Search for molecular crystals with NLO properties: 5-Sulfosalicylic acid with nicotinamide and isonicotinamide

Article abstract of DOI:10.1016/j.molstruc.2014.03.060

Two proton transfer hydrogen-bonded complexes of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid, 5-SSA) with the aromatic amides: nicotinamide (NA) and isonicotinamide (INA), are characterized by X-ray diffraction and spectroscopic studies. In the crystal structures of nicotinamidium 3-carboxy-4-hydroxybenzenesulfonate, 1, and isonicotinamidium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, 2, the ions are linked into three dimensional frameworks by a combination of O-H?O, N-H?O and C-H?O hydrogen bonds and cation-anion π-π stacking interactions. The hydrogen-bonding behavior of the pyridine N atom is different in the two crystals, bonding to a sulfonate O atom of anion in 2 but to a carbonyl O atom of cation in 1. The complex 1 shows relatively efficient second harmonic frequency generation.

Full text of DOI:10.1016/j.molstruc.2014.03.060

Journal of Molecular Structure 1068 (2014) 77–83
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Search for molecular crystals with NLO properties: 5-Sulfosalicylic acid
with nicotinamide and isonicotinamide
b
c
c
Iwona Bryndal a, , Isabelle Ledoux-Rak , Tadeusz Lis , Henryk Ratajczak
⇑
a Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology, Faculty of Engineering and Economics, University of Economics, 180/120 Komandorska,
54-435 Wrocław, Poland
b Laboratoire de Photonique Quantique et Moleculaire, Institut d‘Alembert, Ecole Normal Superieure de Cachan, 61 av. du President Wilson, 94235 Cachan, France
c Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, 50-383 Wrocław, Poland
g r a p h i c a l a b s t r a c t
h i g h l i g h t s
ꢀ
Novel salts 1–2 of nicotinamide and
isonicotinamide with 5-sulfosalicylic
acid are prepared.
ꢀ
These salts are characterized by X-ray
and IR studies as well as SGH
measurements.
ꢀ
ꢀ
Salts 1 and 2 crystallize in Pca21 and
Pbca space groups, respectively.
Crystal structure analysis revealed
different structural hydrogen-bonded
motifs to distinguish 1 and 2.
Salt 1 shows relatively efficient
second harmonic frequency
generation.
ꢀ
a r t i c l e i n f o
a b s t r a c t
Article history:
Two proton transfer hydrogen-bonded complexes of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzene-
sulfonic acid, 5-SSA) with the aromatic amides: nicotinamide (NA) and isonicotinamide (INA), are
characterized by X-ray diffraction and spectroscopic studies. In the crystal structures of nicotinamidium
3-carboxy-4-hydroxybenzenesulfonate, 1, and isonicotinamidium 3-carboxy-4-hydroxybenzenesulfonate
monohydrate, 2, the ions are linked into three dimensional frameworks by a combination of O–HÁ Á ÁO,
Received 15 January 2014
Received in revised form 25 March 2014
Accepted 25 March 2014
Available online 1 April 2014
N–HÁ Á ÁO and C–HÁ Á ÁO hydrogen bonds and cation–anion
p–p stacking interactions. The hydrogen-bonding
Keywords:
behavior of the pyridine N atom is different in the two crystals, bonding to a sulfonate O atom of anion in 2
but to a carbonyl O atom of cation in 1. The complex 1 shows relatively efficient second harmonic
frequency generation.
Nicotinamide
Isonicotinamide
5-Sulfosalicylic acid
Hydrogen bonds
Crystal structure
SGH
Ó 2014 Elsevier B.V. All rights reserved.
Introduction
(NLO) crystals [2–4]. The discovery of new materials exhibiting
nonlinear optical properties in the combination with desirable
The last decades have witnessed a tremendous interest in
molecular materials and soft condensed matter [1]. An important
class of molecular materials is the nonlinear optically active
physical properties (optical transparency, thermal, optical and
mechanical stability) continues to be an important goal in
nonlinear optics. Essential applications of these materials lie in
the areas of optical signal processing, as well as storage and other
information processing tasks [4].
Relatively recently, a very efficient new approach has been
developed for obtaining new molecular materials with NLO
⇑
Corresponding author. Tel.: +48 71 368 0299; fax: +48 71 368 0292.
E-mail addresses: isai@o2.pl, ibryndal@ue.wroc.pl (I. Bryndal).
http://dx.doi.org/10.1016/j.molstruc.2014.03.060
0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

78
I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
Table 1
properties [5,6]. The method is based on acid–base hydrogen bond
interactions and molecular recognition. A molecular crystal is build
from an inorganic or organic acid and an organic base (chromophore
molecule). It is assumed that the acid part is responsible for favor-
able mechanical and thermal properties, due to strong hydrogen
bond interactions which stabilize the crystal lattice [6]. The organic
part, due to its relatively high hyperpolarizability value, is mainly
responsible for nonlinear optical properties of the crystal [4]. Per-
haps it would be interesting to notice that the hydrogen bond also
plays a important role in the creation of non-centrosymmetric
structures of crystals [7] and contributes to the molecular qua-
dratic hyperpolarizability of such systems [8–11].
We previously characterized the molecular complexes of
amides (nicotinamide and isonicotinamide) with 3-nitrophenol
[12]. Both complexes do not involve proton transfer, but reveal
features to distinguish the co-crystals. The primary direct
N(pyridine)Á Á ÁH–O(hydroxyl) hydrogen bonding is found in the
isonicotinamide co-crystal. On the contrary, the nicotinamide
co-crystal contains O(hydroxyl)–HÁ Á ÁO(carboxyl) and N(amine)–
HÁ Á ÁN(pyridine) hydrogen bonds and also shows relatively efficient
second harmonic frequency generation [12].
In the present paper we have replaced 3-nitrophenol by very
strong 5-sulfosalicylic acid which contains five O–H bonds in three
substituent groups (the sulfonic, carboxylic and phenolic groups),
and it may give mono-, di- or tri-anionic ligand species through
deprotonation, and may be useful to build potentially optical mate-
rials. Furthermore with deprotonation of sulfonic group, the three
oxygen atoms provide an additional set of potential acceptor sites
for hydrogen bonding associations. With these adducts three-
dimensional hydrogen bonding network are common, although
Crystal data and structure refinement for salts 1 and 2.
1
2
Empirical formula
Moiety formula
Formula weight (g)
Temperature (K)
k (Å)
Crystal system
Space group
Unit cell dimensions (Å, °)
C
13H12N2O7S
C13H14N2O8S
C6H7N2O+ÁC7H5O6SÀ C6H7N2O+ÁC7H5O6SÀÁH2O
340.31
358.32
90(2)
100(2)
0.71073
Orthorhombic
Pca21
a = 16.141(7)
b = 6.720(2)
c = 12.628(5)
1369.7(9)
4
0.71073
Orthorhombic
Pbca
a = 13.457(3)
b = 12.651(3)
c = 16.790(4)
2858.4(12)
8
Volume (Å3)
Z
Absorption coefficient
0.279
0.277
(mmÀ1
)
Calculated density
(mg mÀ3
F(000)
Crystal size (mm)
h range (°)
1.650
1.665
)
704
1488
0.45 Â 0.25 Â 0.14
0.26 Â 0.24 Â 0.09
2.86–28.78
À17 6 h 6 15
À17 6 k 6 10
À21 6 l 6 13
8385
4.9–35.0
Index ranges
À26 6 h 6 20
À9 6 k 6 8
À20 6 l 6 14
15,436
4257, 0.044
3097
Collected reflections
Unique reflections, Rint
Observed reflections
3303, 0.022
2782
[I > 2r(I)]
Parameters
223
1.001
0.0389
0.0726
238
1.029
0.0337
0.0870
Goodness-of-fit on F2
R1 [I > 2
wR2 [all data]
r
(I)]
Largest diff. peak and hole
0.37 and À0.53
0.38 and À0.45
(e ÅÀ3
)
cation–cation or cation–anion aromatic ring
p–p interactions are
rare. The self-assembly process of crystallization often requires
the incorporation of water molecules in these structures [13–16].
It was interesting to check the possibility to associate the sulfo-
nate groups to nicotinamide and isonicotinamide. This work deals
with the synthesis, crystal structure, spectroscopic studies and
optical characterization of new one proton transfer compounds,
namely nicotinamidium 3-carboxy-4-hydroxybenzenesulfonate,
1, and isonicotinamidium 3-carboxy-4-hydroxybenzenesulfonate
monohydrate, 2.
diffractometer with Onyx (for 1) or Ruby (for 2) CCD camera. The
intensity data were collected at 100(2) and 90(2) K, respectively
for 1 and 2, using graphite-monochromatized Mo K radiation
a
(k = 0.71073 Å). Data collection, cell refinement, and data reduction
and analysis were carried out with the Xcalibur PX software (Cry-
sAlis PRO) [17].
The structures were solved by direct methods using the SHEL-
XS-97 program [18] and refined on F2 by full-matrix least squares
with anisotropic thermal parameters for all non-H atoms using
SHELXL-97 [18]. All H atoms were found in difference Fourier maps
and were refined isotropically. In the final refinement cycles, the C-
bonded H atoms were positioned geometrically and treated as rid-
ing atoms, with C–H = 0.95 Å, and with Uiso(H) = 1.2Ueq(Caryl). The
N- and O-bonded H atoms were refinement with Uiso(H) = 1.2Ueq(N)
and 1.5 Ueq(O), respectively.
Complete crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic Data Centre;
CCDC reference numbers 968379-968380. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retriev-
ing.html (or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223 336033;
e-mail: deposit@ccdc.cam.uk).
Experimental
Synthesis
Nicotinamide (NA), isonicotinamide (INA) and 5-sulfosalicylic
acid (5-SSA) are commercial reagents from Fluka. Reagents and sol-
vents were used as purchased without further purification. The tar-
get compounds were prepared by dissolving a 1:1 ratio of 5-SSA
(0.213 g) and, respectively, NA and INA (0.100 g) in 10 ml of meth-
anol–water mixture (1:2) and heated to dissolve the solid. When
the solutions became homogeneous, they were cooled and crystals
of nicotinamidium 3-carboxy-4-hydroxybenzenesulfonate, 1, and
isonicotinamidium 3-carboxy-4-hydroxybenzenesulfonate mono-
hydrate, 2, were obtained by slow evaporation. Elemental analysis,
IR spectra and X-ray structural investigations confirmed the chem-
ical formulae of the title compounds. 1: C13H12N2O7S found C,
45.93; H, 3.48; N, 8.17; S, 9.76%; 2: C13H14N2O8S found C, 43.43;
H, 3.86; N, 7.89; S, 8.94%.
Spectroscopic measurements
The FT-IR powder spectra of both complexes were recorded on a
Bruker IFS-88 spectrometer with a resolution of 2 cmÀ1 using sam-
ples in KBr pellets at room temperature.
X-ray data collection
SHG measurements
Details of data collections, analyses and refinements for the
studied crystals are given in Table 1. The crystallographic measure-
ments for 1 and 2 were performed on a Xcalibur PX four-circle
The quadratic NLO response of compounds 1 and 2 was evalu-
ated by performing second harmonic generation (SHG) on powder

I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
79
samples of 1 and 2 using the modified Kurtz–Perry method [19].
About 50 mg of compound is inserted into a sample holder, made
of two Pyrex (25 Â 75 Â 1) mm microscope slides separated by a
thin (0.3 mm thick) spacer. The corresponding space is filled with
hydroxyl and carboxyl groups of 5-SAAÀ lie approximately in the
ring plane of anion with deviations of 0.023(3) and À0.051(3) Å
for atoms O31 and O21, respectively. The protonation of the cation
is confirmed by C–N bond distances (1.333(3) and 1.346(3) Å) and
the C–N–C (123.2(2)°) bond angle (Table 2). The pyridine rings of
the nicotinamidium are slightly distorted from planarity with the
largest deviations from an aromatic ring plane occurring for the
atom C4 (À0.016(2) Å). The carboxamide group is twisted with
respect to the aromatic ring; the dihedral angle between the car-
boxamide group and the pyridine ring plane is 19.9(4)°. Nicotinam-
idium cation (NA+) adopts a syn conformation with the heterocyclic
N and amide N atoms located on the same side of the cation
[torsion angle C2–C3–C7–N7 is À21.0(3)° (Table 2)]. A similar
conformation has been observed in the previously described nico-
tinamide-nitrophenol complex [12], and also in other complexes
with NA [22–24].
the NLO powder sandwiched between the two slides. A 1.064 lm
fundamental laser beam is emitted by a Q-switched Nd3+;YAG
nanosecond laser (SAGA from Thales Laser) at a 10 Hz repetition
rate. A Schott RG 1000 filter is used to filter out any remaining vis-
ible light from the IR incident laser beam. The second harmonic
signal at 532 nm is detected by a photomultiplier (Hamamatsu)
and its intensity is measured on an oscilloscope screen. The SHG
signal must be compared to a reference nonlinear material, here
a urea powder.
Results and discussion
Each NA+ is connected to an adjacent NA+ via N1–H1Á Á ÁO7ii
hydrogen bonds, between the pyridine hetero N and the carbonyl
O atoms, to form a C(6) chain along the c-axis (shown as ball-
and-stick style) [25]. Similarly, adjacent 5-SSAÀ ions are joined
via O21–H20Á Á ÁO51i hydrogen bonds, to give an infinite C(8) chain
running down the a-axis (shown as sticks) (Fig. 2a). Cation–cation
chains (C(6)) are alternated with anion–anion chains (C(8)), and
are linked into a three-dimensional network by N7–H71Á Á ÁO61
and N7–H72Á Á ÁO41iii hydrogen bonds formed between the car-
boxyamide groups of cation and the sulfonate O atoms of anions
(Table 3 and Fig. 2b).
Crystal structures
Nicotinamidium 3-carboxy-4-hydroxybenzenesulfonate – 1
Compound 1 exists as an organic–organic salt, the H atom of
sulfonic group being transferred to the pyridine N atom (Fig. 1).
Surprisingly, there is no solvent molecule in 1. The structures of
5-SSA salts usually incorporate at least one solvent molecule and
only few anhydrous compounds are known [13,20,21]. Deprotona-
tion of sulfonic group was confirmed by comparing the S–O
(1.456(1), 1.474(2) and 1.457(1) Å) bond lengths (Table 2). The
Fig. 1. The molecular structure of 1, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small
spheres of arbitrary radii.
Table 2
Selected geometric parameters (Å, °) for salts 1–2.
1
2
1
2
Cation
Anion
N1–C2
N1–C6
C2–C3
C3–C4
C4–C5
C5–C6
C3–C7/C4–C7
C7–O7
C7–N7
N1–C2–C3
C2–N1–C6
O7–C7–N7
N7–C7–C3/N7–C7–C4
O7–C7–C3/O7–C7–C4
C2–C3–C7–O7/C5–C4–C7–O7
C4–C3–C7–O7/C3–C4–C7–O7
C2–C3–C7–N7/C5–C4–C7–N7
C4–C3–C7–N7/C3–C4–C7–N7
1.333 (3)
1.346 (3)
1.383 (3)
1.394 (3)
1.393 (3)
1.376 (3)
1.507 (3)
1.236 (2)
1.330 (2)
119.9 (2)
123.2 (2)
123.7 (2)
117.5 (2)
118.8 (2)
158.3 (2)
À17.7 (3)
À21.0 (3)
163.0 (2)
1.342 (2)
1.340 (2)
1.375 (2)
1.395 (2)
1.397 (2)
1.380 (2)
1.514 (2)
1.232 (2)
S–O41
S–O51
S–O61
S–C51
O11–C71
O21–C71
O31–C21
C11–C21
1.4560 (14)
1.4736 (15)
1.4567 (14)
1.773 (2)
1.225 (2)
1.320 (3)
1.345 (2)
1.399 (3)
1.485 (2)
123.5 (2)
114.5 (2)
123.2 (2)
117.0 (2)
119.4 (2)
À1.2 (3)
1.4567 (11)
1.4798 (11)
1.4464 (11)
1.770 (2)
1.228 (2)
1.324 (2)
1.344 (2)
1.412 (2)
1.482 (2)
1.328 (2)
C11–C71
119.67 (14)
122.59 (14)
124.29 (14)
117.50 (14)
118.21 (13)
165.75 (14)
À12.1 (2)
À13.4 (2)
168.77 (13)
O11–C71–O21
O21–C71–C11
O31–C21–C11
O31–C21–C31
S–C51–C61
O31–C21–C11–C71
O41–S–C51–C61
O51–S–C51–C61
O61–S–C51–C61
122.31 (14)
114.65 (12)
123.76 (13)
116.53 (13)
121.32 (12)
À0.5 (2)
23.9 (2)
17.30 (14)
À101.38 (13)
139.08 (12)
À95.9 (2)
144.5 (2)

80
I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
Fig. 2. A packing diagram of 1 viewed down the b-axis, showing anion–anion and cation–cation interactions via O–HÁ Á ÁO (orange dashed lines) and N–HÁ Á ÁO hydrogen bonds
(black dashed lines), respectively in (a), and showing 3D architecture of the crystal. Symmetry codes are given in Table 3. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)
of N1–C6 ring at (x, y, z) and C11–C61 rings at (x À 1/2, Ày, z)
Table 3
and (x À 1/2, Ày + 1, z) are 3.458(3) and 3.756 Å, with the an inter-
Hydrogen-bond geometry for 1 (Å, °).
planar spacing of 3.254(2) and 3.280(2) Å, and a centroid offset of
1.17 and 1.83 Å, respectively. The angle between the planes of
these rings is 5.76(5)°.
D–HÁ Á ÁA
d(D–H)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
D–HÁ Á ÁA
O21–H20Á Á ÁO51i
O31–H30Á Á ÁO11
N1–H1Á Á ÁO7ii
0.89 (2)
0.77 (2)
0.89 (2)
0.78 (2)
0.88 (3)
0.95
1.71 (2)
1.89 (3)
1.90 (2)
2.10 (2)
1.99 (3)
2.56
2.591 (2)
2.611 (2)
2.662 (2)
2.864 (2)
2.866 (3)
3.339 (3)
3.186 (2)
3.258 (3)
167 (2)
156 (3)
143 (2)
166 (2)
170 (2)
140
N7–H71Á Á ÁO61
N7–H72Á Á ÁO41iii
C2–H2Á Á ÁO41iii
C5–H5Á Á ÁO11iv
C61–H61Á Á ÁO31v
Isonicotinamidium 3-carboxy-4-hydroxybenzenesulfonate
monohydrate - 2
Contrary to 1, complex 2 crystallizes as a monohydrate (Fig. 3).
The C–N (1.342(2) and 1.340(2) Å) and S–O bond distances
(1.457(1), 1.480(1) and 1.446(1) Å) indicate that the pyridine N
atom of INA is protonated and the sulfonic group of 5-SSA is depro-
tonated. The hydroxyl and carboxyl groups of 5-SAAÀ ion deviate
from the benzene ring plane, with deviations of 0.042(3),
À0.077(3) and 0.087(3) Å for atoms O31, O21 and O11, respec-
tively. The pyridine ring of INA+ ion is nearly planar; the largest
deviation from an aromatic ring plane occur for atom N1
(À0.006(2) Å). The carboxamide group is twisted with respect to
0.95
0.95
2.41
2.53
139
133
Symmetry codes: (i) x + 1/2, Ày + 1, z; (ii) Àx + 1, Ày, z + 1/2; (iii) Àx + 3/2, y, z + 1/2;
(iv) x À 1, y, z; (v) Àx + 2, Ày + 1, z À 1/2.
The three-dimensional framework is interlinked by weak
C–HÁ Á ÁO hydrogen bonding interactions (Table 3), and stack down
the b-axis, the alternating cation–anion–cation separation
indicating
p–p interactions. The distances between the centroids

I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
81
Fig. 3. The molecular structure of 2, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small
spheres of arbitrary radii.
Fig. 4. A packing diagram of 2 viewed down the a-axis, showing anions and water molecules organized via O–HÁ Á ÁO hydrogen bonds (orange dashed lines) in (a), and viewed
down the b-axis, showing 3D architecture of the crystal, formed by O–HÁ Á ÁO (orange dashed lines) and N–HÁ Á ÁO hydrogen bonds (black dashed lines) in (b). Symmetry codes
are given in Table 4. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

82
I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
Table 4
Additional stabilization is provided by weak C–HÁ Á ÁO hydrogen
bonds (Table 4) and also cation–anion stacking interactions.
Hydrogen-bond geometry for 2 (Å, °).
p–p
The distance between the centroids of N1–C6 ring at (x, y, z) and
C11–C61 rings at (x, Ày + 3/2, z À 1/2) is 3.530(3) Å, and the inter-
planar spacing and the centroid offset are 3.243(3) and 1.39 Å,
respectively. The angle between the planes of these rings is
1.02(3)°.
D–HÁ Á ÁA
d(D–H)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
D–HÁ Á ÁA
O1W–H1WÁ Á ÁO51
O1W–H2WÁ Á ÁO41i
O21–H20Á Á ÁO51ii
O31–H30Á Á ÁO11
O31–H30Á Á ÁO41iii
N1–H1Á Á ÁO61
0.82 (2)
0.81 (2)
0.86 (2)
0.82 (2)
0.82 (2)
0.86 (2)
0.86 (2)
0.85 (2)
0.89 (2)
0.95
2.18 (2)
2.18 (2)
1.81 (2)
1.88 (2)
2.37 (2)
2.25 (2)
2.05 (2)
2.24 (2)
2.54 (2)
2.38
2.989 (2)
2.985 (2)
2.664 (2)
2.612 (2)
2.868 (2)
2.834 (2)
2.756 (2)
3.091 (2)
3.410 (2)
2.920 (2)
3.453 (2)
168 (2)
171 (2)
174 (2)
149 (2)
120 (2)
125 (2)
138 (2)
174 (2)
166 (2)
116
N1–H1Á Á ÁO7iv
Infrared spectra
N7–H71Á Á ÁO41v
N7–H72Á Á ÁO51vi
C2–H2Á Á ÁO61
The IR spectra of the studied complexes are presented in Figs. 5
and 6. As can be seen in both complexes a large absorption is
observed in the ꢁ1860–3600 cmÀ1 range, though with different
profiles in two salts. In this region one expects to find an absorp-
tion coming from stretching vibrations of v(X–H) modes engaged
in medium strong hydrogen bond of O–HÁ Á ÁO, N+–HÁ Á ÁOÀ and C–
HÁ Á ÁO types. The origin of the observed broad absorption with a
complex structure in the infrared region of hydrogen-bonded sol-
ids has been widely discussed in the literature [26,27]. It is well
established that in solids the main band shaping mechanism of
the v(XH) band is phonon coupling effects, i.e. a strongly anhar-
monic coupling mechanism between the high-frequency hydrogen
stretching vibration and the low-frequency lattice phonons. How-
ever in many cases one should expect also a Fermi resonance inter-
action between the fundamental vibration v(X–H) and the
overtones or combination tones of intramolecular vibrations, lead-
ing to the substructure of bands. The detailed assignment of the
spectra in lower frequency region is difficult and will be the subject
of a separate paper, on the use of DFT calculations.
C61–H61Á Á ÁO31vii
0.95
2.56
157
Symmetry codes: (i) Àx + 1/2, y À 1/2, z; (ii) Àx + 1/2, Ày + 1, z + 1/2; (iii) x + 1/2, y,
Àz + 3/2; (iv) x À 1/2, y, Àz + 1/2; (v) x + 1/2, y, Àz + 1/2; (vi) Àx + 1/2, Ày + 1, z À 1/
2; (vii) x À 1/2, y, Àz + 3/2.
the aromatic ring; the dihedral angle between the carboxamide
group and pyridine ring plane is 12.8(3)°.
In the crystal structure of 2, each adjacent 5-SSAÀ ions are
joined via O21–H20Á Á ÁO51ii hydrogen bonds. These ions are further
organized into corrugated layers via other O31–H30Á Á ÁO41iii
hydrogen bonds formed between the hydroxyl groups and the sul-
fonate O41 atoms. The molecule is involved in hydrogen bonds
with atoms O51 and O41 of two different of 5-SSAÀ ions of adja-
cent layers (O1W–H1WÁ Á ÁO51 and O1W–H2WÁ Á ÁO41i) (Fig. 4a).
The role of water molecule in the overall hydrogen-bonding pat-
tern of the O–HÁ Á ÁO interactions in 2 displays similarities to the
previously reported salts by Meng et al. [15]. Cations (shown as
ball-and-stick style) and anions (shown as sticks) are linked to
each other by the N–HÁ Á ÁO hydrogen bonds. The pyridine atom
N1 acts as a bifurcated hydrogen-bond donor to the carbonyl atom
O7 of INA+ and the sulfonate atom O61 of 5-SSAÀ (N1–H1Á Á ÁO7iv
and N1–H1Á Á ÁO61). Similarly, the amine atom N7 is involved in
bifurcated hydrogen bonds from sulfonate atoms O41 and O51 of
two different 5-SSAÀ ions (N7–H71Á Á ÁO41v and N7–H72Á Á ÁO51vi).
In this way, a three-dimensional network is created (Fig. 4b and
Table 4).
SHG properties
The studied crystals consist of complex
p electronic molecular
hydrogen-bonded systems with the electron donor–acceptor
groups. Due to hydrogen bond interactions and proton transfer,
one should expect some changes of molecular quadratic hyperpo-
larizabilities of the interacting molecules [28]. For example the cal-
culated molecular hyperpolarizabilities for nicotinamide and
Fig. 5. Infrared spectrum of 1 in KBr pellet.

I. Bryndal et al. / Journal of Molecular Structure 1068 (2014) 77–83
83
Fig. 6. Infrared spectrum of 2 in KBr pellet.
isonicotinamide are 1.81 Â 10À30 and 0.74 Â 10À30 esu respectively
References
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Further studies should be focused on single crystal elaboration and
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