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

Research output: Contribution to journalArticlepeer-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 languageEnglish (US)
Pages (from-to)2658-2670
Number of pages13
JournalInorganic chemistry
Volume34
Issue number10
DOIs
StatePublished - May 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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