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Acta Cryst. (2009). E65, o1090    [ doi:10.1107/S1600536809014330 ]

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

S.-P. Tang

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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.

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 title molecule with displacement ellipsoids drawn at the 30% probability level, and H atoms as spheres of arbitrary radius.
[Figure 2] Fig. 2. Packing diagram of the title structure showing the N—H···.N hydrogen bonding interactions as dashed lines.
[1-Phenyl-2-(4-pyridyl)ethylidene]hydrazine top
Crystal data top
C13H13N3F(000) = 448
Mr = 211.26Dx = 1.274 Mg m−3
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 mm−1
c = 17.6358 (18) ÅT = 295 K
V = 1101.4 (2) Å3Prism, light yellow
Z = 40.30 × 0.22 × 0.15 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer		1266 independent reflections
Radiation source: fine-focus sealed tube1117 reflections with I > 2σ(I)
graphiteRint = 0.026
φ 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 top
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 = 1.04 w = 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 Å−3
0 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C13H13N3V = 1101.4 (2) Å3
Mr = 211.26Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.7428 (6) ŵ = 0.08 mm−1
b = 10.8751 (11) ÅT = 295 K
c = 17.6358 (18) Å0.30 × 0.22 × 0.15 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer		1266 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1117 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.982Rint = 0.026
5694 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.105Δρmax = 0.11 e Å−3
S = 1.04Δρmin = −0.13 e Å−3
1266 reflectionsAbsolute structure: ?
145 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

The author thanks Hengyang Normal University for supporting this study.

references
References top

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. [Please check year - 2006 here, but originally 1999 in Comment]

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.