Crystal and molecular structure of two organic acid-base salts from nicotinamide and aromatic acids

Article abstract of DOI:10.1007/s10870-013-0413-2

Two crystalline organic acid-base salts (nicotinamide):(3,5- dinitrosalicylic acid) [(HL⁺)...(3,5-dns^-), 3,5-dns^- = 3,5-dinitrosalicylate] (1), and (nicotinamide):(4-nitro- phthalic acid) [(HL⁺)...(Hnpa^-), Hnpa^- = 4-nitro-hydrogenphthalate] (2) derived from nicotinamide and aromatic carboxylic acids (3,5-dinitrosalicylic acid, and 4-nitro-phthalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. Compound 1 crystallizes in the monoclinic, space group P2(1)/c, with a = 4.7950(3) A, b = 22.290(2) A, c = 14.3901(13) A, β = 104.861(2)°, V = 1486.6(2) A³, Z = 4. Compound 2 crystallizes in the monoclinic, space group P2(1)/c, with a = 15.0173(14) A, b = 12.9849(13) A, c = 7.7281(6) A, β = 111.6040(10)°, V = 1401.1(2) A³, Z = 4. Both supramolecular architectures of the compounds 1-2 involve O-H...O/N-H...O hydrogen bonds as well as other noncovalent association. The role of these noncovalent interactions in the crystal packing is ascertained. For the presence of these weak noncovalent interactions, both compounds displayed 3D framework structure.

Full text of DOI:10.1007/s10870-013-0413-2

J Chem Crystallogr (2013) 43:258–265
DOI 10.1007/s10870-013-0413-2
ORIGINAL PAPER
Crystal and Molecular Structure of Two Organic Acid–Base
Salts from Nicotinamide and Aromatic Acids
•
Shouwen Jin Daqi Wang Qianli Linhe
•
•
•
•
Mingjun Fu Siyuan Wu Jiaqi Ren
Received: 12 November 2012 / Accepted: 4 April 2013 / Published online: 23 April 2013
Ó Springer Science+Business Media New York 2013
Abstract Two crystalline organic acid–base salts (nico-
tinamide):(3,5-dinitrosalicylic acid) [(HL?)ꢀꢀꢀ(3,5-dns-),
3,5-dns- = 3,5-dinitrosalicylate] (1), and (nicotinamide):
(4-nitro-phthalic acid) [(HL?)ꢀꢀꢀ(Hnpa-), Hnpa- = 4-
nitro-hydrogenphthalate] (2) derived from nicotinamide
and aromatic carboxylic acids (3,5-dinitrosalicylic acid,
and 4-nitro-phthalic acid) were prepared and characterized
by X-ray diffraction analysis, IR, mp, and elemental
analysis. Compound 1 crystallizes in the monoclinic, space
Introduction
Intermolecular interactions are responsible for crystal
packing and gaining an understanding of them allows us to
comprehend collective properties and permits the design of
new crystals with specific physical and chemical properties
[1]. Intermolecular forces, such as hydrogen bonding, p–p
stacking, CH–p/CH2–p/CH3–p interactions, CH–O/CH2–
O/CH3–O interactions, ion pairing, and donor–acceptor
interactions are well-known for making aggregates of
molecules and linking discrete molecular building blocks or
low-dimensional structures into high-dimensional supra-
molecular frameworks [2–7]. Hydrogen bonding is one of
the most important noncovalent interactions that determines
and controls the assembly of molecules and ions [8–11].
In recent years, efforts have been made to explore the
synthesis of multicomponent supermolecules or supramo-
lecular arrays utilizing noncovalent bonding. Thus, the
supramolecular synthesis successfully exploits hydrogen-
bonding and other types of non-covalent interactions, in
building supramolecular systems [12]. In this regard, there
are many interesting topological structures such as one-
dimensional (1D) tapes, two-dimensional (2D) sheets, and
three-dimensional (3D) networks which have been con-
structed through hydrogen bonding interactions [13, 14].
The carboxylic acids are capable of functioning as hydrogen
bond donors and/or acceptors resulting in supramolecular
frameworks by intermolecular hydrogen bond interactions
and have been widely utilized in crystal engineering [15].
Carboxylic acids aggregate in the solid state as dimer, ca-
temer, and bridged motifs [16–23]. It is interesting to
exploit the robust and directional recognition of carboxylic
acids with N-containing heterocyclic compounds [24–28].
Nicotinamide is one of the widely used cocrystal
formers, as it is not only classified as a GRAS substance
˚
group P2(1)/c, with a = 4.7950(3) A, b = 22.290(2) A,
˚
3
˚
˚
c = 14.3901(13) A, b = 104.861(2)8, V = 1486.6(2) A ,
Z = 4. Compound 2 crystallizes in the monoclinic, space
˚
group P2(1)/c, with a = 15.0173(14) A, b = 12.9849(13)
˚
˚
A, c = 7.7281(6) A, b = 111.6040(10)8, V = 1401.1(2)
3
˚
A , Z = 4. Both supramolecular architectures of the
compounds 1–2 involve O–HꢀꢀꢀO/N–HꢀꢀꢀO hydrogen bonds
as well as other noncovalent association. The role of these
noncovalent interactions in the crystal packing is ascer-
tained. For the presence of these weak noncovalent inter-
actions, both compounds displayed 3D framework
structure.
Keywords Crystal structure ꢀ Hydrogen bonding ꢀ
Noncovalent interactions ꢀ Organic salts ꢀ Nicotinamide ꢀ
Aromatic acids
S. Jin (&) ꢀ Q. Linhe ꢀ M. Fu ꢀ S. Wu ꢀ J. Ren
Tianmu College, ZheJiang A & F University,
Lin’An 311300, People’s Republic of China
e-mail: jinsw@zafu.edu.cn
D. Wang
Department of Chemistry, Liaocheng University,
Liaocheng 252059, People’s Republic of China
123

J Chem Crystallogr (2013) 43:258–265
259
but also contains two well-known hydrogen-bonding
groups (pyridine N and amide) in the structure [29]. Some
adducts have been successfully prepared from nicotin-
amide and carboxylic acids [30–32]. However, although
both pyridine N and amide of nicotinamide are able to
generate reliable synthons with carboxylic group, only few
organic salts of nicotinamide have been documented [33–
35]. The organic salts from isonicotinamide are also very
rare in the literature [36].
stirred solution of nicotinamide (12.2 mg, 0.1 mmol) in
methanol (3 ml) over a period of 5 min. The solution was
stirred for a few minutes, then the solution was filtered into
a test tube. The solution was left standing at room tem-
perature for several days, colorless block crystals were
isolated after slow evaporation of the methanol solution in
air. The crystals were collected and dried in air to give the
title compound [(HL?)ꢀꢀꢀ(3,5-dns-)] (1). (yield: 28 mg,
79.94 %). mp 154–155 °C. Elemental analysis: Calc. for
C13H10N4O8 (350.25): C, 44.54; H, 2.86; N, 15.99. Found:
C, 44.48; H, 2.83; N, 15.95. Infrared spectrum (cm-1):
3,698s(m(OH), 3,463s(mas(NH)), 3,359s(ms(NH)), 3246m,
3198m, 2971m, 2866m, 1695s(mas(C=O)), 1634s, 1603m,
1572m, 1528s(mas(NO2)), 1426m, 1401s, 1354m,
1317s(ms(NO2)), 1286s(ms(C–O)), 1217m, 1169s, 1094m,
1038w, 956w, 856m, 789w, 697m, 651w, 608m.
Therefore, it is important to investigate supramolecular
interactions between nicotinamide and carboxylic acids by
cocrystallization, herein we report the preparation and struc-
tures of two organic acid–base salts assembled from nicotin-
amide (L) and the corresponding carboxylic compounds
(Scheme 1), respectively. The two organic salts are (nicotin-
amide):(3,5-dinitrosalicylic acid) [(HL?)ꢀꢀꢀ(3,5-dns-), 3,5-dns- =
3,5-dinitrosalicylate] (1), and (nicotinamide):(4-nitro-phthalic
acid) [(HL?)ꢀꢀꢀ(Hnpa-), Hnpa- = 4-nitro-hydrogenphthalate]
(2) (Scheme 2).
O N
2
O
O
H
Experimental Section
N
O
H
Materials and Physical Measurements
H
O N
2
O
NH
2
The chemicals and solvents used in this work are of analytical
grade and available commercially and were used without
further purification. The FT-IR spectra were recorded from
KBr pellets in range 4,000–400 cm-1 on a Mattson Alpha-
Centauri spectrometer. Microanalytical (C, H, and N) data
were obtained with a Perkin–Elmer Model 2400II elemental
analyzer. Melting points of new compounds were recorded on
an XT-4 thermal apparatus without correction.
1
HO
N
O
O
OH
O
H
H
Preparation of the Organic Acid–Base Salts 1–2
N
(Nicotinamide):(3,5-Dinitrosalicylic Acid) [(HL?)ꢀꢀꢀ(3,5-
dns-)] (1)
O N
2
H
2
A solution of 3,5-dinitrosalicylic acid (22.8 mg, 0.1 mmol)
in methanol (10 ml) was added dropwise to a vigorously
Scheme 2 The two organic acid–base salts described in this paper,
1–2
Scheme 1 Hydrogen bond
tectons discussed in this paper
NO2
O2N
O
O
H2N
HO
OH
O
O
N
O2N
OH
OH
4-nitro-phthalic acid
3,5-dinitrosalicylic acid
nicotinamide
123

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J Chem Crystallogr (2013) 43:258–265
(Nicotinamide):(4-Nitro-Phthalic Acid) [(HL?)ꢀꢀꢀ(Hnpa-)]
(2)
and their atom labelling schemes for the two structures are
illustrated in Figs. 1 and 3, respectively. The elemental
analysis data for the two crystalline compounds are in good
agreement with their compositions. The infrared spectra of
the two compounds are consistent with their chemical
formulas determined by elemental analysis and further
confirmed by X-ray diffraction analysis. In 1, only the
phenol group has ionized. In 2, only one proton of the
carboxyl units has transferred to the ring N atom of nico-
tinamide molecule to form the corresponding hydrogen
carboxylate salt. Thus the acids in both 1 and 2 present the
valence number of -1.
The bands at approximately 3,700–3,100 cm-1 in the IR
spectra of the two compounds arise from O–H or N–H
stretching frequencies. Pyridinic ring stretching and bend-
ing are attributed to the medium intensity bands in the
regions of 1,500–1,630 and 600–750 cm-1, respectively.
Compound 1 bears characteristic bands for COOH groups
only, while the salt 2 exhibits the characteristic bands for
both COO- and COOH groups. IR spectroscopy has also
proven to be useful for the recognition of proton transfer
compounds [39, 40]. The most distinct feature in the IR
spectrum of proton transfer compounds are the presence of
strong asymmetrical and symmetrical carboxylate stretch-
ing frequencies at 1,550–1,610 and 1,300–1,420 cm-1
respectively in the compound 2.
A solution of 4-nitro-phthalic acid (21.1 mg, 0.1 mmol) in
methanol (8 ml) was added dropwise to a vigorously stirred
solution of nicotinamide (12.2 mg, 0.1 mmol) in methanol
(3 ml) over a period of 5 min. The solution was stirred for
a few minutes, then the solution was filtered into a test
tube. The solution was left standing at room temperature
for several days, colorless block crystals were isolated after
slow evaporation of the methanol solution in air. The
crystals were collected and dried in air to give the title
compound [(HL?)ꢀꢀꢀ(Hnpa-)] (2). (yield: 26 mg, 78.02 %).
mp 142–144 °C. Elemental analysis: Calc. for C14H11N3O7
(333.26): C, 50.41; H, 3.30; N, 12.60. Found: C, 50.33; H,
3.28; N, 12.54. Infrared spectrum (cm-1): 3,679s(m(OH)),
3,482s(multiple, mas(NH)), 3,348s(ms(NH)), 3268m, 3138m,
3047m, 2989m, 2927m, 2847m, 1728s(m(C=O)), 1638m,
1596s(mas(COO-)), 1558m, 1522s(mas(NO2)), 1474s,
1423s, 1377s(ms(COO-)), 1,324s(ms(NO2)), 1,291s(m(C–
O)), 1241m, 1193m, 1145m, 1091m, 1053m, 999m, 928m,
863m, 804m, 743m, 679m, 614m.
X-Ray Crystallography and Data Collection
Suitable crystals were mounted on a glass fiber on a Bruker
SMART 1000 CCD diffractometer operating at 50 kV and
˚
40 mA using Mo Ka radiation (0.71073 A). Data collec-
tion and reduction were performed using the SMART and
SAINT software [37]. The structures were solved by direct
methods, and the non-hydrogen atoms were subjected to
anisotropic refinement by full-matrix least squares on F2
using SHELXTL package [38].
Structural Descriptions
X-Ray Structure of (Nicotinamide):(3,5-Dinitrosalicylic
Acid) [(HL?)ꢀꢀꢀ(3,5-dns-)] (1)
Hydrogen atoms for the two structures were placed in
calculated positions using riding models. Further details of
the structural analysis are summarized in Table 1. Selected
bond lengths and angles for the compounds 1–2 are listed
in Table 2, the relevant hydrogen bond parameters are
provided in Table 3.
Crystallization of nicotinamide and 3,5-dinitrosalicylic
acid in a 1:1 ratio from the methanol gave single crystals
suitable for X-ray diffraction. Structure determination
(Table 1) revealed that nicotinamide and 3,5-dinitrosali-
cylic acid are present in a 1:1 ratio in the molecular
complex 1. The crystal structure of 1 consists of one
monoprotonated L, and one monoanion of 3,5-dinitrosali-
cylic acid in the asymmetric unit (Fig. 1). Compound 1
crystallizes in the Monoclinic space group P2(1)/c. Dif-
ferent from the salt of isonicotinamide and 3,5-dinitrosal-
icylic acid [36], in 1 the OH groups of 3,5-dinitrosalicylic
acids are ionized by proton transfer to the ring nitrogen
atoms of the nicotinamide moieties, and the COOH group
remains protonized. The O atom of the phenolate are dis-
ordered over two positions with equal occupancies of 0.5,
respectively. There are some differences between 1 and the
documented data [35]. One different is that the volume of
the unit cell in 1 was somewhat larger that the reported
structure. The other difference lies in the fact in 1 all
oxygen atoms were not refined isotropically, while in the
Results and Discussion
Preparation and General Characterization
The preparation of compounds 1–2 were carried out with
nicotinamide and the corresponding carboxylic acids in 1:1
ratio in the methanolic solution, which was allowed to
evaporate at ambient conditions to give the final crystalline
products. In both structures of 1 and 2 the heteroaromatic
Lewis base molecules are protonated, therefore these
structures can be classified as organic salts. The two
compounds are not hygroscopic. The molecular structures
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J Chem Crystallogr (2013) 43:258–265
261
Table 1 Summary of X-ray
crystallographic data for
complexes 1, and 2
1
2
Formula
C13H10N4O8
350.25
C14H11N3O7
333.26
Fw
T, K
298(2)
298(2)
˚
Wavelength, (A)
Crystal system
Space group
0.71073
0.71073
Monoclinic
P2(1)/c
15.0173(14)
12.9849(13)
7.7281(6)
90
Monoclinic
P2(1)/c
˚
a, (A)
4.7950(3)
22.290(2)
14.3901(13)
90
˚
b, (A)
˚
c, (A)
a, deg.
b, deg.
c, deg.
104.861(2)
90
111.6040(10)
90
3
˚
V, A
1486.6(2)
4
1401.1(2)
4
Z
D
calcd, (mg/m3)
1.565
1.580
Absorption coefficient, (mm-1
)
0.133
0.130
F(000)
Crystal size, (mm3)
h range, deg
720
688
0.46 9 0.17 9 0.126
2.93–25.01
-5 B h B 5
-25 B k B 26
-17 B l B 9
6,688
0.42 9 0.39 9 0.13
2.92–28.59
-19 B h B 12
-17 B k B 15
-10 B l B 10
8,748
Limiting indices
Reflections collected
Reflections independent (Rint
Goodness-of-fit on F2
R indices [I [ 2rI]
)
2,599(0.1196)
1.073
3,497(0.0526)
0.961
0.1204, 0.2797
0.1994, 0.3298
0.352, -0.474
0.0541, 0.1239
0.1065, 0.1465
0.288, -0.268
R indices (all data)
˚
Largest diff. peak and hole, e.A
-3
documented structure some O atoms were refined isotrop-
ically [35].
the anion, yet the 3-nitro (O8–N4–O7, 8.7°) deviates
somewhat more from the plane than the 5-nitro (O6–N3–
O5, 5.1°) group, which is similar with the published results
[44]. The rms deviation of the pyridine ring in the cation is
˚
The C–O distances 1.328(10) A (O(4)–C(9)), and
0
˚
1.34(2) A (O(4 )–C(13)) concerning the phenolate are
longer than the proton transfer compound bearing the 3,5-
dns- in which only the phenol group has been deprotonated
[35, 41]. In the COOH group, two C–O bond lengths are
˚
0.0034 A, the amide group deviates by 27.5° from the
pyridine ring plane. The rms deviation of the phenyl ring in
˚
the anion is 0.0102 A, the interplane angle between the
˚
obviously different between O(2)–C(7) (1.240(8) A), and
˚
aromatic rings of the anion and the cation is 9.5 A.
˚
˚
O(3)–C(7) (1.287(9) A) with the D value of 0.047 A. The
relatively larger D value which is expected for neutral C=O
and C–O bond distances [42] are also confirming the reli-
ability of adding H atoms experimentally by different
electron density onto O atoms (Table 3).
Since the potentially hydrogen bonding carboxyl group
is present in the ortho position to the phenolate group in the
anion, it forms the more facile intramolecular hydrogen
bonding. Thus the usual intramolecular hydrogen bond is
found between the phenolate group and a carboxyl OH
˚
Protonation of the nicotinamide base on N2 site is
reflected in a change in bond angle. The angle at unproto-
nated ring N atom is 118.56(13)8 [43], while for protonated
N the angle (C(6)–N(2)–C(2)) is 123.5(7)8. The tor-
sion angles O6–N3–C10–C9, and O8–N4–C12–C11 are
174.40°, and 170.97°, respectively. In this regard, both nitro
groups are nearly in the same plane as the benzene ring of
(O3–H3ꢀꢀꢀO(4), 2.451 A, 155.05°) which is similar to the
˚
corresponding value (2.409 A) in proton-transfer com-
pound of [(hmt)? [(dnsa)-] [45, 46]. Yet the value is as
expected generally smaller than the distance found for the
˚
parent dnsa acid monohydrate [2.566(3) A] [47], and in the
neutral species found in the adduct compound. For the
presence of the intramolecular hydrogen bond, there also
123

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J Chem Crystallogr (2013) 43:258–265
˚
together via the N–HꢀꢀꢀO hydrogen bond between the
amide group and the 5-nitro group of the anion with NꢀꢀꢀO
Table 2 Selected bond lengths (A) and angles (°) for 1–2
1
˚
separation of 3.074(9) A, and CHꢀꢀꢀO interaction between
N(1)–C(1)
1.327(9)
1.364(10)
1.225(9)
1.205(9)
1.491(9)
1.240(8)
1.328(10)
N(2)–C(2)
1.339(9)
1.210(9)
1.433(10)
1.252(9)
1.253(8)
1.287(9)
1.34(2)
the 2-CH of the cation and the same O atom at the 5-nitro
group that is hydrogen-bonded with the amide group with
N(2)–C(6)
N(3)–O(5)
˚
N(3)–O(6)
N(3)–C(10)
N(4)–O(7)
CꢀꢀꢀO distance of 3.576 A to form a tetracomponent
N(4)–O(8)
aggregate. In the tetracomponent aggregate, the corre-
sponding anions and the cations were inversionally related.
The tetracomponent aggregates were linked together by the
N–HꢀꢀꢀO hydrogen bond between the amide group and the
3-nitro group of the anion with NꢀꢀꢀO separation of
N(4)–C(12)
O(2)–C(7)
O(1)–C(1)
O(3)–C(7)
O(4)–C(9)
O(40)–C(13)
O(5)–N(3)–O(6)
O(2)–C(7)–O(3)
C(2)–N(2)–C(6)
O(1)–C(1)–N(1)
123.5(7)
123.6(7)
121.2(8)
122.8(7)
˚
3.032(8) A to form 1D wave chain running along the c axis
direction. The 1D wave chains were joined together by the
interchain CHꢀꢀꢀO association between the 6-CH of the
cation and the carbonyl unit of the cation with CꢀꢀꢀO dis-
2
N(1)–C(6)
1.331(3)
N(1)–C(2)
1.334(3)
˚
N(2)–C(1)
1.323(3)
1.217(3)
1.218(3)
1.240(3)
1.304(3)
N(3)–O(6)
1.213(3)
1.474(3)
1.257(3)
1.206(3)
tance of 3.306 A, and Oꢀꢀꢀp interaction between the phe-
N(3)–O(7)
N(3)–C(12)
O(2)–C(7)
nolate and the aromatic ring of the cation with OꢀꢀꢀCg
˚
distance of 3.101 A to form 2D corrugated sheet (Fig. 2).
O(1)–C(1)
O(3)–C(7)
O(4)–C(8)
Herein the plane defined by the two neighboring chains
were almost perpendicular with each other, while the first
chain was parallel to the third chain, so did the second
chain and the fourth chain. The sheets were further stacked
along the a axis direction via the intersheet Oꢀꢀꢀp interac-
tion (between the 5-nitro group of the anion and the phenyl
O(5)–C(8)
C(6)–N(1)–C(2)
O(1)–C(1)–N(2)
O(4)–C(8)–O(5)
122.0(2)
O(6)–N(3)–O(7)
O(3)–C(7)–O(2)
124.0(2)
125.5(2)
122.4(2)
124.8(2)
˚
exists hydrogen bonded motif with graphical descriptor of
S11(6). The cation adopted the E conformation according to
Borba et al. [48], in which the torsion angle of C2–C3–C1–
O1 (151.39°) is comparable to the corresponding angle
(150.58°) in the reported salt [35].
ring of the anion with OꢀꢀꢀCg distance of 3.192 A, and
between the carbonyl group of the cation and the aromatic
˚
ring of the cation with OꢀꢀꢀCg distance of 3.090 A),
C(carbonyl)ꢀꢀꢀp association between the C atom at COOH
group of the anion and the phenyl ring of the anion with
˚
One anion and one cation formed a heteroadduct via the
CꢀꢀꢀCg distance of 3.394 A, and N–HꢀꢀꢀO hydrogen bond
N–HꢀꢀꢀO hydrogen bond between the NH? cation and the
between the amide group and the carbonyl group of the
˚
carbonyl unit with NꢀꢀꢀO distance of 2.650(8) A, and
cations belonging to two adjacent sheets with NꢀꢀꢀO dis-
˚
tance of 3.028(8) A to form 3D network structure. In this
CHꢀꢀꢀO association between the 6-CH of the cation and the
OH moiety in the COOH of the anion with C–O distance of
˚
3.251 A. Two neighboring heteroadducts were joined
regard, the neighboring sheets were slipped some distance
from its extending direction.
Table 3 Hydrogen bond distances and angles in studied structures 1–2
˚
d(D–H) (A)
˚
˚
D–HꢀꢀꢀA
d(HꢀꢀꢀA) (A)
d(DꢀꢀꢀA) (A)
\(DHA) (°)
1
N(2)–H(2)ꢀꢀꢀO(2)#1
N(1)–H(1B)ꢀꢀꢀO(7)#2
N(1)–H(1B)ꢀꢀꢀO(1)#3
N(1)–H(1A)ꢀꢀꢀO(5)#4
O3–H3ꢀꢀꢀO(4)
0.86
0.86
0.86
0.86
0.82
1.79
2.39
2.34
2.19
1.683
2.650(8)
3.074(9)
3.028(8)
3.032(8)
2.451
176.0
136.7
137.7
165.5
155.05
2
O(5)–H(5)ꢀꢀꢀO(2)#1
N(2)–H(2B)ꢀꢀꢀO(4)
N(2)–H(2A)ꢀꢀꢀO(2)#2
N(1)–H(1)ꢀꢀꢀO(3)#3
0.82
0.86
0.86
0.86
1.74
2.21
2.25
1.79
2.526(2)
3.051(3)
3.087(3)
2.624(2)
160.9
166.7
163.2
162.7
Symmetry transformations used to generate equivalent atoms for 1: #1 x - 1, y, z - 1; #2 -x, -y ? 1, -z ? 1; #3 x - 1, y, z; #4 x ? 1, y, z.
Symmetry transformations used to generate equivalent atoms for 2: #1 x, -y ? 1/2, z - 1/2; #2 x, y, z - 1; #3 -x ? 2, -y ? 1, -z ? 1
123

J Chem Crystallogr (2013) 43:258–265
263
Fig. 1 Molecular structure of 1
showing the atomic numbering
scheme. Displacement
ellipsoids are drawn at the
30 % probability level
Fig. 2 2D corrugated sheet structure of 1
X-Ray Structure of (Nicotinamide):(4-Nitro-Phthalic Acid)
[(HL?)ꢀꢀꢀ(Hnpa-)] (2)
unit (Fig. 3). The compound is also a salt, in which only
one proton of the two carboxyl groups in the 4-nitro-
phthalic acid was ionized. Compound 2 crystallizes in the
Monoclinic space group P2(1)/c. Its single crystal structure
shows the expected proton transfer from the acid to the
pyridyl nitrogen atom. Protonation of the nicotinamide
base on N1 site is reflected in a change in bond angle. The
angle at unprotonated ring N atom is 118.56(13)8 [43],
Similar to 1, the compound 2 of the composition
[(HL?)ꢀꢀꢀ(Hnpa-)] was prepared by reaction equal mol of
nicotinamide and 4-nitro-phthalic acid. The crystal struc-
ture of 2 comprises one monocation of nicotinamide, and
one monoanion of 4-nitro-phthalic acid in the asymmetric
123

264
J Chem Crystallogr (2013) 43:258–265
Fig. 3 Molecular structure of 2
showing the atomic numbering
scheme. Displacement
ellipsoids are drawn at the
30 % probability level
Fig. 4 2D sheet extending on the ac plane
while for protonated N the angle (C(6)–N(1)–C(2)) is
122.0(2)8. And this angle was also smaller than that found
in compound 1.
rotated by 4.0° from the pyridine ring plane. The dihedral
angle between the phenyl ring of C9–C14 and the ring of
N1–C2–C3–C4–C5–C6 was 117.0°.
Different from 1, the cation adopted the Z conformation
according to Borba et al. [48], in which the C2–C3–C1–O1
torsion angle is -2.3°. The rms deviation of the phenyl ring
The cations were connected together by the CHꢀꢀꢀO
associations between the 5-, and 6-CH of the cation and the
carbonyl group of the cation with CꢀꢀꢀO distances of 3.038–
˚
˚
of the anion is 0.0062 A, the carboxyl groups with O2–O3–
3.095 A to form 1D chain running along the c axis direc-
C7, and O4–O5–C8 are rotated from the plane by 33.3°, and
65.2°, respectively. The groups O2–O3–C7, and O4–O5–
C8 intersected at an angle of 65°. The group O1–C1–N2
tion. The discrete chains extending in the same plane were
joined together by the anions through the N–HꢀꢀꢀO, and
CHꢀꢀꢀO associations to form 2D grid structure. In the 2D
123

J Chem Crystallogr (2013) 43:258–265
265
12. Maamen M, Gordon DM (1995) Acc Chem Res 28:37 and ref-
erences therein
13. Weyna DR, Shattock T, Vishweshwar P, Zaworotko MJ (2009)
Cryst Growth Des 9:1106
14. Du M, Zhang ZH, Zhao XJ (2005) Cryst Growth Des 5:1247
15. Desiraju GR (1989) Crystal engineering, the design of organic
solids. Elsevier, Amsterdam
16. Leiserowitz L (1976) Acta Crystallogr B32:775
17. Kolotuchin SV, Fenlon EE, Wilson SR, Loweth CJ, Zimmerman
SC (1995) Angew Chem Int Ed Engl 34:2654
18. Kuduva SS, Craig DC, Nangia A, Desiraju GR (1999) J Am
Chem Soc 121:1936
19. Bernstein J, Etter MC, Leiserowitz L (1994) Struct Correl 2:431
20. Moulton B, Zaworotko MJ (2001) Chem Rev 101:1629
´
21. Reddy LS, Bethune SJ, Kampf JW, Rodrıguez-Hornedo N (2009)
Cryst Growth Des 9:378
grid the OH groups of the COOH were protruded from the
plane of the sheet, so did one O atom of the nitro group and
one O atom of the COO- group. Two neighboring 2D grid
sheets were held together by the same face of the sheet via
the N–HꢀꢀꢀO hydrogen bond between the NH? cation and
˚
the carboxylate with NꢀꢀꢀO separation of 2.624(2) A, Oꢀꢀꢀp
interaction between the carboxylate of the anion and the
˚
phenyl ring of the anion with OꢀꢀꢀCg distance of 3.145 A,
OꢀꢀꢀN contact between the carboxylate and the nitro group
˚
with OꢀꢀꢀN distance of 2.912 A, OꢀꢀꢀC(carbonyl) contact
between the carbonyl unit of the cations with OꢀꢀꢀC dis-
˚
tance of 3.129 A to form double sheet structure (Fig. 4).
The double sheets were further stacked along the b axis
22. Lee IS, Shin DM, Chung YK (2003) Cryst Growth Des 3:521
23. Bhogala BR, Nangia A (2003) Cryst Growth Des 3:547
24. MacDonald JC, Dorrestein PC, Pilley MM (2001) Cryst Growth
Des 1:29
25. Highfill ML, Chandrasekaran A, Lynch DE, Hamilton DG (2002)
Cryst Growth Des 2:15
26. Vishweshwar P, Nangia A, Lynch VM (2002) J Org Chem 67:556
27. Nichol GS, Clegg W (2009) Cryst Growth Des 9:1844
28. Men YB, Sun JL, Huang ZT, Zheng QY (2009) CrystEngComm
11:978
direction by the O–HꢀꢀꢀO hydrogen bond between the
-
˚
COOH and COO group with OꢀꢀꢀO distance of 2.526(2) A,
Oꢀꢀꢀp association between the OH of the carboxyl and the
˚
phenyl ring of the anion with OꢀꢀꢀCg distance of 3.084 A,
and Cꢀꢀꢀp association between the C(carbonyl) of the cation
and the pyridine ring of the cation with CꢀꢀꢀCg distance of
˚
3.247 A to form 3D network structure.
´
29. Bathori NB, Lemmerer A, Venter GA, Bourne SA, Caira MR
(2011) Cryst Growth Des 11:75
30. Nicoli S, Bilzi S, Santi P, Caira MR, Li J, Bettini R (2008) J
Pharm Sci 97:4830
Supporting Information Available
31. Cheney ML, Shan N, Healey ER, Hanna M, Wojtas L, Zaworotko
MJ, Sava V, Song S, Sanchez-Ramos JR (2010) Cryst Growth
Des 10:394
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Cen-
ter, CCDC Nos. 908429 for 1, and 897098 for 2. Copies of
this information may be obtained free of charge from the
?44(1223)336-033 or Email: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk.
´
´
´
32. Arenas-Garcıa JI, Herrera-Ruiz D, Mondragon-Vasquez K,
¨
Morales-Rojas H, Hopfl H (2010) Cryst Growth Des 10:3732
33. Athimoolam S, Natarajan S (2007) Acta Cryst E63:o1811
34. Athimoolam S, Natarajan S (2007) Acta Cryst E63:o2430
35. Koman M, Martiska L, Valigura D, Glowiak T (2003) Acta Cryst
E59:o441
Acknowledgments We gratefully acknowledge the financial sup-
port of the Education Office Foundation of Zhejiang Province (Project
No. Y201017321) and the financial support of the Zhejiang A & F
University Science Foundation (Project No. 2009FK63).
36. Zulfiya A, Zhao FH, Che YX (2010) Chin J Struct Chem 29:1185
37. Bruker (2004) SMART and SAINT. Bruker AXS, Madison, WI
38. Sheldrick GM (2000) SHELXTL, Structure Determination Soft-
ware Suite, version 6.14. Bruker AXS, Madison, WI
39. Lynch DE, Thomas LC, Smith G, Byriel KA, Kennard CHL
(1998) Aust J Chem 51:867
40. Smith G, White JM (2001) Aust J Chem 54:97
41. Smith G, Wermuth UD, Healy PC, White JM (2011) J Chem
Crystallogr 41:1649
¨
42. Aakeroy CB, Fasulo ME, Desper J (2007) Mol Pharm 4:317
43. Orola L, Veidis MV (2009) CrystEngComm 11:415
References
1. Lam CK, Mak TCW (2000) Tetrahedron 56:6657
2. Tanase S, Bouwman E, Long GJ, Shahin AM, Mills AM, Jan
Reedijk ALS (2004) Eur J Inorg Chem 4572
3. Janiak C (2000) J Chem Soc Dalton Trans 3885
4. Takahashi O, Kohno Y, Nishio M (2010) Chem Rev 110:6049
5. Berkovitch-Yellin Z, Leiserowitz L (1984) Acta Cryst B40:159
6. Cho KH, No KT, Scheraga HA (2000) J Phys Chem A 104:6505
7. Koch W, Frenking G, Gauss J, Cremer D (1986) J Am Chem Soc
108:5808
8. Desiraju GR (2002) Acc Chem Res 35:565
9. Braga D, Maini L, Paganelli F, Tagliavini E, Casolari S, Grepioni
F (2001) J Organomet Chem 637–639:609
10. Liu JQ, Wang YY, Ma LF, Zhang WH, Zeng XR, Zhong F, Shi
QZ, Peng SM (2008) Inorg Chim Acta 361:173
´
´
´
44. Gonzalez FV, Jain A, Rodrıguez S, Saez JA, Vicent C, Peris G
(2010) J Org Chem 75:5888
45. Ng SW, Naumov P, Drew MGB, Wojciechowski G, Brzezinski B
(2001) J Mol Struct 595:29
46. Smith G, Wermuth UD, Bott RC, Healy PC, White JM (2002)
Aust J Chem 55:349
47. Smith G, Lynch DE, Byriel KA, Kennard CHL (1995) Aust J
Chem 48:1133
´
48. Borba A, Albrecht M, Gomez-Zavaglia A, Lapinski L, Nowak
MJ, Suhm MA, Fausto R (2008) Phys Chem Chem Phys 10:7010
11. Biswas C, Drew MGB, Escudero D, Frontera A, Ghosh A (2009)
Eur J Inorg Chem 2238
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