Crystal structure of diethyl [(4-nitro­phenyl­amino)(2-hy­droxy­phen­yl)meth­yl]phospho­nate methanol monosolvate

QingMing Wang; Feng Su; TingTing Yang; LiPing Lu; MiaoLi Zhu

doi:10.1107/S1600536814018649

. 2014 Aug 30;70(Pt 9):o1053–o1054. doi: 10.1107/S1600536814018649

Crystal structure of diethyl [(4-nitrophenylamino)(2-hydroxyphenyl)methyl]phosphonate methanol monosolvate

QingMing Wang ^a, Feng Su ^b, TingTing Yang ^a, LiPing Lu ^b, MiaoLi Zhu ^b,^*

PMCID: PMC4186192 PMID: 25309221

Abstract

In the title compound, C₁₇H₂₁N₂O₆P·CH₃OH, the planes of the 4-nitroaniline and 2-hydroxyphenyl groups form a dihedral angle of 84.04 (8)°. The P atom exhibits tetrahedral geometry involving two O-ethyl groups, a Cα atom and a double-bonded O atom. In the crystal, O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the α-aminophosphonic acid and methanol molecules into chains that propagate parallel to the a axis.

Keywords: crystal structure, α-aminophosphonic acids, phosphonate salts, hydrogen bonding

Related literature

For background to the synthesis and properties of α-aminophosphonic acids, see: Allen et al. (1978 ▶); Arizpe et al. (2011 ▶); Cherkasov & Galkin (1998 ▶); Sieńczyk & Oleksyszyn (2009 ▶). For structures of related compounds, see: Li et al. (2008 ▶); Wang et al. (2012 ▶).

Experimental

Crystal data

C₁₇H₂₁N₂O₆P·CH₄O
M _r = 412.37
Triclinic,
a = 9.401 (6) Å
b = 10.061 (6) Å
c = 11.963 (7) Å
α = 101.328 (10)°
β = 94.183 (10)°
γ = 104.549 (9)°
V = 1065.0 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.40 × 0.34 × 0.30 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.935, T _max = 0.951
14569 measured reflections
5230 independent reflections
2934 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.138
S = 1.01
5230 reflections
262 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814018649/pk2529sup1.cif

e-70-o1053-sup1.cif^{(28.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018649/pk2529Isup2.hkl

e-70-o1053-Isup2.hkl^{(256.1KB, hkl)}

Click here for additional data file.^{(7.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018649/pk2529Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S1600536814018649/pk2529fig1.tif

A view of the structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S1600536814018649/pk2529fig2.tif

Crystal packing of the title compound, drawn so as to highlight the hydrogen-bonding interactions between molecules.

CCDC reference: 1019639

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4ⁱ	0.82	2.00	2.819 (3)	172
O1—H1⋯O7	0.82	1.95	2.757 (3)	170
C10—H10⋯O5ⁱⁱ	0.93	2.53	3.308 (4)	141
N1—H1A⋯O4ⁱⁱⁱ	0.82 (2)	2.14 (2)	2.959 (3)	171 (2)

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

Acknowledgments

This work was supported financially by the National Natural Science Foundation for Young Scientists of China (grant No. 21301150), the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (grant No. 13KJB150037), the Foundation of Jiangsu Provincial Key Laboratory of Solonchak (grant No. JKLBS2012022), the Doctor and Professor Foundation of Yancheng Teachers’ University (grant No. 12YSYJB0117) and the Practice Innovation Training Program Projects for the Jiangsu College Students (grant Nos. 201310324034Y and 201410324038Y).

supplementary crystallographic information

S1. Introduction

As mimics of natural amino acids, α-aminophosphonic acids and related derivatives are currently attracting a great deal of interest in medicinal chemistry due to their important biological effects (Arizpe, et al., 2011). They have been reported to possess a wide range of biological functions. These include antibacterial activities (Allen et al., 1978), action as inhibitors of enzymes such as rennin, HIV proteases, serine proteases and so on (Sieńczyk, et al., 2009).

S2. Experimental

S2.1. Synthesis and crystallization

The synthesis of o-cresol α-aminophosphonate N-derivatives with rigid structures was achieved through the Pudovik reaction reaction (Cherkasov et al., 1998). We obtained the title compound following our earlier report (Wang et al., 2012). The synthesis involved two steps: a) the Schiff bases were first prepared in a condensation of 4-nitroaniline and salicylaldehyde in methanol solvent by refluxing equimolar amounts of reagents; b ) reaction of Schiff base with a diethyl phosphonate in methanol solvent under reflux. The title compound was obtained from the filtrate after three days.

S2.2. Refinement

The amine H atom was located in a difference Fourier map and refined freely. All other H atoms were placed in geometrically idealized positions and refined as riding, with C–H = 0.93-0.98 Å, O–H = 0.82 Å, and the Uiso(H) = 1.2Ueq (C) for benzene ring, C7, C14, C16 and Uiso(H) = 1.5Ueq (O, C) for O—H groups and C15, C17, C18.

S3. Results and discussion

The crystal structure of the title compound is triclinic, with space group P1. As seen from Fig. 1, the P atom has tetrahedral geometry involving two O-ethyl groups (O2, O3), one Cα atom (C7), and a double bond O atom (O4), which is the same as our earlier reports (Li et al., 2008; Wang et al., 2012). The C—P and P═O bond lengths are comparable to those in similar structures (Li et al. 2008; Wang et al., 2012). Several hydrogen bonding interactions [O7—H7A···O4ⁱ (i = x+1,y,z), O1—H1···O7, C10—H10···O5ⁱⁱ (ii=-x, -y, -z-1), N1—H1A···O4ⁱⁱⁱ (iii=-x, -y+1, -z)] exist within in the crystal structure. The dihedral angle formed by the planes of the 4-nitroaniline and 2-hydroxyphenyl groups is 84.08 (8)°.