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.     

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.

     

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.      

X-ray Crystal Structures of Silver Based Molecules Containing 5,5′-Dimethyl-2,2′-bipyridine and 2,2′-bipyridine

Abstract  

The reaction of AgBF₄ with 5,5′-dimethy-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 triclinic space group P-1 (No. 2) with a = 13.0069(6), b = 13.5903(6), c = 13.9489(6); and α = 95.677(2), β = 98.995(2), γ = 101.716(2) and Z = 6. Crystallization of 2 occurs in the centrosymmetric monoclinic space group C2/c (No. 15) with a = 23.413(3), b = 11.2116(13), c = 13.0653(13) and β = 123.074(3), and Z = 4. Crystallization of 3 occurs in the centrosymmetric triclinic space group P-1 (No. 2) with a = 12.6843(12), b = 12.8834(13), c = 12.9887(13), and α = 96.172(5), β = 95.149(5), γ = 98.051(6) and Z = 2. Details of the synthesis and the structural characterization of the title compounds are presented and discussed.     

Ground state structures of molecules “prepared” for phototautomerization: 2,2′-bipyridyl-3,3′-diol and 2,2′-bipyridyl-3-ol

The crystal structures of two molecules undergoing fast intramolecular excited state proton transfer (2,2-bipyridyl-3,3-diol, BP(OH)₂, and 2,2-bipyridyl-3-ol, BP(OH)) are reported and compared with the results ofab initio and molecular mechanics calculations. Strong intramolecular hydrogen bonding is observed in both cases. The pyridyl rings are coplanar in BP(OH)₂, whereas in BP(OH) they form an angle of 3.7°.Dedicated to Prof. R. Zahradnik on the occasion of his birthday.     

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.     

Crystal structures and energy refinement of some 2,2′-disubstituted biphenyl compounds

Synthesis and structural determination by X-ray crystallography of three substituted biphenyl structures are reported: (2) is monoclinic P2₁/n witha=10.805(4),b=8.079(3),c=16.232(6)Å, =100.96(5)°: (4) is monoclinic P2₁/n witha=9.966(3),b=10.007(3),c=13.053(4) Å, =96.74(5)°; (5) is triclinic witha=12.033(5),b=16.903(8),c=9.752(4)Å, =94.70(3)°, =112.56(3)° =76.12(3)°. In all compounds the biphenyl has two identical substituents in an ortho position to the center inter-ring bond and present variable inter-ring twist angles. In the process of investigating molecular geometry, we are interested in studying whether the calculated conformations of our molecules can fit the crystallographic structures.     

Crystal structures of two substituted biphenyl derivatives: 5,5′-di t-butyl-2-2′-biphenyldiol and 5,5′-dimethyl-2,2′-biphenyldiol

5,5-Di t-butyl-2,2-biphenyldiol (I), C₂₀H₂₆O₂, crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 18.243(2), b = 9.947(2), c = 9.685(3) Å, and Z = 4; 5,5-dimethyl-2,2-biphenyldiol (II), C₁₄H₁₄O₂, crystallizes in the monoclinic space group P2₁/c with a = 9.959(2), b = 7.932(3), c = 15.392(2) Å, = 105.43(2)°, and Z = 4. The aromatic rings are tilted by 52.7(1) and 43.8(1)° to each other in compounds (I) and (II), respectively. Strong intra- and inter-molecular H-bonds connect the molecules in the crystals.     

Crystal structures of four inclusion compounds of 2,2′-dithiosalicylic acid and tetraalkylammonium

Herein four inclusion compounds of 2,2′-dithiosalicylic acid and tetraalkylammonium, 2(CH₃)₄N⁺·C₁₄H₈O₄S₂^2?·H₂O (1), (C₂H₅)₄N⁺·C₁₄H₉O₄S₂^?·0.25H₂O(2), (n-C₃H₇)₄N⁺·C₁₄H₉O₄S₂^? (3) and (n-C₄H₉)₄N⁺·C₁₄H₉O₄S₂^?(4) are prepared and characterized by X-ray single crystal diffraction. As shown in the results, compounds 1 and 3 belong to orthorhombic crystal system with different space groups of P2₁2₁2₁ and Pca2₁, and 2 and 4 are monoclinic system with similar groups of P2₁/n and P2₁/c. The crystallography data are displayed below: 1: a = 10.5903(7) Å, b = 10.6651(7) Å, c = 21.9476(13) Å, V = 2478.9(3) ų, Z = 4, R₁ = 0.0359; 2: a = 8.13340(1) Å, b = 22.0741(3)Å, c = 13.2143(2)Å, β = 101.6360(1) °, V = 2323.70(6) ų, Z = 1, R₁ = 0.0385; 3: a = 15.7857(2) Å, b = 8.24830(1) Å, c = 20.2599(2) Å, V = 2637.94(5) ų, Z = 4, R₁ = 0.0308_degree4: a = 11.7476(2) Å, b = 17.1346(1) Å, c = 16.3583(3)Å, β = 109.4560(1) °, V = 3104.74(9)ų, Z = 4, R₁ = 0.0562. Interestingly, although the carbon chains of the guest templates vary from methyl group to butyl group, the host molecules of 2,2′-dithiosalicylic acid all construct the similar 2D hydrogen-bonded host layers with or without the existence of water molecules to contain the guest templates to yield analogous sandwich-like inclusion compounds. Obviously, although the guest templates will have certain effects on the ultimate formation of these crystal structures, the host molecule of 2,2′-dithiosalicylic acid is a controlling factor to form these four inclusion compounds.     

Structures of nitrato-(2-hydroxybenzaldehydo) (2,2′-bipyridyl)copper and nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2′-bipyridyl)copper

Nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2′-bipyridyl)copper (I) and nitrato-(2-hydroxybenzaldehydo)(2,2′-bipyridyl)copper (II) were synthesized and characterized by X-ray diffraction. The coordination polyhedron of the central copper atom in complex I can be described as a distorted tetragonal pyramid whose base is formed by the phenol and carbonyl oxygen atoms of the monodeprotonated 2-hydroxy-5nitrobenzaldehyde molecule and the nitrogen atoms of the 2,2′-bipyridyl ligand and whose apex is occupied by the oxygen atom of the nitrato group. In the crystal structure, complexes I are linked by the acido ligands and the NO₂ groups of the aldehyde molecule into infinite chains. In complex II, the central copper atom is coordinated by 2-hydroxybenzaldehyde, 2,2′-bipyridyl, and the nitrato group, resulting in the formation of centrosymmetric dimers. The coordination polyhedron of the central copper atom can be described as a bipyramid (4 + 1 + 1) with the same base as in complex I. The axial vertices of the bipyramid are occupied by the oxygen atom of the nitrato group and the bridging phenol oxygen atom of the adjacent complex related to the initial complex by a center of symmetry. In the crystal structure, complexes II are hydrogen bonded into infinite chains.     

Crystal and molecular structure of the inclusion compound between 1,1′-binaphthyl-2,2′-dicarboxylic acid and acetylacetone (1∶1)

The lattice type crystalline inclusion compound of 1,1-binaphthyl-2,2-dicarboxylic acid (BNDA) with acetylacetone (AcAc) 11 has been investigated by single crystal X-ray diffraction. AcAc is present as the enolic tautomer, stabilized by a notably short intramolecular hydrogen bond. This H-bond closes a six-membered ring with delocalization of the system of conjugated double bonds. In the crystal the AcAc molecules are incorporated into channels, delimited by bulky binaphyl moieties, in a hydrogen-bonded framework of BNDA, and they do not show any disorder. The strictly stoichiometric host:guest ratio seems to be enforced by packing forces only.     

Crystal structures of 1,1′-di(2-propanone)-2,2′-biimidazole dihydrazone and 2,6-diacetylpyridine dihydrazone

The nucleophilic addition reactions between 1,1′-di(2-propanone)-2,2′-biimidazole or 2,6-diacetylpyridine and hydrazine hydrate afford 1,1′-di(2-propanone)-2,2′-biimidazole dihydrazone (1) and 2,6-diacetylpyridine dihydrazone (2), respectively. Compound1 crystallizes in the orthorhombic space groupP2₁2₁2₁, witha=9.042(2),b=9.731(3),c=15.683(4)Å, V = 1379.9(6)Å^? andZ=4. Compound2 crystallizes in the orthorhombic space groupPnma, witha=10.948(2),b=19.742(6),c=4.566(1)Å, V=986.9(4)Å^? andZ=8. A pseudo center of inversion is present at the midpoint of the C?C bond joining the imidazole rings of1, whose substituents crystallize in atrans configuration. The imidazole rings are rotated 2.5(3)° about the C?C bond. In contrast to the essentially planar structure of2, the hydrazone substituent groups of1 are at angles of 89.9(1)° and 88.4(1)° with respect to the plane of the adjacent imidazole moiety.     

Synthesis and crystal structure of 1,1′-di(ethylpropionato)-2,2′-biimidazole, a macromolecular precursor

1,1,-Di(ethylpropionato)-2,2-biimidazole, C₁₆H₂₂N₄O₄, crystallizes from ice-cold ethanol in the space group P , with a = 4.6742(9), b = 9.1119(13), c = 10.175(2) Å, = 96.22(1), = 96.29(2), = 97.53(1)°, and Z = 1. The molecule crystallizes with coplanar rings and the substituents assume a trans conformation with a center of inversion between the bridging carbon atoms.     

Influence of Changes in Central Core on the Mesomorphic Properties of 4,4′-Dialkoxy-2,2′-Dihydroxybenzalazine and Derivatives

Two new series of compounds that have mesomorphic properties were synthesized: the 4,4′-dialkoxy-2,2′-dihydroxy-a-methylbenzalazines and the 4,4′-dialkoxy-2,2′-dihy-droxybenzalazines. The first series shows crystalline and smectic polymorphism.

A comparative study of the mesomorphic properties of these series with those of the 4,4′-dialkoxy-2,2′-dihydroxy-α,α'-dimethylbenzalazines was carried out to establish the influence of the central groups on the mesomorphic properties.     

Synthesis and Characterization of 5′-Hexyl-2,2′-bithiophene Based on Organic Dyes for Dye-Sensitized Solar Cell Applications

A series of new organic dyes, 2-(2,6-bis((E)-2-(5′-hexyl-2,2′-bithiophen-5-yl)vinyl)-pyran-4-ylidene)-2-cyanoacetic acid (OD-1) and 2,2′-(2-((E)-2-(5′-hexyl-2,2′-bithiophen-5-yl)vinyl)-1H-indene-1,3(2H)-diylidene)bis(2-cyanoacetic acid) (OD-2), were synthesized as a sensitizers for the application of dye-sensitized solar cells (DSSCs). The introduction of the 5′-hexyl-2,2′-bithiophene units as an electron donor group and 2,6-dimethyl-pyran-4-one or 1,3-indandione as a π-spacers units increased the conjugation length of the sensitizers and thus improved their molar absorption coefficient and light harvesting efficiency.     

Synthesis and Characterization of Two Pb(II) Complexes of 2,2′-dihydroxy,Dimethoxy-1,1′-binaphthyl-3,3′-dicarboxylic Acid

Two new complexes {[Pb(L¹)(DMSO)₂(H₂O)]·DMF}_n (1, L¹ = 2,2′-dihydroxy-l,l′-dinaphthyl-3,3′-dicarboxylate) and {[Pb(L²)(DMS O)·DMSO}_n (2, L² = 2,2′-dimethoxy-l,l′-dinaphthyl-3,3′-dicarboxylate) have been synthesized under mild conditions and structurally characterized. Crystal structural analysis reveals that complex 1 adopts a 1D infinite chain structure which forms 2D sheet by hydrogen bonds interactions. Complex 2 possesses a 2D sheet structure, which was further assembled into a 3D supramolecular network through the π-π weak interactions. IR spectra indicates the carboxyl group coordinates with the Pb²⁺ ion. TGA shows that complex 2 is highly thermally stable up to 120°C.     

Synthesis and Crystal Structure of Nickel(II) Complex with 2,2′-Biimidazole and 4-Aminobenzoic Acid

Abstract  The Ni(II) complex, [Ni(H₂biim)₂(PABA)₂]Cl₂·2H₂O, H₂biim being 2,2′-biimidazole, PABA being 4-aminobenzoic acid has been synthesized and the crystal structure determined using X-ray crystallography. The complex crystallizes in triclinic system, space group P − 1 with unit cell parameters a = 8.3920(9) ?, b = 9.8436(11) ?, c = 9.8874(11) ?, α = 94.862(2)°, β = 109.142(2)°, γ = 90.992(2)°, V = 767.95(15) ?³ and Z = 1. The molecules of the complex in the crystal assemble by way of N–H⋯Cl, O–H⋯Cl, O–H⋯O hydrogen bonds as well as π–π stacking interactions to provide a two-dimensional supramolecular structure. Index Abstract  Synthesis and Crystal Structure of Nickel(II) Complex with 2,2′-Biimidazole and 4-Aminobenzoic Acid Yanping Li and Pin Yang* The molecules of the title complex [Ni(H₂biim)₂(PABA)₂]Cl₂·2H₂O in the crystal assemble by way of N–H⋯Cl, O–H⋯Cl, O–H⋯O hydrogen bonds as well as π–π stacking interactions to provide a two-dimensional supramolecular structure.      

Hydrogen-Bond Character of 2,2′-Bi-1H-Imidazole Systems

Abstract

The characters of hydrogen-bond of 2,2′-bi-1H-imidazole (H2BIM) system were examined from a viewpoint of the proton-transfer (PT) and electron-transfer (CT) interactions. To make the effects of the dibenzo substitution of H2BIM molecule clear, we prepared the charge-transfer complexes of dibenzo-2,2′-bi-1H-imidazole (H2BBIM) and H2BIM systems with 7,7,8,8- tetracyanoquinodimethane(TCNQ). The one-dimensional column of TCNQ was confirmed by the crystal structural analysis, however, the packing forms of the H2BIM and H2BBIM systems were entirely different to each other. The H2BBIM system in the TCNQ complex formed the one-dimensional column which is parallel to the TCNQ stack, while the H2BIM system was constructed by the hydrogen-bonded dimer unit along the perpendicular direction to the TCNQ column.     

Structure of 2,2′-anhydro-3′-O-acetyl-2′thio-1-β-D-arabinofuranosylcytosine hydrochloride1

2,2-Anhydro-3-O-acetyl-2-thio-1--D-arabinofuranosylcytosine hydrochloride crystallizes in space group P2₁2₁2₁ witha=10.373(1),b=14.517(2),c=9.496(1) Å. Reflections were measured on a diffractometer and the structure was solved by direct methods. Least-squares refinement converged atR=0.056 andR _w =0.063. The study of this crystal structure showed that the alterations in the geometry of 2,2-anhydro-1--D-arabinofuranosylcytosine when the bridge oxygen is replaced by sulfur are localized in the region of the fused ring. The angle at the bridge atom decreases to nearly 90°, with concomitant enlargements of about 5°–7° in the angles opposite to the bridge atom. Angle C(1)-N(1)-C(6) decreases by 4°. Also, the amount of double bond character in the bond formed by C(2) and the bridge atom decreases. A survey of the conformational features of S,2-cyclonucleosides and comparison with O,2-cyclonucleosidcs showed that their preferred conformations are the same. However, S,2-cyclonucleosides exhibit a wider range of P and values. This correlates with a greater ease of the sulfur containing five-membered ring to pucker as compared to the oxygen-cyclo ring.This paper is part of the authors' dissertation (Vitali, 1986).     

Structure of 2,2′-bis(4-cyanatophenyl)isopropylidene

The title compound is monoclinic:a=13.345(3),b=11.393(2),c=10.046(5)Å,=108.48(2)°,Z=4,P2₁/c. The structure was determined by direct methods, using MoK diffractometer data, and refined by full-matrix least squares toR=0.045 for 1463 reflections. The structure shows a central tetrahedral carbon atom surrounded by two methyl and two phenylcyanate groups. The geometry of the cyanate group compares well with that in 4-chloro-3,5-dimethyl-phenyl cyanate, the only example of an organic cyanate in the Cambridge Crystallographic database (V.3). The intermolecular nitrile, C-N, distances were examined for evidence of a possible dimerization interaction; no significant distances were found.