(E)-Methyl N′-[1-(4-hydroxy­phen­yl)ethyl­idene]hydrazinecarboxyl­ate

Lv, L.-P.; Xie, J.-W.; Yu, W.-B.; Li, W.-W.; Hu, X.-C.

doi:10.1107/S1600536808024227

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1675

doi:10.1107/S1600536808024227

Open

access

(E)-Methyl N′-[1-(4-hydroxyphenyl)ethylidene]hydrazinecarboxylate

Lu-Ping Lv,^a Jian-Wu Xie,^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 28 July 2008; accepted 30 July 2008; online 6 August 2008)

The title compound, C₁₀H₁₂N₂O₃, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazine carboxylic acid plane is 8.29 (7)°. Molecules are linked into a three-dimensional network by N—H⋯O, O—H⋯O, O—H⋯N hydrogen bonds and C—H⋯π interactions.

Related literature

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

Experimental

Crystal data

C₁₀H₁₂N₂O₃
M_r = 208.22
Orthorhombic, P b c a
a = 11.2532 (18) Å
b = 10.4310 (17) Å
c = 17.226 (3) Å
V = 2022.1 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 (2) K
0.31 × 0.27 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.972, T_max = 0.978
12287 measured reflections
1794 independent reflections
1626 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.098
S = 1.09
1794 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O21ⁱ	0.82	2.61	3.0523 (14)	116
O1—H1⋯N1ⁱ	0.82	2.03	2.8464 (14)	174
N2—H2A⋯O2ⁱⁱ	0.86	2.44	3.2777 (16)	164
C10—H10B⋯Cg1ⁱⁱⁱ	0.96	2.90	3.7169 (19)	144
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ . 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/S1600536808024227/bg2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024227/bg2200Isup2.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 is an important intermediate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with interesting properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C₁₀H₁₂N₂O₃(Fig.1), is described here.

The title molecule (Fig.1) adopts a trans configuration with respect to the C═N bond. The N1/N2/O2/O3/C9/C10 plane of the hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring, to which it subtends a dihedral angle of 8.29 (7)°. Bond lengths and angles agree with those observed for methyl N'-[(E)-4-methoxybenzylidene] hydrazinecarboxylate (Shang et al., 2007).

The molecules are linked into a three-dimensional network by N–H···O, O–H···O, O–H···N hydrogen bonds and C–H···π interactions. (Table 1).

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al., (1999). For related structures, see: Shang et al. (2007). Cg1 is the centroid of the C1–C6 ring.

Experimental top

4-Hydroxy-acetophenone (1.36 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 80% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 483–485 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 50% probability displacement ellipsoids and the atomic numbering.

(E)-Methyl N'-[1-(4-hydroxyphenyl)ethylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₃	F(000) = 880
M_r = 208.22	D_x = 1.368 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1794 reflections
a = 11.2532 (18) Å	θ = 2.4–25.0°
b = 10.4310 (17) Å	µ = 0.10 mm⁻¹
c = 17.226 (3) Å	T = 273 K
V = 2022.1 (6) Å³	Block, colourless
Z = 8	0.31 × 0.27 × 0.25 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1794 independent reflections
Radiation source: fine-focus sealed tube	1626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→10
T_min = 0.972, T_max = 0.978	k = −12→12
12287 measured reflections	l = −20→20

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0493P)² + 0.6007P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1794 reflections	Δρ_max = 0.17 e Å⁻³
140 parameters	Δρ_min = −0.15 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: 0.0032 (8)

Crystal data top

C₁₀H₁₂N₂O₃	V = 2022.1 (6) Å³
M_r = 208.22	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.2532 (18) Å	µ = 0.10 mm⁻¹
b = 10.4310 (17) Å	T = 273 K
c = 17.226 (3) Å	0.31 × 0.27 × 0.25 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1794 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1626 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.978	R_int = 0.016
12287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.09	Δρ_max = 0.17 e Å⁻³
1794 reflections	Δρ_min = −0.15 e Å⁻³
140 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	0.54458 (12)	0.13035 (13)	0.82724 (8)	0.0330 (3)
H3	0.4976	0.1806	0.8596	0.040*
C7	0.47041 (11)	−0.06505 (12)	0.89717 (7)	0.0287 (3)
C5	0.61590 (11)	−0.07467 (13)	0.78629 (8)	0.0329 (3)
H5	0.6177	−0.1634	0.7913	0.039*
C9	0.22859 (11)	0.01890 (13)	1.01445 (7)	0.0332 (3)
C3	0.68423 (11)	0.11609 (13)	0.72183 (7)	0.0294 (3)
C2	0.61307 (12)	0.18868 (13)	0.77120 (8)	0.0339 (3)
H2	0.6118	0.2775	0.7663	0.041*
C6	0.54416 (11)	−0.00311 (12)	0.83650 (7)	0.0283 (3)
C4	0.68424 (12)	−0.01681 (13)	0.72942 (7)	0.0328 (3)
H4	0.7302	−0.0667	0.6963	0.039*
C8	0.50358 (13)	−0.19457 (13)	0.92764 (8)	0.0366 (3)
H8A	0.5024	−0.1932	0.9834	0.055*
H8B	0.5819	−0.2166	0.9100	0.055*
H8C	0.4477	−0.2571	0.9091	0.055*
N2	0.30927 (11)	−0.05735 (10)	0.97785 (7)	0.0348 (3)
H2A	0.3164	−0.1372	0.9895	0.042*
N1	0.37946 (9)	−0.00106 (10)	0.92106 (6)	0.0299 (3)
O1	0.74919 (9)	0.18049 (9)	0.66825 (5)	0.0381 (3)
H1	0.7828	0.1291	0.6397	0.057*
O3	0.16440 (10)	−0.05274 (10)	1.06350 (6)	0.0471 (3)
O2	0.21727 (9)	0.13304 (9)	1.00534 (6)	0.0433 (3)
C10	0.07785 (16)	0.01597 (17)	1.10905 (10)	0.0540 (5)
H10A	0.1108	0.0965	1.1253	0.081*
H10B	0.0571	−0.0339	1.1539	0.081*
H10C	0.0081	0.0310	1.0783	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0343 (7)	0.0289 (7)	0.0359 (7)	0.0019 (6)	0.0053 (6)	−0.0057 (5)
C7	0.0261 (6)	0.0289 (7)	0.0309 (7)	−0.0016 (5)	−0.0063 (5)	−0.0016 (5)
C5	0.0315 (7)	0.0245 (7)	0.0426 (8)	0.0020 (5)	−0.0003 (6)	−0.0014 (5)
C9	0.0302 (7)	0.0359 (8)	0.0334 (7)	−0.0036 (6)	−0.0026 (5)	−0.0005 (6)
C3	0.0268 (6)	0.0316 (7)	0.0298 (6)	−0.0015 (5)	−0.0012 (5)	−0.0024 (5)
C2	0.0390 (8)	0.0238 (6)	0.0390 (7)	0.0006 (5)	0.0041 (6)	−0.0025 (5)
C6	0.0249 (6)	0.0286 (7)	0.0315 (7)	−0.0005 (5)	−0.0036 (5)	−0.0013 (5)
C4	0.0309 (7)	0.0300 (7)	0.0374 (7)	0.0043 (6)	0.0039 (5)	−0.0051 (5)
C8	0.0345 (7)	0.0321 (7)	0.0432 (8)	−0.0003 (6)	0.0006 (6)	0.0048 (6)
N2	0.0366 (7)	0.0293 (6)	0.0383 (6)	−0.0002 (5)	0.0056 (5)	0.0042 (5)
N1	0.0290 (6)	0.0319 (6)	0.0289 (6)	−0.0010 (5)	0.0005 (4)	0.0029 (4)
O1	0.0434 (6)	0.0314 (5)	0.0396 (5)	0.0003 (4)	0.0132 (4)	−0.0021 (4)
O3	0.0500 (7)	0.0373 (6)	0.0541 (6)	−0.0066 (5)	0.0232 (5)	−0.0039 (5)
O2	0.0437 (6)	0.0358 (6)	0.0505 (6)	0.0056 (5)	0.0053 (5)	0.0056 (5)
C10	0.0557 (10)	0.0507 (10)	0.0558 (10)	−0.0061 (8)	0.0227 (8)	−0.0134 (8)

Geometric parameters (Å, º) top

C1—C2	1.3770 (19)	C3—C4	1.3924 (19)
C1—C6	1.4012 (19)	C2—H2	0.9300
C1—H3	0.9300	C4—H4	0.9300
C7—N1	1.2894 (17)	C8—H8A	0.9600
C7—C6	1.4827 (18)	C8—H8B	0.9600
C7—C8	1.4967 (18)	C8—H8C	0.9600
C5—C4	1.3840 (19)	N2—N1	1.3877 (15)
C5—C6	1.3990 (18)	N2—H2A	0.8600
C5—H5	0.9300	O1—H1	0.8200
C9—O2	1.2076 (17)	O3—C10	1.4416 (18)
C9—O3	1.3394 (16)	C10—H10A	0.9600
C9—N2	1.3618 (18)	C10—H10B	0.9600
C3—O1	1.3556 (16)	C10—H10C	0.9600
C3—C2	1.3920 (18)

C2—C1—C6	121.38 (12)	C5—C4—C3	120.04 (12)
C2—C1—H3	119.3	C5—C4—H4	120.0
C6—C1—H3	119.3	C3—C4—H4	120.0
N1—C7—C6	116.34 (11)	C7—C8—H8A	109.5
N1—C7—C8	123.60 (12)	C7—C8—H8B	109.5
C6—C7—C8	120.07 (11)	H8A—C8—H8B	109.5
C4—C5—C6	121.71 (12)	C7—C8—H8C	109.5
C4—C5—H5	119.1	H8A—C8—H8C	109.5
C6—C5—H5	119.1	H8B—C8—H8C	109.5
O2—C9—O3	125.11 (12)	C9—N2—N1	117.31 (11)
O2—C9—N2	125.88 (12)	C9—N2—H2A	121.3
O3—C9—N2	109.01 (12)	N1—N2—H2A	121.3
O1—C3—C2	117.17 (12)	C7—N1—N2	117.25 (11)
O1—C3—C4	123.86 (11)	C3—O1—H1	109.5
C2—C3—C4	118.96 (12)	C9—O3—C10	115.49 (12)
C1—C2—C3	120.66 (12)	O3—C10—H10A	109.5
C1—C2—H2	119.7	O3—C10—H10B	109.5
C3—C2—H2	119.7	H10A—C10—H10B	109.5
C5—C6—C1	117.25 (12)	O3—C10—H10C	109.5
C5—C6—C7	121.75 (12)	H10A—C10—H10C	109.5
C1—C6—C7	121.01 (11)	H10B—C10—H10C	109.5

C6—C1—C2—C3	0.0 (2)	C6—C5—C4—C3	1.0 (2)
O1—C3—C2—C1	−179.91 (12)	O1—C3—C4—C5	179.43 (12)
C4—C3—C2—C1	0.66 (19)	C2—C3—C4—C5	−1.17 (19)
C4—C5—C6—C1	−0.33 (18)	O2—C9—N2—N1	−4.8 (2)
C4—C5—C6—C7	179.66 (12)	O3—C9—N2—N1	176.23 (11)
C2—C1—C6—C5	−0.20 (19)	C6—C7—N1—N2	−179.99 (10)
C2—C1—C6—C7	179.81 (12)	C8—C7—N1—N2	−0.36 (18)
N1—C7—C6—C5	−156.37 (12)	C9—N2—N1—C7	166.88 (11)
C8—C7—C6—C5	23.98 (18)	O2—C9—O3—C10	−1.4 (2)
N1—C7—C6—C1	23.61 (17)	N2—C9—O3—C10	177.62 (12)
C8—C7—C6—C1	−156.03 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	2.61	3.0523 (14)	116
O1—H1···N1ⁱ	0.82	2.03	2.8464 (14)	174
N2—H2A···O2ⁱⁱ	0.86	2.44	3.2777 (16)	164
C10—H10B···Cg1ⁱⁱⁱ	0.96	2.90	3.7169 (19)	144

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₃
M_r	208.22
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	273
a, b, c (Å)	11.2532 (18), 10.4310 (17), 17.226 (3)
V (Å³)	2022.1 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.31 × 0.27 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.972, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	12287, 1794, 1626
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.098, 1.09
No. of reflections	1794
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

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···O2ⁱ	0.82	2.61	3.0523 (14)	115.8
O1—H1···N1ⁱ	0.82	2.03	2.8464 (14)	173.5
N2—H2A···O2ⁱⁱ	0.86	2.44	3.2777 (16)	164.1
C10—H10B···Cg1ⁱⁱⁱ	0.96	2.90	3.7169 (19)	144.0

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

Acknowledgements

The authors acknowledge financial support from Hangzhou Vocational and Technical College, China.

References

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360. CrossRef CAS Web of Science Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394. 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