Ethyl­enedi­ammonium disulfidodecamolybdate(VI)

The title compound, (C₂H₁₀N₂)[MoO₁₀S₂], consists of [MoO₂(SO₄)₂]²⁻ chains linked to [H₃NCH₂CH₂NH₃]²⁺ ions, both of which have twofold symmetry. The Mo^VI atom is octahedrally surrounded by four sulfate O atoms and two terminal O atoms. The μ₂-O atom connects the MoO₆ octahedra and the SO₄ tetrahedra to form a ring, which extends to form a one-dimensional chain along c.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.020
• wR factor = 0.057
• Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
          Absorption corrections should be applied.
          Tmin and Tmax expected:      0.692     0.769
          RT(exp) =      1.112


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

Polyoxometalates are of continuing interest in important areas of chemistry like a diverse compositional range and considerable structural versatility (Pope, 1983; Pope et al., 1991, 1994), as well as important magnetic (Clemente-Juan et al., 1999), optical and catalytic properties (Pope, 1983; Pope et al., 1991, 1994). Previous studies revealed that sulfate ions react with molybdate to produce many heteropolyions, such as [S₂Mo₁₈O₆₂]⁴⁻ and [S₂Mo₅O₂₃]⁴⁻ (Hori et al., 1989, 1992), α-[H₃S₂Mo₁₈O₆₂]⁵⁻ (Ralf Neier et al., 1995) and [SMo₁₂O₄₀]²⁻ (Hori et al., 1996). However, [MoO₂(SO₄)₂]²⁻ connected with organic cation is rare.

In the title compound, (I), the cation [MoO₂(SO₄)₂]²⁻ is constructed from MoO₆ octahedra and SO₄ tetrahedra, which are joined together via sharing corners into a one-dimensional chain along c (Fig. 1). The cations [H₃N(CH₂)₂NH₃]²⁺ are located between the chains (Fig. 2). The Mo atom lie on twofold axis, and the repetitive sequence of the chain in (I) is Mo_0.5O(SO₄). In the unit of [MoO₂(SO₄)₂]²⁻, the Mo^VI atom is in distorted octahedral coordination, with two short Mo—O5 terminal bonds in cis-configuration, and with two long Mo—O2 bonds in trans-position to the short ones, and with two Mo—O1 bonds of intermediate length, all four bridging O atoms belonging to different sulfate groups (Fig. 1 and Table 1). In SO₄²⁻ tetrahedron, the S═O bond lengths of the terminal O3 and O4 atoms are shorter than those of O1 and O2 atoms, which are coordinated to the Mo. There is extensive hydrogen bonding between the N—H groups from the complex cations and the oxygen atoms or the S atoms from the inorganic anion chains (Table 2).

S2. Experimental

Aqueous solutions of Na₂MoO₄·2H₂O (0.6 g, 1.24 mol l⁻¹) and Ti(SO₄)₂ (0.4 g, 0.83 mol l⁻¹), H₂SO₄ (1.8 ml, 98%), and H₂N(CH₂)₂NH₂ (0.3 ml, chemical purity) were mixed together and stirred with a magnetic bar for a few minutes, then sealed in a stainless steel (25 ml) Teflon-lined vessel under autogenous pressure. The reactant was heated at 393 K for 4 d and cooled at a rate of 279 K h⁻¹ to room temperature. The resulting product was filtered off, washed with water, and dried in air, and well shaped colourless crystals of (I) were obtained.

S3. Refinement

All H atoms were positioned geometrically and fixed. Information of the range of hkl for the original data set are missing, because the authors received only the averaged data and the original data in the machine has been deleted (R_int = 0.034).

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the structure of (I), showing 50% displacement ellipsoids for non-H atoms. A part of the [MoO2(SO4)2]^2− chain is shown with a cation.
	Fig. 2. Crystal structure of (I), in which MoO6 and SO4 are connected by sharing corners.

Ethylenediammonium disulfidodecamolybdate(VI)

Crystal data

(C2H10N2)[MoO10S2]	F(000) = 760
Mr = 382.18	Dx = 2.487 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9305 (7) Å	Cell parameters from 25 reflections
b = 13.6738 (9) Å	θ = 12–18°
c = 8.7309 (4) Å	µ = 1.75 mm^−1
β = 120.583 (3)°	T = 293 K
V = 1020.63 (11) Å^3	Block, colourless
Z = 4	0.25 × 0.18 × 0.15 mm

Data collection

Rigaku Weissenberg IP diffractometer	1085 reflections with I > 2σ(I)
Radiation source: rotor target	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
Detector resolution: none pixels mm^-1	h = 0→12
scintillation counter scans	k = 0→17
1167 measured reflections	l = −11→9
1167 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H-atom parameters not refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.033P)^2 + 1.486P] where P = (Fo^2 + 2Fc^2)/3
1167 reflections	(Δ/σ)max = 0.001
79 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

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. Molecule crystallized in the monoclinic system; space group C2/c from the systematic absences. 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 (Ų)

	x	y	z	Uiso*/Ueq
Mo	0.0000	0.442325 (18)	0.2500	0.01508 (10)
S	−0.24150 (6)	0.57377 (4)	0.32552 (7)	0.01383 (13)
O1	−0.19081 (18)	0.53232 (13)	0.5089 (2)	0.0218 (3)
O2	−0.10199 (19)	0.57069 (11)	0.3039 (2)	0.0189 (3)
O3	−0.36749 (18)	0.51359 (12)	0.1978 (2)	0.0212 (3)
O4	−0.28798 (19)	0.67537 (12)	0.3193 (2)	0.0259 (4)
O5	0.0857 (2)	0.36541 (12)	0.1724 (2)	0.0250 (4)
N	0.9510 (2)	0.82136 (14)	0.4320 (3)	0.0250 (4)
C	1.0503 (3)	0.80767 (19)	0.3512 (3)	0.0262 (5)
H1	1.1056	0.7484	0.3918	0.034 (4)*
H2	1.1096	0.8689	0.3893	0.034 (4)*
H3	0.8852	0.7825	0.3943	0.034 (4)*
H4	0.9162	0.8794	0.4185	0.034 (4)*
H5	1.0024	0.8121	0.5384	0.034 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo	0.01587 (15)	0.01599 (15)	0.01206 (14)	0.000	0.00615 (11)	0.000
S	0.0134 (3)	0.0150 (2)	0.0113 (2)	0.00013 (18)	0.0050 (2)	−0.00005 (17)
O1	0.0188 (8)	0.0310 (9)	0.0132 (7)	−0.0041 (7)	0.0065 (6)	0.0036 (6)
O2	0.0190 (8)	0.0218 (8)	0.0195 (8)	−0.0026 (6)	0.0123 (7)	−0.0027 (6)
O3	0.0184 (8)	0.0245 (8)	0.0166 (8)	−0.0045 (6)	0.0059 (7)	−0.0034 (6)
O4	0.0221 (8)	0.0172 (8)	0.0336 (9)	0.0039 (6)	0.0106 (7)	−0.0007 (7)
O5	0.0275 (9)	0.0242 (9)	0.0214 (8)	0.0062 (7)	0.0111 (7)	−0.0013 (7)
N	0.0251 (10)	0.0205 (10)	0.0232 (10)	−0.0035 (8)	0.0078 (8)	0.0001 (8)
C	0.0213 (11)	0.0286 (12)	0.0232 (12)	−0.0002 (9)	0.0075 (10)	0.0018 (9)

Geometric parameters (Å, º)

Mo—O5	1.6959 (16)	S—O1	1.5223 (16)
Mo—O5^i	1.6959 (16)	O1—Mo^ii	2.0208 (15)
Mo—O1^ii	2.0208 (15)	N—C	1.487 (3)
Mo—O1^iii	2.0208 (15)	N—H3	0.774
Mo—O2^i	2.1938 (16)	N—H4	0.850
Mo—O2	2.1938 (15)	N—H5	0.811
S—O3	1.4376 (15)	C—C^iv	1.525 (5)
S—O4	1.4562 (16)	C—H1	0.941
S—O2	1.4911 (16)	C—H2	0.980
O5—Mo—O5^i	103.34 (12)	O3—S—O1	107.12 (10)
O5—Mo—O1^ii	97.32 (8)	O4—S—O1	108.87 (11)
O5^i—Mo—O1^ii	94.90 (7)	O2—S—O1	106.94 (9)
O5—Mo—O1^iii	94.90 (7)	S—O1—Mo^ii	131.66 (10)
O5^i—Mo—O1^iii	97.32 (8)	S—O2—Mo	127.58 (9)
O1^ii—Mo—O1^iii	160.24 (10)	C—N—H3	109.4
O5—Mo—O2^i	91.74 (7)	C—N—H4	111.9
O5^i—Mo—O2^i	164.17 (7)	H3—N—H4	112.7
O1^ii—Mo—O2^i	78.21 (6)	C—N—H5	110.0
O1^iii—Mo—O2^i	85.98 (7)	H3—N—H5	106.4
O5—Mo—O2	164.17 (7)	H4—N—H5	106.2
O5^i—Mo—O2	91.74 (7)	N—C—C^iv	110.4 (2)
O1^ii—Mo—O2	85.98 (7)	N—C—H1	109.3
O1^iii—Mo—O2	78.21 (6)	C^iv—C—H1	110.43
O2^i—Mo—O2	73.72 (8)	N—C—H2	99.2
O3—S—O4	112.52 (10)	C^iv—C—H2	108.64
O3—S—O2	112.55 (9)	H1—C—H2	118.2
O4—S—O2	108.63 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H3···O4^v	0.77	2.09	2.865 (3)	174
N—H4···O3^vi	0.85	2.03	2.815 (3)	153
N—H5···O4^vii	0.81	2.28	3.039 (3)	157
N—H5···O5^viii	0.81	2.64	3.140 (3)	122
N—H5···S^vii	0.81	2.95	3.537 (3)	131

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