(Z)-2-[2-(4-Methyl­benzyl­idene)hydrazin­yl]pyridine

Yuvaraj, H.; Sundaramoorthy, S.; Velmurugan, D.; Kalkhambkar, R.G.

doi:10.1107/S1600536810052372

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o178

https://doi.org/10.1107/S1600536810052372

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(Z)-2-[2-(4-Methylbenzylidene)hydrazinyl]pyridine

Haldorai Yuvaraj,^a ^* S. Sundaramoorthy,^b D. Velmurugan ^b and Rajesh G. Kalkhambkar ^c

^aSchool of Display and Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749, Republic of Korea, ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cDepartment of Chemistry, Karnatak Universitys Karnatak Science College, Dharwad 580 001, Karnataka, India
^*Correspondence e-mail: yuvraj_pd@yahoo.co.in

(Received 9 December 2010; accepted 14 December 2010; online 18 December 2010)

Molecules of the title compound, C₁₃H₁₃N₃, are essentially planar (r.m.s. deviation for all non-H atoms = 0.054 Å). The dihedral angle between the two aromatic rings is 6.33 (5)°. In the crystal, pairs of centrosymmetrically related molecules are linked through N—H⋯N hydrogen bonds, forming N—H⋯N dimers with graph-set motif R₂²(8).

Related literature

For the biological activity of hydrazone derivatives, see: Savini et al. (2002 ); Silva et al. (2004 ). For a related structure, see: Yuvaraj et al. (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₃N₃
M_r = 211.26
Monoclinic, P 2₁ /c
a = 5.2385 (8) Å
b = 10.7215 (17) Å
c = 20.590 (3) Å
β = 92.699 (5)°
V = 1155.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.981, T_max = 0.984
10622 measured reflections
2850 independent reflections
1341 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.154
S = 1.00
2850 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N3ⁱ	0.86	2.28	3.131 (2)	170
Symmetry code: (i) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810052372/bt5435sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052372/bt5435Isup2.hkl

checkCIF report

Comment top

The title compound was prepared as part of our continuing interest on the nitrogen based heterocycles (Yuvaraj et al., 2010).

In the title molecule, the C2—C3—C7 and C8—N1—N2 bond angles are 121.65 (2)° and 117.46 (2)°, respectively. The benzene and pyridine form a dihedral angle of 6.33 (5)°.

In the crystal structure,the molecules at (x, y, z) and (1 - x,-y,-z) are linked by N(2)—H(2 A)···N(3) hydrogen bonds, generating a centrosymmetric dimeric ring motif R₂²(8) (Bernstein et al., 1995). The centroid of the R₂²(8) motif lies at (1/2,0,0). In addition, there is a weak C—H···N interaction linking the centrosymmetric pair of molecules.

Related literature top

For the biological activity of hydrazone derivatives, see: Savini et al. (2002); Silva et al. (2004). For a related structure, see: Yuvaraj et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 2-hydrazinopyridine and p-tolualdehyde were refluxed in ethanol with a catalytic quantity of con. HCl or gl. AcOH. After the reaction was over, the contents were cooled down and filtered to form the product. Diffraction quality crystals were obtained upon recrystallization in ethanol.

Structure description top

The title compound was prepared as part of our continuing interest on the nitrogen based heterocycles (Yuvaraj et al., 2010).

In the title molecule, the C2—C3—C7 and C8—N1—N2 bond angles are 121.65 (2)° and 117.46 (2)°, respectively. The benzene and pyridine form a dihedral angle of 6.33 (5)°.

For the biological activity of hydrazone derivatives, see: Savini et al. (2002); Silva et al. (2004). For a related structure, see: Yuvaraj et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the molecule showing the displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal packing of the molecules viewed down a axis. For clarity, hydrogen atoms which are not involved in hydrogen bonding are omitted

(Z)-2-[2-(4-Methylbenzylidene)hydrazinyl]pyridine top

Crystal data top

C₁₃H₁₃N₃	F(000) = 448
M_r = 211.26	D_x = 1.215 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 715 reflections
a = 5.2385 (8) Å	θ = 2.0–28.4°
b = 10.7215 (17) Å	µ = 0.08 mm⁻¹
c = 20.590 (3) Å	T = 293 K
β = 92.699 (5)°	Block, colourless
V = 1155.2 (3) Å³	0.26 × 0.23 × 0.21 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	2850 independent reflections
Radiation source: fine-focus sealed tube	1341 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scans	θ_max = 28.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.981, T_max = 0.984	k = −12→14
10622 measured reflections	l = −27→27

Refinement top

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0649P)² + 0.0987P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2850 reflections	Δρ_max = 0.14 e Å⁻³
147 parameters	Δρ_min = −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: 0.011 (3)

Crystal data top

C₁₃H₁₃N₃	V = 1155.2 (3) Å³
M_r = 211.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.2385 (8) Å	µ = 0.08 mm⁻¹
b = 10.7215 (17) Å	T = 293 K
c = 20.590 (3) Å	0.26 × 0.23 × 0.21 mm
β = 92.699 (5)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2850 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1341 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.984	R_int = 0.027
10622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.00	Δρ_max = 0.14 e Å⁻³
2850 reflections	Δρ_min = −0.11 e Å⁻³
147 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.2431 (4)	0.01692 (17)	0.21369 (9)	0.0756 (5)
H1	−0.2750	0.0866	0.1877	0.091*
C2	−0.3858 (4)	−0.00253 (17)	0.26709 (9)	0.0797 (5)
H2	−0.5119	0.0548	0.2766	0.096*
C3	−0.3465 (3)	−0.10558 (17)	0.30708 (8)	0.0712 (5)
C4	−0.1622 (4)	−0.18826 (18)	0.29040 (9)	0.0852 (6)
H4	−0.1341	−0.2594	0.3156	0.102*
C5	−0.0171 (4)	−0.16896 (18)	0.23728 (9)	0.0874 (6)
H5	0.1077	−0.2269	0.2276	0.105*
C6	−0.0525 (3)	−0.06569 (15)	0.19808 (8)	0.0674 (5)
C7	−0.5002 (4)	−0.1260 (2)	0.36606 (9)	0.0936 (6)
H7A	−0.4823	−0.2110	0.3801	0.140*
H7B	−0.6770	−0.1086	0.3553	0.140*
H7C	−0.4395	−0.0714	0.4003	0.140*
C8	0.1072 (3)	−0.04777 (17)	0.14289 (8)	0.0731 (5)
H8	0.2328	−0.1063	0.1347	0.088*
C9	0.1978 (3)	0.15130 (15)	0.01140 (8)	0.0662 (5)
C10	−0.0022 (4)	0.23520 (18)	0.01634 (9)	0.0813 (5)
H10	−0.1154	0.2281	0.0496	0.098*
C11	−0.0290 (4)	0.32800 (19)	−0.02841 (10)	0.0907 (6)
H11	−0.1607	0.3857	−0.0258	0.109*
C12	0.1387 (4)	0.33637 (19)	−0.07751 (11)	0.0951 (6)
H12	0.1231	0.3990	−0.1087	0.114*
C13	0.3290 (4)	0.2497 (2)	−0.07891 (10)	0.0895 (6)
H13	0.4430	0.2554	−0.1121	0.107*
N1	0.0784 (3)	0.04629 (14)	0.10557 (6)	0.0720 (4)
N2	0.2388 (3)	0.05650 (13)	0.05528 (6)	0.0749 (4)
H2A	0.3623	0.0046	0.0513	0.090*
N3	0.3633 (3)	0.15655 (13)	−0.03568 (7)	0.0742 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0777 (12)	0.0642 (10)	0.0860 (12)	0.0007 (9)	0.0162 (9)	0.0076 (9)
C2	0.0744 (12)	0.0739 (12)	0.0927 (12)	0.0054 (10)	0.0244 (10)	0.0042 (10)
C3	0.0665 (11)	0.0751 (11)	0.0727 (10)	−0.0031 (9)	0.0112 (8)	0.0009 (9)
C4	0.0932 (14)	0.0836 (13)	0.0798 (12)	0.0151 (11)	0.0158 (10)	0.0178 (10)
C5	0.0928 (14)	0.0874 (13)	0.0837 (12)	0.0246 (11)	0.0219 (11)	0.0115 (10)
C6	0.0682 (11)	0.0661 (10)	0.0687 (10)	−0.0004 (9)	0.0094 (8)	−0.0022 (8)
C7	0.0926 (14)	0.1023 (15)	0.0878 (13)	0.0005 (12)	0.0244 (11)	0.0100 (11)
C8	0.0754 (12)	0.0720 (11)	0.0729 (10)	0.0023 (9)	0.0137 (9)	−0.0022 (9)
C9	0.0638 (11)	0.0657 (11)	0.0693 (10)	−0.0110 (9)	0.0067 (8)	−0.0058 (8)
C10	0.0767 (12)	0.0795 (12)	0.0884 (12)	0.0016 (11)	0.0117 (10)	−0.0051 (11)
C11	0.0797 (14)	0.0773 (13)	0.1152 (16)	0.0026 (10)	0.0057 (12)	0.0009 (12)
C12	0.0857 (15)	0.0804 (13)	0.1190 (16)	−0.0064 (12)	0.0035 (13)	0.0221 (12)
C13	0.0778 (13)	0.0941 (14)	0.0976 (14)	−0.0129 (12)	0.0151 (10)	0.0157 (12)
N1	0.0709 (9)	0.0764 (10)	0.0699 (8)	−0.0061 (7)	0.0162 (7)	−0.0064 (8)
N2	0.0737 (10)	0.0783 (10)	0.0741 (9)	0.0027 (8)	0.0191 (7)	0.0002 (8)
N3	0.0671 (9)	0.0762 (10)	0.0801 (9)	−0.0092 (7)	0.0115 (8)	0.0036 (8)

Geometric parameters (Å, º) top

C1—C2	1.374 (2)	C8—N1	1.273 (2)
C1—C6	1.383 (2)	C8—H8	0.9300
C1—H1	0.9300	C9—N3	1.332 (2)
C2—C3	1.387 (2)	C9—N2	1.370 (2)
C2—H2	0.9300	C9—C10	1.388 (2)
C3—C4	1.366 (2)	C10—C11	1.359 (2)
C3—C7	1.504 (2)	C10—H10	0.9300
C4—C5	1.377 (3)	C11—C12	1.373 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.378 (2)	C12—C13	1.364 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—C8	1.455 (2)	C13—N3	1.344 (2)
C7—H7A	0.9600	C13—H13	0.9300
C7—H7B	0.9600	N1—N2	1.3680 (17)
C7—H7C	0.9600	N2—H2A	0.8600

C2—C1—C6	120.95 (17)	N1—C8—C6	121.34 (17)
C2—C1—H1	119.5	N1—C8—H8	119.3
C6—C1—H1	119.5	C6—C8—H8	119.3
C1—C2—C3	121.63 (17)	N3—C9—N2	115.09 (16)
C1—C2—H2	119.2	N3—C9—C10	123.05 (17)
C3—C2—H2	119.2	N2—C9—C10	121.86 (17)
C4—C3—C2	117.02 (16)	C11—C10—C9	118.63 (18)
C4—C3—C7	121.33 (17)	C11—C10—H10	120.7
C2—C3—C7	121.65 (17)	C9—C10—H10	120.7
C3—C4—C5	121.69 (18)	C10—C11—C12	119.8 (2)
C3—C4—H4	119.2	C10—C11—H11	120.1
C5—C4—H4	119.2	C12—C11—H11	120.1
C4—C5—C6	121.46 (18)	C13—C12—C11	117.68 (19)
C4—C5—H5	119.3	C13—C12—H12	121.2
C6—C5—H5	119.3	C11—C12—H12	121.2
C5—C6—C1	117.22 (16)	N3—C13—C12	124.55 (19)
C5—C6—C8	119.79 (16)	N3—C13—H13	117.7
C1—C6—C8	122.99 (16)	C12—C13—H13	117.7
C3—C7—H7A	109.5	C8—N1—N2	117.46 (15)
C3—C7—H7B	109.5	N1—N2—C9	118.41 (15)
H7A—C7—H7B	109.5	N1—N2—H2A	120.8
C3—C7—H7C	109.5	C9—N2—H2A	120.8
H7A—C7—H7C	109.5	C9—N3—C13	116.24 (17)
H7B—C7—H7C	109.5

C6—C1—C2—C3	−0.5 (3)	N3—C9—C10—C11	−0.8 (3)
C1—C2—C3—C4	−1.1 (3)	N2—C9—C10—C11	179.07 (15)
C1—C2—C3—C7	179.13 (16)	C9—C10—C11—C12	0.6 (3)
C2—C3—C4—C5	1.6 (3)	C10—C11—C12—C13	−0.3 (3)
C7—C3—C4—C5	−178.62 (18)	C11—C12—C13—N3	0.2 (3)
C3—C4—C5—C6	−0.6 (3)	C6—C8—N1—N2	179.29 (13)
C4—C5—C6—C1	−1.0 (3)	C8—N1—N2—C9	174.71 (14)
C4—C5—C6—C8	179.16 (17)	N3—C9—N2—N1	179.08 (13)
C2—C1—C6—C5	1.5 (3)	C10—C9—N2—N1	−0.8 (2)
C2—C1—C6—C8	−178.67 (16)	N2—C9—N3—C13	−179.22 (14)
C5—C6—C8—N1	179.65 (16)	C10—C9—N3—C13	0.7 (2)
C1—C6—C8—N1	−0.2 (3)	C12—C13—N3—C9	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.86	2.28	3.131 (2)	170

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃N₃
M_r	211.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.2385 (8), 10.7215 (17), 20.590 (3)
β (°)	92.699 (5)
V (Å³)	1155.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.23 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.981, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	10622, 2850, 1341
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.154, 1.00
No. of reflections	2850
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.11

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.86	2.28	3.131 (2)	170

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

HY gratefully acknowledges Yeungnam University for the opportunity to work as a Full-Time Foreign Instructor. SS and DV thank the TBI X-ray Facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection and the University Grants Commission (UGC & SAP) for financial support.

References

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