Synthesis and crystal structure of (S, S, S, S)-N, N′-bis[N-(P-toluenesulfonamido)-1,2-diphenylethyl]ethylenediamine

(S, S, S, S)-N,N′-bis[N-(p-toluenesulfonamido)-1,2-diphenylethyl] ethylenediamine (C₄₄H₄₆N₄O₄S₂), has been synthesized and structurally characterized by elemental analysis, ¹H-NMR, MS, IR and single-crystal X-ray diffraction. The title compound contains four chiral centers with C atoms in S configuration. Molecules are connected to one another by hydrogen bonds between sulfonamide nitrogen and sulfonyl oxygen to form chains alone a axis.     

The molecular structure of 3(5)-methyl-4,5(3)-trimethylenepyrazole hydrochloride and its13C and15N NMR spectroscopy

The title compound (C₇N₂H₁₀, HC1, 1/2H₂O) crystallizes in the space groupC2/c with cell parameters:a=11.651(9),b=16.309(1),c=9.167(1)Å,=94.95(3)°,Z=8, withd=1.287 g cm^–3. One of the chlorine atoms lies on a twofold axis, the second and the oxygen atom of the water molecule have disordered positions. Intermolecular interactions through hydrogen bonds are established between nitrogen atoms of the pyrazole ring and chlorine atoms or the water molecule. In this way, chains of molecules are built; these chains, through van der Waals interactions, form layers which are stacked in the a direction. The¹H,¹³C, and¹⁵N NMR (this last using the double labelled compound) have been recorded in solution and the¹³C NMR spectrum also in the solid state (CP/MAS technique). The NMR parameters ( andJ's) thus obtained are discussed using the molecular structure.     

Crystal and molecular structure of monoglycine nitrate

The crystal and molecular structure of monoglycine nitrate (C₂ H₆ NO⁺ ₂, NO^– ₃) has been determined by single-crystal X-ray diffraction methods. The crystals are orthorhombic: space groupP2₁2₁2₁,a = 16.42(6),b = 6.10(4),c = 5.61(5) Å andZ = 4. The structure has been solved by direct phase determination methods, using visually-estimated intensity data, and was refined to anR -value of 0.064, using counter-measured intensity data for 660 reflections. The anomalous scattering by oxygen and nitrogen atoms suggests the present configuration.The molecule in the structure exists as⁺NH₃CH₂CO₂H, NO^– ₃. The glycinium molecule is planar, except for the N(amino) atom, which deviates by 0.48 Å from the molecular plane defined by the atoms C(1), C(2), O(1) and O(2). The torsion angle N(1), C(2), C(1), O(1) is 20.7 °. The NH₃ group is a donor of three hydrogen bonds of equal strength (N ... 0 = 2.85 Å). Two of the hydrogen atoms of the NH₃ group also form weak bifurcated hydrogen bonds (N ... 0 = 3.04 Å). One of the carboxyloxygen atoms is a donor of a hydrogen bond (0 ... 0 = 2.65 Å). The oxygen atom of the carboxyl group and the oxygen atoms of the nitrate group are all acceptors of hydrogen bonds.The major part of this work was carried out at the Max-Planck Institute for Biochemistry, Martinsried (Munich), and one of the authors (P.N.) expresses his gratitude to Prof. W. Hoppe and his group for the facilities made available to him and for their help. He is also grateful to the Max-Planck Gesellschaft for the award of a research fellowship.     

Crystal structure of the piperazine-1,4-diium (DL-)hydrogen malate (1:2)

The crystalline salt of piperazine-1,4-diium (DL-)hydrogen malate (1:2), (C₄H₁₂N₂)²⁺ (C₄H₅O₅)₂^–, has been prepared and characterized by X-ray crystallography. The title salt crystallizes in monoclinic space group P2₁/n with a = 7.073(1), b = 14.180(2), c = 7.526(1) Å, = 94.66(1), V = 752.33(18) ų and Z = 2. Results indicate that the title salt exists as a racemic compound but a conglomerate. In the structure, axial and equatorial hydrogen atoms of piperiaine-1,4-diium are all involved in different bifurcated hydrogen bonds. The integral structure, formed by the hard hydrogen bonds of N–HsO and O–HsO, is stabilized further by soft hydrogen bond of C–HsO.     

Crystal and molecular structure of morpholine biguanide hydrochloride

Crystals of morpholine biguanide hydrochloride, C₆H₁₃N₅O. HC1, belong to the orthorhombic space groupPbca;a = 19·02 Å,b = 9·92 Å,c = 10·34 Å andZ = 8. The structure has been solved by three-dimensional Patterson and heavy-atom Fourier syntheses. The hydrogen positions have been located from a three-dimensional difference Fourier synthesis. The positional coordinates of all the atoms and their temperature factors (anisotropic for non-hydrogen atoms and isotropic for hydrogen atoms) have been refined by three-dimensional least-squares methods. The finalR value is 0·087.The morpholine ring has been found to assume a chair configuration. The contribution of various valence bond structures to the normal state of the morpholine biguanide hydrochloride molecule has been studied with reference to the characters of the C-N bonds in the biguanide part of the molecule. Both the guanidine groups are planar. Of six available hydrogen atoms, only four take part in forming hydrogen bonds of the type N-H···Cl^–. The molecules in the crystal are linked by a three-dimensional network of hydrogen bonds.Our thanks are due to the staff of the Computing Centres at IIT, Kharagpur and TIFR, Bombay.     

Crystal structure of strontium Di[bis(iminodiacetato)cobaltate(III)] pentahydrate,Sr[<Emphasis Type="Italic">cis</Emphasis>(N)-Co(<Emphasis Type="Italic">Ida</Emphasis>)<Subscript>2</Subscript>]<Subscript>2</Subscript> · 5H<Subscript>2</Subscript>O

Compound Sr[cis(N)-Co(Ida)₂]₂ · 5H₂O (I) is synthesized and its crystal structure is determined. The crystals are built of [Co(Ida)₂]^? anionic complexes, [Sr(H₂O)₃]²⁺ hydrated cations, and crystallization water molecules. Two independent anions are located on rotation axis 2 and have close structures. A distorted octahedral coordination of Co³⁺ atoms is formed by two N atoms and four O atoms of two Ida ^2? ligands [Co-N, 1.932(3) and 1.940(3) Å; Co-O, 1.879–1.899(3) Å]. [Sr(H₂O)₃]²⁺ cations randomly occupy half of the positions in the vicinity of centers of inversion. In addition to three water molecules, the environment of the Sr²⁺ atom includes five O atoms of five Ida ^2? ligands [Sr-O, 2.487(3)-2.889(5) Å]. Because of the disordering of [Sr(H₂O)₃]²⁺ cations, the structural function of the Ida ^2- ligands varies from tridentate chelate to pentadentate bridging chelate. Sr-O and hydrogen bonds connect structural elements into a three-dimensional framework. The structure of I is compared with that of a related compound Sr[CoEdta]₂·9H₂O (II). It is shown that the formation of N-H…O hydrogen bonds, which connect [Co(Ida)₂]^? anionic complexes in I into compact chains, is an important factor leading to the difference between packings I and II.     

Crystal structure of the binary complex of cobalt and zinc chlorides with carbamide [Co(OCN<Subscript>2</Subscript>H<Subscript>4</Subscript>)<Subscript>5</Subscript>(H<Subscript>2</Subscript>O)][ZnCl<Subscript>4</Subscript>]

Mixed single crystals of [Co(OCN₂H₄)₅(H₂O)][ZnCl₄] were grown by the isothermal evaporation of an aqueous solution. The crystal structure of this complex was established by X-ray diffraction (R = 0.052 based on 7003 reflections). The crystals consist of [Co(OCN₂H₄)₅(H₂O)]²⁺ cations containing Co atoms in an octahedral coordination and [ZnCl₄]²⁻] anions containing Zn atoms in a tetrahedral coordination. The carbamide molecules are involved in both intramolecular and interionic hydrogen bonds. The H₂O molecule forms hydrogen bonds with the anions.     

Synthesis and crystal structure of a phthalate-bridged copper(II) complex {[Cu(L)(Phen)(H<Subscript>2</Subscript>O)]⋅H<Subscript>2</Subscript>O}<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A phthalate-bridged copper(II) complex {[Cu(phth)(Phen)(H₂O)] H₂O}_n (H₂phth: phthalic acid, Phen: 1,10-phenanthroline) has been synthesized by the reaction of CuCl₂ and phthalic acid in the presence of 1,10-phenanthroline in aqueous solution. The crystal structure of the complex has been determined by X-ray diffraction analysis to be orthorhombic, with the centrosymmetric space group Pbcm, where a = 11.6652(3) Å, b = 11.1709(3) Å, c = 14.0532(4) Å, V = 1831.28(9) ų, Z = 4. The L^2– (the acid radical of H₂phth) ion is coordinated to the Cu²⁺ ion as a monodentate ligand. Each L^2– ion bridges two adjacent Cu²⁺ ions with its two oxygen atoms from two carboxylic groups to form a one-dimensional zigzag chain. The coordination water and uncoordinated carboxylic oxygen atoms from neighboring chains are linked through hydrogen bonds to form a two-dimensional structure. There is a weak interaction between the coordination water molecule and the Cu²⁺ ion in the neighboring chain.     

Synthesis and Structure of [Fe<Subscript>3</Subscript>O(O<Subscript>2</Subscript>CCH<Subscript>2</Subscript>OMe)<Subscript>6</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>][FeCl<Subscript>4</Subscript>]

Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined. The three iron atoms and the μ₃-oxo are coplanar. Each carboxylic ligand is bidentate and links two iron atoms in the cluster. The clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration. The [FeCl₄]⁻ anion is intercalated between the hydrogen-bonded sheets. Crystal data: space group P2₁/n, a = 10.276(2), b = 22.793(5), c = 17.091(3) ?, β = 96.66(3)°, V = 3976(1) ?³, Z = 4, R = 0.0837, wR ₂ = 0.1836. Graphical Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined in which the clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration.      

Crystal structure of calcium (Ornithinato-N (α), N (δ), N (δ )-triacetato)cobaltate(III) octahydrate Ca[Co(Orntra)]2 ⋅ 8H2O

The X-ray crystal structure of calcium (ornithinato-N _(α) N _(δ) N _{(δ )}-triacetato)cobaltate(III) octahydrate Ca[Co(Orntra)]₂ ? 8H₂O has been determined. The crystals are orthorhombic, a = 21.163(4) Å, b = 8.391(2) Å, c = 19.101(4) Å, V = 3391.9(9) ų, Z = 4, and space group Pca2₁. In the trinuclear linear molecule [Co(μ-Orntra)]₂Ca(H₂O)₅, two independent anions [Co(Orntra)]^? are joined with the Ca²⁺ cation by the bridging bonds through the terminal O atoms. In each [Co(Orntra)]^? anion, the Co atom occurs in the octahedral environment of two N atoms and four O atoms of the Orntra ligand and closes four five-membered and one seven-membered chelate rings. Two O atoms of two anions occupy axial vertices in a pentagonal bipyramid of the Ca²⁺ ion. Five O(H₂O) atoms are located in the equatorial plane. The asymmetric C atoms in the anions bound to the same Ca²⁺ cation have an identical absolute configuration. The crystal involves the molecules belonging to both configurations. The coordinated and outer-sphere H₂O molecules participate in an extended system of hydrogen bonds.     

Crystal structure and spectroscopic study of polymolybdates. The crystal structure and bonding of hexakis(n-pentylammonium) heptamolybdate(VI) trihydrate

Three new heptamolybdates ofn-alkylammonium have been synthesized, with the general formula: (BH)₆[Mo₇O₂₄]·3H₂O, where B=n-butyl-,n-pentyl-, andn-hexylamine (hereafter abbreviated as BUTMO, PENTMO, and HEXMO, respectively). Crystal structure analyses of these compounds show that all of them are isostructural and crystallize in the monoclinic system, the space group beingP2₁/n,Z=4. Crystal data for PENTMO are: (C₅H₁₄N)₆[Mo₇O₂₄]·3H₂O,a=17.085(2),b=31.344(4),c=11.487(12) Å,=93.04(3)°,V=6143(6) ų,F(000)=3288,D _x =1.77, D₀=1.78(1) Mg·m^–3,R=0.059, andR _w =0.066 for 5526 observed reflections. Only slight differences in cell dimensions have been observed for these compounds, except for the parameterb which is significantly different in all of them. Thermogravimetric studies show that the compounds contain three water molecules. IR spectra indicate that the organic bases are protonated and the polyanion presents the well-known infrared spectrum for heptamolybdates in the solid state. The structure solution confirms that the compound PENTMO contains discrete [Mo₇O₂₄]^6– anions, (C₅H₁₄N)⁺ cations, and water molecules, connected through hydrogen bonds; the distinguishing features of the compound PENTMO are its extensive hydrogen bonding. The cations and the water molecules are positioned so as to be able to form hydrogen bonds with either molybdate oxygen atoms or water oxygen atoms. The proposed strong hydrogen bonding interactions appear to stabilize the structure. Some of these hydrogen bonds can play an important role in the possible photochromism of this compound.     

Stability of E′ centers induced by 4.7 eV laser radiation in SiO2

The kinetics of E′ centers ( Si) induced by 4.7 eV pulsed laser irradiation in dry fused silica was investigated by in situ optical absorption spectroscopy. The stability of the defects, conditioned by reaction with mobile hydrogen of radiolytic origin, is discussed and compared to results of similar experiments performed on wet fused silica. A portion of E′ centers and hydrogen are most likely generated by laser-induced breaking of Si–H precursors, while an additional fraction of the paramagnetic centers arise from another formation mechanism. Both typologies of E′ centers participate in the reaction with H₂ leading to the post-irradiation decay of the defects. This annealing process is slowed down on decreasing temperature and is frozen at T = 200 K, consistently with the diffusion properties of H₂ in silica.     

Crystal structure investigation of [Mn(3-CH3C5H4N)2(N3)2(H2O)2]

The crystal structure of the title compound has been determined by single crystal X-ray diffraction methods. [Mn(3-CH₃C₅H₄N)₂(N₃)₂(H₂O)₂] crystallizes in the space group P 1 with a = 7.444(2) Å, b = 7.691(2) Å, c = 8.926(3) Å, α = 99.82(3)°, β = 108.80(2)°, γ = 114.99(2)° and Z = 1. Least squares refinement gave a R value of R_w = 0.046 for 1414 observed reflections. The manganese atom in the title complex is octahedrally coordinated by two oxygen atoms of the water molecules and four nitrogen atoms; two N-atoms are the end atoms of azide groups and the other two nitrogen atoms belong to the 3-methylpyridine molecules. The polyhedra are linked via hydrogen bonds between the water molecules and the azide groups.     

Crystal and molecular structure of the triflate salt of diprotonated 1,4,8,11-tetrakis(2-hydroxyethyl)-1,4,8,11-tetraazacyclotetradecane, [C10H22N4(CH2CH2OH)4 2+]−[CF3SO3 −]2: geometry of a diprotonated octadenate ligand

The title complex crystallizes in the centrosymmetric monoclinic space group P2₁/n with Z=2. The cation is the diprotonated derivative of the neutral octadentate macrocyclic ligand C₁₀H₂₀N₄(CH₂CH₂OH)₄; the two protonated nitrogen atoms are as far apart as is possible in the 14-membered ring (1-and 8-positions) so as to minimize electrostatic repulsions. Each of the [C₁₀H₂₂N₄(CH₂CH₂OH)₄ ²⁺] cations is involved in hydrogen bonding (through the four hydroxy groups) to oxygen atoms on four different peripheral [CF₃SO₃ ⁻] anions.     

A novel two-dimensional 4f-3d coordination polymer Ce2Co3(EDTA)3(H2O)11·12H2O

A novel two-dimensional 4f-3d heterometallic coordination polymer Ce₂Co₃(EDTA)₃(H₂O)₁₁·12H₂O (EDTA = ethylenediamine-N,N,N,N-tetraacetate) has been synthesized using complex Na[Ce(EDTA)] as ligand. The complex crystallines in the space group C2, with lattice parameters a = 15.974(3) Å, b = 14.676(3) Å, c = 14.773(3) Å, = 116.39(3)°,V = 3102.4(11) ų, D_x = 1.858 g/m³, Z = 2. It consists of a two-dimensional sheet in which the Ce(III) is ten-coordinated by six carboxylic O atoms from three EDTA molecules and four O atoms of water molecules, forming a distorted bicapped square antiprism, and the Co(II) atom is seven-coordinated by two N, four O atoms from one EDTA molecule and one O atom from the water molecule, giving rise to a monocapped trigonal prism. Each chelated Co(II) atom is connected to two hydrated Ce(III) atoms through tridendate bridging carboxylate groups, while each Ce(III) atom has three Co(II) atoms as neighbors. These sheets are linked into a three-dimensional network by the water molecules between layers through rich hydrogen bonds.     

Structure of an unusual, 8-coordinate,exclusive cryptate of ytterbium(III) containing multiple nitrato andN-thiocyanato ligands

The first example of an 8-coordinate cryptate of cryptand(2,2,2) [N(CH₂CH₂OCH₂CH₂OCH₂CH₂)₃N], Yb³⁺, and multiple nitrato andN-thiocyanato ligands, H₂Yb(NCS)₃(NO₃)₂(2,2,2)·H₂O (I), has been synthesized. The crystal and molecular structure ofI have been determined by single-crystal X-ray diffraction. The Yb³⁺ cation is not located in the cavity of the cryptand(2,2,2), but is connected to it through a water bridge by two hydrogen bonds to form an exclusive cryptate. The two H⁺ ions are mostly probably bound to the two N atoms of cryptand(2,2,2). The coordinating atoms of the NO ₃ ^– , NCS^–, and H₂O ligands constitute a trigonododecahedron around the central Yb³⁺ ion. CryptateI crystallizes in the monoclinic space groupP2_l/n withZ=4. The finalR factor for 3659 independent reflections, following correction for Lorentz and polarization effects and havingF ₀>5(F ₀), is 0.053. Infrared spectroscopic data for1 are consistent with the X-ray crystal structure results.Presented, in part, at 2nd International Conference on Rare Earth Development and Application, Beijing, China, May 27–31, 1991.     

Synthesis and crystal structures of two copper(I) π-complexes with 1-allyloxybenzotriazole of CuBr?C6H4N3(OC3H5) and 2CuCl?C6H4N3(OC3H5) compositions

Both compounds of CuBr⋅C₆H₄N₃(OC₃H₅) (sp. gr. P1, a = 7.633(1) Å, b = 9.987(1) Å, c = 14.898(2) Å, α = 104.75(1)^∘, β = 94.76(1)^∘, γ = 106.90(1)^∘) (I) and 2CuCl⋅C₆H₄N₃(OC₃H₅) (sp. gr. Cc, a = 11.2483(4) Å, b = 16.7076(6) Å, c = 7.2948(3) Å, β = 118.612(2)^∘) (II) composition were prepared by alternating-current electrochemical synthesis. In I due to a bridging function of organic moieties 16-membered cycles appear which are combined into ribbons {Cu₂Br₂[(C₆H₄N₃(OC₃H₅)]₂}_n. Each of two crystallographically independent copper atom possesses a trigonal-pyramidal arrangement with different degree of tetrahedral distortion. Distinctive numbers of hydrogen bonds around Br1 and Br2 atoms cause rather appreciable distinctions in copper–olefinic bond interaction effectiveness for each metal atom. In II Cu₂Cl₂ rhombs are joined to infinite chains oriented along [010] direction. Each ligand molecule is also coordinated through the C=C—bond of the allylic group to copper atom of one inorganic chain and through the nitrogen atom to a metal atom belonging to another copper-halide chain. Cu1 atoms is tetrahedrally surrounded by three chlorine atoms and nitrogen one, whereas a trigonal-planar arrangement of Cu2 atom is formed by two halogen atoms and slightly disordered olefinic group.     

Supramolecular organization of the crystal structure of <Emphasis Type="Italic">cis</Emphasis>-bis(thiosemicarbazide)palladium(II) <Emphasis Type="Italic">ortho</Emphasis>-hydrophthalate

This paper reports on the synthesis of a new palladium(II) thiosemicarbazide complex of the composition [Pd(HL)₂](HPht)₂ · 4H₂O(I) (where HL is N(1)H₂-N(2)H-C(3)(=S)-N(4)H₂ and HPht ⁻ is a monoanion of ortho-phthalic acid) and the results of an investigation of its structure. It has been demonstrated that two organic ligands are bidentately coordinated in the neutral form through a set of N and S donor atoms, which are located in the cis position with respect to the central metal atom. Three independent water molecules are joined by hydrogen bonds into the centrosymmetric associate {H₂O}₆. In the crystal, thiosemi-carbazide cationic complexes of palladium(II), monophthalate anions, and water molecules are self-organized into a supramolecular system with the formation of a three-dimensional structure based on ionic and hydrogen bonds.     

Crystal and molecular structure of tricyclohexylphosphineethylidenenickel tricarbonyl: a reaction product of Ni(CO)4 and (C6H11)3P=(CH)CH3

The structure of tricyclohexylphosphineethylidenenickel tricarbonyl, (C₆H₁₁)₃P(CH)CH₃.Ni(CO)₃, has been determined by direct methods from 5858 automatic diffractometer data, and refined anisotropically to a finalR value of 0·094 (including hydrogen atoms). The crystals are monoclinic, space group P2₁/n, with a=10·670(1), b=13·879(2), c=16·222(2) Å, =91·80(1)° and z=4. The main feature of the structure determination is the confirmation of the predicted arrangement of the ligand with its bonding to nickel via the secondary carbon of ylid-ligand. This carbon and the nickel atoms show approximate tetrahedral geometry. There seems to be no direct interaction between phosphorus and nickel (closest approach distance is 3·30 Å). The nickel-carbon distance (2·10 Å) is longer than any other Ni-C(sp³) distance previously reported.No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission of Plenum Publishing Company Limited.National Lending Library Supplementary Publication No. 60056 contains 29 pages of structure factor tables on 1 microfiche.     

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.