Syntheses and Crystal Structures of Methyl N-Substituted-N′-Cyanocarbamimidothioates Derived from Dimethyl N-Cyanodithioiminocarbonate

Article abstract of DOI:10.1007/s10870-019-00795-4

Abstract: Reaction of dimethyl N-cyanodithioiminocarbonate and arylamine or alkylamine compounds in the refluxing ethanol solution afforded the according methyl N-substituted-N′-cyanocarbamimidothioates 1–16 in good yields. Compounds 1–16 were characterized by proton nuclear magnetic resonance (¹H NMR) and infrared spectroscopies, of which the structures of compounds 1, 2 and 3 (Elgemeie et al. in Acta Cryst E71:104–111, 2015) were established by X-ray crystallography, showing that weak hydrogen-bonding interactions exist in compounds 1–3. Compound 1 crystallizes in the orthorhombic space group Pbca, with a = 6.997(2), b = 7.395(2), c = 36.112(11) ?, and Z = 8. The unit cell of 2 has a monoclinic P2₁/c symmetry with the cell parameters a = 5.8717(12), b = 4.6598(9), c = 37.799(9) ?, β = 91.126(6)°, and Z = 4. Compound 3 crystallizes in the orthorhombic space group Pbca, with a = 7.123(3), b = 7.374(3), c = 38.538(16) ?, and Z = 8. Graphic Abstract: A series of methyl N-subsituted-N′-cyanocarbamimidothioate compounds were efficiently synthesized via the reaction of arylamine or alkylamine compounds with dimethyl N-cyanodithioiminocarbonate. The structures of compounds 1–3 were characterized by X-Ray crystallography.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-019-00795-4

Journal of Chemical Crystallography
https://doi.org/10.1007/s10870-019-00795-4
ORIGINAL PAPER
Syntheses and Crystal Structures of Methyl N‑Substituted‑
N′‑Cyanocarbamimidothioates Derived from Dimethyl
N‑Cyanodithioiminocarbonate
Jun‑Ling Wang1 · Sen Ma1 · Pei‑Zhi Zhang1 · Ai‑Quan Jia1 · Qian‑Feng Zhang1
Received: 1 March 2019 / Accepted: 20 June 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
Reaction of dimethyl N-cyanodithioiminocarbonate and arylamine or alkylamine compounds in the refuxing ethanol solu-
tion aforded the according methyl N-substituted-N′-cyanocarbamimidothioates 1–16 in good yields. Compounds 1–16
were characterized by proton nuclear magnetic resonance (1H NMR) and infrared spectroscopies, of which the structures of
compounds 1, 2 and 3 (Elgemeie et al. in Acta Cryst E71:104–111, 2015) were established by X-ray crystallography, show-
ing that weak hydrogen-bonding interactions exist in compounds 1–3. Compound 1 crystallizes in the orthorhombic space
group Pbca, with a=6.997(2), b=7.395(2), c=36.112(11) Å, and Z=8. The unit cell of 2 has a monoclinic P21/c symmetry
with the cell parameters a=5.8717(12), b=4.6598(9), c=37.799(9) Å, β=91.126(6)°, and Z=4. Compound 3 crystallizes
in the orthorhombic space group Pbca, with a=7.123(3), b=7.374(3), c=38.538(16) Å, and Z=8.
Graphic Abstract
A series of methyl N-subsituted-N′-cyanocarbamimidothioate compounds were efciently synthesized via the reaction of
arylamine or alkylamine compounds with dimethyl N-cyanodithioiminocarbonate. The structures of compounds 1–3 were
characterized by X-Ray crystallography.
Keywords Dimethyl N-cyanodithioiminocarbonate · Methyl N-substituted-N′-cyanocarbamimidothioate · Synthesis · X-ray
structure
Introduction
* Pei-Zhi Zhang
pzzhang@ahut.edu.cn
It is well known that dimethyl N-cyanodithioiminocarbonate
is an important substrate in the syntheses of various fve-
and six-membered N-heterocycle compounds [1–5]. For
* Qian-Feng Zhang
zhangqf@ahut.edu.cn
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

Journal of Chemical Crystallography
examples, Elgemeie’s group reported that reaction of dime-
thyl N-cyanodithioiminocarbonate and cyanoacetanilides
in the dioxane solution aforded N-aryl-6-methylsulfanyl-
4-pyrimidinones and purine analogues [6]; the same group
also reported that novel mercaptopurine and thioguanine
analogues could be obtained from reactions of dimethyl
N-cyanodithioiminocarbonate with oxo- and amino-diazoles
in the refuxing ethanol [7]. These dimethyl N-cyanodithio-
iminocarbonate derivatives have broad ranges of physical,
chemical, and biological properties. Accordingly, they have
been found wide applications in pharmaceuticals, drugs,
organic and inorganic chemistry [8–17]. A typical case is
the dimethyl N-cyanodithioiminocarbonate derivative cime-
tidine, which is a histamine antagonist used to treat peptic
ulcer and hypersecretory conditions by inhibiting gastric
acid secretion [18].
2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 4-nitrosylaniline,
benzylamine, butylamine, (S)-(−)-α-methylbenzylamine,
(R)-(+)-α-methylbenzylamine, and hexadecylamine were
purchased from Alfa Aesar Ltd. and used without further
purifcation. Melting points were determined in capillaries
using an X4 digital melting-point apparatus and are uncor-
rected. The infrared spectra were recorded on a Digilab FTS-
40 spectrophotometer with use of pressed KBr pellets. NMR
spectra were recorded on a Bruker AV400-MHz Advance
NMR spectrometer at 400 MHz.
Synthesis of Dimethyl
N‑Cyanodithioiminocarbonate
Dimethyl N-cyanodithioiminocarbonate was prepared by
a modifcation of the literature method [22]. To a stirred
mixture of calcium cyanamide (36.0 g, 252 mmol) and
sodium carbonate (26.7 g, 252 mmol) in distilled water
(140 mL) was added dropwise carbon disulfde (18.7 g,
252 mmol). The solution was continuously stirred for 5 h
at 40–45 °C. The suspension was fltered and washed with
water (15 mL × 3). The combined fltrate was dropwise-
added dimethyl sulfate (47.6 g, 378 mmol) at 0 °C. After
stirring at room temperature for additional 2 h, the reaction
mixture was diluted with iso-propyl alcohol (160 mL) and
cooled to −20 °C. The resulting solid product was collected
by fltration and recrystallized from warm ethanol to aford
dimethyl N-cyanodithioiminocarbonate as colorless crystal-
line product, m.p. 48–50 °C, yield: 1.47 g (82%). 1H NMR
(400 MHz, CDCl3): δ (ppm) 2.36 (s, 6H, SCH3). 13C NMR
(100 MHz, CDCl3): δ (ppm) 194.33, 112.31, 16.15. IR (KBr
disc, cm−1): 2988, 2932, 2179 (C=N), 1581, 1486 (C=N),
1036 (C–S), 855.
On the other hand, arylamines and alkylamines are ver-
satile organic chemical materials, and their derivatives
exhibit wide applications in the felds of medicines, indus-
try and biology. In 1970, McCarty et al. tried the reactions
of dimethyl N-cyanodithioiminocarbonate and amines
RNH2 (R=H, C6H5, C6H11, C2H5) from which, the corre-
sponding N-substituted-N′-cyanocarbamimidothioate com-
pounds were isolated [1]. Worthy of comment was that syn-
anti isomerism about the C=N bond was possible in these
N-substituted-N′-cyanocarbamimidothioate compounds,
based on the observation of a shoulder on the main peak of
C≡N group around 2180 cm‒1 [1]. Moreover, treatment of
dimethyl N-cyanodithioiminocarbonate with 4-aminoanti-
pyrine gave the heterocyclic compound 4-{[(cyanoimino)
(methyl- sulfanyl)methyl]amino}-1,5-dimethyl-2-phenyl-
2,3-dihydro-1H-pyrazol-3-one [19]. It has been noted that
few structures of N-substituted-N′-cyanocarbamimidothioate
compounds: methyl N-(4-methoxyphenylmethyl)-N′-
cyanocarbamimidothioate, methyl N-[1-(phenylmethyl)-
4-piperidinyl]-N′-cyanocarbamimidothioate, and methyl
N-(4-chlorophenyl)-N′-cyanocarbamimidothioate were
crystallographically reported [20, 21]. With this in mind,
we are interested to introduce other arylamine or alkylamine
moieties into dimethyl N-cyanodithioiminocarbonate for
further preparations of series of methyl N-substituted-N′-
cyanocarbamimidothioates, the initial results are reported
in this paper.
General Synthetic Route for Methyl N‑Substituted‑N′‑
Cyanocarbamimidothioate Compounds
Arylamines or alkylamines (4.78 mmol) in ethanol (8 mL)
was dropwise added to a stirred solution of dimethyl N-cyan-
odithioiminocarbonate (0.438 g, 3.00 mmol) in ethanol
(15 mL). Then the mixture was heated at 40–45 °C for 4–5 h
and then cooled to 0 °C. The precipitate was isolated by suc-
tion fltration and washed by cool ethanol and diethyl ether
sequentially to give the corresponding products.
Methyl N-phenyl-N′-cyanocarbamimidothioate (1) White
solid, yield: 0.501 g (87.3%), 1H NMR (400 MHz, DMSO-
d6): δ (ppm) 7.38–7.17 (m, 5H, Ph), 2.64 (s, 3H, SCH3), 1.88
(s, 1H, NH). IR (KBr disc, cm−1): 3223, 2183, 2160, 1519.
Methyl N-benzyl-N′-cyanocarbamimidothioate (2) White
solid, yield: 0.509 g (82.6%), 1H NMR (400 MHz, DMSO-
d6): δ (ppm) 7.34–7.23 (m, 5H, Ph), 4.44 (s, 2H, CH2), 2.59
(s, 3H, SCH3), 1.03 (s, 1H, NH). IR (KBr disc, cm−1): 3282,
2162, 1516.
Experimental
General Procedure
All solvents were purifed by routine procedures and dis-
tilled under an atmosphere of dry nitrogen before use.
2,6-Dimethylaniline, 2,4,6-trimethylaniline, 2,6-diisopro-
pylaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline,
1 3

Journal of Chemical Crystallography
Methyl N-(4-chlorophenyl)-N′-cyanocarbamimidothioate
(3) White solid, yield: 0.545 g (82.5%), 1H NMR
(400 MHz, DMSO-d6): δ (ppm) 7.48–7.43 (m, 4H, Ph),
2.69 (s, 3H, SCH3), 2.06 (s, 1H, NH). IR (KBr disc, cm−1):
3220, 2188, 2161, 1519.
S-Methyl-N-(α-methylbenzyl)-N′-cyanocarbamimidothioate
(13) Yellow solid, yield: 0.534 (81.2%), 1H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.87–7.32 (m, 5H, Ph), 5.07 (d, J=7.1 Hz,
1H, Ph-CH), 2.61 (3H, SCH3), 2.48–2.46 (m, 1H, NH), 1.44
(d, J=7.0 Hz, 3H, CH3). IR (KBr disc, cm−1): 3272, 2170,
1542.
Methyl N-(2-chlorophenyl)-N′-cyanocarbamimidothioate
(4) White solid, yield: 0.563 g (83.1%), 1HNMR (400 MHz,
CDCl3): δ (ppm) 8.04–7.00 (m, 4H, Ph), 3.75 (s, 1H, NH),
2.19 (3H, SCH3). IR (KBr disc, cm−1): 3256, 2163, 1519.
Methyl N-(3-chlorophenyl)-N′-cyanocarbamimidothioate
(5) White solid, yield: 0.563 g (83.1%), 1H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.45–6.91 (m, 2H, Ph), 6.96 (t,
J=8.0 Hz, 2H, Ph), 5.55 (s, 1H, NH), 2.68 (s, 3H, SCH3).
IR (KBr disc, cm−1): 3223, 2162, 2183, 1520.
R - M e t h y l - N - ( α - m e t h y l b e n z y l ) - N ′ -
cyanocarbamimidothioate (14) Red solid, yield: 0.537
(81.6%), 1H NMR (400 MHz, DMSO-d6): δ (ppm) 7.79–7.26
(m, 5H, Ph) 5.08 (d, J=7.1 Hz, 1H, Ph-CH), 2.62 (s, 3H,
SCH3), 2.48–2.30 (m, 1H, NH), 1.45 (d, J= 7.0 Hz, 3H,
CH3). IR (KBr disc, cm−1): 3272, 2170, 1542.
Methyl N-(n-butyl)-N′-cyanocarbamimidothioate (15)
1
White solid, yield: 0.399 g (83.5%), H NMR (400 MHz,
Methyl N-(4-nitrophenyl)-N′-cyanocarbamimidothioate
(6) Yellow solid, yield: 0.600 g (84.7%), 1H NMR
(400 MHz, DMSO-d6): δ (ppm) 7.92–7.89 (m, 2H, Ph),
6.69–6.55 (m, 2H, Ph), 2.47 (s, 3H, SCH3), 2.02 (s, 1H,
NH). IR (KBr disc, cm−1): 3218, 2166, 1555.
DMSO-d6): δ (ppm) 3.24 (t, J=7.2 Hz, 2H, NCH2), 2.52
(s, 3H, SCH3), 2.48–1.25 (m, 5H, CH2 and NH), 0.85 (t,
J=7.3 Hz, 3H, CH3). IR (KBr disc, cm−1): 3230, 2170, 1517.
Methyl N-(n-hexadecyl)-N′-cyanocarbamimidothioate
(16) White solid, yield: 0.834 g (84.9%), 1H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.22 (t, J = 7.2 Hz, 2H,
NCH2), 2.55 (s, 3H, SCH3), 2.35–1.41 (m, 29H, (CH2)14),
0.90 (t, J = 7.3 Hz, 3H, CH3). IR (KBr disc, cm−1): 3255,
2170, 1516.
Methyl N-(4-iodophenyl)-N′-cyanocarbamimidothioate
(7) Black solid, yield: 0.757 g (79.6%), 1H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.51–7.49 (m, 1H, Ph), 7.73–7.70 (m,
1H, Ph), 7.26–7.22 (m, 1H, Ph), 6.39–6.37 (m, 1H, Ph),
3.17 (s, 1H, NH), 2.67 (s, 3H, SCH3). IR (KBr disc, cm−1):
3202, 2166, 1515.
X‑ray Crystallography
Methyl N-(2-iodophenyl)-N′-cyanocarbamimidothioate
(8) White solid, yield: 0.763 g (80.2%), 1H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.51–7.49 (m, 2H, Ph), 6.73–6.71 (m,
1H, Ph), 6.30–6.28 (m, 1H, Ph), 3.01 (s, 1H, NH), 2.48 (s,
3H, SCH3). IR (KBr disc, cm−1): 3202, 2161, 1516.
Methyl N-(3-iodophenyl)-N′-cyanocarbamimidothioate
(9) White solid, yield: 0.779 g (81.9%), 1H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.55–7.50 (m, 1H, Ph), 6.75 (s, 1H, Ph),
6.39–6.30 (m, 2H, Ph), 3.10 (s, 1H, NH), 2.54 (s, 3H, SCH3).
IR (KBr disc, cm−1): 3202, 2163, 1516.
A summary of crystallographic data and experimental
details for methyl N-phenyl-N′-cyanocarbamimidothioate
(1), methyl N-benzyl-N′-cyanocarbamimido- thioate (2) and
methyl N-(4-chlorophenyl)-N′-cyanocarbamimidothioate (3)
[19] are summarized in Table 1. Intensity data were collected
on a Bruker SMART APEX 2000 CCD difractometer using
graphite-monochromated Mo-Kα radiation (λ=0.71073 Å)
at 293(2) K. The collected frames were processed with the
software SAINT [23]. The data was corrected for absorption
using the program SADABS [24]. Structures were solved by
the direct methods and refned by full-matrix least-squares
on F2 using the SHELXTL software package [25, 26].
All non-hydrogen atoms were refned anisotropically. The
positions of all hydrogen atoms were generated geometri-
cally (Csp3 −H=0.96 Å) and Csp2 −H=0.93 Å), assigned
isotropic thermal parameters, and allowed to ride on their
respective parent carbon atoms before the fnal cycle of
least-squares refnement.
M e t h y l
N - ( 2 , 4 , 6 - t r i m e t h y l p h e n y l ) - N ′ -
cyanocarbamimidothioate (10) White solid, yield: 0.549 g
(78.5%), 1H NMR (400 MHz, CDCl3): δ (ppm) 6.81 (s, 2H,
Ph), 3.67 (s, 1H, NH), 2.27 (s, 3H, -SCH3), 2.24–2.17 (m,
9H, Ar-CH3). IR (KBr disc, cm−1): 3250, 2166, 1555.
M e t h y l
N - ( 2 , 6 - d i m e t h y l p h e n y l ) - N ′ -
cyanocarbamimidothioate (11) White solid, yield: 0.542 g
(82.4%), 1H NMR (400 MHz, CDCl3): δ (ppm) 7.52–7.08
(m, 3H, Ph), 7.19 (s, 1H, Ph), 7.00 (s, 1H, Ph), 3.68 (s, 1H,
NH), 2.59 (s, 3H, SCH3), 1.76 (s, 3H, Ar-CH3), 1.24 (s, 3H,
Ar-CH3). IR (KBr disc, cm−1): 3250, 2177, 1555.
M e t h y l
N - ( 2 , 6 - d i i s o p r o p y l p h e n y l ) - N ′ -
Results and Discussion
cyanocarbamimidothioate (12) White solid, yield: 0.580 g
(78.2%), 1H NMR (400 MHz, DMSO-d6): δ (ppm) 7.23–7.04
(m, 3H, Ph), 3.69 (s, 1H, NH), 2.57 (s, 3H, SCH3), 2.01–1.97
(m, 2H, CH) 1.23–1.21 (m, 12H, CH3). IR (KBr disc, cm−1):
3250, 2170, 1550.
As shown in Scheme 1, the key substrate dimethyl
N-cyanodithioiminocarbonate was prepared from sequen-
tial reactions of calcium carbimide, carbon disulfide and
dimethyl sulfate in the presence of sodium carbonate in a
1 3

Journal of Chemical Crystallography
Table 1 Crystallographic data and details for compounds 1, 2 and 3
two peaks (a shoulder peak on the main peak) around
2190–2160 cm−1 could be assigned to the C≡N stretching
vibration due to the possible syn-anti isomerism about
the C=N bond [1]. The peaks of 1560–1500 cm−1 may be
ascribed to the C=N stretching vibrations, which compare
well with those found in the reported cyanocarbamimi-
dothioate derivatives [1, 6, 7]. A typical IR spectrum of
compound 3 is shown in Fig. 2.
Compound
1
2
3
C10H11N3S
205.28
C9H8N3SCl
225.69
Orthorhombic
Pbca
7.123 (3)
7.374 (3)
38.538 (16)
90
P21/c
5.8717 (12)
4.6598 (9)
37.799 (9)
90
Molecular structures of compounds 1, 2 and 3 were
further confirmed by X-ray crystallography, as shown
in Figs. 3, 4, 5, respectively. Selected bond lengths and
angles are accordingly given in Tables 2, 3, 4, while the
hydrogen-bond characteristics and geometric parameters
for the three compounds are listed in Table 5. In the struc-
tures of compounds 1–3, the C(3)–N(3) bond lengths are
1.129(8), 1.151(2) and 1.155(7) Å, respectively, which
indicate their predominantly triple-bond character. The
C(2)–N(1), C(2)–N(2) and C(3)–N(2) bond lengths
being of 1.320(8), 1.339(7), and 1.345(7) Å, respec-
tively in 1, being of 1.320(2), 1.317(2) and 1.318(3) Å,
respectively in 2, and according 1.328(6), 1.314(6), and
1.312(6) Å in 3, infer their partial double bonds. More-
over, the N(3)–C(3)–N(2) bond angles are 172.3(7)o for
1, 172.6(2)o for 2, and 173.9(5)o for 3, indicative of the
typical N≡C–N=C(SCH3)–N group of methyl N-cyanocar-
boximidothioate compounds 1–3 [21]. The solid states of
compounds 1‒3 all adopt syn-isomerism about the C=N
bond, which are also found in related methyl N-substituted-
N′-cyanocarbamimidothioate compounds [20, 21].
β (°)
90
90
91.126(6)
90
1034.0 (4)
4
1.319
296 (2)
432
90
90
γ (°)
V(Å3)
1868.7 (9)
8
1.360
296 (2)
800
0.300
10,511
2024.2 (15)
8
1.481
296 (2)
928
0.544
Z
Dcalc (g cm−3
)
Temperature (K)
F(000)
μ(Mo-Kα) (mm−1
Total refn
)
0.276
6053
9207
Independent refn 2109
2344
0.0486
128
1784
0.0308
128
Rint
0.0419
119
Parameters
R1a, wR2b
(I>σ2(I))
0.0719, 0.2037 0.0447, 0.0645 0.0725, 0.1806
R1, wR2 (all data) 0.0964, 0.2195 0.0904, 0.0742 0.0780, 0.1830
GoFc
1.072 1.115 1.167
/
aR1 = Fo − Fc
Fo
ꢀꢀ ꢀ ꢀ ꢀꢀ ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀ ꢀ ꢀꢀ ꢀ
[
[
]
1∕2
/
(
2
(
)
2
bwR2 =
w
F
2
o
2
c
2
o
ꢀ
ꢀ ꢀ
− F
ꢀ ꢀ
ꢀ
ꢀ
ꢀ
w F
ꢀ
ꢀ
ꢀ
The packing views of compounds 1–3 are shown in
Figs. 3b, 4b, and 5b, respectively. Crystal packing in mole-
cules 1–3 are governed by the weak intermolecular N–H···N
hydrogen-bonding interactions (see Table 5). The separa-
tion of H(1)···N(3) in molecules 1–3 are 2.18, 2.25 and
2.16 Å, respectively. The bond angles of N(1)–H(1)···N(3)
in molecules 1–3 are 154.7º, 151.6o, and 154.5º, respec-
tively, similar to that in the related structure of methyl
N-(4-chloro- phenyl)-N′-cyanocarbamimidothioate (154º)
[20], but larger than those in 4-methoxy- phenylmethyl
or 1-(phenylmethyl)-4-piperidinyl substituted analogues
(150.8º and 144.0º) [21]. The intermolecular S···S sepa-
rations in molecules 1–3 are 3.286, 3.313, and 3.268 Å,
respectively, lower than the sum of the van der Waals radii,
which indicates a strong intermolecular interaction between
these atoms. Moreover, the intermolecular Cl···Cl separa-
tion in molecule 3 is 3.562 Å, which also contributes to the
stabilization of the crystal structure.
ꢀ
/
]
1∕2
(
)
)
2
cGoF = w ꢀFꢀ − Fc
Nobs−Nparam
ꢁ
ꢁ
o
ꢁ
ꢁ
mixed iso-propanol-water solution. The 13C NMR spec-
trum of dimethyl N-cyanodithioiminocarbonate in Fig. 1
clearly shows three signals at 16.2 ppm, 112.3 ppm and
194.3 ppm, which are ascribed to be SCH3, C=N and
C≡N groups, respectively. The target compounds 1–16
were conveniently synthesized by treatment of aryl- or
alkyl-amines with dimethyl N-cyanodithioiminocarbonate
in the heating ethanol in good yields (79.6–87.3%). In
1
the H NMR spectra of compounds 1–16, the peaks in
the range of 6.50–8.30 ppm are attributed to the protons
of the aryl moieties. The broad singlet in the range of
1.05–5.08 ppm may be attributed to the NH proton and
the signal in the range of 2.30–2.70 ppm may be assigned
to the protons of SCH3 group, which agree well to those
in the known compounds [6, 7]. In the IR spectra of com-
pounds 1–16, the broad band at around 3400–3200 cm−1
could be assigned to the N–H stretching vibration. The
In summary, we have synthesized a series of methyl
N-substituted- N′-cyanocarbamimidothioates contain-
ing arylamine or alkylamine moieties by the reaction of
dimethyl N-cyanodithioiminocarbonate with arylamines or
1 3

Journal of Chemical Crystallography
Scheme 1 Synthesis of
methyl N-substituted-N′-
cyanocarbamimidothioate 1–16
R
=
Cl
Cl
1
2
6
3
7
4
Cl
I
O2N
I
8
5
CH3
CH3
CH3
I
H3C
CH3
9
11
10
12
CH3
H
H
CH3
n-C16H33
n-C4H9
16
15
14
13
Fig. 1 13C NMR spectrum of
dimethyl N-cyanodithioimino-
carbonate
1 3

Journal of Chemical Crystallography
Fig. 2 IR spectrum of methyl N-(4-chlorophenyl)-N′-cyanocarbamimidothioate (3)
Fig. 3 a Structure of methyl N-phenyl-N′-cyanocarbamimidothioate
(1), showing the atom-labelling scheme of one molecule in the asym-
metric unit. Displacement ellipsoids are drawn at 50% probability
level and H atoms are shown as small spheres of arbitrary radii. The
crystal structure of (b), viewed along the c axis. Dashed lines indicate
N–H…N and C–H…N hydrogen bonds, and S···S short contacts
Fig. 4 a Structure of methyl N-benzyl-N′-cyanocarbamimidothioate
(2), showing the atom-labelling scheme of one molecule in the asym-
metric unit. Displacement ellipsoids are drawn at 50% probability
level and H atoms are shown as small spheres of arbitrary radii. The
crystal structure of (b), viewed along the b axis. Dashed lines indicate
N–H…N and C–H…N hydrogen bonds, and S···S short contacts
1 3

Journal of Chemical Crystallography
Table 3 Selected bond lengths (Å) and angles (°) for compound 2
S(1)–C(1)
N(1)–C(2)
N(2)–C(2)
N(3)–C(3)
C(2)–S(1)–C(1)
C(2)–N(2)–C(3)
N(2)–C(2)–S(1)
N(3)–C(3)–N(2)
1.794 (2)
1.320 (2)
1.317 (2)
1.151 (2)
105.37 (10)
120.36 (18)
118.5 (3)
172.6 (2)
S(1)–C(2)
N(1)–C(4)
N(2)–C(3)
1.742 (2)
1.467 (2)
1.318 (3)
C(2)–N(1)–C(4)
N(2)–C(2)–N(1)
N(1)–C(2)–S(1)
122.48(17)
118.68 (18)
121.94 (15)
Table 4 Selected bond lengths (Å) and angles (°) for compound 3
S(1)–C(1)
N(1)–C(2)
N(2)–C(2)
N(3)–C(3)
C(2)–S(1)–C(1)
C(2)–N(2)–C(3)
N(2)–C(2)–S(1)
N(3)–C(3)–N(2)
1.773 (5)
1.328 (6)
1.314 (6)
1.155 (7)
105.8 (2)
120.4 (4)
118.6 (4)
173.9 (5)
S(1)–C(2)
N(1)–C(4)
N(2)–C(3)
Cl(1)–C(7)
C(2)–N(1)–C(4)
N(2)–C(2)–N(1)
N(1)–C(2)–S(1)
1.738 (5)
1.424 (6)
1.312 (6)
1.739 (5)
124.8 (4)
119.7 (4)
121.9 (4)
characteristic of the C=N bonds [1]. Short halogen–hal-
ogen and sulfur–sulfur interactions have been studied,
showing the intermolecular Cl···Cl distances being of
3.562 Å in compound 3 and S···S distances being in the
range of 3.286 to 3.313 Å in compounds 1‒3, similar to
the S···S contact in methyl N-(4-methoxyphenyl- methyl)-
N′-cyanocarbamimidothioate (3.297 Å) [21]. Classical
C–H···N and N–H···N hydrogen bonds in compounds
1‒3 also contribute to the stabilization of their crystal
structures.
Fig. 5 a
Structure
of
methyl
N-(4-chlorophenyl)-N′-
cyanocarbamimidothioate (3), showing the atom-labelling scheme
of one molecule in the asymmetric unit. Displacement ellipsoids
are drawn at 50% probability level and H atoms are shown as small
spheres of arbitrary radii. The crystal structure of (b), viewed along
the a axis. Dashed lines indicate N–H…N and C–H…N hydrogen
bonds, together with S···S and Cl···Cl short contacts
Table 2 Selected bond lengths (Å) and angles (°) for compound 1
S(1)–C(1)
N(1)–C(2)
N(2)–C(2)
N(3)–C(3)
C(2)–S(1)–C(1)
C(2)–N(2)–C(3)
N(2)–C(2)–S(1)
N(3)–C(3)–N(2)
1.806 (6)
1.320 (8)
1.339 (7)
1.129 (8)
104.5 (3)
119.5 (5)
119.7 (5)
172.3 (7)
S(1)–C(2)
N(1)–C(4)
N(2)–C(3)
1.727 (6)
1.464 (7)
1.349 (7)
Supplementary Material
Crystallographic data for methyl N-phenyl-N′-
cyanocarbamimidothioate (1), methyl N-benzyl-N′-
cyanocarbamimidothioate (2), methyl N-(4-chlorophenyl)-
N′-cyanocarbamimidothioate (3) have been deposited with
the Cambridge Crystallographic Data Centre as supple-
mentary publication nos. CCDC 1899812, 1899813 and
1899814, respectively. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK [fax: (+44)1233-336-033;
e-mail: deposit@ccdc.cam.ac.uk].
C(2)–N(1)–C(4)
N(2)–C(2)–N(1)
N(1)–C(2)–S(1)
124.7 (5)
117.1 (5)
123.2 (4)
alkylamines isolated in good yields, of which three com-
pounds were further characterized by X-ray crystallogra-
phy, displaying the solid states being of syn-isomerism
1 3

Journal of Chemical Crystallography
Table 5 Hydrogen-bonding
system for compounds 1, 2
and 3
compound
D–H···A
d(D–H) (Å)
d(H···A) (Å)
d(D···A) (Å)
(DHA) (deg)
1
2
3
N(1)–H(1)···N(3)i
N(1)–H(1)···N(3)ii
N(1)–H(1)···N(3)iii
C(9)–H(9)···N(2)iv
0.86
0.86
0.86
0.93
2.180
2.251
2.16
2.980 (5)
3.035 (3)
2.962 (6)
3.452 (7)
154.7
151.6
154.5
146.3
2.64
Symmetry codes: (i) x, y−1, z; (ii) x+1, y−1, z; (iii) x, y, z+1; (iv) x, −y, z+½
13. Gara JV, Puccetti L, Fasolis G (2005) Bioorg Med Chem Lett
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Acknowledgements This project was supported by the National Natu-
ral Science Foundation of China (21372007).
14. Diop MB, Sow Y, Diop L, Plasseraud L, Cattey H (2016) Main
Group Met Chem 39:113–117
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16. Diop MB, Diop L, Oliver AG (2016) Acta Cryst E72:417–419
17. Guo W, Zhang J, Zhong L, Qian G, Zhang C (2018) Contact Der-
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Afliations
Jun‑Ling Wang1 · Sen Ma1 · Pei‑Zhi Zhang1 · Ai‑Quan Jia1 · Qian‑Feng Zhang1
1
Institute of Molecular Engineering and Applied Chemistry,
Anhui University of Technology, Ma’anshan, Anhui 243002,
People’s Republic of China
1 3