2,3-Dimethyl-N-[(E)-(1H-pyrrol-2-yl)methyl­idene]aniline

Tahir, M.N.; Tariq, M.I.; Ahmad, S.; Sarfraz, M.; Tariq, R.H.

doi:10.1107/S1600536810031867

organic compounds

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Volume 66| Part 9| September 2010| Page o2295

https://doi.org/10.1107/S1600536810031867

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2,3-Dimethyl-N-[(E)-(1H-pyrrol-2-yl)methylidene]aniline

M. Nawaz Tahir,^a ^* Muhammad Ilyas Tariq,^b Shahbaz Ahmad,^b Muhammad Sarfraz ^b and Riaz H. Tariq ^c

^aDepartment of Physics, University of Sargodha, Sargodha, Pakistan, ^bDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^cInstitute of Chemical and Pharmaceutical Sciences, The University of Faisalabad, Faisalabad, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 8 August 2010; accepted 9 August 2010; online 11 August 2010)

In the title compound, C₁₃H₁₄N₂, the dihedral angle between the aromatic rings is 69.73 (14)°. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R₂²(10) loops. A weak C—H⋯π interaction also occurs.

Related literature

For background to Schiff bases and for related structures, see: Hussain et al. (2010a ,b ), Sarfraz et al. (2010 ); Tariq et al. (2010 ): For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₄N₂
M_r = 198.26
Monoclinic, P 2₁ /c
a = 12.8684 (9) Å
b = 7.1649 (5) Å
c = 12.9517 (9) Å
β = 107.613 (3)°
V = 1138.18 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.30 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.980, T_max = 0.993
8641 measured reflections
2066 independent reflections
1075 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.142
S = 1.01
2066 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C13/N2 pyrrol ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.86	2.20	3.017 (3)	158
C9—H9⋯Cg1ⁱⁱ	0.93	2.80	3.606 (3)	145
Symmetry codes: (i) -x+1, -y+2, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810031867/hb5606sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031867/hb5606Isup2.hkl

checkCIF report

Comment top

We have reported crystal structures of Schiff bases containing 2,3-dimethylaniline (Tariq et al., 2010), (Sarfraz et al., 2010) and (Hussain et al., 2010b) and as a part of this project, we report herein the structure and synthesis of the title compound (I, Fig. 1).

The crystal structure of (II) i.e., N^'-[(E)-(1-methyl-1H-pyrrol-2-yl)methylidene]benzohydrazide (Hussain et al., 2010a) has been published which contain the common 1H-pyrrole-2-carbaldehyde moiety as in (I).

In (I), the 2,3-dimethylanilinic group A (C1—C8/N1) and the 1H-pyrrole-2-carbaldehyde moiety B (C9—C13/N2) are planar with r. m. s. deviations of 0.0197 and 0.0094 Å, respectively. The dihedral angle between A/B is 70.50 (7)°. The molecules form dimers (Fig. 2) due to intermolecular H-bonding of N—H···N type (Table 1) and complete R₂²(10) ring motif (Bernstein et al., 1995). In stabilization of the molecules C—H···π interactions (Table 1) also play important role.

Related literature top

For background to Schiff bases and for related structures, see: Hussain et al. (2010a,b), Sarfraz et al. (2010); Tariq et al. (2010): For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Equimolar quantities of 2,3-dimethylaniline and 1H-pyrrole-2-carbaldehyde were refluxed in methanol for 45 min resulting in a clear solution. The solution was kept at room temperature which afforded colourless needles of (I) after 48 h.

Structure description top

For background to Schiff bases and for related structures, see: Hussain et al. (2010a,b), Sarfraz et al. (2010); Tariq et al. (2010): For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing of (I), which shows that molecules form dimers.

2,3-Dimethyl-N-[(E)-(1H-pyrrol-2-yl)methylidene]aniline top

Crystal data top

C₁₃H₁₄N₂	F(000) = 424
M_r = 198.26	D_x = 1.157 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1075 reflections
a = 12.8684 (9) Å	θ = 3.2–25.3°
b = 7.1649 (5) Å	µ = 0.07 mm⁻¹
c = 12.9517 (9) Å	T = 296 K
β = 107.613 (3)°	Needle, colourless
V = 1138.18 (14) Å³	0.30 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2066 independent reflections
Radiation source: fine-focus sealed tube	1075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
T_min = 0.980, T_max = 0.993	l = −15→15
8641 measured reflections

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0559P)² + 0.0942P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2066 reflections	Δρ_max = 0.15 e Å⁻³
139 parameters	Δρ_min = −0.13 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: 0.019 (4)

Crystal data top

C₁₃H₁₄N₂	V = 1138.18 (14) Å³
M_r = 198.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8684 (9) Å	µ = 0.07 mm⁻¹
b = 7.1649 (5) Å	T = 296 K
c = 12.9517 (9) Å	0.30 × 0.12 × 0.10 mm
β = 107.613 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2066 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1075 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.993	R_int = 0.065
8641 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.01	Δρ_max = 0.15 e Å⁻³
2066 reflections	Δρ_min = −0.13 e Å⁻³
139 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
N1	0.39549 (16)	0.8356 (3)	0.05111 (16)	0.0532 (8)
N2	0.62151 (16)	0.9535 (3)	0.15496 (16)	0.0550 (8)
C1	0.2837 (2)	0.7796 (3)	0.01500 (19)	0.0499 (9)
C2	0.25093 (19)	0.6419 (4)	−0.06368 (19)	0.0539 (9)
C3	0.1406 (2)	0.5922 (4)	−0.1006 (2)	0.0659 (11)
C4	0.0680 (2)	0.6814 (4)	−0.0579 (3)	0.0787 (11)
C5	0.1015 (2)	0.8157 (4)	0.0209 (3)	0.0834 (14)
C6	0.2096 (2)	0.8668 (4)	0.0569 (2)	0.0675 (11)
C7	0.3339 (2)	0.5434 (4)	−0.1043 (2)	0.0766 (11)
C8	0.0995 (3)	0.4408 (5)	−0.1836 (2)	0.1085 (16)
C9	0.44692 (19)	0.8048 (3)	0.1505 (2)	0.0516 (9)
C10	0.55763 (19)	0.8560 (3)	0.20329 (18)	0.0495 (9)
C11	0.6209 (2)	0.8162 (3)	0.3068 (2)	0.0592 (10)
C12	0.7242 (2)	0.8895 (4)	0.3205 (2)	0.0642 (10)
C13	0.7225 (2)	0.9738 (4)	0.2261 (2)	0.0635 (10)
H2	0.60086	0.99538	0.08967	0.0660*
H4	−0.00546	0.64985	−0.08297	0.0945*
H5	0.05137	0.87191	0.04976	0.1003*
H6	0.23263	0.95956	0.10904	0.0810*
H7A	0.39874	0.61809	−0.08930	0.1147*
H7B	0.30476	0.52419	−0.18105	0.1147*
H7C	0.35134	0.42497	−0.06860	0.1147*
H8A	0.13149	0.32366	−0.15456	0.1628*
H8B	0.11924	0.46977	−0.24760	0.1628*
H8C	0.02160	0.43251	−0.20160	0.1628*
H9	0.40938	0.74430	0.19188	0.0620*
H11	0.59856	0.75163	0.35870	0.0711*
H12	0.78356	0.88212	0.38276	0.0770*
H13	0.78071	1.03508	0.21258	0.0763*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0534 (13)	0.0565 (14)	0.0494 (13)	−0.0073 (10)	0.0151 (10)	−0.0022 (10)
N2	0.0577 (14)	0.0540 (13)	0.0507 (12)	−0.0053 (11)	0.0125 (11)	0.0011 (11)
C1	0.0516 (16)	0.0490 (15)	0.0490 (14)	−0.0008 (12)	0.0153 (12)	0.0051 (13)
C2	0.0564 (17)	0.0560 (17)	0.0510 (15)	−0.0043 (13)	0.0186 (13)	0.0053 (13)
C3	0.0591 (19)	0.072 (2)	0.0619 (18)	−0.0102 (15)	0.0113 (15)	0.0075 (15)
C4	0.0465 (17)	0.093 (2)	0.088 (2)	−0.0013 (17)	0.0074 (16)	0.019 (2)
C5	0.062 (2)	0.087 (2)	0.107 (3)	0.0197 (18)	0.0343 (19)	0.009 (2)
C6	0.0686 (19)	0.0597 (18)	0.0789 (19)	0.0044 (15)	0.0294 (16)	−0.0047 (15)
C7	0.081 (2)	0.078 (2)	0.0773 (19)	−0.0120 (16)	0.0337 (16)	−0.0202 (17)
C8	0.096 (3)	0.131 (3)	0.091 (2)	−0.048 (2)	0.017 (2)	−0.027 (2)
C9	0.0581 (16)	0.0438 (16)	0.0572 (16)	−0.0029 (12)	0.0238 (13)	−0.0030 (13)
C10	0.0542 (15)	0.0424 (15)	0.0523 (16)	−0.0024 (12)	0.0166 (13)	−0.0010 (12)
C11	0.0691 (18)	0.0551 (17)	0.0535 (16)	0.0032 (14)	0.0185 (14)	0.0019 (13)
C12	0.0635 (19)	0.0616 (18)	0.0590 (17)	0.0050 (14)	0.0056 (14)	−0.0032 (15)
C13	0.0525 (17)	0.0635 (18)	0.0692 (18)	−0.0074 (14)	0.0103 (14)	−0.0044 (16)

Geometric parameters (Å, º) top

N1—C1	1.429 (3)	C11—C12	1.390 (4)
N1—C9	1.276 (3)	C12—C13	1.358 (4)
N2—C10	1.366 (3)	C4—H4	0.9300
N2—C13	1.354 (3)	C5—H5	0.9300
N2—H2	0.8600	C6—H6	0.9300
C1—C2	1.389 (3)	C7—H7A	0.9600
C1—C6	1.381 (4)	C7—H7B	0.9600
C2—C7	1.502 (4)	C7—H7C	0.9600
C2—C3	1.400 (4)	C8—H8A	0.9600
C3—C4	1.378 (4)	C8—H8B	0.9600
C3—C8	1.506 (4)	C8—H8C	0.9600
C4—C5	1.374 (5)	C9—H9	0.9300
C5—C6	1.376 (4)	C11—H11	0.9300
C9—C10	1.429 (4)	C12—H12	0.9300
C10—C11	1.372 (3)	C13—H13	0.9300

C1—N1—C9	116.4 (2)	C4—C5—H5	120.00
C10—N2—C13	109.3 (2)	C6—C5—H5	120.00
C10—N2—H2	125.00	C1—C6—H6	120.00
C13—N2—H2	125.00	C5—C6—H6	120.00
N1—C1—C2	119.5 (2)	C2—C7—H7A	109.00
N1—C1—C6	119.4 (2)	C2—C7—H7B	109.00
C2—C1—C6	121.1 (2)	C2—C7—H7C	110.00
C1—C2—C3	118.9 (2)	H7A—C7—H7B	109.00
C3—C2—C7	121.1 (2)	H7A—C7—H7C	109.00
C1—C2—C7	120.0 (2)	H7B—C7—H7C	109.00
C2—C3—C8	121.9 (3)	C3—C8—H8A	109.00
C4—C3—C8	119.1 (3)	C3—C8—H8B	109.00
C2—C3—C4	119.0 (3)	C3—C8—H8C	109.00
C3—C4—C5	121.6 (3)	H8A—C8—H8B	109.00
C4—C5—C6	119.7 (3)	H8A—C8—H8C	109.00
C1—C6—C5	119.6 (3)	H8B—C8—H8C	109.00
N1—C9—C10	125.2 (2)	N1—C9—H9	117.00
N2—C10—C11	107.0 (2)	C10—C9—H9	117.00
C9—C10—C11	128.7 (2)	C10—C11—H11	126.00
N2—C10—C9	124.3 (2)	C12—C11—H11	126.00
C10—C11—C12	108.0 (2)	C11—C12—H12	126.00
C11—C12—C13	107.4 (2)	C13—C12—H12	126.00
N2—C13—C12	108.4 (2)	N2—C13—H13	126.00
C3—C4—H4	119.00	C12—C13—H13	126.00
C5—C4—H4	119.00

C9—N1—C1—C2	−116.5 (3)	C1—C2—C3—C8	−178.4 (2)
C9—N1—C1—C6	65.2 (3)	C7—C2—C3—C4	177.5 (3)
C1—N1—C9—C10	−177.7 (2)	C7—C2—C3—C8	−1.0 (4)
C13—N2—C10—C9	−178.2 (2)	C2—C3—C4—C5	−0.9 (5)
C13—N2—C10—C11	0.3 (3)	C8—C3—C4—C5	177.6 (3)
C10—N2—C13—C12	0.0 (3)	C3—C4—C5—C6	1.6 (5)
N1—C1—C2—C3	−178.2 (2)	C4—C5—C6—C1	−1.4 (4)
N1—C1—C2—C7	4.4 (4)	N1—C9—C10—N2	3.4 (4)
C6—C1—C2—C3	0.1 (4)	N1—C9—C10—C11	−174.7 (2)
C6—C1—C2—C7	−177.3 (2)	N2—C10—C11—C12	−0.4 (3)
N1—C1—C6—C5	178.8 (2)	C9—C10—C11—C12	177.9 (2)
C2—C1—C6—C5	0.5 (4)	C10—C11—C12—C13	0.5 (3)
C1—C2—C3—C4	0.1 (4)	C11—C12—C13—N2	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C13/N2 pyrrol ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.20	3.017 (3)	158
C9—H9···Cg1ⁱⁱ	0.93	2.80	3.606 (3)	145

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂
M_r	198.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.8684 (9), 7.1649 (5), 12.9517 (9)
β (°)	107.613 (3)
V (Å³)	1138.18 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.980, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	8641, 2066, 1075
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.142, 1.01
No. of reflections	2066
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

N1—C1	1.429 (3)	N2—C10	1.366 (3)
N1—C9	1.276 (3)	N2—C13	1.354 (3)

C1—N1—C9	116.4 (2)	N1—C9—C10	125.2 (2)
C10—N2—C13	109.3 (2)	N2—C10—C11	107.0 (2)
N1—C1—C2	119.5 (2)	N2—C10—C9	124.3 (2)
N1—C1—C6	119.4 (2)	N2—C13—C12	108.4 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C13/N2 pyrrol ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.20	3.017 (3)	158
C9—H9···Cg1ⁱⁱ	0.93	2.80	3.606 (3)	145

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

References

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