Interpenetrated three-dimensional hydrogen-bonded networks ... · Interpenetrated three-dimensional hydrogen-bonded networks from metal–organic molecular and one- or two-dimensional

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: [email protected]; [email protected] di Chimica Strutturale e Stereochimica Inorganica(DCSSI), Universita di Milano, Via G. Venezian 21, 20133 Milano,Italy. E-mail: [email protected]

† 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

http://www.rsc.org/crystengcomm

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


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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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

,20 -

bip

yri

dyl-

5,5

-dic

arb

oxyla

te-N

,N0 )

3$1

.5H

2O

AA

P� 1

pcu

2II

ai

1.0

0S

MP

BIC

10

Bi(

3-s

ulf

an

ilam

ido

-6-m

eth

oxy-p

yri

dazi

ne)

3C

l 3A

AR

3pcu

2Ia

[0,0

,1]

(10

.31)

1.0

0a,b

BIV

SE

E[N

d(N

O3) 4

(bip

y)(

H2O

) 2](

Hb

ipy)

AB

(A)

P2

12

12

1pcu

2II

a2

1[1

00

]1

.67

GO

ZB

EC

[La

(NO

3) 4

(bip

y)(

H2O

) 2](

Hb

ipy)

AB

(A)

P2

12

12

1pcu

2II

a2

1[1

00

]1

.67

JOS

TE

Q/0

1[E

u(t

bim

) 2](

ClO

4) 3$

3b

ipy$2

H2O

AB

0(A

)R

3pcu

2Ia

[0,0

,1]

(27

.35)

2.0

0JO

SX

AQ

/01

[Tb

(tb

im) 2

](C

lO4) 3$3

bip

y$H

2O

AB

0(A

)R

32

pcu

2Ia

[1,0

,0]

(13

.10)

2.0

0W

ES

SE

S[N

d(t

bim

) 2](

ClO

4) 3$3

bip

y$2

H2O

AB

0(A

)R

32

pcu

2Ia

[1/3

,�1

/3,�

1/3

](1

3.1

8)

2.0

0N

US

GO

X[A

g(i

son

ico

tin

am

ide)

3]B

F4

AA

P2

1/n

acs

2II

ai

1.0

0N

US

GU

D[A

g(i

son

ico

tin

am

ide)

3]C

lO4

AA

P2

1/n

acs

2II

ai

1.0

0P

EJP

UQ

[(m

4-O

) 3(m

4-a

min

o(e

tha

no

l)b

is(e

tha

no

lato

)(m

3-

am

ino

tris

(eth

an

ola

to) 3

(m2-p

rop

ion

ato

) 3F

3F

e 8]$

0.5

CH

3O

H$0

.5H

2O

AA

Pa� 3

lcy

2II

ai

1.0

0a

7-connectednets

KA

MK

EP

W6S

8(4

-(ace

tam

ido

)pyri

din

e)6$D

MF

AA

AP

21/c

ose

2Ia

[1,0

,0]

(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

,0]

(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

](B

F4

) 2(p

oly

mo

rph

I)A

B(A

B)

C2

/cant

3Ia

[0,1

,0]

(6.8

2)

1.0

0a,b

I,pts

3,4,6-connectednets(4.6

2)2(42.6)2(43.6

3.7

6.8

2.9)2(64.7

2)-new

5F

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

) 4(N

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

,0]

(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

,1/2

,0]

(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

,1/2

,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

/mpcu

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

,0]

(13

.24)

a,b

TU

DH

OP

/01

Cu

(ad

ipa

to) 2

(Him

) 2A

ADan

C2

/cpcu

2Ia

[1/2

,1/2

,0]

(9.3

4)

MU

HL

AC

Fe(

bip

y)(

dic

yam

) 2$b

ipy

AB

0(A

)Dan

P� 1

pcu

2Ia

[0,1

,0]

(8.6

9)

PE

QL

EC

01

[Cd

(bip

y)(

H2O

) 2(C

lO4) 2

]$b

ipy

AB

0(A

)Dan

P� 1

pcu

2Ia

[0,1

,0]

(9.0

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

AB

0(A

)Dan

C2

/cpcu

2Ia

[1/2

,1/2

,0]

(10

.00

)a

RIZ

DU

Z[C

u(b

ipy

)(H

2O

) 2(B

F4) 2

]$b

ipy

AB

0(A

)Dan

C2

/cpcu

2Ia

[1/2

,1/2

,0]

(9.8

2)

a,b

GO

TK

AB

[Cd

(bip

y)(

H2O

) 2(C

F3S

O3) 2

]$b

ipy

AB

0(A

)Dan

Pcc

npcu

2II

ai

a,b

LA

DQ

EM

[Mn

(bp

yet

)(H

2O

) 4](

ClO

4) 2

(bp

yet

) 4(H

2O

) 2A

B0

(A)

Dan

C2

/cpcu

2II

a2

-ax

isL

AD

QE

M01(b

)[M

n(b

py

et)(

H2O

) 4](

ClO

4) 2

(bp

yet

) 4(H

2O

) 2A

B0

(A)

Dan

P� 1

pcu

21

+1

—N

AS

ZO

W[Z

n(b

ipy

)(H

2O

) 4](

NO

3) 2$b

ipy

AB

0C

(A)

Dan

P� 1

pcu

2Ia

[1,0

,0]

(10

.63

)IZ

ITE

QC

u2(2

,20 :

40 ,

400 :

200 ,

20 -

qu

ate

rpy

rid

yl-

6,6

00 -d

i-2

-p

yri

din

e)V

2O

4(O

3P

CH

3P

O3H

) 2

AA

Lin

P2

1/n

pcu

2Ia

[1,0

,0]

(10

.71

)a,b

PA

QH

UL

[Cd

(H2O

) 4(b

is-[

3-(

4-p

yri

dy

leth

yle

ne)

-2,4

-p

enta

ned

ion

e]b

ery

lliu

m)]

(ClO

4) 2

AB

(A)

Lin

I41/a

pcu

2II

ai

IIb

TA

VT

OA

[Cu

2(2

,20 :

40 ,

400 :

200 ,

20 -

qu

ate

rpy

rid

yl-

60 ,

600 -

di-

2-

py

rid

ine)

{H

O3P

(CH

2) 2

PO

3H

} 2]

AA

Lin

P� 1

pcu

2Ia

[1,0

,0]

(9.2

0)

a,b

IIa

MU

HJO

OM

n(b

ipy)(

dic

yam

) 2(H

2O

)$0

.5C

H3O

HA

ATub

P4

1pcu

2II

a4

1-s

crew

MU

HJU

UF

e(b

ipy)(

dic

yam

) 2(H

2O

)$0

.5C

H3O

HA

ATub

P4

1pcu

2II

a4

1-s

crew

MU

HK

AB

Co

(bip

y)(

dic

ya

m) 2

(H2O

)$0

.5C

H3O

HA

ATub

P4

1pcu

2II

a4

1-s

crew

8-connected

VA

QS

EL

[Mn

(H2O

) 4(b

ipy

et)]

(ter

eph

tala

te)$

(bip

yet

) 2A

B0C

(A)

Dan

P� 1

hex

3Ia

[1,0

,0]

(10

.55

)a

mixed-connectivity

nets

3,6-connected

BIL

SA

RM

n(c

ya

m) 2

(Him

) 2A

ARoR

P2

1/a

rtl

2Ia

[0,0

,1]

(6.6

6A

)R

AV

JED

/01

Cu

(Him

) 2(m

-cyan

am

ido

nit

rate

) 2A

ARoR

P2

1/c

rtl

2Ia

[1,0

,0]

(7.1

2)

a,b

ZE

CF

AO

Cu

(met

hyli

mid

azo

le) 2

(m-t

ricy

an

om

eth

nid

o) 2

AA

RoR

P2n

artl

2Ia

[0,1

,0]

(10

.00

)a,b

BID

BE

WZ

n(2

-carb

oxy-1

,4-b

enze

ned

icarb

oxyla

to)(

bip

y)

AA

sql

P2

1/n

rtl

2Ia

[1,0

,0]

(9.8

7)

SA

VL

EH

Cu

(2-c

arb

ox

y-1

,4-b

enze

ned

ica

rbo

xy

lato

)(b

ipy

)A

Asql

P2

1/n

rtl

2Ia

[1,0

,0]

(9.9

8)

a,b

TA

BL

OY

[Fe(

CN

) 6][

Sn

(CH

3) 3

(H2O

)]2[S

n(C

H3) 3

]$b

ipy$2

H2O

AB

0(A

)Dan

P2

1/n

sqc27

2Ia

[1,0

,0]

(10

.42

)a,b

ME

KM

AQ

Ni(

dic

yam

) 2(2

-am

ino

pyri

mid

ine)

AA

Tub

P4

2/m

bc

new

12

IIa

2-a

xis

IIa

ME

KL

UJ/

01

Co

(dic

ya

m) 2

(2-a

min

op

yri

mid

ine)

AA

Tub

P4

2/m

bc

new

12

IIa

2-a

xis

IIa

4-connectedbinodal(4.8

5)2(42.8

4)-new

2G

UY

BE

HC

a2(5

,10

,15

,20

-tet

rak

is(4

-ca

rbo

xy

ph

enyl)

po

rph

yri

n)(

H2O

) 8$p

yA

ARoR

Cm

canew

22

Ia[1

/2,1

/2,0

](1

9.6

2)

a

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


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


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).


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


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,


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],


[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).


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


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


theoretical methods for the study of crystal polymorphism:

a multidisciplinary approach.’’

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