Unsolvated 5,10,15,20-tetra-4-pyridylporphyrin, C
40H
26N
8, (I), its sesquihydrate, C
40H
26N
8·1.514H
2O, (II), and its 2-chlorophenol disolvate, C
40H
26N
8·2C
6H
5ClO, (III), reveal different conformational features of the porphyrin core. In (I), the latter is severely deformed from planarity, apparently in order to optimize the intermolecular interactions and efficient crystal packing of the molecular entities. The molecular framework has a
C1 symmetry. In (II), the porphyrin molecules are located on
symmetry axes, preserving the marked deformation from planarity of the porphyrin core. The molecular units are interlinked into a single-framework supramolecular architecture by hydrogen bonding to one another
via molecules of water, which lie on twofold rotation axes. In (III), the porphyrin molecules are located across centres of inversion and are characterized by a planar conformation of the 24-membered macrocyclic porphyrin ring. Two
trans-related pyridyl substituents are hydrogen bonded to the 2-chlorophenol solvent molecules. The interporphyrin organization in (III) is similar to that observed for many other tetraarylporphyrin compounds. However, the organization observed in (I) and (II) is different and of a type rarely observed before. This study reports for the first time the crystal structure of the unsolvated tetrapyridylporphyrin.
Supporting information
CCDC references: 749711; 749712; 749714
The porphyrin compound, as well as all the other reactants and solvents (see
below) were obtained commercially. Crystals of (I) and (II) were obtained as
by-products during attempts to synthesize coordination networks of the
porphyrin moiety with lanthanide ions. Crystals of (I) were obtained by slow
diffusion between layers: TPyP (0.011 mmol) was dissolved in 2 ml of a 1:1
(v/v) methanol:tetrachloroethane mixture, which was heated under
reflux for 2 h and then filtered. A solution of lanthanum chloride
heptahydrate (0.9 mmol) in 5 ml of a 5:3 (v/v) mixture of
methanol and dimethylformamide was carefully layered on top of the TPyP
solution. Crystals were obtained in the porphyrin phase after 12 d. Compound
(I) was obtained in a similar experiment while using gadolinium nitrate
hexahydrate instead of the lanthanum salt. For (II), TPyP (0.013 mmol) and
lanthanum nitrate hexahydrate (0.092 mmol) dissolved in 15 ml of a 1:1
(v/v) mixture of methanol and 1,2-dichlorobenzene. The resulting
solution was heated under reflux, filtered and the solute was kept for
crystallization by slow evaporation. X-ray quality crystals were obtained
after one month. In the third case, an attempt to synthesize hydrogen-bonding
supramolecular networks by reacting TPyP with 2,5-thiophenedicarboxylic acid
(TPDA) failed, yielding instead compound (III). TPyP (0.006 mmol) and TPDA
(0.02 mmol) were dissolved in 5 ml of MeOH containing a few drops of
2-chlorophenol. The resulting solution was heated under reflux for 10 min and
then filtered. Using the slow vapour diffusion method, an open vial of the
solute was placed in a closed vessel with diethyl ether. Crystals of (III)
appeared after one day.
In all three compounds, H atoms bound to C atoms were located in calculated
positions and were constrained to ride on their parent atoms with C—H
distances of 0.95 Å and with Uiso(H) values of 1.2 Ueq(C).
The two N(pyrrole)-bound H atoms were found to be disordered between
the four pyrrole sites. They were located also in calculated positions,
constrained to ride on their parent atoms with N—H distances of 0.88 Å and
with Uiso(H) of 1.2Ueq(N). The H atom bound to O32 in (III)
was located in a difference Fourier map, but its position was not refined. The
water H atom in the asymmetric unit of (II) could not be located reliably, as
the residual electron density peaks which could correspond to this H atom were
very low. One of these peaks was assigned as the H atom, and its position was
restrained in the refinement at an O—H distance of 0.95 (s.u.value?)
Å. These H atoms were assigned Uiso(H) values of 1.5 or 1.2 times
Ueq(O), in (II) and (III), respectively. The refined site occupancy
of the water molecule in (II) was 0.757 (10) for the crystal selected for data
collection, which corresponds approximately to the sesquihydrate with a 1:1.5
porphyrin:water stoichiometry. 14 reflections in (I) and 1 reflection in (II)
were omitted from the final structure factors calculations because of poor
assessment of the intensities (oversaturated or overlapping reflections).
For all compounds, data collection: Collect (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 5,10,15,20-tetra-4-pyridylporphyrin
top
Crystal data top
C40H26N8 | F(000) = 1288 |
Mr = 618.69 | Dx = 1.409 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 4891 reflections |
a = 13.6042 (2) Å | θ = 2.0–27.9° |
b = 20.8734 (4) Å | µ = 0.09 mm−1 |
c = 11.4525 (2) Å | T = 110 K |
β = 116.2786 (11)° | Prism, red |
V = 2916.02 (9) Å3 | 0.40 × 0.40 × 0.30 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 3032 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 27.9°, θmin = 2.0° |
Detector resolution: 12.8 pixels mm-1 | h = −17→17 |
1 deg. ϕ and ω scans | k = −26→27 |
16180 measured reflections | l = −14→14 |
3456 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0818P)2 + 0.7758P] where P = (Fo2 + 2Fc2)/3 |
3456 reflections | (Δ/σ)max < 0.001 |
433 parameters | Δρmax = 0.38 e Å−3 |
2 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C40H26N8 | V = 2916.02 (9) Å3 |
Mr = 618.69 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 13.6042 (2) Å | µ = 0.09 mm−1 |
b = 20.8734 (4) Å | T = 110 K |
c = 11.4525 (2) Å | 0.40 × 0.40 × 0.30 mm |
β = 116.2786 (11)° | |
Data collection top
Nonius KappaCCD diffractometer | 3032 reflections with I > 2σ(I) |
16180 measured reflections | Rint = 0.057 |
3456 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 2 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.38 e Å−3 |
3456 reflections | Δρmin = −0.28 e Å−3 |
433 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 Friedel opposites were merged. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.0339 (2) | 0.24370 (14) | −0.2566 (3) | 0.0202 (6) | |
C2 | 0.0474 (2) | 0.31233 (14) | −0.2507 (3) | 0.0212 (6) | |
H2 | 0.0304 | 0.3405 | −0.3223 | 0.025* | |
C3 | 0.0891 (3) | 0.32897 (14) | −0.1234 (3) | 0.0220 (6) | |
H3 | 0.1051 | 0.3712 | −0.0890 | 0.026* | |
C4 | 0.1048 (3) | 0.27065 (14) | −0.0497 (3) | 0.0201 (6) | |
C5 | 0.1562 (2) | 0.26725 (13) | 0.0868 (3) | 0.0187 (6) | |
C6 | 0.1961 (2) | 0.21059 (14) | 0.1593 (3) | 0.0200 (6) | |
C7 | 0.2548 (3) | 0.20409 (15) | 0.2989 (3) | 0.0226 (6) | |
H7 | 0.2692 | 0.2372 | 0.3613 | 0.027* | |
C8 | 0.2858 (2) | 0.14173 (14) | 0.3243 (3) | 0.0211 (6) | |
H8 | 0.3281 | 0.1238 | 0.4080 | 0.025* | |
C9 | 0.2437 (2) | 0.10768 (14) | 0.2032 (3) | 0.0187 (6) | |
C10 | 0.2487 (2) | 0.04133 (14) | 0.1888 (3) | 0.0201 (6) | |
C11 | 0.1829 (3) | 0.00596 (15) | 0.0776 (3) | 0.0215 (6) | |
C12 | 0.1829 (3) | −0.06329 (14) | 0.0671 (3) | 0.0231 (6) | |
H12 | 0.2313 | −0.0922 | 0.1305 | 0.028* | |
C13 | 0.1009 (3) | −0.07875 (14) | −0.0501 (3) | 0.0232 (6) | |
H13 | 0.0781 | −0.1208 | −0.0828 | 0.028* | |
C14 | 0.0542 (2) | −0.01921 (14) | −0.1167 (3) | 0.0197 (6) | |
C15 | −0.0269 (2) | −0.01431 (14) | −0.2459 (3) | 0.0202 (6) | |
C16 | −0.0536 (2) | 0.04217 (14) | −0.3198 (3) | 0.0209 (6) | |
C17 | −0.1245 (3) | 0.04743 (15) | −0.4573 (3) | 0.0231 (6) | |
H17 | −0.1688 | 0.0143 | −0.5125 | 0.028* | |
C18 | −0.1163 (3) | 0.10833 (14) | −0.4936 (3) | 0.0220 (6) | |
H18 | −0.1517 | 0.1251 | −0.5795 | 0.026* | |
C19 | −0.0445 (2) | 0.14280 (14) | −0.3792 (3) | 0.0190 (6) | |
C20 | −0.0180 (2) | 0.20798 (13) | −0.3725 (3) | 0.0183 (6) | |
N21 | 0.0704 (2) | 0.21949 (12) | −0.1329 (2) | 0.0200 (5) | |
H21 | 0.0715 | 0.1789 | −0.1114 | 0.024* | 0.50 |
N22 | 0.1889 (2) | 0.15073 (12) | 0.1047 (2) | 0.0191 (5) | |
H22 | 0.1551 | 0.1417 | 0.0211 | 0.023* | 0.50 |
N23 | 0.1046 (2) | 0.03168 (12) | −0.0365 (2) | 0.0209 (5) | |
H23 | 0.0898 | 0.0726 | −0.0543 | 0.025* | 0.50 |
N24 | −0.0074 (2) | 0.10116 (11) | −0.2752 (2) | 0.0200 (5) | |
H24 | 0.0381 | 0.1107 | −0.1942 | 0.024* | 0.50 |
C25 | 0.1744 (3) | 0.32853 (14) | 0.1604 (3) | 0.0205 (6) | |
C26 | 0.0863 (3) | 0.36891 (15) | 0.1400 (3) | 0.0256 (6) | |
H26 | 0.0139 | 0.3575 | 0.0797 | 0.031* | |
C27 | 0.1060 (3) | 0.42579 (16) | 0.2090 (3) | 0.0306 (7) | |
H27 | 0.0450 | 0.4524 | 0.1943 | 0.037* | |
N28 | 0.2055 (3) | 0.44571 (13) | 0.2949 (3) | 0.0320 (6) | |
C29 | 0.2892 (3) | 0.40652 (16) | 0.3130 (3) | 0.0290 (7) | |
H29 | 0.3608 | 0.4194 | 0.3733 | 0.035* | |
C30 | 0.2783 (3) | 0.34868 (15) | 0.2499 (3) | 0.0245 (6) | |
H30 | 0.3408 | 0.3229 | 0.2673 | 0.029* | |
C31 | 0.3313 (2) | 0.00532 (14) | 0.3037 (3) | 0.0209 (6) | |
C32 | 0.4426 (3) | 0.01395 (15) | 0.3427 (3) | 0.0266 (6) | |
H32 | 0.4675 | 0.0436 | 0.2987 | 0.032* | |
C33 | 0.5172 (3) | −0.02154 (17) | 0.4470 (3) | 0.0311 (7) | |
H33 | 0.5930 | −0.0163 | 0.4704 | 0.037* | |
N34 | 0.4889 (2) | −0.06267 (14) | 0.5166 (3) | 0.0304 (6) | |
C35 | 0.3813 (3) | −0.07006 (17) | 0.4785 (3) | 0.0301 (7) | |
H35 | 0.3589 | −0.0989 | 0.5263 | 0.036* | |
C36 | 0.3000 (3) | −0.03804 (16) | 0.3729 (3) | 0.0272 (7) | |
H36 | 0.2246 | −0.0458 | 0.3489 | 0.033* | |
C37 | −0.0888 (2) | −0.07341 (14) | −0.3114 (3) | 0.0202 (6) | |
C38 | −0.0404 (3) | −0.12450 (15) | −0.3452 (3) | 0.0251 (6) | |
H38 | 0.0350 | −0.1229 | −0.3259 | 0.030* | |
C39 | −0.1030 (3) | −0.17750 (16) | −0.4070 (3) | 0.0275 (7) | |
H39 | −0.0682 | −0.2119 | −0.4284 | 0.033* | |
N40 | −0.2097 (2) | −0.18314 (13) | −0.4383 (3) | 0.0273 (6) | |
C41 | −0.2552 (3) | −0.13438 (15) | −0.4046 (3) | 0.0248 (6) | |
H41 | −0.3307 | −0.1376 | −0.4246 | 0.030* | |
C42 | −0.1997 (2) | −0.07922 (14) | −0.3421 (3) | 0.0220 (6) | |
H42 | −0.2366 | −0.0460 | −0.3206 | 0.026* | |
C43 | −0.0491 (3) | 0.24248 (14) | −0.4984 (3) | 0.0207 (6) | |
C44 | −0.1560 (3) | 0.25976 (16) | −0.5808 (3) | 0.0286 (7) | |
H44 | −0.2139 | 0.2490 | −0.5594 | 0.034* | |
C45 | −0.1778 (3) | 0.29275 (18) | −0.6945 (3) | 0.0347 (8) | |
H45 | −0.2518 | 0.3036 | −0.7498 | 0.042* | |
N46 | −0.1013 (3) | 0.31039 (15) | −0.7317 (3) | 0.0347 (7) | |
C47 | 0.0012 (3) | 0.29286 (17) | −0.6517 (3) | 0.0331 (8) | |
H47 | 0.0574 | 0.3043 | −0.6756 | 0.040* | |
C48 | 0.0314 (3) | 0.25937 (15) | −0.5369 (3) | 0.0260 (6) | |
H48 | 0.1059 | 0.2480 | −0.4850 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0192 (14) | 0.0203 (14) | 0.0187 (13) | −0.0015 (11) | 0.0062 (11) | 0.0014 (11) |
C2 | 0.0239 (15) | 0.0188 (14) | 0.0188 (13) | 0.0002 (11) | 0.0075 (11) | 0.0027 (11) |
C3 | 0.0256 (15) | 0.0168 (13) | 0.0222 (14) | −0.0024 (11) | 0.0094 (12) | 0.0006 (11) |
C4 | 0.0216 (15) | 0.0187 (14) | 0.0198 (13) | 0.0013 (11) | 0.0090 (12) | 0.0000 (10) |
C5 | 0.0206 (15) | 0.0167 (14) | 0.0177 (13) | −0.0028 (11) | 0.0075 (11) | −0.0016 (10) |
C6 | 0.0214 (15) | 0.0208 (14) | 0.0169 (13) | −0.0037 (11) | 0.0077 (11) | −0.0021 (11) |
C7 | 0.0272 (16) | 0.0207 (14) | 0.0165 (13) | −0.0013 (12) | 0.0065 (12) | −0.0013 (10) |
C8 | 0.0223 (15) | 0.0210 (14) | 0.0162 (13) | 0.0003 (11) | 0.0051 (11) | −0.0009 (11) |
C9 | 0.0200 (14) | 0.0185 (13) | 0.0161 (13) | 0.0009 (11) | 0.0067 (11) | 0.0028 (10) |
C10 | 0.0237 (15) | 0.0196 (13) | 0.0168 (13) | 0.0016 (11) | 0.0088 (12) | 0.0024 (11) |
C11 | 0.0231 (15) | 0.0210 (14) | 0.0193 (13) | 0.0003 (11) | 0.0086 (11) | 0.0028 (11) |
C12 | 0.0275 (16) | 0.0189 (14) | 0.0188 (14) | 0.0016 (12) | 0.0067 (12) | 0.0010 (11) |
C13 | 0.0281 (16) | 0.0172 (13) | 0.0217 (14) | 0.0021 (12) | 0.0087 (12) | 0.0005 (11) |
C14 | 0.0172 (13) | 0.0193 (14) | 0.0202 (13) | −0.0008 (11) | 0.0061 (11) | −0.0002 (11) |
C15 | 0.0217 (14) | 0.0172 (13) | 0.0193 (13) | −0.0014 (11) | 0.0068 (11) | −0.0024 (11) |
C16 | 0.0213 (15) | 0.0192 (14) | 0.0207 (14) | 0.0001 (11) | 0.0079 (12) | −0.0009 (11) |
C17 | 0.0258 (16) | 0.0214 (15) | 0.0186 (13) | −0.0014 (12) | 0.0068 (12) | −0.0045 (11) |
C18 | 0.0250 (16) | 0.0205 (14) | 0.0160 (13) | −0.0006 (12) | 0.0050 (11) | −0.0003 (11) |
C19 | 0.0227 (14) | 0.0168 (13) | 0.0164 (13) | −0.0012 (10) | 0.0078 (11) | 0.0004 (10) |
C20 | 0.0190 (14) | 0.0173 (13) | 0.0162 (13) | 0.0005 (11) | 0.0058 (11) | 0.0024 (10) |
N21 | 0.0245 (13) | 0.0179 (12) | 0.0153 (11) | 0.0004 (10) | 0.0066 (9) | 0.0001 (9) |
N22 | 0.0209 (12) | 0.0163 (12) | 0.0168 (11) | −0.0003 (9) | 0.0053 (10) | 0.0008 (9) |
N23 | 0.0213 (12) | 0.0205 (12) | 0.0170 (11) | −0.0007 (10) | 0.0051 (10) | 0.0001 (9) |
N24 | 0.0240 (13) | 0.0166 (12) | 0.0175 (11) | −0.0021 (9) | 0.0074 (10) | −0.0014 (9) |
C25 | 0.0298 (16) | 0.0170 (14) | 0.0171 (13) | −0.0026 (11) | 0.0125 (12) | −0.0008 (10) |
C26 | 0.0292 (17) | 0.0253 (16) | 0.0219 (14) | 0.0032 (12) | 0.0110 (13) | 0.0008 (12) |
C27 | 0.047 (2) | 0.0236 (16) | 0.0263 (16) | 0.0078 (14) | 0.0212 (15) | 0.0022 (12) |
N28 | 0.0527 (19) | 0.0211 (13) | 0.0256 (14) | −0.0026 (13) | 0.0205 (13) | −0.0014 (11) |
C29 | 0.0398 (19) | 0.0257 (16) | 0.0212 (14) | −0.0081 (14) | 0.0133 (14) | −0.0036 (12) |
C30 | 0.0303 (16) | 0.0227 (14) | 0.0195 (14) | −0.0058 (12) | 0.0102 (12) | −0.0012 (11) |
C31 | 0.0275 (16) | 0.0171 (13) | 0.0153 (13) | 0.0031 (11) | 0.0071 (12) | −0.0005 (10) |
C32 | 0.0280 (17) | 0.0226 (15) | 0.0246 (14) | 0.0018 (12) | 0.0076 (13) | 0.0013 (12) |
C33 | 0.0288 (17) | 0.0302 (17) | 0.0273 (16) | 0.0049 (14) | 0.0060 (14) | 0.0019 (13) |
N34 | 0.0358 (16) | 0.0285 (15) | 0.0215 (13) | 0.0075 (12) | 0.0078 (12) | 0.0010 (11) |
C35 | 0.039 (2) | 0.0309 (18) | 0.0245 (15) | 0.0105 (14) | 0.0176 (15) | 0.0072 (13) |
C36 | 0.0283 (17) | 0.0303 (16) | 0.0236 (14) | 0.0073 (13) | 0.0121 (13) | 0.0066 (13) |
C37 | 0.0231 (14) | 0.0170 (13) | 0.0181 (13) | −0.0011 (11) | 0.0068 (11) | −0.0001 (10) |
C38 | 0.0230 (15) | 0.0218 (15) | 0.0294 (16) | 0.0016 (12) | 0.0106 (13) | −0.0028 (12) |
C39 | 0.0273 (16) | 0.0195 (14) | 0.0312 (16) | 0.0031 (12) | 0.0088 (13) | −0.0039 (12) |
N40 | 0.0290 (14) | 0.0212 (13) | 0.0275 (13) | −0.0035 (11) | 0.0087 (11) | −0.0015 (10) |
C41 | 0.0234 (15) | 0.0237 (15) | 0.0267 (15) | −0.0018 (12) | 0.0104 (12) | 0.0011 (12) |
C42 | 0.0226 (15) | 0.0192 (14) | 0.0207 (14) | 0.0020 (11) | 0.0063 (12) | 0.0003 (11) |
C43 | 0.0246 (16) | 0.0190 (14) | 0.0149 (12) | −0.0025 (11) | 0.0055 (11) | 0.0002 (11) |
C44 | 0.0222 (16) | 0.0298 (17) | 0.0284 (16) | −0.0026 (13) | 0.0063 (13) | 0.0063 (13) |
C45 | 0.036 (2) | 0.0320 (18) | 0.0226 (16) | −0.0071 (15) | 0.0007 (14) | 0.0066 (13) |
N46 | 0.0494 (18) | 0.0299 (15) | 0.0178 (12) | −0.0110 (13) | 0.0084 (12) | 0.0011 (11) |
C47 | 0.044 (2) | 0.0324 (18) | 0.0271 (16) | −0.0095 (15) | 0.0196 (16) | 0.0000 (13) |
C48 | 0.0303 (17) | 0.0240 (15) | 0.0252 (15) | −0.0037 (12) | 0.0137 (13) | −0.0004 (12) |
Geometric parameters (Å, º) top
C1—N21 | 1.373 (4) | N23—H23 | 0.8800 |
C1—C20 | 1.409 (4) | N24—H24 | 0.8800 |
C1—C2 | 1.442 (4) | C25—C30 | 1.393 (4) |
C2—C3 | 1.355 (4) | C25—C26 | 1.398 (4) |
C2—H2 | 0.9500 | C26—C27 | 1.385 (4) |
C3—C4 | 1.442 (4) | C26—H26 | 0.9500 |
C3—H3 | 0.9500 | C27—N28 | 1.339 (5) |
C4—N21 | 1.369 (4) | C27—H27 | 0.9500 |
C4—C5 | 1.403 (4) | N28—C29 | 1.342 (5) |
C5—C6 | 1.408 (4) | C29—C30 | 1.381 (4) |
C5—C25 | 1.491 (4) | C29—H29 | 0.9500 |
C6—N22 | 1.381 (4) | C30—H30 | 0.9500 |
C6—C7 | 1.443 (4) | C31—C36 | 1.388 (4) |
C7—C8 | 1.359 (4) | C31—C32 | 1.389 (5) |
C7—H7 | 0.9500 | C32—C33 | 1.390 (4) |
C8—C9 | 1.433 (4) | C32—H32 | 0.9500 |
C8—H8 | 0.9500 | C33—N34 | 1.339 (5) |
C9—N22 | 1.375 (4) | C33—H33 | 0.9500 |
C9—C10 | 1.400 (4) | N34—C35 | 1.338 (5) |
C10—C11 | 1.399 (4) | C35—C36 | 1.396 (5) |
C10—C31 | 1.500 (4) | C35—H35 | 0.9500 |
C11—N23 | 1.378 (4) | C36—H36 | 0.9500 |
C11—C12 | 1.451 (4) | C37—C38 | 1.394 (4) |
C12—C13 | 1.351 (4) | C37—C42 | 1.395 (4) |
C12—H12 | 0.9500 | C38—C39 | 1.384 (4) |
C13—C14 | 1.449 (4) | C38—H38 | 0.9500 |
C13—H13 | 0.9500 | C39—N40 | 1.336 (4) |
C14—N23 | 1.373 (4) | C39—H39 | 0.9500 |
C14—C15 | 1.404 (4) | N40—C41 | 1.335 (4) |
C15—C16 | 1.403 (4) | C41—C42 | 1.389 (4) |
C15—C37 | 1.495 (4) | C41—H41 | 0.9500 |
C16—N24 | 1.374 (4) | C42—H42 | 0.9500 |
C16—C17 | 1.441 (4) | C43—C44 | 1.385 (4) |
C17—C18 | 1.357 (4) | C43—C48 | 1.396 (4) |
C17—H17 | 0.9500 | C44—C45 | 1.384 (4) |
C18—C19 | 1.433 (4) | C44—H44 | 0.9500 |
C18—H18 | 0.9500 | C45—N46 | 1.338 (5) |
C19—N24 | 1.377 (4) | C45—H45 | 0.9500 |
C19—C20 | 1.401 (4) | N46—C47 | 1.337 (5) |
C20—C43 | 1.496 (4) | C47—C48 | 1.381 (5) |
N21—H21 | 0.8800 | C47—H47 | 0.9500 |
N22—H22 | 0.8800 | C48—H48 | 0.9500 |
| | | |
N21—C1—C20 | 125.3 (3) | C11—N23—H23 | 126.9 |
N21—C1—C2 | 109.7 (2) | C16—N24—C19 | 108.1 (2) |
C20—C1—C2 | 124.8 (3) | C16—N24—H24 | 125.9 |
C3—C2—C1 | 106.8 (3) | C19—N24—H24 | 125.9 |
C3—C2—H2 | 126.6 | C30—C25—C26 | 117.1 (3) |
C1—C2—H2 | 126.6 | C30—C25—C5 | 122.4 (3) |
C2—C3—C4 | 107.2 (3) | C26—C25—C5 | 120.5 (3) |
C2—C3—H3 | 126.4 | C27—C26—C25 | 119.1 (3) |
C4—C3—H3 | 126.4 | C27—C26—H26 | 120.4 |
N21—C4—C5 | 125.8 (3) | C25—C26—H26 | 120.4 |
N21—C4—C3 | 109.5 (2) | N28—C27—C26 | 124.3 (3) |
C5—C4—C3 | 124.5 (3) | N28—C27—H27 | 117.9 |
C4—C5—C6 | 124.8 (3) | C26—C27—H27 | 117.9 |
C4—C5—C25 | 117.5 (3) | C27—N28—C29 | 115.9 (3) |
C6—C5—C25 | 117.6 (2) | N28—C29—C30 | 124.4 (3) |
N22—C6—C5 | 124.2 (3) | N28—C29—H29 | 117.8 |
N22—C6—C7 | 108.0 (3) | C30—C29—H29 | 117.8 |
C5—C6—C7 | 127.7 (3) | C29—C30—C25 | 119.2 (3) |
C8—C7—C6 | 107.1 (3) | C29—C30—H30 | 120.4 |
C8—C7—H7 | 126.4 | C25—C30—H30 | 120.4 |
C6—C7—H7 | 126.4 | C36—C31—C32 | 117.9 (3) |
C7—C8—C9 | 108.3 (3) | C36—C31—C10 | 121.9 (3) |
C7—C8—H8 | 125.8 | C32—C31—C10 | 120.2 (3) |
C9—C8—H8 | 125.8 | C31—C32—C33 | 119.0 (3) |
N22—C9—C10 | 126.0 (3) | C31—C32—H32 | 120.5 |
N22—C9—C8 | 108.0 (2) | C33—C32—H32 | 120.5 |
C10—C9—C8 | 125.8 (3) | N34—C33—C32 | 124.1 (3) |
C9—C10—C11 | 125.7 (3) | N34—C33—H33 | 118.0 |
C9—C10—C31 | 116.7 (2) | C32—C33—H33 | 118.0 |
C11—C10—C31 | 117.6 (3) | C33—N34—C35 | 116.2 (3) |
N23—C11—C10 | 124.9 (3) | N34—C35—C36 | 124.1 (3) |
N23—C11—C12 | 109.7 (3) | N34—C35—H35 | 118.0 |
C10—C11—C12 | 125.3 (3) | C36—C35—H35 | 118.0 |
C13—C12—C11 | 106.9 (3) | C31—C36—C35 | 118.7 (3) |
C13—C12—H12 | 126.6 | C31—C36—H36 | 120.6 |
C11—C12—H12 | 126.6 | C35—C36—H36 | 120.6 |
C12—C13—C14 | 107.1 (3) | C38—C37—C42 | 117.0 (3) |
C12—C13—H13 | 126.4 | C38—C37—C15 | 122.8 (3) |
C14—C13—H13 | 126.4 | C42—C37—C15 | 120.2 (3) |
N23—C14—C15 | 125.1 (3) | C39—C38—C37 | 119.6 (3) |
N23—C14—C13 | 109.8 (3) | C39—C38—H38 | 120.2 |
C15—C14—C13 | 125.0 (3) | C37—C38—H38 | 120.2 |
C14—C15—C16 | 124.8 (3) | N40—C39—C38 | 123.8 (3) |
C14—C15—C37 | 118.3 (3) | N40—C39—H39 | 118.1 |
C16—C15—C37 | 116.9 (2) | C38—C39—H39 | 118.1 |
N24—C16—C15 | 125.1 (3) | C39—N40—C41 | 116.3 (3) |
N24—C16—C17 | 108.2 (3) | N40—C41—C42 | 124.4 (3) |
C15—C16—C17 | 126.4 (3) | N40—C41—H41 | 117.8 |
C18—C17—C16 | 107.5 (3) | C42—C41—H41 | 117.8 |
C18—C17—H17 | 126.3 | C41—C42—C37 | 118.8 (3) |
C16—C17—H17 | 126.3 | C41—C42—H42 | 120.6 |
C17—C18—C19 | 107.8 (3) | C37—C42—H42 | 120.6 |
C17—C18—H18 | 126.1 | C44—C43—C48 | 116.9 (3) |
C19—C18—H18 | 126.1 | C44—C43—C20 | 123.1 (3) |
N24—C19—C20 | 125.3 (3) | C48—C43—C20 | 120.0 (3) |
N24—C19—C18 | 108.3 (2) | C45—C44—C43 | 119.6 (3) |
C20—C19—C18 | 126.3 (3) | C45—C44—H44 | 120.2 |
C19—C20—C1 | 125.1 (3) | C43—C44—H44 | 120.2 |
C19—C20—C43 | 117.3 (3) | N46—C45—C44 | 124.3 (3) |
C1—C20—C43 | 117.6 (2) | N46—C45—H45 | 117.8 |
C4—N21—C1 | 106.7 (2) | C44—C45—H45 | 117.8 |
C4—N21—H21 | 126.6 | C47—N46—C45 | 115.4 (3) |
C1—N21—H21 | 126.6 | N46—C47—C48 | 124.9 (3) |
C9—N22—C6 | 108.5 (2) | N46—C47—H47 | 117.5 |
C9—N22—H22 | 125.8 | C48—C47—H47 | 117.5 |
C6—N22—H22 | 125.8 | C47—C48—C43 | 118.9 (3) |
C14—N23—C11 | 106.3 (3) | C47—C48—H48 | 120.5 |
C14—N23—H23 | 126.9 | C43—C48—H48 | 120.5 |
(II) 5,10,15,20-tetra-4-pyridylporphyrin 1.514-hydrate
top
Crystal data top
C40H26N8·1.514H2O | Dx = 1.369 Mg m−3 |
Mr = 645.96 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42d | Cell parameters from 4891 reflections |
Hall symbol: I -4 2bw | θ = 2.0–27.9° |
a = 15.2155 (4) Å | µ = 0.09 mm−1 |
c = 13.5388 (6) Å | T = 110 K |
V = 3134.39 (18) Å3 | Prism, red |
Z = 4 | 0.35 × 0.25 × 0.15 mm |
F(000) = 1348.9 | |
Data collection top
Nonius KappaCCD diffractometer | 757 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.067 |
Graphite monochromator | θmax = 27.9°, θmin = 2.7° |
Detector resolution: 12.8 pixels mm-1 | h = −19→19 |
1 deg. ω scans | k = −16→18 |
16180 measured reflections | l = −16→17 |
1042 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0618P)2 + 0.3277P] where P = (Fo2 + 2Fc2)/3 |
757 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.13 e Å−3 |
1 restraint | Δρmin = −0.16 e Å−3 |
Crystal data top
C40H26N8·1.514H2O | Z = 4 |
Mr = 645.96 | Mo Kα radiation |
Tetragonal, I42d | µ = 0.09 mm−1 |
a = 15.2155 (4) Å | T = 110 K |
c = 13.5388 (6) Å | 0.35 × 0.25 × 0.15 mm |
V = 3134.39 (18) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 757 reflections with I > 2σ(I) |
16180 measured reflections | Rint = 0.067 |
1042 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.13 e Å−3 |
757 reflections | Δρmin = −0.16 e Å−3 |
118 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 Friedel opposites were merged. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.19666 (18) | 0.03473 (17) | 0.5178 (2) | 0.0401 (7) | |
C2 | 0.2587 (2) | 0.10622 (18) | 0.5225 (2) | 0.0450 (7) | |
H2 | 0.3194 | 0.1017 | 0.5379 | 0.054* | |
C3 | 0.21436 (17) | 0.18090 (18) | 0.5010 (3) | 0.0437 (7) | |
H3 | 0.2384 | 0.2384 | 0.4971 | 0.052* | |
C4 | 0.12407 (18) | 0.15699 (17) | 0.4854 (2) | 0.0385 (7) | |
C5 | 0.05459 (18) | 0.21687 (17) | 0.4719 (2) | 0.0381 (7) | |
N6 | 0.11491 (15) | 0.06812 (15) | 0.49667 (19) | 0.0390 (6) | |
H6 | 0.0658 | 0.0379 | 0.4914 | 0.047* | 0.50 |
C7 | 0.07877 (18) | 0.30931 (19) | 0.4471 (2) | 0.0412 (7) | |
C8 | 0.0751 (2) | 0.3755 (2) | 0.5170 (3) | 0.0613 (9) | |
H8 | 0.0556 | 0.3630 | 0.5822 | 0.074* | |
C9 | 0.1000 (3) | 0.4600 (2) | 0.4915 (3) | 0.0638 (10) | |
H9 | 0.0983 | 0.5040 | 0.5412 | 0.077* | |
N10 | 0.12619 (19) | 0.48306 (18) | 0.4010 (2) | 0.0580 (8) | |
C11 | 0.1281 (2) | 0.4191 (2) | 0.3350 (3) | 0.0632 (10) | |
H11 | 0.1461 | 0.4337 | 0.2698 | 0.076* | |
C12 | 0.1060 (2) | 0.3323 (2) | 0.3534 (3) | 0.0542 (9) | |
H12 | 0.1095 | 0.2895 | 0.3025 | 0.065* | |
O13 | 0.2500 | 0.6193 (2) | 0.3750 | 0.0443 (14) | 0.757 (10) |
H13 | 0.2000 (18) | 0.582 (2) | 0.380 (4) | 0.067* | 0.757 (10) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0379 (15) | 0.0432 (16) | 0.0393 (15) | 0.0019 (12) | −0.0012 (14) | −0.0047 (12) |
C2 | 0.0375 (15) | 0.0467 (16) | 0.0508 (18) | −0.0026 (14) | −0.0039 (13) | −0.0070 (14) |
C3 | 0.0424 (15) | 0.0405 (15) | 0.0481 (17) | −0.0036 (12) | −0.0004 (14) | 0.0006 (14) |
C4 | 0.0386 (15) | 0.0390 (15) | 0.0378 (16) | −0.0049 (13) | 0.0015 (13) | 0.0000 (12) |
C5 | 0.0389 (15) | 0.0380 (15) | 0.0374 (15) | 0.0020 (12) | −0.0026 (12) | 0.0013 (12) |
N6 | 0.0368 (13) | 0.0377 (13) | 0.0424 (14) | 0.0007 (10) | 0.0007 (11) | −0.0024 (11) |
C7 | 0.0343 (15) | 0.0385 (15) | 0.0508 (18) | 0.0000 (12) | −0.0063 (13) | 0.0036 (13) |
C8 | 0.093 (3) | 0.0459 (18) | 0.0449 (18) | −0.0106 (18) | −0.0094 (18) | 0.0062 (16) |
C9 | 0.087 (3) | 0.0426 (18) | 0.062 (2) | −0.0102 (17) | −0.023 (2) | 0.0060 (16) |
N10 | 0.0514 (17) | 0.0483 (16) | 0.074 (2) | −0.0059 (13) | −0.0002 (16) | 0.0120 (15) |
C11 | 0.069 (2) | 0.053 (2) | 0.067 (2) | 0.0017 (18) | 0.0212 (19) | 0.0148 (18) |
C12 | 0.060 (2) | 0.0440 (17) | 0.058 (2) | 0.0023 (15) | 0.0120 (17) | 0.0037 (15) |
O13 | 0.047 (2) | 0.031 (2) | 0.055 (3) | 0.000 | 0.0040 (19) | 0.000 |
Geometric parameters (Å, º) top
C1—N6 | 1.374 (4) | C7—C12 | 1.380 (4) |
C1—C5i | 1.400 (4) | C7—C8 | 1.383 (4) |
C1—C2 | 1.441 (4) | C8—C9 | 1.384 (4) |
C2—C3 | 1.353 (4) | C8—H8 | 0.9500 |
C2—H2 | 0.9500 | C9—N10 | 1.336 (5) |
C3—C4 | 1.437 (4) | C9—H9 | 0.9500 |
C3—H3 | 0.9500 | N10—C11 | 1.322 (5) |
C4—N6 | 1.368 (3) | C11—C12 | 1.384 (5) |
C4—C5 | 1.407 (4) | C11—H11 | 0.9500 |
C5—C1ii | 1.400 (4) | C12—H12 | 0.9500 |
C5—C7 | 1.492 (4) | O13—H13 | 0.950 (2) |
N6—H6 | 0.8800 | | |
| | | |
N6—C1—C5i | 125.3 (2) | C1—N6—H6 | 126.4 |
N6—C1—C2 | 108.8 (2) | C12—C7—C8 | 117.2 (3) |
C5i—C1—C2 | 125.7 (3) | C12—C7—C5 | 121.4 (3) |
C3—C2—C1 | 107.3 (3) | C8—C7—C5 | 121.5 (3) |
C3—C2—H2 | 126.3 | C9—C8—C7 | 119.7 (3) |
C1—C2—H2 | 126.3 | C9—C8—H8 | 120.2 |
C2—C3—C4 | 107.2 (2) | C7—C8—H8 | 120.2 |
C2—C3—H3 | 126.4 | N10—C9—C8 | 123.7 (3) |
C4—C3—H3 | 126.4 | N10—C9—H9 | 118.2 |
N6—C4—C5 | 125.3 (2) | C8—C9—H9 | 118.2 |
N6—C4—C3 | 109.3 (2) | C11—N10—C9 | 115.7 (3) |
C5—C4—C3 | 125.0 (2) | N10—C11—C12 | 125.1 (3) |
C1ii—C5—C4 | 125.0 (3) | N10—C11—H11 | 117.5 |
C1ii—C5—C7 | 118.0 (2) | C12—C11—H11 | 117.5 |
C4—C5—C7 | 117.0 (3) | C7—C12—C11 | 118.7 (3) |
C4—N6—C1 | 107.2 (2) | C7—C12—H12 | 120.6 |
C4—N6—H6 | 126.4 | C11—C12—H12 | 120.6 |
Symmetry codes: (i) y, −x, −z+1; (ii) −y, x, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···N10 | 0.95 (1) | 1.90 (1) | 2.823 (3) | 163 (4) |
(III) 5,10,15,20-tetra-4-pyridylporphyrin 2-chlorophenol disolvate
top
Crystal data top
C40H26N8·2C6H5ClO | Z = 1 |
Mr = 875.79 | F(000) = 454 |
Triclinic, P1 | Dx = 1.418 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5563 (2) Å | Cell parameters from 3736 reflections |
b = 10.0441 (3) Å | θ = 2.6–27.9° |
c = 16.1903 (5) Å | µ = 0.21 mm−1 |
α = 77.841 (2)° | T = 110 K |
β = 88.9097 (19)° | Needles, red |
γ = 79.6939 (14)° | 0.60 × 0.20 × 0.10 mm |
V = 1025.24 (5) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 3617 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 27.9°, θmin = 2.6° |
Detector resolution: 12.8 pixels mm-1 | h = 0→8 |
1 deg. ϕ and ω scans | k = −12→13 |
11144 measured reflections | l = −20→21 |
4834 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.064P)2 + 1.1604P] where P = (Fo2 + 2Fc2)/3 |
4834 reflections | (Δ/σ)max < 0.001 |
289 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
C40H26N8·2C6H5ClO | γ = 79.6939 (14)° |
Mr = 875.79 | V = 1025.24 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.5563 (2) Å | Mo Kα radiation |
b = 10.0441 (3) Å | µ = 0.21 mm−1 |
c = 16.1903 (5) Å | T = 110 K |
α = 77.841 (2)° | 0.60 × 0.20 × 0.10 mm |
β = 88.9097 (19)° | |
Data collection top
Nonius KappaCCD diffractometer | 3617 reflections with I > 2σ(I) |
11144 measured reflections | Rint = 0.036 |
4834 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.42 e Å−3 |
4834 reflections | Δρmin = −0.70 e Å−3 |
289 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.9091 (3) | 0.3183 (2) | 0.46729 (13) | 0.0160 (4) | |
C2 | 1.0192 (3) | 0.2573 (2) | 0.40116 (13) | 0.0187 (4) | |
H2 | 1.1535 | 0.2016 | 0.4057 | 0.022* | |
C3 | 0.8933 (3) | 0.2954 (2) | 0.33259 (13) | 0.0191 (4) | |
H3 | 0.9219 | 0.2727 | 0.2790 | 0.023* | |
C4 | 0.7045 (3) | 0.3783 (2) | 0.35631 (13) | 0.0165 (4) | |
C5 | 0.5302 (3) | 0.4298 (2) | 0.30212 (13) | 0.0177 (4) | |
C6 | 0.3418 (3) | 0.5064 (2) | 0.32100 (13) | 0.0163 (4) | |
C7 | 0.1741 (3) | 0.5711 (2) | 0.26300 (14) | 0.0200 (4) | |
H7 | 0.1660 | 0.5630 | 0.2058 | 0.024* | |
C8 | 0.0279 (3) | 0.6465 (2) | 0.30376 (13) | 0.0192 (4) | |
H8 | −0.0992 | 0.7008 | 0.2799 | 0.023* | |
C9 | 0.0994 (3) | 0.6295 (2) | 0.38891 (13) | 0.0162 (4) | |
C10 | 0.0064 (3) | 0.6968 (2) | 0.45140 (13) | 0.0160 (4) | |
N11 | 0.7190 (3) | 0.39229 (17) | 0.43822 (11) | 0.0155 (4) | |
H11 | 0.6259 | 0.4390 | 0.4662 | 0.019* | 0.50 |
N12 | 0.2887 (3) | 0.54210 (18) | 0.39700 (11) | 0.0158 (4) | |
H12 | 0.3644 | 0.5134 | 0.4438 | 0.019* | 0.50 |
C13 | 0.5466 (3) | 0.3985 (2) | 0.21559 (13) | 0.0200 (4) | |
C14 | 0.6716 (4) | 0.4618 (3) | 0.15515 (14) | 0.0265 (5) | |
H14 | 0.7434 | 0.5303 | 0.1666 | 0.032* | |
C15 | 0.6897 (4) | 0.4229 (3) | 0.07742 (15) | 0.0317 (6) | |
H15 | 0.7760 | 0.4664 | 0.0365 | 0.038* | |
N16 | 0.5926 (3) | 0.3278 (2) | 0.05711 (13) | 0.0313 (5) | |
C17 | 0.4674 (4) | 0.2702 (3) | 0.11446 (16) | 0.0297 (5) | |
H17 | 0.3942 | 0.2042 | 0.1004 | 0.036* | |
C18 | 0.4397 (4) | 0.3025 (3) | 0.19390 (15) | 0.0254 (5) | |
H18 | 0.3488 | 0.2596 | 0.2329 | 0.030* | |
C19 | −0.1898 (3) | 0.7976 (2) | 0.42717 (13) | 0.0166 (4) | |
C20 | −0.2005 (3) | 0.9376 (2) | 0.42684 (13) | 0.0199 (4) | |
H20 | −0.0824 | 0.9702 | 0.4423 | 0.024* | |
C21 | −0.3856 (4) | 1.0287 (2) | 0.40371 (14) | 0.0229 (5) | |
H21 | −0.3904 | 1.1233 | 0.4052 | 0.028* | |
N22 | −0.5574 (3) | 0.9920 (2) | 0.37948 (12) | 0.0242 (4) | |
C23 | −0.5444 (3) | 0.8573 (2) | 0.37953 (15) | 0.0237 (5) | |
H23 | −0.6640 | 0.8280 | 0.3625 | 0.028* | |
C24 | −0.3682 (3) | 0.7579 (2) | 0.40275 (14) | 0.0213 (5) | |
H24 | −0.3692 | 0.6637 | 0.4020 | 0.026* | |
Cl25 | 1.04786 (11) | 0.23131 (8) | −0.01971 (4) | 0.0426 (2) | |
C26 | 0.9931 (4) | 0.1380 (3) | −0.09282 (15) | 0.0292 (5) | |
C27 | 1.1587 (4) | 0.0660 (3) | −0.12998 (17) | 0.0382 (6) | |
H27 | 1.2972 | 0.0642 | −0.1129 | 0.046* | |
C28 | 1.1202 (5) | −0.0027 (3) | −0.19171 (17) | 0.0411 (7) | |
H28 | 1.2319 | −0.0510 | −0.2181 | 0.049* | |
C29 | 0.9168 (5) | −0.0009 (3) | −0.21498 (16) | 0.0361 (6) | |
H29 | 0.8901 | −0.0483 | −0.2574 | 0.043* | |
C30 | 0.7536 (4) | 0.0687 (3) | −0.17740 (16) | 0.0328 (6) | |
H30 | 0.6155 | 0.0688 | −0.1942 | 0.039* | |
C31 | 0.7890 (4) | 0.1396 (3) | −0.11446 (15) | 0.0289 (5) | |
O32 | 0.6204 (3) | 0.2076 (2) | −0.08230 (12) | 0.0404 (5) | |
H32 | 0.6511 | 0.2527 | −0.0409 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0134 (10) | 0.0146 (9) | 0.0203 (10) | −0.0019 (8) | 0.0010 (8) | −0.0046 (8) |
C2 | 0.0151 (10) | 0.0189 (10) | 0.0212 (10) | 0.0007 (8) | 0.0019 (8) | −0.0054 (8) |
C3 | 0.0187 (10) | 0.0207 (10) | 0.0180 (10) | −0.0007 (8) | 0.0035 (8) | −0.0074 (8) |
C4 | 0.0161 (10) | 0.0160 (10) | 0.0176 (10) | −0.0020 (8) | 0.0014 (8) | −0.0049 (8) |
C5 | 0.0177 (10) | 0.0177 (10) | 0.0183 (10) | −0.0025 (8) | 0.0004 (8) | −0.0056 (8) |
C6 | 0.0166 (10) | 0.0161 (10) | 0.0169 (10) | −0.0024 (8) | −0.0007 (8) | −0.0054 (8) |
C7 | 0.0196 (11) | 0.0223 (11) | 0.0185 (10) | −0.0024 (9) | −0.0021 (8) | −0.0064 (8) |
C8 | 0.0167 (10) | 0.0199 (10) | 0.0206 (10) | −0.0003 (8) | −0.0026 (8) | −0.0051 (8) |
C9 | 0.0147 (10) | 0.0146 (9) | 0.0200 (10) | −0.0027 (8) | 0.0002 (8) | −0.0051 (8) |
C10 | 0.0132 (10) | 0.0147 (10) | 0.0196 (10) | −0.0019 (8) | 0.0008 (8) | −0.0032 (8) |
N11 | 0.0139 (8) | 0.0156 (8) | 0.0172 (8) | −0.0011 (7) | 0.0005 (7) | −0.0052 (7) |
N12 | 0.0145 (8) | 0.0165 (8) | 0.0172 (8) | −0.0015 (7) | 0.0004 (7) | −0.0060 (7) |
C13 | 0.0169 (10) | 0.0230 (11) | 0.0183 (10) | 0.0045 (9) | −0.0027 (8) | −0.0072 (8) |
C14 | 0.0287 (13) | 0.0293 (12) | 0.0210 (11) | −0.0026 (10) | 0.0013 (9) | −0.0064 (9) |
C15 | 0.0362 (14) | 0.0356 (14) | 0.0199 (11) | −0.0001 (11) | 0.0052 (10) | −0.0044 (10) |
N16 | 0.0337 (12) | 0.0365 (12) | 0.0224 (10) | 0.0042 (10) | −0.0036 (9) | −0.0115 (9) |
C17 | 0.0295 (13) | 0.0332 (13) | 0.0278 (12) | 0.0011 (11) | −0.0053 (10) | −0.0145 (10) |
C18 | 0.0223 (12) | 0.0304 (12) | 0.0247 (11) | −0.0015 (10) | −0.0021 (9) | −0.0112 (9) |
C19 | 0.0154 (10) | 0.0189 (10) | 0.0153 (9) | −0.0012 (8) | 0.0010 (8) | −0.0045 (8) |
C20 | 0.0200 (11) | 0.0198 (10) | 0.0202 (10) | −0.0021 (9) | −0.0010 (8) | −0.0063 (8) |
C21 | 0.0243 (12) | 0.0177 (10) | 0.0254 (11) | 0.0006 (9) | 0.0002 (9) | −0.0052 (9) |
N22 | 0.0194 (10) | 0.0222 (10) | 0.0289 (10) | −0.0006 (8) | 0.0012 (8) | −0.0033 (8) |
C23 | 0.0158 (11) | 0.0242 (11) | 0.0305 (12) | −0.0040 (9) | −0.0004 (9) | −0.0040 (9) |
C24 | 0.0174 (11) | 0.0181 (10) | 0.0280 (11) | −0.0031 (8) | 0.0001 (9) | −0.0042 (9) |
Cl25 | 0.0351 (4) | 0.0593 (5) | 0.0388 (4) | −0.0081 (3) | −0.0019 (3) | −0.0223 (3) |
C26 | 0.0315 (13) | 0.0327 (13) | 0.0224 (11) | −0.0035 (11) | −0.0001 (10) | −0.0057 (10) |
C27 | 0.0302 (14) | 0.0472 (17) | 0.0304 (13) | 0.0053 (12) | −0.0008 (11) | −0.0030 (12) |
C28 | 0.0425 (16) | 0.0418 (16) | 0.0312 (14) | 0.0123 (13) | 0.0035 (12) | −0.0073 (12) |
C29 | 0.0545 (18) | 0.0278 (13) | 0.0255 (12) | −0.0006 (12) | −0.0026 (12) | −0.0097 (10) |
C30 | 0.0362 (14) | 0.0367 (14) | 0.0263 (12) | −0.0085 (12) | 0.0000 (11) | −0.0065 (11) |
C31 | 0.0293 (13) | 0.0332 (13) | 0.0241 (12) | −0.0039 (11) | 0.0026 (10) | −0.0072 (10) |
O32 | 0.0310 (10) | 0.0616 (13) | 0.0340 (10) | −0.0035 (9) | 0.0048 (8) | −0.0268 (9) |
Geometric parameters (Å, º) top
C1—N11 | 1.367 (3) | C15—H15 | 0.9500 |
C1—C10i | 1.406 (3) | N16—C17 | 1.336 (3) |
C1—C2 | 1.460 (3) | C17—C18 | 1.393 (3) |
C2—C3 | 1.343 (3) | C17—H17 | 0.9500 |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—C4 | 1.456 (3) | C19—C24 | 1.390 (3) |
C3—H3 | 0.9500 | C19—C20 | 1.394 (3) |
C4—N11 | 1.370 (3) | C20—C21 | 1.388 (3) |
C4—C5 | 1.407 (3) | C20—H20 | 0.9500 |
C5—C6 | 1.398 (3) | C21—N22 | 1.336 (3) |
C5—C13 | 1.496 (3) | C21—H21 | 0.9500 |
C6—N12 | 1.374 (3) | N22—C23 | 1.340 (3) |
C6—C7 | 1.428 (3) | C23—C24 | 1.385 (3) |
C7—C8 | 1.362 (3) | C23—H23 | 0.9500 |
C7—H7 | 0.9500 | C24—H24 | 0.9500 |
C8—C9 | 1.431 (3) | Cl25—C26 | 1.736 (3) |
C8—H8 | 0.9500 | C26—C31 | 1.386 (4) |
C9—N12 | 1.377 (3) | C26—C27 | 1.394 (4) |
C9—C10 | 1.403 (3) | C27—C28 | 1.379 (4) |
C10—C1i | 1.406 (3) | C27—H27 | 0.9500 |
C10—C19 | 1.490 (3) | C28—C29 | 1.388 (4) |
N11—H11 | 0.8800 | C28—H28 | 0.9500 |
N12—H12 | 0.8800 | C29—C30 | 1.375 (4) |
C13—C14 | 1.388 (3) | C29—H29 | 0.9500 |
C13—C18 | 1.392 (3) | C30—C31 | 1.405 (3) |
C14—C15 | 1.391 (3) | C30—H30 | 0.9500 |
C14—H14 | 0.9500 | C31—O32 | 1.348 (3) |
C15—N16 | 1.336 (4) | O32—H32 | 0.9286 |
| | | |
N11—C1—C10i | 126.03 (18) | C14—C15—H15 | 118.2 |
N11—C1—C2 | 110.72 (18) | C15—N16—C17 | 117.5 (2) |
C10i—C1—C2 | 123.24 (19) | N16—C17—C18 | 122.9 (2) |
C3—C2—C1 | 106.49 (18) | N16—C17—H17 | 118.6 |
C3—C2—H2 | 126.8 | C18—C17—H17 | 118.6 |
C1—C2—H2 | 126.8 | C13—C18—C17 | 119.3 (2) |
C2—C3—C4 | 106.73 (18) | C13—C18—H18 | 120.4 |
C2—C3—H3 | 126.6 | C17—C18—H18 | 120.4 |
C4—C3—H3 | 126.6 | C24—C19—C20 | 117.1 (2) |
N11—C4—C5 | 125.97 (18) | C24—C19—C10 | 122.16 (19) |
N11—C4—C3 | 110.69 (18) | C20—C19—C10 | 120.78 (19) |
C5—C4—C3 | 123.28 (18) | C21—C20—C19 | 119.3 (2) |
C6—C5—C4 | 126.66 (19) | C21—C20—H20 | 120.4 |
C6—C5—C13 | 116.44 (19) | C19—C20—H20 | 120.4 |
C4—C5—C13 | 116.89 (18) | N22—C21—C20 | 124.2 (2) |
N12—C6—C5 | 126.62 (19) | N22—C21—H21 | 117.9 |
N12—C6—C7 | 106.96 (18) | C20—C21—H21 | 117.9 |
C5—C6—C7 | 126.27 (19) | C21—N22—C23 | 115.8 (2) |
C8—C7—C6 | 108.28 (19) | N22—C23—C24 | 124.4 (2) |
C8—C7—H7 | 125.9 | N22—C23—H23 | 117.8 |
C6—C7—H7 | 125.9 | C24—C23—H23 | 117.8 |
C7—C8—C9 | 107.97 (19) | C23—C24—C19 | 119.2 (2) |
C7—C8—H8 | 126.0 | C23—C24—H24 | 120.4 |
C9—C8—H8 | 126.0 | C19—C24—H24 | 120.4 |
N12—C9—C10 | 125.37 (19) | C31—C26—C27 | 121.8 (2) |
N12—C9—C8 | 106.96 (17) | C31—C26—Cl25 | 119.94 (19) |
C10—C9—C8 | 127.48 (19) | C27—C26—Cl25 | 118.2 (2) |
C9—C10—C1i | 124.75 (19) | C28—C27—C26 | 119.5 (3) |
C9—C10—C19 | 116.90 (18) | C28—C27—H27 | 120.3 |
C1i—C10—C19 | 118.24 (18) | C26—C27—H27 | 120.3 |
C1—N11—C4 | 105.35 (16) | C27—C28—C29 | 119.5 (2) |
C1—N11—H11 | 127.3 | C27—C28—H28 | 120.2 |
C4—N11—H11 | 127.3 | C29—C28—H28 | 120.2 |
C6—N12—C9 | 109.80 (17) | C30—C29—C28 | 120.9 (2) |
C6—N12—H12 | 125.1 | C30—C29—H29 | 119.6 |
C9—N12—H12 | 125.1 | C28—C29—H29 | 119.6 |
C14—C13—C18 | 117.9 (2) | C29—C30—C31 | 120.7 (3) |
C14—C13—C5 | 121.3 (2) | C29—C30—H30 | 119.7 |
C18—C13—C5 | 120.8 (2) | C31—C30—H30 | 119.7 |
C13—C14—C15 | 118.7 (2) | O32—C31—C26 | 125.6 (2) |
C13—C14—H14 | 120.7 | O32—C31—C30 | 116.8 (2) |
C15—C14—H14 | 120.7 | C26—C31—C30 | 117.6 (2) |
N16—C15—C14 | 123.7 (2) | C31—O32—H32 | 113.8 |
N16—C15—H15 | 118.2 | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O32—H32···N16 | 0.93 | 1.90 | 2.764 (3) | 154 |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C40H26N8 | C40H26N8·1.514H2O | C40H26N8·2C6H5ClO |
Mr | 618.69 | 645.96 | 875.79 |
Crystal system, space group | Monoclinic, Cc | Tetragonal, I42d | Triclinic, P1 |
Temperature (K) | 110 | 110 | 110 |
a, b, c (Å) | 13.6042 (2), 20.8734 (4), 11.4525 (2) | 15.2155 (4), 15.2155 (4), 13.5388 (6) | 6.5563 (2), 10.0441 (3), 16.1903 (5) |
α, β, γ (°) | 90, 116.2786 (11), 90 | 90, 90, 90 | 77.841 (2), 88.9097 (19), 79.6939 (14) |
V (Å3) | 2916.02 (9) | 3134.39 (18) | 1025.24 (5) |
Z | 4 | 4 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.21 |
Crystal size (mm) | 0.40 × 0.40 × 0.30 | 0.35 × 0.25 × 0.15 | 0.60 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16180, 3456, 3032 | 16180, 1042, 757 | 11144, 4834, 3617 |
Rint | 0.057 | 0.067 | 0.036 |
(sin θ/λ)max (Å−1) | 0.658 | 0.657 | 0.659 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.127, 1.06 | 0.051, 0.115, 1.04 | 0.058, 0.156, 1.03 |
No. of reflections | 3456 | 757 | 4834 |
No. of parameters | 433 | 118 | 289 |
No. of restraints | 2 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.28 | 0.13, −0.16 | 0.42, −0.70 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···N10 | 0.950 (2) | 1.902 (13) | 2.823 (3) | 163 (4) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O32—H32···N16 | 0.93 | 1.90 | 2.764 (3) | 154 |
Tetrapyridylporphyrin (TPyP; Fleischer, 1962) is one of the most widely studied porphyrin ligands in materials chemistry. It bears laterally diverging pyridyl functions which can readily interact in a cooperative manner with complementary entities through either coordination or hydrogen bonding. Moreover, it can form organometallic complexes with various transition metal ions inserted into the macrocyclic core, the latter potentially providing additional binding sites for further intermolecular coordination. Self-coordination of the Zn-TPyP complex into one-, two- and three-dimensional coordination polymers has been widely reported (Fleischer & Shachter, 1991; Krupitsky et al., 1994, Diskin-Posner et al., 2001; Ring et al., 2005). Facile formation of diverse coordination networks and frameworks of TPyP and M-TPyP via metal ions as bridging nodes between the peripheral pyridyl functions of adjacent species has also been reported (Goldberg, 2000, 2005, 2008, and references therein). More recently, the capacity of this porphyrin to engage in networking by supramolecular hydrogen bonding through complementary components has been demonstrated (Koner & Goldberg, 2009). The molecular framework of TPyP/Zn–TPyP is relatively rigid, and the central core of the porphyrin has an aromatic nature. However, the detailed conformation of this ligand is affected to some extent by the requirement to optimize the intermolecular interactions, and minimize the enthalpy, within the formed supramolecular assembly in a given case. Correspondingly, the macrocyclic framework of TPyP may reveal in most cases either flat or slightly ruffled conformations, as has been observed for various tetrapyrrole macrocycles (Scheidt & Lee, 1987). Like many other tetraarylporphyrins, the TPyP/M–TPyP framework exhibits shape complementarity only in two dimensions (Byrn et al., 1993, and references therein), and therefore it commonly tends to crystallize as a solvate (because of this feature such compounds were nicknamed `porphyrin sponges'), where molecules of the solvent fill the interporphyrin voids in the lattice. This may explain why the crystal structure of unsolvated TPyP has not been characterized before.
We report here for the first time the crystal structure of pure TPyP, (I), and relate it to the unique conformational features of the porphyrin ligand in this case. We also describe the structure of the non-stoichiometric hydrate TPyP.1.514(H2O), (II), in which unusually large deformation of the porphyrin core has again been observed, apparently also in order to facilitate multiple supramolecular hydrogen bonding between the porphyrin and water components. Then, another variant, 2-chlorophenol solvated TPyP, is described, (III), in which, however, the porphyrin macrocycle is characterized by a nearly planar conformation. The molecular structure of (I) is shown in Figs. 1 and 2(a). Of particular interest is the severe deformation of the porphyrin core from planarity, resulting from the optimization of the intermolecular packing in the crystals of pure TPyP. Fig. 2(a) gives the deviations of the individual atoms from the mean plane of the 24-membered porphyrin core, which range from -0.394 Å (for atom C7) to +0.393 Å (C12). The relatively large dihedral angles between the planes of the five-membered pyrrole rings provide further evidence for the severe ruffling of this porphyrin macrocycle. Thus, the torsion angles between the corresponding adjacent pyrrole rings (those containing atoms N22/N21, N23/N22, N24/N23 and N21/N24) are 18.19 (6), 20.20 (10), 20.34 (11) and 17.25 (9)°, respectively. The torsion angles between pyrrole rings located across the macrocycle are even larger [27.44 (9)° for N23/N21 and 26.41 (8)° for N24/N22]. The molecular symmetry of TPyP in this structure is C1. The conformationally distorted porphyrin molecules pack tightly in the crystal structure of (I), without the need to incorporate crystallization solvent into the lattice, as shown in Fig. 3. The intermolecular organization is stabilized effectively by van der Waals forces. The porphyrin core of a given molecule is approached from above and below by edge-on-oriented pyridyl substituents of neighbouring species. Nearly parallel overlap between the pyridyl rings of the laterally displaced units is indicative of possible π–π interactions between them. However, no direction-specific intermolecular contacts, such as those of C—H···N type, significantly shorter than the corresponding sums of the van der Waals radii are present.
The porphyrin molecule in (II) is also characterized by a distorted conformation of the central core (Figs. 2b and 4). In this structure the porphyrin molecular unit is located on the 4 axis of symmetry, while the water species reside on twofold axes. The torsion angles between the adjacent pyrrole rings are 18.27 (8)°; those between the pyrroles across the macrocycle are 25.95 (7)°. The deviations of the individual atoms in the 24-membered macroring are quite significant, as in (I), ranging from -0.382 to +0.382 Å (Fig. 2b). Water molecules located on twofold rotation axes, and with site occupancy 0.757 (10), form hydrogen bonds to the peripheral pyridyl N atoms of two adjacent porphyrin units located at different z-coordinate levels (Fig. 5 and Table 1). These interactions operate at the four corners of the ligand, throughout the crystal, thus creating a continuous three-dimensional hydrogen-bonded architecture. Fig. 6 illustrates the crystal packing of (II) viewed roughly perpendicular to the tetragonal axis, depicting the distorted nature of the porphyrin macrocycle. The TPyP molecules are arranged along the c axis is an offset manner, so that the macrocyclic ring of a given unit is approached from above and below by two pyridyl groups of adjacent porphyrins on each side. The tight arrangement lacks intermolecular contacts that are significantly shorter than common van der Waals diameters, reflecting on further (to the hydrogen bonding interactions) stabilization of the entire structure by common dispersion forces.
While TPyP reveals similarly distorted conformations in the two previous examples, this is not the case in the structure of its 2-chlorophenol disolvate (III) (Fig. 7). The porphyrin molecule is located on the inversion centre at (1/2, 1/2, 1/2), and its two trans-related pyridyl groups are hydrogen bonded to the o-chlorophenol solvent. The macrocyclic core is essentially planar, and the TPyP molecules are stacked in an offset manner along the a axis of the crystal at a mean interplanar distance of 3.55 (2) Å (Fig. 8). In this offset stacked geometry, each porphyrin core is sandwiched between two pyridyl arms of adjacent species from above and below, which are displaced by ±b. Porphyrin stacks displaced along the c axis form a tightly packed layered zones parallel to the ac face of the unit cell. With this zone, the trans-related pyridyl groups of neighboring coplanar porphyrins overlap effectively, stabilizing the layered arrangement by favourable dipolar and dispersive interactions. The other pyridyl substituents directed outwards (perpendicular to the layered porphyrin arrays) are hydrogen bonded to the o-chlorophenol species via O—H···N hydrogen bonds (Table 2). This intermolecular organization is similar to that reported before for the 1:2 TPyP solvates with guaiacol and benzyl alcohol (Krupitsky et al., 1994), and is frequently found in solvates of other tetraarylporphyrins (Byrn et al., 1993, and references therein). The interporphyrin offset stacking geometry is a fundamental property of the porphyrin–porphyrin interaction (Leighton et al., 1988), and structure (III) is in agreement with this principle. It favors in crystals stacked organization of the tetraarylporphyrin molecules with flat cores, and tight packing of these stacks into two-dimensional layers. The crystalline organization of the two-dimensional porphyrin layers along the third dimension is facilitated by solvation of the layers along the interfaces between them.
This study characterizes for the first time the structure of unsolvated TPyP, revealing an unusually distorted conformation of this ligand. This observation is even more striking when compared with the structure of the solvent-free tetraphenylporphyrin analog (TPP), which reveals a planar conformation of the porphyrin core and the common offset stacking arrangement as in (III) (Kano et al., 2000). It is possible that the electron-withdrawing effect of the pyridyl substituents weakens the aromaticity of the porphyrin macrocycle in TPyP (as compared with that in TPP), allowing more readily its deformation from planarity by more dominant crystal packing forces. It appears that this feature is conserved even in the presence of small solvents such as water [as in (II)], while with larger solvent such as 2-chlorophenol the more abundant offset-stacked organization of TPyP is formed. It remains to be seen whether a flat polymorph of unsolvated TPyP will be found in the future.