Diethyl [(4-bromo­phen­yl)(5-chloro-2-hydroxy­anilino)meth­yl]phospho­nate

V H H Surendra Babu; M Krishnaiah; G Syam Prasad; C Suresh Reddy; Rajni Kant

doi:10.1107/S1600536809043062

. 2009 Oct 28;65(Pt 11):o2859. doi: 10.1107/S1600536809043062

Diethyl [(4-bromophenyl)(5-chloro-2-hydroxyanilino)methyl]phosphonate

V H H Surendra Babu ^a, M Krishnaiah ^a,^*, G Syam Prasad ^b, C Suresh Reddy ^b, Rajni Kant ^c

PMCID: PMC2971341 PMID: 21578446

Abstract

In the title compound, C₁₇H₂₀BrClNO₄P, intermolecular C—H⋯O and N—H⋯O hydrogen bonds form centrosymmetric R ₂ ²(10) dimers linked through O—H⋯O intermolecular hydrogen bonds, which form centrosymmetric R ₂ ²(16) dimers. All these hydrogen bonds form chains along [010]. In addition, the crystal structure is stabilized by weak C—H⋯Br hydrogen bonds. The very weak intramolecular N—H⋯O interaction forms a five-membered ring.

Related literature

For related structures, see: Krishnaiah et al. (2009 ▶); Yang et al. (2005 ▶).

Experimental

Crystal data

C₁₇H₂₀BrClNO₄P
M _r = 448.66
Triclinic,
a = 7.8596 (15) Å
b = 9.1887 (13) Å
c = 14.425 (2) Å
α = 82.921 (13)°
β = 80.372 (15)°
γ = 70.701 (16)°
V = 966.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 293 K
0.30 × 0.24 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.511, T _max = 0.653
12477 measured reflections
5846 independent reflections
2891 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.140
S = 1.05
5846 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CryAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CryAlis Pro; data reduction: CryAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ZORTEPII (Zsolnai, 1997 ▶); software used to prepare material for publication: PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043062/hg2579sup1.cif

e-65-o2859-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043062/hg2579Isup2.hkl

e-65-o2859-Isup2.hkl^{(255.1KB, 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
N4—H4⋯O8ⁱ	0.86	2.47	3.287 (4)	159
C24—H24A⋯O5ⁱⁱ	0.97	2.53	3.472 (7)	163
O8—H8⋯O5ⁱ	0.82	1.90	2.615 (4)	145
C15—H15⋯Br2ⁱⁱⁱ	0.98	2.99	3.945 (4)	164
N4—H4⋯O8	0.86	2.27	2.626 (4)	104

Open in a new tab

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

Acknowledgments

MK thanks the University Grants Commission, New Delhi, for sanctioning the major research project for this work.

supplementary crystallographic information

Comment

A similar co-ordination in hydrogen bonding, diethyl[(5-chloro- 2-hydroxyanilino)(4-chlorophenyl)methyl]phosphonate has been reported by us (Krishnaiah et al., 2009). In continuation of our study on series of phosphonate compounds, we are now reporting the conformation of the structure of the title compound. The P=O(2) bond length is in good agreement with related structures (Krishnaiah et al., 2009; Yang et al., 2005). The bond angles O(2)—P(1)—O(1), O(2)—P(1)—O(3), O(2)—P(1)—C(7) are much larger than O(1)—P(1)—O(3) , O(1)—P(1)—C(7), O(3)—P(1)—C(7) bond angles, indicate a distorted tetrahedral around the phosphorus atom. The planar benzene rings are nearly perpendicular to each with dihedral angle of 78.1 (1)°. The P—O—C—C groups are in trans configuration avoiding steric interactions. The P(1)/O(1)/C(14)/C(15) group is nearly planar unlike the P(1)/O(3)/C(16)/C(17) group, the end atoms C(16)and C(17) are completely out of plane due to more thermal vibrations.

The O—H···O intermolecular hydrogen bonds act as a bridge between C—H···O intermolecular bonds, intra and intermolecular N—H···O hydrogen bonds. Here the phosphonate double bonded oxygen atom, which behaves as an acceptor participates in C—H···O intermolecular hydrogen bonding, whereas, the hydroxyl oxygen, which acts as both donor and acceptor, participates in the N—H···O intra and intermolecular hydrogen bonding. These hydrogen bond form chains along [010]. Additionally, the crystal structure is stabilized by C—H···Br hydrogen bonds.

Experimental

To a stirred solution of 2-amino-4-chlorophenol (0.72 g, 0.005 mol), 4-bromo benzaldehyde (0.005 mol) in anhydrous toluene (15 ml) was added dropwise. Stirring was continued at room temperature of lh. Then diethylphosphite (0.7 g, 0.005 mol) in anhydrous toulene (15 ml) was added dropwise. Stirring was continued at room temperature for another 0.5 h, later the mixture was heated under reflux for 4–6 h. After completion of reaction (monitored by TLC) and the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography on silica gel using petroleum ether-ethyl acetate (8:2) as eluent. Colorless, rectangular shaped single crystals were obtained for diffraction studies using methanol by slow evaporation.