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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2340.
Published online 2008 November 13. doi:  10.1107/S1600536808037045
PMCID: PMC2960039

Ammonium 1-ammonio­ethane-1,1-diylbis(hydrogenphospho­nate) dihydrate

Abstract

The title compound, NH4 +·C2H8NO6P2 ·2H2O, was obtained by the reaction between 1-amino­ethane-1,1-diyldiphospho­nic acid and ammonium hydroxide (1:1) in an aqueous solution. The asymmetric unit contains one anion with two H atoms transferred from the phospho­nic acid groups to the amino group of the anion and to an ammonia mol­ecule, giving an ammonium cation. The structure displays N—H(...)O and O—H(...)O hydrogen bonding, which creates a three-dimensional network.

Related literature

Diphospho­nic acids are efficient drugs for the prevention of calcification and the inhibition bone resorption (Tromelin et al., 1986 [triangle], Matczak-Jon & Videnova-Adrabinska, 2005 [triangle]) and are used in the treatment of Pagets disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002 [triangle]). For related structures, see: Bruckmann et al. (1999 [triangle]); Olive et al. (2000 [triangle]); Coiro et al. (1989 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2340-scheme1.jpg

Experimental

Crystal data

  • NH4 +·C2H8NO6P2 ·2H2O
  • M r = 258.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2340-efi1.jpg
  • a = 8.8922 (3) Å
  • b = 6.9390 (3) Å
  • c = 18.9576 (8) Å
  • β = 117.957 (2)°
  • V = 1033.23 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.45 mm−1
  • T = 173 (2) K
  • 0.23 × 0.19 × 0.09 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.906, T max = 0.963
  • 14152 measured reflections
  • 2126 independent reflections
  • 1710 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.074
  • S = 1.05
  • 2126 reflections
  • 180 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037045/rk2118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037045/rk2118Isup2.hkl

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

Acknowledgments

The authors offer special thanks to Dr E. B. Rusanov for his help with the article preparation.

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 two protons transferred from the phosphonic group to the amino group and from another phosphonic group to ammonium cation. In the crystal structure of the title compound the phosphorus atom displays a slightly distorted tetrahedral geometry provided by three oxygen atoms and one carbon atom (Bruckmann et al. (1999); Olive et al. (2000); Coiro et al. (1989)). Bond lengths and angles have normal values (Allen et al., 1987). One ammonium cation and two solvent water molecules are present in asymetric unit. The structure is stabilized by three-dimensional O–H···O and N–H···O hydrogen bonds network (Table 1, Fig.2).

Experimental

The title compound was obtained by the reaction of 1-aminoethane-1,1-diyldiphosphonic 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 1 day staying.

Refinement

All H atoms bonded to O and N atoms were located in a difference map. Other H atoms bonded to C were positioned geometrically and refined using a riding model with C–H = 0.98 Å for CH3 with Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
The asymmetric unit of title compound with the atom numbering scheme. The displacement ellipsoids are shown at 50% probability level. H 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

H4N+·C2H8NO6P2·2H2OF000 = 544
Mr = 258.11Dx = 1.659 Mg m3
Monoclinic, P21/cMelting point: 511 K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 8.8922 (3) ÅCell parameters from 4102 reflections
b = 6.9390 (3) Åθ = 2.4–26.4º
c = 18.9576 (8) ŵ = 0.45 mm1
β = 117.957 (2)ºT = 173 (2) K
V = 1033.23 (7) Å3Needle, colourless
Z = 40.23 × 0.19 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2126 independent reflections
Radiation source: Fine-focus sealed tube1710 reflections with I > 2σ(I)
Monochromator: GraphiteRint = 0.057
T = 173(2) Kθmax = 26.5º
[var phi] and ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −11→11
Tmin = 0.906, Tmax = 0.963k = −8→8
14152 measured reflectionsl = −23→23

Refinement

Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.0326P)2 + 0.4969P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2126 reflectionsΔρmax = 0.50 e Å3
180 parametersΔρmin = −0.42 e Å3
2 restraintsExtinction correction: None
Primary atom site location: Direct

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 > 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
P10.45684 (7)0.78215 (7)0.83905 (3)0.00967 (14)
P20.75545 (7)0.49061 (7)0.90274 (3)0.00998 (14)
C10.6842 (3)0.7385 (3)0.86839 (12)0.0102 (4)
C20.7977 (3)0.8851 (3)0.93146 (13)0.0151 (5)
H2A0.91720.86040.94600.023*
H2B0.78160.87300.97900.023*
H2C0.76681.01570.90970.023*
N10.7091 (2)0.7652 (3)0.79539 (11)0.0110 (4)
N20.4118 (3)0.2940 (3)0.92879 (12)0.0156 (4)
O10.41873 (18)0.6941 (2)0.90108 (8)0.0136 (3)
O20.42601 (18)0.99358 (19)0.82470 (8)0.0138 (3)
O30.35764 (18)0.6661 (2)0.75879 (9)0.0118 (3)
O40.61946 (17)0.3541 (2)0.84970 (8)0.0127 (3)
O50.92422 (18)0.4672 (2)0.90282 (8)0.0137 (3)
O60.7742 (2)0.4803 (2)0.98869 (9)0.0142 (3)
H3O0.366 (3)0.724 (4)0.7255 (16)0.033 (8)*
H6O0.873 (4)0.492 (4)1.0228 (18)0.044 (9)*
H11N0.653 (3)0.669 (4)0.7568 (15)0.022 (6)*
H12N0.822 (3)0.761 (3)0.8110 (14)0.016 (6)*
H13N0.672 (3)0.878 (4)0.7751 (14)0.019 (7)*
H21N0.303 (4)0.265 (4)0.9075 (17)0.036 (8)*
H22N0.453 (3)0.222 (4)0.9061 (16)0.028 (8)*
H23N0.418 (3)0.422 (5)0.9160 (17)0.039 (8)*
H24N0.463 (3)0.275 (3)0.9819 (15)0.013 (6)*
O70.0562 (2)0.2189 (3)0.83327 (12)0.0225 (4)
O8−0.0558 (2)0.3200 (3)0.67241 (11)0.0235 (4)
H71O0.019 (4)0.249 (4)0.786 (2)0.042 (9)*
H72O0.004 (3)0.278 (4)0.8504 (16)0.025 (8)*
H81O−0.145 (3)0.279 (4)0.6455 (15)0.034 (9)*
H82O−0.064 (4)0.431 (3)0.668 (2)0.063 (12)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0092 (3)0.0081 (3)0.0112 (3)0.0005 (2)0.0044 (2)0.0006 (2)
P20.0099 (3)0.0091 (3)0.0099 (3)0.0006 (2)0.0038 (2)0.0007 (2)
C10.0101 (10)0.0095 (10)0.0110 (10)−0.0006 (8)0.0049 (8)0.0002 (8)
C20.0152 (11)0.0123 (11)0.0167 (11)−0.0028 (9)0.0065 (9)−0.0034 (9)
N10.0104 (10)0.0097 (9)0.0125 (9)0.0006 (8)0.0051 (8)0.0019 (8)
N20.0169 (11)0.0169 (11)0.0144 (11)−0.0005 (9)0.0084 (9)−0.0014 (8)
O10.0138 (8)0.0141 (8)0.0144 (8)0.0004 (6)0.0078 (6)0.0025 (6)
O20.0155 (8)0.0104 (7)0.0152 (7)0.0010 (6)0.0069 (6)0.0004 (6)
O30.0130 (8)0.0103 (7)0.0108 (7)−0.0015 (6)0.0044 (6)0.0010 (6)
O40.0131 (8)0.0100 (7)0.0142 (7)−0.0009 (6)0.0058 (6)−0.0007 (6)
O50.0117 (8)0.0144 (8)0.0141 (7)0.0018 (6)0.0052 (6)−0.0001 (6)
O60.0107 (8)0.0194 (8)0.0114 (7)0.0008 (6)0.0042 (7)0.0014 (6)
O70.0173 (9)0.0237 (9)0.0262 (10)0.0030 (7)0.0100 (8)−0.0056 (8)
O80.0164 (10)0.0216 (10)0.0324 (10)0.0009 (8)0.0115 (9)−0.0013 (8)

Geometric parameters (Å, °)

P1—O21.4939 (14)N1—H11N0.94 (3)
P1—O11.4982 (14)N1—H12N0.90 (3)
P1—O31.5760 (15)N1—H13N0.87 (3)
P1—C11.853 (2)N2—H21N0.88 (3)
P2—O41.4933 (15)N2—H22N0.85 (3)
P2—O51.5088 (15)N2—H23N0.93 (3)
P2—O61.5598 (15)N2—H24N0.90 (2)
P2—C11.843 (2)O3—H3O0.78 (3)
C1—N11.512 (3)O6—H6O0.81 (3)
C1—C21.534 (3)O7—H71O0.83 (3)
C2—H2A0.9800O7—H72O0.80 (3)
C2—H2B0.9800O8—H81O0.768 (17)
C2—H2C0.9800O8—H82O0.775 (18)
O2—P1—O1116.99 (8)H2A—C2—H2B109.5
O2—P1—O3110.75 (8)C1—C2—H2C109.5
O1—P1—O3108.61 (9)H2A—C2—H2C109.5
O2—P1—C1107.25 (9)H2B—C2—H2C109.5
O1—P1—C1108.31 (9)C1—N1—H11N111.7 (15)
O3—P1—C1104.13 (9)C1—N1—H12N108.2 (15)
O4—P2—O5115.05 (8)H11N—N1—H12N110 (2)
O4—P2—O6109.31 (8)C1—N1—H13N109.0 (15)
O5—P2—O6112.01 (8)H11N—N1—H13N110 (2)
O4—P2—C1108.55 (9)H12N—N1—H13N108 (2)
O5—P2—C1106.13 (9)H21N—N2—H22N106 (3)
O6—P2—C1105.23 (9)H21N—N2—H23N107 (2)
N1—C1—C2107.87 (16)H22N—N2—H23N110 (3)
N1—C1—P2105.33 (13)H21N—N2—H24N110 (2)
C2—C1—P2110.63 (14)H22N—N2—H24N112 (2)
N1—C1—P1108.22 (14)H23N—N2—H24N112 (2)
C2—C1—P1110.60 (14)P1—O3—H3O107 (2)
P2—C1—P1113.86 (10)P2—O6—H6O112 (2)
C1—C2—H2A109.5H71O—O7—H72O108 (3)
C1—C2—H2B109.5H81O—O8—H82O106 (3)
O4—P2—C1—N1−77.19 (14)O2—P1—C1—N1−71.57 (14)
O5—P2—C1—N147.00 (15)O1—P1—C1—N1161.33 (13)
O6—P2—C1—N1165.88 (13)O3—P1—C1—N145.86 (15)
O4—P2—C1—C2166.50 (13)O2—P1—C1—C246.40 (16)
O5—P2—C1—C2−69.31 (15)O1—P1—C1—C2−80.71 (15)
O6—P2—C1—C249.58 (16)O3—P1—C1—C2163.82 (14)
O4—P2—C1—P141.22 (13)O2—P1—C1—P2171.69 (10)
O5—P2—C1—P1165.41 (10)O1—P1—C1—P244.58 (13)
O6—P2—C1—P1−75.71 (12)O3—P1—C1—P2−70.88 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3O···O4i0.78 (3)1.74 (3)2.523 (2)179 (3)
O6—H6O···O5ii0.81 (3)1.71 (3)2.526 (2)175 (3)
N1—H11N···O2iii0.94 (3)1.83 (3)2.759 (2)169 (2)
N1—H12N···O8i0.90 (3)2.00 (3)2.873 (3)164 (2)
N1—H13N···O3i0.87 (3)2.08 (3)2.928 (2)167 (2)
N2—H21N···O70.88 (3)2.00 (3)2.860 (3)165 (3)
N2—H22N···O2iv0.85 (3)2.14 (3)2.914 (3)151 (2)
N2—H23N···O10.93 (3)1.91 (3)2.832 (3)171 (3)
N2—H24N···O1v0.90 (2)1.97 (3)2.850 (3)165 (2)
O7—H71O···O80.83 (3)1.99 (3)2.817 (3)177 (3)
O7—H72O···O5vi0.80 (3)1.97 (3)2.745 (2)165 (3)
O8—H81O···O1vii0.768 (17)2.244 (19)2.984 (2)162 (3)
O8—H82O···O7viii0.775 (18)1.999 (19)2.770 (3)173 (4)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, y−1, z; (v) −x+1, −y+1, −z+2; (vi) x−1, y, z; (vii) −x, y−1/2, −z+3/2; (viii) −x, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2118).

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.
  • Bruckmann, J., Krüger, C., Lehmann, C. W., Leitner, W., Rust, J. & Six, C. (1999). Acta Cryst. C55, 695–696.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Coiro, V. M. & Lamba, D. (1989). Acta Cryst. C45, 446–448.
  • Matczak-Jon, E. & Videnova-Adrabinska, V. (2005). Coord. Chem. Rev.249, 2458–2488.
  • Olive, G., Ellis, D. D., Siri, D., Le Moigne, F., Lutz, M., Spek, A. L., Tordo, P. & Reboul, J.-P. (2000). Acta Cryst. C56, 720–722. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • 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.

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