Synthesis and crystal structure of n-cyclohexyl-2-nitrobenzamide

Article abstract of DOI:10.1007/s10870-010-9764-0

N-Cyclohexyl-2-nitrobenzamide was synthesized and characterized by spectroscopic data and X-ray diffraction analysis. It crystallizes at room temperature in the monoclinic space group P21/n with cell parameters a = 13.9913(10), b = 8.8475(4), c = 20.5627(15) A, β = 93.278(6)°, V = 2541.3(3) A³ and Z = 8. The structure was refined to final R1 = 0.0626 using all 4950 reflections. The crystal packing is stabilized by N-H...O hydrogen bonds. Graphical Abstract: N-Cyclohexyl-2-nitrobenzamide was synthesized and characterized by spectroscopic data and X-ray diffraction analysis. It crystallizes at room temperature in the monoclinic space group P21/n with cell parameters a = 13.9913(10), b = 8.8475(4), c = 20.5627(15) A, β = 93.278(6)°, V = 2541.3(3) A³ and Z = 8. The structure was refined to final R1 = 0.0626 using all 4950 reflections. The crystal packing is stabilized by N-H...O hydrogen bonds. [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-010-9764-0

J Chem Crystallogr (2010) 40:924–926
DOI 10.1007/s10870-010-9764-0
ORIGINAL PAPER
Synthesis and Crystal Structure of N-Cyclohexyl-2-
Nitrobenzamide
Aamer Saeed
•
Shahid Hussain Michael Bolte
•
Received: 29 July 2008 / Accepted: 7 May 2010 / Published online: 19 May 2010
Springer Science+Business Media, LLC 2010
ꢀ
Abstract N-Cyclohexyl-2-nitrobenzamide was synthe-
sized and characterized by spectroscopic data and X-ray
diffraction analysis. It crystallizes at room temperature in the
We have become interested in the synthesis of 2-nitro-
benzanilides as intermediates towards novel heterocycles
and for the systematic study of their bioactive behavior. We
report on the structure of the title molecule (I), (Fig. 1)
based on a single-crystal X-ray structural analysis.
monoclinic space group P21/n with cell parameters a =
˚
1
9
3.9913(10), b = 8.8475(4), c = 20.5627(15) A, b =
3
˚
3.278(6)ꢁ, V = 2541.3(3) A and Z = 8. The structure was
refined to final R1 = 0.0626 using all 4950 reflections. The
crystal packing is stabilized by N–H_O hydrogen bonds.
Results and Discussion
Keywords X-ray structure Á
N-Cyclohexyl-2-nitrobenzamide Á Synthesis
2-Nitrobenzoyl chloride was refluxed with an equimolar
amount of cyclohexyl amine in dry THF in presences of aq.
potassium carbonate. The product was recrystallized from
benzene. FTIR spectrum showed the stretching vibrations
at 3271 (N–H), 1638 (C=O), 1586 (C=C), and 1150 (C–N)
Introduction
-
1 1
Benzanilides are versatile intermediates towards a diversity
of heterocyclic compounds: benzothiadiazin-4-ones, qui-
nazoline-2,4-diones, benzodiazepine-2,5-diones, and 2,3-
disubstituted 3H-quinazoline-4-ones [1]. Benzanilides con-
taining aminoalkyl groups originally designed as pepti-
domimetics have been incorporated in an Arg–Gly–Asp
cyclic peptide yielding a high affinity GPIIb/IIIa ligand [2].
Pyridylmethyl containing benzanilides are vascular endo-
thelial growth factor receptor and tyrosine kinase inhibitors
cm . H NMR showed a doublet at d 5.92 (J = 7.5 Hz)
for NH, the multiplets for methylene and methine protons
of the cyclohexyl moiety at d 1.14–2.06 and 3.91, respec-
tively, in addition to the multiplet for aromatic protons at d
7.64–8.0, respectively. C NMR showed peaks at d 165.70
for carbonyl, at d 24.8–34.0 and 49.0 for methylene and
methine protons, and d 124.4–146.2 for aromatic protons,
respectively. Mass spectrum of the compound showed the
molecular ion peak at m/z 248, and the base peak at m/z 150
respectively.
1
3
[
3]; others are acetyl-CoA carboxylase and farnesyl trans-
ferase inhibitors [4].
A. Saeed (&) Á S. Hussain
H
N
Department of Chemistry, Quaid-I-Azam University,
Islamabad 45320, Pakistan
e-mail: aamersaeed@yahoo.com
N+
O
-O
O
M. Bolte
Institut f u¨ r Anorganische Chemie, J.-W.-Goethe-Universit a¨ t,
Max-von-Laue-Str. 7, 60438 Frankfurt/Main, Germany
Fig. 1 Structural chemical diagram of (1)
1
23

J Chem Crystallogr (2010) 40:924–926
925
4
Table 2 Atomic coordinates (910 ) and equivalent isotropic dis-
Table 1 Crystal data and experimental details
2
placement parameters (A 9 10 )
3
˚
Empirical formula
Formula weight
Temperature
13 16 2 3
C H N O
x
y
z
U(eq)
248.28
173(2) K
C(1)
2294(1)
2439(1)
2449(1)
2752(1)
2471(1)
3141(1)
1471(1)
1519(1)
741(1)
4690(2)
3951(2)
4415(2)
5822(1)
5311(1)
3694(1)
4154(2)
4155(2)
3876(2)
3590(2)
3577(2)
3853(2)
4388(2)
4002(2)
4360(2)
3583(2)
4020(2)
3627(2)
7275(2)
6528(2)
6995(2)
8413(1)
7879(1)
6256(1)
6717(2)
6750(2)
6484(2)
6146(2)
6059(2)
6345(2)
6901(2)
6483(2)
6773(2)
5971(2)
6426(2)
6104(2)
2160(1)
2720(1)
749(1)
23(1)
27(1)
29(1)
27(1)
40(1)
39(1)
23(1)
24(1)
29(1)
32(1)
33(1)
29(1)
27(1)
33(1)
38(1)
38(1)
39(1)
31(1)
24(1)
28(1)
30(1)
29(1)
42(1)
39(1)
24(1)
25(1)
30(1)
34(1)
34(1)
30(1)
29(1)
41(1)
52(1)
53(1)
46(1)
35(1)
˚
Wavelength
0.71073 A
Monoclinic
P21/n
N(1)
Crystal system
Space group
N(2)
O(1)
2007(1)
293(1)
˚
a = 13.9913(10) A
Unit cell
dimensions
a = 90ꢁ
O(2)
O(3)
970(1)
˚
b = 8.8475(4) A
b = 93.278(6)ꢁ
c = 90ꢁ
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(1A)
N(1A)
N(2A)
O(1A)
O(2A)
O(3A)
C(11A)
C(12A)
C(13A)
C(14A)
C(15A)
C(16A)
C(21A)
C(22A)
C(23A)
C(24A)
C(25A)
C(26A)
1712(1)
1035(1)
609(1)
˚
c = 20.5627(15) A
3
˚
2541.3(3) A
Volume
Z
8
-137(1)
-216(1)
578(1)
864(1)
3
Density
(
1.298 Mg/m
1532(1)
1953(1)
3216(1)
3892(1)
4423(1)
4288(1)
3619(1)
3087(1)
2205(1)
2766(1)
807(1)
calculated)
-1
Absorption
coefficient
0.093 mm
1056
3187(1)
2857(1)
3636(1)
4577(1)
4906(1)
4135(1)
7413(1)
7558(1)
7621(1)
7865(1)
7664(1)
8301(1)
6607(1)
6681(1)
5915(1)
5035(1)
4938(1)
5715(1)
8360(1)
8111(1)
8964(2)
9859(1)
10106(1)
9266(1)
F (000)
3
Crystal size
0.27 9 0.12 9 0.12 mm
2.51–25.95ꢁ
h range for data
collection
Index ranges
-17 B h B 16, -
1
0 B k B 10, -25 B l B 25
Reflections
collected
30869
Independent
reflections
4950 [R(int) = 0.0691]
99.9%
2058(1)
349(1)
Completeness to
h = 25.00ꢁ
1040(1)
1750(1)
1075(1)
636(1)
Absorption
correction
None
Max. and min.
transmission
0.9889 and 0.9753
Full-matrix least-squares on F
4950/0/334
874(1)
2
Refinement
method
1541(1)
1974(1)
3230(1)
3921(1)
4406(1)
4208(1)
3522(1)
3035(1)
Data/restraints/
parameters
Goodness-of-fit on 0.908
2
F
Final R indices
I [ 2r(I)]
R indices (all data) R
R
1
= 0.0380, wR
2
2
= 0.0880
= 0.0957
[
1
= 0.0626, wR
Extinction
coefficient
0.0048(5)
U(eq) is defined as one-third of the trace of the orthogonalized Uij
tensor
-3
˚
Largest diff. peak 0.231 and -0.211 e/A
and hole
CCDC 673357
determination and refinement are given in Table 1. The
atomic coordinates along with their equivalent isotropic
displacement parameters are presented in Table 2. The
chemical diagram of the title compound is depicted in
Fig. 1. The molecular structure with the atom numbering
scheme is depicted in Fig. 2. Selected bond lengths and
angles are given in Table 3.
X-ray Data Collection and Structure Refinement
X-ray measurements were made using a STOE IPDS-II dif-
fractometer 173 K with graphite monochromated radiation,
-1
˚
Geometric parameters of hydrogen bonds are given in
Table 4. The title compound crystallized with two
k(MoKa) = 0.71073 A, l = 0.093 mm . A summary of
the crystal data along with further details of the structure
123

9
26
J Chem Crystallogr (2010) 40:924–926
molecules in the asymmetric unit. Geometric parameters
are in the usual ranges. A least-squares fit of all non H
˚
atoms of the two molecules (r.m.s. deviation 0.109 A)
shows that the conformation of the two molecules is
essentially the same. The nitro group is significantly
twisted out of the plane of the aromatic ring as demon-
strated by the torsion angles C11–C12–N2–O3
[
47.75(19)ꢁ] and C11A–C12A–N2A–O3A [46.75(18)ꢁ].
The cyclohexyl rings adopt a chair conformation. The
crystal packing is stabilized by N–H_O hydrogen bonds.
Acknowledgment The authors gratefully acknowledge a research
grant from higher Education Commission of Pakistan under the
project No. 20-Miscel/R&D/00/3834.
Fig. 2 Molecular structure of (I) with the atom numbering scheme.
Displacement ellipsoids drawn at the 50% probability level. H atoms
drawn as small spheres of arbitrary radius
References
1
2
. Zhichkin P, Kesicki E, Treiberg J, Bourdon L, Ronsheim M, Ooi
HC, White S, Judkins A, Fairfax D (2007) Org Lett 5:1415
. Jackson S, DeGrado W, Dwivedi A, Parthasarathy A, Higley A,
Krywko J, Rockwell A, Markwalder J, Wells G, Wexler R, Mousa
S, Harlow R (1994) J Am Chem Soc 116:3220
˚
Table 3 Selected bond lengths (A) and angles (ꢁ)
C(1)–O(1)
1.2397(17)
1.3284(18)
1.5096(18)
1.4717(17)
1.2249(16)
1.2287(17)
1.4767(18)
1.2362(17)
1.3346(19)
1.5062(18)
1.4681(18)
1.2282(16)
1.2291(17)
1.4707(18)
C(1)–N(1)
C(1)–C(11)
3. Manley PW, Furet P, Bold G, Bruggen J, Mestan J, Meyer T,
Schnell CR, Wood J (2002) J Med Chem 45:5687
4
N(1)–C(21)
N(2)–O(3)
. Igawa H, Nishimura M, Okada K, Nakamura T (1999) Jpn Kokai
Tokkyo Koho. JP 11171848
N(2)–O(2)
N(2)–C(12)
C(1A)–O(1A)
C(1A)–N(1A)
C(1A)–C(11A)
N(1A)–C(21A)
N(2A)–O(3A)
N(2A)–O(2A)
N(2A)–C(12A)
˚
Table 4 Hydrogen bonds (A, ꢁ)
D–H_A
d(D–H) d(H…A) d(D…A) \(DHA)
0.84(2) 2.06(2) 2.8413(17) 154.4(16)
0.809(19) 2.062(19) 2.8464(17) 163.2(17)
a
N(1)–H(1)_O(1)
N(1A)–
H(1A)_O(1A)
b
Symmetry transformations used to generate equivalent atoms
a
-
x ? 1/2, y - 1/2, -z ? 1/2
x ? 3/2, y - 1/2, -z ? 1/2
b
-
1
23