organic compounds
5,10,15,20-Tetrakis(4-acetyloxyphenyl)porphyrin including an unknown solvate
aCEMDRX, Physics Department, University of Coimbra, P-3004-516 Coimbra, Portugal, and bChemistry Department, University of Coimbra, P-3004 Coimbra, Portugal
*Correspondence e-mail: manuela@pollux.fis.uc.pt
Molecules of the title compound, C52H38N4O8, are located on an inversion center so that the asymmetric cell contains one half of the molecule. The macrocycle exhibits a ruffled conformation with a maximum deviation of 0.16 Å for the 24 macrocycle atoms: the dihedral angle between adjacent five-membered rings is 5.13 (19)°. The benzene rings are rotated by 70.25 (19)° with respect to their adjacent protonated five-membered rings, and by 65.56 (19)° with respect to the unprotonated rings. The porphyrin conformation is supported by bifurcated N—H⋯(N,N) hydrogen bonds. The structure contained poorly resolved solvent molecules in voids of volume 217 Å3 per The latter were treated using the SQUEEZE routine in PLATON [Spek (2009). Acta Cryst. D65, 148–155]. As the solvent could not be identified exactly, it was not included in the calculation of the overall formula weight, density and absorption coefficient.
Related literature
For general background on porphyrin and porphyrin precursors synthesized in our group, see Paixão, Matos Beja et al. (2002); Paixão, Ramos Silva et al. (2002); Paixão et al. (2003); Ramos Silva et al. (2002a,b); Sobral et al. (2001a,b). For the applications of see: Zhang et al. (2010); Eichhorn (2000).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812047332/hb6985sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047332/hb6985Isup2.hkl
All reagents were used as purchased, except pyrrole that was distillated under reduced pressure. The tetrakys-(pheny-4-acetate)-21H,22H-porphine was synthesized by the method of Rothemund/Adler/Long [1–2]. The aldehyde 4-formylphenyl acetate (1 g, 6.1 mmol) was added to propionic acid (150 ml). The solution was placed to reflux and then pyrrole (0.5 ml, 7.207 mmol) was added drop wise during 10 minutes. The solution was left at 120 C for 4 h. The solvent was then evaporated and the crude, dissolved in dichloromethane, was washed with aqueous NaHCO3 and distilled water and dried with Na2SO4 anhydrous. The final porphyrin tetrakys-(pheny-4-acetate)-21H,22H-porphine was obtained after purification by
in silica/dichloromethane. Recrystallization in dichloromethane/hexane gives the purple crystals of tetrakys-(pheny-4-acetate)-21H,22H-porphine (yield of 5% relatively to pyrrole). HPLC/MS showed a single signal corresponding to the expected molecular ion m/z 847.H atoms bound to C atoms were placed at calculated positions and were treated as riding on the parent atoms with C—H = 0.93 Å (aromatic) and with Uiso(H) = 1.2 Ueq(C). In a final difference Fourier map highly disordered electron density occupying one cavity of ca 215 Å3 each was observed. This residual electron density was difficult to model and therefore, the SQUEEZE routine in PLATON (Spek, 2009) was used to eliminate this contribution of the electron density in the solvent region from the intensity data. The solvent-free model was employed for the final
One of the methylcarbonyloxy terminal groups shows signs of disorder, possibly occupying two or more sites but such disorder could not be resolved in the present experiment. The solvent molecules were not included in the calculation of the overall formula weight, density and absorption coefficient.Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound. Displacement ellipsoids are drawn at the 50% level. | |
Fig. 2. Packing of the molecules in the unit cell showing the H-bonds as dashed lines. |
C52H38N4O8 | Z = 1 |
Mr = 846.86 | F(000) = 442 |
Triclinic, P1 | Dx = 1.174 Mg m−3 |
a = 6.6203 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.1043 (3) Å | Cell parameters from 4592 reflections |
c = 14.4936 (3) Å | θ = 2.9–21.4° |
α = 113.862 (1)° | µ = 0.08 mm−1 |
β = 97.771 (2)° | T = 293 K |
γ = 98.060 (2)° | Plate, violet |
V = 1197.58 (5) Å3 | 0.30 × 0.12 × 0.04 mm |
Bruker APEX CCD area-detector diffractometer | 4566 independent reflections |
Radiation source: fine-focus sealed tube | 2956 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 25.8°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −8→8 |
Tmin = 0.790, Tmax = 0.999 | k = −17→17 |
24062 measured reflections | l = −17→17 |
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)] = 0.080 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.248 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.1221P)2 + 0.5589P] where P = (Fo2 + 2Fc2)/3 |
4566 reflections | (Δ/σ)max = 0.040 |
291 parameters | Δρmax = 0.98 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C52H38N4O8 | γ = 98.060 (2)° |
Mr = 846.86 | V = 1197.58 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.6203 (2) Å | Mo Kα radiation |
b = 14.1043 (3) Å | µ = 0.08 mm−1 |
c = 14.4936 (3) Å | T = 293 K |
α = 113.862 (1)° | 0.30 × 0.12 × 0.04 mm |
β = 97.771 (2)° |
Bruker APEX CCD area-detector diffractometer | 4566 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2956 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.999 | Rint = 0.031 |
24062 measured reflections |
R[F2 > 2σ(F2)] = 0.080 | 0 restraints |
wR(F2) = 0.248 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.98 e Å−3 |
4566 reflections | Δρmin = −0.51 e Å−3 |
291 parameters |
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 | ||
N1 | 0.7700 (3) | 0.90482 (18) | 0.36681 (17) | 0.0397 (6) | |
H1 | 0.8553 | 0.9529 | 0.4212 | 0.048* | |
N2 | 1.1829 (3) | 1.03171 (17) | 0.41002 (17) | 0.0400 (6) | |
O1 | 0.8965 (4) | 0.7835 (2) | −0.19208 (16) | 0.0709 (7) | |
O2 | 1.2299 (4) | 0.8442 (2) | −0.1891 (2) | 0.0810 (8) | |
O3 | −0.1992 (4) | 0.5305 (2) | 0.3829 (3) | 0.0907 (9) | |
O4 | −0.1461 (12) | 0.4164 (5) | 0.2427 (5) | 0.270 (4) | |
C1 | 0.5249 (4) | 0.8381 (2) | 0.4526 (2) | 0.0404 (7) | |
C2 | 0.5916 (4) | 0.8419 (2) | 0.3666 (2) | 0.0399 (7) | |
C3 | 0.4952 (4) | 0.7749 (2) | 0.2613 (2) | 0.0477 (8) | |
H3 | 0.3713 | 0.7240 | 0.2377 | 0.057* | |
C4 | 0.6157 (5) | 0.7981 (3) | 0.2015 (2) | 0.0511 (8) | |
H4 | 0.5881 | 0.7664 | 0.1297 | 0.061* | |
C5 | 0.7918 (4) | 0.8795 (2) | 0.2676 (2) | 0.0418 (7) | |
C6 | 0.9617 (4) | 0.9196 (2) | 0.2367 (2) | 0.0414 (7) | |
C7 | 1.1447 (4) | 0.9906 (2) | 0.3043 (2) | 0.0419 (7) | |
C8 | 1.3182 (5) | 1.0335 (2) | 0.2720 (2) | 0.0513 (8) | |
H8 | 1.3306 | 1.0176 | 0.2044 | 0.062* | |
C9 | 1.4573 (5) | 1.1004 (3) | 0.3576 (2) | 0.0511 (8) | |
H9 | 1.5846 | 1.1402 | 0.3606 | 0.061* | |
C10 | 1.3752 (4) | 1.1001 (2) | 0.4445 (2) | 0.0410 (7) | |
C11 | 0.9478 (5) | 0.8834 (2) | 0.1239 (2) | 0.0453 (7) | |
C12 | 1.0830 (5) | 0.8245 (3) | 0.0745 (2) | 0.0601 (9) | |
H12 | 1.1829 | 0.8067 | 0.1125 | 0.072* | |
C13 | 1.0738 (6) | 0.7915 (3) | −0.0297 (3) | 0.0672 (10) | |
H13 | 1.1658 | 0.7517 | −0.0620 | 0.081* | |
C14 | 0.9254 (5) | 0.8187 (3) | −0.0849 (2) | 0.0558 (9) | |
C15 | 0.7864 (5) | 0.8749 (3) | −0.0391 (2) | 0.0579 (9) | |
H15 | 0.6848 | 0.8913 | −0.0777 | 0.070* | |
C16 | 0.7987 (5) | 0.9072 (3) | 0.0653 (2) | 0.0529 (8) | |
H16 | 0.7046 | 0.9458 | 0.0969 | 0.063* | |
C17 | 1.0572 (6) | 0.7993 (3) | −0.2359 (3) | 0.0599 (9) | |
C18 | 0.9824 (6) | 0.7539 (3) | −0.3500 (3) | 0.0720 (11) | |
H18A | 0.9996 | 0.8098 | −0.3718 | 0.108* | |
H18B | 0.8375 | 0.7197 | −0.3682 | 0.108* | |
H18C | 1.0620 | 0.7030 | −0.3834 | 0.108* | |
C19 | 0.3332 (4) | 0.7556 (2) | 0.4305 (2) | 0.0411 (7) | |
C20 | 0.1366 (5) | 0.7666 (3) | 0.3969 (3) | 0.0550 (8) | |
H20 | 0.1215 | 0.8276 | 0.3888 | 0.066* | |
C21 | −0.0373 (5) | 0.6893 (3) | 0.3751 (3) | 0.0620 (9) | |
H21 | −0.1685 | 0.6967 | 0.3505 | 0.074* | |
C22 | −0.0155 (5) | 0.6014 (3) | 0.3900 (3) | 0.0575 (9) | |
C23 | 0.1759 (5) | 0.5883 (3) | 0.4238 (3) | 0.0658 (10) | |
H23 | 0.1896 | 0.5280 | 0.4334 | 0.079* | |
C24 | 0.3492 (5) | 0.6658 (3) | 0.4436 (3) | 0.0575 (9) | |
H24 | 0.4804 | 0.6570 | 0.4664 | 0.069* | |
C25 | −0.2590 (11) | 0.4459 (5) | 0.3054 (5) | 0.119 (2) | |
C26 | −0.4600 (7) | 0.3784 (4) | 0.2982 (4) | 0.1021 (16) | |
H26A | −0.4679 | 0.3064 | 0.2502 | 0.153* | |
H26B | −0.5742 | 0.4039 | 0.2748 | 0.153* | |
H26C | −0.4677 | 0.3812 | 0.3649 | 0.153* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0341 (12) | 0.0479 (12) | 0.0322 (12) | −0.0020 (10) | 0.0051 (9) | 0.0165 (10) |
N2 | 0.0370 (13) | 0.0456 (12) | 0.0342 (12) | −0.0015 (10) | 0.0070 (10) | 0.0176 (10) |
O1 | 0.0544 (14) | 0.1086 (19) | 0.0343 (11) | −0.0056 (13) | 0.0089 (10) | 0.0232 (12) |
O2 | 0.0619 (16) | 0.0996 (19) | 0.0612 (15) | −0.0139 (15) | 0.0127 (13) | 0.0248 (14) |
O3 | 0.0685 (18) | 0.0697 (16) | 0.109 (2) | −0.0121 (14) | 0.0007 (16) | 0.0276 (16) |
O4 | 0.299 (7) | 0.196 (5) | 0.175 (5) | −0.122 (5) | 0.121 (5) | −0.023 (4) |
C1 | 0.0297 (14) | 0.0450 (14) | 0.0472 (16) | 0.0001 (12) | 0.0055 (12) | 0.0239 (12) |
C2 | 0.0334 (14) | 0.0447 (14) | 0.0406 (15) | 0.0011 (12) | 0.0046 (11) | 0.0207 (12) |
C3 | 0.0365 (15) | 0.0565 (17) | 0.0412 (16) | −0.0064 (13) | 0.0007 (12) | 0.0199 (14) |
C4 | 0.0438 (17) | 0.0618 (18) | 0.0358 (15) | −0.0013 (14) | −0.0014 (13) | 0.0166 (14) |
C5 | 0.0394 (15) | 0.0483 (15) | 0.0353 (14) | 0.0039 (13) | 0.0025 (12) | 0.0191 (12) |
C6 | 0.0424 (15) | 0.0488 (15) | 0.0327 (14) | 0.0037 (13) | 0.0065 (12) | 0.0196 (12) |
C7 | 0.0421 (16) | 0.0486 (15) | 0.0362 (14) | 0.0010 (13) | 0.0090 (12) | 0.0221 (12) |
C8 | 0.0513 (18) | 0.0622 (18) | 0.0382 (15) | −0.0011 (15) | 0.0123 (13) | 0.0229 (14) |
C9 | 0.0425 (16) | 0.0617 (18) | 0.0452 (16) | −0.0079 (14) | 0.0144 (13) | 0.0236 (14) |
C10 | 0.0362 (15) | 0.0457 (14) | 0.0408 (15) | 0.0016 (12) | 0.0069 (12) | 0.0210 (12) |
C11 | 0.0430 (16) | 0.0534 (16) | 0.0367 (15) | 0.0012 (13) | 0.0084 (12) | 0.0198 (13) |
C12 | 0.0515 (19) | 0.085 (2) | 0.0425 (17) | 0.0186 (17) | 0.0065 (14) | 0.0258 (16) |
C13 | 0.060 (2) | 0.089 (3) | 0.0459 (19) | 0.0179 (19) | 0.0127 (16) | 0.0211 (18) |
C14 | 0.0491 (18) | 0.075 (2) | 0.0317 (15) | −0.0069 (16) | 0.0033 (13) | 0.0195 (15) |
C15 | 0.0530 (19) | 0.079 (2) | 0.0444 (17) | 0.0081 (17) | 0.0056 (14) | 0.0324 (16) |
C16 | 0.0493 (18) | 0.0665 (19) | 0.0443 (17) | 0.0124 (15) | 0.0132 (14) | 0.0243 (15) |
C17 | 0.060 (2) | 0.067 (2) | 0.0448 (18) | 0.0034 (17) | 0.0142 (16) | 0.0192 (16) |
C18 | 0.079 (3) | 0.086 (3) | 0.0442 (19) | 0.010 (2) | 0.0208 (18) | 0.0222 (18) |
C19 | 0.0344 (15) | 0.0481 (15) | 0.0400 (15) | −0.0001 (12) | 0.0073 (11) | 0.0214 (12) |
C20 | 0.0360 (16) | 0.0550 (17) | 0.078 (2) | 0.0039 (14) | 0.0074 (15) | 0.0366 (16) |
C21 | 0.0350 (17) | 0.067 (2) | 0.085 (2) | 0.0023 (15) | 0.0050 (16) | 0.0390 (18) |
C22 | 0.0392 (17) | 0.0559 (18) | 0.068 (2) | −0.0092 (15) | 0.0073 (15) | 0.0252 (16) |
C23 | 0.053 (2) | 0.0539 (18) | 0.092 (3) | −0.0018 (16) | 0.0063 (18) | 0.0406 (18) |
C24 | 0.0377 (17) | 0.0606 (19) | 0.078 (2) | 0.0025 (14) | 0.0046 (15) | 0.0387 (17) |
C25 | 0.136 (5) | 0.106 (4) | 0.081 (3) | −0.023 (4) | 0.005 (3) | 0.027 (3) |
C26 | 0.071 (3) | 0.084 (3) | 0.126 (4) | −0.032 (2) | 0.001 (3) | 0.042 (3) |
N1—C5 | 1.368 (4) | C11—C16 | 1.380 (4) |
N1—C2 | 1.374 (3) | C11—C12 | 1.380 (5) |
N1—H1 | 0.8600 | C12—C13 | 1.378 (5) |
N2—C7 | 1.372 (3) | C12—H12 | 0.9300 |
N2—C10 | 1.376 (3) | C13—C14 | 1.376 (5) |
O1—C17 | 1.348 (4) | C13—H13 | 0.9300 |
O1—C14 | 1.402 (4) | C14—C15 | 1.364 (5) |
O2—C17 | 1.187 (4) | C15—C16 | 1.379 (4) |
O3—C25 | 1.226 (6) | C15—H15 | 0.9300 |
O3—C22 | 1.425 (4) | C16—H16 | 0.9300 |
O4—C25 | 1.235 (8) | C17—C18 | 1.490 (5) |
C1—C2 | 1.395 (4) | C18—H18A | 0.9600 |
C1—C10i | 1.394 (4) | C18—H18B | 0.9600 |
C1—C19 | 1.497 (4) | C18—H18C | 0.9600 |
C2—C3 | 1.425 (4) | C19—C24 | 1.370 (4) |
C3—C4 | 1.356 (4) | C19—C20 | 1.379 (4) |
C3—H3 | 0.9300 | C20—C21 | 1.373 (4) |
C4—C5 | 1.424 (4) | C20—H20 | 0.9300 |
C4—H4 | 0.9300 | C21—C22 | 1.365 (5) |
C5—C6 | 1.396 (4) | C21—H21 | 0.9300 |
C6—C7 | 1.406 (4) | C22—C23 | 1.360 (5) |
C6—C11 | 1.488 (4) | C23—C24 | 1.378 (4) |
C7—C8 | 1.445 (4) | C23—H23 | 0.9300 |
C8—C9 | 1.333 (4) | C24—H24 | 0.9300 |
C8—H8 | 0.9300 | C25—C26 | 1.489 (7) |
C9—C10 | 1.439 (4) | C26—H26A | 0.9600 |
C9—H9 | 0.9300 | C26—H26B | 0.9600 |
C10—C1i | 1.394 (4) | C26—H26C | 0.9600 |
C5—N1—C2 | 109.8 (2) | C15—C14—C13 | 121.4 (3) |
C5—N1—H1 | 125.1 | C15—C14—O1 | 115.9 (3) |
C2—N1—H1 | 125.1 | C13—C14—O1 | 122.5 (3) |
C7—N2—C10 | 105.8 (2) | C14—C15—C16 | 119.0 (3) |
C17—O1—C14 | 121.0 (3) | C14—C15—H15 | 120.5 |
C25—O3—C22 | 118.6 (5) | C16—C15—H15 | 120.5 |
C2—C1—C10i | 126.2 (3) | C11—C16—C15 | 121.4 (3) |
C2—C1—C19 | 116.0 (2) | C11—C16—H16 | 119.3 |
C10i—C1—C19 | 117.6 (3) | C15—C16—H16 | 119.3 |
N1—C2—C1 | 126.8 (2) | O2—C17—O1 | 124.2 (3) |
N1—C2—C3 | 106.9 (2) | O2—C17—C18 | 126.3 (3) |
C1—C2—C3 | 126.2 (3) | O1—C17—C18 | 109.5 (3) |
C4—C3—C2 | 108.1 (2) | C17—C18—H18A | 109.5 |
C4—C3—H3 | 126.0 | C17—C18—H18B | 109.5 |
C2—C3—H3 | 126.0 | H18A—C18—H18B | 109.5 |
C3—C4—C5 | 108.2 (3) | C17—C18—H18C | 109.5 |
C3—C4—H4 | 125.9 | H18A—C18—H18C | 109.5 |
C5—C4—H4 | 125.9 | H18B—C18—H18C | 109.5 |
N1—C5—C6 | 126.7 (2) | C24—C19—C20 | 117.8 (3) |
N1—C5—C4 | 107.0 (3) | C24—C19—C1 | 120.2 (3) |
C6—C5—C4 | 126.2 (3) | C20—C19—C1 | 121.9 (3) |
C5—C6—C7 | 124.7 (3) | C21—C20—C19 | 121.2 (3) |
C5—C6—C11 | 117.3 (2) | C21—C20—H20 | 119.4 |
C7—C6—C11 | 118.0 (3) | C19—C20—H20 | 119.4 |
N2—C7—C6 | 125.5 (3) | C22—C21—C20 | 119.3 (3) |
N2—C7—C8 | 110.0 (2) | C22—C21—H21 | 120.4 |
C6—C7—C8 | 124.5 (3) | C20—C21—H21 | 120.4 |
C9—C8—C7 | 106.8 (3) | C21—C22—C23 | 121.0 (3) |
C9—C8—H8 | 126.6 | C21—C22—O3 | 118.3 (3) |
C7—C8—H8 | 126.6 | C23—C22—O3 | 120.1 (3) |
C8—C9—C10 | 107.8 (3) | C22—C23—C24 | 119.0 (3) |
C8—C9—H9 | 126.1 | C22—C23—H23 | 120.5 |
C10—C9—H9 | 126.1 | C24—C23—H23 | 120.5 |
N2—C10—C1i | 125.9 (3) | C23—C24—C19 | 121.6 (3) |
N2—C10—C9 | 109.6 (2) | C23—C24—H24 | 119.2 |
C1i—C10—C9 | 124.6 (3) | C19—C24—H24 | 119.2 |
C16—C11—C12 | 117.9 (3) | O3—C25—O4 | 120.1 (6) |
C16—C11—C6 | 121.1 (3) | O3—C25—C26 | 116.5 (6) |
C12—C11—C6 | 121.0 (3) | O4—C25—C26 | 123.1 (5) |
C13—C12—C11 | 121.7 (3) | C25—C26—H26A | 109.5 |
C13—C12—H12 | 119.1 | C25—C26—H26B | 109.5 |
C11—C12—H12 | 119.1 | H26A—C26—H26B | 109.5 |
C14—C13—C12 | 118.5 (3) | C25—C26—H26C | 109.5 |
C14—C13—H13 | 120.7 | H26A—C26—H26C | 109.5 |
C12—C13—H13 | 120.7 | H26B—C26—H26C | 109.5 |
C5—N1—C2—C1 | 174.5 (3) | C7—C6—C11—C12 | 63.6 (4) |
C5—N1—C2—C3 | −1.0 (3) | C16—C11—C12—C13 | 1.1 (5) |
C10i—C1—C2—N1 | 1.9 (5) | C6—C11—C12—C13 | −179.2 (3) |
C19—C1—C2—N1 | −175.0 (3) | C11—C12—C13—C14 | 0.1 (6) |
C10i—C1—C2—C3 | 176.6 (3) | C12—C13—C14—C15 | −1.5 (5) |
C19—C1—C2—C3 | −0.3 (4) | C12—C13—C14—O1 | −176.2 (3) |
N1—C2—C3—C4 | 0.2 (3) | C17—O1—C14—C15 | 131.0 (4) |
C1—C2—C3—C4 | −175.3 (3) | C17—O1—C14—C13 | −54.0 (5) |
C2—C3—C4—C5 | 0.6 (4) | C13—C14—C15—C16 | 1.5 (5) |
C2—N1—C5—C6 | −174.2 (3) | O1—C14—C15—C16 | 176.6 (3) |
C2—N1—C5—C4 | 1.4 (3) | C12—C11—C16—C15 | −1.1 (5) |
C3—C4—C5—N1 | −1.2 (4) | C6—C11—C16—C15 | 179.3 (3) |
C3—C4—C5—C6 | 174.4 (3) | C14—C15—C16—C11 | −0.2 (5) |
N1—C5—C6—C7 | 2.8 (5) | C14—O1—C17—O2 | −1.2 (6) |
C4—C5—C6—C7 | −171.9 (3) | C14—O1—C17—C18 | 179.9 (3) |
N1—C5—C6—C11 | −177.8 (3) | C2—C1—C19—C24 | 105.4 (3) |
C4—C5—C6—C11 | 7.5 (5) | C10i—C1—C19—C24 | −71.8 (4) |
C10—N2—C7—C6 | −177.7 (3) | C2—C1—C19—C20 | −74.7 (4) |
C10—N2—C7—C8 | 0.6 (3) | C10i—C1—C19—C20 | 108.2 (3) |
C5—C6—C7—N2 | −0.6 (5) | C24—C19—C20—C21 | −1.3 (5) |
C11—C6—C7—N2 | 179.9 (3) | C1—C19—C20—C21 | 178.7 (3) |
C5—C6—C7—C8 | −178.7 (3) | C19—C20—C21—C22 | 1.9 (6) |
C11—C6—C7—C8 | 1.9 (5) | C20—C21—C22—C23 | −1.4 (6) |
N2—C7—C8—C9 | −0.7 (4) | C20—C21—C22—O3 | 170.2 (3) |
C6—C7—C8—C9 | 177.6 (3) | C25—O3—C22—C21 | 104.7 (5) |
C7—C8—C9—C10 | 0.5 (4) | C25—O3—C22—C23 | −83.6 (6) |
C7—N2—C10—C1i | 178.3 (3) | C21—C22—C23—C24 | 0.3 (6) |
C7—N2—C10—C9 | −0.3 (3) | O3—C22—C23—C24 | −171.1 (3) |
C8—C9—C10—N2 | −0.1 (4) | C22—C23—C24—C19 | 0.3 (6) |
C8—C9—C10—C1i | −178.7 (3) | C20—C19—C24—C23 | 0.2 (5) |
C5—C6—C11—C16 | 63.8 (4) | C1—C19—C24—C23 | −179.9 (3) |
C7—C6—C11—C16 | −116.7 (3) | C22—O3—C25—O4 | 10.6 (10) |
C5—C6—C11—C12 | −115.8 (3) | C22—O3—C25—C26 | −175.6 (4) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2 | 0.86 | 2.35 | 2.885 (3) | 121 |
N1—H1···N2i | 0.86 | 2.42 | 2.944 (3) | 120 |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C52H38N4O8 |
Mr | 846.86 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6203 (2), 14.1043 (3), 14.4936 (3) |
α, β, γ (°) | 113.862 (1), 97.771 (2), 98.060 (2) |
V (Å3) | 1197.58 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.12 × 0.04 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.790, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24062, 4566, 2956 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.080, 0.248, 1.14 |
No. of reflections | 4566 |
No. of parameters | 291 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.98, −0.51 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2 | 0.8600 | 2.3500 | 2.885 (3) | 121.00 |
N1—H1···N2i | 0.8600 | 2.4200 | 2.944 (3) | 120.00 |
Symmetry code: (i) −x+2, −y+2, −z+1. |
Footnotes
‡Additional correspondence author.
Acknowledgements
This work was supported by Fundo Europeu de Desenvolvimento Regional-QREN-COMPETE through project PEst-C/FIS/UI0036/2011, PTDC/AAC-CLI/098308/2008 and PTDC/AAC-CLI/118092/2010 – Fundação para a Ciência e a Tecnologia (FCT).
References
Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Eichhorn, H. (2000). J. Porphyrins Phthalocyanines, 4, 88–102. Web of Science CrossRef CAS Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Paixão, J. A., Matos Beja, A., Ramos Silva, M., Alte da Veiga, L., Sobral, A. J. F. N., Lopes, S. H. & Rocha Gonsalves, A. M. (2002). Z. Kristallogr. New Cryst. Struct. 217, 430–432. Google Scholar
Paixão, J. A., Ramos Silva, M., Matos Beja, A., Sobral, A. J. F. N., Lopes, S. H. & Rocha Gonsalves, A. M. d'A. (2002). Acta Cryst. C58, o721–o723. Web of Science CSD CrossRef IUCr Journals Google Scholar
Paixão, J. A., Ramos Silva, M., Matos Beja, A., Sobral, A. J. F. N., Lopes, S. H. & Rocha Gonsalves, A. M. d'A. (2003). Acta Cryst. E59, o94–o96. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ramos Silva, M., Matos Beja, A., Paixão, J. A., Sobral, A. J. F. N., Lopes, S. H. & Rocha Gonsalves, A. M. d'A. (2002a). Acta Cryst. C58, o572–o574. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ramos Silva, M., Matos Beja, A., Paixão, J. A., Sobral, A. J. F. N., Lopes, S. H. & Rocha Gonsalves, A. M. d'A. (2002b). Acta Cryst. C58, o685–o687. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sobral, A. J. F. N., Gonsalves, A. M. & dA, R. (2001a). J. Porphyrins Phthalocyanines, 5, 428–430. Web of Science CrossRef CAS Google Scholar
Sobral, A. J. F. N., Gonsalves, A. M. & dA, R. (2001b). J. Porphyrins Phthalocyanines, 5, 861–866. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, D., Zhang, L. F., Chen, Y., Wang, H., Ni, Z. H., Wernsdorfer, W. & Jiang, J. (2010). Chem. Commun. 46, 3550–3552. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
This work is part of a project of synthesizing porphyrins and porphyrin percursors (Paixão, Matos Beja et al., 2002; Paixão, Ramos Silva et al., 2002; Paixão et al., 2003; Ramos Silva et al., 2002a,b; Sobral et al., 2001a,b). Our aim is to use the tremendous potential for the manifold applications of porphyrins and obtain molecular magnets (Zhang et al., 2010), liquid crystals (Eichhorn, 2000), multi-porous materials for CO2 sequestering and possibly some properties combined. In the title compound, Fig. 1, 5,10,15,20-Tetrakis[(4-methylcarbonyl)oxy]-phenylporphyrin, the porphyrin moiety shows a non planar ruffled conformation. The phenyl rings are rotated with respect to the porphyrin ring. The angle between the least-squares plane containing the porphyrin core and the least-squares plane of the phenyl ring C11—C16 is 65.29 (14)° [74.18 (13)° for C19—C24]. Intramolecular N—H···N hydrogen bonds are present. The molecules pile in columns along the a axis. There are solvent acessible voids in the crystal structure that accomodate solvent molecules in a very disordered way; these solvent molecules were not included in the calculation of the overall formula weight, density and absorption coefficient.