N-Ethyl-3,5-dinitro­benzamide

Abstract

In the title mol­ecule, C₉H₉N₃O₅, the dihedral angle between the mean planes of the amide group and the benzene ring is 31.24 (14)°. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules to form one-dimensional chains propagating in [100].

Related literature

For the synthesis of the title compound, see: Lee et al. (2009 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₉H₉N₃O₅

• M _r = 239.19

• Triclinic,

• a = 4.854 (1) Å

• b = 10.488 (2) Å

• c = 10.851 (2) Å

• α = 101.49 (3)°

• β = 97.84 (3)°

• γ = 95.25 (3)°

• V = 532.26 (19) ų

• Z = 2

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 293 K

• 0.20 × 0.10 × 0.10 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.976, T _max = 0.988

• 2203 measured reflections

• 1955 independent reflections

• 1321 reflections with I > 2σ(I)

• R _int = 0.021

• 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.161

• S = 1.01

• 1955 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.23 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O5i	0.86	2.13	2.886 (3)	146

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound is an important organic intermediate, and such amide derivatives exhibit biological activities, such as antibacterial and antifungal effects (Lee et al., 2009). Herein we report on the crystal structure of the title substitued benzamide compound.

The molecular structure of the title compound is illustrated in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the amide group [atoms O5,N3,C7,C8, planar to within 0.012 Å] and the benzene ring (C1-C6) is 31.24 (14) °.

In the crystal of the title compound molecules are connected via N—H···O intermolecular hydrogen bonds (Table 1), to form a one-dimensional polymer propagating in [100]. These chains stack along the c axis direction.

Experimental

The title compound was prepared following a literature proceedure (Lee et al., 2009). Crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation, over a period of 5 days, of a solution of the title compound in ethanol [0.2 g, 0.84 mmol in 25 ml ethanol].

Refinement

All the H-atoms were positioned geometrically and constrained to ride on their parent atom: N-H = 0.86 Å, C—H = 0.93, 0.96 and 0.97 Å for CH(aromatic), CH₂ and CH₃ H-atoms, respectively, with U_iso(H) = k × U_eq(C or N), where k = 1.5 for CH₃ H-atoms, and k = 1.2 for all other H-atoms.

Figures

Fig. 1.

The molecular structure of the title molecule, with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

A view of the crystal packing of the title compound. The N—H···O hydrogen bonds are shown as dashed lines.

Crystal data

C9H9N3O5	Z = 2
Mr = 239.19	F(000) = 248
Triclinic, P1	Dx = 1.492 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.854 (1) Å	Cell parameters from 25 reflections
b = 10.488 (2) Å	θ = 10–13°
c = 10.851 (2) Å	µ = 0.12 mm−1
α = 101.49 (3)°	T = 293 K
β = 97.84 (3)°	Block, colourless
γ = 95.25 (3)°	0.20 × 0.10 × 0.10 mm
V = 532.26 (19) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer	1321 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
graphite	θmax = 25.4°, θmin = 1.9°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.976, Tmax = 0.988	l = −13→12
2203 measured reflections	3 standard reflections every 200 reflections
1955 independent reflections	intensity decay: 1%

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.090P)2] where P = (Fo2 + 2Fc2)/3
1955 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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 matrix. 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, conventional 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1490 (5)	0.7075 (2)	0.2465 (2)	0.0428 (6)
H1A	−0.0017	0.6473	0.2494	0.051*
N1	0.0031 (5)	0.6713 (2)	0.0152 (2)	0.0617 (6)
O1	0.0675 (6)	0.6862 (3)	−0.0856 (2)	0.0985 (9)
N2	0.8248 (5)	0.9842 (2)	0.2289 (3)	0.0576 (6)
C2	0.1956 (5)	0.7377 (2)	0.1327 (2)	0.0454 (6)
O2	−0.2072 (5)	0.6034 (2)	0.02613 (19)	0.0795 (7)
N3	0.4868 (4)	0.7427 (2)	0.57021 (18)	0.0453 (5)
H3A	0.6513	0.7677	0.5563	0.054*
C3	0.4127 (5)	0.8280 (2)	0.1236 (2)	0.0492 (6)
H3B	0.4392	0.8480	0.0459	0.059*
O3	0.8469 (5)	1.0119 (2)	0.1269 (2)	0.0911 (8)
C4	0.5890 (5)	0.8874 (2)	0.2352 (2)	0.0449 (6)
O4	0.9911 (4)	1.0292 (2)	0.3254 (2)	0.0743 (6)
O5	0.0241 (3)	0.70717 (19)	0.49151 (17)	0.0574 (5)
C5	0.5555 (5)	0.8591 (2)	0.3510 (2)	0.0414 (6)
H5A	0.6803	0.8997	0.4241	0.050*
C6	0.3318 (4)	0.7688 (2)	0.3573 (2)	0.0388 (5)
C7	0.2693 (4)	0.7366 (2)	0.4798 (2)	0.0408 (6)
C8	0.4582 (5)	0.7087 (2)	0.6918 (2)	0.0497 (6)
H8A	0.2783	0.7293	0.7144	0.060*
H8B	0.6035	0.7612	0.7572	0.060*
C9	0.4794 (7)	0.5668 (3)	0.6881 (3)	0.0712 (9)
H9A	0.4582	0.5484	0.7697	0.107*
H9B	0.6592	0.5465	0.6680	0.107*
H9C	0.3345	0.5145	0.6242	0.107*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0323 (12)	0.0467 (13)	0.0504 (14)	0.0078 (10)	0.0086 (10)	0.0101 (11)
N1	0.0608 (16)	0.0709 (16)	0.0496 (14)	0.0068 (13)	0.0017 (11)	0.0094 (11)
O1	0.113 (2)	0.131 (2)	0.0458 (13)	−0.0138 (16)	0.0034 (12)	0.0245 (13)
N2	0.0512 (14)	0.0510 (13)	0.0797 (17)	0.0095 (11)	0.0225 (13)	0.0255 (12)
C2	0.0424 (14)	0.0518 (15)	0.0425 (13)	0.0125 (11)	0.0041 (10)	0.0101 (11)
O2	0.0575 (13)	0.1052 (18)	0.0627 (13)	−0.0106 (12)	−0.0020 (10)	0.0039 (12)
N3	0.0292 (10)	0.0650 (13)	0.0446 (11)	0.0026 (9)	0.0098 (8)	0.0172 (9)
C3	0.0528 (15)	0.0544 (15)	0.0489 (14)	0.0174 (12)	0.0161 (12)	0.0207 (12)
O3	0.0941 (18)	0.1021 (18)	0.0914 (17)	−0.0079 (14)	0.0313 (14)	0.0522 (14)
C4	0.0396 (13)	0.0423 (13)	0.0586 (15)	0.0087 (10)	0.0153 (11)	0.0176 (11)
O4	0.0597 (13)	0.0651 (13)	0.0940 (16)	−0.0137 (10)	0.0088 (12)	0.0193 (11)
O5	0.0287 (9)	0.0861 (14)	0.0596 (11)	0.0045 (8)	0.0149 (8)	0.0164 (9)
C5	0.0330 (12)	0.0439 (13)	0.0489 (13)	0.0095 (10)	0.0090 (10)	0.0098 (11)
C6	0.0287 (11)	0.0446 (13)	0.0458 (13)	0.0100 (10)	0.0090 (9)	0.0114 (10)
C7	0.0270 (12)	0.0501 (14)	0.0468 (13)	0.0074 (10)	0.0115 (10)	0.0089 (10)
C8	0.0454 (14)	0.0633 (17)	0.0415 (14)	0.0050 (12)	0.0099 (11)	0.0125 (12)
C9	0.089 (2)	0.0671 (19)	0.0588 (18)	0.0082 (17)	0.0087 (16)	0.0185 (15)

Geometric parameters (Å, °)

C1—C2	1.376 (3)	C3—C4	1.380 (4)
C1—C6	1.394 (3)	C3—H3B	0.9300
C1—H1A	0.9300	C4—C5	1.375 (3)
N1—O1	1.212 (3)	O5—C7	1.232 (3)
N1—O2	1.224 (3)	C5—C6	1.392 (3)
N1—C2	1.479 (3)	C5—H5A	0.9300
N2—O4	1.214 (3)	C6—C7	1.498 (3)
N2—O3	1.214 (3)	C8—C9	1.494 (4)
N2—C4	1.477 (3)	C8—H8A	0.9700
C2—C3	1.379 (4)	C8—H8B	0.9700
N3—C7	1.327 (3)	C9—H9A	0.9600
N3—C8	1.454 (3)	C9—H9B	0.9600
N3—H3A	0.8600	C9—H9C	0.9600
C2—C1—C6	118.8 (2)	C4—C5—C6	119.0 (2)
C2—C1—H1A	120.6	C4—C5—H5A	120.5
C6—C1—H1A	120.6	C6—C5—H5A	120.5
O1—N1—O2	124.6 (2)	C5—C6—C1	119.7 (2)
O1—N1—C2	117.6 (2)	C5—C6—C7	123.0 (2)
O2—N1—C2	117.8 (2)	C1—C6—C7	117.3 (2)
O4—N2—O3	123.4 (2)	O5—C7—N3	124.0 (2)
O4—N2—C4	118.2 (2)	O5—C7—C6	119.2 (2)
O3—N2—C4	118.4 (3)	N3—C7—C6	116.78 (19)
C1—C2—C3	122.9 (2)	N3—C8—C9	112.1 (2)
C1—C2—N1	118.7 (2)	N3—C8—H8A	109.2
C3—C2—N1	118.5 (2)	C9—C8—H8A	109.2
C7—N3—C8	122.68 (19)	N3—C8—H8B	109.2
C7—N3—H3A	118.7	C9—C8—H8B	109.2
C8—N3—H3A	118.7	H8A—C8—H8B	107.9
C2—C3—C4	116.8 (2)	C8—C9—H9A	109.5
C2—C3—H3B	121.6	C8—C9—H9B	109.5
C4—C3—H3B	121.6	H9A—C9—H9B	109.5
C5—C4—C3	122.7 (2)	C8—C9—H9C	109.5
C5—C4—N2	118.9 (2)	H9A—C9—H9C	109.5
C3—C4—N2	118.3 (2)	H9B—C9—H9C	109.5
C6—C1—C2—C3	−1.3 (4)	C3—C4—C5—C6	−1.3 (4)
C6—C1—C2—N1	179.3 (2)	N2—C4—C5—C6	179.42 (19)
O1—N1—C2—C1	−170.8 (3)	C4—C5—C6—C1	0.9 (3)
O2—N1—C2—C1	8.0 (4)	C4—C5—C6—C7	−176.8 (2)
O1—N1—C2—C3	9.8 (4)	C2—C1—C6—C5	0.3 (3)
O2—N1—C2—C3	−171.4 (2)	C2—C1—C6—C7	178.2 (2)
C1—C2—C3—C4	0.9 (4)	C8—N3—C7—O5	3.0 (4)
N1—C2—C3—C4	−179.6 (2)	C8—N3—C7—C6	−177.4 (2)
C2—C3—C4—C5	0.4 (4)	C5—C6—C7—O5	147.8 (2)
C2—C3—C4—N2	179.7 (2)	C1—C6—C7—O5	−30.0 (3)
O4—N2—C4—C5	4.5 (3)	C5—C6—C7—N3	−31.9 (3)
O3—N2—C4—C5	−177.4 (2)	C1—C6—C7—N3	150.3 (2)
O4—N2—C4—C3	−174.8 (2)	C7—N3—C8—C9	90.0 (3)
O3—N2—C4—C3	3.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O5i	0.86	2.13	2.886 (3)	146

Symmetry codes: (i) x+1, y, z.