Journal of Molecular Structure 1119 (2016) 205e211

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Tin-porphyrin-assisted formation of coordination frameworks

Hatem M. Titi
School of Chemistry, Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat-Aviv, 69978 Tel-Aviv, Israel

a r t i c l e i n f o a b s t r a c t

Article history: Novel 3D networks synthesized by two different methods are reported in this article. Structure 1
Received 2 February 2016 {[CdL2]$(solvent)}n consists of CdII-single metallic nodes held together by coordinated isonicotinate li-
Received in revised form gands (L) to form a 3D chiral framework (P41212). The resulting structure exhibits threefold-
17 April 2016
interpenetrated dia coordination networks. After a few weeks the crystals were re-measured to form
Accepted 26 April 2016
1a {[Cd(L)2(H2O)]$DMF}n with two interpenetrated dia nets which is thermodynamically more stable. On
Available online 28 April 2016
the other hand, the addition of the tin(IV)-porphyrin to the same reaction mixture led to the formation of
3D pseudo-isostructures, based on oxo-centered CdII and MnII/III cluster nodes, 2 {[Cd3(OH)
Keywords:
Tin porphyrins
L4(H2O)3](ClO4)}n and 3 {[Mn3(O)L4(DMF)3](ClO4)}n. These structures represent topologically bcg nets.
Metal-organic frameworks Possible synthetic mechanism was proposed to emphasize the role of the tin(IV)-porphyrin that led to
Secondary building units the construction of oxo-centered trinuclear clusters in 2 and 3.
Topology © 2016 Elsevier B.V. All rights reserved.
Interpenetration

1. Introduction porphyrin-based MOFs have not been obtained in this work.

In the last few decades, metal-organic frameworks (MOFs) have
gained a considerable attention due to their great potential in
various applications [1,2]. MOFs are considered as a class of porous
materials, where the stability lies on the strength of the coordi-
nated ligands to suitable metal-ion nodes. MOFs with poly-nuclear
metal cluster as secondary building unit (SBU) draw further sci-
entific attention because of the fascinating topology of their
structures [3]. Design of new SBUs is important to target robust
open porous framework with predictable topology, and explore
their specific chemical or physical properties. In addition, the use of
poly-nuclear SBUs increases the odds of successful construction of
multidimensional supramolecular architectures [4,5]. In this work
the original intention was to incorporate isonicotinate in the axial
positions into the tin(IV)eporphyrin scaffolds, in order to enhance
the potential to involve more functional sites in the formulation of
new types of coordination polymeric assemblies with different
metal salts. This idea is based on my pervious findings where the
tin(IV)-porphyrin scaffolds were found to be held together through
a series of non-covalent interactions [6,7]. The use of isonicotinic
acid (L) as an axial ligand is particularly attractive, due to its
nonlinear optical properties [8], blue fluorescence and lumines-
cence properties [9]. This simple ditopic ligand is also known to
display different coordination motifs [10]. However, the anticipated
Instead, 3D coordination polymers were formed by direct associa-
tion of Cd- and Mn-ion centers to the L linker (compounds 1e3),
whether or not the (dihydroxy)Tin(IV)-meso-5,10,15,20-tetra-(3-
pyridyl)porphyrin (SnIV(OH)2-T3PyPr) reagent was present in the
reaction mixture (Scheme 1). Reaction of CdII(ClO4)2 with L in DMF/
MeOH solution yielded structure 1, which incorporates mono-
nuclear tetrahedral metallic nodes linked to each other through
the organic ligands. Structural transformation occurred with the
crystals of 1 when left in the mother solution for a few weeks. A
different structure 1a was formed as a result of incorporation of the
DMF molecules into these crystals, where the coordination envi-
ronment around the cadmium centers transformed from tetrahe-
dral (in 1) to trigonal bi-pyramidal (in 1a). When the
supramolecular reaction between L and cadmium perchlorate was
carried out in the presence of SnIV(OH)2-T3PyPr (Scheme 1, path II) a
different 3D coordination framework (2) wherein the organic
ligand is inter-linked via oxo-centered trinuclear cadmium clusters.
Polymeric structure (3) of similar topology was obtained with the
MnII(ClO4)2 reagent. It was found to contain as the inter-ligand
metallic nodes oxo-centered mixed-valence manganese clusters,
characteristic to materials that behave as single-molecule magnets
[11].
2. Experimental section

E-mail address: hat22t@hotmail.com. In all reactions, commercially available reagents of analytical

http://dx.doi.org/10.1016/j.molstruc.2016.04.093
0022-2860/© 2016 Elsevier B.V. All rights reserved.
206 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211
Scheme 1. A schematic representation of the synthetic approach, where paths I and II led to the construction of 3D supramolecular architectures based on either mono-nuclear or
poly-nuclear metallic nodes, respectively.
grade were used without further purification. The FT-IR spectra was
recorded in Bruker Tensor 27 system spectrophotometer in ATR
mode. UVevis spectra was recorded on a Perkin-Elmer UVevis
spectrometer. The synthesis of SnIV(OH)2-T3PyPr was prepared as
detailed in the literature [6]. Complexes 1e3 were prepared as
detailed below.
Compound 1 was synthesized by mixing L (0.024 mmol, 3 mg),
and CdII(ClO4)2$5H2O (0.036 mmol, 12 mg) in 2 mL 1:1 dime-
thylformamide (DMF)emethanol (MeOH) mixture. The mixture
was sealed and heated for 48 h in a bath-reactor at 100
C. After
cooling the compound to room temperature, it yielded colorless
crystals of complex 1, yield 75%. IR (cm1): 1651 (s, nC]O free
asymmetric), 1582 (s, nC]O coordinated asymmetric), 1396 (s, nC]N
aromatic), 1321 (m, nC]O symmetric), 1093, 1061, 1021, 944, 881,
785, 691, 426.
Compound 1a was obtained after a period of few weeks by
leaving the crystals of 1 in the mother solution without disturbance
in dark and ambient conditions.
Compound 2 was prepared also in solvothermal conditions. A
mixture of L (0.024 mmol, 3 mg), SnIV(OH)2-T3PyPr (0.006 mmol,
5 mg) and CdII(ClO4)2$H2O (0.036 mmol, 12 mg) was dissolved in
2 mL of DMF:MeOH (1:1). The reaction mixture was heated for 48 h
in a bath-reactor at 100
C. After subsequent cooling to room
temperature crystals of 2 were obtained, yield 42%. IR (cm1): 3233
(bs,nOeH coordinated water), 1649 (s, nC]O free asymmetric), 1584
(s, nC]O coordinated asymmetric), 1398 (s, nC]N aromatic), 1252
(m, nC]O symmetric), 1091, 1014, 862, 785, 864, 691, 595, 426, 385.
Compound 3 was obtained by replacing the CdII(ClO4)2$H2O
reagent with MnII(ClO4)2$6H2O (0.091 mmol, 33 mg) dissolved
together with the porphyrin material in 2 mL of DMF:MeOH (1:1).
The solution was heated for three days in a bath-reactor at 100
C.
Gradual cooling to ambient conditions yielded dark brown crystals
of 3 (33%). IR (cm1): 3464 (bs,nOeH coordinated water), 1668 (s,
nC]O free asymmetric), 1603 (s, nC]O coordinated asymmetric),
1410 (s, nC]N aromatic), 1308 (m, nC]O symmetric), 1064, 933, 789,
944, 708, 689, 494, 390.
2.1. Crystal structures determination
Single crystal measurements for compounds 1e3 were collected
at 110 (2) K, using Bruker's Apex-Duo diffractometer with MoKa
(l ¼ 071075 Å) radiation. Crystal structures were solved by direct
methods and refined by full matrix least squares (SHELXT-2014 and
SHELXL-2014) [12,13]. The crystallographic and experimental data
for 1e3 are given in Table 1. All the non-hydrogen atoms were
refined anisotropically except for the disordered oxygen atoms of
the ClO4 anions in 2 and 3. The hydrogen atoms were located in
calculated sites and were refined using a riding model. The intra-
lattice voids in 1 and 2 were found to contain disordered solvent
molecules which couldn't be reliably modeled by discrete atoms.
Therefore, their contribution was subtracted from the diffraction
pattern by the SQUEEZE technique in the PLATON software [14].
Despite the apparent disorder of the perchlorate anions and of the
water solvent, the crystallographic evaluations afforded models of
the coordinated networks of good precision. Structures 1e3 were
refined as inversion twins.
3. Results and discussion
3.1. Crystal structure description
Compound 1 [CdL2]n$(solvent) contains one organic linker in its
deprotonated state (L) and tetrahedral CdII ion centers (located on
special positions) in the asymmetric unit. The crystal structure in
characterized by a chiral tetragonal space group P41212, and it
represents a 3D coordination network (Fig. 1). This reaction was
carried out without the involvement of the tin(IV)-porphyrin
component in the reaction mixture. In 1 four organic linkers were
found coordinated to the CdII centers through the carboxylate and
pyridyl ligating positions. The carboxylate functions are bound in
an asymmetric chelating mode, occupying two sites of the tetra-
hedral Cd-environment. The other two positions are coordinated to
the N-atoms of the pyridyl functions of other ligands. The resulting
coordination distance ranges are CdIIeO ¼ 2.272(6)e2.421(7) Å,
and CdIIeN ¼ 2.289(7) e2.290(7) Å. The topology of the polymeric
 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211 207

architecture can be defined by the node-and-linker terminology

21  h  20, 15  k  15, 24  l  24

[15]. Thus, 1 demonstrates a 3-fold interpenetration of the coor-
dination frameworks, showing very common 3D dia net charac-
teristics. The interpenetrated architecture still contains one-
dimensional channel voids that propagate along the c-axis of the
crystal lattice. These solvent accessible pores account for 32%

R1 ¼ 0.0622, wR2 ¼ 0.1670

R1 ¼ 0.0657, wR2 ¼ 0.1704
(514.29 Å) of the crystal volume (as assessed by PLATON [14]),
being accommodated by severely disordered molecules of the
C33H37ClMn3 N7O16

crystallization solvent.

2.364 and 1.086

When crystals of 1 were left in the mother liquor without

8350/185/546
2.015e26.372
Compound 3

90.8540(18)

creating any disturbance for a number of weeks, interesting

Monoclinic

17.3880(7)
12.4180(5)
19.7091(7)

4255.2(3)

changes in the crystal structure were observed, yielding com-

987.96

0.0296
18267
1.542
1.015

1.135
2016

8350
7827
pound 1a reported (though independently re-determined by this
C2

90

90

author) previously [16]. The crystal structure of 1a reveals also dia-

type networking. However, it involves incorporation of one water
26  h  16, 24  k  22, 16  l  15
moiety in the coordination sphere (which is now characterized by
trigonal bipyramidal geometry) of the metal ion, and reduction of
the degree of interpenetration from 3 to 2 (Fig. 2). One may
tentatively conclude that compound 1 represents a kinetically-

R1 ¼ 0.0509, wR2 ¼ 0.1350

R1 ¼ 0.0526, wR2 ¼ 0.1370
controlled product of the reaction.
Additional experiments were carried out using similar syn-
thetic procedures modified by addition of SnIV(OH)2-T3PyPr to the
C24H17Cd3Cl N4O16

2.115 and 1.384 reaction mixture. Either CdII(ClO4)2 or MnII(ClO4)2 reagents were
Orthorhombic

1.966e28.405

used in this effort, yielding new coordination frameworks 2 and 3,

Compound 2

5326/30/222
18.1754(15)
12.6085(13)

respectively, with no incorporation of the porphyrin scaffolds into

19.707(2)

4516.1(8)
990.06

0.0948
19622

the polymeric architectures. The two compounds are pseudo-

Ama2

1.456
1.515

1.061
1912

5326
5120

isostructural, where the coordination connectivity of the frame-

90
90
90

works remains nearly the same; but different ligands from the
14  h  16, 20  k  12, 25  l  16

solvent coordinate to the metal ion centers (water in 2 and DMF in

3). In 2 as well as in 3 oxo-centered trinuclear metallic clusters
serve as the SBUs that inter-connect the organic ligands.
Compound 2 {[Cd3(OH)L4(H2O)3](ClO4)}n crystallizes in ortho-
rhombic space group Ama2. It represents a 3D coordination
R1 ¼ 0.0333, wR2 ¼ 0.0934
R1 ¼ 0.0369, wR2 ¼ 0.0957

framework supported by trinuclear Cd3 clusters. Two of the Cd-

ions are crystallographically independent and have different co-
ordination environments. A mirror plane is crossing the trinuclear
1.269 and 0.587

cluster through the hydroxyl-ligand and divides it to two halves.

C15H17CdN3O6

Orthorhombic
Compound 1a

2.161e28.406

The coordination patterns around the two ions CdII-1 and CdII-2
12.2463(14)
15.4577(18)
18.8454(19)

4454/0/229
3567.4(7)

exhibit distorted octahedral geometries. The coordination sites on

447.71

0.0238
18677
1.667
1.260

1.055

CdII-1 ions (located on a special position) are occupied by the N-

1792

4454
4076
Pbca

90
90
90

atoms of two cis-related pyridyl linkers, two carboxylates of other

8

linkers, one water ligand, and the hydroxido bridging moiety. The
14  h  19, 19  k  13, 8  l  5

coordination positions of the symmetry-related CdII-2 atoms in the

cluster are surrounded by three carboxylates, a coordinated water
Crystallographic details and refinement parameters of compounds 1e3.

entity, the bridging hydroxido, and a pyridyl N-atom of another

organic linker. The four organic linkers are coordinated to the
R1 ¼ 0.0294, wR2 ¼ 0.0826
R1 ¼ 0.0299, wR2 ¼ 0.0829

metallic cluster through the carboxylate functions in a bidentate

bridging mode, along with four ligands coordinated to the cluster
through the N-atoms of the pyridyls (Fig. 3). The corresponding
0.625 and 0.809

bond distances are within CdeO ¼ 2.250(7)-2.330(7) Å and

2.965e26.347
Compounds 1

C12H8CdN2O4

1607.99(14)

CdeN ¼ 2.320(8)-2.413(12) Å. The hydroxido-bridging moiety lies

1641/51/88
15.3622(6)
15.3622(6)
Tetragonal

6.8136(3)

0.61 Å above the plane defined by the three metal ions. The tri-
P41212
356.60

0.0252
1.473
1.366

1.102
7101
1641
1616

nuclear clusters are further cross-linked in lateral directions to six

696
90
90
90

neighboring clusters through the organic ligands (Fig. 3b). Addi-

tional axially oriented linkers connect between the metallic nodes
Largest diff. peak and hole (e.Å3)

in a perpendicular direction, yielding a 3D coordination frame-

q range for data collection (
)

work. The generated cavities within the framework architecture

Data/restraints/parameters

are occupied by the perchlorate anions (located on, and rotation-

Final R indices [I>2s(I)]
Goodness-of-fit on F2

ally disordered about, the twofold rotation axes).

Reflections collected

R indices (all data)

Reflections I>2s(I)
Unique reflections

Recently, Yang and co-workers reported a trinuclear Cd3-clus-

Formula weight

r (calc) Mg/m3
Crystal system

ter-assembled frameworks engaged by isonicotinate connectors

Index ranges
Volume (Å3)
Space group

[17]. That structure was described as 9-connected ncd net with

m (mm1)
Formula

F (000)

paddlewheel trinuclear cluster connectors, without the presence

R(int)
Table 1

b (Å)
a (Å)

c (Å)

b (
)
g (
)
a (
)

of any bridging species between the metallic atoms within the

Z

cluster. It was obtained as a result of single crystal to single crystal

208 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211

Fig. 1. Compound 1 exhibits a 3D coordination framework with tetrahedral nodes (top right). The simplified node-and-linker network is shown in the top-left corner. The crystal
structure reveal three-fold interpenetration of such networks (bottom left; the individual nets are depicted in green, blue and brown colors). View of intra-lattice channel voids
down the c-axis is shown at the bottom-right corner.

transformation. Yang et al. firstly prepared a 3D coordination
network [a (3,6)-connected rtl net] with single CdII metallic nodes
engaged with the organic molecules in DMF solution, which after
heating transformed into the ncd coordination framework [17]. The
use of the SnIV-porphyrin mediators generated in the present case
trinuclear SBUs held together by the hydroxido-bridge as shown
above.
Replacement the cadmium salt with its manganese analogue in
similar experimental conditions led to the formation of compound
3 {[Mn3(O)L4(DMF)3](ClO4)}n It crystallizes in monoclinic space
group C2 and reveals similarly interconnected 3D coordination
framework as in 2. The oxo-centered three-nuclear Mn-clusters
possess two different coordination surroundings on the individ-
ual metal ion centers of þ2 and 3 oxidation states. The oxo-bridge is
located 0.53 Å above the plane of the three manganese ions of the
cluster. The 3D framework architecture in 3 is similar to that
observed in the previous example (Fig. 3b), with metal-bound DMF
ligands replacing the water ligands in 2. The corresponding coor-
dination distances in 3 are within MnII/III-O ¼ 2.126(4)-2.234 (4) Å
and MnII/III-N ¼ 2.268(5)-2.361(5) Å. Frameworks 2 and 3 can be
described as 8-connected uninodal nets from the topological family
of bcg with point symbol of {36$414$57$6}. The generated networks
consist of distorted hexagonal wave-like 2D sheets connected to
each other through additional axial linkers into 3D frameworks
(Fig. 4a). Fig. 4b shows a schematic representation of the bcgenet as
a particular subnet of 12-connected fcu net, where the broken red
dashed lines present the missing linkers that would convert the bcg
net into a fcu net [18]. Huang and co-workers described the in situ

Fig. 2. Structural transformation of the 3-fold interpenetrated network in 1 (left) to 2-fold interpenetrated network in 1a [16] (right).
 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211 209

Fig. 3. (a) The trinuclear SBUs observed in structures 2 and 3. (b) The crystal packing in 2 (viewed parallel to b-axis) and 3 (a view down of b-axis). The red spheres depict solvent
molecules of water and DMF, while the gold spheres represent the CdII and MnII/III ion centers. Hydrogen atoms and disordered perchlorate anions are omitted for clarity.

Fig. 4. (a) A topological representation of 2 and 3 shows a bcg net (left) and its distorted hex-like net projection when viewed from the top (right). (b) Schematic illustration of the
relationship between the common fcu net and its subnet bcg, where the dashed red lines depict the “missing” connecting linkers in the bcg net.

synthesis of halogen-centered CdII-trinuclear clusters bound
through L ligands by using ionic liquids [19]. The structure exhibits
also a bcg type coordination network, however, the synthesis of this
compounds required aggressive conditions including heating for 6
days at 160
C. In this network the metallic cluster contains three
open sites occupied by 4-methylpyridine, decreasing the possibility
to expand the coordination scheme into a fcu net.
TOPOS Topological Database (TTD) reveals the existence of 18
identified crystal structures that represent the bcg networking
pattern [20]. In addition, we calculated the tiles generated in this
topological net [21]. The network structure exhibits a natural tiling
in the repeat unit with 2 nodes and 8 edges, and it can be repre-
sented as [34$44] with a symmetry of Cccm. The system displays a
high symmetry of dualized natural tiling (not a self-dual) with hex
arrangement having only one kind of tiles [34$44], as shown in
Fig. 5.
The Cambridge Crystallographic database (CCDC, ConQuest
Version 1.18, 2015) contains thousands of entries involving com-
plexes of isonicotinate derivatives with various d and f-shell metal
ions. Due to the high number of entries the search was limited to
structures contain L¡1 only; in which the N-atoms are engaged
with single coordination bond and the carboxylate function with
various coordination modes. The ligand shows the existence of 205
structures coordinated through monodentate h1-mode, and 143
entries are engaged in symmetric and asymmetric chelating h2-
fashion. However, a large number of structures adopt the binding
modes of m2-h1:h1 and m3-h1:h2 (combined 513), while the bridging
modes of m3-h1:h2:h1 demonstrates the lowest entries with four
structures only. The results have shown the high tendency of the
L¡1 to form multidimensional structures, even in low binding
modes, when both of the functional sites are involved. Therefore,
the driving force to generate 1D, 2D and 3D solid-state structures,
with attractive supramolecular architectures is based on incorpo-
ration of both isonicotinate functionalities with suitable cation with
affinity for both N- and O-atoms [17,22]. for example, Chen and co-
workers reported 3D networks of Co and Ni based porous materials,
in which the L¡1 is involved in three different carboxylate coordi-
nation modes like h1, m2-h1:h1 and m3-h1:h2 [22b]. In this case the
N-atom of the pyridine ring is also coordinated to metal ion centers.
On the other hand, Huang and co-workers performed the reactions
210 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211
Fig. 5. Natural tiling in the bcg net, and the dualizing tiling of the natural tile [21].
with lanthanide ions (Ln) in the presence of silver nitrate to form
2D layers. The carboxylate coordination fashions are adopt h1 and
m2-h1:h1. The use of the silver cations is to construct additional
direction due to the lower affinity of Ln towards N-atoms [22c].
Compounds 1e3 have been characterized also by IR-
spectroscopy. Their CeO groups exhibit stretching absorptions in
the region of 1582e1603 cm1 that correspond to the coordinated
asymmetric bonds to metal centers, while the symmetric stretches
are falling in the range of 1321e1252 cm1. On the other hand, the
stretching vibrations at the 1396-1410 cm1 are related to the
stretching absorption of C]N bonds of the pyridine rings. In
compound 2 the OeH vibration stretch 3233 cm1 corresponds to
the coordinated water ligands, while the hydroxido-bridge fre-
quency is located at 862 cm1. The vibration peak of the oxo-bridge
in compound 3 is located at 689 cm1 [23].
3.2. Mechanistic aspects of the synthetic protocol
The different products 1 and 2 obtained in the reaction between
cadmium perchlorate and isonicotinic acid in the absence or
presence of SnIV(OH)2-T3PyPr indicate that the porphyrin entity can
play an important role in the synthesis of the coordination poly-
meric assembly. Correspondingly, we propose hereby a possible
reaction mechanism that involves the porphyrin mediator and
Scheme 2. The proposed cyclic mechanism involving the tin(IV)-porphyrin as reactive
intermediate in the syntheses of 2 and 3.
yields structures 2 (instead of 1 in the absence of the porphyrin)
and 3 (Scheme 2). In solution, the tin(IV)-porphyrin bound to axial
ligands exists in equilibrium with dissociated charge-separated
porphyrin and ligand entities [24]. This reaction equilibrium facil-
itates the replacement of the hydroxyl ligands by other active oxo-
ligands (as e.g. the carboxylate anions) present in the reaction
mixture [25]. In addition, the hydroxyl ligands replaces the acid and
base addition to the mixture, in order to maintain the pH in the
reaction as previously reported by Goldberg and co-workers [26].
The first reaction in the proposed mechanism is thus the axial
ligand replacement, where the porphyrin exchanges the hydroxyls
with carboxylate ligands by releasing water molecules. Binding
mechanism of carboxylic ligands to the tin(IV)-porphyrins has been
proposed by Sanders et al. [27] The occurrence of equilibrium be-
tween binding state to charge separation state generates a reactive
carboxylate functions, which coordinate readily to the oxophilic
transition metal center, forming the ML2 complex. The cyclic re-
action process is completed by recombination of the positively
charged [SnIV-T3PyPr]2þ intermediates with the hydroxyl anions to
SnIV(OH)2-T3PyPr. The hydroxyls are also the source for the oxo-
bridges incorporated into the trinuclear metallic clusters.
The final reaction step involves two ML2 molecules that react
with an additional MII ion in the presence of Sn(OH)2-T3PyPr, to
result in the formation of the M3L4 assembly observed in 2 and 3
(Scheme 3).
Additional experiments to synthesize coordination frameworks
with different tin(IV)-tetra-substituted aryl porphyrins have been
carried out but led to unpredictable results. For example an attempt
to react the isonicotinic acid with CuII ion centers in the presence of
SnIV(OH)2-T4PyPr moieties, resulted also in the formation of a 3D
porphyrin-based framework reported elsewhere [28]. Similar re-
actions of cadmium salts with the isonicotinate ligand L in the
presence of either SnIV(OH)2-T4PyPr scaffolds yielded different co-
ordination patterns, with the CdII ions linked simultaneously to
both L and the porphyrin [29]. Additional efforts with tetraphenyl
(instead of tetrapyridyl) porphyrins, cadmium ions and isonicotinic
acid yielded unidentified amorphous precipitates. It appears that
the substituted 3-pyridyl arms in Sn(OH)2-T3PyPr are relatively
reluctant to coordination with metal centers especially in the
presence of competitive linker. As a result these porphyrins are not
involved in coordination to the metal centers in the above
Scheme 3. The overall reaction mediated by the porphyrin moiety.
 H.M. Titi / Journal of Molecular Structure 1119 (2016) 205e211 211

1e3 and 1a CCDC 1451401e1451404 for complexes 1e3 and 1a.

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