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access2-(1H-Benzotriazol-1-yl)acetohydrazide
aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China
*Correspondence e-mail: kobeecho@163.com
The title compound, C8H9N5O, was synthesized by the reaction of ethyl 2-(benzotriazol-1-yl)acetate with hydrazine hydrate in ethanol. In the amide group, the C—N bond is relatively short [1.3283 (16) Å], suggesting some degree of electronic delocalization in the molecule. In the molecules are linked into infinite chains along the a axis by intermolecular O—H⋯N hydrogen bonding.
Related literature
For general background to multiple-hydrogen-bonding N-heterocyclic systems as potential supramolecular reagents, see: Portalone (2007![[Portalone, G. (2007). Acta Cryst. E63, o3232.]](../../../../../../logos/arrows/e_arr.gif "Portalone, G. (2007). Acta Cryst. E63, o3232.")
); Portalone & Colapietro (2007, 2008); For related structures, see: Shi et al. (2007a,b); Ji et al. (2008); For bond-length data, see: Allen et al. (1987).
![[Scheme 1]](bg2267scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536809021199/bg2267sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809021199/bg2267Isup2.hkl
The title compound was synthesized by the reaction of benzotriazol-1-yl-acetic acid ethyl ester(1 mmol) with hydrazine hydrate 85% (1.1 mmol)in ethanol (20 ml) under reflux conditions (348 K) for 24 h. The solvent was removed and the solid product recrystallized from tetrahydrofuran. After four days colorless crystals suitable for X-ray diffraction study were obtained.
All H atoms were placed in idealized positions (C—H = 0.93— 0.97 Å, N—H = 0.86 Å) and refined as riding atoms. For those bound to C, Uiso(H) = 1.2 or 1.5Ueq(C). while for those bound to N, Uiso(H) = 1.2 Ueq(N).
Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bg2267fig1thm.gif) | Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. |
![[Figure 2]](./bg2267fig2thm.gif) | Fig. 2. The structure of the infinite chains formed via hydrogen bonds, H atoms have been omitted for clarity. The dashed lines indicate hydrogen bonds. |
| C8H9N5O | F(000) = 400 |
| Mr = 191.20 | Dx = 1.459 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2593 reflections |
| a = 5.1434 (9) Å | θ = 2.4–28.0° |
| b = 6.5885 (12) Å | µ = 0.11 mm−1 |
| c = 25.754 (5) Å | T = 295 K |
| β = 94.227 (3)° | Block, colorless |
| V = 870.4 (3) Å3 | 0.12 × 0.10 × 0.06 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 1528 independent reflections |
| Radiation source: fine-focus sealed tube | 1364 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.015 |
| ϕ and ω scans | θmax = 25.1°, θmin = 3.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −4→6 |
| Tmin = 0.988, Tmax = 0.994 | k = −7→7 |
| 4367 measured reflections | l = −28→30 |
| 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) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0333P)2 + 0.233P] where P = (Fo2 + 2Fc2)/3 |
| 1528 reflections | (Δ/σ)max < 0.001 |
| 135 parameters | Δρmax = 0.13 e Å−3 |
| 0 restraints | Δρmin = −0.15 e Å−3 |
| C8H9N5O | V = 870.4 (3) Å3 |
| Mr = 191.20 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.1434 (9) Å | µ = 0.11 mm−1 |
| b = 6.5885 (12) Å | T = 295 K |
| c = 25.754 (5) Å | 0.12 × 0.10 × 0.06 mm |
| β = 94.227 (3)° |
| Bruker APEXII CCD area-detector diffractometer | 1528 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1364 reflections with I > 2σ(I) |
| Tmin = 0.988, Tmax = 0.994 | Rint = 0.015 |
| 4367 measured reflections |
| R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
| wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.13 e Å−3 |
| 1528 reflections | Δρmin = −0.15 e Å−3 |
| 135 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 1.08675 (16) | 0.24854 (14) | 0.01128 (4) | 0.0432 (3) | |
| N1 | 1.3431 (2) | 0.14371 (19) | 0.16751 (5) | 0.0505 (3) | |
| N2 | 1.2038 (2) | 0.05513 (19) | 0.12958 (5) | 0.0496 (3) | |
| N3 | 0.9953 (2) | 0.17411 (18) | 0.11547 (4) | 0.0422 (3) | |
| N4 | 0.65313 (19) | 0.25384 (17) | −0.00905 (4) | 0.0419 (3) | |
| H1 | 0.5024 | 0.2240 | 0.0012 | 0.050* | |
| N5 | 0.6667 (2) | 0.3428 (2) | −0.05866 (5) | 0.0503 (3) | |
| C1 | 1.2246 (2) | 0.3253 (2) | 0.17817 (5) | 0.0406 (3) | |
| C2 | 1.2914 (3) | 0.4759 (2) | 0.21540 (5) | 0.0496 (4) | |
| H2 | 1.4385 | 0.4637 | 0.2384 | 0.060* | |
| C3 | 1.1312 (3) | 0.6408 (2) | 0.21632 (6) | 0.0537 (4) | |
| H3 | 1.1698 | 0.7424 | 0.2407 | 0.064* | |
| C4 | 0.9094 (3) | 0.6612 (2) | 0.18138 (6) | 0.0534 (4) | |
| H4 | 0.8067 | 0.7768 | 0.1832 | 0.064* | |
| C5 | 0.8397 (3) | 0.5166 (2) | 0.14492 (5) | 0.0466 (3) | |
| H5 | 0.6933 | 0.5306 | 0.1218 | 0.056* | |
| C6 | 1.0018 (2) | 0.3468 (2) | 0.14460 (5) | 0.0377 (3) | |
| C7 | 0.8079 (3) | 0.1139 (2) | 0.07360 (5) | 0.0460 (3) | |
| H7A | 0.6341 | 0.1507 | 0.0825 | 0.055* | |
| H7B | 0.8133 | −0.0323 | 0.0695 | 0.055* | |
| C8 | 0.8630 (2) | 0.21429 (19) | 0.02251 (5) | 0.0356 (3) | |
| H9 | 0.723 (3) | 0.250 (2) | −0.0799 (6) | 0.073 (6)* | |
| H8 | 0.785 (3) | 0.441 (2) | −0.0551 (8) | 0.078 (6)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0277 (5) | 0.0555 (6) | 0.0466 (5) | −0.0038 (4) | 0.0045 (4) | −0.0023 (4) |
| N1 | 0.0450 (7) | 0.0599 (8) | 0.0460 (7) | 0.0030 (6) | −0.0010 (5) | 0.0029 (6) |
| N2 | 0.0472 (7) | 0.0518 (7) | 0.0500 (7) | 0.0030 (6) | 0.0051 (5) | 0.0005 (6) |
| N3 | 0.0399 (6) | 0.0508 (7) | 0.0358 (6) | −0.0038 (5) | 0.0024 (5) | −0.0031 (5) |
| N4 | 0.0272 (5) | 0.0526 (7) | 0.0457 (6) | −0.0030 (5) | 0.0021 (4) | −0.0043 (5) |
| N5 | 0.0434 (7) | 0.0582 (8) | 0.0483 (7) | 0.0013 (6) | −0.0040 (6) | 0.0003 (6) |
| C1 | 0.0351 (7) | 0.0530 (8) | 0.0342 (7) | −0.0047 (6) | 0.0054 (5) | 0.0039 (6) |
| C2 | 0.0394 (7) | 0.0720 (10) | 0.0372 (7) | −0.0136 (7) | 0.0009 (6) | −0.0029 (7) |
| C3 | 0.0515 (9) | 0.0611 (10) | 0.0497 (9) | −0.0159 (7) | 0.0114 (7) | −0.0143 (7) |
| C4 | 0.0499 (9) | 0.0521 (9) | 0.0598 (9) | −0.0013 (7) | 0.0145 (7) | −0.0043 (7) |
| C5 | 0.0382 (7) | 0.0574 (9) | 0.0441 (8) | −0.0003 (6) | 0.0025 (6) | 0.0020 (7) |
| C6 | 0.0346 (7) | 0.0484 (8) | 0.0303 (6) | −0.0061 (6) | 0.0053 (5) | 0.0010 (6) |
| C7 | 0.0387 (7) | 0.0582 (9) | 0.0412 (7) | −0.0125 (6) | 0.0044 (6) | −0.0072 (6) |
| C8 | 0.0292 (6) | 0.0384 (7) | 0.0392 (7) | −0.0035 (5) | 0.0027 (5) | −0.0110 (5) |
| O1—C8 | 1.2280 (14) | C1—C2 | 1.405 (2) |
| N1—N2 | 1.3057 (16) | C2—C3 | 1.365 (2) |
| N1—C1 | 1.3795 (19) | C2—H2 | 0.9300 |
| N2—N3 | 1.3559 (16) | C3—C4 | 1.407 (2) |
| N3—C6 | 1.3620 (17) | C3—H3 | 0.9300 |
| N3—C7 | 1.4478 (16) | C4—C5 | 1.367 (2) |
| N4—C8 | 1.3283 (16) | C4—H4 | 0.9300 |
| N4—N5 | 1.4120 (17) | C5—C6 | 1.3957 (19) |
| N4—H1 | 0.8600 | C5—H5 | 0.9300 |
| N5—H9 | 0.884 (9) | C7—C8 | 1.5179 (18) |
| N5—H8 | 0.888 (9) | C7—H7A | 0.9700 |
| C1—C6 | 1.3909 (18) | C7—H7B | 0.9700 |
| N2—N1—C1 | 108.09 (11) | C4—C3—H3 | 119.1 |
| N1—N2—N3 | 108.75 (11) | C5—C4—C3 | 122.15 (14) |
| N2—N3—C6 | 110.41 (10) | C5—C4—H4 | 118.9 |
| N2—N3—C7 | 120.74 (12) | C3—C4—H4 | 118.9 |
| C6—N3—C7 | 128.83 (12) | C4—C5—C6 | 115.87 (13) |
| C8—N4—N5 | 122.88 (10) | C4—C5—H5 | 122.1 |
| C8—N4—H1 | 118.6 | C6—C5—H5 | 122.1 |
| N5—N4—H1 | 118.6 | N3—C6—C1 | 104.05 (11) |
| N4—N5—H9 | 108.2 (12) | N3—C6—C5 | 133.05 (12) |
| N4—N5—H8 | 106.8 (13) | C1—C6—C5 | 122.90 (12) |
| H9—N5—H8 | 108.4 (17) | N3—C7—C8 | 111.69 (10) |
| N1—C1—C6 | 108.69 (12) | N3—C7—H7A | 109.3 |
| N1—C1—C2 | 131.22 (13) | C8—C7—H7A | 109.3 |
| C6—C1—C2 | 120.08 (13) | N3—C7—H7B | 109.3 |
| C3—C2—C1 | 117.16 (13) | C8—C7—H7B | 109.3 |
| C3—C2—H2 | 121.4 | H7A—C7—H7B | 107.9 |
| C1—C2—H2 | 121.4 | O1—C8—N4 | 123.60 (12) |
| C2—C3—C4 | 121.83 (14) | O1—C8—C7 | 121.49 (11) |
| C2—C3—H3 | 119.1 | N4—C8—C7 | 114.87 (10) |
| C1—N1—N2—N3 | −0.50 (14) | C7—N3—C6—C5 | 0.5 (2) |
| N1—N2—N3—C6 | 0.98 (15) | N1—C1—C6—N3 | 0.71 (13) |
| N1—N2—N3—C7 | 179.30 (11) | C2—C1—C6—N3 | −178.58 (12) |
| N2—N1—C1—C6 | −0.15 (14) | N1—C1—C6—C5 | −179.03 (12) |
| N2—N1—C1—C2 | 179.04 (14) | C2—C1—C6—C5 | 1.68 (19) |
| N1—C1—C2—C3 | −179.77 (14) | C4—C5—C6—N3 | 178.92 (13) |
| C6—C1—C2—C3 | −0.66 (19) | C4—C5—C6—C1 | −1.43 (19) |
| C1—C2—C3—C4 | −0.5 (2) | N2—N3—C7—C8 | −97.25 (14) |
| C2—C3—C4—C5 | 0.7 (2) | C6—N3—C7—C8 | 80.72 (16) |
| C3—C4—C5—C6 | 0.2 (2) | N5—N4—C8—O1 | −1.0 (2) |
| N2—N3—C6—C1 | −1.02 (13) | N5—N4—C8—C7 | −178.60 (12) |
| C7—N3—C6—C1 | −179.17 (12) | N3—C7—C8—O1 | 34.61 (18) |
| N2—N3—C6—C5 | 178.67 (14) | N3—C7—C8—N4 | −147.76 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H1···O1i | 0.86 | 2.18 | 2.9977 (14) | 159 |
| Symmetry code: (i) x−1, y, z. |
Experimental details
| Crystal data | |
| Chemical formula | C8H9N5O |
| Mr | 191.20 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 295 |
| a, b, c (Å) | 5.1434 (9), 6.5885 (12), 25.754 (5) |
| β (°) | 94.227 (3) |
| V (Å3) | 870.4 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.11 |
| Crystal size (mm) | 0.12 × 0.10 × 0.06 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
| Tmin, Tmax | 0.988, 0.994 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4367, 1528, 1364 |
| Rint | 0.015 |
| (sin θ/λ)max (Å−1) | 0.596 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.04 |
| No. of reflections | 1528 |
| No. of parameters | 135 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.15 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H1···O1i | 0.86 | 2.18 | 2.9977 (14) | 159.1 |
| Symmetry code: (i) x−1, y, z. |
Acknowledgements
This project was supported by the Postgraduate Foundation of Taishan University (grant No. Y04–2–08).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ji, N.-N. & Shi, Z.-Q. (2008). Acta Cryst. E64, o655. Web of Science CrossRef IUCr Journals Google Scholar
Portalone, G. (2007). Acta Cryst. E63, o3232. Web of Science CSD CrossRef IUCr Journals Google Scholar
Portalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655–o658. Web of Science CSD CrossRef IUCr Journals Google Scholar
Portalone, G. & Colapietro, M. (2008). Acta Cryst. E64, o304. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Shi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007a). Acta Cryst. E63, o4561. Web of Science CSD CrossRef IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
In our previous papers(Shi et al., 2007a; Shi et al., 2007b; Ji et al., 2008;), we have reported a number of Schiff-bases by the reaction of benzotriazol-1-yl-acetic acid hydrazide with relevant aldehyde or ketone. As a part of a more general study of multiple-hydrogen-bonding N-heterocyclic systems as potential supramolecular reagents (Portalone, 2007; Portalone & Colapietro, 2007, 2008), the title compound, (I), was synthesized and its crystal structure determined. The asymmetric unit of the (I) comprises one independent molecule. In (I) (Fig. 1), the bond lengths and angles are in good agreement with the expected values (Allen et al., 1987). In the crystal structure (Fig. 2), the molecules are linked into infinite chains by O—H···N hydrogen bond.