Acta Cryst. (2008). E64, o348 [ doi:10.1107/S160053680706744X ]
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.
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..
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).
![[Figure 1]](./fj2092fig1thm.gif)
| 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. |
| C7H6N6 | F000 = 720 |
| Mr = 174.16 | Dx = 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 = 3.9–30.0º |
| b = 25.896 (5) Å | µ = 0.10 mm−1 |
| c = 5.085 (5) Å | T = 200 (2) K |
| V = 1619.4 (18) Å3 | Needle, colorless |
| Z = 8 | 0.29 × 0.14 × 0.13 mm |
| Oxford Xcalibur3 CCD area-detector diffractometer | 1578 independent reflections |
| Radiation source: fine-focus sealed tube | 956 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.040 |
| Detector resolution: 15.9809 pixels mm-1 | θmax = 26.0º |
| T = 200(2) K | θmin = 4.3º |
| ω scans | h = −15→9 |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | k = −19→31 |
| Tmin = 0.899, Tmax = 0.990 | l = −5→6 |
| 5871 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.030 | H 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 reflections | Δρmax = 0.11 e Å−3 |
| 143 parameters | Δρmin = −0.11 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C7H6N6 | V = 1619.4 (18) Å3 |
| Mr = 174.16 | Z = 8 |
| Orthorhombic, Pccn | Mo Kα |
| a = 12.298 (5) Å | µ = 0.10 mm−1 |
| b = 25.896 (5) Å | T = 200 (2) K |
| c = 5.085 (5) Å | 0.29 × 0.14 × 0.13 mm |
| Oxford Xcalibur3 CCD area-detector diffractometer | 1578 independent reflections |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 956 reflections with I > 2σ(I) |
| Tmin = 0.899, Tmax = 0.990 | Rint = 0.040 |
| 5871 measured reflections |
| R[F2 > 2σ(F2)] = 0.030 | 143 parameters |
| wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.94 | Δρmax = 0.11 e Å−3 |
| 1578 reflections | Δρmin = −0.11 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | 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) |
| 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) |
| 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) |
The University of Munich, the Fonds der Chemischen Industrie, and the Deutsche Forschungsgemeinschaft (KL 636/10–1) are gratefully acknowledged for financial support.
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.
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.
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)°].