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The structures of the title complexes, (C6H15N2)2[MoS4], (I), and (C6H16N2)[MoS4], (II), can be described as consisting of discrete tetra­hedral [MoS4]2- dianions that are linked to the organic ammonium cations via weak hydrogen-bonding inter­actions. The asymmetric unit of (I) consists of a single (±)-trans-2-amino­cyclo­hexyl­ammonium cation in a general position and an [MoS4]2- anion located on a twofold axis, while in (II), two crystallographically independent trans-cyclo­hexane-1,4-diammonium cations located on centres of inversion and one [MoS4]2- anion in a general position are found. The differing dispositions of the amine functionalities in the organic cations in the title complexes lead to different crystal packing arrangements in (I) and (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106001685/av1276sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106001685/av1276Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106001685/av1276IIsup3.hkl
Contains datablock II

CCDC references: 603206; 603207

Comment top

The chemistry of Mo/S compounds is currently a frontier area of research because of the importance of MoS2 in hydrodesulfurization (HDS) catalysis and in nanomaterials. The recent interest in the chemistry of tetrathiomolybdate can be evidenced by the use of (NH4)2[MoS4] as a precursor for the preparation of highly porous MoS2, which exhibits very high HDS activity (Skrabalak & Suslick, 2005). A few years ago we initiated a program aimed at the synthesis of novel precursors for sulfide materials, and as part of this research, we are investigating the synthesis, structural and thermal characterization of organic ammonium tetrathiomolybdates (Srinivasan et al., 2004). For the synthesis of organic ammonium tetrathiomolybdates we have developed a convenient and general method which involves the reaction of an organic amine with ammonium tetrathiomolybdate. In earlier work, we have demonstrated the structural flexibility of the [MoS4]2− ion as it can exist in a variety of structural environments (Ellermeier et al., 1999; Ellermeier & Bensch, 2001, 2002; Srinivasan et al., 2001, 2004; Srinivasan, Dhuri, Näther & Bensch, 2005; Srinivasan, Näther & Bensch, 2005). The tetrathiomolybdate complexes reported by us exhibit weak hydrogen-bonding interactions between the organic ammonium cation and the anion. These hydrogen-bonding interactions can be altered by changing the steric bulk and the number of potential hydrogen-bonding donors attached to the N atoms of the organic amines. In an earlier report we have shown that the compound (pipH2)[MoS4] (pip is piperazine) exhibits one of the longest known Mo—S bond distances [2.2114 (8) Å; Srinivasan et al., 2004]. A careful analysis of the structures indicated a good correlation between the number of S—H interactions and the observed Mo—S bond lengths. In the present work, we have employed two isomeric cyclohexanediamines, namely (±)trans-1,2-aminocyclohexanediamine [(±)trans-1,2-cn] and trans-1,4-cyclohexanediamine (trans-1,4-cn) as the source for the organic cation for the reactions with (NH4)2[MoS4] and have structurally characterized two new complexes [(±)trans-1,2-cnH]2[MoS4], (I), and (trans-1,4-cnH2)[MoS4], (II). The amines used here differ from the cyclic diamine pip in that the amine functional groups are outside the six-membered cyclohexane ring, whereas in pip, the amine N atoms form part of the six-membered ring. The title compounds are two additions to the growing list of structurally characterized tetrathiomolybdates. Interestingly the diamine (±)trans-1,2-cn is monoprotonated in (I), while the isomeric diamine trans-1,4-cn is diprotonated in (II).

The asymmetric unit of (I) consists of the monoprotonated cation of (±)trans-1,2-cn, which adopts the chair conformation, and the [MoS4]2− dianion (Fig. 1). The cation is located in a general position, while the anion is situated on a twofold axis. The MoS4 tetrahedron is slightly distorted, with S—Mo—S angles between 107.91 (3) and 110.85 (2)° (average 109.47°; Table 1). The Mo—S bond lengths range from 2.1751 (5) to 2.1876 (6) Å (Table 1) with a mean Mo—S distance of 2.1814 Å. Two of the bonds are shorter while the other two are longer than the average value of 2.1814 Å. The observed S···H distances are shorter than the sum of the van der Waals radii of S and H (Bondi 1964). All structural parameters of (I) are in good agreement with those reported for other compounds containing the [MoS4]2− moiety, such as (enH2)[MoS4] (en is ethylenediamine; Srinivasan et al., 2001) and (1,3-pnH2)[MoS4] (1,3-pn is 1,3-propanediamine; Srinivasan, Dhuri, Näther & Bensch, 2005). As a result of the hydrogen-bonding interactions, the cations and anions in (I) are organized in a rod-like manner along [100], with the ammonium groups of the organic cations always pointing towards the S atoms of the anion. Hence, the sequence along this direction is ···[MoS4]2−···trans-1,2-cnH ···trans-1,2-cnH···[MoS4]2−. The special arrangement of the constituents may be viewed as layers within the (001) plane. Along [010] and [001], the anions and cations each form individual stacks. Each anion is surrounded by six cations and four short S···H contacts ranging from 2.64 to 2.86 Å (Table 2) are observed. In addition, a very short N—H···N contact at 2.01 Å joins the cations to form pairs. The crystal packing of the resulting hydrogen-bonding network is shown in Fig. 2. The difference between the longest and shortest Mo—S bond, Δ, in (I) is 0.0125 Å and is comparable with the Δ value of 0.0111 Å observed for (enH2)[MoS4].

The structure of (II) consists of diprotonated trans-1,4-cn cations in a chair conformation and [MoS4]2− dianions (Fig. 3). There are two crystallographically independent (trans-1,4-cnH2)2+ cations and both are located on centres of inversion, while the anion is located in a general position. The MoS4 tetrahedron is slightly distorted, with S—Mo—S angles ranging from 107.08 (2) to 110.81 (3)° (average 109.46°). The Mo—S bond lengths range from 2.1774 (7) to 2.1955 (7) Å (Table 3), with a mean Mo—S distance of 2.1865 Å. The geometric parameters match well with those for (1,3-pnH2)[MoS4] and (1,4-bnH2)[MoS4] (1,4-bn is 1,4-butanediamine; Srinivasan, Näther & Bensch, 2005). Two of the Mo—S bonds are longer while the other two are shorter than the average of 2.1865 Å. In all, eight short intermolecular S···H contacts ranging from 2.47 Å to 2.81 Å are observed, and the S···H separations are shorter than the sum of the van der Waals radii (Bondi 1964). The N···S distances for one cation range from 3.3539 (19) to 3.581 (2) Å, with N—H···S angles between 121 and 167°, and for the second cation these distances are slightly shorter and lie between 3.287 (2) and 3.420 (2) Å, accompanied by N—H···S angles from 137 to 170°. Atom S4 has a single short contact, and atoms S1 and S3 have two short contacts each, while atom S2 is involved in three contacts. In general, the Mo—S bond lengths tend to be longer when the S···H contacts are shorter and the N—H···S angles are less acute (Table 4). As a result of the hydrogen-bonding interactions, alternating layers of cations and anions are formed in the crystallographic ac plane (Fig. 4). The value of Δ is 0.0181 Å and is comparable to the values of 0.0183 and 0.0243 Å observed for (1,3-pnH2)[MoS4] and (1,4-bnH2)[MoS4], respectively. Since the amine functionalities in the organic cations in (I) and (II) are differently disposed, they form different numbers of hydrogen bonds, which leads to different crystal packings. The very short N—H···N contact in (I) joins the cations to form pairs. In contrast, two adjacent organic cations in (II) are linked via N—H···S bonds through an intervening [MoS4]2− anion. The observed Δ values for (I) and (II) are in the range observed for tetrathiomolybdates derived from acyclic diamines such as en and 1,3-pn, whose Δ values (0.0111 and 0.0183 Å) are much smaller than the Δ value (0.0431 Å) observed for (pipH2)[MoS4].

Experimental top

Ammonium tetrathiomolybdate (260 mg, 1 mmol) was dissolved in distilled water (15–20 ml), a few drops of aqueous ammonia were added, and the mixture was filtered. Into the clear red filtrate, (±)trans-1,2-cn (0.5 ml) was added and the reaction mixture was left aside for crystallization. After a day, red crystals of (I) separated slowly. The crystals were filtered off, washed with ice-cold water (2 ml) followed by isopropyl alcohol (10 ml) and diethyl ether (10 ml), and air dried (yield 70%). The use of trans-1,4-cn (114 mg) instead of (±)trans-1,2-cn in the above reaction under identical conditions afforded (II) in 75% yield. Both compounds are air stable and were analysed satisfactorily.

Refinement top

H atoms were positioned with idealized geometry (C—H = 0.97 and 0.98 Å, and N—H = 0.89 Å) and refined using a riding model, with Uiso(H) fixed at 1.2Ueq(Cmethylene,Namine) and 1.5Ueq(Nammonium). In (I) the ammonium H atoms were allowed to rotate but not tip, and the amine H atoms were located in a difference map but their bond lengths were set to ideal values.

Computing details top

For both compounds, data collection: DIF4 (Stoe & Cie, 1998); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL.

Figures top
[Figure 1] Fig. 1. : The crystal structure of (I), with the atom labelling; displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, y, −z + 1/2.]
[Figure 2] Fig. 2. : The packing of (I), viewed along the b axis; hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. : The crystal structure of (II), with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (ii) −x + 2, −y + 1, −z + 2; (iii) −x + 1, −y + 1, −z + 1.
[Figure 4] Fig. 4. : The packing of (II), viewed along the a axis; hydrogen bonds are shown as dashed lines.
(I) Bis[(±)trans-2-aminocyclohexylammonium] tetrathiomolybdate(VI) top
Crystal data top
(C6H15N2)2[MoS4]F(000) = 944
Mr = 454.58Dx = 1.536 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 74 reflections
a = 19.279 (3) Åθ = 10–19°
b = 9.4502 (11) ŵ = 1.09 mm1
c = 11.3308 (16) ÅT = 293 K
β = 107.736 (12)°Block, red
V = 1966.2 (5) Å30.1 × 0.09 × 0.08 mm
Z = 4
Data collection top
Stoe AED-II four-circle
diffractometer
2357 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Graphite monochromatorθmax = 30.0°, θmin = 2.2°
ωθ scanh = 2725
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)
k = 132
Tmin = 0.889, Tmax = 0.909l = 015
3593 measured reflections4 standard reflections every 2h min
2863 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0257P)2 + 1.4007P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2863 reflectionsΔρmax = 0.45 e Å3
98 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00056 (14)
Crystal data top
(C6H15N2)2[MoS4]V = 1966.2 (5) Å3
Mr = 454.58Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.279 (3) ŵ = 1.09 mm1
b = 9.4502 (11) ÅT = 293 K
c = 11.3308 (16) Å0.1 × 0.09 × 0.08 mm
β = 107.736 (12)°
Data collection top
Stoe AED-II four-circle
diffractometer
2357 reflections with I > 2σ(I)
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)
Rint = 0.017
Tmin = 0.889, Tmax = 0.9094 standard reflections every 2h min
3593 measured reflections intensity decay: none
2863 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.04Δρmax = 0.45 e Å3
2863 reflectionsΔρmin = 0.32 e Å3
98 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
xyzUiso*/Ueq
Mo10.50000.82240 (2)0.25000.02376 (7)
S10.55341 (3)0.68778 (6)0.14826 (5)0.04393 (13)
S20.42090 (3)0.95861 (6)0.11991 (4)0.03713 (12)
N10.55381 (8)0.21460 (17)0.14460 (14)0.0309 (3)
H1N10.54820.19010.06640.046*
H2N10.51410.25960.14890.046*
H3N10.56070.13730.19170.046*
N20.57529 (10)0.3769 (2)0.36481 (16)0.0415 (4)
H1N20.58580.38720.44640.062*
H2N20.56270.45840.32470.062*
C10.61856 (9)0.31029 (19)0.18984 (15)0.0276 (3)
H10.60540.40370.15210.033*
C20.63856 (10)0.3260 (2)0.33060 (16)0.0322 (4)
H20.65070.23160.36680.039*
C30.70664 (11)0.4177 (2)0.37752 (19)0.0410 (5)
H3A0.69580.51260.34450.049*
H3B0.72040.42370.46720.049*
C40.76993 (12)0.3584 (3)0.3397 (2)0.0460 (5)
H4A0.81180.42030.36930.055*
H4B0.78320.26610.37730.055*
C50.74959 (12)0.3453 (3)0.2005 (2)0.0493 (6)
H5A0.78980.30360.17790.059*
H5B0.74030.43850.16320.059*
C60.68190 (11)0.2533 (3)0.1510 (2)0.0436 (5)
H6A0.66830.25010.06120.052*
H6B0.69280.15760.18190.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.02964 (11)0.02047 (10)0.02143 (10)0.0000.00816 (7)0.000
S10.0601 (3)0.0411 (3)0.0377 (3)0.0161 (3)0.0254 (2)0.0011 (2)
S20.0380 (3)0.0320 (2)0.0331 (2)0.00617 (19)0.00159 (19)0.00118 (19)
N10.0311 (7)0.0337 (8)0.0269 (7)0.0045 (6)0.0074 (6)0.0032 (6)
N20.0503 (10)0.0479 (10)0.0302 (8)0.0091 (8)0.0180 (7)0.0070 (8)
C10.0306 (8)0.0267 (8)0.0251 (7)0.0039 (7)0.0078 (6)0.0002 (7)
C20.0383 (9)0.0307 (9)0.0255 (8)0.0053 (8)0.0066 (7)0.0005 (7)
C30.0460 (11)0.0398 (11)0.0331 (9)0.0122 (9)0.0058 (8)0.0050 (8)
C40.0346 (10)0.0440 (12)0.0510 (12)0.0086 (9)0.0005 (9)0.0051 (10)
C50.0347 (10)0.0609 (16)0.0542 (13)0.0104 (10)0.0167 (9)0.0069 (11)
C60.0364 (10)0.0510 (13)0.0455 (11)0.0052 (10)0.0157 (9)0.0143 (10)
Geometric parameters (Å, º) top
Mo1—S1i2.1751 (5)C2—C31.527 (3)
Mo1—S12.1751 (5)C2—H20.9800
Mo1—S2i2.1876 (6)C3—C41.518 (3)
Mo1—S22.1876 (5)C3—H3A0.9700
N1—C11.500 (2)C3—H3B0.9700
N1—H1N10.8900C4—C51.511 (3)
N1—H2N10.8900C4—H4A0.9700
N1—H3N10.8900C4—H4B0.9700
N2—C21.469 (3)C5—C61.525 (3)
N2—H1N20.8900C5—H5A0.9700
N2—H2N20.8900C5—H5B0.9700
C1—C61.518 (3)C6—H6A0.9700
C1—C21.530 (2)C6—H6B0.9700
C1—H10.9800
S1i—Mo1—S1108.41 (3)C1—C2—H2107.5
S1i—Mo1—S2i109.41 (2)C4—C3—C2111.82 (18)
S1—Mo1—S2i110.85 (2)C4—C3—H3A109.3
S1i—Mo1—S2110.85 (2)C2—C3—H3A109.3
S1—Mo1—S2109.41 (2)C4—C3—H3B109.3
S2i—Mo1—S2107.91 (3)C2—C3—H3B109.3
C1—N1—H1N1109.5H3A—C3—H3B107.9
C1—N1—H2N1109.5C5—C4—C3110.48 (18)
H1N1—N1—H2N1109.5C5—C4—H4A109.6
C1—N1—H3N1109.5C3—C4—H4A109.6
H1N1—N1—H3N1109.5C5—C4—H4B109.6
H2N1—N1—H3N1109.5C3—C4—H4B109.6
C2—N2—H1N2111.4H4A—C4—H4B108.1
C2—N2—H2N2105.5C4—C5—C6110.59 (19)
H1N2—N2—H2N2112.1C4—C5—H5A109.5
N1—C1—C6110.27 (15)C6—C5—H5A109.5
N1—C1—C2109.52 (14)C4—C5—H5B109.5
C6—C1—C2111.56 (16)C6—C5—H5B109.5
N1—C1—H1108.5H5A—C5—H5B108.1
C6—C1—H1108.5C1—C6—C5111.42 (18)
C2—C1—H1108.5C1—C6—H6A109.3
N2—C2—C3114.66 (17)C5—C6—H6A109.3
N2—C2—C1109.94 (15)C1—C6—H6B109.3
C3—C2—C1109.58 (15)C5—C6—H6B109.3
N2—C2—H2107.5H6A—C6—H6B108.0
C3—C2—H2107.5
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S2ii0.892.753.5762 (16)155
N1—H1N1···S1ii0.892.863.4577 (17)126
N1—H2N1···N2i0.892.012.898 (2)171
N1—H3N1···S2iii0.892.663.5238 (17)164
N2—H2N2···S10.892.923.768 (2)161
N2—H1N2···S1iv0.892.643.4193 (18)146
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1, y+1, z; (iii) x+1, y1, z+1/2; (iv) x, y+1, z+1/2.
(II) trans-cyclohexane-1,4-diammonium tetrathiomolybdate(VI) top
Crystal data top
(C6H16N2)[MoS4]Z = 2
Mr = 340.39F(000) = 344
Triclinic, P1Dx = 1.759 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0045 (12) ÅCell parameters from 84 reflections
b = 9.6833 (18) Åθ = 20–38.5°
c = 10.530 (2) ŵ = 1.63 mm1
α = 108.621 (10)°T = 293 K
β = 92.564 (10)°Block, red
γ = 106.24 (1)°0.11 × 0.09 × 0.07 mm
V = 642.7 (2) Å3
Data collection top
Stoe AED-II four-circle
diffractometer
3747 independent reflections
Radiation source: fine-focus sealed tube2951 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ωθ scansθmax = 30.0°, θmin = 3.1°
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)
h = 19
Tmin = 0.832, Tmax = 0.887k = 1313
4363 measured reflectionsl = 1414
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0205P)2 + 0.1519P]
where P = (Fo2 + 2Fc2)/3
3747 reflections(Δ/σ)max = 0.001
118 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
(C6H16N2)[MoS4]γ = 106.24 (1)°
Mr = 340.39V = 642.7 (2) Å3
Triclinic, P1Z = 2
a = 7.0045 (12) ÅMo Kα radiation
b = 9.6833 (18) ŵ = 1.63 mm1
c = 10.530 (2) ÅT = 293 K
α = 108.621 (10)°0.11 × 0.09 × 0.07 mm
β = 92.564 (10)°
Data collection top
Stoe AED-II four-circle
diffractometer
3747 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)
2951 reflections with I > 2σ(I)
Tmin = 0.832, Tmax = 0.887Rint = 0.016
4363 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.053H-atom parameters constrained
S = 1.02Δρmax = 0.39 e Å3
3747 reflectionsΔρmin = 0.45 e Å3
118 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
xyzUiso*/Ueq
Mo10.24692 (3)1.041268 (18)0.777136 (17)0.02342 (5)
S10.04174 (8)1.14316 (6)0.70573 (5)0.03018 (11)
S20.52881 (8)1.10993 (7)0.69860 (6)0.03471 (12)
S30.11410 (9)0.79079 (6)0.69828 (6)0.03552 (12)
S40.30328 (9)1.12716 (7)0.99767 (5)0.03840 (13)
N10.8349 (3)1.24124 (18)0.99412 (18)0.0309 (4)
H1N10.88491.20041.04720.046*
H2N10.89701.23210.92140.046*
H3N10.70391.19240.96830.046*
C10.8669 (3)1.4085 (2)1.0711 (2)0.0295 (4)
H10.79321.41531.14870.035*
C20.7838 (3)1.4826 (2)0.9836 (2)0.0331 (4)
H2A0.77491.58051.04140.040*
H2B0.64871.41810.94070.040*
C30.9102 (3)1.5083 (2)0.8743 (2)0.0336 (4)
H3A0.85861.56780.83080.040*
H3B0.89661.40980.80590.040*
N20.6899 (3)0.81815 (19)0.55111 (19)0.0351 (4)
H1N20.70070.84620.47840.053*
H2N20.80970.81940.58420.053*
H3N20.64520.88310.61380.053*
C110.5455 (3)0.6599 (2)0.5123 (2)0.0278 (4)
H110.41340.66100.47860.033*
C120.6147 (4)0.5502 (2)0.4000 (2)0.0352 (5)
H12A0.74980.55380.42930.042*
H12B0.61750.58090.32080.042*
C130.4728 (3)0.3871 (2)0.3633 (2)0.0317 (4)
H13A0.34110.38120.32480.038*
H13B0.52330.31700.29580.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.02290 (8)0.02057 (7)0.02548 (8)0.00591 (6)0.00234 (6)0.00709 (5)
S10.0275 (2)0.0276 (2)0.0380 (3)0.01124 (19)0.0045 (2)0.0124 (2)
S20.0247 (2)0.0409 (3)0.0386 (3)0.0098 (2)0.0061 (2)0.0139 (2)
S30.0404 (3)0.0215 (2)0.0407 (3)0.0066 (2)0.0021 (2)0.0092 (2)
S40.0470 (3)0.0379 (3)0.0257 (2)0.0112 (3)0.0021 (2)0.0072 (2)
N10.0320 (9)0.0229 (8)0.0366 (9)0.0045 (7)0.0029 (7)0.0123 (7)
C10.0345 (11)0.0240 (9)0.0292 (9)0.0084 (8)0.0068 (8)0.0084 (7)
C20.0269 (10)0.0243 (9)0.0463 (12)0.0090 (8)0.0010 (9)0.0098 (8)
C30.0396 (12)0.0257 (9)0.0330 (10)0.0076 (8)0.0065 (9)0.0105 (8)
N20.0411 (10)0.0228 (8)0.0363 (9)0.0036 (7)0.0005 (8)0.0096 (7)
C110.0297 (10)0.0208 (8)0.0287 (9)0.0038 (7)0.0002 (8)0.0071 (7)
C120.0420 (12)0.0293 (10)0.0301 (10)0.0049 (9)0.0125 (9)0.0089 (8)
C130.0391 (11)0.0255 (9)0.0256 (9)0.0061 (8)0.0066 (8)0.0055 (7)
Geometric parameters (Å, º) top
Mo1—S42.1774 (7)C3—H3A0.9700
Mo1—S12.1851 (6)C3—H3B0.9700
Mo1—S22.1881 (7)N2—C111.495 (2)
Mo1—S32.1955 (7)N2—H1N20.8900
N1—C11.507 (2)N2—H2N20.8900
N1—H1N10.8900N2—H3N20.8900
N1—H2N10.8900C11—C13ii1.517 (3)
N1—H3N10.8900C11—C121.517 (3)
C1—C21.520 (3)C11—H110.9800
C1—C3i1.529 (3)C12—C131.526 (3)
C1—H10.9800C12—H12A0.9700
C2—C31.524 (3)C12—H12B0.9700
C2—H2A0.9700C13—C11ii1.517 (3)
C2—H2B0.9700C13—H13A0.9700
C3—C1i1.529 (3)C13—H13B0.9700
S4—Mo1—S1110.12 (3)C2—C3—H3B108.9
S4—Mo1—S2109.43 (3)C1i—C3—H3B108.9
S1—Mo1—S2107.08 (2)H3A—C3—H3B107.7
S4—Mo1—S3110.81 (3)C11—N2—H1N2109.5
S1—Mo1—S3108.91 (3)C11—N2—H2N2109.5
S2—Mo1—S3110.42 (3)H1N2—N2—H2N2109.5
C1—N1—H1N1109.5C11—N2—H3N2109.5
C1—N1—H2N1109.5H1N2—N2—H3N2109.5
H1N1—N1—H2N1109.5H2N2—N2—H3N2109.5
C1—N1—H3N1109.5N2—C11—C13ii109.23 (16)
H1N1—N1—H3N1109.5N2—C11—C12109.74 (17)
H2N1—N1—H3N1109.5C13ii—C11—C12112.12 (17)
N1—C1—C2111.10 (16)N2—C11—H11108.6
N1—C1—C3i110.18 (17)C13ii—C11—H11108.6
C2—C1—C3i111.68 (17)C12—C11—H11108.6
N1—C1—H1107.9C11—C12—C13110.20 (17)
C2—C1—H1107.9C11—C12—H12A109.6
C3i—C1—H1107.9C13—C12—H12A109.6
C1—C2—C3113.67 (18)C11—C12—H12B109.6
C1—C2—H2A108.8C13—C12—H12B109.6
C3—C2—H2A108.8H12A—C12—H12B108.1
C1—C2—H2B108.8C11ii—C13—C12110.70 (16)
C3—C2—H2B108.8C11ii—C13—H13A109.5
H2A—C2—H2B107.7C12—C13—H13A109.5
C2—C3—C1i113.27 (17)C11ii—C13—H13B109.5
C2—C3—H3A108.9C12—C13—H13B109.5
C1i—C3—H3A108.9H13A—C13—H13B108.1
Symmetry codes: (i) x+2, y+3, z+2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S3iii0.892.653.3639 (19)138
N1—H1N1···S4iii0.892.943.4559 (18)118
N1—H2N1···S1iv0.892.523.398 (2)167
N1—H3N1···S40.892.753.581 (2)155
N1—H3N1···S20.892.813.3539 (19)121
N2—H1N2···S2v0.892.623.339 (2)139
N2—H1N2···S1v0.892.713.420 (2)137
N2—H2N2···S3iv0.892.533.405 (2)170
N2—H3N2···S20.892.473.287 (2)153
Symmetry codes: (iii) x+1, y+2, z+2; (iv) x+1, y, z; (v) x+1, y+2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula(C6H15N2)2[MoS4](C6H16N2)[MoS4]
Mr454.58340.39
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)293293
a, b, c (Å)19.279 (3), 9.4502 (11), 11.3308 (16)7.0045 (12), 9.6833 (18), 10.530 (2)
α, β, γ (°)90, 107.736 (12), 90108.621 (10), 92.564 (10), 106.24 (1)
V3)1966.2 (5)642.7 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)1.091.63
Crystal size (mm)0.1 × 0.09 × 0.080.11 × 0.09 × 0.07
Data collection
DiffractometerStoe AED-II four-circle
diffractometer
Stoe AED-II four-circle
diffractometer
Absorption correctionNumerical
(X-SHAPE; Stoe & Cie, 1998)
Numerical
(X-SHAPE; Stoe & Cie, 1998)
Tmin, Tmax0.889, 0.9090.832, 0.887
No. of measured, independent and
observed [I > 2σ(I)] reflections
3593, 2863, 2357 4363, 3747, 2951
Rint0.0170.016
(sin θ/λ)max1)0.7030.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.061, 1.04 0.022, 0.053, 1.02
No. of reflections28633747
No. of parameters98118
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.320.39, 0.45

Computer programs: DIF4 (Stoe & Cie, 1998), DIF4, REDU4 (Stoe & Cie, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), CIFTAB in SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Mo1—S1i2.1751 (5)C1—C61.518 (3)
Mo1—S12.1751 (5)C1—C21.530 (2)
Mo1—S2i2.1876 (6)C2—C31.527 (3)
Mo1—S22.1876 (5)C3—C41.518 (3)
N1—C11.500 (2)C4—C51.511 (3)
N2—C21.469 (3)C5—C61.525 (3)
S1i—Mo1—S1108.41 (3)C6—C1—C2111.56 (16)
S1i—Mo1—S2i109.41 (2)N2—C2—C3114.66 (17)
S1—Mo1—S2i110.85 (2)N2—C2—C1109.94 (15)
S1i—Mo1—S2110.85 (2)C3—C2—C1109.58 (15)
S1—Mo1—S2109.41 (2)C4—C3—C2111.82 (18)
S2i—Mo1—S2107.91 (3)C5—C4—C3110.48 (18)
N1—C1—C6110.27 (15)C4—C5—C6110.59 (19)
N1—C1—C2109.52 (14)C1—C6—C5111.42 (18)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S2ii0.892.753.5762 (16)155.4
N1—H1N1···S1ii0.892.863.4577 (17)125.8
N1—H2N1···N2i0.892.012.898 (2)171.3
N1—H3N1···S2iii0.892.663.5238 (17)163.9
N2—H2N2···S10.892.923.768 (2)160.7
N2—H1N2···S1iv0.892.643.4193 (18)146.2
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1, y+1, z; (iii) x+1, y1, z+1/2; (iv) x, y+1, z+1/2.
Selected geometric parameters (Å, º) for (II) top
Mo1—S42.1774 (7)C2—C31.524 (3)
Mo1—S12.1851 (6)C3—C1i1.529 (3)
Mo1—S22.1881 (7)N2—C111.495 (2)
Mo1—S32.1955 (7)C11—C13ii1.517 (3)
N1—C11.507 (2)C11—C121.517 (3)
C1—C21.520 (3)C12—C131.526 (3)
C1—C3i1.529 (3)C13—C11ii1.517 (3)
S4—Mo1—S1110.12 (3)C2—C1—C3i111.68 (17)
S4—Mo1—S2109.43 (3)C1—C2—C3113.67 (18)
S1—Mo1—S2107.08 (2)C2—C3—C1i113.27 (17)
S4—Mo1—S3110.81 (3)N2—C11—C13ii109.23 (16)
S1—Mo1—S3108.91 (3)N2—C11—C12109.74 (17)
S2—Mo1—S3110.42 (3)C13ii—C11—C12112.12 (17)
N1—C1—C2111.10 (16)C11—C12—C13110.20 (17)
N1—C1—C3i110.18 (17)C11ii—C13—C12110.70 (16)
Symmetry codes: (i) x+2, y+3, z+2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···S3iii0.892.653.3639 (19)137.5
N1—H1N1···S4iii0.892.943.4559 (18)118.2
N1—H2N1···S1iv0.892.523.398 (2)167.2
N1—H3N1···S40.892.753.581 (2)155.3
N1—H3N1···S20.892.813.3539 (19)120.7
N2—H1N2···S2v0.892.623.339 (2)138.7
N2—H1N2···S1v0.892.713.420 (2)137.2
N2—H2N2···S3iv0.892.533.405 (2)169.7
N2—H3N2···S20.892.473.287 (2)152.8
Symmetry codes: (iii) x+1, y+2, z+2; (iv) x+1, y, z; (v) x+1, y+2, z+1.
 

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