- Email: [email protected]
The interplay of thiophilic and hydrogen bonding interactions in the supramolecular architecture of phenylmercury 4-hydroxypiperidine dithiocarbamate
Accepted Manuscript The interplay of Thiophilic and Hydrogen Bonding Interactions in the Supramolecular Architecture of Phenylmercury 4-Hydroxypiperidine Dithiocarbamate Rajendra Prasad, Reena Yadav, Manoj Trivedi, Gabriele Kociok-Köhn, Abhinav Kumar PII:
S0022-2860(15)30302-1
DOI:
10.1016/j.molstruc.2015.10.001
Reference:
MOLSTR 21846
To appear in:
Journal of Molecular Structure
Received Date: 16 June 2015 Revised Date:
3 August 2015
Accepted Date: 1 October 2015
Please cite this article as: R. Prasad, R. Yadav, M. Trivedi, G. Kociok-Köhn, A. Kumar, The interplay of Thiophilic and Hydrogen Bonding Interactions in the Supramolecular Architecture of Phenylmercury 4-Hydroxypiperidine Dithiocarbamate, Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.10.001. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Table of Contents
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A new phenylmercury(II) dithiocarbamate complex [PhHg(S2CN(CH2)4CH(OH)] synthesized and characterized using integrated experimenatal and computational approach.
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The interplay of Thiophilic and Hydrogen Bonding Interactions in the Supramolecular Architecture of Phenylmercury 4-Hydroxypiperidine Dithiocarbamate Rajendra Prasad,a Reena Yadavb, Manoj Trivedic, Gabriele Kociok-Köhnd*, and Abhinav
a
Department of Chemistry, S.G.B. Amrawati University, Amrawati, India
Department of Chemistry, University of Lucknow, Lucknow 226 007 India Department of Chemistry, University of Delhi, Delhi-110007, India
d
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK
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c
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b
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Kumarb*
Abstract
A new phenylmercury(II) dithiocarbamate complex [PhHg(S2CN(CH2)4CH(OH)], (1) has been synthesized and characterized by elemental analyses, IR, 1H and 13C NMR spectroscopy
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and X-ray crystallography. The crystal structure of 1 shows a linear arrangement at the Hg(II) centre of the molecule through bonding of the sulfur atom of the dithiocarbamate ligand and the carbon atom of the aromatic ring. Weak intermolecular thiophilic Hg···S interactions lead
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to a “head-to-tail” dimer and the presence of a hydroxyl group at the periphery of piperidine moiety generates a 1D-chain network through intermolecular O···H interactions. The nature of weak intra- and intermolecular Hg···S, H···S and intermolecular O···H interactions have
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been assessed with the help of ab initio calculations and atoms-in-molecules (AIM) approach. Keywords: dithiocarbamate, mercury, weak interaction, ab initio, AIM. Email: [email protected] (G.Kociok-Köhn) [email protected] (A. Kumar) Phone: +91-9451891030
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ACCEPTED MANUSCRIPT 1. Introduction A considerable amount of interest is concentrated on the functionalization of the aliphatic and aromatic substituents in the dithiocarbamate chemistry [1-17]. This permits to develop the complicated architectures and this in turn has potential to give rise to tuneable physical properties [1-17]. But still the main problem the crystal engineers are facing is the
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reasonable assembly of molecules into three dimensional arrangements which are capable of controlling wide range of intermolecular interactions.
Organomercury(II) compounds continue to attract attention owing to their importance in the preparation of other organometallics [18-27], as intermediates in organic chemistry
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[18] and their relevance to mercury detoxification [19]. Organmercury(II) dithiocarbamates have been found to be extremely versatile groups in the construction of supramolecular arrays [28-35], exhibit photoluminescence properties [29, 30] and are also used as dyes for solar
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energy harvesting in dye-sensitized solar cells (DSSCs) [31, 35].
The earlier investigation on phenylmercury(II) dithiocarbamate complexes revealed that the bulkiness of the pendant group in the ligands play important role in the construction of the supramolecular architecture through Hg···S interactions [28]. Alcock termed such contacts as “secondary interactions” [36-39]. Organomercury(II) dithiocarbamates having an
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-NH2 group in the periphery of the dithiocarbamate ligand have been reported [28], but because of the steric restrictions, the compounds have not exhibited intermolecular Hg···N secondary interactions. Recently we had reported the organomercury(II) dithiocarabamates displaying weak Hg···N secondary interactions alongwith the Hg···S interaction and their
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nature was addressed using quantum chemical calculations [40]. Additionally the role of weak Hg···N secondary interactions alongwith the Hg···S interaction was also investigated in
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controlling the photoluminescent properties [40]. With these viewpoints and in the quest of new type of secondary interactions in
organomercury(II) dithiocarbamates and to generate the new supramolecular motifs herein we report the synthesis, characterization and X-ray structures of a new phenylmercury(II) dithiocarbamate containing –OH group at the periphery of the dithiocarbamate ligand. The magnitude of intermolecular interaction energies in supramolecular motifs have been estimated at the MP2 level of theory and the intra- as well as the inter-molecular interactions have been validated using atoms-in-molecules (AIM) theory. 2.
Experimental details
2.1
General considerations 2
ACCEPTED MANUSCRIPT All chemicals were of analytical grade obtained from commercial sources and used without further purification. The solvents were purified in accordance with the standard methods. IR as KBr pellet was recorded on Varian 3100 FTIR spectrophotometer. The FT-IR experiment was performed under ambient conditions. A total of 30 scans were accumulated cm-1. The 1H and
13
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for the spectrum to obtain a resonable signal to noise ratio with a spectral resolution of 10 C NMR spectra in DMSO-d6 were recorded on a and JEOL AL300
FTNMR spectrometer. Chemical shifts were reported in parts per million using TMS as
CHN analyzer”. 2.2
Synthesis of [PhHg(S2CN(CH2)4CH(OH)] (1)
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internal standard. Elemental analysis was performed on Exeter analytical Inc “Model CE-440
4-hydroxypiperidine (0.101 g, 1 mmol) was dissolved in 15 mL of anhydrous THF
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and to it was added NaOH (0.040 g, 1 mmol) dissolved in 0.5 mL of water. The mixture was stirred for 10 min and then CS2 (0.114 g, 1.5 mmol) was added. The mixture was stirred for an additional 30 min until the colour of the solution became yellow. To the resulting solution phenylmercury(II) acetate (0.335 g, 1 mmol) dissolved in dichloromethane (15 mL) was added dropwise and the solution was additionally stirred for another 1 h. The resulting
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solution was filtered and evaporated at room temperature to obtain a white coloured powder of [PhHg(S2CN(CH2)4CH(OH)].
[PhHg(S2CN(CH2)4CH(OH)] (1) (0.377 g, yield 83 %); m.p. 187 °C. 1H NMR (DMSO-d6, δ): 7.39-1.18 (m, 5H, C6H5), 4.90 (s, 1H, -OH), 4.23 (s, 4H, -CH2), 3.84 (s, 4H, 13
C NMR (CDCl3, δ): 199.7 (-NCS2), 155.6, 138.2, 137.2, 128.3,
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CH2), 3.56 (s, 1H, -CH).
127.9, 127.7 (C6H5), 64.8, 47.9, 33.8 (piperdine). νmax(KBr)/cm-1 3705 (–OH), 1433 (C=N),
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967 (C=S), 851 (C-S). Anal. Calc. for C12H15HgNOS2: C, 31.75; H, 3.33; N, 3.09. Found: C, 31.90; H, 3.28; N, 3.16%. 2.3
X-ray crystallography Intensity data for 1 were collected at 150(2) K on an Agilent Xcalibur diffractometer
using graphite monochromated Mo-Kα radiation λ = 0.71073 Å. Unit cell determination, data collection and data reduction were performed with CrysAlisPro [41]. The structure was solved by direct methods (SIR97) [42] and refined by a full-matrix least-squares procedure based on F2 [43]. All non-hydrogen atoms were refined anisotropically; hydrogen atoms were located at calculated positions and refined using a riding model. All hetero hydrogen atoms have been located in the difference Fourier map and were refined with bond lengths 3
ACCEPTED MANUSCRIPT restraints. The asymmetric unit consists of half a dimeric Hg complex and one CHCl3 solvent molecule which is located about a two fold axis and therefore disordered with occupation factor of 50%. Two solvent molecule atoms C21 and CL2 had to be refined with ADP restraints. The OH group in the main molecule is disordered over two sites in the ratio 1:1. Bond length restraints were applied for O1, O1A and H1, H1A. Additionally, H1 had to be
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refined riding on its parent atom as the ADP became negative. There is one large peak 2.3 Å from Hg which is an artefact.
Crystal Data: C25H31Cl3Hg2N2O2S4, M = 1027.29, Monoclinic, I2/a, a = 9.1909(3) Å, b = 11.9357(5) Å, c = 31.0086(13) Å, β = 97.783(4)°, V = 3370.3(2) Å3, Z=4, Dcalc=2.025 mg
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m-3, F(000) = 1944, crystal size 0.120 × 0.040 × 0.036 mm, reflections collected 14388, independent reflections 3802 [R(int) = 0.0489], Final indices [I> 2σ(I)] R1 = 0.0509 wR2 = and hole 5.204 and -1.739 e Å−3. 2.4
Computational details
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0.1208, R indices (all data) R1 = 0.0612, wR2 = 0.1260, gof 1.133, Largest difference peak
Molecular geometries were optimized at the level of density functional theory (DFT) using the B3LYP exchange-correlation functional [44]. The split valence basis sets, 6-31G**
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were used at all C, N, O, S and H atom centres. Stephens, Basch, Krauss ECP triple-split basis set, CEP-121G was used for the Hg atom. Vibrational analysis was performed at the same level as geometry optimization. Potential energy distribution along internal coordinates was calculated by VEDA 4 software [45]. Internal coordinate system recommended by Pulay
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et al. was used for the assignment of vibrational modes [46]. The molecular electrostatic potential surfaces for monomer as well as the dimer have been generated using the same level
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of theory. The crystal structure of 1 was used as a starting point for all geometry optimizations. The intermolecular interaction energies have been estimated at the MP2 level of theory. For the interaction energy calculations, the Hg···S distances have been fixed for the dimer while all other degrees of freedom were relaxed in the geometry optimization. The stabilization energies for dimeric motif involving the two molecules (∆Edimer) were calculated from the formula ∆Edimer = Edimer –(2 × Emonomer). Emonomer was calculated by optimizing a single molecule at the same level of theory. The intermolecular interaction strengths are significantly weaker than either ionic or covalent bonding, therefore it was essential to do basis set superposition error (BSSE) corrections. The BSSE corrections in the interaction energies were done using Boys-Bernardi scheme. In this paper all the interaction energies
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ACCEPTED MANUSCRIPT have been reported after BSSE correction [47]. All computational experiments have been performed using the Gaussian 03 programme [48]. S Na HO
NH
CS2 + NaOH
HO
N
THF + H2O
S
S HO
N S
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PhHgOOCCH3 in dichloromethane
Hg
Results and discussion
3.1
Synthesis
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Scheme 1. Synthesis of the complex 1.
Complex [PhHg(S2CN(CH2)4CH(OH)] (1) was obtained by the addition of stoichiometric amount of phenylmercuric acetate to sodium 4-piperidinoldithiocarbamate in a mixture of THF, water and dichloromethane (Scheme 1). Complex 1 was air stable and moderately soluble in DMSO, methanol, acetone, dichloromethane and chloroform. Crystals
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of 1 suitable for X-ray structural analysis were obtained by slow evaporation of a chloroform/methanol mixture. 3.2
Spectroscopy
The purity and composition of the complex was checked by 1H NMR spectroscopy.
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All 1H NMR signals correspond to the piperidine moiety of the dithiocarbamate ligand and the phenyl group attached to mercury centre. Ins
13
C NMR the signal at ~ δ 199 ppm
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corresponds to the thioureide (NCS2) function. The IR spectrum of the compound show distinct vibrational bands at 967 and 851cm-1
which are calculated at 971 and 888 cm-1 can be assigned to the ν(CS2) vibration (supplementary informations). The observed splitting in ν (CS2) may be attributed to monodentate coordination of sulfur atom of the dithiocarbamate ligand to PhHg moiety. The band in the 1433 cm-1 region is associated primarily with the thioureide vibration and can be assigned to the ν(C=N) which is appreciably higher than the free ligand and thereby indicates a significant increase in the partial double bond character in the C-N bond. The observed band is calculated at 1432 cm-1 which is in good agreement with experimental spectral data.
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the free –OH function in the piperidinol moiety.
scheme. Solvent molecule had been omitted for clarity. Molecular Structure Description
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3.3
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Fig. 1 ORTEP diagram of a molecule of 1 at 30% probability with the atom numbering
The immediate coordination geometry about the Hg atom in 1 is defined by the ipso-C atom of the phenyl group and the atom S1 of the dithiocarbamate ligand (Fig. 1). The Hg-S1 bond length is 2.388(2) Å. This is significantly shorter than the Hg···S2 distance of 3.016(2) Å and hence reflecting the propensity of Hg to exist in linear coordination geometry. The proximity of atom S2 is partly responsible for the deviation from the ideal linear geometry, as
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can be seen in the (Ph)C7- Hg-S1 bond angle of 172.1(3)°. These bond lengths and angle are in close agreement with those in complexes reported earlier (Table 1). The deviations from planarity of atoms Hg, S1, S2 and C1, defining the chelate ring are 0.01, 0.02, 0.02 and 0.03
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Å, respectively. Within the dithiocarbamate function, the C1-N bond length of 1.332(1) Å indicates a substantial delocalization of the π-electron density density in the bond [49]. The six member piperidine ring adopts a normal 5C chair conformation.
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Table 1. Selected geometrical parameters for the PhHg(dithiocarabamate) structures Compound
Ref.
Hg-S2/ Å
Hg···S/Åa
C-Hg-S/ °
Hg···S/ Åf
PhHg(S2CN(Bun)2)
29
2.402(2)
2.9465(19)
170.60(19)
3.22; 3.87
PhHg(S2CN(CH2)4O)
29
2.3979(12)
2.9725(13)
169.97(14)
3.17; 3.61
PhHg(S2CNBz2)b
29
2.395(2)
2.905(3)
176.1(3)
3.36
PhHg(S2CNBz2)c
29
2.392(2)
2.924(3)
174.0(3)
3.55
PhHg(S2CN(CH2)4)
32
2.4009(13)
2.9056(13)
172.22(14)
3.1178
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2.4033(9)
2.9093(10)
166.76(10)
3.1809
PhHg(S2CNEt2)d
34
2.385(3)
2.978(3)
171.3(3)
3.191; 3.398
PhHg(S2CNEt2)e
34
2.387(3)
2.923(3)
172.2(3)
3.133; 3.174
PhHgS2CN(CH2Fc)CH2C6H5
30
2.388(2)
2.965(2)
168.5(3)
3.23
PhHgS2CN(CH2Fc)CH2CH(CH3)2
30
2.412(12)
2.9025(11)
170.91(12)
3.08
[PhHgS2CN(CH2Fc)]2(CH2C6H4CH2)
30
2.401(3),
2.876(3),
175.8(3),
2.400(3)
2.882(3)
176.8(4)
2.958(3)
168.5(3)
3.181
2.981(3)
168.3(3)
3.174
2.9327(14)
173.25(17)
3.133
3.016(2)
172.1(3)
3.145(2)
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PhHg(S2CN(Prn)2)
3.303;
31
2.402(3)
PhHgS2CN(CH2Fc)CH2C4H3O
31
2.397(3)
PhHgS2CN(CH2Fc)CH2CH2OH
31
2.3952(14)
PhHg(S2CN(CH2)4CH(OH)
This work
a
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PhHgS2CN(CH2Fc)CH2C5H4N
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3.749;3.640
2.388(2)
The Hg···S2 distance refers to the “chelate” Hg···S2 interaction. bTwo molecules in the asymmetric unit: molecule 1. c
Two molecules in the asymmetric unit: molecule 2. d Two molecules in the asymmetric unit: molecule 1.
e
Two
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molecules in the asymmetric unit: molecule 2. f Intermolecular interactions.
Fig. 2 One dimensional chain of dimer held by O-H···O interactions. As anticipated 1 features interesting intermolecular thiophilic Hg···S secondary
bonding leading to the formation of “head-to-tail” dimer (Fig. 2). These Hg···S contacts with an interaction length of 3.145(2) Å are comparable to the sum of the van der Waals radii of the respective elements (rvdw (Hg) = 1.73 – 2.00 Å and rvdw (S) = 1.80 Å) and are well in the range for organomercury dithiocarbamates [28]. Additionally, within the dithiocarbamate ligand there are pair of intramolecular C-H···S interactions viz. C(2)-H2A···S(1) (2.402 Å; 114.8°) and C6-H6B···S2 (2.567 Å; 113.4°). The incorporation of the –OH group at the C4 7
ACCEPTED MANUSCRIPT position of the piperidine moiety generates one dimensional chain. This one dimensional chain is formed by a pair of O1-H1···O1 intermolecular interactions with bond length of 2.44(11) Å and an angle of O1-H1···O1 166(36)° (Fig. 2). The solvent molecule chloroform also shows an O-H···Cl interaction with a distance of 2.95(19) Å and an interaction angle of 140(23)° but the solvent molecule does not exhibit the properties of the supramolecular
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synthon [50].
(b)
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(a)
Fig. 3 Electrostatic potential surfaces generated at B3LYP/6-31G**/CEP-121G level of theory for (a) monomer and (b) dimer held by inter-molecular Hg···S interaction (blue-green
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and red-yellow colours shows electron deficient and electron rich regions, respectively).
Fig. 4 Molecular graph for the dimer held by intra- and inter-molecular Hg···S interaction. Intramolecular C-H···S interactions are also shown. 3.4
DFT Results Regarding Non-covalent interactions
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ACCEPTED MANUSCRIPT The crystal structure of the compound as discussed above is a good example of the interplay of different molecular interactions that lead to interesting supramolecular aggregates in the solid state. The molecular electrostatic potential surfaces for the monomer as well as the dimer are presented in figure 3 which indicates that the hydroxyl oxygen is electron rich while hydroxyl hydrogen is electron deficient in nature which can lead to O−H···O
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interaction. Also, the Hg center is displaying light blue surface which is primarily responsible for the both intra- and inter-molecular Hg···S interactions with the sulphur atoms of the dithiocarbamate ligand which is displaying yellow coloured surface [40]. The analyses of the interaction energy in the crystal structure of the compound for dimer held by Hg···S
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interaction yields the interaction energy of 6.62 kJ/mol and those calculated for O−H···O interaction gives 7.91 kJ/mol. The interaction energy for the tetramer motif inculcating both intra- and intermolecular Hg···S and intermolecular O−H···O interactions gives the value
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13.83 kJ/mol. The interaction energy calculations indicate that both Hg···S and O−H···O
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interactions display no cooperative effect.
Fig. 5 Molecular graph for the dimer held by inter-molecular O···H interaction.
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Intramolecular C-H···S interactions are also shown. Table 2. Selected topographical features of intra- and inter-molecular Hg···S, C-H···S and O−H···O interactions computed at B3LYP/6-31G**/CEP-121G level of theory for monomer and dimer. Number of
Interactio
Molecular
n
ρbcp
2
(ε)
ρbcp
K
V
G
BPL–GBL
Units Hg···S2
+0.032710
+0.081482
+0.004345
+0.018035
-0.072221
+0.054186
+0.001104
+0.018853
+0.061043
+0.256948
-0.001340
-0.012581
+0.013921
+0.064563
+0.018656
+0.063748
+0.220045
-0.001520
-0.012897
+0.014417
+0.064114
(intra) Monomer
H···S2 (intra) H···S1
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+0.031337
+0.078842
+0.015596
+0.002075
-0023861
+0.021786
+0.007216
+0.018798
+0.060836
+0.251969
-0.001339
-0.012531
+0.013870
+0.062296
+0.018789
+0.063794
+0.216477
-0.001475
-0.012998
+0.014473
+0.062762
+0.031335
+0.078835
+0.015606
+0.002075
-0.023858
+0.021783
+0.007217
+0.018802
+0.060846
+0.251837
-0.001338
-0.012535
+0.013873
+0.062283
+0.018785
+0.063784
+0.216601
-0.001476
-0.012994
+0.014470
+0.062778
+0.013948
+0.035506
+0.080584
-0.000590
-0.007696
+0.008286
+0.000620
+0.013948
+0.035506
+0.080580
-0.000590
-0.007696
+0.008286
+0.000620
+0.007740
+0.028941
+0.042052
-0.001022
-0.005911
+0.006213
+0.023430
+0.032631
+0.081301
+0.004683
+0.002385
-0.025095
+0.022710
+0.007287
+0.018937
+0.061141
+0.251279
-0.001318
-0.012649
+0.013967
+0.063512
+0.018755
+0.063899
+0.213462
-0.001496
-0.012983
+0.014479
+0.062861
(intra) H···S2 (intra) H···S1
Dimer (held by
Hg’···S2’
intermolecular
(intra)
Hg···S
H···S2’
interaction)
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(intra)
(intra) H···S1’
Hg···S2
Hg’···S2’ (inter) O1···H1
Dimer (held by
Hg···S2
intermolecular
(intra)
O···H
H···S2
interaction)
(intra) H···S1 (intra)
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(inter)
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(intra)
QTAIM Results Regarding Non-covalent interactions
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To confirm further the presence of Hg···S, O−H···O and a new C−H···S interactions, bond critical points (bcp) were calculated for the monomer as well as for the dimers (Fig. 4, 5) by using the Atoms in Molecules theory [51]. The bond critical points observed between
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the Hg and S; O and H and H and S in both type of dimers confirms the presence of intra- and inter-molecular Hg···S, intermolecular O···H and intramolecular H···S interactions. The values of electron density (ρ); Laplacian ( 2ρbcp); bond ellipticity (ε), Hamiltonian form of the Kinetic Energy (K), Potential Energy density (V) and Lagrangian form of Kinetic Energy (G) and difference between the BPL and distance between nuclear attractor (BPL-GBL_I) at the bond critical point for Hg···S, O···H and H···S interactions for the compound are presented in Table 2. From table 2 it is evident that the electron density for all types of interactions at bond critical point (ρbcp) are less than +0.10 au which indicates a closed shell hydrogen bonding interactions. Additionally, the Laplacian of the electron density
2
ρbcp in all the
cases are greater than zero which indicates the depletion of electron density in the region of 10
ACCEPTED MANUSCRIPT contact between the Hg···S, O···H and H···S atoms. The bond ellipticity (ε) measures the extent to which the density is preferentially accumulated in a given plane containing the bond path. The ε values for all the interactions indicate that these Hg···S, O···H and H···S interactions are not cylindrically symmetrical in nature. The total electron energy density (Hb = G + V) associated with these interactions indicates that these interaction is not associated
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with the significant sharing of electrons and hence confirming the weak non-covalent interaction nature for these two atomic centers. Also, in comparison to the monomer the bond ellipticity for the intra-molecular Hg···S interaction in dimer is found to increase which indicates the loss of symmetry. This increase in ellipticity for the dimer may be attributed to
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the involvement of the same Hg center in intra- as well as the intermolecular Hg···S interaction. These results clearly indicates that the nature of intra- and intermolecular Hg···S interactions are totally depending on each other However, in the case of dimer held by O···H
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interaction the intra-molecular Hg···S ellipticity remains almost unchanged. These parameters indicate that the intermolecular O···H do not lead to an appreciable change in the nature of intra-molecular Hg···S interaction which indicates that both the interactions are completely independent of each other. As far as the ellipticity parameters for H···S interactions are concerned they were found to decrease for both the dimers held by intermolecular Hg···S or
4. Conclusions
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O···H interactions.
It can be concluded that incorporating the –OH group at the periphery of the alkyl fragment in dithiocarbamates enables the PhHg(II)dithiocarbamates to undergo new
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secondary bonding interactions without disturbing the intra- and intermolecular Hg···S interactions, a characteristic feature of the phenylmercury(II) dithiocarbamtes. Also the
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quantum chemical calculations indicate that the presence of both Hg···S and O···H interactions in the same molecule do not induce cooperative effects as these interactions are completely independent of each other. Also, AIM calculations have indicated that intra- and intermolecular Hg···S interactions are dependent upon each other and the ellipticity parameters for the intramolecular Hg···S changes on dimerization.
Acknowledgements AK is grateful to Department of Science and Technology, New Delhi for the financial assistance in the form of project no. SB/FT/CS-018/2012.
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ACCEPTED MANUSCRIPT Supporting material The crystallographic data in CIF format has been deposited with CCDC (CCDC deposition number is 1049185). This data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (internet.) +44-1223/336-033; E-
IR spectral data. References
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mail: [email protected]]. The supplementary information also include the computed
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I. Haiduc, Secondary Bonding, in Encyclopedia of Supramolecular Chemistry, Ed. J. L. Atwood
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Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl. Crystallogr. 32 (1999)
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Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M.; Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
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Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, W. M. Wong, C. Gonzalez and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004. [49]
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ACCEPTED MANUSCRIPT Bader, R. F. W. In Atoms in Molecules: A Quantum Theory; Oxford University Press:
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New York, 1990.
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[51]
15
ACCEPTED MANUSCRIPT
Research Highlight A new organomercury(II)dithiocarbamate complex synthesized
•
Compound was investigated via multi-technique experimental approach
•
Intermolecular Hg···S interactions lead to a“head-to-tail” dimer.
•
Presence of a hydroxyl group generates a 1D-chain network.
AC C
EP
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SC
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•
ACCEPTED MANUSCRIPT Vibrational assignment (PED%)
S.
IR
IR intensity
No.
unscaled
scaled
Exp.
1
3832
3708.9928
3705
2
3203
3100.1837
3
3194
3091.4726
4
3188
5
ν O29-H26(100)
1.086604
ν C2-H15(85) νC2-H15(12)
1.086604
ν C2-H15(81)
3085.6652
1.086604
ν C2-H15(81) ν C2-H15(13)
3179
3076.9541
1.086327
ν C3-H17(90)
6
3173
3071.1467
1.086604
ν C2-H15(82)
7
3164
3062.4356
1.087982
ν C1-H14(94)
8
3162
3060.4998
1.087982
ν C1-H14(94)
9
3102
3002.4258
1.094946
ν C5-H18(77) ν C1-H13(20)
10
3100
3000.49
1.098394
ν C1-H13(11) ν C5-H18(83)
11
3049
2951.1271
1.094946
ν C5-H18(19) ν C1-H13(73)
12
3037
2939.5123
1.098394
ν C1-H13(82) ν C5-H18(13)
13
3035
2937.5765
1.098394
ν C1-H13(93)
14
3031
2933.7049
1.098394
ν C1-H13(91)
15
3028
2930.8012
1.098394
ν C1-H13(89)
16
1630
1577.677
1.397242
ν C2-C3(10) ν C2-C3(54) θH15-C2-C3(21) θ C2-C3-C8 (10)
17
1627
1574.7733
1.395339
ν C2-C7(68) θH15-C2-C3(14)
18
1524
1475.0796
19
1517
1468.3043
20
1505
1456.6895
21
1498
1449.9142
22
1489
1441.2031
23
1480
1432.492
24
1471
25
1438
26
1402
27
1394
28
SC
1.346765
ν N28-C4(10) θH13-C1-H14(66)
1.397242
ν C2-C3(14) θH15-C2-C3(72)
107.38
θ H18-C5-22(81)
108.29
θ H13-C1-H14 (74)
EP
1470
TE D
2944
M AN U
3053
RI PT
0.967608
107.38
θ H18-C5-H22(87)
1.346765
ν N28-C4(38) θH13-C1-H14 (24)
1423.7809
1.397242
ν C2-C3(25) θH15-C2-C3(55)
1391.8402
107.65
θ H26-O29-C9 (23) Ф C9-C12-C5-H19 (56)
108.29
θ H13-C1-H14 (14) θ H13-C1-N28-C6 (50)
1349.2526
108.47
θ H19-C9-C12 (42)
1390
1345.381
107.65
θ H26-C29-C9 (15) τH14-C1-N28-C6(30)
29
1372
1327.9588
61.16
τ H13-C1-N28-C6(41) τ H13-C1-N28-C6(13)
30
1356
1312.4724
1305
1.397242
ν C2-C3(22) θ H15-C2-C3(13) θH17-C2-C3(58)
31
1340
1296.986
1290
111.24
θ H21-C6-C12 (20) θ H19-C9-C12 (29)
AC C
1433
1356.9958
1357
ACCEPTED MANUSCRIPT ν C2-C7(70)
107.65
τ H26-O29-C9 (16) τ C9-C12-C5-H19 (17)
1.472365
ν N28-C6(15) θ H21-C6-C12(12) θ H24-C12-C6(10)
109.71
θ H18-c5-C1 (21) θ H24-C12-C6 (14)
107.65
θ H26-O29-C9 (12) θ H13-C1-H14 (11) θ H15-C2-C3 (12)
1.397242
ν C2-C3 (15) θH15-C2-C3(60)
1161.48
1.473295
ν N28-C1(18) θ H21-C6-C12(10) θ C1-N28-C4(11)
1188
1149.8652
119.68
ν C2-C7(12) θH15-C2-C3(75)
40
1180
1142.122
109.71
θ H18-C5-C1(12) θ H24-C12-C6 (13) τ H13-C1-N28-C6(16) τ H13-C1-N28-C6(17)
41
1120
1084.048
1.421057
ν O29-C9(29) θC12-C9-C5(10)
42
1112
1076.3048
1.533955
ν C5-C1(14) ν C12-C9(20) ν C6-C12(12)
43
1099
1063.7221
1.397242
ν C2-C3(40) ν C2-C7(10) θH15-C2-C3(23) θH17-C3-C2(17)
44
1091
1055.9789
1064
1.421057
ν O29-C9(27) θH26-O29-C9(17) τ C12-C9-C5-C1(10)
45
1090
1055.011
1020
1.397242
ν C2-C3(52) θH15-C2-C3(23)
46
1040
1006.616
1001
1.397242
ν C2-C3(77)
47
1019
986.2901
1.533955
ν C5-C1(11) ν C6-C12(24)
48
1011
978.5469
1.397242
ν C2-C3(13) θ C2-C3-C8(62)
49
1004
971.7716
1.533955
ν C5-C1(15) ν S30-C4(15)
50
1001
968.8679
51
994
962.0926
52
978
946.6062
53
972
940.7988
54
923
893.3717
55
918
888.5322
56
863
57
862
58
815
59
806
60
1269.8848
34
1287
1245.6873
35
1274
1233.1046
36
1215
1175.9985
37
1214
1175.0306
38
1200
39
1257
1234
1174
1106
967
913
SC
1312
M AN U
33
TE D
1280.5317
111.04
τ H17-C3-C2-C7(77) τ C8-C3-C2-C7(17)
110.4
θ C5-C1-N28 (10) θ C12-C9-C5(11) τH13-C1-N28-C6(16)
61.16
τH13-C1-N28-C6(19)
180
τH15-C2-C3-C8(73) τC2-C7-C10-C11(25)
EP
1323
RI PT
1.395339
32
180.04
τH17-C3-C2-C7(94)
1.533955
ν C5-C1(11) ν S30-C4(16) ν C6-C12(16)
835.2977
1.473295
ν N28-C1(24) ν N28-C6(12)
834.3298
180
τ H15-C2-C3-C8(91)
788.8385
1.53405
ν C9-C5(12) τH13-C1-N28-C6(44)
AC C
851
780.1274
762
1.53405
ν C9-C5(14) ν C12-C9(22)
743
719.1497
730
180
τH15-C2-C3-C8(83) τC2-C7-C10-C11(10)
61
709
686.2411
696
180.04
τ H17-C3-C2-C7(18) τ H15-C2-C3-C8(11) τ C8-C3-C2-C7(61)
62
665
643.6535
2.117558
ν Hg32-C8(15) θC2-C3-C8 (69)
63
645
624.2955
110.4
θ C5-C1-N28 (21)
64
629
608.8091
120.39
θ C2-C3-C8 (88)
ACCEPTED MANUSCRIPT ФS30-N28-S31-C4(75)
517.8265
1.715239
ν S30-C4 (17) ν S31-C4(16) θC12-C9-C5 (11) Ф O29-C5-C12-C9 (10)
481
465.5599
110.4
θ C5-C1 -N28 (12) θ C9-C5-C1(15)
68
474
458.7846
61.16
τH13-C1-N28-C6(10) τH13-C1-N28-C6(15) ФO29-C5-C12-C9(23)
69
457
442.3303
0.01
τC2-C7-C10-C11(88)
70
439
424.9081
1.772326
ν S31-C4(11) θC1-N28-C4 (40)
71
410
396.839
1.772326
ν S31-C4(18) θS30-C4-S31(40)
72
405
391.9995
180
τH15-C2-C3-C8(27) τC2-C7-C10-C11(72)
73
387
374.5773
61.16
τH13-C1-N28-C6(12) ФO29-C5-C12-C9(13) ФC6-C1-C4-N28(20)
74
350
338.765
2.493695
ν Hg32-S31(23)
75
346
334.8934
122.83
θ C1-N28-C4 (24) θ C9-C5-C1 (13) τH26-O29-C9-C5 (29)
76
307
297.1453
122.83
θ C1-N28-C4(12) θ S30-C4-S31(21) τH26-O29-C9-C5 (16)
77
289
279.7231
122.83
θ C1-N28-C4 (24) τH26-O29-C9-C5(46)
78
233
225.5207
2.117558
ν Hg32-C8(57) θC2-C3-C8 (11)
79
202
195.5158
119.28
θ Hg32-C8-C3(61) θ S31-Hg32-C8(10)
80
190
183.901
2.493695
ν Hg32-S31(11) θHg32-C8-C3 (14) τC12-C9-C5-C1 (18) Ф O29-C5-C12-C9(12)
66
535
67
534
448
SC
545.8956
M AN U
564
RI PT
0.07
65
Ф C6-C1-C4-N28(10) 171.3183
82
166
160.6714
83
131
126.7949
84
88
85.1752
85
71
68.7209
86
57
55.1703
87
35
33.8765
88
26
89
18
90
15
55.52
τC9-C5-C1-N28(16)
TE D
177
181.2
τC2-C7-C10-C11(60) τC8-C3-C2-C7(10) τC4-S31-Hg32-C8(20)
2.493695
ν Hg32-S31(28) θC4-S31-Hg32 (32) τC9-C5-C1-N28 (12)
92.6
θ C4-S31-Hg32 (66)
181.2
τC2-C7-C10-C11(13) τC4-S31-Hg32-C8(20) τC1-N28-C4-S31(14) τC4-S31-Hg32-C8(42)
EP
81
τC1-N28-C4-S31(53) τC5-C1-N28-C4(11)
178.25
τC1-N28-C4-S31(23) τC5-C1-N28-C4(28) τC4-S31-Hg32-C8(11)
25.1654
119.28
θ Hg32-C8-C3(12) θ S31-Hg32-C8(73)
17.4222
181.2
τC4-S31-Hg32-C8(83)
14.5185
181.2
τC4-S31-Hg32-C8(60) τC4-S31-Hg32-C8(20)
AC C
178.25
S0022-2860(15)30302-1
DOI:
10.1016/j.molstruc.2015.10.001
Reference:
MOLSTR 21846
To appear in:
Journal of Molecular Structure
Received Date: 16 June 2015 Revised Date:
3 August 2015
Accepted Date: 1 October 2015
Please cite this article as: R. Prasad, R. Yadav, M. Trivedi, G. Kociok-Köhn, A. Kumar, The interplay of Thiophilic and Hydrogen Bonding Interactions in the Supramolecular Architecture of Phenylmercury 4-Hydroxypiperidine Dithiocarbamate, Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.10.001. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
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Table of Contents
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A new phenylmercury(II) dithiocarbamate complex [PhHg(S2CN(CH2)4CH(OH)] synthesized and characterized using integrated experimenatal and computational approach.
ACCEPTED MANUSCRIPT
The interplay of Thiophilic and Hydrogen Bonding Interactions in the Supramolecular Architecture of Phenylmercury 4-Hydroxypiperidine Dithiocarbamate Rajendra Prasad,a Reena Yadavb, Manoj Trivedic, Gabriele Kociok-Köhnd*, and Abhinav
a
Department of Chemistry, S.G.B. Amrawati University, Amrawati, India
Department of Chemistry, University of Lucknow, Lucknow 226 007 India Department of Chemistry, University of Delhi, Delhi-110007, India
d
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK
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c
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b
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Kumarb*
Abstract
A new phenylmercury(II) dithiocarbamate complex [PhHg(S2CN(CH2)4CH(OH)], (1) has been synthesized and characterized by elemental analyses, IR, 1H and 13C NMR spectroscopy
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and X-ray crystallography. The crystal structure of 1 shows a linear arrangement at the Hg(II) centre of the molecule through bonding of the sulfur atom of the dithiocarbamate ligand and the carbon atom of the aromatic ring. Weak intermolecular thiophilic Hg···S interactions lead
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to a “head-to-tail” dimer and the presence of a hydroxyl group at the periphery of piperidine moiety generates a 1D-chain network through intermolecular O···H interactions. The nature of weak intra- and intermolecular Hg···S, H···S and intermolecular O···H interactions have
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been assessed with the help of ab initio calculations and atoms-in-molecules (AIM) approach. Keywords: dithiocarbamate, mercury, weak interaction, ab initio, AIM. Email: [email protected] (G.Kociok-Köhn) [email protected] (A. Kumar) Phone: +91-9451891030
1
ACCEPTED MANUSCRIPT 1. Introduction A considerable amount of interest is concentrated on the functionalization of the aliphatic and aromatic substituents in the dithiocarbamate chemistry [1-17]. This permits to develop the complicated architectures and this in turn has potential to give rise to tuneable physical properties [1-17]. But still the main problem the crystal engineers are facing is the
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reasonable assembly of molecules into three dimensional arrangements which are capable of controlling wide range of intermolecular interactions.
Organomercury(II) compounds continue to attract attention owing to their importance in the preparation of other organometallics [18-27], as intermediates in organic chemistry
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[18] and their relevance to mercury detoxification [19]. Organmercury(II) dithiocarbamates have been found to be extremely versatile groups in the construction of supramolecular arrays [28-35], exhibit photoluminescence properties [29, 30] and are also used as dyes for solar
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energy harvesting in dye-sensitized solar cells (DSSCs) [31, 35].
The earlier investigation on phenylmercury(II) dithiocarbamate complexes revealed that the bulkiness of the pendant group in the ligands play important role in the construction of the supramolecular architecture through Hg···S interactions [28]. Alcock termed such contacts as “secondary interactions” [36-39]. Organomercury(II) dithiocarbamates having an
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-NH2 group in the periphery of the dithiocarbamate ligand have been reported [28], but because of the steric restrictions, the compounds have not exhibited intermolecular Hg···N secondary interactions. Recently we had reported the organomercury(II) dithiocarabamates displaying weak Hg···N secondary interactions alongwith the Hg···S interaction and their
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nature was addressed using quantum chemical calculations [40]. Additionally the role of weak Hg···N secondary interactions alongwith the Hg···S interaction was also investigated in
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controlling the photoluminescent properties [40]. With these viewpoints and in the quest of new type of secondary interactions in
organomercury(II) dithiocarbamates and to generate the new supramolecular motifs herein we report the synthesis, characterization and X-ray structures of a new phenylmercury(II) dithiocarbamate containing –OH group at the periphery of the dithiocarbamate ligand. The magnitude of intermolecular interaction energies in supramolecular motifs have been estimated at the MP2 level of theory and the intra- as well as the inter-molecular interactions have been validated using atoms-in-molecules (AIM) theory. 2.
Experimental details
2.1
General considerations 2
ACCEPTED MANUSCRIPT All chemicals were of analytical grade obtained from commercial sources and used without further purification. The solvents were purified in accordance with the standard methods. IR as KBr pellet was recorded on Varian 3100 FTIR spectrophotometer. The FT-IR experiment was performed under ambient conditions. A total of 30 scans were accumulated cm-1. The 1H and
13
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for the spectrum to obtain a resonable signal to noise ratio with a spectral resolution of 10 C NMR spectra in DMSO-d6 were recorded on a and JEOL AL300
FTNMR spectrometer. Chemical shifts were reported in parts per million using TMS as
CHN analyzer”. 2.2
Synthesis of [PhHg(S2CN(CH2)4CH(OH)] (1)
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internal standard. Elemental analysis was performed on Exeter analytical Inc “Model CE-440
4-hydroxypiperidine (0.101 g, 1 mmol) was dissolved in 15 mL of anhydrous THF
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and to it was added NaOH (0.040 g, 1 mmol) dissolved in 0.5 mL of water. The mixture was stirred for 10 min and then CS2 (0.114 g, 1.5 mmol) was added. The mixture was stirred for an additional 30 min until the colour of the solution became yellow. To the resulting solution phenylmercury(II) acetate (0.335 g, 1 mmol) dissolved in dichloromethane (15 mL) was added dropwise and the solution was additionally stirred for another 1 h. The resulting
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solution was filtered and evaporated at room temperature to obtain a white coloured powder of [PhHg(S2CN(CH2)4CH(OH)].
[PhHg(S2CN(CH2)4CH(OH)] (1) (0.377 g, yield 83 %); m.p. 187 °C. 1H NMR (DMSO-d6, δ): 7.39-1.18 (m, 5H, C6H5), 4.90 (s, 1H, -OH), 4.23 (s, 4H, -CH2), 3.84 (s, 4H, 13
C NMR (CDCl3, δ): 199.7 (-NCS2), 155.6, 138.2, 137.2, 128.3,
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CH2), 3.56 (s, 1H, -CH).
127.9, 127.7 (C6H5), 64.8, 47.9, 33.8 (piperdine). νmax(KBr)/cm-1 3705 (–OH), 1433 (C=N),
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967 (C=S), 851 (C-S). Anal. Calc. for C12H15HgNOS2: C, 31.75; H, 3.33; N, 3.09. Found: C, 31.90; H, 3.28; N, 3.16%. 2.3
X-ray crystallography Intensity data for 1 were collected at 150(2) K on an Agilent Xcalibur diffractometer
using graphite monochromated Mo-Kα radiation λ = 0.71073 Å. Unit cell determination, data collection and data reduction were performed with CrysAlisPro [41]. The structure was solved by direct methods (SIR97) [42] and refined by a full-matrix least-squares procedure based on F2 [43]. All non-hydrogen atoms were refined anisotropically; hydrogen atoms were located at calculated positions and refined using a riding model. All hetero hydrogen atoms have been located in the difference Fourier map and were refined with bond lengths 3
ACCEPTED MANUSCRIPT restraints. The asymmetric unit consists of half a dimeric Hg complex and one CHCl3 solvent molecule which is located about a two fold axis and therefore disordered with occupation factor of 50%. Two solvent molecule atoms C21 and CL2 had to be refined with ADP restraints. The OH group in the main molecule is disordered over two sites in the ratio 1:1. Bond length restraints were applied for O1, O1A and H1, H1A. Additionally, H1 had to be
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refined riding on its parent atom as the ADP became negative. There is one large peak 2.3 Å from Hg which is an artefact.
Crystal Data: C25H31Cl3Hg2N2O2S4, M = 1027.29, Monoclinic, I2/a, a = 9.1909(3) Å, b = 11.9357(5) Å, c = 31.0086(13) Å, β = 97.783(4)°, V = 3370.3(2) Å3, Z=4, Dcalc=2.025 mg
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m-3, F(000) = 1944, crystal size 0.120 × 0.040 × 0.036 mm, reflections collected 14388, independent reflections 3802 [R(int) = 0.0489], Final indices [I> 2σ(I)] R1 = 0.0509 wR2 = and hole 5.204 and -1.739 e Å−3. 2.4
Computational details
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0.1208, R indices (all data) R1 = 0.0612, wR2 = 0.1260, gof 1.133, Largest difference peak
Molecular geometries were optimized at the level of density functional theory (DFT) using the B3LYP exchange-correlation functional [44]. The split valence basis sets, 6-31G**
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were used at all C, N, O, S and H atom centres. Stephens, Basch, Krauss ECP triple-split basis set, CEP-121G was used for the Hg atom. Vibrational analysis was performed at the same level as geometry optimization. Potential energy distribution along internal coordinates was calculated by VEDA 4 software [45]. Internal coordinate system recommended by Pulay
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et al. was used for the assignment of vibrational modes [46]. The molecular electrostatic potential surfaces for monomer as well as the dimer have been generated using the same level
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of theory. The crystal structure of 1 was used as a starting point for all geometry optimizations. The intermolecular interaction energies have been estimated at the MP2 level of theory. For the interaction energy calculations, the Hg···S distances have been fixed for the dimer while all other degrees of freedom were relaxed in the geometry optimization. The stabilization energies for dimeric motif involving the two molecules (∆Edimer) were calculated from the formula ∆Edimer = Edimer –(2 × Emonomer). Emonomer was calculated by optimizing a single molecule at the same level of theory. The intermolecular interaction strengths are significantly weaker than either ionic or covalent bonding, therefore it was essential to do basis set superposition error (BSSE) corrections. The BSSE corrections in the interaction energies were done using Boys-Bernardi scheme. In this paper all the interaction energies
4
ACCEPTED MANUSCRIPT have been reported after BSSE correction [47]. All computational experiments have been performed using the Gaussian 03 programme [48]. S Na HO
NH
CS2 + NaOH
HO
N
THF + H2O
S
S HO
N S
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PhHgOOCCH3 in dichloromethane
Hg
Results and discussion
3.1
Synthesis
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3.
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Scheme 1. Synthesis of the complex 1.
Complex [PhHg(S2CN(CH2)4CH(OH)] (1) was obtained by the addition of stoichiometric amount of phenylmercuric acetate to sodium 4-piperidinoldithiocarbamate in a mixture of THF, water and dichloromethane (Scheme 1). Complex 1 was air stable and moderately soluble in DMSO, methanol, acetone, dichloromethane and chloroform. Crystals
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of 1 suitable for X-ray structural analysis were obtained by slow evaporation of a chloroform/methanol mixture. 3.2
Spectroscopy
The purity and composition of the complex was checked by 1H NMR spectroscopy.
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All 1H NMR signals correspond to the piperidine moiety of the dithiocarbamate ligand and the phenyl group attached to mercury centre. Ins
13
C NMR the signal at ~ δ 199 ppm
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corresponds to the thioureide (NCS2) function. The IR spectrum of the compound show distinct vibrational bands at 967 and 851cm-1
which are calculated at 971 and 888 cm-1 can be assigned to the ν(CS2) vibration (supplementary informations). The observed splitting in ν (CS2) may be attributed to monodentate coordination of sulfur atom of the dithiocarbamate ligand to PhHg moiety. The band in the 1433 cm-1 region is associated primarily with the thioureide vibration and can be assigned to the ν(C=N) which is appreciably higher than the free ligand and thereby indicates a significant increase in the partial double bond character in the C-N bond. The observed band is calculated at 1432 cm-1 which is in good agreement with experimental spectral data.
5
ACCEPTED MANUSCRIPT Additionally, the band observed at ~3705 cm‾1 and calculated at 3708 cm-1 is indicative of
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the free –OH function in the piperidinol moiety.
scheme. Solvent molecule had been omitted for clarity. Molecular Structure Description
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3.3
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Fig. 1 ORTEP diagram of a molecule of 1 at 30% probability with the atom numbering
The immediate coordination geometry about the Hg atom in 1 is defined by the ipso-C atom of the phenyl group and the atom S1 of the dithiocarbamate ligand (Fig. 1). The Hg-S1 bond length is 2.388(2) Å. This is significantly shorter than the Hg···S2 distance of 3.016(2) Å and hence reflecting the propensity of Hg to exist in linear coordination geometry. The proximity of atom S2 is partly responsible for the deviation from the ideal linear geometry, as
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can be seen in the (Ph)C7- Hg-S1 bond angle of 172.1(3)°. These bond lengths and angle are in close agreement with those in complexes reported earlier (Table 1). The deviations from planarity of atoms Hg, S1, S2 and C1, defining the chelate ring are 0.01, 0.02, 0.02 and 0.03
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Å, respectively. Within the dithiocarbamate function, the C1-N bond length of 1.332(1) Å indicates a substantial delocalization of the π-electron density density in the bond [49]. The six member piperidine ring adopts a normal 5C chair conformation.
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Table 1. Selected geometrical parameters for the PhHg(dithiocarabamate) structures Compound
Ref.
Hg-S2/ Å
Hg···S/Åa
C-Hg-S/ °
Hg···S/ Åf
PhHg(S2CN(Bun)2)
29
2.402(2)
2.9465(19)
170.60(19)
3.22; 3.87
PhHg(S2CN(CH2)4O)
29
2.3979(12)
2.9725(13)
169.97(14)
3.17; 3.61
PhHg(S2CNBz2)b
29
2.395(2)
2.905(3)
176.1(3)
3.36
PhHg(S2CNBz2)c
29
2.392(2)
2.924(3)
174.0(3)
3.55
PhHg(S2CN(CH2)4)
32
2.4009(13)
2.9056(13)
172.22(14)
3.1178
6
ACCEPTED MANUSCRIPT 33
2.4033(9)
2.9093(10)
166.76(10)
3.1809
PhHg(S2CNEt2)d
34
2.385(3)
2.978(3)
171.3(3)
3.191; 3.398
PhHg(S2CNEt2)e
34
2.387(3)
2.923(3)
172.2(3)
3.133; 3.174
PhHgS2CN(CH2Fc)CH2C6H5
30
2.388(2)
2.965(2)
168.5(3)
3.23
PhHgS2CN(CH2Fc)CH2CH(CH3)2
30
2.412(12)
2.9025(11)
170.91(12)
3.08
[PhHgS2CN(CH2Fc)]2(CH2C6H4CH2)
30
2.401(3),
2.876(3),
175.8(3),
2.400(3)
2.882(3)
176.8(4)
2.958(3)
168.5(3)
3.181
2.981(3)
168.3(3)
3.174
2.9327(14)
173.25(17)
3.133
3.016(2)
172.1(3)
3.145(2)
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PhHg(S2CN(Prn)2)
3.303;
31
2.402(3)
PhHgS2CN(CH2Fc)CH2C4H3O
31
2.397(3)
PhHgS2CN(CH2Fc)CH2CH2OH
31
2.3952(14)
PhHg(S2CN(CH2)4CH(OH)
This work
a
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PhHgS2CN(CH2Fc)CH2C5H4N
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3.749;3.640
2.388(2)
The Hg···S2 distance refers to the “chelate” Hg···S2 interaction. bTwo molecules in the asymmetric unit: molecule 1. c
Two molecules in the asymmetric unit: molecule 2. d Two molecules in the asymmetric unit: molecule 1.
e
Two
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molecules in the asymmetric unit: molecule 2. f Intermolecular interactions.
Fig. 2 One dimensional chain of dimer held by O-H···O interactions. As anticipated 1 features interesting intermolecular thiophilic Hg···S secondary
bonding leading to the formation of “head-to-tail” dimer (Fig. 2). These Hg···S contacts with an interaction length of 3.145(2) Å are comparable to the sum of the van der Waals radii of the respective elements (rvdw (Hg) = 1.73 – 2.00 Å and rvdw (S) = 1.80 Å) and are well in the range for organomercury dithiocarbamates [28]. Additionally, within the dithiocarbamate ligand there are pair of intramolecular C-H···S interactions viz. C(2)-H2A···S(1) (2.402 Å; 114.8°) and C6-H6B···S2 (2.567 Å; 113.4°). The incorporation of the –OH group at the C4 7
ACCEPTED MANUSCRIPT position of the piperidine moiety generates one dimensional chain. This one dimensional chain is formed by a pair of O1-H1···O1 intermolecular interactions with bond length of 2.44(11) Å and an angle of O1-H1···O1 166(36)° (Fig. 2). The solvent molecule chloroform also shows an O-H···Cl interaction with a distance of 2.95(19) Å and an interaction angle of 140(23)° but the solvent molecule does not exhibit the properties of the supramolecular
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synthon [50].
(b)
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(a)
Fig. 3 Electrostatic potential surfaces generated at B3LYP/6-31G**/CEP-121G level of theory for (a) monomer and (b) dimer held by inter-molecular Hg···S interaction (blue-green
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and red-yellow colours shows electron deficient and electron rich regions, respectively).
Fig. 4 Molecular graph for the dimer held by intra- and inter-molecular Hg···S interaction. Intramolecular C-H···S interactions are also shown. 3.4
DFT Results Regarding Non-covalent interactions
8
ACCEPTED MANUSCRIPT The crystal structure of the compound as discussed above is a good example of the interplay of different molecular interactions that lead to interesting supramolecular aggregates in the solid state. The molecular electrostatic potential surfaces for the monomer as well as the dimer are presented in figure 3 which indicates that the hydroxyl oxygen is electron rich while hydroxyl hydrogen is electron deficient in nature which can lead to O−H···O
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interaction. Also, the Hg center is displaying light blue surface which is primarily responsible for the both intra- and inter-molecular Hg···S interactions with the sulphur atoms of the dithiocarbamate ligand which is displaying yellow coloured surface [40]. The analyses of the interaction energy in the crystal structure of the compound for dimer held by Hg···S
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interaction yields the interaction energy of 6.62 kJ/mol and those calculated for O−H···O interaction gives 7.91 kJ/mol. The interaction energy for the tetramer motif inculcating both intra- and intermolecular Hg···S and intermolecular O−H···O interactions gives the value
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13.83 kJ/mol. The interaction energy calculations indicate that both Hg···S and O−H···O
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interactions display no cooperative effect.
Fig. 5 Molecular graph for the dimer held by inter-molecular O···H interaction.
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Intramolecular C-H···S interactions are also shown. Table 2. Selected topographical features of intra- and inter-molecular Hg···S, C-H···S and O−H···O interactions computed at B3LYP/6-31G**/CEP-121G level of theory for monomer and dimer. Number of
Interactio
Molecular
n
ρbcp
2
(ε)
ρbcp
K
V
G
BPL–GBL
Units Hg···S2
+0.032710
+0.081482
+0.004345
+0.018035
-0.072221
+0.054186
+0.001104
+0.018853
+0.061043
+0.256948
-0.001340
-0.012581
+0.013921
+0.064563
+0.018656
+0.063748
+0.220045
-0.001520
-0.012897
+0.014417
+0.064114
(intra) Monomer
H···S2 (intra) H···S1
9
ACCEPTED MANUSCRIPT (intra) Hg···S2
+0.031337
+0.078842
+0.015596
+0.002075
-0023861
+0.021786
+0.007216
+0.018798
+0.060836
+0.251969
-0.001339
-0.012531
+0.013870
+0.062296
+0.018789
+0.063794
+0.216477
-0.001475
-0.012998
+0.014473
+0.062762
+0.031335
+0.078835
+0.015606
+0.002075
-0.023858
+0.021783
+0.007217
+0.018802
+0.060846
+0.251837
-0.001338
-0.012535
+0.013873
+0.062283
+0.018785
+0.063784
+0.216601
-0.001476
-0.012994
+0.014470
+0.062778
+0.013948
+0.035506
+0.080584
-0.000590
-0.007696
+0.008286
+0.000620
+0.013948
+0.035506
+0.080580
-0.000590
-0.007696
+0.008286
+0.000620
+0.007740
+0.028941
+0.042052
-0.001022
-0.005911
+0.006213
+0.023430
+0.032631
+0.081301
+0.004683
+0.002385
-0.025095
+0.022710
+0.007287
+0.018937
+0.061141
+0.251279
-0.001318
-0.012649
+0.013967
+0.063512
+0.018755
+0.063899
+0.213462
-0.001496
-0.012983
+0.014479
+0.062861
(intra) H···S2 (intra) H···S1
Dimer (held by
Hg’···S2’
intermolecular
(intra)
Hg···S
H···S2’
interaction)
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(intra)
(intra) H···S1’
Hg···S2
Hg’···S2’ (inter) O1···H1
Dimer (held by
Hg···S2
intermolecular
(intra)
O···H
H···S2
interaction)
(intra) H···S1 (intra)
3.5
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(inter)
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(inter)
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(intra)
QTAIM Results Regarding Non-covalent interactions
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To confirm further the presence of Hg···S, O−H···O and a new C−H···S interactions, bond critical points (bcp) were calculated for the monomer as well as for the dimers (Fig. 4, 5) by using the Atoms in Molecules theory [51]. The bond critical points observed between
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the Hg and S; O and H and H and S in both type of dimers confirms the presence of intra- and inter-molecular Hg···S, intermolecular O···H and intramolecular H···S interactions. The values of electron density (ρ); Laplacian ( 2ρbcp); bond ellipticity (ε), Hamiltonian form of the Kinetic Energy (K), Potential Energy density (V) and Lagrangian form of Kinetic Energy (G) and difference between the BPL and distance between nuclear attractor (BPL-GBL_I) at the bond critical point for Hg···S, O···H and H···S interactions for the compound are presented in Table 2. From table 2 it is evident that the electron density for all types of interactions at bond critical point (ρbcp) are less than +0.10 au which indicates a closed shell hydrogen bonding interactions. Additionally, the Laplacian of the electron density
2
ρbcp in all the
cases are greater than zero which indicates the depletion of electron density in the region of 10
ACCEPTED MANUSCRIPT contact between the Hg···S, O···H and H···S atoms. The bond ellipticity (ε) measures the extent to which the density is preferentially accumulated in a given plane containing the bond path. The ε values for all the interactions indicate that these Hg···S, O···H and H···S interactions are not cylindrically symmetrical in nature. The total electron energy density (Hb = G + V) associated with these interactions indicates that these interaction is not associated
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with the significant sharing of electrons and hence confirming the weak non-covalent interaction nature for these two atomic centers. Also, in comparison to the monomer the bond ellipticity for the intra-molecular Hg···S interaction in dimer is found to increase which indicates the loss of symmetry. This increase in ellipticity for the dimer may be attributed to
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the involvement of the same Hg center in intra- as well as the intermolecular Hg···S interaction. These results clearly indicates that the nature of intra- and intermolecular Hg···S interactions are totally depending on each other However, in the case of dimer held by O···H
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interaction the intra-molecular Hg···S ellipticity remains almost unchanged. These parameters indicate that the intermolecular O···H do not lead to an appreciable change in the nature of intra-molecular Hg···S interaction which indicates that both the interactions are completely independent of each other. As far as the ellipticity parameters for H···S interactions are concerned they were found to decrease for both the dimers held by intermolecular Hg···S or
4. Conclusions
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O···H interactions.
It can be concluded that incorporating the –OH group at the periphery of the alkyl fragment in dithiocarbamates enables the PhHg(II)dithiocarbamates to undergo new
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secondary bonding interactions without disturbing the intra- and intermolecular Hg···S interactions, a characteristic feature of the phenylmercury(II) dithiocarbamtes. Also the
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quantum chemical calculations indicate that the presence of both Hg···S and O···H interactions in the same molecule do not induce cooperative effects as these interactions are completely independent of each other. Also, AIM calculations have indicated that intra- and intermolecular Hg···S interactions are dependent upon each other and the ellipticity parameters for the intramolecular Hg···S changes on dimerization.
Acknowledgements AK is grateful to Department of Science and Technology, New Delhi for the financial assistance in the form of project no. SB/FT/CS-018/2012.
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ACCEPTED MANUSCRIPT Supporting material The crystallographic data in CIF format has been deposited with CCDC (CCDC deposition number is 1049185). This data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (internet.) +44-1223/336-033; E-
IR spectral data. References
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mail: [email protected]]. The supplementary information also include the computed
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J. G. Melnick, K. Yurkerwich, G. Parkin, Inorg. Chem. 48 (2009) 6763.
[28]
C. S. Lai, E. R. T. Tiekink, CrystEngComm. 5 (2003) 253.
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N. Singh, A. Kumar, K. C. Molloy, M. F. Mahon, Dalton Trans. (2008) 4999.
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N. Singh, A. Kumar, R. Prasad, K. C. Molloy, M. F. Mahon, Dalton Trans. 39 (2010) 2667.
V. Singh, R. Chauhan, A. Kumar, L. Bahadur, N. Singh, Dalton Trans. 39 (2010)
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[20]
9779.
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C. S. Lai, E. R. T. Tiekink, Acta Crystallogr. Sect. E 58 (2002) m674. C. S. Lai, E. R. T. Tiekink, Appl. Organomet. Chem. 17 (2003) 194. E. R. T. Tiekink, J. Organomet. Chem. 322 (1987) 1. R. Chauhan, G. Kociok-Köhn, M. Trivedi, S. Singh, A. Kumar, D. P. Amalnerkar, J. Solid State Electrochem., 19 (2015) 739-747.
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N. W. Alcock, Adv. Inorg. Chem. Radiochem. 15 (1972) 1.
[37]
N. W. Alcock, Bonding and Structure: Structural Principles in Organic Chemistry, Ellis Horwood, New York, 1990.
13
Inorganic and
ACCEPTED MANUSCRIPT [38]
I. Haiduc, F. T. Edelmann, Supramolecular Organometallic Chemistry, Wiley-VCH, Weinheim, 1999.
[39]
I. Haiduc, Secondary Bonding, in Encyclopedia of Supramolecular Chemistry, Ed. J. L. Atwood
[40]
and J. Steed Marcel Dekker Inc., New York, 2004, 1215.
V. Singh, A. Kumar, R. Prasad, G. Rajput, M. G. B. Drew, N. Singh,
[41]
CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)
[42]
RI PT
CrystEngCommun. 13 (2011) 6817-6826.
SIR97 - A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A.
115-119.
SC
Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl. Crystallogr. 32 (1999)
G. M. Sheldrick, Acta Cryst C71 (2015) 3-8.
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(a) A. D. Becke, J. Chem. Phys. 98 (1993) 5648; (b) C. T. Lee, W. T. Yang, R. G.
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[43]
Parr, Phys. Rev. B: Condens. Matter Mater. Phys. 37 (1998) 1133. M. H. Jamroz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004-10.
[46]
P. Pulay, G. Fogarasi, F. Pang, J.E. Boggs, J. Am. Chem. Soc. 101(1979) 2550-2560.
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S. F. Boys, F. Bernardi, Mol. Phys. 19 (1970) 553.
[48]
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
TE D
[45]
Cheeseman, J. A. Montgomery, T. Vreven Jr., K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
EP
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M.; Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
AC C
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, W. M. Wong, C. Gonzalez and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004. [49]
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[50]
A. Kumar, V. Singh, A. N. Gupta, M. K. Yadav, V. Kumar, N. Singh, J. Coord. Chem., 65 (2012) 431-438. 14
ACCEPTED MANUSCRIPT Bader, R. F. W. In Atoms in Molecules: A Quantum Theory; Oxford University Press:
EP
TE D
M AN U
SC
RI PT
New York, 1990.
AC C
[51]
15
ACCEPTED MANUSCRIPT
Research Highlight A new organomercury(II)dithiocarbamate complex synthesized
•
Compound was investigated via multi-technique experimental approach
•
Intermolecular Hg···S interactions lead to a“head-to-tail” dimer.
•
Presence of a hydroxyl group generates a 1D-chain network.
AC C
EP
TE D
M AN U
SC
RI PT
•
ACCEPTED MANUSCRIPT Vibrational assignment (PED%)
S.
IR
IR intensity
No.
unscaled
scaled
Exp.
1
3832
3708.9928
3705
2
3203
3100.1837
3
3194
3091.4726
4
3188
5
ν O29-H26(100)
1.086604
ν C2-H15(85) νC2-H15(12)
1.086604
ν C2-H15(81)
3085.6652
1.086604
ν C2-H15(81) ν C2-H15(13)
3179
3076.9541
1.086327
ν C3-H17(90)
6
3173
3071.1467
1.086604
ν C2-H15(82)
7
3164
3062.4356
1.087982
ν C1-H14(94)
8
3162
3060.4998
1.087982
ν C1-H14(94)
9
3102
3002.4258
1.094946
ν C5-H18(77) ν C1-H13(20)
10
3100
3000.49
1.098394
ν C1-H13(11) ν C5-H18(83)
11
3049
2951.1271
1.094946
ν C5-H18(19) ν C1-H13(73)
12
3037
2939.5123
1.098394
ν C1-H13(82) ν C5-H18(13)
13
3035
2937.5765
1.098394
ν C1-H13(93)
14
3031
2933.7049
1.098394
ν C1-H13(91)
15
3028
2930.8012
1.098394
ν C1-H13(89)
16
1630
1577.677
1.397242
ν C2-C3(10) ν C2-C3(54) θH15-C2-C3(21) θ C2-C3-C8 (10)
17
1627
1574.7733
1.395339
ν C2-C7(68) θH15-C2-C3(14)
18
1524
1475.0796
19
1517
1468.3043
20
1505
1456.6895
21
1498
1449.9142
22
1489
1441.2031
23
1480
1432.492
24
1471
25
1438
26
1402
27
1394
28
SC
1.346765
ν N28-C4(10) θH13-C1-H14(66)
1.397242
ν C2-C3(14) θH15-C2-C3(72)
107.38
θ H18-C5-22(81)
108.29
θ H13-C1-H14 (74)
EP
1470
TE D
2944
M AN U
3053
RI PT
0.967608
107.38
θ H18-C5-H22(87)
1.346765
ν N28-C4(38) θH13-C1-H14 (24)
1423.7809
1.397242
ν C2-C3(25) θH15-C2-C3(55)
1391.8402
107.65
θ H26-O29-C9 (23) Ф C9-C12-C5-H19 (56)
108.29
θ H13-C1-H14 (14) θ H13-C1-N28-C6 (50)
1349.2526
108.47
θ H19-C9-C12 (42)
1390
1345.381
107.65
θ H26-C29-C9 (15) τH14-C1-N28-C6(30)
29
1372
1327.9588
61.16
τ H13-C1-N28-C6(41) τ H13-C1-N28-C6(13)
30
1356
1312.4724
1305
1.397242
ν C2-C3(22) θ H15-C2-C3(13) θH17-C2-C3(58)
31
1340
1296.986
1290
111.24
θ H21-C6-C12 (20) θ H19-C9-C12 (29)
AC C
1433
1356.9958
1357
ACCEPTED MANUSCRIPT ν C2-C7(70)
107.65
τ H26-O29-C9 (16) τ C9-C12-C5-H19 (17)
1.472365
ν N28-C6(15) θ H21-C6-C12(12) θ H24-C12-C6(10)
109.71
θ H18-c5-C1 (21) θ H24-C12-C6 (14)
107.65
θ H26-O29-C9 (12) θ H13-C1-H14 (11) θ H15-C2-C3 (12)
1.397242
ν C2-C3 (15) θH15-C2-C3(60)
1161.48
1.473295
ν N28-C1(18) θ H21-C6-C12(10) θ C1-N28-C4(11)
1188
1149.8652
119.68
ν C2-C7(12) θH15-C2-C3(75)
40
1180
1142.122
109.71
θ H18-C5-C1(12) θ H24-C12-C6 (13) τ H13-C1-N28-C6(16) τ H13-C1-N28-C6(17)
41
1120
1084.048
1.421057
ν O29-C9(29) θC12-C9-C5(10)
42
1112
1076.3048
1.533955
ν C5-C1(14) ν C12-C9(20) ν C6-C12(12)
43
1099
1063.7221
1.397242
ν C2-C3(40) ν C2-C7(10) θH15-C2-C3(23) θH17-C3-C2(17)
44
1091
1055.9789
1064
1.421057
ν O29-C9(27) θH26-O29-C9(17) τ C12-C9-C5-C1(10)
45
1090
1055.011
1020
1.397242
ν C2-C3(52) θH15-C2-C3(23)
46
1040
1006.616
1001
1.397242
ν C2-C3(77)
47
1019
986.2901
1.533955
ν C5-C1(11) ν C6-C12(24)
48
1011
978.5469
1.397242
ν C2-C3(13) θ C2-C3-C8(62)
49
1004
971.7716
1.533955
ν C5-C1(15) ν S30-C4(15)
50
1001
968.8679
51
994
962.0926
52
978
946.6062
53
972
940.7988
54
923
893.3717
55
918
888.5322
56
863
57
862
58
815
59
806
60
1269.8848
34
1287
1245.6873
35
1274
1233.1046
36
1215
1175.9985
37
1214
1175.0306
38
1200
39
1257
1234
1174
1106
967
913
SC
1312
M AN U
33
TE D
1280.5317
111.04
τ H17-C3-C2-C7(77) τ C8-C3-C2-C7(17)
110.4
θ C5-C1-N28 (10) θ C12-C9-C5(11) τH13-C1-N28-C6(16)
61.16
τH13-C1-N28-C6(19)
180
τH15-C2-C3-C8(73) τC2-C7-C10-C11(25)
EP
1323
RI PT
1.395339
32
180.04
τH17-C3-C2-C7(94)
1.533955
ν C5-C1(11) ν S30-C4(16) ν C6-C12(16)
835.2977
1.473295
ν N28-C1(24) ν N28-C6(12)
834.3298
180
τ H15-C2-C3-C8(91)
788.8385
1.53405
ν C9-C5(12) τH13-C1-N28-C6(44)
AC C
851
780.1274
762
1.53405
ν C9-C5(14) ν C12-C9(22)
743
719.1497
730
180
τH15-C2-C3-C8(83) τC2-C7-C10-C11(10)
61
709
686.2411
696
180.04
τ H17-C3-C2-C7(18) τ H15-C2-C3-C8(11) τ C8-C3-C2-C7(61)
62
665
643.6535
2.117558
ν Hg32-C8(15) θC2-C3-C8 (69)
63
645
624.2955
110.4
θ C5-C1-N28 (21)
64
629
608.8091
120.39
θ C2-C3-C8 (88)
ACCEPTED MANUSCRIPT ФS30-N28-S31-C4(75)
517.8265
1.715239
ν S30-C4 (17) ν S31-C4(16) θC12-C9-C5 (11) Ф O29-C5-C12-C9 (10)
481
465.5599
110.4
θ C5-C1 -N28 (12) θ C9-C5-C1(15)
68
474
458.7846
61.16
τH13-C1-N28-C6(10) τH13-C1-N28-C6(15) ФO29-C5-C12-C9(23)
69
457
442.3303
0.01
τC2-C7-C10-C11(88)
70
439
424.9081
1.772326
ν S31-C4(11) θC1-N28-C4 (40)
71
410
396.839
1.772326
ν S31-C4(18) θS30-C4-S31(40)
72
405
391.9995
180
τH15-C2-C3-C8(27) τC2-C7-C10-C11(72)
73
387
374.5773
61.16
τH13-C1-N28-C6(12) ФO29-C5-C12-C9(13) ФC6-C1-C4-N28(20)
74
350
338.765
2.493695
ν Hg32-S31(23)
75
346
334.8934
122.83
θ C1-N28-C4 (24) θ C9-C5-C1 (13) τH26-O29-C9-C5 (29)
76
307
297.1453
122.83
θ C1-N28-C4(12) θ S30-C4-S31(21) τH26-O29-C9-C5 (16)
77
289
279.7231
122.83
θ C1-N28-C4 (24) τH26-O29-C9-C5(46)
78
233
225.5207
2.117558
ν Hg32-C8(57) θC2-C3-C8 (11)
79
202
195.5158
119.28
θ Hg32-C8-C3(61) θ S31-Hg32-C8(10)
80
190
183.901
2.493695
ν Hg32-S31(11) θHg32-C8-C3 (14) τC12-C9-C5-C1 (18) Ф O29-C5-C12-C9(12)
66
535
67
534
448
SC
545.8956
M AN U
564
RI PT
0.07
65
Ф C6-C1-C4-N28(10) 171.3183
82
166
160.6714
83
131
126.7949
84
88
85.1752
85
71
68.7209
86
57
55.1703
87
35
33.8765
88
26
89
18
90
15
55.52
τC9-C5-C1-N28(16)
TE D
177
181.2
τC2-C7-C10-C11(60) τC8-C3-C2-C7(10) τC4-S31-Hg32-C8(20)
2.493695
ν Hg32-S31(28) θC4-S31-Hg32 (32) τC9-C5-C1-N28 (12)
92.6
θ C4-S31-Hg32 (66)
181.2
τC2-C7-C10-C11(13) τC4-S31-Hg32-C8(20) τC1-N28-C4-S31(14) τC4-S31-Hg32-C8(42)
EP
81
τC1-N28-C4-S31(53) τC5-C1-N28-C4(11)
178.25
τC1-N28-C4-S31(23) τC5-C1-N28-C4(28) τC4-S31-Hg32-C8(11)
25.1654
119.28
θ Hg32-C8-C3(12) θ S31-Hg32-C8(73)
17.4222
181.2
τC4-S31-Hg32-C8(83)
14.5185
181.2
τC4-S31-Hg32-C8(60) τC4-S31-Hg32-C8(20)
AC C
178.25