(E)-Methyl N′-[1-(2-hydroxy­phen­yl)ethyl­idene]hydrazinecarboxyl­ate

Zhu, B.; Cheng, X.-W.

doi:10.1107/S1600536808024434

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1748

doi:10.1107/S1600536808024434

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(E)-Methyl N′-[1-(2-hydroxyphenyl)ethylidene]hydrazinecarboxylate

Bin Zhu ^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 27 July 2008; accepted 30 July 2008; online 13 August 2008)

The molecule of the title compound, C₁₀H₁₂N₂O₃, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 8.98 (7)°. Intramolecular O—H⋯N and C—H⋯N hydrogen bonds are observed. Molecules are linked into chains along the c axis by N—H⋯O hydrogen bonds. In addition, C—H⋯π interactions are observed.

Related literature

For general background, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For a related structure, see: Cheng (2008 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₃
M_r = 208.22
Monoclinic, P 2₁ /c
a = 8.6432 (8) Å
b = 12.6696 (11) Å
c = 9.9810 (9) Å
β = 109.837 (3)°
V = 1028.12 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 (2) K
0.28 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.973, T_max = 0.979
10601 measured reflections
1809 independent reflections
1587 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.107
S = 1.05
1809 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.12 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	1.85	2.5625 (14)	145
N2—H2A⋯O2ⁱ	0.86	2.25	3.0550 (14)	156
C8—H8A⋯N2	0.96	2.47	2.820 (2)	101
C8—H8C⋯Cg1ⁱⁱ	0.96	2.93	3.803 (2)	151
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1. 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/S1600536808024434/ci2645sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024434/ci2645Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone compounds have received considerable attention for a long time 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 properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound is reported here.

The title molecule (Fig.1) adopts a trans configuration with respect to the C═N bond. The C9/C10/N1/N2/O2/O3 plane of 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 C9/C10/N1/N2/O2/O3 plane is 8.98 (7)°. The bond lengths and angles agree with those observed for methyl N'-((E)-1-phenylethylidene)hydrazinecarboxylate (Cheng, 2008). Intramolecular O—H···N and C—H···N hydrogen bonds are observed.

The molecules are linked into chains along the c axis by N—H···O hydrogen bonds. In addition, C—H···π interactions are observed (Table 1, Fig.2).

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Cheng (2008). Cg1 is the centroid of the C1–C6 ring.

Experimental top

2-Hydroxyacetophenone (1.36 g, 0.01 mol) and methyl hydrazinecarboxylate (0.9 g, 0.01 mol) were dissolved in stirred methanol (15 ml) and left for 2 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 85% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 465–467 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 the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. Dashed lines indicate intramolecular hydrogen bonds.
	Fig. 2. Crystal packing of the title compound. Dashed lines indicate intermolecular hydrogen bonds.

(E)-Methyl N'-[1-(2-hydroxyphenyl)ethylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₃	F(000) = 440
M_r = 208.22	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1809 reflections
a = 8.6432 (8) Å	θ = 2.5–25.0°
b = 12.6696 (11) Å	µ = 0.10 mm⁻¹
c = 9.9810 (9) Å	T = 273 K
β = 109.837 (3)°	Block, colourless
V = 1028.12 (16) Å³	0.28 × 0.24 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→9
T_min = 0.973, T_max = 0.979	k = −14→13
10601 measured reflections	l = −11→11

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) = 0.107	w = 1/[σ²(F_o²) + (0.0557P)² + 0.2233P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1809 reflections	Δρ_max = 0.26 e Å⁻³
140 parameters	Δρ_min = −0.12 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: 0.017 (3)

Crystal data top

C₁₀H₁₂N₂O₃	V = 1028.12 (16) Å³
M_r = 208.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6432 (8) Å	µ = 0.10 mm⁻¹
b = 12.6696 (11) Å	T = 273 K
c = 9.9810 (9) Å	0.28 × 0.24 × 0.23 mm
β = 109.837 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1809 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1587 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.979	R_int = 0.019
10601 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
1809 reflections	Δρ_min = −0.12 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	0.62350 (16)	−0.02927 (10)	0.76460 (14)	0.0409 (3)
C6	0.67306 (16)	−0.04195 (10)	0.91401 (14)	0.0403 (3)
C7	0.79166 (16)	0.03028 (10)	1.01395 (13)	0.0404 (3)
C9	1.01051 (17)	0.25416 (11)	0.97214 (14)	0.0430 (3)
C2	0.51172 (17)	−0.09885 (12)	0.67429 (16)	0.0497 (4)
H2	0.4799	−0.0896	0.5762	0.060*
C3	0.44767 (19)	−0.18132 (12)	0.72853 (18)	0.0577 (4)
H3	0.3740	−0.2279	0.6671	0.069*
C5	0.60373 (19)	−0.12639 (12)	0.96486 (17)	0.0538 (4)
H5	0.6335	−0.1365	1.0627	0.065*
C4	0.4927 (2)	−0.19499 (14)	0.87417 (19)	0.0623 (5)
H4	0.4484	−0.2502	0.9109	0.075*
C10	1.1944 (2)	0.39775 (14)	1.01329 (19)	0.0650 (5)
H10A	1.2220	0.3668	0.9365	0.098*
H10B	1.2933	0.4178	1.0883	0.098*
H10C	1.1272	0.4591	0.9794	0.098*
C8	0.8508 (2)	0.00907 (13)	1.17083 (15)	0.0595 (4)
H8A	0.9553	0.0427	1.2149	0.089*
H8B	0.8622	−0.0657	1.1871	0.089*
H8C	0.7727	0.0365	1.2110	0.089*
O1	0.68111 (13)	0.04936 (8)	0.70165 (10)	0.0535 (3)
H1	0.7464	0.0857	0.7631	0.080*
O2	0.98628 (13)	0.25492 (8)	0.84561 (10)	0.0539 (3)
O3	1.10557 (14)	0.32236 (9)	1.06669 (11)	0.0603 (3)
N1	0.83941 (13)	0.10946 (9)	0.95665 (11)	0.0416 (3)
N2	0.94739 (14)	0.18236 (10)	1.04034 (11)	0.0470 (3)
H2A	0.9736	0.1824	1.1315	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0454 (7)	0.0377 (7)	0.0412 (7)	0.0050 (5)	0.0167 (6)	0.0020 (5)
C6	0.0439 (7)	0.0363 (7)	0.0421 (7)	0.0051 (5)	0.0167 (6)	0.0023 (5)
C7	0.0460 (7)	0.0404 (7)	0.0361 (7)	0.0071 (6)	0.0156 (6)	0.0029 (5)
C9	0.0477 (8)	0.0444 (8)	0.0381 (7)	−0.0012 (6)	0.0163 (6)	−0.0035 (6)
C2	0.0521 (8)	0.0504 (9)	0.0447 (8)	0.0007 (6)	0.0138 (6)	−0.0056 (6)
C3	0.0532 (9)	0.0511 (9)	0.0655 (10)	−0.0078 (7)	0.0156 (8)	−0.0084 (7)
C5	0.0632 (9)	0.0506 (9)	0.0495 (8)	−0.0015 (7)	0.0216 (7)	0.0089 (7)
C4	0.0659 (10)	0.0522 (9)	0.0710 (11)	−0.0131 (7)	0.0260 (8)	0.0056 (8)
C10	0.0688 (10)	0.0671 (11)	0.0637 (10)	−0.0237 (9)	0.0284 (8)	−0.0088 (8)
C8	0.0833 (11)	0.0526 (9)	0.0384 (8)	−0.0026 (8)	0.0151 (7)	0.0045 (7)
O1	0.0721 (7)	0.0501 (6)	0.0362 (5)	−0.0107 (5)	0.0155 (5)	0.0007 (4)
O2	0.0721 (7)	0.0544 (7)	0.0368 (6)	−0.0094 (5)	0.0206 (5)	−0.0010 (4)
O3	0.0716 (7)	0.0673 (7)	0.0464 (6)	−0.0274 (6)	0.0258 (5)	−0.0137 (5)
N1	0.0460 (6)	0.0423 (6)	0.0358 (6)	−0.0029 (5)	0.0130 (5)	−0.0021 (5)
N2	0.0563 (7)	0.0524 (7)	0.0319 (6)	−0.0097 (5)	0.0145 (5)	−0.0034 (5)

Geometric parameters (Å, º) top

C1—O1	1.3592 (16)	C5—C4	1.381 (2)
C1—C2	1.390 (2)	C5—H5	0.93
C1—C6	1.4141 (19)	C4—H4	0.93
C6—C5	1.4027 (19)	C10—O3	1.4364 (19)
C6—C7	1.4796 (19)	C10—H10A	0.96
C7—N1	1.2899 (17)	C10—H10B	0.96
C7—C8	1.4974 (18)	C10—H10C	0.96
C9—O2	1.2081 (16)	C8—H8A	0.96
C9—O3	1.3364 (17)	C8—H8B	0.96
C9—N2	1.3567 (17)	C8—H8C	0.96
C2—C3	1.377 (2)	O1—H1	0.82
C2—H2	0.93	N1—N2	1.3757 (16)
C3—C4	1.382 (2)	N2—H2A	0.86
C3—H3	0.93

O1—C1—C2	116.62 (12)	C5—C4—C3	119.71 (15)
O1—C1—C6	122.91 (12)	C5—C4—H4	120.1
C2—C1—C6	120.46 (13)	C3—C4—H4	120.1
C5—C6—C1	117.03 (13)	O3—C10—H10A	109.5
C5—C6—C7	120.73 (12)	O3—C10—H10B	109.5
C1—C6—C7	122.23 (12)	H10A—C10—H10B	109.5
N1—C7—C6	115.77 (11)	O3—C10—H10C	109.5
N1—C7—C8	123.80 (13)	H10A—C10—H10C	109.5
C6—C7—C8	120.43 (12)	H10B—C10—H10C	109.5
O2—C9—O3	125.45 (13)	C7—C8—H8A	109.5
O2—C9—N2	124.98 (13)	C7—C8—H8B	109.5
O3—C9—N2	109.56 (11)	H8A—C8—H8B	109.5
C3—C2—C1	120.68 (14)	C7—C8—H8C	109.5
C3—C2—H2	119.7	H8A—C8—H8C	109.5
C1—C2—H2	119.7	H8B—C8—H8C	109.5
C2—C3—C4	120.09 (14)	C1—O1—H1	109.5
C2—C3—H3	120.0	C9—O3—C10	116.48 (11)
C4—C3—H3	120.0	C7—N1—N2	120.41 (11)
C4—C5—C6	122.01 (14)	C9—N2—N1	116.81 (11)
C4—C5—H5	119.0	C9—N2—H2A	121.6
C6—C5—H5	119.0	N1—N2—H2A	121.6

O1—C1—C6—C5	179.88 (12)	C1—C6—C5—C4	0.4 (2)
C2—C1—C6—C5	−0.42 (19)	C7—C6—C5—C4	179.96 (14)
O1—C1—C6—C7	0.3 (2)	C6—C5—C4—C3	0.2 (3)
C2—C1—C6—C7	−179.99 (12)	C2—C3—C4—C5	−0.8 (3)
C5—C6—C7—N1	−175.42 (12)	O2—C9—O3—C10	−4.6 (2)
C1—C6—C7—N1	4.12 (19)	N2—C9—O3—C10	174.30 (13)
C5—C6—C7—C8	5.3 (2)	C6—C7—N1—N2	178.87 (11)
C1—C6—C7—C8	−175.19 (13)	C8—C7—N1—N2	−1.8 (2)
O1—C1—C2—C3	179.57 (13)	O2—C9—N2—N1	−4.4 (2)
C6—C1—C2—C3	−0.2 (2)	O3—C9—N2—N1	176.72 (11)
C1—C2—C3—C4	0.8 (2)	C7—N1—N2—C9	170.54 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.85	2.5625 (14)	145
N2—H2A···O2ⁱ	0.86	2.25	3.0550 (14)	156
C8—H8A···N2	0.96	2.47	2.820 (2)	101
C8—H8C···Cg1ⁱⁱ	0.96	2.93	3.803 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₃
M_r	208.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	8.6432 (8), 12.6696 (11), 9.9810 (9)
β (°)	109.837 (3)
V (Å³)	1028.12 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.973, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	10601, 1809, 1587
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.107, 1.05
No. of reflections	1809
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.12

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	1.85	2.5625 (14)	145
N2—H2A···O2ⁱ	0.86	2.25	3.0550 (14)	156
C8—H8A···N2	0.96	2.47	2.820 (2)	101
C8—H8C···Cg1ⁱⁱ	0.96	2.93	3.803 (2)	151

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

Acknowledgements

The authors acknowledge financial support from Zhejiang Police 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
Cheng, X.-W. (2008). Acta Cryst. E64, o1384. Web of Science CSD CrossRef IUCr Journals 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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar