K9Y3[Si12O32]F2.

Single-crystals of the title compound, nona-potassium triyttrium dodeca-silicate difluoride, were obtained from flux synthesis experiments in the system SiO2-Y2O3-KF. The crystal structure belongs to the group of single-layer silicates and is based on silicate sheets parallel to (110). A single layer contains secondary (Q (2)) and tertiary (Q (3)) silicate tetra-hedra in the ratio 1:2 and is build up from six-, eight- and twelve-membered rings. The linkage between neighboring layers is achieved by two crystallographically independent Y(3+) cations, which are coordinated by six oxygen ligands in form of distorted octa-hedra. Charge compensation is accomplished by incorporation of additional F(-) anions and K(+) cations in the structural channels, forming anion-centred [F2K7] groups. Apart from one K(+) and one Y(3+) cation (each with site symmetry -1), the 30 crystallographically independent atoms reside on general positions.

Related literature

Oxosilicates which can serve as luminescent materials containing trivalent rare earth elements, monovalent alkali cations as well as fluorine anions have already been characterized (Jacobsen & Meyer, 1994 ▶; Tang et al., 2008 ▶; Schäfer & Schleid, 2007 ▶, 2011 ▶). For structures isotypic to that of the title compound, see: Tang et al. (2008 ▶). For general aspects of the crystal chemistry of silicates, see: Liebau (1985 ▶). For the definition of distortion parameters, see: Robinson et al. (1971 ▶). For bond-valence analysis, see: Brown & Altermatt (1985 ▶). For the Inorganic Crystal Structure Database, see: ICSD (2013 ▶).

Experimental

Crystal data

K9Y3[Si12O32]F2

M = 1505.71

Triclinic,

a = 6.8187 (3) Å

b = 11.3345 (4) Å

c = 11.3727 (5) Å

α = 87.846 (3)°

β = 89.747 (4)°

γ = 80.524 (3)°

V = 866.35 (6) Å3

Z = 1

Mo Kα radiation

μ = 6.60 mm−1

T = 298 K

0.12 × 0.09 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 ▶) T min = 0.801, T max = 1

10508 measured reflections

2842 independent reflections

2231 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.099

S = 1.08

2842 reflections

265 parameters

Δρmax = 0.87 e Å−3

Δρmin = −0.95 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS for Windows (Dowty, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814001470/wm2792sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001470/wm2792Isup2.hkl

Additional supporting information: crystallographic information; 3D view; checkCIF report

F2K9O32Si12Y3	Z = 1
Mr = 1505.71	F(000) = 730
Triclinic, P1	Dx = 2.886 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8187 (3) Å	Cell parameters from 4373 reflections
b = 11.3345 (4) Å	θ = 3.0–29.3°
c = 11.3727 (5) Å	µ = 6.60 mm−1
α = 87.846 (3)°	T = 298 K
β = 89.747 (4)°	Fragment, colourless
γ = 80.524 (3)°	0.12 × 0.09 × 0.05 mm
V = 866.35 (6) Å3

Oxford Diffraction Xcalibur diffractometer	2842 independent reflections
Graphite monochromator	2231 reflections with I > 2σ(I)
Detector resolution: 10.3575 pixels mm-1	Rint = 0.066
ω scans	θmax = 25.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	h = −8→8
Tmin = 0.801, Tmax = 1	k = −13→13
10508 measured reflections	l = −13→13

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.039	Secondary atom site location: difference Fourier map
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.2439P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2842 reflections	Δρmax = 0.87 e Å−3
265 parameters	Δρmin = −0.95 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
K1	0.2651 (3)	−0.38667 (12)	0.01644 (15)	0.0222 (4)
K2	0.1715 (2)	−0.19454 (12)	−0.22364 (14)	0.0184 (4)
K3	0.1624 (3)	−0.15506 (14)	0.21410 (15)	0.0277 (4)
K4	0.5	0	0	0.0334 (6)
K5	0.0227 (2)	0.33078 (11)	0.51133 (13)	0.0161 (3)
F1	0.2472 (7)	−0.1589 (3)	−0.0048 (4)	0.0256 (10)
Y1	0	0	0.5	0.0068 (2)
Y2	0.48856 (9)	0.48851 (5)	0.33734 (5)	0.00691 (17)
Si1	0.5571 (3)	0.23257 (13)	0.51056 (15)	0.0072 (4)
Si2	0.3376 (3)	0.13524 (14)	0.31036 (16)	0.0077 (4)
Si3	0.6564 (3)	−0.09115 (13)	0.30291 (15)	0.0071 (4)
Si4	0.6897 (3)	−0.30506 (13)	0.15893 (16)	0.0076 (4)
Si5	−0.0138 (3)	−0.51249 (14)	0.25833 (15)	0.0077 (4)
Si6	0.2872 (3)	−0.66727 (14)	0.12015 (16)	0.0079 (4)
O1	0.5290 (7)	0.3756 (3)	0.5151 (4)	0.0115 (10)
O2	0.4907 (6)	0.2083 (3)	0.3742 (4)	0.0113 (10)
O3	0.3903 (6)	0.1857 (3)	0.5954 (4)	0.0097 (9)
O4	0.7743 (6)	0.1627 (3)	0.5395 (4)	0.0107 (10)
O5	0.1448 (7)	0.1240 (3)	0.3837 (4)	0.0125 (10)
O6	0.2791 (7)	0.2030 (3)	0.1831 (4)	0.0129 (10)
O7	0.4575 (7)	0.0054 (3)	0.2739 (4)	0.0132 (10)
O8	0.6920 (7)	−0.1638 (3)	0.1818 (4)	0.0102 (10)
O9	0.8444 (7)	−0.0336 (3)	0.3338 (4)	0.0114 (10)
O10	0.9033 (7)	−0.3743 (3)	0.2102 (4)	0.0139 (10)
O11	0.6983 (7)	−0.3156 (3)	0.0189 (4)	0.0169 (11)
O12	0.5030 (7)	−0.3527 (3)	0.2148 (4)	0.0123 (10)
O13	0.1635 (7)	−0.5084 (3)	0.3462 (4)	0.0114 (10)
O14	−0.1887 (6)	−0.5722 (3)	0.3149 (4)	0.0121 (10)
O15	0.0686 (7)	−0.5849 (3)	0.1393 (4)	0.0131 (10)
O16	0.4610 (7)	−0.6045 (3)	0.1658 (4)	0.0123 (10)

	U11	U22	U33	U12	U13	U23
K1	0.0222 (9)	0.0215 (8)	0.0233 (10)	−0.0056 (6)	0.0004 (7)	0.0030 (6)
K2	0.0165 (9)	0.0192 (7)	0.0197 (9)	−0.0036 (6)	0.0005 (7)	0.0013 (6)
K3	0.0204 (10)	0.0421 (10)	0.0197 (9)	−0.0011 (7)	0.0057 (8)	−0.0068 (7)
K4	0.0395 (17)	0.0363 (13)	0.0280 (15)	−0.0195 (11)	−0.0105 (12)	0.0117 (10)
K5	0.0190 (9)	0.0132 (7)	0.0158 (9)	−0.0020 (6)	0.0035 (7)	−0.0012 (5)
F1	0.030 (3)	0.026 (2)	0.022 (2)	−0.0079 (18)	0.004 (2)	−0.0013 (17)
Y1	0.0038 (5)	0.0078 (4)	0.0086 (5)	−0.0007 (3)	0.0021 (4)	−0.0001 (3)
Y2	0.0032 (3)	0.0093 (3)	0.0082 (3)	−0.0010 (2)	0.0010 (2)	0.0001 (2)
Si1	0.0056 (10)	0.0072 (8)	0.0087 (10)	−0.0010 (6)	0.0009 (7)	0.0006 (6)
Si2	0.0053 (10)	0.0080 (8)	0.0099 (9)	−0.0017 (6)	0.0002 (7)	−0.0003 (6)
Si3	0.0038 (9)	0.0078 (8)	0.0101 (10)	−0.0015 (6)	0.0015 (7)	−0.0010 (6)
Si4	0.0064 (10)	0.0076 (8)	0.0089 (9)	−0.0012 (6)	0.0010 (7)	−0.0011 (6)
Si5	0.0035 (9)	0.0104 (8)	0.0087 (9)	0.0002 (6)	0.0009 (7)	−0.0005 (6)
Si6	0.0072 (10)	0.0084 (8)	0.0081 (10)	−0.0014 (6)	0.0014 (7)	−0.0006 (6)
O1	0.017 (3)	0.006 (2)	0.011 (3)	−0.0005 (17)	0.002 (2)	−0.0002 (16)
O2	0.008 (3)	0.014 (2)	0.014 (3)	−0.0057 (17)	−0.001 (2)	−0.0002 (17)
O3	0.009 (3)	0.012 (2)	0.008 (2)	−0.0029 (17)	0.0027 (19)	−0.0004 (17)
O4	0.005 (2)	0.016 (2)	0.011 (3)	−0.0002 (17)	0.0034 (19)	0.0001 (17)
O5	0.010 (3)	0.013 (2)	0.016 (3)	−0.0037 (17)	0.000 (2)	−0.0016 (17)
O6	0.018 (3)	0.012 (2)	0.010 (3)	−0.0063 (18)	0.001 (2)	0.0035 (17)
O7	0.008 (3)	0.009 (2)	0.021 (3)	0.0039 (17)	−0.001 (2)	−0.0031 (18)
O8	0.015 (3)	0.007 (2)	0.008 (2)	−0.0011 (17)	0.003 (2)	0.0002 (16)
O9	0.008 (3)	0.016 (2)	0.011 (3)	−0.0053 (18)	−0.0006 (19)	0.0005 (17)
O10	0.004 (2)	0.012 (2)	0.025 (3)	−0.0003 (17)	−0.003 (2)	0.0032 (18)
O11	0.022 (3)	0.014 (2)	0.015 (3)	−0.0024 (19)	0.004 (2)	−0.0052 (18)
O12	0.009 (3)	0.010 (2)	0.017 (3)	−0.0022 (17)	0.004 (2)	0.0013 (17)
O13	0.006 (2)	0.017 (2)	0.011 (3)	−0.0028 (17)	0.002 (2)	0.0005 (17)
O14	0.004 (2)	0.013 (2)	0.019 (3)	−0.0020 (17)	−0.001 (2)	0.0021 (18)
O15	0.007 (3)	0.018 (2)	0.013 (3)	0.0015 (18)	0.002 (2)	−0.0040 (18)
O16	0.006 (3)	0.017 (2)	0.015 (3)	−0.0054 (17)	0.003 (2)	−0.0045 (17)

K1—F1	2.567 (4)	Si1—O3	1.631 (5)
K1—O16i	2.778 (5)	Si1—O2	1.662 (5)
K1—O12	2.858 (5)	Si2—O5	1.574 (5)
K1—O15ii	2.956 (5)	Si2—O2	1.625 (4)
K1—O16	3.064 (5)	Si2—O7	1.629 (4)
K1—O15	3.088 (5)	Si2—O6	1.633 (5)
K1—O11	3.188 (5)	Si3—O9	1.578 (4)
K1—O10iii	3.289 (5)	Si3—O3vi	1.613 (4)
K1—O11i	3.382 (4)	Si3—O7	1.623 (4)
K2—F1	2.604 (4)	Si3—O8	1.628 (4)
K2—O9iv	2.816 (4)	Si4—O12	1.584 (5)
K2—O5v	2.821 (5)	Si4—O11	1.602 (5)
K2—O2iv	2.851 (5)	Si4—O10	1.635 (5)
K2—O14ii	2.861 (4)	Si4—O8	1.635 (4)
K2—O6v	3.121 (5)	Si5—O13	1.579 (5)
K2—O16i	3.150 (5)	Si5—O14	1.588 (4)
K2—O15ii	3.317 (4)	Si5—O10iii	1.649 (4)
K3—F1	2.554 (5)	Si5—O15	1.657 (5)
K3—O9iii	2.754 (5)	Si6—O16	1.578 (4)
K3—O4vi	2.833 (5)	Si6—O11i	1.601 (5)
K3—O12	2.949 (5)	Si6—O6xi	1.620 (4)
K3—O7	3.021 (4)	Si6—O15	1.642 (5)
K3—O8iii	3.248 (5)	O1—Y2x	2.310 (4)
K3—O10iii	3.279 (4)	O1—K5xii	3.321 (5)
K4—F1iv	2.692 (4)	O2—K2iv	2.851 (5)
K4—F1	2.692 (4)	O3—Si3vi	1.613 (4)
K4—O8iv	2.893 (4)	O4—Y1xii	2.256 (4)
K4—O8	2.893 (4)	O4—K5xii	2.759 (4)
K4—O7	3.129 (5)	O4—K3vi	2.833 (5)
K4—O7iv	3.129 (5)	O5—K2v	2.821 (5)
K4—O6iv	3.330 (4)	O6—Si6vii	1.620 (4)
K4—O6	3.330 (4)	O6—K2v	3.121 (5)
K5—O14vii	2.756 (5)	O8—K3xii	3.248 (5)
K5—O4iii	2.759 (4)	O9—Y1xii	2.247 (4)
K5—O13viii	2.771 (4)	O9—K3xii	2.754 (5)
K5—O5	2.810 (4)	O9—K2iv	2.816 (4)
K5—O13vii	2.842 (5)	O10—Si5xii	1.649 (4)
K5—O3	2.907 (5)	O10—K5vi	3.277 (5)
K5—O10vi	3.277 (5)	O10—K3xii	3.279 (4)
K5—O1iii	3.321 (5)	O10—K1xii	3.289 (5)
Y1—O5	2.237 (4)	O11—Si6i	1.601 (5)
Y1—O5viii	2.237 (4)	O11—K1i	3.382 (4)
Y1—O9vi	2.247 (4)	O12—Y2xi	2.250 (4)
Y1—O9iii	2.247 (4)	O13—Y2xi	2.213 (4)
Y1—O4vi	2.256 (4)	O13—K5viii	2.771 (4)
Y1—O4iii	2.256 (4)	O13—K5xi	2.842 (5)
Y2—O14ix	2.211 (4)	O14—Y2xiii	2.211 (4)
Y2—O13vii	2.213 (4)	O14—K5xi	2.756 (5)
Y2—O12vii	2.250 (4)	O14—K2ii	2.861 (4)
Y2—O16vii	2.275 (4)	O15—K1ii	2.956 (5)
Y2—O1x	2.310 (4)	O15—K2ii	3.317 (4)
Y2—O1	2.345 (4)	O16—Y2xi	2.275 (4)
Si1—O4	1.590 (5)	O16—K1i	2.778 (5)
Si1—O1	1.603 (4)	O16—K2i	3.150 (5)
O5—Y1—O5viii	180	O5—Si2—O7	112.2 (2)
O5—Y1—O9vi	96.02 (15)	O2—Si2—O7	109.0 (2)
O5viii—Y1—O9vi	83.98 (15)	O5—Si2—O6	110.5 (3)
O5—Y1—O9iii	83.98 (15)	O2—Si2—O6	107.2 (2)
O5viii—Y1—O9iii	96.02 (15)	O7—Si2—O6	102.9 (2)
O9vi—Y1—O9iii	180	O9—Si3—O3vi	111.7 (2)
O5—Y1—O4vi	94.15 (15)	O9—Si3—O7	114.3 (2)
O5viii—Y1—O4vi	85.85 (15)	O3vi—Si3—O7	109.8 (2)
O9vi—Y1—O4vi	93.05 (15)	O9—Si3—O8	110.7 (2)
O9iii—Y1—O4vi	86.95 (15)	O3vi—Si3—O8	106.9 (2)
O5—Y1—O4iii	85.85 (15)	O7—Si3—O8	102.9 (2)
O5viii—Y1—O4iii	94.15 (15)	O12—Si4—O11	112.3 (3)
O9vi—Y1—O4iii	86.95 (15)	O12—Si4—O10	114.1 (2)
O9iii—Y1—O4iii	93.05 (15)	O11—Si4—O10	106.7 (3)
O4vi—Y1—O4iii	180.0000 (10)	O12—Si4—O8	113.3 (2)
O14ix—Y2—O13vii	162.32 (14)	O11—Si4—O8	105.2 (2)
O14ix—Y2—O12vii	90.23 (16)	O10—Si4—O8	104.5 (2)
O13vii—Y2—O12vii	100.81 (16)	O13—Si5—O14	113.5 (2)
O14ix—Y2—O16vii	84.41 (16)	O13—Si5—O10iii	107.8 (2)
O13vii—Y2—O16vii	83.37 (16)	O14—Si5—O10iii	110.8 (2)
O12vii—Y2—O16vii	82.65 (15)	O13—Si5—O15	110.3 (2)
O14ix—Y2—O1x	103.85 (16)	O14—Si5—O15	109.2 (2)
O13vii—Y2—O1x	90.94 (16)	O10iii—Si5—O15	104.9 (2)
O12vii—Y2—O1x	85.09 (15)	O16—Si6—O11i	111.4 (3)
O16vii—Y2—O1x	165.26 (15)	O16—Si6—O6xi	114.0 (2)
O14ix—Y2—O1	84.94 (16)	O11i—Si6—O6xi	107.7 (2)
O13vii—Y2—O1	90.07 (16)	O16—Si6—O15	111.7 (2)
O12vii—Y2—O1	156.35 (15)	O11i—Si6—O15	104.5 (2)
O16vii—Y2—O1	119.73 (14)	O6xi—Si6—O15	106.9 (2)
O1x—Y2—O1	73.70 (14)	Si2—O2—Si1	137.7 (3)
O4—Si1—O1	115.9 (2)	Si3vi—O3—Si1	147.0 (3)
O4—Si1—O3	111.7 (2)	Si6vii—O6—Si2	137.6 (3)
O1—Si1—O3	108.3 (2)	Si3—O7—Si2	142.8 (3)
O4—Si1—O2	110.8 (2)	Si3—O8—Si4	129.8 (3)
O1—Si1—O2	104.0 (2)	Si4—O10—Si5xii	134.1 (3)
O3—Si1—O2	105.4 (2)	Si4—O11—Si6i	177.1 (3)
O5—Si2—O2	114.3 (2)	Si6—O15—Si5	127.5 (3)