Literature DB >> 25309188

Crystal structure of bis-(propane-1,3-di-ammonium) hexa-fluorido-aluminate fluoride trihydrate.

I Abdi1, K A Al-Sadhan2, A Ben Ali1.   

Abstract

The title compound, (C3H10N2)2[AlF6]F·3H2O, was obtained using the solvothermal method with aluminium hydroxide, HF and propane-1,3-di-amine as precursors in ethanol as solvent. The structure consists of isolated [AlF6](3-) octa-hedra, diprotonated propane-1,3-di-amine cations [(H2dap)(2+)], free fluoride ions and water mol-ecules of solvation. The Al-F bond lengths in the octa-hedral [AlF6](3-) anions range from 1.7690 (19) to 1.8130 (19) Å, with an average value of 1.794 Å. Each [AlF6](3-) anion is surrounded by three water mol-ecules and by six diprotonated amine cations. The 'free' fluoride ion is hydrogen bonded to four H atoms belonging to four dications and has a distorted tetra-hedral geometry. The three water mol-ecules are connected by hydrogen bonds, forming trimers that connect the AlF6 octa-hedra and dications into a three-dimensional framework.

Entities:  

Keywords:  crystal structure; hexa­fluorido­aluminate; hybrid aluminates; hydrogen bonding

Year:  2014        PMID： 25309188      PMCID： PMC4186155          DOI： 10.1107/S1600536814018844

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For general background to hybrid aluminates, their syntheses and applications, see: Ben Ali et al. (2007 ▶, 2009 ▶); Lhoste et al. (2009 ▶); Adil et al. (2010 ▶); Martineau et al. (2012 ▶); Cadiau et al. (2013 ▶). For a review of hydrogen-bonding inter­actions, see: Steiner (1998 ▶).

Experimental

Crystal data

(C3H10N2)2[AlF6]F·3H2O M = 366.31 Triclinic, a = 9.825 (2) Å b = 9.974 (3) Å c = 10.697 (2) Å α = 70.01 (2)° β = 67.89 (2)° γ = 59.77 (1)° V = 823.8 (3) Å3 Z = 2 Mo Kα radiation μ = 0.21 mm−1 T = 298 K 0.61 × 0.13 × 0.08 mm

Data collection

Siemens AED2 diffractometer Absorption correction: gaussian (SADABS; Sheldrick, 1996 ▶) T min = 0.968, T max = 0.985 3411 measured reflections 3411 independent reflections 3046 reflections with I > 2σ(I) 3 standard reflections every 120 min intensity decay: 4%

Refinement

R[F 2 > 2σ(F 2)] = 0.059 wR(F 2) = 0.183 S = 1.05 3411 reflections 215 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.62 e Å−3 Δρmin = −0.54 e Å−3

Data collection: STADI4 (Stoe, 1998 ▶); cell refinement: STADI4; data reduction: X-RED (Stoe, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and WinGX (Farrugia, 2012 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814018844/cq2011sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018844/cq2011Isup2.hkl Click here for additional data file. . DOI: 10.1107/S1600536814018844/cq2011fig1.tif View of the structure of (I) along the [010] axis. Click here for additional data file. 6 . DOI: 10.1107/S1600536814018844/cq2011fig2.tif The environment of the AlF6 octa­hedron. Click here for additional data file. . DOI: 10.1107/S1600536814018844/cq2011fig3.tif The environment of the isolated fluoride anion. Click here for additional data file. . DOI: 10.1107/S1600536814018844/cq2011fig4.tif The environment of water mol­ecules CCDC reference: 1012356 Additional supporting information: crystallographic information; 3D view; checkCIF report
(C3H10N2)2[AlF6]F·3H2OZ = 2
Mr = 366.31F(000) = 388
Triclinic, P1Dx = 1.477 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.825 (2) ÅCell parameters from 32 reflections
b = 9.974 (3) Åθ = 5.0–20.0°
c = 10.697 (2) ŵ = 0.21 mm−1
α = 70.01 (2)°T = 298 K
β = 67.89 (2)°Platelet, colorless
γ = 59.77 (1)°0.61 × 0.13 × 0.08 mm
V = 823.8 (3) Å3
Siemens AED2 diffractometer3046 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 27.6°, θmin = 2.1°
2θ/ω scanh = −11→12
Absorption correction: gaussian (SADABS; Sheldrick, 1996)k = −11→12
Tmin = 0.968, Tmax = 0.985l = 0→13
3411 measured reflections3 standard reflections every 120 min
3411 independent reflections intensity decay: 4%
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H atoms treated by a mixture of independent and constrained refinement
S = 1.05 ' w = 1/[σ2(Fo2) + (0.1177P)2 + 0.6344P] where P = (Fo2 + 2Fc2)/3'
3411 reflections(Δ/σ)max = 0.009
215 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.54 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.
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 > 2sigma(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.
xyzUiso*/Ueq
Al10.83033 (8)−0.20234 (8)0.29308 (6)0.0238 (2)
F11.0025 (2)−0.3849 (2)0.2527 (3)0.0678 (6)
F20.9474 (2)−0.1577 (3)0.35631 (17)0.0496 (5)
F30.9030 (2)−0.1056 (3)0.12502 (16)0.0518 (5)
F40.7092 (2)−0.2378 (3)0.2304 (2)0.0575 (5)
F50.6596 (2)−0.0158 (2)0.3295 (2)0.0546 (5)
F60.7625 (3)−0.2962 (3)0.4612 (2)0.0747 (8)
F70.80224 (19)−0.13548 (18)0.76019 (15)0.0357 (4)
N10.86118 (18)0.02879 (18)0.8720 (2)0.0295 (4)
H1A0.8503−0.02430.82720.054 (2)*
H1B0.8678−0.02580.95670.054 (2)*
H1C0.95130.04290.82780.054 (2)*
N20.26017 (18)0.32258 (18)0.9923 (2)0.0333 (4)
H2A0.27470.23790.96900.054 (2)*
H2B0.19270.40940.94800.054 (2)*
H2C0.21780.31711.08250.054 (2)*
N30.6255 (3)0.0499 (3)0.5761 (2)0.0348 (5)
H3A0.6799−0.00920.64070.054 (2)*
H3B0.67380.00380.50320.054 (2)*
H3C0.52380.05990.60890.054 (2)*
N40.9607 (3)0.3445 (2)0.4048 (2)0.0326 (5)
H4A0.99320.30300.48230.054 (2)*
H4B0.95840.44030.37190.054 (2)*
H4C1.02960.28280.34330.054 (2)*
C10.7954 (3)0.3567 (3)0.4329 (3)0.0355 (5)
H1D0.75670.40930.35010.054 (2)*
H1E0.72140.41990.50310.054 (2)*
C20.7184 (3)0.1845 (3)0.8795 (3)0.0308 (5)
H2D0.71590.24680.78740.054 (2)*
H2E0.72840.24060.93140.054 (2)*
C30.6240 (3)0.2082 (3)0.5355 (3)0.0334 (5)
H3D0.56880.25970.61440.054 (2)*
H3E0.56460.27270.46520.054 (2)*
C40.5606 (3)0.1665 (3)0.9473 (3)0.0312 (5)
H4D0.54850.11280.89450.054 (2)*
H4E0.56280.10341.03910.054 (2)*
C50.7966 (3)0.1947 (3)0.4807 (3)0.0312 (5)
H5D0.85440.13430.55240.054 (2)*
H5E0.85350.13870.40460.054 (2)*
C60.4188 (3)0.3281 (3)0.9548 (3)0.0351 (5)
H6D0.41990.37201.02230.054 (2)*
H6E0.43130.39760.86630.054 (2)*
OW10.6507 (3)0.2741 (3)0.1872 (3)0.0543 (6)
H110.658 (7)0.173 (3)0.216 (5)0.096 (17)*
H120.536 (3)0.334 (6)0.214 (6)0.12 (2)*
OW21.0850 (3)−0.3475 (3)−0.0480 (3)0.0480 (5)
OW30.6830 (3)0.5567 (4)0.7114 (3)0.0670 (8)
H211.053 (6)−0.325 (5)0.020 (5)0.063 (14)*
H221.160 (6)−0.322 (6)−0.080 (5)0.073 (14)*
H310.712 (5)0.602 (5)0.633 (4)0.052 (10)*
H320.767 (7)0.507 (6)0.735 (6)0.090 (17)*
U11U22U33U12U13U23
Al10.0238 (3)0.0282 (4)0.0245 (3)−0.0153 (3)−0.0087 (2)−0.0013 (2)
F10.0399 (10)0.0365 (9)0.1124 (18)−0.0088 (8)−0.0130 (11)−0.0167 (10)
F20.0553 (10)0.0851 (13)0.0371 (8)−0.0519 (10)−0.0159 (7)−0.0044 (8)
F30.0537 (10)0.0853 (14)0.0284 (8)−0.0501 (10)−0.0160 (7)0.0141 (8)
F40.0516 (11)0.0991 (16)0.0566 (11)−0.0513 (11)−0.0063 (8)−0.0322 (10)
F50.0335 (9)0.0417 (9)0.0857 (14)−0.0117 (7)−0.0063 (9)−0.0258 (9)
F60.0929 (17)0.117 (2)0.0379 (9)−0.0847 (17)−0.0185 (10)0.0246 (11)
F70.0399 (8)0.0398 (8)0.0357 (8)−0.0209 (7)−0.0141 (6)−0.0054 (6)
N10.0270 (9)0.0363 (10)0.0326 (10)−0.0193 (8)−0.0110 (8)−0.0020 (8)
N20.0315 (10)0.0368 (11)0.0344 (10)−0.0175 (9)−0.0079 (8)−0.0058 (8)
N30.0325 (10)0.0493 (12)0.0352 (10)−0.0257 (10)−0.0110 (8)−0.0065 (9)
N40.0341 (11)0.0329 (10)0.0366 (10)−0.0194 (9)−0.0113 (8)−0.0027 (8)
C10.0297 (11)0.0318 (12)0.0465 (14)−0.0128 (10)−0.0151 (10)−0.0035 (10)
C20.0329 (12)0.0322 (12)0.0343 (11)−0.0206 (10)−0.0095 (9)−0.0027 (9)
C30.0271 (11)0.0391 (13)0.0379 (12)−0.0158 (10)−0.0099 (9)−0.0071 (10)
C40.0307 (11)0.0317 (11)0.0367 (12)−0.0184 (10)−0.0101 (9)−0.0031 (9)
C50.0249 (10)0.0349 (12)0.0374 (12)−0.0144 (9)−0.0082 (9)−0.0082 (9)
C60.0303 (12)0.0337 (12)0.0475 (14)−0.0162 (10)−0.0118 (10)−0.0086 (10)
OW10.0534 (13)0.0473 (12)0.0579 (13)−0.0279 (11)−0.0084 (11)−0.0017 (10)
OW20.0400 (11)0.0468 (12)0.0585 (14)−0.0144 (10)−0.0093 (10)−0.0217 (10)
OW30.0425 (13)0.0716 (17)0.0512 (14)−0.0207 (12)−0.0061 (11)0.0162 (12)
Al1—F61.7690 (19)N3—H3B0.8900
Al1—F41.7832 (17)N3—H3C0.8900
Al1—F31.7929 (16)N4—C11.483 (3)
Al1—F11.803 (2)N4—H4A0.8900
Al1—F21.8126 (16)N4—H4B0.8900
Al1—F51.8130 (19)N4—H4C0.8900
F1—F32.499 (3)C1—C51.514 (3)
F1—F42.556 (3)C1—H1D0.9700
F1—F62.570 (4)C1—H1E0.9700
F1—F22.586 (3)C2—C41.518 (3)
F2—F32.507 (2)C2—H2D0.9700
F2—F52.527 (3)C2—H2E0.9700
F2—F62.529 (3)C3—C51.521 (3)
F3—F42.556 (2)C3—H3D0.9700
F3—F52.559 (3)C3—H3E0.9700
F4—F52.529 (3)C4—C61.513 (3)
F4—F62.529 (3)C4—H4D0.9700
F5—F62.522 (3)C4—H4E0.9700
F5—H111.85 (3)C5—H5D0.9700
N1—C21.481 (3)C5—H5E0.9700
N1—H1A0.8900C6—H6D0.9700
N1—H1B0.8900C6—H6E0.9700
N1—H1C0.8900OW1—H110.925 (19)
N2—C61.481 (3)OW1—H120.95 (2)
N2—H2A0.8900OW2—H210.74 (5)
N2—H2B0.8900OW2—H220.82 (5)
N2—H2C0.8900OW3—H310.83 (4)
N3—C31.482 (3)OW3—H320.81 (6)
N3—H3A0.8900
F6—Al1—F490.79 (10)H1A—N1—H1C109.5
F6—Al1—F3177.96 (9)H1B—N1—H1C109.5
F4—Al1—F391.25 (9)C6—N2—H2A109.5
F6—Al1—F192.04 (13)C6—N2—H2B109.5
F4—Al1—F190.93 (11)H2A—N2—H2B109.5
F3—Al1—F188.04 (11)C6—N2—H2C109.5
F6—Al1—F289.84 (9)H2A—N2—H2C109.5
F4—Al1—F2177.63 (11)H2B—N2—H2C109.5
F3—Al1—F288.11 (8)C3—N3—H3A109.5
F1—Al1—F291.33 (11)C3—N3—H3B109.5
F6—Al1—F589.49 (12)H3A—N3—H3B109.5
F4—Al1—F589.36 (10)C3—N3—H3C109.5
F3—Al1—F590.41 (11)H3A—N3—H3C109.5
F1—Al1—F5178.44 (10)H3B—N3—H3C109.5
F2—Al1—F588.36 (10)C1—N4—H4A109.5
F3—F1—F460.73 (8)C1—N4—H4B109.5
F3—F1—F689.25 (9)H4A—N4—H4B109.5
F4—F1—F659.11 (8)C1—N4—H4C109.5
F3—F1—F259.05 (7)H4A—N4—H4C109.5
F4—F1—F288.70 (8)H4B—N4—H4C109.5
F6—F1—F258.74 (8)N4—C1—C5111.0 (2)
F3—F2—F561.11 (8)N4—C1—H1D109.4
F3—F2—F690.00 (8)C5—C1—H1D109.4
F5—F2—F659.83 (8)N4—C1—H1E109.4
F3—F2—F158.74 (8)C5—C1—H1E109.4
F5—F2—F190.00 (8)H1D—C1—H1E108.0
F6—F2—F160.32 (9)N1—C2—C4111.36 (18)
F1—F3—F262.21 (9)N1—C2—H2D109.4
F1—F3—F460.74 (8)C4—C2—H2D109.4
F2—F3—F490.47 (7)N1—C2—H2E109.4
F1—F3—F591.25 (8)C4—C2—H2E109.4
F2—F3—F559.82 (8)H2D—C2—H2E108.0
F4—F3—F559.25 (7)N3—C3—C5110.7 (2)
F5—F4—F659.81 (9)N3—C3—H3D109.5
F5—F4—F360.43 (8)C5—C3—H3D109.5
F6—F4—F388.90 (7)N3—C3—H3E109.5
F5—F4—F190.64 (8)C5—C3—H3E109.5
F6—F4—F160.72 (10)H3D—C3—H3E108.1
F3—F4—F158.52 (7)C6—C4—C2109.45 (19)
F6—F5—F460.10 (9)C6—C4—H4D109.8
F6—F5—F260.13 (8)C2—C4—H4D109.8
F4—F5—F290.65 (8)C6—C4—H4E109.8
F6—F5—F389.00 (9)C2—C4—H4E109.8
F4—F5—F360.32 (7)H4D—C4—H4E108.2
F2—F5—F359.07 (7)C1—C5—C3110.8 (2)
Al1—F5—H11120.3 (17)C1—C5—H5D109.5
F6—F5—H11160.8 (17)C3—C5—H5D109.5
F4—F5—H11120.6 (16)C1—C5—H5E109.5
F2—F5—H11101.0 (17)C3—C5—H5E109.5
F3—F5—H1176.8 (17)H5D—C5—H5E108.1
F5—F6—F260.03 (8)N2—C6—C4112.33 (19)
F5—F6—F460.09 (9)N2—C6—H6D109.1
F2—F6—F490.59 (8)C4—C6—H6D109.1
F5—F6—F190.47 (8)N2—C6—H6E109.1
F2—F6—F160.94 (8)C4—C6—H6E109.1
F4—F6—F160.16 (9)H6D—C6—H6E107.9
C2—N1—H1A109.5H11—OW1—H12100 (5)
C2—N1—H1B109.5H21—OW2—H22100 (5)
H1A—N1—H1B109.5H31—OW3—H32102 (5)
C2—N1—H1C109.5
D—H···AD—HH···AD···AD—H···A
N1—H1A···F70.891.812.696 (3)171
N1—H1B···F3i0.891.792.663 (3)166
N1—H1C···F2ii0.892.082.826 (3)141
N1—H1C···F3ii0.892.092.796 (3)136
N2—H2A···F4iii0.892.082.657 (3)122
N2—H2B···OW2iv0.892.112.804 (3)134
N2—H2C···F7v0.892.042.724 (3)132
N3—H3A···F70.891.792.677 (3)176
N3—H3B···F50.892.002.792 (3)148
N3—H3C···F5iii0.891.892.753 (4)162
N4—H4A···F2ii0.891.902.757 (3)161
N4—H4B···F1vi0.891.922.776 (4)162
N4—H4C···F7ii0.891.842.724 (3)169
OW1—H11···F50.921.852.743 (3)161
OW1—H12···OW3vii0.951.852.789 (5)173
OW2—H21···F10.742.27 (5)2.943 (3)152 (5)
OW2—H22···OW1viii0.82 (7)1.982.785 (5)170
OW3—H31···F6vi0.82 (4)1.79 (4)2.612 (4)176
OW3—H32···F1ii0.81 (7)1.99 (7)2.783 (4)167
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
N1—H1A⋯F70.891.812.696 (3)171
N1—H1B⋯F3i 0.891.792.663 (3)166
N1—H1C⋯F2ii 0.892.082.826 (3)141
N1—H1C⋯F3ii 0.892.092.796 (3)136
N2—H2A⋯F4iii 0.892.082.657 (3)122
N2—H2B⋯OW2iv 0.892.112.804 (3)134
N2—H2C⋯F7v 0.892.042.724 (3)132
N3—H3A⋯F70.891.792.677 (3)176
N3—H3B⋯F50.892.002.792 (3)148
N3—H3C⋯F5iii 0.891.892.753 (4)162
N4—H4A⋯F2ii 0.891.902.757 (3)161
N4—H4B⋯F1vi 0.891.922.776 (4)162
N4—H4C⋯F7ii 0.891.842.724 (3)169
OW1—H11⋯F50.921.852.743 (3)161
OW1—H12⋯OW3vii 0.951.852.789 (5)173
OW2—H21⋯F10.742.27 (5)2.943 (3)152 (5)
OW2—H22⋯OW1viii 0.82 (7)1.982.785 (5)170
OW3—H31⋯F6vi 0.82 (4)1.79 (4)2.612 (4)176
OW3—H32⋯F1ii 0.81 (7)1.99 (7)2.783 (4)167

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

  3 in total

1.  SMARTER crystallography of the fluorinated inorganic-organic compound Zn3Al2F12·[HAmTAZ]6.

Authors:  Charlotte Martineau; Amandine Cadiau; Boris Bouchevreau; Jürgen Senker; Francis Taulelle; Karim Adil
Journal:  Dalton Trans       Date:  2012-04-10       Impact factor: 4.390

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  Structural chemistry of organically-templated metal fluorides.

Authors:  Karim Adil; Marc Leblanc; Vincent Maisonneuve; Philip Lightfoot
Journal:  Dalton Trans       Date:  2010-04-15       Impact factor: 4.390
  3 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.