Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058746/nc2077sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058746/nc2077Isup2.hkl |
CCDC reference: 672719
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.018
- wR factor = 0.043
- Data-to-parameter ratio = 19.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for W1 PLAT480_ALERT_4_C Long H...A H-Bond Reported H2B .. S2 .. 2.92 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B .. S3 .. 2.93 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H15A .. S1 .. 2.95 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
(NH4)2[WS4] (348 mg, 1 mmol) was dissolved in water (20 ml) containing a few drops of liquor ammonia. To this mixture benzyl(methyl)amine (0.6 ml) was added and the reaction mixture filtered and left in the refrigerator for crystallization. After two days crystals of the title compound separated. The product was filtered, washed with ice-cold water (2 ml), followed by 2-propanol (10 ml) and diethyl ether (10 ml) and dried. Yield: 71%.
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).
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.
(C8H12N)2[WS4] | Z = 2 |
Mr = 556.46 | F(000) = 544 |
Triclinic, P1 | Dx = 1.741 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2178 (12) Å | Cell parameters from 9395 reflections |
b = 10.7965 (19) Å | θ = 2.9–26.1° |
c = 14.900 (3) Å | µ = 5.83 mm−1 |
α = 111.057 (2)° | T = 298 K |
β = 90.539 (2)° | Plate, yellow |
γ = 100.584 (2)° | 0.28 × 0.18 × 0.06 mm |
V = 1061.6 (3) Å3 |
Bruker SMART Apex CCD diffractometer | 4189 independent reflections |
Radiation source: fine-focus sealed tube | 3976 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
phi and ω scans | θmax = 26.1°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
Tmin = 0.292, Tmax = 0.711 | k = −13→13 |
11136 measured reflections | l = −18→18 |
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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0224P)2 + 0.0392P] where P = (Fo2 + 2Fc2)/3 |
4189 reflections | (Δ/σ)max = 0.002 |
210 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
(C8H12N)2[WS4] | γ = 100.584 (2)° |
Mr = 556.46 | V = 1061.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2178 (12) Å | Mo Kα radiation |
b = 10.7965 (19) Å | µ = 5.83 mm−1 |
c = 14.900 (3) Å | T = 298 K |
α = 111.057 (2)° | 0.28 × 0.18 × 0.06 mm |
β = 90.539 (2)° |
Bruker SMART Apex CCD diffractometer | 4189 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3976 reflections with I > 2σ(I) |
Tmin = 0.292, Tmax = 0.711 | Rint = 0.021 |
11136 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 0 restraints |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.61 e Å−3 |
4189 reflections | Δρmin = −0.44 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 | 0.5898 (4) | 0.4749 (3) | 0.1050 (2) | 0.0463 (7) | |
C2 | 0.7217 (5) | 0.4217 (4) | 0.0434 (3) | 0.0606 (9) | |
H2 | 0.8281 | 0.4794 | 0.0360 | 0.073* | |
C3 | 0.6967 (6) | 0.2846 (4) | −0.0070 (3) | 0.0747 (12) | |
H3 | 0.7846 | 0.2501 | −0.0493 | 0.090* | |
C4 | 0.5427 (7) | 0.1990 (4) | 0.0051 (3) | 0.0756 (11) | |
H4 | 0.5261 | 0.1062 | −0.0287 | 0.091* | |
C5 | 0.4126 (6) | 0.2505 (4) | 0.0671 (3) | 0.0753 (11) | |
H5 | 0.3089 | 0.1919 | 0.0758 | 0.090* | |
C6 | 0.4338 (5) | 0.3877 (4) | 0.1165 (2) | 0.0613 (9) | |
H6 | 0.3437 | 0.4217 | 0.1575 | 0.074* | |
C7 | 0.6132 (5) | 0.6251 (3) | 0.1563 (2) | 0.0519 (8) | |
H7A | 0.7056 | 0.6709 | 0.1258 | 0.062* | |
H7B | 0.4938 | 0.6516 | 0.1502 | 0.062* | |
C8 | 0.6955 (5) | 0.8154 (3) | 0.3147 (2) | 0.0583 (8) | |
H8A | 0.7747 | 0.8652 | 0.2826 | 0.087* | |
H8B | 0.7516 | 0.8373 | 0.3786 | 0.087* | |
H8C | 0.5731 | 0.8389 | 0.3186 | 0.087* | |
C9 | 0.1084 (4) | 0.1210 (3) | 0.2963 (2) | 0.0394 (6) | |
C10 | 0.0900 (5) | 0.0025 (3) | 0.2165 (2) | 0.0540 (8) | |
H10 | 0.1483 | −0.0665 | 0.2186 | 0.065* | |
C11 | −0.0147 (5) | −0.0135 (4) | 0.1340 (3) | 0.0688 (10) | |
H11 | −0.0303 | −0.0946 | 0.0813 | 0.083* | |
C12 | −0.0958 (5) | 0.0888 (4) | 0.1290 (3) | 0.0674 (10) | |
H12 | −0.1651 | 0.0777 | 0.0727 | 0.081* | |
C13 | −0.0749 (5) | 0.2080 (4) | 0.2071 (3) | 0.0594 (9) | |
H13 | −0.1279 | 0.2784 | 0.2034 | 0.071* | |
C14 | 0.0242 (4) | 0.2233 (3) | 0.2908 (2) | 0.0494 (7) | |
H14 | 0.0347 | 0.3032 | 0.3442 | 0.059* | |
C15 | 0.2195 (5) | 0.1388 (3) | 0.3876 (2) | 0.0495 (7) | |
H15A | 0.1400 | 0.1605 | 0.4409 | 0.059* | |
H15B | 0.2575 | 0.0545 | 0.3810 | 0.059* | |
C16 | 0.5271 (5) | 0.2285 (4) | 0.3352 (3) | 0.0605 (9) | |
H16A | 0.5625 | 0.1426 | 0.3222 | 0.091* | |
H16B | 0.6375 | 0.2995 | 0.3580 | 0.091* | |
H16C | 0.4705 | 0.2299 | 0.2771 | 0.091* | |
W1 | 0.164350 (13) | 0.664901 (10) | 0.381689 (7) | 0.03309 (5) | |
N1 | 0.6756 (3) | 0.6689 (2) | 0.25987 (17) | 0.0436 (5) | |
H1A | 0.5917 | 0.6236 | 0.2871 | 0.052* | |
H1B | 0.7876 | 0.6456 | 0.2649 | 0.052* | |
N2 | 0.3910 (3) | 0.2489 (3) | 0.40902 (18) | 0.0510 (6) | |
H2A | 0.3534 | 0.3271 | 0.4176 | 0.061* | |
H2B | 0.4506 | 0.2582 | 0.4651 | 0.061* | |
S1 | −0.10531 (10) | 0.57374 (8) | 0.41657 (6) | 0.04382 (17) | |
S2 | 0.25800 (13) | 0.86874 (8) | 0.48700 (7) | 0.0594 (2) | |
S3 | 0.13227 (12) | 0.67014 (10) | 0.23646 (6) | 0.0540 (2) | |
S4 | 0.37736 (10) | 0.54331 (7) | 0.38502 (6) | 0.04296 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0473 (17) | 0.0562 (19) | 0.0365 (15) | 0.0147 (14) | −0.0022 (12) | 0.0162 (14) |
C2 | 0.054 (2) | 0.076 (3) | 0.058 (2) | 0.0228 (18) | 0.0114 (16) | 0.0282 (19) |
C3 | 0.089 (3) | 0.088 (3) | 0.055 (2) | 0.049 (3) | 0.012 (2) | 0.020 (2) |
C4 | 0.111 (4) | 0.056 (2) | 0.056 (2) | 0.026 (2) | −0.011 (2) | 0.0129 (18) |
C5 | 0.085 (3) | 0.065 (2) | 0.065 (2) | −0.006 (2) | −0.005 (2) | 0.021 (2) |
C6 | 0.059 (2) | 0.068 (2) | 0.0486 (18) | 0.0061 (18) | 0.0056 (16) | 0.0150 (17) |
C7 | 0.0540 (19) | 0.063 (2) | 0.0458 (17) | 0.0183 (16) | 0.0010 (14) | 0.0248 (15) |
C8 | 0.056 (2) | 0.0446 (18) | 0.067 (2) | 0.0056 (15) | 0.0101 (16) | 0.0139 (16) |
C9 | 0.0366 (15) | 0.0372 (15) | 0.0441 (15) | 0.0058 (12) | 0.0052 (12) | 0.0153 (12) |
C10 | 0.0556 (19) | 0.0400 (17) | 0.061 (2) | 0.0102 (14) | 0.0048 (16) | 0.0114 (15) |
C11 | 0.075 (2) | 0.060 (2) | 0.051 (2) | 0.0095 (19) | −0.0043 (17) | −0.0023 (17) |
C12 | 0.056 (2) | 0.089 (3) | 0.053 (2) | 0.014 (2) | −0.0092 (16) | 0.021 (2) |
C13 | 0.052 (2) | 0.066 (2) | 0.067 (2) | 0.0199 (17) | 0.0012 (16) | 0.0292 (19) |
C14 | 0.0451 (17) | 0.0446 (17) | 0.0546 (18) | 0.0111 (14) | 0.0044 (14) | 0.0125 (14) |
C15 | 0.0531 (18) | 0.0531 (19) | 0.0449 (17) | 0.0108 (15) | 0.0067 (14) | 0.0210 (15) |
C16 | 0.0456 (19) | 0.069 (2) | 0.067 (2) | 0.0126 (17) | 0.0075 (16) | 0.0253 (18) |
W1 | 0.02768 (7) | 0.03355 (7) | 0.03975 (7) | 0.00685 (4) | 0.00315 (4) | 0.01511 (5) |
N1 | 0.0389 (13) | 0.0455 (14) | 0.0473 (14) | 0.0086 (11) | 0.0024 (10) | 0.0180 (11) |
N2 | 0.0448 (14) | 0.0594 (16) | 0.0437 (14) | 0.0114 (12) | −0.0039 (11) | 0.0127 (12) |
S1 | 0.0326 (4) | 0.0491 (4) | 0.0543 (4) | 0.0068 (3) | 0.0087 (3) | 0.0250 (3) |
S2 | 0.0653 (5) | 0.0336 (4) | 0.0685 (5) | 0.0051 (4) | 0.0000 (4) | 0.0085 (4) |
S3 | 0.0483 (4) | 0.0789 (6) | 0.0509 (4) | 0.0229 (4) | 0.0127 (3) | 0.0378 (4) |
S4 | 0.0338 (4) | 0.0437 (4) | 0.0560 (4) | 0.0125 (3) | 0.0033 (3) | 0.0214 (3) |
C1—C6 | 1.383 (5) | C10—H10 | 0.9300 |
C1—C2 | 1.385 (4) | C11—C12 | 1.365 (5) |
C1—C7 | 1.500 (4) | C11—H11 | 0.9300 |
C2—C3 | 1.374 (5) | C12—C13 | 1.372 (5) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.366 (6) | C13—C14 | 1.373 (5) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.372 (6) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—N2 | 1.491 (4) |
C5—C6 | 1.375 (5) | C15—H15A | 0.9700 |
C5—H5 | 0.9300 | C15—H15B | 0.9700 |
C6—H6 | 0.9300 | C16—N2 | 1.466 (4) |
C7—N1 | 1.480 (4) | C16—H16A | 0.9600 |
C7—H7A | 0.9700 | C16—H16B | 0.9600 |
C7—H7B | 0.9700 | C16—H16C | 0.9600 |
C8—N1 | 1.474 (4) | W1—S1 | 2.1703 (8) |
C8—H8A | 0.9600 | W1—S2 | 2.1713 (9) |
C8—H8B | 0.9600 | W1—S3 | 2.1962 (9) |
C8—H8C | 0.9600 | W1—S4 | 2.2083 (7) |
C9—C14 | 1.380 (4) | N1—H1A | 0.9000 |
C9—C10 | 1.382 (4) | N1—H1B | 0.9000 |
C9—C15 | 1.506 (4) | N2—H2A | 0.9000 |
C10—C11 | 1.376 (5) | N2—H2B | 0.9000 |
C6—C1—C2 | 119.0 (3) | C11—C12—C13 | 119.9 (3) |
C6—C1—C7 | 120.6 (3) | C11—C12—H12 | 120.1 |
C2—C1—C7 | 120.4 (3) | C13—C12—H12 | 120.1 |
C3—C2—C1 | 120.6 (4) | C12—C13—C14 | 120.1 (3) |
C3—C2—H2 | 119.7 | C12—C13—H13 | 120.0 |
C1—C2—H2 | 119.7 | C14—C13—H13 | 120.0 |
C4—C3—C2 | 120.0 (4) | C13—C14—C9 | 120.5 (3) |
C4—C3—H3 | 120.0 | C13—C14—H14 | 119.7 |
C2—C3—H3 | 120.0 | C9—C14—H14 | 119.7 |
C3—C4—C5 | 119.8 (4) | N2—C15—C9 | 111.3 (2) |
C3—C4—H4 | 120.1 | N2—C15—H15A | 109.4 |
C5—C4—H4 | 120.1 | C9—C15—H15A | 109.4 |
C4—C5—C6 | 120.8 (4) | N2—C15—H15B | 109.4 |
C4—C5—H5 | 119.6 | C9—C15—H15B | 109.4 |
C6—C5—H5 | 119.6 | H15A—C15—H15B | 108.0 |
C5—C6—C1 | 119.7 (3) | N2—C16—H16A | 109.5 |
C5—C6—H6 | 120.1 | N2—C16—H16B | 109.5 |
C1—C6—H6 | 120.1 | H16A—C16—H16B | 109.5 |
N1—C7—C1 | 112.2 (2) | 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—W1—S2 | 109.69 (3) |
C1—C7—H7B | 109.2 | S1—W1—S3 | 109.18 (3) |
H7A—C7—H7B | 107.9 | S2—W1—S3 | 110.18 (4) |
N1—C8—H8A | 109.5 | S1—W1—S4 | 109.63 (3) |
N1—C8—H8B | 109.5 | S2—W1—S4 | 108.89 (3) |
H8A—C8—H8B | 109.5 | S3—W1—S4 | 109.26 (3) |
N1—C8—H8C | 109.5 | C8—N1—C7 | 114.6 (2) |
H8A—C8—H8C | 109.5 | C8—N1—H1A | 108.6 |
H8B—C8—H8C | 109.5 | C7—N1—H1A | 108.6 |
C14—C9—C10 | 119.0 (3) | C8—N1—H1B | 108.6 |
C14—C9—C15 | 120.5 (3) | C7—N1—H1B | 108.6 |
C10—C9—C15 | 120.5 (3) | H1A—N1—H1B | 107.6 |
C11—C10—C9 | 120.0 (3) | C16—N2—C15 | 115.5 (3) |
C11—C10—H10 | 120.0 | C16—N2—H2A | 108.4 |
C9—C10—H10 | 120.0 | C15—N2—H2A | 108.4 |
C12—C11—C10 | 120.5 (3) | C16—N2—H2B | 108.4 |
C12—C11—H11 | 119.8 | C15—N2—H2B | 108.4 |
C10—C11—H11 | 119.8 | H2A—N2—H2B | 107.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S3i | 0.90 | 2.51 | 3.316 (3) | 150 |
N1—H1B···S1i | 0.90 | 2.79 | 3.356 (2) | 123 |
N1—H1A···S4 | 0.90 | 2.39 | 3.282 (3) | 169 |
N2—H2A···S4 | 0.90 | 2.53 | 3.343 (3) | 151 |
N2—H2B···S4ii | 0.90 | 2.58 | 3.290 (3) | 136 |
N2—H2B···S2ii | 0.90 | 2.92 | 3.599 (3) | 133 |
C7—H7B···S3 | 0.97 | 2.93 | 3.741 (3) | 142 |
C15—H15A···S1iii | 0.97 | 2.95 | 3.648 (3) | 130 |
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[WS4] |
Mr | 556.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.2178 (12), 10.7965 (19), 14.900 (3) |
α, β, γ (°) | 111.057 (2), 90.539 (2), 100.584 (2) |
V (Å3) | 1061.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.83 |
Crystal size (mm) | 0.28 × 0.18 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART Apex CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.292, 0.711 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11136, 4189, 3976 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.043, 1.06 |
No. of reflections | 4189 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.44 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL, DIAMOND (Brandenburg 1999).
W1—S1 | 2.1703 (8) | W1—S3 | 2.1962 (9) |
W1—S2 | 2.1713 (9) | W1—S4 | 2.2083 (7) |
S1—W1—S2 | 109.69 (3) | S1—W1—S4 | 109.63 (3) |
S1—W1—S3 | 109.18 (3) | S2—W1—S4 | 108.89 (3) |
S2—W1—S3 | 110.18 (4) | S3—W1—S4 | 109.26 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S3i | 0.90 | 2.51 | 3.316 (3) | 149.5 |
N1—H1B···S1i | 0.90 | 2.79 | 3.356 (2) | 122.5 |
N1—H1A···S4 | 0.90 | 2.39 | 3.282 (3) | 169.1 |
N2—H2A···S4 | 0.90 | 2.53 | 3.343 (3) | 151.1 |
N2—H2B···S4ii | 0.90 | 2.58 | 3.290 (3) | 136.4 |
N2—H2B···S2ii | 0.90 | 2.92 | 3.599 (3) | 133.1 |
C7—H7B···S3 | 0.97 | 2.93 | 3.741 (3) | 142.1 |
C15—H15A···S1iii | 0.97 | 2.95 | 3.648 (3) | 129.8 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1. |
As part of an ongoing research programme, we are investigating the synthesis and structural characterization of organic ammonium tetrasulfidometalates of the group VI metals Mo and W (Srinivasan, Naik et al., 2007). In earlier work we have structurally characterized several [WS4]2- compounds derived from chiral amines (Srinivasan, Naik et al., 2007), diamines (Srinivasan et al., 2002; 2003a; Srinivasan et al., 2006a), triamines (Srinivasan et al., 2006b), cyclic amines (Srinivasan et al., 2003b; Srinivasan et al., 2006) and a tetraamine (Srinivasan et al., 2005). All the organic ammonium tetrasulfidotungstates exhibit several weak hydrogen bonding interactions between the organic cations and [WS4]2- anions. We have also shown that in some organic [WS4]2- compounds the amines are partially protonated (Srinivasan et al., 2006b). The secondary amine benzyl(methyl)amine used for the synthesis of the title compound is an isomer of the chiral primary amine α-methylbenzylamine used in an earlier study (Srinivasan, Naik et al., 2007).
The title compound is isostructural with the corresponding Mo analogue (C8H12N)2[MoS4] (Srinivasan, Girkar & Raghavaiah 2007). The structure of (I) consists of a discrete tetrahedral [WS4]2- ion and two crystallographically independent benzyl(methyl)ammonium cations (Fig. 1) with all atoms located in general positions. The bond lengths and bond angles of the organic cations are in good agreement with the reported values for the isotypic Mo compound. The (WS4) tetrahedron is slightly distorted with S—W—S angles between 108.89 (3) and 110.18 (4) ° (Table 1). The W—S bond lengths range from 2.1703 (8) to 2.2083 (7) Å with an average value of 2.1865 Å which is comparable to the bond lengths observed in the related chiral [WS4]2- compound synthesized from the isomeric chiral primary amine (Srinivasan, Naik et al., 2007). The W1—S1 and W1—S2 bond distances are indistinguishable within experimental error and are shorter than the average Mo—S bond length while the other two W—S bonds are longer. The weak H-bonding interactions between the cations and anions can explain the observed short and long W—S bond distances. An analysis of the structure reveals that the organic cations and tetrasulfidotungstate anions are linked with the aid of several N—H···S and C—H···S hydrogen bonding interactions. Thus each [WS4]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 [WS4]2- ions while the second organic cation (N2) is surrounded by three different [WS4]2- ions. One H atom on each N atom functions as a singly shared donor with the other functioning as a bifurcated donor (Table 2). A benzilic H atom from each unique cation is involved in a weak C—H···S interaction. S4 atom which makes the longest W—S bond at 2.2083 (7) 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 2.39 Å, which can explain the elongation of this bond. In contrast, S1 atom involved in the shortest W—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 W—S bonds of 0.0380 Å in (I) is slightly longer than the Δ value of 0.0356 Å in the tetrasulfidotungstate compound containing the R-form of the monoprotonated isomeric chiral primary amine α-methylbenzylamine (Srinivasan, Naik et al., 2007).