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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o348.
Published online 2008 January 4. doi:  10.1107/S160053680706744X
PMCID: PMC2960355

2,6-Diazido­toluene

Abstract

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 [triangle]). For the comparable compound, 2-azido­benzyl ­bromide, see: Klapötke et al. (2003 [triangle]).

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Object name is e-64-0o348-scheme1.jpg

Experimental

Crystal data

  • C7H6N6
  • M r = 174.16
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o348-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.061
  • S = 0.94
  • 1578 reflections
  • 143 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.10 e Å−3
  • Δρmin = −0.12 e Å−3

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

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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 Nα–Nβ distances [N1–N2 1.241 (2) and N4–N5 1.253 (2) Å] and shorter terminal Nβ–Nγ 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)°].

Experimental

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, 3JH–H = 8.1 Hz, 6JH—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 (Nβ), -149.0 (Nγ), -291.4 (Nα) p.p.m..

Figures

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.

Crystal data

C7H6N6F000 = 720
Mr = 174.16Dx = 1.429 (1) Mg m3
Orthorhombic, PccnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 1382 reflections
a = 12.298 (5) Åθ = 3.9–30.0º
b = 25.896 (5) ŵ = 0.10 mm1
c = 5.085 (5) ÅT = 200 (2) K
V = 1619.4 (18) Å3Needle, colorless
Z = 80.29 × 0.14 × 0.13 mm

Data collection

Oxford Xcalibur3 CCD area-detector diffractometer1578 independent reflections
Radiation source: fine-focus sealed tube956 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
Detector resolution: 15.9809 pixels mm-1θmax = 26.0º
T = 200(2) Kθmin = 4.3º
ω scansh = −15→9
Absorption correction: multi-scan(CrysAlis RED; Oxford Diffraction, 2007)k = −19→31
Tmin = 0.899, Tmax = 0.990l = −5→6
5871 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061  w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
1578 reflectionsΔρmax = 0.11 e Å3
143 parametersΔρmin = −0.11 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Refinement. Aromatic H atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C–H = 0.95 (CaromH) and with Uiso(H) = kUeq(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)

xyzUiso*/UeqOcc. (<1)
C10.45618 (11)0.14719 (5)0.0665 (3)0.0348 (4)
C20.45326 (12)0.10499 (5)−0.1031 (3)0.0353 (4)
C30.53072 (12)0.06637 (6)−0.0938 (3)0.0415 (4)
H30.52710.0383−0.21360.050*
C40.61302 (13)0.06857 (6)0.0888 (3)0.0426 (4)
H40.66620.04200.09570.051*
C50.61819 (12)0.10957 (5)0.2622 (3)0.0405 (4)
H50.67450.11110.38990.049*
C60.54110 (12)0.14841 (5)0.2495 (3)0.0353 (4)
C70.37338 (17)0.18935 (8)0.0524 (5)0.0462 (4)
H7A0.297 (2)0.1729 (9)0.075 (5)0.042 (10)*0.69 (5)
H7B0.385 (3)0.2132 (11)0.190 (8)0.073 (11)*0.69 (5)
H7C0.381 (3)0.2054 (10)−0.129 (7)0.060 (11)*0.69 (5)
H7D0.323 (4)0.1895 (16)−0.102 (10)0.010 (16)*0.31 (5)
H7E0.334 (4)0.193 (2)0.231 (14)0.04 (2)*0.31 (5)
H7F0.410 (4)0.2239 (18)0.031 (10)0.015 (18)*0.31 (5)
N10.36418 (10)0.10504 (5)−0.2837 (2)0.0440 (4)
N20.35797 (10)0.06789 (5)−0.4371 (3)0.0419 (3)
N30.34235 (11)0.03628 (5)−0.5865 (3)0.0564 (4)
N40.54156 (10)0.19271 (4)0.4164 (3)0.0440 (3)
N50.61378 (11)0.19404 (4)0.5897 (3)0.0409 (3)
N60.67279 (12)0.19998 (5)0.7553 (3)0.0528 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0329 (8)0.0333 (8)0.0382 (9)−0.0034 (8)0.0065 (8)0.0026 (8)
C20.0346 (9)0.0381 (8)0.0332 (9)−0.0052 (8)0.0037 (8)0.0030 (8)
C30.0440 (9)0.0367 (8)0.0436 (10)0.0011 (9)0.0053 (9)−0.0017 (8)
C40.0415 (9)0.0384 (8)0.0480 (10)0.0065 (9)0.0043 (10)0.0052 (9)
C50.0379 (9)0.0444 (9)0.0393 (9)−0.0016 (9)−0.0016 (9)0.0050 (8)
C60.0367 (9)0.0352 (8)0.0340 (8)−0.0039 (8)0.0038 (8)0.0013 (8)
C70.0428 (11)0.0422 (10)0.0537 (13)0.0029 (11)−0.0036 (12)−0.0064 (12)
N10.0455 (8)0.0406 (7)0.0460 (8)−0.0019 (7)−0.0033 (7)−0.0088 (7)
N20.0408 (8)0.0462 (8)0.0387 (8)−0.0031 (8)−0.0005 (7)0.0000 (8)
N30.0611 (9)0.0572 (9)0.0510 (9)−0.0003 (8)−0.0051 (8)−0.0148 (8)
N40.0455 (8)0.0477 (8)0.0388 (8)−0.0006 (7)−0.0065 (8)−0.0063 (7)
N50.0455 (8)0.0416 (8)0.0357 (8)−0.0052 (7)0.0065 (8)0.0007 (7)
N60.0545 (8)0.0650 (10)0.0389 (9)−0.0080 (8)−0.0047 (8)−0.0028 (7)

Geometric parameters (Å, °)

C1—C21.393 (2)C6—N41.4270 (19)
C1—C61.399 (2)C7—H7A1.04 (3)
C1—C71.495 (2)C7—H7B0.94 (3)
C2—C31.382 (2)C7—H7C1.02 (3)
C2—N11.4294 (19)C7—H7D1.00 (5)
C3—C41.375 (2)C7—H7E1.04 (7)
C3—H30.9500C7—H7F1.01 (5)
C4—C51.382 (2)N1—N21.2410 (17)
C4—H40.9500N2—N31.1331 (17)
C5—C61.3836 (19)N4—N51.2518 (19)
C5—H50.9500N5—N61.1222 (17)
C2—C1—C6116.67 (13)H7A—C7—H7C111 (2)
C2—C1—C7121.72 (16)H7B—C7—H7C113 (2)
C6—C1—C7121.60 (15)C1—C7—H7D118 (2)
C3—C2—C1121.93 (15)H7A—C7—H7D62 (2)
C3—C2—N1123.42 (13)H7B—C7—H7D132 (3)
C1—C2—N1114.65 (14)H7C—C7—H7D49 (2)
C4—C3—C2120.03 (15)C1—C7—H7E110 (2)
C4—C3—H3120.0H7A—C7—H7E61 (3)
C2—C3—H3120.0H7B—C7—H7E50 (3)
C3—C4—C5119.80 (15)H7C—C7—H7E143 (3)
C3—C4—H4120.1H7D—C7—H7E113 (3)
C5—C4—H4120.1C1—C7—H7F110 (2)
C4—C5—C6119.80 (14)H7A—C7—H7F141 (2)
C4—C5—H5120.1H7B—C7—H7F55 (2)
C6—C5—H5120.1H7C—C7—H7F60 (2)
C5—C6—C1121.76 (13)H7D—C7—H7F101 (3)
C5—C6—N4123.63 (14)H7E—C7—H7F103 (3)
C1—C6—N4114.61 (13)N2—N1—C2116.77 (13)
C1—C7—H7A108.3 (11)N3—N2—N1172.70 (16)
C1—C7—H7B109.8 (17)N5—N4—C6116.34 (13)
H7A—C7—H7B109 (3)N6—N5—N4172.29 (15)
C1—C7—H7C106.0 (15)
C6—C1—C2—C3−0.6 (2)C4—C5—C6—N4−178.50 (14)
C7—C1—C2—C3178.86 (16)C2—C1—C6—C5−0.2 (2)
C6—C1—C2—N1179.09 (12)C7—C1—C6—C5−179.69 (16)
C7—C1—C2—N1−1.5 (2)C2—C1—C6—N4179.16 (13)
C1—C2—C3—C40.8 (2)C7—C1—C6—N4−0.3 (2)
N1—C2—C3—C4−178.84 (13)C3—C2—N1—N20.2 (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—C10.8 (2)C1—C6—N4—N5177.14 (13)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2092).

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.
  • Brandenburg, K. (1996). DIAMOND University of Bonn, Germany.
  • Chapyshev, S. V. & Tomioka, H. (2003). Bull. Chem. Soc. Jpn, 76, 2075–2089.
  • Klapötke, T. M., Krumm, B., Piotrowski, H., Polborn, K. & Holl, G. (2003). Chem. Eur. J.9, 687–694. [PubMed]
  • Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography