Ethyl 2-[(azido­carbon­yl)amino]­benzoate

Yassine, H.; Hafid, A.; Khouili, M.; Mentre, O.; Ketatni, E.M.

doi:10.1107/S241431461601155X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161155

https://doi.org/10.1107/S241431461601155X

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Ethyl 2-[(azidocarbonyl)amino]benzoate

Hasna Yassine,^a ^* Abderrafia Hafid,^a Mostafa Khouili,^a Olivier Mentre ^b and El Mostafa Ketatni ^c

^aLaboratoire de Chimie Organique et Analytique, University Sultan Moulay Slimane, Faculty of Science and Technology, BP 523, Beni-Mellal, Morocco, ^bUniv. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 – UCCS – Unite de Catalyse et Chimie du Solide, F-59000 Lille, France, and ^cLaboratoire de Spectro-Chimie Applique et Environnement, University Sultan Moulay Slimane, Faculty of Science and Technology, BP 523, Beni-Mellal, Morocco
^*Correspondence e-mail: hasna.yassine@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 6 July 2016; accepted 15 July 2016; online 22 July 2016)

In the almost planar (r.m.s. deviation = 0.038 Å) title compound, C₁₀H₁₀N₄O₃, an intramolecular N—H⋯O interaction closes an S(6) ring. In the crystal, aromatic π–π stacking interactions occur [inter-centroid distance = 3.65 (2) Å].

Keywords: crystal structure; azide; π–π interactions.

CCDC reference: 1493829

Structure description

Direct conversion of carboxylic acids to acyl azides can be achieved by using diphenylphosphoryl azide (DPPA) in the presence of a base (Katritzky et al., 2007 ). In an attempt to synthesize ethyl 2-isocyanatobenzoate, the title compound was formed and its structure is reported here.

The molecular structure is shown in Fig. 1. The molecule is approximately planar, with an r.m.s. deviation of 0.038 Å for the non-H atoms. The geometry of the azide group is normal for covalent azide groups, with longer Nα—Nβ distances [N2—N3 = 1.264 (2) Å] and shorter terminal Nβ—Nγ distances [N3—N4 = 1.131 (2) Å], with more triple-bond character. The azide angle is slightly bent [N2—N3—N4 = 174.7 (2)°]. An intramolecular N—H⋯O interaction closes an S(6) ring (Table 1 and Fig. 1). Aromatic π–π stacking interactions occur in the crystal [inter-centroid distance = 3.653 (2) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.86	1.95	2.6593 (19)	139

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. The intramolecular hydrogen bond is drawn as a dashed line.

Synthesis and crystallization

A solution of 2-(ethoxycarbonyl) benzoic acid (100 mg, 0.53 mmol), DPPA (0.194 ml, 0.90 mmol) and Et₃N (0.127 ml, 0.90 mmol) in toluene (5 ml) was refluxed for 4 h. After cooling to room temperature, the reaction mixture was concentrated. The residue was purified by column chromatography using EtOAc–hexane (1:9 v/v) as eluent to give purple parallelepiped-shaped crystals (yield 71%, m.p. = 337 K).

¹H NMR (300 MHz, CDCl₃): δ 1.37 (3H, H10), 4.40 (2H, H9), 7.13 (1H, H5), 7.58 (1H, H4), 8.06 (1H, H3), 8.51 (1H, H6), 10.90 (1H, NH).

¹³C NMR (75 MHz, CDCl₃): δ 14.17 (C10), 61.62 (C9), 115.50 (C7), 119.52 (C3), 122.83 (C5), 130.94 (C6), 134.62 (C4), 140.64 (C2), 154.43 (C1), 167.98 (C8)

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The reflection $[\overline{3}]$ 39 was removed during refinement due to poor agreement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄O₃
M_r	234.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	300
a, b, c (Å)	9.330 (6), 18.724 (4), 13.484 (3)
β (°)	102.898 (8)
V (Å³)	2296.3 (17)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.32 × 0.24 × 0.17

Data collection
Diffractometer	Bruker DUO APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.695, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	16533, 2352, 1302
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.096, 1.61
No. of reflections	2352
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1493829

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461601155X/hb4066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461601155X/hb4066Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461601155X/hb4066Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Ethyl 2-[(azidocarbonyl)amino]benzoate top

Crystal data top

C₁₀H₁₀N₄O₃	F(000) = 976
M_r = 234.22	D_x = 1.355 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.330 (6) Å	Cell parameters from 2352 reflections
b = 18.724 (4) Å	θ = 2.2–26.4°
c = 13.484 (3) Å	µ = 0.10 mm⁻¹
β = 102.898 (8)°	T = 300 K
V = 2296.3 (17) Å³	Parallelepiped, purple
Z = 8	0.32 × 0.24 × 0.17 mm

Data collection top

Bruker DUO APEXII CCD diffractometer	1302 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 26.4°, θ_min = 2.2°
T_min = 0.695, T_max = 0.746	h = −11→11
16533 measured reflections	k = −22→23
2352 independent reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.022P)²] where P = (F_o² + 2F_c²)/3
S = 1.61	(Δ/σ)_max < 0.001
2352 reflections	Δρ_max = 0.14 e Å⁻³
154 parameters	Δρ_min = −0.15 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
O1	1.03497 (14)	0.23713 (7)	−0.00286 (9)	0.0749 (4)
O2	1.00146 (14)	0.35584 (6)	−0.00214 (9)	0.0742 (4)
O3	0.80897 (14)	0.07009 (6)	0.20144 (9)	0.0828 (4)
N1	0.89748 (15)	0.15816 (8)	0.11107 (10)	0.0644 (4)
H1N	0.9479	0.1624	0.0652	0.077*
N2	0.94011 (18)	0.04318 (9)	0.07886 (11)	0.0757 (5)
N3	0.92839 (18)	−0.02151 (11)	0.10254 (11)	0.0760 (5)
N4	0.9226 (2)	−0.08071 (11)	0.11767 (14)	0.1044 (7)
C1	0.87368 (19)	0.09018 (11)	0.13835 (12)	0.0608 (5)
C2	0.85122 (18)	0.22285 (9)	0.14731 (12)	0.0570 (5)
C3	0.7684 (2)	0.22489 (10)	0.22159 (13)	0.0672 (5)
H3	0.7418	0.1825	0.2487	0.081*
C4	0.7258 (2)	0.28947 (11)	0.25512 (14)	0.0763 (6)
H4	0.6706	0.2900	0.3047	0.092*
C5	0.7638 (2)	0.35352 (11)	0.21619 (14)	0.0787 (6)
H5	0.7347	0.3968	0.2394	0.094*
C6	0.8451 (2)	0.35222 (10)	0.14275 (13)	0.0708 (5)
H6	0.8705	0.3951	0.1165	0.085*
C7	0.89052 (19)	0.28814 (9)	0.10673 (11)	0.0581 (5)
C8	0.9820 (2)	0.28912 (10)	0.02929 (12)	0.0604 (5)
C9	1.0927 (2)	0.36288 (10)	−0.07630 (14)	0.0796 (6)
H9A	1.0502	0.3363	−0.1376	0.096*
H9B	1.1907	0.3446	−0.0485	0.096*
C10	1.0989 (2)	0.44148 (11)	−0.09986 (16)	0.0963 (7)
H10A	1.1583	0.4485	−0.1487	0.144*
H10B	1.0013	0.4588	−0.1272	0.144*
H10C	1.1411	0.4671	−0.0386	0.144*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0898 (10)	0.0688 (9)	0.0801 (9)	0.0021 (7)	0.0486 (8)	−0.0069 (7)
O2	0.0891 (10)	0.0708 (9)	0.0754 (8)	0.0005 (7)	0.0455 (7)	−0.0005 (7)
O3	0.0948 (10)	0.0884 (10)	0.0811 (9)	−0.0028 (8)	0.0532 (8)	0.0071 (7)
N1	0.0729 (11)	0.0685 (11)	0.0612 (9)	−0.0005 (9)	0.0347 (8)	−0.0029 (8)
N2	0.1067 (14)	0.0605 (11)	0.0740 (10)	−0.0056 (10)	0.0501 (10)	−0.0004 (8)
N3	0.0918 (13)	0.0790 (13)	0.0691 (10)	0.0015 (11)	0.0436 (9)	0.0044 (10)
N4	0.1434 (19)	0.0794 (14)	0.1117 (15)	0.0070 (13)	0.0739 (13)	0.0190 (12)
C1	0.0625 (12)	0.0719 (14)	0.0529 (10)	−0.0017 (10)	0.0229 (10)	−0.0007 (9)
C2	0.0504 (11)	0.0710 (13)	0.0514 (10)	0.0027 (10)	0.0152 (9)	−0.0057 (9)
C3	0.0635 (13)	0.0816 (14)	0.0625 (11)	0.0027 (10)	0.0270 (10)	−0.0004 (10)
C4	0.0696 (14)	0.0977 (17)	0.0702 (12)	0.0097 (12)	0.0342 (11)	−0.0065 (12)
C5	0.0806 (15)	0.0854 (16)	0.0789 (13)	0.0172 (12)	0.0363 (11)	−0.0081 (11)
C6	0.0752 (14)	0.0730 (14)	0.0698 (12)	0.0075 (11)	0.0283 (11)	−0.0012 (10)
C7	0.0561 (12)	0.0701 (13)	0.0513 (10)	0.0046 (10)	0.0188 (9)	−0.0027 (9)
C8	0.0617 (13)	0.0654 (14)	0.0561 (11)	−0.0015 (10)	0.0173 (10)	−0.0002 (10)
C9	0.0885 (15)	0.0813 (15)	0.0833 (13)	−0.0096 (12)	0.0495 (12)	−0.0035 (11)
C10	0.1081 (18)	0.0911 (17)	0.1038 (16)	−0.0088 (14)	0.0540 (14)	0.0110 (12)

Geometric parameters (Å, º) top

O1—C8	1.2147 (19)	C4—C5	1.387 (2)
O2—C8	1.3445 (19)	C4—H4	0.9300
O2—C9	1.4566 (19)	C5—C6	1.376 (2)
O3—C1	1.2079 (18)	C5—H5	0.9300
N1—C1	1.357 (2)	C6—C7	1.395 (2)
N1—C2	1.409 (2)	C6—H6	0.9300
N1—H1N	0.8600	C7—C8	1.489 (2)
N2—N3	1.264 (2)	C9—C10	1.510 (2)
N2—C1	1.423 (2)	C9—H9A	0.9700
N3—N4	1.131 (2)	C9—H9B	0.9700
C2—C3	1.395 (2)	C10—H10A	0.9600
C2—C7	1.421 (2)	C10—H10B	0.9600
C3—C4	1.380 (2)	C10—H10C	0.9600
C3—H3	0.9300

C8—O2—C9	116.17 (13)	C5—C6—C7	121.66 (18)
C1—N1—C2	129.11 (14)	C5—C6—H6	119.2
C1—N1—H1N	115.4	C7—C6—H6	119.2
C2—N1—H1N	115.4	C6—C7—C2	118.78 (15)
N3—N2—C1	112.16 (14)	C6—C7—C8	119.97 (16)
N4—N3—N2	174.74 (18)	C2—C7—C8	121.23 (15)
O3—C1—N1	128.37 (16)	O1—C8—O2	122.55 (16)
O3—C1—N2	123.62 (17)	O1—C8—C7	125.65 (17)
N1—C1—N2	108.01 (15)	O2—C8—C7	111.80 (16)
C3—C2—N1	122.27 (16)	O2—C9—C10	106.76 (15)
C3—C2—C7	119.00 (16)	O2—C9—H9A	110.4
N1—C2—C7	118.72 (14)	C10—C9—H9A	110.4
C4—C3—C2	120.35 (17)	O2—C9—H9B	110.4
C4—C3—H3	119.8	C10—C9—H9B	110.4
C2—C3—H3	119.8	H9A—C9—H9B	108.6
C3—C4—C5	121.13 (17)	C9—C10—H10A	109.5
C3—C4—H4	119.4	C9—C10—H10B	109.5
C5—C4—H4	119.4	H10A—C10—H10B	109.5
C6—C5—C4	119.07 (17)	C9—C10—H10C	109.5
C6—C5—H5	120.5	H10A—C10—H10C	109.5
C4—C5—H5	120.5	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.86	1.95	2.6593 (19)	139

Acknowledgements

The authors thank the Unit of Catalysis and Chemistry of Solid (UCCS) UMR CNRS 8181–Lille for the X-ray measurements and for financial support.

References

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