Oxazolochlorins. 14. 8-Oxo-5,10,15,20-tetra­phenyl-7-oxa­porphyrin N²⁴-oxide

The structure of 8-oxo-5,10,15,20-tetra­phenyl-7-oxaporphyrin N²⁴-oxide, C₄₃H₂₈N₄O₃, (4B), shows that N-oxidation of the pyrrole opposite the oxazolidone group cants the pyrrole out of the mean plane of the chromophore. This also affects the oxazolidone group, which is also slightly canted out. This conformation is qualitatively similar to that of the parent meso-tetra­phenyl­porphyrin N-oxide, but dissimilar to that of the porpholactone N-oxide isomer 8-oxo-5,10,15,20-tetra­phenyl-7-oxaporphyrin N²²-oxide, (4A), carrying the N-oxide at the oxazolidone group. While the degree of canting of the N-oxidized groups in both cases is comparable (and more pronounced than in the porphyrin N-oxide case), in (4A) the pyrrolic groups adjacent to the N-oxidized group are more affected than the opposing group. These differences in the conformational modes may contribute to rationalizing the distinctly different electronic properties of (4A) and (4B).

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: APEX2 (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014) and SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

8-Oxo-5,10,15,20-tetraphenyl-7-oxaporphyrin N²⁴-oxide

Crystal data

C43H28N4O3	Z = 1
Mr = 648.69	F(000) = 338
Triclinic, P1	Dx = 1.358 Mg m^−3
a = 6.3512 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.405 (2) Å	Cell parameters from 2036 reflections
c = 12.464 (2) Å	θ = 2.4–30.3°
α = 95.548 (3)°	µ = 0.09 mm^−1
β = 99.348 (3)°	T = 100 K
γ = 100.200 (3)°	Block, black
V = 793.2 (3) Å^3	0.32 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3185 independent reflections
Radiation source: fine-focus sealed tube	2371 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan (APEX2; Bruker, 2009)	h = −7→7
Tmin = 0.469, Tmax = 0.746	k = −12→12
6892 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.4642P] where P = (Fo^2 + 2Fc^2)/3
3185 reflections	(Δ/σ)max < 0.001
283 parameters	Δρmax = 0.28 e Å^−3
152 restraints	Δρmin = −0.27 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	−0.3131 (3)	0.4285 (2)	0.66082 (19)	0.0272 (5)
N1_a	−0.132 (2)	0.5132 (16)	0.6439 (7)	0.0301 (18)	0.3159 (16)
H1A1_a	−0.0917	0.5218	0.5803	0.036*	0.3159 (16)
C2_a	−0.314 (2)	0.4428 (17)	0.7792 (9)	0.0272 (5)	0.3159 (16)
H2_a	−0.4192	0.3959	0.8146	0.033*	0.3159 (16)
C3_a	−0.137 (3)	0.535 (2)	0.8287 (9)	0.0262 (4)	0.3159 (16)
H3_a	−0.0944	0.5635	0.9052	0.031*	0.3159 (16)
N1A1_b	−0.132 (2)	0.5132 (16)	0.6439 (7)	0.0301 (18)	0.2905 (12)
O2A1_b	−0.3357 (16)	0.4401 (12)	0.7628 (7)	0.0272 (5)	0.2905 (12)
O3A1_b	−0.1305 (10)	0.5544 (7)	0.9180 (5)	0.0424 (16)	0.2905 (12)
C3A1_b	−0.160 (2)	0.5349 (17)	0.8218 (11)	0.0262 (4)	0.2905 (12)
N1A2_c	−0.132 (2)	0.5132 (16)	0.6439 (7)	0.0301 (18)	0.0515 (12)
O2A2_c	−0.156 (4)	0.574 (2)	0.8167 (17)	0.0262 (4)	0.0515 (12)
C2A2_c	−0.336 (3)	0.475 (2)	0.7706 (17)	0.0272 (5)	0.0515 (12)
O3A2_c	−0.468 (5)	0.441 (3)	0.821 (2)	0.0272 (5)	0.0515 (12)
N1A_d	−0.149 (5)	0.524 (3)	0.6446 (12)	0.0301 (18)	0.3421 (8)
O1A_d	−0.1322 (7)	0.5743 (4)	0.5521 (3)	0.0239 (9)	0.3421 (8)
C2A_d	−0.2990 (17)	0.4309 (11)	0.7796 (9)	0.0272 (5)	0.3421 (8)
H2A_d	−0.3930	0.3750	0.8151	0.033*	0.3421 (8)
C3A_d	−0.129 (2)	0.5267 (14)	0.8297 (8)	0.0262 (4)	0.3421 (8)
H3A_d	−0.0847	0.5530	0.9064	0.031*	0.3421 (8)
C4	−0.0261 (3)	0.5819 (2)	0.74314 (18)	0.0262 (4)
C5	0.1760 (3)	0.6717 (2)	0.76366 (19)	0.0254 (5)
C6	0.3127 (3)	0.6980 (2)	0.68682 (19)	0.0261 (5)
N2_e	0.2750 (5)	0.6423 (3)	0.5795 (3)	0.0248 (8)	0.6841 (16)
H2A1_e	0.1601	0.5825	0.5475	0.030*	0.6841 (16)
C7_e	0.5221 (9)	0.7860 (6)	0.7068 (4)	0.0281 (9)	0.6841 (16)
H7_e	0.5910	0.8389	0.7740	0.034*	0.6841 (16)
C8_e	0.6032 (11)	0.7794 (10)	0.6122 (5)	0.0311 (11)	0.6841 (16)
H8_e	0.7417	0.8238	0.6026	0.037*	0.6841 (16)
N2B1_f	0.2750 (5)	0.6423 (3)	0.5795 (3)	0.0248 (8)	0.1204 (12)
C7B1_f	0.517 (4)	0.790 (2)	0.6983 (17)	0.0281 (9)	0.1204 (12)
O2B1_f	0.589 (4)	0.786 (3)	0.5993 (18)	0.0311 (11)	0.1204 (12)
O3B1_f	0.630 (2)	0.8609 (12)	0.7705 (11)	0.0281 (9)	0.1204 (12)
N2B2_g	0.2750 (5)	0.6423 (3)	0.5795 (3)	0.0248 (8)	0.0375 (12)
O2B2_g	0.517 (4)	0.771 (3)	0.7143 (17)	0.0281 (9)	0.0375 (12)
C8B2_g	0.605 (4)	0.766 (4)	0.6199 (18)	0.0311 (11)	0.0375 (12)
O3B2_g	0.786 (6)	0.815 (4)	0.619 (4)	0.0311 (11)	0.0375 (12)
N2B_h	0.254 (3)	0.673 (2)	0.574 (2)	0.0248 (8)	0.1579 (8)
O1B_h	0.0475 (14)	0.6399 (9)	0.5187 (8)	0.0239 (9)	0.1579 (8)
C7B_h	0.541 (2)	0.759 (2)	0.7114 (11)	0.0281 (9)	0.1579 (8)
H7B_h	0.6258	0.7881	0.7826	0.034*	0.1579 (8)
C8B_h	0.613 (3)	0.769 (4)	0.6156 (14)	0.0311 (11)	0.1579 (8)
H8B_h	0.7497	0.8157	0.6064	0.037*	0.1579 (8)
C9	0.4418 (3)	0.6931 (2)	0.52916 (18)	0.0269 (5)
C10	0.4587 (3)	0.6664 (2)	0.41797 (19)	0.0257 (5)
C11	0.2558 (4)	0.7396 (2)	0.87888 (19)	0.0284 (5)
C12	0.1378 (4)	0.8249 (3)	0.9251 (2)	0.0394 (6)
H12	0.0059	0.8387	0.8840	0.047*
C13	0.2131 (5)	0.8894 (3)	1.0309 (2)	0.0501 (8)
H13	0.1313	0.9464	1.0620	0.060*
C14	0.4048 (5)	0.8716 (3)	1.0910 (2)	0.0535 (8)
H14	0.4563	0.9171	1.1629	0.064*
C15	0.5222 (5)	0.7875 (3)	1.0464 (2)	0.0540 (8)
H15	0.6549	0.7753	1.0878	0.065*
C16	0.4476 (4)	0.7206 (3)	0.9414 (2)	0.0419 (7)
H16	0.5281	0.6615	0.9121	0.050*
C17	0.6396 (3)	0.7525 (2)	0.37954 (18)	0.0235 (5)
C18	0.6600 (4)	0.8896 (2)	0.39499 (19)	0.0290 (5)
H18	0.5591	0.9274	0.4300	0.035*
C19	0.8262 (4)	0.9711 (2)	0.3597 (2)	0.0335 (6)
H19	0.8390	1.0640	0.3710	0.040*
C20	0.9736 (4)	0.9164 (2)	0.3079 (2)	0.0325 (6)
H20	1.0875	0.9719	0.2839	0.039*
C21	0.9545 (4)	0.7808 (2)	0.2912 (2)	0.0333 (6)
H21	1.0546	0.7435	0.2552	0.040*
C22	0.7888 (4)	0.6994 (2)	0.3272 (2)	0.0296 (5)
H22	0.7772	0.6066	0.3160	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
N1_a	0.022 (2)	0.029 (3)	0.0343 (11)	−0.002 (2)	−0.0022 (10)	0.0058 (10)
C2_a	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
C3_a	0.0205 (10)	0.0227 (9)	0.0333 (10)	0.0042 (7)	0.0010 (7)	0.0000 (7)
N1A1_b	0.022 (2)	0.029 (3)	0.0343 (11)	−0.002 (2)	−0.0022 (10)	0.0058 (10)
O2A1_b	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
O3A1_b	0.035 (3)	0.052 (4)	0.030 (3)	−0.012 (3)	0.005 (3)	−0.007 (3)
C3A1_b	0.0205 (10)	0.0227 (9)	0.0333 (10)	0.0042 (7)	0.0010 (7)	0.0000 (7)
N1A2_c	0.022 (2)	0.029 (3)	0.0343 (11)	−0.002 (2)	−0.0022 (10)	0.0058 (10)
O2A2_c	0.0205 (10)	0.0227 (9)	0.0333 (10)	0.0042 (7)	0.0010 (7)	0.0000 (7)
C2A2_c	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
O3A2_c	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
N1A_d	0.022 (2)	0.029 (3)	0.0343 (11)	−0.002 (2)	−0.0022 (10)	0.0058 (10)
O1A_d	0.022 (2)	0.021 (2)	0.026 (2)	0.0011 (15)	0.0004 (16)	0.0029 (16)
C2A_d	0.0187 (10)	0.0220 (9)	0.0384 (11)	0.0010 (7)	0.0035 (8)	−0.0002 (8)
C3A_d	0.0205 (10)	0.0227 (9)	0.0333 (10)	0.0042 (7)	0.0010 (7)	0.0000 (7)
C4	0.0205 (10)	0.0227 (9)	0.0333 (10)	0.0042 (7)	0.0010 (7)	0.0000 (7)
C5	0.0227 (11)	0.0199 (11)	0.0318 (12)	0.0035 (8)	0.0000 (9)	0.0033 (9)
C6	0.0198 (11)	0.0199 (11)	0.0352 (13)	0.0013 (8)	−0.0010 (9)	0.0019 (9)
N2_e	0.0191 (11)	0.021 (2)	0.0311 (12)	−0.0013 (10)	0.0014 (10)	0.0032 (13)
C7_e	0.0206 (13)	0.023 (2)	0.0361 (15)	0.0006 (11)	−0.0011 (10)	−0.0024 (12)
C8_e	0.0191 (14)	0.0258 (19)	0.0453 (19)	−0.0026 (13)	0.0074 (13)	−0.0010 (15)
N2B1_f	0.0191 (11)	0.021 (2)	0.0311 (12)	−0.0013 (10)	0.0014 (10)	0.0032 (13)
C7B1_f	0.0206 (13)	0.023 (2)	0.0361 (15)	0.0006 (11)	−0.0011 (10)	−0.0024 (12)
O2B1_f	0.0191 (14)	0.0258 (19)	0.0453 (19)	−0.0026 (13)	0.0074 (13)	−0.0010 (15)
O3B1_f	0.0206 (13)	0.023 (2)	0.0361 (15)	0.0006 (11)	−0.0011 (10)	−0.0024 (12)
N2B2_g	0.0191 (11)	0.021 (2)	0.0311 (12)	−0.0013 (10)	0.0014 (10)	0.0032 (13)
O2B2_g	0.0206 (13)	0.023 (2)	0.0361 (15)	0.0006 (11)	−0.0011 (10)	−0.0024 (12)
C8B2_g	0.0191 (14)	0.0258 (19)	0.0453 (19)	−0.0026 (13)	0.0074 (13)	−0.0010 (15)
O3B2_g	0.0191 (14)	0.0258 (19)	0.0453 (19)	−0.0026 (13)	0.0074 (13)	−0.0010 (15)
N2B_h	0.0191 (11)	0.021 (2)	0.0311 (12)	−0.0013 (10)	0.0014 (10)	0.0032 (13)
O1B_h	0.022 (2)	0.021 (2)	0.026 (2)	0.0011 (15)	0.0004 (16)	0.0029 (16)
C7B_h	0.0206 (13)	0.023 (2)	0.0361 (15)	0.0006 (11)	−0.0011 (10)	−0.0024 (12)
C8B_h	0.0191 (14)	0.0258 (19)	0.0453 (19)	−0.0026 (13)	0.0074 (13)	−0.0010 (15)
C9	0.0207 (11)	0.0228 (11)	0.0347 (13)	0.0015 (9)	0.0032 (9)	0.0008 (9)
C10	0.0182 (11)	0.0238 (11)	0.0332 (13)	0.0019 (8)	0.0027 (9)	0.0013 (9)
C11	0.0252 (12)	0.0240 (12)	0.0304 (12)	−0.0060 (9)	−0.0001 (9)	0.0040 (9)
C12	0.0404 (15)	0.0329 (14)	0.0399 (15)	0.0054 (11)	−0.0009 (12)	−0.0022 (11)
C13	0.067 (2)	0.0376 (16)	0.0386 (16)	0.0069 (14)	0.0004 (14)	−0.0074 (12)
C14	0.065 (2)	0.0484 (18)	0.0303 (15)	−0.0127 (15)	−0.0096 (13)	−0.0040 (13)
C15	0.0420 (17)	0.068 (2)	0.0434 (17)	0.0029 (15)	−0.0105 (13)	0.0093 (15)
C16	0.0351 (14)	0.0480 (16)	0.0376 (15)	0.0052 (12)	−0.0050 (11)	0.0056 (12)
C17	0.0158 (10)	0.0247 (11)	0.0264 (11)	−0.0003 (8)	−0.0004 (8)	0.0003 (9)
C18	0.0243 (12)	0.0250 (12)	0.0356 (13)	0.0033 (9)	0.0036 (10)	0.0000 (10)
C19	0.0297 (13)	0.0212 (12)	0.0446 (15)	−0.0025 (9)	0.0016 (11)	0.0027 (10)
C20	0.0220 (12)	0.0325 (13)	0.0387 (14)	−0.0046 (9)	0.0030 (10)	0.0066 (11)
C21	0.0220 (12)	0.0348 (14)	0.0430 (15)	0.0031 (10)	0.0093 (10)	0.0037 (11)
C22	0.0252 (12)	0.0218 (11)	0.0401 (14)	0.0028 (9)	0.0048 (10)	0.0001 (10)

Geometric parameters (Å, º)

C1—O2A1_b	1.299 (10)	C8_e—H8_e	0.9500
C1—N1A_d	1.36 (2)	C7B1_f—O3B1_f	1.16 (2)
C1—N1_a	1.377 (11)	C7B1_f—O2B1_f	1.384 (17)
C1—C10^i	1.410 (3)	O2B1_f—C9	1.349 (18)
C1—C2A2_c	1.448 (19)	O2B2_g—C8B2_g	1.383 (18)
C1—C2A_d	1.466 (11)	C8B2_g—O3B2_g	1.18 (4)
C1—C2_a	1.470 (12)	C8B2_g—C9	1.45 (2)
N1_a—C4	1.372 (7)	N2B_h—O1B_h	1.35 (2)
N1_a—H1A1_a	0.8800	N2B_h—C9	1.386 (14)
C2_a—C3_a	1.357 (12)	C7B_h—C8B_h	1.352 (14)
C2_a—H2_a	0.9500	C7B_h—H7B_h	0.9500
C3_a—C4	1.448 (12)	C8B_h—C9	1.452 (15)
C3_a—H3_a	0.9500	C8B_h—H8B_h	0.9500
O2A1_b—C3A1_b	1.400 (12)	C9—C10	1.412 (3)
O3A1_b—C3A1_b	1.176 (14)	C10—C1^i	1.410 (3)
C3A1_b—C4	1.463 (14)	C10—C17	1.500 (3)
O2A2_c—C4	1.330 (18)	C11—C16	1.392 (3)
O2A2_c—C2A2_c	1.395 (17)	C11—C12	1.399 (4)
C2A2_c—O3A2_c	1.15 (4)	C12—C13	1.389 (4)
N1A_d—O1A_d	1.32 (2)	C12—H12	0.9500
N1A_d—C4	1.364 (11)	C13—C14	1.374 (4)
C2A_d—C3A_d	1.353 (11)	C13—H13	0.9500
C2A_d—H2A_d	0.9500	C14—C15	1.379 (5)
C3A_d—C4	1.462 (11)	C14—H14	0.9500
C3A_d—H3A_d	0.9500	C15—C16	1.387 (4)
C4—C5	1.417 (3)	C15—H15	0.9500
C5—C6	1.408 (3)	C16—H16	0.9500
C5—C11	1.503 (3)	C17—C22	1.395 (3)
C6—O2B2_g	1.35 (2)	C17—C18	1.401 (3)
C6—N2_e	1.371 (5)	C18—C19	1.390 (3)
C6—N2B_h	1.38 (3)	C18—H18	0.9500
C6—C7_e	1.444 (6)	C19—C20	1.389 (4)
C6—C7B1_f	1.45 (2)	C19—H19	0.9500
C6—C7B_h	1.447 (14)	C20—C21	1.387 (3)
N2_e—C9	1.370 (4)	C20—H20	0.9500
N2_e—H2A1_e	0.8800	C21—C22	1.392 (3)
C7_e—C8_e	1.362 (6)	C21—H21	0.9500
C7_e—H7_e	0.9500	C22—H22	0.9500
C8_e—C9	1.441 (6)
O2A1_b—C1—C10^i	120.9 (4)	O3B1_f—C7B1_f—C6	134.5 (18)
N1A_d—C1—C10^i	128.3 (7)	O2B1_f—C7B1_f—C6	109.7 (15)
N1_a—C1—C10^i	126.9 (4)	C9—O2B1_f—C7B1_f	106.2 (14)
C10^i—C1—C2A2_c	128.7 (8)	C6—O2B2_g—C8B2_g	106.2 (15)
N1A_d—C1—C2A_d	107.2 (7)	O3B2_g—C8B2_g—O2B2_g	122 (3)
C10^i—C1—C2A_d	124.2 (4)	O3B2_g—C8B2_g—C9	128 (3)
N1_a—C1—C2_a	107.6 (6)	O2B2_g—C8B2_g—C9	109.6 (15)
C10^i—C1—C2_a	125.1 (5)	O1B_h—N2B_h—C6	124.5 (12)
C4—N1_a—C1	108.4 (8)	O1B_h—N2B_h—C9	126.8 (19)
C4—N1_a—H1A1_a	125.8	C6—N2B_h—C9	108.6 (14)
C1—N1_a—H1A1_a	125.8	C8B_h—C7B_h—C6	108.1 (10)
C3_a—C2_a—C1	107.6 (8)	C8B_h—C7B_h—H7B_h	125.9
C3_a—C2_a—H2_a	126.2	C6—C7B_h—H7B_h	125.9
C1—C2_a—H2_a	126.2	C7B_h—C8B_h—C9	107.4 (10)
C2_a—C3_a—C4	107.1 (8)	C7B_h—C8B_h—H8B_h	126.3
C2_a—C3_a—H3_a	126.4	C9—C8B_h—H8B_h	126.3
C4—C3_a—H3_a	126.4	O2B1_f—C9—C10	121.8 (8)
C1—O2A1_b—C3A1_b	107.7 (9)	N2_e—C9—C10	127.6 (3)
O3A1_b—C3A1_b—O2A1_b	121.1 (11)	N2B_h—C9—C10	127.3 (11)
O3A1_b—C3A1_b—C4	131.4 (10)	N2_e—C9—C8_e	106.9 (3)
O2A1_b—C3A1_b—C4	107.1 (10)	C10—C9—C8_e	125.4 (3)
C4—O2A2_c—C2A2_c	106.2 (14)	C10—C9—C8B2_g	128.9 (9)
O3A2_c—C2A2_c—O2A2_c	121 (2)	N2B_h—C9—C8B_h	106.3 (13)
O3A2_c—C2A2_c—C1	131 (2)	C10—C9—C8B_h	125.7 (6)
O2A2_c—C2A2_c—C1	108.6 (15)	C1^i—C10—C9	125.6 (2)
O1A_d—N1A_d—C1	126.3 (12)	C1^i—C10—C17	117.6 (2)
O1A_d—N1A_d—C4	122.4 (15)	C9—C10—C17	116.69 (19)
C1—N1A_d—C4	109.8 (13)	C16—C11—C12	118.6 (2)
C3A_d—C2A_d—C1	108.0 (8)	C16—C11—C5	121.4 (2)
C3A_d—C2A_d—H2A_d	126.0	C12—C11—C5	120.1 (2)
C1—C2A_d—H2A_d	126.0	C13—C12—C11	120.1 (3)
C2A_d—C3A_d—C4	106.8 (8)	C13—C12—H12	119.9
C2A_d—C3A_d—H3A_d	126.6	C11—C12—H12	119.9
C4—C3A_d—H3A_d	126.6	C14—C13—C12	120.6 (3)
O2A2_c—C4—C5	121.6 (8)	C14—C13—H13	119.7
N1A_d—C4—C5	128.3 (10)	C12—C13—H13	119.7
N1_a—C4—C5	126.6 (6)	C13—C14—C15	119.7 (3)
N1_a—C4—C3_a	109.1 (7)	C13—C14—H14	120.2
C5—C4—C3_a	123.7 (5)	C15—C14—H14	120.2
N1A_d—C4—C3A_d	108.0 (11)	C14—C15—C16	120.4 (3)
C5—C4—C3A_d	123.4 (5)	C14—C15—H15	119.8
C5—C4—C3A1_b	128.6 (5)	C16—C15—H15	119.8
C6—C5—C4	125.6 (2)	C15—C16—C11	120.5 (3)
C6—C5—C11	117.33 (19)	C15—C16—H16	119.8
C4—C5—C11	117.0 (2)	C11—C16—H16	119.8
O2B2_g—C6—C5	123.1 (9)	C22—C17—C18	118.5 (2)
N2_e—C6—C5	126.5 (2)	C22—C17—C10	121.5 (2)
N2B_h—C6—C5	126.8 (6)	C18—C17—C10	119.9 (2)
N2_e—C6—C7_e	106.9 (3)	C19—C18—C17	120.8 (2)
C5—C6—C7_e	126.6 (3)	C19—C18—H18	119.6
C5—C6—C7B1_f	129.9 (8)	C17—C18—H18	119.6
N2B_h—C6—C7B_h	106.9 (8)	C20—C19—C18	119.8 (2)
C5—C6—C7B_h	126.2 (6)	C20—C19—H19	120.1
C9—N2_e—C6	110.2 (3)	C18—C19—H19	120.1
C9—N2_e—H2A1_e	124.9	C21—C20—C19	120.1 (2)
C6—N2_e—H2A1_e	124.9	C21—C20—H20	120.0
C8_e—C7_e—C6	107.8 (4)	C19—C20—H20	120.0
C8_e—C7_e—H7_e	126.1	C20—C21—C22	120.0 (2)
C6—C7_e—H7_e	126.1	C20—C21—H21	120.0
C7_e—C8_e—C9	107.9 (4)	C22—C21—H21	120.0
C7_e—C8_e—H8_e	126.0	C21—C22—C17	120.8 (2)
C9—C8_e—H8_e	126.0	C21—C22—H22	119.6
O3B1_f—C7B1_f—O2B1_f	115.7 (18)	C17—C22—H22	119.6
O2A1_b—C1—N1_a—C4	2.0 (18)	O2B2_g—C6—C7_e—C8_e	116 (10)
N1A_d—C1—N1_a—C4	80 (7)	N2_e—C6—C7_e—C8_e	−0.5 (5)
C10^i—C1—N1_a—C4	−175.3 (6)	N2B_h—C6—C7_e—C8_e	−16.5 (10)
C2A2_c—C1—N1_a—C4	14.0 (18)	C5—C6—C7_e—C8_e	177.9 (5)
C2A_d—C1—N1_a—C4	−9.0 (17)	C7B1_f—C6—C7_e—C8_e	−45 (14)
C2_a—C1—N1_a—C4	−2.1 (18)	C7B_h—C6—C7_e—C8_e	84 (3)
O2A1_b—C1—C2_a—C3_a	−140 (12)	C6—C7_e—C8_e—C9	3.2 (7)
N1A_d—C1—C2_a—C3_a	−7 (2)	O2B2_g—C6—C7B1_f—O3B1_f	−52 (8)
N1_a—C1—C2_a—C3_a	0.5 (15)	N2_e—C6—C7B1_f—O3B1_f	−177 (3)
C10^i—C1—C2_a—C3_a	173.8 (10)	N2B_h—C6—C7B1_f—O3B1_f	167 (3)
C2A2_c—C1—C2_a—C3_a	−77 (3)	C5—C6—C7B1_f—O3B1_f	5 (4)
C2A_d—C1—C2_a—C3_a	90 (6)	C7_e—C6—C7B1_f—O3B1_f	−41 (12)
C1—C2_a—C3_a—C4	1.2 (16)	C7B_h—C6—C7B1_f—O3B1_f	−79 (4)
N1A_d—C1—O2A1_b—C3A1_b	−9 (2)	O2B2_g—C6—C7B1_f—O2B1_f	126 (8)
N1_a—C1—O2A1_b—C3A1_b	−1.5 (14)	N2_e—C6—C7B1_f—O2B1_f	0.3 (12)
C10^i—C1—O2A1_b—C3A1_b	175.9 (8)	N2B_h—C6—C7B1_f—O2B1_f	−15.2 (15)
C2A2_c—C1—O2A1_b—C3A1_b	−57 (4)	C5—C6—C7B1_f—O2B1_f	−177.7 (13)
C2A_d—C1—O2A1_b—C3A1_b	66 (3)	C7_e—C6—C7B1_f—O2B1_f	136 (14)
C2_a—C1—O2A1_b—C3A1_b	39 (11)	C7B_h—C6—C7B1_f—O2B1_f	99 (4)
C1—O2A1_b—C3A1_b—O3A1_b	−172.4 (15)	O3B1_f—C7B1_f—O2B1_f—C9	177 (3)
C1—O2A1_b—C3A1_b—C4	0.6 (12)	C6—C7B1_f—O2B1_f—C9	−1.5 (18)
C4—O2A2_c—C2A2_c—O3A2_c	174 (3)	N2_e—C6—O2B2_g—C8B2_g	2.9 (18)
C4—O2A2_c—C2A2_c—C1	−3.2 (18)	N2B_h—C6—O2B2_g—C8B2_g	−13 (2)
O2A1_b—C1—C2A2_c—O3A2_c	−55 (4)	C5—C6—O2B2_g—C8B2_g	175.2 (12)
N1A_d—C1—C2A2_c—O3A2_c	170 (3)	C7_e—C6—O2B2_g—C8B2_g	−62 (9)
N1_a—C1—C2A2_c—O3A2_c	176 (3)	C7B1_f—C6—O2B2_g—C8B2_g	−55 (8)
C10^i—C1—C2A2_c—O3A2_c	6 (3)	C7B_h—C6—O2B2_g—C8B2_g	59 (9)
C2A_d—C1—C2A2_c—O3A2_c	−81 (3)	C6—O2B2_g—C8B2_g—O3B2_g	−176 (3)
C2_a—C1—C2A2_c—O3A2_c	−77 (4)	C6—O2B2_g—C8B2_g—C9	3.8 (19)
O2A1_b—C1—C2A2_c—O2A2_c	122 (5)	O2B2_g—C6—N2B_h—O1B_h	−158 (2)
N1A_d—C1—C2A2_c—O2A2_c	−13 (2)	N2_e—C6—N2B_h—O1B_h	107 (4)
N1_a—C1—C2A2_c—O2A2_c	−6.8 (16)	C5—C6—N2B_h—O1B_h	13 (3)
C10^i—C1—C2A2_c—O2A2_c	−177.2 (11)	C7_e—C6—N2B_h—O1B_h	−153.0 (17)
C2A_d—C1—C2A2_c—O2A2_c	96 (3)	C7B1_f—C6—N2B_h—O1B_h	−151 (2)
C2_a—C1—C2A2_c—O2A2_c	100 (3)	C7B_h—C6—N2B_h—O1B_h	−166.4 (19)
O2A1_b—C1—N1A_d—O1A_d	−152 (3)	O2B2_g—C6—N2B_h—C9	19 (2)
N1_a—C1—N1A_d—O1A_d	104 (8)	N2_e—C6—N2B_h—C9	−76 (2)
C10^i—C1—N1A_d—O1A_d	23 (5)	C5—C6—N2B_h—C9	−170.5 (7)
C2A2_c—C1—N1A_d—O1A_d	−141 (4)	C7_e—C6—N2B_h—C9	23.9 (16)
C2A_d—C1—N1A_d—O1A_d	−163 (3)	C7B1_f—C6—N2B_h—C9	26.2 (18)
C2_a—C1—N1A_d—O1A_d	−157 (3)	C7B_h—C6—N2B_h—C9	10.6 (18)
O2A1_b—C1—N1A_d—C4	14 (4)	O2B2_g—C6—C7B_h—C8B_h	−110 (9)
N1_a—C1—N1A_d—C4	−90 (8)	N2_e—C6—C7B_h—C8B_h	15.7 (11)
C10^i—C1—N1A_d—C4	−170.9 (13)	N2B_h—C6—C7B_h—C8B_h	−0.3 (13)
C2A2_c—C1—N1A_d—C4	25 (3)	C5—C6—C7B_h—C8B_h	−179.2 (14)
C2A_d—C1—N1A_d—C4	3 (3)	C7_e—C6—C7B_h—C8B_h	−83 (3)
C2_a—C1—N1A_d—C4	9 (3)	C7B1_f—C6—C7B_h—C8B_h	−70 (4)
O2A1_b—C1—C2A_d—C3A_d	−109 (4)	C6—C7B_h—C8B_h—C9	−9.6 (18)
N1A_d—C1—C2A_d—C3A_d	0 (2)	C7B1_f—O2B1_f—C9—N2_e	2 (2)
N1_a—C1—C2A_d—C3A_d	7.3 (14)	C7B1_f—O2B1_f—C9—N2B_h	18 (2)
C10^i—C1—C2A_d—C3A_d	174.1 (7)	C7B1_f—O2B1_f—C9—C10	177.0 (8)
C2A2_c—C1—C2A_d—C3A_d	−76 (2)	C7B1_f—O2B1_f—C9—C8_e	−59 (10)
C2_a—C1—C2A_d—C3A_d	−86 (6)	C7B1_f—O2B1_f—C9—C8B2_g	−58 (6)
C1—C2A_d—C3A_d—C4	−2.7 (10)	C7B1_f—O2B1_f—C9—C8B_h	−71 (5)
C2A2_c—O2A2_c—C4—N1A_d	19 (2)	C6—N2_e—C9—O2B1_f	−1.9 (19)
C2A2_c—O2A2_c—C4—N1_a	12 (2)	C6—N2_e—C9—N2B_h	−82 (5)
C2A2_c—O2A2_c—C4—C5	−179.0 (9)	C6—N2_e—C9—C10	−176.6 (2)
C2A2_c—O2A2_c—C4—C3_a	−77 (3)	C6—N2_e—C9—C8_e	4.4 (5)
C2A2_c—O2A2_c—C4—C3A_d	−77 (2)	C6—N2_e—C9—C8B2_g	10.6 (17)
C2A2_c—O2A2_c—C4—C3A1_b	−58 (4)	C6—N2_e—C9—C8B_h	10.3 (17)
O1A_d—N1A_d—C4—O2A2_c	138 (3)	O1B_h—N2B_h—C9—O2B1_f	148 (2)
C1—N1A_d—C4—O2A2_c	−29 (4)	C6—N2B_h—C9—O2B1_f	−29 (2)
O1A_d—N1A_d—C4—N1_a	−101 (12)	O1B_h—N2B_h—C9—N2_e	−107 (6)
C1—N1A_d—C4—N1_a	92 (12)	C6—N2B_h—C9—N2_e	76 (4)
O1A_d—N1A_d—C4—C5	−23 (5)	O1B_h—N2B_h—C9—C10	−10 (3)
C1—N1A_d—C4—C5	170.3 (13)	C6—N2B_h—C9—C10	173.3 (6)
O1A_d—N1A_d—C4—C3_a	158 (3)	O1B_h—N2B_h—C9—C8_e	154.8 (18)
C1—N1A_d—C4—C3_a	−9 (3)	C6—N2B_h—C9—C8_e	−22.1 (16)
O1A_d—N1A_d—C4—C3A_d	162 (3)	O1B_h—N2B_h—C9—C8B2_g	162 (2)
C1—N1A_d—C4—C3A_d	−4 (4)	C6—N2B_h—C9—C8B2_g	−15 (2)
O1A_d—N1A_d—C4—C3A1_b	154 (3)	O1B_h—N2B_h—C9—C8B_h	161 (2)
C1—N1A_d—C4—C3A1_b	−13 (3)	C6—N2B_h—C9—C8B_h	−16 (2)
C1—N1_a—C4—O2A2_c	−17 (2)	C7_e—C8_e—C9—O2B1_f	116 (12)
C1—N1_a—C4—N1A_d	−78 (12)	C7_e—C8_e—C9—N2_e	−4.7 (7)
C1—N1_a—C4—C5	174.8 (6)	C7_e—C8_e—C9—N2B_h	11.3 (11)
C1—N1_a—C4—C3_a	3 (2)	C7_e—C8_e—C9—C10	176.3 (3)
C1—N1_a—C4—C3A_d	7.4 (17)	C7_e—C8_e—C9—C8B2_g	−62 (9)
C1—N1_a—C4—C3A1_b	−1.5 (17)	C7_e—C8_e—C9—C8B_h	−89 (7)
C2_a—C3_a—C4—O2A2_c	95 (3)	O3B2_g—C8B2_g—C9—O2B1_f	−66 (6)
C2_a—C3_a—C4—N1A_d	4 (2)	O2B2_g—C8B2_g—C9—O2B1_f	115 (7)
C2_a—C3_a—C4—N1_a	−2.6 (19)	O3B2_g—C8B2_g—C9—N2_e	171 (3)
C2_a—C3_a—C4—C5	−174.8 (8)	O2B2_g—C8B2_g—C9—N2_e	−8.8 (19)
C2_a—C3_a—C4—C3A_d	−87 (10)	O3B2_g—C8B2_g—C9—N2B_h	−173 (3)
C2_a—C3_a—C4—C3A1_b	41 (12)	O2B2_g—C8B2_g—C9—N2B_h	7 (2)
C2A_d—C3A_d—C4—O2A2_c	96 (3)	O3B2_g—C8B2_g—C9—C10	−2 (4)
C2A_d—C3A_d—C4—N1A_d	4 (2)	O2B2_g—C8B2_g—C9—C10	178.4 (11)
C2A_d—C3A_d—C4—N1_a	−2.8 (13)	O3B2_g—C8B2_g—C9—C8_e	−65 (8)
C2A_d—C3A_d—C4—C5	−170.6 (6)	O2B2_g—C8B2_g—C9—C8_e	116 (10)
C2A_d—C3A_d—C4—C3_a	94 (10)	O3B2_g—C8B2_g—C9—C8B_h	−13 (42)
C2A_d—C3A_d—C4—C3A1_b	64 (5)	O2B2_g—C8B2_g—C9—C8B_h	167 (44)
O3A1_b—C3A1_b—C4—O2A2_c	−73 (4)	C7B_h—C8B_h—C9—O2B1_f	111 (7)
O2A1_b—C3A1_b—C4—O2A2_c	115 (5)	C7B_h—C8B_h—C9—N2_e	0 (2)
O3A1_b—C3A1_b—C4—N1A_d	179 (3)	C7B_h—C8B_h—C9—N2B_h	16 (2)
O2A1_b—C3A1_b—C4—N1A_d	7 (2)	C7B_h—C8B_h—C9—C10	−173.3 (7)
O3A1_b—C3A1_b—C4—N1_a	173 (2)	C7B_h—C8B_h—C9—C8_e	97 (7)
O2A1_b—C3A1_b—C4—N1_a	0.6 (15)	C7B_h—C8B_h—C9—C8B2_g	−4 (42)
O3A1_b—C3A1_b—C4—C5	−4 (2)	O2B1_f—C9—C10—C1^i	180 (2)
O2A1_b—C3A1_b—C4—C5	−175.6 (6)	N2_e—C9—C10—C1^i	−6.2 (4)
O3A1_b—C3A1_b—C4—C3_a	35 (12)	N2B_h—C9—C10—C1^i	−25.7 (12)
O2A1_b—C3A1_b—C4—C3_a	−137 (14)	C8_e—C9—C10—C1^i	172.6 (6)
O3A1_b—C3A1_b—C4—C3A_d	56 (4)	C8B2_g—C9—C10—C1^i	165 (2)
O2A1_b—C3A1_b—C4—C3A_d	−116 (5)	C8B_h—C9—C10—C1^i	166 (2)
O2A2_c—C4—C5—C6	−172.3 (16)	O2B1_f—C9—C10—C17	−4 (2)
N1A_d—C4—C5—C6	−14 (2)	N2_e—C9—C10—C17	169.7 (2)
N1_a—C4—C5—C6	−5.5 (12)	N2B_h—C9—C10—C17	150.2 (12)
C3_a—C4—C5—C6	165.2 (13)	C8_e—C9—C10—C17	−11.5 (6)
C3A_d—C4—C5—C6	160.1 (8)	C8B2_g—C9—C10—C17	−19 (2)
C3A1_b—C4—C5—C6	169.8 (10)	C8B_h—C9—C10—C17	−18 (2)
O2A2_c—C4—C5—C11	10.8 (16)	C6—C5—C11—C16	−60.3 (3)
N1A_d—C4—C5—C11	169 (2)	C4—C5—C11—C16	116.9 (3)
N1_a—C4—C5—C11	177.5 (11)	C6—C5—C11—C12	119.1 (2)
C3_a—C4—C5—C11	−11.7 (13)	C4—C5—C11—C12	−63.7 (3)
C3A_d—C4—C5—C11	−16.8 (9)	C16—C11—C12—C13	0.5 (4)
C3A1_b—C4—C5—C11	−7.1 (10)	C5—C11—C12—C13	−178.9 (2)
C4—C5—C6—O2B2_g	−171 (2)	C11—C12—C13—C14	0.7 (4)
C11—C5—C6—O2B2_g	6 (2)	C12—C13—C14—C15	−0.9 (5)
C4—C5—C6—N2_e	0.1 (4)	C13—C14—C15—C16	−0.1 (5)
C11—C5—C6—N2_e	177.0 (2)	C14—C15—C16—C11	1.3 (5)
C4—C5—C6—N2B_h	19.4 (12)	C12—C11—C16—C15	−1.5 (4)
C11—C5—C6—N2B_h	−163.7 (12)	C5—C11—C16—C15	177.9 (2)
C4—C5—C6—C7_e	−178.0 (4)	C1^i—C10—C17—C22	−57.5 (3)
C11—C5—C6—C7_e	−1.1 (4)	C9—C10—C17—C22	126.3 (2)
C4—C5—C6—C7B1_f	177.7 (15)	C1^i—C10—C17—C18	121.9 (2)
C11—C5—C6—C7B1_f	−5.4 (15)	C9—C10—C17—C18	−54.4 (3)
C4—C5—C6—C7B_h	−161.8 (12)	C22—C17—C18—C19	−0.5 (3)
C11—C5—C6—C7B_h	15.1 (12)	C10—C17—C18—C19	−179.8 (2)
O2B2_g—C6—N2_e—C9	−9.0 (17)	C17—C18—C19—C20	0.3 (4)
N2B_h—C6—N2_e—C9	82 (3)	C18—C19—C20—C21	0.2 (4)
C5—C6—N2_e—C9	179.1 (2)	C19—C20—C21—C22	−0.6 (4)
C7_e—C6—N2_e—C9	−2.5 (4)	C20—C21—C22—C17	0.5 (4)
C7B1_f—C6—N2_e—C9	0.9 (12)	C18—C17—C22—C21	0.1 (3)
C7B_h—C6—N2_e—C9	−15.9 (10)	C10—C17—C22—C21	179.4 (2)

Symmetry code: (i) −x, −y+1, −z+1.