Bis[4-(2-aza-niumyleth-yl)piperazin-1-ium] di-μ-sulfido-bis-[disulfido-germanate(II)].

In the title compound, (C(6)H(17)N(3))(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 2.164 (2) and 2.272 (8) Å, respectively. The dimeric inorganic anions and the organic piperazinium cations are organized into a three-dimensional network by N-H⋯S hydrogen bonds.

Related literature

For background to main-group metal–chalcogenide compounds, see: Bedard et al. (1989 ▶); Yaghi et al. (1994 ▶); Bowes & Ozin (1996 ▶); Zheng et al. (2005 ▶); Zhang et al. (2008 ▶); Haddadpour et al. (2009 ▶). For related structures, see: Jia et al. (2005 ▶); Xu et al. (2012 ▶).

Experimental

Crystal data

(C6H17N3)2[Ge2S6]

M = 600.10

Triclinic,

a = 7.4985 (1) Å

b = 8.2709 (1) Å

c = 10.4177 (1) Å

α = 72.156 (1)°

β = 78.323 (1)°

γ = 89.792 (1)°

V = 601.11 (1) Å3

Z = 1

Mo Kα radiation

μ = 3.03 mm−1

T = 296 K

0.21 × 0.16 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.568, T max = 0.694

11264 measured reflections

2756 independent reflections

2558 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.044

S = 1.04

2756 reflections

118 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536812022040/mw2068sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022040/mw2068Isup2.hkl

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

(C6H17N3)2[Ge2S6]	Z = 1
Mr = 600.10	F(000) = 308
Triclinic, P1	Dx = 1.657 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4985 (1) Å	Cell parameters from 6350 reflections
b = 8.2709 (1) Å	θ = 2.5–26.4°
c = 10.4177 (1) Å	µ = 3.03 mm−1
α = 72.156 (1)°	T = 296 K
β = 78.323 (1)°	Slab, colorless
γ = 89.792 (1)°	0.21 × 0.16 × 0.13 mm
V = 601.11 (1) Å3

Bruker APEXII CCD area-detector diffractometer	2756 independent reflections
Radiation source: fine-focus sealed tube	2558 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→9
Tmin = 0.568, Tmax = 0.694	k = −10→10
11264 measured reflections	l = −13→13

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.044	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0255P)2 + 0.0568P] where P = (Fo2 + 2Fc2)/3
2756 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.20 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	0.534452 (18)	−0.015013 (17)	0.647883 (13)	0.02329 (5)
S1	0.39310 (5)	0.17306 (4)	0.49657 (4)	0.03133 (9)
S2	0.34914 (5)	−0.14470 (5)	0.84118 (4)	0.03350 (9)
S3	0.77604 (5)	0.09503 (5)	0.68057 (4)	0.03090 (9)
N1	0.6536 (2)	0.80969 (18)	0.03620 (14)	0.0430 (3)
H1A	0.6097	0.8421	−0.0415	0.052*
H1B	0.6380	0.8934	0.0751	0.052*
N2	0.94141 (17)	0.20541 (15)	0.34735 (13)	0.0330 (3)
H2A	0.8730	0.1634	0.4320	0.049*
H2B	1.0236	0.1318	0.3323	0.049*
H2C	0.8707	0.2230	0.2859	0.049*
N3	0.82332 (17)	0.56300 (15)	0.22444 (12)	0.0310 (3)
C3	0.5509 (2)	0.6512 (2)	0.1331 (2)	0.0471 (4)
H3A	0.5581	0.5636	0.0884	0.057*
H3B	0.4234	0.6728	0.1586	0.057*
C4	0.6293 (2)	0.5917 (2)	0.25953 (17)	0.0404 (4)
H4A	0.6139	0.6763	0.3074	0.048*
H4B	0.5638	0.4867	0.3212	0.048*
C5	0.9224 (2)	0.7215 (2)	0.13193 (18)	0.0462 (4)
H5A	1.0512	0.7030	0.1096	0.055*
H5B	0.9088	0.8079	0.1780	0.055*
C6	0.8514 (3)	0.7828 (3)	0.00124 (18)	0.0513 (5)
H6A	0.9172	0.8886	−0.0584	0.062*
H6B	0.8699	0.6992	−0.0475	0.062*
C7	0.9006 (3)	0.5008 (2)	0.34801 (17)	0.0416 (4)
H7A	0.8031	0.4515	0.4279	0.050*
H7B	0.9606	0.5955	0.3625	0.050*
C8	1.0363 (2)	0.3689 (2)	0.33375 (18)	0.0384 (3)
H8A	1.1192	0.4095	0.2445	0.046*
H8B	1.1075	0.3511	0.4044	0.046*

	U11	U22	U33	U12	U13	U23
Ge1	0.02519 (8)	0.02634 (8)	0.02008 (8)	0.00381 (5)	−0.00971 (5)	−0.00663 (6)
S1	0.0419 (2)	0.03052 (18)	0.02880 (19)	0.01500 (14)	−0.01897 (15)	−0.01251 (14)
S2	0.03277 (19)	0.0426 (2)	0.02247 (17)	−0.00458 (15)	−0.00702 (14)	−0.00547 (15)
S3	0.02968 (18)	0.03499 (19)	0.03217 (19)	0.00113 (14)	−0.01403 (14)	−0.01165 (15)
N1	0.0604 (9)	0.0426 (8)	0.0369 (7)	0.0181 (6)	−0.0304 (7)	−0.0153 (6)
N2	0.0350 (6)	0.0325 (6)	0.0308 (6)	0.0071 (5)	−0.0105 (5)	−0.0066 (5)
N3	0.0387 (7)	0.0290 (6)	0.0265 (6)	0.0061 (5)	−0.0144 (5)	−0.0056 (5)
C3	0.0397 (9)	0.0499 (10)	0.0598 (11)	0.0059 (7)	−0.0220 (8)	−0.0214 (9)
C4	0.0414 (9)	0.0377 (8)	0.0375 (9)	0.0026 (7)	−0.0057 (7)	−0.0067 (7)
C5	0.0395 (9)	0.0485 (10)	0.0411 (9)	−0.0035 (7)	−0.0160 (7)	0.0046 (8)
C6	0.0546 (11)	0.0568 (11)	0.0310 (9)	0.0061 (9)	−0.0104 (8)	0.0037 (8)
C7	0.0641 (11)	0.0337 (8)	0.0330 (8)	0.0120 (7)	−0.0255 (8)	−0.0097 (7)
C8	0.0391 (8)	0.0371 (8)	0.0404 (9)	0.0034 (6)	−0.0211 (7)	−0.0062 (7)

Ge1—S3	2.1628 (4)	C3—C4	1.495 (2)
Ge1—S2	2.1658 (4)	C3—H3A	0.9700
Ge1—S1i	2.2668 (4)	C3—H3B	0.9700
Ge1—S1	2.2780 (4)	C4—H4A	0.9700
S1—Ge1i	2.2668 (4)	C4—H4B	0.9700
N1—C6	1.487 (2)	C5—C6	1.504 (2)
N1—C3	1.487 (2)	C5—H5A	0.9700
N1—H1A	0.9000	C5—H5B	0.9700
N1—H1B	0.9000	C6—H6A	0.9700
N2—C8	1.4845 (19)	C6—H6B	0.9700
N2—H2A	0.8900	C7—C8	1.509 (2)
N2—H2B	0.8900	C7—H7A	0.9700
N2—H2C	0.8900	C7—H7B	0.9700
N3—C4	1.464 (2)	C8—H8A	0.9700
N3—C5	1.4637 (19)	C8—H8B	0.9700
N3—C7	1.467 (2)
S3—Ge1—S2	111.635 (15)	N3—C4—H4A	109.4
S3—Ge1—S1i	111.482 (15)	C3—C4—H4A	109.4
S2—Ge1—S1i	114.630 (15)	N3—C4—H4B	109.4
S3—Ge1—S1	113.476 (15)	C3—C4—H4B	109.4
S2—Ge1—S1	112.453 (16)	H4A—C4—H4B	108.0
S1i—Ge1—S1	91.835 (13)	N3—C5—C6	110.83 (14)
Ge1i—S1—Ge1	88.165 (13)	N3—C5—H5A	109.5
C6—N1—C3	110.87 (13)	C6—C5—H5A	109.5
C6—N1—H1A	109.4	N3—C5—H5B	109.5
C3—N1—H1A	109.5	C6—C5—H5B	109.5
C6—N1—H1B	109.5	H5A—C5—H5B	108.1
C3—N1—H1B	109.4	N1—C6—C5	109.21 (15)
H1A—N1—H1B	108.1	N1—C6—H6A	109.8
C8—N2—H2A	109.5	C5—C6—H6A	109.8
C8—N2—H2B	109.5	N1—C6—H6B	109.8
H2A—N2—H2B	109.5	C5—C6—H6B	109.8
C8—N2—H2C	109.5	H6A—C6—H6B	108.3
H2A—N2—H2C	109.5	N3—C7—C8	111.07 (13)
H2B—N2—H2C	109.5	N3—C7—H7A	109.4
C4—N3—C5	109.42 (13)	C8—C7—H7A	109.4
C4—N3—C7	111.63 (13)	N3—C7—H7B	109.4
C5—N3—C7	109.98 (13)	C8—C7—H7B	109.4
N1—C3—C4	109.82 (13)	H7A—C7—H7B	108.0
N1—C3—H3A	109.7	N2—C8—C7	110.74 (13)
C4—C3—H3A	109.7	N2—C8—H8A	109.5
N1—C3—H3B	109.7	C7—C8—H8A	109.5
C4—C3—H3B	109.7	N2—C8—H8B	109.5
H3A—C3—H3B	108.2	C7—C8—H8B	109.5
N3—C4—C3	111.20 (13)	H8A—C8—H8B	108.1

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S2ii	0.90	2.50	3.3864 (14)	170
N1—H1A···S2iii	0.90	2.49	3.2990 (14)	150
N2—H2A···S3	0.89	2.43	3.2781 (13)	160
N2—H2C···S2i	0.89	2.51	3.3467 (13)	157
N2—H2B···S3iv	0.89	2.42	3.3021 (13)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯S2i	0.90	2.50	3.3864 (14)	170
N1—H1A⋯S2ii	0.90	2.49	3.2990 (14)	150
N2—H2A⋯S3	0.89	2.43	3.2781 (13)	160
N2—H2C⋯S2iii	0.89	2.51	3.3467 (13)	157
N2—H2B⋯S3iv	0.89	2.42	3.3021 (13)	172

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