Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027018/pk2027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027018/pk2027Isup2.hkl |
CCDC reference: 654893
During the metallation of H2OETPP (Adler et al. 1970), the reaction solution was washed by 2 mol/L HCl solution. The resulting material was crystallized in toluene, which yielded [H4OETPP]·2Cl crystals as an impurity.
The structures were solved by direct methods using XS (Sheldrick, 2001) and refined against F2 using XL (Sheldrick, 2001); subsequent difference Fourier syntheses led to the location of all the remaining non-hydrogen atoms. For the structure refinement all data were used, including negative intensities. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were idealized with the standard SHELXTL idealization methods. The program SADABS was applied for the absorption correction. The phenyl group of the porphyrin molecule is disordered over two positions. The final refinement gave the occupancy for the major component as 0.58 (4). The toluene solvate is disordered around a threefold axis, its occupancy is fixed as 0.33333 and the phenyl ring was refined as a rigid group. Anisotropic displacement parameters for atoms of these groups were refined by similar Uij restraints (SIMU). Rounding errors create differences between reported formula and that calculated by checkCIF.
Different macrocycle conformations are believed to play an important role in a variety of protein complexes. (Senge 1992; Barkigia et al. 1988) Porphyrins bearing large and sterically interacting substituents at the porphyrin periphery have been synthesized successfully to yield tetrapyrroles with significantly distorted macrocycles. For one such porphyrin, octaethyltetraphenylporphyrin (OETPP), its free base and diacid salts have been reported (Regev et al. 1994; Barkigia et al. 1995; Senge et al. 1994; Senge & Kalisch, 1999). We report herein the molecular structure of another diacid salt of OETPP as a different solvate, [H4OETPP]·2Cl·(C7H8)1.33.
Figure 1 shows the thermal-ellipsoid plot of the cation, H4OETPP2+. This porphyrin has an S4 symmetry axis through the porphyrin center. The asymmetric unit is one-fourth porphyrin. The neighboring pyrrole units are displaced pairwise above and below the mean plane. One of the most important features is the severe saddling of the porphyrin core. The displacements of the porphyrin core are also shown in Figure 1. The average displacement of the β-carbons from the four nitrogen mean plane is 1.23 (9) Å, which is similar to those in other diacid salts of OETPP (Barkigia et al. 1995; Senge et al. 1994; Senge & Kalisch, 1999). Saddling is also shown by the tilt of pyrrole rings away from porphyrin mean plane. In the title compound, the average of the dihedral angle between pyrrole and porphyrin mean plane is 38.25 (4)°.
The four pyrrole N atoms are protonated, they show alternating up- and down- displacements. As shown in Figure 2, two chloride anions are held at both sides of the porphyrin plane by hydrogen-bonds to pyrrole nitrogen. The Cl···N distance is 3.206 (1) Å, which is comparable with 3.15 and 3.23 Å in [H4OETPP]·2Cl·CH2Cl2 (Senge & Kalisch, 1999).
For related literature, see: Barkigia et al. (1988, 1995); Regev et al. (1994); Senge (1992); Senge & Kalisch (1999); Senge et al. (1994).
For related literature, see: Adler et al. (1970).
Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: APEX2 and SAINT (Bruker–Nonius, 2004); data reduction: SAINT and XPREP (Sheldrick, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: XP (Sheldrick, 1998) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.
C60H64N42+·2Cl−·1.33C7H8 | Dx = 1.199 Mg m−3 |
Mr = 1034.90 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, I43d | Cell parameters from 9107 reflections |
Hall symbol: I -4bd 2c 3 | θ = 2.2–27.0° |
a = 25.8135 (2) Å | µ = 0.16 mm−1 |
V = 17200.5 (2) Å3 | T = 100 K |
Z = 12 | Block, red |
F(000) = 6632 | 0.42 × 0.32 × 0.29 mm |
Bruker APEX II CCD area-detector diffractometer | 4414 independent reflections |
Radiation source: fine-focus sealed tube | 3859 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.33 pixels mm-1 | θmax = 30.6°, θmin = 1.9° |
φ and ω scans | h = −36→36 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −36→36 |
Tmin = 0.936, Tmax = 0.955 | l = −36→29 |
176336 measured reflections |
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0734P)2 + 9.3007P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.003 |
4414 reflections | Δρmax = 0.42 e Å−3 |
271 parameters | Δρmin = −0.20 e Å−3 |
42 restraints | Absolute structure: Flack (1983), 2073 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.07 (7) |
C60H64N42+·2Cl−·1.33C7H8 | Z = 12 |
Mr = 1034.90 | Mo Kα radiation |
Cubic, I43d | µ = 0.16 mm−1 |
a = 25.8135 (2) Å | T = 100 K |
V = 17200.5 (2) Å3 | 0.42 × 0.32 × 0.29 mm |
Bruker APEX II CCD area-detector diffractometer | 4414 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3859 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.955 | Rint = 0.040 |
176336 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.139 | Δρmax = 0.42 e Å−3 |
S = 1.15 | Δρmin = −0.20 e Å−3 |
4414 reflections | Absolute structure: Flack (1983), 2073 Friedel pairs |
271 parameters | Absolute structure parameter: −0.07 (7) |
42 restraints |
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 > 2σ(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) | |
Cl1 | 0.5000 | 0.2500 | 0.02930 (2) | 0.03694 (15) | |
N1 | 0.53228 (5) | 0.32591 (5) | 0.12214 (5) | 0.0251 (2) | |
H1A | 0.5196 | 0.3011 | 0.1025 | 0.030* | |
C1 | 0.50375 (6) | 0.36471 (6) | 0.14469 (6) | 0.0249 (3) | |
C2 | 0.53873 (6) | 0.39489 (6) | 0.17608 (6) | 0.0270 (3) | |
C3 | 0.58772 (6) | 0.37522 (6) | 0.16901 (6) | 0.0274 (3) | |
C4 | 0.58334 (6) | 0.33159 (6) | 0.13465 (6) | 0.0256 (3) | |
C5 | 0.52423 (8) | 0.43372 (7) | 0.21691 (7) | 0.0337 (3) | |
H5A | 0.5000 | 0.4594 | 0.2019 | 0.040* | |
H5B | 0.5557 | 0.4524 | 0.2284 | 0.040* | |
C6 | 0.49915 (12) | 0.40811 (10) | 0.26289 (9) | 0.0524 (6) | |
H6A | 0.4912 | 0.4343 | 0.2892 | 0.079* | |
H6B | 0.5228 | 0.3823 | 0.2775 | 0.079* | |
H6C | 0.4670 | 0.3911 | 0.2519 | 0.079* | |
C7 | 0.63502 (7) | 0.39025 (8) | 0.19900 (8) | 0.0370 (4) | |
H7A | 0.6305 | 0.4258 | 0.2128 | 0.044* | |
H7B | 0.6654 | 0.3904 | 0.1755 | 0.044* | |
C8 | 0.64522 (10) | 0.35331 (11) | 0.24360 (10) | 0.0535 (6) | |
H8A | 0.6745 | 0.3661 | 0.2642 | 0.080* | |
H8B | 0.6534 | 0.3189 | 0.2299 | 0.080* | |
H8C | 0.6143 | 0.3511 | 0.2656 | 0.080* | |
C9 | 0.62278 (6) | 0.29898 (6) | 0.11615 (6) | 0.0274 (3) | |
C10A | 0.6751 (4) | 0.3241 (7) | 0.1054 (7) | 0.026 (2) | 0.58 (4) |
C11A | 0.7208 (5) | 0.3005 (5) | 0.1244 (5) | 0.0376 (17) | 0.58 (4) |
H11A | 0.7192 | 0.2695 | 0.1443 | 0.045* | 0.58 (4) |
C12A | 0.7684 (4) | 0.3239 (6) | 0.1133 (4) | 0.048 (3) | 0.58 (4) |
H12A | 0.7994 | 0.3093 | 0.1269 | 0.057* | 0.58 (4) |
C13A | 0.7710 (4) | 0.3681 (6) | 0.0827 (5) | 0.052 (2) | 0.58 (4) |
H13A | 0.8036 | 0.3831 | 0.0747 | 0.062* | 0.58 (4) |
C14A | 0.7261 (5) | 0.3903 (4) | 0.0640 (4) | 0.0441 (18) | 0.58 (4) |
H14A | 0.7281 | 0.4205 | 0.0431 | 0.053* | 0.58 (4) |
C15A | 0.6778 (6) | 0.3686 (6) | 0.0754 (5) | 0.0331 (18) | 0.58 (4) |
H15A | 0.6470 | 0.3843 | 0.0628 | 0.040* | 0.58 (4) |
C10B | 0.6743 (7) | 0.3166 (10) | 0.1126 (10) | 0.039 (5) | 0.42 (4) |
C11B | 0.7144 (7) | 0.2923 (9) | 0.1366 (9) | 0.050 (3) | 0.42 (4) |
H11B | 0.7078 | 0.2648 | 0.1601 | 0.060* | 0.42 (4) |
C12B | 0.7645 (7) | 0.3075 (9) | 0.1268 (11) | 0.060 (4) | 0.42 (4) |
H12B | 0.7918 | 0.2880 | 0.1419 | 0.072* | 0.42 (4) |
C13B | 0.7765 (5) | 0.3469 (12) | 0.0981 (10) | 0.067 (7) | 0.42 (4) |
H13B | 0.8118 | 0.3558 | 0.0925 | 0.081* | 0.42 (4) |
C14B | 0.7372 (9) | 0.3762 (11) | 0.0757 (7) | 0.066 (5) | 0.42 (4) |
H14B | 0.7447 | 0.4064 | 0.0561 | 0.079* | 0.42 (4) |
C15B | 0.6847 (9) | 0.3592 (10) | 0.0833 (9) | 0.046 (4) | 0.42 (4) |
H15B | 0.6571 | 0.3779 | 0.0678 | 0.055* | 0.42 (4) |
C21 | 0.6692 (6) | 0.1960 (7) | 0.2840 (5) | 0.080 (4) | 0.33 |
C22 | 0.6698 (7) | 0.2339 (6) | 0.3206 (6) | 0.092 (4) | 0.33 |
H22A | 0.6514 | 0.2649 | 0.3132 | 0.111* | 0.33 |
C23 | 0.6957 (6) | 0.2311 (6) | 0.3687 (5) | 0.080 (3) | 0.33 |
H23A | 0.6928 | 0.2582 | 0.3935 | 0.096* | 0.33 |
C24 | 0.7247 (5) | 0.1886 (6) | 0.3782 (5) | 0.089 (3) | 0.33 |
H24A | 0.7439 | 0.1857 | 0.4095 | 0.107* | 0.33 |
C25 | 0.7261 (6) | 0.1458 (7) | 0.3383 (6) | 0.094 (4) | 0.33 |
H25A | 0.7455 | 0.1151 | 0.3443 | 0.113* | 0.33 |
C26 | 0.6988 (7) | 0.1521 (6) | 0.2935 (5) | 0.079 (3) | 0.33 |
H26A | 0.7002 | 0.1257 | 0.2679 | 0.095* | 0.33 |
C27 | 0.6384 (7) | 0.1992 (6) | 0.2345 (6) | 0.111 (6) | 0.33 |
H27A | 0.6200 | 0.1665 | 0.2289 | 0.166* | 0.33 |
H27B | 0.6619 | 0.2058 | 0.2054 | 0.166* | 0.33 |
H27C | 0.6133 | 0.2276 | 0.2371 | 0.166* | 0.33 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0396 (3) | 0.0432 (3) | 0.0280 (3) | −0.0041 (3) | 0.000 | 0.000 |
N1 | 0.0245 (6) | 0.0252 (6) | 0.0257 (6) | −0.0014 (5) | −0.0018 (5) | −0.0030 (5) |
C1 | 0.0275 (7) | 0.0229 (6) | 0.0242 (6) | 0.0000 (5) | −0.0019 (5) | −0.0001 (5) |
C2 | 0.0319 (7) | 0.0240 (7) | 0.0250 (7) | −0.0005 (6) | −0.0039 (5) | −0.0011 (5) |
C3 | 0.0295 (7) | 0.0265 (7) | 0.0263 (7) | −0.0026 (6) | −0.0029 (6) | −0.0039 (6) |
C4 | 0.0252 (7) | 0.0257 (7) | 0.0260 (7) | −0.0037 (5) | −0.0014 (5) | −0.0015 (6) |
C5 | 0.0365 (8) | 0.0303 (8) | 0.0343 (8) | 0.0060 (6) | −0.0060 (7) | −0.0076 (6) |
C6 | 0.0664 (14) | 0.0536 (12) | 0.0371 (10) | 0.0086 (11) | 0.0127 (10) | −0.0089 (9) |
C7 | 0.0304 (8) | 0.0403 (9) | 0.0402 (9) | −0.0037 (7) | −0.0043 (7) | −0.0164 (8) |
C8 | 0.0437 (11) | 0.0739 (15) | 0.0429 (11) | 0.0034 (11) | −0.0187 (9) | −0.0073 (11) |
C9 | 0.0253 (7) | 0.0291 (7) | 0.0279 (7) | −0.0028 (6) | −0.0018 (6) | −0.0040 (5) |
C10A | 0.017 (3) | 0.029 (5) | 0.033 (3) | −0.006 (2) | 0.0045 (16) | −0.006 (3) |
C11A | 0.025 (3) | 0.045 (3) | 0.043 (4) | −0.003 (2) | 0.005 (2) | −0.019 (3) |
C12A | 0.021 (3) | 0.064 (8) | 0.058 (5) | −0.018 (4) | 0.010 (3) | −0.027 (5) |
C13A | 0.036 (3) | 0.067 (5) | 0.052 (4) | −0.028 (3) | 0.021 (3) | −0.031 (3) |
C14A | 0.051 (4) | 0.049 (3) | 0.033 (3) | −0.025 (3) | 0.014 (3) | −0.014 (2) |
C15A | 0.040 (4) | 0.030 (3) | 0.030 (3) | −0.011 (3) | 0.013 (3) | −0.001 (2) |
C10B | 0.048 (6) | 0.027 (6) | 0.041 (8) | −0.013 (3) | 0.009 (3) | −0.012 (6) |
C11B | 0.022 (4) | 0.074 (9) | 0.055 (8) | −0.002 (4) | −0.003 (5) | −0.033 (6) |
C12B | 0.030 (4) | 0.063 (8) | 0.086 (11) | −0.013 (5) | 0.004 (5) | −0.036 (7) |
C13B | 0.031 (4) | 0.097 (16) | 0.073 (12) | −0.033 (8) | 0.018 (6) | −0.049 (11) |
C14B | 0.069 (11) | 0.089 (11) | 0.041 (6) | −0.049 (9) | 0.022 (6) | −0.022 (6) |
C15B | 0.039 (4) | 0.049 (10) | 0.049 (8) | −0.009 (5) | 0.006 (5) | −0.011 (6) |
C21 | 0.085 (8) | 0.108 (10) | 0.048 (5) | 0.047 (8) | −0.011 (5) | −0.018 (5) |
C22 | 0.115 (11) | 0.102 (10) | 0.060 (7) | 0.023 (9) | −0.013 (7) | −0.004 (7) |
C23 | 0.080 (8) | 0.088 (8) | 0.072 (7) | 0.031 (6) | −0.014 (5) | −0.019 (6) |
C24 | 0.088 (7) | 0.108 (9) | 0.071 (6) | 0.012 (7) | 0.007 (6) | 0.025 (6) |
C25 | 0.113 (10) | 0.089 (9) | 0.081 (8) | −0.029 (8) | −0.041 (7) | 0.026 (7) |
C26 | 0.098 (9) | 0.075 (7) | 0.065 (6) | −0.018 (7) | −0.037 (6) | −0.004 (5) |
C27 | 0.165 (16) | 0.101 (10) | 0.067 (7) | 0.043 (10) | −0.017 (9) | −0.016 (7) |
N1—C4 | 1.365 (2) | C13A—C14A | 1.379 (14) |
N1—C1 | 1.3729 (19) | C13A—H13A | 0.9500 |
N1—H1A | 0.8800 | C14A—C15A | 1.398 (19) |
C1—C9i | 1.405 (2) | C14A—H14A | 0.9500 |
C1—C2 | 1.442 (2) | C15A—H15A | 0.9500 |
C2—C3 | 1.375 (2) | C10B—C15B | 1.36 (3) |
C2—C5 | 1.502 (2) | C10B—C11B | 1.36 (3) |
C3—C4 | 1.438 (2) | C11B—C12B | 1.374 (18) |
C3—C7 | 1.497 (2) | C11B—H11B | 0.9500 |
C4—C9 | 1.405 (2) | C12B—C13B | 1.296 (18) |
C5—C6 | 1.505 (3) | C12B—H12B | 0.9500 |
C5—H5A | 0.9900 | C13B—C14B | 1.39 (2) |
C5—H5B | 0.9900 | C13B—H13B | 0.9500 |
C6—H6A | 0.9800 | C14B—C15B | 1.44 (3) |
C6—H6B | 0.9800 | C14B—H14B | 0.9500 |
C6—H6C | 0.9800 | C15B—H15B | 0.9500 |
C7—C8 | 1.518 (3) | C21—C22 | 1.360 (19) |
C7—H7A | 0.9900 | C21—C26 | 1.39 (2) |
C7—H7B | 0.9900 | C21—C27 | 1.506 (17) |
C8—H8A | 0.9800 | C22—C23 | 1.411 (19) |
C8—H8B | 0.9800 | C22—H22A | 0.9500 |
C8—H8C | 0.9800 | C23—C24 | 1.352 (18) |
C9—C1ii | 1.405 (2) | C23—H23A | 0.9500 |
C9—C10B | 1.41 (2) | C24—C25 | 1.51 (3) |
C9—C10A | 1.524 (13) | C24—H24A | 0.9500 |
C10A—C15A | 1.39 (2) | C25—C26 | 1.365 (17) |
C10A—C11A | 1.42 (2) | C25—H25A | 0.9500 |
C11A—C12A | 1.398 (12) | C26—H26A | 0.9500 |
C11A—H11A | 0.9500 | C27—H27A | 0.9800 |
C12A—C13A | 1.390 (10) | C27—H27B | 0.9800 |
C12A—H12A | 0.9500 | C27—H27C | 0.9800 |
C4—N1—C1 | 109.84 (13) | C10A—C11A—H11A | 120.8 |
C4—N1—H1A | 125.1 | C13A—C12A—C11A | 120.9 (10) |
C1—N1—H1A | 125.1 | C13A—C12A—H12A | 119.5 |
N1—C1—C9i | 122.92 (14) | C11A—C12A—H12A | 119.5 |
N1—C1—C2 | 107.24 (13) | C14A—C13A—C12A | 120.0 (7) |
C9i—C1—C2 | 129.69 (14) | C14A—C13A—H13A | 120.0 |
C3—C2—C1 | 107.58 (14) | C12A—C13A—H13A | 120.0 |
C3—C2—C5 | 124.67 (15) | C13A—C14A—C15A | 120.6 (8) |
C1—C2—C5 | 126.78 (15) | C13A—C14A—H14A | 119.7 |
C2—C3—C4 | 107.39 (14) | C15A—C14A—H14A | 119.7 |
C2—C3—C7 | 125.87 (15) | C10A—C15A—C14A | 119.6 (10) |
C4—C3—C7 | 125.88 (15) | C10A—C15A—H15A | 120.2 |
N1—C4—C9 | 123.72 (14) | C14A—C15A—H15A | 120.2 |
N1—C4—C3 | 107.82 (13) | C15B—C10B—C11B | 118.4 (19) |
C9—C4—C3 | 128.46 (14) | C15B—C10B—C9 | 119.0 (19) |
C2—C5—C6 | 111.57 (16) | C11B—C10B—C9 | 123 (2) |
C2—C5—H5A | 109.3 | C10B—C11B—C12B | 120.0 (18) |
C6—C5—H5A | 109.3 | C10B—C11B—H11B | 120.0 |
C2—C5—H5B | 109.3 | C12B—C11B—H11B | 120.0 |
C6—C5—H5B | 109.3 | C13B—C12B—C11B | 124 (2) |
H5A—C5—H5B | 108.0 | C13B—C12B—H12B | 118.2 |
C5—C6—H6A | 109.5 | C11B—C12B—H12B | 118.2 |
C5—C6—H6B | 109.5 | C12B—C13B—C14B | 119.3 (15) |
H6A—C6—H6B | 109.5 | C12B—C13B—H13B | 120.4 |
C5—C6—H6C | 109.5 | C14B—C13B—H13B | 120.4 |
H6A—C6—H6C | 109.5 | C13B—C14B—C15B | 117.7 (12) |
H6B—C6—H6C | 109.5 | C13B—C14B—H14B | 121.2 |
C3—C7—C8 | 111.77 (17) | C15B—C14B—H14B | 121.2 |
C3—C7—H7A | 109.3 | C10B—C15B—C14B | 120.6 (16) |
C8—C7—H7A | 109.3 | C10B—C15B—H15B | 119.7 |
C3—C7—H7B | 109.3 | C14B—C15B—H15B | 119.7 |
C8—C7—H7B | 109.3 | C22—C21—C26 | 117.3 (11) |
H7A—C7—H7B | 107.9 | C22—C21—C27 | 123.7 (16) |
C7—C8—H8A | 109.5 | C26—C21—C27 | 119.0 (16) |
C7—C8—H8B | 109.5 | C21—C22—C23 | 125.4 (16) |
H8A—C8—H8B | 109.5 | C21—C22—H22A | 117.3 |
C7—C8—H8C | 109.5 | C23—C22—H22A | 117.3 |
H8A—C8—H8C | 109.5 | C24—C23—C22 | 117.6 (13) |
H8B—C8—H8C | 109.5 | C24—C23—H23A | 121.2 |
C4—C9—C1ii | 122.72 (14) | C22—C23—H23A | 121.2 |
C4—C9—C10B | 120.9 (9) | C23—C24—C25 | 118.9 (13) |
C1ii—C9—C10B | 116.1 (10) | C23—C24—H24A | 120.5 |
C4—C9—C10A | 116.8 (6) | C25—C24—H24A | 120.5 |
C1ii—C9—C10A | 120.4 (6) | C26—C25—C24 | 118.6 (16) |
C15A—C10A—C11A | 120.6 (11) | C26—C25—H25A | 120.7 |
C15A—C10A—C9 | 119.8 (10) | C24—C25—H25A | 120.7 |
C11A—C10A—C9 | 119.6 (13) | C25—C26—C21 | 122.0 (16) |
C12A—C11A—C10A | 118.4 (11) | C25—C26—H26A | 119.0 |
C12A—C11A—H11A | 120.8 | C21—C26—H26A | 119.0 |
Symmetry codes: (i) −y+3/4, x−1/4, −z+1/4; (ii) y+1/4, −x+3/4, −z+1/4. |
Experimental details
Crystal data | |
Chemical formula | C60H64N42+·2Cl−·1.33C7H8 |
Mr | 1034.90 |
Crystal system, space group | Cubic, I43d |
Temperature (K) | 100 |
a (Å) | 25.8135 (2) |
V (Å3) | 17200.5 (2) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.42 × 0.32 × 0.29 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.936, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 176336, 4414, 3859 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.716 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.139, 1.15 |
No. of reflections | 4414 |
No. of parameters | 271 |
No. of restraints | 42 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.20 |
Absolute structure | Flack (1983), 2073 Friedel pairs |
Absolute structure parameter | −0.07 (7) |
Computer programs: APEX2 (Bruker–Nonius, 2004), APEX2 and SAINT (Bruker–Nonius, 2004), SAINT and XPREP (Sheldrick, 2005), SHELXTL (Sheldrick, 2001), SHELXTL, XP (Sheldrick, 1998) and PLATON (Spek, 2003).
Different macrocycle conformations are believed to play an important role in a variety of protein complexes. (Senge 1992; Barkigia et al. 1988) Porphyrins bearing large and sterically interacting substituents at the porphyrin periphery have been synthesized successfully to yield tetrapyrroles with significantly distorted macrocycles. For one such porphyrin, octaethyltetraphenylporphyrin (OETPP), its free base and diacid salts have been reported (Regev et al. 1994; Barkigia et al. 1995; Senge et al. 1994; Senge & Kalisch, 1999). We report herein the molecular structure of another diacid salt of OETPP as a different solvate, [H4OETPP]·2Cl·(C7H8)1.33.
Figure 1 shows the thermal-ellipsoid plot of the cation, H4OETPP2+. This porphyrin has an S4 symmetry axis through the porphyrin center. The asymmetric unit is one-fourth porphyrin. The neighboring pyrrole units are displaced pairwise above and below the mean plane. One of the most important features is the severe saddling of the porphyrin core. The displacements of the porphyrin core are also shown in Figure 1. The average displacement of the β-carbons from the four nitrogen mean plane is 1.23 (9) Å, which is similar to those in other diacid salts of OETPP (Barkigia et al. 1995; Senge et al. 1994; Senge & Kalisch, 1999). Saddling is also shown by the tilt of pyrrole rings away from porphyrin mean plane. In the title compound, the average of the dihedral angle between pyrrole and porphyrin mean plane is 38.25 (4)°.
The four pyrrole N atoms are protonated, they show alternating up- and down- displacements. As shown in Figure 2, two chloride anions are held at both sides of the porphyrin plane by hydrogen-bonds to pyrrole nitrogen. The Cl···N distance is 3.206 (1) Å, which is comparable with 3.15 and 3.23 Å in [H4OETPP]·2Cl·CH2Cl2 (Senge & Kalisch, 1999).