Crystal structure and characterization of the novel NH{sup +} Midline-Horizontal-Ellipsis N hydrogen bonded polar crystal [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}]

Journal Article · Thu Mar 15 04:00:00 EDT 2012 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2011.12.020· OSTI ID:22012036

Wojtas, M ^[1]; Gagor, A ^[2]; Czupinski, O ^[1]; Medycki, W ^[3]; Jakubas, R ^[1]

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1. Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw (Poland)
2. W. Trzebiatowski Institute of Low Temperature and Structure Research, Polish Academy of Science, PO Box 1410, 50-950 Wroclaw (Poland)
3. Institute of Molecular Physics, Polish Academy of Science, Smoluchowskiego 17, 60-179 Poznan (Poland)

Dielectric properties and phase transitions of the piperazinium tetrafluoroborate ([NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}], abbreviated as PFB) crystal are related to the one-dimensional arrangement of the cations linked by the bistable NH{sup +} Midline-Horizontal-Ellipsis N hydrogen bonds and molecular motions of the [BF{sub 4}]{sup -} units. The crystal structure of [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}] is monoclinic at room temperature with the polar space group Pn. The polar/acentric properties of the room temperature phase IV have been confirmed by the piezoelectric and pyroelectric measurements. DSC measurements show that the compound undergoes three first-order structural phase transitions: at 421/411 K (heating/cooling), at 386/372 K and at 364/349 K. {sup 1}H and {sup 19}F NMR measurements indicate the reorientational motions of [BF{sub 4}]{sup -} anions and piperazinium(+) cations as well as the proton motion in the hydrogen-bonded chains of piperazine along the [001] direction. Over the phase I the isotropic reorientational motions or even self-diffusion of the cations and anions are expected. The conductivity measurements in the vicinity of the II-I PT indicate a superionic phase over the phase I. - Graphical abstract: It must be emphasized that the titled compound represents the first organic-inorganic simple salt containing the single-protonated piperazinium cation which was studied by means of the wide variety of experimental techniques. A survey of Cambridge Structural Database (CSD version 5.32 (November 2010) and updates (May 2011)) for structure containing the piperazinium cations yields 248 compounds with the doubly protonated piperazinium(2+) cations and only eight compounds with the singly protonated piperazinium(+) cations. Among these structures only one is the hybrid organic-inorganic material. This is piperazinium nitrate characterized structurally. The crystal packing of [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}], phase IV. The dashed lines stand for the hydrogen bonds. The hydrogen bonds to BF4 groups are not included for the picture quality Highlights: Black-Right-Pointing-Pointer The second organic-inorganic salt containing single-protonated piperazinium cation. Black-Right-Pointing-Pointer The first such a crystal not only structurally characterized. Black-Right-Pointing-Pointer The phase I revealed the features characteristic of super ionic phase. Black-Right-Pointing-Pointer The [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}] crystal is piezoelectric and polar at room temperature. Black-Right-Pointing-Pointer Mechanism of phase transitions was proposed.

• OSTI ID: 22012036
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. . 187; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
CALORIMETRY
CATIONS
CRYSTALS
DIELECTRIC PROPERTIES
FLUOROBORATES
HYDROGEN
MONOCLINIC LATTICES
NITRATES
NUCLEAR MAGNETIC RESONANCE
PIEZOELECTRICITY
PIPERAZINES
SPACE GROUPS