(E)-Methyl N′-(2-hydr­oxy-3-methoxy­benzyl­idene)hydrazinecarboxyl­ate

Lv, L.-P.; Yu, W.-B.; Li, W.-W.; Zhang, Y.-Z.; Hu, X.-C.

doi:10.1107/S1600536809021631

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1548

doi:10.1107/S1600536809021631

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(E)-Methyl N′-(2-hydroxy-3-methoxybenzylidene)hydrazinecarboxylate

Lu-Ping Lv,^a Wen-Bo Yu,^a Wei-Wei Li,^a Yong-Zhao Zhang ^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 28 May 2009; accepted 7 June 2009; online 10 June 2009)

The title compound, C₁₀H₁₂N₂O₄, adopts a trans configuration with respect to the C=N double bond. The non-H atoms of the molecule are essentially coplanar, with a maximum deviation of 0.015 (2) Å. An intramolecular O—H⋯N interaction is observed. In the crystal structure, the molecules are linked into a two-dimensional network parallel to the ac plane by N—H⋯O hydrogen bonds involving the methoxy O atom and by two C—H⋯O hydrogen bonds involving the carbonyl O atom. In addition, an intermolecular C—H⋯π interaction is observed.

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 the use of metal complexes of Schiff bases as model compounds of active centres in various proteins and enzymes, 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, C c
a = 11.4348 (13) Å
b = 14.8717 (18) Å
c = 6.3508 (8) Å
β = 98.538 (4)°
V = 1068.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.24 × 0.22 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.975, T_max = 0.985
5851 measured reflections
1049 independent reflections
948 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.075
S = 1.11
1049 reflections
148 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.93	2.645 (2)	145
N2—H2⋯O2ⁱ	0.86	2.42	3.022 (2)	127
C5—H5⋯O3ⁱⁱ	0.93	2.49	3.320 (2)	149
C7—H7⋯O3ⁱⁱ	0.93	2.45	3.291 (2)	150
C3—H3⋯Cg1ⁱⁱⁱ	0.93	2.85	3.606 (2)	139
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C1–C6 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/S1600536809021631/ci2816sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021631/ci2816Isup2.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.

The title molecule adopts a trans configuration with respect to the C═N bond. The non-hydrogen atoms of the molecule are essentially coplanar, with a maximum deviation of 0.015 (2) Å for atom C(7). The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007). An intramolecular O—H···N interaction is observed.

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

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 the use of metal complexes of Schiff bases as model compounds of active centres in various proteins and enzymes, see: Kahwa et al. (1986); Santos et al. (2001). For a related structure, see: Shang et al. (2007). Cg1 is the centroid of the C1–C6 ring.

Experimental top

2-Hydroxy-3-methoxybenzaldehyde (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90g, 0.01 mol) were dissolved in stirred methanol (20 ml) and left for 3.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 415–418 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.

(E)-Methyl N'-(2-hydroxy-3-methoxybenzylidene)hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₄	F(000) = 472
M_r = 224.22	D_x = 1.394 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1049 reflections
a = 11.4348 (13) Å	θ = 2.3–26.0°
b = 14.8717 (18) Å	µ = 0.11 mm⁻¹
c = 6.3508 (8) Å	T = 223 K
β = 98.538 (4)°	Block, colourles
V = 1068.0 (2) Å³	0.24 × 0.22 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1049 independent reflections
Radiation source: fine-focus sealed tube	948 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→14
T_min = 0.975, T_max = 0.985	k = −16→18
5851 measured reflections	l = −7→7

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0409P)² + 0.1415P] where P = (F_o² + 2F_c²)/3
1049 reflections	(Δ/σ)_max = 0.003
148 parameters	Δρ_max = 0.11 e Å⁻³
2 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O₄	V = 1068.0 (2) Å³
M_r = 224.22	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 11.4348 (13) Å	µ = 0.11 mm⁻¹
b = 14.8717 (18) Å	T = 223 K
c = 6.3508 (8) Å	0.24 × 0.22 × 0.17 mm
β = 98.538 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1049 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	948 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.985	R_int = 0.021
5851 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	2 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.11	Δρ_max = 0.11 e Å⁻³
1049 reflections	Δρ_min = −0.13 e Å⁻³
148 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
C1	0.11401 (17)	0.33419 (13)	0.6468 (3)	0.0412 (5)
C2	0.14440 (19)	0.38079 (15)	0.4705 (4)	0.0446 (5)
C3	0.0578 (2)	0.42357 (16)	0.3309 (4)	0.0513 (6)
H3	0.0779	0.4550	0.2149	0.062*
C4	−0.0596 (2)	0.4195 (2)	0.3646 (4)	0.0584 (6)
H4	−0.1176	0.4484	0.2704	0.070*
C5	−0.0906 (2)	0.37377 (16)	0.5339 (4)	0.0528 (6)
H5	−0.1696	0.3711	0.5531	0.063*
C6	−0.00420 (19)	0.33056 (15)	0.6795 (3)	0.0436 (5)
C7	−0.04116 (18)	0.28326 (16)	0.8601 (3)	0.0469 (5)
H7	−0.1203	0.2836	0.8788	0.056*
C8	0.07691 (19)	0.15569 (15)	1.3010 (3)	0.0451 (5)
C9	0.1022 (3)	0.0689 (2)	1.6128 (5)	0.0690 (8)
H9A	0.1535	0.0304	1.5467	0.103*
H9B	0.0569	0.0334	1.6977	0.103*
H9C	0.1487	0.1118	1.7019	0.103*
C10	0.2979 (3)	0.4277 (2)	0.2805 (5)	0.0767 (9)
H10A	0.2597	0.4021	0.1495	0.115*
H10B	0.3821	0.4231	0.2868	0.115*
H10C	0.2760	0.4898	0.2874	0.115*
N1	0.03469 (15)	0.24138 (13)	0.9926 (3)	0.0462 (4)
N2	−0.00459 (16)	0.19813 (14)	1.1600 (3)	0.0502 (5)
H2	−0.0782	0.1981	1.1743	0.060*
O1	0.20402 (14)	0.29467 (12)	0.7790 (3)	0.0553 (4)
H1	0.1776	0.2697	0.8770	0.083*
O2	0.26239 (14)	0.38043 (11)	0.4552 (3)	0.0561 (4)
O3	0.18042 (15)	0.15245 (13)	1.2939 (3)	0.0660 (5)
O4	0.02356 (14)	0.11544 (12)	1.4512 (3)	0.0572 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0391 (10)	0.0391 (12)	0.0450 (11)	0.0002 (8)	0.0049 (9)	−0.0029 (10)
C2	0.0418 (10)	0.0435 (12)	0.0494 (12)	−0.0029 (8)	0.0099 (9)	−0.0048 (9)
C3	0.0525 (13)	0.0533 (14)	0.0481 (14)	−0.0039 (10)	0.0069 (10)	0.0079 (11)
C4	0.0442 (11)	0.0696 (17)	0.0587 (15)	0.0017 (10)	−0.0016 (10)	0.0162 (12)
C5	0.0377 (10)	0.0573 (15)	0.0632 (15)	0.0004 (10)	0.0066 (10)	0.0057 (11)
C6	0.0419 (10)	0.0420 (12)	0.0477 (12)	−0.0026 (9)	0.0087 (8)	−0.0025 (9)
C7	0.0417 (11)	0.0477 (14)	0.0526 (13)	−0.0010 (9)	0.0114 (10)	−0.0009 (10)
C8	0.0430 (12)	0.0476 (13)	0.0466 (12)	−0.0036 (9)	0.0130 (9)	−0.0022 (10)
C9	0.0701 (16)	0.0767 (18)	0.0617 (17)	0.0157 (14)	0.0148 (13)	0.0164 (14)
C10	0.0583 (15)	0.098 (2)	0.081 (2)	−0.0028 (14)	0.0332 (14)	0.0230 (16)
N1	0.0457 (9)	0.0486 (11)	0.0459 (9)	−0.0044 (8)	0.0120 (8)	0.0006 (9)
N2	0.0388 (9)	0.0593 (12)	0.0544 (12)	−0.0024 (8)	0.0135 (8)	0.0107 (9)
O1	0.0429 (8)	0.0631 (10)	0.0591 (10)	0.0033 (8)	0.0050 (7)	0.0137 (8)
O2	0.0433 (8)	0.0628 (9)	0.0653 (10)	0.0004 (7)	0.0185 (7)	0.0103 (8)
O3	0.0413 (9)	0.0889 (13)	0.0689 (11)	0.0005 (8)	0.0122 (7)	0.0093 (10)
O4	0.0499 (8)	0.0641 (11)	0.0596 (10)	0.0070 (7)	0.0151 (7)	0.0183 (8)

Geometric parameters (Å, º) top

C1—O1	1.361 (2)	C8—O3	1.192 (3)
C1—C6	1.399 (3)	C8—O4	1.347 (3)
C1—C2	1.404 (3)	C8—N2	1.349 (3)
C2—O2	1.367 (3)	C9—O4	1.438 (3)
C2—C3	1.382 (3)	C9—H9A	0.96
C3—C4	1.392 (3)	C9—H9B	0.96
C3—H3	0.93	C9—H9C	0.96
C4—C5	1.363 (4)	C10—O2	1.423 (3)
C4—H4	0.93	C10—H10A	0.96
C5—C6	1.405 (3)	C10—H10B	0.96
C5—H5	0.93	C10—H10C	0.96
C6—C7	1.460 (3)	N1—N2	1.374 (2)
C7—N1	1.277 (3)	N2—H2	0.86
C7—H7	0.93	O1—H1	0.82

O1—C1—C6	123.41 (19)	O3—C8—N2	125.9 (2)
O1—C1—C2	116.80 (17)	O4—C8—N2	109.70 (18)
C6—C1—C2	119.79 (19)	O4—C9—H9A	109.5
O2—C2—C3	125.2 (2)	O4—C9—H9B	109.5
O2—C2—C1	114.75 (19)	H9A—C9—H9B	109.5
C3—C2—C1	120.00 (19)	O4—C9—H9C	109.5
C2—C3—C4	119.8 (2)	H9A—C9—H9C	109.5
C2—C3—H3	120.1	H9B—C9—H9C	109.5
C4—C3—H3	120.1	O2—C10—H10A	109.5
C5—C4—C3	120.9 (2)	O2—C10—H10B	109.5
C5—C4—H4	119.6	H10A—C10—H10B	109.5
C3—C4—H4	119.6	O2—C10—H10C	109.5
C4—C5—C6	120.5 (2)	H10A—C10—H10C	109.5
C4—C5—H5	119.8	H10B—C10—H10C	109.5
C6—C5—H5	119.8	C7—N1—N2	118.03 (16)
C1—C6—C5	119.0 (2)	C8—N2—N1	117.36 (17)
C1—C6—C7	122.28 (19)	C8—N2—H2	121.3
C5—C6—C7	118.7 (2)	N1—N2—H2	121.3
N1—C7—C6	120.31 (18)	C1—O1—H1	109.5
N1—C7—H7	119.8	C2—O2—C10	116.9 (2)
C6—C7—H7	119.8	C8—O4—C9	114.74 (19)
O3—C8—O4	124.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.93	2.645 (2)	145
N2—H2···O2ⁱ	0.86	2.42	3.022 (2)	127
C5—H5···O3ⁱⁱ	0.93	2.49	3.320 (2)	149
C7—H7···O3ⁱⁱ	0.93	2.45	3.291 (2)	150
C3—H3···Cg1ⁱⁱⁱ	0.93	2.85	3.606 (2)	139

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₄
M_r	224.22
Crystal system, space group	Monoclinic, Cc
Temperature (K)	223
a, b, c (Å)	11.4348 (13), 14.8717 (18), 6.3508 (8)
β (°)	98.538 (4)
V (Å³)	1068.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.975, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5851, 1049, 948
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.075, 1.11
No. of reflections	1049
No. of parameters	148
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.13

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
O1—H1···N1	0.82	1.93	2.645 (2)	145
N2—H2···O2ⁱ	0.86	2.42	3.022 (2)	127
C5—H5···O3ⁱⁱ	0.93	2.49	3.320 (2)	149
C7—H7···O3ⁱⁱ	0.93	2.45	3.291 (2)	150
C3—H3···Cg1ⁱⁱⁱ	0.93	2.85	3.606 (2)	139

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

Acknowledgements

The authors are grateful for financial support from the Zhejiang University of Technology Foundation (grant No. 20080169) and the Analysis and Measurement Foundation of Zhejiang Province (grant No. 2008F70003).

References

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