Dimethyl [hydr­oxy(2-nitro­phen­yl)meth­yl]phospho­nate

M Nawaz Tahir; Nurcan Acar; Hamza Yilmaz; Muhammad Ilyas Tariq; Dinçer Ülkü

doi:10.1107/S1600536809005467

. 2009 Feb 21;65(Pt 3):o562. doi: 10.1107/S1600536809005467

Dimethyl [hydroxy(2-nitrophenyl)methyl]phosphonate

M Nawaz Tahir ^a,^*, Nurcan Acar ^b, Hamza Yilmaz ^b, Muhammad Ilyas Tariq ^c, Dinçer Ülkü ^d

PMCID: PMC2968685 PMID: 21582219

Abstract

In the title compound, C₉H₁₂NO₆P, intramolecular C—H⋯O hydrogen bonds form five- and six-membered rings. In the crystal, inversion dimers lined by pairs of C—H⋯O hydrogen bonds occur with ring motifs R ₂ ²(10). The O atom of the hydroxy group behaves as an accepter and the benzene ring as donor. Adjacent dimers are connected through O—H⋯O links.

Related literature

For related structures, see: Acar et al. (2009 ▶); Tahir et al. (2007 ▶); Chen et al. (2008 ▶); Maliha et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₂NO₆P
M _r = 261.17
Monoclinic,
a = 9.8685 (12) Å
b = 7.5081 (11) Å
c = 16.1052 (12) Å
β = 90.341 (1)°
V = 1193.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.26 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (MolEN; Fair, 1990 ▶) T _min = 0.939, T _max = 0.959
2222 measured reflections
2093 independent reflections
1873 reflections with I > 2σ(I)
R _int = 0.017
3 standard reflections frequency: 120 min intensity decay: −1.6%

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.231
S = 1.00
2093 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005467/at2724sup1.cif

e-65-0o562-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005467/at2724Isup2.hkl

e-65-0o562-Isup2.hkl^{(100.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.87 (3)	1.81 (3)	2.674 (3)	171 (4)
C6—H6⋯O1	0.93	2.30	2.688 (3)	104
C6—H6⋯O1ⁱⁱ	0.93	2.58	3.343 (4)	140
C7—H7⋯O2	0.93 (3)	2.29 (3)	2.827 (4)	116 (2)

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

(R)-Dimethyl [(2-chlorophenyl)hydroxymethyl]phosphonate (Tahir et al., 2007) and Dimethyl (1-hydroxy-1,2-diphenylethyl)phosphonate (Acar et al., 2009) have been reported by us. In continuation to the study of phosphonate compounds, we herein report the preparation and crystal structure of the title compound (I), (Fig 1).

Diethyl [hydroxy(2-nitrophenyl)methyl]phosphonate (II) (Chen et al., 2008) have also been published which have similar coordination around the C-atom having α-hydroxy group. But it is observed that the change of diethylphosphonate (II) with dimethylphosphonate (I) results in the S-conformation at the methine. In (I), the P═O is 1.467 (2) Å, whereas P–O and P–C have values of [1.557 (2), 1.563 (2) Å] and 1.829 (2) Å, respectively. The nitro group is oriented at an angle of 27.96 (23)° with the benzene ring A(C1—C6). There exist two intramolecular H-bondings which form five B(O1/C7/C1/C6/H6···O1) and six C(O2/N1/C2/C1/C7/H7···O2) membered rings. The title compound is dimerized (Fig 2) forming ring motifs R₂²(10) (Bernstein et al., 1995) if only intermolecular H-bonding is concerned. This ten membered ring is splitted into three rings through intramolecular H-bonding resulting in the formation of central four membered ring [O···H···O···H···O]. A similar ring has already been observed in 3-[(methylcarbamoyl)amino]-1H-isoindolium chloride (Maliha et al., 2009). The O-atom of hydroxy group behaves as an accepter and the benzene ring as donar. The adjacent dimers are connected through intermolecular H-bonds of O–H···O type, where the accepter is doubly bonded O the phosphonate group.

Experimental

A solution of O-nitrobenzaldehide (3.01 g, 20 mmole) and dimethylphosphonate (2.20 g, 20 mmole) was prepared in THF (50 ml). To this solution, a powder mixture of an equal amount of KF and commercial Al₂O₃ (2.5 g + 2.5 g) was added slowly and stirred for 48 h at 273 K. The product was filtered and the filtrate was evaporated at room temperature. The crystalline material obtained after two days was washed with ether and recrystallized in a solution mixture of petroleum ether and THF(1:1), [m.p: 383 K].