4,6-Dichloro-5-(2-meth­oxy­phen­oxy)-2,2′-bipyrimidine

Ren, T.; Zhang, Z.; Zhong, C.; Yang, Z.; Shi, Z.

doi:10.1107/S160053681101419X

organic compounds

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Volume 67| Part 6| June 2011| Page o1334

doi:10.1107/S160053681101419X

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4,6-Dichloro-5-(2-methoxyphenoxy)-2,2′-bipyrimidine

Tian-tian Ren,^a Zhong Zhang,^a Cong-cong Zhong,^a Zhong-zhi Yang ^a and Zhan-wang Shi ^a ^*

^aDepartment of Chemistry, Guangxi University for Nationalities, Nanning 530006, People's Republic of China
^*Correspondence e-mail: shizhanwang2010@yahoo.cn

(Received 26 December 2010; accepted 15 April 2011; online 7 May 2011)

In the title compound, C₁₅H₁₀Cl₂N₄O₂, the dichloropyrimidine and methoxyphenoxy parts are approximately perpendicular [dihedral angle = 89.9 (9)°]. The dihedral angle between the two pyrimidine rings is 36.3 (4)° In the crystal, there are no hydrogen bonds but the molecules are held together by short intermolecular C⋯N [3.206 (3) Å] contacts and C—H⋯π interactions.

Related literature

For the use of 2,2′-bipyrimidine as a ligand in inorganic and organometallic chemistry, see: Fabrice et al. (2008 ); Hunziker & Ludi (1977 ). It was first synthesized by Bly and Mellon (1962 ) utilizing the Ullmann coupling of 2-bromopyrimidine in the presence of metallic copper.

Experimental

Crystal data

C₁₅H₁₀Cl₂N₄O₂
M_r = 349.17
Monoclinic, P 2₁ /n
a = 10.716 (2) Å
b = 8.1112 (18) Å
c = 18.601 (5) Å
β = 106.486 (3)°
V = 1550.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 296 K
0.22 × 0.20 × 0.18 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.911, T_max = 0.926
8106 measured reflections
2733 independent reflections
2319 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.114
S = 1.08
2733 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
C—H⋯π interactions (Å, °)

Cg is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cgⁱ	0.93	2.87	3.760 (3)	161
Symmetry code: (i) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101419X/fl2331sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101419X/fl2331Isup2.hkl

checkCIF report

Comment top

2,2'-Bipyrimidine has been used as a ligand in inorganic and organometallic chemistry (Hunziker & Ludi, 1977; Fabrice et al., 2008) and exhibits remarkable stability in acidic medium. It was first synthesized by Bly and Mellon (1962) utilizing the Ullmann coupling of 2-bromopyrimidine in the presence of metallic copper. As part of our studies on the synthesis and characterization of these compounds, we report here the crystal structure of (I).

In (I) the dichloropyrimidine and the methoxyphenoxy are approximately perpendicular (dihedral angle of 89.90 (91) °). The dihedral angle between the two pyrimidine rings is 36.25 (38)° (Fig. 1).

The molecules are linked by intermolecular C—H···N , C—H···C and C···N short contacts. C12—H12···N4, C12···N4=3.639 (3), H12···N4=2.728 (3), and C12—H12···N4=166.49; C8···N2=3.206 (3); C1—H1···C12, C1···C12=3.725 (3), H1···C12=2.814 (3), and C1—H1···C12=166.14; C10—H10···C13, C10···C13=3.694 (3)), H10···C13=2.886 (3), and C13—H10···C10=146.05.

Related literature top

For the use of 2,2'-bipyrimidine as a ligand in inorganic and organometallic chemistry, see: Fabrice et al. (2008); Hunziker & Ludi (1977). It was first synthesized by Bly and Mellon (1962) utilizing the Ullmann coupling of 2-bromopyrimidine in the presence of metallic copper.

Experimental top

A solution of 4,6-Dichloro-5-(2-methoxyphenoxy)-2,2'-bipyrimidine (10 mmol) in 50ml toluene was refluxed for 1h with stirring then filtered, washed several times with ethanol and dried in vacuo, to produce a powder of the title compound. The powder was added to 50ml toluene with stirring until completely dissolved. Finally, colourless crystals suitable for data collection were obtained by slow evaporation of the toluene at room temperature. Elemental analysis calculate: Elemental analysis: found: C, 51.60; H, 2.89; N, 16.05; calc. for C₁₅H₁₀Cl₂N₄O₂: C,51.53; H, 2.93; N, 16.11.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of (I) showing the short contacts interactions as dashed lines.

4,6-Dichloro-5-(2-methoxyphenoxy)-2,2'-bipyrimidine top

Crystal data top

C₁₅H₁₀Cl₂N₄O₂	F(000) = 712
M_r = 349.17	D_x = 1.496 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.716 (2) Å	Cell parameters from 3720 reflections
b = 8.1112 (18) Å	θ = 2.6–27.4°
c = 18.601 (5) Å	µ = 0.43 mm⁻¹
β = 106.486 (3)°	T = 296 K
V = 1550.3 (6) Å³	Block, colourless
Z = 4	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2733 independent reflections
Radiation source: fine-focus sealed tube	2319 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.911, T_max = 0.926	k = −9→9
8106 measured reflections	l = −22→16

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0522P)² + 0.7172P] where P = (F_o² + 2F_c²)/3
2733 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₁₅H₁₀Cl₂N₄O₂	V = 1550.3 (6) Å³
M_r = 349.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.716 (2) Å	µ = 0.43 mm⁻¹
b = 8.1112 (18) Å	T = 296 K
c = 18.601 (5) Å	0.22 × 0.20 × 0.18 mm
β = 106.486 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2733 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2319 reflections with I > 2σ(I)
T_min = 0.911, T_max = 0.926	R_int = 0.027
8106 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.08	Δρ_max = 0.26 e Å⁻³
2733 reflections	Δρ_min = −0.54 e Å⁻³
209 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl2	0.35488 (7)	0.23438 (8)	0.95225 (4)	0.0698 (2)
Cl1	−0.12322 (6)	0.00465 (9)	0.81525 (4)	0.0697 (2)
O1	0.09431 (17)	0.24803 (18)	0.84012 (8)	0.0514 (4)
N1	0.04052 (18)	−0.1321 (2)	0.93028 (10)	0.0461 (4)
O2	−0.01418 (17)	0.4733 (2)	0.74474 (9)	0.0564 (4)
N3	0.25212 (18)	−0.0303 (2)	0.99122 (9)	0.0434 (4)
N2	0.07696 (19)	−0.3406 (2)	1.05310 (10)	0.0509 (5)
C4	0.1789 (2)	−0.2855 (3)	1.03313 (11)	0.0394 (5)
C5	0.1558 (2)	−0.1388 (3)	0.98205 (11)	0.0399 (5)
N4	0.29885 (19)	−0.3461 (2)	1.05286 (11)	0.0504 (5)
C9	0.1043 (2)	0.2281 (3)	0.76750 (11)	0.0401 (5)
C8	0.1164 (2)	0.1136 (3)	0.88636 (11)	0.0437 (5)
C13	0.0568 (2)	0.3436 (3)	0.64467 (12)	0.0480 (5)
H13	0.0179	0.4242	0.6099	0.058*
C14	0.0468 (2)	0.3523 (3)	0.71727 (11)	0.0403 (5)
C12	0.1243 (2)	0.2156 (3)	0.62364 (12)	0.0512 (6)
H12	0.1311	0.2112	0.5749	0.061*
C6	0.2308 (2)	0.0942 (3)	0.94339 (11)	0.0446 (5)
C2	0.2172 (3)	−0.5496 (3)	1.11929 (13)	0.0580 (6)
H2	0.2305	−0.6438	1.1490	0.070*
C15	−0.0513 (3)	0.6175 (3)	0.69994 (17)	0.0712 (8)
H15A	−0.1114	0.5880	0.6528	0.107*
H15B	0.0245	0.6674	0.6914	0.107*
H15C	−0.0920	0.6943	0.7255	0.107*
C10	0.1703 (2)	0.1008 (3)	0.74643 (12)	0.0501 (6)
H10	0.2076	0.0185	0.7806	0.060*
C11	0.1813 (2)	0.0952 (3)	0.67400 (13)	0.0537 (6)
H11	0.2272	0.0100	0.6596	0.064*
C3	0.0986 (3)	−0.4745 (3)	1.09680 (13)	0.0564 (6)
H3	0.0303	−0.5180	1.1124	0.068*
C7	0.0238 (2)	−0.0064 (3)	0.88345 (12)	0.0457 (5)
C1	0.3157 (3)	−0.4805 (3)	1.09624 (14)	0.0589 (7)
H1	0.3978	−0.5289	1.1113	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0869 (5)	0.0571 (4)	0.0554 (4)	−0.0231 (3)	0.0039 (3)	0.0114 (3)
Cl1	0.0610 (4)	0.0732 (5)	0.0600 (4)	0.0094 (3)	−0.0073 (3)	0.0149 (3)
O1	0.0831 (11)	0.0397 (9)	0.0335 (8)	0.0168 (8)	0.0197 (8)	0.0094 (6)
N1	0.0521 (11)	0.0438 (10)	0.0403 (10)	0.0047 (8)	0.0095 (8)	0.0056 (8)
O2	0.0784 (11)	0.0468 (9)	0.0461 (9)	0.0198 (8)	0.0209 (8)	0.0144 (7)
N3	0.0577 (11)	0.0390 (10)	0.0316 (9)	0.0020 (8)	0.0094 (8)	0.0035 (7)
N2	0.0617 (12)	0.0495 (11)	0.0446 (10)	0.0045 (9)	0.0203 (9)	0.0101 (9)
C4	0.0534 (12)	0.0357 (11)	0.0291 (10)	0.0028 (9)	0.0115 (9)	−0.0003 (8)
C5	0.0518 (12)	0.0379 (11)	0.0307 (10)	0.0062 (9)	0.0127 (9)	0.0015 (8)
N4	0.0558 (11)	0.0447 (11)	0.0490 (11)	0.0080 (9)	0.0121 (9)	0.0089 (9)
C9	0.0471 (11)	0.0431 (12)	0.0286 (10)	−0.0003 (9)	0.0084 (8)	0.0024 (8)
C8	0.0639 (14)	0.0369 (11)	0.0313 (10)	0.0119 (10)	0.0151 (10)	0.0058 (9)
C13	0.0564 (13)	0.0493 (13)	0.0362 (11)	−0.0062 (10)	0.0095 (10)	0.0082 (10)
C14	0.0436 (11)	0.0402 (12)	0.0357 (11)	−0.0011 (9)	0.0087 (9)	0.0036 (9)
C12	0.0572 (14)	0.0628 (15)	0.0355 (12)	−0.0119 (11)	0.0164 (10)	−0.0054 (11)
C6	0.0624 (13)	0.0374 (11)	0.0334 (10)	−0.0003 (10)	0.0124 (10)	0.0003 (9)
C2	0.0844 (18)	0.0406 (13)	0.0435 (13)	0.0036 (12)	0.0093 (12)	0.0116 (10)
C15	0.0818 (19)	0.0533 (16)	0.0810 (19)	0.0250 (14)	0.0273 (15)	0.0276 (14)
C10	0.0566 (13)	0.0499 (14)	0.0410 (12)	0.0122 (11)	0.0090 (10)	0.0039 (10)
C11	0.0554 (13)	0.0608 (15)	0.0465 (13)	0.0065 (12)	0.0171 (11)	−0.0070 (11)
C3	0.0767 (17)	0.0511 (14)	0.0449 (13)	−0.0041 (12)	0.0228 (12)	0.0099 (11)
C7	0.0530 (13)	0.0463 (13)	0.0350 (11)	0.0105 (10)	0.0079 (9)	0.0040 (9)
C1	0.0678 (16)	0.0462 (14)	0.0581 (15)	0.0152 (12)	0.0103 (13)	0.0121 (11)

Geometric parameters (Å, º) top

Cl2—C6	1.722 (2)	C8—C6	1.384 (3)
Cl1—C7	1.722 (2)	C13—C12	1.384 (3)
O1—C8	1.367 (2)	C13—C14	1.386 (3)
O1—C9	1.394 (2)	C13—H13	0.9300
N1—C7	1.320 (3)	C12—C11	1.371 (3)
N1—C5	1.335 (3)	C12—H12	0.9300
O2—C14	1.358 (3)	C2—C3	1.364 (4)
O2—C15	1.426 (3)	C2—C1	1.368 (4)
N3—C6	1.322 (3)	C2—H2	0.9300
N3—C5	1.330 (3)	C15—H15A	0.9600
N2—C4	1.327 (3)	C15—H15B	0.9600
N2—C3	1.337 (3)	C15—H15C	0.9600
C4—N4	1.328 (3)	C10—C11	1.386 (3)
C4—C5	1.498 (3)	C10—H10	0.9300
N4—C1	1.338 (3)	C11—H11	0.9300
C9—C10	1.370 (3)	C3—H3	0.9300
C9—C14	1.393 (3)	C1—H1	0.9300
C8—C7	1.380 (3)

C8—O1—C9	118.03 (16)	N3—C6—C8	123.3 (2)
C7—N1—C5	115.60 (19)	N3—C6—Cl2	117.29 (17)
C14—O2—C15	117.23 (18)	C8—C6—Cl2	119.36 (17)
C6—N3—C5	116.07 (19)	C3—C2—C1	117.1 (2)
C4—N2—C3	115.4 (2)	C3—C2—H2	121.4
N2—C4—N4	127.39 (19)	C1—C2—H2	121.4
N2—C4—C5	116.39 (19)	O2—C15—H15A	109.5
N4—C4—C5	116.22 (19)	O2—C15—H15B	109.5
N3—C5—N1	126.23 (19)	H15A—C15—H15B	109.5
N3—C5—C4	117.52 (18)	O2—C15—H15C	109.5
N1—C5—C4	116.23 (19)	H15A—C15—H15C	109.5
C4—N4—C1	115.1 (2)	H15B—C15—H15C	109.5
C10—C9—C14	121.26 (19)	C9—C10—C11	119.7 (2)
C10—C9—O1	123.52 (18)	C9—C10—H10	120.1
C14—C9—O1	115.15 (18)	C11—C10—H10	120.1
O1—C8—C7	122.9 (2)	C12—C11—C10	119.8 (2)
O1—C8—C6	122.0 (2)	C12—C11—H11	120.1
C7—C8—C6	114.86 (19)	C10—C11—H11	120.1
C12—C13—C14	120.3 (2)	N2—C3—C2	122.3 (2)
C12—C13—H13	119.9	N2—C3—H3	118.8
C14—C13—H13	119.9	C2—C3—H3	118.8
O2—C14—C13	125.57 (19)	N1—C7—C8	123.9 (2)
O2—C14—C9	116.05 (18)	N1—C7—Cl1	116.80 (18)
C13—C14—C9	118.4 (2)	C8—C7—Cl1	119.30 (16)
C11—C12—C13	120.6 (2)	N4—C1—C2	122.6 (2)
C11—C12—H12	119.7	N4—C1—H1	118.7
C13—C12—H12	119.7	C2—C1—H1	118.7

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cgⁱ	0.93	2.87	3.760 (3)	161

Symmetry code: (i) x+1/2, −y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀Cl₂N₄O₂
M_r	349.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.716 (2), 8.1112 (18), 18.601 (5)
β (°)	106.486 (3)
V (Å³)	1550.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.911, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	8106, 2733, 2319
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 1.08
No. of reflections	2733
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.54

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cgⁱ	0.93	2.87	3.760 (3)	161

Symmetry code: (i) x+1/2, −y−1/2, z+1/2.

Acknowledgements

The authors gratefully acknowledge financial support provided by the National Natural Science Foundation of China (20761002), the Natural Science Foundation of Guangxi (No. 0832080) and the Innovation Project of Guangxi University for Nationlities (No. gxun-chx2010080).

References

Bly, D. D. & Mellon, M. G. (1962). J. Org. Chem. 27, 2945–2946. CrossRef CAS Google Scholar
Fabrice, P., Patr, H., Kamal, B. & Cyri, T. (2008). Inorg Chim Acta, 361, 373–379. Google Scholar
Hunziker, M. & Ludi, A. (1977). J. Am. Chem. Soc. 99, 7370–7371. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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