Cs[Cl₃F₁₀]: A Propeller‐Shaped [Cl₃F₁₀]⁻ Anion in a Peculiar A^[5]B^[5] Structure Type

Abstract

Reaction of CsF with ClF3 leads to Cs[Cl3F10]. It contains a molecular, propeller‐shaped [Cl3F10]− anion with a central μ3‐F atom and three T‐shaped ClF3 molecules coordinated to it. This anion represents the first example of a heteropolyhalide anion of higher ClF3 content than [ClF4]− and is the first Cl‐containing interhalogen species with a μ‐bridging F atom. The chemical bonds to the central μ3‐F atom are highly ionic and quite weak as the bond lengths within the coordinating XF3 units (X = Cl, and also calculated for Br, I) are almost unchanged in comparison to free XF3 molecules. Cs[Cl3F10] crystallizes in a very rarely observed A[5]B[5] structure type, where cations and anions are each pseudohexagonally close packed, and reside, each with coordination number five, in the trigonal bipyramidal voids of the other.

Photochemistry with ClF3 – An Access to [ClOF2]+ Salts

“…Irradiation for a couple of days led to the Overview of selected compounds obtained from reactions with ClF 3 , including those described in this work. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] formation of colorless [ClOF 2 ] 2 [RhF 6 ] (Rh) among unreacted Rh powder (Equation 1).…”

“… Overview of selected compounds obtained from reactions with ClF 3 , including those described in this work [9–24] …”

Non-classical polyinterhalides of chlorine monofluoride: experimental and theoretical characterization of [F(ClF)3]−

“… 16 The Kraus group recently synthesized the first non-classical fluoridochlorate( iii ), the [F(ClF 3 ) 3 ] − anion obtained by solvolysis of CsF in ClF 3 . 17 Here, we present an unprecedented Cl(I) compound, [NMe 4 ][F(ClF) 3 ]. With a formal [F(ClF) 3 ] − anion, it belongs to the non-classical interhalides.…”

“…In the crystal structure of the Cs salt it shows, however, a distorted C 3 -symmetry with a dihedral angle of 136.4(2)°. 17 Other examples are the poly(hydrogenhalide)halogenates of the general type [X(HY) 3 ] − (X, Y = F, Cl, Br, I). For the [F(HF) 3 ] − anion (X, Y = F) a planar structure was predicted to be slightly more stable, but only the K + -salt shows a planar anion, whereas several other solid-state structures show pyramidal anion structures.…”

Trendbericht Anorganik 2022 Teil 1: Hauptgruppen

“…43) Kraus' Team hat diese Verbindung kristallisiert: Das [Cl 3 F 10 ] − -Ion hat eine propellerartige Struktur mit einem μ 3 -F-Atom im Zentrum. Daran koordinieren drei T-förmige ClF 3 -Einheiten (Abbildung 32).…”