Abstract
C8H8N4O, orthorhombic, P212121 (no. 19), a = 5.8085(13) Å, b = 16.533(4) Å, c = 18.171(4) Å, V = 1745.0(7) Å3, Z = 8, Rgt(F) = 0.0399, wRref(F2) = 0.1078, T = 296(2) K.
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.
Data collection and handling.
| Crystal: | Colourless block |
| Size: | 0.40 × 0.32 × 0.30 mm |
| Wavelength: | Cu Kα radiation (1.54178 Å) |
| μ: | 0.79 mm−1 |
| Diffractometer, scan mode: | D8 VENTURE PHOTON 100, ω |
| θmax, completeness: | 72.5°, 99% |
| N(hkl)measured, N(hkl)unique, Rint: | 8365, 3383, 0.032 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 3204 |
| N(param)refined: | 236 |
| Programs: | Bruker [1], SHELX [2], [3], [4], [6], Diamond [5] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| O1 | 0.2355 (3) | 0.29894 (8) | 0.23380 (8) | 0.0657 (4) |
| N1 | 0.3120 (3) | 0.19233 (9) | 0.30918 (9) | 0.0535 (4) |
| H1 | 0.272547 | 0.143385 | 0.319042 | 0.064* |
| N2 | −0.1241 (5) | 0.22663 (13) | 0.17114 (14) | 0.0871 (7) |
| N3 | −0.2933 (4) | 0.19339 (12) | 0.14523 (12) | 0.0707 (5) |
| N4 | −0.4536 (5) | 0.17043 (18) | 0.11761 (17) | 0.0993 (9) |
| C1 | 0.4922 (3) | 0.22590 (11) | 0.35168 (10) | 0.0505 (4) |
| C2 | 0.5078 (4) | 0.30827 (12) | 0.36577 (12) | 0.0625 (5) |
| H2 | 0.397649 | 0.343636 | 0.347233 | 0.075* |
| C3 | 0.6891 (5) | 0.33725 (16) | 0.40772 (14) | 0.0754 (7) |
| H3 | 0.700620 | 0.392420 | 0.417011 | 0.090* |
| C4 | 0.8527 (5) | 0.28540 (18) | 0.43585 (12) | 0.0741 (7) |
| H4 | 0.975150 | 0.305343 | 0.463358 | 0.089* |
| C5 | 0.8324 (5) | 0.20377 (17) | 0.42272 (13) | 0.0729 (6) |
| H5 | 0.941466 | 0.168440 | 0.441990 | 0.087* |
| C6 | 0.6533 (5) | 0.17367 (14) | 0.38152 (11) | 0.0638 (5) |
| H6 | 0.640454 | 0.118259 | 0.373706 | 0.077* |
| C7 | 0.1968 (3) | 0.22964 (11) | 0.25490 (10) | 0.0510 (4) |
| C8 | 0.0165 (4) | 0.17728 (12) | 0.21914 (12) | 0.0617 (5) |
| H8A | 0.089937 | 0.134667 | 0.190952 | 0.074* |
| H8B | −0.079095 | 0.152361 | 0.256584 | 0.074* |
| O2 | 0.6474 (3) | 0.46627 (9) | 0.63830 (10) | 0.0737 (5) |
| N5 | 0.4595 (3) | 0.58698 (10) | 0.62794 (10) | 0.0587 (4) |
| H5A | 0.457556 | 0.635003 | 0.646123 | 0.070* |
| N6 | 0.8264 (4) | 0.50883 (14) | 0.77325 (14) | 0.0826 (7) |
| N7 | 1.0343 (4) | 0.50238 (11) | 0.76906 (11) | 0.0679 (5) |
| N8 | 1.2245 (6) | 0.4922 (2) | 0.7732 (2) | 0.1183 (12) |
| C9 | 0.3063 (4) | 0.57312 (12) | 0.56913 (11) | 0.0561 (5) |
| C10 | 0.3275 (6) | 0.51010 (14) | 0.52004 (13) | 0.0753 (7) |
| H10 | 0.450885 | 0.474455 | 0.523344 | 0.090* |
| C11 | 0.1625 (7) | 0.50050 (18) | 0.46569 (16) | 0.0985 (11) |
| H11 | 0.174874 | 0.457034 | 0.433444 | 0.118* |
| C12 | −0.0139 (7) | 0.5518 (2) | 0.45813 (16) | 0.0967 (10) |
| H12 | −0.122525 | 0.543667 | 0.421252 | 0.116* |
| C13 | −0.0341 (6) | 0.6168 (2) | 0.50528 (16) | 0.0950 (9) |
| H13 | −0.154569 | 0.653305 | 0.499807 | 0.114* |
| C14 | 0.1267 (5) | 0.62718 (18) | 0.56094 (13) | 0.0778 (7) |
| H14 | 0.113588 | 0.670847 | 0.592930 | 0.093* |
| C15 | 0.6087 (4) | 0.53509 (12) | 0.65948 (12) | 0.0565 (5) |
| C16 | 0.7281 (5) | 0.57151 (14) | 0.72602 (15) | 0.0742 (7) |
| H16A | 0.849637 | 0.607510 | 0.709639 | 0.089* |
| H16B | 0.618243 | 0.603172 | 0.754047 | 0.089* |
Source of material
2–Chloro-N-(4-nitrophenyl)acetamide (0.006 mol) and sodium azide (0.0085 mol) were dissolved in a mixture of ethanol/water (70:30, v:v) then refluxed for 24 h at 80 °C. After cooling the title compound precipitated and was filtered off, dried and recrystallized from ethanol, yield: 77%. A portion of the product was dissolved in hot ethanol, the solution was filtered and the filtrate was left undisturbed for 5 days to form clear, colorless block crystals.
Experimental details
Hydrogen atoms were included as riding contributions in idealized positions. The Flack-Parsons parameter was calculated as -0.04(10) based on 1251 quotients [6].
Comment
Azides have found valuable applications in medicinal chemistry [7], molecular biology [8], and an increasing interest in the field of organic synthesis as intermediates for the preparation of heterocycles such as tetrazoles, triazolines, triazoles, etc. [9], [10], [11]. As part of our ongoing research in this area, we report the synthesis and molecular structure of the title azide.
The asymmetric unit consists of two independent molecules differing primarily in the orientation of the azide moiety. Thus in the molecule containing O1, the dihedral angle between the mean planes defined by N1/C7/C8/O1 and C8/N2/N3/N4 is 10.9(2)° (see the Figure), while the corresponding angle in the molecule containing O2 is 80.9(2)°. Also, in the molecule containing O1, the dihedral angle between the mean planes defined by C1⃛C6 and N1/C7/C8/O1 is 28.4(1)°, while the corresponding angle in the other molecule is 16.3(2)°. In the crystal, the two independent molecules are linked in alternating fashion by N1–H1⃛O2 and N5–H5A⃛O1 hydrogen bonds into helical chains extending along the b-axis direction (Table 2). The chains are joined into layers parallel to the bc plane by π interactions between the N3/N4 moiety of the azide substituent and the C1⃛C6 ring at −x, y − 1/2, −z + 1/2 (N4⃛centroid = 3.462(3) Å, N3⃛centroid = 3.695(3) Å, N3/N4⃛centroid = 93.0(2)°.
Funding source: NSF-MRI
Award Identifier / Grant number: 1228232
Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Funding information: The support of NSF-MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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© 2020 Walid Guerrab et al., published by De Gruyter, Berlin/Boston
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