3,9-Dichloro-2,4,8,10-tetra­oxa-3,9-di­phosphaspiro­[5.5]undecane-3,9-dione

Zhan, Z.-S.; Wang, H.; Ding, L.-P.; Dong, C.-M.; Sun, C.-Y.

doi:10.1107/S1600536810043333

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3026

https://doi.org/10.1107/S1600536810043333

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3,9-Dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dione

Zhao-Shun Zhan,^a Hong Wang,^a Li-Ping Ding,^a Chun-Mei Dong ^a and Cai-Ying Sun ^a ^*

^aHeilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retardant Materials, College of Science, Northeast Forestry University, Harbin 150040, People's Republic of China
^*Correspondence e-mail: sundeyee@yahoo.com.cn

(Received 21 October 2010; accepted 24 October 2010; online 31 October 2010)

In the title compound, C₅H₈Cl₂O₆P₂, the two six-membered rings display chair conformations. The P=O bond distances are 1.444 (2) and 1.446 (2) Å. Weak intermolecular C—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For applications of pentaerythritol diphosphonate compounds, see: Granzow (1981 ); Tanabe et al. (2005 ). For details of the preparation of the title compound, see: Li et al. (2002 ). For related compounds, see: Heinemann et al. (1994 ); Zhang et al. (2006 ). For bond-length, see: Allen et al. (1987 ); Elnagar et al. (2000 ).

Experimental

Crystal data

C₅H₈Cl₂O₆P₂
M_r = 296.95
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0630 (5) Å
b = 12.7384 (10) Å
c = 13.4338 (10) Å
V = 1037.53 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 185 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD 1000 area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.896, T_max = 0.929
5317 measured reflections
1849 independent reflections
1662 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.069
S = 1.00
1849 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 747 Friedel pairs
Flack parameter: 0.18 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O5ⁱ	0.99	2.34	3.214 (4)	147
C1—H1B⋯O6ⁱⁱ	0.99	2.31	3.252 (4)	159
C4—H4B⋯O5ⁱ	0.99	2.36	3.260 (4)	150
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810043333/xu5060sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043333/xu5060Isup2.hkl

checkCIF report

Comment top

Studies of pentaerythritol diphosphonate compounds have been significant interested. On one hand, the compounds have been reported to act as one of the most important reaction intermediates of fire retardant agents (Tanabe et al., 2005). On the other hand, it seems to be a good candidate in modifying the stability of polymers (Granzow, 1981). The findings have triggered the development of new flame retardant materials. As an extension of the work on the structural characterization of pentaerythritol diphosphonate compounds, the preparation and crystal structure of the title compound, (I), is proposed here.

The asymmetric unit of (I) contain a spiro[5.5]undecane molecule (Fig. 1). Several compounds with similar structures have been reported previously (Heinemann et al., 1994; Zhang et al., 2006). The bond lengths and angles are within normal ranges (Allen et al., 1987; Elnagar et al., 2000). The six-membered rings of (I) have the chair conformation consistent with the steric difference in this conformation between opposite ends of the molecule. In addition, the C1—C3—C2 and C4—C3—C5 angles are in the range of 109.4 (3)–109.2 (3)°,the P—Cl bond lengths are 2.0050 (14) and 2.0047 (13) Å, respectively. In the crystal structure of (I), The non-classic C—H···O hydrogen bonds ranging from 3.099 (4) to 3.260 (4) Å contributed to the stability of the crystal packing.

Related literature top

For applications of pentaerythritol diphosphonate compounds, see: Granzow (1981); Tanabe et al. (2005). For details of the preparation of the compounds, see: Li et al. (2002). For related compounds, see: Heinemann et al. (1994); Zhang et al. (2006). For bond-length and angle data [or just bond-length?], see: Allen et al. (1987); Elnagar et al. (2000).

Experimental top

The title compound was prepared by reaction of pentaerythritol with phosphorus oxychloride in acetonitrile according to the reported procedures (Li et al., 2002). Crystals were produced at the bottom of the vessel on slow evaporation of acetic acid solution.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing through C—H···O interactions along the c axis

3,9-Dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dione top

Crystal data top

C₅H₈Cl₂O₆P₂	F(000) = 600
M_r = 296.95	D_x = 1.901 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2823 reflections
a = 6.0630 (5) Å	θ = 2.2–25.0°
b = 12.7384 (10) Å	µ = 0.94 mm⁻¹
c = 13.4338 (10) Å	T = 185 K
V = 1037.53 (14) Å³	Block, colorless
Z = 4	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD 1000 area-detector diffractometer	1849 independent reflections
Radiation source: fine-focus sealed tube	1662 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→7
T_min = 0.896, T_max = 0.929	k = −14→15
5317 measured reflections	l = −14→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0283P)² + 0.5846P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1849 reflections	Δρ_max = 0.27 e Å⁻³
136 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 747 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.18 (10)

Crystal data top

C₅H₈Cl₂O₆P₂	V = 1037.53 (14) Å³
M_r = 296.95	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0630 (5) Å	µ = 0.94 mm⁻¹
b = 12.7384 (10) Å	T = 185 K
c = 13.4338 (10) Å	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD 1000 area-detector diffractometer	1849 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1662 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.929	R_int = 0.036
5317 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.27 e Å⁻³
S = 1.00	Δρ_min = −0.23 e Å⁻³
1849 reflections	Absolute structure: Flack (1983), 747 Friedel pairs
136 parameters	Absolute structure parameter: 0.18 (10)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
P2	0.86704 (16)	0.68037 (6)	0.19061 (7)	0.0195 (2)
P1	0.61011 (17)	0.94037 (7)	0.51917 (6)	0.0225 (2)
Cl2	1.00827 (16)	0.75305 (7)	0.07460 (7)	0.0322 (2)
Cl1	0.28767 (15)	0.96781 (7)	0.53971 (7)	0.0299 (2)
O4	0.9665 (4)	0.73565 (16)	0.28413 (16)	0.0197 (5)
O2	0.6224 (4)	0.82146 (16)	0.48872 (15)	0.0218 (5)
O6	0.8993 (4)	0.56810 (17)	0.18897 (18)	0.0274 (6)
O3	0.6190 (4)	0.71416 (16)	0.18620 (16)	0.0206 (5)
O1	0.6715 (4)	1.00446 (16)	0.42462 (16)	0.0227 (6)
O5	0.7431 (5)	0.96565 (19)	0.60521 (16)	0.0338 (6)
C3	0.6534 (6)	0.8561 (2)	0.3088 (2)	0.0170 (7)
C5	0.9032 (6)	0.8438 (2)	0.3065 (3)	0.0208 (8)
H5A	0.9656	0.8912	0.2553	0.025*
H5B	0.9652	0.8644	0.3718	0.025*
C4	0.5581 (6)	0.8229 (2)	0.2084 (2)	0.0198 (8)
H4A	0.3955	0.8295	0.2098	0.024*
H4B	0.6152	0.8697	0.1555	0.024*
C1	0.5966 (6)	0.9720 (2)	0.3254 (2)	0.0211 (7)
H1A	0.6694	1.0155	0.2740	0.025*
H1B	0.4353	0.9822	0.3198	0.025*
C2	0.5455 (6)	0.7897 (3)	0.3905 (2)	0.0207 (8)
H2A	0.3833	0.7978	0.3870	0.025*
H2B	0.5810	0.7147	0.3796	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P2	0.0192 (5)	0.0181 (4)	0.0211 (5)	−0.0002 (4)	0.0003 (4)	−0.0033 (4)
P1	0.0263 (5)	0.0223 (5)	0.0189 (5)	−0.0018 (4)	0.0020 (4)	−0.0028 (4)
Cl2	0.0331 (5)	0.0376 (5)	0.0259 (5)	−0.0039 (5)	0.0073 (4)	0.0002 (4)
Cl1	0.0282 (5)	0.0299 (5)	0.0317 (5)	0.0023 (4)	0.0074 (4)	−0.0002 (4)
O4	0.0187 (13)	0.0183 (12)	0.0221 (12)	0.0044 (11)	−0.0028 (10)	−0.0046 (10)
O2	0.0295 (13)	0.0182 (11)	0.0178 (12)	0.0025 (11)	−0.0017 (11)	0.0003 (9)
O6	0.0283 (14)	0.0192 (12)	0.0346 (14)	0.0004 (11)	0.0046 (13)	−0.0042 (11)
O3	0.0205 (12)	0.0169 (11)	0.0245 (12)	−0.0013 (10)	−0.0035 (12)	−0.0037 (10)
O1	0.0307 (15)	0.0169 (11)	0.0206 (12)	−0.0025 (11)	0.0042 (11)	−0.0037 (10)
O5	0.0393 (16)	0.0398 (15)	0.0223 (12)	−0.0063 (14)	−0.0051 (13)	−0.0065 (11)
C3	0.0198 (18)	0.0146 (15)	0.0166 (16)	0.0006 (13)	−0.0007 (15)	−0.0015 (13)
C5	0.0248 (19)	0.0164 (16)	0.0212 (18)	−0.0009 (15)	−0.0002 (17)	−0.0046 (14)
C4	0.0219 (19)	0.0151 (16)	0.0223 (19)	0.0042 (15)	−0.0024 (15)	−0.0015 (14)
C1	0.028 (2)	0.0183 (17)	0.0167 (17)	0.0027 (16)	0.0007 (16)	0.0000 (14)
C2	0.024 (2)	0.0189 (18)	0.0196 (18)	0.0002 (15)	0.0002 (15)	−0.0014 (14)

Geometric parameters (Å, º) top

P2—O6	1.444 (2)	C3—C5	1.523 (5)
P2—O4	1.561 (2)	C3—C4	1.528 (4)
P2—O3	1.565 (2)	C3—C2	1.532 (4)
P2—Cl2	2.0047 (13)	C3—C1	1.533 (4)
P1—O5	1.446 (2)	C5—H5A	0.9900
P1—O1	1.555 (2)	C5—H5B	0.9900
P1—O2	1.571 (2)	C4—H4A	0.9900
P1—Cl1	2.0050 (14)	C4—H4B	0.9900
O4—C5	1.461 (3)	C1—H1A	0.9900
O2—C2	1.457 (4)	C1—H1B	0.9900
O3—C4	1.464 (4)	C2—H2A	0.9900
O1—C1	1.467 (4)	C2—H2B	0.9900

O6—P2—O4	114.00 (13)	O4—C5—H5A	109.4
O6—P2—O3	113.70 (14)	C3—C5—H5A	109.4
O4—P2—O3	106.12 (13)	O4—C5—H5B	109.4
O6—P2—Cl2	112.82 (11)	C3—C5—H5B	109.4
O4—P2—Cl2	104.61 (10)	H5A—C5—H5B	108.0
O3—P2—Cl2	104.71 (10)	O3—C4—C3	110.2 (3)
O5—P1—O1	113.75 (14)	O3—C4—H4A	109.6
O5—P1—O2	113.36 (14)	C3—C4—H4A	109.6
O1—P1—O2	106.39 (12)	O3—C4—H4B	109.6
O5—P1—Cl1	113.26 (12)	C3—C4—H4B	109.6
O1—P1—Cl1	104.73 (10)	H4A—C4—H4B	108.1
O2—P1—Cl1	104.49 (11)	O1—C1—C3	109.5 (2)
C5—O4—P2	119.3 (2)	O1—C1—H1A	109.8
C2—O2—P1	119.24 (19)	C3—C1—H1A	109.8
C4—O3—P2	119.6 (2)	O1—C1—H1B	109.8
C1—O1—P1	121.3 (2)	C3—C1—H1B	109.8
C5—C3—C4	109.2 (3)	H1A—C1—H1B	108.2
C5—C3—C2	112.5 (3)	O2—C2—C3	111.0 (3)
C4—C3—C2	108.6 (3)	O2—C2—H2A	109.4
C5—C3—C1	109.0 (3)	C3—C2—H2A	109.4
C4—C3—C1	108.0 (3)	O2—C2—H2B	109.4
C2—C3—C1	109.4 (3)	C3—C2—H2B	109.4
O4—C5—C3	111.2 (3)	H2A—C2—H2B	108.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O5ⁱ	0.99	2.34	3.214 (4)	147
C1—H1B···O6ⁱⁱ	0.99	2.31	3.252 (4)	159
C4—H4B···O5ⁱ	0.99	2.36	3.260 (4)	150

Symmetry codes: (i) −x+3/2, −y+2, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₈Cl₂O₆P₂
M_r	296.95
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	185
a, b, c (Å)	6.0630 (5), 12.7384 (10), 13.4338 (10)
V (Å³)	1037.53 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD 1000 area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.896, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	5317, 1849, 1662
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.069, 1.00
No. of reflections	1849
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.23
Absolute structure	Flack (1983), 747 Friedel pairs
Absolute structure parameter	0.18 (10)

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O5ⁱ	0.99	2.34	3.214 (4)	146.6
C1—H1B···O6ⁱⁱ	0.99	2.31	3.252 (4)	159.3
C4—H4B···O5ⁱ	0.99	2.36	3.260 (4)	150.0

Symmetry codes: (i) −x+3/2, −y+2, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

We thank Northeast Forestry University for financial support (graduate innovation funded projects GRAM09).

References

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