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

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.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.077
• Data-to-parameter ratio = 6.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.79
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.01

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total                971
           Count of symmetry unique reflns          975
           Completeness (_total/calc)             99.59%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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).

Related literature

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

S2. 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).

S3. 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).

Computing details

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

	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

Crystal data

C10H12N2O2	F(000) = 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 = 2.0–25.0°
b = 19.8940 (14) Å	µ = 0.09 mm^−1
c = 7.7254 (5) Å	T = 123 K
V = 1025.61 (12) Å^3	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)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 25.0°, θmin = 2.1°
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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: difmap and geom
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 0.0621P] where P = (Fo^2 + 2Fc^2)/3
971 reflections	(Δ/σ)max = 0.048
143 parameters	Δρmax = 0.11 e Å^−3
1 restraint	Δρmin = −0.09 e Å^−3

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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H10···O1^i	0.84 (4)	2.16 (4)	2.977 (2)	167
C2—H2A···Cg1^ii	0.95	2.96	3.827 (2)	156
C5—H5···Cg1^iii	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.