Pb6Co9(TeO6)5

Artner, C.; Weil, M.

doi:10.1107/S1600536812037038

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page i71

doi:10.1107/S1600536812037038

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Pb₆Co₉(TeO₆)₅

Christine Artner ^a and Matthias Weil ^a ^*

^aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, Vienna University of Technology, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
^*Correspondence e-mail: mweil@mail.zserv.tuwien.ac.at

(Received 21 August 2012; accepted 27 August 2012; online 31 August 2012)

Pb₆Co₉(TeO₆)₅, hexalead(II) nonacobalt(II) pentatellurate(VI), is isotypic with its nickel(II) analogue. The asymmetric unit contains two Pb atoms (site symmetries .2., ..2), four Co atoms (..2, ..2, 3.., 3.2) two Te atoms (..2, 3..) and six O atoms (all in general positions), with the Te and Co sites in octahedral coordination environments. The crystal structure can be subdivided into two types of layers parallel to (001). The first layer at z ≃ 0.25 is made up of edge-sharing [CoO₆] and [TeO₆] octahedra, with 1/6 of the octahedral holes not occupied. The second layer, situated at z ≃ 0, consist of an alternating arrangement of Pb^II atoms and of double octahedra that are made up from face-sharing [CoO₆] and [TeO₆] octahedra. The two types of layers are linked together through corner-sharing of [CoO₆] and [TeO₆] octahedra. The Pb^II atoms are situated in the cavities of the framework and are stereochemically active with one-sided [4]- and [6]-coordinations, respectively.

Related literature

For the isotypic nickel analogue, see: Wedel et al. (1998 ). Reviews on the crystal chemistry of oxotellurates(VI) and of the geometry of [Co^IIO₆] polyhedra are given by Levason (1997 ) and Wildner (1992 ), respectively. For Pb₅TeO₈, see: Artner & Weil (2012 ). For the bond-valence method, see: Brown (2002 ).

Experimental

Crystal data

Pb₆Co₉(TeO₆)₅
M_r = 2891.51
Hexagonal, P 6₃ 22
a = 10.3915 (1) Å
c = 13.6273 (2) Å
V = 1274.37 (3) Å³
Z = 2
Mo Kα radiation
μ = 50.89 mm⁻¹
T = 293 K
0.07 × 0.06 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical (HABITUS; Herrendorf, 1997 ) T_min = 0.123, T_max = 0.200
45686 measured reflections
2262 independent reflections
1908 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.056
S = 1.09
2262 reflections
81 parameters
Δρ_max = 2.96 e Å⁻³
Δρ_min = −2.59 e Å⁻³
Absolute structure: Flack (1983 ), 882 Friedel pairs
Flack parameter: 0.134 (10)

Table 1
Selected bond lengths (Å)

Te1—O2	1.906 (5)
Te1—O6	1.991 (4)
Te2—O5	1.917 (6)
Te2—O3	1.937 (7)
Te2—O1ⁱ	1.939 (5)
Co1—O5ⁱⁱ	2.004 (6)
Co1—O6	2.262 (5)
Co2—O2	2.090 (6)
Co2—O3ⁱⁱⁱ	2.090 (8)
Co2—O1	2.108 (6)
Co3—O3	2.107 (4)
Co4—O2	2.067 (7)
Co4—O1^iv	2.071 (4)
Co4—O5^v	2.116 (7)
Symmetry codes: (i) $[x-y, x, z+{\script{1\over 2}}]$ ; (ii) $[-x+y, y, -z+{\script{1\over 2}}]$ ; (iii) y, x, -z; (iv) -x+y, -x+1, z; (v) x-y, -y+1, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS for Windows (Dowty, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812037038/br2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812037038/br2208Isup2.hkl

checkCIF report

Comment top

Single crystals of the title compound, Pb₆Co₉(TeO₆)₅, were serendipitously obtained as a minority phase during phase formation studies in the system Pb^II/Co^II/Te^VI/O intended on crystal growth of cubic Pb₂CoTeO₆.

The crystal structure of Pb₆Co₉(TeO₆)₅ is isotypic with its nickel analogue (Wedel et al., 1998). The two Te(VI) and the four Co(II) atoms are in slightly distorted octahedral coordination environments with mean bond lengths of ¯d(Te—O) = 1.940 Å and ¯d(Co—O) = 2.105 Å, both in good agreement with literature data for oxotellurates (Levason, 1997) and for [CoO₆] octahedra (Wildner, 1992). The two lead(II) atoms exhibit coordination numbers of four and six. The crresponding Pb—O, Te—O and M—O (M = Co, Ni) bond lengths are very similar in the two isotypic structures.

The crystal structure of Pb₆Co₉(TeO₆)₅ can be described in terms of (001) layers A at z ≈ 0.25 and B at z ≈ 0 that stack alternately along [100] (Fig. 1). In layer A [TeO₆] and [CoO₆] octahedra share edges with 1/6 of the octahedral holes at the 2c and 2d positions, both with site symmetry 3.2, not occupied. The corresponding vacancies, denominated as X1 at the 2d position and as X2 at the 2c position, have different sizes. X1 has a diagonal diameter of 4.1076 (8) Å whereas X2 is somewhat larger with a diagonal diameter of 4.3258 (8) Å. This difference might be correlated with the size of the surrounding octahedra. Whereas the smaller X1 vacancy is encircled by a ring of six [CoO₆] octahedra, the larger X2 is encircled by a ring of three [CoO₆] and three slightly smaller [TeO₆] octahedra (Fig. 2). Layer B consists of double octahedra that are made up from face-sharing [CoO₆] and [TeO₆] octahedra, and by surrounding lead(II) atoms (Fig. 3). Adjacent A and B layers are linked together above and below the X1 and X2 vacancies through corner-sharing of [CoO₆] and [TeO₆] octahedra.

The resulting [Co₉Te₅O₃₀]^12- framework anion leaves space for the stereochemically active lead(II) cations. The oxygen coordination of the two Pb²⁺ cations is one-sided, with a [4]-coordination for Pb1 and a [6]-coordination for Pb2, if only Pb—O distances less than 2.75 Å are taken into account. The two cations share a common edge (O6—O6') with the lone pair electrons E pointing towards opposite directions. However, a bond valence calculation (Brown, 2002) shows a significant contribution of the four additional Pb—O distances for each of the two Pb atoms if interactions up to 3.5 Å are considered. Inclusion of these bonds increases the bond valence sum at Pb1 from 1.61 valence units (vu) to 1.83 vu and at Pb2 from 1.64 to 1.96 vu. The bond valence sum at O3 is also raised from 1.60 to 1.80 vu. Therefore the overall coordination of Pb1 might be described as [4 + 4] and that of Pb2 as [6 + 4] (Fig. 4).

Related literature top

For the isotypic nickel analogue, see: Wedel et al. (1998). Reviews on the crystal chemistry of oxotellurates(VI) and of the geometry of [Co^IIO₆] polyhedra are given by Levason (1997) and Wildner (1992), respectively. For Pb₅TeO₈, see: Artner & Weil (2012). For the bond-valence method, see: Brown (2002).

Experimental top

1.281 (5.7 mmol) PbO, 0.216 g (2.9 mmol) CoO and 0.914 g (5.7 mmol) TeO₂ were mixed and thoroughly ground and heated in an alumina crucible under atmospheric conditions during 6 h to 1023 K and held at that temperature for 48 h. Then the furnace was shut-off. Several crystal phases could be identified from the cooled reaction mixture by single-crystal diffraction: Dark blue isometric crystals of Pb₂CoTeO₆, dark-red (nearly black) block-like crystals of Pb₅TeO₈ (Artner & Weil, 2012), colourless crystals of α-Al₂O₃ and dark red crystals of Pb₆Co₉(TeO₆)₅ with a block-like shape.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS for Windows (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The crystal structure of Pb₆Co₉(TeO₆)₅ in a projection along [010]. Displacement ellipsoids are drawn at the 90% probability level. Letters A and B indicate the two types of layers present in the structure.
	Fig. 2. Layer A (situated approximately at z ≈ 1/4) in the crystal structure of Pb₆Co₉(TeO₆)₅. Colour code and probability of the displacement parameters as in Fig. 1.
	Fig. 3. Layer B (situated approximately at z ≈ 0) in the crystal structure of Pb₆Co₉(TeO₆)₅. Colour code and probability of the displacement parameters as in Fig. 1.
	Fig. 4. The coordination spheres around the two lead atoms, considering bond lengths up to 3.5 Å; short Pb—O distances < 2.75 Å are given in black, emphasizing the one-sided [4]-coordination for Pb1 and [6]-coordination for Pb2. Longer bonds augmenting the coordination spheres are given in yellow. Probability of the displacement parameters as in Fig. 1.

hexalead(II) nonacobalt(II) pentatellurate(VI) top

Crystal data top

Pb₆Co₉(TeO₆)₅	D_x = 7.535 Mg m⁻³
M_r = 2891.51	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃22	Cell parameters from 6739 reflections
Hall symbol: P 6c 2c	θ = 2.8–36.8°
a = 10.3915 (1) Å	µ = 50.89 mm⁻¹
c = 13.6273 (2) Å	T = 293 K
V = 1274.37 (3) Å³	Parallelepiped, dark red
Z = 2	0.07 × 0.06 × 0.05 mm
F(000) = 2470

Data collection top

Bruker APEXII CCD diffractometer	2262 independent reflections
Radiation source: fine-focus sealed tube	1908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ω and ϕ scans	θ_max = 37.6°, θ_min = 2.3°
Absorption correction: numerical (HABITUS; Herrendorf, 1997)	h = −16→17
T_min = 0.123, T_max = 0.200	k = −17→17
45686 measured reflections	l = −22→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0244P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.025	(Δ/σ)_max < 0.001
wR(F²) = 0.056	Δρ_max = 2.96 e Å⁻³
S = 1.09	Δρ_min = −2.59 e Å⁻³
2262 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
81 parameters	Extinction coefficient: 0.00019 (3)
0 restraints	Absolute structure: Flack (1983), 882 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.134 (10)

Crystal data top

Pb₆Co₉(TeO₆)₅	Z = 2
M_r = 2891.51	Mo Kα radiation
Hexagonal, P6₃22	µ = 50.89 mm⁻¹
a = 10.3915 (1) Å	T = 293 K
c = 13.6273 (2) Å	0.07 × 0.06 × 0.05 mm
V = 1274.37 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2262 independent reflections
Absorption correction: numerical (HABITUS; Herrendorf, 1997)	1908 reflections with I > 2σ(I)
T_min = 0.123, T_max = 0.200	R_int = 0.068
45686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.056	Δρ_max = 2.96 e Å⁻³
S = 1.09	Δρ_min = −2.59 e Å⁻³
2262 reflections	Absolute structure: Flack (1983), 882 Friedel pairs
81 parameters	Absolute structure parameter: 0.134 (10)

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
Pb1	0.26736 (3)	0.26736 (3)	0.0000	0.01216 (6)
Pb2	0.38848 (3)	1.0000	0.0000	0.01881 (8)
Te1	0.3333	0.6667	−0.09611 (4)	0.00407 (10)
Te2	0.16730 (4)	0.33460 (9)	0.2500	0.00433 (8)
Co1	0.3333	0.6667	0.11832 (9)	0.0066 (2)
Co2	0.16885 (10)	0.3377 (2)	−0.2500	0.00664 (18)
Co3	0.0000	0.0000	0.2500	0.0087 (3)
Co4	0.00992 (19)	0.50496 (10)	−0.2500	0.00566 (18)
O1	0.3366 (5)	0.3241 (5)	−0.1717 (3)	0.0077 (8)
O2	0.1726 (7)	0.5050 (6)	−0.1628 (3)	0.0083 (10)
O3	0.1702 (7)	0.1801 (6)	0.3277 (3)	0.0105 (9)
O5	0.3239 (8)	0.4818 (6)	0.3295 (3)	0.0076 (10)
O6	0.3481 (4)	0.5265 (4)	−0.0034 (4)	0.0069 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01117 (9)	0.01117 (9)	0.01243 (12)	0.00429 (9)	0.00014 (9)	−0.00014 (9)
Pb2	0.01104 (9)	0.01201 (13)	0.03372 (18)	0.00601 (7)	−0.00268 (13)	−0.0054 (3)
Te1	0.00414 (14)	0.00414 (14)	0.0039 (2)	0.00207 (7)	0.000	0.000
Te2	0.00362 (13)	0.00380 (19)	0.00564 (18)	0.00190 (10)	0.0002 (4)	0.000
Co1	0.0066 (3)	0.0066 (3)	0.0066 (5)	0.00332 (16)	0.000	0.000
Co2	0.0057 (3)	0.0069 (5)	0.0077 (4)	0.0035 (2)	0.0006 (10)	0.000
Co3	0.0061 (4)	0.0061 (4)	0.0140 (7)	0.00305 (19)	0.000	0.000
Co4	0.0031 (5)	0.0045 (3)	0.0089 (4)	0.0015 (2)	0.000	−0.0002 (3)
O1	0.011 (2)	0.008 (2)	0.0048 (15)	0.0055 (14)	0.0003 (13)	−0.0022 (13)
O2	0.007 (2)	0.006 (2)	0.012 (2)	0.0022 (17)	−0.0001 (16)	−0.0034 (15)
O3	0.011 (2)	0.012 (2)	0.0077 (16)	0.0059 (15)	0.0000 (15)	0.0011 (15)
O5	0.004 (2)	0.006 (2)	0.0072 (18)	−0.0011 (18)	−0.0005 (18)	0.0009 (15)
O6	0.0058 (14)	0.0070 (14)	0.0075 (15)	0.0029 (11)	−0.001 (2)	0.002 (2)

Geometric parameters (Å, º) top

Pb1—O6ⁱ	2.387 (4)	Te2—O3ⁱⁱⁱ	1.937 (7)
Pb1—O6	2.387 (4)	Te2—O3	1.937 (7)
Pb1—O1ⁱ	2.432 (4)	Te2—O1^xii	1.939 (5)
Pb1—O1	2.432 (4)	Te2—O1ⁱ	1.939 (5)
Pb1—O3ⁱⁱ	3.327 (7)	Co1—O5^x	2.004 (6)
Pb1—O3ⁱⁱⁱ	3.327 (7)	Co1—O5ⁱⁱⁱ	2.004 (6)
Pb1—O3^iv	3.453 (7)	Co1—O5^xiii	2.004 (6)
Pb1—O3^v	3.453 (7)	Co1—O6^vi	2.262 (5)
Pb1—Pb2^vi	3.5764 (4)	Co1—O6^vii	2.262 (5)
Pb1—Pb2^vii	3.5777 (2)	Co1—O6	2.262 (5)
Pb2—O6^viii	2.420 (3)	Co2—O2^xiv	2.090 (6)
Pb2—O6^vii	2.420 (3)	Co2—O2	2.090 (6)
Pb2—O2^ix	2.726 (5)	Co2—O3ⁱ	2.090 (8)
Pb2—O2^vi	2.726 (5)	Co2—O3^iv	2.090 (8)
Pb2—O5^x	2.727 (5)	Co2—O1	2.108 (6)
Pb2—O5^xi	2.727 (5)	Co2—O1^xiv	2.108 (6)
Pb2—O6^vi	3.155 (3)	Co3—O3^xv	2.107 (4)
Pb2—O6^ix	3.155 (3)	Co3—O3	2.107 (4)
Pb2—O3^xi	3.230 (4)	Co3—O3^xvi	2.107 (4)
Pb2—O3^x	3.230 (4)	Co3—O3^xvii	2.107 (4)
Te1—O2^vi	1.906 (5)	Co3—O3ⁱⁱⁱ	2.107 (4)
Te1—O2	1.906 (5)	Co3—O3^v	2.107 (4)
Te1—O2^vii	1.906 (5)	Co4—O2	2.067 (7)
Te1—O6^vi	1.991 (4)	Co4—O2^xviii	2.067 (7)
Te1—O6^vii	1.991 (4)	Co4—O1^vi	2.071 (4)
Te1—O6	1.991 (4)	Co4—O1^xiv	2.071 (4)
Te2—O5	1.917 (6)	Co4—O5^xix	2.116 (7)
Te2—O5ⁱⁱⁱ	1.917 (6)	Co4—O5^iv	2.116 (7)

O6ⁱ—Pb1—O6	84.58 (16)	O5ⁱⁱⁱ—Te2—O1^xii	85.9 (2)
O6ⁱ—Pb1—O1ⁱ	79.26 (18)	O3ⁱⁱⁱ—Te2—O1^xii	87.0 (2)
O6—Pb1—O1ⁱ	77.79 (18)	O3—Te2—O1^xii	93.7 (2)
O6ⁱ—Pb1—O1	77.79 (18)	O5—Te2—O1ⁱ	85.9 (2)
O6—Pb1—O1	79.26 (18)	O5ⁱⁱⁱ—Te2—O1ⁱ	93.3 (2)
O1ⁱ—Pb1—O1	148.79 (19)	O3ⁱⁱⁱ—Te2—O1ⁱ	93.7 (2)
O6ⁱ—Pb1—O3ⁱⁱ	95.87 (13)	O3—Te2—O1ⁱ	87.0 (2)
O6—Pb1—O3ⁱⁱ	133.98 (17)	O1^xii—Te2—O1ⁱ	179.0 (3)
O1ⁱ—Pb1—O3ⁱⁱ	147.68 (15)	O5^x—Co1—O5ⁱⁱⁱ	108.14 (14)
O1—Pb1—O3ⁱⁱ	56.26 (15)	O5^x—Co1—O5^xiii	108.14 (14)
O6ⁱ—Pb1—O3ⁱⁱⁱ	133.98 (17)	O5ⁱⁱⁱ—Co1—O5^xiii	108.14 (14)
O6—Pb1—O3ⁱⁱⁱ	95.87 (13)	O5^x—Co1—O6^vi	87.99 (18)
O1ⁱ—Pb1—O3ⁱⁱⁱ	56.26 (15)	O5ⁱⁱⁱ—Co1—O6^vi	85.39 (19)
O1—Pb1—O3ⁱⁱⁱ	147.68 (15)	O5^xiii—Co1—O6^vi	153.55 (18)
O3ⁱⁱ—Pb1—O3ⁱⁱⁱ	114.8 (2)	O5^x—Co1—O6^vii	85.39 (19)
O6ⁱ—Pb1—O3^iv	138.20 (17)	O5ⁱⁱⁱ—Co1—O6^vii	153.55 (18)
O6—Pb1—O3^iv	95.05 (13)	O5^xiii—Co1—O6^vii	87.99 (18)
O1ⁱ—Pb1—O3^iv	141.63 (15)	O6^vi—Co1—O6^vii	72.17 (17)
O1—Pb1—O3^iv	61.26 (14)	O5^x—Co1—O6	153.55 (18)
O3ⁱⁱ—Pb1—O3^iv	55.44 (13)	O5ⁱⁱⁱ—Co1—O6	87.99 (18)
O3ⁱⁱⁱ—Pb1—O3^iv	87.73 (10)	O5^xiii—Co1—O6	85.39 (18)
O6ⁱ—Pb1—O3^v	95.05 (13)	O6^vi—Co1—O6	72.17 (17)
O6—Pb1—O3^v	138.20 (17)	O6^vii—Co1—O6	72.17 (17)
O1ⁱ—Pb1—O3^v	61.26 (14)	O2^xiv—Co2—O2	87.8 (3)
O1—Pb1—O3^v	141.63 (15)	O2^xiv—Co2—O3ⁱ	92.52 (17)
O3ⁱⁱ—Pb1—O3^v	87.73 (10)	O2—Co2—O3ⁱ	174.4 (3)
O3ⁱⁱⁱ—Pb1—O3^v	55.44 (13)	O2^xiv—Co2—O3^iv	174.4 (3)
O3^iv—Pb1—O3^v	111.4 (2)	O2—Co2—O3^iv	92.52 (17)
O6^viii—Pb2—O6^vii	83.17 (17)	O3ⁱ—Co2—O3^iv	87.7 (2)
O6^viii—Pb2—O2^ix	61.34 (16)	O2^xiv—Co2—O1	89.3 (2)
O6^vii—Pb2—O2^ix	107.91 (19)	O2—Co2—O1	95.5 (2)
O6^viii—Pb2—O2^vi	107.91 (19)	O3ⁱ—Co2—O1	78.9 (2)
O6^vii—Pb2—O2^vi	61.34 (16)	O3^iv—Co2—O1	96.2 (2)
O2^ix—Pb2—O2^vi	166.8 (3)	O2^xiv—Co2—O1^xiv	95.5 (2)
O6^viii—Pb2—O5^x	106.77 (19)	O2—Co2—O1^xiv	89.3 (2)
O6^vii—Pb2—O5^x	68.25 (16)	O3ⁱ—Co2—O1^xiv	96.2 (2)
O2^ix—Pb2—O5^x	66.27 (12)	O3^iv—Co2—O1^xiv	78.9 (2)
O2^vi—Pb2—O5^x	112.94 (13)	O1—Co2—O1^xiv	173.3 (3)
O6^viii—Pb2—O5^xi	68.25 (16)	O3^xv—Co3—O3	175.2 (5)
O6^vii—Pb2—O5^xi	106.77 (19)	O3^xv—Co3—O3^xvi	79.5 (4)
O2^ix—Pb2—O5^xi	112.94 (13)	O3—Co3—O3^xvi	96.96 (14)
O2^vi—Pb2—O5^xi	66.27 (12)	O3^xv—Co3—O3^xvii	86.8 (4)
O5^x—Pb2—O5^xi	173.7 (3)	O3—Co3—O3^xvii	96.96 (14)
O6^viii—Pb2—O6^vi	138.39 (2)	O3^xvi—Co3—O3^xvii	96.96 (14)
O6^vii—Pb2—O6^vi	55.23 (15)	O3^xv—Co3—O3ⁱⁱⁱ	96.96 (14)
O2^ix—Pb2—O6^vi	126.25 (15)	O3—Co3—O3ⁱⁱⁱ	79.5 (4)
O2^vi—Pb2—O6^vi	55.67 (17)	O3^xvi—Co3—O3ⁱⁱⁱ	86.8 (4)
O5^x—Pb2—O6^vi	60.10 (16)	O3^xvii—Co3—O3ⁱⁱⁱ	175.2 (5)
O5^xi—Pb2—O6^vi	120.76 (15)	O3^xv—Co3—O3^v	96.96 (14)
O6^viii—Pb2—O6^ix	55.23 (15)	O3—Co3—O3^v	86.8 (4)
O6^vii—Pb2—O6^ix	138.39 (2)	O3^xvi—Co3—O3^v	175.2 (5)
O2^ix—Pb2—O6^ix	55.67 (17)	O3^xvii—Co3—O3^v	79.5 (4)
O2^vi—Pb2—O6^ix	126.25 (15)	O3ⁱⁱⁱ—Co3—O3^v	96.96 (14)
O5^x—Pb2—O6^ix	120.76 (15)	O2—Co4—O2^xviii	89.8 (3)
O5^xi—Pb2—O6^ix	60.10 (16)	O2—Co4—O1^vi	96.9 (2)
O6^vi—Pb2—O6^ix	166.38 (13)	O2^xviii—Co4—O1^vi	91.0 (2)
O6^viii—Pb2—O3^xi	120.59 (18)	O2—Co4—O1^xiv	91.0 (2)
O6^vii—Pb2—O3^xi	121.18 (18)	O2^xviii—Co4—O1^xiv	96.9 (2)
O2^ix—Pb2—O3^xi	130.9 (2)	O1^vi—Co4—O1^xiv	168.8 (4)
O2^vi—Pb2—O3^xi	60.21 (13)	O2—Co4—O5^xix	174.7 (3)
O5^x—Pb2—O3^xi	132.1 (2)	O2^xviii—Co4—O5^xix	90.92 (16)
O5^xi—Pb2—O3^xi	53.44 (14)	O1^vi—Co4—O5^xix	77.8 (2)
O6^vi—Pb2—O3^xi	86.29 (19)	O1^xiv—Co4—O5^xix	94.2 (2)
O6^ix—Pb2—O3^xi	84.37 (18)	O2—Co4—O5^iv	90.92 (16)
O6^viii—Pb2—O3^x	121.18 (18)	O2^xviii—Co4—O5^iv	174.7 (3)
O6^vii—Pb2—O3^x	120.59 (18)	O1^vi—Co4—O5^iv	94.2 (2)
O2^ix—Pb2—O3^x	60.21 (13)	O1^xiv—Co4—O5^iv	77.8 (2)
O2^vi—Pb2—O3^x	130.9 (2)	O5^xix—Co4—O5^iv	88.9 (3)
O5^x—Pb2—O3^x	53.44 (14)	Te2ⁱⁱ—O1—Co4^vii	98.54 (19)
O5^xi—Pb2—O3^x	132.1 (2)	Te2ⁱⁱ—O1—Co2	96.67 (17)
O6^vi—Pb2—O3^x	84.37 (18)	Co4^vii—O1—Co2	89.3 (2)
O6^ix—Pb2—O3^x	86.29 (19)	Te2ⁱⁱ—O1—Pb1	116.6 (2)
O3^xi—Pb2—O3^x	93.32 (14)	Co4^vii—O1—Pb1	136.07 (18)
O2^vi—Te1—O2	99.15 (18)	Co2—O1—Pb1	110.4 (2)
O2^vi—Te1—O2^vii	99.15 (18)	Te1—O2—Co4	129.1 (3)
O2—Te1—O2^vii	99.15 (18)	Te1—O2—Co2	130.4 (4)
O2^vi—Te1—O6^vi	90.7 (2)	Co4—O2—Co2	89.87 (19)
O2—Te1—O6^vi	85.2 (2)	Te1—O2—Pb2^vii	95.48 (17)
O2^vii—Te1—O6^vi	168.4 (2)	Co4—O2—Pb2^vii	96.4 (2)
O2^vi—Te1—O6^vii	85.2 (2)	Co2—O2—Pb2^vii	111.0 (2)
O2—Te1—O6^vii	168.4 (2)	Te2—O3—Co2^xx	97.34 (17)
O2^vii—Te1—O6^vii	90.7 (2)	Te2—O3—Co3	96.2 (2)
O6^vi—Te1—O6^vii	84.0 (2)	Co2^xx—O3—Co3	92.8 (3)
O2^vi—Te1—O6	168.4 (2)	Te2—O5—Co1^xiii	125.5 (4)
O2—Te1—O6	90.7 (2)	Te2—O5—Co4^xx	97.7 (2)
O2^vii—Te1—O6	85.2 (2)	Co1^xiii—O5—Co4^xx	120.3 (3)
O6^vi—Te1—O6	84.0 (2)	Te2—O5—Pb2^xxi	117.3 (2)
O6^vii—Te1—O6	84.0 (2)	Co1^xiii—O5—Pb2^xxi	97.82 (18)
O5—Te2—O5ⁱⁱⁱ	92.5 (3)	Co4^xx—O5—Pb2^xxi	95.2 (2)
O5—Te2—O3ⁱⁱⁱ	177.8 (2)	Te1—O6—Co1	86.54 (14)
O5ⁱⁱⁱ—Te2—O3ⁱⁱⁱ	89.6 (2)	Te1—O6—Pb1	136.5 (2)
O5—Te2—O3	89.6 (2)	Co1—O6—Pb1	127.8 (2)
O5ⁱⁱⁱ—Te2—O3	177.8 (2)	Te1—O6—Pb2^vi	103.41 (16)
O3ⁱⁱⁱ—Te2—O3	88.2 (2)	Co1—O6—Pb2^vi	100.34 (16)
O5—Te2—O1^xii	93.3 (2)	Pb1—O6—Pb2^vi	96.12 (13)

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

Experimental details

Crystal data
Chemical formula	Pb₆Co₉(TeO₆)₅
M_r	2891.51
Crystal system, space group	Hexagonal, P6₃22
Temperature (K)	293
a, c (Å)	10.3915 (1), 13.6273 (2)
V (Å³)	1274.37 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	50.89
Crystal size (mm)	0.07 × 0.06 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Numerical (HABITUS; Herrendorf, 1997)
T_min, T_max	0.123, 0.200
No. of measured, independent and observed [I > 2σ(I)] reflections	45686, 2262, 1908
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.858

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.056, 1.09
No. of reflections	2262
No. of parameters	81
Δρ_max, Δρ_min (e Å⁻³)	2.96, −2.59
Absolute structure	Flack (1983), 882 Friedel pairs
Absolute structure parameter	0.134 (10)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS for Windows (Dowty, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Te1—O2	1.906 (5)	Co2—O2	2.090 (6)
Te1—O6	1.991 (4)	Co2—O3ⁱⁱⁱ	2.090 (8)
Te2—O5	1.917 (6)	Co2—O1	2.108 (6)
Te2—O3	1.937 (7)	Co3—O3	2.107 (4)
Te2—O1ⁱ	1.939 (5)	Co4—O2	2.067 (7)
Co1—O5ⁱⁱ	2.004 (6)	Co4—O1^iv	2.071 (4)
Co1—O6	2.262 (5)	Co4—O5^v	2.116 (7)

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

Acknowledgements

The X-ray centre of the Vienna University of Technology is acknowledged for providing access to the single-crystal diffractometer.

References

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