Solid state properties of 1,2-epoxy-3-(2-methoxyphenyloxy)-propane—valuable intermediate in non-racemic drug synthesis

Racemic 1,2-epoxy-3-(2-methoxyphenyloxy)-propane 1 undergoes spontaneous resolution upon crystallization. This fact is confirmed by coincidence of the IR spectra of racemic and scalemic crystalline samples of 1, by thermal analysis (single eutectic V-shape binary melting phase diagram), and X-ray analysis (space group P2₁2₁2₁, Z = 4). Racemic 1 could be resolved into (S)-(+)- and (R)-(−)-1 by a preferential crystallization procedure.     

New hydrogen-bonded dimeric and polymeric gold(I) complexes of the heterodifunctional ligand Ph2PNHP(O)Ph2

The preparation of several new gold(I) complexes by chloride metathesis of [AuCl(HL)] [HL=Ph₂PNHP(O)Ph₂] with either HL or K[Ph₂P(E)NP(E)Ph₂] (E=S or Se) is described. All compounds were characterised by a combination of ³¹P{¹H}, ¹H and IR spectroscopy, microanalysis and X-ray crystallography. X-ray structural studies reveal that [Au(HL)₂]Cl [monoclinic, space group P2₁/c, a=9.0726(3) Å, b=21.0847(6) Å, c=12.0131(3) Å, β=105.1090(10)°, V=2219 ų, Z=2, final R=3.97] forms a one dimensional polymeric structure in which alternating [Au(HL)₂]⁺ and Cl⁻ ions are linked through intermolecular N–H⋯Cl hydrogen-bonding. In contrast the three-co-ordinate compound [Au{Ph₂P(Se)NP(Se)Ph₂-Se,Se′}(HL)] [monoclinic, space group P2₁/a, a=21.6752(5) Å, b=9.1200(10) Å, c=24.0742(7) Å, β=106.080(2)°, V=4573 ų, Z=4, final R=8.94] forms hydrogen-bonded dimer pairs analogous to that previously observed in non-complexed HL. The X-ray crystal structure of the gold(I) precursor [AuCl(HL)] has also been determined: monoclinic, space group P2₁/c, a=10.217(8) Å, b=23.256(5) Å, c=20.086(5) Å, β=101.15(4)°, V=4683 ų, Z=8, final R=5.2. The X-ray crystal structure reveals intermolecular N–H⋯OP hydrogen-bonding between adjacent [AuCl(HL)] molecules forming infinite chains.     

New compounds in the cesium sulfobromide rhenium octahedral cluster chemistry: syntheses and crystal structures of Cs4Re6S8Br6 and Cs2Re6S8Br4

The exploration of the CsReSBr system, in order to identify new phases based on octahedral cluster anions, has produced single crystals of Cs₄Re₆S₈Br₆ (1) (trigonal, space group P-6c2, a=9.7825 (3) Å, c=18.7843 (5) Å, V=1556.77 (1) ų, Z=2, density=5.09 g cm⁻³, μ=36.07 mm⁻¹) and Cs₂Re₆S₈Br₄ (2) (monoclinic, space group P2₁/n, a=6.3664 (1) Å, b=18.4483 (4) Å, c=9.3094 (2) Å, β=104.2618 (8)°, V=1059.69 (4) ų, Z=2, density=6.14 g cm⁻³, μ=45.83 mm⁻¹). These two compounds have been obtained by high-temperature solid state route. Their structures have been solved and refined from single crystal X-ray diffraction data. The structure of Cs₄Re₆S₈Br₆ presents isolated anionic cluster units inscribed in a (Cs⁺)₁₂ cuboctahedron and the one of Cs₂Re₆S₈Br₄ exhibits ReS^i-a,a-iRe inter-unit bridges. The framework of the latter presents then a strongly 1-D character.     

Reaction of MeO2C(H)C=C=C(H)CO2Me with Ru3(CO)12. New diruthenium complexes with bridging carboxylate-substituted allene ligands

The reaction of Ru₃(CO)₁₂ with MeO₂C(H)C=C=C(H)CO₂ Me has yielded two isomeric productsanti-Ru₂(CO)₆[μ-η ³-η ¹-MeO₂C(H)CCC(H)CO₂Me],1 in 70% yield andsyn-Ru₂(CO)₆[μ-η ³-η ¹-MeO₂C(H)CCC(H)CO₂Me],2 in 5% yield. Both compounds were characterized by single crystal X-ray diffraction analysis. Both products are diruthenium complexes with bridging di(carboxylate)allene ligands in which the oxygen atom of the carbonyl group of one of the carboxylate groupings is coordinated to one of the metal atoms. Compound1 isomerizes partially to2 at 68°C. Crystal Data for1: space group=P2₁/n,a=11.131(1) Å,b=10.228(2) Å,c=15.978(2) Å,β=102.01(1)°,Z=4, 1653 reflections,R=0.025; for2: space group=P $\bar 1$ ,a=9.340(1) Å,b=14.925(4) Å,c=6.778(2) Å,α=99-02(2)°,β=104 62(2)°,γ=94.58(2)°,Z=2, 1857 reflections,R=0.027.     

The One‐dimensional Polyselenide Compound CsGaSe3

A new one‐dimensional phase, CsGaSe₃ has been synthesized and characterized by single crystal X‐ray diffraction, differential thermal analysis, and single crystal UV/Vis spectroscopy. The structure contains infinite chain anions, [GaSe(Se₂)]^— separated by Cs cations. The Ga³⁺ cation is in a distorted tetrahedral environment coordinated by each two Se^2— and Se₂^2— ions. The red crystals of CsGaSe₃ absorb visible light at energies above 2.25 eV. Differential thermal analysis revealed that the compound does not melt below 1000 °C. Crystal data: CsGaSe₃, monoclinic, space group P2₁/c (No 14), a=7.727(1), b=13.014(3), c=6.705(1), β=106.39(3)°, Z=4, R1=0.0469.     

Two coordination polymers of manganese(II) isophthalate and their preparation,structures, and magnetic properties

Two manganese coordination polymers, [Mn₂(ip)₂(dmf)]·dmf (1) and [Mn₄(ip)₄(dmf)₆]·2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P?1, a=9.716(3) Å, b=12.193(3) Å, c=12.576(3) Å, α=62.19(2)°, β=66.423(17)°, γ=72.72(2)°, Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) Å, b=20.20(2) Å, c=18.01(3) Å, β=108.40(4)°, Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.     

Crystal Structure of [UO<Subscript>2</Subscript>SO<Subscript>4</Subscript>{(CH<Subscript>3</Subscript>)HNCONH(CH<Subscript>3</Subscript>)}<Subscript>2</Subscript>]

The single crystals of [UO₂SO₄{(CH₃)HNCONH(CH₃)}₂] (I) were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 6.847(1) Å, b = 14.259(3) Å, c = 14.297(3) Å, β = 93.451(4)°, space group P2₁/n, Z = 4. The main structural units of crystals I are ribbons whose composition coincides with the composition of the compound. The crystal chemical formula of the complex is AT³M ₂ ¹ (A = UO ₂ ²⁺ ).     

Study of the monocarbonate complex of pentavalent neptunium (NH<Subscript>4</Subscript>)[NpO<Subscript>2</Subscript>(CO<Subscript>3</Subscript>)]

The single crystals of the Np(V) complex (NH₄)[NpO₂(CO₃)] (I) were synthesized and studied by X-ray diffraction. At 100 K, the crystals are hexagonal, space group P6₃ μmc, a = 5.0734(1) Å, c = 10.9191(2) Å, V= 243.399(11) ų, Z = 2, ρ(calcd) = 4.735 g/cm³. The absorption spectra of a crystal of I in the visible and infrared ranges were measured.     

Molecular and crystal structure of 15-acetylsongorine and songoramine isolated from <Emphasis Type="Italic">Aconitum szechenyianum</Emphasis> Gay

Two napelline skeletal diterpenoid alkaloids 15-acetylsongorine, C₂₄H₃₃NO₄ I, and songoramine, C₂₂H₂₉NO₃ II, were first isolated from the roots of Aconitum Szechenyianum Gay. The crystal structures were determined by X-ray single-crystal diffraction analysis. The crystal I is the triclinic system with space group P1 having unit cell parameters of a = 9.360(8) Å, b = 11.593(9) Å, c = 11.830(16) Å, α = 113.223(15)°, β = 105.950(16)°, γ = 101.296(12)°, and Z = 2. Hydrogen bonds O–H···O and O–H···N joint the molecules into dimer. The crystal II belongs to the orthorhombic system with space group P2₁2₁2₁ having unit cell parameters of a = 8.950(2) Å, b = 13.272(3) Å, c = 15.454(4) Å and Z = 4. The O–H···O hydrogen bonding interaction links the molecule into linear chains. The distortion of rings of compound I and II were evaluated by calculation of the Cremer and Pople puckering parameters. The presence of the C–O–C bond in the compound II results in the changes of ring conformations compared with that of the compound I.     

One-dimensional coordination polymers generated from an oxadiazole-containing N,N′-bipyridine-type ligand and Cu(II) salts

Three new Cu(II) coordination polymers have been prepared using Cu(II) salts in combination with 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L2). The compounds were characterized by single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In the solid state, all three new polymeric compounds 1–3 (1: monoclinic, P2/c, a=10.0956(11) Å, b=6.8710(7) Å, c=18.6152(19) Å, β=97.270(2)°, V=1280.9(2) ų, Z=2; 2: monoclinic, P2₁/c, a=9.2275(5) Å, b=16.0479(9) Å, c=18.3403(3) Å, β=91.1260(10)°, V=2715.4(3) ų, Z=4; 3: triclinic, P-1, a=6.9932(7) Å, b=11.5777(12) Å, c=12.5291(13) Å, α=109.401(2)°, β=103.922(2)°, γ=95.316(2)°, V=912.06 ų, Z=2) feature novel one-dimensional single or double-sinusoidal chain motifs with different repeat periods, which result from the different conformations adopted by the L2 ligand.     

An X-ray and 13C CP/MAS NMR study of C,C-linked bipyrazoles and bispyrazolylmethanes

4,4′-Methylene-bispyrazole (1) crystallizes in the P2₁/n space group with Z = 4, a = 5.4199(8) Å, b = 16.194(6) Å, c = 8.381(5) Å, β = 98.18(5)°. 4,4′-Methylene-bis (3,5-dimethylpyrazole) (2) crystallizes in the Pbca space group with Z = 8, a = 8.350(3) Å, b = 16.078(3) Å and c = 17.154(5) Å. Finally, 3,3′-bipyrazole (4) crystallizes in the P2₁/n space group with Z = 2, a = 5.465(2) Å, b = 5.491(3) Å, c = 10.058(4) Å and sol; = 92.88(2)°. The packing adopted by molecules 1 and 2 is related to the disposition of the pyrazole rings. In compound 4, all the molecules are joined to their neighbors by two double hydrogen bond systems forming zigzag chains. Using solid state ¹³C NMR spectroscopy, no dynamic proton transfer was observed in these crystals, and not on those of 3,5,3′,5′-tetramethyl-4,4′-bipyrazole (3) either.     

π-Complexes of copper(I) halides with 3-(allylamino)-(C3H5NHC2H4CN, Apn) and 3-(diallylamino)-((C3H5)2NC2H4CN, Dapn)-propanenitrile. syntheses and crystal structures of compounds [CuCl(Apn)], [(H+Apn)Cu2Cl3], [(H+Dapn)CuCl2], and [(H+Dapn)CuBr2]

The ??-complexes [CuCl(C₃H₅NHC₂H₄CN)] (I), [(C₃H₅NH₂C₂H₄CN)Cu₂Cl₃] (II), [((C₃H₅)₂NHC₂H₄CN)CuCl₂] (III), and [((C₃H₅)₂NHC₂H₄CN)CuBr₂] (IV) are obtained as single crystals by the ac electrochemical synthesis on copper wire electrodes from ethanolic solutions of 3-(allylamino)propanenitrile, 3-(diallylamino)propanenitrile, and CuX₂ (X = Cl, Br). Their crystal structures are determined. The crystals of compounds I, III, and IV are monoclinic, space group P2₁/c, Z = 4. The crystals of compound II are triclinic, space group P $\bar 1$ , Z = 2. The unit cell parameters are a = 11.125(4), b = 8.769(4), c = 8.570(4) ?, ?? = 90.94(4)°, V = 835.9(6) ?³ (I); a = 6.2566(4), b = 7.5975(6), c = 11.1251(8) ?, ?? = 90.896(6)°, ?? = 92.827(5)°, ?? = 94.340(5)°, V = 526.57(7) ?³ (II); a = 11.656(4), b = 6.992(4), c = 14.681(5) ?, ?? = 100.89(4)°, V = 1174.9(9) ?³ (III); a =11.845(4), b = 7.282(4), c=14.855(5) ?, ?? = 100.37(4)°, V = 1260.4(9) ?³ (IV). The coordination mode of the Cu(I) atom in complex I includes two halogen atoms, the C=C bond, and the secondary amine N atom. The coordination environment in isostructural crystals of complexes III and IV is formed by the C=C bond and three halogen atoms as in complex II.     

Crystal and molecular structure of two new Schiff bases: Paeonol-ethylenediamine and paeonol-1,3-propylenediamine

Two new Schiff bases were prepared by the condensation reaction of paeonol with ethylenediamine (for compound 1) and 1,3-propylenediamine (for compound 2). The compounds were studied with single crystal X-ray diffraction method. Compound 1 is monoclinic, space group P2₁/c, a = 10.956(15) Å, b = 6.767(10) Å, c = 12.494(18) Å; β = 104.66(2)°, V = 896(2) ų, Z = 2. Compound 2 is triclinic, space group P-1, a = 6.878(2) Å, b = 12.141(4) Å, c = 12.414(4) Å; α = 101.023(6)°, β = 103.415(6)°, γ = 102.337(6)°, V = 952.8(6) ų, Z = 2. The molecular structures of 1 and 2 are similar; the molecule being centrosymmetric in 1 but asymmetric in 2.     

Crystal structure of 1-(diphenylmethylene)-2-(thiazolo[4,5-b]pyridin-2-yl)hydrazine

The 1-(diphenylmethylene)-2-(thiazolo[4,5-b]pyridin-2-yl)hydrazine compound (IV) is synthesized based on a 3-amion-2-chloropyridine precursor and characterized by single crystal X-ray diffraction. The structural analysis reveals that compound IV belongs to the monoclinic system, space group P2₁/c, a = 11.869(5) Å, b = 13.155(6) Å, c = 10.970(5) Å, β = 102.431(5)°, V = 1672.6(12) ų, Z = 4. In the crystal structure, the molecular species are linked by intermolecular N-H...N hydrogen bonds into onedimensional chains.     

One-dimensional coordination polymers generated from an oxadiazole-containing N,N′-bipyridine-type ligand and inorganic salts

Three new one-dimensional coordination polymers have been prepared using Hg(II), Ag(I) and Zn(II) inorganic salts in combination with 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L6). The compounds were characterized by single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In the solid state, compounds 1 and 3 (1: monoclinic, P2₁/n, a=5.5373(3) Å, b=16.7839(9) Å, c=16.8120(9) Å, β=92.8610(10)°, V=1560.52(15) ų, Z=4; 3: monoclinic, P2₁/n, a=7.2958(4) Å, b=11.7214(6) Å, c=16.3979(9) Å, β=101.1150(10)°, V=1375.99(13) Å³, Z=4) feature novel one-dimensional helical chain motif. Compound 2, however, (2: monoclinic, P2₁/c, a=5.5506(4) Å, b=16.5895(12) Å, c=16.6871(11) Å, β=95.424(2)°, V=1529.70(19) ų, Z=4) exhibits one-dimensional zigzag chain motif, which result from the different conformations adopted by the L6 ligand and also the different metal coordination geometry. The luminescent properties of three new compounds were investigated in the solid state.     

Novel inorganic ring systems. XL: A dimeric cycloalumadisiladiazane

The first cycloalumadisiladiazane (F1) has been prepared by reacting dilithiated 1,2-bis(methylamino)tetramethyldisilane with AlCl₃ at ?80°C. The compound has been characterized by elemental analysis,¹H NMR, mass spectroscopy and single crystal X-ray diffraction. Crystals belong to the orthorhombic space group Pbca witha=8.3506 (4),b=16.1056 (8),c=19.1186 (6) Å,Z=4 andd _calc=1.22 g/cm³. The structure was refined to a conventionalR value of 0.030 using 1 810 counter-measured, observed reflections. The crystal contains discrete nitrogen bridged dimeric molecules possessing crystallographic \(\bar 1\) symmetry. Both NMR and mass spectral data indicate that this structure persists in solution and in the gas phase.     

Synthesis and crystal structure of diferrocenylmethoxyethylamine

The reaction of diethanolamine with diferrocenylmethyl carbonium (2) that was generated by diferrocenylmethanol (1) treated with BF₃ in CH₂Cl₂ provided the synthesis of title compound diferrocenylmethoxyethylamine (3). The structure of 3 was determined by the X-ray diffraction (XRD) with crystal data: monoclinic P2₁/n space group and a=5.8419(14) Å, b=13.572(3) Å, c=23.839(6) Å, α=90°, β=91.827(5)°, γ=90°, V=1889.2(8) Å³, Z=4, D _c =1.558 mg·m^?3, μ=1.548 mm^?1, F(000)=920. The intra- and inter-molecular H bonding modes in 3 were demonstrated both in molecular crystal structure and IR spectral characterization.     

A new 3D supramolecular Zn(II) compound: Crystal structure and important role in treatment of pulpitis

An innovative thermostable 2-D layered Zn(II) compound, chemical terms are written as [Zn(3-pysa)₂(H₂O)₂]_n (1, 3-Hpysa = 3-pyridinesulfonic acid), has been generated from the solvothermal reactions of 3-Hpysa and Zn(NO₃)₂·6H₂O. Its single crystal analysis was implemented via the single crystal X-ray diffraction analysis together with the powder X-ray diffraction, elemental analysis and thermogravimetric analysis. The crystal framework is of monoclinic P2₁/n space group and its crystal cell figures: a = 7.7499(5), b = 10.9923(6), c = 8.3430(5) Å, α = 90, β = 96.924(6), γ = 90°, V = 705.55(7) ų, Z = 4. The 2D layers were finally combined to a 3-D supramolecular conformation through intermolecular H-bonds existing between coordinated H₂O molecules and sulfonate oxygen atoms from adjacent layer. Its practical role in pulpitis treatment was estimated and the relevant mechanism was studied in the meantime.     

Synthesis and crystal structure of (NH<Subscript>4</Subscript>)(CN<Subscript>3</Subscript>H<Subscript>6</Subscript>)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of (NH₄)(CN₃H₆)[UO₂(SeO₃)₂] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) Å, b = 9.4234(3) Å, c = 9.5408(3) Å, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P ₁, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO₂(SeO₃)₂]^2? chains of the crystal-chemical group AB²B₁₁ (A = UO ₂ ²⁺ , B₂= SeO₃ ^2?, B₁₁= SeO₃ ^2?) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.