Synthesis and molecular structure investigation by DFT and X-ray diffraction of ARNO

Article abstract of DOI:10.1007/s10870-011-0165-9

We report here the synthesis of (Z)-5-(4-nitrobenzyliden)-3-N(2- ethoxyphenyl)-2-thioxo-thiazolidin-4-one (ARNO) compound. The crystal structure has been determined by X-ray diffraction. The compound crystallizes in the triclinic system with space group P

Full text of DOI:10.1007/s10870-011-0165-9

J Chem Crystallogr (2011) 41:1729–1736
DOI 10.1007/s10870-011-0165-9
ORIGINAL PAPER
Synthesis and Molecular Structure Investigation by DFT
and X-Ray Diffraction of ARNO
•
Nadia Benhalima Khaled Toubal
•
•
Abdelkader Chouaih Giuseppe Chita
•
•
Sabino Maggi Ayada Djafri Fodil Hamzaoui
•
Received: 30 March 2011 / Accepted: 29 June 2011 / Published online: 14 July 2011
Ó Springer Science+Business Media, LLC 2011
Abstract We report here the synthesis of (Z)-5-(4-nitro-
benzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one
(ARNO) compound. The crystal structure has been deter-
mined by X-ray diffraction. The compound crystallizes in
Keywords Structure ꢀ X-ray diffraction ꢀ Thiazolidin-4-
one ꢀ Ab initio calculations ꢀ ARNO
ꢀ
the triclinic system with space group P1 and cell parameters:
Introduction
˚
a = 9.1289(19), b = 9.3717(7), c = 12.136(3) A,a = 102.133
3
˚
Research on new materials exhibiting nonlinear optical
(NLO) behavior continues to be of primary interest for
basic research as well as for industrial applications. The
research on new materials with NLO properties for tele-
communications and optoelectronics is directly related to
the determination of their three-dimensional structure.
Polymers represent a large family of interesting materials
for nonlinear optics applications. In particular, compounds
derived from thiazoles have recently received particular
attention due to their NLO properties [1–3].
(11)°, b = 90.99(2)°, c = 117.165(9)°, V = 895.4(3) A
and Z = 2. The structure has been refined to a final R = 0.05
for 2591 observed reflections. The refined structure was
found to be significantly non planar. The molecule exhibits
intermolecular hydrogen bond of type C–H_O and
C–H_S. ab initio calculations were also were performed at
Hartree–Fock and density functional theory levels. The full
HF and DFT geometry optimization was carried out using
LANL2DZ, 6-31G* and B3LYP/6-31?G** basis sets. The
optimized geometry of the title compound was found to be
consistent structure determined by X-ray diffraction. The
minimum energy ofgeometrical structure is obtained by using
level HF/LANL2DZ basis sets.
Density functional theory (DFT) is presently considered
one of the most successful models in the world of compu-
tational chemistry since it yields accurate results for several
physico-chemical properties, especially when hybrid DFT is
used. The hybrid DFT functional offers reliable information
for the excited state properties of small molecules [4], donor
and acceptor systems [5], as well as metal complexes [6].
In this paper we present a structural study of the (Z)-5-
(4-nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazo-
lidin-4-one compound, hereafter known as ARNO (to avoid
rewriting the IUPAC name every time), by single-crystal
X-ray diffraction to determine the most stable conformation
in the crystalline state. To gain a better picture of the con-
formational profile of the given compound, we have also
performed theoretical calculations using classical ab initio
methods based on self-consistent field-molecular-orbital
Hartree–Fock (HF) theory and Density Functional Theory
(DFT) with the LANL2DZ, 6-31G* and 6-31?G** basis
sets.
N. Benhalima ꢀ A. Chouaih (&) ꢀ F. Hamzaoui
Laboratoire de Structure, Elaboration et Applications des
´
´
´
´
Materiaux Moleculaires (SEA2M), Departement de Genie
´ ´
´
des Procedes, Faculte des Sciences et de la Technologie,
University of Mostaganem, 27000 Mostaganem, Algeria
e-mail: achouaih@gmail.com
K. Toubal ꢀ A. Djafri
`
Laboratoire de Synthese Organique Appliquee (LSOA),
Departement de Chimie, Faculte de Sciences,
´
´
´
´
University of Oran–Es-Senia, 31000 Oran, Algeria
G. Chita ꢀ S. Maggi
CNR-IC Institute of Crystallography, Via Amendola 122/O,
70126 Bari, Italy
123

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J Chem Crystallogr (2011) 41:1729–1736
The results from X-ray diffraction have been compared
124.46, 128.35, 129.12, 129.77, 130.95, 131.63, 139.44,
147.96, 154.21, 167.19 (C=S), 191.65 (C=O).
to those obtained from ab initio DFT and HF calculations,
finding a good agreement with the structure determined
from the single-crystal measurements.
X-Ray Structure Determination
A yellow prismatic crystal with approximate dimensions of
0.20 9 0.15 9 0.10 mm was selected for data collection.
The X-ray diffraction data were collected on a Kappa CCD
Nonius diffractometer. Reflection data were measured at
298 K using graphite monochromated Mo Ka radiation
Experiment and Computational Methods
Synthesis
˚
The title compound was prepared by reaction of N-aryl-
rhodanine (0.01 M), aldehyde (0.01 M), 5 mL of acetic
acid and sodium acetate (0.02 M) in a 150 mL boiling
flask. Then 2 mL of triethylamine are added to this mix-
ture. The system is refluxed for 4 h, forming a yellow solid.
The crystals obtained are filtered and recrystallized in
ethanol. Synthesis of the compound was performed as
follows (Fig. 1).
(k = 0.71073 A). Intensities for 4080 reflections were
measured with indices -11 \ h \ 11, -12 \ k \ 11,
-15 \ l \ 15. The structure was determined by consider-
ing 2591 reflections with I ꢁ 4rðIÞ. The structure was
solved by direct methods using the SHELXS-97 [7].
A Fourier synthesis revealed the complete structure, which
was refined by full-matrix least squares. All non-H atoms
refined anisotropically. The positions of the H atoms bon-
ded to C atoms were calculated. The H atoms were located
from a difference Fourier map and included in the refine-
ment with the isotropic temperature factor of the carrier
atom. The final least-squares cycle using SHELXL-97 [8]
gave R = 0.05 for the observed reflections with S = 0.95,
Spectral Analysis
All reagents and solvents for synthesis and spectroscopic
studies were commercially available and used as received
without further purification. The IR spectra was recorded
on a JASCO 4200 FT-IR spectrometer as a KBr pellet. The
1H and 13C NMR spectra were measured in CDCl3 with a
BRUKER Ac DPX-200 (300 MHz) spectrometer at 25 °C.
3
3
˚
˚
(Dq)min = -0.425 e/A , (Dq)max = 0.219 e/A . An ORTEP
[9] view of the molecular structure with the atomic num-
bering is shown in Fig. 2. Atomic scattering factors for
heavy atoms were taken from International Tables for
X-ray Crystallography [10] while the factors for H were
Spectral Data of ARNO
(Z)-5-(4-nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-
thiazolidin-4-one (2g, yield 75%, yellow solid, M.p.
210 °C). IR (KBr, cm-1): 3407 broad band, 3035 (C–N),
1710 (C=O),1256 (C=S).
1H NMR, (CDCl3, 300 MHz) d (ppm) J (Hz): 1, 42 (t,
3H, –O–CH2–CH3, J3 = 6.97), 4.06 (oct, 1H, J2 = 2.2,
J3 = 6.95) (–O–CH2–CH3), 4.11 (oct, 1H, J2 = 2.2;
J3 = 6.95), (–O–CH2–CH3), 7.53–7.08 (m, 4H), 7.71 (d,
2H, J = 8.75) 7.79 (s, 1H, –CH=C–), 8.53 (d, 2H,
J = 8.80).
Fig. 2 General view of molecule with atomic numbering scheme
(thermal ellipsoids drawn at 50% probability). H atoms are shown as
small spheres of arbitrary radii
13C NMR, (CDCl3, 300 MHz) d (ppm): 14.17 (O–CH2–
CH3), 64.43 (–O–CH2–CH3), 113.48, 121.00, 123.26,
Fig. 1 Preparation and chemical structure of (Z)-5-(4-nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one (ARNO). Reagents and
conditions: (a) ClCH2CO2H, 70 °C; (b) NO2C6H4CHO, CH3COOH, CH3COONa, 90 °C
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J Chem Crystallogr (2011) 41:1729–1736
1731
Table 1 Crystal data and structure refinement details
Compound
ARNO
C18H14O4N2S2
Empirical formula
CCDC reference no.
Formula weight
805892
386.45
Crystal size (mm)
Temperature (K)
0.20 9 0.15 9 0.10
298(2)
ꢀ
Triclinic, P1
Crystal system, space group
Unit cell dimensions
˚
a (A)
9.1289(19)
9.3717(7)
12.136(3)
102.133(11)
90.99(2)
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
Fig. 3 A perspective view of the crystal packing in the unit cell
117.165(9)
0.71073
˚
Results and Discussion
Wavelength (A)
3
˚
Volume (A )
895.4(3)
Z, calculated density (mg/m3) 2/1.433
Description of the Crystal Structure
F(000)
400
A general view of the molecule with atomic labeling
(thermal ellipsoids are drawn at 50% probability) is shown
in Fig. 2. Figure 3 shows a perspective view of the crystal
packing in the unit cell. Selected bond lengths, bond angles
and torsion angles for all non-hydrogen atoms by X-ray
diffraction are listed in Tables 2, 3, and 4, together with the
calculated parameters, respectively. The average values of
bond distances and angles in the two benzene rings for both
experimental and calculated are in good agreement with
literature values. The three C–S distances, S1–C8, S1–C10
h range for data collection
Limiting indices
5.01–27.50
-11 B h B 11, -12 B k B 11,
-15 B l B 15
Reflections collected/unique
4080/2591
Full-matrix least-squares on F2 data
Refinement method
Parameters
Goodness of fit on F2
227
0.935
Final R indices ½F0 [ 4rðF0Þꢂ
R1
0.0523
0.1316
wR2
˚
and S2 = C10 [1.753(3), 1.753(3) and 1.626(3) A],
R indices (all data)
respectively in the thiazole ring have values intermediate
˚
between those reported for C(Sp3)–S single [1.81 A] and
˚
double [1.61 A] bonds [10]. The mean value of bond
R1
0.0994
0.1607
wR2
angles in thiazole ring is 107.96(2)°. The crystal structure
exhibits intermolecular interaction of the type C–H_O and
C–H_S in which C atoms (C2, C4, C5, C7, C13 and C14)
act as donors and O (O1, O2 and O3) and S1 atoms acts as
acceptors. In the crystalline state, these intermolecular
interactions stabilize the crystal structure. The geometry of
the hydrogen-bonded interactions is listed in Table 5.
Figure 4 shows some hydrogen bonds in the crystal. All
bond angles C–C–C, C–N–C and C–C–N are close to 120°,
indicating that the p electrons in the ARNO molecule are
delocalized.
those of Stewart et al. [11]. The details of crystal data and
refinement are given in Table 1.
Computational Method
For calculations involving hydrogen-bonding interaction
systems it is very important to select an appropriate
method, and carefully considering and evaluating its
accuracy and speed of calculation. DFT methods are fast
and can be used to compute mid-sized and even large
molecular systems. In this work, full geometry optimiza-
tion has been performed using the GAUSSIAN03 package
[12] and the Gauss-View molecular visualization program
[13], at the Becke3-parameter hybrid exchange functions
and Lee-Young–Parr correlation functional (B3LYP) level
[14, 15] and HF theory [16], using the LANL2DZ, 6-31G*
and 6-31?G** basis sets by the Berny method [17, 18].
Crystallographic data (excluding structure factors) for
the structure reported in this article have been deposited
with the Cambridge Crystallographic Data Centre as sup-
plementary publication number CCDC 805892.1
1
Copies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Fax: ?44 1223
336033; e-mail: deposit@ccdc.cam.ac.uk.
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J Chem Crystallogr (2011) 41:1729–1736
B3LYP
Table 2 Bond distances for
non-hydrogen atoms by X-ray
and theoretical calculations
(e.s.d.’s are given in
˚
Bond distances (A) X-ray
HF
LANL2DZ 6-31G* 6-31?G** LANL2DZ 6-31G* 6-31?G**
1.753(3) 1.809
parenthesis)
S1–C10
S1–C8
1.760
1.761
1.629
1.193
1.193
1.186
1.340
1.410
1.458
1.362
1.394
1.432
1.380
1.395
1.383
1.382
1.382
1.394
1.474
1.327
1.491
1.376
1.394
1.386
1.381
1.388
1.386
1.514
1.760
1.760
1.629
1.194
1.194
1.187
1.339
1.412
1.461
1.364
1.393
1.433
1.382
1.396
1.383
1.382
1.383
1.395
1.474
1.328
1.493
1.377
1.395
1.388
1.383
1.389
1.388
1.514
1.846
1.820
1.678
1.280
1.280
1.244
1.388
1.471
1.474
1.388
1.424
1.447
1.398
1.423
1.406
1.406
1.399
1.422
1.462
1.361
1.492
1.398
1.414
1.407
1.406
1.407
1.409
1.524
1.785
1.761
1.640
1.231
1.231
1.213
1.356
1.432
1.470
1.378
1.412
1.437
1.387
1.413
1.394
1.394
1.389
1.412
1.455
1.353
1.492
1.389
1.408
1.395
1.393
1.397
1.399
1.518
1.782
1.761
1.640
1.232
1.232
1.215
1.357
1.435
1.471
1.380
1.410
1.437
1.389
1.414
1.395
1.395
1.390
1.413
1.456
1.354
1.493
1.389
1.408
1.397
1.395
1.398
1.401
1.518
1.753(3) 1.807
1.626(3) 1.667
1.223(3) 1.238
1.227(4) 1.239
1.211(3) 1.216
1.364(3) 1.368
1.447(4) 1.447
1.473(4) 1.461
1.384(3) 1.371
1.398(4) 1.403
1.439(3) 1.438
1.383(4) 1.388
1.392(4) 1.404
1.382(4) 1.390
1.379(4) 1.390
1.394(4) 1.389
1.390(4) 1.404
1.472(4) 1.472
1.331(4) 1.334
1.494(4) 1.487
1.373(4) 1.383
1.404(4) 1.397
1.390(4) 1.395
1.378(5) 1.392
1.380(5) 1.396
1.399(4) 1.393
1.493(6) 1.519
S2–C10
O1–N1
O2–N1
O3–C9
O4–C16
O4–C17
N1–C3
N2–C10
N2–C9
N2–C11
C1–C2
C1–C6
C2–C3
C3–C4
C4–C5
C5–C6
C6–C7
C7–C8
C8–C9
C11–C12
C11–C16
C12–C13
C13–C14
C14–C15
C15–C16
C17–C18
Geometry Optimization
experimental and calculated bond lengths calculated at
the HF level with 6-31G(d) basis set does not exceed
˚
0.037 A (O4–C17), whereas in the case of B3LYP with
The ground state geometries were optimized by the
Hartree Fock and DFT levels of theory, using
LANL2DZ, 6-31G(d) and 6-31?G(d,p) basis sets. The
optimized structure of ARNO is illustrated in Fig. 5 and
the corresponding main geometrical parameters (bonds
lengths, bond angles and torsion angles) are listed in
Tables 2, 3, and 4, as we can see there is a good
agreement between the calculated and the experimental
values. We also checked the effect of basis sets on the
calculations. The largest deviation between X-ray data
and theoretical calculations at the HF/LANL2DZ level is
same basis set, the largest difference between the
˚
observed and the calculated values is about 0.03 A. The
bond angles for HF/631G(d) calculations are very close
to the experimental values (Table 3), and the maximum
difference is about 2.42°. For DFT with 6-31G(d) basis
the bond angle difference does not exceed 2.67°. The
HF/6-31?G(d,p) and B3LYP/6-31?G(d,p) results deviate
˚
in the range from 0.001 to 0.035 A (O4–C17) and 0.001
˚
to 0.029 A for the bond lengths, and from 0.04° to 2.57°
(C16–O4–C17) and 0.04° to 2.48° (C8–C7–C6) for the
bond angles, respectively. X-ray structure of the title
compound is compared with its optimized counterparts
(see Fig. 6).
˚
the S1–C10 distance, around 0.06 A, and the C16–O4–
C17 angle, which is larger than 3°. The B3LYP/
LANL2DZ results deviate in the range from 0.001 to
˚
0.9 A for bond lengths, and from 0.02° to 2.56° (C8–
C7–C6) for bond angles. The difference between the
In summary, the optimized bond lengths and bond
angles obtained using the DFT method are in good
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J Chem Crystallogr (2011) 41:1729–1736
1733
Table 3 Bond angles for non-
Bond angles (°) X-ray
HF
B3LYP
hydrogen atoms by X-ray and
theoretical calculations (e.s.d.’s
are given in parenthesis)
LANL2DZ 6-31G* 6-31?G** LANL2DZ 6-31G* 6-31?G**
C10–S1–C8
C16–O4–C17
O1–N1–O2
O1–N1–C3
O2–N1–C3
C10–N2–C9
C10–N2–C11
C9–N2–C11
C2–C1–C6
93.12(13)
118.0(2)
124.2(3)
118.3(3)
117.5(3)
117.1(2)
122.1(2)
120.8(2)
121.4(3)
118.6(3)
122.1(3)
119.6(3)
118.3(3)
118.0(3)
121.6(3)
118.2(3)
123.1(3)
118.7(3)
128.8(3)
121.8(3)
128.5(2)
91.65
121.95
123.71
118.18
118.11
118.15
122.02
119.43
121.34
118.35
122.03
118.97
119.00
118.95
120.69
118.64
124.63
116.72
131.44
120.03
130.89
92.44
120.42
124.85
117.60
117.56
117.36
122.58
119.77
121.04
118.52
121.99
119.00
119.01
118.86
120.66
118.91
123.28
117.79
129.42
119.80
130.88
109.28
124.05
125.75
110.19
127.74
110.69
121.57
121.16
120.35
118.48
120.14
118.94
121.27
119.78
125.16
116.13
118.70
107.43
92.47
120.57
124.88
117.58
117.54
117.28
122.55
119.87
121.06
118.48
122.04
118.97
118.99
118.85
120.66
118.90
123.41
117.68
129.48
119.79
130.94
109.23
124.04
125.69
110.26
127.61
110.72
121.66
121.18
120.31
118.50
120.16
118.92
121.25
119.77
125.11
116.18
118.71
107.58
91.43
119.20
123.78
118.15
118.08
118.41
121.93
119.46
121.57
118.43
121.86
119.07
119.08
119.03
120.91
118.21
124.70
117.09
131.36
120.02
130.04
109.94
123.32
125.70
110.97
128.43
109.22
122.35
121.00
120.62
118.37
119.92
119.34
120.97
119.68
125.04
115.88
119.08
106.92
92.85
118.92
124.79
117.63
117.58
117.51
122.42
119.85
121.56
118.55
121.79
119.11
119.09
119.06
121.00
118.03
124.62
117.35
131.47
119.18
131.03
109.79
123.70
126.17
110.13
128.11
109.68
122.21
121.13
120.42
118.43
120.0
92.90
119.14
124.57
117.74
117.68
117.43
122.26
120.14
121.58
118.56
121.77
119.13
119.10
119.06
121.03
118.01
124.64
117.35
131.28
119.45
130.83
109.71
123.73
126.05
110.21
127.85
109.72
122.43
121.12
120.25
118.62
120.05
119.17
121.11
119.87
125.25
116.08
118.66
107.59
C3–C2–C1
C2–C3–C4
C2–C3–N1
C4–C3–N1
C3–C4–C5
C6–C5–C4
C5–C6–C1
C5–C6–C7
C1–C6–C7
C8–C7–C6
C7–C8–C9
C7–C8–S1
C9–C8–S1
109.47(19) 109.08
O3–C9–N2
O3–C9–C8
N2–C9–C8
N2–C10–S2
N2–C10–S1
S2–C10–S1
C12–C11–C16
C12–C11–N2
C16–C11–N2
C11–C12–C13
C14–C13–C12
C13–C14–C15
C14–C15–C16
O4–C16–C15
O4–C16–C11
C15–C16–C11
O4–C17–C18
122.8(3)
127.2(3)
110.0(2)
128.0(2)
123.54
125.27
111.19
127.90
110.13(19) 109.89
121.91(17) 122.21
121.4(3)
120.9(2)
117.7(2)
119.5(3)
119.7(3)
121.4(3)
119.6(3)
125.7(3)
115.9(2)
118.4(3)
106.9(3)
121.12
120.92
117.96
119.86
119.22
121.02
119.54
124.90
115.86
119.24
107.03
119.22
121.13
119.87
125.36
115.98
118.65
107.42
agreement with the corresponding X-ray structural
parameters. It is worth noting that some of the optimized
torsion angles have slightly different values from the cor-
responding experimental ones, due to the fact that the
theoretical calculations consider only isolated molecules in
the gaseous phase while the experimental results refer to
molecules in the crystal environment.
Conclusions
In this study, we have synthesized the (Z)-5-(4-nitroben-
zyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one
(ARNO) compound and its crystal structure was deter-
mined by X-ray diffraction. This compound belongs to
ꢀ
the centrosymmetric space group P1. From the crystal
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J Chem Crystallogr (2011) 41:1729–1736
Table 4 Torsion angles involving non H-atoms by X-ray and theoretical calculations (e.s.d.’s are given in parenthesis)
Torsion angles (°)
X-ray
HF
B3LYP
LANL2DZ
6-31G*
6-31?G**
LANL2DZ
6-31G*
6-31?G**
C6–C1–C2–C3
C1–C2–C3–C4
C1–C2–C3–N1
O1–N1–C3–C2
O2–N1–C3–C2
O1–N1–C3–C4
O2–N1–C3–C4
C2–C3–C4–C5
N1–C3–C4–C5
C3–C4–C5–C6
C4–C5–C6–C1
C4–C5–C6–C7
C2–C1–C6–C5
C2–C1–C6–C7
C5–C6–C7–C8
C1–C6–C7–C8
C6–C7–C8–C9
C6–C7–C8–S1
-1.3(5)
-0.2
-0.05
-179.9
-0.09
179.9
-0.92
-0.26
-179.7
-0.38
179.6
-179.8
0.18
-0.88
-0.26
-179.7
-0.53
179.5
0.02
0.02
-0.20
-0.04
-179.9
0.05
-0.12
0.01
0.4(5)
-179.3(3)
-18.1(4)
161.5(3)
162.2(3)
-18.2(4)
0.4(5)
-179.9
0.02
-179.9
0.08
-179.99
-179.98
0.01
-179.97
-179.8
0.17
-179.9
-179.9
0.12
-179.96
0.02
180.0
0.00
0.16
0.68
0.68
-0.03
179.96
0.01
0.16
0.07
-179.9(3)
-0.3(5)
-0.5(5)
-179.8(3)
1.3(5)
-179.97
-0.01
-0.23
-179.95
0.35
-179.9
0.07
-179.9
0.03
-179.98
-0.04
-0.19
-179.99
0.31
-179.99
-0.05
-0.05
-179.89
0.14
-1.21
179.9
1.65
-1.12
-179.98
1.55
0.03
-179.93
-0.04
179.92
0.17
-179.3(3)
21.0(5)
-179.9
-4.77
175.5
-179.4
-29.13
151.98
-178.7
-1.38
-177.3
0.23
-179.5
-28.14
152.98
-178.6
-1.24
-177.5
0.07
-179.88
-3.62
176.58
-179.96
-0.51
-179.48
0.01
179.99
-1.95
178.21
-179.8
-0.40
-179.5
-0.02
-178.9
-3.48
1.61
159.7(3)
-177.4(3)
-3.6(5)
-170.7(3)
3.8(2)
-179.79
179.90
-0.01
179.76
-0.16
-179.0
-4.08
1.61
-179.8
-0.32
-179.8
-0.29
-178.95
-5.95
1.87
C10–S1–C8–C7
C10–S1–C8–C9
C10–N2–C9–O3
C11–N2–C9–O3
C10–N2–C9–C8
C11–N2–C9–C8
C7–C8–C9–O3
S1–C8–C9–O3
178.2(3)
-3.7(4)
-0.4(3)
177.8(2)
-6.2(5)
178.9(3)
172.3(3)
-2.6(3)
-176.4(2)
5.5(4)
-178.5
-4.44
2.36
-178.7
-4.74
2.15
-178.34
-3.57
2.14
174.9
176.4
-2.72
179.4
176.4
-1.41
178.3
4.42
176.1
176.5
0.02
176.90
-1.07
179.37
178.43
-1.12
178.21
3.59
177.0
-0.29
-179.6
178.9
-2.43
179.6
-0.80
179.67
178.70
0.83
179.9
179.4
-0.70
178.4
3.58
C7–C8–C9–N2
S1–C8–C9–N2
176.7
-0.46
178.3
-1.18
178.4
C9–N2–C10–S2
C11–N2–C10–S2
C9–N2–C10–S1
C11–N2–C10–S1
C8–S1–C10–N2
C8–S1–C10–S2
C10–N2–C11–C12
C9–N2–C11–C12
C10–N2–C11–C16
C9–N2–C11–C16
C16–C11–C12–C13
N2–C11–C12–C13
C11–C12–C13–C14
C12–C13–C14–C15
C13–C14–C15–C16
C17–O4–C16–C15
C17–O4–C16–C11
C14–C15–C16–O4
C14–C15–C16–C11
178.8
5.46
4.64
3.48
3.2(3)
-2.07
-174.9
1.27
-2.19
-176.0
1.04
-2.10
-175.8
1.08
-1.70
-176.5
0.99
-2.12
-176.74
1.13
-1.62
-176.9
0.88
-174.91(19)
-4.0(2)
175.66(19)
-82.7(3)
99.2(3)
-179.0
-89.9
97.4
-179.4
-91.40
94.88
89.57
-84.1
-0.33
-179.3
0.13
-179.4
-91.56
94.86
-179.1
-87.3
97.98
93.61
-81.1
-0.29
-179.4
0.18
-179.17
-91.15
94.36
-179.47
-91.84
93.00
98.4(3)
90.8
89.47
90.01
89.32
-79.7(3)
-0.5(5)
-179.4(13)
-1.3(5)
1.2(5)
-81.9
-0.33
-179.7
0.13
-84.11
-0.39
-179.33
0.16
-84.49
-0.31
-179.12
0.15
-85.84
-0.41
-179.2
0.15
0.10
0.07
0.07
0.03
0.05
0.09
0.6(5)
-0.13
1.95
-0.09
2.55
-0.09
1.68
-0.13
-0.50
179.5
-179.96
0.02
-0.09
0.93
-0.08
0.02
-3.1(4)
177.4(3)
178.1(3)
-2.4(4)
-178.3
179.7
-177.6
179.7
-0.10
-178.4
179.79
-0.12
-179.11
179.89
-0.06
-179.96
179.85
-0.17
-0.06
123

J Chem Crystallogr (2011) 41:1729–1736
1735
Table 4 continued
Torsion angles (°)
X-ray
HF
B3LYP
LANL2DZ
6-31G*
6-31?G**
LANL2DZ
6-31G*
6-31?G**
C12–C11–C16–O4
N2–C11–C16–O4
C12–C11–C16–C15
N2–C11–C16–C15
C16–O4–C17–C18
-178.1(3)
0.8(4)
-179.5
-0.15
0.29
-179.5
-0.53
0.3
-179.6
-0.60
0.36
-179.8
-0.71
0.19
-179.70
-0.86
0.26
-179.60
-0.77
0.42
2.4(4)
178.7(2)
-176.1(3)
179.7
179.01
179.3
178.5
179.3
179.0
179.3
179.10
179.18
179.25
179.92
-179.8
Table 5 Geometry of the C–H_O and C–H_S hydrogen bonds in
ARNO crystal by X-ray diffraction
˚
˚
˚
D–H_A
D–H (A) H_A (A) D_A (A) D–H_A (°)
C2–H2_O1
C4–H4_O2
C5–H5_S1
C7–H7_O3
C4–H4_O3i
C7–H7_O3ii
0.93(3)
0.93(4)
0.93(3)
0.93(4)
0.93(4)
0.93(4)
2.49(3)
2.45(2)
2.55(1)
2.61(2)
2.93(3)
2.59(3)
2.80(3)
2.76(3)
2.761(5)
2.724(4)
3.198(3)
2.936(4)
3.278(6)
3.267(4)
3.385(5)
3.373(5)
96.5(3)
96.9(3)
127.0(2)
101.1(2)
103.4(3)
129.5(2)
121.9(3)
124.0(2)
C13–H13_O2iii 0.93(3)
C14–H14_O2iii 0.93(4)
Symmetry code: (i) x - 1, ?y, ?z; (ii) -x ? 2, -y, -z; (iii) x ? 2,
?y ? 1, ?z
Fig. 6 Atom-by-atom superimposition of the structures calculated
(dashed line) [A = HF, B = B3LYP] over the X-ray structure (solid
line) for the title compound
structure, this compound seems to be potentially useful for
non-linear optical applications. The results from X-ray
diffraction were assessed by DFT and HF ab initio calcu-
lations using three different basis set LANL2DZ, 6-31G*
and B3LYP/6-31?G**. The two ab initio computational
methods gave very similar results, which are very close to
those of X-ray data.
In a forthcoming paper, we will present a spectroscopic
study and other theoretical calculations on the same com-
pound in order to evaluate the main physico-chemical prop-
erties, such as the atomic charge distribution and the dipole
moment, necessary to assess the efficiency and applicability
of the title compound in the nonlinear optics field.
Fig. 4 View of the two H-bonds C7–H7_O3 in the ARNO crystal
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