3-(benzo[d]thiazol-2-YL)phenol and 4-(benzo[d]thiazol-2-YL)phenol: Crystal Structure Determination,DFT Calculations and Visualizing Intermolecular Interactions Using Hirshfeld Surface Analysis

This article describes the synthesis and X-ray crystal structure analysis of 3-(benzo[d]thiazol-2-yl) phenol (I) and 4-(benzo[d]thiazol-2-yl)phenol (II), crystallized in centrosymmetric triclinic and orthorhombic space groups respectively. The packing in the unit cell of these two positional isomers are different resulting difference in various types of intermolecular interactions (C-H…S, O-H…O_w and O-H…N) connect the molecules into 2D frameworks. Due to presence of lattice water in compound (I), H-bonding interactions are strong and melting point of (I) is comparatively higher than (II). The DFT optimized molecular geometries in (I) and (II) agree closely with those obtained from crystallographic studies.     

Evolution of crystal structure of Zn:N films under high temperature

Zinc‐nitrogen (Zn:N) compound thin film was prepared from a pure metallic Zn target by rf magnetron sputtering at ambient temperature under the mixture of nitrogen and argon gases with the ratio of 1:1. High temperature x‐ray diffraction (HTXRD) measurement under vacuum was used to examine the evolution of structural properties of the Zn:N film. At ambient temperature, the (002), (100), and (101) planes corresponding to Zn structure were observed while at higher temperature, the left shifts corresponding to the increase of lattice constants a and c of Zn were observed. At temperatures of 320 °C, 481 °C and 554 °C, the (222), (321) and (400) planes corresponding to Zn₃N₂ structure were observed with the decrease in the intensity amplitudes of the peaks belonging to the Zn structure. The results indicate the gradual transformation of the Zn₃N₂ phase in the Zn:N films at temperature greater than 320 °C. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and Structural Chemistry of a Ternary Calix[4]arene Lattice Inclusion System

Abstract  

A ternary calix[4]arene lattice inclusion system 3 has been synthesized, characterized and its crystal structure was determined by single crystal X-ray diffraction study. 3 is orthorhombic, space group Pbca with a = 21.236(3) ?, b = 12.2820(16) ?, c = 25.795(3) ?, α = 90°, β = 90°, γ = 90° and Z = 4. Analyses of single crystals of arene 3 crystallized from DMSO revealed the existence of a ternary system of 3 with DMSO and H₂O. Compound 3 exists in eclipsed form rather than the staggered form. Different types of host–host, host–guest and guest–guest interactions were observed and analysed.     

Synthesis and structure of tris[2-(1-naphthalenyloxy)ethyl]amine and tris[2-(1-naphthalenyloxy)ethyl]amine perchlorate

Syntheses and crystal structures of tris[2-(1-naphthalenyloxy)ethyl]amine 1 and tris[2-(1-naphthalenyloxyl)ethyl]amine perchlorate 2 are reported. Compound 1 crystallizes in the rhombohedral system, space group R3¯ with a = 13.077(4), c = 29.011(8) Å, and D _calc = 1.233g/cm³ for Z = 6; compound 2 crystallizes in the cubic system, space group P2₁3 with lattice parameters a = 14.630(5) Å and D _calc = 1.332g/cm³ for Z = 4. In 1, three naphthalene rings make dihedral angles of 109.21, 70.78, 70.78,° respectively. In 2 they make dihedral angles of 107.3, 72.7, 72.7° respectively. Deviation of N from the plane (C(12),C(12)i,C(12)ii) in 1 is 0.3742 Å which is less than that in (2) (–0.4223 Å). The crystals structure is stabilized by van der Waals interactions in both compounds.     

Crystal Structure and Hirshfeld Surface Analysis of Bis(3-thienoyl) Disulfide

The spectroscopic characterization (¹H, ¹³C{¹H} NMR, UV–Vis) and single-crystal X-ray diffraction (scXRD) analysis accomplished by inspection of the Hirshfeld surface of bis(3-thienoyl) disulfide (1) is described. The title compound 1 crystallizes in the monoclinic space group P2₁/n. The unit cell parameters are a?=?7.9959(3) Å, b?=?6.4348(3) Å, c?=?22.4924(9) Å, β?=?100.108(4)°, V?=?1139.32(8) ų, Z?=?4, R_gt(F)?=?0.0278, wR_ref(F²)?=?0.0667. The packing of 1 is dominated by S?O and S?S interactions, giving a 2D layer structure parallel to (101). The X‐ray crystal structure analysis revealed the packing of 1 is dominated by S?O and S?S interactions, giving a 2D layer structure parallel to (101). The intermolecular interactions in 1 were analyzed using the Hirshfeld surface method including 2D fingerprint plots and enrichment ratios (E), which shows that the most favored intermolecular contacts are the O?H and C?S indicated by E values above 1.30. The interaction energies between molecular pairs revealed the importance of the weak O?H and C?S interactions in stabilizing the molecular structure of 1.

Graphic Abstract

Single crystal X-ray structure analysis, DFT calculations and Hirshfeld surface analysis to identify intermolecular interactions within the solid state structure of bis(3-thienoyl) disulfide (1).

     

Crystal Structures of 1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene and 2,4,6-Trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene

Abstract  

The synthesis and X-ray crystal structure of 2,4,6-trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene (2) and the crystal structure of its core molecule, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (1) are reported. The compounds 1 and 2 crystallize in the triclinic system with space group P ī. The lattice parameters of 1 and 2 are a = 9.454(2) ?, b = 9.478(4) ?, c = 9.573(2) ?, α = 116.53(2)°, β = 109.705(14)°, γ = 101.293(18)°, V = 658.5(4) and a = 15.7707(6) ?, b = 16.3646(5) ?, c = 18.2805(6) ?, α = 83.202(2)°, β = 66.0120(10)°, γ = 73.704(2)°, V = 4137.2(2), respectively. In the crystals of 1 and 2, there are one and three molecules in the asymmetric unit, respectively. The packing of the molecules in the solid is stabilized through van der Waals interactions in 1 and weak C–H···O and C–H···π interactions in 2.     

Synthesis, Structural Characterization and Spectroscopic Properties of 1,2-Bis[4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-oxobutyl]benzene

Abstract  

The crystal structure of the title compound C₂₂H₃₀N₄O₂·H₂O (L), has been determined using X-ray diffraction at 293 K. The crystal of 1,2-bis[4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-oxobutyl]benzene is in triclinic crystal system with space group P(−1) (Z = 2), lattice parameters a = 8.225(6) ?, b = 10.967(6) ?, c = 12.903(6) ?, V = 1119.1(11) ?³. Analyses of single crystals of L, crystallized from dichloromethane/diethyl ether (1:1), revealed that the molecules are arranged in couples, which adopt a pseudo chair conformation, by means of intermolecular O–H···N hydrogen bonding interactions. Moreover, the extended structure revealed a 1D chain caused by several C–H···N intermolecular interactions.     

Montecarlo Simulation of Intercalated Atomic Distributions in Layered Dichalcogenide

Abstract

Atomic distributions of intercalated guest atoms into layered dichalcogenide have been simulated taking into account the interactions between the first and second nearest neighboring guest atoms in the triangular lattices stacked with 6 layers (lattice size 18 × 18 × 6) using a MonteCarlo method. With these distributions, the X-ray patterns of Fe _x TiS₂ with x = 0.25 having the 2√a × 2a × 2c superlattice with the fractional site occupancy have been reproduced qualitatively by averaging the intensities for different patterns obtained by different random seeds.     

Structural Properties and Interlayer Interaction in (MX) x TX2-Type Ternary Chalcogenides with Layered Composite Crystal Structure

Abstract

Structural properties and interlayer interaction in mutually incommensurate (MX) _x TX₂-type ternary chalcogenides with layered composite crystal structure have been investigated on the basis of structure analysis including superspace group symmetry. It has been confirmed that charge transfer between substructures occur in (LaS) _x TiS₂ from the results of Ti K XANES spectra. The lattice stability and interlayer interaction in the (MX) _x TX₂ have been discussed with the use of bond-valence-sum (BVS) method by considering modulated structure analysis.     

Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate

The precursor compound 4,4′-diaminostilbene-2,2′disulphonic acid DAS-(SO₃H)₂ was successfully deprotonated through reactions with (n-Bu₄N)(OH) and NaOH to produce the corresponding salts sodium 4,4′-diaminostilbene-2,2′disulphonate Na₂(DAS-(SO₃)₂) (1) and tetrabutylammonium 4,4′-diaminostilbene-2,2′disulphonate (n-Bu₄N)₂(DAS-(SO₃)₂) (2). The structure of (n-Bu₄N)₂(DAS-(SO₃)₂) (2) was confirmed through the use of single crystal X-ray diffraction. Compound (2) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 10.0645(6), b = 14.2573(9), c = 17.6053(11), and β = 94.3160(10). The reaction of Cu²⁺(aq) with (n-Bu₄N)₂(DAS-(SO₃)₂) resulted in the crystallization of the molecular organocopper cluster, [CuDAS-(SO₃)₂]₂·3H₂O (3), that resembles a molecular parallelogram as revealed by single crystal X-ray diffraction. Compound (3) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 8.8647(6), b = 10.5247(7), c = 21.2265(14), and β = 93.1730(10). Within the structure of (3) each [DAS-(SO₃)₂]²⁻ ligand is shown to bind two copper atoms through interactions with three of the five available metal binding sites.

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Graphical abstract Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate Natalie C. Rader, Heather A. Nees, Paul S. Szalay*, Matthias Zeller and Allen D. Hunter The preparation of 4,4′-diaminostilbene-2,2′disulphonic and its reactivity with copper(II) are described.

     

Three New Complexes Based on a Flexible Bis(benzimidazole) Ligand and Rigid/Flexible Organic Carboxylates

Abstract  

Three new polymeric frameworks, [Ni(bbbm)(L1)₂] _n (1), [Ni(bbbm)(L2)₂] _n (2), and {[Co(bbbm)(L3)]·H₂O} _n (3) (bbbm = 1,4-bis(N-benzimidazolyl) butane, HL1 = 4-bromobenzoic acid, HL2 = 3-methylbenzoic acid, and H₂L3 = glutaric acid) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 features a one-dimensional (1D) linear chain structure bridged by bbbm ligands, which is further connected into a supramolecular double chain structure through intermolecular π–π stacking interactions. Complex 2 contains 1D zigzag chain, which is further arranged into a 2D supramolecular architecture by hydrogen bonding and π–π stacking interactions. In the structure of 3, there are infinite 1D zigzag Co(II)-bbbm chains linked together by L3 ligands to generate an undulated 2D (4,4) sheet, which is further connected by intermolecular π–π stacking interactions to form a 3D supramolecular network. Furthermore, thermal stability and luminescent property of 1–3 were investigated.     

Crystal and molecular structure of adduct of 6-benzylaminopurine and 5-sulfosalicylic acid

The crystal structure of adduct of 6-benzylaminopurine and 5-sulfosalicylic acid C₁₉H₂₅N₅O₁₀S 1 is studied using single-crystal diffraction (R = 0.0482 for 2852 reflections with I > 2σ(I)). The asymmetric unit of 1 contains one 6-benzylaminopurine molecule and one 5-sulfosalicylic acid molecule, as well as four lattice water molecules. Hydrogen bonds, formed by 6-benzylaminopurine and 5-sulfosalicylic acid, link the two molecules into one-dimensional chain (omitting four water molecules), further joined to two-dimensional layer network. Short ring-interactions with intra-chain π-π stacking are observed. The data of IR spectroscopy confirm the formation of the two-dimensional supramolecular layer structure. At last, a 3D supramolecular network constructs via hydrogen bonds.     

Synthesis and crystal structure of the copper(I) complex with 2-[(o-pyridyl)-sulfanylmethyl]-pyrimidine ligand

The reaction of a flexible monothioether ligand, 2-[(o-pyridyl)-sulfanylmethyl]-pyrimidine (L), with CuI leads to the formation of a novel complex [Cu₄I₄(L)₂] (1), which has been characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analysis: monoclinic, space group P2₁/n, with a = 10.921(5), b = 10.824(5), c = 13.128(6) Å, β = 109.333(5)° and Z = 2. Single-crystal X-ray analyses show that complex 1 is tetranuclear structure with a distorted chair-like Cu₄I₄ skeleton. Cu···Cu interactions are found to exist in this tetranuclear molecule. In the packing mode of complex 1, there exist N⋯⋯⋯I weak interactions and intermolecular π–π contacts. These weak interactions not only stabilize the structure of complex, but also further link the tetranuclear molecules into a high-dimensional supramolecular architecture.     

Characterization of nanocrystals in laser condensates deposited through vanadium evaporation in an oxygen atmosphere

The influence of the substrate temperature T _sub (20–360°C) and the oxygen pressure P(O₂) (5 × 10⁻³−0.13 Pa) in an evaporation chamber on the structure and phase composition of films prepared through laser sputtering of a vanadium target is investigated by electron diffraction and in situ transmission electron microscopy (with the use of the bend extinction contour technique for determining the bending of the crystal lattice). It is demonstrated that the oxygen content in the films increases with an increase in the oxygen pressure P(O₂) at a fixed substrate temperature T _sub and decreases with an increase in the substrate temperature T _sub at a fixed oxygen pressure P(O₂). The conditions responsible for the formation and composition of the crystalline (VO_0.9) and amorphous (V₂O₃) phases in the films are determined. It is established that the phase composition of the film depends on the angle of condensation of the vapor-plasma flow. The crystallization of the V₂O₃ amorphous phase is accompanied by an increase in the density by 9.2%. It is revealed that the V₂O₃ spherulites growing in the amorphous film have a bent crystal lattice. The bending of the crystal lattice can be as large as ∼42 deg/μm.

     

Synthesis and crystal structure of a silver(I) complex with dithioether ligand

The reaction of the dithioether ligand, 2,3-bis(5-methyl-1,3,4-thiadiazole-2-thiomethyl) quinoxaline (L) with AgBF₄, leads to the formation of a novel complex {[AgL](BF₄)}_∞ 1, which has been characterized by single-crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 20.316(7) ?, b = 12.401(4) ?, c = 18.039(6) ?, β = 108.404(6)° and V = 4312(3) ?³. The crystal structure of the complex consists of 1D {[AgL]⁺}_∞ cation chain and BF₄ ⁻ anions. In 1, the coordination geometry of Ag^I center can be best described as trigonal planar coordinated by three N from two distinct L ligands. The ligand is polydentate with one end adopting a bidentate conformation to chelate an Ag^I atom and the other end monodentate to bridge another Ag^I resulting in an infinite chain along b axis. There exist Ag⋯N weak coordination, π–π stacking and F⋯S weak interactions in the complex, and these weak interactions link the 1D complex into 3D supramolecular structure and further stabilize the crystal structure in the solid state.     

CoL(SO4)0.5 ?·?4H2O and MnL2 ?· 2H2O (L = 1,10-Phenanthroline-4,5- f -triazolate): Synthesis, Crystal Structures and Hydrogen-Bonded Networks

Abstract  Two metal complexes of 1H-triazo-4,5-f-1,10-phenanthroline (HL), CoL(SO₄)_0.5 · 4H₂O (1) and MnL ₂ · 2H₂O (2) have been synthesized on hydrothermal conditions and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 was further assembled into a three-dimensional (3D) supramolecular network through the hydrogen-bonding interactions and inter-molecular π···π stacking interaction, 2 further assembled into a two-dimensional (2D) layer structure. This result shows that hydrogen-bonding interactions and π···π stacking interaction play important roles in the formation of coordination networks, especially in the aspect of linking the multinuclear discrete subunits or low-dimensional entities into high-dimensional supramolecular frameworks. Index abstract  Two metal complexes of 1H-triazo-4,5-f-1,10-phenanthroline (HL), CoL(SO₄)_0.5 · 4H₂O (1) and MnL₂ · 2H₂O (2) have been synthesized on hydrothermal conditions. Complex 1 was further assembled into a three-dimensional (3D) supramolecular network through the hydrogen-bonding interactions and inter-molecular π···π stacking interaction, 2 further assembled into a two-dimensional (2D) layer structure.      

Co-crystal structures of 2,4-diamino-6-phenyl-1,3,5-triazine – 4-chlorobenzoic acid/4-methoxybenzoic acid: Synthesis,structural and Hirshfeld surface analysis

The co-crystal structure of 2,4-diamino-6-phenyl-1,3,5-triazine with 4-chlorobenzoic acid/4-methoxybenzoic acid molecules are explain the link between the dimension and shape of their hydrogen-bonded assembly. The co-crystal structure of 2,4-diamino-6-phenyl-1,3,5-triazine with 4-chlorobenzoic acid/4-methoxybenzoic acid forming a cyclic R₂²(8) ring motif via N–H?O and O–H?N hydrogen bonding interactions, to form a supramolecular heterosynthon. In both the co-crystal structures, self-association of 2,4-diamino-6-phenyl-1,3,5-triazine moieties are connected via N-H^….N base pairs with cyclic R₂²(8) motif form a supramolecular homosynthon. In co-crystal II, the centrosymmetrically paired methoxy group of 4-methoxy benzoic acid form a supramolecular homosynthon via weak intermolecular C-H^….O hydrogen bonds, generating R₂²(6) ring motif. Both the co-crystal structures are stabilized by weak aromatic π-π and C—Cl???π stacking interactions. Hirshfeld surface and fingerprint plots were used to study the intermolecular interactions both of the crystal structures.     

N–H···π Interactions in Two Isomers of an Amino Group Containing <Emphasis Type="Italic">bis</Emphasis>-Phenol

Abstract  

Crystal structures of two bis-phenols namely bis-(3,5-dimethyl-2-hydroxyphenyl)(3-amino phenyl)methane 1 and bis-(3,5-dimethyl-4-hydroxyphenyl)(3-aminophenyl) methane 2 are determined. The compound 1 crystallises in monoclinic P2₁/c with a = 12.2579(16) ?, b = 16.0906(19) ?, c = 10.6664(13) ?, β = 115.417(7)°, V = 1900.2(4) ?³ whereas 2 crystallizes in monoclinic C2/c, a = 9.2538(2) ?, b = 18.6579(4) ?, c = 23.2725(5) ?, β = 98.796(2)°, V = 3970.89(15) ?³. The crystal lattice of both the compounds shows presence of N–H···π interactions but no O–H···π interactions.     

VERTICALLY SUSPENDED SMECTIC FILMS WITH IN-PLANE TEMPERATURE GRADIENTS

Abstract

We present a study of vertically suspended smectic films under the influence of temperature gradients in the film plane. It is shown that such gradients lead to the transport of smectic material, even against the action of the gravitation forces, from the hot to the cold film edge. In addition, we observe thermally driven convection in these films, and it is demonstrated that the surrounding air plays an essential role for this instability. We compare this result with convective patterns in soap films reported by Martin and Wu in Phys. Rev. Lett. 80 1892 (98) and give some evidence that their interpretation has to be modified, the contact with surrounding air has to be taken into account.     

Hydrothermal Synthesis, Structural Characterization and Luminescent Property of a New 1-D Chain-like [Er(NC6H4O2)3(H2O)2]n

Abstract  

Erbium (III) coordination compound with the formula [Er(IN)₃(H₂O)₂]_n 1 (HIN = isonicotinic acid) was synthesized by mixing Er₂O₃ with isonicotinic acid under hydrothermal condition. The structure of the title compound was determined by single crystal X-ray diffraction analysis, which reveals that the 1-D chain-like structure is formed by the erbium polyhedra through the carboxyl groups of IN. It crystallizes in the monoclinic system, possesses space group C2/c, with lattice parameters: a = 20.229(10) ?, b = 11.594(6) ?, c = 9.871(5) ?, α = γ=90°, β = 115.509(6)°, V = 2089.3(18) ?³, and D _calc = 1.811 mg/cm³ for Z = 4, F(000) = 1108, GOF = 1.109, R1 = 0.0675. Compound 1 has been characterized by IR absorption spectroscopy, ultraviolet excitation and emission spectrum.