(E)-Methyl N′-(4-hydroxy­benzyl­idene)hydrazinecarboxyl­ate

Cheng, X.-W.

doi:10.1107/S1600536808018096

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1302

doi:10.1107/S1600536808018096

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(E)-Methyl N′-(4-hydroxybenzylidene)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 12 June 2008; accepted 14 June 2008; online 19 June 2008)

In the title compound, C₉H₁₀N₂O₃, the hydroxy group and the C=N—N unit are coplanar with the benzene ring. The benzene rings of inversion-related molecules are stacked with their centroids separated by a distance of 3.7703 (9) Å, indicating weak π–π interactions. In the crystal structure, C—H⋯O, O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link molecules into a infinite two-dimensional network along the a axis.

Related literature

For general background, see: Hadjoudis et al. (1987 ); Borg et al. (1999 ); Parashar et al. (2005). For a related structure, see: Shang et al. (2007 ). For related literature, see: Parashar et al. (1988 ).

Experimental

Crystal data

C₉H₁₀N₂O₃
M_r = 194.19
Monoclinic, P 2₁ /c
a = 8.1943 (8) Å
b = 12.0512 (11) Å
c = 10.1067 (9) Å
β = 111.970 (3)°
V = 925.57 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 123 (2) K
0.31 × 0.28 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.969, T_max = 0.978
9552 measured reflections
1623 independent reflections
1487 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.115
S = 0.95
1623 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.84	2.58	3.068 (2)	118
O1—H1⋯N1ⁱ	0.84	2.11	2.941 (2)	169
N2—H2A⋯O2ⁱⁱ	0.88	2.13	2.964 (2)	158
C7—H7⋯O2ⁱⁱ	0.95	2.38	3.188 (2)	143
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (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/S1600536808018096/tk2273sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018096/tk2273Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attention owing to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). In addition, they are important intermediates in the synthesis of 1,3,4-oxadiazoles, which have been reported to be versatile compounds (Borg et al., 1999). As a part of an investigation of this type of derivative, the crystal structure of the title compound, C₉H₁₀N₂O₃ (I), is described herein.

In (I), Fig. 1 & Table 1, all non-hydrogen atoms are co-planar to within ±0.699 (4) Å. The molecule is in the E-conformation with respect to the N=C double bond. The bond lengths and angles defining the C=N—N(H)—C group are close to those of the previously reported N'-(4-Methoxybenzylidene)methoxyformohydrazide structure (shang et al., 2007).

The benzene rings of inversion-related molecules are stacked with their centroids separated by a distance of 3.7703 (9) Å, consistent with π-π interactions.

Related literature top

For general background, see: Hadjoudis et al. (1987); Borg et al., (1999) & Parashar et al. (2005). For related structures, see: Shang et al. (2007). For related literature, see: Parashar et al. (1988).

Experimental top

4-Hydroxy benzaldehyde (12.2 g, 0.1 mol) and methyl hydrazinecarboxylate (9.0 g, 0.1 mol) were dissolved in methanol (50 ml) solution and stirred for 6 h at room temperature. The resulting solid was filtered off and recrystallized from an ethanol solution to give (I) in 80% yield. Crystals suitable for X-ray analysis were obtained by the slow evaporation of an ethanol solution held at room temperature (m.p. 475–478 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. Molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

(E)-Methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate top

Crystal data top

C₉H₁₀N₂O₃	F(000) = 408
M_r = 194.19	D_x = 1.394 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1628 reflections
a = 8.1943 (8) Å	θ = 2.0–25.0°
b = 12.0512 (11) Å	µ = 0.11 mm⁻¹
c = 10.1067 (9) Å	T = 123 K
β = 111.970 (3)°	Block, colourless
V = 925.57 (15) Å³	0.31 × 0.28 × 0.24 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1623 independent reflections
Radiation source: fine-focus sealed tube	1487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
T_min = 0.969, T_max = 0.978	k = −13→14
9552 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) = 0.115	w = 1/[σ²(F_o²) + (0.0871P)² + 0.1838P] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
1623 reflections	Δρ_max = 0.24 e Å⁻³
128 parameters	Δρ_min = −0.19 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: 0.288 (19)

Crystal data top

C₉H₁₀N₂O₃	V = 925.57 (15) Å³
M_r = 194.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1943 (8) Å	µ = 0.11 mm⁻¹
b = 12.0512 (11) Å	T = 123 K
c = 10.1067 (9) Å	0.31 × 0.28 × 0.24 mm
β = 111.970 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1623 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1487 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.978	R_int = 0.021
9552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 0.95	Δρ_max = 0.24 e Å⁻³
1623 reflections	Δρ_min = −0.19 e Å⁻³
128 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
O1	0.38082 (14)	0.30936 (8)	0.37656 (11)	0.0529 (3)
H1	0.3162	0.3134	0.2897	0.079*
O2	0.97787 (14)	−0.29441 (9)	0.29627 (10)	0.0516 (3)
O3	1.11604 (14)	−0.37383 (8)	0.51277 (11)	0.0520 (3)
N2	0.94810 (15)	−0.22777 (9)	0.49593 (12)	0.0440 (3)
H2A	0.9787	−0.2353	0.5887	0.053*
N1	0.83415 (14)	−0.14299 (9)	0.42392 (11)	0.0395 (3)
C5	0.57987 (17)	0.04812 (11)	0.32350 (13)	0.0396 (4)
H5	0.5728	−0.0024	0.2494	0.047*
C6	0.69854 (16)	0.02765 (10)	0.46270 (13)	0.0369 (3)
C3	0.47278 (17)	0.14106 (11)	0.29260 (13)	0.0408 (4)
H3	0.3932	0.1538	0.1976	0.049*
C1	0.48094 (16)	0.21605 (10)	0.39995 (14)	0.0390 (4)
C2	0.59680 (18)	0.19579 (11)	0.53868 (14)	0.0428 (4)
H2	0.6028	0.2459	0.6129	0.051*
C4	0.70306 (17)	0.10317 (12)	0.56872 (14)	0.0410 (4)
H4	0.7815	0.0904	0.6641	0.049*
C8	1.01137 (16)	−0.29807 (11)	0.42353 (14)	0.0386 (4)
C7	0.81502 (16)	−0.06805 (11)	0.50677 (14)	0.0398 (4)
H7	0.8828	−0.0755	0.6058	0.048*
C9	1.1945 (2)	−0.45473 (13)	0.4509 (2)	0.0619 (5)
H9A	1.2675	−0.5054	0.5253	0.093*
H9B	1.2678	−0.4171	0.4071	0.093*
H9C	1.1018	−0.4969	0.3778	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0548 (6)	0.0432 (6)	0.0517 (6)	0.0084 (4)	0.0096 (5)	−0.0039 (4)
O2	0.0574 (6)	0.0589 (7)	0.0365 (6)	0.0024 (5)	0.0154 (5)	−0.0063 (4)
O3	0.0570 (6)	0.0504 (6)	0.0506 (6)	0.0140 (5)	0.0226 (5)	0.0073 (4)
N2	0.0520 (7)	0.0473 (7)	0.0344 (6)	0.0110 (5)	0.0181 (5)	0.0068 (5)
N1	0.0390 (6)	0.0411 (6)	0.0388 (6)	0.0018 (4)	0.0153 (5)	0.0040 (5)
C5	0.0446 (7)	0.0398 (7)	0.0358 (7)	−0.0025 (5)	0.0168 (5)	−0.0020 (5)
C6	0.0376 (6)	0.0367 (7)	0.0384 (7)	−0.0047 (5)	0.0164 (5)	0.0018 (5)
C3	0.0416 (7)	0.0423 (7)	0.0357 (7)	−0.0026 (5)	0.0111 (5)	0.0022 (5)
C1	0.0383 (7)	0.0340 (7)	0.0451 (8)	−0.0036 (5)	0.0161 (6)	0.0005 (5)
C2	0.0464 (7)	0.0408 (7)	0.0405 (7)	−0.0039 (6)	0.0155 (6)	−0.0063 (6)
C4	0.0421 (7)	0.0435 (8)	0.0352 (6)	−0.0041 (5)	0.0118 (5)	−0.0001 (5)
C8	0.0372 (7)	0.0407 (7)	0.0381 (7)	−0.0041 (5)	0.0141 (5)	−0.0006 (5)
C7	0.0419 (7)	0.0423 (8)	0.0351 (7)	−0.0020 (5)	0.0142 (5)	0.0020 (5)
C9	0.0611 (10)	0.0503 (9)	0.0785 (12)	0.0113 (7)	0.0311 (8)	−0.0005 (8)

Geometric parameters (Å, º) top

O1—C1	1.3595 (16)	C6—C4	1.3958 (18)
O1—H1	0.8400	C6—C7	1.4565 (18)
O2—C8	1.2114 (17)	C3—C1	1.3943 (19)
O3—C8	1.3431 (16)	C3—H3	0.9500
O3—C9	1.4339 (18)	C1—C2	1.3895 (19)
N1—N2	1.3917 (15)	C2—C4	1.3778 (19)
N2—H2A	0.8800	C2—H2	0.9500
N1—C7	1.2805 (17)	C4—H4	0.9500
N2—C8	1.3438 (17)	C7—H7	0.9500
C5—C3	1.3846 (18)	C9—H9A	0.9800
C5—C6	1.4007 (18)	C9—H9B	0.9800
C5—H5	0.9500	C9—H9C	0.9800

C1—O1—H1	109.5	C4—C2—C1	120.11 (12)
C8—O3—C9	116.56 (12)	C4—C2—H2	119.9
N1—N2—C8	119.88 (11)	C1—C2—H2	119.9
C8—N2—H2A	120.1	C2—C4—C6	121.73 (12)
N1—N2—H2A	120.1	C2—C4—H4	119.1
N2—N1—C7	113.47 (11)	C6—C4—H4	119.1
C3—C5—C6	120.82 (12)	O2—C8—O3	124.88 (12)
C3—C5—H5	119.6	O2—C8—N2	125.09 (13)
C6—C5—H5	119.6	O3—C8—N2	110.03 (11)
C4—C6—C5	117.73 (12)	N1—C7—C6	125.81 (11)
C4—C6—C7	117.09 (11)	N1—C7—H7	117.1
C5—C6—C7	125.16 (12)	C6—C7—H7	117.1
C5—C3—C1	120.46 (12)	O3—C9—H9A	109.5
C5—C3—H3	119.8	O3—C9—H9B	109.5
C1—C3—H3	119.8	H9A—C9—H9B	109.5
O1—C1—C2	117.44 (12)	O3—C9—H9C	109.5
O1—C1—C3	123.41 (12)	H9A—C9—H9C	109.5
C2—C1—C3	119.14 (12)	H9B—C9—H9C	109.5

C8—N2—N1—C7	−165.18 (12)	C5—C6—C4—C2	−0.82 (19)
C3—C5—C6—C4	0.84 (18)	C7—C6—C4—C2	−179.27 (11)
C3—C5—C6—C7	179.14 (12)	C9—O3—C8—O2	0.9 (2)
C6—C5—C3—C1	−0.14 (19)	C9—O3—C8—N2	−179.72 (12)
C5—C3—C1—O1	179.33 (12)	N1—N2—C8—O2	0.3 (2)
C5—C3—C1—C2	−0.60 (19)	N1—N2—C8—O3	−179.11 (10)
O1—C1—C2—C4	−179.31 (12)	N2—N1—C7—C6	−177.08 (11)
C3—C1—C2—C4	0.62 (19)	C4—C6—C7—N1	−176.85 (12)
C1—C2—C4—C6	0.1 (2)	C5—C6—C7—N1	4.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	2.58	3.068 (2)	118
O1—H1···N1ⁱ	0.84	2.11	2.941 (2)	169
N2—H2A···O2ⁱⁱ	0.88	2.13	2.964 (2)	158
C7—H7···O2ⁱⁱ	0.95	2.38	3.188 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃
M_r	194.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.1943 (8), 12.0512 (11), 10.1067 (9)
β (°)	111.970 (3)
V (Å³)	925.57 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.28 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.969, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	9552, 1623, 1487
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.115, 0.95
No. of reflections	1623
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: SMART (Bruker, 2002), SAINT (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···O2ⁱ	0.84	2.58	3.068 (2)	118
O1—H1···N1ⁱ	0.84	2.11	2.941 (2)	169
N2—H2A···O2ⁱⁱ	0.88	2.13	2.964 (2)	158
C7—H7···O2ⁱⁱ	0.95	2.38	3.188 (2)	143

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

Acknowledgements

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

References

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