Alignment of acentric MoO3F33- anions in a polar material

(Ag3MoO3F3)(Ag 3MoO4)Cl

Paul A. Maggard, Tiffany S. Nault, Charlotte L. Stern, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

232 Citations (Scopus)

Abstract

(Ag3MoO3F3)(Ag3MoO 4)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6)Å, c=5.9190(7)Å). The transparent colorless crystals are comprised of chains of distorted fac-MoO3F33- octahedra and MoO42- tetrahedra anions, as suggested by the formulas Ag3MoO3F3 and Ag 3MoO4+, and are connected through Ag + cations in a polar alignment along the c-axis. One Cl- anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by ∼1/2×c. In MoO 42-, the Mo atom displaces towards a single oxide vertex, and in MoO3F33-, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO 3F33- anion is important to prevent local inversion centers, while the polar organization is directed by the Cl - anion and interchain dipole-dipole interactions. The dipole moments of MoO3F33- and MoO4 2- align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO3F33- and MoO 42- were calculated from bond valence analyses and are 6. 1 and 1.9debye (10-18esucm) respectively, compared to 4.4debye for polar NbO6 octahedra in LiNbO3, and 4.5debye for polar TiO6 octahedra in KTiOPO4 (KTP).

Original languageEnglish
Pages (from-to)27-33
Number of pages7
JournalJournal of Solid State Chemistry
Volume175
Issue number1
DOIs
Publication statusPublished - Oct 2003

Fingerprint

Anions
Negative ions
alignment
Oxides
anions
Dipole moment
oxides
dipole moments
Ligands
dipoles
ligands
Fluorides
tetrahedrons
cancellation
fluorides
Cations
apexes
Positive ions
Single crystals
inversions

Keywords

  • Dipole moment calculation
  • Metal oxyfluoride anions
  • Polar compound

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Alignment of acentric MoO3F33- anions in a polar material : (Ag3MoO3F3)(Ag 3MoO4)Cl. / Maggard, Paul A.; Nault, Tiffany S.; Stern, Charlotte L.; Poeppelmeier, Kenneth R.

In: Journal of Solid State Chemistry, Vol. 175, No. 1, 10.2003, p. 27-33.

Research output: Contribution to journalArticle

Maggard, Paul A. ; Nault, Tiffany S. ; Stern, Charlotte L. ; Poeppelmeier, Kenneth R. / Alignment of acentric MoO3F33- anions in a polar material : (Ag3MoO3F3)(Ag 3MoO4)Cl. In: Journal of Solid State Chemistry. 2003 ; Vol. 175, No. 1. pp. 27-33.
@article{455192711a064e2b96d912fef589f363,
title = "Alignment of acentric MoO3F33- anions in a polar material: (Ag3MoO3F3)(Ag 3MoO4)Cl",
abstract = "(Ag3MoO3F3)(Ag3MoO 4)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6){\AA}, c=5.9190(7){\AA}). The transparent colorless crystals are comprised of chains of distorted fac-MoO3F33- octahedra and MoO42- tetrahedra anions, as suggested by the formulas Ag3MoO3F3 and Ag 3MoO4+, and are connected through Ag + cations in a polar alignment along the c-axis. One Cl- anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by ∼1/2×c. In MoO 42-, the Mo atom displaces towards a single oxide vertex, and in MoO3F33-, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO 3F33- anion is important to prevent local inversion centers, while the polar organization is directed by the Cl - anion and interchain dipole-dipole interactions. The dipole moments of MoO3F33- and MoO4 2- align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO3F33- and MoO 42- were calculated from bond valence analyses and are 6. 1 and 1.9debye (10-18esucm) respectively, compared to 4.4debye for polar NbO6 octahedra in LiNbO3, and 4.5debye for polar TiO6 octahedra in KTiOPO4 (KTP).",
keywords = "Dipole moment calculation, Metal oxyfluoride anions, Polar compound",
author = "Maggard, {Paul A.} and Nault, {Tiffany S.} and Stern, {Charlotte L.} and Poeppelmeier, {Kenneth R}",
year = "2003",
month = "10",
doi = "10.1016/S0022-4596(03)00090-2",
language = "English",
volume = "175",
pages = "27--33",
journal = "Journal of Solid State Chemistry",
issn = "0022-4596",
publisher = "Academic Press Inc.",
number = "1",

}

TY - JOUR

T1 - Alignment of acentric MoO3F33- anions in a polar material

T2 - (Ag3MoO3F3)(Ag 3MoO4)Cl

AU - Maggard, Paul A.

AU - Nault, Tiffany S.

AU - Stern, Charlotte L.

AU - Poeppelmeier, Kenneth R

PY - 2003/10

Y1 - 2003/10

N2 - (Ag3MoO3F3)(Ag3MoO 4)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6)Å, c=5.9190(7)Å). The transparent colorless crystals are comprised of chains of distorted fac-MoO3F33- octahedra and MoO42- tetrahedra anions, as suggested by the formulas Ag3MoO3F3 and Ag 3MoO4+, and are connected through Ag + cations in a polar alignment along the c-axis. One Cl- anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by ∼1/2×c. In MoO 42-, the Mo atom displaces towards a single oxide vertex, and in MoO3F33-, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO 3F33- anion is important to prevent local inversion centers, while the polar organization is directed by the Cl - anion and interchain dipole-dipole interactions. The dipole moments of MoO3F33- and MoO4 2- align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO3F33- and MoO 42- were calculated from bond valence analyses and are 6. 1 and 1.9debye (10-18esucm) respectively, compared to 4.4debye for polar NbO6 octahedra in LiNbO3, and 4.5debye for polar TiO6 octahedra in KTiOPO4 (KTP).

AB - (Ag3MoO3F3)(Ag3MoO 4)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6)Å, c=5.9190(7)Å). The transparent colorless crystals are comprised of chains of distorted fac-MoO3F33- octahedra and MoO42- tetrahedra anions, as suggested by the formulas Ag3MoO3F3 and Ag 3MoO4+, and are connected through Ag + cations in a polar alignment along the c-axis. One Cl- anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by ∼1/2×c. In MoO 42-, the Mo atom displaces towards a single oxide vertex, and in MoO3F33-, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO 3F33- anion is important to prevent local inversion centers, while the polar organization is directed by the Cl - anion and interchain dipole-dipole interactions. The dipole moments of MoO3F33- and MoO4 2- align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO3F33- and MoO 42- were calculated from bond valence analyses and are 6. 1 and 1.9debye (10-18esucm) respectively, compared to 4.4debye for polar NbO6 octahedra in LiNbO3, and 4.5debye for polar TiO6 octahedra in KTiOPO4 (KTP).

KW - Dipole moment calculation

KW - Metal oxyfluoride anions

KW - Polar compound

UR - http://www.scopus.com/inward/record.url?scp=0041326589&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0041326589&partnerID=8YFLogxK

U2 - 10.1016/S0022-4596(03)00090-2

DO - 10.1016/S0022-4596(03)00090-2

M3 - Article

VL - 175

SP - 27

EP - 33

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

IS - 1

ER -