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 diffraction investigation of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′, 12,12′-octamethylcyclohexasiloxane and trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′, 12,12′-decamethyl-5-carbahexacyclosiloxane

The crystal structures of two organosilicon compounds are studied by X-ray diffraction. Crystals of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′,12,12′-octamethylcyclohexasiloxane, C₂₀H₃₆O₈Si₆, (I) are triclinic; at 110 K, a = 11.476(1) Å, b = 12.106(1) Å, c = 13.636(1) Å, α = 94.337(1)°, β = 112.669(1)°, γ = 112.216(1)°, space group $P\bar 1$ , Z = 2, and R = 0.057 for 5069 reflections with F > 4σ(F). Crystals of trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′,12,12′-decamethyl-5-carbahexacyclosiloxane, C₁₁H₃₄O₇ Si₆, (II) are tetragonal; at 293 K, a = b = 15.487(3) Å, c = 11.364(3) Å, space group P4₂/n, Z = 4, and R = 0.055 for 955 reflections with F > 4σ (F). It is found that the structure of compound I, in which the substituents at the Si(1) atom differ in volume and inductive effect, contains two crystallographically independent molecules with different conformations of the hexasiloxane ring. In structure II, the oxygen atom and the methylene group are statistically disordered as a result of the location of the molecule at the center of symmetry. Although the SiCSi angle [122.1(1)°] differs noticeably from the tetrahedral angle, its value is characteristic of cyclohexasiloxanes and is not related to the disorder.     

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.     

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.     

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 structure of syn-1-acetyl-9′aH-8′- methoxyspiro[indole-3,2′-oxeto[3′,2′:4,5]furo[3,2-g][1] benzopyran]2,6′-dione

The crystal structure of syn-1-acetyl-9a-hydro-8-methoxyspiro[3H-indole-3,2(2aH) oxeto[3,2-g]furo[3,2-g]benzo[ b]pyran-2,6-dione 1 was determined by X-ray diffraction analysis. It possesses P2(1)/c space group symmetry, with a = 12.391(3), b = 15.035(3), c = 9.5435(19) Å, = 93.66(3), and D _calc. = 1.517 Mg/m³ for Z = 4.     

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.     

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 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.     

The structure of 20 oximo-5α-pregnano-16-eno[3,4-C]-1′,2′,5′-oxadiazole (HS976)

The crystal and the molecular structure of the steroidal oxadiazole 20-oximo-5-pregnano-16-eno[3,4-C]-1,2,5-oxadiazole (C₂₁H₂₈N₂O₃) has been determined by direct methods, and refined to a finalR of 0.086 for 3100 observed reflections. The compound crystallizes in space groupP2₁, with cell dimensionsa=18.284(6),b=13.992(4),c=7.370(3)Å,=96.97(3)°;V=1885 ų,Z=4,D _x =1.27 g cm^–3, =1.5418 Å, (CuK =5.95 cm^–1. The two independent molecules are related by a pseudo twofold axis. Both molecules exhibit similar overall topography, rings A, B, C, and D adopting distorted sofa, chair, chair, and distorted envelope conformations, respectively.     

Crystal structure of (3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocen-2-yl) carboxylic acid and its bis-[W(CO)5] complex·0.5C5H12: Conformation of 1,1′-diphosphaferrocenes

The structures of (3,3,4,4-tetramethyl-1,1-diphosphaferrocen-2-yl)carboxylic acid (1) and its bis-[W(CO)₅] pentane solvate complex (2) have been determined by X-ray analysis. The compound 1 crystallizes in the monoclinic P2₁ /n space group with Z = 4; a = 7.8404(9), b = 14.9441(16), c = 11.7730(14) Å, = 92.773(10)°, V = 1377.8(3) ų, and D_calc = 1.553 g cm^–3. The compound 2 crystallizes in the triclinic space group with two complex molecules and one pentane molecule in the unit cell. Cell parameters: a = 10.7070(2), b = 12.577(2), c = 13.239(3) Å, = 84.00(2), = 77.58(1), = 66.06(1)°, V = 1591.0(5) ų, and D_calc = 2.100 g cm^–3 .The fully eclipsed conformation of the phospholyl rings with P···P secondary bonding of 3.353(1) Å is observed in 1 and a partially eclipsed conformation is found in 2. The 10 possible conformations of 1,1-diphosphaferrocenes were described as the function of conformational parameter and observed geometry of the phospholyl rings.⁷ We suppose that the earlier conclusions concerning the destabilizing nature of 1,1-diphosphaferrocene conformations with < 100° cannot be considered as general. The mode of W – P coordination, the structural changes of 1 by W(CO)₅ coordination, the structural effect of phospholyl rings substitution by the –COOH group, and hydrogen bonds are analyzed.     

Crystal structure of 2,2′-diformyl 4,4′-dimethyl 6,6′-[piperazine-1,4-diyl bis-(methylene)]bis phenol

The title compund C₂₂H₂₆N₂O₄,Mr=382.46 crystallizes in the orthorhombic space group P2₁2₁2₁ with =8.867(1)Å,b=13.228(2)Å,c=17.029(3)Å,V=1956.7(2)ų,Z=4, D_cal=1.30 Mgm^–3,F(000)=816, =6.89 cm^–1, (CuK)=1.5418 Å andT=298 K. The structure was solved by direct methods and refined by full-matrix least-squares. The finalR=0.046 for 1995 unique reflections. The phenyl rings are coplanar (oriented at an angle of 6.4(1)^o) and orients at an angle of 112.2(1)^o and 115.7(1)^o, respectively with the piperazine ring. The piperazine ring adopts achair conformation and the substituents at the N-atoms are in an equatiorial position.DCB Contribution No. 823.     

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.     

Synthesis and crystal structure of 3-ammoniumphenyl sulfone selenate, 3-aminophenyl sulfone [C12H14N2O2S]SeO4 · [C12H12N2O2S]

The crystal structure of [C₁₂H₁₄N₂O₂S]SeO₄ · [C₁₂H₁₂N₂O₂S] was determined by X-ray diffraction on single crystal. Crystals are orthorhombic, space group Pbca, with cell parameters a = 11.545 (1), b = 8.143 (1), c = 55.783(1)Å, V = 5244.2 (8)ų and Z = 8. The structure can be described as organic layers built by [C₁₂H₁₄N₂O₂S]²⁺ cations and [C₁₂H₁₂N₂O₂S] molecules, parallel to ab plane, between which the inorganic groups SeO ₄ ^2? are inserted. In this atomic arrangement, H-bonds between the different species play an important role in the three-dimensional network cohesion.     

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 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 tris-(2,2′,2″)-triaminoethylamino-salicylidene iron(III) complex

Tris-(2,2,2)-triaminoethylamino-salicylidene iron(III) crystallizes in the monoclinic crystal system witha=7.766(2),b=25.423(5),c=13.318(5) Å, =118.04(3)°, space group P2₁/c,V=2320.8(6) ų,Z=4, andD _x=1.464 g cm^–3. The center of the axially distorted octahedron is occupied by the Fe atom which is coordinated by six donor nitrogen and oxygen atoms infac positions. The planes of coordinated atoms (N and O) with the Fe(III) atom are almost planar and the maximum elevated atom from these planes is O(1) (–0.1065 Å).     

[(CH3)2NH]3[H3PMo12O40]的合成、结构及表征

通过水热合成法,成功合成了化合物[(CH3)2NH]3[H3PMo12O40],并通过单晶X射线衍射,IR,XRD,元素分析和电化学分析对该化合物进行表征.该化合物中,Keggin型磷钼酸之间通过氢键形成二维折叠层,这些层按照ABCD沿c轴方向堆积.二甲胺分子分布在层间,通过氢键连接相邻的来自不同层的两个Keggin型磷钼酸,将二维折叠层进一步拓展成三维超分子骨架.     

The Chair–Envelope Conformation of Two Derivatives of Triethylammonium 3-Oxo-8,9-Dinitro-Bicyclo [3.3.1] Non-7-En-6-Nitronate [I] and [II]

Abstract  

The title compounds C₁₉H₁₈N₃O₉ ⁻·C₆H₁₆N⁺ (I) [triethylammonium 2-benzyl-2-ethoxycarbonyl-3-oxo-8,9-dinitro-bicyclo [3.3.1] non-7-en-6-nitronate] and C₁₉H₁₇N₄O₁₁ ⁻·C₆H₁₆N⁺ (II) [triethylammonium 2(4-nitrophenylmethyl)-2-ethoxycarbonyl-3-oxo-8,9-dinitro-bicyclo [3.3.1] non-7-en-6-nitronate] crystallize in monoclinic crystal system with P2 ₁ /c space group. In compounds I and II, the bicyclo [3.3.1] nonane has chair–envelope conformation. The crystal structure of compound (I) is stabilized by N–H⋯O, N–H⋯N hydrogen bonds. In both the crystal structures weak C–H⋯O hydrogen bond is observed. Both compounds adopt chair–envelope conformation. An examination of puckering parameters, torsion angles and model (Dreiding) of the title compounds clearly indicates that the ring A has slightly distorted chair conformation and ring B has slightly distorted envelope conformation.     

Crystal Structure, Absolute Configuration, Conformational Analysis and Molecular Dynamics Study of the Novel Steroidal Tetrazole Derivative: (25R)-3,12a-diaza-A,C-bishomo-5α-spirostano[3,4-d] [12a,12d] bistetrazole [HS-989]

Abstract  

The X-ray crystal structure of the bistetrazole steroid derivative: (25R)-3,12a-diaza-A,C-bishomo-5α-spirostano[3,4-d] [12a,12d] bistetrazole (HS-989) has been determined at room temperature. The crystals are orthorhombic, space group P2₁2₁2₁ with a = 16.855(1) ?, b = 25.048(2) ?, c = 6.402(1) ?, V = 2702.7(5) ?³ Z = 4, Density (calculated) = 1.250 Mg/m³. The tetrazole-modified 7-membered rings A and C have similar modified uniaxial chair conformations, with pseudo-symmetry m through the extra C–N tetrazole bond; the 6-membered rings B and F are symmetrical chairs; of the 5-membered rings, D is in a half-chair and ring E an envelope conformation; tetrazole rings T1 and T2 are both planar and oriented towards the α-face. The spirostan moiety is β-oriented. Overall the modified steroid skeleton is reasonably flat, with a pseudo-torsion angle C(19)–C(10)···C(13)–C(18) of −6.2°. Conformational sampling, using high temperature SYBYL molecular dynamics was used to investigate different arrangements of the steroid skeleton. Predicted low energy conformations were found to compare favourably in some respects with both X-ray crystallographic and NMR observations but with important differences.