4,4,5,5-Tetra­methyl-1,3,2λ5-dioxa­phospho­lan-2-one

Skarżyńska, A.; Trzeciak, A.M.; Gniewek, A.

doi:10.1107/S160053681102959X

organic compounds

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Volume 67| Part 8| August 2011| Page o2159

doi:10.1107/S160053681102959X

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4,4,5,5-Tetramethyl-1,3,2λ⁵-dioxaphospholan-2-one

Anna Skarżyńska,^a Anna M. Trzeciak ^a and Andrzej Gniewek ^a ^*

^aFaculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, 50-383 Wrocław, Poland
^*Correspondence e-mail: andrzej@netesa.com

(Received 20 July 2011; accepted 21 July 2011; online 30 July 2011)

The five-membered ring in the title compound, C₆H₁₃O₃P, exists in an envelope conformation with one of the ring C atoms at the flap position. The coordination geometry around the P atom is a distorted tetrahedron. The crystal structure is stabilized by several weak C—H⋯O and P—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For a discussion of 1,3,2-dioxaphospholane chemistry, see: Maffei & Buono (2003 ); Zwierzak (1967 ) and for the Heck reaction, see: Beletskaya & Cheprakov (2000 ); Skarżyńska et al. (2011 ). For hydrogen-bond interactions, see: Desiraju & Steiner (1999 ). For bond lengths in organic compounds, see: Allen et al. (1987 ). For details of the temperature control applied during data collection, see: Cosier & Glazer (1986 ) and for specifications of the analytical numeric absorption correction, see: Clark & Reid (1995 ).

Experimental

Crystal data

C₆H₁₃O₃P
M_r = 164.13
Monoclinic, P 2₁ /c
a = 7.144 (2) Å
b = 7.570 (2) Å
c = 15.064 (4) Å
β = 90.98 (2)°
V = 814.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.33 × 0.27 × 0.26 mm

Data collection

Kuma KM-4 diffractometer with CCD detector
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ) T_min = 0.910, T_max = 0.952
7254 measured reflections
1869 independent reflections
1673 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.10
1869 reflections
143 parameters
All H-atom parameters refined
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H113⋯Oⁱ	0.98 (2)	2.70 (2)	3.583 (2)	150 (2)
C12—H123⋯Oⁱ	1.00 (2)	2.60 (2)	3.499 (2)	150 (2)
C21—H213⋯Oⁱ	0.96 (2)	2.68 (2)	3.544 (2)	148 (2)
C22—H222⋯O1ⁱⁱ	0.98 (2)	2.64 (2)	3.515 (2)	148 (2)
P—H⋯O1ⁱⁱⁱ	1.28 (2)	2.58 (2)	3.4713 (12)	124 (1)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102959X/bt5583sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102959X/bt5583Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102959X/bt5583Isup3.cml

checkCIF report

Comment top

Carbon-carbon bond-forming catalytic reactions are very important fundamental processes in synthetic chemistry. Among them, one of the commonly recognized is the Heck reaction employing as the catalyst precursors palladium compounds with phosphorus ligands (Beletskaya & Cheprakov, 2000). Complexes incorporating in their structure 1,3,2-dioxaphospholane heterocyclic rings have been recently found to be efficient catalysts of the Heck reaction carried out under mild conditions (Skarżyńska et al., 2011). In this paper we report the synthesis and crystallization of tetramethyl dioxaphospholane, the title compound.

The geometric parameters around the four-coordinate phosphorus atom (Fig. 1) indicate a deformation of the ideal tetrahedron towards a trigonal pyramid. The O—P—O1 and O—P—O2 angles differ considerably from the ideal value of 109.5° and approach 120°, while O1—P—O2 is close to 90°. Such deformations might be explained by the effect of different substituents and bond types. Bond lengths P—O1, P—O2, P—O, and P—H are typical (Allen et al., 1987). The heterocyclic five-membered ring P/O1/C1/C2/O2 adopts an envelope conformation with the C1 atom deviating from the four-atom plane by about 0.55 Å.

The crystal structure is stabilized by a few hydrogen bonds of the C—H···O and P—H···O types (Desiraju & Steiner, 1999). Consequently, a three-dimensional network of such interactions is formed in the crystal. The C11, C12 and C21 atoms act as hydrogen-bond donors, via H113, H123 and H213, respectively, to the Oⁱ atom [symmetry code: (i) x, –y + 1/2, z + 1/2] as an acceptor (Table 1). As a result, chains running parallel to the [001] direction are formed. The adjacent chains of the molecules are further linked by C22—H222···O1ⁱⁱ and P—H···O1ⁱⁱⁱ hydrogen interactions [symmetry codes: (ii) –x, y – 1/2, –z + 1/2; (iii) –x + 1, y – 1/2, –z + 1/2].

Related literature top

For discussion on 1,3,2-dioxaphospholane chemistry, see: Maffei & Buono (2003); Zwierzak (1967) and for the Heck reaction, see: Beletskaya & Cheprakov (2000); Skarżyńska et al. (2011). For hydrogen-bond interactions, see: Desiraju & Steiner (1999). For bond lengths in organic compounds, see: Allen et al. (1987). For details of the temperature control applied during data collection, see: Cosier & Glazer (1986) and for specifications of the analytical numeric absorption correction, see: Clark & Reid (1995).

Experimental top

The title compound may be prepared according to the known procedures: utilizing pinacol and phosphorus trichloride, followed by hydrolysis (Zwierzak, 1967) or involving a transestrification process between pinacol and diethyl phosphite (Maffei & Buono, 2003). Here we report an alternative route. Crystallization of 2,2,3,3,7,7,8,8-octamethyl-1,4,6,9–5λ⁵-phosphaspiro[4.4]nonane in non-dried diethyl ether leads to hydrolysis of the tetraoxaspirophosphorane. As a result, 4,4,5,5-teramethyl-1,3,2-dioxaphospholane 2-oxide is formed as single crystals.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis RED (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure and atom numbering scheme of the title compound. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

4,4,5,5-Tetramethyl-1,3,2λ⁵-dioxaphospholan-2-one top

Crystal data top

C₆H₁₃O₃P	F(000) = 352
M_r = 164.13	D_x = 1.338 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4820 reflections
a = 7.144 (2) Å	θ = 3.0–27.5°
b = 7.570 (2) Å	µ = 0.29 mm⁻¹
c = 15.064 (4) Å	T = 100 K
β = 90.98 (2)°	Block, colorless
V = 814.5 (4) Å³	0.33 × 0.27 × 0.26 mm
Z = 4

Data collection top

Kuma KM-4 diffractometer with CCD detector	1869 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2010)	h = −9→9
T_min = 0.910, T_max = 0.952	k = −9→9
7254 measured reflections	l = −19→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: difference Fourier map
wR(F²) = 0.096	All H-atom parameters refined
S = 1.10	w = 1/[σ²(F_o²) + (0.0645P)² + 0.1298P] where P = (F_o² + 2F_c²)/3
1869 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₆H₁₃O₃P	V = 814.5 (4) Å³
M_r = 164.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.144 (2) Å	µ = 0.29 mm⁻¹
b = 7.570 (2) Å	T = 100 K
c = 15.064 (4) Å	0.33 × 0.27 × 0.26 mm
β = 90.98 (2)°

Data collection top

Kuma KM-4 diffractometer with CCD detector	1869 independent reflections
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2010)	1673 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.952	R_int = 0.021
7254 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	All H-atom parameters refined
S = 1.10	Δρ_max = 0.49 e Å⁻³
1869 reflections	Δρ_min = −0.30 e Å⁻³
143 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100 K. Analytical numeric absorption correction was carried out with CrysAlis RED (Oxford Diffraction, 2010) using a multifaceted crystal model (Clark & Reid, 1995).

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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
P	0.35196 (5)	0.22996 (4)	0.21158 (2)	0.02085 (14)
H	0.528 (2)	0.199 (2)	0.2076 (11)	0.028 (4)*
O	0.26815 (19)	0.25962 (13)	0.12379 (7)	0.0376 (3)
O1	0.32677 (12)	0.38610 (11)	0.28007 (5)	0.0172 (2)
C1	0.29786 (16)	0.31569 (15)	0.37050 (8)	0.0152 (2)
C11	0.48914 (18)	0.28153 (19)	0.41307 (10)	0.0236 (3)
H111	0.553 (2)	0.190 (2)	0.3832 (12)	0.030 (4)*
H112	0.563 (3)	0.389 (3)	0.4098 (12)	0.044 (5)*
H113	0.476 (3)	0.251 (2)	0.4759 (14)	0.037 (5)*
C12	0.19155 (18)	0.45553 (17)	0.42081 (8)	0.0213 (3)
H121	0.076 (2)	0.494 (2)	0.3871 (11)	0.031 (4)*
H122	0.265 (2)	0.555 (2)	0.4267 (10)	0.026 (4)*
H123	0.163 (2)	0.408 (2)	0.4813 (11)	0.033 (4)*
O2	0.27159 (13)	0.07451 (11)	0.26996 (6)	0.0224 (2)
C2	0.18549 (16)	0.14270 (16)	0.35218 (8)	0.0168 (3)
C21	0.21170 (19)	0.00213 (17)	0.42256 (9)	0.0235 (3)
H211	0.339 (2)	−0.037 (2)	0.4228 (10)	0.028 (4)*
H212	0.131 (3)	−0.095 (3)	0.4074 (12)	0.037 (5)*
H213	0.179 (2)	0.044 (3)	0.4806 (12)	0.040 (5)*
C22	−0.02050 (19)	0.1768 (2)	0.33204 (11)	0.0278 (3)
H221	−0.039 (3)	0.273 (2)	0.2898 (13)	0.034 (5)*
H222	−0.069 (2)	0.063 (3)	0.3105 (11)	0.040 (5)*
H223	−0.082 (3)	0.215 (2)	0.3860 (13)	0.029 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0308 (2)	0.0184 (2)	0.0136 (2)	0.00484 (12)	0.00665 (14)	0.00041 (11)
O	0.0656 (8)	0.0339 (6)	0.0132 (5)	0.0071 (5)	0.0000 (5)	−0.0014 (4)
O1	0.0224 (4)	0.0161 (4)	0.0131 (4)	0.0004 (3)	0.0037 (3)	0.0011 (3)
C1	0.0160 (5)	0.0173 (5)	0.0123 (5)	−0.0012 (4)	0.0002 (4)	0.0012 (4)
C11	0.0167 (6)	0.0305 (7)	0.0235 (7)	−0.0014 (5)	−0.0050 (5)	0.0027 (5)
C12	0.0271 (6)	0.0195 (6)	0.0175 (6)	0.0021 (5)	0.0032 (5)	−0.0034 (5)
O2	0.0343 (5)	0.0159 (4)	0.0171 (4)	0.0007 (4)	0.0071 (4)	−0.0023 (3)
C2	0.0175 (5)	0.0169 (5)	0.0162 (5)	−0.0005 (4)	0.0027 (4)	−0.0012 (4)
C21	0.0282 (6)	0.0194 (6)	0.0232 (7)	−0.0016 (5)	0.0061 (5)	0.0051 (5)
C22	0.0173 (6)	0.0290 (7)	0.0368 (8)	−0.0047 (5)	−0.0031 (5)	−0.0009 (6)

Geometric parameters (Å, º) top

P—O	1.4596 (12)	C12—H123	1.00 (2)
P—H	1.28 (2)	C1—C2	1.5582 (16)
P—O1	1.5812 (10)	O2—C2	1.4850 (14)
P—O2	1.5827 (10)	C2—C21	1.5115 (16)
O1—C1	1.4806 (14)	C2—C22	1.5196 (16)
C1—C12	1.5137 (16)	C21—H211	0.96 (2)
C1—C11	1.5216 (16)	C21—H212	0.96 (2)
C11—H111	0.95 (2)	C21—H213	0.96 (2)
C11—H112	0.98 (2)	C22—H221	0.98 (2)
C11—H113	0.98 (2)	C22—H222	0.98 (2)
C12—H121	1.00 (2)	C22—H223	0.97 (2)
C12—H122	0.92 (2)

O—P—O1	115.26 (6)	H121—C12—H122	106 (2)
O—P—O2	118.08 (6)	H121—C12—H123	113 (2)
O—P—H	112.0 (8)	H122—C12—H123	109 (2)
O1—P—O2	98.44 (6)	C2—O2—P	111.37 (7)
O1—P—H	106.9 (8)	O2—C2—C21	106.99 (10)
O2—P—H	104.7 (8)	O2—C2—C22	107.82 (10)
C1—O1—P	110.52 (7)	C21—C2—C22	111.57 (10)
O1—C1—C11	108.09 (10)	O2—C2—C1	102.73 (9)
O1—C1—C12	106.74 (10)	C21—C2—C1	114.22 (10)
C12—C1—C11	111.25 (10)	C22—C2—C1	112.75 (10)
O1—C1—C2	102.66 (9)	C2—C21—H211	109.1 (12)
C11—C1—C2	112.83 (10)	C2—C21—H212	107.7 (12)
C12—C1—C2	114.52 (10)	C2—C21—H213	112.1 (12)
C1—C11—H111	111.0 (12)	H211—C21—H212	109 (2)
C1—C11—H112	108.7 (12)	H211—C21—H213	110 (2)
C1—C11—H113	110.5 (12)	H212—C21—H213	109 (2)
H111—C11—H112	109 (2)	C2—C22—H221	112.1 (12)
H111—C11—H113	110 (2)	C2—C22—H222	104.5 (12)
H112—C11—H113	108 (2)	C2—C22—H223	109.4 (12)
C1—C12—H121	111.4 (12)	H221—C22—H222	113 (2)
C1—C12—H122	109.0 (12)	H221—C22—H223	105 (2)
C1—C12—H123	108.5 (12)	H222—C22—H223	112 (2)

O—P—O1—C1	143.16 (9)	O1—C1—C2—O2	37.31 (10)
O2—P—O1—C1	16.56 (8)	C11—C1—C2—O2	−78.79 (12)
P—O1—C1—C11	85.34 (8)	C12—C1—C2—O2	152.58 (12)
P—O1—C1—C12	−154.89 (10)	O1—C1—C2—C21	152.79 (10)
P—O1—C1—C2	−34.11 (10)	C11—C1—C2—C21	36.69 (12)
O—P—O2—C2	−116.09 (9)	C12—C1—C2—C21	−91.94 (12)
O1—P—O2—C2	8.52 (8)	O1—C1—C2—C22	−78.47 (10)
P—O2—C2—C21	−149.19 (8)	C11—C1—C2—C22	165.44 (12)
P—O2—C2—C22	90.67 (10)	C12—C1—C2—C22	36.80 (12)
P—O2—C2—C1	−28.61 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H113···Oⁱ	0.98 (2)	2.70 (2)	3.583 (2)	150 (2)
C12—H123···Oⁱ	1.00 (2)	2.60 (2)	3.499 (2)	150 (2)
C21—H213···Oⁱ	0.96 (2)	2.68 (2)	3.544 (2)	148 (2)
C22—H222···O1ⁱⁱ	0.98 (2)	2.64 (2)	3.515 (2)	148 (2)
P—H···O1ⁱⁱⁱ	1.28 (2)	2.58 (2)	3.4713 (12)	124 (1)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₃O₃P
M_r	164.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.144 (2), 7.570 (2), 15.064 (4)
β (°)	90.98 (2)
V (Å³)	814.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.33 × 0.27 × 0.26

Data collection
Diffractometer	Kuma KM-4 diffractometer with CCD detector
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.910, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	7254, 1869, 1673
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.10
No. of reflections	1869
No. of parameters	143
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.30

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H113···Oⁱ	0.98 (2)	2.70 (2)	3.583 (2)	150 (2)
C12—H123···Oⁱ	1.00 (2)	2.60 (2)	3.499 (2)	150 (2)
C21—H213···Oⁱ	0.96 (2)	2.68 (2)	3.544 (2)	148 (2)
C22—H222···O1ⁱⁱ	0.98 (2)	2.64 (2)	3.515 (2)	148 (2)
P—H···O1ⁱⁱⁱ	1.28 (2)	2.58 (2)	3.4713 (12)	124 (1)

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

Acknowledgements

This work was partially supported by the Polish Ministry of Science and Higher Education through grant No. N204 028538. The financial support is gratefully acknowledged.

References

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