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

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ISSN: 2056-9890

2-(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

(Received 29 May 2009; accepted 4 June 2009; online 10 June 2009)

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 crystal structure, 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.]); Portalone & Colapietro (2007[Portalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655-o658.], 2008[Portalone, G. & Colapietro, M. (2008). Acta Cryst. E64, o304.]); For related structures, see: Shi et al. (2007a[Shi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007a). Acta Cryst. E63, o4561.],b[Shi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007b). Acta Cryst. E63, o4642.]); Ji et al. (2008[Ji, N.-N. & Shi, Z.-Q. (2008). Acta Cryst. E64, o655.]); For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C8H9N5O

  • Mr = 191.20

  • Monoclinic, P 21 /c

  • a = 5.1434 (9) Å

  • b = 6.5885 (12) Å

  • c = 25.754 (5) Å

  • β = 94.227 (3)°

  • V = 870.4 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 295 K

  • 0.12 × 0.10 × 0.06 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.988, Tmax = 0.994

  • 4367 measured reflections

  • 1528 independent reflections

  • 1364 reflections with I > 2σ(I)

  • Rint = 0.015

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.079

  • S = 1.04

  • 1528 reflections

  • 135 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.13 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N4—H1⋯O1i 0.86 2.18 2.9977 (14) 159
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

For general background to multiple-hydrogen-bonding N-heterocyclic systems as potential supramolecular reagents, see: Portalone (2007); 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)

Experimental top

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.

Refinement top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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.
2-(1H-Benzotriazol-1-yl)acetohydrazide top
Crystal data top
C8H9N5OF(000) = 400
Mr = 191.20Dx = 1.459 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2593 reflections
a = 5.1434 (9) Åθ = 2.4–28.0°
b = 6.5885 (12) ŵ = 0.11 mm1
c = 25.754 (5) ÅT = 295 K
β = 94.227 (3)°Block, colorless
V = 870.4 (3) Å30.12 × 0.10 × 0.06 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1528 independent reflections
Radiation source: fine-focus sealed tube1364 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ϕ and ω scansθmax = 25.1°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 46
Tmin = 0.988, Tmax = 0.994k = 77
4367 measured reflectionsl = 2830
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H 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 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C8H9N5OV = 870.4 (3) Å3
Mr = 191.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.1434 (9) ŵ = 0.11 mm1
b = 6.5885 (12) ÅT = 295 K
c = 25.754 (5) Å0.12 × 0.10 × 0.06 mm
β = 94.227 (3)°
Data collection top
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 = 0.994Rint = 0.015
4367 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.13 e Å3
1528 reflectionsΔρmin = 0.15 e Å3
135 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.08675 (16)0.24854 (14)0.01128 (4)0.0432 (3)
N11.3431 (2)0.14371 (19)0.16751 (5)0.0505 (3)
N21.2038 (2)0.05513 (19)0.12958 (5)0.0496 (3)
N30.9953 (2)0.17411 (18)0.11547 (4)0.0422 (3)
N40.65313 (19)0.25384 (17)0.00905 (4)0.0419 (3)
H10.50240.22400.00120.050*
N50.6667 (2)0.3428 (2)0.05866 (5)0.0503 (3)
C11.2246 (2)0.3253 (2)0.17817 (5)0.0406 (3)
C21.2914 (3)0.4759 (2)0.21540 (5)0.0496 (4)
H21.43850.46370.23840.060*
C31.1312 (3)0.6408 (2)0.21632 (6)0.0537 (4)
H31.16980.74240.24070.064*
C40.9094 (3)0.6612 (2)0.18138 (6)0.0534 (4)
H40.80670.77680.18320.064*
C50.8397 (3)0.5166 (2)0.14492 (5)0.0466 (3)
H50.69330.53060.12180.056*
C61.0018 (2)0.3468 (2)0.14460 (5)0.0377 (3)
C70.8079 (3)0.1139 (2)0.07360 (5)0.0460 (3)
H7A0.63410.15070.08250.055*
H7B0.81330.03230.06950.055*
C80.8630 (2)0.21429 (19)0.02251 (5)0.0356 (3)
H90.723 (3)0.250 (2)0.0799 (6)0.073 (6)*
H80.785 (3)0.441 (2)0.0551 (8)0.078 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0277 (5)0.0555 (6)0.0466 (5)0.0038 (4)0.0045 (4)0.0023 (4)
N10.0450 (7)0.0599 (8)0.0460 (7)0.0030 (6)0.0010 (5)0.0029 (6)
N20.0472 (7)0.0518 (7)0.0500 (7)0.0030 (6)0.0051 (5)0.0005 (6)
N30.0399 (6)0.0508 (7)0.0358 (6)0.0038 (5)0.0024 (5)0.0031 (5)
N40.0272 (5)0.0526 (7)0.0457 (6)0.0030 (5)0.0021 (4)0.0043 (5)
N50.0434 (7)0.0582 (8)0.0483 (7)0.0013 (6)0.0040 (6)0.0003 (6)
C10.0351 (7)0.0530 (8)0.0342 (7)0.0047 (6)0.0054 (5)0.0039 (6)
C20.0394 (7)0.0720 (10)0.0372 (7)0.0136 (7)0.0009 (6)0.0029 (7)
C30.0515 (9)0.0611 (10)0.0497 (9)0.0159 (7)0.0114 (7)0.0143 (7)
C40.0499 (9)0.0521 (9)0.0598 (9)0.0013 (7)0.0145 (7)0.0043 (7)
C50.0382 (7)0.0574 (9)0.0441 (8)0.0003 (6)0.0025 (6)0.0020 (7)
C60.0346 (7)0.0484 (8)0.0303 (6)0.0061 (6)0.0053 (5)0.0010 (6)
C70.0387 (7)0.0582 (9)0.0412 (7)0.0125 (6)0.0044 (6)0.0072 (6)
C80.0292 (6)0.0384 (7)0.0392 (7)0.0035 (5)0.0027 (5)0.0110 (5)
Geometric parameters (Å, º) top
O1—C81.2280 (14)C1—C21.405 (2)
N1—N21.3057 (16)C2—C31.365 (2)
N1—C11.3795 (19)C2—H20.9300
N2—N31.3559 (16)C3—C41.407 (2)
N3—C61.3620 (17)C3—H30.9300
N3—C71.4478 (16)C4—C51.367 (2)
N4—C81.3283 (16)C4—H40.9300
N4—N51.4120 (17)C5—C61.3957 (19)
N4—H10.8600C5—H50.9300
N5—H90.884 (9)C7—C81.5179 (18)
N5—H80.888 (9)C7—H7A0.9700
C1—C61.3909 (18)C7—H7B0.9700
N2—N1—C1108.09 (11)C4—C3—H3119.1
N1—N2—N3108.75 (11)C5—C4—C3122.15 (14)
N2—N3—C6110.41 (10)C5—C4—H4118.9
N2—N3—C7120.74 (12)C3—C4—H4118.9
C6—N3—C7128.83 (12)C4—C5—C6115.87 (13)
C8—N4—N5122.88 (10)C4—C5—H5122.1
C8—N4—H1118.6C6—C5—H5122.1
N5—N4—H1118.6N3—C6—C1104.05 (11)
N4—N5—H9108.2 (12)N3—C6—C5133.05 (12)
N4—N5—H8106.8 (13)C1—C6—C5122.90 (12)
H9—N5—H8108.4 (17)N3—C7—C8111.69 (10)
N1—C1—C6108.69 (12)N3—C7—H7A109.3
N1—C1—C2131.22 (13)C8—C7—H7A109.3
C6—C1—C2120.08 (13)N3—C7—H7B109.3
C3—C2—C1117.16 (13)C8—C7—H7B109.3
C3—C2—H2121.4H7A—C7—H7B107.9
C1—C2—H2121.4O1—C8—N4123.60 (12)
C2—C3—C4121.83 (14)O1—C8—C7121.49 (11)
C2—C3—H3119.1N4—C8—C7114.87 (10)
C1—N1—N2—N30.50 (14)C7—N3—C6—C50.5 (2)
N1—N2—N3—C60.98 (15)N1—C1—C6—N30.71 (13)
N1—N2—N3—C7179.30 (11)C2—C1—C6—N3178.58 (12)
N2—N1—C1—C60.15 (14)N1—C1—C6—C5179.03 (12)
N2—N1—C1—C2179.04 (14)C2—C1—C6—C51.68 (19)
N1—C1—C2—C3179.77 (14)C4—C5—C6—N3178.92 (13)
C6—C1—C2—C30.66 (19)C4—C5—C6—C11.43 (19)
C1—C2—C3—C40.5 (2)N2—N3—C7—C897.25 (14)
C2—C3—C4—C50.7 (2)C6—N3—C7—C880.72 (16)
C3—C4—C5—C60.2 (2)N5—N4—C8—O11.0 (2)
N2—N3—C6—C11.02 (13)N5—N4—C8—C7178.60 (12)
C7—N3—C6—C1179.17 (12)N3—C7—C8—O134.61 (18)
N2—N3—C6—C5178.67 (14)N3—C7—C8—N4147.76 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H1···O1i0.862.182.9977 (14)159
Symmetry code: (i) x1, y, z.

Experimental details

Crystal data
Chemical formulaC8H9N5O
Mr191.20
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)5.1434 (9), 6.5885 (12), 25.754 (5)
β (°) 94.227 (3)
V3)870.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.12 × 0.10 × 0.06
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.988, 0.994
No. of measured, independent and
observed [I > 2σ(I)] reflections
4367, 1528, 1364
Rint0.015
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.079, 1.04
No. of reflections1528
No. of parameters135
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.15

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H1···O1i0.862.182.9977 (14)159.1
Symmetry code: (i) x1, y, z.
 

Acknowledgements

This project was supported by the Postgraduate Foundation of Taishan University (grant No. Y04–2–08).

References

First citationAllen, 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
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationJi, N.-N. & Shi, Z.-Q. (2008). Acta Cryst. E64, o655.  Web of Science CrossRef IUCr Journals Google Scholar
First citationPortalone, G. (2007). Acta Cryst. E63, o3232.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPortalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655–o658.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPortalone, G. & Colapietro, M. (2008). Acta Cryst. E64, o304.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, 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
First citationShi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007b). Acta Cryst. E63, o4642.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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