DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Single crystal neutron and magnetic measurements of Rb2Mn3(VO4)2CO3 and K2Co3(VO4)2CO3 with mixed honeycomb and triangular magnetic lattices

Journal Article · · Dalton Transactions
DOI: https://doi.org/10.1039/C9DT03389K · OSTI ID:1606707

Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb2Mn3(VO4)2CO3, crystallizes in the trigonal crystal system in the space group P[3 with combining macron]1c, and compound II, K2Co3(VO4)2CO3, crystallizes in the hexagonal space group P63/m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO6 octahedra and MO5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO4] groups. The MO5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO6-honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K2Co3(VO4)2CO3 (II) exhibits a canted antiferromagnetic ordering below TN = 8 K. Here, the Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of –42 K suggesting a dominant antiferromagnetic coupling in the Co2+ magnetic sublattices.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; NSF-DMR-1808371; NSF-OIA-1655740
OSTI ID:
1606707
Journal Information:
Dalton Transactions, Vol. 49, Issue 14; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (39)

Magnetic properties of the triangular lattice magnets A 4 B ′ B 2 O 12 ( A = Ba , Sr, La; B ′ = Co , Ni, Mn; B = W , Re) journal May 2017
Syntheses and Characterization of a Family of Vanadate Compounds Ba 3 M(V 2 O 7 ) 2 (M = Co, Mn, Mg, or Zn) with an Edge-Shared [M 2 O 10 ] Dimer Structure journal March 2015
Generalized Gradient Approximation Made Simple journal October 1996
Strontium manganese vanadates from hydrothermal brines: Synthesis and structure of Sr2Mn2(V3O10)(VO4), Sr3Mn(V2O7)2, and Sr2Mn(VO4)2(OH) journal November 2017
Supercell program: a combinatorial structure-generation approach for the local-level modeling of atomic substitutions and partial occupancies in crystals journal March 2016
Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior journal July 2015
Frustrated magnetism in the S = 1 kagomé lattice BaNi3(OH)2(VO4)2 journal January 2012
Magnetization Process and Collective Excitations in the S = 1 / 2 Triangular-Lattice Heisenberg Antiferromagnet Ba 3 CoSb 2 O 9 journal June 2013
Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines journal March 2017
A short history of SHELX journal December 2007
Implementation of cross correlation for energy discrimination on the time-of-flight spectrometer CORELLI journal March 2018
Synthesis of polyoxovanadates via “chimie douce” journal December 1998
Polar Materials with Isolated V 4+ S = 1/2 Triangles: NaSr 2 V 3 O 3 (Ge 4 O 13 )Cl and KSr 2 V 3 O 3 (Ge 4 O 13 )Cl journal January 2017
Magnetically Driven Ferroelectric Order in Ni 3 V 2 O 8 journal August 2005
BaMn 9 [VO 4 ] 6 (OH) 2 : A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature journal November 2014
The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt-Inclusion Vanadate Hybrids journal May 2008
Hydrothermal synthesis of single crystals of transition metal vanadates in the glaserite phase journal April 2016
Growth of oxygen deficiency-free YVO4 single crystal by top-seeded solution growth technique journal November 1993
Formation enthalpies by mixing GGA and GGA + U calculations journal July 2011
Structural absorption by barbule microstructures of super black bird of paradise feathers journal January 2018
Magnetic phase diagram of the antiferromagnetic cobalt tellurate Co 3 TeO 6 journal December 2011
Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F journal September 2016
Crystal growth, structure, and properties of manganese orthovanadate Mn3(VO4)2 journal January 2000
Magnetic structures of the low temperature phase of Mn 3 (VO 4 ) 2 – towards understanding magnetic ordering between adjacent Kagomé layers journal January 2016
Hydrothermal synthesis as a route to mineralogically-inspired structures journal January 2016
The magnetic order of a manganese vanadate system with two-dimensional striped triangular lattice journal October 2018
Single-ion properties of the S eff = 1 2 XY antiferromagnetic pyrochlores Na A ′ Co 2 F 7 ( A ′ = Ca 2 + ,   Sr 2 + ) journal April 2017
Reproducibility in density functional theory calculations of solids journal March 2016
Synthesis and Structure of Ba5(V2O7)2Cl2 journal October 2008
Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates journal August 2016
Materials Discovery by Flux Crystal Growth: Quaternary and Higher Order Oxides journal January 2012
Structural and magnetic characterization of the one-dimensional S = 5 / 2 antiferromagnetic chain system SrMn ( V O 4 ) ( OH ) journal June 2016
Precision and efficiency in solid-state pseudopotential calculations journal December 2018
The First Vanadate–Carbonate, K 2 Mn 3 (VO 4 ) 2 (CO 3 ): Crystal Structure and Physical Properties journal January 2013
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal January 2005
M 3 (P 2 O 7 ) 2 2– -Type Open Frameworks Featuring [M 2 O 8 ] and [M 3 O 12 ] Multinuclear Transition-Metal Oxide Units. Serendipitous Synthesis of Six Polymorphic Salt-Inclusion Magnetic Solids: Na 2 M 3 (P 2 O 7 ) 2 ·ACl (M = Mn, Fe; A = Rb, Cs) and K 2 M 3 (P 2 O 7 ) 2 ·CsCl (M = Fe, Mn) journal November 2014
The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt-Inclusion Vanadate Hybrids journal May 2008
Precision and efficiency in solid-state pseudopotential calculations text January 2018
The magnetic order of a manganese vanadate system with two-dimensional striped triangular lattice text January 2018