The title compound, C6H4S4+·C9H16NO5S-, which includes an organic diamagnetic anion, was obtained unexpectedly by metathesis of the tetraphenylphosphonium salt of an organic free-radical anion, 2,2,6,6-tetramethylpiperidinyloxy-4-hydroxy-4-sulfonate, with (TTF)3(BF4)2 (TTF = tetrathiafulvalene).
Supporting information
CCDC reference: 225700
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.007 Å
- R factor = 0.067
- wR factor = 0.042
- Data-to-parameter ratio = 10.5
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT155_ALERT_4_C The Triclinic Unitcell is NOT Reduced .......... ?
PLAT156_ALERT_4_C Axial System Input Cell not Standard ........... ?
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... S5
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 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
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C6H4S4+·C9H16NO5S− | Z = 2 |
Mr = 454.63 | F(000) = 474.00 |
Triclinic, P1 | Dx = 1.548 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 10.884 (1) Å | Cell parameters from 25 reflections |
b = 12.132 (2) Å | θ = 14.1–15.0° |
c = 7.948 (1) Å | µ = 0.62 mm−1 |
α = 102.78 (1)° | T = 296 K |
β = 106.02 (1)° | Plate, black |
γ = 79.52 (1)° | 0.18 × 0.15 × 0.05 mm |
V = 975.5 (3) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | 2479 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 2.4° |
ω–2θ scans | h = 0→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −15→15 |
Tmin = 0.950, Tmax = 0.970 | l = −10→9 |
4709 measured reflections | 3 standard reflections every 150 reflections |
4476 independent reflections | intensity decay: 0.4% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.067 | H-atom parameters not refined |
wR(F2) = 0.042 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo)] |
S = 1.71 | (Δ/σ)max < 0.001 |
2479 reflections | Δρmax = 0.55 e Å−3 |
235 parameters | Δρmin = −0.55 e Å−3 |
Special details top
Experimental. The scan width was (1.21 + 0.30tanθ)° with an ω scan speed of 0° per minute
(up to 2 scans to achieve I/σ(I) > 10). Stationary background counts were
recorded at each end of the scan, and the scan time:background time ratio was
2:1. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | −0.0352 (1) | 0.0976 (1) | 0.3360 (2) | 0.0339 (4) | |
S2 | −0.1370 (1) | −0.1126 (1) | 0.1430 (2) | 0.0350 (4) | |
S3 | 0.2382 (1) | −0.0015 (1) | 0.2362 (2) | 0.0346 (4) | |
S4 | 0.1318 (1) | −0.2082 (1) | 0.0340 (2) | 0.0354 (4) | |
S5 | 0.4477 (1) | 0.2049 (1) | 0.2021 (2) | 0.0377 (4) | |
O1 | 0.1583 (3) | 0.6474 (3) | 0.6652 (5) | 0.054 (1) | |
O2 | 0.3190 (3) | 0.2686 (2) | 0.2749 (4) | 0.034 (1) | |
O3 | 0.5460 (3) | 0.2785 (3) | 0.2682 (5) | 0.054 (1) | |
O4 | 0.4774 (3) | 0.1020 (3) | 0.2748 (5) | 0.063 (1) | |
O5 | 0.3977 (3) | 0.1856 (3) | 0.0132 (5) | 0.063 (1) | |
N1 | 0.3295 (3) | 0.3809 (3) | 0.3862 (5) | 0.023 (1) | |
C1 | −0.1908 (4) | 0.0864 (4) | 0.3336 (6) | 0.040 (2) | |
C2 | −0.2385 (4) | −0.0100 (4) | 0.2466 (6) | 0.038 (2) | |
C3 | −0.0069 (4) | −0.0367 (4) | 0.2167 (6) | 0.026 (1) | |
C4 | 0.1100 (4) | −0.0786 (3) | 0.1702 (6) | 0.029 (1) | |
C5 | 0.3367 (4) | −0.1045 (4) | 0.1300 (7) | 0.040 (2) | |
C6 | 0.2886 (4) | −0.1979 (4) | 0.0371 (6) | 0.035 (1) | |
C7 | 0.2313 (4) | 0.5807 (4) | 0.5914 (6) | 0.035 (2) | |
C8 | 0.2392 (5) | 0.5786 (4) | 0.4068 (7) | 0.045 (2) | |
C9 | 0.3269 (5) | 0.4895 (4) | 0.6763 (6) | 0.041 (2) | |
C10 | 0.2325 (4) | 0.4610 (4) | 0.2856 (6) | 0.032 (1) | |
C11 | 0.3201 (4) | 0.3695 (4) | 0.5644 (6) | 0.030 (1) | |
C12 | 0.0924 (4) | 0.4319 (5) | 0.2293 (7) | 0.052 (2) | |
C13 | 0.2731 (5) | 0.4643 (4) | 0.1201 (6) | 0.050 (2) | |
C14 | 0.2001 (5) | 0.3215 (4) | 0.5702 (7) | 0.045 (2) | |
C15 | 0.4383 (5) | 0.2925 (4) | 0.6424 (7) | 0.051 (2) | |
H1 | −0.2410 | 0.1452 | 0.3950 | 0.051* | |
H2 | −0.3234 | −0.0218 | 0.2411 | 0.051* | |
H3 | 0.4225 | −0.0933 | 0.1355 | 0.051* | |
H4 | 0.3390 | −0.2580 | −0.0220 | 0.051* | |
H5 | 0.3195 | 0.6028 | 0.4141 | 0.051* | |
H6 | 0.1708 | 0.6306 | 0.3557 | 0.051* | |
H7 | 0.3118 | 0.4897 | 0.7884 | 0.051* | |
H8 | 0.4118 | 0.5085 | 0.6945 | 0.051* | |
H9 | 0.0611 | 0.4273 | 0.1030 | 0.051* | |
H10 | 0.0400 | 0.4906 | 0.2870 | 0.051* | |
H11 | 0.0911 | 0.3616 | 0.2593 | 0.051* | |
H12 | 0.2019 | 0.4577 | 0.0198 | 0.051* | |
H13 | 0.3392 | 0.4021 | 0.1026 | 0.051* | |
H14 | 0.3063 | 0.5338 | 0.1337 | 0.051* | |
H15 | 0.1989 | 0.3113 | 0.6997 | 0.051* | |
H16 | 0.1266 | 0.3729 | 0.5284 | 0.051* | |
H17 | 0.1965 | 0.2498 | 0.4939 | 0.051* | |
H18 | 0.4860 | 0.2609 | 0.5555 | 0.051* | |
H19 | 0.4137 | 0.2331 | 0.6810 | 0.051* | |
H20 | 0.4916 | 0.3361 | 0.7420 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0328 (8) | 0.0291 (7) | 0.0357 (8) | −0.0021 (6) | 0.0103 (6) | −0.0036 (6) |
S2 | 0.0306 (7) | 0.0320 (7) | 0.0444 (9) | −0.0066 (6) | 0.0151 (7) | 0.0012 (6) |
S3 | 0.0283 (7) | 0.0339 (8) | 0.0398 (8) | −0.0065 (6) | 0.0103 (6) | −0.0016 (6) |
S4 | 0.0349 (8) | 0.0249 (7) | 0.0466 (9) | −0.0019 (6) | 0.0164 (7) | 0.0004 (6) |
S5 | 0.0281 (7) | 0.0312 (7) | 0.0541 (9) | −0.0074 (6) | 0.0233 (7) | −0.0111 (6) |
O1 | 0.051 (2) | 0.042 (2) | 0.066 (3) | −0.007 (2) | 0.034 (2) | −0.022 (2) |
O2 | 0.024 (2) | 0.029 (2) | 0.049 (2) | −0.006 (1) | 0.018 (2) | −0.011 (2) |
O3 | 0.032 (2) | 0.044 (2) | 0.088 (3) | −0.018 (2) | 0.034 (2) | −0.017 (2) |
O4 | 0.054 (3) | 0.034 (2) | 0.111 (3) | 0.010 (2) | 0.043 (2) | 0.016 (2) |
O5 | 0.050 (2) | 0.085 (3) | 0.045 (2) | −0.009 (2) | 0.024 (2) | −0.021 (2) |
N1 | 0.027 (2) | 0.017 (2) | 0.026 (2) | −0.004 (2) | 0.011 (2) | −0.005 (2) |
C1 | 0.034 (3) | 0.045 (3) | 0.041 (3) | 0.002 (3) | 0.019 (3) | 0.004 (3) |
C2 | 0.030 (3) | 0.049 (3) | 0.037 (3) | 0.001 (3) | 0.013 (2) | 0.012 (3) |
C3 | 0.025 (3) | 0.029 (3) | 0.023 (3) | −0.002 (2) | 0.008 (2) | 0.004 (2) |
C4 | 0.032 (3) | 0.026 (3) | 0.029 (3) | −0.007 (2) | 0.006 (2) | 0.002 (2) |
C5 | 0.029 (3) | 0.040 (3) | 0.053 (4) | 0.002 (2) | 0.016 (3) | 0.006 (3) |
C6 | 0.033 (3) | 0.027 (3) | 0.044 (3) | 0.005 (2) | 0.012 (3) | 0.008 (2) |
C7 | 0.033 (3) | 0.030 (3) | 0.043 (3) | −0.014 (2) | 0.016 (3) | −0.005 (2) |
C8 | 0.052 (4) | 0.033 (3) | 0.049 (4) | 0.007 (3) | 0.017 (3) | 0.011 (3) |
C9 | 0.053 (4) | 0.040 (3) | 0.031 (3) | −0.007 (3) | 0.018 (3) | −0.003 (2) |
C10 | 0.034 (3) | 0.033 (3) | 0.025 (3) | 0.001 (2) | 0.006 (2) | 0.004 (2) |
C11 | 0.030 (3) | 0.032 (3) | 0.027 (3) | −0.003 (2) | 0.007 (2) | 0.003 (2) |
C12 | 0.029 (3) | 0.069 (4) | 0.051 (4) | 0.006 (3) | 0.004 (3) | 0.009 (3) |
C13 | 0.060 (4) | 0.061 (4) | 0.029 (3) | 0.001 (3) | 0.011 (3) | 0.017 (3) |
C14 | 0.054 (4) | 0.041 (3) | 0.053 (4) | −0.015 (3) | 0.030 (3) | 0.007 (3) |
C15 | 0.053 (4) | 0.052 (4) | 0.045 (4) | 0.005 (3) | 0.013 (3) | 0.015 (3) |
Geometric parameters (Å, º) top
S1—C1 | 1.718 (6) | C7—C9 | 1.512 (8) |
S1—C3 | 1.716 (5) | C8—C10 | 1.536 (8) |
S2—C2 | 1.730 (6) | C8—H5 | 0.95 |
S2—C3 | 1.724 (5) | C8—H6 | 0.94 |
S3—C4 | 1.717 (5) | C9—C11 | 1.532 (7) |
S3—C5 | 1.723 (6) | C9—H7 | 0.95 |
S4—C4 | 1.719 (5) | C9—H8 | 0.96 |
S4—C6 | 1.726 (6) | C10—C12 | 1.549 (8) |
S5—O2 | 1.659 (4) | C10—C13 | 1.510 (8) |
S5—O3 | 1.430 (4) | C11—C14 | 1.539 (8) |
S5—O4 | 1.437 (5) | C11—C15 | 1.514 (8) |
S5—O5 | 1.430 (5) | C12—H9 | 0.96 |
O1—C7 | 1.201 (6) | C12—H10 | 0.95 |
O2—N1 | 1.456 (5) | C12—H11 | 0.94 |
N1—C10 | 1.484 (7) | C13—H12 | 0.95 |
N1—C11 | 1.485 (7) | C13—H13 | 0.96 |
C1—C2 | 1.334 (8) | C13—H14 | 0.95 |
C1—H1 | 0.95 | C14—H15 | 1.07 |
C2—H2 | 0.95 | C14—H16 | 0.95 |
C3—C4 | 1.398 (7) | C14—H17 | 0.95 |
C5—C6 | 1.318 (8) | C15—H18 | 0.95 |
C5—H3 | 0.96 | C15—H19 | 0.95 |
C6—H4 | 0.95 | C15—H20 | 0.96 |
C7—C8 | 1.487 (8) | | |
| | | |
S1···O1i | 3.141 (5) | O3···C1viii | 3.346 (7) |
S1···S4ii | 3.329 (2) | O3···C8vi | 3.362 (8) |
S1···C3iii | 3.678 (6) | O4···C5 | 3.015 (8) |
S2···O5ii | 2.976 (5) | O4···C2viii | 3.190 (7) |
S2···S3ii | 3.416 (3) | O4···C1viii | 3.486 (7) |
S2···O2ii | 3.673 (4) | O5···C2ii | 3.036 (8) |
S3···O4 | 3.005 (5) | O5···C5vii | 3.303 (7) |
S3···O2 | 3.473 (4) | O5···C6vii | 3.579 (7) |
S4···O1iv | 3.123 (4) | O5···C15ix | 3.631 (8) |
O1···C6v | 3.235 (7) | C1···C6ii | 3.339 (9) |
O1···C1i | 3.310 (8) | C1···C5ii | 3.625 (9) |
O1···O3vi | 3.369 (5) | C2···C5ii | 3.40 (1) |
O1···C12i | 3.413 (8) | C2···C6ii | 3.617 (9) |
O3···C7vi | 3.034 (7) | C3···C4ii | 3.479 (8) |
O3···C9vi | 3.250 (7) | C5···C15x | 3.439 (9) |
O3···C6vii | 3.287 (7) | C6···C15x | 3.538 (9) |
| | | |
C1—S1—C3 | 95.1 (3) | C7—C9—H7 | 108.5 |
C2—S2—C3 | 95.3 (3) | C7—C9—H8 | 108.1 |
C4—S3—C5 | 94.7 (3) | C11—C9—H7 | 109.1 |
C4—S4—C6 | 94.7 (3) | C11—C9—H8 | 108.2 |
O2—S5—O3 | 108.5 (2) | H7—C9—H8 | 108.9 |
O2—S5—O4 | 101.8 (2) | N1—C10—C8 | 105.8 (5) |
O2—S5—O5 | 102.4 (2) | N1—C10—C12 | 115.5 (5) |
O3—S5—O4 | 114.2 (3) | N1—C10—C13 | 108.2 (5) |
O3—S5—O5 | 115.1 (3) | C8—C10—C12 | 110.0 (5) |
O4—S5—O5 | 113.0 (3) | C8—C10—C13 | 108.7 (5) |
S5—O2—N1 | 116.3 (3) | C12—C10—C13 | 108.4 (5) |
O2—N1—C10 | 105.8 (4) | N1—C11—C9 | 105.0 (5) |
O2—N1—C11 | 106.3 (4) | N1—C11—C14 | 116.5 (5) |
C10—N1—C11 | 119.6 (4) | N1—C11—C15 | 107.8 (5) |
S1—C1—C2 | 117.9 (5) | C9—C11—C14 | 110.8 (5) |
S1—C1—H1 | 121.7 | C9—C11—C15 | 108.3 (5) |
C2—C1—H1 | 120.3 | C14—C11—C15 | 108.1 (5) |
S2—C2—C1 | 116.3 (5) | C10—C12—H9 | 108.7 |
S2—C2—H2 | 121.6 | C10—C12—H10 | 109.2 |
C1—C2—H2 | 122.1 | C10—C12—H11 | 109.5 |
S1—C3—S2 | 115.2 (3) | H9—C12—H10 | 109.0 |
S1—C3—C4 | 122.5 (4) | H9—C12—H11 | 109.6 |
S2—C3—C4 | 122.1 (4) | H10—C12—H11 | 110.8 |
S3—C4—S4 | 115.7 (3) | C10—C13—H12 | 110.1 |
S3—C4—C3 | 122.4 (4) | C10—C13—H13 | 109.1 |
S4—C4—C3 | 121.9 (4) | C10—C13—H14 | 109.8 |
S3—C5—C6 | 117.7 (5) | H12—C13—H13 | 109.1 |
S3—C5—H3 | 121.2 | H12—C13—H14 | 109.9 |
C6—C5—H3 | 121.1 | H13—C13—H14 | 108.9 |
S4—C6—C5 | 117.2 (5) | C11—C14—H15 | 114.2 |
S4—C6—H4 | 121.5 | C11—C14—H16 | 107.7 |
C5—C6—H4 | 121.3 | C11—C14—H17 | 108.1 |
O1—C7—C8 | 124.2 (6) | H15—C14—H16 | 108.3 |
O1—C7—C9 | 123.8 (6) | H15—C14—H17 | 108.6 |
C8—C7—C9 | 112.1 (5) | H16—C14—H17 | 109.9 |
C7—C8—C10 | 114.5 (5) | C11—C15—H18 | 109.8 |
C7—C8—H5 | 107.7 | C11—C15—H19 | 110.2 |
C7—C8—H6 | 108.2 | C11—C15—H20 | 109.3 |
C10—C8—H5 | 108.1 | H18—C15—H19 | 109.7 |
C10—C8—H6 | 108.9 | H18—C15—H20 | 108.9 |
H5—C8—H6 | 109.5 | H19—C15—H20 | 109.0 |
C7—C9—C11 | 114.0 (5) | | |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z; (iii) −x, −y, −z+1; (iv) x, y−1, z−1; (v) x, y+1, z+1; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y, −z; (viii) x+1, y, z; (ix) x, y, z−1; (x) −x+1, −y, −z+1. |