A first Mn member in the struvite morphotropic series, CsMn(H2O)6(PO4): hydro­thermal synthesis, crystal structure and inter­connections within the family of related phosphates

Kiriukhina, G.V.; Yakubovich, O.V.; Kochetkova, E.M.; Dimitrova, O.V.; Volkov, A.S.

doi:10.1107/S2053229618009798

A first Mn member in the struvite morphotropic series, CsMn(H₂O)₆(PO₄): hydrothermal synthesis, crystal structure and interconnections within the family of related phosphates

G. V. Kiriukhina, O. V. Yakubovich, E. M. Kochetkova, O. V. Dimitrova and A. S. Volkov

Caesium manganese hexahydrate phosphate, CsMn(H₂O)₆(PO₄), was synthesized under hydrothermal conditions. Its crystal structure was determined from single-crystal X-ray diffraction data. The novel phase crystallizes in the hexagonal space group P6₃mc and represents the first manganese member in the struvite morphotropic series, AM(H₂O)₆(TO₄). Its crystal structure is built from Mn(H₂O)₆ octahedra and PO₄ tetrahedra linked into a framework via hydrogen bonding. The large Cs atoms are encapsulated in the framework cuboctahedral cavities. It is shown that the size of the A⁺ ionic radius within the morphotropic series AM(H₂O)₆(XO₄) results is certain types of crystal structures and affects the values of the unit-cell parameters. Structural relationships with Na(H₂O)Mg(H₂O)₆(PO₄) and the mineral hazenite, KNa(H₂O)₂Mg₂(H₂O)₁₂(PO₄)₂, are discussed.

Keywords: struvite; morphotropic series; phosphates; hydrothermal synthesis; hazenite; crystal structure; manganese hydrate phosphate; biominerals.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618009798/fn3263sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618009798/fn3263Isup2.hkl Contains datablock I

CCDC reference: 1854647

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a) within WinGX (Farrugia, 2012); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b) within WinGX (Farrugia, 2012); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXT (Sheldrick, 2015a) within WinGX (Farrugia, 2012).

Caesium manganese hexahydrate phosphate top

Crystal data top

CsMn(H₂O)₆(PO₄)	D_x = 2.558 Mg m⁻³
M_r = 390.92	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃mc	Cell parameters from 3866 reflections
a = 6.9809 (7) Å	θ = 3.4–32.5°
c = 12.0270 (9) Å	µ = 5.02 mm⁻¹
V = 507.59 (11) Å³	T = 293 K
Z = 2	Hexagonal prism, colourless
F(000) = 374	0.12 × 0.08 × 0.06 mm

Data collection top

Agilent Xcalibur Sapphire3 diffractometer	737 independent reflections
Radiation source: Enhance X-ray Source	687 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	R_int = 0.045
ω scans	θ_max = 32.5°, θ_min = 3.4°
Absorption correction: gaussian Numerical absorption correction based on gaussian integration over a multifaceted crystal model	h = −10→10
T_min = 0.380, T_max = 0.658	k = −10→10
9705 measured reflections	l = −18→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	All H-atom parameters refined
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.020P)² + 0.8P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
737 reflections	Δρ_max = 0.76 e Å⁻³
41 parameters	Δρ_min = −0.79 e Å⁻³
4 restraints	Absolute structure: Flack x determined using 283 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.015 (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
Cs1	0.666667	0.333333	0.43938 (17)	0.0518 (3)
Mn1	0.333333	0.666667	0.31642 (19)	0.0238 (4)
P1	0.000000	0.000000	0.6603 (2)	0.0185 (4)
O1	0.1198 (3)	0.2396 (6)	0.6191 (5)	0.0269 (8)
O2	0.000000	0.000000	0.7891 (6)	0.030 (2)
O3	0.1816 (4)	0.3632 (9)	0.4103 (3)	0.0496 (16)
O4	0.4834 (6)	0.5166 (6)	0.2141 (5)	0.0507 (17)
H1	0.126 (3)	0.252 (6)	0.374 (5)	0.06 (3)*
H2	0.387 (9)	0.413 (7)	0.182 (4)	0.05 (2)*
H3	0.168 (8)	0.337 (15)	0.4755 (16)	0.07 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0498 (4)	0.0498 (4)	0.0558 (6)	0.0249 (2)	0.000	0.000
Mn1	0.0256 (6)	0.0256 (6)	0.0202 (8)	0.0128 (3)	0.000	0.000
P1	0.0214 (6)	0.0214 (6)	0.0127 (9)	0.0107 (3)	0.000	0.000
O1	0.0336 (14)	0.0221 (17)	0.0212 (17)	0.0110 (9)	0.0022 (10)	0.004 (2)
O2	0.040 (3)	0.040 (3)	0.011 (3)	0.0199 (15)	0.000	0.000
O3	0.083 (4)	0.026 (2)	0.021 (2)	0.0128 (12)	0.0016 (11)	0.003 (2)
O4	0.033 (2)	0.033 (2)	0.071 (4)	0.006 (3)	0.0201 (16)	−0.0201 (16)

Geometric parameters (Å, º) top

Cs1—O4ⁱ	3.500 (8)	Mn1—O3ⁱⁱⁱ	2.154 (5)
Cs1—O4ⁱⁱ	3.500 (8)	Mn1—O3	2.154 (5)
Cs1—O4	3.501 (8)	Mn1—O4^ix	2.192 (5)
Cs1—O3ⁱⁱⁱ	3.5125 (6)	Mn1—O4ⁱⁱⁱ	2.192 (5)
Cs1—O3^iv	3.5126 (6)	Mn1—O4	2.192 (5)
Cs1—O3	3.5126 (6)	P1—O1^x	1.531 (4)
Cs1—O3ⁱⁱ	3.5126 (6)	P1—O1^iv	1.531 (4)
Cs1—O3ⁱ	3.5126 (6)	P1—O1	1.531 (4)
Cs1—O3^v	3.5126 (6)	P1—O2	1.550 (8)
Cs1—O4^vi	3.769 (8)	O3—H1	0.8000 (15)
Cs1—O4^vii	3.769 (8)	O3—H3	0.8000 (15)
Cs1—O4^viii	3.769 (8)	O4—H2	0.8000 (15)
Mn1—O3^ix	2.154 (5)	O4—H2^xi	0.8000 (15)

O4ⁱ—Cs1—O4ⁱⁱ	66.50 (13)	O4^vi—Cs1—O4^viii	49.27 (14)
O4ⁱ—Cs1—O4	66.50 (13)	O4^vii—Cs1—O4^viii	49.27 (14)
O4ⁱⁱ—Cs1—O4	66.50 (13)	O3^ix—Mn1—O3ⁱⁱⁱ	95.04 (19)
O4ⁱ—Cs1—O3ⁱⁱⁱ	116.84 (10)	O3^ix—Mn1—O3	95.04 (19)
O4ⁱⁱ—Cs1—O3ⁱⁱⁱ	87.45 (9)	O3ⁱⁱⁱ—Mn1—O3	95.04 (19)
O4—Cs1—O3ⁱⁱⁱ	50.35 (10)	O3^ix—Mn1—O4^ix	86.67 (16)
O4ⁱ—Cs1—O3^iv	50.35 (10)	O3ⁱⁱⁱ—Mn1—O4^ix	177.5 (3)
O4ⁱⁱ—Cs1—O3^iv	116.84 (10)	O3—Mn1—O4^ix	86.67 (16)
O4—Cs1—O3^iv	87.45 (9)	O3^ix—Mn1—O4ⁱⁱⁱ	86.67 (16)
O3ⁱⁱⁱ—Cs1—O3^iv	119.02 (3)	O3ⁱⁱⁱ—Mn1—O4ⁱⁱⁱ	86.67 (16)
O4ⁱ—Cs1—O3	87.45 (9)	O3—Mn1—O4ⁱⁱⁱ	177.5 (3)
O4ⁱⁱ—Cs1—O3	116.84 (10)	O4^ix—Mn1—O4ⁱⁱⁱ	91.6 (3)
O4—Cs1—O3	50.35 (10)	O3^ix—Mn1—O4	177.5 (3)
O3ⁱⁱⁱ—Cs1—O3	53.79 (17)	O3ⁱⁱⁱ—Mn1—O4	86.67 (16)
O3^iv—Cs1—O3	65.56 (17)	O3—Mn1—O4	86.67 (16)
O4ⁱ—Cs1—O3ⁱⁱ	116.84 (10)	O4^ix—Mn1—O4	91.6 (3)
O4ⁱⁱ—Cs1—O3ⁱⁱ	50.35 (10)	O4ⁱⁱⁱ—Mn1—O4	91.6 (3)
O4—Cs1—O3ⁱⁱ	87.45 (9)	O3^ix—Mn1—Cs1	128.24 (15)
O3ⁱⁱⁱ—Cs1—O3ⁱⁱ	65.56 (17)	O3ⁱⁱⁱ—Mn1—Cs1	54.527 (13)
O3^iv—Cs1—O3ⁱⁱ	167.14 (15)	O3—Mn1—Cs1	54.528 (13)
O3—Cs1—O3ⁱⁱ	119.02 (3)	O4^ix—Mn1—Cs1	125.580 (11)
O4ⁱ—Cs1—O3ⁱ	50.35 (10)	O4ⁱⁱⁱ—Mn1—Cs1	125.580 (11)
O4ⁱⁱ—Cs1—O3ⁱ	87.45 (9)	O4—Mn1—Cs1	54.3 (2)
O4—Cs1—O3ⁱ	116.84 (10)	O3^ix—Mn1—Cs1^xii	54.528 (14)
O3ⁱⁱⁱ—Cs1—O3ⁱ	167.14 (15)	O3ⁱⁱⁱ—Mn1—Cs1^xii	54.529 (13)
O3^iv—Cs1—O3ⁱ	53.78 (17)	O3—Mn1—Cs1^xii	128.24 (15)
O3—Cs1—O3ⁱ	119.02 (3)	O4^ix—Mn1—Cs1^xii	125.578 (11)
O3ⁱⁱ—Cs1—O3ⁱ	119.02 (3)	O4ⁱⁱⁱ—Mn1—Cs1^xii	54.3 (2)
O4ⁱ—Cs1—O3^v	87.45 (9)	O4—Mn1—Cs1^xii	125.580 (11)
O4ⁱⁱ—Cs1—O3^v	50.35 (10)	Cs1—Mn1—Cs1^xii	108.79 (2)
O4—Cs1—O3^v	116.84 (10)	O3^ix—Mn1—Cs1^xiii	54.528 (14)
O3ⁱⁱⁱ—Cs1—O3^v	119.02 (3)	O3ⁱⁱⁱ—Mn1—Cs1^xiii	128.24 (15)
O3^iv—Cs1—O3^v	119.02 (3)	O3—Mn1—Cs1^xiii	54.528 (14)
O3—Cs1—O3^v	167.14 (15)	O4^ix—Mn1—Cs1^xiii	54.3 (2)
O3ⁱⁱ—Cs1—O3^v	53.78 (17)	O4ⁱⁱⁱ—Mn1—Cs1^xiii	125.578 (11)
O3ⁱ—Cs1—O3^v	65.56 (17)	O4—Mn1—Cs1^xiii	125.580 (11)
O4ⁱ—Cs1—O4^vi	146.19 (4)	Cs1—Mn1—Cs1^xiii	108.79 (2)
O4ⁱⁱ—Cs1—O4^vi	146.19 (4)	Cs1^xii—Mn1—Cs1^xiii	108.78 (2)
O4—Cs1—O4^vi	111.95 (2)	O1^x—P1—O1^iv	110.1 (2)
O3ⁱⁱⁱ—Cs1—O4^vi	70.16 (11)	O1^x—P1—O1	110.1 (2)
O3^iv—Cs1—O4^vi	96.43 (8)	O1^iv—P1—O1	110.1 (2)
O3—Cs1—O4^vi	70.16 (11)	O1^x—P1—O2	108.9 (2)
O3ⁱⁱ—Cs1—O4^vi	96.43 (8)	O1^iv—P1—O2	108.9 (2)
O3ⁱ—Cs1—O4^vi	119.28 (10)	O1—P1—O2	108.9 (2)
O3^v—Cs1—O4^vi	119.28 (10)	Mn1—O3—Cs1	95.51 (8)
O4ⁱ—Cs1—O4^vii	146.19 (4)	Mn1—O3—Cs1^xiii	95.51 (8)
O4ⁱⁱ—Cs1—O4^vii	111.95 (2)	Cs1—O3—Cs1^xiii	167.14 (15)
O4—Cs1—O4^vii	146.19 (4)	Mn1—O3—H1	115 (5)
O3ⁱⁱⁱ—Cs1—O4^vii	96.43 (8)	Cs1—O3—H1	90.7 (6)
O3^iv—Cs1—O4^vii	119.28 (10)	Cs1^xiii—O3—H1	90.7 (6)
O3—Cs1—O4^vii	119.28 (10)	Mn1—O3—H3	133 (7)
O3ⁱⁱ—Cs1—O4^vii	70.16 (11)	Cs1—O3—H3	83.8 (2)
O3ⁱ—Cs1—O4^vii	96.43 (8)	Cs1^xiii—O3—H3	83.8 (2)
O3^v—Cs1—O4^vii	70.16 (11)	H1—O3—H3	112 (8)
O4^vi—Cs1—O4^vii	49.27 (14)	Mn1—O4—Cs1	95.1 (2)
O4ⁱ—Cs1—O4^viii	111.95 (2)	Mn1—O4—Cs1^xiv	95.4 (2)
O4ⁱⁱ—Cs1—O4^viii	146.19 (4)	Cs1—O4—Cs1^xiv	169.50 (16)
O4—Cs1—O4^viii	146.19 (4)	Mn1—O4—H2	108 (6)
O3ⁱⁱⁱ—Cs1—O4^viii	119.28 (10)	Cs1—O4—H2	110 (5)
O3^iv—Cs1—O4^viii	70.16 (11)	Cs1^xiv—O4—H2	66 (5)
O3—Cs1—O4^viii	96.43 (8)	Mn1—O4—H2^xi	108 (6)
O3ⁱⁱ—Cs1—O4^viii	119.28 (10)	Cs1—O4—H2^xi	110 (5)
O3ⁱ—Cs1—O4^viii	70.16 (11)	Cs1^xiv—O4—H2^xi	66 (5)
O3^v—Cs1—O4^viii	96.43 (8)	H2—O4—H2^xi	122 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O2^xv	0.80 (1)	1.84 (1)	2.636 (7)	179 (7)
O4—H2···O1^xvi	0.80 (1)	1.93 (3)	2.676 (4)	155 (8)
O3—H3···O1	0.80 (1)	1.83 (2)	2.620 (7)	173 (10)

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

Bond-valance data for CsMn(H₂O)₆(PO₄) top

	Cs	Mn	P	H1	H2	H3	Σ
O1			1.28_{×3\downarrow}		0.24_×2?	0.28	2.04
O2			1.17	0.27_×3_→			1.98
O3	0.087_{×6\downarrow×2}_→	0.348_{×3\downarrow}		0.73		0.72	1.97
O4	0.086_{×3\downarrow,} 0.075_{×3\downarrow}	0.318_{×3\downarrow}			0.76_×2_→		2.00
Σ	1	2	5	1	1	1

Algorithm and empirical parameters for calculations were used from (Pyatenko, 1972). The symbols \downarrow and → indicate a multiplication of the corresponding contribution in the columns or rows by symmetry.

Crystallographic characteristics for compounds of the struvite morphotropic series, AM(H₂O)₆[XO₄] (A = K, NH₄, Rb, H₂O, Cs, Tl; M = Mn, Fe, Co, Ni, Mg; X = P, As) and related phosphates top

Compound	Unit-cell parameters a, b, c (Å)	r_A (Å)	<d_A—O> (Å)	Reference
Orthorhombic (space group Pmn2₁, Z = 2)		The sequence of layers (Abc)
Struvite-K, KMg(H₂O)₆(PO₄)	6.903 (3), 6.174 (2), 11.146 (3)	1.59	3.27	Mathew et al. (1979)
Struvite, NH₄Mg(H₂O)₆(PO₄)	6.955 (1), 6.142 (1), 11.218 (2)	1.60	3.31	Ferraris et al. (1986)
NH₄Ni(H₂O)₆(PO₄)	6.9240 (14) , 6.1040 (12), 11.166 (2)	1.60	3.29	Blachnik et al. (1997)
NH₄Co(H₂O)₆(PO₄)	6.946 (2), 6.157 (2), 11.172 (6)	1.60	3.30	El Bali et al. (2005)
(H₂O)Ni(H₂O)₆[HPO₄]	6.9160 (3), 6.1032 (3), 11.1679 (6)		3.30	Wang et al. (2005)
RbMg(H₂O)₆(PO₄)	6.8381 (9), 6.1407 (9), 11.2454 (19)	1.65	3.31	Weil (2008b)
TlMg(H₂O)₆(PO₄)	6.8129 (8), 6.1148 (10), 11.2769 (16)	1.66	3.30	Weil (2008b)
KMg(H₂O)₆[AsO₄]	6.99 (3), 6.22 (2), 11.26 (4)	1.59	3.32	Abdija et al. (2014)
NH₄Mg(H₂O)₆[AsO₄]	7.054 (4), 6.205 (3), 11.368 (6)	1.60	3.35	Ferraris et al. (1973)
RbMg(H₂O)₆[AsO₄]	6.9310 (9), 6.2054 (7), 11.3991 (7)	1.65	3.35	Weil (2008b)
TlMg(H₂O)₆[AsO₄]	6.9591 (7), 6.1937 (5), 11.4306 (6)	1.66	3.34	Weil (2008b)

Hexagonal (space group P6₃mc, Z = 2)		The sequence of layers (AbγA'cβ)
CsMg(H₂O)₆(PO₄)	6.8827 (8), 11.9188 (16)	1.88	3.54	Weil (2008a)
CsMn(H₂O)₆(PO₄)	6.9809 (7), 12.0270 (9)	1.88	3.57	This work

Cubic (space group F43m, Z = 4)		The sequence of layers (AbγBcαCaβ)
CsMg(H₂O)₆(PO₄)	10.0308 (14)	1.88	3.57	Massa et al. (2003)
CsFe(H₂O)₆(PO₄)	10.06024 (5)	1.88	3.58	Carver et al. (2006)
CsFe(D₂O)₆(PO₄)	10.02420 (9)	1.88	3.58	Carver et al. (2006)
CsMg(H₂O)₆[AsO₄]	10.1609 (5)	1.88	3.62	Weil (2009)

Related structures: tetragonal (space group P4₂/mmc, Z = 2) and orthorhombic (space group Pmnb, Z = 4)
Na(H₂O)Mg(H₂O)₆ (PO₄)	6.731 (2), 10.982 (4)	1.02	2.50	Mathew et al. (1982)
Hazenite, KNa(H₂O)₂Mg₂(H₂O)₁₂(PO₄)₂	6.9349 (4), 25.174 (2), 11.2195 (8)	1.59, 1.02	3.29 2.49	Yang et al. (2011)

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A first Mn member in the struvite morphotropic series, CsMn(H2O)6(PO4): hydro­thermal synthesis, crystal structure and inter­connections within the family of related phosphates

Supporting information

A first Mn member in the struvite morphotropic series, CsMn(H₂O)₆(PO₄): hydrothermal synthesis, crystal structure and interconnections within the family of related phosphates