Crystal structure of KMnPO4F with short- and long-range order inside the layered magnetic system.

Potassium manganese fluoride phosphate, KMnPO4F, has been obtained through mild hydrothermal synthesis and characterized by scanning electron microscopy, microprobe analysis and X-ray diffraction. The compound possesses an orthorhombic symmetry and chiral space group P212121 with a = 4.7884(2), b = 9.0172(4), c = 9.5801(4) Å, and Z = 4. Its crystal structure is composed of Mn3+O4F square pyramids sharing vertices with PO4 tetrahedra. This anionic framework is neutralized by K+ cations. As the temperature decreases, a short-range correlation state (Tmax ∼ 35 K) of KMnPO4F is formed, followed by the establishment of antiferromagnetic (AFM) long-range order at TN = 25 K. The latter is marked by sharp λ-type anomalies in both Fisher's specific heat d(χ‖T)/dT and heat capacity Cp. Pulsed magnetic field measurements on the single crystals identify the a axis as the easy magnetic axis and reveal a spin-flop transition at µ0Hspin-flop = 19 T. Density functional theory indicates that in variance with the three-dimensional network of KMnPO4F, it is a two-dimensional Ising magnetic system represented by buckled layers of integer spins S = 2 of Mn3+ ions. The strongest AFM exchange interaction, J1 ∼ -13 K, couples Mn3+ ions into linear chains running along the a axis. The chains themselves are ferromagnetically connected (J3 ∼ -4 K) within the ab plane. The interplane AFM exchange interaction (J2 ∼ -1 K) is weak and frustrated.

Sequence of Structural and Magnetic Phase Transitions in (NO)Mn6(NO3)13.

New nitrosonium manganese(II) nitrate, (NO)Mn6(NO3)13, has been synthesized and structurally characterized. In the temperature range of 45-298 K, the crystal is hexagonal (centrosymmetric sp. gr. P63/m). Mn2+ ions are assembled into tubes along axis c with both NO3- filling and coating. The nitrosonium cation is located in the framework cavity and is disordered by a 3-fold axis. At the temperature TS1 = 190 K, a structural phase transition related to the libration of the intertube NO3 group and a small variation of Mn polyhedron is observed. Moreover, the anomalies in physical properties of (NO)Mn6(NO3)13 allow suggesting that ordering of NO+ units occurs at low temperatures. The antiferromagnetic ordering in this compound is preceded by the formation of a short-range correlation regime at about 25 K and takes place in two steps at TN1 = 12.0 K and TN2 = 8.4 K.

Lamellar Crystal Structure and Haldane Magnetism in NH4 VPO4 OH.

A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.

K2Mn3O(OH)(VO4)(V2O7) with Sawtooth Chains of Multivalent Manganese Triangular Trimer Units: Magnetic Susceptibility Shrouding a Long-Range Antiferromagnetic Order of Ferromagnetic Triangles.

ortho-Pyrovanadate (or ortho-diorthovanadate) K2Mn23+Mn2+O(OH)(VO4)(V2O7) synthesized hydrothermally crystallizes in the orthorhombic space group Pnma with a = 17.9155(5), b = 5.8940(2), c = 10.9971(3) Å, V = 1161.23(6) Å3, and Z = 4. Its crystal structure features linear chains of edge-sharing Mn3+O6 octahedra with every second pair of Mn3+O6 octahedra condensed with a Mn2+O6 octahedron on one side of a chain in a sawtooth pattern so that each sawtooth chain consists of a triangular trimer. These sawtooth chains, running parallel to the b axis and linked by the VO4 and V2O7 groups, form a framework with channels populated by K atoms. The new compound is a structural analogue of the mineral zoisite Ca2Al3O(OH)(SiO4)(Si2O7), showing a striking example of very different chemical compositions. K2Mn3O(OH)(VO4)(V2O7) undergoes a phase transition into an ordered antiferromagnetic (AFM) state at TN = 14.4 K, which was detected by high-frequency electron spin resonance as well as by both specific heat Cp and Fisher's specific heat d(χT)/dT measurements. However, this phase transition was not detected by magnetic susceptibility measurements. The origin of this puzzling observation was resolved by evaluating the spin exchanges of K2Mn3O(OH)(VO4)(V2O7), which revealed that each triangular trimer is a ferromagnetically coupled cluster, and the observed ordering involves an AFM ordering between the ferromagnetic (FM) clusters. This ordering is shrouded in magnetic susceptibility measurements due to the susceptibility contributions from the individual FM triangular trimers even below TN. We showed that the magnetic susceptibility of K2Mn3O(OH)(VO4)(V2O7) between ∼30 K and room temperature is satisfactorily described by an AFM chain made up of ferromagnetically coupled triangular clusters, as described by a few spin-exchange parameters.

Nonstoichiometric Ellenbergerite-Type Phosphates: Hydrothermal Synthesis, Crystal Chemistry, and Magnetic Behavior.

We synthesized single crystals of Na0.55Ni6(OH)3(H0.61PO4)4 (I) and polycrystals of (Na, Ni)0.64Ni5.68(OH)3(H0.67PO4)4 (II) with ellenbergerite-like structures using the hydrothermal method. The phases crystallize in the hexagonal space group P63mc with the following unit cell parameters: a = 12.5342(1) Å, c = 4.9470(1) Å, and V = 673.08(2) Å3 for I; a = 12.4708(2) Å, c = 4.9435(2) Å, and V = 665.82(2) Å3 for II; and Z = 2. Their crystal structures are based on a 3D framework built from NiO6 octahedra and PO4 tetrahedra. The difference between I and II lies in the way the structural channels are filled along the [001] direction. These channels accommodate segments of Na- and (Na, Ni)-centered chains of face-sharing octahedra in the structures I and II, respectively. The magnetic susceptibility χ and the specific heat Cp evidence pronounced low-dimensional magnetic behavior at elevated temperatures and the formation of the weakly ferromagnetic long-range order at TNI = 61 K and TNII = 63 K. Analysis of the χ(T) data within both chain and dimer spin models allows the estimation of the leading exchange interaction parameters in the compounds under study.

Hydrothermal Synthesis and a Composite Crystal Structure of Na6Cu7BiO4(PO4)4[Cl,(OH)]3 as a Candidate for Quantum Spin Liquid.

A novel sodium bismuth oxo-cuprate phosphate chloride, Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], containing square-kagomé layers of Cu2+ has been synthesized by hydrothermal techniques. The compound crystallizes in the tetragonal space group P4/nmm, a = 10.0176(4), c = 10.8545(6), Z = 2, V = 1089.3(1) Å3, R1 = 0.021, wR = 0.053, S = 1.32. Its composite crystal structure includes [O4Cu6Bi]7+ layers, which are formed by the clusters of oxygen-centered tetrahedra [OCu3Bi]. These positively charged two periodic fragments are intercalated in a negatively charged [CuNa6Cl3(PO4)4]7- matrix built by Na-centered polyhedra, PO4 tetrahedra, and CuO4Cl pyramids. The composite character of the crystal structure of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], as well as the way of its self-assembly, are discussed in close connection with the sulfohalite Na6ClF(SO4)2 salt. It is shown that the "host-guest" model of the formation of the tetragonal Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] phase is due to the group-subgroup symmetry relation with the cubic crystal structure of mineral sulfohalite and is also supported by the crystallization condition in excess sodium chloride. The magnetic subsystem of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] is represented by a dense square-kagomé network of 2Cu1 and 4Cu2 ions, decorated with weakly bonded Cu3 ions. Measurements of magnetization and heat capacity indicate the absence of long-range order up to 2 K, which makes this compound a candidate for a highly demanded spin liquid.

An Orthorhombic Modification of KCoPO4 Stabilized under Hydrothermal Conditions: Crystal Chemistry and Magnetic Behavior.

A novel modification of the KCoPO4, δ-phase has been prepared by hydrothermal synthesis at 553 K. The compound crystallizes in the orthorhombic system with the unit-cell parameters a = 8.5031(8), b = 10.2830(5), c = 54.170(4) Å. The crystal structure was determined based on synchrotron low-temperature single-crystal X-ray diffraction data obtained from an inversion twin in the space group P212121 and refined to R = 0.077 for 5156 reflections with I > 3σ(I). The δ-KCoPO4 possesses a new structure type which is based on a framework built from sharing vertices Co- and P-centered tetrahedra. The {CoPO4-}∞ construction of tetrahedra may be described as assembled from networks formed by two topologically diverse six-membered rings of tetrahedra stacked together through vertex-bridging contacts along the a axis. The ratio of the (UUUDDD) and (UUDUDD) rings, where (U) and (D) denote the orientation of the tetrahedra in the six-membered rings up and down relative to the plane grids, is equal to 5:1. The (UUDUDD) rings form bands parallel to the [010] direction each surrounded from both sides along the c axis by slabs of five ribbons width having alternative (UUUDDD) topology. Open in the [100] direction channels incorporate K+ ions; this structural feature permits to suppose ion-conductive and/or electrochemical properties of the title compound. The possible mechanism of the δ → γ phase transition is discussed on the basis of the crystal chemical analysis of the KCoPO4 polymorphs. The title compound orders magnetically at TN = 24.8 K.

Crystal structure and thermodynamic properties of dinickel diphosphate dihydrate Ni2(H2O)2[P2O7].

Single crystals of dinickel diphosphate dihydrate, Ni2(H2O)2[P2O7], have been synthesized by a hydrothermal method. Its structure was refined in the monoclinic P21/n space group (unit cell parameters a = 6.2517(1) Å, b = 13.7892(3) Å, c = 7.2894(2) Å, ß = 94.507(2)°, V = 626.45(2) Å3, and Z = 4) based on low-temperature X-ray diffraction data until R- 0.016. Corrugated chains of NiO5(H2O) octahedra sharing edges are aligned in the [101[combining macron]] direction. They are linked into a three-dimensional framework through diphosphate groups and hydrogen bonds. A detailed crystal chemical analysis of the family Me2(H2O)2[X2O7] revealed correlations between the unit-cell parameters of the isotypic transition metal phosphates and arsenates, their structural features and the sizes of structure forming cations. Despite the isolation of the cis and trans edge-sharing infinite zigzag chains of Ni-centered octahedra from each other no pronounced low dimensionality is seen in the magnetic response of Ni2(H2O)2[P2O7]. The magnetic susceptibility χ evidences a short range correlation maximum at Tmax = 11.9 K accompanied by the onset of long-range magnetic order at TN = 9.4 K. Below TN, the title compound exhibits the features of an archetype three-dimensional easy-axis antiferromagnet which experiences a sequence of spin-flop and spin-flip phase transitions. Basing on specific heat Cp and magnetization M studies, the magnetic phase diagram of Ni2(H2O)2[P2O7] has been established.

Novel K/Mn phosphate hydrates, K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry.

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K2Mn3(H2O)2[P2O7]2, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H2O)2[Al2(PO4)3], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X-ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A2M3(H2O)2[P2O7]2, where A = K, NH4, Rb or Na and M = Mn, Fe, Co or Ni, and AM2+(H2O)2[M3+2(PO4)3], where A = Cs, Rb, K, NH4 or (H3O); M2+ = Mn, Fe, Co or Ni; and M3+ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit-cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO2)2(PO4)2]∞ layers, with a cationic topology similar to the Si/Al-topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.

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, ß = 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.

Magnetically frustrated synthetic end member Mn2(PO4)OH in the triplite-triploidite family.

The manganese end member of triplite-triploidite series of compounds, Mn2(PO4)OH, is synthesized by a hydrothermal method. Its crystal structure is refined in the space group P21/c with a = 12.411(1) Å, b = 13.323(1) Å, c = 10.014(1) Å, ß = 108.16(1), V = 1573.3 Å3, Z = 8, and R = 0.0375. Evidenced in measurements of magnetization M and specific heat Cp, Mn2(PO4)OH reaches a long range antiferromagnetic order at TN = 4.6 K. As opposed to both triplite Mn2(PO4)F and triploidite-type Co2(PO4)F, the title compound is magnetically frustrated being characterized by the ratio of Curie-Weiss temperature Θ to Néel temperature TN of about 20. The large value of frustration strength |Θ|/TN stems from the twisted saw tooth chain geometry of corner sharing triangles of Mn polyhedra, which may be isolated within tubular fragments of a triploidite crystal structure.

Crystal structure and spin-trimer magnetism of Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2].

The novel borophosphate Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2] was prepared under hydrothermal conditions at 553 K. Its crystal structure was determined using single-crystal X-ray diffraction data obtained from a non-merohedral twin and refined against F2 to R = 0.057. The compound crystallizes in the orthorhombic space group Pbcn, with unit-cell parameters a = 20.076(2) Å, b = 9.151(1) Å, c = 12.257(1) Å, V = 2251.8(2) Å3, and Z = 4. The title compound is the first example of a borophosphate with manganese ions adopting both octahedral and tetrahedral coordinations. Its unique crystal structure is formed by borophosphate slabs and chains of Mn2+-centered polyhedra sharing edges and vertices. These 2D and 1D fragments interconnect into a framework with open channels that accommodate Rb+ cations and water molecules. Topological relationships between borophosphates built from three-membered rings of two borate and one phosphate tetrahedra sharing oxygen vertices, amended by additional PO4 and HPO4 tetrahedra, are discussed. The temperature dependence of the magnetic susceptibility of Rb2.3(H2O)0.8Mn3[B4P6O24(O,OH)2] reveals predominant antiferromagnetic exchange interactions and the high-temperature effective magnetic moment corresponding to the high-spin S = 5/2 state of Mn2+ ions. At 12.5 K, a magnetic transition is evidenced by ac-susceptibility and specific heat measurements. A spin-trimer model with the leading exchange interaction J ∼ 3.2 K is derived from density-functional band-structure calculations and accounts for all experimental observations.

Structure-Property Relationships in α-, ß'-, and γ-Modifications of Mn3(PO4)2.

The manganese orthophosphate, Mn3(PO4)2, is characterized by the rich variety of polymorphous modifications, α-, ß'-, and γ-phases, crystallized in monoclinic P21/c (P21/n) space group type with unit cell volume ratios of 2:6:1. The crystal structures of these phases are constituted by three-dimensional framework of corner- and edge-sharing [MnO5] and [MnO6] polyhedra strengthened by [PO4] tetrahedra. All compounds experience long-range antiferromagnetic order at Neel temperature TN = 21.9 K (α-phase), 12.3 K (ß'-phase), and 13.3 K (γ-phase). Additionally, second magnetic phase transition takes place at T* = 10.3 K in ß'-phase. The magnetization curves of α- and ß'-modifications evidence spin-floplike features at B = 1.9 and 3.7 T, while the γ-Mn3(PO4)2 stands out for an extended one-third magnetization plateau stabilized in the range of magnetic field B = 7.5-23.5 T. The first-principles calculations define the main paths of superexchange interaction between Mn spins in these polymorphs. The spin model for α-phase is found to be characterized by collection of uniform and alternating chains, which are coupled in all three directions. The strongest magnetic exchange interaction in γ-phase emphasizes the trimer units, which make chains that are in turn weakly coupled to each other. The spin model of ß'-phase turns out to be more complex compared to α- or γ-phase. It shows complex chain structures involving exchange interactions between Mn2 (Mn2', Mn2″) and Mn3 (Mn3', Mn3″). These chains interact through exchanges involving Mn1 (Mn1', Mn1″) spins.

An open framework crystal structure and physical properties of RbCuAl(PO4)2.

The novel phosphate RbCuAl(PO4)2 was prepared by hydrothermal synthesis at 553 K. Its crystal structure was determined using single-crystal X-ray diffraction data and refined against F(2) to R = 0.026. The compound crystallizes in the monoclinic space group P21/c, with unit-cell parameters a = 5.0723(8) Å, b = 14.070(2) Å, c = 9.352(1) Å, ß = 100.41(1), V = 656.4(2) Å(3), and Z = 4. The crystal structure is based on an open 3D aluminophosphate framework built by AlO5 bipyramids and PO4 tetrahedra sharing oxygen vertices. Channels in the [100] and [001] directions accommodate Rb(+) cations and chains of Cu-centered octahedra alternatively sharing cis- and trans-edges. The new phase is characterized by the structure type established for isotypic iron phosphates KMFe(PO4)2, where M = Fe/Ni, Ni, Mg or Co. It also shows topological relationships with Pb2Ni(PO4)2 and Fe(3+)Fe(2+)0.5(H2O)2(HPO4)2 structures. The RbCuAl(PO4)2 exhibits rather peculiar physical properties evidenced in specific heat and magnetization measurements. It releases a significant part of magnetic entropy well above the Neel temperature TN = 10.5 K and possesses a spontaneous magnetic moment at lower temperatures. The origin of the spontaneous moment is ascribed to the canting of a pristine antiferromagnetic structure due to the interchain Dzyaloshinskii-Moriya exchange interaction.

A novel cobalt sodium phosphate hydroxide with the ellenbergerite topology: crystal structure and physical properties.

The novel phase Na2-xCo6(OH)3[HPO4][Hx/3PO4]3 (x≈ 1.1) was prepared by hydrothermal synthesis at 553 K. Its crystal structure was determined using single-crystal X-ray diffraction data and refined against F(2) to R = 0.052, including positions of all hydrogen atoms. The compound crystallizes in the hexagonal space group P63mc, with unit-cell parameters a = 12.630(3) Å, c = 5.017(1) Å, V = 693.1(3) Å(3), and Z = 2. The crystal structure is based on a 3D framework built from CoO6 octahedra and PO4 tetrahedra. Channels in the [001] direction accommodate columns of Na-centered octahedra sharing faces. The compound is a new structural representative of the topology shown by aluminosilicate mineral ellenbergerite and its numerous natural and synthetic varieties. Magnetic susceptibility measurements revealed a strong antiferromagnetic interaction and magnetic transition to low temperature spin-canted phase at TN = 44 K. The physical properties of the title compound are found to be very similar to those of the structurally related arsenate Co1-xCo6(OH)3[H2x/3AsO4]3[HAsO4] and vanadate Co7(OH)2(H2O)[VO4]4.