Ethyl [(benzyl­aza­nium­yl)(2-hy­droxy­phen­yl)meth­yl]phospho­nate

Zhang, X.; Zhang, R.; Ge, C.; Zhang, X.

doi:10.1107/S1600536811026444

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2006

doi:10.1107/S1600536811026444

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Ethyl [(benzylazaniumyl)(2-hydroxyphenyl)methyl]phosphonate

Xiangdong Zhang,^a ^* Rui Zhang,^a Chunhua Ge ^a and Xiaoyan Zhang ^a

^aCollege of Chemistry, Liaoning University, Shenyang, Liaoning 110036, People's Republic of China
^*Correspondence e-mail: xdzhang@lnu.edu.cn

(Received 21 June 2011; accepted 3 July 2011; online 9 July 2011)

The title compound, C₁₆H₂₀NO₄P, crystallizes as a zwitterion. In the molecule, the two aromatic rings form a dihedral angle of 55.2 (1)°. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules into columns propagating in [010].

Related literature

For related structures, see: Zhang et al. (2005 , 2007 ).

Experimental

Crystal data

C₁₆H₂₀NO₄P
M_r = 321.30
Monoclinic, C 2/c
a = 28.069 (3) Å
b = 6.0927 (7) Å
c = 22.333 (3) Å
β = 124.464 (2)°
V = 3149.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 296 K
0.28 × 0.25 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.955, T_max = 0.969
8453 measured reflections
3104 independent reflections
1918 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.121
S = 1.00
3104 reflections
209 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O1ⁱ	0.97 (3)	1.77 (3)	2.738 (3)	179 (2)
N1—H1NB⋯O4	0.86 (3)	2.50 (3)	2.982 (3)	116 (2)
N1—H1NB⋯O2ⁱⁱ	0.86 (3)	2.08 (3)	2.915 (3)	164 (2)
O4—H4A⋯O1	0.82	1.94	2.738 (3)	164
O4—H4A⋯O2ⁱⁱ	0.82	2.58	2.925 (3)	107
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811026444/cv5124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026444/cv5124Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026444/cv5124Isup3.cml

checkCIF report

Comment top

As a continuation of our structural study of (2-hydroxyphenyl)methylphosphonate derivatives (Zhang et al., 2005; 2007), we present here the crystal structure of the title compound, (I), which crystallizes as a zwitterion.

In the title molecule (Fig. 1), two aromatic rings form a dihedral angle of 55.2 (1)°. In the crystal structure, intermolecular N—H···O and O—H···O hydrogen bonds (Table 1) link molecules into columns propagated in [010].

Related literature top

For related structures, see: Zhang et al. (2005, 2007).

Experimental top

The title compound was synthesized following the reported method (Zhang et al., 2005). Diethyl phosphonate (0.02 mol) was dissolved in 80 ml of ethanol. The solution was added dropwise to a mixture of salicylaldehyde (0.02 mol) and benzylamine (0.02 mol) in 30 ml e thanol which was refluxed for 4 h. The resulting solution was refluxed until solid appeared. The product was filtered and washed with ethanol. Yield 43%.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Ethyl [(benzylazaniumyl)(2-hydroxyphenyl)methyl]phosphonate top

Crystal data top

C₁₆H₂₀NO₄P	F(000) = 1360
M_r = 321.30	D_x = 1.355 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 187 reflections
a = 28.069 (3) Å	θ = 2.6–22.5°
b = 6.0927 (7) Å	µ = 0.19 mm⁻¹
c = 22.333 (3) Å	T = 296 K
β = 124.464 (2)°	Block, colourless
V = 3149.0 (6) Å³	0.28 × 0.25 × 0.19 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	3104 independent reflections
Radiation source: fine-focus sealed tube	1918 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −34→33
T_min = 0.955, T_max = 0.969	k = −7→7
8453 measured reflections	l = −19→27

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0504P)²] where P = (F_o² + 2F_c²)/3
3104 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₆H₂₀NO₄P	V = 3149.0 (6) Å³
M_r = 321.30	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.069 (3) Å	µ = 0.19 mm⁻¹
b = 6.0927 (7) Å	T = 296 K
c = 22.333 (3) Å	0.28 × 0.25 × 0.19 mm
β = 124.464 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3104 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1918 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.969	R_int = 0.057
8453 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.30 e Å⁻³
3104 reflections	Δρ_min = −0.28 e Å⁻³
209 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	0.17738 (3)	0.87761 (11)	0.22830 (4)	0.0315 (2)
O3	0.11541 (7)	0.8149 (3)	0.20942 (10)	0.0399 (5)
N1	0.23047 (10)	0.8251 (4)	0.15689 (12)	0.0303 (5)
O2	0.22470 (8)	0.7684 (3)	0.29547 (9)	0.0393 (5)
C18	0.17490 (11)	0.7697 (4)	0.14969 (13)	0.0301 (6)
H18	0.1735	0.6094	0.1520	0.036*
C8	0.12149 (11)	0.8387 (4)	0.07710 (13)	0.0315 (6)
O1	0.17840 (8)	1.1221 (3)	0.22305 (10)	0.0376 (5)
O4	0.15309 (10)	1.2130 (3)	0.08789 (11)	0.0586 (6)
H4A	0.1652	1.2047	0.1309	0.088*
C2	0.28397 (12)	0.7998 (5)	0.09779 (14)	0.0378 (7)
C10	0.06502 (13)	1.1018 (5)	−0.01849 (15)	0.0448 (7)
H10	0.0610	1.2415	−0.0376	0.054*
C1	0.23072 (12)	0.7379 (5)	0.09411 (15)	0.0424 (7)
H1A	0.2277	0.5791	0.0932	0.051*
H1B	0.1971	0.7936	0.0492	0.051*
C13	0.07828 (12)	0.6856 (5)	0.03567 (15)	0.0399 (7)
H13	0.0826	0.5438	0.0535	0.048*
C9	0.11301 (12)	1.0518 (4)	0.04989 (15)	0.0375 (7)
C11	0.02300 (13)	0.9456 (5)	−0.05861 (16)	0.0474 (8)
H11	−0.0095	0.9812	−0.1042	0.057*
C7	0.32831 (13)	0.6516 (5)	0.12183 (16)	0.0505 (8)
H7	0.3259	0.5144	0.1382	0.061*
C12	0.02899 (12)	0.7382 (5)	−0.03144 (16)	0.0451 (8)
H12	0.0002	0.6339	−0.0578	0.054*
C5	0.38007 (15)	0.9030 (7)	0.09799 (19)	0.0648 (10)
H5	0.4122	0.9375	0.0978	0.078*
C3	0.28884 (14)	1.0027 (5)	0.07376 (17)	0.0511 (8)
H3A	0.2595	1.1056	0.0572	0.061*
C14	0.10333 (14)	0.5962 (5)	0.2229 (2)	0.0629 (10)
H14A	0.1335	0.5506	0.2718	0.075*
H14B	0.1024	0.4934	0.1890	0.075*
C15	0.04702 (15)	0.5964 (7)	0.2139 (2)	0.0851 (13)
H15A	0.0485	0.6956	0.2483	0.128*
H15B	0.0386	0.4511	0.2220	0.128*
H15C	0.0173	0.6426	0.1655	0.128*
C4	0.33690 (16)	1.0534 (6)	0.07413 (19)	0.0635 (10)
H4	0.3399	1.1903	0.0581	0.076*
C6	0.37635 (15)	0.7037 (6)	0.12200 (19)	0.0648 (10)
H6	0.4060	0.6021	0.1386	0.078*
H1NA	0.2628 (13)	0.754 (4)	0.1997 (16)	0.050 (9)*
H1NB	0.2378 (11)	0.963 (4)	0.1627 (14)	0.033 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0278 (4)	0.0342 (4)	0.0320 (4)	−0.0001 (3)	0.0167 (3)	−0.0020 (3)
O3	0.0304 (11)	0.0432 (12)	0.0473 (12)	−0.0015 (9)	0.0227 (10)	0.0046 (9)
N1	0.0311 (14)	0.0301 (14)	0.0293 (13)	0.0002 (11)	0.0169 (12)	−0.0005 (11)
O2	0.0338 (11)	0.0488 (12)	0.0306 (10)	0.0068 (9)	0.0155 (9)	0.0055 (9)
C18	0.0285 (15)	0.0256 (14)	0.0321 (15)	0.0010 (11)	0.0147 (13)	0.0016 (11)
C8	0.0306 (15)	0.0350 (16)	0.0265 (14)	0.0032 (12)	0.0147 (12)	−0.0019 (12)
O1	0.0369 (11)	0.0333 (11)	0.0418 (11)	−0.0045 (9)	0.0218 (10)	−0.0078 (9)
O4	0.0591 (15)	0.0372 (12)	0.0452 (13)	−0.0073 (11)	0.0090 (12)	0.0035 (10)
C2	0.0379 (17)	0.0472 (18)	0.0300 (15)	−0.0016 (14)	0.0202 (14)	−0.0071 (13)
C10	0.0451 (19)	0.0437 (18)	0.0351 (16)	0.0101 (15)	0.0164 (15)	0.0067 (14)
C1	0.0429 (18)	0.0532 (19)	0.0337 (16)	−0.0061 (14)	0.0232 (15)	−0.0111 (14)
C13	0.0319 (17)	0.0465 (18)	0.0390 (16)	−0.0002 (14)	0.0187 (14)	−0.0035 (14)
C9	0.0333 (17)	0.0368 (17)	0.0346 (15)	0.0021 (13)	0.0145 (13)	−0.0016 (13)
C11	0.0347 (18)	0.066 (2)	0.0312 (16)	0.0105 (16)	0.0126 (14)	−0.0002 (16)
C7	0.058 (2)	0.055 (2)	0.0491 (19)	0.0096 (17)	0.0372 (18)	0.0018 (16)
C12	0.0272 (17)	0.060 (2)	0.0375 (17)	−0.0078 (14)	0.0117 (14)	−0.0112 (15)
C5	0.054 (2)	0.096 (3)	0.061 (2)	−0.021 (2)	0.043 (2)	−0.016 (2)
C3	0.057 (2)	0.0476 (19)	0.0494 (19)	0.0017 (16)	0.0301 (17)	−0.0012 (16)
C14	0.054 (2)	0.068 (2)	0.064 (2)	−0.0147 (18)	0.0314 (19)	0.0084 (19)
C15	0.046 (2)	0.119 (3)	0.081 (3)	−0.016 (2)	0.031 (2)	0.024 (2)
C4	0.078 (3)	0.068 (2)	0.062 (2)	−0.020 (2)	0.049 (2)	−0.0062 (19)
C6	0.054 (2)	0.087 (3)	0.066 (2)	0.016 (2)	0.042 (2)	−0.001 (2)

Geometric parameters (Å, º) top

P1—O2	1.4841 (18)	C1—H1B	0.9700
P1—O1	1.4961 (18)	C13—C12	1.384 (4)
P1—O3	1.5874 (18)	C13—H13	0.9300
P1—C18	1.839 (3)	C11—C12	1.370 (4)
O3—C14	1.448 (3)	C11—H11	0.9300
N1—C1	1.503 (3)	C7—C6	1.383 (4)
N1—C18	1.513 (3)	C7—H7	0.9300
N1—H1NA	0.97 (3)	C12—H12	0.9300
N1—H1NB	0.86 (3)	C5—C6	1.355 (5)
C18—C8	1.517 (3)	C5—C4	1.364 (5)
C18—H18	0.9800	C5—H5	0.9300
C8—C13	1.388 (3)	C3—C4	1.380 (4)
C8—C9	1.396 (4)	C3—H3A	0.9300
O4—C9	1.367 (3)	C14—C15	1.477 (4)
O4—H4A	0.8200	C14—H14A	0.9700
C2—C7	1.377 (4)	C14—H14B	0.9700
C2—C3	1.384 (4)	C15—H15A	0.9600
C2—C1	1.498 (4)	C15—H15B	0.9600
C10—C11	1.380 (4)	C15—H15C	0.9600
C10—C9	1.382 (4)	C4—H4	0.9300
C10—H10	0.9300	C6—H6	0.9300
C1—H1A	0.9700

O2—P1—O1	118.69 (11)	C8—C13—H13	119.1
O2—P1—O3	112.33 (10)	O4—C9—C10	118.2 (3)
O1—P1—O3	106.60 (10)	O4—C9—C8	121.3 (2)
O2—P1—C18	109.48 (11)	C10—C9—C8	120.4 (3)
O1—P1—C18	105.86 (11)	C12—C11—C10	120.2 (3)
O3—P1—C18	102.51 (11)	C12—C11—H11	119.9
C14—O3—P1	121.11 (18)	C10—C11—H11	119.9
C1—N1—C18	111.8 (2)	C2—C7—C6	121.0 (3)
C1—N1—H1NA	105.4 (16)	C2—C7—H7	119.5
C18—N1—H1NA	109.7 (16)	C6—C7—H7	119.5
C1—N1—H1NB	111.2 (17)	C11—C12—C13	119.3 (3)
C18—N1—H1NB	112.3 (17)	C11—C12—H12	120.3
H1NA—N1—H1NB	106 (2)	C13—C12—H12	120.3
N1—C18—C8	112.8 (2)	C6—C5—C4	120.4 (3)
N1—C18—P1	109.82 (16)	C6—C5—H5	119.8
C8—C18—P1	113.68 (17)	C4—C5—H5	119.8
N1—C18—H18	106.7	C4—C3—C2	120.6 (3)
C8—C18—H18	106.7	C4—C3—H3A	119.7
P1—C18—H18	106.7	C2—C3—H3A	119.7
C13—C8—C9	117.7 (2)	O3—C14—C15	109.2 (3)
C13—C8—C18	119.2 (2)	O3—C14—H14A	109.8
C9—C8—C18	123.0 (2)	C15—C14—H14A	109.8
C9—O4—H4A	109.5	O3—C14—H14B	109.8
C7—C2—C3	118.1 (3)	C15—C14—H14B	109.8
C7—C2—C1	120.6 (3)	H14A—C14—H14B	108.3
C3—C2—C1	121.2 (3)	C14—C15—H15A	109.5
C11—C10—C9	120.4 (3)	C14—C15—H15B	109.5
C11—C10—H10	119.8	H15A—C15—H15B	109.5
C9—C10—H10	119.8	C14—C15—H15C	109.5
C2—C1—N1	113.0 (2)	H15A—C15—H15C	109.5
C2—C1—H1A	109.0	H15B—C15—H15C	109.5
N1—C1—H1A	109.0	C5—C4—C3	120.1 (3)
C2—C1—H1B	109.0	C5—C4—H4	120.0
N1—C1—H1B	109.0	C3—C4—H4	120.0
H1A—C1—H1B	107.8	C5—C6—C7	119.8 (3)
C12—C13—C8	121.8 (3)	C5—C6—H6	120.1
C12—C13—H13	119.1	C7—C6—H6	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O1ⁱ	0.97 (3)	1.77 (3)	2.738 (3)	179 (2)
N1—H1NB···O4	0.86 (3)	2.50 (3)	2.982 (3)	116 (2)
N1—H1NB···O2ⁱⁱ	0.86 (3)	2.08 (3)	2.915 (3)	164 (2)
O4—H4A···O1	0.82	1.94	2.738 (3)	164
O4—H4A···O2ⁱⁱ	0.82	2.58	2.925 (3)	107

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

Experimental details

Crystal data
Chemical formula	C₁₆H₂₀NO₄P
M_r	321.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	28.069 (3), 6.0927 (7), 22.333 (3)
β (°)	124.464 (2)
V (Å³)	3149.0 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.28 × 0.25 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.955, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	8453, 3104, 1918
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.121, 1.00
No. of reflections	3104
No. of parameters	209
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.28

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O1ⁱ	0.97 (3)	1.77 (3)	2.738 (3)	179 (2)
N1—H1NB···O4	0.86 (3)	2.50 (3)	2.982 (3)	116 (2)
N1—H1NB···O2ⁱⁱ	0.86 (3)	2.08 (3)	2.915 (3)	164 (2)
O4—H4A···O1	0.82	1.94	2.738 (3)	164
O4—H4A···O2ⁱⁱ	0.82	2.58	2.925 (3)	107

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20971062/B010303), the Project for Provincial Key Laboratory of Liaoning Province, China (grant No. 2008S104).

References

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