Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds

Journal Article · Fri Jul 15 00:00:00 EDT 2016 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2016.04.025· OSTI ID:22584156

Gil, D. M. ^[1]; Osiry, H. ^[2]; Pomiro, F.; Varetti, E. L. ^[3]; Carbonio, R. E. ^[4]; Alejandro, R. R. ^[2]; Ben Altabef, A. ^[5]; others, and

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1. Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina)
2. Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México (Mexico)
3. CEQUINOR (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 and 115, 1900, La Plata (Argentina)
4. INFIQC – CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Haya de la Torre esq, Medina Allende, Ciudad Universitaria, X5000HUA Córdoba (Argentina)
5. INQUINOA-UNT-CONICET, Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina)

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.

• OSTI ID: 22584156
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 239; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANTIFERROMAGNETISM
CRYSTALS
CYANIDES
HYDRATES
HYDROGEN
INTERACTIONS
LAYERS
LIGANDS
MAGNETIC PROPERTIES
MAGNETIZATION
NITRIC OXIDE
ORTHORHOMBIC LATTICES
PARAMAGNETISM
POWDERS
SOLIDS
SPACE GROUPS
TRANSITION ELEMENTS
WATER
X RADIATION
X-RAY DIFFRACTION