metal-organic compounds
Bis[benzyl(methyl)ammonium] tetrathiomolybdate(VI)
aDepartment of Chemistry, Goa University, Goa 403 206, India
*Correspondence e-mail: srini@unigoa.ac.in
The title compound, (C8H12N)2[MoS4], was synthesized by the aqueous reaction of ammonium tetrathiomolybdate with benzyl(methyl)amine in a 1:2 molar ratio. The structure consists of a slightly distorted tetrahedral [MoS4]2− dianion and two crystallographically independent benzyl(methyl)ammonium cations, with all atoms located in general positions. The cations and anions are linked by weak N—H⋯S and C—H⋯S interactions, 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 tetrathiomolybdates derived from organic diamines (Srinivasan et al., 2001; Srinivasan, Dhuri et al., 2005; Srinivasan, Näther & Bensch, 2005), chiral amines (Srinivasan, Naik et al., 2007), triamines (Srinivasan, Dhuri et al., 2007), cyclic amines (Srinivasan, Näther & Bensch, 2006), a tetraamine (Srinivasan et al., 2004) and a primary amine (Srinivasan, Näther et al., 2006).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg 1999); software used to prepare material for publication: SHELXTL.
Supporting information
Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807049562/nc2064sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807049562/nc2064Isup2.hkl
(NH4)2[MoS4] (520 mg, 2 mmol) was dissolved in water (15 ml) containing a few drops of liquor ammonia. To this mixture N-methyl-1-phenylmethanamine (1 ml) was added and the reaction mixture filtered and left in the refrigerator for crystallization. After two days small needles of the title compound separated. The crystals were filtered, washed with ice-cold water (2 ml), followed by 2-propanol (10 ml) and diethyl ether (10 ml) and dried. Yield: 60%.
The H atoms were positioned with idealized geometry (C—H = 0.93 (aromatic), O.96 (methyl) and 0.97 (benzilic) Å and N—H = 0.90 Å) and were refined using a riding model, with Uiso(H) fixed at 1.5Ueq(CH3) and 1.2Ueq(NH2, benzilic, aromatic).
As part of an ongoing research programme, we are investigating the synthesis and structural characterization of organic ammonium tetrathiometalates of the group VI metals Mo and W (Srinivasan, Naik et al., 2007). In earlier work we have structurally characterized several [MoS4]2- compounds derived from organic diamines (Srinivasan et al., 2001; Srinivasan, Dhuri et al., 2005; Srinivasan, Näther & Bensch, 2005), chiral amines (Srinivasan, Naik et al., 2007) triamines (Srinivasan, Dhuri et al., 2007), cyclic amines (Srinivasan, Näther & Bensch, 2006), tetraamine (Srinivasan et al., 2004) and primary amine (Srinivasan, Näther et al., 2006). All the organic ammonium tetrathiomolybdates exhibit several weak hydrogen bonding interactions between the organic cations and [MoS4]2- anions. We have also shown that in some organic [MoS4]2- compounds the organic amines are partially protonated (Srinivasan, Dhuri et al., 2007). The secondary amine N-methyl-1-phenylmethanamine used for the synthesis of the title compound (I) is an isomer of the chiral primary amine 1-phenylethanamine used in our earlier report (Srinivasan, Naik et al., 2007).
The structure of (I) consists of discrete tetrahedral [MoS4]2- ions and two crystallographically independent benzyl(methyl)ammonium cations (Fig. 1) with all atoms located in general positions. The [MoS4] tetrahedron is slightly distorted with S—Mo—S angles between 109.01 (6) and 110.28 (7)° (Table 1). The Mo—S bond lengths range from 2.1582 (13) to 2.1908 (14) Å with an average value of 2.1744 Å which is comparable to the bond lengths observed in the related chiral [MoS4]2- compound synthesized from the isomeric chiral primary amine (Srinivasan, Naik et al., 2007). The Mo1—S1 and Mo1—S2 bond distances are indistinguishable within experimental error as also the Mo1—S3 and Mo1—S4 bonds. The weak H-bonding interactions between the cations and anions can explain the observed short and long Mo—S bond distances. A scrutiny of the structure reveals that the organic cations and tetrathiomolybdate anions are linked with the aid of several N—H···S and C—H···S hydrogen bonding interactions. Thus each [MoS4]2- is hydrogen bonded to five different organic cations with the aid of six N—H···S bonds and two weak C—H···S interactions (Fig. 2). An examination of the surroundings of the cations reveals that one organic cation (N1) is H-bonded to two different [MoS4]2- ions while the second organic cation (N2) is surrounded by three different [MoS4]2- ions (Table 2). One H atom on each N atom functions as a singly shared donor with the other functioning as a bifurcated donor. A benzilic H atom from each unique cation is involved in C—H···S interaction. S4 atom which makes the longest Mo—S bond at 2.1908 (14) Å is involved in three N—H···S bonds, two of which are singly shared. S4 also makes the shortest singly shared N—H···S bond at 2.37 Å, which can explain the elongation of this bond. In contrast, S1 atom involved in the shortest Mo—S bond makes a bifurcated N—H···S bond at a longer S···H distance accompanied by a small NH—S angle. S1 also makes a very weak C—H···S contact. The observed difference Δ between the longest and the shortest Mo—S bond of 0.0326 Å in (I) is shorter than the Δ value of 0.0422 Å in the tetrathiomolybdate compound containing the R-form of the monoprotonated isomeric chiral primary amine 1-phenylethanamine (Srinivasan, Naik et al., 2007).
Previous reports give details of the structural characterization of several organic ammonium tetrathiomolybdates derived from organic diamines (Srinivasan et al., 2001; Srinivasan, Dhuri et al., 2005; Srinivasan, Näther & Bensch, 2005), chiral amines (Srinivasan, Naik et al., 2007), triamines (Srinivasan, Dhuri et al., 2007), cyclic amines (Srinivasan, Näther & Bensch, 2006), a tetraamine (Srinivasan et al., 2004) and a primary amine (Srinivasan, Näther et al., 2006).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: DIAMOND (Brandenburg 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
Fig. 1. The crystal structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A view of the surroundings of the [MoS4]2- anion showing its linking to five different organic cations with the aid of six N—H···S and two C—H···S interactions. N—H···S and C—H···S interactions are shown as dashed lines and dotted lines respectively. Symmetry codes: (i) x + 1, y, z (ii) -x + 1, -y + 1, -z + 1; (iii) -x, -y + 1, z - 1 |
(C8H12N)2[MoS4] | Z = 2 |
Mr = 468.55 | F(000) = 480 |
Triclinic, P1 | Dx = 1.480 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1857 (12) Å | Cell parameters from 4674 reflections |
b = 10.7376 (18) Å | θ = 2.9–25.9° |
c = 14.881 (2) Å | µ = 1.02 mm−1 |
α = 110.811 (2)° | T = 298 K |
β = 90.608 (3)° | Thin nedle, red |
γ = 100.504 (3)° | 0.42 × 0.06 × 0.02 mm |
V = 1051.7 (3) Å3 |
Bruker SMART APEX CCD diffractometer | 3639 independent reflections |
Radiation source: fine-focus sealed tube | 3015 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
Tmin = 0.901, Tmax = 0.976 | k = −12→11 |
7363 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0387P)2 + 0.9757P] where P = (Fo2 + 2Fc2)/3 |
3639 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
(C8H12N)2[MoS4] | γ = 100.504 (3)° |
Mr = 468.55 | V = 1051.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1857 (12) Å | Mo Kα radiation |
b = 10.7376 (18) Å | µ = 1.02 mm−1 |
c = 14.881 (2) Å | T = 298 K |
α = 110.811 (2)° | 0.42 × 0.06 × 0.02 mm |
β = 90.608 (3)° |
Bruker SMART APEX CCD diffractometer | 3639 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3015 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.976 | Rint = 0.035 |
7363 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.68 e Å−3 |
3639 reflections | Δρmin = −0.51 e Å−3 |
210 parameters |
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 | ||
C1 | 0.5906 (7) | 0.4755 (6) | 0.1061 (3) | 0.0448 (13) | |
C2 | 0.7203 (8) | 0.4231 (7) | 0.0439 (4) | 0.0575 (15) | |
H2 | 0.8260 | 0.4816 | 0.0361 | 0.069* | |
C3 | 0.6971 (11) | 0.2869 (8) | −0.0068 (4) | 0.0714 (19) | |
H3 | 0.7854 | 0.2531 | −0.0493 | 0.086* | |
C4 | 0.5436 (12) | 0.2006 (7) | 0.0055 (5) | 0.077 (2) | |
H4 | 0.5279 | 0.1075 | −0.0283 | 0.092* | |
C5 | 0.4126 (10) | 0.2507 (7) | 0.0674 (5) | 0.075 (2) | |
H5 | 0.3075 | 0.1918 | 0.0753 | 0.090* | |
C6 | 0.4366 (8) | 0.3879 (7) | 0.1177 (4) | 0.0592 (16) | |
H6 | 0.3478 | 0.4217 | 0.1600 | 0.071* | |
C7 | 0.6150 (8) | 0.6270 (6) | 0.1585 (4) | 0.0510 (14) | |
H7A | 0.7090 | 0.6734 | 0.1287 | 0.061* | |
H7B | 0.4957 | 0.6545 | 0.1521 | 0.061* | |
C8 | 0.6958 (8) | 0.8155 (5) | 0.3161 (4) | 0.0573 (15) | |
H8A | 0.7718 | 0.8658 | 0.2829 | 0.086* | |
H8B | 0.7565 | 0.8372 | 0.3791 | 0.086* | |
H8C | 0.5728 | 0.8392 | 0.3223 | 0.086* | |
C9 | 0.1099 (7) | 0.1225 (5) | 0.2958 (4) | 0.0401 (12) | |
C10 | 0.0895 (8) | 0.0024 (6) | 0.2183 (4) | 0.0528 (14) | |
H10 | 0.1464 | −0.0669 | 0.2221 | 0.063* | |
C11 | −0.0153 (9) | −0.0155 (7) | 0.1348 (5) | 0.0677 (18) | |
H11 | −0.0323 | −0.0979 | 0.0831 | 0.081* | |
C12 | −0.0937 (9) | 0.0877 (7) | 0.1282 (4) | 0.0682 (18) | |
H12 | −0.1609 | 0.0765 | 0.0712 | 0.082* | |
C13 | −0.0739 (8) | 0.2073 (6) | 0.2050 (4) | 0.0583 (16) | |
H13 | −0.1285 | 0.2773 | 0.2006 | 0.070* | |
C14 | 0.0269 (8) | 0.2240 (5) | 0.2887 (4) | 0.0494 (14) | |
H14 | 0.0389 | 0.3052 | 0.3411 | 0.059* | |
C15 | 0.2213 (8) | 0.1417 (6) | 0.3879 (4) | 0.0511 (14) | |
H15A | 0.1415 | 0.1651 | 0.4412 | 0.061* | |
H15B | 0.2585 | 0.0571 | 0.3826 | 0.061* | |
C16 | 0.5316 (8) | 0.2289 (7) | 0.3349 (4) | 0.0640 (17) | |
H16A | 0.5654 | 0.1422 | 0.3224 | 0.096* | |
H16B | 0.6432 | 0.2994 | 0.3579 | 0.096* | |
H16C | 0.4767 | 0.2309 | 0.2764 | 0.096* | |
Mo1 | 0.16547 (6) | 0.66475 (4) | 0.38214 (3) | 0.03200 (14) | |
N1 | 0.6748 (6) | 0.6684 (4) | 0.2609 (3) | 0.0443 (10) | |
H1A | 0.7867 | 0.6441 | 0.2662 | 0.053* | |
H1B | 0.5892 | 0.6228 | 0.2875 | 0.053* | |
N2 | 0.3937 (6) | 0.2507 (5) | 0.4080 (3) | 0.0563 (13) | |
H2A | 0.3565 | 0.3291 | 0.4152 | 0.068* | |
H2B | 0.4529 | 0.2612 | 0.4645 | 0.068* | |
S1 | −0.10243 (18) | 0.57324 (14) | 0.41788 (10) | 0.0458 (3) | |
S2 | 0.2566 (2) | 0.86869 (15) | 0.48604 (12) | 0.0619 (4) | |
S3 | 0.1321 (2) | 0.66870 (17) | 0.23687 (10) | 0.0552 (4) | |
S4 | 0.37925 (19) | 0.54486 (14) | 0.38649 (10) | 0.0466 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.045 (3) | 0.060 (4) | 0.033 (3) | 0.018 (3) | −0.001 (2) | 0.018 (3) |
C2 | 0.056 (4) | 0.068 (4) | 0.051 (3) | 0.018 (3) | 0.006 (3) | 0.023 (3) |
C3 | 0.087 (5) | 0.083 (5) | 0.050 (4) | 0.043 (4) | 0.008 (4) | 0.020 (4) |
C4 | 0.118 (7) | 0.055 (4) | 0.058 (4) | 0.030 (5) | −0.016 (4) | 0.014 (4) |
C5 | 0.080 (5) | 0.067 (5) | 0.064 (4) | −0.006 (4) | −0.009 (4) | 0.017 (4) |
C6 | 0.051 (4) | 0.070 (5) | 0.049 (3) | 0.008 (3) | 0.008 (3) | 0.014 (3) |
C7 | 0.052 (4) | 0.061 (4) | 0.047 (3) | 0.015 (3) | 0.001 (3) | 0.026 (3) |
C8 | 0.058 (4) | 0.044 (4) | 0.065 (4) | 0.008 (3) | 0.010 (3) | 0.014 (3) |
C9 | 0.034 (3) | 0.044 (3) | 0.043 (3) | 0.007 (2) | 0.008 (2) | 0.019 (3) |
C10 | 0.052 (4) | 0.038 (3) | 0.065 (4) | 0.013 (3) | 0.005 (3) | 0.013 (3) |
C11 | 0.069 (4) | 0.055 (4) | 0.056 (4) | 0.010 (3) | −0.004 (3) | −0.006 (3) |
C12 | 0.061 (4) | 0.089 (5) | 0.049 (4) | 0.019 (4) | −0.008 (3) | 0.017 (4) |
C13 | 0.046 (4) | 0.063 (4) | 0.073 (4) | 0.022 (3) | 0.003 (3) | 0.028 (4) |
C14 | 0.047 (3) | 0.038 (3) | 0.056 (3) | 0.009 (3) | −0.002 (3) | 0.008 (3) |
C15 | 0.058 (4) | 0.054 (4) | 0.045 (3) | 0.012 (3) | 0.007 (3) | 0.022 (3) |
C16 | 0.041 (3) | 0.083 (5) | 0.070 (4) | 0.009 (3) | 0.004 (3) | 0.031 (4) |
Mo1 | 0.0265 (2) | 0.0333 (3) | 0.0379 (2) | 0.00674 (17) | 0.00297 (17) | 0.01470 (19) |
N1 | 0.041 (3) | 0.044 (3) | 0.047 (3) | 0.009 (2) | 0.002 (2) | 0.014 (2) |
N2 | 0.051 (3) | 0.068 (3) | 0.046 (3) | 0.017 (3) | −0.005 (2) | 0.015 (2) |
S1 | 0.0340 (7) | 0.0519 (9) | 0.0577 (8) | 0.0090 (6) | 0.0102 (6) | 0.0271 (7) |
S2 | 0.0690 (11) | 0.0358 (8) | 0.0698 (10) | 0.0050 (8) | −0.0012 (8) | 0.0087 (8) |
S3 | 0.0500 (9) | 0.0818 (12) | 0.0498 (8) | 0.0243 (8) | 0.0121 (7) | 0.0375 (8) |
S4 | 0.0360 (8) | 0.0492 (9) | 0.0594 (9) | 0.0137 (6) | 0.0021 (6) | 0.0230 (7) |
C1—C2 | 1.371 (7) | C10—H10 | 0.9300 |
C1—C6 | 1.372 (7) | C11—C12 | 1.363 (9) |
C1—C7 | 1.509 (7) | C11—H11 | 0.9300 |
C2—C3 | 1.364 (8) | C12—C13 | 1.365 (8) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.364 (9) | C13—C14 | 1.372 (7) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.370 (9) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—N2 | 1.487 (7) |
C5—C6 | 1.372 (8) | C15—H15A | 0.9700 |
C5—H5 | 0.9300 | C15—H15B | 0.9700 |
C6—H6 | 0.9300 | C16—N2 | 1.465 (7) |
C7—N1 | 1.463 (6) | C16—H16A | 0.9600 |
C7—H7A | 0.9700 | C16—H16B | 0.9600 |
C7—H7B | 0.9700 | C16—H16C | 0.9600 |
C8—N1 | 1.477 (6) | Mo1—S1 | 2.1582 (13) |
C8—H8A | 0.9600 | Mo1—S2 | 2.1597 (16) |
C8—H8B | 0.9600 | Mo1—S3 | 2.1888 (14) |
C8—H8C | 0.9600 | Mo1—S4 | 2.1908 (14) |
C9—C14 | 1.369 (7) | N1—H1A | 0.9000 |
C9—C10 | 1.372 (7) | N1—H1B | 0.9000 |
C9—C15 | 1.509 (7) | N2—H2A | 0.9000 |
C10—C11 | 1.380 (8) | N2—H2B | 0.9000 |
C2—C1—C6 | 118.7 (6) | C11—C12—C13 | 120.2 (6) |
C2—C1—C7 | 120.4 (5) | C11—C12—H12 | 119.9 |
C6—C1—C7 | 120.9 (5) | C13—C12—H12 | 119.9 |
C3—C2—C1 | 121.3 (6) | C12—C13—C14 | 119.8 (6) |
C3—C2—H2 | 119.4 | C12—C13—H13 | 120.1 |
C1—C2—H2 | 119.4 | C14—C13—H13 | 120.1 |
C4—C3—C2 | 119.6 (6) | C9—C14—C13 | 120.7 (5) |
C4—C3—H3 | 120.2 | C9—C14—H14 | 119.6 |
C2—C3—H3 | 120.2 | C13—C14—H14 | 119.6 |
C3—C4—C5 | 120.1 (7) | N2—C15—C9 | 111.2 (4) |
C3—C4—H4 | 119.9 | N2—C15—H15A | 109.4 |
C5—C4—H4 | 119.9 | C9—C15—H15A | 109.4 |
C4—C5—C6 | 119.9 (7) | N2—C15—H15B | 109.4 |
C4—C5—H5 | 120.0 | C9—C15—H15B | 109.4 |
C6—C5—H5 | 120.0 | H15A—C15—H15B | 108.0 |
C5—C6—C1 | 120.4 (6) | N2—C16—H16A | 109.5 |
C5—C6—H6 | 119.8 | N2—C16—H16B | 109.5 |
C1—C6—H6 | 119.8 | H16A—C16—H16B | 109.5 |
N1—C7—C1 | 112.2 (4) | N2—C16—H16C | 109.5 |
N1—C7—H7A | 109.2 | H16A—C16—H16C | 109.5 |
C1—C7—H7A | 109.2 | H16B—C16—H16C | 109.5 |
N1—C7—H7B | 109.2 | S1—Mo1—S2 | 109.43 (6) |
C1—C7—H7B | 109.2 | S1—Mo1—S3 | 109.32 (6) |
H7A—C7—H7B | 107.9 | S2—Mo1—S3 | 110.28 (7) |
N1—C8—H8A | 109.5 | S1—Mo1—S4 | 109.47 (5) |
N1—C8—H8B | 109.5 | S2—Mo1—S4 | 109.01 (6) |
H8A—C8—H8B | 109.5 | S3—Mo1—S4 | 109.31 (6) |
N1—C8—H8C | 109.5 | C7—N1—C8 | 114.4 (4) |
H8A—C8—H8C | 109.5 | C7—N1—H1A | 108.7 |
H8B—C8—H8C | 109.5 | C8—N1—H1A | 108.7 |
C14—C9—C10 | 119.2 (5) | C7—N1—H1B | 108.7 |
C14—C9—C15 | 120.5 (5) | C8—N1—H1B | 108.7 |
C10—C9—C15 | 120.3 (5) | H1A—N1—H1B | 107.6 |
C9—C10—C11 | 120.1 (5) | C16—N2—C15 | 116.1 (5) |
C9—C10—H10 | 119.9 | C16—N2—H2A | 108.3 |
C11—C10—H10 | 119.9 | C15—N2—H2A | 108.3 |
C12—C11—C10 | 119.9 (6) | C16—N2—H2B | 108.3 |
C12—C11—H11 | 120.0 | C15—N2—H2B | 108.3 |
C10—C11—H11 | 120.0 | H2A—N2—H2B | 107.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S3i | 0.90 | 2.51 | 3.308 (4) | 149 |
N1—H1A···S1i | 0.90 | 2.78 | 3.358 (4) | 124 |
N1—H1B···S4 | 0.90 | 2.37 | 3.253 (4) | 168 |
N2—H2A···S4 | 0.90 | 2.48 | 3.305 (5) | 153 |
N2—H2B···S4ii | 0.90 | 2.54 | 3.264 (5) | 138 |
N2—H2B···S2ii | 0.90 | 2.93 | 3.602 (5) | 132 |
C7—H7B···S3 | 0.97 | 2.92 | 3.727 (6) | 141 |
C15—H15A···S1iii | 0.97 | 2.91 | 3.629 (6) | 132 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C8H12N)2[MoS4] |
Mr | 468.55 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.1857 (12), 10.7376 (18), 14.881 (2) |
α, β, γ (°) | 110.811 (2), 90.608 (3), 100.504 (3) |
V (Å3) | 1051.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.42 × 0.06 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.901, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7363, 3639, 3015 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.100, 1.05 |
No. of reflections | 3639 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.51 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001), DIAMOND (Brandenburg 1999).
Mo1—S1 | 2.1582 (13) | Mo1—S3 | 2.1888 (14) |
Mo1—S2 | 2.1597 (16) | Mo1—S4 | 2.1908 (14) |
S1—Mo1—S2 | 109.43 (6) | S1—Mo1—S4 | 109.47 (5) |
S1—Mo1—S3 | 109.32 (6) | S2—Mo1—S4 | 109.01 (6) |
S2—Mo1—S3 | 110.28 (7) | S3—Mo1—S4 | 109.31 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S3i | 0.90 | 2.51 | 3.308 (4) | 149 |
N1—H1A···S1i | 0.90 | 2.78 | 3.358 (4) | 124 |
N1—H1B···S4 | 0.90 | 2.37 | 3.253 (4) | 168 |
N2—H2A···S4 | 0.90 | 2.48 | 3.305 (5) | 153 |
N2—H2B···S4ii | 0.90 | 2.54 | 3.264 (5) | 138 |
N2—H2B···S2ii | 0.90 | 2.93 | 3.602 (5) | 132 |
C7—H7B···S3 | 0.97 | 2.92 | 3.727 (6) | 141 |
C15—H15A···S1iii | 0.97 | 2.91 | 3.629 (6) | 132 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
Acknowledgements
This work was supported by the Department of Science and Technology (DST), New Delhi, under grant No. SR/S1/IC-41/2003. BRS thanks Dr Samar K. Das, School of Chemistry, University of Hyderabad, for the X-ray intensity data collection.
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As part of an ongoing research programme, we are investigating the synthesis and structural characterization of organic ammonium tetrathiometalates of the group VI metals Mo and W (Srinivasan, Naik et al., 2007). In earlier work we have structurally characterized several [MoS4]2- compounds derived from organic diamines (Srinivasan et al., 2001; Srinivasan, Dhuri et al., 2005; Srinivasan, Näther & Bensch, 2005), chiral amines (Srinivasan, Naik et al., 2007) triamines (Srinivasan, Dhuri et al., 2007), cyclic amines (Srinivasan, Näther & Bensch, 2006), tetraamine (Srinivasan et al., 2004) and primary amine (Srinivasan, Näther et al., 2006). All the organic ammonium tetrathiomolybdates exhibit several weak hydrogen bonding interactions between the organic cations and [MoS4]2- anions. We have also shown that in some organic [MoS4]2- compounds the organic amines are partially protonated (Srinivasan, Dhuri et al., 2007). The secondary amine N-methyl-1-phenylmethanamine used for the synthesis of the title compound (I) is an isomer of the chiral primary amine 1-phenylethanamine used in our earlier report (Srinivasan, Naik et al., 2007).
The structure of (I) consists of discrete tetrahedral [MoS4]2- ions and two crystallographically independent benzyl(methyl)ammonium cations (Fig. 1) with all atoms located in general positions. The [MoS4] tetrahedron is slightly distorted with S—Mo—S angles between 109.01 (6) and 110.28 (7)° (Table 1). The Mo—S bond lengths range from 2.1582 (13) to 2.1908 (14) Å with an average value of 2.1744 Å which is comparable to the bond lengths observed in the related chiral [MoS4]2- compound synthesized from the isomeric chiral primary amine (Srinivasan, Naik et al., 2007). The Mo1—S1 and Mo1—S2 bond distances are indistinguishable within experimental error as also the Mo1—S3 and Mo1—S4 bonds. The weak H-bonding interactions between the cations and anions can explain the observed short and long Mo—S bond distances. A scrutiny of the structure reveals that the organic cations and tetrathiomolybdate anions are linked with the aid of several N—H···S and C—H···S hydrogen bonding interactions. Thus each [MoS4]2- is hydrogen bonded to five different organic cations with the aid of six N—H···S bonds and two weak C—H···S interactions (Fig. 2). An examination of the surroundings of the cations reveals that one organic cation (N1) is H-bonded to two different [MoS4]2- ions while the second organic cation (N2) is surrounded by three different [MoS4]2- ions (Table 2). One H atom on each N atom functions as a singly shared donor with the other functioning as a bifurcated donor. A benzilic H atom from each unique cation is involved in C—H···S interaction. S4 atom which makes the longest Mo—S bond at 2.1908 (14) Å is involved in three N—H···S bonds, two of which are singly shared. S4 also makes the shortest singly shared N—H···S bond at 2.37 Å, which can explain the elongation of this bond. In contrast, S1 atom involved in the shortest Mo—S bond makes a bifurcated N—H···S bond at a longer S···H distance accompanied by a small NH—S angle. S1 also makes a very weak C—H···S contact. The observed difference Δ between the longest and the shortest Mo—S bond of 0.0326 Å in (I) is shorter than the Δ value of 0.0422 Å in the tetrathiomolybdate compound containing the R-form of the monoprotonated isomeric chiral primary amine 1-phenylethanamine (Srinivasan, Naik et al., 2007).