3 results
Crystal Structure of Tetramethylammonium-Exchanged Vermiculite
- A. Vahedi-Faridi, Stephen Guggenheim
-
- Journal:
- Clays and Clay Minerals / Volume 45 / Issue 6 / December 1997
- Published online by Cambridge University Press:
- 28 February 2024, pp. 859-866
-
- Article
- Export citation
-
Vermiculite crystals from Santa Olalla, Spain, were intercalated with tetramethylammonium (TMA) after Na saturation. The resulting TMA-vermiculite showed near perfect 3-dimensional stacking order with cell parameters of a = 5.353(1) Å, b = 9.273(2) Å, c = 13.616(6) Å, β = 97.68(3)°, and space group C2/m, which indicated a 1M polytype. Single crystal X-ray refinement (R = 0.073, wR = 0.082) located the central atom (N) of the TMA (occupancy at 0.418) and the C atom of 1 methyl group (occupancy at about 0.35). The TMA is offset from the center plane between 2 silicate layers by 1.52 Å, and the methyl group is keyed into the silicate ring of the adjacent silicate layer. This arrangement constrains the positions of the C atoms of the other methyl groups to an opposing plane parallel to the oxygen basal plane. Associated H2O is randomly located between the TMA pillars, and no scattering from these molecules was observed. The calculated height of the TMA molecule is shown to be 4.15 Å.
Steric and electrostatic arguments suggesting that adjacent TMA molecules must alternate apex directions (±c) allow for a description of the local TMA arrangement. This model involves the keying of TMA molecules laterally, thereby explaining why perfect 3-dimensional stacking occurs. The offset of TMA from the center of the interlayer region produces a cavity suitable as an adsorption site for small molecules, such as benzene, which is consistent with the higher than expected adsorption of these molecules in TMA-smectites of high layer charge. This offset also explains the easy expandability of TMA-clays, since only very weak interactions occur between TMA and 1 adjacent silicate layer, thereby allowing molecules to enter the interlayer.
Structural Study of Tetramethylphosphonium-Exchanged Vermiculite
- A. Vahedi-Faridi, Stephen Guggenheim
-
- Journal:
- Clays and Clay Minerals / Volume 47 / Issue 2 / April 1999
- Published online by Cambridge University Press:
- 28 February 2024, pp. 219-225
-
- Article
- Export citation
-
Vermiculite from Santa Olalla, Spain, was intercalated with tetramethylphosphonium [P(CH3)4+ = TMP], using a TMP-bromide solution at 70°C for three weeks. The resulting TMP-exchanged vermiculite, which contained a small (<5% of a site) amount of residual interlayer Ca, showed near perfect three-dimensional stacking. Cell parameters are a = 5.3492(8) Å, b = 9.266(2) Å, c = 14.505(6) Å, β = 97.08(2)°, space group is C2/m, and polytype is lM. Single-crystal X-ray refinement (R = 0.052, wR = 0.061) located two crystallographically unique sites for the phosphorus atoms (TMP molecule). The phosphorus atoms are occupied partially [P1 = 0.146(6), P2 = 0.098(5)] and are offset from the central plane of the interlayer by 1.23 Å to form two P-rich planes in the interlayer. Electrostatic interactions between the P cations and basal oxygen atoms essentially balance the negative charge associated with Al for Si substitutions in the tetrahedral sites. In addition, the orientations of the TMP molecules are probably different owing to packing constraints. The H2O site is located in the center of the interlayer, at the center of the silicate ring, and ∼3.09 Å from the Ca, which is also located on the central plane of the interlayer. Other H2O molecules are present in the interlayer, but could not be located by the diffraction experiment because they are randomly positioned in the interlayer. The tetrahedral rotation angle, α, is affected by the intercalation of TMP relative to tetramethylammonium (TMA), thus indicating that 2:1 layers are not simply rigid substrates, and that dynamic interactions occur during reactions involving adsorption and exchange.
Structural Study of Monomethylammonium and Dimethylammonium-Exchanged Vermiculites
- A. Vahedi-Faridi, Stephen Guggenheim
-
- Journal:
- Clays and Clay Minerals / Volume 47 / Issue 3 / June 1999
- Published online by Cambridge University Press:
- 28 February 2024, pp. 338-347
-
- Article
- Export citation
-
Vermiculite crystals from Santa Olalla, Spain, were first Na exchanged and then intercalated with monomethylammonium (= NH3(CH3)+, MMA) and dimethylammonium (= NH2(CH3)2+, DMA) molecules, respectively, by immersion in 1 M ammonium-chloride solutions at 65°C for 2–3 wk. MMA-and DMA-exchange with vermiculite resulted in crystals with near perfect three-dimensional stacking, suitable for single crystal X-ray diffraction analysis. Unit cell parameters are: a = 5.353(2) Å, b = 9.273(3) Å, c = 11.950(6) Å, and ß = 98.45(4)° for MMA-exchanged vermiculite and a = 5.351(2) Å, b = 9.268(4) Å, c = 12.423(8) Å, and ß = 98.33(5)° for DMA-exchanged vermiculite. Refinement results are R = 0.059 and wR = 0.073 (MMA-exchanged vermiculite) and R = 0.059 and wR = 0.064 (DMA-exchanged vermiculite). The results are based on structures which show substitutional disorder, and thus the presented models are derived from average structures.
There are two distinct sites for the MMA molecule in MMA-exchanged vermiculite. One crystallo-graphically unique MMA is oriented such that the N-C axis of the molecule is perpendicular to the basal oxygen plane, with the N ion offset from the center of the interlayer by 1.04 Å. The other MMA is located such that the N ion is at the center of the interlayer between adjacent 2:1 layers, presumably with the N-C axis of the molecule oriented parallel to the basal oxygen plane. This represents the first known occurrence of an organic molecule located exactly between the two adjacent 2:1 layers. Both sites are located between hexagonal cavities of adjacent layers. DMA molecules in DMA-exchanged vermiculite are located such that the N ion is offset from the central plane in the interlayer by 0.95 A. A static model is proposed with two orientations of DMA to produce a DMA “zigzag” orientation of molecules parallel to the (001) plane. The plane defined by the C-N-C atoms in the molecule is perpendicular to the (001) plane. An alternate model is more dynamic, and it involves the rotation of DMA molecules about one C-N axis.
Identical starting material was used in previous studies on tetramethylammonium (TMA)-exchanged vermiculite and tetramethylphosphonium (TMP)-exchanged vermiculite. The effect of onium-ion substitutions on the 2:1 layer shows that the tetrahedral rotation angle, α, is significantly smaller for MMA-and DMA-exchanged vermiculite vs. TMA and TMP-exchanged vermiculite. Tetrahedral and octahedral bond distances of the 2:1 layer of the TMA, TMP, MMA, and DMA-exchanged structures may be explained by the location of the organic cation relative to the basal oxygen atom plane and by the differences in the geometries of the organic molecule. Thus, the 2:1 layer is affected by the interlayer molecule, and the 2:1 layer is not a rigid substrate, but interacts significantly with the onium ions.