Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113001893/cu3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113001893/cu3018Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113001893/cu3018Isup3.cml |
CCDC reference: 934561
For related literature, see: Andresen et al. (2000); Bomkamp et al. (2007); Cote et al. (2005); El-Kaderi, Hunt, Mendoza-Cortes, Cote, Taylor, O'Keefe & Yaghi (2007); Fyfe et al. (2000); Grange et al. (2010); Kocyigit & Guler (2011); Kocyigit et al. (2010); McKinnon et al. (2004); Simonsen (2010); Spitler et al. (2011); Thébault et al. (2011); Toda et al. (2000); Waldvogel et al. (2000); Wallentin et al. (2009, 2012); Wells (1954); Zniber et al. (2002).
2,3,6,7,10,11-Hexamethoxytriphenylene was prepared according to the literature method of Zniber et al. (2002). Other chemicals were purchased from Aldrich and used as received. X-ray diffraction data collection was performed at the University of Stockholm.
Hexahydroxytriphenylene [Should this be 2,3,6,7,10,11-Hexamethoxytriphenylene?] (81 mg, 0.25 mmol) and pyrazole (34 mg, 0.5 mmol) were placed in a round-bottomed flask and dissolved in dry CH3CN (10 ml). To this mixture, a solution of trimethyl borate (52 mg, 0.5 mmol) in dry CH3CN was added dropwise with continuous stirring. The reaction mixture was stirred for 1 h and a white solid was obtained. The solid product was filtered, washed with acetonitrile and dried in air. The isolated product was dissolved in methanol and colourless crystals of (I) were obtained after 2 d.
The hydroxy H atoms of htpp were located in a difference Fourier map, their coordinates were freely refined but their displacement parameters were constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(O). Aromatic H atoms were positioned geometrically and were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). Finally, all methanol H atoms were positioned geometrically. Methyl H atoms were constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C), and the methanol hydroxy H atom was constrained to ride on the parent atom, with Uiso(H) = 1.5Ueq(O).
Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: TOPOS (Blatov et al., 2000) and CrystalExplorer (McKinnon et al., 2004); software used to prepare material for publication: publCIF (Westrip, 2010).
C18H12O6·CH4O | Z = 2 |
Mr = 356.32 | F(000) = 372 |
Triclinic, P1 | Dx = 1.560 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5894 (7) Å | Cell parameters from 1226 reflections |
b = 10.550 (1) Å | θ = 3.4–28.8° |
c = 11.238 (2) Å | µ = 0.12 mm−1 |
α = 62.88 (1)° | T = 293 K |
β = 71.89 (1)° | Prismatic, colourless |
γ = 77.782 (9)° | 0.15 × 0.10 × 0.10 mm |
V = 758.6 (2) Å3 |
Agilent Xcalibur Sapphire3 diffractometer | 1613 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 25.0°, θmin = 3.4° |
Detector resolution: 16.5467 pixels mm-1 | h = −9→8 |
ω scans | k = −12→10 |
4609 measured reflections | l = −13→8 |
2683 independent 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0272P)2] where P = (Fo2 + 2Fc2)/3 |
2673 reflections | (Δ/σ)max < 0.001 |
255 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C18H12O6·CH4O | γ = 77.782 (9)° |
Mr = 356.32 | V = 758.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5894 (7) Å | Mo Kα radiation |
b = 10.550 (1) Å | µ = 0.12 mm−1 |
c = 11.238 (2) Å | T = 293 K |
α = 62.88 (1)° | 0.15 × 0.10 × 0.10 mm |
β = 71.89 (1)° |
Agilent Xcalibur Sapphire3 diffractometer | 1613 reflections with I > 2σ(I) |
4609 measured reflections | Rint = 0.032 |
2683 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.22 e Å−3 |
2673 reflections | Δρmin = −0.24 e Å−3 |
255 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
C1 | 0.3146 (3) | 0.7214 (3) | 0.2703 (2) | 0.0239 (6) | |
C2 | 0.3288 (3) | 0.8232 (3) | 0.1359 (3) | 0.0275 (7) | |
C3 | 0.4466 (3) | 0.7925 (3) | 0.0299 (2) | 0.0284 (7) | |
H3 | 0.4571 | 0.8611 | −0.0604 | 0.034* | |
C4 | 0.5514 (3) | 0.6605 (3) | 0.0547 (2) | 0.0231 (6) | |
C5 | 0.5359 (3) | 0.5573 (3) | 0.1910 (2) | 0.0228 (6) | |
C6 | 0.4140 (3) | 0.5916 (3) | 0.2982 (2) | 0.0252 (6) | |
H6 | 0.4014 | 0.5246 | 0.3892 | 0.030* | |
C7 | 0.6753 (3) | 0.6292 (3) | −0.0595 (2) | 0.0216 (6) | |
C8 | 0.6914 (3) | 0.7293 (3) | −0.1974 (2) | 0.0271 (7) | |
H8 | 0.6223 | 0.8173 | −0.2161 | 0.033* | |
C9 | 0.8055 (3) | 0.7008 (3) | −0.3045 (2) | 0.0267 (7) | |
C10 | 0.9118 (3) | 0.5704 (3) | −0.2788 (2) | 0.0259 (6) | |
C11 | 0.8989 (3) | 0.4713 (3) | −0.1463 (2) | 0.0259 (6) | |
H11 | 0.9701 | 0.3844 | −0.1299 | 0.031* | |
C12 | 0.7807 (3) | 0.4964 (3) | −0.0330 (2) | 0.0216 (6) | |
C13 | 0.6441 (3) | 0.4192 (3) | 0.2191 (2) | 0.0217 (6) | |
C14 | 0.7650 (3) | 0.3904 (3) | 0.1080 (2) | 0.0224 (6) | |
C15 | 0.8691 (3) | 0.2565 (3) | 0.1398 (2) | 0.0283 (7) | |
H15 | 0.9477 | 0.2350 | 0.0682 | 0.034* | |
C16 | 0.8577 (3) | 0.1580 (3) | 0.2720 (2) | 0.0282 (7) | |
C17 | 0.7369 (3) | 0.1865 (3) | 0.3810 (2) | 0.0264 (7) | |
C18 | 0.6328 (3) | 0.3143 (3) | 0.3536 (2) | 0.0250 (6) | |
H18 | 0.5518 | 0.3322 | 0.4267 | 0.030* | |
C19 | 0.2436 (4) | 0.1776 (4) | 0.7644 (3) | 0.0634 (11) | |
H19A | 0.2889 | 0.2103 | 0.8155 | 0.095* | |
H19B | 0.3354 | 0.1103 | 0.7391 | 0.095* | |
H19C | 0.1308 | 0.1322 | 0.8204 | 0.095* | |
O1 | 0.1978 (2) | 0.7616 (2) | 0.37271 (17) | 0.0344 (5) | |
H1A | 0.153 (4) | 0.692 (3) | 0.442 (3) | 0.052* | |
O2 | 0.2335 (3) | 0.9551 (2) | 0.10383 (19) | 0.0490 (7) | |
H2A | 0.169 (4) | 0.958 (4) | 0.173 (3) | 0.073* | |
O9 | 0.8190 (3) | 0.7971 (2) | −0.43977 (17) | 0.0400 (6) | |
H9A | 0.762 (4) | 0.878 (3) | −0.448 (3) | 0.060* | |
O10 | 1.0239 (2) | 0.5496 (2) | −0.39215 (17) | 0.0363 (6) | |
H10A | 1.078 (4) | 0.465 (3) | −0.368 (3) | 0.054* | |
O16 | 0.9705 (3) | 0.0325 (2) | 0.29697 (18) | 0.0418 (6) | |
H16A | 0.958 (4) | −0.024 (3) | 0.381 (3) | 0.063* | |
O17 | 0.7298 (3) | 0.0807 (2) | 0.51404 (19) | 0.0392 (6) | |
H17A | 0.739 (4) | 0.124 (4) | 0.556 (3) | 0.059* | |
O19 | 0.2076 (3) | 0.2963 (2) | 0.6428 (2) | 0.0571 (7) | |
H19 | 0.1792 | 0.2675 | 0.5953 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0267 (14) | 0.0237 (16) | 0.0193 (13) | −0.0005 (11) | 0.0013 (11) | −0.0124 (12) |
C2 | 0.0293 (15) | 0.0217 (16) | 0.0244 (15) | 0.0061 (12) | −0.0043 (12) | −0.0085 (12) |
C3 | 0.0339 (15) | 0.0270 (17) | 0.0168 (13) | 0.0020 (12) | −0.0023 (12) | −0.0074 (12) |
C4 | 0.0241 (14) | 0.0244 (16) | 0.0189 (13) | 0.0000 (11) | −0.0037 (11) | −0.0093 (12) |
C5 | 0.0214 (13) | 0.0253 (16) | 0.0183 (13) | −0.0027 (11) | −0.0023 (11) | −0.0076 (12) |
C6 | 0.0303 (14) | 0.0229 (16) | 0.0171 (13) | 0.0025 (12) | −0.0033 (11) | −0.0076 (11) |
C7 | 0.0211 (13) | 0.0215 (15) | 0.0208 (13) | −0.0012 (11) | −0.0023 (11) | −0.0097 (12) |
C8 | 0.0297 (14) | 0.0219 (16) | 0.0259 (15) | 0.0020 (11) | −0.0032 (12) | −0.0110 (12) |
C9 | 0.0304 (15) | 0.0254 (16) | 0.0180 (14) | −0.0012 (12) | −0.0032 (11) | −0.0059 (12) |
C10 | 0.0287 (14) | 0.0294 (17) | 0.0203 (14) | −0.0028 (12) | 0.0006 (11) | −0.0150 (12) |
C11 | 0.0287 (14) | 0.0230 (16) | 0.0239 (14) | 0.0010 (11) | −0.0050 (12) | −0.0104 (12) |
C12 | 0.0214 (13) | 0.0238 (16) | 0.0190 (13) | −0.0020 (11) | −0.0016 (11) | −0.0106 (11) |
C13 | 0.0256 (14) | 0.0200 (15) | 0.0194 (13) | −0.0017 (11) | −0.0052 (11) | −0.0085 (11) |
C14 | 0.0244 (14) | 0.0235 (15) | 0.0198 (13) | −0.0006 (11) | −0.0057 (11) | −0.0099 (12) |
C15 | 0.0336 (15) | 0.0289 (17) | 0.0201 (14) | 0.0025 (12) | −0.0021 (11) | −0.0135 (12) |
C16 | 0.0332 (15) | 0.0217 (16) | 0.0252 (15) | 0.0058 (12) | −0.0070 (12) | −0.0098 (12) |
C17 | 0.0358 (15) | 0.0231 (16) | 0.0162 (13) | 0.0018 (12) | −0.0058 (11) | −0.0070 (12) |
C18 | 0.0304 (15) | 0.0230 (16) | 0.0199 (14) | 0.0013 (12) | −0.0016 (11) | −0.0118 (12) |
C19 | 0.070 (2) | 0.054 (3) | 0.073 (3) | 0.0022 (19) | −0.033 (2) | −0.026 (2) |
O1 | 0.0467 (12) | 0.0274 (12) | 0.0180 (10) | 0.0062 (9) | 0.0019 (9) | −0.0105 (8) |
O2 | 0.0601 (14) | 0.0326 (13) | 0.0299 (12) | 0.0203 (11) | 0.0014 (10) | −0.0108 (10) |
O9 | 0.0579 (14) | 0.0293 (13) | 0.0174 (10) | 0.0066 (10) | −0.0011 (9) | −0.0065 (9) |
O10 | 0.0497 (13) | 0.0282 (12) | 0.0209 (10) | 0.0030 (9) | 0.0044 (9) | −0.0128 (9) |
O16 | 0.0572 (13) | 0.0278 (13) | 0.0245 (10) | 0.0165 (10) | −0.0051 (10) | −0.0094 (9) |
O17 | 0.0667 (13) | 0.0240 (12) | 0.0197 (11) | 0.0066 (10) | −0.0094 (9) | −0.0082 (9) |
O19 | 0.0813 (16) | 0.0464 (16) | 0.0557 (15) | 0.0184 (12) | −0.0336 (12) | −0.0309 (12) |
C1—C6 | 1.364 (3) | C13—C18 | 1.397 (3) |
C1—C2 | 1.383 (3) | C13—C14 | 1.417 (3) |
C1—O1 | 1.393 (3) | C14—C15 | 1.411 (3) |
C1—O1 | 1.393 (3) | C15—C16 | 1.359 (3) |
C2—O2 | 1.367 (3) | C15—H15 | 0.9300 |
C2—C3 | 1.375 (3) | C16—O16 | 1.377 (3) |
C3—C4 | 1.402 (3) | C16—C17 | 1.397 (3) |
C3—H3 | 0.9300 | C17—C18 | 1.364 (3) |
C4—C5 | 1.403 (3) | C17—O17 | 1.393 (3) |
C4—C7 | 1.465 (3) | C17—O17 | 1.393 (3) |
C5—C6 | 1.414 (3) | C18—H18 | 0.9300 |
C5—C13 | 1.460 (3) | C19—O19 | 1.427 (3) |
C6—H6 | 0.9300 | C19—H19A | 0.9600 |
C7—C8 | 1.406 (3) | C19—H19B | 0.9600 |
C7—C12 | 1.408 (3) | C19—H19C | 0.9600 |
C8—C9 | 1.364 (3) | O1—O1 | 0.000 (6) |
C8—H8 | 0.9300 | O1—H1A | 0.83 (3) |
C9—O9 | 1.375 (3) | O2—H2A | 0.79 (3) |
C9—C10 | 1.393 (3) | O9—H9A | 0.85 (3) |
C10—C11 | 1.361 (3) | O10—H10A | 0.86 (3) |
C10—O10 | 1.377 (3) | O16—H16A | 0.84 (3) |
C11—C12 | 1.412 (3) | O17—O17 | 0.000 (9) |
C11—H11 | 0.9300 | O17—H17A | 0.81 (4) |
C12—C14 | 1.450 (3) | O19—H19 | 0.8200 |
C6—C1—C2 | 120.9 (2) | C18—C13—C14 | 118.8 (2) |
C6—C1—O1 | 123.1 (2) | C18—C13—C5 | 121.5 (2) |
C2—C1—O1 | 116.0 (2) | C14—C13—C5 | 119.7 (2) |
C6—C1—O1 | 123.1 (2) | C15—C14—C13 | 117.8 (2) |
C2—C1—O1 | 116.0 (2) | C15—C14—C12 | 121.7 (2) |
O1—C1—O1 | 0.00 (15) | C13—C14—C12 | 120.5 (2) |
O2—C2—C3 | 118.2 (2) | C16—C15—C14 | 121.8 (2) |
O2—C2—C1 | 122.7 (2) | C16—C15—H15 | 119.1 |
C3—C2—C1 | 119.0 (2) | C14—C15—H15 | 119.1 |
C2—C3—C4 | 121.6 (2) | C15—C16—O16 | 119.2 (2) |
C2—C3—H3 | 119.2 | C15—C16—C17 | 120.0 (2) |
C4—C3—H3 | 119.2 | O16—C16—C17 | 120.7 (2) |
C3—C4—C5 | 119.2 (2) | C18—C17—O17 | 123.1 (2) |
C3—C4—C7 | 120.9 (2) | C18—C17—O17 | 123.1 (2) |
C5—C4—C7 | 119.9 (2) | O17—C17—O17 | 0.0 (3) |
C4—C5—C6 | 118.1 (2) | C18—C17—C16 | 119.6 (2) |
C4—C5—C13 | 120.1 (2) | O17—C17—C16 | 117.3 (2) |
C6—C5—C13 | 121.9 (2) | O17—C17—C16 | 117.3 (2) |
C1—C6—C5 | 121.2 (2) | C17—C18—C13 | 121.9 (2) |
C1—C6—H6 | 119.4 | C17—C18—H18 | 119.0 |
C5—C6—H6 | 119.4 | C13—C18—H18 | 119.0 |
C8—C7—C12 | 118.4 (2) | O19—C19—H19A | 109.5 |
C8—C7—C4 | 121.3 (2) | O19—C19—H19B | 109.5 |
C12—C7—C4 | 120.3 (2) | H19A—C19—H19B | 109.5 |
C9—C8—C7 | 121.8 (2) | O19—C19—H19C | 109.5 |
C9—C8—H8 | 119.1 | H19A—C19—H19C | 109.5 |
C7—C8—H8 | 119.1 | H19B—C19—H19C | 109.5 |
C8—C9—O9 | 122.1 (2) | O1—O1—C1 | 0 (10) |
C8—C9—C10 | 120.1 (2) | O1—O1—H1A | 0 (10) |
O9—C9—C10 | 117.9 (2) | C1—O1—H1A | 111 (2) |
C11—C10—O10 | 123.9 (2) | C2—O2—H2A | 108 (2) |
C11—C10—C9 | 119.5 (2) | C9—O9—H9A | 113 (2) |
O10—C10—C9 | 116.7 (2) | C10—O10—H10A | 111 (2) |
C10—C11—C12 | 122.0 (2) | C16—O16—H16A | 115 (2) |
C10—C11—H11 | 119.0 | O17—O17—C17 | 0 (10) |
C12—C11—H11 | 119.0 | O17—O17—H17A | 0 (10) |
C7—C12—C11 | 118.3 (2) | C17—O17—H17A | 103 (2) |
C7—C12—C14 | 119.6 (2) | C19—O19—H19 | 109.5 |
C11—C12—C14 | 122.1 (2) | ||
C6—C1—C2—O2 | −179.1 (3) | C8—C7—C12—C14 | −179.2 (2) |
O1—C1—C2—O2 | −0.7 (4) | C4—C7—C12—C14 | 0.4 (4) |
O1—C1—C2—O2 | −0.7 (4) | C10—C11—C12—C7 | −0.7 (4) |
C6—C1—C2—C3 | −0.7 (4) | C10—C11—C12—C14 | 179.2 (3) |
O1—C1—C2—C3 | 177.8 (2) | C4—C5—C13—C18 | 179.7 (3) |
O1—C1—C2—C3 | 177.8 (2) | C6—C5—C13—C18 | −0.2 (4) |
O2—C2—C3—C4 | 179.0 (3) | C4—C5—C13—C14 | 0.2 (4) |
C1—C2—C3—C4 | 0.5 (4) | C6—C5—C13—C14 | −179.7 (3) |
C2—C3—C4—C5 | −0.2 (4) | C18—C13—C14—C15 | −0.4 (4) |
C2—C3—C4—C7 | 179.6 (3) | C5—C13—C14—C15 | 179.1 (2) |
C3—C4—C5—C6 | 0.0 (4) | C18—C13—C14—C12 | 180.0 (2) |
C7—C4—C5—C6 | −179.7 (2) | C5—C13—C14—C12 | −0.5 (4) |
C3—C4—C5—C13 | −179.8 (2) | C7—C12—C14—C15 | −179.4 (3) |
C7—C4—C5—C13 | 0.4 (4) | C11—C12—C14—C15 | 0.7 (4) |
C2—C1—C6—C5 | 0.6 (4) | C7—C12—C14—C13 | 0.2 (4) |
O1—C1—C6—C5 | −177.8 (2) | C11—C12—C14—C13 | −179.7 (3) |
O1—C1—C6—C5 | −177.8 (2) | C13—C14—C15—C16 | −1.0 (4) |
C4—C5—C6—C1 | −0.2 (4) | C12—C14—C15—C16 | 178.6 (3) |
C13—C5—C6—C1 | 179.6 (2) | C14—C15—C16—O16 | −176.3 (3) |
C3—C4—C7—C8 | −0.9 (4) | C14—C15—C16—C17 | 1.7 (4) |
C5—C4—C7—C8 | 178.8 (3) | C15—C16—C17—C18 | −0.9 (4) |
C3—C4—C7—C12 | 179.5 (2) | O16—C16—C17—C18 | 177.1 (3) |
C5—C4—C7—C12 | −0.7 (4) | C15—C16—C17—O17 | 179.2 (3) |
C12—C7—C8—C9 | −0.1 (4) | O16—C16—C17—O17 | −2.8 (4) |
C4—C7—C8—C9 | −179.6 (3) | C15—C16—C17—O17 | 179.2 (3) |
C7—C8—C9—O9 | 178.6 (3) | O16—C16—C17—O17 | −2.8 (4) |
C7—C8—C9—C10 | −0.7 (4) | O17—C17—C18—C13 | 179.3 (3) |
C8—C9—C10—C11 | 0.8 (4) | O17—C17—C18—C13 | 179.3 (3) |
O9—C9—C10—C11 | −178.6 (3) | C16—C17—C18—C13 | −0.6 (4) |
C8—C9—C10—O10 | −179.9 (3) | C14—C13—C18—C17 | 1.2 (4) |
O9—C9—C10—O10 | 0.7 (4) | C5—C13—C18—C17 | −178.3 (3) |
O10—C10—C11—C12 | −179.3 (3) | C6—C1—O1—O1 | 0.0 (2) |
C9—C10—C11—C12 | −0.1 (4) | C2—C1—O1—O1 | 0.00 (18) |
C8—C7—C12—C11 | 0.8 (4) | C18—C17—O17—O17 | 0.00 (9) |
C4—C7—C12—C11 | −179.7 (2) | C16—C17—O17—O17 | 0.00 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O16—H16A···O17 | 0.84 (3) | 2.35 (3) | 2.741 (3) | 109 (2) |
O9—H9A···O17i | 0.85 (3) | 1.96 (3) | 2.761 (3) | 158 (3) |
O17—H17A···O1ii | 0.81 (4) | 1.93 (4) | 2.729 (3) | 170 (3) |
O10—H10A···O19iii | 0.86 (3) | 1.81 (3) | 2.655 (3) | 168 (3) |
O2—H2A···O1 | 0.79 (3) | 2.29 (3) | 2.734 (3) | 116 (3) |
O2—H2A···O16iv | 0.79 (3) | 2.00 (3) | 2.756 (2) | 159 (3) |
O1—H1A···O10v | 0.83 (3) | 1.90 (3) | 2.724 (3) | 172 (3) |
O19—H19···O9vi | 0.82 (4) | 2.14 (4) | 2.939 (3) | 164 (4) |
Symmetry codes: (i) x, y+1, z−1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z−1; (iv) x−1, y+1, z; (v) x−1, y, z+1; (vi) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C18H12O6·CH4O |
Mr | 356.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.5894 (7), 10.550 (1), 11.238 (2) |
α, β, γ (°) | 62.88 (1), 71.89 (1), 77.782 (9) |
V (Å3) | 758.6 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Agilent Xcalibur Sapphire3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4609, 2683, 1613 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.114, 0.97 |
No. of reflections | 2673 |
No. of parameters | 255 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), TOPOS (Blatov et al., 2000) and CrystalExplorer (McKinnon et al., 2004), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O16—H16A···O17 | 0.84 (3) | 2.35 (3) | 2.741 (3) | 109 (2) |
O9—H9A···O17i | 0.85 (3) | 1.96 (3) | 2.761 (3) | 158 (3) |
O17—H17A···O1ii | 0.81 (4) | 1.93 (4) | 2.729 (3) | 170 (3) |
O10—H10A···O19iii | 0.86 (3) | 1.81 (3) | 2.655 (3) | 168 (3) |
O2—H2A···O1 | 0.79 (3) | 2.29 (3) | 2.734 (3) | 116 (3) |
O2—H2A···O16iv | 0.79 (3) | 2.00 (3) | 2.756 (2) | 159 (3) |
O1—H1A···O10v | 0.83 (3) | 1.90 (3) | 2.724 (3) | 172 (3) |
O19—H19···O9vi | 0.82 (4) | 2.14 (4) | 2.939 (3) | 164 (4) |
Symmetry codes: (i) x, y+1, z−1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z−1; (iv) x−1, y+1, z; (v) x−1, y, z+1; (vi) −x+1, −y+1, −z+2. |
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2,3,6,7,10,11-Hexahydroxytriphenylene (hhtp) continues to be important both as a starting material for forming discrete supramolecular units and in its own right (Fyfe et al., 2000; Waldvogel et al., 2000; Bomkamp et al., 2007; Cote et al., 2005; El-Kaderi et al., 2007; Kocyigit et al., 2010; Kocyigit & Guler 2011; Spitler et al., 2011; Simonsen, 2010). Thus, reporting new polymorphs or solvates is important as these can then be rapidly detected by powder X-ray diffraction. We report here the isolation of a new methanol solvate of 2,3,6,7,10,11-hexahydroxytriphenylene, the title compound, (I), obtained from an unsuccessful reaction of hexahydroxytriphenylene [Should this be 2,3,6,7,10,11-hexamethoxytriphenylene?], pyrazole and trimethyl borate, a reaction used for the purpose of constructing new covalent organic frameworks.
The crystal structure of (I) is distinctly different from four other solvates reported for this compound, viz. the monohydrate, (II) [space group P21/c, a = 11.127 (2) Å, b = 12.797 (3) Å, c = 11.081 (2) Å and β = 119.32 (3)°; Andresen et al., 2000], the cyclopentanone trisolvate, (III) [space group P21, a = 7.986 (3) Å, b = 10.161 (2) Å, c = 18.554 (2) Å and β = 99.84 (1)°], the cyclopentanone tetrasolvate monohydrate, (IV) [space group P21/c, a = 7.603 (7) Å, b = 20.937 (3) Å, c = 22.245 (3) Å and β = 91.85 (3)°; Toda et al., 2000], and the dihydrate, (V) [space group Pbcn, a = 14.2694 (8) Å, b = 16.5639 (8) Å, c = 7.2237 (4) Å; Thébault et al., 2011].
The methanol solvate, in contrast with the dihydrate (V), is not stable during extended storage due to loss of crystallinity, explaining the somewhat lower than expected quality of the data.
The structure of (I) has a hexahydroxytriphenylene unit very similar to those in the four previously reported structures (Fig. 1). It is important to check this, as there are some indications that radical species may form (Grange et al., 2010).
The hydrogen-bond networks in (I)–(V) are, to a greater or lesser extent, responsible for the overall structures. Diols of rigid hydrocarbon skeletons are well known to give three-dimensional networks of different topologies (Wells, 1954; Wallentin et al., 2009, 2012), but solvated species may be less obvious to interpret in this way, and the large number of hydroxy groups in the present structure makes this even more difficult. Analyzing the previous four structures, we find that in cyclopentanone solvates (III) and (IV), each hhtp molecule forms hydrogen bonds to four other units, forming a (4,4) connected two-dimensional network, with the cyclopentanone molecules hydrogen-bonded and protruding from the network and with a layer of cyclopentanone molecules effectively isolating the flat parts of the aromatic skeletons from each other. In monohydrate (II), each hhtp molecule forms hydrogen bonds to six other hhtp molecules, giving an intricate double layer of two (4,4) networks where each vertex connects to two other vertices in the neighbouring network. The water molecules connect these layers into a complicated three-dimensional network through hydrogen bonding, and in dihydrate (V) the (4,4) two-dimensional network seen in (III) and (IV) is reproduced and further crosslinked by water molecules to form a complex three-dimensional network.
In (I), hexagonal hydrogen-bonded two-dimensional layers are formed with parallel but slightly twisted hhtp molecules. One hhtp molecule interconnects with six neighbouring hhtp molecules via hydrogen bonds. These layers are further connected by one hydrogen bond per hhtp molecule to the closest layer (O17—H17A···O1), giving a two-layer structure (Fig. 2b). These double layers are then further connected into an intricate three-dimensional network by hydrogen bonds to methanol molecules (O19—H19A···O9), only slightly protruding from the plane and with their methyl groups in the open spaces in the hexagonal layer. The interpretation of this network in terms of topology would result in a net with at least four different types of vertices, and we do not see any advantage in this type of exercise for understanding or communicating this structure.
The structure of (I) contains two similar interlayer distances and we would expect substantial π–π stacking, as the hydrogen bonds between any type of layer are few. Moreover, the five different structures give us the opportunity to compare the π–π stacking. This comparison will be done using Hirshfeld surfaces (McKinnon et al., 2004).
To calculate the Hirshfeld surfaces one starts by replacing every atom with a spherically averaged theoretical electron density. The surface is then generated by those points at which the calculated electron density from the chosen molecule equals that from the surrounding molecules in the crystal structure. Inside this surface we now have the volume of the crystal structure wherein the electron density is dominated by the chosen molecule.
The best indicator of π–π stacking on Hirshfeld surfaces is obtained by plotting the shape index. The shape index at a point on the surface is derived from the normal to the surface and the gradient of the surface in two principal directions perpendicular to the normal. For these two directions, the κ1 and κ2 values, which represent how much and in which direction the surface is changing, are generated and then used to compute the shape index as S = (2/π) arctan[(κ1 + κ2)/(κ1 - κ2)] (McKinnon et al., 2004). McKinnon and co-workers further noted that this generates complementary surfaces with different signs (usually drawn in red or blue) on two surfaces that touch each other and that the triangular shapes are especially indicative of π–π stacking.
We found that a striking visual comparison could be made by plotting the shape index only for the regions on the surface with close C···C interactions (these generally fall in the region 3.3–3.9 Å). The plots for solvates (I)–(V) are shown in Fig. 3, presented in decreasing order of π–π stacking.
In view of the solvent layers separating cyclopentanone solvates (III) and (IV), we do not expect significant π–π stacking in these structures, and indeed the C···C interactions form only 0.4–0.5% of the surface area, the surface itself is clearly nonplanar and the shape index showing only C···C interactions is very small. In contrast, the hydrates and the methanol solvate all show significant π–π stacking, with 12–15% C···C interactions on the surface and striking areas of C···C-filtered shape-index plots. For the monohydrate in particular, the difference between the two sides of the hhtp molecules is clearly shown.
In contrast with the marked differences in π–π stacking, the hydrogen bonding of the hhtp molecule varies only slightly in the five solvates. The hhtp O···H interactions account for 36% of the hhtp Hirshfeld surface in (I), 35% in (II), 40% in (II), 37% in (IV) and 39% in (V).