Methyl 3-benzyl­idenecarbazate

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

doi:10.1107/S1600536809045012

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2963

https://doi.org/10.1107/S1600536809045012

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Methyl 3-benzylidenecarbazate

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, C₉H₁₀N₂O₂, the molecules are linked by N—H⋯O hydrogen bonds, generating S(4) chains propagating in [010].

Related literature

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

Experimental

Crystal data

C₉H₁₀N₂O₂
M_r = 178.19
Orthorhombic, P b c a
a = 12.278 (3) Å
b = 7.8035 (16) Å
c = 19.466 (4) Å
V = 1865.1 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
16349 measured reflections
2132 independent reflections
1693 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.147
S = 1.08
2132 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.04	2.8986 (15)	179
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

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/S1600536809045012/hb5195sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809045012/hb5195Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

A mixture of benzaldehyde (0.1 mol), and methyl carbazate (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.089 mol, yield 89%). 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-benzylidenecarbazate top

Crystal data top

C₉H₁₀N₂O₂	F(000) = 752
M_r = 178.19	D_x = 1.269 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1984 reflections
a = 12.278 (3) Å	θ = 3.5–27.5°
b = 7.8035 (16) Å	µ = 0.09 mm⁻¹
c = 19.466 (4) Å	T = 293 K
V = 1865.1 (7) Å³	Block, colourless
Z = 8	0.25 × 0.21 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1693 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
φ and ω scans	h = −15→15
16349 measured reflections	k = −10→8
2132 independent reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2132 reflections	Δρ_max = 0.23 e Å⁻³
119 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (3)

Crystal data top

C₉H₁₀N₂O₂	V = 1865.1 (7) Å³
M_r = 178.19	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.278 (3) Å	µ = 0.09 mm⁻¹
b = 7.8035 (16) Å	T = 293 K
c = 19.466 (4) Å	0.25 × 0.21 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1693 reflections with I > 2σ(I)
16349 measured reflections	R_int = 0.048
2132 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.08	Δρ_max = 0.23 e Å⁻³
2132 reflections	Δρ_min = −0.18 e Å⁻³
119 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	0.87392 (7)	0.13497 (11)	0.52542 (4)	0.0522 (3)
N2	0.72993 (8)	0.24691 (12)	0.62265 (4)	0.0434 (3)
O1	0.85158 (9)	0.38853 (12)	0.47171 (5)	0.0613 (3)
C3	0.65739 (9)	0.31376 (15)	0.66062 (6)	0.0443 (3)
H3A	0.6184	0.4077	0.6445	0.053*
N1	0.74972 (9)	0.33172 (13)	0.56166 (5)	0.0505 (3)
H1A	0.7125	0.4207	0.5504	0.061*
C4	0.63373 (10)	0.24621 (14)	0.72925 (5)	0.0418 (3)
C2	0.82860 (10)	0.27174 (15)	0.52044 (5)	0.0434 (3)
C9	0.70485 (10)	0.13562 (16)	0.76285 (6)	0.0508 (3)
H9A	0.7678	0.0986	0.7408	0.061*
C7	0.58904 (13)	0.13493 (19)	0.86228 (7)	0.0599 (4)
H7A	0.5747	0.0988	0.9069	0.072*
C5	0.54021 (11)	0.29976 (18)	0.76341 (6)	0.0532 (3)
H5A	0.4922	0.3747	0.7419	0.064*
C8	0.68246 (13)	0.08046 (19)	0.82877 (6)	0.0596 (4)
H8A	0.7304	0.0063	0.8508	0.072*
C6	0.51809 (12)	0.24207 (18)	0.82934 (7)	0.0607 (4)
H6A	0.4545	0.2765	0.8513	0.073*
C1	0.93760 (15)	0.3429 (2)	0.42527 (8)	0.0764 (5)
H1B	0.9484	0.4338	0.3928	0.115*
H1C	0.9184	0.2397	0.4013	0.115*
H1D	1.0036	0.3246	0.4507	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0572 (6)	0.0453 (5)	0.0541 (5)	0.0041 (4)	0.0082 (4)	0.0034 (3)
N2	0.0465 (6)	0.0427 (6)	0.0410 (5)	0.0010 (4)	0.0018 (4)	0.0047 (4)
O1	0.0771 (7)	0.0523 (6)	0.0546 (5)	0.0022 (5)	0.0182 (4)	0.0139 (4)
C3	0.0451 (6)	0.0414 (6)	0.0464 (6)	0.0032 (5)	−0.0009 (4)	0.0013 (5)
N1	0.0609 (6)	0.0439 (6)	0.0467 (6)	0.0103 (4)	0.0078 (4)	0.0111 (4)
C4	0.0426 (6)	0.0396 (6)	0.0431 (6)	−0.0032 (4)	0.0012 (4)	−0.0018 (5)
C2	0.0485 (7)	0.0411 (6)	0.0406 (6)	−0.0053 (5)	−0.0008 (4)	0.0020 (4)
C9	0.0478 (7)	0.0529 (7)	0.0517 (7)	0.0042 (5)	0.0020 (5)	0.0018 (5)
C7	0.0777 (9)	0.0568 (8)	0.0452 (7)	−0.0139 (7)	0.0074 (6)	−0.0002 (5)
C5	0.0488 (7)	0.0525 (7)	0.0584 (7)	0.0036 (5)	0.0066 (5)	0.0004 (5)
C8	0.0678 (9)	0.0585 (8)	0.0526 (7)	−0.0012 (6)	−0.0053 (6)	0.0085 (5)
C6	0.0614 (8)	0.0595 (8)	0.0613 (8)	−0.0038 (6)	0.0204 (6)	−0.0057 (6)
C1	0.0882 (11)	0.0756 (10)	0.0652 (9)	−0.0041 (8)	0.0305 (8)	0.0085 (8)

Geometric parameters (Å, º) top

O2—C2	1.2075 (15)	C9—H9A	0.9300
N2—C3	1.2694 (15)	C7—C6	1.367 (2)
N2—N1	1.3808 (13)	C7—C8	1.386 (2)
O1—C2	1.3453 (14)	C7—H7A	0.9300
O1—C1	1.4351 (18)	C5—C6	1.3868 (17)
C3—C4	1.4653 (16)	C5—H5A	0.9300
C3—H3A	0.9300	C8—H8A	0.9300
N1—C2	1.3420 (16)	C6—H6A	0.9300
N1—H1A	0.8600	C1—H1B	0.9600
C4—C9	1.3911 (18)	C1—H1C	0.9600
C4—C5	1.3912 (17)	C1—H1D	0.9600
C9—C8	1.3811 (18)

C3—N2—N1	115.28 (10)	C6—C7—H7A	120.2
C2—O1—C1	115.48 (11)	C8—C7—H7A	120.2
N2—C3—C4	121.47 (11)	C6—C5—C4	120.43 (13)
N2—C3—H3A	119.3	C6—C5—H5A	119.8
C4—C3—H3A	119.3	C4—C5—H5A	119.8
C2—N1—N2	118.29 (10)	C9—C8—C7	120.42 (13)
C2—N1—H1A	120.9	C9—C8—H8A	119.8
N2—N1—H1A	120.9	C7—C8—H8A	119.8
C9—C4—C5	118.66 (11)	C7—C6—C5	120.52 (13)
C9—C4—C3	121.84 (11)	C7—C6—H6A	119.7
C5—C4—C3	119.43 (11)	C5—C6—H6A	119.7
O2—C2—N1	126.35 (10)	O1—C1—H1B	109.5
O2—C2—O1	123.97 (11)	O1—C1—H1C	109.5
N1—C2—O1	109.67 (10)	H1B—C1—H1C	109.5
C8—C9—C4	120.35 (12)	O1—C1—H1D	109.5
C8—C9—H9A	119.8	H1B—C1—H1D	109.5
C4—C9—H9A	119.8	H1C—C1—H1D	109.5
C6—C7—C8	119.60 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.04	2.8986 (15)	179

Symmetry code: (i) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₂
M_r	178.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	12.278 (3), 7.8035 (16), 19.466 (4)
V (Å³)	1865.1 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.21 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16349, 2132, 1693
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.147, 1.08
No. of reflections	2132
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18

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···O2ⁱ	0.86	2.04	2.8986 (15)	179

Symmetry code: (i) −x+3/2, y+1/2, z.

Acknowledgements

The authors 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