Search USGS⌕ Search

USGS · 70018417

Crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O (X = P or As)

Abstract

The orthorhombic crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O for X = P and As have been determined with data collected at room temperature, and for X = P at –100 °C, using Mo-Kα radiation. For the latter the space group is Pna21, a= 21.670(11), b= 14.805(4), c= 20.393(5)Å and Z= 4. The structure consists of chains of α-Keggin-type molecules joined by W–O–links aligned in the a-axis direction. The Co/W occupancy at the link is disordered, with 61% Co on one side and 39% on the other. Further probable disorder, by lamellar merohedral twinning on (001) and by misorientation of the triethylammonium ions, has obscured the ethyl groups and the water molecules. In polarized light the crystals are deep wine-red normal to the chains (in the b direction), but nearly colourless in the a and c directions. The structure of the arsenate is similar to that of the phosphate.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

H. T. Evans, T.J.R. Weakley, G.B. Jameson. 1996. Crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O (X = P or As). https://doi.org/10.1039/dt9960002537

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related USGS reports

Polyoxometalates from heteropoly "brown" precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)W3IVW17VIO 62Hx]n-

Reduction of the α-Keggin anion [X n + O 4 W 12 O 36 ] [8 − n]− (X = H 2 2+ , B 3+ , Si 4+ ) by six electrons results in the known tungsten “brown” species [X n + O 4 (H 2 O) 3 W IV 3 W VI 9 O 33 ] [8 − n ]− in which three W atoms have been reduced from W VI to W IV , forming a metal–metal bonded triad. The W IV atoms have terminal water coordinated in place of terminal oxo groups. Additional tungstate can condense onto these water molecules in aqueous solution between pH = 4 and 6.5 to form the species reported here, [(XO 4 )W IV 3 W VI 17 O 62 H x ] y − . The boron derivative (X = B 3+ ) is more stable than the metatungstate (X = H 2 2+ ), both of which have been characterized by elemental analysis, 183 W NMR and X-ray crystal structure analysis. Eight additional tungstate groups condense in the form of a partial Keggin structure containing two triads and one dyad which is rotated 60° relative to a hypothetical α-isomer.

Journal of the Chemical Society, Dalton Transactio↗

X-ray crystallographic and tungsten-183 nuclear magnetic resonance structural studies of the [M4(H2O)2(XW9O34) 2]10- heteropolyanions (M = COII or Zn, X = P or As)

The crystal structures of K10[Co4(H2O)2(PW9O 34)2]??22H2O (1) and isomorphous K10[Zn4(H2O)2(AsW9O 34)2]??23H2O (2) have been determined {Mo-K?? radiation, space group P21/n, Z = 2; (1) a = 15.794(2), b = 21.360(2), c = 12.312(1) A??, ?? = 91.96??, R = 0.084 for 3 242 observed reflections [I ??? 3??(I)]; (2) a = 15.842(4), b = 21.327(5), c = 12.308(4) A??, ?? = 92.42(4)??, R = 0.066 for 4 675 observed reflections [F ??? 3??(F)]}. The anions have crystallographic symmetry 1 and non-crystallographic symmetry very close to 2/m (C2h). Each consists of two [XW9O34]9- moieties [??-B isomers; X = P (1) or As (2)] linked via four CoIIO6 or ZnO6 groups. Two Co or Zn atoms each carry a water ligand. The 183W n.m.r. spectra of the anions [Zn4(H2O)2(XW9O34) 2]10- (X = P or As) confirm that the anions retain 2/m symmetry in aqueous solution. Homonuclear coupling constants between 183W atoms are 5.8-9.0 Hz for adjacent WO6 octahedra sharing edges, and 19.6-25.0 Hz for octahedra sharing corners.

Journal of the Chemical Society, Dalton Transactio↗

Crystal structure of the heptamolybdate(VI)(paramolybdate) ion, [Mo7O24]6–, in the ammonium and potassium tetrahydrate salts

The crystal structures of the isomorphous salts M I 6 [Mo 7 O 24 ],4H 2 O (M = NH 4 or K) have been refined by three-dimensional X -ray diffraction methods. Unit cell dimensions of these monoclinic compounds, space group P 2 1 / C with Z = 4, are, ammonium salt: a = 8·3934 ± 0·0008, b = 36·1703 ± 0·0045, c = 10·4715 ± 0·0011 Å, β= 115·958°± 0·008°; and potassium salt: a = 8·15 ± 0·02, b = 35·68 ± 0·1, c = 10·30 ± 0·02 Å, β= 115·2°± 02°. By use of multiple Weissenberg patterns, 8197 intensity data (Mo- K α radiation) for the ammonium compound and 2178 (Cu- K α radiation) for the potassium compound were estimated visually and used to test and refine Lindqvist's proposed structure in the space group P 2 1 / c . Lindqvist's structure was confirmed and the full matrix least-squares isotropic refinement led to R 0·076 (ammonium) 0·120 (potassium), with direct unambiguous location of the cations and water molecules in the potassium compound.

Journal of the Chemical Society, Dalton Transactio↗