Ethyl 2-(3,5-dinitrobenzamido)benzoate

Abstract

The title molecule, C16H13N3O7, is slightly twisted, with the
dihedral angle between the two benzene ring planes being
17.4 (1)o. An intramolecular N—H...O hydrogen bond is
observed. In the crystal, weak C—H...O hydrogen bonds link
the molecules into chains along the b axis.

Full text

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Ethyl 2-(3,5-dinitrobenzamido)benzoate
Sohail Saeed,a* Naghmana Rashid,aRizwan Hussainband
Wing-Tak Wongc
aDepartment of Chemistry, Research Complex, Allama Iqbal Open Unicversity,
Islamabad 44000, Pakistan,bNational Engineering & Scientific Commission, PO Box
2801, Islamabad, Pakistan, andcDepartment of Chemistry, The University of Hong
Kong, Pokfulam Road, Pokfulam, Hong Kong SAR, People’s Republic of China
Correspondence e-mail: Sohail262001@yahoo.com
Received 28 November 2011; accepted 9 December 2011
Key indicators: single-crystal X-ray study; T = 296 K; mean ?(C–C) = 0.004 A ˚;
R factor = 0.049; wR factor = 0.174; data-to-parameter ratio = 11.8.
The title molecule, C16H13N3O7, is slightly twisted, with the
dihedral angle between the two benzene ring planes being
17.4 (1)?. An intramolecular N—H???O hydrogen bond is
observed. In the crystal, weak C—H???O hydrogen bonds link
the molecules into chains along the b axis.
Related literature
For background to the biological activity of N-substituted
benzamides and their use in synthesis, see: Saeed et al.
(2011a,b). For the structures of related chlorophenyl-
benzamides, see: Gowda et al. (2007a,b,c). For hydrogen-bond
motifs, see: Bernstein et al. (1995). For bond-length data, see:
Allen et al. (1987). For ortho-hydrogen steric hindrance, see:
Karle & Brockway (1944).
Experimental
Crystal data
C16H13N3O7
Mr= 359.29
Monoclinic, P21=c
a = 12.4662 (4) A˚
b = 17.7213 (5) A˚
c = 7.4352 (2) A˚
? = 96.658 (2)?
V = 1631.49 (8) A˚3
Z = 4
Mo K? radiation
? = 0.12 mm?1
T = 296 K
0.52 ? 0.30 ? 0.26 mm
Data collection
Bruker APEXII CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin= 0.942, Tmax= 0.970
16092 measured reflections
2808 independent reflections
1961 reflections with I > 2?(I)
Rint= 0.040
Refinement
R[F2> 2?(F2)] = 0.049
wR(F2) = 0.174
S = 1.11
2808 reflections
237 parameters
H-atom parameters constrained
??max= 0.18 e A˚?3
??min= ?0.22 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N1—H1???O2
C16—H16A???O3i
Symmetry code: (i) ?x þ 1;y þ1
D—HH???AD???AD—H???A
0.86
0.96
1.92
2.55
2.641 (3)
3.402 (4)
140
148
2;?z þ3
2.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure:SHELXL97(Sheldrick,
Mercury (Macrae et al., 2008); software used to prepare material for
publication: SHELXL97.
2008);moleculargraphics:
Dr. Wesley T. K. Chan, Professor Z. Y. Zhou, and the Hong
Kong Polytechnic University are sincerely thanked for helping
to collect the X-ray data.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: FK2047).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. 341, 555–1573.
Bruker (2007). APEX2 and SAINT, Bruker AXS Inc., Madison, Wisconsin,
USA.
Gowda, B. T., Sowmya, B. P., Koz ˇı ´s ˇek, J., Tokarc ˇı ´k, M. & Fuess, H. (2007a).
Acta Cryst. E63, o2906.
Gowda, B. T., Sowmya, B. P., Tokarc ˇı ´k, M., Koz ˇı ´s ˇek, J. & Fuess, H. (2007b).
Acta Cryst. E63, o3326.
Gowda, B. T., Sowmya, B. P., Tokarc ˇı ´k, M., Koz ˇı ´s ˇek, J. & Fuess, H. (2007c).
Acta Cryst. E63, o3365.
Karle, I. L. & Brockway, L. O. (1944). J. Am. Chem. Soc. 66, 1974–1979.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,
P. A. (2008). J. Appl. Cryst. 41, 466–470.
Saeed, S., Jasinski, J. P. & Butcher, R. J. (2011a). Acta Cryst. E67, o279.
Saeed, S., Rashid, N., Ng, S. W. & Tiekink, E. R. T. (2011b). Acta Cryst. E67,
o1194.
Sheldrick, G. M. (2004). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
organic compounds
Acta Cryst. (2012). E68, o129doi:10.1107/S1600536811053074Saeed et al.
o129
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Acta Cryst. (2012). E68, o129 [ doi:10.1107/S1600536811053074 ]
Ethyl 2-(3,5-dinitrobenzamido)benzoate
S. Saeed, N. Rashid, R. Hussain and W.-T. Wong
Comment
In spite of the fact that the molecule is an extensively conjugated aromatic system, the molecule is not co-planar. This may
be due to the steric hindrance between the ortho-H ··· amide H-atoms. The twisting away from coplanarity may help to relief
this steric hindrance and results in an H14···H1 distance of 2.016 Å. This is in analogy to Karle and Brockway's suggestion
that the steric hindrance between the ortho hydrogen atoms in biphenyl may be the reason for the non-coplanarity of the
structure (Karle and Brockway, 1944). The dihedral angle between the two phenyl ring planes is about 17.4 (1)°. Both nitro
groups are slightly twisted, 4.9 (2)° and 4.0 (2)° respectively, from the phenyl ring plane, C9—C11.
There is an intra-molecular N1—H1···O2 interaction. A weak intermolecular C16—H16A···O3(1 - x,1/2 + y,3/2 - z)
hydrogen bond may help to align the molecules to endless chains along the b-axis in the crystal lattice. In addition, the
conjugated ring planes of the title molecules are stacked along the c-axis with perpendicular distance between ring planes
being 3.38 (1) Å.
Experimental
To a 250 ml round flask fitted with a condenser ethyl ortho-amino benzoate (0.1 mol), dichloromethane (15 ml) and triethyl-
amine (0.5 ml) was added under stirring. 3,5-dinitroenzoyl chloride (0.1 mol) was added gradually. The reaction mixture
was stirred at room temperature for 1 h and then refluxed for 2 h. The product precipitated as a colourless powder, which
was washed three times with water and dichloromethane. Recrystallization from ethyl acetate produced the crystals of the
title compound.
Refinement
The structure was solved by direct methods (SHELXS97, Sheldrick, 2008) and expanded using Fourier techniques. All non-H
atoms were refined anisotropically.
All H atoms are observable from difference Fourier map but were refined riding at idealized geometrical positions with
C—H = 0.93, 0.96 and 0.97Å for phenyl, methyl and methylene H-atoms and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C / N)
and Uiso(H) = 1.5Ueq(C-methyl).
Figures
Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 50%
probability level.

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Fig. 2. The packing diagram of the compound projected along the c-axis.
Ethyl 2-(3,5-dinitrobenzamido)benzoate
Crystal data
C16H13N3O7
F(000) = 744
Dx = 1.463 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 16092 reflections
θ = 2.8–25.0°
µ = 0.12 mm−1
T = 296 K
Block, colourless
Mr = 359.29
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 12.4662 (4) Å
b = 17.7213 (5) Å
c = 7.4352 (2) Å
β = 96.658 (2)°
V = 1631.49 (8) Å3
Z = 4
0.52 × 0.30 × 0.26 mm
Data collection
Bruker APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
ω and φ scan
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin = 0.942, Tmax = 0.970
16092 measured reflections
2808 independent reflections
1961 reflections with I > 2σ(I)
Rint = 0.040
θmax = 25.0°, θmin = 2.8°
h = −14→14
k = −21→21
l = −8→8
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map
Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
R[F2 > 2σ(F2)] = 0.049
H-atom parameters constrained
wR(F2) = 0.174
w = 1/[σ2(Fo2) + (0.0679P)2 + 0.9448P]
where P = (Fo2 + 2Fc2)/3

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S = 1.11
(Δ/σ)max < 0.001
Δρmax = 0.18 e Å−3
Δρmin = −0.22 e Å−3
Extinction correction: SHELXL97 (Sheldrick, 2008),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2808 reflections
237 parameters
0 restraints
Primary atom site location: structure-invariant direct
methods
Extinction coefficient: 0.013 (2)
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-
rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations
between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of
cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.66429 (15)
0.49758 (15)
0.29471 (18)
−0.03437 (19)
−0.11189 (19)
0.0466 (2)
0.19530 (19)
0.40070 (16)
0.4020
−0.0365 (2)
0.1241 (2)
0.5738 (2)
0.57853 (19)
0.6705 (2)
0.7267
0.6794 (2)
0.7408
0.5968 (3)
0.6032
0.5043 (2)
0.4491
0.4936 (2)
0.3099 (2)
0.22294 (19)
0.1393 (2)
y
0.10807 (11)
0.11624 (11)
−0.10623 (12)
−0.05325 (16)
0.05489 (17)
0.24889 (16)
0.22737 (13)
−0.01091 (13)
0.0374
0.01221 (19)
0.20962 (15)
0.07809 (15)
−0.00579 (14)
−0.04275 (16)
−0.0147
−0.12038 (17)
−0.1446
−0.16112 (17)
−0.2133
−0.12685 (16)
−0.1559
−0.04870 (15)
−0.03932 (16)
0.01719 (15)
−0.00719 (16)
z
0.9056 (3)
0.7638 (3)
0.5275 (3)
0.1499 (3)
0.1563 (4)
0.5560 (5)
0.7234 (4)
0.6539 (3)
0.6654
0.2005 (3)
0.6060 (4)
0.8276 (3)
0.8223 (3)
0.9032 (4)
0.9634
0.8952 (4)
0.9502
0.8055 (5)
0.7988
0.7246 (4)
0.6648
0.7326 (3)
0.5632 (4)
0.5044 (3)
0.3779 (3)
Uiso*/Ueq
0.0724 (6)
0.0678 (6)
0.0855 (7)
0.0870 (7)
0.1005 (9)
0.1221 (11)
0.0908 (8)
0.0560 (6)
0.067*
0.0721 (7)
0.0752 (7)
0.0540 (6)
0.0496 (6)
0.0585 (7)
0.070*
0.0691 (8)
0.083*
0.0763 (9)
0.092*
0.0676 (8)
0.081*
0.0524 (6)
0.0582 (7)
0.0518 (6)
0.0560 (7)
O1
O2
O3
O4
O5
O6
O7
N1
H1
N2
N3
C1
C2
C3
H3
C4
H4
C5
H5
C6
H6
C7
C8
C9
C10

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H10
C11
C12
H12
C13
C14
H14
C15
H15A
H15B
C16
H16A
H16B
H16C
0.1405
0.0544 (2)
0.0482 (2)
−0.0095
0.1312 (2)
0.2185 (2)
0.2736
0.6721 (3)
0.6505
0.6251
0.7843 (3)
0.7925
0.8302
0.8039
−0.0555
0.04096 (18)
0.11277 (17)
0.1446
0.13480 (15)
0.08975 (15)
0.1073
0.19029 (18)
0.2096
0.2119
0.2102 (2)
0.2640
0.1870
0.1926
0.3293
0.3248 (3)
0.3938 (4)
0.3568
0.5197 (4)
0.5764 (4)
0.6611
0.9047 (6)
0.7838
0.9863
0.9632 (9)
0.9594
0.8841
1.0847
0.067*
0.0588 (7)
0.0627 (7)
0.075*
0.0587 (7)
0.0545 (6)
0.065*
0.0866 (10)
0.104*
0.104*
0.139 (2)
0.208*
0.208*
0.208*
Atomic displacement parameters (Å2)
U11
0.0586 (11)
0.0540 (11)
0.0770 (14)
0.0805 (15)
0.0623 (14)
0.0978 (19)
0.0794 (15)
0.0480 (12)
0.0546 (15)
0.0634 (15)
0.0465 (14)
0.0458 (13)
0.0506 (15)
0.0638 (17)
0.077 (2)
0.0644 (17)
0.0497 (14)
0.0514 (15)
0.0438 (13)
0.0486 (14)
0.0437 (14)
0.0464 (14)
0.0488 (14)
0.0458 (13)
0.075 (2)
0.086 (3)
U22
0.0578 (12)
0.0594 (11)
0.0613 (13)
0.1026 (19)
0.135 (2)
0.101 (2)
0.0655 (14)
0.0551 (12)
0.105 (2)
0.0656 (15)
0.0586 (15)
0.0576 (15)
0.0693 (17)
0.0657 (18)
0.0551 (17)
0.0556 (16)
0.0573 (15)
0.0647 (17)
0.0612 (16)
0.0701 (17)
0.085 (2)
0.0742 (19)
0.0588 (16)
0.0598 (15)
0.0586 (18)
0.075 (3)
U33
0.0953 (15)
0.0863 (14)
0.1109 (18)
0.0738 (15)
0.0963 (18)
0.158 (3)
0.122 (2)
0.0622 (14)
0.0549 (14)
0.093 (2)
0.0560 (15)
0.0452 (13)
0.0544 (15)
0.0753 (19)
0.094 (2)
0.080 (2)
0.0500 (14)
0.0573 (15)
0.0501 (14)
0.0488 (14)
0.0463 (14)
0.0664 (17)
0.0682 (17)
0.0565 (15)
0.121 (3)
0.243 (6)
U12
−0.0026 (9)
0.0043 (9)
−0.0009 (11)
−0.0281 (14)
0.0002 (14)
0.0457 (16)
−0.0015 (11)
0.0009 (9)
−0.0166 (15)
0.0088 (13)
0.0011 (12)
0.0029 (11)
0.0061 (12)
0.0196 (14)
0.0141 (15)
0.0028 (13)
0.0061 (11)
−0.0025 (12)
−0.0029 (11)
−0.0094 (12)
−0.0120 (13)
0.0013 (13)
−0.0017 (12)
−0.0060 (11)
−0.0012 (16)
−0.011 (2)
U13
−0.0149 (10)
−0.0075 (10)
−0.0198 (13)
−0.0077 (11)
−0.0259 (13)
−0.0271 (18)
−0.0130 (14)
−0.0043 (10)
−0.0023 (11)
−0.0045 (14)
0.0016 (11)
0.0045 (10)
0.0004 (11)
−0.0021 (15)
−0.0024 (17)
−0.0027 (14)
0.0052 (11)
0.0015 (12)
0.0038 (11)
0.0034 (11)
0.0009 (11)
0.0016 (12)
0.0053 (12)
−0.0001 (11)
−0.011 (2)
−0.036 (3)
U23
−0.0026 (10)
0.0016 (10)
−0.0172 (12)
−0.0029 (13)
0.0126 (16)
−0.0201 (18)
−0.0100 (13)
0.0008 (10)
0.0122 (14)
0.0049 (14)
0.0001 (12)
0.0006 (11)
0.0038 (12)
0.0069 (15)
−0.0024 (16)
−0.0031 (14)
0.0035 (11)
−0.0026 (13)
0.0037 (12)
0.0023 (12)
0.0105 (13)
0.0177 (15)
0.0104 (13)
0.0051 (12)
−0.0072 (18)
−0.007 (3)
O1
O2
O3
O4
O5
O6
O7
N1
N2
N3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
Geometric parameters (Å, °)
O1—C1
O1—C15
1.319 (3)
1.460 (4)
C5—C6
C5—H5
1.378 (4)
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O2—C1
O3—C8
O4—N2
O5—N2
O6—N3
O7—N3
N1—C8
N1—C7
N1—H1
N2—C11
N3—C13
C1—C2
C2—C3
C2—C7
C3—C4
C3—H3
C4—C5
C4—H4
1.217 (3)
1.225 (3)
1.221 (4)
1.221 (4)
1.214 (3)
1.212 (3)
1.346 (3)
1.405 (3)
0.8600
1.468 (3)
1.480 (4)
1.488 (4)
1.395 (3)
1.407 (4)
1.382 (4)
0.9300
1.366 (4)
0.9300
C6—C7
C6—H6
C8—C9
C9—C10
C9—C14
C10—C11
C10—H10
C11—C12
C12—C13
C12—H12
C13—C14
C14—H14
C15—C16
C15—H15A
C15—H15B
C16—H16A
C16—H16B
C16—H16C
1.393 (4)
0.9300
1.503 (4)
1.390 (4)
1.396 (4)
1.381 (4)
0.9300
1.378 (4)
1.370 (4)
0.9300
1.376 (4)
0.9300
1.458 (5)
0.9700
0.9700
0.9600
0.9600
0.9600
C1—O1—C15
C8—N1—C7
C8—N1—H1
C7—N1—H1
O5—N2—O4
O5—N2—C11
O4—N2—C11
O7—N3—O6
O7—N3—C13
O6—N3—C13
O2—C1—O1
O2—C1—C2
O1—C1—C2
C3—C2—C7
C3—C2—C1
C7—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C7
C5—C6—H6
C7—C6—H6
C6—C7—C2
C6—C7—N1
C2—C7—N1
117.0 (2)
129.4 (2)
115.3
115.3
123.3 (3)
117.9 (3)
118.7 (3)
124.2 (3)
118.0 (2)
117.8 (3)
122.5 (2)
125.2 (2)
112.3 (2)
119.1 (2)
119.4 (2)
121.5 (2)
121.0 (3)
119.5
119.5
119.2 (3)
120.4
120.4
121.7 (3)
119.2
119.2
119.9 (3)
120.0
120.0
119.1 (2)
122.3 (2)
118.6 (2)
O3—C8—C9
N1—C8—C9
C10—C9—C14
C10—C9—C8
C14—C9—C8
C11—C10—C9
C11—C10—H10
C9—C10—H10
C12—C11—C10
C12—C11—N2
C10—C11—N2
C13—C12—C11
C13—C12—H12
C11—C12—H12
C12—C13—C14
C12—C13—N3
C14—C13—N3
C13—C14—C9
C13—C14—H14
C9—C14—H14
C16—C15—O1
C16—C15—H15A
O1—C15—H15A
C16—C15—H15B
O1—C15—H15B
H15A—C15—H15B
C15—C16—H16A
C15—C16—H16B
H16A—C16—H16B
C15—C16—H16C
H16A—C16—H16C
119.6 (2)
115.6 (2)
119.1 (2)
116.7 (2)
124.1 (2)
119.4 (3)
120.3
120.3
122.6 (2)
118.8 (3)
118.4 (3)
116.6 (3)
121.7
121.7
123.5 (3)
118.2 (2)
118.2 (2)
118.8 (2)
120.6
120.6
107.6 (3)
110.2
110.2
110.2
110.2
108.5
109.5
109.5
109.5
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O3—C8—N1124.8 (3)H16B—C16—H16C109.5
Hydrogen-bond geometry (Å, °)
D—H···A
N1—H1···O2
C16—H16A···O3i
Symmetry codes: (i) −x+1, y+1/2, −z+3/2.
D—H
0.86
H···A
1.92
D···A
2.641 (3)
D—H···A
140.
0.96 2.553.402 (4) 148

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Fig. 1

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Fig. 2