catena-Poly[[cadmium-bis-(μ-triethyl-ene-tetra-mine-κN,N':N'',N''')-cadmium-(μ-triethyl-ene-tetra-mine-κN,N':N'',N''')] hexa-fluoridogermanate].

The title fluoridogermanate, {[Cd(2)(C(6)H(18)N(4))(3)][GeF(6)]}(n), was synthesized hydro-thermally. The crystal structure comprises undulated cationic [Cd(2)(TETA)(3)](4+) chains (TETA is triethyl-ene-tetra-mine) propagating parallel to [101]. The central Cd(II) atom is six-coordinated in a CdN(6) set by three TETA ligands. The isolated [GeF(6)](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 inter-actions. One of the ethyl-ene 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 CdII coordination complexes, see: Bartoszak-Adamska et al. (2002 ▶); Ma et al. (2005 ▶); Bose et al. (2006 ▶).

Experimental

Crystal data

[Cd2(C6H18N4)3][GeF6]

M = 1036.71

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.076

S = 1.00

3385 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.69 e Å−3

Δρmin = −0.55 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811033381/wm2519sup1.cif

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

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

[Cd2(C6H18N4)3][GeF6]	F(000) = 2056
Mr = 1036.71	Dx = 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

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

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(Fo2) + (0.0321P)2] where P = (Fo2 + 2Fc2)/3
3385 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.69 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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

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···F6iv	0.91	2.25	3.076 (4)	150.
N3—H3C···F1i	0.91	2.17	3.026 (4)	155.
N4—H4C···F2v	0.90	2.26	3.130 (4)	162.
N5—H5C···F1	0.90	2.11	2.998 (4)	170.
N5—H5D···F5vi	0.90	2.14	3.013 (4)	165.
N6—H6···F6vii	0.93	2.23	3.134 (5)	164.

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) .

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⋯F2iv	0.90	2.26	3.130 (4)	162
N5—H5C⋯F1	0.90	2.11	2.998 (4)	170
N5—H5D⋯F5v	0.90	2.14	3.013 (4)	165
N6—H6⋯F6vi	0.93	2.23	3.134 (5)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .