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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2117.
Published online 2009 August 8. doi:  10.1107/S1600536809030736
PMCID: PMC2970010

Methyl 2-[2-(6-chloro­pyrimidin-4-yl­oxy)phen­yl]-3,3-dimethoxy­propanoate

Abstract

In the title compound, C16H17ClN2O5, the dihedral angle between the aromatic rings is 77.36 (4)°. An intra­molecular C—H(...)O inter­action results in the formation of a planar [r.m.s. deviation = 0.103 (2) Å] five-membered ring, which is oriented at a dihedral angle of 4.84 (4)° with respect to the adjacent benzene ring. In the crystal structure, weak intermolecular C—H(...)π inter­actions are found.

Related literature

For a related structure, see: Bowden & Brown (1996 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2117-scheme1.jpg

Experimental

Crystal data

  • C16H17ClN2O5
  • M r = 352.77
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2117-efi1.jpg
  • a = 9.5030 (19) Å
  • b = 10.051 (2) Å
  • c = 11.162 (2) Å
  • α = 101.24 (3)°
  • β = 108.47 (3)°
  • γ = 113.42 (3)°
  • V = 862.6 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 294 K
  • 0.20 × 0.20 × 0.05 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.952, T max = 0.988
  • 3346 measured reflections
  • 3140 independent reflections
  • 1427 reflections with I > 2σ(I)
  • R int = 0.035
  • 3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.078
  • wR(F 2) = 0.173
  • S = 1.07
  • 3140 reflections
  • 211 parameters
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.45 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030736/hk2749sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030736/hk2749Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound can be used as an intermediate in the preparation of azoxystrobin, which is an important fungicide (Bowden & Brown, 1996). We report herein the crystal structure of the title compound, which is of interest to us in the field.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C7-C12) and B (N1/N2/C13-C16) are, of course, planar and the dihedral angle between them is A/B = 77.36 (4)°. Intramolecular C-H···O interaction (Table 1) results in the formation of a planar five-membered ring C (O5/C6-C8/H6A), which is oriented with respect to the adjacent ring A at a dihedral angle of A/C = 4.84 (4)°.

In the crystal structure, weak C—H···π interactions (Table 1) are found.

Experimental

The title compound was prepared acording to a literature method (Bowden & Brown, 1996). Crystals suitable for X-ray analysis were obtained by dissolving the title compound in methanol and evaporating the solvent slowly at room temperature for 8 d.

Refinement

H atoms were positioned geometrically with C-H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.

Crystal data

C16H17ClN2O5Z = 2
Mr = 352.77F(000) = 368
Triclinic, P1Dx = 1.358 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.5030 (19) ÅCell parameters from 25 reflections
b = 10.051 (2) Åθ = 9–12°
c = 11.162 (2) ŵ = 0.25 mm1
α = 101.24 (3)°T = 294 K
β = 108.47 (3)°Needle, colorless
γ = 113.42 (3)°0.20 × 0.20 × 0.05 mm
V = 862.6 (5) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer1427 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
graphiteθmax = 25.3°, θmin = 2.1°
ω/2θ scansh = 0→11
Absorption correction: ψ scan (North et al., 1968)k = −12→11
Tmin = 0.952, Tmax = 0.988l = −13→12
3346 measured reflections3 standard reflections every 120 min
3140 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.173w = 1/[σ2(Fo2) + (0.060P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
3140 reflectionsΔρmax = 0.43 e Å3
211 parametersΔρmin = −0.45 e Å3
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
Cl0.16863 (16)0.54848 (17)0.23573 (15)0.0918 (5)
O1−0.7131 (4)0.4178 (4)−0.3468 (3)0.0806 (10)
O2−0.6406 (5)0.2829 (5)−0.4869 (4)0.1119 (14)
O3−0.5192 (5)0.0798 (5)−0.3027 (4)0.1150 (14)
O4−0.7857 (7)−0.0410 (6)−0.4408 (5)0.1371 (18)
O5−0.4458 (3)0.3794 (3)−0.0203 (3)0.0658 (9)
N1−0.3799 (5)0.1982 (4)0.0434 (4)0.0631 (11)
N2−0.0880 (5)0.2702 (5)0.1614 (4)0.0727 (11)
C1−0.8435 (9)0.4438 (9)−0.4217 (6)0.131 (3)
H1B−0.82310.5446−0.37300.196*
H1C−0.95170.3648−0.43450.196*
H1D−0.84430.4398−0.50860.196*
C2−0.6907 (10)0.2967 (8)−0.6060 (6)0.140 (3)
H2B−0.61240.2972−0.64320.210*
H2C−0.69380.3925−0.59500.210*
H2D−0.80260.2105−0.66640.210*
C3−0.7194 (7)0.2788 (5)−0.4025 (5)0.0710 (14)
H3A−0.84000.2004−0.45780.085*
C4−0.5126 (8)−0.0639 (7)−0.3384 (6)0.1142 (16)
H4A−0.3983−0.0432−0.28960.171*
H4B−0.5469−0.1044−0.43430.171*
H4C−0.5883−0.1389−0.31480.171*
C5−0.6598 (11)0.0736 (9)−0.3573 (8)0.1142 (16)
C6−0.6513 (6)0.2253 (6)−0.2981 (5)0.0688 (13)
H6A−0.52980.3025−0.24600.083*
C7−0.7250 (6)0.2132 (5)−0.1948 (5)0.0517 (11)
C8−0.6183 (5)0.2823 (4)−0.0593 (5)0.0464 (10)
C9−0.6753 (6)0.2753 (5)0.0390 (5)0.0609 (13)
H9A−0.59860.32590.13050.073*
C10−0.8481 (7)0.1921 (6)0.0000 (6)0.0699 (14)
H10A−0.88840.18500.06560.084*
C11−0.9602 (6)0.1202 (6)−0.1340 (7)0.0793 (16)
H11A−1.07700.0644−0.16070.095*
C12−0.8968 (6)0.1316 (5)−0.2302 (5)0.0691 (14)
H12A−0.97320.0823−0.32180.083*
C13−0.3283 (6)0.3428 (5)0.0417 (4)0.0536 (11)
C14−0.2533 (6)0.1731 (5)0.1042 (5)0.0720 (14)
H14A−0.28580.07370.10680.086*
C15−0.0453 (6)0.4133 (5)0.1578 (4)0.0586 (12)
C16−0.1620 (5)0.4550 (5)0.0963 (4)0.0575 (12)
H16A−0.12950.55380.09230.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0588 (8)0.0939 (11)0.1023 (11)0.0264 (7)0.0267 (8)0.0357 (8)
O10.104 (3)0.067 (2)0.066 (2)0.047 (2)0.023 (2)0.0268 (18)
O20.161 (4)0.177 (4)0.075 (3)0.115 (3)0.076 (3)0.085 (3)
O30.118 (3)0.119 (3)0.127 (3)0.084 (3)0.050 (3)0.033 (3)
O40.137 (4)0.122 (3)0.136 (4)0.083 (3)0.037 (3)0.013 (3)
O50.0501 (19)0.0528 (18)0.097 (2)0.0245 (16)0.0248 (17)0.0461 (18)
N10.065 (2)0.042 (2)0.092 (3)0.0293 (19)0.037 (2)0.035 (2)
N20.064 (3)0.073 (3)0.099 (3)0.039 (2)0.039 (2)0.050 (3)
C10.169 (7)0.195 (7)0.096 (5)0.143 (6)0.064 (5)0.062 (5)
C20.239 (9)0.150 (6)0.093 (5)0.133 (6)0.082 (6)0.067 (5)
C30.100 (4)0.053 (3)0.064 (3)0.036 (3)0.039 (3)0.028 (3)
C40.127 (4)0.126 (4)0.125 (4)0.092 (3)0.056 (3)0.047 (3)
C50.127 (4)0.126 (4)0.125 (4)0.092 (3)0.056 (3)0.047 (3)
C60.084 (3)0.078 (3)0.058 (3)0.046 (3)0.034 (3)0.032 (2)
C70.059 (3)0.044 (2)0.060 (3)0.029 (2)0.027 (3)0.027 (2)
C80.051 (3)0.038 (2)0.057 (3)0.027 (2)0.020 (3)0.025 (2)
C90.090 (4)0.045 (3)0.053 (3)0.037 (3)0.030 (3)0.024 (2)
C100.085 (4)0.061 (3)0.104 (5)0.044 (3)0.063 (4)0.053 (3)
C110.048 (3)0.063 (3)0.120 (5)0.021 (3)0.032 (4)0.044 (4)
C120.068 (4)0.054 (3)0.065 (3)0.023 (3)0.019 (3)0.014 (3)
C130.062 (3)0.048 (3)0.062 (3)0.032 (2)0.031 (2)0.025 (2)
C140.068 (3)0.053 (3)0.113 (4)0.039 (3)0.041 (3)0.044 (3)
C150.062 (3)0.059 (3)0.060 (3)0.025 (3)0.036 (3)0.027 (2)
C160.053 (3)0.048 (3)0.068 (3)0.021 (2)0.027 (3)0.026 (2)

Geometric parameters (Å, °)

Cl—C151.720 (5)C3—H3A0.9800
O1—C11.410 (6)C4—H4A0.9600
O1—C31.383 (5)C4—H4B0.9600
O2—C21.318 (6)C4—H4C0.9600
O2—C31.373 (5)C5—C61.498 (8)
O3—C41.453 (6)C6—C71.528 (6)
O3—C51.250 (7)C6—H6A0.9800
O4—C51.186 (8)C7—C81.363 (5)
O5—C81.393 (4)C7—C121.376 (6)
O5—C131.341 (5)C8—C91.370 (6)
N1—C131.343 (5)C9—C101.378 (6)
N1—C141.327 (5)C9—H9A0.9300
N2—C141.316 (5)C10—C111.361 (7)
N2—C151.343 (5)C10—H10A0.9300
C1—H1B0.9600C11—C121.390 (7)
C1—H1C0.9600C11—H11A0.9300
C1—H1D0.9600C12—H12A0.9300
C2—H2B0.9600C13—C161.359 (5)
C2—H2C0.9600C14—H14A0.9300
C2—H2D0.9600C15—C161.370 (5)
C3—C61.452 (6)C16—H16A0.9300
C3—O1—C1117.8 (4)C5—C6—C7108.8 (4)
C2—O2—C3126.5 (5)C3—C6—H6A106.1
C5—O3—C4117.8 (5)C5—C6—H6A106.1
C13—O5—C8121.1 (3)C7—C6—H6A106.1
C14—N1—C13114.1 (4)C8—C7—C12116.5 (4)
C14—N2—C15114.3 (4)C8—C7—C6119.9 (4)
O1—C1—H1B109.5C12—C7—C6123.6 (4)
O1—C1—H1C109.5C7—C8—C9123.0 (4)
H1B—C1—H1C109.5C7—C8—O5117.6 (4)
O1—C1—H1D109.5C9—C8—O5118.9 (4)
H1B—C1—H1D109.5C8—C9—C10118.9 (4)
H1C—C1—H1D109.5C8—C9—H9A120.5
O2—C2—H2B109.5C10—C9—H9A120.5
O2—C2—H2C109.5C11—C10—C9120.4 (5)
H2B—C2—H2C109.5C11—C10—H10A119.8
O2—C2—H2D109.5C9—C10—H10A119.8
H2B—C2—H2D109.5C10—C11—C12118.7 (5)
H2C—C2—H2D109.5C10—C11—H11A120.6
O2—C3—O1114.2 (4)C12—C11—H11A120.6
O2—C3—C6109.9 (4)C7—C12—C11122.4 (5)
O1—C3—C6111.5 (4)C7—C12—H12A118.8
O2—C3—H3A107.0C11—C12—H12A118.8
O1—C3—H3A107.0O5—C13—N1119.0 (4)
C6—C3—H3A107.0O5—C13—C16117.2 (4)
O3—C4—H4A109.5N1—C13—C16123.9 (4)
O3—C4—H4B109.5N2—C14—N1128.5 (4)
H4A—C4—H4B109.5N2—C14—H14A115.7
O3—C4—H4C109.5N1—C14—H14A115.7
H4A—C4—H4C109.5N2—C15—C16123.5 (4)
H4B—C4—H4C109.5N2—C15—Cl116.9 (4)
O4—C5—O3123.8 (7)C16—C15—Cl119.6 (4)
O4—C5—C6124.5 (7)C13—C16—C15115.6 (4)
O3—C5—C6111.6 (7)C13—C16—H16A122.2
C3—C6—C5112.0 (5)C15—C16—H16A122.2
C3—C6—C7117.1 (4)
C2—O2—C3—O1−67.6 (7)C13—O5—C8—C7−114.9 (4)
C2—O2—C3—C6166.3 (6)C13—O5—C8—C972.8 (5)
C1—O1—C3—O287.6 (6)C7—C8—C9—C101.4 (6)
C1—O1—C3—C6−147.2 (5)O5—C8—C9—C10173.3 (3)
C4—O3—C5—O4−3.6 (11)C8—C9—C10—C11−1.0 (6)
C4—O3—C5—C6173.0 (5)C9—C10—C11—C120.4 (7)
O2—C3—C6—C5−53.2 (6)C8—C7—C12—C110.5 (6)
O1—C3—C6—C5179.1 (5)C6—C7—C12—C11178.8 (4)
O2—C3—C6—C7−179.9 (4)C10—C11—C12—C7−0.1 (7)
O1—C3—C6—C752.5 (6)C8—O5—C13—N112.4 (6)
O4—C5—C6—C3−54.2 (10)C8—O5—C13—C16−169.3 (4)
O3—C5—C6—C3129.3 (6)C14—N1—C13—O5178.4 (4)
O4—C5—C6—C776.8 (8)C14—N1—C13—C160.2 (6)
O3—C5—C6—C7−99.7 (6)C15—N2—C14—N10.9 (8)
C3—C6—C7—C8−128.5 (4)C13—N1—C14—N20.0 (8)
C5—C6—C7—C8103.3 (5)C14—N2—C15—C16−2.0 (7)
C3—C6—C7—C1253.2 (6)C14—N2—C15—Cl177.9 (4)
C5—C6—C7—C12−75.0 (6)O5—C13—C16—C15−179.4 (4)
C12—C7—C8—C9−1.1 (6)N1—C13—C16—C15−1.2 (7)
C6—C7—C8—C9−179.5 (4)N2—C15—C16—C132.2 (7)
C12—C7—C8—O5−173.1 (3)Cl—C15—C16—C13−177.7 (3)
C6—C7—C8—O58.4 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O50.982.252.777 (6)113
C1—H1B···Cg2i0.962.973.696 (5)134
C16—H16A···Cg1i0.932.853.661 (4)146

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2749).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bowden, M. C. & Brown, S. M. (1996). UK Patent Appl. GB2291874.
  • Enraf–Nonius (1985). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography