Isostructural mercury coordination polymers with amide junction: Interplay of coordination and π-π Stacking

Article abstract of DOI:10.1021/cg300587b

Two coordination polymers [Hg₂Cl₄L·2(DMF)] _n, 1, and [Hg₂Br₄L·2(DMF)]_n, 2, where L is the N,N′-(1,2-diphenylethane-1,2-diyl)diisonicotinamide ligand, have been synthesized and characterized

Full text of DOI:10.1021/cg300587b

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Article
Isostructural Mercury Coordination Polymers with Amide
Junction: Interplay of Coordination and #-# Stacking
Hamid Reza Khavasi, and Bahareh Mir Mohammad Sadegh
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg300587b • Publication Date (Web): 30 Aug 2012
Downloaded from http://pubs.acs.org on August 31, 2012
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Crystal Growth & Design
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Isostructural Mercury Coordination Polymers with
Amide Junction: Interplay of Coordination and π-π
Stacking
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Hamid Reza Khavasi* and Bahareh Mir Mohammad Sadegh
Department of Chemistry, Shahid Beheshti University, General Campus, Evin, Tehran 1983963113,
Iran
E-mail: h-khavasi@sbu.ac.ir
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RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
TITLE RUNNING HEAD: Isostructural Mercury Coordination Polymers
CORRESPONDING AUTHOR FOOTNOTE: Hamid Reza Khavasi, Tel No: +98 21 29903105, Fax
No: +98 21 22431663.
ABSTRACT. Two coordination polymers [Hg2Cl4L.2(DMF)]n, 1 and [Hg2Br4L.2(DMF)]n, 2, where L
is the N,N'-(1,2-diphenylethane-1,2-diyl)diisonicotinamide ligand have been synthesized and
characterized. X-ray single crystal diffraction reveals that both coordination polymers are isostructural
and mercury adopts square based pyramid coordination geometry. Our results show that interplay
between the coordination of the carbonyl group and π…π interaction of adjacent pyridine rings leads to
the formation of 2D structures.
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Introduction
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In the last few decades, crystal engineering of coordination polymers has attracted great attention due
to their usage in different areas such as catalysis, materials and nanotechnology.1 Many factors such as
ligand structure,2 coordination geometry of metal center,3 counter ions4 and experimental conditions5
can affect the final structure of coordination polymers. In addition to coordination bonds, various types
of intermolecular interactions can extend crystal packing into higher dimensions. The influence of
hydrogen bonds on the structure of coordination polymers has been well studied.6 Other than the
hydrogen bonds, the π-π interactions undoubtedly play important roles in determining the crystal
packing and molecular assemblies of the coordination compounds.7 It is notable, that unlike hydrogen
bonding, π-π interaction is very difficult to control due to the lack of strength and directionality. There
are some examples reported in the literature describing the influence of π-π interactions on the structure-
directing of coordination compounds.8 Other than the π…π interactions and the hydrogen bonds, the
anion…π interaction also plays an important role in determining the crystal packing and molecular
assemblies. Anions can influence the final structures either by coordinating directly to the metal centers
or by acting as templates through non-covalent interactions which affect the self-assembly process.9
In recent years, coordination polymers with organic ligands based on two pyridine moieties as
coordination sites and different spacers such as alkyl chain, imine bond and amide functionality have
been designed.10-12 Considering these bispyridyl ligands with amide junction reveals that: (1) two
pyridyl groups are a good choice for connecting metal centers,13 (2) the amide group may participate in
the binding to metal through the oxygen atom of carbonyl moiety,14,15 (3) π-π stacking between pyridine
rings and also the hydrogen bonding of amide functionality can add extra dimensionality to the resulted
structure15,16 and (4) due to the low rotational barrier of the amide group, these ligands can possess
rotational flexibility and adopt a variety of conformations.16c,17 In this regards, reports on the
coordination compounds of N,N'-(1,2-diphenylethane-1,2-diyl)dipyridineamide ligands are rare, with
the exception of Moberg and co-workers (monomeric Zr complex)18, Zhou and co-workers (monomeric
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Ni complex)19 and Williams and co-workers (polymeric Cu complex)20 reports containing the N,N'-(1,2-
diphenylethane-1,2-diyl)dipicolinamide ligand.
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In continuation of our previous study on the effect of π…π interaction on the coordination geometry
of central metal,21 we synthesized the N,N'-(1,2-diphenylethane-1,2-diyl)diisonicotinamide ligand (L)
bearing two pyridines for coordination to the metal center which would facilitate the formation of π..π
stacking which affects the structure of the coordination polymers. For this purpose, two Hg(II)
complexes of this ligand, [Hg2Cl4L.2(DMF)]n, 1, and [Hg2Br4L.2(DMF)]n, 2, have been prepared by
the reaction of equimolar quantities of mercury halides (chloride and bromide), Scheme 1. X-ray
diffraction analysis of these coordination polymers gives details about the interplay of coordination and
π…π interaction in their three-dimensional organizations.
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Experimental section
Chemicals and instrumentation
All solvents such as methanol, chloroform and pyridine and the chemicals, pyridine-4-carboxylic acid,
meso-1,2-diphenylethanediamine, triphenyl phosphate and mercuric (II) halides (chloride and bromide)
were commercially available (reagent grade) and were purchased from Merck and used without further
purification. Infrared spectra (4000–250 cm-1) of solid sample were taken as 1% dispersion in KBr
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pellets using a BOMEM - MB102 spectrometer. H NMR spectra were recorded on a Bruker AC-300
MHz spectrometer at ambient temperature in (CD3)2SO. All chemical shifts are quoted in part per
million (ppm) relative to tetramethylsilane. Melting point was obtained by a Bamstead Electrothermal
type 9200 melting point apparatus and corrected.
Synthesis of N,N'-(1, 2-diphenylethane-1, 2-diyl)diisonicotinamide, L
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A solution of 5 mmol meso-1,2-diphenylethanediamine (1.061 g) in 10 mL pyridine was added to a
solution of 10 mmol pyridine-4-carboxylic acid (1.23 g) in 10 mL pyridine. The resulting solution was
stirred at 313 K for 20 min then 10 mmol of triphenyl phosphite (2.6 mL) was added dropwise, and the
reaction mixture was stirred at 373 K for 5 h and at ambient temperature for 72 h. The resulting yellow
solution was added to distilled water, filtered and then washed with diethylether. A light yellow solid
resulted with a yield of 60%, mp >270 ºC. X-ray quality crystals were obtained by slow solvent
evaporation in dimethyl sulfoxide at room temperature. Anal.Calc. for L (C30H34N4O4S2): C, 62.20; H,
5.87; N, 9.68. Found: C, 62.24; H, 5.90; N, 9.73. FT-IR (KBr pellet,cm-1): 3324s, 3062s, 1642s, 1534s,
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1406m, 1323s, 758s, 702s. H NMR (DMSO, δ from TMS): 9.1254(s, 1H), 8.6322(d, 2H), 7.6647(d,
2H), 7.4701-7.1929(m, 5H), 75.6691(m, 1H).
Synthesis of [Hg2Cl4L.2(DMF)]n, 1 and [Hg2Br4L.2(DMF)]n, 2.
To a solution of 0.5 mmol of mercury (II) halide (HgX2, X=Cl and Br) in 3 mL of methanol, a solution
of 0.5 mmol of N,N'-(1,2-diphenylethane-1,2-diyl)diisonicotinamide (ligand L) in mixure of 3 mL of
methanol and 3 mL of chloroform was added while stirring. The mixture was heated at 313 K for about
10 min and the resulting sediment was filtered and dried outdoor, it was then, solved in dimethyl
foramide solvent. Upon slow evaporation of this solution at room temperature, colorless block crystals
for [Hg2Cl4L.2(DMF)]n and [Hg2Br4L.2(DMF)]n complexes, suitable for X-ray analysis were obtained
after ca. two weeks (yield ca. 63% and 71%, mp 260-261 ºC and 253-254 ºC decompose for
[Hg2Cl4L.2(DMF)]n and [Hg2Br4L.2(DMF)]n, respectively). Anal.Calc. for 1 (C32H39Cl4Hg2N6O4): C,
34.55; H, 3.51; N, 7.56. Found: C, 34.59; H, 3.56; N, 7.60. FT-IR (KBr pellet,cm-1): 3320s, 3065s,
1647s, 1538s, 1403m, 1327s, 758s, 700s. Anal. Calc. for 2 (C32H39Br4Hg2N6O4): C, 29.78; H, 3.02; N,
6.51. Found: C, 29.83; H, 3.06; N, 6.56. FT-IR (KBr pellet, cm-1): 3318s, 3067s, 1644s, 1541s, 1404m,
1327s, 757s, 699s.
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Crystal Growth & Design
Crystal structure determination of complexes
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The x-ray diffraction measurements were made on a STOE IPDS-II diffractometer with graphite
monochromated Mo-Kα radiation. For N,N'-(1,2-diphenylethane-1,2-diyl)diisonicotinamide, L, a
colorless prism crystal with a dimension of 0.37 × 0.36 × 0.32 mm, for [Hg2Cl4L.2(DMF)]n, 1, a
colorless block crystal with a dimension of 0.40 × 0.35 × 0.33 mm and for [Hg2Br4L.2(DMF)]n, 2, a
colorless block crystal with a dimension of 0.21 × 0.18 × 0.14 mm were mounted on a glass fiber and
used for data collection. Cell constants and an orientation matrix for data collection were obtained by
least-squares refinement of diffraction data from 3010 for L, 5002 for 1 and 3780 for 2 unique
reflections. Data were collected at a temperature of 298(2) K to a maximum θ value of 26.00°, 29.21°
and 26.00° for L, 1 and 2 and in an a series of ω scans in 1° oscillations and integrated using the Stoe X-
AREA22 software package. The numerical absorption coefficient, ꢀ, for Mo-Kα radiation are 0.215 mm-
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for L, 8.517 mm-1 for [Hg2Cl4L.2(DMF)]n and 12.126 mm-1 for [Hg2Br4L.2(DMF)]n. A numerical
absorption correction was applied using X-RED and X-SHAPE softwares.23 Data were corrected for
Lorentz and Polarizing effects. The structures were solved by direct methods24 and subsequent different
Fourier maps and then refined on F2 by a full-matrix least-square procedure using anisotropic
displacement parameters. All refinements were performed using the X-STEP32 crystallographic
software package.25 The crystallographic data and selected bond lengths and bond angles for L, 1 and 2
are listed in Tables 1 and 2.
Theoretical Methods.
All calculations have been carried out by means of the GAUSSIAN03 package.26 Calculations between
pyridine aromatic rings were performed with the experimental structure as the starting point at the MP2-
aug-cc-PVDZ level. The interaction energies were counterpoise corrected for the basis set superposition
error (BSSE) with the procedure of Boys and Bernardi.27
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Results and Discussion
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Synthesis
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The combination of L with HgX2 (X=Cl, Br) in 1:1 molar ratio leads to the formation of 2D
[Hg2Cl4L.2(DMF)]n, 1, and [Hg2Br4L.2(DMF)]n, 2 coordination polymers. Upon slow evaporation of
the DMF solution of these complexes, colorless block crystals were obtained after ca. two weeks. X-ray
diffraction on a single crystal of these complexes demonstrates that they are isostructural compounds
and both of them crystallize in the triclinic crystal system with Pī space group, Table 1. X-ray powder
patterns of compounds 1 and 2 are essentially the same to that simulated from the structure determined
by single crystal analysis, see ESI, Fig. S1 and S2. All of the peaks of the two compounds can be
indexed to their respective simulated XRD powder patterns, which indicate each of the two compounds
is pure phase.
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Structural analysis of L, 1 and 2
Based on the comparative direction of the C=O groups, L can adopt anti-anti-anti and anti-syn-anti
conformations, see ESI, Fig. S3. This allows conformational adaptation of L for the generation of
different isomers of mercury(II) complexes. To have a better insight into the structural changes of L
from free ligand to coordination compounds 1 and 2, we determined its structure by X-ray diffraction
study. An ORTEP view of L is shown in Figure 1. The amide N–C and C=O bond distance of 1.337(3)
and 1.224(3)Å, respectively, are in normal ranges. As depicted from Figure 1, in the solid state, L
adopts an anti-anti-anti conformation.
The non-classical C-H…N hydrogen bonds, which are those between C–H pyridine donor and pyridine
nitrogen acceptor, form a one dimensional zigzag. These 1D zigzag chains are further linked to generate
2D sheets by head-to-tail dimeric C=O…H-C(pyridine) non-classical classical hydrogen bonds into
centrosymmetric R2 (10) carbonyl–pyridne synthon, Figure 2a, Table 3. DMSO solvent molecules are
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linked adjacent 2D sheets from one side by S=O…H-N(amide) and S=O…H-C(pyridine) classical and
non-classical hydrogen bonds and from the other side by the weak intermolecular C=O…H-C(methyl)
interactions, Figure 2b, Table 3.
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The coordination ability of L was then tested with mercury(II) halides. Simple reaction between HgX2
and L in methanol/chloroform afforded well-formed colorless crystals of 1 and 2. The asymmetric unit
of 1 and 2 consists of one Hg2+ ion, two halogen anions and a half crystallographically independent
ligand. As depicted in Figure 3, in these compounds, coordination geometry around the Hg(II) centre in
compunds 1 and 2 are square-based pyramid (SBP), Table 2, with trigonality index (τ)28 of 0.016 and
0.023 respectively. In both structures, the plane of square-based pyramid is occupied by three halogen
anions (Hg–Cl: 2.319(2), 2.340(2) and 3.051(2) Å and Hg-Br: 2.450(1), 2.464(1) and 3.163(1) Å, Table
2, and carbonyl oxygen atom (Hg-O: 2.726(5) Å and 2.778(5) for 1 and 2 respectively). The appical
position in both structures is occupied by a nitrogen atom from the pyridine ring of the L ligand at a
normal distance of 2.453(4) and 2.448(5) Å for 1 and 2 respectively. The τ values and geometrical
parameters around central metal atoms clearly show, Table 2, that the coordination geometry around
Hg(II) is almost perfect SBP in both structures. Examining the crystal structures of 1 and 2 also reveal
that L adopts an anti-anti-anti conformation, Figure 3. Reports on the coordination compounds of N,N'-
(1,2-diphenylethane-1,2-diyl)dipyridineamide ligands are rare. A few related compounds in the
literature are discussed below. Compound [Zr(L2-py)(OtBu)2]18 shows a discrete monomeric six-
coordinated Zr complex in which the amide ligand acts as a four-dentate dianion ligand (L2-py = N,N'-
bis(2-pyridinecarboxamido)-1,2-diphenylethane). Two other coordination sites are occupied by
monodentate OtBu anions. In compound [Ni(L2-py)].(C2H5)2O,19 the metal center is four-coordinted
with four-dentate dianion amide ligands. In compound [Cu(L2-py)],20 the metal center coordinates the
four nitrogen donor atoms of amide lagnad, while the carbonyl oxygen atom bridges two adjacent metal
centers to generate of a 1D chain motif. It is notable in all of these compounds that L adopts an anti-syn-
anti conformation.
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In the crystal packing of these complexes, the adjacent Hg2X2(ꢀ-X)2 moieties are linked by L through
Npy to form a one-dimensional, 1D, polymeric chain. The two independent polymeric chains are closely
packed through coordination bonds established between the carbonyl group and Hg(II) centre, Figure 4.
It is notable that the formation of parallel π-π stacks between the pyridyl rings of adjacent 1D chains
influences the C=O-Hg angles. The pyridyl rings of adjacent ligands involved in the intermolecular π-π
stacking interaction is arranged in such a way that the angle between the plane (containing C-CO-N
fragment) normal and O-Hg vector (for geometrical defination see reference 21) reaches about 50.99°
and 47.44° in 1 and 2 respectively. A Cambridge Structural Database (with the help of ConQuest
version 1.14)29 search about the coordination of ligands which contain isonicotinamide as a portion of
their structures was carried out and 326 hits were found. Among these structures only in 15 hits14 both
of the oxygen and nitrogen atoms were coordinated to the transition metal centres and in between them
only 1 hit15 has mercury (II) as its metal center. In these 15 structures additional forces lead to the
coordination of carbonyl and pyridine at the same time. These forces involve factors like π…π stacking
interactions, C-H…π intermolecular interactions and chelating effects.14 In compounds 1 and 2, π…π
stacking interactions between pyridine rings facilitate the coordination of the carbonyl group. It was
thought of interest to investigate further, using theoretical methods, the nature of the π…π stacking
interactions in both compounds 1 and 2. Calculations were performed with the experimental structure of
the stacked pyridine rings as the starting point at the MP2/aug-cc-PVDZ level. The interaction energy
between the two adjacent pyridine rings is 20.3 and 19.8 kJ mol-1 for compounds 1 and 2, respectively.
When energetic factors are taken into account, the coordination can be considered as the primary and
the aromatic interaction as the secondary effect. Therefore, interplay of coordination of carbonyl group,
C=O-Hg, and π...π stacking of pyridine rings lead to the formation of 2D structures. A simple survey in
the CSD shows that the histograms of geometrical parameters of this aromatic interaction such as
centroid-to-centroid distance (3.870 and 3.903 Å for 1 and 2, respectively), displacement angle and
angle of the pyridine rings are in the normal ranges (see ESI, Fig. S4). The scattergram of centriod-to-
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centriod distances vs displacement angles conforms the existence of this interaction, Figure S5. Such π-
π interaction effects on the primary structure directing coordination geometry around the Hg(II)
containing similar ligands with those discussed in this paper has been reported previously in detail by
some of us.21
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As depicted in Figure 4, two different boxes can be defined. In box I, the interchain distance of the
neighboring mercury atoms bridged by different L ligands through the carbonyl group, are about
7.789(1) and 7.685(1) Å in 1 and 2 respectively. The π…π interactions between the pyridine rings are
shown by red dashed lines in box I. In box II, the distance of neighboring mercury atoms bridged by one
L ligand through the carbonyl and pyridine group, are about 13.037(2) and 13.142(2) Å in 1 and 2
respectively. Dimethyl formamide molecules are trapped in box II, Figure4, which is connected through
hydrogen bonding interactions between the oxygen atom of DMF molecules and the hydrogen atom of
the amide ligand, Table 3.
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Phenyl groups in both complexes are in the trans position. This trans conformation is due to anion…π
interactions between phenyl rings and bridged halogen among two metal centres, Figure 5. Over the past
decade, the importance of lone-pair…π interaction has been recognized as a highly directional
supramolecular interaction.30 This interaction forms between an electron-deficient π ring system and an
electron-rich atom such as a halogen atom. Figure S6 shows geometrical parameters which determine
the strenght of this interaction. A CSD search reveals that all parameters for determining these
interactions are in the normal range31 and phenyl groups are in the trans position.
The decomposition behaviour of compounds 1 and 2 was investigated in static air atmosphere from
ambient to 600 °C, Figures S7 and S8 respectively. The thermogravimetric analyses reveal that both
compounds have identical decomposition patterns. As can be seen from the thermograms, 1 and 2 are
stable up to 243 and 250 °C respectively, when the hydrogen bonds between DMF and ligand are
broken and consequently the loss of DMF molecules takes place. The experimental mass loss of 13.5%
and 11.7% for 1 and 2 respectively, is in consistant with the calculated values of 13.2% and 11.3% for
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elemination DMF solvent molecules. At 275-363 °C for 1 and 280-383 °C for 2, both compounds will
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be decomposed.
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Conclusions
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In summary, we have illustrated that 1D coordination polymeric chains further extend into 2D networks
via cooperation of coordination bonds along with π…π interactions. Hence weak non-covalent
interactions seem to play a significant role in the formation of crystal packing and stabilizing of the
supramolecular structures. The results also demonstrate that the flexibility of the ligand enables the
formation of higher dimensional structures.
ACKNOWLEDGMENT. We would like to thanks the Graduate Study Councils of Shahid Beheshti
University, General Campus and the Iran National Science Foundation (Proposal No: 87041984) for
financial support and Prof. S. W. Ng for providing us with the software (Gaussian suite of programs)
and hardware (machine time) facilities and also giving us the opportunity to access some new features
of the Gaussian products.
SUPPORTING INFORMATION PARAGRAPH. Electronic Supplementary Information (ESI)
available: [Figures S1–S5 show conformations of L and diagrams of CSD searches. CCDC reference
numbers for L, 1 and 2 are 875332, 875330 and 875331, respectively]. These materials are free of
charge via Internet at http://pubs.acs.org.
SCHEME AND FIGURE CAPTIONS.
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Scheme 1. Schematic representation of portions of the structure of the 2D isostructural coordination
networks formed between L and HgX2 (X=Cl, Br). DMF solvent molecules are omitted for clarity.
Different colors show different 1D chains.
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Figure 1. The ORTEP diagram of N,N'-(1,2-diphenylethane-1,2-diyl)diisonicotinamide ligand, L.
Ellipsoids are drawn at 30% probability level. Sulfur atom in DMSO solvent is split into two partial
atoms with 50% occupancies. Symmetry code; i) 1-x, -y, 2-z.
Figure 2. (a) A representation of part of the unit cell contents of L shows generation of 2D sheets by
cooperation of C-H…N and C-H…O=C non-classical classical hydrogen bonds and (b) a side view
representation of L showing the presence of S=O…H-N and S=O…H-C classical and non-classical
hydrogen bonds between adjacent 2D sheets. DMSO solvent molecules are shown in ball and stick.
Different colors show different adjacent molecules in (a) or different adjacent 2D sheets in (b).
Figure 3. Portion of the structure of coordination polymers formed between L and HgX2, showing
coordination geometry around centeral metal. Symmetry codes; i) 2–x, 1-y, 1-z, ii) 1-x, 1-y, 1-z, iii) -x,
2-y, -z.
Figure 4. Portion of 1 and 2 which are generated through interplay of Hg–O=C coordination bonds and
π…π interaction of pyridine moieties to form 2D network. In box I, π-π stacking interactions are shown
by dashed red lines. In box II, DMF solvent molecules are shown by ball and stick style and packed via
hydrogen bonding which are displayed by dashed blue lines. All hydrogen atoms except those involved
in hydrogen bonds are omitted for clarity.
Figure 5. Anion…π interactions in crystal packing of [Hg2Cl4L.2(DMF)]n and [Hg2Br4L.2(DMF)]n.
The interactions of anion…centroid and separating distance of phenyl ring are shown by dashed lines.
REFERENCES:
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1 (a) Grepioni, F.; Braga, D. Making Crystals by Design, Methods, Techniques, Applications, Wiley-
VCH: Weinheim, Germany, 2007; (b) Lehn, J.-M. Supramolecular Chemistry: Concepts and
Prespectives, Wiley-VCH: Weinheim, Germany, 1995; (c) Steed, J. W.; Atwood, J. L.
Supramolecular Chemistry, Wiley: Chichester, U. K., 2000; (d) Batten, S. R.; Neville, S. M.;
Turner, D. R. Coordination Polymers: Design, Analysis and Application, Royal Society of
Chemistry: Cambridge, U. K., 2009; (e) Biradha, K.; Su, C.-Y.; Vittal, J. J. Cryst. Growth Des. 2011,
11, 875-886; (f) Aakeröy, C. B.; Champness, N. R.; Janiak, C. CrystEngComm 2010, 12, 22-43; (g)
Desiraju, G. R. Angew. Chem. Int. Ed. 2007, 46, 8342-8356; (h) Braga, D.; Brammer, L.;
Champness, N. R. CrystEngComm 2005, 7, 1-19.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
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24
25
26
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28
29
30
31
32
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36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
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53
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55
56
57
58
59
60
2 (a) Hsu, Y.-F.; Hu, H.-L.; Wu, C.-J.; Yeh, C.-W.; Proserpio, D. M.; Chen, J.-D. CrystEngComm
2009, 11, 168-176; (b) Shin, D. M.; Lee, I. S.; Cho, D.; Chung,Y. K. Inorg. Chem. 2003, 42, 7722-
7724; (c) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Rizzato, S. CrystEngComm 2002, 4, 413-425; (d)
Liu, T.-F.; Lü, J.; Cao, R. CrystEngComm 2010, 12, 660-670.
3 (a) Yang, J.; Wu, B.; Zhuge, F.; Liang, J.; Jia, C.; Wang, Y.-Y.; Tang, N.; Yang, X.-J.; Shi, Q.-Z.
Cryst. Growth Des. 2010, 10, 2331-2341; (b) Gándara, F.; Medina, M. E.; Snejko, N.; Gutiérrez-
Puebla, E.; Proserpio, D. M.; Monge, M. A. CrystEngComm 2010, 12, 711-719; (c) Zheng, S.-R.;
Yang, Q.-Y.; Yang, R.; Pan, M.; Cao, R.; Su, C.-Y. Cryst. Growth Des. 2009, 9, 2341-2353.
4 (a) Notash, B.; Safari, N.; Khavasi, H. R. Inorg. Chem. 2010, 49, 11415-11420; (b) Janssen, F. F. B.
J.; Veraart, L. P. J.; Smits, J. M. M.; Gelder, R.; Rowan, A. E. Cryst. Growth Des. 2011, 11, 4313-
4325; (c) Bu, X.-H.; Chen, W.; Hou, W.-F.; Du, M.; Zhang, R.-H.; Brisse, F. Inorg. Chem. 2002, 41,
3477-3482.
5 (a) Khavasi, H. R.; Sadegh, B. M. M. Inorg. Chem. 2010, 49, 5356-5358; (b) Zheng, B.; Bai, J.;
Zhang, Z. CrystEngComm 2010, 12, 49-51; (c) Wu, B.; Yang, J.; Liu, Y.; Zhuge, F.; Tang, N.; Yang,
X.-J. CrystEngComm 2010, 12, 2755-2761; (d) Yin, P.-X.; Zhang, J.; Qin, Y.-Y.; Cheng, J.-K.; Li,
Z.-J.; Yao, Y.-G. CrystEngComm 2011, 13, 3536-3544; (e) Li, C.-P.; Du, M. Chem. Commun. 2011,
47, 5958-5972; (f) Long, L.-S. CrystEngComm 2010, 12, 1354-1365.
6 (a) Xia, Y.; Li, S.; Wu, B.; Liua, Y.; Yang, X.-J. CrystEngComm 2011, 13, 5763-5772; (b)
Dechambenoit, P.; Ferlay, S.; Hosseini, M. W.; Kyritsakas, N. Chem. Commun. 2007, 4626-4628.
7 (a) Wu, J.-Y.; Hsu, H.-Y.; Chan, C.-C.; Wen, Y.-S.; Tsai, C.; Lu, K.-L. Cryst. Growth Des. 2009, 9,
258-262; (b) Yang, J.; Ma, J.-F.; Liu, Y.-Y.; Ma, J.-C.; Batten, S. R. Cryst. Growth Des. 2009, 9,
1894-1911; (c) Semeniuc, R. F.; Reamera, T. J.; Smith, M. D. New J. Chem. 2010, 34, 439-452.
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8 (a) Yang, S.-Y.; Naumov, P.; Fukuzumi, S. J. Am. Chem. Soc. 2009, 131, 7247-7248. (b) Blanco, V.;
Abella, D.; Pia, E.; Platas-Iglesias, C.; Peinador, C.; Quintela, J.M. Inorg. Chem. 2009, 48, 4098-
4107. (c) Kumagai, H.; Akita-Tanaka, M.; Kawata, S.; Inoue, K.; Kepert, C.J.; Kurmoo, M. Cryst.
Growth Des. 2009, 9, 2734-2741. (d) Banerjee, S.; Adarsh, N.N.; Dastidar, P. CrystEngComm 2009,
11, 746-749.
1
2
3
4
5
6
7
8
9
9 (a) Schottel, B. L.; Chifotides, H. T.; Shatruk, M.; Chouai, A.; Pérez, L. M.; Bacsa, J.; Dunbar, K. R.
J. Am. Chem. Soc. 2006, 128, 5895-5912. (b) Campos-Fernandez, C. S.; Schottel, B. L.; Chifotides,
H. T.; Bera, J. K.; Bacsa, J.; Koomen, J. M.; Russell, D. H.; Dunbar, K. R. J. Am. Chem. Soc. 2005,
127, 12909-12923.
10
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58
59
60
10 (a) Hsu, Y.-F.; Hsu, W.; Wu, C.-J.; Cheng, P.-C.; Yeh, C.-W.; Chang, W.-J.; Chen, J.-D.; Wang, J.-
C. CrystEngComm 2010, 12, 702-710; (b) Plater, M. J.; Gelbrich, T.; Hursthouse, M. B.; De Silva, B.
M. CrystEngComm 2008, 10, 125-130.
11 Bai, Y.; Gao, H.; Dang, D.-B.; Guo, X.-Y.; An, B.; Shang, W.-L. CrystEngComm 2010, 12, 1422-
1432.
12 (a) Hao, Y.; Wu, B.; Li, S.; Jia, C.; Huang, X.; Yang, X.-J. CrystEngComm 2011, 13, 215-222; (b)
Wu, B.; Liang, J.; Zhao, Y.; Li, M.; Li, S.; Liu, Y.; Zhang, Y.; Yang, X.-J. CrystEngComm 2010, 12,
2129-2134; (c) Li, S.; Wu, B.; Hao, Y.; Liu, Y.; Yang, X.-J. CrystEngComm 2010, 12, 2001-2004;
(d) Adarsh, N. N.; Kumar, D. K.; Dastidar, P. Cryst. Growth Des. 2009, 9, 2979-2983; (e) Liang, J.;
Wu, B.; Jia, C.; Yang, X.-J. CrystEngComm 2009, 11, 975-977; (f) Adarsh, N. N.; Kumar, D. K.;
Dastidar, P. CrysEngComm 2008, 10, 1565-1573; (g) Zeng, Q.; Li, M.; Wu, D.; Lei, S.; Liu, C.; Piao,
L.; Yang, Y.; An, S.; Wang, C. Cryst. Growth Des. 2008, 8, 869-876.
13 (a) Kumar, D. K.; Das, A.; Dastidar, P. Cryst. Growth Des. 2006, 6, 1903-1909; (b) Pansanel, J.;
Jouaiti, A.; Ferlay, S.; Hosseini, M. W.; Planeix, J.-M.; Kyritsakas, N. New J. Chem. 2006, 30, 683-
688; (c) Kumar, D. K.; Das A.; Dastidar, P. J. Mol. Struct. 2006, 796, 139-145; (d) Burchell, T. J.;
Eisler, D. J.; Puddephatt, R. J. Inorg. Chem. 2004, 43, 5550-5557; (e) Burchell, T. J.; Eisler, D. J.;
Puddephatt, R. J. Chem. Commun. 2004, 944-945; (f) Uemura, K.; Kitagawa, S.; Fukui, K.; Saito, K.
J. Am. Chem. Soc. 2004, 126, 3817-3828; (g) Burchell, T. J.; Eisler, D. J.; Jennings, M. C.;
Puddephatt, R. J. Chem. Commun. 2003, 2228-2229.
14 (a) Freitas, M. C. R.; António, J. M. S.; Ziolli, R. L.; Yoshida, M. I.; Rey, N. A.; Diniz, R.
Polyhedron 2011, 30,1922-1926; (b) Sun, D.; Wei, Z.-H.; Yang, C.-F.; Wang, D.-F.; Zhang, N.;
Huang, R.-B.; Zhang, L.-S. CrystEngComm 2011, 13,1591-1601; (c) Du, M.; Zhang, Z.-H.; Wang,
X.-G.; Zhao, X.-J. Inorg. Chim. Acta 2009, 362, 1358-1360; (d) Ni, W.-X.; Li, M.; Zhan, S.-Z.; Hou,
J.-Z.; Li, D. Inorg. Chem. 2009, 48, 1433-1441; (e) Niu, C.-Y.; Zheng, X.-F.; Bai, L.-L.; Wu, X.-L.;
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Kou, C.-H. Acta Cryst. 2008, C64, m305-m307; (f) Moncol, J.; Mudra, M.; Lönnecke, P.; Hewitt,
M.; Valko, M.; Morris, H.; Svorec, J.; Melnik, M.; Mazur, M.; Koman, M. Inorg. Chim. Acta 2007,
360, 3213-3225; (g) Lian, Z.-X.; Cai, J.; Chen, C.-H.; Luo, H.-B. CrystEngComm 2007, 9, 319-327;
(h) Yajima, T.; Takamido, R.; Shimazaki, Y.; Odani, A.; Nakabayashi, Y.; Yamauchi, O. Dalton
Trans. 2007, 299-307; (i) Burchell, T. J.; Eisler, D. J.; Puddephatt, R. J. Cryst. Growth Des. 2006, 6,
974-982; (j) Wang, C.-X.; Du, C.-X.; Li, Y-H.; Wu, Y.-J. Inorg. Chem. Commun. 2005, 8, 379-381;
(k) Bhogala, B. R.; Thallapally, P. K.; Nangia, A. Cryst. Growth Des. 2004, 4, 215-218; (l)
Armstrong, C. M.; Bernhardt, P. V.; Chin, P.; Richardson, D. R. Eur. J. Inorg. Chem. 2003, 1145-
1156; (m) Tsintsadze, G. V.; Dzhavakhishvili, Z. O.; Aleksandrov, G. G.; Struchkov, Y. T.;
Narimanidze, A. P. Koord. Khim. 1980, 6, 785-792.
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15 Pansanel, J.; Jouaiti, A.; Ferlay, S.; Hosseini, M. W.; Planeix, J.-M.; Kyritsakas, N. New J. Chem.
2006, 30, 71-76.
16 (a) Baudron, S. A.; Salazar-Mendoza, D.; Hosseini, M. W. CrystEngComm 2009, 11, 1245-1254; (b)
Banerjee, S.; Adarsh, N. N.; Dastidar, P. CrystEngComm 2009, 11, 746-749; (c) Sarkar, M.; Biradha,
K. Cryst. Growth Des. 2006, 6, 1742-1745.
17 Min, T.; Zheng, B.; Bai, J.; Sun, R.; Li, Y.; Zhang, Z. CrystEngComm 2010, 12, 70-72.
18 Belda, O.; Duquesne, S.; Fischer, A.; Moberg, C. J. Organomet. Chem. 2004, 689, 3750-3755.
19 Yang, L.; Deng, D. –Y.; Li, M.; Zhou, X. –G. Acta Crystallogr. 2008, E64, m439.
20 Fenton, R. R.; Stephens, F. S.; Vagg, R. S.; Williams, P. A. J. Coord. Chem. 1991, 23, 291-311.
21 Khavasi, H. R.; Azizpoor Fard, M. Cryst. Growth Des. 2010, 10, 1892-1896.
22 Stoe & Cie, X–AREA, vesion 1.30: Program for the acquisition and analysis of data; Stoe & Cie
GmbH: Darmatadt, Germany, 2005.
23 (a) Stoe & Cie, X–RED, vesion 1.28b: Program for data reduction and absorption correction; Stoe &
Cie GmbH: Darmatadt, Germany, 2005; (b) Stoe & Cie, X–SHAPE, vesion 2.05: Program for crystal
optimization for numerical absorption correction; Stoe & Cie GmbH: Darmatadt, Germany, 2004.
24 Sheldrick, G. M. SHELX97. Program for crystal structure solution and refinement. University of
Göttingen, Germay, 1997.
25 Stoe & Cie, X-STEP32, Version 1.07b: Crystallographic package; Stoe & Cie GmbH: Darmstadt,
Germany, 2000.
26 Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi,
J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada,
M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;
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Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.;
Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski,
V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.;
Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford,
CT, 2004.
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27 Boys S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553-????.
28 Addison, A. W.; Rao, T. N.; Reedijk, J. ; Van Rijn, J.; Verschoor, G. C. J. Chem. Soc., Dalton Trans.
1984, 1349-1356.
29 Cambridge Structural Database, version 5.33, November 2011; CCDC: Cambridge, U. K.
30 (a) Mooibroek, T. J.; Black, C. A.; Gamez, P.; Reedijk, J. Cryst.Growth Des. 2008, 8, 1082-1093; (b)
Mooibroek, T. J.; Gamez, P.; Reedijk, J. CrystEngComm 2008, 10, 1501-1515.
31 Robertazzi, A.; Krull, F.; Knapp, E.-W.; Gamez, P. CrystEngComm 2011, 13, 3293-3300.
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Table 1. Crystal Data and Structural Refinement for Compounds L, 1 and 2
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L
1
2
7
8
9
furmula
fw
C30H34N4O4S2 C32H39Cl4Hg2N6O4 C32H39Br4Hg2N6O4
10
11
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578.75
0.71073
25
1111.64
0.71073
25
1289.44
0.71073
25
λ/Å
T/˚C
cryst. system monoclinic
triclinic
Pī
triclinic
Pī
space group
a/Å
P21/n
10.1703(10)
14.5624(19)
10.7222(10)
90.0
9.8707(8)
10.2064(8)
11.1344(9)
72.266(6)
87.9069(7)
62.061(6)
936.34(13)
1.972
9.9706(11)
10.2954(12)
11.2168(13)
71.308(9)
87.893(9)
63.152(8)
965.15(19)
2.218
b/Å
c/Å
α/˚
β/˚
105.410(7)
90.0
γ/˚
V/Å3
1530.9(3)
1.255
Dcalc/Mg.m-3
Z
2
1
1
ꢀ (mm-1)
F(000)
2θ (˚)
R (int)
GOOF
0.215
8.517
12.126
602
612
530
52.00
58.42
52.00
0.0578
1.109
0.0986
1.097
0.0450
1.196
a
R1 (I>2σ(I))
0.0624
0.0466
0.1108
0.0360
0.0958
b
wR2 (I>2σ(I)) 0.1298
aR1 = Σ||Fo|-|Fc||/Σ|Fo|, bwR2 = [Σ(w(Fo -Fc2)2)/Σw(Fo ) ]
2
2 2 1/2
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Table 2. Bond lengths [Å] and angles [°] around mercury (II) for [Hg2Cl4L.2(DMF)]n, 1, and
[Hg2Br4L.2(DMF)]n, 2.
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Complex
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2
Bond distance Hg1-X1
Hg1-X1a
2.340(2) 2.464(1)
3.051(2) 3.163(1)
2.319(2) 2.450(1)
2.453(4) 2.778(5)
2.453(4) 2.448(5)
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Hg1-X2
Hg1-O1b
Hg1-N1
Bond angle
X1-Hg1-X2 164.35(8) 162.64(3)
X1-Hg1-X1a 85.19(6) 87.86(3)
X1-Hg1-O1b 81.79(11) 80.83(11)
X2-Hg1-O1b 95.17(11) 93.16(11)
X1-Hg1-N1 96.53(12) 97.76(12)
X2-Hg1-N1 99.12(12) 99.48(12)
N1-Hg1-O1b 89.2(5)
Hg1-O1=C6b 50.99
103.3(2)
47.44
Symmetry codes; (a) 2–x, 1-y, 1-z, (b) 1-x, 1-y, 1-z.
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Table 3. Hydrogen bonding parameters (Å and °) for L, [Hg2Cl4L.2(DMF)]n, 1 and
[Hg2Br4L.2(DMF)]n, 2.
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Compound
D-H···A
d(D-H)
0.930
0.930
0.930
0.960
0.960
0.86
d(H···A)
2.690
2.450
2.530
2.550
2.629
2.000
2.000
2.050
d(D···A)
3.435(5)
3.357(3)
3.404(3)
3.488(3)
3.488(5)
2.851(3)
2.821(10)
2.839(11)
<(DHA)
138.0
166.0
157.0
166.0
149.0
168
Symmetry code
-x, -y, 3-z
-x, -y, 2-z
1-x, -y, 2-z
-1/2x, 1/2+y, 3/2-z
-1/2x, 1/2+y, 3/2-z
x, y, 1+z
Ligand, L
C2-H2…N1
C1-H1…O1
C3-H3…O2
C14-H14C…O1
C15-H15B…O1
N2-H2…O2
N2-H2B…O2
N2-H2B…O2
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[Hg2Cl4L.2(DMF)]n, 1
[Hg2Br4L.2(DMF)]n, 2
0.860
0.860
158
-
153
-
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Two coordination polymers [Hg2Cl4L.2(DMF)]n and [Hg2Br4L.2(DMF)]n where L is N,N'-(1,2-
diphenylethane-1,2-diyl)diisonicotinamide ligand have been synthesized and characterized. Our results
show that interplay between the coordination of carbonyl group and π…π interaction of adjacent
pyridine rings lead to the formation of 2D structures.
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