4-[(Dieth-oxy-phosphino-yl)meth-yl]benzoic acid.

In the title compound, C(12)H(17)N(2)O(5)P, the phospho-nate group is almost orthogonal to both the ethyl groups, with a dihedral angle of 83.75 (11)°. In the crystal, mol-ecules are linked into centrosymmetric dimers via pairs of O-H⋯O hydrogen bonds with an R(2) (2)(20) graph-set motif. The crystal structure is further consolidated by weak C-H⋯π inter-actions.

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 = 272.23

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.106

S = 1.04

2960 reflections

165 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.22 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H17O5P	F(000) = 576
Mr = 272.23	Dx = 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

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

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(Fo2) + (0.0578P)2 + 0.272P] where P = (Fo2 + 2Fc2)/3
2960 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) .