Octahedral As in M⁺ arsenates - architecture and seven new members

Arsenates with arsenic in octahedral coordination are very rare. The present paper provides an overview of all known M⁺ arsenates(V) containing octahedrally coordinated arsenic (M⁺ = Li, Na, K, Rb, Cs, Ag) and the crystal structures (determined from single-crystal X-ray diffraction data) of the following seven new hydrothermally synthesized members belonging to six different structure types, four of which are novel: LiH₂As₃O₉, LiH₃As₂O₇, NaHAs₂O₆-type KHAs₂O₆, KH₃As₄O₁₂ and isotypic RbH₃As₄O₁₂, CsAs₃O₈ and NaH₂As₃O₉-type AgH₂As₃O₉. The main building unit of these compounds is usually an As₄O₁₄ cluster of two edge-sharing AsO₆ octahedra sharing two apical corners each with two AsO₄ tetrahedra. The different connectivity between these clusters defines the different structure types. The novel CsAs₃O₈ structure, based on a derivative of the As₄O₁₄ cluster, is the most condensed of all these M⁺ arsenates, with an O/As ratio of only 2.67 compared with values of 2.75-3.5 for the remaining members. This is achieved through polymerization of the cluster derivatives to infinite chains of edge-sharing AsO₆ octahedra. The ^[4]As/^[6]As ratio drops to only 0.5. All but two of the protonated title compounds show protonated AsO₆ octahedra. Hydrogen bonds range from very strong to weak. An analysis of bond-length distribution and average bond lengths in AsO₆ octahedra in inorganic compounds leads to an overall mean As-O distance for all known AsO₆ octahedra (with R factors < 0.072) of 1.830 (2) Å.

Computing details

For all compounds, data collection: COLLECT (Nonius, 2003); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO, SCALEPACK (Otwinowski & Minor, 1997). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for CsAs3O8; SHELXS97 (Sheldrick, 1997b) for KH3As4O12, KHAs2O6, LiH2As3O9, LiH3As2O7, RbH3As4O12, aghas. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for CsAs3O8; SHELXL97 (Sheldrick, 1997a) for KH3As4O12, KHAs2O6, LiH2As3O9, LiH3As2O7, RbH3As4O12, aghas. Molecular graphics: DIAMOND (Brandenburg, 2005) for KH3As4O12, KHAs2O6, RbH3As4O12, aghas; Diamond (Brandenburg, 2005) for LiH2As3O9, LiH3As2O7. Software used to prepare material for publication: DIAMOND (Pennington, 1999) for CsAs3O8; SHELXL97 (Sheldrick, 1997a) for KH3As4O12, KHAs2O6, LiH2As3O9, LiH3As2O7, RbH3As4O12, aghas.

Figures

(CsAs3O8) caesium arsenate(V)

Crystal data

As3CsO8	F(000) = 872
Mr = 485.67	Dx = 4.625 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1602 reflections
a = 8.515 (2) Å	θ = 2.0–35.0°
b = 11.690 (2) Å	µ = 19.44 mm^−1
c = 7.595 (2) Å	T = 293 K
β = 112.70 (3)°	Large strongly distorted octahedra, colorless-white
V = 697.5 (3) Å^3	0.10 × 0.08 × 0.07 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1540 independent reflections
Radiation source: fine-focus sealed tube	1433 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ϕ and ω scans	θmax = 34.9°, θmin = 3.1°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −13→13
Tmin = 0.247, Tmax = 0.343	k = −18→18
3021 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 3.3231P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.054	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 2.18 e Å^−3
1540 reflections	Δρmin = −2.13 e Å^−3
57 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0076 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cs1	1.0000	0.57459 (2)	0.7500	0.02180 (8)
As1	0.5000	0.56900 (2)	0.2500	0.00481 (7)
As2	0.62239 (3)	0.326966 (17)	0.42861 (3)	0.00536 (7)
O1	0.3863 (2)	0.65781 (14)	0.3296 (2)	0.0099 (3)
O2	0.6407 (2)	0.48988 (14)	0.4274 (2)	0.0092 (3)
O3	0.60382 (19)	0.32503 (13)	0.1801 (2)	0.0072 (3)
O4	0.85059 (19)	0.32647 (12)	0.5311 (2)	0.0063 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.02409 (12)	0.02356 (13)	0.02206 (12)	0.000	0.01365 (9)	0.000
As1	0.00600 (12)	0.00404 (12)	0.00509 (12)	0.000	0.00292 (9)	0.000
As2	0.00536 (10)	0.00538 (10)	0.00547 (10)	0.00094 (6)	0.00223 (7)	0.00022 (6)
O1	0.0127 (7)	0.0117 (6)	0.0069 (6)	0.0066 (5)	0.0055 (5)	0.0018 (5)
O2	0.0095 (6)	0.0063 (6)	0.0089 (6)	0.0005 (5)	0.0003 (5)	0.0015 (5)
O3	0.0049 (6)	0.0105 (6)	0.0060 (6)	−0.0003 (4)	0.0017 (5)	0.0001 (5)
O4	0.0053 (6)	0.0037 (6)	0.0103 (6)	0.0000 (4)	0.0035 (5)	0.0003 (4)

Geometric parameters (Å, º)

Cs1—O4^i	3.1001 (17)	As1—O2	1.6917 (16)
Cs1—O4^ii	3.1001 (17)	As2—O3^vi	1.7790 (16)
Cs1—O2	3.249 (2)	As2—O4	1.7929 (17)
Cs1—O2^iii	3.249 (2)	As2—O4^vii	1.8192 (15)
Cs1—O4	3.3412 (16)	As2—O3	1.8323 (16)
Cs1—O4^iii	3.3412 (16)	As2—O1^viii	1.8743 (16)
Cs1—O1^iv	3.3973 (18)	As2—O2	1.9111 (17)
Cs1—O1^v	3.3973 (18)	O1—As2^viii	1.8743 (16)
Cs1—O3^i	3.4143 (17)	O1—Cs1^v	3.3973 (18)
Cs1—O3^ii	3.4143 (17)	O3—As2^vi	1.7790 (16)
As1—O1	1.6833 (16)	O3—Cs1^ii	3.4143 (17)
As1—O1^vi	1.6833 (16)	O4—As2^vii	1.8192 (15)
As1—O2^vi	1.6917 (16)	O4—Cs1^ii	3.1001 (17)
O1—As1—O1^vi	103.84 (12)	O4—As2—O1^viii	91.18 (8)
O1—As1—O2^vi	107.13 (8)	O4^vii—As2—O1^viii	88.80 (7)
O1^vi—As1—O2^vi	112.33 (8)	O3—As2—O1^viii	171.84 (7)
O1—As1—O2	112.33 (8)	O3^vi—As2—O2	94.95 (7)
O1^vi—As1—O2	107.13 (8)	O4—As2—O2	85.89 (7)
O2^vi—As1—O2	113.71 (11)	O4^vii—As2—O2	167.97 (7)
O3^vi—As2—O4	178.03 (7)	O3—As2—O2	88.98 (7)
O3^vi—As2—O4^vii	96.29 (7)	O1^viii—As2—O2	86.80 (7)
O4—As2—O4^vii	83.00 (7)	As1—O1—As2^viii	131.00 (9)
O3^vi—As2—O3	82.77 (8)	As1—O2—As2	120.96 (9)
O4—As2—O3	95.48 (8)	As2^vi—O3—As2	97.22 (8)
O4^vii—As2—O3	96.67 (7)	As2—O4—As2^vii	97.00 (7)
O3^vi—As2—O1^viii	90.64 (8)

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

(KH3As4O12)

Crystal data

H3As4KO12	Z = 1
Mr = 533.80	F(000) = 250
Triclinic, P1	Dx = 3.724 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.154 (1) Å	Cell parameters from 1372 reflections
b = 6.967 (1) Å	θ = 2.0–30.0°
c = 7.532 (2) Å	µ = 14.42 mm^−1
α = 63.90 (3)°	T = 293 K
β = 78.61 (3)°	Tabular, colorless
γ = 84.35 (3)°	0.04 × 0.03 × 0.02 mm
V = 238.08 (11) Å^3

Data collection

Nonius KappaCCD diffractometer	1385 independent reflections
Radiation source: fine-focus sealed tube	1188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ϕ and ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −7→7
Tmin = 0.596, Tmax = 0.761	k = −9→9
2699 measured reflections	l = −10→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0232P)^2 + 0.3298P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
1385 reflections	Δρmax = 1.16 e Å^−3
88 parameters	Δρmin = −0.69 e Å^−3
3 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0088 (14)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
As1	0.15941 (6)	0.32325 (5)	0.31381 (4)	0.01042 (10)
As2	0.59525 (6)	0.12332 (5)	0.57182 (4)	0.00935 (10)
K1	0.0000	0.0000	0.0000	0.0278 (3)
O1	0.1124 (5)	0.5399 (4)	0.1092 (4)	0.0212 (5)
O2	0.2311 (4)	0.1122 (3)	0.2556 (3)	0.0123 (4)
O3	0.4206 (4)	0.3691 (3)	0.3965 (3)	0.0126 (4)
O4	0.8891 (4)	0.2875 (4)	0.4964 (3)	0.0137 (5)
O5	0.4846 (5)	0.1902 (4)	0.7722 (3)	0.0147 (5)
O6	0.6943 (4)	0.0371 (3)	0.3739 (3)	0.0105 (4)
H1	0.483 (9)	0.330 (2)	0.730 (6)	0.029 (12)*
H2	0.055 (13)	0.514 (12)	0.018 (8)	0.000 (16)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.00967 (16)	0.00931 (17)	0.01302 (17)	−0.00015 (11)	−0.00398 (12)	−0.00464 (13)
As2	0.00809 (16)	0.00919 (17)	0.01217 (17)	−0.00060 (11)	−0.00259 (11)	−0.00542 (13)
K1	0.0272 (6)	0.0342 (7)	0.0263 (6)	−0.0120 (5)	0.0014 (5)	−0.0172 (5)
O1	0.0353 (15)	0.0110 (11)	0.0161 (12)	−0.0004 (10)	−0.0138 (11)	−0.0009 (10)
O2	0.0144 (11)	0.0100 (11)	0.0139 (11)	0.0025 (8)	−0.0067 (9)	−0.0051 (9)
O3	0.0115 (11)	0.0097 (11)	0.0173 (11)	−0.0004 (8)	−0.0064 (9)	−0.0047 (9)
O4	0.0091 (10)	0.0138 (11)	0.0203 (12)	−0.0026 (8)	0.0004 (8)	−0.0100 (10)
O5	0.0198 (12)	0.0122 (11)	0.0147 (11)	−0.0009 (9)	−0.0012 (9)	−0.0088 (9)
O6	0.0084 (10)	0.0116 (10)	0.0116 (10)	−0.0023 (8)	−0.0003 (8)	−0.0052 (9)

Geometric parameters (Å, º)

As1—O1	1.656 (2)	K1—O1^vii	2.965 (3)
As1—O2	1.699 (2)	K1—O6^viii	3.048 (2)
As1—O3	1.701 (2)	K1—O6^i	3.048 (2)
As1—O4^i	1.704 (2)	K1—O5^ii	3.296 (3)
As2—O5	1.746 (2)	K1—O5^ix	3.296 (3)
As2—O6	1.808 (2)	O1—K1^x	2.965 (3)
As2—O6^ii	1.824 (2)	O1—H2	0.89 (2)
As2—O4	1.831 (2)	O2—As2^ii	1.864 (2)
As2—O2^ii	1.864 (2)	O4—As1^xi	1.704 (2)
As2—O3	1.914 (2)	O5—K1^xii	2.810 (3)
K1—O5^iii	2.810 (3)	O5—K1^xiii	3.296 (3)
K1—O5^iv	2.810 (3)	O5—H1	0.885 (14)
K1—O2^v	2.855 (2)	O6—As2^ii	1.824 (2)
K1—O2	2.855 (2)	O6—K1^xi	3.048 (2)
K1—O1^vi	2.965 (3)
O1—As1—O2	109.28 (12)	O6—As2—O2^ii	90.52 (10)
O1—As1—O3	107.65 (12)	O6^ii—As2—O2^ii	91.23 (10)
O2—As1—O3	109.48 (11)	O4—As2—O2^ii	90.85 (10)
O1—As1—O4^i	109.01 (13)	O5—As2—O3	91.26 (11)
O2—As1—O4^i	114.03 (11)	O6—As2—O3	90.36 (10)
O3—As1—O4^i	107.19 (11)	O6^ii—As2—O3	89.82 (10)
O5—As2—O6	175.78 (10)	O4—As2—O3	88.15 (10)
O5—As2—O6^ii	93.74 (11)	O2^ii—As2—O3	178.71 (9)
O6—As2—O6^ii	82.36 (10)	As1—O2—As2^ii	117.79 (12)
O5—As2—O4	90.45 (11)	As1—O3—As2	116.78 (12)
O6—As2—O4	93.51 (10)	As1^xi—O4—As2	131.02 (13)
O6^ii—As2—O4	175.39 (9)	As2—O6—As2^ii	97.64 (10)
O5—As2—O2^ii	87.93 (11)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) x, y, z−1; (v) −x, −y, −z; (vi) −x, −y+1, −z; (vii) x, y−1, z; (viii) −x+1, −y, −z; (ix) x−1, y, z−1; (x) x, y+1, z; (xi) x+1, y, z; (xii) x, y, z+1; (xiii) x+1, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O3^xiv	0.89 (1)	1.95 (2)	2.810 (3)	164 (4)
O1—H2···O1^vi	0.89 (2)	1.58 (2)	2.458 (5)	166 (7)

Symmetry codes: (vi) −x, −y+1, −z; (xiv) −x+1, −y+1, −z+1.

(KHAs2O6)

Crystal data

HAs2KO6	F(000) = 536
Mr = 285.95	Dx = 3.574 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2028 reflections
a = 6.051 (1) Å	θ = 2.0–32.6°
b = 9.727 (2) Å	µ = 13.31 mm^−1
c = 9.054 (2) Å	T = 293 K
β = 94.21 (3)°	Tabular-rhombic, colorless
V = 531.46 (18) Å^3	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1922 independent reflections
Radiation source: fine-focus sealed tube	1785 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
ϕ and ω scans	θmax = 32.6°, θmin = 3.1°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.298, Tmax = 0.416	k = −14→14
3747 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	All H-atom parameters refined
wR(F^2) = 0.043	w = 1/[σ^2(Fo^2) + (0.0205P)^2 + 0.3321P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
1922 reflections	Δρmax = 0.71 e Å^−3
87 parameters	Δρmin = −0.77 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0092 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
As1	0.15969 (3)	0.113747 (16)	0.743672 (17)	0.00850 (5)
As2	0.11196 (3)	0.402289 (15)	0.584511 (17)	0.00748 (5)
K1	0.61363 (6)	0.19249 (4)	0.46790 (5)	0.01957 (9)
O1	0.3895 (2)	0.06388 (14)	0.67443 (15)	0.0164 (2)
O2	0.2036 (2)	0.18489 (13)	0.91503 (13)	0.0153 (2)
O3	0.0282 (2)	0.48279 (13)	0.75982 (13)	0.0156 (2)
O4	0.01033 (19)	0.23438 (12)	0.64102 (13)	0.0117 (2)
O5	0.3782 (2)	0.37388 (13)	0.66877 (15)	0.0130 (2)
O6	0.16351 (19)	0.56982 (12)	0.50484 (14)	0.0117 (2)
H1	0.434 (5)	0.438 (3)	0.706 (3)	0.030 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.01098 (8)	0.00661 (8)	0.00785 (8)	−0.00003 (5)	0.00028 (5)	0.00136 (5)
As2	0.00878 (8)	0.00552 (8)	0.00796 (8)	0.00064 (5)	−0.00055 (5)	0.00034 (5)
K1	0.01754 (18)	0.01522 (18)	0.0258 (2)	−0.00280 (13)	0.00040 (14)	−0.00283 (14)
O1	0.0147 (6)	0.0133 (6)	0.0215 (6)	0.0052 (4)	0.0039 (5)	0.0019 (5)
O2	0.0254 (6)	0.0131 (6)	0.0075 (5)	−0.0101 (5)	0.0013 (4)	−0.0003 (4)
O3	0.0251 (6)	0.0127 (6)	0.0090 (5)	0.0097 (5)	0.0006 (4)	−0.0008 (4)
O4	0.0122 (5)	0.0065 (5)	0.0158 (5)	−0.0008 (4)	−0.0028 (4)	0.0040 (4)
O5	0.0102 (5)	0.0105 (5)	0.0175 (6)	0.0005 (4)	−0.0052 (4)	−0.0010 (4)
O6	0.0103 (5)	0.0077 (5)	0.0164 (5)	−0.0009 (4)	−0.0026 (4)	0.0045 (4)

Geometric parameters (Å, º)

As1—O1	1.6403 (13)	K1—O4^v	2.7988 (15)
As1—O2	1.7018 (12)	K1—O1^vi	2.8064 (15)
As1—O3^i	1.7061 (12)	K1—O5	2.9714 (15)
As1—O4	1.7130 (12)	K1—O5^iii	3.0356 (16)
As2—O5	1.7534 (13)	O1—K1^vi	2.8064 (15)
As2—O6	1.8183 (12)	O2—As2^vii	1.8723 (12)
As2—O6^ii	1.8190 (12)	O2—K1^vii	2.7631 (14)
As2—O4	1.8312 (12)	O3—As1^viii	1.7061 (12)
As2—O2^iii	1.8723 (12)	O4—K1^ix	2.7988 (15)
As2—O3	1.8728 (12)	O5—K1^vii	3.0356 (16)
K1—O6^iv	2.6789 (13)	O5—H1	0.77 (3)
K1—O1	2.6967 (15)	O6—As2^ii	1.8190 (12)
K1—O2^iii	2.7631 (14)	O6—K1^iv	2.6789 (13)
O1—As1—O2	112.88 (7)	O1—K1—O2^iii	80.19 (4)
O1—As1—O3^i	110.77 (7)	O6^iv—K1—O4^v	54.37 (3)
O2—As1—O3^i	112.31 (6)	O1—K1—O4^v	97.67 (4)
O1—As1—O4	115.06 (6)	O2^iii—K1—O4^v	139.17 (4)
O2—As1—O4	104.89 (7)	O6^iv—K1—O1^vi	142.72 (4)
O3^i—As1—O4	100.20 (6)	O1—K1—O1^vi	85.37 (4)
O5—As2—O6	97.75 (6)	O2^iii—K1—O1^vi	109.16 (4)
O5—As2—O6^ii	179.24 (6)	O4^v—K1—O1^vi	111.30 (4)
O6—As2—O6^ii	82.42 (6)	O6^iv—K1—O5	72.05 (4)
O5—As2—O4	93.13 (6)	O1—K1—O5	64.09 (4)
O6—As2—O4	168.82 (5)	O2^iii—K1—O5	52.05 (4)
O6^ii—As2—O4	86.66 (5)	O4^v—K1—O5	90.04 (4)
O5—As2—O2^iii	88.13 (6)	O1^vi—K1—O5	145.21 (4)
O6—As2—O2^iii	90.63 (6)	O6^iv—K1—O5^iii	117.77 (4)
O6^ii—As2—O2^iii	91.13 (6)	O1—K1—O5^iii	107.05 (4)
O4—As2—O2^iii	87.17 (6)	O2^iii—K1—O5^iii	65.20 (4)
O5—As2—O3	89.68 (6)	O4^v—K1—O5^iii	149.06 (4)
O6—As2—O3	91.52 (6)	O1^vi—K1—O5^iii	54.15 (4)
O6^ii—As2—O3	91.06 (6)	O5—K1—O5^iii	117.24 (4)
O4—As2—O3	91.08 (6)	As1—O2—As2^vii	121.82 (7)
O2^iii—As2—O3	177.12 (5)	As1^viii—O3—As2	121.19 (7)
O6^iv—K1—O1	127.72 (4)	As1—O4—As2	126.01 (7)
O6^iv—K1—O2^iii	94.76 (4)	As2—O6—As2^ii	97.58 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1^x	0.77 (3)	1.91 (3)	2.6669 (18)	167 (3)

Symmetry code: (x) −x+1, y+1/2, −z+3/2.

(LiH2As3O9)

Crystal data

H2As3LiO9	F(000) = 704
Mr = 377.72	Dx = 3.443 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2800 reflections
a = 9.666 (2) Å	θ = 2.0–32.6°
b = 8.553 (2) Å	µ = 13.70 mm^−1
c = 9.970 (2) Å	T = 293 K
β = 117.86 (3)°	Large plates, colorless
V = 728.7 (3) Å^3	0.15 × 0.08 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2642 independent reflections
Radiation source: fine-focus sealed tube	2426 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
ϕ and ω scans	θmax = 32.6°, θmin = 2.4°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.233, Tmax = 0.407	k = −12→12
5128 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.041	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 0.613P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
2642 reflections	Δρmax = 0.67 e Å^−3
127 parameters	Δρmin = −0.86 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0087 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Li1	0.1185 (4)	0.3960 (5)	−0.0064 (4)	0.0214 (7)
As1	0.678516 (18)	0.31828 (2)	0.246046 (18)	0.00675 (5)
As2	0.23643 (2)	0.74101 (2)	0.14218 (2)	0.01002 (5)
As3	0.512553 (18)	0.621549 (19)	0.093417 (18)	0.00611 (5)
O1	0.57329 (15)	0.22161 (17)	0.30721 (15)	0.0143 (3)
O2	0.87509 (14)	0.29929 (15)	0.35492 (14)	0.0099 (2)
O3	0.64351 (14)	0.27106 (15)	0.06575 (13)	0.0087 (2)
O4	0.66646 (14)	0.51858 (15)	0.25973 (13)	0.0096 (2)
O5	0.10202 (16)	0.61787 (17)	0.03233 (16)	0.0163 (3)
O6	0.2219 (2)	0.92498 (18)	0.07138 (18)	0.0226 (3)
O7	0.23344 (17)	0.77879 (18)	0.30912 (16)	0.0169 (3)
O8	0.42371 (14)	0.67263 (16)	0.21032 (14)	0.0111 (2)
O9	0.40428 (14)	0.43919 (14)	0.02858 (13)	0.0080 (2)
H1	0.207 (5)	0.913 (6)	−0.022 (3)	0.081 (14)*
H2	0.138 (4)	0.770 (4)	0.291 (4)	0.042 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.0224 (18)	0.0220 (18)	0.0200 (16)	−0.0033 (14)	0.0100 (15)	−0.0079 (14)
As1	0.00585 (8)	0.00740 (8)	0.00668 (8)	0.00064 (5)	0.00266 (6)	0.00099 (5)
As2	0.00831 (8)	0.01084 (9)	0.01156 (8)	0.00031 (6)	0.00517 (7)	−0.00260 (6)
As3	0.00527 (8)	0.00650 (8)	0.00599 (7)	−0.00004 (5)	0.00214 (6)	−0.00063 (5)
O1	0.0107 (6)	0.0182 (7)	0.0164 (6)	−0.0005 (5)	0.0083 (5)	0.0060 (5)
O2	0.0060 (5)	0.0081 (5)	0.0110 (5)	0.0015 (4)	0.0002 (4)	0.0009 (4)
O3	0.0078 (5)	0.0103 (6)	0.0059 (5)	0.0033 (4)	0.0015 (4)	−0.0003 (4)
O4	0.0091 (5)	0.0083 (5)	0.0071 (5)	0.0021 (4)	0.0003 (4)	−0.0002 (4)
O5	0.0105 (6)	0.0185 (7)	0.0194 (6)	−0.0035 (5)	0.0065 (5)	−0.0085 (5)
O6	0.0337 (9)	0.0131 (7)	0.0241 (7)	0.0054 (6)	0.0159 (7)	0.0027 (6)
O7	0.0131 (6)	0.0253 (7)	0.0161 (6)	−0.0020 (5)	0.0100 (5)	−0.0069 (5)
O8	0.0085 (5)	0.0172 (6)	0.0084 (5)	0.0017 (4)	0.0047 (4)	−0.0016 (4)
O9	0.0084 (5)	0.0077 (5)	0.0090 (5)	−0.0014 (4)	0.0051 (4)	−0.0015 (4)

Geometric parameters (Å, º)

Li1—O5	1.958 (4)	As3—O2^iv	1.7980 (13)
Li1—O1^i	1.974 (4)	As3—O9^v	1.8192 (12)
Li1—O5^ii	2.027 (4)	As3—O9	1.8203 (12)
Li1—O7^iii	2.072 (4)	As3—O3^v	1.8440 (13)
Li1—O9	2.643 (4)	As3—O4	1.8528 (13)
Li1—Li1^ii	2.950 (8)	As3—As3^v	2.7256 (5)
As1—O1	1.6339 (13)	O1—Li1^vi	1.974 (4)
As1—O2	1.6993 (14)	O2—As3^vii	1.7980 (13)
As1—O3	1.7148 (12)	O3—As3^v	1.8440 (13)
As1—O4	1.7268 (13)	O5—Li1^ii	2.027 (4)
As2—O5	1.6330 (14)	O6—H1	0.877 (19)
As2—O6	1.7033 (16)	O7—Li1^viii	2.072 (4)
As2—O7	1.7090 (14)	O7—H2	0.86 (4)
As2—O8	1.7122 (13)	O9—As3^v	1.8192 (12)
As3—O8	1.7951 (13)
O5—Li1—O1^i	132.6 (2)	O5—As2—O8	114.09 (7)
O5—Li1—O5^ii	84.51 (16)	O6—As2—O8	110.29 (7)
O1^i—Li1—O5^ii	95.34 (17)	O7—As2—O8	100.02 (7)
O5—Li1—O7^iii	111.44 (18)	O8—As3—O2^iv	90.94 (6)
O1^i—Li1—O7^iii	113.4 (2)	O8—As3—O9^v	176.95 (6)
O5^ii—Li1—O7^iii	108.14 (19)	O2^iv—As3—O9^v	92.09 (6)
O5—Li1—O9	90.86 (15)	O8—As3—O9	93.95 (6)
O1^i—Li1—O9	87.33 (14)	O2^iv—As3—O9	175.02 (6)
O5^ii—Li1—O9	175.3 (2)	O9^v—As3—O9	83.01 (6)
O7^iii—Li1—O9	74.13 (13)	O8—As3—O3^v	89.45 (6)
O5—Li1—Li1^ii	43.17 (11)	O2^iv—As3—O3^v	88.12 (6)
O1^i—Li1—Li1^ii	120.9 (2)	O9^v—As3—O3^v	90.36 (6)
O5^ii—Li1—Li1^ii	41.34 (11)	O9—As3—O3^v	91.02 (6)
O7^iii—Li1—Li1^ii	117.2 (2)	O8—As3—O4	87.84 (6)
O9—Li1—Li1^ii	134.0 (2)	O2^iv—As3—O4	91.18 (6)
O1—As1—O2	114.74 (7)	O9^v—As3—O4	92.40 (6)
O1—As1—O3	114.82 (7)	O9—As3—O4	89.92 (6)
O2—As1—O3	105.14 (7)	O3^v—As3—O4	177.18 (5)
O1—As1—O4	113.31 (7)	As1—O2—As3^vii	127.53 (7)
O2—As1—O4	98.10 (6)	As1—O3—As3^v	117.79 (7)
O3—As1—O4	109.21 (6)	As1—O4—As3	117.16 (7)
O5—As2—O6	115.61 (8)	As2—O8—As3	124.29 (7)
O5—As2—O7	113.89 (7)	As3^v—O9—As3	96.99 (6)
O6—As2—O7	101.15 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1···O4^ix	0.88 (2)	2.11 (3)	2.936 (2)	157 (4)
O6—H1···O3^v	0.88 (2)	2.31 (4)	2.834 (2)	118 (4)
O7—H2···O1^viii	0.86 (4)	1.85 (4)	2.676 (2)	161 (3)

Symmetry codes: (v) −x+1, −y+1, −z; (viii) −x+1/2, y+1/2, −z+1/2; (ix) x−1/2, −y+3/2, z−1/2.

(LiH3As2O7)

Crystal data

H3As2LiO7	F(000) = 512
Mr = 271.80	Dx = 3.398 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1018 reflections
a = 11.456 (2) Å	θ = 2.0–32.6°
b = 9.133 (2) Å	µ = 12.55 mm^−1
c = 5.630 (1) Å	T = 293 K
β = 115.56 (3)°	Irregular fragment, colorless
V = 531.4 (2) Å^3	0.08 × 0.07 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1020 independent reflections
Radiation source: fine-focus sealed tube	924 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
ϕ and ω scans	θmax = 32.6°, θmin = 3.0°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −17→17
Tmin = 0.433, Tmax = 0.520	k = −13→13
1933 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	All H-atom parameters refined
wR(F^2) = 0.041	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 0.9444P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
1020 reflections	Δρmax = 1.04 e Å^−3
61 parameters	Δρmin = −0.55 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Li1	0.5000	0.3467 (5)	1.0000	0.0192 (9)
As1	0.27148 (2)	0.0000	0.04473 (4)	0.00887 (7)
As2	0.5000	0.15318 (2)	0.5000	0.00829 (7)
O1	0.13472 (17)	0.0000	0.0696 (4)	0.0144 (3)
O2	0.36385 (12)	0.15401 (13)	0.1637 (2)	0.0127 (2)
O3	0.23459 (17)	0.0000	−0.2852 (3)	0.0122 (3)
O4	0.42544 (13)	0.28002 (15)	0.6282 (2)	0.0157 (2)
O5	0.42362 (16)	0.0000	0.5892 (3)	0.0105 (3)
H1	0.384 (3)	0.334 (3)	0.531 (6)	0.036 (9)*
H2	0.290 (5)	0.0000	−0.303 (9)	0.045 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.018 (2)	0.020 (2)	0.016 (2)	0.000	0.0042 (18)	0.000
As1	0.00689 (11)	0.01061 (12)	0.00783 (11)	0.000	0.00198 (8)	0.000
As2	0.00846 (11)	0.00755 (11)	0.00799 (11)	0.000	0.00273 (8)	0.000
O1	0.0100 (7)	0.0167 (8)	0.0191 (8)	0.000	0.0088 (7)	0.000
O2	0.0113 (5)	0.0106 (5)	0.0105 (5)	−0.0011 (4)	−0.0007 (4)	0.0008 (4)
O3	0.0102 (8)	0.0182 (8)	0.0086 (7)	0.000	0.0044 (6)	0.000
O4	0.0189 (6)	0.0141 (6)	0.0122 (5)	0.0079 (5)	0.0050 (5)	−0.0009 (5)
O5	0.0112 (7)	0.0082 (7)	0.0147 (7)	0.000	0.0080 (6)	0.000

Geometric parameters (Å, º)

Li1—O4	1.985 (2)	As2—O4^v	1.7675 (13)
Li1—O4^i	1.985 (2)	As2—O4	1.7675 (13)
Li1—O1^ii	1.993 (4)	As2—O5^vi	1.8313 (11)
Li1—O1^iii	1.993 (4)	As2—O5	1.8313 (11)
As1—O1	1.6319 (18)	As2—O2^v	1.8628 (14)
As1—O2	1.7132 (12)	As2—O2	1.8628 (14)
As1—O2^iv	1.7132 (12)	O3—H2	0.68 (5)
As1—O3	1.7178 (18)	O4—H1	0.74 (3)
O4—Li1—O4^i	144.3 (3)	O4—As2—O5^vi	169.99 (6)
O4—Li1—O1^ii	111.55 (11)	O4^v—As2—O5	169.99 (6)
O4^i—Li1—O1^ii	93.66 (9)	O4—As2—O5	90.95 (6)
O4—Li1—O1^iii	93.66 (9)	O5^vi—As2—O5	80.38 (8)
O4^i—Li1—O1^iii	111.55 (11)	O4^v—As2—O2^v	94.13 (6)
O1^ii—Li1—O1^iii	90.8 (2)	O4—As2—O2^v	85.56 (6)
O4—Li1—Li1^vii	107.87 (14)	O5^vi—As2—O2^v	89.55 (7)
O4^i—Li1—Li1^vii	107.87 (14)	O5—As2—O2^v	90.81 (7)
O1^ii—Li1—Li1^vii	45.39 (10)	O4^v—As2—O2	85.56 (6)
O1^iii—Li1—Li1^vii	45.39 (10)	O4—As2—O2	94.13 (6)
O1—As1—O2	114.86 (5)	O5^vi—As2—O2	90.81 (7)
O1—As1—O2^iv	114.86 (5)	O5—As2—O2	89.55 (7)
O2—As1—O2^iv	110.37 (8)	O2^v—As2—O2	179.53 (7)
O1—As1—O3	107.17 (10)	As1—O2—As2	119.94 (7)
O2—As1—O3	104.18 (6)	As1—O3—H2	110 (4)
O2^iv—As1—O3	104.18 (6)	As2—O4—H1	114 (2)
O4^v—As2—O4	98.10 (9)	Li1—O4—H1	115 (2)
O4^v—As2—O5^vi	90.95 (6)	As2—O5—As2^vi	99.62 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O3^viii	0.74 (3)	2.11 (3)	2.8410 (19)	174 (3)
O3—H2···O5^ix	0.68 (5)	1.87 (5)	2.552 (2)	171 (5)

Symmetry codes: (viii) −x+1/2, −y+1/2, −z; (ix) x, y, z−1.

(RbH3As4O12)

Crystal data

H3As4O12Rb	Z = 1
Mr = 580.17	F(000) = 268
Triclinic, P1	Dx = 3.879 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.169 (1) Å	Cell parameters from 2175 reflections
b = 7.036 (1) Å	θ = 2.0–35.0°
c = 7.766 (2) Å	µ = 18.27 mm^−1
α = 63.31 (3)°	T = 293 K
β = 79.87 (3)°	Tabular, colorless
γ = 84.38 (3)°	0.17 × 0.13 × 0.05 mm
V = 248.36 (11) Å^3

Data collection

Nonius KappaCCD diffractometer	2190 independent reflections
Radiation source: fine-focus sealed tube	1995 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 35.0°, θmin = 3.0°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.147, Tmax = 0.462	k = −11→11
4335 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 0.1743P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2190 reflections	Δρmax = 1.37 e Å^−3
88 parameters	Δρmin = −1.59 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.059 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
As1	0.15396 (4)	0.32137 (3)	0.31490 (3)	0.00901 (8)
As2	0.59768 (4)	0.12418 (3)	0.56642 (3)	0.00815 (8)
Rb1	0.0000	0.0000	0.0000	0.01993 (9)
O1	0.1052 (4)	0.5354 (3)	0.1122 (3)	0.0209 (4)
O2	0.2239 (3)	0.1092 (3)	0.2642 (2)	0.0116 (3)
O3	0.4152 (3)	0.3674 (2)	0.3963 (3)	0.0109 (3)
O4	0.8874 (3)	0.2888 (3)	0.4888 (3)	0.0129 (3)
O5	0.4984 (4)	0.1927 (3)	0.7587 (3)	0.0131 (3)
O6	0.6886 (3)	0.0366 (3)	0.3769 (2)	0.0101 (3)
H1	0.502 (8)	0.328 (3)	0.712 (6)	0.030 (11)*
H2	0.053 (16)	0.486 (13)	0.035 (11)	0.022 (19)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.00904 (11)	0.00758 (12)	0.01041 (12)	−0.00053 (7)	−0.00326 (7)	−0.00325 (8)
As2	0.00761 (11)	0.00791 (12)	0.01007 (12)	−0.00086 (7)	−0.00199 (7)	−0.00459 (8)
Rb1	0.02122 (17)	0.02220 (18)	0.01891 (17)	−0.00591 (12)	−0.00134 (12)	−0.01081 (14)
O1	0.0342 (11)	0.0093 (7)	0.0167 (8)	0.0004 (7)	−0.0135 (8)	−0.0002 (6)
O2	0.0140 (7)	0.0095 (7)	0.0126 (7)	0.0010 (5)	−0.0055 (5)	−0.0050 (6)
O3	0.0096 (6)	0.0076 (6)	0.0153 (7)	−0.0005 (5)	−0.0055 (5)	−0.0036 (5)
O4	0.0079 (6)	0.0134 (7)	0.0206 (8)	−0.0023 (5)	−0.0003 (5)	−0.0107 (6)
O5	0.0178 (7)	0.0116 (7)	0.0128 (7)	−0.0011 (6)	−0.0005 (6)	−0.0083 (6)
O6	0.0087 (6)	0.0101 (7)	0.0128 (7)	−0.0020 (5)	−0.0005 (5)	−0.0061 (5)

Geometric parameters (Å, º)

As1—O1	1.657 (2)	Rb1—O1^vii	3.000 (2)
As1—O2	1.6994 (17)	Rb1—O6^i	3.1878 (19)
As1—O3	1.7024 (16)	Rb1—O6^viii	3.1878 (19)
As1—O4^i	1.7043 (18)	Rb1—O5^ii	3.288 (2)
As2—O5	1.7474 (18)	Rb1—O5^ix	3.288 (2)
As2—O6	1.8116 (17)	O1—Rb1^x	3.000 (2)
As2—O6^ii	1.8208 (17)	O1—H2	0.901 (10)
As2—O4	1.8281 (17)	O2—As2^ii	1.8618 (18)
As2—O2^ii	1.8618 (18)	O4—As1^xi	1.7043 (18)
As2—O3	1.9119 (18)	O5—Rb1^xii	2.948 (2)
Rb1—O2^iii	2.9264 (18)	O5—Rb1^xiii	3.288 (2)
Rb1—O2	2.9264 (18)	O5—H1	0.852 (19)
Rb1—O5^iv	2.948 (2)	O6—As2^ii	1.8208 (17)
Rb1—O5^v	2.948 (2)	O6—Rb1^xi	3.1878 (19)
Rb1—O1^vi	3.000 (2)
O1—As1—O2	109.12 (10)	O6—As2—O2^ii	90.53 (8)
O1—As1—O3	107.75 (10)	O6^ii—As2—O2^ii	90.96 (8)
O2—As1—O3	109.49 (8)	O4—As2—O2^ii	91.22 (8)
O1—As1—O4^i	109.11 (11)	O5—As2—O3	91.04 (8)
O2—As1—O4^i	114.02 (8)	O6—As2—O3	90.81 (8)
O3—As1—O4^i	107.15 (8)	O6^ii—As2—O3	89.75 (7)
O5—As2—O6	176.13 (8)	O4—As2—O3	88.18 (8)
O5—As2—O6^ii	94.20 (8)	O2^ii—As2—O3	178.56 (7)
O6—As2—O6^ii	82.40 (8)	As1—O2—As2^ii	118.33 (9)
O5—As2—O4	90.07 (8)	As1—O3—As2	117.10 (9)
O6—As2—O4	93.39 (8)	As1^xi—O4—As2	131.55 (10)
O6^ii—As2—O4	175.28 (8)	As2—O6—As2^ii	97.60 (8)
O5—As2—O2^ii	87.66 (8)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z; (iv) −x, −y, −z+1; (v) x, y, z−1; (vi) x, y−1, z; (vii) −x, −y+1, −z; (viii) −x+1, −y, −z; (ix) x−1, y, z−1; (x) x, y+1, z; (xi) x+1, y, z; (xii) x, y, z+1; (xiii) x+1, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O3^xiv	0.85 (2)	1.98 (2)	2.822 (3)	169 (4)
O1—H2···O1^vii	0.90 (1)	1.58 (3)	2.453 (4)	161 (8)

Symmetry codes: (vii) −x, −y+1, −z; (xiv) −x+1, −y+1, −z+1.

(aghas)

Crystal data

H2AgAs3O9	Z = 2
Mr = 478.65	F(000) = 440
Triclinic, P1	Dx = 4.481 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.162 (1) Å	Cell parameters from 2510 reflections
b = 7.678 (2) Å	θ = 2.0–32.6°
c = 7.880 (2) Å	µ = 16.75 mm^−1
α = 110.72 (3)°	T = 293 K
β = 106.47 (3)°	Tabular (010) and dogtoothshaped, colorless
γ = 105.43 (3)°	0.15 × 0.13 × 0.08 mm
V = 354.8 (2) Å^3

Data collection

Nonius KappaCCD diffractometer	2568 independent reflections
Radiation source: fine-focus sealed tube	2375 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 32.5°, θmin = 3.0°
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997)	h = −10→10
Tmin = 0.188, Tmax = 0.348	k = −11→11
4992 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0459P)^2 + 0.211P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
2568 reflections	Δρmax = 1.58 e Å^−3
127 parameters	Δρmin = −2.35 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.068 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ag1	0.29467 (4)	0.83089 (4)	0.03990 (4)	0.02037 (9)
As1	0.37356 (4)	0.35261 (4)	0.16800 (4)	0.00767 (9)
As2	0.15704 (4)	0.43698 (4)	0.47710 (4)	0.00670 (8)
As3	0.18233 (4)	0.83030 (4)	0.45233 (4)	0.00769 (9)
O1	0.4016 (4)	0.1497 (3)	0.0425 (4)	0.0170 (4)
O2	0.2838 (4)	0.4695 (4)	0.0365 (4)	0.0168 (4)
O3	0.0921 (4)	0.7891 (4)	0.2202 (3)	0.0150 (4)
O4	0.1943 (3)	0.2882 (3)	0.2650 (3)	0.0114 (4)
O5	0.0859 (3)	0.5645 (3)	0.6783 (3)	0.0091 (4)
O6	0.3937 (3)	0.4439 (3)	0.6456 (3)	0.0104 (4)
O7	0.3805 (4)	0.0667 (3)	0.6158 (3)	0.0140 (4)
O8	0.0124 (3)	0.1890 (3)	0.4597 (3)	0.0107 (4)
O9	0.3147 (3)	0.6836 (3)	0.4989 (3)	0.0100 (4)
H1	0.168 (5)	0.366 (6)	−0.063 (6)	0.044 (16)*
H2	0.347 (9)	0.164 (10)	0.602 (10)	0.050 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.02240 (15)	0.01973 (14)	0.02115 (14)	0.00676 (10)	0.01377 (11)	0.00942 (10)
As1	0.00758 (14)	0.00779 (14)	0.00823 (14)	0.00386 (10)	0.00388 (11)	0.00336 (10)
As2	0.00590 (14)	0.00767 (14)	0.00857 (14)	0.00411 (10)	0.00373 (11)	0.00434 (10)
As3	0.00693 (14)	0.00798 (14)	0.00944 (14)	0.00342 (10)	0.00380 (10)	0.00479 (10)
O1	0.0202 (11)	0.0107 (9)	0.0220 (11)	0.0081 (8)	0.0145 (10)	0.0038 (8)
O2	0.0145 (11)	0.0175 (11)	0.0157 (10)	0.0055 (9)	0.0008 (9)	0.0100 (9)
O3	0.0141 (10)	0.0227 (11)	0.0110 (9)	0.0076 (9)	0.0051 (8)	0.0109 (8)
O4	0.0115 (9)	0.0103 (9)	0.0124 (9)	0.0041 (7)	0.0086 (8)	0.0026 (7)
O5	0.0084 (9)	0.0112 (9)	0.0089 (8)	0.0057 (7)	0.0044 (7)	0.0041 (7)
O6	0.0059 (8)	0.0093 (9)	0.0132 (9)	0.0034 (7)	0.0003 (8)	0.0049 (7)
O7	0.0090 (9)	0.0073 (9)	0.0182 (10)	0.0006 (7)	0.0012 (8)	0.0036 (8)
O8	0.0103 (9)	0.0100 (9)	0.0174 (9)	0.0057 (7)	0.0098 (8)	0.0079 (7)
O9	0.0083 (9)	0.0097 (9)	0.0167 (9)	0.0059 (7)	0.0069 (8)	0.0081 (7)

Geometric parameters (Å, º)

Ag1—O3	2.339 (2)	As2—O4	1.799 (2)
Ag1—O1^i	2.353 (2)	As2—O6	1.807 (2)
Ag1—O1^ii	2.423 (2)	As2—O5^v	1.816 (2)
Ag1—O5^iii	2.524 (3)	As2—O5	1.832 (2)
Ag1—O7^iv	2.707 (3)	As2—O8	1.844 (2)
Ag1—O2	2.745 (2)	As2—O9	1.848 (2)
As1—O1	1.623 (2)	As3—O3	1.636 (2)
As1—O2	1.697 (2)	As3—O7^i	1.705 (2)
As1—O4	1.721 (2)	As3—O8^v	1.720 (2)
As1—O6^iv	1.726 (2)	As3—O9	1.722 (2)
O1—As1—O2	115.73 (12)	O5^v—As2—O8	92.49 (10)
O1—As1—O4	108.87 (11)	O5—As2—O8	89.68 (10)
O2—As1—O4	106.92 (12)	O4—As2—O9	93.94 (10)
O1—As1—O6^iv	115.47 (12)	O6—As2—O9	90.47 (10)
O2—As1—O6^iv	99.01 (11)	O5^v—As2—O9	90.31 (10)
O4—As1—O6^iv	110.26 (10)	O5—As2—O9	91.55 (10)
O4—As2—O6	90.79 (10)	O8—As2—O9	177.06 (9)
O4—As2—O5^v	92.92 (10)	O3—As3—O7^i	113.81 (12)
O6—As2—O5^v	176.15 (9)	O3—As3—O8^v	112.52 (12)
O4—As2—O5	173.01 (10)	O7^i—As3—O8^v	105.29 (11)
O6—As2—O5	93.49 (10)	O3—As3—O9	114.54 (11)
O5^v—As2—O5	82.72 (10)	O7^i—As3—O9	99.30 (11)
O4—As2—O8	85.04 (10)	O8^v—As3—O9	110.31 (10)
O6—As2—O8	86.78 (10)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O3^vi	0.88 (2)	1.70 (2)	2.551 (4)	162 (5)
O7—H2···O6	0.87 (6)	1.97 (7)	2.796 (3)	157 (6)

Symmetry code: (vi) −x, −y+1, −z.