1,4-Bis(6-chloro­pyrimidin-4-yl­oxy)benzene

Ma, W.; Li, H.

doi:10.1107/S1600536808043511

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o223

doi:10.1107/S1600536808043511

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1,4-Bis(6-chloropyrimidin-4-yloxy)benzene

Wen Ma ^a ^* and Hongyan Li ^b

^aCollege of Chemistry and Chemical Engineering, Xinyang Normal Universty, Xinyang, Henan 464000, People's Republic of China, and ^bCollege of Life Science, Xinyang Normal Universty, Xinyang, Henan 464000, People's Republic of China
^*Correspondence e-mail: maw0809@yahoo.com.cn

(Received 15 December 2008; accepted 22 December 2008; online 8 January 2009)

In the title compound, C₁₄H₈Cl₂N₄O₂, all atoms of the 6-chloropyrimidin-4-yloxy group and the C atoms at the para positions of the central benzene ring lie on a crystallographic mirror plane. The complete benzene ring is generated by the mirror plane and hence the dihedral angles between the pyrimidine rings and the benzene ring are exactly 90°. The crystal structure is stabilized by weak C—H⋯O and C—H⋯N hydrogen bonds.

Related literature

For background information, see: Halim et al. (1999 ); Meng & Huang (2000 ); Maes et al. (2003 ); Friend et al. (1999 ).

Experimental

Crystal data

C₁₄H₈Cl₂N₄O₂
M_r = 335.14
Monoclinic, C 2/m
a = 19.0760 (5) Å
b = 6.9693 (2) Å
c = 10.7893 (3) Å
β = 93.301 (3)°
V = 1432.02 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
6918 measured reflections
1372 independent reflections
1156 reflections with I > 2σ(I)'
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.07
1372 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2ⁱ	0.93	2.57	3.463 (3)	161
C3—H3⋯N2ⁱⁱ	0.93	2.48	3.355 (3)	157
Symmetry codes: (i) -x, y, -z; (ii) -x+1, y, -z+1.

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043511/lh2746sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043511/lh2746Isup2.hkl

checkCIF report

Comment top

In recent publications it has been shown that polymers consisting of heterocyclic building blocks can be used in organic light-emitting diodes (LEDs) because of their electroluminescent properties. (Halim et al., 1999; Friend et al.,1999; Meng & Huang, 2000; Maes et al., 2003). We report here the synthesis and crystal structure the title compound (I) (Fig. 1). All atoms of the 6-chloropyrimidin-4-yloxy group and the C atoms at the para positions of the central benzene ring lie on a crystallographic mirror plane. The symmetry complete benzene ring is generated by the mirror plane and hence the dihedral angles between the pyrimidine rings and the benzene ring are exactly 90°. The crystal packing is stabilized by weak intermolecular hydrogen bonds interactions. Each molecule acts as a donor and acceptor to form C–H···O and C–H···N hydrogen bonds with two other symmetry related molecules, forming a chain run parallel to [101] (Fig. 2; Table 2).

Related literature top

For background information, see: Halim et al. (1999); Meng & Huang (2000); Maes et al. (2003); Friend et al. (1999).

Experimental top

Hydroquinone 0.55 g(5 mmol) was dissolved in 50 ml CH₃CN, the solution was stirred at room temperature for 0.5 h with an excess of anhydrous K₂CO₃(2.5 equiv.). After another 0.5 h of reflux, 4,6-dichloropyrimidine2.59 g (10 mmol) in 20 ml CH₃CN was added and the mixture was refluxed for 4 h. After evaporation of the solvent, water was added and the mixture was extracted with CH₂Cl₂ and dried over MgSO₄. The products were purified by column chromatography (hexanes/ethyl acetate, 5:1) and obtained as white solids. Colourless block-shapped crystals were obtained by evaporation of CH₂Cl₂.

Computing details top

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level [Symmetry codes: (a) x,-y,z].
	Fig. 2. Part of the crystal structure with hydrogen bonds shown by dashed lines.

1,4-Bis(6-chloropyrimidin-4-yloxy)benzene top

Crystal data top

C₁₄H₈Cl₂N₄O₂	F(000) = 680
M_r = 335.14	D_x = 1.555 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 3581 reflections
a = 19.0760 (5) Å	θ = 2.8–27.8°
b = 6.9693 (2) Å	µ = 0.47 mm⁻¹
c = 10.7893 (3) Å	T = 298 K
β = 93.301 (3)°	Block, colorless
V = 1432.02 (7) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1156 reflections with I > 2σ(I)'
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 25.0°, θ_min = 1.9°
ϕ and ω scans	h = −22→22
6918 measured reflections	k = −8→7
1372 independent reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0635P)² + 0.2906P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1372 reflections	Δρ_max = 0.22 e Å⁻³
128 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0062 (13)

Crystal data top

C₁₄H₈Cl₂N₄O₂	V = 1432.02 (7) Å³
M_r = 335.14	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 19.0760 (5) Å	µ = 0.47 mm⁻¹
b = 6.9693 (2) Å	T = 298 K
c = 10.7893 (3) Å	0.20 × 0.10 × 0.10 mm
β = 93.301 (3)°

Data collection top

Bruker SMART CCD diffractometer	1156 reflections with I > 2σ(I)'
6918 measured reflections	R_int = 0.050
1372 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.07	Δρ_max = 0.22 e Å⁻³
1372 reflections	Δρ_min = −0.25 e Å⁻³
128 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
C1	0.34316 (10)	0.0000	0.22381 (18)	0.0495 (5)
H1	0.3002	0.0000	0.1786	0.059*
C2	0.40565 (11)	0.0000	0.16857 (19)	0.0543 (6)
C3	0.46576 (12)	0.0000	0.3504 (2)	0.0666 (7)
H3	0.5089	0.0000	0.3950	0.080*
C4	0.34857 (11)	0.0000	0.35261 (19)	0.0467 (5)
C5	0.22554 (11)	0.0000	0.36269 (19)	0.0512 (6)
C6	0.19419 (8)	0.1719 (3)	0.33512 (14)	0.0589 (4)
H6	0.2162	0.2867	0.3578	0.071*
C7	0.12865 (9)	0.1712 (3)	0.27244 (15)	0.0636 (5)
H7	0.1058	0.2859	0.2523	0.076*
C8	0.09825 (11)	0.0000	0.24084 (19)	0.0581 (7)
C9	−0.02669 (11)	0.0000	0.21792 (19)	0.0529 (6)
C10	−0.08588 (12)	0.0000	0.1385 (2)	0.0570 (6)
H10	−0.0839	0.0000	0.0526	0.068*
C11	−0.14794 (11)	0.0000	0.1964 (2)	0.0525 (5)
C12	−0.09188 (11)	0.0000	0.3830 (2)	0.0553 (6)
H12	−0.0939	0.0000	0.4689	0.066*
Cl1	0.40498 (4)	0.0000	0.00858 (5)	0.0916 (3)
Cl2	−0.22616 (3)	0.0000	0.10747 (6)	0.0829 (3)
N1	0.46804 (10)	0.0000	0.22748 (18)	0.0676 (6)
N2	0.40951 (9)	0.0000	0.41739 (17)	0.0572 (5)
N3	−0.02774 (9)	0.0000	0.33990 (16)	0.0533 (5)
N4	−0.15287 (9)	0.0000	0.31826 (17)	0.0566 (5)
O1	0.29285 (8)	0.0000	0.42430 (14)	0.0619 (5)
O2	0.03558 (8)	0.0000	0.16482 (14)	0.0793 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0393 (11)	0.0687 (14)	0.0399 (11)	0.000	−0.0027 (9)	0.000
C2	0.0453 (12)	0.0777 (15)	0.0400 (11)	0.000	0.0022 (9)	0.000
C3	0.0407 (12)	0.109 (2)	0.0495 (13)	0.000	−0.0062 (10)	0.000
C4	0.0421 (11)	0.0573 (12)	0.0403 (10)	0.000	0.0002 (8)	0.000
C5	0.0397 (11)	0.0797 (16)	0.0345 (10)	0.000	0.0054 (8)	0.000
C6	0.0543 (9)	0.0708 (11)	0.0520 (9)	−0.0059 (8)	0.0062 (7)	0.0019 (8)
C7	0.0528 (9)	0.0824 (12)	0.0561 (9)	0.0116 (9)	0.0073 (7)	0.0109 (9)
C8	0.0390 (11)	0.102 (2)	0.0340 (10)	0.000	0.0072 (8)	0.000
C9	0.0434 (11)	0.0779 (15)	0.0378 (11)	0.000	0.0067 (9)	0.000
C10	0.0484 (12)	0.0836 (16)	0.0389 (11)	0.000	0.0011 (9)	0.000
C11	0.0440 (11)	0.0612 (14)	0.0519 (12)	0.000	−0.0009 (9)	0.000
C12	0.0515 (13)	0.0762 (16)	0.0389 (11)	0.000	0.0078 (9)	0.000
Cl1	0.0605 (4)	0.1762 (9)	0.0387 (4)	0.000	0.0072 (3)	0.000
Cl2	0.0467 (4)	0.1308 (7)	0.0695 (5)	0.000	−0.0106 (3)	0.000
N1	0.0415 (10)	0.1109 (17)	0.0503 (11)	0.000	0.0013 (9)	0.000
N2	0.0441 (10)	0.0836 (14)	0.0429 (9)	0.000	−0.0057 (8)	0.000
N3	0.0452 (10)	0.0774 (13)	0.0375 (9)	0.000	0.0050 (8)	0.000
N4	0.0447 (10)	0.0750 (13)	0.0509 (11)	0.000	0.0095 (8)	0.000
O1	0.0430 (8)	0.1051 (13)	0.0376 (7)	0.000	0.0019 (6)	0.000
O2	0.0403 (9)	0.1598 (19)	0.0379 (8)	0.000	0.0040 (7)	0.000

Geometric parameters (Å, º) top

C1—C2	1.363 (3)	C7—C8	1.361 (2)
C1—C4	1.388 (3)	C7—H7	0.9300
C1—H1	0.9300	C8—C7ⁱ	1.361 (2)
C2—N1	1.317 (3)	C8—O2	1.410 (3)
C2—Cl1	1.725 (2)	C9—N3	1.317 (3)
C3—N2	1.328 (3)	C9—O2	1.348 (3)
C3—N1	1.329 (3)	C9—C10	1.377 (3)
C3—H3	0.9300	C10—C11	1.370 (3)
C4—N2	1.322 (3)	C10—H10	0.9300
C4—O1	1.350 (2)	C11—N4	1.323 (3)
C5—C6ⁱ	1.364 (2)	C11—Cl2	1.727 (2)
C5—C6	1.364 (2)	C12—N4	1.322 (3)
C5—O1	1.411 (3)	C12—N3	1.334 (3)
C6—C7	1.387 (2)	C12—H12	0.9300
C6—H6	0.9300

C2—C1—C4	114.92 (19)	C7ⁱ—C8—C7	122.4 (2)
C2—C1—H1	122.5	C7ⁱ—C8—O2	118.70 (11)
C4—C1—H1	122.5	C7—C8—O2	118.70 (11)
N1—C2—C1	125.3 (2)	N3—C9—O2	119.27 (19)
N1—C2—Cl1	115.94 (16)	N3—C9—C10	124.21 (19)
C1—C2—Cl1	118.76 (17)	O2—C9—C10	116.52 (19)
N2—C3—N1	128.1 (2)	C11—C10—C9	114.6 (2)
N2—C3—H3	115.9	C11—C10—H10	122.7
N1—C3—H3	115.9	C9—C10—H10	122.7
N2—C4—O1	113.24 (18)	N4—C11—C10	124.4 (2)
N2—C4—C1	122.83 (19)	N4—C11—Cl2	116.32 (17)
O1—C4—C1	123.93 (19)	C10—C11—Cl2	119.24 (18)
C6ⁱ—C5—C6	122.8 (2)	N4—C12—N3	127.8 (2)
C6ⁱ—C5—O1	118.57 (10)	N4—C12—H12	116.1
C6—C5—O1	118.57 (10)	N3—C12—H12	116.1
C5—C6—C7	118.36 (17)	C2—N1—C3	113.6 (2)
C5—C6—H6	120.8	C4—N2—C3	115.20 (19)
C7—C6—H6	120.8	C9—N3—C12	114.53 (19)
C8—C7—C6	118.97 (17)	C12—N4—C11	114.45 (18)
C8—C7—H7	120.5	C4—O1—C5	117.07 (16)
C6—C7—H7	120.5	C9—O2—C8	119.40 (16)

C4—C1—C2—N1	0.0	C1—C4—N2—C3	0.0
C4—C1—C2—Cl1	180.0	N1—C3—N2—C4	0.0
C2—C1—C4—N2	0.0	O2—C9—N3—C12	180.0
C2—C1—C4—O1	180.0	C10—C9—N3—C12	0.0
C6ⁱ—C5—C6—C7	−2.3 (3)	N4—C12—N3—C9	0.0
O1—C5—C6—C7	178.76 (14)	N3—C12—N4—C11	0.0
C5—C6—C7—C8	−0.1 (3)	C10—C11—N4—C12	0.0
C6—C7—C8—C7ⁱ	2.4 (3)	Cl2—C11—N4—C12	180.0
C6—C7—C8—O2	−172.75 (14)	N2—C4—O1—C5	180.0
N3—C9—C10—C11	0.0	C1—C4—O1—C5	0.0
O2—C9—C10—C11	180.0	C6ⁱ—C5—O1—C4	90.53 (16)
C9—C10—C11—N4	0.0	C6—C5—O1—C4	−90.53 (16)
C9—C10—C11—Cl2	180.0	N3—C9—O2—C8	0.0
C1—C2—N1—C3	0.0	C10—C9—O2—C8	180.0
Cl1—C2—N1—C3	180.0	C7ⁱ—C8—O2—C9	92.31 (16)
N2—C3—N1—C2	0.0	C7—C8—O2—C9	−92.31 (16)
O1—C4—N2—C3	180.0

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O2ⁱⁱ	0.93	2.57	3.463 (3)	161
C3—H3···N2ⁱⁱⁱ	0.93	2.48	3.355 (3)	157

Symmetry codes: (ii) −x, y, −z; (iii) −x+1, y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₈Cl₂N₄O₂
M_r	335.14
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	298
a, b, c (Å)	19.0760 (5), 6.9693 (2), 10.7893 (3)
β (°)	93.301 (3)
V (Å³)	1432.02 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)'] reflections	6918, 1372, 1156
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.07
No. of reflections	1372
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O2ⁱ	0.93	2.57	3.463 (3)	161.4
C3—H3···N2ⁱⁱ	0.93	2.48	3.355 (3)	156.6

Symmetry codes: (i) −x, y, −z; (ii) −x+1, y, −z+1.

Acknowledgements

This work was supported by Henan Education Government of China (grant No. 2006150023).

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