N 4,N 6-Dimethyl-N 4,N 6-diphenyl­pyrimidine-4,5,6-triamine

Fuqiang Shi; Li-Hong Zhu; Li Mu; Long Zhang; Ya-Feng Li

doi:10.1107/S1600536811046642

. 2011 Nov 9;67(Pt 12):o3249. doi: 10.1107/S1600536811046642

N ⁴,N ⁶-Dimethyl-N ⁴,N ⁶-diphenylpyrimidine-4,5,6-triamine

Fuqiang Shi ^a, Li-Hong Zhu ^a, Li Mu ^b, Long Zhang ^a, Ya-Feng Li ^a,^*

PMCID: PMC3238906 PMID: 22199759

Abstract

In the title compound, C₁₈H₁₉N₅, the pyrimidine ring makes dihedral angles of 56.49 (9) and 70.88 (9)° with the phenyl rings. The dihedral angle between the two phenyl rings is 72.45 (9)°. No significant intermolecular interactions are observed in the crystal structure.

Related literature

For applications and the biological activity of pyrimidine triamines, see: Barillari et al. (2001 ▶); Itoh et al. (2004 ▶); Koppel & Robins (1958 ▶).

Experimental

Crystal data

C₁₈H₁₉N₅
M _r = 305.38
Orthorhombic,
a = 8.8859 (18) Å
b = 14.360 (3) Å
c = 25.121 (5) Å
V = 3205.4 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.32 × 0.28 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.975, T _max = 0.983
28152 measured reflections
3664 independent reflections
2119 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.137
S = 1.03
3664 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046642/is2800sup1.cif

e-67-o3249-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046642/is2800Isup2.hkl

e-67-o3249-Isup2.hkl^{(179.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811046642/is2800Isup3.cml

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

Acknowledgments

The project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars, the State Education Ministry (20071108) and the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

supplementary crystallographic information

Comment

Pyrimidine triamines not only exhibit a wide range of biological activities (Barillari et al., 2001), but also are important intermediate products (Koppel & Robins, 1958; Itoh et al., 2004). Here, the crystal structure of N⁴,N⁶-dimethyl-N⁴,N⁶- diphenylpyrimidine-4,5,6-triamine is reported.

Experimental

N⁴,N⁶-dimethyl-5-nitro-N⁴,N⁶ -diphenylpyrimidine-4, 6-diamine (502.5 mg, 1.5 mmol) was dissolved in a mixture of ethanol (16 mL) and water (4 mL). Then, iron powder (504 mg, 9 mmol) and NH₄Cl (96.3 mg, 1.8 mmol) were added. The mixture was then stirred in reflux for 6 h, cooled to room temperature, and filtered through a pad of celite. The filtrate was concentrated in vacuo. The residue was extracted with EtOAc, and the organic extract was washed with saturated NaHCO₃, water, and brine and dried over anhydrous MgSO₄. It was then filtered and concentrated in vacuo to the crude product which was purified by flash chromatography (elution with 9% EtOAc in petroleum ether followed by 20% EtOAc in petroleum ether) to give N⁴,N⁶-dimethyl-N⁴,N⁶- diphenylpyrimidine-4,5,6-triamine (colorless solid, 310 mg, 67.8%, 88.6-90.6 °C).

Figures

Fig. 1. — The molecular structure of the title compound, with the atom-labelling scheme. Displacement ellipsoid are shown at the 50% probability level.

Crystal data

C₁₈H₁₉N₅	F(000) = 1296
M_r = 305.38	D_x = 1.266 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1000 reflections
a = 8.8859 (18) Å	θ = 3.2–27.5°
b = 14.360 (3) Å	µ = 0.08 mm⁻¹
c = 25.121 (5) Å	T = 293 K
V = 3205.4 (11) Å³	Block, colorless
Z = 8	0.32 × 0.28 × 0.22 mm

Open in a new tab

Data collection

Rigaku R-AXIS RAPID diffractometer	3664 independent reflections
Radiation source: fine-focus sealed tube	2119 reflections with I > 2σ(I)
graphite	R_int = 0.065
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −11→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→18
T_min = 0.975, T_max = 0.983	l = −32→32
28152 measured reflections

Open in a new tab

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0693P)²] where P = (F_o² + 2F_c²)/3
3664 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Open in a new tab

Special details

Experimental. ¹H NMR (CDCl₃, 400 Hz), δ: 8.38 (s, 1H), 7.27 (t, J = 7.6Hz, 4H), 7.00(t, J = 7.2Hz, 2H), 6.90(d, J = 8.0Hz, 4H), 3.50 (s, 6H); 2.90 (s, 2H). ¹³C NMR (CDCl₃, 100 Hz), δ: 151.1, 148.0, 145.7, 129.3, 122.8, 122.7, 120.0, 39.7. ES-MS: 336.1 [(M + H⁺)].

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.

Open in a new tab

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

	x	y	z	U_iso*/U_eq
C1	−0.0279 (3)	0.46280 (13)	0.41196 (8)	0.0660 (6)
H1	−0.0833	0.5128	0.4249	0.079*
C2	0.0751 (2)	0.32120 (11)	0.42746 (6)	0.0483 (4)
C3	0.15006 (19)	0.32587 (11)	0.37827 (6)	0.0460 (4)
C4	0.1152 (2)	0.40201 (11)	0.34631 (6)	0.0484 (4)
C5	0.1622 (2)	0.34917 (11)	0.25472 (6)	0.0480 (4)
C6	0.0766 (2)	0.26882 (12)	0.26084 (7)	0.0563 (5)
H6	0.0287	0.2573	0.2931	0.068*
C7	0.0620 (2)	0.20590 (13)	0.21954 (8)	0.0626 (5)
H7	0.0059	0.1519	0.2245	0.075*
C8	0.1296 (2)	0.22228 (16)	0.17087 (8)	0.0689 (6)
H8	0.1205	0.1795	0.1433	0.083*
C9	0.2099 (2)	0.30237 (15)	0.16412 (8)	0.0679 (6)
H9	0.2534	0.3148	0.1312	0.082*
C10	0.2278 (2)	0.36518 (14)	0.20496 (7)	0.0586 (5)
H10	0.2842	0.4189	0.1994	0.070*
C11	0.0814 (2)	0.15421 (10)	0.44409 (6)	0.0478 (4)
C12	0.1647 (2)	0.08195 (13)	0.46579 (7)	0.0612 (5)
H12	0.2369	0.0943	0.4917	0.073*
C13	0.1404 (3)	−0.00819 (13)	0.44895 (9)	0.0713 (6)
H13	0.1949	−0.0566	0.4642	0.086*
C14	0.0367 (3)	−0.02727 (13)	0.40991 (9)	0.0732 (6)
H14	0.0223	−0.0882	0.3983	0.088*
C15	−0.0447 (3)	0.04322 (13)	0.38829 (8)	0.0688 (6)
H15	−0.1150	0.0305	0.3619	0.083*
C16	−0.0238 (2)	0.13385 (12)	0.40531 (7)	0.0570 (5)
H16	−0.0810	0.1815	0.3905	0.068*
C17	0.2467 (3)	0.50505 (12)	0.28371 (9)	0.0743 (6)
H17A	0.3482	0.4977	0.2713	0.111*
H17B	0.2464	0.5430	0.3152	0.111*
H17C	0.1874	0.5345	0.2566	0.111*
C18	0.0744 (4)	0.26304 (14)	0.51905 (7)	0.0931 (9)
H18A	0.1106	0.3236	0.5290	0.140*
H18B	0.1257	0.2163	0.5395	0.140*
H18C	−0.0318	0.2593	0.5258	0.140*
N1	0.02716 (19)	0.47211 (9)	0.36360 (6)	0.0593 (4)
N2	−0.01344 (19)	0.39000 (10)	0.44460 (6)	0.0602 (4)
N3	0.18291 (19)	0.41347 (9)	0.29607 (6)	0.0578 (4)
N4	0.25718 (18)	0.26103 (9)	0.36391 (6)	0.0583 (4)
H4A	0.3049	0.2669	0.3343	0.070*
H4B	0.2762	0.2147	0.3845	0.070*
N5	0.1029 (2)	0.24762 (9)	0.46223 (5)	0.0568 (4)

Open in a new tab

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0737 (15)	0.0553 (10)	0.0688 (13)	0.0106 (10)	0.0113 (11)	−0.0102 (9)
C2	0.0550 (11)	0.0480 (9)	0.0419 (9)	−0.0040 (8)	−0.0006 (8)	−0.0048 (7)
C3	0.0475 (10)	0.0451 (8)	0.0454 (9)	−0.0010 (8)	0.0001 (8)	−0.0040 (7)
C4	0.0528 (11)	0.0448 (8)	0.0475 (10)	−0.0015 (8)	−0.0008 (8)	−0.0016 (7)
C5	0.0473 (10)	0.0530 (9)	0.0437 (9)	0.0073 (8)	−0.0007 (7)	0.0038 (7)
C6	0.0542 (11)	0.0653 (11)	0.0493 (10)	−0.0004 (9)	0.0027 (9)	0.0004 (8)
C7	0.0603 (13)	0.0644 (11)	0.0631 (12)	0.0040 (10)	−0.0090 (10)	−0.0071 (9)
C8	0.0674 (14)	0.0877 (14)	0.0517 (12)	0.0182 (12)	−0.0070 (10)	−0.0156 (10)
C9	0.0669 (14)	0.0877 (14)	0.0492 (11)	0.0198 (12)	0.0063 (10)	−0.0004 (10)
C10	0.0547 (12)	0.0690 (11)	0.0522 (11)	0.0099 (9)	0.0064 (9)	0.0093 (9)
C11	0.0520 (10)	0.0490 (9)	0.0425 (9)	−0.0001 (8)	0.0037 (8)	0.0017 (7)
C12	0.0571 (12)	0.0726 (12)	0.0540 (11)	0.0066 (10)	0.0002 (9)	0.0098 (9)
C13	0.0785 (16)	0.0578 (11)	0.0776 (14)	0.0206 (11)	0.0180 (12)	0.0118 (10)
C14	0.0905 (18)	0.0519 (11)	0.0770 (15)	−0.0024 (11)	0.0167 (13)	−0.0077 (10)
C15	0.0737 (15)	0.0623 (12)	0.0703 (13)	−0.0102 (11)	−0.0048 (11)	−0.0086 (10)
C16	0.0578 (12)	0.0547 (10)	0.0585 (11)	0.0006 (9)	−0.0063 (9)	0.0003 (8)
C17	0.0932 (17)	0.0561 (11)	0.0734 (14)	−0.0147 (11)	0.0105 (12)	0.0092 (9)
C18	0.164 (3)	0.0758 (13)	0.0391 (11)	−0.0086 (15)	0.0004 (13)	−0.0048 (9)
N1	0.0656 (11)	0.0511 (8)	0.0611 (10)	0.0072 (8)	0.0001 (8)	−0.0028 (7)
N2	0.0707 (11)	0.0551 (8)	0.0548 (9)	0.0016 (8)	0.0109 (8)	−0.0073 (7)
N3	0.0740 (12)	0.0528 (8)	0.0466 (8)	−0.0090 (8)	0.0073 (7)	0.0052 (6)
N4	0.0607 (10)	0.0602 (9)	0.0542 (9)	0.0132 (8)	0.0116 (8)	0.0062 (7)
N5	0.0807 (12)	0.0530 (8)	0.0366 (8)	−0.0063 (8)	−0.0048 (7)	−0.0014 (6)

Open in a new tab

Geometric parameters (Å, °)

C1—N1	1.316 (2)	C11—C16	1.381 (2)
C1—N2	1.335 (2)	C11—C12	1.386 (2)
C1—H1	0.9300	C11—N5	1.429 (2)
C2—N2	1.334 (2)	C12—C13	1.379 (3)
C2—N5	1.393 (2)	C12—H12	0.9300
C2—C3	1.406 (2)	C13—C14	1.374 (3)
C3—N4	1.379 (2)	C13—H13	0.9300
C3—C4	1.391 (2)	C14—C15	1.357 (3)
C4—N1	1.347 (2)	C14—H14	0.9300
C4—N3	1.408 (2)	C15—C16	1.383 (2)
C5—C6	1.391 (2)	C15—H15	0.9300
C5—C10	1.398 (2)	C16—H16	0.9300
C5—N3	1.402 (2)	C17—N3	1.465 (2)
C6—C7	1.382 (2)	C17—H17A	0.9600
C6—H6	0.9300	C17—H17B	0.9600
C7—C8	1.382 (3)	C17—H17C	0.9600
C7—H7	0.9300	C18—N5	1.466 (2)
C8—C9	1.364 (3)	C18—H18A	0.9600
C8—H8	0.9300	C18—H18B	0.9600
C9—C10	1.375 (3)	C18—H18C	0.9600
C9—H9	0.9300	N4—H4A	0.8600
C10—H10	0.9300	N4—H4B	0.8600

N1—C1—N2	127.64 (17)	C14—C13—C12	120.75 (19)
N1—C1—H1	116.2	C14—C13—H13	119.6
N2—C1—H1	116.2	C12—C13—H13	119.6
N2—C2—N5	117.64 (15)	C15—C14—C13	119.64 (19)
N2—C2—C3	121.86 (15)	C15—C14—H14	120.2
N5—C2—C3	120.22 (15)	C13—C14—H14	120.2
N4—C3—C4	122.23 (15)	C14—C15—C16	120.4 (2)
N4—C3—C2	121.66 (15)	C14—C15—H15	119.8
C4—C3—C2	116.04 (15)	C16—C15—H15	119.8
N1—C4—C3	122.05 (15)	C11—C16—C15	120.57 (17)
N1—C4—N3	116.75 (14)	C11—C16—H16	119.7
C3—C4—N3	120.91 (16)	C15—C16—H16	119.7
C6—C5—C10	117.61 (16)	N3—C17—H17A	109.5
C6—C5—N3	122.42 (15)	N3—C17—H17B	109.5
C10—C5—N3	119.97 (16)	H17A—C17—H17B	109.5
C7—C6—C5	120.74 (17)	N3—C17—H17C	109.5
C7—C6—H6	119.6	H17A—C17—H17C	109.5
C5—C6—H6	119.6	H17B—C17—H17C	109.5
C6—C7—C8	120.78 (19)	N5—C18—H18A	109.5
C6—C7—H7	119.6	N5—C18—H18B	109.5
C8—C7—H7	119.6	H18A—C18—H18B	109.5
C9—C8—C7	118.74 (18)	N5—C18—H18C	109.5
C9—C8—H8	120.6	H18A—C18—H18C	109.5
C7—C8—H8	120.6	H18B—C18—H18C	109.5
C8—C9—C10	121.40 (19)	C1—N1—C4	115.94 (15)
C8—C9—H9	119.3	C2—N2—C1	116.00 (16)
C10—C9—H9	119.3	C5—N3—C4	122.09 (14)
C9—C10—C5	120.70 (19)	C5—N3—C17	118.99 (15)
C9—C10—H10	119.7	C4—N3—C17	117.41 (14)
C5—C10—H10	119.7	C3—N4—H4A	120.0
C16—C11—C12	118.70 (16)	C3—N4—H4B	120.0
C16—C11—N5	120.91 (15)	H4A—N4—H4B	120.0
C12—C11—N5	120.38 (16)	C2—N5—C11	119.23 (13)
C13—C12—C11	119.90 (19)	C2—N5—C18	117.72 (15)
C13—C12—H12	120.0	C11—N5—C18	115.39 (14)
C11—C12—H12	120.0

Open in a new tab

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2800).

References

Barillari, C., Barlocco, D. & Raveglia, L. (2001). Eur. J. Org. Chem. pp. 4737–4741.
Brandenburg, K. (2000). DIAMOND Crystal Impact GbR, Bonn, Germany.
Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
Itoh, T., Sato, K. & Mase, T. (2004). Adv. Synth. Catal. 346, 1859–1867.
Koppel, H. & Robins, R. (1958). J. Org. Chem. 23, 1457–1460.
Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046642/is2800sup1.cif

e-67-o3249-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046642/is2800Isup2.hkl

e-67-o3249-Isup2.hkl^{(179.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811046642/is2800Isup3.cml

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

[bb1] Barillari, C., Barlocco, D. & Raveglia, L. (2001). Eur. J. Org. Chem. pp. 4737–4741.

[bb2] Brandenburg, K. (2000). DIAMOND Crystal Impact GbR, Bonn, Germany.

[bb3] Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.

[bb4] Itoh, T., Sato, K. & Mase, T. (2004). Adv. Synth. Catal. 346, 1859–1867.

[bb5] Koppel, H. & Robins, R. (1958). J. Org. Chem. 23, 1457–1460.

[bb6] Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.

[bb7] Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.

[bb8] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

PERMALINK

N ⁴,N ⁶-Dimethyl-N ⁴,N ⁶-diphenylpyrimidine-4,5,6-triamine

Fuqiang Shi

Li-Hong Zhu

Li Mu

Long Zhang

Ya-Feng Li

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Cite

Add to Collections

PERMALINK

N 4,N 6-Dimethyl-N 4,N 6-diphenyl­pyrimidine-4,5,6-triamine

Fuqiang Shi

Li-Hong Zhu

Li Mu

Long Zhang

Ya-Feng Li

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Similar articles

Cited by other articles

Links to NCBI Databases

N ⁴,N ⁶-Dimethyl-N ⁴,N ⁶-diphenylpyrimidine-4,5,6-triamine

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

Atomic displacement parameters (Å²)