The title free base porphyrin compound forms hydrogen-bonded adducts with
N,
N-dimethylformamide, C
44H
30N
4O
4·4C
3H
7NO, (I), a mixture of
N,
N-dimethylformamide and water, C
44H
30N
4O
4·4C
3H
7NO·H
2O, (II), and a mixture of
N,
N-dimethylacetamide and water, C
44H
30N
4O
4·6C
3H
7NO·2H
2O, (III). Total solvation of the four hydroxy functions of the porphyrin molecules characterizes all three compounds, thus preventing its supramolecular association into extended network architectures. In (I), the asymmetric unit consist of two five-component adduct species, while in (III), the nine-component entities reside on centres of inversion. This report provides the first structural characterizations of the free base tetra(hydroxyphenyl)porphyrin. It also demonstrates that the presence of strong Lewis bases, such as dimethylformamide or dimethylacetamide, in the crystallization mixture prevents direct supramolecular networking of the porphyrin ligands
via O—H
O—H hydrogen bonds, due to their competing O—H
N(base) interaction with the hydroxy functions. The crystal packing of compounds (I)–(III) resembles that of other hydrogen-bonding-assisted tetraarylporphyrin clathrates.
Supporting information
CCDC references: 718117; 718118; 718119
TOHPP and all solvents used were obtained commercially. They were reacted
together (with various lanthanide salts) [Please give reagents and their
quantities for each of (I)–(III)] in a sealed reactor at 423 K for about
50 h, and then gradually cooled down to ambient temperature. [Please give
details of recrystallisation here]
C-bound H atoms were located in calculated positions and constrained to ride on
their parent atoms, with C—H = 0.95 or 0.98 Å and with Uiso(H) =
1.2 or 1.5Ueq(C). H atoms bound to O atoms were either located in
difference Fourier maps or placed in calculated positions to correspond to
idealized hydrogen-bonding geometries, with O—H = 0.84 Å for porphyrin O
atoms or O—H = 0.89–0.96 Å for water O atoms. Their atomic positions were
not refined, and they were constrained to ride on their parent atoms with
Uiso(H) = 1.5Ueq(O). In (I), some of the dimethylformamide
components are disordered, namely O115—C119 and O140—C144. The C(methyl)
atoms of the former species show large-amplitude displacement parameters,
while the latter moiety reveals a twofold orientational disorder. DELU
restraints (SHELXL97; Sheldrick, 2008) were applied to the
displacement
parameters of the atoms O140—C144, and DFIX restraints (SHELXL97)
were applied to the N117—C118 and N117—C119 bonds. Restraint-free
least-squares refinements were applied to structures (II) and (III). In all
three structures, the two H atoms bound to N within the porphyrin core could
not be located reliably. As some residual electron density was observed near
all the pyrrole N atoms, the H atoms bound to them were assumed to be
disordered equally between the four pyrrole rings and were located in
calculated positions, with N—H = 0.88 Å and Uiso(H) =
1.2Ueq(N).
Data collection: [Please provide details] for (I); COLLECT (Nonius, 1999) for (II), (III). Cell refinement: [Please provide details] for (I); DENZO (Otwinowski & Minor, 1997) for (II), (III). Data reduction: [Please provide details] for (I); DENZO (Otwinowski & Minor, 1997) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR97 (Altomare et al., 1994) for (II), (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996) for (I); ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006) for (II), (III). Software used to prepare material for publication: [Please provide details] for (I); SHELXL97 (Sheldrick, 2008) for (II), (III).
(I) 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin
N,
N'-dimethylformamide tetrasolvate
top
Crystal data top
C44H30N4O4·4C3H7NO | Z = 4 |
Mr = 971.10 | F(000) = 2056 |
Triclinic, P1 | Dx = 1.282 Mg m−3 |
a = 13.6255 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 16.0184 (3) Å | Cell parameters from 14137 reflections |
c = 26.2466 (5) Å | θ = 2.4–27.9° |
α = 101.7445 (12)° | µ = 0.09 mm−1 |
β = 92.4786 (12)° | T = 110 K |
γ = 114.9158 (8)° | Prism, red |
V = 5032.65 (15) Å3 | 0.40 × 0.40 × 0.20 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 13053 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 27.9°, θmin = 2.4° |
Detector resolution: 12.8 pixels mm-1 | h = −17→17 |
0.7 deg. ϕ and ω scan | k = −21→19 |
50610 measured reflections | l = −34→34 |
23879 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full with fixed elements per cycle | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0777P)2 + 0.4228P] where P = (Fo2 + 2Fc2)/3 |
23877 reflections | (Δ/σ)max = 0.043 |
1370 parameters | Δρmax = 0.36 e Å−3 |
18 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
C44H30N4O4·4C3H7NO | γ = 114.9158 (8)° |
Mr = 971.10 | V = 5032.65 (15) Å3 |
Triclinic, P1 | Z = 4 |
a = 13.6255 (2) Å | Mo Kα radiation |
b = 16.0184 (3) Å | µ = 0.09 mm−1 |
c = 26.2466 (5) Å | T = 110 K |
α = 101.7445 (12)° | 0.40 × 0.40 × 0.20 mm |
β = 92.4786 (12)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 13053 reflections with I > 2σ(I) |
50610 measured reflections | Rint = 0.051 |
23879 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 18 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.36 e Å−3 |
23877 reflections | Δρmin = −0.39 e Å−3 |
1370 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. Two of the DMF species exhibit partial orientational disorder. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.61879 (17) | −0.21510 (15) | 0.02696 (8) | 0.0300 (5) | |
C2 | 0.59874 (18) | −0.27621 (16) | 0.06191 (9) | 0.0327 (5) | |
H2 | 0.5314 | −0.3290 | 0.0619 | 0.039* | |
C3 | 0.69292 (17) | −0.24576 (15) | 0.09538 (9) | 0.0305 (5) | |
H3 | 0.7025 | −0.2744 | 0.1224 | 0.037* | |
C4 | 0.77472 (17) | −0.16381 (15) | 0.08320 (8) | 0.0286 (5) | |
C5 | 0.88423 (17) | −0.11179 (15) | 0.10765 (8) | 0.0271 (5) | |
C6 | 0.96081 (17) | −0.02768 (14) | 0.09677 (8) | 0.0256 (5) | |
C7 | 1.07468 (17) | 0.02043 (15) | 0.12080 (8) | 0.0288 (5) | |
H7 | 1.1096 | −0.0004 | 0.1441 | 0.035* | |
C8 | 1.12116 (18) | 0.10006 (15) | 0.10368 (8) | 0.0297 (5) | |
H8 | 1.1955 | 0.1460 | 0.1121 | 0.036* | |
C9 | 1.03541 (16) | 0.10209 (15) | 0.06969 (8) | 0.0261 (5) | |
C10 | 1.04947 (17) | 0.17895 (14) | 0.04780 (8) | 0.0262 (5) | |
C11 | 0.97072 (17) | 0.17679 (14) | 0.01049 (8) | 0.0260 (5) | |
C12 | 0.97341 (18) | 0.25182 (15) | −0.01101 (8) | 0.0315 (5) | |
H12 | 1.0284 | 0.3156 | −0.0012 | 0.038* | |
C13 | 0.88389 (18) | 0.21714 (15) | −0.04818 (9) | 0.0321 (5) | |
H13 | 0.8664 | 0.2523 | −0.0691 | 0.039* | |
C14 | 0.82122 (17) | 0.11944 (15) | −0.05031 (8) | 0.0280 (5) | |
C15 | 0.72287 (17) | 0.05659 (15) | −0.08390 (8) | 0.0269 (5) | |
C16 | 0.65282 (17) | −0.03429 (15) | −0.07889 (8) | 0.0270 (5) | |
C17 | 0.55465 (17) | −0.09913 (15) | −0.11573 (8) | 0.0299 (5) | |
H17 | 0.5305 | −0.0895 | −0.1476 | 0.036* | |
C18 | 0.50511 (17) | −0.17472 (15) | −0.09627 (8) | 0.0302 (5) | |
H18 | 0.4383 | −0.2290 | −0.1113 | 0.036* | |
C19 | 0.57304 (17) | −0.15796 (15) | −0.04771 (8) | 0.0280 (5) | |
C20 | 0.54700 (17) | −0.22266 (15) | −0.01533 (8) | 0.0284 (5) | |
N21 | 0.72647 (13) | −0.14720 (12) | 0.04161 (7) | 0.0278 (4) | |
H21 | 0.7593 | −0.1003 | 0.0265 | 0.033* | 0.50 |
N22 | 0.93977 (13) | 0.02141 (12) | 0.06458 (6) | 0.0256 (4) | |
H22 | 0.8778 | 0.0048 | 0.0446 | 0.031* | 0.50 |
N23 | 0.87501 (13) | 0.09771 (12) | −0.01321 (6) | 0.0269 (4) | |
H23 | 0.8519 | 0.0420 | −0.0057 | 0.032* | 0.50 |
N24 | 0.66334 (14) | −0.07297 (12) | −0.03854 (7) | 0.0278 (4) | |
H24 | 0.7171 | −0.0483 | −0.0121 | 0.033* | 0.50 |
C25 | 0.91760 (16) | −0.14762 (15) | 0.15054 (8) | 0.0265 (5) | |
C26 | 0.91509 (16) | −0.23755 (15) | 0.14060 (8) | 0.0277 (5) | |
H26 | 0.8951 | −0.2758 | 0.1056 | 0.033* | |
C27 | 0.94123 (17) | −0.27189 (15) | 0.18083 (8) | 0.0293 (5) | |
H27 | 0.9395 | −0.3331 | 0.1734 | 0.035* | |
C28 | 0.97014 (18) | −0.21653 (16) | 0.23233 (8) | 0.0319 (5) | |
C29 | 0.97521 (19) | −0.12630 (16) | 0.24263 (9) | 0.0353 (6) | |
H29 | 0.9967 | −0.0876 | 0.2775 | 0.042* | |
C30 | 0.94908 (18) | −0.09262 (16) | 0.20216 (9) | 0.0327 (5) | |
H30 | 0.9526 | −0.0307 | 0.2097 | 0.039* | |
O31 | 0.99382 (15) | −0.24738 (12) | 0.27390 (6) | 0.0445 (4) | |
H31 | 0.9924 | −0.3010 | 0.2629 | 0.067* | |
C32 | 1.15291 (17) | 0.26854 (15) | 0.06517 (8) | 0.0276 (5) | |
C33 | 1.19204 (17) | 0.31202 (15) | 0.11834 (8) | 0.0302 (5) | |
H33 | 1.1508 | 0.2854 | 0.1441 | 0.036* | |
C34 | 1.29018 (18) | 0.39354 (16) | 0.13428 (9) | 0.0343 (5) | |
H34 | 1.3165 | 0.4211 | 0.1707 | 0.041* | |
C35 | 1.35007 (18) | 0.43495 (16) | 0.09718 (9) | 0.0336 (5) | |
C36 | 1.31099 (18) | 0.39416 (15) | 0.04412 (9) | 0.0323 (5) | |
H36 | 1.3506 | 0.4228 | 0.0185 | 0.039* | |
C37 | 1.21429 (17) | 0.31176 (15) | 0.02854 (9) | 0.0293 (5) | |
H37 | 1.1890 | 0.2839 | −0.0079 | 0.035* | |
O38 | 1.44719 (12) | 0.51479 (11) | 0.11023 (6) | 0.0423 (4) | |
H38 | 1.4559 | 0.5406 | 0.1424 | 0.064* | |
C39 | 0.69269 (17) | 0.09163 (15) | −0.12792 (8) | 0.0289 (5) | |
C40 | 0.75866 (18) | 0.11138 (15) | −0.16746 (8) | 0.0317 (5) | |
H40 | 0.8240 | 0.1037 | −0.1656 | 0.038* | |
C41 | 0.73102 (18) | 0.14171 (15) | −0.20897 (9) | 0.0323 (5) | |
H41 | 0.7762 | 0.1531 | −0.2358 | 0.039* | |
C42 | 0.63652 (18) | 0.15566 (15) | −0.21169 (8) | 0.0310 (5) | |
C43 | 0.57107 (18) | 0.13768 (15) | −0.17246 (9) | 0.0334 (5) | |
H43 | 0.5067 | 0.1470 | −0.1739 | 0.040* | |
C44 | 0.59911 (18) | 0.10612 (15) | −0.13109 (9) | 0.0322 (5) | |
H44 | 0.5535 | 0.0942 | −0.1045 | 0.039* | |
O45 | 0.60583 (13) | 0.18700 (12) | −0.25092 (6) | 0.0392 (4) | |
H45 | 0.6496 | 0.1928 | −0.2730 | 0.059* | |
C46 | 0.43552 (17) | −0.30437 (15) | −0.02774 (8) | 0.0298 (5) | |
C47 | 0.34242 (18) | −0.28926 (17) | −0.02427 (9) | 0.0355 (5) | |
H47 | 0.3502 | −0.2265 | −0.0119 | 0.043* | |
C48 | 0.23823 (18) | −0.36421 (16) | −0.03863 (9) | 0.0383 (6) | |
H48 | 0.1755 | −0.3527 | −0.0357 | 0.046* | |
C49 | 0.22627 (18) | −0.45629 (16) | −0.05729 (9) | 0.0370 (6) | |
C50 | 0.31747 (19) | −0.47270 (17) | −0.06056 (9) | 0.0375 (6) | |
H50 | 0.3094 | −0.5356 | −0.0728 | 0.045* | |
C51 | 0.42128 (18) | −0.39741 (16) | −0.04595 (9) | 0.0345 (5) | |
H51 | 0.4837 | −0.4095 | −0.0484 | 0.041* | |
O52 | 0.12573 (13) | −0.53295 (11) | −0.07239 (7) | 0.0489 (5) | |
H52 | 0.0765 | −0.5146 | −0.0685 | 0.073* | |
C53 | 0.68522 (17) | −0.19749 (14) | 0.53673 (8) | 0.0274 (5) | |
C54 | 0.65216 (17) | −0.25367 (15) | 0.57406 (8) | 0.0302 (5) | |
H54 | 0.6684 | −0.3051 | 0.5763 | 0.036* | |
C55 | 0.59317 (17) | −0.22092 (15) | 0.60609 (8) | 0.0291 (5) | |
H55 | 0.5618 | −0.2454 | 0.6346 | 0.035* | |
C56 | 0.58649 (17) | −0.14332 (14) | 0.58941 (8) | 0.0261 (5) | |
C57 | 0.52688 (17) | −0.09328 (14) | 0.60857 (8) | 0.0257 (5) | |
C58 | 0.52863 (16) | −0.01452 (14) | 0.59219 (8) | 0.0244 (5) | |
C59 | 0.45810 (17) | 0.03071 (15) | 0.60819 (8) | 0.0274 (5) | |
H59 | 0.4009 | 0.0099 | 0.6288 | 0.033* | |
C60 | 0.48911 (17) | 0.10720 (15) | 0.58836 (8) | 0.0266 (5) | |
H60 | 0.4578 | 0.1507 | 0.5919 | 0.032* | |
C61 | 0.57999 (16) | 0.11073 (14) | 0.56034 (8) | 0.0243 (5) | |
C62 | 0.64071 (16) | 0.18640 (14) | 0.53791 (8) | 0.0247 (5) | |
C63 | 0.71602 (16) | 0.18449 (14) | 0.50345 (8) | 0.0243 (5) | |
C64 | 0.78337 (17) | 0.25826 (15) | 0.48018 (8) | 0.0277 (5) | |
H64 | 0.7890 | 0.3208 | 0.4870 | 0.033* | |
C65 | 0.83805 (17) | 0.22336 (15) | 0.44656 (8) | 0.0275 (5) | |
H65 | 0.8873 | 0.2571 | 0.4253 | 0.033* | |
C66 | 0.80923 (16) | 0.12783 (14) | 0.44855 (8) | 0.0249 (5) | |
C67 | 0.84372 (16) | 0.06436 (14) | 0.41913 (8) | 0.0247 (5) | |
C68 | 0.82273 (17) | −0.02531 (15) | 0.42703 (8) | 0.0261 (5) | |
C69 | 0.85031 (17) | −0.09367 (15) | 0.39272 (8) | 0.0287 (5) | |
H69 | 0.8811 | −0.0868 | 0.3612 | 0.034* | |
C70 | 0.82414 (17) | −0.16784 (15) | 0.41412 (8) | 0.0297 (5) | |
H70 | 0.8332 | −0.2235 | 0.4009 | 0.036* | |
C71 | 0.77898 (16) | −0.14656 (15) | 0.46164 (8) | 0.0264 (5) | |
C72 | 0.74315 (17) | −0.20860 (14) | 0.49527 (8) | 0.0266 (5) | |
N73 | 0.64570 (14) | −0.13032 (12) | 0.54814 (7) | 0.0269 (4) | |
H73 | 0.6568 | −0.0855 | 0.5314 | 0.032* | 0.50 |
N74 | 0.59926 (13) | 0.03393 (12) | 0.56140 (6) | 0.0246 (4) | |
H74 | 0.6472 | 0.0188 | 0.5456 | 0.030* | 0.50 |
N75 | 0.73667 (13) | 0.10787 (12) | 0.48453 (6) | 0.0250 (4) | |
H75 | 0.7078 | 0.0538 | 0.4940 | 0.030* | 0.50 |
N76 | 0.77646 (14) | −0.06087 (12) | 0.46786 (6) | 0.0257 (4) | |
H76 | 0.7505 | −0.0340 | 0.4929 | 0.031* | 0.50 |
C77 | 0.45933 (17) | −0.12610 (15) | 0.65029 (8) | 0.0260 (5) | |
C78 | 0.38117 (17) | −0.21947 (15) | 0.64357 (8) | 0.0290 (5) | |
H78 | 0.3681 | −0.2638 | 0.6109 | 0.035* | |
C79 | 0.32181 (18) | −0.24938 (16) | 0.68347 (9) | 0.0322 (5) | |
H79 | 0.2688 | −0.3135 | 0.6780 | 0.039* | |
C80 | 0.34002 (19) | −0.18567 (17) | 0.73120 (9) | 0.0349 (5) | |
C81 | 0.41514 (19) | −0.09244 (17) | 0.73836 (9) | 0.0360 (6) | |
H81 | 0.4265 | −0.0482 | 0.7708 | 0.043* | |
C82 | 0.47429 (18) | −0.06275 (16) | 0.69866 (8) | 0.0314 (5) | |
H82 | 0.5260 | 0.0018 | 0.7043 | 0.038* | |
O83 | 0.28428 (15) | −0.21110 (12) | 0.77211 (7) | 0.0502 (5) | |
H83 | 0.2482 | −0.2704 | 0.7651 | 0.075* | |
C84 | 0.62616 (16) | 0.27508 (14) | 0.55246 (8) | 0.0249 (5) | |
C85 | 0.64041 (17) | 0.32174 (14) | 0.60527 (8) | 0.0285 (5) | |
H85 | 0.6597 | 0.2967 | 0.6318 | 0.034* | |
C86 | 0.62684 (17) | 0.40429 (15) | 0.61963 (9) | 0.0304 (5) | |
H86 | 0.6366 | 0.4348 | 0.6558 | 0.036* | |
C87 | 0.59914 (17) | 0.44229 (15) | 0.58150 (9) | 0.0297 (5) | |
C88 | 0.58501 (17) | 0.39694 (15) | 0.52870 (9) | 0.0298 (5) | |
H88 | 0.5662 | 0.4224 | 0.5022 | 0.036* | |
C89 | 0.59836 (17) | 0.31466 (15) | 0.51486 (8) | 0.0280 (5) | |
H89 | 0.5883 | 0.2842 | 0.4787 | 0.034* | |
O90 | 0.58397 (13) | 0.52276 (10) | 0.59353 (6) | 0.0372 (4) | |
H90 | 0.5945 | 0.5437 | 0.6263 | 0.056* | |
C91 | 0.90542 (17) | 0.09415 (14) | 0.37538 (8) | 0.0265 (5) | |
C92 | 0.85944 (17) | 0.11683 (14) | 0.33468 (8) | 0.0272 (5) | |
H92 | 0.7896 | 0.1162 | 0.3361 | 0.033* | |
C93 | 0.91321 (18) | 0.14012 (15) | 0.29254 (8) | 0.0289 (5) | |
H93 | 0.8802 | 0.1551 | 0.2653 | 0.035* | |
C94 | 1.01525 (18) | 0.14161 (15) | 0.28992 (8) | 0.0289 (5) | |
C95 | 1.06301 (18) | 0.12016 (15) | 0.33039 (8) | 0.0295 (5) | |
H95 | 1.1332 | 0.1214 | 0.3289 | 0.035* | |
C96 | 1.00920 (17) | 0.09709 (14) | 0.37249 (8) | 0.0278 (5) | |
H96 | 1.0429 | 0.0830 | 0.3999 | 0.033* | |
O97 | 1.07319 (12) | 0.16468 (12) | 0.24952 (6) | 0.0375 (4) | |
H97 | 1.0371 | 0.1767 | 0.2277 | 0.056* | |
C98 | 0.76603 (18) | −0.29356 (15) | 0.48330 (8) | 0.0284 (5) | |
C99 | 0.87117 (18) | −0.28551 (16) | 0.49110 (9) | 0.0320 (5) | |
H99 | 0.9293 | −0.2257 | 0.5083 | 0.038* | |
C100 | 0.89357 (19) | −0.36270 (16) | 0.47434 (9) | 0.0354 (5) | |
H100 | 0.9660 | −0.3559 | 0.4807 | 0.042* | |
C101 | 0.80946 (19) | −0.44999 (16) | 0.44826 (9) | 0.0350 (5) | |
C102 | 0.70376 (19) | −0.45984 (16) | 0.44076 (10) | 0.0386 (6) | |
H102 | 0.6457 | −0.5198 | 0.4237 | 0.046* | |
C103 | 0.68254 (19) | −0.38250 (16) | 0.45813 (9) | 0.0362 (6) | |
H103 | 0.6096 | −0.3901 | 0.4528 | 0.043* | |
O104 | 0.82705 (14) | −0.52767 (11) | 0.42967 (8) | 0.0516 (5) | |
H104 | 0.8946 | −0.5110 | 0.4308 | 0.077* | |
O105 | 0.95763 (14) | 0.19200 (12) | 0.17650 (6) | 0.0401 (4) | |
C106 | 0.8681 (2) | 0.12415 (19) | 0.15637 (9) | 0.0390 (6) | |
H106 | 0.8509 | 0.0660 | 0.1660 | 0.047* | |
N107 | 0.79474 (17) | 0.12642 (15) | 0.12250 (8) | 0.0410 (5) | |
C108 | 0.6892 (2) | 0.0453 (2) | 0.10305 (12) | 0.0579 (8) | |
H10A | 0.6855 | −0.0076 | 0.1175 | 0.087* | |
H10B | 0.6800 | 0.0262 | 0.0646 | 0.087* | |
H10C | 0.6309 | 0.0624 | 0.1140 | 0.087* | |
C109 | 0.8147 (2) | 0.2122 (2) | 0.10593 (11) | 0.0535 (7) | |
H10D | 0.7731 | 0.2429 | 0.1245 | 0.080* | |
H10E | 0.7916 | 0.1964 | 0.0679 | 0.080* | |
H10F | 0.8929 | 0.2556 | 0.1142 | 0.080* | |
O110 | 0.74352 (13) | 0.21603 (12) | −0.32175 (6) | 0.0411 (4) | |
C111 | 0.77188 (19) | 0.15508 (19) | −0.34392 (9) | 0.0386 (6) | |
H111 | 0.7368 | 0.0938 | −0.3373 | 0.046* | |
N112 | 0.84610 (16) | 0.16795 (15) | −0.37567 (8) | 0.0425 (5) | |
C113 | 0.8782 (2) | 0.0934 (2) | −0.39607 (11) | 0.0623 (8) | |
H11A | 0.8315 | 0.0357 | −0.3855 | 0.094* | |
H11B | 0.9547 | 0.1138 | −0.3819 | 0.094* | |
H11C | 0.8702 | 0.0804 | −0.4345 | 0.094* | |
C114 | 0.9056 (2) | 0.2592 (2) | −0.38730 (10) | 0.0571 (8) | |
H11D | 0.8664 | 0.2980 | −0.3782 | 0.086* | |
H11E | 0.9120 | 0.2500 | −0.4249 | 0.086* | |
H11F | 0.9789 | 0.2914 | −0.3667 | 0.086* | |
O115 | 0.99135 (15) | −0.41564 (12) | 0.24325 (8) | 0.0568 (5) | |
C116 | 1.0740 (2) | −0.42251 (19) | 0.25599 (10) | 0.0478 (7) | |
H116 | 1.1280 | −0.3712 | 0.2821 | 0.057* | |
N117 | 1.09516 (17) | −0.49425 (15) | 0.23698 (8) | 0.0561 (6) | |
C118 | 1.0171 (2) | −0.57691 (17) | 0.19583 (11) | 0.0705 (9) | |
H11G | 0.9464 | −0.5746 | 0.1926 | 0.106* | |
H11H | 1.0077 | −0.6356 | 0.2055 | 0.106* | |
H11I | 1.0455 | −0.5754 | 0.1622 | 0.106* | |
C119 | 1.2039 (3) | −0.4898 (4) | 0.25047 (17) | 0.135 (2) | |
H11J | 1.2434 | −0.4829 | 0.2201 | 0.203* | |
H11K | 1.1951 | −0.5483 | 0.2601 | 0.203* | |
H11L | 1.2455 | −0.4353 | 0.2802 | 0.203* | |
O120 | −0.02141 (14) | −0.46403 (12) | −0.05977 (8) | 0.0560 (5) | |
C121 | −0.1209 (2) | −0.50605 (17) | −0.06123 (10) | 0.0438 (6) | |
H121 | −0.1520 | −0.4806 | −0.0342 | 0.053* | |
N122 | −0.18868 (16) | −0.58286 (13) | −0.09657 (8) | 0.0404 (5) | |
C123 | −0.1491 (2) | −0.62549 (19) | −0.13972 (10) | 0.0556 (7) | |
H12A | −0.0734 | −0.5820 | −0.1413 | 0.083* | |
H12B | −0.1950 | −0.6382 | −0.1728 | 0.083* | |
H12C | −0.1520 | −0.6852 | −0.1343 | 0.083* | |
C124 | −0.3042 (2) | −0.62999 (19) | −0.09290 (12) | 0.0546 (7) | |
H12D | −0.3212 | −0.5928 | −0.0631 | 0.082* | |
H12E | −0.3227 | −0.6934 | −0.0876 | 0.082* | |
H12F | −0.3470 | −0.6356 | −0.1255 | 0.082* | |
O125 | 1.48787 (15) | 0.61304 (13) | 0.20928 (7) | 0.0564 (5) | |
C126 | 1.5524 (2) | 0.69725 (19) | 0.21336 (10) | 0.0439 (6) | |
H126 | 1.5701 | 0.7165 | 0.1817 | 0.053* | |
N127 | 1.59827 (15) | 0.76199 (14) | 0.25778 (7) | 0.0397 (5) | |
C128 | 1.5648 (3) | 0.7395 (2) | 0.30642 (10) | 0.0647 (8) | |
H12G | 1.5194 | 0.7708 | 0.3193 | 0.097* | |
H12H | 1.6297 | 0.7617 | 0.3325 | 0.097* | |
H12I | 1.5227 | 0.6706 | 0.3006 | 0.097* | |
C129 | 1.6664 (2) | 0.86026 (18) | 0.25941 (12) | 0.0608 (8) | |
H12J | 1.6817 | 0.8666 | 0.2239 | 0.091* | |
H12K | 1.7353 | 0.8825 | 0.2826 | 0.091* | |
H12L | 1.6284 | 0.8985 | 0.2728 | 0.091* | |
O130 | 1.04601 (15) | −0.46155 (13) | 0.43644 (9) | 0.0664 (6) | |
C131 | 1.0999 (2) | −0.50711 (17) | 0.42820 (11) | 0.0458 (6) | |
H131 | 1.1621 | −0.4893 | 0.4533 | 0.055* | |
N132 | 1.07794 (15) | −0.57862 (13) | 0.38727 (8) | 0.0369 (5) | |
C133 | 1.1410 (2) | −0.63312 (17) | 0.38350 (11) | 0.0457 (6) | |
H13A | 1.1996 | −0.6053 | 0.4136 | 0.069* | |
H13B | 1.1730 | −0.6318 | 0.3508 | 0.069* | |
H13C | 1.0930 | −0.6989 | 0.3836 | 0.069* | |
C134 | 0.9868 (2) | −0.60799 (19) | 0.34651 (11) | 0.0530 (7) | |
H13D | 0.9232 | −0.6612 | 0.3532 | 0.079* | |
H13E | 1.0067 | −0.6278 | 0.3122 | 0.079* | |
H13F | 0.9689 | −0.5548 | 0.3465 | 0.079* | |
O135 | 0.61712 (17) | 0.60059 (13) | 0.69760 (7) | 0.0610 (5) | |
C136 | 0.6591 (2) | 0.68716 (19) | 0.71438 (10) | 0.0441 (6) | |
H136 | 0.7233 | 0.7230 | 0.7010 | 0.053* | |
N137 | 0.62302 (15) | 0.73484 (13) | 0.74933 (8) | 0.0390 (5) | |
C138 | 0.6754 (2) | 0.83740 (18) | 0.76594 (11) | 0.0505 (7) | |
H13G | 0.7409 | 0.8624 | 0.7491 | 0.076* | |
H13H | 0.6960 | 0.8574 | 0.8042 | 0.076* | |
H13I | 0.6246 | 0.8619 | 0.7558 | 0.076* | |
C139 | 0.5257 (3) | 0.6852 (2) | 0.77182 (15) | 0.0878 (12) | |
H13J | 0.4732 | 0.7109 | 0.7668 | 0.132* | |
H13K | 0.5456 | 0.6939 | 0.8095 | 0.132* | |
H13L | 0.4925 | 0.6174 | 0.7543 | 0.132* | |
O40A | 0.2034 (4) | −0.3981 (3) | 0.75012 (18) | 0.0729 (12) | 0.50 |
C41A | 0.2395 (5) | −0.4579 (4) | 0.7354 (3) | 0.0613 (16) | 0.50 |
H41A | 0.2460 | −0.4583 | 0.6995 | 0.074* | 0.50 |
N42A | 0.2709 (4) | −0.5165 (4) | 0.7436 (2) | 0.0734 (15) | 0.50 |
C43A | 0.3029 (6) | −0.5096 (5) | 0.8044 (3) | 0.081 (2) | 0.50 |
H4AA | 0.2961 | −0.4556 | 0.8264 | 0.122* | 0.50 |
H4BA | 0.3784 | −0.5009 | 0.8105 | 0.122* | 0.50 |
H4CA | 0.2536 | −0.5683 | 0.8133 | 0.122* | 0.50 |
C44A | 0.2756 (5) | −0.5958 (4) | 0.7091 (3) | 0.0707 (18) | 0.50 |
H4DA | 0.2482 | −0.6007 | 0.6729 | 0.106* | 0.50 |
H4EA | 0.2303 | −0.6541 | 0.7195 | 0.106* | 0.50 |
H4FA | 0.3515 | −0.5869 | 0.7111 | 0.106* | 0.50 |
O40B | 0.2392 (4) | −0.3898 (3) | 0.76925 (19) | 0.0637 (13) | 0.50 |
C41B | 0.2391 (6) | −0.4428 (6) | 0.7735 (3) | 0.075 (2) | 0.50 |
H41B | 0.2113 | −0.4540 | 0.8053 | 0.091* | 0.50 |
N42B | 0.2642 (3) | −0.5166 (3) | 0.75133 (16) | 0.0431 (10) | 0.50 |
C43B | 0.3041 (6) | −0.5623 (5) | 0.7771 (3) | 0.087 (2) | 0.50 |
H4AB | 0.3760 | −0.5530 | 0.7674 | 0.130* | 0.50 |
H4BB | 0.2542 | −0.6303 | 0.7677 | 0.130* | 0.50 |
H4CB | 0.3114 | −0.5371 | 0.8151 | 0.130* | 0.50 |
C44B | 0.2465 (7) | −0.5428 (6) | 0.6908 (3) | 0.096 (2) | 0.50 |
H4DB | 0.3174 | −0.5258 | 0.6782 | 0.144* | 0.50 |
H4EB | 0.2102 | −0.5080 | 0.6780 | 0.144* | 0.50 |
H4FB | 0.2006 | −0.6112 | 0.6778 | 0.144* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0269 (12) | 0.0301 (13) | 0.0325 (13) | 0.0110 (10) | 0.0062 (10) | 0.0095 (10) |
C2 | 0.0267 (12) | 0.0353 (14) | 0.0356 (13) | 0.0110 (10) | 0.0087 (10) | 0.0126 (10) |
C3 | 0.0303 (12) | 0.0328 (13) | 0.0317 (13) | 0.0140 (10) | 0.0082 (10) | 0.0133 (10) |
C4 | 0.0315 (12) | 0.0293 (13) | 0.0271 (12) | 0.0148 (10) | 0.0055 (10) | 0.0079 (9) |
C5 | 0.0288 (12) | 0.0294 (13) | 0.0235 (11) | 0.0148 (10) | 0.0037 (9) | 0.0028 (9) |
C6 | 0.0281 (12) | 0.0256 (12) | 0.0224 (11) | 0.0128 (9) | 0.0040 (9) | 0.0021 (9) |
C7 | 0.0295 (12) | 0.0319 (13) | 0.0283 (12) | 0.0167 (10) | 0.0031 (10) | 0.0069 (10) |
C8 | 0.0263 (12) | 0.0298 (13) | 0.0320 (12) | 0.0127 (10) | 0.0038 (10) | 0.0045 (10) |
C9 | 0.0239 (11) | 0.0306 (13) | 0.0237 (11) | 0.0136 (10) | 0.0055 (9) | 0.0023 (9) |
C10 | 0.0267 (12) | 0.0258 (12) | 0.0245 (11) | 0.0112 (9) | 0.0065 (9) | 0.0030 (9) |
C11 | 0.0258 (11) | 0.0251 (12) | 0.0233 (11) | 0.0097 (9) | 0.0055 (9) | 0.0012 (9) |
C12 | 0.0326 (13) | 0.0249 (13) | 0.0341 (13) | 0.0099 (10) | 0.0044 (10) | 0.0071 (10) |
C13 | 0.0347 (13) | 0.0286 (13) | 0.0344 (13) | 0.0147 (10) | 0.0025 (10) | 0.0094 (10) |
C14 | 0.0286 (12) | 0.0294 (13) | 0.0274 (12) | 0.0139 (10) | 0.0051 (10) | 0.0074 (9) |
C15 | 0.0292 (12) | 0.0301 (13) | 0.0236 (11) | 0.0155 (10) | 0.0034 (9) | 0.0056 (9) |
C16 | 0.0257 (11) | 0.0324 (13) | 0.0260 (12) | 0.0162 (10) | 0.0043 (9) | 0.0061 (9) |
C17 | 0.0292 (12) | 0.0345 (14) | 0.0268 (12) | 0.0161 (10) | 0.0023 (10) | 0.0047 (10) |
C18 | 0.0259 (12) | 0.0305 (13) | 0.0320 (13) | 0.0105 (10) | 0.0019 (10) | 0.0077 (10) |
C19 | 0.0242 (11) | 0.0292 (13) | 0.0300 (12) | 0.0119 (10) | 0.0051 (9) | 0.0054 (9) |
C20 | 0.0246 (11) | 0.0293 (13) | 0.0317 (12) | 0.0119 (10) | 0.0062 (10) | 0.0074 (9) |
N21 | 0.0233 (9) | 0.0300 (10) | 0.0281 (10) | 0.0098 (8) | 0.0021 (8) | 0.0075 (8) |
N22 | 0.0226 (9) | 0.0291 (10) | 0.0239 (9) | 0.0115 (8) | 0.0026 (7) | 0.0042 (8) |
N23 | 0.0266 (10) | 0.0284 (10) | 0.0242 (10) | 0.0109 (8) | 0.0022 (8) | 0.0058 (8) |
N24 | 0.0245 (10) | 0.0309 (11) | 0.0257 (10) | 0.0104 (8) | 0.0007 (8) | 0.0065 (8) |
C25 | 0.0237 (11) | 0.0278 (12) | 0.0277 (12) | 0.0104 (9) | 0.0024 (9) | 0.0083 (9) |
C26 | 0.0254 (11) | 0.0304 (13) | 0.0247 (12) | 0.0113 (10) | 0.0033 (9) | 0.0033 (9) |
C27 | 0.0292 (12) | 0.0250 (12) | 0.0346 (13) | 0.0129 (10) | 0.0046 (10) | 0.0068 (10) |
C28 | 0.0316 (13) | 0.0375 (14) | 0.0275 (13) | 0.0149 (10) | 0.0013 (10) | 0.0110 (10) |
C29 | 0.0433 (14) | 0.0354 (14) | 0.0252 (12) | 0.0187 (11) | −0.0004 (10) | 0.0014 (10) |
C30 | 0.0383 (13) | 0.0295 (13) | 0.0311 (13) | 0.0176 (11) | 0.0015 (10) | 0.0036 (10) |
O31 | 0.0606 (11) | 0.0447 (11) | 0.0338 (9) | 0.0286 (10) | −0.0027 (8) | 0.0110 (8) |
C32 | 0.0249 (11) | 0.0275 (12) | 0.0316 (12) | 0.0137 (9) | 0.0052 (9) | 0.0052 (9) |
C33 | 0.0299 (12) | 0.0310 (13) | 0.0268 (12) | 0.0119 (10) | 0.0046 (10) | 0.0043 (9) |
C34 | 0.0344 (13) | 0.0361 (14) | 0.0274 (12) | 0.0158 (11) | −0.0002 (10) | −0.0022 (10) |
C35 | 0.0247 (12) | 0.0278 (13) | 0.0434 (14) | 0.0095 (10) | 0.0030 (10) | 0.0037 (10) |
C36 | 0.0283 (12) | 0.0315 (13) | 0.0380 (14) | 0.0131 (10) | 0.0079 (10) | 0.0100 (10) |
C37 | 0.0300 (12) | 0.0291 (13) | 0.0289 (12) | 0.0138 (10) | 0.0048 (10) | 0.0058 (9) |
O38 | 0.0317 (9) | 0.0330 (10) | 0.0477 (10) | 0.0048 (7) | 0.0014 (8) | 0.0012 (8) |
C39 | 0.0288 (12) | 0.0235 (12) | 0.0289 (12) | 0.0084 (9) | −0.0017 (10) | 0.0031 (9) |
C40 | 0.0298 (12) | 0.0316 (13) | 0.0340 (13) | 0.0141 (10) | 0.0006 (10) | 0.0084 (10) |
C41 | 0.0323 (13) | 0.0326 (13) | 0.0308 (13) | 0.0127 (10) | 0.0019 (10) | 0.0094 (10) |
C42 | 0.0349 (13) | 0.0269 (13) | 0.0293 (13) | 0.0121 (10) | −0.0021 (10) | 0.0077 (10) |
C43 | 0.0291 (12) | 0.0335 (13) | 0.0395 (14) | 0.0167 (10) | −0.0002 (11) | 0.0076 (10) |
C44 | 0.0280 (12) | 0.0316 (13) | 0.0353 (13) | 0.0119 (10) | 0.0044 (10) | 0.0072 (10) |
O45 | 0.0400 (10) | 0.0457 (10) | 0.0392 (10) | 0.0230 (8) | 0.0034 (8) | 0.0168 (8) |
C46 | 0.0246 (12) | 0.0311 (13) | 0.0311 (12) | 0.0085 (10) | 0.0030 (9) | 0.0106 (10) |
C47 | 0.0303 (13) | 0.0330 (14) | 0.0424 (14) | 0.0136 (11) | 0.0028 (11) | 0.0089 (11) |
C48 | 0.0240 (12) | 0.0375 (15) | 0.0506 (15) | 0.0122 (11) | 0.0027 (11) | 0.0086 (11) |
C49 | 0.0284 (13) | 0.0328 (14) | 0.0391 (14) | 0.0052 (11) | 0.0025 (10) | 0.0054 (10) |
C50 | 0.0334 (13) | 0.0297 (14) | 0.0442 (14) | 0.0122 (11) | 0.0047 (11) | 0.0022 (10) |
C51 | 0.0294 (13) | 0.0341 (14) | 0.0403 (14) | 0.0147 (11) | 0.0043 (10) | 0.0087 (11) |
O52 | 0.0303 (9) | 0.0372 (10) | 0.0682 (12) | 0.0105 (8) | 0.0016 (9) | 0.0008 (9) |
C53 | 0.0303 (12) | 0.0238 (12) | 0.0326 (12) | 0.0152 (10) | 0.0083 (10) | 0.0079 (9) |
C54 | 0.0315 (12) | 0.0323 (13) | 0.0338 (13) | 0.0188 (10) | 0.0085 (10) | 0.0111 (10) |
C55 | 0.0314 (12) | 0.0300 (13) | 0.0292 (12) | 0.0141 (10) | 0.0088 (10) | 0.0118 (9) |
C56 | 0.0289 (12) | 0.0253 (12) | 0.0237 (11) | 0.0117 (9) | 0.0059 (9) | 0.0051 (9) |
C57 | 0.0269 (11) | 0.0264 (12) | 0.0225 (11) | 0.0120 (9) | 0.0037 (9) | 0.0026 (9) |
C58 | 0.0247 (11) | 0.0230 (12) | 0.0232 (11) | 0.0099 (9) | 0.0030 (9) | 0.0019 (9) |
C59 | 0.0239 (11) | 0.0268 (12) | 0.0284 (12) | 0.0100 (9) | 0.0054 (9) | 0.0027 (9) |
C60 | 0.0275 (12) | 0.0272 (12) | 0.0266 (12) | 0.0152 (9) | 0.0040 (9) | 0.0026 (9) |
C61 | 0.0242 (11) | 0.0235 (12) | 0.0236 (11) | 0.0108 (9) | 0.0020 (9) | 0.0016 (9) |
C62 | 0.0255 (11) | 0.0237 (12) | 0.0234 (11) | 0.0116 (9) | −0.0013 (9) | 0.0020 (9) |
C63 | 0.0253 (11) | 0.0230 (12) | 0.0239 (11) | 0.0109 (9) | 0.0010 (9) | 0.0041 (9) |
C64 | 0.0308 (12) | 0.0238 (12) | 0.0288 (12) | 0.0129 (10) | 0.0040 (10) | 0.0052 (9) |
C65 | 0.0285 (12) | 0.0256 (12) | 0.0285 (12) | 0.0117 (10) | 0.0057 (9) | 0.0070 (9) |
C66 | 0.0253 (11) | 0.0265 (12) | 0.0246 (11) | 0.0125 (9) | 0.0040 (9) | 0.0076 (9) |
C67 | 0.0235 (11) | 0.0259 (12) | 0.0258 (11) | 0.0124 (9) | 0.0027 (9) | 0.0053 (9) |
C68 | 0.0264 (11) | 0.0298 (13) | 0.0243 (11) | 0.0143 (10) | 0.0044 (9) | 0.0062 (9) |
C69 | 0.0305 (12) | 0.0325 (13) | 0.0271 (12) | 0.0168 (10) | 0.0098 (10) | 0.0075 (10) |
C70 | 0.0331 (12) | 0.0272 (13) | 0.0325 (12) | 0.0171 (10) | 0.0086 (10) | 0.0056 (10) |
C71 | 0.0222 (11) | 0.0273 (12) | 0.0312 (12) | 0.0132 (9) | 0.0061 (9) | 0.0051 (9) |
C72 | 0.0248 (11) | 0.0256 (12) | 0.0317 (12) | 0.0129 (9) | 0.0065 (9) | 0.0074 (9) |
N73 | 0.0286 (10) | 0.0266 (10) | 0.0297 (10) | 0.0148 (8) | 0.0089 (8) | 0.0088 (8) |
N74 | 0.0252 (9) | 0.0250 (10) | 0.0262 (9) | 0.0137 (8) | 0.0065 (8) | 0.0051 (7) |
N75 | 0.0269 (10) | 0.0259 (10) | 0.0250 (9) | 0.0146 (8) | 0.0060 (8) | 0.0049 (7) |
N76 | 0.0276 (10) | 0.0275 (10) | 0.0272 (10) | 0.0167 (8) | 0.0087 (8) | 0.0064 (8) |
C77 | 0.0269 (11) | 0.0271 (12) | 0.0264 (12) | 0.0148 (10) | 0.0044 (9) | 0.0047 (9) |
C78 | 0.0288 (12) | 0.0309 (13) | 0.0289 (12) | 0.0153 (10) | 0.0052 (10) | 0.0057 (9) |
C79 | 0.0305 (12) | 0.0322 (13) | 0.0382 (13) | 0.0154 (10) | 0.0114 (10) | 0.0126 (10) |
C80 | 0.0408 (14) | 0.0426 (15) | 0.0325 (13) | 0.0247 (12) | 0.0175 (11) | 0.0158 (11) |
C81 | 0.0459 (15) | 0.0352 (14) | 0.0296 (13) | 0.0222 (12) | 0.0075 (11) | 0.0039 (10) |
C82 | 0.0359 (13) | 0.0294 (13) | 0.0294 (12) | 0.0151 (10) | 0.0067 (10) | 0.0064 (10) |
O83 | 0.0653 (13) | 0.0501 (11) | 0.0448 (10) | 0.0278 (10) | 0.0330 (9) | 0.0210 (9) |
C84 | 0.0245 (11) | 0.0235 (12) | 0.0267 (12) | 0.0105 (9) | 0.0049 (9) | 0.0062 (9) |
C85 | 0.0322 (12) | 0.0276 (13) | 0.0272 (12) | 0.0138 (10) | 0.0053 (10) | 0.0083 (9) |
C86 | 0.0353 (13) | 0.0267 (13) | 0.0288 (12) | 0.0152 (10) | 0.0069 (10) | 0.0021 (9) |
C87 | 0.0256 (12) | 0.0235 (12) | 0.0433 (14) | 0.0137 (9) | 0.0101 (10) | 0.0079 (10) |
C88 | 0.0299 (12) | 0.0305 (13) | 0.0333 (13) | 0.0162 (10) | 0.0064 (10) | 0.0101 (10) |
C89 | 0.0275 (12) | 0.0277 (12) | 0.0279 (12) | 0.0125 (10) | 0.0062 (9) | 0.0038 (9) |
O90 | 0.0423 (10) | 0.0272 (9) | 0.0472 (10) | 0.0213 (8) | 0.0076 (8) | 0.0057 (7) |
C91 | 0.0297 (12) | 0.0225 (12) | 0.0268 (12) | 0.0116 (9) | 0.0074 (9) | 0.0041 (9) |
C92 | 0.0284 (12) | 0.0264 (12) | 0.0296 (12) | 0.0151 (10) | 0.0078 (10) | 0.0048 (9) |
C93 | 0.0350 (13) | 0.0289 (13) | 0.0264 (12) | 0.0164 (10) | 0.0062 (10) | 0.0084 (9) |
C94 | 0.0322 (13) | 0.0241 (12) | 0.0287 (12) | 0.0106 (10) | 0.0114 (10) | 0.0055 (9) |
C95 | 0.0290 (12) | 0.0277 (13) | 0.0333 (13) | 0.0142 (10) | 0.0091 (10) | 0.0061 (10) |
C96 | 0.0303 (12) | 0.0261 (12) | 0.0291 (12) | 0.0143 (10) | 0.0050 (10) | 0.0066 (9) |
O97 | 0.0377 (9) | 0.0473 (10) | 0.0342 (9) | 0.0215 (8) | 0.0139 (8) | 0.0160 (8) |
C98 | 0.0328 (13) | 0.0297 (13) | 0.0299 (12) | 0.0180 (10) | 0.0117 (10) | 0.0112 (10) |
C99 | 0.0329 (13) | 0.0299 (13) | 0.0361 (13) | 0.0171 (10) | 0.0040 (10) | 0.0071 (10) |
C100 | 0.0316 (13) | 0.0359 (14) | 0.0453 (14) | 0.0218 (11) | 0.0073 (11) | 0.0080 (11) |
C101 | 0.0391 (14) | 0.0280 (13) | 0.0463 (14) | 0.0214 (11) | 0.0166 (11) | 0.0098 (11) |
C102 | 0.0330 (13) | 0.0279 (13) | 0.0514 (15) | 0.0117 (11) | 0.0104 (11) | 0.0053 (11) |
C103 | 0.0288 (13) | 0.0343 (14) | 0.0494 (15) | 0.0164 (11) | 0.0124 (11) | 0.0116 (11) |
O104 | 0.0421 (10) | 0.0319 (10) | 0.0823 (13) | 0.0224 (8) | 0.0112 (10) | 0.0025 (9) |
O105 | 0.0434 (10) | 0.0506 (11) | 0.0343 (9) | 0.0247 (9) | 0.0133 (8) | 0.0164 (8) |
C106 | 0.0425 (15) | 0.0506 (17) | 0.0343 (14) | 0.0281 (13) | 0.0146 (12) | 0.0133 (12) |
N107 | 0.0437 (12) | 0.0515 (14) | 0.0372 (12) | 0.0301 (11) | 0.0134 (10) | 0.0087 (10) |
C108 | 0.0447 (16) | 0.0599 (19) | 0.0656 (19) | 0.0282 (15) | 0.0029 (14) | −0.0026 (15) |
C109 | 0.0614 (18) | 0.073 (2) | 0.0471 (16) | 0.0446 (16) | 0.0146 (14) | 0.0234 (14) |
O110 | 0.0446 (10) | 0.0468 (11) | 0.0371 (9) | 0.0234 (9) | 0.0036 (8) | 0.0140 (8) |
C111 | 0.0293 (13) | 0.0497 (16) | 0.0338 (14) | 0.0147 (12) | −0.0032 (11) | 0.0117 (12) |
N112 | 0.0309 (11) | 0.0595 (15) | 0.0325 (11) | 0.0176 (10) | 0.0020 (9) | 0.0072 (10) |
C113 | 0.0477 (17) | 0.096 (2) | 0.0465 (17) | 0.0433 (17) | 0.0004 (13) | −0.0022 (16) |
C114 | 0.0411 (16) | 0.077 (2) | 0.0421 (16) | 0.0106 (15) | 0.0039 (13) | 0.0257 (14) |
O115 | 0.0481 (11) | 0.0442 (11) | 0.0779 (14) | 0.0225 (9) | 0.0002 (10) | 0.0116 (9) |
C116 | 0.0528 (17) | 0.0493 (17) | 0.0443 (16) | 0.0273 (14) | 0.0026 (13) | 0.0079 (13) |
N117 | 0.0721 (16) | 0.0647 (17) | 0.0457 (14) | 0.0456 (14) | 0.0049 (12) | 0.0092 (12) |
C118 | 0.088 (2) | 0.0449 (19) | 0.080 (2) | 0.0328 (17) | 0.0176 (19) | 0.0098 (16) |
C119 | 0.135 (4) | 0.196 (5) | 0.103 (3) | 0.139 (4) | −0.040 (3) | −0.042 (3) |
O120 | 0.0342 (11) | 0.0455 (11) | 0.0724 (13) | 0.0118 (9) | 0.0047 (9) | −0.0058 (9) |
C121 | 0.0360 (15) | 0.0345 (15) | 0.0522 (16) | 0.0119 (12) | 0.0049 (12) | 0.0006 (12) |
N122 | 0.0385 (12) | 0.0327 (12) | 0.0443 (12) | 0.0135 (9) | 0.0011 (10) | 0.0036 (9) |
C123 | 0.072 (2) | 0.0462 (17) | 0.0430 (16) | 0.0221 (15) | 0.0093 (14) | 0.0071 (13) |
C124 | 0.0359 (15) | 0.0440 (17) | 0.0691 (19) | 0.0081 (12) | −0.0040 (13) | 0.0063 (14) |
O125 | 0.0561 (12) | 0.0396 (12) | 0.0542 (12) | 0.0088 (9) | 0.0004 (9) | 0.0004 (9) |
C126 | 0.0435 (15) | 0.0495 (18) | 0.0361 (15) | 0.0197 (13) | 0.0051 (12) | 0.0068 (12) |
N127 | 0.0335 (11) | 0.0445 (13) | 0.0334 (12) | 0.0141 (10) | 0.0036 (9) | 0.0006 (9) |
C128 | 0.072 (2) | 0.077 (2) | 0.0364 (16) | 0.0297 (17) | 0.0057 (15) | 0.0022 (14) |
C129 | 0.0459 (17) | 0.0396 (17) | 0.080 (2) | 0.0110 (13) | −0.0107 (15) | 0.0009 (14) |
O130 | 0.0454 (11) | 0.0466 (12) | 0.1014 (16) | 0.0298 (10) | 0.0019 (11) | −0.0136 (11) |
C131 | 0.0359 (14) | 0.0349 (15) | 0.0630 (18) | 0.0182 (12) | 0.0026 (13) | −0.0004 (13) |
N132 | 0.0303 (11) | 0.0310 (11) | 0.0476 (12) | 0.0153 (9) | 0.0047 (9) | 0.0018 (9) |
C133 | 0.0417 (15) | 0.0355 (15) | 0.0630 (17) | 0.0223 (12) | 0.0138 (13) | 0.0051 (12) |
C134 | 0.0481 (16) | 0.0523 (18) | 0.0563 (18) | 0.0218 (14) | −0.0006 (14) | 0.0107 (14) |
O135 | 0.0863 (15) | 0.0365 (12) | 0.0564 (12) | 0.0262 (10) | 0.0227 (11) | 0.0024 (9) |
C136 | 0.0509 (16) | 0.0409 (17) | 0.0447 (15) | 0.0245 (13) | 0.0174 (13) | 0.0074 (12) |
N137 | 0.0356 (11) | 0.0362 (12) | 0.0413 (12) | 0.0156 (9) | 0.0091 (9) | 0.0010 (9) |
C138 | 0.0460 (16) | 0.0444 (17) | 0.0556 (17) | 0.0213 (13) | 0.0096 (13) | −0.0030 (13) |
C139 | 0.072 (2) | 0.058 (2) | 0.111 (3) | 0.0122 (18) | 0.050 (2) | 0.0015 (19) |
O40A | 0.082 (3) | 0.065 (3) | 0.098 (3) | 0.042 (2) | 0.044 (3) | 0.048 (2) |
C41A | 0.055 (4) | 0.043 (4) | 0.097 (5) | 0.022 (3) | 0.044 (3) | 0.033 (3) |
N42A | 0.076 (4) | 0.076 (4) | 0.096 (4) | 0.048 (3) | 0.042 (3) | 0.041 (3) |
C43A | 0.075 (5) | 0.084 (5) | 0.096 (4) | 0.028 (4) | 0.036 (4) | 0.054 (4) |
C44A | 0.074 (4) | 0.064 (4) | 0.093 (5) | 0.043 (4) | 0.027 (4) | 0.030 (3) |
O40B | 0.073 (3) | 0.050 (3) | 0.090 (3) | 0.032 (3) | 0.040 (2) | 0.046 (3) |
C41B | 0.062 (4) | 0.068 (5) | 0.115 (6) | 0.029 (4) | 0.054 (4) | 0.051 (4) |
N42B | 0.038 (2) | 0.037 (2) | 0.043 (2) | 0.0019 (19) | 0.0128 (19) | 0.0167 (19) |
C43B | 0.067 (4) | 0.097 (5) | 0.127 (6) | 0.042 (4) | 0.031 (4) | 0.075 (5) |
C44B | 0.114 (6) | 0.106 (6) | 0.064 (4) | 0.047 (5) | 0.011 (4) | 0.015 (4) |
Geometric parameters (Å, º) top
C1—N21 | 1.386 (3) | C80—O83 | 1.372 (3) |
C1—C20 | 1.398 (3) | C80—C81 | 1.376 (3) |
C1—C2 | 1.427 (3) | C81—C82 | 1.383 (3) |
C2—C3 | 1.363 (3) | C81—H81 | 0.9500 |
C2—H2 | 0.9500 | C82—H82 | 0.9500 |
C3—C4 | 1.427 (3) | O83—H83 | 0.8400 |
C3—H3 | 0.9500 | C84—C89 | 1.394 (3) |
C4—N21 | 1.378 (3) | C84—C85 | 1.397 (3) |
C4—C5 | 1.409 (3) | C85—C86 | 1.391 (3) |
C5—C6 | 1.408 (3) | C85—H85 | 0.9500 |
C5—C25 | 1.497 (3) | C86—C87 | 1.387 (3) |
C6—N22 | 1.362 (3) | C86—H86 | 0.9500 |
C6—C7 | 1.452 (3) | C87—O90 | 1.367 (2) |
C7—C8 | 1.344 (3) | C87—C88 | 1.391 (3) |
C7—H7 | 0.9500 | C88—C89 | 1.384 (3) |
C8—C9 | 1.455 (3) | C88—H88 | 0.9500 |
C8—H8 | 0.9500 | C89—H89 | 0.9500 |
C9—N22 | 1.372 (3) | O90—H90 | 0.8400 |
C9—C10 | 1.408 (3) | C91—C92 | 1.399 (3) |
C10—C11 | 1.406 (3) | C91—C96 | 1.401 (3) |
C10—C32 | 1.493 (3) | C92—C93 | 1.381 (3) |
C11—N23 | 1.382 (3) | C92—H92 | 0.9500 |
C11—C12 | 1.416 (3) | C93—C94 | 1.385 (3) |
C12—C13 | 1.361 (3) | C93—H93 | 0.9500 |
C12—H12 | 0.9500 | C94—O97 | 1.368 (2) |
C13—C14 | 1.420 (3) | C94—C95 | 1.395 (3) |
C13—H13 | 0.9500 | C95—C96 | 1.380 (3) |
C14—N23 | 1.378 (3) | C95—H95 | 0.9500 |
C14—C15 | 1.409 (3) | C96—H96 | 0.9500 |
C15—C16 | 1.402 (3) | O97—H97 | 0.8400 |
C15—C39 | 1.495 (3) | C98—C99 | 1.385 (3) |
C16—N24 | 1.362 (3) | C98—C103 | 1.395 (3) |
C16—C17 | 1.453 (3) | C99—C100 | 1.387 (3) |
C17—C18 | 1.332 (3) | C99—H99 | 0.9500 |
C17—H17 | 0.9500 | C100—C101 | 1.389 (3) |
C18—C19 | 1.450 (3) | C100—H100 | 0.9500 |
C18—H18 | 0.9500 | C101—O104 | 1.363 (3) |
C19—N24 | 1.362 (3) | C101—C102 | 1.382 (3) |
C19—C20 | 1.413 (3) | C102—C103 | 1.382 (3) |
C20—C46 | 1.495 (3) | C102—H102 | 0.9500 |
N21—H21 | 0.8800 | C103—H103 | 0.9500 |
N22—H22 | 0.8800 | O104—H104 | 0.8400 |
N23—H23 | 0.8800 | O105—C106 | 1.241 (3) |
N24—H24 | 0.8800 | C106—N107 | 1.326 (3) |
C25—C30 | 1.393 (3) | C106—H106 | 0.9500 |
C25—C26 | 1.396 (3) | N107—C109 | 1.446 (3) |
C26—C27 | 1.383 (3) | N107—C108 | 1.452 (3) |
C26—H26 | 0.9500 | C108—H10A | 0.9800 |
C27—C28 | 1.393 (3) | C108—H10B | 0.9800 |
C27—H27 | 0.9500 | C108—H10C | 0.9800 |
C28—O31 | 1.365 (3) | C109—H10D | 0.9800 |
C28—C29 | 1.386 (3) | C109—H10E | 0.9800 |
C29—C30 | 1.381 (3) | C109—H10F | 0.9800 |
C29—H29 | 0.9500 | O110—C111 | 1.244 (3) |
C30—H30 | 0.9500 | C111—N112 | 1.314 (3) |
O31—H31 | 0.8400 | C111—H111 | 0.9500 |
C32—C33 | 1.394 (3) | N112—C114 | 1.446 (3) |
C32—C37 | 1.399 (3) | N112—C113 | 1.450 (3) |
C33—C34 | 1.388 (3) | C113—H11A | 0.9800 |
C33—H33 | 0.9500 | C113—H11B | 0.9800 |
C34—C35 | 1.389 (3) | C113—H11C | 0.9800 |
C34—H34 | 0.9500 | C114—H11D | 0.9800 |
C35—O38 | 1.364 (3) | C114—H11E | 0.9800 |
C35—C36 | 1.386 (3) | C114—H11F | 0.9800 |
C36—C37 | 1.383 (3) | O115—C116 | 1.216 (3) |
C36—H36 | 0.9500 | C116—N117 | 1.308 (3) |
C37—H37 | 0.9500 | C116—H116 | 0.9500 |
O38—H38 | 0.8400 | N117—C118 | 1.477 (5) |
C39—C44 | 1.391 (3) | N117—C119 | 1.478 (5) |
C39—C40 | 1.400 (3) | C118—H11G | 0.9800 |
C40—C41 | 1.378 (3) | C118—H11H | 0.9800 |
C40—H40 | 0.9500 | C118—H11I | 0.9800 |
C41—C42 | 1.398 (3) | C119—H11J | 0.9800 |
C41—H41 | 0.9500 | C119—H11K | 0.9800 |
C42—O45 | 1.355 (3) | C119—H11L | 0.9800 |
C42—C43 | 1.386 (3) | O120—C121 | 1.229 (3) |
C43—C44 | 1.389 (3) | C121—N122 | 1.315 (3) |
C43—H43 | 0.9500 | C121—H121 | 0.9500 |
C44—H44 | 0.9500 | N122—C123 | 1.445 (3) |
O45—H45 | 0.8400 | N122—C124 | 1.449 (3) |
C46—C47 | 1.391 (3) | C123—H12A | 0.9800 |
C46—C51 | 1.395 (3) | C123—H12B | 0.9800 |
C47—C48 | 1.390 (3) | C123—H12C | 0.9800 |
C47—H47 | 0.9500 | C124—H12D | 0.9800 |
C48—C49 | 1.392 (3) | C124—H12E | 0.9800 |
C48—H48 | 0.9500 | C124—H12F | 0.9800 |
C49—O52 | 1.371 (3) | O125—C126 | 1.240 (3) |
C49—C50 | 1.377 (3) | C126—N127 | 1.313 (3) |
C50—C51 | 1.389 (3) | C126—H126 | 0.9500 |
C50—H50 | 0.9500 | N127—C128 | 1.438 (3) |
C51—H51 | 0.9500 | N127—C129 | 1.442 (3) |
O52—H52 | 0.8400 | C128—H12G | 0.9800 |
C53—N73 | 1.381 (3) | C128—H12H | 0.9800 |
C53—C72 | 1.397 (3) | C128—H12I | 0.9800 |
C53—C54 | 1.424 (3) | C129—H12J | 0.9800 |
C54—C55 | 1.365 (3) | C129—H12K | 0.9800 |
C54—H54 | 0.9500 | C129—H12L | 0.9800 |
C55—C56 | 1.435 (3) | O130—C131 | 1.233 (3) |
C55—H55 | 0.9500 | C131—N132 | 1.318 (3) |
C56—N73 | 1.376 (3) | C131—H131 | 0.9500 |
C56—C57 | 1.405 (3) | N132—C134 | 1.447 (3) |
C57—C58 | 1.405 (3) | N132—C133 | 1.454 (3) |
C57—C77 | 1.496 (3) | C133—H13A | 0.9800 |
C58—N74 | 1.369 (3) | C133—H13B | 0.9800 |
C58—C59 | 1.457 (3) | C133—H13C | 0.9800 |
C59—C60 | 1.339 (3) | C134—H13D | 0.9800 |
C59—H59 | 0.9500 | C134—H13E | 0.9800 |
C60—C61 | 1.454 (3) | C134—H13F | 0.9800 |
C60—H60 | 0.9500 | O135—C136 | 1.227 (3) |
C61—N74 | 1.367 (3) | C136—N137 | 1.318 (3) |
C61—C62 | 1.410 (3) | C136—H136 | 0.9500 |
C62—C63 | 1.403 (3) | N137—C138 | 1.446 (3) |
C62—C84 | 1.492 (3) | N137—C139 | 1.453 (3) |
C63—N75 | 1.374 (3) | C138—H13G | 0.9800 |
C63—C64 | 1.428 (3) | C138—H13H | 0.9800 |
C64—C65 | 1.361 (3) | C138—H13I | 0.9800 |
C64—H64 | 0.9500 | C139—H13J | 0.9800 |
C65—C66 | 1.423 (3) | C139—H13K | 0.9800 |
C65—H65 | 0.9500 | C139—H13L | 0.9800 |
C66—N75 | 1.382 (3) | O40A—C41A | 1.253 (7) |
C66—C67 | 1.402 (3) | C41A—N42A | 1.234 (7) |
C67—C68 | 1.403 (3) | C41A—H41A | 0.9500 |
C67—C91 | 1.491 (3) | N42A—C44A | 1.429 (8) |
C68—N76 | 1.369 (3) | N42A—C43A | 1.605 (9) |
C68—C69 | 1.458 (3) | C43A—H4AA | 0.9800 |
C69—C70 | 1.337 (3) | C43A—H4BA | 0.9800 |
C69—H69 | 0.9500 | C43A—H4CA | 0.9800 |
C70—C71 | 1.456 (3) | C44A—H4DA | 0.9800 |
C70—H70 | 0.9500 | C44A—H4EA | 0.9800 |
C71—N76 | 1.364 (3) | C44A—H4FA | 0.9800 |
C71—C72 | 1.411 (3) | O40B—C41B | 0.878 (7) |
C72—C98 | 1.497 (3) | C41B—N42B | 1.389 (9) |
N73—H73 | 0.8800 | C41B—H41B | 0.9500 |
N74—H74 | 0.8800 | N42B—C43B | 1.340 (7) |
N75—H75 | 0.8800 | N42B—C44B | 1.538 (8) |
N76—H76 | 0.8800 | C43B—H4AB | 0.9800 |
C77—C78 | 1.392 (3) | C43B—H4BB | 0.9800 |
C77—C82 | 1.401 (3) | C43B—H4CB | 0.9800 |
C78—C79 | 1.390 (3) | C44B—H4DB | 0.9800 |
C78—H78 | 0.9500 | C44B—H4EB | 0.9800 |
C79—C80 | 1.383 (3) | C44B—H4FB | 0.9800 |
C79—H79 | 0.9500 | | |
| | | |
N21—C1—C20 | 125.64 (19) | C79—C78—C77 | 121.6 (2) |
N21—C1—C2 | 106.53 (19) | C79—C78—H78 | 119.2 |
C20—C1—C2 | 127.8 (2) | C77—C78—H78 | 119.2 |
C3—C2—C1 | 108.18 (19) | C80—C79—C78 | 119.9 (2) |
C3—C2—H2 | 125.9 | C80—C79—H79 | 120.1 |
C1—C2—H2 | 125.9 | C78—C79—H79 | 120.1 |
C2—C3—C4 | 108.7 (2) | O83—C80—C81 | 117.9 (2) |
C2—C3—H3 | 125.7 | O83—C80—C79 | 122.5 (2) |
C4—C3—H3 | 125.7 | C81—C80—C79 | 119.6 (2) |
N21—C4—C5 | 126.60 (19) | C80—C81—C82 | 120.5 (2) |
N21—C4—C3 | 106.45 (18) | C80—C81—H81 | 119.8 |
C5—C4—C3 | 126.9 (2) | C82—C81—H81 | 119.8 |
C6—C5—C4 | 125.3 (2) | C81—C82—C77 | 121.2 (2) |
C6—C5—C25 | 118.72 (18) | C81—C82—H82 | 119.4 |
C4—C5—C25 | 115.94 (19) | C77—C82—H82 | 119.4 |
N22—C6—C5 | 126.13 (19) | C80—O83—H83 | 109.5 |
N22—C6—C7 | 110.63 (18) | C89—C84—C85 | 117.46 (19) |
C5—C6—C7 | 123.21 (19) | C89—C84—C62 | 122.33 (18) |
C8—C7—C6 | 106.74 (19) | C85—C84—C62 | 120.21 (18) |
C8—C7—H7 | 126.6 | C86—C85—C84 | 121.1 (2) |
C6—C7—H7 | 126.6 | C86—C85—H85 | 119.5 |
C7—C8—C9 | 106.58 (19) | C84—C85—H85 | 119.5 |
C7—C8—H8 | 126.7 | C87—C86—C85 | 120.4 (2) |
C9—C8—H8 | 126.7 | C87—C86—H86 | 119.8 |
N22—C9—C10 | 125.90 (19) | C85—C86—H86 | 119.8 |
N22—C9—C8 | 110.27 (18) | O90—C87—C86 | 122.70 (19) |
C10—C9—C8 | 123.76 (19) | O90—C87—C88 | 117.99 (19) |
C11—C10—C9 | 123.66 (19) | C86—C87—C88 | 119.30 (19) |
C11—C10—C32 | 117.51 (18) | C89—C88—C87 | 119.8 (2) |
C9—C10—C32 | 118.82 (19) | C89—C88—H88 | 120.1 |
N23—C11—C10 | 125.21 (19) | C87—C88—H88 | 120.1 |
N23—C11—C12 | 106.73 (18) | C88—C89—C84 | 121.95 (19) |
C10—C11—C12 | 128.05 (19) | C88—C89—H89 | 119.0 |
C13—C12—C11 | 108.48 (19) | C84—C89—H89 | 119.0 |
C13—C12—H12 | 125.8 | C87—O90—H90 | 109.5 |
C11—C12—H12 | 125.8 | C92—C91—C96 | 117.76 (19) |
C12—C13—C14 | 108.3 (2) | C92—C91—C67 | 120.77 (18) |
C12—C13—H13 | 125.9 | C96—C91—C67 | 121.43 (19) |
C14—C13—H13 | 125.9 | C93—C92—C91 | 121.6 (2) |
N23—C14—C15 | 126.49 (19) | C93—C92—H92 | 119.2 |
N23—C14—C13 | 106.83 (18) | C91—C92—H92 | 119.2 |
C15—C14—C13 | 126.7 (2) | C92—C93—C94 | 120.0 (2) |
C16—C15—C14 | 125.20 (19) | C92—C93—H93 | 120.0 |
C16—C15—C39 | 118.66 (18) | C94—C93—H93 | 120.0 |
C14—C15—C39 | 116.14 (18) | O97—C94—C93 | 123.0 (2) |
N24—C16—C15 | 125.78 (19) | O97—C94—C95 | 117.71 (19) |
N24—C16—C17 | 110.39 (18) | C93—C94—C95 | 119.31 (19) |
C15—C16—C17 | 123.78 (19) | C96—C95—C94 | 120.6 (2) |
C18—C17—C16 | 106.81 (19) | C96—C95—H95 | 119.7 |
C18—C17—H17 | 126.6 | C94—C95—H95 | 119.7 |
C16—C17—H17 | 126.6 | C95—C96—C91 | 120.8 (2) |
C17—C18—C19 | 106.62 (19) | C95—C96—H96 | 119.6 |
C17—C18—H18 | 126.7 | C91—C96—H96 | 119.6 |
C19—C18—H18 | 126.7 | C94—O97—H97 | 109.5 |
N24—C19—C20 | 125.90 (19) | C99—C98—C103 | 117.73 (19) |
N24—C19—C18 | 110.68 (18) | C99—C98—C72 | 121.81 (19) |
C20—C19—C18 | 123.42 (19) | C103—C98—C72 | 120.06 (19) |
C1—C20—C19 | 124.18 (19) | C98—C99—C100 | 121.5 (2) |
C1—C20—C46 | 118.54 (19) | C98—C99—H99 | 119.2 |
C19—C20—C46 | 117.28 (19) | C100—C99—H99 | 119.2 |
C4—N21—C1 | 110.14 (17) | C99—C100—C101 | 119.6 (2) |
C4—N21—H21 | 124.9 | C99—C100—H100 | 120.2 |
C1—N21—H21 | 124.9 | C101—C100—H100 | 120.2 |
C6—N22—C9 | 105.65 (16) | O104—C101—C102 | 118.1 (2) |
C6—N22—H22 | 127.2 | O104—C101—C100 | 122.2 (2) |
C9—N22—H22 | 127.2 | C102—C101—C100 | 119.7 (2) |
C14—N23—C11 | 109.62 (17) | C101—C102—C103 | 120.0 (2) |
C14—N23—H23 | 125.2 | C101—C102—H102 | 120.0 |
C11—N23—H23 | 125.2 | C103—C102—H102 | 120.0 |
C19—N24—C16 | 105.46 (17) | C102—C103—C98 | 121.4 (2) |
C19—N24—H24 | 127.3 | C102—C103—H103 | 119.3 |
C16—N24—H24 | 127.3 | C98—C103—H103 | 119.3 |
C30—C25—C26 | 118.01 (19) | C101—O104—H104 | 109.5 |
C30—C25—C5 | 120.48 (19) | O105—C106—N107 | 125.1 (2) |
C26—C25—C5 | 121.48 (18) | O105—C106—H106 | 117.4 |
C27—C26—C25 | 121.14 (19) | N107—C106—H106 | 117.4 |
C27—C26—H26 | 119.4 | C106—N107—C109 | 120.8 (2) |
C25—C26—H26 | 119.4 | C106—N107—C108 | 121.6 (2) |
C26—C27—C28 | 119.9 (2) | C109—N107—C108 | 117.4 (2) |
C26—C27—H27 | 120.1 | N107—C108—H10A | 109.5 |
C28—C27—H27 | 120.1 | N107—C108—H10B | 109.5 |
O31—C28—C29 | 117.71 (19) | H10A—C108—H10B | 109.5 |
O31—C28—C27 | 122.7 (2) | N107—C108—H10C | 109.5 |
C29—C28—C27 | 119.6 (2) | H10A—C108—H10C | 109.5 |
C30—C29—C28 | 120.1 (2) | H10B—C108—H10C | 109.5 |
C30—C29—H29 | 120.0 | N107—C109—H10D | 109.5 |
C28—C29—H29 | 120.0 | N107—C109—H10E | 109.5 |
C29—C30—C25 | 121.3 (2) | H10D—C109—H10E | 109.5 |
C29—C30—H30 | 119.4 | N107—C109—H10F | 109.5 |
C25—C30—H30 | 119.4 | H10D—C109—H10F | 109.5 |
C28—O31—H31 | 109.5 | H10E—C109—H10F | 109.5 |
C33—C32—C37 | 117.59 (19) | O110—C111—N112 | 125.7 (2) |
C33—C32—C10 | 121.38 (19) | O110—C111—H111 | 117.1 |
C37—C32—C10 | 121.03 (19) | N112—C111—H111 | 117.1 |
C34—C33—C32 | 121.1 (2) | C111—N112—C114 | 121.3 (2) |
C34—C33—H33 | 119.4 | C111—N112—C113 | 120.7 (2) |
C32—C33—H33 | 119.4 | C114—N112—C113 | 117.8 (2) |
C33—C34—C35 | 120.2 (2) | N112—C113—H11A | 109.5 |
C33—C34—H34 | 119.9 | N112—C113—H11B | 109.5 |
C35—C34—H34 | 119.9 | H11A—C113—H11B | 109.5 |
O38—C35—C36 | 117.4 (2) | N112—C113—H11C | 109.5 |
O38—C35—C34 | 123.1 (2) | H11A—C113—H11C | 109.5 |
C36—C35—C34 | 119.4 (2) | H11B—C113—H11C | 109.5 |
C37—C36—C35 | 120.0 (2) | N112—C114—H11D | 109.5 |
C37—C36—H36 | 120.0 | N112—C114—H11E | 109.5 |
C35—C36—H36 | 120.0 | H11D—C114—H11E | 109.5 |
C36—C37—C32 | 121.6 (2) | N112—C114—H11F | 109.5 |
C36—C37—H37 | 119.2 | H11D—C114—H11F | 109.5 |
C32—C37—H37 | 119.2 | H11E—C114—H11F | 109.5 |
C35—O38—H38 | 109.5 | O115—C116—N117 | 125.8 (3) |
C44—C39—C40 | 117.7 (2) | O115—C116—H116 | 117.1 |
C44—C39—C15 | 121.6 (2) | N117—C116—H116 | 117.1 |
C40—C39—C15 | 120.69 (19) | C116—N117—C118 | 121.3 (2) |
C41—C40—C39 | 121.6 (2) | C116—N117—C119 | 121.0 (2) |
C41—C40—H40 | 119.2 | C118—N117—C119 | 117.2 (3) |
C39—C40—H40 | 119.2 | N117—C118—H11G | 109.5 |
C40—C41—C42 | 120.1 (2) | N117—C118—H11H | 109.5 |
C40—C41—H41 | 120.0 | H11G—C118—H11H | 109.5 |
C42—C41—H41 | 120.0 | N117—C118—H11I | 109.5 |
O45—C42—C43 | 117.9 (2) | H11G—C118—H11I | 109.5 |
O45—C42—C41 | 123.0 (2) | H11H—C118—H11I | 109.5 |
C43—C42—C41 | 119.1 (2) | N117—C119—H11J | 109.5 |
C42—C43—C44 | 120.4 (2) | N117—C119—H11K | 109.5 |
C42—C43—H43 | 119.8 | H11J—C119—H11K | 109.5 |
C44—C43—H43 | 119.8 | N117—C119—H11L | 109.5 |
C43—C44—C39 | 121.2 (2) | H11J—C119—H11L | 109.5 |
C43—C44—H44 | 119.4 | H11K—C119—H11L | 109.5 |
C39—C44—H44 | 119.4 | O120—C121—N122 | 126.4 (2) |
C42—O45—H45 | 109.5 | O120—C121—H121 | 116.8 |
C47—C46—C51 | 117.9 (2) | N122—C121—H121 | 116.8 |
C47—C46—C20 | 120.8 (2) | C121—N122—C123 | 120.7 (2) |
C51—C46—C20 | 121.2 (2) | C121—N122—C124 | 121.8 (2) |
C48—C47—C46 | 121.3 (2) | C123—N122—C124 | 117.4 (2) |
C48—C47—H47 | 119.3 | N122—C123—H12A | 109.5 |
C46—C47—H47 | 119.3 | N122—C123—H12B | 109.5 |
C47—C48—C49 | 119.6 (2) | H12A—C123—H12B | 109.5 |
C47—C48—H48 | 120.2 | N122—C123—H12C | 109.5 |
C49—C48—H48 | 120.2 | H12A—C123—H12C | 109.5 |
O52—C49—C50 | 117.8 (2) | H12B—C123—H12C | 109.5 |
O52—C49—C48 | 122.3 (2) | N122—C124—H12D | 109.5 |
C50—C49—C48 | 119.9 (2) | N122—C124—H12E | 109.5 |
C49—C50—C51 | 120.1 (2) | H12D—C124—H12E | 109.5 |
C49—C50—H50 | 119.9 | N122—C124—H12F | 109.5 |
C51—C50—H50 | 119.9 | H12D—C124—H12F | 109.5 |
C50—C51—C46 | 121.1 (2) | H12E—C124—H12F | 109.5 |
C50—C51—H51 | 119.4 | O125—C126—N127 | 125.4 (2) |
C46—C51—H51 | 119.4 | O125—C126—H126 | 117.3 |
C49—O52—H52 | 109.5 | N127—C126—H126 | 117.3 |
N73—C53—C72 | 125.72 (19) | C126—N127—C128 | 119.5 (2) |
N73—C53—C54 | 106.64 (18) | C126—N127—C129 | 122.3 (2) |
C72—C53—C54 | 127.61 (19) | C128—N127—C129 | 117.2 (2) |
C55—C54—C53 | 108.24 (19) | N127—C128—H12G | 109.5 |
C55—C54—H54 | 125.9 | N127—C128—H12H | 109.5 |
C53—C54—H54 | 125.9 | H12G—C128—H12H | 109.5 |
C54—C55—C56 | 108.48 (19) | N127—C128—H12I | 109.5 |
C54—C55—H55 | 125.8 | H12G—C128—H12I | 109.5 |
C56—C55—H55 | 125.8 | H12H—C128—H12I | 109.5 |
N73—C56—C57 | 125.92 (19) | N127—C129—H12J | 109.5 |
N73—C56—C55 | 106.13 (17) | N127—C129—H12K | 109.5 |
C57—C56—C55 | 127.85 (19) | H12J—C129—H12K | 109.5 |
C58—C57—C56 | 124.73 (19) | N127—C129—H12L | 109.5 |
C58—C57—C77 | 118.64 (18) | H12J—C129—H12L | 109.5 |
C56—C57—C77 | 116.61 (18) | H12K—C129—H12L | 109.5 |
N74—C58—C57 | 125.77 (18) | O130—C131—N132 | 125.0 (2) |
N74—C58—C59 | 109.92 (18) | O130—C131—H131 | 117.5 |
C57—C58—C59 | 124.23 (19) | N132—C131—H131 | 117.5 |
C60—C59—C58 | 107.08 (18) | C131—N132—C134 | 120.8 (2) |
C60—C59—H59 | 126.5 | C131—N132—C133 | 120.7 (2) |
C58—C59—H59 | 126.5 | C134—N132—C133 | 118.4 (2) |
C59—C60—C61 | 106.61 (19) | N132—C133—H13A | 109.5 |
C59—C60—H60 | 126.7 | N132—C133—H13B | 109.5 |
C61—C60—H60 | 126.7 | H13A—C133—H13B | 109.5 |
N74—C61—C62 | 126.40 (19) | N132—C133—H13C | 109.5 |
N74—C61—C60 | 110.42 (18) | H13A—C133—H13C | 109.5 |
C62—C61—C60 | 123.12 (19) | H13B—C133—H13C | 109.5 |
C63—C62—C61 | 124.12 (19) | N132—C134—H13D | 109.5 |
C63—C62—C84 | 117.60 (18) | N132—C134—H13E | 109.5 |
C61—C62—C84 | 118.27 (18) | H13D—C134—H13E | 109.5 |
N75—C63—C62 | 125.31 (18) | N132—C134—H13F | 109.5 |
N75—C63—C64 | 106.59 (17) | H13D—C134—H13F | 109.5 |
C62—C63—C64 | 128.08 (19) | H13E—C134—H13F | 109.5 |
C65—C64—C63 | 108.12 (19) | O135—C136—N137 | 125.7 (2) |
C65—C64—H64 | 125.9 | O135—C136—H136 | 117.1 |
C63—C64—H64 | 125.9 | N137—C136—H136 | 117.1 |
C64—C65—C66 | 108.63 (19) | C136—N137—C138 | 122.4 (2) |
C64—C65—H65 | 125.7 | C136—N137—C139 | 120.5 (2) |
C66—C65—H65 | 125.7 | C138—N137—C139 | 117.1 (2) |
N75—C66—C67 | 125.91 (19) | N137—C138—H13G | 109.5 |
N75—C66—C65 | 106.31 (17) | N137—C138—H13H | 109.5 |
C67—C66—C65 | 127.75 (19) | H13G—C138—H13H | 109.5 |
C66—C67—C68 | 125.11 (19) | N137—C138—H13I | 109.5 |
C66—C67—C91 | 117.07 (18) | H13G—C138—H13I | 109.5 |
C68—C67—C91 | 117.80 (18) | H13H—C138—H13I | 109.5 |
N76—C68—C67 | 125.91 (18) | N137—C139—H13J | 109.5 |
N76—C68—C69 | 110.11 (18) | N137—C139—H13K | 109.5 |
C67—C68—C69 | 123.96 (19) | H13J—C139—H13K | 109.5 |
C70—C69—C68 | 106.99 (19) | N137—C139—H13L | 109.5 |
C70—C69—H69 | 126.5 | H13J—C139—H13L | 109.5 |
C68—C69—H69 | 126.5 | H13K—C139—H13L | 109.5 |
C69—C70—C71 | 106.57 (19) | N42A—C41A—O40A | 151.9 (7) |
C69—C70—H70 | 126.7 | N42A—C41A—H41A | 104.0 |
C71—C70—H70 | 126.7 | O40A—C41A—H41A | 104.0 |
N76—C71—C72 | 126.47 (19) | C41A—N42A—C44A | 131.9 (7) |
N76—C71—C70 | 110.63 (18) | C41A—N42A—C43A | 115.2 (6) |
C72—C71—C70 | 122.90 (19) | C44A—N42A—C43A | 112.6 (5) |
C53—C72—C71 | 124.49 (19) | O40B—C41B—N42B | 143.9 (9) |
C53—C72—C98 | 119.14 (18) | O40B—C41B—H41B | 108.1 |
C71—C72—C98 | 116.32 (18) | N42B—C41B—H41B | 108.1 |
C56—N73—C53 | 110.46 (17) | C43B—N42B—C41B | 126.8 (6) |
C56—N73—H73 | 124.8 | C43B—N42B—C44B | 119.4 (6) |
C53—N73—H73 | 124.8 | C41B—N42B—C44B | 113.8 (6) |
C61—N74—C58 | 105.82 (16) | N42B—C43B—H4AB | 109.5 |
C61—N74—H74 | 127.1 | N42B—C43B—H4BB | 109.5 |
C58—N74—H74 | 127.1 | H4AB—C43B—H4BB | 109.5 |
C63—N75—C66 | 110.26 (16) | N42B—C43B—H4CB | 109.5 |
C63—N75—H75 | 124.9 | H4AB—C43B—H4CB | 109.5 |
C66—N75—H75 | 124.9 | H4BB—C43B—H4CB | 109.5 |
C71—N76—C68 | 105.63 (16) | N42B—C44B—H4DB | 109.5 |
C71—N76—H76 | 127.2 | N42B—C44B—H4EB | 109.5 |
C68—N76—H76 | 127.2 | H4DB—C44B—H4EB | 109.5 |
C78—C77—C82 | 117.24 (19) | N42B—C44B—H4FB | 109.5 |
C78—C77—C57 | 122.41 (18) | H4DB—C44B—H4FB | 109.5 |
C82—C77—C57 | 120.34 (19) | H4EB—C44B—H4FB | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O115 | 0.84 | 1.80 | 2.6366 (18) | 177 |
O38—H38···O125 | 0.84 | 1.82 | 2.6491 (17) | 171 |
O45—H45···O110 | 0.84 | 1.83 | 2.6666 (16) | 174 |
O52—H52···O120 | 0.84 | 1.83 | 2.6686 (18) | 175 |
O83—H83···O40A | 0.84 | 1.82 | 2.642 (4) | 166 |
O83—H83···O40B | 0.84 | 1.89 | 2.647 (4) | 149 |
O90—H90···O135 | 0.84 | 1.86 | 2.6929 (18) | 174 |
O97—H97···O105 | 0.84 | 1.81 | 2.6467 (16) | 174 |
O104—H104···O130 | 0.84 | 1.86 | 2.6961 (18) | 174 |
(II) 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin
N,
N'-dimethylformamide tetrasolvate monohydrate
top
Crystal data top
C44H30N4O4·4C3H7NO·H2O | Z = 2 |
Mr = 989.12 | F(000) = 1048 |
Triclinic, P1 | Dx = 1.297 Mg m−3 |
a = 12.8346 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.6669 (2) Å | Cell parameters from 8903 reflections |
c = 15.3200 (3) Å | θ = 2.0–28.2° |
α = 102.8305 (6)° | µ = 0.09 mm−1 |
β = 90.2339 (6)° | T = 110 K |
γ = 104.3547 (11)° | Plate, red |
V = 2533.39 (7) Å3 | 0.60 × 0.50 × 0.30 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 8881 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 28.2°, θmin = 2.0° |
Detector resolution: 12.8 pixels mm-1 | h = −17→17 |
1 deg. ϕ and ω scans | k = −17→17 |
26977 measured reflections | l = −20→20 |
12018 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0787P)2 + 1.1683P] where P = (Fo2 + 2Fc2)/3 |
12018 reflections | (Δ/σ)max = 0.002 |
670 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
Crystal data top
C44H30N4O4·4C3H7NO·H2O | γ = 104.3547 (11)° |
Mr = 989.12 | V = 2533.39 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.8346 (2) Å | Mo Kα radiation |
b = 13.6669 (2) Å | µ = 0.09 mm−1 |
c = 15.3200 (3) Å | T = 110 K |
α = 102.8305 (6)° | 0.60 × 0.50 × 0.30 mm |
β = 90.2339 (6)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 8881 reflections with I > 2σ(I) |
26977 measured reflections | Rint = 0.030 |
12018 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
12018 reflections | Δρmin = −0.44 e Å−3 |
670 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 | 0.56080 (12) | 0.19555 (12) | 0.64950 (10) | 0.0166 (3) | |
C2 | 0.53238 (13) | 0.26145 (13) | 0.72686 (11) | 0.0185 (3) | |
H2 | 0.5524 | 0.2647 | 0.7874 | 0.022* | |
C3 | 0.47164 (13) | 0.31892 (13) | 0.69897 (11) | 0.0195 (3) | |
H3 | 0.4417 | 0.3687 | 0.7367 | 0.023* | |
C4 | 0.46088 (12) | 0.29134 (12) | 0.60344 (11) | 0.0172 (3) | |
C5 | 0.40455 (12) | 0.33196 (12) | 0.54693 (11) | 0.0168 (3) | |
C6 | 0.41308 (12) | 0.31675 (12) | 0.45343 (11) | 0.0169 (3) | |
C7 | 0.35467 (13) | 0.35920 (13) | 0.39555 (11) | 0.0196 (3) | |
H7 | 0.3004 | 0.3949 | 0.4124 | 0.023* | |
C8 | 0.39269 (13) | 0.33792 (13) | 0.31332 (11) | 0.0201 (3) | |
H8 | 0.3721 | 0.3574 | 0.2613 | 0.024* | |
C9 | 0.47136 (12) | 0.27930 (12) | 0.32015 (11) | 0.0168 (3) | |
C10 | 0.52915 (12) | 0.24391 (12) | 0.24701 (10) | 0.0171 (3) | |
C11 | 0.59708 (12) | 0.17820 (12) | 0.24766 (11) | 0.0178 (3) | |
C12 | 0.65545 (13) | 0.13922 (13) | 0.17448 (11) | 0.0195 (3) | |
H12 | 0.6582 | 0.1565 | 0.1177 | 0.023* | |
C13 | 0.70640 (13) | 0.07296 (13) | 0.20033 (11) | 0.0193 (3) | |
H13 | 0.7504 | 0.0356 | 0.1644 | 0.023* | |
C14 | 0.68251 (12) | 0.06908 (12) | 0.29068 (11) | 0.0171 (3) | |
C15 | 0.71637 (12) | 0.00875 (12) | 0.34241 (10) | 0.0166 (3) | |
C16 | 0.69680 (12) | 0.01359 (12) | 0.43354 (11) | 0.0164 (3) | |
C17 | 0.72678 (13) | −0.05453 (12) | 0.48456 (11) | 0.0184 (3) | |
H17 | 0.7589 | −0.1100 | 0.4624 | 0.022* | |
C18 | 0.70002 (13) | −0.02331 (12) | 0.56960 (11) | 0.0189 (3) | |
H18 | 0.7094 | −0.0526 | 0.6189 | 0.023* | |
C19 | 0.65399 (12) | 0.06410 (12) | 0.57066 (10) | 0.0164 (3) | |
C20 | 0.61980 (12) | 0.12166 (12) | 0.64875 (10) | 0.0164 (3) | |
N21 | 0.51817 (10) | 0.21809 (10) | 0.57605 (9) | 0.0162 (3) | |
H21 | 0.5263 | 0.1899 | 0.5198 | 0.019* | 0.50 |
N22 | 0.48155 (10) | 0.26586 (10) | 0.40497 (9) | 0.0165 (3) | |
H22 | 0.5231 | 0.2318 | 0.4245 | 0.020* | 0.50 |
N23 | 0.61723 (10) | 0.13538 (10) | 0.31727 (9) | 0.0168 (3) | |
H23 | 0.5922 | 0.1484 | 0.3708 | 0.020* | 0.50 |
N24 | 0.65080 (10) | 0.08352 (10) | 0.48694 (9) | 0.0163 (3) | |
H24 | 0.6246 | 0.1311 | 0.4709 | 0.020* | 0.50 |
C25 | 0.33294 (12) | 0.39654 (12) | 0.59124 (10) | 0.0171 (3) | |
C26 | 0.25298 (13) | 0.35684 (13) | 0.64513 (11) | 0.0191 (3) | |
H26 | 0.2450 | 0.2886 | 0.6534 | 0.023* | |
C27 | 0.18497 (13) | 0.41550 (13) | 0.68678 (11) | 0.0205 (3) | |
H27 | 0.1308 | 0.3869 | 0.7227 | 0.025* | |
C28 | 0.19615 (13) | 0.51572 (13) | 0.67598 (11) | 0.0192 (3) | |
C29 | 0.27533 (13) | 0.55676 (13) | 0.62234 (11) | 0.0195 (3) | |
H29 | 0.2831 | 0.6250 | 0.6142 | 0.023* | |
C30 | 0.34274 (12) | 0.49744 (12) | 0.58094 (11) | 0.0182 (3) | |
H30 | 0.3966 | 0.5261 | 0.5449 | 0.022* | |
O31 | 0.13042 (10) | 0.57136 (10) | 0.72111 (9) | 0.0275 (3) | |
H31 | 0.1306 | 0.6221 | 0.6985 | 0.041* | |
C32 | 0.52238 (13) | 0.28101 (13) | 0.16308 (11) | 0.0183 (3) | |
C33 | 0.57589 (14) | 0.38248 (13) | 0.16094 (12) | 0.0237 (4) | |
H33 | 0.6120 | 0.4285 | 0.2143 | 0.028* | |
C34 | 0.57758 (14) | 0.41772 (14) | 0.08266 (12) | 0.0261 (4) | |
H34 | 0.6157 | 0.4868 | 0.0824 | 0.031* | |
C35 | 0.52334 (15) | 0.35162 (14) | 0.00458 (11) | 0.0249 (4) | |
C36 | 0.46762 (15) | 0.25109 (14) | 0.00631 (12) | 0.0270 (4) | |
H36 | 0.4295 | 0.2059 | −0.0466 | 0.032* | |
C37 | 0.46720 (14) | 0.21633 (14) | 0.08461 (11) | 0.0242 (4) | |
H37 | 0.4287 | 0.1474 | 0.0848 | 0.029* | |
O38 | 0.52169 (13) | 0.38207 (11) | −0.07420 (9) | 0.0345 (3) | |
H38 | 0.5686 | 0.4382 | −0.0704 | 0.052* | |
C39 | 0.78044 (12) | −0.06297 (12) | 0.29604 (10) | 0.0171 (3) | |
C40 | 0.73460 (13) | −0.14665 (13) | 0.22490 (11) | 0.0200 (3) | |
H40 | 0.6610 | −0.1586 | 0.2062 | 0.024* | |
C41 | 0.79400 (13) | −0.21273 (13) | 0.18089 (11) | 0.0212 (3) | |
H41 | 0.7608 | −0.2699 | 0.1334 | 0.025* | |
C42 | 0.90236 (14) | −0.19482 (13) | 0.20673 (11) | 0.0211 (3) | |
C43 | 0.94989 (13) | −0.11096 (13) | 0.27621 (12) | 0.0231 (4) | |
H43 | 1.0242 | −0.0978 | 0.2935 | 0.028* | |
C44 | 0.88926 (13) | −0.04628 (13) | 0.32064 (11) | 0.0213 (3) | |
H44 | 0.9225 | 0.0103 | 0.3686 | 0.026* | |
O45 | 0.96531 (10) | −0.25729 (10) | 0.16743 (9) | 0.0290 (3) | |
H45 | 0.9280 | −0.3065 | 0.1279 | 0.044* | |
C46 | 0.64909 (12) | 0.10367 (12) | 0.73713 (10) | 0.0169 (3) | |
C47 | 0.75628 (13) | 0.11671 (13) | 0.76476 (11) | 0.0192 (3) | |
H47 | 0.8114 | 0.1389 | 0.7270 | 0.023* | |
C48 | 0.78475 (13) | 0.09814 (13) | 0.84601 (11) | 0.0217 (3) | |
H48 | 0.8584 | 0.1076 | 0.8633 | 0.026* | |
C49 | 0.70460 (14) | 0.06552 (13) | 0.90199 (11) | 0.0201 (3) | |
C50 | 0.59727 (14) | 0.05538 (13) | 0.87670 (11) | 0.0212 (3) | |
H50 | 0.5424 | 0.0356 | 0.9155 | 0.025* | |
C51 | 0.57033 (13) | 0.07397 (12) | 0.79559 (11) | 0.0192 (3) | |
H51 | 0.4968 | 0.0664 | 0.7792 | 0.023* | |
O52 | 0.72536 (10) | 0.04259 (10) | 0.98108 (8) | 0.0280 (3) | |
H52 | 0.7922 | 0.0589 | 0.9930 | 0.042* | |
O53 | 0.09389 (10) | 0.72612 (10) | 0.65338 (9) | 0.0316 (3) | |
C54 | 0.11087 (15) | 0.75753 (13) | 0.58384 (12) | 0.0263 (4) | |
H54 | 0.1819 | 0.7676 | 0.5638 | 0.032* | |
N55 | 0.03633 (12) | 0.77824 (12) | 0.53496 (11) | 0.0289 (3) | |
C56 | 0.06214 (18) | 0.81358 (18) | 0.45339 (14) | 0.0406 (5) | |
H56A | 0.1379 | 0.8170 | 0.4423 | 0.061* | |
H56B | 0.0497 | 0.8827 | 0.4598 | 0.061* | |
H56C | 0.0162 | 0.7650 | 0.4029 | 0.061* | |
C57 | −0.07409 (17) | 0.76465 (19) | 0.56046 (16) | 0.0414 (5) | |
H57A | −0.0798 | 0.7465 | 0.6190 | 0.062* | |
H57B | −0.1215 | 0.7089 | 0.5155 | 0.062* | |
H57C | −0.0956 | 0.8294 | 0.5642 | 0.062* | |
O58 | 0.86664 (12) | −0.42799 (11) | 0.04797 (10) | 0.0414 (4) | |
C59 | 0.88094 (19) | −0.50648 (16) | 0.06877 (15) | 0.0395 (5) | |
H59 | 0.9058 | −0.4991 | 0.1290 | 0.047* | |
N60 | 0.86483 (16) | −0.59908 (13) | 0.01506 (13) | 0.0421 (4) | |
C61 | 0.8830 (3) | −0.6867 (2) | 0.0472 (2) | 0.0787 (11) | |
H61A | 0.9132 | −0.6626 | 0.1093 | 0.118* | |
H61B | 0.9335 | −0.7173 | 0.0094 | 0.118* | |
H61C | 0.8144 | −0.7390 | 0.0443 | 0.118* | |
C62 | 0.8298 (2) | −0.6178 (2) | −0.07958 (17) | 0.0527 (6) | |
H62A | 0.7528 | −0.6532 | −0.0884 | 0.079* | |
H62B | 0.8709 | −0.6614 | −0.1164 | 0.079* | |
H62C | 0.8421 | −0.5514 | −0.0973 | 0.079* | |
O63 | 0.93357 (12) | 0.08821 (13) | 1.02441 (11) | 0.0448 (4) | |
C64 | 0.98721 (16) | 0.09577 (16) | 1.09406 (14) | 0.0344 (4) | |
H64 | 0.9507 | 0.0681 | 1.1405 | 0.041* | |
N65 | 1.09128 (13) | 0.13954 (13) | 1.10831 (11) | 0.0317 (4) | |
C66 | 1.14945 (18) | 0.14594 (18) | 1.19120 (15) | 0.0419 (5) | |
H66A | 1.1003 | 0.1114 | 1.2303 | 0.063* | |
H66B | 1.1793 | 0.2190 | 1.2213 | 0.063* | |
H66C | 1.2082 | 0.1117 | 1.1782 | 0.063* | |
C67 | 1.1531 (2) | 0.1799 (2) | 1.03880 (18) | 0.0504 (6) | |
H67A | 1.1051 | 0.1692 | 0.9857 | 0.076* | |
H67B | 1.2095 | 0.1434 | 1.0228 | 0.076* | |
H67C | 1.1862 | 0.2542 | 1.0611 | 0.076* | |
O68 | 0.81306 (16) | 0.58539 (16) | −0.20961 (13) | 0.0637 (5) | |
C69 | 0.86683 (17) | 0.57297 (18) | −0.27516 (15) | 0.0384 (5) | |
H69 | 0.9292 | 0.6268 | −0.2773 | 0.046* | |
N70 | 0.84512 (14) | 0.49075 (14) | −0.34320 (14) | 0.0433 (5) | |
C71 | 0.91475 (19) | 0.48164 (19) | −0.41760 (16) | 0.0456 (5) | |
H71A | 0.9706 | 0.5468 | −0.4113 | 0.068* | |
H71B | 0.8719 | 0.4671 | −0.4742 | 0.068* | |
H71C | 0.9487 | 0.4249 | −0.4175 | 0.068* | |
C72 | 0.7531 (3) | 0.4046 (3) | −0.3454 (3) | 0.1008 (14) | |
H72A | 0.7044 | 0.4252 | −0.2998 | 0.151* | |
H72B | 0.7772 | 0.3460 | −0.3331 | 0.151* | |
H72C | 0.7150 | 0.3839 | −0.4048 | 0.151* | |
O73 | 0.68215 (13) | 0.55635 (13) | −0.06864 (12) | 0.0502 (4) | |
H73A | 0.7387 | 0.5612 | −0.0328 | 0.075* | |
H73B | 0.7239 | 0.5657 | −0.1140 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0147 (7) | 0.0198 (8) | 0.0157 (8) | 0.0040 (6) | 0.0023 (6) | 0.0054 (6) |
C2 | 0.0196 (8) | 0.0217 (8) | 0.0150 (8) | 0.0073 (6) | 0.0025 (6) | 0.0037 (6) |
C3 | 0.0198 (8) | 0.0229 (8) | 0.0170 (8) | 0.0087 (6) | 0.0049 (6) | 0.0033 (6) |
C4 | 0.0147 (7) | 0.0185 (8) | 0.0189 (8) | 0.0057 (6) | 0.0037 (6) | 0.0034 (6) |
C5 | 0.0145 (7) | 0.0178 (8) | 0.0184 (8) | 0.0041 (6) | 0.0032 (6) | 0.0049 (6) |
C6 | 0.0147 (7) | 0.0176 (8) | 0.0192 (8) | 0.0051 (6) | 0.0031 (6) | 0.0044 (6) |
C7 | 0.0168 (7) | 0.0228 (8) | 0.0209 (8) | 0.0089 (6) | 0.0021 (6) | 0.0044 (6) |
C8 | 0.0200 (8) | 0.0236 (8) | 0.0190 (8) | 0.0093 (6) | −0.0003 (6) | 0.0055 (6) |
C9 | 0.0158 (7) | 0.0189 (8) | 0.0170 (8) | 0.0058 (6) | 0.0008 (6) | 0.0054 (6) |
C10 | 0.0186 (7) | 0.0178 (8) | 0.0160 (8) | 0.0056 (6) | 0.0017 (6) | 0.0053 (6) |
C11 | 0.0188 (7) | 0.0190 (8) | 0.0157 (8) | 0.0047 (6) | 0.0012 (6) | 0.0043 (6) |
C12 | 0.0211 (8) | 0.0240 (8) | 0.0154 (8) | 0.0081 (6) | 0.0041 (6) | 0.0063 (6) |
C13 | 0.0183 (8) | 0.0249 (8) | 0.0168 (8) | 0.0086 (6) | 0.0057 (6) | 0.0055 (6) |
C14 | 0.0147 (7) | 0.0198 (8) | 0.0171 (8) | 0.0060 (6) | 0.0016 (6) | 0.0034 (6) |
C15 | 0.0148 (7) | 0.0188 (8) | 0.0166 (8) | 0.0062 (6) | 0.0012 (6) | 0.0028 (6) |
C16 | 0.0148 (7) | 0.0180 (8) | 0.0169 (8) | 0.0052 (6) | 0.0015 (6) | 0.0039 (6) |
C17 | 0.0198 (8) | 0.0180 (8) | 0.0185 (8) | 0.0079 (6) | 0.0012 (6) | 0.0031 (6) |
C18 | 0.0211 (8) | 0.0201 (8) | 0.0178 (8) | 0.0078 (6) | 0.0027 (6) | 0.0064 (6) |
C19 | 0.0151 (7) | 0.0179 (8) | 0.0170 (8) | 0.0053 (6) | 0.0018 (6) | 0.0044 (6) |
C20 | 0.0137 (7) | 0.0190 (8) | 0.0168 (8) | 0.0032 (6) | 0.0016 (6) | 0.0056 (6) |
N21 | 0.0177 (6) | 0.0188 (7) | 0.0146 (6) | 0.0088 (5) | 0.0029 (5) | 0.0042 (5) |
N22 | 0.0162 (6) | 0.0179 (7) | 0.0174 (7) | 0.0068 (5) | 0.0026 (5) | 0.0054 (5) |
N23 | 0.0181 (6) | 0.0206 (7) | 0.0145 (6) | 0.0092 (5) | 0.0024 (5) | 0.0051 (5) |
N24 | 0.0172 (6) | 0.0184 (7) | 0.0150 (6) | 0.0072 (5) | 0.0024 (5) | 0.0044 (5) |
C25 | 0.0165 (7) | 0.0193 (8) | 0.0160 (8) | 0.0065 (6) | 0.0013 (6) | 0.0031 (6) |
C26 | 0.0198 (8) | 0.0193 (8) | 0.0198 (8) | 0.0067 (6) | 0.0026 (6) | 0.0056 (6) |
C27 | 0.0187 (8) | 0.0247 (8) | 0.0197 (8) | 0.0074 (6) | 0.0053 (6) | 0.0064 (7) |
C28 | 0.0183 (8) | 0.0246 (8) | 0.0163 (8) | 0.0105 (6) | 0.0009 (6) | 0.0022 (6) |
C29 | 0.0209 (8) | 0.0197 (8) | 0.0189 (8) | 0.0068 (6) | −0.0014 (6) | 0.0045 (6) |
C30 | 0.0165 (7) | 0.0216 (8) | 0.0164 (8) | 0.0051 (6) | 0.0020 (6) | 0.0035 (6) |
O31 | 0.0327 (7) | 0.0301 (7) | 0.0277 (7) | 0.0199 (5) | 0.0121 (5) | 0.0096 (5) |
C32 | 0.0198 (8) | 0.0229 (8) | 0.0160 (8) | 0.0109 (6) | 0.0035 (6) | 0.0062 (6) |
C33 | 0.0266 (9) | 0.0233 (9) | 0.0215 (9) | 0.0058 (7) | −0.0020 (7) | 0.0064 (7) |
C34 | 0.0298 (9) | 0.0250 (9) | 0.0268 (9) | 0.0084 (7) | 0.0024 (7) | 0.0111 (7) |
C35 | 0.0347 (9) | 0.0304 (9) | 0.0190 (8) | 0.0208 (8) | 0.0081 (7) | 0.0107 (7) |
C36 | 0.0395 (10) | 0.0247 (9) | 0.0174 (8) | 0.0120 (7) | −0.0037 (7) | 0.0019 (7) |
C37 | 0.0306 (9) | 0.0220 (9) | 0.0208 (9) | 0.0078 (7) | −0.0007 (7) | 0.0055 (7) |
O38 | 0.0574 (9) | 0.0344 (8) | 0.0194 (7) | 0.0204 (7) | 0.0064 (6) | 0.0121 (6) |
C39 | 0.0189 (7) | 0.0199 (8) | 0.0154 (8) | 0.0088 (6) | 0.0038 (6) | 0.0055 (6) |
C40 | 0.0193 (8) | 0.0233 (8) | 0.0187 (8) | 0.0074 (6) | 0.0029 (6) | 0.0052 (6) |
C41 | 0.0262 (8) | 0.0198 (8) | 0.0179 (8) | 0.0072 (6) | 0.0065 (6) | 0.0031 (6) |
C42 | 0.0262 (8) | 0.0205 (8) | 0.0218 (8) | 0.0127 (6) | 0.0108 (7) | 0.0079 (6) |
C43 | 0.0189 (8) | 0.0262 (9) | 0.0266 (9) | 0.0102 (6) | 0.0035 (7) | 0.0058 (7) |
C44 | 0.0194 (8) | 0.0232 (8) | 0.0211 (8) | 0.0082 (6) | 0.0000 (6) | 0.0018 (7) |
O45 | 0.0296 (7) | 0.0251 (7) | 0.0354 (8) | 0.0156 (5) | 0.0121 (6) | 0.0035 (5) |
C46 | 0.0195 (8) | 0.0178 (8) | 0.0145 (8) | 0.0071 (6) | 0.0020 (6) | 0.0031 (6) |
C47 | 0.0171 (7) | 0.0224 (8) | 0.0190 (8) | 0.0067 (6) | 0.0040 (6) | 0.0047 (6) |
C48 | 0.0197 (8) | 0.0255 (9) | 0.0206 (8) | 0.0090 (6) | −0.0014 (6) | 0.0032 (7) |
C49 | 0.0278 (8) | 0.0186 (8) | 0.0152 (8) | 0.0097 (6) | 0.0005 (6) | 0.0024 (6) |
C50 | 0.0245 (8) | 0.0224 (8) | 0.0182 (8) | 0.0078 (6) | 0.0064 (6) | 0.0057 (6) |
C51 | 0.0173 (7) | 0.0218 (8) | 0.0189 (8) | 0.0060 (6) | 0.0022 (6) | 0.0045 (6) |
O52 | 0.0325 (7) | 0.0374 (7) | 0.0181 (6) | 0.0127 (6) | −0.0001 (5) | 0.0103 (5) |
O53 | 0.0323 (7) | 0.0300 (7) | 0.0355 (8) | 0.0084 (5) | 0.0009 (6) | 0.0133 (6) |
C54 | 0.0272 (9) | 0.0205 (8) | 0.0292 (10) | 0.0037 (7) | −0.0007 (7) | 0.0042 (7) |
N55 | 0.0275 (8) | 0.0302 (8) | 0.0280 (8) | 0.0036 (6) | −0.0011 (6) | 0.0089 (7) |
C56 | 0.0461 (12) | 0.0410 (12) | 0.0297 (11) | −0.0022 (9) | −0.0056 (9) | 0.0130 (9) |
C57 | 0.0302 (10) | 0.0564 (14) | 0.0412 (12) | 0.0130 (9) | −0.0002 (9) | 0.0166 (11) |
O58 | 0.0490 (9) | 0.0322 (8) | 0.0435 (9) | 0.0196 (7) | 0.0070 (7) | −0.0010 (6) |
C59 | 0.0531 (13) | 0.0295 (11) | 0.0320 (11) | 0.0091 (9) | 0.0147 (9) | 0.0003 (8) |
N60 | 0.0532 (11) | 0.0266 (9) | 0.0416 (10) | 0.0089 (8) | 0.0159 (9) | −0.0007 (7) |
C61 | 0.153 (3) | 0.0309 (13) | 0.0527 (17) | 0.0229 (16) | 0.0308 (19) | 0.0118 (12) |
C62 | 0.0555 (15) | 0.0491 (14) | 0.0488 (14) | 0.0271 (11) | −0.0089 (11) | −0.0138 (11) |
O63 | 0.0374 (8) | 0.0505 (9) | 0.0470 (9) | 0.0152 (7) | −0.0132 (7) | 0.0082 (7) |
C64 | 0.0307 (10) | 0.0386 (11) | 0.0348 (11) | 0.0102 (8) | 0.0001 (8) | 0.0086 (9) |
N65 | 0.0293 (8) | 0.0334 (9) | 0.0320 (9) | 0.0062 (7) | −0.0022 (7) | 0.0090 (7) |
C66 | 0.0420 (12) | 0.0385 (12) | 0.0422 (13) | 0.0110 (9) | −0.0145 (10) | 0.0024 (9) |
C67 | 0.0450 (13) | 0.0508 (14) | 0.0546 (15) | 0.0024 (11) | 0.0117 (11) | 0.0211 (12) |
O68 | 0.0700 (12) | 0.0766 (13) | 0.0644 (12) | 0.0361 (10) | 0.0432 (10) | 0.0369 (10) |
C69 | 0.0366 (11) | 0.0422 (12) | 0.0448 (12) | 0.0156 (9) | 0.0121 (9) | 0.0207 (10) |
N70 | 0.0299 (9) | 0.0355 (10) | 0.0603 (13) | 0.0010 (7) | 0.0076 (8) | 0.0109 (9) |
C71 | 0.0418 (12) | 0.0456 (13) | 0.0421 (13) | 0.0061 (10) | −0.0036 (10) | 0.0005 (10) |
C72 | 0.060 (2) | 0.0536 (19) | 0.169 (4) | −0.0155 (15) | 0.034 (2) | 0.017 (2) |
O73 | 0.0487 (9) | 0.0542 (10) | 0.0644 (11) | 0.0254 (8) | 0.0270 (8) | 0.0338 (9) |
Geometric parameters (Å, º) top
C1—N21 | 1.376 (2) | C39—C40 | 1.396 (2) |
C1—C20 | 1.403 (2) | C40—C41 | 1.388 (2) |
C1—C2 | 1.429 (2) | C40—H40 | 0.9500 |
C2—C3 | 1.363 (2) | C41—C42 | 1.391 (2) |
C2—H2 | 0.9500 | C41—H41 | 0.9500 |
C3—C4 | 1.425 (2) | C42—O45 | 1.3645 (19) |
C3—H3 | 0.9500 | C42—C43 | 1.387 (2) |
C4—N21 | 1.3785 (19) | C43—C44 | 1.389 (2) |
C4—C5 | 1.410 (2) | C43—H43 | 0.9500 |
C5—C6 | 1.410 (2) | C44—H44 | 0.9500 |
C5—C25 | 1.492 (2) | O45—H45 | 0.8400 |
C6—N22 | 1.3735 (19) | C46—C47 | 1.394 (2) |
C6—C7 | 1.457 (2) | C46—C51 | 1.398 (2) |
C7—C8 | 1.350 (2) | C47—C48 | 1.389 (2) |
C7—H7 | 0.9500 | C47—H47 | 0.9500 |
C8—C9 | 1.453 (2) | C48—C49 | 1.394 (2) |
C8—H8 | 0.9500 | C48—H48 | 0.9500 |
C9—N22 | 1.362 (2) | C49—O52 | 1.358 (2) |
C9—C10 | 1.408 (2) | C49—C50 | 1.394 (2) |
C10—C11 | 1.400 (2) | C50—C51 | 1.382 (2) |
C10—C32 | 1.493 (2) | C50—H50 | 0.9500 |
C11—N23 | 1.377 (2) | C51—H51 | 0.9500 |
C11—C12 | 1.429 (2) | O52—H52 | 0.8400 |
C12—C13 | 1.362 (2) | O53—C54 | 1.235 (2) |
C12—H12 | 0.9500 | C54—N55 | 1.334 (2) |
C13—C14 | 1.429 (2) | C54—H54 | 0.9500 |
C13—H13 | 0.9500 | N55—C56 | 1.448 (3) |
C14—N23 | 1.3800 (19) | N55—C57 | 1.450 (3) |
C14—C15 | 1.401 (2) | C56—H56A | 0.9800 |
C15—C16 | 1.410 (2) | C56—H56B | 0.9800 |
C15—C39 | 1.496 (2) | C56—H56C | 0.9800 |
C16—N24 | 1.3666 (19) | C57—H57A | 0.9800 |
C16—C17 | 1.457 (2) | C57—H57B | 0.9800 |
C17—C18 | 1.352 (2) | C57—H57C | 0.9800 |
C17—H17 | 0.9500 | O58—C59 | 1.239 (3) |
C18—C19 | 1.455 (2) | C59—N60 | 1.314 (3) |
C18—H18 | 0.9500 | C59—H59 | 0.9500 |
C19—N24 | 1.369 (2) | N60—C61 | 1.459 (3) |
C19—C20 | 1.414 (2) | N60—C62 | 1.464 (3) |
C20—C46 | 1.492 (2) | C61—H61A | 0.9800 |
N21—H21 | 0.8800 | C61—H61B | 0.9800 |
N22—H22 | 0.8800 | C61—H61C | 0.9800 |
N23—H23 | 0.8800 | C62—H62A | 0.9800 |
N24—H24 | 0.8800 | C62—H62B | 0.9800 |
C25—C30 | 1.398 (2) | C62—H62C | 0.9800 |
C25—C26 | 1.400 (2) | O63—C64 | 1.238 (2) |
C26—C27 | 1.391 (2) | C64—N65 | 1.316 (3) |
C26—H26 | 0.9500 | C64—H64 | 0.9500 |
C27—C28 | 1.388 (2) | N65—C66 | 1.445 (3) |
C27—H27 | 0.9500 | N65—C67 | 1.455 (3) |
C28—O31 | 1.3629 (19) | C66—H66A | 0.9800 |
C28—C29 | 1.397 (2) | C66—H66B | 0.9800 |
C29—C30 | 1.390 (2) | C66—H66C | 0.9800 |
C29—H29 | 0.9500 | C67—H67A | 0.9800 |
C30—H30 | 0.9500 | C67—H67B | 0.9800 |
O31—H31 | 0.8400 | C67—H67C | 0.9800 |
C32—C37 | 1.392 (2) | O68—C69 | 1.225 (3) |
C32—C33 | 1.394 (2) | C69—N70 | 1.323 (3) |
C33—C34 | 1.386 (2) | C69—H69 | 0.9500 |
C33—H33 | 0.9500 | N70—C72 | 1.441 (3) |
C34—C35 | 1.390 (3) | N70—C71 | 1.454 (3) |
C34—H34 | 0.9500 | C71—H71A | 0.9800 |
C35—O38 | 1.363 (2) | C71—H71B | 0.9800 |
C35—C36 | 1.389 (3) | C71—H71C | 0.9800 |
C36—C37 | 1.384 (2) | C72—H72A | 0.9800 |
C36—H36 | 0.9500 | C72—H72B | 0.9800 |
C37—H37 | 0.9500 | C72—H72C | 0.9800 |
O38—H38 | 0.8400 | O73—H73A | 0.8887 |
C39—C44 | 1.394 (2) | O73—H73B | 0.8919 |
| | | |
N21—C1—C20 | 126.78 (14) | C44—C39—C15 | 120.90 (14) |
N21—C1—C2 | 106.60 (13) | C40—C39—C15 | 121.33 (14) |
C20—C1—C2 | 126.62 (14) | C41—C40—C39 | 121.60 (15) |
C3—C2—C1 | 108.33 (14) | C41—C40—H40 | 119.2 |
C3—C2—H2 | 125.8 | C39—C40—H40 | 119.2 |
C1—C2—H2 | 125.8 | C40—C41—C42 | 119.69 (15) |
C2—C3—C4 | 108.17 (14) | C40—C41—H41 | 120.2 |
C2—C3—H3 | 125.9 | C42—C41—H41 | 120.2 |
C4—C3—H3 | 125.9 | O45—C42—C43 | 117.49 (15) |
N21—C4—C5 | 126.06 (14) | O45—C42—C41 | 122.93 (15) |
N21—C4—C3 | 106.81 (13) | C43—C42—C41 | 119.57 (14) |
C5—C4—C3 | 127.11 (14) | C42—C43—C44 | 120.23 (15) |
C6—C5—C4 | 124.51 (14) | C42—C43—H43 | 119.9 |
C6—C5—C25 | 119.05 (14) | C44—C43—H43 | 119.9 |
C4—C5—C25 | 116.43 (14) | C43—C44—C39 | 121.16 (16) |
N22—C6—C5 | 125.28 (14) | C43—C44—H44 | 119.4 |
N22—C6—C7 | 110.47 (14) | C39—C44—H44 | 119.4 |
C5—C6—C7 | 124.14 (14) | C42—O45—H45 | 109.5 |
C8—C7—C6 | 106.58 (14) | C47—C46—C51 | 117.55 (14) |
C8—C7—H7 | 126.7 | C47—C46—C20 | 121.13 (14) |
C6—C7—H7 | 126.7 | C51—C46—C20 | 121.31 (14) |
C7—C8—C9 | 106.33 (14) | C48—C47—C46 | 121.83 (14) |
C7—C8—H8 | 126.8 | C48—C47—H47 | 119.1 |
C9—C8—H8 | 126.8 | C46—C47—H47 | 119.1 |
N22—C9—C10 | 126.09 (14) | C47—C48—C49 | 119.59 (15) |
N22—C9—C8 | 111.25 (13) | C47—C48—H48 | 120.2 |
C10—C9—C8 | 122.66 (14) | C49—C48—H48 | 120.2 |
C11—C10—C9 | 124.67 (14) | O52—C49—C48 | 123.26 (15) |
C11—C10—C32 | 116.30 (13) | O52—C49—C50 | 117.46 (14) |
C9—C10—C32 | 118.99 (13) | C48—C49—C50 | 119.27 (15) |
N23—C11—C10 | 126.85 (14) | C51—C50—C49 | 120.36 (15) |
N23—C11—C12 | 106.81 (13) | C51—C50—H50 | 119.8 |
C10—C11—C12 | 126.30 (15) | C49—C50—H50 | 119.8 |
C13—C12—C11 | 108.14 (14) | C50—C51—C46 | 121.32 (15) |
C13—C12—H12 | 125.9 | C50—C51—H51 | 119.3 |
C11—C12—H12 | 125.9 | C46—C51—H51 | 119.3 |
C12—C13—C14 | 108.43 (14) | C49—O52—H52 | 109.5 |
C12—C13—H13 | 125.8 | O53—C54—N55 | 124.46 (17) |
C14—C13—H13 | 125.8 | O53—C54—H54 | 117.8 |
N23—C14—C15 | 126.15 (14) | N55—C54—H54 | 117.8 |
N23—C14—C13 | 106.57 (13) | C54—N55—C56 | 121.25 (17) |
C15—C14—C13 | 127.27 (14) | C54—N55—C57 | 121.42 (16) |
C14—C15—C16 | 124.79 (14) | C56—N55—C57 | 117.32 (17) |
C14—C15—C39 | 115.97 (14) | N55—C56—H56A | 109.5 |
C16—C15—C39 | 119.21 (14) | N55—C56—H56B | 109.5 |
N24—C16—C15 | 125.51 (14) | H56A—C56—H56B | 109.5 |
N24—C16—C17 | 110.61 (13) | N55—C56—H56C | 109.5 |
C15—C16—C17 | 123.85 (14) | H56A—C56—H56C | 109.5 |
C18—C17—C16 | 106.61 (14) | H56B—C56—H56C | 109.5 |
C18—C17—H17 | 126.7 | N55—C57—H57A | 109.5 |
C16—C17—H17 | 126.7 | N55—C57—H57B | 109.5 |
C17—C18—C19 | 106.36 (14) | H57A—C57—H57B | 109.5 |
C17—C18—H18 | 126.8 | N55—C57—H57C | 109.5 |
C19—C18—H18 | 126.8 | H57A—C57—H57C | 109.5 |
N24—C19—C20 | 125.33 (14) | H57B—C57—H57C | 109.5 |
N24—C19—C18 | 110.81 (13) | O58—C59—N60 | 125.9 (2) |
C20—C19—C18 | 123.85 (14) | O58—C59—H59 | 117.1 |
C1—C20—C19 | 124.78 (14) | N60—C59—H59 | 117.1 |
C1—C20—C46 | 117.21 (13) | C59—N60—C61 | 121.3 (2) |
C19—C20—C46 | 118.01 (13) | C59—N60—C62 | 121.3 (2) |
C1—N21—C4 | 110.02 (13) | C61—N60—C62 | 117.5 (2) |
C1—N21—H21 | 125.0 | N60—C61—H61A | 109.5 |
C4—N21—H21 | 125.0 | N60—C61—H61B | 109.5 |
C9—N22—C6 | 105.29 (13) | H61A—C61—H61B | 109.5 |
C9—N22—H22 | 127.4 | N60—C61—H61C | 109.5 |
C6—N22—H22 | 127.4 | H61A—C61—H61C | 109.5 |
C11—N23—C14 | 110.02 (13) | H61B—C61—H61C | 109.5 |
C11—N23—H23 | 125.0 | N60—C62—H62A | 109.5 |
C14—N23—H23 | 125.0 | N60—C62—H62B | 109.5 |
C16—N24—C19 | 105.57 (13) | H62A—C62—H62B | 109.5 |
C16—N24—H24 | 127.2 | N60—C62—H62C | 109.5 |
C19—N24—H24 | 127.2 | H62A—C62—H62C | 109.5 |
C30—C25—C26 | 117.82 (14) | H62B—C62—H62C | 109.5 |
C30—C25—C5 | 121.95 (14) | O63—C64—N65 | 124.6 (2) |
C26—C25—C5 | 120.23 (14) | O63—C64—H64 | 117.7 |
C27—C26—C25 | 121.22 (15) | N65—C64—H64 | 117.7 |
C27—C26—H26 | 119.4 | C64—N65—C66 | 121.95 (18) |
C25—C26—H26 | 119.4 | C64—N65—C67 | 120.64 (19) |
C28—C27—C26 | 120.12 (15) | C66—N65—C67 | 117.37 (18) |
C28—C27—H27 | 119.9 | N65—C66—H66A | 109.5 |
C26—C27—H27 | 119.9 | N65—C66—H66B | 109.5 |
O31—C28—C27 | 117.79 (14) | H66A—C66—H66B | 109.5 |
O31—C28—C29 | 122.62 (15) | N65—C66—H66C | 109.5 |
C27—C28—C29 | 119.56 (14) | H66A—C66—H66C | 109.5 |
C30—C29—C28 | 119.84 (15) | H66B—C66—H66C | 109.5 |
C30—C29—H29 | 120.1 | N65—C67—H67A | 109.5 |
C28—C29—H29 | 120.1 | N65—C67—H67B | 109.5 |
C29—C30—C25 | 121.43 (15) | H67A—C67—H67B | 109.5 |
C29—C30—H30 | 119.3 | N65—C67—H67C | 109.5 |
C25—C30—H30 | 119.3 | H67A—C67—H67C | 109.5 |
C28—O31—H31 | 109.5 | H67B—C67—H67C | 109.5 |
C37—C32—C33 | 118.01 (15) | O68—C69—N70 | 125.4 (2) |
C37—C32—C10 | 122.21 (15) | O68—C69—H69 | 117.3 |
C33—C32—C10 | 119.74 (15) | N70—C69—H69 | 117.3 |
C34—C33—C32 | 121.46 (16) | C69—N70—C72 | 121.3 (2) |
C34—C33—H33 | 119.3 | C69—N70—C71 | 121.64 (18) |
C32—C33—H33 | 119.3 | C72—N70—C71 | 117.0 (2) |
C33—C34—C35 | 119.75 (17) | N70—C71—H71A | 109.5 |
C33—C34—H34 | 120.1 | N70—C71—H71B | 109.5 |
C35—C34—H34 | 120.1 | H71A—C71—H71B | 109.5 |
O38—C35—C36 | 118.26 (17) | N70—C71—H71C | 109.5 |
O38—C35—C34 | 122.37 (17) | H71A—C71—H71C | 109.5 |
C36—C35—C34 | 119.37 (16) | H71B—C71—H71C | 109.5 |
C37—C36—C35 | 120.46 (16) | N70—C72—H72A | 109.5 |
C37—C36—H36 | 119.8 | N70—C72—H72B | 109.5 |
C35—C36—H36 | 119.8 | H72A—C72—H72B | 109.5 |
C36—C37—C32 | 120.93 (16) | N70—C72—H72C | 109.5 |
C36—C37—H37 | 119.5 | H72A—C72—H72C | 109.5 |
C32—C37—H37 | 119.5 | H72B—C72—H72C | 109.5 |
C35—O38—H38 | 109.5 | H73A—O73—H73B | 91.5 |
C44—C39—C40 | 117.74 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O53 | 0.84 | 1.87 | 2.6891 (18) | 166 |
O38—H38···O73 | 0.84 | 1.88 | 2.720 (2) | 175 |
O45—H45···O58 | 0.84 | 1.82 | 2.649 (2) | 168 |
O52—H52···O63 | 0.84 | 1.80 | 2.6356 (19) | 176 |
O73—H73B···O68 | 0.89 | 1.89 | 2.779 (2) | 180 |
O73—H73A···O58i | 0.89 | 2.01 | 2.896 (2) | 180 |
Symmetry code: (i) x, y+1, z. |
(III) 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin
N,
N'-dimethylformamide hexasolvate dihydrate
top
Crystal data top
C44H30N4O4·6C4H9NO·2H2O | F(000) = 2648 |
Mr = 1237.48 | Dx = 1.242 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 35.5243 (8) Å | Cell parameters from 5086 reflections |
b = 6.5265 (2) Å | θ = 1.4–25.5° |
c = 29.2172 (9) Å | µ = 0.09 mm−1 |
β = 102.2713 (10)° | T = 110 K |
V = 6619.2 (3) Å3 | Needle, red |
Z = 4 | 0.50 × 0.15 × 0.15 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4359 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 25.5°, θmin = 2.5° |
Detector resolution: 12.8 pixels mm-1 | h = 0→42 |
1 deg. ϕ and ω scans | k = 0→7 |
16577 measured reflections | l = −35→34 |
6116 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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0425P)2 + 19.1457P] where P = (Fo2 + 2Fc2)/3 |
6116 reflections | (Δ/σ)max = 0.001 |
418 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
C44H30N4O4·6C4H9NO·2H2O | V = 6619.2 (3) Å3 |
Mr = 1237.48 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.5243 (8) Å | µ = 0.09 mm−1 |
b = 6.5265 (2) Å | T = 110 K |
c = 29.2172 (9) Å | 0.50 × 0.15 × 0.15 mm |
β = 102.2713 (10)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4359 reflections with I > 2σ(I) |
16577 measured reflections | Rint = 0.050 |
6116 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0425P)2 + 19.1457P] where P = (Fo2 + 2Fc2)/3 |
6116 reflections | Δρmax = 0.78 e Å−3 |
418 parameters | Δρmin = −0.48 e Å−3 |
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 | 0.21114 (7) | −0.1110 (4) | 1.07824 (8) | 0.0190 (5) | |
C2 | 0.18595 (7) | 0.0466 (4) | 1.09006 (9) | 0.0228 (6) | |
H2 | 0.1772 | 0.0579 | 1.1185 | 0.027* | |
C3 | 0.17734 (7) | 0.1731 (4) | 1.05305 (9) | 0.0228 (6) | |
H3 | 0.1614 | 0.2911 | 1.0502 | 0.027* | |
C4 | 0.19723 (7) | 0.0944 (4) | 1.01820 (8) | 0.0190 (5) | |
C5 | 0.19437 (7) | 0.1876 (4) | 0.97390 (8) | 0.0187 (5) | |
C6 | 0.21534 (7) | 0.1279 (4) | 0.94078 (8) | 0.0200 (6) | |
C7 | 0.21310 (7) | 0.2141 (4) | 0.89528 (8) | 0.0208 (6) | |
H7 | 0.1980 | 0.3290 | 0.8826 | 0.025* | |
C8 | 0.23633 (7) | 0.1027 (4) | 0.87340 (9) | 0.0221 (6) | |
H8 | 0.2406 | 0.1284 | 0.8429 | 0.026* | |
C9 | 0.25316 (7) | −0.0591 (4) | 0.90362 (8) | 0.0192 (5) | |
C10 | 0.27562 (7) | −0.2215 (4) | 0.89262 (8) | 0.0193 (5) | |
N11 | 0.21785 (6) | −0.0769 (3) | 1.03433 (7) | 0.0193 (5) | |
H11 | 0.2324 | −0.1501 | 1.0196 | 0.023* | 0.50 |
N12 | 0.24047 (6) | −0.0356 (3) | 0.94474 (7) | 0.0180 (5) | |
H12 | 0.2474 | −0.1131 | 0.9698 | 0.022* | 0.50 |
C13 | 0.16497 (7) | 0.3524 (4) | 0.95977 (8) | 0.0201 (6) | |
C14 | 0.12583 (7) | 0.3075 (4) | 0.95262 (9) | 0.0271 (6) | |
H14 | 0.1180 | 0.1713 | 0.9572 | 0.033* | |
C15 | 0.09809 (8) | 0.4570 (4) | 0.93896 (10) | 0.0306 (7) | |
H15 | 0.0716 | 0.4221 | 0.9338 | 0.037* | |
C16 | 0.10887 (8) | 0.6570 (4) | 0.93277 (9) | 0.0271 (6) | |
C17 | 0.14775 (7) | 0.7045 (4) | 0.93893 (9) | 0.0272 (6) | |
H17 | 0.1555 | 0.8408 | 0.9341 | 0.033* | |
C18 | 0.17518 (7) | 0.5537 (4) | 0.95200 (9) | 0.0241 (6) | |
H18 | 0.2017 | 0.5879 | 0.9558 | 0.029* | |
O19 | 0.08300 (5) | 0.8139 (3) | 0.92116 (8) | 0.0384 (5) | |
H19 | 0.0605 | 0.7686 | 0.9187 | 0.058* | |
C20 | 0.28576 (7) | −0.2143 (4) | 0.84547 (8) | 0.0199 (6) | |
C21 | 0.30836 (7) | −0.0564 (4) | 0.83368 (8) | 0.0217 (6) | |
H21 | 0.3162 | 0.0521 | 0.8553 | 0.026* | |
C22 | 0.31965 (7) | −0.0542 (4) | 0.79092 (9) | 0.0239 (6) | |
H22 | 0.3350 | 0.0548 | 0.7835 | 0.029* | |
C23 | 0.30832 (7) | −0.2122 (4) | 0.75902 (9) | 0.0245 (6) | |
C24 | 0.28455 (7) | −0.3669 (4) | 0.76948 (9) | 0.0246 (6) | |
H24 | 0.2758 | −0.4723 | 0.7473 | 0.029* | |
C25 | 0.27360 (7) | −0.3670 (4) | 0.81223 (9) | 0.0231 (6) | |
H25 | 0.2574 | −0.4736 | 0.8191 | 0.028* | |
O26 | 0.31952 (6) | −0.2234 (3) | 0.71726 (6) | 0.0317 (5) | |
H26 | 0.3364 | −0.1343 | 0.7165 | 0.048* | |
O27 | 0.00849 (6) | 0.7389 (4) | 0.90642 (9) | 0.0627 (8) | |
H27A | −0.0099 | 0.6688 | 0.9173 | 0.094* | |
H27B | −0.0045 | 0.8158 | 0.8798 | 0.094* | |
O28 | −0.04741 (6) | 0.5393 (4) | 0.93692 (9) | 0.0519 (6) | |
C29 | −0.04581 (9) | 0.3544 (5) | 0.94799 (11) | 0.0392 (8) | |
C30 | −0.00757 (9) | 0.2453 (6) | 0.96095 (14) | 0.0538 (10) | |
H30A | 0.0131 | 0.3389 | 0.9571 | 0.081* | |
H30B | −0.0078 | 0.1259 | 0.9406 | 0.081* | |
H30C | −0.0032 | 0.2003 | 0.9937 | 0.081* | |
N31 | −0.07745 (7) | 0.2487 (4) | 0.94935 (9) | 0.0360 (6) | |
C32 | −0.11481 (8) | 0.3509 (5) | 0.93940 (12) | 0.0423 (8) | |
H32A | −0.1112 | 0.4977 | 0.9349 | 0.063* | |
H32B | −0.1275 | 0.3308 | 0.9658 | 0.063* | |
H32C | −0.1309 | 0.2928 | 0.9109 | 0.063* | |
C33 | −0.07684 (9) | 0.0330 (5) | 0.96300 (13) | 0.0480 (9) | |
H33A | −0.0663 | 0.0207 | 0.9967 | 0.072* | |
H33B | −0.0607 | −0.0446 | 0.9458 | 0.072* | |
H33C | −0.1031 | −0.0218 | 0.9557 | 0.072* | |
O34 | −0.03218 (8) | 0.9012 (4) | 0.82393 (10) | 0.0709 (8) | |
C35 | −0.05666 (16) | 1.0450 (9) | 0.82158 (14) | 0.0814 (14) | |
C36 | −0.09979 (11) | 1.0061 (7) | 0.81677 (17) | 0.0787 (14) | |
H36A | −0.1143 | 1.0830 | 0.7899 | 0.118* | |
H36B | −0.1076 | 1.0511 | 0.8454 | 0.118* | |
H36C | −0.1051 | 0.8594 | 0.8120 | 0.118* | |
N37 | −0.04804 (13) | 1.2275 (6) | 0.82317 (12) | 0.0833 (12) | |
C38 | −0.07399 (12) | 1.4063 (6) | 0.81956 (14) | 0.0619 (11) | |
H38A | −0.0929 | 1.3834 | 0.8390 | 0.093* | |
H38B | −0.0874 | 1.4248 | 0.7869 | 0.093* | |
H38C | −0.0589 | 1.5292 | 0.8304 | 0.093* | |
C39 | −0.00403 (12) | 1.2764 (8) | 0.8273 (2) | 0.0993 (18) | |
H39A | 0.0007 | 1.3070 | 0.7962 | 0.149* | |
H39B | 0.0114 | 1.1575 | 0.8404 | 0.149* | |
H39C | 0.0032 | 1.3950 | 0.8478 | 0.149* | |
O40 | 0.37692 (6) | 0.0156 (3) | 0.70913 (7) | 0.0357 (5) | |
C41 | 0.37196 (8) | 0.1965 (5) | 0.69484 (10) | 0.0312 (7) | |
C42 | 0.33209 (9) | 0.2814 (5) | 0.68095 (12) | 0.0423 (8) | |
H42A | 0.3137 | 0.1820 | 0.6885 | 0.063* | |
H42B | 0.3260 | 0.3088 | 0.6472 | 0.063* | |
H42C | 0.3304 | 0.4092 | 0.6980 | 0.063* | |
N43 | 0.40173 (7) | 0.3143 (4) | 0.69138 (9) | 0.0402 (7) | |
C44 | 0.39836 (11) | 0.5285 (5) | 0.67616 (15) | 0.0582 (11) | |
H44A | 0.3712 | 0.5700 | 0.6700 | 0.087* | |
H44B | 0.4082 | 0.5434 | 0.6475 | 0.087* | |
H44C | 0.4133 | 0.6154 | 0.7008 | 0.087* | |
C45 | 0.44083 (9) | 0.2311 (6) | 0.70293 (13) | 0.0538 (10) | |
H45A | 0.4397 | 0.0811 | 0.7021 | 0.081* | |
H45B | 0.4537 | 0.2766 | 0.7343 | 0.081* | |
H45C | 0.4553 | 0.2799 | 0.6801 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0189 (12) | 0.0183 (14) | 0.0191 (13) | −0.0018 (11) | 0.0026 (10) | −0.0023 (11) |
C2 | 0.0255 (14) | 0.0249 (15) | 0.0191 (13) | 0.0020 (12) | 0.0076 (11) | −0.0014 (11) |
C3 | 0.0234 (13) | 0.0216 (14) | 0.0234 (13) | 0.0048 (12) | 0.0051 (10) | −0.0021 (11) |
C4 | 0.0182 (12) | 0.0172 (14) | 0.0208 (13) | −0.0014 (11) | 0.0020 (10) | −0.0017 (11) |
C5 | 0.0185 (12) | 0.0150 (13) | 0.0219 (13) | −0.0026 (11) | 0.0029 (10) | −0.0015 (11) |
C6 | 0.0200 (13) | 0.0173 (14) | 0.0220 (13) | −0.0020 (11) | 0.0027 (10) | 0.0004 (11) |
C7 | 0.0204 (13) | 0.0203 (14) | 0.0206 (13) | −0.0003 (11) | 0.0017 (10) | 0.0021 (11) |
C8 | 0.0251 (13) | 0.0221 (15) | 0.0191 (13) | −0.0003 (12) | 0.0052 (11) | 0.0016 (11) |
C9 | 0.0195 (12) | 0.0204 (14) | 0.0167 (12) | −0.0039 (11) | 0.0016 (10) | 0.0001 (11) |
C10 | 0.0191 (12) | 0.0205 (14) | 0.0177 (12) | −0.0026 (11) | 0.0031 (10) | −0.0010 (11) |
N11 | 0.0206 (11) | 0.0187 (12) | 0.0189 (11) | 0.0015 (10) | 0.0045 (9) | 0.0001 (9) |
N12 | 0.0204 (11) | 0.0170 (11) | 0.0171 (10) | 0.0007 (9) | 0.0049 (8) | −0.0010 (9) |
C13 | 0.0236 (13) | 0.0207 (14) | 0.0166 (12) | −0.0001 (12) | 0.0056 (10) | −0.0006 (11) |
C14 | 0.0266 (14) | 0.0208 (15) | 0.0347 (15) | −0.0005 (13) | 0.0084 (12) | 0.0028 (12) |
C15 | 0.0197 (14) | 0.0289 (17) | 0.0422 (17) | 0.0012 (13) | 0.0046 (12) | 0.0033 (14) |
C16 | 0.0286 (15) | 0.0218 (15) | 0.0294 (14) | 0.0085 (13) | 0.0030 (12) | 0.0038 (12) |
C17 | 0.0273 (15) | 0.0188 (15) | 0.0335 (15) | −0.0011 (13) | 0.0023 (12) | 0.0016 (12) |
C18 | 0.0202 (13) | 0.0217 (15) | 0.0290 (14) | −0.0016 (12) | 0.0019 (11) | −0.0016 (12) |
O19 | 0.0267 (10) | 0.0273 (12) | 0.0583 (14) | 0.0060 (10) | 0.0025 (10) | 0.0075 (10) |
C20 | 0.0197 (13) | 0.0201 (14) | 0.0187 (12) | 0.0021 (11) | 0.0017 (10) | 0.0012 (11) |
C21 | 0.0244 (13) | 0.0203 (14) | 0.0196 (13) | 0.0006 (12) | 0.0026 (10) | −0.0023 (11) |
C22 | 0.0249 (14) | 0.0253 (15) | 0.0225 (13) | −0.0030 (12) | 0.0073 (11) | 0.0015 (12) |
C23 | 0.0262 (14) | 0.0293 (16) | 0.0179 (13) | 0.0005 (13) | 0.0043 (11) | −0.0004 (12) |
C24 | 0.0283 (14) | 0.0266 (16) | 0.0180 (13) | −0.0010 (12) | 0.0031 (11) | −0.0043 (11) |
C25 | 0.0234 (13) | 0.0225 (15) | 0.0238 (13) | −0.0008 (12) | 0.0057 (11) | 0.0004 (11) |
O26 | 0.0406 (12) | 0.0364 (12) | 0.0213 (9) | −0.0105 (10) | 0.0139 (8) | −0.0056 (9) |
O27 | 0.0295 (12) | 0.0660 (18) | 0.0893 (19) | −0.0021 (12) | 0.0049 (12) | 0.0318 (15) |
O28 | 0.0400 (13) | 0.0383 (15) | 0.0778 (17) | 0.0015 (11) | 0.0132 (12) | 0.0124 (13) |
C29 | 0.0353 (17) | 0.037 (2) | 0.0444 (18) | 0.0014 (16) | 0.0066 (14) | 0.0045 (15) |
C30 | 0.0292 (17) | 0.050 (2) | 0.081 (3) | 0.0032 (17) | 0.0081 (17) | 0.016 (2) |
N31 | 0.0263 (13) | 0.0347 (15) | 0.0459 (15) | 0.0015 (12) | 0.0056 (11) | 0.0054 (12) |
C32 | 0.0295 (16) | 0.044 (2) | 0.053 (2) | 0.0072 (15) | 0.0076 (14) | 0.0018 (16) |
C33 | 0.0346 (18) | 0.035 (2) | 0.073 (2) | −0.0009 (16) | 0.0082 (17) | 0.0133 (18) |
O34 | 0.0729 (18) | 0.0622 (19) | 0.0756 (19) | 0.0339 (16) | 0.0114 (15) | 0.0076 (15) |
C35 | 0.117 (4) | 0.081 (4) | 0.046 (2) | 0.014 (3) | 0.015 (2) | 0.006 (2) |
C36 | 0.042 (2) | 0.086 (3) | 0.107 (4) | −0.004 (2) | 0.015 (2) | −0.004 (3) |
N37 | 0.132 (4) | 0.061 (3) | 0.054 (2) | 0.014 (3) | 0.015 (2) | 0.0031 (19) |
C38 | 0.071 (3) | 0.050 (2) | 0.060 (2) | 0.017 (2) | 0.005 (2) | 0.002 (2) |
C39 | 0.061 (3) | 0.092 (4) | 0.155 (5) | −0.025 (3) | 0.044 (3) | −0.015 (4) |
O40 | 0.0366 (12) | 0.0332 (13) | 0.0397 (12) | 0.0018 (10) | 0.0138 (9) | 0.0069 (10) |
C41 | 0.0380 (17) | 0.0306 (17) | 0.0282 (15) | 0.0038 (15) | 0.0139 (13) | −0.0008 (13) |
C42 | 0.0402 (18) | 0.0356 (19) | 0.053 (2) | 0.0073 (16) | 0.0136 (15) | 0.0031 (16) |
N43 | 0.0391 (15) | 0.0339 (15) | 0.0536 (17) | −0.0033 (13) | 0.0237 (13) | 0.0002 (13) |
C44 | 0.071 (3) | 0.0285 (19) | 0.087 (3) | −0.0064 (18) | 0.044 (2) | −0.0013 (19) |
C45 | 0.0380 (19) | 0.058 (2) | 0.070 (2) | −0.0039 (18) | 0.0222 (17) | 0.002 (2) |
Geometric parameters (Å, º) top
C1—N11 | 1.372 (3) | O26—H26 | 0.8400 |
C1—C10i | 1.404 (4) | O27—H27A | 0.9074 |
C1—C2 | 1.452 (4) | O27—H27B | 0.9569 |
C2—C3 | 1.343 (4) | O28—C29 | 1.248 (4) |
C2—H2 | 0.9500 | C29—N31 | 1.327 (4) |
C3—C4 | 1.451 (3) | C29—C30 | 1.509 (4) |
C3—H3 | 0.9500 | C30—H30A | 0.9800 |
C4—N11 | 1.365 (3) | C30—H30B | 0.9800 |
C4—C5 | 1.414 (3) | C30—H30C | 0.9800 |
C5—C6 | 1.396 (3) | N31—C32 | 1.458 (4) |
C5—C13 | 1.495 (4) | N31—C33 | 1.462 (4) |
C6—N12 | 1.380 (3) | C32—H32A | 0.9800 |
C6—C7 | 1.430 (3) | C32—H32B | 0.9800 |
C7—C8 | 1.357 (4) | C32—H32C | 0.9800 |
C7—H7 | 0.9500 | C33—H33A | 0.9800 |
C8—C9 | 1.424 (4) | C33—H33B | 0.9800 |
C8—H8 | 0.9500 | C33—H33C | 0.9800 |
C9—N12 | 1.379 (3) | O34—C35 | 1.271 (6) |
C9—C10 | 1.404 (4) | C35—N37 | 1.228 (6) |
C10—C1i | 1.404 (4) | C35—C36 | 1.530 (6) |
C10—C20 | 1.497 (3) | C36—H36A | 0.9800 |
N11—H11 | 0.8800 | C36—H36B | 0.9800 |
N12—H12 | 0.8800 | C36—H36C | 0.9800 |
C13—C14 | 1.393 (4) | N37—C38 | 1.477 (5) |
C13—C18 | 1.394 (4) | N37—C39 | 1.575 (6) |
C14—C15 | 1.384 (4) | C38—H38A | 0.9800 |
C14—H14 | 0.9500 | C38—H38B | 0.9800 |
C15—C16 | 1.383 (4) | C38—H38C | 0.9800 |
C15—H15 | 0.9500 | C39—H39A | 0.9800 |
C16—O19 | 1.370 (3) | C39—H39B | 0.9800 |
C16—C17 | 1.389 (4) | C39—H39C | 0.9800 |
C17—C18 | 1.380 (4) | O40—C41 | 1.252 (3) |
C17—H17 | 0.9500 | C41—N43 | 1.329 (4) |
C18—H18 | 0.9500 | C41—C42 | 1.494 (4) |
O19—H19 | 0.8400 | C42—H42A | 0.9800 |
C20—C25 | 1.395 (4) | C42—H42B | 0.9800 |
C20—C21 | 1.394 (4) | C42—H42C | 0.9800 |
C21—C22 | 1.391 (3) | N43—C45 | 1.463 (4) |
C21—H21 | 0.9500 | N43—C44 | 1.464 (4) |
C22—C23 | 1.391 (4) | C44—H44A | 0.9800 |
C22—H22 | 0.9500 | C44—H44B | 0.9800 |
C23—O26 | 1.364 (3) | C44—H44C | 0.9800 |
C23—C24 | 1.391 (4) | C45—H45A | 0.9800 |
C24—C25 | 1.385 (3) | C45—H45B | 0.9800 |
C24—H24 | 0.9500 | C45—H45C | 0.9800 |
C25—H25 | 0.9500 | | |
| | | |
N11—C1—C10i | 126.2 (2) | H27A—O27—H27B | 107.0 |
N11—C1—C2 | 110.2 (2) | O28—C29—N31 | 121.2 (3) |
C10i—C1—C2 | 123.4 (2) | O28—C29—C30 | 120.7 (3) |
C3—C2—C1 | 106.9 (2) | N31—C29—C30 | 118.1 (3) |
C3—C2—H2 | 126.6 | C29—C30—H30A | 109.5 |
C1—C2—H2 | 126.6 | C29—C30—H30B | 109.5 |
C2—C3—C4 | 106.6 (2) | H30A—C30—H30B | 109.5 |
C2—C3—H3 | 126.7 | C29—C30—H30C | 109.5 |
C4—C3—H3 | 126.7 | H30A—C30—H30C | 109.5 |
N11—C4—C5 | 126.7 (2) | H30B—C30—H30C | 109.5 |
N11—C4—C3 | 110.7 (2) | C29—N31—C32 | 119.8 (3) |
C5—C4—C3 | 122.6 (2) | C29—N31—C33 | 123.0 (3) |
C6—C5—C4 | 124.7 (2) | C32—N31—C33 | 117.1 (3) |
C6—C5—C13 | 117.0 (2) | N31—C32—H32A | 109.5 |
C4—C5—C13 | 118.2 (2) | N31—C32—H32B | 109.5 |
N12—C6—C5 | 126.0 (2) | H32A—C32—H32B | 109.5 |
N12—C6—C7 | 106.8 (2) | N31—C32—H32C | 109.5 |
C5—C6—C7 | 127.0 (2) | H32A—C32—H32C | 109.5 |
C8—C7—C6 | 107.9 (2) | H32B—C32—H32C | 109.5 |
C8—C7—H7 | 126.0 | N31—C33—H33A | 109.5 |
C6—C7—H7 | 126.0 | N31—C33—H33B | 109.5 |
C7—C8—C9 | 108.8 (2) | H33A—C33—H33B | 109.5 |
C7—C8—H8 | 125.6 | N31—C33—H33C | 109.5 |
C9—C8—H8 | 125.6 | H33A—C33—H33C | 109.5 |
N12—C9—C10 | 126.2 (2) | H33B—C33—H33C | 109.5 |
N12—C9—C8 | 106.6 (2) | N37—C35—O34 | 123.5 (5) |
C10—C9—C8 | 127.0 (2) | N37—C35—C36 | 113.6 (5) |
C9—C10—C1i | 125.6 (2) | O34—C35—C36 | 122.9 (5) |
C9—C10—C20 | 116.5 (2) | C35—C36—H36A | 109.5 |
C1i—C10—C20 | 117.9 (2) | C35—C36—H36B | 109.5 |
C4—N11—C1 | 105.6 (2) | H36A—C36—H36B | 109.5 |
C4—N11—H11 | 127.2 | C35—C36—H36C | 109.5 |
C1—N11—H11 | 127.2 | H36A—C36—H36C | 109.5 |
C9—N12—C6 | 109.8 (2) | H36B—C36—H36C | 109.5 |
C9—N12—H12 | 125.1 | C35—N37—C38 | 128.1 (5) |
C6—N12—H12 | 125.1 | C35—N37—C39 | 115.8 (5) |
C14—C13—C18 | 117.4 (2) | C38—N37—C39 | 116.1 (4) |
C14—C13—C5 | 120.4 (2) | N37—C38—H38A | 109.5 |
C18—C13—C5 | 122.2 (2) | N37—C38—H38B | 109.5 |
C15—C14—C13 | 121.5 (3) | H38A—C38—H38B | 109.5 |
C15—C14—H14 | 119.3 | N37—C38—H38C | 109.5 |
C13—C14—H14 | 119.3 | H38A—C38—H38C | 109.5 |
C14—C15—C16 | 120.2 (3) | H38B—C38—H38C | 109.5 |
C14—C15—H15 | 119.9 | N37—C39—H39A | 109.5 |
C16—C15—H15 | 119.9 | N37—C39—H39B | 109.5 |
O19—C16—C15 | 123.2 (2) | H39A—C39—H39B | 109.5 |
O19—C16—C17 | 117.5 (2) | N37—C39—H39C | 109.5 |
C15—C16—C17 | 119.3 (2) | H39A—C39—H39C | 109.5 |
C18—C17—C16 | 120.1 (3) | H39B—C39—H39C | 109.5 |
C18—C17—H17 | 120.0 | O40—C41—N43 | 120.9 (3) |
C16—C17—H17 | 120.0 | O40—C41—C42 | 119.9 (3) |
C17—C18—C13 | 121.6 (2) | N43—C41—C42 | 119.2 (3) |
C17—C18—H18 | 119.2 | C41—C42—H42A | 109.5 |
C13—C18—H18 | 119.2 | C41—C42—H42B | 109.5 |
C16—O19—H19 | 109.5 | H42A—C42—H42B | 109.5 |
C25—C20—C21 | 117.8 (2) | C41—C42—H42C | 109.5 |
C25—C20—C10 | 121.3 (2) | H42A—C42—H42C | 109.5 |
C21—C20—C10 | 121.0 (2) | H42B—C42—H42C | 109.5 |
C22—C21—C20 | 121.4 (2) | C41—N43—C45 | 120.0 (3) |
C22—C21—H21 | 119.3 | C41—N43—C44 | 124.1 (3) |
C20—C21—H21 | 119.3 | C45—N43—C44 | 115.9 (3) |
C23—C22—C21 | 119.8 (2) | N43—C44—H44A | 109.5 |
C23—C22—H22 | 120.1 | N43—C44—H44B | 109.5 |
C21—C22—H22 | 120.1 | H44A—C44—H44B | 109.5 |
O26—C23—C22 | 122.8 (2) | N43—C44—H44C | 109.5 |
O26—C23—C24 | 117.6 (2) | H44A—C44—H44C | 109.5 |
C22—C23—C24 | 119.6 (2) | H44B—C44—H44C | 109.5 |
C25—C24—C23 | 119.9 (2) | N43—C45—H45A | 109.5 |
C25—C24—H24 | 120.1 | N43—C45—H45B | 109.5 |
C23—C24—H24 | 120.1 | H45A—C45—H45B | 109.5 |
C24—C25—C20 | 121.5 (2) | N43—C45—H45C | 109.5 |
C24—C25—H25 | 119.2 | H45A—C45—H45C | 109.5 |
C20—C25—H25 | 119.2 | H45B—C45—H45C | 109.5 |
C23—O26—H26 | 109.5 | | |
Symmetry code: (i) −x+1/2, −y−1/2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O19—H19···O27 | 0.84 | 1.82 | 2.636 (3) | 164 |
O26—H26···O40 | 0.84 | 1.79 | 2.618 (3) | 168 |
O27—H27A···O28 | 0.91 | 1.77 | 2.681 (3) | 177 |
O27—H27B···O34 | 0.96 | 1.81 | 2.745 (4) | 166 |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C44H30N4O4·4C3H7NO | C44H30N4O4·4C3H7NO·H2O | C44H30N4O4·6C4H9NO·2H2O |
Mr | 971.10 | 989.12 | 1237.48 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 110 | 110 | 110 |
a, b, c (Å) | 13.6255 (2), 16.0184 (3), 26.2466 (5) | 12.8346 (2), 13.6669 (2), 15.3200 (3) | 35.5243 (8), 6.5265 (2), 29.2172 (9) |
α, β, γ (°) | 101.7445 (12), 92.4786 (12), 114.9158 (8) | 102.8305 (6), 90.2339 (6), 104.3547 (11) | 90, 102.2713 (10), 90 |
V (Å3) | 5032.65 (15) | 2533.39 (7) | 6619.2 (3) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 | 0.60 × 0.50 × 0.30 | 0.50 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50610, 23879, 13053 | 26977, 12018, 8881 | 16577, 6116, 4359 |
Rint | 0.051 | 0.030 | 0.050 |
(sin θ/λ)max (Å−1) | 0.658 | 0.664 | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.169, 1.04 | 0.053, 0.153, 1.03 | 0.069, 0.154, 1.03 |
No. of reflections | 23877 | 12018 | 6116 |
No. of parameters | 1370 | 670 | 418 |
No. of restraints | 18 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
| w = 1/[σ2(Fo2) + (0.0777P)2 + 0.4228P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0787P)2 + 1.1683P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0425P)2 + 19.1457P] where P = (Fo2 + 2Fc2)/3 |
Δρmax, Δρmin (e Å−3) | 0.36, −0.39 | 0.48, −0.44 | 0.78, −0.48 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O115 | 0.84 | 1.80 | 2.6366 (18) | 177 |
O38—H38···O125 | 0.84 | 1.82 | 2.6491 (17) | 171 |
O45—H45···O110 | 0.84 | 1.83 | 2.6666 (16) | 174 |
O52—H52···O120 | 0.84 | 1.83 | 2.6686 (18) | 175 |
O83—H83···O40A | 0.84 | 1.82 | 2.642 (4) | 166 |
O83—H83···O40B | 0.84 | 1.89 | 2.647 (4) | 149 |
O90—H90···O135 | 0.84 | 1.86 | 2.6929 (18) | 174 |
O97—H97···O105 | 0.84 | 1.81 | 2.6467 (16) | 174 |
O104—H104···O130 | 0.84 | 1.86 | 2.6961 (18) | 174 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O53 | 0.84 | 1.87 | 2.6891 (18) | 166 |
O38—H38···O73 | 0.84 | 1.88 | 2.720 (2) | 175 |
O45—H45···O58 | 0.84 | 1.82 | 2.649 (2) | 168 |
O52—H52···O63 | 0.84 | 1.80 | 2.6356 (19) | 176 |
O73—H73B···O68 | 0.89 | 1.89 | 2.779 (2) | 180 |
O73—H73A···O58i | 0.89 | 2.01 | 2.896 (2) | 180 |
Symmetry code: (i) x, y+1, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O19—H19···O27 | 0.84 | 1.82 | 2.636 (3) | 164 |
O26—H26···O40 | 0.84 | 1.79 | 2.618 (3) | 168 |
O27—H27A···O28 | 0.91 | 1.77 | 2.681 (3) | 177 |
O27—H27B···O34 | 0.96 | 1.81 | 2.745 (4) | 166 |
Porphyrin macrocycles tetra-substituted with 4-hydroxyphenyl groups at their meso positions (TOHPP) provide a classical example of an organic moiety with multiple complementary terminal functional groups directed at four diverging directions of the equatorial molecular plane that exhibits a high propensity for self-assembling into flat hydrogen-bonded two-dimensional nets (Goldberg, 2002, 2005). It has been shown that the hydroxy substituents may engage readily in O—H···O—H supramolecular synthons, leading to the formation of extended multiporphyrin arrays. Suitable examples include the zinc-metallated porphyrin Zn-TOHPP platform (Goldberg et al., 1995). In some cases, water species are incorporated into the hydrogen-bonding patterns, bridging neighbouring porphyrin units while preserving the two-dimensional connectivity scheme. In this study, we attempted to use free base TOHPP building blocks in reactions with heavy metal ions as possible interporphyrin connectors under solvothermal conditions, following our earlier successful results to this end with the tetra(4-carboxyphenyl)porphyrin (TCPP) isomer (Goldberg, 2008). These reactions were carried out in a dimethylformamide–water or dimethylacetamide–water solvent environment, as hydrolysis of the amide was found to promote the synthesis of metal–organic frameworks (Burrows et al., 2005; Lipstman et al., 2007; Muniappan et al., 2007). These solvent mixtures are then capable of solubilizing the TOHPP and engaging it in the supramolecular reaction. On the other hand, it is also well documented that the networking of functionalized porphyrin moieties, both via direct intermolecular hydrogen bonding or by intercoordination through bridging metal ions, can be disrupted readily by competing solvation that may prevent supramolecular association. This is common with strong Lewis base reagents, for example dimethylformamide, dimethyl sulfoxide and pyridine, which have rather strong proton affinity for the hydroxylic acid H atom (Lipstman et al., 2006; George et al., 2006). Indeed, present efforts to prepare TOHPP-based extended supramolecular architectures, either by O—H···O—H or O—H···metal···O—H interactions, in the given experimental conditions have failed. Instead, the products obtained represent totally solvated discrete porphyrin–solvent assemblies, held together by hydrogen bonds between the tetradentate porphyrin and the surrounding components, rather than extended network arrays. Similar observations have been reported for the TCPP platform (Lipstman et al., 2006; George et al., 2006).
Within the above context, we describe here the structures of the solid products obtained by crystallizing TOHPP from a mixture of dimethylformamide and water, (I) and (II), and dimethylacetamide and water, (III). The molecular structures of (I)–(III) are shown in Figs. 1–3, respectively. In all cases, various lanthanide salts were also present in the solvothermal reactors, but not incorporated into the crystalline products.
Although compounds (I) and (II) were obtained from crystallization mixtures of similar composition, they represent differently structured adducts. In (I), the TOHPP unit is hydrogen-bonded at the four corners of its molecular framework to a dimethylformamide species, forming a pentameric assembly, without incorporation of any water molecule into the structure (Table 1). The asymmetric unit contains two such adduct assemblies of slightly different geometry and partial disorder of the terminal amide species (Fig. 1).
A different composition (TOHPP:dimethylformamide:water 1:4:1) and connectivity scheme characterizes adduct (II). Here, only three of the OH groups (atoms O31, O45 and O52) form hydrogen bonds directly to the adjacent amide species, while the fourth hydroxyl site (atom O38) interacts with another amide molecule through an intervening water molecule (O73) (Fig. 2 and Table 2).
In (III), the porphyrin:dimethylacetamide:water composition is 1:6:2, and the entire nine-component hydrogen-bonded entity is located on inversion (Fig. 3). The two inversion-related O26 hydroxyl groups form direct O—H···O(═C) hydrogen bonds with the amides. On the other hand, each of the O19 hydroxyl groups forms hydrogen bonds to a water molecule (O27) first, which then donates its two H atoms to the carbonyl groups of two other units of the dimethylacetamide, atoms O28 and O34 (Table 3).
As expected, the conformation of the free base porphyrin macrocycle is significantly distorted from planarity in spite of its aromatic nature. This should be attributed to the repulsion between the inner pyrrole H atoms. In (I) and (II) a marked saddle-type distortion from planarity characterizes the conformation of the porphyrin core (Fig. 4a and b). A somewhat smaller distortion is observed in (III), but it is still evident from Fig. 4(c) that the inner pyrrole H atoms avoid each other as much as possible. The inner pyrrole H atoms could not be located from experimental data, which prevents a detailed discussion of this feature. It can only be said that the observed deformations are such that the minimum distance between the two H atoms (with the assumed N—H `X-ray' bond length of 0.88 Å) across the porphyrin core is at least 2.3 Å.
The observed crystal packing in compounds (I)–(III) is charateristic of the vast number of porphyrin `sponges' and clathrates, whether of purely van der Waals or hydrogen bonding-assisted types, reported previously (e.g. Byrn et al., 1993, and references therein). It generally consists of alternating (columnar or layered) zones of offset-stacked porphyrin moieties and molecules of the solvent. This is nicely demonstrated in Fig. 5, which depicts an intercalating type of molecular organization in (III).
In summary, this study describes the effects of competing solvation on the self-assembly of TOHPP-type porphyrin building blocks by hydrogen bonding, where solvent components bearing dominant (in the amide entities) or comparable (in the water solvent) H-atom accepting capacity interfere with the direct assembly of the porphyrin units into supramolecular porphyrin arrays. It also reports for the first time crystal structures of the free base TOHPP entity.