Crystal structure of bis­(propane-1,3-diaminium) hexa­fluorido­aluminate di­aqua­tetra­fluorido­aluminate tetra­hydrate

Abdi, I.; Al-Sadhan, K.; Ben Ali, A.

doi:10.1107/S1600536814024155

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages 471-473

doi:10.1107/S1600536814024155

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Crystal structure of bis(propane-1,3-diaminium) hexafluoridoaluminate diaquatetrafluoridoaluminate tetrahydrate

Insaf Abdi,^a Khulood Al-Sadhan ^b and Amor Ben Ali ^a ^*

^aUniversité de Carthage, Faculté des Sciences de Bizerte, UR11ES30, 7021 Jarzouna, Tunisia, and ^bDepartment of Chemistry, Girls College of Science, University of Dammam, PO Box 838, Dammam 31113, Saudi Arabia
^*Correspondence e-mail: amor.benali@fsb.rnu.tn

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 30 August 2014; accepted 1 November 2014; online 8 November 2014)

The title compound, (C₃H₁₂N₂)₂[AlF₆][AlF₄(H₂O)₂]·4H₂O, was obtained by a solvothermal method in ethanol as solvent and with aluminium hydroxide, HF and 1,3-diaminopropane as educts. The asymmetric unit contains a quarter each of two crystallographically independent propane-1,3-diammonium dications, [AlF₆]³⁻ and [AlF₄(H₂O)₂]⁻ anions and four water molecules. The cations, anions and three of the independent water molecules are situated on special positions mm, while the fourth water molecule is disordered about a mirror plane. In the crystal, intermolecular N—H⋯F and O—H⋯F hydrogen bonds link the cations and anions into a three-dimensional framework with the voids filled by water molecules, which generate O—H⋯O hydrogen bonds and further consolidate the packing.

Keywords: crystal structure; hybrid organic–inorganic fluoride compound; fluoridoaluminate; aluminium; hydrothermal synthesis; hydrogen bonding.

CCDC reference: 1032262

1. Chemical context

Hybrid organic–inorganic fluoride compounds are composed of both organic and inorganic moieties. The search for new compounds in this class of materials is still intense due to their applications in many domains such as gas storage, catalysis, separation, ion-exchange and biomedicine (Horcajada et al., 2012 ; Stock & Biswas, 2012 ). Various hybrid materials containing fluorine organic ligands have been described in the literature (Ben Ali et al., 2007 ). The dimensionality of the metal fluoride entities are 0D (isolated polyanions) (Adil, Ben Ali et al., 2006 ; Adil, Leblanc & Maisonneuve, 2006 ; Fourquet et al., 1987 ) , 1D (chains) or 2D (layers) (Adil et al., 2010 ). The structural architecture of hybrid materials mainly depends on the metal and an organic part. However, other physical and physicochemical factors affect the resulting products such as the synthesis method (temperature, concentration, time of heating etc.) (Su et al., 2010 ). This work is a continuation of an exploration of chemical systems including metal fluoride and amine, and the study of their structures.

2. Structural commentary

The asymmetric unit of the title compound contains aluminum atoms located in two crystallographically independent sites with different environments, [Al2F₆] and [Al1F₄(H₂O)₂], and two independent 1,3-propane diamine (dap) dications (Fig. 1). The Al—F distances in the two octahedra range from 1.768 (2) to 1.809 (3) Å while the Al1—OW1 distance is longer [1.944 (4) Å]. The [AlF₆] octahedron is regular whereas [AlF₄(H₂O)₂] exhibits a pronounced distortion due to the strong influence of the crystal field created by the heteroligands (F⁻/H₂O). The value of the calculated valences (3.08 for Al1 and 3.01 for Al2) of the individual Al³⁺ cations (Brese & O'Keeffe, 1991 ) is in good agreement with the theoretical value, whereas those for the F⁻ anions are equal to 0.5. These anions complete their valence by establishing strong hydrogen bonds.

Figure 1
A portion of the crystal structure of the title compound showing the atom labelling and 50% probability displacement ellipsoids. Dashed lines denote hydrogen bonds. [Symmetry codes: (i) $[1\over2]$ − x, $[1\over2]$ − y, −1 − z; (ii) 1 − x, y, z; (iii) x, y, −z; (v) $[1\over2]$ − x, $[1\over2]$ − y, 1 + z; (vi) −x, y, z; (vii) x, −y, −1 − z; (viii) x, y, 1 + z.]

3. Supramolecular features

Each [AlF₄(H₂O)₂] octahedron is linked via N—H⋯F or O—H⋯F hydrogen bonds (Table 1) to one type of the organic cations (Fig. 2), with the formation of infinite chains parallel to the a axis. These chains are linked to each other by the AlF₆³⁻ dications and form infinite (H₂dap)[AlF₄(H₂O)₂] layers parallel to the ac plane (Fig. 3) . These layers are connected by the second organic cations and form a three-dimensional framework showing cavities, which are filled with the lattice water molecules.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F2	0.89	1.79	2.679 (6)	177
N1—H1B⋯F5ⁱ	0.89	1.99	2.846 (5)	161
N1—H1C⋯F5ⁱⁱ	0.89	1.99	2.846 (5)	161
N2—H2A⋯F3	0.89	1.84	2.722 (6)	173
N2—H2B⋯F1ⁱⁱⁱ	0.89	2.00	2.841 (5)	158
Ow1—H1⋯F5^iv	0.83 (4)	1.74 (4)	2.569 (5)	178
Ow2—H2⋯F3	0.84 (4)	2.10 (4)	2.880 (5)	178
Ow4—H4⋯Ow5^v	0.84 (4)	2.13	2.910 (5)	154
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-1]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-1]$ ; (iv) x, y, z+1; (v) x, y, -z.

Figure 2
The environment of the AlF₄(H₂O)₂ octahedron. Dashed lines denote hydrogen bonds.

Figure 3
The crystal packing of the title compound, viewed approximately along [001].

4. Database survey

In the Cambridge Structural Database (Version 5.35; Groom & Allen, 2014 ) numerous Class I fluoridoaluminates with isolated (poly)anions or extended 1D inorganic chains, 2D inorganic layers or 3D networks are mentioned. Eight compounds with AlF₆³⁻ anions exist (Grottel et al., 1992 ; Rother et al., 1996 , 1998 ; Touret et al., 2001 ; Adil et al., 2009 ; Bentrup et al., 1996 ) and seven compounds containing the AlF₅(H₂O)²⁻ anion (Cadiau et al., 2008 ; Petrosyants et al., 1997 ; Schröder et al., 1993 ). However, to our knowledge, no fluoridoaluminate hybrid compounds containing both the AlF₆³⁻ and AlF₅(H₂O)²⁻ anions have been reported.

5. Synthesis and crystallization

The title compound was prepared from a starting mixture of AlF₃ (0.5 g) in 40% HF (1.5 ml) and ethanol (5 ml). 1,3-Diaminopropane (0.54 ml) was added and mild hydrothermal conditions (463 K) were applied in a Teflon-lined autoclave (25 ml). The resulting product was washed with ethanol and dried in air giving colourless single crystals.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms of the NH₃ and CH₂ groups of the organic molecule were fixed geometrically [N—H = 0.89 (1) and C—H = 0.97 (1) Å with U_iso(H) = 1.2U_eq(N,C)]. All H atoms of the water molecules were located from a Fourier difference map. The O—H distances and H—O—H angles were fixed [O—H = 0.84 (1) and H⋯H = 1.34 (1) Å with U_iso(H) =1.5U_eq(O)]. The water molecule OW5 is disordered over two positions with the occupanies fixed to 0.5.

Table 2
Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)₂[AlF₆][AlF₄(H₂O)₂]·4H₂O
M_r	504.35
Crystal system, space group	Orthorhombic, Cmmm
Temperature (K)	293
a, b, c (Å)	12.975 (5), 25.115 (9), 6.452 (9)
V (Å³)	2103 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.24 × 0.12 × 0.05

Data collection
Diffractometer	Siemens AED2
No. of measured, independent and observed [I > 2σ(I)] reflections	1371, 1371, 939
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.148, 1.12
No. of reflections	1371
No. of parameters	105
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.48
Computer programs: STADI4 and X-RED (Stoe & Cie, 2002 ), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1032262

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814024155/cv5471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024155/cv5471Isup2.hkl

checkCIF report

Chemical context top

Hybrid organic–inorganic fluoride compounds are composed of both organic and inorganic moieties.The search for new compounds in this class of materials is still intense due to their applications in many domains such as gas storage, catalysis, separation, ion-exchange and biomedicine (Horcajada et al., 2012; Stock & Biswas, 2012). Various hybrid materials containing fluorine organic ligands have been described in the literature (Ben Ali et al., 2007) .The dimensionality of the metal fluoride entities are 0D (isolated polyanions) (Adil, Ben Ali et al., 2006; Adil, Leblanc & Maisonneuve, 2006; Fourquet et al., 1987 ), 1D (chains) or 2D (layers) (Adil et al., 2010). The structural architecture of hybrid materials mainly depends on the metal and an organic part. However, other physical and physicochemical factors affect the resulting products such as the synthesis method (temperature, concentration, time of heating etc.) (Su et al., 2010). This work is a continuation of an exploration of chemical systems including metal fluoride and amine, and the study of their structures.

Structural commentary top

The asymmetric unit of the title compound contains aluminum atoms located in two crystallographically independent sites with different environments, Al2F₆ and Al1F₄(H₂O)₂, and two independent 1,3-propane diamine (dap) dications (Fig. 1). The Al—F distances in the two octahedra range from 1.768 (2) to 1.809 (3) Å while Al1—OW1 distance is longer [1.944 (4) Å]. The AlF₆ octahedron is regular whereas Al1F₄(H₂O)₂ exhibits a pronounced distortion due to the strong influence of the crystal field created by the heteroligands (F^-/H₂O). The value of the calculated valence of Al³⁺ (Brese & O'Keeffe, 1991 ) is in good agreement with the theoretical value, whereas those for the F^- anions are equal to 0.5. These anions complete their valence by establishing strong hydrogen bonds.

Supramolecular features top

Each AlF₄(H₂O)₂ octahedron is linked via N—H···F or O—H···F hydrogen bonds to one type of the organic cations (Fig. 2), with the formation of infinite chains parallel to the a axis. These chains are linked to each other by the AlF₆^3- dications and form infinite (H₂dap)[AlF₄(H₂O)₂] layers parallel to the ac plane (Fig. 3 ). These layers are connected by the second organic cations and form a three-dimensional framework showing cavities filled with the crystalline water molecules.

Database survey top

In the Cambridge Structural Database (Version 5.35; Groom & Allen, 2014) numerous Class I fluoridoaluminates with isolated (poly)anions or extended 1D inorganic chains, 2D inorganic layers or 3D networks are mentioned. Eight compounds with AlF₆^3- anions exist (Grottel et al. 1992; Rother et al. 1996, 1998; Touret et al. 2001; Adil et al. 2009; Bentrup et al. 1996) and seven compounds containing the AlF₅(H₂O)^2- anion (Cadiau et al. 2008; Petrosyants et al. 1997; Schroder et al. 1993). However, to our knowledge, no fluoridoaluminate hybrid compounds containing both AlF₆^3- and AlF₅(H₂O)^2- anions have been reported.

Synthesis and crystallization top

Refinement top

The H atoms of the NH₃ and CH₂ groups of the organic molecule were fixed geometrically using AFIX 33 and AFIX 23 commands, respectively. All H atoms of the water molecule were located from a Fourier difference map. The O—H distances and H—O—H angles were fixed using DFIX and DANG options. The water molecule OW5 is disordered over two positions with the occupanies fixed to 0.5.

Related literature top

For related literature, see: Adil et al. (2009, 2010); Adil, Ben Ali, Leblanc & Maisonneuve (2006); Adil, Leblanc & Maisonneuve (2006); Ben Ali, Dang, Grenèche, Hémon-Ribaud, Leblanc & Maisonneuve (2007); Bentrup et al. (1996); Brese & O'Keeffe (1991); Cadiau et al. (2008); Fourquet et al. (1987); Groom & Allen (2014); Grottel et al. (1992); Horcajada et al. (2012); Petrosyants et al. (1997); Rother et al. (1996, 1998); Schroder et al. (1993); Stock & Biswas (2012); Su et al. (2010); Touret et al. (2001).

Computing details top

Data collection: STADI4 (Stoe & Cie, 2002); cell refinement: STADI4 (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

A portion of the crystal structure of the title compound showing the atom labelling and 50% probability displacement ellipsoids. Dashed lines denote hydrogen bonds. [Symmetry codes: (i) 1/2-x, 1/2-y, -1-z; (ii) 1-x, y, z; (iii) x, y, -z; (v) 1/2-x, 1/2-y, 1+z; (vi) -x, y, z; (vii) x, -y, -1-z; (viii) x, y, 1+z.]

The environment of the AlF₄(H₂O)₂ octahedron. Dashed lines denote hydrogen bonds.

The crystal packing of the title compound, viewed approximately along [001].

Bis(propane-1,3-diaminium) hexafluoridoaluminate diaquatetrafluoridoaluminate tetrahydrate top

Crystal data top

(C₃H₁₂N₂)₂[AlF₆][AlF₄(H₂O)₂]·4H₂O	F(000) = 1056
M_r = 504.35	D_x = 1.593 Mg m⁻³
Orthorhombic, Cmmm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2 2	Cell parameters from 32 reflections
a = 12.975 (5) Å	θ = 2–27.5°
b = 25.115 (9) Å	µ = 0.26 mm⁻¹
c = 6.452 (9) Å	T = 293 K
V = 2103 (3) Å³	Platelets, colourless
Z = 4	0.24 × 0.12 × 0.05 mm

Data collection top

Siemens AED2 diffractometer	R_int = 0.0000
Radiation source: fine-focus sealed tube	θ_max = 27.5°, θ_min = 1.6°
Graphite monochromator	h = 0→16
2θ/ω scan	k = 0→32
1371 measured reflections	l = 0→8
1371 independent reflections	3 standard reflections every 120 min
939 reflections with I > 2σ(I)	intensity decay: 4%

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0452P)² + 2.9098P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
1371 reflections	Δρ_max = 0.46 e Å⁻³
105 parameters	Δρ_min = −0.48 e Å⁻³
10 restraints	Extinction correction: WinGX (Farrugia, 2012), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (7)

Crystal data top

(C₃H₁₂N₂)₂[AlF₆][AlF₄(H₂O)₂]·4H₂O	V = 2103 (3) Å³
M_r = 504.35	Z = 4
Orthorhombic, Cmmm	Mo Kα radiation
a = 12.975 (5) Å	µ = 0.26 mm⁻¹
b = 25.115 (9) Å	T = 293 K
c = 6.452 (9) Å	0.24 × 0.12 × 0.05 mm

Data collection top

Siemens AED2 diffractometer	R_int = 0.0000
1371 measured reflections	3 standard reflections every 120 min
1371 independent reflections	intensity decay: 4%
939 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.047	10 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.46 e Å⁻³
1371 reflections	Δρ_min = −0.48 e Å⁻³
105 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Al1	0.0000	0.37606 (7)	0.0000	0.0234 (4)
Al2	0.2500	0.2500	−0.5000	0.0245 (4)
F1	0.0000	0.42435 (10)	0.2015 (4)	0.0382 (6)
F2	0.13615 (17)	0.37342 (11)	0.0000	0.0374 (6)
F3	0.2107 (2)	0.18091 (10)	−0.5000	0.0493 (8)
F5	0.15743 (14)	0.26362 (8)	−0.7007 (3)	0.0447 (5)
N1	0.3125 (2)	0.31814 (15)	0.0000	0.0325 (8)
H1A	0.2551	0.3375	0.0000	0.049*
H1B	0.3141	0.2977	0.1126	0.049*	0.50
H1C	0.3141	0.2977	−0.1126	0.049*	0.50
N2	0.3447 (3)	0.09755 (14)	−0.5000	0.0331 (8)
H2A	0.3055	0.1266	−0.5000	0.050*
H2B	0.3843	0.0974	−0.6126	0.050*	0.50
H2C	0.3843	0.0974	−0.3874	0.050*	0.50
C1	0.4029 (3)	0.35390 (18)	0.0000	0.0375 (11)
H1D	0.4014	0.3765	0.1219	0.045*	0.50
H1E	0.4014	0.3765	−0.1219	0.045*	0.50
C2	0.5000	0.3205 (2)	0.0000	0.0336 (14)
H2D	0.5000	0.2977	0.1215	0.040*	0.50
H2E	0.5000	0.2977	−0.1215	0.040*	0.50
C3	0.2784 (3)	0.04975 (18)	−0.5000	0.0415 (11)
H3A	0.2346	0.0501	−0.6217	0.050*	0.50
H3B	0.2346	0.0501	−0.3783	0.050*	0.50
C4	0.3432 (5)	0.0000	−0.5000	0.0427 (16)
H4A	0.3872	0.0000	−0.6215	0.051*	0.50
H4B	0.3872	0.0000	−0.3785	0.051*	0.50
OW1	0.0000	0.32173 (12)	0.2146 (6)	0.0400 (8)
OW2	0.0000	0.1449 (3)	−0.5000	0.080 (2)
OW3	0.3272 (7)	0.0000	0.0000	0.104 (3)
OW4	0.3732 (11)	0.5000	0.0000	0.200 (6)
OW5	0.5000	0.5374 (6)	0.342 (2)	0.110 (4)	0.50
H1	0.0517 (4)	0.3034 (11)	0.241 (9)	0.165*
H2	0.0517 (4)	0.1650 (8)	−0.5000	0.165*
H3	0.3669 (15)	0.0267 (2)	0.0000	0.165*
H4	0.4125 (17)	0.5000	−0.1039 (8)	0.165*
H5	0.5516 (4)	0.526 (5)	0.408 (12)	0.165*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0187 (8)	0.0233 (8)	0.0282 (9)	0.000	0.000	0.000
Al2	0.0230 (8)	0.0257 (8)	0.0248 (8)	0.0074 (7)	0.000	0.000
F1	0.0469 (14)	0.0332 (13)	0.0346 (13)	0.000	0.000	−0.0076 (11)
F2	0.0190 (11)	0.0373 (14)	0.0560 (16)	−0.0036 (10)	0.000	0.000
F3	0.0445 (16)	0.0282 (14)	0.075 (2)	0.0027 (12)	0.000	0.000
F5	0.0370 (9)	0.0582 (13)	0.0388 (10)	0.0178 (8)	−0.0120 (8)	−0.0007 (9)
N1	0.0211 (16)	0.043 (2)	0.0338 (18)	0.0014 (15)	0.000	0.000
N2	0.0342 (19)	0.0262 (17)	0.039 (2)	0.0023 (15)	0.000	0.000
C1	0.027 (2)	0.030 (2)	0.056 (3)	0.0028 (17)	0.000	0.000
C2	0.020 (3)	0.029 (3)	0.053 (4)	0.000	0.000	0.000
C3	0.027 (2)	0.033 (2)	0.064 (3)	0.0040 (18)	0.000	0.000
C4	0.028 (3)	0.029 (3)	0.071 (5)	0.000	0.000	0.000
OW1	0.0266 (14)	0.0385 (16)	0.055 (2)	0.000	0.000	0.0203 (16)
OW2	0.065 (4)	0.104 (6)	0.070 (4)	0.000	0.000	0.000
OW3	0.121 (7)	0.090 (6)	0.102 (6)	0.000	0.000	0.000
OW4	0.209 (14)	0.204 (17)	0.188 (13)	0.000	0.000	0.000
OW5	0.101 (8)	0.110 (9)	0.119 (10)	0.000	0.000	0.032 (8)

Geometric parameters (Å, º) top

Al1—F2ⁱ	1.768 (2)	N2—H2C	0.8900
Al1—F2	1.768 (2)	C1—C2	1.514 (5)
Al1—F1	1.778 (3)	C1—H1D	0.9700
Al1—F1ⁱⁱ	1.778 (3)	C1—H1E	0.9700
Al1—OW1	1.944 (4)	C2—C1^vi	1.514 (5)
Al1—OW1ⁱⁱ	1.944 (4)	C2—H2D	0.9700
Al2—F5ⁱⁱⁱ	1.799 (2)	C2—H2E	0.9700
Al2—F5	1.799 (2)	C3—C4	1.505 (5)
Al2—F5^iv	1.799 (2)	C3—H3A	0.9700
Al2—F5^v	1.799 (2)	C3—H3B	0.9700
Al2—F3	1.809 (3)	C4—C3^vii	1.505 (5)
Al2—F3ⁱⁱⁱ	1.809 (3)	C4—H4A	0.9700
N1—C1	1.476 (6)	C4—H4B	0.9700
N1—H1A	0.8900	OW1—H1	0.831 (10)
N1—H1B	0.8900	OW2—H2	0.840 (10)
N1—H1C	0.8900	OW3—H3	0.846 (10)
N2—C3	1.477 (6)	OW4—H4	0.842 (10)
N2—H2A	0.8900	OW5—H5	0.840 (10)
N2—H2B	0.8900

F2ⁱ—Al1—F2	175.7 (2)	H1A—N1—H1C	109.5
F2ⁱ—Al1—F1	91.47 (7)	H1B—N1—H1C	109.5
F2—Al1—F1	91.47 (7)	C3—N2—H2A	109.5
F2ⁱ—Al1—F1ⁱⁱ	91.47 (7)	C3—N2—H2B	109.5
F2—Al1—F1ⁱⁱ	91.47 (7)	H2A—N2—H2B	109.5
F1—Al1—F1ⁱⁱ	94.0 (2)	C3—N2—H2C	109.5
F2ⁱ—Al1—OW1	88.49 (7)	H2A—N2—H2C	109.5
F2—Al1—OW1	88.49 (7)	H2B—N2—H2C	109.5
F1—Al1—OW1	87.59 (16)	N1—C1—C2	108.9 (4)
F1ⁱⁱ—Al1—OW1	178.44 (16)	N1—C1—H1D	109.9
F2ⁱ—Al1—OW1ⁱⁱ	88.49 (7)	C2—C1—H1D	109.9
F2—Al1—OW1ⁱⁱ	88.49 (7)	N1—C1—H1E	109.9
F1—Al1—OW1ⁱⁱ	178.44 (16)	C2—C1—H1E	109.9
F1ⁱⁱ—Al1—OW1ⁱⁱ	87.60 (16)	H1D—C1—H1E	108.3
OW1—Al1—OW1ⁱⁱ	90.8 (2)	C1^vi—C2—C1	112.7 (5)
F5ⁱⁱⁱ—Al2—F5	180.00 (14)	C1^vi—C2—H2D	109.1
F5ⁱⁱⁱ—Al2—F5^iv	87.92 (14)	C1—C2—H2D	109.1
F5—Al2—F5^iv	92.08 (14)	C1^vi—C2—H2E	109.1
F5ⁱⁱⁱ—Al2—F5^v	92.08 (14)	C1—C2—H2E	109.1
F5—Al2—F5^v	87.92 (14)	H2D—C2—H2E	107.8
F5^iv—Al2—F5^v	180.00 (13)	N2—C3—C4	110.5 (4)
F5ⁱⁱⁱ—Al2—F3	90.34 (9)	N2—C3—H3A	109.6
F5—Al2—F3	89.66 (9)	C4—C3—H3A	109.6
F5^iv—Al2—F3	89.66 (9)	N2—C3—H3B	109.6
F5^v—Al2—F3	90.34 (9)	C4—C3—H3B	109.6
F5ⁱⁱⁱ—Al2—F3ⁱⁱⁱ	89.66 (9)	H3A—C3—H3B	108.1
F5—Al2—F3ⁱⁱⁱ	90.34 (9)	C3^vii—C4—C3	112.2 (5)
F5^iv—Al2—F3ⁱⁱⁱ	90.34 (9)	C3^vii—C4—H4A	109.2
F5^v—Al2—F3ⁱⁱⁱ	89.66 (9)	C3—C4—H4A	109.2
F3—Al2—F3ⁱⁱⁱ	180.0	C3^vii—C4—H4B	109.2
C1—N1—H1A	109.5	C3—C4—H4B	109.2
C1—N1—H1B	109.5	H4A—C4—H4B	107.9
H1A—N1—H1B	109.5	Al1—OW1—H1	122 (2)
C1—N1—H1C	109.5

Symmetry codes: (i) −x, y, z; (ii) x, y, −z; (iii) −x+1/2, −y+1/2, −z−1; (iv) x, y, −z−1; (v) −x+1/2, −y+1/2, z; (vi) −x+1, y, z; (vii) x, −y, −z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F2	0.89	1.79	2.679 (6)	177
N1—H1B···F5^viii	0.89	1.99	2.846 (5)	161
N1—H1C···F5ⁱⁱⁱ	0.89	1.99	2.846 (5)	161
N2—H2A···F3	0.89	1.84	2.722 (6)	173
N2—H2B···F1^ix	0.89	2.00	2.841 (5)	158
Ow1—H1···F5^x	0.83 (4)	1.74 (4)	2.569 (5)	178
Ow2—H2···F3	0.84 (4)	2.10 (4)	2.880 (5)	178
Ow4—H4···Ow5ⁱⁱ	0.84 (4)	2.13	2.910 (5)	154

Symmetry codes: (ii) x, y, −z; (iii) −x+1/2, −y+1/2, −z−1; (viii) −x+1/2, −y+1/2, z+1; (ix) −x+1/2, −y+1/2, z−1; (x) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F2	0.89	1.79	2.679 (6)	177
N1—H1B···F5ⁱ	0.89	1.99	2.846 (5)	161
N1—H1C···F5ⁱⁱ	0.89	1.99	2.846 (5)	161
N2—H2A···F3	0.89	1.84	2.722 (6)	173
N2—H2B···F1ⁱⁱⁱ	0.89	2.00	2.841 (5)	158
Ow1—H1···F5^iv	0.83 (4)	1.74 (4)	2.569 (5)	178
Ow2—H2···F3	0.84 (4)	2.10 (4)	2.880 (5)	178
Ow4—H4···Ow5^v	0.84 (4)	2.131	2.910 (5)	154

Symmetry codes: (i) −x+1/2, −y+1/2, z+1; (ii) −x+1/2, −y+1/2, −z−1; (iii) −x+1/2, −y+1/2, z−1; (iv) x, y, z+1; (v) x, y, −z.

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)₂[AlF₆][AlF₄(H₂O)₂]·4H₂O
M_r	504.35
Crystal system, space group	Orthorhombic, Cmmm
Temperature (K)	293
a, b, c (Å)	12.975 (5), 25.115 (9), 6.452 (9)
V (Å³)	2103 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.24 × 0.12 × 0.05

Data collection
Diffractometer	Siemens AED2 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1371, 1371, 939
R_int	0.0000
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.148, 1.12
No. of reflections	1371
No. of parameters	105
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.48

Computer programs: STADI4 (Stoe & Cie, 2002), STADI4 (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Acknowledgements

The authors are indebted to Dr Vincent Maisonneuve (University of Le Mans) for the data collection

References

Adil, K., Ben Ali, A., Leblanc, M. & Maisonneuve, V. (2006). Solid State Sci. 8, 698–703. Web of Science CSD CrossRef CAS Google Scholar
Adil, K., Leblanc, M. & Maisonneuve, V. (2006). J. Fluor. Chem. 127, 1349–1354. Web of Science CSD CrossRef CAS Google Scholar
Adil, K., Leblanc, M. & Maisonneuve, V. (2009). J. Fluor. Chem. 130, 1099–1105. Web of Science CSD CrossRef CAS Google Scholar
Adil, K., Leblanc, M., Maisonneuve, V. & Lightfoot, P. (2010). Dalton Trans. 39, 5983–5993. Web of Science CrossRef CAS PubMed Google Scholar
Ben Ali, A., Trang Dang, M., Grenèche, J.-M., Hémon-Ribaud, A., Leblanc, M. & Maisonneuve, V. (2007). J. Solid State Chem. 180, 1911–1917. Web of Science CSD CrossRef CAS Google Scholar
Bentrup, U., Ahmadi, A., Kang, H.-C. & Massa, W. (1998). Z. Anorg. Allg. Chem. 624, 1465–1470. CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cadiau, A., Hemon-Ribaud, A., Leblanc, M. & Maisonneuve, V. (2008). Acta Cryst. E64, m523–m524. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fourquet, J. L., Plet, F., Calage, Y. & De Pape, R. (1987). J. Solid State Chem. 69, 76–80. CSD CrossRef CAS Web of Science Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Grottel, M., Kozak, A., Maluszyriska, H. & Pajak, Z. (1992). J. Phys. Condens. Matter, 4, 1837–1848. CSD CrossRef CAS Web of Science Google Scholar
Horcajada, P., Gref, R., Baati, T., Allan, P. K., Maurin, G., Couvreur, P., Férey, G., Morris, R. E. & Serre, C. (2012). Chem. Rev. 112, 1232–1268. Web of Science CrossRef CAS PubMed Google Scholar
Petrosyants, S. P., Malyarik, M. A., Ilyukhin, A. B. & Buslaev, Yu. A. (1997). Zh. Neorg. Khim. 42, 1551–1557. Google Scholar
Rother, G., Worzala, H. & Bentrup, U. (1996). Z. Anorg. Allg. Chem. 622, 1991–1996. CSD CrossRef CAS Web of Science Google Scholar
Rother, G., Worzala, H. & Bentrup, U. (1998). Z. Kristallogr. New. Cryst. Struct. 213, 119–120. CAS Google Scholar
Schröder, L., Frenzen, G., Massa, W. & Menz, D. H. (1993). Z. Anorg. Allg. Chem. 619, 1307–1314. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stock, N. & Biswas, S. (2012). Chem. Rev. 112, 933–969. Web of Science CrossRef CAS PubMed Google Scholar
Stoe & Cie (2002). STADI4 and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Su, Z., Fan, J., Okamura, T., Sun, W.-Y. & Ueyama, N. (2010). Cryst. Growth Des. 10, 3515–3521. Web of Science CSD CrossRef CAS Google Scholar
Touret, J., Bourdon, X., Leblanc, M., Retoux, R., Renaudin, J. & Maisonneuve, V. (2001). J. Fluor. Chem. 110, 133–138. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 70| Part 12| December 2014| Pages 471-473

doi:10.1107/S1600536814024155

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of bis­­(propane-1,3-diaminium) hexa­fluorido­aluminate di­aqua­tetra­fluorido­aluminate tetra­hydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of bis(propane-1,3-diaminium) hexafluoridoaluminate diaquatetrafluoridoaluminate tetrahydrate

3. Supramolecular features