supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2009). E65, m459    [ doi:10.1107/S1600536809010599 ]

Tetraaquabis[(1-ammonio-1-phosphonoethyl)phosphonato]zinc(II) tetrahydrate

A. Dudko, V. Bon, A. Kozachkova and V. Pekhnyo

Abstract top

The title compound, [Zn(C2H8NO6P2)2(H2O)4]·4H2O, was synthesized by the reaction of ZnCl2 with 1-aminoethane-1,1-diyldiphosphonic acid in aqueous solution. The asymmetric unit contains one-half of the complex and two water molecules of solvation. The Zn atom occupies a special position on an inversion centre. This results in a slightly distorted octahedral coordination environment, which consists of the O atoms from two phosphonic acids and four water molecules. The crystal structure displays N-H...O and O-H...O hydrogen bonding, which creates a three-dimensional network.

Comment top

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 (Matczak-Jon et al., 2005). Diphosphonic acids and their metal complexes are used in the treatment of Pagets disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002). The asymmetric unit of title compound contains one-half of the formula unit (Fig.1); Zn atom occupy special position at the inversion centre and creates a slightly distorted octahedral coordination environment, which consist of two phosphonic and four aqueous oxygen atoms. The coordinated diphosphonic acids residue exist as zwitterions with positive charge on NH3 group and negative on the oxygen atom of the non-coordinated phosphonic group. The crystal structure displays N—H···O and O—H···O hydrogen bonding, which creates a three-dimensional network (Table 1, Fig.2).

Related literature top

Diphosphonic acids are efficient drugs for the prevention of calcification and the inhibition of bone resorption, see: Matczak-Jon et al. (2005). Diphosphonic acids and their metal complexes are used in the treatment of Pagets disease, osteoporosis and tumoral osteolysis, see: Szabo et al. (2002). For related structures, see: Li et al. (2006, 2007); Lin et al. (2007). [formula implies tetrahydrate; scheme shows dihydrate]

Experimental top

10 ml of the 0.01 M ZnCl2 aqueous solution was added to the 10 ml of 0.02 M water solution of 1-aminoethane-1,1-diyldiphosphonic acid. Colorless crystals of title compound were obtained after 2 weeks of slow evaporation of the resulted solution.

Refinement top

H atoms bonded to N and O were located in a difference map and were freely refined with Uiso(H) = 1.2 Ueq of the carrier atom. Other H atoms which bonded to C were positioned geometrically and refined using a riding model with C—H = 0.98 Å for CH3 [Uiso(H) = 1.5Ueq(C)].

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms [Symmetry code: (i) -x, 1 - y, 1 - z].
[Figure 2] Fig. 2. Crystal packing of title compound, projection along a axis. Dashed lines indicate hydrogen bonds.
Tetraaquabis[(1-ammonio-1-phosphonoethyl)phosphonato]zinc(II) tetrahydrate top
Crystal data top
[Zn(C2H8NO6P2)2(H2O)4]·4H2OZ = 1
Mr = 617.57F(000) = 320
Triclinic, P1Dx = 1.866 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.6712 (4) ÅCell parameters from 2105 reflections
b = 9.3279 (6) Åθ = 2.3–25.9°
c = 10.7009 (7) ŵ = 1.50 mm−1
α = 96.440 (3)°T = 173 K
β = 90.788 (3)°Block, colourless
γ = 102.080 (3)°0.36 × 0.10 × 0.04 mm
V = 549.65 (6) Å3
Data collection top
Bruker APEXII CCD
diffractometer		2244 independent reflections
Radiation source: fine-focus sealed tube1747 reflections with I > 2σ(I)
graphiteRint = 0.058
Detector resolution: 8.26 pixels mm-1θmax = 26.4°, θmin = 2.3°
φ and ω scansh = −7→7
Absorption correction: numerical
(SADABS; Bruker, 2005)		k = −11→10
Tmin = 0.612, Tmax = 0.945l = −13→13
8897 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0395P)2]
where P = (Fo2 + 2Fc2)/3
2244 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.39 e Å−3
1 restraintΔρmin = −0.47 e Å−3
Crystal data top
[Zn(C2H8NO6P2)2(H2O)4]·4H2Oγ = 102.080 (3)°
Mr = 617.57V = 549.65 (6) Å3
Triclinic, P1Z = 1
a = 5.6712 (4) ÅMo Kα radiation
b = 9.3279 (6) ŵ = 1.50 mm−1
c = 10.7009 (7) ÅT = 173 K
α = 96.440 (3)°0.36 × 0.10 × 0.04 mm
β = 90.788 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		2244 independent reflections
Absorption correction: numerical
(SADABS; Bruker, 2005)		1747 reflections with I > 2σ(I)
Tmin = 0.612, Tmax = 0.945Rint = 0.058
8897 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081Δρmax = 0.39 e Å−3
S = 1.00Δρmin = −0.47 e Å−3
2244 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
Zn10.00000.50000.50000.01171 (16)
P10.02405 (14)0.80873 (8)0.37915 (7)0.01033 (19)
P2−0.00669 (14)0.81048 (9)0.09143 (7)0.0116 (2)
C10.1808 (5)0.8672 (3)0.2381 (3)0.0109 (6)
C20.2791 (6)1.0348 (3)0.2544 (3)0.0176 (7)
H2A0.39831.06140.32480.026*
H2B0.14611.08550.27160.026*
H2C0.35571.06440.17700.026*
N10.3905 (5)0.7921 (3)0.2240 (3)0.0133 (6)
H1A0.483 (6)0.830 (4)0.160 (3)0.020*
H1B0.349 (6)0.699 (4)0.208 (3)0.020*
H1C0.485 (6)0.807 (4)0.295 (3)0.020*
O1−0.0090 (4)0.6449 (2)0.37040 (19)0.0135 (5)
O20.2165 (4)0.8783 (2)0.4886 (2)0.0143 (5)
H2O0.206 (6)0.956 (4)0.519 (3)0.017*
O3−0.1966 (4)0.8741 (2)0.39210 (19)0.0139 (5)
O4−0.0857 (4)0.6470 (2)0.0759 (2)0.0181 (5)
O50.1793 (4)0.8548 (2)−0.0123 (2)0.0148 (5)
H5O0.182 (6)0.931 (3)−0.039 (3)0.018*
O6−0.1990 (4)0.8997 (2)0.0930 (2)0.0156 (5)
O70.1908 (4)0.3844 (3)0.3764 (2)0.0183 (5)
H710.319 (7)0.371 (4)0.408 (3)0.022*
H720.204 (7)0.413 (4)0.312 (4)0.022*
O80.3234 (4)0.6366 (3)0.5883 (2)0.0152 (5)
H810.311 (6)0.719 (4)0.571 (3)0.018*
H820.300 (6)0.633 (4)0.667 (4)0.018*
O90.2666 (4)0.6106 (3)0.8304 (2)0.0181 (5)
H910.228 (6)0.681 (4)0.882 (3)0.022*
H920.189 (6)0.532 (4)0.852 (3)0.022*
O100.3107 (4)0.4849 (3)0.1490 (2)0.0187 (5)
H1010.236 (6)0.448 (4)0.079 (4)0.022*
H1020.437 (7)0.460 (4)0.143 (3)0.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0117 (3)0.0109 (3)0.0129 (3)0.0029 (2)0.0003 (2)0.0021 (2)
P10.0105 (4)0.0103 (4)0.0105 (4)0.0031 (3)0.0003 (3)0.0009 (3)
P20.0115 (4)0.0125 (4)0.0116 (4)0.0031 (3)−0.0009 (3)0.0035 (3)
C10.0096 (15)0.0088 (15)0.0146 (16)0.0030 (12)0.0003 (12)0.0007 (12)
C20.0208 (18)0.0114 (16)0.0183 (18)−0.0021 (13)0.0001 (14)0.0017 (13)
N10.0105 (14)0.0155 (15)0.0134 (15)0.0010 (12)−0.0017 (11)0.0032 (12)
O10.0179 (12)0.0093 (11)0.0133 (12)0.0028 (9)0.0007 (9)0.0011 (8)
O20.0164 (12)0.0141 (12)0.0129 (12)0.0067 (10)−0.0032 (9)−0.0032 (9)
O30.0118 (11)0.0150 (12)0.0154 (12)0.0049 (9)−0.0013 (9)−0.0004 (9)
O40.0224 (13)0.0143 (12)0.0158 (12)0.0001 (9)−0.0047 (10)0.0013 (9)
O50.0187 (12)0.0118 (12)0.0167 (12)0.0061 (10)0.0061 (9)0.0080 (9)
O60.0113 (11)0.0206 (12)0.0178 (12)0.0060 (9)0.0024 (9)0.0092 (9)
O70.0186 (13)0.0225 (13)0.0162 (13)0.0090 (10)−0.0004 (11)0.0043 (10)
O80.0146 (12)0.0139 (12)0.0181 (13)0.0034 (10)−0.0017 (10)0.0054 (10)
O90.0201 (13)0.0148 (12)0.0199 (13)0.0042 (10)0.0041 (10)0.0025 (10)
O100.0152 (13)0.0239 (13)0.0176 (13)0.0072 (11)−0.0022 (10)−0.0004 (10)
Geometric parameters (Å, °) top
Zn1—O12.050 (2)C2—H2A0.9800
Zn1—O1i2.050 (2)C2—H2B0.9800
Zn1—O7i2.071 (2)C2—H2C0.9800
Zn1—O72.071 (2)N1—H1A0.93 (4)
Zn1—O8i2.141 (2)N1—H1B0.85 (4)
Zn1—O82.141 (2)N1—H1C0.90 (4)
P1—O11.492 (2)O2—H2O0.78 (3)
P1—O31.504 (2)O5—H5O0.793 (18)
P1—O21.575 (2)O7—H710.84 (4)
P1—C11.839 (3)O7—H720.76 (4)
P2—O41.486 (2)O8—H810.82 (4)
P2—O61.503 (2)O8—H820.86 (4)
P2—O51.571 (2)O9—H910.87 (4)
P2—C11.846 (3)O9—H920.83 (4)
C1—N11.502 (4)O10—H1010.85 (4)
C1—C21.535 (4)O10—H1020.80 (4)
O1—Zn1—O1i179.999 (1)N1—C1—P1107.2 (2)
O1—Zn1—O7i90.77 (9)C2—C1—P1110.6 (2)
O1i—Zn1—O7i89.23 (9)N1—C1—P2106.55 (19)
O1—Zn1—O789.23 (9)C2—C1—P2110.3 (2)
O1i—Zn1—O790.77 (9)P1—C1—P2113.58 (16)
O7i—Zn1—O7180.00 (11)C1—C2—H2A109.5
O1—Zn1—O8i88.74 (9)C1—C2—H2B109.5
O1i—Zn1—O8i91.26 (9)H2A—C2—H2B109.5
O7i—Zn1—O8i92.46 (9)C1—C2—H2C109.5
O7—Zn1—O8i87.54 (9)H2A—C2—H2C109.5
O1—Zn1—O891.27 (9)H2B—C2—H2C109.5
O1i—Zn1—O888.73 (9)C1—N1—H1A108 (2)
O7i—Zn1—O887.54 (9)C1—N1—H1B114 (2)
O7—Zn1—O892.46 (9)H1A—N1—H1B110 (3)
O8i—Zn1—O8180.0C1—N1—H1C113 (2)
O1—P1—O3118.11 (12)H1A—N1—H1C108 (3)
O1—P1—O2107.82 (12)H1B—N1—H1C104 (3)
O3—P1—O2111.01 (12)P1—O1—Zn1133.80 (13)
O1—P1—C1107.13 (13)P1—O2—H2O115 (3)
O3—P1—C1108.84 (13)P2—O5—H5O118 (3)
O2—P1—C1102.79 (13)Zn1—O7—H71113 (2)
O4—P2—O6117.67 (13)Zn1—O7—H72114 (3)
O4—P2—O5108.21 (12)H71—O7—H72114 (4)
O6—P2—O5110.56 (12)Zn1—O8—H81101 (2)
O4—P2—C1108.34 (13)Zn1—O8—H82103 (2)
O6—P2—C1108.52 (13)H81—O8—H82108 (3)
O5—P2—C1102.44 (13)H91—O9—H92106 (3)
N1—C1—C2108.4 (3)H101—O10—H102103 (3)
O1—P1—C1—N1−47.7 (2)O6—P2—C1—C2−54.5 (2)
O3—P1—C1—N1−176.47 (18)O5—P2—C1—C262.5 (2)
O2—P1—C1—N165.8 (2)O4—P2—C1—P1−58.45 (19)
O1—P1—C1—C2−165.7 (2)O6—P2—C1—P170.38 (18)
O3—P1—C1—C265.6 (2)O5—P2—C1—P1−172.68 (15)
O2—P1—C1—C2−52.2 (2)O3—P1—O1—Zn1−92.94 (19)
O1—P1—C1—P269.67 (18)O2—P1—O1—Zn133.8 (2)
O3—P1—C1—P2−59.08 (18)C1—P1—O1—Zn1143.85 (17)
O2—P1—C1—P2−176.85 (15)O7i—Zn1—O1—P141.88 (18)
O4—P2—C1—N159.3 (2)O7—Zn1—O1—P1−138.12 (18)
O6—P2—C1—N1−171.88 (19)O8i—Zn1—O1—P1134.32 (18)
O5—P2—C1—N1−54.9 (2)O8—Zn1—O1—P1−45.68 (18)
O4—P2—C1—C2176.7 (2)
Symmetry codes: (i) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O6ii0.93 (4)1.96 (4)2.796 (4)150 (3)
N1—H1B···O100.85 (4)1.99 (4)2.827 (4)168 (3)
N1—H1C···O3ii0.90 (4)2.01 (4)2.851 (3)153 (3)
O2—H2O···O3iii0.78 (3)1.76 (3)2.536 (3)172 (4)
O5—H5O···O6iv0.79 (2)1.73 (2)2.519 (3)177 (4)
O7—H71···O8v0.84 (4)2.05 (4)2.826 (3)155 (3)
O7—H72···O100.76 (4)2.00 (4)2.748 (3)168 (4)
O8—H81···O20.82 (4)1.97 (4)2.772 (3)163 (3)
O8—H82···O90.86 (4)1.79 (4)2.646 (3)174 (3)
O9—H91···O5vi0.87 (4)1.94 (4)2.810 (3)172 (3)
O9—H92···O4i0.83 (4)1.91 (4)2.715 (3)165 (4)
O10—H101···O4vii0.85 (4)1.90 (4)2.744 (3)175 (3)
O10—H102···O9v0.80 (4)1.96 (4)2.741 (3)167 (4)
Symmetry codes: (ii) x+1, y, z; (iii) −x, −y+2, −z+1; (iv) −x, −y+2, −z; (v) −x+1, −y+1, −z+1; (vi) x, y, z+1; (i) −x, −y+1, −z+1; (vii) −x, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O6i0.93 (4)1.96 (4)2.796 (4)150 (3)
N1—H1B···O100.85 (4)1.99 (4)2.827 (4)168 (3)
N1—H1C···O3i0.90 (4)2.01 (4)2.851 (3)153 (3)
O2—H2O···O3ii0.78 (3)1.76 (3)2.536 (3)172 (4)
O5—H5O···O6iii0.79 (2)1.73 (2)2.519 (3)177 (4)
O7—H71···O8iv0.84 (4)2.05 (4)2.826 (3)155 (3)
O7—H72···O100.76 (4)2.00 (4)2.748 (3)168 (4)
O8—H81···O20.82 (4)1.97 (4)2.772 (3)163 (3)
O8—H82···O90.86 (4)1.79 (4)2.646 (3)174 (3)
O9—H91···O5v0.87 (4)1.94 (4)2.810 (3)172 (3)
O9—H92···O4vi0.83 (4)1.91 (4)2.715 (3)165 (4)
O10—H101···O4vii0.85 (4)1.90 (4)2.744 (3)175 (3)
O10—H102···O9iv0.80 (4)1.96 (4)2.741 (3)167 (4)
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+2, −z+1; (iii) −x, −y+2, −z; (iv) −x+1, −y+1, −z+1; (v) x, y, z+1; (vi) −x, −y+1, −z+1; (vii) −x, −y+1, −z.
references
References top

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Li, M., Chen, S., Xiang, J., He, H., Yuan, L. & Sun, J. (2006). Cryst. Growth Des. 6, 1250–1255.

Li, M. & Sun, J.-T. (2007). Acta Cryst. E63, m1370–m1372.

Lin, L., Zhang, T., Fan, Y., Ding, D. & Hou, H. (2007). J. Mol. Struct. 837, 107–117.

Matczak-Jon, E. & Videnova-Adrabinska, V. (2005). Coord. Chem. Rev. 249, 2458–2488.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Szabo, Ch. M., Martin, M. B. & Oldfield, E. (2002). J. Med. Chem. 45, 2894–2903.

Westrip, S. P. (2009). publCIF. In preparation.