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}. 425
J. CHEM. SOC., CHEM. COMMUN., 1995

A Novel Layered Aluminium Phosphate [Go(en)aAIsP+O16'3H2O] Assembled about a

Chiral Metal Complex
Keith Morgan,* Graeme Gainsford and Neil Milestone
lndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand

The synthesis and structure of a novel layered aluminium phosphate formed about a chiral metal complex is
reported.

The use of structure-directing organic molecules is a well- complex. Heating of the orange crystals at 400 'C for 2 h to
known stategy for synthesising materials such as zeolites and remove the ethylenediamine produced a deep blue compound.
microporous aluminium phosphates.l Although the pores Although visual examination showed that the crystal morpho-
formed must be large enough to accommodate the organic logy was retained, X-ray powder diffraction spectroscopy
molecule, it is not certain what other features the organic indicated that the compound was amorphous.
molecule should have to produce a particular structure-directing Several different layered aluminium phosphates have been
effect. We have recently become interested in the possibility of characterised by single crystal X-ray diffraction.LT The layers
using metal complexes as structure-directing species for the all have an identical composition (A13P4O163-), but a wide
formation of porous solids, since metal complexes could have a range of diverse structural topologies. Each aluminium is
number of unique structure-directing features. We report here tetrahedrally coordinated by four oxygens which are bonded to
the synthesis and characterisation by X-ray crystallography of a phosphorous. The phosphorous is also coordinated to four other
novel layered aluminium phosphate, formed about a cobalt(ut) oxygens in a tetrahedral configuration, but only three of the
trisethylenediamine ICo(en)33+] complex, in which the chirality oxygens are bonded to an aluminium. The fourth oxygen has no
of the complex has been imprinted onto the aluminium other bonding and is formally P=O. The most notable
phosphate layers. The interactions occurring between the cobalt differences between the various layered stmctures occur in the
complex and the aluminium phosphate layers suggest that the network of rings formed by the aluminium and phosphorous
structure-directing effects of the cobalt complex may result oxygen tetrahedra. Reported structures to date include mixtures
from hydrogen bonding interactions. of four- and six-,a four- and eight-,5 four- and twelve-,6 and
In metal complexes, the ligands are organised about the metal solely eight-membered rings.T
ion in a particular spatial configuration. This provides metal The structure reported here consists of three distinct four-
complexes with several unique features. They can -adopt membered rings and six distinct six-membered rings [Fig. 1(a)]
conformations that are difficult to obtain with organic mol- formed into a unique macroanionic sheet, intercalated with a
ecules, and their rigidity and flexibility are also different. In layer containing Co(en)33* cations and water molecules. The
addition, the wide range of oxidation states that metal ions can four-membered rings have a particularly unusual configuration.
achieve give complexes properties not found in orgariic They form a tricyclic structural motif which is similar to a
molecules. If any of these features are important in influencing [3.3.3]propellane [Fig. 1(b)]. This motif is chiral as it has a
the structure-directing properties of a molecular species then distinci twist in one direction. Each of the chirai forms of this
microporous solids formed from metal complexes could have motif is repeated along one direction in the aluminium
unusual structural architecfures. phosphate layers. Between these motifs are two similar
If metal complexes are to be used as templates in the asymmetric six-membered rings below which sits the Co(en)33*
synthesis of microporous zeolites and aluminium phosphates complex in the interlayer space [Fig. 1(c)]. The layer below the
then these complexes must be stable under the reaction interlayer space is related to that above by a twofold screw axis.
conditions. This excludes the use of a wide variety of metal Thus above and below the Co(en)33* complex are the same two
complexes where the ligand can exchange readily. If ligand six-membered rings facing in opposite directions. The
exchange does occur then insoluble metal silicates and Co(en)33* compiex therefore sits inside a chiral pocket. This
phosphates will form under normal reaction conditions. chiral pocket may simply have formed as a distortion of the
A number of metal complexes containing macrocyclic lattice to accommodate the chiral complex' This, however,
ligands are stable to ligand exchange. Balkus er a/. used this appears unlikely as the propellane motifs have to remain chiral
property to assemble zeolites with the faujasite structure about biiause of steric factors even in the absence of the complex.
metal complexes.2 However, not all possible sites in the Also, none of the other types of layer topologies reported to
structure were occupied by the metal complex. Some metal date, all of which have been synthesised using non-chiral
complexes, where the metal is in a specific oxidation state, are templates, show similar chiral pockets. We think that the layer
inert and ligand exchange will be ffiibited. Cobalt in the +3 topotogy of the AIPO reported here will only form in the
oxidation state is a well-known example, and CoItr complexes p.b.".ri. of a chiral temptate.
could be useful as sffucture-directing species in a zeolite or Overall, the crystal structure of this layered aluminium
AIPOa synthesis. phosphate is not chiral since there are equal numbers of chiral
The layered aluminium phosphate reported here was syn- pockits of opposite handedness, containing the other enan-
thesised hydrothermally at 150
oC over 1-2 days, using an iiomer of the complex. Although most of the zeolites and
aqueous mixture of Co(en)3:+ as the hydroxide, aluminium microporous AIPO+ contain asymmetric units, none of these
oxyhydroxide (pseudoboehmite, 0.5 B) and 857o phosphoric excepi zeolite-B have chiral pockets and none to date have been
acid (1.9 g). Tlie aqueous Co(en)3:* hydroxide was isolated by syntiesised in a pure chiral form. Zeolite-B is a highly
filtering off the silver salts formed by the reaction of Co(en)3C13 intergrown hybrid of two distinct stmctures, the so-called
(1.5 e) with AezO (2 g) in water (12 ml) at 90'C for 15 min. polymorphs A and B. The A polymorph is chiral,8'e and can
The major synthetic product formed was orange needles, exiit in eithe. u left-hand or right-hand form. Davis and Lobor0
characterised by single crystal X-ray crystallography.f Small suggest that enantiomerically enriched zeolites and micro-
amounts of berlinite and bright blue concretions were also poious solids may only be synthesised with a chiral template'
produced during the reaction. The latter component was They base this ionclusion, in part, on the preparation of a
identified by X-ray powder diffraction as being isomorphic to zeolite-B phase which had some enantiomeric selectivity as a
nickel hydrogen phosphate hydrate.3 It is therefore probably catalysis.rt They therefore assumed that the zeolite-P phase was
cobalt phosphate, formed by decomposition of the metal enriched in one of the enantiomeric forms of the A polymorph.
426 J. CHEM. SOC., CHEM' COMMUN', 1995

The structure reported here also provides evidence that chiral

molecules can induce chiral features in a lattice, and that
suitable chiral templates could form chiral zeolites and
aluminium phosphates.
There is^ext&sive hydrogen bonding between the amine
groups of the cobalt complex, the interlayer rv-ater and the
IO3u".nt P=O groups JFig. 1(c)1. Typical. (N)-H"'O:(P)
diitances are 1.852.b2.4.. ttre hydrogen bonding appears to be
the dominant interaction binding the layers together' Minimiza-
tion of the elecffostatic energy through hydrogen bonding
interactions is probably important in determining the layer
topology. Thus ihere is probably a direct relationship between
the aningement of the hydrogen bonding grouls. on the metal
complex-and the layer topology. It has recently been foundl2
that the formation oi t r"sopo.ous materials by assembly in acid
media about surfactant-based structures is similarly mediated
by hydrogen bonding from halides to protonated silanols' The
in the layered aluminium
-of that layers
resulis o6tained here suggest
phosphates, the growth the may primarily be
determined by hydrogen bonding interactions between groups
on the template and the oxygens of the phosphates'

Received, 2 I st November 1994 ; Com. 4107 l06l

Footnote
i Crl'sra1 dLlt(.t fot Co(en);Ai,.PrOro 3HlO: orthorhombic' Pna21' a =
r'
8.5lir5r. D = 1i.775(51. c = 11.59-l(8) A. Z = 4.p = l'9tt g cm
Number of retlections collected n'cre 1989, at 130 K' on a Nicolct P'l
diiTractorneter using \{o-Kcr radiation (}' = 0.71073. graphite rnono-
chrornltol. Structuie was solved b1' a direct method (SHELXS-86) using
empirical-absorption corrccted data. and anisotropic temperature factors tbr
were
the Co. P and AI atoms. The h1-drogen atoms in calculated positions
kept in riding mode rvith two common isotropic temperatrrre tlctors' The
strucrure g'as retined to a conventional R of 0'062' Atomic coordinates'
bond Lengths and angles. and thermal parameters have been deposited at the
Cambridge Cnstall,cgraphic Data Centre. See Information fbr Authors'
issue \0. l.

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