3-(4-Bromo­phen­yl)-5-(4-dimethyl­amino­phen­yl)-1-phenyl-2-pyrazoline: X-ray and density functional theory (DFT) studies

In the crystal structure of the title compound, C₂₃H₂₂BrN₃, a strong conjugation of the pyrazoline chromophore with the aromatic rings at positions 1 and 3 is observed, as well as a significant shift in the synclinal→synperiplanar direction. The absolute structure was unequivocally determined. In the absence of clasical hydrogen-bond donors, the structure is stabilized by weak C—H...π inter­actions. This paper also reports the electronic structure of the title compound using NBO (natural bond order) analysis. The contributions of lone pairs to the relevant bonds were revealed.

S1. Comment

Pyrazolines have been reported to show a broad spectrum of biological activities including antibacterial (Nauduri & Reddy, 1998; Azarifar & Shaebanzadeh, 2002), antifungal (Korgaokar et al., 1996), antiprotozoal (Cetin et al., 2003), anti-inflammatory, analgesic (Udupi, Kushnoor et al., 1998; Udupi, Rao et al., 1998) and antidepressant (Bilgin et al., 1993) activities. Moreover, pyrazolines are useful synthons in organic synthesis. In this context, we have prepared several 1,3,5-triaryl-2-pyrazolines using the most straightforward method for the synthesis of 1,3,5-triphenyl-2-pyrazolines involving the one-pot condensation of chalcones with phenylhydrazine in glacial acetic acid. Here, we report the absolute structure determination of one of them, the title compound, (I), with a 4-bromophenyl moiety at position 3 of the pyrazoline ring (Fig. 1).

The values of relevant bond lengths (Table 1) in the C11/N1/N2/C3/C31 structural fragment indicate strong conjugation of the pyrazoline chromophore with the phenyl moieties at the N1 and C3 positions. These observations are in good agreement with those reported for 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline (Rurack et al., 2000) with an unsubstituted phenyl moiety at C3 atom. Comparing this compound and (I), the Ar/C3/N2/N1 fragments are nearly planar in both cases, but in the case of compound (I), the phenyl ring at N1 is directed by ca 8° more to coplanarity with the Ar/C3/N2/N1 fragment. Additionally, although in both cases a synclinal orientation of the Ar/C5 moiety to the pyrazoline ring is observed, the values of the relevant dihedral angles [36.6° for N1—C5—C51—C56 in (I) versus 76.5° for the analogous dihedral angle in 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline (Rurack et al., 2000)] indicate a significant shift in the synclinal→ synperiplanar direction for (I), in contrast with a synclinal→ anticlinal direction for 1,3-diphenyl-5-(4-dimethyaminophenyl)-2-pyrazoline. A similar orientation of the Ar/C5 moiety as demonstrated by the value of the relevant dihedral angle (-34.6°) observed for the (S) isomer of 1-(4-cyanophenyl)-3-phenyl-5-(4-diethyaminophenyl)-2-pyrazoline (Fahrni et al., 2003), while the values of the relevant dihedral angles for the other 5-(4-diethylaminophenyl)-2-pyrazolines of this series vary in the range from -47 to -63°.

The angles between the rings 1–4, defined in Fig. 1, are summarized in Table 2. In the absence of classical hydrogen-bond donors, the structure is stabilized by weak C—H···π interactions, two of them in an edge-to-face manner (Table 3 and Fig. 2).

Natural bond orbital (NBO) analysis (Foster & Weinhold, 1980) of the electronic structure of (I) shows that the bond orders (Wiberg indices) are very close to the expected values. The exceptions are the Br1—C34 (1.042), N2═C3 (1.679), N1—N2 (1.135), N1—C11 (1.072) and N3—C54 (1.123) bonds, where their bond orders are between a single and double bond and indicate electronic delocalization. A detailed analysis of the NBO results reveals that the electrons of the lone pair on atom Br1 contribute slightly to the Br1—C34 bond only, the electrons of the N2 lone pair are mainly delocalized on a double N2═C3 bond, and the electrons of the N1 lone pair contribute to the electronic density of the N1—C11 bond, lending it a partially double-bond character. The N1—N2 bond also has such double-bond character, as a consequence of the partial contributions of the two lone pairs on atoms N1 and N2 to this bond. The lone pair on atom N3 makes a dominant contribution to the N3—C54 bond. This electronic redistribution leads to a shortening of the N1—C11, N1—N2, N2═C3 and N3—C54 bonds.

Related literature

For related literature, see: Azarifar & Shaebanzadeh (2002); Bilgin et al. (1993); Cetin et al. (2003); Fahrni et al. (2003); Foster & Weinhold (1980); Frisch (1998); Glendening et al. (1993); Koóš et al. (1984, 1990); Korgaokar et al. (1996); Nauduri & Reddy (1998); Rurack et al. (2000); Udupi, Kushnoor & Bhat (1998); Udupi, Rao & Bhat (1998).

S2. Experimental

For the preparation of compound (I) (see scheme), 1-(4-bromophenyl)-3-(4-dimethylaminophenyl)prop-2-en-1-one (Koóš et al., 1984) and phenylhydrazine in glacial acetic acid were heated to reflux according to the previously described procedure of Koóš et al. (1990). Compound (I) (m.p. 459–460 K) crystallized from the solution during its cooling. ¹H NMR (DMSO-d₆, δ, p.p.m.): 6.62–7.68 (m, 13H, aromatic), 5.36 (dd, 1H, J = 6.2 and 12.2 Hz, 5-H), 3.81 (dd, 1H, J = 12.2 and 17.4 Hz, 4-H_cis), 3.02 (dd, 1H, J = 6.2 and 17.4 Hz, 4-H_trans), 2.81 (s, 6H, Me₂N); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 149.8, 144.1, 131.8, 131.6, 129.6, 128.9, 127.5, 126.4, 121.6, 118.7, 113.2, 112.8 (aromatic), 146.1 (C-3), 63.1 (C-5), 42.8 (C-4), 39.7 (Me₂N). Yellow single crystals of adequate quality for diffraction analysis were obtained by slow crystallization from ethanol.

S3. Refinement

H atoms were constrained to the ideal geometry using an appropriate riding model (C—H = 0.95–0.99 Å) and were refined isotropically. For the methyl groups, the C—H distances (0.98 Å) and N—C—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis.

NBO (natural bond orbital) calculations were carried out by means of the NBO program (Glendening et al., 1993) included in the GAUSSIAN98 package (Frisch et al., 1998), after full optimization of the geometric parameters of the isolated molecule at the B3LYP/6–31 G+ level of theory.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The numbering scheme of the (R)-isomer of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Bold numbers denote the rings.
	Fig. 2. C—H···π interactions in the structure of (I). For clarity, H atoms not included in these interactions have been omitted and only the acceptor aromatic rings, with numbers in their centres (see Fig. 1), are shown. For symmetry codes, see Table 3.

3-(4-Bromophenyl)-5-(4-dimethylaminophenyl)-1-phenyl-2-pyrazoline

Crystal data

C23H22BrN3	F(000) = 3456
Mr = 420.35	Dx = 1.429 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 8192 reflections
a = 32.3762 (4) Å	θ = 2.3–33.1°
b = 43.4056 (2) Å	µ = 2.12 mm^−1
c = 5.5618 (1) Å	T = 183 K
V = 7816.04 (17) Å^3	Plate, yellow
Z = 16	0.78 × 0.21 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	6946 independent reflections
Radiation source: fine-focus sealed tube	5926 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 120 pixels mm^-1	θmax = 33.1°, θmin = 2.3°
ω scans	h = −48→48
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −64→65
Tmin = 0.289, Tmax = 0.849	l = −8→8
34545 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0626P)^2 + 16.533P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
6946 reflections	Δρmax = 0.41 e Å^−3
268 parameters	Δρmin = −0.56 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 3062 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.003 (7)

Special details

Experimental. Data were collected at 183 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 20 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8196 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003).

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
Br1	0.255810 (9)	0.073372 (5)	0.62951 (7)	0.04393 (9)
N1	0.39126 (7)	−0.07600 (4)	1.0749 (4)	0.0307 (5)
N2	0.37467 (6)	−0.04680 (4)	1.0627 (4)	0.0254 (3)
N3	0.31998 (8)	−0.21392 (6)	1.1861 (5)	0.0466 (6)
C3	0.34988 (6)	−0.04541 (4)	0.8798 (4)	0.0241 (3)
C4	0.34736 (7)	−0.07504 (5)	0.7382 (4)	0.0277 (4)
H4A	0.3551	−0.0718	0.5679	0.036 (9)*
H4B	0.3193	−0.0840	0.7455	0.030 (8)*
C5	0.37926 (6)	−0.09584 (5)	0.8690 (5)	0.0259 (4)
H5	0.4037	−0.0992	0.7625	0.040 (9)*
C6	0.28953 (13)	−0.21477 (9)	1.3753 (7)	0.0641 (10)
H6A	0.2999	−0.2034	1.5152	0.10 (2)*
H6B	0.2842	−0.2362	1.4207	0.074 (14)*
H6C	0.2639	−0.2053	1.3184	0.12 (2)*
C7	0.31722 (10)	−0.23924 (6)	1.0176 (8)	0.0505 (8)
H7A	0.2936	−0.2360	0.9101	0.055 (11)*
H7B	0.3135	−0.2586	1.1059	0.088 (15)*
H7C	0.3427	−0.2403	0.9227	0.050 (10)*
C11	0.42510 (7)	−0.08137 (5)	1.2238 (4)	0.0266 (4)
C12	0.44641 (7)	−0.10933 (6)	1.2108 (5)	0.0328 (5)
H12	0.4388	−0.1243	1.0944	0.034 (8)*
C13	0.47883 (8)	−0.11524 (6)	1.3686 (6)	0.0391 (5)
H13	0.4932	−0.1343	1.3579	0.050 (10)*
C14	0.49063 (9)	−0.09397 (7)	1.5408 (6)	0.0441 (7)
H14	0.5126	−0.0983	1.6488	0.043 (9)*
C15	0.46954 (9)	−0.06604 (7)	1.5519 (6)	0.0418 (6)
H15	0.4774	−0.0512	1.6686	0.051 (10)*
C16	0.43723 (7)	−0.05945 (5)	1.3963 (5)	0.0320 (5)
H16	0.4233	−0.0402	1.4062	0.032 (7)*
C31	0.32751 (6)	−0.01695 (5)	0.8225 (4)	0.0241 (4)
C32	0.32899 (7)	0.00873 (5)	0.9758 (4)	0.0278 (4)
H32	0.3446	0.0076	1.1203	0.035 (8)*
C33	0.30808 (7)	0.03563 (5)	0.9196 (4)	0.0301 (5)
H33	0.3092	0.0530	1.0237	0.044 (9)*
C34	0.28540 (7)	0.03670 (5)	0.7074 (4)	0.0274 (4)
C35	0.28335 (7)	0.01208 (5)	0.5512 (4)	0.0287 (4)
H35	0.2678	0.0135	0.4068	0.046 (9)*
C36	0.30456 (7)	−0.01492 (5)	0.6092 (4)	0.0273 (4)
H36	0.3034	−0.0321	0.5033	0.038 (9)*
C51	0.36262 (6)	−0.12667 (5)	0.9509 (4)	0.0247 (4)
C52	0.37140 (7)	−0.15325 (5)	0.8205 (4)	0.0294 (4)
H52	0.3877	−0.1518	0.6788	0.049 (10)*
C53	0.35678 (8)	−0.18188 (5)	0.8943 (6)	0.0352 (5)
H53	0.3631	−0.1996	0.8011	0.044 (9)*
C54	0.33300 (7)	−0.18512 (5)	1.1028 (5)	0.0314 (5)
C55	0.32390 (8)	−0.15801 (6)	1.2318 (5)	0.0341 (5)
H55	0.3075	−0.1592	1.3729	0.050 (10)*
C56	0.33857 (7)	−0.12955 (5)	1.1560 (5)	0.0307 (4)
H56	0.3320	−0.1117	1.2466	0.042 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.05022 (15)	0.02539 (10)	0.05618 (17)	0.00705 (10)	−0.01657 (14)	0.00363 (12)
N1	0.0330 (9)	0.0216 (8)	0.0376 (12)	0.0034 (7)	−0.0149 (8)	−0.0049 (7)
N2	0.0277 (8)	0.0213 (7)	0.0273 (9)	0.0011 (6)	−0.0041 (7)	0.0007 (6)
N3	0.0434 (12)	0.0365 (11)	0.0601 (17)	−0.0112 (9)	−0.0144 (11)	0.0136 (11)
C3	0.0240 (8)	0.0240 (8)	0.0243 (9)	0.0005 (6)	−0.0011 (8)	−0.0005 (8)
C4	0.0296 (10)	0.0262 (10)	0.0274 (10)	0.0034 (8)	−0.0073 (8)	−0.0032 (8)
C5	0.0253 (9)	0.0250 (8)	0.0274 (9)	0.0012 (7)	−0.0064 (8)	−0.0026 (8)
C6	0.078 (2)	0.068 (2)	0.0466 (17)	−0.0377 (19)	−0.0115 (19)	0.0176 (18)
C7	0.0435 (15)	0.0258 (11)	0.082 (2)	−0.0029 (10)	−0.0160 (15)	0.0085 (13)
C11	0.0252 (9)	0.0266 (9)	0.0281 (10)	−0.0027 (7)	−0.0055 (8)	0.0027 (8)
C12	0.0298 (10)	0.0297 (10)	0.0389 (12)	0.0024 (8)	−0.0111 (9)	−0.0011 (9)
C13	0.0327 (11)	0.0362 (11)	0.0486 (14)	0.0038 (9)	−0.0154 (12)	0.0026 (12)
C14	0.0380 (13)	0.0452 (15)	0.0491 (16)	−0.0018 (11)	−0.0217 (12)	0.0052 (12)
C15	0.0427 (14)	0.0414 (13)	0.0415 (14)	−0.0080 (11)	−0.0175 (11)	−0.0018 (11)
C16	0.0336 (10)	0.0272 (9)	0.0354 (12)	−0.0041 (8)	−0.0087 (10)	−0.0009 (9)
C31	0.0225 (8)	0.0262 (9)	0.0236 (10)	0.0016 (7)	−0.0003 (7)	0.0009 (7)
C32	0.0274 (9)	0.0295 (10)	0.0265 (10)	0.0006 (8)	−0.0045 (8)	−0.0005 (9)
C33	0.0324 (10)	0.0250 (9)	0.0327 (13)	−0.0004 (8)	−0.0034 (9)	−0.0021 (8)
C34	0.0260 (9)	0.0238 (9)	0.0324 (11)	0.0006 (7)	−0.0009 (8)	0.0052 (8)
C35	0.0311 (10)	0.0298 (10)	0.0253 (10)	0.0012 (8)	−0.0037 (8)	0.0028 (8)
C36	0.0299 (9)	0.0268 (9)	0.0250 (10)	0.0026 (7)	−0.0028 (9)	−0.0005 (8)
C51	0.0233 (9)	0.0249 (9)	0.0258 (10)	0.0027 (7)	−0.0066 (7)	−0.0036 (7)
C52	0.0292 (10)	0.0288 (10)	0.0301 (11)	0.0028 (8)	−0.0009 (8)	−0.0054 (8)
C53	0.0330 (10)	0.0254 (10)	0.0474 (14)	0.0038 (8)	−0.0037 (12)	−0.0075 (11)
C54	0.0272 (10)	0.0293 (9)	0.0377 (13)	−0.0014 (8)	−0.0104 (9)	0.0036 (9)
C55	0.0311 (11)	0.0414 (13)	0.0299 (11)	−0.0047 (9)	−0.0045 (9)	0.0007 (10)
C56	0.0314 (10)	0.0312 (10)	0.0293 (11)	−0.0004 (8)	−0.0026 (9)	−0.0077 (9)

Geometric parameters (Å, º)

Br1—C34	1.908 (2)	C13—H13	0.9500
N1—N2	1.378 (3)	C14—C15	1.393 (4)
N1—C11	1.393 (3)	C14—H14	0.9500
N1—C5	1.485 (3)	C15—C16	1.388 (4)
N2—C3	1.297 (3)	C15—H15	0.9500
N3—C54	1.399 (3)	C16—H16	0.9500
N3—C6	1.442 (5)	C31—C36	1.402 (3)
N3—C7	1.447 (4)	C31—C32	1.404 (3)
C3—C31	1.467 (3)	C32—C33	1.386 (3)
C3—C4	1.511 (3)	C32—H32	0.9500
C4—C5	1.553 (3)	C33—C34	1.391 (3)
C4—H4A	0.9900	C33—H33	0.9500
C4—H4B	0.9900	C34—C35	1.379 (3)
C5—C51	1.513 (3)	C35—C36	1.396 (3)
C5—H5	1.0000	C35—H35	0.9500
C6—H6A	0.9800	C36—H36	0.9500
C6—H6B	0.9800	C51—C52	1.392 (3)
C6—H6C	0.9800	C51—C56	1.387 (3)
C7—H7A	0.9800	C52—C53	1.391 (3)
C7—H7B	0.9800	C52—H52	0.9500
C7—H7C	0.9800	C53—C54	1.399 (4)
C11—C12	1.398 (3)	C53—H53	0.9500
C11—C16	1.407 (3)	C54—C55	1.409 (4)
C12—C13	1.392 (3)	C55—C56	1.389 (4)
C12—H12	0.9500	C55—H55	0.9500
C13—C14	1.384 (4)	C56—H56	0.9500
N2—N1—C11	119.32 (18)	C15—C14—H14	120.8
N2—N1—C5	113.16 (17)	C13—C14—H14	120.8
C11—N1—C5	124.57 (19)	C16—C15—C14	121.4 (3)
C3—N2—N1	108.82 (18)	C16—C15—H15	119.3
C54—N3—C6	118.1 (3)	C14—C15—H15	119.3
C54—N3—C7	118.9 (3)	C15—C16—C11	119.8 (2)
C6—N3—C7	114.3 (3)	C15—C16—H16	120.1
N2—C3—C31	121.02 (19)	C11—C16—H16	120.1
N2—C3—C4	113.74 (18)	C36—C31—C32	118.8 (2)
C31—C3—C4	125.2 (2)	C36—C31—C3	119.9 (2)
C3—C4—C5	102.41 (18)	C32—C31—C3	121.3 (2)
C3—C4—H4A	111.3	C33—C32—C31	121.0 (2)
C5—C4—H4A	111.3	C33—C32—H32	119.5
C3—C4—H4B	111.3	C31—C32—H32	119.5
C5—C4—H4B	111.3	C32—C33—C34	118.5 (2)
H4A—C4—H4B	109.2	C32—C33—H33	120.7
N1—C5—C51	112.0 (2)	C34—C33—H33	120.7
N1—C5—C4	101.44 (16)	C35—C34—C33	122.3 (2)
C51—C5—C4	114.75 (17)	C35—C34—Br1	118.65 (18)
N1—C5—H5	109.5	C33—C34—Br1	119.06 (18)
C51—C5—H5	109.5	C34—C35—C36	118.8 (2)
C4—C5—H5	109.5	C34—C35—H35	120.6
N3—C6—H6A	109.5	C36—C35—H35	120.6
N3—C6—H6B	109.5	C35—C36—C31	120.6 (2)
H6A—C6—H6B	109.5	C35—C36—H36	119.7
N3—C6—H6C	109.5	C31—C36—H36	119.7
H6A—C6—H6C	109.5	C52—C51—C56	117.9 (2)
H6B—C6—H6C	109.5	C52—C51—C5	120.2 (2)
N3—C7—H7A	109.5	C56—C51—C5	121.8 (2)
N3—C7—H7B	109.5	C53—C52—C51	121.1 (2)
H7A—C7—H7B	109.5	C53—C52—H52	119.4
N3—C7—H7C	109.5	C51—C52—H52	119.4
H7A—C7—H7C	109.5	C52—C53—C54	121.4 (2)
H7B—C7—H7C	109.5	C52—C53—H53	119.3
N1—C11—C12	120.2 (2)	C54—C53—H53	119.3
N1—C11—C16	120.8 (2)	N3—C54—C53	122.0 (2)
C12—C11—C16	119.0 (2)	N3—C54—C55	121.0 (3)
C13—C12—C11	120.0 (2)	C53—C54—C55	116.9 (2)
C13—C12—H12	120.0	C56—C55—C54	121.1 (3)
C11—C12—H12	120.0	C56—C55—H55	119.4
C12—C13—C14	121.4 (2)	C54—C55—H55	119.4
C12—C13—H13	119.3	C51—C56—C55	121.5 (2)
C14—C13—H13	119.3	C51—C56—H56	119.3
C15—C14—C13	118.4 (2)	C55—C56—H56	119.3
C11—N1—N2—C3	166.5 (2)	C36—C31—C32—C33	0.3 (3)
C5—N1—N2—C3	5.1 (3)	C3—C31—C32—C33	179.4 (2)
N1—N2—C3—C31	179.8 (2)	C31—C32—C33—C34	0.1 (4)
N1—N2—C3—C4	−0.9 (3)	C32—C33—C34—C35	−0.5 (4)
N2—C3—C4—C5	−3.2 (3)	C32—C33—C34—Br1	179.14 (18)
C31—C3—C4—C5	176.1 (2)	C33—C34—C35—C36	0.4 (4)
N2—N1—C5—C51	−129.50 (19)	Br1—C34—C35—C36	−179.21 (17)
C11—N1—C5—C51	70.2 (3)	C34—C35—C36—C31	0.0 (3)
N2—N1—C5—C4	−6.7 (3)	C32—C31—C36—C35	−0.4 (3)
C11—N1—C5—C4	−167.0 (2)	C3—C31—C36—C35	−179.5 (2)
C3—C4—C5—N1	5.4 (2)	N1—C5—C51—C52	−143.1 (2)
C3—C4—C5—C51	126.3 (2)	C4—C5—C51—C52	102.0 (2)
N2—N1—C11—C12	−169.9 (2)	N1—C5—C51—C56	36.6 (3)
C5—N1—C11—C12	−10.7 (4)	C4—C5—C51—C56	−78.3 (3)
N2—N1—C11—C16	13.0 (4)	C56—C51—C52—C53	−0.5 (3)
C5—N1—C11—C16	172.2 (2)	C5—C51—C52—C53	179.3 (2)
N1—C11—C12—C13	−176.6 (3)	C51—C52—C53—C54	−0.5 (4)
C16—C11—C12—C13	0.6 (4)	C6—N3—C54—C53	−168.8 (3)
C11—C12—C13—C14	0.2 (5)	C7—N3—C54—C53	−23.1 (4)
C12—C13—C14—C15	−0.7 (5)	C6—N3—C54—C55	13.6 (4)
C13—C14—C15—C16	0.4 (5)	C7—N3—C54—C55	159.3 (3)
C14—C15—C16—C11	0.4 (5)	C52—C53—C54—N3	−176.5 (2)
N1—C11—C16—C15	176.3 (3)	C52—C53—C54—C55	1.2 (4)
C12—C11—C16—C15	−0.8 (4)	N3—C54—C55—C56	176.7 (2)
N2—C3—C31—C36	172.8 (2)	C53—C54—C55—C56	−1.0 (4)
C4—C3—C31—C36	−6.4 (3)	C52—C51—C56—C55	0.7 (3)
N2—C3—C31—C32	−6.2 (3)	C5—C51—C56—C55	−179.1 (2)
C4—C3—C31—C32	174.5 (2)	C54—C55—C56—C51	0.1 (4)