New allyldithiocarbimate salts: Synthesis, structure and antifungal activity

Article abstract of DOI:10.1016/j.molstruc.2020.128149

Fifteen new allyldithiocarbimates were prepared from different allylic bromides and various potassium dithiocarbimates, yielding (Z)-2-(methoxycarbonyl)-3-(X-nitrophenyl)allyl-(N-R-sulfonyl)dithiocarbimates (where X = 2, 3 and 4; R = phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl and 4-iodophenyl). These anions were isolated as tetraphenylphosphonium salts and characterized by HRMS, infrared, ¹H and ¹³C NMR spectroscopies. Molecular electrostatic potentials were used to evaluate intermolecular interactions present in the new substances and to explain variations observed on their melting points. Single crystal X-ray diffraction experiments confirmed the Z stereochemistry of the allyldithiocarbimate anions. C–H?O, C–H?N, C–H?S and C–H?π intermolecular interactions in the solid state were studied by X-ray diffraction and Hirshfeld surface analyses. The new compounds inhibited the mycelial growth of various fungi species responsible for severe plant diseases. The allylithiocarbimates were especially active against Botrytis cinerea, with IC₅₀ values as low as 20 μM, being more effective than the active principals of the commercial fungicides Ziram and Mancozeb.

Full text of DOI:10.1016/j.molstruc.2020.128149

Journal of Molecular Structure 1214 (2020) 128149
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
New allyldithiocarbimate salts: Synthesis, structure and antifungal
activity
a
a,
Nathalia M. Albuini-Oliveira , Mayura M.M. Rubinger *, Silvana Guilardi b,
Rafael A.C. Souza b, Javier Ellena c, Natalia Alvarez d, Eder C. Tavares e, Carlos H.C. Zacchi f,
Antonio E.C. Vidigal a, Marcelo S. Lima a, Laercio Zambolim g
ꢀ
a Departamento de Química, Universidade Federal de Viçosa, 36570-900 Viçosa, MG, Brazil
Instituto de Química, Universidade Federal de Uberlandia, 39400-902 Uberlandia, MG, Brazil
b
^
^
c
~
~
~
Instituto de Física de Sao Carlos, Universidade de Sao Paulo, 13566-590 Sao Carlos, SP, Brazil
d Facultad de Química, Universidad de la República, General Flores 2124, Montevideo, Uruguay
e
ꢀ
ꢀ
Instituto de Física e Química, Universidade Federal de Itajuba, 37500-903 Itajuba, MG, Brazil
f
~
ꢀ
Departamento de Química, Centro Federal de Educaçao Tecnologica de Minas Gerais, 30421-169 Belo Horizonte, MG, Brazil
g Departamento de Fitopatologia, Universidade Federal Viçosa, 36570-900 Viçosa, MG, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Fifteen new allyldithiocarbimates were prepared from different allylic bromides and various potassium
dithiocarbimates, yielding (Z)-2-(methoxycarbonyl)-3-(X-nitrophenyl)allyl-(N-R-sulfonyl)dithiocarbi-
mates (where X ¼ 2, 3 and 4; R ¼ phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl and 4-
iodophenyl). These anions were isolated as tetraphenylphosphonium salts and characterized by HRMS,
infrared, 1H and 13C NMR spectroscopies. Molecular electrostatic potentials were used to evaluate
intermolecular interactions present in the new substances and to explain variations observed on their
melting points. Single crystal X-ray diffraction experiments confirmed the Z stereochemistry of the
Received 6 December 2019
Received in revised form
25 February 2020
Accepted 27 March 2020
Available online 6 April 2020
Keywords:
allyldithiocarbimate anions. CeH/O, CeH/N, CeH/S and CeH/
p intermolecular interactions in the
Allyldithiocarbimates
Crystal structure
Hirshfeld surface
Antifungal activity
solid state were studied by X-ray diffraction and Hirshfeld surface analyses. The new compounds
inhibited the mycelial growth of various fungi species responsible for severe plant diseases. The allyli-
thiocarbimates were especially active against Botrytis cinerea, with IC50 values as low as 20 mM, being
more effective than the active principals of the commercial fungicides Ziram and Mancozeb.
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
Although chemically similar to the dithiocarbamates, the
dithiocarbimates (RN¼CS22ꢀ) do not have commercial applications
yet. We have recently described that dithiocarbimates can act as
nucleophiles in organic reactions producing allyldithiocarbimates
[6]. The expressive activity against Botrytis cinerea of the salt shown
in Fig. 1 [6] indicated that further studies on the allyldithiocarbi-
mates could lead to new metal-free protectant agrochemicals, as
B. cinerea is one of the top ten most scientifically and economically
important fungi, with devastating effects on crops [7].
Thus, we became very interested in understanding the chem-
istry and the structural properties of this new class of potential
agrochemicals. This work describes the syntheses and structural
studies of fifteen allyldithiocarbimate salts. These new compounds
were fully characterized by elemental analysis, HRMS, infrared, 1H
and 13C NMR spectroscopies. Single crystal X-ray diffraction, mo-
lecular electrostatic potentials and Hirshfeld surface analyses
allowed a better insight into their intermolecular interactions in the
Phytopathogenic fungi that cause significant losses pose one of
the biggest challenges in the agricultural sector. The most efficient
methods to control diseases in crops include the use of agro-
chemicals. Among such compounds, the dithiocarbamates
(R2NCS12ꢀ) are protective broad-spectrum fungicides, with rela-
tively low toxicity to non-target organisms [1,2]. There are few
reports of resistance to fungicides with multiple sites of action. For
example, zinc and manganese dithiocarbamates such as Ziram and
Mancozeb have been in the market for decades [2e4]. Di-
thiocarbamates also have industrial applications, mainly as accel-
erators of the vulcanization of natural rubber [5].
* Corresponding author.
E-mail address: mayura@ufv.br (M.M.M. Rubinger).
https://doi.org/10.1016/j.molstruc.2020.128149
0022-2860/© 2020 Elsevier B.V. All rights reserved.

2
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
nitrobenzaldehyde with methyl acrylate, catalyzed by 1,4-
diazabicyclo[2.2.2]octane (DABCO) [15]. The MBH adducts, in re-
action with lithium bromide and sulfuric acid in acetonitrile, yiel-
ded the respective allylic bromides (Scheme 1) [16e18]. All
reactions were monitored by thin-layer chromatography (TLC) with
Macherey-Nagel silica gel (0.25 mm) plates pre-coated on Polygram
polyester sheets, with fluorescent indicator (254 nm). The MBH
adducts and the allylic bromides were purified by column chro-
matography on silica gel 60 (70e230 mesh), using hexane and ethyl
acetate as eluents. The infrared spectra and melting points of the
allylic bromides and the potassium dithiocarbimates were in
accordance with the literature [9e14,16e18].
Fig. 1. A biologically active allyldithiocarbimate salt [6].
2.2. Synthesis of the allyldithiocarbimate salts
solid state and confirmed the stereochemistry of the allyldithio-
carbimates indicated by the spectroscopic data. We have also
deepened the studies on the biological activity of the allyldithio-
carbimates against phytopatogenic fungi.
The syntheses of the new compounds were performed as shown
in Scheme 2.
A solution of the appropriated allylic bromide (1 mmol) in
acetone (2 mL) was added dropwise to stirring solutions of the
potassium N-R-sulfonyldithiocarbimates (1.2 mmol) in acetone:-
water 1:1 (10 mL). The mixture (monitored by TLC) was stirred for
ca. 15 min at room temperature. Then, water (5 mL) was added and
extractions with ethyl acetate (3 ꢁ 20 mL) were performed. The
combined organic extracts were concentrated under reduced
pressure and the residue was dissolved in water (20 mL). Tetra-
phenylphosphonium chloride (1 mmol) was added to this aqueous
solution and the mixture was stirred for ca. 10 min. The yellow
solids thus formed (compounds 1A-E, 2A-E, 3A-E) were filtered out
of the mixtures, washed with distilled water and dried under
reduced pressure for one day.
2. Experimental
2.1. Methods and materials
Melting points were determined with MQAPF-302 Micro-
quimica apparatus, without correction. IR spectra were recorded on
a Varian 660 FT-IR (ATR) spectrometer. 1H NMR (300 MHz), 13C
(75 MHz) data were obtained with a VARIAN MERCURY 300 spec-
trometer, from solutions in deuterated chloroform (CDCl3) or
dimethyl sulfoxide (DMSO‑d6), with tetramethylsilane (TMS) as
internal reference. Exact mass was determined by high-resolution
electrospray ionization mass spectrometry (HR-ESI-MS) in aceto-
nitrile solutions by direct infusion method using a Bruker Daltonics
MicroTOF-QII-ESI-QQ-TOF mass spectrometer. Microanalyses for C,
H and N were obtained from a Leco TruSpec Micro CHN elemental
analyzer.
2.2.1. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(4-
nitrophenyl)allyl-(N-phenylsulfonyl)dithiocarbimate (1A)
Yield ¼ 92%; mp ¼ 156.9e158.1 ꢂC; IR (ATR, cmꢀ1) ῡmax 3066,
3018, 2956, 1725, 1625, 1591, 1522, 1490, 1440, 1383, 1340, 1271,
1261, 1230, 1203, 1133, 1110, 1085, 1068, 995, 975, 933, 844, 784,
The key intermediates were prepared as shown in Scheme 1. The
755, 723, 686, 636, 565, 523; 1H NMR (300 MHz, CDCl3):
d 3.76 (s,
benzenesulfonamide,
4-chlorobenzenesulfonamide,
4-
3H, OCH3), 4.20 (s, 2H, H1), 7.33e7.34 (m, 3H, H20, H40, H60),
7.58e7.72 (m, 11H, H30, H50, H3, Hb, Hf), 7.73e7.85 (m, 10H, H5, H9,
Hc, He), 7.87e7.98 (m, 4H, Hd), 8.10 (d, 2H, 3J6,5 ¼ 3J8,9 ¼ 9 Hz, H6,
bromobenzenesulfonamide were purchased from Sigma-Aldrich.
The 4-fluorobenzenesulfonamide and 4-iodobenzenesulfonamide
were prepared from the respective sulfonyl chlorides in reaction
with concentrated ammonia solution, as described in the literature
[8]. Then, potassium dithiocarbimates, K2(RSO2N]CS2), where
R ¼ C6H5, 4-FC6H4, 4-ClC6H4, 4-BrC6H4 and 4-IC6H4 were prepared
by reacting the appropriate sulfonamides with carbon disulfide and
potassium hydroxide (Scheme 1) as described in the literature
[9e14]. Morita-Baylis-Hillman (MBH) adducts were prepared from
the reaction of 4-nitrobenzaldehyde, 3-nitrobenzaldehyde or 2-
H8); 13C NMR (75 MHz, CDCl3):
d 33.4 (C1), 52.7 (OCH3), 117.7 (d,
1JCa-P ¼ 89 Hz, Ca), 123.9 (C6, C8), 127.8 (C20, C60), 128.2 (C30, C50),
130.7 (C40), 131.0 (d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf), 131.1 (C2), 131.9 (C5,
C9), 134.6 (d, 3JCe,Cc-P ¼ 9.8 Hz, Cc, Ce), 136.0 (d, 4JCd-P ¼ 3 Hz, Cd),
138.0 (C3), 141.7 (C4), 143.7 (C1’), 147.5 (C7), 167.8 (C¼O), 200.7
(C¼N); HR-ESI-MS, m/z: Calcd for C18H15N2O6S23ꢀ: 451.0092, found
451.0105.
Elemental
analysis:
Found
(calculated
for
C42H35N2O6PS3): C, 63.30 (63.78); H, 4.53 (4.46) and N, 3.69 (3.54)
Scheme 1. Preparation of the synthetic intermediates.

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
3
Scheme 2. Syntheses of tetraphenylphosphonium allyldithiocarbimates and the numbering used for the NMR attributions.
%.
2.2.4. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(4-
nitrophenyl)allyl-(N-4-bromophenylsulfonyl)dithiocarbimate (1D)
Yield ¼ 88%; mp ¼ 105.5e107.0 ꢂC; IR (ATR, cmꢀ1) ῡmax 3055,
2953, 1708, 1591, 1575, 1514, 1483, 1436, 1357, 1344, 1257, 1137, 1110,
1081, 1068, 1010, 997, 939, 848, 824, 778, 755, 721, 686, 604, 558,
2.2.2. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(4-
nitrophenyl)allyl-(N-4-fluorophenylsulfonyl)dithiocarbimate (1B)
Yield ¼ 95%; mp ¼ 147.7e148.9 ꢂC; IR (ATR, cmꢀ1) ῡmax 3060,
3021, 2956, 1723, 1625, 1591, 1522, 1490, 1438, 1383, 1344, 1271,
1261, 1227, 1203, 1133,1110, 1085, 1068, 995, 975, 935, 844, 781, 751,
520, 414; 1H NMR (300 MHz, CDCl3):
d 3.78 (s, 3H, OCH3), 4.21 (s,
2H, H1), 7.43 (d, 2H, 3J3’,2’ ¼ 3J5’,6’ ¼ 9 Hz, H20, H60), 7.58e7.73 (m, 9H,
H3, Hb, Hf) 7.73e7.84 (m, 10H, Hc, He, H5, H9), 7.87e7.92 (m, 6H,
725, 686, 636, 563, 526; 1H NMR (300 MHz, CDCl3):
d 3.76 (s, 3H,
3
H30, H50, Hd), 8.14 (d, 2H, J6,5
¼
3J8,9 ¼ 6 Hz, H6, H8); 13C NMR
OCH3), 4.19 (s, 2H, H1), 6.95 (t, 2H, 3J3’,2’ ¼ 3J5’,6’ ¼ 3J3’,5’,F ¼ 9 Hz, H30,
H50), 7.56e7.73 (m, 9H, H3, Hb, Hf) 7.75e7.86 (m, 10H, Hc, He, H5,
H9), 7.88e7.99 (m, 6H, H20, H60, Hd), 8.11 (d, 2H, 3J6,5 ¼ 3J8,9 ¼ 6 Hz,
(75 MHz, CDCl3):
d
33.5 (C1), 52.6 (OCH3), 117.6 (d, 1JCa-P ¼ 89.3 Hz,
Ca), 123.9 (C6, C8), 125.3 (C40), 130.1 (C20, C60), 130.9 (C30, C50), 131.0
2
3
(d, JCb,Cf-P ¼ 12.8 Hz, Cb, Cf, C5, C9), 131.7 (C2), 134.6 (d, JCe,Cc-
H6, H8); 13C NMR (75 MHz, CDCl3):
d 33.4 (C1), 52.8 (OCH3), 114.6
¼ 10.5 Hz, Cc, Ce), 136.0 (d, 4JCd-P ¼ 3 Hz, Cd), 138.2 (C3), 141.6 (C4),
P
2
(d, JC3’,C5’-F ¼ 22.5 Hz, C50, C30), 117.7 (d, 1JCa-P ¼ 90 Hz, Ca), 123.9
142.6 (C1’), 147.5 (C7), 167.8 (C¼O), 201.6 (C¼N); HR-ESI-MS, m/z:
Calcd for C18H14BrN2O6S23ꢀ: 530.9177, found 530.9190. Elemental
analysis: Found (calculated for C42H34BrN2O6PS3): C, 56.40 (58.00);
H, 4.06 (3.94) and N, 3.56 (3.22) %.
3
2
(C6, C8), 130.8 (d, JF-C2’,C6’ ¼ 9.0 Hz, C20, C60), 131.0 (d, JCb,Cf-
¼ 12.8 Hz, Cb, Cf, C5, C9), 131.8 (C2), 134.6 (d, 3JCe,Cc-P ¼ 9.8 Hz, Cc,
P
Ce), 136.0 (d, 4JCd-P ¼ 3 Hz, Cd), 138.0 (C3), 139.6 (d, 4JC1’-F ¼ 2.3 Hz,
1
C10), 141.6 (C4), 147.5 (C7), 164.1 (d, JC4’-F ¼ 252.8 Hz, C40), 167.8
(C¼O), 201.5 (C¼N); HR-ESI-MS, m/z: Calcd for C18H14FN2O6S32ꢀ
:
2.2.5. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(4-
nitrophenyl)allyl-(N-4-iodophenylsulfonyl)dithiocarbimate (1E)
Yield ¼ 95%; mp ¼ 130.0e131.8 ꢂC; IR (ATR, cmꢀ1) ῡmax 3055,
2950, 1708, 1594, 1567, 1514, 1484, 1435, 1344, 1260, 1203, 1140,
1106, 1079, 940, 852, 810, 755, 725, 685, 600, 559, 526; 1H NMR
469.0004, found 469.0010. Elemental analysis: Found (calculated
for C42H34FN2O6PS3): C, 62.72 (62.36); H, 4.31 (4.24) and N, 3.33
(3.46) %.
(300 MHz, CDCl3): d 3.78 (s, 3H, OCH3), 4.21 (s, 2H, H1), 7.43 (d, 2H,
2.2.3. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(4-
nitrophenyl)allyl-(N-4-chlorophenylsulfonyl)dithiocarbimate (1C)
Yield ¼ 90%; mp ¼ 140.0e141.2 ꢂC; IR (ATR, cmꢀ1) ῡmax 3055,
2955,1707,1589,1515,1481,1436,1357, 1344,1256, 1137, 1109,1085,
1067, 997, 934, 852, 831, 778, 751, 725, 686, 662, 619, 565, 526, 479;
3J3’,2’ ¼ 3J5’,6’ ¼ 9 Hz, H20, H60), 7.59e7.71 (m, 11H, H3, H30, H50, Hb,
Hf) 7.73e7.81 (m, 10H, Hc, He, H5, H9), 7.87e7.92 (m, 4H, Hd), 8.14
(d, 2H, 3J6,5 ¼ 3J8,9 ¼ 9 Hz, H6, H8); 13C NMR (75 MHz, CDCl3):
d 33.5
(C1), 52.9 (OCH3), 97.7 (C40), 117.7 (d, 1JCa-P ¼ 88.5 Hz, Ca), 123.9 (C6,
C8), 130.1 (C20, C60), 131.0 (d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf, C5, C9), 131.7
(C2), 134.6 (d, 3JCe,Cc-P ¼ 10.5 Hz, Cc, Ce), 136.0 (d, 4JCd-P ¼ 3 Hz, Cd),
136.9 (C30, C50), 138.2 (C3), 141.6 (C4), 143.3 (C1’), 147.5 (C7), 167.9
1H NMR (300 MHz, CDCl3):
d 3.76 (s, 3H, OCH3), 4.20 (s, 2H, H1),
7.25 (d, 2H, 3J3’,2’ ¼ 3J5’,6’ ¼ 9 Hz, H20, H60), 7.56e7.73 (m, 9H, H3, Hb,
Hf) 7.75e7.86 (m, 10H, Hc, He, H5, H9), 7.88e7.91 (m, 6H, H30, H50,
(C¼O), 201.5 (C¼N); HR-ESI-MS, m/z: Calcd for C18H14IN2O6S32ꢀ
:
3
Hd), 8.11 (d, 2H, J6,5
¼
3J8,9 ¼ 6 Hz, H6, H8); 13C NMR (75 MHz,
CDCl3):
d
33.5 (C1), 52.7 (OCH3), 117.7 (d, 1JCa-P ¼ 85.5 Hz, Ca), 123.9
576.9064, found 576.9087. Elemental analysis: Found (calculated
for C42H34IN2O6PS3): C, 54.73 (55.02); H, 3.77 (3.74) and N, 3.20
(3.06) %.
(C6, C8), 127.8 (C20, C60), 129.9 (C30, C50), 131.0 (d, 2JCb,Cf-P ¼ 12.8 Hz,
Cb, Cf, C5, C9), 131.7 (C2), 134.6 (d, 3JCe,Cc ¼ 9.8 Hz, Cc, Ce), 136.0 (d,
4JCd-P ¼ 3 Hz, Cd), 136.1 (C40), 138.1 (C3), 141.7 (C4), 142.1 (C1’), 147.5
(C7), 167.8 (C¼O), 201.5 (C¼N); HR-ESI-MS, m/z: Calcd for
2.2.6. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(3-
C
18H14ClN2O6S23ꢀ: 484.9708, found 484.9712. Elemental analysis:
nitrophenyl)allyl-(N-phenylsulfonyl)dithiocarbimate (2A)
Found (calculated for C42H34ClN2O6PS3): C, 59.55 (61.12); H, 4.12
(4.15) and N, 3.40 (3.39) %.
Yield ¼ 97%; mp ¼ 136.4e137.0 ꢂC; IR (ATR, cmꢀ1) ῡmax 3066,
ꢀ
2950, 1705, 1529, 1433, 1371, 1353, 1275, 1209, 1141, 1110, 1085, 947,

4
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
Table 1
Crystallographic data and details of diffraction experiments for compounds 1A, 2A and 3A.
Compound
1A
2A
3A
Empirical formula
Formula weight (g mol l-1
Temperature (K)
Crystal system
C42H35N2O6PS3
790.87
296(2)
Monoclinic
P21
C42H35N2O6PS3
790.87
296(2)
C42H35N2O6PS3
790.87
296(2)
Monoclinic
P2/c
)
Triclinic
Space group
P1
Unit cell dimensions
a (Å)
b (Å)
c (Å)
a
b
g
7.7510(3)
37.121(1)
26.9375(8)
90
90.131(2)
90
7750.5(4), 2
1.359
2.556
10.1543(8)
12.896(1)
14.696(1)
93.251(6)
94.626(7)
104.879(6)
1848.0(3), 2
1.421
22.0350(7)
7.4667(2)
25.0990(7)
90
111.032(2)
90
3854.4(2), 4
1.363
0.285
(ꢂ)
(ꢂ)
(ꢂ)
Volume (Å3), Z
Calculated density (g cm-3
)
m
T
(mm-1
min/Tmax
)
0.297
0.6695/0.7456
824
0.629/0.784
3312
0.916/0.969
1648
F(000)
Crystal size (mm)
q
Limiting indices
Reflections collected
Independent reflections
Goodness
0.200 ꢁ 0.120 ꢁ 0.100
2.891 to 75.053
ꢀ9,9; 0,46; ꢀ33,33
30978
0.197 ꢁ 0.135 ꢁ 0.023
3.121 to 30.507
ꢀ14,14; ꢀ14,18; ꢀ20,20
22845
0.315 ꢁ 0.218 ꢁ 0.110
0.990 to 27.498
ꢀ28,28; ꢀ9,9; ꢀ32,32
34003
range (ꢂ)
16078 [R(int) ¼ 0.0757]
11203 [R(int) ¼ 0.0548]
8845 [R(int) ¼ 0.0428]
1.088
1.058
1.017
Data/restraints/parameters
R indices [I > 2 (I)]
10782/490/1935
R ¼ 0.0790, wR ¼ 0.1445
R ¼ 0.1169, wR ¼ 0.1614
0.440 and ꢀ0.326
7286/0/487
5999/0/488
R ¼ 0.0513, wR ¼ 0.1173
R ¼ 0.0832, wR ¼ 0.1353
0.316 and ꢀ0.255
s
R ¼ 0.0629, wR ¼ 0.1445
R ¼ 0.1116, wR ¼ 0.1724
0.541 and ꢀ0.546
R indices (all data)
Largest diff. peak and hole (e A-3
)
R ¼ S (jjFoj - jFcjj)/SjFoj; wR ¼ [Sw(jF2oj - jFc2j)2/SwjFo2j2]1/2
.
931, 825, 14, 721, 689, 675, 580, 558, 526; 1H NMR (300 MHz,
2.2.8. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(3-
nitrophenyl)allyl-(N-4-chlorophenylsulfonyl)dithiocarbimate (2C)
Yield ¼ 82%; mp ¼ 116.4e117.0 ꢂC; IR (ATR, cmꢀ1) ῡmax 3060,
2949, 1712, 1629, 1583, 1525, 1479, 1435, 1351, 1264, 1205, 1141,
1106, 1082, 947, 816, 752, 720, 676, 615, 559, 526, 474; 1H NMR
DMSO‑d6):
d 3.77 (s, 3H, OCH3), 4.07 (s, 2H, H1), 7.39e7.44 (m, 3H,
H20, H40, H60), 7.72e8.06 (m, 25H, Hb, Hc, Hd, He, Hf, H3, H7, H8,
H30, H50), 8.19e8.29 (m, 1H, H9), 8.37 (s, 1H, H5); 13C NMR (75 MHz,
DMSO):
d
32.2 (C1), 52.2 (OCH3), 117.6 (d, 1JCa-P ¼ 88.5 Hz, Ca), 123.4
(C7), 124.3 (C5), 127.2 (C20, C60), 127.5 (C30, C50), 130.1 (C2, C8), 130.3
(d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf), 130.4 (C40), 134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz,
Cc, Ce), 135.2 (d, 4JCd-P ¼ 3 Hz, Cd), 135.5 (C9), 135.9 (C4), 137.3 (C3),
143.4 (C1’), 147.8 (C6), 166.8 (C¼O), 198.1 (C¼N); HR-ESI-MS, m/z:
Calcd for C18H15N2O6S23ꢀ: 451.0092, found 451.0020. Elemental
analysis: Found (calculated for C42H35N2O6PS3): C, 63.81 (63.78); H,
4.49 (4.46) and N, 3.51 (3.54) %.
(300 MHz, CDCl3): d 3.77 (s, 3H, OCH3), 4.22 (s, 2H, H1), 7.23 (d, 2H,
3J2’,3’
¼
3J5’,6’ ¼ 9 Hz, H20, H60), 7.58e7.64 (m, 10H, Hb, Hf, H3, H8),
7.72e7.79 (m, 8H, Hc, He), 7.87e7.92 (m, 6H, Hd, H30, H50),
8.08e8.16 (m, 3H, H5, H7,H9); 13C NMR (75 MHz, CDCl3):
d 33.0
1
(C1), 52.4 (OCH3), 117.4 (d, JCa-P ¼ 88.5 Hz, Ca), 123.1 (C7), 124.7
2
(C5), 127.6 (C20, C60), 129.6 (C30, C50), 130.2 (C2), 130.8 (d, JCb,Cf-
¼ 12.8 Hz, Cb, Cf), 130.9 (C8), 134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce),
P
135.8 (d, 4JCd-P ¼ 3 Hz, Cd), 135.9 (C9), 136.3 (C40), 136.5 (C4), 137.7
(C3), 142.1 (C1’), 148.0 (C6), 167.6 (C¼O), 201.4 (C¼N); HR-ESI-MS,
m/z: Calcd for
C : 484.9708, found 484.9728.
18H14ClN2O6S23ꢀ
Elemental analysis: Found (calculated for C42H34ClN2O6PS3): C,
59.63 (61.12); H, 4.21 (4.15) and N, 3.41 (3.39) %.
2.2.7. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(3-
nitrophenyl)allyl-(N-4-fluorophenylsulfonyl)dithiocarbimate (2B)
Yield ¼ 80%; mp ¼ 131.2e132.8 ꢂC; IR (ATR, cmꢀ1) ῡmax 3079,
3056, 2991, 2933, 1711, 1633, 1589, 1525, 1494, 1481, 1436, 1360,
1351, 1292, 1272, 1225, 1202, 1163, 1141, 1107, 1085, 995, 944, 835,
814, 782, 756, 721, 685, 649, 555, 542, 521; 1H NMR (300 MHz,
2.2.9. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(3-
nitrophenyl)allyl-(N-4-bromophenylsulfonyl)dithiocarbimate (2D)
Yield ¼ 86%; mp ¼ 83.6e85.2 ꢂC; IR (ATR, cmꢀ1) ῡmax 3085,
3055, 2950, 2929, 1712, 1629, 1572, 1481, 1436, 1351, 1268, 1207,
1141, 1106, 1081, 995, 948, 816, 781, 720, 685, 601, 559, 522, 412; 1H
CDCl3):
d 3.77 (s, 3H, OCH3), 4.21 (s, 2H, H1), 6.94 (t, 2H,
3J3’,2’
¼
3J5’,6’
¼
3J3’,5’,F ¼ 9 Hz, H30, H50), 7.57e7.65 (m, 10H, Hb, Hf,
H3, H8), 7.73e7.79 (m, 8H, Hc, He), 7.87e7.98 (m, 6H, Hd, H20, H60),
NMR (300 MHz, CDCl3): d 3.77 (s, 3H, OCH3), 4.20 (s, 2H, H1), 7.39
8.10 (pseudo-t, 2H, H7, H9), 8.16 (s, 1H, H5); 13C NMR (75 MHz,
(d, 2H, 3J2’,3’ ¼ 3J5’,6’ ¼ 9 Hz, H20, H60), 7.55e7.65 (m, 10H, Hb, Hf, H3,
H8), 7.72e7.82 (m, 10H, Hc, He, H30, H50), 7.86e7.91 (m, 4H, Hd),
8.07 (pseudo-t, 2H, H7, H9), 8.17 (s, 1H, H5); 13C NMR (75 MHz,
2
CDCl3):
d
33.0 (C1), 52.4 (OCH3), 114.4 (d, JC3’,C5’-F ¼ 21.8 Hz,
1
C30,C50), 117.4 (d, JCa-P ¼ 89 Hz, Ca), 123.1 (C7), 124.7 (C5), 130.2
(C2), 130.5 (d, 3JC2’,C6’-F ¼ 9 Hz, C20,C60), 130.8 (d, 2JCb,Cf-P ¼ 12.8 Hz,
Cb, Cf), 130.9 (C8), 134.3 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce), 135.8 (d, 4JCd-
CDCl3):
d
32.0 (C1), 52.4 (OCH3), 117.4 (d, 1JCa-P ¼ 89 Hz, Ca), 123.1
(C7), 124.7 (C5), 125.0 (C40), 129.7 (C20, C60), 130.1 (C2), 130.7 (C8,
2
3
¼ 3, Cd), 135.9 (C9), 136.5 (C4), 137.8 (C3), 139.4 (d, 4JC1’-F ¼ 3 Hz,
C30, C50), 130.8 (d, JCb,Cf-P ¼ 12 Hz, Cb, Cf), 134.4 (d, JCc,Ce-
P
C10), 148.0 (C6), 163.8 (d, 1JC4’-F ¼ 248 Hz, C40), 167.6 (C¼O), 201.2
(C¼N); HR-ESI-MS, m/z: Calcd for C18H14FN2O6S23ꢀ: 469.0004;
found 469.0019. Elemental analysis: Found (calculated for
¼ 10.5 Hz, Cc, Ce),135.8 (d, 4JCd-P ¼ 3 Hz, Cd),135.8 (C9),136.4 (C4),
P
137.8 (C3), 142.4 (C1’), 148.0 (C6), 167.5 (C¼O), 201.6 (C¼N); HR-ESI-
MS, m/z: Calcd for C18H14BrN2O6S23ꢀ: 530.9177, found 530.9124.
Elemental analysis: Found (calculated for C42H34BrN2O6PS3): C,
55.65 (58.00); H, 4.04 (3.94) and N, 3.28 (3.22) %.
C
42H34FN2O6PS3): C, 60.81 (62.36); H, 4.23 (4.24) and N, 3.53 (3.46)
%.

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
5
2.2.10. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(3-
nitrophenyl)allyl-(N-4-iodophenylsulfonyl)dithiocarbimate (2E)
Yield ¼ 63%; mp ¼ 76.4e78.1 ꢂC; IR (ATR, cmꢀ1) ῡmax 3079, 2991,
2939, 1712, 1628, 1566, 1529, 1480, 1435, 1364, 1348, 1267, 1207,
1139, 1107, 1081, 996, 947, 814, 782, 755, 725, 686, 597, 557, 523; 1H
(OCH3), 117.4 (d, 1JCa-P ¼ 89 Hz, Ca), 124.6 (C6), 127.6 (C20, C60), 129.2
(C7), 129.5 (C30, C50), 129.8 (C4), 130.7 (d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf),
130.8 (C2), 132.0 (C9), 134.3 (C8), 134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce),
135.8 (d, 4JCd-P ¼ 3 Hz, Cd), 136.3 (C40), 137.3 (C3), 142.1 (C1’), 147.3
(C5), 167.3 (C¼O), 201.5 (C¼N); HR-ESI-MS, m/z: Calcd for
NMR (300 MHz, CDCl3):
d
3.77 (s, 3H, OCH3), 4.21 (s, 2H, H1),
C
18H14ClN2O6S23ꢀ: 484.9708, found 484.9747. Elemental analysis:
7.58e7.68 (m, 14H, Hb, Hf, H3, H8, H20,H30, H50, H60), 7.72e7.79 (m,
8H, Hc, He), 7.87e7.91 (m, 4H, Hd), 8.09 (d, 2H, 3J5,6 ¼ 3J6,7 ¼ 6 Hz,
Found (calculated for C42H34ClN2O6PS3): C, 57.62 (61.12); H, 4.14
(4.15) and N, 3.54 (3.39) %.
H7, H9), 8.15 (s, 1H, H5); 13C NMR (75 MHz, CDCl3):
d
33.0 (C1), 52.4
1
(OCH3), 97.3 (C40), 117.4 (d, JCa-P ¼ 88.5 Hz, Ca), 123.1 (C7), 124.7
2.2.14. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(2-
nitrophenyl)allyl-(N-4-bromophenylsulfonyl)dithiocarbimate (3D)
Yield ¼ 96%; mp ¼ 60.4e62.0 ꢂC; IR (ATR, cmꢀ1) ῡmax 3068,
2989,1715,1649,1605,1571,1518,1484, 1471,1435,1367,1343,1267,
1205, 1141, 1106, 1080, 1010, 948, 862, 817, 750, 738, 720, 689, 674,
2
(C5), 129.8 (C20, C60), 130.2 (C2), 130.7 (C8), 130.8 (d, JCb,Cf-
¼ 12.8 Hz, Cb, Cf), 134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce), 135.8 (d, 4JCd-
P
¼ 3 Hz, Cd), 135.9 (C9), 136.4 (C4), 136.6 (C30, C50), 137.8 (C3), 143.2
P
(C1’), 148.0 (C6), 167.6 (C¼O), 201.5 (C¼N); HR-ESI-MS, m/z: Calcd
for C18H14IN2O6S23ꢀ: 576.9064, found 576.8990. Elemental analysis:
Found (calculated for C42H34IN2O6PS3): C, 53.87 (55.02); H, 3.80
(3.74) and N, 2.99 (3.06) %.
604, 558, 525, 458, 415; 1H NMR (300 MHz, CDCl3):
d 3.73 (s, 3H,
3
OCH3), 3.99 (s, 2H, H1), 7.37 (d, 2H, J3’,2’
¼
3J5’,6’ ¼ 9 Hz, H20, H60),
7.42e7.51 (m, 1 H, H7), 7.57e7.64 (m, 10H, Hb, Hf, H8, H9),
7.69e7.81 (m, 10H, Hc, He, H30, H50), 7.85e7.93 (m, 5H, Hd, H3), 8.06
2.2.11. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(2-
nitrophenyl)allyl-(N-phenylsulfonyl)dithiocarbimate (3A)
(d, 1H, 3J6,7 ¼ 9 Hz, H6); 13C NMR (75 MHz, CDCl3):
d 33.1 (C1), 52.3
1
(OCH3), 117.4 (d, JCa-P ¼ 89 Hz, Ca), 124.6 (C6), 124.9 (C40), 129.2
Yield ¼ 90%; mp ¼ 53.4e54.9 ꢂC; IR (ATR, cmꢀ1) ῡmax 3060,
(C7), 129.7 (C20, C60), 129.7 (C4), 130.6 (C2), 130.7 (d, JCb,Cf-
2
2956,1712,1520,1366, 1276,1138,1107,1079, 943, 825, 564, 523; 1H
¼ 13.5 Hz, Cb, Cf), 131.9 (C9), 134.3 (C30, C50), 134.4 (d, JCc,Ce-
3
P
NMR (300 MHz, CDCl3):
d
3.72 (s, 3H, OCH3), 4.00 (s, 2H, H1),
¼ 10.5 Hz, Cc, Ce), 135.8 (d, 4JCd-P ¼ 3 Hz, Cd),135.8 (C8), 137.4 (C3),
P
7.26e7.28 (m, 3H, H20, H40, H60), 7.44 (pseudo-t, 1H, H7), 7.57e7.64
(m, 8H, Hb, Hf), 7.70e7.75 (m, 10H, Hc, He, H8, H9), 7.86e7.90 (m,
142.5 (C1’), 147.3 (C5), 167.3 (C¼O), 201.6 (C¼N); HR-ESI-MS, m/z:
Calcd for C18H14BrN2O6S23ꢀ: 530.9177, found 530.9147. Elemental
analysis: Found (calculated for C42H34BrN2O6PS3): C, 54.97 (58.00);
H, 3.86 (3.94) and N, 3.51 (3.22) %.
7H, Hd, H3, H30, H50), 8.04 (d, 1H, J6,7 ¼ 9 Hz, H6); 13C NMR
3
(75 MHz, CDCl3):
d
33.1 (C1), 52.2 (OCH3), 117.4 (d, 1JCa-P ¼ 89 Hz,
Ca), 124.5 (C6), 127.5 (C20, C60), 127.8 (C30, C50), 129.2 (C7), 129.9
(C4), 130.3 (C40), 130.7 (C2), 130.7 (d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf), 132.1
(C9), 134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce, C8), 135.8 (d, 4JCd-P ¼ 3 Hz,
Cd), 137.1 (C3), 143.6 (C1’), 147.3 (C5),167.3 (C¼O), 200.6 (C¼N); HR-
ESI-MS, m/z: Calcd for C18H15N2O6S23ꢀ 451.0092, found 450.9994.
Elemental analysis: Found (calculated for C42H35N2O6PS3): C, 63.96
(63.78); H, 4.60 (4.46) and N, 3.50 (3.54) %.
2.2.15. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(2-
nitrophenyl)allyl-(N-4-iodophenylsulfonyl)dithiocarbimate (3E)
Yield ¼ 97%; mp ¼ 62.6e64.2 ꢂC; IR (ATR, cmꢀ1) ῡmax 3066,
3048, 1713, 1650, 1604, 1567, 1518, 1481, 1436, 1367, 1342, 1278,
1264,1206,1170,1142,1106,1079,1004, 947, 862, 811, 782, 752, 720,
690, 600, 558, 526, 456; 1H NMR (300 MHz, CDCl3):
d 3.73 (s, 3H,
OCH3), 3.99 (s, 2H, H1), 7.43e7.48 (m, 1H, H7), 7.57e7.67 (m, 14H,
2.2.12. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(2-
nitrophenyl)allyl-(N-4-fluorophenylsulfonyl)dithiocarbimate (3B)
Yield ¼ 93%; mp ¼ 62.0e63.6 ꢂC; IR (ATR, cmꢀ1) ῡmax 3056,
2948, 1711, 1587, 1518, 1487, 1436, 1341, 1272, 1216, 1138, 1106, 1081,
996, 940, 833, 790, 751, 720, 686, 558, 526, 456; 1H NMR (300 MHz,
Hb, Hf, H8, H9, H20, H30, H50, H60), 7.70e7.81 (m, 8H, Hc, He),
3
7.87e7.91 (m, 5H, Hd, H3), 8.06 (d, 1H, J6,7 ¼ 9 Hz, H6); 13C NMR
(75 MHz, CDCl3):
d
33.1 (C1), 52.3 (OCH3), 97.3 (C40), 117.4 (d, 1JCa-
¼ 89 Hz, Ca), 124.6 (C6), 129.3 (C7), 129.7 (C20, C60), 129.7 (C4),
P
130.7 (d, 2JCb,Cf-P ¼ 12,8 Hz, Cb, Cf), 130.8 (C2), 131.9 (C9), 134.3 (C8),
134.4 (d, 3JCc,Ce-P ¼ 10.5 Hz, Cc, Ce), 135.8 (d, 4JCd-P ¼ 3 Hz, Cd), 136.6
(C30, C50), 137.4 (C3), 143.2 (C1’), 147.3 (C5), 167.2 (C¼O), 201.5
(C¼N); HR-ESI-MS, m/z: Calcd for C18H14IN2O6S23ꢀ: 576.9064, found
CDCl3):
d 3.73 (s, 3H, OCH3), 4.00 (s, 2H, H1), 6.92 (t, 2H,
3J3’,2’
¼
3J5’,6’
¼
3J3’,5’,F ¼ 9 Hz, H30, H50), 7.43e7.49 (m, 1H, H7),
7.58e7.65 (m, 8H, Hb, Hf), 7.68e7.79 (m, 10H, Hc, He, H8, H9),
7.87e7.94 (m, 7H, Hd, H3, H20, H60), 8.06 (d, 1H, 3J6,7 ¼ 9 Hz, H6); 13
C
576.9019.
Elemental
analysis:
Found
(calculated
for
2
NMR (75 MHz, CDCl3):
d
33.1 (C1), 52.2 (OCH3), 114.3 (d, JC3’,C5’-
C42H34IN2O6PS3): C, 53.27 (55.02); H, 3.77 (3.74) and N, 3.03 (3.06)
¼ 22.5 Hz, C30,C50), 117.4 (d, 1JCa-P ¼ 89 Hz, Ca), 124.5 (C6), 129.2
%.
F
(C7), 129.8 (C4), 130.5 (d, 3JC2’,C6’-F ¼ 9 Hz, C20,C60), 130.7 (C2), 130.8
(d, 2JCb,Cf-P ¼ 12.8 Hz, Cb, Cf), 132.0 (C9), 134.3 (C8), 134.4 (d, 3JCc,Ce-
2.3. X-ray crystallography
¼ 10.5 Hz, Cc, Ce), 135.8 (d, 4JCd-P ¼ 3 Hz, Cd), 137.2 (C3), 139.6 (d,
P
4JC1’-F ¼ 3 Hz, C10), 147.4 (C5), 163.8 (d, 1JC4’-F ¼ 247.5 Hz, C40), 167.3
Slow evaporation of ethanol/water solution (1:1 v/v) of com-
pound 1A, or acetone/water solutions (1:1 v/v) of 2A and 3A at
298 K yielded yellow crystals. The diffraction pattern of 1A was
collected at room temperature on a Bruker APEXII-CCD diffrac-
(C¼O), 201.1 (C¼N); HR-ESI-MS, m/z: Calcd for C18H14FN2O6S32ꢀ
:
469.0004, found 469.0037. Elemental analysis: Found (calculated
for C42H34FN2O6PS3): C, 61.25 (62.36); H, 4.38 (4.24) and N, 3.50
(3.46) %.
tometer using Cu-K
a
radiation (
l
¼ 1.54178 Å) monochromated by
graphite. The software APEX2 [19] was employed to operate the
diffractometer and to plan the data collection strategy. The data
were integrated using the program SAINT [20]. TWINABS-2012/1
[21] was used for absorption correction. Using Olex2 [22], the
structure was solved with the Olex2.solve structure solution pro-
gram [23] using Charge Flipping and refined with the SHELXL-2018
[24]. Compound 1A was refined as a merohedral twin with twin
matrix (ꢀ1, 0, 0; 0, ꢀ1, 0; 0, 0, 1), with a refined BASF value of
0.40899. All hydrogen atoms were stereochemically positioned and
refined with the riding model. Some of the aromatic carbon atoms
of the tetraphenylphosphonium cation of 1A presented
2.2.13. Tetraphenylphosphonium (Z)-2-(methoxycarbonyl)-3-(2-
nitrophenyl)allyl-(N-4-chlorophenylsulfonyl)dithiocarbimate (3C)
Yield ¼ 97%; mp ¼ 57.4e58.9 ꢂC; IR (ATR, cmꢀ1) ῡmax 3060,
2950, 1712, 1637, 1610, 1575, 1518, 1483, 1470, 1436, 1369, 1340,
1265, 1207, 1137, 1107, 1081, 1009, 996, 948, 859, 816, 790, 752, 721,
690, 673, 605, 559, 524, 413; 1H NMR (300 MHz, CDCl3):
d 3.74 (s,
3
3H, OCH3), 4.00 (s, 2H, H1), 7.21 (d, 2H, J3’,2’
¼
3J5’,6’ ¼ 9 Hz, H20,
H60), 7.43e7.50 (m, 1H, H7), 7.57e7.68 (m, 10H, Hb, Hf, H8, H9),
7.72e7.78 (m, 8H, Hc, He), 7.82e7.91 (m, 7H, Hd, H3, H30, H50), 8.06
(d, 1H, 3J6,7 ¼ 9 Hz, H6); 13C NMR (75 MHz, CDCl3):
d 33.1 (C1), 52.3

6
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
Fig. 2. ORTEP representation of the four cations and four anions of the asymmetric unit of 1A.
uncharacteristically large and irregular thermal parameters
compared to those of 2A and 3A, and were constrained using SIMU
in SHELXL-2018 [24].
The X-ray intensity data for compounds 2A and 3A single crys-
tals were collected on a Bruker AXS Proteum X8 diffractometer
scales. The molecular electrostatic potentials on Hirshfeld surfaces
of the anion were mapped using a fixed scale of ꢀ0.04 to 0.03 au for
1A, 2A and 3A. All hydrogen bond lengths were automatically
modified to typical standard neutron values (CeH of 1.083 Å).
using Mo-K
a
radiation (
l
¼ 0.71073 Å) monochromated by
2.5. Biological assays
graphite. The software APEX2 [19] was employed to operate the
diffractometer and to plan the data collection strategy. The data
were integrated using the program SAINT [20], and corrected for
absorption effects using multi-scan and scaled with the program
SADABS [25]. The structures were solved by direct methods and
refined by full-matrix least-square methods against F2, with
SHELXL-2018 [24]. All hydrogen atoms were stereochemically
positioned and refined with the riding model. In the compound 3A,
the O6 atom of the anion was found to have uncharacteristically
large and irregular thermal parameters compared to other oxygen
atoms of the structure and were constrained using SIMU in
SHELXL-2018 [24].
The biological activity of the allyldithiocarbimate salts was
evaluated in vitro through the Poisoned Food method [29]. For the
initial screening with Botrytis cinerea, Rhizoctonia solani, Sclerotinia
sclerotiorum, Alternaria solani, Colletotrichum acutatum and Fusa-
rium oxysporum, the potato dextrose agar culture medium (PDA,
2.34 g) was mixed with dimethyl sulfoxide (DMSO, 0,60 mL), pol-
yoxyethylene (20) sorbitan monooleate (Tween 80, 0,60 mL), the
compound 1C (7.92 mg, for a final concentration of 160 mM) and
distilled water for a final volume of 60,0 mL. This mixture was
distributed in four Petri dishes per treatment. The control (Four
repetitions for each fungus) was prepared with PDA, DMSO, Tween
80 and water only. Each dish was inoculated with one disc of
mycelia (7.4 mm). The dishes were kept under controlled temper-
ature until the fungus colony had taken 90% of the dish area on the
control dishes: three days at 20 ꢂC for B. cinerea, R. solani and
S. slerotiorum, four days at 25 ꢂC for A. solani or seven days at 25 ꢂC
for C. acutatum and F. oxysporum. The mycelial growth was calcu-
lated from the average of the diameters measured in six directions
in each Petri dish, in the last day of each experiment. The inhibition
percentage (I%) of the mycelial growth was calculated with the
equation: I% ¼ 100 x (C e S)/C, where C is the average growth of the
control and S is the average growth of the fungus in the presence of
the substance in test. As B. cinerea showed the highest sensitivity to
the allyldithiocarbimate salt 1C, the test was repeated with this
fungus including treatments with the substances 1A-E, 2A-E and
Structural representations were drawn using ORTEP-3 [26] and
MERCURY [27]. The program WinGX [26] was used to prepare
materials for publication. Table 1 summarizes the data collection
and experimental details for the salts 1A, 2A and 3A.
2.4. Hirshfeld surface (HS)
The Hirshfeld 3D surfaces were generated with the Crystal Ex-
plorer 2.1 program [28]. The strength of the interactions were
calculated by Hirshfeld dnorm (normalized contact distance) sur-
face. Moreover, the 2D fingerprint plots were calculated in order to
analyze the relative contribution of different intermolecular in-
teractions of compounds 1A, 2A and 3A. The 3D dnorm surface was
mapped using a fixed color scale of ꢀ0.1000 (red) to 1.0000 (blue).
Although the compound 1A crystal is twin and present four cations
and four anions in the asymmetric unit, dnorm was generated for
only one set of cation and anion. The 2D fingerprint plots were
displayed on the graph axes (0.4e3.0 Å), using de and di distance
3A-E at various concentrations (5, 10, 20, 40, 120, and 160 mM).
From these data, dose-response curves were plotted, and the con-
centration required to inhibit the mycelial growth of B. cinerea by
50% (IC50) was determined for each substance.

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
7
Fig. 3. ORTEP views of the four anions of the asymmetric unit of 1A with atom-numbering scheme and displacement ellipsoids drawn with 30% probability level.
Fig. 4. ORTEP views of the anions of 2A and 3A with atom-numbering scheme and displacement ellipsoids drawn with 30% probability level.

8
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
the [M]- peaks, thus confirming the allyldithiocarbimate anions
formulae. The molecular peak of tetraphenylphosphonium cation
was observed in the positive mode at m/z 339.1353.
Table 2
Selected geometrical parameters for compounds 1A, 2A and 3A.
Compound
1Aa
2A
3A
The IR spectra of compounds 1A-E, 2A-E and 3A-E showed the
asymmetric and symmetric stretching bands of the NO2 group at
1514e1529 and 1340ꢀ1353 cmꢀ1, respectively, as well as the
Bond length (Å)
C1eC2
C2eC3
C3eC4
C2eC11
C11eO4
C11eO3
C12eO4
C1eS1
C10eS1
C10eN2
C10eS2
N2eS3
S3eC10
1.50(2)
1.31(2)
1.50(2)
1.50(2)
1.33(2)
1.19(2)
1.48(2)
1.82(1)
1.78(1)
1.32(2)
1.68(1)
1.62(1)
1.75(1)
1.498(3)
1.342(4)
1.462(4)
1.498(4)
1.332(3)
1.201(3)
1.455(3)
1.813(3)
1.772(3)
1.318(4)
1.675(3)
1.617(2)
1.768(3)
1.503(3)
1.334(3)
1.477(3)
1.489(3)
1.329(3)
1.196(3)
1.445(3)
1.830(2)
1.776(2)
1.316(3)
1.680(3)
1.623(2)
1.772(3)
intense band in 1705e1725 cmꢀ1, attributed to
nC¼O of the ester
group. The most important bands to characterize the dithiocarbi-
mate moiety were identified at 1340ꢀ1384 cmꢀ1
(
n
C¼N) and
933ꢀ948 cmꢀ1
(nasymCS2). In the spectra of the parent potassium N-
R-sulfonyldithiocarbimates, these bands are observed at
1249e1255 and 962ꢀ970 cmꢀ1, respectively. These data indicated
an increase in the C¼N double bond character with the trans-
formation of the free dianion (dithiocarbimate) into the monoanion
(allyldithiocarbimate), with a less conjugated NCS2 system. The
nasymSO2 and nsymSO2 bands were observed in the expected ranges
of 1256e1276 and 1133ꢀ1142 cmꢀ1 in the spectra of 1A-E, 2A-E and
3A-E.
Torsion angles
N2eS3eC10eC20
N2eS3eC10eC60
S1eC1eC2eC3
S1eC1eC2eC11
103.49
ꢀ75.49
116.98
ꢀ73.77
129.3(2)
ꢀ54.1(2)
ꢀ91.5(3)
93.1(3)
109.5(2)
ꢀ71.1(2)
ꢀ56.5(3)
132.0(2)
In their 1H NMR spectra, the tetraphenylphosphonium cation
signals are observed as multiplets at similar chemical shifts, at
a
Values of the average bond lengths of the four molecules of the asymmetric unit
about
d 7.6e7.7 (Hb and Hf), 7.7e7.8 (Hc and He) and 7.9 (Hd). In
(1Aa-d) and torsion angles of the anion of 1Aa.
most spectra, these signals overlap with those of other aromatic
hydrogens of the anions. The integration curves are consistent with
the number of hydrogens present in the structures of 1A-E, 2A-E
and 3A-E and confirmed the 1:1 proportion between the cation and
3. Results and discussion
3.1. Syntheses
the anions. The singlets at
d 3.72e3.78 and 3.99e4.22 confirmed
Scheme 1 shows the preparation of the key starting materials for
the synthetic route. The five dihydrated potassium N-R-sulfo-
nyldithiocarbimates with the general formula K2(R-SO2N¼CS2)$
2H2O, where R ¼ C6H5, 4-FC6H4, 4-ClC6H4, 4-BrC6H4 and 4-IC6H4,
are yellow salts, soluble in water and insoluble in most organic
solvents. Their infrared spectra were in accordance with the re-
ported data [9e14]. Three Morita-Baylis-Hillman adducts were
prepared by the reactions of p-, m- and o-nitrobenzaldehydes with
methyl acrylate in the presence of DABCO as catalyst (Scheme 1)
[15]. These compounds were converted into allylic bromides in
reaction with lithium bromide and sulfuric acid in acetonitrile
(Scheme 1) [16]. After purification by column chromatography, the
infrared and NMR spectroscopic data of the Morita-Baylis-Hillman
adducts [15] and the allylic bromides reproduced the literature
values [16e18].
Scheme 2 shows the syntheses of the new compounds 1A-E, 2A-
E and 3A-E. As the N-R-sulfonyldithiocarbimates are dianionic
species, a slight excess of these nucleophiles and the slow addition
of the allylic bromides to the reacting system avoided a second
substitution reaction at the free sulfur atom of the allyldithio-
carbimate monoanion thus formed. These substitution reactions
are quite fast (less than 15 minutes). The allyldithiocarbimate po-
tassium salts are very soluble in water and of difficult purification.
Thus, the new allyldithiocarbimates were isolated in high yields
(89% average) as tetraphenylphosphonium salts (Scheme 2).
Compounds 1A-E, 2A-E and 3A-E are yellow solids soluble in
chloroform, dimethylformamide, dimethyl sulfoxide, acetonitrile,
dichloromethane, acetone, ethyl acetate and methanol, and are
practically insoluble in water, hexane and diethyl ether. The melting
point ranges of compounds 1A-E (with the para-nitro group) are
higher than the values observed for the corresponding analogues
2A-E (with the meta-nitro group). Although solids at room tem-
perature, the 3A-E series (with the ortho-nitro group) presented the
lowest melting points, in the range of 53e64 ꢂC, characteristic of
ionic liquids.
Table 3
Hydrogen-bond geometry (Å, ꢂ) for compounds 1Aa, 2A and 3A.
DonoreH/Acceptor
d(DeH)
d(H/A)
d(D/A)
<(DHA)
Compound 1Aa
C20aeH20a/O6a
C1aeH20A/N2a
C3aeH3a/O4a
0.93
0.97
0.93
0.93
0.93
0.93
0.93
0.96
0.93
0.93
0.93
0.93
0.93
0.93
2.49
2.44
2.28
2.94
2.67
2.35
2.67
2.70
2.93
2.84
2.71
2.71
2.90
2.74
2.85(2)
2.94(2)
2.67(2)
3.81(1)
3.60(2)
3.17(2)
3.29(2)
3.54(2)
3.53(2)
3.54(2)
3.32(2)
3.31(2)
3.58(2)
3.66(2)
103
111
105
155
175
147
125
147
123
134
124
123
131
173
C23aeH23a/S3a
C23aeH23a/O5a
C50aeH50a/O6ai
C50ceH50c/O4ai
C12deH12I/O3aii
C14beH14b/S2aiii
C17aeH17a/S2div
C26beH26b/O3aiii
C27beH27b/O3aiii
C33deH33d/S2av
C22aeH22a/
Compound 2A
C20eH20/O6
C3eH3/O3
C9eH9/S1
p
1vi
0.93
0.93
0.93
0.93
0.97
0.93
0.93
0.93
0.93
0.93
0.93
0.93
0.93
2.51
2.35
2.76
2.46
2.81
2.41
2.40
2.60
2.37
2.86
2.77
2.94
2.76
2.8963(3)
2.7538(2)
3.6051(3)
3.1231(3)
3.5801(3)
3.2517(3)
3.0968(3)
3.3416(3)
3.2909(3)
3.4753(3)
3.5610(3)
3.6305(3)
3.5437(3)
105
106
151
129
137
151
132
137
170
125
144
132
143
C17eH17/O2
C1eH1A/p2
C40eH40/O3vii
C8eH8/O6viii
C18eH18/O5iii
C30eH30/O1viii
C35eH35/S2i
C27eH27/
C29eH29/
C34eH34/
p
p
p
4ix
3x
3xi
Compound 3A
C20eH20/O6
C1eH1B/N2
C3eH3/O4
C33eH33/O5
C28eH28/O3xii
C29eH29/O6xiii
C36eH36/O2xiv
0.93
0.97
0.93
0.93
0.93
0.93
0.93
2.59
2.42
2.34
2.74
2.70
2.60
2.58
2.9551(1)
2.9530(1)
2.7182(1)
3.148(4)
3.340(3)
3.3457(1)
3.2307(1)
104
115
104
107
127
138
128
Symmetry codes: (i) 1þx,y,z; (ii) 1þx,y,1þz; (iii) x,y,1þz; (iv) 2-x,-1/2þy,1-z; (v)
-x,1/2þy,1-z; (vi) ꢀ1þx,y,z; (vii) 1-x,1-y,1-z; (viii) 1-x,2-y,2-z; (ix) 1-x,1-y,-z; (x)
3.2. Spectroscopic characterization
-x,-y,-z; (xi) 1-x,1-y,1-z; (xii) 1-x,-y,1-z; (xiii) -x,1-y,-z; (xiv) 1-x,y, 1/2-z.
p1 is ring
C31d to C36d,
p2 is ring C13 to C18,
p p4 is ring C19 to C24.
3 is ring C10 to C60 and
a
HR-ESI-MS in the anionic mode showed the expected values for
Interactions related to 1Aa.

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
9
Fig. 5. Packing diagram of 1A, viewed down the c axis. Dashed lines indicate CeH/O and CeH/S intermolecular interactions.
the presence of the methoxy group and the methylene hydrogens
2A and 3A contain only one anion and one cation.
(H1), respectively, in the allyldithiocarbimates structures.
The four anions present in compound 1A crystal (1Aa, 1Ab, 1Ac,
1Ad) are shown separately in Fig. 3, for clarity. In this picture, it is
possible to see that the anions are present in different conforma-
tions. The X-ray diffraction data of compounds 1A, 2A and 3A
confirmed the (Z)-stereochemistry for the allyldithiocarbimate
anions (Figs. 3 and 4).
The methoxy and the methylene (C1) carbon atoms signals are
observed in their 13C NMR spectra, respectively, at
d
52.2e52.9 and
d
32.0e33.5. The ester carbonyl signal appears at the expected
range of ca.
d
167. It is interesting to note that the C¼N signal (ca.
d
200) is observed in higher field when compared to the corre-
sponding signal observed in the spectra of the parent potassium N-
R-sulfonyldithiocarbimates (ca. 225) [29]. Thus, the NMR and the
Table 2 presents selected bond lengths and torsion angles for the
anions of 1A (average values of the four anions), 2A and 3A. There
d
IR data are strongly influenced by the increase of the C¼N double
are
four
planar
fragments
in
these
anions:
bond character in the allyldithiocarbimates.
C1ꢀS1ꢀC10ꢀS2ꢀN2ꢀS3, C1ꢀC2ꢀC3ꢀC4ꢀC11 and the two aro-
matic rings. In all compounds, the torsion angles around the bonds
S3ꢀC1’ and C1ꢀC2 showed different conformations of these three
last fragments in relation to the least square plan through the
C1ꢀS1ꢀC10ꢀS2ꢀN2ꢀS3 atoms (Table 2).
The 13C NMR signals of the tetraphenylphosphonium cation
appeared as doublets with the expected J values in the spectra of
1A-E, 2A-E and 3A-E, due to coupling with the phosphorus atom:
89 Hz for Ca, 13 Hz for Cb and Cf, 10 Hz for Cc and Ce, and 3 Hz for
Cd.
The distances in the methoxycarbonyl group are within the re-
ported range for related compounds [6,30e32]. The bond length
C2eC3 is consistent with a typical C¼C double bond [33]. The
C3eC4 and C2eC11 distances are shorter than a normal CeC single
bond of ca.1.54 Å [33]. These values are similar to those reported for
related compounds [6]. The C10eN2 distances have a partial double
bond character and are shorter than those observed in the free li-
gands. For example, the C10eN2 distance for the potassium N-4-
iodophenylsulfonyldithiocarbimate is 1.342(9) Å [11].
3.3. X-ray crystallography
To gain a deeper insight into the structures of the allyldithio-
carbimates, we decided to investigate one compound of each series
by X-ray crystallography. After several crystallization attempts, we
managed to obtain suitable crystals of compounds 1A from ethanol/
water solutions (1:1 v/v), 2A and 3A from acetone/water solutions
(1:1 v/v). These compounds presented the nitro group in para, meta
and ortho positions, respectively (Scheme 2).
The X-ray data showed that compound 1A crystallizes in the
non-centrosymmetric space group P21 of the monoclinic system,
while 2A crystallizes in the centrosymmetric space group P1 of the
triclinic system and 3A in the space group P2/c of the monoclinic
system. Four anions and four cations form the asymmetric unit of
compound 1A (Fig. 2), whereas the asymmetric units of compounds
The C1eS1 distances are slightly longer than typical CeS single
bonds in all compounds. The C10eS1 and C10eS3 distances are
shorter than a CeS single bond and the C10eS2 is longer than a
typical C¼S double bond [33]. This fact is due to the conjugated
character of the NCS2 system and is observed in the structures of
other allyldithiocarbimates [6] and disulfides derived from sulfo-
nyldithiocarbimates [30]. These observations agree with the spec-
troscopic data.

10
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
Fig. 6. Packing diagram of 2A, viewed down the a axis. Dashed lines indicate CeH/O and CeH/S intermolecular interactions.
The bond lengths and angles in the tetraphenylphosphonium
3.4. Hirshfeld surface
cation are within the reported range [6,30]. The phosphorus atom
present tetrahedral distorted geometry with the CeC bond lengths
and the CePeC angles in the four phenyl rings ranging from 1.28(2)
Å to 1.47(2) Å and from 104.1(2) to 114.3(6)ꢂ, respectively. In
compound 3A, the phosphorus atom is in a special position (0,y, 1/
4).
The crystal packings in 1A, 2A and 3A are stabilized mainly by
electrostatic interactions between oppositely charged ions.
CeH/O intramolecular interactions are observed in the three
compounds. Other intramolecular interactions are particular to
some crystals such as CeH/N (compounds 1A and 3A), CeH/S
The molecular electrostatic potentials mapped (Fig. 8) on
Hirshfeld surfaces of the anions were calculated over the ꢀ0.04 to
0.03 au range for 1Aa, 2A and 3A. Specifically, the blue (electro-
positive) and red (electronegative) mapping provided a special
insight on the electronic delocalization that occurs in compound 3A
due to the presence of the nitro group in ortho position, which is
not observed in compound 2A where the nitro group is in the meta
position. It is possible to observe in compound 2A a dark blue area
between the nitro group and the ester carbonyl, whereas in com-
pound 3A there is a small white area between these groups, indi-
cating a decrease in polarity. Moreover, in 1Aa, where the nitro
substituent is in para position, a larger blue area is observed be-
tween the nitro and the carbonyl groups. Considering the greater
distance between these groups in 1Aa, an even higher polarity is
expected. These differences partially explain the melting point
decrease from 1A to 2A and 3A (156.9 ꢂC > 136.4 ꢂC > 53.4 ꢂC,
respectively), as the increase in the polarity of the anion favors the
intermolecular interactions. The small number of strong in-
teractions present in the crystalline packaging of 3A (Table 3) ex-
plains its ionic liquid behavior.
(compounds 1A and 2A) and CeH/
the three compounds present contacts between cations and anions:
CeH/O in all compounds, CeH/S (compound 1A) and CeH/
p (compound 2A). In addition,
p
(compound 1A and 2A). The geometric parameters of these in-
teractions are listed in Table 3.
In compound 1A, the C26beH26b/O3a and C27beH27b/O3a
intermolecular interactions form dimmers, generating R12(5) ring
motifs [34]. The CeH/O (between anions) and CeH/S (between
cations and anions) intermolecular interactions form chains which
are interlinked by CeH/p giving rise to a supramolecular network
(Fig. 5).
In order to visualize the importance of intermolecular in-
teractions in the crystal structures of 1A, 2A and 3A, HS analyses
were carried out to investigate the atom/atom interactions. The
HS mapped with dnorm for these compounds highlighted stronger
interactions in the brightest red areas (Fig. 9), indicating both ac-
ceptors and donors. They correspond mainly to strong CeH/O
hydrogen bonds, showing their significant participation in the
crystal structure.
The 2D fingerprint plots are useful to identify particular atom
pair close contacts and show the relative contribution of different
intermolecular interactions to the Hirshfeld surface. Thus, Fig. 10
illustrates a summary of selected percentages of the intermolec-
ular interactions contributions for the crystal structures of 1A, 2A
and 3A. This analysis shows that H/H, C/H, H/C, O/H and H/O,
S/H and H/S contacts determine the crystals packings. All in-
teractions show a similar pattern, except for the H/O and H/S
contacts, which have different values in all structures. The non-
In compound 2A, the C8eH8/O6 interactions between anions
and the C18eH18/O5 contacts between cations and anions form
ribbons along the a axis which are interlinked by CeH/S and
C30eH30/O1 intermolecular interactions forming bidimensional
layers. These layers are linked by C40eH40/O3 hydrogen bonds
along the a axis. Moreover, there are three CeH/p intermolecular
interactions between cations and anions stabilizing the three-
dimensional arrangement (Fig. 6).
In compound 3A, the C28eH28/O3 and C36eH36/O2 inter-
molecular interactions between cations and anions form zigzag
chains along the c axis, which are connected by C29eH29/O6
hydrogen bonds in the a axis direction giving rise to a three-
dimensional network (Fig. 7).

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
11
Fig. 7. Packing diagram of 3A, viewed down the c axis. Dashed lines indicate CeH/O intermolecular interactions.
Fig. 8. Electrostatic potential mapping of the anions of 1Aa, 2A and 3A.
Fig. 9. View of the three-dimensional Hirshfeld surfaces plotted over dnorm of 1Aa, 2A and 3A, respectively. The surfaces are partially transparent for clarity.
classical H/H interactions are the main contributors to the total
Hirshfield surface (42.7% in 1A and ca. 39% in 2A and 3A, Fig. 11).
The C/H/H/C contributions for the crystal packagings (21.6% in
1A, 24.3% in 2A, and 25.5% in 3A) are also important. No significant
p/p interactions were found within the crystals (the C/C contacts
make only 2.8%, 1.9% and 0.7% of the surface area, respectively for
A. solani, R. solani, F. oxysporum and S. sclerotiorum) were carried out
in order to evaluate the agrochemical potential of the new allyldi-
thiocarbimate salts. These microorganisms belong to various fam-
ilies and were chosen due to the enormous losses they can cause in
economically important crops. The gray mold disease caused by
B. cinerea affects more than 200 host plants in different stages of
development and several tissues (shoots, fruits, flowers, leaves and
storage organs), being one of the most important postharvest de-
cays of fruits and vegetables [3,35]. C. acutatum is also a fungus with
a broad host range, being very destructive in olives and strawberry
crops, for example. It can cause anthracnose and other plant
1A, 2A and 3A).
3.5. Biological tests
Biological tests with six fungi species (B. cinerea, C. acutatum,

12
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
Fig. 10. Two-dimensional fingerprint plots for compounds 1A (aeh), 2A (aeh) and 3A (aeh). The di and de values are the closest internal and external distances (in Å) from given
points on the Hirshfeld surface contacts.
Fig. 11. Percentages of contact interactions contributions to the Hirshfeld surface areas in compounds 1A, 2A and 3A.

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
13
Table 4
chlorine atom on the allyldithiocarbimate structure can enhanced
its biological activity [6]. The salt shown in Fig. 1 was very active
against B. cinerea, with an IC50 of 94 mM [6]. Thus the new allyldi-
thiocarbimate 1C, bearing a chlorine atom and a nitro group was
chosen for the screening tests against the six fungi species. The
results are shown in Table 4.
It can be inferred from Table 4 that the allyldithiocarbimate 1C
was active against the six species. It is also clear that the compound
is selective, being more efficient in the control of B. cinerea, with
Inhibition percentage (I%) of the mycelial growth of B. cinerea, R. solani and
S. sclerotiorum (after 3 days of incubation at 20 ꢂC), A. solani (after 4 days of incu-
bation at 25 ꢂC), C. acutatum and F. oxysporum (after seven days of incubation at
25 ꢂC) in the presence of the allyldithiocarbimate salt 1C at 160
mM.
Fungi
I%
Fungi
I%
B. cinerea
A. solani
S. sclerotiorum
70
31
30
R. solani
F. oxysporum
C. acutatum
26
12
9
70% inhibition at 160
mM, while at the same dose, the mycelial
growth inhibition of the other microorganisms were inferior to 31%.
Based on these results (Table 4), in order to deepen the bio-
logical studies on the allyldithiocarbimates, new in vitro tests
against B. cinerea were performed with the whole series of ana-
logues 1A-E, 2A-E and 3A-E, at various concentrations, ranging
Table 5
Inhibition percentages of the mycelial growth of B. cinerea after 72 h of incubation at
20 ꢂC in different concentrations of compounds 1A-E, 2A-E and 3A-E.
Compound
Concentration/
10
mM
5
20
40
120
160
from 5 to 160
mM. Table 5 shows the inhibition percentages
Inhibition (%)
calculated for each treatment. In addition, the Tukey test at 5%
significance was applied to the data aiming the comparison of the
results for each concentration tested.
f
cd
a
ef
c
gh
cdef
1A
1B
1C
1D
1E
2A
2B
2C
2D
2E
3A
3B
3C
3D
3E
1
1
1
6
1
20
12
20
19
51
41
46
46
29
45
51
45
48
40
47
40
41
43
37
55
59
62
59
52
60
65
61
61
57
57
56
57
54
54
65
63
64
65
65
68
76
74
67
65
67
66
70c
73
65
70
69
70
75
78
77
71
67
73
66
f
g
ef
cd
cd
h
d
h
j
ef
c
cde
def
b
gh
gh
gh
cde
a
fgh
hi
gh
bc
a
From Table 5 it can be noted that the nitro group in meta posi-
tion provided the best results, as in most cases the compounds 2A-E
were more active than their analogues 1A-E or 3A-E, with the same
R groups. The halogens also presented a discrete contribution for
the observed differences. The less active compound seems to be the
allyldithiocarbimate 1E, with a para-nitro group and an iodine
atom, although it gets more effective at higher concentrations than
a few other analogues. Compound 2B present the best general
performance, with the highest inhibition effect in almost all tested
concentrations. This compound bears a meta-nitro group and a
fluorine atom in the dithiocarbimate moiety. The fluorine atom
does not cause great steric effects, as fluorine is a relatively small
atom (resembling the hydrogen). However, it can change other
properties related to electronic effects, interfering in intermolec-
ular interactions and in the physical properties of the substance.
Thus, the number of fungicides bearing fluorine atoms is expres-
sive, especially aromatic-fluorine compounds [48,49]. Fig. 12 shows
a comparison of the activity of 2B and the less active allyldithio-
c
def
a
h
h
7
bc
a
c
20
22
26
23
27
14
28
23
17
18
14
cd
a
a
6
4
4
3
7
cdef
cdef
cdef
c
b
a
cd
b
b
b
a
b
def
fgh
def
efg
efgh
ij
g
f
d
a
bc
f
de
de
de
fg
g
cde
j
b
b
f
11
cde
f
5
1
2
74cd
f
ef
g
e
69cd
72b
72defg
77ab
ef
g
a-gValues presenting the same superscript letter, in the same column, do not differ at
5% level of significance by the Tukey test.
diseases [36e38]. The early blight disease due to A. solani causes
significant loss in the potato production worldwide [39]. R. solani
and F. oxysporum are soil-borne fungi. These plant pathogens are
among the most difficult to control. R. solani causes pathogenic
conditions such as black scurf in potato, leaf spot and root rot in
tobacco, out of other plant diseases [40,41]. F. oxysporum affects
various cultures and is the major limiting factor for tomato pro-
duction, even in hydroponic cultivation systems [42,43].
S. sclerotiorum is a necrotrophic pathogen, which can also survive in
the soil and affect hundreds of cultures. This broad host range
makes it difficult to minimize the damages caused by S. sclerotiorum
through crop rotation [44]. It is specially damaging to the soybean
production, as no fungicide is able to offer complete control of the
white mold disease [45e47].
carbimate 1E, at 20 mM.
Using the whole set of data collected for B. cinerea it was
possible to plot dose-response curves, as exemplified in Fig. 13.
From the dose-response equations it was possible to calculate the
IC50 values for each substance (Table 6). Although compounds 1A,
2B and 2D presented similar IC50 values (Table 6), an inspection on
Table 5 shows that 2B was more active than these compounds in
almost all concentrations tested. The results indicate that com-
pound 2B is a target compound for the development of a new
fungicide to control Botrytis diseases.
The presence of a nitro group can change the activity of a
We have previously demonstrated that the presence of a
Fig. 12. Photograph showing the mycelial growth of B. cinerea in the presence of the allyldithiocarbimates 1E and 2B at 20 mM compared to the control.

14
N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
Fig. 13. Inhibition percentages of the mycelial growth of B. cinerea: comparison of dose-response curves for the less (1E) and the most (2B) active allyldithiocarbimates.
Table 6
Table 7
Concentration of compounds 1A-E, 2A-E and 3A-E for the inhibition of 50% of the
mycelial growth of B. cinerea (IC50), over the control.
Concentration of compounds 4A-E and 5A-E for the inhibition of 50% of the mycelial
growth of B. cinerea (IC50), over the control [6].
Compound
IC50
(
mM)
Compound
IC50
(m
M)
Compound
IC50
(
m
M)
Compound
IC50
(m
M)
Compound
IC50 (mM)
1A
1B
1C
1D
1E
20
25
23
24
37
2A
2B
2C
2D
2E
24
20
23
21
28
3A
3B
3C
3D
3E
26
29
29
29
33
4A
4B
4C
4D
4E
100
130
94
95
130
5A
5B
5C
5D
5E
47
41
38
46
49
molecule, interacting with enzymes, cell membranes and target
receptors, or producing secondary activity reactions [50,51]. In fact,
the introduction of the nitro group in the structure of the allyldi-
thiocarbimates was the most important feature for the activity
against B. cinerea. While the allyldithiocarbimates 1A-E, 2A-E and
Ziram and Mancozeb, were also tested against B. cinerea in the same
conditions, at 160 M. The new allyldithiocarbimates were also
more active than these fungicides, which inhibited the growth of
B. cinerea by 16% (Ziram) and 8% (Mancozeb). Thus, the new allyl-
dithiocarbimate salts are more active than dithiocarbamates widely
used as agrochemicals.
m
3A-E presented IC50 between 20 and 37
without the nitro group (Fig. 14, compouds 4A-E) showed IC50
values in the range of 94e130 M (Table 7), using the same testing
mM, their analogues
m
4. Conclusion
methodology [6]. The new compounds were also more active than
other analogues derived from furfuraldehyde (Fig. 14, compouds
In this work, the steps required for the synthesis of 15 new
tetraphenylphosphonium allyldithiocarbimates derived from
Morita-Baylis-Hillman adducts bearing nitro groups have been
described. The new substances were synthesized in good yields
(63e97%) and had their structures confirmed by IR and NMR
spectroscopy, high-resolution mass spectrometry as well as single
crystal X-ray diffraction. The X-ray diffraction evidenced the Z
stereochemistry of the allyldithiocarbimate anions. The X-ray data
for the compounds 1A, 2A and 3A revealed that the crystal packing
are mainly stabilized by the electrostatic interactions between
oppositely charged ions as well as CeH/O intramolecular and
intermolecular interactions. Molecular electrostatic potentials
mapped for these compounds were correlated with the decrease of
melting points depending on the position of the nitro group on the
aromatic ring: para > meta > ortho. This explains the ionic liquid
5A-E) with IC50 of 38e56
The influence of the parent allylic bromides (Scheme 1) on the
mycelial growth of B. cinerea was tested at 160 M, for comparison
mM (Table 7) [6].
m
purposes. The potassium dithiocarbimates were not included in the
tests as they are not very stable in solution, showing high degree of
decomposition after 24 hours in aqueous media. The inhibition
percentages of the treatments with the allylic bromides were of
only 14% (para-nitro group), 25% (meta-nitro group) and 22%
(ortho-nitro group), while at the same concentration, the allyldi-
thiocarbimate salts had inhibition ranges of 65e78%. It is inter-
esting to note that the allylic bromide with the nitro group in meta
position was more active than the para and ortho analogues, as it
was observed with the series 1A-E, 2A-E and 3A-E.
Two metal-dithiocarbamates used as commercial fungicides,

N.M. Albuini-Oliveira et al. / Journal of Molecular Structure 1214 (2020) 128149
15
Fig. 14. Published allyldithiocarbimates [6].
ꢀ
behavior of the salts of the series 3A-E. The 2D fingerprint plots for
the compounds 1A, 2A and 3A, together with the contribution
percentages of different interactions to their Hirshfield surfaces,
provided a more complete understanding of the intermolecular
interactions present in the crystal.
the Laboratorio de Celulose e Papel of the Universidade Federal de
Viçosa for the elemental analysis of C, H and N.
Supplementary material
The allyldithiocarbimates strongly inhibit the mycelial growth
of B. cinerea, with little effect on other fungi species. The new
compounds are more effective against B. cinerea than the active
principals of the commercial fungicides Ziram and Mancozeb. The
presence of a nitro group on the allyldithiocarbimate structure
increases its activity towards B. cinerea, especially when the nitro
group is in meta position, with IC50 values between 20 and 28 mM,
depending on the presence of the various halogen substituents
tested.
Details on data collection, refinement and crystallographic data
in CIF format for structures 1A, 2A and 3A have been deposited at
the Cambridge Crystallographic Data Centre, CCDC 1966804
(compound 1A), CCDC 1966805 (compound 2A) and CCDC 1966806
(compound 3A). Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road, Cambridge,
CB21EZ, UK (fax: þ44 1223 336 033; email: deposit@ccdc.cam.ac.uk
or http://www.ccdc.cam.ac.uk).
The compound 2B, presenting a meta-nitro group and a para-
fluorine atom (in different aromatic rings) presented the best
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