Bis(1-adamantylammonium) hexafluoridogermanate

Cheng, L.; Xu, X.; Xu, Y.

doi:10.1107/S1600536807063702

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m82

https://doi.org/10.1107/S1600536807063702

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Bis(1-adamantylammonium) hexafluoridogermanate

Liying Cheng,^a Xin Xu ^b and Yan Xu ^a ^*

^aInstitute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China, and ^bHeavy Oil Company, Liaohe Petroleum Filiale, China National Petroleum Corporation (CNPC), Shiyou Street No. 96, Panjin 124010, People's Republic of China
^*Correspondence e-mail: yanxu@lnnu.edu.cn

(Received 26 October 2007; accepted 27 November 2007; online 6 December 2007)

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 ); Plévert et al. (2001 ); Xu, Fan, Chino et al. (2004 ); Xu, Fan, Elangovan et al. (2004 ); Xu et al. (2006 ).

Experimental

Crystal data

(C₁₀H₁₈N)₂[GeF₆]
M_r = 491.10
Monoclinic, C 2/m
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 ) 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[F² > 2σ(F²)] = 0.057
wR(F²) = 0.144
S = 1.07
1037 reflections
86 parameters
H-atom parameters constrained
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯F2ⁱ	0.90	1.80	2.639 (5)	155
N1—H1C⋯F1ⁱⁱ	0.90	2.04	2.920 (4)	166
Symmetry codes: (i) x, -y-1, z; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063702/bi2261Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

Bis(amantadinium) hexafluoridogermanate top

Crystal data top

(C₁₀H₁₈N)₂[GeF₆]	F(000) = 512
M_r = 491.10	D_x = 1.551 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 955 reflections
a = 11.099 (2) Å	θ = 3.5–25.1°
b = 6.7458 (13) Å	µ = 1.52 mm⁻¹
c = 14.179 (3) Å	T = 293 K
β = 97.844 (3)°	Plate, colorless
V = 1051.7 (4) Å³	0.20 × 0.18 × 0.10 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1037 independent reflections
Radiation source: fine-focus sealed tube	955 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 25.2°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→13
T_min = 0.751, T_max = 0.863	k = −8→8
2694 measured reflections	l = −17→13

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0862P)² + 0.4272P] where P = (F_o² + 2F_c²)/3
1037 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 1.00 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

(C₁₀H₁₈N)₂[GeF₆]	V = 1051.7 (4) Å³
M_r = 491.10	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 11.099 (2) Å	µ = 1.52 mm⁻¹
b = 6.7458 (13) Å	T = 293 K
c = 14.179 (3) Å	0.20 × 0.18 × 0.10 mm
β = 97.844 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1037 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	955 reflections with I > 2σ(I)
T_min = 0.751, T_max = 0.863	R_int = 0.054
2694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.07	Δρ_max = 1.00 e Å⁻³
1037 reflections	Δρ_min = −0.69 e Å⁻³
86 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)
Ge1	−0.5000	0.0000	0.0000	0.0276 (3)
F1	−0.5435 (3)	0.0000	0.1155 (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)	−0.5000	0.2032 (4)	0.0276 (12)
C1	−0.4579 (5)	−0.5000	0.2134 (4)	0.0400 (15)
H1A	−0.4963	−0.6155	0.1832	0.048*
C2	−0.4722 (6)	−0.5000	0.3188 (4)	0.0383 (14)
H2A	−0.5568	−0.5000	0.3265	0.046*
C3	−0.2621 (4)	−0.3158 (6)	0.2489 (3)	0.0382 (10)
H3A	−0.2989	−0.1991	0.2188	0.046*
H3B	−0.1775	−0.3161	0.2414	0.046*
C4	−0.2760 (4)	−0.3161 (7)	0.3550 (3)	0.0465 (12)
H4A	−0.2383	−0.1998	0.3847	0.056*
N1	−0.3085 (5)	−0.5000	0.1002 (3)	0.0495 (15)
H1B	−0.3439	−0.6089	0.0722	0.074*
H1C	−0.2288	−0.5000	0.0942	0.074*
C6	−0.2157 (6)	−0.5000	0.4014 (5)	0.0523 (19)
H6A	−0.2230	−0.5000	0.4681	0.063*
H6B	−0.1307	−0.5000	0.3948	0.063*
C7	−0.4110 (4)	−0.3163 (7)	0.3658 (4)	0.0478 (12)
H7A	−0.4209	−0.3142	0.4320	0.057*
H7B	−0.4490	−0.1998	0.3362	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0296 (5)	0.0262 (5)	0.0286 (5)	0.000	0.0103 (3)	0.000
F1	0.048 (2)	0.079 (3)	0.031 (2)	0.000	0.0180 (16)	0.000
F2	0.072 (6)	0.032 (3)	0.052 (3)	0.013 (2)	0.000 (5)	−0.001 (3)
F3	0.033 (3)	0.057 (5)	0.058 (3)	−0.008 (2)	0.008 (2)	−0.016 (2)
C5	0.029 (3)	0.035 (3)	0.019 (3)	0.000	0.007 (2)	0.000
C1	0.029 (3)	0.061 (4)	0.031 (3)	0.000	0.005 (2)	0.000
C2	0.033 (3)	0.046 (4)	0.039 (3)	0.000	0.016 (3)	0.000
C3	0.039 (2)	0.030 (2)	0.048 (3)	−0.0047 (19)	0.017 (2)	0.0013 (19)
C4	0.047 (3)	0.049 (3)	0.047 (3)	−0.017 (2)	0.019 (2)	−0.021 (2)
N1	0.033 (3)	0.088 (5)	0.030 (3)	0.000	0.013 (2)	0.000
C6	0.034 (4)	0.093 (6)	0.030 (3)	0.000	0.006 (3)	0.000
C7	0.051 (3)	0.047 (3)	0.050 (3)	0.004 (2)	0.023 (2)	−0.011 (2)

Geometric parameters (Å, º) top

Ge1—F1	1.769 (3)	C2—C7	1.522 (6)
Ge1—F1ⁱ	1.769 (3)	C2—C7^iv	1.522 (6)
Ge1—F3	1.772 (4)	C2—H2A	0.960
Ge1—F3ⁱ	1.772 (4)	C3—C4	1.532 (6)
Ge1—F3ⁱⁱ	1.772 (4)	C3—H3A	0.960
Ge1—F3ⁱⁱⁱ	1.772 (4)	C3—H3B	0.960
Ge1—F2ⁱⁱ	1.778 (4)	C4—C6	1.517 (6)
Ge1—F2ⁱⁱⁱ	1.778 (4)	C4—C7	1.527 (7)
Ge1—F2ⁱ	1.778 (4)	C4—H4A	0.960
Ge1—F2	1.778 (4)	N1—H1B	0.900
C5—N1	1.491 (6)	N1—H1C	0.900
C5—C3	1.518 (5)	C6—C4^iv	1.517 (6)
C5—C3^iv	1.518 (5)	C6—H6A	0.960
C5—C1	1.521 (8)	C6—H6B	0.960
C1—C2	1.524 (8)	C7—H7A	0.960
C1—H1A	0.960	C7—H7B	0.960

F1—Ge1—F1ⁱ	180.0 (2)	C5—C1—H1A	109.8
F1—Ge1—F3	89.6 (2)	C2—C1—H1A	109.8
F1ⁱ—Ge1—F3	90.4 (2)	C7—C2—C7^iv	109.1 (6)
F1—Ge1—F3ⁱ	90.4 (2)	C7—C2—C1	109.2 (3)
F1ⁱ—Ge1—F3ⁱ	89.6 (2)	C7^iv—C2—C1	109.2 (3)
F3—Ge1—F3ⁱ	180.0 (3)	C7—C2—H2A	109.6
F1—Ge1—F3ⁱⁱ	89.6 (2)	C7^iv—C2—H2A	109.6
F1ⁱ—Ge1—F3ⁱⁱ	90.4 (2)	C1—C2—H2A	110.1
F1—Ge1—F3ⁱⁱⁱ	90.4 (2)	C5—C3—C4	108.6 (4)
F1ⁱ—Ge1—F3ⁱⁱⁱ	89.6 (2)	C5—C3—H3A	110.1
F3ⁱⁱ—Ge1—F3ⁱⁱⁱ	180.0 (4)	C4—C3—H3A	110.1
F1—Ge1—F2ⁱⁱ	95.1 (3)	C5—C3—H3B	109.8
F1ⁱ—Ge1—F2ⁱⁱ	84.9 (3)	C4—C3—H3B	109.9
F3ⁱⁱ—Ge1—F2ⁱⁱ	90.3 (2)	H3A—C3—H3B	108.4
F3ⁱⁱⁱ—Ge1—F2ⁱⁱ	89.7 (2)	C6—C4—C7	109.7 (4)
F1—Ge1—F2ⁱⁱⁱ	84.9 (3)	C6—C4—C3	109.2 (4)
F1ⁱ—Ge1—F2ⁱⁱⁱ	95.1 (3)	C7—C4—C3	109.3 (4)
F3ⁱⁱ—Ge1—F2ⁱⁱⁱ	89.7 (2)	C6—C4—H4A	109.7
F3ⁱⁱⁱ—Ge1—F2ⁱⁱⁱ	90.3 (2)	C7—C4—H4A	109.4
F2ⁱⁱ—Ge1—F2ⁱⁱⁱ	180.0	C3—C4—H4A	109.5
F1—Ge1—F2ⁱ	84.9 (3)	C5—N1—H1B	109.4
F1ⁱ—Ge1—F2ⁱ	95.1 (3)	C5—N1—H1C	109.5
F3—Ge1—F2ⁱ	89.7 (2)	H1B—N1—H1C	109.5
F3ⁱ—Ge1—F2ⁱ	90.3 (2)	C4^iv—C6—C4	109.7 (5)
F1—Ge1—F2	95.1 (3)	C4^iv—C6—H6A	109.6
F1ⁱ—Ge1—F2	84.9 (3)	C4—C6—H6A	109.6
F3—Ge1—F2	90.3 (2)	C4^iv—C6—H6B	109.8
F3ⁱ—Ge1—F2	89.7 (2)	C4—C6—H6B	109.8
F2ⁱ—Ge1—F2	180.0 (3)	H6A—C6—H6B	108.2
N1—C5—C3	108.4 (3)	C2—C7—C4	110.0 (4)
N1—C5—C3^iv	108.4 (3)	C2—C7—H7A	109.6
C3—C5—C3^iv	109.9 (5)	C4—C7—H7A	110.0
N1—C5—C1	109.6 (4)	C2—C7—H7B	109.4
C3—C5—C1	110.3 (3)	C4—C7—H7B	109.5
C3^iv—C5—C1	110.3 (3)	H7A—C7—H7B	108.2
C5—C1—C2	109.2 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···F2^iv	0.90	1.80	2.639 (5)	155
N1—H1C···F1^v	0.90	2.04	2.920 (4)	166

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

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₈N)₂[GeF₆]
M_r	491.10
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	293
a, b, c (Å)	11.099 (2), 6.7458 (13), 14.179 (3)
β (°)	97.844 (3)
V (Å³)	1051.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.751, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	2694, 1037, 955
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.144, 1.07
No. of reflections	1037
No. of parameters	86
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.69

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···F2ⁱ	0.90	1.80	2.639 (5)	154.8
N1—H1C···F1ⁱⁱ	0.90	2.04	2.920 (4)	166.2

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

Acknowledgements

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

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