4-[(Dieth­oxy­phosphino­yl)meth­yl]benzoic acid

Karthikeyan, S.; Sethusankar, K.; Rajeshwaran, G.G.; Mohanakrishnan, A.K.

doi:10.1107/S1600536811008282

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o831

doi:10.1107/S1600536811008282

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4-[(Diethoxyphosphinoyl)methyl]benzoic acid

S. Karthikeyan,^a K. Sethusankar,^a ^* Ganesan Gobi Rajeshwaran ^b and Arasambattu K. Mohanakrishnan ^b

^aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^bDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 1 March 2011; accepted 4 March 2011; online 9 March 2011)

In the title compound, C₁₂H₁₇N₂O₅P, the phosphonate group is almost orthogonal to both the ethyl groups, with a dihedral angle of 83.75 (11)°. In the crystal, molecules are linked into centrosymmetric dimers via pairs of O—H⋯O hydrogen bonds with an R₂²(20) graph-set motif. The crystal structure is further consolidated by weak C—H⋯π interactions.

Related literature

For applications of phosphonate derivatives, see: Hirschmann et al. (1994 ). For related structures, see: An et al. (2008 ); Chen et al. (2008 ). For graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₇O₅P
M_r = 272.23
Monoclinic, P 2₁ /n
a = 9.6505 (5) Å
b = 12.1706 (6) Å
c = 11.8156 (6) Å
β = 108.926 (2)°
V = 1312.74 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
13181 measured reflections
2960 independent reflections
2441 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.106
S = 1.04
2960 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱ	0.82	1.87	2.644 (2)	158
C12—H12C⋯Cg1ⁱⁱ	0.96	2.97	3.853 (2)	153
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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, PARST (Nardelli, 1983 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008282/pv2396sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008282/pv2396Isup2.hkl

checkCIF report

Comment top

Phosphonates have also been used as enzyme inhibitors, anti-HIV agents and haptens for catalytic antibodies (Hirschmann et al., 1994). In this regard, the preparation of various phosphonates with a diversity of structures is highly desirable for drug discovery and medicinal chemistry.

In the title compound (Fig. 1), the phosphonate group is almost orthogonal to the diethyl group with a dihedral angle of 83.75 (11)°. The carboxybenzene ring is essentially planar with the maximum deviation of atom C5 being 0.047 (1) Å. The atom C8 is significantly out of the plane formed by the benzene ring atoms C2/C3/C4/C5/C6/C7; the deviation being 0.108 (2) Å. In addition, the atom C1 of the carboxyl group is 0.095 (2) Å out of the plane of the same benzene ring. The dihedral angle between the benzene ring and the carboxyl group is 3.83 (16)°.

In the crystal, molecules are linked into centrosymmetric dimers via pairs of O–H···O hydrogen bonds with a R²₂(20) graph set motif (Bernstein, et al., 1995). The crystal structure is further stabilized by C–H···π interaction, where Cg1 is the centroid of the benzene ring (C2/C3/C4/C5/C6/C7).

Related literature top

For applications of phosphonate derivatives, see: Hirschmann et al. (1994). For related structures, see: An et al. (2008); Chen et al. (2008). For graph-set motifs, see: Bernstein et al. (1995).

Experimental top

To a solution of 4-(bromomethyl)benzoic acid (1 mmol) and triethylphosphite (1.1 mmol) in dry dichloromethane (10 ml) at room temperature, ZnBr₂ (0.2 mmol) was added and allowed to stir for 2 h under N₂. After consumption of 4-(bromomethyl)benzoic acid (monitored by TLC) volatile components were removed under vacuo. The residual mass was poured over crushed ice (200 g) containing conc. HCl (5 ml). The precipitated solid was filtered, washed with water and dried to give crude phosphonate ester. The crude product was purified by flash column chromatography to provide the title compound which was recrystalized from 20% ethylacetate in pure hexane.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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), PARST (Nardelli, 1983) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme, displacement ellipsoids are drawn at 30% probability level. H atoms are represented by small spheres of arbitary radius.
	Fig. 2. A stereo view of the unit cell of the title compound, showing the dimer formed by H-bonding in R²₂(20) graph set motif along a axis.

4-[(Diethoxyphosphinoyl)methyl]benzoic acid top

Crystal data top

C₁₂H₁₇O₅P	F(000) = 576
M_r = 272.23	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2960 reflections
a = 9.6505 (5) Å	θ = 1.0–25.0°
b = 12.1706 (6) Å	µ = 0.22 mm⁻¹
c = 11.8156 (6) Å	T = 293 K
β = 108.926 (2)°	Block, colourless
V = 1312.74 (12) Å³	0.23 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	2441 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 27.3°, θ_min = 2.4°
ω scans	h = −12→12
13181 measured reflections	k = −15→15
2960 independent reflections	l = −15→15

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: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0578P)² + 0.272P] where P = (F_o² + 2F_c²)/3
2960 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₁₇O₅P	V = 1312.74 (12) Å³
M_r = 272.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6505 (5) Å	µ = 0.22 mm⁻¹
b = 12.1706 (6) Å	T = 293 K
c = 11.8156 (6) Å	0.23 × 0.20 × 0.20 mm
β = 108.926 (2)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2441 reflections with I > 2σ(I)
13181 measured reflections	R_int = 0.025
2960 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	Δρ_max = 0.31 e Å⁻³
2960 reflections	Δρ_min = −0.22 e Å⁻³
165 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
C1	0.56048 (16)	−0.02314 (13)	0.81418 (13)	0.0410 (3)
C2	0.40996 (15)	0.00742 (12)	0.81102 (12)	0.0367 (3)
C3	0.34611 (17)	0.10233 (13)	0.75114 (14)	0.0430 (3)
H3	0.3950	0.1433	0.7094	0.052*
C4	0.21059 (18)	0.13606 (14)	0.75341 (14)	0.0451 (4)
H4	0.1691	0.2000	0.7135	0.054*
C5	0.13554 (16)	0.07576 (13)	0.81447 (13)	0.0409 (3)
C6	0.19754 (18)	−0.02041 (14)	0.87045 (14)	0.0457 (4)
H6	0.1467	−0.0632	0.9090	0.055*
C7	0.33374 (18)	−0.05359 (13)	0.86979 (13)	0.0426 (3)
H7	0.3748	−0.1177	0.9093	0.051*
C8	−0.00843 (17)	0.11637 (15)	0.82358 (14)	0.0485 (4)
H8A	−0.0678	0.0540	0.8304	0.058*
H8B	−0.0611	0.1561	0.7512	0.058*
C9	−0.24479 (18)	0.29083 (16)	0.86037 (16)	0.0536 (4)
H9A	−0.2711	0.2456	0.7889	0.064*
H9B	−0.2059	0.3599	0.8428	0.064*
C10	−0.3748 (2)	0.31113 (17)	0.89678 (18)	0.0623 (5)
H10A	−0.4147	0.2423	0.9110	0.094*
H10B	−0.4470	0.3501	0.8344	0.094*
H10C	−0.3473	0.3542	0.9687	0.094*
C11	0.1723 (2)	0.38949 (16)	0.99414 (17)	0.0558 (4)
H11A	0.1735	0.3721	1.0746	0.067*
H11B	0.1314	0.4625	0.9740	0.067*
C12	0.3235 (2)	0.38617 (19)	0.98815 (19)	0.0662 (5)
H12A	0.3629	0.3135	1.0074	0.099*
H12B	0.3837	0.4377	1.0443	0.099*
H12C	0.3217	0.4051	0.9088	0.099*
O1	0.10809 (12)	0.15721 (11)	1.06524 (9)	0.0519 (3)
O2	−0.13529 (11)	0.23494 (10)	0.95801 (9)	0.0451 (3)
O3	0.08356 (12)	0.30987 (10)	0.91015 (10)	0.0502 (3)
O4	0.60874 (12)	−0.11402 (10)	0.87523 (10)	0.0513 (3)
H4A	0.6917	−0.1275	0.8744	0.077*
O5	0.63179 (14)	0.02983 (11)	0.76684 (12)	0.0608 (3)
P1	0.01894 (4)	0.20435 (4)	0.95001 (3)	0.04038 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0400 (8)	0.0442 (8)	0.0372 (7)	0.0009 (6)	0.0103 (6)	−0.0061 (6)
C2	0.0377 (7)	0.0394 (7)	0.0319 (6)	−0.0005 (6)	0.0097 (5)	−0.0043 (6)
C3	0.0455 (8)	0.0437 (9)	0.0428 (8)	0.0007 (7)	0.0183 (6)	0.0053 (6)
C4	0.0467 (8)	0.0460 (9)	0.0420 (8)	0.0080 (7)	0.0134 (7)	0.0067 (6)
C5	0.0366 (7)	0.0496 (9)	0.0349 (7)	−0.0012 (6)	0.0094 (6)	−0.0066 (6)
C6	0.0476 (8)	0.0478 (9)	0.0462 (8)	−0.0064 (7)	0.0215 (7)	0.0007 (7)
C7	0.0486 (8)	0.0392 (8)	0.0404 (8)	0.0031 (6)	0.0149 (6)	0.0035 (6)
C8	0.0349 (8)	0.0628 (11)	0.0454 (8)	−0.0007 (7)	0.0096 (6)	−0.0077 (7)
C9	0.0436 (9)	0.0682 (12)	0.0482 (9)	0.0145 (8)	0.0136 (7)	0.0164 (8)
C10	0.0432 (9)	0.0730 (13)	0.0693 (12)	0.0140 (9)	0.0161 (8)	0.0071 (10)
C11	0.0579 (10)	0.0583 (11)	0.0522 (9)	−0.0065 (8)	0.0193 (8)	−0.0083 (8)
C12	0.0467 (10)	0.0773 (14)	0.0673 (12)	−0.0097 (9)	0.0083 (9)	0.0114 (10)
O1	0.0407 (6)	0.0720 (8)	0.0398 (6)	0.0129 (6)	0.0088 (5)	0.0073 (5)
O2	0.0365 (5)	0.0608 (7)	0.0389 (5)	0.0101 (5)	0.0136 (4)	0.0100 (5)
O3	0.0453 (6)	0.0648 (8)	0.0390 (6)	−0.0090 (5)	0.0115 (5)	0.0004 (5)
O4	0.0428 (6)	0.0574 (7)	0.0518 (6)	0.0115 (5)	0.0128 (5)	0.0075 (5)
O5	0.0500 (7)	0.0632 (8)	0.0783 (9)	0.0047 (6)	0.0333 (6)	0.0109 (7)
P1	0.0314 (2)	0.0556 (3)	0.0334 (2)	0.00373 (16)	0.00944 (15)	0.00211 (16)

Geometric parameters (Å, º) top

C1—O5	1.2049 (19)	C9—C10	1.473 (2)
C1—O4	1.3201 (19)	C9—H9A	0.9700
C1—C2	1.488 (2)	C9—H9B	0.9700
C2—C7	1.381 (2)	C10—H10A	0.9600
C2—C3	1.390 (2)	C10—H10B	0.9600
C3—C4	1.379 (2)	C10—H10C	0.9600
C3—H3	0.9300	C11—O3	1.451 (2)
C4—C5	1.387 (2)	C11—C12	1.484 (3)
C4—H4	0.9300	C11—H11A	0.9700
C5—C6	1.382 (2)	C11—H11B	0.9700
C5—C8	1.511 (2)	C12—H12A	0.9600
C6—C7	1.377 (2)	C12—H12B	0.9600
C6—H6	0.9300	C12—H12C	0.9600
C7—H7	0.9300	O1—P1	1.4708 (11)
C8—P1	1.7867 (16)	O2—P1	1.5666 (11)
C8—H8A	0.9700	O3—P1	1.5654 (12)
C8—H8B	0.9700	O4—H4A	0.8200
C9—O2	1.4558 (18)

O5—C1—O4	123.27 (14)	O2—C9—H9B	110.0
O5—C1—C2	123.67 (15)	C10—C9—H9B	110.0
O4—C1—C2	113.06 (13)	H9A—C9—H9B	108.4
C7—C2—C3	118.85 (14)	C9—C10—H10A	109.5
C7—C2—C1	121.87 (14)	C9—C10—H10B	109.5
C3—C2—C1	119.24 (13)	H10A—C10—H10B	109.5
C4—C3—C2	120.27 (14)	C9—C10—H10C	109.5
C4—C3—H3	119.9	H10A—C10—H10C	109.5
C2—C3—H3	119.9	H10B—C10—H10C	109.5
C3—C4—C5	120.74 (15)	O3—C11—C12	108.69 (15)
C3—C4—H4	119.6	O3—C11—H11A	110.0
C5—C4—H4	119.6	C12—C11—H11A	110.0
C6—C5—C4	118.64 (14)	O3—C11—H11B	110.0
C6—C5—C8	120.56 (15)	C12—C11—H11B	110.0
C4—C5—C8	120.76 (15)	H11A—C11—H11B	108.3
C7—C6—C5	120.77 (14)	C11—C12—H12A	109.5
C7—C6—H6	119.6	C11—C12—H12B	109.5
C5—C6—H6	119.6	H12A—C12—H12B	109.5
C6—C7—C2	120.68 (14)	C11—C12—H12C	109.5
C6—C7—H7	119.7	H12A—C12—H12C	109.5
C2—C7—H7	119.7	H12B—C12—H12C	109.5
C5—C8—P1	111.44 (10)	C9—O2—P1	121.53 (10)
C5—C8—H8A	109.3	C11—O3—P1	123.12 (11)
P1—C8—H8A	109.3	C1—O4—H4A	109.5
C5—C8—H8B	109.3	O1—P1—O3	115.34 (7)
P1—C8—H8B	109.3	O1—P1—O2	108.59 (6)
H8A—C8—H8B	108.0	O3—P1—O2	107.59 (7)
O2—C9—C10	108.36 (14)	O1—P1—C8	115.07 (8)
O2—C9—H9A	110.0	O3—P1—C8	101.85 (8)
C10—C9—H9A	110.0	O2—P1—C8	107.89 (7)

O5—C1—C2—C7	−177.82 (15)	C6—C5—C8—P1	89.85 (17)
O4—C1—C2—C7	1.6 (2)	C4—C5—C8—P1	−87.88 (16)
O5—C1—C2—C3	−0.3 (2)	C10—C9—O2—P1	−178.09 (13)
O4—C1—C2—C3	179.10 (13)	C12—C11—O3—P1	113.06 (15)
C7—C2—C3—C4	1.7 (2)	C11—O3—P1—O1	−31.60 (15)
C1—C2—C3—C4	−175.88 (14)	C11—O3—P1—O2	89.74 (13)
C2—C3—C4—C5	−0.4 (2)	C11—O3—P1—C8	−156.94 (13)
C3—C4—C5—C6	−1.7 (2)	C9—O2—P1—O1	175.49 (13)
C3—C4—C5—C8	176.10 (14)	C9—O2—P1—O3	50.02 (14)
C4—C5—C6—C7	2.6 (2)	C9—O2—P1—C8	−59.17 (15)
C8—C5—C6—C7	−175.21 (14)	C5—C8—P1—O1	−54.31 (15)
C5—C6—C7—C2	−1.4 (2)	C5—C8—P1—O3	71.21 (13)
C3—C2—C7—C6	−0.8 (2)	C5—C8—P1—O2	−175.70 (11)
C1—C2—C7—C6	176.70 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.82	1.87	2.644 (2)	158
C12—H12C···Cg1ⁱⁱ	0.96	2.97	3.853 (2)	153

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇O₅P
M_r	272.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6505 (5), 12.1706 (6), 11.8156 (6)
β (°)	108.926 (2)
V (Å³)	1312.74 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13181, 2960, 2441
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.646

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.106, 1.04
No. of reflections	2960
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), PARST (Nardelli, 1983) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.82	1.87	2.644 (2)	158
C12—H12C···Cg1ⁱⁱ	0.96	2.97	3.853 (2)	153

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

Acknowledgements

SK and KS thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

References

An, L.-T., Gong, G.-X., Liu, X., Xia, M. & Zhou, J.-F. (2008). Acta Cryst. E64, o1320. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, C., Jin, W. & Li, X. (2008). Acta Cryst. E64, o144. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hirschmann, R., Smith, A. B., Taylor, C. M., Benkovic, P. A., Taylor, S., Yager, K. M., Sprengler, P. A. & Benkovic, S. J. (1994). Science, 265, 234–237. CrossRef CAS PubMed Web of Science Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o831

doi:10.1107/S1600536811008282

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