4,5-Bis(2,4-di-tert-butyl­phen­oxy)phthalonitrile

Abstract

In the title compound, C₃₆H₄₄N₂O₂, the dihedral angles between the phthalonitrile ring and the two di-tert-butyl­benzene rings are 68.134 (8) and 70.637 (11)°. The two nitrile groups are almost coplanar with the phthalonitrile ring except for one of the N atoms which deviates from the plane by 0.125 (4) Å. One of the tert-butyl groups is disordered over two orientations, with refined occupancies of 0.814 (6) and 0.186 (6). Intra­molecular C—H⋯O inter­actions stabilize the molecular structure. The crystal packing is stabilized by inter­molecular C—H⋯N inter­actions.

Related literature

For similar structures, see: Kartal et al. (2006 ▶); Petek et al. (2004 ▶); Dinçer et al. (2004 ▶). For other related structures, see: Şahin, et al. (2007 ▶); Wu et al. (2010 ▶); Yazıcı et al. (2004 ▶). For general background to phthalocyanines and metallophthalocyanines, see: Lenznoff & Lever (1989–1996 ▶); McKeown (1998 ▶); Wöhrle (2001 ▶).

Experimental

Crystal data

• C₃₆H₄₄N₂O₂

• M _r = 536.76

• Triclinic,

• a = 10.9468 (3) Å

• b = 11.0416 (4) Å

• c = 15.3133 (5) Å

• α = 99.719 (1)°

• β = 102.996 (1)°

• γ = 110.963 (1)°

• V = 1619.71 (9) ų

• Z = 2

• Mo Kα radiation

• μ = 0.07 mm⁻¹

• T = 175 K

• 0.21 × 0.19 × 0.14 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.986, T _max = 0.990

• 31007 measured reflections

• 7785 independent reflections

• 5255 reflections with I > 2σ(I)

• R _int = 0.031

Refinement

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.148

• S = 1.03

• 7785 reflections

• 399 parameters

• 3 restraints

• H-atom parameters constrained

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenberg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯O1	0.96	2.5	3.117 (2)	122
C20—H20A⋯O1	0.96	2.32	2.982 (3)	125
C36—H36B⋯O2	0.96	2.52	3.122 (3)	121
C37—H37B⋯O2	0.96	2.29	2.966 (2)	127
C22A—H22A⋯N2i	0.96	2.59	3.535 (4)	170

Symmetry code: (i) .

supplementary crystallographic information

Comment

Substituted phthalonitriles have been used as starting materials for synthesizing peripherally substituted phtalocyanines and subphthalocyanines (McKeown, 1998). Phthalocyanines and metallophthalocyanines have been invesitigated for many years because of their wide range of applications, including use in chemical sensors, liquid crystals, Langmiur-Blodgett films, non-linear optics, batteries, and as carrier generation materials in the near-infrared (Lennoff & Lever, 1989–1996). Some phthalocyanines have been used in the petroleum industry as catalysts for the oxidation of sulfur compounds in the gasoline fraction. Applications such as photoconducters in the xerographic double layers of laser printers and coping machines, and as as active materials in writable data-storage disks, are also known. The production of phthalocyanines for use in dyes and pigments is around 80 000 tonnes per year (Wöhrle, 2001). The crystal structure of the title compound is presented here. It containes three aromatic rings. Ring A (C3—C8, r.m.s = 0.0047), ring B (C11—C16, r.m.s = 0.0051) and ring C (C25—C30, r.m.s = 0.0038) are essentialy planar. C1, C2 and N1 is coplanar to ring A but N2 is -0.1252 (41) Å out of the plane formed by ring A. The C1≡N1 and the C2≡N2 triple bond distances are 1.145 (2) Å and 1.143 (2) Å respectively and are consistent with values found in similar compounds (Kartal et al. 2006, Petek et al. 2004 and Dinçer et al. 2004). The N1—C1—C3 and N2—C2—C4 bond angles are 179.26 (18) ° and 178.4 (3) ° respectively, this is consistent with values found for simular compounds (Şahin, et al. 2007, Wu, et al. 2010 and Yazıcı, et al. 2004). The dihedral angles between rings A and B and between rings A and C are 68.134 (8) ° and 70.637 (11) ° respectively. The angle between rings B and C is 48.12 (6) °. The crystal packing is stabilized by C—H···O intermolecular hydrogen interactions.

Experimental

Ground K₂CO₃ (4.91 g; 35.5 mmol; 7 eq.) was added to a solution of 4,5-dichlorophthalonitrile (1.00 g; 5.08 mmol) and 2,4-di-tert-butylphenol (2.20 g; 10.7 mmol; 2.1 eq.) in dry DMF (75 ml) before stirring overnight at 80 °C. The reaction mixture was cooled to room temperature before being transferred to 3M HCl (80 ml conc. HCl in 200 ml H₂O). The precipitate was filtered off, washed with H₂O and allowed to dry in air. The crude product was recrystallized from hot ethyl acetate and ethanol (1:1) to yield the title compound (77.9%). R_f 0.8 (Hexane:Acetone; 8:2); Mp 269.0 °C;

¹H NMR (600 MHz, CDCl₃) δ 7.52 (2H, d, J = 2.3 Hz, H-3', 3"), 7.31 (2H, dd, J = 8.4, 2.3 Hz, H-5', 5"), 7.21 (2H, s, H-3,6), 6.86 (2H, d, J = 8.4 Hz, H-6', 6" H-2,6), 1.39 (36H, s, –C(CH₃)₃). ¹³C NMR (151 MHz, CDCl₃) δ 152.51, 150.60, 148.46, 140.82, 125.13 (C-3',3"), 124.74 (C-5',5"), 121.66 (C-3,6), 120.36 (C-6',6"), 115.42 (–CN), 109.64 (C-1,2), 35.03 (–C(CH₃)₃), 34.82 (–C(CH₃)₃), 31.57 (–C(CH₃)₃), 30.40 (–C(CH₃)₃).

Refinement

The aromatic H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with U_iso (H) = 1.2U_eq(C) and at a distance of 0.93 Å. The methyl H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with U_iso(H) = 1.5U_eq(C) and at a distance of 0.96 Å.

Figures

Fig. 1.

Diamond representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability). Some H atoms and the disorder was left out for clarity.

Crystal data

C36H44N2O2	Z = 2
Mr = 536.76	F(000) = 580
Triclinic, P1	Dx = 1.1 Mg m−3
a = 10.9468 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0416 (4) Å	Cell parameters from 7569 reflections
c = 15.3133 (5) Å	θ = 2.8–28.6°
α = 99.719 (1)°	µ = 0.07 mm−1
β = 102.996 (1)°	T = 175 K
γ = 110.963 (1)°	Cuboid, colourless
V = 1619.71 (9) Å3	0.21 × 0.19 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer	5255 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 28°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.986, Tmax = 0.990	k = −14→14
31007 measured reflections	l = −20→20
7785 independent reflections

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0592P)2 + 0.5205P] where P = (Fo2 + 2Fc2)/3
7785 reflections	(Δ/σ)max = 0.017
399 parameters	Δρmax = 0.29 e Å−3
3 restraints	Δρmin = −0.30 e Å−3

Special details

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 40 s/frame. A total of 2019 frames were collected with a frame width of 0.5° covering up to θ = 28.57° with 99.4% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)
C1	0.32485 (17)	−0.09576 (17)	0.99913 (12)	0.0399 (4)
C2	0.2111 (2)	0.0801 (2)	1.06591 (15)	0.0601 (6)
C3	0.27916 (16)	−0.02106 (15)	0.94090 (12)	0.0350 (3)
C4	0.22520 (18)	0.06741 (17)	0.97435 (12)	0.0399 (4)
C5	0.18274 (18)	0.14119 (17)	0.91845 (12)	0.0428 (4)
H5	0.1479	0.201	0.9412	0.051*
C6	0.19232 (16)	0.12561 (15)	0.82952 (11)	0.0344 (3)
C7	0.24483 (15)	0.03433 (15)	0.79532 (11)	0.0325 (3)
C8	0.28764 (16)	−0.03739 (15)	0.85123 (12)	0.0356 (4)
H8	0.3225	−0.0972	0.8286	0.043*
C11	0.32695 (16)	−0.03783 (15)	0.67397 (11)	0.0341 (3)
C12	0.46705 (18)	0.02362 (17)	0.71765 (12)	0.0422 (4)
H12	0.5042	0.099	0.7687	0.051*
C13	0.55247 (17)	−0.02689 (18)	0.68553 (12)	0.0421 (4)
H13	0.6467	0.0138	0.716	0.05*
C14	0.49885 (16)	−0.13740 (16)	0.60855 (11)	0.0342 (3)
C15	0.35667 (16)	−0.19584 (16)	0.56661 (11)	0.0335 (3)
H15	0.32	−0.2701	0.5148	0.04*
C16	0.26543 (16)	−0.15055 (15)	0.59701 (11)	0.0317 (3)
C17	0.10949 (16)	−0.22154 (16)	0.54796 (12)	0.0364 (4)
C18	0.07343 (19)	−0.33885 (19)	0.46378 (13)	0.0503 (5)
H18A	0.1151	−0.3052	0.419	0.075*
H18B	−0.0247	−0.3829	0.4359	0.075*
H18C	0.1071	−0.4021	0.4836	0.075*
C19	0.03676 (18)	−0.27803 (18)	0.61657 (13)	0.0458 (4)
H19A	−0.0601	−0.327	0.585	0.069*
H19B	0.0516	−0.205	0.6675	0.069*
H19C	0.0734	−0.3373	0.64	0.069*
C20	0.05301 (19)	−0.1242 (2)	0.51307 (14)	0.0495 (5)
H20A	0.0705	−0.0513	0.5649	0.074*
H20B	−0.0443	−0.1713	0.4826	0.074*
H20C	0.0974	−0.0891	0.4698	0.074*
C21	0.58891 (17)	−0.19560 (18)	0.56883 (12)	0.0414 (4)
C25	0.09512 (16)	0.28072 (16)	0.79279 (11)	0.0334 (3)
C26	−0.03540 (17)	0.22322 (16)	0.80045 (12)	0.0406 (4)
H26	−0.0763	0.1312	0.7942	0.049*
C27	−0.10495 (16)	0.30261 (16)	0.81741 (12)	0.0385 (4)
H27	−0.1921	0.2638	0.8236	0.046*
C28	−0.04634 (15)	0.43969 (15)	0.82533 (11)	0.0310 (3)
C29	0.08501 (15)	0.49289 (15)	0.81665 (10)	0.0300 (3)
H29	0.1251	0.5846	0.8218	0.036*
C30	0.16077 (15)	0.41736 (15)	0.80073 (10)	0.0294 (3)
C31	−0.12629 (16)	0.52644 (17)	0.84061 (12)	0.0371 (4)
C32	−0.1880 (2)	0.5004 (2)	0.91925 (15)	0.0562 (5)
H32A	−0.2375	0.5556	0.9278	0.084*
H32B	−0.1156	0.5223	0.9759	0.084*
H32C	−0.2498	0.4071	0.9035	0.084*
C33	−0.0344 (2)	0.6768 (2)	0.8677 (2)	0.0792 (8)
H33A	0.0028	0.698	0.8184	0.119*
H33B	0.0394	0.6995	0.9237	0.119*
H33C	−0.0876	0.7274	0.8781	0.119*
C34	−0.2414 (3)	0.4900 (3)	0.75103 (16)	0.0823 (8)
H34A	−0.203	0.5063	0.7014	0.124*
H34B	−0.2919	0.5442	0.7592	0.124*
H34C	−0.3022	0.3964	0.7358	0.124*
C35	0.30789 (15)	0.48317 (16)	0.79499 (11)	0.0352 (4)
C36	0.40825 (18)	0.4698 (2)	0.87618 (14)	0.0540 (5)
H36A	0.5008	0.517	0.876	0.081*
H36B	0.389	0.3762	0.8696	0.081*
H36C	0.398	0.5077	0.9339	0.081*
C37	0.31886 (19)	0.4175 (2)	0.70201 (13)	0.0485 (4)
H37A	0.2603	0.4318	0.6517	0.073*
H37B	0.2908	0.3224	0.6945	0.073*
H37C	0.4124	0.4571	0.7017	0.073*
C38	0.35244 (18)	0.63396 (18)	0.80263 (15)	0.0504 (5)
H38A	0.29	0.6458	0.7532	0.076*
H38B	0.4437	0.6712	0.7979	0.076*
H38C	0.3515	0.6793	0.8616	0.076*
N1	0.36199 (18)	−0.15552 (17)	1.04487 (12)	0.0546 (4)
N2	0.1971 (3)	0.0875 (3)	1.13809 (15)	0.0937 (8)
O1	0.24505 (12)	0.02227 (11)	0.70557 (8)	0.0384 (3)
O2	0.15855 (12)	0.19450 (11)	0.76953 (8)	0.0400 (3)
C22A	0.7447 (3)	−0.1104 (4)	0.6219 (2)	0.0569 (8)	0.814 (6)
H22A	0.7633	−0.1136	0.6856	0.085*	0.814 (6)
H22B	0.7686	−0.0186	0.6198	0.085*	0.814 (6)
H22C	0.7982	−0.1465	0.593	0.085*	0.814 (6)
C23A	0.5683 (3)	−0.1892 (5)	0.46811 (18)	0.0696 (12)	0.814 (6)
H23A	0.6292	−0.2192	0.4438	0.104*	0.814 (6)
H23B	0.5879	−0.0981	0.4658	0.104*	0.814 (6)
H23C	0.4748	−0.2464	0.4314	0.104*	0.814 (6)
C24A	0.5532 (5)	−0.3364 (4)	0.5778 (5)	0.0921 (16)	0.814 (6)
H24A	0.6091	−0.3733	0.5526	0.138*	0.814 (6)
H24B	0.4579	−0.3913	0.5441	0.138*	0.814 (6)
H24C	0.5696	−0.3348	0.6423	0.138*	0.814 (6)
C22B	0.5042 (14)	−0.2940 (15)	0.4618 (7)	0.050 (3)	0.186 (6)
H22D	0.5663	−0.3179	0.4347	0.075*	0.186 (6)
H22E	0.4646	−0.2471	0.425	0.075*	0.186 (6)
H22F	0.4323	−0.3743	0.4633	0.075*	0.186 (6)
C23B	0.6083 (13)	−0.2968 (14)	0.6183 (9)	0.0414 (4)	0.186 (6)
H23D	0.664	−0.3346	0.5936	0.062*	0.186 (6)
H23E	0.5203	−0.3674	0.6093	0.062*	0.186 (6)
H23F	0.653	−0.2532	0.6837	0.062*	0.186 (6)
C24B	0.7055 (16)	−0.0922 (14)	0.5672 (16)	0.075 (5)	0.186 (6)
H24D	0.7568	−0.0353	0.6294	0.112*	0.186 (6)
H24E	0.6791	−0.04	0.5286	0.112*	0.186 (6)
H24F	0.7615	−0.1295	0.5424	0.112*	0.186 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0435 (9)	0.0387 (9)	0.0422 (10)	0.0193 (8)	0.0179 (8)	0.0111 (8)
C2	0.0913 (16)	0.0783 (14)	0.0484 (12)	0.0639 (13)	0.0374 (11)	0.0255 (11)
C3	0.0367 (8)	0.0329 (8)	0.0402 (9)	0.0163 (7)	0.0168 (7)	0.0114 (7)
C4	0.0487 (9)	0.0455 (9)	0.0374 (10)	0.0275 (8)	0.0209 (8)	0.0120 (8)
C5	0.0564 (10)	0.0455 (10)	0.0435 (10)	0.0343 (9)	0.0254 (8)	0.0112 (8)
C6	0.0411 (8)	0.0319 (8)	0.0388 (9)	0.0208 (7)	0.0184 (7)	0.0099 (7)
C7	0.0371 (8)	0.0290 (7)	0.0362 (9)	0.0164 (6)	0.0180 (7)	0.0059 (6)
C8	0.0411 (8)	0.0318 (8)	0.0425 (10)	0.0208 (7)	0.0202 (7)	0.0091 (7)
C11	0.0445 (9)	0.0340 (8)	0.0359 (9)	0.0234 (7)	0.0224 (7)	0.0100 (7)
C12	0.0461 (9)	0.0396 (9)	0.0378 (10)	0.0166 (8)	0.0173 (8)	−0.0005 (7)
C13	0.0366 (8)	0.0496 (10)	0.0378 (10)	0.0167 (8)	0.0149 (7)	0.0042 (8)
C14	0.0397 (8)	0.0394 (9)	0.0332 (9)	0.0209 (7)	0.0200 (7)	0.0116 (7)
C15	0.0418 (8)	0.0324 (8)	0.0318 (8)	0.0191 (7)	0.0166 (7)	0.0069 (7)
C16	0.0383 (8)	0.0310 (8)	0.0348 (9)	0.0189 (6)	0.0176 (7)	0.0126 (7)
C17	0.0384 (8)	0.0378 (8)	0.0398 (9)	0.0203 (7)	0.0157 (7)	0.0125 (7)
C18	0.0424 (10)	0.0524 (11)	0.0477 (11)	0.0187 (8)	0.0093 (8)	0.0010 (9)
C19	0.0422 (9)	0.0455 (10)	0.0548 (12)	0.0171 (8)	0.0226 (8)	0.0187 (9)
C20	0.0474 (10)	0.0566 (11)	0.0579 (12)	0.0305 (9)	0.0182 (9)	0.0262 (10)
C21	0.0431 (9)	0.0505 (10)	0.0425 (10)	0.0268 (8)	0.0239 (8)	0.0111 (8)
C25	0.0409 (8)	0.0361 (8)	0.0316 (8)	0.0247 (7)	0.0142 (7)	0.0061 (7)
C26	0.0433 (9)	0.0299 (8)	0.0481 (11)	0.0149 (7)	0.0171 (8)	0.0061 (7)
C27	0.0319 (8)	0.0369 (9)	0.0446 (10)	0.0131 (7)	0.0140 (7)	0.0056 (7)
C28	0.0316 (7)	0.0362 (8)	0.0296 (8)	0.0189 (6)	0.0108 (6)	0.0069 (6)
C29	0.0320 (7)	0.0314 (8)	0.0306 (8)	0.0167 (6)	0.0113 (6)	0.0078 (6)
C30	0.0322 (7)	0.0365 (8)	0.0242 (8)	0.0192 (6)	0.0097 (6)	0.0071 (6)
C31	0.0359 (8)	0.0433 (9)	0.0433 (10)	0.0252 (7)	0.0173 (7)	0.0132 (8)
C32	0.0628 (12)	0.0676 (13)	0.0641 (14)	0.0428 (11)	0.0377 (11)	0.0227 (11)
C33	0.0718 (14)	0.0479 (12)	0.150 (3)	0.0396 (11)	0.0676 (16)	0.0295 (14)
C34	0.0867 (17)	0.133 (2)	0.0566 (15)	0.0862 (18)	0.0123 (12)	0.0214 (15)
C35	0.0315 (7)	0.0435 (9)	0.0369 (9)	0.0209 (7)	0.0142 (7)	0.0097 (7)
C36	0.0365 (9)	0.0752 (14)	0.0522 (12)	0.0262 (9)	0.0092 (8)	0.0212 (10)
C37	0.0474 (10)	0.0597 (12)	0.0464 (11)	0.0251 (9)	0.0264 (9)	0.0115 (9)
C38	0.0397 (9)	0.0461 (10)	0.0706 (14)	0.0170 (8)	0.0276 (9)	0.0161 (10)
N1	0.0664 (11)	0.0530 (10)	0.0526 (10)	0.0305 (8)	0.0185 (8)	0.0214 (8)
N2	0.160 (2)	0.137 (2)	0.0594 (13)	0.1165 (19)	0.0640 (14)	0.0490 (13)
O1	0.0530 (7)	0.0419 (6)	0.0368 (7)	0.0314 (6)	0.0243 (5)	0.0116 (5)
O2	0.0580 (7)	0.0415 (6)	0.0394 (7)	0.0352 (6)	0.0242 (6)	0.0129 (5)
C22A	0.0425 (14)	0.089 (2)	0.0473 (17)	0.0339 (14)	0.0231 (13)	0.0108 (15)
C23A	0.0579 (18)	0.117 (3)	0.0391 (15)	0.046 (2)	0.0224 (13)	0.0008 (17)
C24A	0.075 (2)	0.054 (2)	0.178 (5)	0.0412 (18)	0.072 (3)	0.033 (3)
C22B	0.066 (8)	0.061 (8)	0.037 (6)	0.044 (7)	0.023 (5)	0.000 (5)
C23B	0.0431 (9)	0.0505 (10)	0.0425 (10)	0.0268 (8)	0.0239 (8)	0.0111 (8)
C24B	0.059 (9)	0.071 (8)	0.105 (15)	0.029 (7)	0.055 (10)	0.007 (9)

Geometric parameters (Å, °)

C1—N1	1.145 (2)	C27—C28	1.388 (2)
C1—C3	1.438 (2)	C27—H27	0.93
C2—N2	1.143 (3)	C28—C29	1.392 (2)
C2—C4	1.434 (3)	C28—C31	1.534 (2)
C3—C8	1.383 (2)	C29—C30	1.3999 (19)
C3—C4	1.395 (2)	C29—H29	0.93
C4—C5	1.393 (2)	C30—C35	1.542 (2)
C5—C6	1.376 (2)	C31—C34	1.518 (3)
C5—H5	0.93	C31—C33	1.525 (3)
C6—O2	1.3578 (19)	C31—C32	1.528 (2)
C6—C7	1.412 (2)	C32—H32A	0.96
C7—O1	1.3588 (19)	C32—H32B	0.96
C7—C8	1.376 (2)	C32—H32C	0.96
C8—H8	0.93	C33—H33A	0.96
C11—C12	1.379 (2)	C33—H33B	0.96
C11—C16	1.393 (2)	C33—H33C	0.96
C11—O1	1.4110 (17)	C34—H34A	0.96
C12—C13	1.384 (2)	C34—H34B	0.96
C12—H12	0.93	C34—H34C	0.96
C13—C14	1.383 (2)	C35—C36	1.529 (2)
C13—H13	0.93	C35—C38	1.533 (2)
C14—C15	1.394 (2)	C35—C37	1.536 (2)
C14—C21	1.532 (2)	C36—H36A	0.96
C15—C16	1.397 (2)	C36—H36B	0.96
C15—H15	0.93	C36—H36C	0.96
C16—C17	1.536 (2)	C37—H37A	0.96
C17—C18	1.529 (2)	C37—H37B	0.96
C17—C20	1.531 (2)	C37—H37C	0.96
C17—C19	1.539 (2)	C38—H38A	0.96
C18—H18A	0.96	C38—H38B	0.96
C18—H18B	0.96	C38—H38C	0.96
C18—H18C	0.96	C22A—H22A	0.96
C19—H19A	0.96	C22A—H22B	0.96
C19—H19B	0.96	C22A—H22C	0.96
C19—H19C	0.96	C23A—H23A	0.96
C20—H20A	0.96	C23A—H23B	0.96
C20—H20B	0.96	C23A—H23C	0.96
C20—H20C	0.96	C24A—H24A	0.96
C21—C24B	1.384 (13)	C24A—H24B	0.96
C21—C24A	1.500 (4)	C24A—H24C	0.96
C21—C23B	1.501 (12)	C22B—H22D	0.96
C21—C23A	1.525 (3)	C22B—H22E	0.96
C21—C22A	1.557 (3)	C22B—H22F	0.96
C21—C22B	1.650 (11)	C23B—H23D	0.96
C25—C26	1.382 (2)	C23B—H23E	0.96
C25—C30	1.390 (2)	C23B—H23F	0.96
C25—O2	1.4089 (17)	C24B—H24D	0.96
C26—C27	1.380 (2)	C24B—H24E	0.96
C26—H26	0.93	C24B—H24F	0.96
N1—C1—C3	179.26 (18)	C26—C27—C28	120.78 (15)
N2—C2—C4	178.4 (3)	C26—C27—H27	119.6
C8—C3—C4	119.70 (15)	C28—C27—H27	119.6
C8—C3—C1	120.12 (14)	C27—C28—C29	117.23 (13)
C4—C3—C1	120.18 (15)	C27—C28—C31	120.53 (13)
C5—C4—C3	120.20 (15)	C29—C28—C31	122.23 (14)
C5—C4—C2	120.12 (15)	C28—C29—C30	124.32 (14)
C3—C4—C2	119.67 (15)	C28—C29—H29	117.8
C6—C5—C4	119.99 (14)	C30—C29—H29	117.8
C6—C5—H5	120	C25—C30—C29	115.24 (13)
C4—C5—H5	120	C25—C30—C35	122.92 (13)
O2—C6—C5	125.57 (13)	C29—C30—C35	121.83 (14)
O2—C6—C7	114.72 (14)	C34—C31—C33	109.46 (19)
C5—C6—C7	119.68 (14)	C34—C31—C32	109.21 (17)
O1—C7—C8	124.80 (13)	C33—C31—C32	106.95 (16)
O1—C7—C6	115.18 (13)	C34—C31—C28	108.44 (14)
C8—C7—C6	120.00 (14)	C33—C31—C28	112.04 (14)
C7—C8—C3	120.42 (14)	C32—C31—C28	110.70 (13)
C7—C8—H8	119.8	C31—C32—H32A	109.5
C3—C8—H8	119.8	C31—C32—H32B	109.5
C12—C11—C16	122.65 (13)	H32A—C32—H32B	109.5
C12—C11—O1	117.89 (14)	C31—C32—H32C	109.5
C16—C11—O1	119.32 (14)	H32A—C32—H32C	109.5
C11—C12—C13	120.01 (16)	H32B—C32—H32C	109.5
C11—C12—H12	120	C31—C33—H33A	109.5
C13—C12—H12	120	C31—C33—H33B	109.5
C14—C13—C12	120.56 (16)	H33A—C33—H33B	109.5
C14—C13—H13	119.7	C31—C33—H33C	109.5
C12—C13—H13	119.7	H33A—C33—H33C	109.5
C13—C14—C15	117.32 (14)	H33B—C33—H33C	109.5
C13—C14—C21	122.73 (15)	C31—C34—H34A	109.5
C15—C14—C21	119.95 (14)	C31—C34—H34B	109.5
C14—C15—C16	124.54 (15)	H34A—C34—H34B	109.5
C14—C15—H15	117.7	C31—C34—H34C	109.5
C16—C15—H15	117.7	H34A—C34—H34C	109.5
C11—C16—C15	114.91 (14)	H34B—C34—H34C	109.5
C11—C16—C17	123.53 (13)	C36—C35—C38	107.50 (15)
C15—C16—C17	121.56 (14)	C36—C35—C37	110.04 (14)
C18—C17—C20	107.50 (15)	C38—C35—C37	107.12 (14)
C18—C17—C16	111.47 (13)	C36—C35—C30	109.04 (14)
C20—C17—C16	111.28 (14)	C38—C35—C30	111.76 (12)
C18—C17—C19	108.14 (15)	C37—C35—C30	111.30 (14)
C20—C17—C19	109.01 (14)	C35—C36—H36A	109.5
C16—C17—C19	109.35 (14)	C35—C36—H36B	109.5
C17—C18—H18A	109.5	H36A—C36—H36B	109.5
C17—C18—H18B	109.5	C35—C36—H36C	109.5
H18A—C18—H18B	109.5	H36A—C36—H36C	109.5
C17—C18—H18C	109.5	H36B—C36—H36C	109.5
H18A—C18—H18C	109.5	C35—C37—H37A	109.5
H18B—C18—H18C	109.5	C35—C37—H37B	109.5
C17—C19—H19A	109.5	H37A—C37—H37B	109.5
C17—C19—H19B	109.5	C35—C37—H37C	109.5
H19A—C19—H19B	109.5	H37A—C37—H37C	109.5
C17—C19—H19C	109.5	H37B—C37—H37C	109.5
H19A—C19—H19C	109.5	C35—C38—H38A	109.5
H19B—C19—H19C	109.5	C35—C38—H38B	109.5
C17—C20—H20A	109.5	H38A—C38—H38B	109.5
C17—C20—H20B	109.5	C35—C38—H38C	109.5
H20A—C20—H20B	109.5	H38A—C38—H38C	109.5
C17—C20—H20C	109.5	H38B—C38—H38C	109.5
H20A—C20—H20C	109.5	C7—O1—C11	118.38 (12)
H20B—C20—H20C	109.5	C6—O2—C25	120.00 (12)
C24B—C21—C24A	135.6 (7)	C21—C22A—H22A	109.5
C24B—C21—C23B	117.8 (9)	C21—C22A—H22B	109.5
C24A—C21—C23B	27.0 (4)	C21—C22A—H22C	109.5
C24B—C21—C23A	72.6 (9)	C21—C23A—H23A	109.5
C24A—C21—C23A	112.7 (3)	C21—C23A—H23B	109.5
C23B—C21—C23A	133.6 (5)	C21—C23A—H23C	109.5
C24B—C21—C14	110.0 (5)	C21—C24A—H24A	109.5
C24A—C21—C14	109.31 (17)	C21—C24A—H24B	109.5
C23B—C21—C14	108.7 (5)	C21—C24A—H24C	109.5
C23A—C21—C14	108.60 (16)	C21—C22B—H22D	109.5
C24B—C21—C22A	36.7 (9)	C21—C22B—H22E	109.5
C24A—C21—C22A	108.2 (2)	H22D—C22B—H22E	109.5
C23B—C21—C22A	84.1 (5)	C21—C22B—H22F	109.5
C23A—C21—C22A	106.40 (19)	H22D—C22B—H22F	109.5
C14—C21—C22A	111.68 (16)	H22E—C22B—H22F	109.5
C24B—C21—C22B	108.7 (8)	C21—C23B—H23D	109.5
C24A—C21—C22B	75.0 (5)	C21—C23B—H23E	109.5
C23B—C21—C22B	100.4 (6)	H23D—C23B—H23E	109.5
C23A—C21—C22B	40.0 (5)	C21—C23B—H23F	109.5
C14—C21—C22B	110.8 (4)	H23D—C23B—H23F	109.5
C22A—C21—C22B	133.0 (4)	H23E—C23B—H23F	109.5
C26—C25—C30	122.53 (13)	C21—C24B—H24D	109.5
C26—C25—O2	117.88 (14)	C21—C24B—H24E	109.5
C30—C25—O2	119.43 (13)	H24D—C24B—H24E	109.5
C27—C26—C25	119.90 (15)	C21—C24B—H24F	109.5
C27—C26—H26	120	H24D—C24B—H24F	109.5
C25—C26—H26	120	H24E—C24B—H24F	109.5

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O1	0.96	2.5	3.117 (2)	122
C20—H20A···O1	0.96	2.32	2.982 (3)	125
C36—H36B···O2	0.96	2.52	3.122 (3)	121
C37—H37B···O2	0.96	2.29	2.966 (2)	127
C22A—H22A···N2i	0.96	2.59	3.535 (4)	170

Symmetry codes: (i) −x+1, −y, −z+2.