Redetermination of the crystal structure of NaTcO4 at 100 and 296 K based on single-crystal X-ray data

German, K.E.; Grigoriev, M.S.; Garashchenko, B.L.; Kopytin, A.V.; Tyupina, E.A.

doi:10.1107/S2056989017008362

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Volume 73| Part 7| July 2017| Pages 1037-1040

https://doi.org/10.1107/S2056989017008362

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Redetermination of the crystal structure of NaTcO₄ at 100 and 296 K based on single-crystal X-ray data

Konstantin E. German,^a,^b ^* Mikhail S. Grigoriev,^a Bogdan L. Garashchenko,^c Alexander V. Kopytin ^a,^d and Ekaterina A. Tyupina ^c,^e

^aA.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky prospekt, 119071 Moscow, Russian Federation, ^bMedical University Reaviz, 2 Krasnobogatyrskaya, building 2, 107564 Moscow, Russian Federation, ^cD. Mendeleyev University of Chemical Technology of Russia, 9 Miusskaya pl., 125047 Moscow, Russian Federation, ^dKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prospect, 119991 Moscow, Russian Federation, and ^eNational Research Nuclear University, 31 Kashirskoye sh., 115409 Moscow, Russian Federation
^*Correspondence e-mail: guerman_k@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 12 May 2017; accepted 6 June 2017; online 16 June 2017)

The redetermination of the title compound, sodium pertechnate, from single-crystal CCD data recorded both at 296 and 100 K confirms previous studies based on X-ray powder diffraction film data [Schwochau (1962 ). Z. Naturforsch. Teil A, 17, 630; Keller & Kanellakopulos (1963 ). Radiochim. Acta, 1, 107–108] and neutron powder diffraction data using the Rietveld method [Weaver et al. (2017 ). Inorg. Chem. 12, 677–681], but reveals a considerable improvement in precision. The standard uncertainties of the room-temperature structure determination are about seven times lower than those of the neutron diffraction structure determination and about 13 times lower at 100 K, due to the decrease in the amplitude of librations. The crystal expansion could be approximated linearly with a thermal volumic expansion coefficient of 1.19 (12) × 10⁻⁴ K⁻¹. NaTcO₄ adopts the scheelite (CaWO₄) structure type in space group type I4₁/a with Na and Tc atoms (both with site symmetry -4) replacing Ca and W atoms, respectively.

Keywords: Technetium; sodium; redetermination; crystal structure; low temperature; high precision.

CCDC references: 1554512; 1554511

1. Chemical context

Sodium pertechnetate, NaTcO₄, refers to a group of d⁰-tetroxide anion salts. Since the inception of quantum chemistry, compounds of this type have been models (generally with respect to the MnO₄⁻ anion) for which the validity of the proposed equations and approximations for the case of d-electrons are verified. It was believed that, owing to the d⁰ electronic state, they define the least complex class of compounds of d-elements. Such simplicity, due to the absence of d-electrons and their pseudospherical symmetry, does by far not imply that any of these compounds show no complex behavior under changing environmental conditions, e.g. by changing temperature and/or the strength of the crystal field, and publications on the discovery of a more complex behaviour and properties appeared periodically. For example, for sodium (German et al., 1987b , 1993 ), potassium (German et al., 1993; Gafurov & Aliev, 2005 ) and caesium (Tarasov et al., 1991 , 1992 ) tetraoxidotechnates, the existence of phase transitions was noted at high temperatures, while for the rhenium analogue, caesium tetraoxidorhenate, the ability of laser-excited second harmonic generation has been observed (Stefanovich et al., 1991 ). Differences for these systems are also observed in the crystal structures. Potassium permanganate crystallizes in the orthorhombic system (Palenik, 1967 ), whereas the pertechnetate and perrhenate of the same cation crystallize in the tetragonal system (Hoppe et al., 1999 ; Schwochau, 1962). Next to the interest for the TcO₄⁻ anion in its sodium salt, sodium cations in general are worth being investigated in detail. For example, sodium salts are known to form hydrates with different hydration numbers and various coordination numbers for the sodium cation. The change in these numbers often occurs in the vitally important temperature range of 309–313 K (German et al., 1987b; Tarasov et al., 2015 ). Precise structural data of such systems are important for the analyses of transmutation rates in homogeneous systems as noted by Kuo et al. (2017 ) and in this respect, are more useful than the data of previously determined structures (Kuo et al., 2017; Ackerman et al., 2016 ; German et al., 1987a ; Spitsyn et al., 1987 ; Tarasov et al., 1983 , 1991). Likewise, Ackerman et al. (2016) have shown that precise structural data are needed for the estimation of the incorporation possibility for ⁹⁹Tc into stable scheelite matrices of different compositions. Another aspect for obtaining more precise structure data on pertechnates is to clarify if pseudo-Jahn–Teller distortions of d⁰-tetraoxide anions really take place when compared with previous determinations (German et al., 1987a; Spitsyn et al., 1987; Tarasov et al., 1983, 1991). In this context we have reinvestigated the crystal structure of NaTcO₄ that is known from powder diffraction data only, namely by inspection of its X-ray powder diffraction pattern (Schwochau, 1962; Keller & Kanellakopulos, 1963) and Rietveld refinement of neutron powder diffraction data (Weaver et al., 2017).

2. Structural commentary

The structure of anhydrous NaTcO₄, determined here on the basis of X-ray diffraction data of a single crystal recorded both at room and low temperature, belongs to the CaWO₄ structural type (space group type I4₁/a). The obtained bond lengths and angles are similar to those obtained from previous X-ray powder (Keller & Kanellakopulos, 1963; Schwochau, 1962) and neutron powder diffraction studies (Weaver et al., 2017)

Lattice parameters determined here with the precision of 0.0002-0.0005 Å at 296 K (Table 1) are close to those of a = 5.342 (3) Å, c = 11.874 (6) Å given by Weaver et al. (2017). The lattice parameters at 100 K are a = 5.2945 (2) Å, c = 11.7470 (5) Å (single crystal measurement). These values represent the thermal volumic expansion coefficient of 1.19 (12) × 10 ⁻⁴ K⁻¹. The c/a ratio in this structure changes from 2.2187 (7) to 2.2223 (4) as a function of the temperature change from 100 to 296 K.

Table 1
Selected geometric parameters (Å, °) at 100 K

Tc1—O1	1.7208 (3)	Na1—O1ⁱⁱ	2.5980 (4)
Na1—O1ⁱ	2.5107 (4)

O1ⁱⁱⁱ—Tc1—O1	108.439 (12)	O1^iv—Tc1—O1	111.56 (3)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z; (iii) $[-y+{\script{5\over 4}}, x+{\script{1\over 4}}, -z+{\script{1\over 4}}]$ ; (iv) $[-x+1, -y+{\script{3\over 2}}, z]$ .

Our results confirm that NaTcO₄ is isostructural to KTcO₄ and RbTcO₄ (Keller & Kanellakopulos, 1963). The structure is composed of three atom types (Na, Tc, O). The Tc and Na atoms occupy special positions with $[\overline{4}]$ symmetry, Wyckoff positions 4b and 4a, respectively. The configuration of the TeO₄⁻ anion is that of a slightly distorted tetrahedron both at 296 K and at 100 K (Tables 1 and 2). The Tc—O distances are 1.7183 (6) Å at 296 K and 1.7208 (3) Å at 100 K. These distances are in good agreement with values known for these ions from the literature (German et al., 1987a; Tarasov et al., 1992; Kuo et al., 2017; Ackerman et al., 2016). The elongation of bonds (Fig. 1), while decreasing the temperature from 296 K to 100 K, can be attributed to a decrease in the libration effect (German et al., 1987a). A similar phenomenon has previously been observed in the structure of anilinium pertechnetate (Maruk et al., 2010 ).

Table 2
Selected geometric parameters (Å, °) at 296 K

Tc1—O1	1.7183 (6)	O1—Na1ⁱⁱ	2.6304 (6)
O1—Na1ⁱ	2.5357 (6)

O1—Tc1—O1ⁱⁱⁱ	111.53 (5)	O1—Tc1—O1^iv	108.45 (2)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) $[-x+1, -y+{\script{3\over 2}}, z]$ ; (iv) $[y-{\script{1\over 4}}, -x+{\script{5\over 4}}, -z+{\script{1\over 4}}]$ .

Figure 1
The elongation of bonds upon cooling from 296 K [(II), A] to 100 K [(I), B] is associated with a decrease in libration (C). All displacement ellipsoids are drawn at the 50% probability. [Symmetry codes: (a) −y + $[{5\over 4}]$ , x + $[{1\over 4}]$ , −z + $[{1\over 4}]$ ; (b) −x + 1, −y + $[{3\over 2}]$ , z; (c) y + $[{3\over 2}]$ , −x + $[{11\over 4}]$ ., z + $[{3\over 4}]$ .]

The greatest distortion of the TcO₄⁻ anion from an ideal tetrahedral configuration reported by Weaver et al. (2017) is confirmed by our analysis of the O—Tc—O angles in the NaTcO₄ structure, but the difference is not as high as in the model from the neutron diffraction experiment (Weaver et al., 2017). The maximum deviation values are 3.12° at 100 K and 3.08° at 296 K for the sodium salt and are larger in comparison with the potassium and rubidium salts, because the sodium cation has the smallest ionic radius compared to K⁺ and Rb⁺ and hence has the highest polarizing ability. This distortion is insensitive to the temperature change from 100 K to 296 K.

The packing of Na⁺ cations and TcO₄⁻ anions in the crystal is presented in Fig. 2. Each Na⁺ cation is coordinated by eight oxygen atoms that are belonging to four TcO₄⁻ anions. The resulting coordination polyhedron can be described as a distorted dodecahedron (Fig. 3). The two dihedral angles between pairs of two triangular faces sharing an edge that connects two five-edged vertices of the dodecahedron are equal to 21.2 and 30.3°, respectively. The corresponding faces should form an angle of 29.5° for a dodecahedron and 0° for a square anti-prism according to the Aslanov–Porai-Koshits criterion (Porai-Koshits & Aslanov, 1972 ). Hence the coordination polyhedron of the sodium cation is closer to a dodecahedron than to a square anti-prism. Each of the four oxygen atoms of an individual TcO₄⁻ anion is in contact with two sodium cations, so that each TcO₄⁻ anion is directly contacted with eight sodium cations.

Figure 2
View of the crystal packing of the title compound.

Figure 3
The coordination polyhedron of the sodium cation (data from 100 K measurement).

3. Synthesis and crystallization

The synthesis of the title compound was carried out based on neutralization of an aqueous solution of freshly prepared HTcO₄ with an equivalent quantity of 1 M aqueous solution of chemically pure sodium hydroxide. The HTcO₄ solution was made by dissolution of Tc₂O₇ sublimed from TcO₂ in an oxygen flow at 973 K.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Seven (six) reflections at room (and low) temperature were omitted from refinement due to large differences between observed and calculated intensities.

Table 3
Experimental details

	100 K	296 K
Crystal data
Chemical formula	NaTcO₄	NaTcO₄
M_r	185.9	185.9
Crystal system, space group	Tetragonal, I4₁/a	Tetragonal, I4₁/a
Temperature (K)	100	296
a, c (Å)	5.2945 (2), 11.7470 (5)	5.3325 (1), 11.8503 (3)
V (Å³)	329.29 (3)	336.97 (2)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	4.33	4.23
Crystal size (mm)	0.34 × 0.28 × 0.20	0.28 × 0.26 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII area-detector	Bruker Kappa APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.399, 0.478	0.386, 0.485
No. of measured, independent and observed [I > 2σ(I)] reflections	6909, 678, 661	2371, 365, 350
R_int	0.018	0.016
(sin θ/λ)_max (Å⁻¹)	0.995	0.805

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.009, 0.017, 1.31	0.008, 0.019, 1.16
No. of reflections	678	365
No. of parameters	15	15
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.34	0.23, −0.33
Computer programs: APEX2 and SAINT-Plus (Bruker, 2008), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC references: 1554512; 1554511

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989017008362/wm5391sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017008362/wm5391Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017008362/wm5391IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017008362/wm5391Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989017008362/wm5391IIsup5.cml

checkCIF report

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(I) Sodium pertechnetate top

Crystal data top

NaTcO₄	Melting point < 1063 K
M_r = 185.9	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 5622 reflections
a = 5.2945 (2) Å	θ = 4.2–45.4°
c = 11.7470 (5) Å	µ = 4.33 mm⁻¹
V = 329.29 (3) Å³	T = 100 K
Z = 4	Fragment, colourless
F(000) = 344	0.34 × 0.28 × 0.20 mm
D_x = 3.750 Mg m⁻³

Data collection top

Bruker Kappa APEXII area-detector diffractometer	661 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.018
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 45.0°, θ_min = 4.2°
T_min = 0.399, T_max = 0.478	h = −10→10
6909 measured reflections	k = −10→10
678 independent reflections	l = −22→23

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0029P)² + 0.0769P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.009	(Δ/σ)_max < 0.001
wR(F²) = 0.017	Δρ_max = 0.26 e Å⁻³
S = 1.31	Δρ_min = −0.34 e Å⁻³
678 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
15 parameters	Extinction coefficient: 0.0489 (10)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tc1	0.5000	0.7500	0.1250	0.00517 (2)
Na1	0.0000	0.2500	0.1250	0.00980 (7)
O1	0.73565 (6)	0.62081 (7)	0.04262 (3)	0.00879 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tc1	0.00489 (2)	0.00489 (2)	0.00574 (3)	0.000	0.000	0.000
Na1	0.00988 (10)	0.00988 (10)	0.00965 (16)	0.000	0.000	0.000
O1	0.00795 (11)	0.00901 (11)	0.00942 (11)	0.00054 (9)	0.00202 (10)	−0.00104 (10)

Geometric parameters (Å, º) top

Tc1—O1ⁱ	1.7208 (3)	Na1—O1^viii	2.5980 (4)
Tc1—O1ⁱⁱ	1.7208 (3)	Na1—O1^ix	2.5980 (4)
Tc1—O1ⁱⁱⁱ	1.7208 (3)	Na1—O1^x	2.5980 (4)
Tc1—O1	1.7208 (3)	Na1—Na1^xi	3.9538 (1)
Na1—O1^iv	2.5107 (4)	Na1—Na1^xii	3.9538 (1)
Na1—O1^v	2.5107 (4)	Na1—Na1^xiii	3.9538 (1)
Na1—O1^vi	2.5107 (4)	Na1—Na1^xiv	3.9538 (1)
Na1—O1^vii	2.5107 (4)	O1—Na1^vii	2.5107 (4)
Na1—O1ⁱⁱⁱ	2.5980 (4)	O1—Na1^xv	2.5980 (4)

O1ⁱ—Tc1—O1ⁱⁱ	108.439 (12)	O1ⁱⁱⁱ—Na1—Na1^xi	129.596 (8)
O1ⁱ—Tc1—O1ⁱⁱⁱ	111.56 (3)	O1^viii—Na1—Na1^xi	85.180 (8)
O1ⁱⁱ—Tc1—O1ⁱⁱⁱ	108.439 (12)	O1^ix—Na1—Na1^xi	38.498 (8)
O1ⁱ—Tc1—O1	108.439 (12)	O1^x—Na1—Na1^xi	103.255 (8)
O1ⁱⁱ—Tc1—O1	111.56 (3)	O1^iv—Na1—Na1^xii	162.891 (8)
O1ⁱⁱⁱ—Tc1—O1	108.439 (12)	O1^v—Na1—Na1^xii	66.415 (8)
O1^iv—Na1—O1^v	127.954 (10)	O1^vi—Na1—Na1^xii	40.101 (8)
O1^iv—Na1—O1^vi	127.954 (10)	O1^vii—Na1—Na1^xii	102.079 (9)
O1^v—Na1—O1^vi	76.700 (17)	O1ⁱⁱⁱ—Na1—Na1^xii	38.498 (8)
O1^iv—Na1—O1^vii	76.700 (17)	O1^viii—Na1—Na1^xii	103.255 (8)
O1^v—Na1—O1^vii	127.954 (10)	O1^ix—Na1—Na1^xii	85.180 (8)
O1^vi—Na1—O1^vii	127.954 (10)	O1^x—Na1—Na1^xii	129.596 (8)
O1^iv—Na1—O1ⁱⁱⁱ	149.332 (14)	Na1^xi—Na1—Na1^xii	123.484 (2)
O1^v—Na1—O1ⁱⁱⁱ	67.259 (8)	O1^iv—Na1—Na1^xiii	66.415 (8)
O1^vi—Na1—O1ⁱⁱⁱ	78.599 (12)	O1^v—Na1—Na1^xiii	102.079 (9)
O1^vii—Na1—O1ⁱⁱⁱ	73.985 (7)	O1^vi—Na1—Na1^xiii	162.891 (8)
O1^iv—Na1—O1^viii	73.985 (7)	O1^vii—Na1—Na1^xiii	40.101 (8)
O1^v—Na1—O1^viii	78.599 (12)	O1ⁱⁱⁱ—Na1—Na1^xiii	85.180 (8)
O1^vi—Na1—O1^viii	67.259 (8)	O1^viii—Na1—Na1^xiii	129.596 (8)
O1^vii—Na1—O1^viii	149.332 (14)	O1^ix—Na1—Na1^xiii	103.255 (8)
O1ⁱⁱⁱ—Na1—O1^viii	136.261 (16)	O1^x—Na1—Na1^xiii	38.498 (8)
O1^iv—Na1—O1^ix	78.599 (12)	Na1^xi—Na1—Na1^xiii	84.064 (3)
O1^v—Na1—O1^ix	149.332 (14)	Na1^xii—Na1—Na1^xiii	123.484 (2)
O1^vi—Na1—O1^ix	73.985 (7)	O1^iv—Na1—Na1^xiv	102.079 (9)
O1^vii—Na1—O1^ix	67.259 (8)	O1^v—Na1—Na1^xiv	40.101 (8)
O1ⁱⁱⁱ—Na1—O1^ix	97.976 (6)	O1^vi—Na1—Na1^xiv	66.415 (8)
O1^viii—Na1—O1^ix	97.976 (6)	O1^vii—Na1—Na1^xiv	162.891 (8)
O1^iv—Na1—O1^x	67.259 (8)	O1ⁱⁱⁱ—Na1—Na1^xiv	103.255 (8)
O1^v—Na1—O1^x	73.985 (7)	O1^viii—Na1—Na1^xiv	38.498 (8)
O1^vi—Na1—O1^x	149.332 (14)	O1^ix—Na1—Na1^xiv	129.596 (8)
O1^vii—Na1—O1^x	78.599 (12)	O1^x—Na1—Na1^xiv	85.180 (8)
O1ⁱⁱⁱ—Na1—O1^x	97.976 (6)	Na1^xi—Na1—Na1^xiv	123.484 (2)
O1^viii—Na1—O1^x	97.976 (6)	Na1^xii—Na1—Na1^xiv	84.064 (4)
O1^ix—Na1—O1^x	136.261 (16)	Na1^xiii—Na1—Na1^xiv	123.484 (2)
O1^iv—Na1—Na1^xi	40.101 (8)	Tc1—O1—Na1^vii	137.472 (19)
O1^v—Na1—Na1^xi	162.891 (8)	Tc1—O1—Na1^xv	118.781 (18)
O1^vi—Na1—Na1^xi	102.079 (9)	Na1^vii—O1—Na1^xv	101.402 (12)
O1^vii—Na1—Na1^xi	66.415 (8)

Symmetry codes: (i) −y+5/4, x+1/4, −z+1/4; (ii) −x+1, −y+3/2, z; (iii) y−1/4, −x+5/4, −z+1/4; (iv) x−1, y−1/2, −z; (v) y−3/4, −x+5/4, z+1/4; (vi) −y+3/4, x−3/4, z+1/4; (vii) −x+1, −y+1, −z; (viii) −y+1/4, x−3/4, −z+1/4; (ix) −x+1, −y+1/2, z; (x) x−1, y, z; (xi) −x, −y, −z; (xii) −x+1/2, −y+1/2, −z+1/2; (xiii) −x, −y+1, −z; (xiv) −x−1/2, −y+1/2, −z+1/2; (xv) x+1, y, z.

(II) Sodium tetraoxidotechnetate(VII) top

Crystal data top

O₄Tc·Na	D_x = 3.664 Mg m⁻³
M_r = 185.9	Melting point < 1063 K
Tetragonal, I4₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 4ad	Cell parameters from 2097 reflections
a = 5.3325 (1) Å	θ = 4.2–35.2°
c = 11.8503 (3) Å	µ = 4.23 mm⁻¹
V = 336.97 (2) Å³	T = 296 K
Z = 4	Fragment, colourless
F(000) = 344	0.28 × 0.26 × 0.20 mm

Data collection top

Bruker Kappa APEX II area-detector diffractometer	365 independent reflections
Graphite monochromator	350 reflections with I > 2σ(I)
Detector resolution: 9.091 pixels mm^-1	R_int = 0.016
ω– and φ–scans	θ_max = 34.9°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→7
T_min = 0.386, T_max = 0.485	k = −8→8
2371 measured reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0071P)² + 0.0846P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.008	(Δ/σ)_max < 0.001
wR(F²) = 0.019	Δρ_max = 0.23 e Å⁻³
S = 1.16	Δρ_min = −0.33 e Å⁻³
365 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
15 parameters	Extinction coefficient: 0.136 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tc1	0.5000	0.7500	0.1250	0.01434 (6)
Na1	0.0000	0.2500	0.1250	0.02546 (16)
O1	0.73494 (12)	0.62442 (11)	0.04342 (6)	0.02225 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tc1	0.01355 (6)	0.01355 (6)	0.01591 (7)	0.000	0.000	0.000
Na1	0.0261 (2)	0.0261 (2)	0.0242 (4)	0.000	0.000	0.000
O1	0.0200 (2)	0.0225 (2)	0.0242 (3)	0.0005 (2)	0.0050 (2)	−0.0030 (2)

Geometric parameters (Å, º) top

Tc1—O1ⁱ	1.7183 (6)	Na1—O1^vii	2.5357 (6)
Tc1—O1	1.7183 (6)	Na1—O1ⁱⁱⁱ	2.6303 (6)
Tc1—O1ⁱⁱ	1.7183 (6)	Na1—O1^viii	2.6303 (6)
Tc1—O1ⁱⁱⁱ	1.7183 (6)	Na1—O1^ix	2.6303 (6)
Na1—O1^iv	2.5357 (6)	Na1—O1^x	2.6303 (6)
Na1—O1^v	2.5357 (6)	O1—Na1^vii	2.5357 (6)
Na1—O1^vi	2.5357 (6)	O1—Na1^xi	2.6304 (6)

O1ⁱ—Tc1—O1	108.45 (2)	O1ⁱⁱⁱ—Na1—Na1^xii	129.245 (14)
O1ⁱ—Tc1—O1ⁱⁱ	108.45 (2)	O1^viii—Na1—Na1^xii	85.049 (14)
O1—Tc1—O1ⁱⁱ	111.53 (5)	O1^ix—Na1—Na1^xii	38.652 (13)
O1ⁱ—Tc1—O1ⁱⁱⁱ	111.53 (5)	O1^x—Na1—Na1^xii	103.569 (14)
O1—Tc1—O1ⁱⁱⁱ	108.45 (2)	O1^iv—Na1—Na1^xiii	163.325 (14)
O1ⁱⁱ—Tc1—O1ⁱⁱⁱ	108.45 (2)	O1^v—Na1—Na1^xiii	65.896 (14)
O1^iv—Na1—O1^v	128.283 (18)	O1^vi—Na1—Na1^xiii	40.383 (14)
O1^iv—Na1—O1^vi	128.283 (18)	O1^vii—Na1—Na1^xiii	102.250 (15)
O1^v—Na1—O1^vi	76.17 (3)	O1ⁱⁱⁱ—Na1—Na1^xiii	38.652 (13)
O1^iv—Na1—O1^vii	76.17 (3)	O1^viii—Na1—Na1^xiii	103.569 (14)
O1^v—Na1—O1^vii	128.283 (18)	O1^ix—Na1—Na1^xiii	85.049 (14)
O1^vi—Na1—O1^vii	128.283 (18)	O1^x—Na1—Na1^xiii	129.245 (14)
O1^iv—Na1—O1ⁱⁱⁱ	148.68 (2)	Na1^xii—Na1—Na1^xiii	123.539 (1)
O1^v—Na1—O1ⁱⁱⁱ	67.149 (15)	O1^iv—Na1—Na1^xiv	65.896 (14)
O1^vi—Na1—O1ⁱⁱⁱ	79.04 (2)	O1^v—Na1—Na1^xiv	102.250 (15)
O1^vii—Na1—O1ⁱⁱⁱ	73.993 (11)	O1^vi—Na1—Na1^xiv	163.325 (14)
O1^iv—Na1—O1^viii	73.993 (11)	O1^vii—Na1—Na1^xiv	40.383 (14)
O1^v—Na1—O1^viii	79.04 (2)	O1ⁱⁱⁱ—Na1—Na1^xiv	85.049 (14)
O1^vi—Na1—O1^viii	67.149 (15)	O1^viii—Na1—Na1^xiv	129.245 (14)
O1^vii—Na1—O1^viii	148.68 (2)	O1^ix—Na1—Na1^xiv	103.569 (14)
O1ⁱⁱⁱ—Na1—O1^viii	136.88 (3)	O1^x—Na1—Na1^xiv	38.652 (13)
O1^iv—Na1—O1^ix	79.04 (2)	Na1^xii—Na1—Na1^xiv	83.973 (2)
O1^v—Na1—O1^ix	148.68 (2)	Na1^xiii—Na1—Na1^xiv	123.539 (1)
O1^vi—Na1—O1^ix	73.993 (11)	O1^iv—Na1—Na1^xv	102.250 (15)
O1^vii—Na1—O1^ix	67.149 (15)	O1^v—Na1—Na1^xv	40.383 (14)
O1ⁱⁱⁱ—Na1—O1^ix	97.762 (10)	O1^vi—Na1—Na1^xv	65.896 (14)
O1^viii—Na1—O1^ix	97.762 (10)	O1^vii—Na1—Na1^xv	163.325 (14)
O1^iv—Na1—O1^x	67.149 (15)	O1ⁱⁱⁱ—Na1—Na1^xv	103.569 (14)
O1^v—Na1—O1^x	73.993 (11)	O1^viii—Na1—Na1^xv	38.652 (13)
O1^vi—Na1—O1^x	148.68 (2)	O1^ix—Na1—Na1^xv	129.245 (14)
O1^vii—Na1—O1^x	79.04 (2)	O1^x—Na1—Na1^xv	85.049 (14)
O1ⁱⁱⁱ—Na1—O1^x	97.762 (10)	Na1^xii—Na1—Na1^xv	123.539 (1)
O1^viii—Na1—O1^x	97.762 (10)	Na1^xiii—Na1—Na1^xv	83.973 (2)
O1^ix—Na1—O1^x	136.88 (3)	Na1^xiv—Na1—Na1^xv	123.539 (1)
O1^iv—Na1—Na1^xii	40.383 (14)	Tc1—O1—Na1^vii	138.27 (3)
O1^v—Na1—Na1^xii	163.325 (14)	Tc1—O1—Na1^xi	118.74 (3)
O1^vi—Na1—Na1^xii	102.250 (15)	Na1^vii—O1—Na1^xi	100.96 (2)
O1^vii—Na1—Na1^xii	65.896 (14)

Symmetry codes: (i) −y+5/4, x+1/4, −z+1/4; (ii) −x+1, −y+3/2, z; (iii) y−1/4, −x+5/4, −z+1/4; (iv) x−1, y−1/2, −z; (v) y−3/4, −x+5/4, z+1/4; (vi) −y+3/4, x−3/4, z+1/4; (vii) −x+1, −y+1, −z; (viii) −y+1/4, x−3/4, −z+1/4; (ix) −x+1, −y+1/2, z; (x) x−1, y, z; (xi) x+1, y, z; (xii) −x, −y, −z; (xiii) −x+1/2, −y+1/2, −z+1/2; (xiv) −x, −y+1, −z; (xv) −x−1/2, −y+1/2, −z+1/2.

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Volume 73| Part 7| July 2017| Pages 1037-1040

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