The syntheses, representative crystal structures, and some
properties of a new family of
microporous zincophosphate/arsenate materials, denoted
M3Zn4O(XO4)3·nH2O
(M = Li, Na,
K, Rb, Cs, ...; X = P, As; n = ∼3.5−6), are
reported. All these materials are based on a
flexible, anionic Zn4O(XO4)3
network built up from vertex-linked tetrahedral ZnO4 and
XO4
units. Four ZnO4 units share a vertex, resulting in
novel OZn4 centers. The use of mixed
four-coordinate anion types (XO4
3-,
O2-) results in a number of interesting structural
and
stability properties. The
M3Zn4O(XO4)3·nH2O
network contains only pairs of 3-rings (a spiro-5
unit) and 8-rings, and no 4-rings or 6-rings: it encloses roughly
spherical cavities connected
by a three-dimensional network of 8-ring channels propagating in the
orthogonal [100], [010],
and [001] directions (cubic unit-cell axes). Extraframework
cations and water molecules
occupy these cavities and channels. These phases display typical
“zeolitic” dehydration/rehydration and ion-exchange reactions with thermal stabilities up to
600 °C, the highest
known for this type of open-framework Zn(P/As)O material. The
included guest cation (Na,
Rb, K, Li, ...) has a crucial effect on crystal structure, by ordering
in and modifying the
configuration of the intercavity 8-ring channels. The crystal
structures of
Rb3Zn4O(PO4)3·3.5H2O,
K3Zn4O(AsO4)3·4H2O,
and
Na3Zn4O(PO4)3·6H2O
are presented. Crystal data: Rb3Zn4O(PO4)3·3.5H2O,
M
r = 881.40, cubic, space group
F4̄3c (No. 219), a =
15.3423(9) Å, V =
3611.4(6) Å3, Z = 8,
R
p = 5.12%, R
wp =
6.78%, 27 parameters, 1874 data points (X-ray Rietveld
refinement).
K3Zn4O(AsO4)3·4H2O,
M
r = 883.63, cubic, space group
F4̄3c (No. 219), a
=
15.4638(2) Å, V = 3697.9(2) Å3,
Z = 8, R
p = 8.69%,
R
wp = 11.42%, 24 parameters, 2124
data
points (X-ray Rietveld refinement).
Na3Zn4O(PO4)3·6H2O,
M
r = 739.49, trigonal, space
group
R3c (No. 161), a = 10.7489(3)
Å, α = 60.114(2)°, V = 880.4(4)
Å3, Z = 2, R = 2.49%,
R
w =
2.61%, 180 parameters, 846 observed reflections with I >
3σ(I) (single-crystal data).