Acta Crystallographica Section E: Structure Reports Online

Acta Crystallogr Sect E Struct Rep Online. 66(Pt 2): i13-i13

Redetermination of diammonium thiomolybdate

Björn Hilla, Hans-Wolfram Lernera, Michael Boltea*

a. Institut für Anorganische Chemie der Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany

Correspondence e-mail: bolte@chemie.uni-frankfurt.de

© Hill et al. 2010

DOI: 10.1107/S1600536810003016

Published online: 30 January 2010

Abstract

In contrast to the previous structure determinations of the title structure, (NH₄)₂[MoS₄], the present determination at 173 K localized the positions of the H atoms. The title structure belongs to the β-K₂SO₄ family and all the ions are located on crystallographic mirror planes. The ions are held together by N—H⋯S hydrogen bonds (some of which are bifurcated), forming a three-dimensional network. One of the N atoms has nine contacts to the S atoms shorter than 4 Å, and the other has ten.

Related literature

For preparation of the title compound, see: Herzog et al. (1981 ▶). For structures of the β-K₂SO₄ family, see: Fábry & Pérez-Mato (1994 ▶). For other structure determinations of the title compound, see: Lapasset et al. (1976 ▶); Schäfer et al. (1964 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

(NH₄)₂[MoS₄]

M r = 260.26

Orthorhombic,

a = 9.5867 (4) Å

b = 6.9451 (4) Å

c = 12.2005 (5) Å

V = 812.32 (7) Å³

Z = 4

Mo Kα radiation

μ = 2.55 mm⁻¹

T = 173 K

0.25 × 0.24 × 0.11 mm

Data collection

Stoe IPDS II two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2009 ▶; Blessing, 1995 ▶) T min = 0.569, T max = 0.767

14872 measured reflections

859 independent reflections

833 reflections with I > 2σ(I)

R int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.022

wR(F ²) = 0.060

S = 1.19

859 reflections

61 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å⁻³

Δρmin = −0.88 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); 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: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

See full table Table 1. Hydrogen-bond geometry (Å, °)

Supplementary Material

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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2179).

supplementary crystallographic information

Comment

The crystal structure of the title compound, (NH₄)₂MoS₄, previously determined using Weissenberg exposures (Schäfer et al., 1964) and using a point detector diffractometer (Lapasset et al., 1976) has been redetermined at low temperature since the two previous structure determinations did not include the positions of the H atoms.

The crystal structure belongs to the β-K₂SO₄ family (Fábry & Pérez-Mato, 1994). The anions and cations are held together by N—H···S hydrogen bonds forming a three-dimensional network involving all H atoms.

Experimental

The ammonium tetrathiomolybdate (NH₄)₂MoS₄ was synthesized by the reaction from (NH₄)₆Mo₇O₂₄.4H₂O with H₂S in the presence of NH₃ (Herzog et al., 1981) as shown by the equation:

(NH₄)₆Mo₇O₂₄ + 28 H₂S + 8 NH₃→ 7(NH₄)₂MoS₄ + 24 H₂O.

H₂S was bubbled for 30 minutes through a solution of 4.94 g (4.0 mmol) (NH₄)₆Mo₇O₂₄.4H₂O in 50 ml aqueous ammonia. At first the reaction solution became yellow then the colour changed from yellow towards red. The red colour indicated the end of the reaction (Herzog et al., 1981). X-ray quality crystals of (NH₄)₂MoS₄ were grown from the reaction solution at ambient temperature. The crystals are pleochroic, changing colour from red to green according to the view angle.

Refinement

Hydrogen atoms were located in a difference Fourier map and refined isotropically. The N—H distances were restrained to 0.878 (20) Å. The value 0.878Å has been retrieved from the structures XUDGET, TERNOT, TEJMUQ, TEJMOK, KOLKAY, KEVVEN, ICOMUI contained in the Cambridge Crystallographic Database (Version 5.31; Allen, 2002). The condition of the search in the Cambridge Crystallographic Database: The structures contained [NH₄]⁺, K was the possibly heaviest atom in the structure, and the structures have been determined with R-factor 〈 0.03.

Figures

Fig. 1.View larger versionFig. 1. A view of the three molecules in the asymmetric unit of the title compound, with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level and the H atoms are shown as small spheres of arbitrary radii.

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, °)

See full table

Symmetry codes: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, °)

See full table

Symmetry codes: (ii) x+1, y, z; (iii) x+1/2, y, −z+1/2; (i) x, −y+3/2, z; (iv) −x+1, y+1/2, −z+1; (v) −x, −y+1, −z+1; (vi) −x+1/2, y+1/2, z+1/2; (vii) −x+1/2, −y+1, z+1/2.

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References

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Fábry, J. & Pérez-Mato, J. M. (1994). Phase Trans.499, 193–229.

Herzog, S., Gustav, K. & Strähle, J. (1981). Handbuch der Präparativen Chemie, Vol. 3, edited by G. Brauer, pp. 1551–1552. Stuttgart: Ferdinand Enke Verlag.

Lapasset, J., Chezau, N. & Belougne, P. (1976). Acta Cryst. B32, 3087–3088.

Schäfer, H., Schäfer, G. & Weiss, A. (1964). Z. Naturforsch. Teil B, 19, 76.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (2001). X-AREA and X-RED Stoe & Cie, Darmstadt, Germany.

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Fig. 1.

A view of the three molecules in the asymmetric unit of the title compound, with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level and the H atoms are shown as small spheres of arbitrary radii.

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(NH₄)₂[MoS₄] | F(000) = 512
Mr = 260.26 | Dx = 2.128 Mg m⁻³
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n | Cell parameters from 14093 reflections
a = 9.5867 (4) Å | θ = 2.7–26.4°
b = 6.9451 (4) Å | µ = 2.55 mm⁻¹
c = 12.2005 (5) Å | T = 173 K
V = 812.32 (7) Å³ | Plate, dark green
Z = 4 | 0.25 × 0.24 × 0.11 mm

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Stoe IPDS II two-circle diffractometer | 859 independent reflections
Radiation source: fine-focus sealed tube | 833 reflections with I > 2σ(I)
graphite | Rint = 0.072
ω scans | θmax = 25.9°, θmin = 2.7°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −11→11
Tmin = 0.569, Tmax = 0.767 | k = −8→8
14872 measured reflections | l = −14→15

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Refinement on F² | Secondary atom site location: difference Fourier map
Least-squares matrix: full | Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022 | H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060 | w = 1/[σ²(Fo²) + (0.0377P)² + 0.2462P] where P = (Fo² + 2Fc²)/3
S = 1.19 | (Δ/σ)max < 0.001
859 reflections | Δρmax = 0.51 e Å⁻³
61 parameters | Δρmin = −0.88 e Å⁻³
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc²λ³/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0173 (13)

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Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

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| x | y | z | Uiso*/Ueq |
Mo1 | 0.25414 (2) | 0.7500 | 0.42734 (2) | 0.01490 (16) |
S1 | 0.03014 (7) | 0.7500 | 0.38769 (6) | 0.0229 (2) |
S2 | 0.28425 (9) | 0.7500 | 0.60460 (7) | 0.0246 (2) |
S3 | 0.35338 (5) | 0.49616 (7) | 0.35742 (5) | 0.0259 (2) |
N1 | 0.6660 (3) | 0.7500 | 0.3880 (2) | 0.0257 (6) |
H1A | 0.746 (4) | 0.7500 | 0.355 (5) | 0.072 (19)* |
H1B | 0.590 (4) | 0.7500 | 0.347 (4) | 0.089 (19)* |
H1C | 0.665 (5) | 0.850 (5) | 0.433 (3) | 0.114 (18)* |
N2 | −0.0471 (3) | 0.7500 | 0.6609 (2) | 0.0223 (5) |
H2A | −0.002 (5) | 0.7500 | 0.723 (3) | 0.09 (2)* |
H2B | 0.003 (6) | 0.7500 | 0.600 (3) | 0.10 (2)* |
H2C | −0.097 (5) | 0.644 (5) | 0.656 (4) | 0.114 (16)* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
Mo1 | 0.0146 (2) | 0.0149 (2) | 0.0152 (2) | 0.000 | 0.00038 (8) | 0.000
S1 | 0.0161 (4) | 0.0297 (4) | 0.0228 (4) | 0.000 | −0.0034 (3) | 0.000
S2 | 0.0214 (4) | 0.0349 (4) | 0.0175 (4) | 0.000 | −0.0024 (3) | 0.000
S3 | 0.0235 (3) | 0.0196 (3) | 0.0346 (3) | 0.00079 (18) | 0.0062 (2) | −0.0074 (2)
N1 | 0.0235 (14) | 0.0268 (14) | 0.0267 (15) | 0.000 | −0.0028 (11) | 0.000
N2 | 0.0219 (13) | 0.0258 (13) | 0.0193 (13) | 0.000 | 0.0030 (10) | 0.000

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Mo1—S3i | 2.1773 (5) | N1—H1B | 0.88 (2)
Mo1—S3 | 2.1773 (5) | N1—H1C | 0.883 (19)
Mo1—S2 | 2.1818 (9) | N2—H2A | 0.88 (2)
Mo1—S1 | 2.2013 (8) | N2—H2B | 0.88 (2)
N1—H1A | 0.86 (2) | N2—H2C | 0.879 (19)
S3i—Mo1—S3 | 108.13 (3) | H1A—N1—H1B | 118 (6)
S3i—Mo1—S2 | 109.30 (2) | H1A—N1—H1C | 107 (4)
S3—Mo1—S2 | 109.30 (2) | H1B—N1—H1C | 110 (3)
S3i—Mo1—S1 | 109.885 (19) | H2A—N2—H2B | 117 (5)
S3—Mo1—S1 | 109.885 (19) | H2A—N2—H2C | 109 (3)
S2—Mo1—S1 | 110.30 (3) | H2B—N2—H2C | 103 (3)

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D—H···A | D—H | H···A | D···A | D—H···A
N1—H1A···S1ii | 0.86 (2) | 2.76 (4) | 3.491 (3) | 144 (6)
N1—H1B···S1iii | 0.88 (2) | 2.92 (5) | 3.607 (3) | 135 (5)
N1—H1B···S3 | 0.88 (2) | 2.87 (3) | 3.497 (3) | 129 (3)
N1—H1B···S3i | 0.88 (2) | 2.87 (3) | 3.497 (3) | 129 (3)
N1—H1C···S3iv | 0.88 (2) | 2.76 (3) | 3.550 (3) | 150 (4)
N1—H1C···S3iv | 0.88 (2) | 2.76 (3) | 3.550 (3) | 150 (4)
N2—H2C···S3v | 0.88 (2) | 2.65 (3) | 3.405 (2) | 144 (4)
N2—H2A···S3vi | 0.88 (2) | 2.76 (2) | 3.481 (2) | 140 (1)
N2—H2A···S3vii | 0.88 (2) | 2.76 (2) | 3.481 (2) | 140 (1)
N2—H2B···S1 | 0.88 (2) | 2.61 (4) | 3.414 (3) | 153 (6)
N2—H2B···S2 | 0.88 (2) | 2.70 (6) | 3.250 (3) | 122 (5)

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Table 1. Hydrogen-bond geometry (Å, °)

D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A
N1—H1A⋯S1i | 0.86 (2) | 2.76 (4) | 3.491 (3) | 144 (6)
N1—H1B⋯S1ii | 0.88 (2) | 2.92 (5) | 3.607 (3) | 135 (5)
N1—H1B⋯S3 | 0.88 (2) | 2.87 (3) | 3.497 (3) | 129 (3)
N1—H1B⋯S3iii | 0.88 (2) | 2.87 (3) | 3.497 (3) | 129 (3)
N1—H1C⋯S3iv | 0.88 (2) | 2.76 (3) | 3.550 (3) | 150 (4)
N1—H1C⋯S3iv | 0.88 (2) | 2.76 (3) | 3.550 (3) | 150 (4)
N2—H2C⋯S3v | 0.88 (2) | 2.65 (3) | 3.405 (2) | 144 (4)
N2—H2A⋯S3vi | 0.88 (2) | 2.76 (2) | 3.481 (2) | 140 (1)
N2—H2A⋯S3vii | 0.88 (2) | 2.76 (2) | 3.481 (2) | 140 (1)
N2—H2B⋯S1 | 0.88 (2) | 2.61 (4) | 3.414 (3) | 153 (6)
N2—H2B⋯S2 | 0.88 (2) | 2.70 (6) | 3.250 (3) | 122 (5)

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

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