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

Abstract

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,

• a = 5.2385 (8) Å

• b = 10.7215 (17) Å

• c = 20.590 (3) Å

• β = 92.699 (5)°

• V = 1155.2 (3) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with 1.5U_eq(C) for methyl H or 1.2 U_eq(C,N) for other H atoms.

Figures

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

Crystal data

C13H13N3	F(000) = 448
Mr = 211.26	Dx = 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

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

Refinement

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(Fo2) + (0.0649P)2 + 0.0987P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2850 reflections	Δρmax = 0.14 e Å−3
147 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x+1, −y, −z.