Crystal structure of 2-{(R)-1-hydroxy-1-[(2S)-1-tritylaziridin-2-yl] methyl}acrylate and spectroscopic properties of the (R,S) and (S,S) stereoisomers

The crystal and molecular structure of 2-{(R)-1-Hydroxy-1-[(2S)-1-tritylaziridin-2-y1] methy1}acrylate is described. Crystal data: C₂₆H₂₅NO₃, orthorhombic, space group P2₁2₁2₁, a = 9.6954(5), b = 13.1458(5), c = 16.7885(7) Å, V = 2139.8(2) ų, Z = 4. The (R,S) diastereomer shows an intramolecular hydrogen bonding N···H—O under formation of a five-membered ring with N···O distance of 2.664 Å. IR, ¹H NMR and ¹³C NMR data are discussed. The ¹H NMR of the (R,S) diastereomer shows a singlet- whereas the (S,S) diastereomer exhibits a doublet-pattern for the hydroxyl proton.     

The crystal structures of p-halo-N-(p-cyanobenzylidene)aniline and p-cyano-N-(p-halobenzylidene)aniline (halo = bromo and chloro)

p-Bromo-N-(p-cyanobenzylidene)aniline is triclinic, has space group P , at 173 K, with a = 7.3892(15), b = 12.087(2), c = 7.0283(14) Å, = 105.24(2), = 98.11(2), = 98.89(2)°, Z = 2, V = 587.4(2) ų. p-Chloro-N-(p-cyanobenzylidene)aniline is triclinic, space group P , at 173 K, with a = 7.317(2), b = 12.165(3), c = 6.990(2) Å, = 104.02(2), = 100.96(2), = 100.76(2)°, Z = 2, V = 574.7(3) ų. p-Cyano-N-(p-bromobenzylidene)aniline is orthorhombic, has space group P2₁2₁2₁, at 173 K, with a = 10.333(3), b = 4.732(3), c = 23.526(5) Å, Z = 4, V = 1150.3(8) ų. p-Cyano-N-(p-chlorobenzylidene)aniline is orthorhombic, has space group P2₁2₁2₁, at 173 K, with a = 10.161(2), b = 4.713(2), c = 23.509(5) Å, Z = 4, V = 1125.8(4) ų. In the two cyanobenzylidene compounds there are chains of molecules held together by CN······X interactions. The chains form two-dimensional sheets similar to those in the iodo analog, but with a different stacking arrangement between the sheets. In the two halobenzylidene compounds there are no CN······X contacts; rather there are short X······X and C–H······NC contacts.     

Crystal and molecular structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II) thiocyanate

The crystal structure of 1-(2-aminoethyl)biguanide-isothiocyanato-copper(II)thiocyanate, [Cu(aebg)(NCS)] (SCN) (aebg = NH₂. CH₂. CH₂. N=C(NH₂). NH. C(NH). NH₂) has been determined and refined by Fourier methods using three-dimensional X-ray data collected on a Weissenberg automatic diffractometer. The unit cell parameters are:a = 11·41(2),b = 8·81(2),c = 7·45(2) Å; = 87·6° (2); = 67·2° (2); = 70·1° (2);Z = 2.Assuming space group P¯1, the structure was refined down toR = 8·5 %. The coordination around Cu is slightly distorted square planar and concerns three N atoms from the aebg ligand (Cu-N = 1·988(8), 2·019(7), 1·963(5) Å) and the terminal N of an isothiocyanate group (Cu-N = 1·941(5) Å). Two unsymmetrical, long interactions (Cu-N = 3·367(7) and 2·947(7) Å), with the N atoms belonging to two NCS groupstrans with respect to the coordination plane, complete the coordination to a distorted octahedron. In the aebg ligand the double bonds are localized on the C-N groups, whose nitrogen atoms coordinate to the metal.This work was carried out with the aid of financial support from the Consiglio Nazionale delle Ricerche, Roma.     

Crystal and molecular structure of triphenylphosphine (N,N-diethyldithiocarbamato)gold(I)

The crystal and molecular structure of triphenylphosphine (N,N-diethyldithio-carbamato) gold(I), (C₆H₅)₃PAuSSCN(C₂H₅)₂, has been determined by three-dimensional X-ray methods. The compound crystallizes in the monoclinic space groupP2₁/c witha = 13·547(1),b = 12·277(1),c = 14·013(1) Å, = 90·81(1) ° andZ = 4. Three-dimensional intensity data were collected on an automatic diffracto-meter. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·04 for 2318 non-zero observed reflexions.In this complex the diethyldithiocarbamate moiety acts as a monodentate ligand, the double-bond distance being 1·68(1) Å and the bond involving the sulphur atom that is coordinated to the gold atom being 1·75(1) Å. The gold atom is linearly coordinated, the angle being 175·7(1) ° and the and distances being 2·338(3) and 2·251(3) Å, respectively.     

Synthesis and crystal structures of two potential gem-di(pyrazolyl)cycloalkane ligands, 1,1-di(pyrazol-1-yl)cyclohexane [C6H10(C3N2H3)2] and 1,1-di(pyrazol-1-yl)cyclopentane [C5H8(C3N2H3)2]

The species 1,1-di(pyrazol-1-yl)cyclohexane, C₁₂H₁₆N₄, crystallizes in the monoclinic space group P2₁/c with a = 8.340(2), b = 14.281(5), c = 10.153(3) Å, = 106.86(2)°, and Z = 4. The cyclohexane moiety has the chair conformation. The congener, 1,1-di(pyrazol-1-yl)cyclopentane, C₁₁H₁₄N₄, while not isomorphous, also crystallizes in space group P2₁/c with a = 14.350(2), b = 6.776(1), c = 11.043(2) Å, = 100.68(1)°, and Z = 4. The cyclopentane ring has a conformation in which four carbon atoms are essentially coplanar, while the fifth (that with the two pyrazolyl substituents) lies 0.63 Å from this plane, resulting in a bend of 41.3° across the C(2)···C(5) vector. The hydrogen atoms in each structure were located directly and their coordinates refined.     

Stereochemistry of racemic hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) thiocyanate,C16H32N4Ni(SCN)2 · H2O

The diamagnetictrans-diene thiocyanate salt of the macrocyclic hexamethyl-1,4,8,11-tetraazacyclotetradecadienenickel(II) complex crystallizes in the triclinic system with unit cell dimensions:a = 7·334(4),b = 8·808(6),c = 21·04(2) Å; = 63·7(0·9), = 103·8(1·4), = 110·2(1·3) °; space groupP¯1;Z = 2. The positions of all 62 atoms of the formula unit C₁₆H₃₂N₄Ni(SCN)₂.H₂O have been determined and refined by least-squares methods toR= 0·071 for 3536 X-ray diffractometric reflections. The optical activity of the two amine groups yields a racemic isomer. The only local symmetry element of the macrocyclic complex is the twofold rotation axis with the N-H bonds oriented on the same side of the approximate ligand plane. Both the C(CH₃)₂ and the imine groups are in atrans-configuration in the ring. The space group ensures that the crystal is a racemate, containing equal numbers of both enantiomers. One of the (SCN)^– groups is at a distance Ni-S 3·28 Å, the other one is 4·65 Å. No rotational disorder of the CH₃ groups has been observed. The three C-H bonds of the CH₃ groups are in approximately antiprismatic orientations with respect to the three -bonds in the case of bonding to a C(sp³) atom. The average of the C(sp³)-C(sp²) bond lengths is 1·53 Å, and the mean value for the C(sp³)-C(sp²) bonds is 1·50 Å, with 3 = 0·03 to 0·04 Å. The distances N(sp²)-C(sp³) 1·47 Å and 1·48 Å are significantly longer than the bond lengths N(sp²)=C(sp²) of 1·28 and 1·30 Å.     

Crystal structure of hexahydro-cis-(1-H,4a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]thiazine

The crystal and molecular structure of hexahydro-cis-(1-H,4_a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]thiazine, (C₁₄H₁₈BrNS), has been determined from three-dimensional diffractometer data. The space group isI4₁/cd and the unit cell has dimensionsa = 22·906(4),b = 22·906(4),c = 10·646(2) Å withZ = 16. The structure has been refined to a residual of 0·065 using least-squares methods on 1235 independent non-zero reflexions.The molecular geometry and conformation of the bicyclic ring is discussed and compared with the related oxazine compound.     

Crystal structure and conformation of frentizole, [1-(6-methoxy-2-benzothiazolyl)-3-phenylurea, an antiviral agent and an immunosuppressive drug

Crystals of Frentizole (from ethanol/water) are monoclinic, space group P2₁/c, with a = 11.187(4), b = 7.392(2), c = 32.727(6) Å, = 92.77(2)°, Z = 8, D _o = 1.47 g/cm³, and D _c = 1.472 g/cm³. There are two independent molecules in the crystallographic asymmetric unit with very different conformations. In molecule A the urea group is in the plane of the benzothiazole ring (0.9°) whereas in molecule B the dihedral angle between them is 4.4°. The dihedral angle between the planes of the phenyl group and the benzothiazole ring are ±157° and ±12°, respectively, in the two molecules. The molecules are linked by a pair of N–H···N hydrogen bonds involving the urea nitrogen and two other N–H···N bonds involving the urea nitrogen and the nitrogen of the benzothiazole group.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

Crystal and molecular structure of bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C5H4NCONCN)2(OH2)

Bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C₅H₄NCONCN)₂(OH₂), has been prepared and its i.r. spectrum and crystal structure have been determined. The crystals are triclinic (P¯1):a = 11·45(1),b = 10·35(1),c = 7·48(1) Å, = 110·9(1), = 102·2(2), = 108·9(1)°,Z = 2. The X-ray analysis, carried out using three-dimensional Patterson, Fourier and least-squares methods (finalR = 5·7%), showed copper(II) to be pentacoordinated, with two organic ligands chelating through their pyridine [Cu-N = 1·997(4), 1·989(4) Å] and amide nitrogen atoms [Cu-N = 1·980(7), 2·006(6) Å], and with one water molecule at a distance [Cu-OH₂ = 2·335(4) Å] sensibly longer than the usual Cu-O(2·0 Å) coordinate bonds. The coordination polyhedron can be described either as a distorted tetrahedron formed by the nitrogen atoms with an extra position occupied by water or as a trigonal bipyramid having water and two nitrogen atoms in the equatorial plane. The packing determining interactions are the hydrogen bonds formed by water, and a long Cu...N (3·420 Å) contact between the metal and a nitrogen atom from an adjacent molecule.The authors are indebted to Prof. Immirzi who kindly supplied his computer programmes.     

Crystal structure of hexahydro-cis-(1-H,4a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]oxazine

The crystal and molecular structure of hexahydro-cis-(1-H,4a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]oxazine, (C₁₄H₁₈BrNO), has been determined from three-dimensional diffractometer data. The space group isP2₁/c; the unit cell has dimensionsa = 10·682(1),b = 21·606(2),c = 5·856(1) Å, = 90·0 ° (at 20 °C) and contains four molecules. The structure has been refined to a residual (R) of 0·056 using least-squares methods on 1240 independent non-zero reflexions.The molecular geometry and conformation of the bicyclic ring is discussed.     

Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)-gold(III) bis(1,2-dicyanoethene-1,2-dithiolato)aurate(III)

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)gold(III) bis(1,2-dicyanoethene-1,2-dithiolato)aurate(III), Au[S₂CN(C₄H₉)₂]₂Au[S₂C₂(CN)₂]₂, has been determined from a single-crystal X-ray diffraction study. The monoclinic cell, space groupP2₁,/c, witha = 9·930(3),b = 12·517(3),c = 15·632(3) Å and = 110·46(3) °, contains two formula units. Three-dimensional intensity data, up to = 35 ° were collected on an automatic diffractometer. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·04 for 1874 independent non-zero reflections. The structure consists of bis(di-n-butyldithiocarbamato)gold(III) cations and bis(l,2-dicyanoethene-l,2-dithiolato)aurate(III) anions. In both ions, the gold atom is in planar coordination with four sulphur atoms, the Au-S bond lengths being 2·333(4) and 2·337(4) Å in the cation and 2·312(4) and 2·306(5) Å in the anion.     

Crystal and molecular structure of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) aquodysprosium(III), Dy(thd)3H2O

The crystal structure of Dy(thd)₃H₂O has been solved by three-dimensional X-ray methods at room temperature. The space group isP¯1 and the cell dimensions area = 14·21(1),b = 14·88(2),c = 11·60(2) Å, = 99·76(3), = 109·91(1), = 114·08(1) °.Z = 2,D _m = l·24 andD _x = 1·238 gcm^–3, respectively. Full-matrix least-squares refinement of atomic and individual isotropic thermal parameters, using 3015 intensities obtained by counter methods, terminated with a conventionalR of 0·058. The oxygen polyhedron around dysprosium has pure seven-coordination geometry, the seventh ligand being the water molecule. The water is hydrogen bonded to two oxygen atoms of a centre of symmetry related formula unit so that two formula units are in fact held together by hydrogen bonds in a dimer.Supported by National Institute for Metallurgy, Johannesburg.     

Crystal and molecular structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV)

The crystal structure of bis-tetraphenylarsonium-tris-(cis-1,2-dicyano-1,2-ethylenedithiolato)Fe(IV), [(C₆H₅)₃As]₂Fe[S₂C₂(CN)₂]₃, has been determined using 3154 independent, non-zero reflexions collected by counter techniques. The substance crystallizes in the monoclinic system: space groupI2/a,a = 20·153(8),b = 13·411(5),c = 21·497(8) Å and = 95·28(8) °;D _m = 1·41(2),D _c = 1·43 g cm^–3 andZ = 4. The structure consists of Ph₄As⁺ cations in general positions and tris-(cis-1,2-dicyano-1,2-ethylenediothiolato)Fe(IV) anions on two-fold axes. Although the coordination around the arsenic atom is tetrahedral, the overall symmetry of the cation is 1 (C ₁), probably because the phenyl rings are rotated to accommodate the requirements of packing. The coordination of the six sulphur atoms about the iron atom is trigonal antiprismatic, approximating closely to an octahedron: for any pair oftrans sulphur atoms, the S-Fe-S angle is about 171 °.     

The structure of 1-(p-fluorophenylmethyl)-2-(4-methyl-1-piperazinyl)-1H-benzimidazole hydrogen fumarate

The crystal and molecular structure of the title compound has been determined by X-ray analysis. The 1-(p-fluorophenylmethyl)-2-(4-methyl-1-piperazinyl)-1H-benzimidazole ion cocrystallizes with fumaric acid, (C₁₉H₂₂N₄F⁺·C₄H₃O ₄ ^– ), in space group P-1 with cell dimensions a = 9.938(1), b = 10.131(1), c = 12.712(1) Å, = 86.57(1), = 69.41(2), and = 67.22(2)°. The piperazine N4 atom is protonated and contacts the deprotonated O atom of the fumarate anion through a hydrogen bond. The benzimidazole ring is nearly planar and makes a dihedral angle of 111.25(12)° with the fluorophenyl ring. The piperazine ring adopts a chair conformation.     

Crystal and molecular structure of 3,5-bis(N,N-diethylimonium)-1,2,4-trithiolane-tetraiododi-μ-iododiinercurate(II)

The crystal and molecular structure of 3,5-bis(N,N-diethylimonium)-1,2,4-trithiolane-tetraiododi--iododimercurate(II), (S₃C₂N₂(C₂H₅)₄)Hg₂I₆, has been determined from a single-crystal X-ray diffraction study. The monoclinic unit cell, space groupP2₁/c, witha = 12·574(3),b = 15·777(4),c = 14·560(4) Å, and = 90·83(4) °, contains four formula-units. Three-dimensional intensity data were collected on an automatic diffractometer. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·05 for 1380 independent non-zero reflexions. The structure consists of (3,5-bis(N,N-diethyl-imonium)-1,2,4-trithiolane)²⁺ and Hg₂I ₆ ^2– ions. The cation contains a five-membered ring, S-S-C-S-C, which can be formed by oxidation of dithiocarbamato and thiuramdisulfide complexes.     

Crystal and molecular structure ofN-[1-(2-phenylethyl)-4-piperidinylium]-N-phenylpropanamide (fentanyl) citrate-toluene solvate

The crystal structure of fentanyl has been determined as part of a structure-activity relationship study on a congeneric series of 4-anilinopiperidines. The compound crystallizes as a citrate toluene solvate, C₂₂H₂₈N₂O · C₆H₈O₇ · C₇H₈, in the monoclinic space groupP2₁/c witha = 18.292(6),b = 9.825(4),c = 19.479(4) Å, = 107.43(3) °, andZ = 4. The structure was solved by direct methods using the program Simpel, and refined by block-diagonal least squares to anR value of 0.092. The torsion angle that describes the conformation of theN-phenyl ring relative to the piperidine ring is 123 ° and differs from that found in other 4-substituted anilinopiperidines (172–177 °).     

Crystal and molecular structures of the orthorhombic and monoclinic isomers of catena-di-μ-chloro-semicarbazidecopper(II)

The crystal structures of two isomeric complex compounds of formula [Cu(Cl)₂(NH₂NHCONH₂)] have been determined by X-ray diffraction methods. The orthorhombic isomer has space groupPna2₁ and unit cell constants:a = 6·91(1),b = 8·30(1),c = 10·24(1) Å;Z = 4. The monoclinic isomer has space groupP2₁/c and unit cell constants:a = 6·91(1),b = 8·30(1),c = 11·32(1) Å, = 117·1(2)°;Z = 4. In both complexes coordination around copper is octahedral, with chains of coordination polyhedra along [100]. In the monoclinic compound, the two semicarbazide molecules, which are present in two adjacent octahedra along the chain, have the oxygen and nitrogen atoms in thetrans configuration, one with respect to the other, and are correlated by a centre of symmetry. In the orthorhombic compound, the two semicarbazide molecules are in thecis configuration and there is no centre of symmetry. In both compounds packing is determined by the NH···Cl and NH···O hydrogen bonds which join the chains together.The authors are indebted to Mr M. Lanfranchi who prepared the compounds and to Dr A. Immirzi who made abailable his computer programs.     

Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)copper(III) triiodide

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)-copper (III) triiodide, Cu(S₂CN(C₄H₉)₂)₂ ⁺I₃ ^–, has been determined from a single-crystal X-ray diffraction study. The monoclinic unit cell, space groupP2₁/c,a = 14·026(6),b = 8·62(1),c = 25·015(9) Å, = 95·35(5) °, contains four formulaentities. Three-dimensional intensity data were obtained from Weissenberg photographs. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·083 for 950 independent non-zero reflexions. The structure contains two symmetry-independent cations. In both cations, the copper atom is in planar coordination with four sulphur atoms, the mean Cu(III)-S bond length being 2·22(2) Å. Cu(III)-S distances are about 0·08 Å less than Cu(II)-S distances in comparable complexes.     

Crystal structure of 3-methylrhodaninecopper(I) iodide

The crystal structure of the copper(I) complex has been determined by a three-dimensional X-ray analysis. The monoclinic unit cell, space groupP2₁/c,a = 4·195(1),b = 15·581(2),c = 13·885(2) Å and = 114·9(1) °, contains four formula-units. Intensities were collected on an automatic diffractometer. The structural parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·07 for 1809 non-zero observed reflexions.In this complex, the copper atom is in tetrahedral coordination with three iodine atoms and the sulphur atom of the thiocarbonyl group of the ligand. The iodine atom is coordinated with three copper atoms. The distances are 2·683(2), 2·627(2) and 2·665(2) Å. The distances between neighbouring copper atoms are 3·008(3) and 2·960(3) Å and the corresponding angles are 68·44(6) and 68·02(6) °, suggesting weak copper-copper interactions in this complex.