Synthesis, Crystal Structure, and Properties of Mn(PO₃F)(H₂O)₂

Abstract

Abstract. Single crystals of manganese(II) fluorophosphate dihydrate, Mn(PO 3 F)(H 2 O) 2 , were grown in a metathesis reaction from aqueous solutions of MnCl 2 and (NH 4 ) 2 (PO 3 F). The crystal structure [P1, Z = 2, a = 5.5280 (7)

Variable Dimensionality, Valence, and Magnetism in Fluoride-Rich Iron Phosphates BaxFex(PO4)Fy (1 ≤ x ≤ 3, 2 ≤ y ≤ 12)

“…Recently, high concentrations of fluoride stemming from the hydrolysis of HPF 6 were mainly applied to the synthesis of fluorophosphates. However, the resulting networks were frequently associated with PO 2 (OH, F) 2– , PO 3 F 2– , or M­(O, OH, F) n ( n = 4, 6) groups (it should be noted that compounds with PO 3 F 2– and PO 2 (OH, F) 2– anions were strictly categorized as fluorophosphates , whereas those containing the [PO 4 ] 3– anion as fluoride phosphates ) . In this article, we report the synthesis and structural characterization of three fluoride-rich barium iron phosphates, Ba x Fe x (PO 4 )­F y (1 ≤ x ≤ 3, 2 ≤ y ≤ 12), derived from phosphoric and fluorophosphoric acids through fluoride-rich hydrothermal routes .…”

“…However, the resulting networks were frequently associated with PO 2 (OH, F) 2− , PO 3 F 2− , or M(O, OH, F) n (n = 4, 6) groups (it should be noted that compounds with PO 3 F 2− and PO 2 (OH, F) 2− anions were strictly categorized as f luorophosphates, whereas those containing the [PO 4 ] 3− anion as f luoride phosphates). 19 In this article, we report the synthesis and structural characterization of three fluoride-rich barium iron phosphates, Ba x Fe x (PO 4 )F y (1 ≤ x ≤ 3, 2 ≤ y ≤ 12), derived from phosphoric and fluorophosphoric acids through fluoride-rich hydrothermal routes. 10 However, with the aid of hydrazine to adjust the pH of hydrothermal solutions, we successfully found an alternative method to synthesize the fluoride oxysalts without high-temperature supercritical conditions.…”

Transition-Metal Monofluorophosphate Ba2M2(PO3F)F6 (M = Mn, Co, and Ni): Varied One-Dimensional Transition-Metal Chains and Antiferromagnetism

“…In this context, we are interested in organizing [MO n F 6– n ] m + units into [PO 4– p F p ] q − -containing frameworks. Strictly speaking, Li 2 FePO 4 F, containing isolated PO 4 3– tetrahedral and F – anions, belongs to the class of fluoride phosphates , while the compounds containing tetrahedral (PO 3 F) 2– and (PO 2 F 2 ) − anions are designated as fluorophosphates . The structures of the latter not only contain [MO x F y ] z − polyhedra linked in a variety of ways via [PO 4– p F p ] q − polyhedral units but also involve the varied [MO x F y ] z − building units linked together in a variety of ways via O atoms or one, two, or more F atoms of oxyanion or fluorooxyanion groups through corner-, edge-, or face-sharing combinations, thereby yielding chain (one-dimensional, 1D), layered (two-dimensional, 2D), and three-dimensional (3D) frameworks .…”

Ionothermal Synthesis Enables Access to 3D Open Framework Manganese Phosphates Containing Extra-Large 18-Ring Channels

“…For the ammonia containing manganese phosphates ( 2 , 4 ), the vibration modes of the N–H bonds of the (NH 4 ) + ions range between 1384 and 1546 cm –1 (deformation vibrations) and 2784 and 3385 cm –1 (stretching vibrations). − The broad band observed around 3225 cm –1 can be attributed to the stretching vibration of hydroxyl groups of the phosphate tetrahedra in all title compounds 1 – 4 . At lower wavenumbers, all IR spectra are quite similar because the vibrational modes for the P–OH, P–O, and P–F bonds of the various tetrahedral phosphate units (PO 2 (OH) 2 , PO 3 (OH), PO 3 F) arise between 400 and 1300 cm –1 . − The band at 1260 cm –1 , which is for compound 2 notably intense, can be assigned to the P–O–H deformation vibration . The overlapped symmetric and asymmetric P–O stretching vibrations range between 1100 and 1200 cm –1 , − whereas the P–OH and P–F stretching vibrations are observed in the region of 750–960 cm –1 . − Between 400 and 700 cm –1 , O–P–O and O–P–F deformation vibrations occur. − The two sharp modes at about 3587 cm –1 , which emerge only in the compound 1 , can be assigned to the O–H stretching vibrations of the PO 3 (OH) groups in its crystal structures.…”