6-Chloro-N-methyl-N-phenyl-pyrimidine-4,5-diamine.

In the title compound, C(11)H(11)ClN(4), the dihedral angle between the aromatic rings is 66.47 (8)°. In the crystal, mol-ecules are linked by N-H⋯N hydrogen bonds, generating C(5) chains propagating in [010]. Slipped aromatic π-π stacking between centrosymmetrically related pairs of pyrim-idine rings also occurs [centroid-centroid separation = 3.7634 (12)Å and slippage = 1.715 Å].

Related literature

For background to pyrimidines, see: Barillari et al. (2001 ▶); Gangjee et al. (2010 ▶). For slipped π–π stacking inter­actions, see: Glówka et al. (1999 ▶).

Experimental

Crystal data

C11H11ClN4

M = 234.69

Monoclinic,

a = 9.5887 (19) Å

b = 9.948 (2) Å

c = 12.671 (3) Å

β = 109.63 (3)°

V = 1138.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 293 K

0.45 × 0.36 × 0.33 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.872, T max = 0.905

10835 measured reflections

2588 independent reflections

1983 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.105

S = 1.07

2588 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.34 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998) ▶; cell refinement: PROCESS-AUTO ▶; data reduction: CrystalStructure (Rigaku, 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811028303/hb5937sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028303/hb5937Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811028303/hb5937Isup3.cml

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

C11H11ClN4	F(000) = 488
Mr = 234.69	Dx = 1.369 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1000 reflections
a = 9.5887 (19) Å	θ = 3.1–27.5°
b = 9.948 (2) Å	µ = 0.31 mm−1
c = 12.671 (3) Å	T = 293 K
β = 109.63 (3)°	Block, colorless
V = 1138.4 (4) Å3	0.45 × 0.36 × 0.33 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	2588 independent reflections
Radiation source: fine-focus sealed tube	1983 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 10.00 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.872, Tmax = 0.905	l = −16→16
10835 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0596P)2 + 0.0777P] where P = (Fo2 + 2Fc2)/3
2588 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.39218 (4)	0.36966 (4)	0.22870 (4)	0.06006 (16)
N1	0.52906 (15)	0.54876 (12)	0.14917 (12)	0.0536 (3)
N2	0.74328 (16)	0.50645 (12)	0.10019 (11)	0.0533 (3)
N3	0.85704 (14)	0.29788 (13)	0.11914 (11)	0.0515 (3)
N4	0.64945 (17)	0.20317 (13)	0.22608 (13)	0.0607 (4)
H4A	0.5861	0.1794	0.2571	0.073*
H4B	0.7179	0.1483	0.2243	0.073*
C1	0.53371 (16)	0.42063 (14)	0.18003 (12)	0.0439 (3)
C2	0.6380 (2)	0.58510 (16)	0.11281 (15)	0.0590 (4)
H2	0.6410	0.6752	0.0941	0.071*
C3	0.74410 (16)	0.37803 (13)	0.12985 (12)	0.0436 (3)
C4	0.64133 (15)	0.32788 (13)	0.17980 (11)	0.0411 (3)
C5	0.83458 (16)	0.15897 (14)	0.08849 (12)	0.0443 (3)
C6	0.70775 (18)	0.11594 (16)	0.00632 (14)	0.0529 (4)
H6	0.6337	0.1773	−0.0293	0.064*
C7	0.6902 (2)	−0.01899 (18)	−0.02337 (15)	0.0645 (5)
H7	0.6035	−0.0482	−0.0777	0.077*
C8	0.8007 (2)	−0.10947 (17)	0.02737 (17)	0.0659 (5)
H8	0.7892	−0.1997	0.0070	0.079*
C9	0.9276 (2)	−0.0667 (2)	0.10786 (17)	0.0731 (5)
H9	1.0029	−0.1277	0.1416	0.088*
C10	0.9443 (2)	0.06674 (19)	0.13924 (15)	0.0627 (4)
H10	1.0302	0.0948	0.1950	0.075*
C11	0.9716 (2)	0.36428 (19)	0.0848 (2)	0.0854 (7)
H11A	0.9328	0.3842	0.0061	0.128*
H11B	1.0556	0.3058	0.0994	0.128*
H11C	1.0013	0.4462	0.1263	0.128*

	U11	U22	U33	U12	U13	U23
Cl1	0.0518 (2)	0.0508 (2)	0.0909 (3)	−0.00514 (16)	0.0415 (2)	−0.00430 (18)
N1	0.0596 (8)	0.0419 (7)	0.0655 (8)	0.0004 (6)	0.0290 (7)	−0.0013 (5)
N2	0.0625 (8)	0.0450 (7)	0.0612 (8)	−0.0097 (6)	0.0322 (7)	−0.0021 (5)
N3	0.0441 (7)	0.0521 (7)	0.0666 (8)	−0.0087 (5)	0.0294 (6)	−0.0103 (6)
N4	0.0722 (9)	0.0451 (7)	0.0856 (10)	0.0066 (6)	0.0541 (9)	0.0102 (6)
C1	0.0441 (7)	0.0418 (7)	0.0507 (8)	−0.0071 (6)	0.0225 (7)	−0.0064 (6)
C2	0.0754 (11)	0.0386 (7)	0.0744 (11)	−0.0032 (7)	0.0400 (10)	0.0019 (7)
C3	0.0439 (7)	0.0441 (7)	0.0461 (7)	−0.0073 (6)	0.0195 (6)	−0.0064 (6)
C4	0.0426 (7)	0.0372 (7)	0.0457 (7)	−0.0068 (5)	0.0180 (6)	−0.0057 (5)
C5	0.0432 (7)	0.0482 (8)	0.0464 (7)	0.0000 (6)	0.0215 (6)	−0.0025 (6)
C6	0.0468 (8)	0.0577 (9)	0.0529 (8)	0.0021 (7)	0.0148 (7)	−0.0053 (7)
C7	0.0640 (11)	0.0676 (11)	0.0659 (11)	−0.0135 (8)	0.0272 (9)	−0.0210 (8)
C8	0.0855 (14)	0.0476 (9)	0.0830 (13)	−0.0023 (9)	0.0525 (12)	−0.0074 (8)
C9	0.0815 (13)	0.0634 (11)	0.0800 (13)	0.0262 (10)	0.0348 (11)	0.0136 (9)
C10	0.0518 (9)	0.0723 (11)	0.0595 (10)	0.0099 (8)	0.0126 (8)	0.0002 (8)
C11	0.0773 (13)	0.0696 (12)	0.140 (2)	−0.0238 (10)	0.0768 (15)	−0.0253 (12)

Cl1—C1	1.7440 (14)	C5—C6	1.377 (2)
N1—C2	1.326 (2)	C5—C10	1.381 (2)
N1—C1	1.3296 (19)	C6—C7	1.389 (2)
N2—C2	1.329 (2)	C6—H6	0.9300
N2—C3	1.3309 (18)	C7—C8	1.374 (3)
N3—C3	1.3876 (18)	C7—H7	0.9300
N3—C5	1.4320 (19)	C8—C9	1.367 (3)
N3—C11	1.467 (2)	C8—H8	0.9300
N4—C4	1.3633 (18)	C9—C10	1.379 (3)
N4—H4A	0.8600	C9—H9	0.9300
N4—H4B	0.8600	C10—H10	0.9300
C1—C4	1.3850 (19)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.4282 (18)	C11—H11C	0.9600
C2—N1—C1	114.28 (13)	C10—C5—N3	119.55 (15)
C2—N2—C3	117.64 (12)	C5—C6—C7	120.07 (16)
C3—N3—C5	121.99 (11)	C5—C6—H6	120.0
C3—N3—C11	117.18 (13)	C7—C6—H6	120.0
C5—N3—C11	114.41 (12)	C8—C7—C6	120.14 (17)
C4—N4—H4A	120.0	C8—C7—H7	119.9
C4—N4—H4B	120.0	C6—C7—H7	119.9
H4A—N4—H4B	120.0	C9—C8—C7	119.88 (16)
N1—C1—C4	126.12 (12)	C9—C8—H8	120.1
N1—C1—Cl1	115.43 (10)	C7—C8—H8	120.1
C4—C1—Cl1	118.42 (11)	C8—C9—C10	120.19 (17)
N1—C2—N2	126.91 (14)	C8—C9—H9	119.9
N1—C2—H2	116.5	C10—C9—H9	119.9
N2—C2—H2	116.5	C9—C10—C5	120.57 (18)
N2—C3—N3	117.05 (12)	C9—C10—H10	119.7
N2—C3—C4	121.39 (13)	C5—C10—H10	119.7
N3—C3—C4	121.33 (12)	N3—C11—H11A	109.5
N4—C4—C1	122.70 (12)	N3—C11—H11B	109.5
N4—C4—C3	124.08 (13)	H11A—C11—H11B	109.5
C1—C4—C3	113.19 (12)	N3—C11—H11C	109.5
C6—C5—C10	119.13 (15)	H11A—C11—H11C	109.5
C6—C5—N3	121.28 (14)	H11B—C11—H11C	109.5
C2—N1—C1—C4	1.8 (2)	N3—C3—C4—N4	3.9 (2)
C2—N1—C1—Cl1	179.82 (12)	N2—C3—C4—C1	7.6 (2)
C1—N1—C2—N2	3.2 (3)	N3—C3—C4—C1	−178.05 (13)
C3—N2—C2—N1	−2.2 (3)	C3—N3—C5—C6	41.5 (2)
C2—N2—C3—N3	−178.27 (15)	C11—N3—C5—C6	−109.51 (18)
C2—N2—C3—C4	−3.7 (2)	C3—N3—C5—C10	−140.87 (15)
C5—N3—C3—N2	−145.53 (14)	C11—N3—C5—C10	68.1 (2)
C11—N3—C3—N2	4.8 (2)	C10—C5—C6—C7	1.0 (2)
C5—N3—C3—C4	39.9 (2)	N3—C5—C6—C7	178.65 (13)
C11—N3—C3—C4	−169.80 (17)	C5—C6—C7—C8	−1.5 (2)
N1—C1—C4—N4	171.27 (15)	C6—C7—C8—C9	0.5 (3)
Cl1—C1—C4—N4	−6.7 (2)	C7—C8—C9—C10	0.8 (3)
N1—C1—C4—C3	−6.8 (2)	C8—C9—C10—C5	−1.2 (3)
Cl1—C1—C4—C3	175.23 (10)	C6—C5—C10—C9	0.3 (2)
N2—C3—C4—N4	−170.43 (14)	N3—C5—C10—C9	−177.38 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1i	0.86	2.28	3.0993 (18)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N1i	0.86	2.28	3.0993 (18)	159

Symmetry code: (i) .