Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104006754/sk1705sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006754/sk1705IIsup2.hkl |
CCDC reference: 241231
Compound (II) was synthesized from (I) and purified in 72% yield using previously reported procedures (Sankaran & Reynolds, 1997; Lima et al., 1998). During purification/recrystallization in ethyl acetate, white needles were obtained, along with a lesser amount of dark-yellow chunk-like crystals. The 1H NMR data were in agreement with those reported previously (Sankaran & Reynolds, 1997) for (II).
Data collection: IPDS Software (Stoe & Cie, 1996); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: Sir97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
C10H12O6S | F(000) = 1088 |
Mr = 260.27 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7998 reflections |
a = 8.7337 (9) Å | θ = 2.4–25.9° |
b = 19.8208 (14) Å | µ = 0.29 mm−1 |
c = 13.6271 (15) Å | T = 160 K |
β = 99.059 (13)° | Block, yellow |
V = 2329.5 (4) Å3 | 0.48 × 0.23 × 0.1 mm |
Z = 8 |
STOE imaging-plate diffractometer | 4535 independent reflections |
Radiation source: fine-focus sealed tube | 3225 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ϕ scan | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (Blessing, 1995) | h = −10→10 |
Tmin = 0.928, Tmax = 0.971 | k = −24→24 |
20063 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.072 | All H-atom parameters refined |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0369P)2] where P = (Fo2 + 2Fc2)/3 |
4535 reflections | (Δ/σ)max = 0.001 |
403 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C10H12O6S | V = 2329.5 (4) Å3 |
Mr = 260.27 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7337 (9) Å | µ = 0.29 mm−1 |
b = 19.8208 (14) Å | T = 160 K |
c = 13.6271 (15) Å | 0.48 × 0.23 × 0.1 mm |
β = 99.059 (13)° |
STOE imaging-plate diffractometer | 4535 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3225 reflections with I > 2σ(I) |
Tmin = 0.928, Tmax = 0.971 | Rint = 0.069 |
20063 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.072 | All H-atom parameters refined |
S = 0.94 | Δρmax = 0.28 e Å−3 |
4535 reflections | Δρmin = −0.21 e Å−3 |
403 parameters |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS) equipped with an Oxford Cryosystems cooler device. The crystal-to-detector distance was 70 mm. 147 exposures (2.75 min per exposure) were obtained with 0 < ϕ < 220° and with the crystals rotated through 1.5° in ϕ. Crystal decay was monitored by measuring a maximum 200 reflections per image. Crystal orientation was checked with a maximum of 50 reflections per image. |
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. |
x | y | z | Uiso*/Ueq | ||
S11 | 0.85873 (6) | 0.48644 (2) | 0.38516 (3) | 0.02004 (11) | |
O11 | 0.7740 (2) | 0.66417 (7) | 0.48496 (11) | 0.0322 (4) | |
O12 | 0.64258 (17) | 0.56371 (7) | 0.58835 (10) | 0.0260 (3) | |
O13 | 0.95794 (18) | 0.67624 (7) | 0.33965 (11) | 0.0328 (4) | |
O14 | 1.01487 (16) | 0.58045 (6) | 0.26416 (9) | 0.0231 (3) | |
O15 | 0.63195 (17) | 0.42017 (6) | 0.59256 (9) | 0.0270 (3) | |
O16 | 0.72980 (17) | 0.36798 (6) | 0.46918 (10) | 0.0255 (3) | |
C11 | 0.8650 (2) | 0.57350 (9) | 0.39067 (13) | 0.0203 (4) | |
C12 | 0.7873 (2) | 0.59905 (9) | 0.46229 (14) | 0.0212 (4) | |
C13 | 0.7206 (2) | 0.54751 (9) | 0.51480 (13) | 0.0195 (4) | |
C14 | 0.7495 (2) | 0.48445 (9) | 0.48036 (13) | 0.0195 (4) | |
C15 | 0.9491 (2) | 0.61536 (9) | 0.33009 (14) | 0.0211 (4) | |
C16 | 1.1066 (2) | 0.61952 (10) | 0.20410 (15) | 0.0236 (4) | |
C17 | 1.1600 (3) | 0.57140 (11) | 0.13206 (16) | 0.0271 (4) | |
C18 | 0.6973 (2) | 0.42213 (9) | 0.52046 (13) | 0.0203 (4) | |
C19 | 0.6771 (3) | 0.30384 (10) | 0.50360 (18) | 0.0334 (5) | |
C20 | 0.7282 (4) | 0.25021 (11) | 0.4399 (2) | 0.0387 (6) | |
S1 | 0.28102 (6) | 0.46940 (2) | 0.95314 (3) | 0.02113 (12) | |
O1 | 0.31948 (19) | 0.28012 (6) | 0.88187 (11) | 0.0289 (3) | |
O2 | 0.46599 (18) | 0.36389 (7) | 0.76029 (10) | 0.0263 (3) | |
O3 | 0.12833 (19) | 0.29392 (7) | 1.02739 (11) | 0.0350 (4) | |
O4 | 0.10577 (17) | 0.39817 (7) | 1.08905 (10) | 0.0304 (3) | |
O5 | 0.51859 (16) | 0.49875 (6) | 0.73610 (10) | 0.0262 (3) | |
O6 | 0.41913 (16) | 0.57246 (6) | 0.83475 (9) | 0.0233 (3) | |
C1 | 0.2525 (2) | 0.38380 (9) | 0.96184 (13) | 0.0207 (4) | |
C2 | 0.3199 (2) | 0.34747 (9) | 0.89392 (14) | 0.0208 (4) | |
C3 | 0.3956 (2) | 0.38997 (9) | 0.83227 (13) | 0.0204 (4) | |
C4 | 0.3833 (2) | 0.45679 (9) | 0.85669 (13) | 0.0192 (4) | |
C5 | 0.1583 (2) | 0.35385 (9) | 1.02943 (14) | 0.0238 (4) | |
C6 | −0.0067 (3) | 0.37400 (13) | 1.15042 (18) | 0.0375 (5) | |
C7 | 0.0719 (4) | 0.34598 (15) | 1.24700 (19) | 0.0458 (6) | |
C8 | 0.4464 (2) | 0.51090 (9) | 0.80323 (13) | 0.0191 (4) | |
C9 | 0.4858 (3) | 0.62695 (9) | 0.78255 (16) | 0.0276 (5) | |
C10 | 0.4508 (3) | 0.69182 (11) | 0.83122 (19) | 0.0356 (5) | |
H11 | 0.824 (3) | 0.6842 (14) | 0.453 (2) | 0.051 (9)* | |
H12 | 0.619 (3) | 0.5292 (13) | 0.6178 (19) | 0.044 (7)* | |
H1 | 0.266 (3) | 0.2656 (13) | 0.9214 (19) | 0.047 (8)* | |
H2 | 0.496 (3) | 0.3940 (11) | 0.7330 (16) | 0.026 (6)* | |
H161 | 1.191 (3) | 0.6391 (11) | 0.2472 (17) | 0.034 (6)* | |
H172 | 1.071 (3) | 0.5519 (10) | 0.0887 (16) | 0.029 (6)* | |
H162 | 1.042 (2) | 0.6550 (10) | 0.1718 (15) | 0.024 (5)* | |
H102 | 0.493 (3) | 0.6915 (11) | 0.900 (2) | 0.040 (7)* | |
H173 | 1.217 (3) | 0.5349 (12) | 0.1656 (17) | 0.034 (6)* | |
H91 | 0.600 (3) | 0.6196 (11) | 0.7886 (16) | 0.035 (6)* | |
H171 | 1.225 (3) | 0.5938 (12) | 0.0927 (18) | 0.041 (7)* | |
H61 | −0.074 (3) | 0.3404 (13) | 1.114 (2) | 0.053 (8)* | |
H62 | −0.069 (3) | 0.4163 (13) | 1.1661 (19) | 0.058 (8)* | |
H191 | 0.568 (3) | 0.3077 (12) | 0.4997 (19) | 0.051 (8)* | |
H103 | 0.338 (3) | 0.6996 (12) | 0.8245 (18) | 0.044 (7)* | |
H203 | 0.696 (3) | 0.2069 (13) | 0.4614 (18) | 0.047 (7)* | |
H92 | 0.435 (3) | 0.6269 (10) | 0.7154 (17) | 0.029 (6)* | |
H101 | 0.499 (3) | 0.7267 (12) | 0.7987 (18) | 0.043 (7)* | |
H192 | 0.729 (3) | 0.2981 (12) | 0.5712 (19) | 0.041 (7)* | |
H201 | 0.682 (4) | 0.2569 (14) | 0.372 (2) | 0.068 (9)* | |
H202 | 0.840 (4) | 0.2488 (15) | 0.443 (2) | 0.064 (9)* | |
H71 | 0.144 (3) | 0.3805 (14) | 1.283 (2) | 0.063 (8)* | |
H72 | 0.136 (4) | 0.3059 (15) | 1.233 (2) | 0.066 (9)* | |
H73 | −0.011 (4) | 0.3362 (16) | 1.293 (3) | 0.086 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S11 | 0.0222 (3) | 0.0191 (2) | 0.0194 (2) | 0.00026 (18) | 0.00496 (19) | −0.00035 (17) |
O11 | 0.0504 (10) | 0.0184 (7) | 0.0332 (8) | −0.0011 (7) | 0.0228 (8) | 0.0000 (6) |
O12 | 0.0356 (9) | 0.0234 (7) | 0.0222 (7) | −0.0018 (6) | 0.0140 (6) | 0.0002 (6) |
O13 | 0.0471 (10) | 0.0207 (7) | 0.0350 (8) | −0.0026 (6) | 0.0203 (7) | −0.0003 (6) |
O14 | 0.0266 (8) | 0.0231 (6) | 0.0221 (7) | −0.0019 (5) | 0.0117 (6) | 0.0000 (5) |
O15 | 0.0363 (9) | 0.0249 (7) | 0.0219 (7) | −0.0037 (6) | 0.0107 (6) | −0.0002 (5) |
O16 | 0.0342 (8) | 0.0181 (6) | 0.0259 (7) | −0.0012 (6) | 0.0101 (6) | −0.0009 (5) |
C11 | 0.0217 (10) | 0.0191 (9) | 0.0195 (9) | 0.0009 (7) | 0.0018 (8) | 0.0005 (7) |
C12 | 0.0267 (11) | 0.0176 (8) | 0.0196 (9) | 0.0001 (8) | 0.0043 (8) | −0.0005 (7) |
C13 | 0.0205 (10) | 0.0216 (9) | 0.0165 (9) | −0.0006 (7) | 0.0030 (8) | −0.0003 (7) |
C14 | 0.0189 (10) | 0.0217 (9) | 0.0176 (9) | 0.0001 (7) | 0.0018 (7) | 0.0006 (7) |
C15 | 0.0222 (10) | 0.0228 (9) | 0.0186 (9) | 0.0010 (8) | 0.0039 (8) | 0.0010 (7) |
C16 | 0.0237 (11) | 0.0256 (10) | 0.0231 (10) | −0.0028 (9) | 0.0088 (9) | 0.0035 (8) |
C17 | 0.0262 (12) | 0.0304 (11) | 0.0263 (11) | −0.0009 (10) | 0.0091 (10) | 0.0009 (9) |
C18 | 0.0204 (10) | 0.0200 (9) | 0.0193 (9) | −0.0003 (7) | −0.0010 (8) | −0.0008 (7) |
C19 | 0.0460 (16) | 0.0191 (10) | 0.0366 (14) | −0.0063 (9) | 0.0111 (11) | 0.0003 (9) |
C20 | 0.0509 (17) | 0.0231 (11) | 0.0413 (15) | 0.0028 (10) | 0.0049 (12) | −0.0019 (9) |
S1 | 0.0255 (3) | 0.0192 (2) | 0.0203 (2) | −0.00019 (19) | 0.00830 (19) | −0.00020 (18) |
O1 | 0.0372 (9) | 0.0174 (7) | 0.0349 (8) | 0.0001 (6) | 0.0142 (7) | −0.0005 (6) |
O2 | 0.0342 (9) | 0.0229 (7) | 0.0249 (8) | 0.0030 (6) | 0.0138 (7) | 0.0002 (6) |
O3 | 0.0450 (10) | 0.0225 (7) | 0.0402 (9) | −0.0044 (6) | 0.0147 (7) | 0.0046 (6) |
O4 | 0.0384 (9) | 0.0290 (7) | 0.0278 (8) | −0.0007 (6) | 0.0172 (7) | 0.0019 (6) |
O5 | 0.0298 (8) | 0.0276 (7) | 0.0235 (7) | 0.0031 (6) | 0.0117 (6) | 0.0026 (6) |
O6 | 0.0292 (8) | 0.0192 (6) | 0.0233 (7) | −0.0013 (5) | 0.0093 (6) | 0.0008 (5) |
C1 | 0.0215 (10) | 0.0210 (9) | 0.0189 (9) | 0.0008 (7) | 0.0010 (8) | 0.0026 (7) |
C2 | 0.0197 (10) | 0.0193 (9) | 0.0228 (10) | 0.0024 (7) | 0.0015 (8) | 0.0011 (7) |
C3 | 0.0196 (10) | 0.0229 (9) | 0.0184 (9) | 0.0027 (8) | 0.0020 (8) | −0.0014 (7) |
C4 | 0.0189 (10) | 0.0224 (9) | 0.0161 (9) | 0.0012 (7) | 0.0026 (8) | 0.0006 (7) |
C5 | 0.0248 (11) | 0.0244 (10) | 0.0226 (10) | 0.0016 (8) | 0.0048 (8) | 0.0049 (8) |
C6 | 0.0347 (14) | 0.0470 (14) | 0.0340 (12) | −0.0006 (11) | 0.0154 (11) | 0.0064 (10) |
C7 | 0.0524 (17) | 0.0560 (16) | 0.0305 (13) | −0.0036 (14) | 0.0114 (12) | 0.0035 (11) |
C8 | 0.0174 (10) | 0.0223 (9) | 0.0170 (9) | 0.0024 (7) | 0.0013 (8) | 0.0014 (7) |
C9 | 0.0365 (13) | 0.0229 (10) | 0.0245 (11) | −0.0047 (9) | 0.0076 (10) | 0.0054 (8) |
C10 | 0.0479 (17) | 0.0234 (11) | 0.0347 (13) | −0.0027 (10) | 0.0039 (12) | 0.0009 (9) |
S11—C14 | 1.7275 (19) | S1—C4 | 1.7196 (19) |
S11—C11 | 1.7277 (18) | S1—C1 | 1.7217 (18) |
O11—C12 | 1.337 (2) | O1—C2 | 1.345 (2) |
O11—H11 | 0.77 (3) | O1—H1 | 0.82 (3) |
O12—C13 | 1.337 (2) | O2—C3 | 1.340 (2) |
O12—H12 | 0.83 (3) | O2—H2 | 0.77 (2) |
O13—C15 | 1.215 (2) | O3—C5 | 1.216 (2) |
O14—C15 | 1.333 (2) | O4—C5 | 1.326 (2) |
O14—C16 | 1.455 (2) | O4—C6 | 1.467 (3) |
O15—C18 | 1.212 (2) | O5—C8 | 1.214 (2) |
O16—C18 | 1.335 (2) | O6—C8 | 1.327 (2) |
O16—C19 | 1.455 (2) | O6—C9 | 1.464 (2) |
C11—C12 | 1.371 (3) | C1—C2 | 1.376 (3) |
C11—C15 | 1.449 (3) | C1—C5 | 1.455 (3) |
C12—C13 | 1.423 (3) | C2—C3 | 1.424 (3) |
C13—C14 | 1.372 (3) | C3—C4 | 1.374 (3) |
C14—C18 | 1.453 (3) | C4—C8 | 1.453 (3) |
C16—C17 | 1.495 (3) | C6—C7 | 1.492 (3) |
C16—H161 | 0.95 (2) | C6—H61 | 0.97 (3) |
C16—H162 | 0.96 (2) | C6—H62 | 1.04 (3) |
C17—H172 | 0.98 (2) | C7—H71 | 1.01 (3) |
C17—H173 | 0.95 (2) | C7—H72 | 1.01 (3) |
C17—H171 | 0.95 (3) | C7—H73 | 1.05 (4) |
C19—C20 | 1.485 (3) | C9—C10 | 1.500 (3) |
C19—H191 | 0.95 (3) | C9—H91 | 1.00 (2) |
C19—H192 | 0.97 (3) | C9—H92 | 0.95 (2) |
C20—H203 | 0.96 (3) | C10—H102 | 0.95 (3) |
C20—H201 | 0.96 (3) | C10—H103 | 0.98 (3) |
C20—H202 | 0.97 (3) | C10—H101 | 0.96 (3) |
C14—S11—C11 | 90.45 (9) | C4—S1—C1 | 90.43 (9) |
C12—O11—H11 | 107 (2) | C2—O1—H1 | 105.0 (18) |
C13—O12—H12 | 110.9 (18) | C3—O2—H2 | 106.5 (17) |
C15—O14—C16 | 115.88 (14) | C5—O4—C6 | 117.38 (16) |
C18—O16—C19 | 115.43 (16) | C8—O6—C9 | 114.56 (15) |
C12—C11—C15 | 123.13 (17) | C2—C1—C5 | 123.84 (17) |
C12—C11—S11 | 112.57 (14) | C2—C1—S1 | 112.80 (14) |
C15—C11—S11 | 124.24 (14) | C5—C1—S1 | 123.23 (14) |
O11—C12—C11 | 126.31 (18) | O1—C2—C1 | 127.47 (18) |
O11—C12—C13 | 121.31 (17) | O1—C2—C3 | 120.51 (17) |
C11—C12—C13 | 112.37 (16) | C1—C2—C3 | 112.02 (16) |
O12—C13—C14 | 128.17 (17) | O2—C3—C4 | 127.69 (17) |
O12—C13—C12 | 120.11 (16) | O2—C3—C2 | 120.84 (17) |
C14—C13—C12 | 111.73 (17) | C4—C3—C2 | 111.46 (16) |
C13—C14—C18 | 124.08 (17) | C3—C4—C8 | 122.67 (17) |
C13—C14—S11 | 112.88 (14) | C3—C4—S1 | 113.28 (14) |
C18—C14—S11 | 123.03 (13) | C8—C4—S1 | 124.02 (14) |
O13—C15—O14 | 124.11 (17) | O3—C5—O4 | 124.56 (18) |
O13—C15—C11 | 122.47 (18) | O3—C5—C1 | 121.68 (18) |
O14—C15—C11 | 113.42 (15) | O4—C5—C1 | 113.71 (16) |
O14—C16—C17 | 106.62 (15) | O4—C6—C7 | 111.6 (2) |
O14—C16—H161 | 108.2 (13) | O4—C6—H61 | 109.5 (16) |
C17—C16—H161 | 112.0 (14) | C7—C6—H61 | 110.9 (16) |
O14—C16—H162 | 108.2 (13) | O4—C6—H62 | 105.7 (15) |
C17—C16—H162 | 112.7 (12) | C7—C6—H62 | 107.5 (15) |
H161—C16—H162 | 108.9 (17) | H61—C6—H62 | 112 (2) |
C16—C17—H172 | 110.4 (13) | C6—C7—H71 | 110.1 (16) |
C16—C17—H173 | 111.2 (13) | C6—C7—H72 | 108.2 (17) |
H172—C17—H173 | 107.1 (18) | H71—C7—H72 | 108 (2) |
C16—C17—H171 | 110.4 (14) | C6—C7—H73 | 109.3 (19) |
H172—C17—H171 | 109.4 (19) | H71—C7—H73 | 106 (2) |
H173—C17—H171 | 108 (2) | H72—C7—H73 | 115 (2) |
O15—C18—O16 | 124.37 (17) | O5—C8—O6 | 124.53 (16) |
O15—C18—C14 | 123.22 (16) | O5—C8—C4 | 120.95 (16) |
O16—C18—C14 | 112.41 (16) | O6—C8—C4 | 114.52 (16) |
O16—C19—C20 | 107.32 (19) | O6—C9—C10 | 107.05 (18) |
O16—C19—H191 | 106.1 (15) | O6—C9—H91 | 108.8 (13) |
C20—C19—H191 | 114.7 (16) | C10—C9—H91 | 111.0 (13) |
O16—C19—H192 | 106.7 (14) | O6—C9—H92 | 107.9 (13) |
C20—C19—H192 | 109.6 (14) | C10—C9—H92 | 109.3 (13) |
H191—C19—H192 | 112 (2) | H91—C9—H92 | 112.6 (19) |
C19—C20—H203 | 109.3 (15) | C9—C10—H102 | 110.9 (14) |
C19—C20—H201 | 110.3 (18) | C9—C10—H103 | 111.3 (14) |
H203—C20—H201 | 109 (2) | H102—C10—H103 | 108 (2) |
C19—C20—H202 | 113.1 (18) | C9—C10—H101 | 106.3 (15) |
H203—C20—H202 | 108 (2) | H102—C10—H101 | 109 (2) |
H201—C20—H202 | 108 (2) | H103—C10—H101 | 111 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 (3) | 2.10 (3) | 2.799 (2) | 144 (2) |
O1—H1···O11i | 0.82 (3) | 2.44 (3) | 3.116 (2) | 141 (2) |
O2—H2···O5 | 0.77 (2) | 2.09 (2) | 2.7409 (19) | 143 (2) |
O2—H2···O15 | 0.77 (2) | 2.46 (2) | 3.101 (2) | 141 (2) |
O11—H11···O13 | 0.77 (3) | 2.09 (3) | 2.750 (2) | 144 (3) |
O11—H11···O3ii | 0.77 (3) | 2.22 (3) | 2.723 (2) | 123 (2) |
O12—H12···O5 | 0.84 (3) | 2.04 (3) | 2.752 (2) | 142 (2) |
O12—H12···O15 | 0.84 (3) | 2.19 (3) | 2.8475 (19) | 135 (2) |
C7—H71···O12iii | 1.00 (3) | 2.60 (3) | 3.563 (3) | 162 (2) |
C17—H173···O5iv | 0.95 (2) | 2.57 (3) | 3.384 (3) | 144 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2; (iv) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H12O6S |
Mr | 260.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 160 |
a, b, c (Å) | 8.7337 (9), 19.8208 (14), 13.6271 (15) |
β (°) | 99.059 (13) |
V (Å3) | 2329.5 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.48 × 0.23 × 0.1 |
Data collection | |
Diffractometer | STOE imaging-plate diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.928, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20063, 4535, 3225 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.072, 0.94 |
No. of reflections | 4535 |
No. of parameters | 403 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.21 |
Computer programs: IPDS Software (Stoe & Cie, 1996), IPDS Software, Sir97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1996), WinGX (Farrugia, 1999).
S11—C14 | 1.7275 (19) | S1—C4 | 1.7196 (19) |
S11—C11 | 1.7277 (18) | S1—C1 | 1.7217 (18) |
O11—C12 | 1.337 (2) | O1—C2 | 1.345 (2) |
O12—C13 | 1.337 (2) | O2—C3 | 1.340 (2) |
O13—C15 | 1.215 (2) | O3—C5 | 1.216 (2) |
O14—C15 | 1.333 (2) | O4—C5 | 1.326 (2) |
O14—C16 | 1.455 (2) | O4—C6 | 1.467 (3) |
O15—C18 | 1.212 (2) | O5—C8 | 1.214 (2) |
O16—C18 | 1.335 (2) | O6—C8 | 1.327 (2) |
O16—C19 | 1.455 (2) | O6—C9 | 1.464 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 (3) | 2.10 (3) | 2.799 (2) | 144 (2) |
O1—H1···O11i | 0.82 (3) | 2.44 (3) | 3.116 (2) | 141 (2) |
O2—H2···O5 | 0.77 (2) | 2.09 (2) | 2.7409 (19) | 143 (2) |
O2—H2···O15 | 0.77 (2) | 2.46 (2) | 3.101 (2) | 141 (2) |
O11—H11···O13 | 0.77 (3) | 2.09 (3) | 2.750 (2) | 144 (3) |
O11—H11···O3ii | 0.77 (3) | 2.22 (3) | 2.723 (2) | 123 (2) |
O12—H12···O5 | 0.84 (3) | 2.04 (3) | 2.752 (2) | 142 (2) |
O12—H12···O15 | 0.84 (3) | 2.19 (3) | 2.8475 (19) | 135 (2) |
C7—H71···O12iii | 1.00 (3) | 2.60 (3) | 3.563 (3) | 162 (2) |
C17—H173···O5iv | 0.95 (2) | 2.57 (3) | 3.384 (3) | 144 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2; (iv) −x+2, −y+1, −z+1. |
Electrically conducting polymers are a widely and intensively researched class of materials in both industry and academia (Skotheim et al., 1998). One particular family of conducting polymers, poly(ethylenedioxythiophenes) (PEDOTs), have shown extraordinary promise in a variety of applications due to their low oxidation state, high conductivity, oxidation-state stability and thin-film transparency (Groenendaal et al., 2003). Several commercially available products use a PEDOT-based material (Groenendaal et al., 2000). Utilizing the electronic properties of PEDOT, which are superior to those of other conducting polymer systems, we set out to design and synthesize substituted PEDOT-based polymers.
According to previously reported procedures, PEDOTs can be readily derivatized at the ethylenedioxy bridge (Sankaran & Reynolds, 1997; Lima et al., 1998). During purification of the substituted EDOT precursor diethyl-3,4-dihydroxy-2,5-thiophenedicarboxylate, (II), which was prepared from the diethyl thiodiglycolate, (I), in two steps, unexpected dark-yellow chunk-like crystals formed alongside, to a lesser extent, the expected and previously reported white needles. The 1H NMR data for the two samples were the same and agreed with those previously reported (Sankaran & Reynolds, 1997). The stark contrast in crystal morphology and color, yet similar NMR properties, piqued our interest in determining the crystal structure of the unexpected product.
The asymmetric unit of the title compound contains two independent C10H12O6S molecules, named hereafter as A and B (Fig. 1), which lie almost in the same plane, close to (101). The planes of molecules A and B form an angle of ca 1.52 (4)°. Comparison of intramolecular bond lengths and angles does not show any discrepencies between units A and B. For each type of bond, distances are very homogeneous, except for one methyl group (see below). The only structural difference between these two units lies in the conformation of one of the terminal methyl groups. In molecule A, the methyl group that involves atom C7 points out of the plane of the molecule [C7 lies 1.128 (3) Å from the molecular plane], whereas molecule B is almost planar [the largest deviation is 0.164 (1) Å for atom O15].
The result of this non-planarity in molecule A is the existence of one short intermolecular contact, which can be regarded as a potential hydrogen-bond between A and B via atoms C7, H71 and O12(1 − x,1 − y,2 − z) (see Table 2). As a result of these short contacts, the C—H bond lengths around atom C7 [mean distance 1.02 (4) Å] are slightly larger than those of the other methyl groups [mean distance 0.96 (4) Å]. Atom C17 is also involved in a short intermolecular contact with atoms O5(2 − x,1 − y,1 − z) and H173 [C—H = 0.95 (2) Å, H—O = 2.57 (3) Å and C—O = 3.384 (3) Å], but this contact cannot be regarded as a potential hydrogen bond because the C17—H173—O5 angle [144 (2)°] is relatively bent. There is also another short contact, of 3.458 (2) Å, between atoms C17 and S1(1 + x,y,-1 + z). In contrast, the other methyl groups (C10 and C20) are not involved in any intermolecular contacts shorter than the sum of the van der Waals radii.
Contrary to what is observed in C7H8O4S (Hada et al., 1993), the hydroxy groups of C10H12O6S lie in the plane of the molecules. This planarity leads to a larger number of potential intra- and intermolecular hydrogen bonds between units than are present in C7H8O4S (see Table 2); in C10H12O6S, each hydroxy group is involved in one intra- and one intermolecular contact, whereas in C7H8O4S, only half of the OH groups generate such contacts. In addition, there also exist some short intermolecular contacts between non-H atoms. These numerous short intermolecular contacts involve only nearly coplanar molecules, which creates a relatively dense network of interactions, within and between C10H12O6S molecules. Therefore, the overall structure of the title compound can be regarded as sheets of C10H12O6S molecules (Fig. 2), which spread out parallel to the b axis almost in the (101) plane. However, the sheets are not independent of each other, since there exist intersheet contacts (Table 2). These contacts involve? not only the out-of-plane methyl group (C7) and one of the hydroxy groups (O12) but also other hetero atoms in the molecule (see Table 2). As a result of these intersheet contacts, the intersheet distance is relatively short (ca 3.55 Å). The observed hydrogen-bonding and other intermolecular interactions are likely to be the main contributors to the low solubility in lower-polarity solvents. The compound was recrystallized in small portions from large amounts of boiling ethyl acetate. The compound is observed to be more soluble in higher-polarity solvents, such as methanol and, to a lesser extent, ethanol.
The structure of the needle phase has also been determined, but its low quality (due to the very thin morphology and the poor diffracting power of the sample), prevents its presentation in this article. Nevertheless, the needle phase exhibits the same structural arrangement as the block phase, with the same features.