catena-Poly[[cadmium-bis­(μ-triethyl­ene­tetra­mine-κ4N,N′:N′′,N′′′)-cadmium-(μ-triethyl­ene­tetra­mine-κ4N,N′:N′′,N′′′)] hexa­fluoridogermanate]

Wang, G.-M.; Wang, P.

doi:10.1107/S1600536811033381

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1278-m1279

doi:10.1107/S1600536811033381

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catena-Poly[[cadmium-bis(μ-triethylenetetramine-κ⁴N,N′:N′′,N′′′)-cadmium-(μ-triethylenetetramine-κ⁴N,N′:N′′,N′′′)] hexafluoridogermanate]

Guo-Ming Wang ^a ^* and Pei Wang ^b

^aTeachers College, College of Chemistry, Chemical Engineering and Environment of Qingdao University, Shandong 266071, People's Republic of China, and ^bCollege of Chemistry, Chemical Engineering and Environment of Qingdao University, Shandong 266071, People's Republic of China
^*Correspondence e-mail: gmwang_pub@163.com

(Received 5 August 2011; accepted 17 August 2011; online 27 August 2011)

The title fluoridogermanate, {[Cd₂(C₆H₁₈N₄)₃][GeF₆]}_n, was synthesized hydrothermally. The crystal structure comprises undulated cationic [Cd₂(TETA)₃]⁴⁺ chains (TETA is triethylenetetramine) propagating parallel to [101]. The central Cd^II atom is six-coordinated in a CdN₆ set by three TETA ligands. The isolated [GeF₆]²⁻ units, serving as counter-anions, occupy the inter-chain spaces and simultaneously link adjacent chains into a three-dimensional network through extensive N—H⋯F hydrogen-bonding interactions. One of the ethylene bridges of one TETA ligand is disordered around a twofold rotation axis.

Related literature

For background to the structures and applications of microporous materials, see: Cheetham et al. (1999 ); Liang et al. (2006 ); Su et al. (2009 ); Zheng et al. (2003 ); Zou et al. (2005 ). For previously reported structures containing fluoridogermanate anions, see: Hoard & Vincent (1939 ); Brauer et al. (1980 , 1986 ); Lukevics et al. (1997 ); Zhang et al. (2003 ); Wang et al. (2004 ). For polyamine Cd^II coordination complexes, see: Bartoszak-Adamska et al. (2002 ); Ma et al. (2005 ); Bose et al. (2006 ).

Experimental

Crystal data

[Cd₂(C₆H₁₈N₄)₃][GeF₆]
M_r = 1036.71
Monoclinic, C 2/c
a = 16.5034 (3) Å
b = 9.1072 (3) Å
c = 22.1920 (4) Å
β = 100.354 (5)°
V = 3281.14 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.20 mm⁻¹
T = 295 K
0.10 × 0.06 × 0.05 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.741, T_max = 0.857
11087 measured reflections
3385 independent reflections
2642 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.076
S = 1.00
3385 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N5	2.313 (3)
Cd1—N4	2.363 (3)
Cd1—N1ⁱ	2.372 (3)
Cd1—N3	2.406 (3)
Cd1—N6	2.443 (4)
Cd1—N2ⁱ	2.444 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯F4ⁱⁱ	0.90	2.18	3.083 (4)	176
N2—H2C⋯F6ⁱⁱⁱ	0.91	2.25	3.076 (4)	150
N3—H3C⋯F1ⁱ	0.91	2.17	3.026 (4)	155
N4—H4C⋯F2^iv	0.90	2.26	3.130 (4)	162
N5—H5C⋯F1	0.90	2.11	2.998 (4)	170
N5—H5D⋯F5^v	0.90	2.14	3.013 (4)	165
N6—H6⋯F6^vi	0.93	2.23	3.134 (5)	164
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[x, -y+2, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (vi) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033381/wm2519sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033381/wm2519Isup2.hkl

checkCIF report

Comment top

Much interest has been focused on the rational design and construction of microporous materials with intriguing topological architectures and promising applications (Cheetham et al., 1999; Zheng et al., 2003; Zou et al., 2005; Liang et al., 2006; Su et al., 2009). Compared to the rapid development of silicate and phosphate open-framework structures, the progress in the field of fluorides remains moderate. With the exception of some fluoridosilicates, fluoridoaluminates and fluoridotitanates, only a few fluoridogermanates (Brauer et al., 1980, 1986; Lukevics et al., 1997; Wang et al., 2004; Zhang et al., 2003) have been reported. In this structure family, the central Ge(IV) ions are octahedrally coordinated by fluorine atoms. In addition, various organic amines or metal-complex cations have frequently been employed in the synthesis of such fluorides. The main purpose of our work is to explore the construction of novel microporous germanates with Cd^II complexes as counter anions. Unexpectedly, the title compound, (I), was obtained, which represents a new fluoridogermanate with one-dimensional Cd^II complex cations.

As shown in Fig. 1, the asymmetric unit of (I) contains one unique germanium(IV) atom, one cadmium(II) atom, six fluoride anions, as well as one and a half TETA molecules (TETE = triethylenetetramine, C₆H₁₈N₄), the latter being completed by a twofold rotation axis. The cadmium atom is six-coordinated in a distorted octahedral geometry by six amine N atoms from three TETA ligands. The Cd—N bond lengths span the range 2.313 (3)–2.444 (3) Å, which are comparable with those observed in other related compounds, e.g. (Bartoszak-Adamska et al., 2002; Ma et al., 2005; Bose et al., 2006). The Ge—F bond lengths in the fluoridogermanate anion are in the range 1.754 (3)–1.788 (2) Å (average 1.772 Å), similar to the distances observed in the inorganic complex K₂GeF₆ (Ge—F 1.77 Å) (Hoard & Vincent, 1939), or in other fluoridogermanates, such as [(CH₃)₄N][(CF₃)₃GeF₂] (Brauer et al., 1986), [Ni(C₂H₈N₂)(C₆H₁₈N₄)][GeF₆] (Wang et al., 2004) and [Ni(dien)₂][GeF₆] (Zhang et al., 2003).

The crystal structure of (I) features an undulated cationic chain [Cd₂(TETA)₃]⁴⁺, with discrete [GeF₆]^2- groups serving as the counter anions and occupying the inter-chain spaces. As shown in Fig. 2, two neighboring cadmium atoms are linked by two bridging TETA ligands to form a dimeric Cd₂ fragment, with Cd···Cd contacts of 6.311 (2) Å. Such dimeric Cd₂ motifs, which can be considered as secondary building units (SBUs), are interconnected by the third TETA linker to generate one-dimensional corrugated chains parallel the [101] directions (Fig. 3). Adjacent uniform chains are further interlinked and packed together through the [GeF₆]^2- groups into a three-dimensional supramolecular framework (Fig. 4). There are extensive N—H···F hydrogen-bonding interactions between the [GeF₆]^2- ions and amine groups within each of the chains (Table 2).

Related literature top

For background to the structures and applications of microporous materials, see: Cheetham et al. (1999); Liang et al. (2006); Su et al. (2009); Zheng et al. (2003); Zou et al. (2005). For previously reported structures containing fluoridogermanate anions, see: Hoard & Vincent (1939); Brauer et al. (1980, 1986); Lukevics et al. (1997); Zhang et al. (2003); Wang et al. (2004). For polyamine Cd^II coordination complexes, see: Bartoszak-Adamska et al. (2002); Ma et al. (2005); Bose et al. (2006).

Experimental top

The title compound was synthesized under hydrothermal conditions. Typically, a mixture of GeO₂ (0.104 g,1 mmol) CdCO₃ (0.174 g, 1 mmol), TETA (3.00 ml), pyridine (2.50 ml), hydrofluoric acid (40%, 0.20 ml), and H₂O (1.00 ml), in a molar ratio 1:1:20:31:10:56, was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 7 days. The block-shaped crystals obtained were recovered by filtration, washed with distilled water and dried in air.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1/2 - x, 1.5 - y, 1 - z;, (ii) 1 - x, y, 1.5 - z.]
	Fig. 2. Dimeric Cd₂ fragment found in (I); H atoms omitted for clarity.
	Fig. 3. One-dimensional infinite cationic [Cd₂(TETA)₃]_n chains in (I).
	Fig. 4. The crystal packing of (I), projected along the b axis.

catena-Poly[[cadmium-bis(µ-triethylenetetramine- κ⁴N,N':N'',N''')-cadmium- (µ-triethylenetetramine-κ⁴N,N':N'',N''')] hexafluoridogermanate] top

Crystal data top

[Cd₂(C₆H₁₈N₄)₃][GeF₆]	F(000) = 2056
M_r = 1036.71	D_x = 2.099 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3385 reflections
a = 16.5034 (3) Å	θ = 1.9–26.5°
b = 9.1072 (3) Å	µ = 3.20 mm⁻¹
c = 22.1920 (4) Å	T = 295 K
β = 100.354 (5)°	Block, colorless
V = 3281.14 (14) Å³	0.10 × 0.06 × 0.05 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	3385 independent reflections
Radiation source: fine-focus sealed tube	2642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 26.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
T_min = 0.741, T_max = 0.857	k = −11→11
11087 measured reflections	l = −27→27

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0321P)²] where P = (F_o² + 2F_c²)/3
3385 reflections	(Δ/σ)_max = 0.001
218 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Cd₂(C₆H₁₈N₄)₃][GeF₆]	V = 3281.14 (14) Å³
M_r = 1036.71	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.5034 (3) Å	µ = 3.20 mm⁻¹
b = 9.1072 (3) Å	T = 295 K
c = 22.1920 (4) Å	0.10 × 0.06 × 0.05 mm
β = 100.354 (5)°

Data collection top

Bruker APEX area-detector diffractometer	3385 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2642 reflections with I > 2σ(I)
T_min = 0.741, T_max = 0.857	R_int = 0.045
11087 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.00	Δρ_max = 0.69 e Å⁻³
3385 reflections	Δρ_min = −0.55 e Å⁻³
218 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	0.33579 (3)	1.10395 (5)	0.374972 (19)	0.02492 (12)
Cd1	0.329148 (17)	0.90058 (3)	0.624812 (13)	0.02438 (10)
F1	0.28347 (16)	0.9992 (3)	0.42434 (12)	0.0490 (7)
F2	0.33638 (19)	0.9446 (3)	0.32858 (12)	0.0551 (8)
F3	0.24171 (19)	1.1545 (4)	0.32908 (16)	0.0789 (10)
F4	0.38899 (19)	1.2061 (3)	0.32551 (13)	0.0611 (8)
F5	0.33215 (19)	1.2603 (3)	0.42160 (13)	0.0561 (8)
F6	0.43124 (16)	1.0523 (3)	0.41810 (14)	0.0574 (8)
C1	0.0710 (3)	0.8812 (5)	0.32142 (18)	0.0321 (10)
H1A	0.0226	0.8239	0.3048	0.039*
H1B	0.0662	0.9762	0.3013	0.039*
C2	0.0756 (3)	0.9018 (4)	0.38958 (19)	0.0329 (10)
H2A	0.1242	0.9586	0.4062	0.039*
H2B	0.0276	0.9557	0.3969	0.039*
C3	0.0854 (2)	0.7744 (4)	0.48790 (18)	0.0286 (10)
H3A	0.0860	0.6776	0.5062	0.034*
H3B	0.0373	0.8263	0.4964	0.034*
C4	0.1630 (2)	0.8575 (4)	0.51675 (17)	0.0264 (9)
H4A	0.2072	0.8312	0.4953	0.032*
H4B	0.1530	0.9620	0.5110	0.032*
C5	0.1347 (2)	0.8992 (5)	0.61866 (19)	0.0319 (10)
H5A	0.0843	0.8424	0.6147	0.038*
H5B	0.1205	0.9964	0.6023	0.038*
C6	0.1729 (3)	0.9119 (5)	0.68592 (19)	0.0344 (10)
H6A	0.1342	0.9585	0.7080	0.041*
H6B	0.1851	0.8147	0.7030	0.041*
C7	0.3999 (3)	1.1777 (5)	0.5701 (2)	0.0465 (13)
H7A	0.3915	1.2742	0.5514	0.056*
H7B	0.4429	1.1286	0.5532	0.056*
C8	0.4258 (3)	1.1934 (6)	0.6381 (3)	0.0561 (16)
H8A	0.4726	1.2593	0.6467	0.067*
H8B	0.3811	1.2364	0.6551	0.067*
C9	0.4699 (5)	1.0170 (11)	0.7371 (4)	0.030 (2)	0.50
H9A	0.4210	1.0291	0.7552	0.036*	0.50
H9B	0.4871	0.9153	0.7423	0.036*	0.50
C9'	0.4641 (6)	1.1120 (10)	0.7305 (4)	0.036 (2)	0.50
H9'1	0.4820	1.2135	0.7309	0.043*	0.50
H9'2	0.4152	1.1060	0.7490	0.043*	0.50
N1	0.1450 (2)	0.8060 (4)	0.30945 (15)	0.0321 (8)
H1C	0.1884	0.8675	0.3163	0.038*
H1D	0.1376	0.7768	0.2701	0.038*
N2	0.0791 (2)	0.7592 (3)	0.42059 (14)	0.0262 (8)
H2C	0.0282	0.7201	0.4078	0.031*
N3	0.19025 (18)	0.8288 (3)	0.58250 (14)	0.0228 (7)
H3C	0.1867	0.7302	0.5881	0.027*
N4	0.2490 (2)	0.9988 (4)	0.69334 (15)	0.0309 (8)
H4C	0.2765	0.9927	0.7321	0.037*
H4D	0.2373	1.0938	0.6846	0.037*
N5	0.3231 (2)	1.0924 (4)	0.55588 (16)	0.0339 (9)
H5C	0.3168	1.0571	0.5175	0.041*
H5D	0.2798	1.1505	0.5585	0.041*
N6	0.4478 (2)	1.0527 (5)	0.66701 (16)	0.0434 (11)
H6	0.4918	1.0265	0.6480	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0254 (2)	0.0250 (2)	0.0255 (2)	0.00042 (19)	0.00756 (19)	0.00145 (19)
Cd1	0.02349 (17)	0.02780 (17)	0.02159 (16)	−0.00060 (14)	0.00335 (12)	0.00203 (13)
F1	0.0584 (18)	0.0460 (16)	0.0511 (17)	−0.0165 (14)	0.0329 (15)	0.0000 (13)
F2	0.089 (2)	0.0400 (16)	0.0407 (17)	−0.0092 (15)	0.0232 (16)	−0.0141 (13)
F3	0.051 (2)	0.096 (3)	0.078 (2)	0.0250 (18)	−0.0195 (17)	0.013 (2)
F4	0.088 (2)	0.0541 (18)	0.0510 (18)	−0.0172 (17)	0.0385 (17)	0.0112 (15)
F5	0.086 (2)	0.0315 (15)	0.0573 (19)	−0.0009 (15)	0.0303 (17)	−0.0134 (13)
F6	0.0343 (16)	0.067 (2)	0.066 (2)	0.0066 (14)	−0.0047 (14)	0.0115 (16)
C1	0.031 (2)	0.037 (3)	0.025 (2)	0.006 (2)	−0.0024 (19)	0.0038 (19)
C2	0.035 (2)	0.033 (2)	0.030 (2)	0.012 (2)	0.004 (2)	0.004 (2)
C3	0.023 (2)	0.034 (2)	0.030 (2)	−0.0027 (19)	0.0072 (19)	−0.0004 (19)
C4	0.024 (2)	0.032 (2)	0.024 (2)	0.0006 (18)	0.0051 (18)	0.0019 (17)
C5	0.023 (2)	0.041 (2)	0.032 (2)	−0.005 (2)	0.0067 (18)	−0.005 (2)
C6	0.038 (3)	0.043 (3)	0.026 (2)	−0.005 (2)	0.014 (2)	−0.006 (2)
C7	0.047 (3)	0.035 (3)	0.061 (4)	−0.005 (2)	0.020 (3)	0.009 (2)
C8	0.041 (3)	0.048 (3)	0.086 (4)	−0.026 (3)	0.029 (3)	−0.036 (3)
C9	0.029 (5)	0.037 (5)	0.024 (5)	−0.012 (4)	0.007 (4)	0.003 (4)
C9'	0.038 (5)	0.037 (5)	0.030 (5)	0.000 (5)	0.001 (4)	0.000 (5)
N1	0.038 (2)	0.0334 (19)	0.0252 (19)	−0.0037 (18)	0.0061 (16)	0.0030 (16)
N2	0.0225 (18)	0.0313 (19)	0.0237 (18)	−0.0041 (15)	0.0014 (15)	−0.0010 (15)
N3	0.0265 (18)	0.0226 (17)	0.0191 (17)	−0.0001 (15)	0.0031 (14)	−0.0004 (14)
N4	0.037 (2)	0.033 (2)	0.0221 (19)	−0.0009 (17)	0.0039 (16)	−0.0029 (15)
N5	0.033 (2)	0.035 (2)	0.035 (2)	0.0049 (18)	0.0080 (17)	0.0095 (17)
N6	0.029 (2)	0.079 (3)	0.023 (2)	−0.017 (2)	0.0078 (17)	−0.015 (2)

Geometric parameters (Å, º) top

Ge1—F6	1.754 (3)	C6—N4	1.468 (5)
Ge1—F3	1.758 (3)	C6—H6A	0.9700
Ge1—F5	1.768 (2)	C6—H6B	0.9700
Ge1—F2	1.780 (2)	C7—N5	1.471 (5)
Ge1—F4	1.786 (2)	C7—C8	1.500 (7)
Ge1—F1	1.788 (2)	C7—H7A	0.9700
Cd1—N5	2.313 (3)	C7—H7B	0.9700
Cd1—N4	2.363 (3)	C8—N6	1.451 (7)
Cd1—N1ⁱ	2.372 (3)	C8—H8A	0.9700
Cd1—N3	2.406 (3)	C8—H8B	0.9700
Cd1—N6	2.443 (4)	C9—C9'ⁱⁱ	1.474 (10)
Cd1—N2ⁱ	2.444 (3)	C9—N6	1.566 (9)
C1—N1	1.465 (5)	C9—H9A	0.9700
C1—C2	1.513 (6)	C9—H9B	0.9700
C1—H1A	0.9700	C9'—C9ⁱⁱ	1.474 (10)
C1—H1B	0.9700	C9'—N6	1.487 (9)
C2—N2	1.466 (5)	C9'—H9'1	0.9700
C2—H2A	0.9700	C9'—H9'2	0.9700
C2—H2B	0.9700	N1—Cd1ⁱ	2.372 (3)
C3—N2	1.485 (5)	N1—H1C	0.9000
C3—C4	1.526 (5)	N1—H1D	0.9000
C3—H3A	0.9700	N2—Cd1ⁱ	2.444 (3)
C3—H3B	0.9700	N2—H2C	0.9100
C4—N3	1.471 (5)	N3—H3C	0.9100
C4—H4A	0.9700	N4—H4C	0.9000
C4—H4B	0.9700	N4—H4D	0.9000
C5—N3	1.469 (5)	N5—H5C	0.9000
C5—C6	1.517 (6)	N5—H5D	0.9000
C5—H5A	0.9700	N6—H6	0.9335
C5—H5B	0.9700

F6—Ge1—F3	177.73 (16)	H6A—C6—H6B	108.1
F6—Ge1—F5	91.05 (14)	N5—C7—C8	110.1 (4)
F3—Ge1—F5	90.50 (16)	N5—C7—H7A	109.6
F6—Ge1—F2	89.96 (14)	C8—C7—H7A	109.6
F3—Ge1—F2	88.53 (15)	N5—C7—H7B	109.6
F5—Ge1—F2	178.16 (13)	C8—C7—H7B	109.6
F6—Ge1—F4	89.01 (14)	H7A—C7—H7B	108.1
F3—Ge1—F4	89.32 (16)	N6—C8—C7	111.4 (4)
F5—Ge1—F4	90.70 (13)	N6—C8—H8A	109.3
F2—Ge1—F4	90.85 (13)	C7—C8—H8A	109.3
F6—Ge1—F1	90.45 (13)	N6—C8—H8B	109.3
F3—Ge1—F1	91.21 (15)	C7—C8—H8B	109.3
F5—Ge1—F1	90.02 (12)	H8A—C8—H8B	108.0
F2—Ge1—F1	88.44 (12)	C9'ⁱⁱ—C9—N6	112.5 (6)
F4—Ge1—F1	179.11 (14)	C9'ⁱⁱ—C9—H9A	109.1
N5—Cd1—N4	100.20 (12)	N6—C9—H9A	109.1
N5—Cd1—N1ⁱ	171.01 (12)	C9'ⁱⁱ—C9—H9B	109.1
N4—Cd1—N1ⁱ	87.93 (12)	N6—C9—H9B	109.1
N5—Cd1—N3	91.29 (12)	H9A—C9—H9B	107.8
N4—Cd1—N3	75.51 (11)	C9ⁱⁱ—C9'—N6	104.0 (6)
N1ⁱ—Cd1—N3	94.47 (11)	C9ⁱⁱ—C9'—H9'1	111.0
N5—Cd1—N6	76.19 (13)	N6—C9'—H9'1	111.0
N4—Cd1—N6	92.37 (12)	C9ⁱⁱ—C9'—H9'2	111.0
N1ⁱ—Cd1—N6	99.84 (13)	N6—C9'—H9'2	111.0
N3—Cd1—N6	160.93 (13)	H9'1—C9'—H9'2	109.0
N5—Cd1—N2ⁱ	97.66 (11)	C1—N1—Cd1ⁱ	108.8 (2)
N4—Cd1—N2ⁱ	161.89 (11)	C1—N1—H1C	109.9
N1ⁱ—Cd1—N2ⁱ	74.05 (11)	Cd1ⁱ—N1—H1C	109.9
N3—Cd1—N2ⁱ	107.14 (10)	C1—N1—H1D	109.9
N6—Cd1—N2ⁱ	88.99 (12)	Cd1ⁱ—N1—H1D	109.9
N1—C1—C2	110.2 (3)	H1C—N1—H1D	108.3
N1—C1—H1A	109.6	C2—N2—C3	112.3 (3)
C2—C1—H1A	109.6	C2—N2—Cd1ⁱ	108.0 (2)
N1—C1—H1B	109.6	C3—N2—Cd1ⁱ	122.3 (2)
C2—C1—H1B	109.6	C2—N2—H2C	104.1
H1A—C1—H1B	108.1	C3—N2—H2C	104.1
N2—C2—C1	110.5 (3)	Cd1ⁱ—N2—H2C	104.1
N2—C2—H2A	109.5	C5—N3—C4	110.8 (3)
C1—C2—H2A	109.5	C5—N3—Cd1	108.2 (2)
N2—C2—H2B	109.5	C4—N3—Cd1	116.0 (2)
C1—C2—H2B	109.5	C5—N3—H3C	107.1
H2A—C2—H2B	108.1	C4—N3—H3C	107.1
N2—C3—C4	111.7 (3)	Cd1—N3—H3C	107.1
N2—C3—H3A	109.3	C6—N4—Cd1	106.8 (2)
C4—C3—H3A	109.3	C6—N4—H4C	110.4
N2—C3—H3B	109.3	Cd1—N4—H4C	110.4
C4—C3—H3B	109.3	C6—N4—H4D	110.4
H3A—C3—H3B	107.9	Cd1—N4—H4D	110.4
N3—C4—C3	114.3 (3)	H4C—N4—H4D	108.6
N3—C4—H4A	108.7	C7—N5—Cd1	109.0 (3)
C3—C4—H4A	108.7	C7—N5—H5C	109.9
N3—C4—H4B	108.7	Cd1—N5—H5C	109.9
C3—C4—H4B	108.7	C7—N5—H5D	109.9
H4A—C4—H4B	107.6	Cd1—N5—H5D	109.9
N3—C5—C6	112.4 (3)	H5C—N5—H5D	108.3
N3—C5—H5A	109.1	C8—N6—C9'	95.0 (5)
C6—C5—H5A	109.1	C8—N6—C9	128.2 (5)
N3—C5—H5B	109.1	C8—N6—Cd1	102.2 (3)
C6—C5—H5B	109.1	C9'—N6—Cd1	124.4 (4)
H5A—C5—H5B	107.9	C9—N6—Cd1	106.9 (4)
N4—C6—C5	110.3 (3)	C8—N6—H6	100.3
N4—C6—H6A	109.6	C9'—N6—H6	119.8
C5—C6—H6A	109.6	C9—N6—H6	109.5
N4—C6—H6B	109.6	Cd1—N6—H6	108.5
C5—C6—H6B	109.6

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···F4ⁱⁱⁱ	0.90	2.18	3.083 (4)	176
N2—H2C···F6^iv	0.91	2.25	3.076 (4)	150
N3—H3C···F1ⁱ	0.91	2.17	3.026 (4)	155
N4—H4C···F2^v	0.90	2.26	3.130 (4)	162
N5—H5C···F1	0.90	2.11	2.998 (4)	170
N5—H5D···F5^vi	0.90	2.14	3.013 (4)	165
N6—H6···F6^vii	0.93	2.23	3.134 (5)	164

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x−1/2, y−1/2, z; (v) x, −y+2, z+1/2; (vi) −x+1/2, −y+5/2, −z+1; (vii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cd₂(C₆H₁₈N₄)₃][GeF₆]
M_r	1036.71
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	16.5034 (3), 9.1072 (3), 22.1920 (4)
β (°)	100.354 (5)
V (Å³)	3281.14 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.20
Crystal size (mm)	0.10 × 0.06 × 0.05

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.741, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	11087, 3385, 2642
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.076, 1.00
No. of reflections	3385
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.55

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—N5	2.313 (3)	Cd1—N3	2.406 (3)
Cd1—N4	2.363 (3)	Cd1—N6	2.443 (4)
Cd1—N1ⁱ	2.372 (3)	Cd1—N2ⁱ	2.444 (3)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···F4ⁱⁱ	0.90	2.18	3.083 (4)	176.4
N2—H2C···F6ⁱⁱⁱ	0.91	2.25	3.076 (4)	150.0
N3—H3C···F1ⁱ	0.91	2.17	3.026 (4)	155.4
N4—H4C···F2^iv	0.90	2.26	3.130 (4)	161.5
N5—H5C···F1	0.90	2.11	2.998 (4)	169.7
N5—H5D···F5^v	0.90	2.14	3.013 (4)	164.7
N6—H6···F6^vi	0.93	2.23	3.134 (5)	164.3

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, y−1/2, z; (iv) x, −y+2, z+1/2; (v) −x+1/2, −y+5/2, −z+1; (vi) −x+1, −y+2, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20901043), the Young Scientist Foundation of Shandong Province (No. BS2009CL041) and the Qingdao University Research Fund (No. 063–06300522).

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