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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1126.
Published online 2008 May 21. doi:  10.1107/S1600536808013524
PMCID: PMC2961513

Methyl 4-(4-fluoro­phen­yl)-6-isopropyl-2-[N-methyl-N-(methylsulfonyl)amino]­pyrimidine-5-carboxyl­ate

Abstract

In the mol­ecule of the title compound, C17H20FN3O4S, the pyrimidine and benzene rings are oriented at a dihedral angle of 35.59 (3)°. Intra­molecular C—H(...)N and C—H(...)O hydrogen bonds result in the formation of one five- and two six-membered non-planar rings. One of the six-membered rings adopts a chair conformation, while the other six-membered ring and the five-membered ring exhibit envelope conformations with O and N atoms displaced by 0.837 (3) and 0.152 (3) Å, respectively from the planes of the other ring atoms. In the crystal structure, inter­molecular C—H(...)F hydrogen bonds link the mol­ecules into infinite chains.

Related literature

For ring puckering parameters, see: Cremer & Pople (1975 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1126-scheme1.jpg

Experimental

Crystal data

  • C17H20FN3O4S
  • M r = 381.42
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1126-efi1.jpg
  • a = 9.886 (2) Å
  • b = 9.988 (2) Å
  • c = 18.819 (4) Å
  • V = 1858.2 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 294 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.939, T max = 0.979
  • 3641 measured reflections
  • 3641 independent reflections
  • 2501 reflections with I > 2σ(I)
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.075
  • wR(F 2) = 0.182
  • S = 1.04
  • 3641 reflections
  • 235 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.25 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1755 Friedel pairs
  • Flack parameter: 0.14 (16)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [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: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks D, I. DOI: 10.1107/S1600536808013524/hk2456sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013524/hk2456Isup2.hkl

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

supplementary crystallographic information

Comment

Some derivatives of pyrimidine are important chemical materials. We report herein the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1), rings A (N1/N2/C4-C7) and B (C12-C17) are, of course, planar, and the dihedral angle between them is A/B = 35.59 (3)°. The intramolecular C-H···N and C-H···O hydrogen bonds (Table 1) result in the formation of one five- and two six-membered non-planar rings: C (N2/N3/C5/C11/H11A), D (S/N1/N3/C5/C10/H10B) and E (O1/C3/C4/C7/C8/H3B), respectively. Ring D adopts chair [[var phi] = -40.04 (2)° and θ = 134.72 (3)°] conformation, having total puckering amplitude, QT, of 1.188 (3) Å (Cremer & Pople, 1975). Rings C and E have envelope conformations with nitrogen and oxygen atoms displaced by 0.152 (3) Å and 0.837 (3) Å from the planes of the other ring atoms, respectively.

In the crystal structure, intermolecular C-H···F hydrogen bonds (Table 1) link the molecules into infinite chains (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, sodium salt of N-methyl methane sulphonamide (106 g, 631.00 mmol) and methyl 4-(4-fluorophenyl)-6-isopropyl- 2-methyl sulfonylpyrimidine-5-carboxylate (100 g, 284.06 mmol) were added to DMF (1000 ml) in a round bottom flask, and then stirred for 1 h at 303 K. After completion of the reaction, demineralized water (1000 ml) was added and stirred for 1 h. The mixture was filtered, washed with water, and then dried (yield; 95%). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H, 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 30% probability level. Hydrogen bonds are shown as dashed lines.
Fig. 2.
A partial packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C17H20FN3O4SF000 = 800
Mr = 381.42Dx = 1.363 Mg m3
Orthorhombic, Pna21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 25 reflections
a = 9.886 (2) Åθ = 9–13º
b = 9.988 (2) ŵ = 0.21 mm1
c = 18.819 (4) ÅT = 294 (2) K
V = 1858.2 (7) Å3Block, colorless
Z = 40.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.062
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 2.2º
T = 294(2) Kh = 0→12
ω/2θ scansk = 0→12
Absorption correction: ψ scan(North et al., 1968)l = −23→23
Tmin = 0.939, Tmax = 0.9793 standard reflections
3641 measured reflections every 120 min
3641 independent reflections intensity decay: none
2501 reflections with I > 2σ(I)

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.075  w = 1/[σ2(Fo2) + (0.070P)2 + 2.P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.182(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.23 e Å3
3641 reflectionsΔρmin = −0.25 e Å3
235 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1755 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.14 (16)
Secondary atom site location: difference Fourier map

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 > 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)

xyzUiso*/Ueq
S0.55906 (13)0.70239 (15)0.79080 (8)0.0491 (4)
O10.8512 (5)1.1302 (5)0.5173 (3)0.0717 (13)
O21.0367 (4)1.0166 (5)0.5494 (2)0.0611 (12)
O30.5199 (5)0.5777 (4)0.8218 (3)0.0728 (14)
O40.4566 (4)0.7948 (5)0.7692 (2)0.0672 (14)
N10.6898 (5)0.8871 (5)0.6925 (2)0.0463 (12)
N20.7773 (4)0.7113 (4)0.6207 (2)0.0396 (10)
N30.6541 (5)0.6626 (4)0.7201 (2)0.0424 (10)
F1.1194 (5)0.5725 (5)0.3523 (2)0.1013 (16)
C10.5763 (7)1.1558 (7)0.6613 (5)0.088 (3)
H1B0.55381.14250.61210.132*
H1C0.55981.24740.67400.132*
H1D0.52161.09820.69020.132*
C20.7657 (9)1.1427 (7)0.7496 (4)0.077 (2)
H2B0.85961.12130.75570.116*
H2C0.71191.08530.77920.116*
H2D0.75051.23440.76280.116*
C30.7266 (6)1.1227 (6)0.6731 (3)0.0476 (13)
H3B0.78201.18120.64310.057*
C40.7495 (6)0.9773 (5)0.6511 (3)0.0407 (12)
C50.7091 (5)0.7596 (6)0.6763 (3)0.0414 (12)
C60.8381 (5)0.8018 (5)0.5786 (3)0.0384 (11)
C70.8293 (5)0.9380 (5)0.5933 (3)0.0409 (12)
C80.9025 (6)1.0407 (6)0.5488 (3)0.0475 (13)
C91.1203 (7)1.0930 (8)0.5012 (4)0.082 (2)
H9A1.21301.06610.50640.123*
H9B1.11191.18660.51180.123*
H9C1.09161.07700.45320.123*
C100.6696 (6)0.7803 (7)0.8495 (3)0.0590 (17)
H10A0.62140.80670.89150.088*
H10B0.70800.85810.82720.088*
H10C0.74070.71930.86210.088*
C110.6988 (7)0.5213 (5)0.7138 (4)0.0561 (16)
H11A0.75290.51110.67170.084*
H11B0.62110.46400.71070.084*
H11C0.75150.49740.75470.084*
C120.9120 (6)0.7448 (6)0.5171 (3)0.0448 (13)
C130.9775 (6)0.6210 (6)0.5252 (3)0.0517 (14)
H13A0.97240.57620.56840.062*
C141.0499 (7)0.5646 (7)0.4695 (3)0.0630 (17)
H14A1.09740.48510.47560.076*
C151.0497 (7)0.6284 (7)0.4061 (4)0.0628 (18)
C160.9852 (7)0.7473 (7)0.3944 (3)0.0601 (17)
H16A0.98770.78780.34990.072*
C170.9152 (6)0.8071 (7)0.4507 (3)0.0534 (15)
H17A0.87090.88820.44380.064*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0363 (6)0.0583 (8)0.0528 (8)−0.0070 (7)0.0064 (7)0.0028 (8)
O10.079 (3)0.059 (3)0.077 (3)0.018 (3)0.013 (3)0.031 (2)
O20.050 (2)0.082 (3)0.051 (2)−0.014 (2)0.006 (2)0.012 (2)
O30.071 (3)0.062 (3)0.086 (3)−0.019 (2)0.018 (3)0.009 (3)
O40.039 (2)0.073 (3)0.090 (4)0.012 (2)0.006 (2)0.012 (3)
N10.045 (3)0.046 (3)0.048 (3)0.002 (2)0.004 (2)−0.003 (2)
N20.043 (2)0.031 (2)0.045 (2)0.0016 (19)−0.005 (2)−0.001 (2)
N30.048 (2)0.038 (2)0.041 (2)0.000 (2)0.002 (2)0.005 (2)
F0.117 (4)0.110 (3)0.076 (3)0.019 (3)0.038 (3)−0.036 (3)
C10.072 (5)0.048 (4)0.143 (8)0.024 (4)−0.022 (5)−0.020 (5)
C20.114 (7)0.048 (4)0.070 (4)0.011 (4)−0.024 (5)−0.012 (3)
C30.049 (3)0.040 (3)0.054 (3)−0.001 (3)0.002 (3)0.000 (3)
C40.040 (3)0.042 (3)0.040 (3)−0.001 (2)−0.001 (2)0.005 (2)
C50.033 (3)0.047 (3)0.044 (3)0.006 (2)−0.001 (2)0.007 (3)
C60.035 (3)0.043 (3)0.038 (3)0.011 (2)−0.004 (2)0.003 (2)
C70.035 (3)0.044 (3)0.044 (3)0.003 (3)−0.005 (2)0.007 (2)
C80.049 (3)0.047 (3)0.047 (3)0.002 (3)0.001 (3)0.001 (3)
C90.064 (5)0.110 (7)0.072 (5)−0.033 (5)0.014 (4)0.021 (5)
C100.056 (4)0.082 (5)0.039 (3)−0.011 (3)0.004 (3)−0.005 (3)
C110.072 (4)0.032 (3)0.064 (4)0.004 (3)0.001 (3)−0.001 (3)
C120.050 (3)0.041 (3)0.043 (3)0.008 (3)0.001 (3)−0.007 (3)
C130.053 (3)0.052 (3)0.051 (3)0.003 (3)0.007 (3)−0.003 (3)
C140.064 (4)0.066 (4)0.059 (4)0.006 (4)0.014 (3)−0.005 (3)
C150.062 (4)0.071 (4)0.055 (4)−0.003 (4)0.014 (3)−0.017 (4)
C160.067 (4)0.069 (4)0.044 (3)0.004 (4)0.012 (3)−0.003 (3)
C170.053 (4)0.064 (4)0.044 (3)0.010 (3)0.005 (3)−0.003 (3)

Geometric parameters (Å, °)

S—O31.428 (4)C4—C71.399 (7)
S—O41.429 (4)C6—C71.392 (7)
S—N31.677 (5)C6—C121.481 (7)
S—C101.738 (6)C7—C81.509 (8)
O1—C81.187 (7)C9—H9A0.9600
O2—C81.348 (7)C9—H9B0.9600
O2—C91.446 (7)C9—H9C0.9600
N1—C41.329 (7)C10—H10A0.9600
N1—C51.324 (7)C10—H10B0.9600
N2—C51.335 (7)C10—H10C0.9600
N2—C61.345 (6)C11—H11A0.9600
N3—C51.384 (7)C11—H11B0.9600
N3—C111.483 (6)C11—H11C0.9600
F—C151.346 (7)C12—C131.404 (8)
C1—C31.538 (9)C12—C171.398 (8)
C1—H1B0.9600C13—C141.389 (8)
C1—H1C0.9600C13—H13A0.9300
C1—H1D0.9600C14—C151.353 (9)
C2—C31.505 (9)C14—H14A0.9300
C2—H2B0.9600C15—C161.366 (9)
C2—H2C0.9600C16—C171.398 (8)
C2—H2D0.9600C16—H16A0.9300
C3—C41.526 (8)C17—H17A0.9300
C3—H3B0.9800
O4—S—O3119.2 (3)C4—C7—C8120.7 (5)
O4—S—N3109.0 (3)O1—C8—O2124.0 (6)
O3—S—N3105.6 (3)O1—C8—C7125.8 (6)
O4—S—C10109.7 (3)O2—C8—C7110.2 (5)
O3—S—C10107.6 (3)O2—C9—H9A109.5
N3—S—C10104.9 (3)O2—C9—H9B109.5
C8—O2—C9117.6 (5)H9A—C9—H9B109.5
C5—N1—C4117.0 (5)O2—C9—H9C109.5
C5—N2—C6116.4 (4)H9A—C9—H9C109.5
C5—N3—C11120.1 (5)H9B—C9—H9C109.5
C5—N3—S121.8 (4)S—C10—H10A109.5
C11—N3—S117.2 (4)S—C10—H10B109.5
C3—C1—H1B109.5H10A—C10—H10B109.5
C3—C1—H1C109.5S—C10—H10C109.5
H1B—C1—H1C109.5H10A—C10—H10C109.5
C3—C1—H1D109.5H10B—C10—H10C109.5
H1B—C1—H1D109.5N3—C11—H11A109.5
H1C—C1—H1D109.5N3—C11—H11B109.5
C3—C2—H2B109.5H11A—C11—H11B109.5
C3—C2—H2C109.5N3—C11—H11C109.5
H2B—C2—H2C109.5H11A—C11—H11C109.5
C3—C2—H2D109.5H11B—C11—H11C109.5
H2B—C2—H2D109.5C17—C12—C13118.6 (5)
H2C—C2—H2D109.5C17—C12—C6122.6 (5)
C2—C3—C4110.4 (5)C13—C12—C6118.8 (5)
C2—C3—C1111.0 (6)C14—C13—C12120.9 (6)
C4—C3—C1108.0 (5)C14—C13—H13A119.6
C2—C3—H3B109.1C12—C13—H13A119.6
C4—C3—H3B109.1C15—C14—C13118.3 (7)
C1—C3—H3B109.1C15—C14—H14A120.8
N1—C4—C7121.0 (5)C13—C14—H14A120.8
N1—C4—C3114.8 (5)F—C15—C14117.8 (6)
C7—C4—C3124.2 (5)F—C15—C16118.7 (6)
N1—C5—N2126.9 (5)C14—C15—C16123.5 (6)
N1—C5—N3118.7 (5)C15—C16—C17118.8 (6)
N2—C5—N3114.3 (5)C15—C16—H16A120.6
N2—C6—C7120.8 (5)C17—C16—H16A120.6
N2—C6—C12115.0 (5)C12—C17—C16119.9 (6)
C7—C6—C12124.2 (5)C12—C17—H17A120.1
C6—C7—C4117.7 (5)C16—C17—H17A120.1
C6—C7—C8121.6 (5)
O4—S—N3—C550.2 (5)C3—C4—C7—C6−178.4 (5)
O3—S—N3—C5179.3 (4)N1—C4—C7—C8−176.9 (5)
C10—S—N3—C5−67.2 (5)C3—C4—C7—C81.4 (8)
O4—S—N3—C11−141.0 (4)N2—C6—C7—C4−3.3 (7)
O3—S—N3—C11−12.0 (5)C12—C6—C7—C4176.5 (5)
C10—S—N3—C11101.5 (5)N2—C6—C7—C8176.9 (5)
C9—O2—C8—O1−8.8 (9)C12—C6—C7—C8−3.3 (8)
C9—O2—C8—C7171.1 (5)N2—C6—C12—C17143.1 (6)
C5—N1—C4—C7−0.2 (8)C7—C6—C12—C17−36.7 (8)
C5—N1—C4—C3−178.7 (5)N2—C6—C12—C13−34.7 (7)
C4—N1—C5—N2−3.3 (8)C7—C6—C12—C13145.5 (6)
C4—N1—C5—N3176.9 (5)C6—C7—C8—O1121.1 (7)
C6—N2—C5—N13.3 (8)C4—C7—C8—O1−58.6 (8)
C6—N2—C5—N3−176.9 (4)C6—C7—C8—O2−58.8 (7)
C5—N2—C6—C70.3 (7)C4—C7—C8—O2121.5 (6)
C5—N2—C6—C12−179.5 (4)C17—C12—C13—C143.2 (9)
S—N3—C5—N12.5 (7)C6—C12—C13—C14−178.9 (6)
S—N3—C5—N2−177.3 (4)C13—C12—C17—C16−1.3 (9)
C11—N3—C5—N1−165.9 (5)C6—C12—C17—C16−179.1 (6)
C11—N3—C5—N214.2 (7)C12—C13—C14—C15−3.5 (10)
C2—C3—C4—N153.8 (7)C13—C14—C15—F−179.6 (6)
C1—C3—C4—N1−67.7 (7)C13—C14—C15—C161.9 (11)
C2—C3—C4—C7−124.6 (6)C14—C15—C16—C17−0.1 (11)
C1—C3—C4—C7113.9 (7)F—C15—C16—C17−178.6 (6)
N1—C4—C7—C63.3 (8)C15—C16—C17—C12−0.2 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3B···O10.982.523.181 (8)125
C10—H10B···N10.962.563.148 (7)120
C11—H11A···N20.962.232.697 (7)109
C11—H11C···Fi0.962.343.302 (8)177

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2456).

References

  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc 97, 1354–1358.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • 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. (2003). J. Appl. Cryst.36, 7–13.

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