Synthesis and characterization of two vanadium chalcogenides, [NH 4][H(VO)(SeO3)2] and Cs4[(VOS 2)2(μ-O)], prepared solvothermally

Mehtap Emirdag-Eanes; James A. Ibers

doi:10.1016/S0925-8388(03)00417-1

Synthesis and characterization of two vanadium chalcogenides, [NH ₄][H(VO)(SeO₃)₂] and Cs₄[(VOS ₂)₂(μ-O)], prepared solvothermally

Mehtap Emirdag-Eanes, James A. Ibers^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The new compounds [NH₄][H(VO)(SeO₃)₂] and Cs₄[(VOS₂)₂(μ-O)] have been synthesized solvothermally at 170 °C. [NH₄][H(VO)(SeO₃) ₂] was synthesized by the hydrothermal reaction of V and Na ₂Se with NH₄Cl as mineralizer. The compound crystallizes in the space group P2₁/m of the monoclinic system with four formula units in a cell of dimensions a=3.9883(13) Å, b=10.504(3) Å, c=7.953(3) Å, β=98.571(5)°, V=329.45(19) Å³ (T=153 K). The structure is composed of linear chains of repeating [(VO)(SeO₃)₂]^2- units, similar to those found in K[H(VO)(SeO₃)₂]. NH₄⁺ ions reside among the chains and take part in an extensive hydrogen bonding scheme. The H center is involved in a very short, apparently symmetric, O-H-O hydrogen bond 2.479(6) Å in length. The compound displays Curie-Weiss paramagnetism in the range 30-300 K with μ_eff=1.796(5) μ _B, in close agreement with the theoretical spin-only effective moment expected for V⁴⁺. There is antiferromagnetic coupling below 20 K. Cs₄[(VOS₂)₂(μ-O)] was synthesized by the methanothermal reaction of V and Cs₂S₃. It crystallizes in the space group Pnma of the orthorhombic system with four formula units in a cell of dimensions a=13.3280(15) Å, b=8.7912(10) Å, c=12.2140(14) Å, V=1431.1(3) Å³ (T=153 K). Cs₄[(VOS₂)₂(μ-O)] appears to be the first mixed O/S pyrovanadate structure type. Each of the V⁵⁺ centers is tetrahedrally coordinated by an O and two S atoms as well as by another O atom that is corner-shared between the two tetrahedra. Cs⁺ ions reside among the [(VOS₂)₂(μ-O)]^4- units.

Original language	English (US)
Pages (from-to)	66-70
Number of pages	5
Journal	Journal of Alloys and Compounds
Volume	361
Issue number	1-2
DOIs	https://doi.org/10.1016/S0925-8388(03)00417-1
State	Published - Oct 27 2003

Funding

This research was supported by the US National Science Foundation under grant CHE9819385.

Keywords

Chalcogenides
X-ray diffraction

ASJC Scopus subject areas

Mechanics of Materials
Mechanical Engineering
Metals and Alloys
Materials Chemistry

Access to Document

10.1016/S0925-8388(03)00417-1

Cite this

@article{da9e684ed04e4c0cbff3aec5d79bd254,

title = "Synthesis and characterization of two vanadium chalcogenides, [NH 4][H(VO)(SeO3)2] and Cs4[(VOS 2)2(μ-O)], prepared solvothermally",

abstract = "The new compounds [NH4][H(VO)(SeO3)2] and Cs4[(VOS2)2(μ-O)] have been synthesized solvothermally at 170 °C. [NH4][H(VO)(SeO3) 2] was synthesized by the hydrothermal reaction of V and Na 2Se with NH4Cl as mineralizer. The compound crystallizes in the space group P21/m of the monoclinic system with four formula units in a cell of dimensions a=3.9883(13) {\AA}, b=10.504(3) {\AA}, c=7.953(3) {\AA}, β=98.571(5)°, V=329.45(19) {\AA}3 (T=153 K). The structure is composed of linear chains of repeating [(VO)(SeO3)2]2- units, similar to those found in K[H(VO)(SeO3)2]. NH4+ ions reside among the chains and take part in an extensive hydrogen bonding scheme. The H center is involved in a very short, apparently symmetric, O-H-O hydrogen bond 2.479(6) {\AA} in length. The compound displays Curie-Weiss paramagnetism in the range 30-300 K with μeff=1.796(5) μ B, in close agreement with the theoretical spin-only effective moment expected for V4+. There is antiferromagnetic coupling below 20 K. Cs4[(VOS2)2(μ-O)] was synthesized by the methanothermal reaction of V and Cs2S3. It crystallizes in the space group Pnma of the orthorhombic system with four formula units in a cell of dimensions a=13.3280(15) {\AA}, b=8.7912(10) {\AA}, c=12.2140(14) {\AA}, V=1431.1(3) {\AA}3 (T=153 K). Cs4[(VOS2)2(μ-O)] appears to be the first mixed O/S pyrovanadate structure type. Each of the V5+ centers is tetrahedrally coordinated by an O and two S atoms as well as by another O atom that is corner-shared between the two tetrahedra. Cs+ ions reside among the [(VOS2)2(μ-O)]4- units.",

keywords = "Chalcogenides, X-ray diffraction",

author = "Mehtap Emirdag-Eanes and Ibers, {James A.}",

note = "Funding Information: This research was supported by the US National Science Foundation under grant CHE9819385. ",

year = "2003",

month = oct,

day = "27",

doi = "10.1016/S0925-8388(03)00417-1",

language = "English (US)",

volume = "361",

pages = "66--70",

journal = "Journal of Alloys and Compounds",

issn = "0925-8388",

publisher = "Elsevier B.V.",

number = "1-2",

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TY - JOUR

T1 - Synthesis and characterization of two vanadium chalcogenides, [NH 4][H(VO)(SeO3)2] and Cs4[(VOS 2)2(μ-O)], prepared solvothermally

AU - Emirdag-Eanes, Mehtap

AU - Ibers, James A.

N1 - Funding Information: This research was supported by the US National Science Foundation under grant CHE9819385.

PY - 2003/10/27

Y1 - 2003/10/27

N2 - The new compounds [NH4][H(VO)(SeO3)2] and Cs4[(VOS2)2(μ-O)] have been synthesized solvothermally at 170 °C. [NH4][H(VO)(SeO3) 2] was synthesized by the hydrothermal reaction of V and Na 2Se with NH4Cl as mineralizer. The compound crystallizes in the space group P21/m of the monoclinic system with four formula units in a cell of dimensions a=3.9883(13) Å, b=10.504(3) Å, c=7.953(3) Å, β=98.571(5)°, V=329.45(19) Å3 (T=153 K). The structure is composed of linear chains of repeating [(VO)(SeO3)2]2- units, similar to those found in K[H(VO)(SeO3)2]. NH4+ ions reside among the chains and take part in an extensive hydrogen bonding scheme. The H center is involved in a very short, apparently symmetric, O-H-O hydrogen bond 2.479(6) Å in length. The compound displays Curie-Weiss paramagnetism in the range 30-300 K with μeff=1.796(5) μ B, in close agreement with the theoretical spin-only effective moment expected for V4+. There is antiferromagnetic coupling below 20 K. Cs4[(VOS2)2(μ-O)] was synthesized by the methanothermal reaction of V and Cs2S3. It crystallizes in the space group Pnma of the orthorhombic system with four formula units in a cell of dimensions a=13.3280(15) Å, b=8.7912(10) Å, c=12.2140(14) Å, V=1431.1(3) Å3 (T=153 K). Cs4[(VOS2)2(μ-O)] appears to be the first mixed O/S pyrovanadate structure type. Each of the V5+ centers is tetrahedrally coordinated by an O and two S atoms as well as by another O atom that is corner-shared between the two tetrahedra. Cs+ ions reside among the [(VOS2)2(μ-O)]4- units.

AB - The new compounds [NH4][H(VO)(SeO3)2] and Cs4[(VOS2)2(μ-O)] have been synthesized solvothermally at 170 °C. [NH4][H(VO)(SeO3) 2] was synthesized by the hydrothermal reaction of V and Na 2Se with NH4Cl as mineralizer. The compound crystallizes in the space group P21/m of the monoclinic system with four formula units in a cell of dimensions a=3.9883(13) Å, b=10.504(3) Å, c=7.953(3) Å, β=98.571(5)°, V=329.45(19) Å3 (T=153 K). The structure is composed of linear chains of repeating [(VO)(SeO3)2]2- units, similar to those found in K[H(VO)(SeO3)2]. NH4+ ions reside among the chains and take part in an extensive hydrogen bonding scheme. The H center is involved in a very short, apparently symmetric, O-H-O hydrogen bond 2.479(6) Å in length. The compound displays Curie-Weiss paramagnetism in the range 30-300 K with μeff=1.796(5) μ B, in close agreement with the theoretical spin-only effective moment expected for V4+. There is antiferromagnetic coupling below 20 K. Cs4[(VOS2)2(μ-O)] was synthesized by the methanothermal reaction of V and Cs2S3. It crystallizes in the space group Pnma of the orthorhombic system with four formula units in a cell of dimensions a=13.3280(15) Å, b=8.7912(10) Å, c=12.2140(14) Å, V=1431.1(3) Å3 (T=153 K). Cs4[(VOS2)2(μ-O)] appears to be the first mixed O/S pyrovanadate structure type. Each of the V5+ centers is tetrahedrally coordinated by an O and two S atoms as well as by another O atom that is corner-shared between the two tetrahedra. Cs+ ions reside among the [(VOS2)2(μ-O)]4- units.

KW - Chalcogenides

KW - X-ray diffraction

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U2 - 10.1016/S0925-8388(03)00417-1

DO - 10.1016/S0925-8388(03)00417-1

M3 - Article

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JO - Journal of Alloys and Compounds

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