Fourfold alkyl wrapping of a copper(II) por­phy­rin thwarts macrocycle π–π stacking in a com­pact supra­molecular package

Porphyrins are valuable constituents in optoelectronic, catalytic, and other applications, yet control of inter­molecular π–π stacking is invariably essential to attain the desired properties. Superstructures built onto the por­phy­rin, often via meso-aryl groups, can afford facial encumbrance that suppresses π–π stacking, although some mol­ecular designs have provided insufficient facial coverage and many have entailed cumbersome syntheses. In this study, a copper(II) por­phy­rin bearing four meso substituents, namely, {10,20-bis­[2,6-bis­(oct­yloxy)phen­yl]-5,15-di­bromo­porphinato}copper(II), [Cu(C₆₄H₈₂Br₂N₄O₄)], was prepared by metalation of the corresponding free-base por­phy­rin and was characterized by single-crystal X-ray diffraction. The crystal structure reveals a dihedral angle of 111.1 (2)° for the plane of the meso-aryl group relative to the plane of the por­phy­rin, with both aryl groups tilted in the same direction. Each of the four oct­yloxy groups exhibits a gauche con­formation for the –OCH₂CH₂– unit but is extended with four or five anti (–CH₂CH₂–/H) con­formations thereafter, causing each octyl group to span the dimension of the macrocycle. In a global frame of reference where the two Br atoms define the north/south poles and the two aryl groups are at anti­podes on the equator, two octyl groups of one aryl unit project over the northern hemisphere (covering pyrroles A and B), whereas those of the other aryl unit project over the southern hemisphere (covering pyrroles C and D). Together, the four octyl groups ensheath the two faces of the por­phy­rin in a self-wrapped assembly. The closest approach of the Cu atom to an octyl methyl­ene C atom (position 6) is 3.5817 (18) Å, the mean separations of neighboring por­phy­rin planes are 8.059 (4) and 4.693 (8) Å along the a and c axes, respectively, and the center-to-center distances between the Cu atoms of neighboring por­phy­rins are 10.2725 (4), 12.2540 (6), and 12.7472 (6) Å along the a, b, and c axes, respectively. The Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots provide information concerning contact inter­actions in the supra­molecular assembly of the solid crystal.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELX2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury4 (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

{10,20-Bis[2,6-bis(octyloxy)phenyl]-5,15-dibromoporphinato}copper(II)

Crystal data

[Cu(C64H82Br2N4O4)]	Z = 1
Mr = 1194.74	F(000) = 624.9962
Triclinic, P1	Dx = 1.389 Mg m^−3
a = 10.2725 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2540 (6) Å	Cell parameters from 9818 reflections
c = 12.7472 (6) Å	θ = 2.3–33.3°
α = 109.923 (2)°	µ = 1.83 mm^−1
β = 105.202 (2)°	T = 104 K
γ = 94.953 (2)°	Prism, red
V = 1428.23 (12) Å^3	0.24 × 0.18 × 0.10 mm

Data collection

Bruker D8 Venture diffractometer	9497 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	7292 reflections with I ≥ 2u(I)
Mirror optics monochromator	Rint = 0.064
Detector resolution: 7.9 pixels mm^-1	θmax = 31.5°, θmin = 2.3°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −18→18
Tmin = 0.607, Tmax = 0.747	l = −18→18
71914 measured reflections

Refinement

Refinement on F^2	64 constraints
Least-squares matrix: full	Primary atom site location: iterative
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 1.1126P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
9497 reflections	Δρmax = 0.89 e Å^−3
342 parameters	Δρmin = −0.73 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
Br1	0.34332 (2)	0.155486 (15)	0.630731 (17)	0.01886 (6)
Cu1	0.5	0.5	0.5	0.00831 (6)
O1	0.57359 (13)	0.76323 (11)	0.94831 (11)	0.0152 (3)
O2	0.19879 (14)	0.81547 (12)	0.68666 (12)	0.0193 (3)
N1	0.50270 (15)	0.67441 (12)	0.55434 (12)	0.0098 (3)
N2	0.42439 (15)	0.49187 (12)	0.62707 (12)	0.0100 (3)
C1	0.8786 (2)	0.07511 (19)	0.7356 (2)	0.0291 (5)
H1a	0.9547 (9)	0.1111 (7)	0.7177 (14)	0.0437 (7)*
H1b	0.9140 (13)	0.0632 (12)	0.8093 (5)	0.0437 (7)*
H1c	0.8336 (5)	−0.0013 (5)	0.6718 (10)	0.0437 (7)*
C2	0.7748 (2)	0.15653 (17)	0.74772 (19)	0.0222 (4)
H2a	0.7373 (2)	0.16623 (17)	0.67223 (19)	0.0267 (5)*
H2b	0.6975 (2)	0.11911 (17)	0.76453 (19)	0.0267 (5)*
C3	0.8368 (2)	0.27757 (17)	0.84435 (19)	0.0221 (4)
H3a	0.8747 (2)	0.26751 (17)	0.91961 (19)	0.0266 (5)*
H3b	0.9141 (2)	0.31470 (17)	0.82729 (19)	0.0266 (5)*
C4	0.7348 (2)	0.36047 (17)	0.85839 (19)	0.0203 (4)
H4a	0.6923 (2)	0.36637 (17)	0.78174 (19)	0.0244 (5)*
H4b	0.6607 (2)	0.32577 (17)	0.88060 (19)	0.0244 (5)*
C5	0.7989 (2)	0.48418 (16)	0.94984 (18)	0.0185 (4)
H5a	0.8405 (2)	0.47880 (16)	1.02688 (18)	0.0222 (5)*
H5b	0.8733 (2)	0.51914 (16)	0.92813 (18)	0.0222 (5)*
C6	0.69453 (19)	0.56517 (16)	0.96108 (17)	0.0170 (4)
H6a	0.64670 (19)	0.56388 (16)	0.88226 (17)	0.0204 (4)*
H6b	0.62480 (19)	0.53341 (16)	0.98951 (17)	0.0204 (4)*
C7	0.75681 (19)	0.69301 (16)	1.04374 (16)	0.0158 (4)
H7a	0.81226 (19)	0.69439 (16)	1.12065 (16)	0.0189 (4)*
H7b	0.81914 (19)	0.72806 (16)	1.01118 (16)	0.0189 (4)*
C8	0.6483 (2)	0.76729 (16)	1.06170 (15)	0.0153 (4)
H8a	0.6918 (2)	0.84983 (16)	1.11525 (15)	0.0184 (4)*
H8b	0.5861 (2)	0.73478 (16)	1.09603 (15)	0.0184 (4)*
C9	0.46027 (19)	0.81382 (15)	0.93715 (16)	0.0130 (3)
C10	0.38135 (18)	0.78882 (15)	0.82180 (15)	0.0123 (3)
C11	0.41453 (18)	0.70215 (15)	0.72188 (15)	0.0107 (3)
C12	0.46531 (18)	0.74250 (14)	0.64850 (15)	0.0112 (3)
C13	0.39395 (18)	0.58387 (15)	0.70949 (15)	0.0104 (3)
C14	0.4236 (2)	0.88624 (15)	1.03183 (16)	0.0157 (4)
H14	0.4759 (2)	0.90021 (15)	1.11022 (16)	0.0188 (4)*
C15	0.3096 (2)	0.93727 (16)	1.00918 (17)	0.0182 (4)
H15	0.2842 (2)	0.98666 (16)	1.07317 (17)	0.0218 (5)*
C16	0.2318 (2)	0.91817 (16)	0.89580 (17)	0.0167 (4)
H16	0.1550 (2)	0.95526 (16)	0.88195 (17)	0.0200 (4)*
C17	0.26793 (19)	0.84342 (15)	0.80202 (16)	0.0143 (3)
C18	0.54693 (18)	0.75258 (14)	0.50878 (15)	0.0111 (3)
C19	0.40192 (18)	0.28010 (14)	0.58551 (15)	0.0118 (3)
C20	0.38785 (18)	0.39293 (15)	0.64943 (15)	0.0109 (3)
C21	0.33342 (19)	0.42373 (15)	0.74601 (16)	0.0140 (3)
H21	0.30113 (19)	0.37132 (15)	0.77807 (16)	0.0168 (4)*
C22	0.33674 (19)	0.54147 (15)	0.78285 (16)	0.0133 (3)
H22	0.30682 (19)	0.58750 (15)	0.84552 (16)	0.0160 (4)*
C23	0.53542 (19)	0.87075 (15)	0.57466 (16)	0.0145 (3)
H23	0.55832 (19)	0.93996 (15)	0.56027 (16)	0.0174 (4)*
C24	0.48585 (19)	0.86425 (15)	0.66074 (16)	0.0145 (3)
H24	0.46778 (19)	0.92842 (15)	0.71889 (16)	0.0174 (4)*
C25	0.0973 (2)	0.88138 (17)	0.65550 (18)	0.0202 (4)
H25a	0.0129 (2)	0.85778 (17)	0.67252 (18)	0.0242 (5)*
H25b	0.1325 (2)	0.96709 (17)	0.70122 (18)	0.0242 (5)*
C26	0.0661 (2)	0.85525 (17)	0.52592 (18)	0.0230 (4)
H26a	−0.0004 (2)	0.90380 (17)	0.50422 (18)	0.0276 (5)*
H26b	0.1518 (2)	0.88103 (17)	0.51191 (18)	0.0276 (5)*
C27	0.0077 (2)	0.72571 (18)	0.44380 (19)	0.0255 (4)
H27a	−0.0628 (2)	0.69369 (18)	0.47139 (19)	0.0306 (5)*
H27b	−0.0393 (2)	0.72344 (18)	0.36442 (19)	0.0306 (5)*
C28	0.1118 (2)	0.64399 (18)	0.43356 (19)	0.0231 (4)
H28a	0.1895 (2)	0.68043 (18)	0.41650 (19)	0.0277 (5)*
H28b	0.1486 (2)	0.63504 (18)	0.50952 (19)	0.0277 (5)*
C29	0.0484 (2)	0.52265 (18)	0.33750 (19)	0.0228 (4)
H29a	−0.0294 (2)	0.48701 (18)	0.35510 (19)	0.0274 (5)*
H29b	0.0107 (2)	0.53252 (18)	0.26211 (19)	0.0274 (5)*
C30	0.1479 (2)	0.43728 (18)	0.32276 (18)	0.0218 (4)
H30a	0.2275 (2)	0.47347 (18)	0.30769 (18)	0.0262 (5)*
H30b	0.1827 (2)	0.42403 (18)	0.39670 (18)	0.0262 (5)*
C31	0.0810 (2)	0.31868 (17)	0.22242 (19)	0.0220 (4)
H31a	−0.0020 (2)	0.28533 (17)	0.23527 (19)	0.0264 (5)*
H31b	0.0510 (2)	0.33195 (17)	0.14807 (19)	0.0264 (5)*
C32	0.1751 (2)	0.22856 (19)	0.2096 (2)	0.0257 (4)
H32a	0.2565 (8)	0.2598 (6)	0.1946 (14)	0.0386 (7)*
H32b	0.2037 (13)	0.2133 (11)	0.2821 (5)	0.0386 (7)*
H32c	0.1257 (6)	0.1547 (5)	0.1439 (9)	0.0386 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03132 (12)	0.01078 (8)	0.01746 (10)	0.00230 (7)	0.01190 (8)	0.00614 (7)
Cu1	0.01070 (14)	0.00684 (12)	0.00699 (13)	0.00283 (10)	0.00327 (11)	0.00148 (10)
O1	0.0193 (7)	0.0167 (6)	0.0097 (6)	0.0088 (5)	0.0049 (5)	0.0036 (5)
O2	0.0189 (7)	0.0220 (7)	0.0147 (7)	0.0130 (6)	0.0033 (6)	0.0035 (5)
N1	0.0122 (7)	0.0079 (6)	0.0091 (7)	0.0029 (5)	0.0038 (6)	0.0023 (5)
N2	0.0121 (7)	0.0086 (6)	0.0090 (7)	0.0029 (5)	0.0034 (6)	0.0027 (5)
C1	0.0301 (12)	0.0199 (10)	0.0377 (13)	0.0116 (9)	0.0111 (10)	0.0090 (9)
C2	0.0228 (10)	0.0164 (9)	0.0266 (11)	0.0061 (8)	0.0077 (9)	0.0066 (8)
C3	0.0183 (10)	0.0170 (9)	0.0291 (11)	0.0050 (8)	0.0051 (8)	0.0076 (8)
C4	0.0159 (9)	0.0158 (8)	0.0263 (10)	0.0051 (7)	0.0044 (8)	0.0056 (8)
C5	0.0152 (9)	0.0173 (9)	0.0223 (10)	0.0054 (7)	0.0035 (8)	0.0078 (8)
C6	0.0131 (9)	0.0158 (8)	0.0206 (10)	0.0041 (7)	0.0040 (7)	0.0057 (7)
C7	0.0136 (9)	0.0177 (8)	0.0145 (9)	0.0018 (7)	0.0017 (7)	0.0065 (7)
C8	0.0201 (9)	0.0146 (8)	0.0091 (8)	0.0038 (7)	0.0029 (7)	0.0030 (6)
C9	0.0160 (9)	0.0102 (7)	0.0138 (8)	0.0037 (6)	0.0074 (7)	0.0034 (6)
C10	0.0153 (9)	0.0100 (7)	0.0117 (8)	0.0034 (6)	0.0065 (7)	0.0020 (6)
C11	0.0107 (8)	0.0117 (7)	0.0086 (7)	0.0047 (6)	0.0030 (6)	0.0018 (6)
C12	0.0121 (8)	0.0095 (7)	0.0094 (8)	0.0034 (6)	0.0016 (6)	0.0013 (6)
C13	0.0119 (8)	0.0108 (7)	0.0078 (7)	0.0033 (6)	0.0029 (6)	0.0025 (6)
C14	0.0227 (10)	0.0128 (8)	0.0111 (8)	0.0045 (7)	0.0081 (7)	0.0016 (7)
C15	0.0241 (10)	0.0137 (8)	0.0180 (9)	0.0058 (7)	0.0133 (8)	0.0019 (7)
C16	0.0175 (9)	0.0137 (8)	0.0210 (9)	0.0074 (7)	0.0105 (8)	0.0047 (7)
C17	0.0147 (9)	0.0134 (8)	0.0147 (9)	0.0037 (7)	0.0058 (7)	0.0041 (7)
C18	0.0132 (8)	0.0092 (7)	0.0092 (8)	0.0027 (6)	0.0028 (7)	0.0020 (6)
C19	0.0151 (9)	0.0095 (7)	0.0112 (8)	0.0011 (6)	0.0029 (7)	0.0055 (6)
C20	0.0115 (8)	0.0114 (7)	0.0091 (8)	0.0012 (6)	0.0028 (6)	0.0034 (6)
C21	0.0158 (9)	0.0137 (8)	0.0125 (8)	0.0016 (7)	0.0060 (7)	0.0041 (7)
C22	0.0153 (9)	0.0135 (8)	0.0116 (8)	0.0032 (7)	0.0072 (7)	0.0029 (6)
C23	0.0202 (9)	0.0085 (7)	0.0143 (8)	0.0033 (7)	0.0058 (7)	0.0031 (6)
C24	0.0208 (9)	0.0080 (7)	0.0128 (8)	0.0036 (7)	0.0052 (7)	0.0013 (6)
C25	0.0203 (10)	0.0191 (9)	0.0236 (10)	0.0104 (8)	0.0068 (8)	0.0095 (8)
C26	0.0259 (11)	0.0185 (9)	0.0234 (10)	0.0086 (8)	0.0023 (9)	0.0096 (8)
C27	0.0232 (11)	0.0210 (10)	0.0253 (11)	0.0054 (8)	−0.0013 (9)	0.0069 (8)
C28	0.0195 (10)	0.0204 (9)	0.0222 (10)	0.0028 (8)	−0.0002 (8)	0.0047 (8)
C29	0.0201 (10)	0.0199 (9)	0.0226 (10)	0.0037 (8)	0.0004 (8)	0.0055 (8)
C30	0.0187 (10)	0.0208 (9)	0.0219 (10)	0.0022 (8)	0.0016 (8)	0.0069 (8)
C31	0.0202 (10)	0.0186 (9)	0.0246 (11)	0.0015 (8)	0.0034 (8)	0.0082 (8)
C32	0.0245 (11)	0.0218 (10)	0.0302 (12)	0.0058 (8)	0.0085 (9)	0.0087 (9)

Geometric parameters (Å, º)

Br1—C19	1.9104 (16)	C12—C24	1.437 (2)
Cu1—N1	2.0047 (13)	C13—C22	1.434 (2)
Cu1—N1^i	2.0047 (13)	C14—H14	0.9500
Cu1—N2	1.9983 (14)	C14—C15	1.385 (3)
Cu1—N2^i	1.9983 (14)	C15—H15	0.9500
O1—C8	1.429 (2)	C15—C16	1.384 (3)
O1—C9	1.363 (2)	C16—H16	0.9500
O2—C17	1.361 (2)	C16—C17	1.397 (2)
O2—C25	1.430 (2)	C18—C19^i	1.386 (2)
N1—C12	1.378 (2)	C18—C23	1.438 (2)
N1—C18	1.380 (2)	C19—C20	1.387 (2)
N2—C13	1.378 (2)	C20—C21	1.432 (2)
N2—C20	1.380 (2)	C21—H21	0.9500
C1—H1a	0.9800	C21—C22	1.351 (2)
C1—H1b	0.9800	C22—H22	0.9500
C1—H1c	0.9800	C23—H23	0.9500
C1—C2	1.523 (3)	C23—C24	1.347 (3)
C2—H2a	0.9900	C24—H24	0.9500
C2—H2b	0.9900	C25—H25a	0.9900
C2—C3	1.518 (3)	C25—H25b	0.9900
C3—H3a	0.9900	C25—C26	1.509 (3)
C3—H3b	0.9900	C26—H26a	0.9900
C3—C4	1.523 (3)	C26—H26b	0.9900
C4—H4a	0.9900	C26—C27	1.533 (3)
C4—H4b	0.9900	C27—H27a	0.9900
C4—C5	1.520 (3)	C27—H27b	0.9900
C5—H5a	0.9900	C27—C28	1.528 (3)
C5—H5b	0.9900	C28—H28a	0.9900
C5—C6	1.524 (3)	C28—H28b	0.9900
C6—H6a	0.9900	C28—C29	1.519 (3)
C6—H6b	0.9900	C29—H29a	0.9900
C6—C7	1.524 (3)	C29—H29b	0.9900
C7—H7a	0.9900	C29—C30	1.525 (3)
C7—H7b	0.9900	C30—H30a	0.9900
C7—C8	1.513 (3)	C30—H30b	0.9900
C8—H8a	0.9900	C30—C31	1.523 (3)
C8—H8b	0.9900	C31—H31a	0.9900
C9—C10	1.392 (3)	C31—H31b	0.9900
C9—C14	1.397 (2)	C31—C32	1.525 (3)
C10—C11	1.495 (2)	C32—H32a	0.9800
C10—C17	1.401 (2)	C32—H32b	0.9800
C11—C12	1.385 (2)	C32—H32c	0.9800
C11—C13	1.394 (2)
N1—Cu1—N1^i	180.0	C15—C14—H14	120.64 (11)
N2—Cu1—N1^i	90.06 (6)	H15—C15—C14	119.15 (11)
N2—Cu1—N1	89.94 (6)	C16—C15—C14	121.71 (17)
N2^i—Cu1—N1^i	89.94 (6)	C16—C15—H15	119.15 (10)
N2^i—Cu1—N1	90.06 (6)	H16—C16—C15	120.57 (10)
N2^i—Cu1—N2	180.0	C17—C16—C15	118.86 (17)
C9—O1—C8	118.76 (14)	C17—C16—H16	120.57 (11)
C25—O2—C17	119.20 (14)	C10—C17—O2	114.32 (15)
C12—N1—Cu1^i	127.01 (11)	C16—C17—O2	124.79 (16)
C18—N1—Cu1^i	127.66 (11)	C16—C17—C10	120.89 (17)
C18—N1—C12	105.29 (13)	C19^i—C18—N1	123.73 (15)
C13—N2—Cu1	127.22 (11)	C23—C18—N1	110.44 (15)
C20—N2—Cu1	127.68 (11)	C23—C18—C19^i	125.82 (16)
C20—N2—C13	105.08 (14)	C18^i—C19—Br1	116.10 (12)
H1b—C1—H1a	109.5	C20—C19—Br1	116.89 (13)
H1c—C1—H1a	109.5	C20—C19—C18^i	127.00 (16)
H1c—C1—H1b	109.5	C19—C20—N2	123.85 (15)
C2—C1—H1a	109.5	C21—C20—N2	110.48 (14)
C2—C1—H1b	109.5	C21—C20—C19	125.66 (16)
C2—C1—H1c	109.5	H21—C21—C20	126.52 (10)
H2a—C2—C1	109.03 (13)	C22—C21—C20	106.96 (16)
H2b—C2—C1	109.03 (12)	C22—C21—H21	126.52 (11)
H2b—C2—H2a	107.8	C21—C22—C13	107.06 (15)
C3—C2—C1	112.78 (18)	H22—C22—C13	126.47 (10)
C3—C2—H2a	109.03 (11)	H22—C22—C21	126.47 (11)
C3—C2—H2b	109.03 (12)	H23—C23—C18	126.65 (10)
H3a—C3—C2	108.82 (11)	C24—C23—C18	106.69 (15)
H3b—C3—C2	108.82 (12)	C24—C23—H23	126.65 (10)
H3b—C3—H3a	107.7	C23—C24—C12	107.48 (15)
C4—C3—C2	113.73 (17)	H24—C24—C12	126.26 (10)
C4—C3—H3a	108.82 (12)	H24—C24—C23	126.26 (10)
C4—C3—H3b	108.82 (11)	H25a—C25—O2	110.19 (10)
H4a—C4—C3	108.82 (12)	H25b—C25—O2	110.19 (10)
H4b—C4—C3	108.82 (11)	H25b—C25—H25a	108.5
H4b—C4—H4a	107.7	C26—C25—O2	107.60 (16)
C5—C4—C3	113.72 (16)	C26—C25—H25a	110.19 (12)
C5—C4—H4a	108.82 (11)	C26—C25—H25b	110.19 (11)
C5—C4—H4b	108.82 (11)	H26a—C26—C25	108.29 (10)
H5a—C5—C4	109.11 (11)	H26b—C26—C25	108.29 (12)
H5b—C5—C4	109.11 (11)	H26b—C26—H26a	107.4
H5b—C5—H5a	107.8	C27—C26—C25	115.99 (17)
C6—C5—C4	112.44 (16)	C27—C26—H26a	108.29 (11)
C6—C5—H5a	109.11 (11)	C27—C26—H26b	108.29 (12)
C6—C5—H5b	109.11 (10)	H27a—C27—C26	108.30 (12)
H6a—C6—C5	108.72 (11)	H27b—C27—C26	108.30 (11)
H6b—C6—C5	108.72 (11)	H27b—C27—H27a	107.4
H6b—C6—H6a	107.6	C28—C27—C26	115.95 (18)
C7—C6—C5	114.13 (16)	C28—C27—H27a	108.30 (12)
C7—C6—H6a	108.72 (10)	C28—C27—H27b	108.30 (12)
C7—C6—H6b	108.72 (10)	H28a—C28—C27	109.21 (12)
H7a—C7—C6	109.14 (10)	H28b—C28—C27	109.21 (12)
H7b—C7—C6	109.14 (10)	H28b—C28—H28a	107.9
H7b—C7—H7a	107.9	C29—C28—C27	112.02 (17)
C8—C7—C6	112.29 (15)	C29—C28—H28a	109.21 (12)
C8—C7—H7a	109.14 (10)	C29—C28—H28b	109.21 (12)
C8—C7—H7b	109.14 (10)	H29a—C29—C28	108.67 (12)
C7—C8—O1	106.40 (14)	H29b—C29—C28	108.67 (12)
H8a—C8—O1	110.45 (9)	H29b—C29—H29a	107.6
H8a—C8—C7	110.45 (10)	C30—C29—C28	114.37 (17)
H8b—C8—O1	110.45 (9)	C30—C29—H29a	108.67 (11)
H8b—C8—C7	110.45 (10)	C30—C29—H29b	108.67 (12)
H8b—C8—H8a	108.6	H30a—C30—C29	109.13 (11)
C10—C9—O1	114.68 (15)	H30b—C30—C29	109.13 (12)
C14—C9—O1	124.13 (16)	H30b—C30—H30a	107.9
C14—C9—C10	121.19 (16)	C31—C30—C29	112.36 (17)
C11—C10—C9	120.37 (15)	C31—C30—H30a	109.13 (12)
C17—C10—C9	118.54 (16)	C31—C30—H30b	109.13 (11)
C17—C10—C11	121.05 (16)	H31a—C31—C30	108.80 (12)
C12—C11—C10	119.24 (15)	H31b—C31—C30	108.80 (11)
C13—C11—C10	117.08 (15)	H31b—C31—H31a	107.7
C13—C11—C12	123.67 (15)	C32—C31—C30	113.80 (17)
C11—C12—N1	126.17 (15)	C32—C31—H31a	108.80 (11)
C24—C12—N1	110.10 (15)	C32—C31—H31b	108.80 (12)
C24—C12—C11	123.74 (16)	H32a—C32—C31	109.5
C11—C13—N2	125.93 (16)	H32b—C32—C31	109.5
C22—C13—N2	110.41 (14)	H32b—C32—H32a	109.5
C22—C13—C11	123.66 (15)	H32c—C32—C31	109.5
H14—C14—C9	120.64 (11)	H32c—C32—H32a	109.5
C15—C14—C9	118.72 (17)	H32c—C32—H32b	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.