Synthesis and crystal structure of (NEt3Me)2CsP11·5NH3

Synthesis and Crystal Structure of Tricaesium Heptaphosphide–Ammonia(1/3) Cs3P7·3 NH3

“…Each Cs' ion has two contacts with NH, molecules, which in turn means that each NH, molecule serves as a bridging ligand between two of the three crystallographically inequivalent Cs' ions. The corresponding Cs-N distances lie between 3.25 and 3.61 A, which is in good agreement with previously observed values for ammoniates of Cs compounds [4][5][6]. Fig.…”

“…This is especially obvious for Cs (2), which resides over the sides of two cages and is additionally coordinated in a side-on manner by P(2) and P(5). Together with the two contacts to N-atoms of ammonia, this leads to a total coordination number of ten for Cs(2); however, several of the corresponding Cs ... P distances are at the upper limit of the range of previously observed values (Cs-P distances from 3.5 to 4.1 A, beyond 4.1 8, there is usually a clear cut-off [3][4][5][6]). As can be seen in Fig.…”

Synthesis and Crystal Structure of Tricaesium Heptaphosphide–Ammonia(1/3) Cs3P7·3 NH3

“…Each Cs' ion has two contacts with NH, molecules, which in turn means that each NH, molecule serves as a bridging ligand between two of the three crystallographically inequivalent Cs' ions. The corresponding Cs-N distances lie between 3.25 and 3.61 A, which is in good agreement with previously observed values for ammoniates of Cs compounds [4][5][6]. Fig.…”

“…This is especially obvious for Cs (2), which resides over the sides of two cages and is additionally coordinated in a side-on manner by P(2) and P(5). Together with the two contacts to N-atoms of ammonia, this leads to a total coordination number of ten for Cs(2); however, several of the corresponding Cs ... P distances are at the upper limit of the range of previously observed values (Cs-P distances from 3.5 to 4.1 A, beyond 4.1 8, there is usually a clear cut-off [3][4][5][6]). As can be seen in Fig.…”

[Sb11]3− and [As11]3−: Synthesis and Crystal Structure of Two New Ammoniates containing Trishomocubane‐like Polyanions

“…Merely one-di- (6) 3.276(9) 169(7) 12 1, N(9)-H(9C)···N (7) 1.01 (7) 2.32 (7) 3.30(1) 163(9) 16 1, N(9)-H(9E)···N (10) 1.03 (7) 2.45 (7) 3.46(1) 167 (7) (7), Cs(2)-N(1) 3.529(4), Cs(2)-N(4) 3.578 (7), Cs(2)-As(5)#1 3.8931(9), Cs(2)-As (6) mensional chains are formed in 2, because two cesium cations are also coordinated by the chelating 18-crown-6 ligand, which insulates one side of the cesium cations from further coordination by the undecaarsenide anions. A similar situation was found in Cs(PPh 4 ) 2 As 7 · 5NH 3 [15] or in [NEt 3 Me] 2 CsP 11 · 5NH 3 [2]. There, the quaternary phosphonium/ammonium cations take the role of the shielded cesium cations in 2, which also results in infinite chains ( 1 ϱ [CsAs 7 ] 2Ϫ and 1 ϱ [CsP 11 ] 2Ϫ ).…”

Syntheses and Crystal Structures of Four New Ammoniates with Heptaarsenide (As$\rm{_{7}^{3-}}$) Anions

“…Similarly varying dimensionalities of alkali metal ± polypnictide substructures have already been described for the ammoniates of hepta-and undecapolyphosphides. While Cs 3 P 11´3 NH 3 [29] or Cs 3 P 7´3 NH 3 [30] form 3D networks as in 3, the dimensionality is reduced to 2D sheets [33]. The lack of any extended alkali metal ± polypnictide substructure in 1 and 2 shows two general possibilities for the generation of such situations.…”

Synthesis and Crystal Structure of Tricaesium Heptaphosphide–Ammonia(1/3) Cs3P7·3 NH3

“…Each Cs' ion has two contacts with NH, molecules, which in turn means that each NH, molecule serves as a bridging ligand between two of the three crystallographically inequivalent Cs' ions. The corresponding Cs-N distances lie between 3.25 and 3.61 A, which is in good agreement with previously observed values for ammoniates of Cs compounds [4][5][6]. Fig.…”

“…This is especially obvious for Cs (2), which resides over the sides of two cages and is additionally coordinated in a side-on manner by P(2) and P(5). Together with the two contacts to N-atoms of ammonia, this leads to a total coordination number of ten for Cs(2); however, several of the corresponding Cs ... P distances are at the upper limit of the range of previously observed values (Cs-P distances from 3.5 to 4.1 A, beyond 4.1 8, there is usually a clear cut-off [3][4][5][6]). As can be seen in Fig.…”

[Sb11]3− and [As11]3−: Synthesis and Crystal Structure of Two New Ammoniates containing Trishomocubane‐like Polyanions

“…Merely one-di- (6) 3.276(9) 169(7) 12 1, N(9)-H(9C)···N (7) 1.01 (7) 2.32 (7) 3.30(1) 163(9) 16 1, N(9)-H(9E)···N (10) 1.03 (7) 2.45 (7) 3.46(1) 167 (7) (7), Cs(2)-N(1) 3.529(4), Cs(2)-N(4) 3.578 (7), Cs(2)-As(5)#1 3.8931(9), Cs(2)-As (6) mensional chains are formed in 2, because two cesium cations are also coordinated by the chelating 18-crown-6 ligand, which insulates one side of the cesium cations from further coordination by the undecaarsenide anions. A similar situation was found in Cs(PPh 4 ) 2 As 7 · 5NH 3 [15] or in [NEt 3 Me] 2 CsP 11 · 5NH 3 [2]. There, the quaternary phosphonium/ammonium cations take the role of the shielded cesium cations in 2, which also results in infinite chains ( 1 ϱ [CsAs 7 ] 2Ϫ and 1 ϱ [CsP 11 ] 2Ϫ ).…”

Syntheses and Crystal Structures of Four New Ammoniates with Heptaarsenide (As$\rm{_{7}^{3-}}$) Anions

“…Similarly varying dimensionalities of alkali metal ± polypnictide substructures have already been described for the ammoniates of hepta-and undecapolyphosphides. While Cs 3 P 11´3 NH 3 [29] or Cs 3 P 7´3 NH 3 [30] form 3D networks as in 3, the dimensionality is reduced to 2D sheets [33]. The lack of any extended alkali metal ± polypnictide substructure in 1 and 2 shows two general possibilities for the generation of such situations.…”

Synthesis and Crystal Structure of Tricaesium Heptaphosphide–Ammonia(1/3) Cs3P7·3 NH3

“…Each Cs' ion has two contacts with NH, molecules, which in turn means that each NH, molecule serves as a bridging ligand between two of the three crystallographically inequivalent Cs' ions. The corresponding Cs-N distances lie between 3.25 and 3.61 A, which is in good agreement with previously observed values for ammoniates of Cs compounds [4][5][6]. Fig.…”

“…This is especially obvious for Cs (2), which resides over the sides of two cages and is additionally coordinated in a side-on manner by P(2) and P(5). Together with the two contacts to N-atoms of ammonia, this leads to a total coordination number of ten for Cs(2); however, several of the corresponding Cs ... P distances are at the upper limit of the range of previously observed values (Cs-P distances from 3.5 to 4.1 A, beyond 4.1 8, there is usually a clear cut-off [3][4][5][6]). As can be seen in Fig.…”

[Sb11]3− and [As11]3−: Synthesis and Crystal Structure of Two New Ammoniates containing Trishomocubane‐like Polyanions

“…Merely one-di- (6) 3.276(9) 169(7) 12 1, N(9)-H(9C)···N (7) 1.01 (7) 2.32 (7) 3.30(1) 163(9) 16 1, N(9)-H(9E)···N (10) 1.03 (7) 2.45 (7) 3.46(1) 167 (7) (7), Cs(2)-N(1) 3.529(4), Cs(2)-N(4) 3.578 (7), Cs(2)-As(5)#1 3.8931(9), Cs(2)-As (6) mensional chains are formed in 2, because two cesium cations are also coordinated by the chelating 18-crown-6 ligand, which insulates one side of the cesium cations from further coordination by the undecaarsenide anions. A similar situation was found in Cs(PPh 4 ) 2 As 7 · 5NH 3 [15] or in [NEt 3 Me] 2 CsP 11 · 5NH 3 [2]. There, the quaternary phosphonium/ammonium cations take the role of the shielded cesium cations in 2, which also results in infinite chains ( 1 ϱ [CsAs 7 ] 2Ϫ and 1 ϱ [CsP 11 ] 2Ϫ ).…”

Syntheses and Crystal Structures of Four New Ammoniates with Heptaarsenide (As$\rm{_{7}^{3-}}$) Anions

“…Similarly varying dimensionalities of alkali metal ± polypnictide substructures have already been described for the ammoniates of hepta-and undecapolyphosphides. While Cs 3 P 11´3 NH 3 [29] or Cs 3 P 7´3 NH 3 [30] form 3D networks as in 3, the dimensionality is reduced to 2D sheets [33]. The lack of any extended alkali metal ± polypnictide substructure in 1 and 2 shows two general possibilities for the generation of such situations.…”