The free-base porphyrin species was synthesized by a two-step procedure. The
first step is the synthesis of
5-(4-pyridyl)-10,15,20-tris(4-carbomethoxyphenyl)porphyrin by Adler's method
(Adler et al., 1970). This involves the condensation of a 3:1 mixture
of 4-pyridinecarboxaldehyde and 4-carbomethoxybenzaldehyde with distilled
pyrrole in hot propionic acid, and separation of the product on a silica-gel
column using chloroform as solvent and acetone–chloroform mixtures of
gradually varying composition as eluants. Thus isolated
5-(4-pyridyl)-10,15,20-tris(4-carbomethoxyphenyl)porphyrin was then converted
to the corresponding carboxylic acid derivative
5-(4-pyridyl)-10,15,20-tris(4-carboxyphenyl)porphyrin by alkaline hydrolysis
with an aqueous solution of KOH.
5-(4-Pyridyl)-10,15,20-tris(4-carbomethoxyphenyl)porphyrin: 1H NMR
(CDCl3): δ 9.00 (d, J = 5.9 Hz, 2H), 8.79 (m, 8H),
8.43 (d, J = 8 Hz, 6H), 8.25 (d, J = 8.2 Hz, 6H),
8.12 (d, J = 5.9 Hz, 2H), 4.08 (s, 12H), -2.89 (s,
2H). UV–vis (in THF, nm): λmax (logε) 417 (5.71), 513 (4.41), 547 (4.03),
590 (3.92), 649 (3.73). FAB–MS (m/z) for C49H35N5O6:
found 790, calculated 789.85.
5-(4-Pyridyl)-10,15,20-tris(4-carboxyphenyl)porphyrin: 1H NMR
(DMSO-d): δ 13.30 (s, 3H), 9.07 (d, J = 4.8 Hz,
2H), 8.87 (d, J = 2 Hz, 6H), 8.47–8.25 (m, 16H), -2.97
(s, 2H). UV–vis (in THF, nm): λmax (logε) 417 (5.65), 513 (4.30),
546 (3.84), 589 (3.60), 646 (3.14). FAB–MS (m/z) for
C46H29N5O6: found 748, calcualted 747.77. The carboxyphenylporphyrin
was crystallized from a solution in dimethyl sulfoxide (by the solvothermal
technique) as well as from a 4:1 mixture of THF and 4-acetylpyridine (by slow
evaporation). The overall yield in both cases was within 5–10%. The content
of the uncoordinated solvent in the two structure could not be reliably
determined. Most recently, the synthesis and isolation of a series of
meso-(4'-pyridyl)/(4'-carboxyphenyl) porphyrins has been reported
(Gianferrara et al., 2007).
Both crystals diffracted poorly, with a relatively low (<50%) percentage of
observed intensities above the threshold of 2σ(I) within the 0–27.5°
θ range. The crystal packing of the DMSO–porphyrin and
acetylpyridine–porphyrin supramolecular arrays is associated in both cases by
the formation of interporphyrin voids accessible to noncoordinated solvent
molecules, which were found to be severely disordered in these voids. The
noncoordinated solvent molecules could not be modeled by discrete atoms in
either compound. Correspondingly, the contribution of the solvent to the
diffraction pattern was subtracted by the SQUEEZE procedure of PLATON
(Spek, 2003). In (I), these voids consist of about 27% percent of the crystal
volume (1480 Å3 per unit cell, equally distributed across four cavities).
The residual electron density count amounted to 68 e per unit cell,
corresponding to nearly two molecules of DMSO (the content of each of the four
cavities per unit cell being equivalent to one-half of a molecule of DMSO).
Conventional least-squares refinement of the same solvent-excluded structural
model against the original data set converged only at R1 = 0.15.
Refinement calculations with the modified data converged at R1 = 0.070
for 5171 reflections with intensities above 3σ(I) and R1 =
0.085 for 6211 reflections with intensities above the threshold of
2σ(I). The crystal structure of (I) represents a racemic twin in space
group Cc. The choice of the noncentrosymmetric space group was based on
better intensity-statistics indicators, as well as on our inability to obtain
and refine an alternative structure model in space group C2/c.
In (II), about 50% of the crystal volume comprises the solvent-accessible
voids. The interporphyrin channels propagate parallel to the a axis of
the crystal, and appear to accommodate severely diffused molecules of the THF
solvent. Conventional refinement of the ordered supramolecular fragments of
the structure converged only at R1 = 0.20. The SQUEEZE procedure
indicated that the single solvent accessible void in the unit cell has a
volume of 1051 Å3, and that the residual electron density count is 82 e
per unit-cell (which corresponds as a lower limit to at least two molecules of
THF). This assessment seems to be very inaccurate, as independent
thermogravimetric analysis indicated that on heating of this material about
42% weight loss occurs around 387 K, representing a markedly higher amount of
the volatile THF solvent (about ten molecules per unit cell). As the crystals
were out of the solvent for about the same time prior to the diffraction and
thermogravimetric analysis experiments, the latter provided a better estimate
of the actual solvent content. An additional 16% weight loss occurs around 422 K, which corresponds to the evaporation of the two molecules of the
acetylpyridine component. Refinement calculations with the modified data
converged smoothly at R1 = 0.052. Some orientational disorder of the
aromatic substituents (that could not be reliably resolved) is also evident
from the elongated atomic displacement parameters of the corresponding atoms.
Assignment of the correct space group for this structure posed an additional
problem. The distribution of the diffracted intensities suggested that the
structure is centrosymmetric (space group P1 with Z = 1),
which would necessitate a twofold disorder of the porphyrin species associated
with alternating orientations of the inter-porphyrin COOH···N hydrogen bond
along the polymeric chain. Crystallographic refinement of the structural model
in space group P1 was characterized, however, by better convergence and
a more coherent description of the hydrogen-bonding scheme, although the
overall structure remains pseudo-centrosymmetric. In the P1 model, the
observed COOH(porphyrin)···N(porphyrin) hydrogen bond was found ordered and
well defined, suggesting that the space group P1 represents the
preferred choice for describing the supramolecular self-assembly in this
structure.
All of the H atoms were placed in calculated positions and were constrained to
ride on their parent atoms. For H atoms bound to C, the C—H distances are in
the range of 0.95–0.98 Å, with Uiso(H) set at 1.5Ueq(C)
for the methyl groups and 1.2Ueq(C) for other C-bound H atoms. For H
atoms bound to O, the O—H distances were set at 0.84 Å, with
Uiso(H) values of 1.5Ueq(O), and the positions of the H
atoms were based on forming the `best' hydrogen bond to a neighboring
hydrogen-bond acceptor, viz. the O═S [in (I)] or pyridyl [in (II)]
groups (Sheldrick, 1997). The two inner pyrrole H atoms bound to N could not
be located in difference Fourier maps and were assumed to be disordered
between the four N atom sites in the two structures [N—H = 0.88 Å and
Uiso(H) = 1.2Ueq(N)]. In the refinement of (II), five
bond-length restraints were applied to bonds C25—C30, C27—N28, C46—O48,
C58—C63 and N69—C70.
For both compounds, data collection: Collect (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
(I) 20-(4-pyridyl)porphyrin-5
4,10
4,15
4-tribenzoic acid–dimethyl sulfoxide
(2/5)
top
Crystal data top
C46H29N5O6·2.5C2H6SO | F(000) = 1972 |
Mr = 943.06 | Dx = 1.133 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5978 (3) Å | Cell parameters from 5425 reflections |
b = 29.2458 (15) Å | θ = 1.4–27.9° |
c = 28.6630 (13) Å | µ = 0.17 mm−1 |
β = 90.521 (2)° | T = 110 K |
V = 5530.5 (5) Å3 | Plates, red |
Z = 4 | 0.40 × 0.20 × 0.03 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6211 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.071 |
Graphite monochromator | θmax = 27.9°, θmin = 2.6° |
Detector resolution: 12.8 pixels mm-1 | h = −8→8 |
0.3 deg. ω scans | k = −38→37 |
18496 measured reflections | l = −37→37 |
11808 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.085 | H-atom parameters constrained |
wR(F2) = 0.211 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.005 |
11808 reflections | Δρmax = 0.83 e Å−3 |
594 parameters | Δρmin = −0.31 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 5242 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.42 (12) |
Crystal data top
C46H29N5O6·2.5C2H6SO | V = 5530.5 (5) Å3 |
Mr = 943.06 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 6.5978 (3) Å | µ = 0.17 mm−1 |
b = 29.2458 (15) Å | T = 110 K |
c = 28.6630 (13) Å | 0.40 × 0.20 × 0.03 mm |
β = 90.521 (2)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6211 reflections with I > 2σ(I) |
18496 measured reflections | Rint = 0.071 |
11808 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.085 | H-atom parameters constrained |
wR(F2) = 0.211 | Δρmax = 0.83 e Å−3 |
S = 1.06 | Δρmin = −0.31 e Å−3 |
11808 reflections | Absolute structure: Flack (1983), 5242 Friedel pairs |
594 parameters | Absolute structure parameter: 0.42 (12) |
2 restraints | |
Special details top
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. The crystals were characterized by relatively large mosaic spread. The
structure was found to contain additional non-coordinated solvent (DMSO)
within the intra-lattice voids, which exhibited significant disorder and could
not be modeled by discrete atoms. Correspondingly, the contribution of the
disordered solvent was subtracted from the diffraction pattern by the SQUEEZE
procedure with the aid of the PLATON software. (Spek, 2003).
Conventional refinement of the same solvent-excluded structural model against
the original data set converged only at R1=0.15. The solvent accessible voids
amount to 1480 Å3, about 27% of the crystal volume, with a residual
electron-density count of 68 e/Å3 per unit-cell (corresponding to nearly
two molecules of DMSO). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.9735 (8) | 0.75532 (18) | 0.53134 (18) | 0.0333 (13) | |
C2 | 1.0592 (8) | 0.77624 (18) | 0.49060 (17) | 0.0342 (12) | |
H2 | 1.1778 | 0.7946 | 0.4895 | 0.041* | |
C3 | 0.9370 (8) | 0.76457 (18) | 0.45372 (19) | 0.0377 (13) | |
H3 | 0.9548 | 0.7734 | 0.4221 | 0.045* | |
C4 | 0.7784 (7) | 0.73678 (16) | 0.47146 (17) | 0.0297 (12) | |
C5 | 0.6218 (7) | 0.71900 (16) | 0.44393 (16) | 0.0284 (11) | |
C6 | 0.4575 (8) | 0.69214 (18) | 0.46062 (18) | 0.0355 (12) | |
C7 | 0.3114 (8) | 0.6688 (2) | 0.43233 (19) | 0.0423 (14) | |
H7 | 0.2982 | 0.6709 | 0.3994 | 0.051* | |
C8 | 0.1979 (9) | 0.6437 (2) | 0.46015 (19) | 0.0436 (14) | |
H8 | 0.0914 | 0.6240 | 0.4503 | 0.052* | |
C9 | 0.2613 (7) | 0.65105 (17) | 0.50791 (18) | 0.0337 (13) | |
C10 | 0.1910 (7) | 0.62917 (18) | 0.54724 (18) | 0.0332 (12) | |
C11 | 0.2715 (7) | 0.63460 (17) | 0.59217 (17) | 0.0301 (12) | |
C12 | 0.1785 (8) | 0.61323 (18) | 0.63464 (18) | 0.0346 (13) | |
H12 | 0.0585 | 0.5953 | 0.6359 | 0.042* | |
C13 | 0.3009 (8) | 0.62484 (19) | 0.67034 (18) | 0.0367 (13) | |
H13 | 0.2834 | 0.6165 | 0.7021 | 0.044* | |
C14 | 0.4642 (8) | 0.65225 (17) | 0.65190 (17) | 0.0348 (13) | |
C15 | 0.6312 (8) | 0.66854 (19) | 0.67856 (18) | 0.0330 (13) | |
C16 | 0.7873 (8) | 0.69571 (19) | 0.66418 (16) | 0.0346 (12) | |
C17 | 0.9356 (8) | 0.71811 (18) | 0.69097 (18) | 0.0392 (13) | |
H17 | 0.9496 | 0.7161 | 0.7239 | 0.047* | |
C18 | 1.0561 (7) | 0.74306 (18) | 0.66265 (17) | 0.0334 (12) | |
H18 | 1.1689 | 0.7610 | 0.6724 | 0.040* | |
C19 | 0.9858 (7) | 0.73788 (17) | 0.61621 (17) | 0.0313 (12) | |
C20 | 1.0554 (7) | 0.76013 (16) | 0.57531 (19) | 0.0296 (11) | |
N21 | 0.8034 (6) | 0.73098 (14) | 0.51951 (13) | 0.0274 (10) | |
H21 | 0.7259 | 0.7150 | 0.5383 | 0.033* | 0.50 |
N22 | 0.4246 (6) | 0.68098 (13) | 0.50577 (13) | 0.0288 (9) | |
H22 | 0.4952 | 0.6910 | 0.5299 | 0.035* | 0.50 |
N23 | 0.4450 (6) | 0.65841 (14) | 0.60522 (13) | 0.0310 (10) | |
H23 | 0.5256 | 0.6742 | 0.5870 | 0.037* | 0.50 |
N24 | 0.8267 (6) | 0.70782 (14) | 0.61780 (13) | 0.0322 (10) | |
H24 | 0.7593 | 0.6976 | 0.5933 | 0.039* | 0.50 |
C25 | 0.6215 (8) | 0.72942 (19) | 0.39332 (17) | 0.0362 (13) | |
C26 | 0.4565 (9) | 0.7553 (2) | 0.37418 (19) | 0.0470 (15) | |
H26 | 0.3487 | 0.7660 | 0.3930 | 0.056* | |
C27 | 0.4626 (9) | 0.7642 (2) | 0.3257 (2) | 0.0447 (14) | |
H27 | 0.3575 | 0.7824 | 0.3124 | 0.054* | |
N28 | 0.6039 (8) | 0.74902 (17) | 0.29782 (14) | 0.0444 (12) | |
C29 | 0.7603 (9) | 0.7265 (2) | 0.31617 (18) | 0.0454 (14) | |
H29 | 0.8689 | 0.7177 | 0.2966 | 0.055* | |
C30 | 0.7693 (9) | 0.71522 (19) | 0.36370 (19) | 0.0447 (15) | |
H30 | 0.8794 | 0.6975 | 0.3754 | 0.054* | |
C31 | 0.0263 (7) | 0.59407 (19) | 0.53981 (18) | 0.0373 (13) | |
C32 | −0.1661 (8) | 0.6076 (2) | 0.52249 (18) | 0.0412 (14) | |
H32 | −0.1984 | 0.6388 | 0.5171 | 0.049* | |
C33 | −0.3075 (8) | 0.5724 (2) | 0.51358 (18) | 0.0391 (13) | |
H33 | −0.4393 | 0.5803 | 0.5027 | 0.047* | |
C34 | −0.2618 (7) | 0.52780 (18) | 0.52006 (17) | 0.0337 (12) | |
C35 | −0.0735 (7) | 0.51503 (18) | 0.53823 (16) | 0.0327 (12) | |
H35 | −0.0423 | 0.4837 | 0.5434 | 0.039* | |
C36 | 0.0683 (7) | 0.54888 (18) | 0.54863 (18) | 0.0362 (13) | |
H36 | 0.1954 | 0.5406 | 0.5620 | 0.043* | |
C37 | −0.4136 (9) | 0.4912 (2) | 0.5067 (2) | 0.0461 (16) | |
O38 | −0.5799 (6) | 0.50111 (14) | 0.49172 (17) | 0.0608 (12) | |
O39 | −0.3460 (6) | 0.44941 (12) | 0.51125 (13) | 0.0431 (9) | |
H39 | −0.4269 | 0.4312 | 0.4982 | 0.065* | |
C40 | 0.6221 (7) | 0.65808 (17) | 0.73043 (17) | 0.0319 (12) | |
C41 | 0.7675 (9) | 0.6304 (2) | 0.75036 (18) | 0.0437 (14) | |
H41 | 0.8761 | 0.6193 | 0.7320 | 0.052* | |
C42 | 0.7565 (10) | 0.6186 (2) | 0.7969 (2) | 0.0578 (17) | |
H42 | 0.8575 | 0.5994 | 0.8104 | 0.069* | |
C43 | 0.5980 (9) | 0.63466 (19) | 0.82441 (18) | 0.0395 (13) | |
C44 | 0.4605 (8) | 0.6637 (2) | 0.80424 (19) | 0.0437 (14) | |
H44 | 0.3561 | 0.6759 | 0.8231 | 0.052* | |
C45 | 0.4657 (7) | 0.67569 (18) | 0.75958 (17) | 0.0350 (13) | |
H45 | 0.3662 | 0.6958 | 0.7471 | 0.042* | |
C46 | 0.5868 (9) | 0.6189 (2) | 0.87347 (19) | 0.0501 (15) | |
O47 | 0.6918 (8) | 0.5904 (2) | 0.89125 (17) | 0.112 (2) | |
O48 | 0.4421 (7) | 0.63973 (14) | 0.89736 (13) | 0.0588 (11) | |
H48 | 0.4064 | 0.6230 | 0.9197 | 0.088* | |
C49 | 1.2184 (7) | 0.79360 (18) | 0.58330 (16) | 0.0301 (12) | |
C50 | 1.1776 (8) | 0.84015 (19) | 0.57746 (18) | 0.0364 (13) | |
H50 | 1.0493 | 0.8493 | 0.5654 | 0.044* | |
C51 | 1.3197 (9) | 0.8734 (2) | 0.58884 (19) | 0.0416 (15) | |
H51 | 1.2880 | 0.9049 | 0.5848 | 0.050* | |
C52 | 1.5101 (8) | 0.86040 (19) | 0.60628 (17) | 0.0347 (13) | |
C53 | 1.5528 (8) | 0.81516 (19) | 0.6125 (2) | 0.0417 (14) | |
H53 | 1.6797 | 0.8062 | 0.6255 | 0.050* | |
C54 | 1.4113 (8) | 0.78219 (18) | 0.60005 (18) | 0.0384 (13) | |
H54 | 1.4468 | 0.7508 | 0.6030 | 0.046* | |
C55 | 1.6565 (9) | 0.89627 (19) | 0.62124 (18) | 0.0386 (13) | |
O56 | 1.5896 (6) | 0.93832 (13) | 0.61762 (15) | 0.0572 (12) | |
H56 | 1.6871 | 0.9566 | 0.6203 | 0.086* | |
O57 | 1.8275 (5) | 0.88628 (13) | 0.63697 (14) | 0.0497 (10) | |
S58 | 2.0706 (3) | 0.98598 (6) | 0.63830 (7) | 0.0699 (5) | |
O59 | 1.8466 (7) | 0.99532 (16) | 0.6517 (2) | 0.0823 (15) | |
C60 | 2.2050 (14) | 1.0371 (3) | 0.6482 (3) | 0.095 (3) | |
H60A | 2.1990 | 1.0450 | 0.6813 | 0.143* | |
H60B | 2.1441 | 1.0617 | 0.6296 | 0.143* | |
H60C | 2.3466 | 1.0330 | 0.6391 | 0.143* | |
C61 | 2.1660 (11) | 0.9553 (3) | 0.6862 (4) | 0.094 (3) | |
H61A | 2.1170 | 0.9236 | 0.6847 | 0.141* | |
H61B | 2.1198 | 0.9695 | 0.7152 | 0.141* | |
H61C | 2.3145 | 0.9554 | 0.6855 | 0.141* | |
S62 | 0.1583 (2) | 0.59419 (5) | 0.98836 (5) | 0.0471 (4) | |
O63 | 0.3795 (5) | 0.60862 (12) | 0.98094 (11) | 0.0404 (9) | |
C64 | 0.0899 (10) | 0.5602 (2) | 0.9383 (2) | 0.0544 (17) | |
H64A | 0.1658 | 0.5314 | 0.9390 | 0.082* | |
H64B | 0.1224 | 0.5770 | 0.9097 | 0.082* | |
H64C | −0.0558 | 0.5536 | 0.9388 | 0.082* | |
C65 | 0.0242 (10) | 0.6456 (2) | 0.9742 (2) | 0.0582 (17) | |
H65A | 0.0427 | 0.6528 | 0.9411 | 0.087* | |
H65B | 0.0770 | 0.6708 | 0.9932 | 0.087* | |
H65C | −0.1204 | 0.6414 | 0.9804 | 0.087* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.030 (3) | 0.041 (3) | 0.030 (3) | −0.007 (3) | −0.001 (2) | 0.001 (2) |
C2 | 0.038 (3) | 0.035 (3) | 0.029 (3) | −0.007 (2) | −0.002 (2) | −0.004 (2) |
C3 | 0.034 (3) | 0.043 (3) | 0.036 (3) | −0.009 (3) | −0.009 (2) | 0.002 (3) |
C4 | 0.026 (3) | 0.029 (3) | 0.034 (3) | −0.002 (2) | −0.007 (2) | 0.005 (2) |
C5 | 0.028 (3) | 0.026 (3) | 0.030 (3) | 0.002 (2) | −0.005 (2) | −0.003 (2) |
C6 | 0.031 (3) | 0.036 (3) | 0.039 (3) | 0.005 (2) | −0.005 (2) | 0.003 (3) |
C7 | 0.038 (3) | 0.051 (3) | 0.038 (3) | −0.012 (3) | −0.009 (3) | 0.003 (3) |
C8 | 0.038 (3) | 0.058 (4) | 0.035 (3) | −0.005 (3) | −0.001 (3) | 0.003 (3) |
C9 | 0.029 (3) | 0.038 (3) | 0.035 (3) | −0.002 (2) | −0.012 (2) | −0.008 (2) |
C10 | 0.025 (3) | 0.044 (3) | 0.030 (3) | 0.004 (2) | −0.005 (2) | −0.001 (2) |
C11 | 0.025 (3) | 0.031 (3) | 0.035 (3) | −0.002 (2) | −0.002 (2) | 0.000 (2) |
C12 | 0.026 (3) | 0.037 (3) | 0.042 (3) | −0.007 (2) | 0.013 (2) | 0.004 (3) |
C13 | 0.034 (3) | 0.051 (4) | 0.024 (3) | −0.004 (3) | −0.004 (2) | −0.004 (2) |
C14 | 0.043 (3) | 0.035 (3) | 0.026 (3) | 0.006 (3) | 0.007 (2) | −0.003 (2) |
C15 | 0.019 (3) | 0.047 (3) | 0.033 (3) | 0.001 (2) | −0.001 (2) | −0.007 (3) |
C16 | 0.033 (3) | 0.044 (3) | 0.027 (3) | 0.005 (3) | −0.005 (2) | 0.007 (2) |
C17 | 0.044 (4) | 0.047 (3) | 0.026 (3) | −0.009 (3) | −0.016 (3) | −0.008 (3) |
C18 | 0.020 (3) | 0.050 (3) | 0.031 (3) | −0.012 (2) | 0.002 (2) | −0.005 (3) |
C19 | 0.023 (3) | 0.030 (3) | 0.041 (3) | 0.000 (2) | −0.010 (2) | 0.007 (2) |
C20 | 0.024 (3) | 0.023 (3) | 0.041 (3) | −0.002 (2) | −0.001 (2) | 0.001 (2) |
N21 | 0.027 (2) | 0.032 (2) | 0.024 (2) | −0.0091 (19) | −0.0027 (18) | 0.0091 (18) |
N22 | 0.024 (2) | 0.032 (2) | 0.030 (2) | −0.0080 (19) | −0.0023 (17) | 0.0020 (19) |
N23 | 0.029 (2) | 0.033 (2) | 0.031 (2) | −0.0017 (19) | −0.0027 (19) | 0.0006 (19) |
N24 | 0.030 (2) | 0.034 (2) | 0.032 (2) | 0.004 (2) | −0.0044 (19) | 0.0016 (19) |
C25 | 0.035 (3) | 0.043 (3) | 0.030 (3) | −0.009 (3) | −0.005 (3) | −0.001 (2) |
C26 | 0.047 (4) | 0.057 (4) | 0.037 (3) | −0.006 (3) | −0.005 (3) | 0.013 (3) |
C27 | 0.038 (3) | 0.054 (3) | 0.042 (3) | 0.009 (3) | −0.011 (3) | 0.008 (3) |
N28 | 0.052 (3) | 0.055 (3) | 0.026 (2) | −0.012 (2) | −0.008 (2) | 0.008 (2) |
C29 | 0.048 (4) | 0.059 (4) | 0.030 (3) | −0.011 (3) | 0.002 (3) | 0.002 (3) |
C30 | 0.046 (4) | 0.047 (4) | 0.041 (3) | 0.002 (3) | −0.010 (3) | −0.007 (3) |
C31 | 0.027 (3) | 0.048 (4) | 0.037 (3) | −0.011 (3) | 0.004 (2) | −0.008 (3) |
C32 | 0.025 (3) | 0.057 (4) | 0.041 (3) | 0.014 (3) | −0.005 (2) | −0.002 (3) |
C33 | 0.027 (3) | 0.050 (4) | 0.040 (3) | −0.005 (3) | −0.008 (2) | −0.011 (3) |
C34 | 0.029 (3) | 0.037 (3) | 0.035 (3) | −0.014 (2) | 0.004 (2) | −0.013 (2) |
C35 | 0.031 (3) | 0.043 (3) | 0.024 (3) | 0.002 (3) | −0.008 (2) | −0.002 (2) |
C36 | 0.022 (3) | 0.042 (3) | 0.044 (3) | 0.003 (3) | −0.007 (2) | −0.010 (3) |
C37 | 0.032 (4) | 0.056 (4) | 0.051 (4) | −0.013 (3) | 0.011 (3) | −0.019 (3) |
O38 | 0.034 (2) | 0.048 (3) | 0.100 (4) | −0.007 (2) | −0.015 (2) | −0.011 (2) |
O39 | 0.043 (2) | 0.037 (2) | 0.050 (2) | −0.0024 (19) | −0.0038 (18) | −0.0042 (18) |
C40 | 0.026 (3) | 0.040 (3) | 0.030 (3) | −0.003 (2) | −0.008 (2) | −0.001 (2) |
C41 | 0.040 (3) | 0.056 (4) | 0.035 (3) | 0.008 (3) | 0.002 (3) | −0.002 (3) |
C42 | 0.070 (5) | 0.056 (4) | 0.047 (4) | −0.001 (3) | −0.010 (3) | 0.011 (3) |
C43 | 0.037 (3) | 0.056 (4) | 0.026 (3) | −0.009 (3) | 0.002 (2) | 0.002 (3) |
C44 | 0.030 (3) | 0.058 (4) | 0.043 (3) | 0.005 (3) | 0.009 (3) | 0.005 (3) |
C45 | 0.026 (3) | 0.047 (3) | 0.032 (3) | 0.006 (2) | −0.001 (2) | 0.009 (2) |
C46 | 0.033 (3) | 0.080 (4) | 0.037 (3) | −0.001 (3) | −0.001 (3) | 0.018 (3) |
O47 | 0.087 (4) | 0.195 (6) | 0.055 (3) | 0.076 (4) | 0.019 (3) | 0.049 (3) |
O48 | 0.086 (3) | 0.060 (3) | 0.031 (2) | 0.017 (2) | 0.012 (2) | 0.0137 (18) |
C49 | 0.024 (3) | 0.041 (3) | 0.026 (3) | 0.001 (2) | −0.002 (2) | 0.002 (2) |
C50 | 0.032 (3) | 0.046 (4) | 0.031 (3) | −0.001 (3) | −0.014 (2) | 0.010 (3) |
C51 | 0.047 (4) | 0.032 (3) | 0.046 (3) | −0.007 (3) | −0.009 (3) | 0.002 (3) |
C52 | 0.033 (3) | 0.044 (4) | 0.027 (3) | 0.008 (3) | −0.010 (2) | 0.008 (2) |
C53 | 0.025 (3) | 0.043 (4) | 0.057 (4) | 0.000 (3) | 0.003 (3) | 0.005 (3) |
C54 | 0.045 (3) | 0.031 (3) | 0.039 (3) | −0.012 (3) | 0.000 (3) | −0.008 (2) |
C55 | 0.053 (4) | 0.034 (3) | 0.029 (3) | −0.011 (3) | −0.002 (3) | 0.005 (2) |
O56 | 0.050 (3) | 0.048 (3) | 0.073 (3) | −0.016 (2) | −0.026 (2) | 0.006 (2) |
O57 | 0.029 (2) | 0.053 (3) | 0.066 (3) | −0.0072 (19) | −0.015 (2) | −0.004 (2) |
S58 | 0.0711 (14) | 0.0744 (12) | 0.0641 (11) | −0.0179 (10) | 0.0019 (9) | −0.0075 (10) |
O59 | 0.061 (3) | 0.065 (3) | 0.121 (4) | −0.019 (2) | −0.032 (3) | −0.012 (3) |
C60 | 0.132 (8) | 0.068 (5) | 0.086 (6) | −0.026 (5) | 0.031 (5) | −0.019 (4) |
C61 | 0.050 (5) | 0.084 (6) | 0.147 (8) | 0.002 (4) | −0.024 (5) | 0.019 (5) |
S62 | 0.0445 (9) | 0.0525 (9) | 0.0442 (8) | 0.0136 (7) | 0.0031 (7) | 0.0087 (7) |
O63 | 0.041 (2) | 0.047 (2) | 0.0339 (19) | 0.0071 (17) | 0.0003 (16) | 0.0061 (16) |
C64 | 0.056 (4) | 0.062 (4) | 0.045 (4) | 0.013 (3) | −0.010 (3) | −0.007 (3) |
C65 | 0.044 (4) | 0.066 (4) | 0.065 (4) | 0.031 (3) | 0.007 (3) | 0.010 (3) |
Geometric parameters (Å, º) top
C1—C20 | 1.374 (7) | C32—H32 | 0.9500 |
C1—N21 | 1.369 (6) | C33—C34 | 1.351 (7) |
C1—C2 | 1.439 (7) | C33—H33 | 0.9500 |
C2—C3 | 1.367 (7) | C34—C35 | 1.394 (7) |
C2—H2 | 0.9500 | C34—C37 | 1.513 (7) |
C3—C4 | 1.423 (7) | C35—C36 | 1.392 (7) |
C3—H3 | 0.9500 | C35—H35 | 0.9500 |
C4—N21 | 1.396 (6) | C36—H36 | 0.9500 |
C4—C5 | 1.395 (7) | C37—O38 | 1.210 (7) |
C5—C6 | 1.425 (7) | C37—O39 | 1.307 (7) |
C5—C25 | 1.482 (7) | O39—H39 | 0.8400 |
C6—N22 | 1.354 (6) | C40—C41 | 1.376 (7) |
C6—C7 | 1.428 (7) | C40—C45 | 1.429 (7) |
C7—C8 | 1.321 (8) | C41—C42 | 1.381 (8) |
C7—H7 | 0.9500 | C41—H41 | 0.9500 |
C8—C9 | 1.444 (7) | C42—C43 | 1.396 (8) |
C8—H8 | 0.9500 | C42—H42 | 0.9500 |
C9—C10 | 1.380 (7) | C43—C44 | 1.367 (8) |
C9—N22 | 1.390 (6) | C43—C46 | 1.482 (7) |
C10—C11 | 1.398 (7) | C44—C45 | 1.328 (7) |
C10—C31 | 1.509 (7) | C44—H44 | 0.9500 |
C11—N23 | 1.388 (6) | C45—H45 | 0.9500 |
C11—C12 | 1.504 (7) | C46—O47 | 1.195 (7) |
C12—C13 | 1.341 (7) | C46—O48 | 1.328 (7) |
C12—H12 | 0.9500 | O48—H48 | 0.8400 |
C13—C14 | 1.447 (8) | C49—C50 | 1.398 (7) |
C13—H13 | 0.9500 | C49—C54 | 1.397 (7) |
C14—N23 | 1.355 (6) | C50—C51 | 1.388 (7) |
C14—C15 | 1.417 (7) | C50—H50 | 0.9500 |
C15—C16 | 1.367 (7) | C51—C52 | 1.401 (7) |
C15—C40 | 1.520 (7) | C51—H51 | 0.9500 |
C16—C17 | 1.401 (7) | C52—C53 | 1.364 (7) |
C16—N24 | 1.402 (6) | C52—C55 | 1.487 (8) |
C17—C18 | 1.355 (7) | C53—C54 | 1.387 (7) |
C17—H17 | 0.9500 | C53—H53 | 0.9500 |
C18—C19 | 1.414 (7) | C54—H54 | 0.9500 |
C18—H18 | 0.9500 | C55—O57 | 1.246 (6) |
C19—N24 | 1.370 (6) | C55—O56 | 1.311 (6) |
C19—C20 | 1.421 (7) | O56—H56 | 0.8400 |
C20—C49 | 1.471 (7) | S58—O59 | 1.555 (6) |
N21—H21 | 0.8800 | S58—C61 | 1.753 (8) |
N22—H22 | 0.8800 | S58—C60 | 1.759 (8) |
N23—H23 | 0.8800 | C60—H60A | 0.9800 |
N24—H24 | 0.8800 | C60—H60B | 0.9800 |
C25—C30 | 1.363 (8) | C60—H60C | 0.9800 |
C25—C26 | 1.432 (8) | C61—H61A | 0.9800 |
C26—C27 | 1.416 (7) | C61—H61B | 0.9800 |
C26—H26 | 0.9500 | C61—H61C | 0.9800 |
C27—N28 | 1.310 (7) | S62—O63 | 1.536 (4) |
C27—H27 | 0.9500 | S62—C65 | 1.790 (6) |
N28—C29 | 1.329 (7) | S62—C64 | 1.801 (6) |
C29—C30 | 1.402 (7) | C64—H64A | 0.9800 |
C29—H29 | 0.9500 | C64—H64B | 0.9800 |
C30—H30 | 0.9500 | C64—H64C | 0.9800 |
C31—C36 | 1.373 (7) | C65—H65A | 0.9800 |
C31—C32 | 1.415 (7) | C65—H65B | 0.9800 |
C32—C33 | 1.411 (8) | C65—H65C | 0.9800 |
| | | |
C20—C1—N21 | 126.5 (5) | C31—C32—H32 | 121.6 |
C20—C1—C2 | 123.2 (5) | C33—C32—H32 | 121.6 |
N21—C1—C2 | 110.3 (4) | C34—C33—C32 | 122.2 (5) |
C3—C2—C1 | 106.8 (5) | C34—C33—H33 | 118.9 |
C3—C2—H2 | 126.6 | C32—C33—H33 | 118.9 |
C1—C2—H2 | 126.6 | C33—C34—C35 | 120.5 (5) |
C2—C3—C4 | 107.3 (5) | C33—C34—C37 | 120.1 (5) |
C2—C3—H3 | 126.4 | C35—C34—C37 | 119.4 (5) |
C4—C3—H3 | 126.4 | C36—C35—C34 | 119.0 (5) |
N21—C4—C5 | 126.4 (4) | C36—C35—H35 | 120.5 |
N21—C4—C3 | 110.0 (4) | C34—C35—H35 | 120.5 |
C5—C4—C3 | 123.7 (4) | C31—C36—C35 | 120.7 (5) |
C4—C5—C6 | 125.3 (4) | C31—C36—H36 | 119.6 |
C4—C5—C25 | 118.1 (5) | C35—C36—H36 | 119.6 |
C6—C5—C25 | 116.6 (4) | O38—C37—O39 | 124.5 (5) |
N22—C6—C7 | 108.3 (5) | O38—C37—C34 | 121.1 (6) |
N22—C6—C5 | 125.6 (4) | O39—C37—C34 | 114.3 (5) |
C7—C6—C5 | 125.8 (5) | C37—O39—H39 | 109.5 |
C8—C7—C6 | 107.8 (5) | C41—C40—C45 | 118.3 (4) |
C8—C7—H7 | 126.1 | C41—C40—C15 | 119.4 (5) |
C6—C7—H7 | 126.1 | C45—C40—C15 | 122.3 (4) |
C7—C8—C9 | 109.2 (5) | C42—C41—C40 | 120.4 (5) |
C7—C8—H8 | 125.4 | C42—C41—H41 | 119.8 |
C9—C8—H8 | 125.4 | C40—C41—H41 | 119.8 |
C10—C9—N22 | 126.5 (4) | C41—C42—C43 | 120.5 (6) |
C10—C9—C8 | 127.5 (5) | C41—C42—H42 | 119.7 |
N22—C9—C8 | 105.7 (5) | C43—C42—H42 | 119.7 |
C9—C10—C11 | 124.9 (5) | C44—C43—C42 | 117.9 (5) |
C9—C10—C31 | 116.6 (4) | C44—C43—C46 | 123.7 (5) |
C11—C10—C31 | 118.3 (5) | C42—C43—C46 | 118.4 (5) |
N23—C11—C10 | 127.6 (5) | C45—C44—C43 | 123.3 (5) |
N23—C11—C12 | 109.4 (4) | C45—C44—H44 | 118.4 |
C10—C11—C12 | 123.0 (5) | C43—C44—H44 | 118.4 |
C13—C12—C11 | 105.4 (5) | C44—C45—C40 | 119.6 (5) |
C13—C12—H12 | 127.3 | C44—C45—H45 | 120.2 |
C11—C12—H12 | 127.3 | C40—C45—H45 | 120.2 |
C12—C13—C14 | 107.9 (5) | O47—C46—O48 | 121.1 (5) |
C12—C13—H13 | 126.1 | O47—C46—C43 | 126.0 (6) |
C14—C13—H13 | 126.1 | O48—C46—C43 | 112.9 (5) |
N23—C14—C15 | 123.6 (5) | C46—O48—H48 | 109.5 |
N23—C14—C13 | 111.8 (4) | C50—C49—C54 | 116.6 (5) |
C15—C14—C13 | 124.6 (5) | C50—C49—C20 | 119.3 (4) |
C16—C15—C14 | 128.1 (5) | C54—C49—C20 | 123.9 (5) |
C16—C15—C40 | 116.6 (4) | C51—C50—C49 | 121.7 (5) |
C14—C15—C40 | 115.0 (5) | C51—C50—H50 | 119.1 |
C15—C16—C17 | 129.1 (5) | C49—C50—H50 | 119.1 |
C15—C16—N24 | 125.4 (4) | C50—C51—C52 | 119.7 (5) |
C17—C16—N24 | 105.5 (5) | C50—C51—H51 | 120.2 |
C18—C17—C16 | 109.5 (5) | C52—C51—H51 | 120.2 |
C18—C17—H17 | 125.2 | C53—C52—C51 | 119.6 (5) |
C16—C17—H17 | 125.2 | C53—C52—C55 | 120.9 (5) |
C17—C18—C19 | 108.5 (4) | C51—C52—C55 | 119.3 (5) |
C17—C18—H18 | 125.8 | C52—C53—C54 | 120.2 (5) |
C19—C18—H18 | 125.8 | C52—C53—H53 | 119.9 |
N24—C19—C18 | 106.4 (4) | C54—C53—H53 | 119.9 |
N24—C19—C20 | 125.1 (4) | C53—C54—C49 | 122.1 (5) |
C18—C19—C20 | 128.5 (5) | C53—C54—H54 | 118.9 |
C1—C20—C19 | 125.7 (5) | C49—C54—H54 | 118.9 |
C1—C20—C49 | 119.5 (5) | O57—C55—O56 | 123.5 (5) |
C19—C20—C49 | 114.7 (4) | O57—C55—C52 | 121.5 (5) |
C1—N21—C4 | 105.7 (4) | O56—C55—C52 | 114.9 (5) |
C1—N21—H21 | 127.2 | C55—O56—H56 | 109.5 |
C4—N21—H21 | 127.2 | O59—S58—C61 | 103.4 (4) |
C6—N22—C9 | 109.0 (4) | O59—S58—C60 | 106.8 (4) |
C6—N22—H22 | 125.5 | C61—S58—C60 | 97.6 (4) |
C9—N22—H22 | 125.5 | S58—C60—H60A | 109.5 |
C14—N23—C11 | 105.6 (4) | S58—C60—H60B | 109.5 |
C14—N23—H23 | 127.2 | H60A—C60—H60B | 109.5 |
C11—N23—H23 | 127.2 | S58—C60—H60C | 109.5 |
C19—N24—C16 | 110.0 (4) | H60A—C60—H60C | 109.5 |
C19—N24—H24 | 125.0 | H60B—C60—H60C | 109.5 |
C16—N24—H24 | 125.0 | S58—C61—H61A | 109.5 |
C30—C25—C26 | 117.9 (5) | S58—C61—H61B | 109.5 |
C30—C25—C5 | 123.5 (5) | H61A—C61—H61B | 109.5 |
C26—C25—C5 | 118.6 (5) | S58—C61—H61C | 109.5 |
C27—C26—C25 | 116.4 (5) | H61A—C61—H61C | 109.5 |
C27—C26—H26 | 121.8 | H61B—C61—H61C | 109.5 |
C25—C26—H26 | 121.8 | O63—S62—C65 | 101.9 (3) |
N28—C27—C26 | 124.3 (5) | O63—S62—C64 | 105.8 (3) |
N28—C27—H27 | 117.9 | C65—S62—C64 | 99.4 (3) |
C26—C27—H27 | 117.9 | S62—C64—H64A | 109.5 |
C27—N28—C29 | 118.8 (4) | S62—C64—H64B | 109.5 |
N28—C29—C30 | 121.8 (5) | H64A—C64—H64B | 109.5 |
N28—C29—H29 | 119.1 | S62—C64—H64C | 109.5 |
C30—C29—H29 | 119.1 | H64A—C64—H64C | 109.5 |
C25—C30—C29 | 120.6 (5) | H64B—C64—H64C | 109.5 |
C25—C30—H30 | 119.7 | S62—C65—H65A | 109.5 |
C29—C30—H30 | 119.7 | S62—C65—H65B | 109.5 |
C36—C31—C32 | 120.8 (5) | H65A—C65—H65B | 109.5 |
C36—C31—C10 | 119.0 (5) | S62—C65—H65C | 109.5 |
C32—C31—C10 | 120.2 (5) | H65A—C65—H65C | 109.5 |
C31—C32—C33 | 116.7 (5) | H65B—C65—H65C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O56—H56···O59 | 0.84 | 1.78 | 2.565 (6) | 154 |
O48—H48···O63 | 0.84 | 1.82 | 2.599 (5) | 154 |
O39—H39···O63i | 0.84 | 1.79 | 2.624 (5) | 169 |
C17—H17···N28ii | 0.95 | 2.55 | 3.387 (6) | 147 |
Symmetry codes: (i) x−1, −y+1, z−1/2; (ii) x+1/2, −y+3/2, z+1/2. |
(II) 20-(4-pyridyl)porphyrin-5
4,10
4,15
4-tribenzoic
acid–4-acetylpyridine–tetrahydrofuran (1/2/10)
top
Crystal data top
C46H29N5O6·2C7H7NO·10C4H8O | Z = 1 |
Mr = 1711.05 | F(000) = 916 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
a = 7.6005 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.6609 (10) Å | Cell parameters from 7863 reflections |
c = 18.6149 (12) Å | θ = 1.4–28.3° |
α = 77.718 (3)° | µ = 0.09 mm−1 |
β = 89.630 (4)° | T = 110 K |
γ = 78.805 (4)° | Prism, red |
V = 2122.4 (2) Å3 | 0.40 × 0.30 × 0.25 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4725 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 28.2°, θmin = 2.2° |
Detector resolution: 12.8 pixels mm-1 | h = −10→8 |
0.5 deg. ϕ & ω scans | k = −19→20 |
24317 measured reflections | l = −20→24 |
10109 independent reflections | |
Refinement top
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.80 | w = 1/[σ2(Fo2) + (0.0733P)2] where P = (Fo2 + 2Fc2)/3 |
10109 reflections | (Δ/σ)max = 0.019 |
669 parameters | Δρmax = 0.25 e Å−3 |
8 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C46H29N5O6·2C7H7NO·10C4H8O | γ = 78.805 (4)° |
Mr = 1711.05 | V = 2122.4 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6005 (3) Å | Mo Kα radiation |
b = 15.6609 (10) Å | µ = 0.09 mm−1 |
c = 18.6149 (12) Å | T = 110 K |
α = 77.718 (3)° | 0.40 × 0.30 × 0.25 mm |
β = 89.630 (4)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4725 reflections with I > 2σ(I) |
24317 measured reflections | Rint = 0.060 |
10109 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 8 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.80 | Δρmax = 0.25 e Å−3 |
10109 reflections | Δρmin = −0.20 e Å−3 |
669 parameters | |
Special details top
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. The results below refer to crystallographic refinement after application of the
SQUEEZE procedure (Spek, 2003) to the diffraction data in order the subtract
from it the contribution of the severely disordered THF solvent trapped in the
lattice. Due to the apparent pseudo centrosymmetric space symmetry the
crystallographic refinement was based on data set with merged Friedel
opposites. Conventional refinement of the same solvent excluded structural
model against the original data set converged only at R1=0.20. The solvent
accessible voids amount to 1051 Å3, about 50% of the crystal volume, with
a residual electron-density count of 82 e/Å3 per unit-cell (corresponding
to at least 2 molecules of THF). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.3180 (6) | −0.0668 (3) | 0.6753 (3) | 0.0476 (12) | |
C2 | 0.3226 (6) | −0.0884 (4) | 0.6042 (3) | 0.0543 (13) | |
H2 | 0.2471 | −0.1223 | 0.5871 | 0.065* | |
C3 | 0.4493 (7) | −0.0534 (4) | 0.5660 (3) | 0.0620 (15) | |
H3 | 0.4796 | −0.0593 | 0.5174 | 0.074* | |
C4 | 0.5337 (5) | −0.0057 (3) | 0.6086 (2) | 0.0399 (11) | |
C5 | 0.6771 (6) | 0.0389 (3) | 0.5913 (2) | 0.0428 (11) | |
C6 | 0.7563 (5) | 0.0846 (3) | 0.6315 (3) | 0.0384 (11) | |
C7 | 0.8970 (6) | 0.1295 (3) | 0.6083 (2) | 0.0405 (11) | |
H7 | 0.9553 | 0.1303 | 0.5630 | 0.049* | |
C8 | 0.9358 (6) | 0.1711 (3) | 0.6604 (2) | 0.0467 (12) | |
H8 | 1.0218 | 0.2081 | 0.6589 | 0.056* | |
C9 | 0.8194 (5) | 0.1475 (3) | 0.7185 (3) | 0.0431 (12) | |
C10 | 0.8193 (5) | 0.1760 (3) | 0.7860 (2) | 0.0336 (10) | |
C11 | 0.7107 (6) | 0.1487 (3) | 0.8464 (2) | 0.0403 (11) | |
C12 | 0.7136 (6) | 0.1697 (3) | 0.9160 (2) | 0.0496 (13) | |
H12 | 0.7911 | 0.2034 | 0.9320 | 0.060* | |
C13 | 0.5833 (6) | 0.1326 (3) | 0.9577 (3) | 0.0472 (12) | |
H13 | 0.5563 | 0.1358 | 1.0071 | 0.057* | |
C14 | 0.4989 (6) | 0.0893 (3) | 0.9125 (2) | 0.0424 (12) | |
C15 | 0.3533 (5) | 0.0467 (3) | 0.9335 (3) | 0.0409 (11) | |
C16 | 0.2739 (6) | 0.0003 (3) | 0.8876 (2) | 0.0415 (11) | |
C17 | 0.1206 (6) | −0.0468 (3) | 0.9126 (3) | 0.0571 (14) | |
H17 | 0.0612 | −0.0489 | 0.9579 | 0.069* | |
C18 | 0.0865 (5) | −0.0844 (3) | 0.8582 (3) | 0.0436 (12) | |
H18 | −0.0023 | −0.1194 | 0.8574 | 0.052* | |
C19 | 0.2121 (5) | −0.0622 (3) | 0.7986 (2) | 0.0353 (10) | |
C20 | 0.2099 (5) | −0.0866 (3) | 0.7323 (3) | 0.0437 (12) | |
N21 | 0.4514 (4) | −0.0151 (2) | 0.67491 (18) | 0.0375 (9) | |
H21 | 0.4777 | 0.0078 | 0.7118 | 0.045* | 0.50 |
N22 | 0.7111 (4) | 0.0947 (2) | 0.70131 (19) | 0.0371 (9) | |
H22 | 0.6299 | 0.0719 | 0.7288 | 0.045* | 0.50 |
N23 | 0.5828 (4) | 0.0971 (2) | 0.8457 (2) | 0.0430 (10) | |
H23 | 0.5587 | 0.0732 | 0.8091 | 0.052* | 0.50 |
N24 | 0.3243 (4) | −0.0114 (2) | 0.81933 (18) | 0.0389 (9) | |
H24 | 0.4107 | 0.0092 | 0.7937 | 0.047* | 0.50 |
C25 | 0.7530 (6) | 0.0305 (3) | 0.5172 (2) | 0.0528 (13) | |
C26 | 0.8549 (6) | −0.0486 (3) | 0.5058 (3) | 0.0650 (15) | |
H26 | 0.8724 | −0.0997 | 0.5449 | 0.078* | |
C27 | 0.9309 (6) | −0.0555 (3) | 0.4402 (3) | 0.0776 (17) | |
H27 | 0.9995 | −0.1113 | 0.4349 | 0.093* | |
N28 | 0.9116 (6) | 0.0130 (4) | 0.3842 (2) | 0.0971 (19) | |
C29 | 0.8052 (11) | 0.0867 (5) | 0.3918 (3) | 0.119 (3) | |
H29 | 0.7798 | 0.1346 | 0.3501 | 0.143* | |
C30 | 0.7267 (9) | 0.0987 (3) | 0.4580 (3) | 0.116 (3) | |
H30 | 0.6553 | 0.1547 | 0.4611 | 0.139* | |
C31 | 0.9417 (6) | 0.2368 (3) | 0.7977 (2) | 0.0384 (11) | |
C32 | 1.1252 (5) | 0.2165 (3) | 0.7929 (2) | 0.0371 (11) | |
H32 | 1.1784 | 0.1610 | 0.7818 | 0.045* | |
C33 | 1.2353 (6) | 0.2738 (3) | 0.8036 (3) | 0.0450 (12) | |
H33 | 1.3622 | 0.2576 | 0.8020 | 0.054* | |
C34 | 1.1498 (6) | 0.3588 (3) | 0.8174 (2) | 0.0423 (11) | |
C35 | 0.9683 (6) | 0.3788 (3) | 0.8204 (3) | 0.0540 (14) | |
H35 | 0.9135 | 0.4353 | 0.8295 | 0.065* | |
C36 | 0.8597 (5) | 0.3203 (3) | 0.8109 (3) | 0.0492 (13) | |
H36 | 0.7330 | 0.3361 | 0.8132 | 0.059* | |
C37 | 1.2709 (7) | 0.4202 (4) | 0.8286 (3) | 0.0541 (14) | |
O38 | 1.4358 (4) | 0.3999 (2) | 0.8325 (2) | 0.0626 (10) | |
O39 | 1.1830 (4) | 0.4959 (2) | 0.8365 (3) | 0.0744 (12) | |
H39 | 1.2541 | 0.5255 | 0.8490 | 0.112* | |
C40 | 0.2706 (4) | 0.0544 (2) | 1.00409 (13) | 0.0490 (13) | |
C41 | 0.1719 (4) | 0.1355 (2) | 1.01351 (15) | 0.082 (2) | |
H41 | 0.1556 | 0.1862 | 0.9739 | 0.098* | |
C42 | 0.0970 (4) | 0.1425 (2) | 1.08084 (19) | 0.099 (2) | |
H42 | 0.0295 | 0.1980 | 1.0873 | 0.119* | |
C43 | 0.1208 (4) | 0.0684 (3) | 1.13876 (14) | 0.0589 (15) | |
C44 | 0.2195 (4) | −0.0128 (2) | 1.12933 (15) | 0.0695 (15) | |
H44 | 0.2358 | −0.0635 | 1.1689 | 0.083* | |
C45 | 0.2944 (4) | −0.01979 (18) | 1.06200 (18) | 0.0585 (13) | |
H45 | 0.3619 | −0.0753 | 1.0556 | 0.070* | |
C46 | 0.0493 (6) | 0.0673 (4) | 1.2136 (2) | 0.0773 (13) | |
O47 | −0.0269 (6) | 0.1360 (4) | 1.2294 (3) | 0.1349 (17) | |
O48 | 0.0651 (6) | −0.0114 (3) | 1.2632 (2) | 0.1076 (16) | |
H48 | 0.0303 | −0.0017 | 1.3041 | 0.178* | |
C49 | 0.0948 (5) | −0.1540 (3) | 0.7238 (2) | 0.0401 (11) | |
C50 | −0.0953 (5) | −0.1306 (3) | 0.7284 (2) | 0.0455 (12) | |
H50 | −0.1507 | −0.0744 | 0.7377 | 0.055* | |
C51 | −0.1975 (5) | −0.1924 (3) | 0.7189 (2) | 0.0397 (11) | |
H51 | −0.3240 | −0.1776 | 0.7227 | 0.048* | |
C52 | −0.1253 (5) | −0.2721 (3) | 0.7044 (2) | 0.0388 (11) | |
C53 | 0.0650 (5) | −0.2973 (3) | 0.7015 (2) | 0.0411 (11) | |
H53 | 0.1192 | −0.3544 | 0.6938 | 0.049* | |
C54 | 0.1664 (6) | −0.2376 (3) | 0.7102 (2) | 0.0455 (12) | |
H54 | 0.2928 | −0.2537 | 0.7068 | 0.055* | |
C55 | −0.2409 (6) | −0.3346 (3) | 0.6927 (3) | 0.0437 (12) | |
O56 | −0.4000 (4) | −0.3139 (2) | 0.6908 (2) | 0.0655 (10) | |
O57 | −0.1533 (3) | −0.4160 (2) | 0.68678 (19) | 0.0510 (8) | |
H57 | −0.2273 | −0.4456 | 0.6768 | 0.077* | |
C58 | −0.4261 (5) | −0.6417 (3) | 0.6232 (3) | 0.0581 (14) | |
H58 | −0.3760 | −0.6978 | 0.6124 | 0.070* | |
C59 | −0.3117 (6) | −0.5920 (3) | 0.6401 (2) | 0.0467 (12) | |
H59 | −0.1860 | −0.6108 | 0.6367 | 0.056* | |
N60 | −0.3771 (5) | −0.5158 (3) | 0.6616 (3) | 0.0644 (13) | |
C61 | −0.5561 (6) | −0.4914 (4) | 0.6609 (4) | 0.085 (2) | |
H61 | −0.6037 | −0.4361 | 0.6738 | 0.102* | |
C62 | −0.6739 (6) | −0.5379 (3) | 0.6437 (3) | 0.0570 (14) | |
H62 | −0.7993 | −0.5179 | 0.6470 | 0.068* | |
C63 | −0.6062 (5) | −0.6168 (3) | 0.6207 (3) | 0.0465 (12) | |
C64 | −0.7277 (7) | −0.6679 (4) | 0.5991 (3) | 0.0597 (15) | |
O65 | −0.8967 (4) | −0.6356 (2) | 0.5947 (2) | 0.0712 (11) | |
C66 | −0.6626 (7) | −0.7517 (4) | 0.5710 (4) | 0.096 (2) | |
H66A | −0.7659 | −0.7751 | 0.5581 | 0.144* | |
H66B | −0.5877 | −0.7964 | 0.6093 | 0.144* | |
H66C | −0.5919 | −0.7381 | 0.5273 | 0.144* | |
C67 | 1.4501 (4) | 0.7286 (3) | 0.9038 (3) | 0.0476 (12) | |
H67 | 1.4006 | 0.7817 | 0.9198 | 0.057* | |
C68 | 1.3432 (6) | 0.6753 (4) | 0.8810 (3) | 0.0639 (16) | |
H68 | 1.2168 | 0.6957 | 0.8791 | 0.077* | |
N69 | 1.4050 (4) | 0.5984 (3) | 0.8619 (2) | 0.0462 (10) | |
C70 | 1.5831 (4) | 0.5709 (3) | 0.8584 (3) | 0.0481 (12) | |
H70 | 1.6285 | 0.5181 | 0.8413 | 0.058* | |
C71 | 1.7027 (5) | 0.6198 (3) | 0.8800 (3) | 0.0583 (15) | |
H71 | 1.8286 | 0.5987 | 0.8797 | 0.070* | |
C72 | 1.6374 (5) | 0.6978 (3) | 0.9013 (3) | 0.0466 (13) | |
C73 | 1.7685 (6) | 0.7522 (3) | 0.9251 (3) | 0.0497 (13) | |
O74 | 1.9232 (4) | 0.7263 (2) | 0.9260 (2) | 0.0743 (12) | |
C75 | 1.6874 (6) | 0.8395 (3) | 0.9400 (3) | 0.0584 (13) | |
H75A | 1.7821 | 0.8684 | 0.9533 | 0.088* | |
H75B | 1.6056 | 0.8314 | 0.9807 | 0.088* | |
H75C | 1.6204 | 0.8769 | 0.8959 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.049 (3) | 0.043 (3) | 0.055 (3) | −0.015 (2) | 0.001 (2) | −0.015 (2) |
C2 | 0.059 (3) | 0.072 (4) | 0.049 (3) | −0.028 (3) | 0.014 (2) | −0.035 (3) |
C3 | 0.075 (4) | 0.079 (4) | 0.041 (3) | −0.020 (3) | 0.005 (3) | −0.029 (3) |
C4 | 0.038 (2) | 0.047 (3) | 0.042 (3) | −0.015 (2) | 0.005 (2) | −0.017 (2) |
C5 | 0.056 (3) | 0.044 (3) | 0.025 (2) | −0.010 (2) | 0.0196 (19) | 0.000 (2) |
C6 | 0.038 (2) | 0.033 (2) | 0.047 (3) | −0.0075 (19) | 0.012 (2) | −0.014 (2) |
C7 | 0.053 (2) | 0.050 (3) | 0.028 (2) | −0.020 (2) | 0.0075 (18) | −0.019 (2) |
C8 | 0.059 (3) | 0.046 (3) | 0.033 (3) | −0.009 (2) | 0.010 (2) | −0.005 (2) |
C9 | 0.036 (2) | 0.037 (3) | 0.059 (3) | −0.002 (2) | 0.006 (2) | −0.019 (2) |
C10 | 0.037 (2) | 0.037 (2) | 0.027 (2) | −0.0016 (18) | 0.0129 (17) | −0.0098 (19) |
C11 | 0.041 (2) | 0.050 (3) | 0.034 (3) | −0.012 (2) | 0.0148 (19) | −0.016 (2) |
C12 | 0.058 (3) | 0.066 (3) | 0.031 (3) | −0.032 (3) | 0.009 (2) | −0.008 (2) |
C13 | 0.050 (3) | 0.059 (3) | 0.039 (3) | −0.025 (2) | 0.021 (2) | −0.014 (2) |
C14 | 0.055 (3) | 0.055 (3) | 0.022 (2) | −0.019 (2) | 0.014 (2) | −0.013 (2) |
C15 | 0.033 (2) | 0.047 (3) | 0.049 (3) | −0.014 (2) | 0.0096 (19) | −0.019 (2) |
C16 | 0.048 (3) | 0.047 (3) | 0.034 (3) | −0.019 (2) | 0.012 (2) | −0.011 (2) |
C17 | 0.049 (3) | 0.050 (3) | 0.066 (4) | −0.020 (2) | 0.028 (2) | −0.015 (3) |
C18 | 0.043 (2) | 0.046 (3) | 0.053 (3) | −0.025 (2) | 0.021 (2) | −0.023 (2) |
C19 | 0.045 (2) | 0.033 (2) | 0.028 (2) | −0.012 (2) | 0.0124 (18) | −0.0043 (19) |
C20 | 0.031 (2) | 0.038 (3) | 0.044 (3) | −0.0142 (19) | 0.007 (2) | −0.008 (2) |
N21 | 0.044 (2) | 0.043 (2) | 0.033 (2) | −0.0156 (18) | 0.0157 (16) | −0.0178 (18) |
N22 | 0.0365 (19) | 0.035 (2) | 0.042 (2) | −0.0059 (16) | 0.0103 (16) | −0.0131 (18) |
N23 | 0.046 (2) | 0.043 (2) | 0.043 (2) | −0.0154 (19) | 0.0094 (18) | −0.011 (2) |
N24 | 0.043 (2) | 0.049 (2) | 0.031 (2) | −0.0232 (18) | 0.0198 (16) | −0.0122 (18) |
C25 | 0.074 (3) | 0.050 (3) | 0.037 (3) | −0.022 (3) | 0.012 (2) | −0.006 (2) |
C26 | 0.064 (3) | 0.079 (4) | 0.064 (4) | −0.025 (3) | 0.020 (3) | −0.030 (3) |
C27 | 0.106 (4) | 0.059 (3) | 0.078 (4) | −0.016 (3) | 0.025 (4) | −0.038 (3) |
N28 | 0.115 (4) | 0.123 (5) | 0.059 (3) | −0.026 (4) | 0.049 (3) | −0.029 (4) |
C29 | 0.182 (8) | 0.119 (6) | 0.064 (5) | −0.059 (6) | 0.045 (5) | −0.011 (4) |
C30 | 0.165 (6) | 0.109 (6) | 0.055 (4) | −0.001 (5) | 0.055 (4) | −0.004 (4) |
C31 | 0.051 (3) | 0.029 (2) | 0.043 (3) | −0.021 (2) | 0.016 (2) | −0.016 (2) |
C32 | 0.032 (2) | 0.029 (2) | 0.052 (3) | −0.0076 (19) | 0.0057 (19) | −0.012 (2) |
C33 | 0.047 (3) | 0.032 (3) | 0.053 (3) | −0.003 (2) | 0.005 (2) | −0.007 (2) |
C34 | 0.048 (3) | 0.033 (3) | 0.048 (3) | −0.011 (2) | 0.012 (2) | −0.013 (2) |
C35 | 0.034 (3) | 0.049 (3) | 0.088 (4) | −0.008 (2) | 0.012 (2) | −0.034 (3) |
C36 | 0.024 (2) | 0.042 (3) | 0.088 (4) | −0.011 (2) | 0.008 (2) | −0.022 (3) |
C37 | 0.050 (3) | 0.050 (4) | 0.067 (4) | −0.016 (3) | 0.012 (3) | −0.018 (3) |
O38 | 0.0258 (17) | 0.070 (3) | 0.101 (3) | −0.0149 (16) | 0.0026 (16) | −0.034 (2) |
O39 | 0.044 (2) | 0.053 (2) | 0.139 (4) | −0.0201 (18) | 0.016 (2) | −0.041 (2) |
C40 | 0.042 (2) | 0.079 (4) | 0.040 (3) | −0.027 (2) | 0.019 (2) | −0.029 (3) |
C41 | 0.068 (3) | 0.115 (5) | 0.050 (4) | 0.018 (3) | 0.023 (3) | −0.023 (3) |
C42 | 0.077 (4) | 0.181 (7) | 0.034 (3) | −0.003 (4) | 0.023 (3) | −0.033 (4) |
C43 | 0.060 (3) | 0.104 (5) | 0.036 (3) | −0.052 (3) | 0.013 (2) | −0.032 (3) |
C44 | 0.082 (3) | 0.101 (4) | 0.036 (3) | −0.036 (3) | 0.028 (2) | −0.022 (3) |
C45 | 0.072 (3) | 0.064 (3) | 0.050 (3) | −0.028 (3) | 0.022 (2) | −0.023 (3) |
C46 | 0.089 (3) | 0.094 (4) | 0.062 (3) | −0.033 (3) | 0.031 (2) | −0.032 (3) |
O47 | 0.124 (3) | 0.145 (5) | 0.138 (4) | −0.024 (3) | 0.031 (3) | −0.058 (3) |
O48 | 0.118 (3) | 0.089 (4) | 0.111 (3) | −0.030 (3) | 0.029 (3) | −0.029 (3) |
C49 | 0.031 (2) | 0.063 (3) | 0.028 (3) | −0.011 (2) | 0.0064 (18) | −0.011 (2) |
C50 | 0.038 (3) | 0.053 (3) | 0.046 (3) | −0.005 (2) | 0.010 (2) | −0.018 (2) |
C51 | 0.019 (2) | 0.052 (3) | 0.052 (3) | −0.0062 (19) | 0.0134 (18) | −0.022 (2) |
C52 | 0.019 (2) | 0.053 (3) | 0.050 (3) | −0.0095 (19) | 0.0021 (18) | −0.020 (2) |
C53 | 0.036 (2) | 0.042 (3) | 0.052 (3) | −0.012 (2) | 0.006 (2) | −0.019 (2) |
C54 | 0.040 (3) | 0.058 (3) | 0.046 (3) | −0.010 (2) | 0.020 (2) | −0.027 (2) |
C55 | 0.030 (3) | 0.043 (3) | 0.061 (3) | −0.008 (2) | 0.011 (2) | −0.016 (3) |
O56 | 0.048 (2) | 0.051 (2) | 0.105 (3) | −0.0118 (17) | 0.0171 (19) | −0.032 (2) |
O57 | 0.0345 (16) | 0.048 (2) | 0.078 (2) | −0.0104 (15) | −0.0002 (15) | −0.0284 (18) |
C58 | 0.050 (3) | 0.045 (3) | 0.078 (4) | −0.002 (2) | 0.014 (2) | −0.018 (3) |
C59 | 0.031 (2) | 0.055 (3) | 0.057 (3) | −0.001 (2) | 0.009 (2) | −0.024 (3) |
N60 | 0.038 (2) | 0.059 (3) | 0.098 (4) | −0.011 (2) | 0.019 (2) | −0.023 (3) |
C61 | 0.048 (3) | 0.074 (4) | 0.139 (6) | 0.017 (3) | 0.017 (3) | −0.063 (4) |
C62 | 0.045 (3) | 0.050 (3) | 0.081 (4) | −0.017 (3) | 0.015 (3) | −0.019 (3) |
C63 | 0.043 (3) | 0.040 (3) | 0.061 (3) | −0.005 (2) | 0.019 (2) | −0.025 (2) |
C64 | 0.052 (3) | 0.060 (4) | 0.063 (4) | −0.001 (3) | 0.019 (2) | −0.013 (3) |
O65 | 0.046 (2) | 0.068 (2) | 0.108 (3) | −0.0177 (17) | 0.0177 (18) | −0.033 (2) |
C66 | 0.059 (3) | 0.109 (5) | 0.136 (6) | −0.025 (3) | 0.046 (3) | −0.057 (4) |
C67 | 0.026 (2) | 0.051 (3) | 0.070 (3) | −0.011 (2) | 0.0105 (19) | −0.020 (2) |
C68 | 0.037 (3) | 0.057 (4) | 0.103 (5) | −0.016 (3) | −0.002 (3) | −0.023 (3) |
N69 | 0.039 (2) | 0.050 (3) | 0.060 (3) | −0.0176 (19) | 0.0057 (17) | −0.027 (2) |
C70 | 0.046 (3) | 0.037 (2) | 0.072 (3) | −0.028 (2) | 0.009 (2) | −0.018 (2) |
C71 | 0.021 (2) | 0.052 (3) | 0.105 (5) | −0.008 (2) | 0.017 (2) | −0.022 (3) |
C72 | 0.030 (2) | 0.056 (3) | 0.058 (3) | −0.021 (2) | 0.011 (2) | −0.011 (3) |
C73 | 0.037 (3) | 0.050 (3) | 0.075 (3) | −0.029 (2) | 0.007 (2) | −0.022 (3) |
O74 | 0.0269 (18) | 0.069 (2) | 0.136 (4) | −0.0196 (16) | 0.0065 (18) | −0.032 (2) |
C75 | 0.047 (3) | 0.043 (3) | 0.099 (4) | −0.017 (2) | 0.003 (2) | −0.038 (2) |
Geometric parameters (Å, º) top
C1—C20 | 1.358 (6) | C36—H36 | 0.9500 |
C1—N21 | 1.415 (5) | C37—O38 | 1.230 (5) |
C1—C2 | 1.433 (6) | C37—O39 | 1.280 (6) |
C2—C3 | 1.328 (6) | O39—H39 | 0.8400 |
C2—H2 | 0.9500 | C40—C41 | 1.3900 |
C3—C4 | 1.429 (6) | C40—C45 | 1.3900 |
C3—H3 | 0.9500 | C41—C42 | 1.3900 |
C4—N21 | 1.373 (5) | C41—H41 | 0.9500 |
C4—C5 | 1.406 (6) | C42—C43 | 1.3900 |
C5—C6 | 1.355 (6) | C42—H42 | 0.9500 |
C5—C25 | 1.513 (5) | C43—C44 | 1.3900 |
C6—N22 | 1.376 (5) | C43—C46 | 1.490 (4) |
C6—C7 | 1.408 (6) | C44—C45 | 1.3900 |
C7—C8 | 1.340 (6) | C44—H44 | 0.9500 |
C7—H7 | 0.9500 | C45—H45 | 0.9500 |
C8—C9 | 1.427 (6) | C46—O47 | 1.211 (6) |
C8—H8 | 0.9500 | C46—O48 | 1.359 (2) |
C9—N22 | 1.358 (5) | O48—H48 | 0.8400 |
C9—C10 | 1.420 (6) | C49—C54 | 1.392 (6) |
C10—C11 | 1.431 (5) | C49—C50 | 1.427 (5) |
C10—C31 | 1.502 (6) | C50—C51 | 1.392 (6) |
C11—N23 | 1.381 (5) | C50—H50 | 0.9500 |
C11—C12 | 1.405 (6) | C51—C52 | 1.343 (6) |
C12—C13 | 1.394 (6) | C51—H51 | 0.9500 |
C12—H12 | 0.9500 | C52—C53 | 1.427 (5) |
C13—C14 | 1.414 (6) | C52—C55 | 1.486 (6) |
C13—H13 | 0.9500 | C53—C54 | 1.356 (6) |
C14—N23 | 1.386 (5) | C53—H53 | 0.9500 |
C14—C15 | 1.412 (5) | C54—H54 | 0.9500 |
C15—C16 | 1.436 (6) | C55—O56 | 1.188 (5) |
C15—C40 | 1.471 (5) | C55—O57 | 1.344 (5) |
C16—N24 | 1.365 (5) | O57—H57 | 0.8400 |
C16—C17 | 1.517 (6) | C58—C63 | 1.347 (2) |
C17—C18 | 1.325 (6) | C58—C59 | 1.353 (6) |
C17—H17 | 0.9500 | C58—H58 | 0.9500 |
C18—C19 | 1.488 (5) | C59—N60 | 1.342 (6) |
C18—H18 | 0.9500 | C59—H59 | 0.9500 |
C19—C20 | 1.369 (6) | N60—C61 | 1.339 (5) |
C19—N24 | 1.381 (5) | C61—C62 | 1.338 (7) |
C20—C49 | 1.529 (6) | C61—H61 | 0.9500 |
N21—H21 | 0.8800 | C62—C63 | 1.397 (6) |
N22—H22 | 0.8800 | C62—H62 | 0.9500 |
N23—H23 | 0.8800 | C63—C64 | 1.443 (7) |
N24—H24 | 0.8800 | C64—O65 | 1.282 (5) |
C25—C30 | 1.348 (2) | C64—C66 | 1.510 (7) |
C25—C26 | 1.384 (5) | C66—H66A | 0.9800 |
C26—C27 | 1.363 (5) | C66—H66B | 0.9800 |
C26—H26 | 0.9500 | C66—H66C | 0.9800 |
C27—N28 | 1.315 (2) | C67—C68 | 1.399 (6) |
C27—H27 | 0.9500 | C67—C72 | 1.415 (4) |
N28—C29 | 1.308 (7) | C67—H67 | 0.9500 |
C29—C30 | 1.397 (6) | C68—N69 | 1.325 (6) |
C29—H29 | 0.9500 | C68—H68 | 0.9500 |
C30—H30 | 0.9500 | N69—C70 | 1.3444 (19) |
C31—C32 | 1.375 (5) | C70—C71 | 1.408 (6) |
C31—C36 | 1.405 (6) | C70—H70 | 0.9500 |
C32—C33 | 1.384 (6) | C71—C72 | 1.365 (6) |
C32—H32 | 0.9500 | C71—H71 | 0.9500 |
C33—C34 | 1.438 (6) | C72—C73 | 1.552 (6) |
C33—H33 | 0.9500 | C73—O74 | 1.166 (5) |
C34—C35 | 1.358 (5) | C73—C75 | 1.470 (6) |
C34—C37 | 1.499 (6) | C75—H75A | 0.9800 |
C35—C36 | 1.385 (6) | C75—H75B | 0.9800 |
C35—H35 | 0.9500 | C75—H75C | 0.9800 |
| | | |
C20—C1—N21 | 124.7 (4) | C36—C35—H35 | 118.7 |
C20—C1—C2 | 130.3 (4) | C35—C36—C31 | 118.4 (4) |
N21—C1—C2 | 105.1 (4) | C35—C36—H36 | 120.8 |
C3—C2—C1 | 108.9 (4) | C31—C36—H36 | 120.8 |
C3—C2—H2 | 125.5 | O38—C37—O39 | 123.3 (5) |
C1—C2—H2 | 125.5 | O38—C37—C34 | 124.4 (5) |
C2—C3—C4 | 110.1 (5) | O39—C37—C34 | 112.2 (4) |
C2—C3—H3 | 124.9 | C37—O39—H39 | 109.5 |
C4—C3—H3 | 124.9 | C41—C40—C45 | 120.0 |
N21—C4—C5 | 124.5 (4) | C41—C40—C15 | 120.4 (3) |
N21—C4—C3 | 105.8 (4) | C45—C40—C15 | 119.6 (3) |
C5—C4—C3 | 129.6 (4) | C40—C41—C42 | 120.0 |
C6—C5—C4 | 129.6 (4) | C40—C41—H41 | 120.0 |
C6—C5—C25 | 117.6 (4) | C42—C41—H41 | 120.0 |
C4—C5—C25 | 112.8 (4) | C43—C42—C41 | 120.0 |
C5—C6—N22 | 125.3 (4) | C43—C42—H42 | 120.0 |
C5—C6—C7 | 125.4 (4) | C41—C42—H42 | 120.0 |
N22—C6—C7 | 109.3 (4) | C42—C43—C44 | 120.0 |
C8—C7—C6 | 109.3 (4) | C42—C43—C46 | 125.2 (3) |
C8—C7—H7 | 125.4 | C44—C43—C46 | 114.8 (3) |
C6—C7—H7 | 125.4 | C45—C44—C43 | 120.0 |
C7—C8—C9 | 104.7 (4) | C45—C44—H44 | 120.0 |
C7—C8—H8 | 127.7 | C43—C44—H44 | 120.0 |
C9—C8—H8 | 127.7 | C44—C45—C40 | 120.0 |
N22—C9—C10 | 124.8 (4) | C44—C45—H45 | 120.0 |
N22—C9—C8 | 111.8 (4) | C40—C45—H45 | 120.0 |
C10—C9—C8 | 123.4 (4) | O47—C46—O48 | 120.3 (5) |
C9—C10—C11 | 124.0 (4) | O47—C46—C43 | 120.2 (5) |
C9—C10—C31 | 119.8 (4) | O48—C46—C43 | 119.6 (4) |
C11—C10—C31 | 116.1 (3) | C46—O48—H48 | 109.5 |
N23—C11—C12 | 108.1 (4) | C54—C49—C50 | 117.7 (4) |
N23—C11—C10 | 125.3 (4) | C54—C49—C20 | 123.0 (4) |
C12—C11—C10 | 126.6 (4) | C50—C49—C20 | 119.3 (4) |
C13—C12—C11 | 108.2 (4) | C51—C50—C49 | 118.2 (4) |
C13—C12—H12 | 125.9 | C51—C50—H50 | 120.9 |
C11—C12—H12 | 125.9 | C49—C50—H50 | 120.9 |
C12—C13—C14 | 106.9 (4) | C52—C51—C50 | 122.9 (4) |
C12—C13—H13 | 126.6 | C52—C51—H51 | 118.5 |
C14—C13—H13 | 126.5 | C50—C51—H51 | 118.5 |
N23—C14—C15 | 127.3 (4) | C51—C52—C53 | 119.5 (4) |
N23—C14—C13 | 108.3 (4) | C51—C52—C55 | 120.8 (4) |
C15—C14—C13 | 124.4 (4) | C53—C52—C55 | 119.8 (4) |
C14—C15—C16 | 123.5 (4) | C54—C53—C52 | 118.3 (4) |
C14—C15—C40 | 118.7 (4) | C54—C53—H53 | 120.8 |
C16—C15—C40 | 117.7 (3) | C52—C53—H53 | 120.8 |
N24—C16—C15 | 127.3 (4) | C53—C54—C49 | 123.3 (4) |
N24—C16—C17 | 110.5 (4) | C53—C54—H54 | 118.3 |
C15—C16—C17 | 122.2 (4) | C49—C54—H54 | 118.3 |
C18—C17—C16 | 105.7 (4) | O56—C55—O57 | 123.1 (4) |
C18—C17—H17 | 127.2 | O56—C55—C52 | 121.4 (4) |
C16—C17—H17 | 127.2 | O57—C55—C52 | 115.5 (4) |
C17—C18—C19 | 107.9 (4) | C55—O57—H57 | 109.5 |
C17—C18—H18 | 126.1 | C63—C58—C59 | 124.3 (5) |
C19—C18—H18 | 126.1 | C63—C58—H58 | 117.9 |
C20—C19—N24 | 125.9 (4) | C59—C58—H58 | 117.8 |
C20—C19—C18 | 124.1 (4) | N60—C59—C58 | 119.6 (4) |
N24—C19—C18 | 110.0 (4) | N60—C59—H59 | 120.2 |
C1—C20—C19 | 126.8 (4) | C58—C59—H59 | 120.2 |
C1—C20—C49 | 114.7 (4) | C59—N60—C61 | 116.5 (5) |
C19—C20—C49 | 117.9 (4) | C62—C61—N60 | 125.8 (5) |
C4—N21—C1 | 110.1 (3) | C62—C61—H61 | 117.1 |
C4—N21—H21 | 124.9 | N60—C61—H61 | 117.1 |
C1—N21—H21 | 125.0 | C61—C62—C63 | 117.8 (4) |
C9—N22—C6 | 104.9 (3) | C61—C62—H62 | 121.1 |
C9—N22—H22 | 127.6 | C63—C62—H62 | 121.1 |
C6—N22—H22 | 127.6 | C58—C63—C62 | 115.8 (4) |
C14—N23—C11 | 108.4 (4) | C58—C63—C64 | 124.2 (4) |
C14—N23—H23 | 125.8 | C62—C63—C64 | 120.0 (4) |
C11—N23—H23 | 125.8 | O65—C64—C63 | 119.1 (4) |
C16—N24—C19 | 105.9 (3) | O65—C64—C66 | 118.0 (5) |
C16—N24—H24 | 127.0 | C63—C64—C66 | 122.3 (4) |
C19—N24—H24 | 127.0 | C64—C66—H66A | 109.5 |
C30—C25—C26 | 115.3 (4) | C64—C66—H66B | 109.4 |
C30—C25—C5 | 122.8 (4) | H66A—C66—H66B | 109.5 |
C26—C25—C5 | 121.9 (4) | C64—C66—H66C | 109.5 |
C27—C26—C25 | 122.2 (4) | H66A—C66—H66C | 109.5 |
C27—C26—H26 | 118.9 | H66B—C66—H66C | 109.5 |
C25—C26—H26 | 118.9 | C68—C67—C72 | 115.1 (4) |
N28—C27—C26 | 121.6 (4) | C68—C67—H67 | 122.5 |
N28—C27—H27 | 119.2 | C72—C67—H67 | 122.4 |
C26—C27—H27 | 119.2 | N69—C68—C67 | 124.9 (4) |
C29—N28—C27 | 117.3 (4) | N69—C68—H68 | 117.5 |
N28—C29—C30 | 123.7 (5) | C67—C68—H68 | 117.5 |
N28—C29—H29 | 118.2 | C68—N69—C70 | 119.2 (4) |
C30—C29—H29 | 118.2 | N69—C70—C71 | 120.3 (4) |
C25—C30—C29 | 119.6 (4) | N69—C70—H70 | 119.9 |
C25—C30—H30 | 120.2 | C71—C70—H70 | 119.9 |
C29—C30—H30 | 120.2 | C72—C71—C70 | 119.8 (4) |
C32—C31—C36 | 119.5 (4) | C72—C71—H71 | 120.1 |
C32—C31—C10 | 123.7 (4) | C70—C71—H71 | 120.1 |
C36—C31—C10 | 116.8 (4) | C71—C72—C67 | 120.5 (4) |
C31—C32—C33 | 122.7 (4) | C71—C72—C73 | 120.1 (4) |
C31—C32—H32 | 118.7 | C67—C72—C73 | 119.4 (4) |
C33—C32—H32 | 118.7 | O74—C73—C75 | 122.9 (4) |
C32—C33—C34 | 117.2 (4) | O74—C73—C72 | 120.5 (4) |
C32—C33—H33 | 121.4 | C75—C73—C72 | 116.4 (4) |
C34—C33—H33 | 121.4 | C73—C75—H75A | 109.5 |
C35—C34—C33 | 119.6 (4) | C73—C75—H75B | 109.5 |
C35—C34—C37 | 123.8 (4) | H75A—C75—H75B | 109.5 |
C33—C34—C37 | 116.6 (4) | C73—C75—H75C | 109.5 |
C34—C35—C36 | 122.6 (4) | H75A—C75—H75C | 109.5 |
C34—C35—H35 | 118.7 | H75B—C75—H75C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O39—H39···N69 | 0.84 | 1.82 | 2.653 (4) | 172 |
O57—H57···N60 | 0.84 | 1.79 | 2.630 (5) | 175 |
O48—H48···N28i | 0.84 | 1.77 | 2.596 (5) | 167 |
C29—H29···O47ii | 0.95 | 2.68 | 3.273 (8) | 121 |
C61—H61···O56 | 0.95 | 2.75 | 3.375 (7) | 124 |
C70—H70···O38 | 0.95 | 2.61 | 3.221 (5) | 123 |
Symmetry codes: (i) x−1, y, z+1; (ii) x+1, y, z−1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C46H29N5O6·2.5C2H6SO | C46H29N5O6·2C7H7NO·10C4H8O |
Mr | 943.06 | 1711.05 |
Crystal system, space group | Monoclinic, Cc | Triclinic, P1 |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 6.5978 (3), 29.2458 (15), 28.6630 (13) | 7.6005 (3), 15.6609 (10), 18.6149 (12) |
α, β, γ (°) | 90, 90.521 (2), 90 | 77.718 (3), 89.630 (4), 78.805 (4) |
V (Å3) | 5530.5 (5) | 2122.4 (2) |
Z | 4 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.17 | 0.09 |
Crystal size (mm) | 0.40 × 0.20 × 0.03 | 0.40 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18496, 11808, 6211 | 24317, 10109, 4725 |
Rint | 0.071 | 0.060 |
(sin θ/λ)max (Å−1) | 0.657 | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.085, 0.211, 1.06 | 0.052, 0.135, 0.80 |
No. of reflections | 11808 | 10109 |
No. of parameters | 594 | 669 |
No. of restraints | 2 | 8 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −0.31 | 0.25, −0.20 |
Absolute structure | Flack (1983), 5242 Friedel pairs | ? |
Absolute structure parameter | 0.42 (12) | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O56—H56···O59 | 0.84 | 1.78 | 2.565 (6) | 154 |
O48—H48···O63 | 0.84 | 1.82 | 2.599 (5) | 154 |
O39—H39···O63i | 0.84 | 1.79 | 2.624 (5) | 169 |
C17—H17···N28ii | 0.95 | 2.55 | 3.387 (6) | 147 |
Symmetry codes: (i) x−1, −y+1, z−1/2; (ii) x+1/2, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O39—H39···N69 | 0.84 | 1.82 | 2.653 (4) | 172 |
O57—H57···N60 | 0.84 | 1.79 | 2.630 (5) | 175 |
O48—H48···N28i | 0.84 | 1.77 | 2.596 (5) | 167 |
C29—H29···O47ii | 0.95 | 2.68 | 3.273 (8) | 121 |
C61—H61···O56 | 0.95 | 2.75 | 3.375 (7) | 124 |
C70—H70···O38 | 0.95 | 2.61 | 3.221 (5) | 123 |
Symmetry codes: (i) x−1, y, z+1; (ii) x+1, y, z−1. |
Following our earlier studies on the designed construction of framework solids from symmetrically functionalized porphyrin building blocks of square-planar D4h symmetry (Goldberg, 2005, and references therein), the supramolecular chemistry of porphyrin derivatives of reduced symmetry has also deserved considerable attention (Vinodu & Goldberg, 2003; George & Goldberg, 2006; George et al., 2006). Within this context, porphyrin cores substituted with either four, three or two carboxylic acid functions of complementary hydrogen-bonding capacity have been investigated (Diskin-Posner & Goldberg, 1999; Vinodu & Goldberg, 2003, 2004). In most cases, the predominant propensity of such porphyrin species to associate directly via the cyclic dimeric (COOH)2 hydrogen-bonding synthon into polymeric arrays has been demonstrated. However, disruption of this binding mode may occur in the presence of strong pyridyl- and sulfoxide-type Lewis base reagents, owing to competing solvation (Lipstman et al., 2006; George et al., 2006). Thus, lipophilic species, such as dimethyl sulfoxide (DMSO) or 4-acetylpyridine, reveal preferential affinity to associate to the carboxylic acid functions via hydrogen bonds, in competition with the alternative (COOH)2 self-association of the porphyrin units. Furthermore, in porphyrins that bear both the 3-pyridyl as well as the 4-carboxyphenyl functions, intermolecular COOH···pyridyl hydrogen bonding has been observed (Vinodu & Goldberg, 2005).
Within the above context, we report here on the synthesis of the title porphyrin compound, and the structures of its 1:2 adducts with dimethyl sulfoxide, (I), and 4-acetylpyridine, (II), that crystallized as dimethyl sulfoxide and tetrahydrofuran solvates, respectively.
As shown previously, the present study also reveals preferential formation of COOH···O═S and COOH···Npyridine hydrogen bonds, rather than the (COOH)2 interactions. Figs. 1 and 2 depict the molecular structures of adducts (I) and (II), respectively. The DMSO species is a strong acceptor of H atoms in hydrogen bonds, which can associate with either one or two COOH H-atom donors. In (I), they solvate completely the three carboxylic acid groups by relatively strong OH···O═S hydrogen bonds with O···O distances ranging from 2.565 (6) to 2.624 (5) Å (Table 1). While one molecule of DMSO connects to a single COOH group, the other ligand bridges between two neighboring units, thus giving rise to the formation of heterogeneous porphyrin–DMSO hydrogen-bonded zigzag polymeric arrays (Fig. 3). The crystal packing of these chains is associated with occlusion of additional uncoordinated molecules of DMSO between these chains in a disordered manner. It is of further interest to note that in the presence of very strong hydrogen bond acceptors, such as DMSO in excess, the porphyrin's pyridyl function (a somewhat weaker acceptor) is not involved in interporphyrin hydrogen bonds with the carboxylic acid groups, as observed earlier (Vinodu & Goldberg, 2004, 2003). Rather, it is involved in a weak C—H···N contact with a neighboring porphyrin unit (Table 1).
When the DMSO is replaced by a 4-acetylpyridine reagent in the crystallization mixture, a different intermolecular binding pattern emerges. Now the 4-acetylpyridine and the porphyrin-bound pyridyl groups have similar affinity, as hydrogen-bond acceptors, for the formation of COOH···N hydrogen bonds. This is well expressed in the observed structure of (II), crystallized from a 1:1 mixture of 4-acetylpyridine and tetrahydrofuran (THF, which is a very weak H-atom acceptor in hydrogen bonds). Thus, in order to optimally satisfy the hydorgen-bonding capacity of the porphyrin and the 4-acetylpyridine groups, one unit of the former associates with two units of the latter, wherein two of the carboxylic acid functions are solvated by two molecules of 4-acetylpyridine via COOH···N hydrogen bonds. In addition, the porphyrin scaffolds self-associate into homogeneous linear polymeric chains via COOH···N(pyridyl) hydrogen bonds (Fig. 4). The corresponding O···N distances range from 2.596 (5) to 2.653 (4) Å (Table 2). In this arrangement, the hydorgen-bonding potential of all COOH and N(pyridine/pyridyl) sites is used optimally. Side packing of these chains creates open layers, which in turn stack one on top of the other, yielding a stable structure at room temperature. This stability may be attributed to attractive dispersion between the large aromatic surfaces of adjacent layers, as well as to additional weak C—H···O interactions between the molecular entities (Table 2). The crystal packing of the supramolecular arrays creates very wide interporphyrin voids, which propagate parallel to the a axis, accommodating severely diffuse THF solvent molecules (Fig. 5). The van der Waals width of these canals is about 9–10 Å.
This study, along with our earlier observations, confirms the hierarchy of the hydrogen-bonding interactions expressed in the supramolecular assembly of the carboxyphenylporphyrin materials: the COOH···O═S synthon appears more stable than the COOH···N(pyridine) one, while the (COOH)2 interaction seems to be the least preferred among the three types (Lipstman et al., 2006; George et al., 2006; Etter, 1990, 1991). Owing to severe solubility problems, we have not been able so far to crystallize two-dimensionally hydrogen-bonded supramolecular arrays of the title porphyrin compound in the absence of the competing solvents, as was achieved successfully with the tetracarboxyphenyl (Diskin-Posner & Goldberg, 1999) and 3-pyridyltris(4-carboxyphenyl) (Vinodu & Goldberg, 2005) derivatives. Only one single-crystal structure of a compound containing 4-pyridyl and 4-carboxyphenyl functional substituents on the same porphyrin framework has ever been published before (Redman et al., 2001).