Structure of methyl n-(4-methoxyphenylmethyl)-N'-cyanocarbamimidothioate and Methyl N-[1-(phenylmethyl)-4- piperidinyl]-N0-cyanocarbamimidothioate

Article abstract of DOI:10.1007/s10870-011-0110-y

The title compounds, Methyl N-(4-methoxyphenylmethyl)- N0- cyanocarbamimidothioate, I, and Methyl N-[1-(phenylmethyl)-4-piperidinyl]-N0- cyanocarbamimidothioate, II, have been designed and synthesized for use as new potential organic molecular electronic

Full text of DOI:10.1007/s10870-011-0110-y

J Chem Crystallogr (2011) 41:1395–1399
DOI 10.1007/s10870-011-0110-y
ORIGINAL PAPER
Structure of Methyl N-(4-methoxyphenylmethyl)-N0-cyano-
carbamimidothioate and Methyl N-[1-(phenylmethyl)-4-
piperidinyl]-N0-cyanocarbamimidothioate
Yinxiang Lu
Received: 9 September 2009 / Accepted: 21 April 2011 / Published online: 27 May 2011
Ó Springer Science+Business Media, LLC 2011
Abstract The title compounds, Methyl N-(4-methoxy-
phenylmethyl)-N0-cyanocarbamimidothioate, I, and Methyl
N-[1-(phenylmethyl)-4-piperidinyl]-N0-cyanocarbamimido-
thioate, II, have been designed and synthesized for use as
new potential organic molecular electronic materials. The
crystal structure of I and II were determined with crystal
Donor-p-Acceptor heterocyclics have recently attracted
considerable attention due to their applications in ultrafast
and ultrasensitive molecular electronic devices and ultra-
high density data storage [4–7]. Sandwich structure devices
Metal/Organic/Metal are manufactured, where ‘‘Organic’’
can be N-cyanocarbamimidothioate [8, 9]. Systematic study
of the crystal structure of differently substituted N-cya-
nocarbamimidothioate should make it possible to under-
stand the formation of certain structure elements desired for
electronic applications. Besides, the knowledge of the bulk
structure will be helpful to understand the formation of thin
layers, which are needed for microelectronic devices.
˚
data (I: Monoclinic, P21/c, a = 4.746(2) A, b = 5.737(3)
˚
˚
A, c = 17.399(7) A, b = 91.667(7)8, Rall = 0.0703; II:
˚
Orthorhombic, Pna21, a = 18.209(8) A, b = 11.463(5) A,
˚
˚
c = 7.539(3) A, b = 90.00 8, Rall = 0.0481). N–HꢀꢀꢀN
hydrogen bonds were responsible for the formation of one-
dimensional zigzag molecular chains of I, and trifurcated
hydrogen-bonded molecular chains were indicated in
structure of II. C–Hꢀꢀꢀp and C–HꢀꢀꢀN hydrogen bonds were
found in both structures. All these types of interaction
together form an extended three-dimensional network and
stabilize the title crystals.
1
Herein, the synthesis [10], H NMR spectroscopy, FT-IR
spectroscopy and crystal structure of the title compounds,
methyl N-(4-methoxyphenylmethyl)-N0-cyanocarbamimi-
dothioate (I) and methyl N-[1-(phenylmethyl)-4-piperidi-
nyl]-N0-cyano-carbamimidothioate (II), are reported.
Keywords N-cyanocarbamimidothioate ꢀ Molecular
assemblies ꢀ Hydrogen bonds ꢀ X-ray diffraction
Experimental
Melting points were determined in open capillaries and are
uncorrected. IR spectra were recorded on a Nicolet Avatar-
1
360IR spectrometer. H NMR spectra were measured on a
Introduction
Replacing the traditional inorganic semiconductor with the
organic semiconducting materials to modify the electric and
optical signals shows great prospect, according to the
excellent property of the organic materials [1–3]. Much
attention has been paid to organic electronic devices
based on the organic molecular and polymer materials.
Bruker DMX500 spectrometer using TMS as internal stan-
dard. All chemical reagents were obtained from Aldrich,
Merck, Lancaster, or Fluka and used without further
purification.
Synthesis of Methyl N-(4-methoxyphenylmethyl)-N0-
cyanocarbamimidothioate (I)
Y. Lu (&)
To a solution of dimethyl cyanocarbonimidodithioate
(0.1460 g, 1 mmol) in ethanol (5 mL) was added 4-
methoxyyphenylmethylamine (0.137 g, 1 mmol), and the
Department of Materials Science, Fudan University,
Shanghai 200433, People’s Republic of China
e-mail: lvyinxiang@hotmail.com
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J Chem Crystallogr (2011) 41:1395–1399
reaction mixture was stirred at room temperature for 4 h.
Thereafter, the reaction mixture was filtered and precipitate
was washed with EtOAc to give methyl N-(4-methoxy-
phenylmethyl)-N0-cyanocarbamimidothioate (0.224 g, 90%).
Table 1 Crystal data and structure refinement for I and II
I
II
CCDC deposit no.
Color/Shape
745940
745941
1
Yellow/prism
Yellow/prism
C15H20N4S
288.42
m.p. 154–156 °C; H NMR (DMSO-d6, 500 MHz): d 2.60
Empirical formula
Formula weight
Temperature, K
C11H13N3OS
(s, 3 H, SCH3), 3.81 (s, 3 H, OCH3), 4.41–4.56 (d, 2 H,
J = 5.8 Hz, PhCH2), 7.21–7.46 (m, 5 H, ArH), 8.83 (s, 1 H,
NH). IR (KBr) m: 3008, 2965, 2922, 2211, 1665, 1572,
235.30
293(2)
293(2)
1437, 1245, 1193, 1010, 861, 766 cm-1
.
˚
Wavelength (A)
0.71073
Monoclinic
P21/c
0.71073
Methyl N-[1-(phenylmethyl)-4-piperidinyl]-N0-cyanoc-
arbamimidothioate (II) was prepared in the same manner
Crystal system
Orthorhombic
Pna21
Space group
1
as I, yield: 85%, m.p. 160–1162 °C; H NMR (DMSO-d6,
Absorption correction
Multi-scan
(SADABS)
Multi-scan
(SADABS)
500 MHz): d 1.52–2.45 (m, 9H, piperidinyl-H), 2.60 (s, 3
H, SCH3), 3.52 (s, 2 H, PhCH2), 7.20–7.36 (m, 5 H, ArH),
7.84 (d, 1 H, J = 7.8 Hz, NH). IR (KBr) m: 3280, 2985,
Unit cell dimensions
˚
a (A)
4.746(2)
5.737(3)
42.22(2)
91.667(7)
1.360
18.209(8)
11.463(5)
7.539(3)
90.00
2910, 2170, 1540, 1515, 1417, 1265, 1001, 869, 776 cm-1
.
˚
b (A)
˚
c (A)
b (8)
Crystal Structure Determinations and Refinements
Density (calculated)
(Mg/m3)
1.217
l (mm-1
)
0.264
496
0.202
616
Single crystals of I and II suitable for X-ray analysis were
obtained by slow evaporation from ethanol. Single crystal-
line samples of I and II are yellow prisms. The experimental
data were obtained at room temperature using MoKa-radi-
F (000)
Crystal size (mm)
0.40 9 0.20 9 0.20 0.25 9 0.15 9 0.14
H range for data
collection (8)
2.896–27.040
2.857–26.326
˚
ation and a graphite monochromator (k = 0.7107 A) with
Ranges of h, k, l
-6 B h B 6
-7 B k B 7
-53 B l B 29
4811
-21 B h B 18
-12 B k B 13
-8 B l B 8
6112
Bruker SMART diffractometer using phi and omega scans
technique. The structures were solved by direct methods and
refined by a full matrix least-squares procedure in the
anisotropic approximation for non-hydrogen atoms. H atoms
were refined as riding atoms in ideal positions. The isotropic
refinement of the H atoms was likely also constrained to be
1.2 Ueq of their parent atom. For both structures, multi-scan
was used for absorption correction (SADABS; Sheldrick,
1996) [11]. All calculations were carried out with a personal
computer using the Bruker SHELXTL program package [12,
13]. Drawing of these molecules was obtained with the
ORTEP program [14].
Reflections collected
Reflections observed
Independent reflections
Data/parameters
2108
2365
2418
2753
2418/145
1.160
2753/181
1.047
GOF (F2)
Final R1/wR2 indices
[I [ 2r(I)]
Final R1/wR2 indices
0.0620/0.1513
0.0382/0.0859
0.0703/0.1552
0.0481/0.0906
(for all)
Largest diff. Peak/hole
-3
0.503/-0.257
0.165/-0.164
CCDC-745940 (I) and CCDC-745941 (II) contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge at http://www.ccdc.
cam.ac.uk/const/retrieving.html or from the Cambridge-
Crystallographic Data Centre (CCDC), 12 Union Road,
Cambridge CB2 1EZ, UK; fax: ?44 (0) 1223–336033 or
e-mail: deposit@ccdc.cam.ac.uk.
˚
(e.A
)
noteworthy that the presence of a push–pull imine unit,
with the methylthio group as electron donor and the cyano
group as an electron acceptor, most probably leads to
diverse attractive close interactions in their crystal struc-
tures [15].
In the structure of I, the C10–N3 distance shows pre-
dominantly triple-bond character, whereas the C10–N2,
N2–C9 and C9–N1 distances suggest that they are partial
double bonds. Together with the quasilinear N2–C10–N3
angle of the cyano group, this pattern is typical of the
N:C–N=C(SCH3)–N group of methyl N-cyanocarboxim-
idothioate compounds [16]. Further examination of the
Results and Discussion
Important details of the data collection and structure
refinement are summarized in Table 1. Selected geometric
parameters and hydrogen bonding geometry are presented
in Table 2. Structures of I and II are shown in Fig. 1. It is
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J Chem Crystallogr (2011) 41:1395–1399
1397
˚
Table 2 Selected geometric parameters (A, 8), hydrogen-bonding
˚
˚
geometry (A, 8) and short intermolecular contacts (A) for I and II
I
II
N3–C10
1.144(4)
1.315(4)
1.317(3)
1.312(3)
1.787(3)
1.403(5)
172.3(3)
119.7(2)
119.1(2)
122.1(2)
3.000(4)
150.8
N4–C15
1.157(3)
1.324(3)
1.326(3)
1.328(3)
1.804(3)
1.456(3)
174.3(3)
119.0(2)
119.7(2)
124.4(2)
3.145(3)
144.0
N2–C10
N3–C15
N2–C9
N3–C13
N1–C9
N2–C13
S1–C11
S1–C14
O1–C1
N1–C7
N3–C10–N2
C10–N2–C9
N1–C9–N2
C9–N1–C8
N1–H1dꢀꢀꢀN3i
N4–C15–N3
C15–N3–C13
N3–C13–N2
C13–N2–C10
N2–H2bꢀꢀꢀN4#i
C1–H1aꢀꢀꢀO1ii
C4–H4ꢀꢀꢀN2iii
3.410(3)
140.6
C11–H11aꢀꢀꢀN4#i
C14–H14ꢀꢀꢀN4#i
3.605(3)
141.7
3.526(4)
160.8
3.629(4)
165.2
C8–H8bꢀꢀꢀC4iv
(phenyl)
S1ꢀꢀꢀS1v
3.697(3)
162.0
C11–H11bꢀꢀꢀCt1#ii
(phenyl, C1ꢀꢀꢀC6)
C8–H8bꢀꢀꢀC15#iii
(cyano)
3.646(3)
173.0
3.297(4)
3.667(4)
163.6
Fig. 1 Molecular structure of I and II. Displacement ellipsoids are
drawn at the 50% probability level and H atoms are shown as small
spheres of arbitrary radii
Note Symmetry code: (i) x ? 1, y ? 1, z; (ii) -x, y ? 1/2, 3/2 - z;
(iii) x, y ? 1, z; (iv) x ? 1, y, z; (v) -x ? 1, -y, -z ? 2; (#i)
-x ? 3/2, y ? 1/2, z - 1/2; (#ii) x, y, z ? 1; (#iii) x, y, z - 1.
Ct refers to the centroid of the C1ꢀꢀꢀC6 phenyl ring
and NꢀꢀꢀH11a bonds. Thus, the terminal cyano N atom is a
trifurcated hydrogen-bond acceptor as shown in Fig. 4.
Two kinds of C–Hꢀꢀꢀp intermolecular interactions
were shown in structure of II, they are C11–H11bꢀꢀꢀCt1
(Ct refers to the centroid of the C1ꢀꢀꢀC6 phenyl ring)
and C8–H8bꢀꢀꢀC15 (cyano group C15:N4) hydrogen
bonds.
crystal structure of I reveals the existence of several pos-
sible C–HꢀꢀꢀN, C–HꢀꢀꢀO, C–Hꢀꢀꢀp (C4, phenyl) and N–HꢀꢀꢀN
interactions (Table 2), as described in the literature
[17, 18]. Intermolecular N1–H1dꢀꢀꢀN3i hydrogen bonds
[symmetry code: (i) x ? 1, y ? 1, z] form zigzag molec-
ular chains propagating along the b axis direction, as shown
in Fig. 2. The S1ꢀꢀꢀS1v [symmetry code: (v) -x ? 1, -y,
Comparing crystal I to II, it can be found that they have
the similar cyanocarbamimidothioate moiety, which is
responsible for some special electronic properties [19].
N–HꢀꢀꢀN hydrogen bonds form zigzag molecular chains in
both crystals. However, SꢀꢀꢀS short contacts only existed in
structure of I and trifurcated hydrogen bonds were merely
observed in structure of II. C–Hꢀꢀꢀp (phenyl) interactions
were revealed in both structures, which can be divided into
point to point interactions of I and point to face interactions
of II; and C–Hꢀꢀꢀp (C:N) interactions were just disclosed
in structure of II.
In summary, two N0-cyanocarbamimidothioates forming
molecular chains by intermolecular N–HꢀꢀꢀN hydrogen
bonding interactions, has been characterized. The structural
features and the existing similarities and differences are
discussed.
˚
-z ? 2] non-bonded separation is 3.297 (2) A, lower than
the sum of the van der Waals for the corresponding atoms,
which indicates
a strong intermolecular interaction
between these atoms.
In the structure of II, there also exists the similar N:C–
N=C(SCH3)–N group as compound I. The six-membered
piperidinyl ring adopts a chair conformation. Examination
of the crystal structure of II reveals the existence of several
possible C–HꢀꢀꢀN and N–HꢀꢀꢀN interactions (Table 2). A
view down the b axis of the unit cell (Fig. 3) reveals
hydrogen-bonded zigzag molecular chains, which are
formed by cyano-NꢀꢀꢀH2b intermolecular bonds. This same
cyano N atom also accepts other hydrogen bonds that
crosslinks neighboring hydrogen-bonded rings via NꢀꢀꢀH14
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J Chem Crystallogr (2011) 41:1395–1399
Fig. 2 Projections of molecular
packing of I. Dashed lines
indicate N–HꢀꢀꢀN hydrogen
bonds
Fig. 3 Projections of molecular
packing of II. Dashed lines
indicate N–HꢀꢀꢀN hydrogen
bonds
Fig. 4 Trifurcated hydrogen-
bonded molecular chains
propagating in the a-axis
direction; dashed lines indicate
C11–H11aꢀꢀꢀN4#i, C14–
H14ꢀꢀꢀN4#i and N2–H2bꢀꢀꢀN4#i
hydrogen bonds. (Symmetry
code as in Table 2)
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J Chem Crystallogr (2011) 41:1395–1399
1399
Acknowledgments This work was supported by National Natural
Science Foundation of China (no. 60701014) and Shanghai Leading
Academic Discipline Project (no. B113).
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