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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1090.
Published online 2009 April 22. doi:  10.1107/S1600536809014330
PMCID: PMC2977769

[1-Phenyl-2-(4-pyrid­yl)ethyl­idene]hydrazine

Abstract

The title compound, C13H13N3, is non-planar, with the pyridine and phenyl rings inclined at an angle of 80.7 (3)°. The central ethyl­idenehydrazine atoms lie in a plane [mean deviation = 0.013 (1) Å], which forms dihedral angles of 88.5 (1) and 9.4 (1)° with the pyridine and phenyl rings, respectively. In the crystal structure, mol­ecules are linked by inter­molecular N—H(...)N hydrogen bonds into infinite chains propagating along the b axis.

Related literature

For related structures of hydrazine derivatives, see: De et al. (2006 [triangle]); Patra & Goldberg (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1090-scheme1.jpg

Experimental

Crystal data

  • C13H13N3
  • M r = 211.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1090-efi1.jpg
  • a = 5.7428 (6) Å
  • b = 10.8751 (11) Å
  • c = 17.6358 (18) Å
  • V = 1101.4 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 295 K
  • 0.30 × 0.22 × 0.15 mm

Data collection

  • Bruker SMART APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.961, T max = 0.982
  • 5694 measured reflections
  • 1266 independent reflections
  • 1117 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.105
  • S = 1.04
  • 1266 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.11 e Å−3
  • Δρmin = −0.13 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/S1600536809014330/sj2620sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014330/sj2620Isup2.hkl

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

Acknowledgments

The author thanks Hengyang Normal University for supporting this study.

supplementary crystallographic information

Comment

The chemical properties of hydrazine derivatives with various substitution patterns have been investigated extensively, because of their ability to bind to transition metal ions or to form unusual organic helical chains through intermolecular hydrogen bonds (De et al., 2006; Patra & Goldberg, 2003). A new hydrazine derivative has been synthesized and its crystal structure is reported here, Fig. 1.

The whole molecule is nonplanar with a dihedral angle of 80.7 (3)° between the pyridine and phenyl ring. However, the central C6/C7/N2/N3 motifs are planar with the mean deviation from the plane of 0.013 (1) Å, which also generates dihedral angles of 88.5 (1)° and 9.4 (1)° with the pyridine and phenyl rings, respectively. The N2 atom forms an intramolecular C—H···N hydrogen bond with phenyl ring H13 atoms.

The crystal packing (Fig. 2) shows the amino group acts as a donor to form an intermolecular N—H···N hydrogen bond towards pyridine N atom forming infinite chains parallel to the b axis.

Experimental

Benzoyl chloride (4.85 g, 34.5 mmol) was added to a solution of 4-methylpyridine (4.14 g, 44.5 mmol) in chloroform (20 ml) over 1 h at room temperature. The resulting solution was stirred for 5 h and the solvent was evaporated under vacuum to give an orange precipitate, which were triturated with toluene (20 ml) to obtain an orange solution. Then hydrazine hydrate (4 ml, 80%, 66 mmol) was added to this solution and stirred for 10 h. The solvent was removed under reduced pressure and the residue was recrystallized from dichloromethane to give light-yellow prism-like crystals of the title compound. Yield: 0.82 g (11%).

Refinement

The carbon-bound H atoms were placed at calculated positions (C—H = 0.93 Å or 0.97 Å) and refined as riding, with U(H) = 1.2Ueq(C). The amine H atoms were located in a difference Fourier map and allowed to ride on the N atom with N—H = 0.86 Å, Uiso = 1.2Ueq(N). In the absence of significant anomalous dispersion effects, Freidel pairs were merged.

Figures

Fig. 1.
The title molecule with displacement ellipsoids drawn at the 30% probability level, and H atoms as spheres of arbitrary radius.
Fig. 2.
Packing diagram of the title structure showing the N—H···.N hydrogen bonding interactions as dashed lines.

Crystal data

C13H13N3F(000) = 448
Mr = 211.26Dx = 1.274 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1854 reflections
a = 5.7428 (6) Åθ = 2.3–22.4°
b = 10.8751 (11) ŵ = 0.08 mm1
c = 17.6358 (18) ÅT = 295 K
V = 1101.4 (2) Å3Prism, light yellow
Z = 40.30 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX area-detector diffractometer1266 independent reflections
Radiation source: fine-focus sealed tube1117 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→7
Tmin = 0.961, Tmax = 0.982k = −12→13
5694 measured reflectionsl = −21→20

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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0614P)2 + 0.1001P] where P = (Fo2 + 2Fc2)/3
1266 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.11 e Å3
0 restraintsΔρmin = −0.13 e Å3

Special details

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)

xyzUiso*/Ueq
N10.6002 (4)0.87928 (18)0.21104 (10)0.0622 (6)
N20.1584 (3)1.14748 (17)0.45942 (10)0.0530 (5)
N30.1184 (4)1.23449 (18)0.40448 (10)0.0640 (6)
H1N0.23411.26650.38070.077*
H2N0.00761.28190.41940.077*
C10.7655 (5)0.9611 (2)0.22847 (12)0.0602 (6)
H10.89450.96650.19680.072*
C20.7567 (4)1.0378 (2)0.29020 (11)0.0542 (6)
H20.87821.09210.29980.065*
C30.5646 (4)1.03360 (19)0.33835 (10)0.0454 (5)
C40.3919 (4)0.9510 (2)0.31979 (12)0.0533 (6)
H40.25870.94520.34960.064*
C50.4169 (4)0.8766 (2)0.25667 (12)0.0619 (6)
H50.29810.82130.24560.074*
C60.5549 (4)1.11513 (19)0.40763 (11)0.0499 (5)
H6A0.54581.20010.39120.060*
H6B0.69891.10550.43580.060*
C70.3529 (4)1.08934 (19)0.46036 (11)0.0459 (5)
C80.3761 (4)0.98845 (19)0.51709 (11)0.0469 (5)
C90.5659 (4)0.9093 (2)0.51678 (13)0.0591 (6)
H90.68450.92120.48160.071*
C100.5815 (5)0.8131 (2)0.56787 (14)0.0678 (7)
H100.70880.76030.56650.081*
C110.4093 (5)0.7957 (2)0.62054 (13)0.0682 (7)
H110.41970.73120.65500.082*
C120.2215 (5)0.8737 (2)0.62229 (13)0.0655 (7)
H120.10510.86210.65830.079*
C130.2038 (4)0.9687 (2)0.57141 (11)0.0565 (6)
H130.07521.02050.57320.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0694 (14)0.0660 (12)0.0512 (10)0.0081 (11)0.0022 (10)−0.0091 (9)
N20.0551 (11)0.0526 (10)0.0512 (9)0.0007 (10)0.0080 (8)0.0013 (8)
N30.0611 (13)0.0627 (12)0.0683 (11)0.0049 (12)0.0136 (10)0.0125 (10)
C10.0592 (14)0.0672 (15)0.0544 (12)0.0056 (13)0.0122 (11)−0.0001 (12)
C20.0489 (12)0.0587 (14)0.0549 (11)0.0007 (11)0.0078 (10)−0.0002 (10)
C30.0481 (11)0.0444 (10)0.0438 (9)0.0030 (9)0.0022 (9)0.0036 (8)
C40.0509 (12)0.0570 (13)0.0520 (11)−0.0054 (11)0.0076 (10)−0.0032 (10)
C50.0666 (15)0.0620 (14)0.0571 (12)−0.0071 (13)−0.0007 (12)−0.0081 (11)
C60.0482 (11)0.0501 (12)0.0513 (11)−0.0052 (10)0.0064 (9)−0.0052 (9)
C70.0463 (11)0.0457 (11)0.0456 (10)−0.0041 (10)0.0051 (9)−0.0089 (9)
C80.0481 (12)0.0480 (11)0.0448 (9)−0.0043 (10)0.0020 (9)−0.0077 (8)
C90.0553 (13)0.0653 (13)0.0569 (12)0.0047 (12)0.0051 (11)0.0008 (11)
C100.0663 (16)0.0636 (15)0.0735 (15)0.0116 (14)−0.0056 (14)0.0030 (12)
C110.0794 (19)0.0603 (14)0.0648 (14)−0.0024 (14)−0.0045 (13)0.0112 (11)
C120.0658 (16)0.0688 (16)0.0619 (13)−0.0056 (14)0.0096 (12)0.0091 (12)
C130.0535 (13)0.0593 (14)0.0568 (11)0.0026 (12)0.0086 (11)0.0022 (11)

Geometric parameters (Å, °)

N1—C51.325 (3)C6—C71.513 (3)
N1—C11.337 (3)C6—H6A0.9700
N2—C71.283 (3)C6—H6B0.9700
N2—N31.374 (2)C7—C81.491 (3)
N3—H1N0.8600C8—C91.389 (3)
N3—H2N0.8600C8—C131.394 (3)
C1—C21.372 (3)C9—C101.383 (3)
C1—H10.9300C9—H90.9300
C2—C31.393 (3)C10—C111.370 (4)
C2—H20.9300C10—H100.9300
C3—C41.378 (3)C11—C121.373 (4)
C3—C61.511 (3)C11—H110.9300
C4—C51.384 (3)C12—C131.372 (3)
C4—H40.9300C12—H120.9300
C5—H50.9300C13—H130.9300
C5—N1—C1116.04 (19)C7—C6—H6B108.6
C7—N2—N3119.61 (19)H6A—C6—H6B107.6
N2—N3—H1N119.6N2—C7—C8116.69 (18)
N2—N3—H2N108.8N2—C7—C6124.60 (19)
H1N—N3—H2N118.5C8—C7—C6118.71 (19)
N1—C1—C2124.1 (2)C9—C8—C13117.7 (2)
N1—C1—H1117.9C9—C8—C7121.58 (18)
C2—C1—H1117.9C13—C8—C7120.7 (2)
C1—C2—C3119.5 (2)C10—C9—C8121.1 (2)
C1—C2—H2120.2C10—C9—H9119.4
C3—C2—H2120.2C8—C9—H9119.4
C4—C3—C2116.52 (18)C11—C10—C9120.0 (2)
C4—C3—C6123.25 (18)C11—C10—H10120.0
C2—C3—C6120.21 (19)C9—C10—H10120.0
C3—C4—C5119.8 (2)C10—C11—C12119.8 (2)
C3—C4—H4120.1C10—C11—H11120.1
C5—C4—H4120.1C12—C11—H11120.1
N1—C5—C4123.9 (2)C13—C12—C11120.6 (2)
N1—C5—H5118.0C13—C12—H12119.7
C4—C5—H5118.0C11—C12—H12119.7
C3—C6—C7114.62 (17)C12—C13—C8120.9 (2)
C3—C6—H6A108.6C12—C13—H13119.6
C7—C6—H6A108.6C8—C13—H13119.6
C3—C6—H6B108.6
C5—N1—C1—C21.5 (3)C3—C6—C7—C883.3 (2)
N1—C1—C2—C3−0.9 (3)N2—C7—C8—C9171.57 (19)
C1—C2—C3—C4−0.3 (3)C6—C7—C8—C9−7.5 (3)
C1—C2—C3—C6178.50 (18)N2—C7—C8—C13−6.9 (3)
C2—C3—C4—C50.9 (3)C6—C7—C8—C13174.03 (18)
C6—C3—C4—C5−177.9 (2)C13—C8—C9—C100.9 (3)
C1—N1—C5—C4−0.9 (3)C7—C8—C9—C10−177.5 (2)
C3—C4—C5—N1−0.3 (3)C8—C9—C10—C11−0.8 (4)
C4—C3—C6—C76.5 (3)C9—C10—C11—C120.2 (4)
C2—C3—C6—C7−172.19 (19)C10—C11—C12—C130.4 (4)
N3—N2—C7—C8−174.61 (17)C11—C12—C13—C8−0.3 (3)
N3—N2—C7—C64.4 (3)C9—C8—C13—C12−0.4 (3)
C3—C6—C7—N2−95.7 (2)C7—C8—C13—C12178.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H1N···N1i0.862.243.040 (3)154

Symmetry codes: (i) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2620).

References

  • Bruker (2002). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • De, S., Chowdhury, S., Tocher, D. A. & Datta, D. (2006). CrystEngComm, 8, 670–673.
  • Patra, G. K. & Goldberg, I. (2003). Cryst. Growth Des.3, 321–329.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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