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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1880.
Published online 2008 September 6. doi:  10.1107/S1600536808027955
PMCID: PMC2959451

N′-Prop­ylisonicotinohydrazide

Abstract

In the title compound, C9H11N3O, the crystal structure is stabilized by a bifurcated inter­molecular N—H(...)(N,O) hydrogen bond and a C—H(...)O inter­action, leading to chains of mol­ecules.

Related literature

For background on the medicinal uses of isoniazid (isonicotinic acid hydrazide, INH) and INH hydrazide–hydrazones, see: Fox & Mitchison (1975 [triangle]); Kucukguzel et al. (2003 [triangle]). For the synthesis, see: Deng et al. (2005 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o1880-scheme1.jpg

Experimental

Crystal data

  • C9H11N3O
  • M r = 177.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1880-efi1.jpg
  • a = 13.010 (3) Å
  • b = 17.590 (4) Å
  • c = 8.0000 (16) Å
  • V = 1830.8 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 297 (2) K
  • 0.43 × 0.28 × 0.22 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.963, T max = 0.981
  • 9110 measured reflections
  • 1634 independent reflections
  • 986 reflections with I > 2σ(I)
  • R int = 0.062

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.145
  • S = 1.00
  • 1634 reflections
  • 125 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027955/hb2787sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027955/hb2787Isup2.hkl

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

Acknowledgments

The authors are grateful for financial support from the Natural Science Foundation of Heilongjiang Province (D200672) and the Harbin Science and Technology Key Project (2005AA9CS116-4).

supplementary crystallographic information

Comment

Isoniazid (isonicotinic acid hydrazide, INH) continues to be the most widely used chemotherapeutic agent for the treatment of tuberculosis (Fox & Mitchison, 1975). Some INH hydrazide–hydrazones were reported to have lower toxicity than hydrazides because of the blockage of the –NH2 group (Kucukguzel et al.2003). In this paper, we report the structure of the title compound, (I), (Fig. 1).

The bond lengths and angles for (I) are within their normal ranges (Allen et al., 1987). The dihedral angle between the mean planes on the N1/C1–C5 ring and the O1/N2/N3/C6 grouping is 48.97 (12)°.

As shown in Fig. 2, the crystal structure is stabilized by bifurcated intermolecular N—H···(N,O) hydrogen bonds (Table 1) and C—H···O interactions leading to chains of molecules.

Experimental

The title compound was synthesized according to the literature method (Deng et al., 2005): acetone (25 mmol) and isonicotinyl hydrazine (22 mmol) were dissolved in anhydrous ethanol (40 ml) and refluxed for 5 h, and a yellow precipitate was obtained, which was recrystalized from ethanol and diethyl ether (1:1 v/v) to yield yellow blocks of (I) after two days in an ice box.

Refinement

The N-bonded H atom was located in a difference map and freely refined. The C-bonded H atoms were placed in calculated positions with C—H = 0.93–0.96 Å and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms.
Fig. 2.
Part of a chain of molecules of (I) connected by hydrogen bonds (dashed lines).

Crystal data

C9H11N3OF(000) = 752
Mr = 177.21Dx = 1.286 Mg m3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 1634 reflections
a = 13.010 (3) Åθ = 2.0–25.1°
b = 17.590 (4) ŵ = 0.09 mm1
c = 8.0000 (16) ÅT = 297 K
V = 1830.8 (6) Å3Block, yellow
Z = 80.43 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer1634 independent reflections
Radiation source: fine-focus sealed tube986 reflections with I > 2σ(I)
graphiteRint = 0.062
[var phi] and ω scansθmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −15→15
Tmin = 0.963, Tmax = 0.981k = −19→20
9110 measured reflectionsl = −6→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: difmap (N-H) and geom (C-H)
wR(F2) = 0.145H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.070P)2 + 0.2547P] where P = (Fo2 + 2Fc2)/3
1634 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.18 e Å3
1 restraintΔρmin = −0.14 e Å3

Special details

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)

xyzUiso*/Ueq
C10.5785 (2)0.3888 (2)0.6946 (4)0.0774 (9)
H10.55090.40370.79670.093*
C20.6065 (2)0.44485 (16)0.5836 (3)0.0615 (7)
H20.59750.49590.61020.074*
C30.64780 (16)0.42398 (14)0.4339 (3)0.0475 (6)
C40.65648 (19)0.34815 (15)0.4012 (3)0.0599 (7)
H40.68250.33170.29920.072*
C50.6266 (2)0.29651 (16)0.5193 (4)0.0699 (8)
H50.63380.24510.49450.084*
C60.67852 (18)0.48038 (13)0.3061 (3)0.0493 (6)
C70.84373 (18)0.63336 (14)0.2827 (3)0.0494 (6)
C80.8682 (2)0.69467 (16)0.1616 (4)0.0771 (9)
H8A0.81880.69410.07250.116*
H8B0.93580.68660.11680.116*
H8C0.86590.74300.21740.116*
C90.91433 (19)0.62320 (16)0.4257 (3)0.0620 (8)
H9A0.87510.61650.52630.093*
H9B0.95730.66730.43650.093*
H9C0.95650.57920.40730.093*
N10.58839 (18)0.31505 (15)0.6654 (3)0.0767 (8)
N20.73950 (15)0.53574 (12)0.3610 (2)0.0517 (6)
N30.76506 (16)0.59328 (11)0.2493 (2)0.0544 (6)
O10.64977 (13)0.47481 (10)0.1615 (2)0.0676 (6)
H2A0.7650 (17)0.5349 (14)0.4690 (16)0.072 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.092 (2)0.087 (2)0.0534 (18)−0.0139 (18)0.0222 (15)0.0038 (16)
C20.0764 (18)0.0595 (17)0.0486 (16)−0.0105 (14)0.0130 (13)0.0062 (13)
C30.0441 (14)0.0593 (17)0.0391 (13)−0.0091 (11)−0.0025 (11)0.0023 (11)
C40.0596 (17)0.0651 (19)0.0552 (17)−0.0069 (14)0.0043 (12)−0.0020 (14)
C50.0658 (18)0.0616 (18)0.082 (2)−0.0076 (14)−0.0046 (16)0.0095 (16)
C60.0495 (14)0.0609 (16)0.0375 (14)−0.0071 (12)−0.0004 (11)0.0039 (12)
C70.0465 (14)0.0565 (16)0.0453 (14)−0.0012 (12)0.0043 (11)0.0032 (11)
C80.0697 (18)0.078 (2)0.084 (2)−0.0169 (16)0.0030 (16)0.0294 (16)
C90.0562 (15)0.0726 (18)0.0574 (17)−0.0112 (13)−0.0062 (13)0.0025 (13)
N10.0825 (17)0.078 (2)0.0697 (18)−0.0147 (14)0.0044 (13)0.0211 (14)
N20.0602 (13)0.0628 (14)0.0321 (11)−0.0156 (11)−0.0034 (9)0.0091 (10)
N30.0579 (13)0.0647 (14)0.0406 (12)−0.0108 (11)−0.0030 (9)0.0147 (10)
O10.0759 (13)0.0883 (14)0.0387 (10)−0.0241 (10)−0.0097 (8)0.0064 (9)

Geometric parameters (Å, °)

C1—N11.324 (4)C6—N21.331 (3)
C1—C21.376 (4)C7—N31.271 (3)
C1—H10.9300C7—C81.484 (3)
C2—C31.363 (3)C7—C91.478 (3)
C2—H20.9300C8—H8A0.9600
C3—C41.364 (3)C8—H8B0.9600
C3—C61.480 (3)C8—H8C0.9600
C4—C51.367 (4)C9—H9A0.9600
C4—H40.9300C9—H9B0.9600
C5—N11.312 (4)C9—H9C0.9600
C5—H50.9300N2—N31.391 (2)
C6—O11.220 (3)N2—H2A0.926 (10)
N1—C1—C2124.2 (3)N3—C7—C9126.6 (2)
N1—C1—H1117.9C8—C7—C9117.4 (2)
C2—C1—H1117.9C7—C8—H8A109.5
C3—C2—C1118.6 (3)C7—C8—H8B109.5
C3—C2—H2120.7H8A—C8—H8B109.5
C1—C2—H2120.7C7—C8—H8C109.5
C4—C3—C2117.7 (2)H8A—C8—H8C109.5
C4—C3—C6120.0 (2)H8B—C8—H8C109.5
C2—C3—C6122.2 (2)C7—C9—H9A109.5
C5—C4—C3119.6 (3)C7—C9—H9B109.5
C5—C4—H4120.2H9A—C9—H9B109.5
C3—C4—H4120.2C7—C9—H9C109.5
N1—C5—C4124.0 (3)H9A—C9—H9C109.5
N1—C5—H5118.0H9B—C9—H9C109.5
C4—C5—H5118.0C5—N1—C1116.0 (2)
O1—C6—N2123.7 (2)C6—N2—N3117.57 (19)
O1—C6—C3121.2 (2)C6—N2—H2A120.6 (15)
N2—C6—C3115.1 (2)N3—N2—H2A121.8 (15)
N3—C7—C8116.0 (2)C7—N3—N2117.42 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.93 (2)2.17 (2)3.001 (3)149 (2)
N2—H2A···N3i0.93 (2)2.50 (2)3.268 (2)141.(2)
C9—H9A···N3i0.962.583.525 (3)167

Symmetry codes: (i) −x+3/2, y, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2787).

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.
  • Bruker (2001). SADABS and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deng, Q.-L., Yu, M., Chen, X., Diao, C.-H., Jing, Z.-L. & Fan, Z. (2005). Acta Cryst. E61, o2545–o2546.
  • Fox, W. & Mitchison, D. A. (1975). Am. Rev. Respir. Dis.111, 325–352. [PubMed]
  • Kucukguzel, S. G., Mazi, A., Sahin, F., Ozturk, S. & Stables, J. (2003). Eur. J. Med. Chem.38, 1005–1013. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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