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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 [sigma](S-S) = 0.001 Å
R = 0.040
wR = 0.079
Data-to-parameter ratio = 12.5
Details
Open access

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

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-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[Brandl, K. (2009). PhD thesis, Universität Regensburg, Germany.]). For N-H...S hydrogen bonds, see: Rossmeier (2002[Rossmeier, T. (2002). Diploma thesis, Universität Regensburg, Germany.], 2005[Rossmeier, T. (2005). PhD thesis, Universität Regensburg, Germany.]); Meier (2008[Meier, M. (2008). Diploma thesis, Universität Regensburg, Germany.]). For the synthesis of trisulfides of the heavier alkali metals (Na-Cs), see: Böttcher (1977[Böttcher, P. (1977). Z. Anorg. Allg. Chem. 432, 167-172.], 1980a[Böttcher, P. (1980a). Z. Anorg. Allg. Chem. 461, 13-21.],b[Böttcher, P. (1980b). Z. Anorg. Allg. Chem. 467, 149-157.]). For hydrogen bonding, see: Steiner (2002[Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48-76.]).

Experimental

Crystal data
  • [Li(NH3)4][Li(NH3)3S3]

  • Mr = 229.30

  • Monoclinic, P 21 /c

  • a = 12.422 (3) Å

  • b = 9.3721 (19) Å

  • c = 22.269 (5) Å

  • [beta] = 92.46 (3)°

  • V = 2590.2 (9) Å3

  • Z = 8

  • Mo K[alpha] radiation

  • [mu] = 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)[Stoe & Cie (2006). X-AREA, X-SHAPE and X-RED. Stoe & Cie GmbH, Darmstadt, Germany.] Tmin = 0.947, Tmax = 0.981

  • 32304 measured reflections

  • 4788 independent reflections

  • 2989 reflections with I > 2[sigma](I)

  • Rint = 0.097

Refinement
  • R[F2 > 2[sigma](F2)] = 0.040

  • wR(F2) = 0.079

  • S = 0.81

  • 4788 reflections

  • 383 parameters

  • All H-atom parameters refined

  • [Delta][rho]max = 0.53 e Å-3

  • [Delta][rho]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-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...S6iv 0.83 (5) 2.80 (5) 3.632 (4) 179 (4)
N2-H2B...S1v 0.82 (5) 2.71 (5) 3.521 (4) 168 (4)
N2-H2A...S5iv 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...S1v 0.85 (6) 2.84 (6) 3.665 (4) 163 (4)
N3-H3B...S3vi 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...S5iv 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...S2vi 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...S3vi 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...S3vii 0.91 (5) 2.93 (5) 3.787 (4) 157 (3)
N13-H13B...S1viii 0.86 (5) 2.72 (5) 3.571 (4) 168 (4)
N13-H13A...S3ix 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...S3vii 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[Stoe & Cie (2006). X-AREA, X-SHAPE and X-RED. Stoe & Cie GmbH, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2008[Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


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.  [CrossRef] [details]
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48-76.  [ISI] [CrossRef] [ChemPort]
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.  [ISI] [CrossRef] [ChemPort] [details]


Acta Cryst (2012). E68, i84-i85   [ doi:10.1107/S1600536812043863 ]

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