Bis[3,3'-(piperazine-1,4-di-yl)-dipropan-aminium] di-μ(2)-sulfido-bis-[disulfido-german-ate(IV)].

In the title compound, (C(10)H(26)N(4))(2)[Ge(2)S(6)], the dimeric [Ge(2)S(6)](4-) anion formed by two edge-sharing GeS(4) tetra-hedral units lies around an inversion centre. The average terminal and bridging Ge-S bond lengths are 2.162 (7) and 2.267 (15) Å, respectively. The inorganic anions and organic cations are organized into a three-dimensional network by numerous N-H⋯S hydrogen bonds.

Related literature

For background to main group metal–chalcogenide compounds, see: Bedard et al. (1999 ▶); Nellis et al. (1995 ▶); Blachnik & Fehlker (2001 ▶); Zheng et al. (2002 ▶, 2005 ▶). For related structures, see: Jia et al. (2005 ▶); Xu et al. (2012 ▶).

Experimental

Crystal data

(C10H26N4)2[Ge2S6]

M = 742.24

Monoclinic,

a = 12.0111 (4) Å

b = 7.7759 (3) Å

c = 18.9777 (7) Å

β = 103.569 (1)°

V = 1722.99 (11) Å3

Z = 2

Mo Kα radiation

μ = 2.13 mm−1

T = 296 K

0.38 × 0.29 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.498, T max = 0.727

16480 measured reflections

3950 independent reflections

3194 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.113

S = 1.07

3950 reflections

165 parameters

H-atom parameters constrained

Δρmax = 1.15 e Å−3

Δρmin = −0.37 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/S1600536812030334/gk2485sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030334/gk2485Isup2.hkl

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

(C10H26N4)2[Ge2S6]	F(000) = 776
Mr = 742.24	Dx = 1.431 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6783 reflections
a = 12.0111 (4) Å	θ = 2.5–27.0°
b = 7.7759 (3) Å	µ = 2.13 mm−1
c = 18.9777 (7) Å	T = 296 K
β = 103.569 (1)°	Block, colourless
V = 1722.99 (11) Å3	0.38 × 0.29 × 0.16 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	3950 independent reflections
Radiation source: fine-focus sealed tube	3194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
phi and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −15→15
Tmin = 0.498, Tmax = 0.727	k = −10→6
16480 measured reflections	l = −22→24

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0586P)2 + 1.3201P] where P = (Fo2 + 2Fc2)/3
3950 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 1.15 e Å−3
0 restraints	Δρmin = −0.37 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	0.53261 (3)	0.44178 (4)	0.080248 (14)	0.04128 (12)
S1	0.38171 (8)	0.59109 (12)	0.01275 (4)	0.0541 (2)
S2	0.47606 (9)	0.19876 (11)	0.11556 (4)	0.0606 (3)
S3	0.63552 (8)	0.59389 (11)	0.16645 (4)	0.0565 (2)
N1	0.1088 (3)	0.4905 (5)	0.1532 (2)	0.0769 (10)
N2	−0.0300 (3)	0.1852 (5)	0.1210 (3)	0.1023 (15)
N3	0.4526 (3)	0.8528 (4)	0.20970 (15)	0.0630 (8)
H3A	0.4580	0.8401	0.2570	0.094*
H3B	0.4769	0.9572	0.2013	0.094*
H3C	0.4956	0.7738	0.1948	0.094*
N4	−0.3627 (4)	−0.0949 (5)	0.0505 (2)	0.0782 (10)
H4A	−0.3673	−0.1851	0.0785	0.117*
H4B	−0.3923	−0.1222	0.0043	0.117*
H4C	−0.4016	−0.0072	0.0630	0.117*
C6	0.1475 (5)	0.3408 (7)	0.1201 (5)	0.121 (2)
H6A	0.2301	0.3319	0.1362	0.145*
H6B	0.1284	0.3547	0.0679	0.145*
C7	0.0954 (5)	0.1827 (7)	0.1388 (5)	0.146 (3)
H7A	0.1227	0.1621	0.1903	0.175*
H7B	0.1207	0.0875	0.1134	0.175*
C8	−0.0710 (4)	0.3401 (7)	0.1474 (4)	0.0981 (16)
H8A	−0.0559	0.3348	0.1999	0.118*
H8B	−0.1532	0.3475	0.1288	0.118*
C9	−0.0168 (4)	0.4974 (6)	0.1262 (4)	0.0932 (15)
H9A	−0.0357	0.5077	0.0738	0.112*
H9B	−0.0466	0.5979	0.1459	0.112*
C10	0.1646 (4)	0.6473 (6)	0.1389 (3)	0.0880 (13)
H10A	0.1219	0.7451	0.1504	0.106*
H10B	0.1631	0.6528	0.0876	0.106*
C11	0.2881 (4)	0.6607 (6)	0.1822 (2)	0.0713 (10)
H11A	0.2915	0.6441	0.2334	0.086*
H4N	0.3338	0.5716	0.1669	0.086*
C12	0.3349 (4)	0.8321 (5)	0.1708 (2)	0.0725 (11)
H12A	0.3294	0.8485	0.1195	0.087*
H12B	0.2888	0.9201	0.1865	0.087*
C13	−0.0732 (7)	0.0324 (9)	0.1558 (5)	0.151 (3)
H13A	−0.0359	−0.0697	0.1430	0.182*
H13B	−0.0489	0.0458	0.2079	0.182*
C14	−0.1959 (7)	0.0022 (10)	0.1373 (3)	0.129 (3)
H14A	−0.2341	0.1056	0.1479	0.155*
H14B	−0.2130	−0.0889	0.1680	0.155*
C15	−0.2442 (5)	−0.0463 (8)	0.0594 (3)	0.1042 (18)
H15A	−0.2385	0.0503	0.0281	0.125*
H15B	−0.2012	−0.1416	0.0461	0.125*

	U11	U22	U33	U12	U13	U23
Ge1	0.0602 (2)	0.03395 (18)	0.02960 (17)	0.00094 (13)	0.01036 (13)	0.00344 (11)
S1	0.0626 (5)	0.0634 (5)	0.0388 (4)	0.0157 (4)	0.0166 (3)	0.0086 (3)
S2	0.0973 (7)	0.0428 (4)	0.0406 (4)	−0.0147 (4)	0.0140 (4)	0.0072 (3)
S3	0.0768 (6)	0.0487 (5)	0.0396 (4)	−0.0091 (4)	0.0046 (4)	−0.0021 (3)
N1	0.066 (2)	0.0546 (18)	0.111 (3)	0.0014 (16)	0.0225 (19)	−0.0006 (19)
N2	0.076 (2)	0.062 (2)	0.152 (4)	−0.0009 (19)	−0.008 (3)	−0.010 (3)
N3	0.099 (2)	0.0472 (16)	0.0448 (15)	−0.0004 (16)	0.0211 (15)	−0.0012 (12)
N4	0.102 (3)	0.068 (2)	0.066 (2)	−0.0073 (19)	0.0226 (19)	−0.0058 (17)
C6	0.077 (3)	0.074 (3)	0.216 (7)	0.006 (3)	0.040 (4)	−0.035 (4)
C7	0.078 (3)	0.062 (3)	0.271 (10)	0.010 (3)	−0.014 (5)	−0.027 (4)
C8	0.068 (3)	0.083 (3)	0.138 (5)	−0.008 (2)	0.012 (3)	−0.011 (3)
C9	0.073 (3)	0.066 (3)	0.136 (5)	0.013 (2)	0.014 (3)	0.002 (3)
C10	0.088 (3)	0.068 (3)	0.109 (4)	0.005 (2)	0.026 (3)	0.013 (3)
C11	0.074 (2)	0.075 (3)	0.066 (2)	0.000 (2)	0.0193 (19)	−0.001 (2)
C12	0.101 (3)	0.058 (2)	0.056 (2)	0.014 (2)	0.014 (2)	−0.0031 (18)
C13	0.147 (6)	0.091 (4)	0.185 (8)	−0.047 (4)	−0.022 (6)	0.026 (5)
C14	0.157 (6)	0.136 (5)	0.086 (4)	−0.068 (5)	0.012 (4)	0.015 (4)
C15	0.107 (4)	0.128 (5)	0.079 (3)	−0.018 (3)	0.025 (3)	0.004 (3)

Ge1—S3	2.1573 (9)	C7—H7B	0.9700
Ge1—S2	2.1669 (9)	C8—C9	1.485 (7)
Ge1—S1	2.2770 (9)	C8—H8A	0.9700
S1—Ge1i	2.2564 (8)	C8—H8B	0.9700
N1—C10	1.448 (6)	C9—H9A	0.9700
N1—C6	1.450 (6)	C9—H9B	0.9700
N1—C9	1.476 (6)	C10—C11	1.522 (6)
N2—C8	1.435 (7)	C10—H10A	0.9700
N2—C7	1.465 (7)	C10—H10B	0.9700
N2—C13	1.509 (8)	C11—C12	1.482 (6)
N3—C12	1.442 (5)	C11—H11A	0.9700
N3—H3A	0.8900	C11—H4N	0.9700
N3—H3B	0.8900	C12—H12A	0.9700
N3—H3C	0.8900	C12—H12B	0.9700
N4—C15	1.443 (7)	C13—C14	1.451 (10)
N4—H4A	0.8900	C13—H13A	0.9700
N4—H4B	0.8900	C13—H13B	0.9700
N4—H4C	0.8900	C14—C15	1.504 (8)
C6—C7	1.460 (8)	C14—H14A	0.9700
C6—H6A	0.9700	C14—H14B	0.9700
C6—H6B	0.9700	C15—H15A	0.9700
C7—H7A	0.9700	C15—H15B	0.9700
S3—Ge1—S2	114.15 (3)	N1—C9—C8	110.6 (4)
S3—Ge1—S1i	111.71 (4)	N1—C9—H9A	109.5
S2—Ge1—S1i	112.13 (4)	C8—C9—H9A	109.5
S3—Ge1—S1	112.70 (4)	N1—C9—H9B	109.5
S2—Ge1—S1	110.66 (4)	C8—C9—H9B	109.5
S1i—Ge1—S1	93.82 (3)	H9A—C9—H9B	108.1
Ge1i—S1—Ge1	86.18 (3)	N1—C10—C11	113.1 (4)
C10—N1—C6	112.7 (4)	N1—C10—H10A	109.0
C10—N1—C9	112.6 (4)	C11—C10—H10A	109.0
C6—N1—C9	106.5 (4)	N1—C10—H10B	109.0
C8—N2—C7	110.4 (4)	C11—C10—H10B	109.0
C8—N2—C13	109.1 (6)	H10A—C10—H10B	107.8
C7—N2—C13	109.2 (5)	C12—C11—C10	109.7 (4)
C12—N3—H3A	109.5	C12—C11—H11A	109.7
C12—N3—H3B	109.5	C10—C11—H11A	109.7
H3A—N3—H3B	109.5	C12—C11—H4N	109.7
C12—N3—H3C	109.5	C10—C11—H4N	109.7
H3A—N3—H3C	109.5	H11A—C11—H4N	108.2
H3B—N3—H3C	109.5	N3—C12—C11	112.7 (3)
C15—N4—H4A	109.5	N3—C12—H12A	109.1
C15—N4—H4B	109.5	C11—C12—H12A	109.1
H4A—N4—H4B	109.5	N3—C12—H12B	109.1
C15—N4—H4C	109.5	C11—C12—H12B	109.1
H4A—N4—H4C	109.5	H12A—C12—H12B	107.8
H4B—N4—H4C	109.5	C14—C13—N2	117.1 (6)
N1—C6—C7	111.8 (5)	C14—C13—H13A	108.0
N1—C6—H6A	109.3	N2—C13—H13A	108.0
C7—C6—H6A	109.3	C14—C13—H13B	108.0
N1—C6—H6B	109.3	N2—C13—H13B	108.0
C7—C6—H6B	109.3	H13A—C13—H13B	107.3
H6A—C6—H6B	107.9	C13—C14—C15	114.5 (7)
C6—C7—N2	114.2 (5)	C13—C14—H14A	108.6
C6—C7—H7A	108.7	C15—C14—H14A	108.6
N2—C7—H7A	108.7	C13—C14—H14B	108.6
C6—C7—H7B	108.7	C15—C14—H14B	108.6
N2—C7—H7B	108.7	H14A—C14—H14B	107.6
H7A—C7—H7B	107.6	N4—C15—C14	108.9 (5)
N2—C8—C9	112.9 (5)	N4—C15—H15A	109.9
N2—C8—H8A	109.0	C14—C15—H15A	109.9
C9—C8—H8A	109.0	N4—C15—H15B	109.9
N2—C8—H8B	109.0	C14—C15—H15B	109.9
C9—C8—H8B	109.0	H15A—C15—H15B	108.3
H8A—C8—H8B	107.8

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S2ii	0.89	2.48	3.278 (3)	149
N3—H3C···S3	0.89	2.34	3.225 (3)	170
N3—H3A···S2iii	0.89	2.61	3.440 (3)	157
N3—H3A···S3iii	0.89	2.83	3.366 (3)	120
N4—H4C···S2iv	0.89	2.53	3.408 (4)	169
N4—H4B···S2v	0.89	2.34	3.228 (4)	178
N4—H4A···S3vi	0.89	2.39	3.275 (4)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯S2i	0.89	2.48	3.278 (3)	149
N3—H3C⋯S3	0.89	2.34	3.225 (3)	170
N3—H3A⋯S2ii	0.89	2.61	3.440 (3)	157
N3—H3A⋯S3ii	0.89	2.83	3.366 (3)	120
N4—H4C⋯S2iii	0.89	2.53	3.408 (4)	169
N4—H4B⋯S2iv	0.89	2.34	3.228 (4)	178
N4—H4A⋯S3v	0.89	2.39	3.275 (4)	173

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