2,6,7-Trioxa-1-phosphabicyclo­[2.2.2]octan-4-ylmethanol 1-sulfide

Yang, Q.; Zhang, Y.; Huang, J.; Men, J.; Gao, G.

doi:10.1107/S1600536808041937

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o141

doi:10.1107/S1600536808041937

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2,6,7-Trioxa-1-phosphabicyclo[2.2.2]octan-4-ylmethanol 1-sulfide

Qi Yang,^a Ye-qin Zhang,^a Jian-qian Huang,^a Jian Men ^b and Guo-wei Gao ^b ^*

^aCollege of Polymer Science and Engineering, Sichuan University, Chengdu 610065, People's Republic of China, and ^bCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: gaosunday@yahoo.com.cn

(Received 22 November 2008; accepted 10 December 2008; online 17 December 2008)

The title compound, C₅H₉O₄PS, was synthesized by the reaction of pentaerythritol with thiophosphoryl chloride. In the crystal structure, the three six-membered rings all adopt boat conformations. Molecules form chains along the c axis via intermolecular O—H⋯O hydrogen bonds.

Related literature

For a general background to the synthesis and applications of the title compound, see: Bourbigot & Duquesne (2007 ); Fontaine et al. (2008 ); Le Bras et al. (1997 ); Ratz & Aweeting (1964 ).

Experimental

Crystal data

C₅H₉O₄PS
M_r = 196.16
Orthorhombic, P n a 2₁
a = 11.571 (3) Å
b = 9.724 (3) Å
c = 7.112 (4) Å
V = 800.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 292 (2) K
0.44 × 0.40 × 0.24 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: for a sphere (Farrugia, 1999 ) T_min = 0.861, T_max = 0.863
1224 measured reflections
949 independent reflections
864 reflections with > 2s(I)
R_int = 0.009
3 standard reflections every 80 reflections intensity decay: 0.3%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.106
S = 1.04
949 reflections
101 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 137 Friedel pairs
Flack parameter: −0.04 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.82	2.20	2.886 (6)	141
Symmetry code: (i) x, y, z-1.

Data collection: DIFRAC (Gabe et al., 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); 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/S1600536808041937/rk2119sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041937/rk2119Isup2.hkl

checkCIF report

Comment top

Intumescent flame retardant systems appear as an attractive topic and represent a wide and interesting area of research (Bourbigot & Duquesne, 2007). The use of pentaerythritol (Le Bras et al., 1997) as char former in intumescent formulations which composed of three components, i.e. an acid source, a char forming agent and a blowing agent for thermoplastics is associated with migration, water solubility and other problems. Those problems were solved by synthesis of additives that concentrate the three intumescent flame retardant elements in one molecule (Fontaine et al., 2008). The compound synthesized (Ratz & Aweeting, 1964) which has little intumescence is the intermediate product of the concentrate intumescent flame retardant.

In the molecule of the title compound (Fig.1), three six–membered rings adopt boat conformations. The bond angle of C3—C4—C5 is 112.7 (4)° which is bigger than one of sp³ hybrid, it may be the result of the co–existence of the three six–membered rings attached at C5. The torsion angles of S1/P1/O3/C3 and O1/C1/C4/C5 are -178.7 (3)° and -178.4 (4)°, respectively. Intermolecular O—H···O hydrogen bonds link the molecules with formation chains along c axis and effective stabilized the crystal structure (Table).

Related literature top

For a general background to the synthesis and applications of the title compound, see: Bourbigot & Duquesne (2007); Fontaine et al. (2008); Le Bras et al. (1997); Ratz & Aweeting (1964).

Experimental top

A mixture of 62.6 g (0.46 mol) pentaerythritol and 77.9 g (0.46 mol) thiophosphoryl chloride was heated at 418 K in a 250 ml round–bottomed flask equipped for reflux, protected from atmospheric moisture and equipped with magnetic stirrer. Evolution of hydrogen chloride ceased after 5 h. The resulting cake was extracted with 150 ml boiling water and cooled to room temperature. During the extracting some material remained undissolved and collected as a heavy oil at the bottom of the flask. The aqueous solvent was separated from this oil by decantation through a folded filter. The product was crystallized from water and afforded white crystals (62 g, yield 68.7%, m.p. 431–433 K).

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); 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 asymmetric unit of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

2,6,7-Trioxa-1-phosphabicyclo[2.2.2]octan-4-ylmethanol 1-sulfide top

Crystal data top

C₅H₉O₄PS	F(000) = 408
M_r = 196.16	D_x = 1.628 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 16 reflections
a = 11.571 (3) Å	θ = 4.5–7.2°
b = 9.724 (3) Å	µ = 0.57 mm⁻¹
c = 7.112 (4) Å	T = 292 K
V = 800.2 (6) Å³	Block, colourless
Z = 4	0.44 × 0.40 × 0.24 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	864 reflections with > 2s(I)
Radiation source: Fine–focus sealed tube	R_int = 0.009
Graphite monochromator	θ_max = 25.5°, θ_min = 2.7°
ω/2θ scans	h = −13→13
Absorption correction: for a sphere (Farrugia, 1999)	k = −11→11
T_min = 0.861, T_max = 0.863	l = −8→2
1224 measured reflections	3 standard reflections every 80 reflections
949 independent reflections	intensity decay: 0.3%

Refinement top

Refinement on F²	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0792P)² + 0.1948P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
949 reflections	Δρ_max = 0.45 e Å⁻³
101 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 137 Friedel pairs
Primary atom site location: Direct	Absolute structure parameter: −0.04 (19)

Crystal data top

C₅H₉O₄PS	V = 800.2 (6) Å³
M_r = 196.16	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 11.571 (3) Å	µ = 0.57 mm⁻¹
b = 9.724 (3) Å	T = 292 K
c = 7.112 (4) Å	0.44 × 0.40 × 0.24 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	864 reflections with > 2s(I)
Absorption correction: for a sphere (Farrugia, 1999)	R_int = 0.009
T_min = 0.861, T_max = 0.863	3 standard reflections every 80 reflections
1224 measured reflections	intensity decay: 0.3%
949 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.106	Δρ_max = 0.45 e Å⁻³
S = 1.04	Δρ_min = −0.23 e Å⁻³
949 reflections	Absolute structure: Flack (1983), 137 Friedel pairs
101 parameters	Absolute structure parameter: −0.04 (19)
1 restraint

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
S1	0.43219 (11)	0.07576 (14)	1.1866 (2)	0.0617 (4)
P1	0.32384 (8)	0.09916 (9)	0.98909 (19)	0.0389 (3)
O1	0.2853 (3)	−0.0370 (3)	0.8907 (5)	0.0534 (8)
O2	0.2054 (3)	0.1676 (3)	1.0501 (5)	0.0520 (8)
O3	0.3650 (2)	0.1924 (3)	0.8211 (5)	0.0509 (8)
O4	0.1030 (4)	0.0757 (5)	0.3982 (6)	0.0812 (13)
H4	0.1541	0.1153	0.3394	0.122*
C3	0.2796 (4)	0.2118 (5)	0.6721 (8)	0.0575 (12)
H3A	0.3115	0.1806	0.5534	0.069*
H3B	0.2617	0.3089	0.6603	0.069*
C1	0.1994 (4)	−0.0202 (5)	0.7394 (8)	0.0545 (11)
H1A	0.1299	−0.0711	0.7703	0.065*
H1B	0.2302	−0.0566	0.6227	0.065*
C2	0.1224 (3)	0.1837 (5)	0.8992 (7)	0.0470 (10)
H2A	0.1019	0.2801	0.8873	0.056*
H2B	0.0527	0.1329	0.9296	0.056*
C4	0.1702 (3)	0.1327 (4)	0.7147 (7)	0.0401 (9)
C5	0.0792 (4)	0.1483 (5)	0.5622 (7)	0.0557 (12)
H5A	0.0055	0.1173	0.6115	0.067*
H5B	0.0716	0.2450	0.5314	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0617 (7)	0.0732 (7)	0.0503 (7)	0.0055 (5)	−0.0140 (6)	0.0133 (7)
P1	0.0419 (5)	0.0398 (4)	0.0351 (5)	0.0032 (4)	0.0019 (5)	0.0075 (5)
O1	0.072 (2)	0.0367 (14)	0.0515 (19)	0.0077 (13)	−0.0097 (18)	0.0070 (16)
O2	0.0443 (14)	0.077 (2)	0.0349 (15)	0.0123 (14)	0.0007 (14)	−0.0066 (16)
O3	0.0430 (14)	0.0607 (17)	0.049 (2)	−0.0084 (13)	−0.0033 (15)	0.0200 (17)
O4	0.101 (3)	0.106 (3)	0.037 (2)	−0.015 (2)	−0.003 (2)	0.001 (2)
C3	0.052 (2)	0.074 (3)	0.047 (3)	−0.003 (2)	−0.005 (3)	0.025 (3)
C1	0.069 (3)	0.045 (2)	0.048 (3)	0.0042 (19)	−0.004 (2)	−0.003 (2)
C2	0.042 (2)	0.056 (2)	0.043 (3)	0.0064 (17)	−0.003 (2)	−0.004 (2)
C4	0.0401 (19)	0.0421 (18)	0.038 (2)	0.0000 (15)	0.0020 (18)	0.0051 (19)
C5	0.057 (3)	0.065 (3)	0.045 (3)	−0.005 (2)	−0.008 (2)	0.001 (2)

Geometric parameters (Å, º) top

S1—P1	1.8966 (19)	C3—H3B	0.9700
P1—O1	1.562 (3)	C1—C4	1.535 (6)
P1—O3	1.573 (3)	C1—H1A	0.9700
P1—O2	1.583 (3)	C1—H1B	0.9700
O1—C1	1.474 (6)	C2—C4	1.508 (6)
O2—C2	1.449 (5)	C2—H2A	0.9700
O3—C3	1.461 (5)	C2—H2B	0.9700
O4—C5	1.390 (6)	C4—C5	1.519 (7)
O4—H4	0.8200	C5—H5A	0.9700
C3—C4	1.512 (6)	C5—H5B	0.9700
C3—H3A	0.9700

O1—P1—O3	103.55 (19)	C4—C1—H1B	109.7
O1—P1—O2	103.38 (18)	H1A—C1—H1B	108.2
O3—P1—O2	103.18 (18)	O2—C2—C4	111.4 (3)
O1—P1—S1	114.77 (13)	O2—C2—H2A	109.3
O3—P1—S1	115.56 (13)	C4—C2—H2A	109.3
O2—P1—S1	114.78 (15)	O2—C2—H2B	109.3
C1—O1—P1	115.2 (2)	C4—C2—H2B	109.3
C2—O2—P1	114.6 (3)	H2A—C2—H2B	108.0
C3—O3—P1	114.9 (2)	C2—C4—C3	108.3 (4)
C5—O4—H4	109.5	C2—C4—C5	109.5 (3)
O3—C3—C4	110.8 (4)	C3—C4—C5	112.7 (4)
O3—C3—H3A	109.5	C2—C4—C1	107.5 (4)
C4—C3—H3A	109.5	C3—C4—C1	109.3 (3)
O3—C3—H3B	109.5	C5—C4—C1	109.3 (4)
C4—C3—H3B	109.5	O4—C5—C4	114.3 (4)
H3A—C3—H3B	108.1	O4—C5—H5A	108.7
O1—C1—C4	109.9 (4)	C4—C5—H5A	108.7
O1—C1—H1A	109.7	O4—C5—H5B	108.7
C4—C1—H1A	109.7	C4—C5—H5B	108.7
O1—C1—H1B	109.7	H5A—C5—H5B	107.6

O3—P1—O1—C1	−54.2 (3)	O2—C2—C4—C3	−58.1 (5)
O2—P1—O1—C1	53.1 (3)	O2—C2—C4—C5	178.5 (4)
S1—P1—O1—C1	178.9 (3)	O2—C2—C4—C1	59.9 (4)
O1—P1—O2—C2	−53.5 (3)	O3—C3—C4—C2	59.4 (5)
O3—P1—O2—C2	54.1 (3)	O3—C3—C4—C5	−179.2 (4)
S1—P1—O2—C2	−179.3 (3)	O3—C3—C4—C1	−57.4 (5)
O1—P1—O3—C3	54.9 (3)	O1—C1—C4—C2	−59.6 (4)
O2—P1—O3—C3	−52.6 (4)	O1—C1—C4—C3	57.7 (5)
S1—P1—O3—C3	−178.7 (3)	O1—C1—C4—C5	−178.4 (4)
P1—O3—C3—C4	−1.3 (5)	C2—C4—C5—O4	−165.6 (4)
P1—O1—C1—C4	0.8 (5)	C3—C4—C5—O4	73.8 (6)
P1—O2—C2—C4	−1.0 (5)	C1—C4—C5—O4	−48.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.82	2.20	2.886 (6)	141

Symmetry code: (i) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₅H₉O₄PS
M_r	196.16
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	292
a, b, c (Å)	11.571 (3), 9.724 (3), 7.112 (4)
V (Å³)	800.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.44 × 0.40 × 0.24

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (Farrugia, 1999)
T_min, T_max	0.861, 0.863
No. of measured, independent and observed [ > 2s(I)] reflections	1224, 949, 864
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.106, 1.04
No. of reflections	949
No. of parameters	101
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.23
Absolute structure	Flack (1983), 137 Friedel pairs
Absolute structure parameter	−0.04 (19)

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), 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
O4—H4···O2ⁱ	0.82	2.20	2.886 (6)	141.2

Symmetry code: (i) x, y, z−1.

Acknowledgements

The authors acknowledge the National Basic Research Program of China (contract grant No. 2005BC623800) and thank Mr Zhi-Hua Mao of Sichuan University for the X–ray data collection.

References

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