Synthesis and crystal structure of terephthalaldehyde-bis- (thiosemicarbazone)-bis-(dimethyl sulfoxide) solvate

Article abstract of DOI:10.14233/ajchem.2013.13171

A thiosemicarbazone single crystal synthesized with a formula as C ₁₀H₁₂N₆S₂ 2C₂H ₆OS, was synthesized by 1,4-phthalaldehyde and 4- methylthiosemicarbazide. The crystal is triclinic, space group P-1 with unit cell parameters: a = 5.9519(5) A, b = 7.4721(7) A, c = 12.5450(13), α = 77.348(8)°, β = 78.672(8)°, γ = 79.193(7)°, V = 527.64(8) A³, Z = 1, Mr = 436.63, Dc = 1.374 g/cm³, μ = 0.471 mm^-1, F(000) = 230, R = 0.0844, wR = 0.2607 for 1902 reflections with I > 2σ (I).

Full text of DOI:10.14233/ajchem.2013.13171

Asian Journal of Chemistry; Vol. 25, No. 4 (2013), 2319-2320
http://dx.doi.org/10.14233/ajchem.2013.13171
NOTE
Synthesis and Crystal Structure of Terephthalaldehyde-bis-
(thiosemicarbazone)-bis-(dimethyl sulfoxide) Solvate
1,2
1,*
2
1
WEI SU , PEIYUAN LI , LIFENG LIU , RUI CHEN1,3,* and LINI HUO
1College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001, P.R. China
2College of Chemistry and Life Science, Guangxi Teachers Education University, Nanning 530001, P.R. China
3Faculty of Chinese Medicine Science Guangxi University of Chinese Medicine, Nanning 530001 P.R. China
*Corresponding authors: E-mail: lipearpear@yahoo.cn; chrui1980@163.com
(Received: 3 December 2011;
Accepted: 26 October 2012)
AJC-12340
A thiosemicarbazone single crystal synthesized with a formula as C10H12N6S2·2C2H6OS, was synthesized by 1,4-phthalaldehyde and
4-methylthiosemicarbazide. The crystal is triclinic, space group P-1 with unit cell parameters: a = 5.9519(5) Å, b = 7.4721(7) Å, c =
12.5450(13), α = 77.348(8)º, β = 78.672(8)º, γ = 79.193(7)º, V = 527.64(8) Å3, Z = 1, Mr = 436.63, Dc = 1.374 g/cm3, µ = 0.471 mm-1,
F(000) = 230, R = 0.0844, wR = 0.2607 for 1902 reflections with I > 2σ (I).
Key Words: Thiosemicarbazone, Terephthalaldehyde, Single crystal, Dimethyl sulfoxide.
Thiosemicarbazones, which possess several donor atoms
and can bind to a metal atom both in neutral as well as in
anionic forms and have shown a number of bonding modes,
has attracted intensive attentions due to its broad spectrum of
pharmacological properties, including antitumor, antifungal,
antibacterial, antiviral and antimalarial activities1-4. Herein, we
report a novel terephthalaldehyde bis-(thiosemicarbazone)-bis-
(dimethyl sulfoxide) solvate single crystal synthesized with a
formula C10H12N6S2·2C2H6OS.
All reagents for synthesis were commercially available
and employed as received or purified by standard methods
prior to use. Analyses for carbon, hydrogen and nitrogen were
performed on a Perkin-Elmer 140 ºC analyzer.
radiation (λ = 0.71073 Å). A total of 4031 reflections were
collected in the range of 5.66º ≤ θ ≤ 50.5º, of which 1902
reflections were unique with Rint = 0.0414. The data were
collected using SMART and reduced by the program SAINT.
All the structures were solved by direct methods and refined
by full-matrix least squares method on 'F2obs' by using
SHELXTL-PC software package. Non-hydrogen atoms were
placed in geometrically calculated positions. Hydrogen atoms
were added according to theoretical model. The final full-
matrix least-squares refinement including 126 variable para-
meters for 1902 reflections with I > 2σ (I) and converged with
unweighted and weighted agreement factors of
R1 = Σ(||F0| - |FC||)/ S |F0| = 0.0844
(1)
Synthesis: For the synthesis of present compound, 0.134 g
1,4-phthalaldehyde (1 mmol) and 0.212 g 4-methylthiosemi-
carbazide were diluted using 10 mL mixture solution of ethane
and water (1:1). The solution was refluxed and then cooled to
room temperature and filtered. The filtration residue was
recrystallized using dimethyl sulfoxide/acetone (1:1). Single
crystals suitable for X-ray analysis were grown from the
dimethyl sulfoxide/ acetone solution by slow evaporation at
room temperature in air.
Crystal structure determination: A single crystal of
compound with dimensions of 0.21 mm × 0.14 mm × 0.10
mm was selected for crystallographic data collection at 293
(2) K and structure determination on a Bruker SMART CCD-
4 K diffractometer employing graphite-monochromated MoKα
2
and wR2 = {S [w(F02 - FC )2]/ Sw(F02)2}1/2 = 0.2607 (2)
where, w = 1/[σ2(F02) + (0.1014P)2] and P = (F02 + 2FC )/3.
The maximum and minimum peaks on the final difference
Fourier map are corresponding to 0.766 and -0.525 e/Å3,
respectively.
The selected bond lengths and bond angles are listed in
Table-1. Fig. 1 shows the molecular structure of the present
compound. Fig. 2 shows the packing diagram of the present
compound. The present compound crystallizes in the triclinic
system of P-1 space group. The structure of the terephthal-
aldehyde-bis-(thiosemi-carbazone)-bis-(dimethyl sulfoxide)
solvate consists of the thiosemicarbazone and dimethyl
sulfoxide. The average S-C bond distance in thiosemicarbazone
2

2320 Su et al.
Asian J. Chem.
TABLE-1
SELECTED BOND DISTANCES (Å) AND ANGLES (º)
S(1A)-O(1A)
S(2A)-C(1A)
N(2A)-C(1A)
C(3A)-C(4A)
1.522(6)
1.700(7)
1.365(8)
1.391(10)
1.410(11)
97.8(4)
123.3(6)
122.1(7)
121.3(7)
S(1A)-C(6A)
N(1A)-C(1A)
N(3A)-C(2A)
C(3A)-C(5N)
O(1A)-S(1A)-C(6A)
C(1A)-N(2A)-N(3A)
N(1A)-C(1A)-N(2A)
N(4A)-C(3A)-C(2A)
N(5A)-C(4A)-C(3A)
1.769(9)
1.318(9)
1.278(9)
1.410(11)
106.2(4)
119.2(6)
117.3(6)
119.7(7)
121.3(7)
S(1A)-C(7A)
N(2A)-N(3A)
C(2A)-C(3A)
C(4A)-C(5A)
O(1A)-S(1A)-C(7A)
C(1A)-N(3A)-N(2A)
N(2A)-C(1A)-S(2A)
N(4A)-C(3A)-C(5N)
N(4A)-C(5A)-C(3N)
1.782(8)
1.365(8)
1.459(10)
1.379(10)
106.5(4)
116.6(6)
119.4(5)
119.0(7)
119.7(7)
C(5A)-C(3N)
C(6A)-S(1A)-C(7A)
N(1A)-C(1A)-S(2A)
N(3A)-C(2A)-C(3A)
N(5N)-C(3A)-C(2A)
moiety is 1.700 Å, while that in dimethyl sulfoxide is 1.769 Å.
And the average C-N bond distance is 1.320 Å.
Conclusion
Crystal structure of a novel terephthalaldehyde bis-
(thiosemicarbazone) bis(dimethyl sulfoxide) solvate has been
synthesized and characterized by elemental analysis and
X-ray diffraction analysis.
ACKNOWLEDGEMENTS
This research is supported by the Key Project of Chinese
Ministry of Education (Grant No. 2010168), Guangxi Natural
Science Foundation (Grant No. 2010GXNSFB013014), National
Natural Science Foundation of China (Grant No. 21261005,
51263002) and Scientific Research Fund of Guangxi Provincial
Education Department (Grant No. 201106LX273).
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Fig. 1. Molecular structure of the terephthalaldehyde bis-(thiosemi-
carbazone)-bis-(dimethyl sulfoxide) solvate
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Fig. 2. View of a 3D supramolecular framework of the terephthalaldehyde
bis-(thiosemi-carbazone)-bis-(dimethyl sulfoxide) solvate