N-(2-Hydroxy­ethyl)-3,5-dinitro­benzamide

He, L.; Xu, Z.-G.; Jiang, Y.; Mao, Z.-H.; Deng, A.-P.

doi:10.1107/S1600536808019521

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1422

doi:10.1107/S1600536808019521

Open

access

N-(2-Hydroxyethyl)-3,5-dinitrobenzamide

Li He,^a Zhi-Gang Xu,^a Yan Jiang,^a Zhi-Hua Mao ^b and An-Ping Deng ^a ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bAnalytical and Testing Center, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: denganping6119@yahoo.com.cn

(Received 3 May 2008; accepted 27 June 2008; online 5 July 2008)

The title compound, C₉H₉N₃O₆, was synthesized by the condensation of methyl 3,5-dinitrobenzoate and 2-aminoethanol. The non-centrosymmetric space group results in the formation of pseudo-chiral helices in the crystal structure, which exhibits a layer packing structure involving intramolecular N—H⋯O and O—H⋯O interactions.

Related literature

For related literature, see: Lin & Smith (1981 ); Morehouse & McGuire (1959 ); Percec (1981 , 1982 ); Walde (1962 ).

Experimental

Crystal data

C₉H₉N₃O₆
M_r = 255.19
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.514 (4) Å
b = 9.097 (3) Å
c = 18.177 (3) Å
V = 1077.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 294 (2) K
0.46 × 0.45 × 0.33 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
1124 measured reflections
1118 independent reflections
945 reflections with I > 2σ(I)
R_int = 0.015
3 standard reflections every 100 reflections intensity decay: 3.4%

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.10
1118 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2W⋯O1ⁱ	0.82	1.99	2.737 (3)	151
N1—H1N⋯O2ⁱ	0.86	2.12	2.935 (3)	158
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: DIFRAC (Gabe et al., 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019521/lx2057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019521/lx2057Isup2.hkl

checkCIF report

Comment top

Non-ionic contrast agents, which are used in the field of intravascular and central nervous system visualization, are mostly complex molecules. However, the iodine in the molecule provides opacification to the x-rays and the remainder of the molecule provides the framework for transport of the iodine atoms. As a result, the structural arrangement of the molecule is very important in providing stability, solubility and biological safety in various organs (Lin & Smith, 1981). The title compound is an important intermediate in the synthesis of a variety of these molecules. It also can be used against coccidiosis and salmonella infection in poultry (Walde, 1962; Morehouse & McGuire, 1959).In addition, it plays an important role in the synthesis of copolymers (Percec, 1982; Percec, 1981). In this paper, we report the crystal structure of the title compound, N-(2-hydroxyethyl)-3,5-dinitrobenzamide (Fig. 1).

The title compound was crystallized in the non-centrosymmetric space group P212121 in spite of having no asymmetric carbon atom in the molecule. In the packing structure, an intermolecular O—H···O hydrogen bond leads to form pseudo-chiral helix about the 21 screw axis, propagating in the [100] direction. Non-centrosymmetric space group P212121 results in the formation of pseudo-chiral helix in the packing structure (Fig. 2). The crystal structure exhibits a layer packing structure with the intramolecular N—H···O and O—H···O hydrogen bonds (Fig. 2 and Table 1; symmetry code as in Fig. 2). On the other hand, adjacent molecules are linked into chains through van der Waals force to stabilize the crystal structure.

Related literature top

For related literature, see: Dieltiens et al. (2006); Lin & Smith (1981); Morehouse & McGuire (1959); Percec (1981, 1982); Walde (1962).

Experimental top

A mixture of methyl 3,5-dinitrobenzoate (5.65 g, 0.025 mol) and 50% aqueous 2-aminoethanol (30.5 g, 0.5 mol) was stirred for 10 h at room temperture. Then 30 ml water was added and the crystalline product was collected. Recrystallization of the crude product from ethanol gave N-(2-hydroxyethyl)-3,5-dinitrobenzamide (m.p. 416-417 K) (Lin & Smith, 1981). Single crystals of the title compound were obtained and used for X-ray diffraction studies at room temperature.

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the structure projected on the ac plane. Hydrogen bonding shown as dashed lines. [Symmetry code: (i) x+1/2, -y+3/2, -z+1; (ii) x+1, y, z.]

N-(2-Hydroxyethyl)-3,5-dinitrobenzamide top

Crystal data top

C₉H₉N₃O₆	D_x = 1.574 Mg m⁻³
M_r = 255.19	Melting point = 416–417 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2ac 2ab	Cell parameters from 24 reflections
a = 6.514 (4) Å	θ = 4.5–7.8°
b = 9.097 (3) Å	µ = 0.14 mm⁻¹
c = 18.177 (3) Å	T = 294 K
V = 1077.1 (8) Å³	Block, colourless
Z = 4	0.46 × 0.45 × 0.33 mm
F(000) = 528

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.015
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.2°
Graphite monochromator	h = −3→7
ω/2θ scans	k = −4→10
1124 measured reflections	l = −10→21
1118 independent reflections	3 standard reflections every 100 reflections
945 reflections with I > 2σ(I)	intensity decay: 3.4%

Refinement top

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0522P)² + 0.1396P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1118 reflections	Δρ_max = 0.14 e Å⁻³
164 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.219 (12)

Crystal data top

C₉H₉N₃O₆	V = 1077.1 (8) Å³
M_r = 255.19	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.514 (4) Å	µ = 0.14 mm⁻¹
b = 9.097 (3) Å	T = 294 K
c = 18.177 (3) Å	0.46 × 0.45 × 0.33 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.015
1124 measured reflections	3 standard reflections every 100 reflections
1118 independent reflections	intensity decay: 3.4%
945 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.10	Δρ_max = 0.14 e Å⁻³
1118 reflections	Δρ_min = −0.18 e Å⁻³
164 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top

	x	y	z	U_iso*/U_eq
O1	0.2873 (3)	0.5989 (2)	0.34735 (10)	0.0471 (6)
O2	0.5044 (3)	0.7755 (2)	0.56083 (10)	0.0476 (6)
H2W	0.5535	0.8106	0.5985	0.071*
O3	0.5495 (4)	0.6710 (3)	0.02304 (11)	0.0717 (8)
O4	0.3233 (5)	0.5573 (4)	0.08631 (13)	0.1040 (12)
O5	1.0931 (4)	0.9372 (3)	0.26737 (12)	0.0799 (9)
O6	1.1272 (4)	0.8922 (3)	0.15286 (11)	0.0696 (8)
N1	0.5752 (4)	0.6420 (2)	0.41241 (11)	0.0370 (6)
H1N	0.6916	0.6865	0.4132	0.044*
N2	0.4757 (5)	0.6333 (3)	0.08103 (13)	0.0535 (7)
N3	1.0356 (4)	0.8822 (3)	0.21046 (13)	0.0464 (6)
C1	0.5713 (4)	0.6903 (3)	0.28124 (14)	0.0316 (6)
C2	0.7552 (4)	0.7679 (3)	0.27890 (13)	0.0332 (6)
H2A	0.8186	0.7982	0.3222	0.040*
C3	0.8421 (4)	0.7994 (3)	0.21153 (14)	0.0355 (6)
C4	0.7576 (4)	0.7570 (3)	0.14550 (13)	0.0366 (7)
H4	0.8202	0.7779	0.1007	0.044*
C5	0.5739 (5)	0.6816 (3)	0.14983 (14)	0.0386 (7)
C6	0.4801 (4)	0.6487 (3)	0.21553 (14)	0.0358 (6)
H6	0.3556	0.5987	0.2159	0.043*
C7	0.4681 (4)	0.6420 (3)	0.35076 (14)	0.0350 (7)
C8	0.5042 (5)	0.5698 (3)	0.47915 (13)	0.0437 (7)
H8A	0.5403	0.4664	0.4768	0.052*
H8B	0.3557	0.5765	0.4815	0.052*
C9	0.5928 (4)	0.6344 (3)	0.54759 (14)	0.0426 (7)
H9A	0.5652	0.5700	0.5890	0.051*
H9B	0.7404	0.6438	0.5424	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0326 (11)	0.0647 (13)	0.0441 (10)	−0.0133 (11)	0.0046 (9)	−0.0125 (10)
O2	0.0324 (10)	0.0700 (13)	0.0405 (10)	0.0039 (11)	−0.0015 (9)	−0.0121 (9)
O3	0.089 (2)	0.0951 (17)	0.0311 (11)	−0.0176 (17)	−0.0042 (13)	0.0000 (11)
O4	0.103 (2)	0.156 (3)	0.0536 (14)	−0.079 (2)	−0.0175 (15)	−0.0111 (17)
O5	0.0793 (19)	0.113 (2)	0.0478 (13)	−0.0607 (17)	−0.0059 (12)	0.0036 (13)
O6	0.0530 (14)	0.104 (2)	0.0523 (13)	−0.0241 (16)	0.0145 (12)	0.0089 (13)
N1	0.0305 (12)	0.0486 (13)	0.0319 (11)	−0.0083 (12)	0.0060 (10)	0.0000 (10)
N2	0.0617 (19)	0.0631 (16)	0.0356 (13)	−0.0109 (18)	−0.0113 (14)	−0.0048 (12)
N3	0.0415 (14)	0.0577 (14)	0.0400 (13)	−0.0152 (13)	0.0011 (13)	0.0105 (13)
C1	0.0287 (13)	0.0319 (12)	0.0341 (13)	0.0022 (12)	0.0013 (12)	−0.0024 (11)
C2	0.0334 (14)	0.0363 (13)	0.0300 (12)	−0.0038 (12)	−0.0027 (12)	−0.0013 (11)
C3	0.0320 (13)	0.0378 (13)	0.0367 (13)	−0.0040 (12)	0.0003 (13)	0.0023 (12)
C4	0.0415 (17)	0.0383 (14)	0.0300 (12)	0.0006 (14)	0.0033 (13)	0.0031 (11)
C5	0.0442 (17)	0.0414 (14)	0.0303 (13)	0.0005 (15)	−0.0081 (12)	−0.0026 (11)
C6	0.0281 (13)	0.0400 (13)	0.0391 (14)	−0.0011 (12)	−0.0031 (13)	−0.0039 (12)
C7	0.0310 (16)	0.0392 (15)	0.0346 (14)	−0.0051 (14)	0.0027 (12)	−0.0081 (11)
C8	0.0455 (16)	0.0502 (15)	0.0354 (13)	−0.0075 (15)	0.0068 (14)	0.0031 (12)
C9	0.0345 (15)	0.0576 (17)	0.0356 (13)	0.0019 (16)	0.0030 (12)	0.0081 (13)

Geometric parameters (Å, º) top

O1—C7	1.243 (4)	C1—C7	1.498 (4)
O2—C9	1.428 (3)	C2—C3	1.379 (3)
O2—H2W	0.8200	C2—H2A	0.9300
O3—N2	1.208 (3)	C3—C4	1.376 (4)
O4—N2	1.213 (4)	C4—C5	1.382 (4)
O5—N3	1.209 (3)	C4—H4	0.9300
O6—N3	1.209 (3)	C5—C6	1.374 (4)
N1—C7	1.320 (3)	C6—H6	0.9300
N1—C8	1.455 (3)	C8—C9	1.492 (4)
N1—H1N	0.8600	C8—H8A	0.9700
N2—C5	1.472 (4)	C8—H8B	0.9700
N3—C3	1.468 (3)	C9—H9A	0.9700
C1—C6	1.387 (3)	C9—H9B	0.9700
C1—C2	1.391 (4)

C9—O2—H2W	109.5	C6—C5—C4	122.9 (2)
C7—N1—C8	122.7 (2)	C6—C5—N2	118.7 (3)
C7—N1—H1N	118.7	C4—C5—N2	118.4 (3)
C8—N1—H1N	118.7	C5—C6—C1	119.9 (2)
O3—N2—O4	123.8 (3)	C5—C6—H6	120.0
O3—N2—C5	119.0 (3)	C1—C6—H6	120.0
O4—N2—C5	117.3 (3)	O1—C7—N1	122.9 (3)
O6—N3—O5	123.9 (2)	O1—C7—C1	118.4 (2)
O6—N3—C3	118.3 (2)	N1—C7—C1	118.6 (2)
O5—N3—C3	117.8 (2)	N1—C8—C9	113.2 (2)
C6—C1—C2	118.8 (2)	N1—C8—H8A	108.9
C6—C1—C7	117.0 (2)	C9—C8—H8A	108.9
C2—C1—C7	124.2 (2)	N1—C8—H8B	108.9
C3—C2—C1	119.1 (2)	C9—C8—H8B	108.9
C3—C2—H2A	120.5	H8A—C8—H8B	107.7
C1—C2—H2A	120.5	O2—C9—C8	109.8 (2)
C4—C3—C2	123.5 (2)	O2—C9—H9A	109.7
C4—C3—N3	118.4 (2)	C8—C9—H9A	109.7
C2—C3—N3	118.1 (2)	O2—C9—H9B	109.7
C3—C4—C5	115.9 (2)	C8—C9—H9B	109.7
C3—C4—H4	122.1	H9A—C9—H9B	108.2
C5—C4—H4	122.1

C6—C1—C2—C3	−0.8 (3)	O3—N2—C5—C4	−5.8 (4)
C7—C1—C2—C3	176.3 (2)	O4—N2—C5—C4	174.3 (3)
C1—C2—C3—C4	−0.6 (4)	C4—C5—C6—C1	−0.8 (4)
C1—C2—C3—N3	179.6 (2)	N2—C5—C6—C1	178.7 (2)
O6—N3—C3—C4	−10.1 (4)	C2—C1—C6—C5	1.4 (4)
O5—N3—C3—C4	169.5 (3)	C7—C1—C6—C5	−175.9 (3)
O6—N3—C3—C2	169.7 (3)	C8—N1—C7—O1	10.3 (4)
O5—N3—C3—C2	−10.7 (4)	C8—N1—C7—C1	−167.1 (2)
C2—C3—C4—C5	1.2 (4)	C6—C1—C7—O1	−16.4 (4)
N3—C3—C4—C5	−179.0 (2)	C2—C1—C7—O1	166.4 (2)
C3—C4—C5—C6	−0.6 (4)	C6—C1—C7—N1	161.2 (2)
C3—C4—C5—N2	180.0 (3)	C2—C1—C7—N1	−16.0 (4)
O3—N2—C5—C6	174.7 (3)	C7—N1—C8—C9	−154.7 (3)
O4—N2—C5—C6	−5.2 (4)	N1—C8—C9—O2	71.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2W···O1ⁱ	0.82	1.99	2.737 (3)	151
N1—H1N···O2ⁱ	0.86	2.12	2.935 (3)	158

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₆
M_r	255.19
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	6.514 (4), 9.097 (3), 18.177 (3)
V (Å³)	1077.1 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.46 × 0.45 × 0.33

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1124, 1118, 945
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.10
No. of reflections	1118
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2W···O1ⁱ	0.82	1.99	2.737 (3)	150.7
N1—H1N···O2ⁱ	0.86	2.12	2.935 (3)	158.2

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (NSFC, contract No. 20675054) and the Promotion Program Foundation of Sichuan University of China (No. 0082204127090) for financial support of this study.

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J., White, P. S. & Enright, G. D. (1993). DIFRAC. American Crystallographic Association, Pittsburgh meeting. Abstract PA104. Google Scholar
Lin, Y. L. & Smith, K. R. (1981). US Patent 4 284 620. Google Scholar
Morehouse, N. F. & McGuire, W. C. (1959). Poult. Sci. 38, 410–423. CrossRef CAS Google Scholar
Percec, V. (1981). Polym. Bull. 5, 651–657. CAS Google Scholar
Percec, V. (1982). Polym. Prep. 23, 301–302. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Walde, A. W. (1962). US Patent 3 015 606. Google Scholar