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The title compound, (C8H12N)2[WS4], was synthesized by the aqueous reaction of ammonium tetra­sulfidotungstate(VI) with benz­yl(meth­yl)amine in a 1:2 molar ratio. The compound is isotypic with the corresponding Mo analogue, (C8H12N)2[MoS4], and its structure consists of a slightly distorted tetra­hedral [WS4]2− dianion and two crystallographically independent benz­yl(meth­yl)ammonium cations, with all atoms located in general positions. The cations and anion are linked by weak N—H...S and C—H...S inter­actions, the strength and number of which can explain the observed W—S bond distances.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058746/nc2077sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058746/nc2077Isup2.hkl
Contains datablock I

CCDC reference: 672719

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.018
  • wR factor = 0.043
  • Data-to-parameter ratio = 19.9

checkCIF/PLATON results

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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

Comment top

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).

Related literature top

Previous reports give details of the structural characterization of several organic ammonium tetrasulfidotungstates containing organic cations derived from chiral amines (Srinivasan, Naik et al., 2007), diamines (Srinivasan et al., 2002; 2003a; Srinivasan, Näther et al., 2006a), triamines (Srinivasan, Näther et al., 2006b), cyclic amines (Srinivasan et al., 2003b; Srinivasan, Naik et al., 2006) and a tetraamine (Srinivasan et al., 2005). The title compound is isotypic with the corresponding Mo analogue (C8H12N)2[MoS4] (Srinivasan, Girkar & Raghavaiah 2007).

Experimental top

(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%.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The crystal structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the surroundings of the [WS4]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
Bis[benzyl(methyl)ammonium] tetrasulfidotungstate(VI) top
Crystal data top
(C8H12N)2[WS4]Z = 2
Mr = 556.46F(000) = 544
Triclinic, P1Dx = 1.741 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2178 (12) ÅCell parameters from 9395 reflections
b = 10.7965 (19) Åθ = 2.9–26.1°
c = 14.900 (3) ŵ = 5.83 mm1
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
Data collection top
Bruker SMART Apex CCD
diffractometer
4189 independent reflections
Radiation source: fine-focus sealed tube3976 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
phi and ω scansθmax = 26.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 88
Tmin = 0.292, Tmax = 0.711k = 1313
11136 measured reflectionsl = 1818
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)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.043H-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 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
(C8H12N)2[WS4]γ = 100.584 (2)°
Mr = 556.46V = 1061.6 (3) Å3
Triclinic, P1Z = 2
a = 7.2178 (12) ÅMo Kα radiation
b = 10.7965 (19) ŵ = 5.83 mm1
c = 14.900 (3) ÅT = 298 K
α = 111.057 (2)°0.28 × 0.18 × 0.06 mm
β = 90.539 (2)°
Data collection top
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 = 0.711Rint = 0.021
11136 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.043H-atom parameters constrained
S = 1.06Δρmax = 0.61 e Å3
4189 reflectionsΔρmin = 0.44 e Å3
210 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
C10.5898 (4)0.4749 (3)0.1050 (2)0.0463 (7)
C20.7217 (5)0.4217 (4)0.0434 (3)0.0606 (9)
H20.82810.47940.03600.073*
C30.6967 (6)0.2846 (4)0.0070 (3)0.0747 (12)
H30.78460.25010.04930.090*
C40.5427 (7)0.1990 (4)0.0051 (3)0.0756 (11)
H40.52610.10620.02870.091*
C50.4126 (6)0.2505 (4)0.0671 (3)0.0753 (11)
H50.30890.19190.07580.090*
C60.4338 (5)0.3877 (4)0.1165 (2)0.0613 (9)
H60.34370.42170.15750.074*
C70.6132 (5)0.6251 (3)0.1563 (2)0.0519 (8)
H7A0.70560.67090.12580.062*
H7B0.49380.65160.15020.062*
C80.6955 (5)0.8154 (3)0.3147 (2)0.0583 (8)
H8A0.77470.86520.28260.087*
H8B0.75160.83730.37860.087*
H8C0.57310.83890.31860.087*
C90.1084 (4)0.1210 (3)0.2963 (2)0.0394 (6)
C100.0900 (5)0.0025 (3)0.2165 (2)0.0540 (8)
H100.14830.06650.21860.065*
C110.0147 (5)0.0135 (4)0.1340 (3)0.0688 (10)
H110.03030.09460.08130.083*
C120.0958 (5)0.0888 (4)0.1290 (3)0.0674 (10)
H120.16510.07770.07270.081*
C130.0749 (5)0.2080 (4)0.2071 (3)0.0594 (9)
H130.12790.27840.20340.071*
C140.0242 (4)0.2233 (3)0.2908 (2)0.0494 (7)
H140.03470.30320.34420.059*
C150.2195 (5)0.1388 (3)0.3876 (2)0.0495 (7)
H15A0.14000.16050.44090.059*
H15B0.25750.05450.38100.059*
C160.5271 (5)0.2285 (4)0.3352 (3)0.0605 (9)
H16A0.56250.14260.32220.091*
H16B0.63750.29950.35800.091*
H16C0.47050.22990.27710.091*
W10.164350 (13)0.664901 (10)0.381689 (7)0.03309 (5)
N10.6756 (3)0.6689 (2)0.25987 (17)0.0436 (5)
H1A0.59170.62360.28710.052*
H1B0.78760.64560.26490.052*
N20.3910 (3)0.2489 (3)0.40902 (18)0.0510 (6)
H2A0.35340.32710.41760.061*
H2B0.45060.25820.46510.061*
S10.10531 (10)0.57374 (8)0.41657 (6)0.04382 (17)
S20.25800 (13)0.86874 (8)0.48700 (7)0.0594 (2)
S30.13227 (12)0.67014 (10)0.23646 (6)0.0540 (2)
S40.37736 (10)0.54331 (7)0.38502 (6)0.04296 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0473 (17)0.0562 (19)0.0365 (15)0.0147 (14)0.0022 (12)0.0162 (14)
C20.054 (2)0.076 (3)0.058 (2)0.0228 (18)0.0114 (16)0.0282 (19)
C30.089 (3)0.088 (3)0.055 (2)0.049 (3)0.012 (2)0.020 (2)
C40.111 (4)0.056 (2)0.056 (2)0.026 (2)0.011 (2)0.0129 (18)
C50.085 (3)0.065 (2)0.065 (2)0.006 (2)0.005 (2)0.021 (2)
C60.059 (2)0.068 (2)0.0486 (18)0.0061 (18)0.0056 (16)0.0150 (17)
C70.0540 (19)0.063 (2)0.0458 (17)0.0183 (16)0.0010 (14)0.0248 (15)
C80.056 (2)0.0446 (18)0.067 (2)0.0056 (15)0.0101 (16)0.0139 (16)
C90.0366 (15)0.0372 (15)0.0441 (15)0.0058 (12)0.0052 (12)0.0153 (12)
C100.0556 (19)0.0400 (17)0.061 (2)0.0102 (14)0.0048 (16)0.0114 (15)
C110.075 (2)0.060 (2)0.051 (2)0.0095 (19)0.0043 (17)0.0023 (17)
C120.056 (2)0.089 (3)0.053 (2)0.014 (2)0.0092 (16)0.021 (2)
C130.052 (2)0.066 (2)0.067 (2)0.0199 (17)0.0012 (16)0.0292 (19)
C140.0451 (17)0.0446 (17)0.0546 (18)0.0111 (14)0.0044 (14)0.0125 (14)
C150.0531 (18)0.0531 (19)0.0449 (17)0.0108 (15)0.0067 (14)0.0210 (15)
C160.0456 (19)0.069 (2)0.067 (2)0.0126 (17)0.0075 (16)0.0253 (18)
W10.02768 (7)0.03355 (7)0.03975 (7)0.00685 (4)0.00315 (4)0.01511 (5)
N10.0389 (13)0.0455 (14)0.0473 (14)0.0086 (11)0.0024 (10)0.0180 (11)
N20.0448 (14)0.0594 (16)0.0437 (14)0.0114 (12)0.0039 (11)0.0127 (12)
S10.0326 (4)0.0491 (4)0.0543 (4)0.0068 (3)0.0087 (3)0.0250 (3)
S20.0653 (5)0.0336 (4)0.0685 (5)0.0051 (4)0.0000 (4)0.0085 (4)
S30.0483 (4)0.0789 (6)0.0509 (4)0.0229 (4)0.0127 (3)0.0378 (4)
S40.0338 (4)0.0437 (4)0.0560 (4)0.0125 (3)0.0033 (3)0.0214 (3)
Geometric parameters (Å, º) top
C1—C61.383 (5)C10—H100.9300
C1—C21.385 (4)C11—C121.365 (5)
C1—C71.500 (4)C11—H110.9300
C2—C31.374 (5)C12—C131.372 (5)
C2—H20.9300C12—H120.9300
C3—C41.366 (6)C13—C141.373 (5)
C3—H30.9300C13—H130.9300
C4—C51.372 (6)C14—H140.9300
C4—H40.9300C15—N21.491 (4)
C5—C61.375 (5)C15—H15A0.9700
C5—H50.9300C15—H15B0.9700
C6—H60.9300C16—N21.466 (4)
C7—N11.480 (4)C16—H16A0.9600
C7—H7A0.9700C16—H16B0.9600
C7—H7B0.9700C16—H16C0.9600
C8—N11.474 (4)W1—S12.1703 (8)
C8—H8A0.9600W1—S22.1713 (9)
C8—H8B0.9600W1—S32.1962 (9)
C8—H8C0.9600W1—S42.2083 (7)
C9—C141.380 (4)N1—H1A0.9000
C9—C101.382 (4)N1—H1B0.9000
C9—C151.506 (4)N2—H2A0.9000
C10—C111.376 (5)N2—H2B0.9000
C6—C1—C2119.0 (3)C11—C12—C13119.9 (3)
C6—C1—C7120.6 (3)C11—C12—H12120.1
C2—C1—C7120.4 (3)C13—C12—H12120.1
C3—C2—C1120.6 (4)C12—C13—C14120.1 (3)
C3—C2—H2119.7C12—C13—H13120.0
C1—C2—H2119.7C14—C13—H13120.0
C4—C3—C2120.0 (4)C13—C14—C9120.5 (3)
C4—C3—H3120.0C13—C14—H14119.7
C2—C3—H3120.0C9—C14—H14119.7
C3—C4—C5119.8 (4)N2—C15—C9111.3 (2)
C3—C4—H4120.1N2—C15—H15A109.4
C5—C4—H4120.1C9—C15—H15A109.4
C4—C5—C6120.8 (4)N2—C15—H15B109.4
C4—C5—H5119.6C9—C15—H15B109.4
C6—C5—H5119.6H15A—C15—H15B108.0
C5—C6—C1119.7 (3)N2—C16—H16A109.5
C5—C6—H6120.1N2—C16—H16B109.5
C1—C6—H6120.1H16A—C16—H16B109.5
N1—C7—C1112.2 (2)N2—C16—H16C109.5
N1—C7—H7A109.2H16A—C16—H16C109.5
C1—C7—H7A109.2H16B—C16—H16C109.5
N1—C7—H7B109.2S1—W1—S2109.69 (3)
C1—C7—H7B109.2S1—W1—S3109.18 (3)
H7A—C7—H7B107.9S2—W1—S3110.18 (4)
N1—C8—H8A109.5S1—W1—S4109.63 (3)
N1—C8—H8B109.5S2—W1—S4108.89 (3)
H8A—C8—H8B109.5S3—W1—S4109.26 (3)
N1—C8—H8C109.5C8—N1—C7114.6 (2)
H8A—C8—H8C109.5C8—N1—H1A108.6
H8B—C8—H8C109.5C7—N1—H1A108.6
C14—C9—C10119.0 (3)C8—N1—H1B108.6
C14—C9—C15120.5 (3)C7—N1—H1B108.6
C10—C9—C15120.5 (3)H1A—N1—H1B107.6
C11—C10—C9120.0 (3)C16—N2—C15115.5 (3)
C11—C10—H10120.0C16—N2—H2A108.4
C9—C10—H10120.0C15—N2—H2A108.4
C12—C11—C10120.5 (3)C16—N2—H2B108.4
C12—C11—H11119.8C15—N2—H2B108.4
C10—C11—H11119.8H2A—N2—H2B107.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···S3i0.902.513.316 (3)150
N1—H1B···S1i0.902.793.356 (2)123
N1—H1A···S40.902.393.282 (3)169
N2—H2A···S40.902.533.343 (3)151
N2—H2B···S4ii0.902.583.290 (3)136
N2—H2B···S2ii0.902.923.599 (3)133
C7—H7B···S30.972.933.741 (3)142
C15—H15A···S1iii0.972.953.648 (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]
Mr556.46
Crystal system, space groupTriclinic, 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)
V3)1061.6 (3)
Z2
Radiation typeMo Kα
µ (mm1)5.83
Crystal size (mm)0.28 × 0.18 × 0.06
Data collection
DiffractometerBruker SMART Apex CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.292, 0.711
No. of measured, independent and
observed [I > 2σ(I)] reflections
11136, 4189, 3976
Rint0.021
(sin θ/λ)max1)0.620
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.043, 1.06
No. of reflections4189
No. of parameters210
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.61, 0.44

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL, DIAMOND (Brandenburg 1999).

Selected geometric parameters (Å, º) top
W1—S12.1703 (8)W1—S32.1962 (9)
W1—S22.1713 (9)W1—S42.2083 (7)
S1—W1—S2109.69 (3)S1—W1—S4109.63 (3)
S1—W1—S3109.18 (3)S2—W1—S4108.89 (3)
S2—W1—S3110.18 (4)S3—W1—S4109.26 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···S3i0.902.513.316 (3)149.5
N1—H1B···S1i0.902.793.356 (2)122.5
N1—H1A···S40.902.393.282 (3)169.1
N2—H2A···S40.902.533.343 (3)151.1
N2—H2B···S4ii0.902.583.290 (3)136.4
N2—H2B···S2ii0.902.923.599 (3)133.1
C7—H7B···S30.972.933.741 (3)142.1
C15—H15A···S1iii0.972.953.648 (3)129.8
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1.
 

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