The title complex, (C6H16N2)[WS4], consists of tetrahedral [WS4]2- dianions and organic dications. There are two crystallographically independent 1,4-dimethylpiperazinium (1,4-dmpH2) dications in the asymmetric unit, both of which are located around a centre of inversion, while the anions are located in general positions. The anions and cations are connected by hydrogen bonding.
Supporting information
CCDC reference: 221661
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.025
- wR factor = 0.067
- Data-to-parameter ratio = 24.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); 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 SHELXL97.
1,4-dimethylpiperazinium tetrathiotungstate(VI)
top
Crystal data top
(C6H16N2)[WS4] | Dx = 2.253 Mg m−3 |
Mr = 428.30 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8000 reflections |
a = 13.3792 (11) Å | θ = 15–23° |
b = 12.6369 (7) Å | µ = 9.77 mm−1 |
c = 14.9381 (9) Å | T = 293 K |
V = 2525.6 (3) Å3 | Block, yellow |
Z = 8 | 0.14 × 0.09 × 0.06 mm |
F(000) = 1632 | |
Data collection top
Stoe IPDS diffractometer | 2946 independent reflections |
Radiation source: fine-focus sealed tube | 2398 reflections with I > 2s(I) |
Graphite monochromator | Rint = 0.041 |
φ scans | θmax = 28.0°, θmin = 2.6° |
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 1998) | h = −17→17 |
Tmin = 0.360, Tmax = 0.555 | k = −15→15 |
23034 measured reflections | l = −18→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0453P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.004 |
2946 reflections | Δρmax = 1.66 e Å−3 |
119 parameters | Δρmin = −1.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00187 (9) |
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 | x | y | z | Uiso*/Ueq | |
W1 | 0.248391 (6) | 0.345321 (12) | 0.628045 (7) | 0.01946 (8) | |
S1 | 0.10187 (5) | 0.28939 (7) | 0.67238 (5) | 0.03026 (18) | |
S2 | 0.27210 (6) | 0.29591 (8) | 0.48747 (5) | 0.03188 (19) | |
S3 | 0.36779 (6) | 0.28653 (8) | 0.71377 (6) | 0.0422 (2) | |
S4 | 0.24917 (5) | 0.51921 (10) | 0.63317 (6) | 0.0315 (2) | |
N1 | 0.40873 (17) | 0.5130 (2) | 0.44850 (16) | 0.0259 (5) | |
H1 | 0.3655 | 0.4801 | 0.4864 | 0.031* | |
C1 | 0.4875 (2) | 0.4348 (3) | 0.4221 (2) | 0.0301 (7) | |
H1A | 0.5332 | 0.4676 | 0.3801 | 0.036* | |
H1B | 0.4563 | 0.3750 | 0.3924 | 0.036* | |
C2 | 0.5454 (2) | 0.3958 (3) | 0.5027 (2) | 0.0298 (7) | |
H2A | 0.5010 | 0.3577 | 0.5426 | 0.036* | |
H2B | 0.5975 | 0.3476 | 0.4834 | 0.036* | |
C3 | 0.3513 (3) | 0.5492 (4) | 0.3687 (2) | 0.0462 (10) | |
H3A | 0.3226 | 0.4891 | 0.3389 | 0.069* | |
H3B | 0.3953 | 0.5857 | 0.3283 | 0.069* | |
H3C | 0.2990 | 0.5963 | 0.3874 | 0.069* | |
N11 | 0.49326 (17) | 0.5178 (2) | −0.09605 (16) | 0.0242 (5) | |
H11 | 0.5495 | 0.4829 | −0.1135 | 0.029* | |
C11 | 0.5237 (2) | 0.6048 (3) | −0.0332 (2) | 0.0271 (7) | |
H11A | 0.4652 | 0.6450 | −0.0156 | 0.032* | |
H11B | 0.5695 | 0.6524 | −0.0634 | 0.032* | |
C12 | 0.5736 (2) | 0.5597 (3) | 0.0492 (2) | 0.0274 (6) | |
H12A | 0.6352 | 0.5247 | 0.0320 | 0.033* | |
H12B | 0.5904 | 0.6168 | 0.0899 | 0.033* | |
C13 | 0.4438 (3) | 0.5618 (3) | −0.1780 (2) | 0.0386 (8) | |
H13A | 0.4253 | 0.5048 | −0.2172 | 0.058* | |
H13B | 0.4893 | 0.6082 | −0.2084 | 0.058* | |
H13C | 0.3851 | 0.6005 | −0.1609 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W1 | 0.01603 (10) | 0.02096 (13) | 0.02140 (11) | 0.00036 (3) | −0.00050 (3) | −0.00104 (4) |
S1 | 0.0255 (3) | 0.0339 (5) | 0.0315 (4) | −0.0083 (3) | 0.0074 (3) | −0.0023 (3) |
S2 | 0.0328 (3) | 0.0385 (5) | 0.0243 (4) | −0.0032 (3) | 0.0054 (3) | −0.0064 (3) |
S3 | 0.0378 (4) | 0.0442 (6) | 0.0446 (5) | 0.0144 (4) | −0.0204 (4) | −0.0072 (4) |
S4 | 0.0327 (5) | 0.0186 (6) | 0.0431 (5) | −0.0018 (3) | 0.0004 (3) | −0.0012 (3) |
N1 | 0.0238 (11) | 0.0298 (16) | 0.0241 (12) | −0.0004 (10) | 0.0030 (9) | 0.0050 (10) |
C1 | 0.0262 (14) | 0.037 (2) | 0.0277 (16) | 0.0034 (13) | 0.0030 (12) | −0.0074 (13) |
C2 | 0.0298 (15) | 0.023 (2) | 0.0365 (18) | 0.0048 (11) | 0.0044 (13) | 0.0008 (12) |
C3 | 0.042 (2) | 0.061 (3) | 0.035 (2) | 0.0072 (17) | −0.0080 (14) | 0.0092 (16) |
N11 | 0.0244 (11) | 0.0261 (15) | 0.0221 (12) | −0.0003 (10) | 0.0027 (9) | 0.0019 (10) |
C11 | 0.0323 (16) | 0.0216 (19) | 0.0273 (16) | −0.0058 (11) | 0.0018 (12) | 0.0013 (11) |
C12 | 0.0270 (14) | 0.0278 (19) | 0.0274 (16) | −0.0078 (12) | −0.0001 (11) | −0.0009 (13) |
C13 | 0.0475 (19) | 0.045 (2) | 0.0234 (16) | 0.0015 (16) | −0.0049 (14) | 0.0062 (15) |
Geometric parameters (Å, º) top
W1—S3 | 2.1781 (8) | C3—H3B | 0.96 |
W1—S1 | 2.1866 (7) | C3—H3C | 0.96 |
W1—S4 | 2.1988 (12) | N11—C13 | 1.499 (4) |
W1—S2 | 2.2136 (8) | N11—C12ii | 1.500 (4) |
N1—C3 | 1.491 (4) | N11—C11 | 1.502 (4) |
N1—C2i | 1.495 (4) | N11—H11 | 0.91 |
N1—C1 | 1.497 (4) | C11—C12 | 1.512 (5) |
N1—H1 | 0.91 | C11—H11A | 0.97 |
C1—C2 | 1.514 (5) | C11—H11B | 0.97 |
C1—H1A | 0.97 | C12—N11ii | 1.500 (4) |
C1—H1B | 0.97 | C12—H12A | 0.97 |
C2—N1i | 1.495 (4) | C12—H12B | 0.97 |
C2—H2A | 0.97 | C13—H13A | 0.96 |
C2—H2B | 0.97 | C13—H13B | 0.96 |
C3—H3A | 0.96 | C13—H13C | 0.96 |
| | | |
S3—W1—S1 | 111.67 (4) | N1—C3—H3C | 109.5 |
S3—W1—S4 | 108.48 (3) | H3A—C3—H3C | 109.5 |
S1—W1—S4 | 108.46 (3) | H3B—C3—H3C | 109.5 |
S3—W1—S2 | 110.88 (4) | C13—N11—C12ii | 111.1 (2) |
S1—W1—S2 | 108.94 (3) | C13—N11—C11 | 111.1 (3) |
S4—W1—S2 | 108.32 (3) | C12ii—N11—C11 | 110.4 (2) |
C3—N1—C2i | 111.4 (3) | C13—N11—H11 | 108.1 |
C3—N1—C1 | 110.8 (3) | C12ii—N11—H11 | 108.1 |
C2i—N1—C1 | 110.4 (2) | C11—N11—H11 | 108.1 |
C3—N1—H1 | 108.1 | N11—C11—C12 | 110.7 (3) |
C2i—N1—H1 | 108.1 | N11—C11—H11A | 109.5 |
C1—N1—H1 | 108.1 | C12—C11—H11A | 109.5 |
N1—C1—C2 | 111.5 (2) | N11—C11—H11B | 109.5 |
N1—C1—H1A | 109.3 | C12—C11—H11B | 109.5 |
C2—C1—H1A | 109.3 | H11A—C11—H11B | 108.1 |
N1—C1—H1B | 109.3 | N11ii—C12—C11 | 111.3 (2) |
C2—C1—H1B | 109.3 | N11ii—C12—H12A | 109.4 |
H1A—C1—H1B | 108.0 | C11—C12—H12A | 109.4 |
N1i—C2—C1 | 110.3 (3) | N11ii—C12—H12B | 109.4 |
N1i—C2—H2A | 109.6 | C11—C12—H12B | 109.4 |
C1—C2—H2A | 109.6 | H12A—C12—H12B | 108.0 |
N1i—C2—H2B | 109.6 | N11—C13—H13A | 109.5 |
C1—C2—H2B | 109.6 | N11—C13—H13B | 109.5 |
H2A—C2—H2B | 108.1 | H13A—C13—H13B | 109.5 |
N1—C3—H3A | 109.5 | N11—C13—H13C | 109.5 |
N1—C3—H3B | 109.5 | H13A—C13—H13C | 109.5 |
H3A—C3—H3B | 109.5 | H13B—C13—H13C | 109.5 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S2 | 0.91 | 2.64 | 3.347 (3) | 135 |
N1—H1···S4 | 0.91 | 2.73 | 3.489 (2) | 141 |
N11—H11···S1iii | 0.91 | 2.69 | 3.427 (3) | 139 |
N11—H11···S4iii | 0.91 | 2.73 | 3.468 (2) | 139 |
Symmetry code: (iii) x+1/2, y, −z+1/2. |