Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616017534/bp5091sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520616017534/bp5091Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520616017534/bp5091IIsup3.hkl |
CCDC references: 1514174; 1514175
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: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.
(H12N3HfF7) | Mo Kα radiation, λ = 0.71073 Å |
Mr = 365.62 | Cell parameters from 6673 reflections |
Cubic, Fm3m | θ = 3.8–46.1° |
a = 9.3964 (1) Å | µ = 12.65 mm−1 |
V = 829.63 (3) Å3 | T = 296 K |
Z = 4 | Octahedron, colourless |
F(000) = 672 | 0.25 × 0.23 × 0.22 mm |
Dx = 2.927 Mg m−3 |
Bruker APEX-II CCD diffractometer | 293 reflections with I > 2σ(I) |
Detector resolution: 8.33 pixels mm-1 | Rint = 0.019 |
ω scans | θmax = 52.5°, θmin = 3.8° |
Absorption correction: multi-scan Bruker SADABS | h = −20→19 |
Tmin = 0.593, Tmax = 0.750 | k = −20→19 |
8194 measured reflections | l = −20→20 |
293 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.009 | H-atom parameters not refined |
wR(F2) = 0.019 | w = 1/[σ2(Fo2) + (0.0032P)2 + 0.6486P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.005 |
293 reflections | Δρmax = 1.14 e Å−3 |
22 parameters | Δρmin = −0.67 e Å−3 |
0 restraints | Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.01226 (12) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Hf | 0.0000 | 0.0000 | 0.0000 | 0.02423 (2) | |
N1 | 0.2588 (4) | 0.2588 (4) | 0.2588 (4) | 0.0436 (7) | 0.25 |
N2 | 0.5000 | 0.5000 | 0.5000 | 0.0558 (9) | |
F1 | 0.0000 | 0.0000 | 0.2089 (2) | 0.0765 (9) | 0.5 |
F2 | 0.0000 | 0.0637 (6) | 0.2067 (6) | 0.0520 (15) | 0.0833 |
F3 | 0.0000 | 0.1290 (6) | 0.1891 (6) | 0.0484 (12) | 0.0833 |
H11 | 0.2038 | 0.2038 | 0.2038 | 0.086* | 0.25 |
H12 | 0.2038 | 0.3128 | 0.3128 | 0.086* | 0.0833 |
H13 | 0.3128 | 0.3128 | 0.2038 | 0.086* | 0.0833 |
H14 | 0.3128 | 0.2038 | 0.3128 | 0.086* | 0.0833 |
H2 | 0.5930 | 0.4814 | 0.4814 | 0.065* | 0.125 |
H3 | 0.4445 | 0.4445 | 0.4445 | 0.065* | 0.125 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hf | 0.02423 (2) | 0.02423 (2) | 0.02423 (2) | 0.000 | 0.000 | 0.000 |
N1 | 0.0436 (7) | 0.0436 (7) | 0.0436 (7) | 0.0005 (12) | 0.0005 (12) | 0.0005 (12) |
N2 | 0.0558 (9) | 0.0558 (9) | 0.0558 (9) | 0.000 | 0.000 | 0.000 |
F1 | 0.1063 (14) | 0.1063 (14) | 0.0170 (6) | 0.000 | 0.000 | 0.000 |
F2 | 0.062 (3) | 0.065 (3) | 0.0293 (18) | 0.000 | 0.000 | −0.0139 (19) |
F3 | 0.041 (2) | 0.059 (3) | 0.044 (2) | 0.000 | 0.000 | −0.0276 (17) |
Hf—F1 | 1.963 (2) | F1—F2ii | 2.826 (4) |
Hf—F1i | 1.963 (2) | F1—F3xi | 2.912 (4) |
Hf—F1ii | 1.963 (2) | F1—F3ix | 2.912 (4) |
Hf—F2 | 2.032 (5) | F1—F3x | 2.912 (4) |
Hf—F2iii | 2.032 (5) | F1—F3ii | 2.912 (4) |
Hf—F3 | 2.151 (5) | N1—N1xii | 0.234 (10) |
Hf—F3iii | 2.151 (5) | N1—F3xiii | 2.584 (4) |
F1—F2iv | 2.374 (6) | N1—F3xiv | 2.620 (3) |
F1—F2v | 2.374 (6) | N1—H11 | 0.8952 |
F2—F3vi | 2.484 (8) | N1—H12 | 0.8843 |
F3—F3vii | 2.425 (10) | N1—H13 | 0.8843 |
F1—F1i | 2.776 (3) | N1—H14 | 0.8843 |
F1—F1viii | 2.776 (3) | N2—F1xv | 2.735 (2) |
F1—F2ix | 2.826 (4) | N2—F2xvi | 2.820 (6) |
F1—F2x | 2.826 (4) | N2—H2 | 0.9081 |
F1—F2xi | 2.826 (4) | N2—H3 | 0.9033 |
F1—Hf—F1i | 90.0 | F1ii—Hf—F1v | 90.0 |
F1—Hf—F1ii | 90.0 | F1i—Hf—F1xvii | 90.0 |
F1i—Hf—F1ii | 180.0 | F1ii—Hf—F1xvii | 90.0 |
F1—Hf—F1viii | 90.0 | F1ii—Hf—F2 | 72.88 (17) |
F1i—Hf—F1viii | 90.0 | F1i—Hf—F2iii | 72.88 (17) |
F1ii—Hf—F1viii | 90.0 | F2xviii—Hf—F3xix | 72.8 (2) |
F1—Hf—F1v | 90.0 | F2vii—Hf—F3iv | 72.8 (2) |
F1i—Hf—F1v | 90.0 | F3iv—Hf—F3xx | 68.6 (3) |
Symmetry codes: (i) −y, −z, −x; (ii) y, z, x; (iii) −z, −y, x; (iv) −x, z, y; (v) z, x, y; (vi) −x, −z, y; (vii) −x, −y, z; (viii) −z, −x, −y; (ix) z, −y, x; (x) z, y, −x; (xi) −y, z, −x; (xii) x, −y+1/2, −z+1/2; (xiii) z, −y+1/2, x+1/2; (xiv) y, x+1/2, −z+1/2; (xv) −y+1/2, −z+1, −x+1/2; (xvi) −z+1, y+1/2, −x+1/2; (xvii) −x, −y, −z; (xviii) x, y, −z; (xix) x, −z, −y; (xx) x, z, −y. |
(H12N3TiO2F5) | Mo Kα radiation, λ = 0.71073 Å |
Mr = 229.03 | Cell parameters from 7086 reflections |
Cubic, Fm3m | θ = 3.8–37.6° |
a = 9.2327 (1) Å | µ = 1.14 mm−1 |
V = 787.02 (3) Å3 | T = 296 K |
Z = 4 | Octahedron, colourless |
F(000) = 464 | 0.24 × 0.23 × 0.22 mm |
Dx = 1.933 Mg m−3 |
Bruker APEX-II CCD diffractometer | 190 reflections with I > 2σ(I) |
Detector resolution: 8.33 pixels mm-1 | Rint = 0.020 |
w scans | θmax = 43.1°, θmin = 3.8° |
Absorption correction: multi-scan Bruker SADABS | h = −17→17 |
Tmin = 0.695, Tmax = 0.749 | k = −17→17 |
9680 measured reflections | l = −15→17 |
190 independent reflections |
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)] = 0.014 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.040 | H-atom parameters not refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0333P)2 + 0.0481P] where P = (Fo2 + 2Fc2)/3 |
190 reflections | (Δ/σ)max = 0.050 |
24 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ti1 | 0.0000 | 0.0000 | 0.0000 | 0.02239 (3) | |
N1 | 0.2593 (2) | 0.2593 (2) | 0.2593 (2) | 0.0439 (4) | 0.25 |
N2 | 0.5000 | 0.5000 | 0.5000 | 0.0592 (6) | |
O1 | 0.1808 (4) | 0.1142 (3) | 0.0000 | 0.0660 (9) | 0.0833 |
F1 | 0.20425 (11) | 0.01404 (17) | 0.01404 (17) | 0.0462 (4) | 0.125 |
F2 | 0.2000 (3) | 0.0602 (3) | 0.0000 | 0.0498 (8) | 0.0833 |
H11 | 0.2049 | 0.2049 | 0.2049 | 0.098* | 0.25 |
H12 | 0.2049 | 0.3149 | 0.3149 | 0.098* | 0.0833 |
H13 | 0.3149 | 0.2049 | 0.3149 | 0.098* | 0.0833 |
H14 | 0.3149 | 0.3149 | 0.2049 | 0.098* | 0.0833 |
H2 | 0.5930 | 0.4814 | 0.4814 | 0.044* | 0.125 |
H3 | 0.4445 | 0.4445 | 0.4445 | 0.098* | 0.125 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1 | 0.02239 (3) | 0.02239 (3) | 0.02239 (3) | 0.000 | 0.000 | 0.000 |
N1 | 0.0439 (4) | 0.0439 (4) | 0.0439 (4) | 0.0058 (6) | 0.0058 (6) | 0.0058 (6) |
N2 | 0.0592 (6) | 0.0592 (6) | 0.0592 (6) | 0.000 | 0.000 | 0.000 |
O1 | 0.0615 (15) | 0.096 (2) | 0.0406 (14) | −0.0518 (12) | 0.000 | 0.000 |
F1 | 0.0186 (3) | 0.0600 (5) | 0.0600 (5) | −0.0024 (4) | −0.0024 (4) | −0.007 (2) |
F2 | 0.0268 (8) | 0.0619 (17) | 0.0608 (17) | −0.0129 (9) | 0.000 | 0.000 |
Ti1—F1 | 1.8946 (10) | N2—F1xiii | 2.7367 (10) |
Ti1—F1i | 1.8947 (10) | N2—F1xiv | 2.7367 (10) |
N1—N1ii | 0.243 (6) | N2—F1ii | 2.7367 (10) |
N1—N1iii | 0.243 (6) | N2—H2 | 0.8923 |
N1—N1iv | 0.243 (6) | N2—H3 | 0.8875 |
N1—O1v | 2.613 (3) | O1—O1xv | 1.491 (4) |
N1—O1vi | 2.613 (3) | F2—O1xvi | 2.362 (5) |
N1—O1vii | 2.613 (3) | F1—F2xvi | 2.386 (3) |
N1—O1viii | 2.613 (3) | F1—F2xvii | 2.386 (3) |
N1—O1ix | 2.613 (3) | F1—O1xviii | 2.707 (3) |
N1—O1x | 2.613 (3) | F1—O1xix | 2.707 (3) |
N1—O1xi | 2.6530 (19) | F1—F1xx | 2.6732 (15) |
N1—H11 | 0.8701 | F1—F1xxi | 2.6731 (15) |
N1—H12 | 0.8828 | F1—F1xxii | 2.484 (3) |
N1—H13 | 0.8827 | F1—F2xxiii | 2.816 (2) |
N1—H14 | 0.8827 | F1—F2xxiv | 2.816 (2) |
N2—F1xii | 2.7367 (10) | F2—F2xxv | 2.611 (4) |
F1—Ti1—F1xxvi | 81.90 (10) | F1—Ti1—F1xx | 89.732 (7) |
Symmetry codes: (i) −y, −z, −x; (ii) x, −y+1/2, −z+1/2; (iii) −x+1/2, y, −z+1/2; (iv) −x+1/2, −y+1/2, z; (v) −z+1/2, −y+1/2, x; (vi) x, z+1/2, −y+1/2; (vii) −y+1/2, z+1/2, x; (viii) z+1/2, x, −y+1/2; (ix) x, −y+1/2, z+1/2; (x) −y+1/2, x, −z+1/2; (xi) z+1/2, y, −x+1/2; (xii) y+1/2, z+1/2, −x+1; (xiii) −y+1/2, −z+1/2, x; (xiv) −x+1, y+1/2, z+1/2; (xv) x, z, −y; (xvi) y, −x, z; (xvii) y, −z, −x; (xviii) −z, −y, x; (xix) z, x, −y; (xx) −y, z, x; (xxi) −z, x, y; (xxii) z, x, y; (xxiii) z, −y, −x; (xxiv) −z, −x, −y; (xxv) z, y, −x; (xxvi) y, z, x. |