organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1090

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

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[De, S., Chowdhury, S., Tocher, D. A. & Datta, D. (2006). CrystEngComm, 8, 670-673.]); Patra & Goldberg (2003[Patra, G. K. & Goldberg, I. (2003). Cryst. Growth Des. 3, 321-329.]).

[Scheme 1]

Experimental

Crystal data
  • C13H13N3

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.961, Tmax = 0.982

  • 5694 measured reflections

  • 1266 independent reflections

  • 1117 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 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 top
Bruker SMART APEX area-detector
diffractometer
1266 independent reflections
Radiation source: fine-focus sealed tube1117 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 67
Tmin = 0.961, Tmax = 0.982k = 1213
5694 measured reflectionsl = 2120
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 Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C13H13N3V = 1101.4 (2) Å3
Mr = 211.26Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.7428 (6) ŵ = 0.08 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.04Δρmax = 0.11 e Å3
1266 reflectionsΔρmin = 0.13 e Å3
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
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, º) 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—C30.9 (3)N2—C7—C8—C9171.57 (19)
C1—C2—C3—C40.3 (3)C6—C7—C8—C97.5 (3)
C1—C2—C3—C6178.50 (18)N2—C7—C8—C136.9 (3)
C2—C3—C4—C50.9 (3)C6—C7—C8—C13174.03 (18)
C6—C3—C4—C5177.9 (2)C13—C8—C9—C100.9 (3)
C1—N1—C5—C40.9 (3)C7—C8—C9—C10177.5 (2)
C3—C4—C5—N10.3 (3)C8—C9—C10—C110.8 (4)
C4—C3—C6—C76.5 (3)C9—C10—C11—C120.2 (4)
C2—C3—C6—C7172.19 (19)C10—C11—C12—C130.4 (4)
N3—N2—C7—C8174.61 (17)C11—C12—C13—C80.3 (3)
N3—N2—C7—C64.4 (3)C9—C8—C13—C120.4 (3)
C3—C6—C7—N295.7 (2)C7—C8—C13—C12178.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N···N1i0.862.243.040 (3)154
Symmetry code: (i) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H13N3
Mr211.26
Crystal system, space groupOrthorhombic, P212121
Temperature (K)295
a, b, c (Å)5.7428 (6), 10.8751 (11), 17.6358 (18)
V3)1101.4 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.30 × 0.22 × 0.15
Data collection
DiffractometerBruker SMART APEX area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.961, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
5694, 1266, 1117
Rint0.026
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.105, 1.04
No. of reflections1266
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N3—H1N···N1i0.862.243.040 (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

First citationBruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDe, S., Chowdhury, S., Tocher, D. A. & Datta, D. (2006). CrystEngComm, 8, 670–673.  Web of Science CSD CrossRef CAS Google Scholar
First citationPatra, G. K. & Goldberg, I. (2003). Cryst. Growth Des. 3, 321–329.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1090
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