Crystal structure of SrCo4(OH)(PO4)3, a new hy­droxy­phosphate

Cherif, F.-Z.; Taibi, M.; Boukhari, A.; Aride, J.; Assani, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989020007331

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ISSN: 2056-9890

Volume 76| Part 7| July 2020| Pages 1022-1026

https://doi.org/10.1107/S2056989020007331

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Crystal structure of SrCo₄(OH)(PO₄)₃, a new hydroxyphosphate

Fatima-Zahra Cherif,^a ^* Mhamed Taibi,^b Ali Boukhari,^a Jilali Aride,^b Abderrazzak Assani,^a Mohamed Saadi ^a and Lahcen El Ammari ^a

^aLaboratoire de Chimie Appliquée des Matériaux, Centre des Sciences des Matériaux, Faculty of Science, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco, and ^bLaboratoire de Physico-Chimie des Matériaux Inorganiques et Organiques, Centre des Sciences des Matériaux, Ecole Normale Supérieure, Mohammed V University in Rabat, Morocco
^*Correspondence e-mail: fz.cherif@yahoo.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 13 May 2020; accepted 1 June 2020; online 5 June 2020)

Single crystals of strontium tetracobalt tris(orthophosphate) hydroxide, SrCo₄(OH)(PO₄)₃, were grown serendipitously under hydrothermal conditions at 473 K. The crystal structure consists of undulating chains of edge-sharing [CoO₆] octahedra that are linked into (010) layers by common vertices between chains. Adjacent layers are linked along [010] into a framework structure by tetrahedral [CoO₄] units and by PO₄ tetrahedra. The framework delimits channels extending along [100] in which the eleven-coordinate strontium cations are situated. Bifurcated O—H⋯O hydrogen bonds of weak strengths consolidate the crystal packing. The title compound was also characterized by infrared spectroscopy.

Keywords: crystal structure; orthophosphate; cobalt; strontium; bifurcated hydrogen bonding; infrared spectroscopy.

CCDC reference: 2006988

1. Chemical context

The search for new inorganic materials with open-frame structures comprising transition-metal polyhedra, [MO_x], with tetrahedral phosphate or vanadate units by sharing corners or edges is still ongoing (Rghioui et al., 2019 ; Ouaatta et al., 2019 ; Khmiyas et al., 2020 ). Generally, these interconnections can lead to structures with cages, interlayer spaces or channels, and the corresponding compounds are explored extensively for their excellent physical properties and various applications in electrical, electrochemical, magnetic or catalytic processes (Goodenough et al., 1976 ; Borel et al., 1991 ; La Parola et al., 2018 ; Hadouchi et al., 2019 ). The introduction of borate groups (BO₃ or BO₄) to phosphate (PO₄) units leads to a group of borophosphates with specific structural characteristics. Compounds of this family likewise exhibit remarkable physicochemical properties that allow them to be applied in different fields (Kniep et al., 1998 ; Ewald et al., 2007 ; Lin et al., 2008 ; Menezes et al., 2008 ). About a decade ago, we managed to synthesize two borophosphate phases, viz. (Ag_0.57Ni_0.22)Ni(H₂O)₂[BP₂O₈]·0.67H₂O and AgMg(H₂O)₂[BP₂O₈]·H₂O (Zouihri et al., 2011a ,b ). In this context, we attempted to synthesize a strontium- and cobalt-based borophosphate, namely SrCo₂BPO₇, by means of the hydrothermal process. Instead, we have isolated a new hydroxyphosphate, SrCo₄(OH)(PO₄)₃, and report here its crystal structure and its infrared spectrum.

2. Structural commentary

In the three-dimensional framework structure of SrCo₄(OH)(PO₄)₃, an octahedral coordination of three cobalt atoms (Co1, Co2, Co3) and a tetrahedral coordination of the fourth cobalt (Co4) is observed. Atom O13 bears a hydrogen atom and bridges two of the six-coordinate Co atoms (Co1, Co2) and the four-coordinate Co4 atom. The hydroxide group also forms a weak bifurcated hydrogen bond (Table 1) to two phosphate tetrahedra (Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13⋯O8ⁱ	0.82	2.21	2.982 (3)	157
O13—H13⋯O10ⁱ	0.82	2.40	3.010 (3)	132
Symmetry code: (i) x+1, y, z.

Figure 1
The interconnection of [CoO₆] and [CoO₄] polyhedra, and the hydroxide group linked to PO₄ tetrahedra through a bifurcated hydrogen bond (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (ii) −x − $[{1\over 2}]$ , −y + 1, z + $[{1\over 2}]$ ; (iii) x − 1, y, z; (iv) −x + $[{1\over 2}]$ , −y + 1, z + $[{1\over 2}]$ ; (v) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (vi) x + 1, y, z; (vii) x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (viii) −x + $[{1\over 2}]$ , −y + 1, z − $[{1\over 2}]$ ; (ix) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (x) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1].

The [CoO₆] octahedra share edges to form infinite undulating chains extending parallel to [001]. Adjacent chains are cross-linked via common vertex atoms (O3) to build up (010) layers (Fig. 2) with the formation of oval voids surrounded by eight octahedra. Two PO₄ tetrahedra occupy the void space, whereby P1O₄ shares three of its vertices with five [CoO₆] octahedra and P2O₄ shares an edge with an octahedron and a vertex with two opposite octahedra (Fig. 3).

Figure 2
[CoO₆] octahedra sharing edges to form chains that are linked together via a common corner every three octahedra.

Figure 3
Edge-sharing [CoO₆] octahedra and PO₄ tetrahedra building a layer parallel to (010).

The [Co4O₃OH] tetrahedra are linked through corners into zigzag chains running parallel to [100]; the chains are flanked by P2O₄ and P3O₄ tetrahedra into ribbons. The strontium cations and P1O₄ tetrahedra are of the same height as the ribbons, thus defining a second layer parallel to (010) (Fig. 4). The crystal structure can be described by the stacking of the two types of layers along [010], which leads to the formation of channels extending parallel to [100] in which the strontium cations are located (Fig. 5). Each Sr^II atom is surrounded by eleven oxygen atoms, forming a distorted polyhedron.

Figure 4
Ribbons formed by [CoO₄] and P2O₄ and P3O₄ tetrahedra, and strontium atoms and P1O₄ tetrahedra at the same height forming the second layer parallel to (010).

Figure 5
The crystal structure of SrCo₄(OH)(PO₄)₃ in a projection along [100], showing channels in which the strontium cations are located.

Comparison of the metal–oxygen polyhedra in the title structure with the same type of polyhedra in comparable structures shows a similar behaviour. All [CoO₆] octahedra in SrCo₄(OH)(PO₄)₃ are distorted, with the Co—O distance varying between 2.022 (2) and 2.284 (2) Å. The averaged Co—O distances of 2.130 Å for Co1, 2.122 Å for Co2 and 2.124 Å for Co3 are in good agreement with those of Co₅(PO₄)₂(OH)₄ (average Co—O distances are 2.107 Å for Co1, 2.144 Å for Co2, 2.140 Å for Co3, 2.148 Å for Co4 and 2.150 Å for Co5; Ruszala et al., 1977 ). The distorted [Co4O₃OH] tetrahedron shows much shorter Co—O distances ranging from 1.942 (2) to 1.995 (2) Å. These distances are comparable with the averaged ^[4]Co—O distances of 1.966, 1.955, 1.957 and 1.958 Å observed, respectively, in the phosphates NaCoPO₄, KCoPO₄, NH₄CoPO₄-Hex and NH₄CoPO₄-ABW (Feng et al., 1997 ). The PO₄ tetrahedra in the title structure have averaged distances of 1.542 Å for P1, 1.539 Å for P2 and 1.539Å for P3, and are compatible with the P—O distances in the orthophosphate SrCo₂Fe(PO₄)₃ (Bouraima et al., 2016 ).

The structure model of SrCo₄(OH)(PO₄)₃ is in good agreement with calculations of the bond-valence sums (Brown & Altermatt, 1985 ). The obtained values (in valence units) for the cations Sr^II, Co^II, and P^V are close to the expected values: Sr1 (1.95), Co1 (1.89), Co2 (1.89), Co3 (1.88), Co4 (1.92), P1 (4.90), P2 (4.95) and P3 (4.95). The bond-valence sums calculated for the oxygen atoms range between 1.82 and 2.29 valence units.

3. Infrared spectroscopy

An infrared spectrum of SrCo₄(OH)(PO₄)₃ was recorded in order to verify the existence of the hydroxyl and PO₄ groups in the title compound (Fig. 6). The FT-IR spectrum shows characteristic vibration bands of isolated PO₄ groups. The bands observed at around 420 and 463 cm⁻¹ can be assigned to the ν₂ asymmetric stretching mode while the vibration at 573 cm⁻¹ is attributed to ν₄ asymmetric O—P—O deformation. The weak band observed at 750 cm⁻¹ most likely originates from ^[4]Co—O vibrations, as observed in many other phosphates (Rusakov et al., 2006 ; Antony et al., 2011 ; Bushiri et al., 2002 ; De Pedro et al., 2010 ). The vibration at 1014 cm⁻¹ corresponds to the ν₃ asymmetric stretching mode of the phosphate tetrahedra. The remaining vibrations centred at 3566, 3433 and 1632 cm⁻¹ are commonly assigned to the stretching vibration of the bridging –OH group, as in Co₂PO₄OH (Wang et al., 2014 ), in addition to the OH⁻ librational mode, which is observed at 637 cm⁻¹. We also note the presence of bands at 1384 and 875 cm⁻¹, indicating C—O bonds (Ribeiro et al., 2006 ). This observation suggests that the powdered sample contained impurities of a carbonate. The assignments of all vibration bands are summarized in Table 2.

Table 2
Assignments of infrared vibration bands (cm⁻¹) for SrCo₄(OH)(PO₄)₃

Position	Assignment
420	ν₂ asymmetric stretching mode of P—O bonds
463	ν₂ asymmetric stretching mode of P—O bond
573	ν₄ asymmetric deformation of O—P—O
637	ν_L libration mode of the hydroxyl group
750	^[4]Co—O stretching mode
875	ν₂ vibration of C—O bond
1014	ν₃ asymmetric stretching mode of PO₄³⁻
1384	ν₃ vibration of C—O bond
1632	O—H stretching band
3433	O—H stretching band
3566	ν_s stretching mode of the hydroxyl group⁻

Figure 6
Infrared spectrum of SrCo₄(OH)(PO₄)₃.

4. Database survey

A search in the Inorganic Crystal Structure Database (ICSD; Zagorac et al., 2019 ) revealed no match in the pseudo-quaternary system SrO/CoO/P₂O₅/OH. However, five compounds were identified in the pseudo-ternary SrO/CoO/P₂O₅ system, viz. triclinic SrCo₂(PO₄)₂ (P $[\overline{1}]$ , Z = 2; El Bali et al., 1993 ), monoclinic SrCoP₂O₇ (P2₁/n, Z = 4; Riou & Raveau 1991 ), monoclinic Sr₂Co(PO₄)₂ and SrCo₃(P₂O₇)₂ (both P2₁/c, Z = 6 and 2, respectively; Belik et al. 2001 and Yang et al., 2008 ) and hexagonal Sr₅Co_0.18P₃O_12.92 (P6₃/m, Z = 2; Kazin et al., 2017 ).

5. Synthesis and crystallization

Single crystals of SrCo₄(OH)(PO₄)₃ were obtained serendipitously by attempting to synthesize the borophosphate SrCo₂BPO₇ under hydrothermal conditions. The starting materials, Sr(NO₃)₂ (0.3174 g), Co(CH₃COO)₂·4H₂O (0.7473 g), H₃BO₃ (0.0927 g) and H₃PO₄ (12 N; 0.1 ml), were mixed in the molar proportions of 1:2:1:1. The hydrothermal reaction was conducted in a 23 ml Teflon-lined autoclave, filled to 50% with distilled water and heated under autogenous pressure at 473 K for five days. After the end of the heat treatment, the autoclave was taken out of the oven and allowed to cool to room temperature. The reaction product was collected, filtered, rinsed with distilled water and dried in air. Optical microscopy revealed two types of crystals, viz. dark-purple and dark-red rectangular crystals. X-ray diffraction analysis showed the red crystals to be Co₂(OH)PO₄ (Harrison et al., 1995 ). The purple parallelepipeds correspond to the title compound.

Infrared spectroscopic measurements were performed on a VERTEX 70 FT-IR spectrometer, using the MRI transmission technique using KBr pellets. An adequate quantity of the studied phosphate powder, obtained by grinding the SrCo₄(OH)(PO₄)₃ crystals, was diluted in KBr before being pressed into a pellet. The analysis was performed at room temperature, and the spectrum was recorded in the range 4000–400 cm⁻¹.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atom of the OH group was located in a difference-Fourier map and was refined was a fixed O—H bond length of 0.82 Å and U_iso(H) = 1.5U_eq(O). The maximum and minimum remaining electron density was located at 0.69 Å from Sr1 and 0.56 Å from Co4, respectively. The reflection (011) was affected by the beam-stop (F_o² = 0) while reflections (052) and (053), having F_o² > F_c², were probably affected by the Renninger effect. All three reflections were omitted from the refinement.

Table 3
Experimental details

Crystal data
Chemical formula	SrCo₄(OH)(PO₄)₃
M_r	625.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	5.1245 (1), 12.0491 (2), 15.7118 (3)
V (Å³)	970.13 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	12.74
Crystal size (mm)	0.35 × 0.26 × 0.17

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.391, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	34471, 4243, 4038
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.806

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.050, 1.07
No. of reflections	4243
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.60, −0.68
Absolute structure	Flack x determined using 1625 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 ).
Absolute structure parameter	0.008 (3)
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2006988

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007331/wm5562sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007331/wm5562Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Strontium tetracobalt tris(orthophosphate) hydroxide top

Crystal data top

SrCo₄(OH)(PO₄)₃	D_x = 4.281 Mg m⁻³
M_r = 625.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 4243 reflections
a = 5.1245 (1) Å	θ = 2.6–35.0°
b = 12.0491 (2) Å	µ = 12.74 mm⁻¹
c = 15.7118 (3) Å	T = 296 K
V = 970.13 (3) Å³	Parallelepiped, violet
Z = 4	0.35 × 0.26 × 0.17 mm
F(000) = 1184

Data collection top

Bruker X8 APEX Diffractometer	4243 independent reflections
Radiation source: fine-focus sealed tube	4038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 35.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
T_min = 0.391, T_max = 0.748	k = −19→18
34471 measured reflections	l = −25→25

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0221P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.022	(Δ/σ)_max = 0.001
wR(F²) = 0.050	Δρ_max = 1.60 e Å⁻³
S = 1.07	Δρ_min = −0.68 e Å⁻³
4243 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
191 parameters	Extinction coefficient: 0.0042 (3)
0 restraints	Absolute structure: Flack x determined using 1625 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Hydrogen site location: difference Fourier map	Absolute structure parameter: 0.008 (3)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Sr1	0.02677 (6)	0.72309 (2)	0.67782 (2)	0.00840 (6)
Co1	0.51704 (8)	0.48429 (3)	0.35972 (3)	0.00572 (8)
Co2	0.53401 (9)	0.58186 (4)	0.54997 (3)	0.00613 (8)
Co3	0.47299 (8)	0.46200 (3)	0.74367 (3)	0.00580 (8)
Co4	0.28203 (8)	0.32358 (4)	0.51444 (3)	0.00794 (9)
P1	0.51747 (15)	0.85171 (6)	0.57349 (5)	0.00425 (12)
P2	0.01127 (15)	0.45034 (6)	0.65719 (5)	0.00471 (13)
P3	−0.00586 (15)	0.30856 (6)	0.33173 (5)	0.00413 (12)
O1	0.4003 (4)	0.8648 (2)	0.48533 (15)	0.0092 (4)
O2	0.8108 (4)	0.8848 (2)	0.57323 (15)	0.0074 (4)
O3	0.3638 (4)	0.9243 (2)	0.63798 (15)	0.0074 (4)
O4	0.4924 (5)	0.73162 (18)	0.60637 (15)	0.0095 (4)
O5	0.2427 (4)	0.5287 (2)	0.63664 (15)	0.0078 (4)
O6	−0.2433 (4)	0.5173 (2)	0.66027 (15)	0.0075 (4)
O7	0.0710 (4)	0.40910 (19)	0.74879 (15)	0.0068 (4)
O8	−0.0011 (5)	0.3572 (2)	0.59242 (14)	0.0108 (4)
O9	0.1926 (4)	0.40027 (19)	0.30856 (15)	0.0073 (4)
O10	0.0074 (4)	0.29074 (18)	0.43053 (14)	0.0080 (4)
O11	−0.2813 (4)	0.34923 (19)	0.30965 (15)	0.0075 (4)
O12	0.0671 (4)	0.20305 (19)	0.28586 (16)	0.0097 (4)
O13	0.5519 (4)	0.43152 (18)	0.48508 (15)	0.0073 (4)
H13	0.691669	0.405651	0.500919	0.011*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sr1	0.01002 (12)	0.00611 (12)	0.00908 (12)	0.00095 (10)	0.00229 (10)	0.00061 (10)
Co1	0.00609 (16)	0.00557 (17)	0.00550 (17)	−0.00054 (14)	−0.00005 (14)	−0.00035 (13)
Co2	0.00739 (17)	0.00508 (17)	0.00593 (17)	−0.00087 (15)	0.00149 (14)	−0.00104 (13)
Co3	0.00560 (16)	0.00635 (17)	0.00544 (16)	0.00038 (14)	0.00019 (14)	0.00037 (13)
Co4	0.00687 (17)	0.0095 (2)	0.00748 (18)	−0.00059 (14)	−0.00076 (14)	0.00135 (16)
P1	0.0047 (3)	0.0041 (3)	0.0039 (3)	−0.0005 (3)	0.0001 (2)	0.0001 (2)
P2	0.0044 (3)	0.0055 (3)	0.0042 (3)	0.0001 (3)	−0.0001 (2)	0.0002 (2)
P3	0.0051 (3)	0.0035 (3)	0.0038 (3)	−0.0002 (2)	−0.0002 (2)	0.0000 (2)
O1	0.0093 (9)	0.0138 (11)	0.0045 (9)	0.0012 (8)	−0.0026 (8)	−0.0010 (9)
O2	0.0044 (9)	0.0098 (10)	0.0079 (10)	−0.0026 (8)	0.0002 (7)	−0.0008 (8)
O3	0.0069 (9)	0.0083 (10)	0.0071 (10)	0.0033 (8)	−0.0001 (7)	−0.0022 (9)
O4	0.0140 (10)	0.0036 (9)	0.0109 (9)	−0.0001 (9)	0.0049 (8)	0.0008 (7)
O5	0.0058 (9)	0.0099 (10)	0.0077 (10)	−0.0020 (8)	0.0004 (7)	0.0028 (9)
O6	0.0061 (9)	0.0099 (11)	0.0065 (10)	0.0027 (8)	−0.0002 (7)	0.0016 (8)
O7	0.0069 (9)	0.0073 (10)	0.0062 (9)	−0.0016 (7)	−0.0012 (7)	0.0015 (8)
O8	0.0115 (10)	0.0114 (10)	0.0094 (10)	−0.0022 (9)	0.0030 (9)	−0.0059 (8)
O9	0.0077 (9)	0.0055 (9)	0.0088 (10)	−0.0020 (7)	0.0004 (7)	0.0022 (8)
O10	0.0095 (10)	0.0104 (10)	0.0039 (9)	−0.0020 (8)	0.0000 (8)	0.0008 (7)
O11	0.0062 (9)	0.0081 (10)	0.0082 (10)	0.0008 (8)	−0.0016 (7)	−0.0017 (8)
O12	0.0120 (10)	0.0060 (10)	0.0111 (10)	0.0014 (8)	−0.0002 (8)	−0.0035 (8)
O13	0.0068 (9)	0.0058 (9)	0.0092 (9)	0.0006 (7)	−0.0002 (8)	0.0003 (8)

Geometric parameters (Å, º) top

Sr1—O7ⁱ	2.570 (2)	Co3—O6^vi	2.067 (2)
Sr1—O11ⁱⁱ	2.575 (2)	Co3—O3^ix	2.089 (2)
Sr1—O4	2.639 (2)	Co3—O12^x	2.098 (2)
Sr1—O5	2.669 (2)	Co3—O9^iv	2.125 (2)
Sr1—O2ⁱⁱⁱ	2.779 (2)	Co3—O7	2.158 (2)
Sr1—O12^iv	2.829 (2)	Co3—O5	2.206 (2)
Sr1—O1^v	2.848 (2)	Co4—O8	1.942 (2)
Sr1—O6	2.853 (2)	Co4—O13	1.954 (2)
Sr1—O9^iv	2.915 (2)	Co4—O10	1.969 (2)
Sr1—O4ⁱⁱⁱ	2.961 (2)	Co4—O10^x	1.995 (2)
Sr1—O3	3.041 (2)	P1—O1	1.518 (2)
Co1—O13	2.077 (2)	P1—O4	1.542 (2)
Co1—O11^vi	2.082 (2)	P1—O3	1.553 (2)
Co1—O3^vii	2.091 (2)	P1—O2	1.555 (2)
Co1—O9	2.106 (2)	P2—O8	1.517 (2)
Co1—O2^v	2.171 (2)	P2—O6	1.534 (2)
Co1—O7^viii	2.212 (2)	P2—O5	1.550 (2)
Co2—O4	2.022 (2)	P2—O7	1.553 (2)
Co2—O1^vii	2.060 (2)	P3—O12	1.508 (2)
Co2—O13	2.081 (2)	P3—O11	1.534 (2)
Co2—O5	2.120 (2)	P3—O9	1.545 (2)
Co2—O6^vi	2.216 (2)	P3—O10	1.569 (2)
Co2—O2^v	2.284 (2)	O13—H13	0.8200

O7ⁱ—Sr1—O11ⁱⁱ	80.73 (7)	O9—Co1—O2^v	98.63 (9)
O7ⁱ—Sr1—O4	109.46 (7)	O13—Co1—O7^viii	160.47 (9)
O11ⁱⁱ—Sr1—O4	142.85 (7)	O11^vi—Co1—O7^viii	104.92 (9)
O7ⁱ—Sr1—O5	162.67 (7)	O3^vii—Co1—O7^viii	83.16 (8)
O11ⁱⁱ—Sr1—O5	95.77 (7)	O9—Co1—O7^viii	79.48 (8)
O4—Sr1—O5	63.66 (7)	O2^v—Co1—O7^viii	82.02 (9)
O7ⁱ—Sr1—O2ⁱⁱⁱ	64.92 (7)	O4—Co2—O1^vii	86.30 (10)
O11ⁱⁱ—Sr1—O2ⁱⁱⁱ	121.22 (7)	O4—Co2—O13	175.22 (10)
O4—Sr1—O2ⁱⁱⁱ	94.66 (7)	O1^vii—Co2—O13	95.72 (9)
O5—Sr1—O2ⁱⁱⁱ	129.56 (7)	O4—Co2—O5	85.04 (9)
O7ⁱ—Sr1—O12^iv	66.42 (7)	O1^vii—Co2—O5	155.36 (9)
O11ⁱⁱ—Sr1—O12^iv	89.04 (7)	O13—Co2—O5	94.75 (9)
O4—Sr1—O12^iv	65.03 (7)	O4—Co2—O6^vi	91.44 (10)
O5—Sr1—O12^iv	96.69 (7)	O1^vii—Co2—O6^vi	81.43 (9)
O2ⁱⁱⁱ—Sr1—O12^iv	115.29 (7)	O13—Co2—O6^vi	93.14 (9)
O7ⁱ—Sr1—O1^v	133.13 (7)	O5—Co2—O6^vi	75.77 (9)
O11ⁱⁱ—Sr1—O1^v	119.13 (7)	O4—Co2—O2^v	99.31 (9)
O4—Sr1—O1^v	80.64 (7)	O1^vii—Co2—O2^v	99.98 (9)
O5—Sr1—O1^v	63.27 (7)	O13—Co2—O2^v	76.10 (9)
O2ⁱⁱⁱ—Sr1—O1^v	68.76 (7)	O5—Co2—O2^v	104.17 (9)
O12^iv—Sr1—O1^v	145.52 (7)	O6^vi—Co2—O2^v	169.22 (9)
O7ⁱ—Sr1—O6	134.98 (7)	O6^vi—Co3—O3^ix	110.65 (9)
O11ⁱⁱ—Sr1—O6	63.04 (7)	O6^vi—Co3—O12^x	90.20 (10)
O4—Sr1—O6	115.55 (7)	O3^ix—Co3—O12^x	84.17 (10)
O5—Sr1—O6	54.21 (6)	O6^vi—Co3—O9^iv	109.48 (9)
O2ⁱⁱⁱ—Sr1—O6	111.05 (7)	O3^ix—Co3—O9^iv	84.42 (9)
O12^iv—Sr1—O6	133.49 (7)	O12^x—Co3—O9^iv	159.76 (10)
O1^v—Sr1—O6	58.64 (7)	O6^vi—Co3—O7	142.20 (9)
O7ⁱ—Sr1—O9^iv	102.99 (7)	O3^ix—Co3—O7	106.54 (9)
O11ⁱⁱ—Sr1—O9^iv	60.11 (7)	O12^x—Co3—O7	87.01 (9)
O4—Sr1—O9^iv	82.74 (7)	O9^iv—Co3—O7	80.30 (9)
O5—Sr1—O9^iv	61.25 (7)	O6^vi—Co3—O5	77.04 (9)
O2ⁱⁱⁱ—Sr1—O9^iv	166.11 (7)	O3^ix—Co3—O5	166.41 (9)
O12^iv—Sr1—O9^iv	51.30 (6)	O12^x—Co3—O5	107.46 (10)
O1^v—Sr1—O9^iv	123.85 (7)	O9^iv—Co3—O5	82.38 (9)
O6—Sr1—O9^iv	82.19 (6)	O7—Co3—O5	68.00 (8)
O7ⁱ—Sr1—O4ⁱⁱⁱ	87.68 (6)	O8—Co4—O13	122.63 (10)
O11ⁱⁱ—Sr1—O4ⁱⁱⁱ	82.23 (7)	O8—Co4—O10	86.00 (10)
O4—Sr1—O4ⁱⁱⁱ	132.33 (9)	O13—Co4—O10	118.80 (9)
O5—Sr1—O4ⁱⁱⁱ	108.78 (7)	O8—Co4—O10^x	107.64 (10)
O2ⁱⁱⁱ—Sr1—O4ⁱⁱⁱ	51.92 (6)	O13—Co4—O10^x	98.76 (9)
O12^iv—Sr1—O4ⁱⁱⁱ	153.73 (7)	O10—Co4—O10^x	124.43 (5)
O1^v—Sr1—O4ⁱⁱⁱ	57.40 (6)	O1—P1—O4	111.72 (14)
O6—Sr1—O4ⁱⁱⁱ	62.94 (6)	O1—P1—O3	109.66 (13)
O9^iv—Sr1—O4ⁱⁱⁱ	137.82 (6)	O4—P1—O3	105.51 (13)
O7ⁱ—Sr1—O3	60.53 (7)	O1—P1—O2	110.70 (14)
O11ⁱⁱ—Sr1—O3	135.45 (7)	O4—P1—O2	108.80 (14)
O4—Sr1—O3	50.80 (6)	O3—P1—O2	110.33 (13)
O5—Sr1—O3	114.45 (6)	O8—P2—O6	112.00 (14)
O2ⁱⁱⁱ—Sr1—O3	62.97 (6)	O8—P2—O5	110.08 (14)
O12^iv—Sr1—O3	56.98 (7)	O6—P2—O5	109.67 (13)
O1^v—Sr1—O3	103.90 (6)	O8—P2—O7	113.16 (14)
O6—Sr1—O3	161.48 (6)	O6—P2—O7	107.85 (13)
O9^iv—Sr1—O3	105.74 (6)	O5—P2—O7	103.72 (12)
O4ⁱⁱⁱ—Sr1—O3	114.80 (6)	O12—P3—O11	112.92 (13)
O13—Co1—O11^vi	94.38 (9)	O12—P3—O9	109.08 (14)
O13—Co1—O3^vii	94.12 (9)	O11—P3—O9	108.90 (13)
O11^vi—Co1—O3^vii	89.80 (9)	O12—P3—O10	110.29 (14)
O13—Co1—O9	106.41 (9)	O11—P3—O10	107.90 (13)
O11^vi—Co1—O9	82.65 (9)	O9—P3—O10	107.61 (13)
O3^vii—Co1—O9	158.54 (9)	Co4—O13—H13	107.1
O13—Co1—O2^v	78.70 (9)	Co1—O13—H13	118.6
O11^vi—Co1—O2^v	173.06 (9)	Co2—O13—H13	102.7
O3^vii—Co1—O2^v	91.29 (9)

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x−1/2, −y+1, z+1/2; (iii) x−1, y, z; (iv) −x+1/2, −y+1, z+1/2; (v) x−1/2, −y+3/2, −z+1; (vi) x+1, y, z; (vii) x+1/2, −y+3/2, −z+1; (viii) −x+1/2, −y+1, z−1/2; (ix) −x+1, y−1/2, −z+3/2; (x) x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O8^vi	0.82	2.21	2.982 (3)	157
O13—H13···O10^vi	0.82	2.40	3.010 (3)	132

Symmetry code: (vi) x+1, y, z.

Assignments of infrared vibration bands (cm^-1) for SrCo₄(OH)(PO₄)₃ top

Position	Assignment
420	ν₂ asymmetric stretching mode of P—O bonds
463	ν₂ asymmetric stretching mode of P—O bond
573	ν₄ asymmetric deformation of O—P—O
637	ν_L vibration mode of the hydroxyl group
750	^[4]Co—O stretching mode
875	ν₂ vibration of C—O bond
1014	ν₃ asymmetric stretching mode of PO₄^3-
1384	ν₃ vibration of C—O bond
1632	O—H stretching band
3433	O—H stretching band
3566	ν_s stretching mode of the hydroxyl group^-

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and Mohammed V University, Rabat, Morocco, for financial support.

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