Polytype diversity of hydrotalcite-like minerals is mainly a function of the nature of the interlayer anion. Among the varieties with CO32− anions, only two- and three-layer polylypes having the same structure as manasseite and hydrotalcite have been confirmed. Stichtite and reevesite, which have been previously identified as six-layer polytypes, are in fact three-layer polytypes.

Among SO42− varieties, one-layer and three-layer polytypes have been identified, but the one-layer types are only present in more hydrated minerals with larger interlayer spacings. The three-layer varieties are of three different polytypes, with both P- and O-types of interlayers. Both rhombohedral and hexagonal varieties exist. Interlayer type may change during hydration-dehydration or anion exchange. Thus, in contrast with the CO32−-bearing minerals, a complete description of the polytype of the SO42−-bearing minerals cannot be made by simply indicating the number of the brucite-like layers in the unit cell.

The two-layer unit cell seen in refined crystal structures of some minerals with SO42− interlayers is not due to a doubled periodicity of alternation of brucite-like layers but to periodicity of interlayer anions, or layer cations.

All possible polytypes of hydrotalcite-like minerals with a periodicity along the c axis of one-, two- and three-layers, as well as the simplest six-layer polytypes, were derived on the basis of the concept of closely packed brucite-like layers. Multilayer structures were found to be possible in several polytype modifications—three two-layer, nine three-layer, and a set of six-layer polytypes. The neighboring layers may be stacked in two different ways, building two kinds of interlayers: P-type where OH sheets lie one above another forming prisms and O-type where OH groups forms octahedra. Based on the kind of interlayer space, all polytypes may be separated into three groups: homogeneous interlayers of O-, or P-type, and alternating interlayers of both types. For the members of the first two groups, powder XRD patterns were calculated and criteria for distinguishing polytypes with the same number of layers per unit cell are suggested.

A comparative crystallochemical study was performed on natural and synthetic hydrotalcite-like compounds with similar compositions. The nature of the brucite-like sheet stacking was addressed by means of powder X-ray diffraction. From the resulting electron diffraction patterns it was possible to establish the order-disorder of the cations in the brucite-like sheet. The results show that a natural sample from Snarum is an intergrowth of hydrotalcite (3R1 polytype) and manasseite (2H1 polytype) at a ratio of 77:23 (wt.%). An aluminian serpentine is associated with the hydrotalcite and manasseite minerals. The structure of a synthetic sample, Mg:Al = 2:1, was determined as space group $R\overline{3}m$. For a few crystals in this sample, the octahedral cation distribution is compatible with the observed supercell (a = a′ √3). A second synthetic sample showed the presence of stacking faults and was described as a random layer sequence of two polytypes (3R and 2H).