organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N′-(3,4-Di­meth­oxy­benzyl­­idene)acetohydrazide

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

(Received 11 July 2009; accepted 12 July 2009; online 25 July 2009)

In the title mol­ecule, C11H14N2O3, the acetohydrazide group is planar 0.084 (1) Å and forms a dihedral angle of 19.7 (1)° with the benzene ring. One of the meth­oxy groups is coplanar with the attached benzene ring within 0.052 (3) Å, whereas the other is slightly twisted [C—O—C—C = 6.3 (3)°]. The mol­ecule adopts a trans configuration with respect to the C=N bond. In the crystal, the mol­ecules are linked into chains along the a axis by N—H⋯O hydrogen bonds and the chains are cross-linked into a three-dimensional network by C—H⋯O hydrogen bonds.

Related literature

For general background to Schiff bases, see: Cimerman et al. (1997[Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal Chim. Acta, 343, 145-153.]); Offe et al. (1952[Offe, H. A., Siefen, W. & Domagk, G. (1952). Z. Naturforsch. Teil B, 7, 446-447.]); Richardson et al. (1988[Richardson, D., Baker, E., Ponka, P., Wilairat, P., Vitolo, M. L. & Webb, J. (1988). Thalassemia: Pathophysiology and Management, Part B, p. 81. New York: Alan R. Liss Inc.]). For related structures, see: Li & Jian (2008[Li, Y.-F. & Jian, F.-F. (2008). Acta Cryst. E64, o2409.]); Tamboura et al. (2009[Tamboura, F. B., Gaye, M., Sall, A. S., Barry, A. H. & Bah, Y. (2009). Acta Cryst. E65, m160-m161.]).

[Scheme 1]

Experimental

Crystal data
  • C11H14N2O3

  • Mr = 222.24

  • Orthorhombic, P b c a

  • a = 8.794 (3) Å

  • b = 10.920 (3) Å

  • c = 24.418 (7) Å

  • V = 2345.0 (12) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 223 K

  • 0.24 × 0.21 × 0.20 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.977, Tmax = 0.979

  • 11332 measured reflections

  • 2070 independent reflections

  • 1819 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.133

  • S = 1.10

  • 2070 reflections

  • 149 parameters

  • H-atom parameters constrained

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.12 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯O3i 0.86 1.97 2.803 (2) 164
C1—H1C⋯O2ii 0.96 2.55 3.435 (3) 153
C11—H11C⋯O3iii 0.96 2.47 3.425 (3) 174
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]; (ii) [x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]; (iii) -x, -y+3, -z.

Data collection: SMART (Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Schiff bases have attracted much attention due to the possibility of their analytical applications (Cimerman et al., 1997). They are also important ligands, which have been reported to have mild bacteriostatic activity and are used as potential oral iron-chelating drugs for genetic disorders such as thalassemia (Offe et al., 1952; Richardson et al., 1988). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various complexes (Tamboura et al., 2009). We report here the crystal structure of the title compound (Fig. 1).

The acetohydrazide group is planar and it forms a dihedral angle of 19.7 (1)° with the benzene ring. One of the methoxy groups is coplanar with the attached benzene ring [C1—O1—C4—C5 = -1.7 (3)°] whereas the other is slightly twisted [C2—O2—C3—C8 = 6.3 (3)°]. The molecule adopts a trans configuration with respect to the CN bond. Bond lengths and angles are comparable to those observed for N'-[1-(4-methoxyphenyl)ethylidene]acetohydrazide (Li et al., 2008).

The molecules are linked into a chain along the a axis by N—H···O hydrogen bonds (Table 1). The chains are cross-linked into a three-dimensional network by C—H···O hydrogen bonds (Fig.2).

Related literature top

For general background to Schiff bases, see: Cimerman et al. (1997); Offe et al. (1952); Richardson et al. (1988). For related structures, see: Li et al. (2008); Tamboura et al. (2009).

Experimental top

3,4-Dimethoxybenzaldehyde (1.66 g, 0.01 mol) and acetohydrazide (0.74 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 2.5 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. 470–472 K).

Refinement top

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

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
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.
N'-(3,4-Dimethoxybenzylidene)acetohydrazide top
Crystal data top
C11H14N2O3F(000) = 944
Mr = 222.24Dx = 1.259 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2070 reflections
a = 8.794 (3) Åθ = 1.7–25.0°
b = 10.920 (3) ŵ = 0.09 mm1
c = 24.418 (7) ÅT = 223 K
V = 2345.0 (12) Å3Block, colourless
Z = 80.24 × 0.21 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2070 independent reflections
Radiation source: fine-focus sealed tube1819 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1010
Tmin = 0.977, Tmax = 0.979k = 1212
11332 measured reflectionsl = 2728
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.133 w = 1/[σ2(Fo2) + (0.0593P)2 + 0.6946P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
2070 reflectionsΔρmax = 0.15 e Å3
149 parametersΔρmin = 0.12 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0113 (16)
Crystal data top
C11H14N2O3V = 2345.0 (12) Å3
Mr = 222.24Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.794 (3) ŵ = 0.09 mm1
b = 10.920 (3) ÅT = 223 K
c = 24.418 (7) Å0.24 × 0.21 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2070 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
1819 reflections with I > 2σ(I)
Tmin = 0.977, Tmax = 0.979Rint = 0.034
11332 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.10Δρmax = 0.15 e Å3
2070 reflectionsΔρmin = 0.12 e Å3
149 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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) top
xyzUiso*/Ueq
O10.00337 (17)0.67057 (13)0.22113 (6)0.0725 (5)
O20.21387 (16)0.81158 (15)0.18477 (6)0.0738 (5)
O30.07522 (17)1.32783 (14)0.01901 (7)0.0735 (5)
C30.0722 (2)0.83356 (17)0.16379 (7)0.0516 (5)
C70.1114 (2)0.93669 (17)0.10716 (7)0.0519 (5)
C40.0432 (2)0.75598 (17)0.18390 (8)0.0537 (5)
C60.2227 (2)0.8587 (2)0.12649 (8)0.0621 (5)
H60.32160.86630.11350.074*
C80.0381 (2)0.92289 (17)0.12603 (7)0.0507 (5)
H80.11430.97420.11300.061*
C100.0460 (2)1.29542 (18)0.00180 (8)0.0556 (5)
C50.1896 (2)0.76932 (19)0.16500 (9)0.0625 (6)
H50.26630.71840.17800.075*
C90.1527 (2)1.03131 (19)0.06757 (8)0.0564 (5)
H90.25011.03030.05280.068*
C110.1217 (3)1.3670 (2)0.04662 (9)0.0702 (6)
H11A0.07061.35170.08070.105*
H11B0.22611.34230.04960.105*
H11C0.11691.45280.03820.105*
C20.3390 (2)0.8771 (3)0.16274 (10)0.0825 (7)
H2A0.32340.96330.16800.124*
H2B0.43070.85240.18100.124*
H2C0.34760.86000.12430.124*
C10.1076 (3)0.5863 (2)0.24102 (11)0.0827 (8)
H1A0.15180.54290.21080.124*
H1B0.06010.52910.26550.124*
H1C0.18570.63030.26020.124*
N20.12042 (19)1.19408 (15)0.01359 (6)0.0569 (4)
H20.20711.17780.00100.068*
N10.06138 (18)1.11504 (14)0.05240 (6)0.0544 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0779 (10)0.0661 (9)0.0736 (10)0.0030 (7)0.0097 (8)0.0243 (8)
O20.0572 (9)0.0863 (11)0.0779 (10)0.0039 (8)0.0052 (7)0.0262 (8)
O30.0634 (9)0.0642 (10)0.0929 (11)0.0057 (7)0.0005 (8)0.0069 (8)
C30.0533 (11)0.0536 (11)0.0479 (10)0.0003 (9)0.0020 (8)0.0001 (8)
C70.0581 (11)0.0515 (11)0.0462 (10)0.0034 (9)0.0006 (8)0.0017 (8)
C40.0650 (12)0.0477 (10)0.0486 (10)0.0021 (9)0.0085 (9)0.0030 (8)
C60.0545 (11)0.0661 (13)0.0656 (12)0.0041 (10)0.0016 (10)0.0063 (10)
C80.0560 (11)0.0488 (10)0.0473 (10)0.0068 (8)0.0032 (8)0.0010 (8)
C100.0587 (12)0.0505 (11)0.0576 (11)0.0049 (9)0.0092 (9)0.0037 (9)
C50.0624 (12)0.0574 (12)0.0679 (13)0.0097 (10)0.0096 (10)0.0071 (10)
C90.0559 (11)0.0605 (12)0.0529 (10)0.0042 (10)0.0022 (9)0.0027 (9)
C110.0918 (16)0.0530 (12)0.0659 (13)0.0018 (11)0.0030 (12)0.0071 (10)
C20.0548 (12)0.1042 (19)0.0886 (17)0.0095 (13)0.0055 (12)0.0167 (15)
C10.0994 (18)0.0651 (14)0.0836 (16)0.0000 (13)0.0244 (14)0.0224 (13)
N20.0577 (9)0.0551 (10)0.0578 (9)0.0008 (8)0.0040 (8)0.0078 (8)
N10.0572 (9)0.0525 (9)0.0536 (9)0.0042 (8)0.0005 (7)0.0052 (7)
Geometric parameters (Å, º) top
O1—C41.365 (2)C10—C111.501 (3)
O1—C11.427 (3)C5—H50.93
O2—C31.368 (2)C9—N11.272 (2)
O2—C21.419 (3)C9—H90.93
O3—C101.233 (2)C11—H11A0.96
C3—C81.375 (3)C11—H11B0.96
C3—C41.410 (3)C11—H11C0.96
C7—C61.381 (3)C2—H2A0.96
C7—C81.401 (3)C2—H2B0.96
C7—C91.461 (3)C2—H2C0.96
C4—C51.375 (3)C1—H1A0.96
C6—C51.386 (3)C1—H1B0.96
C6—H60.93C1—H1C0.96
C8—H80.93N2—N11.383 (2)
C10—N21.340 (2)N2—H20.86
C4—O1—C1117.52 (18)N1—C9—H9118.5
C3—O2—C2118.41 (16)C7—C9—H9118.5
O2—C3—C8125.05 (17)C10—C11—H11A109.5
O2—C3—C4114.81 (17)C10—C11—H11B109.5
C8—C3—C4120.14 (18)H11A—C11—H11B109.5
C6—C7—C8119.11 (18)C10—C11—H11C109.5
C6—C7—C9119.09 (18)H11A—C11—H11C109.5
C8—C7—C9121.80 (17)H11B—C11—H11C109.5
O1—C4—C5125.20 (18)O2—C2—H2A109.5
O1—C4—C3115.24 (18)O2—C2—H2B109.5
C5—C4—C3119.55 (18)H2A—C2—H2B109.5
C7—C6—C5121.14 (19)O2—C2—H2C109.5
C7—C6—H6119.4H2A—C2—H2C109.5
C5—C6—H6119.4H2B—C2—H2C109.5
C3—C8—C7120.12 (17)O1—C1—H1A109.5
C3—C8—H8119.9O1—C1—H1B109.5
C7—C8—H8119.9H1A—C1—H1B109.5
O3—C10—N2122.96 (19)O1—C1—H1C109.5
O3—C10—C11122.33 (19)H1A—C1—H1C109.5
N2—C10—C11114.71 (19)H1B—C1—H1C109.5
C4—C5—C6119.93 (19)C10—N2—N1121.62 (17)
C4—C5—H5120.0C10—N2—H2119.2
C6—C5—H5120.0N1—N2—H2119.2
N1—C9—C7122.97 (18)C9—N1—N2114.28 (17)
C2—O2—C3—C86.3 (3)C6—C7—C8—C30.7 (3)
C2—O2—C3—C4173.8 (2)C9—C7—C8—C3179.28 (17)
C1—O1—C4—C51.7 (3)O1—C4—C5—C6179.13 (18)
C1—O1—C4—C3177.38 (18)C3—C4—C5—C60.1 (3)
O2—C3—C4—O10.1 (2)C7—C6—C5—C41.1 (3)
C8—C3—C4—O1179.94 (16)C6—C7—C9—N1171.95 (19)
O2—C3—C4—C5179.25 (18)C8—C7—C9—N18.1 (3)
C8—C3—C4—C50.8 (3)O3—C10—N2—N13.4 (3)
C8—C7—C6—C51.5 (3)C11—C10—N2—N1176.62 (17)
C9—C7—C6—C5178.54 (18)C7—C9—N1—N2178.40 (17)
O2—C3—C8—C7179.67 (18)C10—N2—N1—C9171.88 (17)
C4—C3—C8—C70.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O3i0.861.972.803 (2)164
C1—H1C···O2ii0.962.553.435 (3)153
C11—H11C···O3iii0.962.473.425 (3)174
Symmetry codes: (i) x+1/2, y+5/2, z; (ii) x+1/2, y, z+1/2; (iii) x, y+3, z.

Experimental details

Crystal data
Chemical formulaC11H14N2O3
Mr222.24
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)223
a, b, c (Å)8.794 (3), 10.920 (3), 24.418 (7)
V3)2345.0 (12)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.24 × 0.21 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.977, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
11332, 2070, 1819
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.133, 1.10
No. of reflections2070
No. of parameters149
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.12

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···AD—HH···AD···AD—H···A
N2—H2···O3i0.861.972.803 (2)164
C1—H1C···O2ii0.962.553.435 (3)153
C11—H11C···O3iii0.962.473.425 (3)174
Symmetry codes: (i) x+1/2, y+5/2, z; (ii) x+1/2, y, z+1/2; (iii) x, y+3, z.
 

Acknowledgements

The authors thank the Science and Technology Project of Zhejiang Province (grant No. 2007 F70077) and Hangzhou Vocational and Technical College for financial support.

References

First citationBruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCimerman, Z., Galic, N. & Bosner, B. (1997). Anal Chim. Acta, 343, 145–153.  CrossRef CAS Web of Science Google Scholar
First citationLi, Y.-F. & Jian, F.-F. (2008). Acta Cryst. E64, o2409.  Web of Science CrossRef IUCr Journals Google Scholar
First citationOffe, H. A., Siefen, W. & Domagk, G. (1952). Z. Naturforsch. Teil B, 7, 446–447.  Google Scholar
First citationRichardson, D., Baker, E., Ponka, P., Wilairat, P., Vitolo, M. L. & Webb, J. (1988). Thalassemia: Pathophysiology and Management, Part B, p. 81. New York: Alan R. Liss Inc.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTamboura, F. B., Gaye, M., Sall, A. S., Barry, A. H. & Bah, Y. (2009). Acta Cryst. E65, m160–m161.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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