Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012788/ya6045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012788/ya6045Isup2.hkl |
CCDC reference: 172193
Key indicators
- Single-crystal X-ray study
- T = 110 K
- Mean (C-C) = 0.008 Å
- R factor = 0.069
- wR factor = 0.187
- Data-to-parameter ratio = 17.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_731 Alert C Bond Calc 2.073(9), Rep 2.072(3) .... 3.00 s.u-Ratio ZN -N2 1.555 1.555 PLAT_731 Alert C Bond Calc 2.067(9), Rep 2.067(4) .... 2.25 s.u-Ratio ZN -N4 1.555 1.555 PLAT_732 Alert C Angle Calc 95.56(12), Rep 95.6(3) .... 2.50 s.u-Ratio N1 -ZN -O5 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 99.52(12), Rep 99.5(3) .... 2.50 s.u-Ratio N3 -ZN -O5 1.555 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
The free base used for the preparation of the title compound was synthesized according to a previously reported procedure (Collman et al., 1997). A 150 ml three-necked round-bottomed flask equipped with a stirrer bar was charged with the αααβ-atropisomer of 5,10,15,20-tetrakis(2-aminophenyl)porphyrin (TAPP; 337 mg, 0.5 mmol), dry THF (30 ml) and six equivalents of Et3N, then cooled in an ice bath, at which time, five equivalents of chloroacetyl chloride in 30 ml of dry THF were injected dropwise. The solution was allowed to stir for 3 h, after which the THF was removed in vacuo. The α-5,10,15:β-20-[tetrakis(2-chloroacetamido)phenyl]porphyrin was purified by flash chromatography on a silica column and eluted with 3% methanol in CH2Cl2; the yield was 73%·The title compound, (I), was obtained by zinc insertion according to the usual method which consists of refluxing a chloroform solution of the free-base porphyrin with a saturated solution of zinc acetate in methanol (Smith, 1975). Crystals suitable for X-ray data collection were obtained by slow (over a three-month period) diffusion of MeOH in a CHCl3 solution of compound (I) at room temperature.
H atoms were inserted at calculated positions or found in the difference electron-density map (for those of the methanol molecule and those of the amide groups) and treated in the riding model approximation with isotropic displacement parameters set to 1.2 times those of the parent atoms. The highest residual electron-density peak was located near the Cl6 atom of the chloroform solvate molecule.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
Fig. 1. View of (I) with 50% probability displacement ellipsoids. The H atoms and the chloroform solvate molecule have been omitted for clarity. |
[Zn(C52H36Cl4N8O4)(CH4O)]·CHCl3 | F(000) = 2440 |
Mr = 1195.47 | Dx = 1.541 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.078 (6) Å | Cell parameters from 19872 reflections |
b = 17.899 (7) Å | θ = 1.0–27.5° |
c = 22.79 (9) Å | µ = 0.90 mm−1 |
β = 105.009 (2)° | T = 110 K |
V = 5153 (21) Å3 | Prism, red |
Z = 4 | 0.25 × 0.25 × 0.25 mm |
KappaCCD diffractometer | Rint = 0.033 |
ϕ scans (κ = 0) + additional ω scans | θmax = 27.5°, θmin = 2.0° |
19872 measured reflections | h = −16→16 |
11775 independent reflections | k = −16→23 |
7802 reflections with I > 2σ(I) | l = −29→29 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.069 | w = 1/[σ2(Fo2) + (0.0845P)2 + 10.6403P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.187 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 1.27 e Å−3 |
11775 reflections | Δρmin = −1.62 e Å−3 |
676 parameters |
[Zn(C52H36Cl4N8O4)(CH4O)]·CHCl3 | V = 5153 (21) Å3 |
Mr = 1195.47 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.078 (6) Å | µ = 0.90 mm−1 |
b = 17.899 (7) Å | T = 110 K |
c = 22.79 (9) Å | 0.25 × 0.25 × 0.25 mm |
β = 105.009 (2)° |
KappaCCD diffractometer | 7802 reflections with I > 2σ(I) |
19872 measured reflections | Rint = 0.033 |
11775 independent reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0845P)2 + 10.6403P] where P = (Fo2 + 2Fc2)/3 |
11775 reflections | Δρmax = 1.27 e Å−3 |
676 parameters | Δρmin = −1.62 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.18059 (4) | 0.19459 (3) | 0.100060 (19) | 0.01684 (13) | |
Cl1 | −0.13369 (10) | −0.02724 (7) | 0.00181 (5) | 0.0400 (3) | |
Cl2 | −0.04149 (11) | 0.11479 (7) | −0.11408 (5) | 0.0401 (3) | |
Cl3 | 0.42224 (13) | 0.38847 (8) | 0.16719 (6) | 0.0507 (4) | |
Cl4 | 0.37591 (14) | −0.08478 (11) | 0.00903 (6) | 0.0676 (5) | |
Cl5 | 0.56419 (19) | 0.21015 (12) | 0.26300 (11) | 0.0952 (8) | |
Cl6 | 0.6849 (2) | 0.33913 (15) | 0.30878 (10) | 0.1124 (10) | |
Cl7 | 0.6965 (2) | 0.28012 (14) | 0.19549 (12) | 0.1072 (9) | |
O1 | −0.3337 (3) | −0.0486 (3) | 0.10310 (17) | 0.0562 (11) | |
O2 | −0.1883 (3) | 0.27700 (18) | −0.21841 (13) | 0.0363 (8) | |
O3 | 0.6299 (6) | 0.4503 (4) | 0.0801 (3) | 0.135 (3) | |
O4 | 0.3142 (3) | −0.1403 (3) | 0.16143 (18) | 0.0551 (11) | |
O5 | 0.2209 (2) | 0.27919 (16) | 0.16899 (12) | 0.0226 (6) | |
N1 | 0.1751 (3) | 0.10855 (18) | 0.15861 (14) | 0.0182 (7) | |
N2 | 0.0178 (3) | 0.20617 (18) | 0.08284 (14) | 0.0176 (7) | |
N3 | 0.1756 (3) | 0.25910 (19) | 0.02443 (14) | 0.0198 (7) | |
N4 | 0.3322 (3) | 0.16170 (19) | 0.10029 (14) | 0.0199 (7) | |
N5 | −0.1742 (3) | 0.0121 (2) | 0.12119 (16) | 0.0273 (8) | |
N6 | −0.1173 (3) | 0.2688 (2) | −0.11627 (15) | 0.0246 (8) | |
N7 | 0.4979 (4) | 0.3648 (2) | 0.05881 (19) | 0.0426 (11) | |
N8 | 0.4426 (3) | −0.0679 (2) | 0.14126 (16) | 0.0311 (9) | |
C1 | 0.2593 (3) | 0.0649 (2) | 0.18932 (16) | 0.0179 (8) | |
C2 | 0.2239 (3) | 0.0163 (2) | 0.23098 (17) | 0.0197 (8) | |
C3 | 0.1207 (3) | 0.0315 (2) | 0.22560 (17) | 0.0192 (8) | |
C4 | 0.0905 (3) | 0.0897 (2) | 0.18043 (16) | 0.0174 (8) | |
C5 | −0.0113 (3) | 0.1214 (2) | 0.16199 (17) | 0.0181 (8) | |
C6 | −0.0447 (3) | 0.1746 (2) | 0.11593 (17) | 0.0198 (8) | |
C7 | −0.1498 (3) | 0.2066 (3) | 0.09787 (18) | 0.0252 (9) | |
C8 | −0.1491 (3) | 0.2575 (2) | 0.05373 (18) | 0.0248 (9) | |
C9 | −0.0444 (3) | 0.2573 (2) | 0.04498 (17) | 0.0195 (8) | |
C10 | −0.0094 (3) | 0.3032 (2) | 0.00349 (16) | 0.0206 (8) | |
C11 | 0.0915 (3) | 0.3021 (2) | −0.00659 (17) | 0.0190 (8) | |
C12 | 0.1239 (4) | 0.3458 (3) | −0.05169 (19) | 0.0264 (9) | |
C13 | 0.2258 (4) | 0.3297 (3) | −0.04753 (18) | 0.0271 (10) | |
C14 | 0.2588 (3) | 0.2749 (2) | 0.00032 (18) | 0.0223 (9) | |
C15 | 0.3611 (3) | 0.2444 (2) | 0.01932 (18) | 0.0226 (9) | |
C16 | 0.3942 (3) | 0.1930 (2) | 0.06679 (18) | 0.0224 (9) | |
C17 | 0.5004 (3) | 0.1628 (3) | 0.0870 (2) | 0.0277 (10) | |
C18 | 0.5006 (4) | 0.1141 (3) | 0.13163 (19) | 0.0282 (10) | |
C19 | 0.3949 (3) | 0.1126 (2) | 0.13985 (17) | 0.0215 (9) | |
C20 | 0.3618 (3) | 0.0678 (2) | 0.18214 (17) | 0.0198 (8) | |
C21 | −0.0871 (3) | 0.0995 (2) | 0.19834 (18) | 0.0207 (8) | |
C22 | −0.0766 (4) | 0.1313 (3) | 0.25513 (19) | 0.0267 (9) | |
C23 | −0.1439 (4) | 0.1132 (3) | 0.2909 (2) | 0.0310 (10) | |
C24 | −0.2241 (4) | 0.0622 (3) | 0.2700 (2) | 0.0321 (11) | |
C25 | −0.2371 (3) | 0.0289 (3) | 0.2139 (2) | 0.0288 (10) | |
C26 | −0.1678 (3) | 0.0473 (2) | 0.17767 (18) | 0.0235 (9) | |
C27 | −0.2514 (4) | −0.0336 (3) | 0.0896 (2) | 0.0414 (13) | |
C28 | −0.2300 (5) | −0.0704 (3) | 0.0335 (2) | 0.0460 (14) | |
C29 | −0.0872 (3) | 0.3568 (2) | −0.03416 (18) | 0.0214 (8) | |
C30 | −0.1074 (4) | 0.4249 (3) | −0.0110 (2) | 0.0298 (10) | |
C31 | −0.1747 (4) | 0.4768 (3) | −0.0462 (2) | 0.0346 (11) | |
C32 | −0.2231 (4) | 0.4596 (3) | −0.1066 (2) | 0.0291 (10) | |
C33 | −0.2057 (3) | 0.3920 (2) | −0.13123 (19) | 0.0238 (9) | |
C34 | −0.1385 (3) | 0.3400 (2) | −0.09497 (17) | 0.0203 (8) | |
C35 | −0.1417 (4) | 0.2421 (2) | −0.17327 (19) | 0.0277 (10) | |
C36 | −0.1056 (4) | 0.1631 (3) | −0.18201 (19) | 0.0331 (11) | |
C37 | 0.4386 (3) | 0.2695 (3) | −0.01499 (19) | 0.0264 (9) | |
C38 | 0.4413 (4) | 0.2340 (3) | −0.0687 (2) | 0.0324 (10) | |
C39 | 0.5086 (4) | 0.2594 (3) | −0.1028 (2) | 0.0397 (13) | |
C40 | 0.5739 (4) | 0.3187 (3) | −0.0823 (2) | 0.0431 (13) | |
C41 | 0.5750 (4) | 0.3558 (3) | −0.0295 (2) | 0.0410 (12) | |
C42 | 0.5056 (4) | 0.3304 (3) | 0.0046 (2) | 0.0333 (11) | |
C43 | 0.5547 (6) | 0.4195 (4) | 0.0916 (3) | 0.077 (2) | |
C44 | 0.5208 (7) | 0.4452 (4) | 0.1480 (3) | 0.083 (3) | |
C45 | 0.4425 (3) | 0.0193 (2) | 0.22421 (18) | 0.0223 (9) | |
C46 | 0.4768 (3) | 0.0357 (2) | 0.28542 (19) | 0.0255 (9) | |
C47 | 0.5477 (4) | −0.0098 (3) | 0.3253 (2) | 0.0284 (10) | |
C48 | 0.5872 (4) | −0.0731 (3) | 0.3047 (2) | 0.0286 (10) | |
C49 | 0.5540 (4) | −0.0913 (3) | 0.2432 (2) | 0.0304 (10) | |
C50 | 0.4818 (3) | −0.0459 (2) | 0.20367 (18) | 0.0238 (9) | |
C51 | 0.3562 (4) | −0.1117 (3) | 0.1252 (2) | 0.0393 (12) | |
C52 | 0.3084 (5) | −0.1264 (4) | 0.0585 (2) | 0.0539 (16) | |
C53 | 0.1425 (4) | 0.3309 (3) | 0.1765 (2) | 0.0404 (13) | |
C54 | 0.6770 (7) | 0.2590 (4) | 0.2656 (5) | 0.092 (3) | |
H5O | 0.2554 | 0.2580 | 0.2049 | 0.027* | |
H5N | −0.1232 | 0.0240 | 0.1025 | 0.033* | |
H6N | −0.0605 | 0.2393 | −0.0919 | 0.029* | |
H7N | 0.4416 | 0.3436 | 0.0737 | 0.051* | |
H8N | 0.4734 | −0.0454 | 0.1154 | 0.037* | |
H2 | 0.2648 | −0.0189 | 0.2567 | 0.024* | |
H3 | 0.0773 | 0.0088 | 0.2469 | 0.023* | |
H7 | −0.2067 | 0.1946 | 0.1135 | 0.030* | |
H8 | −0.2058 | 0.2868 | 0.0331 | 0.030* | |
H12 | 0.0818 | 0.3792 | −0.0788 | 0.032* | |
H13 | 0.2674 | 0.3499 | −0.0710 | 0.033* | |
H17 | 0.5577 | 0.1750 | 0.0718 | 0.033* | |
H18 | 0.5583 | 0.0864 | 0.1533 | 0.034* | |
H22 | −0.0228 | 0.1658 | 0.2696 | 0.032* | |
H23 | −0.1350 | 0.1353 | 0.3288 | 0.037* | |
H24 | −0.2697 | 0.0503 | 0.2938 | 0.039* | |
H25 | −0.2912 | −0.0055 | 0.2000 | 0.035* | |
H28A | −0.2962 | −0.0725 | 0.0022 | 0.055* | |
H28B | −0.2078 | −0.1215 | 0.0438 | 0.055* | |
H30 | −0.0750 | 0.4361 | 0.0294 | 0.036* | |
H31 | −0.1874 | 0.5224 | −0.0298 | 0.041* | |
H32 | −0.2680 | 0.4943 | −0.1307 | 0.035* | |
H33 | −0.2384 | 0.3811 | −0.1716 | 0.029* | |
H36A | −0.0574 | 0.1653 | −0.2080 | 0.040* | |
H36B | −0.1668 | 0.1342 | −0.2032 | 0.040* | |
H38 | 0.3979 | 0.1929 | −0.0820 | 0.039* | |
H39 | 0.5092 | 0.2361 | −0.1392 | 0.048* | |
H40 | 0.6194 | 0.3346 | −0.1052 | 0.052* | |
H41 | 0.6199 | 0.3962 | −0.0165 | 0.049* | |
H44A | 0.4941 | 0.4959 | 0.1413 | 0.100* | |
H44B | 0.5828 | 0.4462 | 0.1823 | 0.100* | |
H46 | 0.4516 | 0.0785 | 0.3002 | 0.031* | |
H47 | 0.5689 | 0.0023 | 0.3664 | 0.034* | |
H48 | 0.6354 | −0.1033 | 0.3315 | 0.034* | |
H49 | 0.5803 | −0.1338 | 0.2287 | 0.036* | |
H52A | 0.2360 | −0.1083 | 0.0479 | 0.065* | |
H52B | 0.3061 | −0.1799 | 0.0519 | 0.065* | |
H53A | 0.1492 | 0.3585 | 0.2121 | 0.048* | |
H53B | 0.0779 | 0.3022 | 0.1743 | 0.048* | |
H53C | 0.1295 | 0.3645 | 0.1421 | 0.048* | |
H54 | 0.7362 | 0.2271 | 0.2863 | 0.110* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0146 (2) | 0.0212 (2) | 0.0141 (2) | 0.00009 (19) | 0.00265 (16) | 0.00104 (18) |
Cl1 | 0.0427 (7) | 0.0485 (8) | 0.0281 (6) | 0.0024 (6) | 0.0078 (5) | −0.0058 (5) |
Cl2 | 0.0504 (8) | 0.0312 (6) | 0.0332 (6) | 0.0109 (5) | 0.0011 (5) | −0.0038 (5) |
Cl3 | 0.0693 (10) | 0.0421 (8) | 0.0432 (7) | −0.0021 (7) | 0.0192 (7) | −0.0106 (6) |
Cl4 | 0.0629 (10) | 0.1104 (14) | 0.0281 (7) | 0.0351 (10) | 0.0094 (6) | −0.0021 (7) |
Cl5 | 0.1065 (17) | 0.0740 (13) | 0.1310 (18) | −0.0452 (12) | 0.0775 (15) | −0.0468 (12) |
Cl6 | 0.145 (2) | 0.1125 (18) | 0.0733 (13) | −0.0725 (17) | 0.0163 (14) | −0.0197 (13) |
Cl7 | 0.1147 (19) | 0.1098 (17) | 0.1280 (19) | −0.0586 (15) | 0.0870 (16) | −0.0549 (15) |
O1 | 0.046 (2) | 0.080 (3) | 0.043 (2) | −0.034 (2) | 0.0122 (18) | −0.012 (2) |
O2 | 0.051 (2) | 0.0320 (18) | 0.0181 (15) | −0.0016 (16) | −0.0054 (14) | −0.0002 (14) |
O3 | 0.141 (6) | 0.168 (7) | 0.113 (5) | −0.122 (6) | 0.067 (4) | −0.068 (5) |
O4 | 0.041 (2) | 0.078 (3) | 0.047 (2) | −0.020 (2) | 0.0123 (18) | −0.018 (2) |
O5 | 0.0256 (16) | 0.0222 (15) | 0.0173 (13) | 0.0020 (12) | 0.0005 (12) | 0.0022 (11) |
N1 | 0.0174 (17) | 0.0210 (17) | 0.0157 (15) | 0.0000 (14) | 0.0032 (13) | −0.0015 (13) |
N2 | 0.0167 (17) | 0.0200 (18) | 0.0154 (15) | −0.0004 (13) | 0.0030 (13) | 0.0013 (13) |
N3 | 0.0195 (18) | 0.0235 (18) | 0.0151 (15) | 0.0004 (14) | 0.0021 (13) | 0.0015 (13) |
N4 | 0.0186 (18) | 0.0227 (18) | 0.0181 (16) | −0.0005 (14) | 0.0041 (13) | 0.0030 (14) |
N5 | 0.0229 (19) | 0.035 (2) | 0.0241 (18) | −0.0070 (16) | 0.0065 (15) | −0.0034 (16) |
N6 | 0.029 (2) | 0.0219 (19) | 0.0190 (17) | 0.0051 (15) | 0.0000 (14) | 0.0011 (14) |
N7 | 0.044 (3) | 0.046 (3) | 0.040 (2) | −0.021 (2) | 0.015 (2) | −0.007 (2) |
N8 | 0.036 (2) | 0.033 (2) | 0.0249 (18) | 0.0086 (18) | 0.0085 (16) | 0.0010 (16) |
C1 | 0.016 (2) | 0.021 (2) | 0.0152 (17) | 0.0016 (16) | 0.0019 (15) | −0.0025 (15) |
C2 | 0.023 (2) | 0.018 (2) | 0.0177 (18) | 0.0028 (16) | 0.0048 (16) | −0.0010 (16) |
C3 | 0.022 (2) | 0.017 (2) | 0.0190 (19) | −0.0045 (16) | 0.0061 (16) | −0.0003 (15) |
C4 | 0.019 (2) | 0.017 (2) | 0.0154 (17) | −0.0045 (15) | 0.0029 (15) | −0.0018 (15) |
C5 | 0.0159 (19) | 0.023 (2) | 0.0163 (18) | −0.0006 (16) | 0.0050 (15) | −0.0020 (16) |
C6 | 0.017 (2) | 0.027 (2) | 0.0152 (18) | −0.0001 (16) | 0.0035 (15) | −0.0036 (16) |
C7 | 0.016 (2) | 0.037 (3) | 0.022 (2) | 0.0029 (18) | 0.0036 (16) | 0.0043 (18) |
C8 | 0.021 (2) | 0.031 (2) | 0.020 (2) | 0.0051 (18) | 0.0027 (17) | −0.0002 (17) |
C9 | 0.016 (2) | 0.026 (2) | 0.0152 (18) | 0.0014 (16) | 0.0007 (15) | −0.0023 (16) |
C10 | 0.022 (2) | 0.024 (2) | 0.0119 (17) | −0.0009 (17) | −0.0017 (15) | −0.0050 (16) |
C11 | 0.018 (2) | 0.020 (2) | 0.0159 (17) | 0.0011 (16) | −0.0005 (15) | 0.0016 (16) |
C12 | 0.027 (2) | 0.031 (2) | 0.022 (2) | 0.0024 (19) | 0.0070 (17) | 0.0068 (18) |
C13 | 0.028 (2) | 0.035 (2) | 0.019 (2) | −0.0019 (19) | 0.0068 (17) | 0.0087 (18) |
C14 | 0.022 (2) | 0.026 (2) | 0.0199 (19) | −0.0018 (17) | 0.0063 (16) | 0.0044 (17) |
C15 | 0.022 (2) | 0.026 (2) | 0.0199 (19) | −0.0016 (17) | 0.0058 (16) | 0.0002 (17) |
C16 | 0.019 (2) | 0.029 (2) | 0.0193 (19) | −0.0036 (18) | 0.0063 (16) | −0.0001 (17) |
C17 | 0.019 (2) | 0.035 (3) | 0.030 (2) | 0.0041 (19) | 0.0096 (18) | 0.0060 (19) |
C18 | 0.021 (2) | 0.036 (3) | 0.028 (2) | 0.0092 (19) | 0.0067 (18) | 0.0081 (19) |
C19 | 0.018 (2) | 0.029 (2) | 0.0166 (18) | 0.0012 (17) | 0.0035 (15) | 0.0015 (17) |
C20 | 0.019 (2) | 0.022 (2) | 0.0185 (18) | 0.0030 (16) | 0.0055 (16) | 0.0006 (16) |
C21 | 0.015 (2) | 0.026 (2) | 0.0208 (19) | 0.0020 (16) | 0.0037 (16) | 0.0033 (16) |
C22 | 0.026 (2) | 0.032 (2) | 0.024 (2) | −0.0025 (19) | 0.0100 (18) | −0.0006 (18) |
C23 | 0.031 (3) | 0.040 (3) | 0.025 (2) | 0.003 (2) | 0.0141 (19) | −0.003 (2) |
C24 | 0.025 (2) | 0.044 (3) | 0.031 (2) | 0.003 (2) | 0.0144 (19) | 0.006 (2) |
C25 | 0.017 (2) | 0.037 (3) | 0.032 (2) | −0.0007 (19) | 0.0063 (18) | 0.007 (2) |
C26 | 0.019 (2) | 0.027 (2) | 0.024 (2) | 0.0021 (17) | 0.0046 (17) | 0.0050 (17) |
C27 | 0.041 (3) | 0.051 (3) | 0.029 (2) | −0.017 (3) | 0.004 (2) | −0.002 (2) |
C28 | 0.051 (3) | 0.048 (3) | 0.035 (3) | −0.016 (3) | 0.004 (2) | −0.013 (2) |
C29 | 0.019 (2) | 0.025 (2) | 0.0197 (19) | 0.0016 (17) | 0.0048 (16) | 0.0044 (17) |
C30 | 0.034 (3) | 0.028 (2) | 0.023 (2) | 0.002 (2) | 0.0012 (19) | −0.0047 (18) |
C31 | 0.041 (3) | 0.025 (2) | 0.035 (3) | 0.009 (2) | 0.005 (2) | −0.003 (2) |
C32 | 0.027 (2) | 0.029 (2) | 0.031 (2) | 0.0056 (19) | 0.0062 (19) | 0.0096 (19) |
C33 | 0.020 (2) | 0.026 (2) | 0.023 (2) | −0.0042 (17) | 0.0013 (16) | 0.0018 (17) |
C34 | 0.021 (2) | 0.022 (2) | 0.0168 (18) | −0.0018 (17) | 0.0037 (16) | −0.0002 (16) |
C35 | 0.030 (2) | 0.027 (2) | 0.025 (2) | −0.0056 (19) | 0.0049 (18) | −0.0041 (18) |
C36 | 0.041 (3) | 0.033 (3) | 0.022 (2) | 0.003 (2) | 0.003 (2) | −0.0012 (19) |
C37 | 0.020 (2) | 0.034 (3) | 0.026 (2) | 0.0017 (19) | 0.0081 (17) | 0.0092 (19) |
C38 | 0.034 (3) | 0.036 (3) | 0.028 (2) | 0.005 (2) | 0.010 (2) | 0.007 (2) |
C39 | 0.045 (3) | 0.047 (3) | 0.033 (3) | 0.012 (3) | 0.022 (2) | 0.012 (2) |
C40 | 0.028 (3) | 0.057 (4) | 0.049 (3) | 0.004 (2) | 0.018 (2) | 0.024 (3) |
C41 | 0.024 (3) | 0.054 (3) | 0.046 (3) | −0.006 (2) | 0.011 (2) | 0.012 (3) |
C42 | 0.023 (2) | 0.037 (3) | 0.038 (3) | −0.004 (2) | 0.006 (2) | 0.011 (2) |
C43 | 0.081 (5) | 0.087 (5) | 0.071 (5) | −0.056 (5) | 0.031 (4) | −0.021 (4) |
C44 | 0.117 (7) | 0.072 (5) | 0.067 (4) | −0.054 (5) | 0.036 (4) | −0.037 (4) |
C45 | 0.015 (2) | 0.030 (2) | 0.024 (2) | 0.0027 (17) | 0.0082 (16) | 0.0053 (17) |
C46 | 0.024 (2) | 0.028 (2) | 0.025 (2) | 0.0033 (18) | 0.0059 (17) | 0.0010 (18) |
C47 | 0.028 (2) | 0.032 (2) | 0.024 (2) | −0.0014 (19) | 0.0033 (18) | 0.0045 (19) |
C48 | 0.024 (2) | 0.030 (2) | 0.029 (2) | 0.0043 (19) | 0.0013 (18) | 0.0102 (19) |
C49 | 0.024 (2) | 0.030 (3) | 0.035 (2) | 0.0058 (19) | 0.0053 (19) | 0.005 (2) |
C50 | 0.021 (2) | 0.026 (2) | 0.023 (2) | 0.0030 (18) | 0.0040 (17) | 0.0035 (17) |
C51 | 0.035 (3) | 0.046 (3) | 0.034 (3) | 0.008 (2) | 0.003 (2) | −0.008 (2) |
C52 | 0.053 (4) | 0.064 (4) | 0.038 (3) | 0.015 (3) | −0.001 (3) | −0.011 (3) |
C53 | 0.042 (3) | 0.033 (3) | 0.039 (3) | 0.007 (2) | −0.003 (2) | −0.016 (2) |
C54 | 0.068 (5) | 0.053 (4) | 0.168 (9) | 0.017 (4) | 0.055 (6) | 0.020 (5) |
Zn—N1 | 2.051 (5) | C9—C10 | 1.416 (6) |
Zn—N2 | 2.072 (3) | C10—C11 | 1.396 (6) |
Zn—N3 | 2.062 (7) | C10—C29 | 1.496 (6) |
Zn—N4 | 2.067 (4) | C11—C12 | 1.440 (7) |
Zn—O5 | 2.147 (5) | C12—C13 | 1.343 (6) |
Cl1—C28 | 1.781 (6) | C13—C14 | 1.446 (7) |
Cl2—C36 | 1.782 (7) | C14—C15 | 1.406 (6) |
Cl3—C44 | 1.782 (7) | C15—C16 | 1.401 (7) |
Cl4—C52 | 1.767 (8) | C15—C37 | 1.500 (6) |
Cl5—C54 | 1.703 (8) | C16—C17 | 1.449 (6) |
Cl6—C54 | 1.727 (9) | C17—C18 | 1.339 (7) |
Cl7—C54 | 1.724 (12) | C18—C19 | 1.443 (6) |
O1—C27 | 1.223 (6) | C19—C20 | 1.406 (6) |
O2—C35 | 1.223 (6) | C20—C45 | 1.504 (6) |
O3—C43 | 1.214 (8) | C21—C22 | 1.388 (7) |
O4—C51 | 1.217 (7) | C21—C26 | 1.396 (6) |
O5—C53 | 1.425 (6) | C22—C23 | 1.383 (6) |
N1—C1 | 1.384 (5) | C23—C24 | 1.379 (7) |
N1—C4 | 1.367 (5) | C24—C25 | 1.380 (8) |
N2—C6 | 1.370 (6) | C25—C26 | 1.414 (6) |
N2—C9 | 1.371 (5) | C27—C28 | 1.528 (9) |
N3—C11 | 1.378 (5) | C29—C30 | 1.381 (6) |
N3—C14 | 1.370 (5) | C29—C34 | 1.407 (7) |
N4—C16 | 1.369 (6) | C30—C31 | 1.384 (7) |
N4—C19 | 1.369 (6) | C31—C32 | 1.393 (8) |
N5—C26 | 1.416 (7) | C32—C33 | 1.378 (6) |
N5—C27 | 1.353 (6) | C33—C34 | 1.395 (6) |
N6—C34 | 1.416 (5) | C35—C36 | 1.520 (7) |
N6—C35 | 1.343 (7) | C37—C38 | 1.389 (8) |
N7—C42 | 1.406 (8) | C37—C42 | 1.398 (7) |
N7—C43 | 1.335 (8) | C38—C39 | 1.393 (7) |
N8—C50 | 1.437 (7) | C39—C40 | 1.367 (8) |
N8—C51 | 1.346 (7) | C40—C41 | 1.372 (9) |
C1—C2 | 1.449 (6) | C41—C42 | 1.414 (7) |
C1—C20 | 1.392 (6) | C43—C44 | 1.534 (11) |
C2—C3 | 1.351 (6) | C45—C46 | 1.382 (8) |
C3—C4 | 1.445 (6) | C45—C50 | 1.403 (6) |
C4—C5 | 1.408 (6) | C46—C47 | 1.385 (6) |
C5—C6 | 1.399 (6) | C47—C48 | 1.376 (7) |
C5—C21 | 1.500 (6) | C48—C49 | 1.394 (8) |
C6—C7 | 1.447 (6) | C49—C50 | 1.387 (6) |
C7—C8 | 1.359 (7) | C51—C52 | 1.509 (9) |
C8—C9 | 1.434 (6) | ||
N1—Zn—N2 | 89.48 (13) | N4—C19—C20 | 125.4 (4) |
N1—Zn—N3 | 164.92 (13) | N4—C19—C18 | 109.5 (4) |
N1—Zn—N4 | 88.84 (14) | C20—C19—C18 | 125.2 (4) |
N3—Zn—N2 | 88.68 (13) | C1—C20—C19 | 125.4 (4) |
N3—Zn—N4 | 89.11 (14) | C1—C20—C45 | 116.2 (4) |
N4—Zn—N2 | 165.12 (13) | C19—C20—C45 | 118.4 (4) |
N1—Zn—O5 | 95.6 (3) | C22—C21—C26 | 118.2 (4) |
N3—Zn—O5 | 99.5 (3) | C22—C21—C5 | 119.2 (4) |
N4—Zn—O5 | 98.35 (13) | C26—C21—C5 | 122.6 (4) |
N2—Zn—O5 | 96.52 (12) | C23—C22—C21 | 121.9 (4) |
C53—O5—Zn | 119.9 (3) | C24—C23—C22 | 119.7 (4) |
C4—N1—C1 | 106.8 (3) | C23—C24—C25 | 120.4 (4) |
C4—N1—Zn | 126.2 (3) | C24—C25—C26 | 119.8 (5) |
C1—N1—Zn | 126.6 (3) | C21—C26—C25 | 120.1 (4) |
C6—N2—C9 | 106.3 (4) | C21—C26—N5 | 117.8 (4) |
C6—N2—Zn | 125.8 (3) | C25—C26—N5 | 122.1 (4) |
C9—N2—Zn | 126.8 (3) | O1—C27—N5 | 125.6 (5) |
C14—N3—C11 | 106.9 (3) | O1—C27—C28 | 118.7 (5) |
C14—N3—Zn | 126.5 (3) | N5—C27—C28 | 115.7 (5) |
C11—N3—Zn | 126.2 (3) | C27—C28—Cl1 | 117.0 (4) |
C16—N4—C19 | 106.8 (4) | C30—C29—C34 | 118.4 (4) |
C16—N4—Zn | 126.1 (3) | C30—C29—C10 | 121.0 (4) |
C19—N4—Zn | 126.5 (3) | C34—C29—C10 | 120.5 (4) |
C27—N5—C26 | 127.8 (4) | C29—C30—C31 | 121.8 (4) |
C35—N6—C34 | 129.3 (4) | C30—C31—C32 | 118.9 (4) |
C43—N7—C42 | 131.1 (5) | C33—C32—C31 | 121.1 (4) |
C51—N8—C50 | 119.2 (4) | C32—C33—C34 | 119.3 (4) |
N1—C1—C20 | 125.7 (4) | C33—C34—C29 | 120.5 (4) |
N1—C1—C2 | 108.8 (3) | C33—C34—N6 | 123.1 (4) |
C20—C1—C2 | 125.5 (4) | C29—C34—N6 | 116.4 (4) |
C3—C2—C1 | 107.6 (3) | O2—C35—N6 | 125.0 (4) |
C2—C3—C4 | 106.9 (4) | O2—C35—C36 | 118.0 (4) |
N1—C4—C5 | 125.7 (4) | N6—C35—C36 | 117.0 (4) |
N1—C4—C3 | 109.9 (4) | C35—C36—Cl2 | 115.5 (3) |
C5—C4—C3 | 124.5 (4) | C38—C37—C42 | 118.8 (4) |
C6—C5—C4 | 125.8 (4) | C38—C37—C15 | 119.8 (4) |
C6—C5—C21 | 118.1 (4) | C42—C37—C15 | 121.3 (4) |
C4—C5—C21 | 116.0 (4) | C37—C38—C39 | 120.4 (5) |
N2—C6—C5 | 125.4 (4) | C40—C39—C38 | 119.5 (5) |
N2—C6—C7 | 109.8 (4) | C39—C40—C41 | 122.6 (5) |
C5—C6—C7 | 124.8 (4) | C40—C41—C42 | 117.8 (5) |
C8—C7—C6 | 106.8 (4) | C37—C42—N7 | 116.1 (4) |
C7—C8—C9 | 106.9 (4) | C37—C42—C41 | 120.8 (5) |
N2—C9—C10 | 124.4 (4) | N7—C42—C41 | 123.0 (5) |
N2—C9—C8 | 110.3 (4) | O3—C43—N7 | 125.2 (7) |
C10—C9—C8 | 125.3 (4) | O3—C43—C44 | 118.1 (6) |
C11—C10—C9 | 125.8 (4) | N7—C43—C44 | 116.7 (6) |
C11—C10—C29 | 116.5 (4) | C43—C44—Cl3 | 114.8 (4) |
C9—C10—C29 | 117.7 (4) | C46—C45—C50 | 117.5 (4) |
N3—C11—C10 | 125.9 (4) | C46—C45—C20 | 120.8 (4) |
N3—C11—C12 | 109.1 (4) | C50—C45—C20 | 121.6 (4) |
C10—C11—C12 | 125.0 (4) | C45—C46—C47 | 121.7 (4) |
C13—C12—C11 | 107.6 (4) | C48—C47—C46 | 120.4 (4) |
C12—C13—C14 | 107.2 (4) | C47—C48—C49 | 119.3 (4) |
N3—C14—C15 | 126.0 (4) | C50—C49—C48 | 119.9 (4) |
N3—C14—C13 | 109.2 (4) | C49—C50—C45 | 121.2 (4) |
C15—C14—C13 | 124.7 (4) | C49—C50—N8 | 119.4 (4) |
C16—C15—C14 | 124.9 (4) | C45—C50—N8 | 119.4 (4) |
C16—C15—C37 | 119.0 (4) | O4—C51—N8 | 123.8 (5) |
C14—C15—C37 | 116.1 (4) | O4—C51—C52 | 117.9 (5) |
N4—C16—C15 | 126.1 (4) | N8—C51—C52 | 118.3 (5) |
N4—C16—C17 | 109.1 (4) | C51—C52—Cl4 | 115.2 (5) |
C15—C16—C17 | 124.7 (4) | Cl5—C54—Cl7 | 114.5 (6) |
C18—C17—C16 | 107.3 (4) | Cl5—C54—Cl6 | 111.7 (5) |
C17—C18—C19 | 107.3 (4) | Cl7—C54—Cl6 | 110.2 (5) |
Experimental details
Crystal data | |
Chemical formula | [Zn(C52H36Cl4N8O4)(CH4O)]·CHCl3 |
Mr | 1195.47 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 110 |
a, b, c (Å) | 13.078 (6), 17.899 (7), 22.79 (9) |
β (°) | 105.009 (2) |
V (Å3) | 5153 (21) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.90 |
Crystal size (mm) | 0.25 × 0.25 × 0.25 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19872, 11775, 7802 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.187, 1.04 |
No. of reflections | 11775 |
No. of parameters | 676 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0845P)2 + 10.6403P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.27, −1.62 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 and WinGX (Farrugia, 1999).
Zn—N1 | 2.051 (5) | Zn—N4 | 2.067 (4) |
Zn—N2 | 2.072 (3) | Zn—O5 | 2.147 (5) |
Zn—N3 | 2.062 (7) | ||
N1—Zn—N2 | 89.48 (13) | N4—Zn—N2 | 165.12 (13) |
N1—Zn—N3 | 164.92 (13) | N1—Zn—O5 | 95.6 (3) |
N1—Zn—N4 | 88.84 (14) | N3—Zn—O5 | 99.5 (3) |
N3—Zn—N2 | 88.68 (13) | N4—Zn—O5 | 98.35 (13) |
N3—Zn—N4 | 89.11 (14) | N2—Zn—O5 | 96.52 (12) |
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Porphyrins are of biological importance and therefore commonly used as building blocks in biomimetic chemistry. Very elegant heme protein models have been synthesized to elucidate the mechanism of functioning of the native enzymes, such as P-450 cytochromes (Sono et al., 1996), dioxygen carriers (Jameson & Ibers, 1994) or cytochrome c oxidase (Yoshikawa et al., 2000). In the latter case, different porphyrins bearing four pickets on the same side of the porphyrin have been reported and have been shown to be powerful and versatile intermediates (Collman et al., 1994). We recently observed that the spatial arrangement depends not only on the nature of the pickets, but also on the number of pickets per side of the porphyrin (Didier et al., 2001). Additionally, the interactions that the pickets can establish between them via a hydrogen-bonding net may be of prime importance (Ricard et al., 2001). We now report the structure of a zinc(II) porphyrin, (I), bearing three pickets on one side and the fourth on the other side of the porphyrin.
The porphyrin complex crystallizes with a chloroform molecule and an axially coordinated methanol molecule. The porphyrin ring adopts a nearly planar conformation. The coordination geometry is square pyramidal and the Zn atom is displaced from the N4 least-squares plane by 0.269 (2) Å towards the axial methanol O atom. The mean Zn—N(porphyrin) distance is 2.063 (9) Å and the Zn—O(methanol) distance is 2.147 (5) Å [the average Zn—O(methanol) value found for 13 analogous methanol zinc porphyrins is 2.20 (4) Å].
No intramolecular hydrogen bonds are observed in crystal. The O5—HO5···O2i hydrogen bond [O5···O2i 2.726 (11), HO5···O2i 1.82 Å andO5-HO5···O2i 171.8°; symmetry code (I) 0.5 + x, 0.5 - y, 0.5 + z] links the molecules of the complex into infinite chains along the [101] direction.