(NH4)Ga(HAsO4)2 and TlAl(HAsO4)2 - two new RbFe(HPO4)2-type M+M3+ arsenates

Schwendtner, K.; Kolitsch, U.

doi:10.1107/S2056989018013567

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ISSN: 2056-9890

Volume 74| Part 10| October 2018| Pages 1504-1508

https://doi.org/10.1107/S2056989018013567

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(NH₄)Ga(HAsO₄)₂ and TlAl(HAsO₄)₂ - two new RbFe(HPO₄)₂-type M⁺M³⁺ arsenates

Karolina Schwendtner ^a ^* and Uwe Kolitsch ^b

^aInstitute for Chemical Technology and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, 1060 Vienna, Austria, and ^bNaturhistorisches Museum, Burgring 7, 1010 Wien, and Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Wien, Austria
^*Correspondence e-mail: karolina.schwendtner@tuwien.ac.at

Edited by S. Parkin, University of Kentucky, USA (Received 18 September 2018; accepted 24 September 2018; online 28 September 2018)

The crystal structures of hydrothermally synthesized (T = 493 K, 7–9 d) ammonium gallium bis[hydrogen arsenate(V)], (NH₄)Ga(HAsO₄)₂, and thallium aluminium bis[hydrogen arsenate(V)], TlAl(HAsO₄)₂, were solved by single-crystal X-ray diffraction. Both compounds crystallize in the common RbFe(HPO₄)₂ structure type (R $[\overline{3}]$ c) and share the same tetrahedral–octahedral framework topology that houses the M⁺ cations in its channels. One of the two Tl sites is slightly offset from its ideal position. Strong O—H⋯O hydrogen bonds strengthen the network.

Keywords: crystal structure; (NH₄)Ga(HAsO₄)₂; TlAl(HAsO₄)₂.

CCDC references: 1869299; 1869298

1. Chemical context

Compounds with mixed tetrahedral–octahedral (T–O) framework structures feature a broad range of different atomic arrangements. These result in topologies with several interesting properties such as ion exchange (Masquelier et al., 1996 ) and ion conductivity (Chouchene et al., 2017 ), as well as unusual piezoelectric (Ren et al., 2015 ), magnetic (Ouerfelli et al., 2007 ) or non-linear optical features (frequency doubling) (Sun et al., 2017 ).

The two new compounds were obtained during an extensive experimental study of the system M⁺–M³⁺–O–(H)–As⁵⁺ (M⁺ = Li, Na, K, Rb, Cs, Ag, Tl, NH₄; M³⁺ = Al, Ga, In, Sc, Fe, Cr, Tl), which led to an unusually large variety of new structure types (Schwendtner & Kolitsch, 2004 , 2005 , 2007a ,b ,c , 2017a , 2018a ; Schwendtner, 2006 , 2008 ). Among the many different structure types found during our study, one atomic arrangement, the RbFe(HPO₄)₂ type (Lii & Wu, 1994 ; rhombohedral, R $[\overline{3}]$ c), was found to exhibit a large crystal–chemical flexibility, which allows the incorporation of a wide variety of M⁺ and M³⁺ cations. Previously, it was also known for the phosphate members RbAl(HPO₄)₂ and RbGa(HPO₄)₂ (Lesage et al., 2007 ). Currently (including the present paper), a total of eight arsenate members are known with the following M⁺M³⁺ combinations: TlAl and (NH₄)Ga (this work), RbIn, RbGa, RbAl, RbFe, CsIn and CsFe (Schwendtner & Kolitsch, 2017b , 2018a,b ,c ). It is noteworthy that no K members are currently known.

2. Structural commentary

The two compounds are representatives of the RbFe(HPO₄)₂ structure type (R $[\overline{3}]$ c; Lii & Wu, 1994) and show a basic tetrahedral–octahedral framework structure featuring interpenetrating channels, which host the M⁺ cations (Fig. 1). This structure type is closely related to the triclinic (NH₄)Fe(HPO₄)₂ type (P $[\overline{1}]$ ; Yakubovich, 1993 ) in which all other known (NH₄)M³⁺(HTO₄)₂ (T = P, As) compounds crystallize (see Schwendtner & Kolitsch, 2018b for a compilation), the RbAl₂As(HAsO₄)₆ type (R $[\overline{3}]$ c; Schwendtner & Kolitsch, 2018a) and the RbAl(HAsO₄)₂ type (R32; Schwendtner & Kolitsch, 2018a). The fundamental building unit in all these structure types contains M³⁺O₆ octahedra, which are connected via their six corners to six protonated AsO₄ tetrahedra, thereby forming an M³⁺As₆O₂₄ unit. These units are in turn connected via three corners to other M³⁺O₆ octahedra. The free, protonated corner of each AsO₄ tetrahedron forms a hydrogen bond to the neighbouring M³⁺As₆O₂₄ group (Fig. 2). The M³⁺As₆O₂₄ units are arranged in layers perpendicular to the c_hex axis (Fig. 1). The units within these layers are held together by medium–strong hydrogen bonds (Tables 1 and 2). Both title compounds invariably show a very similar crystal habit: strongly pseudo-hexagonal to pseudo-octahedral (cf. Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °) for (NH₄)Ga(HAsO₄)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4^xxi	0.87 (3)	1.74 (3)	2.610 (3)	172 (6)
Symmetry code: (xxi) $[y, x-1, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °) for TlAl(HAsO₄)₂

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4^xxi	0.87 (4)	1.87 (5)	2.584 (5)	139 (6)
Symmetry code: (xxi) $[y, x-1, -z+{\script{3\over 2}}]$ .

Figure 1
Structure drawings of the framework structures of (a) (NH₄)Ga(HAsO₄)₂ and (b) TlAl(HAsO₄)₂ viewed along a. The unit cell is outlined and the alternative position AsB in (b) is shown in light yellow (the main As position is orange). The Tl1 atom shows a slight positional disorder and is slightly offset from the ideal position.

Figure 2
Structure drawings of the framework structures of (a) (NH₄)Ga(HAsO₄)₂ and (b) TlAl(HAsO₄)₂ viewed along c. The unit cells are outlined and the alternative position AsB in (b), which can be generated by a mirror plane in (110), is shown in light yellow (the main As position is orange). The Tl1 atom shows a slight positional disorder.

Figure 3
SEM image showing a flattened pseudo-octahedral crystal of (NH₄)Ga(HAsO₄)₂.

TlAl(HAsO₄)₂ has the smallest unit cell of all the arsenates of this structure type published to date. Still, the size of the M⁺-hosting voids seems to be too large for the Tl⁺ cation, since Tl1 is slightly offset from the ideal position at 0, 0, 3/4 [resulting in some positional disorder for Tl1, with three symmetry-equivalent Tl1 positions in close proximity; Tl1–Tl1^i,ii = 0.28 (3) Å; symmetry codes: (i) −y, x − y, z; (ii) y − x, −x, z] and there are minor, but distinct negative and positive residual electron densities close to the Tl2 atom. The latter is severely underbonded, with a very low bond-valence sum (BVS) of only 0.54 valence units (v.u.) (calculated after Gagné & Hawthorne, 2015 ). The average Tl2—O bond length (Table 3) of 3.321 Å is considerably larger than the longest average Tl—O bond length of 3.304 Å described in the latest review paper (Gagné & Hawthorne, 2018 ), but still shorter than the excessively long average Tl—O bond length found in the related compound TlGa₂As(HAsO₄)₆ (3.439 Å, Schwendtner & Kolitsch, 2018b). The electron-density distribution is well fitted for the Tl1 atom, which has a BVS of 0.74 v.u. and an average Tl1—O bond length of 3.261 Å, which is also significantly longer than the reported average of 3.195 Å (Gagné & Hawthorne, 2018). In contrast, the two Al atoms are considerably overbonded (3.05 and 3.14 v.u. for Al1 and Al2, respectively) and average Al—O bond lengths of 1.898 and 1.887 Å are slightly shorter than the reported average of 1.903 Å (Gagné & Hawthorne, 2018), but well within the general range of Al—O bond lengths. The protonated AsO₄ group shows a fairly typical configuration with slightly above average As—O bond lengths and a BVS of 4.97 v.u. for the As atom. As expected from the strong hydrogen bond [2.584 (5) Å, Table 2] the As—O bond to the donor O3 atom is considerably elongated (Table 3).

Table 3
Selected bond lengths (Å) for TlAl(HAsO₄)₂

Tl1—Tl1ⁱ	0.28 (3)	Tl2—O4^xi	3.516 (3)
Tl1—O3	3.085 (8)	Tl2—O3^xii	3.545 (4)
Tl1—O3ⁱⁱ	3.085 (8)	Tl2—O3^xiii	3.545 (4)
Tl1—O3ⁱⁱⁱ	3.136 (5)	Tl2—O3^xiv	3.545 (4)
Tl1—O3ⁱ	3.136 (5)	Al1—O2^xv	1.895 (4)
Tl1—O2ⁱⁱⁱ	3.233 (13)	Al1—O2^v	1.895 (4)
Tl1—O2ⁱ	3.233 (13)	Al1—O2^xvi	1.895 (4)
Tl1—O3^iv	3.261 (12)	Al1—O4^xvii	1.901 (4)
Tl1—O3^v	3.261 (12)	Al1—O4ⁱ	1.901 (4)
Tl1—O2ⁱⁱ	3.351 (4)	Al1—O4^xviii	1.901 (4)
Tl1—O2	3.351 (4)	Al2—O1^viii	1.887 (4)
Tl1—O2^v	3.501 (15)	Al2—O1^xiv	1.887 (4)
Tl1—O2^iv	3.501 (15)	Al2—O1^xix	1.887 (4)
Tl2—O3ⁱ	2.813 (4)	Al2—O1ⁱ	1.887 (4)
Tl2—O3^v	2.813 (4)	Al2—O1^xviii	1.887 (4)
Tl2—O3	2.813 (4)	Al2—O1^xvii	1.887 (4)
Tl2—O1^vi	3.410 (4)	As—O1^xx	1.661 (3)
Tl2—O1^vii	3.410 (4)	As—O2	1.674 (3)
Tl2—O1^viii	3.410 (4)	As—O4ⁱⁱ	1.679 (3)
Tl2—O4^ix	3.516 (3)	As—O3	1.746 (4)
Tl2—O4^x	3.516 (3)
Symmetry codes: (i) -y, x-y, z; (ii) $[-x, -x+y, -z+{\script{3\over 2}}]$ ; (iii) $[y, x, -z+{\script{3\over 2}}]$ ; (iv) $[x-y, -y, -z+{\script{3\over 2}}]$ ; (v) -x+y, -x, z; (vi) $[-x+{\script{2\over 3}}, -y-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (vii) $[x-y-{\script{4\over 3}}, x-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (viii) $[y+{\script{2\over 3}}, -x+y+{\script{4\over 3}}, -z+{\script{4\over 3}}]$ ; (ix) $[x-{\script{1\over 3}}, x-y-{\script{2\over 3}}, z-{\script{1\over 6}}]$ ; (x) $[-y-{\script{1\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}]$ ; (xi) $[-x+y+{\script{2\over 3}}, y+{\script{1\over 3}}, z-{\script{1\over 6}}]$ ; (xii) $[-x-{\script{1\over 3}}, -y-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (xiii) $[y+{\script{2\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xiv) $[x-y-{\script{1\over 3}}, x+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xv) -y, x-y+1, z; (xvi) x+1, y+1, z; (xvii) x, y+1, z; (xviii) -x+y+1, -x+1, z; (xix) $[-x+{\script{2\over 3}}, -y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xx) x-1, y, z.

For (NH₄)Ga(HAsO₄)₂, the bond-valence sum values for the M³⁺ cations and As are quite similar (Table 4), with overbonded Ga³⁺ (BVS 3.10 and 3.15 v.u., respectively) and numbers for As that are close to the expected values (BVS 5.03 v.u., average bond length of 1.686 Å). The NH₄⁺ cations (average N⋯O = 3.268 Å for N1 and 3.336 Å for N2) seem to fill the M⁺-hosting voids much better, and the BVSs (calculated after García-Rodríguez et al., 2000 ) of 0.74 and 1.03 v.u. for N1 and N2, respectively, are closer to ideal values, although N1 is underbonded.

Table 4
Selected bond lengths (Å) for (NH₄)Ga(HAsO₄)

N1—O3	3.173 (3)	N2—O4^xi	3.493 (5)
N1—O3ⁱ	3.173 (3)	N2—O3^xii	3.557 (4)
N1—O3ⁱⁱ	3.173 (3)	N2—O3^xiii	3.557 (4)
N1—O3ⁱⁱⁱ	3.173 (3)	N2—O3^xiv	3.557 (4)
N1—O3^iv	3.173 (3)	Ga1—O2^xv	1.9619 (16)
N1—O3^v	3.173 (3)	Ga1—O2ⁱⁱⁱ	1.9619 (17)
N1—O2	3.3657 (18)	Ga1—O2^xvi	1.9619 (17)
N1—O2ⁱⁱ	3.3657 (18)	Ga1—O4^v	1.9666 (17)
N1—O2^iv	3.3657 (18)	Ga1—O4^xvii	1.9666 (17)
N1—O2ⁱⁱⁱ	3.3657 (18)	Ga1—O4^xviii	1.9667 (16)
N1—O2ⁱ	3.3657 (17)	Ga2—O1^viii	1.9588 (18)
N1—O2^v	3.3657 (17)	Ga2—O1^xiv	1.9588 (19)
N2—O3^v	2.918 (4)	Ga2—O1^xix	1.9588 (18)
N2—O3ⁱⁱⁱ	2.918 (4)	Ga2—O1^v	1.9589 (18)
N2—O3	2.918 (4)	Ga2—O1^xviii	1.9589 (19)
N2—O1^vi	3.375 (3)	Ga2—O1^xvii	1.9589 (18)
N2—O1^vii	3.375 (3)	As—O1^xx	1.6555 (18)
N2—O1^viii	3.375 (3)	As—O2	1.6700 (16)
N2—O4^ix	3.493 (5)	As—O4ⁱⁱ	1.6783 (17)
N2—O4^x	3.493 (5)	As—O3	1.740 (2)
Symmetry codes: (i) $[x-y, -y, -z+{\script{3\over 2}}]$ ; (ii) $[-x, -x+y, -z+{\script{3\over 2}}]$ ; (iii) -x+y, -x, z; (iv) $[y, x, -z+{\script{3\over 2}}]$ ; (v) -y, x-y, z; (vi) $[-x+{\script{2\over 3}}, -y-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (vii) $[x-y-{\script{4\over 3}}, x-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (viii) $[y+{\script{2\over 3}}, -x+y+{\script{4\over 3}}, -z+{\script{4\over 3}}]$ ; (ix) $[x-{\script{1\over 3}}, x-y-{\script{2\over 3}}, z-{\script{1\over 6}}]$ ; (x) $[-y-{\script{1\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}]$ ; (xi) $[-x+y+{\script{2\over 3}}, y+{\script{1\over 3}}, z-{\script{1\over 6}}]$ ; (xii) $[-x-{\script{1\over 3}}, -y-{\script{2\over 3}}, -z+{\script{4\over 3}}]$ ; (xiii) $[y+{\script{2\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xiv) $[x-y-{\script{1\over 3}}, x+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xv) -y, x-y+1, z; (xvi) x+1, y+1, z; (xvii) x, y+1, z; (xviii) -x+y+1, -x+1, z; (xix) $[-x+{\script{2\over 3}}, -y+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (xx) x-1, y, z.

3. Synthesis and crystallization

The compounds were grown by hydrothermal synthesis at 493 K (autogeneous pressure, slow furnace cooling) using Teflon-lined stainless steel autoclaves with an approximate filling volume of 2 cm³. Reagent-grade NH₄OH, Tl₂CO₃, Ga₂O₃, Al₂O₃ and H₃AsO₄·0.5H₂O were used as starting reagents in approximate volume ratios of M⁺:M³⁺:As of 1:1:3 of the respective M⁺M³⁺ compound for both synthesis batches. For TlAl(HAsO₄)₂, the vessels were filled with distilled water to about 70% of their inner volumes, which led to initial and final pH values of 1 and 0.5, respectively, and the synthesis was allowed to proceed at 493 K for 9 d. (NH₄)Ga(HAsO₄)₂ was grown over a period of 7 d and the initial and final pH values were 3 and 1, respectively. The reaction products were washed thoroughly with distilled water, filtered, and dried at room temperature. (NH₄)Ga(HAsO₄)₂ formed large colourless pseudo-octahedral crystals (Fig. 3), while TlAl(HAsO₄)₂ formed small pseudo-hexagonal platelets. Both compounds are stable in air.

A measured X-ray powder diffraction pattern of (NH₄)Ga(HAsO₄)₂ was deposited at the International Centre for Diffraction Data under PDF number 00-059-0055 (Wohlschlaeger et al., 2007 ).

Semiquantitative SEM–EDX analysis (15 kV) of carbon-coated, horizontally oriented crystals of (NH₄)Ga(HAsO₄)₂ were undertaken to discriminate between H₃O⁺ and NH₄⁺. They confirmed the suspected formula and revealed no impurities.

4. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 5.

Table 5
Experimental details

	(NH₄)Ga(HAsO₄)₂	TlAl(HAsO₄)₂
Crystal data
M_r	367.62	511.21
Crystal system, space group	Trigonal, R $[\overline{3}]$ c:H	Trigonal, R $[\overline{3}]$ c:H
Temperature (K)	293	293
a, c (Å)	8.380 (1), 53.811 (11)	8.290 (1), 52.940 (11)
V (Å³)	3272.6 (10)	3150.8 (10)
Z	18	18
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	12.83	32.58
Crystal size (mm)	0.08 × 0.07 × 0.03	0.08 × 0.07 × 0.03

Data collection
Diffractometer	Nonius KappaCCD single-crystal four-circle diffractometer	Nonius KappaCCD single-crystal four-circle
Absorption correction	Multi-scan (HKL SCALEPACK; Otwinowski et al., 2003 )	Multi-scan (HKL SCALEPACK; Otwinowski et al., 2003)
T_min, T_max	0.427, 0.700	0.180, 0.441
No. of measured, independent and observed [I > 2σ(I)] reflections	4834, 1326, 1156	2478, 698, 685
R_int	0.024	0.022
(sin θ/λ)_max (Å⁻¹)	0.757	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.055, 1.07	0.022, 0.058, 1.21
No. of reflections	1326	698
No. of parameters	61	69
No. of restraints	1	2
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.95	0.82, −1.98
Computer programs: COLLECT (Nonius, 2003 ), HKL DENZO and SCALEPACK (Otwinowski et al., 2003), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2005 ) and publCIF (Westrip, 2010 ).

For the refinement of both compounds, the coordinates of RbFe(HPO₄)₂ (Lii & Wu, 1994) were used for the initial refinement steps. The hydrogen atoms were then located in difference-Fourier maps and added to the models. In both compounds O—H bonds were restrained to 0.9 ± 0.04 Å. In (NH₄)Ga(HAsO₄)₂, several electron-density peaks between 0.4 and 0.75 e Å⁻³ were recognizable that could be attributed to the H atoms of the NH₄⁺ cation. These peaks are located at the following coordinates for the N1 atom: 0.0170, 0.1329, 0.7450; 0.0641, 0.0560, 0.7414 and −0.0910, 0.0000, 0.7500. For the N2 atom, the coordinates are: 0.0478, −0.0330, 0.6635; −0.0655, −0.1106, 0.6786; 0.1301, 0.0094, 0.6695 and −0.0521, −0.0657, 0.6513. However, despite the use of restraints, no sensible coordination geometry for the H atoms around the N atoms could be found. Therefore, they were omitted from the model. As a result of the fact that there are 12 possible N—H⋯O bonds for each N atom, with only two symmetry-equivalent positions for N1 and four for N2, it seems reasonable to assume that the H-atom positions around the N atoms are, in both cases, highly disordered. The final residual electron density in (NH₄)Ga(HAsO₄)₂ is < 1e Å⁻³.

The refinement of TlAl(HAsO₄)₂ revealed a considerable residual electron-density peak of 2.2 e Å⁻³ 1.28 Å away from As and 1.61 Å away from the O1 site. The corresponding position can be generated by a mirror plane in (110) and therefore could be an alternative flipped As position (sharing the same O1 atom). Since the inclusion of the alternative position led to a considerable drop in R₁ and weighting parameters and the highest residual electron density dropped to < 1 e Å⁻³, this position was kept in the model. The occupancy of the alternative position AsB (Fig. 1b, 2b) refined to only 2.1%, which makes it impossible to locate the alternative O ligand positions that should comprise the coordination sphere of the AsB position. For the final refinement, the displacement parameters of the AsB position were restrained to be the same as for the main As position and the sum of As was restrained to give a total occupancy of 1.00. We note that a similar alternative position was also found for isotypic CsIn(HAsO₄)₂ (Schwendtner & Kolitsch, 2017b).

There was also considerable residual electron density of ±2 e Å ⁻³ close to the two Tl positions, similar to what was encountered in the structurally related TlGa₂As(HAsO₄)₆ (Schwendtner & Kolitsch, 2018d ). We tried a similar approach that had worked well for the aforementioned compound, viz. to remove the Tl atoms from their ideal, highly symmetrical positions in this structure type. We obtained a better refinement with a slightly off-centre position for Tl1, in line with a slight disorder (probably static), possibly in part or in whole due to the stereochemical activity of the lone electron pair on the Tl⁺ cations. So, although the Tl1 site is slightly offset from its ideal position (0, 0, 3/4), we unfortunately did not manage to get rid of the negative residual electron density of about −2 e Å⁻³ next to Tl2. The most positive residual electron density peak, however, dropped to < 1 e Å⁻³.

Supporting information

CCDC references: 1869299; 1869298

Crystal structure: contains datablocks NH4GaHAsO42, TlAlHAsO42. DOI: https://doi.org/10.1107/S2056989018013567/pk2608sup1.cif

Structure factors: contains datablock NH4GaHAsO42. DOI: https://doi.org/10.1107/S2056989018013567/pk2608NH4GaHAsO42sup2.hkl

Structure factors: contains datablock TlAlHAsO42. DOI: https://doi.org/10.1107/S2056989018013567/pk2608TlAlHAsO42sup3.hkl

checkCIF report

Computing details top

For both structures, data collection: COLLECT (Nonius, 2003); cell refinement: HKL SCALEPACK (Otwinowski et al., 2003); data reduction: HKL DENZO and SCALEPACK (Otwinowski et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42) top

Crystal data top

(NH₄)Ga(HAsO₄)₂	D_x = 3.358 Mg m⁻³
M_r = 367.62	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c:H	Cell parameters from 2653 reflections
a = 8.380 (1) Å	θ = 2.9–32.5°
c = 53.811 (11) Å	µ = 12.83 mm⁻¹
V = 3272.6 (10) Å³	T = 293 K
Z = 18	Small pseudo-octahedral platelets, colourless
F(000) = 3132	0.08 × 0.07 × 0.03 mm

Data collection top

Nonius KappaCCD single-crystal four-circle diffractometer	1156 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
φ and ω scans	θ_max = 32.5°, θ_min = 2.9°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski et al., 2003)	h = −12→12
T_min = 0.427, T_max = 0.700	k = −10→10
4834 measured reflections	l = −80→81
1326 independent reflections

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)] = 0.022	All H-atom parameters refined
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0273P)² + 16.8283P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
1326 reflections	Δρ_max = 0.75 e Å⁻³
61 parameters	Δρ_min = −0.95 e Å⁻³
1 restraint	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00016 (3)

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
N1	0.000000	0.000000	0.750000	0.051 (2)
N2	0.000000	0.000000	0.66731 (10)	0.0487 (15)
Ga1	0.333333	0.666667	0.75382 (2)	0.00954 (10)
Ga2	0.333333	0.666667	0.666667	0.01164 (13)
As	−0.42915 (3)	−0.39386 (3)	0.71282 (2)	0.01072 (8)
O1	0.4557 (3)	−0.4378 (3)	0.68635 (3)	0.0218 (4)
O2	−0.4457 (2)	−0.2535 (2)	0.73337 (3)	0.0133 (3)
O3	−0.1958 (3)	−0.2785 (3)	0.70541 (4)	0.0243 (4)
O4	0.4778 (2)	−0.1224 (2)	0.77594 (3)	0.0127 (3)
H3	−0.161 (8)	−0.353 (6)	0.7114 (9)	0.075 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.062 (4)	0.062 (4)	0.029 (4)	0.0311 (18)	0.000	0.000
N2	0.060 (2)	0.060 (2)	0.026 (2)	0.0300 (12)	0.000	0.000
Ga1	0.01025 (13)	0.01025 (13)	0.00811 (19)	0.00513 (6)	0.000	0.000
Ga2	0.01394 (18)	0.01394 (18)	0.0070 (2)	0.00697 (9)	0.000	0.000
As	0.01365 (12)	0.01158 (12)	0.00927 (12)	0.00807 (9)	0.00172 (8)	0.00141 (7)
O1	0.0368 (11)	0.0281 (10)	0.0101 (7)	0.0234 (9)	−0.0049 (7)	−0.0010 (7)
O2	0.0137 (7)	0.0121 (7)	0.0135 (7)	0.0061 (6)	0.0030 (6)	−0.0014 (6)
O3	0.0192 (9)	0.0220 (9)	0.0362 (12)	0.0137 (8)	0.0137 (8)	0.0126 (8)
O4	0.0136 (7)	0.0108 (7)	0.0153 (7)	0.0073 (6)	−0.0026 (6)	−0.0047 (6)

Geometric parameters (Å, º) top

N1—O3	3.173 (3)	N2—O3^xii	3.557 (4)
N1—O3ⁱ	3.173 (3)	N2—O3^xiii	3.557 (4)
N1—O3ⁱⁱ	3.173 (3)	N2—O3^xiv	3.557 (4)
N1—O3ⁱⁱⁱ	3.173 (3)	Ga1—O2^xv	1.9619 (16)
N1—O3^iv	3.173 (3)	Ga1—O2ⁱⁱⁱ	1.9619 (17)
N1—O3^v	3.173 (3)	Ga1—O2^xvi	1.9619 (17)
N1—O2	3.3657 (18)	Ga1—O4^v	1.9666 (17)
N1—O2ⁱⁱ	3.3657 (18)	Ga1—O4^xvii	1.9666 (17)
N1—O2^iv	3.3657 (18)	Ga1—O4^xviii	1.9667 (16)
N1—O2ⁱⁱⁱ	3.3657 (18)	Ga2—O1^viii	1.9588 (18)
N1—O2ⁱ	3.3657 (17)	Ga2—O1^xiv	1.9588 (19)
N1—O2^v	3.3657 (17)	Ga2—O1^xix	1.9588 (18)
N2—O3^v	2.918 (4)	Ga2—O1^v	1.9589 (18)
N2—O3ⁱⁱⁱ	2.918 (4)	Ga2—O1^xviii	1.9589 (19)
N2—O3	2.918 (4)	Ga2—O1^xvii	1.9589 (18)
N2—O1^vi	3.375 (3)	As—O1^xx	1.6555 (18)
N2—O1^vii	3.375 (3)	As—O2	1.6700 (16)
N2—O1^viii	3.375 (3)	As—O4ⁱⁱ	1.6783 (17)
N2—O4^ix	3.493 (5)	As—O3	1.740 (2)
N2—O4^x	3.493 (5)	O3—H3	0.87 (3)
N2—O4^xi	3.493 (5)

O3—N1—O3ⁱ	162.83 (7)	O2^xv—Ga1—N1	119.85 (5)
O3—N1—O3ⁱⁱ	123.01 (7)	O2ⁱⁱⁱ—Ga1—N1	32.80 (5)
O3ⁱ—N1—O3ⁱⁱ	69.03 (6)	O2^xvi—Ga1—N1	105.75 (5)
O3—N1—O3ⁱⁱⁱ	69.03 (6)	O4^v—Ga1—N1	77.33 (5)
O3ⁱ—N1—O3ⁱⁱⁱ	102.44 (7)	O4^xvii—Ga1—N1	143.46 (5)
O3ⁱⁱ—N1—O3ⁱⁱⁱ	162.83 (8)	O4^xviii—Ga1—N1	59.54 (5)
O3—N1—O3^iv	102.44 (7)	N2^xxi—Ga1—N1	92.432 (5)
O3ⁱ—N1—O3^iv	69.03 (6)	N1^xvii—Ga1—N1	119.821 (1)
O3ⁱⁱ—N1—O3^iv	69.03 (6)	O2^xv—Ga1—N1^xvi	105.75 (5)
O3ⁱⁱⁱ—N1—O3^iv	123.01 (7)	O2ⁱⁱⁱ—Ga1—N1^xvi	119.85 (5)
O3—N1—O3^v	69.03 (6)	O2^xvi—Ga1—N1^xvi	32.80 (5)
O3ⁱ—N1—O3^v	123.01 (8)	O4^v—Ga1—N1^xvi	143.46 (5)
O3ⁱⁱ—N1—O3^v	102.44 (7)	O4^xvii—Ga1—N1^xvi	59.54 (5)
O3ⁱⁱⁱ—N1—O3^v	69.03 (6)	O4^xviii—Ga1—N1^xvi	77.33 (5)
O3^iv—N1—O3^v	162.83 (7)	N2^xxi—Ga1—N1^xvi	92.432 (5)
O3—N1—O2	48.11 (4)	N1^xvii—Ga1—N1^xvi	119.821 (1)
O3ⁱ—N1—O2	115.51 (5)	N1—Ga1—N1^xvi	119.821 (1)
O3ⁱⁱ—N1—O2	126.51 (5)	O1^viii—Ga2—O1^xiv	93.53 (7)
O3ⁱⁱⁱ—N1—O2	70.41 (5)	O1^viii—Ga2—O1^xix	93.53 (7)
O3^iv—N1—O2	65.01 (5)	O1^xiv—Ga2—O1^xix	93.53 (7)
O3^v—N1—O2	113.56 (5)	O1^viii—Ga2—O1^v	180.0
O3—N1—O2ⁱⁱ	126.52 (5)	O1^xiv—Ga2—O1^v	86.47 (7)
O3ⁱ—N1—O2ⁱⁱ	70.41 (5)	O1^xix—Ga2—O1^v	86.47 (7)
O3ⁱⁱ—N1—O2ⁱⁱ	48.11 (5)	O1^viii—Ga2—O1^xviii	86.47 (7)
O3ⁱⁱⁱ—N1—O2ⁱⁱ	115.51 (5)	O1^xiv—Ga2—O1^xviii	180.0
O3^iv—N1—O2ⁱⁱ	113.56 (5)	O1^xix—Ga2—O1^xviii	86.47 (7)
O3^v—N1—O2ⁱⁱ	65.01 (5)	O1^v—Ga2—O1^xviii	93.53 (7)
O2—N1—O2ⁱⁱ	171.26 (6)	O1^viii—Ga2—O1^xvii	86.47 (7)
O3—N1—O2^iv	65.01 (5)	O1^xiv—Ga2—O1^xvii	86.47 (7)
O3ⁱ—N1—O2^iv	113.56 (5)	O1^xix—Ga2—O1^xvii	180.0
O3ⁱⁱ—N1—O2^iv	70.41 (5)	O1^v—Ga2—O1^xvii	93.53 (7)
O3ⁱⁱⁱ—N1—O2^iv	126.51 (5)	O1^xviii—Ga2—O1^xvii	93.53 (7)
O3^iv—N1—O2^iv	48.11 (4)	O1^viii—Ga2—N2^xix	62.79 (8)
O3^v—N1—O2^iv	115.51 (5)	O1^xiv—Ga2—N2^xix	67.00 (7)
O2—N1—O2^iv	59.00 (6)	O1^xix—Ga2—N2^xix	146.77 (8)
O2ⁱⁱ—N1—O2^iv	113.20 (2)	O1^v—Ga2—N2^xix	117.21 (8)
O3—N1—O2ⁱⁱⁱ	113.56 (5)	O1^xviii—Ga2—N2^xix	113.00 (7)
O3ⁱ—N1—O2ⁱⁱⁱ	65.01 (5)	O1^xvii—Ga2—N2^xix	33.23 (8)
O3ⁱⁱ—N1—O2ⁱⁱⁱ	115.51 (5)	O1^viii—Ga2—N2^xvii	117.21 (8)
O3ⁱⁱⁱ—N1—O2ⁱⁱⁱ	48.11 (5)	O1^xiv—Ga2—N2^xvii	113.00 (7)
O3^iv—N1—O2ⁱⁱⁱ	126.51 (5)	O1^xix—Ga2—N2^xvii	33.23 (8)
O3^v—N1—O2ⁱⁱⁱ	70.41 (5)	O1^v—Ga2—N2^xvii	62.79 (8)
O2—N1—O2ⁱⁱⁱ	113.20 (2)	O1^xviii—Ga2—N2^xvii	66.99 (7)
O2ⁱⁱ—N1—O2ⁱⁱⁱ	74.86 (6)	O1^xvii—Ga2—N2^xvii	146.77 (8)
O2^iv—N1—O2ⁱⁱⁱ	171.26 (6)	N2^xix—Ga2—N2^xvii	180.0
O3—N1—O2ⁱ	115.51 (5)	O1^viii—Ga2—N2	33.23 (8)
O3ⁱ—N1—O2ⁱ	48.11 (4)	O1^xiv—Ga2—N2	117.21 (8)
O3ⁱⁱ—N1—O2ⁱ	113.56 (5)	O1^xix—Ga2—N2	113.01 (8)
O3ⁱⁱⁱ—N1—O2ⁱ	65.01 (5)	O1^v—Ga2—N2	146.77 (8)
O3^iv—N1—O2ⁱ	70.41 (5)	O1^xviii—Ga2—N2	62.79 (8)
O3^v—N1—O2ⁱ	126.51 (5)	O1^xvii—Ga2—N2	67.00 (8)
O2—N1—O2ⁱ	74.86 (6)	N2^xix—Ga2—N2	60.005 (2)
O2ⁱⁱ—N1—O2ⁱ	113.20 (2)	N2^xvii—Ga2—N2	119.995 (2)
O2^iv—N1—O2ⁱ	113.20 (2)	O1^viii—Ga2—N2^xvi	113.01 (7)
O2ⁱⁱⁱ—N1—O2ⁱ	59.00 (6)	O1^xiv—Ga2—N2^xvi	33.23 (8)
O3—N1—O2^v	70.41 (5)	O1^xix—Ga2—N2^xvi	117.21 (8)
O3ⁱ—N1—O2^v	126.51 (5)	O1^v—Ga2—N2^xvi	66.99 (7)
O3ⁱⁱ—N1—O2^v	65.01 (5)	O1^xviii—Ga2—N2^xvi	146.77 (8)
O3ⁱⁱⁱ—N1—O2^v	113.56 (5)	O1^xvii—Ga2—N2^xvi	62.79 (8)
O3^iv—N1—O2^v	115.51 (5)	N2^xix—Ga2—N2^xvi	60.005 (2)
O3^v—N1—O2^v	48.11 (4)	N2^xvii—Ga2—N2^xvi	119.995 (2)
O2—N1—O2^v	113.20 (2)	N2—Ga2—N2^xvi	119.995 (2)
O2ⁱⁱ—N1—O2^v	59.00 (6)	O1^viii—Ga2—N2^xxii	66.99 (7)
O2^iv—N1—O2^v	74.86 (6)	O1^xiv—Ga2—N2^xxii	146.77 (8)
O2ⁱⁱⁱ—N1—O2^v	113.20 (2)	O1^xix—Ga2—N2^xxii	62.79 (8)
O2ⁱ—N1—O2^v	171.26 (6)	O1^v—Ga2—N2^xxii	113.00 (7)
O3^v—N2—O3ⁱⁱⁱ	76.09 (13)	O1^xviii—Ga2—N2^xxii	33.23 (8)
O3^v—N2—O3	76.08 (13)	O1^xvii—Ga2—N2^xxii	117.21 (8)
O3ⁱⁱⁱ—N2—O3	76.08 (13)	N2^xix—Ga2—N2^xxii	119.995 (2)
O3^v—N2—O1^vi	77.21 (6)	N2^xvii—Ga2—N2^xxii	60.005 (2)
O3ⁱⁱⁱ—N2—O1^vi	152.44 (16)	N2—Ga2—N2^xxii	60.005 (2)
O3—N2—O1^vi	91.02 (6)	N2^xvi—Ga2—N2^xxii	180.0
O3^v—N2—O1^vii	152.44 (16)	O1^viii—Ga2—N2^xxiii	146.77 (8)
O3ⁱⁱⁱ—N2—O1^vii	91.02 (6)	O1^xiv—Ga2—N2^xxiii	62.79 (8)
O3—N2—O1^vii	77.21 (6)	O1^xix—Ga2—N2^xxiii	66.99 (8)
O1^vi—N2—O1^vii	110.03 (9)	O1^v—Ga2—N2^xxiii	33.23 (8)
O3^v—N2—O1^viii	91.02 (6)	O1^xviii—Ga2—N2^xxiii	117.21 (8)
O3ⁱⁱⁱ—N2—O1^viii	77.21 (6)	O1^xvii—Ga2—N2^xxiii	113.00 (8)
O3—N2—O1^viii	152.44 (16)	N2^xix—Ga2—N2^xxiii	119.995 (2)
O1^vi—N2—O1^viii	110.03 (9)	N2^xvii—Ga2—N2^xxiii	60.005 (2)
O1^vii—N2—O1^viii	110.03 (9)	N2—Ga2—N2^xxiii	180.0
O3^v—N2—O4^ix	111.48 (7)	N2^xvi—Ga2—N2^xxiii	60.005 (2)
O3ⁱⁱⁱ—N2—O4^ix	156.43 (10)	N2^xxii—Ga2—N2^xxiii	119.994 (2)
O3—N2—O4^ix	126.99 (7)	O1^xx—As—O2	118.81 (9)
O1^vi—N2—O4^ix	45.41 (6)	O1^xx—As—O4ⁱⁱ	105.46 (9)
O1^vii—N2—O4^ix	90.09 (12)	O2—As—O4ⁱⁱ	115.11 (9)
O1^viii—N2—O4^ix	80.30 (10)	O1^xx—As—O3	107.12 (11)
O3^v—N2—O4^x	156.43 (10)	O2—As—O3	103.09 (10)
O3ⁱⁱⁱ—N2—O4^x	126.99 (7)	O4ⁱⁱ—As—O3	106.35 (9)
O3—N2—O4^x	111.48 (7)	O1^xx—As—N2^xii	64.22 (8)
O1^vi—N2—O4^x	80.30 (10)	O2—As—N2^xii	173.25 (6)
O1^vii—N2—O4^x	45.41 (6)	O4ⁱⁱ—As—N2^xii	68.25 (8)
O1^viii—N2—O4^x	90.09 (12)	O3—As—N2^xii	70.17 (8)
O4^ix—N2—O4^x	45.67 (8)	O1^xx—As—N1	142.98 (8)
O3^v—N2—O4^xi	126.99 (7)	O2—As—N1	56.21 (6)
O3ⁱⁱⁱ—N2—O4^xi	111.48 (7)	O4ⁱⁱ—As—N1	108.99 (6)
O3—N2—O4^xi	156.43 (10)	O3—As—N1	50.09 (8)
O1^vi—N2—O4^xi	90.09 (12)	N2^xii—As—N1	117.48 (2)
O1^vii—N2—O4^xi	80.30 (10)	O1^xx—As—N2	81.32 (10)
O1^viii—N2—O4^xi	45.41 (6)	O2—As—N2	99.84 (7)
O4^ix—N2—O4^xi	45.67 (8)	O4ⁱⁱ—As—N2	133.25 (6)
O4^x—N2—O4^xi	45.67 (8)	O3—As—N2	32.26 (8)
O3^v—N2—O3^xii	119.40 (8)	N2^xii—As—N2	74.310 (11)
O3ⁱⁱⁱ—N2—O3^xii	150.86 (8)	N1—As—N2	65.36 (6)
O3—N2—O3^xii	83.78 (6)	O1^xx—As—N1^xxiv	88.02 (8)
O1^vi—N2—O3^xii	46.33 (6)	O2—As—N1^xxiv	94.12 (6)
O1^vii—N2—O3^xii	63.78 (7)	O4ⁱⁱ—As—N1^xxiv	40.77 (6)
O1^viii—N2—O3^xii	123.57 (16)	O3—As—N1^xxiv	147.10 (7)
O4^ix—N2—O3^xii	45.67 (7)	N2^xii—As—N1^xxiv	92.00 (3)
O4^x—N2—O3^xii	43.44 (7)	N1—As—N1^xxiv	127.434 (12)
O4^xi—N2—O3^xii	80.03 (12)	N2—As—N1^xxiv	165.32 (5)
O3^v—N2—O3^xiii	83.77 (6)	O1^xx—As—N2^xxiv	43.28 (9)
O3ⁱⁱⁱ—N2—O3^xiii	119.40 (8)	O2—As—N2^xxiv	127.15 (7)
O3—N2—O3^xiii	150.86 (7)	O4ⁱⁱ—As—N2^xxiv	63.82 (7)
O1^vi—N2—O3^xiii	63.78 (7)	O3—As—N2^xxiv	128.79 (9)
O1^vii—N2—O3^xiii	123.57 (16)	N2^xii—As—N2^xxiv	59.42 (2)
O1^viii—N2—O3^xiii	46.33 (6)	N1—As—N2^xxiv	172.65 (3)
O4^ix—N2—O3^xiii	43.44 (7)	N2—As—N2^xxiv	117.94 (11)
O4^x—N2—O3^xiii	80.03 (12)	N1^xxiv—As—N2^xxiv	48.43 (5)
O4^xi—N2—O3^xiii	45.67 (7)	As^xxv—O1—Ga2^xxvi	137.99 (11)
O3^xii—N2—O3^xiii	88.14 (11)	As^xxv—O1—N2^vi	89.57 (11)
O3^v—N2—O3^xiv	150.86 (8)	Ga2^xxvi—O1—N2^vi	128.22 (11)
O3ⁱⁱⁱ—N2—O3^xiv	83.77 (6)	As^xxv—O1—N2^xxv	76.36 (10)
O3—N2—O3^xiv	119.40 (8)	Ga2^xxvi—O1—N2^xxv	93.37 (8)
O1^vi—N2—O3^xiv	123.57 (16)	N2^vi—O1—N2^xxv	76.98 (4)
O1^vii—N2—O3^xiv	46.33 (6)	As^xxv—O1—N2^xxvi	121.95 (10)
O1^viii—N2—O3^xiv	63.78 (7)	Ga2^xxvi—O1—N2^xxvi	89.12 (8)
O4^ix—N2—O3^xiv	80.03 (12)	N2^vi—O1—N2^xxvi	74.93 (4)
O4^x—N2—O3^xiv	45.67 (7)	N2^xxv—O1—N2^xxvi	145.93 (11)
O4^xi—N2—O3^xiv	43.44 (7)	As—O2—Ga1^xxiv	121.85 (9)
O3^xii—N2—O3^xiv	88.14 (11)	As—O2—N1	99.43 (7)
O3^xiii—N2—O3^xiv	88.14 (11)	Ga1^xxiv—O2—N1	128.79 (7)
O2^xv—Ga1—O2ⁱⁱⁱ	91.61 (7)	As—O2—N2	60.17 (5)
O2^xv—Ga1—O2^xvi	91.61 (7)	Ga1^xxiv—O2—N2	163.08 (8)
O2ⁱⁱⁱ—Ga1—O2^xvi	91.61 (7)	N1—O2—N2	63.03 (5)
O2^xv—Ga1—O4^v	88.91 (7)	As—O3—N2	129.17 (11)
O2ⁱⁱⁱ—Ga1—O4^v	92.29 (8)	As—O3—N1	105.03 (9)
O2^xvi—Ga1—O4^v	176.05 (7)	N2—O3—N1	93.77 (9)
O2^xv—Ga1—O4^xvii	92.29 (8)	As—O3—N2^xii	82.43 (8)
O2ⁱⁱⁱ—Ga1—O4^xvii	176.05 (7)	N2—O3—N2^xii	96.22 (6)
O2^xvi—Ga1—O4^xvii	88.91 (7)	N1—O3—N2^xii	159.27 (9)
O4^v—Ga1—O4^xvii	87.16 (8)	As—O3—H3	102 (4)
O2^xv—Ga1—O4^xviii	176.05 (7)	N2—O3—H3	125 (4)
O2ⁱⁱⁱ—Ga1—O4^xviii	88.91 (7)	N1—O3—H3	91 (3)
O2^xvi—Ga1—O4^xviii	92.29 (7)	N2^xii—O3—H3	69 (3)
O4^v—Ga1—O4^xviii	87.16 (8)	Asⁱⁱ—O4—Ga1^xxvi	130.02 (10)
O4^xvii—Ga1—O4^xviii	87.16 (8)	Asⁱⁱ—O4—N2^xxvii	85.25 (7)
O2^xv—Ga1—N2^xxi	124.12 (5)	Ga1^xxvi—O4—N2^xxvii	100.62 (8)
O2ⁱⁱⁱ—Ga1—N2^xxi	124.12 (5)	Asⁱⁱ—O4—N1^xxv	124.11 (7)
O2^xvi—Ga1—N2^xxi	124.12 (5)	Ga1^xxvi—O4—N1^xxv	96.68 (6)
O4^v—Ga1—N2^xxi	52.75 (5)	N2^xxvii—O4—N1^xxv	118.40 (4)
O4^xvii—Ga1—N2^xxi	52.75 (5)	Asⁱⁱ—O4—N1	51.75 (5)
O4^xviii—Ga1—N2^xxi	52.75 (5)	Ga1^xxvi—O4—N1	79.17 (5)
O2^xv—Ga1—N1^xvii	32.80 (5)	N2^xxvii—O4—N1	104.63 (4)
O2ⁱⁱⁱ—Ga1—N1^xvii	105.75 (5)	N1^xxv—O4—N1	136.70 (4)
O2^xvi—Ga1—N1^xvii	119.85 (5)	Asⁱⁱ—O4—N2^xxviii	98.66 (7)
O4^v—Ga1—N1^xvii	59.54 (5)	Ga1^xxvi—O4—N2^xxviii	129.48 (6)
O4^xvii—Ga1—N1^xvii	77.33 (5)	N2^xxvii—O4—N2^xxviii	66.70 (3)
O4^xviii—Ga1—N1^xvii	143.46 (5)	N1^xxv—O4—N2^xxviii	57.01 (5)
N2^xxi—Ga1—N1^xvii	92.432 (5)	N1—O4—N2^xxviii	150.37 (5)

Symmetry codes: (i) x−y, −y, −z+3/2; (ii) −x, −x+y, −z+3/2; (iii) −x+y, −x, z; (iv) y, x, −z+3/2; (v) −y, x−y, z; (vi) −x+2/3, −y−2/3, −z+4/3; (vii) x−y−4/3, x−2/3, −z+4/3; (viii) y+2/3, −x+y+4/3, −z+4/3; (ix) x−1/3, x−y−2/3, z−1/6; (x) −y−1/3, −x+1/3, z−1/6; (xi) −x+y+2/3, y+1/3, z−1/6; (xii) −x−1/3, −y−2/3, −z+4/3; (xiii) y+2/3, −x+y+1/3, −z+4/3; (xiv) x−y−1/3, x+1/3, −z+4/3; (xv) −y, x−y+1, z; (xvi) x+1, y+1, z; (xvii) x, y+1, z; (xviii) −x+y+1, −x+1, z; (xix) −x+2/3, −y+1/3, −z+4/3; (xx) x−1, y, z; (xxi) −y+1/3, −x+2/3, z+1/6; (xxii) −x−1/3, −y+1/3, −z+4/3; (xxiii) −x+2/3, −y+4/3, −z+4/3; (xxiv) x−1, y−1, z; (xxv) x+1, y, z; (xxvi) x, y−1, z; (xxvii) −y+1/3, −x−1/3, z+1/6; (xxviii) y+1, x, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^xxix	0.87 (3)	1.74 (3)	2.610 (3)	172 (6)

Symmetry code: (xxix) y, x−1, −z+3/2.

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42) top

Crystal data top

TlAl(HAsO₄)₂	D_x = 4.849 Mg m⁻³
M_r = 511.21	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c:H	Cell parameters from 1004 reflections
a = 8.290 (1) Å	θ = 2.9–30.0°
c = 52.940 (11) Å	µ = 32.58 mm⁻¹
V = 3150.8 (10) Å³	T = 293 K
Z = 18	Small pseudo-octahedral platelets, colourless
F(000) = 4068	0.08 × 0.07 × 0.03 mm

Data collection top

Nonius KappaCCD single-crystal four-circle diffractometer	685 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
φ and ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski et al., 2003)	h = −10→10
T_min = 0.180, T_max = 0.441	k = −8→8
2478 measured reflections	l = −64→64
698 independent reflections

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)] = 0.022	All H-atom parameters refined
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.023P)² + 84.2452P] where P = (F_o² + 2F_c²)/3
S = 1.21	(Δ/σ)_max = 0.003
698 reflections	Δρ_max = 0.82 e Å⁻³
69 parameters	Δρ_min = −1.98 e Å⁻³
2 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00049 (3)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Tl1	0.000000	−0.019 (2)	0.750000	0.037 (2)	0.3333
Tl2	0.000000	0.000000	0.66885 (2)	0.0322 (2)
Al1	0.333333	0.666667	0.75439 (5)	0.0051 (5)
Al2	0.333333	0.666667	0.666667	0.0061 (7)
As	−0.43603 (7)	−0.39811 (7)	0.71289 (2)	0.00523 (19)	0.9790 (14)
AsB	−0.596 (3)	−0.559 (3)	0.7127 (4)	0.00523 (19)	0.0210 (14)
O1	0.4431 (5)	−0.4433 (5)	0.68625 (6)	0.0120 (8)
O2	−0.4518 (5)	−0.2576 (5)	0.73421 (6)	0.0080 (7)
O3	−0.2001 (5)	−0.2792 (5)	0.70491 (8)	0.0144 (8)
O4	0.4791 (5)	−0.1259 (5)	0.77571 (6)	0.0083 (7)
H3	−0.126 (8)	−0.323 (8)	0.7074 (11)	0.010 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.0356 (8)	0.051 (5)	0.0190 (4)	0.0178 (4)	−0.003 (2)	−0.0015 (10)
Tl2	0.0411 (3)	0.0411 (3)	0.0145 (3)	0.02053 (13)	0.000	0.000
Al1	0.0069 (7)	0.0069 (7)	0.0014 (11)	0.0035 (4)	0.000	0.000
Al2	0.0085 (11)	0.0085 (11)	0.0014 (16)	0.0042 (5)	0.000	0.000
As	0.0081 (3)	0.0070 (3)	0.0019 (3)	0.0047 (2)	0.00051 (17)	0.00064 (17)
AsB	0.0081 (3)	0.0070 (3)	0.0019 (3)	0.0047 (2)	0.00051 (17)	0.00064 (17)
O1	0.0188 (19)	0.0166 (18)	0.0032 (15)	0.0109 (16)	−0.0020 (14)	−0.0009 (13)
O2	0.0077 (17)	0.0103 (16)	0.0045 (15)	0.0034 (14)	0.0021 (13)	−0.0004 (13)
O3	0.0091 (18)	0.0168 (19)	0.0199 (19)	0.0085 (15)	0.0098 (15)	0.0102 (15)
O4	0.0119 (17)	0.0085 (17)	0.0049 (15)	0.0054 (14)	−0.0011 (13)	−0.0044 (13)

Geometric parameters (Å, º) top

Tl1—Tl1ⁱ	0.28 (3)	Tl2—O3^xiv	3.545 (4)
Tl1—Tl1ⁱⁱ	0.28 (3)	Tl2—O3^xv	3.545 (4)
Tl1—O3	3.085 (8)	Tl2—AsB^xiii	3.74 (2)
Tl1—O3ⁱⁱⁱ	3.085 (8)	Tl2—AsB^xv	3.74 (2)
Tl1—O3^iv	3.136 (5)	Tl2—AsB^xiv	3.74 (2)
Tl1—O3ⁱ	3.136 (5)	Al1—O2^xvi	1.895 (4)
Tl1—O2^iv	3.233 (13)	Al1—O2ⁱⁱ	1.895 (4)
Tl1—O2ⁱ	3.233 (13)	Al1—O2^xvii	1.895 (4)
Tl1—O3^v	3.261 (12)	Al1—O4^xviii	1.901 (4)
Tl1—O3ⁱⁱ	3.261 (12)	Al1—O4ⁱ	1.901 (4)
Tl1—O2ⁱⁱⁱ	3.351 (4)	Al1—O4^xix	1.901 (4)
Tl1—O2	3.351 (4)	Al2—O1^ix	1.887 (4)
Tl1—O2ⁱⁱ	3.501 (15)	Al2—O1^xv	1.887 (4)
Tl1—O2^v	3.501 (15)	Al2—O1^xx	1.887 (4)
Tl1—AsB^vi	3.89 (3)	Al2—O1ⁱ	1.887 (4)
Tl2—O3ⁱ	2.813 (4)	Al2—O1^xix	1.887 (4)
Tl2—O3ⁱⁱ	2.813 (4)	Al2—O1^xviii	1.887 (4)
Tl2—O3	2.813 (4)	As—AsB	1.33 (2)
Tl2—O1^vii	3.410 (4)	As—O1^xxi	1.661 (3)
Tl2—O1^viii	3.410 (4)	As—O2	1.674 (3)
Tl2—O1^ix	3.410 (4)	As—O4ⁱⁱⁱ	1.679 (3)
Tl2—O4^x	3.516 (3)	As—O3	1.746 (4)
Tl2—O4^xi	3.516 (3)	AsB—O4ⁱⁱⁱ	1.35 (2)
Tl2—O4^xii	3.516 (3)	AsB—O1^xxi	1.64 (2)
Tl2—O3^xiii	3.545 (4)	AsB—O2^xxii	2.12 (2)

Tl1ⁱ—Tl1—Tl1ⁱⁱ	60.00 (3)	O1^xix—Al2—O1^xviii	92.71 (15)
Tl1ⁱ—Tl1—O3	127.2 (3)	O1^ix—Al2—Tl2^xx	64.49 (12)
Tl1ⁱⁱ—Tl1—O3	98.0 (3)	O1^xv—Al2—Tl2^xx	64.45 (11)
Tl1ⁱ—Tl1—O3ⁱⁱⁱ	98.0 (3)	O1^xx—Al2—Tl2^xx	145.30 (11)
Tl1ⁱⁱ—Tl1—O3ⁱⁱⁱ	127.2 (2)	O1ⁱ—Al2—Tl2^xx	115.51 (12)
O3—Tl1—O3ⁱⁱⁱ	129.1 (6)	O1^xix—Al2—Tl2^xx	115.55 (11)
Tl1ⁱ—Tl1—O3^iv	114.4 (3)	O1^xviii—Al2—Tl2^xx	34.70 (11)
Tl1ⁱⁱ—Tl1—O3^iv	77.0 (4)	O1^ix—Al2—Tl2^xviii	115.51 (12)
O3—Tl1—O3^iv	104.2 (3)	O1^xv—Al2—Tl2^xviii	115.55 (11)
O3ⁱⁱⁱ—Tl1—O3^iv	70.24 (16)	O1^xx—Al2—Tl2^xviii	34.70 (11)
Tl1ⁱ—Tl1—O3ⁱ	77.0 (3)	O1ⁱ—Al2—Tl2^xviii	64.49 (12)
Tl1ⁱⁱ—Tl1—O3ⁱ	114.4 (2)	O1^xix—Al2—Tl2^xviii	64.45 (11)
O3—Tl1—O3ⁱ	70.24 (16)	O1^xviii—Al2—Tl2^xviii	145.29 (11)
O3ⁱⁱⁱ—Tl1—O3ⁱ	104.2 (3)	Tl2^xx—Al2—Tl2^xviii	180.0
O3^iv—Tl1—O3ⁱ	167.5 (6)	O1^ix—Al2—Tl2^xvii	115.55 (11)
Tl1ⁱ—Tl1—O2^iv	163.77 (15)	O1^xv—Al2—Tl2^xvii	34.70 (11)
Tl1ⁱⁱ—Tl1—O2^iv	112.8 (3)	O1^xx—Al2—Tl2^xvii	115.51 (12)
O3—Tl1—O2^iv	66.4 (3)	O1ⁱ—Al2—Tl2^xvii	64.45 (11)
O3ⁱⁱⁱ—Tl1—O2^iv	74.5 (3)	O1^xix—Al2—Tl2^xvii	145.29 (11)
O3^iv—Tl1—O2^iv	49.68 (16)	O1^xviii—Al2—Tl2^xvii	64.49 (12)
O3ⁱ—Tl1—O2^iv	118.5 (5)	Tl2^xx—Al2—Tl2^xvii	60.1
Tl1ⁱ—Tl1—O2ⁱ	112.84 (18)	Tl2^xviii—Al2—Tl2^xvii	119.9
Tl1ⁱⁱ—Tl1—O2ⁱ	163.77 (10)	O1^ix—Al2—Tl2	34.70 (11)
O3—Tl1—O2ⁱ	74.5 (3)	O1^xv—Al2—Tl2	115.51 (12)
O3ⁱⁱⁱ—Tl1—O2ⁱ	66.4 (3)	O1^xx—Al2—Tl2	115.55 (12)
O3^iv—Tl1—O2ⁱ	118.5 (5)	O1ⁱ—Al2—Tl2	145.29 (11)
O3ⁱ—Tl1—O2ⁱ	49.68 (16)	O1^xix—Al2—Tl2	64.49 (12)
O2^iv—Tl1—O2ⁱ	77.8 (4)	O1^xviii—Al2—Tl2	64.45 (12)
Tl1ⁱ—Tl1—O3^v	48.90 (18)	Tl2^xx—Al2—Tl2	60.1
Tl1ⁱⁱ—Tl1—O3^v	61.10 (14)	Tl2^xviii—Al2—Tl2	119.942 (1)
O3—Tl1—O3^v	158.5 (4)	Tl2^xvii—Al2—Tl2	119.9
O3ⁱⁱⁱ—Tl1—O3^v	68.60 (12)	O1^ix—Al2—Tl2^xxiv	64.45 (11)
O3^iv—Tl1—O3^v	68.01 (16)	O1^xv—Al2—Tl2^xxiv	145.30 (11)
O3ⁱ—Tl1—O3^v	121.2 (3)	O1^xx—Al2—Tl2^xxiv	64.49 (12)
O2^iv—Tl1—O3^v	115.03 (10)	O1ⁱ—Al2—Tl2^xxiv	115.55 (11)
O2ⁱ—Tl1—O3^v	127.04 (11)	O1^xix—Al2—Tl2^xxiv	34.70 (11)
Tl1ⁱ—Tl1—O3ⁱⁱ	61.1 (2)	O1^xviii—Al2—Tl2^xxiv	115.51 (12)
Tl1ⁱⁱ—Tl1—O3ⁱⁱ	48.90 (16)	Tl2^xx—Al2—Tl2^xxiv	119.9
O3—Tl1—O3ⁱⁱ	68.60 (12)	Tl2^xviii—Al2—Tl2^xxiv	60.1
O3ⁱⁱⁱ—Tl1—O3ⁱⁱ	158.5 (4)	Tl2^xvii—Al2—Tl2^xxiv	180.0
O3^iv—Tl1—O3ⁱⁱ	121.2 (3)	Tl2—Al2—Tl2^xxiv	60.1
O3ⁱ—Tl1—O3ⁱⁱ	68.01 (16)	O1^ix—Al2—Tl2^xxv	145.30 (11)
O2^iv—Tl1—O3ⁱⁱ	127.04 (11)	O1^xv—Al2—Tl2^xxv	64.49 (12)
O2ⁱ—Tl1—O3ⁱⁱ	115.03 (10)	O1^xx—Al2—Tl2^xxv	64.45 (12)
O3^v—Tl1—O3ⁱⁱ	97.6 (5)	O1ⁱ—Al2—Tl2^xxv	34.70 (11)
Tl1ⁱ—Tl1—O2ⁱⁱⁱ	62.8 (3)	O1^xix—Al2—Tl2^xxv	115.51 (12)
Tl1ⁱⁱ—Tl1—O2ⁱⁱⁱ	120.68 (19)	O1^xviii—Al2—Tl2^xxv	115.55 (12)
O3—Tl1—O2ⁱⁱⁱ	129.1 (3)	Tl2^xx—Al2—Tl2^xxv	119.9
O3ⁱⁱⁱ—Tl1—O2ⁱⁱⁱ	48.95 (11)	Tl2^xviii—Al2—Tl2^xxv	60.1
O3^iv—Tl1—O2ⁱⁱⁱ	115.18 (11)	Tl2^xvii—Al2—Tl2^xxv	60.1
O3ⁱ—Tl1—O2ⁱⁱⁱ	64.40 (9)	Tl2—Al2—Tl2^xxv	180.0
O2^iv—Tl1—O2ⁱⁱⁱ	117.7 (4)	Tl2^xxiv—Al2—Tl2^xxv	119.9
O2ⁱ—Tl1—O2ⁱⁱⁱ	59.15 (18)	AsB—As—O1^xxi	65.3 (9)
O3^v—Tl1—O2ⁱⁱⁱ	70.66 (15)	AsB—As—O2	108.5 (9)
O3ⁱⁱ—Tl1—O2ⁱⁱⁱ	111.8 (3)	O1^xxi—As—O2	118.77 (18)
Tl1ⁱ—Tl1—O2	120.7 (3)	AsB—As—O4ⁱⁱⁱ	51.8 (9)
Tl1ⁱⁱ—Tl1—O2	62.8 (4)	O1^xxi—As—O4ⁱⁱⁱ	106.18 (18)
O3—Tl1—O2	48.94 (10)	O2—As—O4ⁱⁱⁱ	114.71 (17)
O3ⁱⁱⁱ—Tl1—O2	129.1 (3)	AsB—As—O3	147.0 (10)
O3^iv—Tl1—O2	64.40 (9)	O1^xxi—As—O3	107.52 (19)
O3ⁱ—Tl1—O2	115.18 (11)	O2—As—O3	103.03 (19)
O2^iv—Tl1—O2	59.15 (17)	O4ⁱⁱⁱ—As—O3	105.63 (17)
O2ⁱ—Tl1—O2	117.7 (4)	AsB—As—Tl2^xiii	79.0 (9)
O3^v—Tl1—O2	111.8 (3)	O1^xxi—As—Tl2^xiii	65.02 (13)
O3ⁱⁱ—Tl1—O2	70.66 (15)	O2—As—Tl2^xiii	172.42 (13)
O2ⁱⁱⁱ—Tl1—O2	176.5 (6)	O4ⁱⁱⁱ—As—Tl2^xiii	68.63 (12)
Tl1ⁱ—Tl1—O2ⁱⁱ	14.95 (6)	O3—As—Tl2^xiii	69.39 (14)
Tl1ⁱⁱ—Tl1—O2ⁱⁱ	55.40 (8)	AsB—As—Tl1ⁱⁱ	150.1 (9)
O3—Tl1—O2ⁱⁱ	112.4 (2)	O1^xxi—As—Tl1ⁱⁱ	142.74 (15)
O3ⁱⁱⁱ—Tl1—O2ⁱⁱ	112.3 (2)	O2—As—Tl1ⁱⁱ	54.3 (2)
O3^iv—Tl1—O2ⁱⁱ	122.2 (4)	O4ⁱⁱⁱ—As—Tl1ⁱⁱ	109.18 (17)
O3ⁱ—Tl1—O2ⁱⁱ	70.1 (2)	O3—As—Tl1ⁱⁱ	51.5 (2)
O2^iv—Tl1—O2ⁱⁱ	168.2 (3)	Tl2^xiii—As—Tl1ⁱⁱ	118.4 (2)
O2ⁱ—Tl1—O2ⁱⁱ	113.58 (8)	AsB—As—Tl1	149.5 (9)
O3^v—Tl1—O2ⁱⁱ	61.5 (3)	O1^xxi—As—Tl1	144.6 (2)
O3ⁱⁱ—Tl1—O2ⁱⁱ	46.5 (2)	O2—As—Tl1	57.8 (2)
O2ⁱⁱⁱ—Tl1—O2ⁱⁱ	72.6 (2)	O4ⁱⁱⁱ—As—Tl1	106.1 (2)
O2—Tl1—O2ⁱⁱ	110.7 (4)	O3—As—Tl1	49.19 (16)
Tl1ⁱ—Tl1—O2^v	55.40 (16)	Tl2^xiii—As—Tl1	115.07 (16)
Tl1ⁱⁱ—Tl1—O2^v	14.95 (6)	Tl1ⁱⁱ—As—Tl1	4.1 (4)
O3—Tl1—O2^v	112.3 (2)	AsB—As—Tl1ⁱ	151.5 (9)
O3ⁱⁱⁱ—Tl1—O2^v	112.4 (2)	O1^xxi—As—Tl1ⁱ	142.12 (17)
O3^iv—Tl1—O2^v	70.1 (2)	O2—As—Tl1ⁱ	56.77 (13)
O3ⁱ—Tl1—O2^v	122.2 (4)	O4ⁱⁱⁱ—As—Tl1ⁱ	108.88 (15)
O2^iv—Tl1—O2^v	113.58 (7)	O3—As—Tl1ⁱ	49.06 (16)
O2ⁱ—Tl1—O2^v	168.2 (3)	Tl2^xiii—As—Tl1ⁱ	115.97 (5)
O3^v—Tl1—O2^v	46.5 (2)	Tl1ⁱⁱ—As—Tl1ⁱ	2.5 (3)
O3ⁱⁱ—Tl1—O2^v	61.5 (3)	Tl1—As—Tl1ⁱ	2.8 (3)
O2ⁱⁱⁱ—Tl1—O2^v	110.7 (4)	AsB—As—Tl2	145.5 (9)
O2—Tl1—O2^v	72.6 (2)	O1^xxi—As—Tl2	83.71 (13)
O2ⁱⁱ—Tl1—O2^v	55.3 (3)	O2—As—Tl2	99.45 (13)
Tl1ⁱ—Tl1—AsB^vi	135.2 (4)	O4ⁱⁱⁱ—As—Tl2	131.69 (12)
Tl1ⁱⁱ—Tl1—AsB^vi	141.1 (4)	O3—As—Tl2	30.29 (12)
O3—Tl1—AsB^vi	43.1 (4)	Tl2^xiii—As—Tl2	74.034 (11)
O3ⁱⁱⁱ—Tl1—AsB^vi	89.5 (5)	Tl1ⁱⁱ—As—Tl2	64.11 (8)
O3^iv—Tl1—AsB^vi	109.6 (5)	Tl1—As—Tl2	63.95 (6)
O3ⁱ—Tl1—AsB^vi	58.5 (4)	Tl1ⁱ—As—Tl2	62.34 (12)
O2^iv—Tl1—AsB^vi	60.1 (4)	AsB—As—Tl1^xxvi	23.3 (9)
O2ⁱ—Tl1—AsB^vi	33.0 (4)	O1^xxi—As—Tl1^xxvi	87.98 (15)
O3^v—Tl1—AsB^vi	157.7 (4)	O2—As—Tl1^xxvi	93.41 (14)
O3ⁱⁱ—Tl1—AsB^vi	101.9 (3)	O4ⁱⁱⁱ—As—Tl1^xxvi	41.90 (12)
O2ⁱⁱⁱ—Tl1—AsB^vi	92.0 (4)	O3—As—Tl1^xxvi	147.50 (13)
O2—Tl1—AsB^vi	85.0 (4)	Tl2^xiii—As—Tl1^xxvi	93.30 (5)
O2ⁱⁱ—Tl1—AsB^vi	127.8 (3)	Tl1ⁱⁱ—As—Tl1^xxvi	126.79 (12)
O2^v—Tl1—AsB^vi	155.4 (3)	Tl1—As—Tl1^xxvi	126.30 (17)
O3ⁱ—Tl2—O3ⁱⁱ	79.02 (13)	Tl1ⁱ—As—Tl1^xxvi	128.27 (4)
O3ⁱ—Tl2—O3	79.02 (13)	Tl2—As—Tl1^xxvi	166.91 (6)
O3ⁱⁱ—Tl2—O3	79.02 (13)	AsB—As—Tl1^xxii	22.1 (9)
O3ⁱ—Tl2—O1^vii	75.43 (10)	O1^xxi—As—Tl1^xxii	86.49 (17)
O3ⁱⁱ—Tl2—O1^vii	154.16 (10)	O2—As—Tl1^xxii	93.06 (16)
O3—Tl2—O1^vii	92.26 (10)	O4ⁱⁱⁱ—As—Tl1^xxii	43.7 (2)
O3ⁱ—Tl2—O1^viii	154.16 (10)	O3—As—Tl1^xxii	149.3 (2)
O3ⁱⁱ—Tl2—O1^viii	92.26 (10)	Tl2^xiii—As—Tl1^xxii	93.75 (10)
O3—Tl2—O1^viii	75.43 (10)	Tl1ⁱⁱ—As—Tl1^xxii	127.913 (17)
O1^vii—Tl2—O1^viii	109.19 (6)	Tl1—As—Tl1^xxii	127.56 (3)
O3ⁱ—Tl2—O1^ix	92.26 (10)	Tl1ⁱ—As—Tl1^xxii	129.46 (17)
O3ⁱⁱ—Tl2—O1^ix	75.43 (10)	Tl2—As—Tl1^xxii	166.76 (4)
O3—Tl2—O1^ix	154.15 (10)	Tl1^xxvi—As—Tl1^xxii	1.9 (2)
O1^vii—Tl2—O1^ix	109.19 (6)	As—AsB—O4ⁱⁱⁱ	77.6 (12)
O1^viii—Tl2—O1^ix	109.19 (6)	As—AsB—O1^xxi	67.1 (10)
O3ⁱ—Tl2—O4^x	110.02 (10)	O4ⁱⁱⁱ—AsB—O1^xxi	126.4 (16)
O3ⁱⁱ—Tl2—O4^x	153.52 (10)	As—AsB—O2^xxii	112.5 (13)
O3—Tl2—O4^x	126.54 (10)	O4ⁱⁱⁱ—AsB—O2^xxii	119.3 (13)
O1^vii—Tl2—O4^x	45.33 (8)	O1^xxi—AsB—O2^xxii	111.1 (11)
O1^viii—Tl2—O4^x	88.61 (8)	As—AsB—Tl2^xiii	80.6 (10)
O1^ix—Tl2—O4^x	79.30 (8)	O4ⁱⁱⁱ—AsB—Tl2^xiii	69.9 (9)
O3ⁱ—Tl2—O4^xi	153.52 (10)	O1^xxi—AsB—Tl2^xiii	65.6 (7)
O3ⁱⁱ—Tl2—O4^xi	126.54 (10)	O2^xxii—AsB—Tl2^xiii	164.8 (9)
O3—Tl2—O4^xi	110.02 (11)	As—AsB—Tl1^xxvi	149.0 (12)
O1^vii—Tl2—O4^xi	79.30 (8)	O4ⁱⁱⁱ—AsB—Tl1^xxvi	84.2 (10)
O1^viii—Tl2—O4^xi	45.33 (8)	O1^xxi—AsB—Tl1^xxvi	142.5 (11)
O1^ix—Tl2—O4^xi	88.61 (8)	O2^xxii—AsB—Tl1^xxvi	56.2 (5)
O4^x—Tl2—O4^xi	44.26 (9)	Tl2^xiii—AsB—Tl1^xxvi	116.5 (6)
O3ⁱ—Tl2—O4^xii	126.54 (11)	As—AsB—Tl1^xxii	150.8 (12)
O3ⁱⁱ—Tl2—O4^xii	110.01 (10)	O4ⁱⁱⁱ—AsB—Tl1^xxii	86.9 (10)
O3—Tl2—O4^xii	153.52 (11)	O1^xxi—AsB—Tl1^xxii	140.0 (11)
O1^vii—Tl2—O4^xii	88.61 (8)	O2^xxii—AsB—Tl1^xxii	54.8 (5)
O1^viii—Tl2—O4^xii	79.30 (8)	Tl2^xiii—AsB—Tl1^xxii	117.2 (6)
O1^ix—Tl2—O4^xii	45.33 (8)	Tl1^xxvi—AsB—Tl1^xxii	2.7 (3)
O4^x—Tl2—O4^xii	44.26 (9)	As—AsB—Tl1^xxvii	150.4 (12)
O4^xi—Tl2—O4^xii	44.26 (9)	O4ⁱⁱⁱ—AsB—Tl1^xxvii	83.6 (10)
O3ⁱ—Tl2—O3^xiii	117.91 (14)	O1^xxi—AsB—Tl1^xxvii	141.8 (11)
O3ⁱⁱ—Tl2—O3^xiii	152.25 (13)	O2^xxii—AsB—Tl1^xxvii	58.4 (6)
O3—Tl2—O3^xiii	82.85 (11)	Tl2^xiii—AsB—Tl1^xxvii	114.1 (6)
O1^vii—Tl2—O3^xiii	46.50 (9)	Tl1^xxvi—AsB—Tl1^xxvii	2.4 (3)
O1^viii—Tl2—O3^xiii	62.74 (9)	Tl1^xxii—AsB—Tl1^xxvii	3.9 (4)
O1^ix—Tl2—O3^xiii	122.31 (9)	As—AsB—Tl2^xxvii	146.6 (12)
O4^x—Tl2—O3^xiii	45.47 (8)	O4ⁱⁱⁱ—AsB—Tl2^xxvii	112.1 (11)
O4^xi—Tl2—O3^xiii	42.94 (8)	O1^xxi—AsB—Tl2^xxvii	82.8 (8)
O4^xii—Tl2—O3^xiii	78.63 (8)	O2^xxii—AsB—Tl2^xxvii	91.1 (7)
O3ⁱ—Tl2—O3^xiv	82.85 (11)	Tl2^xiii—AsB—Tl2^xxvii	73.8 (4)
O3ⁱⁱ—Tl2—O3^xiv	117.91 (14)	Tl1^xxvi—AsB—Tl2^xxvii	64.0 (4)
O3—Tl2—O3^xiv	152.25 (12)	Tl1^xxii—AsB—Tl2^xxvii	62.3 (3)
O1^vii—Tl2—O3^xiv	62.74 (9)	Tl1^xxvii—AsB—Tl2^xxvii	62.2 (3)
O1^viii—Tl2—O3^xiv	122.31 (9)	As—AsB—Tl1ⁱⁱ	22.5 (7)
O1^ix—Tl2—O3^xiv	46.50 (9)	O4ⁱⁱⁱ—AsB—Tl1ⁱⁱ	66.6 (9)
O4^x—Tl2—O3^xiv	42.94 (9)	O1^xxi—AsB—Tl1ⁱⁱ	88.7 (8)
O4^xi—Tl2—O3^xiv	78.63 (8)	O2^xxii—AsB—Tl1ⁱⁱ	99.8 (7)
O4^xii—Tl2—O3^xiv	45.47 (8)	Tl2^xiii—AsB—Tl1ⁱⁱ	95.0 (5)
O3^xiii—Tl2—O3^xiv	87.33 (9)	Tl1^xxvi—AsB—Tl1ⁱⁱ	126.5 (5)
O3ⁱ—Tl2—O3^xv	152.25 (13)	Tl1^xxii—AsB—Tl1ⁱⁱ	128.3 (5)
O3ⁱⁱ—Tl2—O3^xv	82.85 (11)	Tl1^xxvii—AsB—Tl1ⁱⁱ	128.0 (5)
O3—Tl2—O3^xv	117.91 (14)	Tl2^xxvii—AsB—Tl1ⁱⁱ	168.1 (5)
O1^vii—Tl2—O3^xv	122.31 (9)	As—AsB—Tl1	22.9 (7)
O1^viii—Tl2—O3^xv	46.50 (9)	O4ⁱⁱⁱ—AsB—Tl1	63.7 (9)
O1^ix—Tl2—O3^xv	62.74 (9)	O1^xxi—AsB—Tl1	89.8 (9)
O4^x—Tl2—O3^xv	78.63 (8)	O2^xxii—AsB—Tl1	102.1 (7)
O4^xi—Tl2—O3^xv	45.47 (8)	Tl2^xiii—AsB—Tl1	92.8 (5)
O4^xii—Tl2—O3^xv	42.94 (8)	Tl1^xxvi—AsB—Tl1	126.1 (5)
O3^xiii—Tl2—O3^xv	87.33 (9)	Tl1^xxii—AsB—Tl1	128.1 (5)
O3^xiv—Tl2—O3^xv	87.33 (9)	Tl1^xxvii—AsB—Tl1	127.5 (5)
O3ⁱ—Tl2—AsB^xiii	90.6 (3)	Tl2^xxvii—AsB—Tl1	166.5 (6)
O3ⁱⁱ—Tl2—AsB^xiii	159.8 (4)	Tl1ⁱⁱ—AsB—Tl1	3.1 (3)
O3—Tl2—AsB^xiii	116.2 (4)	As—AsB—Tl2	26.4 (7)
O1^vii—Tl2—AsB^xiii	25.9 (3)	O4ⁱⁱⁱ—AsB—Tl2	87.6 (10)
O1^viii—Tl2—AsB^xiii	104.1 (4)	O1^xxi—AsB—Tl2	44.9 (7)
O1^ix—Tl2—AsB^xiii	87.9 (4)	O2^xxii—AsB—Tl2	128.4 (8)
O4^x—Tl2—AsB^xiii	21.2 (3)	Tl2^xiii—AsB—Tl2	60.8 (3)
O4^xi—Tl2—AsB^xiii	63.0 (3)	Tl1^xxvi—AsB—Tl2	171.8 (6)
O4^xii—Tl2—AsB^xiii	62.7 (3)	Tl1^xxii—AsB—Tl2	174.5 (6)
O3^xiii—Tl2—AsB^xiii	47.7 (4)	Tl1^xxvii—AsB—Tl2	171.0 (6)
O3^xiv—Tl2—AsB^xiii	42.9 (4)	Tl2^xxvii—AsB—Tl2	120.2 (4)
O3^xv—Tl2—AsB^xiii	99.8 (3)	Tl1ⁱⁱ—AsB—Tl2	48.6 (2)
O3ⁱ—Tl2—AsB^xv	159.8 (4)	Tl1—AsB—Tl2	48.5 (2)
O3ⁱⁱ—Tl2—AsB^xv	116.2 (4)	AsB^xxviii—O1—As^xxviii	47.6 (8)
O3—Tl2—AsB^xv	90.6 (4)	AsB^xxviii—O1—Al2^xxix	138.8 (8)
O1^vii—Tl2—AsB^xv	87.9 (4)	As^xxviii—O1—Al2^xxix	137.7 (2)
O1^viii—Tl2—AsB^xv	25.9 (3)	AsB^xxviii—O1—Tl2^vii	88.4 (8)
O1^ix—Tl2—AsB^xv	104.1 (3)	As^xxviii—O1—Tl2^vii	88.78 (15)
O4^x—Tl2—AsB^xv	62.7 (3)	Al2^xxix—O1—Tl2^vii	126.91 (15)
O4^xi—Tl2—AsB^xv	21.2 (3)	AsB^xxviii—O1—Tl2^xxix	75.1 (8)
O4^xii—Tl2—AsB^xv	63.0 (3)	As^xxviii—O1—Tl2^xxix	121.09 (16)
O3^xiii—Tl2—AsB^xv	42.9 (4)	Al2^xxix—O1—Tl2^xxix	92.35 (12)
O3^xiv—Tl2—AsB^xv	99.8 (3)	Tl2^vii—O1—Tl2^xxix	75.55 (7)
O3^xv—Tl2—AsB^xv	47.7 (4)	AsB^xxviii—O1—Tl2^xxviii	119.6 (8)
AsB^xiii—Tl2—AsB^xv	78.5 (5)	As^xxviii—O1—Tl2^xxviii	73.85 (13)
O3ⁱ—Tl2—AsB^xiv	116.2 (4)	Al2^xxix—O1—Tl2^xxviii	92.31 (12)
O3ⁱⁱ—Tl2—AsB^xiv	90.6 (4)	Tl2^vii—O1—Tl2^xxviii	75.53 (7)
O3—Tl2—AsB^xiv	159.8 (4)	Tl2^xxix—O1—Tl2^xxviii	146.93 (9)
O1^vii—Tl2—AsB^xiv	104.1 (4)	As—O2—Al1^xxvii	122.5 (2)
O1^viii—Tl2—AsB^xiv	87.9 (4)	As—O2—AsB^xxx	104.8 (6)
O1^ix—Tl2—AsB^xiv	25.9 (3)	Al1^xxvii—O2—AsB^xxx	102.5 (6)
O4^x—Tl2—AsB^xiv	63.0 (3)	As—O2—Tl1ⁱⁱ	100.8 (2)
O4^xi—Tl2—AsB^xiv	62.7 (3)	Al1^xxvii—O2—Tl1ⁱⁱ	128.4 (2)
O4^xii—Tl2—AsB^xiv	21.2 (3)	AsB^xxx—O2—Tl1ⁱⁱ	90.8 (7)
O3^xiii—Tl2—AsB^xiv	99.8 (3)	As—O2—Tl1	97.2 (3)
O3^xiv—Tl2—AsB^xiv	47.7 (4)	Al1^xxvii—O2—Tl1	130.04 (17)
O3^xv—Tl2—AsB^xiv	42.9 (4)	AsB^xxx—O2—Tl1	94.2 (7)
AsB^xiii—Tl2—AsB^xiv	78.5 (5)	Tl1ⁱⁱ—O2—Tl1	4.4 (5)
AsB^xv—Tl2—AsB^xiv	78.5 (5)	As—O2—Tl1ⁱ	99.66 (14)
O2^xvi—Al1—O2ⁱⁱ	91.34 (17)	Al1^xxvii—O2—Tl1ⁱ	129.68 (16)
O2^xvi—Al1—O2^xvii	91.34 (17)	AsB^xxx—O2—Tl1ⁱ	90.6 (7)
O2ⁱⁱ—Al1—O2^xvii	91.34 (17)	Tl1ⁱⁱ—O2—Tl1ⁱ	1.27 (13)
O2^xvi—Al1—O4^xviii	92.20 (15)	Tl1—O2—Tl1ⁱ	3.9 (4)
O2ⁱⁱ—Al1—O4^xviii	176.43 (17)	As—O2—Tl2	60.21 (10)
O2^xvii—Al1—O4^xviii	88.17 (15)	Al1^xxvii—O2—Tl2	163.54 (15)
O2^xvi—Al1—O4ⁱ	88.17 (15)	AsB^xxx—O2—Tl2	62.4 (6)
O2ⁱⁱ—Al1—O4ⁱ	92.20 (16)	Tl1ⁱⁱ—O2—Tl2	61.76 (9)
O2^xvii—Al1—O4ⁱ	176.43 (18)	Tl1—O2—Tl2	61.25 (6)
O4^xviii—Al1—O4ⁱ	88.32 (17)	Tl1ⁱ—O2—Tl2	60.58 (8)
O2^xvi—Al1—O4^xix	176.43 (17)	As—O3—Tl2	131.46 (18)
O2ⁱⁱ—Al1—O4^xix	88.16 (15)	As—O3—Tl1	105.45 (17)
O2^xvii—Al1—O4^xix	92.20 (15)	Tl2—O3—Tl1	93.5 (2)
O4^xviii—Al1—O4^xix	88.32 (17)	As—O3—Tl1ⁱⁱ	102.7 (3)
O4ⁱ—Al1—O4^xix	88.32 (17)	Tl2—O3—Tl1ⁱⁱ	92.38 (13)
O2^xvi—Al1—Tl2^xxiii	124.31 (12)	Tl1—O3—Tl1ⁱⁱ	5.0 (5)
O2ⁱⁱ—Al1—Tl2^xxiii	124.31 (12)	As—O3—Tl1ⁱ	107.1 (3)
O2^xvii—Al1—Tl2^xxiii	124.31 (12)	Tl2—O3—Tl1ⁱ	89.8 (3)
O4^xviii—Al1—Tl2^xxiii	53.56 (12)	Tl1—O3—Tl1ⁱ	3.9 (4)
O4ⁱ—Al1—Tl2^xxiii	53.56 (12)	Tl1ⁱⁱ—O3—Tl1ⁱ	4.5 (5)
O4^xix—Al1—Tl2^xxiii	53.56 (12)	As—O3—Tl2^xiii	83.17 (14)
O2^xvi—Al1—Tl1^xviii	32.98 (11)	Tl2—O3—Tl2^xiii	97.14 (11)
O2ⁱⁱ—Al1—Tl1^xviii	104.20 (15)	Tl1—O3—Tl2^xiii	156.2 (3)
O2^xvii—Al1—Tl1^xviii	120.62 (14)	Tl1ⁱⁱ—O3—Tl2^xiii	161.0 (3)
O4^xviii—Al1—Tl1^xviii	79.07 (14)	Tl1ⁱ—O3—Tl2^xiii	158.83 (12)
O4ⁱ—Al1—Tl1^xviii	57.99 (12)	AsBⁱⁱⁱ—O4—Asⁱⁱⁱ	50.7 (10)
O4^xix—Al1—Tl1^xviii	143.97 (14)	AsBⁱⁱⁱ—O4—Al1^xxix	170.4 (10)
Tl2^xxiii—Al1—Tl1^xviii	92.86 (3)	Asⁱⁱⁱ—O4—Al1^xxix	130.5 (2)
O2^xvi—Al1—Tl1ⁱ	120.61 (14)	AsBⁱⁱⁱ—O4—Tl2^xxxi	88.9 (9)
O2ⁱⁱ—Al1—Tl1ⁱ	32.98 (11)	Asⁱⁱⁱ—O4—Tl2^xxxi	84.96 (12)
O2^xvii—Al1—Tl1ⁱ	104.20 (15)	Al1^xxix—O4—Tl2^xxxi	100.65 (14)
O4^xviii—Al1—Tl1ⁱ	143.97 (14)	AsBⁱⁱⁱ—O4—Tl1^xxxii	76.1 (10)
O4ⁱ—Al1—Tl1ⁱ	79.07 (14)	Asⁱⁱⁱ—O4—Tl1^xxxii	121.76 (16)
O4^xix—Al1—Tl1ⁱ	57.99 (13)	Al1^xxix—O4—Tl1^xxxii	98.16 (12)
Tl2^xxiii—Al1—Tl1ⁱ	92.86 (3)	Tl2^xxxi—O4—Tl1^xxxii	119.60 (14)
Tl1^xviii—Al1—Tl1ⁱ	119.753 (11)	AsBⁱⁱⁱ—O4—Tl1^xxviii	77.7 (10)
O2^xvi—Al1—Tl1^xix	104.20 (16)	Asⁱⁱⁱ—O4—Tl1^xxviii	124.1 (3)
O2ⁱⁱ—Al1—Tl1^xix	120.61 (14)	Al1^xxix—O4—Tl1^xxviii	96.88 (19)
O2^xvii—Al1—Tl1^xix	32.98 (12)	Tl2^xxxi—O4—Tl1^xxviii	117.56 (15)
O4^xviii—Al1—Tl1^xix	57.99 (13)	Tl1^xxxii—O4—Tl1^xxviii	2.8 (3)
O4ⁱ—Al1—Tl1^xix	143.97 (14)	AsBⁱⁱⁱ—O4—Tl1^xxxiii	74.5 (10)
O4^xix—Al1—Tl1^xix	79.07 (15)	Asⁱⁱⁱ—O4—Tl1^xxxiii	120.5 (2)
Tl2^xxiii—Al1—Tl1^xix	92.86 (4)	Al1^xxix—O4—Tl1^xxxiii	99.8 (2)
Tl1^xviii—Al1—Tl1^xix	119.753 (7)	Tl2^xxxi—O4—Tl1^xxxiii	118.95 (9)
Tl1ⁱ—Al1—Tl1^xix	119.753 (6)	Tl1^xxxii—O4—Tl1^xxxiii	1.61 (17)
O2^xvi—Al1—Tl1^xvi	32.35 (12)	Tl1^xxviii—O4—Tl1^xxxiii	3.7 (4)
O2ⁱⁱ—Al1—Tl1^xvi	106.6 (2)	AsBⁱⁱⁱ—O4—Tl1	101.3 (10)
O2^xvii—Al1—Tl1^xvi	118.5 (2)	Asⁱⁱⁱ—O4—Tl1	53.74 (18)
O4^xviii—Al1—Tl1^xvi	76.73 (19)	Al1^xxix—O4—Tl1	77.44 (19)
O4ⁱ—Al1—Tl1^xvi	59.94 (18)	Tl2^xxxi—O4—Tl1	103.75 (9)
O4^xix—Al1—Tl1^xvi	144.77 (15)	Tl1^xxxii—O4—Tl1	136.34 (9)
Tl2^xxiii—Al1—Tl1^xvi	92.78 (3)	Tl1^xxviii—O4—Tl1	138.6 (2)
Tl1^xviii—Al1—Tl1^xvi	2.9 (3)	Tl1^xxxiii—O4—Tl1	136.76 (8)
Tl1ⁱ—Al1—Tl1^xvi	122.7 (3)	AsBⁱⁱⁱ—O4—Tl1ⁱ	98.2 (10)
Tl1^xix—Al1—Tl1^xvi	116.9 (3)	Asⁱⁱⁱ—O4—Tl1ⁱ	51.25 (16)
O2^xvi—Al1—Tl1ⁱⁱ	118.5 (2)	Al1^xxix—O4—Tl1ⁱ	80.3 (2)
O2ⁱⁱ—Al1—Tl1ⁱⁱ	32.35 (12)	Tl2^xxxi—O4—Tl1ⁱ	105.06 (14)
O2^xvii—Al1—Tl1ⁱⁱ	106.6 (2)	Tl1^xxxii—O4—Tl1ⁱ	134.6 (3)
O4^xviii—Al1—Tl1ⁱⁱ	144.77 (15)	Tl1^xxviii—O4—Tl1ⁱ	136.94 (8)
O4ⁱ—Al1—Tl1ⁱⁱ	76.7 (2)	Tl1^xxxiii—O4—Tl1ⁱ	134.9 (2)
O4^xix—Al1—Tl1ⁱⁱ	59.94 (19)	Tl1—O4—Tl1ⁱ	3.3 (4)
Tl2^xxiii—Al1—Tl1ⁱⁱ	92.78 (3)	AsBⁱⁱⁱ—O4—Tl2^xxxiv	53.0 (10)
Tl1^xviii—Al1—Tl1ⁱⁱ	116.9 (3)	Asⁱⁱⁱ—O4—Tl2^xxxiv	97.70 (13)
Tl1ⁱ—Al1—Tl1ⁱⁱ	2.9 (3)	Al1^xxix—O4—Tl2^xxxiv	130.13 (14)
Tl1^xix—Al1—Tl1ⁱⁱ	122.7 (3)	Tl2^xxxi—O4—Tl2^xxxiv	67.31 (5)
Tl1^xvi—Al1—Tl1ⁱⁱ	119.767 (7)	Tl1^xxxii—O4—Tl2^xxxiv	56.91 (9)
O1^ix—Al2—O1^xv	92.72 (15)	Tl1^xxviii—O4—Tl2^xxxiv	55.99 (5)
O1^ix—Al2—O1^xx	92.72 (15)	Tl1^xxxiii—O4—Tl2^xxxiv	55.69 (6)
O1^xv—Al2—O1^xx	92.72 (15)	Tl1—O4—Tl2^xxxiv	151.34 (16)
O1^ix—Al2—O1ⁱ	180.0	Tl1ⁱ—O4—Tl2^xxxiv	148.95 (14)
O1^xv—Al2—O1ⁱ	87.28 (15)	AsBⁱⁱⁱ—O4—Tl1ⁱⁱ	99.9 (10)
O1^xx—Al2—O1ⁱ	87.28 (15)	Asⁱⁱⁱ—O4—Tl1ⁱⁱ	52.32 (10)
O1^ix—Al2—O1^xix	87.28 (15)	Al1^xxix—O4—Tl1ⁱⁱ	78.86 (11)
O1^xv—Al2—O1^xix	180.0	Tl2^xxxi—O4—Tl1ⁱⁱ	103.45 (10)
O1^xx—Al2—O1^xix	87.28 (15)	Tl1^xxxii—O4—Tl1ⁱⁱ	136.45 (9)
O1ⁱ—Al2—O1^xix	92.71 (15)	Tl1^xxviii—O4—Tl1ⁱⁱ	138.7 (2)
O1^ix—Al2—O1^xviii	87.28 (15)	Tl1^xxxiii—O4—Tl1ⁱⁱ	136.81 (8)
O1^xv—Al2—O1^xviii	87.28 (15)	Tl1—O4—Tl1ⁱⁱ	1.42 (15)
O1^xx—Al2—O1^xviii	180.00 (17)	Tl1ⁱ—O4—Tl1ⁱⁱ	2.3 (3)
O1ⁱ—Al2—O1^xviii	92.71 (15)	Tl2^xxxiv—O4—Tl1ⁱⁱ	149.95 (8)

Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −x, −x+y, −z+3/2; (iv) y, x, −z+3/2; (v) x−y, −y, −z+3/2; (vi) −x+y, −x−1, z; (vii) −x+2/3, −y−2/3, −z+4/3; (viii) x−y−4/3, x−2/3, −z+4/3; (ix) y+2/3, −x+y+4/3, −z+4/3; (x) x−1/3, x−y−2/3, z−1/6; (xi) −y−1/3, −x+1/3, z−1/6; (xii) −x+y+2/3, y+1/3, z−1/6; (xiii) −x−1/3, −y−2/3, −z+4/3; (xiv) y+2/3, −x+y+1/3, −z+4/3; (xv) x−y−1/3, x+1/3, −z+4/3; (xvi) −y, x−y+1, z; (xvii) x+1, y+1, z; (xviii) x, y+1, z; (xix) −x+y+1, −x+1, z; (xx) −x+2/3, −y+1/3, −z+4/3; (xxi) x−1, y, z; (xxii) −x+y−1, −x−1, z; (xxiii) −y+1/3, −x+2/3, z+1/6; (xxiv) −x−1/3, −y+1/3, −z+4/3; (xxv) −x+2/3, −y+4/3, −z+4/3; (xxvi) −y−1, x−y−1, z; (xxvii) x−1, y−1, z; (xxviii) x+1, y, z; (xxix) x, y−1, z; (xxx) −y−1, x−y, z; (xxxi) −y+1/3, −x−1/3, z+1/6; (xxxii) −x+y+1, −x, z; (xxxiii) −y+1, x−y, z; (xxxiv) y+1, x, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^xxxv	0.87 (4)	1.87 (5)	2.584 (5)	139 (6)

Symmetry code: (xxxv) y, x−1, −z+3/2.

Funding information

Funding for this research was provided by: Doc fForte Fellowship of the Austrian Academy of Sciences to K. Schwendtner. The authors acknowledge the TU Wien University Library for financial support through its Open Access Funding Program.

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Volume 74| Part 10| October 2018| Pages 1504-1508

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