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access2-Methylbenzaldehyde 2-methylbenzylidenehydrazone
aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
*Correspondence e-mail: shanshang@mail.hz.zj.cn
The molecule of the title compound, C16H16N2, is centrosymmetric and the dihedral angle between the benzene ring and the dimethylhydrazine mean plane is 16.11 (15)°.
Related literature
For background, see: Shan et al. (2003![[Shan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003). Acta Cryst. C59, o135-o136.]](../../../../../../logos/arrows/e_arr.gif "Shan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003). Acta Cryst. C59, o135-o136.")
). For related structures, see: Fan et al. (2008); Shan et al. (2004, 2008).
![[Scheme 1]](hb2750scheme1.gif)
Experimental
Crystal data
|
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks I, global. DOI: 10.1107/S160053680801934X/hb2750sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S160053680801934X/hb2750Isup2.hkl
Hydrazine hydrate (0.10 g, 2 mmol) was dissolved in ethanol (10 ml), then acetic acid (0.1 ml) was added slowly to the ethanol solution with stirring. The solution was heated at 333 K for several minutes until the solution cleared. 2-Methylbenzaldehyde (0.24 g, 2 mmol) was then dropped slowly into the solution, and the mixture was kept at 333 K with continuous stirring for 2 h. After the solution had cooled to room temperature yellow powder appeared. The crude title compound was separated and washed with water three times. Recrystallization from an absolute ethanol yielded yellow plates of (I).
Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and the torsion angle was refined to fit the electron density with Uiso(H) = 1.5Ueq(C). The other H atoms were placed in calculated positions with C—H = 0.93 and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./hb2750fig1thm.gif) | Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids for non-H atoms. Symmetry code: (i) -x, 1-y, -z. |
| C16H16N2 | F(000) = 252 |
| Mr = 236.31 | Dx = 1.132 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2246 reflections |
| a = 6.1578 (11) Å | θ = 3.0–25.5° |
| b = 13.248 (2) Å | µ = 0.07 mm−1 |
| c = 8.8161 (16) Å | T = 295 K |
| β = 105.398 (12)° | Plate, yellow |
| V = 693.4 (2) Å3 | 0.32 × 0.28 × 0.12 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID IP diffractometer | 1168 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.020 |
| Graphite monochromator | θmax = 27.0°, θmin = 2.9° |
| Detector resolution: 10.00 pixels mm-1 | h = −7→7 |
| ω scans | k = −15→16 |
| 5451 measured reflections | l = −11→11 |
| 1503 independent reflections |
| 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)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.0481P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 1503 reflections | Δρmax = 0.12 e Å−3 |
| 84 parameters | Δρmin = −0.11 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: 0.099 (12) |
| C16H16N2 | V = 693.4 (2) Å3 |
| Mr = 236.31 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.1578 (11) Å | µ = 0.07 mm−1 |
| b = 13.248 (2) Å | T = 295 K |
| c = 8.8161 (16) Å | 0.32 × 0.28 × 0.12 mm |
| β = 105.398 (12)° |
| Rigaku R-AXIS RAPID IP diffractometer | 1168 reflections with I > 2σ(I) |
| 5451 measured reflections | Rint = 0.020 |
| 1503 independent reflections |
| R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
| wR(F2) = 0.115 | H-atom parameters constrained |
| S = 1.10 | Δρmax = 0.12 e Å−3 |
| 1503 reflections | Δρmin = −0.11 e Å−3 |
| 84 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 | ||
| N | 0.03959 (16) | 0.45944 (7) | 0.05193 (11) | 0.0545 (3) | |
| C1 | 0.33920 (18) | 0.40583 (8) | 0.26999 (12) | 0.0495 (3) | |
| C2 | 0.56653 (19) | 0.41758 (9) | 0.35123 (13) | 0.0553 (3) | |
| C3 | 0.6648 (2) | 0.34407 (11) | 0.46155 (15) | 0.0731 (4) | |
| H3 | 0.8162 | 0.3499 | 0.5151 | 0.088* | |
| C4 | 0.5435 (3) | 0.26319 (11) | 0.49318 (18) | 0.0813 (5) | |
| H4 | 0.6129 | 0.2158 | 0.5682 | 0.098* | |
| C5 | 0.3198 (3) | 0.25229 (10) | 0.41412 (16) | 0.0754 (4) | |
| H5 | 0.2377 | 0.1977 | 0.4356 | 0.090* | |
| C6 | 0.2186 (2) | 0.32277 (9) | 0.30309 (14) | 0.0617 (4) | |
| H6 | 0.0678 | 0.3151 | 0.2492 | 0.074* | |
| C7 | 0.22666 (19) | 0.47938 (8) | 0.15044 (13) | 0.0514 (3) | |
| H7 | 0.2935 | 0.5419 | 0.1466 | 0.062* | |
| C8 | 0.7057 (2) | 0.50502 (11) | 0.32086 (16) | 0.0720 (4) | |
| H8A | 0.6477 | 0.5668 | 0.3517 | 0.108* | |
| H8B | 0.6986 | 0.5078 | 0.2108 | 0.108* | |
| H8C | 0.8593 | 0.4963 | 0.3807 | 0.108* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N | 0.0577 (6) | 0.0502 (6) | 0.0522 (6) | 0.0060 (4) | 0.0086 (4) | 0.0054 (4) |
| C1 | 0.0564 (6) | 0.0494 (6) | 0.0427 (6) | 0.0049 (5) | 0.0129 (5) | −0.0008 (5) |
| C2 | 0.0563 (7) | 0.0624 (7) | 0.0471 (6) | 0.0058 (5) | 0.0137 (5) | −0.0003 (5) |
| C3 | 0.0655 (8) | 0.0849 (10) | 0.0623 (8) | 0.0139 (7) | 0.0055 (6) | 0.0119 (7) |
| C4 | 0.0945 (11) | 0.0741 (9) | 0.0686 (9) | 0.0164 (8) | 0.0097 (8) | 0.0235 (7) |
| C5 | 0.0976 (11) | 0.0571 (8) | 0.0700 (9) | −0.0035 (7) | 0.0198 (8) | 0.0121 (6) |
| C6 | 0.0682 (8) | 0.0567 (7) | 0.0570 (7) | −0.0038 (6) | 0.0112 (6) | 0.0030 (5) |
| C7 | 0.0549 (6) | 0.0492 (6) | 0.0495 (6) | 0.0012 (5) | 0.0126 (5) | 0.0009 (5) |
| C8 | 0.0568 (7) | 0.0860 (10) | 0.0711 (8) | −0.0059 (6) | 0.0135 (6) | 0.0053 (7) |
| N—C7 | 1.2727 (14) | C4—C5 | 1.376 (2) |
| N—Ni | 1.4121 (17) | C4—H4 | 0.9300 |
| C1—C6 | 1.4007 (16) | C5—C6 | 1.3764 (17) |
| C1—C2 | 1.4016 (16) | C5—H5 | 0.9300 |
| C1—C7 | 1.4672 (15) | C6—H6 | 0.9300 |
| C2—C3 | 1.3956 (17) | C7—H7 | 0.9300 |
| C2—C8 | 1.5065 (17) | C8—H8A | 0.9600 |
| C3—C4 | 1.3761 (19) | C8—H8B | 0.9600 |
| C3—H3 | 0.9300 | C8—H8C | 0.9600 |
| C7—N—Ni | 112.25 (11) | C4—C5—H5 | 120.3 |
| C6—C1—C2 | 119.57 (10) | C6—C5—H5 | 120.3 |
| C6—C1—C7 | 119.74 (10) | C5—C6—C1 | 121.08 (12) |
| C2—C1—C7 | 120.70 (10) | C5—C6—H6 | 119.5 |
| C3—C2—C1 | 117.90 (12) | C1—C6—H6 | 119.5 |
| C3—C2—C8 | 119.92 (11) | N—C7—C1 | 121.44 (11) |
| C1—C2—C8 | 122.18 (10) | N—C7—H7 | 119.3 |
| C4—C3—C2 | 121.77 (13) | C1—C7—H7 | 119.3 |
| C4—C3—H3 | 119.1 | C2—C8—H8A | 109.5 |
| C2—C3—H3 | 119.1 | C2—C8—H8B | 109.5 |
| C5—C4—C3 | 120.20 (12) | H8A—C8—H8B | 109.5 |
| C5—C4—H4 | 119.9 | C2—C8—H8C | 109.5 |
| C3—C4—H4 | 119.9 | H8A—C8—H8C | 109.5 |
| C4—C5—C6 | 119.48 (13) | H8B—C8—H8C | 109.5 |
| Symmetry code: (i) −x, −y+1, −z. |
Experimental details
| Crystal data | |
| Chemical formula | C16H16N2 |
| Mr | 236.31 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 295 |
| a, b, c (Å) | 6.1578 (11), 13.248 (2), 8.8161 (16) |
| β (°) | 105.398 (12) |
| V (Å3) | 693.4 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.07 |
| Crystal size (mm) | 0.32 × 0.28 × 0.12 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID IP diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5451, 1503, 1168 |
| Rint | 0.020 |
| (sin θ/λ)max (Å−1) | 0.639 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.115, 1.10 |
| No. of reflections | 1503 |
| No. of parameters | 84 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.12, −0.11 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Acknowledgements
The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
As part of our ongong studies of hydrazone derivatives (Shan et al., 2003), the title compound, (I), has been prepared and its crystal structure is reported here (Fig. 1).
The molecule of (I) is centrosymmetric, with the mid-point of the N—N bond located on an inversion center. The N=C7 double bond distance of 1.2727 (14) Å is shorter than the C=N bond distances found in related hydrazone structures, i.e. 1.295 (2)Å in (E)-3-methoxyacetophenone 4-nitrophenylhydrazone (Fan et al., 2008), 1.2977 (18) Å in (E)-2-furyl methyl ketone 2,4-dinitrophenylhydrazone (Shan et al., 2008) and 1.293 (2) Å in benzylideneacetone 2,4-dinitrophenylhydrazone (Shan et al. 2004). In (I), the terminal benzene ring is twisted with respect to the central dimethylhydrazine plane by 16.11 (15)°. The crystal packing is controlled by van der Waals forces.