PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2326.
Published online 2010 August 18. doi:  10.1107/S1600536810032083
PMCID: PMC3007934

[Amino­(iminio)meth­yl]phospho­nate

Abstract

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 [triangle]); Clearfield (1998 [triangle]); Haga et al. (2007 [triangle]); Vivani et al. (2008 [triangle]); Bao et al. (2007 [triangle]); Cave et al. (2006 [triangle]); Cao et al. (1992 [triangle]); Ma et al. (2006 [triangle], 2008 [triangle]). For a related structure, see Makarov et al. (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2326-scheme1.jpg

Experimental

Crystal data

  • CH5N2O3P
  • M r = 124.04
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2326-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.161
  • S = 1.01
  • 855 reflections
  • 64 parameters
  • H-atom parameters constrained
  • Δρmax = 0.62 e Å−3
  • Δρmin = −0.77 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032083/jj2049Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All non-hydrogen atoms were refined anisotropically, whereas the positions of all H atoms bonded to nitrogen were fixed geometrically (N—H = 0.86 Å), and included in the refinement in the riding mode, with Uĩso~(H) = 1.2U~eq~(N). The H atom in P—O—H was located in a difference Fourier map and refined with a distance restraint of O—H = 0.96 Å, and with Uĩso~(H) = 1.5U~eq~(O).

Figures

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.

Crystal data

CH5N2O3PZ = 2
Mr = 124.04F(000) = 128
Triclinic, P1Dx = 1.836 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.8559 (17) ÅCell parameters from 1436 reflections
b = 5.910 (2) Åθ = 2.6–30.3°
c = 8.101 (3) ŵ = 0.50 mm1
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

Bruker SMART APEX CCD diffractometer855 independent reflections
Radiation source: fine-focus sealed tube840 reflections with I > 2σ(I)
graphiteRint = 0.014
phi and ω scansθmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −5→5
Tmin = 0.907, Tmax = 0.924k = −6→7
1324 measured reflectionsl = −9→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.1046P)2 + 0.7669P] where P = (Fo2 + 2Fc2)/3
855 reflections(Δ/σ)max < 0.001
64 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = −0.77 e Å3

Special details

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)

xyzUiso*/Ueq
P10.66113 (16)0.60637 (13)0.74674 (10)0.0149 (4)
O10.3963 (5)0.6733 (4)0.8092 (3)0.0225 (6)
O20.7837 (5)0.6917 (4)0.5956 (3)0.0224 (6)
O30.8828 (5)0.6695 (5)0.9016 (3)0.0224 (6)
H3B1.04810.61050.86960.034*
N10.7663 (7)0.1822 (5)0.6080 (4)0.0224 (7)
H1A0.74850.03240.59290.027*
H1B0.89180.26510.55660.027*
N20.4088 (7)0.1649 (5)0.7899 (4)0.0229 (7)
H2A0.38540.01480.77760.027*
H2B0.30470.23740.85540.027*
C10.6036 (7)0.2834 (6)0.7084 (4)0.0168 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0130 (6)0.0125 (5)0.0216 (6)0.0045 (3)0.0061 (4)0.0070 (3)
O10.0156 (13)0.0197 (13)0.0350 (14)0.0076 (10)0.0086 (10)0.0073 (10)
O20.0245 (13)0.0199 (13)0.0271 (14)0.0067 (10)0.0113 (10)0.0124 (10)
O30.0150 (13)0.0271 (14)0.0247 (13)0.0047 (10)0.0029 (10)0.0032 (10)
N10.0243 (16)0.0139 (14)0.0318 (17)0.0057 (12)0.0124 (13)0.0088 (12)
N20.0263 (16)0.0145 (14)0.0299 (17)0.0052 (12)0.0138 (13)0.0074 (12)
C10.0170 (16)0.0147 (15)0.0207 (16)0.0044 (12)0.0026 (12)0.0073 (12)

Geometric parameters (Å, °)

P1—O21.487 (2)N1—H1A0.8600
P1—O11.490 (3)N1—H1B0.8600
P1—O31.587 (3)N2—C11.314 (5)
P1—C11.845 (3)N2—H2A0.8600
O3—H3B0.9600N2—H2B0.8600
N1—C11.299 (5)
O2—P1—O1119.46 (15)C1—N1—H1B120.0
O2—P1—O3111.94 (15)H1A—N1—H1B120.0
O1—P1—O3106.97 (15)C1—N2—H2A120.0
O2—P1—C1108.20 (15)C1—N2—H2B120.0
O1—P1—C1107.89 (15)H2A—N2—H2B120.0
O3—P1—C1100.70 (15)N1—C1—N2122.4 (3)
P1—O3—H3B109.3N1—C1—P1118.7 (3)
C1—N1—H1A120.0N2—C1—P1118.8 (3)
O2—P1—C1—N128.6 (3)O2—P1—C1—N2−154.6 (3)
O1—P1—C1—N1159.2 (3)O1—P1—C1—N2−24.1 (3)
O3—P1—C1—N1−88.9 (3)O3—P1—C1—N287.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3B···O1i0.961.752.611 (4)147.
N1—H1A···O2ii0.862.062.903 (4)167.
N2—H2A···O1ii0.862.092.924 (4)164.
N1—H1B···O2iii0.862.022.812 (4)153.
N2—H2B···O3iv0.862.213.008 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JJ2049).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography