Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions
The structures of three 4-methylpyridinium tetrahalogenidoaurate(III) halides, one also including a dichloroiodate(I) anion, are presented. Bis(4-methylpiperidinium) tetrabromidoaurate(III) bromide, (4-Me-pipH)2[AuBr4]Br, 1, crystallizes in space group C2/c with Z = 4. The gold atom lies on the inve...
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International Union of Crystallography
2025-07-01
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| Series: | Acta Crystallographica Section E: Crystallographic Communications |
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| Online Access: | https://journals.iucr.org/paper?S2056989025004918 |
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| author | Cindy Döring Peter G. Jones |
| author_facet | Cindy Döring Peter G. Jones |
| author_sort | Cindy Döring |
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| description | The structures of three 4-methylpyridinium tetrahalogenidoaurate(III) halides, one also including a dichloroiodate(I) anion, are presented. Bis(4-methylpiperidinium) tetrabromidoaurate(III) bromide, (4-Me-pipH)2[AuBr4]Br, 1, crystallizes in space group C2/c with Z = 4. The gold atom lies on the inversion centre 0.75, 0.75, 0.5 and the bromide ion on the twofold axis 0.5, y, 0.25. Bis(4-methylpiperidinium) tetrachloridoaurate(III) chloride, (4-Me-pipH)2[AuCl4]Cl, 2, was obtained as three polymorphs, none of which is isotypic to 1. Polymorph 2a crystallizes in space group P21/c with Z = 4; all atoms lie on general positions. Polymorph 2b crystallizes in space group P2/c with Z = 8; two chloride ions lie on the twofold axes 0, y, 1/4 and 0.5, y, 0.25. Polymorph 2c crystallizes in space group P1 with Z = 10; all atoms lie on general positions. Hexakis(4-methylpiperidinium) tetrakis{tetrachloridoaurate(III)} dichloroiodate(I) chloride, (4-Me-pipH)6[AuCl4]4(ICl2)Cl, 3, crystallizes in space group P1 with Z = 1; two gold atoms occupy inversion centres, as do the iodine atom and one chloride. This is the first time that we have observed the chlorinating agent PhICl2 to be `non-innocent'. The main interest centres on the crystal packings, which involve hydrogen, halogen and coinage bonds, and display prominent substructures, one type involving the cations and the halides, and the other type involving the anions. A common feature in the packing of compounds 1 and 2 is a chain consisting of cations linked by halide ions. In 1, the chains are flanked by tetrabromidoaurate ions via short Br...Br contacts. The anions form zigzag chains via Br...Br−...Br groupings. In polymorph 2a, chains of cations and chloride ions connect to chains of tetrachloridoaurate ions to form a layer structure. In polymorph 2b, cation/chloride chains connect with chains of tetrachloridoaurate and chloride anions to form a layer structure; approximately linear Au...Cl−...Au groupings are a striking feature (these are also seen in 2c and 3). The asymmetric unit of polymorph 2c is an ensemble ca 27 Å long. Cation/chloride chains are linked by tetrachloridoaurates to form one-dimensional polymers. The tetrachloridoaurate and chloride ions associate to form a layer structure. In the packing of compound 3 the chloride/tetrachloridoaurate substructure is dominant. Two tetrachloridoaurate ions associate with the free chloride to form a layer structure; the layers are linked in the third dimension via the third tetrachloroaurate and the dichloroiodate ions. There is no independent cation/chloride substructure; the cations may be considered as being interspersed in the spaces of the anionic substructure, forming hydrogen bonds (some multicentred) to chlorine atoms of the anions. A brief database survey of other structures involving aryl- or alkylammonium cations, tetrahalogenidoaurates and halides is presented, including packing diagrams of selected examples. |
| format | Article |
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| institution | Kabale University |
| issn | 2056-9890 |
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| publishDate | 2025-07-01 |
| publisher | International Union of Crystallography |
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| series | Acta Crystallographica Section E: Crystallographic Communications |
| spelling | doaj-art-1a2e90183d954392b32cc25bb862dc0d2025-08-20T03:50:12ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902025-07-0181760061210.1107/S2056989025004918yz2066Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anionsCindy 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, GermanyThe structures of three 4-methylpyridinium tetrahalogenidoaurate(III) halides, one also including a dichloroiodate(I) anion, are presented. Bis(4-methylpiperidinium) tetrabromidoaurate(III) bromide, (4-Me-pipH)2[AuBr4]Br, 1, crystallizes in space group C2/c with Z = 4. The gold atom lies on the inversion centre 0.75, 0.75, 0.5 and the bromide ion on the twofold axis 0.5, y, 0.25. Bis(4-methylpiperidinium) tetrachloridoaurate(III) chloride, (4-Me-pipH)2[AuCl4]Cl, 2, was obtained as three polymorphs, none of which is isotypic to 1. Polymorph 2a crystallizes in space group P21/c with Z = 4; all atoms lie on general positions. Polymorph 2b crystallizes in space group P2/c with Z = 8; two chloride ions lie on the twofold axes 0, y, 1/4 and 0.5, y, 0.25. Polymorph 2c crystallizes in space group P1 with Z = 10; all atoms lie on general positions. Hexakis(4-methylpiperidinium) tetrakis{tetrachloridoaurate(III)} dichloroiodate(I) chloride, (4-Me-pipH)6[AuCl4]4(ICl2)Cl, 3, crystallizes in space group P1 with Z = 1; two gold atoms occupy inversion centres, as do the iodine atom and one chloride. This is the first time that we have observed the chlorinating agent PhICl2 to be `non-innocent'. The main interest centres on the crystal packings, which involve hydrogen, halogen and coinage bonds, and display prominent substructures, one type involving the cations and the halides, and the other type involving the anions. A common feature in the packing of compounds 1 and 2 is a chain consisting of cations linked by halide ions. In 1, the chains are flanked by tetrabromidoaurate ions via short Br...Br contacts. The anions form zigzag chains via Br...Br−...Br groupings. In polymorph 2a, chains of cations and chloride ions connect to chains of tetrachloridoaurate ions to form a layer structure. In polymorph 2b, cation/chloride chains connect with chains of tetrachloridoaurate and chloride anions to form a layer structure; approximately linear Au...Cl−...Au groupings are a striking feature (these are also seen in 2c and 3). The asymmetric unit of polymorph 2c is an ensemble ca 27 Å long. Cation/chloride chains are linked by tetrachloridoaurates to form one-dimensional polymers. The tetrachloridoaurate and chloride ions associate to form a layer structure. In the packing of compound 3 the chloride/tetrachloridoaurate substructure is dominant. Two tetrachloridoaurate ions associate with the free chloride to form a layer structure; the layers are linked in the third dimension via the third tetrachloroaurate and the dichloroiodate ions. There is no independent cation/chloride substructure; the cations may be considered as being interspersed in the spaces of the anionic substructure, forming hydrogen bonds (some multicentred) to chlorine atoms of the anions. A brief database survey of other structures involving aryl- or alkylammonium cations, tetrahalogenidoaurates and halides is presented, including packing diagrams of selected examples.https://journals.iucr.org/paper?S2056989025004918crystal structuretetrahalogenidoaurate(iii)hydrogen bondhalogen bondcoinage bond |
| spellingShingle | Cindy Döring Peter G. Jones Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions Acta Crystallographica Section E: Crystallographic Communications crystal structure tetrahalogenidoaurate(iii) hydrogen bond halogen bond coinage bond |
| title | Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions |
| title_full | Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions |
| title_fullStr | Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions |
| title_full_unstemmed | Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions |
| title_short | Crystal structures of three 4-methylpiperidinium salts (one as three polymorphs) with tetrahalogenidoaurate(III), halide and (in one case) dichloroiodate(I) counter-anions |
| title_sort | crystal structures of three 4 methylpiperidinium salts one as three polymorphs with tetrahalogenidoaurate iii halide and in one case dichloroiodate i counter anions |
| topic | crystal structure tetrahalogenidoaurate(iii) hydrogen bond halogen bond coinage bond |
| url | https://journals.iucr.org/paper?S2056989025004918 |
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