[Amino­(iminio)meth­yl]phospho­nate

Yang, T.-H.; Zhuang, W.; Wei, W.; Yang, Y.-B.; Chen, Q.

doi:10.1107/S1600536810032083

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2326

https://doi.org/10.1107/S1600536810032083

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[Amino(iminio)methyl]phosphonate

Ting-Hai Yang,^a ^* Wei Zhuang,^a Wei Wei,^b Yong-Bing Yang ^a and Qiang Chen ^a

^aHigh-Tech Institute of Nangjing University, Changzhou 213164, People's Republic of China, and ^bSchool of Chemistry & Chemical Engineering, Changzhou University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: Tinghaiyang@gmail.com, Chem100@nju.edu.cn

(Received 30 July 2010; accepted 10 August 2010; online 18 August 2010)

The title compound, CH₅N₂O₃P, exists as a zwitterion. The N atom of the imino group is protonated and the phosphonic acid group is deprotonated. The molecular geometry about the central C atom of this zwitterionic species was found to be strictly planar with the sum of the three angles about C being precisely 360°. In the crystal, the molecules are interlinked by O—H⋯O and N—H⋯O hydrogen-bonding interactions, forming a three-dimensional supramolecular network structure.

Related literature

For background to phosphonic acid and metal phosphonate compounds, see: Ayyappan et al. (2001 ); Clearfield (1998 ); Haga et al. (2007 ); Vivani et al. (2008 ); Bao et al. (2007 ); Cave et al. (2006 ); Cao et al. (1992 ); Ma et al. (2006 , 2008 ). For a related structure, see Makarov et al. (1999 ).

Experimental

Crystal data

CH₅N₂O₃P
M_r = 124.04
Triclinic, $[P \overline 1]$
a = 4.8559 (17) Å
b = 5.910 (2) Å
c = 8.101 (3) Å
α = 99.570 (6)°
β = 90.784 (6)°
γ = 101.546 (6)°
V = 224.36 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.907, T_max = 0.924
1324 measured reflections
855 independent reflections
840 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.161
S = 1.01
855 reflections
64 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1ⁱ	0.96	1.75	2.611 (4)	147
N1—H1A⋯O2ⁱⁱ	0.86	2.06	2.903 (4)	167
N2—H2A⋯O1ⁱⁱ	0.86	2.09	2.924 (4)	164
N1—H1B⋯O2ⁱⁱⁱ	0.86	2.02	2.812 (4)	153
N2—H2B⋯O3^iv	0.86	2.21	3.008 (4)	154
Symmetry codes: (i) x+1, y, z; (ii) x, y-1, z; (iii) -x+2, -y+1, -z+1; (iv) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810032083/jj2049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032083/jj2049Isup2.hkl

checkCIF report

Comment top

In the last decade considerable attention has been afforded to the synthesis of metal phosphonates due to their potential applications in ion-exchange and sorption, catalysis, magnetism and sensors (Ayyappan et al., 2001; Clearfield, 1998; Haga et al., 2007; Vivani et al., 2008; Bao et al., 2007; Cave et al., 2006; Cao et al., 1992; Ma et al., 2006, 2008). In order to synthseize metal phosphonates with novel structures and properties, many kinds of phosphonic acid ligands have been used. In order to study the crystal structure of phosphonic acid, we synthesized and determined the structure of the title compound (Fig. 1). As shown in Scheme 1, the molecular exists as a zwitterion, the imino group being protonated and the phosphonic acid group being deprotonated. The molecular geometry about the central C atom is strictly planar with the sum of the three angles about C being precisely 360°. The three bonds about the central carbon atom consist of two nearly equivalent C–N1 and C–N2 distances of 1.299 (5) Å and 1.314 (5) Å, respectively, and a C–P bond distance of 1.845 (3) Å. These two C–N bonds are considerably shorter than a typical C–N single bond distance of 1.47 Å, Similar zwitterions have been formed by other aminoiminomethanesulfonic acids (Makarov et al.,1999). The P–O distances in these compounds range from 1.4872 (2) Å to 1.5872 (2) Å. By comparision of individual P—O distances, the H atom can be located on O3. In our crystal structure, three intermolecular hydrogen-bond interactions exist, viz. between the N atom and the phosphonate O atom [N1—H1A···O2, N2—H2A···O1, N1—H1B···O2, N2—H2B···O3], and between two phosphonate O atoms [O3—H3B···O1] (Table 1). Thus the molecules are interlinked by these intermolecular hydrogen bonds, forming a three-dimensional supramolecular network structure (Fig.2).

Related literature top

For background to phosphonic acid and metal phosphonate compounds, see: Ayyappan et al. (2001); Clearfield (1998); Haga et al. (2007); Vivani et al. (2008); Bao et al. (2007); Cave et al. (2006); Cao et al. (1992); Ma et al. (2006, 2008). For a related structure, see Makarov et al. (1999).

Experimental top

All solvents and chemicals were of analytical grade and were used without further purification. The title compound was prepared by the following reaction: A sample of 2,4,6-tri-(phosphonate ethyl)-1,3,5-triazine (9.8 g, 20 mmol) was dissolved in 6 mol/ ml HCl (20 ml), The mixture was heated (100 °C, 10 h) and then evaporated to dryness leaving a white solid. Crystallization was carried out by dissolution of 0.62 g of the title compound (about 0.5 mmol) in 10 ml water, followed by evaporation at room temperature. After two weeks, colorless block crystals obtained.

Structure description top

For background to phosphonic acid and metal phosphonate compounds, see: Ayyappan et al. (2001); Clearfield (1998); Haga et al. (2007); Vivani et al. (2008); Bao et al. (2007); Cave et al. (2006); Cao et al. (1992); Ma et al. (2006, 2008). For a related structure, see Makarov et al. (1999).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, (NH₂)₂CPO₃H, showing 50% probability displacement ellipsoids
	Fig. 2. The cell packing diagram for the title compound viewed down the a axis.

[Amino(iminio)methyl]phosphonate top

Crystal data top

CH₅N₂O₃P	Z = 2
M_r = 124.04	F(000) = 128
Triclinic, P1	D_x = 1.836 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8559 (17) Å	Cell parameters from 1436 reflections
b = 5.910 (2) Å	θ = 2.6–30.3°
c = 8.101 (3) Å	µ = 0.50 mm⁻¹
α = 99.570 (6)°	T = 296 K
β = 90.784 (6)°	Block, colorless
γ = 101.546 (6)°	0.20 × 0.18 × 0.16 mm
V = 224.36 (14) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	855 independent reflections
Radiation source: fine-focus sealed tube	840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
phi and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −5→5
T_min = 0.907, T_max = 0.924	k = −6→7
1324 measured reflections	l = −9→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1046P)² + 0.7669P] where P = (F_o² + 2F_c²)/3
855 reflections	(Δ/σ)_max < 0.001
64 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

CH₅N₂O₃P	γ = 101.546 (6)°
M_r = 124.04	V = 224.36 (14) Å³
Triclinic, P1	Z = 2
a = 4.8559 (17) Å	Mo Kα radiation
b = 5.910 (2) Å	µ = 0.50 mm⁻¹
c = 8.101 (3) Å	T = 296 K
α = 99.570 (6)°	0.20 × 0.18 × 0.16 mm
β = 90.784 (6)°

Data collection top

Bruker SMART APEX CCD diffractometer	855 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	840 reflections with I > 2σ(I)
T_min = 0.907, T_max = 0.924	R_int = 0.014
1324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.01	Δρ_max = 0.62 e Å⁻³
855 reflections	Δρ_min = −0.77 e Å⁻³
64 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	0.66113 (16)	0.60637 (13)	0.74674 (10)	0.0149 (4)
O1	0.3963 (5)	0.6733 (4)	0.8092 (3)	0.0225 (6)
O2	0.7837 (5)	0.6917 (4)	0.5956 (3)	0.0224 (6)
O3	0.8828 (5)	0.6695 (5)	0.9016 (3)	0.0224 (6)
H3B	1.0481	0.6105	0.8696	0.034*
N1	0.7663 (7)	0.1822 (5)	0.6080 (4)	0.0224 (7)
H1A	0.7485	0.0324	0.5929	0.027*
H1B	0.8918	0.2651	0.5566	0.027*
N2	0.4088 (7)	0.1649 (5)	0.7899 (4)	0.0229 (7)
H2A	0.3854	0.0148	0.7776	0.027*
H2B	0.3047	0.2374	0.8554	0.027*
C1	0.6036 (7)	0.2834 (6)	0.7084 (4)	0.0168 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0130 (6)	0.0125 (5)	0.0216 (6)	0.0045 (3)	0.0061 (4)	0.0070 (3)
O1	0.0156 (13)	0.0197 (13)	0.0350 (14)	0.0076 (10)	0.0086 (10)	0.0073 (10)
O2	0.0245 (13)	0.0199 (13)	0.0271 (14)	0.0067 (10)	0.0113 (10)	0.0124 (10)
O3	0.0150 (13)	0.0271 (14)	0.0247 (13)	0.0047 (10)	0.0029 (10)	0.0032 (10)
N1	0.0243 (16)	0.0139 (14)	0.0318 (17)	0.0057 (12)	0.0124 (13)	0.0088 (12)
N2	0.0263 (16)	0.0145 (14)	0.0299 (17)	0.0052 (12)	0.0138 (13)	0.0074 (12)
C1	0.0170 (16)	0.0147 (15)	0.0207 (16)	0.0044 (12)	0.0026 (12)	0.0073 (12)

Geometric parameters (Å, º) top

P1—O2	1.487 (2)	N1—H1A	0.8600
P1—O1	1.490 (3)	N1—H1B	0.8600
P1—O3	1.587 (3)	N2—C1	1.314 (5)
P1—C1	1.845 (3)	N2—H2A	0.8600
O3—H3B	0.9600	N2—H2B	0.8600
N1—C1	1.299 (5)

O2—P1—O1	119.46 (15)	C1—N1—H1B	120.0
O2—P1—O3	111.94 (15)	H1A—N1—H1B	120.0
O1—P1—O3	106.97 (15)	C1—N2—H2A	120.0
O2—P1—C1	108.20 (15)	C1—N2—H2B	120.0
O1—P1—C1	107.89 (15)	H2A—N2—H2B	120.0
O3—P1—C1	100.70 (15)	N1—C1—N2	122.4 (3)
P1—O3—H3B	109.3	N1—C1—P1	118.7 (3)
C1—N1—H1A	120.0	N2—C1—P1	118.8 (3)

O2—P1—C1—N1	28.6 (3)	O2—P1—C1—N2	−154.6 (3)
O1—P1—C1—N1	159.2 (3)	O1—P1—C1—N2	−24.1 (3)
O3—P1—C1—N1	−88.9 (3)	O3—P1—C1—N2	87.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1ⁱ	0.96	1.75	2.611 (4)	147
N1—H1A···O2ⁱⁱ	0.86	2.06	2.903 (4)	167
N2—H2A···O1ⁱⁱ	0.86	2.09	2.924 (4)	164
N1—H1B···O2ⁱⁱⁱ	0.86	2.02	2.812 (4)	153
N2—H2B···O3^iv	0.86	2.21	3.008 (4)	154

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

Experimental details

Crystal data
Chemical formula	CH₅N₂O₃P
M_r	124.04
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	4.8559 (17), 5.910 (2), 8.101 (3)
α, β, γ (°)	99.570 (6), 90.784 (6), 101.546 (6)
V (Å³)	224.36 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.907, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	1324, 855, 840
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.161, 1.01
No. of reflections	855
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.77

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1ⁱ	0.96	1.75	2.611 (4)	147.0
N1—H1A···O2ⁱⁱ	0.86	2.06	2.903 (4)	167.0
N2—H2A···O1ⁱⁱ	0.86	2.09	2.924 (4)	164.0
N1—H1B···O2ⁱⁱⁱ	0.86	2.02	2.812 (4)	153.0
N2—H2B···O3^iv	0.86	2.21	3.008 (4)	154.0

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

Acknowledgements

The authors acknowledge the Science and Technology Bureau of Changzhou City (project No. CQ20090004) for supporting this work.

References

Ayyappan, P., Evans, O. R., Foxman, B. M., Wheeler, K. A., Warren, T. H. & Lin, W. B. (2001). Inorg. Chem. 40, 5954–5961. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bao, S. S., Ma, L. F., Wang, Y., Fang, L., Zhu, C. J., Li, Y. Z. & Zheng, L. M. (2007). Chem. Eur. J. 13, 2333–2343. Web of Science CSD CrossRef PubMed CAS Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany Google Scholar
Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, G., Hong, H. & Mallouk, T. E. (1992). Acc. Chem. Res. 25, 420–427. CrossRef CAS Google Scholar
Cave, D., Coomer, F. C., Molinos, E., Klauss, H. H. & Wood, P. T. (2006). Angew. Chem. Int. Ed. 45, 803–806. Web of Science CSD CrossRef CAS Google Scholar
Clearfield, A. (1998). Prog. Inorg. Chem. 47, 371–510. CrossRef CAS Google Scholar
Haga, M. A., Kobayashi, K. & Terada, K. (2007). Coord. Chem. Rev., 251 2688–2701. Google Scholar
Ma, Y. S., Li, Y. Z., Song, Y. & Zheng, L. M. (2008). Inorg. Chem. 47, 4536–4544. Web of Science CrossRef PubMed CAS Google Scholar
Ma, Y. S., Song, Y., Du, W. X., Li, Y. Z. & Zheng, L. M. (2006). Dalton Trans. pp. 3228–3235. Web of Science CSD CrossRef Google Scholar
Makarov, S. V., Mundoma, C., Penn, J. H., Petersen, J. L., Svarovsky, S. A. & Simoyi, R. H. (1999). Inorg. Chim. Acta, 286, 149–154. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vivani, R., Alberti, G., Costantino, F. & Nocchetti, M. (2008). Microporous Mesoporous Mater. 107, 58–70. Web of Science CrossRef CAS Google Scholar