Crystal structure of silver strontium copper orthophosphate, AgSr4Cu4.5(PO4)6

The transition-metal orthophosphate, AgSr4Cu4.5(PO4)6, crystallizes in an original structure characterized by two trimers [Cu3O12] linked by PO4 tetrahedra to form layers. The strontium and silver cations located between the layers ensure the cohesion of the crystal structure.


Chemical context
The growing role of metal orthophosphates based on PO 4 and MO n (where M is a metal cation) structural units is closely related to their ability to adopt different spatial arrangements. As has been pointed out previously, their physical and chemical properties, dynamic flexibility attributes and structural behaviour (Hadrich et al., 2001) can be correlated with the ionic radius of the metal cation (Jeżowska-Trzebiatowska et al., 1980). Furthermore, the ability of these metal cations to adopt different oxidation states as well as various coordination environments leads, in general, to open anionic three-dimensional frameworks. The structures of these classes of materials can easily accommodate a great variety of substituents, anionic and/or cationic, which can have a significant effect on the stability and on the morphology of structures and crystals, as is shown particularly in the apatite family (LeGeros & Tung, 1983) for which a considerable number of complex and versatile networks were described systematically. Open frameworks involved with various cavities such tunnels or cages, especially in phosphates containing mono, di and trivalent cations, are of particular interest owing to their potential applications in catalysis (Badrour et al., 2001) and as immobilizing carriers for various enzymes, e.g. CaTi 4 (PO 4 ) 6 (Suzuki et al., 1991) as well as for their photocatalytic activities in glass-ceramics containing MgTi 4 (PO 4 ) 6 crystals (Fu, 2014) and ionic-conductivity properties with Ca l-x Na 2x Ti 4 (PO 4 ) 6 belonging to the Nasicon structure type (Mentre & Abraham, 1994). Much attention has been paid to compounds containing six PO 4 tetrahedral units with different transition metal/ phosphate ratios, e.g. Na 4 CaFe 4 (PO 4 ) 6 which adopts the Alluaudite structure in the ideal C2/c space group (Hidouri et al., 2004), Ba 3 V4(PO 4 ) 6 which crystallizes as a Langbeinitetype structure (Dross & Glaum, 2004), CuTi 4 (PO 4 ) 6 which belongs to the Nasicon family (Kasuga et al., 1999), the silver lead apatite Pb 8 Ag 2 (PO 4 ) 6 (Ternane et al., 2000), the mixedvalent iron(II/III) phosphate Fe 7 (PO 4 ) 6 (Belik et al., 2000) and Na 2.5 Y 0.5 Mg 7 (PO 4 ) 6 with a Fillowite-type structure (Jerbi et al., 2010). Through hydrothermal processes, and as part of our systematic studies of the crystal alkaline and alkaline earth monophosphates, we have previously succeeded in elaborating a number of compounds with three-dimensional networks featuring distinctive cavities including AgMg 3 (H-PO 4 ) 2 PO 4 (Assani et al., 2011), Sr 2 Mn 3 (HPO 4 ) 2 (PO 4 ) 2 (Khmiyas et al., 2013), SrMn 2 II Mn III (PO 4 ) 3 (Alhakmi et al., 2013), NaMg 3 (HPO 4 ) 2 PO 4 (Ould Saleck et al., 2015). In an extension of our investigations and structural studies of various mono-divalent transition-metal phosphates a new phosphate copper (Cu II )-based AgSr 4 Cu 4.5 (PO 4 ) 6 was prepared and successfully characterized. Charge-distribution (CHARDI) (Nespolo et al., 2001) and bond-valence-sum (BVS) calculations were used for validating the structural model. A careful examination of the literature as well as various databases reveals that the title compound AgSr 4-Cu 4.5 (PO 4 ) 6 is original and furthermore is not related to any family of reported compounds.

Structural commentary
The principal building units of the crystal structure of AgSr 4 Cu 4.5 (PO 4 ) 6 are more or less distorted polyhedra (AgO 5 , CuO 4 , CuO 5 , SrO 8 , SrO 9 ) and nearly regular PO 4 tetrahedra, as shown in Fig. 1. In this structure, the copper atoms adopt two different environments: CuO 4 and CuO 5 . Indeed, Cu1 and Cu2 exhibit a coordination sphere of four oxygen atoms, forming a flattened parallelogram for Cu1O 4 and a distorted square plane for Cu2O 4 . The other copper atoms Cu3, Cu4 and Cu5 each occupy the centers of CuO 5 square-based pyramids. A close inspection of the geometrical parameters of Cu3O 5 , Cu4O 5 and Cu5O 5 polyhedra reveals that the latter exhibit significant distortion. The phosphorus atoms are tetrahedrally coordinated with bond lengths and angles close to those reported for P 5+ for this geometry. The crystalstructure framework of AgSr 4 Cu 4.5 (PO 4 ) 6 can be viewed as a three-dimensional network of corner-sharing CuO n (n = 4 or 5) units, thereby forming two types of [    The principal building units in the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) Àx + 1, Ày + 1, Àz; (ii) Àx, Ày + 1, Àz; (iii) x, y + 1, z; (iv) x À 1, y, z; (v) Àx + 1, Ày + 1, Àz + 1; (vi) x + 1, y, z; (vii) x, y À 1, z; (viii) Àx, Ày, Àz + 1; (ix) Àx, Ày + 1, Àz + 1.   first trimer results from the zigzag succession in the following order Cu(4)O 5 -Cu(2)O 4 -Cu(5)O 5 . Similarly, the second type of trimer is built up from two-vertex-sharing of a single polyhedra, Cu1O 4 , sandwiched by two neighbouring Cu3O 5 entities as shown in Fig. 2. Each oxygen atom of both trimers is connected to a nearly regular PO 4 tetrahedron in such a way as to form two different [Cu 3 P 10 O 40 ] 24À ribbons (see Fig. 3 and 4). These adjacent ribbons are linked together through the PO 4 tetrahedra, thus building a layer-like [Cu 4.5 (PO 4 ) 6 ] 9À arrangement perpendicular to the [100] direction as shown in Fig. 5.
Crystal cohesion and the junction between the stacked layers along the a-axis direction are ensured by ionic bonds involving the Sr 2+ and Ag + cations as shown in Fig. 6. The insertion of these mono and bivalent cations generates strong interactions inducing, consequently, a morphological defor-mation of the interlayer space, which explains the manifestation of the distorted sites. This result is confirmed by the CHARDI analysis of the coordination polyhedra by means of the effective coordination number (ECoN; Nespolo, 2016). The distortion of the metal-oxygen polyhedron becomes stronger when the ECoN value deviates further from the habitual coordination number (CN). This structural particularity is clearly noticeable when examining the numerical values of ECoN and CN for the various SrO n (n = 8 and 9) and AgO 5 polyhedra. The differences ECoN (Sr1)/CN(Sr1) = 7.61/8, ECoN (Sr2)/CN(Sr2) = 6.96/8 and ECoN (Sr3)/ CN(Sr3) = 6.8/8, reveal an increased distortion in the SrO 8 groups ranging from the Sr1O 8 to Sr3O 8 polyhedra. The Sr2 atom is formally nine-coordinate with bond lengths varying from 2.480 (2) to 2.890 (2) Å . The site hosting Sr4 is very flexible and bulky, resulting in a greatly deformed SrO 9 polyhedron. The geometry ratio ECoN (Ag1)/CN(Ag1) = 3.93/5 of the Ag1O 5 polyhedron indicates a distorted squarepyramidal coordination environment. This behaviour can be attributed to the edge or face-sharing between these polyhedral units. This modality of linkage, as well as the ionic radius of Sr 2+ and Ag + , induces a strong cation-cation electrostatic repulsion, which is reflected in the interatomic distances and consequently on the repetition of the ionic charge and bond-valence-sum (BVS) values.
The CHARDI analysis method gives the distribution of calculated ECoN numbers of a central cation among all the neighbouring anions (Hoppe, 1979). The calculation of this number is related directly to the distribution of charges in crystalline structures. The measure of the correctness of the structure (cation ratio) and of the degree of over or under bonding (anion ratio) is performed via the evaluation of the internal criterion q/Q (where q is the formal oxidation number and Q the computed charge). The charge-distribution method (CD or CHARDI), developed by Hoppe et al. (1989), and the bond -valence (BVS) approach introduced to predict bond lengths in inorganic crystals (Brown, 1977(Brown, , 1978 provide powerful tools for analysis of the connectivity of crystal structures and the validation of structural models. In the present study, both validation tools, BVS and CHARDI, are applied to the structural model of the title compound. Generally, for a well-refined structure, the calculated valences V(i) obtained by the BVS model and the computed charge Q(i) according to the CHARDI analysis must be in close agreement with the oxidation number of the atoms. The CHARDI computations were carried out with the CHARDI2015 program (Nespolo & Guillot, 2016), while BVS was calculated using PLATON (Spek, 2009). In the asymmetric unit, all atoms are located on general positions (Wyckoff position 2i) of space group P1 except for Cu1, which is located on a special position (Wyckoff position 1a). The distribution of the electric charges at the 40 crystallographic sites of the asymmetric unit shows that the Ag + , Sr 2+ , Cu 2+ and P 5+ cations fully occupy 16 sites. Otherwise, charge neutrality requires the location of 24 oxygen atoms in the remaining 2i sites. The first results of BVS calculations for Sr3 suggest a valence V(Sr3) = 1.900 v.u. for a coordination number CN = 7.  This result can be significantly improved by widening the coordination sphere to 3.1410 Å , which allows the integration of a supplemental oxygen, thus inducing valence V(Sr3) = 1.962 v.u. The analysis of the data summarized in Table 1 reveals that the values obtained from charges Q(i) and bondvalence sums V(i) of the cations are all compatible with the weighted oxidation number q(i)Ásof(i). The minor deviations reported from these parameters with respect to the formal oxidation state are closely related to the distortion level of the occupied sites. Despite these irregularities, all the values of the internal criterion q(i)/Q(i) are very close to unity, which confirms the validity of the structural model obtained from the X-ray diffraction data. The convergence of the CHARDI model is evaluated by the mean absolute percentage deviation (MAPD) as shown in the equation below, which measures the agreement between q(i) and Q(i) for the whole sets of PC atoms (polyhedron-centring atoms) and of V atoms (the vertex atoms) (Eon & Nespolo, 2015). For the cationic charges in the structure, we report that the calculated value of MAPD is only 1.7%.
where N is the number of polyhedron-centring or vertex atoms in the asymmetric unit. The calculated anionic charges Q(i) of oxygen show a lowest deviation of the order of 4.5% with respect to q(i). These values of MAPD show that the dual description as cation-centred and anion-centred is satisfactory and adequate for the studied structural model. The ratio q(i)/Q(i) is approximately equal to 1 in most cases (Table 2), with some exceptions: q(O8)/Q(O8) = 1.16, q(O12)/Q(O12) = 0.92 and q(O22)/Q(O22) = 1.15. This anomaly of negative-charge repetition could be due to the OUB effect (over-under bonding effect) (Nespolo et al., 1999), which results from the repulsive interactions of the cations located at the centre of the polyhedra. Therefore the anionic charges of oxygen deviate slightly from the ideal value À2. This also explains the variation of cation-anion distances in the various polyhedra in the crystal structure of AgSr 4 Cu 4.5 (PO 4 ) 6 .
The plausibility of a crystal-structure model may also be tested by the global instability index (GII) (Salinas-Sanchez et al., 1992). The calculated value of the GII index measures the deviation of the bond-valence sums from the formal valence V i averaged over all N atoms of the asymmetric unit. For an unstrained structure, GII is below 0.1 v.u. and may approach 0.2 v.u. in a structure with lattice-induced strains (Adams et al., 2004). Values larger than 0.2 v.u. are typically taken as an indication of the presence of intrinsic strains strong enough to cause instability of the crystal structure (Brown, 1992). For the crystal structure of the title compound, GII = 0.0944, which indicates high stability and rigidity of the proposed structural model.

Database survey
A search in the ICSD database shows that no compounds are currently known in the quaternary system AgO/SrO/CuO/ P 2 O 5 . The same is true within the AgO/SrO/P 2 O 5 ternary system. However, one compound is known in the AgO/CuO/ P 2 O 5 ternary system, viz. -AgCuPO 4 which crystallizes in the Pbca space group (Quarton & Oumba, 1983). There are seven compounds known in the ternary SrO/CuO/P 2 O 5 system, viz. Sr 9.1 Cu 1.4 (PO 4 ) 7 , Sr 3 Cu 3 (PO 4 ) 4 (Belik et al., 2002;Effenberger, 1999) Table 1 CHARDI and BVS analysis for the cations in the title compound. q(i) = formal oxidation number; sof(i) = site occupancy; CN(i) = classical coordination number; Q(i) = calculated charge; V(i) = calculated valence; ECoN(i) = effective coordination number. Cation

Synthesis and crystallization
Single crystals of the title compound were obtained using the hydrothermal method with the following mixture of reagents: silver nitrate, strontium nitrate, metallic copper and 85wt% phosphoric acid in a proportion corresponding to the molar ratio Ag:Cu:Sr:P = 1:3:1:3. The hydrothermal reaction was conducted in a 23 mL Teflon-lined autoclave with 12 mL of distilled water under autogenous pressure. The vessel was heated to 473 K for 4 d. After being filtered off, washed with distilled water and dried in air, the reaction product consisted of a light-blue crystals in various forms corresponding to the title compound.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3. The refinement of the occupation of all atom sites shows full occupancy and leads to the stoichiometric formula AgSr 4 Cu 4.5 (PO 4 ) 6 . However, the difference-Fourier map shows two electron-density peaks of intensity 4.05 and À3.87 e Å À3 located at 0.63 and 0.59 Å from Ag1, respectively. These rather strong peaks could not be removed using a different integration strategy or another absorption model.   (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).