Structural features of the oxidonitridophosphates K3MIII(PO3)3N (MIII = Al, Ga)

Zatovsky, I.V.; Ogorodnyk, I.V.; Baumer, V.N.; Zhilyak, I.D.; Horda, R.V.; Strutynska, N.Y.

doi:10.1107/S2056989021011336

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ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1213-1218

https://doi.org/10.1107/S2056989021011336

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Structural features of the oxidonitridophosphates K₃M^III(PO₃)₃N (M^III = Al, Ga)

Igor V. Zatovsky,^a ^* Ivan V. Ogorodnyk,^b Vyacheslav N. Baumer,^c Ivan D. Zhilyak,^d Ruslana V. Horda ^a and Nataliya Yu. Strutynska ^e

^aF.D. Ovcharenko Institute of Biocolloidal Chemistry, NAS Ukraine, 42 Acad. Vernadskoho blv., 03142 Kyiv, Ukraine, ^bShimUkraine LLC, 18 Chigorina Str., office 429, 01042 Kyiv, Ukraine, ^cSTC "Institute for Single Crystals", NAS of Ukraine, 60 Lenin ave., 61001 Kharkiv, Ukraine, ^dFaculty of Horticulture, Ecology and Plants Protection, Uman National University of Horticulture, 1 Instytutska str., 20305 Uman, Cherkassy region, Ukraine, and ^eDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska str., 01601, Kyiv, Ukraine
^*Correspondence e-mail: zvigo@ukr.net

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 October 2021; accepted 27 October 2021; online 2 November 2021)

Cubic crystals of tripotassium aluminium (or gallium) nitridotriphosphate, K₃M^III(PO₃)₃N (M^III = Al, Ga), were grown by application of the self-flux method. In their isostructural crystal structures, all metal cations and the N atom occupy special positions with site symmetry 3, while the P and O atoms are situated in general positions. The three-dimensional framework of these oxidonitridophosphates is built up from [M^IIIO₆] octahedra linked together via (PO₃)₃N groups. The latter are formed from three PO₃N tetrahedra sharing a common N atom. The coordination environments of the three potassium cations are represented by two types of polyhedra, viz. KO₉ for one and KO₉N for the other two cations. An unusual tetradentate type of coordination for the latter potassium cations by the (PO₃)₃N^6– anion is observed. These K₃M^III(PO₃)₃N (M^III = Al, Ga) compounds are isostructural with the Na₃M^III(PO₃)₃N (M^III = Al, V, Ti) compounds.

Keywords: crystal structure; isotypism; (PO₃)₃N anion; cubic symmetry; self-flux crystal growth.

CCDC references: 2118192; 2118191

1. Chemical context

Oxidonitridophosphates with general compositions M^I₃M^III(PO₃)₃N and M^I₂M^II₂(PO₃)₃N (M^I = Li, Na, K; M^III = Al, Cr, Ga, V and Ti; M^II = Mg, Fe) have been prepared by solid-state synthesis (Feldmann, 1987a ,b ; Massiot et al., 1996 ; Conanec et al., 1996 ), high-temperature thermal ammonolysis (Kim & Kim, 2013 ; Kim et al., 2017 ; Zhang et al., 2017 ), flux-growth (Zatovsky et al., 2006 ) or solid–solid ion-exchange (Liu et al., 2018 ). In recent years, oxidonitridophosphates containing the (PO₃)₃N^6– anion have been intensively studied as promising cathode materials for Na-ion and Li-ion batteries. In particular, ionic conductivities and redox properties were investigated in detail for Na₃Ti(PO₃)₃N (Liu et al., 2014 ), Na₃V(PO₃)₃N (Reynaud et al., 2017 ; Kim et al., 2017; Zhang et al., 2017; Xiao et al., 2021 ; Wang et al., 2021 ), Li₃V(PO₃)₃N (Liu et al., 2018), Na₂Fe₂(PO₃)₃N and Li₂Fe₂(PO₃)₃N (Liu et al., 2013 ), Na₂Mg₂(PO₃)₃N (Cosby et al., 2020 ), and Li₂Mg₂(PO₃)₃N (Liu et al., 2017 ). In addition, rare-earth-doped Na₃Al(PO₃)₃N has been studied as a promising phosphor (Bang et al., 2013 ). However, the structural data for oxidonitridophosphates include only Na- or Li-containing compounds (Massiot et al., 1996; Zatovsky et al., 2006; Kim & Kim, 2013; Liu et al., 2013, 2017, 2018; Zhang et al., 2017).

In this communication, we report the flux-growth synthesis, structural characterization and FTIR spectra for the two K-containing oxidonitridophosphates K₃Al(PO₃)₃N (I) and K₃Ga(PO₃)₃N (II).

2. Structural commentary

Compounds (I) and (II) (Fig. 1) are isotypic and crystallize in the cubic Na₃Al(PO₃)₃N structure in space-group type P2₁3. The K, Al (or Ga) and N atoms are localized on threefold rotation axes (Wyckoff position 4 a), and the P and all O atoms occupy general 12 b sites (Fig. 1). As shown in Fig. 2, the crystal structures of the K₃M^III(PO₃)₃N (M^III = Al, Ga) title compounds consist of [M^IIIO₆] octahedra and (PO₃)₃N^6– anions, which are linked via vertices, forming a three-dimensional framework. The (PO₃)₃N^6– anion is built up from three PO₃N tetrahedra sharing a common N vertex atom. The P—O bond lengths for both structures range between 1.473 (9) and 1.534 (3) Å (Tables 1 and 2), while the P—N bond lengths are 1.7084 (12) and 1.701 (4) Å for (I) and (II), respectively. The lengths of the P—O and P—N bonds are similar to those found in the isotypic oxidonitridophosphates such as Na₃Al(PO₃)₃N (Conanec et al., 1994 , 1996), Na₃Ti(PO₃)₃N (Zatovsky et al., 2006), or Na₃V(PO₃)₃N (Kim & Kim, 2013). The octahedral coordination environments around M^III are slightly distorted, as indicated by the different M^III—O bond lengths (Tables 1 and 2). The [M^IIIO₆] octahedra are slightly squeezed along the cubic cell diagonal. The average Al—O and Ga—O distances are 1.907 (3) and 1.963 (9) Å, respectively. These values are close to the sums of the ionic radii (Shannon, 1976 ) of Al³⁺ and O^2– (1.92 Å) and Ga³⁺ and O²⁻ (2.00 Å), respectively.

Table 1
Selected geometric parameters (Å, °) for (I)

K1—O3ⁱ	2.623 (3)	K3—N1	3.340 (6)
K1—O1ⁱⁱ	2.761 (3)	K3—O3^iv	3.379 (3)
K1—O2ⁱⁱ	3.261 (3)	Al1—O1^v	1.905 (3)
K2—O3ⁱⁱⁱ	2.765 (3)	Al1—O2^iv	1.909 (3)
K2—N1	2.904 (6)	P1—O3	1.493 (3)
K2—O1ⁱⁱⁱ	2.967 (3)	P1—O1	1.530 (3)
K2—O2	3.263 (3)	P1—O2	1.534 (3)
K3—O3	2.679 (3)	P1—N1	1.7084 (12)
K3—O2^iv	2.803 (3)

O3—P1—O1	111.58 (17)	O1—P1—N1	105.82 (13)
O3—P1—O2	113.45 (16)	O2—P1—N1	105.20 (17)
O1—P1—O2	109.85 (16)	P1^vi—N1—P1	118.53 (8)
O3—P1—N1	110.5 (2)
Symmetry codes: (i) $[-y+1, z-{\script{1\over 2}}, -x+{\script{1\over 2}}]$ ; (ii) $[-z+{\script{1\over 2}}, -x, y-{\script{1\over 2}}]$ ; (iii) $[z-{\script{1\over 2}}, -x+{\script{1\over 2}}, -y+1]$ ; (iv) $[-z+1, x+{\script{1\over 2}}, -y+{\script{3\over 2}}]$ ; (v) $[-z+{\script{3\over 2}}, -x+1, y+{\script{1\over 2}}]$ ; (vi) z, x, y.

Table 2
Selected geometric parameters (Å, °) for (II)

K1—O3ⁱ	2.642 (8)	K3—N1	3.310 (18)
K1—O1ⁱⁱ	2.807 (9)	K3—O3^v	3.412 (8)
K1—O2ⁱⁱⁱ	3.216 (8)	Ga1—O2^vi	1.968 (9)
K2—O3^iv	2.808 (9)	Ga1—O2^vii	1.968 (9)
K2—O1ⁱ	2.925 (9)	P1—O3	1.473 (9)
K2—N1	2.977 (18)	P1—O2	1.516 (9)
K2—O2	3.287 (8)	P1—O1	1.524 (9)
K3—O3	2.665 (9)	P1—N1	1.701 (4)
K3—O2^v	2.785 (8)

O3—P1—O2	113.8 (5)	O2—P1—N1	107.0 (5)
O3—P1—O1	112.1 (5)	O1—P1—N1	106.8 (4)
O2—P1—O1	107.9 (5)	P1—N1—P1^viii	118.8 (2)
O3—P1—N1	108.9 (7)
Symmetry codes: (i) $[z-{\script{1\over 2}}, -x+{\script{1\over 2}}, -y+1]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-z+{\script{1\over 2}}, -x, y-{\script{1\over 2}}]$ ; (iv) $[-y+1, z-{\script{1\over 2}}, -x+{\script{1\over 2}}]$ ; (v) $[-z+1, x+{\script{1\over 2}}, -y+{\script{3\over 2}}]$ ; (vi) $[-y+{\script{3\over 2}}, -z+1, x+{\script{1\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (viii) z, x, y.

Figure 1
A view of the asymmetric units of K₃Al(PO₃)₃N (I) and K₃Ga(PO₃)₃N (II), with displacement ellipsoids drawn at the 50% probability level.

Figure 2
[M^IIIO₆] octahedra and `three-blade propeller'-type anions (PO₃)₃N^6– as principle building units for formation of the three-dimensional framework of (I) and (II).

Fig. 3 shows the coordination environments of potassium cations for (I) and (II). K1 has nine O-atom neighbors with K—O distances ranging from 2.623 (3) to 3.261 (3) Å, which includes three mono- and three bidentately coordinating (PO₃)₃N^6– anions. K2O₉N and K3O₉N polyhedra are formed as a result of one tetra- and three bidentately coordinating oxidonitridophosphate anions. In the latter case, the upper boundary for K—O distances is 3.412 (8) Å; K2—N distances are 2.904 (6) and 2.977 (18) Å and K3—N contacts are 3.340 (6) and 3.310 (18) Å for (I) and (II), respectively. The coordination environments around the alkali metal for K-containing oxidonitridophosphates (K2O₉N and K3O₉N polyhedra) differ from those of the Na-containing compounds (Na2O₆N and Na3O₆N polyhedra). In addition, the (PO₃)₃N^6– anions coordinate the two potassium cations in a tetradentate manner (Fig. 4). As is shown schematically in Fig. 4 and in Table 3 for the isotypic M^I₃M^III(PO₃)₃N compounds, the M^I, M^III and N atoms are arranged along the [111] direction in the sequence –M1^I–M2^I–N–M3^I–M^III–M1^I– whereby the M2^I—N—M3^I distances change in a different manner. In case of (I) and (II), the shape of the (PO₃)₃N^6– anion is similar (the P—N distances are about 1.70 Å and the P—N—K3 angles are within 83-84°; Tables 1 and 2). For the Na-containing analogues, the P—N bond is slightly larger (1.71–1.74 Å) and the P—N—Na3 angles are smaller within a wider range from 75 to 78° (Conanec et al., 1994, 1996; Zatovsky et al., 2006; Kim & Kim, 2013).

Table 3
BVS results (v.u.) for (I) and (II)

Central Atom	(I)	(II)
Al1/Ga1	3.004	3.197
K1	1.486	1.400
K2	1.122	1.069
K3	1.315	1.360
P1	3 × 4.903	3 × 5.084
Σ	21.636	22.278

Figure 3
The coordination environment of potassium cations in (I) and (II).

Figure 4
Coordination of K2 and K3 cations by the (PO₃)₃N^6– anion for (I) and (II).

To clarify some points regarding the structural changes we have calculated the bond-valence sums (BVS) for the K, P and Al atoms (I) and Ga atoms (II), respectively. Parameters were taken from Brown & Altermatt (1985 ) and for the K—N bond from Brese & O'Keeffe (1991 ). The BVS for positively charged atoms in (I) is 21.64 v.u. and 22.28 v.u. for (II) while the sum of the charges of nine O and one N atom is equal to 21 v.u. (Table 4). The higher values for the Ga-containing compound might be explained as follows. The BVS for Al in [AlO₆] was found to be 3.00 v.u. while for Ga in [GaO₆] it is 3.20 v.u. The remaining atoms also show a slight overbonding (Table 4). We suppose that the anionic part (PO₃)₃N^6– is rigid enough and cannot be stretched to larger sizes relative to the larger [GaO₆] octahedron into a more expanded framework. This is the reason why shorter interatomic K—O and P—O distances are observed in the structure of (II) compared to that of (I) (Tables 1 and 2). As expected, the unit-cell parameters of (I) are smaller than for (II), in good agreement with the ionic radii of Al³⁺ and Ga³⁺ (Shannon, 1976). In other words, the rigid and almost flat `three-blade propeller' anions combine with [M^IIIO₆] octahedra to form the framework in which the cavities for the alkali cations become smaller as greater octahedra are involved. Moreover, the greater [M^IIIO₆] octahedra strongly influence the `three-blade propeller' anion, resulting in slightly shorter P—O and P—N bonds. On the other hand, the local environments of the K cations should also be mentioned. In the K2O₉N polyhedron, the BVS for K2 is 1.12 v.u. in (I) and 1.07 in (II). The contribution to the K2—N1 bond to the valence sum is 0.12 v.u. for (I) and 0.10 for (II). These high values indicate a strong interaction between the two atoms. The cavities in which K1 and K2 are located become larger with longer or almost the same K⋯O and K⋯N contacts, while the cavities in which K3 is situated become smaller with shortened K⋯O contacts in (II) in comparison with (I). BVS calculations for the phosphate tetrahedra show similar results (Table 4).

Table 4
Distances (Å) between atoms for (I), (II) and isotypic M^I₃M^III(PO₃)₃N compounds along [111]

Compound	Atomic distance between neighboring atoms	Reference
Na₃Al(PO₃)₃N	–Na1–3.438–Na2–2.875–N–3.197–Na3–3.068–Al–3.486–Na1–	Massiot et al. (1996)
Na₃Ti(PO₃)₃N	–Na1–3.448–Na2–3.078–N–3.188–Na3–3.100–Ti–3.638–Na1–	Zatovsky et al. (2006)
Na₃V(PO₃)₃N	–Na1–3.477–Na2–2.947–N–3.234–Na3–3.100–V–3.606–Na1–	Kim & Kim (2013)
K₃Al(PO₃)₃N	–K1–3.723–K2–2.904–N–3.340–K3–3.400–Al–3.429–K1–	This work
K₃Ga(PO₃)₃N	–K1–3.747–K2–2.978–N–3.310–K3–3.350–Ga–3.470–K1–	This work

It should also be noted that further theoretical calculations of the electronic structure can bring final clarity to the principles of bonding of alkali cations with (PO₃)₃N^6– anions in K₃M^III(PO₃)₃N compounds. This could be a way for the creation of new materials with desired properties based on K-containing oxidonitridophosphates.

3. Synthesis and crystallization

For the synthesis of (I) and (II), KH₂PO₄, K₄P₂O₇·10H₂O, urea, Al₂O₃ or Ga₂O₃ (all analytically or extra pure grade) were used as initial reagents. The sequence of preparation procedure was as follows: (1) phosphates KPO₃ and K₄P₂O₇ were each prepared by calcining KH₂PO₄ and K₄P₂O₇·10H₂O at 873 K; (2) a mixture of 20.07 g of KPO₃, 13.21 g of K₄P₂O₇ and 30.03 g of urea (molar ratio K:P = 1:1.32, urea:P = 2:1) ground in an agate mortar, was heated to complete degassing at 623 K in a porcelain dish. The resulting solid was reground and heated to become a homogeneous liquid at 1023 K and then quenched by pouring the melt onto a copper sheet to form a glass. The glass was crushed using a mill, and a powder with a particle size of less than 125 µm was separated. According to chemical analysis, the prepared glass had the composition K_1.32PO_2.43N_0.50; (3) a mixture of 10 g of glass (K_1.32PO_2.43N_0.50) and 0.3 g of Al₂O₃ or 0.7 g of Ga₂O₃ powders were placed into porcelain crucibles and heated up to 1043 K and then cooled to 923 K at a rate of 25 K h⁻¹. After cooling to room temperature, colorless tetrahedral crystals of (I) or (II) were washed with deionized water. Elemental analysis indicated the presence of K, Al (or Ga), P and N in the atomic ratio 3:1:3:1.

The growing of well-shaped crystals of (I) and (II) suitable for single crystal X-ray diffraction analysis was one of main tasks during the present study. Hence, a similar way for the preparation of the potassium-containing phosphates to that for the previously reported sodium-containing compounds was applied, following the self-flux method for the preparation of crystalline nitrogen-containing phosphates (Zatovsky et al., 2006). Thermal decomposition of urea is a multistage process and leads to the formation of C₃N₄ (Wang et al., 2017 ). The initial M^I–P–O–N (M^I = alkali metal) melt can be obtained by the reaction of urea with alkali metal phosphates, when a mixture of phosphates and C₃N₄ interact. The change of the phosphate:C₃N₄ ratio (or phosphate:urea) and the nature of the alkali metal affects the composition of the resulting melt. In our case, the molar ratio of K:P was chosen to be 1:1.32 because a mixture of KPO₃ and K₄P₂O₇ in this ratio has the lowest melting point close to 886 K, and the urea:P ratio was set to 2:1. As a result, a glass of composition K_1.32PO_2.43N_0.50 was obtained.

The solubilities of Al₂O₃ and Ga₂O₃ in the K_1.32PO_2.43N_0.50 self-fluxes differ significantly. Crystallization of compound (I) occurs as a result of the interaction of self-fluxes and 2–4%wt. Al₂O₃. The formation of a mixture of (I) and Al₂O₃ was observed when the initial amount of aluminum oxide was higher than 5%wt. The solubility of Ga₂O₃ in the self-flux is about 7%wt. at 1043 K, and subsequent cooling of the homogeneous melt led to the crystallization of compound (II). In all cases, the amount of nitrogen in the self-fluxes rapidly decreases above 1063 K. This process occurs due to the thermal instability of P—N bonds at high temperatures, and leads to a redox reaction with the release of nitrogen and phosphorus. The latter vaporizes from the phosphate melts and starts to burn, which can be observed by periodical sparks on the melt surface (Zatovsky et al., 2000 ). As a result, K–M^III–P–O (M^III = Al, Ga) melts prone to vitrifying are formed.

The obtained compounds (I) and (II) were further characterized using FTIR spectroscopy; FTIR spectra were collected at room temperature on KBr discs using a Thermo NICOLET Nexus 470 spectrophotometer. As can be seen in Fig. 5, the spectra of (I) and (II) are similar with respect to intensities and band positions (the difference in the band positions does not exceed 27 cm⁻¹). The characteristic bands are in good agreement with the presence of the N(PO₃)₃^6– anion with C_3v symmetry, which provides for a set of vibration modes: 6A1 + 5A2 + 11E (3A1 + A2 + 4E belong to stretching vibrations, and 3A1 + 4A2 + 7E are due to deformation vibrations). As shown in Fig. 5, the following regions can be distinguished in the FTIR spectra: (1) the bands in the region between 980 and 1220 cm⁻¹ are assigned to ν_as and ν_s(PO₃) stretching vibrations [four absorption bands in the frequency range between 1070 and 1220 cm⁻¹ belong to ν_as(P—O), and two bands of between 980 and 1060 cm⁻¹ correspond to ν_s(P—O)]; (2) ν_as(P—N—P) and ν_s(P—N—P) bands can be observed in the regions between 920 and 950 cm⁻¹ and around 920 cm⁻¹, respectively; (3) the range between 400 and 680 cm⁻¹ includes absorption bands due to δ (P—O) and ν (Al—O) or ν (Ga—O) vibrations. In summary, in terms of the set of absorption bands, the FTIR spectra of the N(PO₃)₃^6– anion resemble those of the P₂O₇^4– anion.

Figure 5
FTIR spectra of (I) and (II).

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. As a result of the shapes of the obtained crystals, their cell parameters and chemical compositions, we had expected that both structures should be isostructural with the previously reported Na₃Al(PO₃)₃N and Na₃Ti(PO₃)₃N structures. In fact, analysis of the single-crystal data showed that both compounds crystallize in the same space group type (P2₁3) as the Na-containing oxidonitridophosphates. Originally, the crystal structures were solved by direct methods but we also performed refinements using the atomic coordinates of Na₃Ti(PO₃)₃N as a starting model. The results were the same, confirming that both structures are isostructural with Na₃Ti(PO₃)₃N (as well as with all previously reported cubic oxionitridophosphates with the same formula type).

Table 5
Experimental details

	(I)	(II)
Crystal data
Chemical formula	K₃Al(NP₃O₉)	K₃Ga(NP₃O₉)
M_r	395.2	437.94
Crystal system, space group	Cubic, P2₁3	Cubic, P2₁3
Temperature (K)	293	293
a (Å)	9.6970 (4)	9.7313 (9)
V (Å³)	911.83 (11)	921.5 (3)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	2.16	4.90
Crystal size (mm)	0.15 × 0.12 × 0.1	0.12 × 0.07 × 0.04

Data collection
Diffractometer	Oxford Diffraction Xcalibur-3	Oxford Diffraction Xcalibur-3
Absorption correction	Multi-scan (Blessing, 1995 )	Multi-scan (Blessing, 1995)
T_min, T_max	0.844, 0.869	0.738, 0.804
No. of measured, independent and observed [I > 2σ(I)] reflections	7172, 745, 667	4964, 753, 517
R_int	0.078	0.155
(sin θ/λ)_max (Å⁻¹)	0.660	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.052, 1.05	0.059, 0.102, 1
No. of reflections	745	753
No. of parameters	53	53
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.27	0.67, −0.60
Absolute structure	Flack x determined using 269 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	Flack x determined using 153 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	−0.02 (6)	0.03 (5)
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXS2013/1 (Sheldrick, 2008), SHELXL2018/3 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2006 ), WinGX (Farrugia, 2012 ), enCIFer (Allen et al., 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2118192; 2118191

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989021011336/wm5621sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011336/wm5621Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021011336/wm5621IIsup3.hkl

checkCIF report

Computing details top

For both structures, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006). Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for (I); SHELXS2013/1 (Sheldrick, 2008) for (II). Program(s) used to refine structure: SHELXL (Sheldrick, 2015) for (I); SHELXL2018/3 (Sheldrick, 2015) for (II). For both structures, molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Tripotassium aluminium nitridotriphosphate (I) top

Crystal data top

K₃Al(NP₃O₉)	D_x = 2.879 Mg m⁻³
M_r = 395.2	Mo Kα radiation, λ = 0.71073 Å
Cubic, P2₁3	Cell parameters from 7172 reflections
Hall symbol: P 2ac 2ab 3	θ = 3.0–28.0°
a = 9.6970 (4) Å	µ = 2.16 mm⁻¹
V = 911.83 (11) Å³	T = 293 K
Z = 4	Tetrahedron, colorless
F(000) = 776	0.15 × 0.12 × 0.1 mm

Data collection top

Oxford Diffraction Xcalibur-3 diffractometer	667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
φ and ω scans	θ_max = 28.0°, θ_min = 3.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −12→12
T_min = 0.844, T_max = 0.869	k = −12→10
7172 measured reflections	l = −12→12
745 independent reflections

Refinement top

Refinement on F²	'w = 1/[σ²(F_o²) + (0.0211P)²] where P = (F_o² + 2F_c²)/3'
Least-squares matrix: full	(Δ/σ)_max < 0.001
R[F² > 2σ(F²)] = 0.026	Δρ_max = 0.27 e Å⁻³
wR(F²) = 0.052	Δρ_min = −0.27 e Å⁻³
S = 1.05	Extinction correction: SHELXL2018/3 (Sheldrick, 2015)
745 reflections	Extinction coefficient: 0.0037 (14)
53 parameters	Absolute structure: Flack x determined using 269 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.02 (6)

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
K1	0.04655 (9)	0.04655 (9)	0.04655 (9)	0.0178 (4)
K2	0.26820 (10)	0.26820 (10)	0.26820 (10)	0.0195 (4)
K3	0.63996 (10)	0.63996 (10)	0.63996 (10)	0.0207 (4)
Al1	0.84238 (12)	0.84238 (12)	0.84238 (12)	0.0095 (5)
P1	0.32280 (11)	0.56862 (11)	0.46909 (11)	0.0088 (3)
N1	0.4411 (3)	0.4411 (3)	0.4411 (3)	0.0073 (11)
O1	0.2129 (3)	0.5055 (3)	0.5631 (3)	0.0107 (6)
O2	0.2606 (3)	0.5994 (3)	0.3269 (3)	0.0120 (6)
O3	0.3898 (3)	0.6909 (3)	0.5344 (3)	0.0161 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0178 (4)	0.0178 (4)	0.0178 (4)	−0.0037 (4)	−0.0037 (4)	−0.0037 (4)
K2	0.0195 (4)	0.0195 (4)	0.0195 (4)	−0.0034 (4)	−0.0034 (4)	−0.0034 (4)
K3	0.0207 (4)	0.0207 (4)	0.0207 (4)	−0.0040 (4)	−0.0040 (4)	−0.0040 (4)
Al1	0.0095 (5)	0.0095 (5)	0.0095 (5)	−0.0006 (5)	−0.0006 (5)	−0.0006 (5)
P1	0.0081 (5)	0.0087 (6)	0.0096 (5)	0.0003 (4)	0.0010 (4)	0.0003 (4)
N1	0.0073 (11)	0.0073 (11)	0.0073 (11)	0.0001 (13)	0.0001 (13)	0.0001 (13)
O1	0.0103 (15)	0.0108 (14)	0.0110 (14)	0.0004 (11)	0.0043 (12)	0.0021 (12)
O2	0.0116 (15)	0.0147 (15)	0.0099 (14)	0.0022 (12)	−0.0019 (12)	0.0007 (12)
O3	0.0163 (16)	0.0116 (16)	0.0204 (16)	−0.0023 (12)	−0.0019 (14)	−0.0037 (13)

Geometric parameters (Å, º) top

K1—O3ⁱ	2.623 (3)	K2—P1ⁱⁱ	3.4199 (12)
K1—O3ⁱⁱ	2.623 (3)	K3—O3^viii	2.679 (3)
K1—O3ⁱⁱⁱ	2.623 (3)	K3—O3^ix	2.679 (3)
K1—O1^iv	2.761 (3)	K3—O3	2.679 (3)
K1—O1^v	2.761 (3)	K3—O2^x	2.803 (3)
K1—O1^vi	2.761 (3)	K3—O2^xi	2.803 (3)
K1—O2^iv	3.261 (3)	K3—O2^xii	2.803 (3)
K1—O2^vi	3.261 (3)	K3—N1	3.340 (6)
K1—O2^v	3.261 (3)	K3—O3^x	3.379 (3)
K1—Al1^vii	3.429 (3)	K3—O3^xi	3.379 (3)
K1—P1^iv	3.5911 (13)	K3—O3^xii	3.379 (3)
K1—P1^vi	3.5911 (13)	K3—Al1	3.400 (3)
K2—O3ⁱⁱⁱ	2.765 (3)	K3—P1^xii	3.4997 (14)
K2—O3ⁱ	2.765 (3)	Al1—O1^xiii	1.905 (3)
K2—O3ⁱⁱ	2.765 (3)	Al1—O1^xiv	1.905 (3)
K2—N1	2.904 (6)	Al1—O1^xv	1.905 (3)
K2—O1ⁱⁱⁱ	2.967 (3)	Al1—O2^x	1.909 (3)
K2—O1ⁱ	2.967 (3)	Al1—O2^xi	1.909 (3)
K2—O1ⁱⁱ	2.967 (3)	Al1—O2^xii	1.909 (3)
K2—O2	3.263 (3)	P1—O3	1.493 (3)
K2—O2^viii	3.263 (3)	P1—O1	1.530 (3)
K2—O2^ix	3.263 (3)	P1—O2	1.534 (3)
K2—P1ⁱⁱⁱ	3.4199 (12)	P1—N1	1.7084 (12)

O3ⁱ—K1—O3ⁱⁱ	79.95 (10)	O2^x—K3—O3^xi	60.45 (8)
O3ⁱ—K1—O3ⁱⁱⁱ	79.95 (10)	O2^xi—K3—O3^xi	47.20 (7)
O3ⁱⁱ—K1—O3ⁱⁱⁱ	79.95 (10)	O2^xii—K3—O3^xi	99.58 (8)
O3ⁱ—K1—O1^iv	111.53 (9)	N1—K3—O3^xi	113.91 (5)
O3ⁱⁱ—K1—O1^iv	165.73 (9)	O3^x—K3—O3^xi	104.69 (6)
O3ⁱⁱⁱ—K1—O1^iv	109.72 (8)	O3^viii—K3—O3^xii	143.68 (7)
O3ⁱ—K1—O1^v	109.72 (8)	O3^ix—K3—O3^xii	66.44 (10)
O3ⁱⁱ—K1—O1^v	111.53 (9)	O3—K3—O3^xii	111.63 (2)
O3ⁱⁱⁱ—K1—O1^v	165.73 (9)	O2^x—K3—O3^xii	99.58 (8)
O1^iv—K1—O1^v	57.44 (9)	O2^xi—K3—O3^xii	60.45 (8)
O3ⁱ—K1—O1^vi	165.73 (9)	O2^xii—K3—O3^xii	47.20 (7)
O3ⁱⁱ—K1—O1^vi	109.72 (8)	N1—K3—O3^xii	113.91 (5)
O3ⁱⁱⁱ—K1—O1^vi	111.53 (9)	O3^x—K3—O3^xii	104.69 (6)
O1^iv—K1—O1^vi	57.44 (9)	O3^xi—K3—O3^xii	104.69 (6)
O1^v—K1—O1^vi	57.44 (9)	O3^viii—K3—Al1	129.57 (6)
O3ⁱ—K1—O2^iv	63.69 (8)	O3^ix—K3—Al1	129.57 (6)
O3ⁱⁱ—K1—O2^iv	143.60 (8)	O3—K3—Al1	129.57 (6)
O3ⁱⁱⁱ—K1—O2^iv	94.55 (8)	O2^x—K3—Al1	34.15 (6)
O1^iv—K1—O2^iv	48.34 (7)	O2^xi—K3—Al1	34.15 (6)
O1^v—K1—O2^iv	81.13 (8)	O2^xii—K3—Al1	34.15 (6)
O1^vi—K1—O2^iv	105.77 (8)	N1—K3—Al1	180.00 (9)
O3ⁱ—K1—O2^vi	143.60 (8)	O3^x—K3—Al1	66.09 (5)
O3ⁱⁱ—K1—O2^vi	94.55 (8)	O3^xi—K3—Al1	66.09 (5)
O3ⁱⁱⁱ—K1—O2^vi	63.69 (8)	O3^xii—K3—Al1	66.09 (5)
O1^iv—K1—O2^vi	81.13 (8)	O3^viii—K3—P1^xii	168.66 (7)
O1^v—K1—O2^vi	105.77 (8)	O3^ix—K3—P1^xii	86.65 (6)
O1^vi—K1—O2^vi	48.34 (7)	O3—K3—P1^xii	101.22 (6)
O2^iv—K1—O2^vi	115.34 (4)	O2^x—K3—P1^xii	82.96 (7)
O3ⁱ—K1—O2^v	94.55 (8)	O2^xi—K3—P1^xii	64.96 (6)
O3ⁱⁱ—K1—O2^v	63.69 (8)	O2^xii—K3—P1^xii	25.22 (6)
O3ⁱⁱⁱ—K1—O2^v	143.60 (8)	N1—K3—P1^xii	125.75 (3)
O1^iv—K1—O2^v	105.77 (8)	O3^x—K3—P1^xii	79.71 (6)
O1^v—K1—O2^v	48.34 (7)	O3^xi—K3—P1^xii	112.01 (6)
O1^vi—K1—O2^v	81.13 (8)	O3^xii—K3—P1^xii	24.99 (5)
O2^iv—K1—O2^v	115.34 (4)	Al1—K3—P1^xii	54.25 (3)
O2^vi—K1—O2^v	115.34 (4)	O1^xiii—Al1—O1^xiv	88.28 (14)
O3ⁱ—K1—Al1^vii	132.11 (7)	O1^xiii—Al1—O1^xv	88.28 (14)
O3ⁱⁱ—K1—Al1^vii	132.11 (7)	O1^xiv—Al1—O1^xv	88.28 (14)
O3ⁱⁱⁱ—K1—Al1^vii	132.11 (7)	O1^xiii—Al1—O2^x	92.92 (12)
O1^iv—K1—Al1^vii	33.70 (6)	O1^xiv—Al1—O2^x	175.81 (12)
O1^v—K1—Al1^vii	33.70 (6)	O1^xv—Al1—O2^x	87.74 (11)
O1^vi—K1—Al1^vii	33.70 (6)	O1^xiii—Al1—O2^xi	87.74 (11)
O2^iv—K1—Al1^vii	77.34 (5)	O1^xiv—Al1—O2^xi	92.92 (12)
O2^vi—K1—Al1^vii	77.34 (5)	O1^xv—Al1—O2^xi	175.81 (12)
O2^v—K1—Al1^vii	77.34 (5)	O2^x—Al1—O2^xi	91.14 (13)
O3ⁱ—K1—P1^iv	88.98 (7)	O1^xiii—Al1—O2^xii	175.81 (12)
O3ⁱⁱ—K1—P1^iv	168.77 (7)	O1^xiv—Al1—O2^xii	87.74 (11)
O3ⁱⁱⁱ—K1—P1^iv	100.08 (6)	O1^xv—Al1—O2^xii	92.92 (12)
O1^iv—K1—P1^iv	23.55 (6)	O2^x—Al1—O2^xii	91.14 (14)
O1^v—K1—P1^iv	70.37 (6)	O2^xi—Al1—O2^xii	91.14 (13)
O1^vi—K1—P1^iv	80.83 (7)	O1^xiii—Al1—K3	126.47 (10)
O2^iv—K1—P1^iv	25.29 (5)	O1^xiv—Al1—K3	126.47 (10)
O2^vi—K1—P1^iv	95.49 (6)	O1^xv—Al1—K3	126.47 (10)
O2^v—K1—P1^iv	115.87 (6)	O2^x—Al1—K3	55.54 (10)
Al1^vii—K1—P1^iv	55.54 (3)	O2^xi—Al1—K3	55.54 (10)
O3ⁱ—K1—P1^vi	168.77 (7)	O2^xii—Al1—K3	55.54 (10)
O3ⁱⁱ—K1—P1^vi	100.08 (6)	O1^xiii—Al1—K1^xvi	53.53 (10)
O3ⁱⁱⁱ—K1—P1^vi	88.98 (7)	O1^xiv—Al1—K1^xvi	53.53 (10)
O1^iv—K1—P1^vi	70.37 (6)	O1^xv—Al1—K1^xvi	53.53 (10)
O1^v—K1—P1^vi	80.83 (7)	O2^x—Al1—K1^xvi	124.46 (10)
O1^vi—K1—P1^vi	23.55 (6)	O2^xi—Al1—K1^xvi	124.46 (10)
O2^iv—K1—P1^vi	115.87 (6)	O2^xii—Al1—K1^xvi	124.46 (10)
O2^vi—K1—P1^vi	25.29 (5)	K3—Al1—K1^xvi	180.00 (10)
O2^v—K1—P1^vi	95.49 (6)	O1^xiii—Al1—K2^xv	45.00 (8)
Al1^vii—K1—P1^vi	55.54 (3)	O1^xiv—Al1—K2^xv	125.19 (12)
P1^iv—K1—P1^vi	91.14 (4)	O1^xv—Al1—K2^xv	67.60 (8)
O3ⁱⁱⁱ—K2—O3ⁱ	75.10 (9)	O2^x—Al1—K2^xv	54.13 (8)
O3ⁱⁱⁱ—K2—O3ⁱⁱ	75.10 (9)	O2^xi—Al1—K2^xv	108.53 (8)
O3ⁱ—K2—O3ⁱⁱ	75.10 (9)	O2^xii—Al1—K2^xv	139.06 (9)
O3ⁱⁱⁱ—K2—N1	135.27 (6)	K3—Al1—K2^xv	106.68 (3)
O3ⁱ—K2—N1	135.27 (6)	K1^xvi—Al1—K2^xv	73.32 (3)
O3ⁱⁱ—K2—N1	135.27 (6)	O1^xiii—Al1—K2^xvii	67.60 (8)
O3ⁱⁱⁱ—K2—O1ⁱⁱⁱ	51.57 (8)	O1^xiv—Al1—K2^xvii	45.00 (8)
O3ⁱ—K2—O1ⁱⁱⁱ	123.82 (8)	O1^xv—Al1—K2^xvii	125.19 (12)
O3ⁱⁱ—K2—O1ⁱⁱⁱ	103.08 (8)	O2^x—Al1—K2^xvii	139.06 (9)
N1—K2—O1ⁱⁱⁱ	85.66 (6)	O2^xi—Al1—K2^xvii	54.13 (8)
O3ⁱⁱⁱ—K2—O1ⁱ	103.08 (8)	O2^xii—Al1—K2^xvii	108.53 (8)
O3ⁱ—K2—O1ⁱ	51.57 (8)	K3—Al1—K2^xvii	106.68 (3)
O3ⁱⁱ—K2—O1ⁱ	123.82 (8)	K1^xvi—Al1—K2^xvii	73.32 (3)
N1—K2—O1ⁱ	85.66 (6)	K2^xv—Al1—K2^xvii	112.11 (3)
O1ⁱⁱⁱ—K2—O1ⁱ	119.434 (16)	O1^xiii—Al1—K2^xii	125.19 (12)
O3ⁱⁱⁱ—K2—O1ⁱⁱ	123.82 (8)	O1^xiv—Al1—K2^xii	67.60 (8)
O3ⁱ—K2—O1ⁱⁱ	103.08 (8)	O1^xv—Al1—K2^xii	45.00 (8)
O3ⁱⁱ—K2—O1ⁱⁱ	51.57 (8)	O2^x—Al1—K2^xii	108.53 (8)
N1—K2—O1ⁱⁱ	85.66 (6)	O2^xi—Al1—K2^xii	139.06 (9)
O1ⁱⁱⁱ—K2—O1ⁱⁱ	119.434 (16)	O2^xii—Al1—K2^xii	54.13 (8)
O1ⁱ—K2—O1ⁱⁱ	119.434 (16)	K3—Al1—K2^xii	106.68 (3)
O3ⁱⁱⁱ—K2—O2	120.12 (8)	K1^xvi—Al1—K2^xii	73.32 (3)
O3ⁱ—K2—O2	155.11 (7)	K2^xv—Al1—K2^xii	112.11 (3)
O3ⁱⁱ—K2—O2	89.38 (7)	K2^xvii—Al1—K2^xii	112.11 (3)
N1—K2—O2	49.01 (5)	O3—P1—O1	111.58 (17)
O1ⁱⁱⁱ—K2—O2	78.18 (7)	O3—P1—O2	113.45 (16)
O1ⁱ—K2—O2	131.74 (9)	O1—P1—O2	109.85 (16)
O1ⁱⁱ—K2—O2	52.43 (7)	O3—P1—N1	110.5 (2)
O3ⁱⁱⁱ—K2—O2^viii	89.38 (7)	O1—P1—N1	105.82 (13)
O3ⁱ—K2—O2^viii	120.12 (8)	O2—P1—N1	105.20 (17)
O3ⁱⁱ—K2—O2^viii	155.11 (7)	O3—P1—K2^xviii	52.04 (12)
N1—K2—O2^viii	49.01 (5)	O1—P1—K2^xviii	60.00 (11)
O1ⁱⁱⁱ—K2—O2^viii	52.43 (7)	O2—P1—K2^xviii	124.79 (11)
O1ⁱ—K2—O2^viii	78.18 (7)	N1—P1—K2^xviii	130.01 (13)
O1ⁱⁱ—K2—O2^viii	131.74 (9)	O3—P1—K3^xix	72.98 (11)
O2—K2—O2^viii	81.64 (8)	O1—P1—K3^xix	98.65 (11)
O3ⁱⁱⁱ—K2—O2^ix	155.11 (7)	O2—P1—K3^xix	51.11 (11)
O3ⁱ—K2—O2^ix	89.38 (7)	N1—P1—K3^xix	151.24 (7)
O3ⁱⁱ—K2—O2^ix	120.12 (8)	K2^xviii—P1—K3^xix	75.63 (3)
N1—K2—O2^ix	49.01 (5)	O3—P1—K2	161.98 (12)
O1ⁱⁱⁱ—K2—O2^ix	131.74 (9)	O1—P1—K2	83.96 (11)
O1ⁱ—K2—O2^ix	52.43 (7)	O2—P1—K2	66.87 (11)
O1ⁱⁱ—K2—O2^ix	78.18 (7)	N1—P1—K2	54.41 (18)
O2—K2—O2^ix	81.64 (8)	K2^xviii—P1—K2	143.90 (4)
O2^viii—K2—O2^ix	81.64 (8)	K3^xix—P1—K2	114.96 (3)
O3ⁱⁱⁱ—K2—P1ⁱⁱⁱ	25.20 (6)	O3—P1—K3	43.33 (11)
O3ⁱ—K2—P1ⁱⁱⁱ	99.59 (7)	O1—P1—K3	113.68 (11)
O3ⁱⁱ—K2—P1ⁱⁱⁱ	86.94 (7)	O2—P1—K3	136.05 (12)
N1—K2—P1ⁱⁱⁱ	111.81 (3)	N1—P1—K3	68.57 (19)
O1ⁱⁱⁱ—K2—P1ⁱⁱⁱ	26.52 (6)	K2^xviii—P1—K3	74.83 (3)
O1ⁱ—K2—P1ⁱⁱⁱ	115.21 (6)	K3^xix—P1—K3	114.91 (3)
O1ⁱⁱ—K2—P1ⁱⁱⁱ	123.59 (6)	K2—P1—K3	122.98 (3)
O2—K2—P1ⁱⁱⁱ	98.86 (5)	O3—P1—K1^xx	119.94 (11)
O2^viii—K2—P1ⁱⁱⁱ	71.74 (5)	O1—P1—K1^xx	46.13 (11)
O2^ix—K2—P1ⁱⁱⁱ	152.93 (6)	O2—P1—K1^xx	65.25 (11)
O3ⁱⁱⁱ—K2—P1ⁱⁱ	99.59 (7)	N1—P1—K1^xx	128.30 (17)
O3ⁱ—K2—P1ⁱⁱ	86.94 (7)	K2^xviii—P1—K1^xx	78.82 (3)
O3ⁱⁱ—K2—P1ⁱⁱ	25.20 (6)	K3^xix—P1—K1^xx	61.97 (3)
N1—K2—P1ⁱⁱ	111.81 (3)	K2—P1—K1^xx	77.22 (3)
O1ⁱⁱⁱ—K2—P1ⁱⁱ	115.21 (6)	K3—P1—K1^xx	153.19 (4)
O1ⁱ—K2—P1ⁱⁱ	123.59 (6)	P1^viii—N1—P1^ix	118.53 (8)
O1ⁱⁱ—K2—P1ⁱⁱ	26.52 (6)	P1^viii—N1—P1	118.53 (8)
O2—K2—P1ⁱⁱ	71.74 (5)	P1^ix—N1—P1	118.54 (8)
O2^viii—K2—P1ⁱⁱ	152.93 (6)	P1^viii—N1—K2	97.01 (18)
O2^ix—K2—P1ⁱⁱ	98.86 (5)	P1^ix—N1—K2	97.01 (18)
P1ⁱⁱⁱ—K2—P1ⁱⁱ	107.04 (3)	P1—N1—K2	97.01 (18)
O3^viii—K3—O3^ix	83.76 (9)	P1^viii—N1—K3	82.99 (18)
O3^viii—K3—O3	83.76 (9)	P1^ix—N1—K3	82.99 (18)
O3^ix—K3—O3	83.76 (9)	P1—N1—K3	82.99 (18)
O3^viii—K3—O2^x	104.80 (8)	K2—N1—K3	180.0 (3)
O3^ix—K3—O2^x	162.69 (9)	P1—O1—Al1^xxi	144.58 (18)
O3—K3—O2^x	111.80 (8)	P1—O1—K1^xx	110.32 (14)
O3^viii—K3—O2^xi	111.80 (8)	Al1^xxi—O1—K1^xx	92.77 (12)
O3^ix—K3—O2^xi	104.80 (8)	P1—O1—K2^xviii	93.47 (13)
O3—K3—O2^xi	162.69 (9)	Al1^xxi—O1—K2^xviii	108.00 (11)
O2^x—K3—O2^xi	58.18 (9)	K1^xx—O1—K2^xviii	101.99 (8)
O3^viii—K3—O2^xii	162.69 (9)	P1—O2—Al1^xix	131.82 (18)
O3^ix—K3—O2^xii	111.80 (8)	P1—O2—K3^xix	103.68 (13)
O3—K3—O2^xii	104.80 (8)	Al1^xix—O2—K3^xix	90.31 (11)
O2^x—K3—O2^xii	58.18 (9)	P1—O2—K1^xx	89.45 (12)
O2^xi—K3—O2^xii	58.18 (9)	Al1^xix—O2—K1^xx	138.56 (12)
O3^viii—K3—N1	50.43 (6)	K3^xix—O2—K1^xx	73.60 (7)
O3^ix—K3—N1	50.43 (6)	P1—O2—K2	87.50 (12)
O3—K3—N1	50.43 (6)	Al1^xix—O2—K2	97.57 (11)
O2^x—K3—N1	145.85 (6)	K3^xix—O2—K2	156.49 (11)
O2^xi—K3—N1	145.85 (6)	K1^xx—O2—K2	86.08 (7)
O2^xii—K3—N1	145.85 (6)	P1—O3—K1^xviii	153.19 (17)
O3^viii—K3—O3^x	111.63 (2)	P1—O3—K3	114.19 (14)
O3^ix—K3—O3^x	143.68 (7)	K1^xviii—O3—K3	87.05 (9)
O3—K3—O3^x	66.44 (10)	P1—O3—K2^xviii	102.76 (15)
O2^x—K3—O3^x	47.20 (7)	K1^xviii—O3—K2^xviii	87.38 (8)
O2^xi—K3—O3^x	99.58 (8)	K3—O3—K2^xviii	102.41 (10)
O2^xii—K3—O3^x	60.45 (8)	P1—O3—K3^xix	82.03 (12)
N1—K3—O3^x	113.91 (5)	K1^xviii—O3—K3^xix	73.74 (6)
O3^viii—K3—O3^xi	66.44 (10)	K3—O3—K3^xix	158.41 (11)
O3^ix—K3—O3^xi	111.63 (2)	K2^xviii—O3—K3^xix	86.76 (7)
O3—K3—O3^xi	143.68 (7)

Symmetry codes: (i) −y+1, z−1/2, −x+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) z−1/2, −x+1/2, −y+1; (iv) −z+1/2, −x, y−1/2; (v) y−1/2, −z+1/2, −x; (vi) −x, y−1/2, −z+1/2; (vii) x−1, y−1, z−1; (viii) z, x, y; (ix) y, z, x; (x) −z+1, x+1/2, −y+3/2; (xi) −y+3/2, −z+1, x+1/2; (xii) x+1/2, −y+3/2, −z+1; (xiii) −z+3/2, −x+1, y+1/2; (xiv) y+1/2, −z+3/2, −x+1; (xv) −x+1, y+1/2, −z+3/2; (xvi) x+1, y+1, z+1; (xvii) −x+3/2, −y+1, z+1/2; (xviii) −x+1/2, −y+1, z+1/2; (xix) x−1/2, −y+3/2, −z+1; (xx) −x, y+1/2, −z+1/2; (xxi) −x+1, y−1/2, −z+3/2.

Tripotassium gallium nitridotriphosphate (II) top

Crystal data top

K₃Ga(NP₃O₉)	D_x = 3.157 Mg m⁻³
M_r = 437.94	Mo Kα radiation, λ = 0.71073 Å
Cubic, P2₁3	Cell parameters from 4964 reflections
Hall symbol: P 2ac 2ab 3	θ = 3.0–28.0°
a = 9.7313 (9) Å	µ = 4.90 mm⁻¹
V = 921.5 (3) Å³	T = 293 K
Z = 4	Irregular tetrahedron, colorless
F(000) = 848	0.12 × 0.07 × 0.04 mm

Data collection top

Oxford Diffraction Xcalibur-3 diffractometer	517 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.155
φ and ω scans	θ_max = 28.0°, θ_min = 3.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −12→9
T_min = 0.738, T_max = 0.804	k = −12→9
4964 measured reflections	l = −10→12
753 independent reflections

Refinement top

Refinement on F²	'w = 1/[σ²(F_o²) + (0.0188P)²] where P = (F_o² + 2F_c²)/3'
Least-squares matrix: full	(Δ/σ)_max < 0.001
R[F² > 2σ(F²)] = 0.059	Δρ_max = 0.67 e Å⁻³
wR(F²) = 0.102	Δρ_min = −0.60 e Å⁻³
S = 1	Extinction correction: SHELXL2018/3 (Sheldrick 2015)
753 reflections	Extinction coefficient: 0.0038 (15)
53 parameters	Absolute structure: Flack x determined using 153 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.03 (5)

Special details top

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

	x	y	z	U_iso*/U_eq
K1	0.0456 (3)	0.0456 (3)	0.0456 (3)	0.0326 (13)
K2	0.2679 (3)	0.2679 (3)	0.2679 (3)	0.0329 (13)
K3	0.6410 (3)	0.6410 (3)	0.6410 (3)	0.0358 (14)
Ga1	0.83974 (15)	0.83974 (15)	0.83974 (15)	0.0235 (7)
P1	0.3255 (4)	0.5696 (3)	0.4719 (3)	0.0221 (8)
N1	0.4446 (10)	0.4446 (10)	0.4446 (10)	0.019 (4)
O1	0.2172 (8)	0.5088 (9)	0.5672 (8)	0.024 (2)
O2	0.2578 (8)	0.5989 (8)	0.3347 (9)	0.026 (2)
O3	0.3941 (8)	0.6899 (8)	0.5330 (8)	0.028 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0326 (13)	0.0326 (13)	0.0326 (13)	−0.0026 (14)	−0.0026 (14)	−0.0026 (14)
K2	0.0329 (13)	0.0329 (13)	0.0329 (13)	−0.0034 (14)	−0.0034 (14)	−0.0034 (14)
K3	0.0358 (14)	0.0358 (14)	0.0358 (14)	−0.0040 (16)	−0.0040 (16)	−0.0040 (16)
Ga1	0.0235 (7)	0.0235 (7)	0.0235 (7)	0.0007 (7)	0.0007 (7)	0.0007 (7)
P1	0.0243 (18)	0.0217 (18)	0.0204 (17)	−0.0025 (15)	−0.0006 (15)	−0.0001 (14)
N1	0.019 (4)	0.019 (4)	0.019 (4)	0.003 (5)	0.003 (5)	0.003 (5)
O1	0.022 (5)	0.029 (5)	0.021 (5)	−0.002 (4)	0.007 (4)	0.010 (4)
O2	0.022 (4)	0.031 (5)	0.026 (5)	0.005 (4)	−0.001 (4)	−0.003 (4)
O3	0.039 (6)	0.023 (5)	0.023 (5)	−0.005 (4)	−0.002 (4)	−0.006 (4)

Geometric parameters (Å, º) top

K1—O3ⁱ	2.642 (8)	K2—P1ⁱ	3.409 (4)
K1—O3ⁱⁱ	2.642 (8)	K3—O3	2.665 (9)
K1—O3ⁱⁱⁱ	2.642 (8)	K3—O3^viii	2.665 (9)
K1—O1^iv	2.807 (9)	K3—O3^ix	2.665 (9)
K1—O1^v	2.807 (9)	K3—O2^x	2.785 (8)
K1—O1^vi	2.807 (9)	K3—O2^xi	2.785 (8)
K1—O2^v	3.216 (8)	K3—O2^xii	2.785 (8)
K1—O2^vi	3.216 (8)	K3—N1	3.310 (18)
K1—O2^iv	3.216 (8)	K3—Ga1	3.350 (5)
K1—Ga1^vii	3.470 (6)	K3—O3^x	3.412 (8)
K1—P1^iv	3.624 (5)	K3—O3^xi	3.412 (8)
K1—P1^vi	3.624 (5)	K3—O3^xii	3.412 (8)
K2—O3ⁱⁱ	2.808 (9)	K3—P1^xii	3.516 (4)
K2—O3ⁱ	2.808 (9)	Ga1—O1^xiii	1.958 (8)
K2—O3ⁱⁱⁱ	2.808 (9)	Ga1—O1^xiv	1.958 (8)
K2—O1ⁱ	2.925 (9)	Ga1—O1^xv	1.958 (8)
K2—O1ⁱⁱ	2.925 (9)	Ga1—O2^xi	1.968 (9)
K2—O1ⁱⁱⁱ	2.925 (9)	Ga1—O2^x	1.968 (9)
K2—N1	2.977 (18)	Ga1—O2^xii	1.968 (9)
K2—O2^viii	3.287 (8)	P1—O3	1.473 (9)
K2—O2^ix	3.287 (8)	P1—O2	1.516 (9)
K2—O2	3.287 (8)	P1—O1	1.524 (9)
K2—P1ⁱⁱ	3.409 (4)	P1—N1	1.701 (4)

O3ⁱ—K1—O3ⁱⁱ	80.8 (3)	O2^x—K3—O3^x	46.3 (2)
O3ⁱ—K1—O3ⁱⁱⁱ	80.8 (3)	O2^xi—K3—O3^x	101.1 (2)
O3ⁱⁱ—K1—O3ⁱⁱⁱ	80.8 (3)	O2^xii—K3—O3^x	60.3 (2)
O3ⁱ—K1—O1^iv	111.5 (2)	N1—K3—O3^x	114.13 (16)
O3ⁱⁱ—K1—O1^iv	165.6 (3)	Ga1—K3—O3^x	65.87 (16)
O3ⁱⁱⁱ—K1—O1^iv	108.0 (3)	O3—K3—O3^xi	143.91 (19)
O3ⁱ—K1—O1^v	108.0 (3)	O3^viii—K3—O3^xi	111.65 (7)
O3ⁱⁱ—K1—O1^v	111.5 (2)	O3^ix—K3—O3^xi	67.3 (3)
O3ⁱⁱⁱ—K1—O1^v	165.6 (3)	O2^x—K3—O3^xi	60.3 (2)
O1^iv—K1—O1^v	58.5 (3)	O2^xi—K3—O3^xi	46.3 (2)
O3ⁱ—K1—O1^vi	165.6 (3)	O2^xii—K3—O3^xi	101.1 (2)
O3ⁱⁱ—K1—O1^vi	108.0 (3)	N1—K3—O3^xi	114.13 (16)
O3ⁱⁱⁱ—K1—O1^vi	111.5 (2)	Ga1—K3—O3^xi	65.87 (16)
O1^iv—K1—O1^vi	58.5 (3)	O3^x—K3—O3^xi	104.44 (18)
O1^v—K1—O1^vi	58.5 (3)	O3—K3—O3^xii	111.65 (7)
O3ⁱ—K1—O2^v	93.7 (2)	O3^viii—K3—O3^xii	67.3 (3)
O3ⁱⁱ—K1—O2^v	64.5 (2)	O3^ix—K3—O3^xii	143.91 (19)
O3ⁱⁱⁱ—K1—O2^v	145.2 (3)	O2^x—K3—O3^xii	101.1 (2)
O1^iv—K1—O2^v	106.0 (3)	O2^xi—K3—O3^xii	60.3 (2)
O1^v—K1—O2^v	47.6 (2)	O2^xii—K3—O3^xii	46.3 (2)
O1^vi—K1—O2^v	80.4 (2)	N1—K3—O3^xii	114.13 (16)
O3ⁱ—K1—O2^vi	145.2 (3)	Ga1—K3—O3^xii	65.87 (16)
O3ⁱⁱ—K1—O2^vi	93.7 (2)	O3^x—K3—O3^xii	104.44 (18)
O3ⁱⁱⁱ—K1—O2^vi	64.5 (2)	O3^xi—K3—O3^xii	104.44 (18)
O1^iv—K1—O2^vi	80.4 (2)	O3—K3—P1^xii	101.2 (2)
O1^v—K1—O2^vi	106.0 (3)	O3^viii—K3—P1^xii	86.72 (18)
O1^vi—K1—O2^vi	47.6 (2)	O3^ix—K3—P1^xii	168.3 (2)
O2^v—K1—O2^vi	114.96 (13)	O2^x—K3—P1^xii	85.1 (2)
O3ⁱ—K1—O2^iv	64.5 (2)	O2^xi—K3—P1^xii	66.1 (2)
O3ⁱⁱ—K1—O2^iv	145.2 (3)	O2^xii—K3—P1^xii	24.51 (18)
O3ⁱⁱⁱ—K1—O2^iv	93.7 (2)	N1—K3—P1^xii	125.23 (9)
O1^iv—K1—O2^iv	47.6 (2)	Ga1—K3—P1^xii	54.77 (9)
O1^v—K1—O2^iv	80.4 (2)	O3^x—K3—P1^xii	79.98 (17)
O1^vi—K1—O2^iv	106.0 (3)	O3^xi—K3—P1^xii	112.13 (19)
O2^v—K1—O2^iv	114.96 (13)	O3^xii—K3—P1^xii	24.49 (15)
O2^vi—K1—O2^iv	114.96 (13)	O1^xiii—Ga1—O1^xiv	88.9 (4)
O3ⁱ—K1—Ga1^vii	131.6 (2)	O1^xiii—Ga1—O1^xv	88.9 (4)
O3ⁱⁱ—K1—Ga1^vii	131.6 (2)	O1^xiv—Ga1—O1^xv	88.9 (4)
O3ⁱⁱⁱ—K1—Ga1^vii	131.6 (2)	O1^xiii—Ga1—O2^xi	91.7 (3)
O1^iv—K1—Ga1^vii	34.33 (17)	O1^xiv—Ga1—O2^xi	176.3 (3)
O1^v—K1—Ga1^vii	34.33 (17)	O1^xv—Ga1—O2^xi	87.5 (3)
O1^vi—K1—Ga1^vii	34.33 (17)	O1^xiii—Ga1—O2^x	176.3 (3)
O2^v—K1—Ga1^vii	76.82 (17)	O1^xiv—Ga1—O2^x	87.5 (3)
O2^vi—K1—Ga1^vii	76.82 (17)	O1^xv—Ga1—O2^x	91.7 (4)
O2^iv—K1—Ga1^vii	76.82 (17)	O2^xi—Ga1—O2^x	92.0 (3)
O3ⁱ—K1—P1^iv	89.16 (19)	O1^xiii—Ga1—O2^xii	87.5 (3)
O3ⁱⁱ—K1—P1^iv	169.8 (2)	O1^xiv—Ga1—O2^xii	91.7 (3)
O3ⁱⁱⁱ—K1—P1^iv	98.99 (18)	O1^xv—Ga1—O2^xii	176.3 (3)
O1^iv—K1—P1^iv	23.26 (16)	O2^xi—Ga1—O2^xii	92.0 (3)
O1^v—K1—P1^iv	70.29 (19)	O2^x—Ga1—O2^xii	92.0 (3)
O1^vi—K1—P1^iv	81.7 (2)	O1^xiii—Ga1—K3	126.1 (2)
O2^v—K1—P1^iv	115.3 (2)	O1^xiv—Ga1—K3	126.1 (2)
O2^vi—K1—P1^iv	95.39 (17)	O1^xv—Ga1—K3	126.1 (2)
O2^iv—K1—P1^iv	24.71 (16)	O2^xi—Ga1—K3	56.2 (2)
Ga1^vii—K1—P1^iv	55.56 (9)	O2^x—Ga1—K3	56.2 (2)
O3ⁱ—K1—P1^vi	169.8 (2)	O2^xii—Ga1—K3	56.2 (2)
O3ⁱⁱ—K1—P1^vi	98.99 (18)	O1^xiii—Ga1—K1^xvi	53.9 (2)
O3ⁱⁱⁱ—K1—P1^vi	89.16 (19)	O1^xiv—Ga1—K1^xvi	53.9 (2)
O1^iv—K1—P1^vi	70.29 (19)	O1^xv—Ga1—K1^xvi	53.9 (2)
O1^v—K1—P1^vi	81.7 (2)	O2^xi—Ga1—K1^xvi	123.8 (2)
O1^vi—K1—P1^vi	23.26 (17)	O2^x—Ga1—K1^xvi	123.8 (2)
O2^v—K1—P1^vi	95.39 (17)	O2^xii—Ga1—K1^xvi	123.8 (2)
O2^vi—K1—P1^vi	24.71 (16)	K3—Ga1—K1^xvi	180.00 (7)
O2^iv—K1—P1^vi	115.3 (2)	O1^xiii—Ga1—K2^xiv	124.6 (3)
Ga1^vii—K1—P1^vi	55.56 (9)	O1^xiv—Ga1—K2^xiv	68.5 (3)
P1^iv—K1—P1^vi	91.16 (13)	O1^xv—Ga1—K2^xiv	43.4 (3)
O3ⁱⁱ—K2—O3ⁱ	75.1 (3)	O2^xi—Ga1—K2^xiv	108.3 (2)
O3ⁱⁱ—K2—O3ⁱⁱⁱ	75.1 (3)	O2^x—Ga1—K2^xiv	54.3 (2)
O3ⁱ—K2—O3ⁱⁱⁱ	75.1 (3)	O2^xii—Ga1—K2^xiv	140.0 (2)
O3ⁱⁱ—K2—O1ⁱ	123.7 (3)	K3—Ga1—K2^xiv	107.30 (4)
O3ⁱ—K2—O1ⁱ	51.4 (2)	K1^xvi—Ga1—K2^xiv	72.70 (4)
O3ⁱⁱⁱ—K2—O1ⁱ	102.9 (2)	O1^xiii—Ga1—K2^xvii	43.4 (3)
O3ⁱⁱ—K2—O1ⁱⁱ	51.4 (2)	O1^xiv—Ga1—K2^xvii	124.6 (3)
O3ⁱ—K2—O1ⁱⁱ	102.9 (2)	O1^xv—Ga1—K2^xvii	68.5 (3)
O3ⁱⁱⁱ—K2—O1ⁱⁱ	123.7 (3)	O2^xi—Ga1—K2^xvii	54.3 (2)
O1ⁱ—K2—O1ⁱⁱ	119.49 (5)	O2^x—Ga1—K2^xvii	140.0 (2)
O3ⁱⁱ—K2—O1ⁱⁱⁱ	102.9 (2)	O2^xii—Ga1—K2^xvii	108.3 (2)
O3ⁱ—K2—O1ⁱⁱⁱ	123.7 (3)	K3—Ga1—K2^xvii	107.30 (4)
O3ⁱⁱⁱ—K2—O1ⁱⁱⁱ	51.4 (2)	K1^xvi—Ga1—K2^xvii	72.70 (4)
O1ⁱ—K2—O1ⁱⁱⁱ	119.49 (5)	K2^xiv—Ga1—K2^xvii	111.55 (3)
O1ⁱⁱ—K2—O1ⁱⁱⁱ	119.49 (5)	O1^xiii—Ga1—K2^xii	68.5 (3)
O3ⁱⁱ—K2—N1	135.25 (18)	O1^xiv—Ga1—K2^xii	43.4 (3)
O3ⁱ—K2—N1	135.25 (18)	O1^xv—Ga1—K2^xii	124.6 (3)
O3ⁱⁱⁱ—K2—N1	135.25 (18)	O2^xi—Ga1—K2^xii	140.0 (2)
O1ⁱ—K2—N1	85.89 (18)	O2^x—Ga1—K2^xii	108.3 (2)
O1ⁱⁱ—K2—N1	85.89 (18)	O2^xii—Ga1—K2^xii	54.3 (2)
O1ⁱⁱⁱ—K2—N1	85.89 (18)	K3—Ga1—K2^xii	107.30 (4)
O3ⁱⁱ—K2—O2^viii	90.1 (2)	K1^xvi—Ga1—K2^xii	72.70 (4)
O3ⁱ—K2—O2^viii	156.0 (2)	K2^xiv—Ga1—K2^xii	111.55 (3)
O3ⁱⁱⁱ—K2—O2^viii	119.8 (2)	K2^xvii—Ga1—K2^xii	111.55 (3)
O1ⁱ—K2—O2^viii	131.8 (3)	O3—P1—O2	113.8 (5)
O1ⁱⁱ—K2—O2^viii	53.5 (2)	O3—P1—O1	112.1 (5)
O1ⁱⁱⁱ—K2—O2^viii	77.6 (2)	O2—P1—O1	107.9 (5)
N1—K2—O2^viii	48.52 (15)	O3—P1—N1	108.9 (7)
O3ⁱⁱ—K2—O2^ix	119.8 (2)	O2—P1—N1	107.0 (5)
O3ⁱ—K2—O2^ix	90.1 (2)	O1—P1—N1	106.8 (4)
O3ⁱⁱⁱ—K2—O2^ix	156.0 (2)	O3—P1—K2^xviii	53.9 (4)
O1ⁱ—K2—O2^ix	53.5 (2)	O2—P1—K2^xviii	122.8 (3)
O1ⁱⁱ—K2—O2^ix	77.6 (2)	O1—P1—K2^xviii	58.8 (4)
O1ⁱⁱⁱ—K2—O2^ix	131.8 (3)	N1—P1—K2^xviii	130.2 (4)
N1—K2—O2^ix	48.52 (15)	O3—P1—K3^xix	73.8 (3)
O2^viii—K2—O2^ix	80.9 (2)	O2—P1—K3^xix	49.6 (3)
O3ⁱⁱ—K2—O2	156.0 (2)	O1—P1—K3^xix	98.5 (3)
O3ⁱ—K2—O2	119.8 (2)	N1—P1—K3^xix	150.7 (2)
O3ⁱⁱⁱ—K2—O2	90.1 (2)	K2^xviii—P1—K3^xix	75.90 (10)
O1ⁱ—K2—O2	77.6 (2)	O3—P1—K3	42.8 (3)
O1ⁱⁱ—K2—O2	131.8 (3)	O2—P1—K3	138.4 (3)
O1ⁱⁱⁱ—K2—O2	53.5 (2)	O1—P1—K3	113.1 (3)
N1—K2—O2	48.52 (15)	N1—P1—K3	67.9 (6)
O2^viii—K2—O2	80.9 (2)	K2^xviii—P1—K3	75.44 (8)
O2^ix—K2—O2	80.9 (2)	K3^xix—P1—K3	115.45 (9)
O3ⁱⁱ—K2—P1ⁱⁱ	25.10 (18)	O3—P1—K2	160.8 (4)
O3ⁱ—K2—P1ⁱⁱ	86.7 (2)	O2—P1—K2	66.3 (3)
O3ⁱⁱⁱ—K2—P1ⁱⁱ	99.6 (2)	O1—P1—K2	84.9 (4)
O1ⁱ—K2—P1ⁱⁱ	123.33 (17)	N1—P1—K2	55.6 (6)
O1ⁱⁱ—K2—P1ⁱⁱ	26.44 (17)	K2^xviii—P1—K2	143.62 (12)
O1ⁱⁱⁱ—K2—P1ⁱⁱ	115.25 (16)	K3^xix—P1—K2	113.74 (10)
N1—K2—P1ⁱⁱ	111.98 (9)	K3—P1—K2	123.46 (11)
O2^viii—K2—P1ⁱⁱ	72.82 (16)	O3—P1—K1^xx	121.5 (3)
O2^ix—K2—P1ⁱⁱ	98.30 (15)	O2—P1—K1^xx	62.4 (3)
O2—K2—P1ⁱⁱ	153.45 (17)	O1—P1—K1^xx	46.7 (3)
O3ⁱⁱ—K2—P1ⁱ	99.6 (2)	N1—P1—K1^xx	128.7 (6)
O3ⁱ—K2—P1ⁱ	25.10 (18)	K2^xviii—P1—K1^xx	78.68 (8)
O3ⁱⁱⁱ—K2—P1ⁱ	86.7 (2)	K3^xix—P1—K1^xx	61.82 (9)
O1ⁱ—K2—P1ⁱ	26.44 (17)	K3—P1—K1^xx	153.65 (11)
O1ⁱⁱ—K2—P1ⁱ	115.25 (16)	K2—P1—K1^xx	76.43 (8)
O1ⁱⁱⁱ—K2—P1ⁱ	123.33 (17)	P1—N1—P1^viii	118.8 (2)
N1—K2—P1ⁱ	111.98 (9)	P1—N1—P1^ix	118.8 (2)
O2^viii—K2—P1ⁱ	153.45 (17)	P1^viii—N1—P1^ix	118.8 (2)
O2^ix—K2—P1ⁱ	72.82 (16)	P1—N1—K2	96.3 (6)
O2—K2—P1ⁱ	98.30 (15)	P1^viii—N1—K2	96.3 (6)
P1ⁱⁱ—K2—P1ⁱ	106.85 (10)	P1^ix—N1—K2	96.3 (6)
O3—K3—O3^viii	82.9 (3)	P1—N1—K3	83.7 (6)
O3—K3—O3^ix	82.9 (3)	P1^viii—N1—K3	83.7 (6)
O3^viii—K3—O3^ix	82.9 (3)	P1^ix—N1—K3	83.7 (6)
O3—K3—O2^x	111.2 (2)	K2—N1—K3	180.0 (9)
O3^viii—K3—O2^x	164.8 (3)	P1—O1—Ga1^xxi	143.5 (6)
O3^ix—K3—O2^x	103.8 (2)	P1—O1—K1^xx	110.0 (4)
O3—K3—O2^xi	164.8 (3)	Ga1^xxi—O1—K1^xx	91.7 (3)
O3^viii—K3—O2^xi	103.8 (2)	P1—O1—K2^xviii	94.8 (4)
O3^ix—K3—O2^xi	111.2 (2)	Ga1^xxi—O1—K2^xviii	109.2 (3)
O2^x—K3—O2^xi	61.1 (3)	K1^xx—O1—K2^xviii	102.2 (3)
O3—K3—O2^xii	103.8 (2)	P1—O2—Ga1^xix	129.8 (5)
O3^viii—K3—O2^xii	111.2 (2)	P1—O2—K3^xix	105.8 (4)
O3^ix—K3—O2^xii	164.8 (3)	Ga1^xix—O2—K3^xix	87.9 (3)
O2^x—K3—O2^xii	61.1 (3)	P1—O2—K1^xx	92.9 (4)
O2^xi—K3—O2^xii	61.1 (3)	Ga1^xix—O2—K1^xx	137.2 (4)
O3—K3—N1	49.85 (19)	K3^xix—O2—K1^xx	74.99 (18)
O3^viii—K3—N1	49.85 (19)	P1—O2—K2	88.7 (3)
O3^ix—K3—N1	49.85 (19)	Ga1^xix—O2—K2	96.6 (3)
O2^x—K3—N1	144.05 (18)	K3^xix—O2—K2	156.9 (3)
O2^xi—K3—N1	144.05 (18)	K1^xx—O2—K2	86.6 (2)
O2^xii—K3—N1	144.05 (18)	P1—O3—K1^xviii	153.3 (5)
O3—K3—Ga1	130.15 (19)	P1—O3—K3	115.2 (4)
O3^viii—K3—Ga1	130.15 (19)	K1^xviii—O3—K3	87.5 (3)
O3^ix—K3—Ga1	130.15 (19)	P1—O3—K2^xviii	101.0 (4)
O2^x—K3—Ga1	35.95 (18)	K1^xviii—O3—K2^xviii	86.8 (3)
O2^xi—K3—Ga1	35.95 (18)	K3—O3—K2^xviii	102.2 (3)
O2^xii—K3—Ga1	35.95 (18)	P1—O3—K3^xix	81.7 (3)
N1—K3—Ga1	180.0 (3)	K1^xviii—O3—K3^xix	73.36 (19)
O3—K3—O3^x	67.3 (3)	K3—O3—K3^xix	158.9 (3)
O3^viii—K3—O3^x	143.91 (19)	K2^xviii—O3—K3^xix	85.9 (2)
O3^ix—K3—O3^x	111.65 (7)

Symmetry codes: (i) z−1/2, −x+1/2, −y+1; (ii) −y+1, z−1/2, −x+1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) −z+1/2, −x, y−1/2; (vi) y−1/2, −z+1/2, −x; (vii) x−1, y−1, z−1; (viii) y, z, x; (ix) z, x, y; (x) −z+1, x+1/2, −y+3/2; (xi) −y+3/2, −z+1, x+1/2; (xii) x+1/2, −y+3/2, −z+1; (xiii) y+1/2, −z+3/2, −x+1; (xiv) −x+1, y+1/2, −z+3/2; (xv) −z+3/2, −x+1, y+1/2; (xvi) x+1, y+1, z+1; (xvii) −x+3/2, −y+1, z+1/2; (xviii) −x+1/2, −y+1, z+1/2; (xix) x−1/2, −y+3/2, −z+1; (xx) −x, y+1/2, −z+1/2; (xxi) −x+1, y−1/2, −z+3/2.

BVS results (v.u.) for (I) and (II) top

Central Atom	(I)	(II)
Al1/Ga1	3.004	3.197
K1	1.486	1.400
K2	1.122	1.069
K3	1.315	1.360
P1	3 × 4.903	3 × 5.084
Σ	21.636	22.278

Distances (Å) between atoms for (I), (II) and isotypic M^I₃M^III(PO₃)₃N compounds along [111] top

Compound	Atomic distance between neighboring atoms	Reference
Na₃Al(PO₃)₃N	–Na1–3.438–Na2–2.875–N–3.197–Na3–3.068–Al–3.486–Na1–	Massiot et al. (1996)
Na₃Ti(PO₃)₃N	–Na1–3.448–Na2–3.078–N–3.188–Na3–3.100–Ti–3.638–Na1–	Zatovsky et al. (2006)
Na₃V(PO₃)₃N	–Na1–3.477–Na2–2.947–N–3.234–Na3–3.100–V–3.606–Na1–	Kim & Kim (2013)
K₃Al(PO₃)₃N	–K1–3.723–K2–2.904–N–3.340–K3–3.400–Al–3.429–K1–	This work
K₃Ga(PO₃)₃N	–K1–3.747–K2–2.978–N–3.310–K3–3.350–Ga–3.470–K1–	This work

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Volume 77| Part 12| December 2021| Pages 1213-1218

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