X-ray structure of 6-phenyldiquino[3,2-b;5,6-b′] [1,4]thiazine

The title compound (C₂₄H₁₅N₃S) is monoclinic, with a = 10.816(1), b = 8.193(1), c = 10.892(1), = 104.20(1)° and space group P2₁. The molecule is folded with the central ring in a boat conformation. It can also be considered as folded around the C—C axis between the thiazine and pyridine rings. The butterfly folding angle between the two quinoline planes is 20.5(1)° and between the planes of the two halves of the thiazine ring is 30.6(1)°. The phenyl substituent is in an equatorial location with respect to the thiazine ring with the C—N···S angle of 163.0(2)°. The phenyl plane nearly bisects the pentacyclic ring system and is nearly perpendicular to the C(2), C(3), C(12), C(13) plane.     

Structure of two 1,3-dioxane derivatives from 4′, 5′-dimethylfurocoumarins: 4a, 11a-dihydro-4a, 11a-dimethyl-8H-pyrano[3′,2′∶5,6]benzofuro[3,2-e]-1, 3-dioxan-8-one and 7a,11a-dihydro-7a,11a-dimethyl-2H-pyrano[2′, 3′∶4,5]benzofuro[3,2-d] (1,3) dioxan-2-one

Treatment of dimethylated psoralen and angelicin in the 4, 5-position leads to the formation of 1,3-dioxane derivatives, resulting from the condensation of an 1,3-dioxane ring to the 4, 5-positions of the dihydrofurocoumarin moiety. The structures of these new compounds, 4a, 1 1a-dihydro-4a, 11a-dimethyl-8H-pyrano [3, 25,6]benzofuro[3,2-e]-1, 3-dioxan-8-one (C₁₅H₁₄O₅) (1) and 7a, 11a-dihydro-7a, 11a-dimethyl-2H-pyrano[2, 34, 5]benzofuro[3, 2-d](1, 3)dioxan-2-one (C₁₅H₁₄O₅) (2) have been assigned by¹H and¹³C NMR measurements, mass spectrometry results, and X-ray analysis. Compound (1): triclinic,P¯1,a=9.847(2),b=8.927(2),c=8.334(2) Å,=95.98(2),=108.81(3), =106.73(3)°; compound (2): triclinic,P¯1,a=7.296(4),b=7.481(2),c=11.812(4) Å,=91.67(2),=95.97(4), =94.20(3)°. The structures were solved by direct methods and refined by full-matrix least squares toR=0.050 (1) and 0.056 (2). In both compounds the coumarin rings can be regarded as coplanar, while the five-membered ring adopts an envelope conformation and the 1,3-dioxane ring a chair conformation.     

Crystal and Molecular Structure Studies of 1′-Benzyl-8-(4-fluorobenzyl)-8-azaspiro[bicyclo-[3.2.1]octane-3,4′-imidazolodine]-2′,5′-dione

Abstract  

The title compound, C₂₃H₂₃FN₃O₂ has been synthesized and the structure was investigated by X-ray diffraction studies. The compound crystallizes in the triclinic crystal class in the space group P[`1]P\overline{1} with cell parameters a = 9.345(2) ?, b = 10.940(3) ?, c = 11.986(4) ?, α = 72.349(6)°, β = 68.106(18)°, γ = 66.867(5)°, Z = 2 and V = 1027.8(5) ?³. The hydantoin ring adopts a planar conformation and is affected by the π conjugation. The pyrrolidine and piperidine rings in the bicyclo octane moiety adopt envelope and chair conformations respectively. The structure exhibits both inter and intramolecular hydrogen bonds of the type N–H···O, C–H···O and C–H···N. One of the oxygen atoms attached to the hydantoin ring simultaneously accepts two hydrogen bonds to form a three centered hydrogen bonding pattern.     

Crystal structure of 9,12-ethano-12a-methoxycarbonyl-5, 8a,9,12,12a,12b-hexahydro-6H-[1,2]dioxino[4′,5′:4,5] isoxazolo[3,2-a]isoquinoline, C17H19NO5

The title compound crystallizes in the space group P2₁/n, with a = 18.423(3), b = 9.628(3), c = 19.243(2) Å, = 116.208(8)°, with two independent molecules in the asymmetric unit, which are not enantiomers. The chiral centers C8a, C9, C12, C12a, C12b are either S,R,S,R,R or R,S,R,S,S, respectively, because of the centric space group.     

Self-Assembly of C-Methyl Calix[4]resorcinarene with 5,5′-Bipyrimidine

Abstract The X-ray crystal structure of the complex formed between 5,5′-bipyrimidine and C-methylresorcinarene is described. The structure (C₄₁H₄₅N₅O₁₂) is triclinic with a = 12.8610(10), b = 13.0560(10), c = 13.6068(11)?, α = 104.0730(10), β = 104.9260(10), γ = 111.6430(10)° and space group P-1. The structure reveals that the resorcinarene adopts a boat conformation and forms a three-dimensional network through hydrogen bonding to two water molecules and one dipyrimidine ligand. A single nitromethane molecule is included in the superstructure. Graphical Abstract Self-Assembly of C-Methyl Calix[4]resorcinarene with 5,5’-Bipyrimidine Charles L. Barnes(1) and Eric Bosch(2)* The X-ray crystal structure of the complex formed between 5,5′-bipyrimidine and C-methylresorcinarene is reported.      

Two Isostructural Complexes Constructed from Mixed Ligands of Dipyrido[3,2-d:2′,3′-f]quinoxaline and Phthalate with Novel Oxygen Clusters

Abstract Two isostructural dinuclear complexes [M₂(Dpq)₂(phth)₂(H₂O)₄] · 2H₂O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized and characterized. Crystal data: (1), Mr = 1031.55, monoclinic, C2/c, a = 27.7948(11), b = 10.5196(4), c = 15.0390(5) ?, β = 110.818(1), Z = 4, V = 4110.2 ?³, R ₁ = 0.0277, wR ₂ = 0.0718 [I > 2σ(I)]; (2), Mr = 1018.19, monoclinic, C2/c, a = 27.675(4), b = 10.3601(15), c = 15.082(2) ?, β = 110.954(2), Z = 4, V = 4038.3 ?³, R ₁ = 0.0248, wR ₂ = 0.0668 [I > 2σ(I)]. The dinuclear units are connected into 2-D supramolecular net through O–H···O hydrogen bonding. Moreover, the 2-D networks are ultimately packed into a 3-D supramolecular structure via interlayer π···π stacking interaction between the aromatic rings of Dpq ligands. Furthermore, the photoluminescence property of compound 1 is also studied. Graphical Abstract Two isostructural dinuclear complexes [M₂(Dpq)₂(phth)₂(H₂O)₄] · 2H₂O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized, and the structure study reveals that each dinuclear complex is connected with six other dinuclear units through the O–H···O hydrogen bonding to form 2-D supramolecular networks.      

Synthesis and structural evidence for new diimidazo-[1,5-a:1′,5′-d] pyrazinediones

The synthesis of derivatives of 5H, 10H-diimidazo [1,5-a:l,5-d] pyrazine-5,10-dione is described. The mechanism of the reaction is discussed and the chemical, spectral and X-ray data giving the evidence of the structure of these compounds are presented. X-ray studies were carried out on compound6c (C₂₄H₂₂N₆O₂) witha=9.250(3),b=11.879(3),c=10.250(3),Z=2 and space groupP2₁/a. The structure was solved using direct methods and refined by weighted full-matrix least squares. The refinement, based on 990 reflections withI2.5(I), converged to a finalR of 0.041 andR _w=0.036.     

Annulated bicyclo[2.2.2]octenones: 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.02,6]undeca-4,10-diene-3-spiro(1′-cyclopropane)-8-one and 12-hydroxy-12-chloromethyl-endo-tricyclo [8.2.2.02,9]tetradeca-13-en-11-one

A single crystal X-ray diffraction study of two annulated bicyclo[2.2.2]octenones has been carried out to establish their precise stereostructures. The compounds, with their crystal data, are:1, 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.0^2,6]undeca-4,10-diene-3-spiro(1-cyclopropane)-8-one, C₁₄H₁₅O₂Cl, space group P2₁/c,a=10.540(2),b=9.668(1),c=11.841(4)Å, =95.67(2)°,Z=4, and2, 12-hydroxy-12-chloromethyl-endo-tricyclo[8.2.2.0^2,9]tetradeca-13-en-11-one, C₁₅H₂₁O₂Cl, space group C2/c,a=20.747(8),b=6.498(1),c=20.525(3)Å, =93.04(3)°,Z=8. The molecule of1 has endo stereochemistry at the ring junction and the spirocyclopropane ring is proximal to the hydroxyl group. In2, the eight membered ring deviates from a chair conformation and one ring atom is disordered. Crystals of1 and2 contain centrosymmetric dimers formed by C=O...O–H hydrogen bonds.     

Synthesis and Crystal Structure Determination of Methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and Methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate

Abstract  

Dilithiated C(α), N-carbomethoxyhydrazones were condensed with lithiated methyl 2-(aminosulfonyl)benzoate to afford intermediates that were isolated and not characterized but cyclized with acetic anhydride, which also resulted in N-acetylation. The X-ray crystal structure determinations of methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate products were a follow up for absorption spectra, and they confirmed their structures. Mechanistic intermediates to describe the reaction may include C-acylated intermediates that cyclize to spiro(N-benzoisothiazole dioxide-pyrazole) instead of N-carbomethoxypyrazole-ortho-benzenesulfonamides. Crystals of C₁₉H₁₇N₃O₅S 7 are monoclinic, P2₁/c, a = 11.899(2) ?, b = 17.562(4) ?, c = 9.484(2) ?, β = 111.03(3)°, Z = 4, V = 1849.9(6) ?³, R ₁ = 0.0857 and wR ₂ = 0.2216 for reflections with I > 2σ(I); crystals of C₁₇H₁₅N₃O₅S₂ 8 are orthorhombic, Pbca, a = 16.045(3) ?, b = 10.746(2) ?, c = 20.389(4) ?, Z = 8, V = 3516(1) ?³, R ₁ = 0.0841 and wR ₂ = 0.2179 for all reflections with I > 2σ(I).     

Crystal structure and charge distribution for 20 oximino-5α-pregn-16-eno[3, 4,-c]-1′2′5′-oxadiazole (HS998)

The crystal structure of the modified steroid, 20 oximino-5 pregn-eno [3, 4-c] 125 oxadiazole (HS998) using X-ray diffraction is reported. HS998 crystallizes in the orthorhombic space groupP2₁2₁2₁, having cell parametersa=13.465(3),b=18.792(4),c=7.598(2) Å;Z=4. The structure was solved by direct methods and refined by full matrix least squares toR=0.060 for 3478 reflections.     

Synthesis and crystal structures of 4,4′-bipyridinium and 2,2′-bipyridinium pentachloro complexes containing the polynuclear anions [Bi2Cl10]4− and [Bi4Cl20]8−

The compounds 4,4-bipyridinium(2+) pentachloro-bismuthate(III) (1), [4,4-(C₁₀H₈N₂)BiCl₅] and 2,2-bipyridinium(2+) pentachloro-bismuthate(III) (2), [2,2-(C₁₀H₈N₂)Bi₂Cl₁₀] have been obtained by reacting bismuthate oxide and 4,4-bipyridine or 2,2-bipyridine in HCl acid medium. They have been characterized by single crystal X-ray analysis. (1) crystallizes in the triclinic space group with a = 9.776(2), b = 11.009(3),c = 8.346(1) Å, = 101.58(2), = 98.63(2), and = 112.86(2)°. (2) crystallizes in the monoclinic space group P2₁/c with a = 14.239(2), b = 14.226(2), c = 16.275(3) Å, and = 110.15(2)°. The crystal structure of (1) consists of 4,4-bipyridinium(2+) cations interacting through hydrogen bonding with [Bi₂Cl₁₀]^2– dimers giving rise to endless double chains, while that of (2) is formed by 2,2-bipyridinium(2+) cations and [Bi₄Cl₂₀]^8– tetramers extensively interacting through hydrogen bonding. The different polynuclearity of the anions seems related to the different directions along which each cation can form hydrogen bond interactions.     

Synthesis and optical properties of poly[4-methacryloxy-(4′-carboxy)-azobenzene]

Abstract

In the present work, the homopolymer built from the free radical polymerization of methacrylic monomer incorporating an azobenzene side-group has been synthesized and structurally characterized. The optical properties such as refractive index, extinction coefficient, absorption coefficient and optical energy band gap of poly[4-methacryloxy-(4′-carboxy)-azobenzene] thin film prepared by high vacuum sublimation method were determined using spectroscopic ellipsometry combined with transmittance measurements.

We found that in the spectrum of extinction coefficient there are absorption bands, which are assigned as the n-π* and π-π* electronic transitions of the azo compound.     

Structure of N,N′-bis[3-(aminocarbonyl)propyl]sulfamide

The title compound, C₈H₁₈N₄O₄S, possesses C₂ symmetry, with the S atom lying on a twofold rotational axis in the unit cell. The sulfamide group of each molecule forms four identical hydrogen bonds with those of its four neighboring molecules, resulting in a rhombic two-dimensional hydrogen bonded network. This network assembles in the third dimension via hydrogen bonds between the primary amide groups of the substituents that extend from the 2D sulfamide sheets. The primary amide groups form a hydrogen-bonded eight-membered cyclic dimer around a two-fold rotational axis. These cyclic dimers are linked into a ribbon-like network via hydrogen bonding interaction between the trans-H and the carbonyl of the amide groups. The compound crystallizes in C2/ca with a = 8.6162(1), b = 57716(1), c = 24.8344(b) Å, = 96.298(1)°, D _calc = 1.441 g cm^–3, and Z = 4.     

Synthesis,Characterization and Structural Conformation Studies of 2-Amino-3-ethoxycarbonyl-4-(4′-methoxy Phenyl)-4H-pyrano-[3,2-c]-chromene-6-methyl-5-one

2-amino-3-ethoxycarbonyl-4-(4′-methoxy Phenyl)-4H-pyrano-[3,2-c]-chromene-6-methyl-5-one was synthesized by the two-component reaction of 6-methyl-4-hydroxy coumarin with 4′-methoxy-2-cyano cinnamate, which was synthesized by Knoevenagel reaction with 88% yield. The compound obtained was characterized by spectroscopic techniques and confirmed by X-ray crystallographic studies. The crystallographic data analysis reveals that the title compound crystallizes in the triclinic space group \(P\overline{1}\) with cell parameters a = 7.7750(8) Å, b = 9.0310(6) Å, c = 15.6120(17) Å, α = 77.249(7)°, β = 115.860(3)°, γ = 70.139(7)°, V = 1,003.0(16) Å³ for Z = 4. The structure has been solved by direct methods and refined to R1 = 0.0552 for 3,164 observed reflections with I > 2 σ(I). The pyran ring is in a flattened boat conformation. The carbonyl group is oriented in a -synperiplanar(cis) conformation.

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Synthesis and Structural Characterization of [2-(2-1H-Imidazoly)-1H-imidazolium nitrate] and [2-(2-1H-Imidazoly)-2H-imidazolium phthalyl glycinate] Based on the 2,2′-bi-1H-Imidazole Molecule

Abstract  

Two new compounds (H₃biim)(NO₃)(1) and (H₄biim)(phthgly)₂ (2) (H₂biim=biimidazole; Hphthgly=N-phthaloylglycine) have been synthesized and characterized by luminescence and single crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group C2/c, where a = 14.8078(15), b = 5.9233(6), c = 20.028(2) ?, β = 92.7910(10)°, V = 1754.6(3) ?³ and Z = 8. Compound 2 crystallizes in the monoclinic space group P2(1)/n, where a = 15.3775(14), b = 5.3200(6), c = 6.4689(18)?, β = 115.418(2)° V = 1216.9(2)?³ and Z = 4. In 1, the N–H groups of H₃biim⁺ and the oxygen atoms of NO₃ ⁻ are linked by hydrogen bonds leading to H₃biim⁺(N,N)–R₂²(10) and N–H···O interactions forming infinite 1D helical chains along the b-axis. Compound 2 consists of a planar diprotonated biimidazole moiety and two phthgly anions which connect to the dication by hydrogen bonds phthgly⁻(O,O)–R₂²(9).     

The crystal and molecular structure of spiro[1-(S)-Br-3-(S)-H-4-(R)-l-(1′ R,2′ S,5′R)-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]hexane-2,3′-(R)-(4′-(R)-diphenylmethoxy-5′-l-(1′ R,2′ S,5′ R)-menthyloxy-butyrolactone)]

Crystal structure of C₄₁H₅₃O₇Br has been determined by single-crystal X-ray diffraction. The compound crystalline in the orthorhombic space group P2₁2₁2₁, with a = 11.264(2), b = 12.058(2), c = 29.337(6) Å, Z = 4. The bond angles of cyclopropane moiety in the molecule are approximate to 60° and agree with theoretic values of the internal angles in a cyclopropane, and two chiral menthyloxy groups are located above and under the whole chiral molecule, respectively. The configuration of the pentacyclic lactone is shown as envelope form.     

沿[1 ■00]方向升华法生长6H-SiC单晶

本文采用升华法沿着垂直于c轴方向的[1 ■00]方向生长6H-SiC单晶。利用光学显微镜对晶体表面及腐蚀后的晶片进行观察,发现沿[1 ■00]方向生长出的单晶与传统方法沿[0001]方向生长单晶有很多的不同之处,多型对于籽晶的继承性非常强,但是在生长过程中多型夹杂不会发生,该方法生长的晶体中没有发现螺位错(微管)缺陷。     

Crystal structure of a synthetic anabolic agent: stanazolol ethanol solvate, 17β-hydroxy-17α methylandrostano[3,2-c]pyrazole ethanoate

The crystal and molecular structure of 17-hydroxy-17 methylandrostano[3,2-c]pyrazole ethanoate (stanazolol ethanol solvate), C₂H₃₀N₂OC₂H₅OH, has been determined by direct methods and refined by full-matrix least squares to a final R of 0.0577 for 4021 observed reflections and 245 parameters using Cu K radiation, = 1.54178 Å. The compound crystallizes in space group P2₁2₁2₁ with Z = 4 molecules per unit cell. In the steroid skeleton the ring A adopts a half-chair conformation, being considerably strained, as a consequence of the fused planar pyrazole ring E. Rings B and C however are chairs and ring D has a 13,14 half-chair conformation. All rings of the steroid skeleton are trans-connected. The OH group of the solvated ethanol molecule is hydrogen bonded to the -oriented carbonyl substituent O(20) of ring D. The molecules are further held together in the crystal structure by head–tail hydrogen bonding between N(1)H in the pyrazole ring and O(20), which consequently is an acceptor for the two H-bonds. Overall the molecule lacks any significant curvature with no interplanar dihedral angle greater than 7°. Possible binding modes of stanazolol with the human androgen receptor are discussed.     

A structural model for a new class of conformationally constrained retinoid: (2Z,4E)-4-[3′,4′-dihydro-1′(2′H)-naphthalene-1′-ylidene]-2-butenoic acid

Racemic (2Z,4E)-4-[3′,4′-dihydro-1′(2′H)-naphthalene-1′-ylidene]-2-butenoic acid (1) is a polyene chain-shortened analog of (9Z)-retinoic acid (3) which uses a tetrahydronaphthyl ring to conformationally constrain the C6-C7 single bond (retinoic acid numbering). The structure of (1) was obtained to determine the effects of the tetrahydronaphthyl ring on the ring to polyene chain conformation as compared to a published crystal structure for (9Z)-retinal (2). The results reveal significant differences between the solid state structures of (1) and (2), particularly for torsion angles about C6, C7 and C8, C9. The title compound crystallizes in the centrosymmetric monoclinic space groupP2₁/n withZ=4. (Cell dimensions:a=10.863(2) Å,b=7.637(2) Å,c=15.781(3) and β=106.11(3)°.) The structure was refined toR=3.88% for those 1132 unique data with |F _o|>6σ(F _o). In the crystal structure, the molecules adopt a hydrogen bonded dimeric structure.     

沿[1-100]方向升华法生长6H-SiC单晶

本文采用升华法沿着垂直于c轴方向的[1-100]方向生长6H-SiC单晶.利用光学显微镜对晶体表面及腐蚀后的晶片进行观察,发现沿[1-100]方向生长出的单晶与传统方法沿[0001]方向生长单晶有很多的不同之处,多型对于籽晶的继承性非常强,但是在生长过程中多型夹杂不会发生,该方法生长的晶体中没有发现螺位错(微管)缺陷.