Asymmetric Unit Of Compound Research Articles

Syntheses, crystal structures, and magnetic behaviors of phenoxo-bridged manganese compounds based on tetradentate Schiff bases

Six Mn(II)/Mn(III) coordination compounds with tetradentate Schiff bases, [Mn(L1)(N3)]2 (1), [Mn(L2)(N3)]2 (2), [Mn(L1)(SCN)]2 (3), [Mn(L2)(SCN)]2[Mn(L2)(SCN)(C2H5OH)]2 (4), [Mn(L1)(CH3OH)]2 (5), and [Mn3(L2)2(CH3COO)2] (6) [H2L1 = N,N'-bis(5-chloro-salicylaidimine)-1,2-diaminop-ropane), H2L2 = N,N'-bis(5-chloro-salicylaidimine)-2,2-dimethylpropane-1,3-diami- ne], were structurally and magnetically characterized by X-ray single crystal diffraction, powder X-ray diffraction (PXRD), elemental analysis, infrared (IR) spectroscopy and magnetic susceptibility measurement. Structural analysis reveals that each manganese center displays a typical Jahn-Teller distortion. Compounds 1, 2, 3 and 5 are binuclear systems in which two central manganese atoms are connected by di-u2-phenoxo-bridging from two inverse tetradentate ligands. The asymmetric unit of compound 4 contains two moieties, which is composed of a dimeric unit [Mn(L1)(SCN)]2 and two monomeric units [Mn(L1)(SCN)(C2H5OH)]. Compound 6 is a linear homo-trinuclear structure. Dc variable-temperature magnetic susceptibility measurements show that compounds 1, 2, 4 and 5 exhibit paramagnetic behaviors with J = +0.202 cm−1 for 1, J = +0.203 cm−1 for 2, J = +1.03 cm−1 for 4 and + 0.152 cm−1 for 5, respectively, whereas compounds 3 and 6 show a strong antiferromagnetic interaction between the high-spin metal centers. In addition, we investigated the relationship between the structures and magnetic behaviour.

N-Benzoyl-morpholine-4-carbothioamides: Crystal structures, Hirshfeld surface analysis, and Density functional theory calculations

The current research work describes facile synthesis, single crystal X-ray structures, Hirshfeld surface (HS) analysis, and density functional theory (DFT) calculations of two N-benzoyl-morpholine-4-carbothioamides (NDMC and NMMC). Consequently, the synthesized compounds, C12H12Cl2N2O2S (NDMC) and C13H16N2O2S (NMMC) crystallized in triclinic and monoclinic crystal systems each having respective space groups of P -1 and P 21, with corresponding a = 7.8045 (3) Å, b = 12.8458 (6) Å, c = 13.4946 (7) Å, α = 97.313 (4)°, β = 94.358 (4)°, γ = 93.348 (3)°, Z = 4 and V = 1334.84 (11) Å3 for compound (NDMC). Similarly, for compound (NMMC),a = 7.3322 (2) Å, b = 5.3045 (1) Å, c = 16.3367 (5) Å, α = 90°, β = 94.285 (3)°, γ = 90°, Z = 2 and V = 633.62 (3) Å3. Subsequently, the asymmetric unit of compound (NDMC) contains two molecules, while compound (NMMC) has single molecule. Strong intermolecular NH⋯O, and weaker CH⋯Cl and CH⋯S hydrogen bonds link the molecules of (NDMC) into dimers, enclosing R22(7) and R22(9) ring motifs. Intermolecular CH⋯S, bifurcated NH⋯O and CH⋯O hydrogen bonds, as well as CH⋯π interactions in (NMMC), attach molecules, enclosing R22(7) and R22(14) ring motifs. Furthermore, HS analysis explored, visualized, and quantified the significance of hydrogen bond contacts, and revealed active contributions for the packed crystals encompasses H…H 33.6 % for (NDMC), and 46.6 % for (NMMC), H…S/S…H 17.9 % for (NDMC), and 17.0 % for (NMMC), H…C/C…H 9.0 % for (NDMC), and 19.7 % for (NMMC), H…O/O…H 14.8 % for (NDMC), and 14.3 % for (NMMC), and H…Cl/Cl…H 17.8 % for (NMMC). Hydrogen bonding and van der Waals contacts strongly influence crystal packings of the crystallized compounds. Similarly, evaluation of energy frameworks (electrostatic, dispersion and total energies) indicated stabilization is strongly dominated by dispersion energy contribution in compound (NMMC). Finally, optimum molecular structures of both the compounds (NDMC and NMMC), were related with the experimental ones employing DFT at B3LYP/6–311G**(d,p) level. The most stable optimized conformation was geometrically complementary with the crystal structure. DFT computed frontier molecular energies and isodensities predicted these compounds to exhibit better electron pair acceptance nature than electron pair donor.

Syntheses and crystal structures of bis-(4-methyl-pyridine-κN)bis-(seleno-cyanato-κN)zinc(II) and catena-poly[[bis-(4-methyl-pyridine-κN)cadmium(II)]-di-μ-seleno-cyanato-κ2 N:Se;κ2 Se:N

The reactions of Zn(NO3)2 .6H2O and Cd(NO3)2 .4H2O with KSeCN and 4-meth-yl-pyridine (C6H7N; 4-picoline) lead to the formation of crystals of bis-(4-methyl-pyridine-κN)bis-(seleno-cyanato-κN)zinc(II), [Cd(NCSe)2(C6H7N)2] (1), and catena-poly[[bis-(4-methyl-pyridine-κN)cadmium(II)]-di-μ-seleno-cyanato-κ2 N:Se;κ2 Se:N], [Cd(NCSe)2(C6H7N)2] n (2), suitable for single-crystal X-ray diffraction. The asymmetric unit of compound 1 consists of one Zn cation that is located on a twofold rotation axis as well as one seleno-cyanate anion and one 4-methyl-pyridine ligand in general positions. The Zn cations are tetra-hedrally coordinated by two terminal N-bonding thio-cyanate anions and two 4-methyl-pyridine ligands, forming discrete complexes. The asymmetric unit of compound 2 consists of two crystallographically independent Cd cations, of which one is located on a twofold rotation axis and the second on a center of inversion, as well as two crystallographically independent seleno-cyanate anions and two crystallographically independent 4-methyl-pyridine ligands in general positions. The Cd cations are octa-hedrally coordinated by two N- and two S-bonding seleno-cyanate anions and two 4-methyl-pyridine ligands and are linked into chains by pairs of seleno-cyanate anions. Within the chains, the Cd cations show an alternating cis-cis-trans and all-trans coordination and therefore, the chains are corrugated. PXRD investigations prove that the Zn compound was obtained as a pure phase and that the Cd compound contains a very small amount of an additional and unknown phase. In the IR spectrum of 1, the CN stretching vibration of the seleno-cyanate anion is observed at 2072 cm-1, whereas in the 2 it is shifted to 2094 cm-1, in agreement with the crystal structures.

Crystal Structure of a Bis[1-(benzothiazole-2yl-2<i>κN</i>)(2-Pyridylmethyliden-1<i>κN</i>)(hydrazino-2<i>κN)</i>] Cobalt(II) Complex

The Schiff base 1-(benzothiazol-2-yl)(2-pyridylmethylidene)hydrazine (HL) was synthesis via a condensation of 1-(benzo[d]thiazol-2-yl)hydrazine and 2-pyridine carboxaldehyde in methanol in 1:1 molar ratio reaction. The crystal structure of a mononuclear complex Bis[1-(benzothiazole-2yl-2κN)(2-pyridylmethyliden-1κ<I>N</I>)(hydrazino-2κ<I>N</I>)] cobalt(II) complex (1) (CoC₂₆H₂₀N₈S₂) was obtained by the reaction of HL with Co(CH₃COO)₂.4H₂O, in 2:1 ratio, in methanol at room temperature. The ligand and the complex are characterized by IR, and physical measurement. The spectroscopic study shows that the Schiff base possesses five potential donor sites. Upon coordination the results show that the ligand acts in tridentate mode. Suitable crystals of the compound 1 were grown by slow evaporation of methanol solution for one week. The structure of 1 was elucidated by X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system with a space group of <I>P</I>2₁/c. The asymmetric unit of compound 1 contains a mononuclear complex in which the cobalt ion is coordinated to two monodeprotonated molecules of the Schiff base. Each of the ligand molecule acts through three nitrogen atoms. The Co(II) center is hexacoordinated and the environment is best described as a distorted octahedral geometry. The two ligand molecules occupy mean planes which are quasi-perpendicular with a dihedral angle of 89.77(2)°. Each molecule of complex is connected to its neighbor via hydrogen bond of type C–H•••S resulting in chains along <i>b</i> axis.

Single Crystal X-Ray Structure for the Disordered Two Independent Molecules of Novel Isoflavone: Synthesis, Hirshfeld Surface Analysis, Inhibition and Docking Studies on IKKβ of 3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-6,7-dimethoxy-4H-chromen-4-one

The structure of the isoflavone compound, 3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-6,7-dimethoxy-4H-chromen-4-one (5), was elucidated by 2D-NMR spectra, mass spectrum and single crystal X-ray crystallography. Compound 5, C19H16O6, was crystallized in the monoclinic space group P21/c with the cell parameters; a = 12.0654(5) Å, b =11.0666(5) Å, c = 23.9550(11) Å, β = 101.3757(16)°, V = 3135.7(2) Å3, and Z = 8. The asymmetric unit of compound 5 consists of two independent molecules 5I and 5II. Both molecules exhibit the disorder of each methylene group present in their 1,4-dioxane rings with relative occupancies of 0.599(10) (5I) and 0.812(9) (5II) for the major component A, and 0.401(10) (5I) and 0.188(9) (5II) for the minor component B, respectively. Each independent molecule revealed remarkable discrepancies in bond lengths, bond angles and dihedral angles in the disordered regions of 1,4-dioxane rings. The common feature of the molecules 5I and 5II are a chromone ring and a benzodioxin ring, which are more tilted towards each other in 5I than in 5II. An additional difference between the molecules is seen in the relative disposition of two methoxy substituents. In the crystal, the molecule 5II forms inversion dimers which are linked into chains along an a-axis direction by intermolecular C–H⋯O interactions. Additional C–H⋯O hydrogen bonds connected the molecules 5I and 5II each other to form a three-dimensional network. Hirshfeld surface analysis evaluated the relative intermolecular interactions which contribute to each crystal structure 5I and 5II. Western blot analysis demonstrated that compound 5 inhibited the TNFα-induced phosphorylation of IKKα/β, resulting in attenuating further downstream NF-κB signaling. A molecular docking study predicted the possible binding of compound 5 to the active site of IKKβ. Compound 5 showed an inhibitory effect on the clonogenicity of HCT116 human colon cancer cells. These results suggest that compound 5 can be used as a platform for the development of an anti-cancer agent targeting IKKα/β.

Synthesis, Crystal Structures and Catalytic Activities of Two Copper Coordination Compounds Bearing an N,N’-Dibenzylethylenediamine Ligand

Two copper coordination compounds bearing an N,N’-dibenzylethylenediamine ligand, namely [Cu3L(CH3COO)6]n (1) and [(CuCl4)∙(C6H5CH2NH2CH2)2] (2) (L = N,N’-dibenzylethylenediamine) were synthesized by the ethanol refluxing method. Powder X-ray diffraction (PXRD), infrared spectra (IR), elemental analyses, and single crystal X-ray diffraction were used to characterize and verify their structures. Structural analyses showed that the asymmetric unit of compound (1), composed of two Cu(II) cations, three acetate anions, and half of the ligand, was bridged by one acetate to obtain an infinite 1D chain structure. The analyses further showed that the asymmetric unit of compound (2), composed of two crystallographically independent [C6H5CH2NH2CH2]+ units, four chloride anions, and one central Cu(II) cation is connected into an infinite 2D network structure by the hydrogen bonding interactions. The copper compounds were used to catalyze the decomposition of H2O2, and the results showed that both of the compounds exhibited excellent catalytic activities under optimized conditions.

Chiral Bent‐Shaped Molecules Exhibiting Unusually Wide Range of Blue Liquid‐Crystalline Phases and Multistimuli‐Responsive Behavior

Recently, an unprecedented observation of polar order, thermochromic behavior, and exotic mesophases in new chiral, bent-shaped systems with a -CH3 moiety placed at the transverse position of the central core was reported. Herein, a homologous series of compounds with even-numbered carbon chains from n=4 to 18 were synthesized, in which -Cl was substituted for -CH3 at the kink position and a drastic modification in the phase structure of the bent-shaped molecule was observed. An unusual stabilization of the cubic blue phase (BP) over a wide range of 16.4 °C has been witnessed. Two homologues in this series (1-12 and 1-14) exhibit an interesting phase sequence consisting of BPI/II, chiral nematic, twist grain boundary, smectic A, and smectic X (SmX) phases. The higher homologues (1-16 and 1-18) stabilize the SmX phase enantiotropically over the entire temperature range. Crystal structure analysis confirmed the bent molecular architecture, with a bent angle of 148°, and revealed the presence of two different molecular conformations in an asymmetric unit of compound 1-4. A DFT study corroborated that the -Cl moiety at the central core of the molecule led to an increase in the dipole moment along the transverse direction, which, in turn, facilitated the unusual stabilization of frustrated structures. Crystal polymorphism has been evidenced in three homologues (1-10, 1-12, and 1-14) of the series. On the application of mechanical pressure through grinding, compound 1-10 transformed from a bright yellow crystalline solid to a dark orange-green amorphous solid, which reversed upon dropwise addition of dichloromethane, indicating reversible mechanochromism in this class of compounds. In addition, excellent thermochromic behavior has been observed for compound 1-10 with a controlled temperature-color combination.

Electronic aspects of hydrogen bond patterns of P=O···H in crystal structures of phosphoramido acid derivatives: QSAR study of anti-urease activity, Hirshfeld surface analysis, and DFT calculations

New derivatives of phosphoramido acid with the formula(C6H11NCH3)(NHCOCF3)P(O)(O−)(CH3–+NH2–C6H11)(1) (amidophosphoricacid), (C6H5)2P(O)(O−)(+NH3–C6H4–NH2)(2) (phosphonicacid), (C6H5O)2P(O)(O−)(+NH3–C6H4–NH2) (3) (phosphoricacidester) were synthesized and characterized by X-ray crystallography. The asymmetric unit of compounds 1–3 consists of one molecule with the P atom in a tetrahedral environment. The X-ray structural analysis showed that the H-bond patterns depend on the kind of atoms linked to the P atom. In the crystal packing of compound 1, P(O)···H–N and C(O)···H–N hydrogen bonds in 3 and P(O)···H–N distances in compounds 2 and 3 led to a one-dimensional arrangement. The energy of P–O···H–N hydrogen bond (EHB) model and stabilizing energies (E2) were calculated. Hirshfeld surface analysis demonstrated that the C···H contact is attributed to CH···π contact in the 2 and 3 compounds and the F···H contact is referred to hydrogen bond in one O···H counterion interaction. Quantitative structure–activity relationship (QSAR) was used to comprehend the relationship between molecular structural features and the inhibitory of investigated compounds. The use of density functional theory along with the QSAR model for enzymes revealed the importance of QH parameter in describing the anti-AChE and anti-urease activities of monophosphoramidates including P(O)–NH2 moiety.

Crystal structures of three 6-aryl-2-(4-chlorobenzyl)-5-[(1H-indol-3-yl)methyl]imidazo[2,1-b][1,3,4]thiadiazoles

Three title compounds, namely, 2-(4-chloro-benz-yl)-5-[(1H-indol-3-yl)meth-yl]-6-phenyl-imidazo[2,1-b][1,3,4]thia-diazole, C26H19ClN4S, (I), 2-(4-chloro-benz-yl)-6-(4-fluoro-phen-yl)-5-[(1H-indol-3-yl)meth-yl]imidazo[2,1-b][1,3,4]thia-diazole, C26H18ClFN4S, (II), and 6-(4-bromo-phen-yl)-2-(4-chloro-benz-yl)-5-[(1H-indol-3-yl)meth-yl]imidazo[2,1-b][1,3,4]thia-diazole, C26H18BrClN4S, (III), have been prepared using a reductive condensation of indole with the corresponding 6-aryl-2-(4-chloro-benz-yl)imidazo[2,1-b][1,3,4]thia-diazole-5-carbaldehydes (aryl = phenyl, 4-fluoro-phenyl or 4-bromo-phen-yl), and their crystal structures have been determined. The asymmetric unit of compound (I) consists of two independent mol-ecules and one of the mol-ecules exhibits disorder of the 4-chloro-benzyl substituent with occupancies 0.6289 (17) and 0.3711 (17). Each type of mol-ecule forms a C(8) chain motif built from N-H⋯N hydrogen bonds, which for the fully ordered mol-ecule is reinforced by C-H⋯π inter-actions. In compound (II), the chloro-benzyl unit is again disordered, with occupancies 0.822 (6) and 0.178 (6), and the mol-ecules form C(8) chains similar to those in (I), reinforced by C-H⋯π inter-actions involving only the major disorder component. The chloro-benzyl unit in compound (III) is also disordered with occupancies of 0.839 (5) and 0.161 (5). The mol-ecules are linked by a combination of one N-H⋯N hydrogen bond and four C-H⋯π inter-actions, forming a three-dimensional framework.

N-H…O, C-H… O hydrogen-bonded supramolecular frameworks in 4-fluoroanilinium and dicyclohexylaminium picrate salts

The asymmetric unit of compound (I), 4-fluoroanilinium picrate, C6H7NF+.C6H2N3O7− contain one 4-fluoroanilinium cation and one picrate anion whereas in compound (II), dicyclohexylaminium picrate, C12H22N+.C6H2N3O7− the asymmetric unit contains two sets of dicyclohexylaminium cation and picrate anion due to conformational difference between the molecules. In (I), all three nitro groups of the picrate anion are positionally disordered over two sites refined to major and minor components. The molecular ions of (I), interlinked through N–H‧‧‧O and C–H‧‧‧O hydrogen bonds forming two-dimensional supramolecular sheet along (-1 0 1) plane. Whereas in (II), the symmetry-independent molecules labeled as A and B molecule form independent one-dimensional supramolecular tape extending along (1 1 0) and (1 0 0) direction. The supramolecular tapes are interlinked through C–H‧‧‧O interaction to form three-dimensional network in the crystalline solid in (II).

Crystal structures of (aceto-nitrile-κN)tris-(pyridine-4-thio-amide-κN)bis-(thio-cyanate-κN)cobalt(II) aceto-nitrile disolvate and tetra-kis-(pyridine-4-thio-amide-κN)bis-(thio-cyanate-κN)nickel(II) methanol penta-solvate.

Reaction of Co(NCS)2 or Ni(NCS)2 with pyridine-4-thio-amide in different solvents led to the formation of two compounds with composition [Co(NCS)2(C2H3N)(C6H6N2S)3]·2CH3CN (1) and [Ni(NCS)2(C6H6N2S)4]·5CH3OH (2), respectively. The asymmetric unit of compound 1 consists of one cobalt(II) cation, two thio-cyanate anions, three pyridine-4-thio-amide ligands, one coordinating and two solvate aceto-nitrile mol-ecules. One of the two aceto-nitrile solvate mol-ecules is disordered over two sets of sites in a 0.62:0.38 ratio. The asymmetric unit of compound 2 comprises of one nickel(II) cation, two thio-cyanate anions, four N-bonding pyridine-4-thio-amide ligands and five methanol solvate mol-ecules. In compound 1, the cobalt(II) cations are octa-hedrally coordinated into discrete complexes by two terminal N-bonding thio-cyanate anions, the N atoms of three pyridine-4-thio-amide ligands and one aceto-nitrile mol-ecule. Additional aceto-nitrile solvate mol-ecules are located between the complexes,. The complexes and solvate mol-ecules are linked via inter-molecular hydrogen bonding into a three-dimensional framework. In compound 2, the nickel(II) cations are likewise octa-hedrally coordinated by two terminal N-bonded thio-cyanate anions and four N-bonding pyridine-4-thio-amide ligands into discrete complexes. From their arrangement cavities are formed, in which the methanol solvate mol-ecules are located. Again, the complexes and solvate mol-ecules are linked into a three-dimensional framework by inter-molecular hydrogen bonding.

Crystal structures, spectroscopic characterization, and Hirshfeld surface analyses of three constrained cyclam compounds with perchlorate counteranions

Three constrained cyclam compounds with perchlorate anions, 3,14-diethyl-2,6,13,17-diazadiazoniatricyclo[16.4.0.07,12]docosa-2,13-diene diperchlorate [H2L1](ClO4)2 (1), 3,14-diethyl-2,13-diaza-6,17-diazoniatricyclo(16.4.0.07,12)docosane [H2L2](ClO4)2 (2), and bis(3,14-diethyl-2,6,13,17-tetraazatricyclo(16.4.0.07,12)docosane) di(sodium perchlorate) (L2)2·2NaClO4 (3), have been characterized by elemental analysis and single-crystal X-ray diffraction studies, as well as IR, Raman, and NMR spectroscopy. The asymmetric units of compounds 1 and 2 contain one half dication of [H2L1]2+ or [H2L2]2+ and one perchlorate anion, whereas the asymmetric unit of compound 3 comprises two free L2 molecules, two sodium cations, and two perchlorate anions. The ClO4− ions in 1 and 2 are doubly disordered about a noncrystallographic local threefold axis, and the two ClO4− ions in 3 are fully occupied, although distorted by interactions with adjacent Na+ ions and ligand NH groups. In 1 and 2, the crystals are stabilized by 3D networks of NH⋯O and NH⋯N hydrogen bonds, whereas the crystal structure of 3 is maintained by NH⋯N hydrogen bonds and Na+⋯O/N ion-dipole interactions. Hirshfeld surface analyses with 2D fingerprint plots reveal that the H⋯H and O⋯H interactions are the main intermolecular interactions.

Crystal structures of tetra-kis-(pyridine-4-thio-amide-κN)bis-(thio-cyanato-κN)cobalt(II) monohydrate and bis-(pyridine-4-thio-amide-κN)bis-(thio-cyanato-κN)zinc(II).

Reaction of Co(NCS)2 and Zn(NCS)2 with 4-pyridine-thio-amide led to the formation of compounds with composition [Co(NCS)2(C6H6N2S)4]·H2O (1) and [Zn(NCS)2(C6H6N2S)2] (2), respectively. The asymmetric unit of compound 1, consists of one cobalt(II) cation, two thio-cyanate anions, four 4-pyridine-thio-amide ligands and one water mol-ecule whereas that of compound 2 comprises one zinc(II) cation that is located on a twofold rotation axis as well as one thio-cyanate anion and one 4-pyridine-thio-amide ligand in general positions. In the structure of compound 1, the cobalt(II) cations are octa-hedrally coordinated by two terminal N-bonding thio-cyanate anions and by the N atoms of four 4-pyridine-thio-amide ligands, resulting in discrete and slightly distorted octa-hedral complexes. These complexes are linked into a three-dimensional network via inter-molecular N-H⋯S hydrogen bonding between the amino H atoms and the thio-cyanate S atoms. From this arrangement, channels are formed in which the water mol-ecules are embedded and linked to the host structure by inter-molecular O-H⋯S and N-H⋯O hydrogen bonding. In the structure of compound 2, the zinc(II) cations are tetra-hedrally coordinated by two N-bonding thio-cyanate anions and the N atoms of two 4-pyridine-thio-amide ligands into discrete complexes. These complexes are likewise connected into a three-dimensional network by inter-molecular N-H⋯S hydrogen bonding between the amino H atoms and the thio-amide S atoms.

Crystal structures of bis-[4-(di-methyl-amino)-pyridinium] tetra-kis-(thio-cyanato-κN)manganate(II) and tris-[4-(di-methyl-amino)-pyridinium] penta-kis(thio-cyanato-κN)manganate(II).

The crystal structures of the title salts, (C7H11N2)2[Mn(NCS)4] (1) and (C7H11N2)3[Mn(NCS)5] (2), consist of manganese(II) cations that are tetra-hedrally (1) or trigonal-bipyramidally (2) coordinated to four or five terminal N-bonded thio-cyanate ligands, respectively, into discrete anionic complexes. The negative charge is compensated by two (1) or three (2) 4-(di-methyl-amino)-pyridinium cations, which are protonated at the pyridine N atom. The asymmetric unit of compound 1 consists of one anionic complex and two 4-(di-methyl-amino)-pyridinium cations, whereas that of compound 2 consists of two anionic complexes and six 4-(di-methyl-amino)-pyridinium cations, all of them located in general positions. These complexes are linked by N-H⋯S, C-H⋯S and C-H⋯N hydrogen-bonding inter-actions between the 4-(di-methyl-amino)-pyridinium cations and the thio-cyanate ligands into three-dimensional network structures.

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

Hydrothermal synthesis, structure and properties of a new phosphomolybdate based on novel [Co(H2O)4(HP2Mo5O23)]8- anions and [H8(H2O)16]8+ water cluster cations

A pure inorganic {P2Mo5O23}6– based cobalt complex [H8(H2O)16][Co(H2O)4(HP2Mo5O23)2] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet- visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one {P2Mo5O23}6– anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two {P2Mo5O23}6– clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H8(H2O)16]8+ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.

Syntheses, structural, spectroscopic and magnetic properties of polynuclear Fe(III) complexes containing N and O donor ligands

Syntheses, X-ray structural and spectroscopic properties are reported for [{Fe(L)2}3Fe] (1), [Fe2(L)2(ClCH2COO)2(H2O)] (2) and [Fe(L)(HL)]2 (3) [H2L=a tridentate ONO-donor ligand N-(2-hydroxyphenyl)salicylidenimine]. For (2) and (3), variable temperature magnetic susceptibilities have been measured and modeled. Both are antiferromagnetic overall. Compound 1 has a tetranuclear Fe4O6 core with Fe(III) species at the vertices of a triangle and the fourth Fe(III) at the center of the triangle. The central Fe(III) is surrounded by six phenoxo bridges that connect it to the three peripheral Fe(III) centres. In complex 2, the two six-coordinate Fe(III) centers are bridged by a chloroacetate and two phenoxy oxygens. The remaining three coordination sites on each iron are occupied by a terminal phenoxy oxygen, an imino nitrogen and, in one case, by a water oxygen while in the other by a terminal chloroacetate oxygen. Comparison of 2 with compounds of similar core structure reveals transition between antiferromagnetic and ferromagnetic coupling occurs at a bridgehead angle between ∼97° and ∼102°. The asymmetric unit of compound 3 consists of two symmetry-independent mononuclear species (Z′=2) joined by two statistically equivalent short (2.429(2) and 2.432(2)Å) O⋯H⋯O bridges, each involving two phenolic oxygens and a strongly bound H atom. Unprecedented weak antiferromagnetic coupling between the two high spin Fe(III) species via these very strong hydrogen bonds was detected.

Crystal structures of dual dopamine D2 and serotonin 5-HT1A active arylpiperidinyl-2(1H)-3,4-dihydroquinolinones

8-(1-((5-Cyclopentenylpyridin-3-yl)methyl)piperidin-4-yl)-3,4-dihydroquinolin-2(1H)-one (1) and 8-(1-(3- cyclopentenylbenzyl)piperidin-4-yl)-3,4-dihydroquinolin-2(1H)-one (2) are synthesized and obtained in the crystalline state for X-ray diffraction studies. In the asymmetric unit of compound 1, there are two independent molecules (A and B) having similar conformations. In the crystals of compounds 1 and 2, individual molecules are linked by pairs of N–H•••O hydrogen bonds forming A–A and B–B inversion dimers with R22 (8) ring motifs. The dimers are stabilized by N–H•••O hydrogen bonds and are linked via C–H•••O short contact interactions, forming a three-dimensional and two-dimensional networks in 1 and 2 respectively. The network in 2 is further stabilized by a number of C–H•••π interactions. Compounds 1 and 2 have a dual dopamine D2 and serotonin 5-HT1A receptor profile.

Crystal structures of {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O} n and {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O} n [where Lpn = (R)-propane-1,2-di-amine]: two heterometallic chiral cyanide-bridged coordination polymers.

The title compounds, catena-poly[[[bis-[(R)-propane-1,2-di-amine-κ(2) N,N']copper(II)]-μ-cyanido-κ(2) N:C-[tris-(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ(2) C:N] monohydrate], {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O} n , (I), and poly[[hexa-μ-cyanido-κ(12) C:N-hexa-cyanido-κ(6) C-hexa-kis-[(R)-propane-1,2-di-amine-κ(2) N,N']dichromium(III)tricopper(II)] penta-hydrate], {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O} n , (II) [where Lpn = (R)-propane-1,2-di-amine, C3H10N2], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation-anion units of {[Cu(Lpn)2][Fe(CN)5)(NO)]} and two water mol-ecules. The Fe(III) atoms have distorted octa-hedral geometries, while the Cu(II) atoms can be considered to be penta-coordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the Cu(II) atoms have distorted octa-hedral coordination spheres with extremely long semicoordination Cu-N(cyanido) bridging bonds. The chains are linked by O-H⋯N and N-H⋯N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linked via N-H⋯O and N-H⋯N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)2][Cr(CN)6]}(-) anions bridged by a chiral [Cu(Lpn)2](2+) cation and five water mol-ecules of crystallization. Both the Cr(III) atoms and the central Cu(II) atom have distorted octa-hedral geometries. The coordination spheres of the outer Cu(II) atoms of the asymmetric unit can be considered to be penta-coordinate. In the crystal, these units are bridged by long semicoordination Cu-N(cyanide) bridging bonds forming a two-dimensional network, hence these Cu(II) atoms now have distorted octa-hedral geometries. The networks, which lie parallel to (10-1), are linked via O-H⋯O, O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds involving all five non-coordinating water mol-ecules, the cyanide N atoms and the NH2 groups of the Lpn ligands, forming a three-dimensional framework.

Threefold Interpenetrated Cadmium(II) Organic Framework based on 3‐(5‐(Pyridin‐4‐yl)‐1H‐1,2,4‐triazol‐3‐yl)pyridine and 1,1′‐Biphenyl‐4,4′‐dicarboxylate

AbstractThe coordination polymer [Cd(HL)(BPDA)]n·nH2O (1) based on 3‐(5‐(pyridin‐4‐yl)‐1H‐1,2,4‐triazol‐3‐yl)pyridine (HL) and 1,1′‐biphenyl‐4,4′‐dicarboxylic acid (H2BPDA) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR spectroscopy, and elemental analysis. The asymmetric unit of compound 1 consists of one crystallographically independent CdII ion, one HL ligand, “two half” BPDA2– ligand, and one lattice water molecule. There are two crystallographically different BDPA2– moieties, but each of them is placed in a symmetry element. The BPDA2– ligands and CdII ions connected to2D sheet, and the 2D sheets are connected to a 3D MOF by the HL ligands. Each dimeric CdII unit links six nearest neighbors through the BPDA2– and HL ligands, and the dimeric CdII units are centrosymmetric. Two parallel HL ligands connect two dimeric CdII units, generating long Cd2–HL–Cd2–HL rings, also centrosymmetric. So we can define the dimeric CdII unit as a 6‐connected node. Thus, the 3D structure can be described as a threefold parallel interpenetrated bsn beta‐Sn topology. In addition, the optical properties of compound 1 and the free ligand HL were investigated.