Download citation
Download citation
link to html
Single crystals of tungsten double salt (NH4)3WO2F5 = (NH4)3[WO2F4]F have been synthesized by solid-state reaction or from fluoride solution and its crystal structures at 296 and 193 K were determined by X-ray diffraction. At room temperature, the crystal structure of the compound is dynamically disordered with the ligand atoms statistically distributed on two positions (6e and 24m) of the Pm3m unit cell [a = 6.0298 (1) Å], and the tungsten atom dynamically disordered on 12 orientations forming a spatial cuboctahedron [W12] that enables the real geometry of cis-WO2F4 octahedron to be determined with two short W—O distances. On cooling, the compound undergoes a first-order phase transition with the symmetry change Pm3mPa3 and a doubling of the unit-cell parameter [a = 11.9635 (7) Å]. The ligand F(O) atoms statistically occupy two general 24d sites and form W1X6 and W2X6 octahedra, in which the O and F atoms are not crystallographically different that means a static orientational disorder of (NH4)3WO2F5.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520615010835/bp5078sup1.cif
Contains datablocks 193K, NH43WO2F4F, 296K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520615010835/bp5078296Ksup2.hkl
Contains datablock (NH4)3WO2F5(RT)

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520615010835/bp5078193Ksup3.hkl
Contains datablock (NH4)3WO2F5(LT)

CCDC references: 1404974; 1404975

Computing details top

For both compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
(296K) top
Crystal data top
F4WO2·2(H4N)·F(NH4)Dx = 2.810 Mg m3
Mr = 370.98Mo Kα radiation, λ = 0.71073 Å
Cubic, Pm3mCell parameters from 860 reflections
Hall symbol: -P 4 2 3θ = 3.4–30.0°
a = 6.0298 (1) ŵ = 13.24 mm1
V = 219.23 (1) Å3T = 296 K
Z = 1Sphere, colorless
F(000) = 1700.18 × 0.18 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer
93 independent reflections
Radiation source: fine-focus sealed tube93 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 8.33 pixels mm-1θmax = 30.0°, θmin = 3.4°
ω scansh = 88
Absorption correction: multi-scan
SADABS 2008/1
k = 88
Tmin = 0.199, Tmax = 0.199l = 88
2864 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullH-atom parameters not defined
R[F2 > 2σ(F2)] = 0.016 w = 1/[σ2(Fo2) + (0.0291P)2 + 0.0078P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.035(Δ/σ)max = 0.024
S = 1.21Δρmax = 0.49 e Å3
93 reflectionsΔρmin = 0.63 e Å3
19 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0478 (14)
Primary atom site location: structure-invariant direct methods
Crystal data top
F4WO2·2(H4N)·F(NH4)Z = 1
Mr = 370.98Mo Kα radiation
Cubic, Pm3mµ = 13.24 mm1
a = 6.0298 (1) ÅT = 296 K
V = 219.23 (1) Å30.18 × 0.18 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer
93 independent reflections
Absorption correction: multi-scan
SADABS 2008/1
93 reflections with I > 2σ(I)
Tmin = 0.199, Tmax = 0.199Rint = 0.020
2864 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0160 restraints
wR(F2) = 0.035H-atom parameters not defined
S = 1.21Δρmax = 0.49 e Å3
93 reflectionsΔρmin = 0.63 e Å3
19 parameters
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
xyzUiso*/UeqOcc. (<1)
W10.02378 (2)0.00000.02378 (2)0.04325 (4)0.08
F30.50000.50000.50000.0986 (12)
N10.50000.50000.00000.129 (2)
F10.3108 (10)0.00000.00000.113 (3)0.249 (4)
F20.2033 (4)0.2033 (4)0.0997 (9)0.1345 (17)0.1877 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
W10.04631 (5)0.03712 (7)0.04631 (5)0.0000.00513 (13)0.000
F30.0986 (12)0.0986 (12)0.0986 (12)0.0000.0000.000
N10.1118 (19)0.1118 (19)0.164 (5)0.0000.0000.000
F10.048 (2)0.145 (4)0.145 (4)0.0000.0000.000
F20.1123 (12)0.1123 (12)0.179 (4)0.0585 (15)0.0233 (11)0.0233 (11)
Geometric parameters (Å, º) top
W1—W1i0.2028 (2)F1—F1vii2.650 (9)
W1—W1ii0.2028 (2)F1—F1iii2.650 (9)
W1—W1iii0.2028 (2)F1—F1iv2.650 (9)
W1—W1iv0.2028 (2)F2—F2xiii2.584 (9)
W1—W1v0.2868 (3)F2—F2xiv2.584 (9)
W1—W1vi0.2868 (3)F2—F2xv2.606 (7)
W1—W1vii0.3512 (4)F2—F2xvi2.606 (7)
W1—W1viii0.3512 (4)N1—F2vi2.600 (4)
W1—W1ix0.3512 (4)N1—F2xvii2.600 (4)
W1—W1x0.3512 (4)N1—F2xviii2.600 (4)
W1—W1xi0.4055 (4)N1—F2xix2.600 (4)
W1—F1iii1.736 (6)N1—F2xx2.600 (4)
W1—F11.736 (6)N1—F2xxi2.600 (4)
W1—F1vii1.885 (6)N1—F2xxii2.600 (4)
W1—F1ix1.885 (6)N1—F22.600 (4)
W1—F1xi2.022 (6)N1—F3xxiii3.0149
W1—F1viii2.022 (6)N1—F13.223 (2)
W1—F21.698 (4)N1—F1xviii3.223 (2)
W1—F2iv1.698 (4)N1—F1iv3.223 (2)
W1—F2xii1.846 (4)N1—F1xxiv3.223 (2)
W1—F2xiii1.846 (4)N1—F1xxv3.223 (2)
W1—F2viii1.983 (4)N1—F1xxvi3.223 (2)
W1—F2xi1.983 (4)N1—F1xxvii3.223 (2)
F1—F1viii2.650 (9)N1—F1xxviii3.223 (2)
F1viii—W1—F1vii85.339 (17)F2—W1—F2xv100.3 (3)
F1iv—W1—F1vii85.339 (17)F2xxix—W1—F2viii88.8 (2)
F1viii—W1—F1xi85.339 (17)F2xv—W1—F2xi88.8 (2)
F1iv—W1—F1xi85.339 (17)F2ii—W1—F2ix82.3 (2)
F1iii—W1—F1viii93.986 (12)F2iv—W1—F2xii93.5 (3)
F1—W1—F1viii93.986 (12)F2xxix—W1—F2xii94.6 (3)
F1iii—W1—F1iv93.986 (12)F2xv—W1—F2xiii94.6 (3)
F1—W1—F1iv93.986 (12)F2xii—W1—F2viii85.7 (2)
F1iii—W1—F199.47 (3)F2xiii—W1—F2xi85.7 (2)
F1iii—W1—F1xi89.329 (5)F2xxx—W1—F2viii84.8 (2)
F1—W1—F1vii89.329 (5)F2xvi—W1—F2xi84.8 (2)
F1xi—W1—F1vii81.87 (3)F2xv—W1—F2xvi93.5 (3)
F1viii—W1—F1iv167.65 (4)F2xii—W1—F2xxx167.39 (3)
F1—W1—F1xi171.20 (3)F2iv—W1—F2viii170.97 (3)
F1iii—W1—F1vii171.20 (3)F2—W1—F2xi170.97 (3)
F2iv—W1—F2xxix100.3 (3)
Symmetry codes: (i) y, z, x; (ii) z, x, y; (iii) y, z, x; (iv) z, x, y; (v) x, y, z; (vi) x, y, z; (vii) y, z, x; (viii) z, x, y; (ix) y, z, x; (x) z, x, y; (xi) x, y, z; (xii) y, z, x; (xiii) y, z, x; (xiv) z, x, y; (xv) z, x, y; (xvi) y, z, x; (xvii) x+1, y+1, z; (xviii) x+1, y+1, z; (xix) x+1, y, z; (xx) x, y+1, z; (xxi) x, y+1, z; (xxii) x+1, y, z; (xxiii) x, y, z1; (xxiv) z+1, x+1, y; (xxv) x, y+1, z; (xxvi) z, x+1, y; (xxvii) z+1, x, y; (xxviii) x+1, y, z; (xxix) x, y, z; (xxx) y, z, x.
(193K) top
Crystal data top
F4WO2·F·3(H4N)Dx = 2.878 Mg m3
Mr = 370.98Mo Kα radiation, λ = 0.71073 Å
Cubic, Pa3Cell parameters from 868 reflections
Hall symbol: -P 2ac 2abθ = 1.7–33.0°
a = 11.9635 (7) ŵ = 13.56 mm1
V = 1712.28 (17) Å3T = 193 K
Z = 8Sphere, colorless
F(000) = 13600.18 × 0.18 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer
1134 independent reflections
Radiation source: fine-focus sealed tube696 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 8.33 pixels mm-1θmax = 33.0°, θmin = 1.7°
φ and ω scansh = 1818
Absorption correction: multi-scan
SADABS 2008/1
k = 1618
Tmin = 0.194, Tmax = 0.194l = 1818
27085 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullH-atom parameters not defined
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max < 0.001
S = 0.98Δρmax = 1.90 e Å3
1079 reflectionsΔρmin = 1.32 e Å3
38 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.00054 (7)
Primary atom site location: structure-invariant direct methods
Crystal data top
F4WO2·F·3(H4N)Z = 8
Mr = 370.98Mo Kα radiation
Cubic, Pa3µ = 13.56 mm1
a = 11.9635 (7) ÅT = 193 K
V = 1712.28 (17) Å30.18 × 0.18 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer
1134 independent reflections
Absorption correction: multi-scan
SADABS 2008/1
696 reflections with I > 2σ(I)
Tmin = 0.194, Tmax = 0.194Rint = 0.033
27085 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.101H-atom parameters not defined
S = 0.98 w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P]
where P = (Fo2 + 2Fc2)/3
1079 reflectionsΔρmax = 1.90 e Å3
38 parametersΔρmin = 1.32 e Å3
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
xyzUiso*/Ueq
W10.50000.00000.50000.02738 (16)
W20.50000.50000.50000.04546 (18)
N10.5152 (6)0.2579 (5)0.2331 (7)0.059 (2)
F30.2445 (4)0.2445 (4)0.2445 (4)0.0514 (19)
F10.4455 (3)0.1082 (3)0.3996 (3)0.0398 (8)
F20.4786 (5)0.3465 (3)0.5179 (5)0.0697 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
W10.02738 (16)0.02738 (16)0.02738 (16)0.00399 (10)0.00399 (10)0.00399 (10)
W20.04546 (18)0.04546 (18)0.04546 (18)0.00152 (16)0.00152 (16)0.00152 (16)
N10.078 (5)0.037 (4)0.063 (5)0.019 (4)0.009 (4)0.022 (3)
F30.0514 (19)0.0514 (19)0.0514 (19)0.002 (2)0.002 (2)0.002 (2)
F10.0450 (19)0.0366 (18)0.0379 (19)0.0029 (16)0.0047 (16)0.0123 (15)
F20.099 (5)0.0236 (16)0.086 (4)0.015 (2)0.010 (3)0.009 (2)
Geometric parameters (Å, º) top
W1—F11.882 (3)N1—F12.806 (7)
W1—F1i1.882 (3)N1—F2xii2.894 (11)
W1—F1ii1.882 (3)N1—F1xiii2.946 (8)
W1—F1iii1.882 (3)N1—F2viii2.969 (10)
W1—F1iv1.882 (3)F1—F1iii2.634 (6)
W1—F1v1.882 (3)F1—F1i2.634 (6)
W2—F21.867 (4)F1—F1ii2.688 (6)
W2—F2vi1.867 (4)F1—F1iv2.688 (6)
W2—F2vii1.867 (4)F2—F2viii2.632 (8)
W2—F2viii1.867 (4)F2—F2x2.632 (8)
W2—F2ix1.867 (4)F2—F2vii2.648 (8)
W2—F2x1.867 (4)F2—F2ix2.648 (8)
N1—F3xi2.760 (8)
F1—W1—F1i88.83 (16)F2vi—W2—F2vii89.6 (3)
F1—W1—F1iii88.83 (16)F2—W2—F2viii89.6 (3)
F1i—W1—F1iv88.83 (16)F2vi—W2—F2ix89.6 (3)
F1iv—W1—F1v88.83 (16)F2vii—W2—F2ix89.6 (3)
F1ii—W1—F1v88.83 (16)F2—W2—F2x89.6 (3)
F1ii—W1—F1iii88.83 (16)F2viii—W2—F2x89.6 (3)
F1—W1—F1ii91.17 (16)F2—W2—F2vii90.4 (3)
F1i—W1—F1iii91.17 (16)F2vi—W2—F2viii90.4 (3)
F1—W1—F1iv91.17 (16)F2vii—W2—F2viii90.4 (3)
F1ii—W1—F1iv91.17 (16)F2—W2—F2ix90.4 (3)
F1i—W1—F1v91.17 (16)F2vi—W2—F2x90.4 (3)
F1iii—W1—F1v91.17 (16)F2ix—W2—F2x90.4 (3)
F1i—W1—F1ii180.00 (17)F2—W2—F2vi179.999 (1)
F1iii—W1—F1iv180.00 (17)F2viii—W2—F2ix180.000 (1)
F1—W1—F1v179.999 (1)F2vii—W2—F2x180.0
Symmetry codes: (i) y+1/2, z1/2, x; (ii) y+1/2, z+1/2, x+1; (iii) z, x+1/2, y+1/2; (iv) z+1, x1/2, y+1/2; (v) x+1, y, z+1; (vi) x+1, y+1, z+1; (vii) y+1, z+1, x+1; (viii) z, x, y; (ix) z+1, x+1, y+1; (x) y, z, x; (xi) x+1/2, y, z+1/2; (xii) x, y+1/2, z1/2; (xiii) y+1/2, z, x+1/2.

Experimental details

For all structures: Mr = 370.98. Experiments were carried out with Mo Kα radiation using a Bruker APEXII CCD diffractometer. Absorption was corrected for by multi-scan methods, SADABS 2008/1. H-atom parameters were not defined.

(296K)(193K)
Crystal data
Chemical formulaF4WO2·2(H4N)·F(NH4)F4WO2·F·3(H4N)
Crystal system, space groupCubic, Pm3mCubic, Pa3
Temperature (K)296193
a (Å)6.0298 (1) 11.9635 (7)
V3)219.23 (1)1712.28 (17)
Z18
Dx (Mg m3)2.8102.878
µ (mm1)13.2413.56
Crystal size (mm)0.18 × 0.18 × 0.180.18 × 0.18 × 0.18
Data collection
Tmin, Tmax0.199, 0.1990.194, 0.194
No. of measured, independent and
observed [I > 2σ(I)] reflections
2864, 93, 93 27085, 1134, 696
Rint0.0200.033
(sin θ/λ)max1)0.7040.766
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.016, 0.035, 1.21 0.037, 0.101, 0.98
No. of reflections931079
No. of parameters1938
w = 1/[σ2(Fo2) + (0.0291P)2 + 0.0078P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.031P)2 + 14.1528P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.49, 0.631.90, 1.32

Computer programs: Bruker APEX2, Bruker SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Bruker SHELXTL.

 

Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds