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Langbeinites
Langbeinites are a family of crystalline substances based on the structure of langbeinite with general formula M2M'2(SO4)3, where M is a large univalent cation (such as potassium, rubidium, caesium, or ammonium), and M' is a small divalent cation (for example, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc or cadmium). The sulfate group, SO2−4, can be substituted by other tetrahedral anions with a double negative charge such as tetrafluoroberyllate (BeF2−4), selenate (SeO2−4), chromate (CrO2−4), molybdate (MoO2−4), or tungstates. Although monofluorophosphates are predicted, they have not been described. By redistributing charges other anions with the same shape such as phosphate also form langbeinite structures. In these the M' atom must have a greater charge to balance the extra three negative charges.
At higher temperatures the crystal structure is cubic P213. However, the crystal structure may change to lower symmetries at lower temperatures, for example, P21, P1, or P212121. Usually this temperature is well below room temperature, but in a few cases the substance must be heated to acquire the cubic structure.
The crystal structures of langbeinites consist of a network of oxygen vertex-connected tetrahedral polyanions (such as sulfate) and distorted metal ion-oxygen octahedra. The unit cell contains four formula units. In the cubic form the tetrahedral anions are slightly rotated from the main crystal axes. When cooled, this rotation disappears and the tetrahedra align, resulting in lower energy as well as lower crystal symmetry.
Sulfates include dithallium dicadmium sulfate, dirubidium dicadmium sulfate, dipotassium dicadmium sulfate, dithallium manganese sulfate, and dirubidium dicalcium trisulfate. Dipotassium dinickel sulfate can also be synthesized.
Selenates include diammonium dimanganese selenate. A diammonium dicadmium selenate langbeinite could not be crystallised from water, but a trihydrate exists.
Chromate based langbeinites include dicaesium dimanganese chromate.
Molybdates include Rb2Co2(MoO4)3. Potassium members are absent, as are zinc and copper containing solids, which all crystallize in different forms. Manganese, magnesium, cadmium and some nickel double molybdates exist as langbeinites.
Double tungstates of the form A2B2(WO4)3 are predicted to exist in the langbeinite form.
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Langbeinites
Langbeinites are a family of crystalline substances based on the structure of langbeinite with general formula M2M'2(SO4)3, where M is a large univalent cation (such as potassium, rubidium, caesium, or ammonium), and M' is a small divalent cation (for example, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc or cadmium). The sulfate group, SO2−4, can be substituted by other tetrahedral anions with a double negative charge such as tetrafluoroberyllate (BeF2−4), selenate (SeO2−4), chromate (CrO2−4), molybdate (MoO2−4), or tungstates. Although monofluorophosphates are predicted, they have not been described. By redistributing charges other anions with the same shape such as phosphate also form langbeinite structures. In these the M' atom must have a greater charge to balance the extra three negative charges.
At higher temperatures the crystal structure is cubic P213. However, the crystal structure may change to lower symmetries at lower temperatures, for example, P21, P1, or P212121. Usually this temperature is well below room temperature, but in a few cases the substance must be heated to acquire the cubic structure.
The crystal structures of langbeinites consist of a network of oxygen vertex-connected tetrahedral polyanions (such as sulfate) and distorted metal ion-oxygen octahedra. The unit cell contains four formula units. In the cubic form the tetrahedral anions are slightly rotated from the main crystal axes. When cooled, this rotation disappears and the tetrahedra align, resulting in lower energy as well as lower crystal symmetry.
Sulfates include dithallium dicadmium sulfate, dirubidium dicadmium sulfate, dipotassium dicadmium sulfate, dithallium manganese sulfate, and dirubidium dicalcium trisulfate. Dipotassium dinickel sulfate can also be synthesized.
Selenates include diammonium dimanganese selenate. A diammonium dicadmium selenate langbeinite could not be crystallised from water, but a trihydrate exists.
Chromate based langbeinites include dicaesium dimanganese chromate.
Molybdates include Rb2Co2(MoO4)3. Potassium members are absent, as are zinc and copper containing solids, which all crystallize in different forms. Manganese, magnesium, cadmium and some nickel double molybdates exist as langbeinites.
Double tungstates of the form A2B2(WO4)3 are predicted to exist in the langbeinite form.