Crystal and molecular structure of dichlorotetrakis(propanol-2) titanium (III) chloride,C12H32Cl3O4Ti

The crystal and molecular structure of dichlorotetrakis(propanol-2)titanium (III) chloride, C₁₂H₃₂Cl₃O₄Ti, has been determined by X-ray methods. The complex crystallizes in the monoclinic system:a = 15.968(4),b = 11.610(5),c = 11.90(5) Å, = 94.15(2) °, space groupC2/c andZ = 4. The positions of all non-hydrogen atoms have been refined by least squares to giveR = 0.126 for 1211 observed structure factors. The crystal structure consists of {TiCl₂(HOCH(CH₃)₂)₄}⁺ cations and Cl^– anions. From the space-group symmetry, it follows that the complex cation has 2(C ₂) symmetry. The 2 chlorine and 4 oxygen atoms of the inner coordination sphere are arranged in the form of a distorted octahedron around the central Ti atom. Two chlorine atoms, with the interatomic distance Ti—Cl of 2.32 Å, are in acis-conformation. The interatomic distances Ti—O, two oxygen atoms opposite to the chlorine atoms, are 2.10 Å. The pair oftrans-oriented oxygen atoms are at distances Ti—O= 2.09 Å. The Cl^– ions occupy positions at symmetry centres. Each of them is in contact with four oxygen atoms, the paired Cl—O distances being 3.04 Å and 3.12 Å.     

Structural confirmation of a template reaction mechanism: Structure of dichloro (2,9-dimethyl-3,10-diphenyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)cobalt(III) hexafluorophosphate

The structure of the title compound has been investigated by X-ray diffraction methods. The crystals are monoclinic, space groupP2₁/c, with unit cell parameters:a=11.394(3),b=6.381(2),c=17.413(4)Å, and=95.72(2)°. The structure was refined with 2369 unique reflections by a full-matrix least squares procedure givingR andR _w of 3.2 and 4.2%, respectively. The cobalt complex forms a six coordinate distorted octahedral structure with the cobalt atom at a center of symmetry. The macrocyclic ligand presents eighteen of its 28 nonhydrogen atoms in a planar array about the cobalt atom. Only the two central trimethylene carbon atoms and four carbon atoms of each phenyl ring deviate by more than ±0.05 Å from this plane. Thetrans arrangement of substituents on the ligand of the complex confirms the structural assignment previously made based on NMR data and lends support to the proposed template reaction mechanism by which these complexes form.     

8-Thiatheophylline nitrato silver (I): Spectroscopic characterization and crystal structure

A new metal-theophylline derivative was synthesized from AgNO₃ and 8-thiatheophylline. The thermal stability of the Ag(C₆H₆N₄O₂S)(NO₃) complex was studied by TG and DSC techniques. The silver coordination has been discussed from IR,¹H-NMR and¹³C-NMR spectra. The crystal structure was established by X-ray diffraction. Ag(TTH)(NO₃) crystallizes in space groupP2₁2₁2₁ witha=6.198(1),b=12.576(2),c=13.422(2) Å andZ=4. The structure was refined toR=0.032. This complex reveals interesting features in the coordination mode of the TTH ligand. The sulfur atom and the carbonyl groups are not involved in the coordination. Silver tetrahedral coordination occurs through N7 and N9 of two different TTH ligands (Ag-N7=2.422(3) Å; Ag-N9=2.356(2) Å) and through two oxygen atoms of two different nitrato groups (Ag-O=2.435(4) and 2.518(4) Å) giving a polymeric structure.     

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.     

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.     

Crystal and molecular structure of bis(aminomethylphosphonate)copper(II)

The crystal and molecular structure of bis(aminomethylphosphonate)-copper(II), C₂H₁₀N₂O₆P₂Cu, has been determined from MoK diffractometer data. The compound crystallizes in the monoclinic space groupP2₁/n witha =7.571(2),b = 4.943(1),c = 11.212(3) Å, = 105.84(2) °, andZ = 2. The structure was solved by the heavy-atom technique and refined by full-matrix least-squares methods toR = 0.041, using 1084 reflections for which ¦F _o¦ > 3.92 (¦F _o¦). In this complex, the Cu atom is square-planar coordinated by four O atoms from four phosphonic groups, and not by the amino group. The Cu-O bond lengths are 1.928(3) and 1.937(3) Å, and the phosphonic groups bridge adjacent Cu atoms in polymeric chains. The infrared spectrum of this complex is reported.     

Crystal and molecular structure of the 2,4,7-trinitrofluorenone-hexamethylbenzene charge-transfer complex

The crystal and molecular structure of the charge-transfer complex formed between 2,4,7-trinitrofluorenone and hexamethylbenzene has been determined by single-crystal X-ray diffraction techniques. The complex crystallizes with four charge-transfer pairs in a monoclinic cell (P2₁/c) of dimensionsa = 9.533(1),b = 14.944(2),c= 17.470(2) Å and = 113.18(1) °. The structure was solved by direct methods. The orderly packing of donor and acceptor molecules in parallel crystalline planes made the determination a severe test of direct methods techniques. The 2294 statistically significant reflections were refined to a final value ofR = 0.063. Estimated standard deviations were 0.004 Å in bond distances and 0.5 ° in bond angles among the non-hydrogen atoms. The acceptor and donor molecules lie in alternate (212) planes with a separation of 3.25 Å between the planes.     

Crystal and molecular structure of dimethanolbis(salicylaldehydato)cobalt(II), C16H18CoO6

The structure of dimethanolbis(salicylaldehydato)cobalt(II) has been determined by three-dimensional X-ray diffraction methods. The crystals are monoclinic, space groupP2₁/c,a = 5.099(7),b = 19.446(9),c = 8.889(7) Å, = 111.85(10) °, andZ = 2. The structure consists of discrete centro-symmetric molecules of C₁₆H₁₈CoO₆ in which the oxygen atoms form a distorted octahedron about the cobalt atom, with cobalt-oxygen distances of 2.010(4), 2.076(4) Å (salicylaldehyde) and 2.115(4) Å (methanol). The molecules are linked together along thea-axis by intermolecular hydrogen bonds from the hydrogen atoms of the methanol groups to phenolic oxygen atoms of neighboring molecules. The final conventionalR-factor for 1232 observed reflections is 0.058.     

Separation of 4-aminobenzoic acid by cocrystallization: Crystal structure of the complex of 4-aminobenzoic acid with (2R,3R)-tartaric acid

4-Aminobenzoic acid (PABA) has been successfully separated from a mixture containing 2-aminobenzoic acid and (2R,3R)-tartaric acid. X-ray structure analysis confirms the separating result. The molecular complex formed by PABA and tartaric acid in 1:1 molar ratio crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions of a = 7.329(1) Å, b = 12.095(2) Å, c = 15.231(3) Å, V = 1350.1(4) ų, Z = 4. The crystal structure comprises protonated PABA, monoanion of tartaric acid, and crystalline water. The extensive H-bonding network exists in the crystal structure. H bonding between tartaric acid and both terminal groups on para position of PABA is considered as a possible reason for the successful separation.     

Crystal and molecular structure of bis(quinoxaline)-2,2′,3,3′-disulfide,C16H8N4S2

The crystal and molecular structure of bis(quinoxaline)-2,23,3-disulfide, C₁₆H₈N₄S₂, was determined by direct methods and refined by least-squares methods, using 823 reflections collected with a two-circle Weissenberg diffractometer, including anisotropic temperature factors for nonhydrogen atoms to a finalR of 0.104. The crystals are monoclinic prismatic: space groupP2₁/a,a = 18.98(2),b = 9.27(2),c = 3.89(1) Å, = 100.3 °(1),Z = 2. The structure consists of layers of molecules staggered along thec axis. The molecule is centrosymmetric, and makes an acute angle of 36.9 ° with theab plane; it is planar within an rms atom deviation of 0.02 Å. The S-C (1.752–1.760 Å) distances are normal for a S-C (sp²) bond. The N-C bonds (1.372–1.381 Å) adjacent to the benzene ring are longer than the N-C bonds (1.318–1.322 Å) adjacent to the central C₄S₂ ring.     

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 structure of di-μ-chloro(dicyandiamide)cadmium(II)

The crystal structure of di--chloro(dicyandiamide)cadmium(II) has been determined and refined by Fourier and least-squares methods toR = 0·037 using three-dimensional X-ray data collected at room-temperature on a single-crystal automated diffractometer. Crystal data are as follows:a = 10·796(7),b = 8·933(5),c = 6·847(3) Å, = 99·9(1) °,Z = 4; space groupP2₁/n. The cadmium atom is surrounded by four chlorine (Cu-Cl = 2·572, 2·607, 2·630, 2·647 Å) and two nitrogen atoms (Cd-N (nitrilic) = 2·358 Å; Cd-N (guanidic) = 2·430 Å) so that the whole polyhedron appears as a slightly distorted octahedron. The chlorine atoms form bridges between adjacent metal atoms so that the coordination octahedra are linked in chains running along [001]. These chains are joined together by dicyandiamide bridges.The authors wish to thank Dr. A. Immirzi (Politecnico di Milano) for the use of his compter programmes.     

Crystal structure of copper(II)mellitate, [Cu3.5C6(COO)5(COOH)(OH)2(H2O)8.5]·4.5H2O

The crystal structure of copper(II)mellitate, Cu_3.5C₁₂H₂₉O₂₇, has been determined by X-ray analysis. The complex crystallizes in the orthorhombic space groupIba2, with unit-cell dimensionsa=19.274(3),b=21.054(7),c=12.956(4) Å. The structure was deduced by the direct method with the help of the Patterson method and refined by the block-diagonal least-squares technique to a finalR value of 0.037 for 2995 observed reflections. Among six carboxyl groups of mellitic acid, five groups lose protons and form coordinate bonds to four copper atoms, and the remaining group forms hydrogen bonds to the water of crystallization and coordinated water. The configuration around copper is distorted-pyramidal, with the Cu-O bond distances of 1.896(7) to 2.425(7) Å.     

Synthesis and crystal structure of a 2D (6,3) coordination network, {[Ag(L)1.5]NO3} n [L = 1,3-bis(benzylthio)propane]

A new dithioether silver(I) complex, {[Ag(L)_1.5]NO₃} _n (1) has been prepared by the reaction of AgNO₃ with 1,3-bis(benzylthio)propane (L) in methanol/chloroform. The structure was characterized by single-crystal X-ray diffraction analysis: rhombohedral system, space group R –3c, with a =b = 15.651(7), c = 39.26(4) Å, V = 8328(1) ų, and Z = 6. The crystal structure consists of [Ag(L)_1.5]⁺ cations and NO₃ ^– anions. In 1, each silver(I) center is coordinated equivalently to three sulfur donors from three different ligands to give a trigonal-planar coordination geometry. Each L links two adjacent silver(I) centers in bis-monodentate bridging mode to form a 2D (6,3) network sheet. Furthermore, these 2D sheets are linked by the weak coordination interactions between nitrate ions and silver(I) atoms to form a 3D brick-wall framework.     

Crystal and molecular structure of dipotassium-aquapentachlororhodate (III): (K2)++ [RhCl5(H2O)]2−

The structure of K₂[RhCl₅(H₂O)] has been established by X-ray crystallography. It crystallizes in the orthorhombic space groupPcmn, with cell dimensionsa=7.065(1),b=9.453(1),c=13.567(1) Å,V=906.1(3) ų,Z=4,M _r =376.4,D _x =2.76 g cm^–3,F(000)=712,T=293 K. The final wasR=0.046. The rhodium atom has a distorted octahedral coordination involving five chlorine atoms and an oxygen of the water molecule with Rh, O, and three chlorine atoms on the mirror plane. Rh-Cl distances range from 2.284(7) Å to 2.345(7) Å. The Cl(4)O intermolecular distance, 3.140(12) Å indicates strong hydrogen bonding between oxygen and chlorine atoms of the neighboring octahedra.N. C. L. Communication No. 5353.     

Crystal and molecular structure of tin(IV) dithiocarbamates: III. Tris(N,N-diethyl-dithiocarbamato)n-butyltin(IV)

The crystal structure of the title compound has been determined from 1623 independent reflections measured by scintillation methods. The compound cyrstallizes in the monoclinic space groupP2₁/c witha = 10.60(2),b = 18.40(5),c = 17.05(3) Å, = 116.7(2) °, andZ = 4. The structure was solved by Patterson and Fourier techniques and was refined by full-matrix least-squares methods toR = 0.066. As in tris(N, N-diethyldithiocarbamato)-methyltin(IV) the crystal structure consists of discrete, neutral, sevencoordinated tin complexes. The distorted pentagonal bipyramidal geometry of the tin atom is almost identical to that in the methyl complex, being formed by two sulfur atoms from each dithiocarbamate and a carbon atom of the butyl group which occupies one of the axial positions. Each dithiocarbamate ligand again has one Sn-S distance significantly shorter than the other. For the equatorial ligands the average difference is 0.18 Å with the minimum Sn-S distance 2.619(7) Å and the maximum 2.860(6) Å. For the ligand which bridges axial-equatorial, the Sn-S axial distance is 2.491(6) Å, while the Sn-S equatorial distance is 2.763(8) Å. The axial S-Sn-C angle is 166.3(5) °. The results are compared with those for other seven-coordinated tin(IV) structures and seven coordinated dithiocarbamate complexes of other metals.     

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.     

Synthesis,structure and IR characterization of disodium tetra(9,10-dihydro-9-oxo-10-acridineacetato)zincate(II) bis(ethanol) heptahydrate

The synthesis, crystal structure and IR data are reported for Na₂[Zn(CMA)₄]·2EtOH·7H₂O, where CMA^– is the 9,10-dihydro-9-oxo-10-acridinacetate ion. The complex crystallizes in the monoclinic space group P2/n, with cell dimensionsa=17.335(9),b=8.440(5),c=21.875(12) Å, =91.94(5)°,Z=2. The structure was solved by direct methods and refined to a finalR value of 0.0363 for 3022 non-zero reflections. The Zn²⁺ ion occupies twofold axis and is coordinated to four carboxylate ligands, the ZnO₄ tetrahedron is considerably distorted with Zn–O distances of 1.978(3) and 1.961(3)Å. Each Na⁺ cation interacts with two water, one ethanol, and three carboxylate O atoms comprising distorted octahedron. The Zn²⁺ and Na⁺ cations are linked through monooxygen and syn-syn carboxylate bridges forming a trinuclear, mixed-metal cluster. The Zn...Na separation is 3.267(2)Å and Na...Na distance equals 3.520(2)Å. All oxygen bonded H-atoms are utilized in hydrogen bonds. The acridone rings overlap in the crystal with the 3.5 Å interlayer separations. The compound has been characterized by IR spectroscopy.     

Synthesis and crystal structure of an infinite double- stranded chain manganese(II) coordination polymer bridged through 1,2-bis(imidazol-1-yl)ethane ligand

The manganese complex [Mn(bim)₂(NCO)₂]_n (1) (bim = 1,2-bis(imidazol-1-yl)ethane) has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group C2/c, a = 9.896(3) Å, b = 15.383(4) Å, c = 13.949(4) Å, β = 98.966(5)^∘, V = 2097.5(9) ų, Z = 4. The coordination geometry of Mn(II) atom is distorted octahedral; it is coordinated equatorially by four nitrogen atoms from the imidazole rings of four symmetry-related bim ligands, and axially by two nitrogen atoms from two symmetry-related cyanate anions. The structure is polymeric, with 18-membered spiro-fused rings and each 18-membered ring involving two inversion-related bim molecules.     

Synthesis and crystal structure of a nickel(II) complex involving imino nitroxide radicals

A new complex of formula [Ni(im2-py)₂(SCN)₂]CH₃OH (im2-py = 2-(2-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) has been synthesized and the crystal structure determined by X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁/n with a = 15.525(5) Å, b = 13.405(4) Å, c = 16.167(5) Å, = 113.324(5)°, V = 3089.6(16) ų, and Z = 4. The structure of this complex is mononuclear with the nickel(II) ion octahedrally coordinated and bound to the imino nitroxide radicals through the imino nitrogen atoms. The thiocyanate groups are coordinated to the metal by the nitrogen atoms.