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

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 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,

• a = 8.6432 (8) Å

• b = 12.6696 (11) Å

• c = 9.9810 (9) Å

• β = 109.837 (3)°

• V = 1028.12 (16) ų

• 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[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 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

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, °).

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) ; (ii) . Cg1 is the centroid of the C1–C6 ring.

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

H atoms were positioned geometrically (O-H = 0.82 Å, N-H = 0.86 Å and C-H = 0.93 or 0.96 Å) and refined using a riding model, with U_iso(H) = 1.2–1.5U_eq(C). A rotating group model was used for the methyl groups.

Figures

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.

Crystal data

C10H12N2O3	F000 = 440
Mr = 208.22	Dx = 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 = 2.5–25.0º
b = 12.6696 (11) Å	µ = 0.10 mm−1
c = 9.9810 (9) Å	T = 273 (2) K
β = 109.837 (3)º	Block, colourless
V = 1028.12 (16) Å3	0.28 × 0.24 × 0.23 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1587 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.019
T = 273(2) K	θmax = 25.1º
φ and ω scans	θmin = 2.5º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −10→9
Tmin = 0.973, Tmax = 0.979	k = −14→13
10601 measured reflections	l = −11→11

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.2233P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.26 e Å−3
1809 reflections	Δρmin = −0.12 e Å−3
140 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: 0.017 (3)
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
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 (Ų)

	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, °)

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, °)

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.