Bis[3,3′-(piperazine-1,4-di­yl)­dipropan­aminium] di-μ2-sulfido-bis­[disulfido­german­ate(IV)]

Nian-Nian Wang; Chao Xu; Taike Duan; Qun Chen; Qian-Feng Zhang

doi:10.1107/S1600536812030334

. 2012 Jul 10;68(Pt 8):m1046. doi: 10.1107/S1600536812030334

Bis[3,3′-(piperazine-1,4-diyl)dipropanaminium] di-μ₂-sulfido-bis[disulfidogermanate(IV)]

Nian-Nian Wang ^a, Chao Xu ^a, Taike Duan ^a, Qun Chen ^b, Qian-Feng Zhang ^a,^b,^*

PMCID: PMC3414115 PMID: 22904722

Abstract

In the title compound, (C₁₀H₂₆N₄)₂[Ge₂S₆], the dimeric [Ge₂S₆]⁴⁻ anion formed by two edge-sharing GeS₄ tetrahedral 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 _r = 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
Δρ_max = 1.15 e Å⁻³
Δρ_min = −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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030334/gk2485sup1.cif

e-68-m1046-sup1.cif^{(23.9KB, cif)}

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

e-68-m1046-Isup2.hkl^{(193.6KB, hkl)}

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

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⋯S2^iv	0.89	2.34	3.228 (4)	178
N4—H4A⋯S3^v	0.89	2.39	3.275 (4)	173

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

Acknowledgments

This project was supported by the Program for New Century Excellent Talents in Universities of China (grant No. NCET-08–0618).

supplementary crystallographic information

Comment

Since Bedard reported the first porous metal chalcogenide open framework in 1999 (Bedard et al., 1999), a series of binary and ternary metal chalcogenide open-frameworks have been synthesized (Nellis et al., 1995; Zheng et al., 2005). Among the various synthetic methods, hydrothermal technique is the best choice for preparing related compounds due to gentle reaction conditions. Moreover, organic amines are often used as templates in the hydrothermal reactions. Therefore, amines with different structures play an important role for templating effect in the construction of open-frameworks (Zheng et al., 2002). In this paper, we report the hydrothermal synthesis and crystal structure of an amine-templated thiogermanate, [bappH₂]₂[Ge₂S₆] (bapp = 1,4-bis(3-aminopropyl)piperazine).

The title compound crystallizes in the monoclinic space group P2₁/c with a dimeric anion of [Ge₂S₆]^4-located around inversion centre and with diprotonated 1,4-bis(3-aminopropyl)- piperazine in general position (Fig. 1). The dimeric [Ge₂S₆]^4- anion is constructed by two edge-sharing tetrahedral GeS₄ units forming a planar Ge₂S₂ quadrilateral with the four terminal sulfur atoms lying on a perpendicular plane. The S—Ge—S angles in tetrahedral GeS₄ unit are in the ranges from 93.82 (3) to 114.12 (4)°. The average bond length of Ge—S_t (terminal bond) of 2.162 (7) Å is obviously shorter than that of Ge—S_b (bridging bond) [2.267 (15) Å]. The bond length values are similar to those found in the other thiogermanates (Jia et al. 2005; Xu et al., 2012). The two terminal amine groups of 4-bis(3-aminopropyl)piperazine are protonated to balance negative charges of the dimeric anion. The [Ge₂S₆]^4- anions and [bappH₂]²⁺ cations are organized into an extended three-dimensional network by N—H···S hydrogen bonds (Fig. 2 and Table 1).

Experimental

GeO₂ (104.6 mg, 1.0 mmol) and S powder (128.0 mg, 4.0 mmol) in the distilled water (4.8550 g) were mixed with 1,4-bis(3-aminopropyl)piperazine (2.5640 g) in a 23 mL Teflon-lined stainless steel autoclave to and stirred for 20 min. The vessel was sealed and heated to 190°C for 6 d and then cooled to room temperature. Colorless flake crystals were obtained and air dried. The yield based on GeO₂ is about 45%. Analysis, calculated for C₂₀H₅₂N₈S₆Ge₂: C 32.4, H 7.06, N 15.1%; found C 32.2, H 6.98, N 14.8 %.