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Acta Cryst. (2008). E64, o1748    [ doi:10.1107/S1600536808024434 ]

(E)-Methyl N'-[1-(2-hydroxyphenyl)ethylidene]hydrazinecarboxylate

B. Zhu and X.-W. Cheng

Abstract top

The molecule of the title compound, C10H12N2O3, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 8.98 (7)°. Intramolecular O-H...N and C-H...N hydrogen bonds are observed. Molecules are linked into chains along the c axis by N-H...O hydrogen bonds. In addition, C-H...[pi] interactions are observed.

Comment top

Benzaldehydehydrazone compounds have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermediates of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound is reported here.

The title molecule (Fig.1) adopts a trans configuration with respect to the C═N bond. The C9/C10/N1/N2/O2/O3 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/N1/N2/O2/O3 plane is 8.98 (7)°. The bond lengths and angles agree with those observed for methyl N'-((E)-1-phenylethylidene)hydrazinecarboxylate (Cheng, 2008). Intramolecular O—H···N and C—H···N hydrogen bonds are observed.

The molecules are linked into chains along the c axis by N—H···O hydrogen bonds. In addition, C—H···π interactions are observed (Table 1, Fig.2).

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Cheng (2008). Cg1 is the centroid of the C1–C6 ring.

Experimental top

2-Hydroxyacetophenone (1.36 g, 0.01 mol) and methyl hydrazinecarboxylate (0.9 g, 0.01 mol) were dissolved in stirred methanol (15 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 85% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 465–467 K).

Refinement top

H atoms were positioned geometrically (O-H = 0.82 Å, N-H = 0.86 Å and C-H = 0.93 or 0.96 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C). A rotating group model was used for the methyl groups.

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
[Figure 1] Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. Dashed lines indicate intramolecular hydrogen bonds.
[Figure 2] Fig. 2. Crystal packing of the title compound. Dashed lines indicate intermolecular hydrogen bonds.
(E)-Methyl N'-[1-(2-hydroxyphenyl)ethylidene]hydrazinecarboxylate top
Crystal data top
C10H12N2O3F000 = 440
Mr = 208.22Dx = 1.345 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1809 reflections
a = 8.6432 (8) Åθ = 2.5–25.0º
b = 12.6696 (11) ŵ = 0.10 mm−1
c = 9.9810 (9) ÅT = 273 (2) K
β = 109.837 (3)ºBlock, colourless
V = 1028.12 (16) Å30.28 × 0.24 × 0.23 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1809 independent reflections
Radiation source: fine-focus sealed tube1587 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 273(2) Kθmax = 25.1º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −10→9
Tmin = 0.973, Tmax = 0.979k = −14→13
10601 measured reflectionsl = −11→11
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0557P)2 + 0.2233P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.26 e Å−3
1809 reflectionsΔρmin = −0.12 e Å−3
140 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (3)
Secondary atom site location: difference Fourier map
Crystal data top
C10H12N2O3V = 1028.12 (16) Å3
Mr = 208.22Z = 4
Monoclinic, P21/cMo Kα
a = 8.6432 (8) ŵ = 0.10 mm−1
b = 12.6696 (11) ÅT = 273 (2) K
c = 9.9810 (9) Å0.28 × 0.24 × 0.23 mm
β = 109.837 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		1809 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1587 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.979Rint = 0.019
10601 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035140 parameters
wR(F2) = 0.107H-atom parameters constrained
S = 1.05Δρmax = 0.26 e Å−3
1809 reflectionsΔρmin = −0.12 e Å−3
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
xyzUiso*/Ueq
C10.62350 (16)−0.02927 (10)0.76460 (14)0.0409 (3)
C60.67306 (16)−0.04195 (10)0.91401 (14)0.0403 (3)
C70.79166 (16)0.03028 (10)1.01395 (13)0.0404 (3)
C91.01051 (17)0.25416 (11)0.97214 (14)0.0430 (3)
C20.51172 (17)−0.09885 (12)0.67429 (16)0.0497 (4)
H20.4799−0.08960.57620.060*
C30.44767 (19)−0.18132 (12)0.72853 (18)0.0577 (4)
H30.3740−0.22790.66710.069*
C50.60373 (19)−0.12639 (12)0.96486 (17)0.0538 (4)
H50.6335−0.13651.06270.065*
C40.4927 (2)−0.19499 (14)0.87417 (19)0.0623 (5)
H40.4484−0.25020.91090.075*
C101.1944 (2)0.39775 (14)1.01329 (19)0.0650 (5)
H10A1.22200.36680.93650.098*
H10B1.29330.41781.08830.098*
H10C1.12720.45910.97940.098*
C80.8508 (2)0.00907 (13)1.17083 (15)0.0595 (4)
H8A0.95530.04271.21490.089*
H8B0.8622−0.06571.18710.089*
H8C0.77270.03651.21100.089*
O10.68111 (13)0.04936 (8)0.70165 (10)0.0535 (3)
H10.74640.08570.76310.080*
O20.98628 (13)0.25492 (8)0.84561 (10)0.0539 (3)
O31.10557 (14)0.32236 (9)1.06669 (11)0.0603 (3)
N10.83941 (13)0.10946 (9)0.95665 (11)0.0416 (3)
N20.94739 (14)0.18236 (10)1.04034 (11)0.0470 (3)
H2A0.97360.18241.13150.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0454 (7)0.0377 (7)0.0412 (7)0.0050 (5)0.0167 (6)0.0020 (5)
C60.0439 (7)0.0363 (7)0.0421 (7)0.0051 (5)0.0167 (6)0.0023 (5)
C70.0460 (7)0.0404 (7)0.0361 (7)0.0071 (6)0.0156 (6)0.0029 (5)
C90.0477 (8)0.0444 (8)0.0381 (7)−0.0012 (6)0.0163 (6)−0.0035 (6)
C20.0521 (8)0.0504 (9)0.0447 (8)0.0007 (6)0.0138 (6)−0.0056 (6)
C30.0532 (9)0.0511 (9)0.0655 (10)−0.0078 (7)0.0156 (8)−0.0084 (7)
C50.0632 (9)0.0506 (9)0.0495 (8)−0.0015 (7)0.0216 (7)0.0089 (7)
C40.0659 (10)0.0522 (9)0.0710 (11)−0.0131 (7)0.0260 (8)0.0056 (8)
C100.0688 (10)0.0671 (11)0.0637 (10)−0.0237 (9)0.0284 (8)−0.0088 (8)
C80.0833 (11)0.0526 (9)0.0384 (8)−0.0026 (8)0.0151 (7)0.0045 (7)
O10.0721 (7)0.0501 (6)0.0362 (5)−0.0107 (5)0.0155 (5)0.0007 (4)
O20.0721 (7)0.0544 (7)0.0368 (6)−0.0094 (5)0.0206 (5)−0.0010 (4)
O30.0716 (7)0.0673 (7)0.0464 (6)−0.0274 (6)0.0258 (5)−0.0137 (5)
N10.0460 (6)0.0423 (6)0.0358 (6)−0.0029 (5)0.0130 (5)−0.0021 (5)
N20.0563 (7)0.0524 (7)0.0319 (6)−0.0097 (5)0.0145 (5)−0.0034 (5)
Geometric parameters (Å, °) top
C1—O11.3592 (16)C5—C41.381 (2)
C1—C21.390 (2)C5—H50.93
C1—C61.4141 (19)C4—H40.93
C6—C51.4027 (19)C10—O31.4364 (19)
C6—C71.4796 (19)C10—H10A0.96
C7—N11.2899 (17)C10—H10B0.96
C7—C81.4974 (18)C10—H10C0.96
C9—O21.2081 (16)C8—H8A0.96
C9—O31.3364 (17)C8—H8B0.96
C9—N21.3567 (17)C8—H8C0.96
C2—C31.377 (2)O1—H10.82
C2—H20.93N1—N21.3757 (16)
C3—C41.382 (2)N2—H2A0.86
C3—H30.93
O1—C1—C2116.62 (12)C5—C4—C3119.71 (15)
O1—C1—C6122.91 (12)C5—C4—H4120.1
C2—C1—C6120.46 (13)C3—C4—H4120.1
C5—C6—C1117.03 (13)O3—C10—H10A109.5
C5—C6—C7120.73 (12)O3—C10—H10B109.5
C1—C6—C7122.23 (12)H10A—C10—H10B109.5
N1—C7—C6115.77 (11)O3—C10—H10C109.5
N1—C7—C8123.80 (13)H10A—C10—H10C109.5
C6—C7—C8120.43 (12)H10B—C10—H10C109.5
O2—C9—O3125.45 (13)C7—C8—H8A109.5
O2—C9—N2124.98 (13)C7—C8—H8B109.5
O3—C9—N2109.56 (11)H8A—C8—H8B109.5
C3—C2—C1120.68 (14)C7—C8—H8C109.5
C3—C2—H2119.7H8A—C8—H8C109.5
C1—C2—H2119.7H8B—C8—H8C109.5
C2—C3—C4120.09 (14)C1—O1—H1109.5
C2—C3—H3120.0C9—O3—C10116.48 (11)
C4—C3—H3120.0C7—N1—N2120.41 (11)
C4—C5—C6122.01 (14)C9—N2—N1116.81 (11)
C4—C5—H5119.0C9—N2—H2A121.6
C6—C5—H5119.0N1—N2—H2A121.6
O1—C1—C6—C5179.88 (12)C1—C6—C5—C40.4 (2)
C2—C1—C6—C5−0.42 (19)C7—C6—C5—C4179.96 (14)
O1—C1—C6—C70.3 (2)C6—C5—C4—C30.2 (3)
C2—C1—C6—C7−179.99 (12)C2—C3—C4—C5−0.8 (3)
C5—C6—C7—N1−175.42 (12)O2—C9—O3—C10−4.6 (2)
C1—C6—C7—N14.12 (19)N2—C9—O3—C10174.30 (13)
C5—C6—C7—C85.3 (2)C6—C7—N1—N2178.87 (11)
C1—C6—C7—C8−175.19 (13)C8—C7—N1—N2−1.8 (2)
O1—C1—C2—C3179.57 (13)O2—C9—N2—N1−4.4 (2)
C6—C1—C2—C3−0.2 (2)O3—C9—N2—N1176.72 (11)
C1—C2—C3—C40.8 (2)C7—N1—N2—C9170.54 (12)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.5625 (14)145
N2—H2A···O2i0.862.253.0550 (14)156
C8—H8A···N20.962.472.820 (2)101
C8—H8C···Cg1ii0.962.933.803 (2)151
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.5625 (14)145
N2—H2A···O2i0.862.253.0550 (14)156
C8—H8A···N20.962.472.820 (2)101
C8—H8C···Cg1ii0.962.933.803 (2)151
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1.
Acknowledgements top

The authors acknowledge financial support from Zhejiang Police College, China.

references
References top

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342.

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Cheng, X.-W. (2008). Acta Cryst. E64, o1384.

Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.

Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.