Methyl N′-[(E)-1-phenyl­ethyl­idene]hydrazinecarboxyl­ate

Cheng, X.-W.

doi:10.1107/S1600536808019259

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1384

doi:10.1107/S1600536808019259

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Methyl N′-[(E)-1-phenylethylidene]hydrazinecarboxylate

Xiang-Wei Cheng ^a ^*

^aZhejiang Police College Experience Center, Zhejiang Police College, Hangzhou 310053, People's Republic of China
^*Correspondence e-mail: zpccxw@126.com

(Received 24 June 2008; accepted 25 June 2008; online 5 July 2008)

The molecule of the title compound, C₁₀H₁₂N₂O₂, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the phenyl ring and the hydrazine carboxylic acid mean plane is 25.23 (9)°. In the crystal structure, molecules are linked into chains by N—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For a related structure and background, see: Cheng (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₂
M_r = 192.22
Orthorhombic, P c a 2₁
a = 6.6733 (5) Å
b = 19.8940 (14) Å
c = 7.7254 (5) Å
V = 1025.61 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 123 (2) K
0.26 × 0.25 × 0.23 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.965, T_max = 0.968
10169 measured reflections
971 independent reflections
935 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.076
S = 1.14
971 reflections
143 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.09 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H10⋯O1ⁱ	0.84 (4)	2.16 (4)	2.977 (2)	167
C2—H2A⋯Cg1ⁱⁱ	0.95	2.96	3.827 (2)	156
C5—H5⋯Cg1ⁱⁱⁱ	0.95	2.88	3.753 (2)	156
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 I, global. DOI: 10.1107/S1600536808019259/hb2751sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019259/hb2751Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of benzaldehydehydrazone derivatives (Cheng, 2008), we now report the synthesis and structure of the title compound, (I).

The title molecule (Fig. 1) adopts a trans configuration with respect to the C=N bond. The C9/C10/N2/O1/O2 plane of the hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C1—C6 ring and the C9/C10/N2/O1/O2 plane is 25.23 (9)°. Otherwise, the bond lengths and angles ij (I) agree with those observed for (E)-methyl N'-(4-hydroxybenzylidene) hydrazinecarboxylate (Cheng, 2008).

In the crystal structure, N–H···O hydrogen bonds and C–H···π interactions (Table 1) link the molecules into chains (Fig. 2).

Related literature top

For a related structure and background, see: Cheng (2008). Cg1 is the centroid of the C1–C6 ring

Experimental top

Acetophenone (1.2 g, 0.01 mol) and methyl hydrazinecarboxylate (0.9 g, 0.01 mol) were dissolved in stirred methanol (20 ml) and left for 2 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 450–452 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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), showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
	Fig. 2. Crystal packing of (I), viewed approximately down the a axis. Dashed lines indicate hydrogen bonds.

Methyl N'-[(E)-1-phenylethylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₂	F(000) = 408
M_r = 192.22	D_x = 1.245 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 971 reflections
a = 6.6733 (5) Å	θ = 2.0–25.0°
b = 19.8940 (14) Å	µ = 0.09 mm⁻¹
c = 7.7254 (5) Å	T = 123 K
V = 1025.61 (12) Å³	Block, colourless
Z = 4	0.26 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD diffractometer	971 independent reflections
Radiation source: fine-focus sealed tube	935 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
T_min = 0.965, T_max = 0.968	k = −23→21
10169 measured reflections	l = −8→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)] = 0.028	Hydrogen site location: difmap and geom
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0468P)² + 0.0621P] where P = (F_o² + 2F_c²)/3
971 reflections	(Δ/σ)_max = 0.048
143 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.09 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₂	V = 1025.61 (12) Å³
M_r = 192.22	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 6.6733 (5) Å	µ = 0.09 mm⁻¹
b = 19.8940 (14) Å	T = 123 K
c = 7.7254 (5) Å	0.26 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD diffractometer	971 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	935 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.022
10169 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.11 e Å⁻³
971 reflections	Δρ_min = −0.09 e Å⁻³
143 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	0.8998 (2)	0.42251 (7)	0.4199 (2)	0.0606 (4)
O1	0.9765 (2)	0.37588 (7)	0.1622 (2)	0.0563 (4)
N2	0.7026 (3)	0.34290 (8)	0.3197 (2)	0.0491 (4)
N1	0.6763 (2)	0.28503 (7)	0.2224 (2)	0.0472 (4)
C6	0.5017 (3)	0.18464 (9)	0.1633 (3)	0.0467 (4)
C8	0.5153 (3)	0.25135 (9)	0.2518 (2)	0.0471 (4)
C9	0.8707 (3)	0.37937 (9)	0.2891 (3)	0.0448 (4)
C4	0.6331 (3)	0.16677 (11)	0.0313 (4)	0.0632 (6)
H4	0.7287	0.1986	−0.0087	0.076*
C5	0.3635 (3)	0.13717 (10)	0.2157 (3)	0.0610 (5)
H5	0.2700	0.1480	0.3041	0.073*
C7	0.3524 (4)	0.27326 (16)	0.3717 (4)	0.0703 (7)
C2	0.6270 (4)	0.10375 (11)	−0.0424 (4)	0.0688 (7)
H2A	0.7188	0.0926	−0.1320	0.083*
C1	0.4902 (4)	0.05692 (10)	0.0119 (4)	0.0634 (6)
H1	0.4865	0.0135	−0.0393	0.076*
C10	1.0751 (3)	0.46413 (12)	0.4084 (4)	0.0729 (7)
H10A	1.0816	0.4937	0.5096	0.109*
H10B	1.0684	0.4914	0.3029	0.109*
H10C	1.1949	0.4357	0.4048	0.109*
C3	0.3594 (4)	0.07359 (11)	0.1404 (4)	0.0665 (6)
H3	0.2642	0.0414	0.1792	0.080*
H10	0.642 (4)	0.3456 (12)	0.414 (5)	0.074 (8)*
H11	0.239 (7)	0.2525 (14)	0.336 (5)	0.100 (9)*
H12	0.347 (4)	0.3212 (16)	0.373 (5)	0.092 (9)*
H13	0.400 (8)	0.261 (2)	0.480 (9)	0.16 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0663 (8)	0.0588 (8)	0.0566 (9)	−0.0113 (7)	0.0026 (8)	−0.0173 (7)
O1	0.0578 (7)	0.0621 (9)	0.0488 (8)	−0.0081 (6)	0.0045 (7)	−0.0092 (7)
N2	0.0621 (10)	0.0459 (8)	0.0394 (9)	−0.0059 (7)	0.0030 (8)	−0.0046 (7)
N1	0.0612 (8)	0.0410 (7)	0.0393 (8)	−0.0045 (6)	−0.0020 (7)	−0.0006 (7)
C6	0.0555 (10)	0.0438 (9)	0.0408 (10)	−0.0039 (8)	−0.0054 (8)	0.0032 (8)
C8	0.0562 (10)	0.0469 (9)	0.0381 (10)	−0.0007 (8)	−0.0028 (8)	0.0023 (8)
C9	0.0507 (9)	0.0410 (9)	0.0428 (10)	0.0029 (7)	−0.0068 (8)	−0.0024 (8)
C4	0.0729 (13)	0.0512 (11)	0.0656 (14)	−0.0112 (10)	0.0152 (12)	−0.0035 (11)
C5	0.0684 (12)	0.0596 (11)	0.0549 (12)	−0.0151 (10)	0.0044 (10)	−0.0012 (11)
C7	0.0636 (13)	0.0744 (17)	0.0728 (18)	−0.0115 (12)	0.0119 (12)	−0.0210 (14)
C2	0.0804 (14)	0.0563 (12)	0.0698 (16)	−0.0010 (11)	0.0110 (13)	−0.0104 (12)
C1	0.0815 (14)	0.0429 (11)	0.0660 (14)	−0.0022 (10)	−0.0125 (12)	−0.0032 (10)
C10	0.0673 (13)	0.0730 (15)	0.0786 (16)	−0.0169 (11)	−0.0033 (13)	−0.0243 (14)
C3	0.0798 (13)	0.0547 (12)	0.0650 (15)	−0.0209 (10)	−0.0032 (12)	0.0034 (11)

Geometric parameters (Å, º) top

O2—C9	1.340 (2)	C5—C3	1.392 (3)
O2—C10	1.436 (2)	C5—H5	0.9500
O1—C9	1.211 (3)	C7—H11	0.91 (4)
N2—C9	1.357 (2)	C7—H12	0.95 (3)
N2—N1	1.386 (2)	C7—H13	0.93 (6)
N2—H10	0.84 (3)	C2—C1	1.370 (3)
N1—C8	1.286 (2)	C2—H2A	0.9500
C6—C5	1.381 (3)	C1—C3	1.363 (4)
C6—C4	1.391 (3)	C1—H1	0.9500
C6—C8	1.496 (3)	C10—H10A	0.9800
C8—C7	1.494 (3)	C10—H10B	0.9800
C4—C2	1.378 (3)	C10—H10C	0.9800
C4—H4	0.9500	C3—H3	0.9500

C9—O2—C10	116.16 (17)	C8—C7—H12	109 (2)
C9—N2—N1	117.04 (17)	H11—C7—H12	115 (3)
C9—N2—H10	121.1 (18)	C8—C7—H13	103 (3)
N1—N2—H10	117.8 (18)	H11—C7—H13	116 (4)
C8—N1—N2	116.30 (16)	H12—C7—H13	106 (4)
C5—C6—C4	117.5 (2)	C1—C2—C4	120.8 (2)
C5—C6—C8	120.90 (19)	C1—C2—H2A	119.6
C4—C6—C8	121.57 (17)	C4—C2—H2A	119.6
N1—C8—C7	124.42 (19)	C3—C1—C2	119.0 (2)
N1—C8—C6	115.63 (16)	C3—C1—H1	120.5
C7—C8—C6	119.88 (18)	C2—C1—H1	120.5
O1—C9—O2	124.28 (17)	O2—C10—H10A	109.5
O1—C9—N2	126.33 (18)	O2—C10—H10B	109.5
O2—C9—N2	109.35 (17)	H10A—C10—H10B	109.5
C2—C4—C6	121.1 (2)	O2—C10—H10C	109.5
C2—C4—H4	119.4	H10A—C10—H10C	109.5
C6—C4—H4	119.4	H10B—C10—H10C	109.5
C6—C5—C3	120.8 (2)	C1—C3—C5	120.8 (2)
C6—C5—H5	119.6	C1—C3—H3	119.6
C3—C5—H5	119.6	C5—C3—H3	119.6
C8—C7—H11	107 (2)

C9—N2—N1—C8	−179.38 (17)	N1—N2—C9—O2	−164.20 (15)
N2—N1—C8—C7	4.7 (3)	C5—C6—C4—C2	−0.9 (3)
N2—N1—C8—C6	−172.29 (15)	C8—C6—C4—C2	176.1 (2)
C5—C6—C8—N1	164.0 (2)	C4—C6—C5—C3	1.1 (3)
C4—C6—C8—N1	−12.9 (3)	C8—C6—C5—C3	−175.9 (2)
C5—C6—C8—C7	−13.1 (3)	C6—C4—C2—C1	0.3 (4)
C4—C6—C8—C7	170.0 (3)	C4—C2—C1—C3	0.0 (4)
C10—O2—C9—O1	−3.3 (3)	C2—C1—C3—C5	0.2 (4)
C10—O2—C9—N2	178.85 (18)	C6—C5—C3—C1	−0.8 (4)
N1—N2—C9—O1	18.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H10···O1ⁱ	0.84 (4)	2.16 (4)	2.977 (2)	167
C2—H2A···Cg1ⁱⁱ	0.95	2.96	3.827 (2)	156
C5—H5···Cg1ⁱⁱⁱ	0.95	2.88	3.753 (2)	156

Symmetry codes: (i) −x+3/2, y, z+1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₂
M_r	192.22
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	123
a, b, c (Å)	6.6733 (5), 19.8940 (14), 7.7254 (5)
V (Å³)	1025.61 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.25 × 0.23

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.965, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	10169, 971, 935
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.076, 1.14
No. of reflections	971
No. of parameters	143
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)	0.11, −0.09

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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—H10···O1ⁱ	0.84 (4)	2.16 (4)	2.977 (2)	167
C2—H2A···Cg1ⁱⁱ	0.95	2.96	3.827 (2)	156
C5—H5···Cg1ⁱⁱⁱ	0.95	2.88	3.753 (2)	156

Symmetry codes: (i) −x+3/2, y, z+1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+1/2, y, z+1/2.

Acknowledgements

The author acknowledges financial support from Zhejiang Police College, China.

References

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheng, X.-W. (2008). Acta Cryst. E64, o1302. 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