Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110044884/sk3394sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044884/sk3394Isup2.hkl |
CCDC reference: 810033
Compound (I) was prepared by an adaptation of a reported procedure (Lai et al., 2002). 1-Dodecanethiol (0.02 mol), acetone (0.166 mol) and tricaprylylmethylammonium chloride (0.0008 mol) were mixed under a dinitrogen atmosphere and cooled to 283 K. An aqueous solution (50%) of sodium hydroxide (0.021 mol) was added dropwise over 20 min. The reaction was stirred for an additional 15 min, before a solution of carbon disulfide (0.020 mol) in acetone (0.034 mol) was added over 20 min until the colour turned red. After 10 min, chloroform (0.030 mol) was added in one portion, followed by dropwise addition of a 50% aqueous solution of NaOH (0.1 mol) over 30 min. The mixture was then stirred overnight. After this, water (30 ml) was added, followed by concentrated hydrochloric acid (5 ml) to acidify the solution. The resulting solid was collected by filtration and then stirred in propan-2-ol (50 ml). The resultant solution was concentrated under reduced pressure and the resulting solid product, (I), was recrystallized from hexane to afford yellow crystals [Colourless given in CIF data tables - please clarify] (yield 59%, m.p. 335–337 K).
All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 otherwise. The O-bound H atom was permitted to ride at the location deduced from a difference map, with Uiso(H) = 1.5Ueq(O), giving an O—H distance of 0.82 Å.
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C17H32O2S3 | Z = 2 |
Mr = 364.64 | F(000) = 396 |
Triclinic, P1 | Dx = 1.225 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.775 (4) Å | Cell parameters from 4515 reflections |
b = 6.924 (3) Å | θ = 2.7–27.5° |
c = 22.815 (9) Å | µ = 0.38 mm−1 |
α = 84.69 (3)° | T = 120 K |
β = 84.73 (5)° | Block, pale yellow |
γ = 68.34 (4)° | 0.40 × 0.17 × 0.10 mm |
V = 988.5 (9) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3689 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2727 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.7° |
ϕ and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.839, Tmax = 0.963 | l = −27→27 |
22623 measured reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.9482P] where P = (Fo2 + 2Fc2)/3 |
3689 reflections | (Δ/σ)max = 0.001 |
202 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C17H32O2S3 | γ = 68.34 (4)° |
Mr = 364.64 | V = 988.5 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.775 (4) Å | Mo Kα radiation |
b = 6.924 (3) Å | µ = 0.38 mm−1 |
c = 22.815 (9) Å | T = 120 K |
α = 84.69 (3)° | 0.40 × 0.17 × 0.10 mm |
β = 84.73 (5)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3689 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2727 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 0.963 | Rint = 0.076 |
22623 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.55 e Å−3 |
3689 reflections | Δρmin = −0.29 e Å−3 |
202 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | −0.4011 (5) | 0.2629 (4) | 0.55335 (13) | 0.0215 (6) | |
O11 | −0.3648 (3) | 0.2544 (3) | 0.50054 (8) | 0.0249 (5) | |
O12 | −0.5311 (3) | 0.4286 (3) | 0.57892 (8) | 0.0238 (5) | |
H12 | −0.5574 | 0.5207 | 0.5522 | 0.036* | |
C2 | −0.3130 (5) | 0.0702 (4) | 0.59479 (12) | 0.0203 (6) | |
C21 | −0.1124 (5) | −0.0863 (4) | 0.56778 (13) | 0.0280 (7) | |
H21A | −0.1420 | −0.1235 | 0.5300 | 0.042* | |
H21B | −0.0632 | −0.2114 | 0.5945 | 0.042* | |
H21C | −0.0020 | −0.0254 | 0.5613 | 0.042* | |
C22 | −0.4856 (5) | −0.0239 (5) | 0.60819 (14) | 0.0280 (7) | |
H22A | −0.5267 | −0.0557 | 0.5712 | 0.042* | |
H22B | −0.6101 | 0.0760 | 0.6285 | 0.042* | |
H22C | −0.4305 | −0.1521 | 0.6335 | 0.042* | |
S3 | −0.26797 (12) | 0.13283 (11) | 0.66701 (3) | 0.0221 (2) | |
C4 | −0.1003 (4) | 0.2728 (4) | 0.65333 (13) | 0.0219 (6) | |
S4 | −0.03919 (13) | 0.36860 (12) | 0.58960 (3) | 0.0277 (2) | |
S5 | −0.01197 (13) | 0.29396 (12) | 0.72064 (3) | 0.0265 (2) | |
C6 | 0.1205 (5) | 0.4761 (5) | 0.70370 (13) | 0.0233 (7) | |
H6A | 0.2287 | 0.4294 | 0.6706 | 0.028* | |
H6B | 0.0164 | 0.6150 | 0.6920 | 0.028* | |
C7 | 0.2255 (5) | 0.4878 (4) | 0.75820 (12) | 0.0219 (6) | |
H7A | 0.3267 | 0.3475 | 0.7699 | 0.026* | |
H7B | 0.1158 | 0.5338 | 0.7910 | 0.026* | |
C8 | 0.3436 (5) | 0.6375 (5) | 0.74796 (13) | 0.0243 (7) | |
H8A | 0.4550 | 0.5897 | 0.7157 | 0.029* | |
H8B | 0.2428 | 0.7769 | 0.7353 | 0.029* | |
C9 | 0.4455 (5) | 0.6544 (4) | 0.80229 (13) | 0.0237 (7) | |
H9A | 0.5453 | 0.5145 | 0.8150 | 0.028* | |
H9B | 0.3336 | 0.7024 | 0.8345 | 0.028* | |
C10 | 0.5647 (5) | 0.8020 (5) | 0.79294 (13) | 0.0237 (7) | |
H10A | 0.4654 | 0.9411 | 0.7795 | 0.028* | |
H10B | 0.6779 | 0.7526 | 0.7612 | 0.028* | |
C11 | 0.6649 (5) | 0.8228 (4) | 0.84764 (13) | 0.0237 (7) | |
H11A | 0.5515 | 0.8747 | 0.8792 | 0.028* | |
H11B | 0.7624 | 0.6833 | 0.8615 | 0.028* | |
C12 | 0.7870 (5) | 0.9674 (5) | 0.83778 (13) | 0.0246 (7) | |
H12A | 0.6897 | 1.1064 | 0.8235 | 0.030* | |
H12B | 0.9011 | 0.9147 | 0.8064 | 0.030* | |
C13 | 0.8861 (5) | 0.9910 (5) | 0.89229 (13) | 0.0246 (7) | |
H13A | 0.7724 | 1.0420 | 0.9238 | 0.029* | |
H13B | 0.9853 | 0.8525 | 0.9063 | 0.029* | |
C14 | 1.0049 (5) | 1.1380 (5) | 0.88204 (13) | 0.0249 (7) | |
H14A | 0.9052 | 1.2765 | 0.8682 | 0.030* | |
H14B | 1.1175 | 1.0873 | 0.8502 | 0.030* | |
C15 | 1.1063 (5) | 1.1624 (5) | 0.93599 (13) | 0.0253 (7) | |
H15A | 0.9942 | 1.2127 | 0.9680 | 0.030* | |
H15B | 1.2075 | 1.0245 | 0.9497 | 0.030* | |
C16 | 1.2230 (5) | 1.3123 (5) | 0.92444 (14) | 0.0284 (7) | |
H16A | 1.3357 | 1.2608 | 0.8927 | 0.034* | |
H16B | 1.1218 | 1.4493 | 0.9101 | 0.034* | |
C17 | 1.3233 (6) | 1.3414 (5) | 0.97782 (14) | 0.0362 (8) | |
H17A | 1.2125 | 1.3960 | 1.0092 | 0.054* | |
H17B | 1.3957 | 1.4399 | 0.9671 | 0.054* | |
H17C | 1.4266 | 1.2072 | 0.9918 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0248 (16) | 0.0152 (15) | 0.0271 (17) | −0.0094 (13) | −0.0072 (13) | 0.0002 (12) |
O11 | 0.0327 (12) | 0.0181 (11) | 0.0204 (11) | −0.0050 (9) | −0.0028 (9) | −0.0014 (8) |
O12 | 0.0273 (11) | 0.0163 (11) | 0.0224 (11) | −0.0018 (9) | −0.0008 (9) | −0.0002 (8) |
C2 | 0.0259 (16) | 0.0153 (14) | 0.0212 (15) | −0.0088 (13) | −0.0040 (12) | 0.0000 (12) |
C21 | 0.0376 (19) | 0.0147 (15) | 0.0275 (17) | −0.0052 (14) | −0.0034 (14) | 0.0015 (12) |
C22 | 0.0360 (19) | 0.0222 (16) | 0.0313 (17) | −0.0159 (14) | −0.0060 (14) | −0.0012 (13) |
S3 | 0.0273 (4) | 0.0212 (4) | 0.0209 (4) | −0.0127 (3) | −0.0032 (3) | 0.0008 (3) |
C4 | 0.0202 (15) | 0.0127 (14) | 0.0298 (16) | −0.0015 (12) | −0.0044 (13) | −0.0027 (12) |
S4 | 0.0323 (5) | 0.0268 (4) | 0.0275 (4) | −0.0149 (4) | −0.0042 (3) | 0.0016 (3) |
S5 | 0.0350 (5) | 0.0278 (4) | 0.0231 (4) | −0.0186 (4) | −0.0068 (3) | 0.0022 (3) |
C6 | 0.0272 (17) | 0.0211 (16) | 0.0242 (16) | −0.0124 (13) | −0.0010 (13) | 0.0005 (12) |
C7 | 0.0248 (16) | 0.0185 (15) | 0.0239 (15) | −0.0090 (13) | −0.0041 (13) | −0.0005 (12) |
C8 | 0.0287 (17) | 0.0203 (16) | 0.0246 (16) | −0.0102 (13) | 0.0003 (13) | −0.0012 (12) |
C9 | 0.0300 (17) | 0.0177 (15) | 0.0252 (16) | −0.0103 (13) | −0.0033 (13) | −0.0012 (12) |
C10 | 0.0247 (16) | 0.0190 (15) | 0.0275 (16) | −0.0080 (13) | −0.0006 (13) | −0.0035 (12) |
C11 | 0.0229 (16) | 0.0194 (15) | 0.0287 (16) | −0.0077 (13) | 0.0005 (13) | −0.0030 (13) |
C12 | 0.0281 (17) | 0.0221 (16) | 0.0248 (16) | −0.0098 (14) | −0.0038 (13) | −0.0026 (13) |
C13 | 0.0242 (16) | 0.0226 (16) | 0.0270 (16) | −0.0089 (13) | −0.0009 (13) | −0.0007 (13) |
C14 | 0.0307 (17) | 0.0199 (16) | 0.0258 (16) | −0.0103 (14) | −0.0065 (13) | −0.0008 (13) |
C15 | 0.0304 (17) | 0.0228 (16) | 0.0232 (16) | −0.0102 (14) | −0.0016 (13) | −0.0016 (13) |
C16 | 0.0310 (18) | 0.0241 (17) | 0.0319 (17) | −0.0113 (14) | −0.0068 (14) | −0.0006 (14) |
C17 | 0.042 (2) | 0.0338 (19) | 0.040 (2) | −0.0193 (17) | −0.0090 (16) | −0.0056 (15) |
C1—O11 | 1.210 (3) | C9—H9A | 0.9900 |
C1—O12 | 1.310 (3) | C9—H9B | 0.9900 |
C1—C2 | 1.521 (4) | C10—C11 | 1.517 (4) |
O12—H12 | 0.8214 | C10—H10A | 0.9900 |
C2—C21 | 1.511 (4) | C10—H10B | 0.9900 |
C2—C22 | 1.532 (4) | C11—C12 | 1.508 (4) |
C2—S3 | 1.822 (3) | C11—H11A | 0.9900 |
C21—H21A | 0.9800 | C11—H11B | 0.9900 |
C21—H21B | 0.9800 | C12—C13 | 1.515 (4) |
C21—H21C | 0.9800 | C12—H12A | 0.9900 |
C22—H22A | 0.9800 | C12—H12B | 0.9900 |
C22—H22B | 0.9800 | C13—C14 | 1.506 (4) |
C22—H22C | 0.9800 | C13—H13A | 0.9900 |
S3—C4 | 1.737 (3) | C13—H13B | 0.9900 |
C4—S4 | 1.624 (3) | C14—C15 | 1.515 (4) |
C4—S5 | 1.736 (3) | C14—H14A | 0.9900 |
S5—C6 | 1.796 (3) | C14—H14B | 0.9900 |
C6—C7 | 1.511 (4) | C15—C16 | 1.513 (4) |
C6—H6A | 0.9900 | C15—H15A | 0.9900 |
C6—H6B | 0.9900 | C15—H15B | 0.9900 |
C7—C8 | 1.516 (4) | C16—C17 | 1.512 (4) |
C7—H7A | 0.9900 | C16—H16A | 0.9900 |
C7—H7B | 0.9900 | C16—H16B | 0.9900 |
C8—C9 | 1.507 (4) | C17—H17A | 0.9800 |
C8—H8A | 0.9900 | C17—H17B | 0.9800 |
C8—H8B | 0.9900 | C17—H17C | 0.9800 |
C9—C10 | 1.510 (4) | ||
O11—C1—O12 | 123.9 (3) | H9A—C9—H9B | 107.7 |
O11—C1—C2 | 121.0 (3) | C9—C10—C11 | 113.8 (2) |
O12—C1—C2 | 114.8 (2) | C9—C10—H10A | 108.8 |
C1—O12—H12 | 103.9 | C11—C10—H10A | 108.8 |
C21—C2—C1 | 111.2 (2) | C9—C10—H10B | 108.8 |
C21—C2—C22 | 110.7 (2) | C11—C10—H10B | 108.8 |
C1—C2—C22 | 107.8 (2) | H10A—C10—H10B | 107.7 |
C21—C2—S3 | 110.8 (2) | C12—C11—C10 | 113.5 (2) |
C1—C2—S3 | 112.5 (2) | C12—C11—H11A | 108.9 |
C22—C2—S3 | 103.5 (2) | C10—C11—H11A | 108.9 |
C2—C21—H21A | 109.5 | C12—C11—H11B | 108.9 |
C2—C21—H21B | 109.5 | C10—C11—H11B | 108.9 |
H21A—C21—H21B | 109.5 | H11A—C11—H11B | 107.7 |
C2—C21—H21C | 109.5 | C11—C12—C13 | 114.0 (2) |
H21A—C21—H21C | 109.5 | C11—C12—H12A | 108.8 |
H21B—C21—H21C | 109.5 | C13—C12—H12A | 108.8 |
C2—C22—H22A | 109.5 | C11—C12—H12B | 108.8 |
C2—C22—H22B | 109.5 | C13—C12—H12B | 108.8 |
H22A—C22—H22B | 109.5 | H12A—C12—H12B | 107.6 |
C2—C22—H22C | 109.5 | C14—C13—C12 | 113.4 (2) |
H22A—C22—H22C | 109.5 | C14—C13—H13A | 108.9 |
H22B—C22—H22C | 109.5 | C12—C13—H13A | 108.9 |
C4—S3—C2 | 105.42 (14) | C14—C13—H13B | 108.9 |
S3—C4—S4 | 126.53 (18) | C12—C13—H13B | 108.9 |
S4—C4—S5 | 126.22 (18) | H13A—C13—H13B | 107.7 |
S3—C4—S5 | 107.25 (16) | C13—C14—C15 | 114.2 (2) |
C4—S5—C6 | 103.62 (14) | C13—C14—H14A | 108.7 |
C7—C6—S5 | 108.0 (2) | C15—C14—H14A | 108.7 |
C7—C6—H6A | 110.1 | C13—C14—H14B | 108.7 |
S5—C6—H6A | 110.1 | C15—C14—H14B | 108.7 |
C7—C6—H6B | 110.1 | H14A—C14—H14B | 107.6 |
S5—C6—H6B | 110.1 | C16—C15—C14 | 112.9 (2) |
H6A—C6—H6B | 108.4 | C16—C15—H15A | 109.0 |
C6—C7—C8 | 111.8 (2) | C14—C15—H15A | 109.0 |
C6—C7—H7A | 109.3 | C16—C15—H15B | 109.0 |
C8—C7—H7A | 109.3 | C14—C15—H15B | 109.0 |
C6—C7—H7B | 109.3 | H15A—C15—H15B | 107.8 |
C8—C7—H7B | 109.3 | C15—C16—C17 | 114.0 (3) |
H7A—C7—H7B | 107.9 | C15—C16—H16A | 108.8 |
C9—C8—C7 | 112.5 (2) | C17—C16—H16A | 108.8 |
C9—C8—H8A | 109.1 | C15—C16—H16B | 108.8 |
C7—C8—H8A | 109.1 | C17—C16—H16B | 108.8 |
C9—C8—H8B | 109.1 | H16A—C16—H16B | 107.6 |
C7—C8—H8B | 109.1 | C16—C17—H17A | 109.5 |
H8A—C8—H8B | 107.8 | C16—C17—H17B | 109.5 |
C8—C9—C10 | 113.4 (2) | H17A—C17—H17B | 109.5 |
C8—C9—H9A | 108.9 | C16—C17—H17C | 109.5 |
C10—C9—H9A | 108.9 | H17A—C17—H17C | 109.5 |
C8—C9—H9B | 108.9 | H17B—C17—H17C | 109.5 |
C10—C9—H9B | 108.9 | ||
O11—C1—C2—C21 | 25.8 (4) | S3—C4—S5—C6 | −170.49 (14) |
O12—C1—C2—C21 | −159.8 (2) | C4—S5—C6—C7 | −173.8 (2) |
O11—C1—C2—C22 | −95.8 (3) | S5—C6—C7—C8 | 179.6 (2) |
O12—C1—C2—C22 | 78.6 (3) | C6—C7—C8—C9 | 178.8 (2) |
O11—C1—C2—S3 | 150.7 (2) | C7—C8—C9—C10 | 179.7 (2) |
O12—C1—C2—S3 | −34.9 (3) | C8—C9—C10—C11 | 179.1 (2) |
C21—C2—S3—C4 | 69.2 (2) | C9—C10—C11—C12 | 179.0 (2) |
C1—C2—S3—C4 | −55.9 (2) | C10—C11—C12—C13 | 179.5 (2) |
C22—C2—S3—C4 | −172.00 (19) | C11—C12—C13—C14 | −179.2 (2) |
C2—S3—C4—S4 | 11.7 (2) | C12—C13—C14—C15 | −179.6 (3) |
C2—S3—C4—S5 | −168.94 (14) | C13—C14—C15—C16 | −179.6 (3) |
S4—C4—S5—C6 | 8.9 (2) | C14—C15—C16—C17 | 179.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.82 | 1.82 | 2.638 (3) | 173 |
C6—H6A···O12ii | 0.99 | 2.53 | 3.486 (4) | 162 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C17H32O2S3 |
Mr | 364.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 6.775 (4), 6.924 (3), 22.815 (9) |
α, β, γ (°) | 84.69 (3), 84.73 (5), 68.34 (4) |
V (Å3) | 988.5 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.40 × 0.17 × 0.10 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.839, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22623, 3689, 2727 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.129, 1.05 |
No. of reflections | 3689 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.29 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C1—O11 | 1.210 (3) | C4—S4 | 1.624 (3) |
C1—O12 | 1.310 (3) | C4—S5 | 1.736 (3) |
C2—S3 | 1.822 (3) | S5—C6 | 1.796 (3) |
S3—C4 | 1.737 (3) | ||
S3—C4—S4 | 126.53 (18) | S3—C4—S5 | 107.25 (16) |
S4—C4—S5 | 126.22 (18) | ||
O11—C1—C2—S3 | 150.7 (2) | S5—C6—C7—C8 | 179.6 (2) |
O12—C1—C2—S3 | −34.9 (3) | C6—C7—C8—C9 | 178.8 (2) |
C21—C2—S3—C4 | 69.2 (2) | C7—C8—C9—C10 | 179.7 (2) |
C1—C2—S3—C4 | −55.9 (2) | C8—C9—C10—C11 | 179.1 (2) |
C22—C2—S3—C4 | −172.00 (19) | C9—C10—C11—C12 | 179.0 (2) |
C2—S3—C4—S4 | 11.7 (2) | C10—C11—C12—C13 | 179.5 (2) |
C2—S3—C4—S5 | −168.94 (14) | C11—C12—C13—C14 | −179.2 (2) |
S4—C4—S5—C6 | 8.9 (2) | C12—C13—C14—C15 | −179.6 (3) |
S3—C4—S5—C6 | −170.49 (14) | C13—C14—C15—C16 | −179.6 (3) |
C4—S5—C6—C7 | −173.8 (2) | C14—C15—C16—C17 | 179.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.82 | 1.82 | 2.638 (3) | 173 |
C6—H6A···O12ii | 0.99 | 2.53 | 3.486 (4) | 162 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) x+1, y, z. |
The strong affinity of gold for sulfur makes sulfur derivatives attractive possibilities for use as reagents for the production of gold nanoparticles, which themselves have wide-ranging potential applications in areas as diverse as biology, catalysis and nanotechnology (Daniel & Astruc, 2004). Here, we report the molecular and supramolecular structure of the title compound, (I), which was synthesized for use in this way.
The dodecyl chain in (I) adopts an almost planar all-trans conformation, as shown by the leading torsion angles (Table 1). For the chain fragment between atoms S5 and C17, the maximum deviation of the skeletal torsion angles from 180° is less than 1.5°, and the maximum deviation from the mean plane through the non-H atoms between S5 and C17 is only 0.038 (3)°, for atom C6. In addition, the chain fragment between atoms S5 and C22 also adopts a nearly planar all-trans conformation, with the torsion angles along this chain all within 12° of 180°. It is interesting to note the asymmetric orientation of the –CMe2COOH fragment relative to the trithiocarbonate unit and the hydrocarbon chain, with the carboxyl group synclinal (gauche) to the extended chain; this can probably be attributed to the intermolecular hydrogen bonding (see below).
The bond distances and angles (Table 1) in the trithiocarbonate fragment are very similar to those found in compound (II) [Cambridge Structural Database (CSD; Allen, 2002) refcode ROGHOL; Zeng et al., 2008], where the molecules lie across a twofold rotation axis in space group C2/c with distances C═S = 1.634 (3) Å and C—S = 1.7438 (18) Å, and angles S—C═S = 125.75 (7)° and S—C—Si 108.50 (15)° [symmetry code: (i) 1 - x, y, 1/2 - z]. The C—O distances in (I) are consistent with the position of the fully ordered hydroxyl H atom as located in a difference map. Very similar geometries but at slightly lower precision were found for the corresponding fragments in both the neutral and the anionic components of compound (III) (CSD refcode ZENTAN; Ng, 1995). In (III), which was reported in the non-standard P2/a setting of space group P2/c, the neutral and anionic components in the selected asymmetric unit lie across the twofold rotation axes along (3/4, y, 0) and (3/4, y, 1/2), respectively, so that the asymmetric unit comprises one-half of each of the S-containing components together with one cation, although the original report does not specify the imposed symmetry and its scheme implies the presence of two independent cations.
The supramolecular aggregation in (I) is determined by one O—H···O hydrogen bond and one rather weak C—H···O hydrogen bond (Table 2). The only other short intermolecular contacts all involve C—H bonds from the two methyl groups containing atoms C21 and C22. These bonds are of low acidity and the methyl groups are likely to be undergoing very fast rotation about the C2—C21 and C2—C22 bonds, respectively. Hence, the intermolecular contacts involving these methyl groups are not regarded as structurally significant.
The O—H···O hydrogen bond links pairs of inversion-related molecules to form cyclic centrosymmetric dimers containing the R22(8) motif (Bernstein et al., 1995) so characteristic of simple carboxylic acids (Fig. 2). Dimers of this type, related to one another by translation, are linked by the C—H···O hydrogen bond to form a chain of edge-fused rings running parallel to the [100] direction, which can alternatively be regarded as a molecular ladder, and in which R22(8) rings centred at (n + 1/2, 1/2, 1/2), where n represents an integer, alternate with R44(20) rings centred at (n, 1/2, 1/2), where n again represents an integer (Fig. 2). One ladder of this type passes through each unit cell, but there are no direction-specific interactions between adjacent chains.
The formation of the ladder in (I), containing two types of ring motif, may be contrasted with that in (II), where the unique O—H···O hydrogen bond generates a ladder containing a single type of R22(20) ring (Zeng et al., 2008). The hydrogen bonding in (III), on the other hand, is rather more problematic, in terms of both the location of one of the H atoms and the overall action of the hydrogen bonds.
Although the coordinates of the H atom bonded to an O atom in (III) were refined, and although the structure was described (Ng, 1995) in terms of a neutral acid component and a dianionic component, the interatomic distances do not readily sustain such a description. In the component described as anionic, the two independent C—O distances are 1.224 (4) and 1.266 (4) Å, while in the component described as neutral these distances are 1.225 (4) and 1.283 (4) Å. However, for a fully ionized carboxylate anion, the two C—O distances are expected to be essentially identical, while in an unionized carboxylic acid the C—O distances typically differ by ca 0.10 Å, as found here for (I). By contrast, in (III) the corresponding distances in the two independent components are remarkably similar. In addition, the refined O—H distance is 1.17 (6) Å, while the H···O and O···O distances in the hydrogen bond linking the neutral and anionic components are 1.28 (6) and 2.448 (3) Å, respectively, with no significant difference between the reported O—H and H···O distances. The overall geometry suggests two possibilities other than the fully ordered structure actually reported: either the acidic H atom could be disordered over two sites, or, more plausibly in view of the short O···O distance, the H atom is located at the mid-point of the O···O vector within the hydrogen bond. In this latter case, no chemical distinction could be made between the two independent carboxyl components. Without the reflection data (the FCF data are deposited in printed-journal format rather than in CIF format), it is not possible to establish which of the various possibilities provides the best model, but the ambiguities need to be borne in mind in the following discussion, which is based upon the reported atomic coordinates using a description in terms of neutral and dianionic S-containing components.
In the original report on (III) (Ng, 1995), no details of the hydrogen bonds were provided, and no description or analysis of their actions was provided beyond the statement that the hydrogen-bonded network was three-dimensional. Analysis of the structure of (III) using the reported atomic coordinates shows that the hydrogen-bonded structure is, in fact, two-dimensional, not three-dimensional. A single O—H···O hydrogen bonds links the neutral and anionic components into chains running parallel to the [001] direction. The chain containing the reference components is propagated by means of the twofold rotation axes at x = 3/4, and this chain is linked by the cations to the two analogous chains which are propagated by the twofold rotation axes at x = 1/4 and x = 5/4, respectively, so forming a sheet built from two types of R66(32) ring, both of them centrosymmetric, and lying parallel to (010) (Fig. 3). Within this sheet, each neutral component acts as a twofold donor to anions via O—H···O hydrogen bonds and as a twofold acceptor from cations via N—H···O hydrogen bonds. Each anion acts as a fourfold acceptor, from two neutral acid units via O—H···O hydrogen bonds and from two cations via N—H···O hydrogen bonds. Each cation acts as a twofold donor in N—H···O hydrogen bonds, one each to a neutral component and to an anion. It must be emphasized here that, while the details of the donor/acceptor behaviour of the individual carboxyl units will change if the model of the O—H···O interactions is changed, the overall two-dimensional nature of the hydrogen-bonded structure will not change.
Thus, despite the much greater complexity in terms of chemical constitution of (III) compared with (II), in each of them the hydrogen-bonded structure is two-dimensional. In (I), on the other hand, where the molecular units contain only a single carboxyl group, the hydrogen-bonded structure is only one-dimensional.