Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814004061/wm5004sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536814004061/wm5004Isup2.hkl |
CCDC reference: 988095
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (P-O) = 0.002 Å
- H-atom completeness 72%
- Disorder in main residue
- R factor = 0.039
- wR factor = 0.094
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check PLAT043_ALERT_1_C Calculated and Reported Mol. Weight Differ by .. 16.13 Check PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... Please Check PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. Please Check PLAT354_ALERT_3_C Short O-H (X0.82,N0.98A) OH - H1 ... 0.69 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H12 .. O2 .. 2.75 Ang. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 4 Why ? PLAT976_ALERT_2_C Check Calcd Residual Density 0.70A From OW1 -0.51 eA-3 PLAT976_ALERT_2_C Check Calcd Residual Density 0.72A From OH -0.41 eA-3
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:H28 Al1.07 Ca3.94 Fe2.93 Mg1.0 Atom count from the _atom_site data: H20 Al1.07 Ca3.94 Fe2.93 Mg1.0 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum Al1.07 Ca3.94 Fe2.93 H28 Mg1.01 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff Al 2.14 2.14 0.00 Ca 7.88 7.88 0.00 Fe 5.86 5.86 0.00 H 56.00 40.00 16.00 Mg 2.02 2.02 0.00 O 80.00 80.00 0.00 P 12.00 12.00 0.00 Sr 0.12 0.12 0.00 PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 3 Note PLAT004_ALERT_5_G Polymeric Structure Found with Dimension ....... 2 Info PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 Check PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Fe1 -- OH .. 6.0 su PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Fe1 -- O3 .. 5.3 su PLAT301_ALERT_3_G Main Residue Disorder ............ Percentage = 15 Note PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage = 40 Note PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 5 Note PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms .... ! Info PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 4 Note PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) ..... 1 Why ? PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 27 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 9 ALERT level C = Check. Ensure it is not caused by an omission or oversight 18 ALERT level G = General information/check it is not something unexpected 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
Calcioferrite was originally described by Blum (1858) from a sample found in Battenberg (Rhenish, Bavaria) with the chemical composition (wt.%): P2O5 34.01, Fe2O3 24.34, Al2O3 2.90, CaO 14.81, MgO 2.65, and H2O 20.56 (total = 99.27). Larsen (1940) reported montgomeryite with an ideal chemical formula Ca4Al5(PO4)6(OH)5.11H2O without recognizing its relationship to calcioferrite. Palache et al. (1951), on the basis of the chemistry given by Blum (1858), proposed the chemical formula Ca3Fe3(PO4)4(OH)3.8H2O for calcioferrite. By comparing chemical compositions and X-ray powder diffraction profiles between calcioferrite and montgomeryite, Mead & Mrose (1968) suggested that these two minerals are isostructural. Moore & Araki (1974) first solved the structure of montgomeryite in space group C2/c and revised its chemical formula to Ca4MgAl4(PO4)6(OH)4.12H2O. Nevertheless, Fanfani et al. (1976) observed the presence of some weak reflections that violate the C2/c space group symmetry for montgomeryite, leading them to propose C2 as the actual space group for this mineral. Dunn et al. (1983) studied red montgomeryite from the Tip Top Pegmatite and also concluded that calcioferrite is the Fe3+ analog of montgomeryite based on the similarity between their X-ray powder diffraction patterns. Consequently, they modified the ideal chemical formula of calcioferrite to its present form, Ca4MgFe3+4(PO4)6(OH)4.12H2O.
A second locality for calcioferrite was reported by Henderson & Peisley (1985) at the Moculta quarry in Angaston, South Australia, associated with apatite, jarosite, cacoxenite and altered pyrite, the latter probably being the source of Fe3+. The chemistry and X-ray power data of calcioferrite from this locality are consistent with the previous observations that calcioferrite is isotypic with montgomeryite. However, the structure of calcioferrite has remained undetermined because of its small crystal size and generally poor crystallinity. In the course of identifying minerals for the RRUFF Project (http://rruff.info), we were able to isolate a single crystal of calcioferrite and determine its structure by means of single-crystal X-ray diffraction, demonstrating that its space group is C2/c.
The general composition of the calcioferrite group minerals can be expressed as Ca4AB4(PO4)6(OH)4.12H2O with A = Mg, Fe2+, Mn2+ and B = Al, Fe3+. In addition to calcioferrite, there are three other known members in the group, including montgomeryite (A = Mg, B = Al) (Moore & Araki, 1974; Fanfani et al., 1976), kingsmountite (A = Fe2+, B = Al) (Dunn et al., 1979), and zodacite (A = Mn2+, B = Fe3+) (Dunn et al., 1988). The structure of calcioferrite contains seven non-hydrogen cation sites, two for Ca [((Cal/Sr1); site symmetry 2; occupancy ratio Ca:Sr =0.97:0.03) and Ca2 (site symmetry 2)], two for Fe [((Fe1/Al1); site symmetry 1; occupancy ratio Fe:Al = 0.651:0.349) and (Fe2/Al2; site symmetry 2; occupancy ratio Fe:Al = 0.814:0.186)], one for Mg [site symmetry 2; half-occupation], and two for P [(P1; site symmetry 2) and P2 (site symmetry 1)]. The chains of corner-sharing (Fe/Al)O6 octahedra (parallel to [101]) are linked together by PO4 tetrahedra to form [(Fe/Al)3(PO4)3(OH)2] layers stacking along [010] (Figs. 1, 2). The configuration of such layers has been observed in many others (Fe/Al)3+ phosphates (Huminicki & Hawthorne, 2002). The [(Fe/Al)3(PO4)3(OH)2] layers are connected by Ca2+ cations (coordination numbers of eight) and Mg2+ cations (coordination number of six). The relatively weaker bonds between the layers account for the cleavage of the mineral parallel to (010).
The (Fe/Al)O6 octahedral chains in calcioferrite have a repeat of ~7.1 Å, similar to those examined by Huminicki & Hawthorne (2002). Between the two distinct B sites, the B1 site is strongly preferred by Al. The average (Fe/Al)1—O distance is 1.962 Å, which is evidently shorter than the average (Fe/Al)2—O distance (1.997 Å). The analysis of the anisotropic displacement parameters of atoms indicates that PO4 tetrahedra behave as rigid bodies, as should be expected for such strongly bonded tetrahedral groups (Downs, 2000). Both (Ca/Sr)1 and Ca2 are eight-coordinated, with the former by (4 O + 4 H2O) and the latter by (6 O + 2 H2O). The (Ca/Sr)1O8 polyhedra are situated between the [(Fe/Al)3(PO4)3(OH)2] layers, whereas the Ca2O8 polyhedra are located within the layers (Fig. 2). Hydrogen-bonding interactions involving the water molecules and OH- function are also present between these layers (Table 1).
As observed for the (Ca/Sr)1O8 polyhedra, the MgO6 octahedra are also located between the [(Fe/Al)3(PO4)3(OH)2] layers (Fig. 2). The Mg-site is randomly half-occupied with an average Mg—O bond length of 1.988 Å. The water O atom OW3 appears to be split between two positions (OW3A and OW3B), representing the two sets of water molecules correlated to the occupancy of the Mg-site (Fig. 3). The displacement parameters for OW3A are significantly larger and elongated than those of OW3B, suggesting that OW3A correlates with the vacancy and therefore is in a "softer" potential well. Interatomic distances between Mg—OW3B are more similar to each other (2.145 (8) Å and 2.200 (9) Å) while those between Mg—OW3A are more dissimilar to each other (2.535 (11) Å and 2.117 (10) Å). This is consistent with our suggestion, based on displacement parameters, that OW3A is not bonded to Mg.
The calcioferrite specimen used in this study is from Moculta quarry, Angaston, Australia, and is in the collection of the RRUFF project (deposition R120092: http://rruff.info/R120092). Its chemical composition was determined with a CAMECA SX100 electron microprobe at the conditions of 15kV, 1nA and a beam size of 5µm. These conditions were optimized to minimize sample damage by the electron beam due to the small size of the sample (Fig. 4) and its high hydration. Ten analysis points yielded an average composition (wt. %): CaO 17.40 (41), SrO 0.57 (21), MgO 3.24 (16), Fe2O3 18.51(1.44), Al2O3 4.29 (86) and P2O5 34.97 (86), with H2O 21.02 calculated by difference. Due to the significant dehydration of the sample during the electron microprobe analysis, this composition may not be very accurate and was used only for the estimation of cation ratios. By assuming six P cations per formula, the relative ratio of (Ca, Sr):Mg:(Fe, Al):P is 3.85:0.98:3.85:6.00. The composition of the crystal is then (Ca3.94Sr0.06)Σ=4Mg(Fe2.93Al1.07)Σ=4(PO4)6(OH)4.12H2O as determined by the combination of the electron microprobe and the X-ray structural data.
All non-hydrogen atoms were refined with anisotropic displacement parameters. Only H atoms bonded to OW1, OW2, and OH could be located from difference Fourier syntheses and their positions refined with a fixed isotropic displacement parameter (Uiso = 0.03). The H atoms bonded to the disordered OW3 atom could not be located and were excluded from refinement.
The occupancies of Al and Fe of the two B sites were refined with their ratio determined from the electron microprobe analysis. The small amount of Sr detected from the electron microprobe analysis was assigned into the Ca1 site, because this site is significantly larger than the Ca2 site. The maximum residual electron density in the difference Fourier map, 0.57 e/Å3, was located at (0, 0.0340, 0.25), 0.69 Å from Sr1 and the minimum, -0.60 e/Å3, at (0.8637, 0.3318, 0.0082), 1.31 Å from OW1.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare material for publication: publCIF (Westrip, 2010).
Ca4MgFe4(PO4)6(OH)4·12H2O | F(000) = 1243 |
Mr = 1234.28 | Dx = 2.629 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2019 reflections |
a = 10.1936 (8) Å | θ = 2.2–29.9° |
b = 24.1959 (18) Å | µ = 2.60 mm−1 |
c = 6.3218 (4) Å | T = 293 K |
β = 91.161 (4)° | Plate, pale yellow |
V = 1558.9 (2) Å3 | 0.09 × 0.08 × 0.05 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 2348 independent reflections |
Radiation source: fine-focus sealed tube | 1712 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
φ and ω scan | θmax = 30.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −14→14 |
Tmin = 0.800, Tmax = 0.881 | k = −34→34 |
10490 measured reflections | l = −8→8 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | All H-atom parameters refined |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0509P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
2348 reflections | Δρmax = 0.57 e Å−3 |
160 parameters | Δρmin = −0.60 e Å−3 |
4 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0012 (3) |
Ca4MgFe4(PO4)6(OH)4·12H2O | V = 1558.9 (2) Å3 |
Mr = 1234.28 | Z = 2 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.1936 (8) Å | µ = 2.60 mm−1 |
b = 24.1959 (18) Å | T = 293 K |
c = 6.3218 (4) Å | 0.09 × 0.08 × 0.05 mm |
β = 91.161 (4)° |
Bruker APEXII CCD area-detector diffractometer | 2348 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1712 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.881 | Rint = 0.049 |
10490 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 4 restraints |
wR(F2) = 0.094 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.57 e Å−3 |
2348 reflections | Δρmin = −0.60 e Å−3 |
160 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ca1 | 0.0000 | 0.06262 (3) | 0.2500 | 0.0138 (2) | 0.9700 (1) |
Sr1 | 0.0000 | 0.06262 (3) | 0.2500 | 0.0138 (2) | 0.0300 (1) |
Ca2 | 0.0000 | 0.33191 (4) | 0.2500 | 0.0155 (2) | |
Mg | 0.0000 | 0.47193 (12) | 0.2500 | 0.0130 (6) | 0.5050 (1) |
Fe1 | 0.2500 | 0.2500 | 0.0000 | 0.0076 (2) | 0.651 (3) |
Al1 | 0.2500 | 0.2500 | 0.0000 | 0.0076 (2) | 0.349 (3) |
Fe2 | 0.0000 | 0.16865 (3) | −0.2500 | 0.00762 (17) | 0.814 (3) |
Al2 | 0.0000 | 0.16865 (3) | −0.2500 | 0.00762 (17) | 0.186 (3) |
P1 | 0.5000 | 0.30208 (5) | −0.2500 | 0.0115 (2) | |
P2 | 0.26354 (8) | 0.11351 (3) | 0.96145 (13) | 0.01383 (19) | |
O1 | 0.6135 (2) | 0.26286 (10) | 0.7074 (4) | 0.0198 (5) | |
O2 | 0.4700 (2) | 0.34019 (9) | 0.5625 (3) | 0.0164 (5) | |
O3 | 0.3130 (2) | 0.17285 (9) | 0.0051 (4) | 0.0189 (5) | |
O4 | 0.3782 (2) | 0.08573 (9) | 0.8546 (4) | 0.0201 (5) | |
O5 | 0.1438 (2) | 0.11435 (9) | 0.8055 (4) | 0.0192 (5) | |
O6 | 0.2234 (3) | 0.08585 (10) | 0.1650 (4) | 0.0284 (6) | |
OH | 0.3675 (2) | 0.27149 (10) | 0.2343 (4) | 0.0173 (5) | |
OW1 | 0.1598 (3) | 0.32890 (13) | 0.5225 (4) | 0.0314 (7) | |
OW2 | 0.1120 (2) | 0.02555 (10) | 0.5770 (4) | 0.0229 (5) | |
OW3A | 0.1164 (9) | 0.4665 (4) | 0.6075 (13) | 0.0281 (17) | 0.50 |
OW3B | 0.1193 (8) | 0.4792 (3) | 0.5320 (12) | 0.0199 (15) | 0.50 |
H11 | 0.178 (4) | 0.3424 (18) | 0.620 (6) | 0.030* | |
H12 | 0.213 (4) | 0.3114 (17) | 0.483 (7) | 0.030* | |
H21 | 0.123 (4) | 0.0581 (17) | 0.673 (6) | 0.030* | |
H22 | 0.191 (4) | 0.0156 (17) | 0.553 (6) | 0.030* | |
H1 | 0.372 (4) | 0.2496 (18) | 0.303 (7) | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0177 (4) | 0.0103 (4) | 0.0132 (4) | 0.000 | −0.0008 (3) | 0.000 |
Sr1 | 0.0177 (4) | 0.0103 (4) | 0.0132 (4) | 0.000 | −0.0008 (3) | 0.000 |
Ca2 | 0.0149 (4) | 0.0155 (5) | 0.0160 (5) | 0.000 | 0.0010 (3) | 0.000 |
Mg | 0.0115 (14) | 0.0084 (14) | 0.0192 (16) | 0.000 | 0.0000 (11) | 0.000 |
Fe1 | 0.0081 (4) | 0.0043 (3) | 0.0104 (4) | −0.0008 (3) | 0.0006 (2) | −0.0003 (3) |
Al1 | 0.0081 (4) | 0.0043 (3) | 0.0104 (4) | −0.0008 (3) | 0.0006 (2) | −0.0003 (3) |
Fe2 | 0.0088 (3) | 0.0055 (3) | 0.0087 (3) | 0.000 | 0.0011 (2) | 0.000 |
Al2 | 0.0088 (3) | 0.0055 (3) | 0.0087 (3) | 0.000 | 0.0011 (2) | 0.000 |
P1 | 0.0129 (5) | 0.0102 (5) | 0.0113 (5) | 0.000 | 0.0019 (4) | 0.000 |
P2 | 0.0160 (4) | 0.0093 (4) | 0.0164 (4) | 0.0018 (3) | 0.0049 (3) | 0.0028 (3) |
O1 | 0.0223 (12) | 0.0176 (12) | 0.0198 (12) | 0.0062 (9) | 0.0083 (9) | 0.0031 (9) |
O2 | 0.0220 (12) | 0.0147 (11) | 0.0127 (11) | 0.0020 (9) | 0.0022 (8) | 0.0001 (8) |
O3 | 0.0204 (12) | 0.0129 (11) | 0.0233 (13) | 0.0027 (9) | −0.0031 (9) | −0.0033 (9) |
O4 | 0.0196 (12) | 0.0152 (12) | 0.0258 (13) | 0.0056 (9) | 0.0068 (9) | 0.0019 (9) |
O5 | 0.0160 (12) | 0.0132 (12) | 0.0282 (13) | 0.0031 (9) | −0.0034 (9) | −0.0036 (10) |
O6 | 0.0324 (14) | 0.0273 (15) | 0.0261 (14) | 0.0048 (11) | 0.0138 (11) | 0.0118 (11) |
OH | 0.0197 (12) | 0.0115 (12) | 0.0206 (13) | −0.0040 (9) | −0.0034 (9) | 0.0048 (9) |
OW1 | 0.0299 (16) | 0.0415 (19) | 0.0226 (15) | −0.0034 (13) | −0.0055 (11) | 0.0040 (13) |
OW2 | 0.0221 (13) | 0.0194 (13) | 0.0271 (14) | −0.0027 (11) | −0.0022 (10) | −0.0048 (10) |
OW3A | 0.040 (4) | 0.018 (4) | 0.026 (5) | 0.009 (3) | −0.006 (4) | −0.005 (3) |
OW3B | 0.018 (3) | 0.015 (4) | 0.026 (5) | 0.005 (2) | −0.008 (3) | 0.000 (3) |
Ca1—O6i | 2.417 (2) | Mg—OW3Bviii | 2.200 (9) |
Ca1—O6 | 2.417 (2) | Mg—OW3Ai | 2.535 (8) |
Ca1—OW2i | 2.507 (3) | Mg—OW3A | 2.535 (8) |
Ca1—OW2 | 2.507 (3) | Fe1—O1iii | 1.956 (2) |
Ca1—O2ii | 2.648 (2) | Fe1—O1x | 1.956 (2) |
Ca1—O2iii | 2.648 (2) | Fe1—OHvii | 1.956 (2) |
Ca1—OW2iv | 2.665 (3) | Fe1—OH | 1.956 (2) |
Ca1—OW2v | 2.665 (3) | Fe1—O3 | 1.974 (2) |
Ca2—OW1i | 2.348 (3) | Fe1—O3vii | 1.974 (2) |
Ca2—OW1 | 2.348 (3) | Fe2—OHvii | 1.981 (2) |
Ca2—O4ii | 2.446 (2) | Fe2—OHiii | 1.981 (2) |
Ca2—O4iii | 2.446 (2) | Fe2—O5i | 1.995 (2) |
Ca2—O3vi | 2.524 (2) | Fe2—O5xi | 1.995 (2) |
Ca2—O3vii | 2.524 (2) | Fe2—O2vii | 2.016 (2) |
Ca2—O1ii | 2.585 (3) | Fe2—O2iii | 2.016 (2) |
Ca2—O1iii | 2.585 (3) | P1—O1x | 1.525 (2) |
Mg—O4iii | 1.990 (3) | P1—O1xi | 1.525 (2) |
Mg—O4ii | 1.990 (3) | P1—O2x | 1.528 (2) |
Mg—OW3Aviii | 2.117 (10) | P1—O2xi | 1.528 (2) |
Mg—OW3Aix | 2.117 (10) | P2—O6xii | 1.514 (2) |
Mg—OW3Bi | 2.145 (8) | P2—O4 | 1.519 (2) |
Mg—OW3B | 2.145 (8) | P2—O3xii | 1.545 (2) |
Mg—OW3Bix | 2.200 (9) | P2—O5 | 1.553 (2) |
O4iii—Mg—O4ii | 90.93 (18) | O1iii—Fe1—OHvii | 91.85 (10) |
O4iii—Mg—OW3Aviii | 173.6 (2) | O1x—Fe1—OHvii | 88.15 (10) |
O4ii—Mg—OW3Aviii | 89.6 (2) | OHvii—Fe1—OH | 180.00 (13) |
OW3Aviii—Mg—OW3Aix | 90.5 (5) | O1iii—Fe1—O3 | 94.26 (10) |
O4iii—Mg—OW3Bi | 89.3 (3) | O1x—Fe1—O3 | 85.74 (10) |
O4ii—Mg—OW3Bi | 97.4 (2) | OHvii—Fe1—O3 | 87.43 (10) |
OW3Aviii—Mg—OW3Bi | 84.3 (4) | OH—Fe1—O3 | 92.57 (10) |
OW3Aix—Mg—OW3Bi | 89.0 (2) | O3—Fe1—O3vii | 180.0 |
OW3Bi—Mg—OW3B | 170.5 (5) | OHvii—Fe2—OHiii | 86.06 (14) |
O4iii—Mg—OW3Bix | 79.2 (2) | OHvii—Fe2—O5i | 171.18 (9) |
O4ii—Mg—OW3Bix | 160.24 (19) | OHiii—Fe2—O5i | 88.56 (10) |
OW3Aviii—Mg—OW3Bix | 102.1 (3) | O5i—Fe2—O5xi | 97.60 (13) |
OW3Aix—Mg—OW3Bix | 15.01 (19) | OHvii—Fe2—O2vii | 90.57 (9) |
OW3Bi—Mg—OW3Bix | 99.5 (3) | OHiii—Fe2—O2vii | 98.35 (9) |
OW3B—Mg—OW3Bix | 75.3 (3) | O5xi—Fe2—O2vii | 88.68 (9) |
OW3Bix—Mg—OW3Bviii | 115.1 (4) | O2vii—Fe2—O2iii | 167.81 (13) |
O4iii—Mg—OW3Ai | 88.6 (2) | O1x—P1—O1xi | 103.03 (19) |
O4ii—Mg—OW3Ai | 87.2 (2) | O1x—P1—O2x | 112.29 (12) |
OW3Aviii—Mg—OW3Ai | 85.0 (3) | O1xi—P1—O2x | 111.83 (13) |
OW3Aix—Mg—OW3Ai | 99.2 (4) | O2x—P1—O2xi | 105.75 (18) |
OW3Bi—Mg—OW3Ai | 10.2 (3) | O6xii—P2—O4 | 113.94 (14) |
OW3B—Mg—OW3Ai | 173.1 (4) | O6xii—P2—O3xii | 110.61 (14) |
OW3Bix—Mg—OW3Ai | 109.38 (17) | O4—P2—O3xii | 103.84 (13) |
OW3Bviii—Mg—OW3Ai | 74.0 (3) | O6xii—P2—O5 | 108.83 (14) |
OW3Ai—Mg—OW3A | 174.1 (4) | O4—P2—O5 | 109.00 (13) |
O1iii—Fe1—O1x | 180.0 | O3xii—P2—O5 | 110.54 (13) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x, −y, −z+1; (v) x, −y, z−1/2; (vi) x−1/2, −y+1/2, z+1/2; (vii) −x+1/2, −y+1/2, −z; (viii) x, −y+1, z−1/2; (ix) −x, −y+1, −z+1; (x) −x+1, y, −z+1/2; (xi) x, y, z−1; (xii) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···O3ii | 0.72 (3) | 2.40 (4) | 2.994 (4) | 142 (5) |
OW1—H11···O6ii | 0.72 (3) | 2.41 (3) | 3.079 (4) | 155 (5) |
OW1—H12···OH | 0.74 (3) | 2.45 (3) | 3.145 (4) | 159 (4) |
OW1—H12···O2 | 0.74 (3) | 2.75 (4) | 3.179 (4) | 120 (4) |
OW2—H21···O5 | 1.00 (4) | 1.61 (4) | 2.606 (3) | 174 (4) |
OW2—H22···OW3Bii | 0.86 (4) | 2.02 (4) | 2.841 (9) | 160 (4) |
OW2—H22···OW3Aii | 0.86 (4) | 2.27 (4) | 3.033 (10) | 148 (4) |
OW2—H22···O6xiii | 0.86 (4) | 2.57 (4) | 2.973 (4) | 109 (3) |
OH—H1···OW1ii | 0.69 (4) | 2.22 (4) | 2.891 (4) | 165 (5) |
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (xiii) x, −y, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H11···O3i | 0.72 (3) | 2.40 (4) | 2.994 (4) | 142 (5) |
OW1—H11···O6i | 0.72 (3) | 2.41 (3) | 3.079 (4) | 155 (5) |
OW1—H12···OH | 0.74 (3) | 2.45 (3) | 3.145 (4) | 159 (4) |
OW1—H12···O2 | 0.74 (3) | 2.75 (4) | 3.179 (4) | 120 (4) |
OW2—H21···O5 | 1.00 (4) | 1.61 (4) | 2.606 (3) | 174 (4) |
OW2—H22···OW3Bi | 0.86 (4) | 2.02 (4) | 2.841 (9) | 160 (4) |
OW2—H22···OW3Ai | 0.86 (4) | 2.27 (4) | 3.033 (10) | 148 (4) |
OW2—H22···O6ii | 0.86 (4) | 2.57 (4) | 2.973 (4) | 109 (3) |
OH—H1···OW1i | 0.69 (4) | 2.22 (4) | 2.891 (4) | 165 (5) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z+1/2. |