Studies on the crystal structure and characterization of N-(4-acetylphenyl)-N’-(2-nitrobenzoyl)-thiourea

Article abstract of DOI:10.1080/10426507.2015.1050016

N-(4-acetylphenyl)-N′-(2-nitrobenzoyl)-thiourea has been synthesized in high yield under PEG-400 as the phase-transfer catalyst and its the compound structure was determined by single crystal X-ray diffraction. The compound is also a considerable plant-gr

Full text of DOI:10.1080/10426507.2015.1050016

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Studies on the crystal structure and
characterization of N-(4-acetylphenyl)-N′-(2-
nitrobenzoyl)-thiourea
Jing-Han Hu, Jian-Bin Li, Jing Qi & You Sun
To cite this article: Jing-Han Hu, Jian-Bin Li, Jing Qi & You Sun (2015): Studies on the crystal
structure and characterization of N-(4-acetylphenyl)-N′-(2-nitrobenzoyl)-thiourea, Phosphorus,
Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2015.1050016
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1050016
Accepted author version posted online: 03
Dec 2015.
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Date: 07 January 2016, At: 02:45

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Studies
on
the
crystal
structure
and
characterization
of
N-(4-acetylphenyl)-N'-(2-nitrobenzoyl)-thiourea
Jing-Han Hu*, Jian-Bin Li, Jing Qi, You Sun
College of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou, Gansu,
P. R. China
*Corresponding author: J. H. Hu; E-mail: hujinghan62@163.com
Keywords
Aroylthiourea; Crystal structure; Biological activity; Recognition performance
N-(4-acetylphenyl)-N'-(2-nitrobenzoyl)-thiourea has been synthesized in high yield
under PEG-400 as the phase-transfer catalyst and its the compound structure was
determined by single crystal X-ray diffraction. The compound is also a considerable
plant-growth regulator. In addition, the compound L exhibited selective recognition
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for Hg2+ over other metals ions such as Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+
and Mg2+ in DMSO solutions.
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Introduction
Thiourea derivatives have been known for over a century and are easily synthesized in good
yields. Thiourea derivatives have a long history as a ligand in coordination chemistry and
coordinate to a metal via both sulfur and oxygen1. These hard and soft donor atoms provide a
multitude of bonding possibilities2. Hydrogen bonding behaviors of some thioureas have been
investigated and it is found that the intermolecular hydrogen bond between the sulfur and a
hydrogen atom on N is common3.
Thiourea derivatives are extensively applied in various industries because of their unique
molecular structure, good physical and chemical properties, and comprehensive biological
activities. The literature shows that a number thiourea derivatives have been shown to posses
antibacterial, antifungal, antitubercular, antithyroid and insecticidal properties4. Thioureas serve
as indispensable scaffolds in material chemistry pertaining to electroluminescent organic dyes5,6.
Also, thiourea along with its related molecules are important as structural components in
agricultural and pharmaceutical chemistry7,8. Furthermore, thiourea polymers possessing
coordination sites can act as supports for immobilized catalysts9. In supramolecular chemistry,
thiourea polymers are of interest due to their specific interactions with biologically important
anions10,11. Accordingly, thiourea-based materials are excellent candidates of advanced
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technological significance in the fields of anion sensing, waste recovery of anions through
solid-phase extraction and anion membrane transport for purification and synthesis purposes.
Another promising aspect of these thiourea-based polymers is that they can act as coordinating
resins for selective binding of heavy metal cations such as Hg(II) and Pb(II) from acidic as well
as neutral solutions12,13
.
In continuation of our earlier work14,15, we designed and synthesized the compound of
N-(4-acetylphenyl)-N'-(2-nitrobenzoyl)-thiourea. The compound’s structure was determined by
single crystal X-ray diffraction. In addition, by investigating the biological activity of the title
compound, we found that the compound has high plant growth regulating activity at low
concentration (Table 1, Supplemental Materials) Moreover, sensing performance based on the
compound L were demonstrated, which could be very useful for the compound of molecule
recognition with fast and selective detection for mercury and ions.
Results and discussion
Structure Determination
In the molecule of the title compound, the crystal data and structure refinement details for
C16H13N3O4S are summarized in Table 1, is not planar, selected bond distances and angles are
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listed in Table 2 and Table S 2 (Supplemental Materials) . The dihedral angle between the mean
plane of the thiourea fragment and both benzene rings are 81.32(0.11)° and 27.36(0.11)°. The
molecular conformation is stabilized by an intramolecular N-H···O hydrogen bond. In the crystal
structure, molecules are linked by intermolecular N-H···O hydrogen-bonding interactions into
one-dimensional a ribbon chains along the a-axis direction. The O(2) atom of the -NO2 group is
disordered over two sites with refined occupancies of 0.36 and 0.64.
Crystal Structure
In the crystal structure (Figure 1) of the title compound is similar to those of
N-(2-nitrophenyl)-N'-(methoxycarbonyl)-thiourea
and
N-(4-nitrophenyl)-N'-(ethoxycarbonyl)-thiourea16. The molecule is not planar. The bond lengths
of C=O are 1.216 (3)Å and 1.217 (4)Å while the bond length of C=S is 1.640 (3)Å. At the same
time, in the torsion angle of C8-N2-C7-O3, C7-N2-C8-N3, C9-N3-C8-S1, C7-N2-C8-S1,
C6-C7-N2-C8 and N2-C8-N3-C9 are -0.8 (6)°, 1.8 (5)°, 1.2 (6)°, -177.8 (3)°, 175.30 (0.30)° and
-178.25 (0.30)°. In the crystal, each molecule is joined to an intramolecular N-H···O hydrogen
bond and intermolecular N-H···O hydrogen bond which stabilizes the molecular conformation and
leads to the crystal packing in a supramolecular one-dimensional a ribbon chains along the a-axis
direction as shown in Figure S 1 (Supplemental Materials). A summary of important bond
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lengths and angles are presented in Table 1.
Biological activity
We also investigated the plant growth regulation activity. Here, we adopted the method of
plate culture. The compound was collected to the solution in concentration of 1 ppm, 0.1 ppm, 0.01
ppm, and coleseed was cultured in a 10 cm Petri dish with 10 mL different solution and a circular
filter paper (for the experiment process and data see Supplemental Materials).
Cation recognition properties
To evaluate the recognition studies of ligand L, Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+,
Cr3+ and Mg2+ ions were used to measure the selectivity and sensitivity of L (2×10-4 M) in DMSO,
and absorption spectral were recorded upon the addition of 20 equiv. of each of these metal ions.
Compared to other metal ions examined, changes in the spectral pattern were observed only in the
presence of Hg2+ (4×10-3 M). No change in the spectral pattern for L in the presence of other
cations suggested either a very weak or no interaction between these cations and the ligand L
(Figure 2). As is well-known, for an ideal ion probe, only the target ion should induce drastic
spectral changes, and the coexistence of other competing ions should not disturb the detection of
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the target ion17,20. Thus, competition behavior was checked to further elucidate whether the
coexistence of competing metal cations interferes with the detection of Hg2+. In the solutions of
ligand L, upon addition of Hg2+ (4×10-3 M) together with other competing cations (4×10-3 M)
(Figure 3), similar absorption weakened was clearly observed. Thus, the ligand L displays a good
selectivity for Hg2+ over other competing metal ions in DMSO solution.
Uv-vis titrations were carried out in DMSO at a concentration of 2.0×10-5 M with the addition
of different concentrations of Hg2+ (0.02 M). The strong new band with maximum absorbance
peak at 287 nm was observed after adding of Hg2+, and then the absorbance peak at 325 nm
decreased gradually. The isosbestic points at 312 nm can be clearly observed with increasing
concentrations of Hg2+ (0-10 equiv.), indicating a new and stable complexation of ligand L with
Hg2+ ion (Figure S 2).
The whole reaction process was shown in Scheme 2. This phenomenon may be attributed to
the function of desulfurization of the ligand L toward Hg2+ (Figures S 3 and S 4) 21-23
.
Experimental
Synthesis and characterization
N-(4-acetylphenyl)-N'-(2-nitrobenzoyl)-thiourea was synthesized in high yield (Scheme 1).
Potassium thiocyanate (7.5 mmol), 2-nitrobenzoyl chloride (5 mmol), PEG-400 (3% with respect
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to ammonium thiocyanate) and dichloromethane (20 mL) were placed in a dried flask and stirred
at room temperature for 1h, then 1-(4-aminophenyl)ethanone (5 mmol) was added. The mixture
was stirred for 0.5h at room temperature and a precipitate was formed. This was filtered off,
washed with water and dried. Yellow single crystals of the title compound were obtained slowly
due to evaporation of an ethanol-dimethylformamide (1:1) solution. Yield, 80%; m.p. 162-164 ℃.
1H NMR (600 MHz, cdcl3) δ 12.45 (S, N−H), 12.25 (S, N−H), 8.24-7.81 (m, Ar−H), 3.34 (S,
−CH3). Anal. calcd. (%) for C16H13N3O4S (%): C, 5.97; H, 3.82; N, 12.24; O, 18.64; S, 9.34. Found
(%): C, 5.98; H, 3.84, N, 12.21; O, 18.65; S, 9.36. IR (KBr) v: 3450 cm-1 (−OH), 3179 cm-1, 1519
cm-1 (−NH), 3032 cm-1 (−CH3), 1596 cm-1 (−C=S), 1680 cm-1 (−C=O). ESI-MS calcd for
C16H13N3O4+H 344.06, found 344.16.
Investigation Techniques
The title compound was studied by various physicochemical methods: X-ray diffraction.
X-Ray Diffraction
A single crystal was carefully selected under a polarizing microscope in order to perform its
structural analysis by X-ray diffraction. Data collection: Bruker APEX2; cell refinement: Bruker
SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97
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(Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker
SHELXTL. Crystal data and experimental parameters used for the intensity data collection are
summarized in Table 2. Crystallographic data for the title compound L have been deposited with
the Cambridge Crystallographic Data Center as supplementary publication CCDC reference
numbers 1056740. These data can be obtained free of charge from the Cambridge
Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336 033;
or Email: deposit@ccdc.cam.ac.uk.
Conclusions
In
summary,
we
have
designed
and
synthesized
N-(4-acetylphenyl)-N'-(2-nitrobenzoyl)-thiourea in high yield. The crystal structure show that the
intramolecular hydrogen bonding (N3-H3A···O3 and C10-H10···S1) between the amide-N and
p-nitrobenzoyl-O atoms, and the acetylphenyl-C10 and the thiourea-S, respectively. Moreover, in
the crystals, the compound were linked to a supramolecular one-dimensional a ribbon chains
through the intermolecular hydrogen bonds. In addition, investigation of biological activity shows
the compound show good plant-growth regulation activity and the ligand L demonstrated an
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excellent property of molecule recognition with fast and selective detection for mercury.
Acknowledgment
We gratefully acknowledge the support of the Nature Science Foundation of China (No.
21467012).
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References
1. Burrows, D. A.; Mare, D. C.; Mahon, F. M. Polyhedron, 1999, 18, 2665-2671.
2. Hederson, W.; Nicholson, B. K.; Dinger, M. B.; Bennett, R. L. Inorg. Chim. Acta., 2002, 338,
210-218.
3. Arslan, H.; Florke, U.; Kulcu, N.; Emen, M. F. Journal Coord. Chem., 2006, 59, 223-228.
4. Madan, V. K.; Taneja, A. D. J. Indian Chem., Soc., 1991, 68, 162-163.
5. Reetz, M. T.; Kuhling, K. M.; Deege, A.; Hinrichs, H. and Belder, D. Angew. Chem. Int. Ed.,
2000, 39, 3891-3893.
6. Avalos, M.; Babiano, R.; Cintas, P. M.; Chavero, M.; Higes, F. J.; Jimenez, J. L. Lopez, I. and
Palacios, J. C. J. Org. Chem., 2000, 65, 8882-8892.
7. Liu, S.; Tang, C.; Ho, B.; Ankersen, M.; Stidsen, C. E. and Crider, A. M. J. Med. Chem., 1998,
41, 4693-4705.
8. Hari, A. and Miller, B. L. Org. Lett., 2000, 2, 3667-3670.
9. Michalska, Z. M.; Ostaszewski, B. and Strzelec, K. J. Organomet. Chem., 1995, 496, 19-26.
10. Cheng, X. H.; Zhou, Y.; Qin, J. G. and Li, Z. Appl. Mater. Interfaces. 2012, 4, 2133-2138.
11. Lu, W.; Jiang, H.; Hua, F. Y.; Jiang, L. M.; Shen, Z. Q. Tetrahedron, 2011, 67, 7909-7912.
12. Mahapatra, A. K.; Roy, J.; Sahoo, P.; Mukhopadhyay, S. K.; Banik, A.; Mandal, B. D.
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ACCEPTED MANUSCRIPT
Tetrahedron Lett., 2013, 54, 2946-2951.
13. Guo, Z. Q.; Zhu, W. H.; Zhu, M. M.; Wu, X. M. and Tian, H. Chem. Eur. J. 2010, 16,
14424-14432.
14. Hu, J. H.; Wang, L. C.; Liu, H. and Wei, T. B. Phosphorus Sulfur Silicon Relat. Elem., 2006,
181, 2691-2698.
15. Hu, J. H.; Xu, L.; Wang, J. and Wei, T. B. Phosphorus Sulfur Silicon Relat. Elem., 2008, 183,
1584-1591.
16. Shen, X.; Shi, X.; Kang, B.; Tong, Y.; Liu, Y.; Gu, L.; Liu, Q.; Huang, Y. Polyhedron, 1998, 1,
33-37.
17. Chen, C.; Wang, R. Y.; Guo, L. Q.; Fu, D.; Dong, H.; Yuan, Y. Org. Lett., 2011, 13,
1162-1165.
18. Zhu, W. J.; Yang, L. L.; Fang, M.; Wu, Z. Y.; Zhang, Q.; Yin, F. F.; Huang, Q.; Li, C. J. Lumin.
2015, 158, 38-43.
19. Moorthy, S.; Sandhya, M.; Sanjiv, K. M.; Suresh, E.; Amal, K. M.; Anupama, S.; Amitava, D.
Org. Lett., 2009, 11, 2740-2743.
20. Sait, M.; Serkan, E. Dyes Pigm., 2015, 113, 763-769.
21. Choi, M. G.; Im H. G.; Noh, J. H.; Ryu, D. H.; Chang, S. K. Sens. Actuators B, 2013, 177,
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583-588.
22. Kim, S.; Lee, N. H.; Seo, S. H.; Eom, M. S.; Ahn, S.; Han, M. S. Chem. Asian J. 2010, 5,
2463-2466.
23. Choi, M. G.; Ryu, D. H.; Jeon, H. L.; Cha, S.; Cho, J.; Joo, H. H.; Hong, K. S.; Lee, C.; Ahn, S.;
Chang, S. K. Org. Lett., 2008, 10, 3717-3720.
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Figure 1. The crystal structure of the title compound.
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Figure 2. UV-vis absorption of sensor L (2.0×10-4 M ) in the presence of 20 equiv. various
cations in DMSO.
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Figure 3. UV-vis absorption response of L (2×10-4 M) in the presence of various cations
(4×10-3 M) in DMSO solution in response to Hg2+ (4×10-3 M)
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Scheme 1. Synthetic procedures for the title compound.
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Scheme 2. Possible recognition mechanism.
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