Crystal Structure Investigation of Amide Sulfate Tetrahydrates with Divalent Cations

Author(s)
Ekkehart Tillmanns, Manfred Wildner, Paul Angerer
Abstract

Single crystals of three amide sulfate tetrahydrate compounds, Ca(NH2SO3)2 ⋅ 4H2O, Mn(NH2SO3)2 ⋅ 4H2O and Ni(NH2SO3)2 ⋅ 4H2O, were synthesized by controlled evaporation of aqueous Solutions. The crystal structures were investigated using single-crystal X-ray diffraction methods. Ca(NH2SO3)2 ⋅ 4H2O: space group C2/c, Z = 4, a = 11.616(3) Å, b = 7.761(2) Å, c = 11.638(3) Å, β = 98.93(1)°, V = 1036.47 Å3, R1 = 0.026; Mn(NH2SO3)2 ⋅ 4H2O: space group P21/c, Z = 2, a = 6.143(2) Å, b = 5.324(2) Å, c = 15.441(5) Å, β = 91.72(1)°, V= 504.78 Å3, R1 = 0.024; Ni(NH2SO3)2 ⋅ 4H2O: space group P1̅, Z= 1, a = 6.331(8) Å, b = 6.731(9) Å, c = 6.784(8) Å, α = 88.93(9)°, β = 67.87(5)°, γ = 67.76(6)°, V = 245.27 Å3, R1 = 0.030. In Ca(NH2SO3)2 ⋅ 4H2O antiprismatic CaO8 polyhedra share four oxygen atoms with NH2SO3 tetrahedra forming sheets parallel (001). In Mn(NH2SO3)2 ⋅ 4H2O and Ni(NH2SO3)2 ⋅ 4H2O, MnO6 octahedra and NiN2O4 octahedra, respectively, are linked by common corners with two NH2SO3 tetrahedra forming isolated groups.
These units are interconnected by hydrogen bonds only to form three-dimensional framework structures. The amide sulfate group has a distorted tetrahedral configuration with mean S−O and S−N bond lengths of 1.449 and 1.654 Å, respectively. The average cat-ion-oxygen distances are 2.456 Å (Ca−O), 2.173 Å (Mn-O), and 2.049 Å (Ni−O), both Ni−N bond lengths are 2.153 Å. Three different types of hydrogen bonds are observed in the title compounds, namely O−H⋅⋅⋅O bonds ranging from 2.680 to 2.968 A, N−H⋅⋅⋅O bonds between 2.966 and 3.339 Å, and one O−H⋅⋅⋅N bond with 2.905 Å. Generally, observed interatomic bond lengths and angles comply well with crystal Chemical expectations.

Organisation(s)
Department of Mineralogy and Crystallography
External organisation(s)
Kompetenzzentrum für elektrochemische Oberflächentechnologie GmbH
Journal
Croatica Chemica Acta
Volume
72
Pages
295-310
No. of pages
16
ISSN
0011-1643
Publication date
1999
Peer reviewed
Yes
Austrian Fields of Science 2012
105113 Crystallography
Portal url
https://ucrisportal.univie.ac.at/en/publications/crystal-structure-investigation-of-amide-sulfate-tetrahydrates-with-divalent-cations(ab1ae285-c00b-461f-9a9e-d842abc1f37e).html