Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113011232/mx3095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011232/mx3095Isup2.hkl |
CCDC reference: 950446
For related literature, see: Balaban et al. (2000); Barea et al. (2011); Bhyrappa et al. (2008); Butcher et al. (1985); Chen & Tulinsky (1972); Chen et al. (2010); Chung et al. (2009); Gross & Ini (1999); Heppke et al. (2000); Jakob et al. (2009); Jameson & Ibers (1980); Kugimiya & Takemura (1990); Limbach et al. (1984); Silvers & Tulinsky (1967); Yang et al. (2011); Zhao et al. (2000).
4-(Heptyloxy)benzaldehyde (0.02 mol, 4.4 g) was mixed with propionic acid (40 ml) in a 100 ml flask. The mixture was refluxed for 15 min and then freshly distilled pyrrole (0.02 mol, 1.45 ml) was added dropwise to the reaction mixture. The mixture was refluxed for 1.0 h and then stirred at room temperature, and methanol (40 ml) was added, keeping the temperature [constant?] overnight. The purple solid which formed was filtered off and washed with methanol to remove traces of propionic acid. The title compound, (I), was obtained after purification by column chromatography using neutral alumina and was recrystallized from chloroform–methanol [Solvent ratio?] as a purple solid (yield 12%, m.p. 527–528 K). Single crystals of (I) suitable for X-ray diffraction were obtained by vapour diffusion of hexane into a dichloromethane solution at room temperature.
C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 (aromatic), 0.99 (CH2) or 0.98 Å (CH3), and with Uiso(H) = xUeq(C), where x = 1.5 for methyl and 1.2 for all other H atoms. Electron-density peaks near to atoms N1 and N2 and corresponding to H atoms were found in a difference Fourier map, which means disorder of these H atoms. Atoms H1A and H2A attached to atoms N1 and N2 were refined with a distance restraint of N—H = 0.86 (1) Å and with Uiso(H) = 1.2Ueq(N) (semi-free treatment). The occupancy factors of the disordered H atoms refined to 0.28 (2):0.72 (2) (H1A:H2A).
Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C72H86N4O4 | F(000) = 1156 |
Mr = 1071.45 | Dx = 1.146 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3478 reflections |
a = 15.9611 (10) Å | θ = 2.3–25.2° |
b = 19.1464 (12) Å | µ = 0.07 mm−1 |
c = 10.1620 (6) Å | T = 185 K |
β = 91.335 (1)° | Block, purple |
V = 3104.6 (3) Å3 | 0.25 × 0.12 × 0.09 mm |
Z = 2 |
Bruker APEX CCD area-detector diffractometer | 5897 independent reflections |
Radiation source: fine-focus sealed tube | 4393 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 25.7°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −17→19 |
Tmin = 0.983, Tmax = 0.994 | k = −20→23 |
15401 measured reflections | l = −10→12 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0568P)2 + 0.7417P] where P = (Fo2 + 2Fc2)/3 |
5897 reflections | (Δ/σ)max = 0.001 |
370 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C72H86N4O4 | V = 3104.6 (3) Å3 |
Mr = 1071.45 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.9611 (10) Å | µ = 0.07 mm−1 |
b = 19.1464 (12) Å | T = 185 K |
c = 10.1620 (6) Å | 0.25 × 0.12 × 0.09 mm |
β = 91.335 (1)° |
Bruker APEX CCD area-detector diffractometer | 5897 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 4393 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.994 | Rint = 0.028 |
15401 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.20 e Å−3 |
5897 reflections | Δρmin = −0.17 e Å−3 |
370 parameters |
Experimental. UV–Vis (λ, nm) in chloroform: 422.97, 519.82, 556.96,593.02, 650.91. |
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 | Occ. (<1) | |
O1 | 0.51741 (7) | 0.09266 (7) | 0.42585 (12) | 0.0410 (3) | |
O2 | 1.09423 (8) | 0.46877 (6) | −0.07553 (11) | 0.0349 (3) | |
N1 | 0.93494 (8) | 0.08790 (7) | 0.04215 (13) | 0.0262 (3) | |
H1A | 0.960 (4) | 0.0484 (17) | 0.031 (6) | 0.031* | 0.28 (2) |
N2 | 1.09930 (9) | 0.06192 (7) | −0.06170 (13) | 0.0283 (3) | |
H2A | 1.0594 (11) | 0.0346 (11) | −0.039 (2) | 0.034* | 0.72 (2) |
C1 | 0.85825 (10) | 0.09096 (9) | 0.10027 (15) | 0.0269 (4) | |
C2 | 0.83418 (10) | 0.16273 (9) | 0.11867 (16) | 0.0308 (4) | |
H2 | 0.7842 | 0.1789 | 0.1576 | 0.037* | |
C3 | 0.89564 (10) | 0.20264 (9) | 0.07042 (16) | 0.0303 (4) | |
H3 | 0.8968 | 0.2522 | 0.0670 | 0.036* | |
C4 | 0.95948 (10) | 0.15567 (8) | 0.02476 (15) | 0.0258 (4) | |
C5 | 1.03729 (10) | 0.17813 (8) | −0.02219 (15) | 0.0262 (4) | |
C6 | 1.10158 (10) | 0.13348 (9) | −0.06101 (15) | 0.0276 (4) | |
C7 | 1.18019 (10) | 0.15404 (9) | −0.11416 (16) | 0.0321 (4) | |
H7 | 1.1997 | 0.2006 | −0.1239 | 0.039* | |
C8 | 1.22180 (11) | 0.09537 (9) | −0.14801 (17) | 0.0321 (4) | |
H8 | 1.2755 | 0.0936 | −0.1863 | 0.039* | |
C9 | 1.17105 (10) | 0.03643 (9) | −0.11615 (16) | 0.0280 (4) | |
C10 | 0.80933 (10) | 0.03361 (9) | 0.13792 (16) | 0.0275 (4) | |
C11 | 0.73178 (10) | 0.04817 (8) | 0.21401 (17) | 0.0291 (4) | |
C12 | 0.73573 (11) | 0.04892 (10) | 0.34984 (18) | 0.0389 (5) | |
H12 | 0.7877 | 0.0396 | 0.3937 | 0.047* | |
C13 | 0.66586 (12) | 0.06295 (10) | 0.42414 (18) | 0.0407 (5) | |
H13 | 0.6704 | 0.0628 | 0.5175 | 0.049* | |
C14 | 0.58989 (11) | 0.07708 (9) | 0.36240 (18) | 0.0331 (4) | |
C15 | 0.58460 (12) | 0.07570 (10) | 0.22576 (19) | 0.0416 (5) | |
H15 | 0.5326 | 0.0849 | 0.1818 | 0.050* | |
C16 | 0.65470 (11) | 0.06105 (10) | 0.15357 (18) | 0.0402 (5) | |
H16 | 0.6499 | 0.0598 | 0.0602 | 0.048* | |
C17 | 0.51999 (12) | 0.09014 (10) | 0.56676 (18) | 0.0431 (5) | |
H17A | 0.5666 | 0.1195 | 0.6015 | 0.052* | |
H17B | 0.5295 | 0.0415 | 0.5968 | 0.052* | |
C18 | 0.43755 (12) | 0.11673 (10) | 0.6172 (2) | 0.0456 (5) | |
H18A | 0.4340 | 0.1052 | 0.7119 | 0.055* | |
H18B | 0.3911 | 0.0923 | 0.5701 | 0.055* | |
C19 | 0.42644 (12) | 0.19497 (10) | 0.5995 (2) | 0.0430 (5) | |
H19A | 0.4172 | 0.2051 | 0.5048 | 0.052* | |
H19B | 0.4789 | 0.2187 | 0.6283 | 0.052* | |
C20 | 0.35393 (12) | 0.22543 (10) | 0.6756 (2) | 0.0433 (5) | |
H20A | 0.3006 | 0.2068 | 0.6384 | 0.052* | |
H20B | 0.3589 | 0.2101 | 0.7685 | 0.052* | |
C21 | 0.35147 (13) | 0.30456 (10) | 0.6711 (2) | 0.0490 (5) | |
H21A | 0.3428 | 0.3195 | 0.5785 | 0.059* | |
H21B | 0.4065 | 0.3228 | 0.7020 | 0.059* | |
C22 | 0.28363 (13) | 0.33698 (11) | 0.7534 (2) | 0.0564 (6) | |
H22A | 0.2282 | 0.3211 | 0.7194 | 0.068* | |
H22B | 0.2903 | 0.3202 | 0.8453 | 0.068* | |
C23 | 0.28581 (18) | 0.41588 (13) | 0.7529 (3) | 0.0809 (8) | |
H23A | 0.3408 | 0.4320 | 0.7854 | 0.097* | |
H23B | 0.2421 | 0.4339 | 0.8100 | 0.097* | |
H23C | 0.2759 | 0.4329 | 0.6629 | 0.097* | |
C24 | 1.05164 (10) | 0.25488 (8) | −0.03540 (15) | 0.0268 (4) | |
C25 | 1.00965 (12) | 0.29237 (9) | −0.13296 (17) | 0.0362 (4) | |
H25 | 0.9715 | 0.2685 | −0.1903 | 0.043* | |
C26 | 1.02143 (11) | 0.36351 (9) | −0.14985 (17) | 0.0357 (4) | |
H26 | 0.9914 | 0.3878 | −0.2174 | 0.043* | |
C27 | 1.07736 (10) | 0.39885 (9) | −0.06746 (16) | 0.0285 (4) | |
C28 | 1.11947 (11) | 0.36240 (9) | 0.03157 (17) | 0.0357 (4) | |
H28 | 1.1575 | 0.3863 | 0.0890 | 0.043* | |
C29 | 1.10656 (11) | 0.29164 (9) | 0.04748 (17) | 0.0344 (4) | |
H29 | 1.1357 | 0.2676 | 0.1163 | 0.041* | |
C30 | 1.04834 (11) | 0.50883 (9) | −0.17326 (18) | 0.0348 (4) | |
H30A | 0.9882 | 0.5107 | −0.1515 | 0.042* | |
H30B | 1.0535 | 0.4870 | −0.2610 | 0.042* | |
C31 | 1.08495 (11) | 0.58145 (9) | −0.17379 (18) | 0.0352 (4) | |
H31A | 1.0868 | 0.5998 | −0.0827 | 0.042* | |
H31B | 1.0480 | 0.6124 | −0.2274 | 0.042* | |
C32 | 1.17261 (11) | 0.58327 (9) | −0.22846 (18) | 0.0339 (4) | |
H32A | 1.1706 | 0.5634 | −0.3184 | 0.041* | |
H32B | 1.2093 | 0.5528 | −0.1734 | 0.041* | |
C33 | 1.21197 (11) | 0.65554 (9) | −0.23443 (18) | 0.0358 (4) | |
H33A | 1.1715 | 0.6883 | −0.2766 | 0.043* | |
H33B | 1.2238 | 0.6723 | −0.1437 | 0.043* | |
C34 | 1.29262 (11) | 0.65618 (10) | −0.31055 (18) | 0.0383 (4) | |
H34A | 1.3314 | 0.6212 | −0.2712 | 0.046* | |
H34B | 1.2798 | 0.6415 | −0.4022 | 0.046* | |
C35 | 1.33689 (13) | 0.72612 (11) | −0.3134 (2) | 0.0527 (6) | |
H35A | 1.3525 | 0.7399 | −0.2222 | 0.063* | |
H35B | 1.2977 | 0.7618 | −0.3495 | 0.063* | |
C36 | 1.41502 (15) | 0.72523 (13) | −0.3954 (2) | 0.0642 (7) | |
H36A | 1.4533 | 0.6890 | −0.3622 | 0.077* | |
H36B | 1.4427 | 0.7708 | −0.3897 | 0.077* | |
H36C | 1.3995 | 0.7153 | −0.4874 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0299 (7) | 0.0454 (8) | 0.0483 (8) | 0.0039 (6) | 0.0156 (6) | −0.0035 (6) |
O2 | 0.0421 (8) | 0.0235 (6) | 0.0388 (7) | −0.0047 (5) | −0.0028 (6) | 0.0033 (5) |
N1 | 0.0242 (8) | 0.0248 (8) | 0.0298 (7) | −0.0014 (6) | 0.0058 (6) | −0.0002 (6) |
N2 | 0.0257 (8) | 0.0240 (8) | 0.0354 (8) | −0.0016 (6) | 0.0072 (6) | 0.0006 (6) |
C1 | 0.0247 (9) | 0.0279 (9) | 0.0283 (8) | 0.0008 (7) | 0.0023 (7) | −0.0011 (7) |
C2 | 0.0259 (9) | 0.0304 (10) | 0.0363 (9) | 0.0038 (7) | 0.0056 (7) | −0.0023 (7) |
C3 | 0.0310 (9) | 0.0239 (9) | 0.0364 (9) | 0.0022 (7) | 0.0049 (7) | −0.0009 (7) |
C4 | 0.0272 (9) | 0.0243 (9) | 0.0259 (8) | 0.0000 (7) | 0.0013 (7) | 0.0000 (7) |
C5 | 0.0275 (9) | 0.0240 (9) | 0.0271 (8) | −0.0013 (7) | 0.0009 (7) | −0.0009 (7) |
C6 | 0.0285 (9) | 0.0254 (9) | 0.0289 (9) | −0.0032 (7) | 0.0030 (7) | 0.0015 (7) |
C7 | 0.0309 (9) | 0.0260 (9) | 0.0397 (10) | −0.0042 (7) | 0.0076 (8) | 0.0021 (8) |
C8 | 0.0259 (9) | 0.0310 (10) | 0.0399 (10) | −0.0028 (7) | 0.0097 (7) | 0.0011 (8) |
C9 | 0.0241 (9) | 0.0288 (9) | 0.0314 (9) | −0.0003 (7) | 0.0057 (7) | 0.0006 (7) |
C10 | 0.0231 (9) | 0.0299 (9) | 0.0297 (9) | −0.0002 (7) | 0.0039 (7) | 0.0002 (7) |
C11 | 0.0265 (9) | 0.0235 (9) | 0.0377 (10) | −0.0005 (7) | 0.0083 (7) | 0.0007 (7) |
C12 | 0.0263 (10) | 0.0486 (12) | 0.0420 (11) | 0.0055 (8) | 0.0036 (8) | −0.0035 (9) |
C13 | 0.0352 (11) | 0.0533 (13) | 0.0339 (10) | 0.0050 (9) | 0.0084 (8) | −0.0056 (9) |
C14 | 0.0257 (9) | 0.0276 (9) | 0.0465 (11) | 0.0000 (7) | 0.0129 (8) | −0.0016 (8) |
C15 | 0.0280 (10) | 0.0512 (12) | 0.0457 (11) | 0.0075 (9) | 0.0034 (8) | 0.0035 (9) |
C16 | 0.0321 (10) | 0.0533 (13) | 0.0356 (10) | 0.0038 (9) | 0.0078 (8) | 0.0034 (9) |
C17 | 0.0439 (12) | 0.0392 (11) | 0.0469 (11) | 0.0029 (9) | 0.0153 (9) | −0.0036 (9) |
C18 | 0.0426 (12) | 0.0406 (12) | 0.0546 (12) | −0.0007 (9) | 0.0246 (10) | −0.0038 (9) |
C19 | 0.0362 (11) | 0.0407 (12) | 0.0528 (12) | −0.0001 (9) | 0.0168 (9) | −0.0018 (9) |
C20 | 0.0340 (11) | 0.0387 (11) | 0.0578 (12) | −0.0002 (8) | 0.0159 (9) | −0.0054 (9) |
C21 | 0.0459 (12) | 0.0386 (12) | 0.0630 (13) | 0.0012 (9) | 0.0131 (10) | −0.0022 (10) |
C22 | 0.0452 (13) | 0.0394 (12) | 0.0850 (16) | 0.0042 (10) | 0.0124 (11) | −0.0120 (11) |
C23 | 0.084 (2) | 0.0461 (15) | 0.114 (2) | 0.0120 (13) | 0.0280 (17) | −0.0107 (15) |
C24 | 0.0249 (9) | 0.0255 (9) | 0.0302 (9) | −0.0007 (7) | 0.0062 (7) | −0.0005 (7) |
C25 | 0.0415 (11) | 0.0308 (10) | 0.0360 (10) | −0.0078 (8) | −0.0051 (8) | −0.0002 (8) |
C26 | 0.0431 (11) | 0.0299 (10) | 0.0338 (10) | −0.0021 (8) | −0.0051 (8) | 0.0050 (8) |
C27 | 0.0305 (9) | 0.0226 (9) | 0.0327 (9) | −0.0028 (7) | 0.0062 (7) | −0.0002 (7) |
C28 | 0.0371 (10) | 0.0301 (10) | 0.0395 (10) | −0.0058 (8) | −0.0079 (8) | 0.0005 (8) |
C29 | 0.0336 (10) | 0.0297 (10) | 0.0396 (10) | −0.0011 (8) | −0.0060 (8) | 0.0059 (8) |
C30 | 0.0380 (10) | 0.0285 (10) | 0.0380 (10) | 0.0003 (8) | 0.0026 (8) | 0.0055 (8) |
C31 | 0.0393 (11) | 0.0258 (9) | 0.0409 (10) | 0.0017 (8) | 0.0054 (8) | 0.0039 (8) |
C32 | 0.0382 (11) | 0.0255 (9) | 0.0383 (10) | 0.0026 (8) | 0.0046 (8) | 0.0002 (8) |
C33 | 0.0364 (10) | 0.0291 (10) | 0.0420 (10) | 0.0014 (8) | 0.0059 (8) | 0.0020 (8) |
C34 | 0.0384 (11) | 0.0361 (11) | 0.0405 (10) | 0.0012 (8) | 0.0066 (8) | 0.0008 (8) |
C35 | 0.0521 (13) | 0.0412 (12) | 0.0656 (14) | −0.0072 (10) | 0.0207 (11) | 0.0011 (10) |
C36 | 0.0607 (15) | 0.0595 (15) | 0.0735 (16) | −0.0156 (12) | 0.0266 (12) | 0.0018 (12) |
O1—C14 | 1.370 (2) | C19—H19B | 0.9900 |
O1—C17 | 1.432 (2) | C20—C21 | 1.516 (3) |
O2—C27 | 1.3683 (19) | C20—H20A | 0.9900 |
O2—C30 | 1.441 (2) | C20—H20B | 0.9900 |
N1—C4 | 1.368 (2) | C21—C22 | 1.516 (3) |
N1—C1 | 1.373 (2) | C21—H21A | 0.9900 |
N1—H1A | 0.863 (10) | C21—H21B | 0.9900 |
N2—C6 | 1.371 (2) | C22—C23 | 1.511 (3) |
N2—C9 | 1.373 (2) | C22—H22A | 0.9900 |
N2—H2A | 0.860 (10) | C22—H22B | 0.9900 |
C1—C10 | 1.405 (2) | C23—H23A | 0.9800 |
C1—C2 | 1.440 (2) | C23—H23B | 0.9800 |
C2—C3 | 1.345 (2) | C23—H23C | 0.9800 |
C2—H2 | 0.9500 | C24—C25 | 1.384 (2) |
C3—C4 | 1.444 (2) | C24—C29 | 1.392 (2) |
C3—H3 | 0.9500 | C25—C26 | 1.386 (2) |
C4—C5 | 1.408 (2) | C25—H25 | 0.9500 |
C5—C6 | 1.399 (2) | C26—C27 | 1.386 (2) |
C5—C24 | 1.494 (2) | C26—H26 | 0.9500 |
C6—C7 | 1.433 (2) | C27—C28 | 1.386 (2) |
C7—C8 | 1.354 (2) | C28—C29 | 1.380 (2) |
C7—H7 | 0.9500 | C28—H28 | 0.9500 |
C8—C9 | 1.431 (2) | C29—H29 | 0.9500 |
C8—H8 | 0.9500 | C30—C31 | 1.508 (2) |
C9—C10i | 1.396 (2) | C30—H30A | 0.9900 |
C10—C9i | 1.396 (2) | C30—H30B | 0.9900 |
C10—C11 | 1.501 (2) | C31—C32 | 1.518 (2) |
C11—C12 | 1.380 (2) | C31—H31A | 0.9900 |
C11—C16 | 1.384 (2) | C31—H31B | 0.9900 |
C12—C13 | 1.387 (2) | C32—C33 | 1.521 (2) |
C12—H12 | 0.9500 | C32—H32A | 0.9900 |
C13—C14 | 1.379 (3) | C32—H32B | 0.9900 |
C13—H13 | 0.9500 | C33—C34 | 1.517 (2) |
C14—C15 | 1.389 (3) | C33—H33A | 0.9900 |
C15—C16 | 1.381 (2) | C33—H33B | 0.9900 |
C15—H15 | 0.9500 | C34—C35 | 1.515 (3) |
C16—H16 | 0.9500 | C34—H34A | 0.9900 |
C17—C18 | 1.511 (2) | C34—H34B | 0.9900 |
C17—H17A | 0.9900 | C35—C36 | 1.516 (3) |
C17—H17B | 0.9900 | C35—H35A | 0.9900 |
C18—C19 | 1.519 (3) | C35—H35B | 0.9900 |
C18—H18A | 0.9900 | C36—H36A | 0.9800 |
C18—H18B | 0.9900 | C36—H36B | 0.9800 |
C19—C20 | 1.523 (2) | C36—H36C | 0.9800 |
C19—H19A | 0.9900 | ||
C14—O1—C17 | 117.27 (14) | H20A—C20—H20B | 107.8 |
C27—O2—C30 | 117.67 (13) | C20—C21—C22 | 114.25 (17) |
C4—N1—C1 | 106.02 (13) | C20—C21—H21A | 108.7 |
C4—N1—H1A | 133 (4) | C22—C21—H21A | 108.7 |
C1—N1—H1A | 121 (4) | C20—C21—H21B | 108.7 |
C6—N2—C9 | 109.58 (13) | C22—C21—H21B | 108.7 |
C6—N2—H2A | 128.8 (17) | H21A—C21—H21B | 107.6 |
C9—N2—H2A | 121.4 (17) | C23—C22—C21 | 112.98 (19) |
N1—C1—C10 | 126.18 (15) | C23—C22—H22A | 109.0 |
N1—C1—C2 | 109.86 (14) | C21—C22—H22A | 109.0 |
C10—C1—C2 | 123.95 (15) | C23—C22—H22B | 109.0 |
C3—C2—C1 | 107.20 (15) | C21—C22—H22B | 109.0 |
C3—C2—H2 | 126.4 | H22A—C22—H22B | 107.8 |
C1—C2—H2 | 126.4 | C22—C23—H23A | 109.5 |
C2—C3—C4 | 106.83 (15) | C22—C23—H23B | 109.5 |
C2—C3—H3 | 126.6 | H23A—C23—H23B | 109.5 |
C4—C3—H3 | 126.6 | C22—C23—H23C | 109.5 |
N1—C4—C5 | 126.23 (14) | H23A—C23—H23C | 109.5 |
N1—C4—C3 | 110.05 (14) | H23B—C23—H23C | 109.5 |
C5—C4—C3 | 123.60 (15) | C25—C24—C29 | 117.28 (16) |
C6—C5—C4 | 124.56 (15) | C25—C24—C5 | 120.12 (15) |
C6—C5—C24 | 117.42 (14) | C29—C24—C5 | 122.60 (15) |
C4—C5—C24 | 117.99 (14) | C24—C25—C26 | 122.24 (16) |
N2—C6—C5 | 126.33 (15) | C24—C25—H25 | 118.9 |
N2—C6—C7 | 107.23 (14) | C26—C25—H25 | 118.9 |
C5—C6—C7 | 126.36 (15) | C27—C26—C25 | 119.49 (16) |
C8—C7—C6 | 107.87 (15) | C27—C26—H26 | 120.3 |
C8—C7—H7 | 126.1 | C25—C26—H26 | 120.3 |
C6—C7—H7 | 126.1 | O2—C27—C28 | 116.33 (15) |
C7—C8—C9 | 108.27 (15) | O2—C27—C26 | 124.49 (15) |
C7—C8—H8 | 125.9 | C28—C27—C26 | 119.17 (16) |
C9—C8—H8 | 125.9 | C29—C28—C27 | 120.55 (16) |
N2—C9—C10i | 126.70 (15) | C29—C28—H28 | 119.7 |
N2—C9—C8 | 107.02 (14) | C27—C28—H28 | 119.7 |
C10i—C9—C8 | 126.27 (15) | C28—C29—C24 | 121.26 (16) |
C9i—C10—C1 | 125.40 (15) | C28—C29—H29 | 119.4 |
C9i—C10—C11 | 116.80 (14) | C24—C29—H29 | 119.4 |
C1—C10—C11 | 117.73 (14) | O2—C30—C31 | 107.60 (14) |
C12—C11—C16 | 117.46 (15) | O2—C30—H30A | 110.2 |
C12—C11—C10 | 119.88 (15) | C31—C30—H30A | 110.2 |
C16—C11—C10 | 122.66 (15) | O2—C30—H30B | 110.2 |
C11—C12—C13 | 121.85 (17) | C31—C30—H30B | 110.2 |
C11—C12—H12 | 119.1 | H30A—C30—H30B | 108.5 |
C13—C12—H12 | 119.1 | C30—C31—C32 | 112.52 (14) |
C14—C13—C12 | 119.98 (17) | C30—C31—H31A | 109.1 |
C14—C13—H13 | 120.0 | C32—C31—H31A | 109.1 |
C12—C13—H13 | 120.0 | C30—C31—H31B | 109.1 |
O1—C14—C13 | 124.86 (16) | C32—C31—H31B | 109.1 |
O1—C14—C15 | 116.24 (16) | H31A—C31—H31B | 107.8 |
C13—C14—C15 | 118.90 (16) | C31—C32—C33 | 114.87 (14) |
C16—C15—C14 | 120.24 (17) | C31—C32—H32A | 108.5 |
C16—C15—H15 | 119.9 | C33—C32—H32A | 108.5 |
C14—C15—H15 | 119.9 | C31—C32—H32B | 108.5 |
C15—C16—C11 | 121.55 (17) | C33—C32—H32B | 108.5 |
C15—C16—H16 | 119.2 | H32A—C32—H32B | 107.5 |
C11—C16—H16 | 119.2 | C34—C33—C32 | 112.57 (14) |
O1—C17—C18 | 108.82 (16) | C34—C33—H33A | 109.1 |
O1—C17—H17A | 109.9 | C32—C33—H33A | 109.1 |
C18—C17—H17A | 109.9 | C34—C33—H33B | 109.1 |
O1—C17—H17B | 109.9 | C32—C33—H33B | 109.1 |
C18—C17—H17B | 109.9 | H33A—C33—H33B | 107.8 |
H17A—C17—H17B | 108.3 | C35—C34—C33 | 114.75 (15) |
C17—C18—C19 | 113.11 (16) | C35—C34—H34A | 108.6 |
C17—C18—H18A | 109.0 | C33—C34—H34A | 108.6 |
C19—C18—H18A | 109.0 | C35—C34—H34B | 108.6 |
C17—C18—H18B | 109.0 | C33—C34—H34B | 108.6 |
C19—C18—H18B | 109.0 | H34A—C34—H34B | 107.6 |
H18A—C18—H18B | 107.8 | C34—C35—C36 | 113.00 (17) |
C18—C19—C20 | 113.96 (15) | C34—C35—H35A | 109.0 |
C18—C19—H19A | 108.8 | C36—C35—H35A | 109.0 |
C20—C19—H19A | 108.8 | C34—C35—H35B | 109.0 |
C18—C19—H19B | 108.8 | C36—C35—H35B | 109.0 |
C20—C19—H19B | 108.8 | H35A—C35—H35B | 107.8 |
H19A—C19—H19B | 107.7 | C35—C36—H36A | 109.5 |
C21—C20—C19 | 112.77 (16) | C35—C36—H36B | 109.5 |
C21—C20—H20A | 109.0 | H36A—C36—H36B | 109.5 |
C19—C20—H20A | 109.0 | C35—C36—H36C | 109.5 |
C21—C20—H20B | 109.0 | H36A—C36—H36C | 109.5 |
C19—C20—H20B | 109.0 | H36B—C36—H36C | 109.5 |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.86 (1) | 2.45 (6) | 2.8935 (19) | 113 (5) |
N2—H2A···N1i | 0.86 (1) | 2.35 (2) | 2.928 (2) | 125 (2) |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C72H86N4O4 |
Mr | 1071.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 185 |
a, b, c (Å) | 15.9611 (10), 19.1464 (12), 10.1620 (6) |
β (°) | 91.335 (1) |
V (Å3) | 3104.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.25 × 0.12 × 0.09 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.983, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15401, 5897, 4393 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.123, 1.00 |
No. of reflections | 5897 |
No. of parameters | 370 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.17 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.863 (10) | 2.45 (6) | 2.8935 (19) | 113 (5) |
N2—H2A···N1i | 0.860 (10) | 2.35 (2) | 2.928 (2) | 125 (2) |
Symmetry code: (i) −x+2, −y, −z. |
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Porphyrins and metalloporphyrins have been widely studied in many fields, such as catalysts (Gross & Ini, 1999), dye-sensitized solar cells (Barea et al., 2011) and liquid crystals (Kugimiya & Takemura, 1990). In most cases, the porphyrin macrocycle has been functionalized with carboxyphenyl, hydroxyphenyl or pyridyl groups, and they can be used as molecular scaffolds to construct two- or three-dimensional polymeric materials (Chung et al., 2009) through efficient hydrogen bonds, π–π interactions and metal–ligand interactions.
Owing to the flexibility of long hydrocarbon chains and similar substituents, porphyrin crystals with long flexible chains (such as alkyl and alkoxy) are not easy to obtain (Balaban et al. 2000; Bhyrappa et al., 2008). Recently, we reported the single-crystal structures of metal complexes of meso-tetrakis(4-alkoxyphenyl)porphyrins (Chen et al., 2010; Yang et al., 2011). In order to investigate the structures of porphyrins without the presence of a metal ion, we have now synthesized meso-tetrakis[4-(heptyloxy)phenyl]porphyrin, (I), which is an important intermediate in the synthesis of metalloporphyrins for liquid-crystal materials (Zhao et al., 2000). This type of discotic liquid crystal has been researched in several fields, such as electron-transfer (Jakob et al., 2009) and ferroelectric switching (Heppke et al., 2000).
The 24-membered porphyrin core of (I) (Fig. 1) is planar, with a mean deviation of 0.037 (1) Å; the angle between adjacent pyrrole ring planes (C1–C4/N1 and C6–C9/N2)is 2.20 (9)°, and other bond lengths and angles are close to those found for tetraphenylporphyrin (Silvers & Tulinsky, 1967). This suggests that the long alkoxy chains substituted on the phenyl rings have no significant effect on the geometry of the porphine molecular plane.
The redetermination of the structure of porphine (Chen & Tulinsky, 1972) indicates that there are two structurally different pairs of pyrrole rings. We found that the N-bound H atoms in (I) (Fig. 1) are disordered, which is similar to the situation of tautomerism in free-base porphyrins, such as meso-tetraphenylporphyrin (H2TPP; Limbach et al., 1984) and meso-tetratolylporphyrin (H2TTP; Butcher et al., 1985). The transannular N···N separations [N1···N1i = 4.055 (2) Å and N2···N2i = 4.175 (2) Å; symmetry code: (i) -x + 2, -y, -z] for (I) are comparable with the values found in H2TTP [4.079 (6) and 4.154 (6) Å]. The N···N distances between adjacent N atoms in (I) [2.893 (2) and 2.927 (2) Å] are also similar to those in H2TTP, where the values are 2.894 (4) and 2.940 (4) Å.
In the crystal structure of H2TTP, the H atoms are disordered and it was thought that this disorder could be confirmed unequivocally by indirect means, since several bond angles in the porphyrin skeleton have been shown to be sensitive to imino versus amino N atoms in ordered structures. For example, the C—N—C angles of 107.9 (3) and 107.7 (3)° in H2TTP are midway between the average values for imino and amino N atoms of 105.7 (4) and 109.9 (4)°, respectively (Jameson & Ibers, 1980). However, in (I), the C1—N1—C4 [106.02 (13)°] and C6—N2—C9 [109.58 (13)°] angles are different from those of H2TTP and, in contrast, they are closer to the expected values for distinct imino and amino N atoms. We therefore believe that using the nitrogen angle is not a sufficiently comprehensive and accurate criterion to judge the presence or absence of H-atom disorder in porphyrins.
The planes of the 4-(heptyloxy)phenyl groups in (I) are rotated at angles of 85.92 (5) (C11–C16) and 73.86 (4)° (C24–C29) with respect to the porphyrin mean plane, and these angles are larger than the corresponding dihedral angles in 2,3,12,13-tetrabromo-5,10,15,20-tetrakis(4-butoxyphenyl)porphyrin 1,2-dichloroethane solvate ([Values?]; Bhyrappa et al., 2008). This may be related to steric hindrance, because the heptyloxy group is longer than butoxy. By comparison, the two benzene rings (C11–C16) and (C24–C29) are almost perpendicular to one another, with an interplanar angle of 89.82 (6)°.
The unit-cell packing of (I) along the c axis is shown in Fig. 2. There are no significant π–π interactions between the porphyrins. The benzene groups with long chains around the porphyrin core may hinder interactions between the porphyrins.