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

Cheng, X.-W.

doi:10.1107/S1600536808019788

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1397

doi:10.1107/S1600536808019788

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

Xiang-Wei Cheng ^a ^*

^aZhejiang Police College Experience Center, Zhejiang Police College, Hangzhou 310053, People's Republic of China
^*Correspondence e-mail: zpccxw@126.com

(Received 27 June 2008; accepted 28 June 2008; online 5 July 2008)

The molecule of the title compound, C₁₀H₁₂N₂O₄, adopts a trans configuration with respect to the C=N double bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate mean plane is 36.54 (6)°. The molecules are linked into a two-dimensional network by intermolecular O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds, and by aromatic π–π stacking interactions [ring-centroid separation 3.7689 (9) Å].

Related literature

For a related structure, see: Cheng (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₄
M_r = 224.22
Monoclinic, P 2₁ /c
a = 9.4718 (10) Å
b = 11.0983 (11) Å
c = 10.3220 (11) Å
β = 98.272 (4)°
V = 1073.77 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 123 (2) K
0.29 × 0.27 × 0.26 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.965, T_max = 0.968
11214 measured reflections
1887 independent reflections
1590 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.113
S = 1.02
1887 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84	2.21	2.6695 (15)	114
O1—H1⋯O3ⁱ	0.84	2.34	3.0286 (16)	139
O1—H1⋯N1ⁱ	0.84	2.57	3.2640 (17)	140
N2—H2B⋯O3ⁱⁱ	0.88	2.19	3.0124 (16)	155
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536808019788/hb2754sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019788/hb2754Isup2.hkl

checkCIF report

Comment top

As part of our ongoig 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 dihedral angle between the benzene ring and the C9/C10//N1/N2/O3/O4 plane is 36.54 (6)°. Otherwise, the bond lengths and angles for (I) agree with those observed for (E)-methylN'-(4-hydroxybenzylidene)hydrazinecarboxylate (Cheng, 2008).

In the crystal, the molecules are linked into a two-dimensional network by intramolecular O—H···O and intermolecular O—H···O, N—H···O, O—H···N hydrogen bonds (Table 1). Additionally, neighbouring aromatic rings interact by π–π stacking [centroid separation = 3.7689 (9) Å].

Related literature top

For a related structure, see: Cheng (2008).

Experimental top

4-Hydroxy-3-methoxybenzaldehyde (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.9 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 in 90% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 480–482 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 (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms.

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

Crystal data top

C₁₀H₁₂N₂O₄	F(000) = 472
M_r = 224.22	D_x = 1.387 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1887 reflections
a = 9.4718 (10) Å	θ = 2.2–25.0°
b = 11.0983 (11) Å	µ = 0.11 mm⁻¹
c = 10.3220 (11) Å	T = 123 K
β = 98.272 (4)°	Block, colourless
V = 1073.77 (19) Å³	0.29 × 0.27 × 0.26 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1887 independent reflections
Radiation source: fine-focus sealed tube	1590 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
T_min = 0.965, T_max = 0.968	k = −13→13
11214 measured reflections	l = −11→12

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0687P)² + 0.1817P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.010
1887 reflections	Δρ_max = 0.19 e Å⁻³
146 parameters	Δρ_min = −0.14 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: 0.036 (5)

Crystal data top

C₁₀H₁₂N₂O₄	V = 1073.77 (19) Å³
M_r = 224.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4718 (10) Å	µ = 0.11 mm⁻¹
b = 11.0983 (11) Å	T = 123 K
c = 10.3220 (11) Å	0.29 × 0.27 × 0.26 mm
β = 98.272 (4)°

Data collection top

Bruker SMART CCD diffractometer	1887 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1590 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.029
11214 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
1887 reflections	Δρ_min = −0.14 e Å⁻³
146 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
C1	0.46841 (16)	0.22471 (12)	0.90488 (15)	0.0408 (4)
C2	0.57541 (17)	0.23855 (13)	1.00956 (16)	0.0453 (4)
H2A	0.5760	0.3073	1.0645	0.054*
C3	0.46883 (16)	0.12325 (13)	0.82397 (14)	0.0405 (4)
C4	0.3402 (2)	0.01177 (17)	0.64655 (17)	0.0596 (5)
H4A	0.2550	0.0191	0.5809	0.089*
H4B	0.3309	−0.0589	0.7016	0.089*
H4C	0.4246	0.0026	0.6025	0.089*
C5	0.57560 (15)	0.03861 (13)	0.84778 (14)	0.0406 (4)
H5	0.5761	−0.0291	0.7916	0.049*
C6	0.68260 (16)	0.15212 (14)	1.03504 (15)	0.0439 (4)
H6	0.7554	0.1618	1.1079	0.053*
C7	0.68361 (15)	0.05223 (13)	0.95482 (14)	0.0390 (4)
C8	0.79364 (16)	−0.04036 (13)	0.98484 (15)	0.0425 (4)
H8	0.8497	−0.0414	1.0689	0.051*
C9	0.96010 (15)	−0.28026 (12)	0.85416 (14)	0.0381 (4)
C10	1.0957 (2)	−0.45396 (18)	0.82782 (19)	0.0681 (6)
H10A	1.1524	−0.5152	0.8804	0.102*
H10B	1.1562	−0.4113	0.7734	0.102*
H10C	1.0166	−0.4929	0.7715	0.102*
N1	0.81595 (13)	−0.11952 (11)	0.90087 (12)	0.0409 (3)
N2	0.91622 (13)	−0.20662 (11)	0.94426 (12)	0.0434 (3)
H2B	0.9502	−0.2137	1.0279	0.052*
O1	0.36374 (12)	0.30938 (9)	0.88270 (11)	0.0543 (3)
H1	0.3060	0.2900	0.8164	0.081*
O2	0.35509 (13)	0.11728 (10)	0.72612 (11)	0.0571 (4)
O3	0.93369 (12)	−0.26695 (10)	0.73659 (10)	0.0508 (3)
O4	1.03976 (12)	−0.36926 (10)	0.91342 (10)	0.0520 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0423 (8)	0.0368 (7)	0.0437 (9)	0.0025 (6)	0.0071 (6)	0.0028 (6)
C2	0.0511 (9)	0.0373 (8)	0.0469 (9)	0.0004 (6)	0.0045 (7)	−0.0050 (6)
C3	0.0410 (8)	0.0445 (8)	0.0360 (8)	0.0010 (6)	0.0055 (6)	0.0012 (6)
C4	0.0648 (11)	0.0618 (10)	0.0485 (10)	0.0017 (9)	−0.0038 (8)	−0.0113 (8)
C5	0.0432 (8)	0.0401 (8)	0.0398 (8)	0.0016 (6)	0.0101 (6)	−0.0025 (6)
C6	0.0431 (8)	0.0458 (8)	0.0415 (9)	−0.0022 (7)	0.0018 (6)	0.0014 (6)
C7	0.0387 (8)	0.0403 (7)	0.0390 (8)	−0.0002 (6)	0.0095 (6)	0.0040 (6)
C8	0.0431 (8)	0.0455 (8)	0.0387 (8)	0.0030 (6)	0.0056 (6)	0.0025 (6)
C9	0.0352 (7)	0.0434 (8)	0.0349 (8)	−0.0014 (6)	0.0029 (6)	0.0006 (6)
C10	0.0767 (13)	0.0687 (12)	0.0567 (11)	0.0307 (10)	0.0019 (9)	−0.0149 (9)
N1	0.0393 (7)	0.0442 (7)	0.0393 (7)	0.0059 (5)	0.0064 (5)	0.0070 (5)
N2	0.0465 (7)	0.0500 (7)	0.0328 (7)	0.0132 (6)	0.0033 (5)	0.0023 (5)
O1	0.0565 (7)	0.0465 (6)	0.0559 (7)	0.0137 (5)	−0.0053 (5)	−0.0084 (5)
O2	0.0551 (7)	0.0610 (7)	0.0501 (7)	0.0157 (5)	−0.0093 (5)	−0.0147 (5)
O3	0.0589 (7)	0.0593 (7)	0.0336 (7)	0.0073 (5)	0.0046 (5)	0.0001 (5)
O4	0.0612 (7)	0.0534 (7)	0.0402 (6)	0.0199 (5)	0.0026 (5)	−0.0030 (5)

Geometric parameters (Å, º) top

C1—O1	1.3613 (17)	C6—H6	0.9500
C1—C2	1.380 (2)	C7—C8	1.465 (2)
C1—C3	1.402 (2)	C8—N1	1.2729 (19)
C2—C6	1.394 (2)	C8—H8	0.9500
C2—H2A	0.9500	C9—O3	1.2123 (18)
C3—O2	1.3682 (18)	C9—O4	1.3366 (17)
C3—C5	1.376 (2)	C9—N2	1.3479 (19)
C4—O2	1.4256 (19)	C10—O4	1.4421 (19)
C4—H4A	0.9800	C10—H10A	0.9800
C4—H4B	0.9800	C10—H10B	0.9800
C4—H4C	0.9800	C10—H10C	0.9800
C5—C7	1.402 (2)	N1—N2	1.3837 (16)
C5—H5	0.9500	N2—H2B	0.8800
C6—C7	1.385 (2)	O1—H1	0.8400

O1—C1—C2	119.35 (13)	C6—C7—C8	120.08 (13)
O1—C1—C3	121.23 (13)	C5—C7—C8	120.50 (13)
C2—C1—C3	119.42 (13)	N1—C8—C7	121.53 (13)
C1—C2—C6	120.28 (14)	N1—C8—H8	119.2
C1—C2—H2A	119.9	C7—C8—H8	119.2
C6—C2—H2A	119.9	O3—C9—O4	124.73 (13)
O2—C3—C5	125.38 (13)	O3—C9—N2	125.25 (13)
O2—C3—C1	114.15 (13)	O4—C9—N2	110.01 (12)
C5—C3—C1	120.45 (13)	O4—C10—H10A	109.5
O2—C4—H4A	109.5	O4—C10—H10B	109.5
O2—C4—H4B	109.5	H10A—C10—H10B	109.5
H4A—C4—H4B	109.5	O4—C10—H10C	109.5
O2—C4—H4C	109.5	H10A—C10—H10C	109.5
H4A—C4—H4C	109.5	H10B—C10—H10C	109.5
H4B—C4—H4C	109.5	C8—N1—N2	115.80 (12)
C3—C5—C7	120.09 (13)	C9—N2—N1	117.75 (12)
C3—C5—H5	120.0	C9—N2—H2B	121.1
C7—C5—H5	120.0	N1—N2—H2B	121.1
C7—C6—C2	120.37 (14)	C1—O1—H1	109.5
C7—C6—H6	119.8	C3—O2—C4	117.85 (12)
C2—C6—H6	119.8	C9—O4—C10	115.75 (12)
C6—C7—C5	119.38 (13)

O1—C1—C2—C6	179.17 (14)	C3—C5—C7—C8	176.91 (13)
C3—C1—C2—C6	−0.3 (2)	C6—C7—C8—N1	−165.42 (14)
O1—C1—C3—O2	−1.5 (2)	C5—C7—C8—N1	16.9 (2)
C2—C1—C3—O2	177.96 (14)	C7—C8—N1—N2	−175.85 (12)
O1—C1—C3—C5	179.93 (14)	O3—C9—N2—N1	10.3 (2)
C2—C1—C3—C5	−0.6 (2)	O4—C9—N2—N1	−170.91 (11)
O2—C3—C5—C7	−177.24 (13)	C8—N1—N2—C9	−169.52 (13)
C1—C3—C5—C7	1.1 (2)	C5—C3—O2—C4	4.0 (2)
C1—C2—C6—C7	0.7 (2)	C1—C3—O2—C4	−174.49 (14)
C2—C6—C7—C5	−0.1 (2)	O3—C9—O4—C10	−0.3 (2)
C2—C6—C7—C8	−177.83 (13)	N2—C9—O4—C10	−179.09 (14)
C3—C5—C7—C6	−0.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.21	2.6695 (15)	114
O1—H1···O3ⁱ	0.84	2.34	3.0286 (16)	139
O1—H1···N1ⁱ	0.84	2.57	3.2640 (17)	140
N2—H2B···O3ⁱⁱ	0.88	2.19	3.0124 (16)	155

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −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)	123
a, b, c (Å)	9.4718 (10), 11.0983 (11), 10.3220 (11)
β (°)	98.272 (4)
V (Å³)	1073.77 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.29 × 0.27 × 0.26

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.965, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	11214, 1887, 1590
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.113, 1.02
No. of reflections	1887
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (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···O2	0.84	2.21	2.6695 (15)	114
O1—H1···O3ⁱ	0.84	2.34	3.0286 (16)	139
O1—H1···N1ⁱ	0.84	2.57	3.2640 (17)	140
N2—H2B···O3ⁱⁱ	0.88	2.19	3.0124 (16)	155

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

Acknowledgements

The author acknowledges financial support from Zhejiang Police College, China.

References

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cheng, X.-W. (2008). Acta Cryst. E64, o1302. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar