Synthesis and X-ray structure analysis of 2-acetylamino-benzoic acid

Article abstract of DOI:10.1023/B:JOCC.0000035389.59351.3a

The title compound crystallizes in the orthorhombic space group Fdd2 with unit cell parameters a = 10.848(1) , b = 30.264(1) and c = 10.577(1) , V = 3472.47(2) ³, and Z = 4. The final reliability index is 0.030 for 700 observed reflections. Nitrogen of the amide group and carbon atom of the acid group deviate significantly below and above the plane of the phenyl ring. The crystal cohesion is accentuated by NbondHO and ObondHO hydrogen bonds.

Full text of DOI:10.1023/B:JOCC.0000035389.59351.3a

C
Journal of Chemical Crystallography, Vol. 34, No. 7, July 2004 ( 2004)
Synthesis and X-ray structure analysis
of 2-acetylamino-benzoic acid
Rajnikant,(1) Dinesh,(1) Kamni,(1) and M.B. Deshmukh(2)
Received March 28, 2004
The title compound crystallizes in the orthorhombic space group Fdd2 with unit cell pa-
3
˚
˚
˚
˚
rameters a = 10.848(1) A, b = 30.264(1) A and c = 10.577(1) A, V = 3472.47(2) A ,
and Z = 4. The final reliability index is 0.030 for 700 observed reflections. Nitrogen of the
amide group and carbon atom of the acid group deviate significantly below and above the
plane of the phenyl ring. The crystal cohesion is accentuated by N H O and O H
hydrogen bonds.
O
KEY WORDS: Quinazolinones; molecular structure; organic compound; intra- and intermolecular interactions.
Introduction
anthranilic acid (10 g, 0.07 mol) in pyridine to
which the acetic anhydride (15.3 g, 0.15 mol) in
Alkaloids are renowned for their potent and
pyridine (25 mL) was added dropwise at room
temperature with constant stirring for 0.5 h, fol-
lowed by the treatment with 5% NaHCO3 so-
lution. The separated solid was recrystallized
from ethanol to give the desired compound.
Yield: 82%, melting point: 393 K. The chemi-
cal structure assigned to the title compound as
shown in Fig. 1. was established on the basis
of some chemical studies9 [elemental analysis:
Found: C, 60.3%; H, 5.0%; N, 7.8%. Calcd: C,
60.33%; H, 5.06%; N, 7.82%; Spectral character-
istics: IR(KBr): vmax, 3350 ( NH), 1680 (amido
diverse pharmacological activities.1,2 As a part of
our on-going work on the synthesis and structure
elucidation of alkaloids3–8 and in view of their
immense clinical use, the crystal structure of 2-
acetylamino-benzoic acid has been determined.
The title compound has been synthesized as an in-
termediate for quinazolinones. In this paper we re-
port the X-ray structure of 2-acetylamino-benzoic
acid and possible role of intra- and intermolecular
interactions.
1
1
C O), 1620 cm (C N). HNMR (DMSO-
d6): , 3.8 (3H, s, COCH3), 6.8–7.6(9H,m,
Ar-H), 10.8 (1H, s, Exchangeable with D2O,
COOH)].
Experimental
In a round-bottomed flask carrying a re-
flux condenser and a guard tube the solution of
Three-dimensional intensity data of a plate
shaped crystal (0.3 0.3 0.2 mm) was collected
on an Enraf-Nonius CAD-4 diffractometer (Mo
(1) Condensed Matter Physics Group, Post Graduate Department of
Physics, University of Jammu, Jammu Tawi 180 006, India.
(2) Department of Chemistry, Shivaji University, Kolhapur,
Maharashtra 416 004, India.
To whom correspondence should be addressed; e-mail:
rkantverma@rediffmail.com.
˚
K radiation, = 0.71069 A, ω/2 scan mode).
A total of 798 reflections were found to be unique
(0
h
12, 2
k
35, 0
l
12) and 700
471
C
1074-1542/04/0700-0471/0 2004 Plenum Publishing Corporation

472
Rajnikant, Dinesh, Kamni, and Deshmukh
hydrogen atoms. All the hydrogen atoms were
fixed stereochemically except hydrogen atoms co-
valently bonded to N and O. The final refinement
cycle converged R-factor to 0.030. The flack pa-
rameter has not been determined in view of the
fact that Mo K radiation has been used for data
collection. The residual electron density in the fi-
nal Difference Fourier map ranges from 0.13 to
3
˚
Fig. 1. Chemical structure of 2-acetylamino-benzoic acid.
–0.10 e A . Atomic scattering factors were
taken from International Tables for Crystallogra-
phy (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4).
Structural calculations were obtained from the
PC-version of PARST.12
reflections were considered as observed [Fo >
4
(Fo)]. The reflection data were corrected for
Lorentz and Polarization effects and no absorp-
tion correction was applied.
Results and discussion
The structure has been elucidated by direct
methods using SHELXS86.10 All non-hydrogen
atoms of the molecule were located from the
E-map. Isotropic refinement of the structure by
least-squares methods using SHELXL9311 was
followed by anisotropic refinement of all the non-
Precise crystal data and other structure re-
finement parameters of the title compound are pre-
sented in Table 1. Bond distances and bond angles
are given in Table 2. General view of the molecule
with atomic labeling (thermal ellipsoids drawn at
50% probability) is shown in Fig. 2.
Table 1. Crystal Data and Structure Refinement Details
The molecule consists of a phenyl ring to
which an amide group is attached at C2 and the
acid group ( COOH) at C1. The average value
of the bond distances [1.370(4) A] and exocyclic
bond angles [120.0(3) ] in the phenyl ring have
Empirical formula
CCDC reference no.
Formula weight
C9 H9 N1 O3
218921
716.69
˚
Temperature, K
293(2)
˚
Wavelength, A
0.71069
Crystal system, space group
Unit cell dimensions
Orthorhombic, Fdd2
˚
a = 10.848(5) A
˚
˚
Table 2. Bond Distances (A) and Bond Angles (deg) for Non-
b = 30.264(5) A
˚
Hydrogen Atoms
c = 10.577(5) A
= 90.0(5)
= 90.0(5)
= 90.0(5)
3472(2)
N(1) C(8)
O(1) C(7)
O(3) C(8)
C(1) C(2)
C(2) C(3)
C(4) C(5)
1.342(4) N(1) C(2)
1.310(3) O(2) C(7)
1.238(4) C(1) C(6)
1.403(4) C(1) C(7)
1.401(4) C(3) C(4)
1.371(5) C(5) C(6)
1.489(4)
130.0(2) C(6) C(1) C(2) 119.1(2)
118.6(2) C(2) C(1) C(7) 122.3(2)
118.5(2) C(3) C(2) N(1) 122.9(2)
118.6(2) C(4) C(3) C(2) 120.6(3)
121.2(3) C(4) C(5) C(6) 118.8(3)
121.8(3) O(2) C(7) O(1) 122.7(3)
124.6(2) O(1) C(7) C(1) 112.7(2)
122.9(2) O(3) C(8) C(9) 121.9(3)
115.2(3)
1.409(3)
1.213(3)
1.390(3)
1.493(3)
1.376(4)
1.377(4)
3
˚
Volume, A
Z, Calculated density, mg/m3
4, 1.371
1504
0.3 0.3 0.2
2.69–24.96
F(000)
Crystal size, mm
Range for data collection, deg
Limiting indices
C(8) C(9)
C(8) N(1) C(2)
C(6) C(1) C(7)
C(3) C(2) C(1)
C(1) C(2) N(1)
C(5) C(4) C(3)
C(5) C(6) C(1)
O(2) C(7) C(1)
O(3) C(8) N(1)
N(1) C(8) C(9)
0
h
12,
12
2
k
35,
0
l
Reflections collected/unique
Refinement method
862/798 [R(int) = 0.0112]
Full-matrix least-squares
on F2
798/1/119
1.075
R1 = 0.0303, wR2 = 0.0823
R1 = 0.0377, wR2 = 0.0876
0.127 and 0.099
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [Fo > 4 (Fo)]
R indices (all data)
3
˚
Largest diff. peak and hole, e A
Note. esd’s are given in parentheses.

Analysis of 2-acetylamino-benzoic acid
473
these interactions depicts a graph set C22(4) (where
C refers to chain or catemer, no. of donors—2,
no. of acceptors—2, and no. of atoms involved—
4).17 Geometry of intra- and intermolecular in-
teractions (esd’s are given in parentheses) is pre-
sented below:
˚ ˚
D[X A (A)] d[H A (A)] [X–H A] (deg)
X–H
N1–H1 O2
O1–H1A O3i 2.63(4)
A
2.66(3)
1.94(3)
1.83(3)
139.7(3)
164.6(3)
Note. Symmetry codes: (i) x 1/4, y + 1/4, z + 3/4.
Hydrogen bonding as shown in Fig. 3.
has been drawn by using ORTEP-III18 software.
Molecular staggering is typical of orthorhom-
bic space group Fdd2. There appears to be an
active participation of O1 and N1 which act
as protonated donors for O3 and O2, respec-
tively. This intermolecular bond is responsible
for providing molecular stability to the unit
cell.
Fig. 2. General view of the molecule with thermal ellipsoids
drawn at 50% probability level.
normal values which agrees quite well with the
values reported in the literature for some anal-
ogous structures.13,14 The molecule as such is
close to planar and planarity is further confirmed
by the magnitude of torsion angles [maximum
value of torsion for the C2 N1 C8 O3 bond is
6.0(5) ] which is in agreement with the literature
value.15 This is expected due to the steric hin-
drance of the amide group at C2 and acid group
located at C1 position. Steric hindrance is also re-
lieved due to exocyclic bond angles at C1, C2,
and also the large value of the exocyclic angle at
N1. Nitrogen (N1) of the amide group and carbon
atom (C7) of the acid group are deviated signifi-
cantly below and above the plane of the benzene
˚
ring [deviations being 0.072(2) and 0.035(3) A,
respectively].
The structure exhibits one intra- and one in-
termolecular hydrogen bonded interactions. In-
tramolecular interaction i.e. N1–H1 O2 gives
rise to one six-membered virtual ring and hence
making the present molecule look like a two-ring
structure. The value of intra- and intermolecular
contacts with d(H A) distance of 1.94(3) and
˚
1.83(3) A, respectively, is in conformity with the
theory and predictions as made for the strong hy-
drogen bonds and thus plays an important role in
stabilizing the structure.16 The motif generated by
Fig. 3. Depiction of hydrogen-bonded interactions.

474
Rajnikant, Dinesh, Kamni, and Deshmukh
Supplementary materials Supplementary data of 2-Acetylamino-
benzoic acid:
Acknowledgments
The corresponding author (Rajnikant) is
1. Anisotropic thermal parameters for non-hydrogen
atoms
2. Torsion angles for non-hydrogen atoms
3. Least-squares planes
thankful to the University Grants Commission,
New Delhi for the financial support under its DRS
Research Project no: F.530/3/DRS/2001(SAP-I).
2
˚
Table 1. Anisotropic Thermal Parameters (A ) for Non-Hydrogen Atoms
Atom
U11
U22
U33
U23
U13
U12
N(1)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
0.073(2)
0.117(2)
0.117(2)
0.107(2)
0.045(1)
0.052(1)
0.076(2)
0.076(2)
0.064(2)
0.054(1)
0.059(2)
0.056(2)
0.077(2)
0.039(1)
0.048(1)
0.038(1)
0.058(1)
0.039(1)
0.041(2)
0.045(2)
0.045(1)
0.039(1)
0.038(1)
0.044(2)
0.054(2)
0.052(2)
0.037(1)
0.042(1)
0.051(1)
0.039(1)
0.034(1)
0.035(1)
0.036(1)
0.051(2)
0.054(2)
0.038(1)
0.036(1)
0.041(1)
0.056(2)
0.001(1)
0.002(1)
0.008(1)
0.005(1)
0.002(1)
0.002(1)
0.004(1)
0.014(1)
0.001(1)
0.001(1)
0.003(1)
0.009(2)
0.011(2)
0.010(1)
0.029(1)
0.026(1)
0.019(1)
0.002(1)
0.003(1)
0.010(1)
0.009(2)
0.004(2)
0.002(1)
0.007(1)
0.005(1)
0.007(2)
0.001(1)
0.006(1)
0.003(1)
0.004(1)
0.001(1)
0.000(1)
0.001(1)
0.003(1)
0.000(1)
0.001(1)
0.001(1)
0.002(1)
0.006(1)
Note. esd’s are given in parentheses.
Table 2. Torsion Angles (deg) for Non-Hydrogen Atoms
C(6) C(1) C(2) C(3)
C(6) C(1) C(2) N(1)
C(8) N(1) C(2) C(3)
C(1) C(2) C(3) C(4)
C(2) C(3) C(4) C(5)
C(4) C(5) C(6) C(1)
C(7) C(1) C(6) (5)
C(2) C(1) C(7) (2)
C(2) C(1) C(7) O(1)
C(2) N(1) C(8) C(9)
1.5(4)
176.6(3)
0.7(5)
0.6(4)
0.7(5)
0.2(4)
178.7(2)
3.5(4)
175.3(3)
174.0(3)
C(7) C(1) C(2) C(3)
C(7) C(1) C(2) N(1)
C(8) N(1) C(2) C(1)
N(1) C(2) C(3) C(4)
C(3) C(4) C(5) C(6)
C(2) C(1) C(6) C(5)
C(6) C(1) C(7) O(2)
C(6) C(1) C(7) O(1)
C(2) N(1) C(8) (3)
178.4(3)
3.5(4)
177.3(3)
177.4(3)
1.1(5)
1.1(4)
176.7(3)
4.5(4)
6.0(5)
Note. esd’s are given in parentheses.
Table 3. Least-Squares Planesa
˚
˚
Plane 1 Atom
Deviation (A)
Atom
Deviation (A)
C1
C3
C5
N1b
0.006(2)
0.002(3)
0.005(3)
0.072(2)
C2
C4
C6
C7b
0.008(3)
0.008(3)
0.003(2)
0.035(3)
Note. esd’s are given in parentheses.
aEquation of the plane:- m1 x+m2 y+m3 z = d.
bAtoms not included in the plane.

Analysis of 2-acetylamino-benzoic acid
References
475
10. Sheldrick, G.M. SHELXS86, Program for Crystal Struc-
ture Determination; University of Gottingen: Germany,
1986.
11. Sheldrick, G.M. SHELXL93, Program for Refinement of
Crystal Structures; University of Gottingen: Germany,
1993.
12. Nardelli, M. J. Appl. Crystallogr. 1995, 28, 659.
13. Odabasoglu, M.; Buyukgungor, O.; Lonnecke, P. Acta Crystal-
logr. C 2003, 59, o51–o52.
14. Buyukgungor, O.; Odabasoglu, M. Acta Crystallogr. C 2002,
58, o691–o692.
15. Vedasankari, G.; Murthy, S.; Udupa, M.R. Acta Crystallogr. C
1990, 46, 1709–1711.
16. Desiraju, G.R.; Steiner, T. The Weak Hydrogen Bond in Struc-
tural Chemistry and Biology; IUCr, Oxford University Press,
UK, 1999; pp 48.
1. Babita, M. PhD Thesis, Regional Research Laboratory, Jammu
Tawi, India, 1994.
2. Thappa, R.K.; Agarwal, S.G.; Dhar, K.L.; Gupta, V.K.;
Goswami, V.K. Phytochemistry 1996, 42, 1485.
3. Rajnikant;Gupta, V.K.;Deshmukh, M.B.;Varghese, B.;Dinesh.
Cryst. Res. Technol. 2001, 36(12), 1451.
4. Rajnikant; Gupta, V.K.; Hashmi, S.; Shafiullah; Varghese, B.;
Dinesh. Crystallogr. Rep. 2002, 47(1), 75.
5. Rajnikant; Gupta, V.K.; Khan, E.H.; Shafi, S.; Shafiullah;
Dinesh. J. Chem. Crystallogr. 2002, 32(9), 325.
6. Rajnikant; Gupta, V.K.; Dinesh; Kumar, A. Mol. Cryst. Liq
Cryst. 2002, 383, 99.
7. Rajnikant;Gupta, V.K.;Deshmukh, M.B.;Varghese, B.;Dinesh.
Crystallogr. Rep. 2002, 47, 449.
17. Berstein, J.; Etter, M.C.; Leiserowitz, L. In Structure Correla-
tion; Burgi H.B.; Dunitz, J.D., eds.; VCH: Weinheim, 1994;
Vol. 2, pp 431.
8. Rajnikant; Gupta, V.K.; Suri, O.P.; Lal, M. Ind. J. Pure Appl.
Phys. 2002, 40, 59.
9. Deshmukh, M.B. Private communication, Shivaji University:
Kolhapur, India, 2003.
18. Farrugia, L.J. Appl. Crystallogr. 1997, 30, 565.