Crystal structure of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4] thiadiazole

Article abstract of DOI:10.1134/S0022476613050223

A new compound of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4] thiadiazole is synthesized and its single crystal structure is determined by X-ray diffraction method. The compound belongs to the monoclinic P2 ₁/c space group with cell par

Full text of DOI:10.1134/S0022476613050223

Journal of Structural Chemistry. Vol. 54, No. 5, pp. 983-985, 2013
Original Russian Text Copyright © 2013 by P. Wu
CRYSTAL STRUCTURE OF 6-FERROCENYL-3-
PHENYL-[1,2,4]TRIAZOLO[3,4-b][1,3,4]THIADIAZOLE
P. Wu
UDC 548.73:547.13:546.72
©
A new compound of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole is synthesized and its
single crystal structure is determined by X-ray diffraction method. The compound belongs to the
monoclinic P2 /c space group with cell parameters: a = 10.5523(12) Å, b = 13.8414(16) Å, c =
1
3
11.4303(13) Å, V = 1603.5(3) Å .
DOI: 10.1134/S0022476613050223
Keywords: X-ray diffraction, monoclinic symmetry, triazole, thiadiazole, ferrocenyl.
For their wide spectrum applications in biology [1] 1,2,4-triazoles and 1,3,4-thiadiazoles possess diverse types of
biological properties, such as antimicrobial [2], antibacterial [3], antitubercular [4], anti-inflammatory [5, 6], and
antihypertensive [7] activities, etc. Moreover, triazolothiadiazole can be viewed as a cyclic analogue to two very important
components: thiosemicarbazide and biguanide, which often display diverse biological properties. Herein, a new compound of
the 1,2,4-triazolo[3,4-b][1,3,4]thiadiazole ring system is synthesized and its X-ray crystal structure is revealed.
Experimental. The 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole compound is synthesized by the
previously reported procedure with minor modifications [8], as shown in Scheme 1.
Scheme 1. Synthesis of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole
A mixture of benzoic acid (1 mmol) and thiocarbohydrazide (1 mmol) was warmed up to 170°C for 1 h. After
cooling, water was added into the solution. This solution was acidified by HCl (conc.) to give precipitates, which were
filtered and collected to obtain crude 5-benzoic-4-amino-3-merapto-1,2,4-triazole with the yield of 80%. Then, a mixture of
5-benzoic-4-amino-3-merapto-1,2,4-triazole (1 mmol) and ferrocenecarboxylic acid (1 mmol) in phosphoryl chloride was
refluxed for 6 h. Excess phosphoryl chloride was removed under reduced pressure. The residue was poured into ice water and
the mixture was stirred at room temperature for one hour; sodium bicarbonate was added into the solution gradually until
Department of Chemistry, Dezhou College, Shandong; Key Laboratory of Coordination Chemistry and Functional
Materials at Universities of Shandong, P. R. China; Pingwu.dzu@gmail.com. The text was submitted by the authors in
English. Zhurnal Strukturnoi Khimii, Vol. 54, No. 5, pp. 944-946, September-October, 2013. Original article submitted
April 4, 2012.
0022-4766/13/5405-0983
983

TABLE 1. Crystal Data and Structure Refinement for the Complex
Chemical formula
Molecular weight
Crystal system
Space group
C19H14FeN4S
386.25
F(000)
792
2.37/28.29
θ range, deg.
Monoclinic
Index ranges (h, k, l)
–13/14, –18/18, –15/15
0.0917
P2 /c
1
R
int
10.5523(12), 13.8414(16),
11.4303(13); 106.1690(10)
Refined data, parameter,
restriction
4006, 226, 0
a, b, c, Å; β, deg
Observed reflections with
I > 2σ(I )
3063
T, K
293(2)
1603.5(3)
4
GOOF
0.947
0.0344/0.0760
0.0506
3
V, Å
R /wR [I > 2σ(I )]
1 2
a
Z
R (all data)
1
b
–3
1.600
1.080
wR (all data)
2
0.0810
D , g⋅cm
c
–1
3
0.530/–0.408
μ, mm
(Δρ) /(Δρ) , e/Å
max min
a
R = ∑||F | – |F ||/∑|F |;
1 0 c 0
2
2
wR = |∑w(|F | – |F | )|/∑|w(F ) | , where w = 1/[σ (F ) + (aP) + bP]; P = (F + 2 )/3.
b
2
2
2 1/2
2
2
2
F
2
0
c
0
0
0
c
TABLE 2. Selected Geometric Parameters (Å, deg)
C4–C7
C7–N4
C7–N2
N3–N4
C5–N3
C5–N2
1.466(3)
1.320(2)
1.375(2)
1.403(2)
1.316(2)
1.364(2)
C5–S2
C9–S2
C9–N1
N1–N2
C9–C11
1.733(2)
1.7683(18)
1.307(2)
1.389(2)
1.449(2)
N4–C7–N2
N4–C7–C4
N2–C7–C4
C9–N1–N2
N1–C9–C11
C7–N4–N3
C5–N3–N4
108.12(16)
125.10(17)
126.70(17)
107.07(15)
123.04(17)
109.58(15)
104.86(16)
N3–C5–N2
N1–C9–S2
C5–S2–C9
C5–N2–C7
N2–C5–S2
C5–N2–N1
C11–C9–S2
111.74(17)
117.39(14)
87.51(9)
105.69(15)
109.62(14)
118.40(15)
119.56(14)
the solution was neutral. The precipitated solid was filtered, dried and recrystallized to get the pure product, which was
dissolved in methanol, followed by adding petroleum ether to get the mixed solution. This solution was evaporated slowly at
room temperature to give the desired single crystal.
X-ray crystallography. The crystallographic data collections were carried out on a Bruker Smart Apex II CCD
area-detector diffractometer with graphite monochromated MoK radiation (λ = 0.71073 Å) at 293(2) K using the ω-scan
α
technique. The diffraction data were integrated using the SAINT program [9], which was also used for the intensity
corrections for Lorentz and polarization effects. Semiempirical absorption correction was applied using the SADABS
program [10]. The structures were solved by direct methods and all the non-hydrogen atoms were refined anisotropically on
2
F by the full-matrix least-squares technique using the SHELXL-97 crystallographic software package [11]. Hydrogen atoms
were generated geometrically. Details of crystal parameters are summarized in Table 1. Selected bond lengths and angles are
listed in Table 2.
Results and discussion. The titled compound crystallized in a monoclinic crystal system with a P2 /c space group,
1
as depicted in Fig. 1.
For the ferrocenyl moiety, the distance from Fe(II) to the center of the substituted cyclopentadiene ring (C ) is
ps
1.368(5) Å, while this distance is 1.375(2) Å for the unsubstituted one (C ). The bond angle of C –Fe–C is 177.98(8) Å,
p ps p
which means that central Fe(II) is located almost in the middle of the two cyclopentadiene rings. Furthermore, two
cyclopentadiene rings are not parallel to each other with a small dihedral angle of 4.64(5) Å.
984

Fig. 1. Molecular structure of the titled compound with the atom
numbering scheme. Displacement ellipsoids are drawn at the 30%
probability level.
In the [1,2,4]triazolo[3,4-b][1,3,4]thiadiazole ring, the C7–N4, C5–N3, and C9–N1 bond lengths are 1.320(2) Å,
1.316(2) Å, and 1.307(2) Å respectively, which is consistent with the typical values of C=N double bonds. Meanwhile, the
C5–S2 and C9–S2 bond distances are 1.733(2) Å and 1.7683(18) Å, indicating two single bonds.
Moreover, two weak intramolecular hydrogen bonds were found to be C10–H10⋯N1 and C13–H13⋯N4, as
depicted in Fig. 1. For C10–H10⋯N1 the C10–H10, H10⋯N1, and C10⋯N1 distances are 0.93 Å, 2.49 Å, and 3.153(3) Å;
the bond angle is found to be 120°. As for C13–H13⋯N4, the corresponding C13–H13, H13⋯N4, and C13⋯N4 bond
lengths are 0.93 Å, 2.55 Å, and 2.877(3) Å respectively. The C13–H13⋯N4 bond angle is 101°. Possible π⋯π weak
interactions between the S2 atom and the adjacent ferrocenyl rings were found to be too weak to be considered.
CIF file containing complete information on the studied structure was deposited with CCDC, deposition number
874161, and is freely available upon request from the following web site: http://www.ccdc.cam.ac.uk/data_request/cif.
We thank the Natural Science Foundation of Shandong Province of China (Nos. ZR2009BL004 and
ZR2009BM042) for their financial support.
REFERENCES
1. V. Mathew, J. Keshavayya, and V. P. Vaidya, Eur. J. Med. Chem., 41, 1048 (2006).
2. S. N. Swamy, B. S. Basappa, P. B. Prabhuswamy, B. H. Doreswamy, J. S. Prasad, and K. S. Rangappa, Eur. J. Med.
Chem., 41, 531 (2006).
3. B. S. Holla, B. S. Rao, B. K. Sarojini, P. M. Akberali, and N. S. Kumari, Eur. J. Med. Chem., 41, 657 (2006).
4. M. R. Shiradkar, K. K. Murahari, H. R. Gangadasu, T. Suresh, C. A. Kalyan, D. Panchal, R. Kaur, P. Burange,
J. Ghogare, V. Mokale, and M. Raut, Bioorg. Med. Chem., 15, 3997 (2007).
5. L. Labanauskas, E. Udrenaite, P. Gaidelis, and A. Brukštus, Il Farmaco, 59, 255 (2004).
6. A. R. Rasad, T. Ramalingamat, A. B. Rao, P. W. Diwan, and P. B. Sattur, Indian J. Chem., 25B, 556 (1985).
7. H. F. Czarnocka-Janowicz, A. Nasal, J. Petrusewicz, B. Damasiewicz, A. Radwanska, and R. Kaliszan, Pharmazie, 46,
109 (1991).
8. F. P. Invidiata, G. Furnò, I. Lampronti, and D. Simoni, J. Heterocyclic Chem., 34, 1225 (1997).
9. SAINT, Version 6.02a, Bruker AXS Inc., Madison, WI (2002).
10. G. M. Sheldrick, SADABS, Program for Bruker Area Detector Absorption Correction, Univ. Göttingen, Germany
(1997).
11. a) G. M. Sheldrick, SHELXS-97, Program for Crystal Structure Solution, Univ. Göttingen, Germany (1997);
b) G .M. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement, Univ. Göttingen, Germany (1997).
985