Acta Chim. Slov. 2004, 51, 787-792.
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Short Communication
THE CRYSTAL AND MOLECULAR STRUCTURE OF l-(BIPHENYL-4-CARBONYL)-3-p-TOLYL-THIOUREA
Hakan Arslan,a* Ulrich Flörke,b and Nevzat Külcüa
a Department of Chemistry, Faculty of Arts and Sciences, Mersin University, Mersin, Turkey. Department oflnorganic and Analytical Chemistry, University of Paderborn, Paderborn, Germany.
Received 09-07-2004
Abstract
l-(Biphenyl-4-carbonyl)-3-p-tolyl-thiourea (1) has been synthesized and characterized by elemental analysis and IR spectroscopy. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-l, Z = 4 with a = 9.6482 (17) A, b = 13.271(2) A, c = 14.109(3) A, a= 92.793(4) °, fi= 96.140 (4) °, y= 107.999(4) °, V = 1701.9(5) A3 andZ)caic = 1.352
Key words: Thioureas, benzoylthioureas, syntheses, X-ray stractures, single ciystal, X-ray ciystallography.
Introduction
Most of the thiourea derivatives have been successfully used in the extraction of Cu(II), Ni(II), Co(II), Pd(II), Pt(II), Co(III), Au(III), Rh(III) and Ru(III) from acidic media. These reagents have also been implemented in a solid supported liquid membrane system for the selective transport of relevant metals. Also thioureas have been shown to possess antibacterial, antifungal, antitubercular, antithroid and insecticidal properties.1'2
The structures of several type thiourea derivatives and its several metal complexes have been determined during the past decades.3"8 The title compound derivative acts as a bidentate ligand coordinating through the sulfur atom and the benzoyl oxygen atom. The similar structures of these derivative palladium, nickel and copper complexes and ligands have been determined in previous studies.9"11
We have recently begun to examine the coordination behaviour of a series of substituted benzoylthiourea derivatives that possess a number of interesting properties.5"8'11'12 Based upon the literature search, we could find no synthesis or characterization of title compound. In this paper, we discuss here the synthesis method and the structure of l-(biphenyl-4-carbonyl)-3:p-tolyl-thiourea (1).
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Results and discussion
The molecular structure of l-(biphenyl-4-carbonyl)-3:p-tolyl-thiourea (1), showing the atom numbering scheme and selected bond lengths and angles is given in Fig. 1 and Table 1, respectively. There are two independent molecules A and B per asymmetric unit with almost identical geometries, so the following discussion focuses on A only.
Figure 1. The molecular structure A of the title compound (1). The second independent molecule B (with atom numbering scheme 2xx) shows almost identical geometiy. Displacement ellipsoids are drawn at the 50% probability level.
Table 1.  Selected bond lengths (A) and angles (°) for title compound, molecules A (numbering x = 1) and B (x = 2).
Bond lengths	x=l	x=2	Bond angles	x=l	x=2
Cxl3-Ox	1.217(3)	1.224(3)	Nxl-Cxl4-Nx2	113.7(3)	113.5(3)
Cxl4-Sx	1.647(3)	1.647(3)	Cxl0-Cxl3-Nxl	115.7(3)	115.4(3)
Cxl3-Nxl	1.367(4)	1.362(4)	Cxl4-Nxl-Cxl3	130.6(3)	130.4(3)
Cxl4-Nx2	1.330(3)	1.330(3)	Cxl4-Nx2-Cxl5	129.5(3)	129.3(3)
Cxl4-Nxl	1.387(4)	1.394(4)	Ox-Cxl3-Nxl	122.9(3)	122.5(3)
The bond lengths and angles in the thiourea moiety are typical for thiourea derivatives; the Cxl4-S and Cxl3-0 bonds both show typical double-bond character (x = 1 for molecule A, x = 2 for B). The C-N bonds Cxl3-Nxl (1.365 A), Cxl4-Nxl (1.391 A), Cxl4-Nx2 (1.330 A), and Cxl5-Nx2 (1.424 A) are shorter than the normal single C-N bond length (1.469 A), indicating double bond character. LP electron on nitrogen atoms are shifted towards neighbouring atoms. As a result of this effect, hybrisation on nitrogen atoms changes from sp3 to sp2. These results confirmed by bond angles and lengths (Table 1). This approach is agreement with that of Arslan et al.12
H. Arslan, U. Flörke, N. Külcii: The Crystal and Molecular Structure of l-(Biphenyl-4-carbonyl)...
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Intramolecular hydrogen bonds Nx2-Hx2..0 for molecule A and B each form six-membered rings, well kown from related structures. The conformation of the molecule with respect to the thiocarbonyl and carbonyl moieties is twisted as reflected by the torsional angles Cxl4-Nxl-Cxl3-Ox and Cxl3-Nxl-Cxl4-Nx2 of av. 7.1(5)° and -1.3(5)°, respectively. In the crystal structure (Fig. 2), molecules A and B form dimers each through strong intermolecular hydrogen bonds C111-H11A...01 (-x +1, -y+l, -z) with H...O 2.384 A, C-H...0 132.2°, C...H 3.211(4) A and C209-H20G...O2 (-x +1, -y+l, -z) with H...O 2.427 A, C-H...0 121.7°, C...O 3.133(4) A. These values are normalized for N-H 1.030 and C-H 1.080 A.
There are no significant differences in the bond distance and bond angles comparing with other phenyl thiourea.11"13'16 Ali the other bond lengths fall within the expected range.
Figure 2. Packing diagram for (1) viewed along [100], H-atoms not involved omitted.
Experimental
Synthesis
Ali chemicals used for the preparation of the title compound were of reagent grade quality. Some of the solvent was distilled before use. The compound was prepared by a procedure similar to that reported in the literature.12 A solution of an appropriately 4-phenyl benzoyl chloride (0.01 mol) in acetone (50 cm3) was added dropwise to a suspension of potassiumthiocyanate (0.01  mol) in acetone (30 cm3). The reaction
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Acta Chim. Slov. 2004, 51, 787-792.
mixture was heated under reflux for 30 min, and then cooled to room temperature. A solution of /?-tolyamine (0.01 mol) in acetone (10 cm3) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 cm3) was added and then the solution filtered. The solid product was washed with water and purified by recrystallisation from ethanol/dichloromethane mixture (1:1). l-(biphenyl-4-carbonyl)-3-^-tolyl-thiourea: White. Yield: 84%, m.p. 162-164 °C, Anal. Calcd For C2iHi8N2OS: C 72.8, H 5.2, N 8.1. Found: C 72.1, H 5.1, N 7.9. IR (KBr): v(N-H) 3197 (br), v(C=0) 1674 (s) cm"1.
Table 2. Crystal data and structure refinement for title compound.
Empirical formula	C21H18N2OS
Formula weight / g	346.43
Temperature / K	153(2)
Wavelength (Mo K„) / A	0.71073
Crystal system	Triclinic
Space group	P-l
Unit celi dimensions	
a / A	9.6482(17)
bik	13.271(2)
c / A	14.109(3)
al°	92.793(4)
Pl°	96.140(4)
yl°	107.999(4)
Volume / A3	1701.9(5)
Z	4
Density (calculated) / Mg/m3	1.352
-1 Absorption coefficient / mm	0.201
F(000)	728
Crystal size / mm3	0.35 x 0.10 x 0.08
Theta range for data collection / °	1.46 to 26.19
Index ranges	-11< h <10, -16< k <16, -16< 1 <17
Reflections collected	9993
Independent reflections	6711 [R(int) = 0.0406]
Completeness to theta = 26.19°	98.3 %
Absorption correction	Semi-empirical from equivalents
Max. and min. transmission	0.984 and 0.933
Refinement method	Full-matrix least-squares on F2
Data / restraints / parameters	6711 / 0 / 453
Goodness-of-fit on F2	0.972
Final R indices [I>2sigma(I)]	Rl = 0.0479
R indices (all data)	wR2 = 0.0800
Largest diff. peak and hole / e.A-3	0.23 and -0.25
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Analysis and physical measurements
Fourier transformed infrared (FT-IR) spectra were recorded as KBr pellets on a Shimadzu 435 spectrophotometer, between 4000 - 400 cm"1. C, H and N analyses were carried out on a Carlo Erba MOD 1106 elemental analyzer. Melting points were determined on a digital melting point instrument (Electrothermal model 9200).
Single crystal X-ray data were collected on a Bruker SMART APEX System including SAINT data reduction and SADABS corrections. The structures were solved by direct and conventional Fourier methods. Full-matrix least-squares refmement based on F2. Anisotropic atomic displacement parameters were refined for ali non-hydrogen atoms, hydrogen atoms derived from Fourier maps were refined at idealized positions using a ‘riding model’ with f/eq(H) = 1.2 L/eq(N, Ciso) and 1.5 Ueq(Ciso) for methyl groups, respectively. Two independent but geometrically identical molecules A and B per asymmetric unit. Programs used for calculations: SHELXTL.14 Further details concerning data collection and refmement are given in Table 2. Additional crystallographic data for the structure reported in this paper have been deposited at the Cambridge Crystallographic Data Centre (CCDC) with quotation number CCDC-244044 and can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: (internat.) + 44(1223)336-033, E-mail: deposit@ccdc.cam.ac.uk].
Acknowledgements
This work was supported by Mersin University Research Fund (Project No. BAP.ECZ.F.TB.(HA) 2003-2).
References
1.  O. F. Huebhr, J. L. Marsh, R. H. Mizzoni, R. P. Muli, D.C. Schroeder, H. A. Troxell, C. R. Scholz, J. Am. Chem. Soc. 1953, 75, 2274-2275.
2.  V. K. Madan, A. D. Taneja, Indian Chem. Soc. 1991, 68, 471-172.
3.  L. P. Battaglia, A. C. Bonamartini, G. Pelizzi, T. M. E. Vidoni, J. Chem. Soc, Dalton Trans. 1977, 1141-1144.
4.  E. A. H. Griffith, W. A. Spofford, E. L. Amma, Inorg. Chem. 1978, 17, 1913-1971.
5.  H. Arslan, U. Flörke, N. KMciX, Acta Crystallographica 2003, E59, o641-o642.
6.  H. Arslan, U. Flörke, N. Kiilcii, J. Chem. Crystallography 2003, 33, 919-924.
7.  H. Arslan, D. Vanderveer, F. Emen, N. Külcii, Z. Kristallogr. NCS 2003, 218, 479-480.
8.  D. Ugur, U. Flörke, N. Külcii, H. Arslan, Acta Crystallographica 2003, E59, ol345-ol346.
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9. G. Firzl, L. Beyer, J. Sieler, R. Richter, J. Kaiser, E. Hoyer, Z. Anorg. Allg. Chem. 1977, 433, 237-241.
10.  R. Richter, L. Beyer, J. Kaiser, Z. Anorg. Allg. Chem. 1980, 461, 67-73.
11.   G. Avºar, H. Arslan, H.-J, Haupt, N. Kiilcii, Turk. J. Chem. 2003, 27, 281-285.
12.  H. Arslan, U. Flörke, N. Kiilcii, Transition Metal Chemistry 2003, 28, 816-819.
13.   A. Dago, M. A. Simonov, E. A. Pobedimskaya, A. Macias, A. Martin, Kristallografiya 1987, 32 1024-1026.
14.   G. M. Sheldrick, SHELXTL v. 5.1, Structure Determination Softvvare Suite, Bruker AXS, Madison, Wisconsin, USA, 1998.
Povzetek
Pripravili smo l-(bifenil-4-karbonil)-3-(^-tolil)tioseènino (1) in jo karakterizirali z elementno analizo in IR spektroskopijo. Kristalno in molekulsko strukturo 1 smo doloèili z rentgensko difrakcijsko analizo. Spojina kristalizira v triklinski prostorski skupini P-l, Z = 4, a = 9.6482 (17) A, b = 13.271(2) A, c = 14.109(3) A, «= 92.793(4) °, fi= 96.140 (4) °, Y= 107.999(4) °, V = 1701.9(5) A3 in Dcaic = 1.352 Mg/m3.
H. Arslan, U. Flörke, N. Kiilcii: The Crystal and Molecular Structure of l-(Biphenyl-4-carbonyl)...