N′-Cyclo­pentyl­idene­pyridine-4-carbo­hydrazide

Lemmerer, A.; Bernstein, J.; Kahlenberg, V.

doi:10.1107/S1600536812013815

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1299

doi:10.1107/S1600536812013815

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N′-Cyclopentylidenepyridine-4-carbohydrazide

Andreas Lemmerer,^a ^* Joel Bernstein ^b and Volker Kahlenberg ^c

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO Wits 2050, South Africa, ^bFaculty of Science, NYU Abu Dhabi, PO Box 129188, Abu Dhabi, United Arab Emirates, and ^cInstitute of Mineralogy and Petrography, University of Innsbruck, Innsbruck 6020, Austria
^*Correspondence e-mail: andreas.lemmerer@wits.ac.za

(Received 8 March 2012; accepted 30 March 2012; online 4 April 2012)

The title compound, C₁₁H₁₃N₃O, is a derivative of the antituberculosis drug isoniazid [systematic name: pyridine-4-carbohydrazide]. The crystal structure consists of repeating hydrogen-bonded chains parallel to the b axis. Adjacent molecules in the chains are linked by bifurcated N—H⋯(O,N) hydrogen bonds, which form an R₁²(5) ring motif.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₃N₃O
M_r = 203.24
Orthorhombic, P b c a
a = 15.762 (3) Å
b = 8.1144 (16) Å
c = 16.015 (3) Å
V = 2048.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.35 × 0.22 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Gemini R diffractometer
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.970, T_max = 0.983
11794 measured reflections
1884 independent reflections
1420 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 0.96
1884 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.889 (15)	2.303 (15)	3.1155 (16)	151.9 (12)
N1—H1⋯O1ⁱ	0.889 (15)	2.607 (15)	3.3368 (14)	140.0 (11)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013815/fy2050sup1.cif

Supporting information file. DOI: 10.1107/S1600536812013815/fy2050Isup2.mol

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013815/fy2050Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812013815/fy2050Isup4.cml

checkCIF report

Comment top

Fig. 1 shows the atomic numbering scheme of the title compound. The amide functional groups form a torsion angle of -39.73 (17)° (C5—C1—C6—O1) with the pyridine ring. Fig. 2 shows the R²₁(5) (Bernstein et al., 1995) hydrogen bonded ring formed with adjacent amide functional groups, leading to a chain along the b-axis.

Related literature top

For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A stoichiometric amount in the ratio of 1:1 of isonicotinic acid hydrazide (0.200 g, 1.46 mmol) to cyclopentanone (0.129 g) was dissolved in 5 ml of methanol. The solution was refluxed for a few hours, and left to cool to room temperature. Colourless, block-like crystals were harvested after slow evaporation over a few days at ambient conditions.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of (I) showing the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Hydrogen bonding chain showing the ring shaped hydrogen bonding motif. Intermolecular N—H···O and N—-H···N hydrogen bonds are shown as dashed red lines.

N'-Cyclopentylidenepyridine-4-carbohydrazide top

Crystal data top

C₁₁H₁₃N₃O	F(000) = 864
M_r = 203.24	D_x = 1.318 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5050 reflections
a = 15.762 (3) Å	θ = 2.9–28.5°
b = 8.1144 (16) Å	µ = 0.09 mm⁻¹
c = 16.015 (3) Å	T = 173 K
V = 2048.3 (7) Å³	Block, colourless
Z = 8	0.35 × 0.22 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Gemini R diffractometer	1420 reflections with I > 2σ(I)
ω scans	R_int = 0.034
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2006)	θ_max = 25.5°, θ_min = 3.1°
T_min = 0.970, T_max = 0.983	h = −17→18
11794 measured reflections	k = −9→9
1884 independent reflections	l = −19→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0527P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max < 0.001
S = 0.96	Δρ_max = 0.14 e Å⁻³
1884 reflections	Δρ_min = −0.21 e Å⁻³
140 parameters

Crystal data top

C₁₁H₁₃N₃O	V = 2048.3 (7) Å³
M_r = 203.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.762 (3) Å	µ = 0.09 mm⁻¹
b = 8.1144 (16) Å	T = 173 K
c = 16.015 (3) Å	0.35 × 0.22 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Gemini R diffractometer	1884 independent reflections
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2006)	1420 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.983	R_int = 0.034
11794 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.14 e Å⁻³
1884 reflections	Δρ_min = −0.21 e Å⁻³
140 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.63373 (8)	0.29380 (15)	0.50919 (7)	0.0229 (3)
C2	0.68605 (8)	0.18488 (16)	0.46629 (8)	0.0300 (3)
H2	0.7458	0.1879	0.4736	0.036*
C3	0.64926 (9)	0.07249 (17)	0.41303 (9)	0.0362 (3)
H3	0.6856	−0.0007	0.3836	0.043*
C4	0.51676 (9)	0.16426 (16)	0.44216 (8)	0.0330 (3)
H4	0.4571	0.1569	0.4345	0.04*
C5	0.54713 (8)	0.28276 (16)	0.49627 (7)	0.0265 (3)
H5	0.5093	0.3554	0.5241	0.032*
C6	0.66894 (7)	0.42811 (15)	0.56313 (7)	0.0223 (3)
C7	0.83244 (7)	0.46470 (15)	0.70795 (8)	0.0238 (3)
C8	0.84781 (8)	0.29668 (16)	0.74453 (8)	0.0284 (3)
H8A	0.8763	0.2236	0.7037	0.034*
H8B	0.7939	0.245	0.7624	0.034*
C9	0.90543 (8)	0.33071 (17)	0.81972 (9)	0.0322 (3)
H9A	0.8715	0.3536	0.8705	0.039*
H9B	0.9435	0.2361	0.8307	0.039*
C10	0.95583 (8)	0.48203 (16)	0.79324 (8)	0.0302 (3)
H10A	1.0022	0.4519	0.7544	0.036*
H10B	0.9803	0.5393	0.8422	0.036*
C11	0.88949 (8)	0.58868 (17)	0.74995 (9)	0.0328 (3)
H11A	0.8576	0.6558	0.7909	0.039*
H11B	0.9161	0.6629	0.7085	0.039*
N1	0.73514 (6)	0.38419 (14)	0.61158 (6)	0.0247 (3)
H1	0.7496 (8)	0.2789 (19)	0.6174 (9)	0.036 (4)*
N2	0.56579 (8)	0.05969 (14)	0.40008 (7)	0.0377 (3)
N3	0.78134 (6)	0.50934 (12)	0.65045 (6)	0.0251 (3)
O1	0.63990 (5)	0.56802 (10)	0.56036 (5)	0.0298 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0297 (7)	0.0192 (6)	0.0197 (6)	0.0008 (5)	−0.0020 (5)	0.0038 (5)
C2	0.0304 (7)	0.0305 (7)	0.0292 (7)	0.0059 (6)	−0.0038 (5)	−0.0017 (6)
C3	0.0478 (9)	0.0292 (8)	0.0316 (7)	0.0092 (7)	−0.0051 (6)	−0.0063 (6)
C4	0.0349 (7)	0.0283 (7)	0.0359 (8)	−0.0032 (6)	−0.0117 (6)	0.0051 (6)
C5	0.0295 (7)	0.0238 (7)	0.0260 (7)	0.0008 (6)	−0.0024 (5)	0.0041 (5)
C6	0.0232 (6)	0.0207 (7)	0.0230 (6)	0.0000 (5)	0.0028 (5)	0.0013 (5)
C7	0.0260 (7)	0.0200 (7)	0.0253 (7)	0.0003 (5)	0.0004 (5)	−0.0029 (5)
C8	0.0322 (7)	0.0218 (7)	0.0312 (7)	−0.0027 (6)	−0.0053 (5)	0.0016 (6)
C9	0.0335 (8)	0.0330 (8)	0.0299 (7)	−0.0018 (6)	−0.0052 (5)	0.0016 (6)
C10	0.0296 (7)	0.0332 (8)	0.0279 (7)	−0.0029 (6)	−0.0047 (5)	−0.0027 (6)
C11	0.0349 (8)	0.0244 (7)	0.0390 (8)	−0.0033 (6)	−0.0091 (6)	−0.0044 (6)
N1	0.0319 (6)	0.0146 (6)	0.0277 (6)	−0.0010 (5)	−0.0073 (4)	−0.0016 (5)
N2	0.0499 (8)	0.0289 (7)	0.0343 (6)	−0.0009 (6)	−0.0141 (5)	−0.0026 (5)
N3	0.0284 (6)	0.0189 (6)	0.0281 (6)	−0.0021 (4)	−0.0041 (4)	−0.0023 (5)
O1	0.0298 (5)	0.0221 (5)	0.0374 (5)	0.0048 (4)	−0.0036 (4)	−0.0022 (4)

Geometric parameters (Å, º) top

C1—C5	1.3836 (18)	C7—C11	1.5076 (17)
C1—C2	1.3904 (18)	C8—C9	1.5333 (18)
C1—C6	1.4973 (17)	C8—H8A	0.99
C2—C3	1.3768 (19)	C8—H8B	0.99
C2—H2	0.95	C9—C10	1.5227 (19)
C3—N2	1.3360 (19)	C9—H9A	0.99
C3—H3	0.95	C9—H9B	0.99
C4—N2	1.3309 (18)	C10—C11	1.5243 (18)
C4—C5	1.3801 (18)	C10—H10A	0.99
C4—H4	0.95	C10—H10B	0.99
C5—H5	0.95	C11—H11A	0.99
C6—O1	1.2249 (14)	C11—H11B	0.99
C6—N1	1.3484 (16)	N1—N3	1.3961 (14)
C7—N3	1.2759 (15)	N1—H1	0.889 (15)
C7—C8	1.5035 (17)

C5—C1—C2	118.04 (11)	C9—C8—H8B	111
C5—C1—C6	119.94 (11)	H8A—C8—H8B	109
C2—C1—C6	121.87 (11)	C10—C9—C8	103.63 (10)
C3—C2—C1	118.51 (12)	C10—C9—H9A	111
C3—C2—H2	120.7	C8—C9—H9A	111
C1—C2—H2	120.7	C10—C9—H9B	111
N2—C3—C2	124.23 (13)	C8—C9—H9B	111
N2—C3—H3	117.9	H9A—C9—H9B	109
C2—C3—H3	117.9	C9—C10—C11	103.09 (10)
N2—C4—C5	124.11 (13)	C9—C10—H10A	111.1
N2—C4—H4	117.9	C11—C10—H10A	111.1
C5—C4—H4	117.9	C9—C10—H10B	111.1
C4—C5—C1	118.76 (12)	C11—C10—H10B	111.1
C4—C5—H5	120.6	H10A—C10—H10B	109.1
C1—C5—H5	120.6	C7—C11—C10	103.49 (10)
O1—C6—N1	123.71 (11)	C7—C11—H11A	111.1
O1—C6—C1	121.01 (11)	C10—C11—H11A	111.1
N1—C6—C1	115.24 (10)	C7—C11—H11B	111.1
N3—C7—C8	129.82 (11)	C10—C11—H11B	111.1
N3—C7—C11	120.59 (11)	H11A—C11—H11B	109
C8—C7—C11	109.59 (10)	C6—N1—N3	117.90 (10)
C7—C8—C9	103.78 (10)	C6—N1—H1	120.9 (9)
C7—C8—H8A	111	N3—N1—H1	121.2 (9)
C9—C8—H8A	111	C4—N2—C3	116.34 (11)
C7—C8—H8B	111	C7—N3—N1	116.39 (10)

C5—C1—C2—C3	0.30 (18)	C7—C8—C9—C10	−30.69 (13)
C6—C1—C2—C3	−175.20 (12)	C8—C9—C10—C11	40.97 (13)
C1—C2—C3—N2	−0.6 (2)	N3—C7—C11—C10	−163.83 (11)
N2—C4—C5—C1	−0.92 (19)	C8—C7—C11—C10	15.97 (14)
C2—C1—C5—C4	0.40 (17)	C9—C10—C11—C7	−34.78 (13)
C6—C1—C5—C4	175.99 (11)	O1—C6—N1—N3	−10.45 (17)
C5—C1—C6—O1	−39.73 (17)	C1—C6—N1—N3	167.52 (9)
C2—C1—C6—O1	135.69 (13)	C5—C4—N2—C3	0.65 (19)
C5—C1—C6—N1	142.25 (11)	C2—C3—N2—C4	0.1 (2)
C2—C1—C6—N1	−42.34 (16)	C8—C7—N3—N1	−3.79 (18)
N3—C7—C8—C9	−171.14 (12)	C11—C7—N3—N1	175.96 (10)
C11—C7—C8—C9	9.09 (14)	C6—N1—N3—C7	166.86 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.889 (15)	2.303 (15)	3.1155 (16)	151.9 (12)
N1—H1···O1ⁱ	0.889 (15)	2.607 (15)	3.3368 (14)	140.0 (11)

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₃O
M_r	203.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	15.762 (3), 8.1144 (16), 16.015 (3)
V (Å³)	2048.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.22 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Gemini R diffractometer
Absorption correction	Multi-scan (ABSPACK in CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.970, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	11794, 1884, 1420
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 0.96
No. of reflections	1884
No. of parameters	140
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.21

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.889 (15)	2.303 (15)	3.1155 (16)	151.9 (12)
N1—H1···O1ⁱ	0.889 (15)	2.607 (15)	3.3368 (14)	140.0 (11)

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

This work was supported in part by grant No. 2004118 from the United States–Israel Binational Science Foundation (Jerusalem). AL thanks the South African National Research Foundation for a postdoctoral scholarship (SFP2007070400002), the Oppenheimer Memorial Trust for financial support and the Molecular Sciences Institute for infrastructure.

References

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