228
M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
Table 1
HO
Crystal and experimental data
S
Compound
1
2
Formula
Color/shape
Formula weight
Crystal system
Space group
C8H9N3O2S
Yellow/plate
211.24
C10H10N4S
Yellow/plate
218.28
N
C
C
H
N
H
NH2
Monoclinic
C2/c
Triclinic
ꢀ
P1
0.25 Â 0.30 Â 0.35 mm3
0.30 Â 0.38 Â 0.45 mm3
OH
Crystal dimension
Unit cell parameters
a = 21.421(1) Å
b = 4.131(2) Å
b = 122.6(1)°
a = 7.232(1) Å a = 69.0(1)°
b = 11.166(1) Å
b = 85.3(1)°
(E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone (1)
c = 24.942(2) Å
c = 13.648(1) Å
H
C
H
N
c
= 82.4(1)°
V
Z
1856.1(6) Å3
8
1019.5(1) Å3
4
S
H
Dc (g cmÀ3
(Mo Ka)
)
1.512 g cmÀ3
0.325 mmÀ1
880
1.422 g cmÀ3
0.287 mmÀ1
456
N
N
C
l
F (000)
NH2
2hmax
53.52°
55.14°
h, k, l range
À26 6 h 6 26
À5 6 k 6 5
À9 6 h 6 9
À14 6 k 6 14
À17 6 l 6 17
À31 6 l 6 30
No. of measured
reflections
No. of independent
reflections
13406
1977
1662
19971
4699
3968
(E)-2-[(1H-indol-3-yl)methylene]thiosemicarbazone (2)
Scheme 1. Chemical formula of the title compounds.
No. of observed
reflections
Goodness-of-fit on F2
Measurement
1.029
1.069
STOE IPDS 2
STOE X-AREA
SHELXS-97
STOE IPDS 2
STOE X-AREA
SHELXS-97
determined on an Electro Thermal IA 9100 apparatus using a
capillary tube. Thiosemicarbazide, indoline-3-carbaldehyde, 2,4-
dihydroxybenzaldehyde, THF, DMSO were purchased from Merck
(Germany).
Program system
Structure determination
Refinement method
Full-matrix least squares
Full-matrix least squares
on F2
on F2
R, Rw (I > 2
r
D
(I))
0.035, 0.086
0.201, À0.230 e ÅÀ3
0.032, 0.083
(D
q)max, (
q)min
0.267, À0.209 e ÅÀ3
2.2. Synthetic procedures
2.2.1. (E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone (1)
Thiosemicarbazide (0.91 g; 1.0 Â 10À2 mol) was added to a dry
THF (100 mL) solution of 2,4-dihydroxybenzaldehyde (1.38 g;
1.0 Â 10À2 mol). The mixture was stirred and heated for 2 h. Com-
pound 1 was obtained from the evaporation of THF. It was crystal-
lized from chloroform/n-heptane as a yellow crystals, m.p. 191 °C,
1.84 g (87%) yield. Found: C, 45.39; H, 4.26; N, 19.90. Calc. for
Mo K
a radiation (k = 0.71073 Å). Data collection, reduction and
corrections for absorption and crystal decomposition for com-
pound 1 and for compound 2 were achieved using X-AREA, X-
RED software [36]. The structures were solved by SHELXS-97 and
refined with SHELXL-97 [37,38]. The positions of the H atoms
bonded to C atoms were calculated (CAH distance 0.96 Å), and re-
fined using a riding model. The H atom displacement parameters
were restricted to be 1.2Ueq of the parent atom. The crystal struc-
tures were solved by direct methods and refined by full-matrix
least squares. The details of the X-ray data collection, structure
solution and structure refinements are given in Table 1. Bond dis-
tances and angles are listed in Table 2. The molecular structure
with the atom-numbering scheme is shown in Fig. 1 [39]. Crystal-
lographic data (excluding structure factors) for the structure re-
ported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC 691504 & 691505 [40].
C8H9N3O2S; C, 45.49; H, 4.29; N, 19.89%. IR (KBr, cmÀ1);
3477–3339–3175 s, ArAH; 3055 w, C@N; 1632 s, C@C; 1556
s, CAN; 1466 s, CAO; 1317 s,
C@S; 1239. 1H NMR (DMSO); d
mNAH;
m
m
m
m
m
m
ppm, 11.20 (s, 1H, Ar-OH); 9.78 (s, 2H, Ar-OH and NAH); 8.25 (s,
1H, Ar-CH@ NA); 7.96 (s, 2H, ANH2A); 7.76; 7.76–6.25 (m, 3H,
Ar-H).
2.2.2. (E)-2-[(1H-indol-3-yl)methylene]thiosemicarbazone (2)
Thiosemicarbazide (0.91 g; 1.0 Â 10À2 mol) was added to a dry
THF (100 mL) solution of indoline-3-carbaldehyde (1.47 g; 1.0 Â
10À2 mol). The mixture was stirred and heated for 2 h. Compound
2 was obtained from the evaporation of THF. It was crystallized
from chloroform/n-heptane as
0.65 g (67%) yield. Found: C, 54.50; H, 5.49; N, 25.43. Calc. for
C10H10N4S; C, 55.05; H, 4.59; N, 25.68%. IR (KBr, cmÀ1);
NAH;
3448–3310–3224 s, Ar-H; 3042 m, CAH; 2974–2922–2878 m,
C@N; 1611 s, C@C; 1576 s, CAN; 1441 s,
C@S; 1251. 1H
a yellow crystals, m.p. 92 °C,
3. Results and discussion
m
m
m
3.1. FT-IR, 1H NMR, 13C NMR and UV–visible spectroscopic studies
m
m
m
m
NMR (DMSO); d ppm, 11.57 (s, 1H, NAH); 11.17 (s, 1H, NAH);
8.22 (d, 1H, ACH@NA); 7.43 (s, 2H, NH2); 8.24–7.02 (m, 5H, Ar-
H + C = CH).
The FT-IR data of the compounds are given in synthetic pro-
cedures. Vibration bands with the wave numbers of 3477–3339–
3175 and 3448–3310–3224 cmÀ1 NAH), 3055 and 3042 cmÀ1
(m
(m
CAH, Ar-H), 1632 and 1611 cmÀ1
(m
C@N), 1556 and 1576 cmÀ1
2.3. Crystallography
(m
C@C), 1239 and 1251 cmÀ1
(m
C@S) were observed for compounds
1 and 2, respectively (Fig. 2). The stretching frequency observed
at 2804, 2738 and 2811, 2733 cmÀ1 in 1 and 2 shows the pres-
ence of OAH. . .N and NAH. . .N intramolecular hydrogen bonds
The data collection for both compounds was performed on a
STOE IPDS-2 diffractometer employing graphite-monochromatized