Anion-Anion Interactions Involving the [Mo 3 Se 13 ] 2− Cluster. Syntheses and Characterization of (Me 4 N) 2 Mo 3 Se 13 , K 2 Mo 3 Se 12.5 O 0.5 , and K 6 M o6 Se 27 •6H 2 O

Ju Hsiou Liao; Jing Li; Mercouri G. Kanatzidis

doi:10.1021/ic00114a026

Anion-Anion Interactions Involving the [Mo ₃ Se ₁₃ ] ²⁻ Cluster. Syntheses and Characterization of (Me ₄ N) ₂ Mo ₃ Se ₁₃ , K ₂ Mo ₃ Se _12.5 O _0.5 , and K ₆ M _o6 Se ₂₇ •6H ₂ O

Ju Hsiou Liao, Jing Li, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

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

33 Scopus citations

Abstract

The hydrothermal reaction of M0O ₃ , Na ₂ Se ₂ and Me ₄ NCl (molar ratio, 1:3:2) at 135 °C for 3 days gave dark red needles of (Me ₄ N)2Mo ₃ Se ₁₃ (I); the reaction of M0O ₃ and K ₂ Se ₂ (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135 °C gave black needle-like crystals of K ₂ Mo ₃ Se _12.5 O ₀ . ₅ (II) and black chunky crystals of K ₆ Mo ₆ -Se ₂₇ 6H ₂ O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P3 ₁ m (No. 157), Z = 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å ³ . d _calc = 3.42 g/cm ³ , 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/R _w = 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) Å ³ , d _cale = 4.45 g/cm ³ , 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/R _W = 4.3/5.3%. III crystallizes in the monoclinic space group P2 ₁ /n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, ß = 98.8(1)°, V = 4868(21) Å ³ , d _Calc = 4.15 g/cm ³ . 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 [Mo ₃ Se ₁₃ ] ²⁻ in I and [Mo ₃ Se _12.5 O _0.5 ] ²⁻ in II are isostructural with [Mo ₃ S ₁₃ ] ²⁻ , while III is the cocrystallization of two K ₂ Mo ₃ Se ₁₃ clusters and one K ₂ Se. 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 [Mo ₃ Se ₁₃ ] 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 Hiickel calculations were performed to explain the unusual [Mo ₃ Se ₁₃ ] ²⁻ Se ²⁻ interactions in these compounds. The calculations show that the Se atoms (of the bridging Se ₂ ²⁻ ), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

Original language	English (US)
Pages (from-to)	2658-2670
Number of pages	13
Journal	Inorganic chemistry
Volume	34
Issue number	10
DOIs	https://doi.org/10.1021/ic00114a026
State	Published - May 1 1995

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{546856a66be346f8b08d1bfba5bcc529,

title = "Anion-Anion Interactions Involving the [Mo 3 Se 13 ] 2− Cluster. Syntheses and Characterization of (Me 4 N) 2 Mo 3 Se 13 , K 2 Mo 3 Se 12.5 O 0.5 , and K 6 M o6 Se 27 •6H 2 O",

abstract = " The hydrothermal reaction of M0O 3 , Na 2 Se 2 and Me 4 NCl (molar ratio, 1:3:2) at 135 °C for 3 days gave dark red needles of (Me 4 N)2Mo 3 Se 13 (I); the reaction of M0O 3 and K 2 Se 2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135 °C gave black needle-like crystals of K 2 Mo 3 Se 12.5 O 0 . 5 (II) and black chunky crystals of K 6 Mo 6 -Se 27 6H 2 O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P3 1 m (No. 157), Z = 1, a = 11.578(1) {\AA}, c = 6.110(2) {\AA}, V = 709.4(3) {\AA} 3 . d calc = 3.42 g/cm 3 , 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/R w = 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 , d cale = 4.45 g/cm 3 , 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/R W = 4.3/5.3%. III crystallizes in the monoclinic space group P2 1 /n (No. 14), Z = 4, a = 10.21(2) {\AA}, b = 17.84(1) {\AA}, c = 27.04(2) {\AA}, {\ss} = 98.8(1)°, V = 4868(21) {\AA} 3 , d Calc = 4.15 g/cm 3 . 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 [Mo 3 Se 13 ] 2− in I and [Mo 3 Se 12.5 O 0.5 ] 2− in II are isostructural with [Mo 3 S 13 ] 2− , while III is the cocrystallization of two K 2 Mo 3 Se 13 clusters and one K 2 Se. 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 [Mo 3 Se 13 ] 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 Hiickel calculations were performed to explain the unusual [Mo 3 Se 13 ] 2− Se 2− interactions in these compounds. The calculations show that the Se atoms (of the bridging Se 2 2− ), 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",

month = may,

day = "1",

doi = "10.1021/ic00114a026",

language = "English (US)",

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 [Mo 3 Se 13 ] 2− Cluster. Syntheses and Characterization of (Me 4 N) 2 Mo 3 Se 13 , K 2 Mo 3 Se 12.5 O 0.5 , and K 6 M o6 Se 27 •6H 2 O

AU - Liao, Ju Hsiou

AU - Li, Jing

AU - Kanatzidis, Mercouri G.

PY - 1995/5/1

Y1 - 1995/5/1

N2 - The hydrothermal reaction of M0O 3 , Na 2 Se 2 and Me 4 NCl (molar ratio, 1:3:2) at 135 °C for 3 days gave dark red needles of (Me 4 N)2Mo 3 Se 13 (I); the reaction of M0O 3 and K 2 Se 2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135 °C gave black needle-like crystals of K 2 Mo 3 Se 12.5 O 0 . 5 (II) and black chunky crystals of K 6 Mo 6 -Se 27 6H 2 O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P3 1 m (No. 157), Z = 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å 3 . d calc = 3.42 g/cm 3 , 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/R w = 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) Å 3 , d cale = 4.45 g/cm 3 , 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/R W = 4.3/5.3%. III crystallizes in the monoclinic space group P2 1 /n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, ß = 98.8(1)°, V = 4868(21) Å 3 , d Calc = 4.15 g/cm 3 . 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 [Mo 3 Se 13 ] 2− in I and [Mo 3 Se 12.5 O 0.5 ] 2− in II are isostructural with [Mo 3 S 13 ] 2− , while III is the cocrystallization of two K 2 Mo 3 Se 13 clusters and one K 2 Se. 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 [Mo 3 Se 13 ] 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 Hiickel calculations were performed to explain the unusual [Mo 3 Se 13 ] 2− Se 2− interactions in these compounds. The calculations show that the Se atoms (of the bridging Se 2 2− ), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

AB - The hydrothermal reaction of M0O 3 , Na 2 Se 2 and Me 4 NCl (molar ratio, 1:3:2) at 135 °C for 3 days gave dark red needles of (Me 4 N)2Mo 3 Se 13 (I); the reaction of M0O 3 and K 2 Se 2 (molar ratio of 1:2 for one month and 1:3-5 for 3 days) at 135 °C gave black needle-like crystals of K 2 Mo 3 Se 12.5 O 0 . 5 (II) and black chunky crystals of K 6 Mo 6 -Se 27 6H 2 O (III) respectively. The structures were determined by single crystal X-ray diffraction techniques. Compound I crystallizes in the trigonal space group P3 1 m (No. 157), Z = 1, a = 11.578(1) Å, c = 6.110(2) Å, V = 709.4(3) Å 3 . d calc = 3.42 g/cm 3 , 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/R w = 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) Å 3 , d cale = 4.45 g/cm 3 , 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/R W = 4.3/5.3%. III crystallizes in the monoclinic space group P2 1 /n (No. 14), Z = 4, a = 10.21(2) Å, b = 17.84(1) Å, c = 27.04(2) Å, ß = 98.8(1)°, V = 4868(21) Å 3 , d Calc = 4.15 g/cm 3 . 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 [Mo 3 Se 13 ] 2− in I and [Mo 3 Se 12.5 O 0.5 ] 2− in II are isostructural with [Mo 3 S 13 ] 2− , while III is the cocrystallization of two K 2 Mo 3 Se 13 clusters and one K 2 Se. 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 [Mo 3 Se 13 ] 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 Hiickel calculations were performed to explain the unusual [Mo 3 Se 13 ] 2− Se 2− interactions in these compounds. The calculations show that the Se atoms (of the bridging Se 2 2− ), which form the points of interaction of the cluster with the anionic species, are weakly positively charged.

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JF - Inorganic Chemistry

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