Ethane-1,2-diylbis(methyl­phosphinic acid)

Reiss, G.J.; Engel, J.S.

doi:10.1107/S1600536807068122

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o400

doi:10.1107/S1600536807068122

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Ethane-1,2-diylbis(methylphosphinic acid)

Guido J. Reiss ^a ^* and Judith S. Engel ^a

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl für Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: reissg@uni-duesseldorf.de

(Received 4 December 2007; accepted 21 December 2007; online 9 January 2008)

In the title compound, C₄H₁₂O₄P₂, there are two crystallographically independent half-molecules in the asymmetric unit, both molecules lying on centres of symmetry. Each molecule is connected on both sides to neighbouring molecules via strong O—H⋯O hydrogen bonds. The –POOH groups accept and donate one hydrogen bond in interactions with the neighbouring –POOH group of the adjacent molecule, to give one-dimensional chains along [10 $[\overline{1}]$ ]. As each phosphinic acid group donates and accepts one hydrogen bond, the connection between the molecules is best described by a ring motif which can be classified by the Etter symbol R₂²(8).

Related literature

For related literature, see: Bruckmann et al. (1999 ); Etter et al. (1990 ); Sicken et al. (2000 ).

Experimental

Crystal data

C₄H₁₂O₄P₂
M_r = 186.08
Monoclinic, P 2₁ /c
a = 6.7761 (18) Å
b = 18.703 (8) Å
c = 6.8401 (15) Å
β = 102.09 (3)°
V = 847.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 290 (2) K
0.40 × 0.35 × 0.30 mm

Data collection

Nicolet/Siemens P2₁/P3 four-circle diffractometer
Absorption correction: none
4847 measured reflections
2466 independent reflections
1879 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.079
S = 1.01
2466 reflections
139 parameters
All H-atom parameters refined
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2	0.95 (4)	1.55 (4)	2.504 (2)	178 (3)
O1—H1⋯O3	0.94 (4)	1.56 (4)	2.499 (2)	179 (4)

Data collection: R3m/V Software (Siemens, 1989 ); cell refinement: R3m/V Software; data reduction: R3m/V Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068122/pk2077sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068122/pk2077Isup2.hkl

checkCIF report

Comment top

The title compound, [HOO(CH₃)P-(CH₂)₂-P(CH₃)OOH, crystallizes in the monoclinic centrosymmetric space group P2₁/c with two crystallographically independent molecules in the asymmetric unit both of them lying on a centre of symmetry. The molecules are connected on both sides to the next molecules via strong O—H···H hydrogen bonds. The bond lengths and angles in the two crystallographic independent molecules are identical within the ranges of their standard uncertainties. As each posphinic acid group donates and accepts one hydrogen bond the motif of this connection between the molecules is best described by an eight-membered ring (Fig.1) which can be classified by the Etter symbol R²₂(8) (Etter et al., 1990). A motif which is well known for acetic acid and its derivatives. Each –POOH group accepts and donates one hydrogen bond to the neighbouring –POOH groups of the next molecules to give a one-dimensional chains along [10–1]. This was surprising to us, as the very similar ethane-1,2-diylbis(phosphinic acid) forms a two-dimensional hydrogen bonded network (Bruckmann et al., 1999).

Related literature top

For related literature, see: Bruckmann et al. (1999); Etter et al. (1990); Sicken et al. (2000).

Experimental top

The title compound is generally available by methods described in the literature (Sicken et al., 2000). Recrystallization of the raw material from ethanolic solution at room temperature gave block shaped, colourless crystals.

Computing details top

Data collection: R3m/V Software (Siemens, 1989); cell refinement: R3m/V Software (Siemens, 1989); data reduction: R3m/V Software (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. : Part of the hydrogen bonded chain of the title structure. (displacement ellipsoids at the 50% probability level, H-atoms drawn with arbitrary radius, ' = -x, 1 - y, 2 - z; '' = 1 - x, 1 - y, 1 - z)

Ethane-1,2-diylbis(methylphosphinic acid) top

Crystal data top

C₄H₁₂O₄P₂	F(000) = 392
M_r = 186.08	D_x = 1.458 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 37 reflections
a = 6.7761 (18) Å	θ = 5.1–14.3°
b = 18.703 (8) Å	µ = 0.47 mm⁻¹
c = 6.8401 (15) Å	T = 290 K
β = 102.09 (3)°	Block, colourless
V = 847.7 (5) Å³	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection top

Nicolet/Siemens P21/P3-four-circle diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 2.2°
Graphite monochromator	h = 0→9
ω scans	k = −26→26
4847 measured reflections	l = −9→9
2466 independent reflections	3 standard reflections every 100 reflections
1879 reflections with I > 2σ(I)	intensity decay: none

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) = 0.079	All H-atom parameters refined
S = 1.01	w = 1/[σ²(F_o²) + (0.025P)² + 0.41P] where P = (F_o² + 2F_c²)/3
2466 reflections	(Δ/σ)_max = 0.003
139 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₄H₁₂O₄P₂	V = 847.7 (5) Å³
M_r = 186.08	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7761 (18) Å	µ = 0.47 mm⁻¹
b = 18.703 (8) Å	T = 290 K
c = 6.8401 (15) Å	0.40 × 0.35 × 0.30 mm
β = 102.09 (3)°

Data collection top

Nicolet/Siemens P21/P3-four-circle diffractometer	R_int = 0.023
4847 measured reflections	3 standard reflections every 100 reflections
2466 independent reflections	intensity decay: none
1879 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.079	All H-atom parameters refined
S = 1.01	Δρ_max = 0.35 e Å⁻³
2466 reflections	Δρ_min = −0.34 e Å⁻³
139 parameters

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 > 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
P1	0.10537 (7)	0.60187 (2)	0.89929 (7)	0.03542 (12)
O1	0.0298 (2)	0.59213 (9)	0.6716 (2)	0.0477 (3)
H1	0.114 (6)	0.606 (2)	0.586 (6)	0.145 (15)*
O2	0.32968 (19)	0.59006 (8)	0.96702 (19)	0.0455 (3)
C1	0.0385 (5)	0.68801 (12)	0.9733 (4)	0.0563 (6)
H11	0.067 (4)	0.6933 (14)	1.116 (4)	0.070 (8)*
H12	0.106 (5)	0.7222 (17)	0.917 (5)	0.094 (10)*
H13	−0.088 (4)	0.6940 (15)	0.925 (4)	0.075 (9)*
C2	−0.0220 (3)	0.53869 (9)	1.0246 (3)	0.0371 (4)
H21	0.017 (3)	0.5445 (12)	1.163 (3)	0.047 (6)*
H22	−0.157 (3)	0.5475 (12)	0.984 (3)	0.051 (6)*
P2	0.48253 (7)	0.61724 (2)	0.51341 (7)	0.03302 (11)
O3	0.25753 (19)	0.62778 (7)	0.44442 (18)	0.0412 (3)
O4	0.5560 (2)	0.62903 (7)	0.7409 (2)	0.0421 (3)
H4	0.470 (5)	0.6132 (18)	0.826 (5)	0.117 (12)*
C3	0.6086 (4)	0.67852 (12)	0.3826 (4)	0.0501 (5)
H31	0.575 (4)	0.7228 (16)	0.410 (4)	0.078 (8)*
H32	0.565 (4)	0.6729 (14)	0.247 (4)	0.065 (8)*
H33	0.738 (4)	0.6751 (15)	0.426 (4)	0.079 (9)*
C4	0.5508 (3)	0.52908 (9)	0.4481 (3)	0.0343 (3)
H41	0.693 (3)	0.5257 (11)	0.494 (3)	0.042 (5)*
H42	0.513 (3)	0.5270 (11)	0.311 (3)	0.044 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0352 (2)	0.0375 (2)	0.0329 (2)	−0.00097 (17)	0.00569 (17)	0.00385 (18)
O1	0.0359 (7)	0.0712 (10)	0.0338 (7)	−0.0062 (6)	0.0024 (5)	0.0038 (6)
O2	0.0350 (7)	0.0632 (9)	0.0364 (7)	−0.0004 (6)	0.0030 (5)	0.0047 (6)
C1	0.0677 (16)	0.0365 (10)	0.0624 (16)	0.0033 (10)	0.0087 (12)	0.0018 (10)
C2	0.0403 (9)	0.0362 (9)	0.0361 (9)	0.0017 (7)	0.0108 (7)	0.0015 (7)
P2	0.0359 (2)	0.02862 (19)	0.0346 (2)	−0.00337 (16)	0.00759 (17)	0.00217 (17)
O3	0.0379 (7)	0.0472 (7)	0.0371 (7)	0.0038 (5)	0.0047 (5)	0.0049 (5)
O4	0.0374 (7)	0.0493 (8)	0.0378 (7)	−0.0064 (6)	0.0037 (5)	−0.0068 (6)
C3	0.0576 (14)	0.0369 (10)	0.0563 (13)	−0.0105 (9)	0.0133 (11)	0.0095 (9)
C4	0.0380 (9)	0.0299 (8)	0.0357 (9)	−0.0019 (7)	0.0095 (7)	0.0018 (7)

Geometric parameters (Å, º) top

P1—O2	1.5096 (14)	P2—O3	1.5115 (14)
P1—O1	1.5452 (15)	P2—O4	1.5468 (14)
P1—C1	1.776 (2)	P2—C3	1.779 (2)
P1—C2	1.7850 (19)	P2—C4	1.7942 (19)
O1—H1	0.94 (4)	O4—H4	0.95 (4)
C1—H11	0.96 (3)	C3—H31	0.89 (3)
C1—H12	0.92 (3)	C3—H32	0.92 (3)
C1—H13	0.86 (3)	C3—H33	0.87 (3)
C2—C2ⁱ	1.529 (3)	C4—C4ⁱⁱ	1.539 (3)
C2—H21	0.93 (2)	C4—H41	0.95 (2)
C2—H22	0.91 (2)	C4—H42	0.92 (2)

O2—P1—O1	113.08 (8)	O3—P2—O4	112.74 (8)
O2—P1—C1	110.24 (12)	O3—P2—C3	108.55 (11)
O1—P1—C1	110.11 (12)	O4—P2—C3	109.08 (11)
O2—P1—C2	108.23 (9)	O3—P2—C4	109.76 (8)
O1—P1—C2	108.33 (9)	O4—P2—C4	109.63 (8)
C1—P1—C2	106.60 (11)	C3—P2—C4	106.90 (11)
P1—O1—H1	119 (2)	P2—O4—H4	118 (2)
P1—C1—H11	112.0 (16)	P2—C3—H31	108.9 (18)
P1—C1—H12	109.5 (19)	P2—C3—H32	110.5 (16)
H11—C1—H12	110 (2)	H31—C3—H32	106 (2)
P1—C1—H13	107.7 (19)	P2—C3—H33	109.7 (19)
H11—C1—H13	110 (2)	H31—C3—H33	106 (3)
H12—C1—H13	107 (3)	H32—C3—H33	115 (2)
C2ⁱ—C2—P1	112.62 (17)	C4ⁱⁱ—C4—P2	111.78 (16)
C2ⁱ—C2—H21	107.8 (14)	C4ⁱⁱ—C4—H41	108.8 (12)
P1—C2—H21	110.3 (13)	P2—C4—H41	106.0 (12)
C2ⁱ—C2—H22	109.4 (15)	C4ⁱⁱ—C4—H42	112.7 (13)
P1—C2—H22	106.6 (14)	P2—C4—H42	105.1 (13)
H21—C2—H22	110.1 (18)	H41—C4—H42	112.3 (17)

O2—P1—C2—C2ⁱ	−61.3 (2)	O3—P2—C4—C4ⁱⁱ	−62.1 (2)
O1—P1—C2—C2ⁱ	61.7 (2)	O4—P2—C4—C4ⁱⁱ	62.3 (2)
C1—P1—C2—C2ⁱ	−179.8 (2)	C3—P2—C4—C4ⁱⁱ	−179.64 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2	0.95 (4)	1.55 (4)	2.504 (2)	178 (3)
O1—H1···O3	0.94 (4)	1.56 (4)	2.499 (2)	179 (4)

Experimental details

Crystal data
Chemical formula	C₄H₁₂O₄P₂
M_r	186.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	6.7761 (18), 18.703 (8), 6.8401 (15)
β (°)	102.09 (3)
V (Å³)	847.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Nicolet/Siemens P21/P3-four-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4847, 2466, 1879
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.079, 1.01
No. of reflections	2466
No. of parameters	139
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.34

Computer programs: R3m/V Software (Siemens, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2	0.95 (4)	1.55 (4)	2.504 (2)	178 (3)
O1—H1···O3	0.94 (4)	1.56 (4)	2.499 (2)	179 (4)

Acknowledgements

The authors thank L. Langner for technical support.

References

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Bruckmann, J., Krüger, C., Lehmann, C. W., Leitner, W., Rust, J. & Six, C. (1999). Acta Cryst. C55, 695–696. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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