Diethyl­enetriaminium hexa­fluorido­titanate(IV) fluoride

J Lhoste; K Adil; M Leblanc; V Maisonneuve

doi:10.1107/S1600536808009781

. 2008 Oct 9;64(Pt 11):m1375. doi: 10.1107/S1600536808009781

Diethylenetriaminium hexafluoridotitanate(IV) fluoride

J Lhoste ^a, K Adil ^a,^*, M Leblanc ^a, V Maisonneuve ^a

PMCID: PMC2959685 PMID: 21580831

Abstract

The title compound, (C₆H₂₁N₄)[TiF₆]F, was synthesized by the reaction of TiO₂, tris(2-aminoethyl)amine, HF and ethanol at 463 K in a microwave oven. The crystal structure consists of two crystallographically independent [TiF₆]²⁻ anions, two fluoride anions and two triply-protonated tris(2-aminoethyl)amine cations. The Ti atoms are coordinated by six F atoms within slightly distorted octahedra. The anions and cations are connected by intermolecular N—H⋯F hydrogen bonds.

Related literature

For background, see: Adil et al. (2006 ▶). For related structures, see: Calov et al. (1992 ▶); Dadachov et al. (2000 ▶); Tang et al. (2001 ▶).

Experimental

Crystal data

(C₆H₂₁N₄)[TiF₆]F
M _r = 330.14
Monoclinic,
a = 16.265 (4) Å
b = 8.089 (3) Å
c = 21.778 (5) Å
β = 110.54 (2)°
V = 2683.1 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 298 (2) K
0.18 × 0.13 × 0.06 mm

Data collection

Siemens AED2 diffractometer
Absorption correction: Gaussian (SHELX76; Sheldrick, 2008 ▶) T _min = 0.850, T _max = 0.929
6191 measured reflections
6133 independent reflections
3531 reflections with I > 2σ(I)
3 standard reflections frequency: 120 min intensity decay: 15%

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.155
S = 1.12
6133 reflections
332 parameters
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: STADI4 (Stoe & Cie, 1998 ▶); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009781/nc2095sup1.cif

e-64-m1375-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009781/nc2095Isup2.hkl

e-64-m1375-Isup2.hkl^{(294.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ti1—F1	1.796 (3)
Ti1—F2	1.826 (3)
Ti1—F4	1.856 (3)
Ti1—F5	1.865 (3)
Ti1—F3	1.868 (3)
Ti1—F6	1.882 (3)
Ti2—F8	1.803 (3)
Ti2—F7	1.821 (3)
Ti2—F9	1.825 (3)
Ti2—F10	1.827 (3)
Ti2—F11	1.832 (3)
Ti2—F12	1.856 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯F13	0.89	1.90	2.773 (5)	165
N2—H2D⋯F6ⁱ	0.89	2.04	2.865 (5)	154
N2—H2E⋯F13ⁱ	0.89	1.84	2.725 (5)	172
N3—H3C⋯F13	0.89	1.86	2.700 (5)	157
N3—H3C⋯N1	0.89	2.52	2.948 (6)	110
N3—H3D⋯F3	0.89	1.90	2.726 (5)	154
N3—H3E⋯F9	0.89	1.84	2.717 (5)	167
N4—H4C⋯F13	0.89	1.83	2.692 (5)	162
N4—H4D⋯F12ⁱ	0.89	2.01	2.835 (5)	153
N4—H4E⋯F5	0.89	1.84	2.712 (5)	168
N6—H6C⋯F14	0.89	1.84	2.696 (5)	162
N6—H6D⋯F10ⁱⁱ	0.89	2.00	2.823 (5)	154
N6—H6E⋯F4ⁱⁱⁱ	0.89	1.90	2.749 (5)	160
N7—H7C⋯F14	0.89	1.82	2.699 (5)	169
N7—H7D⋯F2ⁱⁱⁱ	0.89	2.24	2.876 (5)	129
N7—H7E⋯F7ⁱ	0.89	2.08	2.916 (5)	157
N7—H7E⋯F10ⁱ	0.89	2.41	2.972 (5)	121
N8—H8C⋯F14	0.89	1.91	2.791 (5)	168
N8—H8D⋯F6	0.89	2.14	2.879 (5)	140
N8—H8E⋯F14^iv	0.89	1.81	2.702 (5)	177

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

To date, only a few organic-inorganic fluorotitanates were reported. The first compound {(CN₃H₆)[TiF₆]}, described by Calov et al. (1992), is built up from (TiF₆) monomers and guanidinium cations. Dadachov et al. (2000) and Tang et al. (2001) reported the synthesis of piperazinium {(C₄N₂H₁₂)₂[Ti₂F₁₀]2(H₂O)} and piperidinium {[C₅H₆N₂]2(Ti₂F₁₁)(H₃O)(H₂0)} fluorotitanates respectively, built up from (Ti₂F₁₀)^2- or (Ti₂F₁₁)^3- dimers. As a part of our ongoing investigations in this field (Adil et al., 2006)) we now report the synthesis and structure of the title compound, (I).

The asymmetric unit of (I) consits of two crystallographically independent (TiF₆)^2- anions, two fluoride anions and two triprotonated tris(2-aminoethyl)amine (tren) cations, all of them located in general positions (Fig. 1). The TiF₆ anions form sligthly distorted octahedra and the environnement of both independent anions is different (Table 1). Both TiF₆ anions are connected to the cations via N—H···F hydrogen bonding (Figure 2 and Table 2).

The two isolated fluoride anions are also hydrogen bonded to the [H₃tren]³⁺ cations with N—H···F distances ranging from 2.692 (5)Å to 2.791 (5)Å (Figure 2 and Table 2).

Experimental

The synthetis was performed by using a microwave-assisted route. Crystals were prepared from a mixture of titanium(IV) oxide (79 mg, 1 mmol), tris(2-aminoethyl)amine (0.230 ml, 1.52 mmol), hydrogen fluoride (40%, 0.130 ml, 2.95 mmol) and ethanol (10 ml, 35 mmol). The mixture was transferred into a teflon autoclave installed in a CEM microwave oven at 493 K for 1 hour under a constant pressure of 22 bar. Finally, the solid product was washed with ethanol and dried in air at room temperature to yield colourless paralellepipeds of (I).