Coordination Polymers of Small Cyano Anions

Batten, Stuart Robert; Deacon, Glen B.; Murray, Keith S.; Turner, David R.

doi:10.2533/chimia.2013.379

Cited by 6 publications

(1 citation statement)

References 34 publications

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“…Conjugated cyano-and polycyanoanions (thiocyanate, dicyanoamide, tricyanomethanide, polycyanopropenides etc.) have attracted significant interest as valuable building blocks in the development of coordination polymers (Batten et al, 2013;Turner et al, 2011) and for transmitting electronic effects between metal ions (Batten & Murray, 2003), in particular for spin cross-over (SCO) systems (Gü tlich et al, 2013). The ability of such anions to sustain secondary host-guest interactions is also prominent, while complementing their behaviour as N-donor acido-ligands.…”

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confidence: 99%

Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

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In the ionic structure of the title compound, [Fe(C12H8N2)3](C9H5N4O2)2·H2O, the octahedral tris-chelate [Fe(phen)3](2+) dications [Fe-N = 1.9647 (14)-1.9769 (14) Å; phen is 1,10-phenathroline] afford one-dimensional chains by a series of slipped π-π stacking interactions [centroid-to-centroid distances = 3.792 (3) and 3.939 (3) Å]. The 1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide anions, denoted tcnoetOH(-), reveal an appreciable delocalization of π-electron density, involving the central propenide [C-C = 1.383 (3)-1.401 (2) Å] fragment and four nitrile groups, and this is also supported by density functional theory (DFT) calculations at the B97D/6-311+G(2d,2p) level. Primary noncovalent inter-moiety interactions comprise conventional O-H...O(N) and weak C-H...O(N) hydrogen bonding [O...O(N) = 2.833 (2)-3.289 (5) Å and C...O(N) = 3.132 (2)-3.439 (2) Å]. The double anion...π interaction involving a nitrile group of tcnoetOH(-) and two cis-positioned pyridine rings (`π-pocket') of [Fe(phen)3](2+) [N...centroid = 3.212 (2) and 3.418 (2) Å] suggest the relevance of anion...π stackings for charge-diffuse polycyanoanions and common M-chelate species.

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Section: Introductionmentioning

confidence: 99%

Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

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ChemInform Abstract: Coordination Polymers of Small Cyano Anions

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Sodium Salts of Substituted Tetracyanocyclopentadienides [C₅(CN)₄X]⁻ (X= H, CN, NH₂, NO₂): Substituent Influence on the Crystal Structures of Potential Coordination Polymers.

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Metathesis reactions of NaCl with the silver salts of substituted tetracyanocyclopentadienides [C 5 (CN) 4 X] À (X = H, CN, NO 2 , NH 2 ) gives the corresponding sodium salts 1-4. While 1-3 give polymeric networks, held together by Pi-stacking as well as multiply bridging polydentate cyanocyclopentadienides and in part hydrogen bonda, the aminotetracyanocyclo-pentadienide 4 forms only a water-bridged dinuclear complexes, which are connected only by an intensive hydrogen bond network. Quite surprisingly, only the NO 2 -substituent in 3 coordinates to Na + besides the cyano groups, while the NH 2 group in 4 is only involved in hydrogen bonds.

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Coordination Polymers of Small Cyano Anions

Cited by 6 publications

References 34 publications

Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

ChemInform Abstract: Coordination Polymers of Small Cyano Anions

Sodium Salts of Substituted Tetracyanocyclopentadienides [C₅(CN)₄X]⁻ (X= H, CN, NH₂, NO₂): Substituent Influence on the Crystal Structures of Potential Coordination Polymers.

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Coordination Polymers of Small Cyano Anions

Cited by 6 publications

References 34 publications

Multiple anion...π interactions in tris(1,10-phenanthroline-κ2N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

Multiple anion...π interactions in tris(1,10-phenanthroline-κ2N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

ChemInform Abstract: Coordination Polymers of Small Cyano Anions

Sodium Salts of Substituted Tetracyanocyclopentadienides [C5(CN)4X]− (X= H, CN, NH2, NO2): Substituent Influence on the Crystal Structures of Potential Coordination Polymers.

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Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

Multiple anion...π interactions in tris(1,10-phenanthroline-κ²N,N′)iron(II) bis[1,1,3,3-tetracyano-2-(2-hydroxyethyl)propenide] monohydrate

Sodium Salts of Substituted Tetracyanocyclopentadienides [C₅(CN)₄X]⁻ (X= H, CN, NH₂, NO₂): Substituent Influence on the Crystal Structures of Potential Coordination Polymers.