Supramolecular confinement of C60, S8, P4Se3 and toluene by metal(II) macrocyclic complexes

Article abstract of DOI:10.1039/a903669e

Treatment of S₈ or P₄Se₃ with {5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulenato}metal(II) [= M(TMTAA)] in carbon disulfide afforded the solid state 1:2 inclusion complexes [(S₈){M(TMTAA)}₂], M = Ni or Cu (isostructural), or [(P₄Se₃){Ni(TMTAA)}₂]. A toluene inclusion complex [(MeC₆H₅)Ni(TMTAA)] resulted from the recrystallisation of [Ni(TMTAA)] from toluene. Recrystallisation of [Ni(TMTAA)] from CS₂-hexane resulted in the unsolvated complex. All complexes are comprised of interlocking dimers of the macrocycle, and in the inclusion complexes these dimers act as homotopic divergent receptors either through the methyl- or phenyl-lined surfaces. Solid state 1:1 C₆₀ inclusion complexes of [M(TMTAA)], M = Cu or Zn, have individual macrocycle molecules acting as heterotopic divergent receptors.

Full text of DOI:10.1039/a903669e

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Supramolecular confinement of C60, S8, P4Se3 and toluene by
metal(II) macrocyclic complexes
Philip C. Andrews,a Jerry L. Atwood,b Leonard J. Barbour,b Paul D. Croucher,a
Peter J. Nichols,a Naomi O. Smith,a Brian W. Skelton,c Allan H. Whitec and Colin L. Raston*a
a Department of Chemistry, Monash University, Clayton, Melbourne, Victoria 3168, Australia
b Department of Chemistry, University of Missouri - Columbia, Columbia, Missouri 65211,
USA
c Department of Chemistry, University of Western Australia, Nedlands,
Western Australia 6907, Australia
Received 7th May 1999, Accepted 7th July 1999
Treatment of S8 or P4Se3 with {5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulenato}metal()
[᎐ M(TMTAA)] in carbon disulfide afforded the solid state 1:2 inclusion complexes [(S ){M(TMTAA)} ], M = Ni
᎐
8
2
or Cu (isostructural), or [(P4Se3){Ni(TMTAA)}2]. A toluene inclusion complex [(MeC6H5)Ni(TMTAA)] resulted
from the recrystallisation of [Ni(TMTAA)] from toluene. Recrystallisation of [Ni(TMTAA)] from CS2–hexane
resulted in the unsolvated complex. All complexes are comprised of interlocking dimers of the macrocycle, and in
the inclusion complexes these dimers act as homotopic divergent receptors either through the methyl- or phenyl-lined
surfaces. Solid state 1:1 C60 inclusion complexes of [M(TMTAA)], M = Cu or Zn, have individual macrocycle
molecules acting as heterotopic divergent receptors.
light the adaptability of [Ni(TMTAA)] in self dimerisation in
the confinement of globular molecules involving inherently
weak interactions, as well as the confinement of a planar mole-
Introduction
Non-planar metal macrocycles based on arrays of unsaturated
units for which there are many1 have the potential to
cule. The only other related studies of P4E3 species are the
associate via weak intermolecular forces with molecules
formation of [Ni(P4E3){N(CH2CH2PPh2Ϫ2)3}] (E = S10 or
(or ions), especially if the interacting surfaces have curv-
Se11) where the nickel() centre is attached strongly to the
ature complementarity. A readily available macrocycle formed
unique P of the cage. Other attempts to complex this cage
from condensation of 1,2-diaminobenzene with acetylacetone
resulted in cluster fragmentation.12 We also report the prepar-
in the presence of nickel() acetate, notably {5,7,12,14-tetra-
ation and structures of the supramolecular complexes [(C60)-
methyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulenato}nickel()
M(TMTAA)], M = Cu or Zn, and [(S8){Cu(TMTAA)}2] which
[Ni(TMTAA)], falls into this category. It adopts a rigid saddle
are isostructural with the nickel() analogues, as well as the
shape2,3 due to the otherwise unfavourable non-bonding inter-
actions between the hydrogen atoms on methyl groups and the
o-hydrogen atoms on the aromatic rings, and potentially can act
preparation and structure determination of unsolvated weakly
associated, dimeric [Zn(TMTAA)].
as a divergent heterotopic receptor. Nickel can be removed from
the macrocycle and be replaced by many other metal ions.3
We recently established the ability of [Ni(TMTAA)] to
bind a range of disparate globular molecules in two ways. First,
as a divergent receptor with C60 in a 1:1 complex where there is
a fullerene cage perched in each cavity in an infinite zigzag
array.2 Secondly, for the smaller globular molecules 1,2-dicar-
Results and discussion
P4Se3 and S8 complexes
Slow evaporation of CS2–hexane solutions of the macrocyclic
complex with P4Se3 or S8 gave the discrete crystalline 1:2
complexes [(P4Se3){Ni(TMTAA)}2] and [(S8){Ni(TMTAA)}2]
respectively, eqn. (1). The 1:2 complex is favoured even for an
excess of the cage, and indeed these conditions are best for
badodecaborane(12) (᎐ o-C B H ) and the phosphorus sulfide,
᎐
2
10 12
P4S3, the macrocycle self associates through aromatic faces into
dimers. These dimers now act as divergent homotopic receptors,
the complexes having a 1:2 ratio of guest to host species.2 Other
studies have demonstrated the ability of C60 and o-C2B10H12 to
bind to cyclotriveratrylene which is also a rigid non-planar
molecule, albeit bowl shaped4–7 in contrast to the saddle
structure of [Ni(TMTAA)]. Similarly bowl shaped calix[5]arene
forms complexes with the same cage molecules.8,9 The complex
of [Ni(TMTAA)] with P4S3 is the only authenticated inclusion
complex of a Group 15 chalcogenide cage species.
We now report new findings on the supramolecular/host–
guest chemistry of the nickel() macrocycle, notably: (i) the
heavier Group 15 chalcogenide P4Se3 forms a 1:2 inclusion
complex with [Ni(TMTAA)]; (ii) S8 also gives a 1:2 inclusion
complex; (iii) unsolvated [Ni(TMTAA)] as well as a toluene
inclusion complex of [Ni(TMTAA)] exist in the solid state with
a different extended motif based on macrocyclic dimers associ-
ated through methyl-lined faces. These findings further high-
J. Chem. Soc., Dalton Trans., 1999, 2927–2932
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group P21/c, and therefore is not isomorphous with [(P4S3)-
{Ni(TMTAA)}2], although it exhibits the same structural motif
with two supermolecules of {Ni(TMTAA)}2, locked through
their pendant aromatic rings, associated with an S8 molecule,
Fig. 1. There are no inter-S8 contacts and unlike the structures
of the P4Se3 and P4S3 complexes there is no disorder. The closest
sulfur to metal centre distances are 3.32 and 3.52 Å to the
separate [Ni(TMTAA)] molecules respectively. The next nearest
sulfur atom is 4.04 Å from the first [Ni(TMTAA)] molecule.
Methyl hydrogen distances on these two [Ni(TMTAA)] mole-
cules range from 2.76 to 3.67 Å for the sulfur atoms in the
S8 ring. Three other [Ni(TMTAA)] molecules have hydrogen
atoms within 3.6 Å of sulfur atoms, two with phenyl hydrogens
closest at 3.11 and 3.21 Å and the third with a methyl hydrogen
at 3.21 Å.
The complex [(S8){Cu(TMTAA)}2] crystallised in an iso-
structural form to [(S8){Ni(TMTAA)}2] described above. The S8
again lies in the phenyl-lined cavities of two [Cu(TMTAA)]
molecules and the closest sulfur to metal centre distances are
3.34 and 3.50 Å to the separate [Cu(TMTAA)] molecules. The
Cu atoms are displaced by 0.03 Å from the N4 plane towards
the phenyl-lined surface.
Unsolvated [M(TMTAA)] (M = Ni or Zn) and the toluene
solvate of [Ni(TMTAA)]
The complex [Ni(TMTAA)] can be crystallised from CHCl3
as discrete monomeric units.13 Another report14 gives
[Ni(TMTAA)] isomorphous with [Cu(TMTAA)]15 where the
macrocyclic complex self-associates through the methyl-lined
surfaces as well as through the aromatic faces, as described
in the S8 and P4Se3 inclusion complexes above. The com-
plex [Zn(TMTAA)] crystallises as dimers from toluene in the
space group P21/c isomorphous to the [Ni(TMTAA)]14 and
[Cu(TMTAA)]15
Fig. 1 Projection of the supramolecular interplay found in (a) [(P4Se3)-
{Ni(TMTAA)}2] and (b) [(S8){Ni(TMTAA)}2].
dimers. It was prepared as a hydrolytically
unstable complex from the reaction of diethylzinc with the
metal free macrocycle, [H2TMTAA], in toluene under dry,
anaerobic conditions, eqn. (2).
driving the precipitation of the complex from solution, the
complex being more soluble than [Ni(TMTAA)] itself.
Similarly, [(S8){Cu(TMTAA)}2] crystallised from CS2–hexane
solutions containing an excess of S8 over [Cu(TMTAA)].
The complex [(P4Se3){Ni(TMTAA)}2] crystallises in the
space group Pnma and is isomorphous with the P4S3 analogue.2
Supermolecules of {Ni(TMTAA)}2 are locked through their
pendant aromatic rings. The P4Se3 cages are cradled within the
methyl-lined faces of two supermolecules in a bent arrange-
ment, with additional contacts to hydrogen atoms of other
[Ni(TMTAA)] dimers, which also involve weak intermolecular
forces, Fig. 1. The formation of dimers of the macrocycle is
driven by the complementarity of curvature of the two com-
ponents, as well as by nickel–π-arene interactions (see below).
There are no inter-cage contacts and P4Se3 is disordered over
two sites related by a mirror plane perpendicular to the crystal-
lographic mirror plane passing through Se–P–Se. At 173 K
P4Se3 is apparently disordered over the two sites in a 75:25
ratio but was difficult to resolve. At 123 K the disorder was
at a 90:10 ratio and refined giving the major component well
resolved and yielding meaningful contact distances. The major
site has the same orientation as the major component of P4S3 in
[(P4S3){Ni(TMTAA)}2].2
In the dominant orientation a selenium atom and the
unique phosphorus are closest to the metal centre of one
[Ni(TMTAA)] molecule at 3.26 and 3.72 Å respectively. A
phosphorus in the P3 ring of P4Se3 is 3.18 Å from the metal
centre in the second [Ni(TMTAA)] molecule. The other two
phosphorus atoms of the P3 ring are 2.97 and 3.02 Å from a
methyl hydrogen of this second [Ni(TMTAA)]. The third and
fourth [Ni(TMTAA)] molecules have closest contacts at 3.49
(phosphorus in P3 ring to phenyl hydrogen) and 3.22 Å (one of
the two adjacent selenium atoms to phenyl hydrogen).
Red crystals of [{Zn(TMTAA)}2] were deposited from tolu-
ene solutions and in the solid state the complex forms discrete
dimers with zinc atom A situated over the pentanediiminato
ring and displaced 0.32 Å out of the N4 plane toward the
phenyl-lined surface, Fig. 2. Zinc atom B is situated over a
phenyl group of the other Zn(TMTAA) molecule and is dis-
placed 0.20 Å again towards the phenyl-lined surface. The
dimer has the same arrangement as for {Ni(TMTAA)}2
dimers in the P4Se3 and S8 complexes described above. The
structure extends into columns of [{Zn(TMTAA)}2] dimers
through the interlocking of the methyl-lined surfaces. One
interaction consists of a symmetrical overlay of the pentane-
diiminato rings over the ZnN4 plane with the central CH
immediately above zinc atom A (of a dimer as described above).
The other interaction consists of an offset of the methyl-lined
surfaces related to the ZnN4 plane such that a methyl hydrogen
lies above zinc atom B and the central CH.
A third form of [Ni(TMTAA)] can be crystallised from
methanol or CS2–hexane, Fig. 3. The asymmetric unit consists
of two molecules of [Ni(TMTAA)] arranged such that one of
the phenyl rings of one molecule points into the phenyl-lined
face of the other in a pseudo host–guest relationship. One of
the meta aromatic hydrogen atoms of the “guest” molecule
The complex [(S8){Ni(TMTAA)}2] crystallises in the space
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Fig. 4 Projection of the supramolecular interplay found in [(MeC6H5)-
Ni(TMTAA)].
Fig. 2 Intramolecular interactions in [{Zn(TMTAA)}2].
sheets of the pentanediimine wrapped dimers. These sheets in
turn stack together in an alternating fashion so that the gross
dimples in each sheet are complemented by those in alternating
sheets. Although many points of van der Waals contact are
made between molecules in alternating sheets, they do not
appear significant in this context.
The complex [Ni(TMTAA)] crystallised from toluene
produces the toluene inclusion complex containing two
[Ni(TMTAA)] molecules associated through the methyl lined
surfaces, Fig. 4. Toluene molecules are perched in the exposed
phenyl lined cavity of the [{Ni(TMTAA)}2] dimer with closest
approaches being for one hydrogen atom, ortho to the methyl
group of toluene, at 3.21 (to nickel atom), 3.11 (to nitrogen) and
3.11 Å (to phenyl carbon bound to nitrogen, the centre of the
C ؒ ؒ ؒ N bond being 3.03 Å from the hydrogen atom). One
methyl hydrogen atom of the toluene is 3.81, 3.51 and 3.11 Å
from the nickel atom and the nitrogen and carbon atoms
diagonally opposed to the above nitrogen/carbon pair respect-
ively. Toluene has hydrogen–carbon distances of less than 3.5 Å
to two other [Ni(TMTAA)] molecules which comprise the
walls of the channel within the extended structure. Within the
channel toluene molecules are almost coplanar and alternate in
methyl group orientation but are offset. Closest approaches are
for hydrogen–hydrogen at 2.82 Å and carbon–carbon at 3.39 Å.
Fig.
3
Projection of the supramolecular interplay found in
[Ni(TMTAA)].
makes close contact with the “host” nickel atom (H ؒ ؒ ؒ Ni 2.92
Å) while the other is nearest one of the nitrogen atoms
(H ؒ ؒ ؒ N, 3.43 Å). The closest contact between the molecules,
however, is between one of the pentanediimine methyl
groups of the “guest” and the meta aromatic carbon atoms
of the “host” (CH3 ؒ ؒ ؒ C 2.86, 3.04; CH3 ؒ ؒ ؒ C 3.41, 3.55 Å).
To maximise this interaction the phenyl of the “host” is tilted
3.05Њ toward the “guest” methyl. These units stack together
through an interlocking of the methyl-lined surfaces of each
[Ni(TMTAA)] molecule. The molecules are slightly offset with
the central hydrogen in the pentanediimine group making
closest contact to the nickel atom at 3.06 Å. This interaction is
within the extremes of the two similar interlocks described for
[{Zn(TMTAA)}2] above. The “host–guest” and dimer inter-
actions for [Ni(TMTAA)] form the basis of two dimensional
C60 Complexes
The complexes [(C60)M(TMTAA)] (M = Ni, Cu or Zn) form
on mixing [M(TMTAA)] and C60 solutions (toluene– or CS2–
hexane) with either equimolar or up to 2:1 equivalent ratios of
reagents, eqn. (3).
CS2–hexane
(3)
[M(TMTAA)] ϩ C60
[(C60)M(TMTAA)]
or toluene–hexane
The complex [(C60)Cu(TMTAA)] crystallises from CS2–
hexane in the monoclinic space group P21/n, isostructural to
the previously reported [(C60)Ni(TMTAA)]2 and [(C70)-
J. Chem. Soc., Dalton Trans., 1999, 2927–2932
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Table 1 Intramolecular contacts for [{M(TMTAA)}2] (phenyl-lined
surface/methyl-lined surface linkage) in [M(TMTAA)] and its inclusion
complexes
Metal–phenyl
centroid
distance/Å
(M ؒ ؒ ؒ C
Metal–imine
geometric centre
distance/Å
(M ؒ ؒ ؒ C
Complex
range/Å)
range/Å)
[(o-C2B10H12){Ni(TMTAA)}2]2
[(P4S3){Ni(TMTAA)}2]2
[(P4Se3){Ni(TMTAA)}2]
[(S8){Ni(TMTAA)}2]
[(S8){Cu(TMTAA)}2]
[{Zn(TMTAA)}2]
3.55 (3.78–3.85) 3.66 (3.84–3.85)
3.51 (3.73–3.85) 3.60 (3.76–3.77)
3.51 (3.76–3.82) 3.62 (3.75–3.79)
3.40 (3.69–3.89) 3.52 (3.59–3.74)
3.37 (3.55–3.75) 3.36 (3.41–3.60)
3.26 (3.45–3.60) 2.71 (2.62–3.08)
3.49 (3.67–3.83) 3.29 (3.23–3.53)
[{Cu(TMTAA)}2]15
Table 2 Intramolecular contacts for [{M(TMTAA)}2] (methyl-lined
surface/methyl-lined surface linkage) in [M(TMTAA)] and its inclusion
complexes
Metal–imine
geometric
centre
M ؒ ؒ ؒ C
Complex
distance/Å
distance/Å
Fig. 5 The C60 interactions with Cu(TMTAA) in [(C60)Cu(TMTAA)].
[(MeC6H5)Ni(TMTAA)]
[{Ni(TMTAA)}2]
3.71
3.83
4.93, 5.06
4.17
4.31
3.76
4.31
3.46–4.05
3.57–4.36
4.37–6.01
3.98–4.63
3.91–5.17
3.54–4.18
3.91–5.17
Ni(OMTAA)]16 (OMTAA = 2,3,6,8,11,12,15,17-octamethyl-
dibenzo[b,i]-1,4,8,11-tetraaza[14]annulene). The structure con-
sists of sheets of C60 (five close C60 geometric centre to centre
distances at 9.96–10.08 Å and a sixth fullerene at 12.82 Å)
isolated by layers of Cu(TMTAA) such that each C60 molecule
lies in a phenyl-lined surface of one Cu(TMTAA) and a methyl-
lined surface of another Cu(TMTAA) molecule with a third
Cu(TMTAA) molecule interacting through a smaller surface
defined by a phenyl and two methyl groups, Fig. 5. The closest
contacts between C60 and the copper centres are at 3.18 and
3.37 Å for the phenyl- and methyl-lined surfaces respectively.
The Cu atoms are displaced from the N4 plane of the macro-
cycle by 0.04 Å towards the phenyl-lined surface (cf. displace-
ment in [{Cu(TMTAA)}2],15 0.069 and 0.071 Å towards the
phenyl-lined surface).
The complex [Zn(TMTAA)] also reacts with C60 and
although suitable single crystals of [(C60)Zn(TMTAA)] could
not be obtained the powder diffraction pattern indicated a
material isomorphous with [(C60)Ni(TMTAA)]2 and [(C60)-
Cu(TMTAA)].
Bond distances and angles within the macrocycles in the
present study are unexceptional,2,3 as for the bond distances and
angles in the P4Se3 cage11,17 and S8.18
[{Zn(TMTAA)}2] (offset)
[{Zn(TMTAA)}2]
[{Cu(TMTAA)}2]15 (offset)
[{Cu(TMTAA)}2]15
[{Fe(TMTAA)}2]19
In [(MeC6H5)Ni(TMTAA)] and [{Ni(TMTAA)}2] described
above the interplay of the macrocycles is different to that of
the foregoing complexes, now with the methyl-lined faces
locked together. This association is also evident in the structure
of unsolvated [Zn(TMTAA)] and [Cu(TMTAA)].15 Here there
is greater variation in packing with the “symmetrical” arrange-
ment placing the metal closest to the pentanediimine geometric
centre, Table 2. The arrangement occurs for [(MeC6H5)Ni-
(TMTAA)], [Zn(TMTAA)] and [Cu(TMTAA)].15 A slight
offset occurs in [Ni(TMTAA)] and a greater mismatch is seen
in [Zn(TMTAA)], [Cu(TMTAA)]15 and [Fe(TMTAA)].20
The opposite interaction of the macrocycles to above
(methyl-lined surface linkage) occurs in [{Fe(TMTAA)}2]20
whereby the phenyl-lined surfaces are locked together. The
iron–phenyl centroid contact distance is 3.58 Å with two
carbon atoms at 2.98 and 3.21 Å from the Fe and the other
phenyl carbon atoms span out to 4.55 Å.
The complexes [M(TMTAA)] are rigid, remarkably adapt-
able macrocycles, able to accommodate molecules of different
size and shape, either as discrete macrocycles or associated
dimers of the macrocycles. As evident in the structures of
unsolvated [Ni(TMTAA)],11 [Cu(TMTAA)],12 [Zn(TMTAA)]
and [Fe(TMTAA)]20 the macrocyclic complexes associate
through both the phenyl- and methyl-lined surfaces. In the
presence of toluene the association through the phenyl-lined
surface is broken in preference for incorporation of toluene into
the structure. The globular molecules o-carborane,2 P4S3,2 P4Se3
and S8 compete for the methyl-lined surface leaving the phenyl-
Solution studies
We have evidence (uv-vis spectra) for a strong interaction
between [Ni(OMTAA)] and C60 in toluene solution19 however
[Ni(TMTAA)], [Zn(TMTAA)] and [Cu(TMTAA)] interactions
with C60 have proved difficult to study due to stability and
solubility problems. The other ligands do not appear to bind
strongly in solution (uv-vis studies).
Conclusion
2
The extended structures for the inclusion complexes differ with
P4Se3 or S8 units being situated in isolated pockets and toluene
molecules occupying channels. The self assembly of two
M(TMTAA) moieties at 90Њ to each other is common as in the
Ni(TMTAA) supermolecules containing o-dicarborane, P4S3,
P4Se3 and S8 guests, [(S8){Cu(TMTAA)}2] and also with the
structures of [Zn(TMTAA)] and [Cu(TMTAA)].15 The M2ϩ ion
of one macrocycle sits below a phenyl ring of the other macro-
cycle common for all seven compounds, Table 1.
lined surface association intact; C60 effectively competes for
both the methyl-lined surface (as a globular molecule) as well as
for the phenyl-lined surface (as an aromatic guest).
Experimental
All solvents and starting materials were obtained from Aldrich
and used without further purification. X-ray powder diffrac-
tions patterns were collected on a Scintag PADV, with a
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J. Chem. Soc., Dalton Trans., 1999, 2927–2932

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Table 3 Crystal data and details of the data collection and structure refinement for [(S8){Ni(TMTAA)}2] 1, [(S8){Cu(TMTAA)}2] 2, [(P4Se3){Ni-
(TMTAA)}2] 3, [{Ni(TMTAA)}2] 4, [(MeC6H5)Ni(TMTAA)] 5, [{Zn(TMTAA)}2] 6 and [(C60)Cu(TMTAA)] 7
1
2
3
4
5
6
7
Formula
Collection
C44H44N8Ni2S8
123
C44H44Cu2N8S8
123
C44H44N8Ni2P4Se3
123
C22H22N4Ni
123
C29H30N4Ni
173
C44H44N8Zn2
298
C82H22CuN4
123
temperature/K
M
1058.77
1068.46
1163.06
401.15
493.28
815.7
1126.65
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
Monoclinic
P21/c (no. 14)
18.0406(6)
13.8560(2)
18.1661(6)
Monoclinic
P21/c (no. 14)
18.1070(6)
13.8843(3)
18.0489(5)
Orthorhombic
Pnma (no. 62)
19.0407(8)
17.3568(8)
13.5731(4)
Monoclinic
P21/c (no. 14)
15.9494(8)
14.9208(8)
15.6235(7)
Triclinic
P1 (no. 2)
Monoclinic
P21/c (no. 14)
14.107(6)
16.371(8)
16.670(1)
Monoclinic
P21/n (no. 14)
14.5538(6)
17.5225(8)
18.3011(7)
¯
10.4126(5)
13.3634(7)
17.5322(9)
92.595(1)
90.591(1)
101.863(1)
2384.5(2)
1.374
4
8.39
14446
10009
97.2162(5)
96.791(1)
91.070(3)
99.94(3)
107.8447(9)
γ/Њ
V/Å3
4505.0(0.2)
1.561
4
12.51
11252
4925
4496.0(0.2)
1.575
4
13.59
12943
4621
4485.7(6)
1.722
4
34.61
5602
2521
0.062
0.060
3717.4(3)
1.434
8
10.58
18550
4286
3792(3)
1.429
4
4442.6(3)
1.68
4
Dc/g cmϪ3
Z
µ/cmϪ1
13.1
5.6
Unique reflections
No. observed data
R
RЈ
6662
4047
0.041
0.049
11332
2698
0.111
0.104
0.060
0.054
0.080
0.073
0.092
0.162
0.0900
0.2204
Complexes 1, 2, 3, 4 and 7: Enraf-Nonius KappaCCD diffractometer, crystal mounted in oil; no absorption correction, Mo-Kα radiation, I > 3σ(I),
refined on F. Complex 5: Siemens SMART CCD, crystal mounted in oil; no absorption correction, Mo-Kα radiation, I > 2σ(I), refined on F.
Complex 6: Cad4 single counter diffractometer, crystal mounted in a Lindemann capillary; absorption correction applied, Mo-Kα radiation,
I > 3σ(I), refined on F.
germanium solid state detector. Elemental analyses were
performed by Chemical and Micro Analytical Services. The
complexes [M(TMTAA)], M = Ni or Cu, and H2TMTAA were
prepared according to published procedures.15,21
was removed and the filtrate left to crystallise. Satisfactory
microanalyses could not be obtained for this complex, however
infrared, uv-visible and mass spectra were consistent with the
given formulation. X-Ray powder diffraction indicated a
compound isomorphous with [(C60){Ni(TMTAA)}].
Syntheses
[(C60){Cu(TMTAA)}]. Carbon disulfide solutions (50 ml
each) containing C60 (100 mg, 0.14 mmol) and [Cu(TMTAA)]
(62 mg, 0.15 mmol) were mixed and allowed to evaporate
slowly. The complex precipitated and was collected and washed
with toluene then hexane. Yield: 0.130 mg, 80%. Mp decomp.
>400 ЊC. Found (calc.): C, 87.13 (87.42); H, 1.74 (1.97); N, 4.97
(4.80)%.
[(S8){M(TMTAA)}2] and [(P4Se3){Ni(TMTAA)}2]. Carbon
disulfide solutions (10 ml each) containing S8 (10 mg, 0.10
mmol) or P4Se3 (18 mg, 0.05 mmol) and [Ni(TMTAA)] (50 mg,
0.10 mmol) were mixed and allowed to evaporate slowly.
The complex precipitated and was collected and washed with
toluene then hexane. A CS2 solution (10 ml) of [Cu(TMTAA)]
(25 mg, 0.06 mmol) was added to a CS2 solution (10 ml) of S8
(32 mg, 0.125 mmol), stirred and layered with an equal volume
of hexane. On standing and partial evaporation dark crystals
formed. [(S8){Ni(TMTAA)}2]: mp decomp. >220–221 ЊC.
Found (calc.): C, 50.30 (49.92); H, 3.81 (4.19); N, 10.83
(10.58)%. [(S8){Cu(TMTAA)}2]: we were unable to separ-
ate this compound from coprecipitated S8. [(P4Se3){Ni-
(TMTAA)}2]: mp decomp. >240 ЊC. Found (calc.): C, 44.98
(45.44); H, 3.82 (3.81); N, 9.82 (10.10)%.
Crystallography
Crystallographic data given in Table 3.
CCDC reference number 186/1563.
See http://www.rsc.org/suppdata/dt/1999/2927/ for crystallo-
graphic files in .cif format.
Acknowledgements
[{Ni(TMTAA)}2] and [(MeC6H5)Ni(TMTAA)]. The complex
[Ni(TMTAA)] was recrystallised from CS2–hexane or toluene
respectively. [{Ni(TMTAA)}2]: we were unable to separate the
compound from the coprecipitated solvated species
[(CS2)Ni(TMTAA)].22 [(MeC6H5)Ni(TMTAA)]: mp 278.5–
279.5 ЊC. Found (calc.): C, 71.05 (70.61); H, 6.41 (6.13); N,
11.85 (11.36)%.
The authors thank R. Mackie (Department of Physics, Monash
University, Clayton) for collection of the X-ray powder diffrac-
tion patterns. This work was supported by the Australian
Research Council and the National Research Foundation.
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