Structure of 2,3-dicarboxy-1-methylpyridinium chloride studied by X-ray diffraction, DFT calculation, NMR, FTIR and Raman spectra

Article abstract of DOI:10.1016/j.molstruc.2011.11.009

The structure of 2,3-dicarboxy-1-methylpyridinium chloride (1) has been studied by X-ray diffraction, DFT calculations, NMR, FTIR and Raman spectra. The crystals are monoclinic, space group P2₁/c. Chloride anion links two 2,3-dicarboxy-1-methylpyridinium cations into infinite zigzag chains down the [0 0 1] direction by the OH?Cl^-?HO hydrogen bonds of 2.970(2) and 3.011(2) ?. Hydrogen bond lengths in single molecules (2-4) optimized by the B3LYP/6-311++G(d,p) approach depend on the environment and intramolecular O·H·O hydrogen bond. Linear correlations between the experimental ¹³C and ¹H chemical shifts (δ_exp) of the investigated compound in DMSO-d₆ and the GIAO/B3LYP/6-311++G(d.p) magnetic isotropic shielding constants (σ_calc) calculated using the screening solvation model (COSMO), δ_exp = a + b σ_calc, are reported. The FTIR spectrum of the solid compound is consistent with the X-ray structure. The deformation in-plane and out-of-plane OH vibrations, both in FTIR and second-derivative (d²) spectra, appear as two bands consistent with the OH?Cl^-?HO arrangement.

Full text of DOI:10.1016/j.molstruc.2011.11.009

Journal of Molecular Structure 1018 (2012) 21–27
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Structure of 2,3-dicarboxy-1-methylpyridinium chloride studied by X-ray
diffraction, DFT calculation, NMR, FTIR and Raman spectra
⇑
´
P. Barczynski, M. Szafran , M. Ratajczak-Sitarz, Ł. Nowaczyk, Z. Dega-Szafran, A. Katrusiak
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60780 Poznan´, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 29 November 2011
The structure of 2,3-dicarboxy-1-methylpyridinium chloride (1) has been studied by X-ray diffraction, DFT
calculations, NMR, FTIR and Raman spectra. The crystals are monoclinic, space group P21/c. Chloride anion
links two 2,3-dicarboxy-1-methylpyridinium cations into infinite zigzag chains down the [001] direction
by the OHÁ Á ÁClÀÁ Á ÁHO hydrogen bonds of 2.970(2) and 3.011(2) Å. Hydrogen bond lengths in single mol-
ecules (2–4) optimized by the B3LYP/6-311++G(d,p) approach depend on the environment and intramo-
lecular OÁHÁO hydrogen bond. Linear correlations between the experimental 13C and 1H chemical shifts
(dexp) of the investigated compound in DMSO-d6 and the GIAO/B3LYP/6-311++G(d.p) magnetic isotropic
Keywords:
2,3-Dicarboxy-1-methylpyridinium chloride
X-ray diffraction
B3LYP calculations
FTIR and NMR spectra
Hydrogen bonds
Electrostatic interactions
shielding constants (rcalc) calculated using the screening solvation model (COSMO), dexp = a + b rcalc, are
reported. The FTIR spectrum of the solid compound is consistent with the X-ray structure. The deformation
in-plane and out-of-plane OH vibrations, both in FTIR and second-derivative (d2) spectra, appear as two
bands consistent with the OHÁ Á ÁClÀÁ Á ÁHO arrangement.
Ó 2011 Published by Elsevier B.V.
1. Introduction
orated. To the yellow crystals obtained, absolute ethanol (20 cm3)
was added and the contents were refluxed for 1 h. Then ethanol
The crystal structure of 2,3-pyridinedicarboxylic acid (quino-
linic acid) was determined by X-ray [1] and neutron diffractions
[2,3]. Quinolinic acid in the crystal is zwitterion (betaine) with
one acidic hydrogen atom transferred to the nitrogen atom. The
second acidic hydrogen atom is involved in a short intramolecular
and asymmetric OHO hydrogen bond of 2.398(3) Å.
was distilled off, the residue was treated with a water solution of
potassium carbonate to pH 7.7–8.0, extracted with diethyl ether
(5 Â 30 cm3), and dried with magnesium sulfate. The solvent was
distilled off and the residue redistilled under vacuum, (153 °C/
1.2 mm Hg, 167–170/6 mm Hg [14] and yield 87%).
Pyridine carboxylic acids, at first heated with methyl iodide [4–6]
or methyl sulfate [7] and then subjected to treatment with propyl-
ene oxide [8,9] or ion-exchange resins, Dovex-22C [5,9] or Amberlite
[4], convert to carboxy-1-methylpyridinum inner salts (betaines).
In our earlier works, we have described H-bonding and electro-
static interactions in the structures of homarinium chloride [10], trig-
onellinium chloride [11], 4-carboxy-1-methylpyridinium chloride
[12] and 3,4-dicarboxy-1-methylpyridinium chloride [13]. In this
work we have synthesized 2,3-dicarboxy-1-methylpyridinium chlo-
ride (Scheme 1) and characterized it by single-crystal X-ray diffrac-
tion, FTIR, Raman and NMR spectroscopy and by DFT calculations.
2.2. 2,3-Diethoxycarbonyl-1-methylpyridinium iodide
To 2,3-diethoxycarbonylpyridine (9.7 g) methyl iodide (15 g)
was added and left for 4 days at room temperature. The excess of
methyl iodide was evaporated and the solid yellow residue recrys-
tallized from a 1:1 mixture of n-hexane with n-butanol; m.p.
134 °C, yield 87%. Elemental analysis calculated for C12H16INO4:
%N 3.84, %C 39.47, %H 4.42; found: %N 3.79, %C 39.38, %H 4.58.
2.3. 2,3-Diethoxycarbonyl-1-methylpyridinium nitrate
2. Experimental and calculations
2,3-Diethoxycarbonyl-1-methylpyridinium iodide (5 g) was
converted into its nitrate salt by adding aqueous solution of silver
nitrate (2.3 g). Silver iodide was filtered off, water from filtrate
evaporated under reduced pressure and to the solid residue abso-
lute ethanol was added. Solvent was evaporated and the residue
was recrystallized from isopropanol, m.p. 130–131 °C, yield 79%.
Elemental analysis calculated for C12H16N2O7: %N 9.33, %C 48.00,
%H 5.37; found: %N 9.27, %C 47.83, %H 5.57.
2.1. 2,3-Diethoxycarbonylpyridine
2,3-Pyridinedicarboxylic acid (10 g) and thionyl chloride
(20 cm3) were refluxed for 2 h. Excess of thionyl chloride was evap-
⇑
Corresponding author. Tel.: +48 61 8291320; fax: +48 61 8291505.
E-mail address: szafran@amu.edu.pl (M. Szafran).
0022-2860/$ - see front matter Ó 2011 Published by Elsevier B.V.
doi:10.1016/j.molstruc.2011.11.009

´
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
22
COOC2H5
COOC2H5
COOC2H5
COOH
COOH
COOH
1. SOCl2
1. CH3I
36% HCl
2. C2H2OH
2. AgNO3
COOC2H5
X-
COOH
Cl-
N
N
N
+
CH3
N
+
CH3
1
X = I, NO3
Scheme 1. Synthesis of 2,3-dicarboxy-1-methylpyridinium chloride (1) from 2,3-pyridinedicarboxylic acid.
Table 2
2.4. 2,3-Dicarboxy-1-methylpyridinium chloride (1)
Atomic coordinates (Â104) and equivalent isotropic displacement parameters
(Å2 Â 103) for 2,3-dicarboxy-1-methylpyridinium chloride (1). U(eq) is defined as
one third of the trace of the orthogonalized Uij tensor.
A portion of 5 g of 2,3-diethoxycarbonyl-1-methylpyridinium
nitrate was heated under reflux with excess of 36% aqueous hydro-
chloride for 12 h. After cooling 3.2 g of 2,3-dicarboxy-1-methylpy-
ridinium chloride was separated and the crude white crystals were
recrystallized from methanol, m.p. 236–238 °C. Elemental analysis:
calculated for C8H8ClNO4: %N 6.44, %C 44.16, %H 3.71; found: %N
6.35, %C 43.90, %H 3.84.
Atom
x
y
z
Ueq/Uiso
Cl(1)
N(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
O(1)
O(2)
O(3)
O(4)
H(71)
H(72)
H(73)
H(4)
H(5)
H(6)
H(1)
H(3)
3204(1)
1975(2)
2126(3)
2498(3)
2712(3)
2531(3)
2164(3)
1673(4)
1817(3)
2622(3)
3367(2)
294(2)
3284(3)
2138(4)
1596
542
2688
2976
2657
2044
3180(50)
3180(50)
À5232(1)
À4647(2)
À4329(2)
À5189(2)
À6360(2)
À6655(2)
À5782(2)
À3740(2)
À3024(2)
À4827(2)
À2434(2)
À2639(2)
À5667(2)
À3880(2)
À4121
1434(1)
7732(2)
6616(2)
5828(2)
6202(2)
7347(2)
8096(2)
8614(2)
6309(2)
4584(2)
6540(2)
5966(2)
4006(2)
4186(2)
9353
8313
8747
5685
7605
8868
6500(30)
3250(40)
50(1)
37(1)
33(1)
34(1)
41(1)
47(1)
45(1)
53(1)
37(1)
37(1)
51(1)
53(1)
54(1)
77(1)
80
80
80
50
56
54
88(13)
97(13)
2.5. Measurements and calculations
The crystals (1) were stable under normal conditions and the X-
ray diffraction measurements were carried out on an Oxford Dif-
fraction Super Nova diffractometer using Cu K radiation at room
a
temperature: -scan data collection with Dx = 1° frames and
x
À3321
40 s exposures were applied. The structure was solved by direct
methods using SHELXS-97 program and refined on F2 by full-ma-
trix least-squares with the SHELXL-97 program [15]. Two acidic
H-atoms at O(1) and O(3) were located from difference Fourier
maps and refined with isotropic temperature factors. The positions
of all other hydrogen atoms were determined from molecular
geometry (CAH distances of 0.93 and 0.96 Å) and their Uiso’s were
related to the thermal vibrations of their carriers. The crystal data,
together with the details concerning data collection and structure
refinement are given in Table 1 and the atomic coordinates in Ta-
ble 2. The parameters in the CIF form are available as Electronic
Supplementary Information from the Cambridge Crystallographic
À3191
À6943
À7439
À5976
À1760(40)
À5460(30
Database Centre (842381). Molecular illustrations were prepared
using programs ORTEPII [16] and XP [17].
FTIR spectra were recorded in Nujol and Fluorolube suspension
between KBr plates on a Bruker IFS 66v/S spectrometer, evacuated
to avoid water and CO2 absorptions, at a 2 cmÀ1 resolution. Each
FTIR spectrum was measured by acquisition of 64 scans. The Ra-
man spectrum of crystalline sample was measured on a Bruker
Table 1
Crystal data and structure refinement for 2,3-dicarboxy-1-methylpyridinium chloride
(1).
Empirical formula
Formula weight
Temperature
C8H8ClNO4
217.60
293(2)
Wavelength
1.54178 Å
Crystal system
Space group
Monoclinic
P21/c
Unit cell dimensions
a = 7.3767(2) Å
b = 11.2790(2) Å
c = 11.4339(2) Å
b = 101.590(2)°
931.92(3) Å3
Volume
Z
4
Calculated density
Absorption coefficient
F(000)
1.551 g cmÀ3
3.585 mmÀ1
448
Crystal size
0.25 Â 0.20 Â 0.15 mm
h range for data collection
Max/min. indices h,k,l
Reflections collected/unique
Completeness to hmax = 73.96°
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
5.57–73.96°
À8 6 h 6 5, À14 6 k 6 13, À14 6 l 6 13
6436/1846 Rint = 0.0115
98.1%
Full-matrix least-squares on F2
1846/0/135
1.048
Final R indices [I > 2rI
R indices (all data)
Largest diff. peak and hole
]
R1 = 0.0443, wR2 = 0.1305
R1 = 0.0446, wR2 = 0.1307
0.560 and À0.294 eÅÀ3
Fig. 1. Atom numbering for 2,3-dicarboxy-1-methylpyridinium chloride (1). The
hydrogen bond is indicated by the dashed line, and the thermal ellipsoids are drawn
at the 50% probability level.

´
23
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
Table 3
Lee et al. [21] and the split-valence polarized 6-311++G(d,p) basis
set [22]. The X-ray geometry of 1 was used as a starting point of
the calculations. The magnetic isotropic shielding constants were
calculated using the standard GIAO/B3LYP/6-311++G(d,p) (Gauge-
Independent Atomic Orbital) approach with the Gaussian 03 pro-
gram package using the conductor-like screening solvation model
(COSMO) [23–25].
X-ray and calculated bond lengths (Å), bond and torsion angles (°) for 2,3-dicarboxy-
1-methylpyridinium chloride.
Parameter
X-ray
B3LYP/6-311++G(d,p)
1
2
3 DMSO
4 DMSO
Bond lengths
N(1)AC(2)
N(1)AC(6)
N(1)AC(7)
C(2)AC(3)
C(2)AC(8)
C(3)AC(4)
C(3)AC(9)
C(4)AC(5)
C(5)AC(6)
O(1)AC(8)
O(2)AC(8)
O(3)AC(9)
O(4)AC(9)
1.352(3)
1.345(3)
1.484(3)
1.388(3)
1.520(3)
1.388(3)
1.500(3)
1.384(3)
1.367(3)
1.303(3)
1.195(3)
1.305(3)
1.187(3)
1.3601
1.3563
1.4837
1.3879
1.5217
1.3912
1.5410
1.3939
1.3782
1.3431
1.2027
1.2495
1.2406
1.3568
1.3515
1.4883
1.3907
1.5220
1.3974
1.5065
1.3873
1.3793
1.3280
1.2034
1.3166
1.2147
1.3622
1.3517
1.4899
1.4022
1.5438
1.3982
1.5154
1.3852
1.3769
1.2670
1.2304
1.3038
1.2287
3. Results and discussion
3.1. Crystal structure
The molecular structure and atom numbering of 2,3-dicarboxy-
1-methylpyridinium chloride (1) are shown in Fig. 1. The bond
lengths, bond and torsion angles determined in the X-ray study
are summarized in Tables 3 and 4.
Bond angles
The linking of cations and anions is governed by hydrogen
bonds OHÁ Á ÁClÀÁ Á ÁHO, forming infinite zigzag chains down the
[001] direction, as illustrated in Fig. 2, and by electrostatic attrac-
tions. The ribbon-like chains are arranged in such a manner that
the chloride anions are located close to the nitrogen atoms in pyr-
idine rings of the neighboring ribbons located below and above in
the [100] direction. The ClÀÁ Á ÁN distances are 3.495(2) and
4.121(2) Å, while four short ClÀÁ Á ÁHC contacts (ClÀÁ Á ÁH distance
from 2.74 to 3.29 Å) are formed to the pyridine and methyl H-
atoms of two cations along the (100) plane. Thus each ClÀ anion
is sixfold coordinated by cations, two of which are OHÁ Á ÁCl bonded
and four others attracted electrostatically (Table 4). An analogous
octahedral coordination arrangement of six ClÀ anions is formed
about each of the cations (Fig. 3). The angles between pyridine ring
and carboxylate groups at 2 and 3 positions are 87.5(1)° and
12.3(2)°, respectively; the angle between the two carboxyl groups
is 84.9(3)°.
N(1)AC(2)AC(3)
N(1)AC(6)AC(5)
N(1)AC(2)AC(8)
C(7)AN(1)AC(2)
C(7)AN(1)AC(6)
C(2)AN(1)AC(6)
C(2)AC(3)AC(4)
C(2)AC(3)AC(9)
C(3)AC(4)AC(5)
C(3)AC(2)AC(8)
C(4)AC(3)AC(9)
C(4)AC(5)AC(6)
O(1)AC(8)AO(2)
O(1)AC(8)AC(2)
O(2)AC(8)AC(2)
O(3)AC(9)AO(4)
O(3)AC(9)AC(3)
O(4)AC(9)AC(3)
119.5(2)
120.9(2)
116.0(2)
120.7(2)
117.8(2)
121.4(2)
119.4(2)
118.9(2)
119.6(2)
124.5(2)
121.8(2)
119.2(2)
127.6(2)
111.3(2)
121.0(2)
125.0(2)
112.5(2)
122.5(2)
120.339
121.012
117.431
120.203
119.118
120.674
119.184
118.332
119.771
122.129
122.476
119.014
125.958
111.133
121.516
132.194
114.164
113.641
120.138
121.072
116.508
120.331
118.688
120.979
118.983
119.417
119.852
123.289
121.599
118.975
126.539
111.385
121.898
125.873
112.357
121.771
118.770
121.266
117.219
121.025
117.188
121.781
119.204
125.516
120.383
123.946
115.279
118.517
128.683
114.672
116.640
121.207
120.332
118.397
Torsion angles
N(1)AC(2)AC(3)AC(4)
N(1)AC(2)AC(3)AC(8)
N(1)AC(2)AC(8)AO(1)
N(1)AC(2)AC(8)AO(2)
N(1)AC(6)AC(5)AC(4)
C(7)AN(1)AC(2)AC(3)
C(7)AN(1)AC(2)AC(8)
C(7)AN(1)AC(6)AC(5)
C(2)AN(1)AC(6)AC(5)
C(6)AN(1)AC(2)AC(3)
C(6)AN(1)AC(2)AC(8)
C(2)AC(3)AC(4)AC(5)
C(3)AC(4)AC(5)AC(6)
C(4)AC(3)AC(2)AC(8)
C(5)AC(4)AC(3)AC(9)
C(8)AC(2)AC(3)AC(9)
O(1)AC(8)AC(2)AC(3)
O(2)AC(8)AC(2)AC(3)
O(3)AC(9)AC(3)AC(2)
O(3)AC(9)AC(3)AC(4)
O(4)AC(9)AC(3)AC(2)
O(4)AC(9)AC(3)AC(4)
À0.2(3)
178.7(2)
91.4(2)
À0.59
178.42
94.38
À72.90
À0.13
À179.32
À2.92
179.70
0.53
À0.17
176.23
0.98
À0.63
À176.82
À177.98
2.19
0.04
179.90
91.90
3.09
À176.52
126.82
À53.89
1.64
3.2. Optimized structures
À84.8(2)
À83.56
0.2(3)
0.04
The structures of the molecules optimized by the B3LYP/6-
311++G(d,p) approach of monomers in vacuum (2) and DMSO (3
and 4) are shown in Fig. 4. The calculated geometrical parameters,
total energies and dipole moments of the optimized molecules are
listed in Tables 3 and 4. In 2 (vacuum) and 4 (DMSO) the hydrogen
bonded proton is linked with chloride atom (ClAHÁ Á ÁO(3)), while in
176.9(2)
À4.7(3)
À176.9(2)
0.5(3)
À0.4(3)
178.0(2)
0.8(3)
À0.8(3)
À178.5(2)
À178.1(2)
0.4(3)
À179.69
À2.51
179.63
0.06
À0.12
177.06
0.10
À0.16
À176.94
À179.76
2.92
177.77
À5.05
179.79
À1.09
À1.32
175.86
À2.53
0.20
3
(DMSO) the structure is similar to that in the crystal
À173.89
177.10
6.51
À56.16
123.13
26.31
À153.31
À156.59
23.80
(ClÁ Á ÁHAO(3)). In 4 the intramolecular O(3)AHÁ Á ÁO(1) hydrogen
bond is present. The energy of 3 is by 9.57 kcal/mol lower in com-
parison to that in 4. In 3 the angles between pyridine ring and car-
À19.2(2)
À89.29
103.43
176.05
À4.98
À4.34
174.63
À91.02
93.5(3)
93.52
boxylate groups at
2 and 3 positions are 82.3° and 1.3°,
168.9(2)
À12.2(3)
À12.0(3)
166.9(2)
179.79
À1.36
À1.32
178.54
respectively, while the angle between the two carboxyl groups is
106.8°.
3.3. 13C and 1H NMR spectra
The 13C and 1H chemical shifts for 1 in DMSO-d6 are listed in Ta-
ble 5. The relations between the experimental 13C and 1H chemical
shifts (dexp) and Gauge Inducting Atomic Orbitals (GIAO) isotropic
magnetic shielding constants (rcalc, Table 5) calculated for the opti-
mized structures 3 and 4, which are now widely used [26–28], are
FRA-106/S instrument operating at the 1064 nm exciting line of
Nd:YAG laser, with the resolution of 1 cmÀ1. The spectrum was
measured by acquisition of 200 scans.
NMR spectra in DMSO-d6 solution relative to TMS were re-
corded on a Bruker Advance DRX spectrometer operating at
599.93 and 150.85 MHz for 1H and 13C, respectively.
The DFT calculations were performed using the Gaussian 03 pro-
gram package [18]. The calculations employed the B3LYP
exchange–correlation functional, which combines the hybrid func-
tional of Becke [19,20] with the gradient-correlation functional of
usually linear and described by the following equation: dexp = a + b
r
calc. The slope and intercept of the least-square correlation lines
are used to scale the GIAO isotropic magnetic shielding constants,
, and to predict the chemical shifts, dpred = a + b rcalc (Fig. 5). As
r
shown by the data in Table 5, the agreement between the experi-
mental and calculated data is satisfactory both for carbon-13 and
hydrogen. The r.m.s. data for 4 are lower than for 3, which suggests

´
24
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
Table 4
Energies (Hartree, a.u.), dipole moments (
l
, Debye), hydrogen bond distances (Å), the shortest intermolecular contacts (Å), angels (°) in the crystals (1), vacuum (2) and DMSO (3–
4) for 2,3-dicarboxy-1-methylpyridinium chloride.
Compounds
Energy
l
D–HÁÁÁA
D–H
HÁÁÁA
DÁÁÁA
D–HÁÁÁA
N+ÁÁÁClÀ
X-ray
1
O(3)AH(3)ÁÁÁCl(1)
O(1)AH(1)ÁÁÁCl(1)a
0.88(5)
0.77(4)
2.10(5)
2.25(4)
2.970(2)
3.011(2)
171
169
7.4663b
3.495(2)c
4.121(2)c
4.199(2)d
B3LYP/6-311++G(d,p)
2 Vacuum
3 DMSO
À1125.7351966
À1125.8076926
À1125.7924472
17.5222
32.4765
19.2640
Cl(1)AHÁÁÁO(3)
O(3)AH(3)ÁÁÁCl(1)
Cl(1)AHÁÁÁO(4)
O(3)AHÁÁÁO(1)
1.3444
1.0120
1.3424
1.0300
1.6418
1.9823
1.6499
1.4774
2.9805
2.9831
2.9888
2.4856
172.92
169.57
174.50
164.64
7.6290b
7.5542b
7.6194b
4 DMSO
Symmetry codes:
a
x, À0.5Ày, À0.5 + z.
b
x, y, z.
c
Àx, ÀyÀ1, Àz + 1.
d
x, y, z + 1.
Fig. 2. Autostereographic projection [35] of two chains of hydrogen bonded ionic pairs in the crystal structure of (1). The hydrogen bonds are indicated by the dashed line,
and the thermal ellipsoids are shown at the 50% probability level.
that in DMSO solution the intramolecular OÁHÁO hydrogen bond is
The fine structure of the mOH and mOD absorptions observed in
the investigated chlorides are generated by the strong anharmonic
formed.
coupling mechanism, in which the most prominent role is played
by the high frequency proton stretching vibration
ically coupled with the low frequency AAHÁ Á ÁB hydrogen bond
stretching vibration
(AAHÁ Á ÁB) [29,30]. Further contribution to
the absorption is brought by the Fermi resonance between the
mAH, anharmon-
3.4. FTIR and Raman spectra
m
The FTIR spectra of 1 and its deuterated analog measured in the
solid state are shown in Fig. 6a and frequencies are listed in Table
6. The broad and strong absorption with three maxima at 2709,
overtones and mAH vibration [31].
The intense doublets at 1750 and 1729 cmÀ1 correspond to the
2562 and 2467 cmÀ1 arise from the
m
OH stretching vibration. In
m
C@O vibrations. In deuterated complex these bands are shifted to
the Raman spectrum, the intensity of this absorption is much
1747 and 1725 cmÀ1. In Raman spectrum the single
mC@O band is
weaker (Fig. 6c). In the spectrum of deuterated sample the
m
OD
at 1725 cmÀ1
.
bands are located at 2087, 1990 and 1926 cmÀ1. In general the FTIR
spectra of the compounds investigated are similar to those of 3,4-
dicarboxy-1-methylpyridinium chloride and its deuterated sample
[13].
In the spectrum of 1 the OH deformation in-plane and out-of-
plane vibrations appear as doublets at 1398 and 1381 cmÀ1 (bOH)
and 890 and 868 cmÀ1
(c
OH) which on deuteration are shifted to
1028, 1016 and 635, 626 cmÀ1, respectively. The absorption at

´
25
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
Fig. 3. Autostereographic projection [35] of the ionic packing in crystal structure of 2,3-dicarboxy-1-methylpyridinium chloride. The hydrogen bonds are indicated by the
dashed line.
Fig. 4. Comparison of the X-ray (1) and B3LYP/6-311++G(d,p) (2–4) structures of 2,3-dicarboxy-1-methylpyridinium chloride.
Table 5
Experimental, predicted (dpred = a + b rcalc
(ppm) and calculated GIAO/B3LYP/6-311G(d,p) isotropic magnetic shielding con-
stants ( calc) for 2,3-dicarboxy-1-methypyridinium chloride in DMSO.
) carbon-13 and proton chemical shifts
higher frequencies corresponds to the shorter OHÁ Á ÁClÀ hydrogen
bonds. Two bands of deformation OH and OD vibrations are in good
agreement with the X-ray data.
r
Atoma
dexp
dpred (3)
dpred (4)
rcalc (3)
rcalc (4)
In the second-derivative spectra, d2, the minima have the same
wavenumbers as the maxima in the absorbance spectra [29,32–
34]. The intensity of relative amplitudes of bands in d2 spectra var-
ies inversely to the square of their half-width ratio. The half-widths
Carbon
C(2)
C(3)
C(4)
C(5)
149.47
128.29
146.67
127.26
149.25
46.54
148.15
129.70
148.31
128.82
147.62
45.87
151.28
127.11
147.58
124.28
147.16
47.93
27.6592
46.9872
27.4888
47.9166
28.2136
134.8489
13.3969
13.6755
174.5361
À0.9541
0.9993
23.1598
48.3205
27.0114
51.2630
27.4530
130.7285
12.6663
6.8635
of the mOH and mOD bands are too large and therefore intensities of
C(6)
C(7)
these bands in the d2 spectra are very weak (Fig. 6b).
The band at 1227 cmÀ1 in the spectrum of 1 which disappears
on deuteration (Fig. 6a) does not correspond to a fundamental
transition, but it should be assigned to a combination of skeletal
C(8)OO
C(9)OO
ab
161.21
163.02
161.62
161.49
161.36
165.02
173.5333
À0.9608
0.9988
bc
vibrations with
c
OH. An analogous new band at 1335 cmÀ1 in
rd
Av. dif.e
R.m.sf
0.02
1.44
À0.02
the deuterated IR spectrum should be a combination of skeletal
vibrations with bOD.
1.91
Proton
H(4)
H(5)
H(6)
NCH3
8.98 (d)
8.24 (dd)
9.28 (d)
4.33
8.96
9.03
8.39
4.46
9.42
8.23
8.78
4.39
22.4128
22.3254
23.0737
27.8359
27.4893
27.5507
27.6253
28.3030
À0.8632
0.9532
22.7277
23.8791
23.3457
27.9142
26.9951
27.9214
27.6102
32.8075
À1.0291
0.9858
4. Conclusions
The molecular and crystal structures of 2,3-dicarboxy-1-meth-
ylpyridinium chloride (1) have been determined by X-ray diffrac-
tion and the B3LYP/6-311++G(d,p) calculations. In the crystal,
each ClÀ ion is engaged in two hydrogen bonds with the COOH
groups of two molecules, OHÁ Á ÁClÀÁ Á ÁHO, of 2.970(2) and
3.011(2) Å. According to the B3LYP/6-311++G(d,p) calculations, in
molecule 2 (vacuum) and 4 (DMSO) the hydrogen bonded proton
is linked with chlorine atom, ClAHÁ Á ÁO, while in 3 (DMSO) the
ClÀ anion interacts with COOH group, similarly as in the crystal
(ClÀÁ Á ÁHAO). The correlations between the experimental 13C and
1H chemical shifts in DMSO-d6 and the isotropic magnetic shield-
ing constants obtained by the GIAO/B3LYP/6311++G(d,p)
NCH3 av
ab
bc
rd
Av. dif.e
R.m.sf
À0.003
À0.003
0.69
0.39
a
b
c
d
e
f
Numbering of atoms is given in Fig. 1.
Intercept.
Slope.
Correlation coefficient.
Average (signed) differences between experimental and predicted chemical shifts.
Root-mean-square errors.

´
26
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
180
150
120
90
10
(a)
(b)
9
8
7
6
5
4
60
30
0
30
60
90 120 150
22 23 24 25 26 27 28
Magnetic isotropic shielding constants
Fig. 5. Plot of the experimental chemical shifts in DMSO-d6 (dexp) vs. the magnetic isotropic shielding constants (
2,3-dicarboxy-1-methylpyridinium chloride (3) in DMSO; (a) carbon-13, (b) proton.
rcalc) from the GIAO/B3LYP/6-311++G(d,p) calculations for
2.0
(a)
1.6
1.2
0.8
0.4
0.0
(b)
0.2
0.0
-0.2
-0.4
(c)
0.08
0.04
0.00
3600
3000
2400
1800
1500
1200
900
600
Wavenumbers (cm-1)
Fig. 6. Spectra of 2,3-dicarboxy-1-methylpyridinium chloride (1): (a) FTIR spectra in Nujol and Fluorolube, (b) second-derivative spectra, and (c) Raman spectrum in solid
state. Dashed line denotes spectra of deuterated sample.
Table 6
Experimental vibrational data for 2,3-dicarboxy-1-methylpyridinium chloride.
Raman
FTIR
H
Aproximate assign.a
H
D
3181
3127
3104
3093
3079
2971
2800–2400
1725
m
m
m
m
m
m
m
m
m
m
m
CH
CH
CH
CH3
CH3
CH3
OH/
C@O
C@O
CC
3123
3089
3124
3089
2900–2300
1750
1729
1618
1590
2100–1900
1747
1725
1617
1591
mOD
1621
1594
CC

´
27
P. Barczynski et al. / Journal of Molecular Structure 1018 (2012) 21–27
Table 6 (continued)
Raman
FTIR
Aproximate assign.a
1503
1471
1458
1416
1400
1381
1289
1272
1241
1229
1180
1148
1124
1066
960
1498
1442
1498
1442
bCH
mCC
mCC
mCC
1398
1381
1028
1016
1282
1260
1233
1335
1188
1148
1124
bOH/bOD
bOH/bOD
bCH
1267
1238
1227
1182
1146
1123
m
CN
bCH
CC +
m
cOH/cOD
bCH3, bCH
bCH3
mCC
bCH3
957
915
890
868
839
802
780
745
727
675
666
576
556
524
448
c
m
c
c
CH
919
901
635
626
837
802
781
754
740
689
677
569
554
521
447
CN,
OH/
OH/
mCC
c
OD
cOD
839
808
Ring,
Ring,
Ring,
m
m
m
CN
CN
CN
744
729
669
s
c
CO
CH
Ring + bCO
Ring + bCO
Ring + bCO
Ring + bCO
Ring + bCO
578
527
450
Ring + mCN
a
Abbreviations:
m, stretching; b, deformation in plane;
c
, deformation out-of-plane; s, torsion.
[16] C.K. Johnson, ORTEPII. Report ORNL-5138, Oak Ridge National Laboratory,
Tennessee, USA, 1976.
[17] Stereochemical Workstation Operation Manual, Release 3.4, Siemens
Analytical X-ray Instruments INC. Madison, 1989.
approaches are linear with good correlation coefficients. The broad
bands in the 2900–2400 cmÀ1 region correspond to the OH stretch-
ing vibrations. In the Raman spectrum, the intensity of this absorp-
tion is much weaker. The half-width of this absorption is too large
and in the d2 spectrum the corresponding negative peak is very
weak. The deformation in-plane and out-of-plane OH modes, both
in FTIR and d2 spectra, appear as two bands corresponding to two
OHÁ Á ÁClÀ bonds. In FTIR spectrum there are two bands correspond-
[18] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
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H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
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Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
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mC@O vibration, while only one in Raman spectrum.
Acknowledgment
´
The calculations were performed at the Poznan Supercomput-
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