Thallium(I) copper(I) thorium(IV) tris­elenide, TlCuThSe3

Koscielski, L.A.; Ibers, J.A.

doi:10.1107/S1600536812026669

inorganic compounds

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Volume 68| Part 7| July 2012| Pages i52-i53

https://doi.org/10.1107/S1600536812026669

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Thallium(I) copper(I) thorium(IV) triselenide, TlCuThSe₃

Lukasz A. Koscielski ^a and James A. Ibers ^a ^*

^aDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA
^*Correspondence e-mail: ibers@chem.northwestern.edu

(Received 1 June 2012; accepted 12 June 2012; online 20 June 2012)

Thallium(I) copper(I) thorium(IV) triselenide, TlCuThSe₃, crystallizes with four formula units in the space group Cmcm in the KCuZrS₃ structure type. There is one crystallographically independent Th, Tl, and Cu atom at a site of symmetry 2/m.., m2m, and m2m, respectively. There are two crystallographically independent Se atoms at sites of symmetry m.. and m2m. The structure consists of sheets of edge-sharing ThSe₆ octahedra and CuSe₄ tetrahedra stacked parallel to the (010) face, separated by layers filled with chains of Tl running parallel to [100]. Each Tl is coordinated by a trigonal prism of Se atoms.

Related literature

For compounds of type AMM'Q₃, see: Pell & Ibers (1996 ); Klepp & Gurtner (1996 ) for A = Tl; Pell et al. (1997 ); Yao et al. (2008 ); Wells et al. (2009 ) for M = Ag; Bugaris & Ibers (2009 ) for M = Au; Mansuetto et al. (1993 ); Pell & Ibers (1996) for M′ = Ti; Mansuetto et al. (1992 , 1993); Huang et al. (2001 ); Pell et al. (1997) for M′ = Zr; Klepp & Sturmayr (1997 , 1998 ); Pell et al. (1997) for M′ = Hf; Seldy et al. (2005 ); Narducci & Ibers (2000 ) for M′ = Th; Yao et al. (2008); Sutorik et al. (1996 ); Bugaris & Ibers (2009); Huang et al. (2001); Cody & Ibers (1995 ) for M′ = U; Wells et al. (2009) for M′ = Np. For computational details, see: Gelato & Parthé (1987 ). For additional synthetic details, see: Witt et al. (1956 ).

Experimental

Crystal data

TlCuThSe₃
M_r = 736.83
Orthorhombic, C m c m
a = 4.1678 (2) Å
b = 14.2227 (7) Å
c = 10.8476 (5) Å
V = 643.02 (5) Å³
Z = 4
Mo Kα radiation
μ = 68.19 mm⁻¹
T = 100 K
0.10 × 0.07 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 2008b ) T_min = 0.101, T_max = 0.489
7476 measured reflections
474 independent reflections
451 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.046
S = 1.59
474 reflections
24 parameters
Δρ_max = 2.01 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Th1—Se2ⁱ	2.8844 (4)
Th1—Se2	2.8844 (4)
Th1—Se1ⁱⁱ	2.9057 (5)
Th1—Se1ⁱⁱⁱ	2.9057 (5)
Th1—Se1^iv	2.9057 (5)
Th1—Se1^v	2.9057 (5)
Tl1—Se2^vi	3.2831 (9)
Tl1—Se2^vii	3.2831 (9)
Tl1—Se1^viii	3.3564 (6)
Tl1—Se1^vi	3.3564 (6)
Tl1—Se1^ix	3.3564 (6)
Tl1—Se1^vii	3.3564 (6)
Cu1—Se1	2.4617 (11)
Cu1—Se1^x	2.4617 (11)
Cu1—Se2^vii	2.5517 (11)
Cu1—Se2^vi	2.5517 (11)
Symmetry codes: (i) -x, -y, -z; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (v) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (vi) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (viii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ix) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (x) $[x, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a); molecular graphics: CrystalMaker (Palmer, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812026669/wm2644sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026669/wm2644Isup2.hkl

checkCIF report

Comment top

Thallium(I) copper(I) thorium(IV) triselenide, TlCuThSe₃, crystallizes in the KCuZrS₃ structure type. The structure (Figs. 1, 2) is layered and consists of sheets of edge-sharing ThSe₆ octahedra and CuSe₄ tetrahedra stacked parallel to the (010) face separated by layers filled with chains of Tl running parallel to [100]. Each Tl is coordinated by a trigonal prism of Se atoms. Because there are no Se—Se bonds in the structure, oxidation states can be assigned as Tl⁺, Cu⁺, Th⁴⁺, and Se^2-.

The compound TlCuThSe₃ is of the type AMM'Q₃, where A is an alkali metal or thallium, M is a coinage metal, M' is a tetravalent group IV metal or an actinide, and Q is a chalcogen. Including the title compound, 39 such compounds are known (Pell & Ibers, 1996; Klepp & Gurtner, 1996; Pell et al., 1997; Yao et al., 2008; Wells et al., 2009; Bugaris & Ibers, 2009; Sutorik et al., 1996; Huang et al., 2001; Cody & Ibers, 1995; Mansuetto et al., 1993, 1992; Klepp & Sturmayr, 1997, 1998; Seldy et al., 2005; Narducci & Ibers, 2000). In all cases, crystallographic data have been collected on single crystals. Most often, the A site contains an alkali metal and only 6 Tl analogues are known (Pell & Ibers, 1996; Klepp & Gurtner, 1996). The M site contains Cu in 28 analogues, Ag in 7 analogues (Pell et al., 1997; Yao et al., 2008; Wells et al., 2009), and Au in 4 analogues (Bugaris & Ibers, 2009). The tetravalent metal is most often U with 14 analogues (Yao et al., 2008; Sutorik et al., 1996; Bugaris & Ibers, 2009; Huang et al., 2001; Cody & Ibers, 1995), followed by Zr with 9 analogues (Mansuetto et al., 1992, 1993; Huang et al., 2001; Pell et al., 1997), Hf with 5 analogues (Klepp & Sturmayr, 1997, 1998; Pell et al., 1997), Np with 5 analogues (Wells et al., 2009), Th with 4 analogues (Seldy et al., 2005; Narducci & Ibers, 2000), and Ti with 2 analogues (Mansuetto et al., 1993; Pell & Ibers, 1996). This is the first compound of the type AMM'Q₃ to contain both Tl and Th.

The compounds fall into three structure types. All the Na analogues, except for NaCuZrS₃, are of the NaCuTiS₃ type (space group Pnma) (Mansuetto et al., 1993; Klepp & Sturmayr, 1997); the compounds TlCuTiTe₃ and RbAgHfTe₃ are of the TlCuTiTe₃ type (space group P2₁/m) (Pell & Ibers, 1996; Pell et al., 1997); and the remaining compounds are of the KCuZrS₃ type (space group Cmcm).

Interatomic distances in TlCuThSe₃ are listed in Table 1 and are nearly identical to those in the analogues ACuThSe₃ (A = K, Cs) (Narducci & Ibers, 2000). The TlCuThSe₃ Th—Se distances of 2.8844 (4) and 2.9057 (5) Å match those in KCuThSe₃ (2.893 (1) and 2.900 (1) Å) and CsCuThSe₃ (2.878 (1) and 2.906 (1) Å). The Cu—Se distances of 2.4617 (11) and 2.5517 (11) Å also match those in KCuThSe₃ (2.459 (2) and 2.545 (2) Å) and CsCuThSe₃ (2.464 (2) and 2.556 (2) Å).

Related literature top

For compounds of type AMM'Q₃, see: Pell & Ibers (1996); Klepp & Gurtner (1996) for A = Tl; Pell et al. (1997); Yao et al. (2008); Wells et al. (2009) for M = Ag; Bugaris & Ibers (2009) for M = Au; Mansuetto et al. (1993); Pell & Ibers (1996) for M' = Ti; Mansuetto et al. (1992, 1993); Huang et al. (2001); Pell et al. (1997) for M' = Zr; Klepp & Sturmayr (1997, 1998); Pell et al. (1997) for M' = Hf; Seldy et al. (2005); Narducci & Ibers (2000) for M' = Th; Yao et al. (2008); Sutorik et al. (1996); Bugaris & Ibers (2009); Huang et al. (2001); Cody & Ibers (1995) for M' = U; Wells et al. (2009) for M' = Np. For computational details, see: Gelato & Parthé (1987). For additional synthetic details, see: Witt et al. (1956).

Experimental top

Cu (Aldrich, 99.5%), Tl₂Se (Aldrich, 99.999%), and Se (Cerac, 99.999%) were used as received. Th chunks were powdered according to a literature procedure (Witt et al., 1956). A fused-silica tube was loaded with Th (30 mg, 0.129 mmol), Cu (7.0 mg, 0.110 mmol), Tl₂Se (36.6 mg, 0.075 mmol), and Se (20.4 mg, 0.258 mmol), evacuated to near 10 ^-4 Torr, flame sealed, and placed in a computer-controlled furnace. It was heated to 597 K in 3 h, kept at 597 K for 24 h, heated to 1073 K in 24 h, kept at 1073 K for 96 h, cooled to 597 K in 96 h, cooled to 547 in 24 h, and then rapidly cooled to 298 K in 3 h. The reaction produced orange-red plates of TlCuThSe₃. The elemental composition of the crystals was determined to be Tl/Cu/Th/Se in an approximate ratio of 1/1/1/3 on an EDX-equipped Hitachi S-3400 SEM.

Structure description top

For compounds of type AMM'Q₃, see: Pell & Ibers (1996); Klepp & Gurtner (1996) for A = Tl; Pell et al. (1997); Yao et al. (2008); Wells et al. (2009) for M = Ag; Bugaris & Ibers (2009) for M = Au; Mansuetto et al. (1993); Pell & Ibers (1996) for M' = Ti; Mansuetto et al. (1992, 1993); Huang et al. (2001); Pell et al. (1997) for M' = Zr; Klepp & Sturmayr (1997, 1998); Pell et al. (1997) for M' = Hf; Seldy et al. (2005); Narducci & Ibers (2000) for M' = Th; Yao et al. (2008); Sutorik et al. (1996); Bugaris & Ibers (2009); Huang et al. (2001); Cody & Ibers (1995) for M' = U; Wells et al. (2009) for M' = Np. For computational details, see: Gelato & Parthé (1987). For additional synthetic details, see: Witt et al. (1956).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008a).

Figures top

	Fig. 1. Structure of TlCuThSe₃ viewed approximately down the a-axis. The 95% probability displacement ellipsoids are depicted with the unit cell outlined in red. Color key: black – Th, green – Cu, blue – Tl, orange – Se.
	Fig. 2. Polyhedral view of TlCuThSe₃ showing sheets of edge-sharing ThSe₆ octahedra (black) and CuSe₄ tetrahedra (green) separated by voids filled with Tl (blue). The unit cell is outlined in red.

Thallium(I) copper(I) thorium(IV) triselenide top

Crystal data top

TlCuThSe₃	F(000) = 1208
M_r = 736.83	D_x = 7.611 Mg m⁻³
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 1794 reflections
a = 4.1678 (2) Å	θ = 2.9–28.2°
b = 14.2227 (7) Å	µ = 68.19 mm⁻¹
c = 10.8476 (5) Å	T = 100 K
V = 643.02 (5) Å³	Rectangular plate, orange
Z = 4	0.10 × 0.07 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	474 independent reflections
Radiation source: fine-focus sealed tube	451 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 28.5°, θ_min = 2.9°
Absorption correction: numerical (SADABS; Sheldrick, 2008b)	h = −5→5
T_min = 0.101, T_max = 0.489	k = −18→18
7476 measured reflections	l = −14→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	[1.00000 + 0.00000exp(0.00(sinθ/λ)²)]/ [σ²(F_o²) + 0.0000 + 0.0000*P + (0.0193P)² + 0.0000sinθ/λ] where P = 1.00000F_o² + 0.00000F_c²
wR(F²) = 0.046	(Δ/σ)_max < 0.001
S = 1.59	Δρ_max = 2.01 e Å⁻³
474 reflections	Δρ_min = −1.34 e Å⁻³
24 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00066 (7)

Crystal data top

TlCuThSe₃	V = 643.02 (5) Å³
M_r = 736.83	Z = 4
Orthorhombic, Cmcm	Mo Kα radiation
a = 4.1678 (2) Å	µ = 68.19 mm⁻¹
b = 14.2227 (7) Å	T = 100 K
c = 10.8476 (5) Å	0.10 × 0.07 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	474 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 2008b)	451 reflections with I > 2σ(I)
T_min = 0.101, T_max = 0.489	R_int = 0.032
7476 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	24 parameters
wR(F²) = 0.046	0 restraints
S = 1.59	Δρ_max = 2.01 e Å⁻³
474 reflections	Δρ_min = −1.34 e Å⁻³

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
Th1	0.0000	0.0000	0.0000	0.00558 (15)
Tl1	0.0000	0.74746 (3)	0.2500	0.01247 (16)
Se1	0.0000	0.36628 (5)	0.06410 (7)	0.0067 (2)
Se2	0.0000	0.06909 (8)	0.2500	0.0059 (2)
Cu1	0.0000	0.46554 (10)	0.2500	0.0085 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Th1	0.0050 (2)	0.0078 (2)	0.0040 (2)	0.000	0.000	−0.00012 (14)
Tl1	0.0101 (3)	0.0092 (3)	0.0181 (3)	0.000	0.000	0.000
Se1	0.0062 (4)	0.0071 (4)	0.0067 (4)	0.000	0.000	−0.0002 (3)
Se2	0.0069 (5)	0.0064 (5)	0.0043 (5)	0.000	0.000	0.000
Cu1	0.0100 (7)	0.0096 (7)	0.0060 (6)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Th1—Se2ⁱ	2.8844 (4)	Se1—Th1^ix	2.9057 (5)
Th1—Se2	2.8844 (4)	Se1—Th1^viii	2.9057 (5)
Th1—Se1ⁱⁱ	2.9057 (5)	Se1—Tl1^v	3.3564 (6)
Th1—Se1ⁱⁱⁱ	2.9057 (5)	Se1—Tl1ⁱⁱⁱ	3.3564 (6)
Th1—Se1^iv	2.9057 (5)	Se1—Tl1^xii	3.7717 (8)
Th1—Se1^v	2.9057 (5)	Se1—Tl1^xiv	5.6211 (6)
Th1—Cu1^iv	3.4550 (2)	Se1—Tl1^xv	5.6211 (6)
Th1—Cu1^v	3.4550 (2)	Se2—Cu1ⁱⁱⁱ	2.5517 (11)
Th1—Cu1ⁱⁱ	3.4550 (2)	Se2—Cu1^v	2.5517 (11)
Th1—Cu1ⁱⁱⁱ	3.4550 (2)	Se2—Th1^xvi	2.8844 (4)
Th1—Th1^vi	4.1678 (2)	Se2—Tl1^v	3.2831 (9)
Th1—Th1^vii	4.1678 (2)	Se2—Tl1ⁱⁱⁱ	3.2831 (9)
Tl1—Se2^viii	3.2831 (9)	Se2—Tl1^xvii	4.5744 (12)
Tl1—Se2^ix	3.2831 (9)	Cu1—Se1	2.4617 (11)
Tl1—Se1^x	3.3564 (6)	Cu1—Se1^xviii	2.4617 (11)
Tl1—Se1^viii	3.3564 (6)	Cu1—Se2^ix	2.5517 (11)
Tl1—Se1^xi	3.3564 (6)	Cu1—Se2^viii	2.5517 (11)
Tl1—Se1^ix	3.3564 (6)	Cu1—Th1^xix	3.4550 (2)
Tl1—Cu1^ix	3.7368 (13)	Cu1—Th1^viii	3.4550 (2)
Tl1—Cu1^viii	3.7368 (13)	Cu1—Th1^xx	3.4550 (2)
Tl1—Se1^xii	3.7717 (8)	Cu1—Th1^ix	3.4550 (2)
Tl1—Se1^xiii	3.7717 (8)	Cu1—Tl1ⁱⁱⁱ	3.7368 (13)
Tl1—Cu1	4.0095 (16)	Cu1—Tl1^v	3.7368 (13)
Tl1—Tl1^vii	4.1678 (2)

Se2ⁱ—Th1—Se2	180.0	Th1^ix—Se1—Tl1^v	91.607 (8)
Se2ⁱ—Th1—Se1ⁱⁱ	89.89 (2)	Th1^viii—Se1—Tl1^v	156.72 (3)
Se2—Th1—Se1ⁱⁱ	90.11 (2)	Cu1—Se1—Tl1ⁱⁱⁱ	78.26 (3)
Se2ⁱ—Th1—Se1ⁱⁱⁱ	90.11 (2)	Th1^ix—Se1—Tl1ⁱⁱⁱ	156.72 (3)
Se2—Th1—Se1ⁱⁱⁱ	89.89 (2)	Th1^viii—Se1—Tl1ⁱⁱⁱ	91.607 (8)
Se1ⁱⁱ—Th1—Se1ⁱⁱⁱ	180.00 (4)	Tl1^v—Se1—Tl1ⁱⁱⁱ	76.761 (17)
Se2ⁱ—Th1—Se1^iv	89.89 (2)	Cu1—Se1—Tl1^xii	170.40 (4)
Se2—Th1—Se1^iv	90.11 (2)	Th1^ix—Se1—Tl1^xii	93.702 (18)
Se1ⁱⁱ—Th1—Se1^iv	91.64 (2)	Th1^viii—Se1—Tl1^xii	93.702 (18)
Se1ⁱⁱⁱ—Th1—Se1^iv	88.36 (2)	Tl1^v—Se1—Tl1^xii	109.076 (17)
Se2ⁱ—Th1—Se1^v	90.11 (2)	Tl1ⁱⁱⁱ—Se1—Tl1^xii	109.076 (17)
Se2—Th1—Se1^v	89.89 (2)	Cu1—Se1—Tl1^xiv	131.422 (8)
Se1ⁱⁱ—Th1—Se1^v	88.36 (2)	Th1^ix—Se1—Tl1^xiv	125.11 (2)
Se1ⁱⁱⁱ—Th1—Se1^v	91.64 (2)	Th1^viii—Se1—Tl1^xiv	60.762 (10)
Se1^iv—Th1—Se1^v	180.00 (4)	Tl1^v—Se1—Tl1^xiv	132.816 (19)
Se2^viii—Tl1—Se2^ix	78.80 (3)	Tl1ⁱⁱⁱ—Se1—Tl1^xiv	76.051 (8)
Se2^viii—Tl1—Se1^x	141.551 (14)	Tl1^xii—Se1—Tl1^xiv	47.856 (6)
Se2^ix—Tl1—Se1^x	89.713 (15)	Cu1—Se1—Tl1^xv	131.422 (9)
Se2^viii—Tl1—Se1^viii	89.713 (15)	Th1^ix—Se1—Tl1^xv	60.763 (10)
Se2^ix—Tl1—Se1^viii	141.551 (14)	Th1^viii—Se1—Tl1^xv	125.11 (2)
Se1^x—Tl1—Se1^viii	119.54 (3)	Tl1^v—Se1—Tl1^xv	76.051 (8)
Se2^viii—Tl1—Se1^xi	89.713 (15)	Tl1ⁱⁱⁱ—Se1—Tl1^xv	132.816 (19)
Se2^ix—Tl1—Se1^xi	141.551 (14)	Tl1^xii—Se1—Tl1^xv	47.856 (6)
Se1^x—Tl1—Se1^xi	76.760 (17)	Tl1^xiv—Se1—Tl1^xv	95.712 (12)
Se1^viii—Tl1—Se1^xi	73.86 (2)	Cu1ⁱⁱⁱ—Se2—Cu1^v	109.50 (7)
Se2^viii—Tl1—Se1^ix	141.551 (14)	Cu1ⁱⁱⁱ—Se2—Th1	78.662 (19)
Se2^ix—Tl1—Se1^ix	89.713 (15)	Cu1^v—Se2—Th1	78.662 (19)
Se1^x—Tl1—Se1^ix	73.86 (2)	Cu1ⁱⁱⁱ—Se2—Th1^xvi	78.662 (19)
Se1^viii—Tl1—Se1^ix	76.760 (17)	Cu1^v—Se2—Th1^xvi	78.662 (19)
Se1^xi—Tl1—Se1^ix	119.54 (3)	Th1—Se2—Th1^xvi	140.17 (4)
Se2^viii—Tl1—Se1^xii	70.645 (11)	Cu1ⁱⁱⁱ—Se2—Tl1^v	164.65 (4)
Se2^ix—Tl1—Se1^xii	70.645 (11)	Cu1^v—Se2—Tl1^v	85.85 (3)
Se1^x—Tl1—Se1^xii	139.351 (12)	Th1—Se2—Tl1^v	105.262 (13)
Se1^viii—Tl1—Se1^xii	70.924 (17)	Th1^xvi—Se2—Tl1^v	105.262 (13)
Se1^xi—Tl1—Se1^xii	139.351 (11)	Cu1ⁱⁱⁱ—Se2—Tl1ⁱⁱⁱ	85.85 (3)
Se1^ix—Tl1—Se1^xii	70.924 (17)	Cu1^v—Se2—Tl1ⁱⁱⁱ	164.65 (4)
Cu1^ix—Tl1—Se1^xii	110.855 (11)	Th1—Se2—Tl1ⁱⁱⁱ	105.262 (13)
Cu1^viii—Tl1—Se1^xii	110.855 (11)	Th1^xvi—Se2—Tl1ⁱⁱⁱ	105.262 (13)
Se2^viii—Tl1—Se1^xiii	70.645 (11)	Tl1^v—Se2—Tl1ⁱⁱⁱ	78.80 (3)
Se2^ix—Tl1—Se1^xiii	70.645 (11)	Cu1ⁱⁱⁱ—Se2—Tl1^xvii	54.75 (3)
Se1^x—Tl1—Se1^xiii	70.924 (17)	Cu1^v—Se2—Tl1^xvii	54.75 (3)
Se1^viii—Tl1—Se1^xiii	139.351 (11)	Th1—Se2—Tl1^xvii	70.08 (2)
Se1^xi—Tl1—Se1^xiii	70.924 (17)	Th1^xvi—Se2—Tl1^xvii	70.08 (2)
Se1^ix—Tl1—Se1^xiii	139.351 (11)	Tl1^v—Se2—Tl1^xvii	140.600 (14)
Cu1^ix—Tl1—Se1^xiii	110.855 (11)	Tl1ⁱⁱⁱ—Se2—Tl1^xvii	140.600 (14)
Cu1^viii—Tl1—Se1^xiii	110.855 (11)	Se1—Cu1—Se1^xviii	110.01 (7)
Se1^xii—Tl1—Se1^xiii	129.21 (3)	Se1—Cu1—Se2^ix	109.328 (14)
Cu1—Se1—Th1^ix	79.67 (3)	Se1^xviii—Cu1—Se2^ix	109.328 (14)
Cu1—Se1—Th1^viii	79.67 (3)	Se1—Cu1—Se2^viii	109.328 (14)
Th1^ix—Se1—Th1^viii	91.64 (2)	Se1^xviii—Cu1—Se2^viii	109.328 (14)
Cu1—Se1—Tl1^v	78.26 (3)	Se2^ix—Cu1—Se2^viii	109.51 (7)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, −y+1/2, −z; (iii) x−1/2, y−1/2, z; (iv) −x−1/2, −y+1/2, −z; (v) x+1/2, y−1/2, z; (vi) x−1, y, z; (vii) x+1, y, z; (viii) x−1/2, y+1/2, z; (ix) x+1/2, y+1/2, z; (x) x+1/2, y+1/2, −z+1/2; (xi) x−1/2, y+1/2, −z+1/2; (xii) −x, −y+1, −z; (xiii) −x, −y+1, z+1/2; (xiv) −x−1, −y+1, −z; (xv) −x+1, −y+1, −z; (xvi) −x, −y, z+1/2; (xvii) x, y−1, z; (xviii) x, y, −z+1/2; (xix) −x+1/2, −y+1/2, z+1/2; (xx) −x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	TlCuThSe₃
M_r	736.83
Crystal system, space group	Orthorhombic, Cmcm
Temperature (K)	100
a, b, c (Å)	4.1678 (2), 14.2227 (7), 10.8476 (5)
V (Å³)	643.02 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	68.19
Crystal size (mm)	0.10 × 0.07 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Numerical (SADABS; Sheldrick, 2008b)
T_min, T_max	0.101, 0.489
No. of measured, independent and observed [I > 2σ(I)] reflections	7476, 474, 451
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.046, 1.59
No. of reflections	474
No. of parameters	24
Δρ_max, Δρ_min (e Å⁻³)	2.01, −1.34

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008a), SHELXL97 (Sheldrick, 2008a), CrystalMaker (Palmer, 2009).

Selected bond lengths (Å) top

Th1—Se2ⁱ	2.8844 (4)	Tl1—Se1^viii	3.3564 (6)
Th1—Se2	2.8844 (4)	Tl1—Se1^vi	3.3564 (6)
Th1—Se1ⁱⁱ	2.9057 (5)	Tl1—Se1^ix	3.3564 (6)
Th1—Se1ⁱⁱⁱ	2.9057 (5)	Tl1—Se1^vii	3.3564 (6)
Th1—Se1^iv	2.9057 (5)	Cu1—Se1	2.4617 (11)
Th1—Se1^v	2.9057 (5)	Cu1—Se1^x	2.4617 (11)
Tl1—Se2^vi	3.2831 (9)	Cu1—Se2^vii	2.5517 (11)
Tl1—Se2^vii	3.2831 (9)	Cu1—Se2^vi	2.5517 (11)

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

Acknowledgements

The research was supported at Northwestern University by the U. S. Department of Energy, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division and Division of Materials Sciences and Engineering Grant ER-15522. The research was also supported by funding received from the DOE Office of Nuclear Energy's Nuclear Energy University Programs. A special thanks to Professor Thomas E. Albrecht-Schmitt at the University of Notre-Dame for his donation of thorium metal.

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