Methyl 3-(4-methyl­benzyl­idene)carbazate

Li, Y.-F.; Zhang, F.-G.; Jian, F.-F.

doi:10.1107/S160053681001799X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1429

https://doi.org/10.1107/S160053681001799X

Open

access

Methyl 3-(4-methylbenzylidene)carbazate

Yu-Feng Li,^a Fu-Gong Zhang ^b and Fang-Fang Jian ^c ^*

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

(Received 12 May 2010; accepted 15 May 2010; online 22 May 2010)

The title compound, C₁₀H₁₂N₂O₂, was prepared by the reaction of methyl carbazate and 4-methylbenzaldehyde. The dihedral angle between the benzene ring and the carbazate fragment is 20.86 (10)°. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen bonds.

Related literature

For background to Schiff bases, see: Cimerman et al. (1997 ). For C=N bond lengths, see: Girgis (2006 ). For a related structure, see: Li et al. (2009 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₂
M_r = 192.22
Monoclinic, P 2₁ /c
a = 10.038 (2) Å
b = 13.308 (3) Å
c = 7.7923 (16) Å
β = 99.71 (3)°
V = 1026.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
9493 measured reflections
2322 independent reflections
1528 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.175
S = 1.06
2322 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.00	2.8615 (18)	176
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S160053681001799X/hg2684sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001799X/hg2684Isup2.hkl

checkCIF report

Comment top

Schiff bases have received considerable attention in the literature. They are attractive from several points of view, such as the possibility of analytical application (Cimerman, et al., 1997). As part of our search for new Schiff base compounds we synthesized the title compound (I), and describe its structure here.

The molcular structure of (I) is shown in Fig. 1. The C8—N2 bond length of 1.273 (2)Å is comparable with C—N double bond [1.281 (2) Å] reported (Girgis, 2006). In the crystal structure, molecules are linked by intermolecular N—H···O hydrogen bonds.

Related literature top

For background to Schiff bases, see: Cimerman et al. (1997). For C═ N bond lengths, see: Girgis (2006). For a related structure, see: Li et al. (2009).

Experimental top

A mixture of methyl carbazate (0.1 mol), and 4-methylbenzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.085 mol, yield 85%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Structure description top

For background to Schiff bases, see: Cimerman et al. (1997). For C═ N bond lengths, see: Girgis (2006). For a related structure, see: Li et al. (2009).

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 and the atom-numbering scheme.

Methyl 3-(4-methylbenzylidene)carbazate top

Crystal data top

C₁₀H₁₂N₂O₂	F(000) = 408
M_r = 192.22	D_x = 1.244 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1798 reflections
a = 10.038 (2) Å	θ = 3.5–25.2°
b = 13.308 (3) Å	µ = 0.09 mm⁻¹
c = 7.7923 (16) Å	T = 293 K
β = 99.71 (3)°	Blcok, colorless
V = 1026.1 (4) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1528 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
phi and ω scans	h = −13→12
9493 measured reflections	k = −17→17
2322 independent reflections	l = −9→10

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1077P)²] where P = (F_o² + 2F_c²)/3
2322 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₂	V = 1026.1 (4) Å³
M_r = 192.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.038 (2) Å	µ = 0.09 mm⁻¹
b = 13.308 (3) Å	T = 293 K
c = 7.7923 (16) Å	0.22 × 0.20 × 0.18 mm
β = 99.71 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1528 reflections with I > 2σ(I)
9493 measured reflections	R_int = 0.043
2322 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.06	Δρ_max = 0.26 e Å⁻³
2322 reflections	Δρ_min = −0.23 e Å⁻³
127 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.44060 (12)	0.82548 (9)	0.19195 (16)	0.0656 (4)
C9	0.55062 (16)	0.81674 (12)	0.1159 (2)	0.0531 (4)
N2	0.75692 (13)	0.73089 (10)	0.14969 (17)	0.0559 (4)
O1	0.56744 (12)	0.86340 (9)	−0.01208 (15)	0.0636 (4)
C5	0.95735 (16)	0.62998 (12)	0.1941 (2)	0.0540 (4)
N1	0.63541 (14)	0.74964 (11)	0.20247 (18)	0.0617 (4)
H1A	0.6141	0.7184	0.2906	0.074*
C8	0.82561 (17)	0.66004 (13)	0.2311 (2)	0.0580 (4)
H8A	0.7903	0.6261	0.3176	0.070*
C3	1.15344 (17)	0.65532 (14)	0.0599 (2)	0.0661 (5)
H3A	1.2004	0.6951	−0.0078	0.079*
C2	1.20961 (17)	0.56483 (14)	0.1252 (2)	0.0623 (5)
C7	1.13692 (18)	0.50763 (15)	0.2245 (2)	0.0683 (5)
H7A	1.1719	0.4465	0.2692	0.082*
C6	1.01357 (17)	0.53927 (13)	0.2585 (2)	0.0629 (5)
H6A	0.9668	0.4992	0.3260	0.076*
C4	1.02987 (18)	0.68754 (13)	0.0931 (2)	0.0647 (5)
H4A	0.9947	0.7484	0.0475	0.078*
C10	0.3380 (2)	0.89244 (15)	0.1047 (3)	0.0789 (6)
H10A	0.2630	0.8938	0.1665	0.118*
H10B	0.3080	0.8693	−0.0120	0.118*
H10C	0.3749	0.9589	0.1017	0.118*
C1	1.3469 (2)	0.53239 (18)	0.0914 (3)	0.0857 (6)
H1B	1.3699	0.4687	0.1463	0.128*
H1C	1.4131	0.5815	0.1383	0.128*
H1D	1.3449	0.5263	−0.0317	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0612 (7)	0.0707 (8)	0.0700 (8)	0.0078 (5)	0.0254 (6)	0.0082 (6)
C9	0.0607 (10)	0.0489 (8)	0.0527 (9)	−0.0029 (7)	0.0181 (8)	−0.0056 (7)
N2	0.0573 (8)	0.0566 (8)	0.0561 (8)	0.0004 (6)	0.0165 (6)	−0.0012 (6)
O1	0.0813 (9)	0.0577 (7)	0.0566 (7)	0.0059 (6)	0.0251 (6)	0.0061 (5)
C5	0.0561 (9)	0.0530 (9)	0.0517 (9)	−0.0046 (7)	0.0059 (7)	−0.0048 (7)
N1	0.0632 (9)	0.0686 (9)	0.0580 (9)	0.0076 (7)	0.0241 (7)	0.0119 (7)
C8	0.0613 (10)	0.0600 (10)	0.0535 (9)	−0.0063 (8)	0.0121 (8)	0.0016 (7)
C3	0.0633 (10)	0.0656 (11)	0.0719 (12)	−0.0027 (8)	0.0187 (9)	0.0010 (8)
C2	0.0575 (9)	0.0670 (11)	0.0597 (10)	0.0026 (8)	0.0025 (8)	−0.0105 (8)
C7	0.0672 (11)	0.0635 (11)	0.0698 (11)	0.0086 (8)	−0.0011 (9)	0.0068 (8)
C6	0.0629 (10)	0.0635 (10)	0.0606 (10)	−0.0035 (8)	0.0052 (8)	0.0096 (8)
C4	0.0675 (11)	0.0547 (9)	0.0736 (12)	0.0034 (8)	0.0169 (9)	0.0050 (8)
C10	0.0678 (12)	0.0721 (12)	0.0987 (15)	0.0134 (9)	0.0196 (11)	0.0115 (11)
C1	0.0677 (12)	0.1015 (15)	0.0883 (14)	0.0137 (11)	0.0145 (10)	−0.0081 (12)

Geometric parameters (Å, º) top

O2—C9	1.343 (2)	C3—H3A	0.9300
O2—C10	1.442 (2)	C2—C7	1.379 (3)
C9—O1	1.2108 (19)	C2—C1	1.509 (3)
C9—N1	1.335 (2)	C7—C6	1.375 (2)
N2—C8	1.273 (2)	C7—H7A	0.9300
N2—N1	1.3742 (19)	C6—H6A	0.9300
C5—C4	1.389 (2)	C4—H4A	0.9300
C5—C6	1.390 (2)	C10—H10A	0.9600
C5—C8	1.456 (2)	C10—H10B	0.9600
N1—H1A	0.8600	C10—H10C	0.9600
C8—H8A	0.9300	C1—H1B	0.9600
C3—C4	1.378 (2)	C1—H1C	0.9600
C3—C2	1.389 (3)	C1—H1D	0.9600

C9—O2—C10	114.86 (13)	C6—C7—H7A	119.4
O1—C9—N1	126.40 (15)	C2—C7—H7A	119.4
O1—C9—O2	123.93 (15)	C7—C6—C5	121.34 (17)
N1—C9—O2	109.67 (14)	C7—C6—H6A	119.3
C8—N2—N1	114.77 (14)	C5—C6—H6A	119.3
C4—C5—C6	117.63 (16)	C3—C4—C5	120.62 (17)
C4—C5—C8	122.74 (16)	C3—C4—H4A	119.7
C6—C5—C8	119.61 (16)	C5—C4—H4A	119.7
C9—N1—N2	119.52 (13)	O2—C10—H10A	109.5
C9—N1—H1A	120.2	O2—C10—H10B	109.5
N2—N1—H1A	120.2	H10A—C10—H10B	109.5
N2—C8—C5	122.59 (16)	O2—C10—H10C	109.5
N2—C8—H8A	118.7	H10A—C10—H10C	109.5
C5—C8—H8A	118.7	H10B—C10—H10C	109.5
C4—C3—C2	121.59 (17)	C2—C1—H1B	109.5
C4—C3—H3A	119.2	C2—C1—H1C	109.5
C2—C3—H3A	119.2	H1B—C1—H1C	109.5
C7—C2—C3	117.61 (17)	C2—C1—H1D	109.5
C7—C2—C1	121.67 (17)	H1B—C1—H1D	109.5
C3—C2—C1	120.70 (18)	H1C—C1—H1D	109.5
C6—C7—C2	121.21 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.00	2.8615 (18)	176

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₂
M_r	192.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.038 (2), 13.308 (3), 7.7923 (16)
β (°)	99.71 (3)
V (Å³)	1026.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9493, 2322, 1528
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.175, 1.06
No. of reflections	2322
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

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···O1ⁱ	0.86	2.00	2.8615 (18)	176.0

Symmetry code: (i) x, −y+3/2, z+1/2.

References

Bruker (1997). SMART, SAINT and SADABS. 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
Girgis, A. S. (2006). J. Chem. Res. pp. 81–85. CrossRef Google Scholar
Li, Y.-F., Liu, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2959. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1429

https://doi.org/10.1107/S160053681001799X

Open

access