The crystal structure of the title compound, [Zn(C
46H
24N
8)(CH
4O)], consists of two-dimensional supramolecular arrays sustained by O—H
N(pyridyl) hydrogen bonding and weak Zn
NC coordination. The interlayer organization in the crystal structure is characterized by tight stacking of the corrugated layers.
Supporting information
CCDC reference: 625677
The free-base porphyrin moiety was synthesized by a standard literature procedure (Adler et al., 1970), by condensation of a 3:1 mixture of 4-cyanobenzaldehyde and 4-pyridinecarboxaldehyde with distilled pyrrole in hot propionic acid. It was then separated from the mixture of the various possible substitutional isomers by elution with 2% methanol on a silica-gel column, and subsequently metallated with zinc. Both the free-base and the metalloporphyrin species were fully characterized by 1H NMR, UV–vis and mass spectroscopic techniques. Crystallization of the title porphyrin was carried out by evaporation of a solution in a mixture of methanol and N,N'-dimethylacetamide (Ratio?).
The H atoms were treated as riding, with C—H distances in the range 0.95–0.98 Å and O—H = 1.00 Å, and with Uiso(H) = 1.2Ueq(C,O), or 1.5Ueq(C) for the methyl group. The resulting structure represents a racemic twin, with a refined Flack parameter (Flack, 1983) of 0.38 (2). Two relatively high residual peaks and troughs of 0.8 and −1.5 e Å−3 near the Zn atom are associated with the twinning or slight axial disorder of this atom, as reflected in its axially elongated displacement ellipsoid.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and
Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
(methanol)[10,15,20-tris(4-cyanophenyl)-5-(4-pyridyl)porphyrinato]zinc(II)
top
Crystal data top
[Zn(C46H24N8)(CH4O)] | F(000) = 808 |
Mr = 786.14 | Dx = 1.412 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yac | Cell parameters from 4371 reflections |
a = 9.2505 (4) Å | θ = 1.4–27.9° |
b = 9.6600 (5) Å | µ = 0.72 mm−1 |
c = 21.1032 (10) Å | T = 110 K |
β = 101.422 (3)° | Prism, red |
V = 1848.43 (15) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6328 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 27.9°, θmin = 2.1° |
Detector resolution: 12.8 pixels mm-1 | h = −12→12 |
1° ϕ and ω scans | k = −12→10 |
17749 measured reflections | l = −27→27 |
7371 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0348P)2 + 3.736P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.013 |
7371 reflections | Δρmax = 0.83 e Å−3 |
517 parameters | Δρmin = −1.55 e Å−3 |
2 restraints | Absolute structure: Flack (1983), with 2936 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.381 (17) |
Crystal data top
[Zn(C46H24N8)(CH4O)] | V = 1848.43 (15) Å3 |
Mr = 786.14 | Z = 2 |
Monoclinic, Pn | Mo Kα radiation |
a = 9.2505 (4) Å | µ = 0.72 mm−1 |
b = 9.6600 (5) Å | T = 110 K |
c = 21.1032 (10) Å | 0.30 × 0.20 × 0.20 mm |
β = 101.422 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 6328 reflections with I > 2σ(I) |
17749 measured reflections | Rint = 0.032 |
7371 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.139 | Δρmax = 0.83 e Å−3 |
S = 1.11 | Δρmin = −1.55 e Å−3 |
7371 reflections | Absolute structure: Flack (1983), with 2936 Friedel pairs |
517 parameters | Absolute structure parameter: 0.381 (17) |
2 restraints | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn | 0.79964 (9) | 0.23826 (6) | 0.58572 (5) | 0.03553 (17) | |
C1 | 0.7068 (6) | 0.4362 (5) | 0.6854 (3) | 0.0248 (11) | |
C2 | 0.7066 (6) | 0.4488 (5) | 0.7539 (3) | 0.0293 (12) | |
H2 | 0.6673 | 0.5230 | 0.7747 | 0.035* | |
C3 | 0.7743 (6) | 0.3327 (5) | 0.7823 (3) | 0.0287 (12) | |
H3 | 0.7915 | 0.3115 | 0.8272 | 0.034* | |
C4 | 0.8147 (7) | 0.2489 (5) | 0.7329 (3) | 0.0284 (15) | |
C5 | 0.8912 (6) | 0.1254 (5) | 0.7428 (3) | 0.0246 (11) | |
C6 | 0.9360 (6) | 0.0429 (5) | 0.6947 (3) | 0.0257 (11) | |
C7 | 1.0234 (6) | −0.0836 (5) | 0.7093 (3) | 0.0287 (12) | |
H7 | 1.0584 | −0.1244 | 0.7504 | 0.034* | |
C8 | 1.0435 (6) | −0.1300 (5) | 0.6504 (3) | 0.0291 (12) | |
H8 | 1.0934 | −0.2124 | 0.6427 | 0.035* | |
C9 | 0.9771 (6) | −0.0341 (5) | 0.6030 (3) | 0.0267 (11) | |
C10 | 0.9802 (6) | −0.0417 (5) | 0.5362 (3) | 0.0289 (12) | |
C11 | 0.9278 (6) | 0.0580 (5) | 0.4897 (3) | 0.0299 (12) | |
C12 | 0.9339 (7) | 0.0494 (6) | 0.4211 (3) | 0.0335 (13) | |
H12 | 0.9767 | −0.0231 | 0.4006 | 0.040* | |
C13 | 0.8676 (7) | 0.1636 (5) | 0.3924 (3) | 0.0330 (13) | |
H13 | 0.8553 | 0.1867 | 0.3479 | 0.040* | |
C14 | 0.8181 (7) | 0.2453 (5) | 0.4421 (4) | 0.0291 (15) | |
C15 | 0.7442 (6) | 0.3714 (5) | 0.4317 (3) | 0.0274 (12) | |
C16 | 0.7003 (6) | 0.4536 (5) | 0.4788 (3) | 0.0263 (11) | |
C17 | 0.6250 (6) | 0.5820 (5) | 0.4676 (3) | 0.0284 (12) | |
H17 | 0.5972 | 0.6262 | 0.4268 | 0.034* | |
C18 | 0.5992 (6) | 0.6312 (6) | 0.5237 (3) | 0.0295 (12) | |
H18 | 0.5499 | 0.7147 | 0.5302 | 0.035* | |
C19 | 0.6630 (6) | 0.5294 (5) | 0.5730 (3) | 0.0246 (11) | |
C20 | 0.6526 (6) | 0.5377 (5) | 0.6384 (3) | 0.0257 (11) | |
N21 | 0.7734 (5) | 0.3145 (4) | 0.6740 (2) | 0.0268 (10) | |
N22 | 0.9082 (5) | 0.0702 (4) | 0.6308 (2) | 0.0255 (10) | |
N23 | 0.8575 (5) | 0.1779 (4) | 0.5005 (2) | 0.0272 (10) | |
N24 | 0.7223 (5) | 0.4219 (4) | 0.5441 (2) | 0.0265 (10) | |
C25 | 0.9298 (6) | 0.0718 (5) | 0.8118 (3) | 0.0241 (11) | |
C26 | 1.0556 (7) | 0.1183 (6) | 0.8535 (3) | 0.0345 (13) | |
H26 | 1.1199 | 0.1827 | 0.8391 | 0.041* | |
C27 | 1.0858 (7) | 0.0690 (6) | 0.9165 (3) | 0.0379 (14) | |
H27 | 1.1704 | 0.1035 | 0.9452 | 0.045* | |
N28 | 1.0019 (6) | −0.0247 (5) | 0.9391 (2) | 0.0346 (11) | |
C29 | 0.8804 (7) | −0.0722 (6) | 0.8974 (3) | 0.0361 (14) | |
H29 | 0.8196 | −0.1394 | 0.9120 | 0.043* | |
C30 | 0.8430 (7) | −0.0247 (6) | 0.8339 (3) | 0.0355 (13) | |
H30 | 0.7573 | −0.0592 | 0.8059 | 0.043* | |
C31 | 1.0566 (6) | −0.1668 (5) | 0.5150 (3) | 0.0257 (12) | |
C32 | 1.0001 (7) | −0.2995 (7) | 0.5207 (3) | 0.0318 (14) | |
H32 | 0.9158 | −0.3117 | 0.5395 | 0.038* | |
C33 | 1.0683 (7) | −0.4146 (6) | 0.4985 (3) | 0.0341 (13) | |
H33 | 1.0333 | −0.5054 | 0.5041 | 0.041* | |
C34 | 1.1882 (7) | −0.3946 (6) | 0.4680 (3) | 0.0332 (13) | |
C35 | 1.2424 (7) | −0.2638 (6) | 0.4623 (3) | 0.0323 (14) | |
H35 | 1.3248 | −0.2513 | 0.4422 | 0.039* | |
C36 | 1.1777 (6) | −0.1492 (6) | 0.4856 (3) | 0.0277 (12) | |
H36 | 1.2161 | −0.0592 | 0.4815 | 0.033* | |
C37 | 1.2446 (7) | −0.5131 (6) | 0.4387 (3) | 0.0384 (14) | |
N38 | 1.2884 (7) | −0.6051 (6) | 0.4128 (3) | 0.0499 (16) | |
C39 | 0.7138 (6) | 0.4263 (5) | 0.3644 (3) | 0.0295 (12) | |
C40 | 0.5869 (6) | 0.3855 (6) | 0.3205 (3) | 0.0327 (13) | |
H40 | 0.5207 | 0.3209 | 0.3332 | 0.039* | |
C41 | 0.5579 (7) | 0.4396 (6) | 0.2580 (3) | 0.0363 (14) | |
H41 | 0.4714 | 0.4125 | 0.2283 | 0.044* | |
C42 | 0.6555 (7) | 0.5331 (5) | 0.2392 (3) | 0.0316 (13) | |
C43 | 0.7786 (9) | 0.5736 (7) | 0.2812 (3) | 0.0439 (17) | |
H43 | 0.8447 | 0.6375 | 0.2678 | 0.053* | |
C44 | 0.8080 (7) | 0.5219 (5) | 0.3437 (3) | 0.0345 (13) | |
H44 | 0.8938 | 0.5519 | 0.3730 | 0.041* | |
C45 | 0.6269 (7) | 0.5892 (6) | 0.1743 (3) | 0.0459 (15) | |
N46 | 0.6023 (7) | 0.6327 (5) | 0.1210 (3) | 0.0512 (14) | |
C47 | 0.5832 (6) | 0.6618 (6) | 0.6604 (3) | 0.0259 (13) | |
C48 | 0.6392 (6) | 0.7950 (5) | 0.6548 (3) | 0.0270 (12) | |
H48 | 0.7215 | 0.8072 | 0.6347 | 0.032* | |
C49 | 0.5758 (6) | 0.9092 (6) | 0.6784 (3) | 0.0314 (12) | |
H49 | 0.6131 | 0.9994 | 0.6735 | 0.038* | |
C50 | 0.4587 (7) | 0.8915 (6) | 0.7089 (3) | 0.0282 (13) | |
C51 | 0.3980 (6) | 0.7600 (6) | 0.7134 (3) | 0.0288 (13) | |
H51 | 0.3152 | 0.7484 | 0.7333 | 0.035* | |
C52 | 0.4603 (6) | 0.6469 (6) | 0.6883 (3) | 0.0295 (12) | |
H52 | 0.4181 | 0.5577 | 0.6903 | 0.035* | |
C53 | 0.3967 (7) | 1.0081 (6) | 0.7366 (3) | 0.0378 (14) | |
N54 | 0.3550 (7) | 1.1013 (6) | 0.7606 (3) | 0.0566 (17) | |
O55 | 0.5795 (4) | 0.1371 (4) | 0.56084 (19) | 0.0350 (9) | |
H55 | 0.5479 | 0.0928 | 0.5174 | 0.023 (13)* | |
C56 | 0.4487 (7) | 0.2068 (7) | 0.5745 (3) | 0.0520 (16) | |
H56A | 0.4717 | 0.2474 | 0.6179 | 0.078* | |
H56B | 0.3684 | 0.1396 | 0.5723 | 0.078* | |
H56C | 0.4182 | 0.2801 | 0.5426 | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.0603 (4) | 0.0251 (3) | 0.0233 (2) | 0.0134 (3) | 0.0132 (2) | 0.0031 (3) |
C1 | 0.030 (3) | 0.026 (3) | 0.020 (3) | −0.001 (2) | 0.008 (2) | −0.002 (2) |
C2 | 0.039 (3) | 0.025 (3) | 0.023 (3) | 0.001 (2) | 0.004 (2) | −0.002 (2) |
C3 | 0.044 (3) | 0.023 (3) | 0.020 (3) | 0.001 (2) | 0.010 (2) | −0.001 (2) |
C4 | 0.040 (3) | 0.033 (4) | 0.014 (3) | −0.005 (3) | 0.009 (2) | −0.0016 (19) |
C5 | 0.027 (3) | 0.021 (2) | 0.023 (3) | 0.000 (2) | −0.001 (2) | −0.001 (2) |
C6 | 0.028 (3) | 0.025 (3) | 0.026 (3) | −0.002 (2) | 0.011 (2) | 0.003 (2) |
C7 | 0.031 (3) | 0.025 (3) | 0.026 (3) | 0.006 (2) | −0.002 (2) | 0.003 (2) |
C8 | 0.035 (3) | 0.026 (3) | 0.026 (3) | 0.000 (2) | 0.006 (2) | 0.000 (2) |
C9 | 0.032 (3) | 0.027 (3) | 0.022 (3) | 0.001 (2) | 0.006 (2) | −0.004 (2) |
C10 | 0.039 (3) | 0.024 (2) | 0.027 (3) | −0.004 (2) | 0.015 (2) | −0.001 (2) |
C11 | 0.037 (3) | 0.025 (3) | 0.028 (3) | −0.001 (2) | 0.007 (2) | −0.003 (2) |
C12 | 0.044 (3) | 0.032 (3) | 0.028 (3) | 0.007 (3) | 0.014 (3) | −0.005 (2) |
C13 | 0.042 (3) | 0.033 (3) | 0.026 (3) | 0.005 (3) | 0.012 (2) | −0.001 (2) |
C14 | 0.046 (3) | 0.014 (3) | 0.029 (3) | −0.005 (2) | 0.009 (3) | −0.0001 (19) |
C15 | 0.039 (3) | 0.022 (2) | 0.024 (3) | 0.000 (2) | 0.012 (2) | 0.000 (2) |
C16 | 0.035 (3) | 0.020 (2) | 0.024 (3) | −0.001 (2) | 0.007 (2) | 0.000 (2) |
C17 | 0.032 (3) | 0.031 (3) | 0.022 (3) | 0.005 (2) | 0.007 (2) | 0.002 (2) |
C18 | 0.031 (3) | 0.028 (3) | 0.030 (3) | 0.005 (2) | 0.006 (2) | −0.001 (2) |
C19 | 0.026 (3) | 0.021 (2) | 0.026 (3) | 0.003 (2) | 0.004 (2) | 0.006 (2) |
C20 | 0.024 (3) | 0.024 (3) | 0.027 (3) | 0.004 (2) | 0.001 (2) | −0.001 (2) |
N21 | 0.033 (3) | 0.018 (2) | 0.029 (3) | 0.0033 (18) | 0.006 (2) | 0.0029 (18) |
N22 | 0.035 (2) | 0.023 (2) | 0.020 (2) | −0.0003 (18) | 0.0092 (19) | 0.0003 (17) |
N23 | 0.039 (3) | 0.023 (2) | 0.020 (2) | 0.0059 (19) | 0.0068 (19) | 0.0015 (17) |
N24 | 0.032 (2) | 0.024 (2) | 0.023 (3) | 0.0020 (18) | 0.0030 (19) | −0.0013 (17) |
C25 | 0.035 (3) | 0.018 (2) | 0.021 (3) | 0.005 (2) | 0.009 (2) | 0.0000 (19) |
C26 | 0.037 (3) | 0.034 (3) | 0.031 (3) | 0.001 (2) | 0.004 (3) | 0.000 (2) |
C27 | 0.045 (4) | 0.039 (3) | 0.030 (3) | 0.001 (3) | 0.007 (3) | 0.000 (2) |
N28 | 0.046 (3) | 0.030 (2) | 0.026 (3) | 0.012 (2) | 0.004 (2) | 0.0015 (19) |
C29 | 0.055 (4) | 0.028 (3) | 0.026 (3) | −0.002 (3) | 0.013 (3) | 0.002 (2) |
C30 | 0.044 (3) | 0.032 (3) | 0.028 (3) | −0.008 (3) | 0.001 (3) | −0.004 (2) |
C31 | 0.030 (3) | 0.022 (3) | 0.021 (3) | 0.003 (2) | −0.004 (2) | −0.003 (2) |
C32 | 0.032 (3) | 0.035 (4) | 0.029 (3) | 0.006 (3) | 0.008 (2) | 0.003 (3) |
C33 | 0.047 (4) | 0.023 (3) | 0.030 (3) | −0.003 (3) | 0.001 (3) | −0.003 (2) |
C34 | 0.044 (4) | 0.030 (3) | 0.027 (3) | 0.014 (3) | 0.011 (3) | −0.001 (2) |
C35 | 0.038 (3) | 0.028 (3) | 0.032 (3) | 0.012 (3) | 0.009 (3) | 0.000 (2) |
C36 | 0.029 (3) | 0.025 (3) | 0.034 (3) | 0.003 (2) | 0.017 (2) | 0.001 (2) |
C37 | 0.047 (4) | 0.027 (3) | 0.042 (4) | 0.008 (3) | 0.009 (3) | 0.002 (2) |
N38 | 0.055 (4) | 0.031 (3) | 0.066 (4) | 0.011 (3) | 0.018 (3) | −0.007 (3) |
C39 | 0.040 (3) | 0.022 (3) | 0.025 (3) | 0.006 (2) | 0.003 (2) | −0.003 (2) |
C40 | 0.032 (3) | 0.040 (3) | 0.028 (3) | 0.000 (2) | 0.011 (2) | 0.004 (2) |
C41 | 0.033 (3) | 0.043 (3) | 0.028 (3) | 0.008 (3) | −0.004 (2) | 0.004 (2) |
C42 | 0.049 (3) | 0.025 (3) | 0.023 (3) | 0.014 (2) | 0.011 (2) | 0.007 (2) |
C43 | 0.070 (5) | 0.028 (3) | 0.035 (4) | −0.003 (3) | 0.014 (3) | 0.000 (2) |
C44 | 0.053 (4) | 0.028 (3) | 0.022 (3) | −0.003 (3) | 0.006 (3) | 0.005 (2) |
C45 | 0.058 (4) | 0.045 (3) | 0.035 (3) | 0.021 (3) | 0.011 (3) | 0.003 (3) |
N46 | 0.075 (4) | 0.047 (3) | 0.034 (3) | 0.016 (3) | 0.016 (3) | 0.008 (2) |
C47 | 0.028 (3) | 0.030 (3) | 0.022 (3) | −0.003 (2) | 0.010 (2) | −0.001 (2) |
C48 | 0.028 (3) | 0.023 (3) | 0.029 (3) | −0.001 (2) | 0.004 (2) | −0.002 (2) |
C49 | 0.037 (3) | 0.030 (3) | 0.029 (3) | −0.002 (2) | 0.011 (3) | 0.003 (2) |
C50 | 0.036 (3) | 0.020 (3) | 0.028 (3) | −0.002 (2) | 0.003 (2) | −0.001 (2) |
C51 | 0.035 (3) | 0.028 (3) | 0.025 (3) | −0.002 (3) | 0.011 (2) | 0.000 (2) |
C52 | 0.035 (3) | 0.024 (3) | 0.027 (3) | −0.001 (2) | 0.001 (2) | −0.001 (2) |
C53 | 0.045 (4) | 0.028 (3) | 0.041 (4) | 0.003 (3) | 0.010 (3) | 0.000 (3) |
N54 | 0.082 (5) | 0.033 (3) | 0.062 (4) | 0.010 (3) | 0.034 (4) | −0.006 (3) |
O55 | 0.030 (2) | 0.043 (2) | 0.031 (2) | −0.0059 (17) | 0.0055 (16) | −0.0039 (16) |
C56 | 0.046 (4) | 0.066 (4) | 0.043 (3) | −0.008 (3) | 0.007 (3) | −0.010 (3) |
Geometric parameters (Å, º) top
Zn—N21 | 2.062 (5) | C26—H26 | 0.9500 |
Zn—N22 | 2.042 (4) | C27—N28 | 1.339 (8) |
Zn—N23 | 2.059 (4) | C27—H27 | 0.9500 |
Zn—N24 | 2.044 (4) | N28—C29 | 1.362 (8) |
Zn—O55 | 2.226 (4) | C29—C30 | 1.393 (9) |
Zn—N46i | 3.020 (6) | C29—H29 | 0.9500 |
C1—N21 | 1.371 (6) | C30—H30 | 0.9500 |
C1—C20 | 1.415 (7) | C31—C36 | 1.395 (8) |
C1—C2 | 1.450 (8) | C31—C32 | 1.398 (9) |
C2—C3 | 1.364 (8) | C32—C33 | 1.404 (8) |
C2—H2 | 0.9500 | C32—H32 | 0.9500 |
C3—C4 | 1.428 (8) | C33—C34 | 1.402 (9) |
C3—H3 | 0.9500 | C33—H33 | 0.9500 |
C4—N21 | 1.380 (8) | C34—C35 | 1.374 (8) |
C4—C5 | 1.382 (7) | C34—C37 | 1.447 (8) |
C5—C6 | 1.414 (7) | C35—C36 | 1.393 (8) |
C5—C25 | 1.521 (7) | C35—H35 | 0.9500 |
C6—N22 | 1.348 (7) | C36—H36 | 0.9500 |
C6—C7 | 1.464 (7) | C37—N38 | 1.158 (8) |
C7—C8 | 1.368 (8) | C39—C44 | 1.398 (8) |
C7—H7 | 0.9500 | C39—C40 | 1.401 (8) |
C8—C9 | 1.412 (8) | C40—C41 | 1.394 (8) |
C8—H8 | 0.9500 | C40—H40 | 0.9500 |
C9—N22 | 1.384 (6) | C41—C42 | 1.389 (9) |
C9—C10 | 1.418 (8) | C41—H41 | 0.9500 |
C10—C11 | 1.392 (8) | C42—C43 | 1.355 (10) |
C10—C31 | 1.512 (7) | C42—C45 | 1.448 (8) |
C11—N23 | 1.370 (7) | C43—C44 | 1.386 (9) |
C11—C12 | 1.461 (8) | C43—H43 | 0.9500 |
C12—C13 | 1.346 (8) | C44—H44 | 0.9500 |
C12—H12 | 0.9500 | C45—N46 | 1.180 (7) |
C13—C14 | 1.455 (9) | C47—C52 | 1.387 (8) |
C13—H13 | 0.9500 | C47—C48 | 1.401 (8) |
C14—N23 | 1.378 (8) | C48—C49 | 1.387 (8) |
C14—C15 | 1.393 (7) | C48—H48 | 0.9500 |
C15—C16 | 1.393 (7) | C49—C50 | 1.375 (8) |
C15—C39 | 1.489 (8) | C49—H49 | 0.9500 |
C16—N24 | 1.388 (7) | C50—C51 | 1.399 (8) |
C16—C17 | 1.420 (7) | C50—C53 | 1.440 (8) |
C17—C18 | 1.339 (8) | C51—C52 | 1.389 (8) |
C17—H17 | 0.9500 | C51—H51 | 0.9500 |
C18—C19 | 1.467 (8) | C52—H52 | 0.9500 |
C18—H18 | 0.9500 | C53—N54 | 1.138 (8) |
C19—N24 | 1.372 (7) | O55—C56 | 1.463 (7) |
C19—C20 | 1.404 (8) | O55—H55 | 1.0008 |
C20—C47 | 1.478 (8) | C56—H56A | 0.9800 |
C25—C30 | 1.371 (8) | C56—H56B | 0.9800 |
C25—C26 | 1.387 (8) | C56—H56C | 0.9800 |
C26—C27 | 1.389 (9) | | |
| | | |
N21—Zn—N22 | 89.86 (17) | C30—C25—C26 | 118.7 (5) |
N21—Zn—N23 | 171.0 (2) | C30—C25—C5 | 121.0 (5) |
N21—Zn—N24 | 89.09 (17) | C26—C25—C5 | 120.3 (5) |
N22—Zn—N23 | 89.61 (17) | C25—C26—C27 | 118.7 (6) |
N22—Zn—N24 | 171.0 (2) | C25—C26—H26 | 120.7 |
N23—Zn—N24 | 90.02 (17) | C27—C26—H26 | 120.7 |
N21—Zn—O55 | 95.96 (16) | N28—C27—C26 | 123.5 (6) |
N22—Zn—O55 | 95.93 (16) | N28—C27—H27 | 118.3 |
N23—Zn—O55 | 93.07 (17) | C26—C27—H27 | 118.3 |
N24—Zn—O55 | 93.07 (16) | C27—N28—C29 | 117.4 (5) |
N21—C1—C20 | 125.5 (5) | N28—C29—C30 | 121.8 (5) |
N21—C1—C2 | 109.7 (4) | N28—C29—H29 | 119.1 |
C20—C1—C2 | 124.8 (5) | C30—C29—H29 | 119.1 |
C3—C2—C1 | 106.2 (5) | C25—C30—C29 | 120.0 (6) |
C3—C2—H2 | 126.9 | C25—C30—H30 | 120.0 |
C1—C2—H2 | 126.9 | C29—C30—H30 | 120.0 |
C2—C3—C4 | 107.9 (5) | C36—C31—C32 | 119.8 (5) |
C2—C3—H3 | 126.0 | C36—C31—C10 | 119.9 (5) |
C4—C3—H3 | 126.0 | C32—C31—C10 | 120.2 (5) |
N21—C4—C5 | 125.1 (6) | C31—C32—C33 | 119.8 (5) |
N21—C4—C3 | 109.4 (5) | C31—C32—H32 | 120.1 |
C5—C4—C3 | 125.4 (6) | C33—C32—H32 | 120.1 |
C4—C5—C6 | 126.3 (5) | C34—C33—C32 | 119.5 (5) |
C4—C5—C25 | 117.0 (5) | C34—C33—H33 | 120.2 |
C6—C5—C25 | 116.7 (4) | C32—C33—H33 | 120.2 |
N22—C6—C5 | 125.6 (5) | C35—C34—C33 | 120.2 (5) |
N22—C6—C7 | 111.2 (5) | C35—C34—C37 | 121.4 (6) |
C5—C6—C7 | 123.2 (5) | C33—C34—C37 | 118.2 (5) |
C8—C7—C6 | 104.6 (5) | C34—C35—C36 | 120.6 (6) |
C8—C7—H7 | 127.7 | C34—C35—H35 | 119.7 |
C6—C7—H7 | 127.7 | C36—C35—H35 | 119.7 |
C7—C8—C9 | 108.0 (5) | C31—C36—C35 | 120.0 (5) |
C7—C8—H8 | 126.0 | C31—C36—H36 | 120.0 |
C9—C8—H8 | 126.0 | C35—C36—H36 | 120.0 |
N22—C9—C8 | 110.5 (5) | N38—C37—C34 | 177.3 (7) |
N22—C9—C10 | 124.1 (5) | C44—C39—C40 | 118.1 (5) |
C8—C9—C10 | 125.4 (5) | C44—C39—C15 | 121.5 (5) |
C11—C10—C9 | 126.4 (5) | C40—C39—C15 | 120.4 (5) |
C11—C10—C31 | 117.6 (5) | C41—C40—C39 | 120.0 (5) |
C9—C10—C31 | 116.0 (5) | C41—C40—H40 | 120.0 |
N23—C11—C10 | 125.3 (5) | C39—C40—H40 | 120.0 |
N23—C11—C12 | 109.0 (5) | C42—C41—C40 | 119.9 (6) |
C10—C11—C12 | 125.7 (5) | C42—C41—H41 | 120.0 |
C13—C12—C11 | 107.2 (5) | C40—C41—H41 | 120.0 |
C13—C12—H12 | 126.4 | C43—C42—C41 | 120.7 (6) |
C11—C12—H12 | 126.4 | C43—C42—C45 | 118.9 (6) |
C12—C13—C14 | 107.5 (6) | C41—C42—C45 | 120.4 (6) |
C12—C13—H13 | 126.2 | C42—C43—C44 | 119.9 (6) |
C14—C13—H13 | 126.2 | C42—C43—H43 | 120.0 |
N23—C14—C15 | 126.1 (6) | C44—C43—H43 | 120.0 |
N23—C14—C13 | 108.8 (5) | C43—C44—C39 | 121.3 (6) |
C15—C14—C13 | 125.1 (6) | C43—C44—H44 | 119.4 |
C14—C15—C16 | 126.1 (6) | C39—C44—H44 | 119.3 |
C14—C15—C39 | 117.1 (5) | N46—C45—C42 | 178.8 (7) |
C16—C15—C39 | 116.7 (5) | C52—C47—C48 | 118.6 (5) |
N24—C16—C15 | 125.2 (5) | C52—C47—C20 | 119.5 (5) |
N24—C16—C17 | 109.1 (4) | C48—C47—C20 | 121.9 (5) |
C15—C16—C17 | 125.7 (5) | C49—C48—C47 | 120.7 (5) |
C18—C17—C16 | 109.4 (5) | C49—C48—H48 | 119.6 |
C18—C17—H17 | 125.3 | C47—C48—H48 | 119.6 |
C16—C17—H17 | 125.3 | C50—C49—C48 | 119.7 (5) |
C17—C18—C19 | 105.8 (5) | C50—C49—H49 | 120.1 |
C17—C18—H18 | 127.1 | C48—C49—H49 | 120.1 |
C19—C18—H18 | 127.1 | C49—C50—C51 | 120.6 (5) |
N24—C19—C20 | 126.2 (5) | C49—C50—C53 | 120.4 (5) |
N24—C19—C18 | 109.4 (5) | C51—C50—C53 | 119.0 (5) |
C20—C19—C18 | 124.2 (5) | C52—C51—C50 | 119.1 (5) |
C19—C20—C1 | 124.5 (5) | C52—C51—H51 | 120.5 |
C19—C20—C47 | 118.3 (5) | C50—C51—H51 | 120.5 |
C1—C20—C47 | 117.2 (5) | C47—C52—C51 | 121.1 (5) |
C1—N21—C4 | 106.8 (5) | C47—C52—H52 | 119.4 |
C1—N21—Zn | 127.1 (4) | C51—C52—H52 | 119.4 |
C4—N21—Zn | 126.1 (3) | N54—C53—C50 | 176.3 (7) |
C6—N22—C9 | 105.6 (4) | C56—O55—Zn | 120.3 (3) |
C6—N22—Zn | 126.9 (3) | C56—O55—H55 | 106.0 |
C9—N22—Zn | 127.3 (4) | Zn—O55—H55 | 119.4 |
C11—N23—C14 | 107.5 (5) | O55—C56—H56A | 109.5 |
C11—N23—Zn | 126.8 (4) | O55—C56—H56B | 109.5 |
C14—N23—Zn | 125.4 (4) | H56A—C56—H56B | 109.5 |
C19—N24—C16 | 106.3 (4) | O55—C56—H56C | 109.5 |
C19—N24—Zn | 127.1 (4) | H56A—C56—H56C | 109.5 |
C16—N24—Zn | 126.0 (3) | H56B—C56—H56C | 109.5 |
Symmetry code: (i) x+1/2, −y+1, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O55—H55···N28ii | 1.00 | 1.75 | 2.751 (6) | 175 |
Symmetry code: (ii) x−1/2, −y, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Zn(C46H24N8)(CH4O)] |
Mr | 786.14 |
Crystal system, space group | Monoclinic, Pn |
Temperature (K) | 110 |
a, b, c (Å) | 9.2505 (4), 9.6600 (5), 21.1032 (10) |
β (°) | 101.422 (3) |
V (Å3) | 1848.43 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17749, 7371, 6328 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.139, 1.11 |
No. of reflections | 7371 |
No. of parameters | 517 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −1.55 |
Absolute structure | Flack (1983), with 2936 Friedel pairs |
Absolute structure parameter | 0.381 (17) |
Selected geometric parameters (Å, º) topZn—N21 | 2.062 (5) | Zn—N24 | 2.044 (4) |
Zn—N22 | 2.042 (4) | Zn—O55 | 2.226 (4) |
Zn—N23 | 2.059 (4) | Zn—N46i | 3.020 (6) |
| | | |
N21—Zn—N22 | 89.86 (17) | N23—Zn—N24 | 90.02 (17) |
N21—Zn—N23 | 171.0 (2) | N21—Zn—O55 | 95.96 (16) |
N21—Zn—N24 | 89.09 (17) | N22—Zn—O55 | 95.93 (16) |
N22—Zn—N23 | 89.61 (17) | N23—Zn—O55 | 93.07 (17) |
N22—Zn—N24 | 171.0 (2) | N24—Zn—O55 | 93.07 (16) |
Symmetry code: (i) x+1/2, −y+1, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O55—H55···N28ii | 1.00 | 1.75 | 2.751 (6) | 175 |
Symmetry code: (ii) x−1/2, −y, z−1/2. |
The supramolecular chemistry of porphyrins in the context of crystal engineering has been widely studied during the past decade or so. Effort has been focused mostly on the meso-tetra(4-pyridyl)porphyrin and meso-tetra(4-carboxyphenyl)porphyrin building blocks, in both their free-base and metallated forms, taking advantage of the square-planar functionality of these units and the versatile coordination and hydrogen-bonding capacity of the peripheral pyridyl and carboxylic acid groups (Goldberg, 2005; Kosal et al., 2002; Diskin-Posner et al., 2000; Diskin-Posner & Goldberg, 1999; Krupitsky et al., 1994; Abrahams et al., 1994). Attempts to induce the formation of non-centrosymmetric materials using moieties of reduced (lower than D4h) symmetry have been reported as well (George et al., 2006; George & Goldberg, 2006; Vinodu & Goldberg, 2003). As part of our systematic investigation of porphyrin-based crystalline solids, we have been exploring the networking capacity of porphyrin scaffolds bearing various combinations of peripheral functional groups (Goldberg, 2005). Here, we report on the self-assembly of the title compound, (I).
Compound (I) (Fig. 1) is characterized by its low symmetry, while bearing substituent groups suitable for hydrogen bonding as well as coordinative interactions. Both types come into play in the interesting crystal structure of (I). The molecular structure exhibits a slightly domed conformation, with the central Zn ion deviating by only 0.161 (3) Å from the mean plane of the four pyrrole N atoms towards the methanol ligand. This value should be compared with a commonly observed deviation of about 0.3 Å in otherwise unconstrained five-coordinate complexes of zinc porphyrins (e.g. Lipstman & Goldberg, 2006). An apparent weak coordination to the central Zn ion from the opposite axial direction (Table 1, see also below) provides an explanation of this discrepancy.
Fig. 2 depicts the supramolecular interaction scheme for (I), and the self-assembly process can be best described in a modular way. Firstly, the strongest intermolecular attraction that can be utilized in this structure is provided by hydrogen bonding between the axial methanol ligand of one porphyrin (acting as H-atom donor) to the pyridyl arm (the strongest H-atom acceptor) of an adjacent unit (Table 2). Each porphyrin molecule is involved in two such bonds in opposite directions, thus creating a hydrogen-bonded zigzag chain of the porphyrin species. However, adjacent chains combine into a layered array via additional weak coordinations. These involve the cyanophenyl substituent trans to the pyridyl group of one unit and the uncoordinated (slightly concave) face of the core Zn(methanol) of an adjacent glide-related moiety (Table 1). This Zn···N distance is somewhat longer than previously observed in coordination polymers of six-coordinate zinc tetra(4-cyanophenyl)porphyrin (2.7–2.8 Å; Krishna Kumar et al., 1998), and in the present case this should be attributed to the bias introduced by the markedly stronger methanol binding to the Zn, as is also reflected in the slighly domed conformation of the porphyrin species. However, the Zn···NC attraction creates an interporphyrin `linkage' along an axis nearly perpendicular to the O55—H55···N28 hydrogen-bonding direction, thus affording a supramolecular porphyrin array of two-dimensional connectivity.
The crystal structure of (I) naturally consists of a stacked arrangement of the two-dimensional arrays. The corrugated surfaces of neighbouring layers seem to fit effectively into one another, and no solvent is included between them. Two of the cyanophenyl substituents (related trans to each other) are directed at the interlayer interface from above and below, contributing stabilizing dipolar attractions between these CN dipoles of adjacent layers that point in opposite directions (Fig. 3). However, the structure of (I) is not centrosymmetric. This is consistent with our earlier correlations between the symmetry of the individual building blocks and that of the resulting crystalline architectures in porphyrin solids (George & Goldberg, 2006; Vinodu & Goldberg, 2003). The use of metalloporphyrin scaffolds of D4h symmetry almost uniformly leads to centrosymmetric crystal structures, while the presence of directional inter-porphyrin interactions combined with lateral and/or axial asymmetry of the individual building blocks may afford non-centrosymmetric architectures (George et al., 2006; George & Goldberg, 2006; Vinodu & Goldberg, 2003). In summary, the structure of (I) consists of uniquely assembled two-dimensional multi-porphyrin arrays, via a combination of hydrogen-bonding and weak coordination.