The HfIV atoms in the centrosymmetric title compound, (C4H12N)2][Hf2F10(H2O)2], are bridged by two F atoms. The HfIV atoms show pentagonal–bipyramidal coordination. The dianions are linked by water–fluorine hydrogen bonds into layers.
Supporting information
CCDC reference: 298379
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (N-C) = 0.007 Å
- R factor = 0.021
- wR factor = 0.055
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.72
Alert level C
CRYSR01_ALERT_1_C _exptl_crystal_size_rad not in the CIF when expected.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Hf1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1
PLAT731_ALERT_1_C Bond Calc 0.86(4), Rep 0.850(10) ...... 4.00 su-Rat
O1 -H1 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat
O1 -H2 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.86(4), Rep 0.850(10) ...... 4.00 su-Rat
O1 -H1 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat
O1 -H2 1.555 1.555
PLAT736_ALERT_1_C H...A Calc 1.84(5), Rep 1.84(2) ...... 2.50 su-Rat
H1 -F4 1.555 4.566
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
10 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXS97.
Bis(tetramethylammonium) di-µ-fluoro-bis[aquatetrafluorohafnate(IV)]
top
Crystal data top
(C4H12N)2][Hf2F10(H2O)2] | F(000) = 1360 |
Mr = 731.30 | Dx = 2.572 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 754 reflections |
a = 9.919 (1) Å | θ = 27.0–44.7° |
b = 9.687 (1) Å | µ = 11.08 mm−1 |
c = 19.656 (2) Å | T = 295 K |
V = 1888.6 (4) Å3 | Sphere, colourless |
Z = 4 | 0.16 × 0.16 × 0.16 mm |
Data collection top
Bruker SMART 1000 area-detector diffractometer | 2168 independent reflections |
Radiation source: fine-focus sealed tube | 1942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
φ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −12→12 |
Tmin = 0.141, Tmax = 0.170 | l = −20→25 |
11359 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0221P)2 + 3.7908P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2168 reflections | Δρmax = 0.91 e Å−3 |
118 parameters | Δρmin = −0.81 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0026 (1) |
Special details top
Experimental. The crystal was measured up to a 2θmax of 90°; the cell was refined from 754
reflections in the 27.0 to 44.7° range as the cell would be more accurately
determined from higher angle reflections. However, the refinement used only
those below the 55° maximum. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Hf1 | 0.53921 (2) | 0.59702 (2) | 0.42352 (1) | 0.01665 (8) | |
F1 | 0.5859 (3) | 0.5589 (3) | 0.5282 (1) | 0.0306 (6) | |
F2 | 0.4156 (3) | 0.5306 (3) | 0.3519 (1) | 0.0372 (6) | |
F3 | 0.5968 (3) | 0.7156 (3) | 0.3463 (1) | 0.0333 (6) | |
F4 | 0.4054 (3) | 0.7374 (3) | 0.4540 (2) | 0.0364 (6) | |
F5 | 0.6708 (3) | 0.4487 (3) | 0.4010 (2) | 0.0379 (7) | |
O1 | 0.7045 (3) | 0.7357 (3) | 0.4587 (2) | 0.0356 (8) | |
N1 | 0.0513 (4) | 0.5903 (4) | 0.3353 (2) | 0.0278 (8) | |
C1 | −0.0895 (6) | 0.6159 (7) | 0.3122 (3) | 0.056 (2) | |
C2 | 0.1360 (6) | 0.7132 (5) | 0.3213 (3) | 0.043 (1) | |
C3 | 0.1079 (6) | 0.4701 (5) | 0.2976 (3) | 0.044 (1) | |
C4 | 0.0508 (8) | 0.5613 (8) | 0.4094 (3) | 0.056 (2) | |
H1 | 0.755 (5) | 0.730 (5) | 0.494 (2) | 0.06 (2)* | |
H2 | 0.730 (5) | 0.803 (3) | 0.434 (2) | 0.03 (1)* | |
H1a | −0.0896 | 0.6359 | 0.2643 | 0.084* | |
H1b | −0.1264 | 0.6930 | 0.3366 | 0.084* | |
H1c | −0.1434 | 0.5354 | 0.3206 | 0.084* | |
H2a | 0.1353 | 0.7324 | 0.2734 | 0.064* | |
H2b | 0.2268 | 0.6955 | 0.3359 | 0.064* | |
H2c | 0.1007 | 0.7912 | 0.3456 | 0.064* | |
H3a | 0.1079 | 0.4897 | 0.2497 | 0.067* | |
H3b | 0.0536 | 0.3899 | 0.3062 | 0.067* | |
H3c | 0.1985 | 0.4532 | 0.3125 | 0.067* | |
H4a | −0.0040 | 0.4816 | 0.4183 | 0.084* | |
H4b | 0.0147 | 0.6393 | 0.4333 | 0.084* | |
H4c | 0.1413 | 0.5441 | 0.4245 | 0.084* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Hf1 | 0.0165 (1) | 0.0167 (1) | 0.0168 (1) | 0.0003 (1) | 0.0000 (1) | 0.0024 (1) |
F1 | 0.035 (1) | 0.036 (1) | 0.021 (1) | −0.019 (1) | −0.008 (1) | 0.007 (1) |
F2 | 0.045 (2) | 0.042 (2) | 0.025 (1) | −0.014 (1) | −0.011 (1) | 0.005 (1) |
F3 | 0.035 (1) | 0.040 (1) | 0.025 (1) | −0.008 (1) | −0.000 (1) | 0.012 (1) |
F4 | 0.035 (2) | 0.030 (1) | 0.044 (2) | 0.010 (1) | 0.014 (1) | 0.003 (1) |
F5 | 0.041 (2) | 0.030 (1) | 0.043 (2) | 0.018 (1) | 0.010 (1) | 0.008 (1) |
O1 | 0.038 (2) | 0.039 (2) | 0.031 (2) | −0.024 (2) | −0.010 (1) | 0.014 (2) |
N1 | 0.029 (2) | 0.028 (2) | 0.026 (2) | 0.000 (2) | −0.0013 (1) | 0.000 (2) |
C1 | 0.025 (3) | 0.091 (5) | 0.053 (3) | 0.009 (3) | −0.003 (2) | −0.002 (3) |
C2 | 0.050 (3) | 0.025 (2) | 0.054 (3) | −0.004 (2) | 0.001 (2) | 0.004 (2) |
C3 | 0.047 (3) | 0.033 (3) | 0.053 (3) | 0.003 (2) | 0.000 (2) | −0.012 (2) |
C4 | 0.078 (5) | 0.061 (4) | 0.028 (3) | −0.011 (3) | −0.002 (3) | 0.000 (3) |
Geometric parameters (Å, º) top
Hf1—F1 | 2.141 (2) | C1—H1a | 0.96 |
Hf1—F1i | 2.173 (2) | C1—H1b | 0.96 |
Hf1—F2 | 1.975 (3) | C1—H1c | 0.96 |
Hf1—F3 | 1.987 (2) | C2—H2a | 0.96 |
Hf1—F5 | 1.991 (2) | C2—H2b | 0.96 |
Hf1—F4 | 1.992 (2) | C2—H2c | 0.96 |
Hf1—O1 | 2.230 (3) | C3—H3a | 0.96 |
N1—C2 | 1.482 (6) | C3—H3b | 0.96 |
N1—C4 | 1.483 (7) | C3—H3c | 0.96 |
N1—C1 | 1.490 (6) | C4—H4a | 0.96 |
N1—C3 | 1.491 (6) | C4—H4b | 0.96 |
O1—H1 | 0.85 (1) | C4—H4c | 0.96 |
O1—H2 | 0.85 (1) | | |
| | | |
F1—Hf1—F1i | 65.4 (1) | Hf1—O1—H1 | 130 (3) |
F1—Hf1—F2 | 139.7 (1) | Hf1—O1—H2 | 120 (3) |
F1—Hf1—F3 | 140.5 (1) | H1—O1—H2 | 109 (2) |
F1—Hf1—F4 | 88.5 (1) | N1—C1—H1a | 109.5 |
F1—Hf1—F5 | 87.0 (1) | N1—C1—H1b | 109.5 |
F1—Hf1—O1 | 69.3 (1) | H1a—C1—H1b | 109.5 |
F1i—Hf1—F2 | 74.4 (1) | N1—C1—H1c | 109.5 |
F1i—Hf1—F3 | 154.1 (1) | H1a—C1—H1c | 109.5 |
F1i—Hf1—F4 | 87.8 (1) | H1b—C1—H1c | 109.5 |
F1i—Hf1—F5 | 88.3 (1) | N1—C2—H2a | 109.5 |
F1i—Hf1—O1 | 134.7 (1) | N1—C2—H2b | 109.5 |
F2—Hf1—F3 | 79.8 (1) | H2a—C2—H2b | 109.5 |
F2—Hf1—F4 | 91.3 (1) | N1—C2—H2c | 109.5 |
F2—Hf1—F5 | 90.7 (1) | H2a—C2—H2c | 109.5 |
F2—Hf1—O1 | 150.9 (1) | H2b—C2—H2c | 109.5 |
F3—Hf1—F4 | 91.5 (1) | N1—C3—H3a | 109.5 |
F3—Hf1—F5 | 93.4 (1) | N1—C3—H3b | 109.5 |
F3—Hf1—O1 | 71.2 (1) | H3a—C3—H3b | 109.5 |
F5—Hf1—F4 | 175.0 (1) | N1—C3—H3c | 109.5 |
F4—Hf1—O1 | 89.2 (1) | H3a—C3—H3c | 109.5 |
F5—Hf1—O1 | 91.3 (1) | H3b—C3—H3c | 109.5 |
Hf1—F1—Hf1i | 114.6 (1) | N1—C4—H4a | 109.5 |
C2—N1—C4 | 109.7 (4) | N1—C4—H4b | 109.5 |
C2—N1—C1 | 110.0 (4) | H4a—C4—H4b | 109.5 |
C4—N1—C1 | 109.2 (5) | N1—C4—H4c | 109.5 |
C2—N1—C3 | 108.8 (4) | H4a—C4—H4c | 109.5 |
C4—N1—C3 | 109.9 (4) | H4b—C4—H4c | 109.5 |
C1—N1—C3 | 109.3 (4) | | |
| | | |
F2—Hf1—F1—Hf1i | −1.9 (3) | F4—Hf1—F1—Hf1i | 88.3 (2) |
F3—Hf1—F1—Hf1i | 178.9 (1) | O1—Hf1—F1—Hf1i | 178.0 (2) |
F5—Hf1—F1—Hf1i | −89.5 (2) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···F4ii | 0.85 (1) | 1.84 (2) | 2.643 (4) | 156 (5) |
O1—H2···F5iii | 0.85 (1) | 1.84 (2) | 2.660 (4) | 162 (4) |
Symmetry codes: (ii) x+1/2, −y+3/2, −z+1; (iii) −x+3/2, y+1/2, z. |