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PAPER www.rsc.org/crystengcomm | CrystEngComm
Interpenetrated three-dimensional hydrogen-bonded networks frommetal–organic molecular and one- or two-dimensional polymeric motifs†
Igor A. Baburin,*a Vladislav A. Blatov,*a Lucia Carlucci,b Gianfranco Cianib and Davide M. Proserpio*b
Received 14th July 2008, Accepted 3rd September 2008
First published as an Advance Article on the web 26th September 2008
DOI: 10.1039/b811855h
The occurrence of interpenetrated three-dimensional networks has been systematically investigated
by the analysis of the crystallographic structural databases, using the program package TOPOS. After
our previous reports on interpenetration observed in valence-bonded MOFs, inorganic arrays and
hydrogen-bonded organic supramolecular architectures, in this paper we have focused our research on
the interpenetrated 3D networks based on hydrogen-bonded metal–organic molecular (0D) and
polymeric (1D and 2D) complexes from the Cambridge Structural Database. The current interest
for the crystal engineering of new functional materials has prompted many research groups to adopt
synthetic strategies implying the use of molecular metal complexes (0D) with suitably exo-oriented
hydrogen-bond donor and acceptor groups for the assembly of extended networks. With regard to this
we have examined 3D hydrogen-bonded supramolecular arrays formed by finite and infinite motifs of
lower dimensionality, analyzing their topologies and looking for their entanglements. We have
extracted a comprehensive list including 135 different motifs (71 assembled from 0D, 43 from 1D and
21 from 2D metal–organic motifs) showing the phenomenon of interpenetration (about two thirds not
detected in the original papers). These hydrogen-bonded networks include species assembled by one or
more building blocks, that are classified within the previously introduced Classes of interpenetration. It
is observed that the maximum interpenetration degree is limited to 5-fold and the main (overall)
topology is 412.63-pcu. An analysis of the possible relationships between the dimensionality of the
building blocks and the resulting network connectivity and topology, and of some factors determining
the interpenetration is also attempted, together with a comparison of the present results with those
for other families of interpenetrated materials.
Introduction
The explosive growth of the investigations focused in these years
on new molecule-based functional materials has produced
a plethora of extended architectures in the field of crystal engi-
neering of metal–organic and inorganic networks supported
by coordinative/valence bonds, as well as in the design of
supramolecular arrays of organic and metal–organic molecules
sustained by hydrogen bonds or other weak interactions.1 Many
of these species exhibit the intriguing feature of interpenetration
or other types of entanglements.2 Since the properties of these
materials can result not only from their molecular structures but
also from the nature of the extended originating architectures,
i.e. from the topology of the individual networks as well as from
the way in which the individual nets are multiply entangled (the
‘‘topology of interpenetration’’),2 we have planned a systematic
investigation of the interpenetration phenomena in 3D networks,
aSamara State University, Ac. Pavlov St. 1, 443011 Samara, Russia.E-mail: baburinssu@gmail.com; blatov@ssu.samara.rubDipartimento di Chimica Strutturale e Stereochimica Inorganica(DCSSI), Universita di Milano, Via G. Venezian 21, 20133 Milano,Italy. E-mail: davide.proserpio@unimi.it
† Electronic supplementary information (ESI) available: A complete listof the 135 crystal structures described in this work including theX(-H)/B H-bond distances and a list of new 14 organicinterpenetrated hydrogen-bonded frames from the last CSD update(November, 2007). See DOI: 10.1039/b811855h
1822 | CrystEngComm, 2008, 10, 1822–1838
using the program package TOPOS.3 We have already described
our studies on interpenetration in metal–organic (MOFs) and
inorganic networks, and in supramolecular arrays formed by
hydrogen-bonded organic molecules.4 We report here the
comprehensive results of our analysis of interpenetration in
metal–organic hydrogen-bonded 3D arrays from the Cambridge
Structural Database (CSD, version 5.29 of November 2007).
These species include networks both assembled from molecular
complexes (0D) and from polymeric 1D and 2D metal–organic
species; in all cases the hydrogen bonds increase the dimension-
ality of the constituent motifs to 3D networks.
The self-assembly of metal complexes possessing ligands with
exo-oriented functionalities suitable for hydrogen bonding is
a subject of great current interest in the crystal engineering of
functional supermolecules. New synthetic strategies have been
investigated in a number of recent papers in an attempt to extend
to metal–organic tectons the well established criteria for the
construction of organic hydrogen-bonded supramolecular
arrays. As previously observed,5 the contemporary presence of
both robust coordinative bonds and flexible hydrogen bond
bridges can result in additional possibilities in the engineering
of periodic supermolecules.
The analysis and classification of 3D hydrogen-bonded metal–
organic systems follow the lines previously adopted in our study
of interpenetrated 3D hydrogen-bonded organic networks.
Moreover, in two recent papers the same type of topological
This journal is ª The Royal Society of Chemistry 2008
analysis with TOPOS has been applied to single (i.e. non-inter-
penetrated) hydrogen-bonded frameworks in molecular organic
(1777 Refcodes) and metal–organic crystals (674 Refcodes).6 We
have thus the possibility of useful comparisons of the trends in
interpenetrated and non-interpenetrated networks based on
building blocks of similar type, with similar intermolecular
interactions.
The use of the ‘‘network approach’’ or topological approach to
crystal chemistry has allowed also in this case an useful analysis
of the structures via a simplification to schematized nets.
However, as already observed,4c the topological rationalization
of hydrogen-bonded frames is more difficult than that of MOFs
because the nodes and spacers are usually more ambiguous to
select [for instance, we are often faced with the alternative choice
of a single molecular complex (tecton) or of an oligomeric group
(synthon) as the node]. This difficulty is particularly evident
when polymeric 1D or 2D metal–organic motifs are involved,
where the resulting 3D interpenetrated nets can present
additional nodes arising from the formation of the hydrogen
bond bridges. Except for papers explicitly devoted to the crystal
engineering of hydrogen-bonded networks based on metal–
organic molecular tectons, scarce attention has been generally
devoted to the supramolecular interactions and to net formation
in these species: the topology is often ignored and the entangle-
ment and interpenetration features often overlooked (only about
one third of the structures described in this paper have been
explicitly recognized as interpenetrated).
Analysis of the crystal structures with TOPOS
We have recovered the information on metal–organic crystal
structures from the Cambridge Structural Database (release 5.29,
November 2007) using the program package TOPOS. Only
strong or moderately strong hydrogen bonds7 were considered.
The structures with completely or partially undetermined
hydrogens were studied as well. To determine the intermolecular
hydrogen bonds X–H/A (intramolecular hydrogen bonds are
irrelevant to our topological analysis) we have used the same
geometrical approach adopted in the previous papers on 3D
single and interpenetrated networks of hydrogen-bonded organic
molecules4c,6a and 3D single networks of hydrogen-bonded
metal–organic molecular species.6b The automatic calculation of
hydrogen bonds was carried out with the geometrical criteria that
are here briefly summarized: in a bridge X–H/A (X]N, O;
A]N, O, F) the H/A contact is assumed to be a hydrogen bond
if (i) d(H/A) # 2.5 A; (ii) d(X/A) # 3.5 A; (iii) the X–H/A
angle $ 120� (three- and four-centered, symmetrical and reso-
nance hydrogen bonds can be recognized as well). If the
hydrogen atoms were not allocated, only condition (ii) was
applied. In all cases we have used additional geometrical condi-
tions that included the parameters of Voronoi–Dirichlet
polyhedra. Further details on the criteria adopted can be found
in our previous paper.4c
The dimensionality of the extended frameworks formed
by hydrogen bonds in the case of 0D metal–organic species or
by valence bonds plus hydrogen bonds in the case of polymeric
1D and 2D metal–organic motifs was ascertained using the ADS
program of the TOPOS package. We consider here crystal
structures that contain finite or polymeric metal–organic species
This journal is ª The Royal Society of Chemistry 2008
only (except for some cases containing also inorganic counter-
anions and guest solvents). Since often the location of solvent
(not coordinated) water molecules is poorly determined, we
discarded cases where such molecules take part in the hydrogen-
bonded network. 135 3D interpenetrating arrays were revealed,
71 assembled from 0D, 43 from 1D and 21 from 2D metal–
organic motifs (Tables 1 and 2).
The assignment of topology to molecular hydrogen-bonded
3D frameworks was done in the same way as in the previous
papers on hydrogen-bonded frames.4c,6 Any molecular metal–
organic hydrogen-bonded framework was reduced to its under-
lying net whose nodes symbolize molecular centers of gravity and
their coordination numbers indicate to how many molecular
units a given molecule is hydrogen-bonded. We refer to this
description of topology as standard. However, as in organic
frames, the nodes can be also ascribed to supramolecular ‘ring’
synthons (see below). The alternative descriptions of topology
(where possible) are also given in Table 1.
The topology of a hydrogen-bonded framework formed by
polymeric species (1D or 2D) is more difficult to describe. To this
end, interatomic bonds responsible for periodicity within
a polymeric unit were properly cut in order to treat it formally as
an ensemble of finite fragments. Thus, when assigning topology
for a single 3D net, it was considered as built up from molecular-
like fragments connected to each other by both hydrogen bonds
and ‘cut’ bonds. This treatment gives the possibility to apply to
these species the same methodology as for molecular frames. In
most cases, the nodes of a net correspond to metal atoms or both
metal atoms and ligands. To illustrate this, let us consider the
crystal structure UO2(m-F)2(isonicotinic acid) [ASEFUZ] that
consists of chains extending along [100]. The periodicity within
a chain is determined by the U–F bonds of the double bridges
while isonicotinic acid is a ‘dangling’ ligand responsible for
hydrogen bonding between chains (Fig. 1). By cutting U–F
bonds, we get molecular units [UO2F2(isonicotinic acid)] that are
connected to four others by both hydrogen bonds and ‘cut’ U–F
bonds forming a framework with diamondoid topology (66-dia).
However, if we consider the U atoms and the isonicotinic acid
ligand as distinct 3-connected nodes, we get 103-ths topology
(Fig. 1). This example demonstrates some ambiguity in the
topological description of hydrogen-bonded frameworks formed
by polymeric species but let us emphasize that all possible ways
of assigning topology are interrelated and, for instance, the
relationship between 66-dia and 103-ths net was discussed a long
time ago.8 Indeed, the description for these 1D/2D species may
‘‘follow some intuition’’ because there is no unique way of cutting
a polymeric unit.
A similar approach is possible also in the case of 2D polymeric
layers. However, the choice to cut the bonds in the polymeric
species to produce pseudo-0D motifs, then proceeding with
the standard representation, is not always possible (e.g. when the
mid-points of the ligands are involved in hydrogen bonding) so
that ad hoc solutions are needed. A possible one is that used
for the isomorphic series [M(squarato)2(H2O)2][1,3-bis(4-pyr-
idinium)propane)] (KEZQEM etc.): we consider in these cases as
nodes, besides the metals, also all the ligands (coordinatively- or
hydrogen-bonded, see Fig. 2). It must be clear that whatsoever
net description we choose the kind of interpenetration (class and
degree, see below) is invariant to the choice of the net, but our
CrystEngComm, 2008, 10, 1822–1838 | 1823
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1824 | CrystEngComm, 2008, 10, 1822–1838 This journal is ª The Royal Society of Chemistry 2008
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py
rid
yl)
eth
an
e)3$T
HF
AB
(A)
P2
1/c
pcu
3Ia
[0,1
,0]
(11
.70)
2.0
0
DA
RQ
OC
Fe(
tmco
x)$
(C2H
5) 2
O$C
H3O
H;
tmco
x¼
N,N
,N-
tris
(2-(
3-(
Met
hyla
min
oca
rbo
ny
l)-2
-o
xy
ben
zam
ido
)eth
yl)
am
ine-
O,O
0 ,O
00 ,O
0 ,O
0 ,O
00 )
AA
P� 1
pcu
2II
ai
1.0
0a,b
DA
RQ
UI
Ga
(tm
cox
)$(C
2H
5) 2
O$C
H3O
HA
AP� 1
pcu
2II
ai
1.0
0a,b
NIP
LO
NM
n(4
-ace
tylp
yr)
(H2O
) 2(O
CN
) 2A
AP
21/c
pcu
2Ia
[1,0
,0]
(7.5
1)
1.3
3a,b
IMC
UC
LC
u(H
im) 4
(ClO
4) 2
AA
P2
1/n
pcu
2Ia
[1,0
,0]
(8.2
0)
1.3
3a,b
LIP
FA
RC
o(2
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bip
yri
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5,5
-dic
arb
oxyla
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P� 1
pcu
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1.0
0S
MP
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eth
oxy-p
yri
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ne)
3C
l 3A
AR
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d(N
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Hb
ipy)
AB
(A)
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12
12
1pcu
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00
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.67
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ZB
EC
[La
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3) 4
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y)(
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Hb
ipy)
AB
(A)
P2
12
12
1pcu
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00
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TE
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u(t
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3b
ipy$2
H2O
AB
0(A
)R
3pcu
2Ia
[0,0
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(27
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2.0
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SX
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im) 2
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lO4) 3$3
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y$H
2O
AB
0(A
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32
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2Ia
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ES
SE
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bim
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son
ico
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ide)
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AA
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acs
2II
ai
1.0
0P
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UQ
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4-O
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4-a
min
o(e
tha
no
l)b
is(e
tha
no
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3-
am
ino
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an
ola
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rop
ion
ato
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3F
e 8]$
0.5
CH
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H$0
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AA
Pa� 3
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MK
EP
W6S
8(4
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tam
ido
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din
e)6$D
MF
AA
AP
21/c
ose
2Ia
[1,0
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(16
.46)
1.7
1VI
8-connectednets
ZU
RS
EK
[Cd
(Him
) 4][
Ag
(CN
) 2] 2
AA
Pb
mn
bcu
2II
ai
1.0
0a
mixed
connectivity
nets
3,4-connectednets
NA
BY
OF
[Ag(i
son
ico
tin
am
ide)
2]B
F4
AB
(AB
)P� 1
sqc69
5Ia
[1,0
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(6.8
1)
1.1
4(IIa)(VII),cds
3,6-connectednets
DO
QZ
ISC
o(H
im) 4
(cyan
am
ido
nit
rate
) 2A
AP
21/n
rtl
1+
11
.00
a,b
ZO
KB
OQ
[Fe(
4-(
4-i
mid
azo
lylm
eth
yl)
-2-(
2-i
mid
azo
lylm
eth
yl)
-im
ida
zole
) 2]F
2
AB
(AB
)P
2/n
ant
2Ia
[0,1
,0]
(8.4
3)
1.0
0a
IX
IMZ
NP
C[Z
n(H
im) 4
](C
lO4) 2
AB
(AB
)C
2/c
ant
3Ia
[0,1
,0]
(7.1
1)
1.0
0a,b
I,pts
FO
GF
OX
01/0
2[Z
n(H
im) 4
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F4
) 2(p
oly
mo
rph
I)A
B(A
B)
C2
/cant
3Ia
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2)
1.0
0a,b
I,pts
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2)2(42.6)2(43.6
3.7
6.8
2.9)2(64.7
2)-new
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OG
FO
X[Z
n(H
im) 4
](B
F4
) 2(p
oly
mo
rph
II)
AB
(AB
)C
2/c
new
53
Ia[0
,1,0
](7
.02
)1
.6a,b
I,4ctrinodal
4-connectedbinodal
VA
SB
UN
[Zn
(male
on
itri
led
ith
iola
to) 2
]H2b
ipy
AB
(AB
)C
2/c
stb-4,4-P2/c
2Ia
[1/2
,1/2
,0]
(32
.61)
1.0
0a
4,8-connectednets
RA
XM
OT
[Co
(H2O
) 4I 2
](b
pd
o) 2
AB
0(A
B)
I41/a
cdscu
2II
ai
1.0
0a
X,pcu
ICIF
EF
[Co
(H2O
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O3) 2
](b
pd
o) 2
AB
0(A
B)
I41/a
scu
2II
ai
1.0
0X,pcu
ICIF
IJ[N
i(H
2O
) 4(N
O3) 2
](b
pd
o) 2
AB
0(A
B)
I41cd
scu
2II
ad
-gli
de
1.0
0X,pcu
6-connectedbinodal
FO
BJE
MC
u(N
-nit
rocy
an
am
idato
-N) 2
(Him
) 4A
AP� 1
tcj-6,6-C
ccm
2Ia
[0,0
,1]
(15
.23)
1.3
3a
aH
im¼
imid
azo
le;
H2b
iim
¼2
,20 -
bis
-im
ida
zole
;b
ipy¼
4,4
0 -b
ipy
rid
ine;
en¼
1,2
-eth
yle
ned
iam
ine;
H2b
ipy¼
4,4
0 -b
ipy
rid
iniu
m;
Hb
ipy¼
4-(
4-p
yri
dyl)
pyri
din
ium
;b
pd
o¼
4,4
0 -b
ipy
rid
ine-
N,N
0 -d
iox
ide;
tbim
¼b
is(t
ris(
2-b
enzi
mid
azo
lylm
eth
yl)
am
ine)
;DM
FA¼
N,N
0 -d
imet
hy
lfo
rma
mid
e;D
MS
O¼
dim
eth
yls
ulf
ox
ide;
TH
F¼
tetr
ah
yd
rofu
ran
e.
This journal is ª The Royal Society of Chemistry 2008 CrystEngComm, 2008, 10, 1822–1838 | 1825
Table
2In
terp
enet
rati
ng
hy
dro
gen
-bo
nd
edm
eta
l–o
rga
nic
net
wo
rks
fro
mp
oly
mer
icsp
ecie
s(1
D,
2D
).10
Fo
rth
eco
lum
n‘N
ote
’se
ete
xt.
Fo
rth
esu
bn
etse
eF
ig.
3a
nd
4
Ref
cod
eN
am
eaT
yp
e(n
od
e)S
ub
-net
Sp
ace
gro
up
Net
ZC
lass
Sy
mm
etry
No
teS
yn
tho
n
3-connectednets
RE
NP
AC
Ag
(m-b
is(4
-py
rid
yl)
am
ine)
ClO
4A
AHel
P6
52
2eta
4Ib
[1,0
,0],
[0,1
,0],
[1,1
,0]
(8.0
1)
(PIV
s)XII,qtz
RE
NP
EG
Ag
(m-b
is(4
-py
rid
yl)
am
ine)
NO
3A
B(A
B)
Hel
R3
2srs
4Ib
[1,0
,0],
[0,1
,0],
[1,1
,0]
(9.4
6)
(PIV
s)Y
OD
KU
XA
g(d
iall
yla
min
o)(
ClO
4)
AA
Hel
I41cd
srs
2II
ac-
gli
de
a,b
V,dia
WE
NB
AS
01
Cu
(dia
lly
lam
ino
)(N
O3)
AA
Hel
I41cd
srs
2II
ac-
gli
de
a,b
V,dia
AS
EF
UZ
UO
2(m
-F) 2
(iso
nic
oti
nic
aci
d)
AA
ZZ
Pm
cnths
3Ia
[0,1
,0]
(8.6
3)
a,b
KE
XW
AM
(3,3
0 -a
zo-b
is(6
-hy
dro
xy
ben
zoa
to)(
H2O
)(1
,10-
ph
ena
nth
roli
ne)
2C
d2
AA
ZZ
C2
/cths
3Ia
[1/2
,1/2
,0]
(11
.50)
a,b
KE
XW
EQ
(3,3
0 -a
zo-b
is(6
-hy
dro
xy
ben
zoa
to)(
H2O
)(1
,10-
ph
ena
nth
roli
ne)
2C
o2
AA
ZZ
C2
/cths
3Ia
[1/2
,1/2
,0](
11.5
0)
a,b
4-connectednets
RA
GY
AZ
(Ni(
bip
y) 2
(H2O
) 2) 2
(Mo
8O
26)
AA
hcb
P� 1
dia
3Ia
[1,0
,0]
(10
.18)
a,b
HU
WR
UM
Cd
(en
)(b
ipy
)(N
O3) 2
AA
ZZ
C2
/cdia
3Ia
[1,0
,0]
(8.1
6)
aJE
CR
UF
[Cd
(bp
f)(a
nil
ine)
2(N
O3) 2
]b
pf¼
1,4
-bis
(4-p
yri
dy
lmet
hy
l)-
2,3
,5,6
-tet
rafl
uo
rob
enze
ne
AA
ZZ
C2
/cdia
3Ia
[0,1
,0]
(11
.13)
a,b
JEC
SA
MC
d(b
pf)
(p-t
olu
idin
e)2(N
O3) 2
AA
ZZ
C2
/cdia
3Ia
[0,1
,0]
(10
.93)
a,b
ME
NL
UN
Cu
(py
rid
ine-
2,6
-dic
arb
ox
yla
to)(
2-m
eth
yli
mid
azo
le)
AA
ZZ
Pca
21
dia
2Ia
[0,1
,0]
(11
.02)
aF
AX
GU
H[A
g(b
ipy
)(H
2P
O4)]$2
H2O
AA
Lin
P2
/cdia
2Ia
[0,1
,0]
(8.8
1)
a,b
IIa
BE
NC
ED
Yb
(NO
3) 3
(1,2
-bis
(4-p
yri
dy
l)et
hen
eN
,N0 -
dio
xid
e)(C
H3O
H)
AA
ZZ
P2
1/c
dmp
2Ia
[1,0
,0]
(11
.09)
aK
EZ
QE
M[M
n(s
qu
ara
to) 2
(H2O
) 2](
1,3
-bis
(4-p
yri
din
ium
)pro
pa
ne)
AB
(A)
sql
P2
/ncds
2Ia
[1,0
,0]
(9.6
7)
aK
EZ
QIQ
[Co
(sq
uara
to) 2
(H2O
) 2](
1,3
-bis
(4-p
yri
din
ium
)pro
pa
ne)
AB
(A)
sql
P2
/ncds
2Ia
[1,0
,0]
(9.6
7)
aK
EZ
QO
W[N
i(sq
ua
rato
) 2(H
2O
) 2](
1,3
-bis
(4-p
yri
din
ium
)pro
pa
ne)
AB
(A)
sql
P2
/ncds
2Ia
[1,0
,0]
(9.6
7)
aK
EZ
QU
C[C
u(s
qu
ara
to) 2
(H2O
) 2](
1,3
-bis
(4-p
yri
din
ium
)pro
pa
ne)
AB
(A)
sql
P2
/ncds
2Ia
[1,0
,0]
(9.6
7)
aK
EZ
RA
J[Z
n(s
qu
ara
to) 2
(H2O
) 2](
1,3
-bis
(4-p
yri
din
ium
)pro
pan
e)A
B(A
)sql
P2
/ncds
2Ia
[1,0
,0]
(9.6
7)
a5-connectednets
IBU
DIT
Zn
2(O
H)(
5-(
4-p
yri
dyl)
tetr
azo
lato
-N,N
0 )A
Asql2f
P� 1
bnn
2Ia
[1,0
,0]
(10
.07)
aJE
XN
OQ
Co
2(b
iph
enyl-
4,4
0 -d
ica
rbo
xy
lato
) 2(2
-(2
-p
yri
dyl)
ben
zim
idazo
le) 2
AA
ZZ
P� 1
bnn
2Ia
[1,0
,0]
(8.8
8)
6-connectednets
YA
HP
IHN
i(b
ipy
)(3
,5-d
ica
rbo
xy
ben
zen
eca
rbo
xy
lato
) 2A
ALin
C2
/cbsn
3Ia
[1/2
,1/2
,0]
(7.7
1)
a,b
PA
RT
OS
[Cu
(hy
dro
gen
iso
ph
tha
lato
) 2(b
ipy
)]n
AA
Lin
Fdd
2bsn
3Ia
[0,1
/2,1
/2]
(7.5
9)
a,b
HA
CB
UJ
[Cu
(bip
y)(
1,4
-ben
zen
edic
arb
ox
ilate
)]$1
,4-
ben
zen
edic
arb
ox
yli
ca
cid
AB
0(A
)sql
C2
/cbsn
3Ia
[1/2
,1/2
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(7.6
8)
a,b
XA
MB
UJ
Cd
(4,4
0 -o
xyd
iben
zoa
to) 2
(1,2
-bis
(4-p
yri
dy
l)et
hen
e)A
AZZ
C2
/cpcu
3Ia
[0,1
,0]
(5.9
4)
a,b
WU
NP
IE[C
d(4
,40 -
azo
bip
yri
din
e)3(H
2O
) 2](
PF
6) 2$4
,40 -
azo
bip
yri
din
eA
B0
(A)
Dan
P� 1
pcu
3Ia
[1,0
,0]
(9.6
7)
a,b
NE
PW
OU
Zn
(5,1
0,1
5,2
0-t
etra
kis
(4-c
arb
ox
yp
hen
yl)
po
rph
yri
na
to)
(1,2
-b
is(4
,40 -
bip
yri
din
ium
)eth
an
e)2
AA
Lin
P2
1/n
pcu
3Ia
[1,0
,0]
(8.0
7)
a,b
OD
IZIK
Ni(
4-p
yri
dy
lacr
ila
to) 2
(H2O
) 2A
Asqlcat
Pbcn
pcu
2II
a2
-ax
isa,b
OD
IZU
WC
u(4
-py
rid
yla
cril
ato
) 2(H
2O
) 2A
Asqlcat
Pbcn
pcu
2II
a2
-ax
isa,b
LO
TP
OZ
[Ni[
9,1
0-b
is(4
-pyri
dyl)
an
thra
cen
e]2(H
2O
) 2](
NO
3) 2
AB
(A)
sqlcat
Iba2
pcu
2II
ac-
gli
de
LO
TN
OX
[Ni(
bip
y) 2
(H2O
) 2](
NO
3) 2$5
CH
3O
H$C
6H
6A
B0C
(A)
sql
Cc
pcu
2Ia
[1/2
,1/2
,0]
(11
.49)
QE
WF
II{[m
-Au
(CN
) 2] 2
[(C
o(N
H3) 2
) 2(m
-bip
yri
mid
ine)
]}[A
u(C
N) 2
] 2A
Asql
C2
/mpcu
2Ia
[1/2
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(8.9
3A
)a,b
QE
WF
OO
{[m
-Au
(CN
) 2] 2
[(N
i(N
H3) 2
) 2(m
-bip
yri
mid
ine)
]}[A
u(C
N) 2
] 2A
Asql
C2
/mpcu
2Ia
[1/2
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,0]
(8.9
3A
)a,b
QE
WF
UU
{[m
-Au
(CN
) 2] 2
[(C
u(N
H3) 2
) 2(m
-bip
yri
mid
ine)
]}[A
u(C
N) 2
] 2A
Asql
C2
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2Ia
[1/2
,1/2
,0]
(8.9
3A
)a,b
XA
QW
OC
[Cu
(1,3
-bis
(im
idazo
l-1-y
lmet
hyl)
-5-
met
hy
lben
zen
e)2(H
2O
) 2](
NO
3) 2
AB
(A)
sql
Pbcn
pcu
2II
ai
a,b
VE
TD
UT
Fe(
CN
) 6[S
n(C
H3) 3
(H2O
)]2[S
n(C
H3) 3
] 2$d
iox
an
eA
B(A
)sql
P2
1/n
pcu
2Ia
[1,0
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(13
.24)
a,b
TU
DH
OP
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Cu
(ad
ipa
to) 2
(Him
) 2A
ADan
C2
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2Ia
[1/2
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,0]
(9.3
4)
MU
HL
AC
Fe(
bip
y)(
dic
yam
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ipy
AB
0(A
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P� 1
pcu
2Ia
[0,1
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9)
PE
QL
EC
01
[Cd
(bip
y)(
H2O
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lO4) 2
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ipy
AB
0(A
)Dan
P� 1
pcu
2Ia
[0,1
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3)
1826 | CrystEngComm, 2008, 10, 1822–1838 This journal is ª The Royal Society of Chemistry 2008
TO
KP
AK
[Cd
(bip
y)(
H2O
) 2(C
lO4) 2
]$b
ipy
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0(A
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NO
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ipy
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ate
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yl-
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,0]
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yle
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ned
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ery
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m)]
(ClO
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(A)
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TA
VT
OA
[Cu
2(2
,20 :
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20 -
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ate
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O3P
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0)
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IIa
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HJO
OM
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ipy)(
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yam
) 2(H
2O
)$0
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ipy)(
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yam
) 2(H
2O
)$0
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)$0
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VA
QS
EL
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(ter
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B0C
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ipy
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OY
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CN
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Sn
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3) 3
(H2O
)]2[S
n(C
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]$b
ipy$2
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0(A
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P2
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ino
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KL
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01
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BE
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a2(5
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-tet
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yA
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22
Ia[1
/2,1
/2,0
](1
9.6
2)
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4,5-connected(32.6
2.7
2)(32.6
5.7
3)2-new
3X
AH
TU
V[N
i(tr
is(2
-am
ino
eth
yl)
am
ine)
Au
(CN
) 2][
Au
(CN
) 2]
AB
(AB
)ZZ
P2
1/n
new
32
Ia[1
,0,0
](8
.14
A)
a,b
4,6-connectedtrinodal(42.8
4)(46.8
9)(46)2-new
4O
BA
PU
CZ
n2(b
isT
CN
Q)(
TC
NQ
) 2(C
H3O
H) 4
;T
CN
Q¼
7,7
,8,8
-te
tra
cya
no
qu
ino
dim
eth
an
e,b
isT
CN
Q¼
7,7
0 -b
is(T
CN
Q)
AA
kgm
C2
/cnew
42
Ia[1
/2,1
/2,0
](1
5.4
0)
a
RE
CT
EY
/01
Mn
2(b
isT
CN
Q)(
TC
NQ
) 2(C
H3O
H) 4
AA
kgm
C2
/cnew
42
Ia[1
/2,1
/2,0
](1
5.4
4)
a
aen
¼1
,2-e
thy
len
edia
min
e;b
ipy¼
bip
yri
din
e;d
icy
am¼
dic
ya
na
mid
o;
bip
yet¼
1,2
-bis
(4-p
yri
dyl)
eth
an
e;cy
am¼
cyan
am
ido
.b
LA
DQ
EM
01
(lik
ely)
was
rep
ort
edw
ith
the
wro
ng
space
gro
up
,se
eL
AD
QE
M.
This journal is ª The Royal Society of Chemistry 2008 CrystEngComm, 2008, 10, 1822–1838 | 1827
Fig. 1 Topological description of UO2(m-F)2(isonicotinic acid) [ASE-
FUZ]: the 1D zig-zag chains can be cut to give ‘molecular’ units
[UO2F2(isonicotinic acid)]. These units are connected to four others by
both valence bonds (U–F bridges) and hydrogen bonds resulting in a 3D
framework with the 66-dia topology. On the other hand, considering the
U atoms and the isonicotinic acid ligand as distinct 3-connected nodes,
we obtain the 103-ths topology.
description of topology may be different from the one reported
in literature.
We must emphasize that this investigation and classification
of the metal–organic 3D interpenetrated hydrogen-bonded
Fig. 2 Formation of 2-fold 65.8-cds nets from the hydrogen-bond
interactions between 44-sql in M(squarato)2(H2O)2][1,3-bis(4-pyr-
idinium)propane) [M ¼ Mn (KEZQEM), Co (KEZQIQ), Ni (KEZ-
QOW), Cu (KEZQUC), Zn (KEZRAJ)].
1828 | CrystEngComm, 2008, 10, 1822–1838
networks have been carried out by strict use of computer
algorithms, an approach which leads to finding out all the cases
in spite of structural complexity and which avoids faults and
misses of the traditional human analysis. To assign unambigu-
ously the ‘topology of interpenetration’ we use moreover
a number of previously proposed descriptors to classify the
interpenetration patterns.4
Results
The results of the analysis are listed in Table 1 for the molecular
metal–organic building blocks (0D) and in Table 2 for the
polymeric species (1D and 2D), resulting in a total number of 135
different interpenetrating 3D arrays. These species are reported
in CSD with a greater number of entries since different Refcodes
are attributed in CSD to multiple crystal structure determina-
tions (e.g., KUSGEK, KUSGEK10 in Table 1). The columns of
Tables 1 and 2 report, besides the Refcode, the chemical formula
and the space group, the following information, similar to those
used in the previous paper on interpenetrated 3D hydrogen-
bonded organic frameworks:4c
(i) TYPE (NODE): the AA notation means that there is only
one type of motif (0D, 1D or 2D) that extends via hydrogen
bonds to give 3D interpenetrated frames (the same notation
holds when the motif is present in more than one crystallo-
graphically independent position). With AB (or AB0) we indicate
that besides the basic motif A there is a second molecular species
(B0 if neutral, and B if charged, usually an anion) involved in the
network (solvent molecules are not included). Note, however,
that these symbols do not give the actual ratio of the compo-
nents. The networks nodes, when necessary, are also specified;
i.e., with TYPE (NODE) AB(A) or AB0(A) the nodes are only in
the A moiety, while with AB(AB) and similar notations the nodes
are placed both in A and in B. A few cases with three types of
components are also observed, like AB0C(A) (see Table 2).
(ii) NET TOPOLOGY (and SUBNET in Table 2): we give,
also in this paper, the three-letter symbol of the net, proposed by
M. O’Keeffe, that can be retrieved from the RCSR database
(Reticular Chemistry Structure Resource, http://rcsr.anu.edu.au/).
Four nets found here are not listed in RCSR, but two (sqc27,
sqc69) were found in the EPINET database11a (Euclidean
Patterns in Non-Euclidean Tilings, http://epinet.anu.edu.au/,
names starting with sqc) and two (tcj-6,6-Cccm, stb-4,4-P2/c) in
the recent lists produced by Blatov and Proserpio.11b,c Tables 1
and 2 include also five new nets with complex topologies that
have been called new1, new2. new5. For their classification in
the tables and text we have used the corresponding Schlafli
symbol before the symbol new1, new2. and so on.
The column SUBNET in Table 2 reports the type of motif that
generates the 3D interpenetrated network via hydrogen bonds,
i.e. the type of 1D chain or the topology of the 2D layer (see
Fig. 3 and 4).
(iii) Z/Class/Symmetry: the degree of interpenetration Z (the
total number of 3D nets in the structure)4 and the class of
interpenetration4 are reported. The column Symmetry gives the
interpenetration vectors (A) and/or the symmetry operations that
relate equivalent interpenetrating nets.
(iv) HBRI (H-bond ratio index, in Table 1): this parameter
was introduced in our study on the interpenetrated 3D
This journal is ª The Royal Society of Chemistry 2008
Fig. 3 Different 1D sub-nets observed in 3D interpenetrated frame-
works (with the abbreviations used in Table 2). From top: linear (Lin),
zig-zag (ZZ), dangling arms (Dan), ribbon-of-rings (RoR), helical (Hel),
tube-like (Tub).
Fig. 4 The three topological types observed in the 2D sub-nets: square,
hexagonal and Kagome.
hydrogen-bonded organic networks4c and gives the ratio (No. of
total effective hydrogen bonds per asymmetric unit/No. of
theoretical single bonds required by the connectivity of the
nodes). As already pointed out, it depends on the choice of
the nodes and can be considered as an index of the stability of the
framework (i.e. values >1 are due to the presence of multiple
hydrogen-bond bridges joining the different metal–organic
complexes). Moreover, in homomolecular species (type AA) the
requirement of a balance between the number of hydrogen-bond
donor and acceptor groups in the building block can lead only to
an even number of hydrogen bonds (in order to achieve an exact
match HBRI ¼ 1)12 and, therefore, favours even node connec-
tivities,6 while with odd connectivity the values of HBRI should
be >1.
(v) NOTE: we have examined all the original papers reporting
the 135 interpenetrated structures and have classified them with
the letters: (a) when the interpenetration was not recognized
(87 cases), (b) when the 3D hydrogen-bonded net was not
detected (58 cases) and (c) when the connectivity and/or topology
of the net were wrongly assigned and/or some hydrogen bonds
were missed (only 2 cases). As already mentioned, many of these
investigations are explicitly devoted to the crystal engineering of
supramolecular architectures starting from molecular metal–
organic complexes and, therefore, the majority of these papers
give a correct description of the nets or a possible alternative
description, on the basis of a different choice of the nodes. In
many papers, on the other hand, the attention is exclusively
This journal is ª The Royal Society of Chemistry 2008
devoted to the valence-bonded units and the supramolecular
array is neglected.
(vi) SYNTHON: this column reports some extra information
concerning the presence of a certain supramolecular ‘‘ring syn-
thon’’,13 labelled as in the Fig. 5 (I–XIII). When a ‘‘ring synthon’’
gives rise to a ‘‘ring synthon net’’ the alternative topology is also
indicated. With ‘‘ring synthon net’’ we mean that the nodes of
this net are located at the centers of the supramolecular synthons.
This demonstrates that some arbitrariness is unavoidable in the
topology assignment of hydrogen-bonded supramolecular nets.
It must be stressed, however, that the topologies of the ‘‘stan-
dard’’ net and the corresponding ‘‘ring synthon net’’ are rigor-
ously interrelated.6a Moreover, this alternative choice does not
modify the kind of interpenetration (class and degree). Examples
containing more then one type of synthons are also present.
General statistics of the framework topologies andinterpenetration descriptors
Out of the 135 examples observed we can first divide them by the
nature of the basic constituent motifs: 0D (coordination
compounds) and 1D/2D (chain/layer coordination polymers).
The distribution is approximately 1:1 (exactly 52.6%: 47.4%).
Further we give for each type also the distribution of cases
containing a single (AA) or different (AB) chemical nodes
(see Fig. 6, left) and we can observe that there is no particular
preference (56%:44% for AA:AB). Looking in more detail to the
relationship between connectivity and node types (AA or AB) we
have the distribution shown in Fig. 6 (right).
It can be useful also to analyse the node connectivity of the
3D hydrogen-bonded nets vs. the dimensionality of the basic
constituent motifs (see Fig. 7). We can see that for low connec-
tivity (up to 4-c) the 0D motifs are preferred with respect to
the polymeric 1D/2D species (approximately 2.2: 1) while for
connectivity higher than 4 the reverse behaviour is observed
(approximately 1: 1.6).
The network topologies are distributed as shown in Fig. 8
(left). The most frequent topology is 412.63-pcu (28.9%) followed
by 66-dia (23.7%). Interestingly, this results comes out from the
fact that 412.63-pcu is very common in polymeric 1D/2D species
(27/64 ¼ 42.2%); on the other hand 66-dia is dominant in the 0D
species (26/71 ¼ 36.6%), as illustrated in Fig. 8 (right). Evidently,
the presence of extended coordinative chain or layer motifs
forces the outcome of certain preferred net topologies.
These interpenetrating nets mainly possess common topolo-
gies; nevertheless some cases with quite rare topologies have also
been observed (see e.g. Fig. 9), as well as five examples of
completely new ones. There are 21 and 16 distinct topologies for
0D and 1D/2D species, respectively, six of them (cds, dia, dmp,
pcu, srs, ths) are common for the two samples.
For the large majority of the nets the value of the degree of
interpenetration Z is equal to 2 (see Fig. 10) and the classes
of interpenetration are either Ia or IIa. The maximum value for
Z /it> is 5 in NABYOF, with the sqc69 topology.
Networks from molecular 0D motifs
Molecular metal–organic species suitable for giving hydrogen-
bond bridges can represent useful building blocks for the crystal
CrystEngComm, 2008, 10, 1822–1838 | 1829
Fig. 5 The ‘ring synthons’ observed in this work. We use different labels for synthons of the same type when they are metal-including synthons or not
(see IIb and IVb vs. IIa and IVa).
engineering of extended arrays. They have been therefore widely
investigated for this purpose and the papers reporting these
studies deserve great attention to the supramolecular architec-
tures, so that generally the topologies and entanglements are
correctly described. Their interactions and the resulting supra-
molecular nets (single and interpenetrated) are expected to be
similar to those for organic molecules because the metal atoms
are essentially screened by the organic ligands and, as a result, the
patterns of intermolecular contacts are close to those formed by
organic molecules.14 It is worth thus a more strict comparison of
Fig. 6 Distribution of the structures on the basis of node types (AA or A
1830 | CrystEngComm, 2008, 10, 1822–1838
the distribution of the dominant connectivities and topologies in
hydrogen-bonded 3D single and interpenetrated nets, based on
molecular organic and metal–organic units (see Fig. 11). For
a correct comparison only the AA type is considered, i.e. there is
only one type of 0D motif that extends via hydrogen bonds to
give 3D interpenetrated frames
With respect to connectivity, major differences in trends are
observed between hydrogen-bonded frameworks and MOFs.
For both organic and metal–organic nets the preferred connec-
tivity is 6-c (single) and 4-c (interpenetrated); for these families
B) (left) and relationship between connectivity and node types (right).
This journal is ª The Royal Society of Chemistry 2008
Fig. 7 Distribution of the connectivity of the nodes (n-c) in relation to
the dimensionality of the motifs.
Fig. 9 Three less common nets observed in 9 structures: (3,6)-c
(42.6)2(44.62.88.10)-ant (anatase), (4,8)-c (44.62)2(416.612)-scu, 6-c (48.54.63)-
bsn (b-Sn).
Fig. 10 Distribution of the values of Z (degree of interpenetration).
we have a parallel marked decrease of value of the major
connectivity on passing from the single nets to the inter-
penetrated ones (not observed in MOFs).
Indeed molecular species (organic or metal–organic) mainly
show ‘dense’ packing patterns with a marked tendency to close-
packed arrays6 without significant influence of hydrogen bonding
on the overall packing topology. According to Kitaigorodskii15
the trends to form close packing and to saturate all hydrogen
Fig. 8 Overall distribution of the top
This journal is ª The Royal Society of Chemistry 2008
bonds operate simultaneously: it has been shown recently6 that
the topologies of molecular packings realised in the organic and
metal–organic molecular crystals with hydrogen-bonded frame-
works and in those without hydrogen bonds are essentially the
ologies within the 135 structures.
CrystEngComm, 2008, 10, 1822–1838 | 1831
Fig. 11 Comparison of the distributions of the dominant connectivities and topologies in 3D single and interpenetrated nets. In each family the first
column gives the % values. a Ref. 6a. b Ref. 4c AA only 91 cases + 9 new added examples (see ESI).† c Ref. 6b. d this work (0D AA only). e Ref. 16 and
Ref. 6b. f Ref. 4a.
same. The tendency to form close packing can explain the
preference in hydrogen-bonded molecular nets for topologies
with high connectivity (6-c, 8-c), unusual in the rather porous
MOFs, where there are different packing trends mainly directed
by the stereochemical requirements of the nodal building blocks
(dominated by the tetrahedral and octahedral coordinations).
Checking for porosity in the interpenetrated molecular metal–
organic structures here described we have found that all of them
are really dense (non-porous). So we may conclude that, what-
ever the overall network type, hydrogen bonds do not signifi-
cantly influence the degree of space-filling (for a majority of
crystals). The observed decrease of the preferred net connectivity
on passing from the single hydrogen-bonded molecular frames
(6-c) to the interpenetrated ones (4-c) can reflect possible alter-
native arrangements of a flexible hydrogen bond system, even-
tually accompanied by an increase of the HBRI. For instance,
considering a body-centered sphere packing, alternative orien-
tations of the main interactions could result in a single 424.64-bcu,
in a 2-fold 412.63-pcu network or even 2-fold 42.84 lvt net (Fig. 12).
As for the 3D network topology distribution, this is more
difficult to be rationalized. The most frequent topology (though
with rather different percentages) is 66-dia in all but one family (it
is 412.63-pcu in single metal–organic nets).6b Still the differences
can be related to the underlying fact that the structures of
Fig. 12 The relations between 424.64-bcu and interpenetrating arrays,
2-fold 412.63-pcu and 2-fold 42.84-lvt, on changing the intermolecular
preferred interactions, without changing the overall bcu-x 14-neighbours
packing.
1832 | CrystEngComm, 2008, 10, 1822–1838
molecular species are mainly controlled by packing requirements
while those of MOFs by stereochemical requirements.6b, 16 It was
suggested16 that the topological type for MOFs mainly depends
on the stereochemistry of the metal-containing nodes (very
frequently tetrahedral and octahedral coordinations). Thus,
66-dia and 412.63-pcu (in this order) are the two main topologies in
MOFs. Surprisingly, the same is true also for organic single
frameworks. In contrast to this, in hydrogen-bonded metal–
organic single frames the tendency of ligands to saturate all
possible hydrogen bonds and to form an efficient spatial packing
of molecules leads to the preference of highly connected 6-c and
8-c topologies. On the other hand, the observed decrease of
connectivity in interpenetrated metal–organic frameworks turns
again the preferred topology to 66-dia, followed by 412.63-pcu.
Among the interpenetrated 3-connected nets in Table 1
(8 cases), besides the examples of the more usual 103-srs and
103-ths topologies, there are two cases belonging to the rare
103-utp topology, namely FIZZIY (3-fold) and CABFIV (4-fold).
The second one is particularly interesting: it is comprised of
tris(chelate) Co(Hbiim)3 complexes (Hbiim ¼ monoanion of
2,20-biimidazole) that are hydrogen-bonded to three adjacent
similar units as shown in Fig. 13. A schematized single net and
the 4-fold interpenetrated array are also shown in the same
Figure. Uncommon is also the class of interpenetration (IIIa), i.e.
the four nets are generated by translation plus rotation about
2-fold axis.
Within the species from 0D metal–organic complexes 66-dia is
the dominant topology (showing a maximum Z value of 4).
Particularly interesting, because obtained in the proper context
of crystal engineering, is a family based on the use of cubane-like
M4(OH)4(CO)12 complexes as nodes and hydrogen-bond
acceptor guests as spacers, giving n-fold (n ¼ 2–4) inter-
penetrated 66-dia arrays. The clathrates of M4(OH)4(CO)12 (M ¼Mn, Re) have been extensively studied by Zaworotko and
coworkers.9 They found some correlation between the length of
the bridging clathrate molecule and the degree of interpenetra-
tion (see Fig. 14): the longer 4,40-bipyridine (PEHKIW/10,
This journal is ª The Royal Society of Chemistry 2008
Fig. 13 The rare 3-connected net 103-utp as observed in CABFIV, 4-fold
interpenetrated.
Fig. 14 The interpenetration observed in 66-dia nets for the different
clathrates of M4(OH)4(CO)12 (M]Mn,Re): two different views of the
3-fold KUSGEK/10, ZEBGOC (top), 2-fold ZEBGAO, PEHKOC/10
(bottom left) and 4-fold PEHKIW/10, ZEBHIX (bottom right).
Fig. 15 The 5-fold interpenetrated NABYOF, the record of interpene-
tration among hydrogen-bonded coordination compounds: (top)
the standard description with three independent nodes giving the
3-connected trinodal sqc69 net and (bottom) the ring synthon description
giving 4-connected 65.8-cds net.
Fig. 16 The alternative topological description of FOGFOX01/02.
ZEBHIX) affords the highest Z value of 4 (with edges of the
derived 66-dia net of approximately 15 A). Given the similar
values of the edge lengths in the 2- and 3-fold interpenetrated
cases (ca. 11–12 A), it is difficult to find the driving force origi-
nating the rare 3-fold interpenetration (Class IIa, with the nets
related by a three-fold axis) in KUSGEK/10 and ZEBGOC.
Note that this is the second example known of this interpene-
tration pattern that was first theoretically derived in 197617 and
later observed only in the MOF Cu(2,7-diazapyrene)2PF6
[NIGLUK]18 as reported in our study of interpenetrated
MOFs.4a Interestingly 2-fold 66-dia are formed also when the
clathrate molecule is able to form only OH/p interactions,
keeping the edge length within 10–12 A.
Many examples exhibit mixed connectivities. One of these is
remarkable, i.e. the 5-fold interpenetrated NABYOF, [Ag(iso-
nicotinamide)2]BF4, type AB(AB), shown in Fig. 15. The
standard description with three independent nodes [Ag(1)L2],
This journal is ª The Royal Society of Chemistry 2008
[Ag(2)L2] and BF4� gives the trinodal (3,4)-c net
(4.82)2(42.82.102)(8.104.12)-sqc69. The alternative ring synthon
description (proposed in the original paper) uses two distinct
synthons (IIa and VII) and results into the simpler uninodal 4-c
net 65.8-cds topology. Among the other examples containing
nodes of different connectivity we must cite also [Zn(Him)4]
(ClO4)2 (IMZNPC), 3-fold interpenetrated, with the rare 3,6-c
topology (42.6)2(44.62.88.10)-ant (for anatase), Type AB(AB). In
Fig. 16 we show the isomorphic species [Zn(Him)4](BF4)2
CrystEngComm, 2008, 10, 1822–1838 | 1833
(FOGFOX01/02, polymorph I) in its standard description (with
the metals 6-c and the anions 3-c) and with the ring synthon
description as 4-connected binodal 42.84-pts.
Note that the three examples of interpenetrated nets with the
(42.6)2(44.62.88.10)-ant topology reported in Table 1 are unique;
indeed we have found with TOPOS TTO collection3 many
examples of this topology in valence-bonded coordination
polymers (AHOJUC, AHOKAJ, HECQUB, SALRON,
UGIGAS01, WOHYOH, WOHYOH01, WOHYUN, XIQHIO)
that are all non-interpenetrated. A second polymorph of
[Zn(Him)4](BF4)2 (FOGFOX) has also been characterized, that
exhibits a 3-fold interpenetrated array of 3,4,6-connected
tetranodal nets with the unprecedented topology (4.62)2(42.6)2
(43.63.76.82.9)2(64.72)-new5.
Networks from polymeric 1D/2D motifs
Coordination 1D or 2D polymers can increase their dimension-
ality by forming 3D nets via hydrogen bonds. Those showing
interpenetration are reported in Table 2. The 43 1D metal–
organic species show six different types of subnets (illustrated in
Fig. 3), all but four (GUYBEH, KEXWAM, KEXWEQ,
BENCED, see below) with the 1D motifs running in the same
direction. Few remarkable 3-connected nets are observed, like in
Fig. 17 The 83-eta net formed by 1D helical chains in RENPAC (4-fold
interpenetrated).
1834 | CrystEngComm, 2008, 10, 1822–1838
the case of Ag(m-bis(4-pyridyl)amine)ClO4 (RENPAC) with
helical chains cross-linked to give a 4-fold interpenetrated array
of 83-eta nets (see Fig. 17). Note that similar interpenetration
pattern was observed in the interpenetrated MOF [Cu2
(tetraacetylethane)(bipy)2](NO3)2 [LEQQII].19 Three cases of
3-fold interpenetrated architectures with the 103-ths net topology
are formed from 1D parallel zigzag chains in ASEFUZ, and 1D
perpendicular on parallel plane for KEXWAM and KEXWEQ
as clearly illustrated in Fig. 18.
The majority of the networks in Table 2 show 6-c 412.63-pcu
topology: indeed, this topology seems naturally favoured by the
variety of side linking modes that can associate parallel 1D
chains, whichever the subnet type, into a 3D array (see Fig. 19).
Other possibilities of linking chains to give different 3D topol-
ogies are illustrated in Fig. 20.
The 21 2D coordination polymers that generate 3D inter-
penetrated hydrogen-bonded arrays show only three subnet
topologies (see Fig. 4), mainly the 44-sql one, as summarized in
Table 3.
The generation of the 3D net topologies from 44-sql layers is
illustrated in Fig. 21.
The 412.63-pcu nets are formed in a simple way via hydrogen-
bond bridges connecting the nodes of the adjacent stacked layers.
A different linking of adjacent 44-sql layers is observed for the
6-c nets 48.54.63-bsn (see also Fig. 9). As already mentioned,
for the case of the family [M(squarato)2(H2O)2][1,3-bis(4-
pyridinium)propane)] (illustrated in Fig. 2) the origin of the 65.
8-cds nets comes from hydrogen bonding between the mid-point
of ligands of the M(L)2 44-sql layers above and below the plane.
In (4.62)2(42.610.83)-rtl nets the nodes of a layer form two
hydrogen-bond bridges with the mid-points of the ligands of
Fig. 18 Examples of 103-ths topology formed by 1D zigzag chains
parallel (center) or perpendicular on parallel planes (bottom).
This journal is ª The Royal Society of Chemistry 2008
Fig. 20 Arrangements of the hydrogen-bonding systems that connect
1D chains to give (4.62)2(42.610.83)-rtl (BILSAR, RAVJED/01, ZECFAO)
on the left, 66-dia (HUWRUM, JECRUF, JECSAM, MENLUN)
(center), and on the right the less common 65.8-dmp from ZZ chains
running perpendicular on parallel planes observed only in BENCED.
Table 3 Summary of the 3D nets formed from 2D coordination layers
Topology 2D subnet 3D hydrogen-bonded net
sql 18 9 pcua, 5 cds, 2 rtl, 1 bnn (5-c), 1 bsn (6-c)kgm 2 new 4,6-chcb 1 dia (obvious stacking of hcb)
Fig. 21 Hydrogen-bonded nets generated from 44-sql layers: 412.63-pcu
(LOTNOX, QEWFII, QEWFOO, QEWFUU, XAQWOC, VETDUT);
48.54.63-bsn (HACBUJ); 65.8-cds (KEZQEM. KEZQIQ, KEZQOW,
KEZQUC, KEZRAJ); (4.62)2(42.610.83)-rtl (BIBDEV, SAVLEV).
Fig. 22 The polythreaded layer formed by ribbons of rings in GUYBEH
(top), a single ribbon of rings (middle) and a single net (4.85)2(42.84)-new2
from the 2-fold resulting array.
Fig. 19 Different kinds of 412.63-pcu nets derived from 1D chains. With
the Dan subnet we have 10 cases: WUNPIE, TUDHOP/01, MUHLAC,
PEQLEC01, TOKPAK, RIZDUZ, GOTKAB, LADQEM, LAD-
QEM01, NASZOW.
adjacent layers and these 3-c ligands are linked via hydrogen
bonds one half above and one half below the plane.
The Kagome layers found in M2(bisTCNQ)(TCNQ)2
(CH3OH)4 [OBAPUC: M ¼ Zn; RECTEY/01: M ¼ Mn] are
stacked with an ABAB sequence and are connected in a complex
way to saturate all possible hydrogen bonds from the four cyano-
groups of the TCNQ derivatives. The resulting 4,6-c trinodal
(42.84)(46.89)(46)2-new4 net is a very rare net with collisions.20,2d
This journal is ª The Royal Society of Chemistry 2008
Networks from entangled polymers
In the 3D hydrogen-bonded interpenetrated networks originated
from polymeric motifs we should consider the possibility that
they are already interpenetrated, polycatenated or entangled in
some way.2c Indeed, we observed few examples of such situa-
tions. One case Ca2(5,10,15,20-tetrakis(4-carboxyphenyl)-
porphyrin)(H2O)8$py (GUYBEH) consists of 1D ribbons of
rings (RoR) spanning perpendicular directions of propagation in
such a way to give 2D polythreaded layers2c (see Fig. 22).
Hydrogen-bond bridges involving the water molecules
CrystEngComm, 2008, 10, 1822–1838 | 1835
coordinated to the Ca ions on adjacent ribbons join them into
a 2-fold interpenetrated 3D 4-connected binodal network with
the novel (4.85)2(42.84)-new2 topology.
Inclined polycatenation of 44-sql type layers with density of
catenation2b doc (1/1) of the diagonal-diagonal type2b is observed
in M(4-pyridylacrilato)2(H2O)2 (M]Ni, Cu) [ODIZIK, ODI-
ZUW] and [Ni[9,10-bis(4-pyridyl)anthracene]2(H2O)2](NO3)2
[LOTPOZ]. The hydrogen bonds connect layers of the same
orientation resulting in 412.63-pcu 2-fold interpenetration, where
the two 3D nets are related by the same symmetry operation
that relates the 2D inclined sets of 44-sql layers (obviously not
a translation; it is a 2-fold axis in ODIZIK/ODIZUW and
a c-glide plane in LOTPOZ) (see Fig. 23). Finally, we must cite
the case of Zn2(OH)(5-(4-pyridyl)tetrazolato-N,N0) [IBUDIT]
Fig. 24 The 2-fold intepenetrated 44-sql layers observed in IBUDIT. The
chosen simplification considers as a single node the dimeric unit Zn2(OH)
(illustrated at bottom right). The dotted lines in the top image are the
hydrogen bonds to the adjacent (above and below) layers.
Fig. 25 From the simplified 2-fold 44-sql (top) observed in IBUDIT to
the 2-fold interpenetrated array of 5-connected 46.64-bnn nets (middle). At
the bottom right a single idealized 46.64-bnn net is shown.
Fig. 23 Structure of M(4-pyridylacrilato)2(H2O)2 [ODIZIK (M ¼ Ni),
ODIZUW (M ¼ Cu)]: one square unit from the 44-sql layer (top left); the
inclined polycatenation of layers with doc (1/1) of the diagonal-diagonal
type (top right, the dotted lines are the hydrogen bonds that interlace the
44-sql layers to give the 412.63-pcu nets); two views of the 2-fold inter-
penetration of 412.63-pcu (bottom).
1836 | CrystEngComm, 2008, 10, 1822–1838
consisting of 2-fold interpenetrated 44-sql layers (Fig. 24).
Hydrogen bonds interlinking the layers generate the 2-fold
interpenetrated 46.64-bnn network as illustrated in Fig. 25.
Conclusions
The analysis of interpenetrating 3D networks based on
hydrogen-bonded metal–organic molecular (0D) and polymeric
(1D and 2D) complexes in CSD using the TOPOS package has
produced a list of 135 distinct entangled frames. We have found
that the maximum interpenetration is limited to 5-fold and the
main (overall) topology is 412.63-pcu. However the results are
rather different when dealing with nets from 0D or from 1D/2D
building motifs: in the former case the preferred net connectivity
is 4-c while in the latter case it is 6-c. The presence of valence-
bonded motifs (especially 2D) has direct influence on the
resulting 3D net topology. Interpenetration was previously not
seen in most (ca. two thirds) of the listed species that exhibit
a number of topological types, five of which are unprecedented.
The networks from 0D motifs are analysed in more detail and
their connectivities and topologies are compared with the
distributions in the other families of single and interpenetrated
3D arrays. For the nets derived from 1D/2D motifs the rela-
tionship with the original subnets (6 types of 1D and 3 of 2D) is
investigated. A few noteworthy cases involving entangled orig-
inal subnets are also discussed. Tables 1 and 2 (and ESI†) contain
a lot of further information that could be useful for comparisons
and classification of new future interpenetrated species.
Acknowledgements
L.C., G.C. and D.M.P. thank MIUR for financing the
PRIN 2006–2007 ‘‘POLYM2006: Innovative experimental and
This journal is ª The Royal Society of Chemistry 2008
theoretical methods for the study of crystal polymorphism:
a multidisciplinary approach.’’
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