Na₃DyCl₆

Abstract

Single crystals of the title compound, tris­odium hexa­chloridodysprosate, Na₃DyCl₆, were obtained as a by-product of synthesis using dysprosium(III) chloride and sodium chloride among others. The monoclinic structure with its typical β angle close to 90° [90.823 (4)°] is isotypic with the mineral cryolite (Na₃AlF₆) and the high-temperature structure of the Na₃ MCl₆ series, with M = Eu–Lu, Y and Sc. The isolated, almost perfect [DyCl₆]³⁻ octa­hedra are inter­connected via two crystallographically different Na⁺ cations: while one Na⁺ resides on centres of symmetry (as well as Dy³⁺) and also builds almost perfect, isolated [NaCl₆]⁵⁻ octa­hedra, the other Na⁺ is surrounded by seven chloride anions forming a distorted [NaCl₇]⁶⁻ trigonal prism with just one cap as close secondary contact.

Related literature

The first structural descriptions of the Na₃ MCl₆ series (M = Eu–Lu, Y and Sc) on a single crystal in the cryolite-type structure (Hawthorne &, Ferguson, 1975 ▶) were given for M = Er by Meyer et al. (1987 ▶), for M = Ho by Böcker et al. (2001 ▶) and for M = Y by Liao & Dronskowski (2004 ▶). For the correlation between the two temperature-dependent phases, see: Meyer (1984 ▶); Meyer et al. (1987 ▶); Wickleder & Meyer (1995 ▶). For a planned synthesis of Dy₂NCl₃, compare with those for Gd₂NCl₃ (Schwanitz-Schüller & Simon, 1985 ▶) and Y₂NCl₃ (Meyer et al., 1989 ▶).

Experimental

Crystal data

• Na₃DyCl₆

• M _r = 444.17

• Monoclinic,

• a = 6.8791 (5) Å

• b = 7.2816 (5) Å

• c = 10.1734 (7) Å

• β = 90.823 (4)°

• V = 509.54 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 8.96 mm⁻¹

• T = 293 K

• 0.20 × 0.15 × 0.10 mm

Data collection

• Nonius Kappa-CCD diffractometer

• Absorption correction: numerical (X-SHAPE; Stoe & Cie 1999 ▶) T _min = 0.218, T _max = 0.414

• 12026 measured reflections

• 1245 independent reflections

• 1124 reflections with I > 2σ(I)

• R _int = 0.071

Refinement

• R[F ² > 2σ(F ²)] = 0.019

• wR(F ²) = 0.045

• S = 1.08

• 1245 reflections

• 50 parameters

• Δρ_max = 0.84 e Å⁻³

• Δρ_min = −1.05 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Na1—Cl2i	2.7358 (8)
Na1—Cl3iii	2.7902 (8)
Na1—Cl1	2.8687 (8)
Na2—Cl1	2.8295 (19)
Na2—Cl2vi	2.8341 (19)
Na2—Cl1iv	2.8492 (19)
Na2—Cl3i	2.8612 (19)
Na2—Cl3vii	3.204 (2)
Na2—Cl2iv	3.325 (2)
Na2—Cl2	3.488 (2)
Dy—Cl2	2.6176 (8)
Dy—Cl3	2.6320 (8)
Dy—Cl1viii	2.6447 (8)

Symmetry codes: (i) ; (iii) ; (iv) ; (vi) ; (vii) ; (viii) .

supplementary crystallographic information

Comment

Trisodiumhexachlorodysprosate(III) belongs to a group of ternary chlorides Na₃MCl₆ with M = Eu – Lu, Y and Sc (Meyer et al., 1987), which crystallize in the cryolite-type structure (Hawthorne et al., 1975). The Dy³⁺ and (Na1)⁺ occupy the 2a and 2b Wyckoff positions at centres of symmetry, whereas the three crystallographically different chloride anions and (Na2)⁺ reside at the 4e position with the site symmetry 1. A l l cations have six primary contacts to Cl^-, but the [(Na2)Cl₆]^5- polyhedron can not only be described as distorted trigonal prism instead of the usual octahedra that are realised for [DyCl₆]^3- and [(Na1)Cl₆]^5-, it moreover carries a seventh capping Cl^- anion. The isolated [DyCl₆]^3- octahedra are interconnected to a three-dimensional texture via sodium cations (Fig. 1). This structure represents the high-temperature phase of the Na₃MCl₆ series with M = Eu – Lu, Y and Sc. The transition into the low-temperature phase with its trigonal structure (Meyer, 1984) depends on the radius of the actual lanthanoid(III) cation (Wickleder et al., 1995) and is estimated for M = Dy at around 290 K, hence not far below the temperature of the measurement.

Experimental

Colourless and transparent single crystals of Na₃DyCl₆ were obtained as by-product from the reaction of sodium azide (NaN₃), dysprosium metal (Dy) and its the corresponding trichloride (DyCl₃) in presence of sodium chloride (NaCl) as flux, originally designed to produce Dy₂NCl₃ in analogy to Gd₂NCl₃ (Schwanitz-Schüller et al., 1985) and Y₂NCl₃ (Meyer et al., 1989) instead. The reaction mixture was placed into a torch- sealed evacuated fused-silica vessel, which was heated at 1143 K for seven days, followed by cooling to room temperature within one day.

Figures

Fig. 1.

Crystal structure of cryolite-type Na3DyCl6. Displacement ellipsoids are drawn at 90% probability level.

Crystal data

Na3DyCl6	F(000) = 402
Mr = 444.17	Dx = 2.895 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -p2yn	Cell parameters from 8457 reflections
a = 6.8791 (5) Å	θ = 3.4–28.1°
b = 7.2816 (5) Å	µ = 8.96 mm−1
c = 10.1734 (7) Å	T = 293 K
β = 90.823 (4)°	Block, colourless
V = 509.54 (6) Å3	0.20 × 0.15 × 0.10 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1245 independent reflections
Radiation source: fine-focus sealed tube	1124 reflections with I > 2σ(I)
graphite	Rint = 0.071
charge cpouled device scans	θmax = 28.1°, θmin = 3.4°
Absorption correction: numerical (X-SHAPE; Stoe & Cie 1999)	h = −9→9
Tmin = 0.218, Tmax = 0.414	k = −9→9
12026 measured reflections	l = −13→13

Refinement

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)] = 0.019	w = 1/[σ2(Fo2) + (0.0199P)2 + 0.2881P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.045	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.84 e Å−3
1245 reflections	Δρmin = −1.05 e Å−3
50 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0043 (5)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Na1	0.0000	0.0000	0.5000	0.0291 (4)
Na2	0.5218 (2)	−0.0749 (2)	0.24225 (18)	0.0499 (4)
Dy	0.0000	0.0000	0.0000	0.01593 (9)
Cl1	0.13816 (12)	0.06522 (12)	0.23941 (8)	0.02834 (18)
Cl2	−0.31489 (12)	0.17894 (12)	0.06382 (9)	0.0358 (2)
Cl3	0.16836 (13)	0.30521 (11)	−0.07742 (9)	0.0358 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.0323 (11)	0.0244 (10)	0.0303 (10)	−0.0038 (7)	−0.0033 (9)	0.0027 (7)
Na2	0.0462 (9)	0.0341 (9)	0.0694 (12)	−0.0069 (7)	0.0029 (8)	0.0033 (8)
Dy	0.01762 (12)	0.01512 (12)	0.01509 (12)	−0.00060 (6)	0.00126 (7)	−0.00138 (6)
Cl1	0.0334 (4)	0.0333 (4)	0.0182 (3)	0.0032 (3)	−0.0037 (3)	−0.0035 (3)
Cl2	0.0322 (4)	0.0323 (4)	0.0431 (5)	0.0149 (3)	0.0120 (4)	0.0090 (4)
Cl3	0.0350 (4)	0.0271 (4)	0.0450 (5)	−0.0123 (3)	−0.0069 (4)	0.0122 (4)

Geometric parameters (Å, °)

Na1—Cl2i	2.7358 (8)	Na2—Dyiv	4.0608 (17)
Na1—Cl2ii	2.7358 (8)	Na2—Na1x	4.2126 (17)
Na1—Cl3iii	2.7902 (8)	Dy—Cl2	2.6176 (8)
Na1—Cl3iv	2.7902 (8)	Dy—Cl2xii	2.6176 (8)
Na1—Cl1	2.8687 (8)	Dy—Cl3	2.6320 (8)
Na1—Cl1v	2.8687 (8)	Dy—Cl3xii	2.6320 (8)
Na1—Na2vi	3.9579 (18)	Dy—Cl1xii	2.6447 (8)
Na1—Na2vii	3.9580 (18)	Dy—Cl1	2.6447 (8)
Na1—Na2viii	4.2126 (17)	Dy—Na2xiii	4.0608 (17)
Na1—Na2ix	4.2126 (17)	Dy—Na2vi	4.0608 (17)
Na2—Cl1	2.8295 (19)	Cl1—Na2vi	2.8492 (19)
Na2—Cl2x	2.8341 (19)	Cl2—Na1xiv	2.7358 (8)
Na2—Cl1iv	2.8492 (19)	Cl2—Na2viii	2.8342 (19)
Na2—Cl3i	2.8612 (19)	Cl2—Na2vi	3.325 (2)
Na2—Cl3xi	3.204 (2)	Cl2—Na2	3.488 (2)
Na2—Cl2iv	3.325 (2)	Cl3—Na1vi	2.7902 (8)
Na2—Cl2	3.488 (2)	Cl3—Na2xv	2.8611 (19)
Na2—Na1iv	3.9580 (18)	Cl3—Na2xi	3.204 (2)
Cl2i—Na1—Cl2ii	180.0	Cl3xi—Na2—Na1iv	44.32 (3)
Cl2i—Na1—Cl3iii	90.49 (3)	Cl2iv—Na2—Na1iv	88.01 (4)
Cl2ii—Na1—Cl3iii	89.51 (3)	Cl1—Na2—Dyiv	103.79 (5)
Cl2i—Na1—Cl3iv	89.51 (3)	Cl2x—Na2—Dyiv	158.34 (6)
Cl2ii—Na1—Cl3iv	90.49 (3)	Cl1iv—Na2—Dyiv	40.43 (3)
Cl3iii—Na1—Cl3iv	180.0	Cl3i—Na2—Dyiv	97.19 (5)
Cl2i—Na1—Cl1	85.33 (3)	Cl3xi—Na2—Dyiv	88.29 (4)
Cl2ii—Na1—Cl1	94.67 (3)	Cl2iv—Na2—Dyiv	39.98 (2)
Cl3iii—Na1—Cl1	86.30 (3)	Na1iv—Na2—Dyiv	78.73 (3)
Cl3iv—Na1—Cl1	93.71 (3)	Cl1—Na2—Na1x	132.81 (6)
Cl2i—Na1—Cl1v	94.67 (3)	Cl2x—Na2—Na1x	90.06 (4)
Cl2ii—Na1—Cl1v	85.33 (3)	Cl1iv—Na2—Na1x	112.16 (5)
Cl3iii—Na1—Cl1v	93.71 (3)	Cl3i—Na2—Na1x	41.17 (3)
Cl3iv—Na1—Cl1v	86.29 (3)	Cl3xi—Na2—Na1x	82.78 (4)
Cl1—Na1—Cl1v	180.00 (3)	Cl2iv—Na2—Na1x	40.45 (2)
Cl2i—Na1—Na2vi	59.53 (3)	Na1iv—Na2—Na1x	120.74 (4)
Cl2ii—Na1—Na2vi	120.47 (3)	Dyiv—Na2—Na1x	74.49 (3)
Cl3iii—Na1—Na2vi	53.35 (3)	Cl2—Dy—Cl2xii	180.0
Cl3iv—Na1—Na2vi	126.65 (3)	Cl2—Dy—Cl3	91.33 (3)
Cl1—Na1—Na2vi	45.99 (3)	Cl2xii—Dy—Cl3	88.67 (3)
Cl1v—Na1—Na2vi	134.01 (3)	Cl2—Dy—Cl3xii	88.67 (3)
Cl2i—Na1—Na2vii	120.47 (3)	Cl2xii—Dy—Cl3xii	91.33 (3)
Cl2ii—Na1—Na2vii	59.53 (3)	Cl3—Dy—Cl3xii	180.0
Cl3iii—Na1—Na2vii	126.65 (3)	Cl2—Dy—Cl1xii	91.73 (3)
Cl3iv—Na1—Na2vii	53.35 (3)	Cl2xii—Dy—Cl1xii	88.27 (3)
Cl1—Na1—Na2vii	134.01 (3)	Cl3—Dy—Cl1xii	91.71 (3)
Cl1v—Na1—Na2vii	45.99 (3)	Cl3xii—Dy—Cl1xii	88.29 (3)
Na2vi—Na1—Na2vii	180.0	Cl2—Dy—Cl1	88.28 (3)
Cl2i—Na1—Na2viii	127.96 (3)	Cl2xii—Dy—Cl1	91.72 (3)
Cl2ii—Na1—Na2viii	52.04 (3)	Cl3—Dy—Cl1	88.29 (3)
Cl3iii—Na1—Na2viii	42.45 (3)	Cl3xii—Dy—Cl1	91.71 (3)
Cl3iv—Na1—Na2viii	137.55 (3)	Cl1xii—Dy—Cl1	180.00 (3)
Cl1—Na1—Na2viii	73.28 (3)	Cl2—Dy—Na2xiii	125.31 (3)
Cl1v—Na1—Na2viii	106.72 (3)	Cl2xii—Dy—Na2xiii	54.69 (3)
Na2vi—Na1—Na2viii	72.02 (3)	Cl3—Dy—Na2xiii	115.46 (3)
Na2vii—Na1—Na2viii	107.98 (3)	Cl3xii—Dy—Na2xiii	64.54 (3)
Cl2i—Na1—Na2ix	52.04 (3)	Cl1xii—Dy—Na2xiii	44.32 (3)
Cl2ii—Na1—Na2ix	127.96 (3)	Cl1—Dy—Na2xiii	135.68 (3)
Cl3iii—Na1—Na2ix	137.55 (3)	Cl2—Dy—Na2vi	54.69 (3)
Cl3iv—Na1—Na2ix	42.45 (3)	Cl2xii—Dy—Na2vi	125.31 (3)
Cl1—Na1—Na2ix	106.72 (3)	Cl3—Dy—Na2vi	64.54 (3)
Cl1v—Na1—Na2ix	73.28 (3)	Cl3xii—Dy—Na2vi	115.46 (3)
Na2vi—Na1—Na2ix	107.98 (3)	Cl1xii—Dy—Na2vi	135.68 (3)
Na2vii—Na1—Na2ix	72.02 (3)	Cl1—Dy—Na2vi	44.32 (3)
Na2viii—Na1—Na2ix	180.0	Na2xiii—Dy—Na2vi	180.0
Cl1—Na2—Cl2x	97.84 (6)	Dy—Cl1—Na2	105.51 (5)
Cl1—Na2—Cl1iv	88.35 (5)	Dy—Cl1—Na2vi	95.24 (4)
Cl2x—Na2—Cl1iv	143.02 (7)	Na2—Cl1—Na2vi	133.80 (6)
Cl1—Na2—Cl3i	94.53 (6)	Dy—Cl1—Na1	134.58 (3)
Cl2x—Na2—Cl3i	79.84 (5)	Na2—Cl1—Na1	104.61 (4)
Cl1iv—Na2—Cl3i	136.23 (7)	Na2vi—Cl1—Na1	87.61 (4)
Cl1—Na2—Cl3xi	144.16 (7)	Dy—Cl2—Na1xiv	138.63 (3)
Cl2x—Na2—Cl3xi	74.54 (5)	Dy—Cl2—Na2viii	99.86 (4)
Cl1iv—Na2—Cl3xi	79.25 (5)	Na1xiv—Cl2—Na2viii	121.47 (5)
Cl3i—Na2—Cl3xi	117.64 (5)	Dy—Cl2—Na2vi	85.33 (4)
Cl1—Na2—Cl2iv	139.29 (7)	Na1xiv—Cl2—Na2vi	87.50 (4)
Cl2x—Na2—Cl2iv	119.28 (5)	Na2viii—Cl2—Na2vi	102.36 (4)
Cl1iv—Na2—Cl2iv	72.36 (4)	Dy—Cl3—Na1vi	134.93 (3)
Cl3i—Na2—Cl2iv	77.55 (4)	Dy—Cl3—Na2xv	128.25 (5)
Cl3xi—Na2—Cl2iv	68.06 (4)	Na1vi—Cl3—Na2xv	96.38 (4)
Cl1—Na2—Na1iv	104.40 (5)	Dy—Cl3—Na2xi	90.78 (4)
Cl2x—Na2—Na1iv	97.07 (5)	Na1vi—Cl3—Na2xi	82.33 (4)
Cl1iv—Na2—Na1iv	46.40 (3)	Na2xv—Cl3—Na2xi	104.74 (4)
Cl3i—Na2—Na1iv	161.07 (6)

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