KInAs2O7, a new diarsenate with the TlInAs2O7 structure type.

Potassium indium diarsenate(V) was grown under mild hydro-thermal conditions (T = 493 K, 7 d) at a pH value of about 1. It adopts the TlInAs2O7 structure type (P-1, Z = 4) and is closely related to the KAlP2O7 (P21/c) and RbAlAs2O7 (P-1) structure types. The framework topology of KInAs2O7 is built of two symmetrically non-equivalent As2O7 groups which share corners with InO6 octa-hedra. The K atoms are located in channels extending along [010].

Chemical context

Metal arsenates often form tetra­hedral–octa­hedral framework structures exhibiting potentially inter­esting properties, such as ion conductivity, ion exchange and catalytic properties (Masquelier et al., 1990 ▸, 1994a ▸,b ▸, 1995 ▸, 1996 ▸, 1998 ▸; Mesa et al., 2000 ▸; Ouerfelli et al., 2007a ▸, 2008 ▸; Pintard-Scrépel et al., 1983 ▸; Rousse et al., 2013 ▸). During a detailed study of the system M +–M 3+–As–O–(H) by hydro­thermal syntheses, a large variety of new compounds and structure types were found (Kolitsch, 2004 ▸; Schwendtner, 2006 ▸; Schwendtner & Kolitsch, 2004a ▸,b ▸, 2005 ▸, 2007a ▸,b ▸,c ▸,d ▸, 2017a ▸,b ▸). KInAs2O7 is another example of a microporous metal diarsenate compound forming a tetra­hedral–octa­hedral framework structure.

M + M 3+As2O7 compounds crystallize in six known structure types (for a short review, see: Schwendtner & Kolitsch, 2017b ▸), some of these diarsenates being also isotypic to diphosphates or disilicates. For several of the structures, the M + cation is the relevant factor that determines which structure type is adopted, while a wide range of different M 3+ cations are usually accepted. For example, the CaZrSi2O7 structure type (mineral gittinsite; Roelofsen-Ahl & Peterson, 1989 ▸) is formed by all Li members (and one Na member), with M 3+ cations ranging from M = Al, Ga, Fe to Sc (Schwendtner & Kolitsch, 2007d ▸; Wang et al., 1994 ▸). The inter­mediate-sized M + cations Ag+ and Na+ generally form either of two structure types, the NaInAs2O7 type (Belam et al., 1997 ▸) or the NaAlAs2O7 type (Driss & Jouini, 1994 ▸). While the former is only known from the comparatively large M 3+ cation In3+ (Belam et al., 1997 ▸, ICDD-PDF 059-0058; Wohlschlaeger et al., 2007 ▸), the latter is adopted by the smaller M 3+ representatives (M = Al, Fe, Ga) (Ouerfelli et al., 2004 ▸; Schwendtner & Kolitsch, 2017b ▸). The larger M + cations (M = K, Rb, Cs, Tl, NH4) favour three structure types, the stabilities of which seem to be determined mainly by the M 3+ cations. While the RbAlAs2O7 type (Boughzala et al., 1993 ▸) is favoured by the smaller cations Al3+, Ga3+, Cr3+ and Fe3+ (Boughzala & Jouini, 1992 ▸, 1995 ▸; Bouhassine & Boughzala, 2017 ▸; Lin & Lii, 1996 ▸; Siegfried et al., 2004 ▸; Ouerfelli et al., 2007a ▸), the KAlP2O7 type (Ng & Calvo, 1973 ▸), which is extremely common among M + M 3+P2O7 compounds, is favoured by the somewhat larger Sc3+ cation (Baran et al., 2006 ▸; Kolitsch, 2004 ▸; Schwendtner & Kolitsch, 2004a ▸) and the CsCr member CsCrAs2O7 (Bouhassine & Boughzala, 2015 ▸). The third type, TlInAs2O7, is very closely related to the two former types and favoured by the large In3+ cation (Schwendtner, 2006 ▸), with also one Fe member (KFeAs2O7; Ouerfelli et al., 2007b ▸). The title compound, KInAs2O7, is a new member of the latter structure type.

Structural commentary

KInAs2O7 crystallizes in space group P and adopts the TlInAs2O7 structure type (Schwendtner, 2006 ▸), which is also known for RbInAs2O7 and NH4InAs2O7 (Schwendtner, 2006 ▸) and KFeAs2O7 (Ouerfelli et al., 2007b ▸) (see comparison in Table 1 ▸).

Table 1

Comparison of the unit-cell parameters of diarsenates isotypic with KInAs2O7 and closely related structure types

Compound	a (Å)	b (Å)	c (Å)	α (°)	β (°)	γ (°)	V (Å3)
TlInAs2O7 type 1
KInAs2O7	7.712 (2)	8.554 (2)	10.461 (2)	88.58 (3)	89.82 (3)	73.97 (3)	663.1 (3)
RbInAs2O7 1	7.845 (2)	8.678 (2)	10.492 (2)	88.85 (3)	89.93 (3)	74.38 (3)	687.5 (3)
TlInAs2O7 1	7.827 (2)	8.625 (2)	10.494 (2)	88.83 (3)	89.98 (3)	74.31 (3)	682.1 (3)
(NH4)InAs2O7 1	7.858 (2)	8.649 (2)	10.515 (2)	88.96 (3)	89.94 (3)	74.34 (3)	688.0 (3)
KFeAs2O7 2	7.662 (1)	8.402 (2)	10.100 (3)	89.58 (3)	89.74 (2)	73.61 (2)	623.8 (3)
KAlP2O7 type 3
RbScAs2O7 4	7.837 (2)	10.625 (2)	8.778 (2)	90.00	106.45 (3)	90.00	701.0 (3)
TlScAs2O7 5	7.814 (2)	10.613 (2)	8.726 (2)	90.00	106.31 (3)	90.00	694.5 (3)
CsCrAs2O7 6	7.908 (1)	10.0806 (10)	8.6371 (10)	90.00	105.841 (1)	90.00	662.38 (13)
(NH4)ScAs2O7 7	7.842 (2)	10.656 (2)	8.765 (2)	90.00	106.81 (3)	90.00	701.1 (3)
RbAlAs2O7 type 8
KGaAs2O7 9	6.271 (1)	6.376 (1)	8.169 (1)	96.45 (1)	103.86 (1)	103.87 (1)	302.84 (8)
KAlAs2O7 10	6.192 (4)	6.297 (3)	8.106 (1)	96.600 (8)	104.517 (8)	102.864 (7)	293.4
RbAlAs2O7 8	6.241 (5)	6.34 (2)	8.233 (5)	96.7 (1)	103.89 (7)	102.6 (1)	303.9
CsAlAs2O7 11	6.494 (8)	6.709 (7)	8.360 (8)	97.07 (9)	103.23 (9)	102.62 (8)	340.4
TlAlAs2O7 11	6.267 (4)	6.324 (4)	8.168 (8)	97.07 (7)	103.83 (8)	102.99 (8)	300.9
KCr0.25Al0.75 As2O7 12	6.243 (3)	6.349 (3)	8.153 (4)	96.57 (2)	104.45 (3)	103.08 (4)	299.8 (8)
TlFe0.22Al0.78As2O7 13	6.296 (2)	6.397 (2)	8.242 (2)	96.74 (2)	103.78 (2)	102.99 (3)	309.0 (2)
KCrAs2O7 14	6.316 (1)	6.420 (1)	8.179 (2)	96.29 (3)	104.27 (3)	103.66 (3)	307.4 (1)

Notes: (1) Schwendtner (2006 ▸), P , Z = 4; (2) Ouerfelli et al. (2007b ▸), transformed to reduced cell; (3) Ng & Calvo (1973 ▸), P21/c, Z = 4; (4) Schwendtner & Kolitsch (2004a ▸); (5) Baran et al. (2006 ▸); (6) Bouhassine & Boughzala (2015 ▸); (7) Kolitsch (2004 ▸); (8) Boughzala et al. (1993 ▸), P , Z = 2, transformed to reduced cell; (9) Lin & Lii (1996 ▸); (10) Boughzala & Jouini (1995 ▸); (11) Boughzala & Jouini (1992 ▸), transformed to reduced cell; (12) Bouhassine & Boughzala (2017 ▸); (13) Ouerfelli et al. (2007a ▸); (14) Siegfried et al. (2004 ▸).

The asymmetric unit contains 22 atoms, all of which lie on general positions. Each InO6 octa­hedron shares corners with five different AsO4 tetra­hedra, thus creating a framework structure. Two of these connections are to two AsO4 tetra­hedra of the same As2O7 group (see Fig. 1 ▸). The K+ cations are situated in small channels extending along [010] (see Fig. 2 ▸) and have irregular coordination spheres, with ten (K1) and seven (K2) O atoms within 3.5 Å.

Figure 1

The principal building unit of KInAs2O7, shown as displacement ellipsoids at the 70% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x, y + 1, z; (iii) x, y − 1, z; (iv) −x + 1, −y + 1, −z; (v) −x + 2, −y + 1, −z + 1; (vi) −x + 2, −y + 1, −z.]

Figure 2

The framework structure of KInAs2O7, viewed along [010]. The K+ cations are hosted in the channels extending along [010]. The unit cell is outlined.

The AsO4 tetra­hedra are strongly distorted, with bond-length distortion (Brown & Shannon, 1973 ▸) ranging from 0.0020 to 0.0024, while the average As—O distances (1.685, 1.687, 1.689 and 1.690 Å for As1–4, respectively, see Table 2 ▸) are typical for As—O bond lengths in diarsenates [average = As—O 1.688 (6) Å; Schwendtner & Kolitsch, 2007d ▸]. In addition, the elongated As—O bond lengths to the bridging O atoms (Table 2 ▸), ranging from 1.7485 (16) to 1.7607 (16) Å, are typical for diarsenates [average As—Obridge distance is 1.755 (17); Schwendtner & Kolitsch, 2007d ▸]. The As—Obridge—As angles are 120.04 (9) and 118.77 (9)°, and therefore very similar to those of the related TlIn, RbIn and NH4In compounds (Schwendtner 2006 ▸), but are smaller than the grand mean value in diarsenates, 124 (5)° (Schwendtner & Kolitsch, 2007d ▸).

Table 2

Selected geometric parameters (Å, °)

K1—O6i	2.7321 (18)	In2—O9iv	2.1243 (16)
K1—O2ii	2.7836 (18)	In2—O13viii	2.1373 (16)
K1—O8	2.8150 (19)	In2—O3	2.1419 (16)
K1—O6	2.892 (2)	In2—O8	2.1551 (17)
K1—O13ii	3.060 (2)	In2—O7	2.1560 (16)
K1—O14ii	3.109 (2)	In2—O12iii	2.1666 (17)
K1—O10	3.1604 (19)	As1—O1	1.6542 (17)
K1—O1	3.225 (2)	As1—O2	1.6609 (16)
K1—O7	3.289 (2)	As1—O3	1.6761 (16)
K1—O1i	3.405 (2)	As1—O4	1.7485 (16)
K2—O10iii	2.6849 (19)	As2—O5	1.6592 (16)
K2—O9iv	2.7016 (18)	As2—O7	1.6647 (16)
K2—O3ii	2.7645 (19)	As2—O6	1.6677 (17)
K2—O7	2.8609 (19)	As2—O4	1.7549 (16)
K2—O12iv	2.930 (2)	As3—O8	1.6550 (15)
K2—O9iii	3.244 (2)	As3—O9	1.6708 (16)
K2—O5v	3.4261 (18)	As3—O10	1.6763 (16)
In1—O5vi	2.0946 (17)	As3—O11	1.7538 (16)
In1—O1	2.1036 (17)	As4—O12	1.6579 (17)
In1—O14	2.1502 (17)	As4—O13	1.6697 (16)
In1—O6i	2.1618 (16)	As4—O14	1.6727 (16)
In1—O10	2.1643 (16)	As4—O11	1.7607 (16)
In1—O2vii	2.1737 (16)
As1—O4—As2	120.04 (9)	As3—O11—As4	118.77 (9)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

The In1O6 octa­hedron is considerably more distorted than the In2-centred octa­hedron. In fact, the In1O6 octa­hedron shows the strongest distortion among all of the isotypic In compounds (Schwendtner, 2006 ▸) that are so far known [bond-length distortion (Brown & Shannon, 1973 ▸): 0.0012 (In1), 0.0003 (In2); bond-angle distortion (Robinson et al., 1971 ▸): 66.93 (In1), 20.69 (In2)].

The bond-valence sums, calculated using recently refined parameters (Gagné & Hawthorne, 2015 ▸), amount to 0.94/0.88 (K1/K2), 3.01/2.96 (In1/In2), 5.05/5.03/4.99/4.98 (As1/As2/As3/As4) and 2.00/1.97/1.95/2.08/1.94/1.98/1.99/2.00/2.07/2.02/2.04/1.94/1.89/1.86 (O1–O14) valence units and are thus reasonably close to the theoretical values. As expected, the bridging O4 and O11 ligands are slightly overbonded.

The structure shares a practically identical connectivity with two related structure types, the main difference being differences in space-group symmetry and distortion of the structures. It is most closely related to that of KAlP2O7 (Ng & Calvo, 1973 ▸), with many of the corresponding Sc-members crystallizing in this structure type. The main difference is a higher space-group symmetry (P21/c) of the KAlP2O7 type, which is lost in the In compounds due to the larger ionic radius of In3+ and a greater distortion of the structure. The second closely related structure type is that of RbAlAs2O7 (Boughzala et al., 1993 ▸). Many of the arsenates with large M + and small M 3+ cations crystallize in this structure type, which is also triclinic (P ), but actually shows higher symmetry, as Z is halved and the two distinct positions for the As2O7 groups, M 3+O6 and M + present in the KAlP2O7 and TlInAs2O7 structure types are equivalent in the RbAlAs2O7 structure type. A more detailed comparison of these three related structure types is given in Schwendtner (2006 ▸).

Synthesis and crystallization

KInAs2O7 was synthesized under mild hydro­thermal conditions at 493 K (7 d, autogeneous pressure, slow furnace cooling) using a Teflon-lined stainless steel autoclave with an approximate filling volume of 2 cm3. Reagent-grade K2CO3, In2O3 and H3AsO4·5H2O were used as starting reagents in approximate volume ratios of M +:M 3+:As of 1:1:2. The vessel was filled with distilled water to about 70% of its inner volume. Initial and final pH was about 1. The reaction products were thoroughly washed with distilled water, filtered and dried at room temperature. KInAs2O7 grew as thick tabular crystals and was accompanied by about 5 vol.% of K(H2O)In(H1.5AsO4)2(H2AsO4) (Schwendtner & Kolitsch, 2007c ▸).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸.

Table 3

Experimental details

Crystal data
Chemical formula	KInAs2O7
M r	415.76
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	7.712 (2), 8.554 (2), 10.461 (2)
α, β, γ (°)	88.58 (3), 89.82 (3), 73.97 (3)
V (Å3)	663.1 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	14.09
Crystal size (mm)	0.15 × 0.10 × 0.09
Data collection
Diffractometer	Nonius KappaCCD single-crystal four-circle
Absorption correction	Multi-scan (SCALEPACK; Otwinowski et al., 2003 ▸)
T min, T max	0.226, 0.364
No. of measured, independent and observed [I > 2σ(I)] reflections	11497, 5787, 5467
R int	0.017
(sin θ/λ)max (Å−1)	0.806
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.019, 0.043, 1.16
No. of reflections	5787
No. of parameters	200
Δρmax, Δρmin (e Å−3)	0.91, −0.80

Computer programs: COLLECT (Nonius, 2003 ▸), DENZO and SCALEPACK (Otwinowski et al., 2003 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2016 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 2005 ▸), publCIF (Westrip, 2010 ▸).

The largest residual electron densities in the final difference-Fourier map are below 1 e Å−3 and are located close to the In atoms.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017011318/pk2604sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017011318/pk2604Isup2.hkl

CCDC reference: 1565954

Additional supporting information: crystallographic information; 3D view; checkCIF report

KInAs2O7	Z = 4
Mr = 415.76	F(000) = 760
Triclinic, P1	Dx = 4.165 Mg m−3
a = 7.712 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.554 (2) Å	Cell parameters from 5760 reflections
c = 10.461 (2) Å	θ = 2.5–35.0°
α = 88.58 (3)°	µ = 14.09 mm−1
β = 89.82 (3)°	T = 293 K
γ = 73.97 (3)°	Thick tabular, colourless
V = 663.1 (3) Å3	0.15 × 0.10 × 0.09 mm

Nonius KappaCCD single-crystal four-circle diffractometer	5467 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
φ and ω scans	θmax = 35.0°, θmin = 2.5°
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 2003)	h = −12→12
Tmin = 0.226, Tmax = 0.364	k = −13→13
11497 measured reflections	l = −16→16
5787 independent reflections

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)] = 0.019	w = 1/[σ2(Fo2) + (0.0098P)2 + 1.0091P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.043	(Δ/σ)max = 0.002
S = 1.16	Δρmax = 0.91 e Å−3
5787 reflections	Δρmin = −0.80 e Å−3
200 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00818 (16)

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.

	x	y	z	Uiso*/Ueq
K1	0.34522 (8)	0.53997 (7)	0.32187 (5)	0.02034 (10)
K2	0.31660 (7)	0.05934 (7)	0.17988 (6)	0.02080 (10)
In1	0.73419 (2)	0.73879 (2)	0.40711 (2)	0.00661 (3)
In2	0.73416 (2)	0.23051 (2)	0.10125 (2)	0.00664 (3)
As1	0.94019 (3)	0.32576 (2)	0.35376 (2)	0.00635 (4)
As2	0.66173 (3)	0.14940 (2)	0.42785 (2)	0.00643 (4)
As3	0.62526 (3)	0.66936 (2)	0.10396 (2)	0.00657 (4)
As4	0.95282 (3)	0.79448 (2)	0.13500 (2)	0.00698 (4)
O1	0.7706 (2)	0.49230 (19)	0.36618 (17)	0.0159 (3)
O2	1.1358 (2)	0.3418 (2)	0.40953 (15)	0.0119 (3)
O3	0.9650 (2)	0.2482 (2)	0.20709 (14)	0.0113 (3)
O4	0.8725 (2)	0.1851 (2)	0.45195 (15)	0.0118 (3)
O5	0.6925 (2)	−0.03518 (19)	0.49288 (15)	0.0126 (3)
O6	0.5122 (2)	0.29000 (18)	0.50933 (15)	0.0110 (3)
O7	0.6078 (2)	0.1721 (2)	0.27322 (14)	0.0140 (3)
O8	0.5977 (2)	0.48491 (18)	0.12146 (15)	0.0115 (3)
O9	0.5133 (2)	0.78072 (19)	−0.01871 (14)	0.0114 (3)
O10	0.5710 (2)	0.78104 (19)	0.23508 (14)	0.0106 (3)
O11	0.8537 (2)	0.65005 (19)	0.07271 (15)	0.0116 (3)
O12	0.8338 (2)	0.97121 (19)	0.07213 (16)	0.0149 (3)
O13	1.1666 (2)	0.7361 (2)	0.08550 (15)	0.0118 (3)
O14	0.9563 (2)	0.7698 (2)	0.29418 (15)	0.0151 (3)

	U11	U22	U33	U12	U13	U23
K1	0.0218 (2)	0.0215 (2)	0.0207 (2)	−0.0113 (2)	0.00072 (19)	0.00221 (18)
K2	0.0139 (2)	0.0180 (2)	0.0283 (3)	−0.00121 (18)	0.00082 (19)	0.00371 (19)
In1	0.00685 (6)	0.00706 (6)	0.00621 (5)	−0.00241 (4)	0.00060 (4)	−0.00022 (4)
In2	0.00646 (6)	0.00762 (6)	0.00602 (5)	−0.00223 (4)	0.00010 (4)	−0.00027 (4)
As1	0.00562 (8)	0.00642 (8)	0.00720 (8)	−0.00194 (6)	−0.00088 (6)	−0.00041 (6)
As2	0.00676 (8)	0.00649 (8)	0.00648 (8)	−0.00255 (6)	0.00150 (6)	−0.00048 (6)
As3	0.00675 (8)	0.00614 (8)	0.00705 (8)	−0.00214 (6)	−0.00117 (6)	−0.00007 (6)
As4	0.00620 (8)	0.00841 (8)	0.00674 (8)	−0.00270 (7)	0.00132 (6)	−0.00005 (6)
O1	0.0121 (7)	0.0076 (6)	0.0253 (8)	0.0021 (5)	−0.0034 (6)	−0.0053 (6)
O2	0.0096 (6)	0.0171 (7)	0.0110 (6)	−0.0072 (6)	−0.0046 (5)	0.0047 (5)
O3	0.0088 (6)	0.0177 (7)	0.0075 (6)	−0.0037 (5)	0.0004 (5)	−0.0050 (5)
O4	0.0083 (6)	0.0151 (7)	0.0138 (7)	−0.0067 (5)	−0.0023 (5)	0.0052 (5)
O5	0.0165 (7)	0.0069 (6)	0.0148 (7)	−0.0040 (5)	0.0026 (6)	0.0002 (5)
O6	0.0095 (6)	0.0095 (6)	0.0146 (7)	−0.0035 (5)	0.0051 (5)	−0.0035 (5)
O7	0.0126 (7)	0.0258 (8)	0.0061 (6)	−0.0096 (6)	−0.0002 (5)	0.0017 (6)
O8	0.0129 (7)	0.0067 (6)	0.0156 (7)	−0.0041 (5)	−0.0011 (5)	0.0003 (5)
O9	0.0119 (6)	0.0129 (7)	0.0111 (6)	−0.0067 (5)	−0.0055 (5)	0.0062 (5)
O10	0.0113 (6)	0.0100 (6)	0.0087 (6)	0.0003 (5)	−0.0021 (5)	−0.0022 (5)
O11	0.0083 (6)	0.0111 (6)	0.0166 (7)	−0.0044 (5)	0.0017 (5)	−0.0043 (5)
O12	0.0167 (7)	0.0070 (6)	0.0189 (7)	0.0004 (6)	−0.0004 (6)	0.0010 (5)
O13	0.0067 (6)	0.0177 (7)	0.0104 (6)	−0.0024 (5)	0.0028 (5)	0.0015 (5)
O14	0.0111 (7)	0.0298 (9)	0.0069 (6)	−0.0100 (6)	0.0011 (5)	0.0010 (6)

K1—O6i	2.7321 (18)	In1—O14	2.1502 (17)
K1—O2ii	2.7836 (18)	In1—O6i	2.1618 (16)
K1—O8	2.8150 (19)	In1—O10	2.1643 (16)
K1—O6	2.892 (2)	In1—O2vii	2.1737 (16)
K1—O13ii	3.060 (2)	In2—O9iv	2.1243 (16)
K1—O14ii	3.109 (2)	In2—O13viii	2.1373 (16)
K1—O10	3.1604 (19)	In2—O3	2.1419 (16)
K1—O1	3.225 (2)	In2—O8	2.1551 (17)
K1—O7	3.289 (2)	In2—O7	2.1560 (16)
K1—O1i	3.405 (2)	In2—O12iii	2.1666 (17)
K1—As3	3.5000 (12)	As1—O1	1.6542 (17)
K1—As2	3.6985 (16)	As1—O2	1.6609 (16)
K2—O10iii	2.6849 (19)	As1—O3	1.6761 (16)
K2—O9iv	2.7016 (18)	As1—O4	1.7485 (16)
K2—O3ii	2.7645 (19)	As2—O5	1.6592 (16)
K2—O7	2.8609 (19)	As2—O7	1.6647 (16)
K2—O12iv	2.930 (2)	As2—O6	1.6677 (17)
K2—O9iii	3.244 (2)	As2—O4	1.7549 (16)
K2—O5v	3.4261 (18)	As3—O8	1.6550 (15)
K2—As3iii	3.6275 (15)	As3—O9	1.6708 (16)
K2—As1ii	3.6671 (15)	As3—O10	1.6763 (16)
K2—As3iv	3.8247 (13)	As3—O11	1.7538 (16)
K2—As4iv	3.8903 (14)	As4—O12	1.6579 (17)
K2—As2	3.9601 (13)	As4—O13	1.6697 (16)
In1—O5vi	2.0946 (17)	As4—O14	1.6727 (16)
In1—O1	2.1036 (17)	As4—O11	1.7607 (16)
O6i—K1—O2ii	120.26 (5)	O2vii—In1—K1	114.30 (5)
O6i—K1—O8	102.77 (5)	K1i—In1—K1	68.45 (3)
O2ii—K1—O8	128.48 (5)	O9iv—In2—O13viii	89.55 (6)
O6i—K1—O6	78.11 (5)	O9iv—In2—O3	172.63 (6)
O2ii—K1—O6	63.78 (5)	O13viii—In2—O3	97.43 (6)
O8—K1—O6	102.93 (5)	O9iv—In2—O8	84.32 (7)
O6i—K1—O13ii	114.87 (5)	O13viii—In2—O8	93.94 (7)
O2ii—K1—O13ii	109.47 (5)	O3—In2—O8	92.81 (7)
O8—K1—O13ii	71.53 (5)	O9iv—In2—O7	81.95 (6)
O6—K1—O13ii	166.51 (5)	O13viii—In2—O7	170.02 (6)
O6i—K1—O14ii	100.17 (6)	O3—In2—O7	91.30 (6)
O2ii—K1—O14ii	77.84 (5)	O8—In2—O7	90.42 (7)
O8—K1—O14ii	123.20 (5)	O9iv—In2—O12iii	87.43 (7)
O6—K1—O14ii	132.49 (5)	O13viii—In2—O12iii	87.02 (7)
O13ii—K1—O14ii	51.67 (5)	O3—In2—O12iii	95.25 (7)
O6i—K1—O10	57.03 (5)	O8—In2—O12iii	171.69 (6)
O2ii—K1—O10	176.42 (5)	O7—In2—O12iii	87.39 (7)
O8—K1—O10	55.10 (5)	O9iv—In2—K2	39.85 (4)
O6—K1—O10	116.56 (5)	O13viii—In2—K2	125.79 (5)
O13ii—K1—O10	70.97 (5)	O3—In2—K2	134.41 (5)
O14ii—K1—O10	100.08 (5)	O8—In2—K2	97.40 (5)
O6i—K1—O1	55.08 (5)	O7—In2—K2	44.56 (5)
O2ii—K1—O1	128.24 (5)	O12iii—In2—K2	75.47 (5)
O8—K1—O1	56.90 (5)	O9iv—In2—K2ix	54.43 (5)
O6—K1—O1	65.27 (5)	O13viii—In2—K2ix	59.83 (5)
O13ii—K1—O1	118.16 (5)	O3—In2—K2ix	131.59 (5)
O14ii—K1—O1	149.48 (5)	O8—In2—K2ix	127.99 (5)
O10—K1—O1	52.91 (5)	O7—In2—K2ix	110.57 (5)
O6i—K1—O7	113.18 (5)	O12iii—In2—K2ix	46.10 (5)
O2ii—K1—O7	77.31 (5)	K2—In2—K2ix	71.84 (3)
O8—K1—O7	59.57 (5)	O9iv—In2—K1	76.25 (5)
O6—K1—O7	51.60 (5)	O13viii—In2—K1	130.97 (5)
O13ii—K1—O7	116.67 (5)	O3—In2—K1	97.27 (5)
O14ii—K1—O7	145.31 (5)	O8—In2—K1	38.84 (5)
O10—K1—O7	105.77 (5)	O7—In2—K1	51.90 (5)
O1—K1—O7	64.43 (5)	O12iii—In2—K1	137.44 (5)
O6i—K1—O1i	64.20 (5)	K2—In2—K1	66.80 (2)
O2ii—K1—O1i	56.14 (5)	K2ix—In2—K1	130.47 (2)
O8—K1—O1i	152.21 (5)	O1—As1—O2	114.49 (9)
O6—K1—O1i	51.80 (5)	O1—As1—O3	114.04 (9)
O13ii—K1—O1i	135.76 (5)	O2—As1—O3	110.79 (8)
O14ii—K1—O1i	84.23 (5)	O1—As1—O4	102.79 (9)
O10—K1—O1i	120.95 (5)	O2—As1—O4	107.73 (8)
O1—K1—O1i	97.62 (5)	O3—As1—O4	106.13 (8)
O7—K1—O1i	101.37 (5)	O1—As1—K2x	152.44 (7)
O6i—K1—As3	83.20 (4)	O2—As1—K2x	69.60 (6)
O2ii—K1—As3	154.87 (4)	O3—As1—K2x	45.51 (6)
O8—K1—As3	27.77 (3)	O4—As1—K2x	101.41 (6)
O6—K1—As3	118.04 (4)	O5—As2—O7	116.83 (9)
O13ii—K1—As3	62.61 (4)	O5—As2—O6	111.77 (8)
O14ii—K1—As3	108.68 (4)	O7—As2—O6	109.04 (9)
O10—K1—As3	28.57 (3)	O5—As2—O4	102.19 (8)
O1—K1—As3	55.76 (4)	O7—As2—O4	109.84 (8)
O7—K1—As3	85.32 (4)	O6—As2—O4	106.52 (8)
O1i—K1—As3	146.83 (4)	O5—As2—K1	148.49 (6)
O6i—K1—As2	91.93 (4)	O7—As2—K1	62.78 (7)
O2ii—K1—As2	73.27 (4)	O6—As2—K1	48.98 (6)
O8—K1—As2	78.71 (4)	O4—As2—K1	107.28 (6)
O6—K1—As2	25.79 (3)	O5—As2—K1i	111.45 (6)
O13ii—K1—As2	143.34 (4)	O7—As2—K1i	130.87 (7)
O14ii—K1—As2	150.96 (4)	O6—As2—K1i	40.86 (6)
O10—K1—As2	108.62 (4)	O4—As2—K1i	66.62 (6)
O1—K1—As2	56.71 (4)	K1—As2—K1i	71.63 (3)
O7—K1—As2	26.75 (3)	O5—As2—K2	89.90 (7)
O1i—K1—As2	77.42 (4)	O7—As2—K2	38.85 (6)
As3—K1—As2	98.85 (3)	O6—As2—K2	96.95 (6)
O10iii—K2—O9iv	103.29 (6)	O4—As2—K2	146.96 (6)
O10iii—K2—O3ii	148.68 (5)	K1—As2—K2	71.29 (3)
O9iv—K2—O3ii	108.00 (6)	K1i—As2—K2	136.85 (2)
O10iii—K2—O7	77.31 (6)	O8—As3—O9	115.24 (8)
O9iv—K2—O7	60.53 (5)	O8—As3—O10	113.16 (8)
O3ii—K2—O7	119.83 (6)	O9—As3—O10	107.16 (8)
O10iii—K2—O12iv	107.93 (6)	O8—As3—O11	108.46 (8)
O9iv—K2—O12iv	75.74 (5)	O9—As3—O11	105.13 (8)
O3ii—K2—O12iv	78.86 (6)	O10—As3—O11	107.11 (8)
O7—K2—O12iv	135.65 (5)	O8—As3—K1	52.42 (6)
O10iii—K2—O9iii	53.02 (5)	O9—As3—K1	113.45 (6)
O9iv—K2—O9iii	77.12 (5)	O10—As3—K1	64.39 (6)
O3ii—K2—O9iii	133.51 (5)	O11—As3—K1	141.33 (6)
O7—K2—O9iii	103.15 (5)	O8—As3—K2vi	129.12 (6)
O12iv—K2—O9iii	57.14 (5)	O9—As3—K2vi	63.41 (6)
O10iii—K2—O5v	76.92 (6)	O10—As3—K2vi	43.92 (6)
O9iv—K2—O5v	131.30 (5)	O11—As3—K2vi	121.20 (6)
O3ii—K2—O5v	83.57 (6)	K1—As3—K2vi	80.29 (3)
O7—K2—O5v	72.55 (5)	O8—As3—K2iv	135.36 (6)
O12iv—K2—O5v	151.70 (5)	O9—As3—K2iv	37.63 (6)
O9iii—K2—O5v	128.64 (5)	O10—As3—K2iv	109.87 (6)
O10iii—K2—As3iii	25.66 (3)	O11—As3—K2iv	68.47 (6)
O9iv—K2—As3iii	91.84 (5)	K1—As3—K2iv	149.98 (2)
O3ii—K2—As3iii	148.57 (4)	K2vi—As3—K2iv	77.40 (3)
O7—K2—As3iii	90.99 (5)	O12—As4—O13	114.01 (9)
O12iv—K2—As3iii	82.93 (5)	O12—As4—O14	118.28 (9)
O9iii—K2—As3iii	27.42 (3)	O13—As4—O14	107.10 (8)
O5v—K2—As3iii	101.70 (4)	O12—As4—O11	104.77 (8)
O10iii—K2—As1ii	135.28 (4)	O13—As4—O11	104.59 (8)
O9iv—K2—As1ii	114.06 (5)	O14—As4—O11	106.99 (8)
O3ii—K2—As1ii	25.63 (3)	O12—As4—K1x	151.68 (6)
O7—K2—As1ii	99.90 (5)	O13—As4—K1x	53.94 (6)
O12iv—K2—As1ii	104.49 (4)	O14—As4—K1x	55.64 (7)
O9iii—K2—As1ii	156.93 (3)	O11—As4—K1x	103.26 (6)
O5v—K2—As1ii	60.25 (4)	O12—As4—K2iv	43.87 (7)
As3iii—K2—As1ii	154.03 (2)	O13—As4—K2iv	103.15 (6)
O10iii—K2—As3iv	120.46 (5)	O14—As4—K2iv	149.68 (6)
O9iv—K2—As3iv	22.19 (3)	O11—As4—K2iv	66.53 (6)
O3ii—K2—As3iv	89.60 (5)	K1x—As4—K2iv	153.30 (2)
O7—K2—As3iv	80.16 (4)	As1—O1—In1	137.71 (10)
O12iv—K2—As3iv	58.83 (4)	As1—O1—K1	129.03 (8)
O9iii—K2—As3iv	80.57 (4)	In1—O1—K1	93.24 (6)
O5v—K2—As3iv	143.46 (3)	As1—O1—K1i	100.72 (8)
As3iii—K2—As3iv	102.60 (3)	In1—O1—K1i	84.15 (6)
As1ii—K2—As3iv	102.46 (3)	K1—O1—K1i	82.38 (5)
O10iii—K2—As4iv	130.07 (5)	As1—O2—In1vii	129.48 (9)
O9iv—K2—As4iv	67.39 (4)	As1—O2—K1x	129.19 (8)
O3ii—K2—As4iv	63.75 (4)	In1vii—O2—K1x	99.93 (6)
O7—K2—As4iv	125.94 (4)	As1—O3—In2	120.25 (8)
O12iv—K2—As4iv	23.09 (3)	As1—O3—K2x	108.86 (8)
O9iii—K2—As4iv	77.51 (4)	In2—O3—K2x	126.82 (7)
O5v—K2—As4iv	147.12 (4)	As1—O4—As2	120.04 (9)
As3iii—K2—As4iv	104.51 (3)	As2—O5—In1iii	130.44 (9)
As1ii—K2—As4iv	88.12 (3)	As2—O5—K2v	116.32 (8)
As3iv—K2—As4iv	46.153 (19)	In1iii—O5—K2v	113.24 (6)
O10iii—K2—As2	71.17 (4)	As2—O6—In1i	125.62 (8)
O9iv—K2—As2	81.89 (4)	As2—O6—K1i	115.60 (8)
O3ii—K2—As2	114.46 (4)	In1i—O6—K1i	107.02 (6)
O7—K2—As2	21.41 (3)	As2—O6—K1	105.23 (7)
O12iv—K2—As2	156.80 (4)	In1i—O6—K1	96.99 (6)
O9iii—K2—As2	112.01 (4)	K1i—O6—K1	101.89 (5)
O5v—K2—As2	51.49 (3)	As2—O7—In2	135.63 (9)
As3iii—K2—As2	91.82 (3)	As2—O7—K2	119.75 (8)
As1ii—K2—As2	90.09 (3)	In2—O7—K2	103.52 (6)
As3iv—K2—As2	100.84 (3)	As2—O7—K1	90.47 (8)
As4iv—K2—As2	145.27 (2)	In2—O7—K1	97.04 (7)
O5vi—In1—O1	166.27 (7)	K2—O7—K1	92.93 (5)
O5vi—In1—O14	93.20 (7)	As3—O8—In2	142.75 (9)
O1—In1—O14	96.26 (8)	As3—O8—K1	99.81 (8)
O5vi—In1—O6i	90.56 (7)	In2—O8—K1	112.46 (7)
O1—In1—O6i	81.66 (7)	As3—O9—In2iv	127.85 (8)
O14—In1—O6i	170.49 (6)	As3—O9—K2iv	120.18 (8)
O5vi—In1—O10	106.60 (7)	In2iv—O9—K2iv	109.90 (6)
O1—In1—O10	83.61 (7)	As3—O9—K2vi	89.16 (7)
O14—In1—O10	88.56 (6)	In2iv—O9—K2vi	93.39 (6)
O6i—In1—O10	81.99 (6)	K2iv—O9—K2vi	102.88 (5)
O5vi—In1—O2vii	80.65 (7)	As3—O10—In1	123.52 (8)
O1—In1—O2vii	87.70 (7)	As3—O10—K2vi	110.42 (7)
O14—In1—O2vii	101.65 (6)	In1—O10—K2vi	123.98 (7)
O6i—In1—O2vii	87.57 (6)	As3—O10—K1	87.04 (6)
O10—In1—O2vii	167.27 (6)	In1—O10—K1	93.87 (6)
O5vi—In1—K1i	103.80 (5)	K2vi—O10—K1	103.39 (6)
O1—In1—K1i	62.60 (6)	As3—O11—As4	118.77 (9)
O14—In1—K1i	138.00 (5)	As4—O12—In2vi	145.24 (10)
O6i—In1—K1i	48.79 (5)	As4—O12—K2iv	113.04 (8)
O10—In1—K1i	121.39 (5)	In2vi—O12—K2iv	101.71 (7)
O2vii—In1—K1i	45.94 (4)	As4—O13—In2viii	127.33 (9)
O5vi—In1—K1	124.31 (5)	As4—O13—K1x	99.88 (7)
O1—In1—K1	54.63 (5)	In2viii—O13—K1x	132.34 (7)
O14—In1—K1	130.46 (5)	As4—O14—In1	124.72 (9)
O6i—In1—K1	41.42 (4)	As4—O14—K1x	97.99 (8)
O10—In1—K1	52.98 (5)	In1—O14—K1x	122.74 (7)