Tetra­amminelithium triamminelithium tris­ulfide, [Li(NH3)4][Li(NH3)3S3]

Christian Guentner; Nikolaus Korber

doi:10.1107/S1600536812043863

. 2012 Oct 27;68(Pt 11):i84–i85. doi: 10.1107/S1600536812043863

Tetraamminelithium triamminelithium trisulfide, [Li(NH₃)₄][Li(NH₃)₃S₃]

Christian Guentner ^a, Nikolaus Korber ^a,^*

PMCID: PMC3515087 PMID: 23284314

Abstract

The title compound, [Li(NH₃)₄]⁺[Li(NH₃)₃S₃]⁻, an ammoniate of the previously unknown lithium trisulfide, was obtained from the reaction of lithium and sulfur in liquid ammonia. The asymmetric unit consists of two crystallographically independent formula units. The [Li(NH₃)₄]⁺ cations are close to regular LiN₄ tetrahedra. The anions contain LiSN₃ tetrahedra; the S—S—S bond angles are 110.43 (5) and 109.53 (5)°. In the crystal, the components are linked by multiple N—H⋯S hydrogen bonds. A weak N—H⋯N hydrogen bond is also present.

Related literature

For structural details of [Li(NH₃)₄]Se₃, see: Brandl (2009 ▶). For N—H⋯S hydrogen bonds, see: Rossmeier (2002 ▶, 2005 ▶); Meier (2008 ▶). For the synthesis of trisulfides of the heavier alkali metals (Na–Cs), see: Böttcher (1977 ▶, 1980a ▶,b ▶). For hydrogen bonding, see: Steiner (2002 ▶).

Experimental

Crystal data

[Li(NH₃)₄][Li(NH₃)₃S₃]
M _r = 229.30
Monoclinic,
a = 12.422 (3) Å
b = 9.3721 (19) Å
c = 22.269 (5) Å
β = 92.46 (3)°
V = 2590.2 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 123 K
0.1 × 0.1 × 0.1 mm

Data collection

Stoe IPDS 1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie 2006) ▶ T _min = 0.947, T _max = 0.981
32304 measured reflections
4788 independent reflections
2989 reflections with I > 2σ(I)
R _int = 0.097

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.079
S = 0.81
4788 reflections
383 parameters
All H-atom parameters refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2006 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(22.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043863/hb6966sup1.cif

e-68-00i84-sup1.cif^{(22.2KB, cif)}

Click here for additional data file.^{(234.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043863/hb6966Isup2.hkl

e-68-00i84-Isup2.hkl^{(234.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Li1—N2	2.059 (7)
Li1—N3	2.061 (6)
Li1—N1	2.099 (7)
Li1—N4	2.104 (7)
Li2—N7	2.033 (7)
Li2—N5	2.066 (7)
Li2—N6	2.071 (7)
Li2—S1	2.547 (6)
Li3—N10	2.081 (6)
Li3—N11	2.082 (7)
Li3—N9	2.085 (7)
Li3—N8	2.105 (7)
Li4—N13	2.052 (7)
Li4—N14	2.058 (7)
Li4—N12	2.084 (7)
Li4—S4	2.503 (5)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯S4	0.89 (5)	2.84 (5)	3.677 (4)	158 (4)
N5—H5B⋯S4ⁱ	0.93 (5)	2.70 (5)	3.613 (3)	167 (4)
N7—H7C⋯S2	0.89 (5)	2.86 (4)	3.542 (4)	135 (3)
N7—H7C⋯S3	0.89 (5)	2.80 (5)	3.656 (4)	162 (4)
N10—H10B⋯S6	0.89 (6)	2.84 (6)	3.718 (4)	169 (4)
N10—H10A⋯S6ⁱⁱ	0.93 (5)	2.65 (5)	3.545 (4)	163 (3)
N14—H14C⋯S5	0.93 (5)	2.90 (5)	3.552 (4)	128 (4)
N14—H14C⋯S6	0.93 (5)	2.86 (5)	3.781 (4)	170 (4)
N1—H1C⋯S3ⁱⁱⁱ	0.88 (5)	2.98 (5)	3.782 (4)	154 (4)
N1—H1A⋯S5ⁱ	0.90 (5)	2.87 (5)	3.741 (4)	165 (4)
N1—H1B⋯S6^iv	0.83 (5)	2.80 (5)	3.632 (4)	179 (4)
N2—H2B⋯S1^v	0.82 (5)	2.71 (5)	3.521 (4)	168 (4)
N2—H2A⋯S5^iv	0.83 (5)	2.76 (5)	3.566 (4)	166 (4)
N2—H2C⋯S6ⁱⁱ	0.91 (5)	2.66 (5)	3.569 (4)	171 (4)
N3—H3C⋯S1^v	0.85 (6)	2.84 (6)	3.665 (4)	163 (4)
N3—H3B⋯S3^vi	0.92 (5)	2.92 (5)	3.813 (4)	164 (4)
N4—H4A⋯S6ⁱⁱ	0.90 (6)	2.95 (6)	3.834 (4)	168 (4)
N5—H5B⋯S5ⁱ	0.93 (5)	2.91 (5)	3.587 (4)	130 (3)
N6—H6C⋯S5^iv	0.81 (5)	2.91 (6)	3.663 (4)	156 (4)
N6—H6B⋯S6ⁱⁱ	0.90 (5)	2.78 (5)	3.664 (4)	169 (3)
N7—H7A⋯S4	0.83 (5)	2.89 (5)	3.691 (4)	161 (4)
N7—H7B⋯S6ⁱⁱ	0.84 (6)	2.85 (6)	3.600 (4)	150 (5)
N8—H8B⋯S1ⁱ	0.92 (5)	2.83 (5)	3.734 (4)	169 (3)
N8—H8C⋯S2^vi	0.77 (5)	2.89 (5)	3.641 (4)	168 (5)
N8—H8A⋯S4ⁱ	0.83 (5)	2.68 (6)	3.507 (4)	177 (5)
N9—H9A⋯S1ⁱ	0.87 (5)	2.96 (5)	3.803 (4)	163 (4)
N9—H9C⋯S3ⁱⁱ	0.88 (5)	2.85 (5)	3.729 (4)	179 (4)
N9—H9B⋯S6	0.86 (5)	2.99 (5)	3.805 (4)	157 (4)
N11—H11B⋯S3^vi	0.83 (5)	2.90 (5)	3.717 (4)	170 (4)
N12—H12A⋯S2	0.86 (5)	3.01 (5)	3.842 (4)	166 (4)
N12—H12C⋯S3^vii	0.91 (5)	2.93 (5)	3.787 (4)	157 (3)
N13—H13B⋯S1^viii	0.86 (5)	2.72 (5)	3.571 (4)	168 (4)
N13—H13A⋯S3^ix	0.85 (5)	3.01 (5)	3.855 (4)	175 (4)
N13—H13C⋯N4ⁱ	0.86 (5)	2.62 (5)	3.412 (6)	154 (4)
N14—H14B⋯S3^vii	0.85 (5)	2.83 (5)	3.603 (4)	153 (4)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

supplementary crystallographic information

Comment

In contrast to the trisulfides of the heavier alkali metals (Na–Cs) which were synthesized by Böttcher (1977, 1980a,b) under ammonothermalic conditions (130–400 °C, 500–3000 bar), [Li(NH₃)₄][Li(NH₃)₃S₃] was formed in the reaction of lithium and sulfur in liquid ammonia. The crystal structure of [Li(NH₃)₄][Li(NH₃)₃S₃] was determined in the course of investigations concerning the reactivity of sulfur containing components in solutions of alkali metals in liquid ammonia.

In the title compound, two crystallographically independent formula units represent the asymmetric unit (Fig. 1). The independent trisulfide anions S₃^2– have an angled shape with angles of 110.43 (5)° and 109.53 (5)°. The average of the sulfur-sulfur distances is 2.083 Å and agrees with known S—S-distances of other trisulfides (Böttcher, 1977, 1980a,b). In contrast to the isolated Se₃^2–-anion in [Li(NH₃)₄]Se_3, the two crystallographically different S₃^2–-anions build mono anionic [Li(NH₃)₃S₃]^--aggregates with triammine complexes. Therein, the lithium atoms are pseudo-tetrahedrally surrounded by three nitrogen and one sulfur atom. Mono cationic lithium tetrammine complexes compensate the remaining negative charges. In the [Li(NH₃)₄]⁺– and [Li(NH₃)₃S₃]^--units the Li—N-distances range from 2.033 (7) Å to 2.105 (7) Å, the two Li—S-distances from 2.503 (5) Å to 2.547 (6) Å. The title compound represents after Na₂S₃ × NH₃ the second trisulfide compound that contains ammonia molecules of crystallization. Every ammonia molecule forms hydrogen bonds and acts as a donor molecule. The sulfur atoms and the nitrogen atom N(4) operate as hydrogen bond acceptors. The proton···sulfur distance corresponds to similar hydrogen bonds in compounds synthesized by Rossmeier (2002, 2005) or Meier (2008). Distances and angles are shown in Table 1. Figure 2 illustrates the unit cell of the title compound but hydrogen bonds are not depicted.

Experimental

All preparations were carried out in an atmosphere of dried and purified argon using standard Schlenk techniques. Liquid ammonia was dried and stored over sodium. 100 mg (14.2 mmol) Li and 231 mg (7.2 mmol) S₈ were placed in a baked out U-Schlenk tube inside a glove box. Approximately 25 ml ammonia were condensed into the tube at -78°C, yielding a blue solution of the alkali metal. After a storage at -38°C for three weeks the solution colour turned to yellow-orange and after four months orange crystals were formed. One was subjected to low temperature X-ray diffraction.