Crystal and molecular structures of the 4-(1H)-pyridone (=L) lanthanide complexes {[GdL(NO3)3(H2O)]·CH3OH}2 and [DyL4(NO3)2](NO3) and of L2HNO3

The crystal structures of the title compounds have been determined by single crystal diffraction methods. Crystals of the dysprosium compound are monoclinic, space groupP2₁/c witha=14.133(4),b=13.438(5),c=14.401 (4)Å,=103.98(2)°,V=2654(1)ų,Z=4,D _c =1.82 g cm^–3, finalR=0.035. The Dy atom is eight-coordinate with a distorted dodecahedral coordination geometry involving two bidentate nitrate groups and four pyridone oxygen atoms. An erbium complex with analogous stoichiometry was also prepared but not structurally characterized. Crystals of the Gd compound are monoclinic, space groupP2₁/n, witha=11.226(2),b=9.075(2),c=16.737(3)Å,=93.88(3)°,V=1701(1)ų,Z=2,D _c =1.91 g cm^–3, finalR=0.042. Each Gd atom is bonded to one pyridone oxygen atom, a water molecule and three bidentate nitrate groups. An oxygen atom of one of the bidentate nitrates additionally serves to bridge pairs of Gd atoms so as to form a dinuclear complex in which each Gd atom is nine-coordinate with a tricapped trigonal prismatic geometry. Crystals of L₂HNO₃ are monoclinic, space groupI2/a witha=12.479(4),b=6.535(2),c=14.297(6)Å,=96.07(3)°,V=1159(1)ų,Z=4,D _c =1.45 g cm^–3, finalR=0.057. The pyridones are linked in pairs by very short (2.44 Å) symmetrical OHO hydrogen bonds. Each pair is further linked via a nitrate ion by means of N-HO(nitrate)H-N hydrogen bonds, so as to form an extended chevron-like pyridone-pyridone-nitrate-pyridone-pyridone array. Adjacent chains are linked via weak C-HO(NO₃) interactions.     

Preparation,spectral studies and X-ray crystal structure of 1,3,5-triphenyl-1,5-pentanedione,C23H20O2

1,3,5-triphenyl-1,5-pentanedione, C₂₃H₂₀O₂, has been prepared and characterized by spectroscopic methods and single crystal X-ray analysis. Crystals are monoclinic, space groupP2₁/n, a=28.124(4),b=5.997(1),c=10.434(1)Å, -98.42(1)Å,Z=4. The structure has been refined to a finalR-value of 0.040 for 1625 reflections withF _o>3(F _o). The compound contains the two carbonyl groups in a mutuallycis arrangement.     

Structure of 9-oxa-2,3-(4′-methoxy)-benzo bicyclo[4,3,0]non-1(6)-ene-7,8-dione: C13H10O4

The crystal and molecular structure of the title compound: C₁₃H₁₀O₄,M _r=230.22, determined by single crystal X-ray diffraction is reported. Crystals are monoclinic, space groupP2_l/c,a=3.991(3),b=21.381(4),c=12.289(4)Å,b=91.15(1)°,V=1048(1)Å₃,z=4,D _x=1.46Mg m^–3, (MoK)=0.7107 Å,m=0.87 mm^–1,F(000)=480,T=298 K. The structure was solved by direct methods and the finalR value is 0.071 (wR=0.055) for 795 independent observed reflections. The cyclohexadienic moiety of the molecule adopt a twist conformation.     

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 and molecular structure of (Z)-2-(1,3-benzothiazol-2-yl)-2-(6,7,8,9-tetrahydro-5H-benzocyclohepten-5-ylidene)ethanonitrile

The title compound C₂₀H₁₆N₂S is crystallized in the monoclinic space groupP2₁/c with cell parametersa=10.663(4),b=17.585(9),c=9.418(5)Å,=115.23°(4),V=1598(3)ų,Z=4. The structure was refined by full-matrix least-squares methods using X-ray data set collected at room temperature. A finalR _F =0.033 andR _w =0.048 for 2225 unique reflections withI> 3(I) and 272 variables was obtained. The X-ray crystallographic study establishes theZ stereochemistry of the title compound.     

Crystal and molecular structure of 2,2-diphenyl-5-dichloromethylene-3-oxazoline-4-ethylcarboxylate

The structure of an oxazoline compound: 2,2-diphenyl-5-dichloromethylene-3-oxazoline-4-ethylcarboxylate has been established uniquely by X-ray crystallography. C₁₉H₁₅Cl₂NO₃ is monoclinic, space groupP2₁/n, with the cell dimensionsa=8.170(1),b=23.559(2),c=9.962(1) Å,=105.53(1)°,V=1847.5(3) ų,Z=4,M _r=376.2,D _x=1.35,D _o=1.36 g cm^–3,F(000)=776,T=293 K,=33.2 cm^–1, finalR=0.062 for 2321 observed reflections. Two phenyl rings make a dihedral angle of 83.3(4)° and are equally inclined to oxazoline ring plane. The ethylcarboxylate group is planar and is at an angle of 76.1(4)° with respect to oxazoline ring plane.N.C.L. Communication No. 5360.     

X-ray crystal structure of (6-n-propyl-2-thiouracilato)(triethylphosphine)gold(I)

The crystal structure of the title compound [Et₃PAu(PTU)] is reported. There are two molecules in the asymmetric unit and each of the independent Au atoms exists in a linear geometry defined by a P atom of the phosphine ligand and a thiolate S atom derived from the thionucleobase; molecule 1: Au-P 2.255(5), Au-S 2.314(5)Å, P-Au-S 176.9(2)° and molecule 2: Au-P 2.249(5), Au-S 2.328(4)Å and P-Au-S 175.0(2)°. The lattice features weak AuAu contacts of 3.486(1)Å and hydrogen bonding interactions involving theOxo and N-H groups. Crystals are monoclinic, space groupP2₁/c with unit cell dimensions:a=21.445(2),b=8.931(2),c=17.956(3)Å;=96.09(1)° andZ=8. The structure was refined by a full-matrix least-squares procedure to finalR=0.053 using 2875 reflections withI3.0(I).     

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.     

Synthesis and crystal structure of [(η5-C9H11)TiCl(μ-0)]4

The tetramer, prepared by passing Cl₂ gas into a solution of [(⁵-C₉H₁₁)₂-TiCl₂] in CCl₄, crystallizes in the tetragonal space groupP¯42₁ c (No. 114). The unit cell parameters area=b=15.704(7),c=7.776(4) Å, and _cal=1.52g cm^–1 forZ=2 (tetramers). Full-matrix least-squares refinement gave a finalR value of 0.032 for 554 observed reflections. The molecule lies on a crystallographic ¯4 site. Both independent Ti-O distances are equal, 1.802(5) and 1.809(5) Å, and the Ti-Cl length is 2.281(3) Å. The five Ti-C() distances show the expected variation associated with an indenyl moiety: 2.310(9) to 2.437(9) Å.     

The crystal structure of LiBr·(CH3OCH2CH2OCH3)2

The crystal structure of LiBr·(CH₃OCH₂CH₂OCH₃)₂ has been determined from counter data and refined by full-matrix least-squares techniques. The crystals belong to the monoclinic space groupC2/c (C _2h ⁶ , No. 15) witha=13.518(4),b=8.007(3),c=12.252(4) Å,=98.08(2)°, andD _calc=1.35 gcm^–3 forZ=4. The finalR value for 489 observed reflections is 0.033. The lithium and bromine atoms lie on a crystallographic two-fold axis. The structure consists of discrete LiBr·(CH₃OCH₂CH₂OCH₃)₂ units. The Li-Br separation is 2.57(1) Å. The two DME molecules are coordinated to the lithium atom through the four oxygen atoms at an average LiO separation of 2.09(3) Å.     

Structural and spectral study of 7-bromo-1,3-dihydro-5-(2-pyridyl)-2H-1,4-benzodiazepin-2-one (bromazepam) platinum(II) dichloride bisdimethylsulfoxide

The synthesis and crystal and molecular structure of the title compound are reported. It belongs to the monoclinic space groupC2/c, witha=17.889(2),b=13.511(1),c=19.912(2) Å,=99.841(4)°, andZ=8. The structure was refined to a finalR of 2.77% (R _w =2.88%) for 3617 observed reflections. Vibrational spectra are recorded and discussed.     

Crystal structure of bis-(rhodanine)copper(I) iodide,C6H6CuIN2O2S4

The structure of the polymeric rhodanine compound, C₆H₆CuIN₂O₂S₄, was determined by X-rays.M _r =456.8, monoclinic, space groupP2₁/c,a=4.1947(7),b=17.6999(12),c=17.1048(8) Å,=96.15(1)°,V _c =1262.6 ų,Z=4,D _c =2.40Mg m^–3, CuK radiation (graphite crystal monochromator, =1.54056 Å),(CuK)=278.9 cm^s-1,F(000)=872,T=290 K. Final conventionalR-factor=0.029, andR _w =0.044 for 2384 unique reflections and 153 variables. The structure was solved using Patterson methods andDirdif, and refined by full-matrix least-squares methods. The compound forms zigzag chains alonga. The copper atom is in trigonal pyramidal coordination, with two sulfur atoms of the thiocarbonyl group and two bridging iodine atoms. The copper-sulfur distances are 2.278(1) and 2.299(1) Å, and the copper-iodine distances are 2.657(1) and 2.814(1) Å.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Crystal structure of (E)-5-hydroxypyrrolizidin-3-one and (Z)-5-thioketalpyrrolizidin-3-one

The crystal structures of (E)-5-hydroxypyrrolizidin-3-one (2) and (Z)-5-thioketalpyrrolizidin-3-one (3) have been determined by single-crystal x-ray diffraction techniques and refined by full-matrix least squares. Molecule2 crystallizes in the monoclinic space groupP2₁/a(No. 14) witha=7.887(3) Å,b=9.788(5) Å,c=9.316(4) Å,=100.6(1), andZ=4. Molecule 3 crystallizes in the monoclinic space groupP2₁/c witha=12.947(14) Å,b=10.553(14) Å,c=9.629(14) Å,=101.4(1), andZ=4. The calculated density for both molecules is 1.33 g cm^–1. FinalR-factors were 5.1% for2 and 8.59% for3. The x-ray results showed that a change in configuration occurred in the reaction going from2 to3.     

Metal complexes of chiral pyridine ligands. X-ray structure of nitratobis {2-(2S)-2-pyrrolidinyl]pyridine} copper (II) nitrate

Cobalt(II), nickel(II), and copper(II) complexes of 2-[(2S)-2-pyrrolidinyllpyridine (L) have been synthesized and characterized. The crystal structure of the complex [Cu(L)₂(NO₃)]NO₃ has been determined by X-ray diffraction. Crystals are monoclinic, space groupP2+, witha=10.766(3).b=7.525(2),c=13.447(4) Å. =104.64(2)°. and Z=2. The structure consists of [Cu(L)₂(NO₃)]⁺ cations and NO ₃ ^t- anions. The copper atom has a distorted trigonal bipyramidal coordination geometry with the two pyrrolidine nitrogens and one nitrate oxygen occupying the equatorial positions and the two pyridine nitrogens at the apices. The crystalline cohesion is ensured by a network of hydrogen bonds involving the pyrrolidine groups as donors and both coordinate and uncoordinate nitrates as acceptors.     

Crystal and molecular structure of 12(S)-acetoxy-4(S),8(R)-dimethyl-3-oxo-1(R)-5(S)-9(S)-2-oxatricyclo[4.4.7.01,9.3.4.8.01,5]tridecane

The structure of the title compound, a cyclic ether acetate lactone, has been established uniquely by X-ray crystallography. C₁₆H₂₄O₄ is orthorhombic, space groupP2₁2₁2₁, with the cell dimensionsa=7.524(2),b=10.686(2),c=19.472(2) Å,V=1565.6(4) ų,Z=4,M _r=280.4,D _x=1.19 g cm^–3,D _o=1.20 g cm^–3,F(000)=608,T=293 K, finalR=0.050. The two cyclohexane ring junction iscis while the lactone ring junction istrans. Both the cyclohexane rings have the chair conformation and the -lactone ring has an envelope conformation with C(7) being at the tip of the flap. The acetoxy side chain is-equatorial. There is an intramolecular C-H---O interaction C(4)O(4)=2.666(4) Å.N. C. L. Communication No. 5064.     

Crystal structure and spectroscopic study of 2-[(2,6-dichlorophenyl)amino]phenylacetoxyacetic acid (Aceclofenac)

The crystal structure of the title compound has been determined. The crystals are monoclinic:P2₁ n(NO. 14),a=12.279(7),b=8.223(1),c=15.504(7)Å,=96.16(2)°,V _c =1556(2)ų,Z=4,D _x =1.511 g cm^–3,=(MoK)=0.71069 Å. The structure was solved by direct methods and refined with 1970 reflections to a finalR value of 0.057. Analytical, mass, spectral, and physicochemical data are also reported.     

Crystal and molecular structures of trans-bis(acetonitrile)bis(bipyridine)ruthenium(II) perchlorate and trans-diamminebis(bipyridine)ruthenium(II) perchlorate

The structures of trans-[(MeCN)₂(bpy)₂Ru](ClO₄)₂(I) andtrans-[(NH₃)₂(bpy)₂Ru](ClO₄)₂(II) have been determined by single crystal X-ray diffraction methods. (I) forms monoclinic crystals in the space groupP2₁/c witha=8.399(2),b=10.406(2),c=15.590(3) Å,=93.78(2)° andZ=2 atT=293 K. The final refinement gaveR=0.040 for 2448 reflections withF _o ² >3(F _o ² ). (II) crystallizes in the triclinic space groupP¯1 witha=1.702(1),b=8.439(2),c=10.525(2) Å,=107.56(2),=104.63(1), =100.89(2)° andZ=1 atT=293 K. Refinement using 1878 reflections withF _o ² >3(F _o ² ) produced a finalR value of 0.036. Both of these structures have the ruthenium atom located on a crystallographic inversion center. The bipyridine ligands in both structures are in the bowed conformation as a means of circumventing the steric problems associated with the trans arrangement of the bipyridine ligands. The Ru-N(monodentate) distance is longer for the ammonia complex (2.106(3) Å) than for the acetonitrile complex (2.008(4) Å); there are no significant differences in the distances and angles of the two Ru(bpy)₂ frameworks.     

Crystal structure of the orthorhombic basic copper nitrate,Cu2(OH)3NO3

The crystal structure of the orthorhombic copper salt Cu₂(OH)₃NO₃ (natural gerhardtite) has been determined from X-ray diffractometer data by means of three-dimensional Patterson and Fourier syntheses, and refined by difference Fourier syntheses and least-squares methods to a finalR index of 0.097 for 532 reflections. Crystals of Cu₂(OH)₃NO₃ are orthorhombic:a=6.087(2),b=13.813(4),c=5.597(2) Å,Z=4, space groupP2₁2₁2₁. The Cu atoms form deformed hexagonal pseudocells (010). Each Cu(1) ion is surrounded by an approximately square planar arrangement of four OH ions at 1.929, 1.952, 1.993 and 1.998 Å and by two O (of NO₃ ions) at 2.359 and 2.480 Å, completing a deformed coordination octahedron; each Cu(2) ion is similarly coordinated by four OH at 1.989, 1.997, 2.009 and 2.018 Å, one OH at 2.309 Å, and one O at 2.384 Å. The structure involves layers of such deformed octahedra, of theC6-type, linked together by hydrogen bonds through the NO₃ ions. Similarities to and differences from the structure of the monoclinic polymorphous form are discussed.     

Crystal and molecular structures of 1-(2-iso butylylcarbamoyl propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (1) (C21H31N2O3Cl) and 1-(2-isobutyloxycarbonylo propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (2) (C21H30NO4Cl)

This paper shows the crystal structures of two new-adrenergic antagonists, derivatives of propranolol, which were determined with three-dimensional x-ray diffraction data. The space groups and unit-cell parameters are: compound1 (C₂₁H₃₁N₂O₃Cl) monoclinic space groupP2₁/c,a=20.523(4),b=6.909(2),c=15.950(2) Å,=105.03(1)°; compound2 (C₂₁H₃₁NO₄Cl) monoclinic space groupP2₁/c,a=6.364(2),b=36.043(8),c=10.149(1) Å,=104.48(2)°. The structures were solved with direct methods, and refined with full-matrix least-squares techniques toR indices of 0.059 and 0.067, respectively. The-CH(OH)-CH₂-NH-sections of the side chains show the conformation approximate togauche.