The crystal and molecular structure of phenothiazine-10-propionitrile. The effect of crystal packing on the dihedral angle of phenothiazine heterocycles

Phenothiazine-10-propionitrile, C₁₂H₈SNC₂H₄CN, crystallizes in the centrosymmetric monoclinic space group P2₁/n, with a = 5.785(1)Å, b = 15.427(3)Å, c = 14.497(4)Å, β = 92.50(1)°, Z = 4, D_meas = 1.29(1) g cm³ and D_calc = 1.28 g cm³ at 23°. Three dimensional X-ray data were collected with a manual diffractometer using MoKα (λ 0.71069Å) radiation and by multiple film Weissenberg techniques using CuKα (λ 1.5418Å) radiation. The structure was determined by Patterson and Fourier methods and refined with 519 observed reflections by full matrix least-squares methods to an R of 0.077. The dihedral angle between the two planes of the o-phenylene rings is 135.4(3)°. In the folded heterocyclic ring the C-S-C angle is 97.8(7)° and the average C? S bond is 1.76(1)Å. A comparison of this structure to that of phenothiazine-10-propionic acid shows the two chemically similar molecules have the same dihedral angles in spite of completely different solid state packing patterns.     

The C—H⃛O hydrogen bond in (di­cyano­methyl)­ammonium p‐toluene­sulfonate

In the title compound, C₃H₄N₃⁺·C₇H₇O₃S^?, the activated C—H group of the cation forms a short but bent C—H?O hydrogen bond with a sulfonate O atom of the anion; C?O = 3.075 (5) Å and C—H?O = 130°.     

The crystal and molecular structure of phenothiazine-10-propionic acid

The crystal structure of phenothiazine-10-propionic acid, C₁₂H₈SNC₂H₄COOH, was determined from three-dimensional X-ray diffraction data collected with a manual diffractomer using MoKα (λ 0.71069 Å) radiation. The space group is P2₁/c with a = 7.888 (2)Å, b = 8.703 (2)Å, c = 19.700 (8)Å, β = 101.42 (1)°, Z = 4, D_meas = 1.35(2) g. cm^?3 and D_calc = 1.36 g. cm^?3 at 23°. The structure was determined by the direct method and refined with 500 observed reflections by full-matrix least squares to an R of 0.072. The molecule is folded along the S-N axis and the dihedral angle is 136.5°. The C-S-C angle is 98.5(7)° and the average C-S bond is 1.77(2)Å. The shortening of the C-S bond, the small value of the C-S-C angle and the folding of the molecule are typical of the phenothiazine class of compounds and are assumed to be due to sulfur d orbital participation in ring bonding.     

Novel Motif of Hydrogen Bonds in the Water-assisted Supramolecular Self-assembly of 2-acetylamino-6-methylpyridine-N-oxide and Hetero-assembly of 1:1 Co-crystal of o-Phenylenediamine with Catechol

Abstract

Water assisted supramolecular structures of 2-acetylamino-6-methylpyridine-1-oxide (1) and 1:1 complex of o-phenylenediamine with catechol (2) were determined. The crystal structure of 2-acetylamino-6-methylpyridine-1-oxide. H₂O (1), triclinic, a = 7.1276 (6), b = 7.8860 (6), c = 8.9938 (7) Å, α = 100. 143 (2), β = 91.493 (2), γ = 110.972 (1)°, V =462.47 (6) ų, Z = 2, D _calc = 1.323 mg.m^?3(293°K) reveals a novel centrosymmetric supramolecular assembly that is sustained by water molecules linking the dimers of pyridine-1-oxide through C—H…O, N—H…O, N⁺—O^? … H hydrogen bonds. The pyridine rings of the dimers are stacked at 3.473 Å apart, involving π- stacking interactions. Complex (2), C₆H₈N₂.—C₆ H₆O₂. 1/2H₂O crystallises in the monoclinic space group P2/c: a = 9.0498(2), b = 5.2275(1), c = 25.0771(2) A, β = 97.71°, V= 1175.62(4) ų, Z = 4. Refinement led to a final conventional R value of 0.041 for 2016 reflections. In these crystals (2), the water molecules lie on the twofold axis and they are linked to the pyrocatechol molecules through an O—H…O hydrogen bond.     

Hydrothermal Synthesis,Crystal Structures and Characterization of Two Hydrogen Phosphates Templated by 4-Amino-2,2,6,6-tetramethylpiperidine

Abstract

Chemical preparations, crystal structures, thermal analyses, and IR spectroscopic studies are given for two new hydrogen phosphates templated by 4-amino-2,2,6,6-tetramethylpiperidine: (C₉H₂₂N₂)₂·(H₂PO₄)·(HPO₄)·(F)·H₂O (I) and (C₉H₂₂N₂)·(H₂PO₄)₂(II). The structures are determined by single crystal X-ray diffraction. Both compounds crystallize in the P2₁/c (N°14) monoclinic space group with the unit cell parameters: a = 14.856 (1) Å, b = 14.092 (2) Å, c = 14.7166 (9) Å, β = 118.434 (7)°, V = 2709.2 (4) Å ³, and Z = 4 for (I) and a = 9.803 (2) Å, c = 0.466 (2) Å, c = 15.640 (8) Å, β = 94.990 (4), V = 1598.68 (7) ų, and Z = 4 for (II).

The structure of I, refined to R = 0.042 and R_w = 0.067 for 6009 reflections (I ≥ 2σ (I)), exhibits infinite inorganic chains _∞((H₂PO₄)·(HPO₄)·(F)·H₂O)^4? linked together through weak hydrogen bonds to form layers onto which the diprotonated [C₉H₂₂N₂]^{2 +} amine molecules are anchored.

The structure of II, refined to R = 0.060 and R_w = 0.086 for 1435 reflections (I ≥ 2σ (I)), consists of _∞(H₂PO₄)^? (100) layers between which [C₉H₂₂N₂]²⁺ cations are inserted. A network of hydrogen bonds connects the different components. IR spectra of I and II show the characteristic bands of amine groups and phosphate anions.     

Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] und (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3

Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ . Reaction of Mo₆Cl₁₂ with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] ( 1 ), which can be converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo₆ClCl(OR^a)₂]^2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Clⁱ) 2.471(3) Å to 2.493(4) Å, d(Mo—Cl^a) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Clⁱ) 2.468(8) Å to 2.506(7) Å, d(Mo—Cl^a) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å).     

Molecular ordering in some liquid aromatic hydrocarbons

This study presents a comparison of the structures and molecular correlations for the linear aromatic hydrocarbons: benzene, naphthalene, and anthracene in the liquid phase, performed for the first time by the method of X-ray diffraction. Also for the first time the X-ray diffraction results obtained for anthracene at 513?K have been reported. Monochromatic radiation CuK_α was used to determine the scattered radiation intensity between S _min?=?4π?sin?Θ_min/λ?=?0.417?Å^?1 and S _max?=?4π?sin?Θ_max/λ?=?7.06?Å^?1. The mean angular distributions of X-ray scattered intensity were measured and the differential radial distribution functions of electron density (DRDFs) were calculated. The mean distances between the neighbouring molecules and the mean coordination numbers were found. The most probable models of local ordering of these molecules were suggested. Correlations have been found between the number of benzene rings in the molecules studied and their physical properties.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Investigation of complexes of zinc(II) and cadmium(II)DI-n-butyldithiocarbamates with 2,2′-bipyridyl

A new mixed-ligand complex, Cd(S₂CN(C₄H₉)_{2 2})₂(2,2′-Bipy), was synthesized. A polycrystal X-ray diffraction analysis was performed (DRON-3M and DRON-UM1 diffractometers, CuK_α radiation, Ni filter) and the crystal structure was determined [Enraf-Nonius CAD-4 automatic diffractometer, MoK_α radiation, 2440 nonzero independent reflections, 153 refined structural parameters, R is 0.11 for I>2σ(I)]. Crystal data for C₂₈H₄₄CdN₄S₄ : a = 28.716(4), b = 6.848(6), c = 17.188(2) Å, space group Pcca, V-3380.2(7) ų, Z = 4, M = 679.42, dcaU.= 1.335 g/cm3. The structure consists of monomeric molecules in which the cadmium atom has a distorted octahedral environment. The polycrystal diffraction analysis revealed that the complex is isostructural with the defined complex Zn(S₂CN(C₄Hg)₂)₂(2,2′-Bipy). A crystal-chemical search on metal dialkyldithiocarbamates in the Cambridge Structural Database was accomplished and isostructural pairs of Zn and Cd metal complexes were found.     

A cobalt(III) compound of a 13‐membered cyclic tetra­amine: trans‐(12,12‐dimethyl‐1,4,7,10‐tetra­aza­cyclo­tetra­decane)diisothio­cyanato­cobalt(III) tetra­isothio­cyanato­zinc(II) ethanol solvate

The title compound, [Co(NCS)₂(C₁₁H₂₆N₄)]₂[Zn(NCS)₄]·C₂H₅OH, has two similar cations with the Co^III atom coordinated in a planar fashion by the 13‐membered cyclic tetra­amine, in the 1R,4S,7R,10S configuration, and with trans isothio­cyanate ligands. The six‐membered chelate ring is in a chair conformation, with one axially and one equatorially oriented methyl substituent [mean Co—N = 1.948 (2) Å]. The `opposite' chelate ring (N<sup>4</sup> and N<sup>7</sup>) is in an eclipsed conformation [mean Co—N = 1.928 (2) Å], and the `side' chelate rings have gauche conformations. The mean Co—N_NCS distance is 1.928 (2) Å. Both cations have one Co—N—C group nearly linear and the other appreciably bent, with mean Co—N—C angles of 178.7 (1) and 160.4 (1)°, respectively. The [Zn(NCS)₄]²⁻ anion is approximately tetra­hedral, with Zn—N = 1.951 (1)–1.986 (1) Å, N—Zn—N = 104.5 (1)–111.9 (1)° and Zn—N—C = 152.5 (1)–179.4 (1)°. One NH group is hydrogen bonded to the ethanol O atom and the other NH groups are bonded to thio­cyanate S atoms, forming a network.     

Synthesis and crystal structure of tris(ɛ-caprolactamium) hexa(isothiocyanato)chromate(III) tricaprolactam (C6H14NO)3[Cr(NCS)6] · 3(C6H13NO)

A novel complex, tris(?-caprolactamium) hexa(isothiocyanato)chromate(III) tricaprolactam (C₆H₁₂NO)₃[Cr(NCS)₆] · 3(C₆H₁₁NO), has been synthesized and characterized by X-ray diffraction. The structure can be referred to the discrete ionic type. The coordination polyhedron of the chromium atom is a nearly regular octahedron. The crystals of the complex (C₄₂H₆₉CrN₁₂O₆S₆, FW = 1082.45) are triclinic, space group P $\overline 1 $ , Z = 1, V = 1359.3(2) ų, d _calcd = 1.322 g/cm³. Unit cell parameters: a = 11.1784(9) Å, b = 11.3196(7) Å, c = 12.580(2) Å, α = 109.347(5)°, β = 106.304(5)°, γ = 102.025(4)°. The unit cell contains three caprolactamium cations and three caprolactam molecules related by the inversion center of the space group, which leads to random occupancy of the positions of the cations and solvation molecules.     

Two bis­(ammonium) 1,5‐naphthalene­disulfonate salts

The title compounds, bis­(ammonium) naphthalene‐1,5‐di­sul­fon­ate, 2NH₄⁺·C₁₀H₆O₆S₂²⁻, and bis­[1‐(hydroxy­methyl)‐3,5,7‐tri­aza‐1‐azoniatri­cyclo­[3.3.1.1^3,7]­decane] 1,5‐naphthalene­di­sul­fon­ate, 2C₇H₁₅N₄O⁺·C₁₀H₆O₆S₂²⁻, were prepared from the acid‐promoted reaction of hexa­methyl­enetetr­amine. In both structures, the di­sulfonate anion is positioned on an inversion center, with each sulfonate group contributing to the supramolecular assemblies via hydrogen bonds. The ammonium cations are linked to sulfonate groups by four distinct N⁺—H⃛⁻O—S contacts [N⃛O = 2.846 (2)–2.898 (2) Å and N—H⃛O = 160 (2)–175 (2)°], whereas the 1‐(hydroxy­methyl)‐3,5,7‐tri­aza‐1‐azoniatri­cyclo­[3.3.1.1^3,7]­decane cations form one O—H⃛⁻O—S [O⃛O = 2.628 (2) Å and O—H⃛O = 176°] and three C—H⃛⁻O—S [C⃛O = 3.359 (2)–3.380 (2) Å and C—H⃛O = 148–155°] interactions to neighboring sulfonate groups.     

Die Kristall- und MolekülStruktur von S4N4·2C7H8

Crystal and Molecular Structure, of S₄N₄ · 2C₇H₈ The structure of the title compound has been determined from threedimensional X-ray data. Crystals are monoclinic, with unit cell dimenions a = 16.532 Å, b = 8.563 Å, c = 10.880 Å, β = 103.2°, space group C? C2/c and Z = 4. Least squares refinement, by use of 1132 independent reflections measured on a diffractometer has reached 3.9%. In the S₄N₄·2C₇H₈ molecules the organic components are linked to two sulfur atoms of the S₄N₄, ring each.     

The molecular structure of high‐spin (S = ) manganese(II) phthalocyanine in tetrabutylammonium bromido(phthalocyaninato)manganese(II)

The title complex salt, (C₁₆H₃₆N)[MnBr(C₃₂H₁₆N₈)] or (TBA)[Mn^IIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [Mn^IIBr(Pc)]⁻ macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the Mn^II cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the Mn^IIN₄ fragment in [Mn^IIBr(Pc)]⁻ is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [Mn^II(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).     

Short-Range Ordering in Liquid Bicyclohexyl by X-Ray Diffraction

Abstract

The paper reports results of the X-ray diffraction structural studies of liquid bicyclohexyl, C₆H₁₁—C₆H₁₁ at room temperature, using CuK _α radiation. Angular distribution of X-ray scattered intensity was measured, and the electron-density radial-distribution function was calculated. Computer techniques were used to minimize the effects of experimental errors, uncertainties in the scattering factors, and termination errors. Good agreement between the theoretical and experimental functions was obtained on assuming the statistically most probable model of this molecule. The structural data obtainable by X-ray analysis for liquid bicyclohexyl were discussed. The mean distances between the neighbouring molecules and the radii of coordination spheres were found. The maxima in the differential radial distribution function were at: r ₁ = 4.68, r ₂ = 5.57, r ₃ = 6.62, r ₄ = 8.05 Å. X-ray structural analysis was applied to determine the packing coefficient of bicyclohexyl molecules. A simple model of short-range arrangement of the molecules in liquid bicyclohexyl was proposed.     

Aqua(dipicolinato‐κ3O,N,O′)(1H‐imidazole‐κN3)(1,10‐phenanthroline‐N,N′)manganese(II)

In the title compound, [Mn(C₇H₃NO₄)(C₃H₄N₂)(C₁₂H₈N₂)(H₂O)], the Mn^II centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.383 (3) and 2.421 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.300 (3) Å, and Mn—O = 2.300 (2) and 2.357 (2) Å], one monodentate imidazole ligand [Mn—N = 2.238 (3) Å] and one water molecule [Mn—O = 2.157 (3) Å]. It displays a distorted pentagonal‐bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10)°. Intermolecular O—H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two‐dimensional network sheet packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and π–π stacking interactions involving the phenanthroline rings.     

Hexahydroxybenzene–2,2′-bipyridine (1/2)

2,2′-Bi­pyridine (2BPY) and hexa­hydroxy­benzene (HHB) crystallize in a 2:1 ratio as a neutral molecular adduct, C₆H₆O₆·2C₁₀H₈N₂, in space group P with Z = 1 and with the HHB molecule lying on an inversion centre. HHB, of which this is the first single-crystal X-ray structure determination, forms O—H⃛O hydrogen-bonded chains parallel to the a axis, with O⃛O distances of 2.761 (1) and 2.782 (1) Å. O—H⃛N hydrogen bonds to the 2BPY molecules crosslink these chains, with O⃛N distances of 2.707 (1) and 2.735 (1) Å.     

rac‐1‐Phenyl­ethyl­ammonium carboxy­methyl­phospho­nate(1–): hydrogen‐bonded anion sheets with pendent cations

In the title compound, C₈H₁₂N⁺·C₂H₄O₅P⁻, the anions are linked by two O—H⋯O hydrogen bonds [H⋯O both 1.75 Å, O⋯O = 2.5781 (15) and 2.5834 (15) Å, and O—H⋯O = 169 and 176°] into sheets built from alternating (8) and (32) rings. Each cation is linked to an anion sheet by three N—H⋯O hydrogen bonds [H⋯O = 1.88–2.04 Å, N⋯O = 2.7603 (16)–2.9334 (17) Å and N—H⋯O = 162–166°], such that all the cations pendent from one face of the sheet are of the R configuration, while all those pendent from the opposite face are of the S configuration.     

meso‐5,5,7,12,12,14‐Hexamethyl‐1,4‐diaza‐8,11‐diazoniacyclotetradecane bis(2‐naphthoate) ethanol disolvate: centrosymmetric five‐component aggregates linked into sheets by C—H⃛π(arene) hydrogen bonding

The title compound is an ethanol‐solvated salt, C₁₆H₃₈N₄²⁺·2C₁₁H₇O₂⁻·2C₂H₆O, in which the cation lies across a centre of inversion in P2₁/c. The ions are linked by N—H⃛O hydrogen bonds [H⃛O = 1.70 and 2.30 Å, N⃛O = 2.624 (2) and 3.136 (2) Å, and N—H⃛O = 178 and 151°], and the ethanol mol­ecule is linked to the anion by an O—H⃛O hydrogen bond [H⃛O = 1.90 Å, O⃛O = 2.728 (2) Å and O—H⃛O = 171°], to form a centrosymmetric five‐component aggregate. C—H⃛O hydrogen bonds and aromatic π–π‐stacking interactions are absent, but the aggregates are linked into sheets by a single C—H⃛π(arene) hydrogen bond.     

Triethylaluminum-Based Ferrocenylalanes. Synthesis and Crystal Structure of (η5−C5H5)Fe[η5−C5H4Al2(C2H5)4Cl]

Abstract

The trietheylaluminum based ferrocenylalane (η⁵?C₅H₅)Fe[η⁵?C₅H₄Al₂(C₂H₅)₄Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for D_c = 1.27 g cm^?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).