Christina Zitzer

1,4-Benzenedisulfonic acid (H2BDS) as terephthalic acid analogue for the preparation of coordination polymers: the examples of M(BDS)(NMP)3 (M = Mn, Fe, Co; NMP = N-methylpyrrolidone)

The solvothermal reactions of 1,4-benzenedisulfonic acid, H2BDS, with suitable salts of manganese, iron, and cobalt led to the new disulfonates M(BDS)(NMP)3 (M = Mn, Fe, Co), when N-methylpyrrolidone (NMP) was used as the solvent. The isotypic compounds crystallize with triclinic symmetry (P, Z = 2; M = Mn: a = 916.84(3) pm, b = 965.57(3) pm, c = 1437.87(5) pm, α = 95.297(2)°, β = 97.834(2)°, γ = 92.576(2)°, R1/wR2(I0 > 2σ(I0)) = 0.0300/0.0701; M = Fe: a = 911.98(5) pm, b = 960.75(5) pm, c = 1432.41(8) pm, α = 94.951(2)°, β = 98.050(3)°, γ = 92.029(2)°, R1/wR2(I0 > 2σ(I0)) = 0.0238/0.0689; M = Co: a = 911.3(1) pm, b = 959.5(1) pm, c = 1428.6(2) pm, α = 94.791(5)°, β = 98.229(5)°, γ = 91.873(6)°, R1/wR2(I0 > 2σ(I0)) = 0.0264/0.0684). In the crystal structure, the M2+ ions (Mn2+, Fe2+ and Co2+) are in octahedral oxygen coordination of three monodentate disulfonate groups and three NMP molecules. The disulfonate groups link the metal ions into infinite layers. Thermoanalytical investigations showed that the desolvation of the compounds occurred in a temperature range between 50 °C and 330 °C. The solvent free sulfonates showed remarkable high stabilities up to nearly 500 °C. The thermal behaviour was investigated by DSC/TG measurements and X-ray powder diffraction.

1,2,4,5-Benzenetetrasulfonic acid and 1,4-benzenedisulfonic acid as sulfo analogues of pyromellitic and terephthalic acids for building coordination polymers of manganese

The new polysulfonic acids H4B4S (1,2,4,5-benzenetetrasulfonic acid) and H2BDS (1,4-benzenedisulfonic acid) were used for the preparation of five manganese coordination polymers. The reactions of H4B4S and MnCO3 were performed in dimethylformamide (DMF) or N-methylpyrrolidone (NMP) as solvent in sealed glass ampoules at elevated temperatures. Two benzenetetrasulfonates could be obtained, [NH2(CH3)2]2{Mn(B4S)(DMF)2} (I) (P21/c, Z = 2, a = 942.02(5) pm, b = 1684.86(6) pm, c = 918.45(5) pm, β = 97.746(6)°, R1; wR2 (Io > 2σ(Io)) = 0.0357; 0.0771) and [HNMP]2{Mn(B4S)(NMP)2} (II) (P21/c, Z = 2, a = 931.7(1) pm, b = 1049.2(1) pm, c = 1944.9(1) pm, β = 113.529(3)°, R1; wR2 (Io > 2σ(Io)) = 0.0470; 0.0952). Both compounds exhibit anionic chains according to ∞1{Mn(B4S)2/2(L)2}2− (L = DMF, NMP). The Mn2+ ions are in octahedral coordination of oxygen atoms. The charge of the anionic chains is either compensated by dimethylammonium cations, [NH2(CH3)2+], or by protonated NMP molecules, HNMP+. Solvothermal reactions of H2BDS and MnCO3 in the solvents DMF, NMP and dimethylacetamide (DMA), respectively, yielded the disulfonates Mn(BDS)(DMF)2 (III) (P, Z = 1, a = 514.3(1) pm, b = 926.2(1) pm, c = 940.2(1) pm, α = 93.552(8)°, β = 99.993(7)°, γ = 99.237(7)°, R1; wR2 (Io > 2σ(Io)) = 0.0290; 0.0637), Mn(BDS)(DMA)2 (IV) (P, Z = 2, a = 936.00(4) pm, b = 984.94(4) pm, c = 1034.75(5) pm, α = 81.606(2)°, β = 88.941(2)°, γ = 82.364(2)°, R1; wR2 (Io > 2σ(Io)) = 0.0387; 0.1046) and Mn(BDS)(NMP)2 (V) (P, Z = 2, a = 962.97(3) pm, b = 976.76(3) pm, c = 1034.23(3) pm, α = 89.371(1)°, β = 78.839(1)°, γ = 87.604(2)°, R1; wR2 (Io > 2σ(Io)) = 0.0243; 0.0713). In the crystal structures of the three compounds, the octahedrally coordinated Mn2+ ions are linked by the disulfonate ions to layers according to ∞2{Mn(BDS)4/4(L)2} (L = DMF, DMA, NMP). The thermal analysis of all compounds shows that they can be desolvated completely and that the remaining solvent-free sulfonates exhibit decomposition temperatures up to 500 °C that is exceptionally high when compared to the respective carboxylates. Temperature-dependent magnetic susceptibility measurements of [NH2(CH3)2]2{Mn(B4S)(DMF)2} show paramagnetic behavior of the Mn2+ ions.

Crystal structure of iron(II)-benzenedisulfonate-triaqua-bis(Nmethylpyrrolidone), Fe(BDS)(H2O)3(NMP)2, C16H28FeN2O11S2

Abstract C16H28FeN2O11S2, monoclinic, Pc (no. 7), a = 14.6849(5) Å, b = 7.7856(2) Å, c = 20.1174(7) Å, β = 98.020(2)°, V = 2277.6 Å3, Z = 4, Rgt(F) = 0.0346, wRref(F2) = 0.0675, T = 120 K.