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 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.     

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 and molecular structures of three 2,2′-thio- and 2,2′-sulfonyl-bis(1,3-diarylprop-2-en-1-ones)

The X-ray crystal structures of 2,2-thio- and 2,2-sulfonylbis(1,3-diarylprop-2-en-1-ones) are determined [1: 2,2-thiobis(3-(p-chlorophenyl)-1-phenylprop-2-en-1-one), C₃₀H₂₀Cl₂O₂S, space group C2/c, a = 14.275(3), b = 6.280(1), c = 26.533(5) Å, = 94.55(3)°, Z = 1/2; 2: 2,2-sulfonylbis(1,3-diphenylprop-2-en-1-one), C₃₀H₂₂O₄S, space group P , a = 9.652(1), b = 12.044(1), c = 12.182(1) Å, = 61.985(6), = 77.511(5), = 74.340(6)°, Z = 1; 3: 2,2-sulfonylbis(3-(p-chlorophenyl)-1-phenylprop-2-en-1-one), C₃₀H₂₀Cl₂O₄S, space group P , a = 8.294(1), b = 13.175(2), c = 13.470(1) Å, = 62.870(9), = 83.796(7), = 85.282(8)°, Z = 1]. The C=C double bonds are all clearly defined. The sulfide 1 crystallizes on a crystallographic twofold axis, leading to a symmetric molecular conformation. The sulfones 2 and 3 crystallize on general positions, with different and irregular conformations.     

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.     

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.     

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.      

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.     

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.     

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.

     

Crystal structures of two thienyl analogs of benzil – 1,2-dithien-2-ylethanedione (2,2′-thenil) and 1,2-dithien-3-ylethanedione (3,3′-thenil)

2,2-Thenil crystallizes in P2₁/c with a = 7.2501(12) Å, b = 4.7846(8) Å, c = 13.9867(23) Å, = 96.897(3), V = 481.67(14) ų, and Z = 2. The molecule resides on an inversion center and is planar. 3,3-Thenil also crystallizes in P2₁/c with a = 3.9904(8) Å, b = 21.310(4) Å, c = 11.618(2) Å, = 101.83(3), V = 966.9(3) ų, and Z = 4. Refinement of 3,3-thenil data indicated that 10.3(2)% of both thienyl rings are flip-disordered in this nonplanar molecule. A brief discussion of disorder in molecules containing terminal, unsubstituted 2- and 3-thienyl rings is presented.     

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.     

Complexes of 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (4,13-diaza-18-crown-6) with 2,5-pyridinedicarboxylic and 2,2′-dithiosalicylic acids

A 1:2:2 complex of 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane with 2,5-pyridinedicarboxylic acid and water (1) and its 1:1:1.75 complex with 2,2-dithiosalicylic acid and water (2) have been obtained and characterized by x-ray diffraction. C₂₆H₄₀N₄O₁₄ (1), triclinic, , a = 9.574(1) Å, b = 9.632(1) Å, c = 9.723(1) Å, = 112.70(1)°, = 91.07(1)°, = 115.45(1)°, V = 728.35(13) ų, Z = 1. C₂₆H_39.5N₂O_9.75S₂ (2), M = 600.22, triclinic, , a = 10.492(1) Å, b = 10.945(1) Å, c = 14.535(2) Å, = 102.74(1)°, = 109.08(1)°, = 90.68(1)°, V = 1532.2(3) ų, Z = 2. In complex 1, both N-atoms of the macrocyclic ring are protonated. The following types of H-bonding have been found: (1) between protonated aza groups of the macrocycle and ionized carboxylic groups; (2) between the protonated aza groups and N-atoms of the pyridine nuclei (D–A distance slightly exceeds 3 Å); (3) between water molecules and C=O groups of the non-ionized carboxylic groups; and (4) between the nonionized and ionized groups of the carboxylic acid. The above interactions give rise to the formation of a developed supramolecular network in the crystals of 1. In complex 2, despite the presence of several types of hydrogen bonds involving the aza crown, 2,2-dithiosalicylic acid and water, the aromatic anions are H-bound only to the two other components, and not to each other. The H-bonds found in complex 2 are between (1) one of the protonated aza groups and water, (2) protonated aza groups and O-atoms of the ionized carboxylic groups, (3) water molecule and carboxylic O-atom, (4) water molecule and sulfur atom, and (5) water molecule and O-atom of diaza-18-crown-6.     

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.      

Structure and molecular chirality of the 2∶1 salt of quinine with biphenyl 2,2′-dicarboxylic acid (diphenic acid)

The molecule of the salt consists of two quinine cations and a biphenyl 2,2-dicarboxylic dianion. Both of the quinine cations are protonated at the nitrogen atoms of the quinuclidine fragments. Each carboxylic group of the diphenic dianion acts as a proton donor with respect to the quinuclidine N(1) atom of one of the quinine cations, and as a proton acceptor with respect to the carbinol O(12)-H(12) group of the other. Thus, the interlocking hydrogen-bond system forms a rigid structure. The molecular conformation around the C(8)-C(9) bond is synclinal. The conformational parameters of the diphenic dianion are considerably different from those of diphenic acid in solid state. The absolute configuration of the biphenyl 2,2-dicarboxylic dianion (S) is defined by the positive torsion angle around the line which connects the centers of both phenyl rings. The molecular chirality of the salt arises from the coupling between the quinoline and the biphenyl chromophores, as well as from the coupling of the quinoline-quinoline long-axis polarized-band transition moments.     

Structure and molecular chirality of the acetonitrile adduct of the 2:1 salt of quinidine with biphenyl 5,5′-dinitro-2,2′-dicarboxylic acid (5,5′-dinitrodiphenic acid)

The molecule of the 21 salt consists of two quinidine cations and the 5,5-dinitrodiphenic anion. Both of the quinidine cations are protonated at the nitrogen atoms of the quinuclidine fragments. Owing to the interlocking hydrogen bonds between quinidine and the dinitrodiphenic ions, a rigid structure of the salt molecule has been formed. The alkaloid molecular conformation around the C(8)-C(9) bond is open. The conformational parameters of 5,5-dinitrodiphenic anion are considerably changed in comparison with the conformation of diphenic acid in the solid state. The absolute configuration of biphenyl 5,5-dinitro-2,2-dicarboxylic anion (R) is defined by the negative torsion angles around the line which connects the centers of both phenyl rings, and is the reverse of that observed in the diphenic acid-quinine salt. The present data confirm the observation that the chirality of the salt is controlled by the chirality of theCinchona alkaloid molecule.     

Crystal and Molecular Structure of 6,6′-Dimethoxy-gossypol:Acetic acid (1:1)

Abstract By crystallization from dilute solutions of acetic acid (2–4%) in diethyl ether, acetone, or methyl ethyl ketone, 6,6′-dimethoxy-gossypol forms a solvate with acetic acid in a one-to-one molar ratio. The compound crystallizes in the triclinic P space group and has unit cell dimensions of a = 7.5793(10) ?, b = 14.7211(19) ? and c = 14.740(2) ?, α = 106.260(3)°, β = 102.310(3)°, γ = 95.975(3)°, Z = 2. The structure was solved by direct methods and refined to an R1 value of 0.0394 on 4252 observed reflections. Enantiomeric pairs of dimethoxy-gossypol molecules form centrosymmetic dimers that are characterized by a pair of intermolecular hydrogen bonds and by hydrophobic stacking between pairs of naphthalene rings. The acetic acid molecule accepts a hydrogen bond from a gossypol hydroxyl group and donates to a hydrogen bond with one of the aldehyde groups of an adjacent gossypol molecule. Although there is less hydrogen bonding in this structure than in the gossypol:acetic acid (1:1) structure, the molecular packing of the two compounds is similar. Graphical abstract Crystal and molecular structure of 6,6′-dimethoxy-gossypol:acetic acid (1:1) Michael K. Dowd and Edwin D. Stevens The molecular structure of the acetic acid solvate of 6,6′-dimethoxy-gossypol is presented.      

Crystal and molecular structure of aquabis(2,2′-bipyridine)nitratomanganese(II) nitrate monohydrate

A new monomeric manganese(II) nitrate complex with 2,2-bipyridine (bpy), [Mn(bpy)₂(NO₃)(H₂O)](NO₃)·H₂O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group witha=9.721(3),b=14.691(5),c=8.578(3) Å, =106.79(3), =96.05(3), =82.55(3)°,V=1159.9 ų andZ=2. The structure comprises discrete cation [Mn(bpy)₂(NO₃)(H₂O)]⁺ in which the metal atom is coordinated by a pair of bidentate bpy ligands [Mn–N=2.261(4)–2.299(4) Å], a unidentate nitrato [Mn–O=2.284(4) Å] and aqua [Mn–O=2.160(3) Å] ligands in a highly distorted octahedral arrangement.     

Crystal structures of 4,7-phenanthrolino-5,6:5′,6′-pyrazine tetrahydrate and 1,4,5,8,9,12-hexaazatriphenylene dihydrate

The crystal structures of 4,7-phenanthrolino-5,6:5,6-pyrazine tetrahydrate (I) and 1,4,5,8,9,12-hexaazatriphenylene dihydrate (II) have been determined from low temperature (173 K) x-ray single crystal diffraction data. I crystallizes in the triclinic system, space group P with a = 11.2687(6), b = 12.4766(6), c = 12.7068(7) Å, = 113.4740(10), = 91.605(2), = 114.587(2)°, V = 1449.33(13) ų, and Z = 4. II crystallizes in the orthorhombic system, space group Pca2₁ with a = 18.187(2), b = 9.2576(11), c = 6.9672(8) Å, V = 1173.0(2) ų, and Z = 4. In both structures the planar heterocyclic molecules stack with interplanar distances down to 3.3 Å, which is consistent with self--complexation. The crystal water molecules provide links between the columns of stacked molecules through hydrogen bonds. In each compound the N-C bond lengths fall into two distinct groups (mean values 1.330(3) vs 1.361(1) Å in I and 1.320(3) vs 1.357(5) Å in II), as do the C-C bonds of the central phenyl rings (1.411(4) vs 1.467(1) Å in I and 1.405(5) vs 1.458(4) Å in II).