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

Guentner, C.; Korber, N.

doi:10.1107/S1600536812043863

Volume 68
Part 11
Pages i84-i85
November 2012

Received 4 October 2012
Accepted 23 October 2012
Online 27 October 2012

Key indicators
Single-crystal X-ray study
T = 123 K
Mean (S-S) = 0.001 Å
R = 0.040
wR = 0.079
Data-to-parameter ratio = 12.5
Details

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

Christian Guentner ^a and Nikolaus Korber ^a ^*

^aInstitut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany
Correspondence e-mail: nikolaus.korber@chemie.uni-regensburg.de

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-HS hydrogen bonds. A weak N-HN hydrogen bond is also present.

Related literature

For structural details of [Li(NH₃)₄]Se₃, see: Brandl (2009). For N-HS 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, P 2₁ /c
a = 12.422 (3) Å
b = 9.3721 (19) Å
c = 22.269 (5) Å
= 92.46 (3)°
V = 2590.2 (9) Å³
Z = 8
Mo K radiation
= 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 > 2(I)
R_int = 0.097

Refinement

R[F² > 2(F²)] = 0.040
wR(F²) = 0.079
S = 0.81
4788 reflections
383 parameters
All H-atom parameters refined
_max = 0.53 e Å^-3
_min = -0.26 e Å^-3

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)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N5-H5AS4	0.89 (5)	2.84 (5)	3.677 (4)	158 (4)
N5-H5BS4ⁱ	0.93 (5)	2.70 (5)	3.613 (3)	167 (4)
N7-H7CS2	0.89 (5)	2.86 (4)	3.542 (4)	135 (3)
N7-H7CS3	0.89 (5)	2.80 (5)	3.656 (4)	162 (4)
N10-H10BS6	0.89 (6)	2.84 (6)	3.718 (4)	169 (4)
N10-H10AS6ⁱⁱ	0.93 (5)	2.65 (5)	3.545 (4)	163 (3)
N14-H14CS5	0.93 (5)	2.90 (5)	3.552 (4)	128 (4)
N14-H14CS6	0.93 (5)	2.86 (5)	3.781 (4)	170 (4)
N1-H1CS3ⁱⁱⁱ	0.88 (5)	2.98 (5)	3.782 (4)	154 (4)
N1-H1AS5ⁱ	0.90 (5)	2.87 (5)	3.741 (4)	165 (4)
N1-H1BS6^iv	0.83 (5)	2.80 (5)	3.632 (4)	179 (4)
N2-H2BS1^v	0.82 (5)	2.71 (5)	3.521 (4)	168 (4)
N2-H2AS5^iv	0.83 (5)	2.76 (5)	3.566 (4)	166 (4)
N2-H2CS6ⁱⁱ	0.91 (5)	2.66 (5)	3.569 (4)	171 (4)
N3-H3CS1^v	0.85 (6)	2.84 (6)	3.665 (4)	163 (4)
N3-H3BS3^vi	0.92 (5)	2.92 (5)	3.813 (4)	164 (4)
N4-H4AS6ⁱⁱ	0.90 (6)	2.95 (6)	3.834 (4)	168 (4)
N5-H5BS5ⁱ	0.93 (5)	2.91 (5)	3.587 (4)	130 (3)
N6-H6CS5^iv	0.81 (5)	2.91 (6)	3.663 (4)	156 (4)
N6-H6BS6ⁱⁱ	0.90 (5)	2.78 (5)	3.664 (4)	169 (3)
N7-H7AS4	0.83 (5)	2.89 (5)	3.691 (4)	161 (4)
N7-H7BS6ⁱⁱ	0.84 (6)	2.85 (6)	3.600 (4)	150 (5)
N8-H8BS1ⁱ	0.92 (5)	2.83 (5)	3.734 (4)	169 (3)
N8-H8CS2^vi	0.77 (5)	2.89 (5)	3.641 (4)	168 (5)
N8-H8AS4ⁱ	0.83 (5)	2.68 (6)	3.507 (4)	177 (5)
N9-H9AS1ⁱ	0.87 (5)	2.96 (5)	3.803 (4)	163 (4)
N9-H9CS3ⁱⁱ	0.88 (5)	2.85 (5)	3.729 (4)	179 (4)
N9-H9BS6	0.86 (5)	2.99 (5)	3.805 (4)	157 (4)
N11-H11BS3^vi	0.83 (5)	2.90 (5)	3.717 (4)	170 (4)
N12-H12AS2	0.86 (5)	3.01 (5)	3.842 (4)	166 (4)
N12-H12CS3^vii	0.91 (5)	2.93 (5)	3.787 (4)	157 (3)
N13-H13BS1^viii	0.86 (5)	2.72 (5)	3.571 (4)	168 (4)
N13-H13AS3^ix	0.85 (5)	3.01 (5)	3.855 (4)	175 (4)
N13-H13CN4ⁱ	0.86 (5)	2.62 (5)	3.412 (6)	154 (4)
N14-H14BS3^vii	0.85 (5)	2.83 (5)	3.603 (4)	153 (4)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) x+1, y, z; (vii) -x, -y+1, -z+1; (viii) -x, -y+2, -z+1; (ix) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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 data and figures for this paper are available from the IUCr electronic archives (Reference: HB6966 ).

References

Böttcher, P. (1977). Z. Anorg. Allg. Chem. 432, 167-172.
Böttcher, P. (1980a). Z. Anorg. Allg. Chem. 461, 13-21.
Böttcher, P. (1980b). Z. Anorg. Allg. Chem. 467, 149-157.
Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Brandl, K. (2009). PhD thesis, Universität Regensburg, Germany.
Meier, M. (2008). Diploma thesis, Universität Regensburg, Germany.
Rossmeier, T. (2002). Diploma thesis, Universität Regensburg, Germany.
Rossmeier, T. (2005). PhD thesis, Universität Regensburg, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48-76.
Stoe & Cie (2006). X-AREA, X-SHAPE and X-RED. Stoe & Cie GmbH, Darmstadt, Germany.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.

inorganic compounds