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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1961.
Published online 2009 July 22. doi:  10.1107/S1600536809028323
PMCID: PMC2977313

Ammonium dihydrogen (1-ammonio­pentane-1,1-di­yl)diphospho­nate

Abstract

The title compound, NH4 +·C5H14NO6P2 , was obtained from 1-ammonio-1-phosphono­pentane-1-phospho­nic acid and ammonium hydroxide in aqueous solution. The asymmetric unit of title compound contains one molecule, which consists of an ammonium cation and an aminodiphosphonic anion with the H atoms transferred from the phosphonic acid group to the amino group. The crystal structure shows a three-dimensional network of O—H(...)O and N—H(...)O hydrogen bonds which stabilize the structure.

Related literature

For general background to the use of organic diphospho­nic acids as chelating agents in metal extraction and as drugs to prevent calcification and inhibit bone resorption, see: Matczak-Jon & Videnova-Adrabinska (2005 [triangle]); Tromelin et al. (1986 [triangle]); Szabo et al. (2002 [triangle]). For related structures, see: Bon et al. (2008 [triangle]). For bond–length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1961-scheme1.jpg

Experimental

Crystal data

  • NH4 +·C5H14NO6P2
  • M r = 264.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1961-efi1.jpg
  • a = 9.6007 (6) Å
  • b = 5.7239 (4) Å
  • c = 20.3259 (15) Å
  • β = 98.100 (3)°
  • V = 1105.84 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 mm−1
  • T = 296 K
  • 0.50 × 0.12 × 0.04 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.824, T max = 0.982
  • 5297 measured reflections
  • 2256 independent reflections
  • 1532 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.122
  • S = 1.02
  • 2256 reflections
  • 173 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028323/rk2155sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028323/rk2155Isup2.hkl

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

supplementary crystallographic information

Comment

The organic diphosphonic acids are potentially very powerful chelating agents used in metal extractions and are tested by the pharmaceutical industry for use as efficient drugs preventing calcification and inhibiting bone resorption (Tromelin et al., 1986, Matczak-Jon & Videnova-Adrabinska, 2005). Diphosphonic acids are used in the treatment of Paget disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002). The asymmetric unit of title compound (Fig. 1) contains one molecule, which exists as anion with protons transferred from the phosphonic group to the amino group. The ammonium cation attendant in structure neutralizes the negatively charged phosphonic acid residual. The phosphorus atom displays a slightly distorted tetrahedral geometry provided by three oxygen atoms and one carbon atom. Bond lengths and angles have normal values (Allen et al., 1987). The crystal structure of title compound shows three–dimensional network of O—H···O and N—H···O hydrogen bonds which additionally stabilized the structure (Table 1, Fig. 2).

Experimental

The title compound was obtained by the reaction of 1–ammonio–1–phosphonopentane–1–phosphonic acid and ammonium hydroxide (1:1) in the aqueous solution. The solution was left at room temperature. Colourless crystals of the title compound were obtained after 5 days staying.

Refinement

The H atoms bonded to O and N atoms were located in a difference map and refined freely. Other H atoms which bonded to C were positioned geometrically and refined using a riding model with C—H = 0.96 Å for CH3 with Uiso(H) = 1.5Ueq(C) and C—H = 0.97 Å for CH2 with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The asymmetric unit of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. Hydrogen atoms are presented as a small spheres of arbitrary rAdius.
Fig. 2.
Crystal packing of title compound, projection along b axis. Dashed lines indicate hydrogen bonds.

Crystal data

NH4+·C5H14NO6P2F(000) = 560
Mr = 264.15Dx = 1.587 Mg m3
Monoclinic, P21/cMelting point: 495 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 9.6007 (6) ÅCell parameters from 824 reflections
b = 5.7239 (4) Åθ = 2.7–21.1°
c = 20.3259 (15) ŵ = 0.41 mm1
β = 98.100 (3)°T = 296 K
V = 1105.84 (13) Å3Needle, colourless
Z = 40.50 × 0.12 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer2256 independent reflections
Radiation source: fine–focus sealed tube1532 reflections with I > 2σ(I)
graphiteRint = 0.056
Detector resolution: 8.26 pixels mm-1θmax = 26.4°, θmin = 2.0°
[var phi] and ω scansh = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −7→5
Tmin = 0.824, Tmax = 0.982l = −24→25
5297 measured reflections

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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0435P)2 + 0.4298P] where P = (Fo2 + 2Fc2)/3
2256 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.38 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
P10.22481 (10)0.43513 (17)0.29915 (4)0.0195 (3)
P20.00587 (9)0.47871 (16)0.39608 (4)0.0184 (2)
C10.1590 (3)0.3149 (6)0.37310 (16)0.0161 (7)
C20.2832 (4)0.3109 (7)0.43011 (17)0.0243 (8)
H2A0.36350.24390.41290.029*
H2B0.30700.47150.44210.029*
C30.2649 (4)0.1806 (7)0.49344 (17)0.0295 (9)
H3A0.17870.23160.50880.035*
H3B0.25670.01460.48410.035*
C40.3877 (4)0.2227 (8)0.54735 (18)0.0374 (11)
H4A0.38850.38600.56020.045*
H4B0.47450.19090.52970.045*
C50.3827 (5)0.0731 (9)0.6084 (2)0.0506 (13)
H5A0.29850.10740.62710.076*
H5B0.46340.10590.64070.076*
H5C0.3831−0.08890.59620.076*
N10.1106 (3)0.0689 (5)0.35619 (16)0.0200 (7)
N20.3682 (4)0.9144 (7)0.2109 (2)0.0297 (8)
O10.3514 (2)0.2924 (4)0.28929 (11)0.0247 (6)
O20.2493 (3)0.6898 (4)0.31012 (12)0.0279 (6)
O30.1056 (3)0.3928 (5)0.23993 (12)0.0282 (7)
O4−0.0725 (3)0.2932 (4)0.43385 (13)0.0263 (6)
O5−0.0902 (2)0.5374 (5)0.33383 (12)0.0280 (6)
O60.0601 (3)0.6800 (4)0.43945 (11)0.0237 (6)
H3O0.107 (5)0.279 (9)0.217 (2)0.065 (18)*
H4O−0.061 (5)0.303 (9)0.475 (2)0.070 (18)*
H11N0.180 (4)−0.059 (7)0.3428 (19)0.047 (12)*
H12N0.078 (5)−0.001 (8)0.392 (2)0.060 (14)*
H13N0.038 (4)0.063 (7)0.321 (2)0.040 (12)*
H21N0.336 (5)0.810 (9)0.247 (3)0.083 (18)*
H22N0.449 (5)0.874 (7)0.2012 (19)0.040 (13)*
H23N0.295 (6)0.919 (10)0.176 (3)0.10 (2)*
H24N0.377 (5)1.058 (8)0.231 (2)0.048 (14)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0216 (5)0.0158 (5)0.0220 (5)−0.0005 (4)0.0066 (4)0.0005 (4)
P20.0181 (5)0.0165 (5)0.0213 (5)0.0008 (4)0.0054 (4)0.0007 (4)
C10.0180 (17)0.0085 (18)0.0212 (17)−0.0008 (15)0.0006 (14)0.0005 (13)
C20.0189 (18)0.026 (2)0.0263 (19)−0.0043 (17)−0.0025 (15)−0.0006 (16)
C30.028 (2)0.034 (3)0.0250 (19)−0.002 (2)0.0005 (17)0.0037 (17)
C40.037 (2)0.043 (3)0.029 (2)0.004 (2)−0.0054 (19)0.0001 (19)
C50.052 (3)0.068 (4)0.030 (2)0.011 (3)0.000 (2)0.007 (2)
N10.0237 (16)0.0152 (17)0.0211 (16)−0.0026 (14)0.0028 (14)−0.0007 (13)
N20.026 (2)0.026 (2)0.040 (2)0.0035 (18)0.0115 (18)0.0002 (17)
O10.0194 (13)0.0244 (15)0.0314 (13)0.0026 (12)0.0074 (11)−0.0023 (11)
O20.0360 (15)0.0154 (15)0.0347 (14)−0.0015 (13)0.0132 (12)−0.0007 (11)
O30.0297 (15)0.0329 (18)0.0216 (13)0.0049 (14)0.0019 (12)−0.0045 (13)
O40.0315 (15)0.0229 (16)0.0265 (15)−0.0089 (12)0.0108 (12)−0.0013 (12)
O50.0198 (12)0.0329 (17)0.0305 (14)0.0030 (12)0.0002 (11)0.0063 (12)
O60.0317 (14)0.0131 (14)0.0278 (13)−0.0043 (12)0.0097 (11)−0.0040 (10)

Geometric parameters (Å, °)

P1—O21.488 (3)C4—C51.514 (5)
P1—O11.501 (2)C4—H4A0.9700
P1—O31.559 (3)C4—H4B0.9700
P1—C11.844 (3)C5—H5A0.9600
P2—O51.495 (2)C5—H5B0.9600
P2—O61.499 (2)C5—H5C0.9600
P2—O41.564 (3)N1—H11N1.05 (4)
P2—C11.858 (3)N1—H12N0.93 (5)
C1—N11.507 (4)N1—H13N0.93 (4)
C1—C21.541 (5)N2—H21N1.02 (6)
C2—C31.519 (5)N2—H22N0.86 (4)
C2—H2A0.9700N2—H23N0.93 (6)
C2—H2B0.9700N2—H24N0.92 (5)
C3—C41.511 (5)O3—H3O0.80 (5)
C3—H3A0.9700O4—H4O0.82 (5)
C3—H3B0.9700
O2—P1—O1116.04 (14)C2—C3—H3B109.4
O2—P1—O3110.56 (16)H3A—C3—H3B108.0
O1—P1—O3109.44 (15)C3—C4—C5113.1 (4)
O2—P1—C1107.97 (15)C3—C4—H4A109.0
O1—P1—C1106.42 (15)C5—C4—H4A109.0
O3—P1—C1105.83 (15)C3—C4—H4B109.0
O5—P2—O6116.53 (15)C5—C4—H4B109.0
O5—P2—O4106.61 (15)H4A—C4—H4B107.8
O6—P2—O4112.60 (14)C4—C5—H5A109.5
O5—P2—C1108.42 (14)C4—C5—H5B109.5
O6—P2—C1108.33 (14)H5A—C5—H5B109.5
O4—P2—C1103.51 (14)C4—C5—H5C109.5
N1—C1—C2109.8 (3)H5A—C5—H5C109.5
N1—C1—P1107.0 (2)H5B—C5—H5C109.5
C2—C1—P1107.5 (2)C1—N1—H11N122 (2)
N1—C1—P2107.4 (2)C1—N1—H12N110 (3)
C2—C1—P2112.0 (2)H11N—N1—H12N101 (3)
P1—C1—P2113.01 (17)C1—N1—H13N113 (2)
C3—C2—C1118.3 (3)H11N—N1—H13N102 (3)
C3—C2—H2A107.7H12N—N1—H13N107 (4)
C1—C2—H2A107.7H21N—N2—H22N112 (4)
C3—C2—H2B107.7H21N—N2—H23N107 (4)
C1—C2—H2B107.7H22N—N2—H23N116 (4)
H2A—C2—H2B107.1H21N—N2—H24N103 (4)
C4—C3—C2111.4 (3)H22N—N2—H24N108 (4)
C4—C3—H3A109.4H23N—N2—H24N109 (4)
C2—C3—H3A109.4P1—O3—H3O120 (4)
C4—C3—H3B109.4P2—O4—H4O116 (4)
O2—P1—C1—N1170.1 (2)O5—P2—C1—C2162.9 (2)
O1—P1—C1—N1−64.7 (2)O6—P2—C1—C235.6 (3)
O3—P1—C1—N151.7 (3)O4—P2—C1—C2−84.2 (3)
O2—P1—C1—C2−72.0 (3)O5—P2—C1—P141.3 (2)
O1—P1—C1—C253.2 (3)O6—P2—C1—P1−86.01 (19)
O3—P1—C1—C2169.6 (2)O4—P2—C1—P1154.25 (17)
O2—P1—C1—P252.1 (2)N1—C1—C2—C3−53.3 (4)
O1—P1—C1—P2177.27 (16)P1—C1—C2—C3−169.4 (3)
O3—P1—C1—P2−66.4 (2)P2—C1—C2—C365.9 (4)
O5—P2—C1—N1−76.5 (2)C1—C2—C3—C4−171.9 (3)
O6—P2—C1—N1156.2 (2)C2—C3—C4—C5−172.9 (3)
O4—P2—C1—N136.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H11N···O2i1.05 (4)1.75 (4)2.777 (4)163 (3)
N1—H13N···O3ii0.93 (4)1.98 (4)2.828 (4)152 (3)
N1—H12N···O6i0.93 (5)2.08 (5)2.879 (4)143 (4)
O3—H3O···O5ii0.80 (5)1.72 (5)2.519 (4)174 (5)
O4—H4O···O6iii0.82 (5)1.75 (5)2.566 (3)173 (5)
N2—H22N···O1iv0.86 (4)1.95 (4)2.781 (4)161 (4)
N2—H21N···O21.02 (6)1.77 (6)2.769 (4)165 (4)
N2—H23N···O5v0.93 (6)2.07 (6)2.787 (5)134 (5)
N2—H24N···O1vi0.92 (5)1.83 (5)2.705 (5)159 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2155).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bon, V. V., Dudko, A. V., Kozachkova, A. N. & Pekhnyo, V. I. (2008). Acta Cryst. E64, o2436. [PMC free article] [PubMed]
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Matczak-Jon, E. & Videnova-Adrabinska, V. (2005). Coord. Chem. Rev 249, 2458–2488.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Szabo, Ch. M., Martin, M. B. & Oldfield, E. (2002). J. Med. Chem 45, 2894–2903. [PubMed]
  • Tromelin, A., El Manouni, D. & Burgada, R. (1986). Phosphorus Sulfur Relat. Elem.27, 301–312.
  • Westrip, S. P. (2009). publCIF In preparation.

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