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Analysis of the atomic arrangement in anhydrous aminoguanidinium hexafluorozirconate, CN4H8ZrF6, reported by Bukvetskii, Gerasimenko & Davidovich [Koord. Khim. (1990), 16, 1479–1484], led to the prediction that it is a new ferroelectric [Abrahams, Mirsky & Nielson (1996). Acta Cryst. B52, 806–809]. Initial attempts to verify the prediction were inconclusive because of the variety of closely related materials produced under the original preparation conditions. Clarification of these conditions led to the formation of pure CN4H8ZrF6 and the growth of single crystals with dimensions as large as 7 × 7 × 2 mm. Highly reproducible calorimetric and dielectric permittivity anomalies reveal the Curie temperature Tc = 383 (1) K. At this temperature, the heat capacity Cp exhibits an entropy change of 0.7 (1) J mol−1 K−1, while the relative permittivity ![[epsilon]](/logos/entities/epsiv_rmgif.gif)
r exhibits an inflection and the dielectric loss a distinct peak; the dielectric anomaly at Tc is observed only at the lowest (0.1–1 kHz) frequencies used. Dielectric hysteresis is demonstrable at 295 K under the application of ∼1 MV m−1 alternating fields and remains observable at all T < Tc but not at T ≥ Tc; the prediction of ferroelectricity is hence confirmed. The value of the spontaneous polarization Ps is 0.45 (9) × 10−2 C m−2 at 298 K, with piezoelectric coefficient d33 = 1.9 (5) pC N−1 and pyroelectric coefficient p3 = 4 (1) µC m−2 K−1. Tilts of less than ∼11° by the two symmetry-independent CN4H
ions, combined with rotations of ∼20° or less by the N—NH3 and C—(NH2)2 groups about the central C—N bond in each cation, as all H atoms rotate into or become symmetrically distributed about the planes at z = 0 or ½, allow them to conform to mirror symmetry via polar atomic displacements of ∼0.4 Å or less by N or C, and of 0.7 Å or less by H. Corresponding displacements of less than 0.08 Å within the two symmetry-independent ZrF
anions also result in mirror symmetry, satisfying the structural criteria required for the development of ferroelectricity.
r exhibits an inflection and the dielectric loss a distinct peak; the dielectric anomaly at Tc is observed only at the lowest (0.1–1 kHz) frequencies used. Dielectric hysteresis is demonstrable at 295 K under the application of ∼1 MV m−1 alternating fields and remains observable at all T < Tc but not at T ≥ Tc; the prediction of ferroelectricity is hence confirmed. The value of the spontaneous polarization Ps is 0.45 (9) × 10−2 C m−2 at 298 K, with piezoelectric coefficient d33 = 1.9 (5) pC N−1 and pyroelectric coefficient p3 = 4 (1) µC m−2 K−1. Tilts of less than ∼11° by the two symmetry-independent CN4H
ions, combined with rotations of ∼20° or less by the N—NH3 and C—(NH2)2 groups about the central C—N bond in each cation, as all H atoms rotate into or become symmetrically distributed about the planes at z = 0 or ½, allow them to conform to mirror symmetry via polar atomic displacements of ∼0.4 Å or less by N or C, and of 0.7 Å or less by H. Corresponding displacements of less than 0.08 Å within the two symmetry-independent ZrF
anions also result in mirror symmetry, satisfying the structural criteria required for the development of ferroelectricity.
