Molecular and Crystal Structure of 1-(4-Fluorophenyl)-1,4-Dihydro-1H-Tetrazole-5-Thione and Its Complex with Cadmium(II)

Article abstract of DOI:10.1134/S0022476618070193

The molecular and crystal structures of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione (I) and its complex with cadmium(II) (II) are studied by single crystal XRD. Free ligand I is thione; it has a nonplanar structure (the torsion angle between the

Full text of DOI:10.1134/S0022476618070193

Journal of Structural Chemistry. Vol. 59, No. 7, pp. 1658-1663, 2018.
Original Russian Text © 2018 R. K. Askerov, A. M. Maharramov, V. K. Osmanov, E. V. Baranov, G. N. Borisova, P. V. Dorovatovskii,
V. N. Khrustalev, A. V. Borisov.
MOLECULAR AND CRYSTAL STRUCTURE
OF 1-(4-FLUOROPHENYL)-1,4-DIHYDRO-1H-
TETRAZOLE-5-THIONE AND ITS COMPLEX
WITH CADMIUM(II)
1 1
R. K. Askerov , A. M. Maharramov ,
2
3
V. K. Osmanov , E. V. Baranov , G. N. Borisova ,
2
4 4,5
P. V. Dorovatovskii , V. N. Khrustalev ,
2
and A. V. Borisov
The molecular and crystal structures of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione (I) and its
complex with cadmium(II) (II) are studied by single crystal XRD. Free ligand I is thione; it has a non-
planar structure (the torsion angle between the tetrazole and benzene rings is 54.99(7)°) and forms
H-bonded centrosymmetric dimers via two N–H…S hydrogen bonds in the crystal. The dimers contain
a central planar eight-membered {S=C–N–H…S=C–N–H…} ring. Complex II has a chain structure with
7 4 4 2 n
the composition [(C H N FS) Cd] . The environment of the Cd(II) atom consists of two nitrogen atoms and
two sulfur atoms from four ligands I and represents a distorted tetrahedron. When complex II forms, ligand
I converts into the thiol form. Infinite 1D chains contain eight-membered {←S=C–N–Cd←S=C–N–Cd}
rings in a chair conformation. The chains in the crystal are arranged in layers parallel to the (101) plane due
to secondary intermolecular F…F and π–π-stacking interactions.
DOI: 10.1134/S0022476618070193
Keywords: 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione, cadmium(II) complex, crystal structure,
secondary F…F interactions, synchrotron radiation.
INTRODUCTION
The article studies the structure of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione (I) and its complex with
cadmium(II) (II).
N-Substituted mercaptotetrazoles have several electron-donor centers and can be used as polydentate ligands in
complexing reactions with different metals to produce various supramolecular architectures [1-6].
As is known from the literature data, these heterocyclic compounds can exist in both thione (a) and thiol forms (b).
However, the thione form is considered to be more stable for mercaptotetrazoles [7].
1
2
Baku State University, Azerbaijan; rizvankam@bk.ru. Alekseev Nizhny Novgorod State Technical University,
3
Russia. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia.
4
5
National Research Center “Kurchatov Institute”, Moscow, Russia. People’s Friendship University of Russia, Moscow,
Russia. Translated from Zhurnal Strukturnoi Khimii, Vol. 59, No. 7, pp. 1717-1722, September-October, 2018. Original
article submitted March 4, 2018.
1658
0022-4766/18/5907-1658 © 2018 by Pleiades Publishing, Ltd.

First we prepared initial compound I according to the known procedure and then synthesized complex II by the
complexing reaction of organic ligand I with cadmium(II) chloride. The structure of synthesized compounds I and II was
studied by single crystal X-ray diffraction (XRD).
EXPERIMENTAL
3 2
The initial NaN , CdCl reagents were of at least chemically pure grade and used without additional purification. 4-
Fluorophenylisothiocyanate was bought from Acros Organics (Belgium) and used without further purification.
Synthesis of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione (I). To a solution of 1.9 g (29 mmol) of NaN
3
in 50 ml of H
2
O 3 g (19.6 mmol) of 4-fluorophenylisothiocyanate were added at 20 °C. The reaction mixture was boiled for
2
h, cooled to 20 °C; then the aqueous solution was filtered from undissolved impurities and a 10% aqueous solution of HCl
was added to it with stirring to рH = 2. The precipitate of compound I was filtered off, washed with 200 ml of water, and
dried at 80 °C. Yield was 2.43 g (63.23%). White crystals. Тmelt = 150-152 °C. Found (%): C 42.37, H 2.41, N 28.73.
C H FN S. Calculated (%): C 42.85, H 2.57, N 28.56.
7
5
4
Synthesis of compound (II). To a solution of 0.392 g (2 mmol) of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-
thione I in 25 ml of 96% C OH a solution of 0.112 g (1 mmol) of CdCl in 15 ml of 96% C OH was added. The reaction
mixture was boiled for 2 h and cooled to 20 °C. The precipitate of compound II was filtered off, washed with 50 ml of
OH, and dried at 80 °C. The substance was recrystallized from ethanol. Yield was 0.067 g (15.47%). White crystals.
melt = 255-256 °C. Found (%): C 33.21, H 1.54, N 22.76. C14 CdF . Calculated (%): C 33.44, H 1.6, N 22.63.
Single crystal XRD. Crystals for XRD experiments were obtained by recrystallization of I and II from ethanol. The
2
H
5
2
2 5
H
2 5
C H
Т
H
8
2 8 2
N S
single crystal XRD study was carried out on the “BELOK” synchrotron beamline at the National Research Center “Kurchatov
Institute” (λ = 0.96990 Å, Rayonix SX165 CCD detector, ϕ-scanning) (compound I) and a Bruker Smart Apex diffractometer
α
(MoK radiation, λ = 0.71073 Å, ϕ- and ω-scanning) (compound II). Importantly that it is synchrotron radiation that allowed
us to determine the structure of compound I with a high accuracy of measuring geometric parameters because the single
crystals of this compound were of rather poor quality which we failed to improve. The experimental sets of reflection
intensities were collected and integrated using the MARCCD [8] and iMOSFLM programs respectively, being the
subroutines of the CCP4 program suite [9] (for compound I), and SMART [10] and SAINT [11] (for compound II). The
2
structures were solved by a direct method and refined by full-matrix LSM against Fhkl in the anisotropic approximation for
non-hydrogen atoms. The hydrogen atom of the amino group in I was identified objectively in the difference Fourier maps
and refined isotropically with fixed displacement parameters (Uiso(H) = 1.2Ueq(N)). The positions of the other hydrogen
atoms in I and II were calculated geometrically and included in the refinement with fixed positional parameters (riding
model) and isotropic displacement parameters (Uiso(H) = 1.2Uiso(C)). X-ray absorption correction was applied using the Scala
[12] (compound I) and SADABS [13] (compound II) softwares respectively. All calculations related to the crystal structure
refinement were performed using the SHELXTL software [14]. The crystallographic data and the parameters of the single
crystal XRD experiments are given in Table 1. The structures have been deposited with CCDC under numbers 1479807 (I),
1479766 (II) and are available at the address: ccdc.cam.ac.uk/getstructures.
RESULTS AND DISCUSSION
The selected valence bond lengths, bond and torsion angles for compound I are given in Table 2.
1659

TABLE 1. Main Crystallographic Data and Refinement Parameters for Compounds I and II
Parameters
I
II
Chemical formula
Molecular weight
Temperature, K
Crystal size, mm
Crystal symmetry
Space group
C
7
H
5
FN
196.21
100
4
S
C
14
H
8
2 8 2
CdF N S
502.80
100
0.15×0.15×0.10
0.21×0.16×0.16
Triclinic
Monoclinic
P-1
C2/c
a, b, c, Å
3.8649(8), 10.705(2), 11.130(2)
26.4468(13), 8.9421(4), 7.3009(3)
α, β, γ, deg
65.71(3), 86.29(3), 82.21(3)
β 101.856(1)
1689.76(13)
4
3
V, Å
415.83(17)
2
Z
3
d(calc.), g/cm
1.567
1.976
–
1
μ, mm
0.844
1.579
F(000)
200
984
θ range of data collection, deg
Meas. / indep. reflections
Refined parameters
38
25
5814 / 1301
122
8303 / 1996
123
R
1
[I > 2σ(I)] / wR
2
(all data)
0.0534 / 0.1265
1.000
0.0421 / 0.0909
1.047
GOOF
T
min; Tmax
0.868; 0.909
–0.463 / 0.366
0.384; 0.746
–1.331 / 2.484
Residual electron density,
3
(ρmin / ρmax), e/Å
TABLE 2. Selected Valence Bond Distances, Bond and Torsion Angles in Compound I
Bond
d, Å
Bond
d, Å
Bond
d, Å
S(1)–C(5)
N(1)–C(5)
N(1)–N(2)
N(2)–N(3)
1.676(3)
1.370(3)
1.380(3)
1.287(3
N(3)–N(4)
N(4)–C(5)
N(1)–C(6)
1.363(3)
1.361(3)
1.444(3)
C(6)–C(7)
C(6)–C(11)
F(1)–C(9)
1.386(4)
1.397(3)
1.364(3)
Angle
ω, deg
Angle
ω, deg
Torsion angle
ω, deg
C(5)–N(1)–C(6)
N(2)–N(1)–C(6)
C(11)–C(6)–N(1)
128.9(2)
120.38(19)
119.0(2)
N(1)–C(5)–S(1)
C(7)–C(6)–N(1)
N(4)–C(5)–S(1)
129.03(19)
119.0(2)
C(5)–N(1)–C(6)–C(11)
57.3(4)
129.14(18)
Compound I is 1-(4-fluoro-phenyl)-1,4-dehydro-5H-tetrazole-5-thione and consists of two planar moieties: п-
fluorophenyl and mercaptotetrazole rings. The angle between these planes is 54.99(7)°. The N(1)–N(2) (1.363(3) Å), N(1)–
C(5) (1.370(3) Å), N(3)–N(4) (1.361(3) Å), and N(4)–C(5) (1.380(3) Å) bond lengths in the mercaptotetrazole moiety
correspond to single bonds, while the N(2)=N(3) (1.287(3) Å) and C(5)=S(1) (1.676(3) Å) bonds are double (Table 2), which
confirms the existence of compound I in thione form in the free state. The C(5)–N(1)–C(6)–C(11) torsion angle is 57.3(4)°.
The analysis of bond lengths in the structure of I showed that all of them correspond to average values [15].
In the crystal, molecules of I form H-bonded centrosymmetric dimers via two N(4)–H(4)…S(1) (1–x, 1–y, 1–z)
hydrogen bonds (N–H is 0.91(2) Å, H…S is 2.34(2) Å, the N–H… angle is 177(2)°) (Fig. 1) [16-18]. The dimers contain
a central planar eight-membered ring {S=C–N–H…S=C–N–H… (rms = 0.009 Å)}. The C(5)=S(1) bond length (1.676(2) Å)
corresponds to that of double bonds.
1660

Fig. 1. Structure of H-bonded dimers in the crystal of compound I.
The dimers of compound I are located in the crystal in such a way that the phenyl and tetrazole rings are arranged in
pairs parallel to each other to form stacks along the а axis (Fig. 2). The distance between the ring centers is 3.865(2) Å, which
exceeds the geometric criterion of the π–π stacking interaction [19].
The bond lengths, bond and torsion angles in complex II are given in Table 3.
7 4 4 2 n
Complex II has a one-dimensional chain structure of the composition [(C H N FS) Cd] . The coordination
environment of the cadmium cation is a distorted tetrahedron containing two nitrogen atoms and two sulfur atoms from four
ligands I. The Cd–S and Cd–N distances are 2.4972(11) Å and 2.228 (4) Å respectively. The N–Cd–N and S–Cd–S angles
are 103.44(19)° and 105.06(5)° respectively. Note that the character of bonds in the mercaptotetrazole moiety of ligand I
Fig. 2. Fragment of the crystal packing of I along the а axis.
TABLE 3. Selected Valence Bond Distances, Bond and Torsion Angles in Complex II
Bond
d, Å
Bond
d, Å
Bond
d, Å
Cd(1)–N(4)#1
Cd(1)–N(4)
2.228(4)
2.228(4)
S(1)–C(5)
N(1)–C(5)
N(1)–N(2)
N(2)–N(3)
N(3)–N(4)
1.728(4)
1.354(5)
1.371(5)
1.288(5)
1.365(5)
N(4)–C(5)
N(1)–C(6)
C(6)–C(7)
C(6)–C(11)
F(1)–C(9)
1.332(5)
1.432(5)
1.390(6)
1.388(6)
1.357(5)
Cd(1)–S(1)#2
Cd(1)–S(1)#3
Cd(1)#3–S(1)
2.4972(11)
2.4972(11)
2.4972(11)
Angle
ω, deg
Angle
ω, deg
Torsion angle
ω, deg
N(4)#1–Cd(1)–N(4)
S(1)#2–Cd(1)–S(1)#3
C(5)–N(1)–C(6)
103.44(19)
105.06(5)
128.9(2)
C(11)–C(6)–N(1)
N(1)–C(5)–S(1)
C(7)–C(6)–N(1)
N(4)–C(5)–S(1)
119.9(4)
125.7(3)
118.5(4)
128.1(3)
C(5)–N(1)–C(6)–C(11)
46.5(6)
N(2)–N(1)–C(6)
120.38(19)
1661

changes when complex II forms. Thus, the C(5)–S(1) bond (1.728(4) Å) becomes single and the N(4)=C(5) bond
1.332(5) Å) becomes double (Table 3) due to a higher chemical affinity of the cadmium cation to a sulfur atom than to
(
a nitrogen atom. Hence, unlike the free state, in complex II mercaptotetrazole ligand I takes the thiol form. The angle
between the planes of the phenyl and mercaptotetrazole moieties is 45.56(16)°. Infinite 1D chains contain eight-membered
{
←S=C–N–Cd←S=C–N–Cd} rings in a chair conformation. The distance between the metal atoms Cd…Cd is 4.165 Å.
One-dimensional polymer chains of complex II in the crystal are arranged along the c axis (Fig. 3).
The detailed analysis of the crystal packing of complex II shows that between the neighboring one-dimensional
chains along the b axis there is a parallel packing of phenyl moieties of the chains extending along the c axis. The shortest
C…C distances are observed between the carbon atoms C(7)…C(10) (3.404(3) Å) and C(6)…C(9) (3.479(3) Å) and indicate
the presence of weak π–π stacking interactions [19]. The distance between the ring centers is 3.651(3) Å, which only slightly
exceeds the geometric criteria of the said π–π stacking interactions [19].
In addition, it was revealed that there were short intermolecular fluorine-fluorine contacts between the adjacent
chains along the а axis. The F…F distances are 2.736(2) Å and correspond to weak secondary F…F interactions (between
2.80 Å and 2.65 Å [20]) (Fig. 3).
Fig. 3. F…F contacts in the crystal of complex II.
1662

CONCLUSIONS
Thus, by single crystal XRD it is established that in the crystal compound I is in the thione form. These heterocyclic
compounds have several electron-donor centers and the use of I as a ligand in the complexing reaction with cadmium(II)
chloride gives complex II, which has a 1D polymeric chain structure. It is shown that when complex II forms,
mercaptotetrazole ligand I converts into the thiol form. The crystal structure of II is stabilized by intermolecular secondary
F…F and π–π stacking interactions.
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