2,6-Diazido­toluene

Klapötke, T.M.; Krumm, B.; Scherr, M.; Spiess, G.

doi:10.1107/S160053680706744X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o348

doi:10.1107/S160053680706744X

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2,6-Diazidotoluene

Thomas M. Klapötke,^a ^* Burkhard Krumm,^a Matthias Scherr ^a and Gunnar Spiess ^a

^aDepartment of Chemistry and Biochemistry, Ludwig-Maximilian University, Butenandtstrasse 5–13, D-81377 Munich, Germany
^*Correspondence e-mail: tmk@cup.uni-muenchen.de

(Received 10 December 2007; accepted 17 December 2007; online 4 January 2008)

The structure of the title compound, C₇H₆N₆, consists of almost planar molecules with C—N distances of 1.429 (2) and 1.428 (2) Å. The H atoms of the methyl group are disordered over two sites with occupancy factors of 0.69 and 0.31. The azide groups show typical geometry for covalently bound azides.

Related literature

The preparation of the title compound by a slightly different procedure was reported by Chapyshev & Tomioka (2003 ). For the comparable compound, 2-azidobenzyl bromide, see: Klapötke et al. (2003 ).

Experimental

Crystal data

C₇H₆N₆
M_r = 174.16
Orthorhombic, P c c n
a = 12.298 (5) Å
b = 25.896 (5) Å
c = 5.085 (5) Å
V = 1619.4 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 (2) K
0.29 × 0.14 × 0.13 mm

Data collection

Oxford Xcalibur3 CCD area-detector diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.899, T_max = 0.990
5871 measured reflections
1578 independent reflections
956 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.061
S = 0.94
1578 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: DIAMOND (Brandenburg, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706744X/fj2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680706744X/fj2092Isup2.hkl

checkCIF report

Comment top

The structure of the title compound exhibits C–N distances [C2–N1 1.429 (2) and C6–N4 1.428 (2) Å] similar to the distance in 2-N₃C₆H₄CH₂Br [1.428 (5) Å, Klapötke et al., 2003]. The values of both azide groups are in the common range for covalent azide groups with longer N_α–N_β distances [N1–N2 1.241 (2) and N4–N5 1.253 (2) Å] and shorter terminal N_β–N_γ distances [N2–N3 1.133 (2) and N5–N6 1.122 (2) Å] with more triple bond character. The azide angles are slightly bent [N1–N2–N3 172.98 (18) and N4–N5–N6 172.36 (17)°].

Related literature top

The preparation of the title compound by a slightly different procedure was reported by Chapyshev & Tomioka (2003). For the comparable compound, 2-azidobenzylbromide, see: Klapötke et al. 2003.

Experimental top

The title compound was prepared according the literature [Chapyshev & Tomioka (2003)], slightly modified, e.g. the column chromatography was performed with hexane/chloroform (1:4) as an eluent. Colorless crystals were obtained by slow evaporation of a chloroform solution. ¹H NMR (400 MHz, CDCl₃, Me₄Si): δ 7.23 (tq, 4-H, ³J_H–H = 8.1 Hz, ⁶J_H—H = 0.5 Hz, 1H), 6.89 (d, 3-H, 2H), 2.05 (m, CH₃, 3H) p.p.m.; ¹³C NMR (400 MHz, CDCl₃, Me₄Si): δ 140.0/127.2/121.3/114.0 (Ar—C), 11.2 (CH₃) p.p.m.; ¹⁵N NMR (400 MHz, CDCl₃, MeNO₂) δ -139.5 (N_β), -149.0 (N_γ), -291.4 (N_α) p.p.m..

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction,2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. Molecular structure of C₇H₆N₆ with displacement ellipsoids drawn at the 50% probability level. The minor disorder component of the methyl hydrogen atoms has been omitted.

2,6-Diazidotoluene top

Crystal data top

C₇H₆N₆	F(000) = 720
M_r = 174.16	D_x = 1.429 (1) Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1382 reflections
a = 12.298 (5) Å	θ = 3.9–30.0°
b = 25.896 (5) Å	µ = 0.10 mm⁻¹
c = 5.085 (5) Å	T = 200 K
V = 1619.4 (18) Å³	Needle, colorless
Z = 8	0.29 × 0.14 × 0.13 mm

Data collection top

Oxford Xcalibur3 CCD area-detector diffractometer	1578 independent reflections
Radiation source: fine-focus sealed tube	956 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 15.9809 pixels mm^-1	θ_max = 26.0°, θ_min = 4.3°
ω scans	h = −15→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −19→31
T_min = 0.899, T_max = 0.990	l = −5→6
5871 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0396P)²] where P = (F_o² + 2F_c²)/3
1578 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₇H₆N₆	V = 1619.4 (18) Å³
M_r = 174.16	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 12.298 (5) Å	µ = 0.10 mm⁻¹
b = 25.896 (5) Å	T = 200 K
c = 5.085 (5) Å	0.29 × 0.14 × 0.13 mm

Data collection top

Oxford Xcalibur3 CCD area-detector diffractometer	1578 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	956 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.990	R_int = 0.040
5871 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.11 e Å⁻³
1578 reflections	Δρ_min = −0.12 e Å⁻³
143 parameters

Special details top

Refinement. Aromatic H atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C–H = 0.95 (C_aromH) and with U_iso(H) = kU_eq(carrier atom), where k = 1.2 for CH. The H atoms attached to methyl C7 are disordered over two sites. These were freely refined; the occupancy of the major disorder component is 0.69 (5). The highest peak and deepest hole in the final difference map were located 0.93 Å from atom H7B and 0.32 Å from atom H7A, respectively.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.45618 (11)	0.14719 (5)	0.0665 (3)	0.0348 (4)
C2	0.45326 (12)	0.10499 (5)	−0.1031 (3)	0.0353 (4)
C3	0.53072 (12)	0.06637 (6)	−0.0938 (3)	0.0415 (4)
H3	0.5271	0.0383	−0.2136	0.050*
C4	0.61302 (13)	0.06857 (6)	0.0888 (3)	0.0426 (4)
H4	0.6662	0.0420	0.0957	0.051*
C5	0.61819 (12)	0.10957 (5)	0.2622 (3)	0.0405 (4)
H5	0.6745	0.1111	0.3899	0.049*
C6	0.54110 (12)	0.14841 (5)	0.2495 (3)	0.0353 (4)
C7	0.37338 (17)	0.18935 (8)	0.0524 (5)	0.0462 (4)
H7A	0.297 (2)	0.1729 (9)	0.075 (5)	0.042 (10)*	0.69 (5)
H7B	0.385 (3)	0.2132 (11)	0.190 (8)	0.073 (11)*	0.69 (5)
H7C	0.381 (3)	0.2054 (10)	−0.129 (7)	0.060 (11)*	0.69 (5)
H7D	0.323 (4)	0.1895 (16)	−0.102 (10)	0.010 (16)*	0.31 (5)
H7E	0.334 (4)	0.193 (2)	0.231 (14)	0.04 (2)*	0.31 (5)
H7F	0.410 (4)	0.2239 (18)	0.031 (10)	0.015 (18)*	0.31 (5)
N1	0.36418 (10)	0.10504 (5)	−0.2837 (2)	0.0440 (4)
N2	0.35797 (10)	0.06789 (5)	−0.4371 (3)	0.0419 (3)
N3	0.34235 (11)	0.03628 (5)	−0.5865 (3)	0.0564 (4)
N4	0.54156 (10)	0.19271 (4)	0.4164 (3)	0.0440 (3)
N5	0.61378 (11)	0.19404 (4)	0.5897 (3)	0.0409 (3)
N6	0.67279 (12)	0.19998 (5)	0.7553 (3)	0.0528 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0329 (8)	0.0333 (8)	0.0382 (9)	−0.0034 (8)	0.0065 (8)	0.0026 (8)
C2	0.0346 (9)	0.0381 (8)	0.0332 (9)	−0.0052 (8)	0.0037 (8)	0.0030 (8)
C3	0.0440 (9)	0.0367 (8)	0.0436 (10)	0.0011 (9)	0.0053 (9)	−0.0017 (8)
C4	0.0415 (9)	0.0384 (8)	0.0480 (10)	0.0065 (9)	0.0043 (10)	0.0052 (9)
C5	0.0379 (9)	0.0444 (9)	0.0393 (9)	−0.0016 (9)	−0.0016 (9)	0.0050 (8)
C6	0.0367 (9)	0.0352 (8)	0.0340 (8)	−0.0039 (8)	0.0038 (8)	0.0013 (8)
C7	0.0428 (11)	0.0422 (10)	0.0537 (13)	0.0029 (11)	−0.0036 (12)	−0.0064 (12)
N1	0.0455 (8)	0.0406 (7)	0.0460 (8)	−0.0019 (7)	−0.0033 (7)	−0.0088 (7)
N2	0.0408 (8)	0.0462 (8)	0.0387 (8)	−0.0031 (8)	−0.0005 (7)	0.0000 (8)
N3	0.0611 (9)	0.0572 (9)	0.0510 (9)	−0.0003 (8)	−0.0051 (8)	−0.0148 (8)
N4	0.0455 (8)	0.0477 (8)	0.0388 (8)	−0.0006 (7)	−0.0065 (8)	−0.0063 (7)
N5	0.0455 (8)	0.0416 (8)	0.0357 (8)	−0.0052 (7)	0.0065 (8)	0.0007 (7)
N6	0.0545 (8)	0.0650 (10)	0.0389 (9)	−0.0080 (8)	−0.0047 (8)	−0.0028 (7)

Geometric parameters (Å, º) top

C1—C2	1.393 (2)	C6—N4	1.4270 (19)
C1—C6	1.399 (2)	C7—H7A	1.04 (3)
C1—C7	1.495 (2)	C7—H7B	0.94 (3)
C2—C3	1.382 (2)	C7—H7C	1.02 (3)
C2—N1	1.4294 (19)	C7—H7D	1.00 (5)
C3—C4	1.375 (2)	C7—H7E	1.04 (7)
C3—H3	0.9500	C7—H7F	1.01 (5)
C4—C5	1.382 (2)	N1—N2	1.2410 (17)
C4—H4	0.9500	N2—N3	1.1331 (17)
C5—C6	1.3836 (19)	N4—N5	1.2518 (19)
C5—H5	0.9500	N5—N6	1.1222 (17)

C2—C1—C6	116.67 (13)	H7A—C7—H7C	111 (2)
C2—C1—C7	121.72 (16)	H7B—C7—H7C	113 (2)
C6—C1—C7	121.60 (15)	C1—C7—H7D	118 (2)
C3—C2—C1	121.93 (15)	H7A—C7—H7D	62 (2)
C3—C2—N1	123.42 (13)	H7B—C7—H7D	132 (3)
C1—C2—N1	114.65 (14)	H7C—C7—H7D	49 (2)
C4—C3—C2	120.03 (15)	C1—C7—H7E	110 (2)
C4—C3—H3	120.0	H7A—C7—H7E	61 (3)
C2—C3—H3	120.0	H7B—C7—H7E	50 (3)
C3—C4—C5	119.80 (15)	H7C—C7—H7E	143 (3)
C3—C4—H4	120.1	H7D—C7—H7E	113 (3)
C5—C4—H4	120.1	C1—C7—H7F	110 (2)
C4—C5—C6	119.80 (14)	H7A—C7—H7F	141 (2)
C4—C5—H5	120.1	H7B—C7—H7F	55 (2)
C6—C5—H5	120.1	H7C—C7—H7F	60 (2)
C5—C6—C1	121.76 (13)	H7D—C7—H7F	101 (3)
C5—C6—N4	123.63 (14)	H7E—C7—H7F	103 (3)
C1—C6—N4	114.61 (13)	N2—N1—C2	116.77 (13)
C1—C7—H7A	108.3 (11)	N3—N2—N1	172.70 (16)
C1—C7—H7B	109.8 (17)	N5—N4—C6	116.34 (13)
H7A—C7—H7B	109 (3)	N6—N5—N4	172.29 (15)
C1—C7—H7C	106.0 (15)

C6—C1—C2—C3	−0.6 (2)	C4—C5—C6—N4	−178.50 (14)
C7—C1—C2—C3	178.86 (16)	C2—C1—C6—C5	−0.2 (2)
C6—C1—C2—N1	179.09 (12)	C7—C1—C6—C5	−179.69 (16)
C7—C1—C2—N1	−1.5 (2)	C2—C1—C6—N4	179.16 (13)
C1—C2—C3—C4	0.8 (2)	C7—C1—C6—N4	−0.3 (2)
N1—C2—C3—C4	−178.84 (13)	C3—C2—N1—N2	0.2 (2)
C2—C3—C4—C5	−0.2 (2)	C1—C2—N1—N2	−179.43 (13)
C3—C4—C5—C6	−0.6 (2)	C5—C6—N4—N5	−3.5 (2)
C4—C5—C6—C1	0.8 (2)	C1—C6—N4—N5	177.14 (13)

Experimental details

Crystal data
Chemical formula	C₇H₆N₆
M_r	174.16
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	200
a, b, c (Å)	12.298 (5), 25.896 (5), 5.085 (5)
V (Å³)	1619.4 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.29 × 0.14 × 0.13

Data collection
Diffractometer	Oxford Xcalibur3 CCD area-detector diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.899, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	5871, 1578, 956
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.061, 0.94
No. of reflections	1578
No. of parameters	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.12

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction,2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1996).

Acknowledgements

The University of Munich, the Fonds der Chemischen Industrie, and the Deutsche Forschungsgemeinschaft (KL 636/10–1) are gratefully acknowledged for financial support.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. (1996). DIAMOND. University of Bonn, Germany. Google Scholar
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Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
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