(E)-Methyl N′-(2-hydroxy­benzyl­idene)­hydrazinecarboxyl­ate at 123 K

Sun, R.; Cheng, X.-W.

doi:10.1107/S1600536808022332

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1563

doi:10.1107/S1600536808022332

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(E)-Methyl N′-(2-hydroxybenzylidene)hydrazinecarboxylate at 123 K

Rong Sun ^a and 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 9 July 2008; accepted 16 July 2008; online 23 July 2008)

In the title molecule, C₉H₁₀N₂O₃, the hydrazinecarboxylic acid mean plane and the benzene ring form a dihedral angle of 11.1 (1)°. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into chains extending along the b axis. An intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For applications of benzaldehydehydrazone derivatives, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For related structures, see: Cheng (2008 ).

Experimental

Crystal data

C₉H₁₀N₂O₃
M_r = 194.19
Orthorhombic, P b c a
a = 9.3998 (17) Å
b = 9.0945 (16) Å
c = 22.319 (4) Å
V = 1908.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 123 (2) K
0.27 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.965, T_max = 0.968
18306 measured reflections
1679 independent reflections
1427 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.120
S = 1.05
1679 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.19 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⋯N1	0.84	1.89	2.6234 (16)	145
N2—H2⋯O2ⁱ	0.88	2.02	2.8881 (16)	169
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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/S1600536808022332/cv2431sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022332/cv2431Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attentions for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). Meanwhile, it's an important intermidiate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many useful properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C₉H₁₀N₂O₃, is described here.

The title molecule (Fig. 1) adopts a trans configuration with respect to the C=N bond. Intramolecular O—H···N hydrogen bond (Table 1) influences the molecular conformation. The hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C1-C6 ring and the C8/C9/N1/N2/O2/O3 plane is 11.1 (1)°. The bond lengths and angles agree with those observed for (E)-Methyl N'-(4-hydroxybenzylidene) hydrazinecarboxylate (Cheng, 2008).

In the crystal, intermolecular N–H···O (Table 1) hydrogen bonds link the molecules into chains extended along b axis.

Related literature top

For applications of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For related structures, see: Cheng (2008).

Experimental top

2-hydroxy benzaldehyde (1.22 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (20 ml) and left for 3 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 465–468 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. Dashed line denotes intramolecular hydrogen bond.

(E)-Methyl N'-(2-hydroxybenzylidene)hydrazinecarboxylate top

Crystal data top

C₉H₁₀N₂O₃	F(000) = 816
M_r = 194.19	D_x = 1.352 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1679 reflections
a = 9.3998 (17) Å	θ = 2.0–25.0°
b = 9.0945 (16) Å	µ = 0.10 mm⁻¹
c = 22.319 (4) Å	T = 123 K
V = 1908.0 (6) Å³	Block, colourless
Z = 8	0.27 × 0.24 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1679 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→11
T_min = 0.965, T_max = 0.968	k = −10→10
18306 measured reflections	l = −26→26

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0674P)² + 0.4536P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.028
1679 reflections	Δρ_max = 0.19 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: 0.018 (2)

Crystal data top

C₉H₁₀N₂O₃	V = 1908.0 (6) Å³
M_r = 194.19	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.3998 (17) Å	µ = 0.10 mm⁻¹
b = 9.0945 (16) Å	T = 123 K
c = 22.319 (4) Å	0.27 × 0.24 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1679 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1427 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.026
18306 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1679 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
O3	0.37197 (12)	0.41375 (11)	−0.07538 (5)	0.0513 (3)
O2	0.36215 (12)	0.62287 (11)	−0.02044 (5)	0.0576 (4)
O1	0.16149 (12)	0.69567 (13)	0.13213 (5)	0.0625 (4)
H1	0.1906	0.6525	0.1012	0.094*
N2	0.22056 (13)	0.42471 (13)	−0.00032 (5)	0.0480 (4)
H2	0.1929	0.3365	−0.0116	0.058*
N1	0.16212 (12)	0.49157 (13)	0.04907 (5)	0.0452 (3)
C6	−0.00199 (15)	0.48908 (16)	0.13011 (6)	0.0429 (4)
C8	0.32185 (15)	0.49856 (15)	−0.03107 (6)	0.0431 (4)
C5	0.05028 (15)	0.61971 (16)	0.15591 (6)	0.0459 (4)
C7	0.06038 (16)	0.42561 (15)	0.07632 (6)	0.0461 (4)
H7	0.0255	0.3347	0.0613	0.055*
C1	−0.01226 (17)	0.67565 (18)	0.20764 (7)	0.0558 (4)
H1A	0.0236	0.7634	0.2251	0.067*
C4	−0.11726 (17)	0.41942 (18)	0.15784 (7)	0.0527 (4)
H4	−0.1537	0.3311	0.1411	0.063*
C2	−0.12633 (18)	0.6040 (2)	0.23379 (7)	0.0568 (5)
H2A	−0.1685	0.6431	0.2690	0.068*
C3	−0.17925 (17)	0.4760 (2)	0.20895 (7)	0.0573 (4)
H3	−0.2577	0.4272	0.2269	0.069*
C9	0.47848 (19)	0.4811 (2)	−0.11312 (7)	0.0617 (5)
H9A	0.5081	0.4111	−0.1441	0.093*
H9B	0.5610	0.5087	−0.0887	0.093*
H9C	0.4386	0.5690	−0.1321	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0596 (7)	0.0459 (6)	0.0484 (6)	0.0025 (5)	0.0093 (5)	−0.0070 (4)
O2	0.0665 (7)	0.0388 (6)	0.0674 (7)	−0.0022 (5)	0.0054 (5)	−0.0070 (5)
O1	0.0605 (7)	0.0593 (7)	0.0678 (7)	−0.0134 (5)	0.0108 (5)	−0.0181 (6)
N2	0.0567 (8)	0.0389 (7)	0.0484 (7)	−0.0020 (5)	0.0070 (6)	−0.0121 (5)
N1	0.0476 (7)	0.0430 (7)	0.0451 (7)	0.0051 (5)	0.0001 (5)	−0.0081 (5)
C6	0.0434 (8)	0.0435 (8)	0.0419 (8)	0.0047 (6)	−0.0069 (6)	0.0001 (6)
C8	0.0478 (8)	0.0366 (7)	0.0448 (8)	0.0075 (6)	−0.0035 (6)	−0.0040 (6)
C5	0.0457 (8)	0.0472 (8)	0.0449 (8)	0.0032 (6)	−0.0052 (6)	−0.0023 (6)
C7	0.0491 (8)	0.0406 (8)	0.0487 (8)	−0.0001 (6)	−0.0032 (6)	−0.0054 (6)
C1	0.0603 (10)	0.0578 (10)	0.0491 (8)	0.0048 (8)	−0.0057 (7)	−0.0124 (7)
C4	0.0526 (9)	0.0508 (9)	0.0548 (9)	−0.0005 (7)	−0.0012 (7)	−0.0002 (7)
C2	0.0586 (9)	0.0722 (11)	0.0395 (8)	0.0159 (8)	−0.0004 (7)	−0.0001 (7)
C3	0.0530 (9)	0.0651 (10)	0.0536 (9)	0.0043 (8)	0.0057 (7)	0.0105 (8)
C9	0.0589 (10)	0.0734 (11)	0.0528 (9)	0.0014 (8)	0.0107 (7)	0.0036 (8)

Geometric parameters (Å, º) top

O3—C8	1.3397 (17)	C5—C1	1.392 (2)
O3—C9	1.4445 (19)	C7—H7	0.9500
O2—C8	1.2158 (18)	C1—C2	1.384 (2)
O1—C5	1.3607 (18)	C1—H1A	0.9500
O1—H1	0.8400	C4—C3	1.380 (2)
N2—C8	1.3522 (19)	C4—H4	0.9500
N2—N1	1.3736 (16)	C2—C3	1.383 (3)
N2—H2	0.8800	C2—H2A	0.9500
N1—C7	1.2823 (19)	C3—H3	0.9500
C6—C4	1.399 (2)	C9—H9A	0.9800
C6—C5	1.409 (2)	C9—H9B	0.9800
C6—C7	1.455 (2)	C9—H9C	0.9800

C8—O3—C9	115.49 (12)	C2—C1—C5	120.34 (15)
C5—O1—H1	109.5	C2—C1—H1A	119.8
C8—N2—N1	117.97 (12)	C5—C1—H1A	119.8
C8—N2—H2	121.0	C3—C4—C6	121.58 (15)
N1—N2—H2	121.0	C3—C4—H4	119.2
C7—N1—N2	118.15 (12)	C6—C4—H4	119.2
C4—C6—C5	118.10 (14)	C3—C2—C1	120.42 (15)
C4—C6—C7	119.81 (13)	C3—C2—H2A	119.8
C5—C6—C7	122.09 (14)	C1—C2—H2A	119.8
O2—C8—O3	124.74 (14)	C4—C3—C2	119.56 (16)
O2—C8—N2	125.61 (14)	C4—C3—H3	120.2
O3—C8—N2	109.65 (12)	C2—C3—H3	120.2
O1—C5—C1	117.55 (13)	O3—C9—H9A	109.5
O1—C5—C6	122.45 (13)	O3—C9—H9B	109.5
C1—C5—C6	120.00 (14)	H9A—C9—H9B	109.5
N1—C7—C6	120.40 (13)	O3—C9—H9C	109.5
N1—C7—H7	119.8	H9A—C9—H9C	109.5
C6—C7—H7	119.8	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.89	2.6234 (16)	145
N2—H2···O2ⁱ	0.88	2.02	2.8881 (16)	169

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃
M_r	194.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	9.3998 (17), 9.0945 (16), 22.319 (4)
V (Å³)	1908.0 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.27 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector 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	18306, 1679, 1427
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.120, 1.05
No. of reflections	1679
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

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	0.84	1.89	2.6234 (16)	145.3
N2—H2···O2ⁱ	0.88	2.02	2.8881 (16)	168.6

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

We acknowledge financial support from Zhejiang Police College, China.

References

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