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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m82.
Published online 2007 December 6. doi:  10.1107/S1600536807063702
PMCID: PMC2914959

Bis(1-adamantylammonium) hexafluoridogermanate

Abstract

The title compound, (C10H18N)2[GeF6], was obtained hydro­thermally from an aqueous solution of GeO2, H3BO3, NiCl2, adamantylammonium chloride, butanol and hydro­fluoric acid. The structure consists of discrete bis(1-adamantylammonium) cations lying on crystallographic mirror planes and hexa­fluoridogermanate anions disordered about sites of 2/m point symmetry. In the latter, the Ge atom lies on the site of 2/m symmetry, one F atom lies on the mirror plane and two further F atoms are included in general positions with 50% site occupancy. The cations and anions lie in layers with N—H(...)F hydrogen bonds formed between them.

Related literature

For related literature concerning germanium framework materials, see: Li et al. (1998 [triangle]); Plévert et al. (2001 [triangle]); Xu, Fan, Chino et al. (2004 [triangle]); Xu, Fan, Elangovan et al. (2004 [triangle]); Xu et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m82-scheme1.jpg

Experimental

Crystal data

  • (C10H18N)2[GeF6]
  • M r = 491.10
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m82-efi1.jpg
  • a = 11.099 (2) Å
  • b = 6.7458 (13) Å
  • c = 14.179 (3) Å
  • β = 97.844 (3)°
  • V = 1051.7 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.52 mm−1
  • T = 293 (2) K
  • 0.20 × 0.18 × 0.10 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.751, T max = 0.863
  • 2694 measured reflections
  • 1037 independent reflections
  • 955 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.144
  • S = 1.07
  • 1037 reflections
  • 86 parameters
  • H-atom parameters constrained
  • Δρmax = 1.00 e Å−3
  • Δρmin = −0.69 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063702/bi2261sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063702/bi2261Isup2.hkl

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

Acknowledgments

This work was supported by the Natural Science Foundation of Liaoning Province (20062139).

supplementary crystallographic information

Comment

Over the past decades, germanium has been used to synthesize inorganic framework materials (Li et al., 1998; Plévert et al., 2001; Xu, Fan, Chino et al., 2004; Xu, Fan, Elangovan et al., 2004; Xu et al., 2006). In this work, we used a typical method to synthesize germanate frameworks under hydrothermal conditions, but obtained instead a simple salt of adamantamine and germanium fluoride.

Experimental

Colorless plate-like crystals were synthesized hydrothermally from a mixture of GeO2, H3BO3, NiCl2, (C10H18N)Cl, C4H9OH, HF and H2O. In a typical synthesis, GeO2 (0.100 g), H3BO3 (0.006 g), NiCl2 (0.23 g), and (C10H18N)Cl (0.300 g) were dissolved in a mixture of C4H9OH (2.170 g), 47% HF (0.10 ml) and 1 ml water with constant stirring. The mixture was kept in a 25 ml Teflon-lined steel autoclave at 443 K for 7 days. The autoclave was slowly cooled to room temperature, then the product was filtered, washed with distilled water, and dried at room temperature.

Refinement

The GeF62- anion is disordered about a site of 2/m point symmetry. Atoms F2 and F3 are included with site occupancy factor 0.5. H atoms were placed geometrically and allowed to ride during subsequent refinement with C—H = 0.96 Å, Uiso(H) = 1.2Ueq(C), and with N—H = 0.90 Å, Uiso(H) = 1.5Ueq(N),

Figures

Fig. 1.
The molecular structure of title compound showing displacement ellipsoids at the 70% probability level for non-H atoms (the occupancy factors for F1 and F2 are 1/2).
Fig. 2.
Unit-cell contents.

Crystal data

(C10H18N)2[GeF6]F000 = 512
Mr = 491.10Dx = 1.551 Mg m3
Monoclinic, C2/mMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 955 reflections
a = 11.099 (2) Åθ = 3.5–25.1º
b = 6.7458 (13) ŵ = 1.52 mm1
c = 14.179 (3) ÅT = 293 (2) K
β = 97.844 (3)ºPlate, colorless
V = 1051.7 (4) Å30.20 × 0.18 × 0.10 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer1037 independent reflections
Radiation source: fine-focus sealed tube955 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
T = 293(2) Kθmax = 25.2º
ω scansθmin = 3.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)h = −10→13
Tmin = 0.751, Tmax = 0.863k = −8→8
2694 measured reflectionsl = −17→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.144  w = 1/[σ2(Fo2) + (0.0862P)2 + 0.4272P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1037 reflectionsΔρmax = 1.00 e Å3
86 parametersΔρmin = −0.69 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/UeqOcc. (<1)
Ge1−0.50000.00000.00000.0276 (3)
F1−0.5435 (3)0.00000.1155 (2)0.0516 (10)
F2−0.4626 (5)−0.2563 (7)0.0005 (6)0.0527 (19)0.50
F3−0.3490 (4)0.0578 (7)0.0500 (4)0.0490 (17)0.50
C5−0.3233 (5)−0.50000.2032 (4)0.0276 (12)
C1−0.4579 (5)−0.50000.2134 (4)0.0400 (15)
H1A−0.4963−0.61550.18320.048*
C2−0.4722 (6)−0.50000.3188 (4)0.0383 (14)
H2A−0.5568−0.50000.32650.046*
C3−0.2621 (4)−0.3158 (6)0.2489 (3)0.0382 (10)
H3A−0.2989−0.19910.21880.046*
H3B−0.1775−0.31610.24140.046*
C4−0.2760 (4)−0.3161 (7)0.3550 (3)0.0465 (12)
H4A−0.2383−0.19980.38470.056*
N1−0.3085 (5)−0.50000.1002 (3)0.0495 (15)
H1B−0.3439−0.60890.07220.074*
H1C−0.2288−0.50000.09420.074*
C6−0.2157 (6)−0.50000.4014 (5)0.0523 (19)
H6A−0.2230−0.50000.46810.063*
H6B−0.1307−0.50000.39480.063*
C7−0.4110 (4)−0.3163 (7)0.3658 (4)0.0478 (12)
H7A−0.4209−0.31420.43200.057*
H7B−0.4490−0.19980.33620.057*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ge10.0296 (5)0.0262 (5)0.0286 (5)0.0000.0103 (3)0.000
F10.048 (2)0.079 (3)0.031 (2)0.0000.0180 (16)0.000
F20.072 (6)0.032 (3)0.052 (3)0.013 (2)0.000 (5)−0.001 (3)
F30.033 (3)0.057 (5)0.058 (3)−0.008 (2)0.008 (2)−0.016 (2)
C50.029 (3)0.035 (3)0.019 (3)0.0000.007 (2)0.000
C10.029 (3)0.061 (4)0.031 (3)0.0000.005 (2)0.000
C20.033 (3)0.046 (4)0.039 (3)0.0000.016 (3)0.000
C30.039 (2)0.030 (2)0.048 (3)−0.0047 (19)0.017 (2)0.0013 (19)
C40.047 (3)0.049 (3)0.047 (3)−0.017 (2)0.019 (2)−0.021 (2)
N10.033 (3)0.088 (5)0.030 (3)0.0000.013 (2)0.000
C60.034 (4)0.093 (6)0.030 (3)0.0000.006 (3)0.000
C70.051 (3)0.047 (3)0.050 (3)0.004 (2)0.023 (2)−0.011 (2)

Geometric parameters (Å, °)

Ge1—F11.769 (3)C2—C71.522 (6)
Ge1—F1i1.769 (3)C2—C7iv1.522 (6)
Ge1—F31.772 (4)C2—H2A0.960
Ge1—F3i1.772 (4)C3—C41.532 (6)
Ge1—F3ii1.772 (4)C3—H3A0.960
Ge1—F3iii1.772 (4)C3—H3B0.960
Ge1—F2ii1.778 (4)C4—C61.517 (6)
Ge1—F2iii1.778 (4)C4—C71.527 (7)
Ge1—F2i1.778 (4)C4—H4A0.960
Ge1—F21.778 (4)N1—H1B0.900
C5—N11.491 (6)N1—H1C0.900
C5—C31.518 (5)C6—C4iv1.517 (6)
C5—C3iv1.518 (5)C6—H6A0.960
C5—C11.521 (8)C6—H6B0.960
C1—C21.524 (8)C7—H7A0.960
C1—H1A0.960C7—H7B0.960
F1—Ge1—F1i180.0 (2)C5—C1—H1A109.8
F1—Ge1—F389.6 (2)C2—C1—H1A109.8
F1i—Ge1—F390.4 (2)C7—C2—C7iv109.1 (6)
F1—Ge1—F3i90.4 (2)C7—C2—C1109.2 (3)
F1i—Ge1—F3i89.6 (2)C7iv—C2—C1109.2 (3)
F3—Ge1—F3i180.0 (3)C7—C2—H2A109.6
F1—Ge1—F3ii89.6 (2)C7iv—C2—H2A109.6
F1i—Ge1—F3ii90.4 (2)C1—C2—H2A110.1
F1—Ge1—F3iii90.4 (2)C5—C3—C4108.6 (4)
F1i—Ge1—F3iii89.6 (2)C5—C3—H3A110.1
F3ii—Ge1—F3iii180.0 (4)C4—C3—H3A110.1
F1—Ge1—F2ii95.1 (3)C5—C3—H3B109.8
F1i—Ge1—F2ii84.9 (3)C4—C3—H3B109.9
F3ii—Ge1—F2ii90.3 (2)H3A—C3—H3B108.4
F3iii—Ge1—F2ii89.7 (2)C6—C4—C7109.7 (4)
F1—Ge1—F2iii84.9 (3)C6—C4—C3109.2 (4)
F1i—Ge1—F2iii95.1 (3)C7—C4—C3109.3 (4)
F3ii—Ge1—F2iii89.7 (2)C6—C4—H4A109.7
F3iii—Ge1—F2iii90.3 (2)C7—C4—H4A109.4
F2ii—Ge1—F2iii180.0C3—C4—H4A109.5
F1—Ge1—F2i84.9 (3)C5—N1—H1B109.4
F1i—Ge1—F2i95.1 (3)C5—N1—H1C109.5
F3—Ge1—F2i89.7 (2)H1B—N1—H1C109.5
F3i—Ge1—F2i90.3 (2)C4iv—C6—C4109.7 (5)
F1—Ge1—F295.1 (3)C4iv—C6—H6A109.6
F1i—Ge1—F284.9 (3)C4—C6—H6A109.6
F3—Ge1—F290.3 (2)C4iv—C6—H6B109.8
F3i—Ge1—F289.7 (2)C4—C6—H6B109.8
F2i—Ge1—F2180.0 (3)H6A—C6—H6B108.2
N1—C5—C3108.4 (3)C2—C7—C4110.0 (4)
N1—C5—C3iv108.4 (3)C2—C7—H7A109.6
C3—C5—C3iv109.9 (5)C4—C7—H7A110.0
N1—C5—C1109.6 (4)C2—C7—H7B109.4
C3—C5—C1110.3 (3)C4—C7—H7B109.5
C3iv—C5—C1110.3 (3)H7A—C7—H7B108.2
C5—C1—C2109.2 (5)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···F2iv0.901.802.639 (5)155
N1—H1C···F1v0.902.042.920 (4)166

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2261).

References

  • Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconson, USA.
  • Li, H., Eddaoudi, M., Richardson, D. A. & Yaghi, O. M. (1998). J. Am. Chem. Soc.120, 8567–8568.
  • Plévert, J., Gentz, T. M., Laine, A., Li, H., Young, V. G., Yaghi, O. M. & O’Keeffe, M. (2001). J. Am. Chem. Soc.123, 12706–12707. [PubMed]
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
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  • Xu, Y., Cheng, L. & You, W. (2006). Inorg. Chem.45, 7705–7708. [PubMed]
  • Xu, Y., Fan, W., Chino, N., Uehara, K., Hikichi, S., Mizuno, N., Ogura, M. & Okubo, T. (2004). Chem. Lett.33, 74–75.
  • Xu, Y., Fan, W., Elangovan, S. P., Ogura, M. & Okubo, T. (2004). Eur. J. Inorg. Chem. pp. 4547–4549.

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