N′-Prop­ylisonicotinohydrazide

Wang, S.-Y.; Song, X.-M.; Duan, L.-X.

doi:10.1107/S1600536808027955

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1880

doi:10.1107/S1600536808027955

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N′-Propylisonicotinohydrazide

Shu-Ye Wang,^a Xue-Ming Song ^a ^* and Li-Xiang Duan ^a

^aThe First Affiliated Hospital, Harbin Medical University, Harbin 150001, People's Republic of China
^*Correspondence e-mail: song_xueming@sina.com

(Received 26 August 2008; accepted 1 September 2008; online 6 September 2008)

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 ); Kucukguzel et al. (2003 ). For the synthesis, see: Deng et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁N₃O
M_r = 177.21
Orthorhombic, P c c n
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 ) 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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.145
S = 1.00
1634 reflections
125 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.926 (15)	2.172 (19)	3.001 (3)	149 (2)
N2—H2A⋯N3ⁱ	0.926 (15)	2.497 (16)	3.268 (2)	140.9 (19)
C9—H9A⋯N3ⁱ	0.96	2.58	3.525 (3)	167
Symmetry code: (i) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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).

N'-Propylisonicotinohydrazide top

Crystal data top

C₉H₁₁N₃O	F(000) = 752
M_r = 177.21	D_x = 1.286 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1634 reflections
a = 13.010 (3) Å	θ = 2.0–25.1°
b = 17.590 (4) Å	µ = 0.09 mm⁻¹
c = 8.0000 (16) Å	T = 297 K
V = 1830.8 (6) Å³	Block, yellow
Z = 8	0.43 × 0.28 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	1634 independent reflections
Radiation source: fine-focus sealed tube	986 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→15
T_min = 0.963, T_max = 0.981	k = −19→20
9110 measured reflections	l = −6→9

Refinement top

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)] = 0.047	Hydrogen site location: difmap (N-H) and geom (C-H)
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.070P)² + 0.2547P] where P = (F_o² + 2F_c²)/3
1634 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₉H₁₁N₃O	V = 1830.8 (6) Å³
M_r = 177.21	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 13.010 (3) Å	µ = 0.09 mm⁻¹
b = 17.590 (4) Å	T = 297 K
c = 8.0000 (16) Å	0.43 × 0.28 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	1634 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	986 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.981	R_int = 0.062
9110 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.18 e Å⁻³
1634 reflections	Δρ_min = −0.14 e Å⁻³
125 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

	x	y	z	U_iso*/U_eq
C1	0.5785 (2)	0.3888 (2)	0.6946 (4)	0.0774 (9)
H1	0.5509	0.4037	0.7967	0.093*
C2	0.6065 (2)	0.44485 (16)	0.5836 (3)	0.0615 (7)
H2	0.5975	0.4959	0.6102	0.074*
C3	0.64780 (16)	0.42398 (14)	0.4339 (3)	0.0475 (6)
C4	0.65648 (19)	0.34815 (15)	0.4012 (3)	0.0599 (7)
H4	0.6825	0.3317	0.2992	0.072*
C5	0.6266 (2)	0.29651 (16)	0.5193 (4)	0.0699 (8)
H5	0.6338	0.2451	0.4945	0.084*
C6	0.67852 (18)	0.48038 (13)	0.3061 (3)	0.0493 (6)
C7	0.84373 (18)	0.63336 (14)	0.2827 (3)	0.0494 (6)
C8	0.8682 (2)	0.69467 (16)	0.1616 (4)	0.0771 (9)
H8A	0.8188	0.6941	0.0725	0.116*
H8B	0.9358	0.6866	0.1168	0.116*
H8C	0.8659	0.7430	0.2174	0.116*
C9	0.91433 (19)	0.62320 (16)	0.4257 (3)	0.0620 (8)
H9A	0.8751	0.6165	0.5263	0.093*
H9B	0.9573	0.6673	0.4365	0.093*
H9C	0.9565	0.5792	0.4073	0.093*
N1	0.58839 (18)	0.31505 (15)	0.6654 (3)	0.0767 (8)
N2	0.73950 (15)	0.53574 (12)	0.3610 (2)	0.0517 (6)
N3	0.76506 (16)	0.59328 (11)	0.2493 (2)	0.0544 (6)
O1	0.64977 (13)	0.47481 (10)	0.1615 (2)	0.0676 (6)
H2A	0.7650 (17)	0.5349 (14)	0.4690 (16)	0.072 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.092 (2)	0.087 (2)	0.0534 (18)	−0.0139 (18)	0.0222 (15)	0.0038 (16)
C2	0.0764 (18)	0.0595 (17)	0.0486 (16)	−0.0105 (14)	0.0130 (13)	0.0062 (13)
C3	0.0441 (14)	0.0593 (17)	0.0391 (13)	−0.0091 (11)	−0.0025 (11)	0.0023 (11)
C4	0.0596 (17)	0.0651 (19)	0.0552 (17)	−0.0069 (14)	0.0043 (12)	−0.0020 (14)
C5	0.0658 (18)	0.0616 (18)	0.082 (2)	−0.0076 (14)	−0.0046 (16)	0.0095 (16)
C6	0.0495 (14)	0.0609 (16)	0.0375 (14)	−0.0071 (12)	−0.0004 (11)	0.0039 (12)
C7	0.0465 (14)	0.0565 (16)	0.0453 (14)	−0.0012 (12)	0.0043 (11)	0.0032 (11)
C8	0.0697 (18)	0.078 (2)	0.084 (2)	−0.0169 (16)	0.0030 (16)	0.0294 (16)
C9	0.0562 (15)	0.0726 (18)	0.0574 (17)	−0.0112 (13)	−0.0062 (13)	0.0025 (13)
N1	0.0825 (17)	0.078 (2)	0.0697 (18)	−0.0147 (14)	0.0044 (13)	0.0211 (14)
N2	0.0602 (13)	0.0628 (14)	0.0321 (11)	−0.0156 (11)	−0.0034 (9)	0.0091 (10)
N3	0.0579 (13)	0.0647 (14)	0.0406 (12)	−0.0108 (11)	−0.0030 (9)	0.0147 (10)
O1	0.0759 (13)	0.0883 (14)	0.0387 (10)	−0.0241 (10)	−0.0097 (8)	0.0064 (9)

Geometric parameters (Å, º) top

C1—N1	1.324 (4)	C6—N2	1.331 (3)
C1—C2	1.376 (4)	C7—N3	1.271 (3)
C1—H1	0.9300	C7—C8	1.484 (3)
C2—C3	1.363 (3)	C7—C9	1.478 (3)
C2—H2	0.9300	C8—H8A	0.9600
C3—C4	1.364 (3)	C8—H8B	0.9600
C3—C6	1.480 (3)	C8—H8C	0.9600
C4—C5	1.367 (4)	C9—H9A	0.9600
C4—H4	0.9300	C9—H9B	0.9600
C5—N1	1.312 (4)	C9—H9C	0.9600
C5—H5	0.9300	N2—N3	1.391 (2)
C6—O1	1.220 (3)	N2—H2A	0.926 (10)

N1—C1—C2	124.2 (3)	N3—C7—C9	126.6 (2)
N1—C1—H1	117.9	C8—C7—C9	117.4 (2)
C2—C1—H1	117.9	C7—C8—H8A	109.5
C3—C2—C1	118.6 (3)	C7—C8—H8B	109.5
C3—C2—H2	120.7	H8A—C8—H8B	109.5
C1—C2—H2	120.7	C7—C8—H8C	109.5
C4—C3—C2	117.7 (2)	H8A—C8—H8C	109.5
C4—C3—C6	120.0 (2)	H8B—C8—H8C	109.5
C2—C3—C6	122.2 (2)	C7—C9—H9A	109.5
C5—C4—C3	119.6 (3)	C7—C9—H9B	109.5
C5—C4—H4	120.2	H9A—C9—H9B	109.5
C3—C4—H4	120.2	C7—C9—H9C	109.5
N1—C5—C4	124.0 (3)	H9A—C9—H9C	109.5
N1—C5—H5	118.0	H9B—C9—H9C	109.5
C4—C5—H5	118.0	C5—N1—C1	116.0 (2)
O1—C6—N2	123.7 (2)	C6—N2—N3	117.57 (19)
O1—C6—C3	121.2 (2)	C6—N2—H2A	120.6 (15)
N2—C6—C3	115.1 (2)	N3—N2—H2A	121.8 (15)
N3—C7—C8	116.0 (2)	C7—N3—N2	117.42 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.93 (2)	2.17 (2)	3.001 (3)	149 (2)
N2—H2A···N3ⁱ	0.93 (2)	2.50 (2)	3.268 (2)	141 (2)
C9—H9A···N3ⁱ	0.96	2.58	3.525 (3)	167

Symmetry code: (i) −x+3/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O
M_r	177.21
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	297
a, b, c (Å)	13.010 (3), 17.590 (4), 8.0000 (16)
V (Å³)	1830.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.963, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	9110, 1634, 986
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.145, 1.00
No. of reflections	1634
No. of parameters	125
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.926 (15)	2.172 (19)	3.001 (3)	149 (2)
N2—H2A···N3ⁱ	0.926 (15)	2.497 (16)	3.268 (2)	140.9 (19)
C9—H9A···N3ⁱ	0.96	2.58	3.525 (3)	167

Symmetry code: (i) −x+3/2, y, z+1/2.

Acknowledgements

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).

References

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