A rare alb-4,8-Cmce metal-coordination network based on tetrazolate and phosphonate functionalized 1,3,5,7-tetraphenyladamantane

Article abstract of DOI:10.1039/c2ce26819a

Symmetric tetrahedral ligands are prominent, but somewhat under-investigated building blocks for the generation of coordination polymeric networks. Coordination networks [Mn₅Cl₂(L ¹)₂(H₂O)₄

Full text of DOI:10.1039/c2ce26819a

View Article Online / Journal Homepage
CrystEngComm
Accepted Manuscript
This is an Accepted Manuscript, which has been through the RSC Publishing peer
review process and has been accepted for publication.
CrystEngComm
Accepted Manuscripts are published online shortly after acceptance, which is prior
to technical editing, formatting and proof reading. This free service from RSC
Publishing allows authors to make their results available to the community, in
citable form, before publication of the edited article. This Accepted Manuscript will
be replaced by the edited and formatted Advance Article as soon as this is available.
www.rsc.org/crystengcomm
Volume 12 | Number 5 | May 2010 | Pages 1317–1658
To cite this manuscript please use its permanent Digital Object Identifier (DOI®),
which is identical for all formats of publication.
More information about Accepted Manuscripts can be found in the
Information for Authors.
Please note that technical editing may introduce minor changes to the text and/or
graphics contained in the manuscript submitted by the author(s) which may alter
content, and that the standard Terms & Conditions and the ethical guidelines
that apply to the journal are still applicable. In no event shall the RSC be held
responsible for any errors or omissions in these Accepted Manuscript manuscripts or
any consequences arising from the use of any information contained in them.
HOT ARTICLE
COMMUNICATION
Hall et al.
HIGHLIGHT
Wang, Su et al.
Alginate-mediated routes to the
selective synthesis of complex metal
oxide nanostructures
Long
Ionothermal synthesis of a new
open-framework zinc phosphate
NIS-3 with low framework density
pH effect on the assembly of
metal–organic architectures
www.rsc.org/crystengcomm
Registered Charity Number 207890

Page 1 of 10
CrystEngComm
Dynamic Article Links ►
CrystEngComm
View Article Online
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
A rare alb-4,8-Cmce metal-coordination network based on tetrazolate
and phosphonate functionalized 1,3,5,7-tetraphenyladamantane†
Ishtvan Boldog,a Konstantin V. Domasevitch,*b Igor A. Baburin,*c Holger Ott,d Beatriz Gil-Hernández,e
Joaquín Sanchiz,*e Christoph Janiak*a
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Symmetric tetrahedral ligands are prominent, but somewhat underꢀinvestigated building blocks for the
generation of coordination polymeric networks. Coordination networks
[Mn5Cl2(L1)2(H2O)4(DMF)4] ⋅ 3 H2O ⋅ 7 DMF, 1 and the [La2(H5L2)2(H2O)6], 2 are synthesized under
10 mild solvothermal methods in DMF from the adamantaneꢀbased tetrahedral ligands, 1,3,5,7ꢀtetrakis(4ꢀ
phenyltetrazolꢀ5ꢀyl)adamantane (H4L1), reported for the first time, and 1,3,5,7ꢀtetrakis(4ꢀ
phenylphosphonic acid)adamantane (H8L2), respectively. Compounds 1 and 2 are based on completely
different pentanuclear and binuclear secondary metal building units, respectively, and have different
symmetries, but demonstrate an interesting coincidence of underlying topologies, which could be
15 interpreted as a directing or 'imprinting' effect of the symmetry of the rigid tetrahedral ligands. Both
structures represent examples of a rarely observed (4,8)ꢀcoordinated net. The
temperature is slightly lower than the expected for five Mn(II) ions with S = 5/2 and g ≈ 1.98 and on
lowering the temperature MT approaches the expected value for a single Mn(II) as a result of the
χMT product for 1 at room
χ
antiferromagnetic coupling through the tetrazolate bridges.
20
pronounced. Two reasons could be given why: lesser synthetic
accessibility and the close vicinity of the functional groups for
small tetrahedral ligands, which leads to the formation of denser
structures. A lesser utility of tetrahedral building blocks is
50 sometimes assumed, because the most frequent diamondoid
topology40 is prone to interpenetration.41 We believe that this
reasoning is not generally applicable, since it does not take into
account the benefits of the rigid symmetric tetrahedral building
units in PCPs built up from nonꢀtetrahedral metal SBUs, where
55 the symmetric ligand may ‘imprint’ symmetry into the resultant
structure. Analysis of such ‘imprinting’ is important for the
development of new PCPs under conditions when predictions still
remain uncertain.
The most important classes of scarce tetrahedral organic
60 ligands are represented by tetraphenylmethane42,43,44,45 and
adamantane derivatives (Scheme 1).44,46,47 Results with these
perfect symmetrical ligands can be traced back to the first, most
seminal PCP work.48 Elongated tetrakis(4ꢀbiphenyl)methane and
1,3,5,7ꢀtetraphenyladamantane derivatives (Scheme 1) are even
65 less used, but exactly these extended ligands are most interesting
in the context of highly porous PCPs. About five PCPs were
obtained with deprotonated 1,3,5,7ꢀadamantaneꢀtetraphenꢀ4ꢀyl
tetracarboxylic,46 tetraphosphonic,49,50 or tetrasulfonic49,51 acid,
respectively. Very recent examples also include prospective PCPs
70 based on the tetrakis(biphenyl)methane building block reflecting
the gradually growing interest in the tetrahedral ligand
class.45,52,53
Introduction
Metalꢀorganic frameworks (MOFs) or threeꢀdimensional porous
coordination polymers (PCPs)1 are the subject of continuous
attention.2ꢀ7 The reason for that is their porosity, the large inner
25 surface areas, the tuneable pore sizes and the topologies,8 which
provides for versatile architectures9,10 and potential
applications.2,11,12,13 Such applications include ion exchange, gas
adsorption and storage of, in particular, hydrogen and methane,14ꢀ
18
water sorption for heat transformation,19 gas20,21,22 and liquid23
30 separation processes, drug delivery,24,25 sensor technology,26,27
heterogeneous catalysis,28 hosts for metal colloids or
nanoparticles29,30 or polymerization reactions,31 pollutant
sequestration,32 microelectronics,33 luminescence,34 nonꢀlinear
optics35 and magnetism.36
35
A fundamental problem in the synthesis of PCPs is to increase
the porosity (surface area and/or pore size), while preserving the
framework robustness. The designs of known rigid PCPs involves
mostly the use of rigid bidentate or tridentate ligands.
Prototypical ligands are linear benzeneꢀ1,4ꢀdicarboxylate and
40 trigonalꢀplanar benzeneꢀ1,3,5ꢀtricarboxylate together with their
extended homologues.2,3,8,37 These ligands act as organic spacers
connecting metal ions or metalꢀcontaining secondary building
units (SBUs) according to Robson’s concept.38,39 On the contrary,
the use of rigid symmetric tetrahedral ligands, a next step in the
45 series of rigid linear and trigonalꢀplanar ligands, is much less
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

CrystEngComm
Page 2 of 10
View Article Online
D
Some remaining nonꢀcrystalline admixtures were separated by
35 suspending the crystalline precipitate multiple times in a 1:1
mixture of DMF:MeOH and removing the supernatant with a
Pasteur pipette followed by double rinsing of the deposit with the
same solvent mixture and suction filtration. Subsequent overnight
drying in vacuo (10–2 Torr) at r.t. yielded 312 mg (85 % based on
40 H4L1 ⋅ 6.5H2O) of almost colorless crystalline product.
D
The product is slightly soluble in DMF, insoluble in nonꢀpolar
organic solvents and is sensitive to moist air, which leads to a
color change to dark brown after prolonged time. The compound
is stable for at least one hour in air without significant visible
45 deterioration. FTꢀIR (neat) ν, cm–1: 3500ꢀ2900 (w, br),
2928 (w, sh), 2854 (w), 1645 (vs), 1496 (w), 1450 (m), 1418 (m),
1384(s, sh), 1253 (w), 1105 (m), 1060 (w), 1008 (m), 841 (m),
D
D
D
D
D
elongation
D
788 (w),
761 (s),
729(w),
678 (m),
662 (m).
D
C109H147Cl2Mn5N43O18 (2693.21, 1) calc. C 48.61, H 5.50,
50 N 22.36; found C 48.72, H5.61, N 22.31%.
D
D
N
N
D
D
HN
N
D
D
N
N
D = donor group,
e.g. COOH or CN4H (tetrazol-5-yl)
N
D
N
H
H4L1
H
N
N
Scheme 1 Tetrahedral linkers based on the methane and adamantane
N
cores.
N
5
Here we present two coordination polymers based on not yet
reported 1,3,5,7ꢀtetrakis(4ꢀphenyltetrazolꢀ5ꢀyl)adamantane, H4L1,
and scarcely investigated 1,3,5,7ꢀtetrakis(4ꢀphenylphosphonic
acid)adamantane, H8L2,50 (Scheme 2) with the coincidence of the
rare (4,8)ꢀcoordinated network topology. The results are
OH
P
HO
O
N
NH
N
N
10 discussed in the context of interest towards frameworks with
highꢀconnectivity and long internodal bridges for the generation
of nonꢀinterpenetrated structures with large pores and elongated
ligands. Comparison is made with the only known geometrical
analogue of H4L1, the smaller tetrakis(4ꢀphenyltetrazolꢀ5ꢀ
15 yl)methane ligand (H4ttpm) (cf. Fig. 2).54
HO
HO
H8L2
P
O
OH
P
OH
O
Experimental
P
All inorganic salts were of reagent grade and used without further
purification. Dimethylformamide, DMF (VWR, ACSꢀgrade) and
MeOH (Acros, spectroscopic grade) were used as delivered. The
20 syntheses of H4L1 is described in the ESI†. H8L2 was obtained as
described in ref.49 Details concerning the physical methods of
investigation are given in the ESI†.
O
OH
OH
Scheme 2 Tetrahedral linkers with the adamantane core used in this
work.
Synthesis of [La2(H2O)6(H5L2)2] ⋅ Solv, 2
55 La(NO3)3 ⋅ 6H2O (17 mg, 39 ꢁmol) of was dissolved in 50 ꢀL of
water in a small test tube (din = 6mm). Methanol (2 mL) was
layered over the aqueous solution, followed by a solution of
5.0 mg (6.5 ꢁmol) of H8L2 in 1 mL of MeOH. Within two days at
r.t. small droplets of liquid precipitated on the wall of the tube
60 and crystals were growing within the droplets during the next two
weeks. The crystals were separated by centrifugation, washed
with 0.5 mL of water and after final separation were dried in air.
Yield: 1.6 mg (25 % based on H8L2) of colorless microcrystalline
powder.
Synthesis of [Mn5Cl2(L1)2(H2O)4(DMF)4] ⋅ 3 H2O ⋅ 7 DMF, 1
Anhydrous MnCl2 (398 mg, 3.16 mmol) and H4L1 ⋅ 6.5H2O
25 (225 mg, 0.27 mmol) , were dissolved in a mixture of DMF
(22.5 mL) and MeOH (22.5 mL) inside a 50 mL glass vial sealed
with a Teflon lined screw cap. The solution was heated for 8 days
at 70 °C. Large spherical polycrystalline conglomerates of almost
colorless crystals were deposited starting from the second day of
30 heating. The supernatant, containing a minor amount of nonꢀ
crystalline deposit, was decanted and the crystalline precipitate
was quickly transferred into a Schenk funnel with a frit for the
subsequent washing and filtration operations under inert gas.
65
FTꢀIR (KBr) ν, cm–1: 3410 (vs, br), 2926 (w), 2898 (w),
2851 (w), 1604 (s, sh), 1501 (w), 1445 (w), 1395 (m), 1360 (w),
2
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 10
CrystEngComm
View Article Online
1138 (vs), 1055 (vs), 1016 (m), 918 (m), 829 (m), 703 (m),
566 (s), 492 (m).
X-ray crystallography
dipolar cycloaddition of azide to the nitrile catalyzed by
anhydrous zinc chloride (Fig. 1). This transformation sequence is
composed of simple highꢀyielding steps, which leave room for
further optimization. Thus, the affordable parent 1,3,5,7ꢀ
45 tetraphenyladamantane compound58 renders the class of paraꢀ
substituted tetraphenyladamantane molecules as accessible
building blocks for the construction of PCPs.
The reaction of MnCl2 with H4L1 under standard mild
solvothermal conditions59 in DMF, typical for the preparation of a
50 range of carboxylate and azolate complexes,8 produced almost
transparent crystals in a form of large spherical coꢀgrown
conglomerates. The product after washing and drying in vacuo at
Single crystal Xꢀray diffraction experiments were performed on a
Bruker APEX II QUAZAR system equipped with a multilayer
mirror and an IꢁS MoꢀKα source (λ = 0.71073 Å).
Crystals of the asꢀsynthesized form of 1 grew inherently as
polycrystalline aggregates with some singleꢀcrystalline domains
(Fig. S3 in ESI†). All attempts to separate a single crystal from
10 the bulk material were unsuccessful and a two component nonꢀ
merohedral twin was measured. The indexing of the two twin
domains was done using the Reciprocal Lattice Viewer tool in
APEX2.55 All nonꢀhydrogen atoms of the framework residue in 1
were refined anisotropically, except for disordered guest and
15 coordinated solvent molecules. The high Rꢀvalues of 1 can be
traced to the disordered guest solvent molecules in the pores and
are not due to twinning or data quality.
5
room
temperature
corresponded
to
the
formula
[Mn5Cl2(L1)2(H2O)4(DMF)4] ⋅ 3 H2O ⋅ 7 DMF, 1. Crystallinity
55 was preserved when 1 was protected from moist air as evidenced
by the powder Xꢀray diffraction (PXRD) pattern (Fig. S19 in
ESI†).
Small single crystals of 2 were found in the crystalline bulk
material next to larger intergrown crystals (Fig. S5 in ESI†). It
Singleꢀcrystal Xꢀray analysis on a small single crystal from the
freshly prepared conglomerates of 1-as (as synthesized) before
60 washing and drying revealed a 3D frameworkꢀstructure of
formula {Mn5(ꢀꢀCl)2(L1)2(H2O)4(DMF)4} based on an extended
pentanuclear manganese cluster, with a geometry close to linear
(Fig. 1b). All three different manganese atom types of this
centrosymmetric cluster, the terminal facꢀ{MnClN2O3}, the
65 middle {MnClN4O} and the central {MnN6} atom octahedrally
coordinated. The octahedra are connected in a faceꢀtoꢀface
fashion. MnꢀN bond lengths are in the range of 2.22ꢀ2.40 Å and
fit the expected MnꢀN bond length range of 2.20ꢀ2.35 Å extracted
from the CSD for MnꢀN(azole/~ate) bonds (Fig. S9 and S10 in
70 ESI†). Interestingly, 1 is only the third tetrazolate complex where
the {MnN6} coordination environment is observed besides the
structures of iminoꢀ5,5'ꢀditetrazole60,61 and H4ttpm (Fig. 2).54
However, the {MnN6} arrangement is quite typical for other
azolates, especially pyrazolates and imidazolates (52 occurrences
75 found in CSD with typical MnꢀN bond lengths in the 2.2ꢀ2.3 Å
interval (Fig. S10). The two known tetrazolate complexes with
the {MnN6} fragment have bond lengths within the range of 2.20ꢀ
2.40 Å.
20 was possible to perform the measurement on
a
tiny
0.03×0.07×0.08 mm single crystal, which was only diffracting to
a resolution of 0.87 Å. The low diffracting power originates from
the crystal size, guest molecules in the MOF cavities and disorder
in the crystal. A combination of weak highꢀangle data and pores
25 in the crystal is typical for a lowerꢀthanꢀusedꢀto Xꢀray data
quality in MOF structures. All nonꢀhydrogen atoms in 2 were
refined using anisotropic displacement parameters including the
guest molecules, i.e. water and MeOH. Due to diffuse packing of
solvent molecules in combination with an average data
30 resolution, not all solvent molecules could be located. SQUEEZE
(PLATON)56 could be used to decrease the R1 to 7.12 % but was
not included for the reported structure as some of the guest
molecules are participating in the hydrogen bonded network.
Further details, including crystal data and structure refinement
35 are given in the ESI†.
Results and Discussion
The synthesis of the H4L1 ligand was performed starting from the
57
known 1,3,5,7ꢀtetrakis(4ꢀiodophenyl)adamantane, Ad(PhI)4 in
two steps: Formation of the tetranitrile Ad(PhCN)4 by the
40 Rosenmundꢀvon Braun reaction followed by a Huisgen 1,3ꢀ
80
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

CrystEngComm
Page 4 of 10
Dynamic Article Links ►
CrystEngComm
View Article Online
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
I
OOCCF3
I
, I2
OOCCF3
I
CHCl3, r.t.
I
N
N
CuCN, DMF
reflux
HN
N
Ad(PhI)4
I
CN
N
N
N
N
ZnCl2, NaN3
DMF, reflux
H
H
N
NC
N
N
N
CN
N
NH
Ad(PhCN)4
H4L1
N
N
CN
Scheme 3 Synthesis of the 1,3,5,7ꢀtetrakis(4ꢀphenyltetrazolꢀ5ꢀyl)adamantane, H4L1 ligand.
Fig. 1 The basic building blocks in [Mn5Cl2(L1)2(H2O)4(DMF)4] ⋅ x H2O ⋅ y DMF z H2O, 1-as (aꢀd, top), and [La2(H2O)6(H5L2)2] ⋅ Solv, 2 (a'ꢀd', bottom):
The tetraꢀconnected tetraphenylꢀadamantane ligands (L1)4– (a) and (H5L2)3– (a'), the octaꢀconnected coordination clusters {Mn5Cl2(H2O)4(DMF)4} (b) and
{La2(H2O)6} (b') with their bridging ligand coordination, sections of the complete frameworks (c, c') and the topological network representation (d, d').
5
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 4

Page 5 of 10
CrystEngComm
View Article Online
.
The aboveꢀmentioned complex of manganese with H4ttpm,
[Mn6(ttpm)3] ⋅ 5DMF ⋅ 3H2O,54 where the ligand is metrically
isomorphous with H4L1, is worth
comparison with 1.
[Mn6(ttpm)3] ⋅ 5DMF ⋅ 3H2O is based on a {Mn3(tetrazolate)6}
hexagonal bipyramid) is a probable reason why the observed net
was not included into the compilation of ‘default’ binodal nets for
crystal design.71 However, this net was generated by Blatov and
Proserpio as a subnet of the (6,12)ꢀcoordinated alb net and could
a
5
linear trinuclear cluster (Fig. 2), serving as a sixꢀconnected node 50 be given a name albꢀ4,8ꢀCmce as analyzed by the program
in a framework with the (4,6) garnet (gar) topology,62 rare for
coordination polymers. The terminal {MnN3O3} and center
package TOPOS.72 Groupꢀsubgroup relations show that with two
symmetryꢀindependent SBUs this net can be realized in
orthorhombic space groups Pbca (the Mn compound in ref. 66),
Pbcn, Pccn, Pcca, Aea2, C2221 as well as in the two monoclinic
{MnN6} manganese atoms of the cluster have
a similar
10 coordination environment compared to 1. Thus, scalingꢀup the
ligand causes an expansion of the cluster from triꢀ to pentanuclar 55 space groups P21/c and C2/c. The latter two symmetry groups are
with preservation of its linear geometry, by the inclusion of a
{MnClN4O} fragment with a bridging chloride ion, which also
substitutes one Oꢀligand at the terminal manganese atom. Such
15 extension could, in principle, be continued by formation of linear
those of compound 1, the cobalt, zinc and cerium compound in
ref. 66,68,69, respectively, and 2.
The chance to observe the same network for the second time in
a rather unrelated case could be viewed as a complete serendipity.
2n+1 nuclear clusters with some adjustment in their connectivity 60 Yet, it occured during the screening of crystallization conditions
by substitution of tetrazolate bridges with halidoꢀ or oxidoꢀ
bridges. Interestingly, 1 is one of the first porous coordination
polymers with a secondary building unit consisting of at least five
20 manganese atoms in a row joined by azole/azolate bridges. Two
aiming for the preparation of novel phosphonate complexes of
lanthanids with another elongated tetrahedral ligand, the 1,3,5,7ꢀ
tetrakis(4ꢀphenylphosphonic acid)adamantane, H8L2.50 Slow
interdiffusion of an aqueous layer containing La(NO3)3 ⋅ 6H2O
are 65 and a methanol ligand solution afforded a mingled deposit. The
other
examples
of
coordination
polymers
benzeneꢀ
[Mn2(BDT)Cl2(DMF)2] ⋅ 1.5CH3OH ⋅ H2O, BDT
=
main constituent and optically the only crystalline phase of this
ditetrazolate,63 a mixed ligand tetrazolate/triazolate polymer,64
and eight molecular complexes with a metal chain equal or longer
25 than five atoms.
deposit was [La2(H2O)6(H5L2)2] ⋅ Solv, 2.
The structure of 2 is built upon binuclear {La2(H2O)4(ꢀꢀ
Phos)2(Phos)3} units (Phos = ꢀPO(OH)O– or ꢀPO(OH)2), where
70 the lanthanum ions are bridged by two Phos moieties and
supported by two additional hydrogen bonds (O(H)ꢂꢂꢂO 2.89 Å)
between pairs of axially coordinated water molecules. The
coordination environment of the eightꢀcoordinated lanthanum
ions is a slightly distorted tetragonal antiprism, a typical {LnO8}
75 configuration for lanthanides.
N
N
N
NH
The absence of base during the crystallization ensured autoꢀ
acidification of the solution and, hence, slow crystallization in
favorable reversible conditions. At the same time only a threefold
deprotonation was achieved against the eightfold possible,
80 yielding a quite open, but presumably not very stable framework,
sustained only by two coordinationꢀbonded bridges. A structural
search for lanthanide (lanthanum included) complexes with
phenylphosphonates revealed that exactly the same dinuclear unit
is present in the structure of the coordination polymer
N
N
H
N
N
N
H
N
N
N
N
HN
N
N
Fig. 2 H4ttpm ligand and the trinuclear coordinationꢀbonded cluster
constituting the sixꢀconnected framework with a garnet topology in
[Mn6(ttpm)3] ⋅ 5DMF ⋅ 3H2O.54
85 [Nd2(HL)(MeOH)8] ⋅ 3HCl ⋅ H4L ⋅ 6H2O,
H4L = 2,2'ꢀ(O,O ꢀ
pentaethyleneglycol)ꢀ6,6'ꢀ(1,1'ꢀbinaphthyl)ꢀdiphosphonic acid73
and in slightly distorted form in the molecular complex
30
The {Mn5(ꢀꢀCl)2(H2O)4(DMF)4} cluster in 1 serves as an 8ꢀ
connected node with a hexagonalꢀbipyramidal geometry, while
the adamantaneꢀbased ligand gives rise to a tetrahedral node (Fig.
1b) thereby yielding the binodal (4,8)ꢀconnected underlying net
[La2(HL)2(H2L)2(H2O)8],
H3L = 3ꢀcarboxyphenylphosphonic
acid. Taking into account the surprising scarcity of
90 phenylphosphonate complexes with lanthanides (~18 examples),
we conjecture the prevalence of such a motif in slightly acidic
synthetic conditions (i.e., if only a partial deprotonation of the
phenylphosphonic acid is possible). In a more basic medium, at
least in principle, the high coordination number of lanthanum
95 would allow for the realization of a twelveꢀconnected ‘paddleꢀ
wheel’ꢀlike cluster node, possibly of higher stability. Such a high
connectivity of a cluster node would probably exceed the
reasonable nodal density for a still relatively short organic
building block, but represent an interesting possibility for a
100 further elongated ligand.
35 {45.6}2{410.614.84}.65 To the best of our knowledge, there are only
five recently published coordination polymers, namely of Co, Mg
and Mn with the 5,5'ꢀmethylenediisophthalate ligand,66,67 of Zn
with mꢀsulfonatophenylphosphonato and 4,4′ꢀbipyridine ligands68
and of Ce with the N,N′,N″ꢀtris(4ꢀcarboxylatephenyl)ꢀ1,3,5ꢀ
40 benzenetricarboxamide ligand69 which possess exactly the same
underlying topology. The maximal space group symmetry of this
net70 is Cmce with hexagonalꢀbipyramidal vertices at 4a (site
symmetry C2h) and tetrahedral vertices at 8f (site symmetry Cs)
Wyckoff positions (see ESI† for more details). Such unusual
45 combination of coordination polyhedra (tetrahedron and
It is interesting to note that 2 is the first coordination polymer
of a lanthanide with a truly multifunctional phenylphosphonate,
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 5

CrystEngComm
Page 6 of 10
View Article Online
i.e., with more than two phosphonate moieties in one ligand. We
believe, that this points to an interesting, still undiscovered niche
for designing lanthanide PCPs of high connectivity based on rigid
phenylphosphonates. Not much is known on lanthanide with
rigids phenylphosphonates with the exception of three
compounds with long bifunctional phosphonates and a few other
simpler compounds.73,74,75 In contrast, nonꢀrigid aliphatic
phosphonates, i.e. characterized by the {CalkPO(OH)2} fragment,
account for 273 polymeric structures reflecting the high interest
5
10 fuelled by phosphonate chelators for lanthanide separation.76
Both complexes, 1 and 2 possess potentially open framework
structures with maximal calculated porosity of 63% and 40%
(VOID/SOLV procedures of PLATON56 were performed on
structural data with all the solvent molecules removed). As the
15 manganese coordination polymer, 1, sustained by a priori robust
coordinationꢀbonded clusters, was obtained phaseꢀpure in
significant quantities, it was tried to prepare it in a solventꢀfree
form and determine the surface area experimentally.
Unfortunately, both direct degassing and solvent exchange
20 (methanol and dichloromethane were attempted) ended in
framework collapse (all attempts at >120 °C) or incomplete
solvent exchange. The best sample, after exchange with methanol
and degassing at 70 °C, demonstrated minor hydrogen sorption of
about 0.45 wt% at 1 bar (Fig. S11 in ESI†), but complete lack of
25 nitrogen sorption. The instability of framework 1 resembles that
of the [Mn6(ttpm)3] ⋅ 5DMF ⋅ 3H2O compound,54 where the
preparation of the porous framework also failed. We believe that
milder methods of solvent removal, e.g. supercritical CO2
drying,77 or freeze drying45 could be more successful. A probable
30 reason for instability of framework 1 may be hydrolytic cleavage
of the Mn–Ntetrazole and Mn–Cl bonds by minor rests of water at
elevated temperatures causing fragmentation of clusters and
structural collapse. However, further efforts were not invested
since 1 is unstable in moist air (oxidation and/or hydrolysis with
35 turning brown), which qualifies the material as nonꢀpromising for
PCPs. The stability of 2 was not investigated in depth, but it
slowly loses crystallinity in air, in accordance with the heavily
hydrated and seemingly labile structure observed.
Fig. 3 Temperature dependence of the χMT product for 1. The line
corresponds to the best fit to the Fisher equation for a regular chain of
classical spins with S = 5/2.
60 As described above, the structure of compound 1 consists of
extended pentanuclear clusters with geometry close to linear, in
which chloride ions and tetrazolate ligands with ꢁ2ꢀ1,2 and ꢁ2ꢀ1,3
bridging modes connect the Mn(II) ions. A view of the cluster
with the magnetic coupling arrangement is shown in Scheme 4.
65
Scheme 4 Magnetic coupling exchangeꢀpathways in 1.
The zeroꢀfield Hamiltonian for such a system is then H =
40 Magnetic properties of 1
J12(S1S2)
J23(S2S3)
J34(S3S4)
J45(S4S5)
J13(S1S3)
The manganese complex
1 was subjected to magnetic
J35(S3S5). J12 and J45 involve a ꢁ2ꢀCl and two ꢁ2ꢀ1,2ꢀtetrazolate
70 bridges, J23 and J34 three ꢁ2ꢀ1,2 tetrazolate bridges and J13 and J35
a ꢁ2ꢀ1,3 one. As Mn(1) and Mn(2) are equivalent to Mn(5) and
Mn(4), respectively, we can do J1 = J12 = J45, J2 =J23 =J34, and J3
=J13 =J35, thus the spin Hamiltonian can be rewritten as H =
J1(S1S2+ S4S5) J2(S2S3+S3S4) J3(S1S3+S3S5). We have tried to
75 analyze the magnetic susceptibility data with that Hamiltonian by
means of the Magpack code.82 However, we failed all our
attempts probably because the multiplicity of the system is
2(S+1)5 = 65= 7776 which implies the program to diagonalize,
and solve a matrix of 7776 x 7776 for each (T,χMT) experimental
80 pair of values to calculate the three magnetic coupling constants
and g, the Landé factor. In order to simplify somewhat the system
we have made J3 = 0 (since the coupling is very weak through
this magnetic exchangeꢀpathway),80,83 also we made J = J1 = J2
(since both magnetic exchangeꢀpathways are similar), and
85 reduced the experimental data set to 11, equally spaced in a
logarithm scale from 2 to 300 K. However, the system worked for
measurements, also to assess the purity of the material (absence
of higher valence states of manganese). The magnetic behavior is
consistent with a Mn(II) linear pentanuclear complex exhibiting
45 weak antiferromagnetic coupling mediated by the tetrazolate
bridges.78,79,80 Figure 3 shows the temperature dependence of the
χMT product for compound 1. At room temperature the χMT
product is slightly lower than the expected for five highꢀspin
Mn(II) ions (observed 20.90 cm3 mol–1 K–1; calculated χMT =
50 5(Nβ2g2/3kT) S(S+1) = 21.44 cm3 mol–1 K–1, with S = 5/2 and g ≈
1.98).81 On lowering temperature, χMT continuously decreases
and tends to the value for a single Mn(II), 4.30 cm3 mol–1 K–1, the
limit value for antiferromagnetically coupled clusters with an odd
number of Mn(II) ions.
55
6
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 10
CrystEngComm
View Article Online
55 d Bruker AXS GmbH, Östliche Rheinbrückenstraße 49, Dꢀ76187
a week without convergence. Finally, we have analyzed the high
Karlsruhe, Germany
temperature data (T > 50 K) with the Fisher expression (based in
the H= –JΣSiSi+1 Hamiltonian) for a regular chain of classical
spins (S = 5/2).79,84 We took this decision since the other attempts
e Grupo de Materiales Magnéticos, Departamento de Química
Inorgánica, Universidad de La Laguna, La Laguna 38206, Spain. Email:
jsanchiz@ull.es
5
failed, the cluster is rather large (pentanuclear), and in the high 60 † Electronic supplementary information (ESI) available: Synthesis of
ligands, structural data and related information of 1 and 2, topological
temperature region — when the magnetic correlation is small —
the magnetic behavior of the cluster and that of the chain are
expected to be very similar. Best fit parameters are g = 1.98, J = –
analysis, TGA, PXRD. CCDC reference numbers 910535 and 910536.
For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c2ceXXXX
2.01cm–1 and R =1.88ꢂ10–5 (R is the agreement factor defined as
10 Σi[(χMT)obs(i)−(χMT)calc(i)]2/Σi[(χMT)obs(i)]2). The value obtained for
the magnetic coupling constant is an averaged value of J1, J2 and
J3. The theoretical plot reproduces very well the magnetic
susceptibility data at temperatures above 50 K. However, the plot
deviates at low temperatures since the low temperature limit of
15 the χMT product for an antiferromagnetic chain is zero (as a result
of the cancellation of the spins), whereas the low temperature
value for an antiferromagnetically coupled Mn(II) cluster with an
odd number of Mn(II) ions is 4.30 cm3 mol–1 K–1, that of a single
Mn(II). The good value obtained for g and the reproducibility of
20 the data at high temperatures support the purity of the sample and
the oxidation state +2 for manganese. Additionally, the value of
the magnetic coupling constant is not far from that found in other
studies.78,79,80
1 S. Kitagawa and R. Matsuda, Coord. Chem. Rev., 2007, 251, 2490ꢀ
2509; T. K. Maji and S. Kitagawa, Pure Appl. Chem., 2007, 79,
2155ꢀ2177.
2 C. Janiak, Dalton Trans., 2003, 2781ꢀ2804.
3 C. Janiak and J. K. Vieth, New. J. Chem., 2010, 34, 2366ꢀ2388.
4 J. R. Long and O. M. Yaghi, Chem. Soc. Rev., 2009, 38, 1213ꢀ1214.
Introduction in 2009 special MOF issue.
5 K. Biradha and M. J. Zaworotko, New. J. Chem., 2010, 34, 2353ꢀ2356.
Introduction in 2010 special MOF issue.
6 K. Hindson, Eur. J. Inorg. Chem. 2010, 3683; S. Kitagawa and S.
Natarajan, Eur. J. Inorg. Chem., 2010, 3685. Introduction in 2010
MOF special issue.
7 H.ꢀC. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012, 112, 673ꢀ
674. Editorial to 2012 MOF special issue.
8 N. Stock and S. Biswas, Chem. Rev., 2012, 112, 933–969.
9 M. O'Keeffe, Chem. Soc. Rev., 2009, 38, 1215ꢀ1217.
10 M. O'Keeffe and O. M. Yaghi, Chem. Rev., 2012, 112, 675–702.
11 A. U. Czaja, N. Trukhan, U. Müller, Chem. Soc. Rev., 2009, 38, 1284ꢀ
1293.
12 G. Férey, Dalton Trans., 2009, 4400ꢀ4415; M. J. Prakash and M. S.
Lah, Chem. Commun., 2009, 3326ꢀ3341.
13 J.ꢀP. Zhang, Y.ꢀB. Zhang, J.ꢀB. Lin and X.ꢀM. Chen, Chem. Rev.,
2012, 112, 1001ꢀ1033; H. Wu, Q. Gong, D. H. Olson and J. Li,
Chem. Rev., 2012, 112, 836–868;
Conclusions
25 The occurrence of the rare albꢀ4,8ꢀCmce network topology in
coordination polymers of quite different tetrahedral adamantaneꢀ
based tetrazolate and phosphonate ligands reflects subtle
relationships. We would interpret this finding of identical
topologies as a 'structureꢀdirecting role' or 'symmetry imprinting'
30 by the tetrahedral ligand towards adaptable metal secondary
building units. It was demonstrated that manganese tetrazolate
14 L. J. Murray, M. Dinca and J. R. Long, Chem. Soc. Rev., 2009, 38,
1294ꢀ1314; R. E. Morris and P. S. Wheatley, Angew. Chem. Int. Ed.,
2008, 47, 4966ꢀ4981.
clusters,
namely
the
{Mn3(tetrazolate)6}
versus
15 J.ꢀR. Li, R. J. Kuppler and H.ꢀC. Zhou, Chem. Soc. Rev., 2009, 38,
1477ꢀ1504.
16 M. P. Suh, Y. E. Cheon and E. Y. Lee, Coord. Chem. Rev., 2008, 252,
1007ꢀ1026; C. J. Kepert, Chem. Commun., 2006, 695ꢀ700.
17 M. P. Suh, H. J. Park, T. K. Prasad and D.ꢀW. Lim, Chem. Rev., 2012,
112, 782–835.
{Mn5Cl2(tetrazolate)8} could 'grow' as the ligand is elongated.
We are on the way to address the problem of symmetry
35 'imprinting' and elongation of tetrahedral ligands aiming for
stable porous coordination frameworks with large pore sizes.
18 T. Düren, Y.ꢀS. Bae and R. Q. Snurr, Chem. Soc. Rev., 2009, 38, 1237ꢀ
1247; S. S. Han, J. L. MendozaꢀCortés and W. A. Goddard III, Chem.
Soc. Rev., 2009, 38, 1460ꢀ1476. R. B. Getman, Y.ꢀS. Bae, C. E.
Wilmer and R. Q. Snurr, Chem. Rev., 2012, 112, 703–723.
19 S. K. Henninger, H. A. Habib and C. Janiak, J. Am. Chem. Soc., 2009,
131, 2776ꢀ2777; G. Akiyama, R. Matsuda and S. Kitagawa, Chem.
Lett., 2010, 39, 360ꢀ361; S. K. Henninger, F. Jeremias, H. Kummer
and C. Janiak, Eur. J. Inorg. Chem., 2012, 2625ꢀ2634; Y.ꢀK. Seo, J.
W. Yoon, J. S. Lee, Y. K. Hwang, C.ꢀH. Jun, J.ꢀS. Chang, S. Wuttke,
P. Bazin, A. Vimont, M. Daturi, S. Bourrelly, P. L. Llewellyn, P.
Horcajada, C. Serre and G. Férey, Adv. Mater., 2012, 24, 806ꢀ810; G.
Akiyama, R. Matsuda, H. Sato, A. Hori, T. Takata and S. Kitagawa,
Micropor. Mesopor. Mater., 2012, 157, 89ꢀ93; F. Jeremias, A.
Khutia, S. K. Henninger and C. Janiak, J. Mater. Chem., 2012, 22,
10148ꢀ10151.
20 M. Fischer, M. Sartor and M. Fröba, Nachr. Chemie, 2010, 58, 1003ꢀ
1007; S. Ma, D. Sun, M. Ambrogio, J. A. Fillinger, S. Parkin and H.
C. Zhou, J. Am. Chem. Soc., 2007, 129, 1858; J.ꢀR. Li, J. Sculley and
H.ꢀC. Zhou, Chem. Rev., 2012, 112, 869–932.
21 J.ꢀR. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H.ꢀK. Jeong, P. B.
Balbuena and H.ꢀC. Zhou, Coord. Chem. Rev., 2011, 255, 1791–
1823.
Acknowledgements
IB would like to express his sincere gratitude to the Alexander
von Humboldt foundation for the postdoctoral fellowship
40 (1135450 STP). We thank Dr. P. Mayer (Dpt. Chemie, Ludwigꢀ
MaximiliansꢀUniversität München, Germany) and Dr. Alexandra
Griffin (Agilent Technologies, Oxford, UK) for their efforts in
collecting preliminary data for 1. Part of this work was funded by
DFG grant Ja466/25ꢀ1.
45 Notes and references
a Institut für Anorganische Chemie und Strukturchemie, HeinrichꢀHeine
Universität Düsseldorf, Universitätsstraße 1, Dꢀ40225 Düsseldorf,
Germany. Email: janiak@uniꢀduesseldorf.de
b Inorganic Chemistry Department, Taras Schevchenko National
50 University of Kiev, Volodymyrska Street 64, Kyiv 01033, Ukraine. Email:
dk@univ.kiev.ua
c Institut für Physikalische Chemie und Elektrochemie, Technische
Universität Dresden, Mommsenstr. 13, Dꢀ01062 Dresden, Germany.
Email: igor.baburin@chemie.tuꢀdresden.de
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7

CrystEngComm
Page 8 of 10
View Article Online
22 H. B. Tanh Jeazet, C. Staudt and C. Janiak, Dalton Trans., 2012, 41, in
press. http://dx.doi.org/10.1039/C2DT31550E; K. Hunger, N.
Schmeling, H. B. Tanh Jeazet, C. Janiak, C. Staudt and K.
Kleinermanns, Membranes, 2012, 2, 727ꢀ763; H. B. Tanh Jeazet, C.
Staudt and C. Janiak, Chem. Commun., 2012, 48, 2140ꢀ2142.
23 J. Reboul, S. Furukawa, N. Horike, M. Tsotsalas, K.Hirai, H. Uehara,
M. Kondo, N. Louvain, O. Sakata and S. Kitagawa, Nat. Mater.,
2012, 11, 717–723.
24 G. Férey, Chem. Soc. Rev., 2008, 37, 191ꢀ214; P. Horcajada, R. Gref,
T. Baati, P. K. Allan, G. Maurin, P. Couvreur, G. Férey, R. E. Morris
and C. Serre, Chem. Rev., 2012, 112, 1232–1268.
25 M. R. Lohe, K. Gedrich,T. Freudenberg, E. Kockrick,T. Dellmann and
S. Kaskel, Chem. Commun., 2011, 47, 3075–3077.
49 G. K. H. Shimizu, R. Vaidhyananthan and J. M. Taylor, Chem. Soc.
Rev., 2009, 38, 1430ꢀ1449.
50 A. H. M. Jared, M. Taylor and G. K. H. Shimizu, Angew. Chem. Int.
Ed., 2007, 46, 795ꢀ798.
51 D. J. Hoffart, S. A. Dalrymple, G. K. H. Shimizu, Inorg. Chem. 2005,
44, 8868ꢀ8875; D. J. Hoffart, A. P. Cote, G. K. H. Shimizu, Inorg.
Chem. 2003, 42, 8603ꢀ8605.
52 C. B. Caputo, V. N. Vukotic, N. M. Sirizzotti and S. J. Loeb, Chem.
Commun., 2011, 47, 8545ꢀ8547.
53 C. R. Tan, S. H. Yang, N. R. Champness, X. A. Lin, A. J. Blake, W.
Lewis and M. Schröder, Chem. Commun., 2011, 47, 4487.
54 M. Dinca, A. Dailly and J. R. Long, Chem.ꢀEur. J., 2008, 14, 10280.
55 APEX2 2011.3 (Bruker AXS Inc., 2011).
26 G. J. Halder, C. J. Kepert, B. Moubaraki, K. S. Murray and J. D.
Cashion, Science, 2002, 298, 1762; A. Bétard and R. A. Fischer,
Chem. Rev., 2012, 112, 1055–1083.
56 A. L. Spek, J. Appl. Cryst., 2003, 36, 7ꢀ13. PLATON – A Multipurpose
Crystallographic Tool, Utrecht University, Utrecht, The Netherlands,
A.L. Spek (2008); Windows implementation: L.J. Farrugia,
University of Glasgow, Scotland, Version 40608 (2008).
57 V. R. Reichert and L. J. Mathias, Macromolecules, 1994, 27, 7015.
58 H. Newman, Synthesis, 1972, 692.
59 S. T. Meek, J. A. Greathouse and M. D. Allendorf, Adv. Mater., 2011,
23, 249.
60 E. Q. Gao, N. Liu, A. L. Cheng and S. Gao, Chem. Commun., 2007,
2470.
27 Y. Takashima, V. M. Martínez, S. Furukawa, M. Kondo, S.
Shimomura, H. Uehara, M. Nakahama, K. Sugimoto and S.
Kitagawa, Nat. Commun., 2011, 2:168, doi:10.1038/ncomms1170.
28 J.ꢀY. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J.
T. Hupp, Chem. Soc. Rev., 2009, 38, 1450ꢀ1459; L. Ma, C. Abney
and W. Lin, Chem. Soc. Rev., 2009, 38, 1248ꢀ1256; D. Farrusseng, S.
Aguado and C. Pinel, Angew. Chem. Int. Ed., 2009, 48, 7502ꢀ7513;
M. Yoon, R. Srirambalaji and K. Kim, Chem. Rev., 2012, 112, 1196ꢀ
1231.
61 N. Liu, Q. Yue, Y. Q. Wang, A. L. Cheng and E. Q. Gao, Dalton
Trans., 2008, 4621.
29 M. Meilikhov, K. Yusenko, D. Esken, S. Turner, G. Van Tendeloo and
R. A. Fischer, Eur. J. Inorg. Chem., 2010, 3701ꢀ3714.
62 M. O'Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi, Acc.
Chem. Res., 2008, 41, 1782ꢀ1789; the three letter symbols, proposed
by M. O’Keeffe, can be retrieved with examples and further
information from the Reticular Chemistry Structure Resource
database, http://rcsr.anu.edu.au/.
30 P. Falcaro, A. J. Hill, K. M. Nairn, J. Jasieniak, J. I. Mardel, T. J.
Bastow, S. C. Mayo, M. Gimona, D. Gomez, H. J. Whitfield, R.
Riccò, A. Patelli, B. Marmiroli, H. Amenitsch, T. Colson, L.
Villanova and D. Buso, Nat. Commun., 2011, 2:237,
doi:10.1038/ncomms1234.
63 M. Dinca, A. F. Yu and J. R. Long, J. Am. Chem. Soc., 2006, 128,
8904.
31 T. Uemura, N. Yanai and S. Kitagawa, Chem. Soc. Rev., 2009, 38,
1228ꢀ1236.
32 C. M. Doherty, E. Knystautas, D. Buso, L. Villanova, K. Konstas, A.
J. Hill, M. Takahashif and P. Falcaro, J. Mater. Chem., 2012, 22,
11470–11474.
64 T. W. Wang, D. S. Liu, C. C. Huang, Y. Sui, X. H. Huang, J. Z. Chen
and X. Z. You, Cryst. Growth Des., 2010, 10, 3429.
65 V. A. Blatov, M. O'Keeffe and D. M. Proserpio, CrystEngComm,
2010, 12, 44ꢀ48.
66 S. Q. Su, C. Qin, S. Y. Song, Z. Y. Guo, R. P. Deng, W. Chen, X. Z.
Song, S. Wang, G. H. Li and H. J. Zhang, CrystEngComm, 2011, 13,
6057.
33 K. Zagorodniy, G. Seifert and H. Hermann, Appl. Phys. Lett., 2010,
97, 251905 (1ꢀ2).
34 M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem.
Soc. Rev., 2009, 38, 1330ꢀ1352; Y. Cui, Y. Yue, G. Qian and B.
Chen, Chem. Rev., 2012, 112, 1126–1162.
67 The nets reported in ref. 66 and 69 are indeed albꢀ4,8ꢀCmce and not
‘(4,8)ꢀconnected alb’ as stated in the title. The alb net is (6,12)ꢀ
connected.
35 O. R. Evans and W. Lin, Acc. Chem. Res., 2002, 35, 511ꢀ522; C.
Wang, T. Zhang and W. Lin, Chem. Rev., 2012, 112, 1084ꢀ1104.
36 M. Kurmoo, Chem. Soc. Rev., 2009, 38, 1353ꢀ1379.
68 Z.ꢀY. Du, H.ꢀB. Xu and J.ꢀG. Mao, Inorg. Chem., 2006, 45, 6424.
69 R. Ma, C. Chen, B. Sun, X. Zhao and N. Zhang, Inorg. Chem.
Commun., 2011, 14, 1532ꢀ1536.
37
I. Boldog, L. Xing, A. Schulz and C. Janiak, Comptes rendus chimie,
70 O. DelgadoꢀFriedrichs and M. O'Keeffe, Acta Cryst., Sect. A, 2003, 59,
2012, 15, 866ꢀ877.
351ꢀ360;
(see
the
software
implementation
on
38 R. Robson, Dalton Trans., 2000, 3735.
http://gavrog.sourceforge.net/)
39 O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi
and J. Kim, Nature, 2003, 423, 705.
71 O. DelgadoꢀFriedrichs and M. O'Keeffe, Acta Cryst., 2007, A63, 344–
347.
40 N. W. Ockwig, O. DelgadoꢀFriedrichs, M. O'Keeffe and O. M. Yaghi,
Acc. Chem. Res., 2005, 38, 176ꢀ182.
41 H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi, A. O.
Yazaydin, R. Q. Snurr, M. O'Keeffe, J. Kim and O. M. Yaghi,
Science, 329, 424.
42 Y. E. Cheon and M. P. Suh, Chem. Commun., 2009, 2296ꢀ2298.
43 H. Chun, D. Kim, D. N. Dybtsev and K. Kim, Angew. Chem. Int. Ed.,
2004, 43, 971ꢀ974.
72 E. V. Alexandrov, V. A. Blatov, A. V. Kochetkov and D. M.
Proserpio, CrystEngComm, 2011, 13, 3947ꢀ3958; V. A. Blatov and
D. M. Proserpio, Acta Cryst., 2009, A65, 202ꢀ212; V. A. Blatov,
IUCr
(http://www.iucr.org/iucrꢀtop/comm/ccom/newsletters).
73 H. L. Ngo and W. B. Lin, J. Am. Chem. Soc., 2002, 124, 14298.
Compcomm.
Newsletter,
2006,
7,
4ꢀ38
74 O. R. Evans, H. L. Ngo and W. B. Lin, J. Am. Chem. Soc., 2001, 123,
10395.
44 O. Plietzsch, C. I. Schilling, M. Tolev, M. Nieger, C. Richert, T.
Muller and S. Bräse, Org. Biomol. Chem., 2009, 7, 4734ꢀ4743.
45 L. Q. Ma, A. Jin, Z. G. Xie and W. B. Lin, Angew. Chem Int. Ed.,
2009, 48, 9905.
46 J. Kim, B. Chen, T. M. Reineke, H. Li, M. Eddaoudi, D. B. Moler, M.
O'Keeffe and O. M. Yaghi, J. Am. Chem. Soc., 2001, 123, 8239ꢀ
8247.
47 B. Chen, M. Eddaoudi, T. M. Reineke, J. W. Kampf, M. O'Keeffe and
O. M. Yaghi, J. Am. Chem. Soc., 2000, 122, 11559ꢀ11560.
48 B. F. Hoskins and R. Robson, J. Am. Chem. Soc., 1990, 112, 1546.
75 J. Plutnar, J. Rohovec, J. Kotek, Z. Zak and I. Lukes, Inorg. Chim.
Acta, 2002, 335, 27.
76 A. Clearfield, Curr. Op. in Solid State Mat. Science, 2002, 6, 495.
77 O. K. Farha and J. T. Hupp, Acc. Chem. Res., 2010, 43, 1166.
78 R. Herchel, D. Novosad and Z. Travnicek, Polyhedron, 2012, 42, 50ꢀ
56
79 Q. X. Jia, X. B. Qian, H. H. Wu, Q. L. Wang and E. Q. Gao, Inorg.
Chim. Acta, 2009, 362, 2213ꢀ2216
80 Y. B. Lu, M. S. Wang, W. W. Zhou, G. Xu, G. C. Guo and J. S.
Huang, Inorg. Chem., 2008, 47, 8935ꢀ8942.
8
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 9 of 10
CrystEngComm
View Article Online
81 O. Kahn, Molecular Magnetism, VCH, New York, 1993.
82 J. J. BorrásꢀAlmenar, J. M. ClementeꢀJuan, E. Coronado and B. S.
Tsukerblat, J. Comput. Chem., 2001, 22, 985.
83 X.ꢀL. Tong, T.ꢀL. Hu, J.ꢀP. Zhao, Y.ꢀK. Wang, H. Zhang and X.ꢀH.
Bu, Chem. Commun., 2010, 46, 8543ꢀ8545.
84 M. E. Fisher, Am. J. Phys., 1964, 32, 343.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 9

CrystEngComm
Page 10 of 10
View Article Online
Graphical Abstract
A rare alb-4,8-Cmce metal-coordination network based on
tetrazolate and phosphonate functionalized 1,3,5,7-
tetraphenyladamantane
Ishtvan Boldog,a Konstantin Domasevitch,*b Igor A. Baburin,*c Holger Ott,d Beatriz Gil-
Hernández,e Joaquín Sanchiz,*e Christoph Janiak*a
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Coincidence? Two different elongated adamantane-based ligands 'imprint' the same rare
network topology with different metal secondary building units.