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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Jun 18;67(Pt 7):i41. doi: 10.1107/S1600536811022598

Disilver(I) tricobalt(II) hydrogenphos­phate bis­(phosphate), Ag2Co3(HPO4)(PO4)2

Abderrazzak Assani a,*, Lahcen El Ammari a, Mohammed Zriouil a, Mohamed Saadi a
PMCID: PMC3152109  PMID: 21836826

Abstract

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.

Related literature

Compounds prepared hydro­thermally in the Ag2O–MO–P2O5 (M = divalent cation) system 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 ▶).

Experimental

Crystal data

  • Ag2Co3(HPO4)(PO4)2

  • M r = 678.44

  • Orthorhombic, Inline graphic

  • a = 12.9814 (4) Å

  • b = 6.5948 (2) Å

  • c = 10.7062 (3) Å

  • V = 916.55 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 10.11 mm−1

  • T = 296 K

  • 0.26 × 0.12 × 0.09 mm

Data collection

  • Bruker X8 APEX diffractometer

  • Absorption correction: multi-scan (MULABS; Blessing, 1995 ▶) T min = 0.365, T max = 0.424

  • 3966 measured reflections

  • 1388 independent reflections

  • 1368 reflections with I > 2σ(I)

  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028

  • wR(F 2) = 0.064

  • S = 1.05

  • 1388 reflections

  • 99 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 1.81 e Å−3

  • Δρmin = −1.54 e Å−3

  • Absolute structure: Flack (1983 ▶), 653 Friedel pairs

  • Flack parameter: 0.55 (3)

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022598/mg2119sup1.cif

e-67-00i41-sup1.cif (20.9KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022598/mg2119Isup2.hkl

e-67-00i41-Isup2.hkl (68.6KB, hkl)

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O4—H4⋯O4i 0.86 1.86 2.626 (7) 148
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Symmetry code: (i) Inline graphic.

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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.

Figures

Fig. 1.

Fig. 1.

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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.

Fig. 2.

Fig. 2.

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Polyhedral representation of Ag2Co3(HPO4)(PO4)2, showing tunnels running along the a direction at x 1/2 0 and x 0 1/2.

Crystal data

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
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Data collection

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
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Refinement

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)
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Special details

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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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
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Atomic displacement parameters (Å2)

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)
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Geometric parameters (Å, °)

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)
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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.

Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A
O4—H4···O4xviii 0.86 1.86 2.626 (7) 148.
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Symmetry codes: (xviii) −x−1/2, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: MG2119).

References

  1. Assani, A., Saadi, M. & El Ammari, L. (2010). Acta Cryst. E66, i74. [DOI] [PMC free article] [PubMed]
  2. Assani, A., Saadi, M., Zriouil, M. & El Ammari, L. (2011a). Acta Cryst. E67, i5. [DOI] [PMC free article] [PubMed]
  3. Assani, A., El Ammari, L., Zriouil, M. & Saadi, M. (2011b). Acta Cryst. E67, i40. [DOI] [PMC free article] [PubMed]
  4. Ben Smail, R. & Jouini, T. (2002). Acta Cryst. C58, i61–i62. [DOI] [PubMed]
  5. Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [DOI] [PubMed]
  6. Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  7. Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  8. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  9. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  10. Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  11. Guesmi, A. & Driss, A. (2002). Acta Cryst. C58, i16–i17. [DOI] [PubMed]
  12. Leroux, F., Mar, A., Guyomard, D. & Piffard, Y. (1995). J. Solid State Chem. 117, 206–212.
  13. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022598/mg2119sup1.cif

e-67-00i41-sup1.cif (20.9KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022598/mg2119Isup2.hkl

e-67-00i41-Isup2.hkl (68.6KB, hkl)

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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