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

Abstract

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,

• a = 6.6733 (5) Å

• b = 19.8940 (14) Å

• c = 7.7254 (5) Å

• V = 1025.61 (12) ų

• 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[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

Anomalous dispersion was negligible and Friedel pairs were merged before refinement. The H atoms attached to C7 and N2 were located in a difference map and their positions and U_iso values were freely refined. The other H atoms were geometrically placed (C—H = 0.95-0.98Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C).

Figures

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.

Crystal data

C10H12N2O2	F000 = 408
Mr = 192.22	Dx = 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 = 2.0–25.0º
b = 19.8940 (14) Å	µ = 0.09 mm−1
c = 7.7254 (5) Å	T = 123 (2) K
V = 1025.61 (12) Å3	Block, colourless
Z = 4	0.26 × 0.25 × 0.23 mm

Data collection

Bruker SMART CCD diffractometer	971 independent reflections
Radiation source: fine-focus sealed tube	935 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.022
T = 123(2) K	θmax = 25.0º
ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −7→7
Tmin = 0.965, Tmax = 0.968	k = −23→21
10169 measured reflections	l = −8→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0468P)2 + 0.0621P] where P = (Fo2 + 2Fc2)/3
S = 1.14	(Δ/σ)max = 0.048
971 reflections	Δρmax = 0.11 e Å−3
143 parameters	Δρmin = −0.08 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.