynyl)benzene (dmpeb). The compounds all form dimers consisting of two metal cations bridged by two ligand molecules. Charge balance is provided by halide ligands, and the four-coordinate metal centers are distorted from the ideal tetrahedral environment. [CoCl₂(dmpeb)]₂ (1) crystallizes in the monoclinic space group P2₁/n with a = 8.5272(6) Å, b = 18.3653(13) Å, c = 13.3493(9) Å, β = 103.574(2)^°, V = 2032.2(2) ų, Z = 2. [ZnCl₂(dmpeb)]₂ (2) is isostructural to 1 and has the cell parameters a = 8.5495(4) Å, b = 18.4049(8) Å, c = 13.3692(6) Å, β = 103.4460(10)^°, V = 2046.01(16) ų, Z = 2. [ZnBr₂(dmpeb)]₂ (3) is also isostructural to 1 with a = 8.7882(5) Å, b = 18.7260(12) Å, c = 13.3857(8) Å, β = 102.5990(10)^°, V = 2149.8(2) ų, Z = 2. Additionally, the compounds [ZnI₂(dmpeb)]₂ (4, cell parameters: a = 8.9650(5) Å, b = 19.1251(10) Å, c = 13.4160(7) Å, β = 101.1660(10)^°, V = 2256.7(2) ų, Z = 2), [HgCl₂(dmpeb)]₂ (5, cell parameters: a = 8.8457(7) Å, b = 18.4030(15) Å, c = 13.3711(11) Å, β = 104.246(2)^°, V = 2109.7(3) ų, Z = 2), and [HgBr₂(dmpeb)]₂ (6, cell parameters: a = 9.0576(5) Å, b = 18.8634(11) Å, c = 13.4535(8) Å, β = 102.9780(10)^°, V = 2239.9(2) ų, Z = 2) are also isostructural to 1. A seventh dimeric compound, [HgI₂(dmpeb)]₂, not isostructural to the others was also characterized by X-ray crystallography. [HgI₂(dmpeb)]₂ (7) crystallizes in the triclinic space group P-1 with a = 8.8028(5) Å, b = 12.0990(7) Å, c = 12.4082(7) Å, α = 109.7240(10)^°, β = 107.3680(10)^°, γ = 93.0880(10)^°, V = 1169.57(12) ų, Z = 1.     

Synthesis and Structure of Di(1,2,4,6-tetraphenylpyridinium) Octachlorodirhenate(III)

The (NC₅H₂(C₆H₅)₄)₂[Re₂Cl₈] · 2CH₃CN compound was prepared by the reaction of (n-Bu₄N)₂[Re₂Cl₈] with the 1,2,4,6-tetraphenylpyridinium tosylate in the acetonitrile; it crystallizes upon cooling of the solution at –15°C. The structure consists of the ((C₆H₅)₄C₅H₂N)⁺ cation and Re₂Cl ₈ ^2? anion with virtual D_4h symmetry. The average Re–Re and Re–Cl bond distances are 2.2205 and 2.3431 Å, respectively. In the structure, the Re₂Cl ₈ ^2? anions are disordered, such that 71.34% of the Re–Re units are aligned in one direction while 28.66% are aligned orthogonal to it. The principal crystallographic data are as follows: sp. gr. R?3; a = 26.554(1) Å, c = 23.666(1) Å; V = 14451.6(1) ų; Z = 9; D_x = 1.643 g cm^–3.     

X-ray mapping in heterocyclic design: XV. Tricyclic heterocycles based on 2-oxo-2,5,6,7-tetrahydro-1<Emphasis Type="Italic">H</Emphasis>-cyclopenta[<Emphasis Type="Italic">b</Emphasis>]pyridine-3-carbonitrile

The structures of five compounds are studied using single-crystal X-ray diffraction: 2-oxo-2,5,6,7-tetrahydro-1H-cyclopenta[b]pyridine-3-carbonitrile [a = 15.641(8) Å, b = 9.373(5) Å, c = 7.387(4) Å, β = 92.91(5)°, Z = 4, space group P2₁/c]; 1-[2-(4-chlorophenyl)-2-oxoethyl]-2-oxo-2,5,6,7-tetrahydro-1H-cyclopenta[b]pyridine-3-carbonitrile [a = 4.728(4) Å, b = 28.035(11) Å, c = 11.184(3) Å, Z = 4, space group P2₁2₁2₁]; 2-[2-(4-chlorophenyl)-2-oxoethoxy]-6,7-dihydro-5H-cyclopenta[b]pyridine-3-carbonitrile [a = 10.1202(13) Å, b = 11.2484(18) Å, c = 13.4323(19) Å, β = 102.05(1)°, Z = 4, space group P2₁/c]; 2-(4-chlorophenyl)-3a, 6,7,8-tetrahydrocyclopenta[e][1.3]oxazolo[3.2-a]pyridine-4-carboxamide perchlorate [a = 7.702(2) Å, b = 9.599(3) Å, c = 23.798(5) Å, β = 93.44(2)°, Z = 4, space group P2₁/c]; and (3-amino-6,7-dihydro-5H-cyclopenta[b]furo[3.2-e]pyridin-2-yl)(4-chlorophenyl)methanone [a = 7.3273(2) Å, b = 13.390(3) Å, c = 28.792(8) Å, Z = 8, space group Pbca]. The structures are solved using direct methods and refined by the full-matrix least-squares procedure in the anisotropic approximation to R = 0.0580, 0.0724, 0.0469, 0.0477, and 0.0418, respectively.     

High-pressure synthesis and magnetic properties of Bi<Subscript>0.5</Subscript>D<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> (<Emphasis Type="Italic">D</Emphasis> = Pb,Ba) solid solutions

Perovskites Bi_0.5D_0.5MnO₃(D = Pb, Ba) were prepared under high pressure (4 GPa) at 1200–1300°C. According to the X-ray diffraction data, crystalline Bi_0.5Pb_0.5MnO₃ has a tetragonal unit cell with the parameters a = 3.940 Å and c = 3.800 Å, whereas Bi_0.5Ba_0.5MnO₃ crystals are cubic with a = 3.940 Å. It is concluded from magnetic studies that lead-containing manganite is an antiferromagnet with T_N = 120 K, whereas Bi_0.5Ba_0.5MnO₃ is a spin glass with spin-freezing temperature T _f = 38 K. Both compounds are decomposed upon heating in air at temperatures above 500°C. With the use of synthesis in air, Bi_0.5Ca_{0.5 ? x}D _x MnO₃ solid solutions with x as high as 0.25 were obtained.     

Crystal structure analysis of 4-phenylquinolin-2-(1<Emphasis Type="Italic">H</Emphasis>)-one

The crystal structure of 4-phenylquinolin-2-(1H)-one (C₁₅H₁₁NO) is determined by X-ray diffraction. The compound crystallizes in the orthorhombic crystal system (space group Pbca) with the unit cell parameters a = 7.382(2) Å, b = 21.795(3) Å, c = 14.066(5) Å, and Z = 8. The structure is solved by direct methods and refined to an R-value of 0.0398 for 1360 observed reflections [F₀ > 4σ (F₀)]. The quinoline moiety and the substituted phenyl ring are nearly planar. The dihedral angle between these two moieties is 64.65(6)°. The crystal structure is stabilized by two intermolecular N-H?O and C-H?O interactions.     

The synthesis and crystal structure of (4<Emphasis Type="Italic">E</Emphasis>)-5(3-chlorophenyl)-<Emphasis Type="Italic">N</Emphasis>-(4-chlorophenyl)-2-diazo3-oxopent-4-enoic acid amide

(4E)-5-(3-Chlorophenyl)-N-(4-chlorophenyl)-2-diazo-3-oxopent-4-enoic acid amide (5) was synthesized from p-chloroaniline to N-(4-chlorophenyl)-2-diazo-3-oxo-butyramide (4) with 3-chlorobenzaldehyde. The yielded product 5 was investigated with X-ray crystallographic, NMR, MS, and IR techniques. Compound 5 (C₁₇H₁₁Cl₂N₃O₂, Formula wt = 360.19), crystallizes in the monoclinic space group P21/c with unit cell parameters a = 10.516(2), b = 17.996(4), c = 8.902(2) Å, α = 90.00, β = 105.36(3), γ = 90.00^°. V = 1624.5(6) ų, Z = 4, D _x = 1.473 Mg m^?3. The final R was 0.0511.     

Crystal structures of complexes of the <Emphasis Type="Italic">cys-syn-cys</Emphasis> isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][TaF₆] and [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) Å, b = 11.947(5) Å, c = 27.392(12) Å, β = 93.11(1)°, Z = 4, and space group P2₁/n for modification I; and a = 10.828(1) Å, b = 11.204(1) Å, c = 12.378(1) Å, α = 72.12(1)°, β = 79.40(1)°, γ = 73.70(1)°, Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 · H₃O)][NbF₆] (III) with the unit cell parameters a = 10.796(3) Å, b = 11.183(3) Å, c = 12.352(3) Å, α = 72.364(5)°, β = 79.577(5)°, γ = 73.773(4)°, Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I–III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48–2.58 Å). The conformation of the macrocycle in complex I differs substantially from that in complex II (III).     

Disaccharide nucleosides: The crystal and molecular structure of 2′-<Emphasis Type="Italic">O</Emphasis>-β-<Emphasis Type="Italic">D</Emphasis>-ribopyranosylcytidine

The crystal structure of a disaccharide nucleoside, 2′-O-β-D-ribopyranosylcytidine, is studied using X-ray diffraction (space group P2₁, a = 6.827(2) Å, b = 12.813(3) Å, c = 9.532(2) Å, β = 92.934(5)°, V = 832.7(4) ų, Z = 2). The stereochemical features of the molecular structure of 2′-O-β-D-ribopyranosylcytidine are analyzed, and the structural data are compared with those obtained for the previously studied disaccharide nucleoside 2′-O-β-D-ribofuranosyluridine.     

Crystal structure of <Emphasis Type="Italic">L</Emphasis>-alanine phosphate

The crystal structure of L-alanine phosphate (C₃O₂NH₇ · H₃PO₄) is determined by the single-crystal diffraction technique; a = 11.918(1) Å, b = 9.117(1) Å, c = 7.285(1) Å, γ = 104.7(1)°, space group P2₁, and Z = 4. The amino group of the alanine is protonated by the hydrogen atom of the phosphoric acid. Pairs of H₂PO ₄ ^? hydrogen-bonded ions are packed into layers alternating with layers of alanine molecules in the crystal. No hydrogen bonds are formed immediately between the alanine molecules.     

Growth and crystal structure of binary molybdate CsFe(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>

CsFe(MoO₄)₂ single crystals have been grown by solution-melt crystallization with a charge-to-solvent ratio of 1: 3 (with Cs₂Mo₃O₁₀ used as a solvent). The crystal structure of this compound has been refined by X-ray diffraction (X8 APEX automatic diffractometer, MoK _α radiation, 356 F(hkl), R = 0.0178). The trigonal unit cell has the following parameters: a = b = 5.6051(2) Å, c = 8.0118(4) Å, V = 217.985(15) ų, Z = 1, ρ_calc = 3.875 g/cm³, and sp. gr. P \(\bar 3\) m1. The structure is composed of alternating layers of FeO₆ octahedra (with MoO₄ tetrahedra attached by sharing vertices) and CsO₁₂ icosahedra.     

Synthesis,Characterization, and Crystal Structure of (2<Emphasis Type="Italic">E</Emphasis>)-3-(4-Fluorophenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one

The title chalcone, of formula C₁₅H₁₁F₁O_2, crystallized in the orthorhombic space group P2₁2₁2₁ (# 19) with crystal parameters a?=?6.9998(8) Å, b?=?12.6740(15) Å, c?=?12.8997(15) Å, V?=?1144.4(2) ų, Z?=?4, determined at 100 K with MoKα radiation. The solid-state structure displays an intramolecular S(6) hydrogen bond and the crystal architecture is maintained by intermolecular F?H, O?H, and C?C short contacts. A DFT geometry optimization is compared with the experimental structure. As ¹⁹F NMR spectroscopy can be used for metabolic tagging of biologically active compounds (including chalcones), the solution-state ¹⁹F chemical shift and ¹³C¹⁹F coupling constants (ⁿJ) are also reported.

Graphical Abstract

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Structure of 1-(2,6-dimethylphenyl)-<Emphasis Type="Italic">N</Emphasis>-hydroxy-4,4-dimethyl-2,5-dioxo-<Emphasis Type="Italic">N</Emphasis>-phenyl-3-pyrrolidine carboxamide

The title compound is crystallized in the monoclinic space group P2₁/c with cell parameters a = 7.499, b = 13.336, c = 19.390 Å, β = 99.716°, V = 1911.4 ų, Z = 4, D _cal = 1.273 Mg/m³ at T = 120 K. The structure is refined by full-matrix least-squares procedures to final R ₁ = 0.0548 and wR ₂ = 0.1089 for 3424 reflections. Two phenyl rings are noncoplanar with regard to each other and pyrrolidine core. The structure contains intramolecular hydrogen bond.