2,6-diphenylpyridine-4-carboxylic acid

Article abstract of DOI:10.1107/S0108270101017693

The crystal structure of 2,6-diphenylpyridine-4-carboxylic acid, C₁₈H₁₃NO₂ was studied. Dihedral angles between the plane of pyridine and those of the phenyl substituents were found to be 8.7 and 9.8 (1)°. The shortest int

Full text of DOI:10.1107/S0108270101017693

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
2
,6-Diphenylpyridine-4-carboxylic
acid
Alessandra Crispini and Francesco Neve*
Dipartimento di Chimica, Universit a della Calabria, 87030 Arcavacata di Rende (CS),
Italy
Correspondence e-mail: f.neve@unical.it
Received 15 October 2001
Accepted 18 October 2001
Online 22 December 2001
Figure 1
The molecular structure of (I) showing the atom-labelling scheme and
displacement ellipsoids at the 50% probability level.
The distinctive feature of the crystal structure of 2,6-
diphenylpyridine-4-carboxylic acid, C H NO , is the forma-
1
8
13
2
tion of intermolecular OÐHÁ Á ÁO hydrogen bonds that lead to
2
2
the formation of centrosymmetric cyclic dimers with R (8)
topology. Molecules related by translation along the b axis
exhibit strong ꢀ±ꢀ stacking of aromatic rings, with an average
Ê
interplanar distance of 3.3 A.
Comment
The most common packing motif of carboxylic acids is based
on the formation of cyclic dimers through a pair of OÐHÁ Á ÁO
bonds (Leiserowitz, 1976). By contrast, the solid-state chem-
istry of pyridinecarboxylic acids is dominated by the formation
of an intermolecular OÐHÁ Á ÁN hydrogen bond between the
carboxylic acid group and the pyridine N atom of a second
molecule (Takusagawa & Shimada, 1976; Wright & King,
1
953). The latter hydrogen-bonding interaction can be
+
described more accurately as occurring via OÐHÁ Á ÁN or NÐ
�
HÁ Á ÁO , bonds depending on the tautomeric form present.
Figure 2
The crystal packing of (I) viewed down the b axis.
Similar arguments also apply to other heterocyclic aromatic
carboxylic acids, such as pyrazinic acid (Takusagawa et al.,
1
1
974) and quinoline-4-carboxylic acid (Dobson & Gerkin,
998). The directional nature of the OÐHÁ Á ÁN bonding
cocrystallized water molecule are still present (Takusagawa et
al., 1973).
interaction for the isonicotinic acid has been exploited in the
The molecular structure of (I) is shown in Fig. 1. Geometric
parameters are normal (Table 1) and compare well with those
of other 2,6-diphenylpyridines (Krygowski et al., 1994; Silva et
al., 1997). The whole molecule is nearly planar, as clearly
shown by the values of the torsion angles reported in Table 1.
Dihedral angles between the best-®t plane of the pyridine and
those of the phenyl substituents are 8.7 (1) (ring atoms C8±
ꢀ
C13) and 9.8 (1) (ring atoms C14±C19).
promotion of highly oriented structures (O'Shea et al., 2001).
On the other hand, when carboxylic acid groups occupy both ꢁ
and ꢁ positions of the pyridine ring, as in dipicolinic acid, the
N atom is not involved in head-to-tail interactions of the type
The supramolecular structure of (I) can be described in
terms of ꢀ±ꢀ interactions and intermolecular hydrogen
bonding (Table 2). In the crystal packing, the molecules are
stacked along the b axis (Fig. 2). The shortest interplanar
0
Ê
described, although OÐHÁ Á ÁN hydrogen bonds with a
distance of 2.919 (2) A is found between the C14±C19 phenyl
o34 # 2002 International Union of Crystallography
DOI: 10.1107/S0108270101017693
Acta Cryst. (2002). C58, o34±o35

organic compounds
ring and its translation-related ring. The stacks are organized
in a pseudo-herring-bone fashion since the ꢀÁ Á ÁH interactions
do not seem to be dominant like in a classical herring-bone
stacking mode (Gavezzotti & Desiraju, 1988; Andr e et al.,
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
N1ÐC2
N1ÐC6
O1ÐC7
O2ÐC7
C2ÐC3
1.343 (3)
1.350 (3)
1.297 (3)
1.243 (3)
1.393 (3)
C3ÐC4
C4ÐC5
C4ÐC7
C5ÐC6
1.378 (3)
1.365 (3)
1.478 (3)
1.394 (3)
1
997). The dominant supramolecular interaction is the
OÐHÁ Á ÁO hydrogen bonding between centrosymmetric
carboxylic acid groups (Fig. 3). The corresponding graph-set is
O2ÐC7ÐO1
O2ÐC7ÐC4
122.8 (3)
121.6 (2)
O1ÐC7ÐC4
115.6 (3)
C3ÐC4ÐC7ÐO2
C5ÐC4ÐC7ÐO1
0.7 (4)
4.1 (4)
N1ÐC6ÐC8ÐC13
N1ÐC2ÐC14ÐC15
� 7.6 (4)
� 8.6 (3)
Table 2
Hydrogen-bonding geometry (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
i
O1ÐH1Á Á ÁO2
0.82
0.93
1.83
2.70
2.640 (3)
3.406 (3)
172
134
ii
C11ÐH11Á Á ÁO2
Symmetry codes: (i) 2 � x; 2 � y; 1 � z; (ii) ‡ x; � y; ‡ z.
1
2
1
2
1
2
Re®nement
2
Re®nement on F
R(F) = 0.045
H-atom parameters constrained
2 2 2
w = 1/[ꢅ (F
where P = (F
(Á/ꢅ)max < 0.001
o
) + (0.0250P) ]
2
wR(F ) = 0.089
S = 0.87
2 2
+ 2F )/3
o c
Ê
� 3
2
1
469 re¯ections
90 parameters
Áꢆmax = 0.13 e A
Áꢆmin = � 0.13 e AÊ
� 3
Figure 3
A partial view of the crystal structure of (I) showing the formation of ring
Data collection: XPREP (Bruker, 1997); cell re®nement: XPREP;
2
motifs with graph-set R (8) that further interact through lateral CÐ
4
2
data reduction: XPREP; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker,
1997).
HÁ Á ÁO interactions to afford larger rings with graph-set R (44).
6
2
2
therefore R (8) (Etter et al., 1990), which is typical for
carboxyl dimers. In addition, a second motif with graph-set
4
6
R (44) can be identi®ed in the crystal packing when weaker
hydrogen bonds of the CÐHÁ Á ÁO type are considered (Fig. 3).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1541). Services for accessing these data are
described at the back of the journal.
Experimental
References
The title compound was prepared in one step from 3-benzoylacrylic
acid and N-phenacylpyridinium bromide in the presence of excess
ammonium acetate (Blumbergs et al., 1972). The compound was
recrystallized from hot acetic acid as pale-yellow crystals.
Andr e , I., Foces-Foces, C., Cano, F. H. & Martinez-Ripoll, M. (1997). Acta
Cryst. B53, 996±1005.
Blumbergs, P., LaMontagne, M. P., Markovac, A., Moehring, J. G., Ash, A. B. &
Stevens, C. L. (1972). J. Med. Chem. 15, 808±812.
Bruker (1997). XPREP and XP. Bruker AXS Inc., Madison, Wisconsin, USA.
Dobson, A. J. & Gerkin, R. E. (1998). Acta Cryst. C54, 1883±1885.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256±262.
Gavezzotti, A. & Desiraju, G. R. (1988). Acta Cryst. B44, 427±434.
Krygowski, T. M., Anulewicz, R., Jarmula, A., Bak, T., Rasala, D. & Howard, S.
(1994). Tetrahedron, 50, 13155±13164.
Leiserowitz, L. (1976). Acta Cryst. B32, 775±802.
O'Shea, J. N., Schnadt, J., Br uÈ hwiler, P. A., Hillesheimer, H., M aÊ rtensson, N.,
Ê
Patthey, L., Krempasky, J., Wang, C.-K. & Agren, H. (2001). J. Phys. Chem.
Crystal data
�
3
C
18
H13NO
2
D
x
= 1.32 Mg m
M
r
= 275.29
Monoclinic, P2
Mo Kꢁ radiation
1
Ê
Ê
/n
Cell parameters from 25
re¯ections
a = 16.524 (4) A
b = 5.2898 (9) A
Ê
c = 17.021 (3) A
ꢂ = 111.229 (17)
Ê
V = 1386.8 (5) A
Z = 4
ꢀ
ꢃ = 8.0±12.9
� 1
ꢄ = 0.09 mm
T = 293 (2) K
ꢀ
3
105, 1917±1920.
Block, pale yellow
0.23 Â 0.20 Â 0.17 mm
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
Silva, A. M. S., Almeida, L. M. P. M., Cavaleiro, J. A. S., Foces-Foces, C.,
Llamas-Saiz, A. L., Fontenas, C., Jagerovic, N. & Elguero, J. (1997).
Tetrahedron, 53, 11645±11658.
Takusagawa, F., Higuchi, T., Shimada, A., Tamura, C. & Sasada, Y. (1974).
Bull. Chem. Soc. Jpn, 47, 1409±1413.
Takusagawa, F., Hirotsu, K. & Shimada, A. (1973). Bull. Chem. Soc. Jpn, 46,
2020±2027.
Data collection
Siemens R3m/V diffractometer
ꢃ/2ꢃ scans
h = 0 ! 19
k = 0 ! 6
2
2
9
559 measured re¯ections
469 independent re¯ections
80 re¯ections with I > 2ꢅ(I)
l = � 20 ! 18
2 standard re¯ections
frequency: 48 min
intensity decay: none
R
int = 0.069
Takusagawa, F. & Shimada, A. (1976). Acta Cryst. B32, 1925±1927.
Wright, W. B. & King, G. S. D. (1953). Acta Cryst. 6, 305±317.
ꢀ
ꢃ
max = 25.1
ꢁ
Acta Cryst. (2002). C58, o34±o35
Crispini and Neve
18
C H13NO
2
o35