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The title compound, (C2H10N2)[MoO10S2], consists of [MoO2(SO4)2]2− chains linked to [H3NCH2CH2NH3]2+ ions, both of which have twofold symmetry. The MoVI 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012418/ob6247sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012418/ob6247Isup2.hkl
Contains datablock I

CCDC reference: 200552

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


Yellow Alert 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

Comment top

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 Mo0.5O(SO4). In the unit of [MoO2(SO4)2]2−, the MoVI 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 SO 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).

Experimental top

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.

Refinement top

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 (Rint = 0.034).

Computing details top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. Crystal structure of (I), in which MoO6 and SO4 are connected by sharing corners.
Ethylenediammonium disulfidodecamolybdate(VI) top
Crystal data top
(C2H10N2)[MoO10S2]F(000) = 760
Mr = 382.18Dx = 2.487 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 9.9305 (7) ÅCell parameters from 25 reflections
b = 13.6738 (9) Åθ = 12–18°
c = 8.7309 (4) ŵ = 1.75 mm1
β = 120.583 (3)°T = 293 K
V = 1020.63 (11) Å3Block, colourless
Z = 40.25 × 0.18 × 0.15 mm
Data collection top
Rigaku Weissenberg IP
diffractometer
1085 reflections with I > 2σ(I)
Radiation source: rotor targetRint = 0.000
Graphite monochromatorθmax = 27.5°, θmin = 2.8°
Detector resolution: none pixels mm-1h = 012
scintillation counter scansk = 017
1167 measured reflectionsl = 119
1167 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters not refined
S = 1.00 w = 1/[σ2(Fo2) + (0.033P)2 + 1.486P]
where P = (Fo2 + 2Fc2)/3
1167 reflections(Δ/σ)max = 0.001
79 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
(C2H10N2)[MoO10S2]V = 1020.63 (11) Å3
Mr = 382.18Z = 4
Monoclinic, C2/cMo Kα radiation
a = 9.9305 (7) ŵ = 1.75 mm1
b = 13.6738 (9) ÅT = 293 K
c = 8.7309 (4) Å0.25 × 0.18 × 0.15 mm
β = 120.583 (3)°
Data collection top
Rigaku Weissenberg IP
diffractometer
1085 reflections with I > 2σ(I)
1167 measured reflectionsRint = 0.000
1167 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.057H-atom parameters not refined
S = 1.00Δρmax = 0.46 e Å3
1167 reflectionsΔρmin = 0.66 e Å3
79 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. 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 (Å2) top
xyzUiso*/Ueq
Mo0.00000.442325 (18)0.25000.01508 (10)
S0.24150 (6)0.57377 (4)0.32552 (7)0.01383 (13)
O10.19081 (18)0.53232 (13)0.5089 (2)0.0218 (3)
O20.10199 (19)0.57069 (11)0.3039 (2)0.0189 (3)
O30.36749 (18)0.51359 (12)0.1978 (2)0.0212 (3)
O40.28798 (19)0.67537 (12)0.3193 (2)0.0259 (4)
O50.0857 (2)0.36541 (12)0.1724 (2)0.0250 (4)
N0.9510 (2)0.82136 (14)0.4320 (3)0.0250 (4)
C1.0503 (3)0.80767 (19)0.3512 (3)0.0262 (5)
H11.10560.74840.39180.034 (4)*
H21.10960.86890.38930.034 (4)*
H30.88520.78250.39430.034 (4)*
H40.91620.87940.41850.034 (4)*
H51.00240.81210.53840.034 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo0.01587 (15)0.01599 (15)0.01206 (14)0.0000.00615 (11)0.000
S0.0134 (3)0.0150 (2)0.0113 (2)0.00013 (18)0.0050 (2)0.00005 (17)
O10.0188 (8)0.0310 (9)0.0132 (7)0.0041 (7)0.0065 (6)0.0036 (6)
O20.0190 (8)0.0218 (8)0.0195 (8)0.0026 (6)0.0123 (7)0.0027 (6)
O30.0184 (8)0.0245 (8)0.0166 (8)0.0045 (6)0.0059 (7)0.0034 (6)
O40.0221 (8)0.0172 (8)0.0336 (9)0.0039 (6)0.0106 (7)0.0007 (7)
O50.0275 (9)0.0242 (9)0.0214 (8)0.0062 (7)0.0111 (7)0.0013 (7)
N0.0251 (10)0.0205 (10)0.0232 (10)0.0035 (8)0.0078 (8)0.0001 (8)
C0.0213 (11)0.0286 (12)0.0232 (12)0.0002 (9)0.0075 (10)0.0018 (9)
Geometric parameters (Å, º) top
Mo—O51.6959 (16)S—O11.5223 (16)
Mo—O5i1.6959 (16)O1—Moii2.0208 (15)
Mo—O1ii2.0208 (15)N—C1.487 (3)
Mo—O1iii2.0208 (15)N—H30.774
Mo—O2i2.1938 (16)N—H40.850
Mo—O22.1938 (15)N—H50.811
S—O31.4376 (15)C—Civ1.525 (5)
S—O41.4562 (16)C—H10.941
S—O21.4911 (16)C—H20.980
O5—Mo—O5i103.34 (12)O3—S—O1107.12 (10)
O5—Mo—O1ii97.32 (8)O4—S—O1108.87 (11)
O5i—Mo—O1ii94.90 (7)O2—S—O1106.94 (9)
O5—Mo—O1iii94.90 (7)S—O1—Moii131.66 (10)
O5i—Mo—O1iii97.32 (8)S—O2—Mo127.58 (9)
O1ii—Mo—O1iii160.24 (10)C—N—H3109.4
O5—Mo—O2i91.74 (7)C—N—H4111.9
O5i—Mo—O2i164.17 (7)H3—N—H4112.7
O1ii—Mo—O2i78.21 (6)C—N—H5110.0
O1iii—Mo—O2i85.98 (7)H3—N—H5106.4
O5—Mo—O2164.17 (7)H4—N—H5106.2
O5i—Mo—O291.74 (7)N—C—Civ110.4 (2)
O1ii—Mo—O285.98 (7)N—C—H1109.3
O1iii—Mo—O278.21 (6)Civ—C—H1110.43
O2i—Mo—O273.72 (8)N—C—H299.2
O3—S—O4112.52 (10)Civ—C—H2108.64
O3—S—O2112.55 (9)H1—C—H2118.2
O4—S—O2108.63 (10)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y+1, z+1; (iii) x, y+1, z1/2; (iv) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H3···O4v0.772.092.865 (3)174
N—H4···O3vi0.852.032.815 (3)153
N—H5···O4vii0.812.283.039 (3)157
N—H5···O5viii0.812.643.140 (3)122
N—H5···Svii0.812.953.537 (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.

Experimental details

Crystal data
Chemical formula(C2H10N2)[MoO10S2]
Mr382.18
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)9.9305 (7), 13.6738 (9), 8.7309 (4)
β (°) 120.583 (3)
V3)1020.63 (11)
Z4
Radiation typeMo Kα
µ (mm1)1.75
Crystal size (mm)0.25 × 0.18 × 0.15
Data collection
DiffractometerRigaku Weissenberg IP
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1167, 1167, 1085
Rint0.000
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.057, 1.00
No. of reflections1167
No. of parameters79
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.46, 0.66

Computer programs: TEXRAY (Molecular Structure Corporation, 1999), TEXRAY, TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
Mo—O51.6959 (16)S—O41.4562 (16)
Mo—O1i2.0208 (15)S—O21.4911 (16)
Mo—O22.1938 (15)S—O11.5223 (16)
S—O31.4376 (15)
O5—Mo—O5ii103.34 (12)O5—Mo—O2164.17 (7)
O5—Mo—O1i97.32 (8)O1i—Mo—O285.98 (7)
O5—Mo—O1iii94.90 (7)O1iii—Mo—O278.21 (6)
O1i—Mo—O1iii160.24 (10)O2ii—Mo—O273.72 (8)
O5—Mo—O2ii91.74 (7)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z+1/2; (iii) x, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H3···O4iv0.772.092.865 (3)174
N—H4···O3v0.852.032.815 (3)153
N—H5···O4vi0.812.283.039 (3)157
N—H5···O5vii0.812.643.140 (3)122
N—H5···Svi0.812.953.537 (3)131
Symmetry codes: (iv) x+1, y, z; (v) x+1/2, y+1/2, z+1/2; (vi) x+3/2, y+3/2, z+1/2; (vii) x+1, y+1, z+1/2.
 

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