organic papers
o2040
Liuet al. C14H15ClN2O doi:10.1107/S1600536805017460 Acta Cryst.(2005). E61, o2040–o2041
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
4-(4-
tert
-Butylphenoxy)-2-chloropyrimidine
Wei-Min Liu, You-Quan Zhu, Yi-Feng Wang, Gong-Chun Li and Hua-Zheng Yang*
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study T= 294 K
Mean(C–C) = 0.004 A˚ Disorder in main residue Rfactor = 0.055 wRfactor = 0.134
Data-to-parameter ratio = 15.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
In the title compound, C14H15ClN2O, the benzene and pyrimidine rings are nearly perpendicular, the dihedral angle between them being 84.7 (2).
Comment
Pyrimidine derivatives are very important molecules in biology and have many applications in the areas of pesticide and pharmaceutical agents (Condonet al., 1993). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990). Pyri-midine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely used anti-AIDS drug (Gilchrist, 1997). In order to discover further biologically active pyrimidine compounds, the title compound, (I), was synthesized and its crystal structure determined (Fig. 1).
The benzene and pyrimidine rings of (I) are nearly perpendicular, the dihedral angle between them being 84.7 (2). The C3—C4—O1—C5, N1—C4—O1—C5, C10—
C5—O1—C4 and C6—C5—O1—C4 torsion angles are 6.8 (4),
174.0 (3),93.2 (3) and 91.2 (3), respectively (Table 1).
Experimental
2,4-Dichloropyrimidine (0.30 g, 2 mmol) and anhydrous potassium carbonate (0.35 g, 2.5 mmol) were mixed in acetone (20 ml). A solution of 4-tert-butylphenol (0.32 g, 2.1 mmol) in acetone (5 ml) was then added dropwise with stirring. The mixture was stirred at room temperature overnight. The solvent was then evaporated in vacuo and the residue was washed with water. The resulting light-yellow precipitate was filtered off and recrystallized from ethanol and well shaped crystals of (I) were obtained.
Crystal data
C14H15ClN2O
Mr= 262.73 Monoclinic,C2=c a= 20.692 (11) A˚
b= 12.456 (6) A˚
c= 11.792 (6) A˚
= 114.510 (8)
V= 2765 (2) A˚3
Z= 8
Dx= 1.262 Mg m
3 MoKradiation Cell parameters from 602
reflections
= 2.2–21.2
= 0.27 mm1
T= 294 (2) K Block, yellow 0.200.180.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.932,Tmax= 0.958 6731 measured reflections
2788 independent reflections 1384 reflections withI> 2(I)
Rint= 0.052
max= 26.3
h=25!25
k=9!15
l=12!14
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.055
wR(F2) = 0.134
S= 1.00 2788 reflections 182 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0558P)2 + 0.1813P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.18 e A˚
3 min=0.20 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
O1—C4 1.354 (3)
O1—C5 1.406 (3)
N2—C1 1.310 (3)
N2—C2 1.336 (3)
C2—C3 1.365 (3)
C6—C5—O1 119.5 (3) C10—C5—O1 119.7 (3)
C5—C6—C7 119.4 (3)
C1—N1—C4—O1 179.9 (2) C1—N1—C4—C3 0.7 (4) C5—O1—C4—N1 174.0 (3) C5—O1—C4—C3 6.8 (4) C2—C3—C4—O1 179.7 (3)
C4—O1—C5—C6 91.2 (3) C4—O1—C5—C10 93.2 (3) O1—C5—C6—C7 175.2 (2) O1—C5—C10—C9 174.8 (2)
The three methyl groups show positional disorder. At the final stage of the refinement, the occupancy factors of two possible sites, C12/C13/C14 and C120/C130/C140, were fixed at 0.87 and 0.13,
respectively. H atoms were placed in calculated positions and treated as riding atoms, with C—H = 0.93 A˚ (aromatic H) or 0.96 A˚ (methyl H), andUiso(H) = 1.2Ueq(C) orUiso(H) = 1.5Ueq(methyl C).
Data collection:SMART(Bruker, 1998); cell refinement:SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker 1999); software used to prepare material for publication:SHELXTL.
This work was supported by the National Key Project for Basic Research (grant No. 2003CB114400), the National Natural Science Foundation of China (grant No. 20372040) and the Research Fund for the Doctoral Programme of Higher Education.
References
Bruker (1998).SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison,
Wisconsin, USA.
Condon, M. E., Brady, T. E., Feist, D., Malefyt, T., Marc, P., Quakenbush, L. S., Rodaway, S. J., Shaner, D. L. & Tecle, B. (1993).Brighton Crop Prot. Conf. Weeds, pp. 41–46.
Maeno, S., Miura, I., Masuda, K. & Nagata, T. (1990).Brighton Crop Prot. Conf. Pests and Diseases, pp. 415–422.
Gilchrist, T. L. (1997).Heterocyclic Chemistry, 3rd ed., pp. 261–276. Singapore: Addison Wesley Longman.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
[image:2.610.310.568.78.199.2]Go¨ttingen, Germany. Figure 1
supporting information
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Acta Cryst. (2005). E61, o2040–o2041
supporting information
Acta Cryst. (2005). E61, o2040–o2041 [https://doi.org/10.1107/S1600536805017460]
4-(4-
tert
-Butylphenoxy)-2-chloropyrimidine
Wei-Min Liu, You-Quan Zhu, Yi-Feng Wang, Gong-Chun Li and Hua-Zheng Yang
4-(4-tert-Butylphenoxy)-2-chloropyrimidine
Crystal data
C14H15ClN2O
Mr = 262.73
Monoclinic, C2/c
Hall symbol: -C 2yc
a = 20.692 (11) Å
b = 12.456 (6) Å
c = 11.792 (6) Å
β = 114.510 (8)°
V = 2765 (2) Å3
Z = 8
F(000) = 1104
Dx = 1.262 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 602 reflections
θ = 2.2–21.2°
µ = 0.27 mm−1
T = 294 K
Block, yellow
0.20 × 0.18 × 0.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.932, Tmax = 0.958
6731 measured reflections 2788 independent reflections 1384 reflections with I > 2σ(I)
Rint = 0.052
θmax = 26.3°, θmin = 2.0°
h = −25→25
k = −9→15
l = −12→14
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.055
wR(F2) = 0.134
S = 1.00
2788 reflections 182 parameters 21 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0558P)2 + 0.1813P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 0.18 e Å−3 Δρmin = −0.20 e Å−3
Special details
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)
x y z Uiso*/Ueq Occ. (<1)
Cl1 0.40694 (5) 1.22543 (6) 0.25627 (7) 0.0777 (3)
O1 0.38020 (12) 0.84917 (15) 0.31959 (18) 0.0769 (7)
N1 0.39398 (12) 1.02521 (17) 0.3017 (2) 0.0529 (6)
N2 0.41741 (13) 1.14932 (17) 0.4668 (2) 0.0638 (7)
C1 0.40606 (14) 1.1210 (2) 0.3531 (3) 0.0517 (7)
C2 0.41597 (16) 1.0671 (2) 0.5384 (3) 0.0651 (8)
H2 0.4236 1.0817 0.6204 0.078*
C3 0.40400 (15) 0.9630 (2) 0.4990 (3) 0.0569 (8)
H3 0.4035 0.9072 0.5511 0.068*
C4 0.39272 (14) 0.9461 (2) 0.3766 (3) 0.0512 (7)
C5 0.37069 (18) 0.7597 (2) 0.3837 (3) 0.0564 (8)
C6 0.30387 (17) 0.7328 (2) 0.3701 (3) 0.0635 (8)
H6 0.2654 0.7764 0.3240 0.076*
C7 0.29395 (15) 0.6402 (2) 0.4257 (3) 0.0570 (8)
H7 0.2484 0.6225 0.4164 0.068*
C8 0.34992 (14) 0.5727 (2) 0.4948 (2) 0.0460 (7)
C9 0.41660 (15) 0.6037 (2) 0.5063 (3) 0.0584 (8)
H9 0.4554 0.5607 0.5523 0.070*
C10 0.42759 (16) 0.6963 (2) 0.4520 (3) 0.0636 (8)
H10 0.4731 0.7152 0.4618 0.076*
C11 0.33683 (15) 0.4698 (2) 0.5517 (2) 0.0542 (7)
C12 0.3003 (3) 0.4941 (3) 0.6372 (5) 0.1043 (15) 0.87
H12A 0.3313 0.5361 0.7067 0.157* 0.87
H12B 0.2890 0.4280 0.6669 0.157* 0.87
H12C 0.2573 0.5336 0.5920 0.157* 0.87
C13 0.4038 (2) 0.4055 (3) 0.6253 (5) 0.1038 (15) 0.87
H13A 0.4352 0.4476 0.6943 0.156* 0.87
H13B 0.4269 0.3876 0.5721 0.156* 0.87
H13C 0.3913 0.3408 0.6558 0.156* 0.87
C14 0.2884 (3) 0.3951 (3) 0.4465 (4) 0.1115 (17) 0.87
H14A 0.2446 0.4313 0.3980 0.167* 0.87
H14B 0.2787 0.3311 0.4821 0.167* 0.87
H14C 0.3118 0.3764 0.3939 0.167* 0.87
C12′ 0.3797 (12) 0.487 (2) 0.6911 (10) 0.084 (8)* 0.13
H12D 0.4294 0.4884 0.7093 0.126* 0.13
H12E 0.3703 0.4298 0.7365 0.126* 0.13
H12F 0.3664 0.5543 0.7153 0.126* 0.13
C13′ 0.3649 (14) 0.3776 (17) 0.503 (3) 0.113 (11)* 0.13
H13D 0.3445 0.3117 0.5151 0.170* 0.13
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H13F 0.3524 0.3879 0.4157 0.170* 0.13
C14′ 0.2591 (6) 0.453 (2) 0.526 (3) 0.105 (10)* 0.13
H14D 0.2553 0.3981 0.5795 0.158* 0.13
H14E 0.2332 0.4320 0.4403 0.158* 0.13
H14F 0.2398 0.5190 0.5406 0.158* 0.13
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl1 0.1021 (7) 0.0595 (5) 0.0724 (6) −0.0104 (4) 0.0370 (5) 0.0079 (4)
O1 0.131 (2) 0.0497 (12) 0.0607 (13) −0.0141 (11) 0.0507 (13) −0.0059 (10)
N1 0.0622 (16) 0.0494 (14) 0.0475 (14) −0.0061 (11) 0.0231 (12) −0.0029 (12)
N2 0.0817 (19) 0.0556 (15) 0.0615 (17) −0.0106 (12) 0.0371 (15) −0.0099 (13)
C1 0.0490 (18) 0.0523 (18) 0.055 (2) −0.0010 (13) 0.0229 (15) 0.0013 (15)
C2 0.079 (2) 0.071 (2) 0.0504 (19) −0.0125 (16) 0.0312 (17) −0.0101 (17)
C3 0.070 (2) 0.0546 (19) 0.0501 (19) −0.0068 (14) 0.0282 (16) 0.0008 (14)
C4 0.0559 (19) 0.0501 (18) 0.0497 (18) −0.0032 (13) 0.0240 (15) −0.0039 (14)
C5 0.081 (2) 0.0430 (17) 0.0503 (18) −0.0033 (16) 0.0325 (18) −0.0028 (14)
C6 0.068 (2) 0.0557 (18) 0.062 (2) 0.0172 (16) 0.0225 (17) 0.0092 (15)
C7 0.0489 (19) 0.0568 (18) 0.0633 (19) 0.0055 (14) 0.0211 (16) 0.0065 (15)
C8 0.0459 (18) 0.0483 (16) 0.0429 (16) 0.0006 (13) 0.0174 (14) −0.0081 (12)
C9 0.052 (2) 0.0579 (18) 0.0586 (19) 0.0063 (14) 0.0164 (16) 0.0029 (15)
C10 0.057 (2) 0.068 (2) 0.068 (2) −0.0131 (16) 0.0289 (18) −0.0075 (16)
C11 0.061 (2) 0.0488 (16) 0.0493 (17) 0.0046 (14) 0.0192 (16) 0.0031 (14)
C12 0.154 (5) 0.080 (3) 0.127 (4) 0.019 (3) 0.107 (4) 0.027 (3)
C13 0.094 (3) 0.084 (3) 0.128 (4) 0.027 (2) 0.041 (3) 0.052 (3)
C14 0.157 (5) 0.071 (3) 0.084 (3) −0.046 (3) 0.028 (3) −0.004 (2)
Geometric parameters (Å, º)
Cl1—C1 1.736 (3) C11—C13 1.521 (4)
O1—C4 1.354 (3) C11—C14′ 1.521 (9)
O1—C5 1.406 (3) C11—C12 1.522 (4)
N1—C1 1.315 (3) C11—C12′ 1.525 (9)
N1—C4 1.330 (3) C11—C14 1.541 (4)
N2—C1 1.310 (3) C12—H12A 0.9600
N2—C2 1.336 (3) C12—H12B 0.9600
C2—C3 1.365 (3) C12—H12C 0.9600
C2—H2 0.9300 C13—H13A 0.9600
C3—C4 1.380 (4) C13—H13B 0.9600
C3—H3 0.9300 C13—H13C 0.9600
C5—C6 1.366 (4) C14—H14A 0.9600
C5—C10 1.368 (4) C14—H14B 0.9600
C6—C7 1.383 (3) C14—H14C 0.9600
C6—H6 0.9300 C12′—H12D 0.9600
C7—C8 1.389 (4) C12′—H12E 0.9600
C7—H7 0.9300 C12′—H12F 0.9600
C8—C11 1.523 (3) C13′—H13E 0.9600
C9—C10 1.382 (4) C13′—H13F 0.9600
C9—H9 0.9300 C14′—H14D 0.9600
C10—H10 0.9300 C14′—H14E 0.9600
C11—C13′ 1.504 (9) C14′—H14F 0.9600
C4—O1—C5 118.8 (2) C14′—C11—C8 113.1 (11)
C1—N1—C4 114.8 (2) C12—C11—C8 110.6 (2)
C1—N2—C2 113.5 (2) C13′—C11—C12′ 112.1 (10)
N2—C1—N1 129.4 (2) C13—C11—C12′ 58.3 (9)
N2—C1—Cl1 115.2 (2) C14′—C11—C12′ 109.3 (9)
N1—C1—Cl1 115.4 (2) C12—C11—C12′ 59.0 (9)
N2—C2—C3 124.2 (3) C8—C11—C12′ 103.0 (10)
N2—C2—H2 117.9 C13′—C11—C14 57.1 (10)
C3—C2—H2 117.9 C13—C11—C14 106.0 (3)
C2—C3—C4 115.4 (3) C14′—C11—C14 58.4 (10)
C2—C3—H3 122.3 C12—C11—C14 108.5 (3)
C4—C3—H3 122.3 C8—C11—C14 109.2 (2)
N1—C4—O1 112.6 (2) C12′—C11—C14 147.8 (10)
N1—C4—C3 122.7 (2) C11—C12—H12A 109.5
O1—C4—C3 124.7 (2) C11—C12—H12B 109.5
C6—C5—C10 120.6 (3) C11—C12—H12C 109.5
C6—C5—O1 119.5 (3) C11—C13—H13A 109.5
C10—C5—O1 119.7 (3) C11—C13—H13B 109.5
C5—C6—C7 119.4 (3) C11—C13—H13C 109.5
C5—C6—H6 120.3 C11—C14—H14A 109.5
C7—C6—H6 120.3 C11—C14—H14B 109.5
C6—C7—C8 122.1 (3) C11—C14—H14C 109.5
C6—C7—H7 119.0 C11—C12′—H12D 109.5
C8—C7—H7 119.0 C11—C12′—H12E 109.5
C9—C8—C7 116.3 (3) H12D—C12′—H12E 109.5
C9—C8—C11 122.9 (2) C11—C12′—H12F 109.5
C7—C8—C11 120.7 (2) H12D—C12′—H12F 109.5
C10—C9—C8 122.4 (3) H12E—C12′—H12F 109.5
C10—C9—H9 118.8 C11—C13′—H13D 109.5
C8—C9—H9 118.8 C11—C13′—H13E 109.5
C5—C10—C9 119.2 (3) H13D—C13′—H13E 109.5
C5—C10—H10 120.4 C11—C13′—H13F 109.5
C9—C10—H10 120.4 H13D—C13′—H13F 109.5
C13′—C11—C13 54.0 (10) H13E—C13′—H13F 109.5
C13′—C11—C14′ 111.3 (10) C11—C14′—H14D 109.5
C13—C11—C14′ 132.8 (11) C11—C14′—H14E 109.5
C13′—C11—C12 141.5 (11) H14D—C14′—H14E 109.5
C13—C11—C12 108.2 (3) C11—C14′—H14F 109.5
C14′—C11—C12 52.1 (10) H14D—C14′—H14F 109.5
C13′—C11—C8 107.9 (11) H14E—C14′—H14F 109.5
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Acta Cryst. (2005). E61, o2040–o2041
C2—N2—C1—N1 −0.2 (4) C6—C7—C8—C11 −178.3 (2)
C2—N2—C1—Cl1 179.7 (2) C7—C8—C9—C10 −0.3 (4)
C4—N1—C1—N2 0.5 (4) C11—C8—C9—C10 178.6 (2)
C4—N1—C1—Cl1 −179.3 (2) C6—C5—C10—C9 0.7 (4)
C1—N2—C2—C3 0.1 (4) O1—C5—C10—C9 −174.8 (2)
N2—C2—C3—C4 −0.2 (4) C8—C9—C10—C5 −0.4 (4)
C1—N1—C4—O1 −179.9 (2) C9—C8—C11—C13′ −56.2 (12)
C1—N1—C4—C3 −0.7 (4) C7—C8—C11—C13′ 122.6 (12)
C5—O1—C4—N1 −174.0 (3) C9—C8—C11—C13 1.6 (4)
C5—O1—C4—C3 6.8 (4) C7—C8—C11—C13 −179.6 (3)
C2—C3—C4—N1 0.6 (4) C9—C8—C11—C14′ −179.7 (12)
C2—C3—C4—O1 179.7 (3) C7—C8—C11—C14′ −0.9 (12)
C4—O1—C5—C6 91.2 (3) C9—C8—C11—C12 123.8 (3)
C4—O1—C5—C10 −93.2 (3) C7—C8—C11—C12 −57.3 (4)
C10—C5—C6—C7 −0.4 (4) C9—C8—C11—C12′ 62.4 (10)
O1—C5—C6—C7 175.2 (2) C7—C8—C11—C12′ −118.7 (10)
C5—C6—C7—C8 −0.3 (4) C9—C8—C11—C14 −116.8 (3)
