Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)

trans-Dibromidobis(3,5-lutidine)gold(III) tribromide, [AuBr2(C7H9N)2](Br3) or [(3,5-Lut)2AuBr2](Br3), 1, polymorph a, crystallizes in the space group P1 with Z = 1. The gold atom and the central bromine of the tribromide ion lie on inversion centres. Polymorph b crystallizes in C2221 with Z = 4. The...

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Main Authors: Cindy Döring, Peter G. Jones
Format: Article
Language:English
Published: International Union of Crystallography 2025-08-01
Series:Acta Crystallographica Section E: Crystallographic Communications
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Online Access:https://journals.iucr.org/paper?S2056989025006401
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author Cindy Döring
Peter G. Jones
author_facet Cindy Döring
Peter G. Jones
author_sort Cindy Döring
collection DOAJ
description trans-Dibromidobis(3,5-lutidine)gold(III) tribromide, [AuBr2(C7H9N)2](Br3) or [(3,5-Lut)2AuBr2](Br3), 1, polymorph a, crystallizes in the space group P1 with Z = 1. The gold atom and the central bromine of the tribromide ion lie on inversion centres. Polymorph b crystallizes in C2221 with Z = 4. The gold atom, the nitrogen atoms and the ring atoms at the 4-position of the lutidine ligands, and the central bromine of the tribromide ion all lie on twofold axes. The formula units of 1a and 1b are closely similar (including the relative orientations of anion and cation). 3,5-Lutidinium tetrabromidoaurate(III), (C7H10N)[AuBr4] or (3,5-LutH)[AuBr4], 2, crystallizes as a new polymorph in P32 with Z = 3. Bis(3,5-lutidinium) tetrabromidoaurate(III) bromide, (C7H10N)2[AuBr4]Br or (3,5-LutH)2[AuBr4]Br, 3, polymorph a, crystallizes in C2/c with Z = 4. The gold atom lies on an inversion centre and the bromide ion on a twofold axis. Polymorph b crystallizes in P21/c with Z = 8 (Z′ = 2) and all atoms on general positions. Tris(3,5-lutidinium) bis[tetrabromidoaurate(III)] bromide, (C7H10N)3[AuBr4]2Br or (3,5-LutH)3[AuBr4]2Br, 4, crystallizes in P1 with Z = 2. One gold atom lies on a general position and two on inversion centres. The main interest centres on the crystal packing patterns. In structure 1a, a short Au...Branion contact, presumably a ‘coinage bond', combines with a ‘weak' hydrogen bond Hortho...Branion and a further contact Brcation...Branion to form a layer structure parallel to the ac plane. Polymorph 1b shows similar Au...Branion and Hortho...Branion contacts, resulting in a chain of residues parallel to the c axis. The most striking feature of the previous polymorph of compound 2 was a topologically square, but distorted, network of tetrabromidoaurate ions. The packing of the new polymorph of 2 involves three-centre hydrogen bonds Br...H...Br′, an axial coinage bond Au...Br, and two Br...Br contacts, one of which completes an unusual AuBr2 three-centre system. The extended packing shows three one-dimensional arrays of residues parallel to the threefold axis, linked by one Br...Br contact to form a layer. In polymorph a of compound 3, the packing is based on a dimeric unit with twofold symmetry, centred on the free bromide ion, which is involved in two hydrogen bonds and two Br...Br interactions. The dimers are connected via further Br...Br contacts to form a zigzag chain parallel to the c axis. Polymorph b displays two hydrogen-bonded (3,5-LutH...)2Br groupings to the two free bromides, together with two tetrabromidoaurate ions linked by a Br...Br contact; the second anion is also connected to a free bromide. The residues thus linked form a broad band parallel to the c axis. There are also infinite stacks of planar residues with the repeating sequence (...[AuBr4]−...lutidinium...lutidinium...) parallel to the a axis. In compound 4, all three cations are hydrogen bonded to the free bromide. The anions at two gold centres (Au1/Au2) form a chain parallel to the a axis via Br...Br contacts. The anions at Au3 combine with the free bromide to form a chain of Au2Br4 rings parallel to the a axis, via Au...Br and Br...Br contacts, and these chains link with those at Au1 via another Br...Br contact to form a broad ribbon of residues. The ribbons are in turn linked by a Br...π contact.
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spelling doaj-art-419161a2d6dc4871ab4d516531bbf69f2025-08-20T03:40:38ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902025-08-0181875376410.1107/S2056989025006401yz2069Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)Cindy Döring0Peter G. Jones1Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, GermanyInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germanytrans-Dibromidobis(3,5-lutidine)gold(III) tribromide, [AuBr2(C7H9N)2](Br3) or [(3,5-Lut)2AuBr2](Br3), 1, polymorph a, crystallizes in the space group P1 with Z = 1. The gold atom and the central bromine of the tribromide ion lie on inversion centres. Polymorph b crystallizes in C2221 with Z = 4. The gold atom, the nitrogen atoms and the ring atoms at the 4-position of the lutidine ligands, and the central bromine of the tribromide ion all lie on twofold axes. The formula units of 1a and 1b are closely similar (including the relative orientations of anion and cation). 3,5-Lutidinium tetrabromidoaurate(III), (C7H10N)[AuBr4] or (3,5-LutH)[AuBr4], 2, crystallizes as a new polymorph in P32 with Z = 3. Bis(3,5-lutidinium) tetrabromidoaurate(III) bromide, (C7H10N)2[AuBr4]Br or (3,5-LutH)2[AuBr4]Br, 3, polymorph a, crystallizes in C2/c with Z = 4. The gold atom lies on an inversion centre and the bromide ion on a twofold axis. Polymorph b crystallizes in P21/c with Z = 8 (Z′ = 2) and all atoms on general positions. Tris(3,5-lutidinium) bis[tetrabromidoaurate(III)] bromide, (C7H10N)3[AuBr4]2Br or (3,5-LutH)3[AuBr4]2Br, 4, crystallizes in P1 with Z = 2. One gold atom lies on a general position and two on inversion centres. The main interest centres on the crystal packing patterns. In structure 1a, a short Au...Branion contact, presumably a ‘coinage bond', combines with a ‘weak' hydrogen bond Hortho...Branion and a further contact Brcation...Branion to form a layer structure parallel to the ac plane. Polymorph 1b shows similar Au...Branion and Hortho...Branion contacts, resulting in a chain of residues parallel to the c axis. The most striking feature of the previous polymorph of compound 2 was a topologically square, but distorted, network of tetrabromidoaurate ions. The packing of the new polymorph of 2 involves three-centre hydrogen bonds Br...H...Br′, an axial coinage bond Au...Br, and two Br...Br contacts, one of which completes an unusual AuBr2 three-centre system. The extended packing shows three one-dimensional arrays of residues parallel to the threefold axis, linked by one Br...Br contact to form a layer. In polymorph a of compound 3, the packing is based on a dimeric unit with twofold symmetry, centred on the free bromide ion, which is involved in two hydrogen bonds and two Br...Br interactions. The dimers are connected via further Br...Br contacts to form a zigzag chain parallel to the c axis. Polymorph b displays two hydrogen-bonded (3,5-LutH...)2Br groupings to the two free bromides, together with two tetrabromidoaurate ions linked by a Br...Br contact; the second anion is also connected to a free bromide. The residues thus linked form a broad band parallel to the c axis. There are also infinite stacks of planar residues with the repeating sequence (...[AuBr4]−...lutidinium...lutidinium...) parallel to the a axis. In compound 4, all three cations are hydrogen bonded to the free bromide. The anions at two gold centres (Au1/Au2) form a chain parallel to the a axis via Br...Br contacts. The anions at Au3 combine with the free bromide to form a chain of Au2Br4 rings parallel to the a axis, via Au...Br and Br...Br contacts, and these chains link with those at Au1 via another Br...Br contact to form a broad ribbon of residues. The ribbons are in turn linked by a Br...π contact.https://journals.iucr.org/paper?S2056989025006401crystal structurepolymorphismlutidinetetrabromidoaurate(iii)hydrogen bondhalogen bondcoinage bondstacking
spellingShingle Cindy Döring
Peter G. Jones
Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
Acta Crystallographica Section E: Crystallographic Communications
crystal structure
polymorphism
lutidine
tetrabromidoaurate(iii)
hydrogen bond
halogen bond
coinage bond
stacking
title Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
title_full Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
title_fullStr Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
title_full_unstemmed Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
title_short Crystal structures of trans-dibromidobis(3,5-lutidine)gold(III) tribromide and three 3,5-lutidinium salts containing tetrabromidoaurate(III) anions (including three cases of polymorphism)
title_sort crystal structures of trans dibromidobis 3 5 lutidine gold iii tribromide and three 3 5 lutidinium salts containing tetrabromidoaurate iii anions including three cases of polymorphism
topic crystal structure
polymorphism
lutidine
tetrabromidoaurate(iii)
hydrogen bond
halogen bond
coinage bond
stacking
url https://journals.iucr.org/paper?S2056989025006401
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