Synthesis of new metal-free 1,2,4,5,9,10,12,13-octaaza[16]annulene derivatives using the reaction of vinamidinium salts with thiocarbohydrazide

Article abstract of DOI:10.1002/jhet.4218

A new series of marcocyclic ligands, 1,2,4,5,9,10,12,13-octaaza[16]annulene derivatives were synthesized by using the condensation reaction of the correspondingly [2+2] 2-heteroaryl-substituted vinamidinium salts or phenyl vinamidinium salts and derivativ

Full text of DOI:10.1002/jhet.4218

Received: 19 July 2020
DOI: 10.1002/jhet.4218
Revised: 27 October 2020
Accepted: 22 December 2020
A R T I C L E
Synthesis of new metal-free 1,2,4,5,9,10,12,13-octaaza[16]
annulene derivatives using the reaction of vinamidinium
salts with thiocarbohydrazide
Askar Sabet | Abdolmohammad Mehranpour
Department of Chemistry, Faculty of
Abstract
Sciences, Persian Gulf University,
Bushehr, Iran
A new series of marcocyclic ligands, 1,2,4,5,9,10,12,13-octaaza[16]annulene
derivatives were synthesized by using the condensation reaction of the corre-
spondingly [2+2] 2-heteroaryl-substituted vinamidinium salts or phenyl vin-
amidinium salts and derivatives or halo-substituted vinamidinum salt [1A-
10A] with thiocarbohydrazide in ethanolic medium under mild condition.
Metal complexes were formed by reacting of ethanolic solution of Co, Ni, and
Zn with macrocyclic ligand in ethanolic medium under mild condition. Pur-
posed complexes have been characterized with the help of elemental analyses,
comparative absorption band of ν(C=N), mass, and NMR. Geometry and com-
plex formulation are out of scope of this work. The biological activities of caro-
hydrazide and thiocarbohydrazide base of the ligands and purposed complexes
such as antimicrobial, antitumor, and insecticides have attracted significant
attention in bioorganic chemistry.
Correspondence
Abdolmohammad Mehranpour,
Department of Chemistry, Faculty of
Sciences, Persian Gulf University,
Bushehr 75169, Iran.
Email: ammehranpour@hotmail.com
Funding information
Persian Gulf University
K E Y W O R D S
marcocyclic complexes, marcocyclic ligands, thiocarbohydrazid, Vilsmier–Haack reaction
conditions, vinamidinium salt
1 | INTRODUCTION
within the 16-membered inner ring are antiaromatic and
their central cavity is smaller than in porphyrins and, as
Substituted functional macrocycles play an important
role in supramolecular chemistry.[1,2] The chemistry of
heteromacrocyclic compounds has been investigated in
recent years on account of its various applications in bio-
inorganic chemistry and biological processes.[3] Transi-
tion metal complexes have been applied in wide variety
fields such as antifungal, analgesic, sedative, antipyretic,
and anti-inflammatory agents.[4–8] Synthesis of
heteromacrocyclic compounds via vinamidinium salts is
easy and suitable method.[9–11] Vinamidinium salts are
prepared under Vilsmeier–Haack conditions from aryl
acetic acids and undergo condensation reaction to pro-
duce heteromacrocyclic ligands.[12] Heteromacrocyclic
complexes contain a Hückel anti-aromatic 4n π-system
a consequence, the metal-nitrogen distance is shorter and
the complexes are more stable.[13] Some macrocycles con-
taining heteroatoms and functional groups have been
investigated as functional molecules.[14] Ring size and
metal ion are key function in macrocycles.[15] A novel
Schiff base decaaza complex synthesized by Shakir
et al.[16] A number of octa-aza annulene are synthesized
and studied. The synthesis of 14-membered octaaza mac-
rocycle benzyl bis(hydrazone) with aldehyde has been
reported.[17] Hydrazones are used for the synthesis of het-
erocycles, drug design, and as ligands for metal com-
plexes, antimicrobial, antitumor, and insecticides.[18–21]
The condensation reactions of [2+2] carbohydrazide or
thiocarbohydrazide with 3,4-hexanedione are used for
J Heterocyclic Chem. 2021;58:833–840.
wileyonlinelibrary.com/journal/jhet
© 2020 Wiley Periodicals LLC.
833

834
SABET AND MEHRANPOUR
synthesis of octaaza macrocyclic Schiff base.[22,23] Medicinal
applications of carbohydrazide and thiocarbohydrazide are
important reason for synthesize and characterize such mac-
rocyclic complexes.[24] In this work, we report the synthesis
and characterization of 16-membered octaaza macrocyclic
ligands obtained via the condensation reaction between
thiocarbohydrazide (TCH) and vinamidinium salts in
ethanolic solvent under mild condition. In continuation of
our research on the applications of macrocyclic ligands, we
report herein a simple method for the synthesis of three
macrocyclic complexes via the condensation reaction
between 16-membered octaaza macrocyclic ligand and tran-
sition metals Co, Ni, and Zn in ethanolic solvent under mild
condition.
signal at 12.98 ppm(broad,2H) in the ligand spectrum
can be assigned to NH. Benzo-H was appeared in
7.408–7.785 ppm(m,8H). The HC=C H-NMR spectrum
1
signals were appeared in 8.1 ppm(s,2H) and 8.8 ppm
(s,2H) and 13C-NMR at 167.2 and 151.4 ppm (Figure 1).
Phenyl vinamidinum salt as a first material 1H-NMR
HC=C appeared in 7.7 ppm(s,2H) and 13C-NMR at
163.38 because of conjugation. According to these evi-
dences including SH group, two NH groups, two phenyl
groups, two groups of HC=C and absent of NH2, indicate
formation of macrocyclic ligand [1B-10B].
Purposed mechanism for the synthesis of 7,15-bis(R)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-2,5,7,10,13,15-
hexaene-3,11-dithiol(B) (Scheme 1), by using the con-
densation reaction of the correspondingly [2+2] 2-
heteroaryl-substituted vinamidinium salts or phenyl
and derivatives vinamidinium salts or halo-substituted
vinamidinum salt [1A-10A] with thiocarbohydrazide in
ethanolic medium under mild condition. Vin-
amidinium salt was attacked by amine group of TCH
in presence of i-Pr2NEt and then elimination of
dimethylamine was occurred (Scheme 2). Product
(B) was obtained by an intramolecular nucleophilic
cyclization on the iminium salt[31] (Scheme 2).
2 | RESULTS AND DISCUSSION
2.1 | IR spectra
The IR information about the thiocarbohydrazide (TCH)
was showed the pair bands of NH2 in ν (3275, 3307), but
these bands were disappeared in spectrum of the free
ligands.[25,26] Characteristic IR bands (cm−1) of the ligand
and complex were showed in Table 1. The appearance of
N–H stretch single band in ν(3,250–3650) and imine
group (C=N) formation in ν(1607) indicate the formation
of macrocyclic ligand.[27,28] The ν(C=N) shifting to the
lower value in the complex showed a drift of lone pair
density of azomethine nitrogen toward the metal atom
and was coordinated with metal.[29] Appearance of
ν(653–685) indicates coordination of (M-N).[30]
The effect of reagent, solvent, temperature, and time
is illustrated in Table 2. i-Pr2NEt in EtOH at 50ꢀC proved
to be the best (Table 2, entry 8).
Metal complexes were prepared by reaction of ligands
[1B-10B] with metals [Co, Ni, and Zn] in ethanolic
solution under mild condition (Scheme 3). Proposed
geometry was suggested as octahedral.[32] Geometry and
complex formulation are out of scope of this work.
2.2 | NMR
3 | CONCLUSION
In the 13C-NMR spectrum of the TCH, a signal was
appeared at 180 ppm due to C=S, but this signal in the
ligand was shifted to 138 ppm, in addition a signal in the
1H-NMR spectrum of ligand in 3.4 ppm(s, H) was attrib-
uted to C-SH. In TCH 1H-NMR spectrum, NH2 was
appeared in 4.48 ppm and NH 7.98 ppm but this signals
was absent in ligand. Signals at 10.8–10.9 ppm(d,2H) and
Our study shows the feasibility of synthesizing 16-
membered
octaaza
macrocyclic
ligands.
The
thiocarbohydrazide acted as bidentate ligand. The con-
densation of vnamidinium salts with thiocarbohydrazide
leads to the synthesis of 16-membered annulene. The for-
mation of the macrocyclic ligand was confirmed by FT-
IR, NMR, and mass. The macrocyclic Schiff base ligand
acts as a tetradentate is coordinated through the four
nitrogen atoms with the metal ion to form complex.
TABLE 1 Table characteristic IR bands (cm−1) of the ligand
and complex
Entry
ν(C=N)
1582
ν(NH)
3430
3390
3392
3397
ν(M-N)
4 | EXPERIMENTAL SECTION
4.1 | General information
Ligand
Co-Ligand
Ni-Ligand
Zn-Ligand
1425
683
673
685
1448
Materials and measurements: Chemicals were purchased
from Merck and Sigmaaldrich. Vinamidinium salts
1504

SABET AND MEHRANPOUR
835
FIGURE 1 (A) 1H.NMR, (B) 13C.
NMR of 7,15-bis(4-chlorophenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (1B)
[1A-10A] were prepared according to literature
procedures.[33–36] Thiocarbohydrazide was synthesized
according to literature procedures.[37,38] 1H and 13C-
NMR spectra were recorded with a Bruker Avance DRX-
300. d6-DMSO was used as solvent and TMS as internal
standard. Mass spectral data were obtained on a
Finnigan-Matt 8430 (70-eV) spectrometer. The IR spectra
were obtained with a Perkin-Elmer 781 spectrophotome-
ter. Elemental analyses were made with a CHN Analyzer
(Flash, 1112 series EA, Thermo Finnigan Company) and
Electrothermal 9200 (Germany) was used for determina-
tion of melting points.

836
SABET AND MEHRANPOUR
SCHEME 1 Vinamidinium salts
synthesis via Vilsmier-Haack reaction
conditions (A) and condensation
reaction with TCH lead to product (B)
[Colour figure can be viewed at
wileyonlinelibrary.com]
SCHEME 2 Purposed mechanism
for the synthesis of 7,15-bis(phenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol and
derivatives [1B-10B]
TABLE 2 Effects of reagent and
solvent on the reaction of 2-substituted
vinamidinium salts with
Entry
Solvent
EtOH
Reagent
Temp(ꢀC)
reflux
reflux
reflux
reflux
reflux
reflux
50
Time (h)
Yield (%)a
1
AcOH 5 drops
AcOH 5 drops
AcOH 5 drops
AcOH 5 drops
AcOH 5 drops
i-Pr2Net 5 drops
i-Pr2NEt 5 drops
i-Pr2NEt 5 drops
i-Pr2Net 10 drops
i-Pr2NEt 5 drops
i-Pr2NEt 5 drops
24
24
24
24
24
7
-
2
MeOH
CH3CN
CH2Cl2
DMF
-
thiocarbohydrazid under different
conditions
3
-
4
-
5
-
6
CH3CN
MeOH
EtOH
50
58
63
63
65
67
7
15
3
8
50
9
EtOH
50
3
10
11
EtOH
50
15
20
EtOH
60
aIsolated yields.

SABET AND MEHRANPOUR
837
SCHEME 3 The purposed structure
of the complex [M(L)Cl2], M = Co,
Ni, Zn [Colour figure can be viewed at
wileyonlinelibrary.com]
1
4.1.1 | General procedure for the
synthesis of ligand of 7,15-bis(phenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol
1585 (s) cm−1(C=N), H-NMR (d6-DMSO) δ /ppm: 3.382
(s,2H,SH), 7.408–7.785 (m,8H, benzo-H), 8.108(s,2H,
HC=C), 8.833(s,2H, HC=C), 10.815–10. 861 (d,J =
13.8.2 Hz, 2H,NH), 12.970 (broad,2H,NH). 13C-NMR
(d6-DMSO) δ /ppm: 102.727, 121.426, 126.649, 127.436,
129.271, 131.037, 131.193, 131.399, 132.104, 138.816,
151.473, 167.233, Mass spectrum: m/e = 505, Anal. calcd
for (C20H18N8S2Cl2): C, 47.52; H, 3.56; N, 22.18.
Found: C, 47.78; H, 3.49; N, 21.97.
Thiocarbohydrazide 1.0 mmol was added in 7.0 mL of etha-
nol in a round-bottom flask. The solution was heated up to
50ꢀC and then 1.0 mmol vinamidinium salt and 5 drops of
i-Pr2NEt were added. The reaction mixture was refluxed at
50ꢀC for 3 hours. After the formation of red precipitate, Dis-
tilled water 50 mL was added and heated at 50ꢀC for
30 minutes. The red precipitate was collected by filtration,
washed with warm water and dried. The residue was
washed with 7 mL warm ethyl acetate, warm distilled
water, and dried under vacuum at 50ꢀC (Table 3).
4.1.4 | 7,15-bis(4-bromoophenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (2B)
Red powder; m.p. 198–200ꢀC; Yield 68%; %; UV–Vis:
292, 453 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1584 (s) cm−1(C=N), 1H-NMR (d6-DMSO): δ/ppm
= 3.132(s,2H,SH), 7.557–7.586 (m,8H, benzo-H), 8.097
(s,2H,HC=C), 8.828(s,2H, HC=C), 10.810–10.855
(d,J = 13.5 Hz, 2H,NH),12.975 (broad,2H,NH). 13C-NMR
(d6-DMSO): δ /ppm = 103.710, 119.844, 126.510, 127.782,
129.743, 130.944, 131.151, 131.560, 131.901, 140.777,
151.617, 167.810, Mass spectrum: m/e = 595, Anal. calcd
for (C20H18N8S2Br2): C, 40.34; H, 3.02; N, 18.82.
Found: C, 39.95; H, 2.99; N, 18.84.
4.1.2 | General procedure for the
synthesis of complex of 7,15-bis(phenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol
Ligand (L) (436 mg, 1 mmol.) was added to 25 mL ethanol
and heated up to 50ꢀC. Hot ethanolic solution (10 mL) of
CoCl2.6H2O (237 mg, 1 mmol) or NiCl2.6H2O (237 mg,
1 mmol) or ZnCl2 (136 mg, 1 mmol.) was added to ligand
solution with constant stirring. The mixture was refluxed
for (5) hours at 50ꢀC. A precipitate was formed. It was fil-
tered, washed several times with EtOH, and then washed
with diethyl ether and dried under vacuum at 50ꢀC.
4.1.5 | 7,15-bis(phenyl)-1,2,4,5,9,10,12,
13-octaazacyclohexadeca-2,5,7,10,13,
15-hexaene-3,11-dithiol (3B)
4.1.3 | 7,15-bis(4-chlorophenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (1B)
Light red powder; m.p. 196–198ꢀC; Yield 63%; %; UV–Vis:
303, 395 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1
1582 (s) cm−1 (C=N), H-NMR (d6-DMSO): δ/ppm: 3.403
(s,2H,SH), 7.198–7.728 (m,8H, benzo-H), 8.089(s,2H,
HC=C), 8.800(s,2H, HC=C), 10.869–10.914(d,J = 13.5 Hz,
2H,NH),12.834 (broad,2H,NH). 13C-NMR (d6-DMSO):
Red powder; m.p. 198–200ꢀC; Yield 65%;UV–Vis:
337, 387 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),

838
SABET AND MEHRANPOUR
TABLE 3 The synthesis of 7,15-bis(phenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-2,5,7,10,13,15-hexaene-
3,11-dithiol and derivatives via the reaction of 2-substituted
vinamidinium salts with thiocarbohydrazid in the presence of i-
Pr2NEt in ethanol at 50ꢀC
4.1.6 | 7,15-bis(4-methylphenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (4B)
Light red powder; m.p. 195–199ꢀC; Yield 60%; UV–Vis:
330, 384 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1
(NH), 1579 (s) cm−1(C=N), 1H-NMR (d6-DMSO):
δ/ppm = 3.430(s,2H,SH), 7.491–7.828 (m,8H, benzo-H),
8.189(s,2H,HC=C), 8.908(s,2H, HC=C), 10.9469–10.991
(d,J = 13.8 Hz, 2H,NH),12.891 (broad,2H,NH). 13C-
NMR (d6-DMSO): δ/ppm = 21.249, 106.827, 121.064,
121.916, 125.470, 125.591, 127.576, 128.824, 130.052,
132.427, 133.408, 139.931, 151.587, 164.276 Mass spec-
trum: m/e = 464, Anal. calcd for (C22H24N8S2): C,
56.89; H, 5.17; N, 24.14. Found: C, 56.68; H,
5.12; N, 24.18.
4.1.7 | 7,15-bis(3,5-dimethylpyridin)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol
perchlorate (5B)
Brown powder; m.p. 192–195ꢀC; Yield 70%; UV–Vis:
367, 410 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1580 (s) cm−1 (C=N), 1090 (s) cm−1(ClO4−); 1H-NMR
(d6-DMSO): δ/ppm
8.134–8.391 (m,6H, benzo-H), 8.894(s,2H,HC=C),), 9.219
11.7 Hz,2H,
= 2.531(s,12H), 3.291(s,2H,SH),
(s,2H, HC=C), 11.170–11.209(d,J
=
NH),13.708 (broad,2H,NH), 13C-NMR (d6-DMSO):
δ/ppm = 18.179, 110.742, 125.511, 126.932, 133.635,
138.331, 139.892, 141.716, 142.059, 145.259, 146.784,
160.766, Mass spectrum: m/e = 496 [M + -2ClO4-], Anal.
calcd for 695 (C22H28N10S2)(ClO4-)2: C, 37.98; H, 4.03; N,
20.14. Found: C, 38.07; H, 3.98; N, 20.19.
4.1.8 | 7,15-bis(naphtalin)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (6B)
Dark brown powder; m.p. 193–195ꢀC; Yield 64%; UV–
Vis: 345, 388 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1
(NH), 1575 (s) cm−1 (C=N), 1H-NMR (d6-DMSO):
δ/ppm:3.285 (s,2H,SH), 7.520–7.716 (m,8H, benzo-H),
7.766–7.910(m,2H,HC=C), 7.968–8.145 (m,6H, benzo-H),
8.573–8.575(d, J = 0.6 Hz, 2H, HC=C), 10.433–10.479
(d,J = 13.8 Hz, 2H,NH), 12.461 (broad,2H,NH). 13C-NMR
(d6-DMSO): δ/ppm = 102.820, 121.574, 125.750, 126.510,
127.319, 127.612, 128.091, 128.775, 129.021, 129.417,
129.743, 130.260, 130.944, 131.151, 131.325, 131.962,
132.651, 132.627, 134.020, 135.174, 135.492, 138.553,
149.101, 164.587, Mass spectrum: m/e = 536, Anal. calcd
δ/ppm: 103.987, 125.591, 125.697, 126.248, 126.901, 129.241,
129.372, 129.928, 130.908, 138.717, 151.454, 167.182, Mass
spectrum: m/e = 436 Anal. calcd for (C20H20N8S2): C,
55.04; H, 4.59; N, 25.69. Found: C, 54.87; H, 4.48; N, 25.73.

SABET AND MEHRANPOUR
839
for (C28H24N8S2): C, 62.68; H, 4.48; N, 20.89. Found: C,
62.75; H, 4.59; N, 24.27.
NMR (d6-DMSO): δ/ppm = 103.710, 138.543, 154.680,
160.702, Mass spectrum: m/e = 352, Anal. calcd for
(C8H10N8S2)Cl2: C, 27.27; H, 2.84; N, 31.82. Found: C,
27.33; H, 2.88; N, 31.76.
4.1.9 | 3,11-dimercapto-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-7,15-diyl)bis
(quinolin-1-ium) perchlorate(7B)
4.1.12 | 7,15-dibromo-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (10B)
Dark brown powder; m.p. 201–203ꢀC; Yield 61%; UV–
Vis: 318 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1583 (s) cm−1 (C=N), 1080 (s) cm−1(ClO4−); 1H-NMR
(d6-DMSO): δ/ppm = 3.396(s,2H,SH), 8.021–8.567 (m,
14H, benzo-H), 9.175(s,2H, HC=C), 9.667(s,2H, HC=C),
10.264(broad,2H,NH), 12.967 (broad,2H,NH). 13C-NMR
(d6-DMSO): δ/ppm = 102.622, 121.340, 125.945, 126.574,
127.220, 127.664, 128.266, 128.859, 128.987, 129.177,
129.907, 130.354, 130.568, 131.037, 131.325, 131.495,
132.181, 133.919, 134.020, 138.012, 151.287, 166.822, Mass
spectrum: m/e = 540 [M + -2ClO4-], Anal. calcd for
738 (C26H24N10S2)(ClO4−)2: C, 42.28; H, 3.25; N, 18.97.
Found: C, 42.19; H, 3.29; N, 19.03.
Brown powder; m.p. 198–201ꢀC; Yield 61%; UV–Vis:
309, 341 nm; IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1587 (s) cm−1 (C=N), 1H-NMR (d6-DMSO): δ/ppm = 3.486
(s,2H,SH), 8.070–8.109 (d,J = 11.7, 4H, HC=C), 11.683
(broad,2H,NH),12.995 (s,2H,NH). 13C-NMR (d6-DMSO):
δ/ppm = 104.791, 138.568, 153.448, 166.550, Mass spec-
trum: m/e = 442, Anal. calcd for (C8H10N8S2)Br2: C,
21.72; H, 2.26; N, 25.34. Found: C, 21.68; H, 2.24; N, 25.37.
4.1.13 | 7,15-bis(phenyl)-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol
complex (3C)
4.1.10 | 3,11-dimercapto-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-7,15-diyl)bis
(isoquinolin-2-ium) perchlorate(8B)
Ligand (L) (436 mg, 1 mmol.) was added to 25 mL etha-
nol and heated up to 50ꢀC. Hot ethanolic solution
(10 mL) of CoCl2.6H2O(237 mg, 1 mmol) or NiCl2.6H2O
(237 mg, 1 mmol) or ZnCl2 (136 mg, 1 mmol.) was added
to ligand solution with constant stirring. The mixture
was refluxed for (5) hours at 50ꢀC. A precipitate was
formed. It was filtered, washed several times with EtOH,
and then washed with diethyl ether and dried under vac-
uum at 50ꢀC.
Ligand: Mass spectrum: m/e = 436 Anal. calcd for
(C20H20N8S2): C, 55.04; H, 4.59; N, 25.69. Found: C,
54.87; H, 4.48; N, 25.73.
Complex-Co:
UV–Vis: 318, 337,421, 479 nm.
IR(KBr): ύ = 1425 cm-1 (C=N), 3390 cm-1 (NH),
683 cm-1 (M-N).
Dark brown powder; m.p. 201–202ꢀC; Yield 61%; UV–
Vis: 319 nm;IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1583 (s) cm−1 (C=N), 1085 (s) cm−1 (ClO4−); 1H-NMR
(d6-DMSO): δ/ppm = 3.859(s,2H,SH), 8.074–8.418 (m,
14H, benzo-H), 9.047(s,2H, HC=C), 10.128(s,2H, HC=C),
11.550(broad,2H,NH), 13.06 (broad,2H,NH). 13C-NMR
(d6-DMSO): δ/ppm = 102.859, 121.325, 125.987, 126.495,
127.037, 127.568, 128.287, 128.622, 128.945, 129.119,
129.919, 130.409, 131.020, 131.340, 131.574, 132.822,
132.354, 133.907, 134.220, 138.054, 151.266, 166.181, Mass
spectrum: m/e = 536, Anal. calcd for 738 (C26H24N10S2)
(ClO4−)2: C, 42.28; H, 3.25; N, 18.97. Found: C, 42.32; H,
3.23; N, 18.93.
Complex-Ni:
UV–Vis: 339, 390 nm.
IR(KBr): ύ = 1448 cm-1 (C=N), 3392 cm-1 (NH),
673 cm-1 (M-N).
4.1.11 | 7,15-dichloro-
1,2,4,5,9,10,12,13-octaazacyclohexadeca-
2,5,7,10,13,15-hexaene-3,11-dithiol (9B)
Complex-Zn:
UV–Vis: 295, 322 nm.
IR(KBr): ύ = 1504 cm-1 (C=N), 3397 cm-1 (NH),
685 cm-1 (M-N).
Brown powder; m.p. 198–201ꢀC; Yield 60%; UV–Vis:
305,340 nm;IR(KBr): ύ = 3250–3650 (broad) cm−1 (NH),
1589 (s) cm−1 (C=N), 1H-NMR (d6-DMSO):
δ/ppm = 3.487(s,2H,SH), 8.074–8.133 (d,J = 17.7 Hz, 4H,
HC=C), 11.688(broad,2H,NH), 13.071 (s,2H,NH). 13C-
ACKNOWLEDGMENTS
Financial support of this work by the Research Council of
the Persian Gulf University is gratefully acknowledged.

840
SABET AND MEHRANPOUR
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DATA AVAILABILITY STATEMENT
The data that support the findings of this study are avail-
able in the supplementary material of this article.
ORCID
Abdolmohammad Mehranpour https://orcid.org/0000-
0002-0074-6027
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How to cite this article: Sabet A, Mehranpour A.
Synthesis of new metal-free 1,2,4,5,9,10,12,13-
octaaza[16]annulene derivatives using the reaction
of vinamidinium salts with thiocarbohydrazide.
J Heterocyclic Chem. 2021;58:833–840. https://doi.
org/10.1002/jhet.4218