Acta Cryst. (2009). E65, m1394 [ doi:10.1107/S1600536809042159 ]
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2O,O')cobaltate(II)In the salt, (NH4)2[Co(CH4O6P2)2(H2O)2], the methylenediphosphonate acts as a bidentate ligand and the CoII ion (site symmetry 
) assumes an octahedral CoO6 coordination geometry. The acid H atom of the ligand is distributed over two O atoms. In the crystal, a three-dimensional network is formed through O-H
O and N-HO hydrogen bonds between the cations and anions.
CoCl2.6H2O (0,1696 g, 0,00071 mol) was dissolved in water (7 cm3) and heated to 70°C. The pH of the solution was 4,89 and deep pink in colour. Ammonium bicarbonate was added to raise the pH to 5,61 after which methylene disphosphonate (0,25 g, 0,00142 mol), dissolved in water (5 cm3) was added dropwise. The final pH of the solution was adjusted to 1.50 with ammonium bicarbonate. (Yield: 84.1%)
The aliphatic H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with U<i/>iso(H) = 1.2U<i/>eq(C). The hydroxyl H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with U<i/>iso(H) = 1.5U<i/>eq(O). A 50% positional disorder was assigned to these hydrogen atoms and provided the best fits of the data. The highest electron density lies within 0.74 Å from O7.
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ng2665fig1thm.gif)
| Fig. 1. View of (I) (50% probability displacement ellipsoids). The ammonium cations have been omitted for clarity. |
| (NH4)2[Co(CH4O6P2)2(H2O)2] | Z = 1 |
| Mr = 479.01 | F(000) = 237 |
| Triclinic, P1 | Dx = 2.069 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
| a = 7.455 (5) Å | Cell parameters from 4649 reflections |
| b = 7.560 (5) Å | θ = 3.2–28.3° |
| c = 8.035 (5) Å | µ = 1.63 mm−1 |
| α = 88.282 (5)° | T = 103 K |
| β = 62.450 (5)° | Rod, pink |
| γ = 71.834 (5)° | 0.28 × 0.16 × 0.11 mm |
| V = 378.0 (4) Å3 |
| Bruker SMART diffractometer | 1875 independent reflections |
| Radiation source: sealed tube | 1735 reflections with I > 2σ(I) |
| graphite | Rint = 0.029 |
| φ and ω scans | θmax = 28.4°, θmin = 3.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
| Tmin = 0.739, Tmax = 0.830 | k = −9→10 |
| 8419 measured reflections | l = −10→9 |
| Refinement on F2 | 6 restraints |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.4031P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
| S = 1.23 | Δρmax = 0.58 e Å−3 |
| 1875 reflections | Δρmin = −0.48 e Å−3 |
| 134 parameters |
| (NH4)2[Co(CH4O6P2)2(H2O)2] | γ = 71.834 (5)° |
| Mr = 479.01 | V = 378.0 (4) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.455 (5) Å | Mo Kα radiation |
| b = 7.560 (5) Å | µ = 1.63 mm−1 |
| c = 8.035 (5) Å | T = 103 K |
| α = 88.282 (5)° | 0.28 × 0.16 × 0.11 mm |
| β = 62.450 (5)° |
| Bruker SMART diffractometer | 1875 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1735 reflections with I > 2σ(I) |
| Tmin = 0.739, Tmax = 0.830 | Rint = 0.029 |
| 8419 measured reflections | θmax = 28.4° |
| R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.097 | Δρmax = 0.58 e Å−3 |
| S = 1.23 | Δρmin = −0.48 e Å−3 |
| 1875 reflections | Absolute structure: ? |
| 134 parameters | Flack parameter: ? |
| 6 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.5 | 0 | 1 | 0.00601 (14) | |
| P1 | 0.79673 (9) | 0.26243 (8) | 0.74506 (8) | 0.00547 (16) | |
| P2 | 0.40236 (9) | 0.26654 (8) | 0.71287 (8) | 0.00548 (15) | |
| C1 | 0.5577 (4) | 0.3956 (3) | 0.7338 (3) | 0.0069 (4) | |
| H51 | 0.4658 | 0.487 | 0.847 | 0.008* | |
| H61 | 0.5984 | 0.465 | 0.6264 | 0.008* | |
| O2 | 0.3230 (3) | 0.1616 (2) | 0.8790 (2) | 0.0082 (3) | |
| O3 | 0.7476 (3) | 0.1227 (2) | 0.8847 (2) | 0.0079 (3) | |
| O6 | 0.5476 (3) | 0.1357 (2) | 0.5238 (2) | 0.0103 (4) | |
| H6A | 0.4935 | 0.058 | 0.5191 | 0.016* | 0.5 |
| O1 | 0.3253 (3) | 0.2144 (3) | 1.2321 (2) | 0.0101 (4) | |
| N1 | 0.8609 (4) | 0.1904 (3) | 0.1800 (3) | 0.0114 (4) | |
| O7 | 0.2170 (3) | 0.4231 (2) | 0.7030 (2) | 0.0092 (3) | |
| H7 | 0.1063 | 0.3971 | 0.7569 | 0.014* | 0.5 |
| O5 | 0.9736 (3) | 0.1640 (2) | 0.5452 (2) | 0.0091 (3) | |
| H5A | 0.9708 | 0.0583 | 0.5301 | 0.014* | 0.5 |
| O4 | 0.8575 (3) | 0.4110 (2) | 0.8125 (2) | 0.0083 (3) | |
| H4 | 0.9866 | 0.3715 | 0.7787 | 0.013* | 0.5 |
| H1N | 0.860 (5) | 0.298 (3) | 0.197 (4) | 0.010 (8)* | |
| H2N | 0.779 (5) | 0.165 (6) | 0.282 (4) | 0.029 (10)* | |
| H3N | 0.984 (3) | 0.121 (4) | 0.149 (5) | 0.020 (9)* | |
| H4N | 0.829 (6) | 0.175 (5) | 0.098 (4) | 0.020 (9)* | |
| H1A | 0.233 (5) | 0.201 (5) | 1.334 (3) | 0.020 (9)* | |
| H1B | 0.274 (6) | 0.323 (3) | 1.212 (5) | 0.027 (10)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0060 (2) | 0.0058 (2) | 0.0061 (2) | −0.00256 (17) | −0.00242 (18) | 0.00160 (16) |
| P1 | 0.0050 (3) | 0.0051 (3) | 0.0066 (3) | −0.0025 (2) | −0.0026 (2) | 0.0016 (2) |
| P2 | 0.0056 (3) | 0.0052 (3) | 0.0062 (3) | −0.0025 (2) | −0.0028 (2) | 0.0017 (2) |
| C1 | 0.0074 (11) | 0.0060 (10) | 0.0083 (10) | −0.0026 (8) | −0.0043 (9) | 0.0013 (8) |
| O2 | 0.0077 (8) | 0.0087 (8) | 0.0093 (8) | −0.0042 (6) | −0.0043 (7) | 0.0044 (6) |
| O3 | 0.0071 (8) | 0.0083 (8) | 0.0087 (8) | −0.0038 (6) | −0.0036 (6) | 0.0034 (6) |
| O6 | 0.0115 (9) | 0.0112 (8) | 0.0081 (8) | −0.0071 (7) | −0.0023 (7) | −0.0008 (6) |
| O1 | 0.0107 (9) | 0.0075 (8) | 0.0085 (8) | −0.0032 (7) | −0.0017 (7) | 0.0011 (6) |
| N1 | 0.0107 (11) | 0.0102 (10) | 0.0108 (10) | −0.0006 (8) | −0.0051 (9) | 0.0010 (8) |
| O7 | 0.0077 (8) | 0.0076 (8) | 0.0147 (9) | −0.0033 (6) | −0.0069 (7) | 0.0055 (6) |
| O5 | 0.0086 (8) | 0.0067 (8) | 0.0083 (8) | −0.0033 (6) | −0.0006 (6) | −0.0003 (6) |
| O4 | 0.0056 (8) | 0.0087 (8) | 0.0113 (8) | −0.0026 (6) | −0.0042 (7) | 0.0002 (6) |
| Co1—O2 | 2.0714 (18) | P2—C1 | 1.793 (2) |
| Co1—O2i | 2.0714 (18) | C1—H51 | 0.97 |
| Co1—O1i | 2.102 (2) | C1—H61 | 0.97 |
| Co1—O1 | 2.102 (2) | O6—H6A | 0.82 |
| Co1—O3i | 2.135 (2) | O1—H1A | 0.819 (18) |
| Co1—O3 | 2.135 (2) | O1—H1B | 0.835 (19) |
| P1—O3 | 1.5166 (18) | N1—H1N | 0.825 (18) |
| P1—O4 | 1.5304 (19) | N1—H2N | 0.825 (18) |
| P1—O5 | 1.5403 (19) | N1—H3N | 0.821 (18) |
| P1—C1 | 1.795 (3) | N1—H4N | 0.821 (18) |
| P2—O2 | 1.5032 (18) | O7—H7 | 0.82 |
| P2—O6 | 1.5363 (19) | O5—H5A | 0.82 |
| P2—O7 | 1.5469 (19) | O4—H4 | 0.82 |
| O2—Co1—O2i | 180 | O2—P2—C1 | 111.74 (11) |
| O2—Co1—O1i | 92.53 (8) | O6—P2—C1 | 106.30 (11) |
| O2i—Co1—O1i | 87.47 (8) | O7—P2—C1 | 102.44 (12) |
| O2—Co1—O1 | 87.47 (8) | P2—C1—P1 | 116.96 (14) |
| O2i—Co1—O1 | 92.53 (8) | P2—C1—H51 | 108.1 |
| O1i—Co1—O1 | 180.0000 (10) | P1—C1—H51 | 108.1 |
| O2—Co1—O3i | 84.72 (8) | P2—C1—H61 | 108.1 |
| O2i—Co1—O3i | 95.28 (8) | P1—C1—H61 | 108.1 |
| O1i—Co1—O3i | 88.91 (8) | H51—C1—H61 | 107.3 |
| O1—Co1—O3i | 91.09 (8) | P2—O2—Co1 | 126.71 (11) |
| O2—Co1—O3 | 95.28 (8) | P1—O3—Co1 | 133.61 (10) |
| O2i—Co1—O3 | 84.72 (8) | P2—O6—H6A | 109.5 |
| O1i—Co1—O3 | 91.09 (8) | Co1—O1—H1A | 121 (2) |
| O1—Co1—O3 | 88.91 (8) | Co1—O1—H1B | 117 (3) |
| O3i—Co1—O3 | 180.00 (7) | H1A—O1—H1B | 106 (4) |
| O3—P1—O4 | 111.68 (11) | H1N—N1—H2N | 108 (4) |
| O3—P1—O5 | 111.77 (11) | H1N—N1—H3N | 105 (3) |
| O4—P1—O5 | 110.47 (11) | H2N—N1—H3N | 108 (4) |
| O3—P1—C1 | 109.61 (11) | H1N—N1—H4N | 114 (3) |
| O4—P1—C1 | 103.92 (11) | H2N—N1—H4N | 111 (4) |
| O5—P1—C1 | 109.08 (11) | H3N—N1—H4N | 110 (3) |
| O2—P2—O6 | 112.62 (11) | P2—O7—H7 | 109.5 |
| O2—P2—O7 | 112.39 (10) | P1—O5—H5A | 109.5 |
| O6—P2—O7 | 110.73 (11) | P1—O4—H4 | 109.5 |
| Symmetry codes: (i) −x+1, −y, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O5ii | 0.82 (2) | 1.99 (2) | 2.795 (3) | 166 (4) |
| O1—H1B···O4iii | 0.84 (2) | 1.99 (2) | 2.827 (3) | 175 (4) |
| N1—H1N···O7iv | 0.83 (2) | 2.09 (2) | 2.892 (3) | 166 (3) |
| N1—H2N···O6 | 0.83 (2) | 1.98 (2) | 2.796 (3) | 171 (4) |
| N1—H3N···O3v | 0.82 (2) | 2.17 (2) | 2.959 (3) | 161 (3) |
| N1—H4N···O3vi | 0.82 (2) | 2.15 (2) | 2.966 (3) | 177 (3) |
| O6—H6A···O6vii | 0.82 | 1.66 | 2.463 (4) | 165 |
| O7—H7···O4viii | 0.82 | 1.66 | 2.435 (3) | 156 |
| Symmetry codes: (ii) x−1, y, z+1; (iii) −x+1, −y+1, −z+2; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y, −z+1; (vi) x, y, z−1; (vii) −x+1, −y, −z+1; (viii) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O5i | 0.82 (2) | 1.99 (2) | 2.795 (3) | 166 (4) |
| O1—H1B···O4ii | 0.84 (2) | 1.99 (2) | 2.827 (3) | 175 (4) |
| N1—H1N···O7iii | 0.83 (2) | 2.09 (2) | 2.892 (3) | 166 (3) |
| N1—H2N···O6 | 0.83 (2) | 1.98 (2) | 2.796 (3) | 171 (4) |
| N1—H3N···O3iv | 0.82 (2) | 2.17 (2) | 2.959 (3) | 161 (3) |
| N1—H4N···O3v | 0.82 (2) | 2.15 (2) | 2.966 (3) | 177 (3) |
| O6—H6A···O6vi | 0.82 | 1.66 | 2.463 (4) | 165 |
| O7—H7···O4vii | 0.82 | 1.66 | 2.435 (3) | 156 |
| Symmetry codes: (i) x−1, y, z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y, −z+1; (v) x, y, z−1; (vi) −x+1, −y, −z+1; (vii) x−1, y, z. |
We thank the University of the Free State for financial support and Professor A. Roodt for helpful discussions.
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Diphosphonic acids are useful for the synthesis of metalorganic frameworks exhibiting microporous properties (Barthelet et al., 2002).
The CoII ion in the title complex, (NH4)2[Co(C2H8O12)2(H2O)2], is in a slightly distorted octahedral environment with O—Co—O bonding angles ranging from 84.72 (8) to 95.28 (8) o. All the bonding distances and angles fall within the normal range observed for complexes of this nature (DeLaMatter et al., 1973; Jurisson et al., 1983 and Stahl et al., 2006). In the bidentate ligand, the distances of uncoordinated O atoms to their respective P atoms do not vary much with values ranging from 1.5304 (19) and 1.5469 (19) Å. This, together with the fact that the best fits of our data were obtained when a 50% positional disorder was applied to the hydrogen atoms bonded to these O atoms, probably is enough to validate the slight disorder. A three-dimensional network is provided by numerous hydrogen bonds between the oxygen atoms of the anionic species and the ammonium cations.