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Synthesis and crystal structure of 2-azido-N-(4-nitrophenyl)acetamide, C8H7N5O3

  • Mohcine Missioui , Walid Guerrab , Joel T. Mague and Youssef Ramli ORCID logo EMAIL logo
Published/Copyright: August 8, 2020

Abstract

C8H7N5O3, monoclinic, P21/n (no. 14), a = 5.0340(2) Å, b = 21.1023(9) Å, c = 9.2880(4) Å, β = 94.909(1)°, V = 983.04(7) Å3, Z = 4, Rgt(F) = 0.0470, wRref(F2) = 0.1496, T = 298(2) K.

CCDC no.: 2020512

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow block
Size:0.44 × 0.35 × 0.19 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.12 mm−1
Diffractometer, scan mode:Bruker Smart APEX, φ and ω
θmax, completeness:29.2°, >99%
N(hkl)measured, N(hkl)unique, Rint:18819, 2649, 0.034
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1983
N(param)refined:145
Programs:Bruker [1], SHELX [2], [3], Diamond [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
O10.1437(2)0.54487(5)0.40669(12)0.0653(3)
O2−0.1688(3)0.53494(6)0.23586(16)0.0889(5)
O30.7374(3)0.25286(5)0.32470(11)0.0712(4)
N10.0325(2)0.51581(5)0.30461(13)0.0533(3)
N20.4732(2)0.28701(5)0.12922(11)0.0444(3)
H2A0.4107230.2762010.0400750.053*
N30.9953(3)0.17236(7)0.13885(14)0.0638(4)
N41.0544(2)0.14690(6)0.25608(13)0.0571(3)
N51.1386(3)0.12232(9)0.35748(17)0.0869(5)
C10.3655(2)0.34342(5)0.18049(12)0.0395(3)
C20.4709(3)0.37451(6)0.30479(13)0.0452(3)
H20.6161000.3574360.3602420.054*
C30.3590(3)0.43074(6)0.34531(13)0.0468(3)
H30.4273050.4516340.4285580.056*
C40.1459(3)0.45563(6)0.26177(13)0.0433(3)
C50.0379(3)0.42568(7)0.13825(15)0.0540(3)
H5−0.1070070.4431490.0832610.065*
C60.1484(3)0.36958(7)0.09812(15)0.0517(3)
H60.0777400.3488430.0151620.062*
C70.6453(3)0.24659(6)0.20002(14)0.0469(3)
C80.7163(3)0.19014(7)0.10932(16)0.0573(4)
H8A0.6041700.1544520.1298970.069*
H8B0.6817990.2005430.0077170.069*

Source of material

2-Chloro-N-(4-nitrophenyl)acetamide (0.011 moles) and sodium azide (0.015 moles) were dissolved in a mixture of ethanol/water (70:30) and refluxed for 24 h at 80 °C. After cooling the title compound precipitated. The crude product was filtered off and dried. Recrystallization from ethanol yielded yellow crystals, yield: 69%.

Experimental details

H-atoms attached to carbon were placed in calculated positions while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91 Å. All were included as riding contributions.

Comment

Azides have found valuable applications in medicinal chemistry [5], molecular biology [6], and an increasing interest in the field of organic synthesis as intermediates for the preparation of heterocycles such as tetrazoles, triazolines, triazoles, etc. [7], [8], [9].

In the title molecule (see the figure), the plane of the nitro group (C4/N1/O1/O2) is inclined to that of the C1⋯C6 phenyl ring by 5.9(1)° while the N2/C7/O3/C8 plane is inclined by 14.8(1)°. This latter feature is likely due in part to the intramolecular C2—H2⋯O3 hydrogen bond and more likely by the π-system constructed by the phenyl-(NH)-(C=O) which is also seen in a directly related structure [10]. The azido group is rotated well out of this aforementioned plane as indicated by the C7—C8—N3—N4 torsion angle of 72.07(17)°. In the crystal, N2—H2A⋯O3 hydrogen bonds form chains extending parallel to (10-1). Weak C3—H3⋯O1 hydrogen bonds link the chains into zig zag layers which are associated via weak C6—H6⋯N5 hydrogen bonds.

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

References

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Received: 2020-07-09
Accepted: 2020-08-02
Published Online: 2020-08-08
Published in Print: 2020-10-27

©2020 Mohcine Missioui et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  79. The crystal structure of (3S,8R,10R,14R)-17-((2S,5S)-5-(2-hydroxypropan-2-yl)-2-methyltetrahydrofuran-2-yl)-4,4,8,10,14-pentamethyl-12-oxohexadecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate, C32H52O5
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