4-Chloro-N-(pyrimidin-2-yl)aniline

Maizathul Akmam, A.B.; Abdullah, Z.; Ng, S.W.

doi:10.1107/S1600536808041184

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o94

doi:10.1107/S1600536808041184

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4-Chloro-N-(pyrimidin-2-yl)aniline

A. Bakar Maizathul Akmam,^a Zanariah Abdullah ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 4 December 2008; accepted 5 December 2008; online 10 December 2008)

The two aromatic rings in the title compound, C₁₀H₈ClN₃, open the angle at the planar N atom to 128.00 (12)°. The amino N atom of one molecule forms a hydrogen bond to the 1-N atom of an adjacent pyrimidyl ring, generating a hydrogen-bonded dimer.

Related literature

For other 4-chloroanilino substituted N-heterocycles, see: Fairuz et al. (2008 ); Idris et al. (2008 ).

Experimental

Crystal data

C₁₀H₈ClN₃
M_r = 205.64
Triclinic, $[P \overline 1]$
a = 3.7750 (1) Å
b = 10.0589 (3) Å
c = 12.0116 (3) Å
α = 89.237 (1)°
β = 89.037 (1)°
γ = 89.399 (2)°
V = 455.98 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 100 (2) K
0.35 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.880, T_max = 0.982
3625 measured reflections
2032 independent reflections
1757 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.080
S = 1.02
2032 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.85 (2)	2.18 (2)	3.028 (2)	174 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041184/tk2341sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041184/tk2341Isup2.hkl

checkCIF report

Related literature top

For other 4-chloroanilino substituted N-heterocycles, see: Fairuz et al. (2008); Idris et al. (2008).

Experimental top

2-Chloropyrimidine (2.88 g, 2.5 mmol) and 4-chloroaniline (3.20 g, 25 mmol) were mixed with ethanol (2 ml) and the mixture was heated at 423–433 K for 8 h. The product was dissolved in water and the solution extracted with ether. The ether phase was dried over sodium sulfate; the evaporation of the solvent gave well shaped crystals along with some unidentified brown material.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of hydrogen-bonded dimeric structure of C₁₀H₈ClN₃ at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Hydrogen bonds are shown as red dashed lines.

4-Chloro-N-(pyrimidin-2-yl)aniline top

Crystal data top

C₁₀H₈ClN₃	Z = 2
M_r = 205.64	F(000) = 212
Triclinic, P1	D_x = 1.498 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.7750 (1) Å	Cell parameters from 2160 reflections
b = 10.0589 (3) Å	θ = 2.6–28.2°
c = 12.0116 (3) Å	µ = 0.38 mm⁻¹
α = 89.237 (1)°	T = 100 K
β = 89.037 (1)°	Plate, yellow
γ = 89.399 (2)°	0.35 × 0.15 × 0.05 mm
V = 455.98 (2) Å³

Data collection top

Bruker SMART APEX diffractometer	2032 independent reflections
Radiation source: fine-focus sealed tube	1757 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.880, T_max = 0.982	k = −13→13
3625 measured reflections	l = −14→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0319P)² + 0.3201P] where P = (F_o² + 2F_c²)/3
2032 reflections	(Δ/σ)_max = 0.001
131 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₀H₈ClN₃	γ = 89.399 (2)°
M_r = 205.64	V = 455.98 (2) Å³
Triclinic, P1	Z = 2
a = 3.7750 (1) Å	Mo Kα radiation
b = 10.0589 (3) Å	µ = 0.38 mm⁻¹
c = 12.0116 (3) Å	T = 100 K
α = 89.237 (1)°	0.35 × 0.15 × 0.05 mm
β = 89.037 (1)°

Data collection top

Bruker SMART APEX diffractometer	2032 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1757 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.982	R_int = 0.014
3625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.34 e Å⁻³
2032 reflections	Δρ_min = −0.24 e Å⁻³
131 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	1.12780 (11)	0.77439 (4)	1.04792 (3)	0.02641 (13)
N1	0.6990 (3)	0.63747 (13)	0.59185 (10)	0.0156 (3)
H1	0.642 (5)	0.556 (2)	0.5875 (16)	0.028 (5)*
N2	0.5390 (3)	0.64905 (12)	0.40908 (10)	0.0150 (3)
N3	0.7907 (3)	0.83808 (12)	0.49717 (10)	0.0156 (3)
C1	0.8101 (4)	0.67719 (14)	0.69743 (11)	0.0136 (3)
C2	0.7505 (4)	0.80454 (15)	0.73923 (11)	0.0156 (3)
H2	0.6416	0.8710	0.6941	0.019*
C3	0.8504 (4)	0.83405 (15)	0.84683 (12)	0.0178 (3)
H3	0.8117	0.9208	0.8752	0.021*
C4	1.0064 (4)	0.73655 (16)	0.91245 (11)	0.0172 (3)
C5	1.0687 (4)	0.60984 (15)	0.87278 (12)	0.0175 (3)
H5	1.1767	0.5436	0.9184	0.021*
C6	0.9703 (4)	0.58131 (15)	0.76498 (12)	0.0156 (3)
H6	1.0131	0.4947	0.7368	0.019*
C7	0.6752 (4)	0.71254 (14)	0.49723 (11)	0.0132 (3)
C8	0.7695 (4)	0.90471 (14)	0.40058 (12)	0.0156 (3)
H8	0.8469	0.9943	0.3975	0.019*
C9	0.6401 (4)	0.84960 (15)	0.30478 (12)	0.0165 (3)
H9	0.6296	0.8981	0.2365	0.020*
C10	0.5268 (4)	0.71961 (15)	0.31431 (11)	0.0159 (3)
H10	0.4358	0.6785	0.2502	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0288 (2)	0.0384 (2)	0.01228 (18)	−0.00173 (17)	−0.00450 (14)	−0.00490 (15)
N1	0.0213 (7)	0.0124 (6)	0.0133 (6)	−0.0040 (5)	−0.0022 (5)	−0.0008 (5)
N2	0.0171 (6)	0.0139 (6)	0.0141 (6)	−0.0007 (5)	−0.0017 (5)	−0.0020 (4)
N3	0.0169 (6)	0.0151 (6)	0.0146 (6)	−0.0028 (5)	0.0002 (5)	−0.0010 (5)
C1	0.0129 (6)	0.0158 (7)	0.0121 (6)	−0.0037 (5)	0.0005 (5)	−0.0004 (5)
C2	0.0173 (7)	0.0159 (7)	0.0136 (6)	−0.0006 (5)	0.0002 (5)	0.0005 (5)
C3	0.0184 (7)	0.0185 (7)	0.0164 (7)	−0.0019 (6)	0.0022 (5)	−0.0043 (5)
C4	0.0152 (7)	0.0260 (8)	0.0103 (6)	−0.0035 (6)	0.0003 (5)	−0.0020 (5)
C5	0.0141 (7)	0.0224 (8)	0.0158 (7)	−0.0005 (6)	0.0003 (5)	0.0030 (6)
C6	0.0153 (7)	0.0154 (7)	0.0162 (7)	−0.0012 (5)	0.0016 (5)	−0.0009 (5)
C7	0.0118 (6)	0.0145 (7)	0.0133 (6)	0.0001 (5)	0.0007 (5)	−0.0018 (5)
C8	0.0159 (7)	0.0138 (7)	0.0170 (7)	−0.0013 (5)	0.0017 (5)	−0.0001 (5)
C9	0.0182 (7)	0.0177 (7)	0.0135 (6)	0.0008 (6)	0.0004 (5)	0.0012 (5)
C10	0.0161 (7)	0.0180 (7)	0.0136 (6)	0.0010 (5)	−0.0019 (5)	−0.0030 (5)

Geometric parameters (Å, º) top

Cl1—C4	1.7458 (14)	C3—C4	1.383 (2)
N1—C7	1.3599 (18)	C3—H3	0.9500
N1—C1	1.4067 (17)	C4—C5	1.383 (2)
N1—H1	0.85 (2)	C5—C6	1.3875 (19)
N2—C10	1.3346 (18)	C5—H5	0.9500
N2—C7	1.3552 (17)	C6—H6	0.9500
N3—C8	1.3353 (18)	C8—C9	1.383 (2)
N3—C7	1.3404 (18)	C8—H8	0.9500
C1—C6	1.392 (2)	C9—C10	1.383 (2)
C1—C2	1.397 (2)	C9—H9	0.9500
C2—C3	1.3890 (19)	C10—H10	0.9500
C2—H2	0.9500

C7—N1—C1	128.00 (12)	C4—C5—H5	120.7
C7—N1—H1	116.9 (14)	C6—C5—H5	120.7
C1—N1—H1	115.1 (14)	C5—C6—C1	121.22 (13)
C10—N2—C7	115.63 (12)	C5—C6—H6	119.4
C8—N3—C7	116.05 (12)	C1—C6—H6	119.4
C6—C1—C2	119.06 (13)	N3—C7—N2	125.91 (13)
C6—C1—N1	117.44 (13)	N3—C7—N1	119.22 (12)
C2—C1—N1	123.41 (13)	N2—C7—N1	114.85 (12)
C3—C2—C1	120.03 (14)	N3—C8—C9	123.14 (13)
C3—C2—H2	120.0	N3—C8—H8	118.4
C1—C2—H2	120.0	C9—C8—H8	118.4
C4—C3—C2	119.69 (14)	C10—C9—C8	115.99 (13)
C4—C3—H3	120.2	C10—C9—H9	122.0
C2—C3—H3	120.2	C8—C9—H9	122.0
C5—C4—C3	121.30 (13)	N2—C10—C9	123.27 (13)
C5—C4—Cl1	119.40 (12)	N2—C10—H10	118.4
C3—C4—Cl1	119.31 (12)	C9—C10—H10	118.4
C4—C5—C6	118.70 (14)

C7—N1—C1—C6	−150.50 (14)	N1—C1—C6—C5	−176.11 (13)
C7—N1—C1—C2	33.1 (2)	C8—N3—C7—N2	−0.4 (2)
C6—C1—C2—C3	−0.1 (2)	C8—N3—C7—N1	178.01 (13)
N1—C1—C2—C3	176.32 (13)	C10—N2—C7—N3	1.0 (2)
C1—C2—C3—C4	−0.5 (2)	C10—N2—C7—N1	−177.43 (13)
C2—C3—C4—C5	0.6 (2)	C1—N1—C7—N3	5.1 (2)
C2—C3—C4—Cl1	−179.51 (11)	C1—N1—C7—N2	−176.27 (13)
C3—C4—C5—C6	−0.2 (2)	C7—N3—C8—C9	−0.6 (2)
Cl1—C4—C5—C6	179.93 (11)	N3—C8—C9—C10	0.8 (2)
C4—C5—C6—C1	−0.4 (2)	C7—N2—C10—C9	−0.7 (2)
C2—C1—C6—C5	0.5 (2)	C8—C9—C10—N2	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.85 (2)	2.18 (2)	3.028 (2)	174 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₈ClN₃
M_r	205.64
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	3.7750 (1), 10.0589 (3), 12.0116 (3)
α, β, γ (°)	89.237 (1), 89.037 (1), 89.399 (2)
V (Å³)	455.98 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.35 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.880, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	3625, 2032, 1757
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.02
No. of reflections	2032
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.85 (2)	2.18 (2)	3.028 (2)	174 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank the University of Malaya for supporting this study (PS077/2007 C).

References

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