The highly saddled octa­ethyl­tetra­phenyl­porphyrin-[H₄OETPP] dichloride toluene 1.33-solvate

The title compound, 2,3,7,8,12,13,17,18-octa­ethyl-5,10,15,20-tetra­phenyl­porphyrin dichloride toluene 1.33-solvate, C₆₀H₆₄N₄²⁺·2Cl⁻·1.33C₇H₈, displays a highly S₄-saddled porphyrin core with the Cβ atoms displaced 1.23 (9) Å out of the N₄ plane. All N atoms are protonated and form hydrogen bonds [N...Cl = 3.206 (1) Å] with chloride anions. An S₄ symmetry axis passes through the porphyrin center. The phenyl group of the porphyrin is disordered over two sites, with occupancies approximately 0.6:0.4.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
Some non-H atoms missing
• Disorder in main residue
• R factor = 0.046
• wR factor = 0.139
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT301_ALERT_3_B Main Residue  Disorder .........................      28.00 Perc.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.10
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         20 Ang.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.69 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.25
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C69.33 H74.67 Cl2 N4
            Atom count from _chemical_formula_moiety:C69.31 H74.64 Cl2 N4
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C69.33 H74.67 Cl2 N4
            Atom count from the _atom_site data:  C69.24 H74.56 Cl2 N4
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z   12
           From the CIF: _chemical_formula_sum  C69.33 H74.67 Cl2 N4
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        831.96    830.88    1.08
           H        896.04    894.72    1.32
           Cl        24.00     24.00    0.00
           N         48.00     48.00    0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.60
           From the CIF: _reflns_number_total               4414
           Count of symmetry unique reflns         2341
           Completeness (_total/calc)            188.55%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2073
           Fraction of Friedel pairs measured     0.886
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         42

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

---

S1. Comment

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).

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U^ij restraints (SIMU). Rounding errors create differences between reported formula and that calculated by checkCIF.

Computing details

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.

Figures

	Fig. 1. The molecular structure showing 50% probability displacement ellipsoids. Only the major component of the phenyl group is displayed. The displacements of the atoms of the porphyrin core from the mean plane defined by the four nitrogen porphyrin atoms are also given in 0.01 Å.
	Fig. 2. Crystal structure of the title compound with hydrogen bonds as shown in dashed lines.

2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin dichloride toluene 1.33-solvate

Crystal data

C60H64N4^2+·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) Å^3	T = 100 K
Z = 12	Block, red
F(000) = 6632	0.42 × 0.32 × 0.29 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0734P)^2 + 9.3007P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C9^i	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—C1^ii	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—C9^i	122.92 (14)	C11A—C12A—H12A	119.5
N1—C1—C2	107.24 (13)	C14A—C13A—C12A	120.0 (7)
C9^i—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—C1^ii	122.72 (14)	C22—C23—H23A	121.2
C4—C9—C10B	120.9 (9)	C23—C24—C25	118.9 (13)
C1^ii—C9—C10B	116.1 (10)	C23—C24—H24A	120.5
C4—C9—C10A	116.8 (6)	C25—C24—H24A	120.5
C1^ii—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.