Methyl 3-(3-pyridylmethyl­ene)carbazate

Li, Y.-F.; Liu, H.-X.; Jian, F.-F.

doi:10.1107/S1600536809045024

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2959

https://doi.org/10.1107/S1600536809045024

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Methyl 3-(3-pyridylmethylene)carbazate

Yu-Feng Li,^a Hai-Xing Liu ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 27 October 2009; accepted 28 October 2009; online 31 October 2009)

In the crystal of the title compound, C₈H₉N₃O₂, molecules are linked by N—H⋯N hydrogen bonds, forming S(7) chains propagating in [010].

Related literature

For background to Schiff bases, see: Cimerman et al. (1997 ).

Experimental

Crystal data

C₈H₉N₃O₂
M_r = 179.18
Orthorhombic, P b c a
a = 10.585 (2) Å
b = 10.019 (2) Å
c = 16.311 (3) Å
V = 1729.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.26 × 0.21 × 0.19 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
15411 measured reflections
1984 independent reflections
1794 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.128
S = 1.08
1984 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.86	2.12	2.9751 (14)	171
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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 global, I. DOI: https://doi.org/10.1107/S1600536809045024/hb5196sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809045024/hb5196Isup2.hkl

checkCIF report

Related literature top

For background to Schiff bases, see: Cimerman et al. (1997).

Experimental top

A mixture of nicotinaldehyde (0.1 mol), and methyl carbazate (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.082 mol, yield 82%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Structure description top

For background to Schiff bases, see: Cimerman et al. (1997).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 structure of the title compound showing 30% probability displacement ellipsoids.

Methyl 3-(3-pyridylmethylene)carbazate top

Crystal data top

C₈H₉N₃O₂	D_x = 1.376 Mg m⁻³
M_r = 179.18	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1985 reflections
a = 10.585 (2) Å	θ = 3.4–27.5°
b = 10.019 (2) Å	µ = 0.10 mm⁻¹
c = 16.311 (3) Å	T = 293 K
V = 1729.8 (6) Å³	Block, colourless
Z = 8	0.26 × 0.21 × 0.19 mm
F(000) = 752

Data collection top

Bruker SMART CCD diffractometer	1794 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→13
15411 measured reflections	k = −13→12
1984 independent reflections	l = −21→21

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0867P)² + 0.1822P] where P = (F_o² + 2F_c²)/3
1984 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₈H₉N₃O₂	V = 1729.8 (6) Å³
M_r = 179.18	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.585 (2) Å	µ = 0.10 mm⁻¹
b = 10.019 (2) Å	T = 293 K
c = 16.311 (3) Å	0.26 × 0.21 × 0.19 mm

Data collection top

Bruker SMART CCD diffractometer	1794 reflections with I > 2σ(I)
15411 measured reflections	R_int = 0.028
1984 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.08	Δρ_max = 0.24 e Å⁻³
1984 reflections	Δρ_min = −0.32 e Å⁻³
118 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
O2	0.18815 (8)	0.11348 (8)	0.57072 (5)	0.0433 (2)
C3	0.35300 (9)	−0.17778 (10)	0.74434 (7)	0.0343 (3)
H3A	0.4286	−0.1375	0.7291	0.041*
N4	0.48145 (8)	−0.43908 (10)	0.88319 (6)	0.0390 (3)
C5	0.35393 (9)	−0.28611 (10)	0.80449 (6)	0.0311 (2)
N1	0.26042 (8)	−0.03820 (9)	0.65555 (6)	0.0372 (2)
H1A	0.3336	−0.0124	0.6391	0.045*
C4	0.24493 (9)	−0.34567 (12)	0.83549 (7)	0.0377 (3)
H4B	0.1656	−0.3156	0.8194	0.045*
N2	0.24948 (8)	−0.13809 (9)	0.71265 (5)	0.0345 (2)
C2	0.15392 (9)	0.01936 (10)	0.62537 (6)	0.0339 (3)
O1	0.04701 (7)	−0.00686 (10)	0.64392 (6)	0.0541 (3)
C6	0.46946 (9)	−0.33613 (11)	0.83129 (6)	0.0358 (3)
H6A	0.5428	−0.2957	0.8120	0.043*
C8	0.37535 (11)	−0.49405 (11)	0.91219 (7)	0.0393 (3)
H8A	0.3819	−0.5651	0.9486	0.047*
C7	0.25615 (10)	−0.44962 (12)	0.89025 (7)	0.0414 (3)
H7A	0.1845	−0.4896	0.9123	0.050*
C1	0.08717 (14)	0.19038 (13)	0.53648 (8)	0.0523 (3)
H1B	0.1209	0.2546	0.4987	0.078*
H1C	0.0430	0.2359	0.5796	0.078*
H1D	0.0298	0.1322	0.5082	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0420 (5)	0.0450 (5)	0.0429 (5)	0.0031 (3)	0.0027 (3)	0.0115 (3)
C3	0.0289 (5)	0.0385 (5)	0.0355 (5)	−0.0040 (4)	−0.0007 (4)	0.0006 (4)
N4	0.0315 (5)	0.0440 (5)	0.0415 (5)	0.0086 (4)	−0.0001 (4)	0.0016 (4)
C5	0.0289 (5)	0.0341 (5)	0.0302 (5)	−0.0005 (4)	−0.0009 (3)	−0.0034 (4)
N1	0.0277 (4)	0.0426 (5)	0.0413 (5)	−0.0042 (3)	−0.0005 (3)	0.0102 (4)
C4	0.0257 (5)	0.0467 (6)	0.0407 (6)	−0.0008 (4)	−0.0037 (4)	0.0042 (4)
N2	0.0325 (4)	0.0364 (5)	0.0346 (4)	−0.0039 (3)	−0.0018 (3)	0.0033 (3)
C2	0.0324 (5)	0.0363 (5)	0.0330 (5)	−0.0018 (4)	−0.0015 (4)	0.0005 (4)
O1	0.0284 (4)	0.0685 (6)	0.0656 (6)	−0.0020 (4)	−0.0018 (4)	0.0220 (5)
C6	0.0263 (5)	0.0430 (6)	0.0380 (5)	0.0009 (4)	0.0026 (4)	−0.0003 (4)
C8	0.0400 (6)	0.0373 (5)	0.0407 (5)	0.0030 (4)	−0.0004 (4)	0.0038 (4)
C7	0.0312 (5)	0.0465 (6)	0.0463 (6)	−0.0069 (4)	0.0005 (4)	0.0064 (5)
C1	0.0603 (8)	0.0478 (6)	0.0489 (7)	0.0117 (6)	−0.0049 (6)	0.0102 (5)

Geometric parameters (Å, º) top

O2—C2	1.3472 (13)	N1—H1A	0.8600
O2—C1	1.4312 (15)	C4—C7	1.3771 (16)
C3—N2	1.2752 (13)	C4—H4B	0.9300
C3—C5	1.4631 (14)	C2—O1	1.2005 (13)
C3—H3A	0.9300	C6—H6A	0.9300
N4—C8	1.3373 (14)	C8—C7	1.3850 (15)
N4—C6	1.3403 (14)	C8—H8A	0.9300
C5—C6	1.3920 (13)	C7—H7A	0.9300
C5—C4	1.3940 (13)	C1—H1B	0.9600
N1—C2	1.3586 (13)	C1—H1C	0.9600
N1—N2	1.3719 (12)	C1—H1D	0.9600

C2—O2—C1	115.73 (9)	O2—C2—N1	108.28 (9)
N2—C3—C5	120.59 (9)	N4—C6—C5	123.96 (9)
N2—C3—H3A	119.7	N4—C6—H6A	118.0
C5—C3—H3A	119.7	C5—C6—H6A	118.0
C8—N4—C6	117.44 (9)	N4—C8—C7	122.77 (10)
C6—C5—C4	117.33 (9)	N4—C8—H8A	118.6
C6—C5—C3	118.92 (8)	C7—C8—H8A	118.6
C4—C5—C3	123.73 (8)	C4—C7—C8	119.29 (10)
C2—N1—N2	119.05 (8)	C4—C7—H7A	120.4
C2—N1—H1A	120.5	C8—C7—H7A	120.4
N2—N1—H1A	120.5	O2—C1—H1B	109.5
C7—C4—C5	119.18 (9)	O2—C1—H1C	109.5
C7—C4—H4B	120.4	H1B—C1—H1C	109.5
C5—C4—H4B	120.4	O2—C1—H1D	109.5
C3—N2—N1	115.47 (8)	H1B—C1—H1D	109.5
O1—C2—O2	124.99 (10)	H1C—C1—H1D	109.5
O1—C2—N1	126.73 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.12	2.9751 (14)	171

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₉N₃O₂
M_r	179.18
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.585 (2), 10.019 (2), 16.311 (3)
V (Å³)	1729.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.21 × 0.19

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15411, 1984, 1794
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.128, 1.08
No. of reflections	1984
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
N1—H1A···N4ⁱ	0.86	2.12	2.9751 (14)	171

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

The authors would like to thank the Science Foundation of Weifang University (No. 2009Z24).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar