Crystal and molecular structures of 1-(2-methyloxycarbonylo-propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol hydrochloride (1) (C18H24NO4Cl) and 1-(2-methylcarbamoylpropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C18H24N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol, are reported in this paper. The space groups and unit-cell parameters are: compound1 (C₁₈H₂₄NO₄Cl), monoclinic,P2₁,a=7.215(1),b=8.591(1),c=15.017(1)Å,=95.64(1)°; compound2 (C₁₈H₂₄N₂O₃), monoclinic,P2₁/c,a=10.218(3),b=21.616(5),c=8.124(2)Å,=101.28(2)°. The structures were solved with direct methods and refined by full-matrix least-squares techniques toR indices of 0.036 and 0.066, respectively. The molecule of compound1 has an extended external chain, and thus its structure is linear, whereas the molecule of compound2 is compact, and its external chain is twisted in a characteristic way, as is the case of peptides.     

Crystal and molecular structures of 1-(2-carboxypropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (1) (C17H21NO4) and 1-(2-carbamoyl propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C17H22N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol containing 2-methylalanine fragment are described in this paper. The space groups and unit-cell parameters are: compound1 (C₁₇H₂₁NO₄): monoclinic, space groupP2₁/n,a=5.787(1),b=18.703(4),c=23.526(5)Å,=96.49(2)°; compound2 (C₁₇H₂₂N₂O₃): triclinic, space groupP¯1,a=8.321(1),b=10.121(1),c=10.368(1)Å,=109.49(1)°,=90.49(1)°, =103.48(1)°. The structures were solved by direct methods and refined with full matrix least-squares techniques toR indices of 0.055 and 0.049, respectively. The molecules of compound1 exist in the crystal as dual ions. The molecules of compound2 are compact and their external chain is twisted in a characteristic way (similar to that found in peptides).     

Crystal and molecular structures of 1-(2-ethyloxycarbonylo propan-2-ylamino)-3-(1-napthyloxy) propan-2-ol-hydrochloride (1) (C19H26NO4Cl) and 1-(2-isopropyloxycarbonylo-propan-2-ylamino)-3-(1-napthyloxy) propan-2-ol hydrochloride (2) (C20H28N04Cl)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol, are shown in this paper. The space groups and unit-cell parameters are: compound1 (C₁₉H₂₆NO₄Cl): triclinic, space groupP1,a=6.420(1),b=10.161(1),c=15.823(1) Å,=82.47(1),=84.16(1), =77.55(1)°; compound 2 (C₂₀H₂₈NO₄Cl): monoclinic, space groupP2₁/c,a=6.460(1),b=33.285(2),c=10.120(1) Å,=104.83(1)°. The structures were solved by direct methods and refined with full-matrix least-squares techniques toR indices of 0.055 and 0.048, respectively. The –CH(OH)-CH₂-NH-sections of the side chains show the conformation approximate togauche.     

Crystal and molecular structure of 1-(2-isopropylcarbamoylpropan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol (C20H28N2O3)

The crystal structure of the title compound has been determined with three-dimensional MoK X-ray diffraction data. The space group and unit-cell parameters are:P2₁/c,a=8.610(3) Å,b=13.516(5) Å,c=16.818(5) Å,=94.95(3)° andV=1950.0(7) ų. The structure was solved by direct methods, and refined by full-matrix least-squares techniques toR=0.0608 andR _w=0.0648. The compound is a derivative of the popular-adrenolytic propranolol, and in the propanol part of the side chain shows the typicalgauche conformation.     

Crystal structures of baclofen analogs: 3-thienyl- and 3-furylaminobutyric acids

X-ray crystal structures of 4-amino-3-(2-thienyl) butyric acid (compound1), 4-amino-3-(4-bromo-2-thienyl) butyric acid (compound2), and 4-amino-3-(5-methyl-2-furyl) butyric acid (compound3) are reported. Space groups and unit/cell parameters are: compound1, monoclinic,P2₁ c,a=13.288(3),b=5.231(1),c=12.388(2)Å,=92.3(1)°; compound2, monoclinic,P2₁/c,a=12.610(7),b=5.156(1),c=15.814(8)Å,=101.8(1)°; compound3, orthorhombic, Pccn,a=11.461(1),b=25.284(2),c=6.977(1)Å. FinalR indices are: compound1, 0.057; compound2, 0.069; compound3, 0.060. Conformations of their -aminobutyric chains are compared with the one of -amino--(p-chlorophenyl)-butyric acid (baclofen, compound4). Two different types of conformations are observed, i.e., conformations (i) with folding (compound3) or (ii) without folding (compounds1,2, and4) of the ammonium group toward the heteroaromatic or aromatic ring. However, distances between ionized groups are constant.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

Isolation and crystal structures of triethylenediamine-hydroquinone (1/1) and triethylenediamine-phenol (1/2)

Two crystalline adducts of triethylenediamine with hydroquinone [N(CH₂CH₂)₃N·C₆H₄(OH)₂,I] and phenol [N(CH₂CH₂)₃N·2C₆H₅OH,II] have been isolated and characterized by X-ray analysis. ComplexI crystallizes in the monoclinic space groupC2/c, witha=11.944(2),b=9.491(2),c=11.986(2) Å,=121.70(1)°, andZ=4. Both molecular components occupy sites of symmetry 2, and are linked alternately by N H-O hydrogen bonds to form infinite zigzag chains. Crystals ofII are also monoclinic, with space groupP2₁/c,a=12.987(2),b=6.376(1),c=21.350(3) Å,=106.94(1)°, andZ=4. The structure is composed of discrete hydrogen-bonded molecular aggregates corresponding to the stoichiometric formula. The triethylenediamine moieties in both adducts closely approximate to the idealizedD ₃ h conformation. The structures have been refined toR values of 0.097 (I) and 0.092 (II) using, respectively, 479 and 1580 observed MoK data.     

Crystal and molecular structure of 1-phenyl-3-(2-hydroxyphenylamino)-2-buten-1-one,C16H15NO2

Orange, yellow, and colorless crystals were obtained for the title compound. The orange crystals are triclinic, space groupP¯1,a=9.181(2),b=10.734(2),c=15.245(3) Å,=73.06(2),=79.21(2), =67.83(2)°,V=1325.9(5) ų,Z=4. Two different symmetry-independent molecules (moleculeA andB) were determined in the crystal unit. The conformation ofA is stabilized by an intramolecular H bond from the amino NH to the keto and phenolic O atoms [1.89(2) and 2.38(2) Å, respectively]. The conformation ofB is stabilized by only one intramolecular H bond, from the amino NH to the keto O atom [1.925(2) Å]. The colorless crystals (moleculeC) are monoclinic, space groupP2₁/n,a=11.883(3),b=11.004(3),c=10.053(3) Å,=95.93(3)°,V=1307.5(6) ų,Z=4. This conformation is stabilized by one intramolecular H bond, the same as in B, with N-HO, 1.84(3) Å. An intermolecular H bond is observed forA,B, and C, O-HO, 2.634(2), 2.640(2), and 2.697(2) Å, respectively. The yellow crystals are adducts with ethanol (¹H NMR, infrared and GC measurements).     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

Synthesis and X-ray analysis of 1-((1S)-phenylethyl)-azetidine-(2R)-piperidinamide

The crystal and molecular structure of a new azetidine-2-carboxylic amide derivative is described. The structure was solved by direct methods and refined by least squares methods toR1=0.0393 for 4264 reflections (withI>2(I)) The structure consists of two independent molecules which are chemically the same with slight differences in geometry. Crystal data: C₁₇H₂₄N₂O, monoclinic, space groupP2₁,a=8.3782(4),b=20.0342(13),c=9.7769(8) Å, =109.687(6)°,V=1545.1(2)ų,Z=4.     

Crystal structures of anhydro-bases of 1- and 2-(ethoxycarbonylmethylo)-4-hydroxycinnolinium hydroxides

C₁₂H₁₂N₂O₃,M _r=232.24. (1): C2/c,Z=8,a=14.658(1),b=4.9375(4),c=31.859(4) Å, =91.710(6)°. (2): P2₁/c,Z=4,a=11.422(2),b=4.8864(2),c=21.176(3)Å, =103.29(3)°. The study confirms significant contribution of quinoid diazine ring form in anhydrobase of 1-substituted 4-hydroxycinnolinium hydroxides. The phenomenon corresponds with a negative net charge at formerly positively charged N(1) atom, with fewer hydrogen contacts of less negatively charged O(4) and with increased stacking in 1-substituted derivative, in comparison with 2-substituted structure.     

Synthesis, spectroscopy, and X-ray structures of fac-(CO)3(dppe)MnSC(S)H, fac-(CO)3(dppe)ReSC(S)H, fac-(CO)3(dppp)ReSC(S)H, and fac-(CO)3(dppb)ReSC(S)H

The monodentate dithioformato complexes, fac-(CO)₃(dppe)MnSC(S)H (1), fac- (CO)₃(dppe)ReSC(S)H (2), fac-(CO)₃(dppp)ReSC(S)H (3), and fac-(CO)₃ (dppb)ReSC(S)H (4), where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane, were synthesized from the treatment of the corresponding hydrides, fac-(CO)₃ (P-P)MSC(S)H with CS₂. Compounds 1–4 crystallize in the monoclinic crystal system: for 1, space group = P2₁/c, a = 15.3139(3) Å, b = 9.7297(4) Å, c = 19.0991(6) Å, = 105.928(1), V = 2736.5 ų, Z = 4; for 2, space group = P2₁/c, a = 15.6395(8) Å, b = 9.8182(5) Å, c = 19.4153(11) Å, = 106.741(1), V = 2854.9(3) ų, Z = 4; for 3, space group = P2₁/n, a = 11.3570(10) Å, b = 19.465(2) Å, c = 15.5702(14) Å, = 104.776(2), V = 3328.3(5) ų, Z = 4; and for 4, space group = C2/c, a = 32.078(2) Å, b = 10.4741(6) Å, c = 19.0608(9) Å, = 94.315(2), V = 6386.1(6) ų, Z = 8.     

Steroids and related studies. Part 60. Crystal and molecular structures of 17β-(2-hydroxyethyl)-3β-and 3α-pyrrolidino-17a-aza-D-homo-5-androstenes: HS-625 form 1, (3β-pyrrolidino) and HS-625 form 2 (mixed-3α and -3β-pyrrolidino epimers)

The crystal structures of two forms of 17-(2-hydroxyethyl)-3-pyrrolidino-17a-aza-D-homo-5-androstene (HS-625) are reported. In HS-625 (aqueous solvate) form 1, moleculeA, and HS-625 (anhydride) form 2, moleculeB, the pyrrolidine group is 3- substituted, while in HS-625 (anhydride) form 2, moleculeC has its pyrrolidine ring -substituted. HS-625 form 1 is orthorhombic, space groupP2₁2₁2₁, witha=7.089(4),b=11.502(6),c=28.975(16) Å,Z=4; form 2 is triclinic, space groupP1, witha=14.013(8),b=12.572(6),c=6.688(4) Å, =95.187(20), =103.491(21); =86.210(20)°,Z=2. MoleculesA andB have similar geometry, differences in moleculeC being related to strain caused by the unusual 3- ring substituent which also produces a pronounced kink in the backbone of the molecule. An unusual feature of the analysis of form 1 is the location of the water hydrogens in the difference electron density well above background. None of the OH hydrogens was located. Both structures are hydrogen bonded, but the pyrrolidine nitrogen N(31) in moleculeC is heavily congested and is unable to act as an acceptor. The hydroxyethyl side chain, important for activity, has a different conformation in the three molecules (t,g, t,-g, andt,t respectively).     

Crystal and molecular structure of [rac-1S,2S,-3S,4R]methyl 2-benzoyl-3,4-dimethyl-4-phenylcyclobutane-1-carboxylate,C21H22O3

The structure of the title compound C₂₁H₂₂O₃, was determined by X-rays.Minr=322.4, monoclinic, space groupP2₁/a,a=11.960(2),b=14.275(3),c=10.858(2) Å,=103.20(2)°,V _c =1804.8 ų,Z=4,D _x =1.223 Mg m^–3. CuK radiation (graphite crystal monochromator,=1.54184 Å),(CuK)=6.53 cm^–1,F(000)=688, T=290 K. Final conventionalR factor=0.050,R _w =0.069 for 1679 unique reflections and 284 variables. The structure was solved usingMultan.     

Crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF2(C16H13O3)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C16H13O3)2]

The crystal structures of difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]boron(III), [BF₂(C₁₆H₁₃O₃)], and bis[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II), [Cu(C₁₆H₁₃O₃)₂], have been determined by single-crystal X-ray diffraction methods. The structures were solved by direct methods and electron density calculations and were refined by the full-matrix least-squares method. Difluoro[2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato]-boron(III) crystallizes as yellow rhombs in the monoclinic space groupP2₁/c witha=11.429(3),b=11.364(4),c=11.412(4) Å,=92.19(2)°,V=1481.0(8) ų andZ=4. A total of 2754 unique reflections were collected. Of these 1342 were considered observed [I>3(I)] leading to a finalR-value of 0.045. Boron is tetrahedrally coordinated to the two fluorine atoms and to two oxygen atoms of the bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligand, C₁₆H₁₃O ₃ ^– . Average bond distances: C-C (aromatic) 1.378(10) Å, B-O 1.473(7) Å and B-F 1.343(4) Å. bis[2-(4-Methoxyphenyl)-3-oxo-3-phenylpropanalato]copper(II) crystallizes as dark yellow-green plates in the monoclinic space groupC2/c witha=23.410(7),b=13.856(3),c=8.039(3) Å,=101.79(2)°,V=2553(1) ų andZ=4. Of the unique set of 3076 scanned reflections 2401 hadI>3(I) for whichR became 0.040. Copper is coordinated to four oxygen atoms, two from each of the two bidentate 2-(4-methoxyphenyl)-3-oxo-3-phenylpropanalato ligands, in a distorted square planar manner. The molecule hasC ₂ symmetry. Average bond distances: C-C (aromatic) 1.383(6) Å and Cu-O 1.896(8) Å. The crystals of both compounds consist of monomeric molecular complexes held together by van der Waals forces.     

Crystal and molecular structure of pyridinium di-μ-oxo-bis(oxodichloroaquomolybdate(V)) monohydrate, (pyh)2[Mo2O4Cl4(H2O)2] · H2O

The crystal and molecular structure of pyridinium di--oxo-bis(oxodichloroaquomolybdate(V)) monohydrate has been determined from MoK diffractometer data. The compound crystallizes in the monoclinic space groupP2 ₁/m witha = 7.544(1),b= 17.046(3),c = 7.894(1) Å, = 106.00(1) ° andZ = 2. The structure was solved by the heavy-atom technique and refined by full-matrix least-squares method toR = 0.046, using 1800 reflections for whichF> 4(F). Molybdenum atoms are linked by the double oxygen bridge with an Mo—O distance of 1.943(4) Å and an Mo—O—Mo angle of 83.4(2) °. The Mo—Mo distance is 2.584(1) Å, indicating direct Mo—Mo bonding. The pyridinium and [Mo₂O₄C1₄(H₂O)₂]^2- ions are hydrogen bonded through N—H ... O bonds. The N ... O contact is 2.656(8) Å.     

Crystal and molecular structure of 1-methyl-2,3,5,6-tetraphenylpiperidin-4-ol,C30H29NO

The structure of the the title compound, C₃₀H₂₉NO, was determined by X-rays.M _r =419.57, triclinic, space groupP1,a=5.8922(12),b=8.5855(11),c=12.2216(20) Å,=78.145(12)°,=79.181(15)°, =76.108(14)°,V _c =581.1(1) ų,Z=1,D _x =1.199 Mg m^–3. CuK radiation (graphite crystal monochromator, =1.54184 Å),(CuK)=5.17 cm^–1,T=290K. Final conventionalR-factor=0.039,R _w =0.042 for 2795 observed reflections and 377 variables. The structure was solved usingMultan andDirdif. With a view to determining the conformational preference of the piperidine ring when it is highly sustituted with a bulky group like the phenyl group, the present X-ray investigation was undertaken.     

Crystal and molecular structures of 5,7-dimethyl-1,8-naphthyridine-2-ol (=LH) and of its mercury (II) complex HgL2 and synthesis of some lanthanide/HgL2 heterometallic complexes

The crystal structures of the title compounds have been determined by single crystal diffraction methods. Crystals of 5,7-dimethyl-1,8-naphthyridine-2-ol (1) are monoclinic, space groupP2₁/n witha=7.336(2),b=8.989(2),c=13.125(3)Å,=95.72(3)°,V=861.2(4)ų,Z=4,D _c =1.34 g cm^–3, finalR=0.052. The molecules are linked in pairs by two N-HO hydrogen bonds, and these dimers are stacked in a discontinuous, stepped fashion. Crystals of HgL₂ (2) are monoclinic space groupP2₁,/c witha=4.044(2),b=12.147(2),c=18.093(5)Å,=93.32(2)°,V=887.3(4)ų,Z=2,D _c =2.05 g cm^–3, finalR=0.051. In2 the mercury binds to N(1) to form a linear N-Hg-N coordination geometry, and the HgL₂ molecules form a continuous stacked structure. The syntheses of the compounds ML₄(NO₃)₃·H₂O (M=Nd, Gd, and Er), PrHg₂L₄(NO₃)₃, andM ₂Hg₃L₆(NO₃)₆ (M=Gd, Er) are also reported.     

Crystal structures of three 1-arylpropane-1,2-diol 2-aryl ether derivatives and the acetate of 2,6-dimethoxy-4-(1-(E)-propenyl)phenol

The crystal structures ofthreo-2-[2,6-dimethoxy-4-(1-(Z)-propenyl)phenoxy]-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanol (7b),threo-2-(2,6-dimethoxy-4-propylphenoxy)-1-(3,4-5-trimethoxyphenyl)-1-propanol (7c), the diacetate oferythro-2-[2,6-dimethoxy-4-(1-(Z)-propenyl)phenoxy]-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanol (8d) and the acetate of 2,6-dimethoxy-4-(1-(E)-propenyl)phenol (9) have been determined by single-crystal X-ray diffraction methods;7b,7c, and8d are structurally closely related to a class of optically-active neolignans of 1-arylpropane-1,2-diol 2-aryl ether type occurring in plant extracts. The reflection intensities were recorded at room temperature for7b and8d, at -140°C for7c and at -120°C for9. Compound7b crystallized as needles in the orthorhombic space groupPna2₁ witha=27.055(3),b=11.850(8),c=6.717(4)Å andZ=4.R became 0.041 for 1792 observed [I>3(I)] reflections used in the refinement of the structure. Compound7c crystallized as prisms in the monoclinic space groupP2₁/a witha=12.565(4),b=13.96(1),c=12.846(7)Å,=93.86(3)° andZ=4. The refinement gaveR=0.051 for 2101 observed [I>3(I)], unique reflections. Compound8d crystallized as prisms in the monoclinic space groupP2₁/n witha=13.182(4),b=8.518(5),c=23.322(5)Å,=106.12(2)° andZ=4. The finalR-valuebecame 0.042 for 2131 observed [I>3(I)], unique reflections. Compound9 crystallized as prisms in the orthorhombic space groupPca2₁ witha=18.216(4),b=9.483(3),c=7.416(2)Å andZ=4. TheR-value became 0.038 for 1502 observed [I>3(I)], unique reflections. The crystals of7b are stabilized by moderately strong hydrogen bonds. All the 1-arylpropane-1,2-diol 2-aryl ethers examined adopted conformations in which the aromatic groups tend to be as remote as possible. Observed double bond lengths in the propenyl groups of the compounds examined (1.30 Å) deviate significantly from the expected value (1.34 Å). The cause of this discrepancy is discussed.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.