Novel first-row transition-metal phosphates: hydro­thermal synthesis and crystal structures

Kiriukhina, G.V.; Yakubovich, O.V.; Verchenko, P.A.; Volkov, A.S.; Dimitrova, O.V.

doi:10.1107/S2053229622003692

Novel first-row transition-metal phosphates: hydrothermal synthesis and crystal structures

G. V. Kiriukhina, O. V. Yakubovich, P. A. Verchenko, A. S. Volkov and O. V. Dimitrova

Two new compounds, sodium copper nickel diorthophosphate, Na₂CuNi(PO₄)₂ (I), and dimanganese copper diorthophosphate, Mn₂Cu(PO₄)₂ (II), were synthesized hydrothermally, yielding single crystals, and were studied by X-ray diffraction. In the crystal structures, various transition metals of d-elements occupy symmetrically independent crystallographic positions with different coordination geometries. In the crystal structure of Na₂NiCu(PO₄)₂, NiO₆ and CuO₆ octahedra share edges to form chains that PO₄ groups link into a framework with cavities filled with Na atoms. Layered cationic fragments formed from dimers of MnO₅ trigonal bipyramids and CuO₄ square planes, sharing vertices, are connected through PO₄ tetrahedra into a 3-periodic Mn₂Cu(PO₄)₂ crystal structure. Structural correlations between Na₂NiCu(PO₄)₂ and NaCuPO₄ are discussed, and crystal–chemical details of the currently known exclusively synthetic mixed Mn/Cu and Ni/Cu phosphates are presented.

Keywords: transition-metal phosphate; crystal structure; double-metal phosphate; coordination geometry; hydrothermal synthesis; magnetic material.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229622003692/ov3158sup1.cif Contains datablocks I, II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622003692/ov3158Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622003692/ov3158IIsup3.hkl Contains datablock II
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229622003692/ov3158sup4.pdf Supplementary material

CCDC references: 2164157; 2164158

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Sodium copper nickel diorthophosphate (I) top

Crystal data top

Na₂CuNi(PO₄)₂	F(000) = 346
M_r = 358.17	D_x = 3.935 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.1300 (1) Å	Cell parameters from 2144 reflections
b = 8.6729 (2) Å	θ = 4.6–30.5°
c = 6.8473 (2) Å	µ = 7.32 mm⁻¹
β = 97.104 (3)°	T = 293 K
V = 302.31 (1) Å³	Asymmetric, light green
Z = 2	0.15 × 0.12 × 0.09 mm

Data collection top

Rigaku OD Xcalibur Sapphire3 diffractometer	863 independent reflections
Radiation source: fine-focus sealed X-ray tube	741 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	R_int = 0.036
ω scans	θ_max = 30.0°, θ_min = 4.6°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	h = −7→7
T_min = 0.447, T_max = 0.605	k = −12→12
4614 measured reflections	l = −9→9

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)] = 0.024	w = 1/[σ²(F_o²) + (0.026P)² + 0.250P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max < 0.001
S = 1.13	Δρ_max = 0.58 e Å⁻³
863 reflections	Δρ_min = −0.50 e Å⁻³
68 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0151 (18)

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
Cu1	1.000000	0.500000	0.500000	0.00953 (16)
Ni1	1.000000	0.500000	0.000000	0.00901 (16)
P1	0.55035 (13)	0.31773 (8)	0.21763 (10)	0.00698 (18)
Na1	0.5394 (2)	0.35311 (14)	0.71180 (17)	0.0129 (3)
O1	0.5516 (4)	0.1372 (2)	0.2405 (3)	0.0097 (4)
O2	0.6902 (4)	0.3876 (2)	0.4086 (3)	0.0110 (4)
O3	0.7043 (4)	0.3521 (2)	0.0458 (3)	0.0120 (4)
O4	0.2702 (4)	0.3796 (2)	0.1928 (3)	0.0107 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0097 (3)	0.0084 (3)	0.0095 (3)	−0.00294 (17)	−0.00285 (18)	0.00193 (17)
Ni1	0.0085 (3)	0.0094 (3)	0.0090 (3)	−0.00042 (18)	0.00037 (19)	0.00068 (18)
P1	0.0071 (3)	0.0065 (3)	0.0073 (3)	−0.0007 (3)	0.0002 (2)	0.0000 (2)
Na1	0.0121 (5)	0.0139 (6)	0.0126 (5)	0.0009 (4)	0.0011 (4)	−0.0001 (5)
O1	0.0123 (9)	0.0057 (9)	0.0107 (9)	0.0005 (7)	0.0001 (7)	−0.0012 (7)
O2	0.0117 (9)	0.0122 (10)	0.0090 (9)	−0.0041 (8)	0.0005 (7)	−0.0008 (7)
O3	0.0124 (9)	0.0141 (10)	0.0098 (9)	−0.0032 (8)	0.0025 (8)	0.0000 (8)
O4	0.0100 (9)	0.0092 (10)	0.0126 (9)	0.0015 (7)	0.0003 (7)	0.0005 (7)

Geometric parameters (Å, º) top

Cu1—O2	1.9029 (19)	Ni1—Na1ⁱⁱⁱ	3.3838 (12)
Cu1—O2ⁱ	1.9029 (19)	P1—O4	1.5239 (19)
Cu1—O1ⁱⁱ	2.0223 (18)	P1—O3	1.5251 (19)
Cu1—O1ⁱⁱⁱ	2.0223 (18)	P1—O2	1.5362 (19)
Cu1—Na1	3.1870 (12)	P1—O1	1.573 (2)
Cu1—Na1ⁱ	3.1870 (12)	P1—Na1^viii	2.9182 (13)
Cu1—Na1^iv	3.2235 (11)	P1—Na1^iv	2.9412 (14)
Cu1—Na1^v	3.2235 (11)	P1—Na1^x	3.0069 (13)
Ni1—O3^vi	2.0406 (19)	P1—Na1	3.4050 (12)
Ni1—O3	2.0406 (19)	Na1—O2	2.323 (2)
Ni1—O4^vii	2.0740 (19)	Na1—O3^xi	2.338 (2)
Ni1—O4^v	2.0740 (19)	Na1—O4ⁱⁱ	2.351 (2)
Ni1—O1^viii	2.1821 (19)	Na1—O1^xii	2.536 (2)
Ni1—O1ⁱⁱⁱ	2.1821 (19)	Na1—O4^iv	2.569 (2)
Ni1—Na1ⁱ	3.1539 (11)	Na1—O1ⁱⁱ	2.612 (2)
Ni1—Na1^ix	3.1539 (11)	Na1—O2^iv	2.624 (2)
Ni1—Na1^viii	3.3838 (12)	Na1—O3^xii	2.633 (2)

O2—Cu1—O2ⁱ	180.0	Na1^viii—P1—Na1	100.32 (3)
O2—Cu1—O1ⁱⁱ	89.22 (8)	Na1^iv—P1—Na1	74.16 (4)
O2ⁱ—Cu1—O1ⁱⁱ	90.78 (8)	Na1^x—P1—Na1	86.34 (3)
O2—Cu1—O1ⁱⁱⁱ	90.78 (8)	O2—Na1—O3^xi	138.99 (8)
O2ⁱ—Cu1—O1ⁱⁱⁱ	89.22 (8)	O2—Na1—O4ⁱⁱ	80.53 (8)
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	180.0	O3^xi—Na1—O4ⁱⁱ	85.83 (8)
O2—Cu1—Na1	46.29 (6)	O2—Na1—O1^xii	120.39 (8)
O2ⁱ—Cu1—Na1	133.71 (6)	O3^xi—Na1—O1^xii	99.53 (8)
O1ⁱⁱ—Cu1—Na1	54.83 (6)	O4ⁱⁱ—Na1—O1^xii	122.76 (8)
O1ⁱⁱⁱ—Cu1—Na1	125.17 (6)	O2—Na1—O4^iv	87.29 (8)
O2—Cu1—Na1ⁱ	133.71 (6)	O3^xi—Na1—O4^iv	71.01 (7)
O2ⁱ—Cu1—Na1ⁱ	46.29 (6)	O4ⁱⁱ—Na1—O4^iv	127.62 (5)
O1ⁱⁱ—Cu1—Na1ⁱ	125.17 (6)	O1^xii—Na1—O4^iv	107.36 (7)
O1ⁱⁱⁱ—Cu1—Na1ⁱ	54.83 (6)	O2—Na1—O1ⁱⁱ	67.66 (7)
Na1—Cu1—Na1ⁱ	180.0	O3^xi—Na1—O1ⁱⁱ	71.81 (7)
O2—Cu1—Na1^iv	54.47 (6)	O4ⁱⁱ—Na1—O1ⁱⁱ	61.51 (7)
O2ⁱ—Cu1—Na1^iv	125.53 (6)	O1^xii—Na1—O1ⁱⁱ	170.55 (10)
O1ⁱⁱ—Cu1—Na1^iv	128.14 (6)	O4^iv—Na1—O1ⁱⁱ	66.71 (6)
O1ⁱⁱⁱ—Cu1—Na1^iv	51.86 (6)	O2—Na1—O2^iv	78.17 (8)
Na1—Cu1—Na1^iv	73.69 (3)	O3^xi—Na1—O2^iv	113.87 (8)
Na1ⁱ—Cu1—Na1^iv	106.31 (3)	O4ⁱⁱ—Na1—O2^iv	158.08 (8)
O2—Cu1—Na1^v	125.53 (6)	O1^xii—Na1—O2^iv	65.60 (6)
O2ⁱ—Cu1—Na1^v	54.47 (6)	O4^iv—Na1—O2^iv	56.51 (6)
O1ⁱⁱ—Cu1—Na1^v	51.86 (6)	O1ⁱⁱ—Na1—O2^iv	113.86 (7)
O1ⁱⁱⁱ—Cu1—Na1^v	128.14 (6)	O2—Na1—O3^xii	88.46 (7)
Na1—Cu1—Na1^v	106.31 (3)	O3^xi—Na1—O3^xii	123.88 (7)
Na1ⁱ—Cu1—Na1^v	73.69 (3)	O4ⁱⁱ—Na1—O3^xii	72.68 (7)
Na1^iv—Cu1—Na1^v	180.0	O1^xii—Na1—O3^xii	57.16 (6)
O3^vi—Ni1—O3	180.0	O4^iv—Na1—O3^xii	158.03 (8)
O3^vi—Ni1—O4^vii	92.09 (7)	O1ⁱⁱ—Na1—O3^xii	130.64 (7)
O3—Ni1—O4^vii	87.91 (7)	O2^iv—Na1—O3^xii	101.52 (7)
O3^vi—Ni1—O4^v	87.91 (7)	O2—Na1—P1^xii	117.36 (6)
O3—Ni1—O4^v	92.09 (7)	O3^xi—Na1—P1^xii	101.08 (6)
O4^vii—Ni1—O4^v	180.00 (9)	O4ⁱⁱ—Na1—P1^xii	90.26 (6)
O3^vi—Ni1—O1^viii	92.89 (7)	O1^xii—Na1—P1^xii	32.58 (5)
O3—Ni1—O1^viii	87.11 (7)	O4^iv—Na1—P1^xii	139.05 (6)
O4^vii—Ni1—O1^viii	83.98 (7)	O1ⁱⁱ—Na1—P1^xii	150.91 (7)
O4^v—Ni1—O1^viii	96.02 (7)	O2^iv—Na1—P1^xii	94.94 (5)
O3^vi—Ni1—O1ⁱⁱⁱ	87.11 (7)	O3^xii—Na1—P1^xii	31.36 (4)
O3—Ni1—O1ⁱⁱⁱ	92.89 (7)	O2—Na1—P1^iv	95.62 (7)
O4^vii—Ni1—O1ⁱⁱⁱ	96.02 (7)	O3^xi—Na1—P1^iv	83.58 (6)
O4^v—Ni1—O1ⁱⁱⁱ	83.98 (7)	O4ⁱⁱ—Na1—P1^iv	158.79 (7)
O1^viii—Ni1—O1ⁱⁱⁱ	180.00 (8)	O1^xii—Na1—P1^iv	77.24 (5)
O3^vi—Ni1—Na1ⁱ	47.82 (6)	O4^iv—Na1—P1^iv	31.19 (4)
O3—Ni1—Na1ⁱ	132.18 (6)	O1ⁱⁱ—Na1—P1^iv	97.64 (6)
O4^vii—Ni1—Na1ⁱ	125.78 (6)	O2^iv—Na1—P1^iv	31.39 (4)
O4^v—Ni1—Na1ⁱ	54.22 (6)	O3^xii—Na1—P1^iv	128.30 (6)
O1^viii—Ni1—Na1ⁱ	124.96 (5)	P1^xii—Na1—P1^iv	109.77 (4)
O1ⁱⁱⁱ—Ni1—Na1ⁱ	55.04 (5)	O2—Na1—P1ⁱⁱ	71.90 (6)
O3^vi—Ni1—Na1^ix	132.18 (6)	O3^xi—Na1—P1ⁱⁱ	77.05 (6)
O3—Ni1—Na1^ix	47.82 (6)	O4ⁱⁱ—Na1—P1ⁱⁱ	29.98 (5)
O4^vii—Ni1—Na1^ix	54.22 (6)	O1^xii—Na1—P1ⁱⁱ	151.92 (7)
O4^v—Ni1—Na1^ix	125.78 (6)	O4^iv—Na1—P1ⁱⁱ	97.93 (5)
O1^viii—Ni1—Na1^ix	55.04 (5)	O1ⁱⁱ—Na1—P1ⁱⁱ	31.53 (4)
O1ⁱⁱⁱ—Ni1—Na1^ix	124.96 (5)	O2^iv—Na1—P1ⁱⁱ	141.56 (6)
Na1ⁱ—Ni1—Na1^ix	180.0	O3^xii—Na1—P1ⁱⁱ	101.21 (6)
O3^vi—Ni1—Na1^viii	128.96 (6)	P1^xii—Na1—P1ⁱⁱ	119.94 (5)
O3—Ni1—Na1^viii	51.04 (6)	P1^iv—Na1—P1ⁱⁱ	129.05 (4)
O4^vii—Ni1—Na1^viii	136.75 (6)	O2—Na1—Ni1^xi	101.57 (6)
O4^v—Ni1—Na1^viii	43.25 (6)	O3^xi—Na1—Ni1^xi	40.29 (5)
O1^viii—Ni1—Na1^viii	81.29 (5)	O4ⁱⁱ—Na1—Ni1^xi	92.18 (6)
O1ⁱⁱⁱ—Ni1—Na1^viii	98.71 (5)	O1^xii—Na1—Ni1^xi	127.48 (6)
Na1ⁱ—Ni1—Na1^viii	95.566 (17)	O4^iv—Na1—Ni1^xi	40.92 (4)
Na1^ix—Ni1—Na1^viii	84.434 (17)	O1ⁱⁱ—Na1—Ni1^xi	43.21 (4)
O3^vi—Ni1—Na1ⁱⁱⁱ	51.04 (6)	O2^iv—Na1—Ni1^xi	97.06 (5)
O3—Ni1—Na1ⁱⁱⁱ	128.96 (6)	O3^xii—Na1—Ni1^xi	160.37 (6)
O4^vii—Ni1—Na1ⁱⁱⁱ	43.25 (6)	P1^xii—Na1—Ni1^xi	140.84 (4)
O4^v—Ni1—Na1ⁱⁱⁱ	136.75 (6)	P1^iv—Na1—Ni1^xi	68.01 (3)
O1^viii—Ni1—Na1ⁱⁱⁱ	98.71 (5)	P1ⁱⁱ—Na1—Ni1^xi	66.82 (3)
O1ⁱⁱⁱ—Ni1—Na1ⁱⁱⁱ	81.29 (5)	P1—O1—Cu1^xiii	120.42 (11)
Na1ⁱ—Ni1—Na1ⁱⁱⁱ	84.434 (17)	P1—O1—Ni1^xiii	128.63 (11)
Na1^ix—Ni1—Na1ⁱⁱⁱ	95.566 (17)	Cu1^xiii—O1—Ni1^xiii	108.98 (8)
Na1^viii—Ni1—Na1ⁱⁱⁱ	180.0	P1—O1—Na1^viii	87.21 (9)
O4—P1—O3	114.60 (11)	Cu1^xiii—O1—Na1^viii	89.29 (7)
O4—P1—O2	106.92 (11)	Ni1^xiii—O1—Na1^viii	107.54 (8)
O3—P1—O2	110.34 (11)	P1—O1—Na1^x	88.22 (9)
O4—P1—O1	110.70 (11)	Cu1^xiii—O1—Na1^x	85.90 (7)
O3—P1—O1	105.95 (11)	Ni1^xiii—O1—Na1^x	81.74 (7)
O2—P1—O1	108.21 (11)	Na1^viii—O1—Na1^x	170.55 (10)
O4—P1—Na1^viii	167.91 (8)	P1—O2—Cu1	139.94 (12)
O3—P1—Na1^viii	63.93 (8)	P1—O2—Na1	122.52 (11)
O2—P1—Na1^viii	84.27 (8)	Cu1—O2—Na1	97.40 (8)
O1—P1—Na1^viii	60.21 (8)	P1—O2—Na1^iv	85.79 (9)
O4—P1—Na1^iv	60.80 (8)	Cu1—O2—Na1^iv	89.35 (8)
O3—P1—Na1^iv	92.51 (8)	Na1—O2—Na1^iv	101.83 (8)
O2—P1—Na1^iv	62.82 (8)	P1—O3—Ni1	135.00 (12)
O1—P1—Na1^iv	161.51 (8)	P1—O3—Na1^ix	126.59 (11)
Na1^viii—P1—Na1^iv	130.34 (4)	Ni1—O3—Na1^ix	91.89 (8)
O4—P1—Na1^x	50.45 (8)	P1—O3—Na1^viii	84.71 (9)
O3—P1—Na1^x	128.29 (8)	Ni1—O3—Na1^viii	91.90 (7)
O2—P1—Na1^x	121.36 (8)	Na1^ix—O3—Na1^viii	124.25 (9)
O1—P1—Na1^x	60.25 (8)	P1—O4—Ni1^xiv	142.67 (12)
Na1^viii—P1—Na1^x	119.94 (5)	P1—O4—Na1^x	99.56 (10)
Na1^iv—P1—Na1^x	109.06 (3)	Ni1^xiv—O4—Na1^x	99.56 (8)
O4—P1—Na1	87.02 (8)	P1—O4—Na1^iv	88.02 (9)
O3—P1—Na1	145.36 (8)	Ni1^xiv—O4—Na1^iv	84.86 (7)
O2—P1—Na1	35.12 (8)	Na1^x—O4—Na1^iv	159.84 (9)
O1—P1—Na1	89.50 (7)

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

Dimanganese copper diorthophosphate (II) top

Crystal data top

Mn₂Cu(PO₄)₂	Z = 1
M_r = 363.36	F(000) = 173
Triclinic, P1	D_x = 3.935 Mg m⁻³
a = 4.8292 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.4051 (5) Å	Cell parameters from 1224 reflections
c = 6.5968 (6) Å	θ = 3.2–29.8°
α = 72.716 (8)°	µ = 8.02 mm⁻¹
β = 86.579 (8)°	T = 293 K
γ = 69.064 (9)°	Flattened, light green
V = 153.35 (3) Å³	0.10 × 0.05 × 0.05 mm

Data collection top

Rigaku OD Xcalibur Sapphire3 diffractometer	846 independent reflections
Radiation source: fine-focus sealed X-ray tube	723 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	R_int = 0.043
ω scans	θ_max = 29.9°, θ_min = 3.2°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	h = −6→6
T_min = 0.600, T_max = 0.749	k = −7→7
2449 measured reflections	l = −9→9

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)] = 0.032	w = 1/[σ²(F_o²) + (0.020P)² + 0.006P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.068	(Δ/σ)_max < 0.001
S = 1.14	Δρ_max = 1.19 e Å⁻³
846 reflections	Δρ_min = −0.81 e Å⁻³
62 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.023 (4)

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.500000	0.000000	0.500000	0.01030 (19)
Mn1	0.21184 (13)	0.73817 (12)	0.19171 (9)	0.00965 (18)
P	0.8665 (2)	0.3392 (2)	0.28146 (15)	0.0064 (2)
O1	1.1796 (6)	0.3337 (5)	0.3316 (4)	0.0096 (5)
O2	0.7335 (5)	0.2257 (5)	0.4930 (4)	0.0073 (5)
O3	0.8902 (6)	0.1502 (5)	0.1410 (4)	0.0100 (6)
O4	0.6756 (6)	0.6372 (5)	0.1722 (4)	0.0124 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0083 (3)	0.0090 (4)	0.0134 (4)	−0.0048 (3)	−0.0019 (3)	−0.0005 (3)
Mn1	0.0118 (3)	0.0083 (3)	0.0079 (3)	−0.0027 (2)	−0.0003 (2)	−0.0020 (2)
P	0.0064 (5)	0.0072 (5)	0.0062 (4)	−0.0032 (4)	0.0006 (3)	−0.0018 (4)
O1	0.0073 (12)	0.0116 (14)	0.0111 (13)	−0.0058 (11)	0.0004 (10)	−0.0019 (11)
O2	0.0072 (12)	0.0085 (13)	0.0069 (12)	−0.0038 (10)	0.0012 (10)	−0.0025 (10)
O3	0.0115 (13)	0.0112 (14)	0.0088 (12)	−0.0036 (11)	0.0012 (10)	−0.0059 (11)
O4	0.0125 (14)	0.0098 (14)	0.0123 (14)	−0.0035 (11)	0.0016 (11)	−0.0001 (11)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.925 (2)	Mn1—O1ⁱⁱ	2.164 (3)
Cu1—O2	1.925 (2)	Mn1—O2^vi	2.186 (2)
Cu1—O1ⁱⁱ	1.975 (3)	P—O4	1.514 (3)
Cu1—O1ⁱⁱⁱ	1.975 (3)	P—O3	1.543 (3)
Mn1—O4	2.113 (3)	P—O2	1.550 (2)
Mn1—O3^iv	2.134 (2)	P—O1	1.555 (3)
Mn1—O3^v	2.152 (3)

O2ⁱ—Cu1—O2	180.00 (9)	O4—P—O3	111.58 (15)
O2ⁱ—Cu1—O1ⁱⁱ	90.92 (10)	O4—P—O2	110.45 (14)
O2—Cu1—O1ⁱⁱ	89.08 (10)	O3—P—O2	108.03 (15)
O2ⁱ—Cu1—O1ⁱⁱⁱ	89.08 (10)	O4—P—O1	107.78 (15)
O2—Cu1—O1ⁱⁱⁱ	90.92 (10)	O3—P—O1	110.22 (15)
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	180.00 (14)	O2—P—O1	108.75 (14)
O4—Mn1—O3^iv	96.73 (10)	P—O1—Cu1^vii	123.91 (15)
O4—Mn1—O3^v	125.32 (10)	P—O1—Mn1^vii	110.66 (14)
O3^iv—Mn1—O3^v	79.75 (11)	Cu1^vii—O1—Mn1^vii	125.43 (12)
O4—Mn1—O1ⁱⁱ	101.81 (10)	P—O2—Cu1	119.17 (14)
O3^iv—Mn1—O1ⁱⁱ	106.77 (10)	P—O2—Mn1^vi	129.51 (14)
O3^v—Mn1—O1ⁱⁱ	131.75 (10)	Cu1—O2—Mn1^vi	111.23 (11)
O4—Mn1—O2^vi	86.87 (9)	P—O3—Mn1^iv	129.12 (16)
O3^iv—Mn1—O2^vi	160.81 (10)	P—O3—Mn1^viii	125.17 (15)
O3^v—Mn1—O2^vi	82.80 (9)	Mn1^iv—O3—Mn1^viii	100.25 (11)
O1ⁱⁱ—Mn1—O2^vi	90.81 (9)	P—O4—Mn1	116.27 (15)

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

Bond-valence data top

Na₂NiCu(PO₄)₂ (I)
	Na	Ni	Cu	P	Σ
O1	0.137, 0.111	0.240_?2	0.395_?2	1.087	1.97
O2	0.243, 0.108		0.546_?2	1.201	2.10
O3	0.234, 0.105	0.352_?2		1.238	1.93
O4	0.226, 0.125	0.321_?2	0.042_?2	1.242	1.96
	1.29	1.83	1.97	4.77
Mn₂Cu(PO₄)₂ (II)
	Mn	Cu	P	Σ
O1	0.364	0.449_?2	1.148	1.96
O2	0.343	0.514_?2	1.157	2.01
O3	0.395, 0.376	0.025_?2	1.179	1.98
O4	0.418, 0.057		1.275	1.75
	1.96	1.98	4.76

The symbols \downarrow 2 indicate a multiplication of the corresponding contribution along the column due to the symmetry. The long-distance bonds improve the total charges of the O atoms.

Selected geometric parameters (Å) top

I
Cu1—O2	1.9029 (19)	P1—O4	1.5239 (19)
Cu1—O2ⁱ	1.9029 (19)	P1—O3	1.5251 (19)
Cu1—O1ⁱⁱ	2.0223 (18)	P1—O2	1.5362 (19)
Cu1—O1ⁱⁱⁱ	2.0223 (18)	P1—O1	1.573 (2)
Cu1—O4^iv	2.856 (2)	Na1—O2	2.323 (2)
Cu1—O4^xv	2.856 (2)	Na1—O3^viii	2.338 (2)
Ni1—O3^iv	2.0406 (19)	Na1—O4ⁱⁱ	2.351 (2)
Ni1—O3	2.0406 (19)	Na1—O1^ix	2.536 (2)
Ni1—O4^v	2.0740 (19)	Na1—O4^x	2.569 (2)
Ni1—O4^vi	2.0740 (19)	Na1—O1ⁱⁱ	2.612 (2)
Ni1—O1^vii	2.1821 (19)	Na1—O2^x	2.624 (2)
Ni1—O1ⁱⁱⁱ	2.1821 (19)	Na1—O3^ix	2.633 (2)

O2—Cu1—O2ⁱ	180	O2—Cu1—O1ⁱⁱⁱ	90.78 (8)
O2—Cu1—O1ⁱⁱ	89.22 (8)	O2ⁱ—Cu1—O1ⁱⁱⁱ	89.22 (8)
O2ⁱ—Cu1—O1ⁱⁱ	90.78 (8)	O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	180
O3^iv—Ni1—O3	180	O3^iv—Ni1—O4^v	87.91 (7)
O3^iv—Ni1—O4^vi	92.09 (7)	O3—Ni1—O4^v	92.09 (7)
O3—Ni1—O4^vii	87.91 (7)	O4^vi—Ni1—O4^v	180

II
Cu1—O2^xi	1.925 (2)	Mn1—O3^xiv	2.152 (3)
Cu1—O2	1.925 (2)	Mn1—O1^xii	2.164 (3)
Cu1—O1^xii	1.975 (3)	Mn1—O2^x	2.186 (2)
Cu1—O1^xiii	1.975 (3)	Mn1—O4 ^xii	2.848 (3)
Cu1—O3^xi	3.039 (3)	P—O4	1.514 (3)
Cu1—O3	3.039 (3)	P—O3	1.543 (3)
Mn1—O4	2.113 (3)	P—O2	1.550 (2)
Mn1—O3^v	2.134 (2)	P—O1	1.555 (3)

O2^xi—Cu1—O2	180	O2^xi—Cu1—O1^xiii	89.08 (10)
O2^xi—Cu1—O1^xii	90.92 (10)	O2—Cu1—O1^xiii	90.92 (10)
O2—Cu1—O1^xii	89.08 (10)	O1^xii—Cu1—O1^xiii	180
O4—Mn1—O3^v	96.73 (10)	O3^xiv—Mn1—O1^xii	131.75 (10)
O4—Mn1—O3^xiv	125.32 (10)	O4—Mn1—O2^x	86.87 (9)
O3^v—Mn1—O3^xiv	79.75 (11)	O3^v—Mn1—O2^x	160.81 (10)
O4—Mn1—O1^xii	101.81 (10)	O3^xiv—Mn1—O2^x	82.80 (9)
O3^v—Mn1—O1^xii	106.77 (10)	O1^xii—Mn1—O2^x	90.81 (9)

Symmetry code(s): (i) -x+2, -y+1, -z+1; (ii) x+1/2, -y+1/2, z+1/2; (iii) -x+3/2, y+1/2, -z+1/2; (iv) -x+2, -y+1, -z; (v) -x+1, -y+1, -z; (vi) x+1, y, z; (vii) x+1/2, -y+1/2, z-1/2; (viii) x, y, z+1; (ix) x-1/2, -y+1/2, z+1/2; (x) -x+1, -y+1, -z+1; (xi) -x+1, -y, -z+1; (xii) x-1, y, z; (xiii) -x+2, -y, -z+1; (xiv) x-1, y+1, z; (xv) -x, -y, -z.

Crystal data for mixed Cu,Ni and Cu,Mn phosphates (with or without additional Na, Ca, Ba and Cs metal atoms) top

Compound	Unit-cell parameters, a, b, c (Å) and α, β and γ (°)		Volume (Å³); Z	Space group	Me-centered coordination polyhedra	Me—O distances (Å)	Periodicity of the MeO_n framework	Structure type	Reference
Ba(Mn_0.66Cu_0.34)P₂O₇*	5.4268 (3)	102.184 (4)	288.89 (3)	P1	⁴⁺¹[(Mn,Cu)O₅]	2.04–2.15, 2.28	0-periodic	BaZnP₂O₇	Lopes et al. (2013)
	7.5965 (5)	85.624 (4)	2				(isolated dimers)
	7.1925 (5)	89.474 (4)
NaCs(Cu_0.65Mn_0.35)P₂O₇	5.208 (2)		762.1 (5)	Cmc2₁	⁴⁺¹[(Cu,Mn)O₅]	2.01–2.09	0-periodic	K₂CuP₂O₇	Huang & Hwu (1998)
	15.073 (5)		4				(isolated pyramids)
	9.708 (3)
Ca₃Cu₂Ni(PO₄)₄*	17.71388 (9)		635.81 (1)	P2₁/a	⁴[CuO₄]	1.92–1.95	0-periodic	CaCu₃(PO₄)₄	Pomjakushin et al. (2007)
	4.88512 (2)	123.8436 (3)	2		⁵[(Cu_0.5Ni_0.5)O₅]	1.95–2.12	(trimers)
	8.84635 (5)
Ca₃CuNi₂(PO₄)₄*	17.7174 (1)		1269.22 (2)	C2/c	⁴[CuO₄]	1.94–1.94	0-periodic	CaCu₃(PO₄)₄-derivative	Pomjakushin et al. (2007)
	4.82109 (4)	123.6373 (5)	4		⁵[NiO₅]	1.98–2.06	(trimers)
	17.8475 (1)
Na₂CuNi(PO₄)₂	5.1300 (1)		302.31 (1)	P2₁/n	⁶[NiO₆]	2.04–2.18	1-periodic	β-NaCuPO₄	This paper
	8.6729 (2)	97.104 (3)	2		⁴⁺²[CuO₆]	1.90–2.02, 2.86	(chains)
	6.8473 (2)
(Cu,Ni)₂P₂O₇*	4.52 (1)		238 (2)	A2/m	⁴⁺²[(Cu,Ni)O₆]	No data	2-periodic	Thortveitite	Handizi et al. (1993)
	8.19 (1)	106.90 (1)	2				(gibbsite-type layers)	Sc₂Si₂O₇
	6.71 (1)
(Mn_0.54Cu_0.46)₂P₂O₇	4.504 (2)		244.35 (21)	A2/m	⁴⁺²[(Mn,Cu)O₆]	2.02–2.07, 2.46	2-periodic	Thortveitite	Handizi et al. (1994)
	8.422 (3)	106.26 (4)	2				(gibbsite-type layers)	Sc₂Si₂O₇
	6.710 (4)
Mn_2.5Cu_0.5(PO₄)₂	8.8428 (3)		610.28 (4)	P2₁/c	⁶[MnO₆]	2.09–2.41	2-periodic	Graftonite	Bond et al. (2011)
	11.5331 (4)	98.712 (2)	4		³⁺²[MnO₅]	1.88–2.05, 2.30, 2.49	(corrugated layers)	(Mn,Fe,Ca,Mg)₃(PO₄)₂
	6.0539 (2)				⁴[CuO₄]	1.95–1.99
Cu₂Mn(PO₄)₂(H₂O)	5.381 (2)		671.84 (36)	P2₁/n	⁶[MnO₆]	2.05–2.41	2-periodic	Unique	Liao et al. (1995)
	6.181 (2)	96.08 (2)	4		⁴⁺¹[CuO₅]	1.93–2.01, 2.34	(corrugated blocks)
	20.314 (4)				⁴⁺¹⁺¹[CuO₆]	1.90–2.03, 2.55, 2.86
Mn₂Cu(PO₄)₂	4.8292 (5)	72.716 (8)	153.35 (3)	P1	⁵[MnO₅]	2.11–2.19	2-periodic	Cu₃(PO₄)₂	This paper
	5.4051 (5)	86.579 (8)	1		⁴[CuO₄]	1.93–1.98	(layers)
	6.5968 (6)	69.064 (9)
CuNi₂(PO₄)₂*	6.393 (1)		281.24 (8)	P2₁/n	⁵[NiO₅]	199–2.06	3-periodic	Cu₃(PO₄)₂-derivative	Goni et al. (1999)
	9.325 (1)	90.71 (1)	2		⁴⁺²[CuO₆]	1.97–2.01, 2.61	(framework)
	4.718 (1)
Mn₂Cu(PO₄)₂(H₂O)	8.332 (1)		692.40 (19)	P2₁/n	⁵⁺¹[MnO₆]	2.12–2.17, 2.53	3-periodic	Unique	Liao et al. (1995)
	10.094 (2)	115.11 (1)	4		⁶[MnO₆]	2.11–2.25	(framework)
	9.092 (1)				⁴⁺¹[CuO₅]	1.92–2.02, 2.33
Cu_2.5Mn(PO₄)₂(OH)	8.833 (3)	101.33 (3)	327.46 (3)	P1	⁴⁺²[CuO₆]	1.94–1.97, 2.80	3-periodic	Unique	Yakubovich & Melnikov (1993)
	7.556 (3)	95.80 (3)	2		⁵[CuO₅]	1.92–2.18	(framework)
	5.334 (1)	108.62 (3)			⁴⁺²[CuO₆]	1.95–2.00, 2.49, 2.63
					⁵[MnO₅]	2.11-2.21
Cu₃NiO(PO₄)₂	8.2288 (2)		640.50 (3)	P2₁/n	⁴[CuO₄]	1.86–2.11	3-periodic	Unique	Weimann et al. (2017)
	9.8773 (2)	107.826 (3)	4		⁴⁺¹[CuO₅]	1.92–2.21, 2.69	(framework)
	8.2777 (3)				⁴⁺²[CuO₆]	1.93–2.15, 2.26, 2.32
					⁶[NiO₆]	2.02–2.23

Note: (*) based on powder diffraction (including neutron sources).

Selected geometric parameters (Å, °) top

I
Cu1—O2	1.9029 (19)	Na1—O2^ix	2.624 (2)
Cu1—O1ⁱⁱ	2.0223 (18)	Na1—O3^viii	2.633 (2)
Cu1—O4^iv	2.856 (2)	Ni1—O3	2.0406 (19)
Na1—O2	2.323 (2)	Ni1—O4^v	2.0740 (19)
Na1—O3^vii	2.338 (2)	Ni1—O1ⁱⁱⁱ	2.1821 (19)
Na1—O4ⁱⁱ	2.351 (2)	P1—O4	1.5239 (19)
Na1—O1^viii	2.536 (2)	P1—O3	1.5251 (19)
Na1—O4^ix	2.569 (2)	P1—O2	1.5362 (19)
Na1—O1ⁱⁱ	2.612 (2)	P1—O1	1.573 (2)

O2—Cu1—O2ⁱ	180.0	O2—Cu1—O1ⁱⁱⁱ	90.78 (8)
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	180.0	O3^iv—Ni1—O3	180.0
O3^iv—Ni1—O4^v	87.91 (7)	O4^vi—Ni1—O4^v	180.00

II
Mn1—O1^xi	2.164 (3)	Cu1—O2	1.925 (2)
Mn1—O2^ix	2.186 (2)	Cu1—O3	3.039 (3)
Mn1—O3^v	2.134 (2)	P—O1	1.555 (3)
Mn1—O3^xiii	2.152 (3)	P—O2	1.550 (2)
Mn1—O4^xi	2.848 (3)	P—O3	1.543 (3)
Mn1—O4	2.113 (3)	P—O4	1.514 (3)
Cu1—O1^xi	1.975 (3)

O2^x—Cu1—O2	180.00	O2^x—Cu1—O1^xii	89.08 (10)
O1^xi—Cu1—O1^xii	180.00 (14)	O4—Mn1—O3^v	96.73 (10)
O3^xiv=ii—Mn1—O1^xi	131.75 (10)	O4—Mn1—O3^xiii	125.32 (10)
O4—Mn1—O2^ix	86.87 (9)	O3^v—Mn1—O3^xiii	79.75 (11)
O3^v—Mn1—O2^ix	160.81 (10)	O4—Mn1—O1^xi	101.81 (10)
O3^xiii—Mn1—O2^ix	82.80 (9)	O3^v—Mn1—O1^xi	106.77 (10)
O1^xi—Mn1—O2^ix	90.81 (9)

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

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Novel first-row transition-metal phosphates: hydro­thermal synthesis and crystal structures

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Novel first-row transition-metal phosphates: hydrothermal synthesis and crystal structures