Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015264/ci6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015264/ci6042Isup2.hkl |
CCDC reference: 175342
Key indicators
- Single-crystal X-ray study
- T = 203 K
- Mean (C-C) = 0.006 Å
- Disorder in main residue
- R factor = 0.065
- wR factor = 0.169
- Data-to-parameter ratio = 18.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 3.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The 5,15-bis(4-pyridyl)porphyrin was synthesized according to a previously reported method (Forsyth et al., 1995). Zinc insertion: zinc acetate (4.61 mg, 21.0 µM) dissolved in MeOH (3 ml) was added to 5,15-bis(4-pyridyl)porphyrin (15.5 mg, 20.8 microM) in CH2Cl2 (20 ml). The mixture was refluxed for 20 min, at which point thin-layer chromatography (1% MeOH/CH2Cl2) showed the reaction was complete. The solvent was removed and the residue was dissolved in CH2Cl2 (10 ml), washed with water (10 ml) and dried (MgSO4). Quantitative yield. Crystals were grown by the slow evaporation of a 1:1 solvent mixture of CHCl3/MeOH. 1H NMR (400 MHz, CDCl3): 9.95 (s, 2H), 7.06 (s br, 4H), 3.78 (t, 8H), 1.98 (quint, 8H), 1.61 (m, 8H), 1.62 (s br, 4H), 1.24 (s, 12H), 1.00 (t, 12H).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Zn(C50H58N6)]·CHCl3 | F(000) = 1952 |
Mr = 927.76 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 17.8146 (2) Å | Cell parameters from 6496 reflections |
b = 13.1650 (2) Å | θ = 1.5–28.3° |
c = 20.2171 (4) Å | µ = 0.73 mm−1 |
β = 90.84 (1)° | T = 203 K |
V = 4741.00 (13) Å3 | Plate, red |
Z = 4 | 0.30 × 0.22 × 0.02 mm |
Siemens SMART CCD area-detector diffractometer | 10404 independent reflections |
Radiation source: fine-focus sealed tube | 6454 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (Blessing, 1995) | h = −23→23 |
Tmin = 0.800, Tmax = 0.986 | k = 0→17 |
10404 measured reflections | l = 0→26 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0548P)2 + 7.9269P] where P = (Fo2 + 2Fc2)/3 |
10404 reflections | (Δ/σ)max = 0.020 |
564 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
[Zn(C50H58N6)]·CHCl3 | V = 4741.00 (13) Å3 |
Mr = 927.76 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 17.8146 (2) Å | µ = 0.73 mm−1 |
b = 13.1650 (2) Å | T = 203 K |
c = 20.2171 (4) Å | 0.30 × 0.22 × 0.02 mm |
β = 90.84 (1)° |
Siemens SMART CCD area-detector diffractometer | 10404 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6454 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.986 | Rint = 0.000 |
10404 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.78 e Å−3 |
10404 reflections | Δρmin = −1.03 e Å−3 |
564 parameters |
Experimental. One n-butyl chain was found disordered (59/41 occupation factors). The n-butyl carbon atoms (C22 and C23) were refined with two split positions, and the hydrogen atoms attach to C21, C22, C23 and C24 have been fixed taking into account the different orientation of the minor(A) and major(B) components of the disordered n-butyl chain. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn | 0.60265 (3) | 0.09136 (3) | 0.87486 (2) | 0.02432 (13) | |
N1 | 0.59162 (18) | 0.0451 (2) | 0.77638 (16) | 0.0275 (7) | |
N2 | 0.67608 (18) | −0.0304 (2) | 0.88531 (15) | 0.0255 (7) | |
N3 | 0.58646 (18) | 0.0988 (3) | 0.97568 (16) | 0.0276 (7) | |
N4 | 0.51031 (18) | 0.1856 (2) | 0.86596 (16) | 0.0257 (7) | |
N5 | 0.81503 (18) | −0.2932 (2) | 0.65123 (16) | 0.0275 (7) | |
N15 | 0.3798 (3) | 0.4412 (3) | 1.1122 (2) | 0.0583 (13) | |
C1 | 0.5463 (2) | 0.0939 (3) | 0.73144 (19) | 0.0271 (8) | |
C2 | 0.5573 (2) | 0.0530 (3) | 0.6659 (2) | 0.0316 (9) | |
C3 | 0.6100 (2) | −0.0206 (3) | 0.6716 (2) | 0.0342 (10) | |
C4 | 0.6331 (2) | −0.0241 (3) | 0.7417 (2) | 0.0285 (9) | |
C5 | 0.6896 (2) | −0.0858 (3) | 0.77056 (19) | 0.0266 (8) | |
C6 | 0.7118 (2) | −0.0865 (3) | 0.8377 (2) | 0.0272 (8) | |
C7 | 0.7731 (2) | −0.1447 (3) | 0.8688 (2) | 0.0290 (9) | |
C8 | 0.7710 (2) | −0.1234 (3) | 0.9344 (2) | 0.0303 (9) | |
C9 | 0.7101 (2) | −0.0541 (3) | 0.9445 (2) | 0.0277 (9) | |
C10 | 0.6836 (2) | −0.0250 (3) | 1.0060 (2) | 0.0301 (9) | |
H10 | 0.7091 | −0.0530 | 1.0428 | 0.036* | |
C11 | 0.6245 (2) | 0.0397 (3) | 1.02050 (19) | 0.0286 (9) | |
C12 | 0.5972 (2) | 0.0571 (3) | 1.0867 (2) | 0.0327 (10) | |
C13 | 0.5445 (2) | 0.1315 (3) | 1.0822 (2) | 0.0326 (10) | |
C14 | 0.5371 (2) | 0.1571 (3) | 1.01127 (19) | 0.0281 (9) | |
C15 | 0.4893 (2) | 0.2301 (3) | 0.9824 (2) | 0.0284 (9) | |
C16 | 0.4756 (2) | 0.2435 (3) | 0.9140 (2) | 0.0277 (9) | |
C17 | 0.4242 (2) | 0.3153 (3) | 0.8813 (2) | 0.0327 (10) | |
C18 | 0.4285 (2) | 0.2988 (3) | 0.8151 (2) | 0.0306 (9) | |
C19 | 0.4813 (2) | 0.2166 (3) | 0.8062 (2) | 0.0281 (9) | |
C20 | 0.4980 (2) | 0.1734 (3) | 0.7457 (2) | 0.0296 (9) | |
H20 | 0.4729 | 0.2020 | 0.7090 | 0.036* | |
C21 | 0.5154 (3) | 0.0867 (4) | 0.6050 (2) | 0.0424 (11) | |
H21A | 0.5510 | 0.0973 | 0.5691 | 0.051* | 0.408 (19) |
H21B | 0.4906 | 0.1517 | 0.6137 | 0.051* | 0.408 (19) |
H21C | 0.5411 | 0.0603 | 0.5660 | 0.051* | 0.592 (19) |
H21D | 0.5168 | 0.1611 | 0.6027 | 0.051* | 0.592 (19) |
C22A | 0.4577 (10) | 0.0101 (16) | 0.5836 (8) | 0.055 (5) | 0.408 (19) |
H22A | 0.4352 | 0.0322 | 0.5415 | 0.066* | 0.408 (19) |
H22B | 0.4829 | −0.0549 | 0.5759 | 0.066* | 0.408 (19) |
C23A | 0.3967 (9) | −0.0060 (17) | 0.6322 (9) | 0.066 (6) | 0.408 (19) |
H23A | 0.3694 | 0.0576 | 0.6390 | 0.079* | 0.408 (19) |
H23B | 0.4183 | −0.0274 | 0.6748 | 0.079* | 0.408 (19) |
C22B | 0.4301 (7) | 0.0506 (10) | 0.6022 (6) | 0.050 (3) | 0.592 (19) |
H22C | 0.4035 | 0.0798 | 0.6398 | 0.060* | 0.592 (19) |
H22D | 0.4063 | 0.0764 | 0.5615 | 0.060* | 0.592 (19) |
C23B | 0.4221 (7) | −0.0641 (10) | 0.6039 (7) | 0.066 (4) | 0.592 (19) |
H23C | 0.4459 | −0.0940 | 0.5651 | 0.079* | 0.592 (19) |
H23D | 0.4474 | −0.0911 | 0.6436 | 0.079* | 0.592 (19) |
C24 | 0.3399 (4) | −0.0923 (6) | 0.6045 (4) | 0.106 (3) | |
H24A | 0.3562 | −0.1150 | 0.5614 | 0.158* | 0.408 (19) |
H24B | 0.2896 | −0.0643 | 0.6007 | 0.158* | 0.408 (19) |
H24C | 0.3396 | −0.1494 | 0.6349 | 0.158* | 0.408 (19) |
H24D | 0.3111 | −0.0420 | 0.5799 | 0.158* | 0.592 (19) |
H24E | 0.3227 | −0.0945 | 0.6498 | 0.158* | 0.592 (19) |
H24F | 0.3330 | −0.1585 | 0.5842 | 0.158* | 0.592 (19) |
C31 | 0.6376 (3) | −0.0827 (5) | 0.6143 (2) | 0.0606 (16) | |
H31A | 0.6100 | −0.0638 | 0.5744 | 0.091* | |
H31B | 0.6297 | −0.1543 | 0.6233 | 0.091* | |
H31C | 0.6907 | −0.0701 | 0.6082 | 0.091* | |
C51 | 0.7311 (2) | −0.1561 (3) | 0.72602 (19) | 0.0262 (9) | |
C52 | 0.7951 (2) | −0.1255 (3) | 0.6933 (2) | 0.0312 (10) | |
H52 | 0.8112 | −0.0576 | 0.6956 | 0.037* | |
C53 | 0.8351 (2) | −0.1957 (3) | 0.6574 (2) | 0.0307 (9) | |
H53 | 0.8788 | −0.1739 | 0.6362 | 0.037* | |
C54 | 0.7511 (2) | −0.3214 (3) | 0.6802 (2) | 0.0356 (10) | |
H54 | 0.7344 | −0.3886 | 0.6746 | 0.043* | |
C55 | 0.7084 (2) | −0.2561 (3) | 0.7179 (2) | 0.0349 (10) | |
H55 | 0.6644 | −0.2794 | 0.7380 | 0.042* | |
C71 | 0.8303 (3) | −0.2148 (4) | 0.8388 (2) | 0.0443 (12) | |
H71A | 0.8648 | −0.2384 | 0.8731 | 0.066* | |
H71B | 0.8580 | −0.1786 | 0.8053 | 0.066* | |
H71C | 0.8049 | −0.2726 | 0.8189 | 0.066* | |
C81 | 0.8247 (3) | −0.1589 (4) | 0.9879 (2) | 0.0439 (12) | |
H81A | 0.8493 | −0.2217 | 0.9736 | 0.053* | |
H81B | 0.7968 | −0.1738 | 1.0281 | 0.053* | |
C82 | 0.8846 (3) | −0.0776 (5) | 1.0029 (3) | 0.0739 (18) | |
H82A | 0.9091 | −0.0595 | 0.9614 | 0.089* | |
H82B | 0.8594 | −0.0166 | 1.0191 | 0.089* | |
C83 | 0.9440 (4) | −0.1074 (6) | 1.0522 (3) | 0.082 (2) | |
H83A | 0.9197 | −0.1372 | 1.0908 | 0.099* | |
H83B | 0.9706 | −0.0462 | 1.0670 | 0.099* | |
C84 | 1.0000 (4) | −0.1816 (6) | 1.0264 (4) | 0.100 (3) | |
H84A | 0.9758 | −0.2466 | 1.0187 | 0.150* | |
H84B | 1.0405 | −0.1899 | 1.0585 | 0.150* | |
H84C | 1.0201 | −0.1564 | 0.9851 | 0.150* | |
C121 | 0.6213 (3) | −0.0045 (4) | 1.1456 (2) | 0.0375 (11) | |
H12A | 0.6261 | −0.0754 | 1.1317 | 0.045* | |
H12B | 0.5812 | −0.0017 | 1.1783 | 0.045* | |
C122 | 0.6949 (3) | 0.0275 (4) | 1.1798 (2) | 0.0440 (12) | |
H12C | 0.6867 | 0.0901 | 1.2049 | 0.053* | |
H12D | 0.7327 | 0.0416 | 1.1462 | 0.053* | |
C123 | 0.7244 (3) | −0.0559 (4) | 1.2268 (2) | 0.0508 (13) | |
H12E | 0.7628 | −0.0265 | 1.2563 | 0.061* | |
H12F | 0.6830 | −0.0794 | 1.2543 | 0.061* | |
C124 | 0.7577 (3) | −0.1466 (5) | 1.1912 (3) | 0.0652 (16) | |
H12G | 0.7189 | −0.1801 | 1.1651 | 0.098* | |
H12H | 0.7784 | −0.1940 | 1.2234 | 0.098* | |
H12I | 0.7973 | −0.1237 | 1.1623 | 0.098* | |
C131 | 0.5015 (3) | 0.1713 (4) | 1.1406 (2) | 0.0450 (12) | |
H13A | 0.5155 | 0.1332 | 1.1799 | 0.068* | |
H13B | 0.4480 | 0.1638 | 1.1321 | 0.068* | |
H13C | 0.5132 | 0.2425 | 1.1473 | 0.068* | |
C151 | 0.4504 (2) | 0.3022 (3) | 1.0279 (2) | 0.0317 (9) | |
C152 | 0.4875 (3) | 0.3876 (3) | 1.0510 (2) | 0.0408 (11) | |
H152 | 0.5374 | 0.4005 | 1.0392 | 0.049* | |
C153 | 0.4495 (3) | 0.4542 (4) | 1.0921 (3) | 0.0527 (14) | |
H153 | 0.4752 | 0.5126 | 1.1067 | 0.063* | |
C154 | 0.3455 (3) | 0.3584 (4) | 1.0903 (3) | 0.0573 (15) | |
H154 | 0.2959 | 0.3469 | 1.1037 | 0.069* | |
C155 | 0.3778 (3) | 0.2875 (4) | 1.0489 (3) | 0.0474 (13) | |
H155 | 0.3505 | 0.2299 | 1.0352 | 0.057* | |
C171 | 0.3725 (3) | 0.3938 (4) | 0.9109 (2) | 0.0447 (12) | |
H17A | 0.3514 | 0.4358 | 0.8759 | 0.067* | |
H17B | 0.4006 | 0.4360 | 0.9417 | 0.067* | |
H17C | 0.3323 | 0.3598 | 0.9340 | 0.067* | |
C181 | 0.3889 (3) | 0.3553 (4) | 0.7601 (2) | 0.0408 (11) | |
H18A | 0.3371 | 0.3694 | 0.7731 | 0.049* | |
H18B | 0.3870 | 0.3125 | 0.7205 | 0.049* | |
C182 | 0.4287 (3) | 0.4575 (5) | 0.7433 (3) | 0.0746 (19) | |
H18C | 0.3987 | 0.4928 | 0.7094 | 0.090* | |
H18D | 0.4293 | 0.5002 | 0.7830 | 0.090* | |
C183 | 0.5049 (4) | 0.4485 (6) | 0.7199 (4) | 0.084 (2) | |
H18E | 0.5035 | 0.4127 | 0.6774 | 0.100* | |
H18F | 0.5334 | 0.4062 | 0.7513 | 0.100* | |
C184 | 0.5475 (5) | 0.5486 (6) | 0.7108 (4) | 0.105 (3) | |
H18G | 0.5127 | 0.6011 | 0.6965 | 0.158* | |
H18H | 0.5858 | 0.5396 | 0.6777 | 0.158* | |
H18I | 0.5710 | 0.5682 | 0.7525 | 0.158* | |
Cl1 | 0.70050 (9) | 0.38210 (13) | 0.00052 (8) | 0.0716 (4) | |
Cl2 | 0.71226 (16) | 0.30932 (17) | 0.13248 (9) | 0.1208 (9) | |
Cl3 | 0.80486 (12) | 0.22346 (17) | 0.02792 (16) | 0.1368 (10) | |
C1S | 0.7187 (3) | 0.2770 (4) | 0.0496 (3) | 0.0608 (15) | |
H1S | 0.6792 | 0.2261 | 0.0399 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0264 (2) | 0.0218 (2) | 0.0249 (2) | 0.0009 (2) | 0.00566 (17) | −0.0003 (2) |
N1 | 0.0290 (18) | 0.0251 (18) | 0.0284 (18) | 0.0016 (14) | 0.0042 (15) | −0.0020 (15) |
N2 | 0.0287 (18) | 0.0226 (17) | 0.0253 (18) | 0.0008 (14) | 0.0040 (14) | −0.0002 (14) |
N3 | 0.0302 (17) | 0.0268 (18) | 0.0259 (17) | −0.0015 (15) | 0.0065 (14) | −0.0015 (15) |
N4 | 0.0262 (17) | 0.0244 (17) | 0.0267 (18) | 0.0023 (14) | 0.0056 (14) | −0.0040 (14) |
N5 | 0.0309 (18) | 0.0266 (18) | 0.0253 (18) | 0.0019 (15) | 0.0067 (14) | −0.0010 (14) |
N15 | 0.066 (3) | 0.046 (3) | 0.064 (3) | 0.004 (2) | 0.027 (2) | −0.018 (2) |
C1 | 0.030 (2) | 0.025 (2) | 0.027 (2) | −0.0027 (18) | 0.0028 (16) | 0.0012 (18) |
C2 | 0.033 (2) | 0.036 (2) | 0.025 (2) | 0.0015 (19) | 0.0016 (18) | 0.0011 (18) |
C3 | 0.041 (3) | 0.038 (3) | 0.024 (2) | 0.002 (2) | 0.0044 (19) | −0.0041 (19) |
C4 | 0.026 (2) | 0.029 (2) | 0.030 (2) | −0.0003 (17) | 0.0068 (17) | −0.0035 (18) |
C5 | 0.0258 (19) | 0.025 (2) | 0.029 (2) | 0.0008 (17) | 0.0084 (16) | −0.0022 (18) |
C6 | 0.028 (2) | 0.0206 (19) | 0.033 (2) | 0.0021 (17) | 0.0066 (17) | 0.0015 (18) |
C7 | 0.026 (2) | 0.027 (2) | 0.035 (2) | 0.0008 (17) | 0.0058 (18) | 0.0046 (18) |
C8 | 0.031 (2) | 0.029 (2) | 0.030 (2) | 0.0012 (17) | 0.0005 (18) | 0.0036 (18) |
C9 | 0.032 (2) | 0.022 (2) | 0.029 (2) | 0.0004 (17) | 0.0024 (17) | 0.0013 (17) |
C10 | 0.034 (2) | 0.028 (2) | 0.028 (2) | 0.0002 (18) | 0.0012 (18) | 0.0003 (18) |
C11 | 0.035 (2) | 0.025 (2) | 0.026 (2) | −0.0040 (18) | 0.0035 (17) | −0.0033 (17) |
C12 | 0.035 (2) | 0.034 (2) | 0.029 (2) | −0.0070 (19) | 0.0058 (18) | −0.0023 (18) |
C13 | 0.039 (2) | 0.030 (2) | 0.030 (2) | −0.0074 (19) | 0.0092 (19) | −0.0039 (18) |
C14 | 0.030 (2) | 0.028 (2) | 0.027 (2) | −0.0042 (17) | 0.0083 (17) | −0.0039 (17) |
C15 | 0.028 (2) | 0.024 (2) | 0.034 (2) | −0.0048 (17) | 0.0113 (18) | −0.0062 (17) |
C16 | 0.024 (2) | 0.022 (2) | 0.037 (2) | −0.0006 (16) | 0.0073 (17) | −0.0022 (18) |
C17 | 0.029 (2) | 0.025 (2) | 0.044 (3) | 0.0029 (17) | 0.0070 (19) | −0.0023 (19) |
C18 | 0.027 (2) | 0.026 (2) | 0.039 (2) | 0.0034 (17) | 0.0017 (18) | −0.0024 (19) |
C19 | 0.023 (2) | 0.025 (2) | 0.036 (2) | 0.0012 (16) | 0.0031 (17) | 0.0014 (18) |
C20 | 0.031 (2) | 0.028 (2) | 0.029 (2) | 0.0026 (18) | −0.0026 (17) | 0.0031 (18) |
C21 | 0.048 (3) | 0.048 (3) | 0.031 (2) | 0.009 (2) | −0.003 (2) | 0.001 (2) |
C22A | 0.048 (10) | 0.078 (14) | 0.038 (8) | 0.021 (9) | −0.006 (7) | −0.001 (8) |
C23A | 0.044 (9) | 0.089 (15) | 0.065 (11) | −0.008 (9) | −0.002 (8) | −0.022 (10) |
C22B | 0.045 (7) | 0.060 (8) | 0.045 (6) | 0.015 (5) | −0.016 (5) | −0.009 (5) |
C23B | 0.058 (7) | 0.059 (8) | 0.082 (8) | −0.001 (6) | −0.010 (6) | −0.018 (6) |
C24 | 0.065 (5) | 0.116 (7) | 0.135 (7) | −0.022 (5) | −0.016 (5) | −0.026 (6) |
C31 | 0.069 (4) | 0.080 (4) | 0.032 (3) | 0.037 (3) | −0.004 (2) | −0.013 (3) |
C51 | 0.030 (2) | 0.023 (2) | 0.026 (2) | 0.0015 (16) | 0.0055 (17) | −0.0005 (16) |
C52 | 0.037 (2) | 0.024 (2) | 0.033 (2) | 0.0003 (17) | 0.0107 (19) | 0.0004 (18) |
C53 | 0.032 (2) | 0.029 (2) | 0.031 (2) | −0.0003 (18) | 0.0099 (18) | 0.0007 (18) |
C54 | 0.030 (2) | 0.027 (2) | 0.050 (3) | −0.0028 (18) | 0.012 (2) | −0.008 (2) |
C55 | 0.029 (2) | 0.028 (2) | 0.048 (3) | −0.0039 (18) | 0.014 (2) | −0.007 (2) |
C71 | 0.041 (3) | 0.055 (3) | 0.037 (3) | 0.021 (2) | 0.003 (2) | 0.004 (2) |
C81 | 0.039 (3) | 0.051 (3) | 0.042 (3) | 0.012 (2) | −0.003 (2) | 0.001 (2) |
C82 | 0.064 (4) | 0.079 (5) | 0.077 (4) | −0.001 (3) | −0.029 (3) | −0.002 (4) |
C83 | 0.061 (4) | 0.109 (6) | 0.076 (5) | 0.007 (4) | −0.022 (3) | −0.008 (4) |
C84 | 0.083 (5) | 0.107 (6) | 0.110 (6) | 0.031 (5) | −0.011 (5) | −0.008 (5) |
C121 | 0.043 (3) | 0.039 (3) | 0.030 (2) | −0.007 (2) | 0.007 (2) | 0.001 (2) |
C122 | 0.052 (3) | 0.044 (3) | 0.036 (3) | −0.014 (2) | −0.001 (2) | −0.003 (2) |
C123 | 0.053 (3) | 0.062 (3) | 0.037 (3) | −0.007 (3) | −0.008 (2) | 0.006 (2) |
C124 | 0.061 (4) | 0.067 (4) | 0.067 (4) | 0.003 (3) | −0.010 (3) | 0.002 (3) |
C131 | 0.057 (3) | 0.049 (3) | 0.029 (2) | 0.003 (2) | 0.016 (2) | 0.001 (2) |
C151 | 0.035 (2) | 0.027 (2) | 0.033 (2) | 0.0004 (18) | 0.0114 (19) | −0.0026 (18) |
C152 | 0.042 (3) | 0.033 (3) | 0.048 (3) | −0.003 (2) | 0.011 (2) | −0.006 (2) |
C153 | 0.064 (4) | 0.038 (3) | 0.057 (3) | −0.003 (3) | 0.009 (3) | −0.019 (2) |
C154 | 0.052 (3) | 0.050 (3) | 0.070 (4) | 0.002 (3) | 0.035 (3) | −0.003 (3) |
C155 | 0.043 (3) | 0.035 (3) | 0.064 (3) | −0.001 (2) | 0.020 (2) | −0.009 (2) |
C171 | 0.042 (3) | 0.044 (3) | 0.048 (3) | 0.014 (2) | 0.005 (2) | −0.007 (2) |
C181 | 0.033 (2) | 0.041 (3) | 0.049 (3) | 0.013 (2) | −0.003 (2) | 0.002 (2) |
C182 | 0.063 (4) | 0.077 (4) | 0.084 (5) | 0.017 (3) | −0.001 (3) | 0.045 (4) |
C183 | 0.065 (4) | 0.091 (5) | 0.095 (5) | 0.001 (4) | 0.002 (4) | 0.038 (4) |
C184 | 0.125 (7) | 0.095 (6) | 0.095 (6) | −0.053 (5) | −0.026 (5) | 0.049 (5) |
Cl1 | 0.0767 (10) | 0.0792 (11) | 0.0593 (9) | 0.0040 (8) | 0.0188 (8) | 0.0005 (8) |
Cl2 | 0.215 (3) | 0.0942 (15) | 0.0530 (10) | −0.0451 (16) | −0.0115 (13) | 0.0024 (10) |
Cl3 | 0.0775 (14) | 0.0852 (15) | 0.249 (3) | 0.0179 (11) | 0.0294 (17) | 0.0114 (17) |
C1S | 0.055 (3) | 0.060 (4) | 0.067 (4) | −0.015 (3) | 0.004 (3) | −0.006 (3) |
Zn—N3 | 2.065 (3) | C13—C14 | 1.477 (6) |
Zn—N4 | 2.066 (3) | C13—C131 | 1.512 (6) |
Zn—N2 | 2.078 (3) | C14—C15 | 1.405 (6) |
Zn—N1 | 2.088 (3) | C15—C16 | 1.412 (6) |
Zn—N5i | 2.182 (3) | C15—C151 | 1.498 (5) |
N1—C1 | 1.367 (5) | C16—C17 | 1.466 (6) |
N1—C4 | 1.372 (5) | C17—C18 | 1.360 (6) |
N2—C9 | 1.369 (5) | C17—C171 | 1.514 (6) |
N2—C6 | 1.376 (5) | C18—C19 | 1.446 (5) |
N3—C11 | 1.367 (5) | C18—C181 | 1.505 (6) |
N3—C14 | 1.378 (5) | C19—C20 | 1.385 (6) |
N4—C19 | 1.369 (5) | C21—C22A | 1.498 (19) |
N4—C16 | 1.387 (5) | C21—C22B | 1.592 (13) |
N5—C53 | 1.337 (5) | C22A—C23A | 1.49 (3) |
N5—C54 | 1.341 (5) | C23A—C24 | 1.617 (18) |
N5—Znii | 2.182 (3) | C22B—C23B | 1.52 (2) |
N15—C153 | 1.322 (7) | C23B—C24 | 1.512 (13) |
N15—C154 | 1.323 (7) | C51—C55 | 1.386 (5) |
C1—C20 | 1.388 (5) | C51—C52 | 1.387 (5) |
C1—C2 | 1.446 (5) | C52—C53 | 1.379 (5) |
C2—C3 | 1.354 (6) | C54—C55 | 1.384 (6) |
C2—C21 | 1.498 (6) | C81—C82 | 1.539 (7) |
C3—C4 | 1.471 (6) | C82—C83 | 1.495 (8) |
C3—C31 | 1.506 (6) | C83—C84 | 1.496 (9) |
C4—C5 | 1.413 (6) | C121—C122 | 1.533 (6) |
C5—C6 | 1.408 (6) | C122—C123 | 1.539 (7) |
C5—C51 | 1.494 (5) | C123—C124 | 1.521 (8) |
C6—C7 | 1.469 (6) | C151—C155 | 1.381 (6) |
C7—C8 | 1.358 (6) | C151—C152 | 1.382 (6) |
C7—C71 | 1.508 (6) | C152—C153 | 1.391 (6) |
C8—C9 | 1.433 (6) | C154—C155 | 1.384 (7) |
C8—C81 | 1.507 (6) | C181—C182 | 1.560 (8) |
C9—C10 | 1.392 (6) | C182—C183 | 1.448 (8) |
C10—C11 | 1.389 (6) | C183—C184 | 1.533 (9) |
C11—C12 | 1.450 (5) | Cl1—C1S | 1.731 (6) |
C12—C13 | 1.359 (6) | Cl2—C1S | 1.734 (6) |
C12—C121 | 1.497 (6) | Cl3—C1S | 1.751 (6) |
N3—Zn—N4 | 86.27 (13) | C13—C12—C121 | 129.3 (4) |
N3—Zn—N2 | 91.89 (13) | C11—C12—C121 | 123.6 (4) |
N4—Zn—N2 | 166.24 (13) | C12—C13—C14 | 106.4 (4) |
N3—Zn—N1 | 160.42 (13) | C12—C13—C131 | 123.7 (4) |
N4—Zn—N1 | 91.62 (13) | C14—C13—C131 | 129.8 (4) |
N2—Zn—N1 | 85.55 (12) | N3—C14—C15 | 123.5 (4) |
N3—Zn—N5i | 108.03 (13) | N3—C14—C13 | 109.3 (4) |
N4—Zn—N5i | 95.62 (13) | C15—C14—C13 | 127.2 (4) |
N2—Zn—N5i | 97.92 (13) | C14—C15—C16 | 126.0 (4) |
N1—Zn—N5i | 91.54 (12) | C14—C15—C151 | 117.4 (4) |
C1—N1—C4 | 106.9 (3) | C16—C15—C151 | 116.6 (4) |
C1—N1—Zn | 122.9 (3) | N4—C16—C15 | 123.0 (4) |
C4—N1—Zn | 129.5 (3) | N4—C16—C17 | 108.7 (3) |
C9—N2—C6 | 106.6 (3) | C15—C16—C17 | 128.3 (4) |
C9—N2—Zn | 122.3 (3) | C18—C17—C16 | 107.3 (4) |
C6—N2—Zn | 129.7 (3) | C18—C17—C171 | 122.8 (4) |
C11—N3—C14 | 106.6 (3) | C16—C17—C171 | 129.9 (4) |
C11—N3—Zn | 123.5 (3) | C17—C18—C19 | 106.7 (4) |
C14—N3—Zn | 129.9 (3) | C17—C18—C181 | 128.0 (4) |
C19—N4—C16 | 106.7 (3) | C19—C18—C181 | 125.3 (4) |
C19—N4—Zn | 123.1 (2) | N4—C19—C20 | 125.0 (4) |
C16—N4—Zn | 129.2 (3) | N4—C19—C18 | 110.6 (3) |
C53—N5—C54 | 116.9 (3) | C20—C19—C18 | 124.4 (4) |
C53—N5—Znii | 120.8 (3) | C19—C20—C1 | 129.4 (4) |
C54—N5—Znii | 119.4 (3) | C2—C21—C22A | 111.6 (7) |
C153—N15—C154 | 115.8 (4) | C2—C21—C22B | 113.8 (5) |
N1—C1—C20 | 125.3 (4) | C22A—C21—C22B | 30.6 (6) |
N1—C1—C2 | 110.4 (3) | C23A—C22A—C21 | 114.2 (16) |
C20—C1—C2 | 124.3 (4) | C22A—C23A—C24 | 109.3 (15) |
C3—C2—C1 | 106.9 (4) | C23B—C22B—C21 | 112.7 (11) |
C3—C2—C21 | 128.3 (4) | C24—C23B—C22B | 109.6 (11) |
C1—C2—C21 | 124.8 (4) | C23B—C24—C23A | 39.5 (6) |
C2—C3—C4 | 106.8 (4) | C55—C51—C52 | 117.4 (4) |
C2—C3—C31 | 123.8 (4) | C55—C51—C5 | 120.9 (3) |
C4—C3—C31 | 129.4 (4) | C52—C51—C5 | 121.7 (4) |
N1—C4—C5 | 123.9 (4) | C53—C52—C51 | 119.4 (4) |
N1—C4—C3 | 109.0 (4) | N5—C53—C52 | 123.6 (4) |
C5—C4—C3 | 127.1 (4) | N5—C54—C55 | 123.0 (4) |
C6—C5—C4 | 126.1 (4) | C54—C55—C51 | 119.6 (4) |
C6—C5—C51 | 116.3 (3) | C8—C81—C82 | 110.9 (4) |
C4—C5—C51 | 117.6 (3) | C83—C82—C81 | 115.5 (5) |
N2—C6—C5 | 123.0 (4) | C82—C83—C84 | 114.0 (6) |
N2—C6—C7 | 109.2 (3) | C12—C121—C122 | 116.3 (4) |
C5—C6—C7 | 127.8 (4) | C121—C122—C123 | 111.4 (4) |
C8—C7—C6 | 106.2 (3) | C124—C123—C122 | 113.6 (4) |
C8—C7—C71 | 123.2 (4) | C155—C151—C152 | 117.0 (4) |
C6—C7—C71 | 130.5 (4) | C155—C151—C15 | 123.0 (4) |
C7—C8—C9 | 107.6 (4) | C152—C151—C15 | 120.0 (4) |
C7—C8—C81 | 127.6 (4) | C151—C152—C153 | 118.7 (4) |
C9—C8—C81 | 124.8 (4) | N15—C153—C152 | 124.7 (5) |
N2—C9—C10 | 124.5 (4) | N15—C154—C155 | 124.3 (5) |
N2—C9—C8 | 110.4 (3) | C151—C155—C154 | 119.5 (5) |
C10—C9—C8 | 124.6 (4) | C18—C181—C182 | 112.1 (4) |
C11—C10—C9 | 128.7 (4) | C183—C182—C181 | 115.6 (5) |
N3—C11—C10 | 125.4 (4) | C182—C183—C184 | 116.0 (7) |
N3—C11—C12 | 110.7 (4) | Cl1—C1S—Cl2 | 110.1 (3) |
C10—C11—C12 | 123.8 (4) | Cl1—C1S—Cl3 | 109.6 (3) |
C13—C12—C11 | 107.0 (4) | Cl2—C1S—Cl3 | 114.3 (4) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C50H58N6)]·CHCl3 |
Mr | 927.76 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 203 |
a, b, c (Å) | 17.8146 (2), 13.1650 (2), 20.2171 (4) |
β (°) | 90.84 (1) |
V (Å3) | 4741.00 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.30 × 0.22 × 0.02 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.800, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10404, 10404, 6454 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.169, 1.08 |
No. of reflections | 10404 |
No. of parameters | 564 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −1.03 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
The formation of porphyrin assemblies using coordination chemistry has been an active area of research for the last few years. The formation of coordination polymers using zinc porphyrins with pyridyl substituents was pioneered by the Fleischer group (Shachter et al., 1988). Recently, we have explored the use of pyridyl porphyrins to prepare porphyrin assemblies (Burrell et al., 1998). In general, the number of pyridyl groups on the porphyrin has little effect on the nature of solid-state structure of the polymer obtained upon insertion of zinc. Thus, the monopyridyl porphyrin (Shachter et al., 1988) has essentially the same structure as the tetrapyridyl analogue (Krupitsky et al., 1994).
In the title compound, (I), the porphyrin has β-alkyl groups which have a different steric requirement than phenyls or pyridyls (Fig. 1). However, the same structural motif is conserved with a single pyridyl group being utilized in formation of the coordination polymer (Fig. 2). The linear chains are stacked one upon another with the closest approach being approximately 4 Å. The sheets that result from this stacking are separated by channels that contain the chloroform solvate.