Alternating C6H14N22+ and [BeF4]2- units within the ac plane of 1,4-diazoniabicyclo[2.2.2]octane tetrafluoroberyllium hemihydrate, (C6H14N2)[BeF4]·0.5H2O, combine to form double chains via hydrogen bonding. These double chains connect through bifurcated hydrogen bonds to water molecules, which lie on twofold axes, producing a two-dimensional sheet. Very weak hydrogen-bond interactions, along the b axis, join the sheets to produce a three-dimensional network.
Supporting information
CCDC reference: 192952
Beryllium(II) fluoride (0.1 g, 0.002 mol) was dissolved in an acidic aqueous
solution of distilled water (2 ml) and 30% hydrofluoric acid (0.085 ml, 0.002 mol). 1,4-Diazabicyclo[2.2.2]octane (dabco) (0.224 g, 0.002 mol) was added to
give an overall molar ratio of 1:1:1. The solution was placed in a 23 ml
Teflon-lined autoclave and heated at 423 K for 24 h. The resulting solution
was placed in a plastic sample vial and left to evaporate slowly. The title
compound crystallized as a colourless crystalline solid. Finally, the product
was recovered by filtration and air-dried.
Two of the three dabconium ethylene groups show slight disorder. Each group has
one C atom with an elongated displacement parameter perpendicular to the C—C
and C—N bonds. A static disorder model was investigated as an alternative to
the dynamic disorder model but the latter was preferred due to the instability
of the former model during refinement. H atoms were initially located in
difference maps and their positions idealized. Thereafter they were refined
riding on their parent atoms, with C—H distances of 0.99 Å and
Uiso(H) values of 1.2Ueq(C) for Csp3 atoms. The H
atoms of the N—H and O—H groups were located and freely refined.
Data collection: COLLECT (Hooft, 1998); cell refinement: SCALEPACK (Otwinoski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: COLLECT, DENZO and maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1999); software used to prepare material for publication: WinGX (Farrugia, 1998).
Crystal data top
(C6H14N2)[BeF4]·0.5H2O | Dx = 1.537 Mg m−3 |
Mr = 208.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 14284 reflections |
a = 19.523 (4) Å | θ = 2.9–27.5° |
b = 9.2726 (19) Å | µ = 0.15 mm−1 |
c = 9.939 (2) Å | T = 293 K |
V = 1799.3 (6) Å3 | Block, colourless |
Z = 8 | 0.12 × 0.10 × 0.10 mm |
F(000) = 872 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1814 reflections with I > 2σ(I) |
Radiation source: Nonius FR591 rotating anode | Rint = 0.051 |
Graphite monochromator | θmax = 27.5°, θmin = 3.2° |
Detector resolution: 9.091 pixels mm1 pixels mm-1 | h = −24→25 |
ϕ and ω scans to fill the Ewald sphere | k = −12→11 |
14284 measured reflections | l = −12→12 |
2041 independent reflections | |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.051P)2 + 1.245P] where P = (Fo2 + 2Fc2)/3 |
2040 reflections | (Δ/σ)max = 0.001 |
135 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
(C6H14N2)[BeF4]·0.5H2O | V = 1799.3 (6) Å3 |
Mr = 208.21 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 19.523 (4) Å | µ = 0.15 mm−1 |
b = 9.2726 (19) Å | T = 293 K |
c = 9.939 (2) Å | 0.12 × 0.10 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1814 reflections with I > 2σ(I) |
14284 measured reflections | Rint = 0.051 |
2041 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.39 e Å−3 |
2040 reflections | Δρmin = −0.40 e Å−3 |
135 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 | Uiso*/Ueq | |
Be1 | 0.12801 (9) | 0.2660 (2) | 0.97524 (19) | 0.0226 (4) | |
F1 | 0.16538 (5) | 0.16332 (9) | 0.87368 (10) | 0.0277 (2) | |
F2 | 0.07625 (5) | 0.36227 (10) | 0.89402 (10) | 0.0315 (3) | |
F3 | 0.09067 (5) | 0.17170 (10) | 1.07715 (10) | 0.0293 (2) | |
F4 | 0.17983 (5) | 0.37152 (9) | 1.03947 (9) | 0.0274 (2) | |
N1 | 0.36198 (6) | 0.39678 (13) | 0.93155 (13) | 0.0224 (3) | |
H1 | 0.3573 (10) | 0.493 (3) | 0.922 (2) | 0.040 (5)* | |
N2 | 0.37643 (8) | 0.13232 (15) | 0.95264 (16) | 0.0341 (4) | |
H2 | 0.3807 (13) | 0.037 (3) | 0.957 (3) | 0.063 (8)* | |
C1 | 0.31404 (8) | 0.32307 (16) | 0.83630 (15) | 0.0243 (3) | |
H1A | 0.3241 | 0.3530 | 0.7427 | 0.029* | |
H1B | 0.2662 | 0.3501 | 0.8573 | 0.029* | |
C2 | 0.32331 (8) | 0.16037 (16) | 0.85081 (17) | 0.0280 (3) | |
H2A | 0.2796 | 0.1154 | 0.8787 | 0.034* | |
H2B | 0.3372 | 0.1181 | 0.7635 | 0.034* | |
C3 | 0.34629 (9) | 0.35374 (19) | 1.07268 (16) | 0.0301 (4) | |
H3A | 0.2987 | 0.3809 | 1.0958 | 0.036* | |
H3B | 0.3777 | 0.4035 | 1.1357 | 0.036* | |
C4 | 0.35522 (19) | 0.1922 (2) | 1.0840 (2) | 0.0738 (10) | |
H4A | 0.3904 | 0.1700 | 1.1527 | 0.089* | |
H4B | 0.3115 | 0.1475 | 1.1126 | 0.089* | |
C5 | 0.43452 (8) | 0.35848 (18) | 0.89909 (18) | 0.0291 (4) | |
H5A | 0.4660 | 0.4065 | 0.9630 | 0.035* | |
H5B | 0.4461 | 0.3910 | 0.8070 | 0.035* | |
C6 | 0.44201 (10) | 0.1979 (2) | 0.9093 (3) | 0.0688 (9) | |
H6A | 0.4555 | 0.1581 | 0.8208 | 0.083* | |
H6B | 0.4784 | 0.1740 | 0.9750 | 0.083* | |
O1 | 0.0000 | 0.16025 (18) | 0.7500 | 0.0318 (4) | |
H7 | 0.0216 (13) | 0.218 (2) | 0.796 (3) | 0.053 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Be1 | 0.0232 (9) | 0.0193 (8) | 0.0254 (9) | −0.0002 (7) | 0.0010 (7) | 0.0002 (7) |
F1 | 0.0308 (5) | 0.0212 (4) | 0.0311 (5) | −0.0013 (4) | 0.0059 (4) | −0.0019 (4) |
F2 | 0.0317 (5) | 0.0235 (5) | 0.0391 (6) | 0.0022 (4) | −0.0093 (4) | 0.0015 (4) |
F3 | 0.0280 (5) | 0.0293 (5) | 0.0306 (5) | −0.0041 (4) | 0.0032 (4) | 0.0032 (4) |
F4 | 0.0286 (5) | 0.0241 (5) | 0.0295 (5) | −0.0035 (3) | −0.0024 (4) | −0.0017 (4) |
N1 | 0.0219 (6) | 0.0186 (6) | 0.0266 (6) | 0.0004 (5) | −0.0007 (5) | −0.0003 (5) |
N2 | 0.0431 (9) | 0.0180 (6) | 0.0411 (8) | −0.0017 (6) | −0.0199 (7) | 0.0009 (6) |
C1 | 0.0231 (7) | 0.0238 (7) | 0.0260 (7) | 0.0009 (5) | −0.0030 (6) | 0.0006 (6) |
C2 | 0.0289 (8) | 0.0237 (7) | 0.0313 (8) | −0.0006 (6) | −0.0088 (6) | −0.0020 (6) |
C3 | 0.0317 (8) | 0.0359 (8) | 0.0227 (7) | −0.0010 (7) | 0.0019 (6) | −0.0028 (6) |
C4 | 0.165 (3) | 0.0324 (10) | 0.0237 (9) | −0.0399 (15) | −0.0110 (13) | 0.0032 (8) |
C5 | 0.0192 (7) | 0.0322 (8) | 0.0360 (9) | −0.0012 (6) | 0.0019 (6) | 0.0018 (6) |
C6 | 0.0215 (9) | 0.0307 (10) | 0.154 (3) | 0.0044 (7) | −0.0109 (12) | −0.0290 (13) |
O1 | 0.0302 (8) | 0.0282 (8) | 0.0369 (9) | 0.000 | −0.0060 (7) | 0.000 |
Geometric parameters (Å, º) top
Be1—F1 | 1.567 (2) | C1—H1B | 0.9900 |
Be1—F2 | 1.572 (2) | C2—H2A | 0.9900 |
Be1—F3 | 1.524 (2) | C2—H2B | 0.9900 |
Be1—F4 | 1.546 (2) | C3—C4 | 1.512 (3) |
N1—C3 | 1.490 (2) | C3—H3A | 0.9900 |
N1—C5 | 1.4953 (19) | C3—H3B | 0.9900 |
N1—C1 | 1.4964 (19) | C4—H4A | 0.9900 |
N1—H1 | 0.90 (2) | C4—H4B | 0.9900 |
N2—C2 | 1.472 (2) | C5—C6 | 1.500 (3) |
N2—C4 | 1.478 (3) | C5—H5A | 0.9900 |
N2—C6 | 1.481 (3) | C5—H5B | 0.9900 |
N2—H2 | 0.89 (3) | C6—H6A | 0.9900 |
C1—C2 | 1.526 (2) | C6—H6B | 0.9900 |
C1—H1A | 0.9900 | O1—H7 | 0.82 (2) |
| | | |
F1—Be1—F2 | 108.27 (13) | N2—C2—H2B | 109.9 |
F1—Be1—F3 | 107.60 (12) | C1—C2—H2B | 109.9 |
F1—Be1—F4 | 110.24 (12) | H2A—C2—H2B | 108.3 |
F2—Be1—F3 | 111.08 (12) | N1—C3—C4 | 108.16 (14) |
F2—Be1—F4 | 105.86 (12) | N1—C3—H3A | 110.1 |
F3—Be1—F4 | 113.69 (13) | C4—C3—H3A | 110.1 |
C3—N1—C5 | 109.52 (12) | N1—C3—H3B | 110.1 |
C3—N1—C1 | 110.16 (12) | C4—C3—H3B | 110.1 |
C5—N1—C1 | 110.33 (12) | H3A—C3—H3B | 108.4 |
C3—N1—H1 | 110.4 (14) | N2—C4—C3 | 109.80 (15) |
C5—N1—H1 | 107.9 (13) | N2—C4—H4A | 109.7 |
C1—N1—H1 | 108.5 (14) | C3—C4—H4A | 109.7 |
C2—N2—C4 | 110.09 (18) | N2—C4—H4B | 109.7 |
C2—N2—C6 | 109.65 (17) | C3—C4—H4B | 109.7 |
C4—N2—C6 | 110.18 (18) | H4A—C4—H4B | 108.2 |
C2—N2—H2 | 106.0 (17) | N1—C5—C6 | 108.28 (14) |
C4—N2—H2 | 110.8 (18) | N1—C5—H5A | 110.0 |
C6—N2—H2 | 110.0 (17) | C6—C5—H5A | 110.0 |
N1—C1—C2 | 108.51 (12) | N1—C5—H5B | 110.0 |
N1—C1—H1A | 110.0 | C6—C5—H5B | 110.0 |
C2—C1—H1A | 110.0 | H5A—C5—H5B | 108.4 |
N1—C1—H1B | 110.0 | N2—C6—C5 | 110.05 (15) |
C2—C1—H1B | 110.0 | N2—C6—H6A | 109.7 |
H1A—C1—H1B | 108.4 | C5—C6—H6A | 109.7 |
N2—C2—C1 | 108.85 (12) | N2—C6—H6B | 109.7 |
N2—C2—H2A | 109.9 | C5—C6—H6B | 109.7 |
C1—C2—H2A | 109.9 | H6A—C6—H6B | 108.2 |
| | | |
C3—N1—C1—C2 | −60.47 (16) | C6—N2—C4—C3 | 59.7 (3) |
C5—N1—C1—C2 | 60.56 (16) | N1—C3—C4—N2 | 0.1 (3) |
C4—N2—C2—C1 | 60.91 (18) | C3—N1—C5—C6 | 62.4 (2) |
C6—N2—C2—C1 | −60.47 (18) | C1—N1—C5—C6 | −59.0 (2) |
N1—C1—C2—N2 | −0.38 (18) | C2—N2—C6—C5 | 62.7 (2) |
C5—N1—C3—C4 | −61.1 (2) | C4—N2—C6—C5 | −58.6 (3) |
C1—N1—C3—C4 | 60.4 (2) | N1—C5—C6—N2 | −2.1 (3) |
C2—N2—C4—C3 | −61.3 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1i | 0.90 (2) | 1.71 (2) | 2.5932 (16) | 166 (2) |
N1—H1···F3i | 0.90 (2) | 2.48 (2) | 3.0737 (17) | 123 (2) |
N2—H2···F2ii | 0.89 (3) | 1.93 (3) | 2.7320 (18) | 149 (2) |
N2—H2···F4ii | 0.89 (3) | 2.10 (3) | 2.7927 (18) | 134 (2) |
O1—H7···F2 | 0.82 (2) | 1.97 (2) | 2.7881 (15) | 176 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | (C6H14N2)[BeF4]·0.5H2O |
Mr | 208.21 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 19.523 (4), 9.2726 (19), 9.939 (2) |
V (Å3) | 1799.3 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.12 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14284, 2041, 1814 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.117, 1.07 |
No. of reflections | 2040 |
No. of parameters | 135 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.40 |
Selected geometric parameters (Å, º) topBe1—F1 | 1.567 (2) | Be1—F3 | 1.524 (2) |
Be1—F2 | 1.572 (2) | Be1—F4 | 1.546 (2) |
| | | |
F1—Be1—F2 | 108.27 (13) | F2—Be1—F3 | 111.08 (12) |
F1—Be1—F3 | 107.60 (12) | F2—Be1—F4 | 105.86 (12) |
F1—Be1—F4 | 110.24 (12) | F3—Be1—F4 | 113.69 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1i | 0.90 (2) | 1.71 (2) | 2.5932 (16) | 166 (2) |
N1—H1···F3i | 0.90 (2) | 2.48 (2) | 3.0737 (17) | 123 (2) |
N2—H2···F2ii | 0.89 (3) | 1.93 (3) | 2.7320 (18) | 149 (2) |
N2—H2···F4ii | 0.89 (3) | 2.10 (3) | 2.7927 (18) | 134 (2) |
O1—H7···F2 | 0.82 (2) | 1.97 (2) | 2.7881 (15) | 176 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z. |
The title compound, (I), has been prepared as a precursor in the formation of beryllium-containing framework materials. The cocrystallization of the templating agent as a beryllium salt aids in the formation of these frameworks.
The beryllium coordination geometry is fairly regular tetrahedral, with the four Be—F bond distances ranging from 1.524 (2) to 1.572 (2) Å, and the F—Be—F angles ranging from 105.8 (1) to 113.7 (1)°. These values are in good agreement with other [BeF4]2- geometries in the literature (Le Fur et al., 1991; Srivastava et al., 1999; Tedenac et al., 1971). In the doubly protonated 1,4-diazabicyclo[2.2.2]octane (dabco), the C—N distances of 1.485 (3) Å and C—C distances of 1.509 (3) Å are typical of the average values found for this group (Fig. 1 and Table 1).
Each [BeF4l2- unit is linked to two dabconium moieties and one water molecule through bifurcated N—H···F and O—H···F interactions, which have D···A distances of 2.5932 (16)–3.0737 (17) Å (Table 2) [weaker interactions, namely C—H···F contacts characterized by C···F distances of 3.091 (2)–3.339 (2) Å, have not been tabulated]. Thus, one-dimensional hydrogen-bonded chains consisting of C6H14N22+ and [BeF4]2- units run parallel to the b axis. These chains are linked in the ab plane by weak hydrogen-bonding interactions involving water molecules, linking pairs of parallel chains (Fig. 2) into hydrogen-bonded double-chain units. These units lie parallel to one another, intersecting the normal to the ac plane. Water molecules lie in between the hydrogen-bonded double-chain units, where each parallel set is rotated through 90° to give an alternating pattern.
Other possible hydrogen bonds have been found using PLATON (Spek, 1990, 1998), which indicates very weak C—H···F interactions between the C—H groups on the dabconium and the F atoms of the [BeF4]2- dianion. For each water link there are two C—H···F crosslinks between the parallel double chains (Fig. 3). Overall, these hydrogen bonds result in the formation of a three-dimensional network.