MgO-Template Synthesis of Extremely High Capacity Hard Carbon for Na-Ion Battery.

Extremely high capacity hard carbon for Na-ion battery, delivering 478 mAh g-1 , is successfully synthesized by heating a freeze-dried mixture of magnesium gluconate and glucose by a MgO-template technique. Influences of synthetic conditions and nano-structures on electrochemical Na storage properties in the hard carbon are systematically studied to maximize the reversible capacity. Nano-sized MgO particles are formed in a carbon matrix prepared by pre-treatment of the mixture at 600 °C. Through acid leaching of MgO and carbonization at 1500 °C, resultant hard carbon demonstrates an extraordinarily large reversible capacity of 478 mAh g-1 with a high Coulombic efficiency of 88 % at the first cycle.

Bis(4-meth-oxy-3,4-di-hydro-quinazolin-1-ium) chloranilate.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: bis-(4-meth-oxy-3,4-di-hydro-quinazolin-1-ium) 2,5-di-chloro-3,6-dioxo-cyclo-hexa-1,4-diene-1,4-diolate], 2C9H11N2O(+)·C6Cl2O4 (2-), the chloranil-ate anion lies about an inversion center. The 4-meth-oxy-3,4-di-hydro-quinazolin-1-ium cations are linked on both sides of the anion via bifurcated N-H⋯(O,O) and weak C-H⋯O hydrogen bonds, giving a centrosymmetric 2:1 aggregate. The 2:1 aggregates are linked by another N-H⋯O hydrogen bond into a tape running along [1-10]. The tapes are further linked by a C-H⋯O hydrogen bond into a layer parallel to the ab plane.

Bis(tri-ethyl-ammonium) chloranilate.

IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND [SYSTEMATIC NAME: bis-(tri-ethyl-ammonium) 2,5-di-chloro-3,6-dioxo-cyclo-hexa-1,4-diene-1,4-diolate], 2C6H16N(+)·C6Cl2O4 (2-), the chloranilate anion lies on an inversion center. The tri-ethyl-ammonium cations are linked on both sides of the anion via bifurcated N-H⋯(O,O) and weak C-H⋯O hydrogen bonds to give a centrosymmetric 2:1 aggregate. The 2:1 aggregates are further linked by C-H⋯O hydrogen bonds into a zigzag chain running along [01-1].

Temperature dependence of one-dimensional hydrogen bonding in morpholinium hydrogen chloranilate studied by 35Cl nuclear quadrupole resonance and multi-temperature X-ray diffraction.

The temperature dependence of (35)Cl NQR frequencies and the spin-lattice relaxation times T(1) has been measured in the wide temperature range of 4.2-420 K for morpholinium hydrogen chloranilate in which a one-dimensional O-HO hydrogen-bonded molecular chain of hydrogen chloranilate ions is formed. An anomalous temperature dependence of the NQR frequencies was analyzed to deduce a drastic temperature variation of the electronic state of the hydrogen-bonded molecular chain. The hydrogen atom distribution in the OHO hydrogen bond is discussed from the results of NQR as well as multi-temperature X-ray diffraction. Above ca. 330 K, the T(1) showed a steep decrease with an activation energy of ca. 70 kJ mol(-1) and with an isotope ratio (37)Cl T(1)/(35)Cl T(1) = 0.97 ± 0.2. The orientational change of the z axis of electric field gradient tensor in conjunction with the hydrogen transfer between adjacent hydrogen chloranilate ions is suggested as a possible relaxation mechanism.

A triclinic polymorph of 4-cyano-pyridinium hydrogen chloranilate.

THE ASYMMETRIC UNIT OF THE TRICLINIC POLYMORPH OF THE TITLE COMPOUND (SYSTEMATIC NAME: 4-cyano-pyridinium 2,5-dichloro-4-hy-droxy-3,6-dioxocyclo-hexa-1,4-dien-1-olate), C(6)H(5)N(2) (+)·C(6)HCl(2)O(4) (-), consists of two crystallographically independent cation-anion units, in each of which the cation and the anion are linked by an N-H⋯O hydrogen bond. In the units, the dihedral angles between the cation and anion rings are 78.43 (11) and 80.71 (11)°. In the crystal, each unit independently forms a chain through N-H⋯O and O-H⋯N hydrogen bonds; one chain runs along the c axis while the other runs along [011]. Weak C-H⋯O, C-H⋯N and C-H⋯Cl inter-actions are observed between the chains.

Rh-catalyzed carbonylation of arylzinc compounds yielding symmetrical diaryl ketones by the assistance of oxidizing agents.

Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homocoupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh(3+) intermediate occurred.

Synthesis of ternary and quaternary graphite intercalation compounds containing alkali metal cations and diamines.

A series of ternary graphite intercalation compounds (GICs) of alkali metal cations (M = Li, Na, K) and diamines [EN (ethylenediamine), 12DAP (1,2-diaminopropane), and DMEDA (N,N-dimethylethylenediamine)] are reported. These include stage 1 and 2 M-EN-GIC (M = Li, d(i) = 0.68-0.84 nm; M = Na, d(i) = 0.68 nm), stage 2 Li-12DAP-GIC (d(i) = 0.83 nm), and stage 1 and 2 Li-DMEDA-GIC (d(i) = 0.91 nm), where d(i) is the gallery height. For M = Li, a perpendicular-to-parallel transition of EN is observed upon evacuation, whereas for M = Na, the EN remains in parallel orientation. Li-12DAP-GIC and Li-DMEDA-GIC contain chelated Li(+) and do not show the perpendicular-to-parallel transition. We also report the quaternary compounds of mixed cations (Li,Na)-12DAP-GIC and mixed amines Na-(EN,12DAP)-GIC, with d(i) values in both cases between those of the ternary end members. (Li,Na)-12DAP-GIC is a solid solution with lattice dimensions dependent on composition, whereas for Na-(EN,12DAP)-GIC, the lattice dimension does not vary with amine content.

A 14N nuclear quadrupole resonance study of phase transitions and molecular dynamics in hydrogen bonded organic antiferroelectrics 55DMBP-H2ca and 1,5-NPD-H2ca.

The temperature dependence of the (14)N NQR frequencies has been measured in antiferroelectric and paraelectric 55DMBP-H(2)ca and 1,5-NPD-H(2)ca. In both compounds we observe two non-equivalent nitrogen positions (N(+)-H···O(-) and N···H-O) in the antiferroelectric phase. The two nitrogen positions become equivalent (N···H···O) in the paraelectric phase. The critical exponent of the local antiferroelectric order parameter has been determined from the NQR data. The principal values of the quadrupole coupling tensor correlate in both compounds. The correlation diagrams clearly show how a proton migrates from the antiferroelectric position towards the paraelectric position in the bifurcated hydrogen bond on increasing the temperature. A slow motion has been observed in 55DMBP-H(2)ca by the (1)H and (14)N spin-lattice relaxation. An analysis of the spin-lattice relaxation data suggests a slow exchange between two non-planar conformations of the bipyridine molecule.

Hydrogen-bonded structures of the 1:1 and 1:2 compounds of chloranilic acid with pyrrolidin-2-one and piperidin-2-one.

In the four compounds of chloranilic acid (2,5-dichloro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione) with pyrrolidin-2-one and piperidin-2-one, namely, chloranilic acid-pyrrolidin-2-one (1/1), C(6)H(2)Cl(2)O(4)·C(4)H(7)NO, (I), chloranilic acid-pyrrolidin-2-one (1/2), C(6)H(2)Cl(2)O(4)·2C(4)H(7)NO, (II), chloranilic acid-piperidin-2-one (1/1), C(6)H(2)Cl(2)O(4)·C(5)H(9)NO, (III), and chloranilic acid-piperidin-2-one (1/2), C(6)H(2)Cl(2)O(4)·2C(5)H(9)NO, (IV), the shortest interactions between the two components are O-H...O hydrogen bonds, which act as the primary intermolecular interaction in the crystal structures. In (II), (III) and (IV), the chloranilic acid molecules lie about inversion centres. For (III), this necessitates the presence of two independent acid molecules. In (I), there are two formula units in the asymmetric unit. The O···O distances are 2.4728 (11) and 2.4978 (11) Å in (I), 2.5845 (11) Å in (II), 2.6223 (11) and 2.5909 (10) Å in (III), and 2.4484 (10) Å in (IV). In the hydrogen bond of (IV), the H atom is disordered over two positions with site occupancies of 0.44 (3) and 0.56 (3). This indicates that proton transfer between the acid and base has partly taken place to form ion pairs. In (I) and (II), N-H...O hydrogen bonds, the secondary intermolecular interactions, connect the pyrrolidin-2-one molecules into a dimer, while in (III) and (IV) these hydrogen bonds link the acid and base to afford three- and two-dimensional hydrogen-bonded networks, respectively.

Hydrogen-bonded structures of the isomeric compounds of phthalazine with 3-chloro-2-nitrobenzoic acid, 4-chloro-2-nitrobenzoic acid and 4-chloro-3-nitrobenzoic acid.

The structures of three isomeric compounds, C(7)H(4)ClNO(4)·C(8)H(6)N(2), of phthalazine with chloro- and nitro-substituted benzoic acid, namely, 3-chloro-2-nitrobenzoic acid-phthalazine (1/1), (I), 4-chloro-2-nitrobenzoic acid-phthalazine (1/1), (II), and 4-chloro-3-nitrobenzoic acid-phthalazine (1/1), (III), have been determined at 190 K. In the asymmetric unit of each compound, there are two crystallographically independent chloronitrobenzoic acid-phthalazine units, in each of which the two components are held together by a short hydrogen bond between an N atom of the base and a carboxyl O atom. In one hydrogen-bonded unit of (I) and in two units of (II), a weak C-H···O interaction is also observed between the two components. The N···O distances are 2.5715 (15) and 2.5397 (17) Å for (I), 2.5655 (13) and 2.6081 (13) Å for (II), and 2.613 (2) and 2.589 (2) Å for (III). In both hydrogen-bonded units of (I) and (II), the H atoms are each disordered over two positions with (N site):(O site) occupancies of 0.35 (3):0.65 (3) and 0.31 (3):0.69 (3) for (I), and 0.32 (3):0.68 (3) and 0.30 (3):0.70 (3) for (II). The H atoms in the hydrogen-bonded units of (III) are located at the O-atom sites.

2-Chloro-4-nitro-benzoic acid-quinoline (1/1).

In the title compound, C(7)H(4)ClNO(4)·C(9)H(7)N, the two components are connected by an O-H⋯N hydrogen bond. In the hydrogen-bonded unit, the dihedral angle between the quinoline ring system and the benzene ring of benzoic acid is 3.15 (7)°. In the crystal, units are linked by inter-molecular C-H⋯O hydrogen bonds, forming a tape along the c axis. The tapes are stacked along the b axis through a C-H⋯O hydrogen bond into a layer parallel to the bc plane.

4-Chloro-2-nitro-benzoic acid-pyrazine (2/1).

In the title co-crystal, 2C(7)H(4)ClNO(4)·C(4)H(4)N(2), the pyrazine mol-ecule is located on an inversion centre, so that the asymmetric unit consists of one mol-ecule of 4-chloro-2-nitro-benzoic acid and a half-mol-ecule of pyrazine. The components are connected by O-H⋯N and C-H⋯O hydrogen bonds, forming a 2:1 unit. In the hydrogen-bonded unit, the dihedral angle between the pyrazine ring and the benzene ring of the benzoic acid is 16.55 (4)°. The units are linked by inter-molecular C-H⋯O hydrogen bonds, forming a sheet structure parallel to ([Formula: see text]04). A C-H⋯O hydrogen-bond linkage is also observed between these sheets.

Morpholinium hydrogen chloranilate methanol monosolvate.

In the crystal structure of the title compound, C(4)H(10)NO(+)·C(6)HCl(2)O(4) (-)·CH(4)O, the components are held together by bifurcated O-H⋯(O,O), O-H⋯(O,Cl) and N-H⋯(O,O) hydrogen bonds into a centrosymmetric 2+2+2 aggregate. The aggregates are further connected by another bifurcated N-H⋯(O, O) hydrogen bond, forming a double-tape structure along the b axis. A weak C-H⋯O inter-action is observed between the tapes.

2-[4-(2-Formyl-phen-oxy)-but-oxy]-benzaldehyde.

In the crystal structure of the title compound, C(18)H(18)O(4), the full mol-ecule is generated by the application of an inversion centre. The mol-ecule is essentially planar, with an r.m.s. deviation of 0.017 (1) Šfor all non-H atoms. The mol-ecules are linked through inter-molecular C-H⋯O inter-actions to form a mol-ecular sheet parallel to the ([Formula: see text]02) plane.

Two solid phases of pyrimidin-1-ium hydrogen chloranilate monohydrate determined at 225 and 120 K.

The crystal structures of two solid phases of the title compound, C(4)H(5)N(2)(+) x C(6)HCl(2)O(4)(-) x H(2)O, have been determined at 225 and 120 K. In the high-temperature phase, stable above 198 K, the transition temperature of which has been determined by (35)Cl nuclear quadrupole resonance and differential thermal analysis measurements, the three components are held together by O-H...O, N...H...O, C-H...O and C-H...Cl hydrogen bonds, forming a centrosymmetric 2+2+2 aggregate. In the N...H...O hydrogen bond formed between the pyrimidin-1-ium cation and the water molecule, the H atom is disordered over two positions, resulting in two states, viz. pyrimidin-1-ium-water and pyrimidine-oxonium. In the low-temperature phase, the title compound crystallizes in the same monoclinic space group and has a similar molecular packing, but the 2+2+2 aggregate loses the centrosymmetry, resulting in a doubling of the unit cell and two crystallographically independent molecules for each component in the asymmetric unit. The H atom in one N...H...O hydrogen bond between the pyrimidin-1-ium cation and the water molecule is disordered, while the H atom in the other hydrogen bond is found to be ordered at the N-atom site with a long N-H distance [1.10 (3) A].

4-Chloro-benzoic acid-quinoline (1/1).

In the title compound, C(7)H(5)ClO(2)·C(9)H(7)N, the 4-chloro-benzoic acid mol-ecule is almost planar, with a dihedral angle of 2.9 (14)° between the carb-oxy group and the benzene ring. In the crystal, the two components are connected by an O-H⋯N hydrogen bond. In the hydrogen-bonded unit, the dihedral angle between the quinoline ring system and the benzene ring of the benzoic acid is 44.75 (4)°. The two components are further linked by inter-molecular C-H⋯O hydrogen bonds, forming a layer parallel to the ab plane.

Triethyl-ammonium hydrogen chloranilate.

IN THE CRYSTAL STRUCTURE OF THE TITLE COMPOUND (SYSTEMATIC NAME: triethyl-ammonium 2,5-dichloro-4-hy-droxy-3,6-dioxo-cyclo-hexa-1,4-dien-1-olate), C(6)H(16)N(+)·C(6)HCl(2)O(4) (-), two hydrogen chloranilate anions are connected by a pair of bifurcated O-H⋯O hydrogen bonds into a dimeric unit. The triethyl-ammonium cations are linked on both sides of the dimer via bifurcated N-H⋯O hydrogen bonds into a centrosymmetric 2:2 aggregate. The 2:2 aggregates are further linked by inter-molecular C-H⋯O hydrogen bonds.

Bis[(3-chloro-benz-yl)ammonium] 2-phenyl-propane-dioate dihydrate.

In the asymmetric unit of the title compound, 2C(7)H(9)ClN(+)·C(9)H(6)O(4) (2-)·2H(2)O, there are two crystallographically independent cations, one dianion and two water mol-ecules. The dihedral angle between the two carboxyl-ate groups of the dianion is 78.1 (2)°. In the crystal, the components are held together by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, forming a layer parallel to the bc plane, with the hydro-philic and hydro-phobic groups located in the inner and outer regions of the layers, respectively.

Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methyl-quinoline with 2-chloro-4-nitro-benzoic acid, 2-chloro-5-nitro-benzoic acid, 3-chloro-2-nitro-benzoic acid and 4-chloro-2-nitro-benzoic acid.

The structures of the four isomeric compounds of 6-methyl-quinoline with chloro- and nitro-substituted benzoic acids, C7H4ClNO4·C10H9N, namely, 2-chloro-4-nitro-benzoic acid-6-methyl-quinoline (1/1), (I), 2-chloro-5-nitro-benzoic acid-6-methyl-quinoline (1/1), (II), 3-chloro-2-nitro-benzoic acid-6-methyl-quinoline (1/1), (III), and 4-chloro-2-nitro-benzoic acid-6-methyl-quinoline (1/1), (IV), have been determined at 185-190 K. In each compound, the acid and base mol-ecules are linked by a short hydrogen bond between a carboxyl O atom and an N atom of the base. The O⋯N distances are 2.5452 (12), 2.6569 (13), 2.5640 (17) and 2.514 (2) Å, respectively, for compounds (I)-(IV). In the hydrogen-bonded acid-base units of (I), (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.65 (3):0.35 (3), 0.59 (4):0.41 (4) and 0.48 (5):0.52 (5), respectively, for (I), (III) and (IV). The H atom in the hydrogen-bonded unit of (II) is located at the O-atom site. In all of the crystals of (I)-(IV), π-π inter-actions between the quinoline ring system and the benzene ring of the acid mol-ecule are observed. In addition, a π-π inter-action between the benzene rings of adjacent acid mol-ecules and a C-H⋯O hydrogen bond are observed in the crystal of (I), and C-H⋯O hydrogen bonds and O⋯Cl contacts occur in the crystals of (III) and (IV). These inter-molecular inter-actions connect the acid and base mol-ecules, forming a layer structure parallel to the bc plane in (I), a column along the a-axis direction in (II), a layer parallel to the ab plane in (III) and a three-dimensional network in (IV). Hirshfeld surfaces for the title compounds mapped over d norm and shape index were generated to visualize the weak inter-molecular inter-actions.

Reaction Behavior of a Silicide Electrode with Lithium in an Ionic-Liquid Electrolyte.

Silicides are attractive novel active materials for use in the negative-electrodes of next-generation lithium-ion batteries that use certain ionic-liquid electrolytes; however, the reaction mechanism of the above combination is yet to be clarified. Possible reactions at the silicide electrode are as follows: deposition and dissolution of Li metal on the electrode, lithiation and delithiation of Si, which would result from the phase separation of the silicide, and alloying and dealloying of the silicide with Li. Herein, we examined these possibilities using various analysis methods. The results revealed that the lithiation and delithiation of silicide occurred.