caa a22 4500 463240367 CHVBK 20180405153311.0 cr unu---uuuuu 170326e20070901xx s 000 0 eng 10.1007/s10947-007-0138-1 doi (NATIONALLICENCE)springer-10.1007/s10947-007-0138-1 Structure and stability of a clathrate of bis(dibenzoylmethanato)-dipyridine-nickel(II) with acetone (1:2) [Elektronische Daten] [D. Soldatov, É. Ukraintseva, V. Logvinenko] An inclusion compound of constant composition [Ni(DBM)2Py2]·2(CH3COCH3) is synthesized, Ni = Ni(II), DBM is dibenzoylmethanate-anion (C6H5CO)2CH−, Py is pyridine. The compound and its dissociation products are examined by structural and thermal analysis, as well as vapor pressure measurements. The crystal structure of the clathrate is solved in the monoclinic space group P21/n (temperature 173 K, a = 11.8617(9) Å, b = 10.0096(6) Å, c = 17.2895(9) Å, β = 96.72(1)°, V = 2038.7(2) Å3, Z = 2, final R 1 = 0.032). The host molecule [Ni(DBM)2Py2] is an uncharged octahedral complex, the central Ni(II) atom being surrounded by two DBM-anions in the equatorial plane and two terminal pyridines in the axial positions. Pairs of guest molecules are located in the voids of the molecular crystal. Calculated packing coefficients of the clathrate and the stable form of the host complex are 0.685(2) and 0.668(1) at 173 K, respectively. Isochoric melting of the clathrate has incongruent nature and occurs at 58-60°C to yield the solid phase of the host complex, while in air the complex decomposes in gaseous acetone and a metastable form of the host (apohost). The collapse of the metastable form of [Ni(DBM)2Py2] to the stable one takes place at 131°C with the release of 11 kJ/mol. The equilibrium vapor pressure of acetone over the clathrate is measured with the spoon gauge technique in a temperature interval from 292 K to 310 K (at 298 K the pressure is 0.48P 0, P 0 is the saturated vapor pressure of liquid acetone at this temperature). The experimental dependence logP − 1/T is used to derive thermodynamic parameters of the process of clathrate dissociation 1/2[Ni(DBM)2Py2]· 2(CH3COCH3)(s) = 1/2[Ni(DBM)2Py2](s) + CH3COCH3(gas): ΔH av 0 = 53±3 kJ/mol, ΔS av 0 = 160±10 J/(mol·K), ΔG 298 0 = 4.74±0.07 kJ/mol. Springer Science+Business Media, Inc., 2007 molecular crystal nationallicence inclusion compound nationallicence polymorphism nationallicence apohost nationallicence thermal analysis nationallicence static vapor pressure measurements nationallicence vapor pressure nationallicence thermodynamic stability nationallicence clathration enthalpy nationallicence β-diketonate nationallicence Soldatov D. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut Ukraintseva É. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut Logvinenko V. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut Journal of Structural Chemistry Springer US 48/5(2007-09-01), 938-948 0022-4766 48:5<938 2007 48 10947 https://doi.org/10.1007/s10947-007-0138-1 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10947-007-0138-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Soldatov D. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut NATIONALLICENCE 700 1- Ukraintseva É. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut NATIONALLICENCE 700 1- Logvinenko V. A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk aut NATIONALLICENCE 773 0- Journal of Structural Chemistry Springer US 48/5(2007-09-01), 938-948 0022-4766 48:5<938 2007 48 10947 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer