1,3-Dimethyl-5-(2-methyl­benzyl­idene)pyrimidine-2,4,6(1H,3H,5H)-trione

Panchatcharam, R.; Dhayalan, V.; Mohanakrishnan, A.K.; Chakkaravarthi, G.; Manivannan, V.

doi:10.1107/S1600536809035521

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2394

doi:10.1107/S1600536809035521

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1,3-Dimethyl-5-(2-methylbenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione

R. Panchatcharam,^a V. Dhayalan,^b A. K. Mohanakrishnan,^b G. Chakkaravarthi ^c and V. Manivannan ^a ^*

^aCentre for Research and Development, PRIST University, Vallam, Thanjavur 613 403, Tamil Nadu, India, ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: manivan_1999@yahoo.com

(Received 2 September 2009; accepted 2 September 2009; online 9 September 2009)

In the title compound, C₁₄H₁₄N₂O₃, the dihedral angle between the pyrimidine and benzene rings is 14.9 (1)°. The molecular structure is stabilized by weak intramolecular C—H⋯O interactions and the crystal structure exhibits a weak intermolecular π–π interaction [centroid–centroid distance = 3.575 (3) Å].

Related literature

For the biological activity of pyrimidine derivatives, see: Cody et al. (1997 ); Li et al. (1995 ). For related structures, see: Da Silva et al. (2005 ); Rezende et al. (2005 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₄N₂O₃
M_r = 258.27
Monoclinic, P 2₁ /n
a = 8.182 (5) Å
b = 8.334 (4) Å
c = 18.202 (5) Å
β = 94.267 (5)°
V = 1237.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.30 × 0.28 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.982
16198 measured reflections
3837 independent reflections
2517 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.238
S = 1.04
3837 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2	0.93	2.26	2.893 (3)	125

Data collection: APEX2 (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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035521/bt5051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035521/bt5051Isup2.hkl

checkCIF report

Comment top

Pyrimidine derivatives show biological activities such as antitumor, antibacterial, insulin releasing and anti-inflammatory activities (Cody et al., 1997; Li et al., 1995). The geometric parameters in (I) (Fig. 1) agree with the reported values of similar structures (Da Silva et al., 2005; Rezende et al., 2005).

The dihedral angle between the pyrimidine ring (N1/C11/N2/C10/C9/C12) and benzene ring (C1—C6) is 14.9 (1)°. The molecular structure is stabilized by weak intramolecular C—H···O interactions. The crystal structure exhibits an intermolecular weak π–π interaction[Cg1···Cg2 = 3.575 (3) Å; symmetry code: -x, -y, 1 - z; Cg1 and Cg2 are the centroids of N1/C11/N2/C10/C9/C12 and C1—C6 rings, respectively].

The intramolecular C8—H8···O1 and C13—H13B···O3 interactions generate five-membered rings, each with graph-set motif S(5) and C2—H2···O2 interaction generates a seven-membered ring, with graph-set motif S(7) (Bernstein et al., 1995).

Related literature top

For related literature, see: Bernstein et al. (1995); Cody et al. (1997); Da Silva et al. (2005); Li et al. (1995); Rezende et al. (2005).

Experimental top

To a solution of o-tolualdehyde (4.0 g, 33.29 mmol) in dry benzene (80 ml), N,N-dimethylbarbituric acid (5.72 g, 36.63 mmol), piperidine (0.6 ml) and acetic acid (0.3 ml) were added and refluxed in a RB flask fitted with Dean-Stark apparatus for 12 h. Removal of solvent followed by recrystallizaton from CDCl3 afforded the compound.

Computing details top

Data collection: APEX2 (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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

1,3-Dimethyl-5-(2-methylbenzylidene)pyrimidine- 2,4,6(1H,3H,5H)-trione top

Crystal data top

C₁₄H₁₄N₂O₃	F(000) = 544
M_r = 258.27	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6022 reflections
a = 8.182 (5) Å	θ = 2.2–29.8°
b = 8.334 (4) Å	µ = 0.10 mm⁻¹
c = 18.202 (5) Å	T = 295 K
β = 94.267 (5)°	Block, colourless
V = 1237.7 (10) Å³	0.30 × 0.28 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	3837 independent reflections
Radiation source: fine-focus sealed tube	2517 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and ϕ scans	θ_max = 30.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.971, T_max = 0.982	k = −8→11
16198 measured reflections	l = −26→26

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.238	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1214P)² + 0.5641P] where P = (F_o² + 2F_c²)/3
3837 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₄H₁₄N₂O₃	V = 1237.7 (10) Å³
M_r = 258.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.182 (5) Å	µ = 0.10 mm⁻¹
b = 8.334 (4) Å	T = 295 K
c = 18.202 (5) Å	0.30 × 0.28 × 0.18 mm
β = 94.267 (5)°

Data collection top

Bruker Kappa APEXII diffractometer	3837 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2517 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.982	R_int = 0.024
16198 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.238	H-atom parameters constrained
S = 1.04	Δρ_max = 0.52 e Å⁻³
3837 reflections	Δρ_min = −0.34 e Å⁻³
175 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.0138 (2)	0.2553 (2)	0.49118 (10)	0.0391 (4)
C2	−0.1183 (3)	0.2104 (3)	0.44177 (12)	0.0547 (6)
H2	−0.1974	0.1406	0.4573	0.066*
C3	−0.1326 (3)	0.2681 (4)	0.37060 (12)	0.0589 (6)
H3	−0.2205	0.2370	0.3384	0.071*
C4	−0.0168 (3)	0.3713 (3)	0.34746 (12)	0.0548 (6)
H4	−0.0285	0.4147	0.3003	0.066*
C5	0.1166 (3)	0.4106 (3)	0.39422 (12)	0.0519 (5)
H5	0.1961	0.4785	0.3775	0.062*
C6	0.1363 (2)	0.3521 (3)	0.46527 (11)	0.0424 (5)
C7	0.2861 (3)	0.4007 (4)	0.51198 (15)	0.0714 (8)
H7A	0.3586	0.3105	0.5188	0.107*
H7B	0.2552	0.4370	0.5590	0.107*
H7C	0.3408	0.4859	0.4881	0.107*
C8	0.0343 (3)	0.2024 (3)	0.56714 (11)	0.0447 (5)
H8	0.1412	0.2161	0.5873	0.054*
C9	−0.0641 (2)	0.1379 (2)	0.61602 (10)	0.0390 (4)
C10	0.0217 (3)	0.0920 (3)	0.68754 (10)	0.0429 (5)
C11	−0.2160 (2)	−0.0676 (2)	0.71455 (10)	0.0396 (4)
C12	−0.2395 (3)	0.1068 (3)	0.60570 (11)	0.0449 (5)
C13	0.0281 (3)	−0.0647 (3)	0.79980 (12)	0.0584 (6)
H13A	0.1247	−0.1223	0.7885	0.088*
H13B	−0.0416	−0.1340	0.8257	0.088*
H13C	0.0589	0.0263	0.8300	0.088*
C14	−0.4706 (3)	−0.0581 (4)	0.63701 (16)	0.0715 (8)
H14A	−0.4822	−0.1675	0.6524	0.107*
H14B	−0.5004	−0.0496	0.5851	0.107*
H14C	−0.5409	0.0093	0.6636	0.107*
N1	−0.3007 (2)	−0.0073 (2)	0.65217 (9)	0.0433 (4)
N2	−0.0600 (2)	−0.0100 (2)	0.73120 (8)	0.0397 (4)
O1	0.1595 (2)	0.1369 (3)	0.70726 (9)	0.0682 (6)
O2	−0.3317 (2)	0.1744 (3)	0.56044 (11)	0.0748 (6)
O3	−0.2774 (2)	−0.1642 (2)	0.75393 (10)	0.0587 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0383 (9)	0.0465 (10)	0.0326 (8)	0.0012 (8)	0.0033 (7)	0.0046 (7)
C2	0.0453 (11)	0.0775 (16)	0.0407 (10)	−0.0112 (11)	−0.0004 (9)	0.0047 (11)
C3	0.0505 (12)	0.0883 (18)	0.0367 (10)	0.0003 (12)	−0.0041 (9)	0.0010 (11)
C4	0.0654 (14)	0.0672 (15)	0.0323 (9)	0.0100 (11)	0.0064 (9)	0.0082 (9)
C5	0.0614 (13)	0.0556 (13)	0.0403 (10)	−0.0084 (10)	0.0144 (9)	0.0035 (9)
C6	0.0407 (10)	0.0498 (11)	0.0371 (9)	−0.0012 (8)	0.0061 (7)	−0.0031 (8)
C7	0.0539 (14)	0.104 (2)	0.0549 (14)	−0.0309 (15)	−0.0017 (11)	0.0038 (14)
C8	0.0417 (10)	0.0534 (12)	0.0382 (9)	−0.0060 (9)	−0.0016 (8)	0.0071 (9)
C9	0.0413 (10)	0.0433 (10)	0.0320 (8)	−0.0013 (8)	−0.0009 (7)	0.0049 (7)
C10	0.0415 (10)	0.0535 (11)	0.0330 (9)	−0.0047 (9)	−0.0017 (7)	0.0061 (8)
C11	0.0460 (10)	0.0390 (10)	0.0350 (9)	−0.0009 (8)	0.0100 (7)	−0.0014 (7)
C12	0.0391 (10)	0.0608 (13)	0.0345 (9)	0.0025 (9)	0.0008 (7)	0.0053 (9)
C13	0.0598 (14)	0.0761 (16)	0.0384 (10)	0.0067 (12)	−0.0022 (9)	0.0186 (11)
C14	0.0449 (13)	0.108 (2)	0.0611 (15)	−0.0255 (14)	0.0006 (11)	−0.0008 (15)
N1	0.0378 (8)	0.0532 (10)	0.0387 (8)	−0.0071 (7)	0.0025 (6)	−0.0027 (7)
N2	0.0408 (8)	0.0466 (9)	0.0315 (7)	0.0021 (7)	0.0020 (6)	0.0070 (6)
O1	0.0512 (9)	0.1035 (15)	0.0473 (9)	−0.0257 (9)	−0.0139 (7)	0.0199 (9)
O2	0.0443 (9)	0.1221 (17)	0.0570 (10)	0.0125 (10)	−0.0022 (8)	0.0328 (11)
O3	0.0673 (11)	0.0574 (10)	0.0536 (9)	−0.0123 (8)	0.0186 (8)	0.0089 (7)

Geometric parameters (Å, º) top

C1—C6	1.396 (3)	C9—C12	1.457 (3)
C1—C2	1.404 (3)	C9—C10	1.482 (3)
C1—C8	1.449 (3)	C10—O1	1.217 (3)
C2—C3	1.379 (3)	C10—N2	1.371 (3)
C2—H2	0.9300	C11—O3	1.212 (2)
C3—C4	1.369 (4)	C11—N2	1.376 (3)
C3—H3	0.9300	C11—N1	1.380 (3)
C4—C5	1.373 (4)	C12—O2	1.214 (3)
C4—H4	0.9300	C12—N1	1.391 (3)
C5—C6	1.380 (3)	C13—N2	1.467 (3)
C5—H5	0.9300	C13—H13A	0.9600
C6—C7	1.495 (3)	C13—H13B	0.9600
C7—H7A	0.9600	C13—H13C	0.9600
C7—H7B	0.9600	C14—N1	1.460 (3)
C7—H7C	0.9600	C14—H14A	0.9600
C8—C9	1.355 (3)	C14—H14B	0.9600
C8—H8	0.9300	C14—H14C	0.9600

C6—C1—C2	118.38 (18)	C12—C9—C10	117.69 (17)
C6—C1—C8	117.61 (18)	O1—C10—N2	120.04 (18)
C2—C1—C8	123.97 (19)	O1—C10—C9	123.19 (19)
C3—C2—C1	121.1 (2)	N2—C10—C9	116.74 (18)
C3—C2—H2	119.5	O3—C11—N2	121.34 (19)
C1—C2—H2	119.5	O3—C11—N1	121.6 (2)
C4—C3—C2	119.7 (2)	N2—C11—N1	117.08 (17)
C4—C3—H3	120.1	O2—C12—N1	119.8 (2)
C2—C3—H3	120.1	O2—C12—C9	124.2 (2)
C3—C4—C5	119.7 (2)	N1—C12—C9	116.06 (17)
C3—C4—H4	120.1	N2—C13—H13A	109.5
C5—C4—H4	120.1	N2—C13—H13B	109.5
C4—C5—C6	121.9 (2)	H13A—C13—H13B	109.5
C4—C5—H5	119.0	N2—C13—H13C	109.5
C6—C5—H5	119.0	H13A—C13—H13C	109.5
C5—C6—C1	118.95 (19)	H13B—C13—H13C	109.5
C5—C6—C7	118.1 (2)	N1—C14—H14A	109.5
C1—C6—C7	122.9 (2)	N1—C14—H14B	109.5
C6—C7—H7A	109.5	H14A—C14—H14B	109.5
C6—C7—H7B	109.5	N1—C14—H14C	109.5
H7A—C7—H7B	109.5	H14A—C14—H14C	109.5
C6—C7—H7C	109.5	H14B—C14—H14C	109.5
H7A—C7—H7C	109.5	C11—N1—C12	124.58 (17)
H7B—C7—H7C	109.5	C11—N1—C14	117.58 (19)
C9—C8—C1	135.66 (19)	C12—N1—C14	117.7 (2)
C9—C8—H8	112.2	C10—N2—C11	124.92 (16)
C1—C8—H8	112.2	C10—N2—C13	117.15 (18)
C8—C9—C12	127.86 (18)	C11—N2—C13	117.91 (18)
C8—C9—C10	114.43 (18)

C6—C1—C2—C3	−4.0 (4)	C10—C9—C12—O2	159.2 (2)
C8—C1—C2—C3	178.4 (2)	C8—C9—C12—N1	158.5 (2)
C1—C2—C3—C4	−0.2 (4)	C10—C9—C12—N1	−20.2 (3)
C2—C3—C4—C5	3.1 (4)	O3—C11—N1—C12	178.2 (2)
C3—C4—C5—C6	−1.7 (4)	N2—C11—N1—C12	−0.2 (3)
C4—C5—C6—C1	−2.5 (4)	O3—C11—N1—C14	2.9 (3)
C4—C5—C6—C7	179.6 (3)	N2—C11—N1—C14	−175.4 (2)
C2—C1—C6—C5	5.2 (3)	O2—C12—N1—C11	−166.3 (2)
C8—C1—C6—C5	−177.0 (2)	C9—C12—N1—C11	13.1 (3)
C2—C1—C6—C7	−177.0 (3)	O2—C12—N1—C14	8.9 (4)
C8—C1—C6—C7	0.7 (3)	C9—C12—N1—C14	−171.7 (2)
C6—C1—C8—C9	164.5 (3)	O1—C10—N2—C11	179.7 (2)
C2—C1—C8—C9	−17.9 (4)	C9—C10—N2—C11	−2.3 (3)
C1—C8—C9—C12	−3.4 (4)	O1—C10—N2—C13	−2.0 (3)
C1—C8—C9—C10	175.4 (2)	C9—C10—N2—C13	176.01 (19)
C8—C9—C10—O1	14.5 (3)	O3—C11—N2—C10	176.1 (2)
C12—C9—C10—O1	−166.7 (2)	N1—C11—N2—C10	−5.6 (3)
C8—C9—C10—N2	−163.5 (2)	O3—C11—N2—C13	−2.2 (3)
C12—C9—C10—N2	15.4 (3)	N1—C11—N2—C13	176.12 (18)
C8—C9—C12—O2	−22.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.26	2.893 (3)	125
C8—H8···O1	0.93	2.28	2.732 (3)	110
C13—H13B···O3	0.96	2.26	2.706 (4)	107

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂O₃
M_r	258.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	8.182 (5), 8.334 (4), 18.202 (5)
β (°)	94.267 (5)
V (Å³)	1237.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.28 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	16198, 3837, 2517
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.238, 1.04
No. of reflections	3837
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.34

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.26	2.893 (3)	125
C8—H8···O1	0.93	2.28	2.732 (3)	110
C13—H13B···O3	0.96	2.26	2.706 (4)	107

Acknowledgements

The authors acknowledge SAIF, IIT, Madras, for the data collection.

References

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