Syntheses and structures of ammonium transition-metal dialuminium tris­(phosphate) dihydrates (NH4)MAl4(PO4)3·2H2O (M = Mn and Ni)

Tokuda, M.; Tanaka, K.; Sugiyama, K.

doi:10.1107/S2056989023000555

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ISSN: 2056-9890

Volume 79| Part 2| February 2023| Pages 116-119

https://doi.org/10.1107/S2056989023000555

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Syntheses and structures of ammonium transition-metal dialuminium tris(phosphate) dihydrates (NH₄)MAl₄(PO₄)₃·2H₂O (M = Mn and Ni)

Makoto Tokuda,^a ^* Keita Tanaka ^a and Kazumasa Sugiyama ^a

^aInstitute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
^*Correspondence e-mail: makoto.tokuda.b7@tohoku.ac.jp

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 20 July 2022; accepted 23 January 2023; online 26 January 2023)

The structures of ammonium manganese(II) dialuminium tris(phosphate) dihydrate, (NH₄)MnAl₂(PO₄)₃·2H₂O, and ammonium nickel(II) dialuminium tris(phosphate) dihydrate, (NH₄)NiAl₂(PO₄)₃·2H₂O, were determined using single-crystal diffraction data. The structures of title compounds are isotypic to cobalt aluminophosphate, (NH₄)CoAl₂(PO₄)₃·2H₂O (LMU-3) [Panz et al. (1998 ). Inorg. Chim. Acta, 269, 73–82], in which a three-dimensional network of vertex-sharing AlO₅ and PO₄ moieties delineate twelve-membered channels in which ammonium, NH₄⁺, and transition-metal cations (M = Mn²⁺ and Ni²⁺) reside as charge compensators for the anionic [Al₂(PO₄)₃]^3– aluminophosphate framework. In both structures, the N atom of the ammonium cation, the transition-metal ion and one of the P atoms lie on crystallographic twofold axes.

Keywords: single-crystal diffraction; crystal structure; aluminophosphate.

CCDC references: 2237562; 2237561

1. Chemical context

The mixed-metal phosphate composed of tetrahedral, bipyramidal and octahedral building units with chemical formula KNiAl₂(PO₄)₃·2H₂O was firstly reported by Meyer & Haushalter (1994 ). Isotypic structures were found in the alumino-, ferri- and gallophosphates; (NH₄)CoAl₂(PO₄)₃·2H₂O (Panz et al. 1998), KMnAl₂(PO₄)₃·2H₂O (Kiriukhina et al. 2020 ), CsFe₃(PO₄)₃·2H₂O (Lii & Huang 1995 ), (NH₄)CoGa₂(PO₄)₃·2H₂O (Chippindale et al. 1996 ), (NH₄)MnGa₂(PO₄)₃·2H₂O (Chippindale et al. 1998 ), (NH₄)NiGa₂(PO₄)₃·2H₂O (Bieniok et al. 2008 ) and KNiGa₂(PO₄)₃·2H₂O (Chippindale et al. 2009 ).

Herein, we report the syntheses and structures of (NH₄)MAl₂(PO₄)₃·2H₂O [M = Mn in (I) and Ni in (II)] using a hydrothermal technique and structural analysis by single-crystal X-ray diffraction. These compounds are isotypic to (NH₄)CoAl₂ (PO₄)₃·2H₂O (LMU-3), crystallizing from a hydrothermal synthesis (Panz et al., 1998).

2. Structural commentary

The aluminophosphate framework of the title compounds with the chemical formula (NH₄)MAl₂(PO₄)₃·2H₂O (M = Mn and Ni) is composed of [PO₄] tetrahedra and [AlO₅] trigonal-bipyramids. Fig. 1(a) shows the [Al₂(PO₄)₃]_∞ layers, which are built up from four- and eight-membered rings connected via Al—O—P bonds. These layers stack along the a-axis direction, with the [P2O₄] tetrahedra (atom P2 lies on a crystallographic twofold axis) bridging between them, leading to the formation of a three-dimensional network encapsulating twelve-membered channels propagating in the [001] direction. The ammonium and transition-metal cations are respectively located in and on these channels, compensating the negative charge of the aluminophosphate framework [Fig. 1(b)].

Figure 1
(a) Two-dimensional layer formed by four- and eight-membered rings in the bc plane and (b) the three-dimensional channels formed by twelve-membered rings in the aluminophosphate framework of Al₂M(NH₄)(PO₄)₃·2H₂O (M = Mn and Ni) illustrated using VESTA (Momma & Izumi, 2011

There are two axial and three equatorial Al—O bonds within the [AlO₅] trigonal bipyramids (Table 1). The axial Al—O bond distances for M = Mn are 1.8886 (19) and 1.9320 (18) Å and those for Ni are 1.8818 (14) and 1.9271 (14) Å, and the equatorial ones are in the ranges 1.7847 (19)–1.8080 (18) Å (Mn) and 1.7731 (14)–1.7979 (14) Å (Ni), thus the average axial Al—O bond distances are larger than the equatorial ones. Previous studies on [AlO₅] trigonal bipyramids in LMU-3, KNiAl₂(PO₄)₃·2H₂O, KMnAl₂(PO₄)₃·2H₂O and (NH₄)₃Al₂(PO₄)₃ (Panz et al., 1998; Meyer & Haushalter 1994; Kiriukhina et al., 2020; Medina et al. 2004 ) showed similar geometrical features with longer axial Al—O bonds distances.

Table 1
Selected bond lengths (Å) in (NH₄)MAl₂(PO₄)₃·2H₂O [M = Mn (I) and Ni (II)]

	(I)	(II)
PO₄ tetrahedra
P1—O6^iv	1.5152 (19)	1.5180 (14)
P1—O2	1.5342 (19)	1.5361 (14)
P1—O3	1.5350 (18)	1.5371 (13)
P1—O1	1.5493 (18)	1.5502 (13)
P2—O5	1.5294 (18)	1.5253 (13)
P2—O4	1.5420 (18)	1.5444 (13)

AlO₅ trigonal bipyramid
Al—O2ⁱⁱ	1.7847 (19)	1.7731 (14)
Al—O1	1.8013 (19)	1.7908 (14)
Al—O5^iv	1.8080 (18)	1.7979 (14)
Al—O3^iv	1.8886 (19)	1.8818 (14)
Al—O4	1.9320 (18)	1.9271 (14)

MnO₆ octahedra
M—O6	2.0799 (19)	2.0052 (13)
M—O7	2.1990 (20)	2.0799 (15)
M—O4	2.2805 (18)	2.1512 (13)
O4⋯O4ⁱ	2.407 (5)	2.387 (4)
O6⋯O7	2.950 (3)	2.785 (2)
O6⋯O7ⁱ	2.962 (4)	2.844 (3)
O4⋯O6	3.192 (3)	3.065 (2)
O4⋯O7	3.254 (3)	3.089 (2)
O4⋯O7ⁱ	3.291 (3)	3.094 (3)
O6⋯O6ⁱ	3.372 (5)	3.132 (4)
Symmetry codes: (i) −x, y, −z + $[{1\over 2}]$ ; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x, −y + 1, z − $[{1\over 2}]$ ; (vi) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + 1.

The transition-metal cations, which lie on crystallographic twofold axes, are octahedrally coordinated by two oxygen atoms of water molecules and four oxygen atoms of the framework (Fig. 2). The mean M—O bond distances for the Mn and Ni compounds are 2.186 Å and 2.079 Å, respectively, which are consistent with the ionic radii of ^VIMn²⁺ (0.83 Å) and ^VINi²⁺ (0.69 Å; Shannon 1976 ). The MO₆ octahedron shares an edge O4⋯O4 with the adjacent [P2O₄] tetrahedron. The length of the shared-edge O4⋯O4 is the shortest among the twelve edges of octahedrally coordinated transition-metal cations in accordance with the P⁵⁺–M²⁺ cation repulsion (Pauling, 1929 , 1960 ).

Figure 2
Positions of the MO₆ [M = Mn (I) and Ni (II)] octahedra in the twelve-membered-ring channel of the aluminophosphate framework. Displacement ellipsoids are presented at the 80% probability level. [Symmetry codes: (i) −x, y, −z + $[{1\over 2}]$ ; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z; (iv) x, −y + 1, z − $[{1\over 2}]$ ; (v) −x, −y + 1, −z + 1.]

The positions of the hydrogen atoms in the water molecule, H71 and H72, could be determined by analysing the residual peaks in the difference-Fourier maps. The oxygen atom O7 of the water molecule is coordinated to the transition-metal ions, and hydrogen atoms of H71 and H72 form O—H⋯O hydrogen bonds with the oxygen atoms O1 and O3 of the [Al₂(PO₄)₃]_∞ layer, respectively (Tables 2 and 3). Thus, the H71⋯O1 and H72⋯O3 hydrogen bonds contribute to the accumulation of the layers.

Table 2
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯O1ⁱ	0.89	1.95	2.831 (3)	178
O7—H72⋯O3ⁱⁱ	0.87	2.04	2.897 (3)	166
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Table 3
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯O1ⁱ	0.81	1.99	2.790 (2)	167
O7—H72⋯O3ⁱⁱ	0.86	2.11	2.961 (2)	170
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

As for the hydrogen-bonding interactions of the ammonium cation (N atom site symmetry 2) within the title compounds, not all the H atoms could be definitively located from difference maps but some structural information could be obtained from the observed distances N1⋯O5 = 3.085 (5) and 3.103 (4) Å and N1⋯O6 = 2.906 (4) and 2.862 (3) Å for (NH₄)MAl₂(PO₄)₃·2H₂O (M = Mn and Ni), respectively. The longer N1⋯O5 distance and the large isotropic atomic displacement parameters, U_iso, of the N1 atom clearly indicate the relatively weaker hydrogen bonding for the presumed N1—H⋯O5 cases. This structural feature did not allow us to definitively located the positions of hydrogen atoms within the N1—H⋯O5 cases. Nevertheless, some of the hydrogen-atom positions around the ammonium cations could be located in the difference-Fourier maps and coordinates are (0.5382, 0.3998, 0.2391) and (0.5357, 0.4204, 0.2296) for (NH₄)MAl₂(PO₄)₃·2H₂O (M = Mn and Ni), respectively. These possible hydrogen-atom positions correspond to those for the N1—H⋯O6 cases. Weak hydrogen bonds between NH₄⁺ and the framework suggests that NH₄⁺ and a monovalent cation (e.g., alkali cation or H₃O⁺) are exchangeable akin to zeolitic cations in this unique framework structure (Meyer & Haushalter 1994; Kiriukhina et al., 2020). The chemical formula for the group of compounds reported in this study can be denoted by A⁺M²⁺Al₂(PO₄)₃·2H₂O (A = monovalent cation, M = divalent transition-metal cation).

3. Synthesis and crystallization

Single crystals of (NH₄)MAl₂(PO₄)₃·2H₂O (M = Mn and Ni) were obtained as by-products of the laumontite-type zeolite imidazole-templated hydrothermal technique. The precursor solution was prepared by dissolving the chemical agents of imidazole, aluminium-isopropoxide and H₃PO₄ (85% solution): the transition-metal component (Ni or Mn) was added to the solution. For the insertion of nickel in the system, (CH₃COO)₂Ni·4H₂O was used and for corresponding manganese analogue (CH₃COO)₂Mn·4H₂O was added to the as-prepared precursor solution. In each case, the resultant gel mixture was then sealed in a Teflon-lined tube and heated at 453 K for three days.

A few colorless, transparent crystals of (NH₄)MnAl₂(PO₄)₃·2H₂O with a plate-like form were separated from the microcrystalline material together with the laumontite-type aluminophosphate, Mn-hureaulite Mn₅[PO₃(OH)]₂(PO₄)₂·4H₂O. In the case of Ni, the product comprises NH₄NiAl₂(PO₄)₃·2H₂O, which forms colorless, transparent plate-like crystals and organic compounds.

The chemical analyses of the synthesized products were performed using energy-dispersive X-ray spectroscopy (EDS). The EDS profile clearly showed the presence of nitrogen. This supports the idea that NH₄⁺, a decomposition product of imidazole, was incorporated within the framework as a charge-compensating cation.

4. Refinement details

The crystal data, data collection methods, and structure refinement details are summarized in Table 4. The positions of the hydrogen atoms bonded to O7 were estimated using the residual peaks in the difference Fourier maps and refined using a riding model. The U_iso parameters for hydrogen atoms were fixed at 1.5 × the U_iso of O7.

Table 4
Experimental details

	(NH₄)MnAl₂(PO₄)₃·2H₂O	(NH₄)NiAl₂(PO₄)₃·2H₂O
Crystal data
M_r	447.88	451.65
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	298	298
a, b, c (Å)	13.3577 (7), 10.2279 (5), 8.7922 (5)	13.0711 (3), 10.1772 (2), 8.74476 (19)
β (°)	108.885 (6)	108.527 (3)
V (Å³)	1136.53 (11)	1103.00 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.85	2.44
Crystal size (mm)	0.05 × 0.04 × 0.02	0.11 × 0.04 × 0.03

Data collection
Diffractometer	XtaLAB Synergy, Single source at offset/far, HyPix	XtaLAB Synergy, Single source at offset/far, HyPix
Absorption correction	Numerical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Numerical (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.938, 0.968	0.853, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	5256, 1316, 1178	9320, 1328, 1281
R_int	0.027	0.021
(sin θ/λ)_max (Å⁻¹)	0.653	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.077, 1.11	0.018, 0.056, 1.14
No. of reflections	1316	1328
No. of parameters	97	97
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.51	0.42, −0.36
Computer programs: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ) and VESTA (Momma & Izumi, 2011 ).

Supporting information

CCDC references: 2237562; 2237561

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989023000555/hb8032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023000555/hb8032Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989023000555/hb8032IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2021); cell refinement: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2021); data reduction: CrysAlis PRO 1.171.40.43a (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b).

Ammonium manganese(II) dialuminium tris(phosphate) dihydrate (I) top

Crystal data top

(NH₄)MnAl₂(PO₄)₃·2H₂O	F(000) = 956.0
M_r = 447.88	D_x = 2.618 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3577 (7) Å	Cell parameters from 3620 reflections
b = 10.2279 (5) Å	θ = 3.9–27.6°
c = 8.7922 (5) Å	µ = 1.85 mm⁻¹
β = 108.885 (6)°	T = 298 K
V = 1136.53 (11) Å³	Plate, colourless
Z = 4	0.05 × 0.04 × 0.02 mm

Data collection top

XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	1316 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1178 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.0000 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
ω scans	h = −17→17
Absorption correction: numerical (CrysAlisPro; Rigaku OD, 2021)	k = −13→11
T_min = 0.938, T_max = 0.968	l = −11→11
5256 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0358P)² + 3.6714P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1316 reflections	Δρ_max = 0.90 e Å⁻³
97 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints

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
Mn	0.000000	0.21386 (5)	0.250000	0.01325 (16)
Al	0.16968 (5)	0.42298 (7)	0.07597 (8)	0.00506 (17)
P1	0.29135 (5)	0.62403 (6)	0.33188 (7)	0.00855 (16)
P2	0.000000	0.49748 (8)	0.250000	0.00678 (19)
N1	0.500000	0.3634 (4)	0.250000	0.0357 (10)
O1	0.20881 (14)	0.57892 (18)	0.1720 (2)	0.0129 (4)
O2	0.27155 (14)	0.77104 (18)	0.3420 (2)	0.0130 (4)
O3	0.27207 (14)	0.55150 (18)	0.4727 (2)	0.0132 (4)
O4	0.07105 (14)	0.40324 (18)	0.1938 (2)	0.0118 (4)
O5	0.06242 (14)	0.58669 (18)	0.3876 (2)	0.0116 (4)
O6	0.09702 (14)	0.09481 (19)	0.1661 (2)	0.0179 (4)
O7	0.11844 (17)	0.1969 (2)	0.4904 (3)	0.0262 (5)
H71	0.148203	0.266954	0.546232	0.039*
H72	0.160636	0.130057	0.499139	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0131 (3)	0.0113 (3)	0.0168 (3)	0.000	0.0069 (2)	0.000
Al	0.0059 (3)	0.0047 (3)	0.0043 (3)	0.0007 (2)	0.0013 (3)	−0.0007 (2)
P1	0.0090 (3)	0.0086 (3)	0.0088 (3)	−0.0016 (2)	0.0039 (2)	−0.0006 (2)
P2	0.0071 (4)	0.0071 (4)	0.0063 (4)	0.000	0.0024 (3)	0.000
N1	0.041 (2)	0.0174 (19)	0.048 (3)	0.000	0.013 (2)	0.000
O1	0.0152 (9)	0.0132 (9)	0.0101 (8)	−0.0029 (7)	0.0039 (7)	−0.0037 (7)
O2	0.0168 (9)	0.0095 (9)	0.0137 (9)	−0.0030 (7)	0.0063 (7)	−0.0024 (7)
O3	0.0165 (9)	0.0124 (9)	0.0126 (9)	0.0010 (7)	0.0071 (7)	0.0029 (7)
O4	0.0125 (9)	0.0099 (8)	0.0153 (9)	0.0006 (7)	0.0078 (7)	0.0000 (7)
O5	0.0114 (8)	0.0123 (9)	0.0095 (8)	−0.0013 (7)	0.0010 (7)	−0.0036 (7)
O6	0.0107 (9)	0.0185 (10)	0.0265 (10)	−0.0019 (7)	0.0089 (8)	−0.0045 (8)
O7	0.0275 (12)	0.0201 (11)	0.0223 (10)	0.0016 (9)	−0.0040 (9)	−0.0044 (8)

Geometric parameters (Å, º) top

Mn—O6	2.0799 (19)	Al—O4	1.9320 (18)
Mn—O6ⁱ	2.0799 (19)	P1—O6^iv	1.5152 (19)
Mn—O7	2.199 (2)	P1—O2	1.5342 (19)
Mn—O7ⁱ	2.199 (2)	P1—O3	1.5350 (18)
Mn—O4	2.2805 (18)	P1—O1	1.5493 (18)
Mn—O4ⁱ	2.2805 (18)	P2—O5	1.5294 (18)
Mn—P2	2.9008 (10)	P2—O5ⁱ	1.5294 (18)
Al—O2ⁱⁱ	1.7847 (19)	P2—O4	1.5420 (18)
Al—O1	1.8013 (19)	P2—O4ⁱ	1.5420 (18)
Al—O5ⁱⁱⁱ	1.8080 (18)	O7—H71	0.8867
Al—O3ⁱⁱⁱ	1.8886 (19)	O7—H72	0.8736

O6—Mn—O6ⁱ	108.33 (11)	O5ⁱⁱⁱ—Al—O4	90.54 (8)
O6—Mn—O7	87.58 (8)	O3ⁱⁱⁱ—Al—O4	176.17 (8)
O6ⁱ—Mn—O7	87.13 (8)	O6^iv—P1—O2	112.34 (11)
O6—Mn—O7ⁱ	87.13 (8)	O6^iv—P1—O3	108.44 (11)
O6ⁱ—Mn—O7ⁱ	87.58 (8)	O2—P1—O3	110.49 (10)
O7—Mn—O7ⁱ	170.96 (12)	O6^iv—P1—O1	111.15 (11)
O6—Mn—O4	93.99 (7)	O2—P1—O1	105.01 (10)
O6ⁱ—Mn—O4	157.67 (7)	O3—P1—O1	109.38 (10)
O7—Mn—O4	93.15 (7)	O5—P2—O5ⁱ	106.74 (14)
O7ⁱ—Mn—O4	94.53 (7)	O5—P2—O4	113.09 (9)
O6—Mn—O4ⁱ	157.67 (7)	O5ⁱ—P2—O4	110.71 (9)
O6ⁱ—Mn—O4ⁱ	93.99 (7)	O5—P2—O4ⁱ	110.71 (9)
O7—Mn—O4ⁱ	94.53 (7)	O5ⁱ—P2—O4ⁱ	113.09 (9)
O7ⁱ—Mn—O4ⁱ	93.15 (7)	O4—P2—O4ⁱ	102.63 (14)
O4—Mn—O4ⁱ	63.72 (9)	O5—P2—Mn	126.63 (7)
O6—Mn—P2	125.84 (6)	O5ⁱ—P2—Mn	126.63 (7)
O6ⁱ—Mn—P2	125.84 (6)	O4—P2—Mn	51.31 (7)
O7—Mn—P2	94.52 (6)	O4ⁱ—P2—Mn	51.31 (7)
O7ⁱ—Mn—P2	94.52 (6)	P1—O1—Al	134.62 (12)
O4—Mn—P2	31.86 (4)	P1—O2—Al^iv	144.61 (13)
O4ⁱ—Mn—P2	31.86 (4)	P1—O3—Al^v	131.12 (11)
O2ⁱⁱ—Al—O1	123.95 (9)	P2—O4—Al	134.74 (11)
O2ⁱⁱ—Al—O5ⁱⁱⁱ	115.92 (9)	P2—O4—Mn	96.83 (9)
O1—Al—O5ⁱⁱⁱ	120.10 (9)	Al—O4—Mn	127.51 (9)
O2ⁱⁱ—Al—O3ⁱⁱⁱ	91.29 (8)	P2—O5—Al^v	139.42 (12)
O1—Al—O3ⁱⁱⁱ	87.58 (8)	P1ⁱⁱ—O6—Mn	127.16 (12)
O5ⁱⁱⁱ—Al—O3ⁱⁱⁱ	92.86 (8)	Mn—O7—H71	121.5
O2ⁱⁱ—Al—O4	88.81 (8)	Mn—O7—H72	112.9
O1—Al—O4	89.19 (8)	H71—O7—H72	115.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O1^v	0.89	1.95	2.831 (3)	178
O7—H72···O3^vi	0.87	2.04	2.897 (3)	166

Symmetry codes: (v) x, −y+1, z+1/2; (vi) −x+1/2, −y+1/2, −z+1.

Ammonium nickel(II) dialuminium tris(phosphate) dihydrate (II) top

Crystal data top

(NH₄)NiAl₂(PO₄)₃·2H₂O	F(000) = 904
M_r = 451.65	D_x = 2.720 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.0711 (3) Å	Cell parameters from 14220 reflections
b = 10.1772 (2) Å	θ = 2.6–44.8°
c = 8.74476 (19) Å	µ = 2.44 mm⁻¹
β = 108.527 (3)°	T = 298 K
V = 1103.00 (4) Å³	Plate, colourless
Z = 4	0.11 × 0.04 × 0.03 mm

Data collection top

XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	1328 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1281 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.021
Detector resolution: 10.0000 pixels mm^-1	θ_max = 28.0°, θ_min = 2.6°
ω scans	h = −17→17
Absorption correction: numerical (CrysAlisPro; Rigaku OD, 2021)	k = −13→13
T_min = 0.853, T_max = 0.962	l = −11→11
9320 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0245P)² + 3.4224P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
1328 reflections	Δρ_max = 0.42 e Å⁻³
97 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Ni	0.000000	0.22315 (3)	0.250000	0.00786 (10)
Al	0.17218 (4)	0.42251 (5)	0.07491 (6)	0.00453 (12)
P1	0.29302 (4)	0.62530 (5)	0.32906 (5)	0.00592 (11)
P2	0.000000	0.49528 (6)	0.250000	0.00488 (13)
N1	0.500000	0.3647 (3)	0.250000	0.0282 (7)
O1	0.20866 (11)	0.57928 (13)	0.16956 (15)	0.0093 (3)
O2	0.26781 (11)	0.77156 (13)	0.34168 (16)	0.0091 (3)
O3	0.27630 (11)	0.54936 (13)	0.47120 (15)	0.0092 (3)
O4	0.07228 (11)	0.39900 (13)	0.19411 (16)	0.0085 (3)
O5	0.06302 (11)	0.58454 (13)	0.38790 (15)	0.0088 (3)
O6	0.09292 (11)	0.10007 (14)	0.17281 (17)	0.0119 (3)
O7	0.11014 (13)	0.20652 (15)	0.48072 (18)	0.0185 (3)
H71	0.147718	0.262282	0.538535	0.028*
H72	0.150318	0.137982	0.497836	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.00760 (16)	0.00725 (17)	0.00974 (17)	0.000	0.00416 (12)	0.000
Al	0.0051 (2)	0.0041 (2)	0.0044 (2)	0.00028 (18)	0.00137 (19)	0.00000 (17)
P1	0.0066 (2)	0.0055 (2)	0.0065 (2)	−0.00124 (15)	0.00321 (16)	−0.00082 (15)
P2	0.0047 (3)	0.0056 (3)	0.0045 (3)	0.000	0.0017 (2)	0.000
N1	0.0316 (16)	0.0160 (13)	0.0391 (17)	0.000	0.0143 (14)	0.000
O1	0.0120 (6)	0.0080 (6)	0.0078 (6)	−0.0016 (5)	0.0028 (5)	−0.0024 (5)
O2	0.0106 (6)	0.0065 (6)	0.0110 (6)	−0.0018 (5)	0.0044 (5)	−0.0021 (5)
O3	0.0111 (6)	0.0091 (6)	0.0090 (6)	0.0006 (5)	0.0056 (5)	0.0019 (5)
O4	0.0093 (6)	0.0073 (6)	0.0114 (6)	0.0005 (5)	0.0069 (5)	−0.0001 (5)
O5	0.0087 (6)	0.0097 (6)	0.0064 (6)	−0.0007 (5)	0.0002 (5)	−0.0020 (5)
O6	0.0085 (6)	0.0111 (6)	0.0183 (7)	−0.0002 (5)	0.0075 (5)	−0.0026 (5)
O7	0.0192 (8)	0.0153 (7)	0.0149 (7)	0.0010 (6)	−0.0032 (6)	−0.0033 (6)

Geometric parameters (Å, º) top

Ni—O6	2.0052 (13)	Al—O4	1.9271 (14)
Ni—O6ⁱ	2.0052 (13)	P1—O6^iv	1.5180 (14)
Ni—O7ⁱ	2.0799 (15)	P1—O2	1.5361 (14)
Ni—O7	2.0799 (15)	P1—O3	1.5371 (13)
Ni—O4	2.1512 (13)	P1—O1	1.5502 (13)
Ni—O4ⁱ	2.1513 (13)	P2—O5ⁱ	1.5253 (13)
Ni—P2	2.7695 (7)	P2—O5	1.5253 (13)
Al—O2ⁱⁱ	1.7731 (14)	P2—O4	1.5444 (13)
Al—O1	1.7908 (14)	P2—O4ⁱ	1.5444 (13)
Al—O5ⁱⁱⁱ	1.7979 (14)	O7—H71	0.8131
Al—O3ⁱⁱⁱ	1.8818 (14)	O7—H72	0.8572

O6—Ni—O6ⁱ	102.68 (8)	O5ⁱⁱⁱ—Al—O4	90.50 (6)
O6—Ni—O7ⁱ	85.94 (6)	O3ⁱⁱⁱ—Al—O4	176.10 (6)
O6ⁱ—Ni—O7ⁱ	88.23 (6)	O6^iv—P1—O2	113.48 (8)
O6—Ni—O7	88.23 (6)	O6^iv—P1—O3	108.43 (8)
O6ⁱ—Ni—O7	85.94 (6)	O2—P1—O3	109.89 (8)
O7ⁱ—Ni—O7	170.66 (9)	O6^iv—P1—O1	111.07 (8)
O6—Ni—O4	94.96 (5)	O2—P1—O1	104.47 (8)
O6ⁱ—Ni—O4	162.34 (5)	O3—P1—O1	109.41 (8)
O7ⁱ—Ni—O4	93.78 (6)	O5ⁱ—P2—O5	106.90 (11)
O7—Ni—O4	93.98 (6)	O5ⁱ—P2—O4	111.02 (7)
O6—Ni—O4ⁱ	162.34 (5)	O5—P2—O4	113.39 (7)
O6ⁱ—Ni—O4ⁱ	94.96 (5)	O5ⁱ—P2—O4ⁱ	113.39 (7)
O7ⁱ—Ni—O4ⁱ	93.98 (6)	O5—P2—O4ⁱ	111.02 (7)
O7—Ni—O4ⁱ	93.78 (6)	O4—P2—O4ⁱ	101.24 (10)
O4—Ni—O4ⁱ	67.41 (7)	O5ⁱ—P2—Ni	126.55 (5)
O6—Ni—P2	128.66 (4)	O5—P2—Ni	126.55 (5)
O6ⁱ—Ni—P2	128.66 (4)	O4—P2—Ni	50.62 (5)
O7ⁱ—Ni—P2	94.67 (4)	O4ⁱ—P2—Ni	50.62 (5)
O7—Ni—P2	94.67 (4)	P1—O1—Al	133.93 (9)
O4—Ni—P2	33.70 (3)	P1—O2—Al^iv	142.39 (9)
O4ⁱ—Ni—P2	33.71 (3)	P1—O3—Al^v	128.58 (8)
O2ⁱⁱ—Al—O1	124.32 (7)	P2—O4—Al	132.86 (8)
O2ⁱⁱ—Al—O5ⁱⁱⁱ	117.33 (7)	P2—O4—Ni	95.68 (6)
O1—Al—O5ⁱⁱⁱ	118.28 (7)	Al—O4—Ni	130.40 (7)
O2ⁱⁱ—Al—O3ⁱⁱⁱ	92.12 (6)	P2—O5—Al^v	140.21 (9)
O1—Al—O3ⁱⁱⁱ	87.71 (6)	P1ⁱⁱ—O6—Ni	126.87 (8)
O5ⁱⁱⁱ—Al—O3ⁱⁱⁱ	93.10 (6)	Ni—O7—H71	129.9
O2ⁱⁱ—Al—O4	87.54 (6)	Ni—O7—H72	115.6
O1—Al—O4	89.27 (6)	H71—O7—H72	104.1

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O1^v	0.81	1.99	2.790 (2)	167
O7—H72···O3^vi	0.86	2.11	2.961 (2)	170

Symmetry codes: (v) x, −y+1, z+1/2; (vi) −x+1/2, −y+1/2, −z+1.

Selected bond lengths (Å) in (NH₄)MAl₂(PO₄)₃·2H₂O [M = Mn (I) and Ni (II)] top

	(I)	(II)
PO₄ tetrahedra
P1—O6^iv	1.5152 (19)	1.5180 (14)
P1—O2	1.5342 (19)	1.5361 (14)
P1—O3	1.5350 (18)	1.5371 (13)
P1—O1	1.5493 (18)	1.5502 (13)
P2—O5	1.5294 (18)	1.5253 (13)
P2—O4	1.5420 (18)	1.5444 (13)

AlO₅ trigonal bipyramid
Al—O2ⁱⁱ	1.7847 (19)	1.7731 (14)
Al—O1	1.8013 (19)	1.7908 (14)
Al—O5^iv	1.8080 (18)	1.7979 (14)
Al—O3^iv	1.8886 (19)	1.8818 (14)
Al—O4	1.9320 (18)	1.9271 (14)

MnO₆ octahedra
M—O6	2.0799 (19)	2.0052 (13)
M—O7	2.1990 (20)	2.0799 (15)
M—O4	2.2805 (18)	2.1512 (13)
O4···O4ⁱ	2.407 (5)	2.387 (4)
O6···O7	2.950 (3)	2.785 (2)
O6···O7ⁱ	2.962 (4)	2.844 (3)
O4···O6	3.192 (3)	3.065 (2)
O4···O7	3.254 (3)	3.089 (2)
O4···O7ⁱ	3.291 (3)	3.094 (3)
O6···O6ⁱ	3.372 (5)	3.132 (4)

Symmetry codes: (i) -x, y, -z + 1/2; (ii) -x + 1/2, y - 1/2, -z + 1/2; (iv) x, -y + 1, z - 1/2; (vi) -x + 1/2, y + 1/2, -z + 1.

Funding information

This work was supported financially by Grant-in-Aid for Scientific Research on Innovative Areas No. 18H05456.

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