Anion-anion interactions involving the [Mo3Se13]2- cluster. Syntheses and characterization of (Me4N)2Mo3Se13, K2Mo3Se12.5O0.5, and K6Mo6Se27·6H2O

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Abstract

The hydrothermal reaction of MoO3, Na2Se2 and Me4NCl (molar ratio, 1:3:2) at 135°C for 3 days gave dark red needles of (Me4N)2Mo3Se13 (I); the reaction of MoO3 and K2Se2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135°C gave black needle-like crystals of K2Mo3Se12.5O0.5 (II) and black chunky crystals of K6Mo6Se27·6H2O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P31m (No. 157), Z= 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å3, dcalc = 3.42 g/cm3, μ = 177.99 cm-1. Number of data measured: 992. Number of unique data: 502. Number of data having I > 3.0σ(I): 438. Number of variables = 49. R/Rw = 6.0/7.5%. Compound II crystallizes in the monoclinic space group Cm (No. 8), Z = 2, a = 11.874(3) Å, b = 16.834(3) Å, c = 5.820(3) Å, β = 116.65(2)°, V = 1040(1) Å3, dcalc = 4.45 g/cm3. μ = 246.64 cm-1. Number of data measured: 997. Number of unique data: 951. Number of data having I > 3.0σ(I): 849. Number of variables = 89. R/Rw = 4.3/5.3%. III crystallizes in the monoclinic space group P21/n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, β = 98.8(1)°, V = 4868(21) Å3, dcalc = 4.15 g/cm3. μ = 219.98 cm-1. Number of data measured: 8706. Number of unique data: 7920. Number of data having I > 3.0σ(I): 3520. Number of variables = 391. The [Mo3Se13]2- in I and [Mo3Se12.5O0.5]2- in II are isostructural with [Mo3S13]2-, while III is the cocrystallization of two K2Mo3Se13 clusters and one K2Se. The anions of I and II are the same except that the triply bridging Se site is partially occupied by O atoms in II. Solid state IR and UV/vis spectra are reported. The [Mo3Se13]2- cluster has been found to possess significant affinity for anionic species, and this has been manifested in all currently known compounds containing this trinuclear cluster. The new compounds reported in this paper also exhibit clearly defined anion-anion weakly bonding interactions. Extended Hückel calculations were performed to explain the unusual [Mo3Se13]2-·Se2- interactions in these compounds. The calculations show that the Se atoms (of the bridging Se22-), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

Original languageEnglish
Pages (from-to)2658-2670
Number of pages13
JournalInorganic Chemistry
Volume34
Issue number10
Publication statusPublished - 1995

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Anions
anions
Needles
synthesis
needles
Atoms
Crystals
interactions
Single crystals
crystals
atoms
affinity
X ray diffraction
solid state
single crystals
diffraction
x rays
molybdenum trioxide

ASJC Scopus subject areas

  • Inorganic Chemistry

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@article{e70286d1be7c4907875ea2b4893ed197,
title = "Anion-anion interactions involving the [Mo3Se13]2- cluster. Syntheses and characterization of (Me4N)2Mo3Se13, K2Mo3Se12.5O0.5, and K6Mo6Se27·6H2O",
abstract = "The hydrothermal reaction of MoO3, Na2Se2 and Me4NCl (molar ratio, 1:3:2) at 135°C for 3 days gave dark red needles of (Me4N)2Mo3Se13 (I); the reaction of MoO3 and K2Se2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135°C gave black needle-like crystals of K2Mo3Se12.5O0.5 (II) and black chunky crystals of K6Mo6Se27·6H2O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P31m (No. 157), Z= 1, a = 11.578(1) {\AA}, c = 6.110(2) {\AA}, V = 709.4(3) {\AA}3, dcalc = 3.42 g/cm3, μ = 177.99 cm-1. Number of data measured: 992. Number of unique data: 502. Number of data having I > 3.0σ(I): 438. Number of variables = 49. R/Rw = 6.0/7.5{\%}. Compound II crystallizes in the monoclinic space group Cm (No. 8), Z = 2, a = 11.874(3) {\AA}, b = 16.834(3) {\AA}, c = 5.820(3) {\AA}, β = 116.65(2)°, V = 1040(1) {\AA}3, dcalc = 4.45 g/cm3. μ = 246.64 cm-1. Number of data measured: 997. Number of unique data: 951. Number of data having I > 3.0σ(I): 849. Number of variables = 89. R/Rw = 4.3/5.3{\%}. III crystallizes in the monoclinic space group P21/n (No. 14), Z = 4, a = 10.21(2) {\AA}, b = 17.84(1) {\AA}, c = 27.04(2) {\AA}, β = 98.8(1)°, V = 4868(21) {\AA}3, dcalc = 4.15 g/cm3. μ = 219.98 cm-1. Number of data measured: 8706. Number of unique data: 7920. Number of data having I > 3.0σ(I): 3520. Number of variables = 391. The [Mo3Se13]2- in I and [Mo3Se12.5O0.5]2- in II are isostructural with [Mo3S13]2-, while III is the cocrystallization of two K2Mo3Se13 clusters and one K2Se. The anions of I and II are the same except that the triply bridging Se site is partially occupied by O atoms in II. Solid state IR and UV/vis spectra are reported. The [Mo3Se13]2- cluster has been found to possess significant affinity for anionic species, and this has been manifested in all currently known compounds containing this trinuclear cluster. The new compounds reported in this paper also exhibit clearly defined anion-anion weakly bonding interactions. Extended H{\"u}ckel calculations were performed to explain the unusual [Mo3Se13]2-·Se2- interactions in these compounds. The calculations show that the Se atoms (of the bridging Se22-), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.",
author = "Liao, {Ju Hsiou} and Jing Li and Kanatzidis, {Mercouri G}",
year = "1995",
language = "English",
volume = "34",
pages = "2658--2670",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Anion-anion interactions involving the [Mo3Se13]2- cluster. Syntheses and characterization of (Me4N)2Mo3Se13, K2Mo3Se12.5O0.5, and K6Mo6Se27·6H2O

AU - Liao, Ju Hsiou

AU - Li, Jing

AU - Kanatzidis, Mercouri G

PY - 1995

Y1 - 1995

N2 - The hydrothermal reaction of MoO3, Na2Se2 and Me4NCl (molar ratio, 1:3:2) at 135°C for 3 days gave dark red needles of (Me4N)2Mo3Se13 (I); the reaction of MoO3 and K2Se2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135°C gave black needle-like crystals of K2Mo3Se12.5O0.5 (II) and black chunky crystals of K6Mo6Se27·6H2O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P31m (No. 157), Z= 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å3, dcalc = 3.42 g/cm3, μ = 177.99 cm-1. Number of data measured: 992. Number of unique data: 502. Number of data having I > 3.0σ(I): 438. Number of variables = 49. R/Rw = 6.0/7.5%. Compound II crystallizes in the monoclinic space group Cm (No. 8), Z = 2, a = 11.874(3) Å, b = 16.834(3) Å, c = 5.820(3) Å, β = 116.65(2)°, V = 1040(1) Å3, dcalc = 4.45 g/cm3. μ = 246.64 cm-1. Number of data measured: 997. Number of unique data: 951. Number of data having I > 3.0σ(I): 849. Number of variables = 89. R/Rw = 4.3/5.3%. III crystallizes in the monoclinic space group P21/n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, β = 98.8(1)°, V = 4868(21) Å3, dcalc = 4.15 g/cm3. μ = 219.98 cm-1. Number of data measured: 8706. Number of unique data: 7920. Number of data having I > 3.0σ(I): 3520. Number of variables = 391. The [Mo3Se13]2- in I and [Mo3Se12.5O0.5]2- in II are isostructural with [Mo3S13]2-, while III is the cocrystallization of two K2Mo3Se13 clusters and one K2Se. The anions of I and II are the same except that the triply bridging Se site is partially occupied by O atoms in II. Solid state IR and UV/vis spectra are reported. The [Mo3Se13]2- cluster has been found to possess significant affinity for anionic species, and this has been manifested in all currently known compounds containing this trinuclear cluster. The new compounds reported in this paper also exhibit clearly defined anion-anion weakly bonding interactions. Extended Hückel calculations were performed to explain the unusual [Mo3Se13]2-·Se2- interactions in these compounds. The calculations show that the Se atoms (of the bridging Se22-), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

AB - The hydrothermal reaction of MoO3, Na2Se2 and Me4NCl (molar ratio, 1:3:2) at 135°C for 3 days gave dark red needles of (Me4N)2Mo3Se13 (I); the reaction of MoO3 and K2Se2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135°C gave black needle-like crystals of K2Mo3Se12.5O0.5 (II) and black chunky crystals of K6Mo6Se27·6H2O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P31m (No. 157), Z= 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å3, dcalc = 3.42 g/cm3, μ = 177.99 cm-1. Number of data measured: 992. Number of unique data: 502. Number of data having I > 3.0σ(I): 438. Number of variables = 49. R/Rw = 6.0/7.5%. Compound II crystallizes in the monoclinic space group Cm (No. 8), Z = 2, a = 11.874(3) Å, b = 16.834(3) Å, c = 5.820(3) Å, β = 116.65(2)°, V = 1040(1) Å3, dcalc = 4.45 g/cm3. μ = 246.64 cm-1. Number of data measured: 997. Number of unique data: 951. Number of data having I > 3.0σ(I): 849. Number of variables = 89. R/Rw = 4.3/5.3%. III crystallizes in the monoclinic space group P21/n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, β = 98.8(1)°, V = 4868(21) Å3, dcalc = 4.15 g/cm3. μ = 219.98 cm-1. Number of data measured: 8706. Number of unique data: 7920. Number of data having I > 3.0σ(I): 3520. Number of variables = 391. The [Mo3Se13]2- in I and [Mo3Se12.5O0.5]2- in II are isostructural with [Mo3S13]2-, while III is the cocrystallization of two K2Mo3Se13 clusters and one K2Se. The anions of I and II are the same except that the triply bridging Se site is partially occupied by O atoms in II. Solid state IR and UV/vis spectra are reported. The [Mo3Se13]2- cluster has been found to possess significant affinity for anionic species, and this has been manifested in all currently known compounds containing this trinuclear cluster. The new compounds reported in this paper also exhibit clearly defined anion-anion weakly bonding interactions. Extended Hückel calculations were performed to explain the unusual [Mo3Se13]2-·Se2- interactions in these compounds. The calculations show that the Se atoms (of the bridging Se22-), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

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VL - 34

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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