N4,N6-Dimethyl-5-nitro-N4,N6-diphenyl­pyrimidine-4,6-diamine

Shi, F.; Zhu, L.-H.; Zhang, L.; Li, Y.-F.

doi:10.1107/S1600536811035094

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2559

https://doi.org/10.1107/S1600536811035094

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N⁴,N⁶-Dimethyl-5-nitro-N⁴,N⁶-diphenylpyrimidine-4,6-diamine

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

^aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 25 August 2011; accepted 27 August 2011; online 3 September 2011)

In the title compound, C₁₈H₁₇N₅O₂, the pyrimidine ring makes dihedral angles of 66.09 (12), 71.39 (13) and 56.7 (3)° with two phenyl rings and the nitro group, respectively. The dihedral angle between the two phenyl rings is 44.05 (14)°.

Related literature

For applications of pyrimidine diamines, see: Barillari et al. (2001 ); Che et al. (2008 ); Itoh et al. (2004 ); Koppel & Robins (1958 ); Shi et al. (2011 ).

Experimental

Crystal data

C₁₈H₁₇N₅O₂
M_r = 335.37
Monoclinic, P 2₁ /c
a = 10.794 (2) Å
b = 7.0019 (14) Å
c = 23.650 (6) Å
β = 109.02 (3)°
V = 1689.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.50 × 0.12 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.956, T_max = 0.991
15784 measured reflections
3843 independent reflections
2018 reflections with I > 2σ(I)
R_int = 0.108

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.146
S = 1.05
3843 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811035094/is2768sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035094/is2768Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035094/is2768Isup3.cml

checkCIF report

Comment top

Pyrimidine diamines, important intermediate products (Koppel et al., 1958; Itoh et al., 2004; Che et al., 2008; Shi et al., 2011), exhibit a wide range of biological activities (Barillari et al., 2001). Here, the crystal structure of N⁴,N⁶- dimethyl-5-nitro-N⁴, N⁶-diphenylpyrimidine-4,6-diamine is determined by X-ray single crystal diffraction.

In the structure of the title compound (Fig. 1), the dihedral angles between pyrimidyl and two phenyl rings and between two phenyl rings are 66.09 (12), 71.39 (13) and 44.05 (14)°, respectively.

Related literature top

For applications of pyrimidine diamines, see: Barillari et al. (2001); Che et al. (2008); Itoh et al. (2004); Koppel & Robins (1958); Shi et al. (2011).

Experimental top

4,6-Dichloro-5-nitro-pyrimidine (192 mg, 1 mmol), N-methylbenzenamine (0.33 mL, 3 mmol) and triethylamine (0.22 mL, 2 mmol) were dissolved in anhydrous THF (10 mL). The reaction mixture was stirred in reflux overnight. The product was concentrated in vacuo, diluted with water, and extracted with EtOAc. The organic phase was washed with 1mol/L HCl, brine, and dried over anhydrous MgSO₄. The crude product was purified by flash chromatography (elution with 15% EtOAc in petroleum ether) to give N⁴,N⁶-dimethyl-5-nitro-N⁴, N⁶-diphenylpyrimidine- 4,6-diamine (yellow solid, 256 mg, 76.4%, 166.4-168.6 °C). ¹H NMR (CDCl₃, 400 Hz), δ: 8.46 (s, 1H), 7.23-7.19(m, 4H), 7.13-7.11(m, 2H), 7.02-6.99(m, 4H), 3.50 (s, 6H); ¹³C NMR (CDCl₃, 100 Hz), δ: 156.0, 155.7, 144.2, 129.2, 126.6, 125.1, 121.0, 42.0; ES-MS: 336.1 [(M + H⁺)].

Structure description top

In the structure of the title compound (Fig. 1), the dihedral angles between pyrimidyl and two phenyl rings and between two phenyl rings are 66.09 (12), 71.39 (13) and 44.05 (14)°, respectively.

For applications of pyrimidine diamines, see: Barillari et al. (2001); Che et al. (2008); Itoh et al. (2004); Koppel & Robins (1958); Shi et al. (2011).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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 (Sheldrick, 2008).

Figures top

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

N⁴,N⁶-Dimethyl-5-nitro-N⁴,N⁶- diphenylpyrimidine-4,6-diamine top

Crystal data top

C₁₈H₁₇N₅O₂	F(000) = 704
M_r = 335.37	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 500 reflections
a = 10.794 (2) Å	θ = 3.1–27.5°
b = 7.0019 (14) Å	µ = 0.09 mm⁻¹
c = 23.650 (6) Å	T = 293 K
β = 109.02 (3)°	Block, colorless
V = 1689.8 (6) Å³	0.50 × 0.12 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3843 independent reflections
Radiation source: fine-focus sealed tube	2018 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.108
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −14→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
T_min = 0.956, T_max = 0.991	l = −30→30
15784 measured reflections

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0524P)² + 0.0764P] where P = (F_o² + 2F_c²)/3
3843 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₈H₁₇N₅O₂	V = 1689.8 (6) Å³
M_r = 335.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.794 (2) Å	µ = 0.09 mm⁻¹
b = 7.0019 (14) Å	T = 293 K
c = 23.650 (6) Å	0.50 × 0.12 × 0.10 mm
β = 109.02 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3843 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2018 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.991	R_int = 0.108
15784 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.05	Δρ_max = 0.17 e Å⁻³
3843 reflections	Δρ_min = −0.20 e Å⁻³
228 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
O1	0.84317 (18)	0.0703 (3)	0.35192 (9)	0.0577 (6)
O2	0.85674 (17)	0.2808 (3)	0.42079 (8)	0.0586 (6)
N1	0.5774 (2)	0.2175 (3)	0.41820 (9)	0.0435 (6)
N2	0.45045 (19)	0.3519 (3)	0.32882 (10)	0.0434 (6)
N3	0.52690 (19)	0.3954 (3)	0.24557 (9)	0.0412 (5)
N4	0.7997 (2)	0.2043 (3)	0.37282 (10)	0.0424 (6)
N5	0.74616 (19)	0.3627 (3)	0.25459 (9)	0.0393 (5)
C1	0.7275 (3)	−0.2635 (4)	0.44234 (13)	0.0553 (8)
H1	0.7216	−0.3782	0.4218	0.066*
C2	0.8135 (3)	−0.2471 (5)	0.49962 (14)	0.0639 (9)
H2	0.8663	−0.3498	0.5176	0.077*
C3	0.8210 (3)	−0.0796 (5)	0.53010 (13)	0.0678 (10)
H3	0.8784	−0.0692	0.5690	0.081*
C4	0.6587 (2)	0.0578 (4)	0.44551 (10)	0.0387 (6)
C5	0.6500 (3)	−0.1108 (4)	0.41512 (11)	0.0446 (7)
H5	0.5921	−0.1224	0.3763	0.054*
C6	0.7441 (3)	0.0745 (4)	0.50349 (12)	0.0562 (8)
H6	0.7496	0.1885	0.5243	0.067*
C7	0.4741 (3)	0.2699 (5)	0.44293 (13)	0.0705 (10)
H7A	0.4531	0.4028	0.4354	0.085*
H7B	0.5041	0.2470	0.4853	0.085*
H7C	0.3975	0.1943	0.4243	0.085*
C8	0.6703 (2)	0.2779 (3)	0.33805 (10)	0.0338 (6)
C9	0.5681 (2)	0.2799 (3)	0.36205 (11)	0.0362 (6)
C10	0.6494 (2)	0.3447 (3)	0.27970 (11)	0.0359 (6)
C11	0.4380 (2)	0.3965 (4)	0.27283 (13)	0.0456 (7)
H11	0.3545	0.4341	0.2493	0.055*
C12	0.8912 (3)	0.5770 (4)	0.32865 (12)	0.0461 (7)
H12	0.8181	0.6442	0.3303	0.055*
C13	0.9840 (3)	0.3278 (4)	0.28633 (12)	0.0474 (7)
H13	0.9742	0.2256	0.2601	0.057*
C14	1.0143 (3)	0.6310 (4)	0.36414 (13)	0.0573 (8)
H14	1.0246	0.7332	0.3904	0.069*
C15	1.1078 (3)	0.3861 (4)	0.32153 (13)	0.0573 (8)
H15	1.1815	0.3241	0.3184	0.069*
C16	1.1223 (3)	0.5339 (5)	0.36078 (13)	0.0604 (9)
H16	1.2056	0.5690	0.3853	0.072*
C17	0.8759 (2)	0.4228 (3)	0.29054 (10)	0.0365 (6)
C18	0.7094 (3)	0.3940 (4)	0.19040 (10)	0.0503 (7)
H18A	0.6509	0.2945	0.1697	0.060*
H18B	0.7865	0.3927	0.1786	0.060*
H18C	0.6664	0.5154	0.1805	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0466 (12)	0.0511 (12)	0.0785 (14)	0.0176 (10)	0.0247 (11)	0.0139 (11)
O2	0.0418 (11)	0.0717 (14)	0.0505 (11)	−0.0089 (10)	−0.0010 (9)	0.0050 (11)
N1	0.0423 (12)	0.0468 (13)	0.0451 (12)	0.0077 (11)	0.0194 (10)	0.0064 (11)
N2	0.0315 (12)	0.0430 (13)	0.0557 (14)	0.0047 (10)	0.0143 (10)	0.0090 (11)
N3	0.0313 (12)	0.0410 (12)	0.0469 (12)	0.0030 (10)	0.0066 (10)	0.0064 (10)
N4	0.0323 (12)	0.0434 (14)	0.0507 (14)	0.0013 (11)	0.0126 (11)	0.0124 (12)
N5	0.0314 (11)	0.0470 (13)	0.0389 (12)	0.0007 (10)	0.0108 (10)	0.0015 (10)
C1	0.065 (2)	0.0434 (16)	0.0620 (18)	0.0039 (15)	0.0270 (16)	0.0043 (15)
C2	0.059 (2)	0.064 (2)	0.066 (2)	0.0128 (17)	0.0162 (16)	0.0262 (18)
C3	0.058 (2)	0.084 (2)	0.0471 (17)	−0.0004 (19)	−0.0025 (15)	0.0157 (18)
C4	0.0346 (14)	0.0434 (15)	0.0364 (13)	−0.0024 (12)	0.0091 (11)	0.0021 (12)
C5	0.0439 (15)	0.0456 (17)	0.0420 (14)	−0.0041 (13)	0.0107 (12)	0.0034 (13)
C6	0.0603 (19)	0.0576 (19)	0.0424 (15)	−0.0027 (15)	0.0054 (14)	−0.0024 (14)
C7	0.069 (2)	0.092 (2)	0.0630 (19)	0.0289 (19)	0.0377 (17)	0.0118 (18)
C8	0.0234 (12)	0.0313 (13)	0.0417 (14)	0.0007 (10)	0.0037 (11)	0.0031 (11)
C9	0.0312 (13)	0.0316 (13)	0.0450 (14)	0.0009 (11)	0.0112 (12)	−0.0002 (12)
C10	0.0302 (13)	0.0311 (13)	0.0424 (14)	−0.0017 (11)	0.0063 (12)	−0.0019 (11)
C11	0.0287 (14)	0.0426 (16)	0.0610 (18)	0.0040 (12)	0.0087 (13)	0.0123 (14)
C12	0.0433 (16)	0.0426 (15)	0.0566 (16)	−0.0036 (13)	0.0219 (13)	−0.0039 (14)
C13	0.0416 (15)	0.0460 (16)	0.0568 (16)	0.0059 (13)	0.0188 (13)	−0.0010 (13)
C14	0.059 (2)	0.0513 (17)	0.0600 (18)	−0.0148 (16)	0.0176 (15)	−0.0084 (15)
C15	0.0347 (15)	0.064 (2)	0.073 (2)	0.0080 (15)	0.0174 (15)	0.0161 (17)
C16	0.0452 (18)	0.068 (2)	0.0580 (18)	−0.0170 (17)	0.0033 (15)	0.0101 (17)
C17	0.0321 (13)	0.0390 (14)	0.0393 (13)	−0.0003 (12)	0.0129 (11)	0.0038 (12)
C18	0.0465 (16)	0.0653 (19)	0.0403 (15)	0.0101 (15)	0.0157 (13)	0.0026 (14)

Geometric parameters (Å, º) top

O1—N4	1.223 (3)	C5—H5	0.9300
O2—N4	1.224 (3)	C6—H6	0.9300
N1—C9	1.370 (3)	C7—H7A	0.9600
N1—C4	1.438 (3)	C7—H7B	0.9600
N1—C7	1.464 (3)	C7—H7C	0.9600
N2—C11	1.324 (3)	C8—C9	1.395 (3)
N2—C9	1.355 (3)	C8—C10	1.404 (3)
N3—C11	1.319 (3)	C11—H11	0.9300
N3—C10	1.353 (3)	C12—C14	1.374 (4)
N4—C8	1.464 (3)	C12—C17	1.382 (3)
N5—C10	1.366 (3)	C12—H12	0.9300
N5—C17	1.444 (3)	C13—C17	1.375 (4)
N5—C18	1.455 (3)	C13—C15	1.385 (4)
C1—C2	1.375 (4)	C13—H13	0.9300
C1—C5	1.381 (4)	C14—C16	1.374 (4)
C1—H1	0.9300	C14—H14	0.9300
C2—C3	1.365 (4)	C15—C16	1.365 (4)
C2—H2	0.9300	C15—H15	0.9300
C3—C6	1.382 (4)	C16—H16	0.9300
C3—H3	0.9300	C18—H18A	0.9600
C4—C5	1.369 (3)	C18—H18B	0.9600
C4—C6	1.386 (3)	C18—H18C	0.9600

C9—N1—C4	121.6 (2)	C9—C8—N4	120.7 (2)
C9—N1—C7	118.9 (2)	C10—C8—N4	119.2 (2)
C4—N1—C7	116.6 (2)	N2—C9—N1	116.1 (2)
C11—N2—C9	116.0 (2)	N2—C9—C8	118.9 (2)
C11—N3—C10	115.8 (2)	N1—C9—C8	125.0 (2)
O1—N4—O2	124.5 (2)	N3—C10—N5	117.0 (2)
O1—N4—C8	117.7 (2)	N3—C10—C8	119.1 (2)
O2—N4—C8	117.8 (2)	N5—C10—C8	123.9 (2)
C10—N5—C17	120.2 (2)	N3—C11—N2	129.4 (2)
C10—N5—C18	118.7 (2)	N3—C11—H11	115.3
C17—N5—C18	116.9 (2)	N2—C11—H11	115.3
C2—C1—C5	120.4 (3)	C14—C12—C17	120.0 (3)
C2—C1—H1	119.8	C14—C12—H12	120.0
C5—C1—H1	119.8	C17—C12—H12	120.0
C3—C2—C1	119.8 (3)	C17—C13—C15	119.3 (3)
C3—C2—H2	120.1	C17—C13—H13	120.4
C1—C2—H2	120.1	C15—C13—H13	120.4
C2—C3—C6	120.5 (3)	C16—C14—C12	119.9 (3)
C2—C3—H3	119.8	C16—C14—H14	120.0
C6—C3—H3	119.8	C12—C14—H14	120.0
C5—C4—C6	120.1 (2)	C16—C15—C13	120.5 (3)
C5—C4—N1	120.5 (2)	C16—C15—H15	119.8
C6—C4—N1	119.4 (2)	C13—C15—H15	119.8
C4—C5—C1	119.7 (2)	C15—C16—C14	120.2 (3)
C4—C5—H5	120.1	C15—C16—H16	119.9
C1—C5—H5	120.1	C14—C16—H16	119.9
C3—C6—C4	119.5 (3)	C13—C17—C12	120.1 (2)
C3—C6—H6	120.3	C13—C17—N5	120.0 (2)
C4—C6—H6	120.3	C12—C17—N5	119.9 (2)
N1—C7—H7A	109.5	N5—C18—H18A	109.5
N1—C7—H7B	109.5	N5—C18—H18B	109.5
H7A—C7—H7B	109.5	H18A—C18—H18B	109.5
N1—C7—H7C	109.5	N5—C18—H18C	109.5
H7A—C7—H7C	109.5	H18A—C18—H18C	109.5
H7B—C7—H7C	109.5	H18B—C18—H18C	109.5
C9—C8—C10	120.1 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₅O₂
M_r	335.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.794 (2), 7.0019 (14), 23.650 (6)
β (°)	109.02 (3)
V (Å³)	1689.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.956, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	15784, 3843, 2018
R_int	0.108
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.146, 1.05
No. of reflections	3843
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.20

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).

Acknowledgements

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

References

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