The centrosymmetric title compound, C54H66N4, is a 5,15 diaryloctaalkyl free base porphyrin. The planar 24-atom porphyrin core has a significant in-plane distortion commonly observed in these types of molecules along the 5,15 direction. The porphyrin molecules are arranged in the crystal structure in two-dimensional assemblies via phenyl-edge-to-porphyrin-face interactions.
Supporting information
CCDC reference: 608404
Key indicators
- Single-crystal X-ray study
- T = 83 K
- Mean (C-C) = 0.004 Å
- R factor = 0.067
- wR factor = 0.154
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) ..... 10 Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C18
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C17
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al.,
2002); software used to prepare material for publication: WinGX (Farrugia, 1999).
5,15-Bis(
p-methylphenyl)-2,8,12,18-tetrabutyl-3,7,13,17-
tetramethylporphyrin
top
Crystal data top
C54H66N4 | Z = 1 |
Mr = 771.11 | F(000) = 418 |
Triclinic, P1 | Dx = 1.177 Mg m−3 |
a = 7.0708 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.8464 (2) Å | Cell parameters from 4112 reflections |
c = 15.4009 (1) Å | θ = 1.4–25.8° |
α = 108.474 (1)° | µ = 0.07 mm−1 |
β = 102.774 (1)° | T = 83 K |
γ = 91.093 (1)° | Needle, purple |
V = 1087.46 (3) Å3 | 0.52 × 0.16 × 0.04 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2863 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 25.8°, θmin = 1.4° |
ω scans | h = −8→8 |
9807 measured reflections | k = −13→12 |
4112 independent reflections | l = 0→18 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0219P)2 + 1.3557P] where P = (Fo2 + 2Fc2)/3 |
4112 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.30 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) |
N1 | −0.1824 (3) | 0.1244 (2) | 0.06884 (14) | 0.0194 (5) | |
H1A | −0.1165 | 0.0759 | 0.0329 | 0.023* | 0.50 |
C1 | 0.3788 (3) | −0.0610 (2) | 0.13118 (17) | 0.0181 (5) | |
N2 | 0.2140 (3) | 0.0030 (2) | 0.11738 (14) | 0.0198 (5) | |
H2A | 0.1429 | 0.0014 | 0.0639 | 0.024* | 0.50 |
C2 | 0.1838 (4) | 0.0693 (2) | 0.20396 (17) | 0.0199 (5) | |
C3 | 0.3376 (4) | 0.0496 (2) | 0.27649 (17) | 0.0201 (5) | |
C4 | 0.4597 (4) | −0.0295 (3) | 0.23256 (18) | 0.0211 (6) | |
C5 | 0.0312 (4) | 0.1428 (2) | 0.22369 (17) | 0.0209 (6) | |
H5A | 0.0403 | 0.1829 | 0.2877 | 0.025* | |
C6 | −0.1333 (4) | 0.1678 (2) | 0.16527 (17) | 0.0197 (5) | |
C7 | −0.3555 (4) | 0.1718 (2) | 0.03922 (17) | 0.0189 (5) | |
C8 | −0.4214 (4) | 0.2468 (2) | 0.12171 (18) | 0.0199 (5) | |
C9 | −0.4453 (3) | 0.1461 (2) | −0.05685 (17) | 0.0179 (5) | |
C10 | −0.2838 (4) | 0.2431 (2) | 0.19885 (18) | 0.0210 (6) | |
C11 | −0.6078 (4) | 0.2251 (2) | −0.08076 (17) | 0.0200 (5) | |
C12 | −0.8026 (4) | 0.1858 (3) | −0.09221 (18) | 0.0223 (6) | |
H12A | −0.8362 | 0.1073 | −0.0844 | 0.027* | |
C13 | −0.9474 (4) | 0.2627 (3) | −0.11522 (18) | 0.0238 (6) | |
H13A | −1.0771 | 0.2346 | −0.1231 | 0.029* | |
C14 | −0.9020 (4) | 0.3803 (3) | −0.12654 (18) | 0.0252 (6) | |
C15 | −0.7087 (4) | 0.4199 (3) | −0.11504 (19) | 0.0262 (6) | |
H15A | −0.6756 | 0.4986 | −0.1225 | 0.031* | |
C16 | −0.5630 (4) | 0.3431 (3) | −0.09230 (19) | 0.0246 (6) | |
H16A | −0.4335 | 0.3714 | −0.0847 | 0.030* | |
C17 | −0.6040 (4) | 0.3134 (3) | 0.12585 (19) | 0.0248 (6) | |
H17A | −0.6070 | 0.3554 | 0.1905 | 0.037* | |
H17B | −0.7150 | 0.2501 | 0.0950 | 0.037* | |
H17C | −0.6073 | 0.3776 | 0.0947 | 0.037* | |
C18 | 0.6430 (4) | −0.0709 (3) | 0.28213 (18) | 0.0273 (6) | |
H18A | 0.6584 | −0.0347 | 0.3491 | 0.041* | |
H18B | 0.7530 | −0.0400 | 0.2652 | 0.041* | |
H18C | 0.6344 | −0.1645 | 0.2637 | 0.041* | |
C19 | 0.3467 (4) | 0.1008 (3) | 0.38014 (17) | 0.0249 (6) | |
H19A | 0.3088 | 0.1892 | 0.3963 | 0.030* | |
H19B | 0.4801 | 0.1042 | 0.4150 | 0.030* | |
C20 | 0.2142 (4) | 0.0166 (3) | 0.41044 (18) | 0.0277 (6) | |
H20A | 0.2270 | 0.0546 | 0.4778 | 0.033* | |
H20B | 0.0800 | 0.0194 | 0.3793 | 0.033* | |
C21 | 0.2576 (4) | −0.1258 (3) | 0.38830 (19) | 0.0295 (6) | |
H21A | 0.2468 | −0.1638 | 0.3211 | 0.035* | |
H21B | 0.3908 | −0.1291 | 0.4205 | 0.035* | |
C22 | 0.1217 (5) | −0.2070 (3) | 0.4175 (2) | 0.0376 (7) | |
H22A | 0.1554 | −0.2954 | 0.4016 | 0.056* | |
H22B | −0.0103 | −0.2055 | 0.3849 | 0.056* | |
H22C | 0.1344 | −0.1714 | 0.4843 | 0.056* | |
C23 | −0.2870 (4) | 0.3086 (3) | 0.29996 (18) | 0.0245 (6) | |
H23A | −0.2228 | 0.2571 | 0.3371 | 0.029* | |
H23B | −0.4213 | 0.3107 | 0.3051 | 0.029* | |
C24 | −0.1869 (4) | 0.4482 (3) | 0.34117 (19) | 0.0288 (6) | |
H24A | −0.0469 | 0.4445 | 0.3543 | 0.035* | |
H24B | −0.2216 | 0.4916 | 0.2945 | 0.035* | |
C25 | −0.2418 (4) | 0.5292 (3) | 0.4317 (2) | 0.0345 (7) | |
H25A | −0.2310 | 0.4785 | 0.4741 | 0.041* | |
H25B | −0.1504 | 0.6067 | 0.4627 | 0.041* | |
C26 | −0.4469 (5) | 0.5698 (3) | 0.4132 (2) | 0.0445 (9) | |
H26A | −0.4747 | 0.6202 | 0.4718 | 0.067* | |
H26B | −0.5383 | 0.4934 | 0.3837 | 0.067* | |
H26C | −0.4577 | 0.6216 | 0.3724 | 0.067* | |
C27 | −1.0585 (4) | 0.4667 (3) | −0.1483 (2) | 0.0341 (7) | |
H27A | −0.9996 | 0.5440 | −0.1531 | 0.051* | |
H27B | −1.1263 | 0.4906 | −0.0987 | 0.051* | |
H27C | −1.1488 | 0.4202 | −0.2069 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0180 (11) | 0.0202 (11) | 0.0189 (11) | 0.0064 (9) | 0.0026 (8) | 0.0059 (9) |
C1 | 0.0170 (12) | 0.0186 (13) | 0.0205 (13) | 0.0050 (10) | 0.0031 (10) | 0.0095 (10) |
N2 | 0.0206 (11) | 0.0206 (11) | 0.0180 (11) | 0.0061 (9) | 0.0039 (9) | 0.0065 (9) |
C2 | 0.0222 (13) | 0.0192 (13) | 0.0198 (13) | 0.0052 (10) | 0.0051 (10) | 0.0086 (10) |
C3 | 0.0179 (13) | 0.0219 (13) | 0.0192 (13) | 0.0050 (10) | 0.0024 (10) | 0.0063 (10) |
C4 | 0.0196 (13) | 0.0231 (14) | 0.0207 (13) | 0.0051 (11) | 0.0023 (10) | 0.0089 (11) |
C5 | 0.0235 (13) | 0.0224 (13) | 0.0156 (12) | 0.0042 (11) | 0.0042 (10) | 0.0051 (10) |
C6 | 0.0218 (13) | 0.0191 (13) | 0.0177 (12) | 0.0048 (10) | 0.0051 (10) | 0.0052 (10) |
C7 | 0.0194 (13) | 0.0166 (13) | 0.0210 (13) | 0.0032 (10) | 0.0040 (10) | 0.0071 (10) |
C8 | 0.0199 (13) | 0.0175 (13) | 0.0230 (13) | 0.0037 (10) | 0.0061 (10) | 0.0069 (10) |
C9 | 0.0142 (12) | 0.0185 (13) | 0.0215 (13) | 0.0031 (10) | 0.0025 (10) | 0.0083 (10) |
C10 | 0.0226 (13) | 0.0192 (13) | 0.0208 (13) | 0.0049 (11) | 0.0048 (10) | 0.0060 (10) |
C11 | 0.0195 (13) | 0.0226 (14) | 0.0162 (12) | 0.0071 (11) | 0.0026 (10) | 0.0050 (10) |
C12 | 0.0206 (13) | 0.0210 (14) | 0.0262 (14) | 0.0054 (11) | 0.0047 (11) | 0.0094 (11) |
C13 | 0.0178 (13) | 0.0274 (15) | 0.0254 (14) | 0.0025 (11) | 0.0045 (10) | 0.0081 (11) |
C14 | 0.0241 (14) | 0.0287 (15) | 0.0229 (14) | 0.0092 (12) | 0.0043 (11) | 0.0089 (11) |
C15 | 0.0275 (15) | 0.0245 (14) | 0.0301 (15) | 0.0079 (12) | 0.0084 (12) | 0.0127 (12) |
C16 | 0.0217 (14) | 0.0248 (14) | 0.0298 (15) | 0.0072 (11) | 0.0082 (11) | 0.0107 (11) |
C17 | 0.0248 (14) | 0.0267 (15) | 0.0248 (14) | 0.0099 (11) | 0.0080 (11) | 0.0091 (11) |
C18 | 0.0239 (14) | 0.0348 (16) | 0.0218 (14) | 0.0098 (12) | 0.0024 (11) | 0.0092 (12) |
C19 | 0.0221 (14) | 0.0317 (15) | 0.0160 (13) | 0.0076 (12) | 0.0000 (10) | 0.0039 (11) |
C20 | 0.0241 (14) | 0.0406 (17) | 0.0168 (13) | 0.0088 (13) | 0.0030 (11) | 0.0082 (12) |
C21 | 0.0313 (16) | 0.0361 (16) | 0.0220 (14) | 0.0077 (13) | 0.0063 (12) | 0.0107 (12) |
C22 | 0.0378 (18) | 0.0456 (19) | 0.0351 (17) | 0.0092 (15) | 0.0101 (14) | 0.0199 (15) |
C23 | 0.0250 (14) | 0.0275 (15) | 0.0223 (14) | 0.0092 (11) | 0.0073 (11) | 0.0083 (11) |
C24 | 0.0311 (15) | 0.0285 (15) | 0.0237 (14) | 0.0023 (12) | 0.0083 (12) | 0.0032 (12) |
C25 | 0.0374 (17) | 0.0335 (17) | 0.0266 (15) | 0.0020 (13) | 0.0106 (13) | −0.0001 (12) |
C26 | 0.047 (2) | 0.0385 (19) | 0.0392 (18) | 0.0160 (16) | 0.0129 (15) | −0.0016 (15) |
C27 | 0.0315 (16) | 0.0316 (16) | 0.0439 (18) | 0.0155 (13) | 0.0091 (14) | 0.0183 (14) |
Geometric parameters (Å, º) top
N1—C6 | 1.368 (3) | C17—H17A | 0.96 |
N1—C7 | 1.377 (3) | C17—H17B | 0.96 |
N1—H1A | 0.86 | C17—H17C | 0.96 |
C1—N2 | 1.379 (3) | C18—H18A | 0.96 |
C1—C9i | 1.403 (3) | C18—H18B | 0.96 |
C1—C4 | 1.463 (3) | C18—H18C | 0.96 |
N2—C2 | 1.365 (3) | C19—C20 | 1.536 (4) |
N2—H2A | 0.86 | C19—H19A | 0.97 |
C2—C5 | 1.384 (3) | C19—H19B | 0.97 |
C2—C3 | 1.448 (3) | C20—C21 | 1.525 (4) |
C3—C4 | 1.363 (4) | C20—H20A | 0.97 |
C3—C19 | 1.501 (3) | C20—H20B | 0.97 |
C4—C18 | 1.506 (3) | C21—C22 | 1.520 (4) |
C5—C6 | 1.393 (3) | C21—H21A | 0.97 |
C5—H5A | 0.93 | C21—H21B | 0.97 |
C6—C10 | 1.441 (3) | C22—H22A | 0.96 |
C7—C9 | 1.409 (3) | C22—H22B | 0.96 |
C7—C8 | 1.454 (3) | C22—H22C | 0.96 |
C8—C10 | 1.371 (3) | C23—C24 | 1.532 (4) |
C8—C17 | 1.496 (3) | C23—H23A | 0.97 |
C9—C1i | 1.403 (3) | C23—H23B | 0.97 |
C9—C11 | 1.497 (3) | C24—C25 | 1.531 (4) |
C10—C23 | 1.498 (3) | C24—H24A | 0.97 |
C11—C16 | 1.387 (4) | C24—H24B | 0.97 |
C11—C12 | 1.390 (4) | C25—C26 | 1.517 (4) |
C12—C13 | 1.389 (4) | C25—H25A | 0.97 |
C12—H12A | 0.93 | C25—H25B | 0.97 |
C13—C14 | 1.382 (4) | C26—H26A | 0.96 |
C13—H13A | 0.93 | C26—H26B | 0.96 |
C14—C15 | 1.380 (4) | C26—H26C | 0.96 |
C14—C27 | 1.513 (4) | C27—H27A | 0.96 |
C15—C16 | 1.391 (4) | C27—H27B | 0.96 |
C15—H15A | 0.93 | C27—H27C | 0.96 |
C16—H16A | 0.93 | | |
| | | |
C6—N1—C7 | 108.2 (2) | C4—C18—H18A | 109.5 |
C6—N1—H1A | 125.9 | C4—C18—H18B | 109.5 |
C7—N1—H1A | 125.9 | H18A—C18—H18B | 109.5 |
N2—C1—C9i | 123.1 (2) | C4—C18—H18C | 109.5 |
N2—C1—C4 | 108.8 (2) | H18A—C18—H18C | 109.5 |
C9i—C1—C4 | 128.0 (2) | H18B—C18—H18C | 109.5 |
C2—N2—C1 | 107.7 (2) | C3—C19—C20 | 112.8 (2) |
C2—N2—H2A | 126.2 | C3—C19—H19A | 109.0 |
C1—N2—H2A | 126.2 | C20—C19—H19A | 109.0 |
N2—C2—C5 | 127.6 (2) | C3—C19—H19B | 109.0 |
N2—C2—C3 | 109.4 (2) | C20—C19—H19B | 109.0 |
C5—C2—C3 | 123.0 (2) | H19A—C19—H19B | 107.8 |
C4—C3—C2 | 107.5 (2) | C21—C20—C19 | 114.4 (2) |
C4—C3—C19 | 127.7 (2) | C21—C20—H20A | 108.7 |
C2—C3—C19 | 124.7 (2) | C19—C20—H20A | 108.7 |
C3—C4—C1 | 106.5 (2) | C21—C20—H20B | 108.7 |
C3—C4—C18 | 125.0 (2) | C19—C20—H20B | 108.7 |
C1—C4—C18 | 128.5 (2) | H20A—C20—H20B | 107.6 |
C2—C5—C6 | 131.8 (2) | C22—C21—C20 | 113.1 (2) |
C2—C5—H5A | 114.1 | C22—C21—H21A | 109.0 |
C6—C5—H5A | 114.1 | C20—C21—H21A | 109.0 |
N1—C6—C5 | 127.0 (2) | C22—C21—H21B | 109.0 |
N1—C6—C10 | 108.8 (2) | C20—C21—H21B | 109.0 |
C5—C6—C10 | 124.2 (2) | H21A—C21—H21B | 107.8 |
N1—C7—C9 | 122.6 (2) | C21—C22—H22A | 109.5 |
N1—C7—C8 | 108.7 (2) | C21—C22—H22B | 109.5 |
C9—C7—C8 | 128.8 (2) | H22A—C22—H22B | 109.5 |
C10—C8—C7 | 106.5 (2) | C21—C22—H22C | 109.5 |
C10—C8—C17 | 124.8 (2) | H22A—C22—H22C | 109.5 |
C7—C8—C17 | 128.7 (2) | H22B—C22—H22C | 109.5 |
C1i—C9—C7 | 123.9 (2) | C10—C23—C24 | 113.3 (2) |
C1i—C9—C11 | 118.0 (2) | C10—C23—H23A | 108.9 |
C7—C9—C11 | 117.7 (2) | C24—C23—H23A | 108.9 |
C8—C10—C6 | 107.7 (2) | C10—C23—H23B | 108.9 |
C8—C10—C23 | 126.1 (2) | C24—C23—H23B | 108.9 |
C6—C10—C23 | 126.1 (2) | H23A—C23—H23B | 107.7 |
C16—C11—C12 | 118.1 (2) | C25—C24—C23 | 113.4 (2) |
C16—C11—C9 | 118.8 (2) | C25—C24—H24A | 108.9 |
C12—C11—C9 | 123.1 (2) | C23—C24—H24A | 108.9 |
C13—C12—C11 | 120.5 (3) | C25—C24—H24B | 108.9 |
C13—C12—H12A | 119.7 | C23—C24—H24B | 108.9 |
C11—C12—H12A | 119.7 | H24A—C24—H24B | 107.7 |
C14—C13—C12 | 121.1 (2) | C26—C25—C24 | 112.5 (2) |
C14—C13—H13A | 119.4 | C26—C25—H25A | 109.1 |
C12—C13—H13A | 119.4 | C24—C25—H25A | 109.1 |
C15—C14—C13 | 118.6 (2) | C26—C25—H25B | 109.1 |
C15—C14—C27 | 120.1 (3) | C24—C25—H25B | 109.1 |
C13—C14—C27 | 121.3 (3) | H25A—C25—H25B | 107.8 |
C14—C15—C16 | 120.6 (3) | C25—C26—H26A | 109.5 |
C14—C15—H15A | 119.7 | C25—C26—H26B | 109.5 |
C16—C15—H15A | 119.7 | H26A—C26—H26B | 109.5 |
C11—C16—C15 | 121.0 (3) | C25—C26—H26C | 109.5 |
C11—C16—H16A | 119.5 | H26A—C26—H26C | 109.5 |
C15—C16—H16A | 119.5 | H26B—C26—H26C | 109.5 |
C8—C17—H17A | 109.5 | C14—C27—H27A | 109.5 |
C8—C17—H17B | 109.5 | C14—C27—H27B | 109.5 |
H17A—C17—H17B | 109.5 | H27A—C27—H27B | 109.5 |
C8—C17—H17C | 109.5 | C14—C27—H27C | 109.5 |
H17A—C17—H17C | 109.5 | H27A—C27—H27C | 109.5 |
H17B—C17—H17C | 109.5 | H27B—C27—H27C | 109.5 |
Symmetry code: (i) −x, −y, −z. |