Crystal structures of methyl and benzyl 5-ferrocenyl-3,5-dimethyl-2- pyrazoline-1-dithiocarboxylate

Article abstract of DOI:10.1134/S0022476613060152

Reactions of E-4-ferrocenylpent-3-en-2-one with S-methyldithiocarbazate or S-benzyldithiocarbazate result in the formation of methyl 5-ferrocenyl-3,5- dimethyl-2-pyrazoline-1-dithiocarboxylate (1) or benzyl 5- ferrocenyl-3,5- dimethyl-2-pyrazoline-1-dithiocarboxylate (2). The single crystals of both products are obtained and their structures are identified by X-ray diffraction method with triclinic P-1 space groups. The cell parameters for compound 1 are as follows: a = 7.7029(8) A, b = 10.1631(11) A, c = 10.7305(12) A, α = 101.3270(10)°, β = 90.6740(10)°, γ = 94.8390(10)°, and V = 820.40(15) A³. For compound 2, the crystallographic data are: a = 7.953(3) A, b = 10.970(5) A, c = 12.534(3) A, α = 84.718(5)°, β = 81.651(3)°, γ = 76.274(4)°, and V = 1049.1(7) A³.

Full text of DOI:10.1134/S0022476613060152

Journal of Structural Chemistry. Vol. 54, No. 6, pp. 1107-1111, 2013
Original Russian Text © 2013 X. Zhu, D.-S. Xiang, W.-Y. Shi
CRYSTAL STRUCTURES OF METHYL AND BENZYL
5-FERROCENYL-3,5-DIMETHYL-2-PYRAZOLINE-
1-DITHIOCARBOXYLATE
1,2 1
X. Zhu, D.-S. Xiang, and W.-Y. Shi
3
UDC 548.73:547.13:546.72
Reactions of E-4-ferrocenylpent-3-en-2-one with S-methyldithiocarbazate or S-benzyldithiocarbazate result
in the formation of methyl 5-ferrocenyl-3,5-dimethyl-2-pyrazoline-1-dithiocarboxylate (1) or benzyl 5-
ferrocenyl-3,5-dimethyl-2-pyrazoline-1-dithiocarboxylate (2). The single crystals of both products are
obtained and their structures are identified by X-ray diffraction method with triclinic P-1 space groups. The
cell parameters for compound 1 are as follows: a = 7.7029(8) Å, b = 10.1631(11) Å, c = 10.7305(12) Å,
3
= 90.6740(10°,) γ = 94.8390(10)°, and V = 820.40(15) Å . For compound 2, the
= 81.651(3°,)
α = 101.3270(10)°, βꢀ
crystallographic data are: a = 7.953(3) Å, b = 10.970(5) Å, c = 12.534(3) Å, α = 84.718(5)°, βꢀ
3
γ = 76.274(4)°, and V = 1049.1(7) Å .
DOI: 10.1134/S0022476613060152
Keywords: pyrazoline, ferrocenyl, dithiocarboxylate, X-ray.
Pyrazolines were first reported by Knorr and Blank in 1885 [1]. Since then, a large number of pyrazoline derivatives
were synthesized due to their wide variety of biological activities such as antidepressant [2], anti-inflammatory [3], antimicrobial
[4], antimycobacterial [5], anticancer [6], antibacterial [7], and photoluminiscence activities [8], etc. Besides, pyrazoline
derivatives were also used as fluorescent brightening agents for their strong blue fluorescence in solution [9] and high
fluorescence quantum yields [10]. While several new methodologies have been applied to the synthesis of pyrazolines and their
derivatives [11] recently, we, herein, present the syntheses and the crystal structures of two new pyrazoline derivatives.
EXPERIMENTAL
Synthesis of E-4-ferrocenylpent-3-en-2-one. In a sealed tube, acetylferrocene (5.0 mmol) was dissolved in 20 ml
of ethanol, followed by adding 6.0 M NaOH solution (5.0 ml) and acetone (5.0 mmol). This solution was shaken at room
temperature for 48 h. The precipitate was collected by filtration to obtain the crude product, which was purified by
recrystallization from ethanol, giving a pure orange product with a yield of 75% (Scheme 1).
Synthesis of compounds 1 and 2. A solution of E-4-ferrocenylpent-3-en-2-one (1.0 mmol) and S-methyldithio-
carbazate (1.0 mmol) or S-benzyldithiocarbazate (1.0 mmol) in 10 ml of ethanol was refluxed for 48 h. This solution was
1
Department of Chemical Engineering, Yancheng Textile Vocational Technology College, Yancheng, P. R. China;
2
xunzhu.yc@gmail.com. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, P. R.
3
China. School of Chemical and Biological Engineering, Yancheng Institute of Technology, Yancheng, P. R. China. The text
was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 54, No. 6, pp. 1077-1081, November-December,
2013. Original article submitted May 17, 2012.
0022-4766/13/5406-1107 © 2013 by Pleiades Publishing, Ltd.
1107

Scheme 1. Synthesis of E-4-ferrocenylpent-3-en-2-one
Scheme 2. Synthesis of methyl 5-ferrocenyl-3,5-dimethyl-2-
pyrazoline-1-dithiocarboxylate (1) and benzyl 5-ferrocenyl-3,5-
dimethyl-2-pyrazoline-1-dithiocarboxylate (2)
cooled and stored in a freezer at 0°C for 12 h with the formation of yellow precipitates. The crude products were collected by
filtration and recrystallized from ethanol to give pure products, which were redissolved in dichloromethane and slowly
evaporated to obtain the desired crystal (Scheme 2).
X-ray crystallography. For single crystal X-ray diffraction studies a Bruker Smart Apex II CCD area-detector
diffractometer with graphite-monochromated MoK radiation (λ = 0.71073 Å) is used at 296(2) K to collect the
α
crystallographic data using the ω-scan technique. The diffraction data were integrated using the SAINT program [12], which
was also used for the intensity corrections for the Lorentz and polarization effects. Semi-empirical absorption correction was
applied using the SADABS program [13]. The structures were solved by direct methods and all the non-hydrogen atoms were
2
refined anisotropically on F by the full-matrix least-squares technique using the SHELXL-97 crystallographic software
package [14]. Hydrogen atoms were generated geometrically. Table 1 collects the details of the crystal parameters, while
Table 2 and Table 3 give the selected bond lengths and angles for each crystal.
RESULTS AND DISCUSSION
For the single crystals, both compounds crystallized in triclinic crystal systems and P-1 space groups, as depicted in
Figs. 1 and 2.
For the ferrocenyl moieties, the distances from Fe(II) to the center of the substituted cyclopentadiene ring (C ) and
ps
unsubstituted cyclopentadiene (C ) are nearly the same, being 1.653(2) Å and 1.658(9) Å for compound 1 and 1.653(3) Å and
p
1.654(1) Å for compound 2. The C –Fe–C bond angles are 176.53(1)° and 177.35(3)° for each compound. These values
ps p
indicate that for both compounds, the central Fe(II) atom locates almost in the middle of the two cyclopentadiene rings.
Besides, two cyclopentadiene rings are not parallel to each other. Small dihedral angles are found to be 4.63 Å and 3.44 Å for
compounds 1 and 2.
For the pyrazolinyl rings, C11 is the only stereocenter with four different substituents. The N2–C11–C13 bond
angles are 99.57(1)° and 99.5(6)° for corresponding compoundы 1 and 2, which can be explained by the restriction of the
pyrazolinyl rings. All other bond angles are similar to the regular tetrahedral values, ranging from 108.34(2)° to 113.6(7)°,
which results in distorted tetrahedral geometries for the C11 stereocenters. The C14=N1 and C11–N2 are typical double and
1108

TABLE 1. Crystal Data and Structure Refinement for Both Compounds
Formula
C H FeN S (1)
17 20 2 2
C H FeN S (2)
23 24 2 2
M
372.32
Triclinic
P-1
448.41
Triclinic
P-1
r
Crystal system
Space group
a, b, c, Å
7.7029(8), 10.1631(11), 10.7305(12)
7.953(3), 10.970(5), 12.534(3)
101.3270(10), 90.6740(10), 94.8390(10)
84.718(5), 81.651(3), 76.274(4)
α, β, γ, deg
T, K
296(2)
820.40(15)
2
296(2)
1049.1(7)
2
3
V, Å
Z
–3
1.507
1.419
0.929
468
ρ
calc
, g⋅cm
–1
1.170
μ, mm
F(000)
388
2.5-27.6
2.6-27.5
θ range, deg
Radiation type, λ, Å
Index ranges (h, k, l)
MoK , 0.71073
α
MoK , 0.71073
α
–9/9, –12/12, –13/13
–9/9, –11/13, –15/15
R
0.0187
3310
202
0.0301
int
Parameter refined
Refinement parameters
Refinement restrictions
Reflections with I > 2σ(I )
GOOF
4065
255
0
0
3037
1.130
3286
1.176
a
b
R = 0.0274, wR = 0.0751
R = 0.0803, wR = 0.2323
1 2
Final R factor [I > 2σ(I )]
R factor (all data)
1
2
R = 0.0306, wR = 0.0799
1 2
R = 0.0935, wR = 0.2376
1 2
3
0.276/–0.391
1.334/–0.515
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
o
0
0
c
TABLE 2. Selected Geometric Parameters (Å, deg) for Compound 1
C11–N2
C13–C14
1.529(2)
1.492(2)
1.343(2)
112.81(2)
99.57(1)
108.64(1)
129.16(1)
C11–C13
C14–N1
1.541(2)
1.280(2)
C10–C11
N1–N2
1.508(2)
1.408(2)
C16–N2
C16–S3
1.6607(2)
108.34(2)
104.62(1)
111.87(1)
124.77(1)
C16–S4
1.7813(2)
112.24(2)
114.30(2)
117.73(1)
123.49(1)
C10–C11–C12
N2–C11–C13
C14–N1–N2
C16–N2–C11
N2–C11–C12
C14–C13–C11
N1–N2–C11
N2–C16–S3
C10–C11–C13
N1–C14–C13
C16–N2–N1
S3–C16–S4
TABLE 3. Selected Geometric Parameters (Å, deg) for Compound 2
C11–N2
C13–C14
1.541(9)
1.492(1)
1.337(1)
113.6(7)
99.5(6)
C11–C13
C14–N1
1.531(1)
1.274(1)
1.670(8)
111.7(6)
104.8(7)
111.6(6)
123.8(6)
C10–C11
N1–N2
1.511(1)
1.418(9)
1.763(8)
113.2(7)
114.9(7)
118.0(6)
124.1(5)
C16–N2
C16–S1
C16–S2
C10–C11–C12
N2–C11–C13
C14–N1–N2
C16–N2–C11
N2–C11–C12
C14–C13–C11
N1–N2–C11
N2–C16–S1
C10–C11–C13
N1–C14–C13
C16–N2–N1
S1–C16–S2
108.2(7)
129.3(7)
1109

Fig. 1. Molecular structure of compound 1 with
the atom numbering scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Fig. 2. Molecular structure of compound 2 with the
atom numbering scheme. Displacement ellipsoids are
drawn at the 30% probability level.
Fig. 3. Bimolecular system of compound 1 via
the intermolecular C9–H9⋯N1′ hydrogen bond.
single bonds with the bond lengths being 1.280(2) Å, 1.529(2) Å and 1.274(1) Å, 1.541(9) Å for compounds 1 and 2
respectively. However, N1–N2 and C16–N2 bonds are slightly shorter with the values of 1.408(2) Å and 1.343(2) Å for
2
compound 1 and 1.418(9) Å and 1.337(1) Å for compound 2. This is attributed to the conjugation of the sp hybridized N2
atom with C14=N1 and C16=S3 (or C16=S1) double bonds, generating a large conjugated system involving C14, N1, N2,
C16, and S3 atoms for compound 1 (or C14, N1, N2, C16, and S1 for compound 2).
Compared with compound 2, which has no weak interactions, an intermolecular hydrogen bond is revealed in
compound 1 as C9–H9⋯N1′. The C9–H9, N1′⋯H9, and C9⋯N1′ bond lengths are 0.930 Å, 2.739(3) Å, and 3.528 Å, while
the bond angle is 143.20° for C9–H9⋯N1′. With this intermolecular hydrogen bond, a bimolecular system can be found, as
shown in Fig. 3.
CIF files containing complete information on the studied structures were deposited with CCDC, deposition
Nos. 882159 and 882160, and are freely available upon request from the following web site: http://www.ccdc.cam.ac.uk/
data_request/cif.
This work is financially supported by the “Six Talented Summit” funding of Jiangsu Province of P. R. China
(No. NO2011-JZ-017).
REFERENCES
1. L. Knorr and A. Blank, Ber. Dtsch. Chem. Ges., 18, 316 (1885).
1110

2. a) N. G. Kelekci, S. Koyunoglu, S. Yabanoglu, K. Yelekci, O. Ozgen, G. Ucar, K. Erol, E. Kendi, and A. Yesilada,
Bioorg. Med. Chem., 22, 23 (2008); b) E. Palaskaa, M. Aytemira, I. T. Uzbay, and D. Erola, Eur. J. Med. Chem., 36,
539 (2001); c) Y. R. Prasad, A. L. Rao, L. Prasoona, K. Murali, and P. R. Kumar, Bioorg. Med. Chem. Lett., 15, 5030
(2005); d) V. Jayaprakash, B. N. Sinha, G. Ucar, and A. Ercan, Bioorg. Med. Chem. Lett., 18, 6362 (2008); e) F.-B. Li,
T.-X. Liu, Y.-S. Huang, and G.-W. Wang, J. Org. Chem., 74, 7743 (2009); f) Y.-S. Huang and G.-W. Wang,
Theochem., 860, 24 (2008).
3. a) F. F. Barsoum and A. S. Girgis, Eur. J. Med. Chem., 15, 1 (2008); b) M. Amir, H. Kumar, and S. A. Khan, Bioorg.
Med. Chem. Lett., 18, 918 (2008); c) X. Chen and N. Ayres, Macromolecules, 43, 1341 (2010); d) X. Chen, K. Ding,
and N. Ayres, Polum. Chem., 2, 2635 (2011).
4. A. Ozdemir, G. TuranZitouni, Z. A. Kaplancıklı, G. Revial, and K. Guven, Eur. J. Med. Chem., 42, 403 (2007).
5. M. Shaharyar and A. A. Siddiqui, Bioorg. Med. Chem. Lett., 16, 4571 (2006).
6. B. A. Bhat, K. L. Dhar, S. C. Puri, A. K. Saxena, M. Shanmugavel, and G. N. Qazi, Bioorg. Med. Chem. Lett., 15, 3177
(2005).
7. F. Chimenti, B. Bizzarri, F. Manna, A. Bolasco, D. Secci, P. Chimenti, A. Granese, D. Rivanera, D. Lilli,
M. M. Scaltrito, and M. I. Brenciaglia, Bioorg. Med. Chem. Lett., 15, 603 (2005).
8. M. Jina, Y. J. Liang, R. Lua, X. H. Chuai, Z. H. Yi, Y. Y. Zhao, and H. J. Zhang, Syn. Met., 140, 37 (2004).
9. G. Bai, J. Li, D. Li, C. Dong, X. Han, and P. Lin, Dy. Pigmen., 75, 93 (2007).
10. a) F. Wilkerson, G. P. Kelly, C. Michael, and D. Oelkrug, J. Photochem. Photobiol. A, 52, 309 (1990); b) D. E. Rivett,
J. Rosevear, and J. F. K. Wilshire, Aust. J. Chem., 32, 1601 (1979).
11. a) Y. Ju and R. S. Varma, J. Org. Chem., 71, 135 (2006); b) K. Alex, A. Tillack, N. Schwarz, and M. Beller, Org. Lett.,
10, 2377 (2008); c) J. P. Waldo, S. Mehta, and R. C. Larock, J. Org. Chem., 73, 6666 (2008); d) S.-L. Cui, J. Wang, and
Y.-G. Wang, Org. Lett., 10, 13 (2008).
12. SAINT, Version 6.02a, Bruker AXS Inc., Madison, WI (2002).
13. G. M. Sheldrick, SADABS, Program for Bruker Area Detector Absorption Correction, Univ. Göttingen, Germany
(1997).
14. 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).
1111