Ammonium iron(III) phosphate(V) fluoride, (NH₄)_0.5[(NH₄)_0.375K_0.125]FePO₄F, with ammonium partially substituted by potassium

The title compound, ammonium potassium iron(III) phosphate fluoride, (NH₄)_0.875K_0.125FePO₄F, is built from zigzag chains _∞¹{[FeO₄F₂]⁷⁻}, with Fe³⁺ in a distorted octahedral coordination, extending along both the [011] and [01] directions. These chains are made up of alternating trans-[FeO₄F₂] and cis-[FeO₄F₂] octa­hedra via shared F-atom corners, and are linked by PO₄ tetra­hedra, resulting in an open-framework structure with channels along the [010] and [100] directions. There are two crystallographically independent ammonium sites: one in the [010] channels and the other, partially substituted by K⁺ ions, in the [100] channels. The ammonium in the [010] channels is fixed to the framework via eight hydrogen bonds (six N—H...O and two N—H...F).

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](P-O) = 0.004 Å
• H-atom completeness 58%
• Disorder in main residue
• R factor = 0.031
• wR factor = 0.054
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT073_ALERT_1_A H-atoms ref, but _hydrogen_treatment reported as     constr

Alert level B
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...          n
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...          n
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  N1      ..       2.83 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O4     ..  N1      ..       2.75 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O5     ..  N1      ..       2.74 Ang.
PLAT431_ALERT_2_B Short Inter HL..A Contact  F1     ..  N1      ..       2.70 Ang.
PLAT115_ALERT_5_B ADDSYM Detects Noncrystallographic Inversion ...         93 PerFi

Alert level C
            Value of measurement temperature given =   173.000
            Value of melting point given =     0.000
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT301_ALERT_3_C Main Residue  Disorder .........................       1.00 Perc.
PLAT430_ALERT_2_C Short Inter D...A Contact  O7     ..  N1      ..       2.89 Ang.
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?

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:H7 F2 Fe2 K0.25 N1.75 O8 P2
            Atom count from the _atom_site data:  H4 F2 Fe2 K0.249 N1.75 O8 P2
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    4
           From the CIF: _chemical_formula_sum  F2 Fe2 H7 K0.25 N1.75 O8 P2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           F          8.00      8.00    0.00
           Fe         8.00      8.00    0.00
           H         28.00     16.00   12.00
           K          1.00      1.00    0.00
           N          7.00      7.00    0.00
           O         32.00     32.00    0.00
           P          8.00      8.00    0.00
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           32.53
           From the CIF: _reflns_number_total               2162
           Count of symmetry unique reflns         1683
           Completeness (_total/calc)            128.46%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       479
           Fraction of Friedel pairs measured     0.285
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5

   1 ALERT level A = In general: serious problem
   7 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Compounds of the KTiOPO₄ (KTP) group have attracted great attention in the past decades owing to their non-linear optical properties, and became a large family of compositions with formula MM'OXO₄ (M = Na, K, Rb, Cs or Tl; M' = Ti, Ge, Sn and X = P or As), where M and M' can be partially replaced by two or more different cations (Hagerman et al., 1995). Tetravalent M' ions can be replaced by trivalent ions such as Fe³⁺ and Cr³⁺ with oxygen being substituted simultaneously by fluorine for charge balance. Many examples of fluorophosphates with the KTP-type structure are known, such as (NH₄)Fe(PO₄)F, (NH₄)Ga(PO₄)F (Loiseau et al., 1994, 2000 ), and (NH₄)V(PO₄)F (Alda et al., 2003) in the ammonium series, and KAl(PO₄)F (Slovokhotova et al., 1991), KGa(PO₄)F (Harrison et al., 1995), KFe(PO₄)F (Matvienko et al., 1979), and KCr(PO₄)F (Slobodyanik et al., 1991) in the potassium series. However, to the best of our knowledge, sodium fluorophosphate compounds with the KTP-type structure have not been reported to date. Our attempt to synthesize KTP-type sodium fluorophophates failed as well, instead we obtained a solid-solution ammonium fluorophosphate, (NH₄)((NH₄)_0.75K_0.25)[Fe₂(PO₄)₂F₂], partially substituted by potassium.

The crystal structure of the title compound is built from one-dimensional zigzag ferric octahedral chains _∞¹{[FeO₄F₂]^7-} (see Fig. 1) linked by PO₄ tetrahedra via common O-corners, resulting in a three dimensional open framework structure (see Fig.2). The zigzag ferric octahedral chains are made up of alternating trans-[FeO₄F₂] and cis-[FeO₄F₂] octahedra via common fluorine-corners, and are along both [011] and [0-11] directions. Each PO₄ tetrahedron shares all oxygen corners with four neighboring [FeO₄F₂] octahedra, and each [FeO₄F₂] octahedron shares its four oxygen atoms with four PO₄ tetrahedra. The negative charge of the framework is compensated by ammonium ions and potassium cations. Two crystallographically independent ammonium sites are found. One resides in the channels along [010], linking to the framework via hydrogen bonds (N-H···O(F)). If this ammonium ion is considered as a normal cation, its coordination number is 8 with an average bond distance of 2.969Å (i.e., to neighboring oxygen and fluorine atoms). The other ammonium site, partially occupied by K⁺ ions, resides in the channels along [100]. The potassium (ammonium) has a coordination number of 8 with a mean bond distance of 2.882Å. Therefore, the ammonium site in the [010] channels is slightly larger in size than its counterpart in the [100] channels. Consequently, potassium ions preferentially substitute for the ammonium ions in the [100] channels. We suggest that the potassium-to-ammonium ratio in the title compound is controlled by the size effect. It is possible that the size effect in hydrothermally synthesized crystals at lower temperatures is more pronounced than those from a solid state reaction route.

Related literature

For general background, see: Hagerman & Poeppelmeier (1995). For related structures, see: Loiseau et al. (1994) for (NH₄)Fe(PO₄)F; Loiseau et al. (2000) for (NH₄)Ga(PO₄)F; Alda et al. (2003) for (NH₄)V(PO₄)F; Slovokhotova et al. (1991) for KAl(PO₄)F; Harrison et al. (1995) for KGa(PO₄)F; Matvienko et al. (1979) for KFe(PO₄)F; Slobodyanik et al. (1991) for KCr(PO₄)F; Tordjman et al. (1974) for K(TiO)(PO₄).

S2. Experimental

Transparent, colorless single crystals of the title compound were synthesized hydrothermally. A mixture of 0.055 g NaBF₄, 1.035 g NH₄H₂PO₄, 0.342 g NH₄HF₂ and 0.048 g Fe₂O₃ in an approximate molar ratio of Na: NH₄: P: Fe = 0.5: 15: 9: 6, was dissolved in 9 ml distilled water while stirring. The prepared solution was transferred to a Teflon-lined stainless steel autoclave (internal volume 30 ml, degree of filling 33%) and held at 453 K for three days under autogenous pressure. Then the autoclave was cooled to room temperature by turning off the power. Products were filtered off, washed with distilled water and dried at room temperature. The presence of potassium in the crystal that was used for single crystal X-ray data collection, was determined by semi-quantitative chemical analysis on an Oxford Instruments Energy Dispersive Spectrometer(EDS)(calcd K: 2.56 %, Obsd K: ~3%). Sodium was not detectable in the crystal by EDS. It is supposed that potassium should be introduced into the sample as impurities in the reagents.

S3. Refinement

There are two possible space groups Pna2₁(abc) and Pnna(acb) for the KTP-type compounds. Initially, the centrosymmetric Pnna( No.52) space group was selected according to the observed systematic absences. All the framework atoms fit to the centrosymmetric model, except that the ammonium ions resided in the channel are in disordered manner and have abnormally short (1.46 Å) N–N distances. Furthermore, the structural refinement converged to only R1(gt)=0.0783 and wR(all)=0.1813, which are much higher than those from the noncentrosymmetric model (i.e., all anisotropic atoms resulting in R1(gt)=0.031,and wR(all)=0.054 using 155 parameters). Therefore, the noncentrosymmetric space group Pna2₁(No.33) was chosen to solve and refine the crystal structure as an inversion twin with twin components 0.48 (3)/0.52 (3). During the structure refinement, five constrained parameters were set, one for the constraint of N1 and K1 atoms (i.e., EXYZ and EADP) sharing the same site, the other four for geometrical constraints (i.e., HFIX: fixed bond distance 0.89 Å) of N2–H1, N2–H2, N2–H3, and N2–H4, respectively. Hydrogen coordinate parameters linked to N2 were obtained from difference electron density synthesis and refined by constrained N–H bond distances, their displacement parameters refined via setting to a common variable. Hydrogen atoms linked to N1 were not determined in the present paper.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005) and ATOMS (Dowty, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Unit cell of (NH4)((NH4)0.75K0.25) [Fe2(PO4)2F2] in a view along b. Trans-[FeO4F2], in blue octahedra; cis-[FeO4F2], in pink octahedra; PO4, in red tetrahedra; black spheres: disordered K/NH4; green spheres: NH4.
	Fig. 2. Left: (1). Coordination environment of eight coordinated potassium/ammonium ions(upper); (2). Coordination environment of ammonium ions via hydrogen bonds(down).Right: chains built up of alternate trans-[FeO4F2] and cis-[FeO4F2] octahedra running along [011] and [0-11] respectively;
	Fig. 3. Coordination environment of Fe and P atoms, with displacement ellipsoids drawn at the 50% probability level (symmetry codes: (i) x, 1+y, z; (ii) 1/2-x, 1/2+y, 1/2+z; (iii) -1/2+x, 1/2-y, z; (iv) 1/2+x, 1/2-y, z).

Ammonium iron(III) phosphate(V) fluoride

Crystal data

(NH4)0.875K0.125FePO4F	F(000) = 752
Mr = 190.49	Dx = 2.854 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5001 reflections
a = 12.9402 (4) Å	θ = 3.0–32.5°
b = 6.4382 (2) Å	µ = 3.82 mm^−1
c = 10.6428 (3) Å	T = 173 K
V = 886.67 (5) Å^3	Prism, colorless
Z = 8	0.12 × 0.09 × 0.09 mm

Data collection

Oxford Diffraction CCD area-detector diffractometer	2162 independent reflections
Radiation source: fine-focus sealed tube	1636 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
326 images,Δω=1°, Exp time: 40 s. scans	θmax = 32.5°, θmin = 2.5°
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2005)	h = −19→16
Tmin = 0.657, Tmax = 0.725	k = −4→9
5371 measured reflections	l = −10→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.054	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0164P)^2] where P = (Fo^2 + 2Fc^2)/3
2162 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.52 e Å^−3
5 restraints	Δρmin = −0.56 e Å^−3

Special details

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.

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 > 2sigma(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. The crystal structure of the title compound was refined by a inversion twin matrix so the Flack parameter is equal to zero.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.11299 (4)	0.48776 (11)	0.41908 (14)	0.00427 (10)
Fe2	0.25117 (7)	0.25076 (13)	0.16711 (14)	0.00434 (9)
K1	0.1161 (2)	0.7780 (4)	0.1155 (3)	0.0243 (9)	0.249 (5)
N1	0.1161 (2)	0.7780 (4)	0.1155 (3)	0.0243 (9)	0.75
N2	0.4008 (3)	0.6749 (6)	0.3543 (4)	0.0094 (7)
P1	0.18531 (6)	0.9964 (2)	0.4152 (2)	0.00453 (15)
P2	0.49699 (14)	0.17105 (12)	0.1701 (2)	0.00426 (15)
F1	0.2694 (3)	0.0303 (7)	0.0365 (3)	0.0067 (8)
F2	0.2233 (3)	0.4707 (7)	0.2864 (3)	0.0070 (8)
O1	0.2426 (3)	0.4522 (9)	0.0261 (4)	0.0082 (9)
O2	0.4023 (3)	0.3113 (6)	0.1847 (4)	0.0075 (8)
O3	0.2540 (3)	0.0417 (9)	0.2989 (4)	0.0076 (9)
O4	0.0953 (3)	0.1996 (6)	0.1474 (4)	0.0056 (8)
O5	0.4803 (4)	0.0316 (8)	0.0535 (3)	0.0095 (9)
O6	0.1173 (3)	0.1868 (5)	0.4430 (4)	0.0069 (8)
O7	0.1172 (3)	0.8075 (5)	0.3867 (4)	0.0061 (8)
O8	0.5104 (3)	0.0264 (8)	0.2834 (3)	0.0057 (9)*
H1	0.372 (3)	0.678 (8)	0.427 (3)	0.020 (7)*
H2	0.386 (4)	0.580 (7)	0.299 (4)	0.020 (7)*
H3	0.385 (4)	0.780 (6)	0.310 (4)	0.020 (7)*
H4	0.462 (2)	0.634 (8)	0.365 (5)	0.020 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0045 (2)	0.0046 (2)	0.00376 (18)	0.0002 (3)	−0.0004 (5)	0.0001 (2)
Fe2	0.00452 (18)	0.00472 (17)	0.00377 (17)	0.00037 (17)	0.00040 (18)	0.0003 (2)
K1	0.0311 (16)	0.0146 (14)	0.0271 (14)	−0.0069 (11)	0.0077 (11)	−0.0039 (10)
N1	0.0311 (16)	0.0146 (14)	0.0271 (14)	−0.0069 (11)	0.0077 (11)	−0.0039 (10)
N2	0.0038 (17)	0.0161 (18)	0.0083 (17)	−0.0023 (15)	0.0024 (14)	0.0011 (15)
P1	0.0048 (4)	0.0048 (3)	0.0039 (4)	−0.0008 (6)	−0.0017 (9)	0.0010 (3)
P2	0.0041 (4)	0.0046 (3)	0.0041 (3)	−0.0001 (6)	−0.0001 (3)	−0.0030 (7)
F1	0.0066 (18)	0.0067 (14)	0.0070 (16)	−0.0007 (14)	0.0021 (13)	−0.0002 (13)
F2	0.0077 (18)	0.0096 (15)	0.0037 (15)	−0.0016 (15)	0.0019 (13)	−0.0036 (13)
F1	0.0066 (18)	0.0067 (14)	0.0070 (16)	−0.0007 (14)	0.0021 (13)	−0.0002 (13)
F2	0.0077 (18)	0.0096 (15)	0.0037 (15)	−0.0016 (15)	0.0019 (13)	−0.0036 (13)
O1	0.008 (2)	0.0123 (18)	0.0045 (19)	0.0027 (19)	0.0029 (15)	0.0042 (17)
O2	0.005 (2)	0.0119 (15)	0.005 (2)	−0.0012 (15)	0.0027 (18)	0.0014 (15)
O3	0.007 (2)	0.0091 (18)	0.0067 (19)	0.0002 (18)	0.0000 (14)	0.0012 (17)
O4	0.0036 (19)	0.0049 (14)	0.008 (2)	0.0006 (13)	−0.0034 (17)	0.0000 (14)
O5	0.0102 (18)	0.0095 (15)	0.0089 (16)	0.0032 (14)	−0.0035 (12)	−0.0052 (11)
O6	0.0095 (18)	0.0063 (13)	0.005 (2)	0.0009 (17)	0.0009 (19)	0.0017 (13)
O7	0.0070 (17)	0.0053 (13)	0.006 (2)	0.0005 (16)	−0.0013 (19)	−0.0034 (12)

Geometric parameters (Å, º)

Fe1—O5^i	1.893 (4)	N2—O7^iv	2.823 (5)
Fe1—O6	1.955 (4)	N2—O2	2.956 (6)
Fe1—O8^ii	1.963 (4)	N2—F1^i	3.079 (6)
Fe1—F1^i	1.988 (4)	N2—O3^iii	3.088 (7)
Fe1—F2	2.010 (4)	N2—O4^i	3.124 (6)
Fe1—O7	2.088 (4)	N2—O1^i	3.159 (7)
Fe2—F2	1.936 (4)	P1—O1^i	1.531 (5)
Fe2—O3	1.944 (5)	P1—O7	1.532 (4)
Fe2—O1	1.986 (5)	P1—O6^iii	1.538 (4)
Fe2—F1	2.001 (4)	P1—O3^iii	1.551 (5)
Fe2—O2	2.003 (4)	P2—O2	1.530 (4)
Fe2—O4	2.055 (3)	P2—O8	1.533 (5)
K1—F1^iii	2.697 (5)	P2—O4^v	1.539 (4)
K1—O5^ii	2.739 (6)	P2—O5	1.547 (5)
K1—O4^iii	2.749 (4)	F1—Fe1^vi	1.988 (4)
K1—O1	2.825 (6)	F1—K1^vii	2.697 (5)
K1—O7	2.893 (5)	O1—P1^vi	1.531 (5)
K1—O8^ii	2.985 (5)	O3—P1^vii	1.551 (5)
K1—F2	3.025 (5)	O3—K1^vii	3.142 (6)
K1—O3^iii	3.142 (6)	O4—P2^ii	1.539 (4)
N2—H1	0.86 (2)	O4—K1^vii	2.749 (4)
N2—H2	0.87 (2)	O5—Fe1^vi	1.893 (4)
N2—H3	0.85 (2)	O5—K1^v	2.739 (6)
N2—H4	0.84 (2)	O6—P1^vii	1.538 (4)
N2—F2	2.744 (6)	O8—Fe1^v	1.963 (4)
N2—O8^iii	2.775 (6)	O8—K1^v	2.985 (5)
O5^i—Fe1—O6	93.9 (2)	F1^iii—K1—O3^iii	56.70 (12)
O5^i—Fe1—O8^ii	97.58 (10)	O5^ii—K1—O3^iii	155.13 (16)
O6—Fe1—O8^ii	94.0 (2)	O4^iii—K1—O3^iii	56.31 (13)
O5^i—Fe1—F1^i	89.56 (19)	O1—K1—O3^iii	106.34 (16)
O6—Fe1—F1^i	91.87 (18)	O7—K1—O3^iii	48.85 (13)
O8^ii—Fe1—F1^i	170.45 (17)	O8^ii—K1—O3^iii	104.06 (15)
O5^i—Fe1—F2	172.51 (19)	F2—K1—O3^iii	73.71 (16)
O6—Fe1—F2	90.97 (18)	H1—N2—H2	122 (5)
O8^ii—Fe1—F2	87.76 (17)	H1—N2—H3	112 (5)
F1^i—Fe1—F2	84.57 (10)	H2—N2—H3	98 (5)
O5^i—Fe1—O7	89.7 (2)	H1—N2—H4	107 (5)
O6—Fe1—O7	176.27 (15)	H2—N2—H4	95 (5)
O8^ii—Fe1—O7	86.68 (19)	H3—N2—H4	124 (5)
F1^i—Fe1—O7	87.03 (17)	O1^i—P1—O7	110.8 (3)
F2—Fe1—O7	85.37 (17)	O1^i—P1—O6^iii	110.4 (3)
F2—Fe2—O3	92.1 (2)	O7—P1—O6^iii	109.98 (13)
F2—Fe2—O1	90.43 (16)	O1^i—P1—O3^iii	107.56 (14)
O3—Fe2—O1	176.3 (3)	O7—P1—O3^iii	108.7 (3)
F2—Fe2—F1	175.3 (2)	O6^iii—P1—O3^iii	109.4 (3)
O3—Fe2—F1	90.44 (16)	O2—P2—O8	111.7 (3)
O1—Fe2—F1	86.9 (2)	O2—P2—O4^v	111.00 (12)
F2—Fe2—O2	88.75 (18)	O8—P2—O4^v	111.0 (2)
O3—Fe2—O2	92.82 (18)	O2—P2—O5	108.2 (3)
O1—Fe2—O2	89.87 (19)	O8—P2—O5	107.11 (13)
F1—Fe2—O2	95.06 (17)	O4^v—P2—O5	107.7 (3)
F2—Fe2—O4	90.05 (17)	Fe1^vi—F1—Fe2	128.6 (2)
O3—Fe2—O4	88.90 (18)	Fe1^vi—F1—K1^vii	132.5 (2)
O1—Fe2—O4	88.46 (18)	Fe2—F1—K1^vii	97.14 (16)
F1—Fe2—O4	86.05 (18)	Fe2—F2—Fe1	129.3 (2)
O2—Fe2—O4	177.9 (2)	Fe2—F2—K1	99.74 (15)
F1^iii—K1—O5^ii	146.65 (16)	Fe1—F2—K1	93.52 (16)
F1^iii—K1—O4^iii	61.07 (13)	P1^vi—O1—Fe2	132.1 (3)
O5^ii—K1—O4^iii	133.26 (16)	P1^vi—O1—K1	118.3 (3)
F1^iii—K1—O1	85.20 (17)	Fe2—O1—K1	105.24 (19)
O5^ii—K1—O1	75.57 (15)	P2—O2—Fe2	131.1 (2)
O4^iii—K1—O1	146.27 (16)	P1^vii—O3—Fe2	134.0 (3)
F1^iii—K1—O7	105.53 (14)	P1^vii—O3—K1^vii	94.0 (2)
O5^ii—K1—O7	106.92 (14)	Fe2—O3—K1^vii	85.15 (16)
O4^iii—K1—O7	79.17 (13)	P2^ii—O4—Fe2	135.1 (2)
O1—K1—O7	112.44 (15)	P2^ii—O4—K1^vii	129.4 (2)
F1^iii—K1—O8^ii	156.77 (16)	Fe2—O4—K1^vii	94.26 (14)
O5^ii—K1—O8^ii	51.09 (8)	P2—O5—Fe1^vi	141.5 (3)
O4^iii—K1—O8^ii	121.95 (15)	P2—O5—K1^v	98.0 (2)
O1—K1—O8^ii	88.83 (16)	Fe1^vi—O5—K1^v	118.9 (2)
O7—K1—O8^ii	56.47 (12)	P1^vii—O6—Fe1	141.4 (3)
F1^iii—K1—F2	104.14 (16)	P1—O7—Fe1	139.9 (2)
O5^ii—K1—F2	87.88 (16)	P1—O7—K1	104.6 (2)
O4^iii—K1—F2	128.06 (15)	Fe1—O7—K1	95.74 (14)
O1—K1—F2	56.72 (12)	P2—O8—Fe1^v	133.1 (3)
O7—K1—F2	55.97 (11)	P2—O8—K1^v	88.85 (19)
O8^ii—K1—F2	54.57 (13)	Fe1^v—O8—K1^v	95.74 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···F1^i	0.86 (4)	2.37 (5)	3.079 (6)	140 (4)
N2—H1···O4^i	0.86 (4)	2.39 (3)	3.124 (6)	144 (4)
N2—H1···O1^i	0.86 (4)	2.54 (5)	3.159 (7)	130 (4)
N2—H2···O2	0.87 (4)	2.13 (4)	2.956 (6)	159 (4)
N2—H2···F2	0.87 (4)	2.22 (5)	2.744 (6)	118 (4)
N2—H3···O8^iii	0.85 (4)	2.29 (5)	2.775 (6)	117 (4)
N2—H3···O3^iii	0.85 (4)	2.39 (5)	3.088 (7)	139 (4)
N2—H4···O7^iv	0.84 (3)	2.06 (3)	2.823 (5)	151 (4)

Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (iii) x, y+1, z; (iv) x+1/2, −y+3/2, z.