PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2401–o2402.
Published online 2010 August 25. doi:  10.1107/S1600536810033684
PMCID: PMC3008086

(E,E)-1,2-Bis(2,4,6-trimeth­oxy­benzyl­idene)hydrazine

Abstract

The title mol­ecule, C20H24N2O6, lies on an inversion centre. All non-H atoms are essentially coplanar, with an r.m.s. deviation of 0.0415 (1) Å and a maximum deviation of 0.1476 (1) Å for the meth­oxy C atom at the 4-position of the benzene ring. The crystal structure is stabilized by weak C—H(...)N and C—H(...)π inter­actions.

Related literature

For standard bond-length data, see: Allen et al. (1987 [triangle]). For related structures, see: Jansrisewangwong et al. (2010 [triangle]); Zhao et al. (2006 [triangle]). For background and the biological activity of hydro­zones, see: El-Tabl et al. (2008 [triangle]); Qin et al. (2009 [triangle]); Ramamohan et al. (1995 [triangle]); Rollas & Küçükgüzel (2007 [triangle]). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2401-scheme1.jpg

Experimental

Crystal data

  • C20H24N2O6
  • M r = 388.41
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2401-efi1.jpg
  • a = 7.3851 (2) Å
  • b = 7.4043 (2) Å
  • c = 9.5440 (2) Å
  • α = 71.412 (1)°
  • β = 78.095 (1)°
  • γ = 79.449 (1)°
  • V = 480.13 (2) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 100 K
  • 0.29 × 0.14 × 0.08 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.972, T max = 0.992
  • 11100 measured reflections
  • 2791 independent reflections
  • 2244 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.115
  • S = 1.03
  • 2791 reflections
  • 134 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810033684/lh5117sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033684/lh5117Isup2.hkl

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

Acknowledgments

PJ thanks the Center of Excellence for Innovation in Chemistry (PERCH-CIC), the Commission on Higher Education, Ministry of Education and the Graduate School, Prince of Songkla University, for financial support. The authors thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit (CMRU) and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Hydrazones and their complexes are interesting due to their fluorescence properties (Qin et al., 2009) and various biological activities such as insecticidal, antitumor, antioxidant, antifungal, antibacterial and antiviral properties (El-Tabl et al., 2008; Ramamohan et al., 1995; Rollas & Küçükgüzel, 2007). These interesting properties led us to synthesize the title hydrazone derivative (I) in order to study its antibacterial activity and fluorescence property. Experiments show that (I) does not possess antibacterial activities, however it does exhibit fluorescence with the maximum emission at 410 nm when the compound is excited at 280 nm. Herein the crystal structure of (I) is reported.

The asymmetric unit of (I), (Fig. 1), C20H24N2O6, contains one half-molecule and the complete molecule is generated by an inversion centre (symmetry code -x, 2-y, 1-z). The mean plane through the C=N-N=C bridge forms a dihedral angle of 4.96 (9)° with the benzene rings. The methoxy groups attached to atoms C1 and C5 (positions 2 and 6) are approximately coplanar with the benzene ring whereas the one attached to atom C3 (position 4) is slightly twisted with respect to the benzene ring as described by the torsion angles of C8–O1–C1–C2 = 2.86 (15)°, C10–O3–C5–C4 = 3.58 (14)° and C9–O2–C3–C4 = 8.39 (15)°, respectively. The N-N bond length, 1.4117 (18) Å is comparable with 1.419 (3) Å and the C=N-N angle = 110.7 (2)°, is almost similar to 112.2 (2)° observed in (E,E)-1,2-bis(3,4,5-trimethoxybenzylidene)hydrazine (Zhao et al., 2006). The bond distances have normal values (Allen et al., 1987) and are comparable with related structures (Jansrisewangwong et al., 2010; Zhao et al., 2006). The crystal structure is stabilized by weak C—H···N and C—H···π interactions (Fig. 2).

Experimental

The title compound was synthesized by mixing a solution (1:2 molar ratio) of hydrazine hydrate (0.097 ml, 2 mmol) and 2,4,6-trimethoxybenzaldehyde (0.785 mg, 4 mmol) in ethanol (20 ml). The resulting solution was refluxed for 5 h, yielding the yellow solid. The resultant solid was filtered off and washed with methanol. Yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from acetone by slow evaporation of the solvent at room temperature over several days, mp. 484–486 K.

Refinement

The H atom attached to C7 was located in a difference map and refined isotropically. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Atoms with suffix A were generated by symmetry code -x, 2 - y, 1 - z.
Fig. 2.
Part of the crystal structure showing weak hydrogen bonds as dashed lines.

Crystal data

C20H24N2O6Z = 1
Mr = 388.41F(000) = 206
Triclinic, P1Dx = 1.343 Mg m3
Hall symbol: -P 1Melting point = 484–486 K
a = 7.3851 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.4043 (2) ÅCell parameters from 2791 reflections
c = 9.5440 (2) Åθ = 2.3–30.0°
α = 71.412 (1)°µ = 0.10 mm1
β = 78.095 (1)°T = 100 K
γ = 79.449 (1)°Block, yellow
V = 480.13 (2) Å30.29 × 0.14 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer2791 independent reflections
Radiation source: sealed tube2244 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −10→10
Tmin = 0.972, Tmax = 0.992k = −10→10
11100 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0603P)2 + 0.1087P] where P = (Fo2 + 2Fc2)/3
2791 reflections(Δ/σ)max = 0.001
134 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.
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 (Å2)

xyzUiso*/Ueq
O10.20858 (11)0.87907 (11)0.08848 (8)0.01756 (18)
O20.82788 (11)0.57545 (11)0.12544 (8)0.01906 (19)
O30.44058 (10)0.78425 (11)0.53298 (8)0.01517 (17)
N10.09376 (12)0.95751 (13)0.49155 (10)0.0163 (2)
C10.35619 (14)0.81164 (14)0.16438 (11)0.0142 (2)
C20.52565 (15)0.72803 (15)0.10450 (11)0.0158 (2)
H2A0.54430.71780.00780.019*
C30.66759 (14)0.65957 (15)0.19168 (11)0.0148 (2)
C40.64415 (14)0.67699 (14)0.33540 (11)0.0143 (2)
H4A0.74060.63180.39170.017*
C50.47341 (14)0.76345 (14)0.39383 (10)0.0133 (2)
C60.32381 (14)0.83151 (14)0.31125 (11)0.0134 (2)
C70.14037 (15)0.91807 (15)0.36584 (11)0.0147 (2)
C80.22823 (17)0.85390 (17)−0.05710 (12)0.0205 (2)
H8A0.11270.9008−0.09540.031*
H8B0.26010.7199−0.04990.031*
H8C0.32510.9241−0.12340.031*
C90.96932 (16)0.47848 (17)0.21582 (12)0.0212 (2)
H9A1.06970.41730.15850.032*
H9B0.91730.38340.30220.032*
H9C1.01570.56980.24730.032*
C100.59168 (15)0.72427 (16)0.61730 (11)0.0167 (2)
H10A0.55160.74950.71230.025*
H10B0.69450.79390.56310.025*
H10C0.63020.58920.63300.025*
H70.0407 (19)0.9430 (19)0.3064 (15)0.022 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0168 (4)0.0235 (4)0.0134 (3)0.0022 (3)−0.0047 (3)−0.0080 (3)
O20.0149 (4)0.0236 (4)0.0163 (4)0.0049 (3)0.0002 (3)−0.0082 (3)
O30.0145 (4)0.0196 (4)0.0124 (3)0.0013 (3)−0.0034 (3)−0.0073 (3)
N10.0125 (4)0.0186 (4)0.0173 (4)−0.0003 (3)−0.0004 (3)−0.0069 (3)
C10.0156 (5)0.0131 (4)0.0133 (4)−0.0010 (4)−0.0031 (4)−0.0032 (4)
C20.0175 (5)0.0173 (5)0.0122 (4)−0.0009 (4)−0.0001 (4)−0.0058 (4)
C30.0134 (5)0.0145 (5)0.0150 (4)−0.0007 (4)0.0012 (4)−0.0049 (4)
C40.0133 (5)0.0149 (5)0.0144 (4)−0.0008 (4)−0.0028 (4)−0.0043 (4)
C50.0153 (5)0.0120 (4)0.0123 (4)−0.0028 (4)−0.0003 (4)−0.0040 (3)
C60.0140 (5)0.0134 (4)0.0126 (4)−0.0010 (4)−0.0014 (3)−0.0046 (4)
C70.0137 (5)0.0151 (5)0.0151 (4)−0.0006 (4)−0.0027 (4)−0.0049 (4)
C80.0240 (6)0.0251 (6)0.0143 (5)0.0020 (4)−0.0061 (4)−0.0093 (4)
C90.0159 (5)0.0242 (5)0.0198 (5)0.0043 (4)−0.0014 (4)−0.0061 (4)
C100.0157 (5)0.0207 (5)0.0157 (4)−0.0010 (4)−0.0051 (4)−0.0071 (4)

Geometric parameters (Å, °)

O1—C11.3632 (12)C4—H4A0.9300
O1—C81.4347 (12)C5—C61.4135 (14)
O2—C31.3642 (12)C6—C71.4564 (14)
O2—C91.4328 (13)C7—H70.976 (14)
O3—C51.3528 (11)C8—H8A0.9600
O3—C101.4322 (12)C8—H8B0.9600
N1—C71.2882 (13)C8—H8C0.9600
N1—N1i1.4117 (18)C9—H9A0.9600
C1—C21.3866 (14)C9—H9B0.9600
C1—C61.4226 (13)C9—H9C0.9600
C2—C31.3944 (15)C10—H10A0.9600
C2—H2A0.9300C10—H10B0.9600
C3—C41.3909 (13)C10—H10C0.9600
C4—C51.3974 (14)
C1—O1—C8118.01 (8)N1—C7—C6125.41 (9)
C3—O2—C9117.79 (8)N1—C7—H7115.8 (8)
C5—O3—C10117.61 (8)C6—C7—H7118.7 (8)
C7—N1—N1i110.66 (11)O1—C8—H8A109.5
O1—C1—C2122.94 (9)O1—C8—H8B109.5
O1—C1—C6115.10 (9)H8A—C8—H8B109.5
C2—C1—C6121.95 (9)O1—C8—H8C109.5
C1—C2—C3118.90 (9)H8A—C8—H8C109.5
C1—C2—H2A120.5H8B—C8—H8C109.5
C3—C2—H2A120.5O2—C9—H9A109.5
O2—C3—C4123.44 (9)O2—C9—H9B109.5
O2—C3—C2115.02 (9)H9A—C9—H9B109.5
C4—C3—C2121.55 (9)O2—C9—H9C109.5
C3—C4—C5118.99 (9)H9A—C9—H9C109.5
C3—C4—H4A120.5H9B—C9—H9C109.5
C5—C4—H4A120.5O3—C10—H10A109.5
O3—C5—C4122.15 (9)O3—C10—H10B109.5
O3—C5—C6116.17 (9)H10A—C10—H10B109.5
C4—C5—C6121.67 (9)O3—C10—H10C109.5
C5—C6—C1116.93 (9)H10A—C10—H10C109.5
C5—C6—C7124.92 (9)H10B—C10—H10C109.5
C1—C6—C7118.15 (9)
C8—O1—C1—C22.86 (15)C3—C4—C5—C60.69 (15)
C8—O1—C1—C6−176.61 (9)O3—C5—C6—C1179.70 (8)
O1—C1—C2—C3−178.70 (9)C4—C5—C6—C1−1.27 (15)
C6—C1—C2—C30.74 (16)O3—C5—C6—C7−0.86 (15)
C9—O2—C3—C48.39 (15)C4—C5—C6—C7178.16 (9)
C9—O2—C3—C2−171.46 (9)O1—C1—C6—C5−179.97 (8)
C1—C2—C3—O2178.49 (9)C2—C1—C6—C50.55 (15)
C1—C2—C3—C4−1.37 (16)O1—C1—C6—C70.55 (14)
O2—C3—C4—C5−179.18 (9)C2—C1—C6—C7−178.93 (9)
C2—C3—C4—C50.67 (16)N1i—N1—C7—C6179.28 (10)
C10—O3—C5—C43.58 (14)C5—C6—C7—N15.52 (17)
C10—O3—C5—C6−177.40 (8)C1—C6—C7—N1−175.05 (10)
C3—C4—C5—O3179.66 (9)

Symmetry codes: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.977 (14)2.332 (14)2.6886 (12)100.6 (10)
C10—H10B···N1ii0.962.493.3876 (15)155
C8—H8C···Cgiii0.972.793.6678 (13)152
C10—H10C···Cgiv0.972.633.4385 (13)142

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+2, −z; (iv) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5117).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • El-Tabl, A. S., El-Saied, F. A., Plass, W. & Al-Hakimi, A. N. (2008). Spectrochim. Acta Part A, 71, 90–99. [PubMed]
  • Jansrisewangwong, P., Chantrapromma, S. & Fun, H.-K. (2010). Acta Cryst. E66, o2170. [PMC free article] [PubMed]
  • Qin, D.-D., Yang, Z.-Y. & Qi, G.-F. (2009). Spectrochim. Acta Part A, 74, 415–420. [PubMed]
  • Ramamohan, L., Shikkaragol, R. K., Angadi, S. D. & Kulkarni, V. H. (1995). Asian J. Pure Appl. Chem 1, 86.
  • Rollas, S. & Küçükgüzel, Ş. G. (2007). Molecules, 12, 1910–1939. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Zhao, Z., Feng, F., Guo, G. & Wang, W. (2006). Acta Cryst. E62, o2413–o2414.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography