Tetra­thia­fulvalenium 4-oxo-2,2,6,6-tetra­methyl­piperidin-1-sulfate

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).

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](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

---

Computing details

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.

(3)

Crystal data

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) Å^3

Data collection

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

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters not refined
wR(F^2) = 0.042	Weighting scheme based on measured s.u.'s w = 1/[σ^2(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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···O1^i	3.141 (5)	O3···C1^viii	3.346 (7)
S1···S4^ii	3.329 (2)	O3···C8^vi	3.362 (8)
S1···C3^iii	3.678 (6)	O4···C5	3.015 (8)
S2···O5^ii	2.976 (5)	O4···C2^viii	3.190 (7)
S2···S3^ii	3.416 (3)	O4···C1^viii	3.486 (7)
S2···O2^ii	3.673 (4)	O5···C2^ii	3.036 (8)
S3···O4	3.005 (5)	O5···C5^vii	3.303 (7)
S3···O2	3.473 (4)	O5···C6^vii	3.579 (7)
S4···O1^iv	3.123 (4)	O5···C15^ix	3.631 (8)
O1···C6^v	3.235 (7)	C1···C6^ii	3.339 (9)
O1···C1^i	3.310 (8)	C1···C5^ii	3.625 (9)
O1···O3^vi	3.369 (5)	C2···C5^ii	3.40 (1)
O1···C12^i	3.413 (8)	C2···C6^ii	3.617 (9)
O3···C7^vi	3.034 (7)	C3···C4^ii	3.479 (8)
O3···C9^vi	3.250 (7)	C5···C15^x	3.439 (9)
O3···C6^vii	3.287 (7)	C6···C15^x	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.