organic compounds
4,6-Dichloro-5-(2-methoxyphenoxy)-2,2′-bipyrimidine
aDepartment of Chemistry, Guangxi University for Nationalities, Nanning 530006, People's Republic of China
*Correspondence e-mail: shizhanwang2010@yahoo.cn
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
|
Refinement
|
Data collection: SMART (Siemens, 1996); cell 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
10.1107/S160053681101419X/fl2331sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681101419X/fl2331Isup2.hkl
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.
Data collection-2102 independent reflections but 2101 in
H atoms on C atoms were positoned geometrically and refined using a riding model with C—H = 0.96Å and Uiso(H) = 1.2Ueq(C).Data collection: SMART (Siemens, 1996); cell
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).C15H10Cl2N4O2 | F(000) = 712 |
Mr = 349.17 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 2733 independent reflections |
Radiation source: fine-focus sealed tube | 2319 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.911, Tmax = 0.926 | k = −9→9 |
8106 measured reflections | l = −22→16 |
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(Fo2) + (0.0522P)2 + 0.7172P] where P = (Fo2 + 2Fc2)/3 |
2733 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C15H10Cl2N4O2 | V = 1550.3 (6) Å3 |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 2733 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2319 reflections with I > 2σ(I) |
Tmin = 0.911, Tmax = 0.926 | Rint = 0.027 |
8106 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.26 e Å−3 |
2733 reflections | Δρmin = −0.54 e Å−3 |
209 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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 |
Mr | 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) |
Tmin, Tmax | 0.911, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8106, 2733, 2319 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.26, −0.54 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.