Crystal Structures and Low-Dimensional Ferromagnetism of Sodium Nickel Phosphates Na₅Ni₂(PO₄)₃·H₂O and Na₆Ni₂(PO₄)₃OH

Two new sodium nickel phosphates, Na₅Ni₂(PO₄)₃·H₂O (I) and Na₆Ni₂(PO₄)₃OH (II), have been synthesized hydrothermally and characterized by synchrotron X-ray diffraction, electron diffraction, low-temperature thermodynamic and magnetic measurements, and ab initio calculations. Unlike the majority of Ni²⁺ compounds, I and II show predominant ferromagnetic exchange couplings. I crystallizes in the monoclinic space group P2₁/n (a = 14.0395(4) Å, b = 5.1847(14) Å, c = 16.4739(4) Å, β = 110.4186(14)°) and features chains of ferromagnetically coupled Ni²⁺ ions. In II with the orthorhombic space group Pcmb (a = 7.5007(15) Å, b = 21.4661(4) Å, c = 7.1732(15) Å), the ferromagnetically coupled Ni²⁺ ions form dimers arranged on a spin ladder. Both compounds represent rare examples of quasi-one-dimensional ferromagnets. Structural features behind this unusual magnetic behavior are discussed.