Meth­yl(phen­yl)phosphinic acid

Burrow, R.A.; Siqueira da Silva, R.M.

doi:10.1107/S1600536811025530

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2005

doi:10.1107/S1600536811025530

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Methyl(phenyl)phosphinic acid

Robert A. Burrow ^a ^* and Rubia M. Siqueira da Silva ^a

^aLaboratório de Materiais Inorgânicos, Universidade Federal de Santa Maria, Av. Roraima, 1000 - Camobi, 97105-900 Santa Maria, RS, Brazil
^*Correspondence e-mail: rburrow@ewald.base.ufsm.br

(Received 18 January 2011; accepted 28 June 2011; online 9 July 2011)

The crystal structure of the title compound, C₇H₉O₂P, displays O—H⋯O hydrogen bonding , which links individual molecules related via the c-glide plane and translational symmetry along the crystallographic b-axis direction into continuous chains.

Related literature

For background to phosphinic acids and their applications, see: Beckmann et al. (2009 ); Burrow et al. (2000 ); Burrow & Siqueira da Silva (2011 ); Chen & Suslick (1993 ); Siqueira et al. (2006 ); Vioux et al. (2004 ). For a description of the Cambridge Structural Database, see: Allen (2002 ) and for geometrical analysis using Mogul, see: Bruno et al. (2004 ).

Experimental

Crystal data

C₇H₉O₂P
M_r = 156.11
Orthorhombic, P b c a
a = 12.4231 (8) Å
b = 7.8464 (5) Å
c = 15.9801 (10) Å
V = 1557.69 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.34 × 0.34 × 0.18 mm

Data collection

Bruker X8 Kappa APEXII diffractometer
Absorption correction: Gaussian (SADABS; Bruker 2009 ) T_min = 0.668, T_max = 0.950
19802 measured reflections
2342 independent reflections
1506 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.145
S = 1.04
2342 reflections
95 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.89 (3)	1.62 (3)	2.494 (2)	168 (3)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025530/zb2012sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025530/zb2012Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025530/zb2012Isup3.cml

checkCIF report

Comment top

Phosphinic acids have been used for the synthesis of coordination polymers [Siqueira et al., 2006; Beckmann et al.,2009] which have the potential for a wide range of applications [Vioux et al., 2004; Chen & Suslick, 1993]. As part of our ongoing research on phosphinic acids [Burrow et al., 2000; Burrow & Siqueira da Silva, 2011], we report the synthesis and crystal structure of the title compound, C₇H₉O₂P, (I).

The title compound, Fig. 1, crystallizes as a racemic mixture of enantiomers in the centrosymmetric space group Pbca. An analysis of the geometry of (I) by Mogul [Bruno et al., 2004] using the Cambridge Structural Database [CSD, Allen, 2002] shows no unusual features; all absolute values of the z scores were below 1.0. An enhanced figure is provided, Fig. 2.

The crystal structure of (I) shows hydrogen bonding between the phosphinic acid moieties of the type OH···O=P—OH···O=P related by the c glide plane and translational symmetry along the crystallographic b direction to form continuous chains, Table 1. The very short P—O···O=P distance of 2.494 (2) Å indicates a strong hydrogen bond. This is very slightly shorter than the average O···O interaction distance in the CSD of 2.51 (5) Å for 45 observations for other phosphinic acids.

The packing diagram, Fig. 3, shows that the hydrogen bonded chains of (I) pack together in a head-to-head fashion in the crystallographic b direction to form columns. Neighboring columns in the crystallographic a direction run in the opposite direction with the neighboring methyl groups packing together. The effect creates a pseudo-lamellar structure parallel to the crystallographic ab plane where the phosphinate groups and methyl groups are in a plane surrounded by phenyl groups on either side. There are no phenyl-phenyl interactions. The distance between layers is half the c axis distance, 7.9900 (5) Å.

Related literature top

For background to phosphinic acids and their applications, see: Beckmann et al. (2009); Burrow et al. (2000); Burrow & Siqueira da Silva (2011); Chen & Suslick (1993); Siqueira et al. (2006); Vioux et al. (2004). For a description of the Cambridge Structural Database, see: Allen (2002) and for geometrical analysis using Mogul, see: Bruno et al. (2004).

Experimental top

To a solution of phenylphosphinic acid (2.0 g, 14.1 mmol) in dichloromethane, 30 ml diisopropylethylamine (5.16 ml, 29.6 mmol) and trimethylsilyl chloride (3.74 ml, 29.6 mmol) were separately added at 0 °C under argon. The reaction mixture was stirred at room temperature for 2–3 h, cooled to 0 °C and iodomethane (0.97 ml, 15.6 mmol) was added. After further stirring at room temperature for 24 h, the solvent was removed under vacuum. The residue was suspended in hydrochloric acid (2 M, 20 ml) and filtered on a glass frit under vacuum. The white solid was washed with acetone and dried giving a yield of 1.60 g (66%) of pure product. Crystals were obtained by slow evaporation from a methanol solution. IR (KBr): 1439 (s), 1304 (w), 1266 (m), 1171 (s), 1134 (s), 1049 (m, br), 1026 (m), 982 (versus), 881 (s), 779 (s), 745 (s), 700 (m), 512 (m), 482 (m), 439 (w) cm^-1. C₇H₉O₂P (156.12): calc.: C 53.85, H 5.81; found: C 52.77, H 6.01%.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic labelling scheme. The anisotropic displacement parameters are at the 30% level; H atoms are represented by circles of arbitrary size.
	Fig. 2. The packing diagram of (I) looking down the crystallographic a direction with the crystallographic b axis up. The H bonding are shown as red dashed lines and phenyl (C₆H₅) groups shown as sticks for clarity.

Methyl(phenyl)phosphinic acid top

Crystal data top

C₇H₉O₂P	D_x = 1.331 Mg m⁻³
M_r = 156.11	Melting point = 402–408 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 12.4231 (8) Å	Cell parameters from 788 reflections
b = 7.8464 (5) Å	θ = 2.5–22.7°
c = 15.9801 (10) Å	µ = 0.29 mm⁻¹
V = 1557.69 (17) Å³	T = 296 K
Z = 8	Irregular block, colourless
F(000) = 656	0.34 × 0.34 × 0.18 mm

Data collection top

Bruker X8 Kappa APEXII diffractometer	2342 independent reflections
Radiation source: fine focus ceramic X-ray tube	1506 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.5°, θ_min = 3.0°
0.5° ϕ and ω scans	h = −17→16
Absorption correction: gaussian (SADABS; Bruker 2009)	k = −11→11
T_min = 0.668, T_max = 0.950	l = −22→22
19802 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0622P)² + 0.898P] where P = (F_o² + 2F_c²)/3
2342 reflections	(Δ/σ)_max < 0.001
95 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₇H₉O₂P	V = 1557.69 (17) Å³
M_r = 156.11	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.4231 (8) Å	µ = 0.29 mm⁻¹
b = 7.8464 (5) Å	T = 296 K
c = 15.9801 (10) Å	0.34 × 0.34 × 0.18 mm

Data collection top

Bruker X8 Kappa APEXII diffractometer	2342 independent reflections
Absorption correction: gaussian (SADABS; Bruker 2009)	1506 reflections with I > 2σ(I)
T_min = 0.668, T_max = 0.950	R_int = 0.057
19802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.35 e Å⁻³
2342 reflections	Δρ_min = −0.39 e Å⁻³
95 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 > 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
P1	0.82414 (4)	0.86402 (6)	0.46093 (3)	0.03532 (18)
O1	0.85676 (12)	1.0170 (2)	0.51708 (10)	0.0413 (4)
H1	0.823 (2)	1.114 (4)	0.504 (2)	0.062*
O2	0.71118 (12)	0.8030 (2)	0.47403 (10)	0.0456 (4)
C1	0.9197 (2)	0.7033 (2)	0.48579 (17)	0.0505 (5)
H1A	0.9154	0.6771	0.5444	0.076*
H1B	0.9907	0.7433	0.4727	0.076*
H1C	0.9044	0.6026	0.4537	0.076*
C11	0.84247 (18)	0.9303 (2)	0.35447 (12)	0.0384 (5)
C12	0.9378 (2)	1.0107 (2)	0.32936 (16)	0.0503 (5)
H12	0.9933	1.0267	0.3676	0.06*
C13	0.9496 (2)	1.0661 (4)	0.24804 (17)	0.0626 (7)
H13	1.0128	1.1201	0.2317	0.075*
C14	0.8681 (2)	1.0420 (4)	0.19095 (17)	0.0684 (8)
H14	0.8762	1.0804	0.1363	0.082*
C15	0.7754 (2)	0.9616 (4)	0.21438 (17)	0.0735 (9)
H15	0.7211	0.9447	0.1752	0.088*
C16	0.7612 (2)	0.9050 (2)	0.29563 (17)	0.0559 (7)
H16	0.6977	0.8504	0.3109	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0314 (2)	0.0321 (2)	0.0425 (2)	−0.0001 (2)	0.0008 (2)	0.0015 (2)
O1	0.0458 (9)	0.0356 (8)	0.0426 (9)	0.0015 (7)	−0.0052 (7)	0.0003 (7)
O2	0.0328 (8)	0.0381 (8)	0.0660 (11)	−0.0008 (7)	0.0059 (7)	0.0031 (7)
C1	0.0406 (13)	0.0406 (13)	0.0703 (16)	0.0049 (10)	−0.0013 (11)	0.0057 (11)
C11	0.0404 (11)	0.0356 (11)	0.0391 (11)	−0.0005 (9)	−0.0005 (9)	−0.0028 (9)
C12	0.0444 (13)	0.0555 (15)	0.0511 (14)	−0.0032 (11)	0.0031 (11)	0.0012 (11)
C13	0.0661 (18)	0.0662 (17)	0.0555 (16)	−0.0018 (15)	0.0193 (14)	0.0039 (14)
C14	0.100 (3)	0.0658 (18)	0.0395 (14)	0.0060 (18)	0.0101 (15)	0.0029 (13)
C15	0.095 (2)	0.078 (2)	0.0473 (16)	−0.007 (2)	−0.0204 (15)	−0.0019 (15)
C16	0.0537 (16)	0.0614 (16)	0.0525 (14)	−0.0097 (13)	−0.0108 (11)	−0.0034 (11)

Geometric parameters (Å, º) top

P1—O2	1.4976 (16)	C12—C13	1.378 (4)
P1—O1	1.5526 (16)	C12—H12	0.93
P1—C1	1.777 (2)	C13—C14	1.375 (4)
P1—C11	1.794 (2)	C13—H13	0.93
O1—H1	0.89 (3)	C14—C15	1.366 (5)
C1—H1A	0.96	C14—H14	0.93
C1—H1B	0.96	C15—C16	1.383 (4)
C1—H1C	0.96	C15—H15	0.93
C11—C16	1.394 (3)	C16—H16	0.93
C11—C12	1.401 (3)

O2—P1—O1	114.29 (9)	C13—C12—C11	120.1 (2)
O2—P1—C1	111.56 (10)	C13—C12—H12	119.9
O1—P1—C1	104.21 (11)	C11—C12—H12	119.9
O2—P1—C11	110.13 (10)	C14—C13—C12	120.3 (3)
O1—P1—C11	106.92 (10)	C14—C13—H13	119.9
C1—P1—C11	109.45 (11)	C12—C13—H13	119.9
P1—O1—H1	114 (2)	C15—C14—C13	120.1 (3)
P1—C1—H1A	109.5	C15—C14—H14	119.9
P1—C1—H1B	109.5	C13—C14—H14	119.9
H1A—C1—H1B	109.5	C14—C15—C16	120.9 (3)
P1—C1—H1C	109.5	C14—C15—H15	119.6
H1A—C1—H1C	109.5	C16—C15—H15	119.6
H1B—C1—H1C	109.5	C15—C16—C11	119.7 (3)
C16—C11—C12	118.9 (2)	C15—C16—H16	120.2
C16—C11—P1	120.4 (2)	C11—C16—H16	120.2
C12—C11—P1	120.63 (17)

O2—P1—C11—C16	−6.3 (2)	P1—C11—C12—C13	−177.8 (2)
O1—P1—C11—C16	−131.0 (2)	C11—C12—C13—C14	−0.4 (4)
C1—P1—C11—C16	116.7 (2)	C12—C13—C14—C15	−0.5 (5)
O2—P1—C11—C12	172.62 (18)	C13—C14—C15—C16	0.7 (5)
O1—P1—C11—C12	47.9 (2)	C14—C15—C16—C11	0.0 (5)
C1—P1—C11—C12	−64.4 (2)	C12—C11—C16—C15	−0.9 (4)
C16—C11—C12—C13	1.1 (4)	P1—C11—C16—C15	178.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.89 (3)	1.62 (3)	2.494 (2)	168 (3)

Symmetry code: (i) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₇H₉O₂P
M_r	156.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	12.4231 (8), 7.8464 (5), 15.9801 (10)
V (Å³)	1557.69 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.34 × 0.34 × 0.18

Data collection
Diffractometer	Bruker X8 Kappa APEXII diffractometer
Absorption correction	Gaussian (SADABS; Bruker 2009)
T_min, T_max	0.668, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	19802, 2342, 1506
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.145, 1.04
No. of reflections	2342
No. of parameters	95
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.39

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.89 (3)	1.62 (3)	2.494 (2)	168 (3)

Symmetry code: (i) −x+3/2, y+1/2, z.

Acknowledgements

Financial support from the Conselho Nacional de Desenvolvimento Científico (CNPq, Brazil; grants 485245/2007–8 and 479747/2009–1) and the Fundação de Amparo à Pesquisa (FAPERGS, Rio Grande do Sul) is gratefully acknowledged, as are fellowships from CNPq (RAB) and the Coordenação de Aperfeiçoamento de Pessoas de Nível Superior (CAPES, Brazil; RMSS). The diffractometer was funded by a CT-INFRA grant from the Financiadora de Estrutos e Projetos (FINEP, Brazil).

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