Synthesis, spectroscopic studies and crystal structure of (E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone and (E)-2-[(1H-indol-3-yl)methylene]thiosemicarbazone

Article abstract of DOI:10.1016/j.molstruc.2008.09.008

Thiosemicarbazone Schiff bases (1 and 2) derived from 2,4-dihydroxybenzaldehyde, indoline-3-carbaldehyde and thiosemicarbazone have been synthesized and their structures were elucidated by elemental analysis, FT-IR, ¹H NMR, ¹³C NMR a

Full text of DOI:10.1016/j.molstruc.2008.09.008

Journal of Molecular Structure 919 (2009) 227–234
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, spectroscopic studies and crystal structure of
(E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone and
(E)-2-[(1H-indol-3-yl)methylene]thiosemicarbazone
b
a
c
d
Mustafa Yıldız a, , Hüseyin Ünver , Dig˘dem Erdener , Aßskın Kiraz , Nazan Ocak Iskeleli
_
*
a Department of Chemistry, Faculty of Science and Arts, Çanakkale Onsekiz Mart University, TR-17100 Çanakkale, Turkey
b Department of Physics, Faculty of Science, Ankara University, TR-06100 Tandog˘an, Ankara, Turkey
c Department of Natural Sciences, Faculty of Education, Çanakkale Onsekiz Mart University, 17100 Çanakkale, Turkey
d Department of Physics, Faculty of Science and Arts, Ondokuz Mayıs University, TR-55139 Kurupelit, Samsun, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 July 2008
Received in revised form 21 August 2008
Accepted 9 September 2008
Available online 19 September 2008
Thiosemicarbazone Schiff bases (1 and 2) derived from 2,4-dihydroxybenzaldehyde, indoline-3-carbalde-
hyde and thiosemicarbazone have been synthesized and their structures were elucidated by elemental
analysis, FT-IR, 1H NMR, 13C NMR and UV–visible spectroscopic techniques. The structures of compounds
1 and 2 have also been examined cyrstallographically. The title compounds 1 and 2 crystallize in the
ꢀ
monoclinic space group C2/c and triclinic space group P1, with unit cell parameters: a = 21.421(1) and
7.233(1), b = 4.131(1) and 11.166(1), c = 24.942(2) and 13.648(1) Å, V = 1856.1(2) and 1019.5(1) Å3,
Keywords:
Thiosemicarbazone
Crystal structure
Dx = 1.512 and 1.422 g cmÀ3 and Z = 8 and 4, respectively.
Ó 2008 Elsevier B.V. All rights reserved.
Indoline-3-carbaldehyde
Hydrogen bonding
Spectroscopic studies
1. Introduction
and tautomerism between enol-imine and keto-amine form. In
these compounds, short hydrogen bonds between the OH group
Thiosemicarbazones and their metal complexes are a broad
class of biologically active compounds [1,2]. Due to this biological
activity, there is considerable interest in metal complexes of het-
erocyclic thiosemicarbazones [3]. Spectral and structural investiga-
tions of a series of biologically active heterocyclic base adducts of
copper(II) complexes of salicylaldehyde and 5-bromosalicylalde-
hyde thiosemicarbazones [4–6] have been studied. The thiosemi-
carbazone ligand usually coordinates with the metal through the
imine nitrogen and sulfur atom. The ligands feature more than
two covalent sites, the number of which depends on the aldehyde
and on the tautomeric equilibrium of the thiosemicarbazone,
although the most common way to coordinate is through the thio-
late form [7]. Thiosemicarbazones are an important group of mul-
tidentate ligands with potential binding sites available for a wide
variety of metal ions [8–10]. Tautomerism in Schiff bases with
OH group in ortho position to the imino group both in solution
and in solid state were investigated using spectroscopy and X-ray
crystallography techniques [11–19]. Schiff bases with OH group in
ortho position to the imino group are of interest mainly due to the
existence of either OAH. . .N or O. . .HAN type of hydrogen bond
in ortho position to the imino group and the imine nitrogen is
due to the stereochemistry.
Although a series of thiosemicarbazone Schiff base complexes
have been investigated crystallographically, there are only a few
reports about free Schiff base ligands [20–35]. We report here
the syntheses and characterization of two thiosemicarbazone
Schiff base ligands derived from 2,4-dihydroxybenzaldehyde and
indoline-3-carbaldehyde (Scheme 1). The structural analysis and
tautomerism studies were carried out utilizing FT-IR, 1H NMR,
13C NMR, UV–visible spectroscopic and X-ray crystallographic
techniques.
2. Experimental procedures
2.1. Reagents and techniques
The 1H and 13C NMR spectra were recorded on a Bruker DPX
FT-NMR spectrometer operating at 400 and 101.6 MHz. Infrared
absorption spectra were obtained from a Perkin-Elmer BX II spec-
trometer in KBr discs and were reported in cmÀ1 units. The UV–vis-
ible spectra were measured using a SHIMADZU 1208 series
spectrometer. Carbon, nitrogen and hydrogen analyses were
performed on a LECO CHNS-932 analyzer. Melting points were
* Corresponding author. Tel.: +90 286 2180018x1861.
E-mail address: myildiz@comu.edu.tr (M. Yıldız).
0022-2860/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2008.09.008

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

M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
229
Table 2
H2
C6
Bond lengths (Å), bond angles (°) and torsion angles (°) for compounds 1 and 2
H5
H1
C7
H4
N2
Compound 1
S1AC8
N2AC8
N2AN1
N1AC7
C8AN3
1.698(2)
1.327(2)
1.389(2)
1.281(2)
1.317(2)
O2AC4
C1AC6
C1AC2
C1AC7
O1AC2
1.363(2)
1.393(2)
1.404(2)
1.441(2)
1.355(2)
C1
C2
C5
C4
S1
H9
N1
C8
O2
C8AN2AN1
C8AN2AH4
N1AN2AH4
C7AN1AN2
N3AC8AN2
N3AC8AS1
121.7(1)
120.4(1)
117.7(1)
114.7(1)
118.4(2)
122.4(1)
N2AC8AS1
O1AC2AC3
O1AC2AC1
N1AC7AC1
N1AC7AH1
119.3(1)
118.3(1)
121.1(1)
123.4(1)
119.7(1)
N3
O1
C3
H3
H7
H6
H8
(1)
C8AN2AN1AC7
N1AN2AC8AN3
N1AN2AC8AS1
C6AC1AC2AO1
À163.8(2)
2.7(3)
C7AC1AC2AO1
N2AN1AC7AC1
C6AC1AC7AN1
C2AC1AC7AN1
À5.2(3)
N2
S1
À172.7(2)
À177.9(2)
6.7(3)
C2
C1
C4
À177.6(1)
N3
C3
C10
N4
179.4(2)
Compound 2
S1AC1
N3AC2
N3AN2
C3AC4
1.687(1)
1.280(2)
1.386(1)
1.372(2)
1.432(2)
1.438(2)
1.332(2)
1.330(2)
1.350(2)
1.371(2)
S2AC11
N6AC11
N6AN7
N7AC12
N8AC14
N8AC15
C12AC13
C13AC14
C13AC20
C11AN5
1.693(1)
1.333(2)
1.383(1)
1.278(2)
1.357(2)
1.370(2)
1.437(2)
1.368(2)
1.439(2)
1.323(2)
C9
C5
N1
C7
C6
C3AC2
C8
C3AC10
N2AC1
N1AC1
N4AC4
N4AC5
N6
S2
C13
C20
N8
N7
C14
C15
C11
C12
C2AN3AN2
C4AC3AC2
C4AC3AC10
C2AC3AC10
C1AN2AN3
N3AC2AC3
N3AC2AH2
C3AC2AH2
C4AN4AC5
N1AC1AN2
N1AC1AS1
N2AC1AS1
114.5(1)
123.8(1)
106.3(1)
129.8(1)
120.1(1)
122.5(1)
119.0(1)
118.4(1)
109.4(1)
117.1(1)
122.7(1)
120.3(1)
N4AC4AC3
110.2(1)
122.1(1)
119.1(1)
113.4(1)
109.2(1)
123.3(1)
119.3(1)
117.6(1)
123.4(1)
119.0(1)
110.3(1)
120.7(1)
C11AN6AN7
N7AN6AH6A
C12AN7AN6
C14AN8AC15
N7AC12AC13
N7AC12AH12
N5AC11AN6
N5AC11AS2
N6AC1AS2
N5
C19
C16
C18
C17
N8AC14AC13
N8AC14AH14
(2)
Fig. 1. The molecular structure of the compounds 1 and 2.
C2AN3AN2AC1
N2AN3AC2AC3
C4AC3AC2AN3
C10AC3AC2AN3
N3AN2AC1AN1
N3AN2AC1AS1
C4AN4AC5AC6
C5AN4AC4AC3
C2AC3AC4AN4
C10AC3AC4AN4
173.2(1)
177.8(1)
178.3(1)
À4.9(2)
1.0(2)
À178.2(1)
À177.1(1)
À0.7(2)
177.8(1)
0.3(2)
C2AC3AC10AC5
À177.2(1)
À178.6(1)
À178.5(1)
À179.7(1)
1.5(2)
C11AN6AN7AC12
N6AN7AC12AC13
N7AC12AC13AC14
N7AC12AC13AC20
N7AN6AC11AN5
N7AN6AC11AS2
C14AN8AC15AC20
C19AC20AC15AN8
C15AN8AC14AC13
The UV–visible studies of the compounds 1 and 2 were done in
DMSO solvent (Fig. 5). The Schiff bases show absorption in the
range greater than 400 nm in polar and nonpolar solvents [11–
13]. It is point out that the new band belongs to the keto-amine
form of the Schiff bases with OH group in ortho position to the imi-
no group in polar and nonpolar solvents in both acidic and basic
media [11–13,16–19]. The compound 1 showed no absorption
above 400 nm in DMSO. So the enol-imine tautomer is dominant
only in the DMSO solution for compound 1. In conclusion, UV–vis-
ible, 1H NMR and 13C NMR results show that the compound 1 exist
in the enol-imino form in DMSO solution.
0.7(2)
À178.5(1)
0.9(1)
À180.0(1)
À1.3(2)
[41,11]. The C@N bond which is accountable partially for the
existence enol-imine form can also be inferred from the FT-IR
spectra of compound 1. The
tions band overlap with each other in compound 1. The com-
pound
with strong band at 1286 cmÀ1 possesses highest
mCAOH, mCANH and mCANH2 vibra-
1
3.2. Crystallographic study
percentage of enol-imine tautomer due to the stabilization of
phenolic CAO bond [42].
Schiff base ligands consist of a variety of substituents with dif-
ferent electron-donating and electron-withdrawing groups, and
therefore may have interesting electro-chemical properties. The
Schiff bases compounds have been also under investigation during
last years because of their potential applicability in optical com-
munications and many of them have NLO behavior [43–45].
Conjugated organic molecules containing both donor and
acceptor groups are of great interest for molecular electronic
devices. Second-order NLO organic materials that contain stable
molecules with large molecular hyperpolarizabilities in noncentro-
symmetric packing are of great interest for device applications
[46], but according to a statistical study, an overwhelming majority
of achiral molecules crystallize centrosymmetrically.
The 1H NMR data for compound 1 show that the tautomeric
equilibrium favours the enol-imine in DMSO. The OH protons are
observed 11.20 and 9.78 ppm singlets for compound 1. The azome-
thine protons are observed as singlets 8.25 ppm singlets and
8.34 ppm singlets for 1 and 2 (Fig. 3). The amine protons resonate
at d = 9.78, 7.96 ppm and d = 11.57, 11.17, 7.43 ppm singlets,
respectively, for compounds 1 and 2. The phenyl protons of the
compounds 1 and 2 gave a multiplets at d = 7.76À6.25 ppm and
d = 8.24À7.02 ppm, respectively.
According to the 13C NMR spectra compounds 1 and 2 have 8 and
10 signals (Fig. 4). 13C NMR chemical shifts are given in Scheme 2 for
compounds 1 and 2.

230
M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
25.3
24
22
20
18
16
14
12
10
%T
7.5
4000.0
3000
2000
1500
1000
400.0
cm-1
(1)
29.1
28
26
24
22
20
18
16
14
12
10
8
%T
6
4
2
-0.4
4000.0
3000
2000
1500
1000
400.0
cm-1
(2)
Fig. 2. FT-IR spectra of the compounds 1 and 2.
The title molecules 1 and 2 are not planar. For 1, the two Schiff
molecules, however, are inclined at angle of 11.3(1)° and 4.2(1)°,
respectively.
base moieties (C1AC7, O1, O2) [planar with a maximum deviation
of 0.072(1) Å for the C7 atom] and (N1AN3, C8, S1) [planar with a
maximum deviation of 0.021(1) Å for the N2 atom] are inclined at
angle of 27.5(1)°. The compound 2 has two independent molecules
in asymmetric unit. The two planar phenyl rings bridged by the
C@N imino moiety in the two cyrstallographically independent
The crystal structures are stabilized by intramolecular and
intermolecular hydrogen bonding and their geometrical details are
listed Table 3 [42,47,48]. Intramolecular hydrogen bonds occur
between N3AH6. . .N1 [2.683(3) Å], O1AH8. . .N1 [2.683(2) Å] atoms
for the molecule 1 and N1AH1B. . .N3 [2.633(2) Å], N5AH5B. . .N7

M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
231
Fig. 3. 1H NMR spectra of the compounds 1 and 2.
[2.682(2) Å] atoms for the molecule 2 (Fig. 1). The sum of the Van der
Waals radius of the O and N atoms (3.07 Å) is significantly longer
than the intramolecular O. . .N hydrogen bond length [49]. There is
also intermolecular hydrogen bond between N2. . .S1 [3.400(2) Å],
N3. . .O1 [2.972(2) Å], and O2. . .S1 [3.290(2) Å] for the molecule 1
and N2 and S1 [3.401(1) Å], N4. . .S1 [3.355(1) Å], N8. . .S2
[3.399(2) Å], atoms of neighbouring molecules for the compound 2
(Fig. 6).
The thiosemicarbazone moiety in both compounds shows an E
configuration about C1AN2 and C2AN3 or C11AN6 and C12AN7.
The angles between the mean planes of the indoline and dihydr-
oxybenzylidene ring and thiosemicarbazone moiety present a
significant difference in the two compounds. The C@S bonds
[1.699(2) and 1.687(1) Å] have a length intermediate between a sin-
gle and double bond for 1 and 2. The sum of the valence angles
around atoms N2 and N3 and N6 and N5 or N2 and N1 indicate that
these atoms are sp2 hybridized. The N3AC8AN2 and N5AC11AN6 or
N1AC1AN2 angles [118.4(2) and 117.6(1) or 117.1(1)°] being nar-
row than N3AC8AS1 and N5AC11AS2 or N1AC1AS1 [122.4(1)
and 123.4(1) or 122.7(1)°], as observed in compounds 1 and 2. This
may be due to the intramolecular hydrogen bonding between the
free NH2 group and the imine nitrogen. The S1AC1AN2AN3
[À177.6(1)°] and N3AC2AC3AC4 [À178.1(2)°] torsion angles indi-
cate a trans conformation with respect to the thiosemicarbazone
moiety and the phenyl ring. The trans conformation adopted by
the side chain is evident from the values of the C1AN2AN3-AC2

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M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
Fig. 4. 13C NMR spectra of the compounds 1 and 2.
108.22
HO
128.80
S
141.17
112.22
N
C
102.72
177.41
160.91 C
N
H
NH2
158.45
OH
H
(1)
H
C
H
131.37
141.34
N
S
H
N
N
C
Fig. 5. UV–vis spectra of the compounds 1 and 2 in the DMSO, compound 1 (—),
compound 2 (- - -).
111.62
124.48
177.10
137.53
NH2
C@O bond distance indicates the presence of the keto form, with
a partial double bond character of the CO group (>C@O M C+AOÀ).
X-ray structure determinations reveal that the enol-imine tauto-
mer is favored over the keto-amine tautomer for the compound.
This is evident from the observed O1AC2 bond distance of
1.355(2) Å, which is consistent with the OAC single bond; similarly
the N1AC7 distance of 1.281(2) Å is also consistent with the N@C
double bonding. From the X-ray diffraction experiment and spec-
troscopic studies, we were only able to detect the existence of
the enol-imine tautomer for compound 1.
112.24
123.12
122.54
121.11
(2)
Scheme 2. 13C NMR Chemical shifts of the compounds in solution.
[172.8(2)°],
N2AN3AC2AC3
[À178.6(1)°],
N3AC2AC3AC4
[À178.1(2)°] and C2AC3AC4AC5 [À178.4(2)°] torsion angles.
In compound 1 CAN group seems to have a strong electron-
withdrawing character. Thus, the O1AC2 bond distance of
1.355(2) Å is also consistent with the CAO single bonding. The
In compound 2 the N2AC1 and N1AC1 bond distances are
1.332(2) and 1.330(2) Å while the N3AC2 distance is 1.280(2) Å.
This is consistent with the N2AC1 and N1AC1 single bond; simi-
larly is also consistent with the N3@C2 double bonding.

M. Yıldız et al. / Journal of Molecular Structure 919 (2009) 227–234
233
Table 3
Geometric details of intra- and inter-molecular hydrogen bonding for the title compounds
DAH. . .A (Å)
DAH
H. . .A (Å)
D. . .A (Å)
\DAH. . .A (°)
For compound 1
N3AH6. . .N1
O1AH8. . .N1
N2AH4. . .S1i
N3AH6. . .O1ii
O2AH9. . .S1iii
0.83(3)
0.87(4)
0.87(2)
0.83(3)
0.87(3)
2.37(3)
1.90(3)
2.56(2)
2.23(3)
2.43(3)
2.683(3)
2.683(2)
3.400(2)
2.972(2)
3.290(2)
103(2)
149(3)
163(2)
149(3)
171(3)
For compound 2
N1AH1B. . .N3
N5AH5B. . .N7
N2AH2A. . .S1iv
N4AH4A. . .S1v
N8AH8A. . .S2v
0.88(2)
0.86(2)
0.85(2)
0.83(2)
0.84(2)
2.31(2)
2.32(2)
2.56(2)
2.56(1)
2.60(2)
2.633(2)
2.682(2)
3.401(1)
3.355(1)
3.399(1)
101.9(2)
105.9(2)
171.2(2)
160.0(2)
158.9(2)
Note: D, donor; A, acceptor. Symmetry transformation used to generate equivalent atoms: (i) ½ À x, À1/2 À y, 1 À z; (ii) Àx, y, ½ À z; (iii) À1/2 + x, 3/2 + y, z; (iv) 1 À x, 1 À y,
Àz; (v) x, 1 + y, z.
Fig. 6. In the crystal structure a perspective view of the molecules 1 and 2, respectively. The intermolecular and intramolecular hydrogen bonds have been indicated by
dashed lines.
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