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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1766.
Published online 2008 August 16. doi:  10.1107/S1600536808025191
PMCID: PMC2960505

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

Abstract

In the mol­ecule of the title compound, C11H14N2O3, the dihedral angle between the benzene ring and the hydrazinecarboxyl­ate mean plane is 3.65 (12)°. Intra­molecular C—H(...)N and O—H(...)N hydrogen bonds result in the formation of a nearly planar six-membered ring, which is oriented at a dihedral angle of 2.38 (3)° with respect to the benzene ring, and a five-membered ring having an envelope conformation. In the crystal structure, inter­molecular N—H(...)O and C—H(...)N hydrogen bonds link the mol­ecules. There is a C—H(...)π contact between the benzene ring and the methyl group of the ethyl substituent.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1766-scheme1.jpg

Experimental

Crystal data

  • C11H14N2O3
  • M r = 222.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1766-efi1.jpg
  • a = 8.0841 (7) Å
  • b = 23.052 (2) Å
  • c = 6.6019 (6) Å
  • β = 111.584 (3)°
  • V = 1144.03 (18) 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 [triangle]) T min = 0.973, T max = 0.981
  • 12167 measured reflections
  • 2018 independent reflections
  • 1360 reflections with I > 2σ(I)
  • R int = 0.089

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.117
  • S = 1.05
  • 2018 reflections
  • 149 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.12 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025191/hk2507sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025191/hk2507Isup2.hkl

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

Acknowledgments

The author acknowledges the financial support of Zhejiang Police College, China.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attention for a long time, due to their pharmacological activities (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermidiates fot 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, we report herein the crystal structure of the title compound.

The title molecule (Fig. 1) adopts a trans configuration with respect to the C═N bond. The bond lengths and angles agree with those observed for (E)-ethyl N'-(4-bromobenzylidene)hydrazinecarboxylate (Gao, 2008). The ring A (C1-C6) is, of course, planar and it is oriented with respect to the mean plane of (C9/C10/C11/N1/N2/O2/O3) at a dihedral angle of 3.65 (12)°. The intramolecular C-H···N and O-H···N hydrogen bonds (Table 1) result in the formation of five- and six-membered rings: B (N1/N2/C7/C8/H8A) and C (N1/O1/H1/C1/C6/C7). Ring B adopts envelope conformation, with H8A atom displaced by -0.413 (3) Å from the plane of the other ring atoms. Ring C is nearly planar and it is oriented with respect to ring A at a dihedral angle of 2.38 (3)°.

In the crystal structure, intermolecular N-H···O and C-H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. A C—H···π contact (Table 1) between the benzene ring and the methyl group further stabilize the structure.

Experimental

2-Hydroxy-acetophenone (1.36 g, 0.01 mol) and ethyl hydrazinecarboxylate (1.04 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 (yield; 85%, m.p. 487-489 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with O-H = 0.82 Å (for OH), N-H = 0.86 Å (for NH) and C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N,O), where x = 1.5 for OH H and methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
Fig. 2.
A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C11H14N2O3F000 = 472
Mr = 222.24Dx = 1.290 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1018 reflections
a = 8.0841 (7) Åθ = 1.8–25.0º
b = 23.052 (2) ŵ = 0.10 mm1
c = 6.6019 (6) ÅT = 273 (2) K
β = 111.584 (3)ºBlock, colourless
V = 1144.03 (18) Å30.28 × 0.24 × 0.23 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2018 independent reflections
Radiation source: fine-focus sealed tube1360 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.089
T = 273(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −9→9
Tmin = 0.973, Tmax = 0.981k = −27→25
12167 measured reflectionsl = −7→7

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040  w = 1/[σ2(Fo2) + (0.0565P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.117(Δ/σ)max = 0.004
S = 1.05Δρmax = 0.21 e Å3
2018 reflectionsΔρmin = −0.12 e Å3
149 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.003 (2)
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 > 2sigma(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)

xyzUiso*/Ueq
O10.48727 (18)0.67615 (6)−0.1086 (2)0.0764 (4)
H10.47140.6532−0.02260.115*
O20.33133 (16)0.55003 (5)0.4805 (2)0.0700 (4)
O30.30739 (14)0.62476 (5)0.25268 (17)0.0577 (4)
N10.54972 (18)0.58512 (6)0.1300 (2)0.0547 (4)
N20.50506 (17)0.55461 (6)0.2812 (2)0.0575 (4)
H2A0.55830.52260.33330.069*
C10.6180 (2)0.65614 (8)−0.1721 (3)0.0596 (5)
C20.6542 (3)0.68841 (9)−0.3299 (3)0.0758 (6)
H20.59010.7221−0.38490.091*
C30.7839 (3)0.67078 (11)−0.4046 (3)0.0849 (7)
H30.80640.6925−0.51050.102*
C40.8806 (3)0.62129 (11)−0.3238 (4)0.0840 (6)
H40.96900.6095−0.37360.101*
C50.8453 (3)0.58970 (9)−0.1696 (3)0.0704 (5)
H50.91120.5562−0.11660.084*
C60.7148 (2)0.60525 (7)−0.0876 (3)0.0534 (4)
C70.6823 (2)0.56945 (7)0.0794 (3)0.0524 (4)
C80.7998 (2)0.51833 (8)0.1808 (3)0.0721 (6)
H8A0.79860.51140.32360.108*
H8B0.91920.52640.19150.108*
H8C0.75640.48460.09180.108*
C90.3771 (2)0.57519 (7)0.3476 (3)0.0521 (4)
C100.1786 (2)0.65209 (8)0.3283 (3)0.0606 (5)
H10A0.23130.65940.48370.073*
H10B0.07600.62710.30020.073*
C110.1244 (3)0.70765 (8)0.2071 (3)0.0771 (6)
H11A0.22660.73230.23840.116*
H11B0.03740.72670.25100.116*
H11C0.07440.69990.05350.116*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0824 (9)0.0654 (9)0.0859 (10)0.0151 (7)0.0364 (8)0.0187 (7)
O20.0769 (8)0.0633 (8)0.0855 (9)0.0117 (6)0.0484 (7)0.0207 (7)
O30.0619 (7)0.0571 (8)0.0613 (7)0.0126 (6)0.0310 (6)0.0104 (6)
N10.0578 (8)0.0550 (9)0.0557 (8)0.0027 (6)0.0262 (7)0.0052 (7)
N20.0613 (8)0.0538 (9)0.0651 (9)0.0103 (7)0.0323 (7)0.0122 (7)
C10.0621 (10)0.0590 (11)0.0553 (10)−0.0084 (9)0.0188 (9)−0.0026 (9)
C20.0857 (14)0.0681 (13)0.0640 (12)−0.0163 (11)0.0163 (11)0.0106 (10)
C30.1013 (16)0.1014 (18)0.0584 (13)−0.0409 (14)0.0370 (12)−0.0050 (12)
C40.0921 (15)0.1005 (18)0.0737 (14)−0.0166 (14)0.0471 (13)−0.0061 (13)
C50.0756 (12)0.0776 (14)0.0682 (12)−0.0021 (10)0.0385 (10)−0.0014 (10)
C60.0561 (10)0.0547 (11)0.0507 (10)−0.0066 (8)0.0211 (8)−0.0052 (8)
C70.0522 (9)0.0510 (10)0.0548 (10)0.0002 (8)0.0207 (8)−0.0033 (8)
C80.0722 (12)0.0655 (13)0.0891 (14)0.0136 (10)0.0420 (11)0.0129 (10)
C90.0533 (9)0.0509 (11)0.0545 (10)0.0019 (8)0.0227 (8)0.0032 (8)
C100.0572 (10)0.0685 (12)0.0602 (11)0.0091 (8)0.0266 (8)−0.0005 (9)
C110.0907 (14)0.0644 (13)0.0770 (13)0.0209 (11)0.0319 (11)0.0041 (10)

Geometric parameters (Å, °)

O1—H10.8200C7—N11.286 (2)
N2—N11.3735 (18)C7—C81.507 (2)
N2—H2A0.8600C8—H8A0.9600
C1—O11.353 (2)C8—H8B0.9600
C2—C31.374 (3)C8—H8C0.9600
C2—C11.396 (3)C9—O21.2168 (18)
C2—H20.9300C9—O31.3251 (19)
C3—C41.375 (3)C9—N21.350 (2)
C3—H30.9300C10—O31.4537 (19)
C4—H40.9300C10—C111.488 (3)
C5—C41.365 (3)C10—H10A0.9700
C5—H50.9300C10—H10B0.9700
C6—C51.398 (2)C11—H11A0.9600
C6—C11.407 (2)C11—H11B0.9600
C6—C71.476 (2)C11—H11C0.9600
C1—O1—H1109.5N1—C7—C6115.56 (14)
C9—O3—C10116.40 (13)N1—C7—C8123.60 (15)
C7—N1—N2120.80 (14)C6—C7—C8120.84 (14)
C9—N2—N1119.60 (14)C7—C8—H8A109.5
C9—N2—H2A120.2C7—C8—H8B109.5
N1—N2—H2A120.2H8A—C8—H8B109.5
O1—C1—C2116.86 (18)C7—C8—H8C109.5
O1—C1—C6123.05 (16)H8A—C8—H8C109.5
C2—C1—C6120.09 (18)H8B—C8—H8C109.5
C3—C2—C1120.5 (2)O2—C9—O3124.27 (15)
C3—C2—H2119.7O2—C9—N2122.61 (16)
C1—C2—H2119.7O3—C9—N2113.11 (14)
C2—C3—C4120.43 (19)O3—C10—C11107.12 (14)
C2—C3—H3119.8O3—C10—H10A110.3
C4—C3—H3119.8C11—C10—H10A110.3
C5—C4—C3119.1 (2)O3—C10—H10B110.3
C5—C4—H4120.4C11—C10—H10B110.3
C3—C4—H4120.4H10A—C10—H10B108.5
C4—C5—C6123.2 (2)C10—C11—H11A109.5
C4—C5—H5118.4C10—C11—H11B109.5
C6—C5—H5118.4H11A—C11—H11B109.5
C5—C6—C1116.69 (16)C10—C11—H11C109.5
C5—C6—C7120.86 (16)H11A—C11—H11C109.5
C1—C6—C7122.45 (15)H11B—C11—H11C109.5
C9—N2—N1—C7173.35 (15)C5—C6—C7—N1−174.51 (15)
C3—C2—C1—O1−179.43 (16)C1—C6—C7—N15.5 (2)
C3—C2—C1—C60.2 (3)C5—C6—C7—C85.6 (2)
C1—C2—C3—C4−0.4 (3)C1—C6—C7—C8−174.34 (16)
C2—C3—C4—C50.5 (3)C6—C7—N1—N2179.08 (13)
C6—C5—C4—C3−0.3 (3)C8—C7—N1—N2−1.1 (2)
C5—C6—C1—O1179.61 (16)O2—C9—O3—C105.1 (2)
C7—C6—C1—O1−0.4 (3)N2—C9—O3—C10−175.28 (14)
C5—C6—C1—C20.0 (2)O2—C9—N2—N1179.74 (14)
C7—C6—C1—C2179.98 (15)O3—C9—N2—N10.1 (2)
C1—C6—C5—C40.0 (3)C11—C10—O3—C9177.71 (14)
C7—C6—C5—C4−179.95 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.852.5604 (18)145
N2—H2A···O2i0.862.072.9175 (18)167
C8—H8A···N20.962.492.825 (2)100
C8—H8A···O2i0.962.403.217 (2)142
C11—H11C···Cg1ii0.963.003.748 (3)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2507).

References

  • Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem 42, 433–4342. [PubMed]
  • Bruker (2002). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, B. (2008). Acta Cryst. E64, o1646. [PMC free article] [PubMed]
  • Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
  • Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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