Crystal structure of dimanganese(II) zinc bis­[ortho­phosphate(V)] monohydrate

Alhakmi, G.; Assani, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2056989015000341

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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages 154-156

doi:10.1107/S2056989015000341

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Crystal structure of dimanganese(II) zinc bis[orthophosphate(V)] monohydrate

Ghaleb Alhakmi,^a ^* Abderrazzak Assani,^a Mohamed Saadi ^a and Lahcen El Ammari ^a

^aLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: g_alhakmi@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 December 2014; accepted 7 January 2015; online 14 January 2015)

The title compound, Mn₂Zn(PO₄)₂·H₂O, was obtained under hydrothermal conditions. The structure is isotypic with other transition metal phosphates of the type M₃₋_xM′_x(PO₄)₂·H₂O, but shows no statistical disorder of the three metallic sites. The principal building units are distorted [MnO₆] and [MnO₅(H₂O)] octahedra, a distorted [ZnO₅] square pyramid and two regular PO₄ tetrahedra. The connection of the polyhedra leads to a framework structure. Two types of layers parallel to (-101) can be distinguished in this framework. One layer contains [Zn₂O₈] dimers linked to PO₄ tetrahedra via common edges. The other layer is more corrugated and contains [Mn₂O₈(H₂O)₂] dimers and [MnO₆] octahedra linked together by common edges. The PO₄ tetrahedra link the two types of layers into a framework structure with channels parallel to [101]. The H atoms of the water molecules point into the channels and form O—H⋯O hydrogen bonds (one of which is bifurcated) with framework O atoms across the channels.

Keywords: crystal structure; transition metal phosphates; hydrothermal synthesis; Fe₃(PO₄)₂·H₂O structure type.

CCDC reference: 1042563

1. Chemical context

The great structural diversity of metal-based phosphates, associated with their physical properties makes this family of compounds interesting as potential functional materials, e.g. as catalysts (Viter & Nagornyi, 2009 ; Weng et al., 2009 ) or ion-exchangers (Jignasa et al., 2006 ). Among the wide variety of metal phosphates, one of our interests is focused on mixed metallic orthophosphates of general formula M₃₋_xM′_x(PO₄)₂·H₂O. The present communication reports the hydrothermal synthesis and structural characterization of a new member of this family, Mn₂Zn(PO₄)₂·H₂O.

2. Structural commentary

The structure of the title compound is built up from four different types of building units: [MnO₆] and [MnO₅(H₂O)] octahedra, [ZnO₅] square pyramids and PO₄ tetrahedra, as shown in Fig. 1. Whereas the [MnO₆] octahedron is more or less regular with Mn—O distances in the range 2.1254 (13) to 2.2590 (13) Å, the [MnO₅(H₂O)] octahedron is significantly distorted with five equal Mn—O distances in the range 2.1191 (13) to 2.1556 (16) and one considerably longer Mn—O distance to the water ligand of 2.5163 (15) Å; the ZnO₅ square pyramid is also distorted with four shorter Zn—O distances between 1.9546 (13) and 2.0347 (12) Å and one longer Zn—O distance, likewise to the water O atom [2.3093 (14) Å]; the two PO₄ tetrahedra are rather regular [P—O distances between 1.5322 (13) and 1.5570 (13) Å; O—P—O angles between 102.92 (7) and 111.62 (8)°]. These polyhedra are arranged in such a way as to build up two types of layers parallel to ( $[\overline{1}]$ 01). One layer contains two [ZnO₅] polyhedra linked together by edge-sharing into a [Zn₂O₈] dimer that in turn is linked to PO₄ tetrahedra. The other layer contains dimers of the type [Mn₂O₈(H₂O)₂] (also formed by edge-sharing of two [MnO₅(H₂O)] octahedra), connecting [MnO₆] octahedra and PO₄ tetrahedra through common vertices. The two types of layers are linked by common edges and vertices into a framework structure with channels parallel to [101]. The water molecules of the [MnO₅(H₂O)] octahedra protrude into these channels and develop hydrogen bonds (one bifurcated) of medium-to-weak strength to framework O atoms across the channels (Fig. 2; Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H1⋯O7	0.89	1.97	2.7866 (19)	151
O9—H2⋯O5ⁱ	0.91	2.16	2.8687 (19)	134
O9—H2⋯O1ⁱⁱ	0.91	2.48	3.0494 (19)	120
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The principal building units in the structure of Mn₂Zn(PO₄)₂·H₂O. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iii) −x + 2, −y + 1, −z + 1; (iv) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (v) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vi) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (viii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 2
Polyhedral representation of Mn₂Zn(PO₄)₂·H₂O showing channels extending parallel to [101]. Hydrogen bonds are shown as dashed lines.

The title compound adopts the Fe₃(PO₄)₂·H₂O structure type (Moore & Araki, 1975 ) and is isotypic with various structures of general formula M₃₋_xM′_x(PO₄)₂·H₂O: CuMn₂(PO₄)₂·H₂O (Liao et al., 1995 ); Co_2.59Zn_0.41(PO₄)₂·H₂O (Sørensen et al., 2005 ); Co_2.39Cu_0.61(PO₄)₂·H₂O (Assani et al., 2010 ); Mg_1.65Cu_1.35(PO₄)₂·H₂O (Khmiyas et al. 2015 ).

3. Synthesis and crystallization

Crystals of Mn₂Zn(PO₄)₂·H₂O were obtained by hydrothermal treatment of zinc oxide (0.0406 g), metallic manganese (0.0824 g), phosphoric acid (0.1 ml) and 12.5 ml of distilled water, in a proportion corresponding to the molar ratio Zn: Mn: P = 1: 3: 3. The hydrothermal reaction was conducted in a 23 ml Teflon-lined autoclave under autogenous pressure at 493 K for five days. After being filtered, washed with deionized water and dried in air, the reaction product consisted of two types of crystals, the first as off-white parallelepipeds corresponding to Mn₇(PO₄)₂(HPO₄)₄ (Riou et al., 1987 ) and the second as colourless parallelepipeds corresponding to the title compound.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The O-bound H atoms were initially located in a difference map. In the last refinement cycle the distances were fixed at 0.89 and 0.91 Å, respectively, and the H atoms refined in the riding-model approximation with U_iso(H) set to 1.5U_eq(O). The highest peak and the deepest hole in the final Fourier map are at 0.32 Å and 0.30 Å, respectively, from Mn1 and Zn1.

Table 2
Experimental details

Crystal data
Chemical formula	Mn₂Zn(PO₄)₂·H₂O
M_r	383.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.1784 (2), 10.1741 (2), 9.0896 (2)
β (°)	114.142 (1)
V (Å³)	690.17 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.54
Crystal size (mm)	0.32 × 0.27 × 0.19

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.574, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	11327, 2407, 2305
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.052, 1.11
No. of reflections	2407
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.84
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1042563

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015000341/wm5102sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000341/wm5102Isup2.hkl

checkCIF report

Chemical context top

The great structural diversity of metal-based phosphates, associated with their physical properties makes this family of compounds interesting as potential functional materials, e.g. as catalysts (Viter & Nagornyi, 2009; Weng et al., 2009) or ion-exchangers (Jignasa et al., 2006). Among the wide variety of metal phosphates, one of our interests is focused on mixed metallic orthophosphates of general formula M_3-_xM'_x(PO₄)₂·H₂O. The present communication reports the hydrothermal synthesis and structural characterization of a new member of this family, Mn₂Zn(PO₄)₂·H₂O.

Structural commentary top

The structure of the title compound is built up from four different types of building units: [MnO₆] and [MnO₅(H₂O)] octahedra, [ZnO₅] square pyramids and PO₄ tetrahedra, as shown in Fig. 1. Whereas the [MnO₆] octahedron is more or less regular with Mn—O distances in the range 2.1254 (13) to 2.2590 (13) Å, the [MnO₅(H₂O)] octahedron is significantly distorted with five equal Mn—O distances in the range 2.1191 (13) to 2.1556 (16) and one considerably longer Mn—O distance to the water ligand of 2.5163 (15) Å; the ZnO₅ square pyramid is also distorted with four shorter Zn—O distances between 1.9546 (13) and 2.0347 (12) Å and one longer Zn—O distance, likewise to the water O atom [2.3093 (14) Å]; the two PO₄ tetrahedra are rather regular [P—O distances between 1.5322 (13) and 1.5570 (13) Å; O—P—O angles between 102.92 (7) and 111.62 (8)°]. These polyhedra are arranged in such a way as to build up two types of layers parallel to (101). One layer contains two [ZnO₅] polyhedra linked together by edge-sharing into a [Zn₂O₈] dimer that in turn is linked to PO₄ tetrahedra. The other layer contains dimers of the type [Mn₂O₈(H₂O)₂] (also formed by edge-sharing of two [MnO₅(H₂O)] octahedra), connecting [MnO₆] octahedra and PO₄ tetrahedra through common vertices. The two types of layers are linked by common edges and vertices into a framework structure with channels parallel to [101]. The water molecules of the [MnO₅(H₂O)] octahedra protrude into these channels and develop hydrogen bonds (one bifurcated) of medium-to-weak strength to framework O atoms across the channels (Fig 2; Table 1).

The title compound adopts the Fe₃(PO₄)₂·H₂O structure type (Moore & Araki, 1975) and is isotypic with various structures of general formula M_3-_xM'_x(PO₄)₂·H₂O: CuMn₂(PO₄)₂·H₂O (Liao et al., 1995); Co_2.59Zn_0.41(PO₄)₂·H₂O (Sørensen et al., 2005); Co_2.39Cu_0.61(PO₄)₂·H₂O (Assani et al., 2010); Mg_1.65Cu_1.35(PO₄)₂·H₂O (Khmiyas et al. 2015).

Synthesis and crystallization top

Crystals of Mn₂Zn(PO₄)₂·H₂O were obtained by hydrothermal treatment of of zinc oxide (0.0406 g), metallic manganese (0.0824 g), phosphoric acid (0.1 ml) and 12.5 ml of distilled water, in a proportion corresponding to the molar ratio Zn: Mn: P = 1: 3: 3. The hydrothermal reaction was conducted in a 23 ml Teflon-lined autoclave under autogenous pressure at 493 K for five days. After being filtered, washed with deionized water and dried in air, the reaction product consisted of two types of crystals, the first as off-white parallelepipeds corresponding to Mn₇(PO₄)₂(HPO₄)₄ (Riou et al., 1987) and the second as colourless parallelepipeds corresponding to the title compound.

Refinement top

Related literature top

For related literature, see: Assani et al. (2010); Jignasa et al. (2006); Khmiyas et al. (2015); Liao et al. (1995); Moore & Araki (1975); Riou et al. (1987); Sørensen et al. (2005); Viter & Nagornyi (2009); Weng et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

Fig. 1. The principal building units in the structure of Mn₂Zn(PO₄)₂·H₂O. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x + 1/2, -y + 1/2, z + 1/2; (iii) -x + 2, -y + 1, -z + 1; (iv) -x + 3/2, y + 1/2, -z + 1/2; (v) -x + 1/2, y - 1/2, -z + 1/2; (vi) x - 1/2, -y + 1/2, z - 1/2; (vii) x - 1/2, -y + 3/2, z - 1/2; (viii) -x + 1/2, y + 1/2, -z + 1/2.]

Fig. 2. Polyhedral representation of Mn₂Zn(PO₄)₂·H₂O showing channels extending parallel to [101]. Hydrogen bonds are shown as dashed lines.

Dimanganese(II) zinc bis[orthophosphate(V)] monohydrate top

Crystal data top

Mn₂Zn(PO₄)₂·H₂O	F(000) = 736
M_r = 383.21	D_x = 3.688 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2407 reflections
a = 8.1784 (2) Å	θ = 2.8–32.0°
b = 10.1741 (2) Å	µ = 7.54 mm⁻¹
c = 9.0896 (2) Å	T = 296 K
β = 114.142 (1)°	Parallelepiped, off-white
V = 690.17 (3) Å³	0.32 × 0.27 × 0.19 mm
Z = 4

Data collection top

Bruker X8 APEX diffractometer	2407 independent reflections
Radiation source: fine-focus sealed tube	2305 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 32.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.574, T_max = 0.748	k = −14→15
11327 measured reflections	l = −13→13

Refinement top

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: inferred from neighbouring sites
wR(F²) = 0.052	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0248P)² + 1.0141P] where P = (F_o² + 2F_c²)/3
2407 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

Mn₂Zn(PO₄)₂·H₂O	V = 690.17 (3) Å³
M_r = 383.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1784 (2) Å	µ = 7.54 mm⁻¹
b = 10.1741 (2) Å	T = 296 K
c = 9.0896 (2) Å	0.32 × 0.27 × 0.19 mm
β = 114.142 (1)°

Data collection top

Bruker X8 APEX diffractometer	2407 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2305 reflections with I > 2σ(I)
T_min = 0.574, T_max = 0.748	R_int = 0.023
11327 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.052	H-atom parameters constrained
S = 1.11	Δρ_max = 0.94 e Å⁻³
2407 reflections	Δρ_min = −0.84 e Å⁻³
127 parameters

Special details top

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 > 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.

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

	x	y	z	U_iso*/U_eq
Mn1	0.88638 (3)	0.35884 (3)	0.46580 (3)	0.00768 (6)
Mn2	0.48057 (3)	0.38305 (3)	0.21880 (3)	0.00726 (6)
Zn1	0.12609 (3)	0.62028 (2)	0.06179 (2)	0.00934 (6)
P1	0.70438 (5)	0.08456 (4)	0.32706 (5)	0.00553 (8)
P2	0.38560 (5)	0.67442 (4)	0.36388 (5)	0.00613 (8)
O1	0.58212 (17)	0.03301 (13)	0.40831 (15)	0.0102 (2)
O2	0.87050 (16)	0.15076 (13)	0.45546 (15)	0.0094 (2)
O3	0.59293 (17)	0.18429 (12)	0.19887 (15)	0.0092 (2)
O4	0.76145 (17)	−0.03217 (12)	0.25178 (15)	0.0092 (2)
O5	0.23736 (18)	0.77279 (13)	0.26723 (16)	0.0123 (2)
O6	0.36400 (17)	0.63194 (13)	0.51688 (15)	0.0104 (2)
O7	0.57269 (16)	0.73311 (13)	0.41028 (15)	0.0110 (2)
O8	0.35411 (17)	0.55914 (13)	0.24330 (15)	0.0107 (2)
O9	0.88135 (18)	0.58568 (14)	0.57419 (16)	0.0130 (2)
H1	0.7876	0.6203	0.4923	0.019*
H2	0.8793	0.5969	0.6731	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.00519 (11)	0.00776 (11)	0.00860 (11)	−0.00070 (8)	0.00129 (8)	0.00274 (8)
Mn2	0.00657 (11)	0.00704 (11)	0.00777 (11)	−0.00016 (8)	0.00254 (9)	−0.00025 (8)
Zn1	0.00839 (10)	0.00949 (10)	0.00884 (9)	0.00028 (6)	0.00219 (7)	0.00093 (6)
P1	0.00538 (16)	0.00594 (17)	0.00519 (16)	0.00046 (13)	0.00209 (13)	−0.00030 (13)
P2	0.00556 (16)	0.00676 (17)	0.00569 (16)	0.00008 (13)	0.00193 (13)	−0.00044 (13)
O1	0.0107 (5)	0.0111 (5)	0.0126 (5)	0.0015 (4)	0.0087 (5)	0.0025 (4)
O2	0.0079 (5)	0.0105 (5)	0.0073 (5)	−0.0020 (4)	0.0008 (4)	−0.0025 (4)
O3	0.0099 (5)	0.0080 (5)	0.0081 (5)	0.0022 (4)	0.0020 (4)	0.0013 (4)
O4	0.0083 (5)	0.0091 (5)	0.0099 (5)	0.0017 (4)	0.0033 (4)	−0.0027 (4)
O5	0.0121 (5)	0.0135 (6)	0.0108 (5)	0.0070 (5)	0.0041 (4)	0.0035 (4)
O6	0.0106 (5)	0.0137 (6)	0.0071 (5)	−0.0006 (4)	0.0038 (4)	0.0016 (4)
O7	0.0081 (5)	0.0129 (6)	0.0120 (5)	−0.0031 (4)	0.0041 (4)	−0.0030 (4)
O8	0.0107 (5)	0.0093 (5)	0.0099 (5)	0.0011 (4)	0.0021 (4)	−0.0035 (4)
O9	0.0109 (5)	0.0181 (6)	0.0106 (5)	0.0020 (5)	0.0051 (4)	0.0007 (5)

Geometric parameters (Å, º) top

Mn1—O6ⁱ	2.1191 (13)	Zn1—O1^vi	2.0242 (13)
Mn1—O2	2.1208 (14)	Zn1—O1^viii	2.0347 (12)
Mn1—O3ⁱⁱ	2.1464 (12)	Zn1—O5	2.3093 (14)
Mn1—O9ⁱⁱⁱ	2.1504 (14)	P1—O3	1.5327 (13)
Mn1—O4^iv	2.1556 (13)	P1—O4	1.5355 (13)
Mn1—O9	2.5163 (15)	P1—O2	1.5377 (13)
Mn2—O8	2.1254 (13)	P1—O1	1.5570 (13)
Mn2—O5^v	2.1533 (13)	P2—O7	1.5322 (13)
Mn2—O4^iv	2.1921 (13)	P2—O6	1.5340 (13)
Mn2—O2^vi	2.2126 (13)	P2—O5	1.5401 (13)
Mn2—O6ⁱ	2.2166 (13)	P2—O8	1.5532 (13)
Mn2—O3	2.2590 (13)	O9—H1	0.8939
Zn1—O7^vii	1.9546 (13)	O9—H2	0.9131
Zn1—O8	2.0174 (13)

O6ⁱ—Mn1—O2	90.23 (5)	O4^iv—Mn2—O3	87.66 (5)
O6ⁱ—Mn1—O3ⁱⁱ	109.27 (5)	O2^vi—Mn2—O3	76.87 (5)
O2—Mn1—O3ⁱⁱ	81.31 (5)	O6ⁱ—Mn2—O3	87.34 (5)
O6ⁱ—Mn1—O9ⁱⁱⁱ	161.48 (5)	O7^vii—Zn1—O8	132.60 (5)
O2—Mn1—O9ⁱⁱⁱ	107.27 (5)	O7^vii—Zn1—O1^vi	100.19 (6)
O3ⁱⁱ—Mn1—O9ⁱⁱⁱ	80.06 (5)	O8—Zn1—O1^vi	99.81 (5)
O6ⁱ—Mn1—O4^iv	81.32 (5)	O7^vii—Zn1—O1^viii	117.98 (5)
O2—Mn1—O4^iv	118.14 (5)	O8—Zn1—O1^viii	107.48 (5)
O3ⁱⁱ—Mn1—O4^iv	158.49 (5)	O1^vi—Zn1—O1^viii	80.41 (5)
O9ⁱⁱⁱ—Mn1—O4^iv	84.99 (5)	O7^vii—Zn1—O5	87.57 (5)
O6ⁱ—Mn1—O9	76.07 (5)	O8—Zn1—O5	67.61 (5)
O2—Mn1—O9	157.28 (5)	O1^vi—Zn1—O5	167.20 (5)
O3ⁱⁱ—Mn1—O9	86.18 (5)	O1^viii—Zn1—O5	105.05 (5)
O9ⁱⁱⁱ—Mn1—O9	89.00 (5)	O3—P1—O4	111.58 (7)
O4^iv—Mn1—O9	78.15 (5)	O3—P1—O2	110.68 (7)
O8—Mn2—O5^v	89.03 (5)	O4—P1—O2	109.99 (7)
O8—Mn2—O4^iv	98.10 (5)	O3—P1—O1	106.62 (7)
O5^v—Mn2—O4^iv	167.53 (5)	O4—P1—O1	108.79 (7)
O8—Mn2—O2^vi	104.14 (5)	O2—P1—O1	109.08 (7)
O5^v—Mn2—O2^vi	90.14 (5)	O7—P2—O6	109.42 (7)
O4^iv—Mn2—O2^vi	97.96 (5)	O7—P2—O5	111.62 (8)
O8—Mn2—O6ⁱ	91.85 (5)	O6—P2—O5	110.15 (7)
O5^v—Mn2—O6ⁱ	91.25 (5)	O7—P2—O8	110.32 (7)
O4^iv—Mn2—O6ⁱ	78.36 (5)	O6—P2—O8	112.31 (8)
O2^vi—Mn2—O6ⁱ	163.97 (5)	O5—P2—O8	102.92 (7)
O8—Mn2—O3	173.90 (5)	H1—O9—H2	114.6
O5^v—Mn2—O3	84.95 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H1···O7	0.89	1.97	2.7866 (19)	151
O9—H2···O5^ix	0.91	2.16	2.8687 (19)	134
O9—H2···O1ⁱⁱ	0.91	2.48	3.0494 (19)	120

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (ix) x+1/2, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H1···O7	0.89	1.97	2.7866 (19)	150.7
O9—H2···O5ⁱ	0.91	2.16	2.8687 (19)	134.2
O9—H2···O1ⁱⁱ	0.91	2.48	3.0494 (19)	120.4

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	Mn₂Zn(PO₄)₂·H₂O
M_r	383.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.1784 (2), 10.1741 (2), 9.0896 (2)
β (°)	114.142 (1)
V (Å³)	690.17 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.54
Crystal size (mm)	0.32 × 0.27 × 0.19

Data collection
Diffractometer	Bruker X8 APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.574, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	11327, 2407, 2305
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.052, 1.11
No. of reflections	2407
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.84

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 and Mohammed V University, Rabat, Morocco, for financial support.

References

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Volume 71| Part 2| February 2015| Pages 154-156

doi:10.1107/S2056989015000341

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