Synthesis and Crystal Structure of 5,7,12,13b,13c,14-Hexahydro-1,4,-dibromo-8,11-dimethoxy-13b,13c-bis(ethoxycarbonyl)-6H,13H-5a,6a,12a,13a-tetra azbenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-6,13-dione

The title compound has been synthesized by the reaction of 4 with 1,4-dimethoxybenzene. The yielded product 5 was investigated with X-ray crystallographic, NMR, EI-MS, and IR techniques. The crystal belongs to a monoclinic system, space group P2₁/c with unit cell parameters a = 12.7790(17) Å, b = 21.565(3) Å, c = 12.2544(16) Å, α = 90°, β = 107.014(2)°, γ = 90°, V = 3229.3(7) Å³, Z = 4, D_c = 1.661, M_r = 807.32, μ = 2.732 mm^?1, F(000) = 1632, R₁ = 0.0540 and wR₂ = 0.0989.     

The Simultaneous Presence of Different Varieties of Intermolecular Hydrogen Bonds in a New Layer-Type Anionic Host Lattice Built of Thiourea,Fumaric Acid and Fumarate Anion

A new inclusion complex (n-C₄H₉)₄N⁺C₄H₃O ₄ ^?  · C₄H₄O₄ · (NH₂)₂CS has been prepared and characterized by X-ray crystallography. Crystal data: space group P \( \overline 1 \), a = 8.799(2) Å, b = 9.590(1) Å, c = 18.684(4) Å, α = 89.63(1)°, β = 79.56(1)°, γ = 79.74(1)°, V = 1525.2(5) ų, Z = 2, R ₁ = 0.0562 and wR = 0.1033. In the title compound, thiourea molecules, fumaric acid and fumarate anions are joined together by typical O–H···O, N–H···O and N–H···S, plus weak C–H···O and C–H···S, hydrogen bonds to generate a hydrogen-bonded layer corresponding to the (100) family of planes. The tetra-n-butylammonium cations are orderly arranged in a sandwich-like packing mode between the stacked layers. The simultaneous presence of different varieties of intermolecular hydrogen bonds is an interesting feature of the title compound.     

Synthesis and Crystal Structure of Tert-butyl 2-((phenylthio)-carbonyl)pyrrolidine-1-carboxylate

Tert-butyl 2-((phenylthio)carbonyl)pyrrolidine-1-carboxylate, was synthesized by using iso-butoxycarbonyl chloride (i-BuOCOCl) via mixed anhydride method. The obtained product was characterized spectroscopically and finally confirmed by X-ray diffraction studies. The title compound C₁₆ H₂₁ N O₃ S crystallizes in the triclinic space group P1 with the cell parameters a = 6.0250(7) Å, b = 8.2820(13) Å, c = 8.7700(14) Å, α = 102.352(4)°, β = 102.993(11)°, γ = 90.279(8)°, V = 415.89(10) Å³ and Z = 1. The proline ring in the structure is in a envelope conformation. The structure exhibits intermolecular hydrogen bonds of the type C–H...O.     

X-Ray Crystal Structure of <Emphasis Type="Italic">trans</Emphasis>-PdCl<Subscript>2</Subscript>(PPh<Subscript>2</Subscript>C<Subscript>12</Subscript>H<Subscript>7</Subscript>S<Subscript>3</Subscript>)<Subscript>2</Subscript>, a New Morphology

Herein we report the crystal structure of trans-PdCl₂(PPh₂C₁₂H₇S₃)₂, 1, in a different morphology than has previously been reported [Stott et al. (Dalton Trans (4):652–653, 2005]. This structure crystallizes in a P-1 space group with a = 9.4249(19) Å, b = 11.540(2) Å, c = 12.559(3) Å, α = 79.07(3)°, β = 78.04(3)°, γ = 69.44(3)°, Z = 1. The earlier structure possessed a P2₁/n space group. Additionally the terthienyl moieties of 1 demonstrate the anti orientation exclusively while the P2₁/n space group structure has some syn and even syn/anti mixed geometries included.     

Crystal Structures of Diphosphinated Chromium Fischer Amino Carbenes

The crystal structures of four new diphosphinated chromium Fischer amino carbenes with the compositions fac-[(P-P)(CO)₃Cr=C(NR₂′)(R)] (R = Me, NR₂′ = pyrrolidino, P-P = dppe, 1; R = Me, NR₂′ = pyrrolidino, P-P = dppp, 2; R = Me, R′ = Me, P-P = dppe, 3; R = Me, R′ = Me, P-P = dppp, 4) have been determined at 243 K. Compound 1 crystallizes in the monoclinic system, space group P2₁ /n with a = 12.1597(11) Å, b = 20.1556(17) Å, c = 14.0557(12) Å, β = 114.163(3)°, V = 3143.0(5) Å³, and Z = 4. Compound 2 crystallizes in the triclinic system, space group P ? 1 with a = 7.4424(3) Å, b = 10.8830(5) Å, c = 20.6040(9) Å, α = 100.9880(10)°, β = 91.7650(10)°, γ = 97.6610(10)°, V = 1620.90(12) Å³, and Z = 2. Compound 3 crystallizes in the monoclinic system as a mono-solvate of d⁵-pyridine, space group P2₁ /c with a = 11.485(2) Å, b = 22.825(5) Å, c = 14.092(3) Å, β = 108.53(3)°, V = 3502.7(12) Å³, and Z = 4. Compound 4 crystallizes in the orthorhombic system, space group P2 ₁ 2 ₁ 2 ₁ with a = 8.359(3) Å, b = 15.364(6) Å, c = 23.784(9) Å, V = 3055(2) Å³, and Z = 4. Steric repulsions with the diphosphine ligand favor a conformation with the amino moiety directed away from the diphosphine backbone in 1–4.     

Hydrogen Bonding Network Assembled with 2-Amino-3-hydroxypyridium and Isonicotinate-N-oxide

The crystal structure of the compound (C₅H₇N₂O)·(C₆H₄NO₃)·H₂O (1) consisting of 2-amino-3-hydroxypyridium, isoniconate-N-oxide and lattice water was characterized by single-crystal X-ray diffraction analysis: monoclinic, P2₁/c, a = 9.6905(8), b = 6.0040(4), c = 21.039(2) Å, β = 101.062(8)°, V = 1201.34(18) Å³, Z = 4. In 1, the deprotonated isoniconate-N-oxide, the protonated 2-amino-3-hydroxypyridium and the lattice water are linked by a series of classical hydrogen bonds to form 2-D layer. Then, these 2-D sheets assemble to a 3-D network via weak hydrogen bonds.     

Synthesis,Crystal Structure and Spectral Properties of [Fe<Subscript>3</Subscript>(2,2′-bipy)<Subscript>6</Subscript>(ox)<Subscript>3</Subscript>]·12.25H<Subscript>2</Subscript>O Complex

A novel iron (II) complex of formula [Fe₃(2,2′-bipy)₆(ox)₃]·12.25H₂O (2,2′-bipy = 2,2′-bipyridine, ox = oxalate) has been prepared and structurally characterized by X-ray crystallography. In the complex, the metal atoms are six-coordinated in distorted octahedral environment. In the complex [Fe(ox)₃]^4? anions and water molecules are linked together into 1D chain structure by hydrogen interaction. The red crystal of the complex is monoclinic, space group P2₁/c, with a = 22.932(6) Å, b = 13.715(4) Å, c = 22.493(6) Å, β = 93.177(5)°, and V = 7063(3) Å³ with Z = 4.     

Synthesis and structural characterization of 2,5-dihalo-3,4-dinitrothiophenes

Using new nitration protocols, we have been able to efficiently dinitrate 2,5-dihalothiophenes with yields of ～80–95%. The resulting products 2,5-dibromo-3,4-dinitrothiophene (1), 2,5-dichloro-3,4-dinitrothiophene (2), 2-bromo-5-chloro-3,4-dinitrothiophene (3), as well as the analogous 2-bromo-3,4-dinitrothiophene (4), all crystallize easily allowing their characterization via X-ray crystallography. Crystallization of 1 occurs in the monoclinic space group C2/c with a = 14.547(3) Å, b = 7.3534(15) Å, c = 10.775(2) Å, β = 128.89(3)°, and Z = 4. Crystallization of 2 occurs in the tetragonal space group I-42d with a = 9.9398(14) Å, b = 9.9398(14) Å, c = 16.866(3) Å, and Z = 8. Crystallization of 3 occurs as a pseudo-merohedral twin in the triclinic space group P-1 with a = 7.340(5) Å, b = 8.094(5) Å, c = 9.112(5) Å, α = 82.059(5)°, β = 66.232(5)°, γ = 63.021(5)°, and Z = 2. Crystallization of 4 occurs in the triclinic space group P-1 with a = 7.1787(14) Å, b = 7.4092(15) Å, c = 8.3151(17) Å, α = 101.67(3)°, β = 96.00(3)°, γ = 116.13(3)°, and Z = 2. The structures of all compounds exhibit the formation of interesting solid-state assemblies due to halogen-bonding interactions between the halogen and nitro groups.     

Synthesis and Characterization of the Osmium Compound <Emphasis Type="Italic">cis</Emphasis>(CO)<Emphasis Type="Italic">–</Emphasis>ClOs(CO)<Subscript>2</Subscript>(bpcd)[C(O)Et]

Photochemical activation of the triosmium cluster Os₃(CO)₁₂ in CH₂Cl₂ solvent and ethylene, followed by treatment with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd), furnishes the new octahedral compound cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] in low yield. The title compound has been isolated and characterized in solution by IR and ¹H NMR spectroscopies, with the solid-state structure of cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] determined by X-ray diffraction analysis. cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] crystallizes in the triclinic space group P-1, a = 10.043(2), b = 11.455(2), c = 16.221(3) Å, α = 74.900(3)°, β = 76.150(3)°, γ = 76.221(2)°, V = 1718.2(5) ų, Z = 2, D _cacl = 1.717 Mg/m³; R = 0.0453, R _w = 0.0778 for 6703 observed reflections with I > 2σ(I). The presence of the chlorine and propanioyl groups in cis(CO)–ClOs(CO)₂(bpcd)[C(O)Et] is structurally confirmed, and the origin of the these groups from the reaction solvent and ethylene is discussed.     

Two-dimensional Supramolecular Architecture of Oxamido-bridged Binuclear Copper(II) Complex Cu<Subscript>2</Subscript>(oxen)(NCS)<Subscript>2</Subscript>(DMF)<Subscript>2</Subscript>

An oxamido-bridged binuclear copper(II) complex, Cu₂(oxen)(NCS)₂(DMF)₂ (1) (H₂oxen = N,N′-bis(2-aminoethyl)oxamide, DMF = dimethylformamide), has been synthesized by the reaction of Cu(oxen) · 2H₂O with CuCl₂ · 2H₂O and KSCN in DMF/CH₃OH solution, and characterized by elementary analysis, FT-IR spectra and X-ray single-crystal diffraction. Structural analysis reveals that complex 1 forms a centrosymmetric binuclear molecule in which an oxamido group in the trans conformation bridges two crystallographically equivalent five-coordinate copper(II) ions with Cu–Cu distance of 5.279(2) Å. The complex molecules are assembled into a novel 2D layer through weak Cu?S interactions (d _Cu–S = 3.341(4) Å) and intermolecular hydrogen bonds. Viewed along the crystallographic b axis, layers display an interesting hydrophobic–hydrophilic–hydrophobic sandwich arrangement, with the hydrophobic layers dominated by dipole interaction of DMF molecules.     

Synthesis and Crystal Structure Studies of a Novel Bioactive Heterocycle: 1-Benzhydryl-4-phenylmethane Sulfonyl Piperazine

1-Benzhydryl-4-phenylmethane sulfonyl piperazine was synthesized from 1-benzhydryl piperazine with phenylmethane sulfonyl chloride. The product obtained was characterized by ¹H NMR, MS and IR techniques and finally confirmed by X-ray crystallography. The title compound C₂₄H₂₆N₂O₂S, M _r   =   406.53, crystallizes in the orthorhombic crystal class in the space group Pbca with unit cell parameters a  =  11.1240(10)Å, b  =   9.4940(15)Å, c  =  40.239(4)Å, Z  =  8 and V = 4249.7(9)ų. The structure was solved by direct methods and refined to R ₁=0.0561 for 2,445 reflections with [I > 2 σ(I)]. The piperazine ring adopts a chair conformation. The sulfonyl moiety is in a distorted tetrahedral configuration.     

Synthesis,Spectroscopic and Crystal Structure Analysis of <Emphasis Type="Italic">N</Emphasis>-[imidazolidin-2-ylidene]-5-(thien-2-yl)[1,3,4]thiadiazole-2-amine

The crystal structure of the title compound has been determined. The compound crystallizes in the monoclinic space group P2₁/c with a = 5.9885(2) Å, b = 14.7345(4) Å, c = 12.3719(4) Å, β = 96.655(5)°, V = 1084.31(8) Å³, z = 4. An intramolecular N–H···N hydrogen bond forms a pseudo-six-membered ring with graph set S ¹ ₁(6). The crystal structure is stabilized by intermolecular interactions of the type N–H···N and C–H···N. The packing motifs in accordance with Etter’s analysis are R ² ₂(8) corresponding to N–H···N dimer and that generated by the chain is C(7).     

Stereoselective Synthesis and X-Ray Structure Determination of Labeled [1, 2, 3-<Superscript>13</Superscript>C<Subscript>3</Subscript>]-1-(Phenylsulfinyl)-3-Benzyloxyacetone

[1,2,3-¹³C₃]-1-(Phenylsulfinyl)-3-benzyloxyacetone, C₁₆H₁₆O₃S, (3) has been synthesized and its crystal structure has been determined by a single-crystal X-ray diffraction analysis. The X-ray diffraction study revealed that compound 3 crystallizes in the monoclinic crystal system in the acentric space group Pc, with cell constants at T = 100 K: a = 16.073(5), b = 5.5079(16), c = 7.949(2) Å, β = 100.221(4)^°, V = 692.6(3) ų, Z = 2, d _calc = 1.383 g/cm³. Compound 3 contains the chiral tetravalent three-coordinated sulfur atom, which has a distorted tetrahedral configuration with a lone electron pair occupying one of the tetrahedron vertices. In the crystal, the molecules are packed in stacks along the b axis; the stacks consist of the molecules of the same chirality. Furthermore, the stacks of the molecules of the opposite chirality alternate along the c axis. The molecules in neighboring stacks are arranged by head-to-tail orientations. There are no short intermolecular contacts in the crystal of 3.     

Solvent-induced Polymorphism of 2-[(2-Amino-phenylimino)-phenyl-methyl]-phenol

The title compound C₁₉H₁₆N₂O crystallize as either triclinic or monoclinic polymorph depending on the solvent used. Polymorph [1] crystallizes from methanol in the space group P \( \mathop 1\limits^ - \) with unit cell dimensions: a = 8.723(2), b = 9.344(2), c = 10.544(2) Å, α = 71.54(2), ß = 78.74(2), γ = 74.15(2)°, and Z = 2. Polymorph [2] crystallizes from benzene with space group P2₁/n with unit cell dimensions: a = 10.230(3), b = 20.536(7), c = 14.563(4) Å, ß = 97.14(3)°, and Z = 8. The only similarity between molecules of [1] and two independent molecules of [2] can be found in almost co-planar phenyl moiety with chelate ring. Both structures are characterized with strong intramolecular O-H···N hydrogen bond. Whereas the molecular interconnections in [2] are based on van der Waals attractions between discrete molecules, molecules of [1] associate in dimers via intermolecular N-H···O hydrogen bonding by the operation of crystallographic centre of inversion.     

C–H...O,C–H...π and π–π stacking interactions in 3-(2,4-dimethylphenyloxymethyl)-3,4-dihydroisocoumarin

3-(2,4-Dimethylphenyloxymethyl)-3,4-dihydroisocoumarin (C₁₈H₁₈O₃) was prepared by the alkylation of o-lithio N-methyl benzamide with 2-(2,4-dimethylphenoxy)methyl oxirane, followed by alkaline hydrolysis. The compound crystallizes in the orthorhombic space group Pbca with unit cell parameters : a = 8.239(2) Å, b = 14.918(5) Å, c = 24.831(9) Å, Z = 8. The crystal structure was solved by direct methods and refined to R = 0.0514 for 1564 observed reflections. The heterocyclic ring adopts a distorted half-chair conformation. Molecules are connected by π–π interactions between phenyl rings of the isocoumarin nucleus forming dimers. Dimers are connected via C–H...O hydrogen bonds forming chains. Further intermolecular C–H...π hydrogen bonds link the dimer chains to form supramolecular structure.     

Tyrphostin Tumor Growth Inhibitors of EGFR and ErbB2 Tyrosine Kinase

Tyrosine kinase inhibitors are small molecules that bind to the ATP binding site of the tyrosine kinase domain of the epidermal growth factor receptor (EGFR) and disrupt the uncontrolled signaling reactions in cancer cells by inhibiting tyrosine phosphorylation. Tyrphostins (or malononitriles) are one class of compounds known to function as tyrosine kinase inhibitors. Our focus is to determine the structural features of these molecules that make them candidates for tyrosine kinase inhibitors. In this study, the X-ray crystal structures of four compounds shown to have EGFR tyrosine kinase inhibition have been determined. They are 4-methoxybenzylidenemalononitrile, (3,4,5-trihydroxybenzylidene) malononitrile, α-cyano-(3,5-di-t-butyl-4-hydroxy)thiocinnamide, and N-(3′,4′-dihydroxybenzylidenecyanoacetyl)indoline. Crystallographic data: 4-methoxybenzylidenemalononitrile, P2₁/c, a = 3.9173(6) Å, b = 24.909(3) Å, c = 9.6487(9) Å, β = 91.10(1)°, V = 941.3(2) ų; (3,4,5-trihydroxybenzylidene) malononitrile, P2₁/c, a = 7.0065(5) Å, b = 10.7158(9) Å, c = 13.4191(10) Å, β = 102.986(6)°, V = 981.7(1) ų; α-cyano-(3,5-di-t-butyl-4-hydroxy)thiocinnamide, P1bar, a = 9.6640(19) Å, b = 9.7204(13) Å, c = 10.3305(18) Å, α = 88.93(1)°, β = 83.88(2)°, γ = 66.12(1)°, V = 882.0(3) ų; N-(3′,4′-dihydroxybenzylidenecyanoacetyl)indoline, P1bar, a = 7.8887(7) Å, b = 8.220(1) Å, c = 12.967(2) Å, α = 94.42(1)°, β = 99.45(9)°, γ = 118.37(8)°, V = 718.0(2) Å³.     

Crystallization,crystal-structure refinement,and IR spectroscopy of a synthetic hexahydroborite analog

The crystal structure of the hexahydroborite analog Ca[B(OH)₄]₂ · 2H₂O (a = 7.9941(3) Å, b = 6.6321(2) Å, c = 7.9871(3) Å, β = 104.166(4)°, V = 410.58(3) ų, sp. gr. P2/c, Z = 2, ρ_calc = 1.891 g/cm³; Xcalibur S CCD automated diffractometer, 1196 reflections with I > 2σ(I), λMoK _α), which was synthesized by the hydrothermal method via the recrystallization of calciborite CaB₂O₄ (M) in the M ? B₂O₃ ? H₂O system (t = 250°C and P = 70–80 atm), was refined by the least-squares method with anisotropic displacement parameters (H atoms were located; R ₁ = 0.0260). The structure of synthetic hexahydroborite consists of infinite columns running along the c axis. The columns are formed by Ca polyhedra linked together and to [B(OH)₄] orthotetrahedra by sharing edges. Along the two other axes, the translationally equivalent columns are linked only by hydrogen bonds. The presence of a stronger bond between the discrete (Ca-B-O) columns along the shortest (b = 6.6 Å) axis accounts for the possibility of the shift of the columns by 1/2T _b and the formation of the second modification of Ca[B(OH)₄]₂ · 2H₂O. The crystals of synthetic hexahydroborite were studied by IR spectroscopy. A crystal-chemical analysis was performed for a series of natural metaborates with the general formula CaB₂O₄ · nH₂O (CaO: B₂O₃ = 1: 1, n = 0–6), including calciborite CaB₂O₄ and hexahydroborite CaB₂O₄ · 6H₂O as the end members.     

Synthesis and Crystal Structure of μ-oxo-bis[(octaethyloxoporphinato)iron(III)] Tetrafluoroborate

Exposure of dichloromethane solution of [OEOPFe(BF₄)], where OEOP is the monoanion of octaethyloxoporphyrin, to dioxygen results in its transformation into the μ-oxo bridged compound, [(OEOPFe)₂O)](BF₄)₂. The molecular structure of the title compound, [(OEOPFe)₂O](BF₄)₂, was determined by single-crystal X-ray diffraction. It contains a binuclear centrosymmetric [(OEOPFe)₂O]²⁺ cation (the bridging O atom lies on an inversion centre) and two tetrafluoroborate anions. The Fe atom is five-coordinate to four N atoms of the porphyrin ring and to one bridging O atom. The compound is characterized by an average Fe–N bond length of 2.064 Å. The Fe–O bond distance is 1.7665(11) Å and the Fe–O–Fe bond angle is 180.0° and the two porphyrin rings are parallel. Crystal data: crystal system, monoclinic, a = 8.867(3), b = 26.104(9), c = 15.748(6) Å, β = 105.40(3)°, space group, P2₁/c, V = 3514(2) Å³, Z = 2.     

Crystal structure of the molecular complex of 3-[1-(4-nitrophenyl)-3-oxobutyl]-4-hydroxychromen-2-one with ethanol

The crystal structure of 2,3H-2-methyl-4-(4-nitrophenyl)-5-oxobenzopyrano[3,4-e]dihydropyran-2-ol is investigated using X-ray diffraction. The unit cell contains an ethanol molecule that forms hydrogen bonds with O-H and C-O groups of two molecules of the main compound and acts as a proton donor and a proton acceptor in these hydrogen bonds. Owing to these interactions, infinite chains are formed in the crystal. The crystallographic data for the structure of C₁₉H₁₅NO₆·C₂H₅OH (M = 399.39) are as follows: the crystals are triclinic, space group P1, a = 5.5340(3) Å, b = 8.0109(4) Å, c = 11.0112(5) Å, α = 88.773(2)°, β = 84.788(2)°, γ = 79.958(2)°, and Z = 1.     

Synthesis and Structure Determination of 1, 4, 7, 11, 14, 17, 21, 24, 27-Nonaoxatriacontan-8, 10, 18, 20, 28, 30-Esaone

The title compound crystallizes in the trigonal space group R-3, with unit-cell parameters: a = 23.261(4), c = 9.537(2) Å; λ(MoKα) = 0.71073 Å, V = 4469(2) Å³, and Z = 6. The structure has been solved by direct methods using X-ray diffraction techniques. The final reliability index for the computed structure is 0.0826 for 929 observed reflections and 121 refined parameters. Crown ether adopts an almost circular shape and macrocycles are piled up in a columnar arrangement forming tubular nanochannels. The channels are filled with guest CDCl₃ molecules, characterised by rotational disorder.