Back to Search
Start Over
Crystal structures of seven mixed-valence gold compounds of the form [(R¹ R² R³ PE)2AuI ] + [AuIIIX4] (R = tert-butyl or isopropyl, E = S or Se, and X = Cl or Br.
- Source :
- Acta Crystallographica Section E: Crystallographic Communications; Oct2024, Vol. 80 Issue 10, p1087-1096, 54p
- Publication Year :
- 2024
-
Abstract
- During our studies of the oxidation of gold(I) complexes of tri­alkyl­phosphane chalcogenides, general formula R¹R²R³PEAuX, (R = tert-butyl or isopropyl, E = S or Se, X = Cl or Br) with PhICl<subscript>2</subscript> or elemental bromine, we have isolated a set of seven mixed-valence by-products, the bis­(tri­alkyl­phosphane chalcogenido)gold(I) tetra­halogenidoaurates(III) [(R¹R²R³PE)<subscript>2</subscript>Au]<superscript>+</superscript>[AuX<subscript>4</subscript>]<superscript>−</superscript>. These corres­pond to the addition of one halogen atom per gold atom of the Au<superscript>I</superscript> precursor. Com­pound 1, bis­(triiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aur­ate(III), [Au(C<subscript>9</subscript>H<subscript>21</subscript>PS)<subscript>2</subscript>][AuCl<subscript>4</subscript>] or [(<superscript>i</superscript>Pr<subscript>3</subscript>PS)<subscript>2</subscript>Au][AuCl<subscript>4</subscript>], crystallizes in space group P2<subscript>1</subscript>/n with Z = 4; the gold(I) atoms of the two cations lie on twofold rotation axes, and the gold(III) atoms of the two anions lie on inversion centres. Compound 2, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C<subscript>10</subscript>H<subscript>23</subscript>PS)<subscript>2</subscript>][AuCl<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<superscript>i</superscript>Pr<subscript>2</subscript>PS)<subscript>2</subscript>Au][AuCl<subscript>4</subscript>], crystallizes in space group P1 with Z = 4; the asymmetric unit contains two cations and two anions with no imposed symmetry. A least-squares fit of the two cations gave an r.m.s. deviation of 0.19 Å. Compound 3, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C<subscript>12</subscript>H<subscript>27</subscript>PS)<subscript>2</subscript>][AuCl<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<subscript>3</subscript>PS)<subscript>2</subscript>Au][AuCl<subscript>4</subscript>], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 4a, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­bromi­doaurate(III), [Au(C<subscript>10</subscript>H<subscript>23</subscript>PS)<subscript>2</subscript>][AuBr<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<superscript>i</superscript>Pr<subscript>2</subscript>PS)<subscript>2</subscript>Au][AuBr<subscript>4</subscript>], crystallizes in space group P2<subscript>1</subscript>/c with Z = 4; the cation lies on a general position, whereas the gold(III) atoms of the two anions lie on inversion centres. Compound 4b, bis­(tert-butyl­diiso­propyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C<subscript>10</subscript>H<subscript>23</subscript>PSe)<subscript>2</subscript>][AuBr<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<superscript>i</superscript>Pr<subscript>2</subscript>PSe)<subscript>2</subscript>Au][AuBr<subscript>4</subscript>], is isotypic with 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C<subscript>12</subscript>H<subscript>27</subscript>PS)<subscript>2</subscript>][AuBr<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<subscript>3</subscript>PS)<subscript>2</subscript>Au][AuBr<subscript>4</subscript>], is isotypic with compound 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C<subscript>12</subscript>H<subscript>27</subscript>PS)<subscript>2</subscript>][AuBr<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<subscript>3</subscript>PS)<subscript>2</subscript>Au][AuBr<subscript>4</subscript>], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 5b, bis­(tri-tert-butyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C<subscript>12</subscript>H<subscript>27</subscript>PSe)<subscript>2</subscript>][AuBr<subscript>4</subscript>] or [(<superscript>t</superscript>Bu<subscript>3</subscript>PSe)<subscript>2</subscript>Au][AuBr<subscript>4</subscript>], is isotypic with 5a. All Au<superscript>I</superscript> atoms are linearly coordinated and all Au<superscript>III</superscript> atoms exhibit a square-planar coordination environment. The ligands at the Au<superscript>I</superscript> atoms are anti­periplanar to each other across the S⋯S vectors. There are several short intra­molecular H⋯Au and H⋯E contacts. Average bond lengths (Å) are: P—S = 2.0322, P—Se = 2.1933, S—Au = 2.2915, and Se—Au = 2.4037. The complex three-dimensional packing of 1 involves two short C—H<subscript>methine</subscript>⋯Cl contacts (and some slightly longer contacts). For 2, four C—H<subscript>methine</subscript>⋯Cl inter­actions combine to produce zigzag chains of residues parallel to the c axis. Additionally, an S⋯Cl contact is observed that might qualify as a ‘chalcogen bond’. The packing of 3 is three-dimensional, but can be broken down into two layer structures, each involving an S⋯Cl and an H⋯Cl contact. For the bromido derivatives 4a/b and 5a/b, loose associations of the anions form part of the packing patterns. For all four compounds, these combine with an E⋯Br contact to form layers parallel to the ab plane. [ABSTRACT FROM AUTHOR]
- Subjects :
- GOLD compounds
SPACE groups
CHEMICAL bond lengths
CRYSTAL structure
CHALCOGENIDES
Subjects
Details
- Language :
- English
- ISSN :
- 20569890
- Volume :
- 80
- Issue :
- 10
- Database :
- Complementary Index
- Journal :
- Acta Crystallographica Section E: Crystallographic Communications
- Publication Type :
- Academic Journal
- Accession number :
- 180142518
- Full Text :
- https://doi.org/10.1107/S2056989024009095