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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o99.
Published online 2009 December 12. doi:  10.1107/S160053680905260X
PMCID: PMC2980027

Bis(propan-2-yl) [(1S)-1-(4-fluoro­phen­yl)-1-hydr­oxy-2-nitro­ethyl]phospho­nate

Abstract

In the title compound, C14H21FNO6P, a staggered conformation about the central P—C bond occurs, with the oxo and hydroxyl groups occupying diagonally opposite positions. The crystal structure features supra­molecular chains mediated by O—H(...)O hydrogen bonds, which propagate in the a-axis direction. A C—H(...)O inter­action consolidates the chains. Disorder was resolved for one of the isopropyl groups with a 0.60 (2):0.40 (2) occupancy ratio for the two components.

Related literature

For background to the enanti­oselective nitro­aldol reaction of α-ketophospho­nates and nitro­methane and for the synthesis, see: Mandal et al. (2007 [triangle]).

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Object name is e-66-00o99-scheme1.jpg

Experimental

Crystal data

  • C14H21FNO6P
  • M r = 349.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o99-efi1.jpg
  • a = 5.8267 (12) Å
  • b = 15.931 (3) Å
  • c = 18.273 (4) Å
  • V = 1696.2 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 173 K
  • 0.31 × 0.15 × 0.06 mm

Data collection

  • Rigaku AFC12/SATURN724 diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.790, T max = 1
  • 6049 measured reflections
  • 3391 independent reflections
  • 3248 reflections with I > 2σ(I)
  • R int = 0.027
  • Standard reflections: 0

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.117
  • S = 1.04
  • 3391 reflections
  • 211 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.43 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1354 Friedel pairs
  • Flack parameter: −0.11 (13)

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680905260X/hb5270sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905260X/hb5270Isup2.hkl

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

Acknowledgments

CGZ thanks the Welch Foundation (grant No. AX-1593) and the NIH-MBRS program (S06 GM08194) for support.

supplementary crystallographic information

Comment

In connection with previous studies on the enantioselective nitroaldol reaction of α-ketophosphonates and nitromethane for the synthesis of optically active α-hydroxy-β-nitrophosphonates, the title compound, (I), was investigated. The crystal structure analysis of (I), Fig. 1, shows an S-configuration about the C7 atom. When viewed down the P–C7 axis, the molecule has a staggered conformation with the P═O and OH groups being diagonally opposite. The presence of O–H···O hydrogen bonding formed between the hydroxyl-O4—H and O═P atoms leads to the formation of supramolecular chains along [1 0 0], Fig. 2 and Table 1. Stability to these chains of linear topology is afforded by C–H···O contacts, Table 1.

Experimental

The title compound was prepared as described in the literature (Mandal et al., 2007).

Refinement

The C-bound H atoms were geometrically placed (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The methyl H-atoms were rotated to fit the electron density. The O–H H atom was located from a difference map and refined with O–H = 0.840±0.001 Å, and with Uiso(H) = 1.5Ueq(O). Disorder is evident in the structure as seen in the anisotropic displacement parameters associated with several residues. However, multiple sites were only resolved for the C6 atom. Two distinct sites were resolved from isotropic refinement of C6/C60 with the major component having a site occupancy factor of 0.60 (2).

Figures

Fig. 1.
Molecular structure of (I), showing displacement ellipsoids at the 50% probability level. Only the major component of the C6 position is shown (the atom was refined isotropically).
Fig. 2.
Supramolecular chain along the a axis in (I) mediated by O–H···O (orange dashed lines) hydrogen bonding. Colour scheme: P, pink; F, orange; O, red; N, blue; C, grey; and H, green.

Crystal data

C14H21FNO6PF(000) = 736
Mr = 349.29Dx = 1.368 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6077 reflections
a = 5.8267 (12) Åθ = 4.2–30.5°
b = 15.931 (3) ŵ = 0.20 mm1
c = 18.273 (4) ÅT = 173 K
V = 1696.2 (6) Å3Block, colourless
Z = 40.31 × 0.15 × 0.06 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer3391 independent reflections
Radiation source: fine-focus sealed tube3248 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 26.5°, θmin = 4.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −7→5
Tmin = 0.790, Tmax = 1k = −20→13
6049 measured reflectionsl = −22→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.117w = 1/[σ2(Fo2) + (0.0528P)2 + 0.8973P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3391 reflectionsΔρmax = 0.48 e Å3
211 parametersΔρmin = −0.43 e Å3
1 restraintAbsolute structure: Flack (1983), 1354 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.11 (13)

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)
P10.90429 (11)0.45039 (4)0.97285 (3)0.02753 (16)
F11.1808 (4)0.75747 (13)0.76550 (11)0.0698 (7)
O11.1339 (3)0.41823 (11)0.95590 (10)0.0332 (4)
O20.8946 (3)0.52834 (11)1.02505 (10)0.0351 (4)
O30.7358 (3)0.38649 (12)1.00898 (10)0.0367 (5)
O40.5136 (3)0.50239 (11)0.90853 (11)0.0321 (4)
H4O0.42450.46480.92370.048*
O50.3934 (4)0.36867 (16)0.78091 (14)0.0629 (7)
O60.6260 (6)0.45661 (17)0.73135 (13)0.0832 (10)
N10.5743 (5)0.40835 (15)0.77945 (14)0.0468 (6)
C11.0726 (5)0.59419 (18)1.02606 (16)0.0428 (7)
H11.13520.60240.97560.051*
C20.9465 (7)0.6725 (2)1.0502 (2)0.0619 (10)
H2A0.82520.68561.01490.093*
H2B1.05450.71961.05290.093*
H2C0.87820.66301.09850.093*
C31.2628 (6)0.5689 (2)1.07709 (18)0.0539 (9)
H3A1.33730.51801.05850.081*
H3B1.19920.55781.12580.081*
H3C1.37580.61431.08020.081*
C40.7057 (8)0.3642 (3)1.08354 (19)0.0803 (15)0.60 (2)
H40.64890.41551.10920.096*0.60 (2)
C50.5148 (8)0.3014 (3)1.0862 (2)0.0710 (12)0.60 (2)
H5A0.39310.31831.05220.107*0.60 (2)
H5B0.45280.29871.13600.107*0.60 (2)
H5C0.57350.24601.07210.107*0.60 (2)
C60.9077 (14)0.3372 (7)1.1220 (5)0.058 (2)*0.60 (2)
H6A1.01680.38391.12510.087*0.60 (2)
H6B0.97860.29031.09570.087*0.60 (2)
H6C0.86550.31911.17150.087*0.60 (2)
C400.7057 (8)0.3642 (3)1.08354 (19)0.0803 (15)0.40 (2)
H400.61320.41431.09830.096*0.40 (2)
C500.5148 (8)0.3014 (3)1.0862 (2)0.0710 (12)0.40 (2)
H50A0.39310.31831.05220.107*0.40 (2)
H50B0.45280.29871.13600.107*0.40 (2)
H50C0.57350.24601.07210.107*0.40 (2)
C600.8713 (15)0.3703 (8)1.1382 (5)0.041 (3)*0.40 (2)
H60A0.99490.40751.12180.062*0.40 (2)
H60B0.93420.31451.14850.062*0.40 (2)
H60C0.80140.39321.18270.062*0.40 (2)
C70.7379 (4)0.47723 (15)0.88976 (14)0.0258 (5)
C80.7355 (5)0.39729 (16)0.84242 (14)0.0328 (6)
H8A0.89200.38580.82390.039*
H8B0.68630.34880.87250.039*
C90.8523 (4)0.55250 (16)0.85275 (12)0.0274 (5)
C101.0637 (5)0.54344 (19)0.81713 (14)0.0376 (6)
H101.13270.48960.81340.045*
C111.1721 (5)0.6126 (2)0.78744 (17)0.0464 (8)
H111.31490.60690.76290.056*
C121.0702 (6)0.68921 (19)0.79409 (16)0.0457 (8)
C130.8621 (6)0.70094 (18)0.82673 (16)0.0435 (7)
H130.79330.75500.82850.052*
C140.7536 (5)0.63162 (16)0.85730 (15)0.0344 (6)
H140.61060.63850.88150.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0271 (3)0.0296 (3)0.0259 (3)−0.0048 (3)0.0000 (3)0.0023 (3)
F10.0853 (16)0.0602 (12)0.0640 (12)−0.0366 (12)0.0008 (12)0.0286 (10)
O10.0281 (9)0.0341 (9)0.0373 (9)−0.0007 (8)−0.0010 (8)0.0052 (8)
O20.0347 (9)0.0391 (9)0.0316 (8)−0.0100 (8)0.0013 (9)−0.0067 (8)
O30.0377 (10)0.0416 (10)0.0307 (9)−0.0140 (9)−0.0015 (8)0.0084 (8)
O40.0241 (9)0.0320 (10)0.0402 (11)−0.0023 (8)0.0052 (8)0.0023 (9)
O50.0469 (13)0.0661 (15)0.0756 (16)0.0048 (13)−0.0221 (14)−0.0285 (13)
O60.135 (3)0.0656 (16)0.0492 (13)−0.018 (2)−0.0420 (18)0.0132 (13)
N10.0594 (17)0.0359 (12)0.0451 (14)0.0120 (13)−0.0185 (14)−0.0116 (12)
C10.0459 (16)0.0463 (15)0.0363 (14)−0.0209 (14)−0.0003 (15)−0.0061 (13)
C20.076 (3)0.0427 (17)0.067 (2)−0.0038 (18)−0.015 (2)−0.0106 (16)
C30.0390 (16)0.076 (2)0.0469 (17)−0.0115 (17)−0.0008 (15)−0.0171 (17)
C40.092 (3)0.110 (3)0.0382 (17)−0.061 (3)−0.021 (2)0.032 (2)
C50.081 (3)0.084 (3)0.0478 (18)−0.056 (2)−0.0012 (19)0.015 (2)
C400.092 (3)0.110 (3)0.0382 (17)−0.061 (3)−0.021 (2)0.032 (2)
C500.081 (3)0.084 (3)0.0478 (18)−0.056 (2)−0.0012 (19)0.015 (2)
C70.0230 (11)0.0238 (11)0.0308 (12)−0.0007 (9)0.0024 (10)−0.0012 (9)
C80.0378 (14)0.0271 (12)0.0334 (13)0.0034 (12)−0.0096 (12)−0.0024 (10)
C90.0310 (13)0.0290 (12)0.0223 (10)−0.0019 (11)0.0005 (10)0.0033 (10)
C100.0320 (13)0.0476 (15)0.0333 (13)0.0033 (13)0.0049 (12)0.0111 (13)
C110.0352 (14)0.062 (2)0.0421 (15)−0.0051 (14)0.0041 (14)0.0217 (15)
C120.0546 (19)0.0472 (17)0.0352 (14)−0.0202 (16)−0.0075 (15)0.0172 (13)
C130.060 (2)0.0307 (13)0.0398 (14)−0.0088 (14)−0.0010 (15)0.0025 (12)
C140.0402 (14)0.0287 (12)0.0344 (13)−0.0039 (12)0.0011 (13)−0.0005 (11)

Geometric parameters (Å, °)

P1—O11.4656 (19)C5—H5C0.9800
P1—O31.5609 (19)C6—H6A0.9800
P1—O21.5670 (19)C6—H6B0.9800
P1—C71.851 (3)C6—H6C0.9800
F1—C121.368 (3)C40—C601.392 (9)
O2—C11.476 (3)C40—C501.496 (5)
O3—C401.419 (4)C40—H401.0000
O3—C41.419 (4)C50—H50A0.9800
O4—C71.409 (3)C50—H50B0.9800
O4—H4O0.8401C50—H50C0.9800
O5—N11.229 (4)C60—H60A0.9800
O6—N11.206 (4)C60—H60B0.9800
N1—C81.496 (4)C60—H60C0.9800
C1—C31.503 (5)C7—C91.529 (3)
C1—C21.514 (5)C7—C81.540 (3)
C1—H11.0000C8—H8A0.9900
C2—H2A0.9800C8—H8B0.9900
C2—H2B0.9800C9—C141.388 (4)
C2—H2C0.9800C9—C101.401 (4)
C3—H3A0.9800C10—C111.382 (4)
C3—H3B0.9800C10—H100.9500
C3—H3C0.9800C11—C121.362 (5)
C4—C61.436 (8)C11—H110.9500
C4—C51.496 (5)C12—C131.364 (5)
C4—H41.0000C13—C141.390 (4)
C5—H5A0.9800C13—H130.9500
C5—H5B0.9800C14—H140.9500
O1—P1—O3115.82 (11)C60—C40—O3125.8 (5)
O1—P1—O2116.03 (11)C60—C40—C50122.6 (4)
O3—P1—O2103.69 (10)O3—C40—C50106.9 (3)
O1—P1—C7112.66 (11)C60—C40—H4097.2
O3—P1—C799.68 (11)O3—C40—H4097.2
O2—P1—C7107.29 (11)C50—C40—H4097.2
C1—O2—P1123.06 (17)C40—C50—H50A109.5
C40—O3—P1130.3 (2)C40—C50—H50B109.5
C4—O3—P1130.3 (2)H50A—C50—H50B109.5
C7—O4—H4O116.8C40—C50—H50C109.5
O6—N1—O5123.9 (3)H50A—C50—H50C109.5
O6—N1—C8118.6 (3)H50B—C50—H50C109.5
O5—N1—C8117.5 (3)C40—C60—H60A109.5
O2—C1—C3109.6 (2)C40—C60—H60B109.5
O2—C1—C2104.4 (3)H60A—C60—H60B109.5
C3—C1—C2113.5 (3)C40—C60—H60C109.5
O2—C1—H1109.8H60A—C60—H60C109.5
C3—C1—H1109.8H60B—C60—H60C109.5
C2—C1—H1109.8O4—C7—C9106.77 (19)
C1—C2—H2A109.5O4—C7—C8111.3 (2)
C1—C2—H2B109.5C9—C7—C8113.8 (2)
H2A—C2—H2B109.5O4—C7—P1110.58 (17)
C1—C2—H2C109.5C9—C7—P1108.40 (16)
H2A—C2—H2C109.5C8—C7—P1105.94 (16)
H2B—C2—H2C109.5N1—C8—C7109.9 (2)
C1—C3—H3A109.5N1—C8—H8A109.7
C1—C3—H3B109.5C7—C8—H8A109.7
H3A—C3—H3B109.5N1—C8—H8B109.7
C1—C3—H3C109.5C7—C8—H8B109.7
H3A—C3—H3C109.5H8A—C8—H8B108.2
H3B—C3—H3C109.5C14—C9—C10119.1 (2)
O3—C4—C6116.3 (5)C14—C9—C7120.3 (2)
O3—C4—C5106.9 (3)C10—C9—C7120.5 (2)
C6—C4—C5113.2 (4)C11—C10—C9120.2 (3)
O3—C4—H4106.6C11—C10—H10119.9
C6—C4—H4106.6C9—C10—H10119.9
C5—C4—H4106.6C12—C11—C10118.7 (3)
C4—C5—H5A109.5C12—C11—H11120.6
C4—C5—H5B109.5C10—C11—H11120.6
H5A—C5—H5B109.5C11—C12—C13123.3 (3)
C4—C5—H5C109.5C11—C12—F1118.2 (3)
H5A—C5—H5C109.5C13—C12—F1118.5 (3)
H5B—C5—H5C109.5C12—C13—C14118.1 (3)
C4—C6—H6A109.5C12—C13—H13120.9
C4—C6—H6B109.5C14—C13—H13120.9
H6A—C6—H6B109.5C9—C14—C13120.6 (3)
C4—C6—H6C109.5C9—C14—H14119.7
H6A—C6—H6C109.5C13—C14—H14119.7
H6B—C6—H6C109.5
O1—P1—O2—C133.2 (2)O1—P1—C7—C855.3 (2)
O3—P1—O2—C1161.4 (2)O3—P1—C7—C8−68.07 (19)
C7—P1—O2—C1−93.7 (2)O2—P1—C7—C8−175.81 (17)
O1—P1—O3—C4085.5 (4)O6—N1—C8—C769.9 (4)
O2—P1—O3—C40−42.8 (4)O5—N1—C8—C7−108.5 (3)
C7—P1—O3—C40−153.4 (4)O4—C7—C8—N150.9 (3)
O1—P1—O3—C485.5 (4)C9—C7—C8—N1−69.8 (3)
O2—P1—O3—C4−42.8 (4)P1—C7—C8—N1171.2 (2)
C7—P1—O3—C4−153.4 (4)O4—C7—C9—C1413.7 (3)
P1—O2—C1—C3−86.8 (3)C8—C7—C9—C14137.0 (2)
P1—O2—C1—C2151.4 (2)P1—C7—C9—C14−105.4 (2)
C40—O3—C4—C60(100)O4—C7—C9—C10−169.6 (2)
P1—O3—C4—C6−54.1 (7)C8—C7—C9—C10−46.4 (3)
C40—O3—C4—C50(8)P1—C7—C9—C1071.2 (3)
P1—O3—C4—C5178.4 (3)C14—C9—C10—C110.4 (4)
C4—O3—C40—C600(100)C7—C9—C10—C11−176.3 (3)
P1—O3—C40—C60−25.6 (9)C9—C10—C11—C120.5 (4)
C4—O3—C40—C500(8)C10—C11—C12—C13−2.1 (5)
P1—O3—C40—C50178.4 (3)C10—C11—C12—F1179.0 (3)
O1—P1—C7—O4176.02 (15)C11—C12—C13—C142.7 (5)
O3—P1—C7—O452.65 (17)F1—C12—C13—C14−178.4 (3)
O2—P1—C7—O4−55.09 (18)C10—C9—C14—C130.3 (4)
O1—P1—C7—C9−67.26 (19)C7—C9—C14—C13177.0 (2)
O3—P1—C7—C9169.37 (17)C12—C13—C14—C9−1.8 (4)
O2—P1—C7—C961.64 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4o···O1i0.841.942.728 (3)156
C10—H10···O5ii0.952.523.447 (4)164

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5270).

References

  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Mandal, T., Samanta, S. & Zhao, C.-G. (2007). Org. Lett.9, 943–945. [PubMed]
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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