Crystal structure of 5,15-bis-(4-methyl-phen-yl)-10,20-bis-(4-nitro-phen-yl)porphyrin nitro-benzene disolvate.

The whole mol-ecule of the title porphyrin, C46H32N6O4·2C6H5NO2, which crystallized as a nitro-benzene disolvate, is generated by inversion symmetry. The porphyrin macrocycle is almost planar, the maximum deviation from the mean plane of the non-hydrogen atoms is 0.097 (2) Å. The aryl rings at the meso positions are inclined to this mean plane by 74.84 (6)° for the nitro-phenyl rings and 73.37 (7)° for the tolyl rings. In the crystal, the porphyrin mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains along [100]. The solvent mol-ecules are also linked by C-H⋯O hydrogen bonds, forming chains along [100]. Inter-digitation of the p-tolyl groups along the c axis creates rectangular channels in which the solvent mol-ecules are located.

Chemical context

Porphyrins and their n class="Chemical">metallated derivatives have been studied extensively for their host–guest properties (Byrn et al., 1991 ▸), catalytic activity (Shultz et al., 2009 ▸) and for applications in dye-sensitized solar cells (Urbani et al., 2014 ▸). The presence or absence of a metal ion at the porphyrin core can greatly affect its physical properties, such as catalytic activity and crystal packing. The title compound is the free-base analogue of a previously reported zinc derivative (Adilov & Thalladi, 2007 ▸). The absence of the metal ion alters the crystal packing and these changes in the crystal structure of its nitro­benzene disolvate are discussed herein.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1 ▸. The asymmetric unit consists of half of the porphyrin mol­ecule and one n class="Chemical">nitro­benzene solvent mol­ecule. The whole mol­ecule of the porphyrin is generated by inversion symmetry. The porphyrin macrocycle is almost planar, the maximum deviation from the mean plane of the non-hydrogen atoms being 0.0970 (19) Å for atom C1 (and the symmetry-related atom). The dihedral angles between the porphyrin ring mean plane and the aryl rings at the meso positions are similar; 74.84 (6)° for the nitro­phenyl rings and 73.37 (7)° for the tolyl rings.

Figure 1

The mol­ecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by inversion symmetry (symmetry operation: −x, 2 − y, −z), and only one solvent mol­ecule is shown.

Supra­molecular features

In the crystal, the solvent mol­ecules are linked by C—H⋯O hydrogen bonds [2.58 (5) Å, 129.9 (3)°] forming chains along the n class="Species">a-axis direction (Fig. 2 ▸ and Table 1 ▸). The nitro­phenyl groups of the macrocyle are projected into the inter­layer space where an oxygen of a nitro group (O2) forms a C—H⋯O hydrogen bond [2.453 (3) Å, 158.6 (2)°] with neighbouring mol­ecules, leading to the formation of chains along [100] (Fig. 2 ▸ and Table 1 ▸). Inter­digitation of the p-tolyl groups along the c-axis creates rectangular channels in which the solvent mol­ecules are located, as illustrated in Fig. 3 ▸.

Figure 2

A partial view along the b axis of the crystal packing of the title compound. The C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2i	0.95 (1)	2.45 (1)	3.355 (3)	159 (1)
C104—H104⋯O102i	0.95 (1)	2.58 (1)	3.272 (4)	130 (1)

Symmetry code: (i) .

Figure 3

A view along the a axis of the inter­layer stacking in the crystal of the title compound, also showing the inter­calation of the nitro­benzene groups between the layers.

Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ▸) for trans nitro­phenyl­phenyl n class="Chemical">porphyrins gave 29 hits. Apart from the zinc-metallated complex of the title compound, catena-[[μ3-5,15-bis­(p-tol­yl)-10,20-bis­(4-nitro­phen­yl)porphyrinato]zinc(II) nitro­benzene solvate] (CEZTUX; Adilov & Thalladi, 2007 ▸), mentioned previously, the crystal structure of the meso-tetra­kis­(4-nitro­phen­yl) analogue of the title compound, viz. meso-tetra­kis­(4-nitro­phen­yl)porphyrin nitro­benzene disolvate (BOMTEE; Seredyuk et al., 2014 ▸), is of particular inter­est. While CEZTUX has the same 1:2 porphyrin-solvent ratio, it has a totally different crystal packing. Both structures, however, contain porphyrin layers and the solvent mol­ecules are inter­calated between the layers. In the title free-base, the nitro groups of the macrocycle form C—H⋯O hydrogen bonds with neighbouring mol­ecules resulting in continuous offset stacks along the a-axis direction. The same situation is observed in the crystal of the tetra­kis­(4-nitro­phen­yl) analogue, BOMTEE.

Synthesis and crystallization

The synthesis of the title compound has been described previously (Adilov & Thalladi, 2007 ▸). It crystallized as a nitro­benzene disolvate on slow evaporation of a solution in chloro­form/n class="Chemical">nitro­benzene (v:v 1:2).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C-bound and N-bound n class="Disease">H atoms were included in calculated positions and refined as riding atoms: C—H = 0.95–0.98 Å, N—H = 0.88 Å with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(N, C) for other H atoms. The two NH H atoms in the porphyrin core are disordered over the four pyrrole N-atoms, and were refined with occupancies of 0.5 each.

Table 2

Experimental details

Crystal data
Chemical formula	C46H32N6O4·2C6H5NO2
M r	979.03
Crystal system, space group	Triclinic, P
Temperature (K)	193
a, b, c (Å)	7.957 (3), 9.656 (3), 16.568 (5)
α, β, γ (°)	76.710 (5), 79.440 (5), 78.173 (5)
V (Å3)	1200.1 (7)
Z	1
Radiation type	Mo Kα
μ (mm−1)	0.09
Crystal size (mm)	0.2 × 0.15 × 0.1
Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005 ▸)
T min, T max	0.830, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	7891, 5512, 4072
R int	0.066
(sin θ/λ)max (Å−1)	0.658
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.064, 0.189, 1.05
No. of reflections	5512
No. of parameters	334
H-atom treatment	All H-atom parameters refined
Δρmax, Δρmin (e Å−3)	0.80, −0.37

Computer programs: SMART and SAINT (Bruker, 2005 ▸), SIR2004 (Burla et al., 2007 ▸), Olex2.refine (Bourhis et al., 2015 ▸), OLEX2 (Dolomanov et al., 2009 ▸), Mercury (Macrae et al., 2008 ▸), SHELXTL (Sheldrick, 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017017868/su5408sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017017868/su5408Isup2.hkl

CCDC reference: 1811082

Additional supporting information: crystallographic information; 3D view; checkCIF report

C46H32N6O4·2C6H5NO2	Z = 1
Mr = 979.03	F(000) = 510.2496
Triclinic, P1	Dx = 1.355 Mg m−3
a = 7.957 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.656 (3) Å	Cell parameters from 832 reflections
c = 16.568 (5) Å	θ = 5.5–55.4°
α = 76.710 (5)°	µ = 0.09 mm−1
β = 79.440 (5)°	T = 193 K
γ = 78.173 (5)°	Plate, dark red
V = 1200.1 (7) Å3	0.2 × 0.15 × 0.1 mm

Bruker SMART CCD area detector diffractometer	5512 independent reflections
Radiation source: fine-focus sealed tube	4072 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
φ and ω scans	θmax = 27.9°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.830, Tmax = 0.991	k = −12→12
7891 measured reflections	l = −14→21

Refinement on F2	42 constraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.064	All H-atom parameters refined
wR(F2) = 0.189	w = 1/[σ2(Fo2) + (0.0885P)2 + 0.7087P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
5512 reflections	Δρmax = 0.80 e Å−3
334 parameters	Δρmin = −0.37 e Å−3
0 restraints

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	−0.4023 (2)	1.1991 (2)	−0.03569 (12)	0.0242 (4)
N1	−0.2172 (2)	1.08626 (18)	0.07401 (10)	0.0253 (4)
H1	−0.1213 (2)	1.05861 (18)	0.04157 (10)	0.0304 (4)*	0.500000
O1	−1.0421 (2)	1.6738 (2)	−0.15516 (13)	0.0524 (5)
C2	−0.3711 (2)	1.1584 (2)	0.04770 (13)	0.0254 (4)
N2	0.1210 (2)	0.91439 (18)	0.10379 (10)	0.0249 (4)
H2	0.0670 (2)	0.94670 (18)	0.05953 (10)	0.0299 (4)*	0.500000
O2	−1.1746 (2)	1.4941 (2)	−0.09963 (14)	0.0598 (6)
C3	−0.4958 (3)	1.1826 (2)	0.11990 (13)	0.0293 (4)
H3	−0.6126 (3)	1.2307 (2)	0.11960 (13)	0.0351 (5)*
N3	−1.0444 (2)	1.5482 (2)	−0.11856 (12)	0.0348 (4)
C4	−0.4157 (3)	1.1240 (2)	0.18851 (13)	0.0294 (4)
H4	−0.4667 (3)	1.1223 (2)	0.24519 (13)	0.0353 (5)*
C5	−0.2391 (3)	1.0648 (2)	0.15975 (13)	0.0257 (4)
C6	−0.1130 (3)	0.9975 (2)	0.21153 (12)	0.0258 (4)
C7	0.0548 (3)	0.9304 (2)	0.18412 (12)	0.0263 (4)
C8	0.1855 (3)	0.8648 (3)	0.23783 (13)	0.0331 (5)
H8	0.1742 (3)	0.8620 (3)	0.29623 (13)	0.0397 (6)*
C9	0.3270 (3)	0.8079 (3)	0.18946 (13)	0.0328 (5)
H9	0.4332 (3)	0.7571 (3)	0.20771 (13)	0.0394 (6)*
C10	0.2867 (2)	0.8387 (2)	0.10502 (12)	0.0253 (4)
C11	−0.5730 (2)	1.2911 (2)	−0.05372 (12)	0.0245 (4)
C12	−0.5801 (3)	1.4362 (2)	−0.08993 (16)	0.0356 (5)
H12	−0.4777 (3)	1.4775 (2)	−0.10072 (16)	0.0427 (6)*
C13	−0.7349 (3)	1.5219 (2)	−0.11066 (15)	0.0360 (5)
H13	−0.7399 (3)	1.6216 (2)	−0.13496 (15)	0.0432 (6)*
C14	−0.8809 (2)	1.4592 (2)	−0.09523 (13)	0.0274 (4)
C15	−0.8795 (3)	1.3162 (3)	−0.05707 (17)	0.0395 (6)
H15	−0.9830 (3)	1.2761 (3)	−0.04532 (17)	0.0474 (7)*
C16	−0.7239 (3)	1.2319 (2)	−0.03617 (16)	0.0370 (5)
H16	−0.7207 (3)	1.1332 (2)	−0.00974 (16)	0.0443 (6)*
C17	−0.1603 (3)	0.9982 (2)	0.30326 (12)	0.0274 (4)
C18	−0.1736 (4)	1.1229 (3)	0.33314 (15)	0.0439 (6)
H18	−0.1544 (4)	1.2097 (3)	0.29475 (15)	0.0526 (7)*
C19	−0.2144 (4)	1.1238 (3)	0.41821 (16)	0.0493 (7)
H19	−0.2223 (4)	1.2108 (3)	0.43721 (16)	0.0591 (8)*
C20	−0.2439 (3)	0.9990 (3)	0.47565 (14)	0.0382 (5)
C21	−0.2353 (4)	0.8755 (3)	0.44615 (15)	0.0463 (6)
H21	−0.2577 (4)	0.7895 (3)	0.48459 (15)	0.0556 (7)*
C22	−0.1943 (3)	0.8742 (3)	0.36067 (14)	0.0414 (6)
H22	−0.1895 (3)	0.7877 (3)	0.34163 (14)	0.0497 (7)*
C23	−0.2861 (4)	0.9995 (4)	0.56844 (16)	0.0555 (8)
H23a	−0.1805 (7)	0.963 (2)	0.5947 (3)	0.0833 (12)*
H23b	−0.332 (3)	1.0984 (5)	0.57653 (16)	0.0833 (12)*
H23c	−0.373 (2)	0.9378 (19)	0.5942 (3)	0.0833 (12)*
C101	0.6144 (3)	0.4878 (3)	0.62860 (17)	0.0449 (6)
N101	0.4624 (4)	0.4425 (3)	0.6107 (2)	0.0671 (8)
O101	0.4858 (4)	0.3604 (3)	0.5613 (2)	0.0894 (9)
C102	0.5908 (4)	0.5772 (3)	0.68566 (18)	0.0520 (7)
H102	0.4780 (4)	0.6110 (3)	0.71179 (18)	0.0624 (8)*
O102	0.3212 (3)	0.4896 (4)	0.6447 (3)	0.1102 (11)
C103	0.7342 (4)	0.6154 (4)	0.70340 (19)	0.0574 (8)
H103	0.7214 (4)	0.6759 (4)	0.74271 (19)	0.0689 (9)*
C104	0.8975 (4)	0.5666 (3)	0.66456 (19)	0.0528 (7)
H104	0.9964 (4)	0.5943 (3)	0.67696 (19)	0.0633 (8)*
C105	0.9175 (4)	0.4789 (3)	0.60842 (18)	0.0504 (7)
H105	1.0305 (4)	0.4455 (3)	0.58236 (18)	0.0605 (8)*
C106	0.7757 (4)	0.4377 (3)	0.58887 (17)	0.0472 (6)
H106	0.7891 (4)	0.3771 (3)	0.54953 (17)	0.0566 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0182 (9)	0.0227 (9)	0.0314 (10)	−0.0003 (7)	−0.0061 (7)	−0.0052 (8)
N1	0.0216 (8)	0.0256 (8)	0.0279 (9)	0.0008 (6)	−0.0059 (6)	−0.0060 (7)
O1	0.0374 (10)	0.0453 (11)	0.0675 (13)	0.0024 (8)	−0.0168 (9)	0.0018 (9)
C2	0.0206 (9)	0.0225 (9)	0.0323 (10)	0.0002 (7)	−0.0044 (8)	−0.0066 (8)
N2	0.0204 (8)	0.0260 (8)	0.0276 (8)	0.0002 (6)	−0.0061 (6)	−0.0054 (7)
O2	0.0261 (9)	0.0670 (14)	0.0843 (15)	−0.0090 (9)	−0.0175 (9)	−0.0028 (11)
C3	0.0224 (9)	0.0308 (11)	0.0326 (11)	0.0015 (8)	−0.0029 (8)	−0.0084 (8)
N3	0.0203 (9)	0.0442 (12)	0.0388 (10)	−0.0004 (8)	−0.0083 (7)	−0.0074 (9)
C4	0.0243 (10)	0.0304 (11)	0.0315 (11)	0.0002 (8)	−0.0015 (8)	−0.0084 (8)
C5	0.0242 (9)	0.0230 (9)	0.0294 (10)	−0.0018 (7)	−0.0035 (8)	−0.0063 (8)
C6	0.0253 (10)	0.0247 (10)	0.0273 (10)	−0.0020 (8)	−0.0043 (8)	−0.0063 (8)
C7	0.0251 (10)	0.0261 (10)	0.0272 (10)	−0.0004 (8)	−0.0067 (8)	−0.0059 (8)
C8	0.0304 (11)	0.0401 (12)	0.0271 (10)	0.0026 (9)	−0.0099 (8)	−0.0064 (9)
C9	0.0254 (10)	0.0397 (12)	0.0309 (11)	0.0040 (9)	−0.0106 (8)	−0.0054 (9)
C10	0.0211 (9)	0.0249 (10)	0.0298 (10)	−0.0009 (7)	−0.0072 (8)	−0.0047 (8)
C11	0.0185 (9)	0.0260 (10)	0.0289 (10)	−0.0008 (7)	−0.0045 (7)	−0.0070 (8)
C12	0.0185 (9)	0.0302 (11)	0.0546 (14)	−0.0057 (8)	−0.0073 (9)	0.0015 (10)
C13	0.0237 (10)	0.0265 (11)	0.0529 (14)	−0.0019 (8)	−0.0103 (9)	0.0034 (10)
C14	0.0173 (9)	0.0333 (11)	0.0309 (10)	0.0008 (8)	−0.0060 (7)	−0.0073 (8)
C15	0.0232 (10)	0.0350 (12)	0.0637 (16)	−0.0092 (9)	−0.0140 (10)	−0.0068 (11)
C16	0.0282 (11)	0.0241 (11)	0.0595 (15)	−0.0053 (9)	−0.0127 (10)	−0.0044 (10)
C17	0.0240 (9)	0.0308 (10)	0.0259 (10)	0.0011 (8)	−0.0052 (8)	−0.0068 (8)
C18	0.0649 (17)	0.0350 (13)	0.0320 (12)	−0.0109 (12)	−0.0054 (11)	−0.0064 (10)
C19	0.0735 (19)	0.0401 (14)	0.0374 (13)	−0.0074 (13)	−0.0073 (12)	−0.0167 (11)
C20	0.0360 (12)	0.0456 (14)	0.0303 (11)	0.0030 (10)	−0.0069 (9)	−0.0092 (10)
C21	0.0621 (17)	0.0396 (14)	0.0324 (12)	−0.0089 (12)	−0.0013 (11)	−0.0019 (10)
C22	0.0579 (15)	0.0334 (12)	0.0321 (12)	−0.0090 (11)	−0.0008 (10)	−0.0082 (9)
C23	0.0658 (18)	0.0635 (19)	0.0312 (13)	0.0071 (15)	−0.0060 (12)	−0.0139 (12)
C101	0.0386 (13)	0.0421 (14)	0.0511 (15)	−0.0067 (11)	−0.0121 (11)	0.0008 (11)
N101	0.0556 (17)	0.0549 (16)	0.092 (2)	−0.0197 (13)	−0.0255 (15)	0.0042 (15)
O101	0.103 (2)	0.0722 (17)	0.111 (2)	−0.0413 (15)	−0.0389 (17)	−0.0134 (16)
C102	0.0391 (14)	0.0584 (17)	0.0512 (16)	0.0049 (12)	−0.0012 (12)	−0.0121 (13)
O102	0.0402 (14)	0.114 (3)	0.179 (3)	−0.0187 (15)	−0.0151 (16)	−0.029 (2)
C103	0.0534 (17)	0.0654 (19)	0.0557 (17)	0.0089 (14)	−0.0165 (13)	−0.0266 (15)
C104	0.0424 (14)	0.0585 (17)	0.0599 (17)	−0.0046 (13)	−0.0170 (12)	−0.0125 (14)
C105	0.0374 (13)	0.0565 (17)	0.0517 (15)	−0.0014 (12)	−0.0001 (11)	−0.0103 (13)
C106	0.0528 (15)	0.0420 (14)	0.0444 (14)	−0.0029 (12)	−0.0046 (12)	−0.0103 (11)

C1—C2	1.400 (3)	C15—H15	0.9500
C1—C10i	1.403 (3)	C15—C16	1.390 (3)
C1—C11	1.501 (2)	C16—H16	0.9500
N1—H1	0.8800	C17—C18	1.382 (3)
N1—C2	1.372 (2)	C17—C22	1.388 (3)
N1—C5	1.371 (3)	C18—H18	0.9500
O1—N3	1.226 (3)	C18—C19	1.389 (3)
C2—C3	1.438 (3)	C19—H19	0.9500
N2—H2	0.8800	C19—C20	1.386 (4)
N2—C7	1.370 (3)	C20—C21	1.374 (4)
N2—C10	1.372 (2)	C20—C23	1.513 (3)
O2—N3	1.213 (3)	C21—H21	0.9500
C3—H3	0.9500	C21—C22	1.396 (3)
C3—C4	1.357 (3)	C22—H22	0.9500
N3—C14	1.468 (2)	C23—H23a	0.9800
C4—H4	0.9500	C23—H23b	0.9800
C4—C5	1.442 (3)	C23—H23c	0.9800
C5—C6	1.399 (3)	C101—N101	1.466 (4)
C6—C7	1.402 (3)	C101—C102	1.385 (4)
C6—C17	1.498 (3)	C101—C106	1.378 (4)
C7—C8	1.444 (3)	N101—O101	1.231 (4)
C8—H8	0.9500	N101—O102	1.210 (4)
C8—C9	1.352 (3)	C102—H102	0.9500
C9—H9	0.9500	C102—C103	1.368 (4)
C9—C10	1.443 (3)	C103—H103	0.9500
C11—C12	1.385 (3)	C103—C104	1.381 (4)
C11—C16	1.389 (3)	C104—H104	0.9500
C12—H12	0.9500	C104—C105	1.364 (4)
C12—C13	1.388 (3)	C105—H105	0.9500
C13—H13	0.9500	C105—C106	1.382 (4)
C13—C14	1.374 (3)	C106—H106	0.9500
C14—C15	1.379 (3)
C10i—C1—C2	125.44 (17)	H15—C15—C14	120.65 (12)
C11—C1—C2	118.19 (17)	C16—C15—C14	118.7 (2)
C11—C1—C10i	116.37 (17)	C16—C15—H15	120.65 (13)
C2—N1—H1	126.02 (11)	C15—C16—C11	120.4 (2)
C5—N1—H1	126.02 (10)	H16—C16—C11	119.82 (12)
C5—N1—C2	107.95 (16)	H16—C16—C15	119.82 (13)
N1—C2—C1	125.50 (18)	C18—C17—C6	121.0 (2)
C3—C2—C1	125.69 (17)	C22—C17—C6	121.06 (19)
C3—C2—N1	108.79 (17)	C22—C17—C18	118.0 (2)
C7—N2—H2	126.28 (10)	H18—C18—C17	119.36 (14)
C10—N2—H2	126.28 (11)	C19—C18—C17	121.3 (2)
C10—N2—C7	107.43 (16)	C19—C18—H18	119.36 (15)
H3—C3—C2	126.37 (11)	H19—C19—C18	119.68 (15)
C4—C3—C2	107.25 (18)	C20—C19—C18	120.6 (2)
C4—C3—H3	126.37 (12)	C20—C19—H19	119.68 (14)
O2—N3—O1	123.68 (19)	C21—C20—C19	118.4 (2)
C14—N3—O1	118.12 (18)	C23—C20—C19	120.6 (2)
C14—N3—O2	118.2 (2)	C23—C20—C21	121.0 (2)
H4—C4—C3	126.23 (12)	H21—C21—C20	119.43 (15)
C5—C4—C3	107.55 (18)	C22—C21—C20	121.1 (2)
C5—C4—H4	126.23 (12)	C22—C21—H21	119.43 (15)
C4—C5—N1	108.44 (17)	C21—C22—C17	120.6 (2)
C6—C5—N1	126.46 (18)	H22—C22—C17	119.72 (13)
C6—C5—C4	125.10 (19)	H22—C22—C21	119.72 (15)
C7—C6—C5	125.03 (19)	H23a—C23—C20	109.5
C17—C6—C5	117.50 (17)	H23b—C23—C20	109.5
C17—C6—C7	117.47 (17)	H23b—C23—H23a	109.5
C6—C7—N2	126.41 (17)	H23c—C23—C20	109.5
C8—C7—N2	109.04 (17)	H23c—C23—H23a	109.5
C8—C7—C6	124.54 (19)	H23c—C23—H23b	109.5
H8—C8—C7	126.39 (12)	C102—C101—N101	118.9 (3)
C9—C8—C7	107.22 (18)	C106—C101—N101	118.6 (3)
C9—C8—H8	126.39 (12)	C106—C101—C102	122.5 (3)
H9—C9—C8	126.33 (12)	O101—N101—C101	118.2 (3)
C10—C9—C8	107.34 (18)	O102—N101—C101	117.9 (3)
C10—C9—H9	126.33 (11)	O102—N101—O101	123.9 (3)
N2—C10—C1i	126.24 (18)	H102—C102—C101	120.88 (16)
C9—C10—C1i	124.76 (17)	C103—C102—C101	118.2 (2)
C9—C10—N2	108.96 (17)	C103—C102—H102	120.88 (17)
C12—C11—C1	119.81 (17)	H103—C103—C102	119.77 (17)
C16—C11—C1	120.80 (18)	C104—C103—C102	120.5 (3)
C16—C11—C12	119.37 (18)	C104—C103—H103	119.77 (18)
H12—C12—C11	119.57 (11)	H104—C104—C103	119.89 (18)
C13—C12—C11	120.86 (19)	C105—C104—C103	120.2 (3)
C13—C12—H12	119.57 (13)	C105—C104—H104	119.89 (17)
H13—C13—C12	120.77 (13)	H105—C105—C104	119.47 (17)
C14—C13—C12	118.5 (2)	C106—C105—C104	121.1 (3)
C14—C13—H13	120.77 (12)	C106—C105—H105	119.47 (16)
C13—C14—N3	118.88 (19)	C105—C106—C101	117.5 (3)
C15—C14—N3	118.92 (18)	H106—C106—C101	121.26 (17)
C15—C14—C13	122.19 (18)	H106—C106—C105	121.26 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ii	0.95 (1)	2.45 (1)	3.355 (3)	159 (1)
C104—H104···O102ii	0.95 (1)	2.58 (1)	3.272 (4)	130 (1)