Methyl (E)-N′-[1-(2,4-dihydroxy­phen­yl)ethyl­idene]hydrazinecarboxyl­ate

Lv, L.-P.; Li, W.-W.; Yu, W.-B.; Yu, T.-M.; Hu, X.-C.

doi:10.1107/S1600536809027317

organic compounds

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Volume 65| Part 8| August 2009| Page o1896

doi:10.1107/S1600536809027317

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Methyl (E)-N′-[1-(2,4-dihydroxyphenyl)ethylidene]hydrazinecarboxylate

Lu-Ping Lv,^a Wei-Wei Li,^a Wen-Bo Yu,^a Tie-Ming Yu ^a and Xian-Chao Hu ^b ^*

^aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, and ^bResearch Center for Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 11 July 2009; accepted 11 July 2009; online 18 July 2009)

The molecule of the title compound, C₁₀H₁₂N₂O₄, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the methyl hydrazinecarboxylate plane is 3.01 (6)°. An intramolecular O—H⋯N hydrogen bond is observed. In the crystal, molecules are linked into a two-dimensional network parallel to (10 $[\overline{1}]$ ) by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to the properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For a related structure, see: Lv et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₄
M_r = 224.22
Monoclinic, P 2₁ /n
a = 10.714 (5) Å
b = 8.700 (4) Å
c = 11.682 (6) Å
β = 107.872 (6)°
V = 1036.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.24 × 0.23 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS, Bruker, 2002 ) T_min = 0.977, T_max = 0.980
5096 measured reflections
1815 independent reflections
1355 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.131
S = 1.05
1815 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.84	2.557 (2)	145
O1—H1⋯O3ⁱ	0.82	1.98	2.791 (2)	170
N2—H2B⋯O2ⁱⁱ	0.86	2.35	3.185 (2)	164
C2—H2A⋯O3ⁱ	0.93	2.42	3.141 (3)	135
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536809027317/ci2854sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027317/ci2854Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attention for a long time, due to their pharmacological activities (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermidiates for 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, we report herein the crystal structure of the title compound.

The title molecule (Fig. 1) adopts a trans configuration with respect to the C═N double bond. The bond lengths and angles are comparable to those observed for (E)-methyl N'-[1-(4-methoxyphenyl)ethylidene]hydrazinecarboxylate (Lv et al., 2008). The dihedral angle between benzene (C1-C6) and O3/O4/N1/N2/C7-C10 planes is 3.01 (6)°. An intramolecular O2—H2···N1 hydrogen bond is observed.

In the crystal structure, intermolecular O—H···O, N—H···O and C–H···O hydrogen bonds (Table 1) link the molecules into a two-dimensional network parallel to the (101) (Fig. 2).

Related literature top

For general background to the properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Lv et al. (2008).

Experimental top

2,4-Dihydroxy-acetophenone (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (15 ml) and left for 2.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound (yield 93%, m.p. 475-478 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

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 the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Methyl (E)-N'-[1-(2,4-dihydroxyphenyl)ethylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₄	F(000) = 472
M_r = 224.22	D_x = 1.437 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1915 reflections
a = 10.714 (5) Å	θ = 2.3–25.0°
b = 8.700 (4) Å	µ = 0.11 mm⁻¹
c = 11.682 (6) Å	T = 223 K
β = 107.872 (6)°	Block, colourless
V = 1036.3 (9) Å³	0.24 × 0.23 × 0.19 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1815 independent reflections
Radiation source: fine-focus sealed tube	1355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS, Bruker, 2002)	h = −12→12
T_min = 0.977, T_max = 0.980	k = −10→10
5096 measured reflections	l = −13→13

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) = 0.131	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0586P)² + 0.2997P] where P = (F_o² + 2F_c²)/3
1815 reflections	(Δ/σ)_max = 0.025
149 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₄	V = 1036.3 (9) Å³
M_r = 224.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.714 (5) Å	µ = 0.11 mm⁻¹
b = 8.700 (4) Å	T = 223 K
c = 11.682 (6) Å	0.24 × 0.23 × 0.19 mm
β = 107.872 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1815 independent reflections
Absorption correction: multi-scan (SADABS, Bruker, 2002)	1355 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.980	R_int = 0.027
5096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
1815 reflections	Δρ_min = −0.18 e Å⁻³
149 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 > 2sigma(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
O4	0.75341 (14)	0.02754 (18)	0.04159 (13)	0.0531 (4)
O2	0.30274 (15)	0.34157 (19)	−0.17412 (12)	0.0549 (5)
H2	0.3710	0.2990	−0.1355	0.082*
O1	−0.00973 (15)	0.70770 (19)	−0.13812 (14)	0.0615 (5)
H1	−0.0390	0.6873	−0.2100	0.092*
O3	0.59381 (15)	0.1012 (2)	−0.12508 (13)	0.0592 (5)
C6	0.32217 (19)	0.4395 (2)	0.02586 (17)	0.0403 (5)
C7	0.44242 (19)	0.3525 (2)	0.08526 (18)	0.0426 (5)
C2	0.1513 (2)	0.5234 (2)	−0.15377 (18)	0.0461 (5)
H2A	0.1139	0.5203	−0.2369	0.055*
C9	0.64512 (19)	0.1050 (2)	−0.01725 (18)	0.0443 (5)
C1	0.26013 (19)	0.4342 (2)	−0.09982 (17)	0.0404 (5)
C3	0.0972 (2)	0.6171 (2)	−0.08632 (19)	0.0458 (5)
C5	0.2630 (2)	0.5360 (3)	0.09052 (19)	0.0501 (6)
H5	0.3002	0.5422	0.1735	0.060*
C4	0.1528 (2)	0.6219 (3)	0.03705 (19)	0.0522 (6)
H4	0.1160	0.6829	0.0836	0.063*
C10	0.8151 (2)	−0.0586 (3)	−0.0320 (2)	0.0615 (7)
H10A	0.7509	−0.1217	−0.0874	0.092*
H10B	0.8830	−0.1225	0.0184	0.092*
H10C	0.8526	0.0113	−0.0760	0.092*
C8	0.5058 (2)	0.3622 (3)	0.21894 (19)	0.0646 (7)
H8A	0.5988	0.3485	0.2374	0.097*
H8B	0.4708	0.2833	0.2577	0.097*
H8C	0.4882	0.4611	0.2471	0.097*
N2	0.60110 (16)	0.1850 (2)	0.06181 (15)	0.0469 (5)
H2B	0.6418	0.1831	0.1377	0.056*
N1	0.48811 (16)	0.2697 (2)	0.01548 (15)	0.0448 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0468 (9)	0.0614 (10)	0.0448 (9)	0.0087 (7)	0.0047 (7)	0.0031 (7)
O2	0.0550 (9)	0.0643 (11)	0.0377 (8)	0.0175 (8)	0.0030 (7)	−0.0073 (7)
O1	0.0555 (10)	0.0627 (11)	0.0593 (10)	0.0148 (8)	0.0072 (8)	−0.0074 (8)
O3	0.0557 (9)	0.0700 (11)	0.0409 (9)	−0.0038 (8)	−0.0012 (7)	−0.0013 (8)
C6	0.0421 (11)	0.0408 (12)	0.0367 (11)	−0.0074 (9)	0.0102 (9)	0.0013 (9)
C7	0.0427 (11)	0.0445 (12)	0.0380 (11)	−0.0073 (9)	0.0084 (9)	0.0079 (9)
C2	0.0478 (12)	0.0482 (13)	0.0362 (11)	0.0001 (10)	0.0041 (9)	−0.0042 (9)
C9	0.0403 (11)	0.0470 (13)	0.0401 (12)	−0.0083 (10)	0.0044 (9)	0.0045 (10)
C1	0.0432 (11)	0.0401 (12)	0.0361 (11)	−0.0026 (9)	0.0096 (9)	−0.0024 (9)
C3	0.0423 (11)	0.0439 (12)	0.0489 (12)	−0.0008 (9)	0.0107 (10)	−0.0023 (10)
C5	0.0568 (13)	0.0568 (14)	0.0357 (11)	−0.0069 (11)	0.0127 (10)	−0.0018 (10)
C4	0.0574 (13)	0.0538 (14)	0.0482 (13)	0.0002 (11)	0.0202 (11)	−0.0081 (11)
C10	0.0548 (14)	0.0669 (16)	0.0635 (16)	0.0034 (12)	0.0191 (12)	−0.0028 (13)
C8	0.0664 (15)	0.0796 (18)	0.0404 (13)	0.0092 (13)	0.0053 (11)	0.0068 (12)
N2	0.0413 (10)	0.0562 (11)	0.0370 (9)	0.0021 (8)	0.0031 (8)	0.0065 (8)
N1	0.0377 (9)	0.0485 (11)	0.0435 (10)	−0.0013 (8)	0.0055 (7)	0.0078 (8)

Geometric parameters (Å, º) top

O4—C9	1.335 (2)	C2—H2A	0.93
O4—C10	1.445 (3)	C9—N2	1.352 (3)
O2—C1	1.362 (2)	C3—C4	1.381 (3)
O2—H2	0.82	C5—C4	1.375 (3)
O1—C3	1.369 (2)	C5—H5	0.93
O1—H1	0.82	C4—H4	0.93
O3—C9	1.210 (2)	C10—H10A	0.96
C6—C5	1.404 (3)	C10—H10B	0.96
C6—C1	1.414 (3)	C10—H10C	0.96
C6—C7	1.472 (3)	C8—H8A	0.96
C7—N1	1.291 (3)	C8—H8B	0.96
C7—C8	1.502 (3)	C8—H8C	0.96
C2—C3	1.378 (3)	N2—N1	1.378 (2)
C2—C1	1.381 (3)	N2—H2B	0.86

C9—O4—C10	116.06 (17)	C4—C5—H5	118.4
C1—O2—H2	109.5	C6—C5—H5	118.4
C3—O1—H1	109.5	C5—C4—C3	119.5 (2)
C5—C6—C1	115.61 (19)	C5—C4—H4	120.2
C5—C6—C7	121.90 (19)	C3—C4—H4	120.2
C1—C6—C7	122.48 (19)	O4—C10—H10A	109.5
N1—C7—C6	115.85 (18)	O4—C10—H10B	109.5
N1—C7—C8	123.37 (19)	H10A—C10—H10B	109.5
C6—C7—C8	120.8 (2)	O4—C10—H10C	109.5
C3—C2—C1	121.02 (19)	H10A—C10—H10C	109.5
C3—C2—H2A	119.5	H10B—C10—H10C	109.5
C1—C2—H2A	119.5	C7—C8—H8A	109.5
O3—C9—O4	124.6 (2)	C7—C8—H8B	109.5
O3—C9—N2	125.6 (2)	H8A—C8—H8B	109.5
O4—C9—N2	109.78 (17)	C7—C8—H8C	109.5
O2—C1—C2	116.30 (17)	H8A—C8—H8C	109.5
O2—C1—C6	122.56 (18)	H8B—C8—H8C	109.5
C2—C1—C6	121.14 (19)	C9—N2—N1	117.11 (17)
O1—C3—C2	121.94 (19)	C9—N2—H2B	121.4
O1—C3—C4	118.56 (19)	N1—N2—H2B	121.4
C2—C3—C4	119.5 (2)	C7—N1—N2	120.52 (17)
C4—C5—C6	123.2 (2)

C5—C6—C7—N1	−178.96 (18)	C1—C2—C3—O1	179.24 (19)
C1—C6—C7—N1	−0.3 (3)	C1—C2—C3—C4	0.1 (3)
C5—C6—C7—C8	0.9 (3)	C1—C6—C5—C4	−0.6 (3)
C1—C6—C7—C8	179.6 (2)	C7—C6—C5—C4	178.17 (19)
C10—O4—C9—O3	3.7 (3)	C6—C5—C4—C3	−1.2 (3)
C10—O4—C9—N2	−177.44 (17)	O1—C3—C4—C5	−177.7 (2)
C3—C2—C1—O2	177.60 (19)	C2—C3—C4—C5	1.5 (3)
C3—C2—C1—C6	−2.0 (3)	O3—C9—N2—N1	−0.1 (3)
C5—C6—C1—O2	−177.40 (18)	O4—C9—N2—N1	−178.99 (16)
C7—C6—C1—O2	3.8 (3)	C6—C7—N1—N2	179.30 (16)
C5—C6—C1—C2	2.2 (3)	C8—C7—N1—N2	−0.5 (3)
C7—C6—C1—C2	−176.56 (19)	C9—N2—N1—C7	−178.00 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.84	2.557 (2)	145
O1—H1···O3ⁱ	0.82	1.98	2.791 (2)	170
N2—H2B···O2ⁱⁱ	0.86	2.35	3.185 (2)	164
C2—H2A···O3ⁱ	0.93	2.42	3.141 (3)	135

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₄
M_r	224.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	223
a, b, c (Å)	10.714 (5), 8.700 (4), 11.682 (6)
β (°)	107.872 (6)
V (Å³)	1036.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.23 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS, Bruker, 2002)
T_min, T_max	0.977, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	5096, 1815, 1355
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.05
No. of reflections	1815
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18

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
O2—H2···N1	0.82	1.84	2.557 (2)	145
O1—H1···O3ⁱ	0.82	1.98	2.791 (2)	170
N2—H2B···O2ⁱⁱ	0.86	2.35	3.185 (2)	164
C2—H2A···O3ⁱ	0.93	2.42	3.141 (3)	135

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

Acknowledgements

The authors thank Hangzhou Vocational and Technical College, China, for financial support.

References

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