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

Krishnaiah, M.; Surendra Babu, V.H.H.; Syam Prasad, G.; Suresh Reddy, C.; Puranik, V.G.

doi:10.1107/S1600536809037039

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages o2506-o2507

doi:10.1107/S1600536809037039

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

M. Krishnaiah,^a ^* V. H. H. Surendra Babu,^a G. Syam Prasad,^b C. Suresh Reddy ^b and Vedavati G. Puranik ^c

^aDepartment of Physics, S.V. University, Tirupati 517 502, India, ^bDepartment of Chemistry, S.V. University, Tirupati 517 502, India, and ^cCentre of Material Characterization, National Chemical Laboratory, Pune 411 008, India
^*Correspondence e-mail: profkrishnaiah.m@gmail.com

(Received 23 August 2009; accepted 13 September 2009; online 19 September 2009)

In the title compound, C₁₇H₂₀Cl₂NO₄P, the P atom is bonded in a distorted tetrahedral environment. The dihedral angle between the two benzene rings is 80.5 (1)°. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link pairs of molecules into centrosymmetric dimers. These dimers, are in turn, linked by weak intermolecular C—H⋯O hydrogen bonds into one-dimensional chains along [010]. Additional stabilization is provided by very weak C—H⋯Cl interactions.

Related literature

For applications of α-aminophosphonates, see: Allen et al. (1989 ); Baylis et al. (1984 ); Fields (1999 ); Hirschmann et al. (1994 ); Kafarski & Lejczak (1991 ); Miliszkiewicz et al. (1992 ). For the antibacterial activity of the title compound, see: Syam Prasad et al. (2007 ). For related structures, see: Boehlow et al. (1997 ); Yang et al. (2005 ); Sawka-Dobrowolska & Kowalik (1985 ); Sawka-Dobrowolska & Rułko (1987 ); Sanders et al. (1996 ); Ezra & Collin (1973 ). For P—C bond lengths in related structures, see: Rużić-Toroš et al. (1978 ).

Experimental

Crystal data

C₁₇H₂₀Cl₂NO₄P
M_r = 404.21
Triclinic, $[P \overline 1]$
a = 7.790 (3) Å
b = 9.297 (4) Å
c = 14.372 (6) Å
α = 82.817 (6)°
β = 80.842 (6)°
γ = 70.323 (6)°
V = 964.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 294 K
0.25 × 0.25 × 0.13 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.896, T_max = 0.944
10997 measured reflections
4863 independent reflections
3635 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.159
S = 1.05
4863 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O8ⁱ	0.86	2.48	3.286 (3)	157
C24—H24B⋯O5ⁱⁱ	0.97	2.57	3.504 (4)	162
O8—H8⋯O5ⁱ	0.82	1.92	2.636 (2)	145
C15—H15⋯Cl2ⁱⁱⁱ	0.98	2.91	3.872 (3)	165
N4—H4⋯O8	0.86	2.28	2.634 (3)	105
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z; (iii) x+1, y, z.

Data collection: SMART (Bruker 2001 ); cell refinement: SAINT (Bruker 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ZORTEPII (Zsolnai, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: enCIFer (Allen et al., 2004 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037039/lh2891sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037039/lh2891Isup2.hkl

checkCIF report

Comment top

The synthesis of α-aminophosphonates has attracted much interest because of their biological activity and structural analogy to α-amino acids (Fields, 1999). They also act as peptide mimics (Kafarski et al., 1991), enzyme inhibitors (Allen et al., 1989), haptens of catalytic antibodies (Hirschmann et al., 1994), antibiotics and pharmacological agents (Baylis et al., 1984) and the analogues of amino acids, aminophosphonic and aminophophinic acids as plant growth regulators and herbicides (Miliszkiewicz et al., 1992). As a result, a variety of synthetic approaches have been developed for the synthesis of α-aminophosphonates. The title compound (I) exhibits antibacterial activity against Gram positive as well as Gram negative bacteria (Syam et al., 2007)

The molecular structure of the title compound is shown in Fig. 1. (I). The P—O bond distances are in good agreement with those in related structures (Boehlow et al., 1997; Yang et al., 2005). The P1—C15 bond length is in good agreement with the reported values of 1.821 (6) Å, 1.808 (9) Å, 1.813 (6)Å in related structures (Rużić-Toroš et al., 1978; Sawka-Dobrowolska & Rułko, 1987; Sanders et al., 1996). The C9–N4 bond length (1.384 (2) Å) is intermediate between C—N and C=N double bond distances, which shows influence of the delocalization of electrons from the benzene ring. The P atom adopts a distorted tetrahedral configuration, with the angles in the range of 101.1 (1)° - 115.8 (1)°. The deformation of the PO3C tetrahedra may be explained in terms of steric effects from the adjacent bulky ethoxy groups. There are some differences between similar bonds in the P-O-C-C groups and this may be attributed to the larger than normal anisotropic displacement parameters of the atoms in the groups. This was not considered severe enough to model as disorder (Ezra & Collin, 1973; Sawka-Dobrowolska & Kowalik, 1985; Sanders et al., 1996). In the crystal structure, intermolecular O-H···O and N-H···O hydrogen bonds link pairs of molecules into centrosymmetric dimers. These dimers, are in turn, linked by weak intermolecular C-H···O hydrogen bonds into one-dimensional chains along [010](see Fig. 2). Additional stabilization is provided by very weak C—H···Cl interactions. .

Related literature top

For applications of α-aminophosphonates, see: Allen et al. (1989); Baylis et al. (1984); Fields (1999); Hirschmann et al. (1994); Kafarski & Lejczak (1991); Miliszkiewicz et al. (1992). For the antibacterial activity of the title compound, see: Syam Prasad et al. (2007). For related structures, see: Boehlow et al. (1997); Yang et al. (2005); Sawka-Dobrowolska & Kowalik (1985); Sawka-Dobrowolska & Rułko (1987); Sanders et al. (1996); Ezra & Collin (1973). For P—C bond lengths in related structures, see: Rużić-Toroš et al. (1978);

Experimental top

To a stirred solution of 2-amino-4-chlorophenol (0.72 g, 0.005 mol), 4-chloro benzaldehyde (0.005 mol) in anhydrous toluene (15 ml) was added dropwise. Stirring was continued at room temperature for 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 the reaction (monitored by TLC) 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, prism shaped single crystals suitable for diffraction studies were grown by slow evaporation of a methanol solution of the title compound.

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT (Bruker 2002); data reduction: SAINT (Bruker 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ZORTEP-II (Zsolnai, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: 'enCIFer (Allen et al., 2004) and PARST (Nardelli, 1995)'.

Figures top

	Fig. 1. The molecular structure of the itle compound with displacement ellipsoids drawn at the 40% probability level. H atoms have been omitted.
	Fig. 2. Part of the crystal structure showing one-dimensional chains along [010]. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₁₇H₂₀Cl₂NO₄P	Z = 2
M_r = 404.21	F(000) = 420
Triclinic, P1	D_x = 1.391 Mg m⁻³ D_m = 1.390 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.790 (3) Å	Cell parameters from 4863 reflections
b = 9.297 (4) Å	θ = 2.3–28.4°
c = 14.372 (6) Å	µ = 0.44 mm⁻¹
α = 82.817 (6)°	T = 294 K
β = 80.842 (6)°	Prism, colorless
γ = 70.323 (6)°	0.25 × 0.25 × 0.13 mm
V = 964.7 (7) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	4863 independent reflections
Radiation source: fine-focus sealed tube	3635 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.896, T_max = 0.944	k = −12→12
10997 measured reflections	l = −19→19

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0937P)² + 0.273P] where P = (F_o² + 2F_c²)/3
4863 reflections	(Δ/σ)_max < 0.001
226 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₇H₂₀Cl₂NO₄P	γ = 70.323 (6)°
M_r = 404.21	V = 964.7 (7) Å³
Triclinic, P1	Z = 2
a = 7.790 (3) Å	Mo Kα radiation
b = 9.297 (4) Å	µ = 0.44 mm⁻¹
c = 14.372 (6) Å	T = 294 K
α = 82.817 (6)°	0.25 × 0.25 × 0.13 mm
β = 80.842 (6)°

Data collection top

Siemens SMART CCD area-detector diffractometer	4863 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3635 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.944	R_int = 0.017
10997 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.05	Δρ_max = 0.56 e Å⁻³
4863 reflections	Δρ_min = −0.34 e Å⁻³
226 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
P1	0.39158 (8)	0.81933 (6)	0.17033 (4)	0.05033 (18)
Cl3	0.76222 (12)	0.10544 (8)	0.42621 (5)	0.0856 (3)
Cl2	−0.32728 (10)	0.63628 (13)	0.43963 (6)	0.0973 (3)
O8	0.6784 (2)	0.33466 (17)	0.03123 (10)	0.0610 (4)
H8	0.7402	0.2713	−0.0061	0.092*
C15	0.4115 (3)	0.6327 (2)	0.23264 (13)	0.0462 (4)
H15	0.4946	0.6167	0.2803	0.055*
O5	0.2676 (2)	0.86066 (17)	0.09700 (11)	0.0619 (4)
C16	0.2269 (3)	0.6284 (2)	0.28494 (13)	0.0449 (4)
N4	0.4997 (3)	0.51803 (19)	0.16550 (12)	0.0555 (5)
H4	0.4846	0.5413	0.1069	0.067*
C10	0.6279 (3)	0.3174 (2)	0.28709 (14)	0.0506 (5)
H10	0.5652	0.3800	0.3356	0.061*
C14	0.7033 (3)	0.2733 (2)	0.12175 (14)	0.0474 (4)
O7	0.5926 (3)	0.8172 (2)	0.13357 (14)	0.0790 (5)
C9	0.6079 (2)	0.3719 (2)	0.19319 (14)	0.0435 (4)
O6	0.3313 (3)	0.92357 (18)	0.25403 (11)	0.0662 (5)
C11	0.7415 (3)	0.1695 (2)	0.30794 (15)	0.0550 (5)
C13	0.8153 (3)	0.1274 (3)	0.14481 (17)	0.0600 (6)
H13	0.8783	0.0637	0.0969	0.072*
C12	0.8360 (3)	0.0736 (3)	0.23795 (18)	0.0634 (6)
H12	0.9121	−0.0251	0.2529	0.076*
C21	0.1714 (3)	0.6774 (3)	0.37545 (15)	0.0567 (5)
H21	0.2495	0.7088	0.4048	0.068*
C19	−0.1119 (3)	0.6310 (3)	0.38023 (17)	0.0622 (6)
C20	0.0014 (3)	0.6800 (3)	0.42263 (16)	0.0646 (6)
H20	−0.0357	0.7150	0.4828	0.078*
C17	0.1099 (3)	0.5794 (3)	0.24381 (17)	0.0646 (6)
H17	0.1460	0.5448	0.1835	0.078*
C18	−0.0595 (4)	0.5810 (4)	0.2904 (2)	0.0754 (7)
H18	−0.1376	0.5487	0.2616	0.091*
C22	0.3166 (5)	1.0826 (3)	0.2469 (2)	0.0840 (9)
H22A	0.2271	1.1403	0.2048	0.101*
H22B	0.4343	1.0945	0.2209	0.101*
C24	0.6719 (5)	0.8128 (4)	0.0351 (2)	0.0952 (10)
H24A	0.5890	0.7947	−0.0023	0.114*
H24B	0.6872	0.9110	0.0124	0.114*
C23	0.2602 (5)	1.1411 (4)	0.3403 (2)	0.0903 (10)
H23A	0.2494	1.2477	0.3353	0.135*
H23B	0.3504	1.0850	0.3813	0.135*
H23C	0.1437	1.1292	0.3657	0.135*
C25	0.8425 (6)	0.6970 (6)	0.0239 (3)	0.148 (2)
H25A	0.8922	0.6963	−0.0417	0.222*
H25B	0.8271	0.5996	0.0455	0.222*
H25C	0.9252	0.7158	0.0601	0.222*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0602 (3)	0.0418 (3)	0.0429 (3)	−0.0107 (2)	0.0019 (2)	−0.0079 (2)
Cl3	0.1068 (6)	0.0725 (4)	0.0536 (4)	0.0006 (4)	−0.0165 (3)	0.0075 (3)
Cl2	0.0603 (4)	0.1562 (8)	0.0703 (5)	−0.0335 (4)	0.0017 (3)	−0.0068 (5)
O8	0.0729 (10)	0.0504 (8)	0.0449 (8)	0.0014 (7)	−0.0067 (7)	−0.0104 (6)
C15	0.0516 (10)	0.0384 (9)	0.0407 (9)	−0.0028 (8)	−0.0057 (8)	−0.0070 (7)
O5	0.0798 (11)	0.0474 (8)	0.0463 (8)	−0.0043 (7)	−0.0086 (7)	−0.0038 (6)
C16	0.0524 (10)	0.0355 (8)	0.0401 (9)	−0.0045 (7)	−0.0078 (8)	−0.0038 (7)
N4	0.0666 (11)	0.0432 (9)	0.0396 (8)	0.0062 (8)	−0.0066 (8)	−0.0081 (7)
C10	0.0520 (11)	0.0473 (10)	0.0449 (10)	−0.0069 (8)	−0.0017 (8)	−0.0071 (8)
C14	0.0460 (10)	0.0457 (10)	0.0455 (10)	−0.0072 (8)	−0.0037 (8)	−0.0088 (8)
O7	0.0733 (11)	0.0911 (13)	0.0722 (12)	−0.0324 (10)	0.0114 (9)	−0.0145 (10)
C9	0.0404 (9)	0.0386 (9)	0.0463 (10)	−0.0062 (7)	−0.0030 (7)	−0.0062 (7)
O6	0.0935 (12)	0.0494 (8)	0.0552 (9)	−0.0257 (8)	0.0070 (8)	−0.0162 (7)
C11	0.0576 (12)	0.0496 (11)	0.0498 (11)	−0.0071 (9)	−0.0092 (9)	−0.0002 (9)
C13	0.0604 (12)	0.0482 (11)	0.0565 (12)	0.0038 (9)	−0.0036 (10)	−0.0140 (9)
C12	0.0623 (13)	0.0452 (11)	0.0655 (14)	0.0060 (9)	−0.0101 (11)	−0.0042 (10)
C21	0.0623 (13)	0.0642 (13)	0.0442 (11)	−0.0187 (10)	−0.0053 (9)	−0.0129 (9)
C19	0.0513 (11)	0.0742 (15)	0.0531 (12)	−0.0124 (10)	−0.0051 (9)	0.0004 (11)
C20	0.0677 (14)	0.0764 (15)	0.0436 (11)	−0.0162 (12)	0.0013 (10)	−0.0124 (10)
C17	0.0645 (13)	0.0807 (16)	0.0500 (12)	−0.0205 (12)	−0.0052 (10)	−0.0212 (11)
C18	0.0658 (15)	0.103 (2)	0.0634 (15)	−0.0306 (14)	−0.0073 (12)	−0.0221 (14)
C22	0.120 (2)	0.0619 (15)	0.0744 (17)	−0.0419 (16)	0.0128 (16)	−0.0183 (13)
C24	0.084 (2)	0.097 (2)	0.079 (2)	−0.0163 (17)	0.0210 (16)	0.0078 (17)
C23	0.119 (3)	0.0762 (18)	0.083 (2)	−0.0425 (18)	0.0148 (18)	−0.0354 (15)
C25	0.090 (3)	0.164 (4)	0.123 (4)	0.017 (3)	0.034 (2)	0.008 (3)

Geometric parameters (Å, º) top

P1—O5	1.4712 (17)	C13—C12	1.384 (3)
P1—O6	1.5531 (16)	C13—H13	0.9300
P1—O7	1.565 (2)	C12—H12	0.9300
P1—C15	1.819 (2)	C21—C20	1.382 (3)
Cl3—C11	1.743 (2)	C21—H21	0.9300
Cl2—C19	1.745 (3)	C19—C20	1.367 (4)
O8—C14	1.370 (2)	C19—C18	1.380 (4)
O8—H8	0.8200	C20—H20	0.9300
C15—N4	1.447 (2)	C17—C18	1.377 (4)
C15—C16	1.523 (3)	C17—H17	0.9300
C15—H15	0.9800	C18—H18	0.9300
C16—C17	1.381 (3)	C22—C23	1.457 (4)
C16—C21	1.387 (3)	C22—H22A	0.9700
N4—C9	1.384 (2)	C22—H22B	0.9700
N4—H4	0.8600	C24—C25	1.402 (5)
C10—C11	1.388 (3)	C24—H24A	0.9700
C10—C9	1.394 (3)	C24—H24B	0.9700
C10—H10	0.9300	C23—H23A	0.9600
C14—C13	1.376 (3)	C23—H23B	0.9600
C14—C9	1.407 (3)	C23—H23C	0.9600
O7—C24	1.450 (4)	C25—H25A	0.9600
O6—C22	1.436 (3)	C25—H25B	0.9600
C11—C12	1.377 (3)	C25—H25C	0.9600

O5—P1—O6	115.79 (10)	C20—C21—C16	120.8 (2)
O5—P1—O7	114.61 (11)	C20—C21—H21	119.6
O6—P1—O7	104.38 (10)	C16—C21—H21	119.6
O5—P1—C15	113.51 (10)	C20—C19—C18	120.8 (2)
O6—P1—C15	101.05 (9)	C20—C19—Cl2	119.40 (19)
O7—P1—C15	106.08 (11)	C18—C19—Cl2	119.8 (2)
C14—O8—H8	109.5	C19—C20—C21	119.6 (2)
N4—C15—C16	115.71 (17)	C19—C20—H20	120.2
N4—C15—P1	107.67 (14)	C21—C20—H20	120.2
C16—C15—P1	111.24 (12)	C18—C17—C16	121.3 (2)
N4—C15—H15	107.3	C18—C17—H17	119.4
C16—C15—H15	107.3	C16—C17—H17	119.4
P1—C15—H15	107.3	C17—C18—C19	119.2 (2)
C17—C16—C21	118.4 (2)	C17—C18—H18	120.4
C17—C16—C15	121.66 (18)	C19—C18—H18	120.4
C21—C16—C15	119.92 (18)	O6—C22—C23	109.6 (2)
C9—N4—C15	121.70 (16)	O6—C22—H22A	109.8
C9—N4—H4	119.1	C23—C22—H22A	109.8
C15—N4—H4	119.1	O6—C22—H22B	109.8
C11—C10—C9	119.82 (18)	C23—C22—H22B	109.8
C11—C10—H10	120.1	H22A—C22—H22B	108.2
C9—C10—H10	120.1	C25—C24—O7	111.0 (3)
O8—C14—C13	124.40 (18)	C25—C24—H24A	109.4
O8—C14—C9	115.33 (17)	O7—C24—H24A	109.4
C13—C14—C9	120.25 (19)	C25—C24—H24B	109.4
C24—O7—P1	124.7 (2)	O7—C24—H24B	109.4
N4—C9—C10	123.96 (17)	H24A—C24—H24B	108.0
N4—C9—C14	117.57 (17)	C22—C23—H23A	109.5
C10—C9—C14	118.47 (17)	C22—C23—H23B	109.5
C22—O6—P1	125.27 (17)	H23A—C23—H23B	109.5
C12—C11—C10	121.7 (2)	C22—C23—H23C	109.5
C12—C11—Cl3	119.93 (17)	H23A—C23—H23C	109.5
C10—C11—Cl3	118.42 (17)	H23B—C23—H23C	109.5
C14—C13—C12	121.27 (19)	C24—C25—H25A	109.5
C14—C13—H13	119.4	C24—C25—H25B	109.5
C12—C13—H13	119.4	H25A—C25—H25B	109.5
C11—C12—C13	118.53 (19)	C24—C25—H25C	109.5
C11—C12—H12	120.7	H25A—C25—H25C	109.5
C13—C12—H12	120.7	H25B—C25—H25C	109.5

O5—P1—C15—N4	65.76 (17)	O5—P1—O6—C22	−65.0 (3)
O6—P1—C15—N4	−169.61 (14)	O7—P1—O6—C22	62.0 (3)
O7—P1—C15—N4	−60.97 (16)	C15—P1—O6—C22	172.0 (2)
O5—P1—C15—C16	−62.00 (16)	C9—C10—C11—C12	−0.2 (4)
O6—P1—C15—C16	62.62 (15)	C9—C10—C11—Cl3	−179.79 (16)
O7—P1—C15—C16	171.27 (13)	O8—C14—C13—C12	179.0 (2)
N4—C15—C16—C17	−30.9 (3)	C9—C14—C13—C12	0.5 (4)
P1—C15—C16—C17	92.4 (2)	C10—C11—C12—C13	−0.2 (4)
N4—C15—C16—C21	150.44 (18)	Cl3—C11—C12—C13	179.4 (2)
P1—C15—C16—C21	−86.3 (2)	C14—C13—C12—C11	0.1 (4)
C16—C15—N4—C9	−84.7 (2)	C17—C16—C21—C20	−1.3 (3)
P1—C15—N4—C9	150.18 (17)	C15—C16—C21—C20	177.43 (19)
O5—P1—O7—C24	−16.7 (3)	C18—C19—C20—C21	−1.0 (4)
O6—P1—O7—C24	−144.4 (2)	Cl2—C19—C20—C21	−179.39 (19)
C15—P1—O7—C24	109.4 (2)	C16—C21—C20—C19	1.3 (4)
C15—N4—C9—C10	6.3 (3)	C21—C16—C17—C18	1.0 (4)
C15—N4—C9—C14	−173.55 (18)	C15—C16—C17—C18	−177.7 (2)
C11—C10—C9—N4	−179.1 (2)	C16—C17—C18—C19	−0.7 (4)
C11—C10—C9—C14	0.7 (3)	C20—C19—C18—C17	0.7 (4)
O8—C14—C9—N4	0.3 (3)	Cl2—C19—C18—C17	179.1 (2)
C13—C14—C9—N4	179.0 (2)	P1—O6—C22—C23	−178.8 (2)
O8—C14—C9—C10	−179.55 (19)	P1—O7—C24—C25	−130.1 (4)
C13—C14—C9—C10	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O8ⁱ	0.86	2.48	3.286 (3)	157
C24—H24B···O5ⁱⁱ	0.97	2.57	3.504 (4)	162
O8—H8···O5ⁱ	0.82	1.92	2.636 (2)	145
C15—H15···Cl2ⁱⁱⁱ	0.98	2.91	3.872 (3)	165
N4—H4···O8	0.86	2.28	2.634 (3)	105
C24—H24A···O5	0.97	2.59	3.029 (5)	107

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₀Cl₂NO₄P
M_r	404.21
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.790 (3), 9.297 (4), 14.372 (6)
α, β, γ (°)	82.817 (6), 80.842 (6), 70.323 (6)
V (Å³)	964.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.25 × 0.25 × 0.13

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.896, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	10997, 4863, 3635
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.159, 1.05
No. of reflections	4863
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.34

Computer programs: SMART (Bruker 2001), SAINT (Bruker 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ZORTEP-II (Zsolnai, 1997) and PLATON (Spek, 2009), 'enCIFer (Allen et al., 2004) and PARST (Nardelli, 1995)'.

Selected geometric parameters (Å, º) top

P1—O5	1.4712 (17)	P1—O7	1.565 (2)
P1—O6	1.5531 (16)	P1—C15	1.819 (2)

O5—P1—O6	115.79 (10)	O5—P1—C15	113.51 (10)
O5—P1—O7	114.61 (11)	O6—P1—C15	101.05 (9)
O6—P1—O7	104.38 (10)	O7—P1—C15	106.08 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O8ⁱ	0.86	2.48	3.286 (3)	157
C24—H24B···O5ⁱⁱ	0.97	2.57	3.504 (4)	162
O8—H8···O5ⁱ	0.82	1.92	2.636 (2)	145
C15—H15···Cl2ⁱⁱⁱ	0.98	2.91	3.872 (3)	165
N4—H4···O8	0.86	2.28	2.634 (3)	105

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

Acknowledgements

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

References

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