Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103012824/ob1128sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103012824/ob1128Isup2.hkl |
CCDC reference: 219568
For the preparation of (I), the corresponding sodium salt was prepared by reacting 4-oxo-TEMPO (1.0 g, 5.9 mmol) with NaHSO3 (1.8 g, 18 mmol) in a mixed solvent of tetrahydrofuran (10 ml), water (10 ml) and H2SO4 (30%, 1.7 g) at 278–280 K, with stirring for 1–2 min. Exchange of the counter-cation with tetraphenylphosphonium chloride gave the title salt, (I), as orange needle-like crystals after recrystallization from CH2Cl2/toluene (overall yield 62%).
There is positional disorder in one of the sulfonate O atoms, and this O atom was refined over two possible positions (O31 and O32), each with an occupancy of 50%. The elongated displacement ellipsoids of the sulfonate O atoms suggest rotational disorder of the –SO3 group. All H atoms were located from difference density maps and assigned fixed distances and Uiso values of 0.0507 Å2.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Coorporation, 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: CRYSTALS (Watkin et al., 2001); software used to prepare material for publication: TEXSAN for Windows.
Fig. 1. A view of the anions in (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) −x, 1 − y, 2 − z.] |
C24H20P+·C9H17NO5S− | Z = 2 |
Mr = 590.69 | F(000) = 626.00 |
Triclinic, P1 | Dx = 1.299 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 11.733 (2) Å | Cell parameters from 24 reflections |
b = 12.212 (3) Å | θ = 14.9–15.0° |
c = 11.501 (3) Å | µ = 0.20 mm−1 |
α = 103.79 (2)° | T = 296 K |
β = 96.89 (2)° | Block, orange |
γ = 70.82 (1)° | 0.50 × 0.50 × 0.30 mm |
V = 1510.1 (6) Å3 |
Rigaku AFC-7R diffractometer | 4180 reflections with I > 3σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.032 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ω/2θ scans | h = 0→15 |
Absorption correction: psi scan (North et al., 1968) | k = −14→15 |
Tmin = 0.888, Tmax = 0.941 | l = −14→14 |
7269 measured reflections | 3 standard reflections every 150 reflections |
6933 independent reflections | intensity decay: 0.5% |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters not refined |
wR(F2) = 0.051 | Method = Prince modified Chebychev polynomial (Watkin, 1994)
W = [weight] * [1-(deltaF/6*sigmaF)2]2 3.99 -1.74 2.77 |
S = 1.19 | (Δ/σ)max = 0.000202 |
4185 reflections | Δρmax = 0.56 e Å−3 |
379 parameters | Δρmin = −0.46 e Å−3 |
C24H20P+·C9H17NO5S− | γ = 70.82 (1)° |
Mr = 590.69 | V = 1510.1 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.733 (2) Å | Mo Kα radiation |
b = 12.212 (3) Å | µ = 0.20 mm−1 |
c = 11.501 (3) Å | T = 296 K |
α = 103.79 (2)° | 0.50 × 0.50 × 0.30 mm |
β = 96.89 (2)° |
Rigaku AFC-7R diffractometer | 4180 reflections with I > 3σ(I) |
Absorption correction: psi scan (North et al., 1968) | Rint = 0.032 |
Tmin = 0.888, Tmax = 0.941 | 3 standard reflections every 150 reflections |
7269 measured reflections | intensity decay: 0.5% |
6933 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters not refined |
S = 1.19 | Δρmax = 0.56 e Å−3 |
4185 reflections | Δρmin = −0.46 e Å−3 |
379 parameters |
Experimental. The scan width was (1.78 + 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.02847 (9) | 0.32821 (8) | 1.10460 (8) | 0.0642 | |
P1 | 0.63854 (6) | 0.30107 (6) | 0.61523 (6) | 0.0338 | |
O1 | −0.0535 (3) | 0.4399 (2) | 1.0929 (4) | 0.1280 | |
O2 | −0.0326 (3) | 0.2411 (2) | 1.0915 (2) | 0.0784 | |
O31 | 0.0990 (16) | 0.3649 (11) | 1.2027 (12) | 0.1239 | 0.5000 |
O32 | 0.1124 (13) | 0.3037 (9) | 1.2150 (11) | 0.0881 | 0.5000 |
O4 | 0.1925 (2) | 0.3617 (2) | 0.9900 (2) | 0.0722 | |
O5 | 0.2667 (2) | 0.0418 (2) | 0.66355 (19) | 0.0666 | |
N1 | 0.2189 (2) | 0.1111 (2) | 0.75956 (19) | 0.0437 | |
C1 | 0.7352 (2) | 0.3395 (2) | 0.5325 (2) | 0.0375 | |
C2 | 0.7856 (3) | 0.2583 (3) | 0.4296 (3) | 0.0454 | |
C3 | 0.8631 (3) | 0.2844 (3) | 0.3660 (3) | 0.0554 | |
C4 | 0.8904 (3) | 0.3895 (4) | 0.4049 (3) | 0.0620 | |
C5 | 0.8419 (3) | 0.4688 (3) | 0.5050 (3) | 0.0622 | |
C6 | 0.7632 (3) | 0.4445 (3) | 0.5696 (3) | 0.0493 | |
C7 | 0.7262 (2) | 0.1841 (2) | 0.6897 (2) | 0.0369 | |
C8 | 0.7806 (3) | 0.0725 (2) | 0.6215 (3) | 0.0458 | |
C9 | 0.8519 (3) | −0.0168 (3) | 0.6773 (3) | 0.0552 | |
C10 | 0.8702 (3) | 0.0036 (3) | 0.7999 (3) | 0.0565 | |
C11 | 0.8174 (4) | 0.1140 (3) | 0.8673 (3) | 0.0640 | |
C12 | 0.7453 (3) | 0.2039 (3) | 0.8132 (3) | 0.0541 | |
C13 | 0.5319 (2) | 0.2491 (2) | 0.5107 (2) | 0.0362 | |
C14 | 0.4792 (3) | 0.1731 (3) | 0.5396 (3) | 0.0462 | |
C15 | 0.3904 (3) | 0.1392 (3) | 0.4629 (3) | 0.0557 | |
C16 | 0.3549 (3) | 0.1805 (3) | 0.3589 (3) | 0.0557 | |
C17 | 0.4070 (3) | 0.2553 (3) | 0.3294 (3) | 0.0513 | |
C18 | 0.4957 (3) | 0.2906 (2) | 0.4057 (3) | 0.0424 | |
C19 | 0.5585 (2) | 0.4259 (2) | 0.7246 (2) | 0.0373 | |
C20 | 0.6206 (3) | 0.4883 (3) | 0.8139 (3) | 0.0515 | |
C21 | 0.5575 (4) | 0.5817 (3) | 0.8978 (3) | 0.0667 | |
C22 | 0.4342 (4) | 0.6145 (3) | 0.8963 (3) | 0.0690 | |
C23 | 0.3710 (3) | 0.5533 (3) | 0.8114 (3) | 0.0619 | |
C24 | 0.4334 (3) | 0.4594 (3) | 0.7243 (3) | 0.0465 | |
C25 | 0.1268 (3) | 0.2807 (3) | 0.9762 (3) | 0.0465 | |
C26 | 0.2127 (3) | 0.1579 (3) | 0.9812 (3) | 0.0594 | |
C27 | 0.0505 (2) | 0.2746 (3) | 0.8611 (3) | 0.0445 | |
C28 | 0.2891 (3) | 0.0927 (3) | 0.8721 (3) | 0.0562 | |
C29 | 0.1211 (2) | 0.2211 (3) | 0.7458 (3) | 0.0454 | |
C30 | 0.3268 (5) | −0.0408 (4) | 0.8696 (4) | 0.0951 | |
C31 | 0.4017 (3) | 0.1322 (5) | 0.8752 (4) | 0.0901 | |
C32 | 0.0351 (4) | 0.1852 (5) | 0.6452 (3) | 0.0887 | |
C33 | 0.1728 (4) | 0.3077 (3) | 0.7104 (4) | 0.0750 | |
H1 | 0.1400 | 0.4350 | 0.9754 | 0.0507* | |
H2 | 0.7646 | 0.1902 | 0.4059 | 0.0507* | |
H3 | 0.8972 | 0.2301 | 0.2957 | 0.0507* | |
H4 | 0.9427 | 0.4066 | 0.3593 | 0.0507* | |
H5 | 0.8617 | 0.5398 | 0.5307 | 0.0507* | |
H6 | 0.7314 | 0.5002 | 0.6367 | 0.0507* | |
H8 | 0.7690 | 0.0563 | 0.5366 | 0.0507* | |
H9 | 0.8873 | −0.0942 | 0.6291 | 0.0507* | |
H10 | 0.9195 | −0.0607 | 0.8327 | 0.0507* | |
H11 | 0.8314 | 0.1316 | 0.9524 | 0.0507* | |
H12 | 0.7162 | 0.2813 | 0.8568 | 0.0507* | |
H14 | 0.5056 | 0.1444 | 0.6110 | 0.0507* | |
H15 | 0.3584 | 0.0863 | 0.4887 | 0.0507* | |
H16 | 0.2939 | 0.1586 | 0.3065 | 0.0507* | |
H17 | 0.3818 | 0.2861 | 0.2590 | 0.0507* | |
H18 | 0.5299 | 0.3459 | 0.3859 | 0.0507* | |
H20 | 0.7103 | 0.4624 | 0.8169 | 0.0507* | |
H21 | 0.5949 | 0.6249 | 0.9532 | 0.0507* | |
H22 | 0.3912 | 0.6778 | 0.9554 | 0.0507* | |
H23 | 0.2858 | 0.5758 | 0.8116 | 0.0507* | |
H24 | 0.3931 | 0.4186 | 0.6677 | 0.0507* | |
H261 | 0.1644 | 0.1117 | 0.9891 | 0.0507* | |
H262 | 0.2685 | 0.1667 | 1.0466 | 0.0507* | |
H271 | 0.0020 | 0.2277 | 0.8602 | 0.0507* | |
H272 | −0.0051 | 0.3562 | 0.8554 | 0.0507* | |
H301 | 0.2984 | −0.0517 | 0.9381 | 0.0507* | |
H302 | 0.2945 | −0.0788 | 0.7991 | 0.0507* | |
H303 | 0.4132 | −0.0713 | 0.8713 | 0.0507* | |
H311 | 0.4721 | 0.0645 | 0.8757 | 0.0507* | |
H312 | 0.3993 | 0.1615 | 0.8057 | 0.0507* | |
H313 | 0.4032 | 0.1905 | 0.9447 | 0.0507* | |
H321 | −0.0445 | 0.2131 | 0.6720 | 0.0507* | |
H322 | 0.0382 | 0.2169 | 0.5784 | 0.0507* | |
H323 | 0.0595 | 0.1004 | 0.6215 | 0.0507* | |
H331 | 0.2268 | 0.3280 | 0.7691 | 0.0507* | |
H332 | 0.2091 | 0.2716 | 0.6384 | 0.0507* | |
H333 | 0.1086 | 0.3752 | 0.6997 | 0.0507* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0720 (6) | 0.0542 (5) | 0.0545 (5) | −0.0084 (4) | 0.0260 (4) | −0.0063 (4) |
P1 | 0.0321 (3) | 0.0340 (3) | 0.0359 (3) | −0.0101 (3) | 0.0046 (3) | 0.0072 (3) |
O1 | 0.139 (3) | 0.0517 (16) | 0.192 (4) | 0.0171 (17) | 0.126 (3) | 0.0320 (19) |
O2 | 0.119 (2) | 0.0614 (15) | 0.0626 (15) | −0.0285 (15) | 0.0402 (15) | 0.0095 (12) |
O31 | 0.144 (11) | 0.163 (12) | 0.050 (6) | −0.064 (11) | 0.030 (6) | −0.042 (8) |
O32 | 0.088 (5) | 0.116 (8) | 0.033 (3) | −0.011 (6) | 0.004 (3) | −0.006 (5) |
O4 | 0.0531 (13) | 0.0586 (14) | 0.0931 (18) | −0.0212 (12) | 0.0189 (13) | −0.0191 (13) |
O5 | 0.0806 (17) | 0.0633 (15) | 0.0403 (12) | −0.0112 (12) | 0.0127 (11) | −0.007 (1) |
N1 | 0.0487 (14) | 0.0435 (13) | 0.0325 (12) | −0.0106 (11) | 0.002 (1) | 0.001 (1) |
C1 | 0.0281 (12) | 0.0424 (14) | 0.0432 (14) | −0.0059 (11) | 0.0049 (11) | 0.0167 (12) |
C2 | 0.0392 (15) | 0.0525 (17) | 0.0434 (15) | −0.0096 (13) | 0.0055 (12) | 0.0130 (13) |
C3 | 0.0396 (16) | 0.076 (2) | 0.0477 (17) | −0.0062 (15) | 0.0099 (14) | 0.0214 (16) |
C4 | 0.0428 (17) | 0.091 (3) | 0.067 (2) | −0.0260 (18) | 0.0101 (16) | 0.034 (2) |
C5 | 0.056 (2) | 0.065 (2) | 0.082 (2) | −0.0308 (17) | 0.0111 (18) | 0.0235 (18) |
C6 | 0.0472 (17) | 0.0472 (16) | 0.0588 (18) | −0.0170 (14) | 0.0135 (14) | 0.0126 (14) |
C7 | 0.0361 (14) | 0.0395 (14) | 0.0384 (14) | −0.0132 (11) | 0.0002 (11) | 0.0133 (11) |
C8 | 0.0527 (17) | 0.0387 (15) | 0.0425 (15) | −0.0119 (13) | −0.0011 (13) | 0.0070 (12) |
C9 | 0.062 (2) | 0.0398 (16) | 0.060 (2) | −0.0111 (15) | −0.0022 (16) | 0.0121 (14) |
C10 | 0.0583 (19) | 0.0541 (19) | 0.064 (2) | −0.0161 (16) | −0.0085 (16) | 0.0332 (16) |
C11 | 0.081 (2) | 0.070 (2) | 0.0429 (17) | −0.020 (2) | −0.0025 (17) | 0.0225 (16) |
C12 | 0.070 (2) | 0.0504 (18) | 0.0404 (16) | −0.0130 (16) | 0.0108 (15) | 0.0108 (13) |
C13 | 0.0359 (14) | 0.0309 (13) | 0.0408 (14) | −0.0095 (11) | 0.0044 (11) | 0.0053 (11) |
C14 | 0.0470 (16) | 0.0481 (16) | 0.0486 (16) | −0.0192 (13) | 0.0029 (13) | 0.0134 (13) |
C15 | 0.0558 (19) | 0.0554 (19) | 0.065 (2) | −0.0314 (16) | 0.0013 (16) | 0.0115 (16) |
C16 | 0.0529 (18) | 0.0574 (19) | 0.057 (2) | −0.0271 (16) | −0.0078 (15) | 0.0035 (15) |
C17 | 0.0554 (18) | 0.0526 (18) | 0.0448 (16) | −0.0168 (15) | −0.0069 (14) | 0.0128 (14) |
C18 | 0.0435 (15) | 0.0405 (15) | 0.0459 (15) | −0.0158 (12) | −0.0020 (12) | 0.0123 (12) |
C19 | 0.0406 (14) | 0.0355 (14) | 0.0362 (13) | −0.0120 (11) | 0.0078 (11) | 0.0049 (11) |
C20 | 0.0563 (19) | 0.0554 (18) | 0.0469 (17) | −0.0261 (15) | 0.0036 (14) | 0.0057 (14) |
C21 | 0.101 (3) | 0.058 (2) | 0.0443 (17) | −0.040 (2) | 0.0120 (18) | −0.0082 (15) |
C22 | 0.097 (3) | 0.0504 (19) | 0.0502 (19) | −0.0091 (19) | 0.032 (2) | −0.0018 (15) |
C23 | 0.0549 (19) | 0.062 (2) | 0.059 (2) | 0.0016 (16) | 0.0213 (16) | 0.0141 (17) |
C24 | 0.0440 (16) | 0.0478 (16) | 0.0455 (16) | −0.0092 (13) | 0.0077 (13) | 0.0103 (13) |
C25 | 0.0430 (16) | 0.0412 (15) | 0.0459 (16) | −0.0062 (13) | 0.0093 (13) | −0.0024 (12) |
C26 | 0.063 (2) | 0.059 (2) | 0.0348 (15) | 0.0051 (16) | −0.0017 (14) | 0.0058 (14) |
C27 | 0.0353 (14) | 0.0482 (16) | 0.0512 (16) | −0.0073 (12) | 0.0070 (12) | 0.0181 (13) |
C28 | 0.0539 (18) | 0.0522 (18) | 0.0393 (16) | 0.0087 (14) | −0.0018 (13) | 0.0039 (13) |
C29 | 0.0362 (15) | 0.0573 (18) | 0.0432 (15) | −0.0071 (13) | 0.0018 (12) | 0.0218 (13) |
C30 | 0.115 (3) | 0.064 (2) | 0.062 (2) | 0.039 (2) | 0.016 (2) | 0.0180 (19) |
C31 | 0.0427 (19) | 0.125 (4) | 0.066 (2) | −0.003 (2) | −0.0083 (17) | −0.009 (2) |
C32 | 0.054 (2) | 0.153 (4) | 0.048 (2) | −0.018 (2) | −0.0109 (17) | 0.027 (2) |
C33 | 0.072 (2) | 0.066 (2) | 0.092 (3) | −0.0010 (18) | 0.040 (2) | 0.036 (2) |
S1—O1 | 1.413 (3) | C15—H15 | 0.961 |
S1—O2 | 1.437 (3) | C16—C17 | 1.373 (4) |
S1—O31 | 1.392 (16) | C16—H16 | 0.944 |
S1—O32 | 1.536 (13) | C17—C18 | 1.391 (4) |
S1—C25 | 1.846 (3) | C17—H17 | 0.948 |
P1—C1 | 1.798 (3) | C18—H18 | 0.972 |
P1—C7 | 1.800 (3) | C19—C20 | 1.406 (4) |
P1—C13 | 1.792 (3) | C19—C24 | 1.389 (4) |
P1—C19 | 1.794 (3) | C20—C21 | 1.368 (4) |
O31—O32 | 0.756 (16) | C20—H20 | 0.993 |
O4—C25 | 1.412 (4) | C21—C22 | 1.368 (6) |
O4—H1 | 0.945 | C21—H21 | 0.896 |
O5—N1 | 1.281 (3) | C22—C23 | 1.379 (5) |
N1—C28 | 1.471 (4) | C22—H22 | 0.943 |
N1—C29 | 1.481 (4) | C23—C24 | 1.390 (4) |
C1—C2 | 1.399 (4) | C23—H23 | 0.947 |
C1—C6 | 1.385 (4) | C24—H24 | 0.906 |
C2—C3 | 1.388 (4) | C25—C26 | 1.517 (4) |
C2—H2 | 0.915 | C25—C27 | 1.507 (4) |
C3—C4 | 1.383 (5) | C26—C28 | 1.529 (4) |
C3—H3 | 0.950 | C26—H261 | 0.946 |
C4—C5 | 1.360 (5) | C26—H262 | 0.946 |
C4—H4 | 0.953 | C27—C29 | 1.538 (4) |
C5—C6 | 1.393 (4) | C27—H271 | 0.929 |
C5—H5 | 0.942 | C27—H272 | 1.008 |
C6—H6 | 0.922 | C28—C30 | 1.536 (5) |
C7—C8 | 1.385 (4) | C28—C31 | 1.542 (6) |
C7—C12 | 1.387 (4) | C29—C32 | 1.523 (5) |
C8—C9 | 1.380 (4) | C29—C33 | 1.528 (5) |
C8—H8 | 0.952 | C30—H301 | 0.943 |
C9—C10 | 1.376 (5) | C30—H302 | 0.938 |
C9—H9 | 0.959 | C30—H303 | 0.958 |
C10—C11 | 1.367 (5) | C31—H311 | 0.959 |
C10—H10 | 0.940 | C31—H312 | 0.945 |
C11—C12 | 1.377 (5) | C31—H313 | 0.938 |
C11—H11 | 0.958 | C32—H321 | 0.945 |
C12—H12 | 0.929 | C32—H322 | 0.948 |
C13—C14 | 1.388 (4) | C32—H323 | 0.959 |
C13—C18 | 1.386 (4) | C33—H331 | 0.917 |
C14—C15 | 1.387 (4) | C33—H332 | 0.921 |
C14—H14 | 0.948 | C33—H333 | 0.939 |
C15—C16 | 1.374 (5) | ||
O1—S1—O2 | 111.4 (2) | C13—C18—H18 | 120.699 |
O1—S1—O31 | 99.3 (6) | C17—C18—H18 | 119.505 |
O2—S1—O31 | 127.6 (6) | P1—C19—C20 | 121.1 (2) |
O1—S1—O32 | 125.2 (4) | P1—C19—C24 | 119.7 (2) |
O2—S1—O32 | 100.8 (5) | C20—C19—C24 | 119.1 (3) |
O31—S1—O32 | 29.4 (6) | C19—C20—C21 | 119.9 (3) |
O1—S1—C25 | 105.40 (16) | C19—C20—H20 | 119.483 |
O2—S1—C25 | 106.50 (14) | C21—C20—H20 | 120.581 |
O31—S1—C25 | 104.8 (7) | C20—C21—C22 | 120.6 (3) |
O32—S1—C25 | 106.4 (5) | C20—C21—H21 | 121.366 |
C1—P1—C7 | 110.09 (12) | C22—C21—H21 | 118.003 |
C1—P1—C13 | 107.89 (12) | C21—C22—C23 | 120.8 (3) |
C7—P1—C13 | 108.81 (12) | C21—C22—H22 | 120.184 |
C1—P1—C19 | 111.79 (12) | C23—C22—H22 | 119.006 |
C7—P1—C19 | 109.01 (12) | C22—C23—C24 | 119.5 (3) |
C13—P1—C19 | 109.19 (12) | C22—C23—H23 | 120.362 |
S1—O31—O32 | 86 (2) | C24—C23—H23 | 120.107 |
S1—O32—O31 | 64.7 (19) | C19—C24—C23 | 120.1 (3) |
C25—O4—H1 | 109.461 | C19—C24—H24 | 119.376 |
O5—N1—C28 | 115.9 (2) | C23—C24—H24 | 120.547 |
O5—N1—C29 | 116.9 (2) | S1—C25—O4 | 107.71 (19) |
C28—N1—C29 | 124.5 (2) | S1—C25—C26 | 107.4 (2) |
P1—C1—C2 | 118.2 (2) | O4—C25—C26 | 110.0 (3) |
P1—C1—C6 | 122.0 (2) | S1—C25—C27 | 109.4 (2) |
C2—C1—C6 | 119.8 (2) | O4—C25—C27 | 112.9 (3) |
C1—C2—C3 | 119.3 (3) | C26—C25—C27 | 109.4 (2) |
C1—C2—H2 | 118.225 | C25—C26—C28 | 116.3 (3) |
C3—C2—H2 | 122.467 | C25—C26—H261 | 106.421 |
C2—C3—C4 | 120.1 (3) | C28—C26—H261 | 107.584 |
C2—C3—H3 | 119.873 | C25—C26—H262 | 107.306 |
C4—C3—H3 | 120.073 | C28—C26—H262 | 105.608 |
C3—C4—C5 | 121.0 (3) | H261—C26—H262 | 113.895 |
C3—C4—H4 | 118.852 | C25—C27—C29 | 115.4 (2) |
C5—C4—H4 | 120.176 | C25—C27—H271 | 109.798 |
C4—C5—C6 | 119.8 (3) | C29—C27—H271 | 105.839 |
C4—C5—H5 | 120.049 | C25—C27—H272 | 110.101 |
C6—C5—H5 | 120.103 | C29—C27—H272 | 108.291 |
C1—C6—C5 | 120.1 (3) | H271—C27—H272 | 107.044 |
C1—C6—H6 | 122.167 | N1—C28—C26 | 111.5 (2) |
C5—C6—H6 | 117.745 | N1—C28—C30 | 106.9 (3) |
P1—C7—C8 | 119.2 (2) | C26—C28—C30 | 107.6 (3) |
P1—C7—C12 | 121.8 (2) | N1—C28—C31 | 108.1 (3) |
C8—C7—C12 | 119.0 (3) | C26—C28—C31 | 112.4 (3) |
C7—C8—C9 | 119.8 (3) | C30—C28—C31 | 110.3 (3) |
C7—C8—H8 | 120.821 | N1—C29—C27 | 109.9 (2) |
C9—C8—H8 | 119.427 | N1—C29—C32 | 106.7 (3) |
C8—C9—C10 | 120.9 (3) | C27—C29—C32 | 107.9 (3) |
C8—C9—H9 | 118.842 | N1—C29—C33 | 110.3 (2) |
C10—C9—H9 | 120.289 | C27—C29—C33 | 113.0 (3) |
C9—C10—C11 | 119.5 (3) | C32—C29—C33 | 109.0 (3) |
C9—C10—H10 | 116.938 | C28—C30—H301 | 108.821 |
C11—C10—H10 | 123.603 | C28—C30—H302 | 109.116 |
C10—C11—C12 | 120.5 (3) | H301—C30—H302 | 111.118 |
C10—C11—H11 | 121.176 | C28—C30—H303 | 108.488 |
C12—C11—H11 | 118.339 | H301—C30—H303 | 109.377 |
C7—C12—C11 | 120.5 (3) | H302—C30—H303 | 109.871 |
C7—C12—H12 | 117.846 | C28—C31—H311 | 108.422 |
C11—C12—H12 | 121.237 | C28—C31—H312 | 109.033 |
P1—C13—C14 | 119.3 (2) | H311—C31—H312 | 109.196 |
P1—C13—C18 | 120.57 (19) | C28—C31—H313 | 109.469 |
C14—C13—C18 | 120.0 (2) | H311—C31—H313 | 109.730 |
C13—C14—C15 | 119.6 (3) | H312—C31—H313 | 110.945 |
C13—C14—H14 | 119.184 | C29—C32—H321 | 109.980 |
C15—C14—H14 | 121.193 | C29—C32—H322 | 109.713 |
C14—C15—C16 | 120.2 (3) | H321—C32—H322 | 110.102 |
C14—C15—H15 | 114.887 | C29—C32—H323 | 108.987 |
C16—C15—H15 | 124.922 | H321—C32—H323 | 109.139 |
C15—C16—C17 | 120.6 (3) | H322—C32—H323 | 108.893 |
C15—C16—H16 | 120.871 | C29—C33—H331 | 109.889 |
C17—C16—H16 | 118.568 | C29—C33—H332 | 108.142 |
C16—C17—C18 | 119.9 (3) | H331—C33—H332 | 111.300 |
C16—C17—H17 | 121.456 | C29—C33—H333 | 108.322 |
C18—C17—H17 | 118.605 | H331—C33—H333 | 110.433 |
C13—C18—C17 | 119.8 (3) | H332—C33—H333 | 108.672 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1···O1i | 0.95 | 1.83 | 2.754 (5) | 165 |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C24H20P+·C9H17NO5S− |
Mr | 590.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 11.733 (2), 12.212 (3), 11.501 (3) |
α, β, γ (°) | 103.79 (2), 96.89 (2), 70.82 (1) |
V (Å3) | 1510.1 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.50 × 0.50 × 0.30 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Psi scan (North et al., 1968) |
Tmin, Tmax | 0.888, 0.941 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 7269, 6933, 4180 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.051, 1.19 |
No. of reflections | 4185 |
No. of parameters | 379 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.56, −0.46 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Coorporation, 1994), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 2001), TEXSAN for Windows.
S1—O1 | 1.413 (3) | C25—C26 | 1.517 (4) |
S1—O2 | 1.437 (3) | C25—C27 | 1.507 (4) |
S1—O31 | 1.392 (16) | C26—C28 | 1.529 (4) |
S1—O32 | 1.536 (13) | C27—C29 | 1.538 (4) |
S1—C25 | 1.846 (3) | C28—C30 | 1.536 (5) |
O4—C25 | 1.412 (4) | C28—C31 | 1.542 (6) |
O5—N1 | 1.281 (3) | C29—C32 | 1.523 (5) |
N1—C28 | 1.471 (4) | C29—C33 | 1.528 (5) |
N1—C29 | 1.481 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1···O1i | 0.95 | 1.83 | 2.754 (5) | 165 |
Symmetry code: (i) −x, −y+1, −z+2. |
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In recent decades, many stable organic radicals and their derivatives have been synthesized because they are suitable for use in studying the magnetic properties of molecular materials (Kahn, 1993). Our current interests are in the preparation, elucidation of structure and characterization of stable organic radical anions that are useful not only as components of magnetic materials but also as counter-ions of organic conductors (Akutsu et al., 2001a, 2001b). We have examined the anion that is the bisulfide adduct of 4-Oxo-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-oxyl), and we report here the structure of the tetraphenylphosphonium salt, viz. the title compound, (I).
The crystal is constructed from the tetraphenyphosphonium cation and the anion. A view of the anion is shown in Fig. 1 and selected dimensions are presented in Table 1. The anion forms a dimer about the centre of symmetry, with hydrogen bonds between sulfonate atom O1 and hydroxy atom O4 in the centrosymmetrically related molecule (Fig. 1 and Table 2). Similar hydrogen bonds are observed in another dimeric bisulfide adduct, namely potassium hydroxymethanesulfonate (Cameron & Chute, 1979).
The O5···O5(-x, 1 − y, 2 − z) distance between the spin centres of the TEMPO anions in the dimer is 12.192 (5) Å, indicating that magnetic interactions are unlikely via this intradimer route. Each dimer is also surrounded by tetraphenylphosphonium cations, which add to the magnetic isolation. In fact, the nearest distance, O5···O5(1 − x, −y, 1 − z), is 6.678 (5) Å, which is too large to allow any significant magnetic interactions in the crystal. These results are consistent with the bulk magnetic properties of this salt (Currie-Weiss behaviour from 2–300 K with C = 0.391 emu mol−1 K−1 and θ = −0.137 K).