Buy article online - an online subscription or single-article purchase is required to access this article.
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.
Supporting information
CCDC reference: 1854647
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) | Dx = 2.558 Mg m−3 |
Mr = 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 | Rint = 0.045 |
ω scans | θmax = 32.5°, θmin = 3.4° |
Absorption correction: gaussian Numerical absorption correction based on gaussian
integration over a multifaceted crystal model | h = −10→10 |
Tmin = 0.380, Tmax = 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(Fo2) + (0.020P)2 + 0.8P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
737 reflections | Δρmax = 0.76 e Å−3 |
41 parameters | Δρmin = −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 | Uiso*/Ueq | |
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—O4ix | 2.192 (5) |
Cs1—O3iii | 3.5125 (6) | Mn1—O4iii | 2.192 (5) |
Cs1—O3iv | 3.5126 (6) | Mn1—O4 | 2.192 (5) |
Cs1—O3 | 3.5126 (6) | P1—O1x | 1.531 (4) |
Cs1—O3ii | 3.5126 (6) | P1—O1iv | 1.531 (4) |
Cs1—O3i | 3.5126 (6) | P1—O1 | 1.531 (4) |
Cs1—O3v | 3.5126 (6) | P1—O2 | 1.550 (8) |
Cs1—O4vi | 3.769 (8) | O3—H1 | 0.8000 (15) |
Cs1—O4vii | 3.769 (8) | O3—H3 | 0.8000 (15) |
Cs1—O4viii | 3.769 (8) | O4—H2 | 0.8000 (15) |
Mn1—O3ix | 2.154 (5) | O4—H2xi | 0.8000 (15) |
| | | |
O4i—Cs1—O4ii | 66.50 (13) | O4vi—Cs1—O4viii | 49.27 (14) |
O4i—Cs1—O4 | 66.50 (13) | O4vii—Cs1—O4viii | 49.27 (14) |
O4ii—Cs1—O4 | 66.50 (13) | O3ix—Mn1—O3iii | 95.04 (19) |
O4i—Cs1—O3iii | 116.84 (10) | O3ix—Mn1—O3 | 95.04 (19) |
O4ii—Cs1—O3iii | 87.45 (9) | O3iii—Mn1—O3 | 95.04 (19) |
O4—Cs1—O3iii | 50.35 (10) | O3ix—Mn1—O4ix | 86.67 (16) |
O4i—Cs1—O3iv | 50.35 (10) | O3iii—Mn1—O4ix | 177.5 (3) |
O4ii—Cs1—O3iv | 116.84 (10) | O3—Mn1—O4ix | 86.67 (16) |
O4—Cs1—O3iv | 87.45 (9) | O3ix—Mn1—O4iii | 86.67 (16) |
O3iii—Cs1—O3iv | 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) | O4ix—Mn1—O4iii | 91.6 (3) |
O4—Cs1—O3 | 50.35 (10) | O3ix—Mn1—O4 | 177.5 (3) |
O3iii—Cs1—O3 | 53.79 (17) | O3iii—Mn1—O4 | 86.67 (16) |
O3iv—Cs1—O3 | 65.56 (17) | O3—Mn1—O4 | 86.67 (16) |
O4i—Cs1—O3ii | 116.84 (10) | O4ix—Mn1—O4 | 91.6 (3) |
O4ii—Cs1—O3ii | 50.35 (10) | O4iii—Mn1—O4 | 91.6 (3) |
O4—Cs1—O3ii | 87.45 (9) | O3ix—Mn1—Cs1 | 128.24 (15) |
O3iii—Cs1—O3ii | 65.56 (17) | O3iii—Mn1—Cs1 | 54.527 (13) |
O3iv—Cs1—O3ii | 167.14 (15) | O3—Mn1—Cs1 | 54.528 (13) |
O3—Cs1—O3ii | 119.02 (3) | O4ix—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) | O3ix—Mn1—Cs1xii | 54.528 (14) |
O3iii—Cs1—O3i | 167.14 (15) | O3iii—Mn1—Cs1xii | 54.529 (13) |
O3iv—Cs1—O3i | 53.78 (17) | O3—Mn1—Cs1xii | 128.24 (15) |
O3—Cs1—O3i | 119.02 (3) | O4ix—Mn1—Cs1xii | 125.578 (11) |
O3ii—Cs1—O3i | 119.02 (3) | O4iii—Mn1—Cs1xii | 54.3 (2) |
O4i—Cs1—O3v | 87.45 (9) | O4—Mn1—Cs1xii | 125.580 (11) |
O4ii—Cs1—O3v | 50.35 (10) | Cs1—Mn1—Cs1xii | 108.79 (2) |
O4—Cs1—O3v | 116.84 (10) | O3ix—Mn1—Cs1xiii | 54.528 (14) |
O3iii—Cs1—O3v | 119.02 (3) | O3iii—Mn1—Cs1xiii | 128.24 (15) |
O3iv—Cs1—O3v | 119.02 (3) | O3—Mn1—Cs1xiii | 54.528 (14) |
O3—Cs1—O3v | 167.14 (15) | O4ix—Mn1—Cs1xiii | 54.3 (2) |
O3ii—Cs1—O3v | 53.78 (17) | O4iii—Mn1—Cs1xiii | 125.578 (11) |
O3i—Cs1—O3v | 65.56 (17) | O4—Mn1—Cs1xiii | 125.580 (11) |
O4i—Cs1—O4vi | 146.19 (4) | Cs1—Mn1—Cs1xiii | 108.79 (2) |
O4ii—Cs1—O4vi | 146.19 (4) | Cs1xii—Mn1—Cs1xiii | 108.78 (2) |
O4—Cs1—O4vi | 111.95 (2) | O1x—P1—O1iv | 110.1 (2) |
O3iii—Cs1—O4vi | 70.16 (11) | O1x—P1—O1 | 110.1 (2) |
O3iv—Cs1—O4vi | 96.43 (8) | O1iv—P1—O1 | 110.1 (2) |
O3—Cs1—O4vi | 70.16 (11) | O1x—P1—O2 | 108.9 (2) |
O3ii—Cs1—O4vi | 96.43 (8) | O1iv—P1—O2 | 108.9 (2) |
O3i—Cs1—O4vi | 119.28 (10) | O1—P1—O2 | 108.9 (2) |
O3v—Cs1—O4vi | 119.28 (10) | Mn1—O3—Cs1 | 95.51 (8) |
O4i—Cs1—O4vii | 146.19 (4) | Mn1—O3—Cs1xiii | 95.51 (8) |
O4ii—Cs1—O4vii | 111.95 (2) | Cs1—O3—Cs1xiii | 167.14 (15) |
O4—Cs1—O4vii | 146.19 (4) | Mn1—O3—H1 | 115 (5) |
O3iii—Cs1—O4vii | 96.43 (8) | Cs1—O3—H1 | 90.7 (6) |
O3iv—Cs1—O4vii | 119.28 (10) | Cs1xiii—O3—H1 | 90.7 (6) |
O3—Cs1—O4vii | 119.28 (10) | Mn1—O3—H3 | 133 (7) |
O3ii—Cs1—O4vii | 70.16 (11) | Cs1—O3—H3 | 83.8 (2) |
O3i—Cs1—O4vii | 96.43 (8) | Cs1xiii—O3—H3 | 83.8 (2) |
O3v—Cs1—O4vii | 70.16 (11) | H1—O3—H3 | 112 (8) |
O4vi—Cs1—O4vii | 49.27 (14) | Mn1—O4—Cs1 | 95.1 (2) |
O4i—Cs1—O4viii | 111.95 (2) | Mn1—O4—Cs1xiv | 95.4 (2) |
O4ii—Cs1—O4viii | 146.19 (4) | Cs1—O4—Cs1xiv | 169.50 (16) |
O4—Cs1—O4viii | 146.19 (4) | Mn1—O4—H2 | 108 (6) |
O3iii—Cs1—O4viii | 119.28 (10) | Cs1—O4—H2 | 110 (5) |
O3iv—Cs1—O4viii | 70.16 (11) | Cs1xiv—O4—H2 | 66 (5) |
O3—Cs1—O4viii | 96.43 (8) | Mn1—O4—H2xi | 108 (6) |
O3ii—Cs1—O4viii | 119.28 (10) | Cs1—O4—H2xi | 110 (5) |
O3i—Cs1—O4viii | 70.16 (11) | Cs1xiv—O4—H2xi | 66 (5) |
O3v—Cs1—O4viii | 96.43 (8) | H2—O4—H2xi | 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···O2xv | 0.80 (1) | 1.84 (1) | 2.636 (7) | 179 (7) |
O4—H2···O1xvi | 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 topCompound | Unit-cell parameters a, b, c (Å) | rA (Å) | <dA—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) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.