Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045953/pv2028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045953/pv2028Isup2.hkl |
CCDC reference: 299597
Key indicators
- Single-crystal X-ray study
- T = 85 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.046
- wR factor = 0.122
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT413_ALERT_2_B Short Inter XH3 .. XHn H24C .. H34C .. 2.08 Ang.
Alert level C PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C34 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 30.00 Perc. PLAT413_ALERT_2_C Short Inter XH3 .. XHn H26C .. H34B .. 2.14 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 93
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrinato zinc(II) was synthesized according to a typical procedure (Mele et al., 2003), applying ZnCl2 as the metal source. Pure monocrystals for X-ray diffraction measurements were obtained by multiple re-crystallization from toluene (reagent grade) at room temperature, yielding the final product in the form of a toluene solvate.
The hydrogen atoms were included in the refinement at geometrically idealized positions with C—H distances 0.96 Å for methyl and toluene solvate and 0.93 Å for the rest of the hydrogen atoms and Ueq = 1.5 and 1.2 times Ueq of the parent atoms, respectively. The toluene solvate was lying about inversion centers and was disordered.
Physicochemical properties of metallo-porphyrins depend on the complexed metal and the kind of peripherally and/or axially fixed substituents. These factors influence the electronic density distribution within the core of the macrocycle, thus determining both its stability and reactivity (Berezin, 1981). Therefore, structural details are essential in learning the basic chemistry of such compounds featuring unique properties, e.g. photocatalytic activity (Mele et al., 2007). 5,10,15,20-Tetrakis(4-tert-butylphenyl)porphyrinato zinc(II) (ZnPp), when crystallized from a toluene solution yielded a typical lattice clathrate with ZnPp (host) to toluene (guest) 1:1 stoichiometry. The structure of the title tert-butylphenyl meso-substituted ZnPp derivative has been solved and reported for the first time in this work.
The crystal lattice consists of discrete centrosymmetrical molecules of ZnPp (Fig. 1) and disordered molecules of toluene, located at the inversion centre. This is a typical case of toluene disorder exhibiting two discrete positions; one molecule is staggered 180° with respect to the other one. The zinc atom is found in a plane defined by the four pyrrole-nitrogen atoms and the N—Zn—N bond angles are ca 90°, showing ideal square-planar coordination. The macrocycle itself shows no apparent distortion and one may consider it as "perfectly flat". The meso substituted benzene rings are not perpendicular to the plane of the macrocycle, yielding dihedral angles of 78.44 (7)° and 79.17 (7)°. The geometry of the porphyrin core proved typical as for the family of similar zinc porphyrins substituted in their meso position by four identical phenyl derivatives (Allen, 2002). The unit cell packing of the title compound is shown in Fig. 2.
For related literature, see: Berezin (1981); Mele et al. (2003, 2007); Allen (2002).
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Zn(C60H60N4)]·C7H8 | F(000) = 1056 |
Mr = 994.64 | Dx = 1.277 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4533 reflections |
a = 16.0277 (16) Å | θ = 3.2–25.0° |
b = 9.5884 (14) Å | µ = 0.52 mm−1 |
c = 16.8714 (16) Å | T = 85 K |
β = 93.892 (8)° | Plate, colourless |
V = 2586.8 (5) Å3 | 0.25 × 0.20 × 0.10 mm |
Z = 2 |
Oxford Diffraction Xcalibur diffractometer | 3375 reflections with I > 2σ(I) |
Radiation source: Enhanced (Mo) X-ray Source | Rint = 0.060 |
Graphite monochromator | θmax = 25.0°, θmin = 3.2° |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | h = −18→19 |
ω scans | k = −7→11 |
14020 measured reflections | l = −20→19 |
4533 independent reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters not refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0778P)2 + 0.1154P] where P = (Fo2 + 2Fc2)/3 |
4533 reflections | (Δ/σ)max < 0.001 |
341 parameters | Δρmax = 0.42 e Å−3 |
93 restraints | Δρmin = −0.37 e Å−3 |
[Zn(C60H60N4)]·C7H8 | V = 2586.8 (5) Å3 |
Mr = 994.64 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.0277 (16) Å | µ = 0.52 mm−1 |
b = 9.5884 (14) Å | T = 85 K |
c = 16.8714 (16) Å | 0.25 × 0.20 × 0.10 mm |
β = 93.892 (8)° |
Oxford Diffraction Xcalibur diffractometer | 3375 reflections with I > 2σ(I) |
14020 measured reflections | Rint = 0.060 |
4533 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 93 restraints |
wR(F2) = 0.122 | H-atom parameters not refined |
S = 1.05 | Δρmax = 0.42 e Å−3 |
4533 reflections | Δρmin = −0.37 e Å−3 |
341 parameters |
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) | |
Zn1 | 0.5000 | 0.5000 | 0.5000 | 0.01341 (15) | |
N1 | 0.62401 (12) | 0.5020 (2) | 0.47623 (12) | 0.0138 (4) | |
N2 | 0.46708 (13) | 0.5079 (2) | 0.38213 (12) | 0.0140 (5) | |
C1 | 0.69152 (15) | 0.5006 (3) | 0.53100 (15) | 0.0132 (5) | |
C2 | 0.76805 (15) | 0.5049 (3) | 0.49013 (15) | 0.0141 (5) | |
H2A | 0.8222 | 0.5045 | 0.5136 | 0.017* | |
C3 | 0.74594 (15) | 0.5094 (3) | 0.41128 (16) | 0.0155 (5) | |
H3A | 0.7821 | 0.5131 | 0.3704 | 0.019* | |
C4 | 0.65585 (15) | 0.5073 (3) | 0.40256 (15) | 0.0132 (5) | |
C5 | 0.60800 (15) | 0.5118 (2) | 0.32961 (15) | 0.0134 (5) | |
C6 | 0.52031 (15) | 0.5115 (2) | 0.32132 (15) | 0.0134 (5) | |
C7 | 0.47170 (16) | 0.5157 (3) | 0.24613 (15) | 0.0150 (5) | |
H7A | 0.4924 | 0.5188 | 0.1960 | 0.018* | |
C8 | 0.39000 (16) | 0.5143 (3) | 0.26257 (15) | 0.0158 (6) | |
H8A | 0.3442 | 0.5167 | 0.2257 | 0.019* | |
C9 | 0.38730 (15) | 0.5085 (2) | 0.34701 (15) | 0.0126 (5) | |
C10 | 0.31249 (15) | 0.5036 (3) | 0.38640 (15) | 0.0132 (5) | |
C11 | 0.65151 (15) | 0.5163 (3) | 0.25357 (15) | 0.0144 (5) | |
C12 | 0.68218 (15) | 0.3966 (3) | 0.21983 (16) | 0.0185 (6) | |
H12A | 0.6849 | 0.3143 | 0.2490 | 0.022* | |
C13 | 0.70888 (16) | 0.3972 (3) | 0.14360 (16) | 0.0179 (6) | |
H13A | 0.7290 | 0.3150 | 0.1226 | 0.021* | |
C14 | 0.70640 (15) | 0.5172 (3) | 0.09771 (15) | 0.0161 (6) | |
C15 | 0.68138 (16) | 0.6404 (3) | 0.13437 (15) | 0.0187 (6) | |
H15A | 0.6832 | 0.7244 | 0.1070 | 0.022* | |
C16 | 0.65410 (16) | 0.6393 (3) | 0.21022 (16) | 0.0199 (6) | |
H16A | 0.6372 | 0.7223 | 0.2327 | 0.024* | |
C17 | 0.23273 (15) | 0.5053 (3) | 0.33498 (14) | 0.0136 (5) | |
C18 | 0.20367 (16) | 0.3871 (3) | 0.29459 (16) | 0.0194 (6) | |
H18A | 0.2318 | 0.3030 | 0.3031 | 0.023* | |
C19 | 0.13317 (16) | 0.3916 (3) | 0.24153 (16) | 0.0200 (6) | |
H19A | 0.1156 | 0.3108 | 0.2149 | 0.024* | |
C20 | 0.08848 (15) | 0.5146 (3) | 0.22766 (15) | 0.0152 (5) | |
C21 | 0.11813 (16) | 0.6330 (3) | 0.26884 (16) | 0.0202 (6) | |
H21A | 0.0900 | 0.7172 | 0.2607 | 0.024* | |
C22 | 0.18838 (16) | 0.6282 (3) | 0.32149 (16) | 0.0202 (6) | |
H22A | 0.2061 | 0.7089 | 0.3482 | 0.024* | |
C23 | 0.72525 (16) | 0.5201 (3) | 0.00997 (15) | 0.0169 (6) | |
C24 | 0.74775 (18) | 0.3764 (3) | −0.02088 (17) | 0.0249 (7) | |
H24A | 0.7967 | 0.3423 | 0.0089 | 0.037* | |
H24B | 0.7587 | 0.3831 | −0.0760 | 0.037* | |
H24C | 0.7020 | 0.3134 | −0.0149 | 0.037* | |
C25 | 0.79766 (17) | 0.6211 (3) | −0.00308 (16) | 0.0224 (6) | |
H25A | 0.8472 | 0.5898 | 0.0268 | 0.034* | |
H25B | 0.7833 | 0.7128 | 0.0143 | 0.034* | |
H25C | 0.8077 | 0.6238 | −0.0585 | 0.034* | |
C26 | 0.64640 (17) | 0.5725 (3) | −0.03894 (16) | 0.0245 (7) | |
H26A | 0.6006 | 0.5103 | −0.0316 | 0.037* | |
H26B | 0.6572 | 0.5755 | −0.0942 | 0.037* | |
H26C | 0.6324 | 0.6643 | −0.0214 | 0.037* | |
C27 | 0.01147 (16) | 0.5261 (3) | 0.16840 (16) | 0.0183 (6) | |
C28 | −0.01266 (18) | 0.3852 (3) | 0.13143 (17) | 0.0258 (7) | |
H28A | −0.0257 | 0.3211 | 0.1725 | 0.039* | |
H28B | 0.0332 | 0.3494 | 0.1038 | 0.039* | |
H28C | −0.0607 | 0.3964 | 0.0948 | 0.039* | |
C29 | 0.03216 (18) | 0.6284 (3) | 0.10215 (17) | 0.0253 (7) | |
H29A | −0.0153 | 0.6368 | 0.0646 | 0.038* | |
H29B | 0.0792 | 0.5939 | 0.0757 | 0.038* | |
H29C | 0.0455 | 0.7180 | 0.1249 | 0.038* | |
C30 | −0.06321 (17) | 0.5829 (4) | 0.21073 (18) | 0.0303 (7) | |
H30A | −0.0765 | 0.5197 | 0.2522 | 0.045* | |
H30B | −0.1107 | 0.5921 | 0.1732 | 0.045* | |
H30C | −0.0492 | 0.6725 | 0.2333 | 0.045* | |
C31 | 0.9921 (2) | 0.5396 (5) | 0.4346 (2) | 0.0522 (10) | |
H31 | 0.9935 | 0.5212 | 0.3788 | 0.063* | |
C32 | 0.9924 (4) | 0.5772 (9) | 0.5186 (4) | 0.0404 (15) | 0.50 |
C33 | 0.9924 (4) | 0.5879 (8) | 0.5862 (4) | 0.0391 (16) | 0.50 |
H33 | 0.9930 | 0.6022 | 0.6426 | 0.047* | 0.50 |
C34 | 0.9744 (2) | 0.7095 (5) | 0.5393 (3) | 0.0689 (12) | |
H34A | 0.9773 | 0.7163 | 0.5962 | 0.103* | 0.50 |
H34B | 1.0141 | 0.7724 | 0.5186 | 0.103* | 0.50 |
H34C | 0.9191 | 0.7334 | 0.5184 | 0.103* | 0.50 |
H34 | 0.9632 | 0.8016 | 0.5582 | 0.083* | 0.50 |
C35 | 0.9769 (4) | 0.6616 (10) | 0.4494 (5) | 0.0597 (19) | 0.50 |
H35 | 0.9667 | 0.7277 | 0.4072 | 0.072* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0123 (2) | 0.0152 (2) | 0.0127 (2) | 0.00000 (17) | 0.00079 (15) | 0.00060 (18) |
N1 | 0.0152 (11) | 0.0134 (11) | 0.0128 (11) | 0.0002 (9) | −0.0001 (8) | 0.0003 (9) |
N2 | 0.0113 (10) | 0.0149 (11) | 0.0159 (11) | 0.0009 (9) | 0.0011 (8) | 0.0009 (9) |
C1 | 0.0151 (12) | 0.0092 (12) | 0.0153 (13) | −0.0010 (10) | 0.0014 (10) | 0.0022 (11) |
C2 | 0.0100 (12) | 0.0140 (13) | 0.0181 (13) | −0.0007 (10) | −0.0005 (10) | 0.0005 (11) |
C3 | 0.0141 (12) | 0.0137 (13) | 0.0190 (14) | 0.0005 (11) | 0.0046 (10) | 0.0003 (11) |
C4 | 0.0133 (12) | 0.0111 (12) | 0.0154 (13) | 0.0003 (10) | 0.0022 (10) | 0.0001 (11) |
C5 | 0.0163 (13) | 0.0078 (12) | 0.0162 (13) | 0.0002 (10) | 0.0002 (10) | −0.0003 (11) |
C6 | 0.0173 (13) | 0.0092 (12) | 0.0136 (13) | −0.0015 (10) | 0.0010 (10) | −0.0011 (11) |
C7 | 0.0177 (13) | 0.0161 (13) | 0.0113 (13) | −0.0021 (11) | 0.0020 (10) | 0.0008 (11) |
C8 | 0.0156 (13) | 0.0174 (14) | 0.0137 (13) | 0.0019 (11) | −0.0037 (10) | −0.0011 (11) |
C9 | 0.0158 (13) | 0.0070 (12) | 0.0146 (13) | 0.0000 (10) | −0.0019 (10) | −0.0015 (11) |
C10 | 0.0149 (12) | 0.0089 (12) | 0.0156 (13) | −0.0005 (10) | −0.0007 (10) | −0.0013 (11) |
C11 | 0.0109 (12) | 0.0188 (14) | 0.0130 (13) | −0.0024 (10) | −0.0018 (9) | −0.0014 (11) |
C12 | 0.0156 (13) | 0.0185 (14) | 0.0214 (15) | 0.0052 (11) | 0.0018 (11) | 0.0049 (12) |
C13 | 0.0185 (14) | 0.0154 (14) | 0.0202 (14) | 0.0033 (11) | 0.0046 (11) | 0.0001 (11) |
C14 | 0.0106 (12) | 0.0207 (14) | 0.0167 (13) | −0.0010 (11) | −0.0019 (10) | −0.0012 (12) |
C15 | 0.0217 (14) | 0.0147 (14) | 0.0199 (15) | −0.0017 (11) | 0.0032 (11) | 0.0016 (12) |
C16 | 0.0210 (14) | 0.0164 (14) | 0.0226 (15) | −0.0022 (11) | 0.0039 (11) | −0.0037 (12) |
C17 | 0.0130 (12) | 0.0160 (13) | 0.0120 (12) | −0.0005 (11) | 0.0035 (10) | 0.0011 (11) |
C18 | 0.0208 (14) | 0.0144 (14) | 0.0223 (15) | 0.0036 (11) | −0.0041 (11) | −0.0003 (12) |
C19 | 0.0227 (15) | 0.0151 (14) | 0.0213 (15) | −0.0020 (11) | −0.0049 (11) | −0.0040 (12) |
C20 | 0.0125 (12) | 0.0185 (14) | 0.0146 (13) | −0.0016 (11) | 0.0002 (10) | 0.0022 (11) |
C21 | 0.0200 (14) | 0.0153 (14) | 0.0248 (15) | 0.0043 (11) | −0.0033 (11) | 0.0039 (12) |
C22 | 0.0169 (14) | 0.0165 (14) | 0.0266 (16) | −0.0017 (11) | −0.0037 (11) | −0.0030 (12) |
C23 | 0.0163 (13) | 0.0180 (14) | 0.0163 (14) | 0.0013 (11) | 0.0011 (10) | 0.0007 (11) |
C24 | 0.0306 (16) | 0.0256 (16) | 0.0192 (15) | 0.0001 (13) | 0.0067 (12) | −0.0024 (13) |
C25 | 0.0220 (15) | 0.0262 (16) | 0.0196 (15) | −0.0001 (12) | 0.0054 (11) | 0.0011 (13) |
C26 | 0.0236 (15) | 0.0333 (17) | 0.0160 (15) | 0.0008 (13) | −0.0016 (11) | −0.0021 (13) |
C27 | 0.0147 (13) | 0.0233 (15) | 0.0165 (14) | 0.0010 (11) | −0.0023 (10) | −0.0013 (11) |
C28 | 0.0249 (15) | 0.0256 (16) | 0.0253 (16) | −0.0056 (12) | −0.0094 (12) | 0.0000 (13) |
C29 | 0.0240 (15) | 0.0263 (16) | 0.0245 (16) | −0.0014 (13) | −0.0048 (12) | 0.0062 (13) |
C30 | 0.0159 (15) | 0.048 (2) | 0.0259 (17) | 0.0046 (14) | −0.0048 (12) | −0.0033 (15) |
C31 | 0.0228 (18) | 0.096 (3) | 0.038 (2) | −0.014 (2) | −0.0018 (15) | 0.016 (2) |
C32 | 0.013 (3) | 0.072 (4) | 0.035 (3) | −0.013 (3) | 0.002 (3) | −0.001 (3) |
C33 | 0.022 (3) | 0.062 (4) | 0.033 (3) | −0.012 (3) | 0.001 (3) | −0.001 (3) |
C34 | 0.0255 (19) | 0.086 (3) | 0.095 (3) | −0.011 (2) | 0.003 (2) | 0.004 (2) |
C35 | 0.031 (4) | 0.071 (4) | 0.075 (4) | −0.017 (4) | −0.011 (3) | 0.044 (4) |
Zn1—N2 | 2.024 (2) | C21—H21A | 0.9300 |
Zn1—N1 | 2.054 (2) | C22—H22A | 0.9300 |
N1—C1 | 1.374 (3) | C23—C24 | 1.525 (4) |
N1—C4 | 1.376 (3) | C23—C25 | 1.539 (4) |
N1—N2 | 2.882 (3) | C23—C26 | 1.546 (4) |
N2—C9 | 1.372 (3) | C24—H24A | 0.9600 |
N2—C6 | 1.379 (3) | C24—H24B | 0.9600 |
C1—C10i | 1.400 (4) | C24—H24C | 0.9600 |
C1—C2 | 1.448 (3) | C25—H25A | 0.9600 |
C2—C3 | 1.354 (4) | C25—H25B | 0.9600 |
C2—H2A | 0.9300 | C25—H25C | 0.9600 |
C3—C4 | 1.442 (3) | C26—H26A | 0.9600 |
C3—H3A | 0.9300 | C26—H26B | 0.9600 |
C4—C5 | 1.406 (4) | C26—H26C | 0.9600 |
C5—C6 | 1.403 (4) | C27—C28 | 1.527 (4) |
C5—C11 | 1.502 (3) | C27—C30 | 1.535 (4) |
C6—C7 | 1.444 (3) | C27—C29 | 1.540 (4) |
C7—C8 | 1.357 (4) | C28—H28A | 0.9600 |
C7—H7A | 0.9300 | C28—H28B | 0.9600 |
C8—C9 | 1.429 (3) | C28—H28C | 0.9600 |
C8—H8A | 0.9300 | C29—H29A | 0.9600 |
C9—C10 | 1.411 (3) | C29—H29B | 0.9600 |
C10—C1i | 1.400 (4) | C29—H29C | 0.9600 |
C10—C17 | 1.496 (3) | C30—H30A | 0.9600 |
C11—C12 | 1.386 (4) | C30—H30B | 0.9600 |
C11—C16 | 1.390 (4) | C30—H30C | 0.9600 |
C12—C13 | 1.383 (4) | C31—C35 | 1.224 (10) |
C12—H12A | 0.9300 | C31—C33ii | 1.300 (9) |
C13—C14 | 1.386 (4) | C31—C32ii | 1.383 (9) |
C13—H13A | 0.9300 | C31—C32 | 1.461 (8) |
C14—C15 | 1.404 (4) | C31—H31 | 0.9601 |
C14—C23 | 1.531 (4) | C32—C33 | 1.146 (9) |
C15—C16 | 1.380 (4) | C32—C34 | 1.352 (9) |
C15—H15A | 0.9300 | C32—C31ii | 1.383 (9) |
C16—H16A | 0.9300 | C32—C35 | 1.427 (11) |
C17—C18 | 1.386 (4) | C33—C31ii | 1.300 (9) |
C17—C22 | 1.387 (4) | C33—C34 | 1.428 (9) |
C18—C19 | 1.394 (4) | C33—H33 | 0.9600 |
C18—H18A | 0.9300 | C34—C35 | 1.588 (11) |
C19—C20 | 1.392 (4) | C34—H34A | 0.9600 |
C19—H19A | 0.9300 | C34—H34B | 0.9600 |
C20—C21 | 1.397 (4) | C34—H34C | 0.9600 |
C20—C27 | 1.539 (3) | C34—H34 | 0.9600 |
C21—C22 | 1.387 (4) | C35—H35 | 0.9599 |
N2—Zn1—N2i | 180 | C23—C25—H25A | 109.5 |
N2—Zn1—N1i | 90.06 (8) | C23—C25—H25B | 109.5 |
N2i—Zn1—N1i | 89.94 (8) | H25A—C25—H25B | 109.5 |
N2—Zn1—N1 | 89.94 (8) | C23—C25—H25C | 109.5 |
N2i—Zn1—N1 | 90.06 (8) | H25A—C25—H25C | 109.5 |
N1i—Zn1—N1 | 180.000 (1) | H25B—C25—H25C | 109.5 |
C1—N1—C4 | 106.52 (19) | C23—C26—H26A | 109.5 |
C1—N1—Zn1 | 126.63 (16) | C23—C26—H26B | 109.5 |
C4—N1—Zn1 | 126.84 (16) | H26A—C26—H26B | 109.5 |
C1—N1—N2 | 171.20 (17) | C23—C26—H26C | 109.5 |
C4—N1—N2 | 82.24 (14) | H26A—C26—H26C | 109.5 |
C9—N2—C6 | 106.5 (2) | H26B—C26—H26C | 109.5 |
C9—N2—Zn1 | 126.69 (17) | C28—C27—C30 | 108.7 (2) |
C6—N2—Zn1 | 126.79 (17) | C28—C27—C29 | 109.1 (2) |
C9—N2—N1 | 172.12 (17) | C30—C27—C29 | 109.0 (2) |
C6—N2—N1 | 81.34 (14) | C28—C27—C20 | 111.8 (2) |
Zn1—N2—N1 | 45.45 (6) | C30—C27—C20 | 109.9 (2) |
C6—N2—N1iii | 134.36 (14) | C29—C27—C20 | 108.3 (2) |
Zn1—N2—N1iii | 96.26 (6) | C27—C28—H28A | 109.5 |
N1—N2—N1iii | 139.30 (6) | C27—C28—H28B | 109.5 |
N1—C1—C10i | 125.6 (2) | H28A—C28—H28B | 109.5 |
N1—C1—C2 | 109.5 (2) | C27—C28—H28C | 109.5 |
C10i—C1—C2 | 124.9 (2) | H28A—C28—H28C | 109.5 |
C3—C2—C1 | 107.2 (2) | H28B—C28—H28C | 109.5 |
C3—C2—H2A | 126.4 | C27—C29—H29A | 109.5 |
C1—C2—H2A | 126.4 | C27—C29—H29B | 109.5 |
C2—C3—C4 | 107.1 (2) | H29A—C29—H29B | 109.5 |
C2—C3—H3A | 126.5 | C27—C29—H29C | 109.5 |
C4—C3—H3A | 126.5 | H29A—C29—H29C | 109.5 |
N1—C4—C5 | 125.3 (2) | H29B—C29—H29C | 109.5 |
N1—C4—C3 | 109.8 (2) | C27—C30—H30A | 109.5 |
C5—C4—C3 | 124.9 (2) | C27—C30—H30B | 109.5 |
C6—C5—C4 | 124.8 (2) | H30A—C30—H30B | 109.5 |
C6—C5—C11 | 115.8 (2) | C27—C30—H30C | 109.5 |
C4—C5—C11 | 119.4 (2) | H30A—C30—H30C | 109.5 |
N2—C6—C5 | 126.3 (2) | H30B—C30—H30C | 109.5 |
N2—C6—C7 | 109.3 (2) | C35—C31—C33ii | 176.1 (6) |
C5—C6—C7 | 124.4 (2) | C35—C31—C32ii | 133.5 (6) |
C8—C7—C6 | 106.9 (2) | C33ii—C31—C32ii | 50.5 (4) |
C8—C7—H7A | 126.5 | C35—C31—C32 | 63.5 (6) |
C6—C7—H7A | 126.5 | C33ii—C31—C32 | 120.4 (6) |
C7—C8—C9 | 107.4 (2) | C32ii—C31—C32 | 70.0 (6) |
C7—C8—H8A | 126.3 | C35—C31—H31 | 113.2 |
C9—C8—H8A | 126.3 | C33ii—C31—H31 | 62.9 |
N2—C9—C10 | 126.4 (2) | C32ii—C31—H31 | 113.3 |
N2—C9—C8 | 109.9 (2) | C32—C31—H31 | 175.9 |
C10—C9—C8 | 123.7 (2) | C33—C32—C34 | 69.1 (6) |
C1i—C10—C9 | 124.6 (2) | C33—C32—C31ii | 61.0 (6) |
C1i—C10—C17 | 118.8 (2) | C34—C32—C31ii | 130.2 (6) |
C9—C10—C17 | 116.5 (2) | C33—C32—C35 | 138.8 (9) |
C12—C11—C16 | 117.6 (2) | C34—C32—C35 | 69.6 (6) |
C12—C11—C5 | 121.7 (2) | C31ii—C32—C35 | 160.0 (8) |
C16—C11—C5 | 120.4 (2) | C33—C32—C31 | 170.8 (9) |
C11—C12—C13 | 121.3 (2) | C34—C32—C31 | 119.7 (6) |
C11—C12—H12A | 119.4 | C31ii—C32—C31 | 110.0 (6) |
C13—C12—H12A | 119.4 | C35—C32—C31 | 50.1 (5) |
C12—C13—C14 | 121.6 (2) | C33—C32—C32ii | 118.2 (9) |
C12—C13—H13A | 119.2 | C34—C32—C32ii | 172.0 (8) |
C14—C13—H13A | 119.2 | C31ii—C32—C32ii | 57.2 (5) |
C13—C14—C15 | 116.8 (2) | C35—C32—C32ii | 102.9 (8) |
C13—C14—C23 | 123.7 (2) | C31—C32—C32ii | 52.7 (4) |
C15—C14—C23 | 119.4 (2) | C32—C33—C31ii | 68.5 (6) |
C16—C15—C14 | 121.3 (2) | C32—C33—C34 | 62.2 (6) |
C16—C15—H15A | 119.3 | C31ii—C33—C34 | 130.7 (6) |
C14—C15—H15A | 119.3 | C32—C33—H33 | 176.9 |
C15—C16—C11 | 121.1 (2) | C31ii—C33—H33 | 114.4 |
C15—C16—H16A | 119.4 | C34—C33—H33 | 114.8 |
C11—C16—H16A | 119.4 | C32—C33—H34A | 103.4 |
C18—C17—C22 | 117.5 (2) | C31ii—C33—H34A | 171.9 |
C18—C17—C10 | 121.4 (2) | H33—C33—H34A | 73.7 |
C22—C17—C10 | 120.9 (2) | C32—C34—C33 | 48.6 (4) |
C17—C18—C19 | 121.4 (2) | C32—C34—C35 | 57.4 (5) |
C17—C18—H18A | 119.3 | C33—C34—C35 | 106.0 (5) |
C19—C18—H18A | 119.3 | C32—C34—H34A | 109.0 |
C20—C19—C18 | 121.3 (2) | C33—C34—H34A | 60.5 |
C20—C19—H19A | 119.3 | C35—C34—H34A | 166.4 |
C18—C19—H19A | 119.3 | C32—C34—H34B | 109.7 |
C19—C20—C21 | 116.8 (2) | C33—C34—H34B | 127.0 |
C19—C20—C27 | 123.4 (2) | C35—C34—H34B | 76.9 |
C21—C20—C27 | 119.7 (2) | H34A—C34—H34B | 109.5 |
C22—C21—C20 | 121.7 (2) | C32—C34—H34C | 109.7 |
C22—C21—H21A | 119.1 | C33—C34—H34C | 123.1 |
C20—C21—H21A | 119.1 | C35—C34—H34C | 78.4 |
C17—C22—C21 | 121.2 (2) | H34A—C34—H34C | 109.5 |
C17—C22—H22A | 119.4 | H34B—C34—H34C | 109.5 |
C21—C22—H22A | 119.4 | C32—C34—H34 | 175.5 |
C24—C23—C14 | 112.4 (2) | C33—C34—H34 | 127.0 |
C24—C23—C25 | 108.8 (2) | C35—C34—H34 | 126.9 |
C14—C23—C25 | 110.5 (2) | H34A—C34—H34 | 66.6 |
C24—C23—C26 | 108.4 (2) | H34B—C34—H34 | 71.8 |
C14—C23—C26 | 108.3 (2) | H34C—C34—H34 | 73.3 |
C25—C23—C26 | 108.4 (2) | C31—C35—C32 | 66.4 (5) |
C23—C24—H24A | 109.5 | C31—C35—C34 | 119.3 (6) |
C23—C24—H24B | 109.5 | C32—C35—C34 | 52.9 (5) |
H24A—C24—H24B | 109.5 | C31—C35—H35 | 120.4 |
C23—C24—H24C | 109.5 | C32—C35—H35 | 173.1 |
H24A—C24—H24C | 109.5 | C34—C35—H35 | 120.3 |
H24B—C24—H24C | 109.5 | ||
N2—Zn1—N1—C1 | 178.9 (2) | C12—C13—C14—C23 | −172.5 (2) |
N2i—Zn1—N1—C1 | −1.1 (2) | C13—C14—C15—C16 | −5.1 (4) |
N2—Zn1—N1—C4 | 0.1 (2) | C23—C14—C15—C16 | 172.1 (2) |
N2i—Zn1—N1—C4 | −179.9 (2) | C14—C15—C16—C11 | 0.9 (4) |
N2i—Zn1—N1—N2 | 180.0 | C12—C11—C16—C15 | 3.9 (4) |
N1i—Zn1—N2—C9 | −0.8 (2) | C5—C11—C16—C15 | −169.3 (2) |
N1—Zn1—N2—C9 | 179.2 (2) | C1i—C10—C17—C18 | −103.8 (3) |
N1i—Zn1—N2—C6 | −179.6 (2) | C9—C10—C17—C18 | 77.2 (3) |
N1—Zn1—N2—C6 | 0.4 (2) | C1i—C10—C17—C22 | 81.0 (3) |
N1i—Zn1—N2—N1 | 180.0 | C9—C10—C17—C22 | −98.0 (3) |
N1i—Zn1—N2—N1iii | −15.84 (6) | C22—C17—C18—C19 | 0.8 (4) |
N1—Zn1—N2—N1iii | 164.16 (6) | C10—C17—C18—C19 | −174.5 (2) |
C4—N1—N2—C6 | 0.37 (18) | C17—C18—C19—C20 | −0.8 (4) |
Zn1—N1—N2—C6 | −179.72 (16) | C18—C19—C20—C21 | 0.5 (4) |
C4—N1—N2—Zn1 | −179.92 (16) | C18—C19—C20—C27 | 178.6 (2) |
C4—N1—N2—N1iii | 155.51 (13) | C19—C20—C21—C22 | −0.4 (4) |
Zn1—N1—N2—N1iii | −24.58 (8) | C27—C20—C21—C22 | −178.6 (2) |
C4—N1—C1—C10i | 179.6 (2) | C18—C17—C22—C21 | −0.7 (4) |
Zn1—N1—C1—C10i | 0.6 (4) | C10—C17—C22—C21 | 174.7 (2) |
C4—N1—C1—C2 | −0.2 (3) | C20—C21—C22—C17 | 0.5 (4) |
Zn1—N1—C1—C2 | −179.16 (16) | C13—C14—C23—C24 | −0.5 (3) |
N1—C1—C2—C3 | 0.3 (3) | C15—C14—C23—C24 | −177.5 (2) |
C10i—C1—C2—C3 | −179.5 (2) | C13—C14—C23—C25 | −122.2 (3) |
C1—C2—C3—C4 | −0.3 (3) | C15—C14—C23—C25 | 60.8 (3) |
C1—N1—C4—C5 | −179.3 (2) | C13—C14—C23—C26 | 119.2 (3) |
Zn1—N1—C4—C5 | −0.3 (4) | C15—C14—C23—C26 | −57.8 (3) |
N2—N1—C4—C5 | −0.2 (2) | C19—C20—C27—C28 | 3.7 (4) |
C1—N1—C4—C3 | 0.0 (3) | C21—C20—C27—C28 | −178.3 (2) |
Zn1—N1—C4—C3 | 178.98 (15) | C19—C20—C27—C30 | 124.5 (3) |
N2—N1—C4—C3 | 179.06 (19) | C21—C20—C27—C30 | −57.5 (3) |
C2—C3—C4—N1 | 0.2 (3) | C19—C20—C27—C29 | −116.6 (3) |
C2—C3—C4—C5 | 179.4 (2) | C21—C20—C27—C29 | 61.4 (3) |
N1—C4—C5—C6 | 0.0 (4) | C35—C31—C32—C34 | 1.4 (6) |
C3—C4—C5—C6 | −179.2 (2) | C33ii—C31—C32—C34 | −178.6 (5) |
N1—C4—C5—C11 | −179.5 (2) | C32ii—C31—C32—C34 | −176.6 (8) |
C3—C4—C5—C11 | 1.3 (4) | C35—C31—C32—C31ii | 178.1 (6) |
C9—N2—C6—C5 | −179.8 (2) | C33ii—C31—C32—C31ii | −2.0 (6) |
Zn1—N2—C6—C5 | −0.7 (4) | C32ii—C31—C32—C31ii | 0.0 |
N1—N2—C6—C5 | −0.5 (2) | C33ii—C31—C32—C35 | 180.0 (6) |
N1iii—N2—C6—C5 | −157.91 (17) | C32ii—C31—C32—C35 | −178.1 (6) |
C9—N2—C6—C7 | 0.5 (3) | C35—C31—C32—C32ii | 178.1 (6) |
Zn1—N2—C6—C7 | 179.57 (16) | C33ii—C31—C32—C32ii | −2.0 (6) |
N1—N2—C6—C7 | 179.82 (19) | C34—C32—C33—C31ii | 178.7 (4) |
N1iii—N2—C6—C7 | 22.4 (3) | C35—C32—C33—C31ii | 176.6 (9) |
C4—C5—C6—N2 | 0.6 (4) | C32ii—C32—C33—C31ii | 2.1 (6) |
C11—C5—C6—N2 | −179.9 (2) | C31ii—C32—C33—C34 | −178.7 (4) |
C4—C5—C6—C7 | −179.8 (2) | C35—C32—C33—C34 | −2.0 (8) |
C11—C5—C6—C7 | −0.3 (4) | C32ii—C32—C33—C34 | −176.6 (8) |
N2—C6—C7—C8 | −0.1 (3) | C31ii—C32—C34—C33 | 1.5 (5) |
C5—C6—C7—C8 | −179.8 (2) | C35—C32—C34—C33 | 178.6 (6) |
C6—C7—C8—C9 | −0.3 (3) | C31—C32—C34—C33 | 177.4 (7) |
C6—N2—C9—C10 | 179.0 (2) | C33—C32—C34—C35 | −178.6 (6) |
Zn1—N2—C9—C10 | 0.0 (3) | C31ii—C32—C34—C35 | −177.0 (8) |
N1iii—N2—C9—C10 | 27.91 (17) | C31—C32—C34—C35 | −1.2 (5) |
C6—N2—C9—C8 | −0.7 (3) | C31ii—C33—C34—C32 | −1.6 (6) |
Zn1—N2—C9—C8 | −179.78 (16) | C32—C33—C34—C35 | 1.3 (5) |
N1iii—N2—C9—C8 | −151.8 (3) | C31ii—C33—C34—C35 | −0.4 (8) |
C7—C8—C9—N2 | 0.7 (3) | C32ii—C31—C35—C32 | 2.5 (8) |
C7—C8—C9—C10 | −179.1 (2) | C32ii—C31—C35—C34 | 1.3 (10) |
N2—C9—C10—C1i | 1.0 (4) | C32—C31—C35—C34 | −1.2 (5) |
C8—C9—C10—C1i | −179.3 (2) | C33—C32—C35—C31 | −176.6 (9) |
N2—C9—C10—C17 | −180.0 (2) | C34—C32—C35—C31 | −178.7 (5) |
C8—C9—C10—C17 | −0.3 (4) | C31ii—C32—C35—C31 | −5.3 (17) |
C6—C5—C11—C12 | −98.2 (3) | C32ii—C32—C35—C31 | −1.6 (5) |
C4—C5—C11—C12 | 81.3 (3) | C33—C32—C35—C34 | 2.0 (8) |
C6—C5—C11—C16 | 74.7 (3) | C31ii—C32—C35—C34 | 173.3 (17) |
C4—C5—C11—C16 | −105.8 (3) | C31—C32—C35—C34 | 178.7 (5) |
C16—C11—C12—C13 | −4.5 (4) | C32ii—C32—C35—C34 | 177.1 (7) |
C5—C11—C12—C13 | 168.6 (2) | C32—C34—C35—C31 | 1.4 (5) |
C11—C12—C13—C14 | 0.2 (4) | C33—C34—C35—C31 | 0.3 (7) |
C12—C13—C14—C15 | 4.6 (4) | C33—C34—C35—C32 | −1.1 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x−1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C60H60N4)]·C7H8 |
Mr | 994.64 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 85 |
a, b, c (Å) | 16.0277 (16), 9.5884 (14), 16.8714 (16) |
β (°) | 93.892 (8) |
V (Å3) | 2586.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.52 |
Crystal size (mm) | 0.25 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14020, 4533, 3375 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.122, 1.05 |
No. of reflections | 4533 |
No. of parameters | 341 |
No. of restraints | 93 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.42, −0.37 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990).
Zn1—N2 | 2.024 (2) | Zn1—N1 | 2.054 (2) |
N2—Zn1—N2i | 180 | N2—Zn1—N1 | 89.94 (8) |
N2—Zn1—N1i | 90.06 (8) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Physicochemical properties of metallo-porphyrins depend on the complexed metal and the kind of peripherally and/or axially fixed substituents. These factors influence the electronic density distribution within the core of the macrocycle, thus determining both its stability and reactivity (Berezin, 1981). Therefore, structural details are essential in learning the basic chemistry of such compounds featuring unique properties, e.g. photocatalytic activity (Mele et al., 2007). 5,10,15,20-Tetrakis(4-tert-butylphenyl)porphyrinato zinc(II) (ZnPp), when crystallized from a toluene solution yielded a typical lattice clathrate with ZnPp (host) to toluene (guest) 1:1 stoichiometry. The structure of the title tert-butylphenyl meso-substituted ZnPp derivative has been solved and reported for the first time in this work.
The crystal lattice consists of discrete centrosymmetrical molecules of ZnPp (Fig. 1) and disordered molecules of toluene, located at the inversion centre. This is a typical case of toluene disorder exhibiting two discrete positions; one molecule is staggered 180° with respect to the other one. The zinc atom is found in a plane defined by the four pyrrole-nitrogen atoms and the N—Zn—N bond angles are ca 90°, showing ideal square-planar coordination. The macrocycle itself shows no apparent distortion and one may consider it as "perfectly flat". The meso substituted benzene rings are not perpendicular to the plane of the macrocycle, yielding dihedral angles of 78.44 (7)° and 79.17 (7)°. The geometry of the porphyrin core proved typical as for the family of similar zinc porphyrins substituted in their meso position by four identical phenyl derivatives (Allen, 2002). The unit cell packing of the title compound is shown in Fig. 2.