PMID- 27564229 OWN - NLM STAT- PubMed-not-MEDLINE DCOM- 20180117 LR - 20180117 IS - 1520-510X (Electronic) IS - 0020-1669 (Linking) VI - 55 IP - 18 DP - 2016 Sep 19 TI - Honeycomb-like S = 5/2 Spin-Lattices in Manganese(II) Vanadates. PG - 9240-9 LID - 10.1021/acs.inorgchem.6b01286 [doi] AB - New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown from Mn2O3 and V2O5 in 3 M CsOH at 580 degrees C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn6O(VO4)2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn5(VO4)2(OH)4: C2/m, Z = 2, a = 9.6568(9) A, b = 9.5627(9) A, c = 5.4139(6) A, beta = 98.529(8) degrees ; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) A, b = 6.4678(8) A, c = 10.4478(13) A, beta = 99.798(3) degrees ), revealing interesting low-dimensional transition-metal features. Mn5(VO4)2(OH)4 possesses complex honeycomb-type Mn-O layers, built from edge-sharing [MnO6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn6O(VO4)2(OH) presents a more complicated structure with both octahedral [MnO6] and trigonal bipyramidal [MnO5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristic Raman scattering due to vanadate groups. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn5(VO4)2(OH)4 and below 45 K in Mn6O(VO4)2(OH). Members of another class of compounds, K2M3(VO4)2(OH)2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals. FAU - Sanjeewa, Liurukara D AU - Sanjeewa LD AD - Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University , Clemson, South Carolina 29634-0973, United States. FAU - McGuire, Michael A AU - McGuire MA AD - Materials Science and Technology Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States. FAU - McMillen, Colin D AU - McMillen CD AD - Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University , Clemson, South Carolina 29634-0973, United States. FAU - Willett, Daniel AU - Willett D AD - Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University , Clemson, South Carolina 29634-0973, United States. FAU - Chumanov, George AU - Chumanov G AD - Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University , Clemson, South Carolina 29634-0973, United States. FAU - Kolis, Joseph W AU - Kolis JW AD - Department of Chemistry and Center for Optical Materials Science and Engineering Technologies, Clemson University , Clemson, South Carolina 29634-0973, United States. LA - eng PT - Journal Article DEP - 20160826 PL - United States TA - Inorg Chem JT - Inorganic chemistry JID - 0366543 EDAT- 2016/08/27 06:00 MHDA- 2016/08/27 06:01 CRDT- 2016/08/27 06:00 PHST- 2016/08/27 06:00 [entrez] PHST- 2016/08/27 06:00 [pubmed] PHST- 2016/08/27 06:01 [medline] AID - 10.1021/acs.inorgchem.6b01286 [doi] PST - ppublish SO - Inorg Chem. 2016 Sep 19;55(18):9240-9. doi: 10.1021/acs.inorgchem.6b01286. Epub 2016 Aug 26.