Methyl 2-[(E)-3-hydr­oxy-4-methoxy­benzyl­idene]hydrazinecarboxyl­ate

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

doi:10.1107/S1600536809018996

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1384

doi:10.1107/S1600536809018996

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Methyl 2-[(E)-3-hydroxy-4-methoxybenzylidene]hydrazinecarboxylate

Lu-Ping Lv,^a Tie-Ming Yu,^a Wen-Bo Yu,^a Wei-Wei Li ^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 of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 15 May 2009; accepted 19 May 2009; online 23 May 2009)

The title compound, C₁₀H₁₂N₂O₄, adopts a trans configuration with respect to the C=N bond. The hydrazinecarboxylate group is twisted from the benzene ring by 6.62 (5)° and an intramolecular O—H⋯O hydrogen bond occurs. In the crystal structure, molecules are linked into a two-dimensional network parallel to (100) by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds. In addition, weak C—H⋯π interactions are observed.

Related literature

For properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For Schiff base metal complexes, see: Kahwa et al. (1986 ); Santos et al. (2001 ). For a related structure, see: Shang et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₄
M_r = 224.22
Monoclinic, P 2₁ /c
a = 7.7223 (12) Å
b = 9.2106 (14) Å
c = 15.092 (2) Å
β = 100.944 (6)°
V = 1054.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.18 × 0.16 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.978, T_max = 0.982
5767 measured reflections
1944 independent reflections
1657 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.098
S = 1.05
1944 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.19 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⋯O1	0.82	2.28	2.6871 (13)	112
O2—H2⋯O3ⁱ	0.82	2.20	2.9303 (13)	148
N2—H2A⋯O3ⁱⁱ	0.86	2.44	3.1951 (15)	147
C8—H8⋯O3ⁱⁱ	0.93	2.51	3.3185 (16)	146
C10—H10A⋯Cg1ⁱⁱⁱ	0.96	2.87	3.6878 (18)	143
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C2–C7 ring.

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/S1600536809018996/ci2804sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018996/ci2804Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have attracted much attention 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 interesting properties (Borg et al., 1999). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). We report here the crystal structure of the title compound (Fig. 1).

The title molecule adopts a trans configuration with respect to the C═N bond. The hydrazinecarboxylate group is twisted from the benzene ring by 6.62 (5)°. The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007). An intramolecular O—H···O interaction is observed.

In the crystal structure, the molecules are linked into a two-dimensional network parallel to the (100) by O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1 and Fig.2). In addition, a C—H···π interaction is observed.

Related literature top

For properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For Schiff base metal complexes, see: Kahwa et al. (1986); Santos et al. (2001). For a related structure, see: Shang et al. (2007). Cg1 is the centroid of the C2–C7 ring.

Experimental top

3-Hydroxy-4-methoxy-benzaldehyde (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 4 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 75% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 398–401 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 the title compound. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Methyl 2-[(E)-3-hydroxy-4-methoxybenzylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₄	F(000) = 472
M_r = 224.22	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1944 reflections
a = 7.7223 (12) Å	θ = 2.6–25.5°
b = 9.2106 (14) Å	µ = 0.11 mm⁻¹
c = 15.092 (2) Å	T = 223 K
β = 100.944 (6)°	Block, colourless
V = 1054.0 (3) Å³	0.18 × 0.16 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1944 independent reflections
Radiation source: fine-focus sealed tube	1657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→8
T_min = 0.978, T_max = 0.982	k = −11→11
5767 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0545P)² + 0.1597P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1944 reflections	Δρ_max = 0.19 e Å⁻³
149 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (4)

Crystal data top

C₁₀H₁₂N₂O₄	V = 1054.0 (3) Å³
M_r = 224.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7223 (12) Å	µ = 0.11 mm⁻¹
b = 9.2106 (14) Å	T = 223 K
c = 15.092 (2) Å	0.18 × 0.16 × 0.15 mm
β = 100.944 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1944 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1657 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.982	R_int = 0.024
5767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1944 reflections	Δρ_min = −0.18 e Å⁻³
149 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
C9	1.14900 (17)	0.19752 (13)	0.79259 (8)	0.0395 (3)
C8	0.89788 (18)	0.11117 (13)	0.58309 (9)	0.0435 (3)
H8	0.8814	0.0133	0.5941	0.052*
C3	0.78128 (16)	0.37223 (13)	0.39017 (8)	0.0386 (3)
C5	0.84592 (17)	0.31881 (13)	0.47483 (8)	0.0392 (3)
H5	0.9053	0.3802	0.5193	0.047*
C7	0.82305 (17)	0.17208 (13)	0.49464 (8)	0.0399 (3)
C2	0.68958 (16)	0.28075 (14)	0.32243 (8)	0.0401 (3)
C6	0.73162 (19)	0.08300 (14)	0.42746 (9)	0.0475 (3)
H6	0.7149	−0.0143	0.4401	0.057*
C4	0.66479 (18)	0.13636 (14)	0.34190 (9)	0.0466 (3)
H4	0.6035	0.0753	0.2978	0.056*
C10	1.3093 (2)	0.17575 (17)	0.94154 (9)	0.0564 (4)
H10A	1.3936	0.2432	0.9261	0.085*
H10B	1.3697	0.1025	0.9810	0.085*
H10C	1.2281	0.2263	0.9714	0.085*
C1	0.5523 (2)	0.25850 (18)	0.16765 (10)	0.0575 (4)
H1A	0.6295	0.1791	0.1614	0.086*
H1B	0.5317	0.3150	0.1132	0.086*
H1C	0.4422	0.2214	0.1787	0.086*
O1	0.63158 (13)	0.34761 (10)	0.24138 (6)	0.0500 (3)
O4	1.21426 (13)	0.10865 (10)	0.86081 (6)	0.0513 (3)
O3	1.17310 (14)	0.32803 (9)	0.79258 (6)	0.0529 (3)
O2	0.80571 (14)	0.51620 (9)	0.37432 (6)	0.0520 (3)
H2	0.7894	0.5307	0.3197	0.078*
N1	0.98497 (14)	0.18969 (11)	0.64511 (7)	0.0420 (3)
N2	1.05406 (15)	0.12010 (11)	0.72457 (7)	0.0442 (3)
H2A	1.0369	0.0287	0.7307	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C9	0.0475 (7)	0.0337 (6)	0.0380 (7)	0.0026 (5)	0.0096 (5)	0.0032 (5)
C8	0.0531 (8)	0.0325 (6)	0.0440 (7)	−0.0037 (5)	0.0067 (6)	0.0023 (5)
C3	0.0427 (7)	0.0331 (6)	0.0406 (7)	0.0000 (5)	0.0091 (5)	−0.0006 (5)
C5	0.0441 (7)	0.0354 (6)	0.0372 (6)	−0.0039 (5)	0.0057 (5)	−0.0032 (5)
C7	0.0425 (7)	0.0369 (6)	0.0397 (7)	−0.0015 (5)	0.0067 (5)	0.0002 (5)
C2	0.0412 (7)	0.0415 (7)	0.0369 (7)	0.0025 (5)	0.0060 (5)	−0.0007 (5)
C6	0.0571 (8)	0.0335 (6)	0.0497 (8)	−0.0070 (6)	0.0045 (6)	−0.0007 (5)
C4	0.0518 (8)	0.0417 (7)	0.0430 (7)	−0.0061 (6)	0.0003 (6)	−0.0079 (5)
C10	0.0626 (9)	0.0631 (9)	0.0391 (8)	−0.0074 (7)	−0.0015 (6)	0.0067 (6)
C1	0.0618 (9)	0.0646 (9)	0.0411 (8)	−0.0054 (7)	−0.0030 (6)	−0.0032 (7)
O1	0.0606 (6)	0.0474 (5)	0.0377 (5)	0.0009 (4)	−0.0018 (4)	0.0008 (4)
O4	0.0664 (6)	0.0407 (5)	0.0416 (5)	−0.0009 (4)	−0.0027 (4)	0.0066 (4)
O3	0.0776 (7)	0.0341 (5)	0.0440 (5)	−0.0049 (4)	0.0038 (5)	0.0007 (4)
O2	0.0772 (7)	0.0348 (5)	0.0415 (5)	−0.0048 (4)	0.0053 (5)	0.0044 (4)
N1	0.0517 (6)	0.0348 (5)	0.0380 (6)	0.0009 (4)	0.0049 (5)	0.0046 (4)
N2	0.0602 (7)	0.0300 (5)	0.0393 (6)	−0.0015 (5)	0.0015 (5)	0.0040 (4)

Geometric parameters (Å, º) top

C9—O3	1.2164 (15)	C6—C4	1.3864 (19)
C9—O4	1.3369 (15)	C6—H6	0.93
C9—N2	1.3469 (16)	C4—H4	0.93
C8—N1	1.2698 (16)	C10—O4	1.4371 (16)
C8—C7	1.4621 (17)	C10—H10A	0.96
C8—H8	0.93	C10—H10B	0.96
C3—O2	1.3669 (14)	C10—H10C	0.96
C3—C5	1.3717 (17)	C1—O1	1.4241 (16)
C3—C2	1.4078 (17)	C1—H1A	0.96
C5—C7	1.4025 (17)	C1—H1B	0.96
C5—H5	0.93	C1—H1C	0.96
C7—C6	1.3885 (18)	O2—H2	0.82
C2—O1	1.3668 (15)	N1—N2	1.3750 (14)
C2—C4	1.3831 (19)	N2—H2A	0.86

O3—C9—O4	124.74 (12)	C2—C4—H4	120.1
O3—C9—N2	125.75 (11)	C6—C4—H4	120.1
O4—C9—N2	109.51 (10)	O4—C10—H10A	109.5
N1—C8—C7	121.11 (11)	O4—C10—H10B	109.5
N1—C8—H8	119.4	H10A—C10—H10B	109.5
C7—C8—H8	119.4	O4—C10—H10C	109.5
O2—C3—C5	118.24 (11)	H10A—C10—H10C	109.5
O2—C3—C2	121.38 (11)	H10B—C10—H10C	109.5
C5—C3—C2	120.37 (11)	O1—C1—H1A	109.5
C3—C5—C7	120.40 (11)	O1—C1—H1B	109.5
C3—C5—H5	119.8	H1A—C1—H1B	109.5
C7—C5—H5	119.8	O1—C1—H1C	109.5
C6—C7—C5	118.74 (12)	H1A—C1—H1C	109.5
C6—C7—C8	119.87 (11)	H1B—C1—H1C	109.5
C5—C7—C8	121.36 (11)	C2—O1—C1	117.31 (11)
O1—C2—C4	126.04 (11)	C9—O4—C10	116.53 (10)
O1—C2—C3	114.48 (11)	C3—O2—H2	109.5
C4—C2—C3	119.47 (11)	C8—N1—N2	116.16 (10)
C4—C6—C7	121.22 (12)	C9—N2—N1	118.88 (10)
C4—C6—H6	119.4	C9—N2—H2A	120.6
C7—C6—H6	119.4	N1—N2—H2A	120.6
C2—C4—C6	119.79 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	2.28	2.6871 (13)	112
O2—H2···O3ⁱ	0.82	2.20	2.9303 (13)	148
N2—H2A···O3ⁱⁱ	0.86	2.44	3.1951 (15)	147
C8—H8···O3ⁱⁱ	0.93	2.51	3.3185 (16)	146
C10—H10A···Cg1ⁱⁱⁱ	0.96	2.87	3.6878 (18)	143

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₄
M_r	224.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	7.7223 (12), 9.2106 (14), 15.092 (2)
β (°)	100.944 (6)
V (Å³)	1054.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.978, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5767, 1944, 1657
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.098, 1.05
No. of reflections	1944
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −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···O1	0.82	2.28	2.6871 (13)	112
O2—H2···O3ⁱ	0.82	2.20	2.9303 (13)	148
N2—H2A···O3ⁱⁱ	0.86	2.44	3.1951 (15)	147
C8—H8···O3ⁱⁱ	0.93	2.51	3.3185 (16)	146
C10—H10A···Cg1ⁱⁱⁱ	0.96	2.87	3.6878 (18)	143

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

Acknowledgements

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

References

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