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

Abstract

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,

• a = 11.342 (3) Å

• b = 7.6114 (17) Å

• c = 24.986 (5) Å

• V = 2157.0 (9) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯Cg1iv	0.93	2.97	3.636 (2)	130
C5—H5⋯Cg1v	0.93	2.77	3.613 (2)	151

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

H atoms were positioned geometrically (N—H = 0.86 Å, O—H = 0.82 Å and C—H = 0.93–0.97 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N) and 1.5U_eq(O).

Figures

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.

Crystal data

C10H12N2O3	F000 = 880
Mr = 208.22	Dx = 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 = 1.6–25.0º
b = 7.6114 (17) Å	µ = 0.10 mm−1
c = 24.986 (5) Å	T = 123 (2) K
V = 2157.0 (9) Å3	Block, colourless
Z = 8	0.26 × 0.25 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1900 independent reflections
Radiation source: fine-focus sealed tube	1521 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.040
T = 123(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.6º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −13→13
Tmin = 0.965, Tmax = 0.968	k = −8→9
21084 measured reflections	l = −28→29

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0722P)2 + 0.4536P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.125	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.21 e Å−3
1900 reflections	Δρmin = −0.18 e Å−3
137 parameters	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)
Secondary atom site location: difference Fourier map

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···Cg1iv	0.93	2.97	3.636 (2)	130
C5—H5···Cg1v	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.