(S)-2,2′-Bis(4-nitro-2-pyridyl­oxy)-1,1′-bi­naphthalene

The title compound, C₃₀H₁₈N₄O₆, is formed when two 4-nitro-2-pyridyl units link, in a trans fashion, to the two O atoms of optically active (S)-BINOL (1,1′-bi-2-naphthol). The mol­ecule exhibits some dramatic deviations from planarity due to the steric hindrance caused by the presence of the two nitro­pyridyl­oxyl moieties. C—H...O hydrogen bonding between adjacent mol­ecules links them into a chain-like structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.092
• Data-to-parameter ratio = 7.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.52
         From the CIF: _reflns_number_total               3405
         Count of symmetry unique reflns         2882
         Completeness (_total/calc)            118.15%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       523
         Fraction of Friedel pairs measured     0.181
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.

---

S1. Comment

The designed synthesis of functional supramolecular complexes has received intensive interest because of the interesting structural topologies of these complexes and their potential application in material science (Kitagawa & Kondo, 1998; Swiegers & Maleftse, 2002). The structures and functional properties of complexes can be adjusted by changing and controlling the type, angle and size of the spacers between coordination sites in the bridging ligands (Breuning et al., 2001; Fujita, 1998; Leininger et al., 2000). Rigid or flexible spacers, such as alkyl and aryl groups as well as organometallic complexes, have been employed as auxiliary of metal coordination sites (Hong et al., 2000; Horikoshi et al., 2002; Sun et al., 2000; Wang et al., 2002). From the viewpoint of constructing functional supramolecules, it may be more valuable to directly introduce functional groups into organic ligands as the spacer.

Optically active 1,1'-bi-2-naphthol (BINOL) derivatives have been used successfully in asymmetric catalysis, molecular recognition and optical materials (Lee & Lin, 2002; Noyori, 2002; Pu, 1998). Their success is due to the fact that the axial chirality of ligands can be well expressed in the steric environment of the active sites and the chiral configuration of BINOL molecules is known to be stable at high temperature over extended periods of time. Thus, BINOL may be used as a preferred starting material or auxiliary for the synthesis of homochiral functional supramolecular complexes. Herein, we report the synthesis and crystal structure of a homochiral organic ligand, namely (S)-2,2'-bis(4-nitro-2-pyridyloxy)-1,1'-binaphthalene [(S)—L], (I).

The single-crystal X-ray diffraction analysis of (I) reveals that the compound crystallized in the triclinic space group P1. As shown in Fig. 1, the ligand (S)—L is formed by two 4-nitro-2-pyridyl units being linked, in a trans fashion, to the two O atoms (2,2'-) of the optically active (S)-BINOL. The bond distances of C11—O1 and C41—O2 are 1.362 (3) and 1.363 (3) Å, respectively. The separation between atoms O1 and O2 is 3.028 Å, similar to what has been reported in 2,2'-O-substituted complexes (Goldberg, 1980). A great twisting between the two naphthyl groups produces a dihedral angle of 105.2°, which compares well with the angle of 101.7° found in (S)-BINOL itself (Mori et al., 1993; Toda et al., 1997). The naphthyl groups are also dramatically twisted with respect to their covaently linked pyridyl groups, with dihedral angles of 96.7 and 110.3°, respectively. These twistings may be ascribed to steric repulsion and results in the two nitropyridyl units lying on opposite sides of the binaphthyl backbone. Both nitro groups are approximately coplanar with their correspondingly linked pyridyl rings, with dihedral angles of 1.0 and 4.7°, respectively. The absolute configuration of (I) could not be reliably determined from the experimental X-ray data. It was set based on the minus value of the optical rotation of the BINOL and from the known configurations of the starting materials.

As shown in Fig. 2, (S)—L molecules are extended into a chain structure through C—H.·O hydrogen-bonding interactions [O2···H = 2.547 Å, O2···H—C15ⁱ = 144°; symmetry code: (i) x, y + 1, z; Desiraju & Steiner, 1999]. There are no other short contacts or noteworthy aryl–aryl interactions between adjacent molecules or between adjacent chains. It may be interesting to compare crystal structure of (I) with that of (S)-BINOL which crystallized in the trigonal space group P3₂. (S)-BINOL forms an infinite right-handed helical chain arranged along a 3₂ screw axis through intermolecular O—H.·O hydrogen bonds, with an O···O distance of 2.96 Å (Mori et al., 1993; Toda et al., 1997).

S2. Experimental

A mixture of (S)-BINOL (1.14 g, 4 mmol) and NaOH (0.32 g, 8 mmol) in MeOH (10 ml) was stirred for 6 h at room temperature. The solvent was removed under reduced pressure, the residue and 2-chloro-5-nitropyridine (1.40 g, 8.8 mmol) were dissolved in tetrahydrofuran (15 ml) and refluxed overnight. The resulting solution was diluted with EtOAc (20 ml) and then washed three times with water and once with brine; the organic layer was dried over anhydrous sodium sulfate. After removal of the solvent, the residue was recrystallized from acetone/MeOH to afford a colorless solid (S)—L. Slow evaporation of a methanol solution of (S)—L in air gave colorless crystals suitable for X-ray analysis.

S3. Refinement

The positions of the H atoms were defined with isotropic displacement parameters before the final cycle of least-squares refinement.

Computing details

Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1997); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. View of molecular structure in (I). Displacement ellipsoids are plotted at the 30% probability level.
	Fig. 2. One-dimensional chain is formed thorugh C–H···O hydrogen bonds.

(S)-2,2'-Bis(4-nitro-2-pyridyloxy)-1,1'-binaphthalene

Crystal data

C30H18N4O6	Z = 1
Mr = 530.48	F(000) = 274
Triclinic, P1	Dx = 1.409 Mg m^−3
a = 7.4573 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9472 (15) Å	θ = 3.0–27.5°
c = 11.748 (2) Å	µ = 0.10 mm^−1
α = 96.859 (3)°	T = 293 K
β = 104.061 (4)°	Needle, colorless
γ = 108.599 (3)°	0.38 × 0.17 × 0.10 mm
V = 625.3 (2) Å^3

Data collection

Siemens SMART CCD diffractometer	3405 independent reflections
Radiation source: fine-focus sealed tube	2651 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scan	θmax = 27.5°, θmin = 3.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.980, Tmax = 0.990	k = −10→10
4222 measured reflections	l = −13→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0549P)^2] where P = (Fo^2 + 2Fc^2)/3
3405 reflections	(Δ/σ)max < 0.001
434 parameters	Δρmax = 0.16 e Å^−3
3 restraints	Δρmin = −0.15 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.

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 > σ(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
N11	0.8994 (3)	1.4718 (3)	0.6792 (2)	0.0508 (6)
N12	0.6068 (5)	1.1724 (5)	0.3822 (3)	0.0904 (11)
N41	0.7372 (3)	2.0857 (3)	0.9541 (2)	0.0474 (5)
N42	1.0922 (5)	2.3974 (4)	1.2341 (3)	0.0731 (8)
O1	1.0205 (3)	1.7844 (2)	0.73700 (16)	0.0497 (5)
O2	0.7769 (3)	2.0176 (2)	0.76743 (16)	0.0488 (5)
O11	0.5237 (6)	1.1860 (5)	0.2832 (3)	0.1308 (14)
O12	0.6097 (6)	1.0278 (4)	0.4060 (3)	0.1287 (13)
O41	0.9873 (5)	2.3671 (5)	1.2999 (2)	0.1033 (9)
O42	1.2626 (4)	2.5062 (4)	1.2671 (3)	0.1033 (10)
C11	0.9116 (4)	1.6301 (3)	0.6509 (2)	0.0424 (6)
C12	0.8244 (5)	1.6532 (4)	0.5391 (3)	0.0534 (7)
H12	0.828 (5)	1.771 (5)	0.532 (3)	0.072 (10)*
C13	0.7217 (5)	1.5043 (5)	0.4508 (3)	0.0659 (9)
H13	0.661 (6)	1.500 (5)	0.371 (4)	0.090 (12)*
C14	0.7100 (5)	1.3369 (4)	0.4771 (3)	0.0583 (8)
C15	0.7973 (5)	1.3243 (4)	0.5909 (3)	0.0578 (8)
H15	0.791 (5)	1.205 (5)	0.606 (3)	0.078 (10)*
C21	0.8549 (4)	1.7445 (3)	0.8889 (2)	0.0382 (5)
C22	1.0261 (4)	1.7775 (3)	0.8561 (2)	0.0421 (6)
C23	1.2132 (4)	1.8250 (4)	0.9397 (3)	0.0506 (7)
H23	1.325 (5)	1.842 (3)	0.909 (3)	0.050 (8)*
C24	1.2296 (5)	1.8401 (4)	1.0582 (3)	0.0561 (7)
H24	1.360 (5)	1.884 (4)	1.116 (3)	0.069 (10)*
C25	1.0741 (6)	1.8291 (5)	1.2218 (3)	0.0698 (9)
H25	1.211 (6)	1.869 (5)	1.282 (4)	0.085 (11)*
C26	0.9127 (6)	1.8030 (5)	1.2592 (3)	0.0775 (11)
H26	0.914 (5)	1.813 (5)	1.338 (4)	0.078 (11)*
C27	0.7244 (6)	1.7488 (5)	1.1766 (3)	0.0702 (10)
H27	0.619 (6)	1.731 (5)	1.200 (4)	0.082 (12)*
C28	0.7024 (5)	1.7237 (4)	1.0560 (3)	0.0519 (7)
H28	0.569 (5)	1.684 (4)	0.996 (3)	0.061 (9)*
C29	0.8705 (4)	1.7559 (3)	1.0132 (2)	0.0409 (6)
C30	1.0604 (4)	1.8066 (4)	1.0991 (2)	0.0506 (7)
C31	0.6645 (4)	1.7068 (3)	0.7939 (2)	0.0376 (5)
C32	0.6342 (4)	1.8412 (3)	0.7370 (2)	0.0400 (6)
C33	0.4739 (4)	1.8067 (4)	0.6340 (2)	0.0457 (6)
H33	0.456 (4)	1.901 (4)	0.597 (3)	0.049 (7)*
C34	0.3444 (4)	1.6336 (4)	0.5859 (3)	0.0490 (6)
H34	0.245 (4)	1.613 (4)	0.517 (3)	0.048 (7)*
C35	0.2345 (4)	1.3073 (4)	0.5902 (3)	0.0531 (7)
H35	0.138 (4)	1.286 (4)	0.518 (3)	0.049 (8)*
C36	0.2542 (5)	1.1708 (4)	0.6439 (3)	0.0593 (8)
H36	0.167 (5)	1.057 (5)	0.611 (3)	0.066 (9)*
C37	0.4052 (4)	1.2072 (4)	0.7517 (3)	0.0536 (7)
H37	0.414 (4)	1.116 (4)	0.784 (3)	0.048 (8)*
C38	0.5363 (4)	1.3783 (3)	0.8012 (3)	0.0440 (6)
H38	0.643 (4)	1.406 (3)	0.881 (3)	0.045 (7)*
C39	0.5218 (4)	1.5258 (3)	0.7474 (2)	0.0383 (5)
C40	0.3639 (4)	1.4893 (3)	0.6404 (2)	0.0420 (6)
C41	0.8507 (4)	2.1131 (3)	0.8834 (2)	0.0426 (6)
C42	1.0413 (5)	2.2406 (4)	0.9151 (3)	0.0615 (8)
H42	1.119 (5)	2.250 (5)	0.859 (3)	0.084 (11)*
C43	1.1225 (5)	2.3363 (5)	1.0316 (3)	0.0662 (9)
H43	1.257 (6)	2.419 (5)	1.063 (3)	0.074 (10)*
C44	1.0086 (5)	2.3035 (4)	1.1081 (3)	0.0536 (7)
C45	0.8172 (5)	2.1804 (4)	1.0673 (3)	0.0512 (7)
H45	0.733 (4)	2.153 (4)	1.120 (3)	0.057 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0540 (14)	0.0487 (13)	0.0472 (14)	0.0149 (11)	0.0168 (11)	0.0077 (11)
N12	0.094 (2)	0.076 (2)	0.066 (2)	−0.0103 (19)	0.0276 (19)	−0.0103 (18)
N41	0.0520 (14)	0.0459 (12)	0.0401 (13)	0.0146 (11)	0.0117 (11)	0.0067 (10)
N42	0.074 (2)	0.0799 (19)	0.0485 (16)	0.0237 (17)	0.0035 (15)	−0.0089 (14)
O1	0.0528 (11)	0.0472 (10)	0.0394 (10)	0.0046 (9)	0.0161 (9)	0.0072 (8)
O2	0.0625 (12)	0.0382 (9)	0.0367 (10)	0.0086 (9)	0.0122 (9)	0.0075 (8)
O11	0.136 (3)	0.122 (3)	0.0596 (19)	−0.019 (2)	0.0010 (18)	−0.0141 (18)
O12	0.178 (4)	0.0638 (17)	0.109 (3)	0.005 (2)	0.048 (2)	−0.0153 (17)
O41	0.107 (2)	0.134 (2)	0.0467 (15)	0.0247 (18)	0.0216 (15)	−0.0090 (15)
O42	0.0763 (19)	0.118 (2)	0.0663 (17)	0.0072 (17)	−0.0051 (14)	−0.0273 (16)
C11	0.0392 (14)	0.0466 (14)	0.0378 (14)	0.0083 (12)	0.0154 (11)	0.0073 (11)
C12	0.0643 (19)	0.0532 (17)	0.0385 (16)	0.0131 (15)	0.0173 (14)	0.0130 (13)
C13	0.065 (2)	0.078 (2)	0.0387 (18)	0.0080 (17)	0.0118 (15)	0.0110 (16)
C14	0.0589 (18)	0.0562 (17)	0.0443 (17)	−0.0001 (14)	0.0221 (14)	−0.0011 (13)
C15	0.067 (2)	0.0508 (16)	0.0561 (19)	0.0145 (15)	0.0298 (16)	0.0087 (14)
C21	0.0398 (13)	0.0352 (12)	0.0336 (13)	0.0091 (10)	0.0062 (10)	0.0069 (10)
C22	0.0424 (15)	0.0371 (12)	0.0375 (14)	0.0062 (11)	0.0078 (11)	0.0050 (11)
C23	0.0389 (16)	0.0513 (15)	0.0539 (18)	0.0092 (13)	0.0119 (14)	0.0069 (13)
C24	0.0416 (17)	0.0584 (16)	0.0525 (19)	0.0094 (14)	−0.0006 (14)	0.0086 (14)
C25	0.070 (2)	0.080 (2)	0.0402 (18)	0.0107 (19)	0.0028 (17)	0.0156 (16)
C26	0.090 (3)	0.092 (3)	0.0344 (18)	0.015 (2)	0.0140 (18)	0.0161 (17)
C27	0.082 (3)	0.086 (2)	0.052 (2)	0.027 (2)	0.035 (2)	0.0241 (18)
C28	0.0531 (18)	0.0589 (17)	0.0440 (17)	0.0166 (15)	0.0168 (14)	0.0175 (13)
C29	0.0443 (14)	0.0387 (12)	0.0374 (14)	0.0128 (11)	0.0099 (12)	0.0107 (11)
C30	0.0530 (17)	0.0499 (15)	0.0379 (15)	0.0129 (13)	0.0017 (13)	0.0101 (12)
C31	0.0370 (13)	0.0410 (12)	0.0321 (13)	0.0110 (11)	0.0101 (10)	0.0074 (10)
C32	0.0438 (15)	0.0364 (12)	0.0333 (13)	0.0091 (11)	0.0095 (11)	0.0029 (11)
C33	0.0548 (17)	0.0448 (14)	0.0363 (15)	0.0208 (13)	0.0069 (12)	0.0104 (12)
C34	0.0429 (15)	0.0585 (17)	0.0359 (14)	0.0172 (13)	−0.0008 (12)	0.0038 (12)
C35	0.0373 (15)	0.0512 (16)	0.0542 (19)	0.0065 (13)	0.0023 (14)	0.0000 (14)
C36	0.0468 (17)	0.0447 (16)	0.072 (2)	0.0039 (14)	0.0132 (16)	0.0037 (15)
C37	0.0551 (18)	0.0401 (14)	0.066 (2)	0.0137 (13)	0.0218 (16)	0.0160 (14)
C38	0.0387 (14)	0.0423 (14)	0.0481 (16)	0.0112 (12)	0.0116 (13)	0.0116 (12)
C39	0.0340 (13)	0.0420 (12)	0.0372 (14)	0.0118 (10)	0.0115 (11)	0.0061 (11)
C40	0.0354 (13)	0.0433 (13)	0.0415 (15)	0.0111 (11)	0.0083 (12)	0.0032 (12)
C41	0.0540 (16)	0.0370 (12)	0.0342 (13)	0.0164 (12)	0.0090 (12)	0.0076 (11)
C42	0.059 (2)	0.0575 (17)	0.0560 (19)	0.0037 (15)	0.0249 (16)	0.0002 (15)
C43	0.053 (2)	0.0618 (18)	0.059 (2)	0.0008 (15)	0.0109 (16)	−0.0089 (15)
C44	0.0566 (18)	0.0507 (15)	0.0436 (15)	0.0167 (14)	0.0066 (13)	−0.0018 (12)
C45	0.0601 (19)	0.0489 (15)	0.0446 (17)	0.0187 (14)	0.0180 (15)	0.0079 (13)

Geometric parameters (Å, º)

N11—C11	1.321 (3)	C26—C27	1.397 (6)
N11—C15	1.336 (4)	C26—H26	0.91 (4)
N12—O11	1.213 (5)	C27—C28	1.369 (4)
N12—O12	1.221 (5)	C27—H27	0.87 (4)
N12—C14	1.462 (4)	C28—C29	1.422 (4)
N41—C41	1.312 (3)	C28—H28	0.99 (3)
N41—C45	1.335 (4)	C29—C30	1.425 (4)
N42—O41	1.219 (4)	C31—C32	1.375 (3)
N42—O42	1.222 (4)	C31—C39	1.432 (3)
N42—C44	1.458 (4)	C32—C33	1.406 (4)
O1—C11	1.362 (3)	C33—C34	1.358 (4)
O1—C22	1.398 (3)	C33—H33	0.94 (3)
O2—C41	1.363 (3)	C34—C40	1.408 (4)
O2—C32	1.403 (3)	C34—H34	0.91 (3)
C11—C12	1.379 (4)	C35—C36	1.348 (5)
C12—C13	1.344 (5)	C35—C40	1.414 (4)
C12—H12	0.94 (4)	C35—H35	0.93 (3)
C13—C14	1.382 (5)	C36—C37	1.402 (5)
C13—H13	0.93 (4)	C36—H36	0.90 (4)
C14—C15	1.368 (4)	C37—C38	1.353 (4)
C15—H15	0.97 (4)	C37—H37	0.87 (3)
C21—C22	1.377 (3)	C38—C39	1.417 (3)
C21—C29	1.427 (3)	C38—H38	1.02 (3)
C21—C31	1.493 (4)	C39—C40	1.424 (3)
C22—C23	1.402 (4)	C41—C42	1.386 (4)
C23—C24	1.355 (4)	C42—C43	1.369 (5)
C23—H23	0.96 (3)	C42—H42	0.97 (4)
C24—C30	1.415 (4)	C43—C44	1.373 (4)
C24—H24	0.97 (4)	C43—H43	0.95 (4)
C25—C26	1.343 (5)	C44—C45	1.374 (4)
C25—C30	1.405 (4)	C45—H45	0.98 (3)
C25—H25	1.02 (4)
C11—N11—C15	116.6 (3)	C28—C29—C21	122.2 (2)
O11—N12—O12	123.0 (4)	C30—C29—C21	119.7 (2)
O11—N12—C14	118.6 (4)	C25—C30—C24	122.2 (3)
O12—N12—C14	118.4 (4)	C25—C30—C29	118.8 (3)
C41—N41—C45	117.0 (2)	C24—C30—C29	118.9 (2)
O41—N42—O42	123.6 (3)	C32—C31—C39	117.9 (2)
O41—N42—C44	118.5 (3)	C32—C31—C21	120.3 (2)
O42—N42—C44	117.9 (3)	C39—C31—C21	121.2 (2)
C11—O1—C22	118.1 (2)	C31—C32—O2	121.8 (2)
C41—O2—C32	120.5 (2)	C31—C32—C33	122.7 (2)
N11—C11—O1	118.5 (2)	O2—C32—C33	114.9 (2)
N11—C11—C12	125.1 (2)	C34—C33—C32	119.5 (3)
O1—C11—C12	116.4 (2)	C34—C33—H33	119.4 (18)
C13—C12—C11	118.0 (3)	C32—C33—H33	121.1 (18)
C13—C12—H12	124 (2)	C33—C34—C40	121.0 (3)
C11—C12—H12	117 (2)	C33—C34—H34	118.5 (17)
C12—C13—C14	118.2 (3)	C40—C34—H34	120.6 (17)
C12—C13—H13	127 (2)	C36—C35—C40	121.3 (3)
C14—C13—H13	114 (2)	C36—C35—H35	121.6 (17)
C15—C14—C13	120.5 (3)	C40—C35—H35	117.1 (17)
C15—C14—N12	119.8 (3)	C35—C36—C37	120.2 (3)
C13—C14—N12	119.7 (3)	C35—C36—H36	119 (2)
N11—C15—C14	121.7 (3)	C37—C36—H36	120 (2)
N11—C15—H15	119 (2)	C38—C37—C36	120.7 (3)
C14—C15—H15	119 (2)	C38—C37—H37	121 (2)
C22—C21—C29	117.9 (2)	C36—C37—H37	118 (2)
C22—C21—C31	118.7 (2)	C37—C38—C39	121.0 (3)
C29—C21—C31	123.3 (2)	C37—C38—H38	120.8 (15)
C21—C22—O1	119.9 (2)	C39—C38—H38	118.0 (15)
C21—C22—C23	122.8 (2)	C38—C39—C40	118.1 (2)
O1—C22—C23	117.0 (2)	C38—C39—C31	122.4 (2)
C24—C23—C22	119.6 (3)	C40—C39—C31	119.4 (2)
C24—C23—H23	123.2 (18)	C34—C40—C35	122.1 (3)
C22—C23—H23	117.2 (18)	C34—C40—C39	119.3 (2)
C23—C24—C30	121.1 (3)	C35—C40—C39	118.6 (2)
C23—C24—H24	119.2 (19)	N41—C41—O2	119.2 (2)
C30—C24—H24	119.6 (19)	N41—C41—C42	125.1 (2)
C26—C25—C30	121.5 (3)	O2—C41—C42	115.6 (2)
C26—C25—H25	120 (2)	C43—C42—C41	117.4 (3)
C30—C25—H25	118 (2)	C43—C42—H42	121 (2)
C25—C26—C27	120.7 (3)	C41—C42—H42	121 (2)
C25—C26—H26	125 (2)	C42—C43—C44	118.1 (3)
C27—C26—H26	115 (2)	C42—C43—H43	123 (2)
C28—C27—C26	120.2 (3)	C44—C43—H43	119 (2)
C28—C27—H27	118 (3)	C43—C44—C45	120.5 (3)
C26—C27—H27	121 (3)	C43—C44—N42	119.8 (3)
C27—C28—C29	120.6 (3)	C45—C44—N42	119.7 (3)
C27—C28—H28	120.8 (18)	N41—C45—C44	121.8 (3)
C29—C28—H28	118.6 (17)	N41—C45—H45	115.9 (19)
C28—C29—C30	118.1 (2)	C44—C45—H45	122.3 (18)