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

Tang, S.-P.

doi:10.1107/S1600536809014330

organic compounds

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Volume 65| Part 5| May 2009| Page o1090

doi:10.1107/S1600536809014330

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

Si-Ping Tang ^a ^*

^aDepartment of Chemistry and Material Science, Hengyang Normal University, Hengyang, Hunan 421008, People's Republic of China
^*Correspondence e-mail: sptang88@163.com

(Received 15 April 2009; accepted 17 April 2009; online 22 April 2009)

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 ); Patra & Goldberg (2003 ).

Experimental

Crystal data

C₁₃H₁₃N₃
M_r = 211.26
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.04
1266 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N⋯N1ⁱ	0.86	2.24	3.040 (3)	154
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014330/sj2620sup1.cif

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

checkCIF report

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%).

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

	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.

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

Crystal data top

C₁₃H₁₃N₃	F(000) = 448
M_r = 211.26	D_x = 1.274 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1854 reflections
a = 5.7428 (6) Å	θ = 2.3–22.4°
b = 10.8751 (11) Å	µ = 0.08 mm⁻¹
c = 17.6358 (18) Å	T = 295 K
V = 1101.4 (2) Å³	Prism, light yellow
Z = 4	0.30 × 0.22 × 0.15 mm

Data collection top

Bruker SMART APEX area-detector diffractometer	1266 independent reflections
Radiation source: fine-focus sealed tube	1117 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.961, T_max = 0.982	k = −12→13
5694 measured reflections	l = −21→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0614P)² + 0.1001P] where P = (F_o² + 2F_c²)/3
1266 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₃H₁₃N₃	V = 1101.4 (2) Å³
M_r = 211.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.7428 (6) Å	µ = 0.08 mm⁻¹
b = 10.8751 (11) Å	T = 295 K
c = 17.6358 (18) Å	0.30 × 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)
T_min = 0.961, T_max = 0.982	R_int = 0.026
5694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.04	Δρ_max = 0.11 e Å⁻³
1266 reflections	Δρ_min = −0.13 e Å⁻³
145 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

	x	y	z	U_iso*/U_eq
N1	0.6002 (4)	0.87928 (18)	0.21104 (10)	0.0622 (6)
N2	0.1584 (3)	1.14748 (17)	0.45942 (10)	0.0530 (5)
N3	0.1184 (4)	1.23449 (18)	0.40448 (10)	0.0640 (6)
H1N	0.2341	1.2665	0.3807	0.077*
H2N	0.0076	1.2819	0.4194	0.077*
C1	0.7655 (5)	0.9611 (2)	0.22847 (12)	0.0602 (6)
H1	0.8945	0.9665	0.1968	0.072*
C2	0.7567 (4)	1.0378 (2)	0.29020 (11)	0.0542 (6)
H2	0.8782	1.0921	0.2998	0.065*
C3	0.5646 (4)	1.03360 (19)	0.33835 (10)	0.0454 (5)
C4	0.3919 (4)	0.9510 (2)	0.31979 (12)	0.0533 (6)
H4	0.2587	0.9452	0.3496	0.064*
C5	0.4169 (4)	0.8766 (2)	0.25667 (12)	0.0619 (6)
H5	0.2981	0.8213	0.2456	0.074*
C6	0.5549 (4)	1.11513 (19)	0.40763 (11)	0.0499 (5)
H6A	0.5458	1.2001	0.3912	0.060*
H6B	0.6989	1.1055	0.4358	0.060*
C7	0.3529 (4)	1.08934 (19)	0.46036 (11)	0.0459 (5)
C8	0.3761 (4)	0.98845 (19)	0.51709 (11)	0.0469 (5)
C9	0.5659 (4)	0.9093 (2)	0.51678 (13)	0.0591 (6)
H9	0.6845	0.9212	0.4816	0.071*
C10	0.5815 (5)	0.8131 (2)	0.56787 (14)	0.0678 (7)
H10	0.7088	0.7603	0.5665	0.081*
C11	0.4093 (5)	0.7957 (2)	0.62054 (13)	0.0682 (7)
H11	0.4197	0.7312	0.6550	0.082*
C12	0.2215 (5)	0.8737 (2)	0.62229 (13)	0.0655 (7)
H12	0.1051	0.8621	0.6583	0.079*
C13	0.2038 (4)	0.9687 (2)	0.57141 (11)	0.0565 (6)
H13	0.0752	1.0205	0.5732	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0694 (14)	0.0660 (12)	0.0512 (10)	0.0081 (11)	0.0022 (10)	−0.0091 (9)
N2	0.0551 (11)	0.0526 (10)	0.0512 (9)	0.0007 (10)	0.0080 (8)	0.0013 (8)
N3	0.0611 (13)	0.0627 (12)	0.0683 (11)	0.0049 (12)	0.0136 (10)	0.0125 (10)
C1	0.0592 (14)	0.0672 (15)	0.0544 (12)	0.0056 (13)	0.0122 (11)	−0.0001 (12)
C2	0.0489 (12)	0.0587 (14)	0.0549 (11)	0.0007 (11)	0.0078 (10)	−0.0002 (10)
C3	0.0481 (11)	0.0444 (10)	0.0438 (9)	0.0030 (9)	0.0022 (9)	0.0036 (8)
C4	0.0509 (12)	0.0570 (13)	0.0520 (11)	−0.0054 (11)	0.0076 (10)	−0.0032 (10)
C5	0.0666 (15)	0.0620 (14)	0.0571 (12)	−0.0071 (13)	−0.0007 (12)	−0.0081 (11)
C6	0.0482 (11)	0.0501 (12)	0.0513 (11)	−0.0052 (10)	0.0064 (9)	−0.0052 (9)
C7	0.0463 (11)	0.0457 (11)	0.0456 (10)	−0.0041 (10)	0.0051 (9)	−0.0089 (9)
C8	0.0481 (12)	0.0480 (11)	0.0448 (9)	−0.0043 (10)	0.0020 (9)	−0.0077 (8)
C9	0.0553 (13)	0.0653 (13)	0.0569 (12)	0.0047 (12)	0.0051 (11)	0.0008 (11)
C10	0.0663 (16)	0.0636 (15)	0.0735 (15)	0.0116 (14)	−0.0056 (14)	0.0030 (12)
C11	0.0794 (19)	0.0603 (14)	0.0648 (14)	−0.0024 (14)	−0.0045 (13)	0.0112 (11)
C12	0.0658 (16)	0.0688 (16)	0.0619 (13)	−0.0056 (14)	0.0096 (12)	0.0091 (12)
C13	0.0535 (13)	0.0593 (14)	0.0568 (11)	0.0026 (12)	0.0086 (11)	0.0022 (11)

Geometric parameters (Å, º) top

N1—C5	1.325 (3)	C6—C7	1.513 (3)
N1—C1	1.337 (3)	C6—H6A	0.9700
N2—C7	1.283 (3)	C6—H6B	0.9700
N2—N3	1.374 (2)	C7—C8	1.491 (3)
N3—H1N	0.8600	C8—C9	1.389 (3)
N3—H2N	0.8600	C8—C13	1.394 (3)
C1—C2	1.372 (3)	C9—C10	1.383 (3)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.393 (3)	C10—C11	1.370 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.378 (3)	C11—C12	1.373 (4)
C3—C6	1.511 (3)	C11—H11	0.9300
C4—C5	1.384 (3)	C12—C13	1.372 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300

C5—N1—C1	116.04 (19)	C7—C6—H6B	108.6
C7—N2—N3	119.61 (19)	H6A—C6—H6B	107.6
N2—N3—H1N	119.6	N2—C7—C8	116.69 (18)
N2—N3—H2N	108.8	N2—C7—C6	124.60 (19)
H1N—N3—H2N	118.5	C8—C7—C6	118.71 (19)
N1—C1—C2	124.1 (2)	C9—C8—C13	117.7 (2)
N1—C1—H1	117.9	C9—C8—C7	121.58 (18)
C2—C1—H1	117.9	C13—C8—C7	120.7 (2)
C1—C2—C3	119.5 (2)	C10—C9—C8	121.1 (2)
C1—C2—H2	120.2	C10—C9—H9	119.4
C3—C2—H2	120.2	C8—C9—H9	119.4
C4—C3—C2	116.52 (18)	C11—C10—C9	120.0 (2)
C4—C3—C6	123.25 (18)	C11—C10—H10	120.0
C2—C3—C6	120.21 (19)	C9—C10—H10	120.0
C3—C4—C5	119.8 (2)	C10—C11—C12	119.8 (2)
C3—C4—H4	120.1	C10—C11—H11	120.1
C5—C4—H4	120.1	C12—C11—H11	120.1
N1—C5—C4	123.9 (2)	C13—C12—C11	120.6 (2)
N1—C5—H5	118.0	C13—C12—H12	119.7
C4—C5—H5	118.0	C11—C12—H12	119.7
C3—C6—C7	114.62 (17)	C12—C13—C8	120.9 (2)
C3—C6—H6A	108.6	C12—C13—H13	119.6
C7—C6—H6A	108.6	C8—C13—H13	119.6
C3—C6—H6B	108.6

C5—N1—C1—C2	1.5 (3)	C3—C6—C7—C8	83.3 (2)
N1—C1—C2—C3	−0.9 (3)	N2—C7—C8—C9	171.57 (19)
C1—C2—C3—C4	−0.3 (3)	C6—C7—C8—C9	−7.5 (3)
C1—C2—C3—C6	178.50 (18)	N2—C7—C8—C13	−6.9 (3)
C2—C3—C4—C5	0.9 (3)	C6—C7—C8—C13	174.03 (18)
C6—C3—C4—C5	−177.9 (2)	C13—C8—C9—C10	0.9 (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—C7	6.5 (3)	C9—C10—C11—C12	0.2 (4)
C2—C3—C6—C7	−172.19 (19)	C10—C11—C12—C13	0.4 (4)
N3—N2—C7—C8	−174.61 (17)	C11—C12—C13—C8	−0.3 (3)
N3—N2—C7—C6	4.4 (3)	C9—C8—C13—C12	−0.4 (3)
C3—C6—C7—N2	−95.7 (2)	C7—C8—C13—C12	178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···N1ⁱ	0.86	2.24	3.040 (3)	154

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃N₃
M_r	211.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	5.7428 (6), 10.8751 (11), 17.6358 (18)
V (Å³)	1101.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.22 × 0.15

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5694, 1266, 1117
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.04
No. of reflections	1266
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.13

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···A	D—H	H···A	D···A	D—H···A
N3—H1N···N1ⁱ	0.86	2.24	3.040 (3)	154.4

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

Acknowledgements

The author thanks Hengyang Normal University for supporting this study.

References

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