Hydrogen bonding interactions and supramolecular networks of pyridine-aryl based thiosemicarbazides and their Zn(II) complexes

Article abstract of DOI:10.1039/c2ce26718g

The synthesis of five pyridyl derived thiosemicarbazides, 1-5, is presented. All five were formed in a single step from 2-hydrazinopyridine with commercially available isothiocyanates using microwave assisted synthesis. Compounds 1-4 were structurally characterised by single crystal diffraction analysis, and showed extended supramolecular hydrogen bonding arrays. Furthermore, the Zn(ii) complexes 6 and 7 have been prepared using ligands 1 and 5, and structurally characterised, again showing elegant assemblies of metal-supramolecular structures with solvent accessible channels, demonstrating that these building units are excellent candidates for use in supramolecular chemistry and crystal engineering.

Full text of DOI:10.1039/c2ce26718g

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Hydrogen bonding interactions and supramolecular networks of
pyridine-aryl based thiosemicarbazides and their Zn(II) complexes
Komala Pandurangan, Jonathan A. Kitchen, Thomas McCabe and Thorfinnur Gunnlaugsson*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
The synthesis of five pyridyl derived thiosemicarbazides, 1-5, is presented. All five were formed in a single step from 2ꢀ
hydrazinopyridine with commercially available isothiocyanates using microwave assisted synthesis. Compounds 1-4 were structurally
characterised by single crystal diffraction analysis, and showed extended supramolecular hydrogen bonding arrays. Furthermore, the
Zn(II) complexes 6 and 7 have been prepared using ligands 1 and 5, and structurally characterised, again showing elegant assemblies of
10 metalꢀsupramolecular structures with solvent assessible channels, demonstrating that these building units are excellent candidates for use
in supramolecular chemistry and crystal engineering.
designed various families of amidoꢀthiourea16 and
Introduction
thiosemicarbazide based structures. Herein, we present the
50 results from the structural investigations of the
thiosemicarbazide based structures 1-5, Scheme 1. These are
formed by condensing 2ꢀhydrazinopyridine with various
isothiocyanates, giving rise to pyridine structures that have the
potential to generate ordered hydrogen bonded supramolecular
55 structures; but to our surprise, their use in crystal engineering
and supramolecular chemistry in general, has received limited
attention to date.17 Thiosemicarbazides have been used to
generate coordination networks using transition metal ions in
the past,18ꢀ22 most notably by Burrow et al.18ꢀ20 Given that 1-5
60 all possess one or more pyridine ligands, we extended our
investigation into studying the complexation of 1-5 with
transition metal ions; with the view of capitalising on the dual
functionality of these structures.23 Hence, we also report herein,
the structural characterisation of two such Zn(II) complexes,
65 where the combination of metal coordination and hydrogen
bonding results in extensive supramolecular networks,
possessing porous channels.
The investigation of selfꢀassembly processes in supramolecular
chemistry and crystal engineering between ‘purely’ organic
15 molecules (i.e. not metal directed systems such as in MOFS)
has become an active area of research in recent times.1 Such
systems rely mainly on short contact van der Waals, hydrogen
bonding,2 πꢀπ interactions,3 as well as CꢀHꢀꢀꢀπ interctions.4
The interactions between hydrogen bonding donors and organic
20 anions has also been explored for the formation of such selfꢀ
assembly systems.5 Hydrogen bonding is
a particularly
powerful building motif for use in crystal engineering6 and a
great variety of hydrogen bonding donors/acceptors exists,
making them a particularly good choice for the construction of
25 selfꢀassemblies. Hydrogen bonds provide unique directionality,
they are usually easily introduced into structures and their
numbers can be varied through simple design; all of which can
facilitate the formation of highly stable hostꢀguest complexes
(or conjugates) as recently demonstrated by Leigh and Hunter,
30 et al.7a using arrays of four/ hydrogen bonding
donors/acceptors within single aromatic structures.7 Functional
groups such as amines, amides, ureas and thioureas,8ꢀ12 have all
been explored as hydrogen bonding donors in this manner. In
the past, we have investigated their use in the development of
35 charge neutral receptors for anions.13,14 As part of this work, we
developed thiosemicarbazide and semicarbazide based 1,8ꢀ
naphthlimide structures5c and showed that these were excellent
luminescent and colorimetric sensors for anions in buffered
aqueous or organic solutions.15 Of these structures, the
40 thiosemicarbazides also gave rise to highly ordered honeycomb
solid state structures, formed through hydrogen bonding
interactions and weak F….F bonds, that were porous, with
channels filled with disordered counter ions and solvent
molecules. With the view of extending our investigation into
45 the use of such charge neutral hydrogen bonding motifs in
anion recognition, sensing and as potential novel building
blocks for the generation of networks and polymers, we have
Results and Discussion
70 Synthesis of 1-5
Thiosemicarbazides 1-5 were synthesised by reacting
equimolar ratios of 2ꢀhydrazinoꢀpyridine and substituted
isothiocyanates; 4ꢀnitrophenyl (1), 4ꢀfluorophenyl (2), 2,6ꢀ
dimethylphenyl (3), 3ꢀpyridyl (4) and 4ꢀtrifluoromethylꢀphenyl
Scheme 1: Synthesis of compounds 1-5 used in the current study.
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(5), in acetonitrile under microwave irradiation (Scheme 1). 1
was isolated as a yellow powder while 2-5 were colourless
powders. All compounds were fully characterised using
standard analytical techniques (see experimental section). In
addition, Xꢀray quality single crystals were obtained of 1–4 and
the low temperature (106(2) – 133(2) K) Xꢀray structures
determined. Unfortunately despite many attempts utilising
different solvents, solvent mixtures and crystallisation methods,
Xꢀray quality crystals of 5 were not obtained; but its structural
5
10 connectivity was later demined as part of a Zn(II) complex (7).
Structural Analysis of 1-4
Single crystals of 1-4 were grown by the slow evaporation of
acetonitrile at 6ꢀ 12°C and resulted in large block like crystals
15 of 1 (red), 2 (colourless), and 3 (colourless) and large yellow
plates of 4 (Table 1). Compound 1 crystallised in the chiral
monoclinic space group Pc and contained one molecule in the
asymmetric unit; compound 2 crystallised in the triclinic space
group Pꢀ1 and contained two molecules in the asymmetric unit;
20 compound 3 crystallised in the chiral orthorhombic space group
Pbca with one molecule in the asymmetric unit; and compound
4 crystallised in the chiral monoclinic spacegroup P21 and
contained two molecules in the asymmetric unit. The structures
were all crystallised under the same conditions, contained no
Fig 2. View of Hꢀbonding in thiourea 1. (N(3)ꢁꢁꢁN(1), (N(2)ꢁꢁꢁS(1),
N(4)ꢁꢁꢁO(2) interactions are shown in black dotted bonds.
40 Analysis of the mean plane angles formed between the
thiourea portion of the thiosemicarbazide (N3, C6, N4, and S1)
and the substituted phenyl ring reveals that the paraꢀsubstituted
systems of 1 and 2 are more in plane (43.20(7) Å and 48.31(8)
Å respectively) than the diꢀortho substituted pyridyl systems 3
45 and pyridyl substituted
respectively).
4 (83.53(5) Å and 80.57(7) Å
Analysis of the hydrogen bonding interactions involving the
relatively acidic thiosemicarbazide protons were undertaken in
order to ascertain what effect, if any, the differing substitution
50 patterns had on the packing of the molecules. Three distinct
intermolecular hydrogen bonding interactions were observed in
1, involving all of the NꢀH protons (Fig. 2) of the
thiosemicarbazide. The molecules form a staggered chain via
interactions between H(3X) and the pyridyl nitrogen atom,
55 N(1) on an adjacent molecule [(N(3)ꢁꢁꢁN(1)’ = 2.993(2) Å and
<(N(3)ꢀH(3X)ꢁꢁꢁN(1)’) = 173.8°], (Fig. 2 and Table 3) and
between the sulphur atom, S(1), and proton of N(2),
[(N(2)ꢁꢁꢁS(1)’ = 3.421(2) Å and <(N(2)ꢀH(2X)ꢁꢁꢁS(1)’) =
172.8°] (Fig. 2 and Table 3). The third interaction involves
60 H(4X) and the nitro oxygen atom, O(2), on a symmetry
generated adjacent molecule, linking together the chains to
form a network with [N(4)ꢁꢁꢁO(2) = 3.059(2)’ Å and <(N(4)ꢀ
Fig 1. Perspective view of 1. Hydrogen atom and other NH protons are
omitted for clarity. Thermal ellipsoids shown at 50% probability level.
25 interstitial solvent molecules, a feature that makes structural
comparisons much more straightforward.
The thiourea motif of these thiosemicarbazides, adopts in all
four structures the antiꢀconformation a common occurrence in
thiourea systems. All C=S bond distances are consistent with
30 those expected for thio urea moieties [1.681(17) Å – 1.695(2)
Å] as are the bond lengths angles of all other functional groups.
Another common feature of these systems is the twisting out of
plane of the pyridyl group i.e, the thiosemicarbazide C(5)ꢀN(2)ꢀ
N(3)ꢀC(6) dihedral angle in each compound is ca. 100 Å (Table
35 2).
Table 2: Selected bond length and bond angles of 1-4.
Bond Length of
C=S (Å)
Mean plane
Angle (Å)
Dihedral angle, (Å)
C(5)ꢀN(2)ꢀN(3)ꢀC(6)
1
2a
1.681(17)
1.695(2) and
1.695(2)
43.20(7)
124.9(2)
106.6(2)
48.31(8) and 42.82(9)
3
4a
1.6842(17)
1.693(2) and
1.683(2)
83.53(5)
119.0(2)
101.0(2)
80.27(7) and 82.57(7)
a
Asymmetric units of 2 and 4 contain two molecules.
Fig 3. Network arrangement of 1 formed through intermolecular hydrogen
bonding interactions.
2
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Fig 6. Perspective view of 3. Hydrogen atoms other than NH protons
omitted for clarity. Thermal ellipsoids shown at 50% probability level.
fluorine atoms is not involved in Hꢀbonding.
Fig. 4. Perspective view of 2. Hydrogen atoms other than NH protons
The molecular structure of the dimethylphenyl analogue 3
crystallises in the orthorhombic space group Pbca and is shown
30 in Fig. 6, where it can be seen that 3 exhibits two distinct
intermolecular hydrogen bonding interactions. The strongest
between N(3) and the pyridyl nitrogen atoms on a neighbouring
molecule (N(1)) [N(3)ꢁꢁꢁN(1)’ = 2.973(2) Å and <(N(3)ꢀ
H(3X)ꢁꢁꢁN(1)’) = 172 (3)°] and a weaker interaction between
35 hydrazino amine N(2) part of the thiosemicarbazide and the
sulphur atom (S(1)’) on a neighbouring molecule [N(2)ꢁꢁꢁS(1)’
omitted for clarity. Thermal ellipsoids shown at 50% probability level.
H(4X)ꢁꢁꢁO(2)’) = 151.3°], Fig 2. These three hydrogen bonding
interactions between neighbouring urea molecules generate the
supramolecular 3D network arrangement as depicted in Fig. 3.
5
The crystal structure of the pꢀfluoro substituted derivative 2 is
shown in Fig. 4. In 2, two crystallographically independent
molecules dimerise through complementary hydrogen bonding
interactions between the thiosemicarbazide protons H(4X) and
H(24X) and the pyridyl nitrogen atoms N(1) and N(21);
10 [N(4)ꢁꢁꢁN(21)’ =2.861(3) Å and <(N(4)ꢀH(4X)ꢁꢁꢁN(21)’) =
145(3)°; N(24)ꢁꢁꢁN(1)’
H(24X)ꢁꢁꢁN(1)’) = 149(2)°]. These dimers are then extended
along the crystallographic axis through further
=
2.892(3)
Å
and <(N(24)ꢀ
a
complementary hydrogen bonding interactions between
15 thiosemicarbazide protons H(3X) and H(23X) and the sulphur
atoms S(1) and S(21) on adjacent molecules [N(3)ꢁꢁꢁS(21) =
3.329(2) Å and <(N(3)ꢀH(3X)ꢁꢁꢁS(21)) = 165(2)°; N(23)ꢁꢁꢁS(1)
= 3.414(2) Å and <(N(23)ꢀH(23X)ꢁꢁꢁS(1) = 170(2)°]. These
hydrogen bonding interactions result in the formation of a 1D
20 polymeric chain, where strands of this polymer are linked
though hydrogen bonding interactions between the amino
proton H(22X) and sulphur atom S(1); [N(22)ꢁꢁꢁS(1) = 3.303(2)
Å and <(N(22)ꢀH(22X)ꢁꢁꢁS(1)) = 146(2)°] These interactions
lead to the polymeric network shown in Fig. 5, in contrast to
25 the network arrangement of 1. Unlike the structure of 1, the Hꢀ
bonding does not involve the phenyl substituent, i.e. the
Fig 7. Hydrogen bonded polymeric chain of 3 viewed down the cꢀaxis.
N(3)ꢁꢁꢁN(1), N(2)ꢁꢁꢁS(1), interactions are shown in black and red bonds
respectively.
= 3.301(2) Å and <(N(2)ꢀH(2X)ꢁꢁꢁS(1)’) = 161(3)°]. The result
of these hydrogen bonding interactions is a one dimensional
Fig 5. Hydrogen bonded polymeric chain of 2. N(4)ꢁꢁꢁN(21); N(24)ꢁꢁꢁN(1)
are shown in red dotted bonds and N(3)ꢁꢁꢁS(21) and N(22)ꢁꢁꢁS(1) black
dotted bonds.
Fig 8. Perspective view of 4. Hydrogen atom and other NH protons are
omitted for clarity. Thermal ellipsoids shown at 50% probability level.
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<(N(22)ꢀH(22X)ꢁꢁꢁN(25)’) = 170°]. Detailed hydrogen bonding
30 parameters are given in Table 3.
Complexation studies with Zinc(II)
Having investigated the hydrogen bonding properties of 1-4,
we next set out to investigate their potential use in metalloꢀ
supramolecular chemistry. Complexation reactions were
35 carried out between all five ligands and Zn(NO3)2 by stirring at
reflux in acetonitrile. Despite many attempts to obtain single
crystals for all five ligand systems, Xꢀray quality crystals were
only obtained from reactions using ligands 1 and 5 by the slow
evaporation of DMF and acetonitrile respectively. Structural
Fig 9. Hydrogen bonding interactions in thiourea 4, N(1)ꢀN(24) and
N(21)ꢀN(4); N(3)ꢁꢁꢁS(21) and N(23)ꢁꢁꢁS(1) interactions are shown in black
and red dotted bonds respectively.
polymeric chain, Fig. 7.
The inclusion of second pyridyl functionality into the
thiosemicarbazide family was also investigated as it was
thought that the extra hydrogen bond acceptor would alter the
hydrogen bonding and therefore the packing interactions. The
crystal structure of 4 with pyridyl functionality is shown in Fig.
8. The presence of the extra pyridyl ring in 4 contributes to
additional hydrogen bonding unlike 1ꢀ3 with phenyl based
substituents, and 4 exhibits six distinct intermolecular hydrogen
5
10 bonding interactions, Fig. 9.
The molecules form 1D hydrogen bonded chains through
four hydrogen bonds in a similar manner to the Hꢀbonding
pattern in 2. Dimers of molecules are formed through
interactions between the sulphur atoms S(21) and S(1) and NH
15 protons of N(3) and N(23) on an adjacent thiosemicarbazide
molecule [N(3)ꢁꢁꢁS(21)’
=
3.274(2)
Å
and <(N(3)ꢀ
H(3X)ꢁꢁꢁS(21)’)=166°; N(23)ꢁꢁꢁS(1)’ = 3.320(2) Å, <(N(23)ꢀ
H(23X)ꢁꢁꢁS(1)’) = 157°] respectively. These dimers are then
linked into the aforementioned 1D chain though two more
20 hydrogen bonding interactions between the NH protons of N(4)
and N(24) and the 2ꢀpyridyl nitrogen atoms of N(1) and N(21)
on adjacent molecules [N(4)ꢁꢁꢁN(21)’ = 2.972(2) Å and <(N(4)ꢀ
H(4X)ꢁꢁꢁN(21)’)= 149°; N(24)ꢁꢁꢁN(1)’ = 2.989(2) Å, <(N(24)ꢀ
H(24X)ꢁꢁꢁN(1)’) = 158°] (Fig.9). These 1D chains are then
25 cross linked to other symmetry generated chains via the 3ꢀ
pyridyl nitrogen atoms and the proton on an adjacent
thiosemicarbazide molecule [N(2)ꢁꢁꢁN(5)’ = 2.955(3) Å and
<(N(2)ꢀH(2X)ꢁꢁꢁN(5)’)= 172°; N(22)ꢁꢁꢁN(25)’ = 2.937(3) Å,
Fig 10. View of crystal structures of [Zn(1)2]ꢁDMF (top) and [Zn(5)2](bottom).
Thermal ellipsoids shown at 50% probability.
40 analysis revealed neutral, mononuclear complexes of formulae
[Zn(1)2]ꢁDMF (6) and [Zn(5)2] (7). The crystal structures of
both Zn(II) complexes are shown in Fig. 10.
Both complexes crystallised in the orthorhombic space group
Pnna and contain half of the complex in the asymmetric unit
45 with the Zn(II) located on a twoꢀfold rotation axis. Within the
asymmetric unit the Zn(II) is coordinated by one, deprotonated
nitrogen atom N(2), and the sulphur atom S(1) to give a five
membered chelate ring. The twoꢀfold axis generates the other
half of the complexes giving the Zn(II) a tetrahedral geometry
50 and an overall N2S2 coordination environment. Bond lengths
and angles are consistent with those expected for tetrahedral
Zn(II) complexes of this coordination environment. 27, 28
In both 6 and 7 the pyridine nitrogen atom N(1) is
protonated, rather than the thiourea nitrogen atom N(3), a
55 feature likely arising from the highly acidic thiourea nitrogen
atom involved in the chelate ring. In a similar fashion to the
structures of ligands 1 – 4, the Zn(II) complexes 6 and 7 both
exhibit inter molecular hydrogen bonding that results in the
formation of extended coordination polymeric structures. In
60 contrast to the ligand packing interactions, both 6 and 7 pack in
such a way that they form channels within the structure (Fig.
11). In the case of complex 6, the disordered DMF solvent
Table 3: Hydrogen bonding parameters for 1ꢀ4.
DꢀH...A
d(H...A)
d(D...A)
<(DHA)
172.8
173.8
151.3
165
145
146
170
149
1
N(2)ꢀH(2X)...S(1)a
N(3)ꢀH(3X)...N(1)b
N(4)ꢀH(4X)...O(2)c
N(3)ꢀH(3X)...S(21)
N(4)ꢀH(4X)...N(21)d
N(22)ꢀH(22X)...S(1)e
N(23)ꢀH(23X)...S(1)
N(24)ꢀH(24X)...N(1)f
2.53
2.19
2.26
2.47
2.12
2.51
2.56
2.13
3.421(2)
2.992(2)
3.059(2)
3.329(2)
2.861(3)
3.303(2)
3.414(2)
2.892(3)
2
3
4
N(2)ꢀH(2X)...S(1)g
N(3)ꢀH(3X)...N(1)h
N(2)ꢀH(2X)...N(5)i
2.44
2.08
2.10
2.34
2.17
1.99
2.52
2.17
b
3.301(14)
2.972(19)
2.955(3)
3.274(2)
2.972(2)
2.937(3)
3.320(2)
2.989(2)
161.0
172.6
172
166
149
170
157
158
N(3)ꢀH(3X)...S(21)j
N(4)ꢀH(4X)...N(21)i
N(22)ꢀH(22X)...N(25)k
N(23)ꢀH(23X)...S(1)l
N(24)ꢀH(24X)...N(1)m
a
c
d
Symmetry equivalents used: x,ꢀy+1,z+1/2, x,ꢀy+1,zꢀ1/2 , x+1,ꢀy,z+1/2, xꢀ
1,y,z, e ꢀx+1,ꢀy+1,ꢀ z, f x+1,y,z, g xꢀ1/2,y,ꢀz+1/2, x+1/2,y,ꢀz+1/2, ꢀx+1,y+1/2,ꢀ
h
i
z+2, j ꢀx+1,y+1/2,ꢀz+1, k ꢀx,yꢀ1/2,ꢀz+1, l ꢀx+1,yꢀ1/2,ꢀz+1, m ꢀx+1,yꢀ1/2,ꢀz+2 .
4
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a)
b)
Fig 12. View of intermolecular hydrogen bonding interactions in [Zn(1)2]ꢁDMF
(6). a) NꢀHꢁꢁꢁO interactions in 6. b) NꢀHꢁꢁꢁS interactions in 6.
<(N(1)ꢀH(1X)ꢁꢁꢁO(1)’) = 137°; for 7 N(1)ꢁꢁꢁF(2)’ = 3.046(7) Å
15 and <(N(1)ꢀH(1X)ꢁꢁꢁF(2)’) = 138°] (Fig. 12 and 13). These
chains are then linked to neighbouring chains though hydrogen
bonds involving the coordinated sulphur atom S(1) and the NH
thiosemicarbazide proton of N(4) on a neighbouring molecule
[for 6 N(4)ꢁꢁꢁS(1)’ = 3.417(4) Å and <(N(4)ꢀH(4X)ꢁꢁꢁS(1)’) =
20 165°; for 7 N(4)ꢁꢁꢁS(1)’ = 3.445(6) Å and <(N(4)ꢀH(4X)ꢁꢁꢁS(1)’)
= 174°]. The result of these intermolecular
Fig 11. Spacefill representations of the packing of 6 (top) and 7 (bottom)
showing the solvent accessible channels.
hydrogen bonding interactions is the formation of the
aforementioned channels.
molecule resides within the cavity of these channels. In
contrast, no solvent molecules were found within the channels
of 7. Thermal stability of the zinc complex 6 was studied by
thermal gravimetric analysis (TGA). The thermogram of 6
showed a gradual weight loss ~10% (20ꢀ 220ºC)30 which
corresponds to the loss of one N,Nꢀdimethyl formamide (DMF)
from the pores of the crystalline 6, (Supporting information Fig
S1 and S2).
25
Analysis of the void space of the channels of 6 and 7 was
carried out using MERCURY and the voids appear to adopt
channels through the crystal lattice where the solvent accessible
surface is continuous to a probe radius of 1.2ꢀ1.7 Å for 6 and
1.2ꢀ1.5 Å for 7 (see Table 4, Fig 14 aꢀd). In both 6 and 7, the
5
30 voids form interconnected infinite channels that might
a)
Each of the complexes display the same hydrogen bonding
10 pattern in that the protonated pyridine nitrogen atom N(1)
hydrogen bonds to the phenyl substituent on a neighbouring
molecule (NO2 or CF3 for 6 and 7 respectively) giving rise to
an extended 1D chain [for 6 N(1)ꢁꢁꢁO(1)’ = 2.928(5) Å and
Table 4. Calculated values of cavity volumes for solvent accessible
surface of [Zn(1)2] and [Zn(5)2], Fig 14.
b)
[Zn(1)2] a
[Zn(5)2]
Probe radius Void volume (
Void volume ( Å3
)
(Å)
1.7
1.6
1.5
1.4
1.3
1.2
Å3)
23.14 (0.7)
34.76 (1.1)
51.67 (1.7)
70.14 (2.2)
91.82 (2.9)
118.80 (3.8)
3.07 (0.1)b
8.22 (0.3)b
17.37 (0.5)
28.66 (0.9)
44.42 (1.4)
64.13 (2.0)
a Squeeze command was used to remove the disordered DMF for analysis use
only. b Channels are not continuous.
Fig 13. View of intermolecular hydrogen bonding interactions in [Zn(5)2] (7). a)
NꢀHꢁꢁꢁF interactions in 7. b) NꢀHꢁꢁꢁS interactions in 7.
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Fig 14. Void analyses of zinc(II) complexes 6 and 7. a) Continuous contact surfaces generated using a probe radius of 1.8
Å
in 6. b) Continuous solvent
accessible voids generated using a probe radius of 1.5
solvent accessible surface generated using a probe radius of 1.5
Å
in 6. c) Continuous contact surfaces generated using a probe radius of 1.5 Å in 7. d) Continuous
. Solvent accessible voids are continuous and can participate in solvent inclusion.
Å
potentially allow for uptake of small molecules such as H2,
CH4 etc.31 The solvent accessible void in the asymmetric unit
of 6 is occupied by a disordered DMF molecule and the void
may not be stable to removal of DMF.
25 however, in investigating these luminescent properties further.
800
5
700
600
500
400
300
200
100
0
Em_280nm
Ex_440nm
Whilst the void analysis of both 6 and 7 indicates that the
crystals might be porous, we are hesitant to describe them as
such without further experimental data (solvent uptake and
crystal stability under vacuum).31,32 Nonetheless these are
10 encouraging results and further investigations into the porosity
are onꢀgoing. Research is onꢀgoing in our group to incorporate
new donorꢀacceptor functional groups into the ligand design
and subsequently prepare and study the dꢀmetal ion complexes
and their hostꢀguest interactions.
300 350 400 450 500 550 600 650 700 750
Wavelength (nm)
15
Photo luminescent properties of 7
Fig 15. Excitation and emission spectra of [Zn(5)2], 7 in CH3CN; Inset image
shows luminescent [Zn(5)2], 7.
Both the Zinc complexes 6 and 7 have been investigated for
their photoluminescent properties. Complex 7 with a pꢀCF3
group exhibits blue luminescence (λmax = 440 nm) when
20 excited at 290 nm, Fig 15.33 Conversely, thiosemicarbazide
ligand 5 does not exhibit luminescent properties suggesting that
the photoluminescence arises from ligand to metal charge
transfer (LMCT). Zinc complex 6 with pꢀnitro group does not
exhibit any luminescent property, Fig S3. We are in the process
Conclusions
In this article, we have presented the synthesis and structural
characterisation of thiosemicarbazide based ligands which
contain a variety of aromatic substituents (4ꢀnitrophenyl (1), 4ꢀ
6
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fluorophenyl (2), 2,6ꢀdimethylphenyl (3), 3ꢀpyridyl (4) and 4ꢀ
trifluoromethyl (5). These ligands are all rich in hydrogen bond
donors and acceptors and as such the solid state packing
interactions were complex in nature and significantly
influenced by the nature of the substituents. The introduction of
hydrogen bond acceptors to the substituents allows the
compounds to form extended networks whereas 2, which has
no additional acceptors (other than the sulphur and
thiosemicarbazide/pyridine nitrogen atoms) forms a simple 1D
10 chain. All of the structures 1 – 4 formed well packed systems
with no porous networks; however, the incorporation of Zn(II)
resulted in porous, hydrogen bonded networks. Complexes
formed only with ligands 1 and 5 via coordination to the
sulphur atom and the hydrazino nitrogen atom of the
15 thiosemicarbazide functionality to give neutral bis ligand
30
complexes of general formulae, [Zn(L)2] (6 and 7). The large
channels formed through extended Hꢀbonding interactions are
of sufficient size to include solvent molecules,29 and although
no solvent was occupying the channels in 7, a disordered DMF
20 molecule was located in the pores of 6. These porous Zn(II)
networks represent our first step towards the development of
systems that might act as storage compounds, or indeed Zn(II)
based luminescent sensing materials where inclusion of a guest
molecule within the pores might modulate the
25 fluorescent/luminescent properties of the Zn(II) centre.
5
In summary, we have developed a structurally simple family
of hydrogen bonding donors that possess an additional one or
two metal coordination sites. We demonstrated that while the
Table 1: Crystal structure data for thiosemicarbazides analogues 1ꢀ4, [Zn(1)2]ꢁDMF, 6 and [Zn(5)2] 7.
1
2
3
4
6 [Zn(1)2]ꢁDMF
7 [Zn(5)2]
CCDC deposition
number
906518
906515
906516
906517
906513
906514
Temperature
106(2) K
108(2) K
108(2) K
133(2) K
100(2) K
100(2) K
Formula
C12H11N5O2S
289.32
C12H11FN4S
262.31
C14H16N4S
272.37
C11H11N5S
245.3
C27H27N11O5S2Zn
715.09
C26H20N8F6S2Zn
687.99
Molecular weight
Crystal size (mm)
0.43 x 0.35 x 0.26
0.54 x 0.31 x 0.23
0.44 x 0.34 x 0.25
0.60 x 0.25 x 0.25
0.07 x 0.06 x 0.05
0.08 x 0.07 x 0.07
Crystal system
Space group
a, b, c (Å)
Monoclinic
Pc
Triclinic
Pꢀ1
Orthorhombic
pbca
Monoclinic
P2(1)
Orthorhombic
Pnna
Orthorhombic
Pnna
a = 7.0476(14)
b = 9.2828(19)
c = 10.069(2)
a = 9.928(2)
b = 11.123(2)
c = 12.860(3)
a = 8.7107(8)
b = 16.0126(15)
c = 20.772(2)
a = 8.6158(17)
b = 14.713(3)
c = 9.833(2)
a = 16.9576(9)
b = 13.3003(5)
c = 13.7986(6)
a = 17.0484(5)
b = 13.4943(5)
c = 13.7277(4)
α, β, γ (°)
a= 90°
α = 74.09(3)°
β = 89.89(3)°
γ = 65.90(3)°
α = 90°
β = 90°
γ = 90°
α = 90°
α = 90°
β = 90°
γ = 90°
α = 90°
β = 90°
γ = 90°
b= 105.45(3)°
γ = 90°
β = 111.82(3)°
γ = 90°
Volume (Å)
Z
634.9(2)
2
1236.8(4)
4
2897.2(5)
8
1157.2(4)
4
3112.2(2)
4
3158.14(16)
4
Dc(calcd) (mg/m3)
ꢂ (mmꢀ1)
1.513
0.265
300
1.409
0.261
544
1.249
0.216
1152
1.406
0.263
512
1.526
2.840
1472
1.447
2.907
1392
F(000)
Collected reflns
Independent reflns
4606
8664
15239
8636
10478
11662
1903 [R(int) =
0.0133]
4139 [R(int) =
0.0274]
2555 [R(int) =
0.0264]
3639[R(int) =
0.0149]
2599[R(int) =
0.0410]
2664[R(int) =
0.0411]
2
Goof on F
1.046
1.139
1.028
1.070
1.118
1.047
R1 [I>2σ(I)]
R1 = 0.0193
wR2 = 0.0517
R1 = 0.0426
wR2 =0.0917
R1 = 0.0373
wR2 = 0.0948
R1 = 0.0238
wR2 = 0.0595
R1 = 0.0411
wR2 = 0.1046
R1 = 0.0316
wR2 = 0.0858
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crystalline samples in the case of 1, 3 and 4. Thiourea 5 was
obtained as pale yellow coloured powder after column
60 chromatography. Thioureas 1ꢀ5 were recrystallised using hot
acetonitrile.
thiosemicarbazides 1-4 all gave rise to extensive interꢀ
molecular hydrogen bonding interactions, they can also be
employed in the formation of Hꢀbonded coordination networks
with Zn(II). We are in the process of further evaluating the
application of these and related systems based on the
thiosemicarbazide structure for use in supramolecular
chemistry and crystal engineering.
5
1: Red crystals were obtained from acetonitrile. Yield =180mg
(68%). 1H NMR (400MHz, DMSOꢀd6): 10.31 (s, 1H), 10.13 (s,
65 1H), 8.67 (s, 1H), 8.20ꢀ8.14 (m, 3H), 7.90ꢀ8.06 (m, 2H), 7.68ꢀ
7.20 (m, 1H), 6.85 (s, 1H), and 6.66 (d, 1H, J=8Hz). 13C NMR
(400MHz, DMSOꢀd6): 180.92, 158.88, 147.69, 145.78, 143.06,
137.86, 124.15, 123.52, 116.06 and 107.51. IR (cmꢀ1): 3293.9,
3153.2, 2915.6, 1591.8, 1544.9, 1448.9, 1499.6, 1329.4,
70 1268.9, 1109.8, 991.5, 857.9 and 744.8. HRMS calcd. for
C12H12N5O2S = 290.0712; Found mass = 290.0712. Elemental
analysis calcd. for C12H11N5O2S: C, 49.82; H, 3.83; N, 24.21.
Found: C, 49.83; H, 3.85; N, 24.33. Melting point: 169.1ꢀ
169.3ºC.
10 Experimental
All chemical were purchased from SigmaꢀAldrich and Fluka
chemical company and used without purification. Synthesis of
1 - 5 were carried out in 10–20 mL Biotage Microwave Vials in
a Biotage Initiator Eight EXP microwave reactor. Column
15 chromatography was performed using silica gel 60 (230 – 40
mesh ASTM). Melting points were recorded on an Electro
thermal IA9000 digital melting point apparatus. Infraꢀred
spectra were recorded on a Perkin Elmer spectrum one FTꢀIR
75
2: Trituration was performed to remove trace amounts of an
impurity from the white coloured powder. White crystals were
obtained by slow evaporation of acetonitrile. Yield = 142mg
spectrometer equipped with
a universal ATR sampling
20 accessory. 1H and 13C NMR spectra were recorded using a
Bruker DPXꢀ400 instrument. The samples were dissolved in
DMSOꢀd6 and spectra were recorded in a 5ꢀmm NMR tube.
Chemical shifts are reported relative to tetramethylsilane and
coupling constants are given in Hertz. The elemental analysis
25 for C, H and N was performed on an Exeter analytical CEꢀ450
Elemental analyzer in University College Dublin. Electrospray
mass spectra were recorded on a Mass Lynx NT V 3.4 on a
Waters 600 controller. Thermal gravimetric analysis (TGA)
was performed on Perkin Elmer Pyrus 1 TGA equipped with an
30 ultraꢀmicro balance with a sensitivity of 0.1microgram. The
temperature range is from 20ꢀ700 C with a scan rate 10
ºC/min. Xꢀray data (Table 1) were collected on either a Rigaku
1
(59.1%). H NMR (400MHz, DMSOꢀd6): 9.88 (s, 1H), 9.75 (s,
80 1H), 8.55 (s, 1H), 8.16 (m, 1H), 7.66ꢀ7.62 (m, 1H), 7.52ꢀ7.49
(m, 2H), 7.17ꢀ7.10 (m, 2H), 6.84ꢀ6.81 (m, 1H), 6.66ꢀ6.64 (m,
1H). 13C NMR (400MHz, DMSOꢀd6): 182.02, 160.94, 159.64,
158.54, 148.11, 138.24, 136.05, 127.96, 116.20, 115.03, 114.80
and 107.63. IR (cmꢀ1): 3146.7, 2942, 1603, 1579, 1542.5,
85 1507.6, 1412.3, 1444.2, 1412.3, 1351.5, 1289.3, 1262.4,
1215.6, 1149.9, 1126.9, 1087.0, 992.7, 925.2, 835.5, 819.8,
766.4 and 732.3. HRMS calcd. for C12H12N4FS = 263.0767,
Found = 263.0766. C12H11FN4S: C, 54.95; H, 4.23; N, 21.36.
Found: C, 54.50; H, 4.10; N, 21.07; Melting point: 162.5ꢀ
90 162.7°C.
Saturn
724
CCD
Diffractometer
using
graphiteꢀ
3: Slow evaporation of the reaction mixture for ~16h yielded
white coloured crystals. Yield = 152mg (60.9%). 1H NMR
(400MHz, DMSOꢀd6): 9.61 (s, 1H), 9.44 (s, 1H), 8.61 (s, 1H),
95 8.13ꢀ8.14 (d, 1H, J =4Hz), 7.65 (t, J = 8Hz, 1H), 7.01ꢀ7.08 (m,
3H), 6.81 (t, J = 8Hz, 1H), 6.67ꢀ6.69 (d, J= 8Hz, 1H) and 2.14
(s, 6H).13C NMR (400MHz, DMSOꢀd6): 181.82, 159.47,
147.64, 137.69, 137.18, 136.36, 127.43, 126.55, 115.49, 106.77
and 18.06. IR (cmꢀ1): 3289.5, 3138.3, 2920.0, 1583.45,
100 1506.93, 1451.8, 1300.6, 1255.1, 1122.7, 1081.4, 996.6, 931.2,
812.2, 769.8 and 738.9. HRMS calcd. for C14H17N4S =
273.1174, Found mass =273.1161. Elemental analysis calcd.
for C14H16N4S: C, 54.50; H, 4.10; N, 21.07; Found: C, 54.95;
H, 4.23; N, 21.36. Melting point: 193.1ꢀ193.4°C.
monochromated MoꢀKα radiation (λ = 0.71073 Å) or a Bruker
35 Apex2 Duo using a high intensity CuꢀKα radiation source (λ =
1.54178 Å). The data sets from the Rigaku Saturnꢀ724
diffractometer were collected using CrystalclearꢀSM 1.4.0
software. Data integration, reduction and correction for
absorption and polarisation effects were all performed using the
40 CrystalclearꢀSM 1.4.0 software. Space group determination,
was obtained using Crystalstructure ver.3.8 software. Datasets
collected on the Bruker Apex2 Duo were processed using
Bruker APEXv2011.8ꢀ0 software. The structures were solved
by direct methods (SHELXSꢀ97) and refined against all F2 data
45 (SHELXLꢀ97).34 All Hꢀatoms, except for NꢀH protons, were
positioned geometrically and refined using a riding model with
d(CHaro) =0.95 Å, Uiso = 1.2Ueq (C) for aromatic and 0.98 Å,
Uiso = 1.2Ueq (C) for CH3. NꢀH protons were found from the
difference map and either freely refined or fixed to the attached
50 atoms with UH = 1.2UN.
105 4: Pale yellow crystals. Yield = 210 mg (93%). 1H NMR
(400MHz, DMSOꢀd6): 10.06 (s, 1H), 9.94 (s, 1H), 8.62 (s, 2H),
8.31 (d, 1H, J = 4Hz), 8.16 (d, 1H, J = 8.4Hz), 7.94 (d, 1H, J=
7.5Hz), 7.65 (t, 1H, J= 14.8Hz), 7.35 (dd, 1H, J = 8.0 Hz), 6.83
(t, 1H, J= 12Hz), 6.66 (d, 1H, J=8Hz). 13C NMR (400MHz,
110 DMSOꢀd6): 182.27, 159.49, 148.14, 147.23, 145.97, 138.34,
136.53, 133.44, 123.19, 116.37 and 107.74. IR (cmꢀ1): 3137.05,
2962.72, 1601.82, 1579.18, 1515.91, 1547.26, 1453.72,
1424.70, 1287.84, 1265.78, 1233.48, 1192.07, 1087.79,
1027.28, 825.64, 770.91 and 707.96. Elemental analysis calcd.
General Procedure for the Synthesis of ligands 1-5
Pyridyl amine (1mmol) was treated with the appropriate
isothiocyanate (1.1mmol) in 20ml acetonitrile. Reactions were
55 carried out in a microwave reactor for 40 mins at 1000C. The
resulting reaction mixture was gravity filtered and slow
evaporation of the solvents yielded amorphous powers and
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† Electronic Supplementary Information (ESI) available: CCDC
906513ꢀ906518. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/b000000x/
for C11H11N5S: C, 53.86; H, 4.52; N, 28.55; Found: C , 53.82;
H, 4.33; N, 28.59. HRMS calcd. for C11H10N5S: 244.0665,
Found mass: 244.0657. Melting point: 188.6 – 188.9°C.
60
65
70
1
5: Pale yellow amorphous powder: Yield: 74.2 % (212mg). H
1
a) J. T. Lenthall, J. A. Foster, K. M. Anderson, M. R. Probert, J. A.
K. Howard, J. W. Steed, CrystEngComm., 2011, 13, 3202ꢀ3212; b)
J. W. Steed, Chem. Commun, 2011, 47, 1379ꢀ1383; c) J. A. Foster,
M. O. M. Piepenbrock, G. O. Lloyd, N. Clarke, J. A. K. Howard, J.
5
NMR (400MHz, DMSOꢀd6): 10.14 (S, 1H), 9.97 (S, 1H), 8.63
(S, 1H), 8.15 (S, 1H), 7.85 (d, 2H, J= 8 Hz), 7.66 (d, 3H,
J=12Hz), 6.84 (s, 1H) and 6.66 (d, 1H, J= 8 Hz). 13C NMR
(400MHz, DMSOꢀd6): 181.14, 159.01, 147.68, 143.06, 137.84,
125.72, 125.08, 124.89, 124.40, 123.01, 115.93 and 107.35.
10 HRMS calcd. for C13H12N4F3S: 313.0735. Found: 313.0723.
Melting point: 184.7ꢀ 184.9 C. IR (cmꢀ1): 3136.10, 2923.2,
1600.7, 1585.3, 1523.5, 1505.1, 1451.1, 1321.8, 1294.6,
1164.8, 1102.3, 1064.5, 992.3, 845.5, 791.4, 776.7, 731.4,
658.0.
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2
15
Synthesis of Zn(II) complexes 6 and 7
75
80
Synthesis of 6: To a well stirred solution of thiourea 1
(0.16mmol) in acetonitrile was added Zn(NO3)2 (0.16mmol).
On the addition of the Zn(II) salt, a red colouration appeared
20 and the solution was heated to reflux for 16h. The reaction
mixture was filtered and the filtrate left to evaporate over 24
3
4
hours. Micro crystalline
6 was isolated after the slow
evaporation of acetonitrile. These crystals were not good
enough for diffraction analysis. The microcrystalline 6 was
25 dissolved in DMF which on slow evaporation yielded Xꢀray
quality red crystals of 6 over a 24ꢀ48h period. 61% (w.r.t
ligand 1). HRMS calcd. for C24H19N10O4S2Zn: 639.0324.
Found: 639.0333. 1H NMR (600MHz, DMSOꢀd6): 10.97 (d,
1H, J=6Hz), 9.58 (S, 2H), 8.15 (d, J=12Hz, 2H), 7.84 (d,
30 J=6Hz, 2H), 7.53 (t, 1H, J= 12Hz), 7.3ꢀ7.27 (m, 1H), 6.63 (d,
1H, J=6Hz) and 6.63 (t, 1H, J=12Hz). Elemental analysis calcd.
for C27H27N11O5S2Zn: C, 45.35; H, 3.81; N, 21.55; Found: C,
45.02; H, 3.06; N, 21.38. IR (cmꢀ1): 3257.7, 1665.0, 1637.7,
1525.8, 1560.5, 1586.9, 1495.2, 1470.7, 1315.9, 1297.2,
35 1261.8, 1158.5, 1059.1, 992.6, 846.7, 736.04 and 675.6.
85
5
90
95
Synthesis of 7: To a well stirred solution of 5 (0.16mmol) in
acetonitrile, was added Zn(NO3)2 (0.16mmol). As soon as the
addition of the Zn(II) salt a yellow coloration was observed and
40 the solution was heated to reflux. After 16h, the reaction
mixture was filtered and left to slow evaporation over a 24 h
period. This yielded Xꢀray quality yellow crystals of 7 (33mg,
30%, w.r.t ligand 5). HRMS calcd. for C26H19N8F6S2Zn:
685.0370. Found: 685.0374. IR (cmꢀ1): 3256.7, 1639.60,
45 1590.96, 1492.39, 1406.85, 1314.56, 1256.99, 1163.75,
1095.73, 1054.05, 982.01, 814.90 and 746.71.
6
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Acknowledgements
Financial support from Science Foundation Ireland (SFI RFP
50 2008 and SFI PI 2010 grants awarded to TG) as well as IRSET
Postdoctoral Fellowship (JAK) is greatly acknowledged.
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55 Eꢀmail:gunnlaut@tcd.ie
Fax: +353 1 671 2826; Tel: +353 1 896 3459.
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