Thallium(III) selenite, Tl2(SeO3)3

Harrison, W.T.A.

doi:10.1107/S0108270105018111

inorganic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 7| July 2005| Pages i76-i78

doi:10.1107/S0108270105018111

Thallium(III) selenite, Tl₂(SeO₃)₃

William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 17 May 2005; accepted 7 June 2005; online 22 June 2005)

The structure of Tl₂(SeO₃)₃ [dithallium(III) triselenium(IV) nonaoxide] is monoclinic (P2₁/n symmetry), with all atoms in general positions. It is built up from TlO₆ octahedra, distorted TlO₇ pentagonal bipyramids and (SeO₃)²⁻ pyramids sharing vertices and edges to form corrugated (001) layers. The Se lone pairs of electrons are accommodated in the interlayer regions.

Comment

Inorganic selenites containing the pyramidal (SeO₃)²⁻ ion are of ongoing crystallochemical interest because of the way the inherently asymmetric selenite ion packs into extended structures and the space requirements of the Se^IV lone pair of electrons (Wontcheu & Schleid, 2005 ). Metal selenites have also been studied for their potentially useful physical properties, such as second-harmonic generation (Ok & Halasyamani, 2002 ). As part of our ongoing studies of metal selenites (Johnston & Harrison, 2004a ,b ), we report here the structure of the title compound, Tl₂(SeO₃)₃, (I).

A compound of the same stoichiometry as (I) was first reported almost 100 years ago (Marino, 1909 ). Much later, Gospodinov (1984 ) reported a lemon-yellow compound of stoichiometry Tl₂(SeO₃)₃, although its crystal structure was not determined. The simulated X-ray powder pattern of (I) (colourless compound) does not match the powder data reported by Gospodinov. Thus, the yellow phase could represent a second polymorph of Tl₂(SeO₃)₃. We could find no other detailed structural studies of thallium(III) selenites, although the structures of thallium(I) `trihydroselenite', TlH₃(SeO₃)₂ (Shuvalov et al., 1983 ), and thallium(I) selenate, Tl₂SeO₄ (Fábry & Breczewski, 1993 ), have been determined from single-crystal data.

There are two Tl, three Se and nine O atoms in the asymmetric unit of (I), all of which occupy general positions in the unit cell. The three selenite groups show their expected (Verma, 1999 ) pyramidal coordination (Table 1), with the unobserved lone pair of electrons assumed to occupy the fourth tetrahedral vertex about each Se atom. The mean Se—O bond lengths are 1.716 (2), 1.709 (2) and 1.706 (2) Å for Se1, Se2 and Se3, respectively. The bond-valence sums (BVS) for the Se atoms, calculated using the Brown (1996 ) formalism, are 3.88, 3.98 and 3.99 for Se1, Se2 and Se3, respectively. These are in satisfactory agreement with the expected value of 4.00. The Se atoms are displaced from the plane formed by their three attached O atoms by 0.794 (6) (Se1), 0.807 (6) (Se2) and 0.794 (6) Å (Se3). The O—Se—O bond angles in (I) show more variation than is typical for selenite groups (Johnston & Harrison, 2004a) [for Se1, θ = 95.4 (5)–102.7 (5)°, range = 7.3°; for Se2, θ = 89.7 (5)–107.3 (5)°, range = 17.6°; for Se3, θ = 93.4 (5)–103.9 (5)°, range = 10.5°]. These distortions in the O—Se—O bond angles correlate well with their edge-sharing connectivity to adjacent thallium polyhedra (see below).

Atom Tl1 is approximately octahedrally coordinated by six O atoms. The mean Tl—O bond length of 2.24 (2) Å is in excellent agreement with the value of 2.25 Å expected on the basis of the ionic radius sum for Tl^III and O^−II (Shannon, 1976 ). The BVS for Tl1 is 3.28, compared with an expected value of 3.00 for Tl^III. This discrepancy perhaps suggests a degree of `overbonding' for this species, assuming that the BVS parameters for this species are reliable. The next-nearest O atom is 3.45 Å away from Tl1.

The coordination about atom Tl2 is unusual (Fig. 1). There are seven near-neighbour O atoms, with the Tl2—O1^iv bond of 2.496 (10) Å being significantly longer than the other six [mean = 2.28 (2) Å] (see Table 1 for symmetry codes). However, we feel that it is appropriate to consider it to be a bond because it contributes a significant 0.27 valence units to the Tl2 BVS of 3.20. The next-nearest neighbouring O atom is 3.78 Å distant from Tl2. There are no fewer than three edge-sharing selenite groups bonded to Tl2, involving the six shorter Tl2—O bonds. The three acute O—Se—O bond angles noted above are involved in these three edge-sharing interactions and the corresponding O—Tl2—O edge-sharing bond angles are grouped in the narrow range of 64.7 (3)–66.0 (4)°. The Tl2O₇ polyhedron could be described as a very distorted pentagonal bipyramid, with atoms O5 and O7 in the axial positions [θ(O5—Tl2—O7) = 166.0 (4)°]. The equatorial atoms Tl2, O1, O1^iv and O3 are approximately coplanar (r.m.s. deviation from the best plane is 0.008 Å). However, atom O9, and especially atom O4, are substantially displaced from their nominal equatorial positions by 0.632 (15) and −1.179 (16) Å, respectively.

Of the nine O atoms in the structure of (I), four, namely O1 [bond angle sum = 359.6 (5)°], O4 [359.6 (6)°], O5 [354.2 (6)°] and O9 [358.9 (5)°], are tricoordinate to two Tl plus one Se neighbours. There is a wide variation in these angles, e.g. the Tl—O1—Tl angle is the most obtuse around O1, whereas a Tl—O4—Se angle is the largest around O4 (Table 1). The remaining five O atoms form bicoordinate Tl—O—Se bridges [mean θ(Tl—O—Se) = 120.3°]. The bicoordinate bond-angle distribution is sharply bimodal, with two angles of around 104° and three angles of around 131° (Table 1).

The polyhedral connectivity in (I) results in corner-sharing (involving the long Tl2—O1 bond) chains of the Tl2O₇ groups propagating in the [100] direction. These are crosslinked by the Tl1O₆ groups to form (001) sheets (Fig. 2). The Tl1O₆ groups do not bond to other Tl1-centred polyhedra, but make four bonds to Tl2-centred moieties. Finally, the thallium/oxygen layers are decorated on both sides of the sheet by Se atoms (as parts of selenite groups).

When viewed down [100] (Fig. 3), the (001) layers are seen to be significantly corrugated, with the Se^IV lone pairs of electrons appearing to point into the interlayer regions of the structure. This suggests that, at least in part, the Se lone pairs are responsible for the layered nature of (I).

Figure 1
A view of a fragment of (I), showing 50% probability displacement ellipsoids. Symmetry codes are as given in Table 1

Figure 2
Part of an (001) layer in (I), showing the [100] chains of Tl2O₇ groups (dark shading) crosslinked by the Tl1O₆ octahedra (light shading). Se and O atoms are represented by large and small spheres, respectively.

Figure 3
The unit-cell packing in (I), projected on to (100). Drawing conventions are as in Fig. 2

Experimental

Tl₂O₃ (0.761 g, 1.66 mmol) was added to a 0.5 M H₂SeO₃ (20 ml) aqueous solution (i.e. dissolved SeO₂) and heated to 353 K in a plastic bottle. Thin colourless plates and shards of (I) grew over a few days and were recovered by vacuum filtration; they were accompanied by a small amount of black residue of Tl₂O₃. [Caution! All thallium compounds are exceedingly toxic. All appropriate safety precautions must be taken during their handling, especially with respect to dust contamination.]

Crystal data

Tl₂(SeO₃)₃
M_r = 789.62
Monoclinic, P 2₁ /n
a = 4.5666 (3) Å
b = 11.2194 (10) Å
c = 16.7595 (13) Å
β = 96.549 (6)°
V = 853.06 (12) Å³
Z = 4
D_x = 6.148 Mg m⁻³
Mo Kα radiation
Cell parameters from 1734 reflections
θ = 2.9–27.5°
μ = 50.56 mm⁻¹
T = 120 (2) K
Shard, colourless
0.13 × 0.05 × 0.01 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω and φ scans
Absorption correction: multi-scan(SADABS; Bruker, 2003 )T_min = 0.053, T_max = 0.632
10219 measured reflections
1948 independent reflections
1690 reflections with I > 2σ(I)
R_int = 0.059
θ_max = 27.5°
h = −5 → 5
k = −14 → 14
l = −21 → 21

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.121
S = 1.08
1948 reflections
127 parameters
w = 1/[σ²(F_o²) + (0.0696P)² + 26.3163P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 2.53 e Å⁻³
Δρ_min = −3.22 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Tl1—O2	2.131 (10)
Tl1—O9ⁱ	2.229 (10)
Tl1—O5	2.231 (10)
Tl1—O6ⁱⁱ	2.251 (10)
Tl1—O8ⁱⁱⁱ	2.269 (10)
Tl1—O4ⁱⁱⁱ	2.298 (10)
Tl2—O3^iv	2.198 (10)
Tl2—O7	2.207 (11)
Tl2—O4	2.280 (11)
Tl2—O1	2.293 (10)
Tl2—O5	2.299 (10)
Tl2—O9	2.382 (10)
Tl2—O1^iv	2.496 (10)
Se1—O3	1.706 (10)
Se1—O1	1.718 (10)
Se1—O2	1.724 (11)
Se2—O6	1.650 (10)
Se2—O5	1.734 (10)
Se2—O4	1.743 (10)
Se3—O8	1.681 (10)
Se3—O7	1.713 (10)
Se3—O9	1.725 (10)

Se1—O1—Tl2	121.2 (5)
Se1—O1—Tl2ⁱⁱ	93.5 (4)
Tl2—O1—Tl2ⁱⁱ	144.9 (5)
Se1—O2—Tl1	132.3 (6)
Se1—O3—Tl2ⁱⁱ	105.1 (5)
Se2—O4—Tl2	102.8 (5)
Se2—O4—Tl1^v	132.4 (6)
Tl2—O4—Tl1^v	124.4 (5)
Se2—O5—Tl1	124.8 (5)
Se2—O5—Tl2	102.4 (4)
Tl1—O5—Tl2	127.0 (5)
Se2—O6—Tl1^iv	130.6 (6)
Se3—O7—Tl2	102.8 (5)
Se3—O8—Tl1^v	130.8 (5)
Se3—O9—Tl1^vi	122.3 (5)
Se3—O9—Tl2	95.8 (4)
Tl1^vi—O9—Tl2	140.8 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

The highest difference peak is 0.94 Å from O2 and 1.40 Å from Tl1; the deepest hole is 0.92 Å from O5 and 1.38 Å from Tl2.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and ATOMS (Dowty, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270105018111/bc1073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105018111/bc1073Isup2.hkl

Comment top

Inorganic selenites containing the pyramidal (SeO₃)²⁻ ion are of ongoing crystallochemical interest because of the way the inherently asymmetric selenite ion packs into extended structures and the space requirements of the Se^IV lone pair of electrons (Wontcheu & Schleid, 2005). Metal selenites have also been studied for their potentially useful physical properties, such as second-harmonic generation (Ok & Halasyamani, 2002). As part of our ongoing studies of metal selenites (Johnston & Harrison, 2004a,b), we report here the structure of the title compound, Tl₂(SeO₃)₃, (I).

A compound of the same stoichiometry as (I) was first reported almost 100 years ago (Marino, 1909). Much later, Gospodinov (1984) reported a lemon-yellow compound of stoichiometry Tl₂(SeO₃)₃, although its crystal structure was not determined. The simulated X-ray powder pattern of (I) (colourless compound) does not match the powder data reported by Gospodinov. Thus, the yellow phase could represent a second polymorph of Tl₂(SeO₃)₃. We could find no other detailed structural studies of thallium(III) selenites, although the structures of thallium(I) `trihydroselenite', TlH₃(SeO₃)₂ (Shuvalov et al., 1983) and thallium(I) selenate, Tl₂SeO₄ (Fabry & Breczewski, 1993) have been determined from single-crystal data.

There are two Tl, three Se and nine O atoms in the asymmetric unit of (I), all of which occupy general positions in the unit cell. The three selenite groups show their expected (Verma, 1999) pyramidal coordination (Table 1), with the unobserved lone pair of electrons assumed to occupy the fourth tetrahedral vertex about each Se atom. The mean Se—O bond lengths are 1.716 (2), 1.709 (2) and 1.706 (2) Å, for Se1, Se2 and Se3, respectively. The bond-valence sums (BVS) for the Se atoms, calculated using the Brown (1996) formalism, are 3.88, 3.98 and 3.99 for Se1, Se2 and Se3, respectively. These are in satisfactory agreement with the expected value of 4.00. The Se atoms are displaced from the plane formed by their three attached O atoms by 0.794 (6) Å (Se1), 0.807 (6) Å (Se2) and 0.794(60 Å (Se3). The O—Se—O bond angles in (I) show somewhat more variation than is typical for selenite groups (Johnston & Harrison, 2004a) [for Se1, θ = 95.4 (5)–102.7 (5)°, range = 7.3°; for Se2, θ = 89.7 (5)–107.3 (5)°, range = 17.6°; for Se3, θ = 93.4 (5)–103.9 (5)°, range = 10.5°]. These distortions in the O—Se—O bond angles correlate well with their edge-sharing connectivity to adjacent thallium polyhedra (see below).

Atom Tl1 is approximately octahedrally coordinated by six O atoms. The mean Tl—O bond length of 2.24 (2) Å is in excellent agreement with the value of 2.25 Å expected on the basis of the ionic radius sum for Tl^III and O^—II (Shannon, 1976). The BVS for Tl1 is 3.28, compared with an expected value of 3.00 for Tl^III. This discrepancy perhaps suggests a degree of `overbonding' for this species, assuming that the BVS parameters for this species are reliable. The next-nearest O atom is 3.45 Å away from Tl1.

Of the nine O atoms in the structure of (I), four {O1 [bond angle sum 359.6 (5)°], O4 [359.6 (6)°], O5 [354.2 (6)°] and O9 [358.9 (5)°]} are tri-coordinate to two Tl plus one Se neighbours. There is a wide variation in these angles, e.g. the Tl—O1—Tl angle is the most obtuse around O1, whereas a Tl—O4—Se angle is the largest around O4 (Table 1). The remaining five O atoms form bi-coordinate Tl—O—Se bridges [mean θ(Tl—O—Se) = 120.3°]. The bi-coordinate bond-angle distribution is sharply bimodal, with two angles of around 104° and three angles of around 131° (Table 1).

The polyhedral connectivity in (I) results in corner sharing (involving the long Tl2—O1 bond) chains of the Tl2O₇ groups propagating in the [100] direction. These are crosslinked by the Tl1O₆ groups to form (001) sheets (Fig. 2). The Tl1O₆ groups do not bond to other Tl1-centred polyhedra, but make four bonds to Tl2-centred moieties. Finally, the thallium/oxygen layers are decorated on both sides of the sheet by Se atoms (as parts of selenite groups).

When viewed down [100] (Fig. 3), the (001) layers are seen to be significantly corrugated, with the Se^IV lone pairs of electrons appearing to point into the inter-layer regions of the structure. This suggests that, at least in part, the Se lone pairs are responsible for the layered nature of (I).

Experimental top

Tl₂O₃ (0.761 g, 1.66 mmol) was added to 0.5 M H₂SeO₃ (20 ml) aqueous solution (i.e. dissolved SeO₂) and heated to 353 K in a plastic bottle. Thin colourless plates and shards of (I) grew over a few days and were recovered by vacuum filtration, accompanied by a small amount of black residue of Tl₂O₃. Caution! All thallium compounds are exceedingly toxic. All appropriate safety precautions must be taken during their handling, especially with respect to dust contamination.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 2000); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. A view of a fragment of (I), showing 50% displacement ellipsoids. Symmetry codes are as given in Table 1.
	Fig. 2. Part of an (001) layer in (I), showing the [100] chains of Tl2O₇ groups (dark shading) crosslinked by the Tl1O₆ octahedra (light shading). Se and O atoms are represented by large and small spheres, respectively.
	Fig. 3. The unit-cell packing in (I), projected onto (100). Drawing conventions are as in Fig. 2.

dithallium(III) triselenium(IV) oxide top

Crystal data top

Tl₂(SeO₃)₃	F(000) = 1344
M_r = 789.62	D_x = 6.148 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1734 reflections
a = 4.5666 (3) Å	θ = 2.9–27.5°
b = 11.2194 (10) Å	µ = 50.56 mm⁻¹
c = 16.7595 (13) Å	T = 120 K
β = 96.549 (6)°	Shard, colourless
V = 853.06 (12) Å³	0.13 × 0.05 × 0.01 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	1948 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ω and ϕ scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −5→5
T_min = 0.053, T_max = 0.632	k = −14→14
10219 measured reflections	l = −21→21

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.044	Secondary atom site location: difference Fourier map
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0696P)² + 26.3163P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.002
1948 reflections	Δρ_max = 2.53 e Å⁻³
127 parameters	Δρ_min = −3.22 e Å⁻³

Crystal data top

Tl₂(SeO₃)₃	V = 853.06 (12) Å³
M_r = 789.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.5666 (3) Å	µ = 50.56 mm⁻¹
b = 11.2194 (10) Å	T = 120 K
c = 16.7595 (13) Å	0.13 × 0.05 × 0.01 mm
β = 96.549 (6)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1948 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1690 reflections with I > 2σ(I)
T_min = 0.053, T_max = 0.632	R_int = 0.059
10219 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0696P)² + 26.3163P] where P = (F_o² + 2F_c²)/3
S = 1.08	Δρ_max = 2.53 e Å⁻³
1948 reflections	Δρ_min = −3.22 e Å⁻³
127 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Tl1	0.32538 (11)	0.43917 (4)	0.20541 (3)	0.01094 (19)
Tl2	0.76747 (11)	0.64964 (4)	0.37514 (3)	0.01019 (18)
Se1	0.2205 (3)	0.44351 (11)	0.41081 (9)	0.0105 (3)
Se2	0.8131 (3)	0.67867 (12)	0.18924 (9)	0.0106 (3)
Se3	0.7198 (3)	0.89568 (12)	0.45399 (8)	0.0102 (3)
O1	0.297 (2)	0.5895 (9)	0.3902 (7)	0.016 (2)
O2	0.217 (3)	0.3759 (10)	0.3183 (6)	0.018 (2)
O3	−0.145 (2)	0.4663 (9)	0.4177 (7)	0.017 (2)
O4	0.940 (2)	0.7586 (9)	0.2755 (6)	0.017 (2)
O5	0.677 (2)	0.5697 (8)	0.2484 (6)	0.012 (2)
O6	1.099 (2)	0.6081 (9)	0.1597 (6)	0.013 (2)
O7	0.892 (2)	0.7637 (9)	0.4808 (7)	0.019 (2)
O8	0.974 (2)	0.9728 (8)	0.4102 (6)	0.014 (2)
O9	0.507 (2)	0.8338 (8)	0.3728 (6)	0.012 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.0118 (3)	0.0083 (3)	0.0125 (3)	−0.00085 (17)	0.0008 (2)	0.00000 (17)
Tl2	0.0112 (3)	0.0080 (3)	0.0115 (3)	−0.00027 (18)	0.0015 (2)	−0.00023 (17)
Se1	0.0114 (7)	0.0085 (6)	0.0117 (7)	0.0005 (5)	0.0021 (5)	0.0009 (5)
Se2	0.0113 (7)	0.0091 (6)	0.0113 (7)	0.0006 (5)	0.0012 (5)	0.0010 (5)
Se3	0.0115 (7)	0.0076 (6)	0.0117 (7)	0.0001 (5)	0.0022 (5)	−0.0018 (5)
O1	0.010 (5)	0.013 (5)	0.024 (6)	−0.005 (4)	0.000 (4)	0.002 (4)
O2	0.032 (7)	0.017 (5)	0.010 (5)	−0.001 (4)	0.015 (5)	0.001 (4)
O3	0.006 (5)	0.017 (5)	0.027 (6)	0.002 (4)	0.004 (4)	0.010 (4)
O4	0.022 (6)	0.014 (5)	0.014 (6)	−0.004 (4)	−0.004 (4)	−0.001 (4)
O5	0.020 (6)	0.010 (5)	0.007 (5)	−0.005 (4)	0.003 (4)	0.002 (4)
O6	0.013 (5)	0.010 (5)	0.015 (5)	0.002 (4)	0.000 (4)	−0.002 (4)
O7	0.019 (6)	0.013 (5)	0.024 (6)	0.005 (4)	0.004 (5)	−0.001 (4)
O8	0.016 (5)	0.007 (5)	0.020 (6)	−0.001 (4)	0.006 (4)	−0.001 (4)
O9	0.013 (5)	0.009 (4)	0.015 (6)	−0.007 (4)	−0.002 (4)	−0.004 (4)

Geometric parameters (Å, º) top

Tl1—O2	2.131 (10)	Se1—O1	1.718 (10)
Tl1—O9ⁱ	2.229 (10)	Se1—O2	1.724 (11)
Tl1—O5	2.231 (10)	Se2—O6	1.650 (10)
Tl1—O6ⁱⁱ	2.251 (10)	Se2—O5	1.734 (10)
Tl1—O8ⁱⁱⁱ	2.269 (10)	Se2—O4	1.743 (10)
Tl1—O4ⁱⁱⁱ	2.298 (10)	Se3—O8	1.681 (10)
Tl2—O3^iv	2.198 (10)	Se3—O7	1.713 (10)
Tl2—O7	2.207 (11)	Se3—O9	1.725 (10)
Tl2—O4	2.280 (11)	O1—Tl2ⁱⁱ	2.496 (10)
Tl2—O1	2.293 (10)	O3—Tl2ⁱⁱ	2.198 (10)
Tl2—O5	2.299 (10)	O4—Tl1^v	2.298 (10)
Tl2—O9	2.382 (10)	O6—Tl1^iv	2.251 (10)
Tl2—O1^iv	2.496 (10)	O8—Tl1^v	2.269 (10)
Se1—O3	1.706 (10)	O9—Tl1^vi	2.229 (10)

O2—Tl1—O9ⁱ	97.7 (4)	O7—Tl2—O1^iv	85.2 (4)
O2—Tl1—O5	99.4 (4)	O4—Tl2—O1^iv	78.9 (4)
O9ⁱ—Tl1—O5	162.8 (4)	O1—Tl2—O1^iv	144.9 (5)
O2—Tl1—O6ⁱⁱ	116.0 (4)	O5—Tl2—O1^iv	93.4 (4)
O9ⁱ—Tl1—O6ⁱⁱ	89.5 (3)	O9—Tl2—O1^iv	135.4 (3)
O5—Tl1—O6ⁱⁱ	80.9 (4)	O3—Se1—O1	95.4 (5)
O2—Tl1—O8ⁱⁱⁱ	166.3 (4)	O3—Se1—O2	102.6 (6)
O9ⁱ—Tl1—O8ⁱⁱⁱ	84.3 (4)	O1—Se1—O2	102.7 (5)
O5—Tl1—O8ⁱⁱⁱ	79.7 (4)	O6—Se2—O5	100.4 (5)
O6ⁱⁱ—Tl1—O8ⁱⁱⁱ	77.5 (4)	O6—Se2—O4	107.3 (5)
O2—Tl1—O4ⁱⁱⁱ	74.6 (4)	O5—Se2—O4	89.7 (5)
O9ⁱ—Tl1—O4ⁱⁱⁱ	83.7 (3)	O8—Se3—O7	103.9 (5)
O5—Tl1—O4ⁱⁱⁱ	103.1 (4)	O8—Se3—O9	102.5 (5)
O6ⁱⁱ—Tl1—O4ⁱⁱⁱ	168.2 (4)	O7—Se3—O9	93.4 (5)
O8ⁱⁱⁱ—Tl1—O4ⁱⁱⁱ	92.2 (4)	Se1—O1—Tl2	121.2 (5)
O3^iv—Tl2—O7	105.2 (4)	Se1—O1—Tl2ⁱⁱ	93.5 (4)
O3^iv—Tl2—O4	132.4 (4)	Tl2—O1—Tl2ⁱⁱ	144.9 (5)
O7—Tl2—O4	101.4 (4)	Se1—O2—Tl1	132.3 (6)
O3^iv—Tl2—O1	80.0 (4)	Se1—O3—Tl2ⁱⁱ	105.1 (5)
O7—Tl2—O1	104.0 (4)	Se2—O4—Tl2	102.8 (5)
O4—Tl2—O1	130.1 (4)	Se2—O4—Tl1^v	132.4 (6)
O3^iv—Tl2—O5	86.7 (4)	Tl2—O4—Tl1^v	124.4 (5)
O7—Tl2—O5	166.0 (4)	Se2—O5—Tl1	124.8 (5)
O4—Tl2—O5	64.7 (3)	Se2—O5—Tl2	102.4 (4)
O1—Tl2—O5	85.1 (4)	Tl1—O5—Tl2	127.0 (5)
O3^iv—Tl2—O9	152.7 (4)	Se2—O6—Tl1^iv	130.6 (6)
O7—Tl2—O9	66.0 (4)	Se3—O7—Tl2	102.8 (5)
O4—Tl2—O9	74.7 (4)	Se3—O8—Tl1^v	130.8 (5)
O1—Tl2—O9	77.6 (4)	Se3—O9—Tl1^vi	122.3 (5)
O5—Tl2—O9	106.6 (4)	Se3—O9—Tl2	95.8 (4)
O3^iv—Tl2—O1^iv	64.9 (3)	Tl1^vi—O9—Tl2	140.8 (5)

O3^iv—Tl2—Se2—O6	−42.9 (5)	O3^iv—Tl2—O4—Se2	62.6 (7)
O7—Tl2—Se2—O6	99.4 (5)	O7—Tl2—O4—Se2	−174.4 (5)
O4—Tl2—Se2—O6	91.8 (6)	O1—Tl2—O4—Se2	−54.9 (7)
O1—Tl2—Se2—O6	−129.3 (5)	O5—Tl2—O4—Se2	3.8 (4)
O5—Tl2—Se2—O6	−81.8 (6)	O9—Tl2—O4—Se2	−113.4 (5)
O9—Tl2—Se2—O6	154.0 (5)	O1^iv—Tl2—O4—Se2	102.9 (5)
O1^iv—Tl2—Se2—O6	18.5 (4)	Se3—Tl2—O4—Se2	−146.9 (5)
Se3—Tl2—Se2—O6	127.1 (4)	Se1^iv—Tl2—O4—Se2	82.0 (5)
Se1^iv—Tl2—Se2—O6	−13.1 (4)	O3^iv—Tl2—O4—Tl1^v	−123.2 (6)
O3^iv—Tl2—Se2—O5	38.9 (6)	O7—Tl2—O4—Tl1^v	−0.2 (7)
O7—Tl2—Se2—O5	−178.8 (6)	O1—Tl2—O4—Tl1^v	119.3 (6)
O4—Tl2—Se2—O5	173.6 (7)	O5—Tl2—O4—Tl1^v	177.9 (7)
O1—Tl2—Se2—O5	−47.5 (6)	O9—Tl2—O4—Tl1^v	60.7 (5)
O9—Tl2—Se2—O5	−124.1 (6)	O1^iv—Tl2—O4—Tl1^v	−83.0 (6)
O1^iv—Tl2—Se2—O5	100.3 (6)	Se3—Tl2—O4—Tl1^v	27.3 (5)
Se3—Tl2—Se2—O5	−151.1 (5)	Se1^iv—Tl2—O4—Tl1^v	−103.8 (5)
Se1^iv—Tl2—Se2—O5	68.7 (5)	Se2—Tl2—O4—Tl1^v	174.1 (10)
O3^iv—Tl2—Se2—O4	−134.7 (6)	O6—Se2—O5—Tl1	−93.5 (7)
O7—Tl2—Se2—O4	7.6 (6)	O4—Se2—O5—Tl1	159.0 (7)
O1—Tl2—Se2—O4	138.9 (6)	Tl2—Se2—O5—Tl1	154.5 (9)
O5—Tl2—Se2—O4	−173.6 (7)	O6—Se2—O5—Tl2	112.0 (5)
O9—Tl2—Se2—O4	62.3 (6)	O4—Se2—O5—Tl2	4.5 (5)
O1^iv—Tl2—Se2—O4	−73.3 (6)	O2—Tl1—O5—Se2	−165.4 (6)
Se3—Tl2—Se2—O4	35.3 (5)	O9ⁱ—Tl1—O5—Se2	6.6 (17)
Se1^iv—Tl2—Se2—O4	−104.9 (5)	O6ⁱⁱ—Tl1—O5—Se2	−50.4 (6)
O3^iv—Tl2—Se3—O8	123.7 (5)	O8ⁱⁱⁱ—Tl1—O5—Se2	28.5 (6)
O7—Tl2—Se3—O8	98.8 (7)	O4ⁱⁱⁱ—Tl1—O5—Se2	118.3 (6)
O4—Tl2—Se3—O8	−24.7 (5)	O2—Tl1—O5—Tl2	−17.2 (6)
O1—Tl2—Se3—O8	−154.5 (5)	O9ⁱ—Tl1—O5—Tl2	154.8 (9)
O5—Tl2—Se3—O8	−65.3 (5)	O6ⁱⁱ—Tl1—O5—Tl2	97.9 (6)
O9—Tl2—Se3—O8	−97.3 (6)	O8ⁱⁱⁱ—Tl1—O5—Tl2	176.7 (6)
O1^iv—Tl2—Se3—O8	51.2 (5)	O4ⁱⁱⁱ—Tl1—O5—Tl2	−93.5 (6)
Se1^iv—Tl2—Se3—O8	79.5 (4)	O3^iv—Tl2—O5—Se2	−144.5 (5)
Se2—Tl2—Se3—O8	−43.0 (4)	O7—Tl2—O5—Se2	3.7 (19)
O3^iv—Tl2—Se3—O7	24.9 (7)	O4—Tl2—O5—Se2	−3.8 (4)
O4—Tl2—Se3—O7	−123.6 (6)	O1—Tl2—O5—Se2	135.2 (5)
O1—Tl2—Se3—O7	106.7 (6)	O9—Tl2—O5—Se2	59.7 (5)
O5—Tl2—Se3—O7	−164.1 (7)	O1^iv—Tl2—O5—Se2	−79.9 (5)
O9—Tl2—Se3—O7	163.8 (7)	Se3—Tl2—O5—Se2	41.8 (7)
O1^iv—Tl2—Se3—O7	−47.6 (6)	Se1^iv—Tl2—O5—Se2	−112.5 (4)
Se1^iv—Tl2—Se3—O7	−19.3 (6)	O3^iv—Tl2—O5—Tl1	61.8 (6)
Se2—Tl2—Se3—O7	−141.8 (5)	O7—Tl2—O5—Tl1	−150.0 (13)
O3^iv—Tl2—Se3—O9	−138.9 (6)	O4—Tl2—O5—Tl1	−157.5 (7)
O7—Tl2—Se3—O9	−163.8 (7)	O1—Tl2—O5—Tl1	−18.5 (6)
O4—Tl2—Se3—O9	72.6 (5)	O9—Tl2—O5—Tl1	−94.0 (6)
O1—Tl2—Se3—O9	−57.2 (5)	O1^iv—Tl2—O5—Tl1	126.4 (6)
O5—Tl2—Se3—O9	32.1 (6)	Se3—Tl2—O5—Tl1	−112.0 (5)
O1^iv—Tl2—Se3—O9	148.5 (5)	Se1^iv—Tl2—O5—Tl1	93.8 (5)
Se1^iv—Tl2—Se3—O9	176.8 (5)	Se2—Tl2—O5—Tl1	−153.7 (9)
Se2—Tl2—Se3—O9	54.4 (5)	O5—Se2—O6—Tl1^iv	−13.9 (8)
O3—Se1—O1—Tl2	177.6 (7)	O4—Se2—O6—Tl1^iv	79.1 (8)
O2—Se1—O1—Tl2	−78.2 (7)	Tl2—Se2—O6—Tl1^iv	31.7 (8)
Tl2ⁱⁱ—Se1—O1—Tl2	−174.4 (8)	O8—Se3—O7—Tl2	−91.4 (5)
O3—Se1—O1—Tl2ⁱⁱ	−8.0 (5)	O9—Se3—O7—Tl2	12.4 (6)
O2—Se1—O1—Tl2ⁱⁱ	96.2 (5)	O3^iv—Tl2—O7—Se3	−162.3 (5)
O3^iv—Tl2—O1—Se1	−8.4 (6)	O4—Tl2—O7—Se3	57.6 (6)
O7—Tl2—O1—Se1	−111.7 (7)	O1—Tl2—O7—Se3	−79.1 (5)
O4—Tl2—O1—Se1	129.9 (6)	O5—Tl2—O7—Se3	50.6 (18)
O5—Tl2—O1—Se1	79.1 (7)	O9—Tl2—O7—Se3	−9.8 (4)
O9—Tl2—O1—Se1	−172.7 (7)	O1^iv—Tl2—O7—Se3	135.3 (5)
O1^iv—Tl2—O1—Se1	−9.8 (15)	Se1^iv—Tl2—O7—Se3	165.4 (4)
Se3—Tl2—O1—Se1	−144.1 (6)	Se2—Tl2—O7—Se3	53.4 (7)
Se1^iv—Tl2—O1—Se1	−4.8 (7)	O7—Se3—O8—Tl1^v	66.3 (8)
Se2—Tl2—O1—Se1	102.4 (6)	O9—Se3—O8—Tl1^v	−30.5 (8)
O3^iv—Tl2—O1—Tl2ⁱⁱ	−178.6 (10)	Tl2—Se3—O8—Tl1^v	21.0 (7)
O7—Tl2—O1—Tl2ⁱⁱ	78.2 (9)	O8—Se3—O9—Tl1^vi	−76.8 (7)
O4—Tl2—O1—Tl2ⁱⁱ	−40.3 (11)	O7—Se3—O9—Tl1^vi	178.1 (6)
O5—Tl2—O1—Tl2ⁱⁱ	−91.1 (9)	Tl2—Se3—O9—Tl1^vi	−170.6 (8)
O9—Tl2—O1—Tl2ⁱⁱ	17.1 (8)	O8—Se3—O9—Tl2	93.8 (5)
O1^iv—Tl2—O1—Tl2ⁱⁱ	180.0	O7—Se3—O9—Tl2	−11.2 (5)
Se3—Tl2—O1—Tl2ⁱⁱ	45.8 (9)	O3^iv—Tl2—O9—Se3	85.7 (9)
Se1^iv—Tl2—O1—Tl2ⁱⁱ	−175.0 (7)	O7—Tl2—O9—Se3	9.5 (4)
Se2—Tl2—O1—Tl2ⁱⁱ	−67.8 (9)	O4—Tl2—O9—Se3	−100.7 (5)
O3—Se1—O2—Tl1	105.3 (9)	O1—Tl2—O9—Se3	121.2 (5)
O1—Se1—O2—Tl1	6.8 (10)	O5—Tl2—O9—Se3	−157.8 (4)
Tl2ⁱⁱ—Se1—O2—Tl1	61.3 (9)	O1^iv—Tl2—O9—Se3	−44.9 (7)
O9ⁱ—Tl1—O2—Se1	−145.9 (8)	Se1^iv—Tl2—O9—Se3	−9.3 (13)
O5—Tl1—O2—Se1	31.7 (9)	Se2—Tl2—O9—Se3	−130.3 (4)
O6ⁱⁱ—Tl1—O2—Se1	−52.7 (10)	O3^iv—Tl2—O9—Tl1^vi	−106.9 (10)
O8ⁱⁱⁱ—Tl1—O2—Se1	116.5 (15)	O7—Tl2—O9—Tl1^vi	177.0 (9)
O4ⁱⁱⁱ—Tl1—O2—Se1	132.8 (9)	O4—Tl2—O9—Tl1^vi	66.7 (7)
O1—Se1—O3—Tl2ⁱⁱ	9.4 (6)	O1—Tl2—O9—Tl1^vi	−71.4 (8)
O2—Se1—O3—Tl2ⁱⁱ	−94.9 (6)	O5—Tl2—O9—Tl1^vi	9.6 (8)
O6—Se2—O4—Tl2	−105.4 (5)	O1^iv—Tl2—O9—Tl1^vi	122.5 (7)
O5—Se2—O4—Tl2	−4.5 (5)	Se3—Tl2—O9—Tl1^vi	167.4 (11)
O6—Se2—O4—Tl1^v	81.2 (8)	Se1^iv—Tl2—O9—Tl1^vi	158.1 (4)
O5—Se2—O4—Tl1^v	−178.0 (8)	Se2—Tl2—O9—Tl1^vi	37.1 (7)
Tl2—Se2—O4—Tl1^v	−173.5 (11)

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

Experimental details

Crystal data
Chemical formula	Tl₂(SeO₃)₃
M_r	789.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	4.5666 (3), 11.2194 (10), 16.7595 (13)
β (°)	96.549 (6)
V (Å³)	853.06 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	50.56
Crystal size (mm)	0.13 × 0.05 × 0.01

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.053, 0.632
No. of measured, independent and observed [I > 2σ(I)] reflections	10219, 1948, 1690
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.121, 1.08
No. of reflections	1948
No. of parameters	127
	w = 1/[σ²(F_o²) + (0.0696P)² + 26.3163P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.53, −3.22

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 2000), SHELXL97.

Selected geometric parameters (Å, º) top

Tl1—O2	2.131 (10)	Tl2—O9	2.382 (10)
Tl1—O9ⁱ	2.229 (10)	Tl2—O1^iv	2.496 (10)
Tl1—O5	2.231 (10)	Se1—O3	1.706 (10)
Tl1—O6ⁱⁱ	2.251 (10)	Se1—O1	1.718 (10)
Tl1—O8ⁱⁱⁱ	2.269 (10)	Se1—O2	1.724 (11)
Tl1—O4ⁱⁱⁱ	2.298 (10)	Se2—O6	1.650 (10)
Tl2—O3^iv	2.198 (10)	Se2—O5	1.734 (10)
Tl2—O7	2.207 (11)	Se2—O4	1.743 (10)
Tl2—O4	2.280 (11)	Se3—O8	1.681 (10)
Tl2—O1	2.293 (10)	Se3—O7	1.713 (10)
Tl2—O5	2.299 (10)	Se3—O9	1.725 (10)

Se1—O1—Tl2	121.2 (5)	Se2—O5—Tl2	102.4 (4)
Se1—O1—Tl2ⁱⁱ	93.5 (4)	Tl1—O5—Tl2	127.0 (5)
Tl2—O1—Tl2ⁱⁱ	144.9 (5)	Se2—O6—Tl1^iv	130.6 (6)
Se1—O2—Tl1	132.3 (6)	Se3—O7—Tl2	102.8 (5)
Se1—O3—Tl2ⁱⁱ	105.1 (5)	Se3—O8—Tl1^v	130.8 (5)
Se2—O4—Tl2	102.8 (5)	Se3—O9—Tl1^vi	122.3 (5)
Se2—O4—Tl1^v	132.4 (6)	Se3—O9—Tl2	95.8 (4)
Tl2—O4—Tl1^v	124.4 (5)	Tl1^vi—O9—Tl2	140.8 (5)
Se2—O5—Tl1	124.8 (5)

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

Acknowledgements

The authors thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

References

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Volume 61| Part 7| July 2005| Pages i76-i78

doi:10.1107/S0108270105018111

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