4-{[3,4-Di­hydro-5-methyl-3-oxo-2-phenyl-2H-pyrazol-4-yl­idene](phenyl)­methyl­amino}-1,5-di­methyl-2-phenyl-1H-pyrazol-3(2H)-one

In the title compound, C₂₈H₂₅N₅O₂, the carbonyl group of the 5-methyl-2-phenyl­pyrazol-3-one moiety, the adjacent double bond and the amine N atom of antipyrine are essentially coplanar, the largest deviation from the mean plane being 0.049 (2) Å. The compound is a neutral tridentate ligand in an en­amine–keto tautomeric form, due to a strong intramolecular N—H...O hydrogen bond. The dihedral angle between the two pyrazolone rings is 86.2 (3)°, reducing steric hindrance.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.053
• wR factor = 0.151
• Data-to-parameter ratio = 13.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

4-Acyl-5-pyrazolones, a family of flexible β-diketonates, are widely used and well known for their applications as analgesics, antipyretics, anti-inflammatory agents and insecticides (Hodnett & Paul, 1972). Therefore, the study of derivatives of 4-acyl-5-pyrazolones is the focus of many research groups working in the fields of coordination chemistry, biomedicine and pharmaceutical chemistry.

The title compound, (I), prepared by condensation of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and antipyrine (ATP), is a neutral tridentate ligand in which two O atoms of pyrazolone moieties and the N atom of antipyrine are possible coordinating atoms.

A view of the molecule of (I) is shown in Fig. 1. Atoms O1, C1, C2 and C5 of the PMBP moiety and atom N3 of ATP form a plane, the largest deviation being 0.048 (3) Å for atom C5. The dihedral angle between this mean plane and the pyrazoline ring of PMBP is 3.56 (3)°, close to the value of 5.05 (3)° in 4-[(2-hydroxyphenylamino)phenylmethylene]-5-methyl-2-phenyl-2H-pyrazol-3(4H)- one (Wang, Zhang & Miao, 2002). The bond lengths within this part of the molecule (Table 1) lie between the classical single- and double-bond lengths, indicating extensive conjugation.

Atoms O2, C6, C7 and N3 of ATP also are coplanar, the largest deviation from the mean plane being 0.010 (2) Å for C7. The dihedral angle between this plane and the adjacent pyrazoline ring of ATP is 6.64 (3)°. The bond lengths in this part of the molecule (Table 1) also indicate delocalization for the ATP group. The dihedral angle between the two pyrazoline rings is 86.2 (3)°, reducing their steric hindrance.

A strong intramolecular N3—H3···O1 hydrogen bond (Table 2) is observed, leading to an enamine–keto tautomerism. This case is similar to that in 1,5-dimethyl-4-{[E-3-oxo-3-(2-thienyl)-1-(trifluoromethyl)-1-propenyl]amino}- 2-phenyl-1,2-dihydro-3H-pyrazol-3-one [N···O = 2.702 (4) Å and the angle at H = 139°; Yu et al., 2002]. Intermolecular C—H···O hydrogen bonds are also found.

The displacements of atoms C10 and C31 from the pyrazoline ring of ATP are 0.625 (6) and −0.419 (6) Å, respectively, showing that the methyl group bonded to N5 and the phenyl group bonded to N4 are on opposite sides of the ring. The same result was observed in 3-(2,3-dihydro-1,5-dimethyl-3-oxo-2- phenylpyrazol-4-ylimino)-4,4,4-trifluoro-1-(2-thienyl)butane-1,2-dione (Wang, Yu et al., 2002). The torsion angle C10—N5—N4—C31 is 57.4 (4)°, close to the value of 55.6 (3)° in 4-(salicylideneamino)-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (Chumakov et al., 2000) and different from the value of 7.75 (2)° in 4-(antipyrin-4-yliminomethyl)benzoic acid (Zhang et al., 2002). Small torsion angles for O1—C1—C2—C5 [−7.5 (6)°] and O2—C7—C6—N3 [2.7 (6)°] show that atoms O1, N3 and O2 could act as the coordinating atoms in this tridentate ligand.

S2. Experimental

0.1 mol of PMBP in 20 ml e thanol solution and 0.1 mol of ATP in 20 ml e thanol solution were refluxed together for 3–4 h over a steam bath. Excess solvent was removed by evaporation and the solution was cooled in an ice bath with stirring. The product separated out as a cream-colored powder, which was collected and dried in air. After washing with cold anhydrous ethanol several times, the compound was dried in a vacuum over CaCl₂. Yellow–green single crystals suitable for X-ray analysis were obtained by slow cooling of a warmed ethanol solution. Elemental analysis for C₂₈H₂₅N₅O₂: calculated C 72.6, H 5.44, N 15.1%; found: C 71.2, H 5.32, N 15.3%.

S3. Refinement

The high value of R_int is due to the relatively poor crystal quality, compounded by the room-temperature data collection. All aryl and methyl H atoms were positioned geometrically (C—H = 0.93 and 0.96 Å, respectively) and refined as riding atoms. The amine H atom was located from a difference map and refined with an isotropic displacement parameters; N—H = 0.84 (4) Å.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids. Hydrogen bonding is shown as dashed lines.

4-{[3,4-Dihydro-5-methyl-3-oxo-2-phenyl-2H-pyrazol-4- ylidene](phenyl)methylamino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

Crystal data

C28H25N5O2	F(000) = 976
Mr = 463.53	Dx = 1.272 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 890 reflections
a = 6.986 (3) Å	θ = 2.3–21.9°
b = 27.904 (11) Å	µ = 0.08 mm^−1
c = 12.804 (5) Å	T = 293 K
β = 104.127 (8)°	Block, yellow–green
V = 2420.4 (16) Å^3	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1677 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.097
Graphite monochromator	θmax = 25.0°, θmin = 1.5°
ϕ and ω scans	h = −8→8
10034 measured reflections	k = −33→33
4285 independent reflections	l = −15→10

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0577P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.007
4285 reflections	Δρmax = 0.16 e Å^−3
324 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0098 (10)

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.

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

	x	y	z	Uiso*/Ueq
N1	0.8053 (4)	0.30110 (11)	1.2087 (3)	0.0609 (9)
N2	0.7831 (5)	0.33165 (12)	1.2917 (3)	0.0696 (10)
N3	0.3035 (4)	0.34004 (12)	0.9759 (3)	0.0540 (9)
H3	0.379 (5)	0.3176 (13)	0.969 (3)	0.082 (16)*
N4	0.1191 (4)	0.40868 (10)	0.7347 (2)	0.0493 (8)
N5	−0.0430 (4)	0.37926 (10)	0.7359 (2)	0.0503 (8)
O1	0.6275 (3)	0.28144 (9)	1.0348 (2)	0.0632 (8)
O2	0.4422 (3)	0.41282 (9)	0.83848 (19)	0.0673 (8)
C1	0.6489 (5)	0.30525 (14)	1.1194 (3)	0.0519 (10)
C2	0.5266 (5)	0.34211 (12)	1.1459 (3)	0.0473 (9)
C3	0.6174 (6)	0.35534 (14)	1.2548 (3)	0.0590 (11)
C4	0.5472 (6)	0.38901 (15)	1.3281 (3)	0.0858 (14)
H4A	0.6293	0.3860	1.3998	0.129*
H4B	0.4132	0.3814	1.3283	0.129*
H4C	0.5538	0.4213	1.3033	0.129*
C5	0.3677 (5)	0.36127 (12)	1.0725 (3)	0.0477 (9)
C6	0.1894 (5)	0.36341 (12)	0.8828 (3)	0.0463 (9)
C7	0.2749 (5)	0.39689 (13)	0.8237 (3)	0.0471 (9)
C8	0.0003 (5)	0.35498 (12)	0.8306 (3)	0.0490 (9)
C9	−0.1482 (5)	0.32477 (14)	0.8645 (3)	0.0721 (12)
H9A	−0.0848	0.3064	0.9267	0.108*
H9B	−0.2084	0.3035	0.8069	0.108*
H9C	−0.2475	0.3449	0.8819	0.108*
C10	−0.2392 (5)	0.39900 (14)	0.6880 (3)	0.0702 (12)
H10A	−0.3355	0.3738	0.6781	0.105*
H10B	−0.2400	0.4132	0.6196	0.105*
H10C	−0.2707	0.4230	0.7350	0.105*
C11	0.9878 (5)	0.27704 (14)	1.2193 (4)	0.0622 (11)
C12	1.1368 (6)	0.28490 (15)	1.3102 (4)	0.0856 (15)
H12	1.1160	0.3046	1.3650	0.128*
C13	1.3200 (7)	0.2628 (2)	1.3189 (5)	0.106 (2)
H13	1.4218	0.2681	1.3798	0.158*
C14	1.3505 (8)	0.2337 (2)	1.2387 (6)	0.113 (2)
H14	1.4723	0.2190	1.2455	0.170*
C15	1.2029 (7)	0.22617 (17)	1.1490 (5)	0.1022 (18)
H15	1.2248	0.2067	1.0942	0.153*
C16	1.0204 (6)	0.24739 (15)	1.1388 (4)	0.0764 (13)
H16	0.9194	0.2417	1.0777	0.115*
C21	0.2617 (5)	0.40465 (13)	1.0930 (3)	0.0464 (9)
C22	0.3457 (5)	0.44941 (15)	1.0920 (3)	0.0635 (11)
H22	0.4677	0.4524	1.0755	0.095*
C23	0.2496 (7)	0.48979 (15)	1.1153 (3)	0.0754 (13)
H23	0.3080	0.5198	1.1165	0.113*
C24	0.0683 (8)	0.48528 (18)	1.1364 (3)	0.0815 (14)
H24	0.0019	0.5126	1.1499	0.122*
C25	−0.0172 (6)	0.44145 (19)	1.1381 (4)	0.0795 (13)
H25	−0.1396	0.4389	1.1542	0.119*
C26	0.0791 (6)	0.40100 (14)	1.1158 (3)	0.0643 (11)
H26	0.0207	0.3711	1.1161	0.096*
C31	0.1463 (5)	0.42656 (14)	0.6359 (3)	0.0512 (10)
C32	0.2479 (5)	0.46887 (14)	0.6354 (3)	0.0601 (11)
H32	0.2949	0.4857	0.6992	0.090*
C33	0.2795 (6)	0.48598 (14)	0.5408 (4)	0.0696 (12)
H33	0.3517	0.5140	0.5415	0.104*
C34	0.2073 (6)	0.46276 (16)	0.4455 (3)	0.0688 (12)
H34	0.2264	0.4753	0.3815	0.103*
C35	0.1053 (6)	0.42031 (16)	0.4455 (3)	0.0681 (12)
H35	0.0568	0.4040	0.3812	0.102*
C36	0.0752 (5)	0.40208 (13)	0.5395 (3)	0.0598 (11)
H36	0.0072	0.3734	0.5389	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.052 (2)	0.065 (2)	0.058 (2)	0.0004 (17)	−0.0017 (19)	0.0036 (18)
N2	0.070 (2)	0.077 (3)	0.052 (2)	−0.0075 (19)	−0.0036 (19)	−0.002 (2)
N3	0.0487 (19)	0.061 (2)	0.048 (2)	0.0098 (18)	0.0034 (18)	−0.0002 (18)
N4	0.0385 (16)	0.062 (2)	0.0457 (19)	−0.0060 (15)	0.0069 (16)	−0.0005 (16)
N5	0.0334 (16)	0.069 (2)	0.0474 (19)	−0.0030 (15)	0.0084 (15)	0.0049 (17)
O1	0.0571 (16)	0.0741 (19)	0.0553 (17)	0.0100 (14)	0.0076 (15)	−0.0017 (15)
O2	0.0430 (15)	0.090 (2)	0.0650 (18)	−0.0124 (13)	0.0051 (14)	0.0043 (15)
C1	0.043 (2)	0.066 (3)	0.042 (2)	−0.004 (2)	0.001 (2)	0.010 (2)
C2	0.040 (2)	0.053 (2)	0.042 (2)	−0.0025 (18)	−0.0031 (19)	0.0036 (19)
C3	0.055 (2)	0.067 (3)	0.049 (3)	−0.004 (2)	0.002 (2)	0.005 (2)
C4	0.093 (3)	0.102 (4)	0.055 (3)	0.006 (3)	0.005 (3)	−0.021 (3)
C5	0.043 (2)	0.056 (2)	0.043 (2)	−0.0105 (18)	0.0082 (19)	0.001 (2)
C6	0.041 (2)	0.056 (2)	0.038 (2)	0.0033 (18)	0.0025 (19)	−0.0002 (19)
C7	0.034 (2)	0.059 (3)	0.045 (2)	0.0031 (19)	0.0053 (19)	−0.0040 (19)
C8	0.046 (2)	0.058 (2)	0.045 (2)	−0.0002 (18)	0.014 (2)	−0.0008 (19)
C9	0.056 (2)	0.092 (3)	0.069 (3)	−0.012 (2)	0.016 (2)	0.014 (2)
C10	0.041 (2)	0.093 (3)	0.069 (3)	0.007 (2)	0.001 (2)	0.009 (2)
C11	0.046 (2)	0.060 (3)	0.072 (3)	0.001 (2)	−0.002 (2)	0.026 (2)
C12	0.061 (3)	0.086 (3)	0.089 (3)	−0.005 (2)	−0.021 (3)	0.029 (3)
C13	0.062 (3)	0.096 (4)	0.133 (5)	−0.005 (3)	−0.027 (4)	0.056 (4)
C14	0.060 (3)	0.098 (5)	0.175 (7)	0.010 (3)	0.014 (4)	0.060 (4)
C15	0.061 (3)	0.095 (4)	0.150 (5)	0.020 (3)	0.026 (3)	0.038 (4)
C16	0.060 (3)	0.077 (3)	0.091 (3)	0.016 (2)	0.014 (3)	0.020 (3)
C21	0.048 (2)	0.050 (2)	0.040 (2)	0.0025 (19)	0.0071 (18)	0.0000 (18)
C22	0.059 (2)	0.059 (3)	0.069 (3)	−0.004 (2)	0.011 (2)	0.000 (2)
C23	0.088 (3)	0.059 (3)	0.071 (3)	0.003 (3)	0.004 (3)	−0.006 (2)
C24	0.094 (4)	0.078 (3)	0.067 (3)	0.025 (3)	0.010 (3)	−0.007 (3)
C25	0.062 (3)	0.097 (4)	0.082 (3)	0.016 (3)	0.023 (3)	−0.005 (3)
C26	0.059 (2)	0.069 (3)	0.067 (3)	−0.001 (2)	0.019 (2)	0.006 (2)
C31	0.048 (2)	0.061 (3)	0.046 (2)	0.004 (2)	0.014 (2)	0.004 (2)
C32	0.063 (2)	0.061 (3)	0.059 (3)	−0.005 (2)	0.020 (2)	0.000 (2)
C33	0.078 (3)	0.071 (3)	0.065 (3)	−0.016 (2)	0.026 (3)	0.002 (3)
C34	0.080 (3)	0.078 (3)	0.055 (3)	−0.003 (2)	0.027 (2)	0.007 (2)
C35	0.079 (3)	0.084 (3)	0.045 (2)	0.000 (2)	0.022 (2)	−0.008 (2)
C36	0.059 (2)	0.066 (3)	0.053 (3)	0.000 (2)	0.011 (2)	−0.002 (2)

Geometric parameters (Å, º)

N1—C1	1.380 (4)	C11—C16	1.383 (5)
N1—N2	1.401 (4)	C12—C13	1.400 (6)
N1—C11	1.417 (4)	C12—H12	0.930
N2—C3	1.316 (4)	C13—C14	1.367 (7)
N3—C5	1.346 (4)	C13—H13	0.930
N3—C6	1.421 (4)	C14—C15	1.359 (7)
N3—H3	0.84 (4)	C14—H14	0.930
N4—N5	1.402 (3)	C15—C16	1.383 (5)
N4—C7	1.409 (4)	C15—H15	0.930
N4—C31	1.416 (4)	C16—H16	0.930
N5—C8	1.356 (4)	C21—C26	1.380 (5)
N5—C10	1.466 (4)	C21—C22	1.382 (4)
O1—C1	1.249 (4)	C22—C23	1.381 (5)
O2—C7	1.221 (4)	C22—H22	0.930
C1—C2	1.430 (5)	C23—C24	1.364 (6)
C2—C5	1.375 (4)	C23—H23	0.930
C2—C3	1.432 (5)	C24—C25	1.364 (5)
C3—C4	1.492 (5)	C24—H24	0.930
C4—H4A	0.960	C25—C26	1.380 (5)
C4—H4B	0.960	C25—H25	0.930
C4—H4C	0.960	C26—H26	0.930
C5—C21	1.476 (4)	C31—C32	1.378 (5)
C6—C8	1.348 (4)	C31—C36	1.392 (5)
C6—C7	1.423 (5)	C32—C33	1.369 (5)
C8—C9	1.482 (4)	C32—H32	0.930
C9—H9A	0.960	C33—C34	1.365 (5)
C9—H9B	0.960	C33—H33	0.930
C9—H9C	0.960	C34—C35	1.382 (5)
C10—H10A	0.960	C34—H34	0.930
C10—H10B	0.960	C35—C36	1.369 (5)
C10—H10C	0.960	C35—H35	0.930
C11—C12	1.376 (5)	C36—H36	0.930
C1—N1—N2	111.4 (3)	C12—C11—N1	118.8 (4)
C1—N1—C11	129.1 (4)	C16—C11—N1	121.3 (4)
N2—N1—C11	118.7 (3)	C11—C12—C13	119.0 (5)
C3—N2—N1	106.5 (3)	C11—C12—H12	120.5
C5—N3—C6	124.2 (3)	C13—C12—H12	120.5
C5—N3—H3	111 (3)	C14—C13—C12	120.6 (5)
C6—N3—H3	120 (3)	C14—C13—H13	119.7
N5—N4—C7	108.8 (3)	C12—C13—H13	119.7
N5—N4—C31	120.1 (3)	C15—C14—C13	120.1 (5)
C7—N4—C31	124.0 (3)	C15—C14—H14	120.0
C8—N5—N4	107.3 (3)	C13—C14—H14	120.0
C8—N5—C10	122.9 (3)	C14—C15—C16	120.4 (5)
N4—N5—C10	116.8 (3)	C14—C15—H15	119.8
O1—C1—N1	125.2 (4)	C16—C15—H15	119.8
O1—C1—C2	129.6 (3)	C15—C16—C11	120.1 (5)
N1—C1—C2	105.2 (3)	C15—C16—H16	119.9
C5—C2—C1	123.1 (3)	C11—C16—H16	119.9
C5—C2—C3	131.1 (4)	C26—C21—C22	119.1 (3)
C1—C2—C3	105.6 (3)	C26—C21—C5	120.5 (3)
N2—C3—C2	111.2 (4)	C22—C21—C5	120.4 (3)
N2—C3—C4	119.1 (3)	C23—C22—C21	120.4 (4)
C2—C3—C4	129.7 (4)	C23—C22—H22	119.8
C3—C4—H4A	109.5	C21—C22—H22	119.8
C3—C4—H4B	109.5	C24—C23—C22	119.5 (4)
H4A—C4—H4B	109.5	C24—C23—H23	120.3
C3—C4—H4C	109.5	C22—C23—H23	120.3
H4A—C4—H4C	109.5	C25—C24—C23	121.2 (4)
H4B—C4—H4C	109.5	C25—C24—H24	119.4
N3—C5—C2	119.3 (3)	C23—C24—H24	119.4
N3—C5—C21	117.1 (3)	C24—C25—C26	119.5 (4)
C2—C5—C21	123.6 (3)	C24—C25—H25	120.2
C8—C6—N3	128.1 (3)	C26—C25—H25	120.2
C8—C6—C7	109.8 (3)	C25—C26—C21	120.4 (4)
N3—C6—C7	121.7 (3)	C25—C26—H26	119.8
O2—C7—N4	124.2 (3)	C21—C26—H26	119.8
O2—C7—C6	131.8 (3)	C32—C31—C36	119.3 (4)
N4—C7—C6	103.9 (3)	C32—C31—N4	119.2 (3)
C6—C8—N5	109.5 (3)	C36—C31—N4	121.5 (3)
C6—C8—C9	128.7 (3)	C33—C32—C31	119.8 (4)
N5—C8—C9	121.8 (3)	C33—C32—H32	120.1
C8—C9—H9A	109.5	C31—C32—H32	120.1
C8—C9—H9B	109.5	C34—C33—C32	121.4 (4)
H9A—C9—H9B	109.5	C34—C33—H33	119.3
C8—C9—H9C	109.5	C32—C33—H33	119.3
H9A—C9—H9C	109.5	C33—C34—C35	119.0 (4)
H9B—C9—H9C	109.5	C33—C34—H34	120.5
N5—C10—H10A	109.5	C35—C34—H34	120.5
N5—C10—H10B	109.5	C36—C35—C34	120.6 (4)
H10A—C10—H10B	109.5	C36—C35—H35	119.7
N5—C10—H10C	109.5	C34—C35—H35	119.7
H10A—C10—H10C	109.5	C35—C36—C31	119.9 (4)
H10B—C10—H10C	109.5	C35—C36—H36	120.0
C12—C11—C16	119.8 (4)	C31—C36—H36	120.0
C1—N1—N2—C3	−1.2 (4)	N4—N5—C8—C6	−7.2 (4)
C11—N1—N2—C3	169.5 (3)	C10—N5—C8—C6	−147.0 (3)
C7—N4—N5—C8	8.5 (4)	N4—N5—C8—C9	172.6 (3)
C31—N4—N5—C8	160.0 (3)	C10—N5—C8—C9	32.8 (5)
C7—N4—N5—C10	151.2 (3)	C1—N1—C11—C12	168.2 (4)
C31—N4—N5—C10	−57.4 (4)	N2—N1—C11—C12	−0.6 (5)
N2—N1—C1—O1	−178.1 (3)	C1—N1—C11—C16	−9.6 (6)
C11—N1—C1—O1	12.5 (6)	N2—N1—C11—C16	−178.3 (3)
N2—N1—C1—C2	2.9 (4)	C16—C11—C12—C13	0.5 (6)
C11—N1—C1—C2	−166.5 (3)	N1—C11—C12—C13	−177.3 (4)
O1—C1—C2—C5	−7.5 (6)	C11—C12—C13—C14	−0.4 (8)
N1—C1—C2—C5	171.5 (3)	C12—C13—C14—C15	0.6 (9)
O1—C1—C2—C3	177.6 (4)	C13—C14—C15—C16	−0.9 (8)
N1—C1—C2—C3	−3.4 (4)	C14—C15—C16—C11	1.0 (7)
N1—N2—C3—C2	−1.2 (4)	C12—C11—C16—C15	−0.8 (6)
N1—N2—C3—C4	176.5 (3)	N1—C11—C16—C15	176.9 (4)
C5—C2—C3—N2	−171.4 (3)	N3—C5—C21—C26	75.9 (4)
C1—C2—C3—N2	2.9 (4)	C2—C5—C21—C26	−104.5 (4)
C5—C2—C3—C4	11.3 (7)	N3—C5—C21—C22	−105.5 (4)
C1—C2—C3—C4	−174.4 (4)	C2—C5—C21—C22	74.1 (5)
C6—N3—C5—C2	−158.4 (3)	C26—C21—C22—C23	1.1 (6)
C6—N3—C5—C21	21.2 (5)	C5—C21—C22—C23	−177.5 (3)
C1—C2—C5—N3	10.6 (5)	C21—C22—C23—C24	−1.8 (6)
C3—C2—C5—N3	−175.9 (4)	C22—C23—C24—C25	2.0 (7)
C1—C2—C5—C21	−169.0 (3)	C23—C24—C25—C26	−1.4 (7)
C3—C2—C5—C21	4.4 (6)	C24—C25—C26—C21	0.7 (6)
C5—N3—C6—C8	−112.8 (4)	C22—C21—C26—C25	−0.6 (6)
C5—N3—C6—C7	74.8 (5)	C5—C21—C26—C25	178.0 (4)
N5—N4—C7—O2	172.2 (3)	N5—N4—C31—C32	153.4 (3)
C31—N4—C7—O2	22.0 (5)	C7—N4—C31—C32	−59.6 (5)
N5—N4—C7—C6	−6.3 (3)	N5—N4—C31—C36	−27.5 (5)
C31—N4—C7—C6	−156.5 (3)	C7—N4—C31—C36	119.5 (4)
C8—C6—C7—O2	−176.3 (4)	C36—C31—C32—C33	−0.7 (6)
N3—C6—C7—O2	−2.7 (6)	N4—C31—C32—C33	178.4 (3)
C8—C6—C7—N4	2.0 (4)	C31—C32—C33—C34	2.0 (6)
N3—C6—C7—N4	175.7 (3)	C32—C33—C34—C35	−2.0 (6)
N3—C6—C8—N5	−169.9 (3)	C33—C34—C35—C36	0.7 (6)
C7—C6—C8—N5	3.2 (4)	C34—C35—C36—C31	0.5 (6)
N3—C6—C8—C9	10.3 (6)	C32—C31—C36—C35	−0.5 (6)
C7—C6—C8—C9	−176.6 (3)	N4—C31—C36—C35	−179.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O2^i	0.96	2.67	3.302 (5)	123
C23—H23···O2^ii	0.93	2.53	3.428 (5)	161
N3—H3···O1	0.84 (4)	2.01 (4)	2.745 (4)	146 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2.