organic compounds
Methyl 2-[(E)-3-hydroxy-4-methoxybenzylidene]hydrazinecarboxylate
aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, and bResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
*Correspondence e-mail: zgdhxc@126.com
The title compound, C10H12N2O4, adopts a trans configuration with respect to the C=N bond. The hydrazinecarboxylate group is twisted from the benzene ring by 6.62 (5)° and an intramolecular O—H⋯O hydrogen bond occurs. In the molecules are linked into a two-dimensional network parallel to (100) by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds. In addition, weak C—H⋯π interactions are observed.
Related literature
For properties of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For Schiff base metal complexes, see: Kahwa et al. (1986); Santos et al. (2001). For a related structure, see: Shang et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2002); cell 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
10.1107/S1600536809018996/ci2804sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809018996/ci2804Isup2.hkl
3-Hydroxy-4-methoxy-benzaldehyde (1.52 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 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 in 75% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 398–401 K).
H atoms were positioned geometrically (N-H = 0.86 Å and C-H = 0.93 or 0.96 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 2002); cell
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).Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond. | |
Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines. |
C10H12N2O4 | F(000) = 472 |
Mr = 224.22 | Dx = 1.413 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1944 reflections |
a = 7.7223 (12) Å | θ = 2.6–25.5° |
b = 9.2106 (14) Å | µ = 0.11 mm−1 |
c = 15.092 (2) Å | T = 223 K |
β = 100.944 (6)° | Block, colourless |
V = 1054.0 (3) Å3 | 0.18 × 0.16 × 0.15 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1944 independent reflections |
Radiation source: fine-focus sealed tube | 1657 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→8 |
Tmin = 0.978, Tmax = 0.982 | k = −11→11 |
5767 measured reflections | l = −18→18 |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.1597P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1944 reflections | Δρmax = 0.19 e Å−3 |
149 parameters | Δρmin = −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: 0.035 (4) |
C10H12N2O4 | V = 1054.0 (3) Å3 |
Mr = 224.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7223 (12) Å | µ = 0.11 mm−1 |
b = 9.2106 (14) Å | T = 223 K |
c = 15.092 (2) Å | 0.18 × 0.16 × 0.15 mm |
β = 100.944 (6)° |
Bruker SMART CCD area-detector diffractometer | 1944 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1657 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.982 | Rint = 0.024 |
5767 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.19 e Å−3 |
1944 reflections | Δρmin = −0.18 e Å−3 |
149 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C9 | 1.14900 (17) | 0.19752 (13) | 0.79259 (8) | 0.0395 (3) | |
C8 | 0.89788 (18) | 0.11117 (13) | 0.58309 (9) | 0.0435 (3) | |
H8 | 0.8814 | 0.0133 | 0.5941 | 0.052* | |
C3 | 0.78128 (16) | 0.37223 (13) | 0.39017 (8) | 0.0386 (3) | |
C5 | 0.84592 (17) | 0.31881 (13) | 0.47483 (8) | 0.0392 (3) | |
H5 | 0.9053 | 0.3802 | 0.5193 | 0.047* | |
C7 | 0.82305 (17) | 0.17208 (13) | 0.49464 (8) | 0.0399 (3) | |
C2 | 0.68958 (16) | 0.28075 (14) | 0.32243 (8) | 0.0401 (3) | |
C6 | 0.73162 (19) | 0.08300 (14) | 0.42746 (9) | 0.0475 (3) | |
H6 | 0.7149 | −0.0143 | 0.4401 | 0.057* | |
C4 | 0.66479 (18) | 0.13636 (14) | 0.34190 (9) | 0.0466 (3) | |
H4 | 0.6035 | 0.0753 | 0.2978 | 0.056* | |
C10 | 1.3093 (2) | 0.17575 (17) | 0.94154 (9) | 0.0564 (4) | |
H10A | 1.3936 | 0.2432 | 0.9261 | 0.085* | |
H10B | 1.3697 | 0.1025 | 0.9810 | 0.085* | |
H10C | 1.2281 | 0.2263 | 0.9714 | 0.085* | |
C1 | 0.5523 (2) | 0.25850 (18) | 0.16765 (10) | 0.0575 (4) | |
H1A | 0.6295 | 0.1791 | 0.1614 | 0.086* | |
H1B | 0.5317 | 0.3150 | 0.1132 | 0.086* | |
H1C | 0.4422 | 0.2214 | 0.1787 | 0.086* | |
O1 | 0.63158 (13) | 0.34761 (10) | 0.24138 (6) | 0.0500 (3) | |
O4 | 1.21426 (13) | 0.10865 (10) | 0.86081 (6) | 0.0513 (3) | |
O3 | 1.17310 (14) | 0.32803 (9) | 0.79258 (6) | 0.0529 (3) | |
O2 | 0.80571 (14) | 0.51620 (9) | 0.37432 (6) | 0.0520 (3) | |
H2 | 0.7894 | 0.5307 | 0.3197 | 0.078* | |
N1 | 0.98497 (14) | 0.18969 (11) | 0.64511 (7) | 0.0420 (3) | |
N2 | 1.05406 (15) | 0.12010 (11) | 0.72457 (7) | 0.0442 (3) | |
H2A | 1.0369 | 0.0287 | 0.7307 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C9 | 0.0475 (7) | 0.0337 (6) | 0.0380 (7) | 0.0026 (5) | 0.0096 (5) | 0.0032 (5) |
C8 | 0.0531 (8) | 0.0325 (6) | 0.0440 (7) | −0.0037 (5) | 0.0067 (6) | 0.0023 (5) |
C3 | 0.0427 (7) | 0.0331 (6) | 0.0406 (7) | 0.0000 (5) | 0.0091 (5) | −0.0006 (5) |
C5 | 0.0441 (7) | 0.0354 (6) | 0.0372 (6) | −0.0039 (5) | 0.0057 (5) | −0.0032 (5) |
C7 | 0.0425 (7) | 0.0369 (6) | 0.0397 (7) | −0.0015 (5) | 0.0067 (5) | 0.0002 (5) |
C2 | 0.0412 (7) | 0.0415 (7) | 0.0369 (7) | 0.0025 (5) | 0.0060 (5) | −0.0007 (5) |
C6 | 0.0571 (8) | 0.0335 (6) | 0.0497 (8) | −0.0070 (6) | 0.0045 (6) | −0.0007 (5) |
C4 | 0.0518 (8) | 0.0417 (7) | 0.0430 (7) | −0.0061 (6) | 0.0003 (6) | −0.0079 (5) |
C10 | 0.0626 (9) | 0.0631 (9) | 0.0391 (8) | −0.0074 (7) | −0.0015 (6) | 0.0067 (6) |
C1 | 0.0618 (9) | 0.0646 (9) | 0.0411 (8) | −0.0054 (7) | −0.0030 (6) | −0.0032 (7) |
O1 | 0.0606 (6) | 0.0474 (5) | 0.0377 (5) | 0.0009 (4) | −0.0018 (4) | 0.0008 (4) |
O4 | 0.0664 (6) | 0.0407 (5) | 0.0416 (5) | −0.0009 (4) | −0.0027 (4) | 0.0066 (4) |
O3 | 0.0776 (7) | 0.0341 (5) | 0.0440 (5) | −0.0049 (4) | 0.0038 (5) | 0.0007 (4) |
O2 | 0.0772 (7) | 0.0348 (5) | 0.0415 (5) | −0.0048 (4) | 0.0053 (5) | 0.0044 (4) |
N1 | 0.0517 (6) | 0.0348 (5) | 0.0380 (6) | 0.0009 (4) | 0.0049 (5) | 0.0046 (4) |
N2 | 0.0602 (7) | 0.0300 (5) | 0.0393 (6) | −0.0015 (5) | 0.0015 (5) | 0.0040 (4) |
C9—O3 | 1.2164 (15) | C6—C4 | 1.3864 (19) |
C9—O4 | 1.3369 (15) | C6—H6 | 0.93 |
C9—N2 | 1.3469 (16) | C4—H4 | 0.93 |
C8—N1 | 1.2698 (16) | C10—O4 | 1.4371 (16) |
C8—C7 | 1.4621 (17) | C10—H10A | 0.96 |
C8—H8 | 0.93 | C10—H10B | 0.96 |
C3—O2 | 1.3669 (14) | C10—H10C | 0.96 |
C3—C5 | 1.3717 (17) | C1—O1 | 1.4241 (16) |
C3—C2 | 1.4078 (17) | C1—H1A | 0.96 |
C5—C7 | 1.4025 (17) | C1—H1B | 0.96 |
C5—H5 | 0.93 | C1—H1C | 0.96 |
C7—C6 | 1.3885 (18) | O2—H2 | 0.82 |
C2—O1 | 1.3668 (15) | N1—N2 | 1.3750 (14) |
C2—C4 | 1.3831 (19) | N2—H2A | 0.86 |
O3—C9—O4 | 124.74 (12) | C2—C4—H4 | 120.1 |
O3—C9—N2 | 125.75 (11) | C6—C4—H4 | 120.1 |
O4—C9—N2 | 109.51 (10) | O4—C10—H10A | 109.5 |
N1—C8—C7 | 121.11 (11) | O4—C10—H10B | 109.5 |
N1—C8—H8 | 119.4 | H10A—C10—H10B | 109.5 |
C7—C8—H8 | 119.4 | O4—C10—H10C | 109.5 |
O2—C3—C5 | 118.24 (11) | H10A—C10—H10C | 109.5 |
O2—C3—C2 | 121.38 (11) | H10B—C10—H10C | 109.5 |
C5—C3—C2 | 120.37 (11) | O1—C1—H1A | 109.5 |
C3—C5—C7 | 120.40 (11) | O1—C1—H1B | 109.5 |
C3—C5—H5 | 119.8 | H1A—C1—H1B | 109.5 |
C7—C5—H5 | 119.8 | O1—C1—H1C | 109.5 |
C6—C7—C5 | 118.74 (12) | H1A—C1—H1C | 109.5 |
C6—C7—C8 | 119.87 (11) | H1B—C1—H1C | 109.5 |
C5—C7—C8 | 121.36 (11) | C2—O1—C1 | 117.31 (11) |
O1—C2—C4 | 126.04 (11) | C9—O4—C10 | 116.53 (10) |
O1—C2—C3 | 114.48 (11) | C3—O2—H2 | 109.5 |
C4—C2—C3 | 119.47 (11) | C8—N1—N2 | 116.16 (10) |
C4—C6—C7 | 121.22 (12) | C9—N2—N1 | 118.88 (10) |
C4—C6—H6 | 119.4 | C9—N2—H2A | 120.6 |
C7—C6—H6 | 119.4 | N1—N2—H2A | 120.6 |
C2—C4—C6 | 119.79 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 2.28 | 2.6871 (13) | 112 |
O2—H2···O3i | 0.82 | 2.20 | 2.9303 (13) | 148 |
N2—H2A···O3ii | 0.86 | 2.44 | 3.1951 (15) | 147 |
C8—H8···O3ii | 0.93 | 2.51 | 3.3185 (16) | 146 |
C10—H10A···Cg1iii | 0.96 | 2.87 | 3.6878 (18) | 143 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) x+1, −y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H12N2O4 |
Mr | 224.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 223 |
a, b, c (Å) | 7.7223 (12), 9.2106 (14), 15.092 (2) |
β (°) | 100.944 (6) |
V (Å3) | 1054.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.18 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.978, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5767, 1944, 1657 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.098, 1.05 |
No. of reflections | 1944 |
No. of parameters | 149 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 2.28 | 2.6871 (13) | 112 |
O2—H2···O3i | 0.82 | 2.20 | 2.9303 (13) | 148 |
N2—H2A···O3ii | 0.86 | 2.44 | 3.1951 (15) | 147 |
C8—H8···O3ii | 0.93 | 2.51 | 3.3185 (16) | 146 |
C10—H10A···Cg1iii | 0.96 | 2.87 | 3.6878 (18) | 143 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) x+1, −y−1/2, z−1/2. |
Acknowledgements
The authors thank Hangzhou Vocational and Technical College for financial support.
References
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Benzaldehydehydrazone derivatives have attracted much attention 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 interesting properties (Borg et al., 1999). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). We report here the crystal structure of the title compound (Fig. 1).
The title molecule adopts a trans configuration with respect to the C═N bond. The hydrazinecarboxylate group is twisted from the benzene ring by 6.62 (5)°. The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007). An intramolecular O—H···O interaction is observed.
In the crystal structure, the molecules are linked into a two-dimensional network parallel to the (100) by O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1 and Fig.2). In addition, a C—H···π interaction is observed.