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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

4,6-Di­methyl-2-p-tolyl­pyrimidine

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[Beletskaya, I. P., Tsvetkov, A. V., Latyshev, G. V., Tafeenko, V. A. & Lukashev, N. V. (2001). J. Organomet. Chem. 637, 653-663.]); Braga et al. (2004[Braga, D., D'Addario, D. & Polito, M. (2004). Organometallics 23, 2810-2812.]). For a related structure, see: Santoni et al. (2008[Santoni, M.-P. C., Yu, S. H., Hanan, G. S., Proust, A. & Hasenknopf, B. (2008). Acta Cryst. E64, o584.]). For the synthesis, see: Xu et al. (2009a[Xu, C., Hao, X.-Q., Liu, F., Wu, X.-J. & Song, M.-P. (2009a). Acta Cryst. E65, m517.],b[Xu, C., Wang, Z. Q., Fu, W. J., Lou, X. H., Li, Y. F., Cen, F. F., Ma, H. J. & Ji, B. M. (2009b). Organometallics 28, 1909-1916.]).

[Scheme 1]

Experimental

Crystal data
  • C13H14N2

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.976, Tmax = 0.985

  • 7934 measured reflections

  • 1089 independent reflections

  • 777 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.131

  • S = 1.06

  • 1089 reflections

  • 78 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.14 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). 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: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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.

Refinement top

H atoms attached to C atoms of the title compound were placed in geometrically idealized positions and treated as riding with C—H distances constrained to 0.93–0.96 Å, and with Uiso(H)=1.2–1.5Ueq(C).

Structure description 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).

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.

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
[Figure 1] 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).
[Figure 2] 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
C13H14N2Dx = 1.179 Mg m3
Mr = 198.26Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 1634 reflections
a = 7.2086 (10) Åθ = 2.3–23.3°
b = 12.4668 (18) ŵ = 0.07 mm1
c = 12.4335 (18) ÅT = 296 K
V = 1117.4 (3) Å3Block, colourless
Z = 40.35 × 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 tube777 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
phi and ω scansθmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.976, Tmax = 0.985k = 1515
7934 measured reflectionsl = 1514
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0557P)2 + 0.291P]
where P = (Fo2 + 2Fc2)/3
1089 reflections(Δ/σ)max < 0.001
78 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C13H14N2V = 1117.4 (3) Å3
Mr = 198.26Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.2086 (10) ŵ = 0.07 mm1
b = 12.4668 (18) ÅT = 296 K
c = 12.4335 (18) Å0.35 × 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)
Tmin = 0.976, Tmax = 0.985Rint = 0.025
7934 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.06Δρmax = 0.19 e Å3
1089 reflectionsΔρmin = 0.14 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.8988 (4)0.25000.6728 (2)0.0709 (8)
H1A0.87810.28700.73940.106*0.50
H1B0.99520.28560.63320.106*0.50
H1C0.93550.17740.68740.106*0.50
C20.7231 (3)0.25000.60770 (17)0.0499 (6)
C30.6383 (2)0.34507 (13)0.57708 (13)0.0544 (5)
H30.69340.41000.59530.065*
C40.4741 (2)0.34546 (12)0.52012 (13)0.0522 (5)
H40.42010.41050.50090.063*
C50.3884 (3)0.25000.49107 (16)0.0449 (5)
C60.2078 (3)0.25000.43367 (17)0.0468 (5)
C70.0325 (2)0.34504 (13)0.36089 (13)0.0529 (5)
C80.1188 (3)0.25000.33466 (18)0.0549 (6)
H80.23310.25000.30000.066*
C90.1170 (3)0.45227 (14)0.33570 (16)0.0732 (6)
H9A0.09740.50010.39510.110*
H9B0.24770.44380.32350.110*
H9C0.05980.48140.27240.110*
N10.13292 (18)0.34589 (10)0.41062 (10)0.0509 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0703 (17)0.0703 (18)0.0720 (17)0.0000.0169 (14)0.000
C20.0541 (14)0.0531 (13)0.0425 (11)0.0000.0007 (10)0.000
C30.0600 (11)0.0446 (9)0.0584 (10)0.0043 (8)0.0036 (8)0.0048 (7)
C40.0588 (10)0.0390 (9)0.0589 (10)0.0022 (7)0.0028 (8)0.0002 (7)
C50.0507 (12)0.0407 (11)0.0433 (11)0.0000.0027 (10)0.000
C60.0545 (13)0.0430 (12)0.0428 (11)0.0000.0018 (10)0.000
C70.0550 (10)0.0541 (10)0.0496 (9)0.0045 (8)0.0009 (7)0.0034 (7)
C80.0510 (13)0.0608 (15)0.0528 (13)0.0000.0047 (11)0.000
C90.0702 (12)0.0598 (12)0.0896 (14)0.0091 (10)0.0128 (10)0.0094 (10)
N10.0546 (8)0.0449 (8)0.0532 (8)0.0031 (6)0.0025 (6)0.0021 (6)
Geometric parameters (Å, º) top
C1—C21.503 (3)C5—C61.485 (3)
C1—H1A0.9600C6—N1i1.3426 (16)
C1—H1B0.9600C6—N11.3426 (16)
C1—H1C0.9600C7—N11.343 (2)
C2—C3i1.387 (2)C7—C81.378 (2)
C2—C31.387 (2)C7—C91.502 (2)
C3—C41.380 (2)C8—C7i1.378 (2)
C3—H30.9300C8—H80.9300
C4—C51.3885 (19)C9—H9A0.9600
C4—H40.9300C9—H9B0.9600
C5—C4i1.3885 (19)C9—H9C0.9600
C2—C1—H1A109.5C4i—C5—C6121.00 (11)
C2—C1—H1B109.5N1i—C6—N1125.8 (2)
H1A—C1—H1B109.5N1i—C6—C5117.07 (10)
C2—C1—H1C109.5N1—C6—C5117.07 (10)
H1A—C1—H1C109.5N1—C7—C8121.12 (16)
H1B—C1—H1C109.5N1—C7—C9116.67 (15)
C3i—C2—C3117.4 (2)C8—C7—C9122.20 (16)
C3i—C2—C1121.28 (11)C7—C8—C7i118.7 (2)
C3—C2—C1121.28 (11)C7—C8—H8120.7
C4—C3—C2121.48 (16)C7i—C8—H8120.7
C4—C3—H3119.3C7—C9—H9A109.5
C2—C3—H3119.3C7—C9—H9B109.5
C3—C4—C5120.81 (16)H9A—C9—H9B109.5
C3—C4—H4119.6C7—C9—H9C109.5
C5—C4—H4119.6H9A—C9—H9C109.5
C4—C5—C4i118.0 (2)H9B—C9—H9C109.5
C4—C5—C6121.00 (11)C6—N1—C7116.62 (15)
C3i—C2—C3—C41.2 (3)C4i—C5—C6—N1178.65 (17)
C1—C2—C3—C4178.02 (19)N1—C7—C8—C7i0.3 (3)
C2—C3—C4—C50.3 (3)C9—C7—C8—C7i179.77 (14)
C3—C4—C5—C4i0.7 (3)N1i—C6—N1—C70.6 (3)
C3—C4—C5—C6177.47 (16)C5—C6—N1—C7178.53 (15)
C4—C5—C6—N1i178.65 (17)C8—C7—N1—C60.4 (3)
C4i—C5—C6—N1i0.6 (3)C9—C7—N1—C6179.62 (16)
C4—C5—C6—N10.6 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···Cg1ii0.932.793.638 (2)152
Symmetry code: (ii) x1, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC13H14N2
Mr198.26
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)296
a, b, c (Å)7.2086 (10), 12.4668 (18), 12.4335 (18)
V3)1117.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.35 × 0.25 × 0.22
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.976, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
7934, 1089, 777
Rint0.025
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.131, 1.06
No. of reflections1089
No. of parameters78
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C8—H8···Cg1i0.932.793.638 (2)152
Symmetry code: (i) x1, y+1/2, z.
 

Acknowledgements

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

References

First citationBeletskaya, I. P., Tsvetkov, A. V., Latyshev, G. V., Tafeenko, V. A. & Lukashev, N. V. (2001). J. Organomet. Chem. 637, 653–663.  Web of Science CSD CrossRef Google Scholar
First citationBraga, D., D'Addario, D. & Polito, M. (2004). Organometallics 23, 2810–2812.  Web of Science CSD CrossRef CAS Google Scholar
First citationBruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSantoni, M.-P. C., Yu, S. H., Hanan, G. S., Proust, A. & Hasenknopf, B. (2008). Acta Cryst. E64, o584.  Web of Science CSD CrossRef IUCr Journals 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
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXu, C., Hao, X.-Q., Liu, F., Wu, X.-J. & Song, M.-P. (2009a). Acta Cryst. E65, m517.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationXu, C., Wang, Z. Q., Fu, W. J., Lou, X. H., Li, Y. F., Cen, F. F., Ma, H. J. & Ji, B. M. (2009b). Organometallics 28, 1909–1916.  Web of Science CSD CrossRef CAS 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
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds