Redetermination of diammonium thio­molybdate

Hill, B.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S1600536810003016

inorganic compounds

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Volume 66| Part 2| February 2010| Page i13

https://doi.org/10.1107/S1600536810003016

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Redetermination of diammonium thiomolybdate

Björn Hill,^a Hans-Wolfram Lerner ^a and Michael Bolte ^a ^*

^aInstitut 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

(Received 6 January 2010; accepted 25 January 2010; online 30 January 2010)

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, P n m a
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[F² > 2σ(F²)] = 0.022
wR(F²) = 0.060
S = 1.19
859 reflections
61 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.88 e Å⁻³

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⋯S3^iv	0.88 (2)	2.76 (3)	3.550 (3)	150 (4)
N1—H1C⋯S3^iv	0.88 (2)	2.76 (3)	3.550 (3)	150 (4)
N2—H2C⋯S3^v	0.88 (2)	2.65 (3)	3.405 (2)	144 (4)
N2—H2A⋯S3^vi	0.88 (2)	2.76 (2)	3.481 (2)	140 (1)
N2—H2A⋯S3^vii	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) x+1, y, z; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (v) -x, -y+1, -z+1; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810003016/fb2179sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810003016/fb2179Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

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.

diammonium thiomolybdate top

Crystal data top

(NH₄)₂[MoS₄]	F(000) = 512
M_r = 260.26	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0377P)² + 0.2462P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max < 0.001
859 reflections	Δρ_max = 0.51 e Å⁻³
61 parameters	Δρ_min = −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)

Crystal data top

(NH₄)₂[MoS₄]	V = 812.32 (7) Å³
M_r = 260.26	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 9.5867 (4) Å	µ = 2.55 mm⁻¹
b = 6.9451 (4) Å	T = 173 K
c = 12.2005 (5) Å	0.25 × 0.24 × 0.11 mm

Data collection top

Stoe IPDS II two-circle diffractometer	859 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	833 reflections with I > 2σ(I)
T_min = 0.569, T_max = 0.767	R_int = 0.072
14872 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	6 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	Δρ_max = 0.51 e Å⁻³
859 reflections	Δρ_min = −0.88 e Å⁻³
61 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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

Geometric parameters (Å, º) top

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)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

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···S3^iv	0.88 (2)	2.76 (3)	3.550 (3)	150 (4)
N1—H1C···S3^iv	0.88 (2)	2.76 (3)	3.550 (3)	150 (4)
N2—H2C···S3^v	0.88 (2)	2.65 (3)	3.405 (2)	144 (4)
N2—H2A···S3^vi	0.88 (2)	2.76 (2)	3.481 (2)	140 (1)
N2—H2A···S3^vii	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) x, −y+3/2, z; (ii) x+1, y, z; (iii) x+1/2, y, −z+1/2; (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.

Experimental details

Crystal data
Chemical formula	(NH₄)₂[MoS₄]
M_r	260.26
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	9.5867 (4), 6.9451 (4), 12.2005 (5)
V (Å³)	812.32 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.55
Crystal size (mm)	0.25 × 0.24 × 0.11

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.569, 0.767
No. of measured, independent and observed [I > 2σ(I)] reflections	14872, 859, 833
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.060, 1.19
No. of reflections	859
No. of parameters	61
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.88

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···S3^iv	0.883 (19)	2.76 (3)	3.550 (3)	150 (4)
N1—H1C···S3^iv	0.883 (19)	2.76 (3)	3.550 (3)	150 (4)
N2—H2C···S3^v	0.879 (19)	2.65 (3)	3.405 (2)	144 (4)
N2—H2A···S3^vi	0.88 (2)	2.762 (17)	3.481 (2)	140.3 (12)
N2—H2A···S3^vii	0.88 (2)	2.762 (17)	3.481 (2)	140.3 (12)
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) x+1, y, z; (ii) x+1/2, y, −z+1/2; (iii) 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.

References

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Herzog, S., Gustav, K. & Strähle, J. (1981). Handbuch der Präparativen Chemie, Vol. 3, edited by G. Brauer, pp. 1551–1552. Stuttgart: Ferdinand Enke Verlag. Google Scholar
Lapasset, J., Chezau, N. & Belougne, P. (1976). Acta Cryst. B32, 3087–3088. CrossRef CAS IUCr Journals Web of Science Google Scholar
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page i13

https://doi.org/10.1107/S1600536810003016

Open

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