165

Chapter 9

Nets with higher connectivity than four

Nets with higher connectivity than four are not so common, possibly since there
are no obvious commercially available organic building blocks that can be used.
This one of the reason often cited for turning to coordination chemistry when it
comes to network building. The number of coordination geometries is much
extended compared to carbon, and for example six-connected nodes are readily
available. The problem is, however, that the commonly used coordination
polymer linkers such as 4,4'-bipyridine are sterically demanding and it is
difficult to fit six of these around a small transition metal ion as Fe 3+.
In Chapter 5 we saw the important class of compounds based on the six-
connected pcu (primitive cubic packing, or a-Polonium) net, and we also
encountered the five-connected bnn or boron nitride net. In this chapter we will
explore higher connectivities further, starting with the five-connected and six
connected nets and then going on to the mixed 3;5, 3;6, 4;5 4:6 and 5;6 nets. We
will also briefly look at some seven and eight connected nets.
Wells did not treat the higher connected nets in as much detail as the others in
his books, [1-3] so our major source of data for the nets in this chapter is the
RCSR database [4]. There is also a website dedicated to six-connected nets [5].

9.1. Five connected nets

9.1.1. The 44. 66-sqp net

This net is based on square planar pyramidal nodes and is less common than
the bnn net (section 5.2.7) based on nodes with trigonal bipyramidal
coordination. This is likely an effect of the fact that the trigonal bipyramid is
slightly energetically favoured over the square planar pyramid in VSEPR
(valence shell electron pair repulsion) theory [6].
The sqp net has vertex symbol 4"4"4"4"6'6"65"65"65"65 and genus 4, see Figure
9.1. (For comparison the bnn net has vertex symbol 4.4.4.4.4.4.6.6.6.*.)
166 L. (~rstrim & K. Larsson

Figure 9.1 The sqp net is based on nodes with square planar pyramidal geometries.

This net can be found in the compounds M2(C3H204)2(H20)2(pt2-

hexamethylenetetramine)] (M=Zn(II), Cu(II)), see Figure 9.2 [7].

o o
Zn Zn OA >O
~.¢~ o~ ~o
O O O
\/ r-,"-~ \/O
H20--Zn--N ~1...__-N - - Z n - - OH2
o / \ ' " " o,'o

Figure 9.2 The sqp net can be found in the compounds M2(C;H204)2(H20)2(la2-
hexamethylenetetramine)] (M=Zn(II), Cu(II)) [7].

9.1.2. The 44. 66-nov net

The nov net has vertex symbol 4'4"4"4"6"6"63"65"65"65 and genus 4, see Figure
9.3.
9. Nets with higher connectivity than four 167

~ Z

Figure 9.3 The nov net also has approximately square pyramidal nodes.

This net can be found in the compound [Cu2(2,5-

dimethylpyrazine)(N(CN)2)4], see Figure 9.4 [8]. This compound exhibits
antiferromagnetic order below 5K.

/Cu

Cu

Figure 9.4 The nov net can be found doubly interpenetrated in the compound [Cu2(2,5-
dimethylpyrazine )(N( CN )a)4] [8].
A large number of other five-connected nets have been described (the RCSR
lists 184 uninodal five-connected nets) but only a handful of other molecule
based nets are known [9]. We will just pick one of these 184 and show in the
next section.
168 L. (~rstrOrz & K. Larsson

9.1.3. The 46.64-beu-I net

The beu-1 net has vertex symbol 4"4"4"4"6"6"6"6"62"62 and genus 37, see Figure
9.5. You may see that it is based on the so called body centred cubic packing,
that is a cube with one atom in the centre and one in each comer. It is nicely
describe as an infinite polyehdron (Figure 9.5 right).

<z
m

Figure 9.5 The beu-1 net has vertex symbol 4.4.4,4,6.6,6-6.62.6 z and genus 37.

9.1.4. The 34.42.84-cab net and other five-connected nets with cubic symmetry

Wells lists a number of five-connected nets with cubic symmetry with cubic
symmetry, the cab, peu-i and ubt nets [1]. They all contain three-rings (vertex
symbols 3.3.3.3.4.4.8.8.8.8, 3.4.4.4.4.4.8.8.8.8, 3.3.4.4.6.6.6.6.6.6, genus 10, 37,
19 respectively), however we do not know of any molecular based examples of
these nets. The cab net is illustrated in Figure 9.6.

Figure 9.6 The cab net. A five-connected net with cubic symmetry
9. Nets with higher connectivity than four 169

9.2. Six-connected nets

There are two basic geometries for six-connected nodes; octahedral and
trigonal prismatic, one or both may be present in these nets. We encountered
octahedral nodes in the pcu-net in Chapter 5, now we will look at some other
nets.

9.2.1. The NiAs or the (412)(49.66)-nia net

This is the net formed by the nickel and arsenic atoms in NiAs (a classical
inorganic "type structure" [ 10]) at it is shown in Figure 9.7. The vertex symbols
are 4,4,4,4.4.4.4,4.4.4.4,4,*,*.* and 4"4"4"4"4"4"42"42"42"64"64"64"64"64"64and the
genus is 9. Note that half of the six-connected nodes are not octahedral but have
a trigonal prismatic geometry.
This means that ordinary transition metal complexes will not normally adopt
this geometry since their six-coordinated geometries are almost exclusively
octahedral. However, the ions of the rare-earth metals are larger and have often
higher coordination numbers and for example with eight coordination it is
normal that six of the ligands are arranged in a trigonal prismatic geometry.

Figure 9.7. The NiAs or nia net. Note that half of the six-connected nodes have a trigonal
prismatic geometry,and thus not octahedral.
This is exactly what was found in praseodymium hexacyanoferrate(III)
tetrahydrate, see Figure 9.8 [11].
170 L, ~rstrim & K, Larsson

PF
PrN /
N N

Pr ~ N~ Cl~--'Fe.,,rt#C..~_.N____pr

/
Pr ~,..I
I
N~Pr?,,-~'~. OH2
I N"N
N

Figure 9.8 The NiAs or nia net in praseodymium hexacyanoferrate(III) tetrahydrate [11]. White
nodes are eight coordinated praseodymium ions where the cyanide ligands adopt a trigonal
prismatic geometry. Grey nodes are octahedral Fe(llI) nodes.

9.2.2. The 48.54.6Cbsn net

T h e b s n net f r o m one angle looks exactly like the p e u net, h o w e v e r , v i e w e d

at 90 ° w e can clearly see that it is twisted (Figure 9.9). It has v e r t e x s y m b o l
4"4"4"4"4"4"4'4"53"53"53"53"*'*'* and g e n u s 5.
F

Figure 9.9 The bsn net from one angle look very much like the peu-net, but in this view it is
evident that they are different!
This net c a n be f o u n d d o u b l y interpenetrated in [ C d ( b i p h e n y l - 4 , 4 ' -
dicarboxylate)(1,2-bis(4-pyridyl)ethane)(H20)], prepared via a hydrothermal
route, [12] see Figure 9.10.
9. Nets with higher connectivity than four 171

Cd ~0.: ~ 0 .
i

Figure 9.10 The bsn net can be found doubly interpenetrated in [Cd(biphenyl-4,4'-dicarboxylate)
(1,2-Bis(4-pyridyl)ethane)(H20)] [ 12]. Nodes are placed at the centre of the Cd204C2 units.

9.2.3. The 49. 6~-acs net

The aes net is a way to connect nodes with trigonal prismatic geometry, see
Figure 9.11. It has vertex symbol 4"4"4"4"4'4"42"42'42"64"64"64"64"64'64 and genus
5.

Figure 9.11. The aes net is a way to connect nodes with trigonal prismatic geometry.

This net was recently found in [Fe30(1,4-benzenedicarboxylate)3(DMF)3]

[FeC14].3DMF (see Figure 9.11) and also in [Fe30(1,3-benzenedicarboxylate)3
(pyridine)3].0.5pyridine 1.5H20 [ 13 ]. There are also other recent reports of this
172 L. ~rstron & K. Larsson

net [14,15]. Interestingly, the very similar building blocks in [V30(H20))(1,3-

benzenedicarboxylate)3]C1,.9H20 instead give the pcu net, [16] see discussion
in ref. 13.

Figure 9.11 The aes net was recemly found in [Fe30(1,4-benzenedicarboxylate)3(DMF)3]

[FeCI4].3DMF (this picture) and also in [Fe30(1,3-benzenedicarboxylate)3(pyridine)3]0.5pyridine
1.5H20 [13].

9.2.4. The 4~.53. 64-stun net

The stun net has vertex symbols 4'4"4-4-4-4-4-4-52-52-55-64'64-*-* and genus

13, see Figure 9.12.
X

Figure 9.12. The stun net.

9. Nets with higher connectivity than four 173

An example is found as the copper dimer net in [Cu2(isonicotinato)3]"

(I52/312)H20, see Figure 9.13. Note that this compound, obtained under
hydrothermal conditions, also contain a polyiodide network [17].

Cu.
N"'%. Ii "~ ~ ..Cu
N

o,-c,i cu.w6
~N~ \~ N
0 ..,~0

o ik J o" ,
I
Cu

Figure 9.13 The stun net can be found in a copper dimer net (nodes in the middle of the mixed
square-planar/square-pyramidal binnclear units) in [Cn2(isonicotinato)3]-(Is-2/312)'H20, Note that
this compund contain a polyiodide network in the channels [17].

9.3. S e v e n - c o n n e c t e d nets

The RCSR currently contains some 75 uninodal seven-connected nets, but

only two contain four-membered rings, s v n and wfq, the remaining having
three-membered rings as shortest circuits. In general, we get closer and closer to
close packing as we draw more and more lines, so that the links between the
nodes need to be long if we should consider the structure as 3D-net.
Chemical considerations also move us away from the transition metals, at
least if we consider building coordination networks where the nodes are single
metal ions, since they are too small to accommodate sufficient number of
ligands. However, there is clearly a possibility to have cluster compounds as
nodes with higher connectivity, although at present we know of no such
examples.

9.3. I. The 416.54.62-wfq net

We have found only one example of molecule based seven-connected nets

and it seems to contain the wfq net. This net is shown in its ideal form in Figure
9.14, it is based on body centred cubic packing, but with one link missing,
making the nodes seven-connected. It has vertex symbol
4"4"4"4"4"4"4"4"4"4"4"43"43"43'43"5"5"53"53'*'* and genus 21.
174 L. ~rstrim & K. Larsson

Figure 9.14. The wfq seven-connected net.

The example o f this net is found in the eight coordinated compound [La(2,2'-
bipyridine-N,N'-dioxide)a](BPh4)(CIO4)2.2.75MeOH, [ 18] see Figure 9.15.

La La

Figure 9.15 The wfq net is found in the eight coordinated compound [La(2,2'-bipyridine-N,N'-
dioxide)4](BPh4)(C104)2.2.75MeOH [18]. Note that one pair of N-oxide bipy ligands binds to the
same lanthanum ions making the nodes seven-connecting.

9.4. Eight-connected nets

Eight connected nets are extremely rare, but strategies to synthesis them have
evolved the last years, so that we now know o f a handful o f examples [18-21].
9. Nets with higher connectivity than four 175

9.4.1. The CsCl or 424.64-bcu net

First we will consider the net based on the body centred cubic structure, or, as
it is also known, the CsC1 structure, giving the beu net, see Figure 9.16.

Figure 9.16 The body centred cubic structure, or, as it is also known, the CsC1 structure, is the
or[gine of the beu net.

Interestingly, our example of the ben net is taken from the same publications
as the seven-connected wfq net, and it contains the same ligands but other
counter ions, the formula being [La(2,2'-bipyridine-N,N'-dioxide)a](CF3S03)3.
4.2MeOH, [18] see Figure 9.17.

La - - 0 • N~.,lt~ ~"'f~ N N " ~~ ~,,N'o " ~ "~

La/0 ,, T.,.~

Figure 9.17 [La(2,2'-bipyridine-N,N'-dioxide)4](CF3SO3)3-4.2MeOH, [18] contains the bcu net

(compare Figure 9.15).

9.4.2. A 33.415.58.62 net

A 334155862 net was recent found by the same group. Using different reaction
conditions (slow diffusion crystal growth) but identical ligands the compound
176 L, ~rstrim & K, Larsson

[La(2,2'-bipyridine-N,N'-dioxide)4](C104)3 was obtained and its 3D nets

analysed, see Figure 9.18 [ 19]. As the nets become quite complicated with these
high connectivities it may be some advantage to view them as "combinations o f
interconnected layered 2-D sheets or subnet tectons" [22].
La La
\ f
ONe
~'~X ~.~,~,O ~

NO..~_ ~).....~ ~,:,..,N . N,O---....La

L, o o ,- ;Y'x\ ,~ \\/)~/1F,\//XX ',\//V/li\V/~'
'N~oI#- 4~o~N ~,,.~ ~ \ V / A l l }xX/A\ &\//All/3,V/
N ~ "N"" Og"L8"~0"*"N"'~'~

O O
i.~/ La

Figure 9.18 Using different reaction conditions (slow diffusion crystal growth) but identical
ligands as in Figure 9.17 the compound [La(2,2'-bipyridine-N,N'-dioxide)4](C104)~containing a
334155s62net was recent found by the same group [19].

9.5. Nets with three- and five-connected nodes

This is another unusual way to build 3D-nets, although one o f the members o f
this class is the very symmetric net built by stacked hexagonal layers.

9.5.1. The stacked hexagonal layer net, or (63)(69. 8)-hms net

The h m s net has vertex symbols 6.6.6.62.62.62.62.62.62.*, 63.63.63 and genus 3,

see Figure 9.19.

xJ
Figure 9.19 The hms net built by stacked hexagonal layers.
9. Nets with higher connectivity than four 177

We can find this net in a few compounds, [23,24] among them

Ag(tricyanomethanide)(4,4'-bipyridine) where it is doubly imerpenetrated, [24]
see Figure 9.20.

J N -'~

Figure 9.20 The hms net can be found doubly interpenetrated in Ag(tr[cyanomethanide)(4,4'-
bipyridine) [24].

9. 5.2. The graphite or (6~)(69. 8)-gra net

Closely related to the hms net is the graphite or gra net. In this net the
hexagonal layers are no longer stacked on top of each other, but are eclipsed,
see Figure 9.21. The vertex symbols are identical, but the genus is 5. We know
of no examples of a molecular variation of this net, and this may be due to the
different arrangement of the voids in the two structures, the nice channels that
can harbor a second net within the hms net (all known hms nets are
interpenetrated) are clearly blocked in the gra net.

Figure 9.21 The gra net, compareto the hms net in Figure 9.19.
178 L. ~rstrim & K. Larsson

9.5.3. The (4. 82) (4. 56. 6. 8e)-mcf-d net

Another net for which we lack examples, but that seem relevant, is the mcf-d
net, see Figure 9.22. This net has vertex symbols 4.5.5.5.5.52.52.8.8.*, 4.83.83
and genus 5. Note that this net has not alternating nodes of different
connectivity, thus making a coordination polymer with nodes based on metal
coordination and p.3-1igands less likely to adopt this net.

Figure 9.22 The mcf-d net.

9.6. Nets with three- and six-connected nodes

This is a more common class of nets, and it includes a net that may be
familiar from your undergraduate studies, the rutile net.

9.6.1. The rutile or (4.62)(42.6:°.8~)-rtl net

The name of this net come from the Latin word, "rutilus" meaning reddish,
and that is often the colour of the TiO2 mineral where the arrangement of Ti and
O atoms form the rtl net, see Figure 9.23. This net has vertex symbols
4.4.6.6.6-6-6-6-6-6-62-62-*-*-*, 4-62-62 and genus 7. Note that the stoichiometry is
ntrigonal/rloctahedra] = 2.
9. Nets with higher connectivity than four 179

Figure 9.23 The rutile or rtl net.

The rtl net can be found in [Zn(1,3,5-
benzenetricarboxylate)]NH2(CH3)2.DMF prepared by solvothermal methods,
see Figure 9.24. The DMF molecules can be removed by heating and vacuum
without breaking the framework [25]. Note that the net stoichiometry is
maintained since each six-connected node needs two Zn(lI) ions, thus giving the
correct node ratio 2/1.
o o

o,,.(~
o
o¢.o
o b,,,W 0 }n'''°
o

,o "r"

0 O"0~0 0 0
Figure 9.24 [Zn(1,3,5-benzenetricarboxylate)]NH2(CH3)2.DMFcontain the ruffle or rtl net. The
DMF molecules can be removed by heating and vacuum without breaking the framework [25].
Grey and white circles in the left pictm-eindicatethe nodes used in the rtl net to the right.

9.6.2. The pyrite or (63)(6~2.83)-pyr net

Another of the "inorganic type structures" has given name to the pyrite (FeS2)
or p y r net, see Figure 9.25. This net has vertex symbols
6.6.6.6.6.6.62.62.62.62.62.62.*.*.*, 63.63.63 and genus 13.
180 L. ~rstrim & K. Larsson

Figure 9.25 The pyrite or pyr net.

An example of the p y r net can be found as the two nets in [Zn40(4,4,'4"-
nitrilotrisbenzoate)2].N,N'-diethylformamide.EtOH, see Figure 9.26 [26,27].
This doubly interpenetrated structure absorbs hydrogen (1.9 wt % at 77 K and 1
atm) remains crystalline even at 400 °C and 10 -5 Torr, and the ligands undergo
reversible dynamics, mainly rotational motion, in response to removal and
rebinding of the guest molecules. Figure 9.27 shows all atoms (except
hydrogens) for the two nets and the channel structure is readily seen.
R

0-# Z.r.,,.. Zn-O

Zn~..0 HOyR 0 0tZn

Zn"~O~ N~"~O*"Zn

Figure 9.26 The pyr net can be found doubly interpenetrated in [Zn40(4,4,'4"-
nitrilotrisbenzoate)2]. N,N'-diethylformamide.EtOH, see also Figure 9.27 [26,27].
9. Nets with higher connectivity than four 181

Figure 9.27 All atoms (except hydrogens) for the two interpenetrated pyr nets (see Figure 9.26) in
[Zn40(4,4,'4"-nitrilotrisbenzoate)2]-N,N'-diethylformamide.EtOH [26,27]. The channels are
approximately 4 A wide.

6.2.1. The five nodal qom net containing only six-rings

The qom net was recently demonstrated in [Zn40(1,3,5-
benzenetribenzoate)2]. 15N, N-diethylformamide.3H20 containing the familiar
Zn40-core coordinating six carboxylates. This compound has a record surface
area estimated at 4,500 mZg-1 [28].
The qom net has genus 25 but as the net has five nodes the vertex symbols
become quite cumbersome and we will not cite them here. The net is shown in
Figure 9.28 and a comparison between the p y r and the q o m net is shown in
Figure 9.29.

Figure 9.28 The five-nodal qom net found in [Zn40(1,3,5-benzenetribenzoate)2].15(N,N-

diethylformamide).3(H20) [28].
182 L. ~rstrOrz & K. Larsson

F¢

Figure 9.29 The difference between the pyr net (left, six-connected nodes have cubic close
packing) and the qom net (right, having hexagonal close packing between the six-connected
nodes).

We will consider one more net of this class since it is important to see how
trigonal prismatic nodes can connect to trigonal nodes (the RCSR lists another
seven three- and six-connected nets).

9.6.3. The (4.62)(42.61°.82)-sit net

The sit net has vertex symbols 4-4-6-6-6-6-6-6-6-6-62-62-8-8-86, 4-62-62 and

genus 4, see Figure 9.30.
Y

Figure 9.30 The sit net connects trigonal prismatic nodes to trigonal nodes.

We know of no examples of this net and will therefore move on to the four-
and six-connected nets.
9. Nets with higher connectivity than four 183

9.7. Nets with four- and six-connected nodes

Although rare in the field of molecular based nets, we will also in this class
have well known "inorganic type structures". We have, moreover, four basic
geometries to chose from: square planar, tetrahedral, octahedral and trigonal
prismatic. We thus in principal need to consider at least four different
subclasses of nets in this section. Moreover, as with all nets of this type, there is
also the stoichiometry between the nodes to consider.
However, as the examples are very scarce we will restrict this section to a few
selected cases, all based on more or less distorted tetrahedral and octahedral
nodes.

9.7.1. Tetrahedrons and octahedrons; the corundum or (43.63)3(46.69)2-cor net

In the cortmdum (A1203) o r eor net the stoichiometry is ntetrahedral/noetahedrat =

3/2, vertex symbols 4.4.4.4.4.4.6r62.6r6r63.63.*.*.*, 4.4.42.64.62.62 and genus
4. In Figure 9.31 we can see that the node geometries are not perfect tetrahedra
and octahedra.

z Y

Figure 9.31 The e o r or corundum net. It is evident that the node geometries are not perfect
tetmhedra an octahedra.

The eor net was found in the compound formulated as [Zn(3,3',5,5'-

tetrakis(4-pyridyl)bimesityl)t.5](C104)2.nH20, see Figure 9.32 [29]. Note the
alternative formulation assigning the tetrakis(4-pyridyl)bimesityl as a pair of
three-connected nodes [29].
184 L, ~lrstrOn & K, Larsson

N N
\/
¶ N_
N~Zn~N
/\
N
< _

Figure 9.32 The eor net was recently found in [Zn(3,3',5,5'-tetrakis(4-pyridyl)bimesityl)l.s ]

(C104)2-nH20 [29]. White and grey circles to the left correpspond to nodes in the net to the right,

9. Z 2. Square planar and octahedral nodes, the (44.62)(4s. 67)-fsg net

The fsg net has vertex symbols 4.4.4.4.4.4.4.4.6.6.6.6.*.*.*, 4.4.4.4.62.* and

genus 4, see Figure 9.33. In its ideal form it has the same packing of the nodes
as the primitive cubic packing (ot-Po), pea net but with two links removed per
node in every second layer. Note the different stoichiometry (1:1) of this net.

Figure 9.33 The fsg net has in its ideal form the same node packing as the primitive cubic
packing, peu net (ct-Po) but with two links removed per node in every second layer.

We have no examples of this net, but if we take the peu net and remove links
in a slightly different way we will get a related net prepared not so long ago by
Batten, Murray and co-workers.
9. Nets with higher connectivity than four 185

9. 7. 3. Tetr ahedrons and octahedrons, another (44. 62) (48. 6~.8) net

The compound in question, [Mn2(dicyanamide)3(NO3)(methylpyrazine)2],

forms the net shown in Figure 9.34 [30]. This net has vertex symbols
4.4.4.4.4.4.4.4.62.62.62.62.*.*.*, 4.4.4.4.62.62 and is thus clearly topologically
different from the fsg net. It was noted that the introduction of a methyl group
on the pyrazine ring induced a shift in 3D-net from the pcu-net (~x-polonium)
of the [Mn(dicyanamide)z(pyrazine)] compounds [30].

Figure 9.34 The doubly interpenetratednet in [Mn2(dicyanamide)3(NO3)(methyl-pyrazine)2][30].

The dieyanmnideligands are all bridging and only one net is shown. This net has short symbols
(44.62)(48.66.8)just as the fgs net.
It is worth noting that there are several more ways in which links may be
removed from the pcu net to give new four- and six-connected nets.

9. 7. 4. Tetr ahedrons and octahedrons ; the (43. 6 s) (46. 66. 83) -fsh net

The fsh net has vertex symbols 4.4.4.4.4.4.6r62.6r6r62.6r *. *. *,

4.62.4.62.4.62 and genus 5, see Figure 9.35.
This net can be found doubly interpenetrated in [Cd2(SO4)2(1,2-bis(4-
pyridyl)ethane,)3(H20)zT].4.5H20, see Figure 9.36 [31 ].

9.8. Nets with four- and eight-connected nodes

9. 8.1. The fluorite or flu net

The fluorite (CaF2) or flu net is illustrated in Figure 9.36. It is built from
perfect tetrahedra and cubes and has genus 6.
This net was deliberately prepared from tetrakis(4-carboxyphenyl)methane
and Cd(NO3)2"4H20 by hydrothermal synthesis to give [Cd4(tetrakis(4-
carboxyphenyl)methane)2(DMF)4]-4DMF-4H20, see Figure 9.37 [32].
186 L. 4lrstrim & K. Larsson

Yz
L~

Figure 9.35 The fsh net.

©
H20.~ ,..-OH2
H201 da~OH2

o ~ o ..-

.~ -.~,

-'"N...~0
Figure 9.36 doubly interpenetrated in [Cdz(SO4)2(1,2-bis(4-pyridyl)ethane,)3(H20)2.7]-4.5HzO.
The structure contains three different Cd(II) ions, one is a six-connected node, another the four-
connected node and the third is just bridging [31].
9, Nets with higher connectivity than four 187

Figure 9.37 The four- and eight-cormeeted fluorite (CaF2) or flu net is built from perfect
tetrahedra and cubes.

Cd.0 0~Cd
Cd.o~' ~ ~'~0 ~cd

dd ~d

Figure 9.38 [Cd4(tetmkis(4-carboxyphenyl)methane)2(DMF)4]-4DMF.4H20 contains the flu

net [32]. Upper left shows the ligm~d structure, bottom left show the Cd4-eluster giving the eight-
connected nodes.

9.9. Summary of higher connected nets

T h e table on the next p a g e c o n c l u d e s this chapter.

188 L. ~ r s t r i m & K. Larsson

Table 9.1 Summary of the four-connected nets discussed in this chapter and in chapter 5
Net Vertex Symbol Short Symbol Connect Nodes"
sqp 4"4"4"4"6'6'6f6f @65 44,6~ 5 Sqpy
nov 4"4"4"4"6'6'63'6s'65'65 44.66 5 Trbp
beu-I 4"4"4'4'6'6'6'6"62'62 46.64 5 Trbp
cab 3"3"3"3'4'4'8'8'8"8 34.42.84 5 Sqpy
nia 4"4"4"4"4"4"4"4"4"4"4"4"*'*'* 41:,6 s 6 Oct+Trpr
4"4"4"4"4'4'42'42'42'6a'6a'6a'64"64"64 4966
bsn 4"4"4"4'4'4'4'4"53'53"53"53"*'*'* 4s.54.63 6 Oct
aes 4"4"4"4"4"4"4z'4z'42"64"64"6¢64"64"64 49.66 6 Trpr
stun 4"4"4"4'4'4'4'4"52'52"55"64"6¢*'* 4s.53.64 6
wfq 42"4"42'4~'4'42"42"42"4"42"4"4"42"42"4' 415.55.62 7
64"64'64'66'66'66
beu 4"4"4"4"4'4 '4'4'4"4"4"4"43"43"43"43"43" 424.64 8 Cub
43-43'43'43'4~'43-43"*'*'*'*
3"3'3'4'4'4'4'4'4"42"42"42"42"42"42"42" 334155862 8 Cub
42.42.5.5.5.5.5L 5L52.52.*.*
hms 6-6.6.62.6z.6a.62.62-62-*,63-63-63 (63)(69.8) 3;5 l'rig--l'rbp
gra 6"6'6'62'62'62'62'62-6r *, 63"63"63 (63)(69.8) 3:5 Trig+Trbp
mef-d 4-5.5.5.5.52.52.8.8.*, 4-83-83 (4.82)(4.56.6.82) 3;5 Trig+Trbp

rtl 4.4.6.6.6.6.6.6.6.6.62.6r*.*-*, 4.62.62 (4.62)(42.6l°.83) 3;6 Oct+Trig

pyr 6.6.6.6.6.6.62.62.62.62.62.62.*.*.*, (63)(612.83) 3;6 Oct+Trig
63"63"63
qom five-nodal, see appendix see appendix 3;6
sit 4-4.6.6.6.6.6.6.6.6-62-62-8-8-86,4-62-62 (4.62)(42.6t°.83) 3;6 l'rig+Trpr
eor 4-4"4"4"4"4"62"62"62"6r63-63-*-*-*,4.4.42. (43.63)(46.69) 4;6 Tetr+Oct
64-62"62
fsg 4-4.4.4.4.4.4.4.6.6-6-6-*.*-*, 4-4-4-4.62.* (42.62)(4s.67) 4;6 Tetr+Oct
- 4.4.4.4.4.4.4.4.62.6r6r62.*.*.*, 4.4.4.4. (44.62)(48.66.8) 4;6 Tetr+Oct
62-62
fsh 4.4.4.4.4.4.62.62.62.62.62.6r *. *. *, (43.63)(46.66.8) 4;6 Tetr+Oct
4.62.4.62.4.62
flu 4-4-4-4-4-4, (46)(412.612.84 ) 4;8 l'etr+Cub
4"4"4"4"4-4'4'4'4'4'4-4-6~-62'6~'6~'6~"
62"6z'6z'62"62"62"62"*'*'*'*
Tetrahedral, octahedral, square planar, trigonal, trigonal prismatic, trigonal
bipyramidal, square pyramidal, and cubic (eight-connected) respectively.
9. Nets with higher connectivity than four 189

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