Bis(isopropyl-ammonium) tetra-sulfido-molybdate(VI).

The title compound, (C(3)H(10)N)(2)[MoS(4)], was synthesized by passing a rapid stream of H(2)S into an aqueous isopropyl-amine solution of molybdic acid. The title compound is isotypic with the corresponding W analogue (C(3)H(10)N)(2)[WS(4)]; its structure consists of a slightly distorted tetra-hedral [MoS(4)](2-) dianion and two crystallographically independent isopropyl-ammonium cations, with all atoms located in general positions. The cations and anion are linked by weak N-H⋯S and C-H⋯S inter-actions, the strength and number of which can explain the observed Mo-S bond distances.

Related literature

Previous reports give details of the structural characterization of several organic ammonium tetra­sulfidomolybdates derived from chiral amines (Srinivasan, Naik et al., 2007 ▶), diamines (Srinivasan et al., 2001 ▶; Srinivasan, Dhuri et al., 2005 ▶; Srinivasan, Näther & Bensch 2005 ▶), triamines (Srinivasan, Dhuri et al., 2007 ▶), cyclic amines (Srinivasan, Näther & Bensch 2006 ▶), a tetra­amine (Srinivasan et al., 2004 ▶), a primary amine (Srinivasan, Näther, Naik & Bensch 2006 ▶) and a secondary amine (Srinivasan, Girkar & Raghavaiah 2007 ▶). The title compound is isotypic with the corresponding W analogue (C3H10N)2[WS4] (Srinivasan, Näther, Dhuri & Bensch 2006 ▶).

Experimental

Crystal data

(C3H10N)2[MoS4]

M = 344.42

Monoclinic,

a = 20.2640 (14) Å

b = 13.9118 (12) Å

c = 11.0933 (8) Å

β = 110.076 (8)°

V = 2937.3 (4) Å3

Z = 8

Mo Kα radiation

μ = 1.43 mm−1

T = 170 (2) K

0.13 × 0.1 × 0.08 mm

Data collection

Stoe IPDS 1 diffractometer

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998 ▶) T min = 0.756, T max = 0.830

10806 measured reflections

3134 independent reflections

2716 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.071

S = 1.03

3134 reflections

125 parameters

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.72 e Å−3

Data collection: IPDS Program Package (Stoe & Cie, 1998 ▶); cell refinement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063337/si2062sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063337/si2062Isup2.hkl

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

(C3H10N)2[MoS4]	F000 = 1408
Mr = 344.42	Dx = 1.558 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8000 reflections
a = 20.2640 (14) Å	θ = 12.5–28.0º
b = 13.9118 (12) Å	µ = 1.43 mm−1
c = 11.0933 (8) Å	T = 170 (2) K
β = 110.076 (8)º	Needle, red
V = 2937.3 (4) Å3	0.13 × 0.1 × 0.08 mm
Z = 8

STOE IPDS 1 diffractometer	3134 independent reflections
Radiation source: fine-focus sealed tube	2716 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.025
T = 170(2) K	θmax = 27.1º
Phi Scan scans	θmin = 2.4º
Absorption correction: numerical(X-SHAPE; Stoe & Cie, 1998)	h = −23→25
Tmin = 0.756, Tmax = 0.830	k = −17→17
10806 measured reflections	l = −13→14

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026	w = 1/[σ2(Fo2) + (0.0498P)2 + 0.8301P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.071	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.64 e Å−3
3134 reflections	Δρmin = −0.72 e Å−3
125 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00132 (18)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
Mo	0.277534 (8)	0.660872 (11)	0.763180 (16)	0.01395 (9)
S1	0.16255 (3)	0.66070 (4)	0.71330 (6)	0.02148 (14)
S2	0.32646 (3)	0.64606 (4)	0.96951 (5)	0.02172 (14)
S3	0.31057 (3)	0.79621 (4)	0.70333 (5)	0.02302 (14)
S4	0.31079 (3)	0.53985 (4)	0.66851 (6)	0.02458 (14)
N1	0.34948 (9)	0.61362 (13)	0.41696 (19)	0.0219 (4)
H1N1	0.3314	0.6038	0.4805	0.033*
H2N1	0.3318	0.5690	0.3541	0.033*
H3N1	0.3376	0.6735	0.3835	0.033*
C1	0.42792 (12)	0.60477 (18)	0.4708 (3)	0.0292 (6)
H1	0.4404	0.5389	0.5075	0.035*
C2	0.45832 (14)	0.61919 (19)	0.3658 (3)	0.0346 (6)
H2A	0.4421	0.5676	0.3023	0.052*
H2B	0.5097	0.6180	0.4027	0.052*
H2C	0.4429	0.6814	0.3241	0.052*
C3	0.45457 (18)	0.6778 (3)	0.5776 (3)	0.0557 (10)
H3A	0.4450	0.7428	0.5417	0.084*
H3B	0.5053	0.6695	0.6204	0.084*
H3C	0.4306	0.6684	0.6400	0.084*
N2	0.17411 (10)	0.40310 (14)	0.51513 (19)	0.0247 (4)
H1N2	0.1828	0.3534	0.5719	0.037*
H2N2	0.2062	0.4506	0.5478	0.037*
H3N2	0.1773	0.3820	0.4397	0.037*
C4	0.10154 (11)	0.44146 (15)	0.4922 (2)	0.0197 (4)
H4	0.0987	0.4646	0.5756	0.024*
C5	0.08879 (15)	0.52564 (17)	0.4005 (3)	0.0323 (6)
H5A	0.0933	0.5043	0.3195	0.048*
H5B	0.1234	0.5761	0.4386	0.048*
H5C	0.0414	0.5510	0.3842	0.048*
C6	0.04982 (13)	0.35982 (18)	0.4430 (3)	0.0307 (6)
H6A	0.0022	0.3828	0.4303	0.046*
H6B	0.0616	0.3073	0.5057	0.046*
H6C	0.0522	0.3366	0.3612	0.046*

	U11	U22	U33	U12	U13	U23
Mo	0.01492 (12)	0.01177 (12)	0.01591 (12)	−0.00135 (6)	0.00626 (8)	0.00189 (6)
S1	0.0147 (3)	0.0242 (3)	0.0243 (3)	−0.00166 (18)	0.0051 (2)	0.0059 (2)
S2	0.0215 (3)	0.0247 (3)	0.0167 (3)	−0.0033 (2)	0.0038 (2)	0.00321 (19)
S3	0.0266 (3)	0.0171 (3)	0.0275 (3)	−0.0053 (2)	0.0121 (2)	0.0054 (2)
S4	0.0337 (3)	0.0184 (3)	0.0257 (3)	0.0004 (2)	0.0154 (3)	−0.0027 (2)
N1	0.0182 (9)	0.0205 (9)	0.0258 (10)	−0.0003 (7)	0.0060 (8)	0.0033 (7)
C1	0.0181 (11)	0.0290 (12)	0.0371 (14)	0.0021 (9)	0.0049 (10)	0.0151 (10)
C2	0.0260 (12)	0.0357 (14)	0.0461 (16)	−0.0012 (10)	0.0174 (12)	−0.0046 (12)
C3	0.0378 (17)	0.103 (3)	0.0258 (14)	−0.0309 (17)	0.0098 (13)	−0.0058 (16)
N2	0.0184 (9)	0.0315 (10)	0.0242 (10)	−0.0023 (8)	0.0073 (8)	0.0044 (8)
C4	0.0190 (10)	0.0219 (10)	0.0211 (10)	−0.0015 (8)	0.0107 (9)	−0.0011 (8)
C5	0.0462 (15)	0.0203 (11)	0.0348 (13)	0.0051 (10)	0.0195 (12)	0.0037 (10)
C6	0.0205 (11)	0.0278 (12)	0.0444 (15)	−0.0041 (9)	0.0118 (11)	0.0000 (11)

Mo—S2	2.1695 (6)	C3—H3B	0.9800
Mo—S3	2.1769 (5)	C3—H3C	0.9800
Mo—S1	2.2023 (6)	N2—C4	1.502 (3)
Mo—S4	2.2085 (6)	N2—H1N2	0.9100
N1—C1	1.499 (3)	N2—H2N2	0.9100
N1—H1N1	0.9100	N2—H3N2	0.9100
N1—H2N1	0.9100	C4—C5	1.514 (3)
N1—H3N1	0.9100	C4—C6	1.514 (3)
C1—C2	1.506 (4)	C4—H4	1.0000
C1—C3	1.513 (4)	C5—H5A	0.9800
C1—H1	1.0000	C5—H5B	0.9800
C2—H2A	0.9800	C5—H5C	0.9800
C2—H2B	0.9800	C6—H6A	0.9800
C2—H2C	0.9800	C6—H6B	0.9800
C3—H3A	0.9800	C6—H6C	0.9800
S2—Mo—S3	109.08 (2)	C1—C3—H3C	109.5
S2—Mo—S1	109.02 (3)	H3A—C3—H3C	109.5
S3—Mo—S1	109.51 (2)	H3B—C3—H3C	109.5
S2—Mo—S4	109.01 (2)	C4—N2—H1N2	109.5
S3—Mo—S4	109.78 (2)	C4—N2—H2N2	109.5
S1—Mo—S4	110.42 (2)	H1N2—N2—H2N2	109.5
C1—N1—H1N1	109.5	C4—N2—H3N2	109.5
C1—N1—H2N1	109.5	H1N2—N2—H3N2	109.5
H1N1—N1—H2N1	109.5	H2N2—N2—H3N2	109.5
C1—N1—H3N1	109.5	N2—C4—C5	108.67 (19)
H1N1—N1—H3N1	109.5	N2—C4—C6	108.12 (18)
H2N1—N1—H3N1	109.5	C5—C4—C6	113.6 (2)
N1—C1—C2	109.9 (2)	N2—C4—H4	108.8
N1—C1—C3	107.5 (2)	C5—C4—H4	108.8
C2—C1—C3	112.7 (2)	C6—C4—H4	108.8
N1—C1—H1	108.9	C4—C5—H5A	109.5
C2—C1—H1	108.9	C4—C5—H5B	109.5
C3—C1—H1	108.9	H5A—C5—H5B	109.5
C1—C2—H2A	109.5	C4—C5—H5C	109.5
C1—C2—H2B	109.5	H5A—C5—H5C	109.5
H2A—C2—H2B	109.5	H5B—C5—H5C	109.5
C1—C2—H2C	109.5	C4—C6—H6A	109.5
H2A—C2—H2C	109.5	C4—C6—H6B	109.5
H2B—C2—H2C	109.5	H6A—C6—H6B	109.5
C1—C3—H3A	109.5	C4—C6—H6C	109.5
C1—C3—H3B	109.5	H6A—C6—H6C	109.5
H3A—C3—H3B	109.5	H6B—C6—H6C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S4	0.91	2.43	3.310 (2)	162
N1—H2N1···S4i	0.91	2.47	3.359 (2)	165
N1—H3N1···S1ii	0.91	2.54	3.4297 (19)	165
N1—H3N1···S3ii	0.91	2.85	3.3019 (19)	112
N2—H1N2···S3iii	0.91	2.58	3.376 (2)	147
N2—H1N2···S2iii	0.91	2.92	3.580 (2)	131
N2—H2N2···S4	0.91	2.43	3.309 (2)	164
N2—H3N2···S1i	0.91	2.50	3.393 (2)	169
C2—H2A···S4i	0.98	2.97	3.759 (3)	139
C5—H5B···S3ii	0.98	2.98	3.639 (6)	126

Mo—S2	2.1695 (6)
Mo—S3	2.1769 (5)
Mo—S1	2.2023 (6)
Mo—S4	2.2085 (6)

S2—Mo—S3	109.08 (2)
S2—Mo—S1	109.02 (3)
S3—Mo—S1	109.51 (2)
S2—Mo—S4	109.01 (2)
S3—Mo—S4	109.78 (2)
S1—Mo—S4	110.42 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S4	0.91	2.43	3.310 (2)	162
N1—H2N1⋯S4i	0.91	2.47	3.359 (2)	165
N1—H3N1⋯S1ii	0.91	2.54	3.4297 (19)	165
N1—H3N1⋯S3ii	0.91	2.85	3.3019 (19)	112
N2—H1N2⋯S3iii	0.91	2.58	3.376 (2)	147
N2—H1N2⋯S2iii	0.91	2.92	3.580 (2)	131
N2—H2N2⋯S4	0.91	2.43	3.309 (2)	164
N2—H3N2⋯S1i	0.91	2.50	3.393 (2)	169
C2—H2A⋯S4i	0.98	2.97	3.759 (3)	139
C5—H5B⋯S3ii	0.98	2.98	3.639 (6)	126

Symmetry codes: (i) ; (ii) ; (iii) .