Ethyl N′-[(E)-4-hydroxy­benzyl­idene]hydrazinecarboxyl­ate at 123 K

Cheng, X.-W.

doi:10.1107/S1600536808019818

organic compounds

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Volume 64| Part 8| August 2008| Page o1396

doi:10.1107/S1600536808019818

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Ethyl N′-[(E)-4-hydroxybenzylidene]hydrazinecarboxylate at 123 K

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 19 June 2008; accepted 29 June 2008; online 5 July 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 14.6 (1)°. Molecules are linked into a three-dimensional network by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, and by C—H⋯π interactions.

Related literature

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

Experimental

Crystal data

C₁₀H₁₂N₂O₃
M_r = 208.22
Orthorhombic, P b c a
a = 11.342 (3) Å
b = 7.6114 (17) Å
c = 24.986 (5) Å
V = 2157.0 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 123 (2) K
0.26 × 0.25 × 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
21084 measured reflections
1900 independent reflections
1521 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.125
S = 1.02
1900 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.96	2.752 (2)	161
N2—H2A⋯O2ⁱⁱ	0.86	2.11	2.936 (2)	161
C9—H9B⋯O1ⁱⁱⁱ	0.97	2.57	3.425 (3)	148
C2—H2⋯Cg1^iv	0.93	2.97	3.636 (2)	130
C5—H5⋯Cg1^v	0.93	2.77	3.613 (2)	151
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iv) $[-x-{\script{1\over 2}}, y-{\script{3\over 2}}, z]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536808019818/ci2620sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019818/ci2620Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives 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 intermidiates for 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 hydrazine carboxylic acid ethyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C1–C6 ring and the C7/C8/N1/N2/O2/O3 plane is 14.6 (1)°. The bond lengths and angles agree with those observed for N'-(4-methoxybenzylidene)methoxyformohydrazide (Shang et al., 2007).

In the crystal structure, O—H···O, N—H···O and C—H···O hydrogen bonds and C—H···π interactions (Table 1) link the molecules into a three-dimensional network (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: Shang et al. (2007). Cg1 is the centroid of the C1–C6 ring.

Experimental top

4-Hydroxybenzaldehyde (12.2 g, 0.1 mol) and ethyl hydrazinecarboxylate (10.4 g, 0.1 mol) were dissolved in methanol (50 ml) with stirring and left for 6 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 460–462 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.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds.

Ethyl N'-[(E)-4-hydroxybenzylidene]hydrazinecarboxylate top

Crystal data top

C₁₀H₁₂N₂O₃	F(000) = 880
M_r = 208.22	D_x = 1.282 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1900 reflections
a = 11.342 (3) Å	θ = 1.6–25.0°
b = 7.6114 (17) Å	µ = 0.10 mm⁻¹
c = 24.986 (5) Å	T = 123 K
V = 2157.0 (9) Å³	Block, colourless
Z = 8	0.26 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1900 independent reflections
Radiation source: fine-focus sealed tube	1521 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→13
T_min = 0.965, T_max = 0.968	k = −8→9
21084 measured reflections	l = −28→29

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0722P)² + 0.4536P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
1900 reflections	Δρ_max = 0.21 e Å⁻³
137 parameters	Δρ_min = −0.18 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: 0.0110 (18)

Crystal data top

C₁₀H₁₂N₂O₃	V = 2157.0 (9) Å³
M_r = 208.22	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.342 (3) Å	µ = 0.10 mm⁻¹
b = 7.6114 (17) Å	T = 123 K
c = 24.986 (5) Å	0.26 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1900 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1521 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.040
21084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.02	Δρ_max = 0.21 e Å⁻³
1900 reflections	Δρ_min = −0.18 e Å⁻³
137 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
O2	0.38975 (10)	0.12445 (15)	0.06297 (5)	0.0550 (4)
O1	0.10016 (11)	0.07264 (18)	0.38449 (5)	0.0662 (4)
H1	0.0396	0.1121	0.3978	0.099*
O3	0.31948 (13)	0.34186 (17)	0.01045 (5)	0.0708 (4)
N1	0.23119 (12)	0.22542 (18)	0.13972 (5)	0.0472 (4)
N2	0.23619 (13)	0.29838 (19)	0.08895 (5)	0.0533 (4)
H2A	0.1859	0.3769	0.0794	0.064*
C4	0.21890 (13)	0.1206 (2)	0.25066 (6)	0.0451 (4)
H4	0.2850	0.0839	0.2317	0.054*
C6	0.13472 (13)	0.2248 (2)	0.22515 (6)	0.0422 (4)
C1	0.10857 (14)	0.1271 (2)	0.33239 (6)	0.0459 (4)
C3	0.02413 (14)	0.2324 (2)	0.30815 (7)	0.0493 (4)
H3	−0.0410	0.2707	0.3275	0.059*
C7	0.14800 (14)	0.2813 (2)	0.16958 (7)	0.0471 (4)
H7	0.0940	0.3608	0.1555	0.056*
C2	0.20628 (14)	0.0712 (2)	0.30315 (6)	0.0481 (4)
H2	0.2629	0.0004	0.3192	0.058*
C5	0.03729 (14)	0.2800 (2)	0.25500 (7)	0.0491 (4)
H5	−0.0197	0.3501	0.2389	0.059*
C8	0.32053 (15)	0.2449 (2)	0.05487 (6)	0.0489 (4)
C9	0.3972 (3)	0.2864 (3)	−0.03288 (9)	0.1029 (9)
H9A	0.4749	0.2601	−0.0188	0.123*
H9B	0.3663	0.1809	−0.0495	0.123*
C10	0.4055 (3)	0.4246 (4)	−0.07193 (10)	0.1096 (10)
H10A	0.4564	0.3880	−0.1005	0.164*
H10B	0.4372	0.5282	−0.0554	0.164*
H10C	0.3285	0.4497	−0.0859	0.164*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0572 (7)	0.0535 (7)	0.0542 (7)	0.0039 (6)	0.0023 (5)	0.0014 (5)
O1	0.0693 (8)	0.0818 (9)	0.0475 (8)	0.0116 (7)	0.0088 (6)	0.0139 (6)
O3	0.1000 (10)	0.0651 (8)	0.0472 (7)	0.0138 (7)	0.0168 (7)	0.0131 (6)
N1	0.0533 (8)	0.0472 (8)	0.0412 (8)	0.0007 (6)	0.0011 (6)	0.0059 (6)
N2	0.0639 (9)	0.0534 (8)	0.0426 (8)	0.0116 (7)	0.0048 (7)	0.0112 (6)
C4	0.0428 (8)	0.0455 (9)	0.0469 (9)	0.0038 (7)	0.0050 (7)	−0.0010 (7)
C6	0.0431 (8)	0.0387 (8)	0.0447 (9)	−0.0018 (6)	−0.0001 (6)	0.0012 (6)
C1	0.0508 (9)	0.0447 (9)	0.0421 (9)	−0.0033 (7)	0.0001 (7)	0.0022 (7)
C3	0.0426 (8)	0.0528 (10)	0.0526 (10)	0.0030 (7)	0.0077 (7)	0.0009 (8)
C7	0.0495 (9)	0.0447 (9)	0.0471 (10)	0.0040 (7)	−0.0013 (7)	0.0053 (7)
C2	0.0484 (8)	0.0478 (9)	0.0483 (10)	0.0063 (7)	−0.0029 (7)	0.0024 (7)
C5	0.0437 (8)	0.0501 (9)	0.0534 (10)	0.0061 (7)	0.0001 (7)	0.0069 (7)
C8	0.0592 (10)	0.0455 (9)	0.0418 (9)	−0.0046 (8)	0.0000 (7)	0.0011 (7)
C9	0.155 (3)	0.0936 (18)	0.0598 (14)	0.0209 (17)	0.0467 (16)	0.0063 (12)
C10	0.107 (2)	0.155 (3)	0.0666 (15)	0.0021 (19)	0.0209 (13)	0.0293 (16)

Geometric parameters (Å, º) top

O2—C8	1.224 (2)	C1—C3	1.388 (2)
O1—C1	1.3695 (19)	C1—C2	1.394 (2)
O1—H1	0.82	C3—C5	1.385 (2)
O3—C8	1.3329 (19)	C3—H3	0.93
O3—C9	1.458 (3)	C7—H7	0.93
N1—C7	1.276 (2)	C2—H2	0.93
N1—N2	1.3860 (18)	C5—H5	0.93
N2—C8	1.344 (2)	C9—C10	1.437 (3)
N2—H2A	0.86	C9—H9A	0.97
C4—C2	1.372 (2)	C9—H9B	0.97
C4—C6	1.395 (2)	C10—H10A	0.96
C4—H4	0.93	C10—H10B	0.96
C6—C5	1.398 (2)	C10—H10C	0.96
C6—C7	1.462 (2)

C1—O1—H1	109.5	C4—C2—C1	120.03 (14)
C8—O3—C9	116.92 (16)	C4—C2—H2	120.0
C7—N1—N2	115.58 (13)	C1—C2—H2	120.0
C8—N2—N1	119.19 (14)	C3—C5—C6	121.20 (15)
C8—N2—H2A	120.4	C3—C5—H5	119.4
N1—N2—H2A	120.4	C6—C5—H5	119.4
C2—C4—C6	121.41 (14)	O2—C8—O3	123.93 (15)
C2—C4—H4	119.3	O2—C8—N2	125.36 (15)
C6—C4—H4	119.3	O3—C8—N2	110.71 (15)
C4—C6—C5	117.91 (15)	C10—C9—O3	109.4 (2)
C4—C6—C7	122.06 (14)	C10—C9—H9A	109.8
C5—C6—C7	119.99 (14)	O3—C9—H9A	109.8
O1—C1—C3	122.78 (14)	C10—C9—H9B	109.8
O1—C1—C2	117.48 (14)	O3—C9—H9B	109.8
C3—C1—C2	119.74 (15)	H9A—C9—H9B	108.2
C5—C3—C1	119.70 (15)	C9—C10—H10A	109.5
C5—C3—H3	120.1	C9—C10—H10B	109.5
C1—C3—H3	120.1	H10A—C10—H10B	109.5
N1—C7—C6	122.24 (15)	C9—C10—H10C	109.5
N1—C7—H7	118.9	H10A—C10—H10C	109.5
C6—C7—H7	118.9	H10B—C10—H10C	109.5

C7—N1—N2—C8	−179.28 (15)	C3—C1—C2—C4	0.2 (2)
C2—C4—C6—C5	0.9 (2)	C1—C3—C5—C6	−0.3 (3)
C2—C4—C6—C7	178.80 (15)	C4—C6—C5—C3	−0.3 (2)
O1—C1—C3—C5	−178.91 (15)	C7—C6—C5—C3	−178.25 (15)
C2—C1—C3—C5	0.4 (2)	C9—O3—C8—O2	7.1 (3)
N2—N1—C7—C6	−176.50 (13)	C9—O3—C8—N2	−173.16 (19)
C4—C6—C7—N1	6.8 (3)	N1—N2—C8—O2	6.4 (3)
C5—C6—C7—N1	−175.38 (15)	N1—N2—C8—O3	−173.41 (14)
C6—C4—C2—C1	−0.9 (2)	C8—O3—C9—C10	−166.9 (2)
O1—C1—C2—C4	179.54 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.96	2.752 (2)	161
N2—H2A···O2ⁱⁱ	0.86	2.11	2.936 (2)	161
C9—H9B···O1ⁱⁱⁱ	0.97	2.57	3.425 (3)	148
C2—H2···Cg1^iv	0.93	2.97	3.636 (2)	130
C5—H5···Cg1^v	0.93	2.77	3.613 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₃
M_r	208.22
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	11.342 (3), 7.6114 (17), 24.986 (5)
V (Å³)	2157.0 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.25 × 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	21084, 1900, 1521
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.125, 1.02
No. of reflections	1900
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18

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	1.96	2.752 (2)	161
N2—H2A···O2ⁱⁱ	0.86	2.11	2.936 (2)	161
C9—H9B···O1ⁱⁱⁱ	0.97	2.57	3.425 (3)	148
C2—H2···Cg1^iv	0.93	2.97	3.636 (2)	130
C5—H5···Cg1^v	0.93	2.77	3.613 (2)	151

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

Acknowledgements

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

References

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