Structure and detonation performance of a novel HMX/LLM‐105 cocrystal explosive

Intermolecular interactions and properties of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐ tetrazocine (HMX) / 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) cocrystal were studied by using the dispersion‐corrected density functionals (ωB97XD, B97D) and meta‐hybrid functional (M062x) methods. Binding energies, heats of formation, thermodynamic properties, atoms in molecules, and natural bond orbital analysis were performed to investigate HMX/LLM‐105 complexes. Results show that the main intermolecular interactions between HMX and LLM‐105 are CH…O, NH…O, N…O, and O…O interactions. In addition, Monte Carlo simulation was employed to predict the crystal structure of HMX/LLM‐105 cocrystal. The HMX/LLM‐105 cocrystal is most likely to crystallize in C2/c space group, and its corresponding cell parameters are Z = 8, a = 41.63 Å, b = 6.77 Å, c = 45.63 Å, ß = 164.55°, and ρ = 1.99 g/cm³. Detonation velocity and pressure of HMX/LLM‐105 cocrystal are 8.95 km/s, 37.69GPa, a little lower than those of HMX (9.10 km/s, 37.76GPa). However, according to the net charges of nitro group, HMX/LLM‐105 cocrystal exhibits less sensitive than HMX. Finally, bond dissociation energy calculation shows that HMX/LLM‐105 complexes are thermally stable. Considering thermal stability, sensitivity, and detonation performance, HMX/LLM‐105 cocrystal meets the requirements of insensitive high energy density materials. Copyright © 2013 John Wiley & Sons, Ltd.     

Manifestation of intramolecular and intermolecular interactions in infrared absorption spectra of biologically active aminophenols

FTIR methods were used to study intramolecular and intermolecular interactions in solutions and the solid state of the biologically active aminophenols 2-anilino-4,6-di-tert-butylphenol, N-(3,5-di-tert-butyl-2-methoxyphenyl)aniline, and 2,4-di-tert-butyl-10H-1-phenothiazinol. An analysis of the IR spectra has shown that intramolecular interactions between the OH and NH groups occur in solutions of 2-anilino-4,6-di-tertbutylphenol in CCl₄ to form O-H⋯N hydrogen bonds. The NH groups in solutions of N-(3,5-di-tert-butyl-2-methoxyphenyl)aniline in CCl₄ are present in the non-associated state because of the absence of hydroxyl groups in the molecular structure. The OH and NH groups in solutions of 2,4-di-tert-butyl-10H-1-phenothiazinol in CCl₄ do not interact within the molecule due to a decrease in the conformational mobility of the molecular fragments due to the presence of the rigid C_Ar-S-C_Ar molecular bond in this compound. Intermolecular interactions involving the NH groups occur in the solid state of these compounds. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 68–73, January–February, 2008.     

Polyamide 11/Poly(vinylidene fluoride) Blends as Novel Flexible Materials for Capacitors

A novel capacitor with high dielectric constant (ε) has been developed by blending poly(vinylidene fluoride) (PVDF) with polyamide (PA11). The blends show high dielectric constants (ε_blend = 40), which give better frequency stability (1 MHz), and excellent mechanical properties. Based on certain volume fractions, the measured dielectric constants (ε _blend ) were found to exceed those of the corresponding polymers, in contrasted to conventional composites, where ε_polymerA < ε_composite < ε_polymerB. SEM investigations suggest that the enhanced dielectric behavior originates from significant interfacial polymer‐polymer interactions. DSC and XRD demonstrate that blending PA11 with PVDF affects the crystalline behavior of each component. However, the PA11/PVDF blends exhibit a slightly high dielectric loss (tanδ ≈ 0.17), which is a great disadvantage to a capacitor. Adding a copolymer of styrene and maleic anhydride decreased the dielectric loss (tanδ ≈ 0.057) and increased the dielectric constant (ε_blend = 60). Our findings suggest that the high‐ε polymeric blends created represent a novel type of material that is flexible and easy to process, of relatively high dielectric constant, of high breakdown strength and, moreover, is suited to applications in flexible electronics.

     

Multiple Luminescence Responses towards Mechanical Stimulus and Photo-Induction: The Key Role of the Stuck Packing Mode and Tunable Intermolecular Interactions

Organic luminescence with different forms continues to be one of the most active research fields in science and technology. Herein, an ultra-simple organic molecule (TPA-B), which exhibits both mechanoluminescence (ML) and photo-induced room-temperature phosphorescence (RTP) in the crystalline state, provides an opportunity to reveal the internal mechanism of ML and the dynamic process of photo-induced RTP in the same molecule. Through the detailed investigation of photophysical properties together with crystal structures, the key role of molecular packing and intermolecular interactions was highlighted in the luminescence response by mechanical and light stimulus, affording efficient strategies to design potential smart functional materials with multiple luminescence properties.     

A cubane-type nickel single-molecule magnet with exchange-biased quantum tunneling of magnetization

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Synthesis,characterization, crystal structure,and antimicrobial studies of novel thiourea derivative ligands and their platinum complexes

N,N-Di-R-N′-(4-chlorobenzoyl)thiourea (Di-R: diethyl, di-n-propyl, di-n-butyl and diphenyl) ligands (HL^1–4) and their Pt(II) complexes (cis-[Pt(L^1–4-S,O)₂]) have been synthesized and structurally characterized by elemental analyses, FT-IR and NMR spectroscopy. HL² ligand and cis-[Pt(L⁴-S,O)₂] metal complex have been also characterized by a single-crystal X-ray diffraction study. HL², C₁₄H₁₉ClN₂OS, crystallizes in the monoclinic space group P2₁/n (no. 14), with Z = 4, and unit cell parameters, a = 11.1405(16) Å, b = 9.7015(12) Å, c = 14.790(2) Å, β = 106.547(7)°. The cis-[Pt(L⁴-S,O)₂], C₄₀H₂₈Cl₂N₄O₂PtS₂: triclinic, space group P-1 (no. 2), a = 8.9919(3) Å, b = 14.7159(6) Å, c = 15.7954(6) Å, α = 113.9317(18)°, β = 97.4490(18)°, and γ = 105.0492(16)°. Single crystal analysis of complex, cis-[Pt(L^1–4-S,O)₂], revealed that a square planar coordination geometry is formed around the platinum atom by two sulfur and two oxygen atoms of the related ligands, which are in a cis configuration. In addition, the thiourea derivative ligands and their complexes were evaluated for both their in-vitro antibacterial and antifungal activity. The results have been reported, explained, and compared with fluconazole and ampicillin, used as reference drugs.     

Packing effects in organometallic compounds: A study of five mixed crystals

A series of cocrystals of an organometallic tungsten complex with organic small molecules has been prepared and studied by single-crystal X-ray diffraction. Comparison of the five structures thus obtained allowed the measurement of the effects of the crystal environment on the molecular structure under investigation. Not only soft torsional degrees of freedom but also bond angles, the point symmetry, and other geometrical features of the reference molecule have been found to vary significantly. It is concluded that parameters commonly ascribed to themolecular structure may in reality depend onintermolecular interactions.Dedicated to Prof. Dr. J. Strähle on the occasion of his 60th birthday.     

X-ray structure of 2,6-dimethoxy-7-methylpurine

The title compound (C₈H₁₀N₄O₂) is monoclinic, with a = 7.740(2), b = 17.044(7), c = 6.992(3) Å, = 100.60(1)°, and space group P2₁/c. Two O-methyl groups are coplanar with the pyrimidine ring. Whereas, the O(6)-methyl group is directed away from the imidazole ring toward the N(1) atom, the O(2)-methyl is pointed away from the N(1) atom toward the N(3) atom. Two intermolecular hydrogen bonds H(8)···N(1) and H(711)···O(2) of 2.48(2) and 2.58(3) Å make a linear arrangement of the molecules. The conformation of the O-methyl groups explains some results of thermal rearrangement of 2,6-dialkoxy-7-methylpurines and differences in alkylations of 2,4-dialkoxypyrimidines and 2,6-dialkoxy-7-methylpurines.     

Synthesis and X-ray structural analysis of (2<Emphasis Type="Italic">Z</Emphasis>)-3(4-hydroxyphenyl)-2-pyridin-4-ylacrylonitrile and (2<Emphasis Type="Italic">Z</Emphasis>)-3-(3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-4-hydroxyphenyl)2-pyridin-4-ylacrylonitrile

Synthesis and X-ray structural investigations have been carried out for the two title compounds C₁₄H₁₀N₂O (3a) and C₂₂H₂₆N₂O (3b). Compound 3a crystallizes in the monoclinic space group P2₁/c, with a = 3.843(1) Å, b = 24.618(5) Å, c = 11.318(2) Å, = 92.61(3), V = 1069.7(4) Å,³ and Z = 4. Compound 3b crystallizes in the triclinic space group P-1, with a = 9.004(2) Å, b = 9.447(2) Å, c = 11.713(2) Å, = 76.70(3), = 83.12(3), = 82.16(3), V = 956.5(3) Å,³ and Z = 2. Both stilbazole derivatives have Z-geometry about the ethylene bridge which links the heterocyclic and aromatic rings. The molecular skeleton of 3a is slightly non-planar: the dihedral angles between the acrylonitrile linkage and the pyridine ring, and between this linkage and the p-hydroxyphenyl ring are 7.2(2) and 4.1(2), respectively. The molecular skeleton of 3b is less planar: the values of similar dihedral angles are 17.0(2) and 20.8(2), respectively. In the crystal of 3a, the molecules are packed in stacks along the a axis with head-to-head orientation. Intermolecular hydrogen bonds O=H s N and C=H s N link molecules into sheets parallel to (100) plane. In the crystals of 3b, the molecules have a head-to-tail orientation and intermolecular hydrogen bonds O=H s N link the molecules into infinite chains along [01-1] direction.