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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o582.
Published online 2008 February 13. doi:  10.1107/S1600536808003735
PMCID: PMC2960863

2-[3-(Trifluoro­meth­yl)phen­oxy]ethyl 1-oxo-2,6,7-trioxa-1λ5-phosphabicyclo­[2.2.2]octane-4-carboxyl­ate

Abstract

In the crystal structure of the title compound, C14H14F3O7P, the central chain, which connects the phosphate bicyclic system and the benzene ring, is made up of an approximately planar C—C(O)—O—C(H2) fragment and a C(H2)—O—C(Ph) link; the mean planes make a dihedral angle of 75.9 (2)°. The F atoms are disordered over two positions; the site occupancy factors are ca 0.6 and 0.4.

Related literature

For industrial and biological applications of heterocyclic compounds involving bicyclic phosphate, see: Ratz (1966 [triangle]); Li et al., (2002 [triangle]). Many related derivatives have been prepared by Verkade & Reynolds (1960 [triangle]) and Sheng & He (2006 [triangle]). For the synthesis of the starting material, see: Chen & Jin (2000 [triangle]). For related literature, see: Nimrod et al. (1968 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o582-scheme1.jpg

Experimental

Crystal data

  • C14H14F3O7P
  • M r = 382.22
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o582-efi1.jpg
  • a = 5.7824 (3) Å
  • b = 27.5060 (16) Å
  • c = 10.2878 (6) Å
  • β = 96.738 (1)°
  • V = 1624.98 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 295 (2) K
  • 0.30 × 0.20 × 0.06 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 18233 measured reflections
  • 3547 independent reflections
  • 2332 reflections with I > 2σ(I)
  • R int = 0.091

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.137
  • S = 0.98
  • 3547 reflections
  • 254 parameters
  • 30 restraints
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT-Plus (Bruker, 2000 [triangle]); data reduction: SAINT-Plus; 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]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003735/ya2064sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003735/ya2064Isup2.hkl

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

Acknowledgments

We gratefully acknowledge financial support of this work by the National Basic Research Program of China (2003CB114400) and the National Natural Science Foundation of China (No. 20772042).

supplementary crystallographic information

Comment

Heterocyclic derivatives containing bicyclic phosphate system are important compounds with versatile industrial and biological applications (Ratz, 1966; Li et al., 2002). In continuation of our work on new biologically active heterocyclic derivatives, we report here the crystal structure of the title compound,(I) (Fig.1).Bond lengths and angles of the phosphorus-containing bicyclic cage of (I) are close to those observed previously in similar compounds (Nimrod et al., 1968; Sheng & He, 2006). The central chain of the molecule, which connects phosphate bicyclic system and benzene ring, is made up of approximately planar C4—C5—O6—C6 fragment and C7—O7—C8 link; their mean planes form dihedral angle of 75.9 (2)°.

Experimental

The solution of anhydrous 1-oxo-2,6,7-trioxa-1λ5-phospha-bicyclo[2.2.2] octane-4-carbonyl chloride (Chen & Jin, 2000) (1.14 g, 0.0055 mol) in 5 ml of acetonitrile was added dropwise under stirring to the solution of 2-(3-trifluoromethylphenoxy)ethanol (1.03 g, 0.005 mol) and triethylamine (0.61 g, 0.006 mol) in 25 ml of acetonitrile. The stirring was continued for about 3 h. Then, the solvent was removed under reduced pressure and the residue was washed with water (20 ml). The raw product was recrystallized from acetonitrile, yielding the title compound as a white solid with 81% yield. Colourless crystals of (I) suitable for X-ray structure analysis were grown from the mixture of dichloromethane and n-hexane (v/v, 1:8).

Refinement

It was apparent at an early stage, that the CF3 group showed rotational disorder, and two alternative positions were revealed for each of the F atoms. Refinement of the s.o.f.'s for the F atoms indicated noticeable differences in occupancies of each of the two orientations of the CF3 group [0.59 (2) versus. 0.41 (2)]. The C—F bond distances were restrained during the refinement using the SADI command (SHELXL97; Sheldrick, 2008). H atoms were included in the refinement in riding model approximation with C—H = 0.93 Å for aromatic and 0.97 Å for all other H atoms; Uiso(H) = 1.2Ueq of the carrier C atom.

Figures

Fig. 1.
The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme; the minor component of the CF3 group disorder is omitted. H atoms are shown as small spheres of arbitrary radius.
Fig. 2.
Packing diagram for (I).
Fig. 3.
The formation of the title compound, (I).

Crystal data

C14H14F3O7PF000 = 784
Mr = 382.22Dx = 1.562 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4355 reflections
a = 5.7824 (3) Åθ = 2.4–19.3º
b = 27.5060 (16) ŵ = 0.24 mm1
c = 10.2878 (6) ÅT = 295 (2) K
β = 96.738 (1)ºPlate, colourless
V = 1624.98 (16) Å30.30 × 0.20 × 0.06 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2332 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.091
Monochromator: graphiteθmax = 27.0º
T = 295(2) Kθmin = 1.5º
[var phi] and ω scansh = −7→7
Absorption correction: nonek = −35→35
18233 measured reflectionsl = −13→11
3547 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.137  w = 1/[σ2(Fo2) + (0.0771P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
3547 reflectionsΔρmax = 0.27 e Å3
254 parametersΔρmin = −0.22 e Å3
30 restraintsExtinction correction: none
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*/UeqOcc. (<1)
C10.3969 (4)0.14250 (8)0.3106 (2)0.0518 (6)
H1A0.53000.13560.37440.062*
H1B0.30310.11330.29850.062*
C20.4076 (4)0.22884 (9)0.3762 (2)0.0502 (6)
H2A0.32540.25520.41340.060*
H2B0.54730.22180.43500.060*
C30.0422 (4)0.19358 (11)0.2599 (2)0.0579 (7)
H3A−0.05850.16530.25230.069*
H3B−0.04590.22070.28860.069*
C40.2525 (3)0.18376 (8)0.3603 (2)0.0405 (5)
C50.1682 (4)0.16870 (8)0.4885 (2)0.0479 (6)
C60.2903 (5)0.15256 (10)0.7125 (2)0.0630 (7)
H6A0.19080.12410.70300.076*
H6B0.21080.17780.75590.076*
C70.5158 (5)0.14044 (9)0.7905 (2)0.0602 (7)
H7A0.62660.16660.78530.072*
H7B0.49380.13560.88170.072*
C80.8002 (4)0.07776 (9)0.7983 (2)0.0497 (6)
C90.8907 (5)0.03932 (9)0.7345 (2)0.0567 (7)
H90.81380.02810.65570.068*
C101.0948 (5)0.01744 (10)0.7873 (3)0.0665 (8)
C111.2075 (6)0.03407 (13)0.9055 (3)0.0844 (9)
H111.34520.01950.94180.101*
C121.1166 (6)0.07149 (13)0.9678 (3)0.0832 (9)
H121.19330.08241.04690.100*
C130.9127 (5)0.09386 (10)0.9166 (2)0.0657 (7)
H130.85160.11940.96100.079*
C141.1925 (6)−0.02293 (13)0.7178 (4)0.0947 (11)
F11.0315 (9)−0.0476 (3)0.6324 (13)0.136 (3)0.591 (16)
F21.3280 (17)−0.0092 (4)0.6315 (8)0.136 (4)0.591 (16)
F31.295 (3)−0.0570 (4)0.7881 (7)0.202 (7)0.591 (16)
F1'1.0849 (18)−0.0629 (3)0.7297 (14)0.115 (5)0.409 (16)
F2'1.4149 (10)−0.0324 (4)0.7722 (12)0.113 (4)0.409 (16)
F3'1.218 (3)−0.0137 (5)0.5991 (8)0.135 (6)0.409 (16)
O10.4623 (3)0.22048 (7)0.00883 (16)0.0676 (5)
O20.4701 (3)0.24307 (6)0.24834 (15)0.0583 (5)
O30.4763 (3)0.15669 (6)0.18650 (16)0.0570 (5)
O40.1178 (3)0.20463 (7)0.13298 (16)0.0661 (5)
O5−0.0280 (3)0.15716 (8)0.49924 (19)0.0766 (6)
O60.3411 (3)0.16937 (6)0.58442 (16)0.0580 (5)
O70.5992 (3)0.09700 (6)0.73729 (15)0.0592 (5)
P10.38795 (10)0.20768 (2)0.13331 (6)0.0473 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0521 (14)0.0443 (13)0.0594 (15)0.0020 (10)0.0080 (11)−0.0002 (11)
C20.0553 (15)0.0499 (13)0.0472 (14)−0.0098 (11)0.0134 (11)−0.0049 (11)
C30.0347 (13)0.0757 (17)0.0628 (16)0.0004 (11)0.0039 (11)0.0092 (13)
C40.0319 (11)0.0415 (12)0.0478 (13)−0.0008 (9)0.0041 (9)−0.0008 (9)
C50.0428 (13)0.0444 (13)0.0577 (15)−0.0006 (10)0.0116 (12)0.0022 (11)
C60.0696 (18)0.0645 (16)0.0583 (16)0.0197 (13)0.0215 (13)0.0145 (13)
C70.0821 (19)0.0515 (14)0.0485 (14)0.0154 (13)0.0141 (13)−0.0017 (11)
C80.0545 (14)0.0476 (13)0.0467 (13)0.0021 (11)0.0042 (11)0.0045 (11)
C90.0610 (16)0.0507 (14)0.0583 (16)−0.0001 (12)0.0065 (13)−0.0031 (12)
C100.0608 (17)0.0529 (15)0.086 (2)0.0086 (13)0.0088 (16)0.0105 (14)
C110.070 (2)0.086 (2)0.092 (2)0.0152 (17)−0.0144 (18)0.018 (2)
C120.085 (2)0.089 (2)0.0686 (19)−0.0008 (18)−0.0211 (17)0.0045 (17)
C130.083 (2)0.0616 (16)0.0499 (15)0.0021 (14)−0.0007 (14)−0.0002 (12)
C140.085 (3)0.079 (3)0.120 (3)0.024 (2)0.012 (3)−0.001 (2)
F10.126 (4)0.084 (4)0.202 (9)0.010 (3)0.037 (5)−0.061 (5)
F20.108 (5)0.159 (6)0.151 (8)−0.032 (5)0.055 (5)−0.069 (6)
F30.268 (16)0.152 (9)0.190 (7)0.147 (11)0.042 (9)0.040 (6)
F1'0.123 (6)0.066 (5)0.163 (11)−0.031 (4)0.044 (7)−0.051 (6)
F2'0.062 (4)0.092 (5)0.178 (10)0.033 (3)−0.018 (4)−0.038 (5)
F3'0.165 (12)0.141 (11)0.099 (5)0.060 (10)0.018 (7)−0.018 (6)
O10.0735 (13)0.0802 (13)0.0510 (11)−0.0054 (10)0.0153 (9)0.0008 (9)
O20.0748 (12)0.0507 (9)0.0518 (10)−0.0220 (8)0.0168 (8)−0.0027 (8)
O30.0627 (11)0.0535 (10)0.0572 (11)0.0088 (8)0.0178 (8)−0.0041 (8)
O40.0411 (10)0.1008 (14)0.0544 (11)0.0014 (9)−0.0035 (8)0.0136 (9)
O50.0527 (11)0.0998 (15)0.0798 (14)−0.0187 (10)0.0189 (10)0.0094 (11)
O60.0479 (10)0.0716 (11)0.0551 (10)0.0023 (8)0.0082 (8)0.0188 (9)
O70.0657 (11)0.0579 (10)0.0524 (10)0.0154 (8)−0.0006 (8)−0.0095 (8)
P10.0443 (4)0.0516 (4)0.0460 (4)−0.0027 (3)0.0054 (3)−0.0017 (3)

Geometric parameters (Å, °)

C1—O31.460 (3)C8—O71.361 (3)
C1—C41.532 (3)C8—C91.380 (3)
C1—H1A0.9700C8—C131.384 (3)
C1—H1B0.9700C9—C101.378 (4)
C2—O21.458 (2)C9—H90.9300
C2—C41.528 (3)C10—C111.388 (4)
C2—H2A0.9700C10—C141.469 (5)
C2—H2B0.9700C11—C121.351 (5)
C3—O41.457 (3)C11—H110.9300
C3—C41.525 (3)C12—C131.378 (4)
C3—H3A0.9700C12—H120.9300
C3—H3B0.9700C13—H130.9300
C4—C51.516 (3)C14—F3'1.274 (7)
C5—O51.196 (3)C14—F1'1.277 (6)
C5—O61.320 (3)C14—F31.284 (5)
C6—O61.459 (3)C14—F21.307 (6)
C6—C71.487 (3)C14—F2'1.366 (6)
C6—H6A0.9700C14—F11.382 (6)
C6—H6B0.9700O1—P11.4416 (18)
C7—O71.422 (3)O2—P11.5625 (16)
C7—H7A0.9700O3—P11.5689 (17)
C7—H7B0.9700O4—P11.5642 (18)
O3—C1—C4109.50 (18)C9—C10—C11119.6 (3)
O3—C1—H1A109.8C9—C10—C14119.9 (3)
C4—C1—H1A109.8C11—C10—C14120.5 (3)
O3—C1—H1B109.8C12—C11—C10119.9 (3)
C4—C1—H1B109.8C12—C11—H11120.1
H1A—C1—H1B108.2C10—C11—H11120.1
O2—C2—C4109.03 (16)C11—C12—C13121.5 (3)
O2—C2—H2A109.9C11—C12—H12119.3
C4—C2—H2A109.9C13—C12—H12119.3
O2—C2—H2B109.9C12—C13—C8119.1 (3)
C4—C2—H2B109.9C12—C13—H13120.5
H2A—C2—H2B108.3C8—C13—H13120.5
O4—C3—C4110.18 (18)F3'—C14—F1'112.2 (6)
O4—C3—H3A109.6F3'—C14—F3125.9 (8)
C4—C3—H3A109.6F1'—C14—F361.0 (5)
O4—C3—H3B109.6F3'—C14—F231.0 (6)
C4—C3—H3B109.6F1'—C14—F2130.6 (7)
H3A—C3—H3B108.1F3—C14—F2108.7 (5)
C5—C4—C3108.98 (18)F3'—C14—F2'102.7 (6)
C5—C4—C2111.94 (18)F1'—C14—F2'104.0 (5)
C3—C4—C2109.88 (19)F3—C14—F2'44.0 (5)
C5—C4—C1109.37 (18)F2—C14—F2'73.9 (5)
C3—C4—C1109.12 (19)F3'—C14—F168.6 (6)
C2—C4—C1107.51 (18)F1'—C14—F148.5 (4)
O5—C5—O6125.3 (2)F3—C14—F1103.3 (5)
O5—C5—C4124.0 (2)F2—C14—F197.1 (5)
O6—C5—C4110.72 (18)F2'—C14—F1134.3 (5)
O6—C6—C7107.6 (2)F3'—C14—C10114.3 (6)
O6—C6—H6A110.2F1'—C14—C10112.7 (4)
C7—C6—H6A110.2F3—C14—C10117.1 (5)
O6—C6—H6B110.2F2—C14—C10114.0 (5)
C7—C6—H6B110.2F2'—C14—C10110.0 (5)
H6A—C6—H6B108.5F1—C14—C10114.4 (3)
O7—C7—C6107.2 (2)C2—O2—P1115.51 (13)
O7—C7—H7A110.3C1—O3—P1114.91 (13)
C6—C7—H7A110.3C3—O4—P1114.44 (13)
O7—C7—H7B110.3C5—O6—C6117.12 (18)
C6—C7—H7B110.3C8—O7—C7117.31 (18)
H7A—C7—H7B108.5O1—P1—O2115.14 (10)
O7—C8—C9115.4 (2)O1—P1—O4114.40 (10)
O7—C8—C13124.7 (2)O2—P1—O4104.46 (10)
C9—C8—C13119.9 (2)O1—P1—O3114.17 (10)
C10—C9—C8120.1 (2)O2—P1—O3103.61 (9)
C10—C9—H9119.9O4—P1—O3103.71 (10)
C8—C9—H9119.9
O4—C3—C4—C5−175.80 (19)C9—C10—C14—F1'−76.8 (9)
O4—C3—C4—C261.2 (3)C11—C10—C14—F1'103.7 (9)
O4—C3—C4—C1−56.4 (3)C9—C10—C14—F3−144.7 (10)
O2—C2—C4—C5−176.43 (17)C11—C10—C14—F335.8 (11)
O2—C2—C4—C3−55.2 (2)C9—C10—C14—F286.9 (7)
O2—C2—C4—C163.4 (2)C11—C10—C14—F2−92.6 (7)
O3—C1—C4—C5179.40 (17)C9—C10—C14—F2'167.6 (7)
O3—C1—C4—C360.3 (2)C11—C10—C14—F2'−11.9 (8)
O3—C1—C4—C2−58.9 (2)C9—C10—C14—F1−23.6 (8)
C3—C4—C5—O513.7 (3)C11—C10—C14—F1156.9 (7)
C2—C4—C5—O5135.5 (2)C4—C2—O2—P1−5.5 (2)
C1—C4—C5—O5−105.5 (3)C4—C1—O3—P1−2.6 (2)
C3—C4—C5—O6−167.4 (2)C4—C3—O4—P1−4.5 (3)
C2—C4—C5—O6−45.6 (3)O5—C5—O6—C62.9 (4)
C1—C4—C5—O673.4 (2)C4—C5—O6—C6−175.99 (19)
O6—C6—C7—O7−71.8 (3)C7—C6—O6—C5161.0 (2)
O7—C8—C9—C10179.5 (2)C9—C8—O7—C7−172.2 (2)
C13—C8—C9—C10−1.0 (4)C13—C8—O7—C78.4 (4)
C8—C9—C10—C110.5 (4)C6—C7—O7—C8−176.9 (2)
C8—C9—C10—C14−179.0 (3)C2—O2—P1—O1−176.46 (15)
C9—C10—C11—C120.0 (5)C2—O2—P1—O457.23 (18)
C14—C10—C11—C12179.5 (3)C2—O2—P1—O3−51.09 (18)
C10—C11—C12—C130.0 (5)C3—O4—P1—O1−177.70 (18)
C11—C12—C13—C8−0.5 (5)C3—O4—P1—O2−50.93 (19)
O7—C8—C13—C12−179.5 (3)C3—O4—P1—O357.31 (19)
C9—C8—C13—C121.0 (4)C1—O3—P1—O1−178.26 (15)
C9—C10—C14—F3'52.8 (10)C1—O3—P1—O255.75 (17)
C11—C10—C14—F3'−126.7 (10)C1—O3—P1—O4−53.13 (17)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2064).

References

  • Bruker (2000). SMART) and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, W. Q. & Jin, G. Y. (2000). J. Chin. Appl. Chem.Vol? 479–480.
  • Li, X., Ou, Y. X. & Zhang, Y. H. (2002). Chem. J. Chin. Univ.23, 695–699.
  • Nimrod, D. M., Fitzwater, D. R. & Verkade, J. G. (1968). J. Am. Chem. Soc.90, 2780–2784.
  • Ratz, R. F. W. (1966). US Patent No. 3 287 448.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sheng, X. J. & He, H. W. (2006). Acta Cryst E62, o4398–o4399.
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Verkade, J. G. & Reynolds, L. J. (1960). J. Org. Chem.25, 663–667.

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