2 Hydr­­oxy 5,5 di­methyl 4 phenyl 1,3,2 dioxa­phospho­rinan 2 one monohydrate

organic papers

o1276

11H15O4PH2O doi:10.1107/S1600536807006496 Acta Cryst.(2007). E63, o1276–o1278

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

2-Hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinan-2-one monohydrate

Brian Samas,* Todd Groendyke, Anthony C Blackburn and Delara B Godrej

Pfizer Global Research and Devlopment, Pharmaceutical Sciences, Ann Arbor, MI 48105, USA

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 173 K

Mean(C–C) = 0.002 A˚ Rfactor = 0.034 wRfactor = 0.085

Data-to-parameter ratio = 18.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 2 February 2007 Accepted 7 February 2007

#2007 International Union of Crystallography All rights reserved

The title compound, C11H15O4PH2O, commonly called (S )-phencyphos monohydrate, belongs to a class of phosphori-nanes. Molecules form a hydrogen-bond network of corru-gated ribbons.

Comment

Phosphorinanes have been popular in classical chiral resolu-tion (CCR) for several decades (Ten Hoeve & Wynberg, 1985). Although the crystal structure has not been deter-mined, the title compound, (I), has been used in CCR and also in Dutch Resolution (Lohet al., 2006).

One end of the molecule of compound (I) is polar and the other is non-polar. The hydrophilic end interacts with the water molecule. These interactions form a layer parallel to both theaaxis and thebaxis. The hydrophobic phenyl ring interleaves in a layer, also parallel to both theaaxis and theb

axss. These hydrophobic and hydrophilic layers alternate along the c axis. The phenyl rings are stacked, but none of these interactions are–in nature.

The structure has a contact present within the van der Waals radius, from a metahydrogen on the phenyl group to one of the O atoms of the phosphorinane. Although the phenyl ring has room to rotate, it is configured within the van der Waals

Figure 1

radius; hence this contact is considered to be a weak hydrogen bond (Table 1).

The most important close contacts are hydrogen bonds between the acid group and the water molecule. The hydrogen bonding between these groups forms an uncommon 10-membered ring (Table 1 and Fig. 2). The hydrogen-bonded rings stack back-to-back, forming a puckered ribbon propa-gating in the direction of both the b axis and the c axis. Molecules are hydrogen bonded to equivalent molecules generated by the 21 screw symmetry. All strong donors and acceptors are used in this crystal structure and form strong hydrogen bonds, which are almost linear.

The acidic proton forms a very strong hydrogen bond with the water molecule. This P O(—OH) group is chiral in the solid state (R); this chirality is not inherent to the compound as the proton is exchangable in the solution state.

The water molecule is in a very stable environment. The O atom accepts one strong hydrogen bond, along a lone pair, while the water also donates two hydrogen bonds. This is the most common hydrogen-bond conformation for a hydrate (Gillonet al., 2003). We measured the critical water activity of compound (I) at room temperature to be less than 0.2 (Golles, 1962). Both the hydrate and the anhydrous forms were observed in the course of our experiments.

The dioxaphosphorinane ring is in the expected chair conformation. This compound has the P O oxygen and the phenyl group in the expected equatorial positions.

Experimental

A stock solution of (I) was made in methanol (0.05M). A 1 ml aliquot of the stock solution was added to a 1.8 ml HPLC screw-capped vial. This was allowed to evaporate over 24 h. A crystal of (I) was removed from the vial and mounted on a mitogen loop with paratone-Noil. The water activity was measured by setting up slurries in mixtures of water and ethanol. Suspended solids were allowed to slurry for two weeks, filtered and then analysed. The powder X-ray patterns of

resulting solids from these slurries were measured and compared with the predicted powder X-ray pattern of compound (I).

Crystal data

C11H15O4PH2O

Mr= 260.22

Orthorhombic,P2₁2₁2₁ a= 6.017 (2) A˚ b= 8.219 (3) A˚ c= 25.475 (10) A˚ V= 1259.7 (8) A˚3

Z= 4

Dx= 1.372 Mg m

3

MoKradiation

= 0.23 mm1 T= 173 (2) K Column, colourless 0.610.090.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Tmin= 0.861,Tmax= 0.991

23045 measured reflections 3004 independent reflections 2899 reflections withI> 2(I) Rint= 0.030

max= 28.2

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.034 wR(F2_{) = 0.085}

S= 1.11 3004 reflections 167 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2_(F

o2) + (0.0515P)2

+ 0.1668P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.45 e A˚

3

min=0.23 e A˚

3

Absolute structure: Flack (1983), 1213 friedel pairs

Flack parameter:0.03 (8)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O1—H99B O2i

0.83 (3) 1.85 (3) 2.670 (2) 171 (2) O1—H99A O2ii 0.81 (3) 1.91 (3) 2.7179 (19) 176 (2) C9—H9 O4iii

0.95 2.68 3.625 (2) 174

O3—H99C O1iv

0.988 (10) 1.475 (11) 2.4395 (18) 164 (2)

Symmetry codes: (i) x;yþ1;z; (ii) xþ1 2;yþ

1

2;z; (iii) x;yþ 1 2;zþ

1 2; (iv)

x1;y1;z.

All H atoms were found in a Fourier difference map. H atoms bound to C atoms were placed in idealized positions and refined using a riding model, with C—H = 0.95 A˚ for Csp2, 0.98 A˚ for CH3, 0.99 A˚

for CH2and 1.00 A˚ for CH.Uiso(H) values were set at 1.5Ueq(C) for

the methyl groups and at 1.2Ueq(C) in all other cases. H atoms bound

to the water molecule and the acidic group were located in difference Fourier maps and their positions were refined freely with isotropic displacement parameters. The PO—H distance was restrained to 0.98 (1) A˚ .

Data collection:SMART(Bruker, 2003); cell refinement:SAINT (Bruker, 2003); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury(Brunoet al., 2002); software used to prepare material for publication:SHELXL97.

References

Bruker (2003).SMARTfor WNT/2000 (Version 5.630),SAINT-Plus(Version 6.45) andSHELXTL(Version 6.14). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst.B58, 389–397.

Flack, H. D. (1983).Acta Cryst.A39, 876–881.

organic papers

Acta Cryst.(2007). E63, o1276–o1278 Samaset al. _C

11H15O4PH2O

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Figure 2

Gillon, A. L., Feeder, N., Davey, R. J. & Storey, R. (2003).Cryst. Growth Des.

3, 663–673.

Golles, F. (1962).Monatsh. Chem.93, 191–220.

Loh, J. S. C., Van Enckevort, W. J. P., Vlieg, E., Gervais, C., Grimbergen, R. F. P. & Kaptein, B. (2006).Cryst. Growth Des.6, 861–865.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Sheldrick, G. M. (2003).SADABS. Version 2.10. University of Go¨ttingen, Germany.

Ten Hoeve, W. & Wynberg, H. (1985).J. Org. Chem.50, 4508–4514.

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Acta Cryst. (2007). E63, o1276–o1278

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Acta Cryst. (2007). E63, o1276–o1278 [https://doi.org/10.1107/S1600536807006496]

2-Hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinan-2-one monohydrate

Brian Samas, Todd Groendyke, Anthony C Blackburn and Delara B Godrej

2-Hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinan-2-one monohydrate

Crystal data

C11H15O4P·H2O Mr = 260.22

Orthorhombic, P212121

Hall symbol: P 2ac 2ab

a = 6.017 (2) Å

b = 8.219 (3) Å

c = 25.475 (10) Å

V = 1259.7 (8) Å3 Z = 4

F(000) = 552

Dx = 1.372 Mg m−3

Melting point: 86.5 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 983 reflections

θ = 2.6–27.3°

µ = 0.23 mm−1 T = 173 K

Columnar, colourless 0.61 × 0.09 × 0.04 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, 2003)

Tmin = 0.861, Tmax = 0.991

23045 measured reflections 3004 independent reflections 2899 reflections with I > 2σ(I)

Rint = 0.030

θmax = 28.2°, θmin = 1.6°

h = −7→7

k = −10→10

l = −32→33

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.034} wR(F2_{) = 0.085} S = 1.11 3004 reflections 167 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(Fo2_{) + (0.0515P)}2 _{+ 0.1668P]}

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max < 0.001

Δρmax = 0.45 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983), 1213 friedel pairs

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Acta Cryst. (2007). E63, o1276–o1278

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

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Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

P1 0.01937 (18) 0.02179 (18) 0.02406 (18) −0.00055 (14) −0.00106 (14) −0.00604 (14) O4 0.0261 (5) 0.0180 (5) 0.0208 (5) 0.0002 (4) −0.0004 (4) −0.0023 (4) O5 0.0345 (6) 0.0287 (6) 0.0185 (5) −0.0015 (5) −0.0003 (5) −0.0027 (4) O1 0.0240 (6) 0.0282 (6) 0.0333 (6) −0.0021 (5) 0.0020 (5) −0.0075 (5) O2 0.0264 (6) 0.0295 (6) 0.0350 (6) 0.0019 (5) −0.0021 (5) −0.0132 (5) O3 0.0201 (5) 0.0275 (6) 0.0527 (7) −0.0007 (5) −0.0012 (5) −0.0121 (6) C1 0.0363 (8) 0.0201 (7) 0.0297 (7) 0.0035 (7) −0.0010 (6) −0.0005 (6) C2 0.0186 (7) 0.0178 (6) 0.0210 (6) 0.0009 (5) 0.0016 (5) −0.0016 (5) C3 0.0331 (8) 0.0227 (7) 0.0218 (7) −0.0002 (7) −0.0029 (7) 0.0024 (5) C4 0.0234 (7) 0.0192 (7) 0.0194 (6) −0.0008 (6) 0.0007 (6) 0.0000 (5) C5 0.0330 (8) 0.0269 (7) 0.0250 (7) −0.0007 (7) 0.0066 (7) 0.0002 (6) C6 0.0251 (8) 0.0252 (7) 0.0293 (7) −0.0057 (6) 0.0021 (6) 0.0015 (6) C7 0.0270 (7) 0.0204 (7) 0.0187 (6) −0.0032 (6) 0.0014 (6) 0.0002 (5) C8 0.0337 (9) 0.0306 (8) 0.0249 (7) 0.0039 (7) −0.0017 (7) −0.0007 (6) C9 0.0538 (12) 0.0312 (9) 0.0205 (7) −0.0058 (8) 0.0083 (7) −0.0024 (6) C10 0.0401 (10) 0.0389 (9) 0.0311 (8) 0.0027 (9) −0.0108 (8) 0.0045 (7) C11 0.0565 (12) 0.0356 (9) 0.0212 (7) −0.0101 (9) −0.0062 (8) 0.0026 (7)

Geometric parameters (Å, º)

P1—O2 1.4841 (13) C3—H3A 0.9900 P1—O3 1.5284 (13) C3—H3B 0.9900 P1—O5 1.5678 (12) C4—C6 1.539 (2) P1—O4 1.5778 (12) C5—C7 1.394 (2) O4—C2 1.4731 (17) C5—C9 1.395 (2) O5—C3 1.4564 (18) C5—H5 0.9500 O1—H99A 0.81 (3) C6—H6A 0.9800 O1—H99B 0.83 (3) C6—H6B 0.9800 O3—H99C 0.988 (10) C6—H6C 0.9800 C1—C4 1.531 (2) C7—C8 1.393 (2) C1—H1A 0.9800 C8—C10 1.392 (2) C1—H1B 0.9800 C8—H8 0.9500 C1—H1C 0.9800 C9—C11 1.383 (3) C2—C7 1.5080 (19) C9—H9 0.9500 C2—C4 1.548 (2) C10—C11 1.387 (3) C2—H2 1.0000 C10—H10 0.9500 C3—C4 1.535 (2) C11—H11 0.9500

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C3—O5—P1 116.29 (9) C9—C5—H5 119.9 H99A—O1—H99B 106 (2) C4—C6—H6A 109.5 P1—O3—H99C 115.1 (14) C4—C6—H6B 109.5 C4—C1—H1A 109.5 H6A—C6—H6B 109.5 C4—C1—H1B 109.5 C4—C6—H6C 109.5 H1A—C1—H1B 109.5 H6A—C6—H6C 109.5 C4—C1—H1C 109.5 H6B—C6—H6C 109.5 H1A—C1—H1C 109.5 C8—C7—C5 119.06 (15) H1B—C1—H1C 109.5 C8—C7—C2 121.32 (13) O4—C2—C7 107.06 (11) C5—C7—C2 119.61 (14) O4—C2—C4 109.18 (11) C10—C8—C7 120.29 (16) C7—C2—C4 115.63 (12) C10—C8—H8 119.9 O4—C2—H2 108.3 C7—C8—H8 119.9 C7—C2—H2 108.3 C11—C9—C5 120.37 (16) C4—C2—H2 108.3 C11—C9—H9 119.8 O5—C3—C4 112.25 (12) C5—C9—H9 119.8 O5—C3—H3A 109.2 C11—C10—C8 120.46 (18) C4—C3—H3A 109.2 C11—C10—H10 119.8 O5—C3—H3B 109.2 C8—C10—H10 119.8 C4—C3—H3B 109.2 C9—C11—C10 119.55 (16) H3A—C3—H3B 107.9 C9—C11—H11 120.2 C1—C4—C3 106.29 (12) C10—C11—H11 120.2

O2—P1—O4—C2 169.94 (10) C7—C2—C4—C3 178.55 (12) O3—P1—O4—C2 −62.95 (11) O4—C2—C4—C6 −63.82 (14) O5—P1—O4—C2 50.95 (11) C7—C2—C4—C6 56.93 (16) O2—P1—O5—C3 −167.49 (10) C9—C5—C7—C8 1.3 (2) O3—P1—O5—C3 65.40 (12) C9—C5—C7—C2 −177.73 (15) O4—P1—O5—C3 −48.74 (12) O4—C2—C7—C8 32.12 (19) P1—O4—C2—C7 175.61 (10) C4—C2—C7—C8 −89.78 (18) P1—O4—C2—C4 −58.53 (14) O4—C2—C7—C5 −148.88 (13) P1—O5—C3—C4 56.37 (16) C4—C2—C7—C5 89.22 (17) O5—C3—C4—C1 −175.98 (13) C5—C7—C8—C10 −0.9 (3) O5—C3—C4—C6 64.48 (16) C2—C7—C8—C10 178.12 (15) O5—C3—C4—C2 −57.92 (16) C7—C5—C9—C11 −0.5 (3) O4—C2—C4—C1 173.59 (12) C7—C8—C10—C11 −0.4 (3) C7—C2—C4—C1 −65.65 (17) C5—C9—C11—C10 −0.8 (3) O4—C2—C4—C3 57.79 (15) C8—C10—C11—C9 1.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H99B···O2i _{0.83 (3) 1.85 (3) 2.670 (2) 171 (2)}

O1—H99A···O2ii _{0.81 (3) 1.91 (3) 2.7179 (19) 176 (2)}

C9—H9···O4iii _{0.95 2.68 3.625 (2) 174}

O3—H99C···O1iv _{0.99 (1) 1.48 (1) 2.4395 (18) 164 (2)}