(NH₄)Ga(HAsO₄)₂ and TlAl(HAsO₄)₂ - two new RbFe(HPO₄)₂-type M ⁺ M ³⁺ arsenates

The crystal structures of hydro­thermally synthesized (NH₄)Ga(HAsO₄)₂ and TlAl(HAsO₄)₂ were solved by single-crystal X-ray diffraction. They both crystallize in the common RbFe(HPO₄)₂ structure type (R c).

Abstract

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 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.

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 ⁺–M ³⁺–O–(H)–As⁵⁺ (M ⁺ = Li, Na, K, Rb, Cs, Ag, Tl, NH₄; M ³⁺ = 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 c), was found to exhibit a large crystal–chemical flexibility, which allows the incorporation of a wide variety of M ⁺ and M ³⁺ 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 ⁺ M ³⁺ 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.

Structural commentary  

The two compounds are representatives of the RbFe(HPO₄)₂ structure type (R 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 ; Yakubovich, 1993 ▸) in which all other known (NH₄)M^{3 +}(HTO₄)₂ (T = P, As) compounds crystallize (see Schwendtner & Kolitsch, 2018b ▸ for a compilation), the RbAl₂As(HAsO₄)₆ type (R c; Schwendtner & Kolitsch, 2018a ▸) and the RbAl(HAsO₄)₂ type (R32; Schwendtner & Kolitsch, 2018a ▸). The fundamental building unit in all these structure types contains M ³⁺O₆ octa­hedra, which are connected via their six corners to six protonated AsO₄ tetra­hedra, thereby forming an M ³⁺As₆O₂₄ unit. These units are in turn connected via three corners to other M ³⁺O₆ octa­hedra. The free, protonated corner of each AsO₄ tetra­hedron forms a hydrogen bond to the neighbouring M ³⁺As₆O₂₄ group (Fig. 2 ▸). The M ³⁺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 ▸).

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.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4xxi	0.87 (3)	1.74 (3)	2.610 (3)	172 (6)

Symmetry code: (xxi) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4xxi	0.87 (4)	1.87 (5)	2.584 (5)	139 (6)

Symmetry code: (xxi) .

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—O4xi	3.516 (3)
Tl1—O3	3.085 (8)	Tl2—O3xii	3.545 (4)
Tl1—O3ii	3.085 (8)	Tl2—O3xiii	3.545 (4)
Tl1—O3iii	3.136 (5)	Tl2—O3xiv	3.545 (4)
Tl1—O3i	3.136 (5)	Al1—O2xv	1.895 (4)
Tl1—O2iii	3.233 (13)	Al1—O2v	1.895 (4)
Tl1—O2i	3.233 (13)	Al1—O2xvi	1.895 (4)
Tl1—O3iv	3.261 (12)	Al1—O4xvii	1.901 (4)
Tl1—O3v	3.261 (12)	Al1—O4i	1.901 (4)
Tl1—O2ii	3.351 (4)	Al1—O4xviii	1.901 (4)
Tl1—O2	3.351 (4)	Al2—O1viii	1.887 (4)
Tl1—O2v	3.501 (15)	Al2—O1xiv	1.887 (4)
Tl1—O2iv	3.501 (15)	Al2—O1xix	1.887 (4)
Tl2—O3i	2.813 (4)	Al2—O1i	1.887 (4)
Tl2—O3v	2.813 (4)	Al2—O1xviii	1.887 (4)
Tl2—O3	2.813 (4)	Al2—O1xvii	1.887 (4)
Tl2—O1vi	3.410 (4)	As—O1xx	1.661 (3)
Tl2—O1vii	3.410 (4)	As—O2	1.674 (3)
Tl2—O1viii	3.410 (4)	As—O4ii	1.679 (3)
Tl2—O4ix	3.516 (3)	As—O3	1.746 (4)
Tl2—O4x	3.516 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) ; (xii) ; (xiii) ; (xiv) ; (xv) ; (xvi) ; (xvii) ; (xviii) ; (xix) ; (xx) .

For (NH₄)Ga(HAsO₄)₂, the bond-valence sum values for the M ³⁺ 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—O4xi	3.493 (5)
N1—O3i	3.173 (3)	N2—O3xii	3.557 (4)
N1—O3ii	3.173 (3)	N2—O3xiii	3.557 (4)
N1—O3iii	3.173 (3)	N2—O3xiv	3.557 (4)
N1—O3iv	3.173 (3)	Ga1—O2xv	1.9619 (16)
N1—O3v	3.173 (3)	Ga1—O2iii	1.9619 (17)
N1—O2	3.3657 (18)	Ga1—O2xvi	1.9619 (17)
N1—O2ii	3.3657 (18)	Ga1—O4v	1.9666 (17)
N1—O2iv	3.3657 (18)	Ga1—O4xvii	1.9666 (17)
N1—O2iii	3.3657 (18)	Ga1—O4xviii	1.9667 (16)
N1—O2i	3.3657 (17)	Ga2—O1viii	1.9588 (18)
N1—O2v	3.3657 (17)	Ga2—O1xiv	1.9588 (19)
N2—O3v	2.918 (4)	Ga2—O1xix	1.9588 (18)
N2—O3iii	2.918 (4)	Ga2—O1v	1.9589 (18)
N2—O3	2.918 (4)	Ga2—O1xviii	1.9589 (19)
N2—O1vi	3.375 (3)	Ga2—O1xvii	1.9589 (18)
N2—O1vii	3.375 (3)	As—O1xx	1.6555 (18)
N2—O1viii	3.375 (3)	As—O2	1.6700 (16)
N2—O4ix	3.493 (5)	As—O4ii	1.6783 (17)
N2—O4x	3.493 (5)	As—O3	1.740 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) ; (xii) ; (xiii) ; (xiv) ; (xv) ; (xvi) ; (xvii) ; (xviii) ; (xix) ; (xx) .

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 ⁺:M ³⁺:As of 1:1:3 of the respective M ⁺ M ³⁺ 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.

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 c:H	Trigonal, R 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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 R ₁ 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. 1 ▸ b, 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.

Supplementary Material

CCDC references: 1869299, 1869298

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

supplementary crystallographic information

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Crystal data

(NH4)Ga(HAsO4)2	Dx = 3.358 Mg m−3
Mr = 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

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Data collection

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

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Refinement

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(Fo2) + (0.0273P)2 + 16.8283P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.003
1326 reflections	Δρmax = 0.75 e Å−3
61 parameters	Δρmin = −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)

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

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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)*

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Atomic displacement parameters (Ų)

	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)

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Geometric parameters (Å, º)

N1—O3	3.173 (3)	N2—O3xii	3.557 (4)
N1—O3i	3.173 (3)	N2—O3xiii	3.557 (4)
N1—O3ii	3.173 (3)	N2—O3xiv	3.557 (4)
N1—O3iii	3.173 (3)	Ga1—O2xv	1.9619 (16)
N1—O3iv	3.173 (3)	Ga1—O2iii	1.9619 (17)
N1—O3v	3.173 (3)	Ga1—O2xvi	1.9619 (17)
N1—O2	3.3657 (18)	Ga1—O4v	1.9666 (17)
N1—O2ii	3.3657 (18)	Ga1—O4xvii	1.9666 (17)
N1—O2iv	3.3657 (18)	Ga1—O4xviii	1.9667 (16)
N1—O2iii	3.3657 (18)	Ga2—O1viii	1.9588 (18)
N1—O2i	3.3657 (17)	Ga2—O1xiv	1.9588 (19)
N1—O2v	3.3657 (17)	Ga2—O1xix	1.9588 (18)
N2—O3v	2.918 (4)	Ga2—O1v	1.9589 (18)
N2—O3iii	2.918 (4)	Ga2—O1xviii	1.9589 (19)
N2—O3	2.918 (4)	Ga2—O1xvii	1.9589 (18)
N2—O1vi	3.375 (3)	As—O1xx	1.6555 (18)
N2—O1vii	3.375 (3)	As—O2	1.6700 (16)
N2—O1viii	3.375 (3)	As—O4ii	1.6783 (17)
N2—O4ix	3.493 (5)	As—O3	1.740 (2)
N2—O4x	3.493 (5)	O3—H3	0.87 (3)
N2—O4xi	3.493 (5)
O3—N1—O3i	162.83 (7)	O2xv—Ga1—N1	119.85 (5)
O3—N1—O3ii	123.01 (7)	O2iii—Ga1—N1	32.80 (5)
O3i—N1—O3ii	69.03 (6)	O2xvi—Ga1—N1	105.75 (5)
O3—N1—O3iii	69.03 (6)	O4v—Ga1—N1	77.33 (5)
O3i—N1—O3iii	102.44 (7)	O4xvii—Ga1—N1	143.46 (5)
O3ii—N1—O3iii	162.83 (8)	O4xviii—Ga1—N1	59.54 (5)
O3—N1—O3iv	102.44 (7)	N2xxi—Ga1—N1	92.432 (5)
O3i—N1—O3iv	69.03 (6)	N1xvii—Ga1—N1	119.821 (1)
O3ii—N1—O3iv	69.03 (6)	O2xv—Ga1—N1xvi	105.75 (5)
O3iii—N1—O3iv	123.01 (7)	O2iii—Ga1—N1xvi	119.85 (5)
O3—N1—O3v	69.03 (6)	O2xvi—Ga1—N1xvi	32.80 (5)
O3i—N1—O3v	123.01 (8)	O4v—Ga1—N1xvi	143.46 (5)
O3ii—N1—O3v	102.44 (7)	O4xvii—Ga1—N1xvi	59.54 (5)
O3iii—N1—O3v	69.03 (6)	O4xviii—Ga1—N1xvi	77.33 (5)
O3iv—N1—O3v	162.83 (7)	N2xxi—Ga1—N1xvi	92.432 (5)
O3—N1—O2	48.11 (4)	N1xvii—Ga1—N1xvi	119.821 (1)
O3i—N1—O2	115.51 (5)	N1—Ga1—N1xvi	119.821 (1)
O3ii—N1—O2	126.51 (5)	O1viii—Ga2—O1xiv	93.53 (7)
O3iii—N1—O2	70.41 (5)	O1viii—Ga2—O1xix	93.53 (7)
O3iv—N1—O2	65.01 (5)	O1xiv—Ga2—O1xix	93.53 (7)
O3v—N1—O2	113.56 (5)	O1viii—Ga2—O1v	180.0
O3—N1—O2ii	126.52 (5)	O1xiv—Ga2—O1v	86.47 (7)
O3i—N1—O2ii	70.41 (5)	O1xix—Ga2—O1v	86.47 (7)
O3ii—N1—O2ii	48.11 (5)	O1viii—Ga2—O1xviii	86.47 (7)
O3iii—N1—O2ii	115.51 (5)	O1xiv—Ga2—O1xviii	180.0
O3iv—N1—O2ii	113.56 (5)	O1xix—Ga2—O1xviii	86.47 (7)
O3v—N1—O2ii	65.01 (5)	O1v—Ga2—O1xviii	93.53 (7)
O2—N1—O2ii	171.26 (6)	O1viii—Ga2—O1xvii	86.47 (7)
O3—N1—O2iv	65.01 (5)	O1xiv—Ga2—O1xvii	86.47 (7)
O3i—N1—O2iv	113.56 (5)	O1xix—Ga2—O1xvii	180.0
O3ii—N1—O2iv	70.41 (5)	O1v—Ga2—O1xvii	93.53 (7)
O3iii—N1—O2iv	126.51 (5)	O1xviii—Ga2—O1xvii	93.53 (7)
O3iv—N1—O2iv	48.11 (4)	O1viii—Ga2—N2xix	62.79 (8)
O3v—N1—O2iv	115.51 (5)	O1xiv—Ga2—N2xix	67.00 (7)
O2—N1—O2iv	59.00 (6)	O1xix—Ga2—N2xix	146.77 (8)
O2ii—N1—O2iv	113.20 (2)	O1v—Ga2—N2xix	117.21 (8)
O3—N1—O2iii	113.56 (5)	O1xviii—Ga2—N2xix	113.00 (7)
O3i—N1—O2iii	65.01 (5)	O1xvii—Ga2—N2xix	33.23 (8)
O3ii—N1—O2iii	115.51 (5)	O1viii—Ga2—N2xvii	117.21 (8)
O3iii—N1—O2iii	48.11 (5)	O1xiv—Ga2—N2xvii	113.00 (7)
O3iv—N1—O2iii	126.51 (5)	O1xix—Ga2—N2xvii	33.23 (8)
O3v—N1—O2iii	70.41 (5)	O1v—Ga2—N2xvii	62.79 (8)
O2—N1—O2iii	113.20 (2)	O1xviii—Ga2—N2xvii	66.99 (7)
O2ii—N1—O2iii	74.86 (6)	O1xvii—Ga2—N2xvii	146.77 (8)
O2iv—N1—O2iii	171.26 (6)	N2xix—Ga2—N2xvii	180.0
O3—N1—O2i	115.51 (5)	O1viii—Ga2—N2	33.23 (8)
O3i—N1—O2i	48.11 (4)	O1xiv—Ga2—N2	117.21 (8)
O3ii—N1—O2i	113.56 (5)	O1xix—Ga2—N2	113.01 (8)
O3iii—N1—O2i	65.01 (5)	O1v—Ga2—N2	146.77 (8)
O3iv—N1—O2i	70.41 (5)	O1xviii—Ga2—N2	62.79 (8)
O3v—N1—O2i	126.51 (5)	O1xvii—Ga2—N2	67.00 (8)
O2—N1—O2i	74.86 (6)	N2xix—Ga2—N2	60.005 (2)
O2ii—N1—O2i	113.20 (2)	N2xvii—Ga2—N2	119.995 (2)
O2iv—N1—O2i	113.20 (2)	O1viii—Ga2—N2xvi	113.01 (7)
O2iii—N1—O2i	59.00 (6)	O1xiv—Ga2—N2xvi	33.23 (8)
O3—N1—O2v	70.41 (5)	O1xix—Ga2—N2xvi	117.21 (8)
O3i—N1—O2v	126.51 (5)	O1v—Ga2—N2xvi	66.99 (7)
O3ii—N1—O2v	65.01 (5)	O1xviii—Ga2—N2xvi	146.77 (8)
O3iii—N1—O2v	113.56 (5)	O1xvii—Ga2—N2xvi	62.79 (8)
O3iv—N1—O2v	115.51 (5)	N2xix—Ga2—N2xvi	60.005 (2)
O3v—N1—O2v	48.11 (4)	N2xvii—Ga2—N2xvi	119.995 (2)
O2—N1—O2v	113.20 (2)	N2—Ga2—N2xvi	119.995 (2)
O2ii—N1—O2v	59.00 (6)	O1viii—Ga2—N2xxii	66.99 (7)
O2iv—N1—O2v	74.86 (6)	O1xiv—Ga2—N2xxii	146.77 (8)
O2iii—N1—O2v	113.20 (2)	O1xix—Ga2—N2xxii	62.79 (8)
O2i—N1—O2v	171.26 (6)	O1v—Ga2—N2xxii	113.00 (7)
O3v—N2—O3iii	76.09 (13)	O1xviii—Ga2—N2xxii	33.23 (8)
O3v—N2—O3	76.08 (13)	O1xvii—Ga2—N2xxii	117.21 (8)
O3iii—N2—O3	76.08 (13)	N2xix—Ga2—N2xxii	119.995 (2)
O3v—N2—O1vi	77.21 (6)	N2xvii—Ga2—N2xxii	60.005 (2)
O3iii—N2—O1vi	152.44 (16)	N2—Ga2—N2xxii	60.005 (2)
O3—N2—O1vi	91.02 (6)	N2xvi—Ga2—N2xxii	180.0
O3v—N2—O1vii	152.44 (16)	O1viii—Ga2—N2xxiii	146.77 (8)
O3iii—N2—O1vii	91.02 (6)	O1xiv—Ga2—N2xxiii	62.79 (8)
O3—N2—O1vii	77.21 (6)	O1xix—Ga2—N2xxiii	66.99 (8)
O1vi—N2—O1vii	110.03 (9)	O1v—Ga2—N2xxiii	33.23 (8)
O3v—N2—O1viii	91.02 (6)	O1xviii—Ga2—N2xxiii	117.21 (8)
O3iii—N2—O1viii	77.21 (6)	O1xvii—Ga2—N2xxiii	113.00 (8)
O3—N2—O1viii	152.44 (16)	N2xix—Ga2—N2xxiii	119.995 (2)
O1vi—N2—O1viii	110.03 (9)	N2xvii—Ga2—N2xxiii	60.005 (2)
O1vii—N2—O1viii	110.03 (9)	N2—Ga2—N2xxiii	180.0
O3v—N2—O4ix	111.48 (7)	N2xvi—Ga2—N2xxiii	60.005 (2)
O3iii—N2—O4ix	156.43 (10)	N2xxii—Ga2—N2xxiii	119.994 (2)
O3—N2—O4ix	126.99 (7)	O1xx—As—O2	118.81 (9)
O1vi—N2—O4ix	45.41 (6)	O1xx—As—O4ii	105.46 (9)
O1vii—N2—O4ix	90.09 (12)	O2—As—O4ii	115.11 (9)
O1viii—N2—O4ix	80.30 (10)	O1xx—As—O3	107.12 (11)
O3v—N2—O4x	156.43 (10)	O2—As—O3	103.09 (10)
O3iii—N2—O4x	126.99 (7)	O4ii—As—O3	106.35 (9)
O3—N2—O4x	111.48 (7)	O1xx—As—N2xii	64.22 (8)
O1vi—N2—O4x	80.30 (10)	O2—As—N2xii	173.25 (6)
O1vii—N2—O4x	45.41 (6)	O4ii—As—N2xii	68.25 (8)
O1viii—N2—O4x	90.09 (12)	O3—As—N2xii	70.17 (8)
O4ix—N2—O4x	45.67 (8)	O1xx—As—N1	142.98 (8)
O3v—N2—O4xi	126.99 (7)	O2—As—N1	56.21 (6)
O3iii—N2—O4xi	111.48 (7)	O4ii—As—N1	108.99 (6)
O3—N2—O4xi	156.43 (10)	O3—As—N1	50.09 (8)
O1vi—N2—O4xi	90.09 (12)	N2xii—As—N1	117.48 (2)
O1vii—N2—O4xi	80.30 (10)	O1xx—As—N2	81.32 (10)
O1viii—N2—O4xi	45.41 (6)	O2—As—N2	99.84 (7)
O4ix—N2—O4xi	45.67 (8)	O4ii—As—N2	133.25 (6)
O4x—N2—O4xi	45.67 (8)	O3—As—N2	32.26 (8)
O3v—N2—O3xii	119.40 (8)	N2xii—As—N2	74.310 (11)
O3iii—N2—O3xii	150.86 (8)	N1—As—N2	65.36 (6)
O3—N2—O3xii	83.78 (6)	O1xx—As—N1xxiv	88.02 (8)
O1vi—N2—O3xii	46.33 (6)	O2—As—N1xxiv	94.12 (6)
O1vii—N2—O3xii	63.78 (7)	O4ii—As—N1xxiv	40.77 (6)
O1viii—N2—O3xii	123.57 (16)	O3—As—N1xxiv	147.10 (7)
O4ix—N2—O3xii	45.67 (7)	N2xii—As—N1xxiv	92.00 (3)
O4x—N2—O3xii	43.44 (7)	N1—As—N1xxiv	127.434 (12)
O4xi—N2—O3xii	80.03 (12)	N2—As—N1xxiv	165.32 (5)
O3v—N2—O3xiii	83.77 (6)	O1xx—As—N2xxiv	43.28 (9)
O3iii—N2—O3xiii	119.40 (8)	O2—As—N2xxiv	127.15 (7)
O3—N2—O3xiii	150.86 (7)	O4ii—As—N2xxiv	63.82 (7)
O1vi—N2—O3xiii	63.78 (7)	O3—As—N2xxiv	128.79 (9)
O1vii—N2—O3xiii	123.57 (16)	N2xii—As—N2xxiv	59.42 (2)
O1viii—N2—O3xiii	46.33 (6)	N1—As—N2xxiv	172.65 (3)
O4ix—N2—O3xiii	43.44 (7)	N2—As—N2xxiv	117.94 (11)
O4x—N2—O3xiii	80.03 (12)	N1xxiv—As—N2xxiv	48.43 (5)
O4xi—N2—O3xiii	45.67 (7)	Asxxv—O1—Ga2xxvi	137.99 (11)
O3xii—N2—O3xiii	88.14 (11)	Asxxv—O1—N2vi	89.57 (11)
O3v—N2—O3xiv	150.86 (8)	Ga2xxvi—O1—N2vi	128.22 (11)
O3iii—N2—O3xiv	83.77 (6)	Asxxv—O1—N2xxv	76.36 (10)
O3—N2—O3xiv	119.40 (8)	Ga2xxvi—O1—N2xxv	93.37 (8)
O1vi—N2—O3xiv	123.57 (16)	N2vi—O1—N2xxv	76.98 (4)
O1vii—N2—O3xiv	46.33 (6)	Asxxv—O1—N2xxvi	121.95 (10)
O1viii—N2—O3xiv	63.78 (7)	Ga2xxvi—O1—N2xxvi	89.12 (8)
O4ix—N2—O3xiv	80.03 (12)	N2vi—O1—N2xxvi	74.93 (4)
O4x—N2—O3xiv	45.67 (7)	N2xxv—O1—N2xxvi	145.93 (11)
O4xi—N2—O3xiv	43.44 (7)	As—O2—Ga1xxiv	121.85 (9)
O3xii—N2—O3xiv	88.14 (11)	As—O2—N1	99.43 (7)
O3xiii—N2—O3xiv	88.14 (11)	Ga1xxiv—O2—N1	128.79 (7)
O2xv—Ga1—O2iii	91.61 (7)	As—O2—N2	60.17 (5)
O2xv—Ga1—O2xvi	91.61 (7)	Ga1xxiv—O2—N2	163.08 (8)
O2iii—Ga1—O2xvi	91.61 (7)	N1—O2—N2	63.03 (5)
O2xv—Ga1—O4v	88.91 (7)	As—O3—N2	129.17 (11)
O2iii—Ga1—O4v	92.29 (8)	As—O3—N1	105.03 (9)
O2xvi—Ga1—O4v	176.05 (7)	N2—O3—N1	93.77 (9)
O2xv—Ga1—O4xvii	92.29 (8)	As—O3—N2xii	82.43 (8)
O2iii—Ga1—O4xvii	176.05 (7)	N2—O3—N2xii	96.22 (6)
O2xvi—Ga1—O4xvii	88.91 (7)	N1—O3—N2xii	159.27 (9)
O4v—Ga1—O4xvii	87.16 (8)	As—O3—H3	102 (4)
O2xv—Ga1—O4xviii	176.05 (7)	N2—O3—H3	125 (4)
O2iii—Ga1—O4xviii	88.91 (7)	N1—O3—H3	91 (3)
O2xvi—Ga1—O4xviii	92.29 (7)	N2xii—O3—H3	69 (3)
O4v—Ga1—O4xviii	87.16 (8)	Asii—O4—Ga1xxvi	130.02 (10)
O4xvii—Ga1—O4xviii	87.16 (8)	Asii—O4—N2xxvii	85.25 (7)
O2xv—Ga1—N2xxi	124.12 (5)	Ga1xxvi—O4—N2xxvii	100.62 (8)
O2iii—Ga1—N2xxi	124.12 (5)	Asii—O4—N1xxv	124.11 (7)
O2xvi—Ga1—N2xxi	124.12 (5)	Ga1xxvi—O4—N1xxv	96.68 (6)
O4v—Ga1—N2xxi	52.75 (5)	N2xxvii—O4—N1xxv	118.40 (4)
O4xvii—Ga1—N2xxi	52.75 (5)	Asii—O4—N1	51.75 (5)
O4xviii—Ga1—N2xxi	52.75 (5)	Ga1xxvi—O4—N1	79.17 (5)
O2xv—Ga1—N1xvii	32.80 (5)	N2xxvii—O4—N1	104.63 (4)
O2iii—Ga1—N1xvii	105.75 (5)	N1xxv—O4—N1	136.70 (4)
O2xvi—Ga1—N1xvii	119.85 (5)	Asii—O4—N2xxviii	98.66 (7)
O4v—Ga1—N1xvii	59.54 (5)	Ga1xxvi—O4—N2xxviii	129.48 (6)
O4xvii—Ga1—N1xvii	77.33 (5)	N2xxvii—O4—N2xxviii	66.70 (3)
O4xviii—Ga1—N1xvii	143.46 (5)	N1xxv—O4—N2xxviii	57.01 (5)
N2xxi—Ga1—N1xvii	92.432 (5)	N1—O4—N2xxviii	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.

Ammonium gallium bis[hydrogen arsenate(V)] (NH4GaHAsO42). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4xxix	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). Crystal data

TlAl(HAsO4)2	Dx = 4.849 Mg m−3
Mr = 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

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Data collection

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

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Refinement

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(Fo2) + (0.023P)2 + 84.2452P] where P = (Fo2 + 2Fc2)/3
S = 1.21	(Δ/σ)max = 0.003
698 reflections	Δρmax = 0.82 e Å−3
69 parameters	Δρmin = −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)

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

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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)*

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Atomic displacement parameters (Ų)

	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)

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Geometric parameters (Å, º)

Tl1—Tl1i	0.28 (3)	Tl2—O3xiv	3.545 (4)
Tl1—Tl1ii	0.28 (3)	Tl2—O3xv	3.545 (4)
Tl1—O3	3.085 (8)	Tl2—AsBxiii	3.74 (2)
Tl1—O3iii	3.085 (8)	Tl2—AsBxv	3.74 (2)
Tl1—O3iv	3.136 (5)	Tl2—AsBxiv	3.74 (2)
Tl1—O3i	3.136 (5)	Al1—O2xvi	1.895 (4)
Tl1—O2iv	3.233 (13)	Al1—O2ii	1.895 (4)
Tl1—O2i	3.233 (13)	Al1—O2xvii	1.895 (4)
Tl1—O3v	3.261 (12)	Al1—O4xviii	1.901 (4)
Tl1—O3ii	3.261 (12)	Al1—O4i	1.901 (4)
Tl1—O2iii	3.351 (4)	Al1—O4xix	1.901 (4)
Tl1—O2	3.351 (4)	Al2—O1ix	1.887 (4)
Tl1—O2ii	3.501 (15)	Al2—O1xv	1.887 (4)
Tl1—O2v	3.501 (15)	Al2—O1xx	1.887 (4)
Tl1—AsBvi	3.89 (3)	Al2—O1i	1.887 (4)
Tl2—O3i	2.813 (4)	Al2—O1xix	1.887 (4)
Tl2—O3ii	2.813 (4)	Al2—O1xviii	1.887 (4)
Tl2—O3	2.813 (4)	As—AsB	1.33 (2)
Tl2—O1vii	3.410 (4)	As—O1xxi	1.661 (3)
Tl2—O1viii	3.410 (4)	As—O2	1.674 (3)
Tl2—O1ix	3.410 (4)	As—O4iii	1.679 (3)
Tl2—O4x	3.516 (3)	As—O3	1.746 (4)
Tl2—O4xi	3.516 (3)	AsB—O4iii	1.35 (2)
Tl2—O4xii	3.516 (3)	AsB—O1xxi	1.64 (2)
Tl2—O3xiii	3.545 (4)	AsB—O2xxii	2.12 (2)
Tl1i—Tl1—Tl1ii	60.00 (3)	O1xix—Al2—O1xviii	92.71 (15)
Tl1i—Tl1—O3	127.2 (3)	O1ix—Al2—Tl2xx	64.49 (12)
Tl1ii—Tl1—O3	98.0 (3)	O1xv—Al2—Tl2xx	64.45 (11)
Tl1i—Tl1—O3iii	98.0 (3)	O1xx—Al2—Tl2xx	145.30 (11)
Tl1ii—Tl1—O3iii	127.2 (2)	O1i—Al2—Tl2xx	115.51 (12)
O3—Tl1—O3iii	129.1 (6)	O1xix—Al2—Tl2xx	115.55 (11)
Tl1i—Tl1—O3iv	114.4 (3)	O1xviii—Al2—Tl2xx	34.70 (11)
Tl1ii—Tl1—O3iv	77.0 (4)	O1ix—Al2—Tl2xviii	115.51 (12)
O3—Tl1—O3iv	104.2 (3)	O1xv—Al2—Tl2xviii	115.55 (11)
O3iii—Tl1—O3iv	70.24 (16)	O1xx—Al2—Tl2xviii	34.70 (11)
Tl1i—Tl1—O3i	77.0 (3)	O1i—Al2—Tl2xviii	64.49 (12)
Tl1ii—Tl1—O3i	114.4 (2)	O1xix—Al2—Tl2xviii	64.45 (11)
O3—Tl1—O3i	70.24 (16)	O1xviii—Al2—Tl2xviii	145.29 (11)
O3iii—Tl1—O3i	104.2 (3)	Tl2xx—Al2—Tl2xviii	180.0
O3iv—Tl1—O3i	167.5 (6)	O1ix—Al2—Tl2xvii	115.55 (11)
Tl1i—Tl1—O2iv	163.77 (15)	O1xv—Al2—Tl2xvii	34.70 (11)
Tl1ii—Tl1—O2iv	112.8 (3)	O1xx—Al2—Tl2xvii	115.51 (12)
O3—Tl1—O2iv	66.4 (3)	O1i—Al2—Tl2xvii	64.45 (11)
O3iii—Tl1—O2iv	74.5 (3)	O1xix—Al2—Tl2xvii	145.29 (11)
O3iv—Tl1—O2iv	49.68 (16)	O1xviii—Al2—Tl2xvii	64.49 (12)
O3i—Tl1—O2iv	118.5 (5)	Tl2xx—Al2—Tl2xvii	60.1
Tl1i—Tl1—O2i	112.84 (18)	Tl2xviii—Al2—Tl2xvii	119.9
Tl1ii—Tl1—O2i	163.77 (10)	O1ix—Al2—Tl2	34.70 (11)
O3—Tl1—O2i	74.5 (3)	O1xv—Al2—Tl2	115.51 (12)
O3iii—Tl1—O2i	66.4 (3)	O1xx—Al2—Tl2	115.55 (12)
O3iv—Tl1—O2i	118.5 (5)	O1i—Al2—Tl2	145.29 (11)
O3i—Tl1—O2i	49.68 (16)	O1xix—Al2—Tl2	64.49 (12)
O2iv—Tl1—O2i	77.8 (4)	O1xviii—Al2—Tl2	64.45 (12)
Tl1i—Tl1—O3v	48.90 (18)	Tl2xx—Al2—Tl2	60.1
Tl1ii—Tl1—O3v	61.10 (14)	Tl2xviii—Al2—Tl2	119.942 (1)
O3—Tl1—O3v	158.5 (4)	Tl2xvii—Al2—Tl2	119.9
O3iii—Tl1—O3v	68.60 (12)	O1ix—Al2—Tl2xxiv	64.45 (11)
O3iv—Tl1—O3v	68.01 (16)	O1xv—Al2—Tl2xxiv	145.30 (11)
O3i—Tl1—O3v	121.2 (3)	O1xx—Al2—Tl2xxiv	64.49 (12)
O2iv—Tl1—O3v	115.03 (10)	O1i—Al2—Tl2xxiv	115.55 (11)
O2i—Tl1—O3v	127.04 (11)	O1xix—Al2—Tl2xxiv	34.70 (11)
Tl1i—Tl1—O3ii	61.1 (2)	O1xviii—Al2—Tl2xxiv	115.51 (12)
Tl1ii—Tl1—O3ii	48.90 (16)	Tl2xx—Al2—Tl2xxiv	119.9
O3—Tl1—O3ii	68.60 (12)	Tl2xviii—Al2—Tl2xxiv	60.1
O3iii—Tl1—O3ii	158.5 (4)	Tl2xvii—Al2—Tl2xxiv	180.0
O3iv—Tl1—O3ii	121.2 (3)	Tl2—Al2—Tl2xxiv	60.1
O3i—Tl1—O3ii	68.01 (16)	O1ix—Al2—Tl2xxv	145.30 (11)
O2iv—Tl1—O3ii	127.04 (11)	O1xv—Al2—Tl2xxv	64.49 (12)
O2i—Tl1—O3ii	115.03 (10)	O1xx—Al2—Tl2xxv	64.45 (12)
O3v—Tl1—O3ii	97.6 (5)	O1i—Al2—Tl2xxv	34.70 (11)
Tl1i—Tl1—O2iii	62.8 (3)	O1xix—Al2—Tl2xxv	115.51 (12)
Tl1ii—Tl1—O2iii	120.68 (19)	O1xviii—Al2—Tl2xxv	115.55 (12)
O3—Tl1—O2iii	129.1 (3)	Tl2xx—Al2—Tl2xxv	119.9
O3iii—Tl1—O2iii	48.95 (11)	Tl2xviii—Al2—Tl2xxv	60.1
O3iv—Tl1—O2iii	115.18 (11)	Tl2xvii—Al2—Tl2xxv	60.1
O3i—Tl1—O2iii	64.40 (9)	Tl2—Al2—Tl2xxv	180.0
O2iv—Tl1—O2iii	117.7 (4)	Tl2xxiv—Al2—Tl2xxv	119.9
O2i—Tl1—O2iii	59.15 (18)	AsB—As—O1xxi	65.3 (9)
O3v—Tl1—O2iii	70.66 (15)	AsB—As—O2	108.5 (9)
O3ii—Tl1—O2iii	111.8 (3)	O1xxi—As—O2	118.77 (18)
Tl1i—Tl1—O2	120.7 (3)	AsB—As—O4iii	51.8 (9)
Tl1ii—Tl1—O2	62.8 (4)	O1xxi—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)
O3iv—Tl1—O2	64.40 (9)	O1xxi—As—O3	107.52 (19)
O3i—Tl1—O2	115.18 (11)	O2—As—O3	103.03 (19)
O2iv—Tl1—O2	59.15 (17)	O4iii—As—O3	105.63 (17)
O2i—Tl1—O2	117.7 (4)	AsB—As—Tl2xiii	79.0 (9)
O3v—Tl1—O2	111.8 (3)	O1xxi—As—Tl2xiii	65.02 (13)
O3ii—Tl1—O2	70.66 (15)	O2—As—Tl2xiii	172.42 (13)
O2iii—Tl1—O2	176.5 (6)	O4iii—As—Tl2xiii	68.63 (12)
Tl1i—Tl1—O2ii	14.95 (6)	O3—As—Tl2xiii	69.39 (14)
Tl1ii—Tl1—O2ii	55.40 (8)	AsB—As—Tl1ii	150.1 (9)
O3—Tl1—O2ii	112.4 (2)	O1xxi—As—Tl1ii	142.74 (15)
O3iii—Tl1—O2ii	112.3 (2)	O2—As—Tl1ii	54.3 (2)
O3iv—Tl1—O2ii	122.2 (4)	O4iii—As—Tl1ii	109.18 (17)
O3i—Tl1—O2ii	70.1 (2)	O3—As—Tl1ii	51.5 (2)
O2iv—Tl1—O2ii	168.2 (3)	Tl2xiii—As—Tl1ii	118.4 (2)
O2i—Tl1—O2ii	113.58 (8)	AsB—As—Tl1	149.5 (9)
O3v—Tl1—O2ii	61.5 (3)	O1xxi—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—O2v	55.40 (16)	Tl2xiii—As—Tl1	115.07 (16)
Tl1ii—Tl1—O2v	14.95 (6)	Tl1ii—As—Tl1	4.1 (4)
O3—Tl1—O2v	112.3 (2)	AsB—As—Tl1i	151.5 (9)
O3iii—Tl1—O2v	112.4 (2)	O1xxi—As—Tl1i	142.12 (17)
O3iv—Tl1—O2v	70.1 (2)	O2—As—Tl1i	56.77 (13)
O3i—Tl1—O2v	122.2 (4)	O4iii—As—Tl1i	108.88 (15)
O2iv—Tl1—O2v	113.58 (7)	O3—As—Tl1i	49.06 (16)
O2i—Tl1—O2v	168.2 (3)	Tl2xiii—As—Tl1i	115.97 (5)
O3v—Tl1—O2v	46.5 (2)	Tl1ii—As—Tl1i	2.5 (3)
O3ii—Tl1—O2v	61.5 (3)	Tl1—As—Tl1i	2.8 (3)
O2iii—Tl1—O2v	110.7 (4)	AsB—As—Tl2	145.5 (9)
O2—Tl1—O2v	72.6 (2)	O1xxi—As—Tl2	83.71 (13)
O2ii—Tl1—O2v	55.3 (3)	O2—As—Tl2	99.45 (13)
Tl1i—Tl1—AsBvi	135.2 (4)	O4iii—As—Tl2	131.69 (12)
Tl1ii—Tl1—AsBvi	141.1 (4)	O3—As—Tl2	30.29 (12)
O3—Tl1—AsBvi	43.1 (4)	Tl2xiii—As—Tl2	74.034 (11)
O3iii—Tl1—AsBvi	89.5 (5)	Tl1ii—As—Tl2	64.11 (8)
O3iv—Tl1—AsBvi	109.6 (5)	Tl1—As—Tl2	63.95 (6)
O3i—Tl1—AsBvi	58.5 (4)	Tl1i—As—Tl2	62.34 (12)
O2iv—Tl1—AsBvi	60.1 (4)	AsB—As—Tl1xxvi	23.3 (9)
O2i—Tl1—AsBvi	33.0 (4)	O1xxi—As—Tl1xxvi	87.98 (15)
O3v—Tl1—AsBvi	157.7 (4)	O2—As—Tl1xxvi	93.41 (14)
O3ii—Tl1—AsBvi	101.9 (3)	O4iii—As—Tl1xxvi	41.90 (12)
O2iii—Tl1—AsBvi	92.0 (4)	O3—As—Tl1xxvi	147.50 (13)
O2—Tl1—AsBvi	85.0 (4)	Tl2xiii—As—Tl1xxvi	93.30 (5)
O2ii—Tl1—AsBvi	127.8 (3)	Tl1ii—As—Tl1xxvi	126.79 (12)
O2v—Tl1—AsBvi	155.4 (3)	Tl1—As—Tl1xxvi	126.30 (17)
O3i—Tl2—O3ii	79.02 (13)	Tl1i—As—Tl1xxvi	128.27 (4)
O3i—Tl2—O3	79.02 (13)	Tl2—As—Tl1xxvi	166.91 (6)
O3ii—Tl2—O3	79.02 (13)	AsB—As—Tl1xxii	22.1 (9)
O3i—Tl2—O1vii	75.43 (10)	O1xxi—As—Tl1xxii	86.49 (17)
O3ii—Tl2—O1vii	154.16 (10)	O2—As—Tl1xxii	93.06 (16)
O3—Tl2—O1vii	92.26 (10)	O4iii—As—Tl1xxii	43.7 (2)
O3i—Tl2—O1viii	154.16 (10)	O3—As—Tl1xxii	149.3 (2)
O3ii—Tl2—O1viii	92.26 (10)	Tl2xiii—As—Tl1xxii	93.75 (10)
O3—Tl2—O1viii	75.43 (10)	Tl1ii—As—Tl1xxii	127.913 (17)
O1vii—Tl2—O1viii	109.19 (6)	Tl1—As—Tl1xxii	127.56 (3)
O3i—Tl2—O1ix	92.26 (10)	Tl1i—As—Tl1xxii	129.46 (17)
O3ii—Tl2—O1ix	75.43 (10)	Tl2—As—Tl1xxii	166.76 (4)
O3—Tl2—O1ix	154.15 (10)	Tl1xxvi—As—Tl1xxii	1.9 (2)
O1vii—Tl2—O1ix	109.19 (6)	As—AsB—O4iii	77.6 (12)
O1viii—Tl2—O1ix	109.19 (6)	As—AsB—O1xxi	67.1 (10)
O3i—Tl2—O4x	110.02 (10)	O4iii—AsB—O1xxi	126.4 (16)
O3ii—Tl2—O4x	153.52 (10)	As—AsB—O2xxii	112.5 (13)
O3—Tl2—O4x	126.54 (10)	O4iii—AsB—O2xxii	119.3 (13)
O1vii—Tl2—O4x	45.33 (8)	O1xxi—AsB—O2xxii	111.1 (11)
O1viii—Tl2—O4x	88.61 (8)	As—AsB—Tl2xiii	80.6 (10)
O1ix—Tl2—O4x	79.30 (8)	O4iii—AsB—Tl2xiii	69.9 (9)
O3i—Tl2—O4xi	153.52 (10)	O1xxi—AsB—Tl2xiii	65.6 (7)
O3ii—Tl2—O4xi	126.54 (10)	O2xxii—AsB—Tl2xiii	164.8 (9)
O3—Tl2—O4xi	110.02 (11)	As—AsB—Tl1xxvi	149.0 (12)
O1vii—Tl2—O4xi	79.30 (8)	O4iii—AsB—Tl1xxvi	84.2 (10)
O1viii—Tl2—O4xi	45.33 (8)	O1xxi—AsB—Tl1xxvi	142.5 (11)
O1ix—Tl2—O4xi	88.61 (8)	O2xxii—AsB—Tl1xxvi	56.2 (5)
O4x—Tl2—O4xi	44.26 (9)	Tl2xiii—AsB—Tl1xxvi	116.5 (6)
O3i—Tl2—O4xii	126.54 (11)	As—AsB—Tl1xxii	150.8 (12)
O3ii—Tl2—O4xii	110.01 (10)	O4iii—AsB—Tl1xxii	86.9 (10)
O3—Tl2—O4xii	153.52 (11)	O1xxi—AsB—Tl1xxii	140.0 (11)
O1vii—Tl2—O4xii	88.61 (8)	O2xxii—AsB—Tl1xxii	54.8 (5)
O1viii—Tl2—O4xii	79.30 (8)	Tl2xiii—AsB—Tl1xxii	117.2 (6)
O1ix—Tl2—O4xii	45.33 (8)	Tl1xxvi—AsB—Tl1xxii	2.7 (3)
O4x—Tl2—O4xii	44.26 (9)	As—AsB—Tl1xxvii	150.4 (12)
O4xi—Tl2—O4xii	44.26 (9)	O4iii—AsB—Tl1xxvii	83.6 (10)
O3i—Tl2—O3xiii	117.91 (14)	O1xxi—AsB—Tl1xxvii	141.8 (11)
O3ii—Tl2—O3xiii	152.25 (13)	O2xxii—AsB—Tl1xxvii	58.4 (6)
O3—Tl2—O3xiii	82.85 (11)	Tl2xiii—AsB—Tl1xxvii	114.1 (6)
O1vii—Tl2—O3xiii	46.50 (9)	Tl1xxvi—AsB—Tl1xxvii	2.4 (3)
O1viii—Tl2—O3xiii	62.74 (9)	Tl1xxii—AsB—Tl1xxvii	3.9 (4)
O1ix—Tl2—O3xiii	122.31 (9)	As—AsB—Tl2xxvii	146.6 (12)
O4x—Tl2—O3xiii	45.47 (8)	O4iii—AsB—Tl2xxvii	112.1 (11)
O4xi—Tl2—O3xiii	42.94 (8)	O1xxi—AsB—Tl2xxvii	82.8 (8)
O4xii—Tl2—O3xiii	78.63 (8)	O2xxii—AsB—Tl2xxvii	91.1 (7)
O3i—Tl2—O3xiv	82.85 (11)	Tl2xiii—AsB—Tl2xxvii	73.8 (4)
O3ii—Tl2—O3xiv	117.91 (14)	Tl1xxvi—AsB—Tl2xxvii	64.0 (4)
O3—Tl2—O3xiv	152.25 (12)	Tl1xxii—AsB—Tl2xxvii	62.3 (3)
O1vii—Tl2—O3xiv	62.74 (9)	Tl1xxvii—AsB—Tl2xxvii	62.2 (3)
O1viii—Tl2—O3xiv	122.31 (9)	As—AsB—Tl1ii	22.5 (7)
O1ix—Tl2—O3xiv	46.50 (9)	O4iii—AsB—Tl1ii	66.6 (9)
O4x—Tl2—O3xiv	42.94 (9)	O1xxi—AsB—Tl1ii	88.7 (8)
O4xi—Tl2—O3xiv	78.63 (8)	O2xxii—AsB—Tl1ii	99.8 (7)
O4xii—Tl2—O3xiv	45.47 (8)	Tl2xiii—AsB—Tl1ii	95.0 (5)
O3xiii—Tl2—O3xiv	87.33 (9)	Tl1xxvi—AsB—Tl1ii	126.5 (5)
O3i—Tl2—O3xv	152.25 (13)	Tl1xxii—AsB—Tl1ii	128.3 (5)
O3ii—Tl2—O3xv	82.85 (11)	Tl1xxvii—AsB—Tl1ii	128.0 (5)
O3—Tl2—O3xv	117.91 (14)	Tl2xxvii—AsB—Tl1ii	168.1 (5)
O1vii—Tl2—O3xv	122.31 (9)	As—AsB—Tl1	22.9 (7)
O1viii—Tl2—O3xv	46.50 (9)	O4iii—AsB—Tl1	63.7 (9)
O1ix—Tl2—O3xv	62.74 (9)	O1xxi—AsB—Tl1	89.8 (9)
O4x—Tl2—O3xv	78.63 (8)	O2xxii—AsB—Tl1	102.1 (7)
O4xi—Tl2—O3xv	45.47 (8)	Tl2xiii—AsB—Tl1	92.8 (5)
O4xii—Tl2—O3xv	42.94 (8)	Tl1xxvi—AsB—Tl1	126.1 (5)
O3xiii—Tl2—O3xv	87.33 (9)	Tl1xxii—AsB—Tl1	128.1 (5)
O3xiv—Tl2—O3xv	87.33 (9)	Tl1xxvii—AsB—Tl1	127.5 (5)
O3i—Tl2—AsBxiii	90.6 (3)	Tl2xxvii—AsB—Tl1	166.5 (6)
O3ii—Tl2—AsBxiii	159.8 (4)	Tl1ii—AsB—Tl1	3.1 (3)
O3—Tl2—AsBxiii	116.2 (4)	As—AsB—Tl2	26.4 (7)
O1vii—Tl2—AsBxiii	25.9 (3)	O4iii—AsB—Tl2	87.6 (10)
O1viii—Tl2—AsBxiii	104.1 (4)	O1xxi—AsB—Tl2	44.9 (7)
O1ix—Tl2—AsBxiii	87.9 (4)	O2xxii—AsB—Tl2	128.4 (8)
O4x—Tl2—AsBxiii	21.2 (3)	Tl2xiii—AsB—Tl2	60.8 (3)
O4xi—Tl2—AsBxiii	63.0 (3)	Tl1xxvi—AsB—Tl2	171.8 (6)
O4xii—Tl2—AsBxiii	62.7 (3)	Tl1xxii—AsB—Tl2	174.5 (6)
O3xiii—Tl2—AsBxiii	47.7 (4)	Tl1xxvii—AsB—Tl2	171.0 (6)
O3xiv—Tl2—AsBxiii	42.9 (4)	Tl2xxvii—AsB—Tl2	120.2 (4)
O3xv—Tl2—AsBxiii	99.8 (3)	Tl1ii—AsB—Tl2	48.6 (2)
O3i—Tl2—AsBxv	159.8 (4)	Tl1—AsB—Tl2	48.5 (2)
O3ii—Tl2—AsBxv	116.2 (4)	AsBxxviii—O1—Asxxviii	47.6 (8)
O3—Tl2—AsBxv	90.6 (4)	AsBxxviii—O1—Al2xxix	138.8 (8)
O1vii—Tl2—AsBxv	87.9 (4)	Asxxviii—O1—Al2xxix	137.7 (2)
O1viii—Tl2—AsBxv	25.9 (3)	AsBxxviii—O1—Tl2vii	88.4 (8)
O1ix—Tl2—AsBxv	104.1 (3)	Asxxviii—O1—Tl2vii	88.78 (15)
O4x—Tl2—AsBxv	62.7 (3)	Al2xxix—O1—Tl2vii	126.91 (15)
O4xi—Tl2—AsBxv	21.2 (3)	AsBxxviii—O1—Tl2xxix	75.1 (8)
O4xii—Tl2—AsBxv	63.0 (3)	Asxxviii—O1—Tl2xxix	121.09 (16)
O3xiii—Tl2—AsBxv	42.9 (4)	Al2xxix—O1—Tl2xxix	92.35 (12)
O3xiv—Tl2—AsBxv	99.8 (3)	Tl2vii—O1—Tl2xxix	75.55 (7)
O3xv—Tl2—AsBxv	47.7 (4)	AsBxxviii—O1—Tl2xxviii	119.6 (8)
AsBxiii—Tl2—AsBxv	78.5 (5)	Asxxviii—O1—Tl2xxviii	73.85 (13)
O3i—Tl2—AsBxiv	116.2 (4)	Al2xxix—O1—Tl2xxviii	92.31 (12)
O3ii—Tl2—AsBxiv	90.6 (4)	Tl2vii—O1—Tl2xxviii	75.53 (7)
O3—Tl2—AsBxiv	159.8 (4)	Tl2xxix—O1—Tl2xxviii	146.93 (9)
O1vii—Tl2—AsBxiv	104.1 (4)	As—O2—Al1xxvii	122.5 (2)
O1viii—Tl2—AsBxiv	87.9 (4)	As—O2—AsBxxx	104.8 (6)
O1ix—Tl2—AsBxiv	25.9 (3)	Al1xxvii—O2—AsBxxx	102.5 (6)
O4x—Tl2—AsBxiv	63.0 (3)	As—O2—Tl1ii	100.8 (2)
O4xi—Tl2—AsBxiv	62.7 (3)	Al1xxvii—O2—Tl1ii	128.4 (2)
O4xii—Tl2—AsBxiv	21.2 (3)	AsBxxx—O2—Tl1ii	90.8 (7)
O3xiii—Tl2—AsBxiv	99.8 (3)	As—O2—Tl1	97.2 (3)
O3xiv—Tl2—AsBxiv	47.7 (4)	Al1xxvii—O2—Tl1	130.04 (17)
O3xv—Tl2—AsBxiv	42.9 (4)	AsBxxx—O2—Tl1	94.2 (7)
AsBxiii—Tl2—AsBxiv	78.5 (5)	Tl1ii—O2—Tl1	4.4 (5)
AsBxv—Tl2—AsBxiv	78.5 (5)	As—O2—Tl1i	99.66 (14)
O2xvi—Al1—O2ii	91.34 (17)	Al1xxvii—O2—Tl1i	129.68 (16)
O2xvi—Al1—O2xvii	91.34 (17)	AsBxxx—O2—Tl1i	90.6 (7)
O2ii—Al1—O2xvii	91.34 (17)	Tl1ii—O2—Tl1i	1.27 (13)
O2xvi—Al1—O4xviii	92.20 (15)	Tl1—O2—Tl1i	3.9 (4)
O2ii—Al1—O4xviii	176.43 (17)	As—O2—Tl2	60.21 (10)
O2xvii—Al1—O4xviii	88.17 (15)	Al1xxvii—O2—Tl2	163.54 (15)
O2xvi—Al1—O4i	88.17 (15)	AsBxxx—O2—Tl2	62.4 (6)
O2ii—Al1—O4i	92.20 (16)	Tl1ii—O2—Tl2	61.76 (9)
O2xvii—Al1—O4i	176.43 (18)	Tl1—O2—Tl2	61.25 (6)
O4xviii—Al1—O4i	88.32 (17)	Tl1i—O2—Tl2	60.58 (8)
O2xvi—Al1—O4xix	176.43 (17)	As—O3—Tl2	131.46 (18)
O2ii—Al1—O4xix	88.16 (15)	As—O3—Tl1	105.45 (17)
O2xvii—Al1—O4xix	92.20 (15)	Tl2—O3—Tl1	93.5 (2)
O4xviii—Al1—O4xix	88.32 (17)	As—O3—Tl1ii	102.7 (3)
O4i—Al1—O4xix	88.32 (17)	Tl2—O3—Tl1ii	92.38 (13)
O2xvi—Al1—Tl2xxiii	124.31 (12)	Tl1—O3—Tl1ii	5.0 (5)
O2ii—Al1—Tl2xxiii	124.31 (12)	As—O3—Tl1i	107.1 (3)
O2xvii—Al1—Tl2xxiii	124.31 (12)	Tl2—O3—Tl1i	89.8 (3)
O4xviii—Al1—Tl2xxiii	53.56 (12)	Tl1—O3—Tl1i	3.9 (4)
O4i—Al1—Tl2xxiii	53.56 (12)	Tl1ii—O3—Tl1i	4.5 (5)
O4xix—Al1—Tl2xxiii	53.56 (12)	As—O3—Tl2xiii	83.17 (14)
O2xvi—Al1—Tl1xviii	32.98 (11)	Tl2—O3—Tl2xiii	97.14 (11)
O2ii—Al1—Tl1xviii	104.20 (15)	Tl1—O3—Tl2xiii	156.2 (3)
O2xvii—Al1—Tl1xviii	120.62 (14)	Tl1ii—O3—Tl2xiii	161.0 (3)
O4xviii—Al1—Tl1xviii	79.07 (14)	Tl1i—O3—Tl2xiii	158.83 (12)
O4i—Al1—Tl1xviii	57.99 (12)	AsBiii—O4—Asiii	50.7 (10)
O4xix—Al1—Tl1xviii	143.97 (14)	AsBiii—O4—Al1xxix	170.4 (10)
Tl2xxiii—Al1—Tl1xviii	92.86 (3)	Asiii—O4—Al1xxix	130.5 (2)
O2xvi—Al1—Tl1i	120.61 (14)	AsBiii—O4—Tl2xxxi	88.9 (9)
O2ii—Al1—Tl1i	32.98 (11)	Asiii—O4—Tl2xxxi	84.96 (12)
O2xvii—Al1—Tl1i	104.20 (15)	Al1xxix—O4—Tl2xxxi	100.65 (14)
O4xviii—Al1—Tl1i	143.97 (14)	AsBiii—O4—Tl1xxxii	76.1 (10)
O4i—Al1—Tl1i	79.07 (14)	Asiii—O4—Tl1xxxii	121.76 (16)
O4xix—Al1—Tl1i	57.99 (13)	Al1xxix—O4—Tl1xxxii	98.16 (12)
Tl2xxiii—Al1—Tl1i	92.86 (3)	Tl2xxxi—O4—Tl1xxxii	119.60 (14)
Tl1xviii—Al1—Tl1i	119.753 (11)	AsBiii—O4—Tl1xxviii	77.7 (10)
O2xvi—Al1—Tl1xix	104.20 (16)	Asiii—O4—Tl1xxviii	124.1 (3)
O2ii—Al1—Tl1xix	120.61 (14)	Al1xxix—O4—Tl1xxviii	96.88 (19)
O2xvii—Al1—Tl1xix	32.98 (12)	Tl2xxxi—O4—Tl1xxviii	117.56 (15)
O4xviii—Al1—Tl1xix	57.99 (13)	Tl1xxxii—O4—Tl1xxviii	2.8 (3)
O4i—Al1—Tl1xix	143.97 (14)	AsBiii—O4—Tl1xxxiii	74.5 (10)
O4xix—Al1—Tl1xix	79.07 (15)	Asiii—O4—Tl1xxxiii	120.5 (2)
Tl2xxiii—Al1—Tl1xix	92.86 (4)	Al1xxix—O4—Tl1xxxiii	99.8 (2)
Tl1xviii—Al1—Tl1xix	119.753 (7)	Tl2xxxi—O4—Tl1xxxiii	118.95 (9)
Tl1i—Al1—Tl1xix	119.753 (6)	Tl1xxxii—O4—Tl1xxxiii	1.61 (17)
O2xvi—Al1—Tl1xvi	32.35 (12)	Tl1xxviii—O4—Tl1xxxiii	3.7 (4)
O2ii—Al1—Tl1xvi	106.6 (2)	AsBiii—O4—Tl1	101.3 (10)
O2xvii—Al1—Tl1xvi	118.5 (2)	Asiii—O4—Tl1	53.74 (18)
O4xviii—Al1—Tl1xvi	76.73 (19)	Al1xxix—O4—Tl1	77.44 (19)
O4i—Al1—Tl1xvi	59.94 (18)	Tl2xxxi—O4—Tl1	103.75 (9)
O4xix—Al1—Tl1xvi	144.77 (15)	Tl1xxxii—O4—Tl1	136.34 (9)
Tl2xxiii—Al1—Tl1xvi	92.78 (3)	Tl1xxviii—O4—Tl1	138.6 (2)
Tl1xviii—Al1—Tl1xvi	2.9 (3)	Tl1xxxiii—O4—Tl1	136.76 (8)
Tl1i—Al1—Tl1xvi	122.7 (3)	AsBiii—O4—Tl1i	98.2 (10)
Tl1xix—Al1—Tl1xvi	116.9 (3)	Asiii—O4—Tl1i	51.25 (16)
O2xvi—Al1—Tl1ii	118.5 (2)	Al1xxix—O4—Tl1i	80.3 (2)
O2ii—Al1—Tl1ii	32.35 (12)	Tl2xxxi—O4—Tl1i	105.06 (14)
O2xvii—Al1—Tl1ii	106.6 (2)	Tl1xxxii—O4—Tl1i	134.6 (3)
O4xviii—Al1—Tl1ii	144.77 (15)	Tl1xxviii—O4—Tl1i	136.94 (8)
O4i—Al1—Tl1ii	76.7 (2)	Tl1xxxiii—O4—Tl1i	134.9 (2)
O4xix—Al1—Tl1ii	59.94 (19)	Tl1—O4—Tl1i	3.3 (4)
Tl2xxiii—Al1—Tl1ii	92.78 (3)	AsBiii—O4—Tl2xxxiv	53.0 (10)
Tl1xviii—Al1—Tl1ii	116.9 (3)	Asiii—O4—Tl2xxxiv	97.70 (13)
Tl1i—Al1—Tl1ii	2.9 (3)	Al1xxix—O4—Tl2xxxiv	130.13 (14)
Tl1xix—Al1—Tl1ii	122.7 (3)	Tl2xxxi—O4—Tl2xxxiv	67.31 (5)
Tl1xvi—Al1—Tl1ii	119.767 (7)	Tl1xxxii—O4—Tl2xxxiv	56.91 (9)
O1ix—Al2—O1xv	92.72 (15)	Tl1xxviii—O4—Tl2xxxiv	55.99 (5)
O1ix—Al2—O1xx	92.72 (15)	Tl1xxxiii—O4—Tl2xxxiv	55.69 (6)
O1xv—Al2—O1xx	92.72 (15)	Tl1—O4—Tl2xxxiv	151.34 (16)
O1ix—Al2—O1i	180.0	Tl1i—O4—Tl2xxxiv	148.95 (14)
O1xv—Al2—O1i	87.28 (15)	AsBiii—O4—Tl1ii	99.9 (10)
O1xx—Al2—O1i	87.28 (15)	Asiii—O4—Tl1ii	52.32 (10)
O1ix—Al2—O1xix	87.28 (15)	Al1xxix—O4—Tl1ii	78.86 (11)
O1xv—Al2—O1xix	180.0	Tl2xxxi—O4—Tl1ii	103.45 (10)
O1xx—Al2—O1xix	87.28 (15)	Tl1xxxii—O4—Tl1ii	136.45 (9)
O1i—Al2—O1xix	92.71 (15)	Tl1xxviii—O4—Tl1ii	138.7 (2)
O1ix—Al2—O1xviii	87.28 (15)	Tl1xxxiii—O4—Tl1ii	136.81 (8)
O1xv—Al2—O1xviii	87.28 (15)	Tl1—O4—Tl1ii	1.42 (15)
O1xx—Al2—O1xviii	180.00 (17)	Tl1i—O4—Tl1ii	2.3 (3)
O1i—Al2—O1xviii	92.71 (15)	Tl2xxxiv—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.

Thallium aluminium bis[hydrogen arsenate(V)] (TlAlHAsO42). Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4xxxv	0.87 (4)	1.87 (5)	2.584 (5)	139 (6)

Symmetry code: (xxxv) y, x−1, −z+3/2.

Funding Statement

This work was funded by Doc fForte Fellowship of the Austrian Academy of Sciences to K. Schwendtner grant . Technische Universitat Wien grant .