4,6-Dimethyl-2-p-tolyl­pyrimidine

Xu, C.; Wang, Z.-Q.; Cen, F.-F.; Cheng, L.; Ji, B.-M.

doi:10.1107/S160053680904210X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2785

https://doi.org/10.1107/S160053680904210X

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4,6-Dimethyl-2-p-tolylpyrimidine

Chen Xu,^a ^* Zhi-Qiang Wang,^a Fei-Fei Cen,^b Lin Cheng ^b and Bao-Ming Ji ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China, and ^bChemical Engineering and Pharmaceutics School, Henan University of Science and Technology, Luoyang 471003, People's Republic of China
^*Correspondence e-mail: xubohan@163.com

(Received 5 October 2009; accepted 14 October 2009; online 17 October 2009)

The molecule of the title compound, C₁₃H₁₄N₂, is located on a crystallographic mirror plane. The aromatic rings make a dihedral angle of 3.4 (2)°. The H atoms of the methyl groups on the benzene ring are disordered over two positions; their site-occupation factors were fixed at 0.5. In the crystal, intermolecular C—H⋯π contacts form infinite chains perpendicular to the b axis.

Related literature

The title compound was derived from the reaction of p-tolylmercutic chlorides and 4,6-dimethyl-2-iodopyrimidine. For general background to the use of organomercury compounds in cross-coupling reactions, see: Beletskaya et al. (2001 ); Braga et al. (2004 ). For a related structure, see: Santoni et al. (2008 ). For the synthesis, see: Xu et al. (2009a ,b ).

Experimental

Crystal data

C₁₃H₁₄N₂
M_r = 198.26
Orthorhombic, P n m a
a = 7.2086 (10) Å
b = 12.4668 (18) Å
c = 12.4335 (18) Å
V = 1117.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.35 × 0.25 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.976, T_max = 0.985
7934 measured reflections
1089 independent reflections
777 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.131
S = 1.06
1089 reflections
78 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cg1ⁱ	0.93	2.79	3.638 (2)	152
Symmetry code: (i) $[-x-1, y+{\script{1\over 2}}, -z]$ . Cg1 is the centroid of the pyrimidine ring.

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680904210X/si2211sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904210X/si2211Isup2.hkl

checkCIF report

Comment top

The organomercury compounds have a number of notable advantages over other organometallic compounds commonly used in cross-coupling reactions, including higher selectivity of reactions, extra stability and easy availability by a direct mercuration (Beletskaya et al., 2001; Braga et al., 2004). We have recently reported ferrocene-heterocycles were obtained from the coupling reaction(Xu et al., 2009a,b). Here we report the crystal structure of the title compound, derived from the reaction of p-tolylmercutic chlorides and 4,6-dimethyl-2-iodopyrimidine.

Due to the molecular mirror symmetry m of the title compound (Fig.1), and coincidence with the crystallographic mirror plane m (space group Pnma),the atoms C1, C2, C5, C8, H8 are half occupied and the H atoms of the methyl groups in the benzene ring are disordered over two positions; their site-occupation factors were fixed at 0.5. The aromatic rings have very small angles between their planes (dihedral angle is 3.4 (2)°) due to the absence of H—H repulsion (Santoni et al., 2008). Fig.2 shows that in the crystal there exist intermolecular C—H···π interactions (Table 1, Cg1 is the centroid of the pyrimidine ring).

Related literature top

For general background, see: Beletskaya et al. (2001); Braga et al. (2004). For a related structure, see: Santoni et al. (2008). For the synthesis, see: Xu et al. (2009a,b). Cg1 is the centroid of the pyrimidine ring.

Experimental top

The title compound was obtained from the coupling reaction of p-tolylmercutic chlorides and 4,6-dimethyl-2-iodopyrimidine as described in literature (Xu et al., 2009b) and recrystallized from ethanol at room temperature to give the desired crystals suitable for single-crystal X-ray diffraction.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 30% probability level, the disordered H atoms are omitted (Symmetry code A: -x + 2, -y, -z).
	Fig. 2. Partial view of the crystal packing showing the formation of the infinite chain of molecules formed by the C—H···π interactions.

4,6-Dimethyl-2-p-tolylpyrimidine top

Crystal data top

C₁₃H₁₄N₂	D_x = 1.179 Mg m⁻³
M_r = 198.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1634 reflections
a = 7.2086 (10) Å	θ = 2.3–23.3°
b = 12.4668 (18) Å	µ = 0.07 mm⁻¹
c = 12.4335 (18) Å	T = 296 K
V = 1117.4 (3) Å³	Block, colourless
Z = 4	0.35 × 0.25 × 0.22 mm
F(000) = 424

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1089 independent reflections
Radiation source: fine-focus sealed tube	777 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.976, T_max = 0.985	k = −15→15
7934 measured reflections	l = −15→14

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0557P)² + 0.291P] where P = (F_o² + 2F_c²)/3
1089 reflections	(Δ/σ)_max < 0.001
78 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₃H₁₄N₂	V = 1117.4 (3) Å³
M_r = 198.26	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.2086 (10) Å	µ = 0.07 mm⁻¹
b = 12.4668 (18) Å	T = 296 K
c = 12.4335 (18) Å	0.35 × 0.25 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1089 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	777 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.985	R_int = 0.025
7934 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	Δρ_max = 0.19 e Å⁻³
1089 reflections	Δρ_min = −0.14 e Å⁻³
78 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	Occ. (<1)
C1	0.8988 (4)	0.2500	0.6728 (2)	0.0709 (8)
H1A	0.8781	0.2870	0.7394	0.106*	0.50
H1B	0.9952	0.2856	0.6332	0.106*	0.50
H1C	0.9355	0.1774	0.6874	0.106*	0.50
C2	0.7231 (3)	0.2500	0.60770 (17)	0.0499 (6)
C3	0.6383 (2)	0.34507 (13)	0.57708 (13)	0.0544 (5)
H3	0.6934	0.4100	0.5953	0.065*
C4	0.4741 (2)	0.34546 (12)	0.52012 (13)	0.0522 (5)
H4	0.4201	0.4105	0.5009	0.063*
C5	0.3884 (3)	0.2500	0.49107 (16)	0.0449 (5)
C6	0.2078 (3)	0.2500	0.43367 (17)	0.0468 (5)
C7	−0.0325 (2)	0.34504 (13)	0.36089 (13)	0.0529 (5)
C8	−0.1188 (3)	0.2500	0.33466 (18)	0.0549 (6)
H8	−0.2331	0.2500	0.3000	0.066*
C9	−0.1170 (3)	0.45227 (14)	0.33570 (16)	0.0732 (6)
H9A	−0.0974	0.5001	0.3951	0.110*
H9B	−0.2477	0.4438	0.3235	0.110*
H9C	−0.0598	0.4814	0.2724	0.110*
N1	0.13292 (18)	0.34589 (10)	0.41062 (10)	0.0509 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0703 (17)	0.0703 (18)	0.0720 (17)	0.000	−0.0169 (14)	0.000
C2	0.0541 (14)	0.0531 (13)	0.0425 (11)	0.000	−0.0007 (10)	0.000
C3	0.0600 (11)	0.0446 (9)	0.0584 (10)	−0.0043 (8)	−0.0036 (8)	−0.0048 (7)
C4	0.0588 (10)	0.0390 (9)	0.0589 (10)	0.0022 (7)	−0.0028 (8)	0.0002 (7)
C5	0.0507 (12)	0.0407 (11)	0.0433 (11)	0.000	0.0027 (10)	0.000
C6	0.0545 (13)	0.0430 (12)	0.0428 (11)	0.000	0.0018 (10)	0.000
C7	0.0550 (10)	0.0541 (10)	0.0496 (9)	0.0045 (8)	0.0009 (7)	0.0034 (7)
C8	0.0510 (13)	0.0608 (15)	0.0528 (13)	0.000	−0.0047 (11)	0.000
C9	0.0702 (12)	0.0598 (12)	0.0896 (14)	0.0091 (10)	−0.0128 (10)	0.0094 (10)
N1	0.0546 (8)	0.0449 (8)	0.0532 (8)	0.0031 (6)	−0.0025 (6)	0.0021 (6)

Geometric parameters (Å, º) top

C1—C2	1.503 (3)	C5—C6	1.485 (3)
C1—H1A	0.9600	C6—N1ⁱ	1.3426 (16)
C1—H1B	0.9600	C6—N1	1.3426 (16)
C1—H1C	0.9600	C7—N1	1.343 (2)
C2—C3ⁱ	1.387 (2)	C7—C8	1.378 (2)
C2—C3	1.387 (2)	C7—C9	1.502 (2)
C3—C4	1.380 (2)	C8—C7ⁱ	1.378 (2)
C3—H3	0.9300	C8—H8	0.9300
C4—C5	1.3885 (19)	C9—H9A	0.9600
C4—H4	0.9300	C9—H9B	0.9600
C5—C4ⁱ	1.3885 (19)	C9—H9C	0.9600

C2—C1—H1A	109.5	C4ⁱ—C5—C6	121.00 (11)
C2—C1—H1B	109.5	N1ⁱ—C6—N1	125.8 (2)
H1A—C1—H1B	109.5	N1ⁱ—C6—C5	117.07 (10)
C2—C1—H1C	109.5	N1—C6—C5	117.07 (10)
H1A—C1—H1C	109.5	N1—C7—C8	121.12 (16)
H1B—C1—H1C	109.5	N1—C7—C9	116.67 (15)
C3ⁱ—C2—C3	117.4 (2)	C8—C7—C9	122.20 (16)
C3ⁱ—C2—C1	121.28 (11)	C7—C8—C7ⁱ	118.7 (2)
C3—C2—C1	121.28 (11)	C7—C8—H8	120.7
C4—C3—C2	121.48 (16)	C7ⁱ—C8—H8	120.7
C4—C3—H3	119.3	C7—C9—H9A	109.5
C2—C3—H3	119.3	C7—C9—H9B	109.5
C3—C4—C5	120.81 (16)	H9A—C9—H9B	109.5
C3—C4—H4	119.6	C7—C9—H9C	109.5
C5—C4—H4	119.6	H9A—C9—H9C	109.5
C4—C5—C4ⁱ	118.0 (2)	H9B—C9—H9C	109.5
C4—C5—C6	121.00 (11)	C6—N1—C7	116.62 (15)

C3ⁱ—C2—C3—C4	1.2 (3)	C4ⁱ—C5—C6—N1	178.65 (17)
C1—C2—C3—C4	−178.02 (19)	N1—C7—C8—C7ⁱ	0.3 (3)
C2—C3—C4—C5	−0.3 (3)	C9—C7—C8—C7ⁱ	−179.77 (14)
C3—C4—C5—C4ⁱ	−0.7 (3)	N1ⁱ—C6—N1—C7	0.6 (3)
C3—C4—C5—C6	177.47 (16)	C5—C6—N1—C7	−178.53 (15)
C4—C5—C6—N1ⁱ	−178.65 (17)	C8—C7—N1—C6	−0.4 (3)
C4ⁱ—C5—C6—N1ⁱ	−0.6 (3)	C9—C7—N1—C6	179.62 (16)
C4—C5—C6—N1	0.6 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Cg1ⁱⁱ	0.93	2.79	3.638 (2)	152

Symmetry code: (ii) −x−1, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂
M_r	198.26
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	7.2086 (10), 12.4668 (18), 12.4335 (18)
V (Å³)	1117.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.35 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.976, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7934, 1089, 777
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.131, 1.06
No. of reflections	1089
No. of parameters	78
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), 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
C8—H8···Cg1ⁱ	0.93	2.79	3.638 (2)	152

Symmetry code: (i) −x−1, y+1/2, −z.

Acknowledgements

This work was supported by the Natural Science Foundation of Henan Education Department (No. 2009B150019).

References

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