Two Molecular-Type Complexes of the Octahedral Rhenium(III) Cyanocluster Anion [Re6Se8(CN)6]4− with M2+ (Mn2+, Ni2+)

Abstract

Two novel octahedral rhenium(III) selenocyanide cluster complexes [(nBu) 4 N] 2 Ni(H 2 O) 5 [Re 6 Se 8 (CN) 6 ]·2H 2 O (1) and [(nBu) 4 N] 2 Mn(H 2 O) 4 [Re 6 Se 8 (CN) 6 ]·2H 2 O (2) have been prepared by the reaction of K 4 [Re 6 Se 8 (CN) 6 ]·3.5H 2 O, (nBu) 4 NBr and Ni(OAc) 2 (or MnSO 4 ) in aqueous solution. The complexes have been structurally solved in the orthorhombic unit cell Pbca with parameters: a = 19.393(2), b = 17.292(2), c = 37.255(4) Å for 1, and a = 19.518(4), b = 17.488(3), c = 37.997(5) Å for 2. The cluster anions and M 2+ form ionic pairs

Playing with [{Mo6Bri6Sei2}(CN)a6]4− Cluster Building Blocks and Mn(salen)+ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

“…The MoÀ L (L = Br/Se) distances range from 2.5822 (7) to 2.6115(9) Å in 1 and from 2.5818(5) to 2.6182(5) Å in 2. These distances are within the range observed in Cs 0.5 K 0.5 (Et 4 N) 11 [{Mo 6 Br i 6 Se i 2 }(CN) 6 ] 3 • 16H 2 O [13] which is built up from the same [{Mo 6 Br i 6 Se i 2 }(CN) a 6 ] 4À cluster unit. Relevant selected bond lengths and angles are listed in Table 2.…”

“…Indeed, it was demonstrated that when Cs + cation, [3a] Me 4 N + (tetramethyammonium) [11b] and Et 4 N + (tetraethylammonium) [11b] cations were used, it led to the formation of three dimensional polymers compounds based on {M 3 [{Re 6 Q i 8 }(CN) 6 ] 2 } 2− complexes and the counter‐cations counterbalancing this charge were located in the cavities of the framework. On the other hand, in the cases of Pr 4 N + (tetrapropylammonium) [15] and of Bu 4 N + (tetrabutylammonium), [11a] a decrease of the dimensionality was observed and 1‐D polymers or molecular complexes were formed. The same trend is observed when comparing the structures of 1 and 2 .…”

Playing with [{Mo6Bri6Sei2}(CN)a6]4− Cluster Building Blocks and Mn(salen)+ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

“…The MoÀ L (L = Br/Se) distances range from 2.5822 (7) to 2.6115(9) Å in 1 and from 2.5818(5) to 2.6182(5) Å in 2. These distances are within the range observed in Cs 0.5 K 0.5 (Et 4 N) 11 [{Mo 6 Br i 6 Se i 2 }(CN) 6 ] 3 • 16H 2 O [13] which is built up from the same [{Mo 6 Br i 6 Se i 2 }(CN) a 6 ] 4À cluster unit. Relevant selected bond lengths and angles are listed in Table 2.…”

“…Indeed, it was demonstrated that when Cs + cation, [3a] Me 4 N + (tetramethyammonium) [11b] and Et 4 N + (tetraethylammonium) [11b] cations were used, it led to the formation of three dimensional polymers compounds based on {M 3 [{Re 6 Q i 8 }(CN) 6 ] 2 } 2− complexes and the counter‐cations counterbalancing this charge were located in the cavities of the framework. On the other hand, in the cases of Pr 4 N + (tetrapropylammonium) [15] and of Bu 4 N + (tetrabutylammonium), [11a] a decrease of the dimensionality was observed and 1‐D polymers or molecular complexes were formed. The same trend is observed when comparing the structures of 1 and 2 .…”

Structure of a new molecular rhenium cluster complex: trans-{[Ni(NH3)5]2×[Re6Se8(CN)4(OH)2]}·6H2O

“…The lengths of Re-Re (2.6147-2.640 Å), Re-Se (2.5159-2.5395 Å), Re-C (2.090-2.106 Å), and C-N (1.145-1.149 Å) bonds are comparable to the data for other complexes containing the [Re 6 Se 8 (CN) 6 ] 4cluster core [10][11][12][13][14][15][16][17][18][19][20], but are somewhat longer (∼0.02 Å) than Re-Re, Re-Se, Re-O (2.080 Å) bonds in the complexes with the [Re 6 Se 8 (OH) 6 ] 4cluster core [5,21]. Molecular complexes and crystallization water molecules are joined by an extended system of hydrogen bonds.…”

Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines

“…Of course five-coordinate complexes are well-known among transition metals and are found to adopt both trigonal bipyramidal and square pyramidal coordination. , Typically however the trigonal bipyramidal environment is more common among the five-coordinate species for low to midvalent d-block ions . There are several examples of square pyramidal Mn­(III) complexes, − but fewer square pyramidal Mn­(II) complexes are known. , …”

Playing with [{Mo6Bri6Sei2}(CN)a6]4− Cluster Building Blocks and Mn(salen)+ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

“…The MoÀ L (L = Br/Se) distances range from 2.5822 (7) to 2.6115(9) Å in 1 and from 2.5818(5) to 2.6182(5) Å in 2. These distances are within the range observed in Cs 0.5 K 0.5 (Et 4 N) 11 [{Mo 6 Br i 6 Se i 2 }(CN) 6 ] 3 • 16H 2 O [13] which is built up from the same [{Mo 6 Br i 6 Se i 2 }(CN) a 6 ] 4À cluster unit. Relevant selected bond lengths and angles are listed in Table 2.…”

“…Indeed, it was demonstrated that when Cs + cation, [3a] Me 4 N + (tetramethyammonium) [11b] and Et 4 N + (tetraethylammonium) [11b] cations were used, it led to the formation of three dimensional polymers compounds based on {M 3 [{Re 6 Q i 8 }(CN) 6 ] 2 } 2− complexes and the counter‐cations counterbalancing this charge were located in the cavities of the framework. On the other hand, in the cases of Pr 4 N + (tetrapropylammonium) [15] and of Bu 4 N + (tetrabutylammonium), [11a] a decrease of the dimensionality was observed and 1‐D polymers or molecular complexes were formed. The same trend is observed when comparing the structures of 1 and 2 .…”

Structure of a new molecular rhenium cluster complex: trans-{[Ni(NH3)5]2×[Re6Se8(CN)4(OH)2]}·6H2O

“…The lengths of Re-Re (2.6147-2.640 Å), Re-Se (2.5159-2.5395 Å), Re-C (2.090-2.106 Å), and C-N (1.145-1.149 Å) bonds are comparable to the data for other complexes containing the [Re 6 Se 8 (CN) 6 ] 4cluster core [10][11][12][13][14][15][16][17][18][19][20], but are somewhat longer (∼0.02 Å) than Re-Re, Re-Se, Re-O (2.080 Å) bonds in the complexes with the [Re 6 Se 8 (OH) 6 ] 4cluster core [5,21]. Molecular complexes and crystallization water molecules are joined by an extended system of hydrogen bonds.…”

Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines

“…Of course five-coordinate complexes are well-known among transition metals and are found to adopt both trigonal bipyramidal and square pyramidal coordination. , Typically however the trigonal bipyramidal environment is more common among the five-coordinate species for low to midvalent d-block ions . There are several examples of square pyramidal Mn­(III) complexes, − but fewer square pyramidal Mn­(II) complexes are known. , …”

Playing with [{Mo6Bri6Sei2}(CN)a6]4− Cluster Building Blocks and Mn(salen)+ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

“…The MoÀ L (L = Br/Se) distances range from 2.5822 (7) to 2.6115(9) Å in 1 and from 2.5818(5) to 2.6182(5) Å in 2. These distances are within the range observed in Cs 0.5 K 0.5 (Et 4 N) 11 [{Mo 6 Br i 6 Se i 2 }(CN) 6 ] 3 • 16H 2 O [13] which is built up from the same [{Mo 6 Br i 6 Se i 2 }(CN) a 6 ] 4À cluster unit. Relevant selected bond lengths and angles are listed in Table 2.…”

“…Indeed, it was demonstrated that when Cs + cation, [3a] Me 4 N + (tetramethyammonium) [11b] and Et 4 N + (tetraethylammonium) [11b] cations were used, it led to the formation of three dimensional polymers compounds based on {M 3 [{Re 6 Q i 8 }(CN) 6 ] 2 } 2− complexes and the counter‐cations counterbalancing this charge were located in the cavities of the framework. On the other hand, in the cases of Pr 4 N + (tetrapropylammonium) [15] and of Bu 4 N + (tetrabutylammonium), [11a] a decrease of the dimensionality was observed and 1‐D polymers or molecular complexes were formed. The same trend is observed when comparing the structures of 1 and 2 .…”

Structure of a new molecular rhenium cluster complex: trans-{[Ni(NH3)5]2×[Re6Se8(CN)4(OH)2]}·6H2O

“…The lengths of Re-Re (2.6147-2.640 Å), Re-Se (2.5159-2.5395 Å), Re-C (2.090-2.106 Å), and C-N (1.145-1.149 Å) bonds are comparable to the data for other complexes containing the [Re 6 Se 8 (CN) 6 ] 4cluster core [10][11][12][13][14][15][16][17][18][19][20], but are somewhat longer (∼0.02 Å) than Re-Re, Re-Se, Re-O (2.080 Å) bonds in the complexes with the [Re 6 Se 8 (OH) 6 ] 4cluster core [5,21]. Molecular complexes and crystallization water molecules are joined by an extended system of hydrogen bonds.…”

Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines

“…Of course five-coordinate complexes are well-known among transition metals and are found to adopt both trigonal bipyramidal and square pyramidal coordination. , Typically however the trigonal bipyramidal environment is more common among the five-coordinate species for low to midvalent d-block ions . There are several examples of square pyramidal Mn­(III) complexes, − but fewer square pyramidal Mn­(II) complexes are known. , …”