1-(2-Methoxyphenyl)-1,4-Dihydro-5H-Tetrazole-5-Thione and Its Complex with Cd(II): Molecular and Crystal Structures

Article abstract of DOI:10.1134/S1070328419020039

Abstract: The molecular and crystal structures of 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione (L) and its complex with cadmium(II) (II) are studied by X-ray diffraction analysis (CIF files CCDC nos.?1567109 (L) and 1547252 (II)). Free ligand L is nonplanar thione. The dihedral angle between the tetrazole and benzene cycles is 85.21(7)°. These cycles form centrosymmetric dimers in the crystal by two hydrogen bonds N–H···S. The dimers contain the central planar eight-membered ring {S=C–N–H···S=C–N–H···}. Complex II has a chain structure of the composition [(C₈H₇N₄OS)₂Cd]_n. The coordination mode of the Сd(II) atom is a distorted tetrahedron consisting of two nitrogen atoms and two sulfur atoms of four ligands L. The 1D chains contain the eight-membered rings {←S=C–N–Cd ← S=C–N–Cd} in the boat conformation. Weak intermolecular hydrogen bonds C–H···N are observed between the adjacent 1D chains along the c axis in the crystal.

Full text of DOI:10.1134/S1070328419020039

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2019, Vol. 45, No. 2, pp. 112–118. © Pleiades Publishing, Ltd., 2019.
Russian Text © R.K. Askerov, A.M. Magerramov, V.K. Osmanov, E.V. Baranov, G.N. Borisova, A.D. Samsonova, A.V. Borisov, 2019, published in Koordinatsionnaya Khimiya,
2019, Vol. 45, No. 2, pp. 99–105.
1
-(2-Methoxyphenyl)-1,4-Dihydro-5H-Tetrazole-5-Thione
and Its Complex with Cd(II): Molecular and Crystal Structures
a,
a
b
c, d
b
R. K. Askerov *, A. M. Magerramov , V. K. Osmanov , E. V. Baranov , G. N. Borisova ,
b
b
A. D. Samsonova , and A. V. Borisov
a
Baku State University, Baku, Azerbaijan
b
Nizhny Novgorod State Technical University, Nizhny Novgorod, Russia
c
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia
d
Nizhny Novgorod State University, Nizhny Novgorod, Russia
*e-mail: rizvankam@bk.ru
Received May 29, 2018; Revised August 21, 2018; Accepted August 24, 2018
Abstract—The molecular and crystal structures of 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione
L) and its complex with cadmium(II) (II) are studied by X-ray diffraction analysis (CIF files CCDC
(
nos. 1567109 (L) and 1547252 (II)). Free ligand L is nonplanar thione. The dihedral angle between the tetra-
zole and benzene cycles is 85.21(7)°. These cycles form centrosymmetric dimers in the crystal by two hydro-
gen bonds N–H···S. The dimers contain the central planar eight-membered ring {S=C–N–H···S=C–N–
H···}. Complex II has a chain structure of the composition [(C H N OS) Cd] . The coordination mode of
8
7
4
2
n
the Сd(II) atom is a distorted tetrahedron consisting of two nitrogen atoms and two sulfur atoms of four
ligands L. The 1D chains contain the eight-membered rings {←S=C–N–Cd ← S=C–N–Cd} in the boat
…
conformation. Weak intermolecular hydrogen bonds C–H N are observed between the adjacent 1D chains
along the c axis in the crystal.
Keyword: 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione, crystal structure, polymer complex
DOI: 10.1134/S1070328419020039
INTRODUCTION
It is known from the literature data that similar het-
erocyclic compounds can exist in both the thione (a)
The structures of 1-(2-methoxyphenyl)-1,4-dihy-
dro-5H-tetrazole-5-thione (L) and its complex with and thiol (b) forms (Scheme 1). The thione form is
cadmium(II) (II) were studied in this work.
considered to be more stable for mercaptotetrazoles
7]. These compounds should be transformed into
[
N-Substituted mercaptotetrazoles with several elec-
tron-donor centers can be used as ligands for the prepa- alkaline metal thiolates to substitute them at the sulfur
ration of various coordination compounds [1–6].
atoms.
S
HS
R
R
N
NH
N
N
N
R-NCS + NaN3
N
N
N
(
a)
(b)
Scheme 1.
We synthesized ligand L, which was transformed into the ylate, and compound Iwas used without isolation in the reac-
corresponding thiolate (I) by the treatment with sodium eth- tion with cadmium chloride to form complex II (Scheme 2).
112

1-(2-METHOXYPHENYL)-1,4-DIHYDRO-5H-TETRAZOLE-5-THIONE AND ITS COMPLEX
113
H
N
N
N
N
N
N
S
+
C2H5ONa
SNa
N
N
O
O
(L)
(I)
CdCl2
(II)
Scheme 2.
The structures of compounds L and II were deter- was recrystallized from ethanol. The yield of com-
mined by X-ray diffraction analysis.
pound II as white crystals with mp = 202–204°С
with decomposition) was 0.093 g (18.06%).
(
EXPERIMENTAL
For C H N O S Cd
16
14
8
2 2
The starting reagents NaN , CdCl (not lower than
3
2
Anal. calcd., %
Found, %
C, 36.50
C, 36.03
H, 2.66
H, 2.48
N, 21.29
N, 21.57
reagent grade), and o-methoxyphenyl isothiocyanate
(
Acros Organics, Belgium) were used without addi-
tional purification.
Synthesis of thione L. o-Methoxyphenyl isothiocy-
X-ray diffraction analyses of compounds L and II
anate (6.431 g, 39 mmol) was added to a solution of
were carried out on a Bruker Smart Apex diffractome-
NaN (2.53 g, 39 mmol) in Н О (50 mL) at 20°С. The
3
2
ter (ω scan mode, МоK radiation, λ = 0.71073 Å, T =
α
reaction mixture was refluxed for 2 h, cooled to 20°С,
and filtered to remove nondissolved impurities. A 10%
aqueous solution of HCl was added with stirring to the
obtained solution to pH 2. The precipitate formed was
filtered off, washed with water (200 mL), and dried at
2
96 K). Experimental sets of reflection intensities
were collected and integrated using the SMART [8]
and SAINT [9] programs, respectively. The structures
were solved by a direct method and refined by full-
2
3
53 K. The product for X-ray diffraction analysis was matrix least squares for F in the anisotropic approx-
hkl
recrystallized from ethanol. The yield of L as white imation for non-hydrogen atoms. The hydrogen atom
crystals with mp = 162–164°С (with decomposition) involved in the intermolecular hydrogen bond N–
was 7.036 g (33.82%).
…
H S in L was localized from the difference electron
density synthesis and refined in the isotropic approxi-
mation. Other hydrogen atoms in L and II were placed
in geometrically calculated positions and refined iso-
For C H N OS (L)
8
8
4
Anal. calcd., %
Found, %
C, 46.15
C, 46.28
H, 3.85
H, 3.97
N, 26.92
N, 26.43
tropically with fixed thermal parameters U (H) =
iso
1
.2U (C). The structure was refined and an absorp-
iso
Synthesis of compound II. A solution of sodium
ethylate (0.136 g, 2 mmol) in anhydrous C H OH
tion correction was applied using the SHELXTL [10]
and SADABS [11] program packages. The crystallo-
graphic data and X-ray diffraction experimental
parameters are presented in Table 1.
2
5
(
15 mL) was added to a solution of thione L (0.416 g, 2
mmol) in anhydrous C H OH (25 mL). A solution of
2
5
CdCl (0.184 g, 1 mmol) in anhydrous C H OH
2
2
5
(15 mL) was added. The reaction mixture was refluxed
The structures were deposited with the Cambridge
for 5 h and cooled to 20°С. The precipitate formed was Crystallographic Data Centre (CIF files CCDC
filtered off, washed with C H OH (50 mL), and dried nos. 1567109 (L) and 1547252 (II); ccdc.cam.ac.uk/
2
5
at 353 K. The product for X-ray diffraction analysis getstructures).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 2 2019

1
14
ASKEROV et al.
Table 1. Main crystallographic data and refinement parameters for compounds L and II
Value
Parameter
L
C H N OS
II
Empirical formula
FW
C H N O S Cd
8
8
4
16 14
8
2 2
208.24
526.87
Crystal sizes, mm
Crystal system
Space group
a, Å
0.21 × 0.17 × 0.10
Monoclinic
0.65 × 0.074 × 0.06
Orthorhombic
Pccn
P2 /c
1
5.0808(7)
19.402(3)
9.9024(14)
90.967(3)
12.8945(8)
18.9350(12)
8.5599(6)
90
b, Å
c, Å
β, deg
V, Å3
976.0(2)
2090(6)
Z
4
4
ρcalcd, g/cm3
1.417
1.674
μ, mm–1
0.303
1.274
F(000)
432
25
1048
25
Range of data collection over θ, deg
Measured reflections
Independent reflections
Number of refined parameters
10754
2793
131
19754
2517
133
R (I > 2σ(I))
0.0471
0.0943
0.0216
0.0565
1.007
1
wR (all data)
2
GOОF
1.007
Tmin; Tmax
0.6474; 0.7461
0.384; 0.746
–0.156/0.781
Residual electron density (ρmin/ρmax), e Å–3
–0.318/0.378
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1-(2-METHOXYPHENYL)-1,4-DIHYDRO-5H-TETRAZOLE-5-THIONE AND ITS COMPLEX
115
C(11)
C(10)
N(2)
N(3)
N(1)
C(6)
C(9)
N(4)
C(5)
S(1)
C(7)
C(8)
O(1)
С(12)
Fig. 1. Molecular structure of L. Thermal ellipsoids are presented with 30% probability.
N(3A)
N(2A)
N(1A)
N(4A)
S(1)
C(11)
C(10)
C(9)
C(5)
C(6)
N(1)
C(7)
O(1)
C(8)
N(4)
N(3)
S(1A)
N(2)
C(12)
Fig. 2. Crystal structure of the H-bonded dimers in compound L. Thermal ellipsoids are presented with 30% probability.
RESULTS AND DISCUSSION
correspond to ordinary bonds, whereas the N(2)=N(3)
(
1.2773(19) Å) and С(5)=S(1) (1.6680(18) Å) distances
The molecular structure of L is shown in Fig. 1.
Selected bond lengths and bond and torsion angles in
compounds L and II are presented in Table 2.
correspond to double bonds, which confirms the thione
form of compound L in the free state. All bonds in the
structure of L correspond to statistical averages [12].
Compound L consists of two planar fragments:
In crystal molecules L form centrosymmetric
o-methoxyphenyl and mercaptotetrazole cycles. The
…
dihedral angle between their planes is 85.21(7)°, and the dimers by two hydrogen bonds N(4)–H(4) S(1) (1 –
torsion angle C(7)–C(6)–N(1)–C(5) is 93.3(2)°. The
methyl group in the methoxyphenyl fragment lies in the
cycle plane. The torsion angle C(8)–C(7)–O(1)–C(12)
is 0.4(2)°. The N(1)–N(2) (1.3675(19) Å), N(1)–C(5)
…
x, 1 – y, 1 – z) (N–H 0.93(2), H S 2.30(2) Å, angle
N–H–S 178(3)°) (Fig. 2).
The dimers contain the central planar (+0.0169 Å)
…
(
(
1.351(2) Å), N(3)–N(4) (1.354(2) Å), and N(4)–C(5) eight-membered ring {S=C–N–H S=C–N–H}.
1.346(2) Å) distances in the mercaptotetrazole fragment The dimers of compound L are linked into zigzag lay-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 45 No. 2 2019

1
16
ASKEROV et al.
b
0
a
c
…
Fig. 3. Fragment of the crystal packing of zigzag layers in compound L along the b axis. Weak hydrogen bonds C–H S are shown
by dashed lines.
ers along the b axis. The layers are connected by weak (Table 2), which is determined by a higher chemical
…
affinity of the cadmium cation to the sulfur atom than
to the nitrogen atom. Therefore, unlike the free state,
the tetrazole ligand L in complex II takes the thiol
form. The dihedral angle between the planes of the
phenyl and mercaptotetrazole fragments is 66.34(7)°,
and the torsion angles C(7)–C(6)–N(1)–C(5) and
C(8)–C(7)–O(1)–C(12) are 69.6(2)° and 4.5(3)°,
respectively. The 1D chains in the crystal of com-
pound II contain the eight-membered rings
intermolecular hydrogen bonds C(11)–H(11A S(1)
…
(
x – 1, y, z) (C–H 0.930(2), H S 2.915(2) Å, angle
…
C–H S 156(2)°) [13] along the а axis (Fig. 3).
Complex II has the 1D chain structure and the
composition [(C H N OS) Cd] . The coordination
8
7
4
2
n
polyhedron of the cadmium(II) cation is a distorted
tetrahedron containing two nitrogen atoms and two
sulfur atoms of four ligands L [6]. The Cd–S and Cd–
N distances (2.5035(4) and 2.2300(14) Å, respec-
tively) and the NCdN and SCdS angles (119.80(7)°
and 129.12(2)°, respectively) are correspondingly
equal. It should be mentioned that the character of
bonds in the tetrazole fragment of ligand L changes
{←N=C–S–Cd–S–C=N → Cd} in the boat confor-
…
mation. The Cd Cd distance is 4.280 Å. The chains
of complex II in the crystal are arranged along the с
axis (Fig. 4).
Weak intermolecular hydrogen bonds C(10)–
…
upon the formation of complex II, namely, the C(5)– H(10A) N(2) (–x + 3/2, y, –1/2 + z) (C–H
S(1) bond (1.716(2) Å) becomes ordinary and the 0.930(2), H…S 2.706(2) Å, angle C–H…N 148(2)°
N(4)=C(5) bond (1.326(2) Å) becomes double [13] (Fig. 5)) are observed between the adjacent 1D
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1-(2-METHOXYPHENYL)-1,4-DIHYDRO-5H-TETRAZOLE-5-THIONE AND ITS COMPLEX
117
Table 2. Selected bond lengths (d) and bond (ω) and torsion (γ) angles in compounds L and II
L
Bond
S(1)–C(5)
N(1)–C(5)
N(1)–N(2)
N(2)–N(3)
d, Å
Bond
d, Å
Bond
d, Å
1.6680(18)
1.351(2)
1.3675(19)
1.2773(19)
N(3)–N(4)
N(4)–C(5)
N(1)–C(6)
O(1)–C(7)
1.354(2)
1.346(2)
1.437(2)
1.356(2)
O(1)–C(12)
C(6)–C(11)
1.427(2)
1.374(2)
Angle
ω, deg
Angle
ω, deg
Angle
γ, deg
N(1)C(5)N(4)
C(5)N(1)N(2)
C(5)N(4)N(3)
N(3)N(2)N(1)
N(2)N(3)N(4)
102.11(15)
111.00(14)
111.79(16)
107.48(15)
107.62(15)
N(4)C(5)S(1)
N(1)C(5)S(1)
C(11)C(6)N(1)
C(7)C(6)N(1)
C(7)O(1)C(12)
129.35(14)
128.53(13)
118.52(15)
117.65(14)
C(5)N(1)C(6)C(11)
C(5)N(1)C(6)C(7)
C(12)O(1)C(7)C(8)
C(6)N(1)C(5)S(1)
87.3(2)
93.3(2)
0.4(3)
3.0(3)
II
Bond
d, Å
Bond
d, Å
Bond
d,Å
Cd(1)–N(4)
Cd(1)–S(1)
S(1)–C(5)
N(1)–C(5)
N(1)–N(2)
2.228(4)
N(2)–N(3)
N(3)–N(4)
N(4)–C(5)
N(1)–C(6)
1.280(2)
1.357(2)
1.326(2)
1.434(2)
C(6)–C(7)
C(6)–C(11)
O(1)–C(7)
O(1)–C(12)
1.392(3)
1.374(2)
1.354(2)
1.427(3)
2.4972(11)
1.7155(16)
1.349(2)
1.3616(19)
Angle
ω, deg
Angle
ω, deg
Angle
γ, deg
N(4)Cd(1)N(4A)
S(1)Cd(1)S(1E)
C(5)N(1)C(6)
N(2)N(1)C(6)
119.80(7)
129.12(2)
131.99(14)
118.97(14)
C(11)C(6)N(1)
N(1)C(5)S(1)
C(7)C(6)N(1)
N(4)C(5)S(1)
119.17(16)
127.52(12)
119.16(15)
126.35(12)
C(7)C(6)N(1)C(5)
C(8)C(7)O(1)C(12)
69.6(2)
4.5(3)
a
N(4A)
N(4B)
N(4G)
N(4C)
N(4D)
S(1D)
S(1A)
Cd(1)
S(1B)
S(1C)
Cd(1B)
S(1H)
S(1)
S(1E)
Cd(1A)
Cd(1C)
S(1D)
S(1F)
S(1G)
N(4F)
N(4H)
N(4D)
0
c
b
Fig. 4. Crystal structure of 1D polymer chains in compound II along the с axis.
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ASKEROV et al.
a
H(10)
N(2E)
0
H(10A)
N(2F)
H(10B)
H(10C)
N(2H)
N(2G)
c
b
Fig. 5. Fragment of the crystal packing of compound II in the projection onto the a0c plane. Weak hydrogen bonds С–Н…
between the adjacent polymer chains along the с axis are shown by dashed lines.
N
chains along the c axis in the crystal packing of com-
plex II.
7. Shtefan, E.D. and Vvedenskii, V.Yu., Usp. Khim., 1995,
vol. 65, no. 4, p. 326.
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. SMART. Bruker Molecular Analysis Research Tool.
Version 5.632, Madison: Bruker AXS, 2005.
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Translated by E. Yablonskaya
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