K2Ho(PO4)(WO4)

Terebilenko, K.V.; Zatovsky, I.V.; Baumer, V.N.; Slobodyanik, N.S.; Shishkin, O.V.

doi:10.1107/S160053680803287X

inorganic compounds

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Volume 64| Part 11| November 2008| Page i75

doi:10.1107/S160053680803287X

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K₂Ho(PO₄)(WO₄)

Katherina V. Terebilenko,^a ^* Igor V. Zatovsky,^a Vyacheslav N. Baumer,^b Nikolay S. Slobodyanik ^a and Oleg V. Shishkin ^b

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University, 64 Volodymyrska Street, 01033 Kyiv, Ukraine, and ^bSTC `Institute for Single Crystals', NAS of Ukraine, 60 Lenin Avenue, 61001 Kharkiv, Ukraine
^*Correspondence e-mail: Tereb@bigmir.net

(Received 5 September 2008; accepted 10 October 2008; online 18 October 2008)

A new compound, dipotassium holmium(III) phosphate(V) tungstate(VI), K₂Ho(PO₄)(WO₄), has been obtained during investigation of the K₂O–P₂O₅–WO₃–HoF₃ phase system using the flux technique. The compound is isotypic with K₂Bi(PO₄)(WO₄). Its framework structure consists of flat _∞²[HoPO₄] layers parallel to (100) that are made up of _∞¹[HoO₈] zigzag chains interlinked via slightly distorted PO₄ tetrahedra. WO₄ tetrahedra are attached above and below these layers, leaving space for the K⁺ counter-cations. The HoO₈, PO₄ and WO₄ units exhibit 2 symmetry.

Related literature

For related structures, see: Ben Amara & Dabbabi (1987 ); Marsh (1987 ); Zatovsky, Terebilenko, Slobodyanik & Baumer (2006 ); Zatovsky, Terebilenko, Slobodyanik, Baumer & Shishkin (2006 ).

Experimental

Crystal data

K₂Ho(PO₄)(WO₄)
M_r = 585.95
Orthorhombic, I b c a
a = 6.8820 (10) Å
b = 12.1485 (18) Å
c = 19.695 (3) Å
V = 1646.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 24.72 mm⁻¹
T = 293 (2) K
0.10 × 0.09 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur-3 CCD diffractometer
Absorption correction: multi-scan based on the method by Blessing (1995 ) T_min = 0.102, T_max = 0.177
8608 measured reflections
1561 independent reflections
1257 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.071
S = 1.15
1561 reflections
62 parameters
Δρ_max = 1.90 e Å⁻³
Δρ_min = −1.73 e Å⁻³

Table 1
Selected bond lengths (Å)

W1—O2	1.749 (4)
W1—O1	1.788 (3)
Ho1—O4ⁱ	2.274 (3)
Ho1—O1	2.342 (3)
Ho1—O3ⁱⁱ	2.401 (3)
Ho1—O4	2.428 (3)
P1—O3	1.525 (3)
P1—O4	1.552 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abington, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abington, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; 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: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803287X/wm2196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803287X/wm2196Isup2.hkl

checkCIF report

Comment top

The co-existence of different anionic units in crystal structures represents an interesting field of investigation. One of the first structural examples of a combination of PO₄ with MoO₄/WO₄ tetrahedra, viz. Na₂Y(MoO₄)(PO₄), was reported to be monoclinic with space group C2/c (Ben Amara & Dabbabi, 1987). Later this structure was reinvestigated and described as orthorhombic, space group Ibca (Marsh, 1987). Recently, the compounds K₂Bi(PO₄)(MO₄) (M=Mo, W) with isotypic structures were obtained by application of the flux method (Zatovsky, Terebilenko, Slobodyanik & Baumer, 2006; Zatovsky, Terebilenko, Slobodyanik, Baumer & Shishkin, 2006). Herein, we report the flux synthesis and crystal structure of a new member of the A₂B(PO₄)(AO₄) (A = Na, K; B = lanthanide, Y, Bi; M = Mo, W) family.

One of the characteristic features of this structure type is the "segregation" of slightly distorted PO₄ and WO₄ tetrahedra into adjacent layers (Fig. 1). The first layer with composition ²_∞[HoPO₄] contains ¹_∞[HoO₈] zigzag chains (Fig. 2). The connection between neighboring chains is achieved via PO₄ tetrahedra. On the top and on the bottom of the ²_∞[HoPO₄] layer, WO₄ tetrahedra are attached. All [HoO₈], PO₄ and WO₄ units exhibit 2 symmetry with bond lengths in the typical ranges (Table 1). The K⁺ cations are situated in the resulting interlayer space and are surrounded by 8 oxygen atoms with K—O bond lengths ranging from 2.683 (4) Å to 3.133 (4) Å.

Related literature top

For related structures, see: Ben Amara & Dabbabi (1987); Marsh (1987); Zatovsky, Terebilenko, Slobodyanik & Baumer (2006); Zatovsky, Terebilenko, Slobodyanik, Baumer & Shishkin (2006).

Experimental top

Single crystals of the title compound were grown from a multicomponent high-temperature solution. A mixture of 4.645 g K₂W₂O₇, 0.865 g KPO₃, and 1.150 g K₄P₂O₇ was heated in a platinum crucible up to 1173 K which is above the melting temperature. Then 0.200 g of HoF₃ were added to this melt under stirring. The final mixture was held at this temperature for 1 h and cooled down to room temperature with a rate of 30 Kh^-1. The solidified melt was leached out with warm water to dissolve the superfluous flux. The final product consisted of beige needle-like crystals with a maximum length of up to 5 mm.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); 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: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The layered structure of K₂Ho(PO₄)(WO₄), leaving space where the K⁺ ions are located.
	Fig. 2. View of K₂Ho(PO₄)(WO₄) with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1,5-x; y; 1-z; (ii) 1-x; 0.5-y; z].

Dipotassium holmium(III) phosphate(V) tungstate(VI) top

Crystal data top

K₂Ho(PO₄)(WO₄)	F(000) = 2064
M_r = 585.95	D_x = 4.727 Mg m⁻³
Orthorhombic, Ibca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2c	Cell parameters from 8608 reflections
a = 6.882 (1) Å	θ = 3.4–33.0°
b = 12.1485 (18) Å	µ = 24.72 mm⁻¹
c = 19.695 (3) Å	T = 293 K
V = 1646.6 (4) Å³	Prism, pale beige
Z = 8	0.10 × 0.09 × 0.07 mm

Data collection top

Oxford Diffraction XCalibur-3 CCD diffractometer	1561 independent reflections
Radiation source: fine-focus sealed tube	1257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 33.0°, θ_min = 3.4°
Absorption correction: multi-scan based on the method by Blessing (1995)	h = −10→10
T_min = 0.102, T_max = 0.177	k = −18→18
8608 measured reflections	l = −30→29

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0397P)² + 3.2575P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.029	(Δ/σ)_max < 0.001
wR(F²) = 0.071	Δρ_max = 1.90 e Å⁻³
S = 1.15	Δρ_min = −1.73 e Å⁻³
1561 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
62 parameters	Extinction coefficient: 0.00010 (2)

Crystal data top

K₂Ho(PO₄)(WO₄)	V = 1646.6 (4) Å³
M_r = 585.95	Z = 8
Orthorhombic, Ibca	Mo Kα radiation
a = 6.882 (1) Å	µ = 24.72 mm⁻¹
b = 12.1485 (18) Å	T = 293 K
c = 19.695 (3) Å	0.10 × 0.09 × 0.07 mm

Data collection top

Oxford Diffraction XCalibur-3 CCD diffractometer	1561 independent reflections
Absorption correction: multi-scan based on the method by Blessing (1995)	1257 reflections with I > 2σ(I)
T_min = 0.102, T_max = 0.177	R_int = 0.055
8608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	62 parameters
wR(F²) = 0.071	0 restraints
S = 1.15	Δρ_max = 1.90 e Å⁻³
1561 reflections	Δρ_min = −1.73 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.

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

	x	y	z	U_iso*/U_eq
W1	0.5	0.25	0.334530 (12)	0.01088 (5)
Ho1	0.75	0.325113 (17)	0.5	0.00662 (5)
K1	0.96872 (15)	0.07992 (10)	0.34389 (5)	0.0196 (2)
P1	0.75	0.07042 (10)	0.5	0.0065 (2)
O1	0.7088 (4)	0.2796 (3)	0.38536 (17)	0.0146 (7)
O2	0.4420 (6)	0.3643 (4)	0.2845 (2)	0.0269 (8)
O3	0.7308 (4)	−0.0047 (2)	0.43834 (16)	0.0102 (6)
O4	0.9229 (4)	0.1514 (2)	0.49215 (17)	0.0105 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01432 (9)	0.01167 (9)	0.00666 (9)	−0.00095 (8)	0	0
Ho1	0.00652 (9)	0.00523 (9)	0.00811 (10)	0	−0.00005 (9)	0
K1	0.0204 (4)	0.0248 (5)	0.0137 (4)	−0.0002 (4)	0.0021 (3)	0.0039 (4)
P1	0.0064 (5)	0.0034 (5)	0.0098 (6)	0	0.0000 (5)	0
O1	0.0154 (14)	0.0171 (14)	0.0113 (14)	−0.0035 (11)	−0.0012 (11)	−0.0031 (11)
O2	0.0308 (17)	0.0296 (19)	0.0203 (17)	−0.0008 (17)	0.0013 (15)	0.0126 (16)
O3	0.0126 (13)	0.0079 (11)	0.0101 (13)	−0.0018 (10)	−0.0002 (11)	−0.0010 (9)
O4	0.0052 (10)	0.0066 (11)	0.0198 (16)	−0.0017 (9)	0.0011 (10)	−0.0016 (11)

Geometric parameters (Å, º) top

W1—O2ⁱ	1.749 (4)	Ho1—K1^vii	3.8119 (11)
W1—O2	1.749 (4)	Ho1—K1^vi	3.8119 (12)
W1—O1	1.788 (3)	K1—O3	2.683 (3)
W1—O1ⁱ	1.788 (3)	K1—O2^v	2.689 (4)
W1—K1	3.8352 (12)	K1—O3^x	2.747 (3)
W1—K1ⁱ	3.8352 (12)	K1—O1^vi	2.916 (3)
W1—K1ⁱⁱ	4.0181 (13)	K1—O2^xi	2.934 (5)
W1—K1ⁱⁱⁱ	4.0181 (13)	K1—O4	3.063 (3)
W1—K1^iv	4.0821 (12)	K1—O1	3.122 (4)
W1—K1^v	4.0821 (12)	K1—O2ⁱ	3.133 (4)
Ho1—O4^vi	2.274 (3)	K1—P1	3.4251 (11)
Ho1—O4^vii	2.274 (3)	K1—Ho1^vi	3.8119 (11)
Ho1—O1	2.342 (3)	K1—K1ⁱⁱⁱ	3.9511 (13)
Ho1—O1^viii	2.342 (3)	P1—O3	1.525 (3)
Ho1—O3^ix	2.401 (3)	P1—O3^viii	1.525 (3)
Ho1—O3ⁱⁱ	2.401 (3)	P1—O4	1.552 (3)
Ho1—O4^viii	2.428 (3)	P1—O4^viii	1.552 (3)
Ho1—O4	2.428 (3)	P1—Ho1^xii	2.9802 (13)
Ho1—P1^ix	2.9802 (13)	P1—K1^viii	3.4251 (11)
Ho1—P1	3.0941 (13)

O2ⁱ—W1—O2	111.4 (3)	O3^x—K1—O4	61.07 (8)
O2ⁱ—W1—O1	106.94 (17)	O1^vi—K1—O4	69.23 (9)
O2—W1—O1	109.83 (19)	O2^xi—K1—O4	130.90 (10)
O2ⁱ—W1—O1ⁱ	109.83 (19)	O3—K1—O1	76.52 (9)
O2—W1—O1ⁱ	106.94 (17)	O2^v—K1—O1	100.44 (12)
O1—W1—O1ⁱ	111.9 (2)	O3^x—K1—O1	117.21 (9)
O4^vi—Ho1—O4^vii	165.59 (15)	O1^vi—K1—O1	84.72 (10)
O4^vi—Ho1—O1	94.81 (11)	O2^xi—K1—O1	156.62 (10)
O4^vii—Ho1—O1	88.59 (11)	O4—K1—O1	58.09 (8)
O4^vi—Ho1—O1^viii	88.59 (11)	O3—K1—O2ⁱ	77.94 (10)
O4^vii—Ho1—O1^viii	94.81 (11)	O2^v—K1—O2ⁱ	78.50 (9)
O1—Ho1—O1^viii	152.68 (18)	O3^x—K1—O2ⁱ	156.48 (11)
O4^vi—Ho1—O3^ix	88.91 (10)	O1^vi—K1—O2ⁱ	131.64 (12)
O4^vii—Ho1—O3^ix	78.65 (10)	O2^xi—K1—O2ⁱ	103.49 (13)
O1—Ho1—O3^ix	133.18 (11)	O4—K1—O2ⁱ	101.64 (9)
O1^viii—Ho1—O3^ix	73.88 (12)	O1—K1—O2ⁱ	54.04 (10)
O4^vi—Ho1—O3ⁱⁱ	78.65 (10)	O3—P1—O3^viii	106.4 (2)
O4^vii—Ho1—O3ⁱⁱ	88.91 (10)	O3—P1—O4	111.52 (16)
O1—Ho1—O3ⁱⁱ	73.88 (12)	O3^viii—P1—O4	113.10 (16)
O1^viii—Ho1—O3ⁱⁱ	133.18 (12)	O3—P1—O4^viii	113.10 (16)
O3^ix—Ho1—O3ⁱⁱ	61.17 (15)	O3^viii—P1—O4^viii	111.52 (16)
O4^vi—Ho1—O4^viii	126.77 (7)	O4—P1—O4^viii	101.3 (2)
O4^vii—Ho1—O4^viii	67.63 (12)	W1—O1—Ho1	133.20 (16)
O1—Ho1—O4^viii	78.27 (12)	W1—O1—K1^vi	124.93 (16)
O1^viii—Ho1—O4^viii	78.03 (12)	Ho1—O1—K1^vi	92.27 (11)
O3^ix—Ho1—O4^viii	133.56 (10)	W1—O1—K1	99.08 (14)
O3ⁱⁱ—Ho1—O4^viii	143.86 (10)	Ho1—O1—K1	111.49 (12)
O4^vi—Ho1—O4	67.63 (12)	K1^vi—O1—K1	86.88 (9)
O4^vii—Ho1—O4	126.77 (8)	W1—O2—K1^v	132.6 (2)
O1—Ho1—O4	78.03 (12)	W1—O2—K1ⁱⁱ	115.89 (19)
O1^viii—Ho1—O4	78.27 (12)	K1^v—O2—K1ⁱⁱ	95.86 (13)
O3^ix—Ho1—O4	143.86 (10)	W1—O2—K1ⁱ	99.64 (16)
O3ⁱⁱ—Ho1—O4	133.56 (10)	K1^v—O2—K1ⁱ	120.18 (15)
O4^viii—Ho1—O4	59.26 (13)	K1ⁱⁱ—O2—K1ⁱ	81.21 (11)
O3—K1—O2^v	152.62 (12)	P1—O3—Ho1^xii	96.20 (15)
O3—K1—O3^x	78.69 (8)	P1—O3—K1	105.64 (14)
O2^v—K1—O3^x	124.78 (11)	Ho1^xii—O3—K1	130.32 (12)
O3—K1—O1^vi	119.65 (10)	P1—O3—K1ⁱⁱⁱ	142.66 (16)
O2^v—K1—O1^vi	86.67 (12)	Ho1^xii—O3—K1ⁱⁱⁱ	95.30 (9)
O3^x—K1—O1^vi	60.35 (9)	K1—O3—K1ⁱⁱⁱ	93.37 (11)
O3—K1—O2^xi	93.55 (11)	P1—O4—Ho1^vi	146.28 (18)
O2^v—K1—O2^xi	78.59 (14)	P1—O4—Ho1	99.72 (13)
O3^x—K1—O2^xi	80.53 (10)	Ho1^vi—O4—Ho1	111.83 (11)
O1^vi—K1—O2^xi	118.34 (11)	P1—O4—K1	89.66 (13)
O3—K1—O4	52.05 (8)	Ho1^vi—O4—K1	89.92 (10)
O2^v—K1—O4	148.06 (12)	Ho1—O4—K1	110.96 (11)

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

Experimental details

Crystal data
Chemical formula	K₂Ho(PO₄)(WO₄)
M_r	585.95
Crystal system, space group	Orthorhombic, Ibca
Temperature (K)	293
a, b, c (Å)	6.882 (1), 12.1485 (18), 19.695 (3)
V (Å³)	1646.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	24.72
Crystal size (mm)	0.10 × 0.09 × 0.07

Data collection
Diffractometer	Oxford Diffraction XCalibur-3 CCD diffractometer
Absorption correction	Multi-scan based on the method by Blessing (1995)
T_min, T_max	0.102, 0.177
No. of measured, independent and observed [I > 2σ(I)] reflections	8608, 1561, 1257
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.766

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.071, 1.15
No. of reflections	1561
No. of parameters	62
Δρ_max, Δρ_min (e Å⁻³)	1.90, −1.73

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

W1—O2	1.749 (4)	Ho1—O3ⁱⁱ	2.401 (3)
W1—O1	1.788 (3)	Ho1—O4	2.428 (3)
Ho1—O4ⁱ	2.274 (3)	P1—O3	1.525 (3)
Ho1—O1	2.342 (3)	P1—O4	1.552 (3)

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

Acknowledgements

The authors acknowledge the ICDD for financial support (grant No. 03-02).

References

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