X-ray structure and NMR assignment of 4-methoxy-4′-methylthio-3,3′-diquinolinyl sulfidea

The title compound (C₂₀H₁₆N₂OS₂) is monoclinic, witha=7.786(3).,b=13.252(3),c=17.162(4) Å, =99.16(3)° and space groupP2₁/n. Two quinoline moieties are nearly perpendicular to each other (112.9(2)°). Both methoxy and methylthio groups are trans-orientated with the respect to the C(3)–S(1)–C(13) plane. Two pairs of the heteroatoms in ortho-positions are in very close contact. The conformation of the molecule explains an unusual¹H NMR spectrum     

X-ray structure of 3′,4-dimethylthio-3,4′-diquinolinyl sulfide

The title compound (C₂₀H₁₆N₂S₃) is monoclinic, witha=31.550(9),b=8.504(3),c=14.745(3) Å,=114.14(3)°,Z=8 and space groupC2/c. The structure was solved by direct methods and refined toR=0.038 for 3012 reflections. The molecule exists in an uncommon conformation. Two quinoline moieties are nearly perpendicular to each other (80.9(3)°). Both methylthio groups have different orientation (the 4-SCH₃ group is nearly perpendicular and the 3-SCH₃ is nearly coplanar to the quinoline moieties). Two pairs of sulfur atoms in ortho-positions remain in very close contact. The conformation of the molecule explains an unusual¹H NMR spectrum.Part XVI in the series of Azinyl Sulfides.     

X-ray structure and 1H NMR assignment of 1-methyl-1,4-dihydro-4-oxo-4′-methylthio-3,3′-diquinolinyl sulfide

The title compound (C₂₀H₁₆N₂OS₂) is orthorhombic, with a = 9.290(2), b = 11.874(3), c = 15.971(4) Å and space group P2₁2₁2₁. Two quinoline moieties are nearly perpendicular to each other (103.5(2)°). Two pairs of heteroatoms in ortho-positions are in very close contact. The 4-oxo and 4-methylthio groups are trans-orientated to the central sulfur bridge. The sulfide preserves a skew conformation. The unusual H-2 proton upfield shift is induced by the ring current effect.     

X-ray structure of 4-chloro-3′-methylthio-3,4′-diquinolinyl sulfide

The title compound crystallizes in a monoclinic space groupP2₁/n witha=9.524(3),b=6.782(2),c=26.217(6) Å, =92.52(4)°. The values of the Cl...S and S...S distances are well below the sum of the van der Waals radii of the heteroatoms. Also, the Cl–C–C(S) and (Cl)C–C–S bond angles are below the standard 120°. This indicates a attractive interaction between both pairs ofortho-situated heteroatoms.Part XXXVIII in the Series of Azinyl Sulfides.     

X-ray structure of 3,3′-bis(4-methylthioquinolinyl) sulfide

The structure of the title compound has been solved by direct methods, and refined to anR value of 0.035 for 1613 reflections. Both methyl carbon atoms deviate from the plane of the pyridine ring by 1.505(3) Å in opposite directions. Both sulfur atoms S(1) and S(2) remain in short contact, at 3.247(1) Å. The two pyridine rings are inclined at 61.4(2)° to each other.Part XIV in the series of Azinyl Sulfides.     

Crystal structure of 1,4-dihydro-1-methyl-3′-methylsulfinyl-4-oxo-6-nitro-3,4′-diquinolinyl sulfide complex with DMF

The title compound crystallized as a complex with N,N-dimethylformamide (DMF) in a monoclinic space group P2 ₁ /c with a = 9.469(2), b = 25.168(5), c = 9.860(3) Å, and = 97.48(3)°. The two quinoline moieties are nearly perpendicular. The sulfoxide oxygen is pointed toward the H-2 proton. The S-methyl group is perpendicular to the parent pyridine ring plane.     

Synthesis and X-ray structure of 5′-methoxy-2,4,6-trimethyl-2′-nitrosobiphenyl

The synthesis and X-ray crystal structure of 5-methoxy-2,4,6-trimethyl-2-nitrosobiphenyl is reported. The compound (C₁₆H₁₇NO₂) is monoclinic, with a = 11.080(4), b = 16.899(6), c = 15.410(5) Å, = 108.329(5)°, and space group P2₁/n. There are two independent molecules within the crystal. In each of these molecules the two phenyl rings are mutually orthogonal, with interplanar dihedral angles of 85.09 and 89.43° respectively. The nitroso substituents are essentially coplanar with the phenyl ring, with torsional angles of only 3.5 and 2.2°, respectively, while the methoxy groups make angles of 5.2 and 10.0°, respectively, with the phenyl ring.     

Chemical preparation and crystal structure of 6′-butoxy-2,6-diamino-3,3′azo-dipyridine monohydrate

Chemical preparation, X-ray single crystal, and calorimetric studies of C₁₄H₁₈N₆O·H₂O are described. The compound crystallizes in the triclinic space group, P with unit cell dimensions: a = 6.2640(3), b = 10.9840(4), c = 12.2220(3) Å, = 105.03(2), = 96.96(2), = 101.6(2)°, V = 712.10(5) ų, and Z = 2. The 6-butoxy-2,6-diamino-3,3-azo-dipyridine monohydrate structure is built up from organic layers parallel to the (120) plane linked via O—H···N bond.     

A novel class of naturally occurring halogenated pyrroles, 1,1′-dimethyl-3,3′,4,4′,5,5′-hexabromo-2,2′-bipyrrole, 5,5′-dichloro-1,1′-dimethyl-3,3′,4,4′-tetrabromo-2,2′-bipyrrole, and 1,1′-dimethyl-3,3′,4,4′,5,5′-hexachloro-2,2′-bipyrrole

Crystal structure determinations of the three title hexahalogenated bipyrroles, (I) C₁₀H₆Br₆N₂, (II) C₁₀H₆Br₄Cl₂N₂, and (III) C₁₀H₆Cl₆N₂, reveal essentially planar pyrrole rings having dihedral angles of 64.7, 65.1, and 64.2° between the least-squares planes, favoring in each case a closer methyl–halogen conformation. All three complexes crystallize in the orthorhombic space group Pbcn with the following cell dimensions: (I) a = 12.654(3) Å, b = 8.853(2) Å, c = 13.753(3) Å, = = = 90°, Z = 4; (II) a = 12.438(6) Å, b = 8.753(6) Å, c = 13.696(3) Å, = = = 90°, Z = 4; (III) a = 12.088(6) Å, b = 8.566(4) Å, c = 13.486(8) Å, = = = 90°, Z = 4.     

X-ray Crystal Structures of Discrete and Polymeric Silver Based Molecules Containing 4,4′-Dimethyl-2,2′-Bipyridine and 2,2′-Bipyridine

Abstract  The reaction of AgBF₄ with 4,4′-dimethyl-2,2′-bipyridine and 2,2′-bipyridine yields three previously unreported compounds. The molecular structures of these compounds were obtained by single-crystal X-ray diffraction. Crystallization of 1 occurs in the centrosymmetric monoclinic space group C2/c (No. 15) with a = 23.407(3), b = 10.7552(13), c = 13.9332(17); and β = 111.893(2) and Z = 8. Crystallization of 2 occurs in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 11.178(3), b = 23.590(6), c = 29.339(8) and Z = 8. Crystallization of 3 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 11.2250(6), b = 8.7713(5), c = 15.4048(8), and β = 109.333(2) and Z = 4. Details of the synthesis and the structural characterization of the title compounds are presented and discussed. Index Abstract  The organic ligands 4,4′-dimethyl-2,2′-bipyridine and 2,2′-bipyridine, were used to synthesize three new complexes with AgBF₄, whose structures are dependent on the type of solvent used in the reaction as well as solvent of crystallization.      

The electronic nature of the substituents and the structure of 4,4′-dipyridilium dications. The crystal structure of N,N′-di(carbethoxymethyl)-4,4′-dipyridilium diperchlorate

The crystal structure of N,N′-di(carbethoxymethyl)-4,4′-dipyridilium diperchlorate (I) C₁₈H₂₂Cl₂N₂O₁₂ at 293 K is determined by the X-ray diffraction technique. The crystals are monoclinic, a = 5.501(1) Å, b = 26.460(5) Å, c = 8.140(2) Å, β = 100.63(3)°, space group P2₁/n, Z = 2, 2271 reflections measured (2052 reflections unique), R ₁ = 0.062, and wR2 = 0.141 for 1161 reflections with F ≥ 4σ(F). The interaction between the lone-electron pair of the carbonyl oxygen atom of the electron-withdrawing ester group and the π system of the dication manifests itself as the intramolecular O(1)?N contact (2.780 Å). In the absence of charge transfer from the counterion to the dication, this interaction contributes to the stabilization of a planar structure of the dication fragment of the molecule despite the electron-withdrawing nature of the ester groups.     

Crystal structure of 3,3′-dimethoxybenzydine (2-hydroxybenzal)diimine

Molecular and crystal structure of 3,3'-dimethoxybenzydine(2-hydroxybenzal)diimine, C₂₈H₂₄N₂O₄, have been determined by single crystal X-ray diffraction study. The title compound is monoclinic, with a= 18.045(2) Å, b= 11.725(4) Å, c= 12.436(6) Å, = 120.03(3)°, Z=4, D _x =1.32 g/cm³, (MoK) =0.089 mm^–1, and space group is C2/c. The structure was solved by direct methods and refined to a final R=0.056 for 2325 reflections with I > 2(I). There is half independent molecule in the asymmetric unit. The molecule has a twofold symmetry on the mid point of the C4 C4 ⁱ bond. The N1-C8 imine bond length of 1.284(3) Å is typical of a double bond. The molecule of the title compound is not planar. There is a strong intramolecular hydrogen bond between hydroxy oxygen atom and imine nitrogen atom. The crystal structure is stabilized by a weak intermolecular hydrogen bond of the C H O type forming three-dimensional cage.     

Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate

The precursor compound 4,4′-diaminostilbene-2,2′disulphonic acid DAS-(SO₃H)₂ was successfully deprotonated through reactions with (n-Bu₄N)(OH) and NaOH to produce the corresponding salts sodium 4,4′-diaminostilbene-2,2′disulphonate Na₂(DAS-(SO₃)₂) (1) and tetrabutylammonium 4,4′-diaminostilbene-2,2′disulphonate (n-Bu₄N)₂(DAS-(SO₃)₂) (2). The structure of (n-Bu₄N)₂(DAS-(SO₃)₂) (2) was confirmed through the use of single crystal X-ray diffraction. Compound (2) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 10.0645(6), b = 14.2573(9), c = 17.6053(11), and β = 94.3160(10). The reaction of Cu²⁺(aq) with (n-Bu₄N)₂(DAS-(SO₃)₂) resulted in the crystallization of the molecular organocopper cluster, [CuDAS-(SO₃)₂]₂·3H₂O (3), that resembles a molecular parallelogram as revealed by single crystal X-ray diffraction. Compound (3) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 8.8647(6), b = 10.5247(7), c = 21.2265(14), and β = 93.1730(10). Within the structure of (3) each [DAS-(SO₃)₂]²⁻ ligand is shown to bind two copper atoms through interactions with three of the five available metal binding sites.

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Graphical abstract Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate Natalie C. Rader, Heather A. Nees, Paul S. Szalay*, Matthias Zeller and Allen D. Hunter The preparation of 4,4′-diaminostilbene-2,2′disulphonic and its reactivity with copper(II) are described.

     

Synthesis and crystal structure of a new organic compound: Bis(4,4′-diaminodiphenylmethane) (4,4′-diammoniodiphenylmethane) dichloride monohydrate

A new organic compound with the formula C₃₉H₄₆Cl₂N₆O was synthesized from aqueous solution of 4,4′-diaminodiphenylmethane and hydrochloric acid at room temperature. This compound crystallizes in the monoclinic space group C2: a = 25.6525(16), b = 5.7107(3), c = 13.7777(8) Å, β = 118.862(2)°, V = 1767.64(22) ų and Z = 2, giving D _x = 1.288 g cm^?3. The refinement converged to R ₁ = 0.027 and wR ₂ = 0.0649. The structural arrangement can be described as infinite layers parallel to bc plane. In these layers cations and non protonated molecules are linked with N-H...N hydrogen bonds building [C₃₉H₄₄N₆]²⁺ organic clusters. These clusters, in turn, are linked by N-H...Cl and O-H...Cl hydrogen bonds.     

Electron effects of the substituents on the structure of 4,4′-dipyridylium dications

The crystal structure of N,N′-di(2-hydroxyethyl)-4,4′-dipyridylium diperchlorate C₁₄H₁₈Cl₂N₂O₁₀ is determined by X-ray diffraction at 293 K. The crystals are monoclinic, a = 6.446(1) Å, b = 14.479(3) Å, c = 9.912(1) Å, β = 99.24(2)°, space group P2₁/c, and Z = 2; 1562 reflections measured; and wR2 = 0.086 and R1 = 0.033 for 1209 reflections with F > 4σ(F). It is found that, in the absence of charge transfer from the counterion to the dication, the planarity of the dipyridylium skeleton of the molecule is primarily due to the conjugation between the lone electron pairs of the hydroxyl groups and the π system of the dication. This inference is supported by the intramolecular O?N contact (2.847 Å).     

Crystal and molecular structure of 1,1′-ferrocene-dicarbaldehyde

The crystal and molecular structure of 1,1-ferrocene-dicarbaldehyde 1 is reported. Crystal data for 1: monoclinic, space group P2₁/n, a = 5.876(1), b = 11.349(1), c = 29.460(3) Å, = 95.067(2)°, V = 1956.9(3) ų, and D _c = 1.64 g/cm³, for Z = 8. The complex crystallizes such that two molecules are located in the asymmetric unit in which the complexes display different degrees of twisting of the cyclopentadienyl (Cp) rings and formyl substituents about the Cp—Fe—Cp and Cp—COH axes, respectively. The molecule self-assembles in the solid state to form a 2D layered structure held together by - interactions and C—H···O hydrogen bonds.     

Synthesis and structure of 5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-di(methylthio)-3,3′-biisoquinoline

Title compound, C₂₀H₂₄N₂S₂, crystallizes in the orthorhombic system, space group Pbca, with cell constants a = 5.1968(5) Å, b = 15.6692(11) Å, c = 22.3881(11) Å , Z = 4, T = 293 K, D_cal = 1.299 g cm^–3. The structure was solved by direct methods and refined to R value of 0.0465 for 1566 reflections. Two methylthio-octahydroisoquinoline parts of molecule are related by the center of symmetry and possess the trans conformation. This conformation is more energetically stable than cis but the molecule can rotate about the C(6)–C(6) central bond at room temperature (molecular mechanics calculations). There is a short intramolecular contact C(5)–H(51) N(1) in the molecule. The molecules in the crystal form molecular layers parallel to (001) crystallographic plane and the molecular packing is determined by the van der Waals forces only.     

Hydrogen-Bonded Molecular Ladders and Interlaced Networks in Complexes Built of V-Shaped Molecules 4,4′-Isopropylidenediphenol or 4,4′-Oxydibenzoic Acid with 4,4′-Bipyridine

Abstract  

The title compounds, C₁₀H₈N₂·C₁₅H₁₆O₂ (1) and C₁₀H₈N₂·C₁₄H₁₀O₅ (2), were synthesized by 4,4′-bipyridyl and two similar V-shaped molecules. The two complexes both crystallized in the same space group P2₁/n with the crystal cell parameters: a = 16.0536(3) ?, b = 6.42730(1) ?, c = 21.2717(4) ?, β = 102.330°, V = 2144.21(7) ?³, Z = 4 in compound 1 and a = 7.45020(10) ?, b = 10.0784(2) ?, c = 26.9430(5) ?, β = 92.1140(10)°, V = 2021.67(6) ?³, Z = 4 in compound 2. Compound 1 forms regular molecular chains containing alternative 4,4′-bipyridyl and 4,4′-isopropylidenediphenol units; the molecular components are linked by two types of O–H···N hydrogen bonds. Additionally, every two neighboring chains are connected to be a ladder structure by means of weak C–H···O interactions. In compound 2, 4,4′-bipyridyl and 4,4′-oxydibenzoic acid first construct one-dimensional architecture by strong O–H···N hydrogen bonds, which are similar with the interactions in compound 1. Secondly, two types of weak C–H···O contacts formed between 4,4′-bipyridyl and the acid link one-dimensional chains to be interlaced three-dimensional hydrogen-bonded networks.     

Crystal structures of 3,5,5′-trichloro-2,2′-bithiophene and 3,3′,5,5′-tetrachloro-2,2′-bithiophene

The crystal structures of 3,5,5-trichloro-2,2-bithiophene (I) and 3,3,5,5-tetrachloro-2,2-bithiophene (II) have been determined by single crystal X-ray diffraction techniques. BothI andII crystallize in the monoclinic crystal system. ForI,a=3.895(2),b=11.928(2),c=10.701(2)Å,=97.70(1)°, space groupP2₁,Z=2 and forII,a=8.942(2),b=3.900(2),c=15.180(2)Å,=92.30(1)°, space groupP2₁/n,Z=2. The structures have been solved by direct methods and all nonhydrogen atoms refined with anisotropic thermal parameters. ForI the final residual is 0.035 (all 1185 independent reflections, MoK radiation) and forII, 0.034 (all 1209 independent reflections, MoK radiation). BothI andII have theanti conformation butI has a torsion angle of 3.4(5)° between the two thiophene rings whileII is completely planar.     

Electronic nature of substituents and the structure of 4,4′-dipyridylium dications: Crystal structure of <Emphasis Type="Italic">N,N′</Emphasis>-di(2-carboxyethyl)-4,4′-dipyridylium diperchlorate

The crystal structure of N,N′-di(2-carboxyethyl)-4,4′-dipyridylium diperchlorate, C₁₆H₁₈Cl₂N₂O₁₂, is determined using X-ray diffraction analysis at 293 K. The crystals are orthorhombic, a = 20.084(4) Å, b = 8.687(2) Å, c = 11.725(2) Å, space group Pna2₁, and Z = 4; 1688 reflections measured; and R = 0.056 and R _w = 0.059 for 1244 reflections with I > 3σ(I). It is found that, in the absence of charge transfer or short intramolecular O?N contacts, the nucleus of the dication adopts a twist conformation (the angle of rotation between the planes of the pyridine rings is equal to 23°).