Butyl 2-[(azido­carbon­yl)amino]­benzoate

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

doi:10.1107/S2414314616014541

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161454

doi:10.1107/S2414314616014541

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access

Butyl 2-[(azidocarbonyl)amino]benzoate

Hasna Yassine,^a ^* Mostafa Khouili,^a Abderrafia Hafid,^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 J. Simpson, University of Otago, New Zealand (Received 8 September 2016; accepted 13 September 2016; online 16 September 2016)

The title compound, C₁₂H₁₄N₄O₃, is planar with an r.m.s deviation of 0.025 Å from the plane through all 19 non-hydrogen atoms. An intramolecular N—H⋯O interaction closes an S(6) ring. In the crystal, molecules are linked by C—H⋯π and weak offset π–π stacking interactions [inter-centroid distance = 3.614 (2) Å], forming undulating sheets parallel to (001).

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

CCDC reference: 1504127

Structure description

As part of our ongoing studies of azide derivatives, we now describe the title compound, C₁₂H₁₄N₄O₃, with the molecular structure shown in Fig. 1. All non-hydrogen atoms are almost co-planar, with an r.m.s deviation of 0.025 Å from the plane through all 19 non-hydrogen atoms. Bond lengths and angles in the azide group are normal, with the N2—N3 bond [1.246 (3) Å] longer than the terminal N1—N2 distance [1.114 (3) Å] which has more triple-bond character. The azide angle is slightly bent [N1—N2—N3 = 175.2 (2)°]. An intramolecular N—H⋯O interaction closes an S(6) ring (Table 1; Fig. 1). A closely similar structure, ethyl 2-[(azidocarbonyl)amino]benzoate was reported recently (Yassine et al., 2016 ).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯O2	0.86	1.93	2.644 (2)	139
C9—H9A⋯Cg1ⁱ	0.97	2.89	3.681 (3)	139
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+1]$ .

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level and the Intramolecular hydrogen bond is shown as a dashed line.

In the crystal, molecules are linked by C—H⋯π and weak offset π–π stacking interactions [Cg1⋯Cg1ⁱ = 3.614 (2) Å, where Cg1 is the centroid of the C2–C7 ring; symmetry code: (i) −x, y, $[{1\over 2}]$ − z], forming sheets parallel to (001) (Table 1 and Fig. 2).

Figure 2
Partial crystal packing for the title compound showing π–π and C—H⋯π interactions between inversion-related molecules as dashed lines.

Synthesis and crystallization

A solution of 2-(butoxycarbonyl)benzoic acid (100 mg, 0.45 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 recrystallized from EtOAc–hexane (1:9 v/v) to give blue block-shaped crystals in a yield of 63%, m.p. = 317 K.

¹H NMR (300 MHz, CDCl₃, δ p.p.m.): 10.87 (1H, NH), 8.48 (1H, H6), 8.03 (1H, H3), 7.55 (1H, H4), 7.11 (1H, H5), 4.32 (2H, H9), 1.76 (2H, H10), 1.48 (2H, H11), 0.98 (3H, H12). ¹³C NMR (75 MHz, CDCl₃, δ p.p.m.): 168.00(C8), 154.40(C1), 140.58(C2), 134.59(C4), 130.89(C6), 122.85(C5), 119.50(C3), 115.54(C7), 65.44(C9), 30.53(C10), 19.22(C11), 13.70(C12).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The reflection (0 6 12) affected by the beam-stop was removed during refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₄O₃
M_r	262.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	299
a, b, c (Å)	9.780 (3), 17.698 (5), 15.819 (4)
β (°)	105.985 (16)
V (Å³)	2632.2 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.22 × 0.15

Data collection
Diffractometer	Bruker DUO APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker,2009 )
T_min, T_max	0.662, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	28366, 2318, 1370
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 0.98
No. of reflections	2318
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1504127

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616014541/sj4055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014541/sj4055Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014541/sj4055Isup3.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) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Butyl 2-[(azidocarbonyl)amino]benzoate top

Crystal data top

C₁₂H₁₄N₄O₃	F(000) = 1104
M_r = 262.27	D_x = 1.324 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.780 (3) Å	Cell parameters from 2318 reflections
b = 17.698 (5) Å	θ = 2.3–25.0°
c = 15.819 (4) Å	µ = 0.10 mm⁻¹
β = 105.985 (16)°	T = 299 K
V = 2632.2 (12) Å³	Block, purple
Z = 8	0.30 × 0.22 × 0.15 mm

Data collection top

Bruker DUO APEXII CCD diffractometer	1370 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.064
Absorption correction: multi-scan (SADABS; Bruker,2009)	θ_max = 25.0°, θ_min = 2.3°
T_min = 0.662, T_max = 0.746	h = −11→11
28366 measured reflections	k = −20→20
2318 independent reflections	l = −18→18

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0486P)² + 1.1042P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max < 0.001
S = 0.98	Δρ_max = 0.18 e Å⁻³
2318 reflections	Δρ_min = −0.14 e Å⁻³
173 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00046 (17)

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	0.82291 (15)	−0.05566 (8)	0.54241 (9)	0.0619 (4)
O2	0.78779 (17)	0.06864 (9)	0.53246 (10)	0.0711 (5)
O3	1.13563 (18)	0.25170 (9)	0.69941 (11)	0.0749 (5)
N1	0.9649 (2)	0.40575 (13)	0.63239 (15)	0.0870 (7)
N2	0.9465 (2)	0.34416 (13)	0.61991 (13)	0.0656 (5)
N3	0.9168 (2)	0.27669 (11)	0.60087 (12)	0.0664 (6)
C1	1.0288 (2)	0.22860 (13)	0.64945 (14)	0.0555 (6)
C2	1.0654 (2)	0.09038 (12)	0.66053 (13)	0.0514 (5)
C7	1.0039 (2)	0.02017 (12)	0.62878 (13)	0.0522 (5)
C8	0.8622 (2)	0.01555 (13)	0.56352 (14)	0.0555 (6)
N4	0.99075 (19)	0.15649 (9)	0.62810 (11)	0.0581 (5)
H4N	0.9102	0.1502	0.5896	0.070*
C3	1.1961 (2)	0.09132 (13)	0.72320 (14)	0.0604 (6)
H3	1.2379	0.1372	0.7446	0.072*
C4	1.2644 (2)	0.02473 (14)	0.75398 (15)	0.0645 (6)
H4	1.3521	0.0263	0.7961	0.077*
C5	1.2056 (2)	−0.04399 (14)	0.72361 (15)	0.0668 (7)
H5	1.2529	−0.0886	0.7449	0.080*
C6	1.0765 (2)	−0.04600 (13)	0.66150 (15)	0.0621 (6)
H6	1.0365	−0.0924	0.6408	0.075*
C9	0.6860 (2)	−0.06591 (12)	0.47901 (15)	0.0600 (6)
H9A	0.6846	−0.0407	0.4243	0.072*
H9B	0.6115	−0.0444	0.5013	0.072*
C10	0.6622 (2)	−0.14899 (11)	0.46373 (14)	0.0567 (6)
H10A	0.6634	−0.1734	0.5188	0.068*
H10B	0.7390	−0.1700	0.4434	0.068*
C11	0.5212 (2)	−0.16541 (12)	0.39631 (15)	0.0673 (7)
H11A	0.4447	−0.1445	0.4170	0.081*
H11B	0.5199	−0.1403	0.3416	0.081*
C12	0.4946 (3)	−0.24873 (13)	0.37882 (17)	0.0868 (9)
H12A	0.4046	−0.2557	0.3360	0.130*
H12B	0.5688	−0.2697	0.3570	0.130*
H12C	0.4935	−0.2738	0.4324	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0566 (10)	0.0519 (9)	0.0651 (10)	0.0001 (7)	−0.0033 (8)	−0.0033 (7)
O2	0.0679 (11)	0.0531 (10)	0.0743 (11)	0.0064 (8)	−0.0106 (8)	−0.0025 (8)
O3	0.0629 (11)	0.0601 (10)	0.0861 (12)	−0.0046 (8)	−0.0058 (9)	−0.0045 (9)
N1	0.0811 (16)	0.0590 (15)	0.1032 (18)	0.0072 (12)	−0.0046 (13)	−0.0056 (13)
N2	0.0610 (13)	0.0582 (15)	0.0685 (13)	0.0045 (11)	0.0025 (10)	−0.0006 (11)
N3	0.0684 (13)	0.0497 (12)	0.0701 (13)	−0.0028 (10)	0.0006 (10)	−0.0021 (10)
C1	0.0562 (15)	0.0542 (14)	0.0525 (13)	−0.0018 (12)	0.0088 (12)	−0.0007 (11)
C2	0.0491 (13)	0.0511 (13)	0.0523 (13)	0.0007 (11)	0.0111 (11)	0.0007 (10)
C7	0.0501 (13)	0.0535 (13)	0.0506 (12)	0.0011 (11)	0.0096 (10)	−0.0008 (10)
C8	0.0591 (15)	0.0519 (14)	0.0536 (13)	0.0016 (12)	0.0122 (11)	−0.0030 (11)
N4	0.0552 (11)	0.0491 (12)	0.0602 (11)	−0.0004 (9)	−0.0005 (9)	−0.0003 (9)
C3	0.0557 (14)	0.0585 (15)	0.0614 (14)	−0.0027 (12)	0.0069 (11)	−0.0013 (11)
C4	0.0523 (14)	0.0653 (16)	0.0675 (15)	0.0023 (12)	0.0021 (11)	0.0035 (13)
C5	0.0604 (16)	0.0602 (15)	0.0726 (16)	0.0092 (12)	0.0064 (13)	0.0057 (13)
C6	0.0599 (15)	0.0534 (14)	0.0674 (15)	0.0004 (11)	0.0080 (12)	−0.0012 (12)
C9	0.0562 (14)	0.0536 (14)	0.0617 (14)	0.0035 (11)	0.0022 (11)	−0.0019 (11)
C10	0.0543 (13)	0.0528 (13)	0.0567 (14)	0.0018 (10)	0.0047 (11)	0.0003 (10)
C11	0.0585 (15)	0.0610 (16)	0.0707 (15)	−0.0001 (12)	−0.0021 (12)	−0.0023 (12)
C12	0.083 (2)	0.0685 (18)	0.090 (2)	−0.0093 (15)	−0.0069 (15)	−0.0108 (14)

Geometric parameters (Å, º) top

O1—C8	1.333 (2)	C4—H4	0.9300
O1—C9	1.446 (2)	C5—C6	1.371 (3)
O2—C8	1.207 (2)	C5—H5	0.9300
O3—C1	1.195 (2)	C6—H6	0.9300
N1—N2	1.114 (2)	C9—C10	1.498 (3)
N2—N3	1.246 (3)	C9—H9A	0.9700
N3—C1	1.433 (3)	C9—H9B	0.9700
C1—N4	1.346 (3)	C10—C11	1.521 (3)
C2—C3	1.385 (3)	C10—H10A	0.9700
C2—N4	1.400 (2)	C10—H10B	0.9700
C2—C7	1.411 (3)	C11—C12	1.510 (3)
C7—C6	1.393 (3)	C11—H11A	0.9700
C7—C8	1.485 (3)	C11—H11B	0.9700
N4—H4N	0.8600	C12—H12A	0.9600
C3—C4	1.376 (3)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C5	1.374 (3)

C8—O1—C9	116.14 (16)	C5—C6—C7	121.3 (2)
N1—N2—N3	175.2 (2)	C5—C6—H6	119.4
N2—N3—C1	110.28 (19)	C7—C6—H6	119.4
O3—C1—N4	128.4 (2)	O1—C9—C10	107.97 (17)
O3—C1—N3	123.5 (2)	O1—C9—H9A	110.1
N4—C1—N3	108.10 (19)	C10—C9—H9A	110.1
C3—C2—N4	122.53 (19)	O1—C9—H9B	110.1
C3—C2—C7	119.0 (2)	C10—C9—H9B	110.1
N4—C2—C7	118.50 (19)	H9A—C9—H9B	108.4
C6—C7—C2	119.0 (2)	C9—C10—C11	111.82 (17)
C6—C7—C8	119.6 (2)	C9—C10—H10A	109.3
C2—C7—C8	121.38 (19)	C11—C10—H10A	109.3
O2—C8—O1	122.3 (2)	C9—C10—H10B	109.3
O2—C8—C7	125.7 (2)	C11—C10—H10B	109.3
O1—C8—C7	112.08 (19)	H10A—C10—H10B	107.9
C1—N4—C2	128.32 (19)	C12—C11—C10	113.11 (19)
C1—N4—H4N	115.8	C12—C11—H11A	109.0
C2—N4—H4N	115.8	C10—C11—H11A	109.0
C4—C3—C2	120.4 (2)	C12—C11—H11B	109.0
C4—C3—H3	119.8	C10—C11—H11B	109.0
C2—C3—H3	119.8	H11A—C11—H11B	107.8
C5—C4—C3	121.2 (2)	C11—C12—H12A	109.5
C5—C4—H4	119.4	C11—C12—H12B	109.5
C3—C4—H4	119.4	H12A—C12—H12B	109.5
C6—C5—C4	119.2 (2)	C11—C12—H12C	109.5
C6—C5—H5	120.4	H12A—C12—H12C	109.5
C4—C5—H5	120.4	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O2	0.86	1.93	2.644 (2)	139
C9—H9A···Cg1ⁱ	0.97	2.89	3.681 (3)	139

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

Acknowledgements

The X-rays diffractometer is funded by Région NPDC, FEDER, CNRS and MESR.

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Yassine, H., Hafid, A., Khouili, M., Mentre, O. & Ketatni, E. M. (2016). IUCrData, 1, x161155. Google Scholar

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ISSN: 2414-3146

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doi:10.1107/S2414314616014541

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Butyl 2-[(azido­carbon­yl)amino]­benzoate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

Butyl 2-[(azidocarbonyl)amino]benzoate