Crystal chemistry of natural layered double hydroxides. 5. Single-crystal structure refinement of hydrotalcite, [Mg6Al2(OH)16](CO3)(H2O)4

Abstract

AbstractHydrotalcite, ideally [Mg6Al2(OH)16](CO3)(H2O)4, was studied in samples from Dypingdal, Snarum, Norway (3Rand 2H), Zelentsovskaya pit (2H) and Praskovie–Evgenievskaya pit (2H) (both Southern Urals, Russia), Talnakh, Siberia, Russia (3R), Khibiny, Kola, Russia (3R), and St. Lawrence, New York, USA (3Rand 2H). Two polytypes, 3Rand 2H(both ‘classical’), were confirmed on the basis of single-crystal and powder X-ray diffraction data. Their chemical composition was studied by electron-microprobe analysis, infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The crystal structure of hydrotalcite-3Rwas solved by direct methods in the space groupR$ {\bar 3} $mon three crystals (two data collections at 290 K and one at 120 K). The unit-cell parameters are as follows (290/290/120 K):a= 3.0728(9)/3.0626(3)/3.0617(4),c= 23.326(9)/23.313(3)/23.203(3) Å andV= 190.7(1)/189.37(4)/188.36(4) Å3. The crystal structures were refined on the basis of 304/150/101 reflections toR1= 0.075/0.041/0.038. Hydrotalcite-2Hcrystallises in theP63/mmcspace group; unit-cell parameters for two crystals are (data collection at 290 K and 93 K):a= 3.046(1)/3.0521(9),c= 15.447(6)/15.439(4) Å,V= 124.39(8)/124.55(8) Å3. The crystal structures were refined on the basis of 160/142 reflections toR1= 0.077/0.059. This paper reports the first single-crystal structure data on hydrotalcite. Hydrotalcite distribution in Nature, diagnostic features, polytypism, interlayer topology and localisation ofM2+–M3+cations within metal hydroxide layers are discussed.