inorganic compounds
Distrontium trimanganese(II) bis(hydrogenphosphate) bis(orthophosphate)
aLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: j_khmiyas@yahoo.fr
The title compound, Sr2Mn3(HPO4)2(PO4)2, was synthesized under hydrothermal conditions. In the structure, one of two Mn atoms is located on an inversion centre, whereas all others atoms are located in general positions. The framework structure is built up from two types of MnO6 octahedra (one almost undistorted, one considerably distorted), one PO3OH and one PO4 tetrahedron. The centrosymmetric MnO6 octahedron is linked to two other MnO6 octahedra by edge-sharing, forming infinite zigzag chains parallel to [010]. The PO3OH and PO4 tetrahedra connect these chains through common vertices or edges, resulting in the formation of sheets parallel to (100). The Sr2+ cation is located in the interlayer space and is bonded to nine O atoms in form of a distorted polyhedron and enhances the cohesion of the layers. Additional stabilization is achieved by a strong interlayer O—H⋯O hydrogen bond between the PO3OH and PO4 units. The structure of the title phosphate is isotypic to that of Pb2Mn3(HPO4)2(PO4)2.
Related literature
For isotypic Pb2Mn3(HPO4)2(PO4)2, see: Assani et al. (2012b). For related structures, see: Assani et al. (2012a); Effenberger (1999). For the thermal stability of similar compounds, see: Morozov et al. (2003). For applications of phosphates, see: Cheetham et al. (1999); Viter & Nagornyi (2009); Forster et al. (2003); Clearfield (1988); Joschi et al. (2008); Trad et al. (2010).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); 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, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536813018898/wm2758sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813018898/wm2758Isup2.hkl
Transparent crystals of Sr2Mn3(HPO4)2(PO4)2 were isolated from hydrothermal treatment of the reaction mixture of strontium, manganese, sodium and phosphate precursors in a proportion corresponding to the molar ratio Sr: Mn: Na: P: = 4: 4.5: 1: 6. The hydrothermal reaction was conducted in a 23 ml Teflon-lined autoclave filled to 50% with distilled water and under autogenously pressure at 473 K for five days. After being filtered off, washed with deionized water and air-dried, the reaction product consisted of colourless crystals with a platy form.
The O-bound H atom was initially located in a difference map and refined with O—H distance restraint of 0.82 (1) Å. In the last cycle it was refined in the riding model approximation with Uiso(H) set to 1.5Ueq(O). The highest peak and the deepest hole in the final Fourier map are at 0.64 Å and 0.55 Å, from Mn2.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Sr2Mn3(HPO4)2(PO4)2 | F(000) = 682 |
Mr = 721.96 | Dx = 3.689 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3138 reflections |
a = 7.8535 (1) Å | θ = 2.7–36.3° |
b = 8.7793 (2) Å | µ = 11.58 mm−1 |
c = 9.6165 (2) Å | T = 296 K |
β = 101.434 (1)° | Sheet, colourless |
V = 649.88 (2) Å3 | 0.33 × 0.24 × 0.12 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 3138 independent reflections |
Radiation source: fine-focus sealed tube | 2874 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 36.3°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker (2009) | h = −13→12 |
Tmin = 0.046, Tmax = 0.215 | k = −14→14 |
12425 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.019 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0211P)2 + 0.239P] where P = (Fo2 + 2Fc2)/3 |
3138 reflections | (Δ/σ)max = 0.002 |
115 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Sr2Mn3(HPO4)2(PO4)2 | V = 649.88 (2) Å3 |
Mr = 721.96 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8535 (1) Å | µ = 11.58 mm−1 |
b = 8.7793 (2) Å | T = 296 K |
c = 9.6165 (2) Å | 0.33 × 0.24 × 0.12 mm |
β = 101.434 (1)° |
Bruker APEXII CCD diffractometer | 3138 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker (2009) | 2874 reflections with I > 2σ(I) |
Tmin = 0.046, Tmax = 0.215 | Rint = 0.025 |
12425 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.58 e Å−3 |
3138 reflections | Δρmin = −0.54 e Å−3 |
115 parameters |
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 > 2σ(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 | ||
Sr1 | 0.573794 (17) | 0.478038 (15) | 0.234323 (14) | 0.00999 (3) | |
Mn1 | 1.0000 | 0.5000 | 0.5000 | 0.00677 (5) | |
Mn2 | 0.89650 (3) | 0.85638 (2) | 0.40357 (2) | 0.00891 (4) | |
P1 | 0.14462 (4) | 0.70256 (4) | 0.22974 (3) | 0.00542 (6) | |
P2 | 0.65079 (4) | 0.71451 (4) | 0.56233 (3) | 0.00649 (6) | |
O1 | 0.06059 (13) | 0.67784 (12) | 0.35944 (10) | 0.00966 (17) | |
O2 | 0.06622 (13) | 0.59473 (11) | 0.10796 (10) | 0.01019 (17) | |
O3 | 0.11920 (13) | 0.86980 (11) | 0.18530 (11) | 0.01016 (17) | |
O4 | 0.34252 (13) | 0.67330 (12) | 0.27411 (10) | 0.01050 (17) | |
O5 | 0.70244 (14) | 0.69325 (14) | 0.72158 (10) | 0.0141 (2) | |
O6 | 0.75819 (13) | 0.62546 (12) | 0.47491 (11) | 0.01179 (18) | |
O7 | 0.65059 (15) | 0.88211 (12) | 0.51673 (11) | 0.01383 (19) | |
O8 | 0.45824 (13) | 0.65486 (13) | 0.53325 (11) | 0.01209 (19) | |
H8 | 0.4169 | 0.6607 | 0.4482 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sr1 | 0.00960 (6) | 0.01026 (6) | 0.01085 (5) | 0.00204 (4) | 0.00384 (4) | 0.00216 (4) |
Mn1 | 0.00742 (11) | 0.00597 (11) | 0.00692 (11) | 0.00076 (8) | 0.00144 (8) | −0.00002 (8) |
Mn2 | 0.00962 (9) | 0.00758 (9) | 0.00837 (8) | 0.00006 (6) | −0.00103 (6) | −0.00030 (6) |
P1 | 0.00572 (12) | 0.00557 (12) | 0.00475 (12) | −0.00013 (10) | 0.00052 (9) | 0.00000 (9) |
P2 | 0.00632 (13) | 0.00796 (13) | 0.00540 (12) | 0.00034 (10) | 0.00167 (10) | −0.00007 (10) |
O1 | 0.0108 (4) | 0.0108 (4) | 0.0085 (4) | 0.0003 (3) | 0.0047 (3) | 0.0012 (3) |
O2 | 0.0137 (4) | 0.0079 (4) | 0.0073 (4) | −0.0001 (3) | −0.0019 (3) | −0.0020 (3) |
O3 | 0.0126 (4) | 0.0057 (4) | 0.0109 (4) | 0.0000 (3) | −0.0007 (3) | 0.0021 (3) |
O4 | 0.0064 (4) | 0.0154 (5) | 0.0093 (4) | 0.0019 (3) | 0.0007 (3) | 0.0004 (3) |
O5 | 0.0105 (4) | 0.0256 (6) | 0.0055 (4) | −0.0009 (4) | 0.0002 (3) | 0.0008 (4) |
O6 | 0.0109 (4) | 0.0151 (5) | 0.0104 (4) | 0.0054 (4) | 0.0047 (3) | −0.0002 (3) |
O7 | 0.0202 (5) | 0.0076 (4) | 0.0148 (4) | −0.0001 (4) | 0.0061 (4) | 0.0003 (3) |
O8 | 0.0074 (4) | 0.0203 (5) | 0.0083 (4) | −0.0033 (4) | 0.0008 (3) | 0.0009 (3) |
Sr1—O3i | 2.5641 (10) | Mn2—O1vi | 2.1248 (10) |
Sr1—O4 | 2.5806 (10) | Mn2—O5iii | 2.1256 (10) |
Sr1—O8ii | 2.5775 (11) | Mn2—O2v | 2.1875 (9) |
Sr1—O7iii | 2.5981 (11) | Mn2—O7 | 2.4079 (12) |
Sr1—O5ii | 2.7409 (11) | Mn2—O6 | 2.4609 (11) |
Sr1—O4i | 2.7599 (11) | P1—O3 | 1.5312 (10) |
Sr1—O6 | 2.7923 (10) | P1—O2 | 1.5365 (10) |
Sr1—O7i | 2.8207 (11) | P1—O1 | 1.5377 (10) |
Sr1—O5iii | 3.0680 (12) | P1—O4 | 1.5494 (10) |
Mn1—O6 | 2.1670 (10) | P2—O5 | 1.5160 (10) |
Mn1—O6iv | 2.1670 (10) | P2—O6 | 1.5201 (11) |
Mn1—O3v | 2.1672 (9) | P2—O7 | 1.5352 (11) |
Mn1—O3i | 2.1672 (9) | P2—O8 | 1.5721 (11) |
Mn1—O1ii | 2.1786 (10) | P2—Sr1viii | 3.2838 (4) |
Mn1—O1vi | 2.1786 (10) | O8—H8 | 0.8200 |
Mn2—O2vii | 2.1189 (10) | ||
O3i—Sr1—O4 | 148.09 (3) | O6iv—Mn1—O3i | 92.85 (4) |
O3i—Sr1—O8ii | 79.54 (3) | O3v—Mn1—O3i | 180.0 |
O4—Sr1—O8ii | 88.83 (3) | O6—Mn1—O1ii | 97.99 (4) |
O3i—Sr1—O7iii | 93.63 (3) | O6iv—Mn1—O1ii | 82.01 (4) |
O4—Sr1—O7iii | 95.05 (3) | O3v—Mn1—O1ii | 88.84 (4) |
O8ii—Sr1—O7iii | 172.09 (3) | O3i—Mn1—O1ii | 91.16 (4) |
O3i—Sr1—O5ii | 118.41 (3) | O6—Mn1—O1vi | 82.01 (4) |
O4—Sr1—O5ii | 74.91 (4) | O6iv—Mn1—O1vi | 97.99 (4) |
O8ii—Sr1—O5ii | 53.21 (3) | O3v—Mn1—O1vi | 91.16 (4) |
O7iii—Sr1—O5ii | 134.52 (3) | O3i—Mn1—O1vi | 88.84 (4) |
O3i—Sr1—O4i | 55.56 (3) | O1ii—Mn1—O1vi | 180.0 |
O4—Sr1—O4i | 145.79 (2) | O2vii—Mn2—O1vi | 128.50 (4) |
O8ii—Sr1—O4i | 69.60 (3) | O2vii—Mn2—O5iii | 104.08 (4) |
O7iii—Sr1—O4i | 109.86 (3) | O1vi—Mn2—O5iii | 92.78 (4) |
O5ii—Sr1—O4i | 70.92 (3) | O2vii—Mn2—O2v | 77.72 (4) |
O3i—Sr1—O6 | 67.65 (3) | O1vi—Mn2—O2v | 92.21 (4) |
O4—Sr1—O6 | 80.44 (3) | O5iii—Mn2—O2v | 171.78 (4) |
O8ii—Sr1—O6 | 67.36 (3) | O2vii—Mn2—O7 | 93.58 (4) |
O7iii—Sr1—O6 | 106.45 (3) | O1vi—Mn2—O7 | 137.06 (4) |
O5ii—Sr1—O6 | 114.99 (3) | O5iii—Mn2—O7 | 83.28 (4) |
O4i—Sr1—O6 | 112.72 (3) | O2v—Mn2—O7 | 88.62 (4) |
O3i—Sr1—O7i | 122.54 (3) | O2vii—Mn2—O6 | 154.34 (4) |
O4—Sr1—O7i | 89.23 (3) | O1vi—Mn2—O6 | 76.51 (4) |
O8ii—Sr1—O7i | 117.08 (3) | O5iii—Mn2—O6 | 77.09 (4) |
O7iii—Sr1—O7i | 69.95 (4) | O2v—Mn2—O6 | 97.77 (4) |
O5ii—Sr1—O7i | 65.75 (3) | O7—Mn2—O6 | 60.88 (4) |
O4i—Sr1—O7i | 78.31 (3) | O3—P1—O2 | 111.57 (5) |
O6—Sr1—O7i | 168.81 (3) | O3—P1—O1 | 107.97 (6) |
O3i—Sr1—O5iii | 93.62 (3) | O2—P1—O1 | 111.08 (6) |
O4—Sr1—O5iii | 68.17 (3) | O3—P1—O4 | 107.70 (6) |
O8ii—Sr1—O5iii | 123.36 (3) | O2—P1—O4 | 109.65 (6) |
O7iii—Sr1—O5iii | 52.59 (3) | O1—P1—O4 | 108.76 (6) |
O5ii—Sr1—O5iii | 143.06 (3) | O5—P2—O6 | 115.38 (6) |
O4i—Sr1—O5iii | 145.93 (3) | O5—P2—O7 | 113.04 (6) |
O6—Sr1—O5iii | 58.42 (3) | O6—P2—O7 | 107.71 (6) |
O7i—Sr1—O5iii | 113.67 (3) | O5—P2—O8 | 101.19 (6) |
O6—Mn1—O6iv | 180.0 | O6—P2—O8 | 110.48 (6) |
O6—Mn1—O3v | 92.85 (4) | O7—P2—O8 | 108.78 (6) |
O6iv—Mn1—O3v | 87.15 (4) | O5—P2—Mn2 | 120.08 (4) |
O6—Mn1—O3i | 87.15 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z−1/2; (iv) −x+2, −y+1, −z+1; (v) x+1, −y+3/2, z+1/2; (vi) x+1, y, z; (vii) −x+1, y+1/2, −z+1/2; (viii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | Sr2Mn3(HPO4)2(PO4)2 |
Mr | 721.96 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.8535 (1), 8.7793 (2), 9.6165 (2) |
β (°) | 101.434 (1) |
V (Å3) | 649.88 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.58 |
Crystal size (mm) | 0.33 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker (2009) |
Tmin, Tmax | 0.046, 0.215 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12425, 3138, 2874 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.833 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.045, 1.06 |
No. of reflections | 3138 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.54 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Widespread studies were devoted to metal-based phosphates, either with open-framework structures, or in terms of porous materials. Within those materials, the anionic framework, generally constructed from PO4 tetrahedra connected to metal (M) cations in different coordination environments MOn (with n = 4, 5 and 6), can generate pores and channels offering a suitable environment to accommodate various other cations. Besides their high chemical activity and their thermal stability (Morozov et al., 2003), such metal-based phosphates have some interesting properties leading to applications such as in catalysis (Cheetham et al., 1999; Viter & Nagornyi, 2009), ion-exchangers (Clearfield, 1988; Joschi et al., 2008), gas sorption (Forster et al., 2003), or batteries (Trad et al., 2010).
Our interest is particularly focused on hydrothermally synthesized orthophosphates within the ternary systems MO–M'O–P2O5 with M and M' = divalent cations. We have recently characterized some new lead cobalt or manganese phosphates, viz. Co2Pb(HPO4)(PO4)OH.H2O (Assani et al., 2012a) and Pb2Mn3(HPO4)2(PO4)2 (Assani et al., 2012b). In line with the focus of our research, the present paper describes the hydrothermal synthesis and the structural characterization of a new strontium manganese phosphate, Sr2Mn3(HPO4)2(PO4)2, that is isotypic with its lead analogue, Pb2Mn3(HPO4)2(PO4)2. These two phosphates are characterized by an Mn:P ratio = 3:4, which is rarely observed, with the exception of some copper-based orthophosphates, Pb3Cu3(PO4)4 and Sr3Cu3(PO4)4 (Effenberger, 1999), also with Cu:P = 3:4.
In the structure of the title compound, one of the two manganese sites (Mn1) is located on a centre of inversion, while all remaining atoms are in general positions. A part of the structure, as given in Fig. 1, shows the different types of polyhedra around the metal positions and the P atoms. The centrosymmetric Mn1O6 octahedron is linked to two distorted Mn2O6 octahedra by a common edge, thus forming infinite zigzag chains with composition [Mn3O14]∞ running parallel to [010] (Fig. 2). Adjacent chains are linked to each other through PO4 and PO3OH tetrahedra, via common corners or edges, leading to the formation of layers parallel to (100). The cohesion of the crystal structure is ensured on one hand by the presence of the Sr2+ cations in the interlayer space and on the other hand by strong O—H···O hydrogen bonds between sheets (Fig. 2 and Table 2).
In the structure of the title compound, the Sr2+ cation is surrounded by nine O atoms instead of eight as in the case of Pb2Mn3(HPO4)2(PO4)2. All other bond lengths and angles are similar in the two structures, with the exception of the Mn2—O bond lengths. In the title structure, four medium-long bonds in the range 2.1189 (10) to 2.1875 (9) Å and two longer bonds of 2.4079 (12) and 2.4609 (11) Å are observed, whereas in the lead analogue five medium-long bonds in the range 2.094 (4) to 2.235 (4) Å and one considerably long bond of 2.610 (4) Å is observed.