(Terpyridine)manganese(II) Coordination Polymers with Thio‐ and Selenidoarsenate(III) Ligands: Coligand Influence on the Chalcogenidoarsenate(III) Species and Coordination Mode

Abstract

Hydrothermal reaction of [MnCl2(terpy)] with elemental As and Se at 150 °C in 1:2:4 and 1:4:8 molar ratios in the presence of Cs2CO3 affords the complexes [{Mn(terpy)}2 (As2Se5)]2 (1) and [{Mn(terpy)}2 (As4Se8)] (2), respectively. 1 contains dipyramidal [As2Se5]4− ligands that bridge three MnII atoms in a tetradentate μ3‐1κ2Se1,Se2:2κSe4:3κSe5 manner. The tetranuclear complex is centrosymmetric and exhibits a central 8‐membered (MnSeAsSe)2 ring. Cyclic [As4Se8]4− ligands are present in the centrosymmetric dinuclear complex 2 and chelate the Mn(II) atoms through adjacent terminal Se atoms. Both 1 and 2 are linked into infinite chains through weak Mn···Se interactions. [{Mn(terpy)}2(As4S8)] (3) and $_{\infty}^{1}\rm [{Mn(terpy)}(As_{2}S_{4})]$ (4) can be obtained by hydrothermal reaction of [MnCl2(terpy)] with As2S3 at respectively 150 °C and 190 °C. Whereas 3 exhibits an identical connectivity pattern to that of 2, the coordination polymer 4 contains vierer $_{\infty}^{1}\rm [AsS_{2}^{-}]$ chains that coordinate {(terpy)Mn}2+ fragments in a bidentate manner through terminal S atoms. The complex $_{\infty}^{1}\rm [{Mn(tren)}\textrm{ } (As_{4}S_{7})]$ (5) contains $_{\infty}^{1}\rm [As_{4}S_{7}^{2-}]$ double chains and results from the analogous hydrothermal reaction of [MnCl2(tren)] with As2S3 at 150 °C.

Infinite Anionic Chains Formed by Alternating Bidentately Acting [SbS4]3- Anions and [Mn(dien)]2+ Complexes in the Compound [Mn(dien)2][Mn(dien)SbS4]2

“…2) The Mn-S bond lengths are between 2.452(2) und 2.509(2)Å, and the Mn-N bonds vary from 2.211(7) to 2.326(6)Å, thus being in the range reported for other Mn containing thiometalates [42]. The MnN 3 S 2 coordination environment in the thioantimonate chain is rather unusual, and only few examples are known for such a coordination geome- try, like in [{Mn(terpy)}(As 2 S 4 )] (terpy = 2,2 ;6 ,2 -terpyridine) [42] or in a complex with a pentadentate SNNNS ligand [43]. The Sb-S bond lengths (Table 2) can be grouped into two short terminal bonds (Sb-S: 2.300(2) -2.3070(17)Å) and two bridging bonds (2.3478 (16) The S-Sb-S angles around Sb1 range from 105.56(6) to 113.40(8) • , and for Sb2 they are between 105.56(7) and 113.25(8) • , i. e. the distortion from ideal tetrahedral geometry is very similar for both [SbS 4 ] 3− units.…”

“…The final coordination polyhedron may be described as a distorted rectangular pyramid with one S atom and three N atoms forming the rectangular plane and one S atom at the apical position (Fig. 2) The Mn-S bond lengths are between 2.452(2) und 2.509(2)Å, and the Mn-N bonds vary from 2.211(7) to 2.326(6)Å, thus being in the range reported for other Mn containing thiometalates [42]. The MnN 3 S 2 coordination environment in the thioantimonate chain is rather unusual, and only few examples are known for such a coordination geome- try, like in [{Mn(terpy)}(As 2 S 4 )] (terpy = 2,2 ;6 ,2 -terpyridine) [42] or in a complex with a pentadentate SNNNS ligand [43].…”

Solvent effect on condensation of pyramidal [AsSe3]3–: solvothermal syntheses of new selenidoarsenates containing transition metal(II) complexes with 1,10-phenanthroline

“…Hydro-or solvothermal synthesis from 100-200 C and extraction technique at room temperature have proven to be useful for access to chalcogenidoarsenate [6][7][8][9] [22], [TM(dien) 2 ]As 2 Se 6 (dien ¼ diethylenetriamine) (TM ¼ Co, Ni), and [Mn(dap) 3 ]As 2 Se 6 (dap ¼ 1,2-diaminopropane) [23]. Recently, selenidoarsenates -As 2 Se 4 , -As 2 Se 5 , -As 4 Se 7 , and -As 4 Se 8 were obtained in manganese complexes with the tridentate terpy (terpy ¼ 2,2 0 ;6 0 , 2 00 -terpyridine) or tetradentate tren as the coligands [24][25][26] [34,35] were prepared by reactions of TMCl 2 , As 2 O 3 , Se, and phen under methanol-thermal conditions. Now, the TM/As/Se/phen system is investigated in water and CH 3 OH aqueous solution, and selenidoarsenates(III) [TM(phen) 3 ] 2 [As 8 Se 14 ] (TM ¼ Ni (1), Zn (2)) and polyselenidoarsenates(III) [TM(phen) 3 ][As 2 Se 6 ] (TM ¼ Co (3), Ni (4)) were synthesized and characterized.…”

Review. Solvothermal Synthesis and Structure of Chalcogenidoarsenate Anions

“…A structure-directing influence of the incorporated metal atoms on both the nuclearity and connectivity pattern of the building units is often apparent in ternary thioarsenate(III) anions. For instance, the construction of the lamellar [48].…”

“…10), and the Mn(II) atoms exhibit a distorted trigonal bipyramidal coordination sphere. The ∞ [{Mn(terpy)} As 2 S 4 ] can be readily generated from such an arrangement with E = S by simple coordination of the remaining terminal S atoms at the vacant sites of the {Mn(terpy)} 2+ fragments [48].…”