Bis{2,2'-[(2-amino-eth-yl)aza-nedi-yl]diethanaminium} di-μ-sulfido-bis-(disulfido-germanate).

In the title compound, (C(6)H(20)N(4))(2)[Ge(2)S(6)], the dimeric [Ge(2)S(6)](4-) anion is formed by two edge-sharing GeS(4) tetra-hedral units. The average terminal and bridging Ge-S bond lengths are 2.158 (14) and 2.276 (6) Å, respectively. The anions and the diprotonated ammonium cations are organized into a three-dimensional network by N-H⋯S and N-H⋯N hydrogen bonds.

Related literature

For background to main group metal–chalcogenide compounds, see: Bowes & Ozin (1996 ▶); Zheng et al. (2002 ▶, 2005 ▶). For a related structure, see: Jia et al. (2005 ▶).

Experimental

Crystal data

(C6H20N4)2[Ge2S6]

M = 634.06

Monoclinic,

a = 25.2845 (17) Å

b = 7.3173 (4) Å

c = 16.6001 (9) Å

β = 122.637 (4)°

V = 2586.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.83 mm−1

T = 296 K

0.19 × 0.16 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.616, T max = 0.677

11988 measured reflections

2952 independent reflections

2243 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.111

S = 1.03

2952 reflections

159 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.05 e Å−3

Δρmin = −1.08 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200092X/hy2497sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200092X/hy2497Isup2.hkl

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

(C6H20N4)2[Ge2S6]	F(000) = 1312
Mr = 634.06	Dx = 1.628 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3750 reflections
a = 25.2845 (17) Å	θ = 2.9–26.8°
b = 7.3173 (4) Å	µ = 2.83 mm−1
c = 16.6001 (9) Å	T = 296 K
β = 122.637 (4)°	Block, colorless
V = 2586.3 (3) Å3	0.19 × 0.16 × 0.15 mm
Z = 4

Bruker APEXII CCD diffractometer	2952 independent reflections
Radiation source: fine-focus sealed tube	2243 reflections with I > 2σ(I)
graphite	Rint = 0.051
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −28→32
Tmin = 0.616, Tmax = 0.677	k = −9→9
11988 measured reflections	l = −21→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0694P)2] where P = (Fo2 + 2Fc2)/3
2952 reflections	(Δ/σ)max = 0.001
159 parameters	Δρmax = 1.05 e Å−3
0 restraints	Δρmin = −1.07 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ge1	0.046082 (16)	0.40953 (4)	0.47830 (2)	0.02516 (14)
S1	−0.02392 (4)	0.64364 (11)	0.40812 (6)	0.0284 (2)
S2	0.14075 (4)	0.50236 (13)	0.53795 (7)	0.0368 (2)
S3	0.01711 (4)	0.17923 (11)	0.38125 (6)	0.0322 (2)
N1	0.16919 (14)	0.0976 (3)	0.2936 (2)	0.0291 (7)
N2	0.10013 (18)	0.4325 (5)	0.3045 (3)	0.0375 (8)
H1N	0.074 (2)	0.358 (6)	0.263 (3)	0.042 (12)*
H2N	0.096 (3)	0.399 (9)	0.342 (6)	0.11 (3)*
H3N	0.0834 (19)	0.559 (6)	0.295 (3)	0.043 (11)*
N3	0.08225 (18)	−0.1798 (5)	0.3167 (3)	0.0411 (8)
H4N	0.061 (2)	−0.179 (7)	0.340 (4)	0.062 (17)*
H5N	0.066 (2)	−0.111 (6)	0.277 (3)	0.040 (14)*
N4	0.09320 (16)	0.0946 (5)	0.0738 (2)	0.0344 (7)
H6N	0.070 (2)	0.112 (6)	0.100 (4)	0.054 (14)*
H7N	0.1009 (18)	0.199 (6)	0.058 (3)	0.038 (11)*
H8N	0.0691 (18)	0.031 (5)	0.019 (3)	0.034 (10)*
C1	0.19669 (17)	0.2513 (5)	0.3611 (3)	0.0353 (8)
H1A	0.2403	0.2653	0.3812	0.042*
H1B	0.1957	0.2233	0.4174	0.042*
C2	0.16258 (18)	0.4298 (5)	0.3188 (3)	0.0370 (9)
H2A	0.1874	0.5293	0.3610	0.044*
H2B	0.1584	0.4496	0.2578	0.044*
C3	0.18437 (18)	−0.0753 (5)	0.3472 (3)	0.0375 (9)
H3A	0.2283	−0.0737	0.3987	0.045*
H3B	0.1784	−0.1755	0.3048	0.045*
C4	0.14468 (19)	−0.1096 (5)	0.3891 (3)	0.0396 (9)
H4A	0.1659	−0.1972	0.4409	0.048*
H4B	0.1401	0.0035	0.4152	0.048*
C5	0.19364 (17)	0.0959 (5)	0.2311 (3)	0.0342 (8)
H5A	0.2350	0.0400	0.2652	0.041*
H5B	0.1983	0.2209	0.2165	0.041*
C6	0.15200 (18)	−0.0063 (5)	0.1386 (3)	0.0372 (8)
H6A	0.1745	−0.0252	0.1070	0.045*
H6B	0.1419	−0.1252	0.1526	0.045*

	U11	U22	U33	U12	U13	U23
Ge1	0.0285 (2)	0.0261 (2)	0.0180 (2)	0.00119 (14)	0.01058 (16)	0.00061 (12)
S1	0.0353 (5)	0.0292 (4)	0.0177 (4)	0.0043 (3)	0.0123 (4)	0.0038 (3)
S2	0.0288 (5)	0.0419 (6)	0.0347 (5)	−0.0023 (4)	0.0138 (4)	0.0004 (4)
S3	0.0412 (5)	0.0293 (5)	0.0231 (4)	0.0015 (4)	0.0153 (4)	−0.0034 (3)
N1	0.0328 (16)	0.0249 (14)	0.0219 (14)	0.0012 (12)	0.0097 (12)	0.0013 (11)
N2	0.045 (2)	0.036 (2)	0.0295 (18)	0.0025 (16)	0.0191 (17)	0.0009 (15)
N3	0.047 (2)	0.043 (2)	0.035 (2)	0.0016 (17)	0.0230 (18)	−0.0023 (16)
N4	0.0356 (18)	0.0358 (18)	0.0248 (16)	0.0000 (15)	0.0116 (15)	0.0001 (14)
C1	0.0354 (19)	0.0322 (19)	0.0274 (18)	−0.0033 (15)	0.0097 (15)	−0.0042 (14)
C2	0.041 (2)	0.0298 (19)	0.037 (2)	−0.0050 (16)	0.0187 (18)	−0.0034 (15)
C3	0.044 (2)	0.0283 (19)	0.039 (2)	0.0064 (16)	0.0216 (18)	0.0079 (15)
C4	0.050 (2)	0.036 (2)	0.029 (2)	−0.0008 (17)	0.0186 (18)	0.0017 (15)
C5	0.0314 (19)	0.038 (2)	0.0273 (18)	0.0032 (15)	0.0119 (16)	0.0041 (14)
C6	0.044 (2)	0.035 (2)	0.0268 (18)	0.0076 (16)	0.0151 (16)	−0.0008 (15)

Ge1—S2	2.1482 (10)	N4—H8N	0.90 (4)
Ge1—S3	2.1677 (9)	C1—C2	1.514 (5)
Ge1—S1i	2.2715 (9)	C1—H1A	0.9700
Ge1—S1	2.2804 (9)	C1—H1B	0.9700
N1—C5	1.466 (5)	C2—H2A	0.9700
N1—C1	1.471 (4)	C2—H2B	0.9700
N1—C3	1.473 (4)	C3—C4	1.519 (6)
N2—C2	1.465 (5)	C3—H3A	0.9700
N2—H1N	0.85 (4)	C3—H3B	0.9700
N2—H2N	0.73 (8)	C4—H4A	0.9700
N2—H3N	0.99 (4)	C4—H4B	0.9700
N3—C4	1.467 (5)	C5—C6	1.511 (5)
N3—H4N	0.81 (5)	C5—H5A	0.9700
N3—H5N	0.75 (5)	C5—H5B	0.9700
N4—C6	1.479 (5)	C6—H6A	0.9700
N4—H6N	0.90 (5)	C6—H6B	0.9700
N4—H7N	0.87 (4)
S2—Ge1—S3	115.74 (4)	N2—C2—C1	112.4 (3)
S2—Ge1—S1i	112.57 (4)	N2—C2—H2A	109.1
S3—Ge1—S1i	110.36 (4)	C1—C2—H2A	109.1
S2—Ge1—S1	111.28 (4)	N2—C2—H2B	109.1
S3—Ge1—S1	110.26 (3)	C1—C2—H2B	109.1
S1i—Ge1—S1	94.69 (3)	H2A—C2—H2B	107.9
Ge1i—S1—Ge1	85.31 (3)	N1—C3—C4	113.4 (3)
C5—N1—C1	109.8 (3)	N1—C3—H3A	108.9
C5—N1—C3	110.4 (3)	C4—C3—H3A	108.9
C1—N1—C3	109.5 (3)	N1—C3—H3B	108.9
C2—N2—H1N	116 (3)	C4—C3—H3B	108.9
C2—N2—H2N	120 (6)	H3A—C3—H3B	107.7
H1N—N2—H2N	94 (6)	N3—C4—C3	111.6 (3)
C2—N2—H3N	112 (2)	N3—C4—H4A	109.3
H1N—N2—H3N	113 (4)	C3—C4—H4A	109.3
H2N—N2—H3N	101 (5)	N3—C4—H4B	109.3
C4—N3—H4N	108 (4)	C3—C4—H4B	109.3
C4—N3—H5N	109 (3)	H4A—C4—H4B	108.0
H4N—N3—H5N	102 (5)	N1—C5—C6	113.3 (3)
C6—N4—H6N	112 (3)	N1—C5—H5A	108.9
C6—N4—H7N	111 (3)	C6—C5—H5A	108.9
H6N—N4—H7N	109 (4)	N1—C5—H5B	108.9
C6—N4—H8N	110 (2)	C6—C5—H5B	108.9
H6N—N4—H8N	107 (4)	H5A—C5—H5B	107.7
H7N—N4—H8N	107 (4)	N4—C6—C5	111.6 (3)
N1—C1—C2	112.9 (3)	N4—C6—H6A	109.3
N1—C1—H1A	109.0	C5—C6—H6A	109.3
C2—C1—H1A	109.0	N4—C6—H6B	109.3
N1—C1—H1B	109.0	C5—C6—H6B	109.3
C2—C1—H1B	109.0	H6A—C6—H6B	108.0
H1A—C1—H1B	107.8

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···S3ii	0.85 (4)	2.61 (5)	3.445 (4)	170 (4)
N2—H2N···S2	0.73 (8)	2.91 (8)	3.470 (4)	136 (6)
N2—H2N···S3	0.73 (8)	2.89 (8)	3.514 (4)	145 (7)
N2—H3N···N3iii	0.99 (4)	1.95 (4)	2.897 (5)	159 (4)
N4—H6N···S3ii	0.90 (5)	2.44 (5)	3.311 (4)	163 (4)
N4—H7N···S2iv	0.87 (4)	2.50 (4)	3.357 (4)	170 (3)
N4—H8N···S3v	0.90 (4)	2.47 (4)	3.362 (4)	171 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯S3i	0.85 (4)	2.61 (5)	3.445 (4)	170 (4)
N2—H2N⋯S2	0.73 (8)	2.91 (8)	3.470 (4)	136 (6)
N2—H2N⋯S3	0.73 (8)	2.89 (8)	3.514 (4)	145 (7)
N2—H3N⋯N3ii	0.99 (4)	1.95 (4)	2.897 (5)	159 (4)
N4—H6N⋯S3i	0.90 (5)	2.44 (5)	3.311 (4)	163 (4)
N4—H7N⋯S2iii	0.87 (4)	2.50 (4)	3.357 (4)	170 (3)
N4—H8N⋯S3iv	0.90 (4)	2.47 (4)	3.362 (4)	171 (3)

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