Hydrothermal polychalcogenide chemistry. Stabilization of [Mo9Se40]8-, a cluster of clusters, and [Mo3Se18]n2n-, a polymeric polyselenide. Novel phases based on trinuclear [Mo3Se7]4+ building blocks

Ju Hsiou Liao, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

94 Citations (Scopus)

Abstract

A polymeric Mo polyselenide, K2Mo3Se18, and a large molecular cluster Mo polyselenide, K8Mo9Se40·4H2O, were synthesized by the hydrothermal method. The reaction of Mo, K2Se4, and H2O in a 1:1.5:22.2 ratio in a vacuum-sealed Pyrex tube at 135 °C for 3 days yielded black platelike crystals of K2Mo3Se18 (I). The reaction of MoO3, K2Se2, and H2O in a 1:2:22.2 ratio under the same conditions as above yielded black chunky crystals of K8Mo9Se40·4H2O (II). Both compounds were obtained in ∼20% yield. The structures were determined by single-crystal X-ray diffraction techniques. Crystal data for K2Mo3Se18: monoclinic P21, Z = 2, a = 10.277 (6) Å, b = 12.66 (1) Å, c 10.624 (8) Å, β = 116.82 (5)°, V = 1233 (2) Å3; 2θmax(MO Kα) = 45°; number of data measured 1824, number of unique data 1608, number of data having Fo2 > 3σ(Fo2) 1382, number of variables 207, number of atoms 23; μ = 267 cm-1; final R = 0.052 and Rw = 0.086. Crystal data for K8Mo9Se40·4H2O: triclinic P1, Z = 2, a 10.312 (8) Å, b = 18.55 (3) Å, c = 18.57 (2) Å, α = 87.6 (1)°, β = 87.57 (7)°, γ 84.0 (1)°, V = 3523 (8) Å3; 2θmax(MO Kα) = 45°; number of data measured 9888, number of unique data 8638, number of data having Fo2 > 4σ(Fo2) 3592, number of variables 546, number of atoms 65; μ = 224 cm-1; final R = 0.092 and Rw = 0.108. I and II have rather complicated structures. I contains the [Mo3(Se)(Se2)3(Se3)(Se 4)2]n2n- polymeric anion which contains [Mo3Se7]4+ clusters as building blocks. It has a zigzag chain structure which is formed by two parallel sets of face-to-face [Mo3Se7]4+ clusters cross-linked by Se42- ligands. The zigzag chains are then arranged side by side and interact through weak Se⋯Se contacts generated by a Se atom of a Se32- ligand of one chain and the triangular face of Se atoms from the three bridging Se22- ligands of a [Mo3Se7]4+ cluster in another chain. [Mo9Se40]8- contains three trinuclear [Mo3Se7]4+ subclusters which are "glued" together by the two monoselenide ions. One monoselenide ion belongs to a [Mo3Se7]4+ core being coordinated to three Mo atoms and at the same time interacting with the triangular face of three Se atoms of Se22- bridging ligands of another [Mo3Se7]4+ subcluster. The other monoselenide ion interacts with six Se atoms of Se22- bridging ligands of two [Mo3Se7]4+ subclusters. Two separate [Mo9Se40]8- clusters come in close contact (2.98 Å) in the solid state through two terminal Se22- ligands related by an inversion center.

Original languageEnglish
Pages (from-to)431-439
Number of pages9
JournalInorganic Chemistry
Volume31
Issue number3
Publication statusPublished - 1992

Fingerprint

Stabilization
stabilization
chemistry
Atoms
Ligands
ligands
atoms
Crystals
Ions
crystals
ions
molecular clusters
borosilicate glass
Anions
Single crystals
Vacuum
inversions
tubes
anions
solid state

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{5ac8c023d49443098132401a4708a775,
title = "Hydrothermal polychalcogenide chemistry. Stabilization of [Mo9Se40]8-, a cluster of clusters, and [Mo3Se18]n2n-, a polymeric polyselenide. Novel phases based on trinuclear [Mo3Se7]4+ building blocks",
abstract = "A polymeric Mo polyselenide, K2Mo3Se18, and a large molecular cluster Mo polyselenide, K8Mo9Se40·4H2O, were synthesized by the hydrothermal method. The reaction of Mo, K2Se4, and H2O in a 1:1.5:22.2 ratio in a vacuum-sealed Pyrex tube at 135 °C for 3 days yielded black platelike crystals of K2Mo3Se18 (I). The reaction of MoO3, K2Se2, and H2O in a 1:2:22.2 ratio under the same conditions as above yielded black chunky crystals of K8Mo9Se40·4H2O (II). Both compounds were obtained in ∼20{\%} yield. The structures were determined by single-crystal X-ray diffraction techniques. Crystal data for K2Mo3Se18: monoclinic P21, Z = 2, a = 10.277 (6) {\AA}, b = 12.66 (1) {\AA}, c 10.624 (8) {\AA}, β = 116.82 (5)°, V = 1233 (2) {\AA}3; 2θmax(MO Kα) = 45°; number of data measured 1824, number of unique data 1608, number of data having Fo2 > 3σ(Fo2) 1382, number of variables 207, number of atoms 23; μ = 267 cm-1; final R = 0.052 and Rw = 0.086. Crystal data for K8Mo9Se40·4H2O: triclinic P1, Z = 2, a 10.312 (8) {\AA}, b = 18.55 (3) {\AA}, c = 18.57 (2) {\AA}, α = 87.6 (1)°, β = 87.57 (7)°, γ 84.0 (1)°, V = 3523 (8) {\AA}3; 2θmax(MO Kα) = 45°; number of data measured 9888, number of unique data 8638, number of data having Fo2 > 4σ(Fo2) 3592, number of variables 546, number of atoms 65; μ = 224 cm-1; final R = 0.092 and Rw = 0.108. I and II have rather complicated structures. I contains the [Mo3(Se)(Se2)3(Se3)(Se 4)2]n2n- polymeric anion which contains [Mo3Se7]4+ clusters as building blocks. It has a zigzag chain structure which is formed by two parallel sets of face-to-face [Mo3Se7]4+ clusters cross-linked by Se42- ligands. The zigzag chains are then arranged side by side and interact through weak Se⋯Se contacts generated by a Se atom of a Se32- ligand of one chain and the triangular face of Se atoms from the three bridging Se22- ligands of a [Mo3Se7]4+ cluster in another chain. [Mo9Se40]8- contains three trinuclear [Mo3Se7]4+ subclusters which are {"}glued{"} together by the two monoselenide ions. One monoselenide ion belongs to a [Mo3Se7]4+ core being coordinated to three Mo atoms and at the same time interacting with the triangular face of three Se atoms of Se22- bridging ligands of another [Mo3Se7]4+ subcluster. The other monoselenide ion interacts with six Se atoms of Se22- bridging ligands of two [Mo3Se7]4+ subclusters. Two separate [Mo9Se40]8- clusters come in close contact (2.98 {\AA}) in the solid state through two terminal Se22- ligands related by an inversion center.",
author = "Liao, {Ju Hsiou} and Kanatzidis, {Mercouri G}",
year = "1992",
language = "English",
volume = "31",
pages = "431--439",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Hydrothermal polychalcogenide chemistry. Stabilization of [Mo9Se40]8-, a cluster of clusters, and [Mo3Se18]n2n-, a polymeric polyselenide. Novel phases based on trinuclear [Mo3Se7]4+ building blocks

AU - Liao, Ju Hsiou

AU - Kanatzidis, Mercouri G

PY - 1992

Y1 - 1992

N2 - A polymeric Mo polyselenide, K2Mo3Se18, and a large molecular cluster Mo polyselenide, K8Mo9Se40·4H2O, were synthesized by the hydrothermal method. The reaction of Mo, K2Se4, and H2O in a 1:1.5:22.2 ratio in a vacuum-sealed Pyrex tube at 135 °C for 3 days yielded black platelike crystals of K2Mo3Se18 (I). The reaction of MoO3, K2Se2, and H2O in a 1:2:22.2 ratio under the same conditions as above yielded black chunky crystals of K8Mo9Se40·4H2O (II). Both compounds were obtained in ∼20% yield. The structures were determined by single-crystal X-ray diffraction techniques. Crystal data for K2Mo3Se18: monoclinic P21, Z = 2, a = 10.277 (6) Å, b = 12.66 (1) Å, c 10.624 (8) Å, β = 116.82 (5)°, V = 1233 (2) Å3; 2θmax(MO Kα) = 45°; number of data measured 1824, number of unique data 1608, number of data having Fo2 > 3σ(Fo2) 1382, number of variables 207, number of atoms 23; μ = 267 cm-1; final R = 0.052 and Rw = 0.086. Crystal data for K8Mo9Se40·4H2O: triclinic P1, Z = 2, a 10.312 (8) Å, b = 18.55 (3) Å, c = 18.57 (2) Å, α = 87.6 (1)°, β = 87.57 (7)°, γ 84.0 (1)°, V = 3523 (8) Å3; 2θmax(MO Kα) = 45°; number of data measured 9888, number of unique data 8638, number of data having Fo2 > 4σ(Fo2) 3592, number of variables 546, number of atoms 65; μ = 224 cm-1; final R = 0.092 and Rw = 0.108. I and II have rather complicated structures. I contains the [Mo3(Se)(Se2)3(Se3)(Se 4)2]n2n- polymeric anion which contains [Mo3Se7]4+ clusters as building blocks. It has a zigzag chain structure which is formed by two parallel sets of face-to-face [Mo3Se7]4+ clusters cross-linked by Se42- ligands. The zigzag chains are then arranged side by side and interact through weak Se⋯Se contacts generated by a Se atom of a Se32- ligand of one chain and the triangular face of Se atoms from the three bridging Se22- ligands of a [Mo3Se7]4+ cluster in another chain. [Mo9Se40]8- contains three trinuclear [Mo3Se7]4+ subclusters which are "glued" together by the two monoselenide ions. One monoselenide ion belongs to a [Mo3Se7]4+ core being coordinated to three Mo atoms and at the same time interacting with the triangular face of three Se atoms of Se22- bridging ligands of another [Mo3Se7]4+ subcluster. The other monoselenide ion interacts with six Se atoms of Se22- bridging ligands of two [Mo3Se7]4+ subclusters. Two separate [Mo9Se40]8- clusters come in close contact (2.98 Å) in the solid state through two terminal Se22- ligands related by an inversion center.

AB - A polymeric Mo polyselenide, K2Mo3Se18, and a large molecular cluster Mo polyselenide, K8Mo9Se40·4H2O, were synthesized by the hydrothermal method. The reaction of Mo, K2Se4, and H2O in a 1:1.5:22.2 ratio in a vacuum-sealed Pyrex tube at 135 °C for 3 days yielded black platelike crystals of K2Mo3Se18 (I). The reaction of MoO3, K2Se2, and H2O in a 1:2:22.2 ratio under the same conditions as above yielded black chunky crystals of K8Mo9Se40·4H2O (II). Both compounds were obtained in ∼20% yield. The structures were determined by single-crystal X-ray diffraction techniques. Crystal data for K2Mo3Se18: monoclinic P21, Z = 2, a = 10.277 (6) Å, b = 12.66 (1) Å, c 10.624 (8) Å, β = 116.82 (5)°, V = 1233 (2) Å3; 2θmax(MO Kα) = 45°; number of data measured 1824, number of unique data 1608, number of data having Fo2 > 3σ(Fo2) 1382, number of variables 207, number of atoms 23; μ = 267 cm-1; final R = 0.052 and Rw = 0.086. Crystal data for K8Mo9Se40·4H2O: triclinic P1, Z = 2, a 10.312 (8) Å, b = 18.55 (3) Å, c = 18.57 (2) Å, α = 87.6 (1)°, β = 87.57 (7)°, γ 84.0 (1)°, V = 3523 (8) Å3; 2θmax(MO Kα) = 45°; number of data measured 9888, number of unique data 8638, number of data having Fo2 > 4σ(Fo2) 3592, number of variables 546, number of atoms 65; μ = 224 cm-1; final R = 0.092 and Rw = 0.108. I and II have rather complicated structures. I contains the [Mo3(Se)(Se2)3(Se3)(Se 4)2]n2n- polymeric anion which contains [Mo3Se7]4+ clusters as building blocks. It has a zigzag chain structure which is formed by two parallel sets of face-to-face [Mo3Se7]4+ clusters cross-linked by Se42- ligands. The zigzag chains are then arranged side by side and interact through weak Se⋯Se contacts generated by a Se atom of a Se32- ligand of one chain and the triangular face of Se atoms from the three bridging Se22- ligands of a [Mo3Se7]4+ cluster in another chain. [Mo9Se40]8- contains three trinuclear [Mo3Se7]4+ subclusters which are "glued" together by the two monoselenide ions. One monoselenide ion belongs to a [Mo3Se7]4+ core being coordinated to three Mo atoms and at the same time interacting with the triangular face of three Se atoms of Se22- bridging ligands of another [Mo3Se7]4+ subcluster. The other monoselenide ion interacts with six Se atoms of Se22- bridging ligands of two [Mo3Se7]4+ subclusters. Two separate [Mo9Se40]8- clusters come in close contact (2.98 Å) in the solid state through two terminal Se22- ligands related by an inversion center.

UR - http://www.scopus.com/inward/record.url?scp=0037716957&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037716957&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0037716957

VL - 31

SP - 431

EP - 439

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -