Quaternary salts of oxo-sparteines: Crystal structure of N(16)-methyl-2-oxo-α-isosparteine iodide monohydrate

The molecular and crystal structure of N(16)-methyl-2-oxo--isosparteine iodide monohydrate have been determined by single crystal X-ray analysis using diffraction data collected on a diffractometer. The finalR for 1211 reflections and 196 parameters was 0.036. The configuration on the parent base, 2-oxo--isosparteine, remains unchanged after methyl substitution at thecisoidally oriented N(16) tertiary amino nitrogen. Because of an internal stress, four rings of the quaternary cation adopt a distorted conformation. The water molecule of crystallization links cation and anion by O_(lactam)H-O-HI^– hydrogen bonds. Weak C-HI^– interactions between the ions have been found in the crystal. Both the cation conformation and cation-anion interactions influence the position and shape ofv _CH bands in the IR spectrum of solid. The methyl C-H stretching vibrations are observed at 3090 and 3025 cm^–1, and the methylene absorption is observed in the region 3000-2800 cm^–1. Thev _OH water molecule absorption at 3490 and 3420 cm^–1 indicates two types of hydrogen bonding.     

Crystal structure of 1,3-(N,N′-benzamide)-2-methyl-1-pentene

Crystals of the title compound are monoclinic (C20H22N2O2): space groupP2₁/n,a=11.800(3),b=13.820(2),c=11.004(3) Å,=92.74(3)°. The structure was solved by direct methods and refined by block-matrix least-squares procedure to giveR=0.078 andRw=0.076 for 1960 reflections above 3(I). The two amide groups are not coplanar with respect to their benzene rings. An intramolecular N-HO hydrogen bond was found in the molecules which are joined in chains by other strong N-HO hydrogen bonds.     

Crystal and molecular structure of 17-β-methyl-α-isolupanineN-(16)-oxide perchlorate monohydrate

[C₁₆H₂₇N₂O₂]⁺·ClO ₄ ^– ·H₂O,M _r=396.87, orthorhombicP2₁2₁2₁ a=13.708(4),b=16.930(7),c=8.311(3) Å,V=1928.3(13) ų,Z=4,D _x=1.367(2) g cm^–3,(MoK)=0.71068 Å,(MoK)=1.95 cm^–1,F(000)=848,T=292 K,R=0.061 for 1324 unique reflections. RingsA,B,C,D have half-chair, chair, chair and chair conformations, respectively; the quinolizidone moietyA/E has a quasi-trans and the quinolizidine moietyC/D has a trans configuration. The cations are connected into chains along the crystallographic direction [001] by strong hydrogen bonds utilizing the water molecule: C(2)=O(5)O(W)O(6)-N(16) of 2.623(7) and 2.574(7) Å, respectively. The water molecule is also hydrogen-bonded to one oxygen atom of the perchlorate anion: O(W)O(2) is 3.106(10) Å. A very short intramolecular distance between N(1) and O(6) of 2.696(7) Å, due to the quasitrans-trans configuration of the-isolupanine skeleton, is observed.     

Molecular and crystal structure ofβ-isosparteine monoperchlorate

The crystal structure; determined by X rays, and the¹³C-NMR spectra of-isosparteine perchlorate are presented. The quinolizidine moieties are present in acis ring-juncture; all piperidine rings are in a chair conformation. The two nitrogen atoms are linked by a hydrogen bond of 2.704(5) Å. The proton at N(16) is also involved in a weak hydrogen bond with the O(2) of the perchlorate anion. The two quinolizidine moieties-protonated and unprotonated-differ only slightly in conformation; the protonation caused small but significant changes in the length of the bonds about the nitrogen atoms. The title compound was obtained by chemical transformations of 17-oxosparteine and protonation with an equimolar amount of HClO₄ in methanol.¹³C-NMR spectra in DMSO-²H₆ revealed the presence of the symmetricalcis-cis bis-quinolizidine structure of the salt in solution.     

Crystal structure of 17β-hydroxy-17α-methyl-5α-androstano [2,3-C] Furazan (Furazabol)

The crystal and molecular structure of 17-hydroxy-17-5-androstano [2,3-C] Furazan, Furazabol (C₂₀H₂₄N₂O₂), has been determined by direct methods and refined by full matrix least squares to a final R of 0.0528 for 1927 observed reflections and 216 parameters, CuK, = 1.54178 Å. The compound crystallizes with two molecules in the asymmetric unit, Z = 4, Dc = 1.131 Mg m^–3 space group P2₁, with unit cell parameters a = 18.747(3), b = 6.346(5), c = 15.647(4) Å, = 99.96(2)°, V = 1833.9 ų, (CuK) = 0.584 mm^–1. Whilst the two independent molecules have similar overall geometry there are small differences in bond lengths, bond angles and torsion angles in rings A and D and significant conformational differences in ring A. The A ring adopts a half-chair conformation in molecule A and an intermediate between a half-chair and a sofa in molecule B. The D ring in molecule A has a 13/14 half-chair conformation and in molecule B a conformation between an envelope and half-chair.     

Synthesis and crystal structure of iodo-1-(2′-aminophenyl)-2,6-diaza-6-methyl-9-amino-1-noneno copper(II) iodide

Reaction of equimolar amounts of 2-aminobenzaldehyde and 3,3-diamino-N-methyldipropyl-amine in methanol affords a novel 11 condensation product, abaMedpt, which has been isolated as the copper(II) complex, [Cu(abaMedpt)I]I. The crystal structure of the complex has been determined from single crystal diffractometer data and refined to a finalR factor of 0.0353 with 2492 unique observations and 206 variables. The complex crystallizes in the monoclinic space group P2₁/c (N° 14) witha=9.263(2),b=18.189(3),c=11.740(3) Å,=92.97(4)°,Z=4,D _c =1.902 g cm^–3. The structure involves a five-coordinate square-pyramid CuN₄I chromophore and an uncoordinated iodide anion. Nitrogen atoms constitute the basal plane, while the bonded iodine occupies the apical position. The structure contrasts with the more usual distorted trigonal-bipyramidal stereochemistries of CuN₄I chromophores reported so far.     

Synthesis and crystal structure of N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)- N′-salicylidene hydrazine

A novel Schiff base compound, N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-salicylidene hydrazine (PMBP-SAH), has been synthesized and characterized by X-ray diffraction: monoclinic, space group C2/c with a = 21.796(5) Å, b = 18.370(3) Å, c = 20.843(3) Å, = 95.440(10)°, V = 8308(3) ų, and Z = 16. The title compound contains two kinds of tautomers: the red compound is the keto form and the other is the enol form. Changes in color are due to the isomerization of the enol and keto forms by the intramolecular proton transfer.     

Crystal and molecular structure of calcium L(–)-malate trihydrate

The new crystal and molecular structures of a less common hydrated calcium L(–)-malate (calcium (2S) 2-hydroxybutanedioate trihydrate) Ca(C₄H₄O₅)3H₂O, are reported. X-ray crystallographic data are as follows: a = 6.6460(3) Å, b = 8.3795(3) Å, c = 8.2707(4) Å, = 112.640(2)°, V = 425.1(4) ų, space group P2₁ (No. 4), Z = 2, D _calc = 1.767 g cm^–3. The calcium ion coordination number is seven. One of the three water molecules present in the unit cell is less strongly bound, only interacting with a calcium ion. In aqueous or hydroalcoholic solution, both di- and trihydrated species crystallize simultaneously.     

Crystal structure of N,N ′-bis(cyclohexyl)-1-(N,N-dihexylamino)perylene-3,4:9,10-bis(dicarboximide)

An asymmetric dialkylamino-substituted perylene bisimide (1), N,N′-bis(cyclohexyl)-1-(N,N-dihexylamino)perylene-3,4:9,10-bis(dicarboximide), was synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P–1, with a = 9.8924(6), b = 14.6338(10), c = 15.6221(10) Å, α= 105.098(3)°, β = 103.386(2)°, γ = 107.772(3)°, and Z = 2. The central perylene core of 1 is twisted with dihedral angles of 14.9(3)° and 11.6(3)°; this twist configuration induces the axial chirality in this family of perylene bisimide dyes. In the crystal structure, the intermolecular C–H···O interaction links a pair of molecules into a cyclic centrosymmetric dimer that is connected to one another via the intermolecular π–π stacking, so linking the molecules into a continuous one-dimensional framework along the [100] direction.     

Crystal and molecular structure of two isomeric N-methyl iodides of thiobinupharidine:trans,trans-N,N′-dmethyl-thiobinupharidine diiodide dihydrate acetone solvate andcis,trans-N,N′-dimethylthiobinupharidine diiodide dihydrate methanol solvate

The crystal structures of two quaternary salts,trans,trans- andcis,trans-N,N-dimethylthiobinupharidine diiodide, whose stereochemistries have been previously characterized by¹³C NMR spectroscopy, have now been determined by X-ray analysis. Differences in the nitrogen atom configuration of the AB quinolizidine fragment result in different conformations of the central part of the cations, the spiro tetrahydrothiophene ring, and specific selectivity toward solvent molecules. Thetrans,trans isomer crystals obtained from an acetone/methanol/water solution contained two water and one acetone molecule, while thecis,trans cocrystallized from the same solvent mixture with methanol and two water molecules. Very weak hydrogen bonds of the C-HI^– type determine interactions between the quaternary cations and the I^– anions in the solid state. Water molecules form a dimer, and this dimer is hydrogen bonded to the I^– anions. Organic solvent molecules included in crystals show different type of interactions with surrounding molecules: (i) the acetone molecule is trapped in the cavity of thetrans,trans cation by very weak C-HO interactions; (ii) methanol is hydrogen bonded to a water molecule while with thecis,trans cation and I^– anion interacts only by van der Waals forces.     

Crystal structure of tris(triphenylsiloxy)borane·triphenylsilanol (1:1) adduct

The title compound crystallizes in the triclinic space group , with a = 14.458(6), b = 14.630(5), c = 14.721(8) Å, = 79.75(2), = 80.11(3), = 80.50(3)°, and Z = 2. The crystal structure consists of molecules of (Ph₃SiO)₃B and Ph₃SiOH linked by an weak B···(silanol) acceptor-donor bond, additionally stabilized by OH(silanol)···O(siloxy) hydrogen bonds. The average B–O, Si–O distances and B–O–Si angle are 1.369, 1.649 Å and 137.2°, respectively.     

Crystal structure of 5α-cholest-6-one

The crystal and molecular structure of the steroid 5α-cholest-6-one has been determined by X-ray diffraction analysis. The compound crystallizes in space group P2₁ with the unit cell parameters a = 10.575(1) Å, b = 7.698(1) Å, c = 15.284(2) Å, β= 99.34(1)°, V = 1227.72 ų, Z = 2, and R = 0.054 for 1634 observed reflections. The six-membered rings (A, B, and C) have the chair conformations, whereas the five-membered ring Dis intermediate between 13β-envelope and 13β-14α half-chair. All the rings of the steroid skeleton are trans connected. The molecules are linked together by the intermolecular C-H?O hydrogen bonds.     

Crystal structure of zinc iodide complex with carbamide, ZnI2 · 2CO(NH2)2

The structure of ZnI₂ · 2CO(NH₂)₂ is determined by single-crystal X-ray diffraction. The crystals are monoclinic, a = 12.694(3) Å, b = 6.886(2) Å, c = 13.161(3) Å, β = 110.58(2)°, Z = 4, space group P2₁/a, and R = 0.0337 for 2481 reflections. Similar to the chloride analogue, the structure consists of discrete molecules with tetrahedrally coordinated Zn atoms. The bond lengths and angles are as follows: Zn-I, 2.5749(8) and 2.5473(8) Å; Zn-O, 1.954(3) and 1.985(4) Å; IZnI, 113.74(3)°; OZnO, 100.5(2)°; and IZnO, 108.5°–113.1(1)°. The crystal structure agrees with the IR and electronic absorption spectra of the crystals.     

Crystal structure of the addition compound of N,N′-bi(2-pyridylmethyl)-oxamide and complex of manganese with 1,10-phenanthroline

The structure of the addition compound, Mn(phen)₃(PMoxdH₂)(ClO₄)₂ was established by X-ray crystallography, where PMoxdH₂ is N,N-bi(2-pyridylmethyl)-oxamide. Six nitrogen atoms of the three 1,10-phenanthroline bind to the manganese ion and the oxygen atom of PMoxdH₂ is uncoordinated. The addition compound crystallizes in the monoclinic space group C2/c, with lattice parameters a = 23.780(6), b = 11.948(5), c = 18.466(6) Å, = 117.38(3)°, V = 4659(3) ų, and Z = 4.     

Crystal and molecular structure of β-resorcylidene aminoguanidine copper(II) complex

The tridentate Schiff base, -resorcylidene aminoguanidine (RAG)1 was synthesized from 2,4-dihydroxybenzaldehyde and aminoguanidine and complexed with copper(II) to form a copper(II)--resorcylidene aminoguanidine (Cu-RAG)2 complex. X-ray diffraction analysis of compound2 (orthorhombic, Pnma,a=11.674(1);b=6.7198(7);c=17.836(2) ) revealed a square-planar copper(II) cation with a tridentate·ligand bound through two nitrogen atoms (N1 and N3) of the aminoguanidine moiety and an oxygen (O1) of the monodeprotonated dihydroxybenzaldehyde function. The remaining coordination site was occupied by chloride and the structure was rigidly planar as demanded by the restrictions of the crystallographic space group. The unit cell contents exhibited an extended sheet-like structure constructed via hydrogen bonds both intermolecularly and involving two water molecules (O3 and O4) also restricted by the same mirror symmetry. The remaining water (O5) provided for interlayer hydrogen bonding.     

Crystal and molecular structure of 1-chloro-1,2-benziodoxolin-3(1H)-one·tetra-n-butylammonium chloride

The title compound,6, a novel 11 complex of 1-chloro-1,2-benziodoxolin-3(1H)-one (5) andtetra-n-butylammonium chloride, was prepared from tetra-n-butylammoniumo-iodoxybenzoate (7) and acetyl chloride. A single crystal of6 was subjected to X-ray analysis: triclinic, space group a=10.239(2),b=11.518(2),c=11.523(3)Å; =73.20(2); =87.85(2), =87.72(2)°; R1=0.0326. The most notable structural feature of crystalline6 is the existence of a secondary bond [I· ·Cl(2), 2.943(1)Å] between the chloride ion and the iodine atom of the chlorobenziodoxolinone moiety. Further coordination at iodine includes three primary bonds: I–C [2.115(4) Å], I–O [2.145(3) Å], I–Cl(1) [2.454(1) Å]. The entire 1-chlorobenziodoxolinone-chloride sub-structure is planar and exhibits iodine-centered bond angles of 78.8(1)° [C–I–O], 92.0(1)° [C–I–Cl(1)], 97.6(1)° [Cl(2)–I–O] and 91.6(1)° [Cl(2)–I–Cl(1)]. The unit cell of6 contains two loosely packed formula units. The chlorobenziodoxolinone-chloride sub-structures occupy a common plane and exhibit a centrosymmetric relationship, while the tetra-n-butylammonium ions are situated one above and one below the plane. Bonding at the iodine atom in6 is more consistent with a 10-I-3 species electrostatically associated with the chloride ion than a 12-I-4 species such as the tetrachloroiodate ion.     

Crystal and molecular structure of the spin-crossover complex bis(pyridine) [N,N′-ethylenebis (3-carboxysalicylaldimine)] cobalt (II)

The average structure of the title compound, Co(H₂fsa₂en)(py)₂, which has been shown previously to exhibit a thermally induced high-spin low-spin crossover, has been investigated by single-crystal X-ray diffraction. This structure has been solved in the monoclinic space groupC2/c (No. 15), with cell dimensionsa=16.641(5),b=9.496(4),c=16.329(6) Å, and=95.47(3)°;V=2569(3) ų,M _r =571.46,Z=4,D _x =1.478 mg m^–3; MoK radiation (graphite crystal monochromator),=0.71073 Å,(MoK)=7.138 cm^–1;T=295 K andR=0.081 for 681 observed [I>3(I)] independent reflections. The cobalt(II) ion resides on a twofold axis in an elongated octahedral environment, the length of the apical bond (formed with pyridine) being 2.262(12) Å and the mean length of the equatorial bonds (formed with the Schiff base) 2.079(12) Å. These values are consistent with the magnetic behavior, which suggested a distorted surrounding for the metal atom. The packing is essentially governed by the parallelism of the salicylaldimine ligands. The two pyridine rings of the molecule are twisted by ~98° on each side of the basal plane; they are probably affected by orientational disorder or, if ordered, they might be described in a superstructure not yet established.     

Crystal structure of (ethylenediammonium-N,N′-di-3-propanoic acid) tetrachloropalladate(II) complex

The title compound was obtained by a synthesis from ethylenediamine-N,N-di-3-propanoic acid dihydrochloride (H₂eddp2HCl) and potassium hexachloropalladate(IV) (molar ratio 1:1, in water). Its structure has been determined by single-crystal X-ray diffraction: monoclinic space group P2₁/n, a = 8.198(1), b = 10.282(1), c = 9.080(1) Å, = 103.62(1)°, V = 743.9(2) ų, and Z = 2. The dianionic complex has a square-planar coordination geometry with four chloro ligands, and ethylenediamine-N,N-di-3-propanoic acid as dication in the second coordination sphere. This is the first reported Pd(II) structure with uncoordinated H₂eddp.     

Crystal structure of 5-fluoro-1-(2,3,6-trideoxy-α-l-glycero-hex-2-enopyranos-4-ulosyl)uracil

The present compound crystallizes in the space groupP2₁2₁2₁ withZ=4 and cell parametersa=21.687(2),b=8.155(3),c=5.883(2)Å. The structure was solved by direct methods and refined by full-matrix least-squares to a finalR value of 0.045 for 1153 observed reflections. The N-glycosidic torsion angle _CN is in the anti-range and the pyranosyl ring adopts a distorted half-chair conformation with ₂=142.7(4)°, ₂=124.4(3)° andQ=0.456(2)Å. In the crystal packing the molecules are linked together by N-HO hydrogen bonds and C-HO contacts.     

Synthesis,Crystal Structure and Biological Activity of N′-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine

Abstract  

The title compound, N′-tert-butyl-N-(3-methoxylbenzoyl)-N-(4-methyl-1,2,3-thiadiazole-5-formylhydrazine (C₁₆H₂₀N₄O₃S) was prepared from the reaction of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride with N′-tert-Butyl-3-methoxylbenzohydrazine, and its structure was characterized by ¹Hydrogen Nuclear Magnetic Resonance, High-Resolution Mass Spectrometry, IR spectra, and single crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group P 21/c with cell parameters a = 17.986(2) ?, b = 8.0180(10) ?, c = 12.0190(14) ?, α = 90°, β = 91.160(5)°, γ = 90°, V = 1732.9(4) ?³, Z = 4, D _c  = 1.335 g/cm³, μ (Mo Ka) = 0.209 mm⁻¹, F (000) = 736, R = 0.0367 and wR = 0.0932. X-ray diffraction analysis indicates that all rings in the title compound are non-planar. The bioassay results indicated that, the title compound had good fungicide activity against Sclerotinia sclerotiorum, certain extent of insecticidal activity against Plutella xylostella L.