Acta Cryst. (2011). E67, i41 [ doi:10.1107/S1600536811022598 ]
Ag2Co3(HPO4)(PO4)2 contains CoO6 octahedra and phosphate groups linked to form a three-dimensional network defining tunnels parallel to the a axis that are occupied by Ag+ ions.
A mixture of 0.0849 g AgNO3, 0.0529 g CoCO3.Co(OH)2, 10 mL of 85 wt.% H3PO4, and 10 mL of distilled water was placed in a 23-mL Teflon-lined autoclave, which was heated at 468 K under autogeneous pressure for two days. Pink crystals of the title compound were obtained after the product was filtered, washed with deionized water, and dried in air.
The O-bound H atom was initially located in a difference map and refined with O—H distance restraints of 0.86 (1) in a riding model approximation with Uiso(H) set to 1.2Ueq(O). The highest and deepest hole in the final difference Fourier map are located at 0.70 Å and 0.51 Å, respectively, from Ag1.
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: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./mg2119fig1thm.gif)
| Fig. 1. Connectivity of metal-centred coordination polyhedra in Ag2Co3(HPO4)(PO4)2. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) -x, -y + 1, z; (ii) x + 1/2, -y+ 1, z; (iii) x, -y + 3/2, z - 1/2; (iv) -x + 1/2, -y + 3/2, z - 1/2; (v) -x + 1/2, -y + 1/2, z - 1/2; (vi) -x, y + 1/2, z - 1/2; (vii) x + 1/2, y + 1/2, z - 1/2; (viii) x, -y + 1/2, z - 1/2; (ix) -x, -y, z; (x) -x, y + 1/2, z + 1/2; (xi) x, -y + 1/2, z + 1/2; (xii) -x + 1/2, y, z. |
![[Figure 2]](./mg2119fig2thm.gif)
| Fig. 2. Polyhedral representation of Ag2Co3(HPO4)(PO4)2, showing tunnels running along the a direction at x 1/2 0 and x 0 1/2. |
| Ag2Co3(HPO4)(PO4)2 | F(000) = 1268 |
| Mr = 678.44 | Dx = 4.917 Mg m−3 |
| Orthorhombic, Ima2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: I 2 -2a | Cell parameters from 1388 reflections |
| a = 12.9814 (4) Å | θ = 3.1–30.0° |
| b = 6.5948 (2) Å | µ = 10.11 mm−1 |
| c = 10.7062 (3) Å | T = 296 K |
| V = 916.55 (5) Å3 | Prism, pink |
| Z = 4 | 0.26 × 0.12 × 0.09 mm |
| Bruker X8 APEX diffractometer | 1388 independent reflections |
| Radiation source: fine-focus sealed tube | 1368 reflections with I > 2σ(I) |
| graphite | Rint = 0.021 |
| φ and ω scans | θmax = 30.0°, θmin = 3.1° |
| Absorption correction: multi-scan (MULABS; Blessing, 1995) | h = −17→18 |
| Tmin = 0.365, Tmax = 0.424 | k = −3→9 |
| 3966 measured reflections | l = −14→15 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.036P)2 + 2.5641P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 1388 reflections | Δρmax = 1.81 e Å−3 |
| 99 parameters | Δρmin = −1.54 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 653 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.55 (3) |
| Ag2Co3(HPO4)(PO4)2 | V = 916.55 (5) Å3 |
| Mr = 678.44 | Z = 4 |
| Orthorhombic, Ima2 | Mo Kα radiation |
| a = 12.9814 (4) Å | µ = 10.11 mm−1 |
| b = 6.5948 (2) Å | T = 296 K |
| c = 10.7062 (3) Å | 0.26 × 0.12 × 0.09 mm |
| Bruker X8 APEX diffractometer | 1388 independent reflections |
| Absorption correction: multi-scan (MULABS; Blessing, 1995) | 1368 reflections with I > 2σ(I) |
| Tmin = 0.365, Tmax = 0.424 | Rint = 0.021 |
| 3966 measured reflections | θmax = 30.0° |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.064 | Δρmax = 1.81 e Å−3 |
| S = 1.05 | Δρmin = −1.54 e Å−3 |
| 1388 reflections | Absolute structure: Flack (1983), 653 Friedel pairs |
| 99 parameters | Flack parameter: 0.55 (3) |
| 1 restraint |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Ag1 | 0.2500 | 0.61215 (8) | −0.01381 (7) | 0.03097 (16) | |
| Ag2 | 0.0000 | 0.5000 | −0.03770 (5) | 0.0448 (2) | |
| Co1 | 0.13632 (3) | 0.24907 (9) | 0.20816 (6) | 0.00759 (11) | |
| Co2 | 0.0000 | 0.5000 | 0.45678 (7) | 0.00474 (13) | |
| P1 | −0.07308 (7) | 0.25700 (17) | 0.20656 (12) | 0.00728 (17) | |
| P2 | 0.2500 | 0.40742 (18) | 0.45614 (14) | 0.0051 (2) | |
| O1 | −0.1344 (3) | 0.4442 (5) | 0.1740 (3) | 0.0117 (6) | |
| O2 | 0.0039 (3) | 0.2072 (5) | 0.1002 (3) | 0.0084 (6) | |
| O3 | 0.0017 (3) | 0.2766 (5) | 0.3204 (3) | 0.0078 (6) | |
| O4 | −0.1489 (3) | 0.0787 (5) | 0.2349 (3) | 0.0116 (7) | |
| O5 | 0.15460 (18) | 0.5409 (4) | 0.4551 (3) | 0.0102 (5) | |
| O6 | 0.2500 | 0.2616 (7) | 0.3410 (4) | 0.0109 (11) | |
| O7 | 0.2500 | 0.2663 (7) | 0.5736 (4) | 0.0083 (10) | |
| H4 | −0.2103 | 0.0633 | 0.2635 | 0.010* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ag1 | 0.0498 (3) | 0.0187 (2) | 0.0244 (3) | 0.000 | 0.000 | 0.0049 (2) |
| Ag2 | 0.1126 (6) | 0.0094 (2) | 0.0124 (3) | −0.0022 (2) | 0.000 | 0.000 |
| Co1 | 0.00546 (19) | 0.0103 (2) | 0.0070 (2) | 0.0005 (2) | 0.0001 (2) | −0.00120 (18) |
| Co2 | 0.0051 (2) | 0.0051 (3) | 0.0040 (3) | 0.00074 (19) | 0.000 | 0.000 |
| P1 | 0.0069 (3) | 0.0078 (4) | 0.0071 (4) | 0.0000 (4) | −0.0003 (5) | 0.0005 (4) |
| P2 | 0.0043 (5) | 0.0066 (5) | 0.0044 (6) | 0.000 | 0.000 | −0.0005 (5) |
| O1 | 0.0133 (15) | 0.0094 (14) | 0.0124 (14) | 0.0018 (11) | −0.0027 (10) | 0.0002 (11) |
| O2 | 0.0096 (17) | 0.0072 (12) | 0.0083 (14) | −0.0004 (13) | −0.0014 (11) | −0.0031 (13) |
| O3 | 0.0080 (17) | 0.0091 (14) | 0.0063 (13) | 0.0030 (12) | −0.0020 (10) | −0.0015 (12) |
| O4 | 0.0107 (17) | 0.0083 (15) | 0.0159 (18) | −0.0018 (11) | 0.0039 (10) | 0.0001 (10) |
| O5 | 0.0067 (9) | 0.0115 (10) | 0.0123 (13) | 0.0014 (9) | 0.0003 (12) | 0.0000 (12) |
| O6 | 0.011 (3) | 0.014 (2) | 0.008 (2) | 0.000 | 0.000 | −0.0033 (15) |
| O7 | 0.007 (3) | 0.010 (2) | 0.0083 (19) | 0.000 | 0.000 | 0.0021 (15) |
| Ag1—O1i | 2.537 (3) | Co2—O2xi | 2.056 (3) |
| Ag1—O1ii | 2.537 (3) | Co2—O3i | 2.074 (3) |
| Ag1—O5iii | 2.623 (3) | Co2—O3 | 2.074 (3) |
| Ag1—O5iv | 2.623 (3) | P1—O1 | 1.510 (3) |
| Ag1—O7v | 2.666 (4) | P1—O2 | 1.550 (4) |
| Ag1—O6v | 2.914 (5) | P1—O4 | 1.563 (3) |
| Ag1—O4vi | 3.001 (3) | P1—O3 | 1.563 (4) |
| Ag1—O4vii | 3.001 (3) | P2—O5 | 1.519 (3) |
| Ag1—Ag2 | 3.33837 (16) | P2—O5xii | 1.520 (3) |
| Ag2—O3viii | 2.374 (3) | P2—O6 | 1.563 (5) |
| Ag2—O3vi | 2.374 (3) | P2—O7 | 1.564 (5) |
| Ag2—O2 | 2.431 (4) | O1—Co1i | 2.055 (3) |
| Ag2—O2i | 2.431 (4) | O1—O4 | 2.504 (4) |
| Ag2—O1 | 2.884 (3) | O1—O2 | 2.509 (5) |
| Ag2—O1i | 2.884 (3) | O1—Ag1i | 2.536 (3) |
| Ag2—O4viii | 3.151 (3) | O2—Co2xiii | 2.056 (3) |
| Ag2—O4vi | 3.151 (3) | O3—Ag2xiv | 2.374 (3) |
| Ag2—Ag1i | 3.33837 (16) | O4—Ag1xv | 3.001 (3) |
| Co1—O6 | 2.051 (3) | O4—Ag2xiv | 3.151 (3) |
| Co1—O1i | 2.055 (3) | O4—H4 | 0.8598 |
| Co1—O7v | 2.065 (3) | O5—Ag1xvi | 2.623 (3) |
| Co1—O2 | 2.090 (3) | O6—Co1xii | 2.051 (3) |
| Co1—O3 | 2.128 (4) | O6—Ag1xvii | 2.914 (5) |
| Co1—O4ix | 2.187 (3) | O7—Co1xi | 2.065 (3) |
| Co2—O5i | 2.025 (2) | O7—Co1xvii | 2.065 (3) |
| Co2—O5 | 2.025 (2) | O7—Ag1xvii | 2.666 (4) |
| Co2—O2x | 2.056 (3) | ||
| O1i—Ag1—O1ii | 72.52 (15) | O2—Ag2—O4vi | 125.96 (10) |
| O1i—Ag1—O5iii | 87.09 (10) | O2i—Ag2—O4vi | 110.56 (10) |
| O1ii—Ag1—O5iii | 120.52 (10) | O1—Ag2—O4vi | 177.68 (9) |
| O1i—Ag1—O5iv | 120.52 (10) | O1i—Ag2—O4vi | 102.42 (8) |
| O1ii—Ag1—O5iv | 87.09 (10) | O4viii—Ag2—O4vi | 78.84 (11) |
| O5iii—Ag1—O5iv | 56.35 (11) | Ag1i—Ag2—Ag1 | 171.21 (3) |
| O1i—Ag1—O7v | 65.44 (10) | O6—Co1—O1i | 95.28 (16) |
| O1ii—Ag1—O7v | 65.44 (10) | O6—Co1—O7v | 88.38 (11) |
| O5iii—Ag1—O7v | 149.47 (7) | O1i—Co1—O7v | 86.15 (16) |
| O5iv—Ag1—O7v | 149.47 (7) | O6—Co1—O2 | 168.69 (14) |
| O1i—Ag1—O6v | 107.39 (11) | O1i—Co1—O2 | 91.26 (14) |
| O1ii—Ag1—O6v | 107.39 (11) | O7v—Co1—O2 | 101.28 (12) |
| O5iii—Ag1—O6v | 132.08 (10) | O6—Co1—O3 | 101.28 (13) |
| O5iv—Ag1—O6v | 132.08 (10) | O1i—Co1—O3 | 90.38 (13) |
| O7v—Ag1—O6v | 52.78 (11) | O7v—Co1—O3 | 170.01 (13) |
| O1i—Ag1—O4vi | 116.18 (10) | O2—Co1—O3 | 69.40 (10) |
| O1ii—Ag1—O4vi | 163.45 (9) | O6—Co1—O4ix | 84.00 (15) |
| O5iii—Ag1—O4vi | 75.15 (9) | O1i—Co1—O4ix | 175.52 (12) |
| O5iv—Ag1—O4vi | 99.02 (9) | O7v—Co1—O4ix | 89.40 (15) |
| O7v—Ag1—O4vi | 104.24 (11) | O2—Co1—O4ix | 90.18 (13) |
| O6v—Ag1—O4vi | 57.31 (10) | O3—Co1—O4ix | 94.10 (13) |
| O1i—Ag1—O4vii | 163.45 (9) | O5i—Co2—O5 | 178.97 (18) |
| O1ii—Ag1—O4vii | 116.18 (10) | O5i—Co2—O2x | 94.06 (13) |
| O5iii—Ag1—O4vii | 99.02 (9) | O5—Co2—O2x | 86.71 (13) |
| O5iv—Ag1—O4vii | 75.15 (9) | O5i—Co2—O2xi | 86.71 (13) |
| O7v—Ag1—O4vii | 104.24 (11) | O5—Co2—O2xi | 94.06 (13) |
| O6v—Ag1—O4vii | 57.31 (10) | O2x—Co2—O2xi | 83.4 (2) |
| O4vi—Ag1—O4vii | 51.87 (13) | O5i—Co2—O3i | 94.45 (13) |
| O3viii—Ag2—O3vi | 100.42 (17) | O5—Co2—O3i | 84.82 (13) |
| O3viii—Ag2—O2 | 77.19 (9) | O2x—Co2—O3i | 93.07 (11) |
| O3vi—Ag2—O2 | 177.52 (14) | O2xi—Co2—O3i | 176.32 (16) |
| O3viii—Ag2—O2i | 177.52 (14) | O5i—Co2—O3 | 84.82 (13) |
| O3vi—Ag2—O2i | 77.19 (9) | O5—Co2—O3 | 94.45 (13) |
| O2—Ag2—O2i | 105.21 (15) | O2x—Co2—O3 | 176.32 (16) |
| O3viii—Ag2—O1 | 114.25 (11) | O2xi—Co2—O3 | 93.07 (11) |
| O3vi—Ag2—O1 | 126.53 (11) | O3i—Co2—O3 | 90.51 (18) |
| O2—Ag2—O1 | 55.53 (11) | O1—P1—O2 | 110.1 (2) |
| O2i—Ag2—O1 | 67.13 (10) | O1—P1—O4 | 109.14 (18) |
| O3viii—Ag2—O1i | 126.53 (11) | O2—P1—O4 | 112.90 (19) |
| O3vi—Ag2—O1i | 114.25 (11) | O1—P1—O3 | 116.08 (18) |
| O2—Ag2—O1i | 67.13 (10) | O2—P1—O3 | 100.93 (14) |
| O2i—Ag2—O1i | 55.53 (11) | O4—P1—O3 | 107.57 (19) |
| O1—Ag2—O1i | 76.38 (13) | O1—P1—Co1 | 122.99 (14) |
| O3viii—Ag2—O4viii | 52.04 (11) | O5—P2—O5xii | 109.2 (2) |
| O3vi—Ag2—O4viii | 68.06 (10) | O5—P2—O6 | 110.52 (15) |
| O2—Ag2—O4viii | 110.56 (10) | O5xii—P2—O6 | 110.52 (15) |
| O2i—Ag2—O4viii | 125.96 (10) | O5—P2—O7 | 110.52 (15) |
| O1—Ag2—O4viii | 102.42 (8) | O5xii—P2—O7 | 110.53 (15) |
| O1i—Ag2—O4viii | 177.68 (9) | O6—P2—O7 | 105.5 (2) |
| O3viii—Ag2—O4vi | 68.06 (10) | P1—O4—H4 | 137.9 |
| O3vi—Ag2—O4vi | 52.04 (11) |
| Symmetry codes: (i) −x, −y+1, z; (ii) x+1/2, −y+1, z; (iii) x, −y+3/2, z−1/2; (iv) −x+1/2, −y+3/2, z−1/2; (v) −x+1/2, −y+1/2, z−1/2; (vi) −x, y+1/2, z−1/2; (vii) x+1/2, y+1/2, z−1/2; (viii) x, −y+1/2, z−1/2; (ix) −x, −y, z; (x) −x, y+1/2, z+1/2; (xi) x, −y+1/2, z+1/2; (xii) −x+1/2, y, z; (xiii) −x, y−1/2, z−1/2; (xiv) −x, y−1/2, z+1/2; (xv) x−1/2, y−1/2, z+1/2; (xvi) −x+1/2, −y+3/2, z+1/2; (xvii) −x+1/2, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O4xviii | 0.86 | 1.86 | 2.626 (7) | 148 |
| Symmetry codes: (xviii) −x−1/2, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O4i | 0.86 | 1.86 | 2.626 (7) | 148 |
| Symmetry codes: (i) −x−1/2, y, z. |
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
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Compounds prepared hydrothermally in the Ag2O–MO–P2O5 (M = divalent cation) systems include AgMg3(PO4)(HPO4)2 (Assani et al., 2011a), AgMn3(PO4)(HPO4)2 (Leroux et al., 1995), AgCo3(PO4)(HPO4)2 (Guesmi & Driss, 2002), AgNi3(PO4)(HPO4)2 (Ben Smail & Jouini, 2002), Ag2Ni3(HPO4)(PO4)2 (Assani et al., 2011b), and γ-AgZnPO4 (Assani et al., 2010). Ag2Co3(HPO4)(PO4)2, isostructural to the Ni analogue, contains CoO6 octahedra and PO4 and PO3(OH) tetrahedra which share corners and edges to form a three-dimensional framework (Fig. 1). Two types of tunnels aligned parallel to the a-direction accommodate Ag+ cations (Fig. 2).