(E)-3-[(Di­methyl­amino)­methyl­idene]-4-phenyl-1H-1,5-benzodiazepin-2(3H)-one

Loughzail, M.; Baouid, A.; Fernandes, J.A.; Driss, M.; Soumhi, E.H.

doi:10.1107/S1600536813034739

organic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Page o126

doi:10.1107/S1600536813034739

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(E)-3-[(Dimethylamino)methylidene]-4-phenyl-1H-1,5-benzodiazepin-2(3H)-one

Mohamed Loughzail,^a Abdesselam Baouid,^a José A. Fernandes,^b Mohamed Driss ^c and El Hassane Soumhi ^d ^*

^aLaboratoire de Chimie Moléculaire, Département de Chimie, Faculté des Sciences-Semlalia, BP 2390, Université Cadi Ayyad, 40001, Marrakech, Morocco, ^bDepartment of Chemistry, University of Aveiro, CICECO, 3810-193, Aveiro, Portugal, ^cLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis ElManar, 2092 ElManar II, Tunis, Tunisia, and ^dEquipe de Chimie des Matériaux et de l'Environnement, FSTG-Marrakech, Université Cadi Ayyad, Bd Abdelkrim Khattabi, BP. 549, Marrakech, Morocco
^*Correspondence e-mail: eh_soumhi@yahoo.fr

(Received 26 December 2013; accepted 28 December 2013; online 11 January 2014)

The asymmetric unit of the title compound, C₁₈H₁₇N₃O, consists of two independent molecules, each having an E conformation with respect to the C=C bond between the benzodiazepinone and dimethylamine groups. In the crystal, the two independent molecules are linked into a dimer by a pair of N—H⋯O hydrogen bonds.

CCDC reference: 978905

Related literature

For background to natural benzodiazepines and their properties, see: Di Braccio et al. (2001 ); Kavita et al. (1988 ). For the synthesis, see: Nardi et al. (1973 ). For a related structure, see: Loughzail et al. (2014 ).

Experimental

Crystal data

C₁₈H₁₇N₃O
M_r = 291.35
Monoclinic, P 2₁ /n
a = 11.281 (2) Å
b = 14.005 (4) Å
c = 20.124 (3) Å
β = 95.97 (1)°
V = 3162.1 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 300 K
0.3 × 0.15 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.521, T_max = 0.992
8620 measured reflections
6879 independent reflections
3575 reflections with I > 2σ(I)
R_int = 0.034
2 standard reflections every 60 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.158
S = 1.01
6879 reflections
402 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—HN1⋯O2ⁱ	0.86	2.17	2.861 (2)	137
N4—HN4⋯O1ⁱⁱ	0.86	2.41	2.939 (2)	121
Symmetry codes: (i) x+1, y+1, z; (ii) x-1, y-1, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 978905

Crystal structure: contains datablocks I, hassi4. DOI: 10.1107/S1600536813034739/is5330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813034739/is5330Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813034739/is5330Isup3.cml

checkCIF report

Comment top

The benzodiazepine nucleus is a pharmacophoric scaffold and represents a class of heterocycles with a wide range of applications. In particular, several representative benzodiazepines possess significant biological activity as antiviral (Di Braccio et al., 2001), antipsychotic agents (Kavita et al., 1988) and may be considered support for the synthesis of more active heterocyclic systems. Research in this area is highly active being directed towards the synthesis of compounds with enhanced pharmacological activity. Following the research efforts from some of us concerning novel synthetic pathways of new benzodiazepines (Loughzail et al., 2014).

The reaction of N,N-dimethylformamide dimethylacetal (DMF-DMA) in 4-phenyl-1H-1,5-benzodiazepin-2(3H)-one (Nardi et al., 1973) at reflux leads to the formation of the title compound, (E)-3-[(dimethylamino)methylene]-4-phenyl-1H-1,5-benzodiazepin-2(3H)-one with a good yield of 75%. The main geometric feature determined by X-ray diffraction is in good agreement with that observed in a similar compound (Loughzail et al., 2014).

Related literature top

For background to natural benzodiazepines and their properties, see: Di Braccio et al. (2001); Kavita et al. (1988). For the synthesis, see: Nardi et al. (1973). For a related structure, see: Loughzail et al. (2014).

Experimental top

A mixture of 0.47 g (1.98 mmol) of 4-phenyl-1H-1,5-benzodiazepin-2(3H)-one in 4.5 ml of dimethylformamide-dimethylacetal (DMF-DMA) was stirred at 100 °C for 4 h and then cooled to ambient temperature. Filtration and washing with a little cold diethyl ether gave 0.46 g of (E)-3-[(dimethylamino)methylene]-4-phenyl-1H-1,5-benzodiazepin-2(3H)-one. The product obtained was recrystallized from diethyl ether. Yield: 75%. Melting point: 497–498 K. ¹H NMR (CDCl₃, 300 MHz): δ 2.55 (s, 6H, (CH₃)₂N), 2.80 (s, 1H, NH), 6.32 (s, 1H, C=CH—N), 7.04–7.92 (m, 9H, H—Ar); ¹³C NMR (CDCl₃, 75 MHz): δ 43.50 (N(CH₃)₂), 98.02 (C=), 121.47–141.86 (12 C-Ar), 151.18 (CH—N(CH₃)₂), 167.40 (Ph—C=N), 178.57 (CO). MS (m/z, %): 292 ([M+H]⁺.

Structure description top

For background to natural benzodiazepines and their properties, see: Di Braccio et al. (2001); Kavita et al. (1988). For the synthesis, see: Nardi et al. (1973). For a related structure, see: Loughzail et al. (2014).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. The molecule structure of the title compound with 50% probability ellipsoids.

(E)-3-[(Dimethylamino)methylidene]-4-phenyl-1H-1,5-benzodiazepin-2(3H)-one top

Crystal data top

C₁₈H₁₇N₃O	F(000) = 1232
M_r = 291.35	D_x = 1.224 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 11.281 (2) Å	θ = 10–15°
b = 14.005 (4) Å	µ = 0.08 mm⁻¹
c = 20.124 (3) Å	T = 300 K
β = 95.97 (1)°	Prism, colourless
V = 3162.1 (12) Å³	0.3 × 0.15 × 0.1 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	3575 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 27.0°, θ_min = 2.0°
ω/2θ scans	h = −14→2
Absorption correction: ψ scan (North et al., 1968)	k = −1→17
T_min = 0.521, T_max = 0.992	l = −25→25
8620 measured reflections	2 standard reflections every 60 min
6879 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.0688P)² + 0.4349P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
6879 reflections	Δρ_max = 0.29 e Å⁻³
402 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (2)

Crystal data top

C₁₈H₁₇N₃O	V = 3162.1 (12) Å³
M_r = 291.35	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.281 (2) Å	µ = 0.08 mm⁻¹
b = 14.005 (4) Å	T = 300 K
c = 20.124 (3) Å	0.3 × 0.15 × 0.1 mm
β = 95.97 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3575 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.521, T_max = 0.992	2 standard reflections every 60 min
8620 measured reflections	intensity decay: 1%
6879 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
6879 reflections	Δρ_min = −0.23 e Å⁻³
402 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.87561 (14)	0.89599 (11)	0.18529 (8)	0.0622 (4)
O2	0.10910 (14)	−0.10731 (12)	0.31490 (8)	0.0642 (4)
N1	0.90374 (15)	0.78432 (12)	0.26535 (9)	0.0539 (5)
HN1	0.9796	0.7923	0.2677	0.065*
N2	0.74209 (15)	0.62029 (12)	0.23855 (9)	0.0511 (4)
N3	0.51730 (17)	0.83342 (15)	0.14714 (10)	0.0680 (6)
N4	0.08974 (16)	0.00488 (14)	0.23437 (10)	0.0601 (5)
HN4	0.0145	0.0109	0.2371	0.072*
N5	0.28648 (17)	0.14261 (13)	0.24917 (10)	0.0567 (5)
N6	0.47471 (16)	−0.10080 (14)	0.32360 (10)	0.0585 (5)
C1	0.83674 (18)	0.82566 (15)	0.21290 (11)	0.0486 (5)
C2	0.85993 (18)	0.72976 (14)	0.31600 (11)	0.0486 (5)
C3	0.9039 (2)	0.75029 (17)	0.38144 (12)	0.0652 (6)
H3	0.9601	0.7986	0.3898	0.078*
C4	0.8659 (3)	0.7007 (2)	0.43365 (13)	0.0836 (9)
H4	0.8957	0.7155	0.4773	0.100*
C5	0.7829 (3)	0.6283 (2)	0.42131 (14)	0.0809 (8)
H5	0.7547	0.5957	0.4567	0.097*
C6	0.7425 (2)	0.60485 (16)	0.35695 (12)	0.0623 (6)
H6	0.6893	0.5544	0.3492	0.075*
C7	0.77890 (18)	0.65458 (14)	0.30303 (11)	0.0477 (5)
C8	0.71591 (17)	0.67685 (15)	0.18894 (11)	0.0469 (5)
C9	0.71974 (18)	0.78242 (14)	0.19149 (10)	0.0477 (5)
C10	0.6341 (2)	0.84542 (16)	0.16682 (11)	0.0549 (6)
H10	0.6611	0.9077	0.1629	0.066*
C11	0.4533 (2)	0.7461 (2)	0.15408 (15)	0.0837 (8)
H111	0.4967	0.7066	0.1872	0.126*
H211	0.4443	0.7131	0.1121	0.126*
H311	0.3761	0.7602	0.1676	0.126*
C12	0.4456 (3)	0.9158 (2)	0.12312 (16)	0.0989 (10)
H112	0.4955	0.9713	0.1234	0.148*
H212	0.3840	0.9264	0.1518	0.148*
H312	0.4102	0.9038	0.0784	0.148*
C13	0.68919 (18)	0.63175 (15)	0.12197 (11)	0.0512 (5)
C14	0.6549 (2)	0.53721 (17)	0.11563 (13)	0.0635 (6)
H14	0.6437	0.5018	0.1536	0.076*
C15	0.6372 (2)	0.4951 (2)	0.05380 (15)	0.0791 (8)
H15	0.6151	0.4312	0.0503	0.095*
C16	0.6517 (2)	0.5463 (2)	−0.00301 (14)	0.0776 (8)
H16	0.6382	0.5174	−0.0447	0.093*
C17	0.6853 (3)	0.6380 (2)	0.00206 (14)	0.0797 (8)
H17	0.6958	0.6727	−0.0363	0.096*
C18	0.7045 (2)	0.68149 (18)	0.06404 (12)	0.0703 (7)
H18	0.7281	0.7451	0.0668	0.084*
C19	0.15585 (18)	−0.04443 (15)	0.28393 (11)	0.0500 (5)
C20	0.13736 (19)	0.04637 (15)	0.17907 (11)	0.0531 (5)
C21	0.0847 (2)	0.02598 (18)	0.11569 (13)	0.0697 (7)
H21	0.0178	−0.0131	0.1106	0.084*
C22	0.1294 (3)	0.0624 (2)	0.06001 (14)	0.0822 (8)
H22	0.0942	0.0465	0.0176	0.099*
C23	0.2269 (3)	0.1228 (2)	0.06716 (14)	0.0815 (8)
H23	0.2584	0.1467	0.0296	0.098*
C24	0.2770 (2)	0.14734 (18)	0.13008 (13)	0.0701 (7)
H24	0.3405	0.1900	0.1347	0.084*
C25	0.2344 (2)	0.10956 (15)	0.18699 (12)	0.0539 (6)
C26	0.31176 (18)	0.08457 (15)	0.29803 (11)	0.0497 (5)
C27	0.28278 (18)	−0.01887 (14)	0.29681 (10)	0.0467 (5)
C28	0.35540 (19)	−0.09421 (15)	0.31387 (10)	0.0499 (5)
H28	0.3156	−0.1512	0.3199	0.060*
C29	0.5536 (2)	−0.0227 (2)	0.31182 (14)	0.0718 (7)
H129	0.5744	0.0112	0.3528	0.108*
H229	0.5142	0.0199	0.2793	0.108*
H329	0.6245	−0.0474	0.2955	0.108*
C30	0.5312 (2)	−0.19260 (19)	0.33861 (13)	0.0728 (7)
H130	0.5894	−0.1863	0.3767	0.109*
H230	0.5695	−0.2138	0.3008	0.109*
H330	0.4719	−0.2384	0.3482	0.109*
C31	0.3668 (2)	0.12737 (16)	0.36159 (11)	0.0536 (6)
C32	0.3746 (2)	0.07799 (18)	0.42135 (12)	0.0730 (7)
H32	0.3446	0.0162	0.4223	0.088*
C33	0.4262 (3)	0.1191 (2)	0.47966 (14)	0.0976 (11)
H33	0.4293	0.0854	0.5196	0.117*
C34	0.4727 (3)	0.2090 (2)	0.47906 (15)	0.1087 (12)
H34	0.5081	0.2364	0.5183	0.130*
C35	0.4668 (3)	0.2583 (2)	0.42020 (15)	0.1003 (11)
H35	0.4987	0.3194	0.4196	0.120*
C36	0.4145 (3)	0.21896 (18)	0.36220 (13)	0.0740 (7)
H36	0.4107	0.2539	0.3227	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0509 (9)	0.0479 (8)	0.0874 (11)	−0.0082 (7)	0.0046 (8)	0.0143 (8)
O2	0.0491 (9)	0.0686 (10)	0.0742 (11)	−0.0202 (8)	0.0027 (8)	0.0177 (9)
N1	0.0366 (9)	0.0559 (11)	0.0683 (12)	−0.0045 (8)	0.0019 (8)	0.0091 (9)
N2	0.0454 (10)	0.0447 (10)	0.0626 (12)	−0.0035 (8)	0.0027 (8)	−0.0017 (9)
N3	0.0468 (12)	0.0712 (13)	0.0834 (15)	0.0108 (10)	−0.0054 (10)	0.0044 (11)
N4	0.0365 (9)	0.0664 (12)	0.0765 (13)	−0.0051 (9)	0.0013 (9)	0.0148 (10)
N5	0.0551 (11)	0.0481 (10)	0.0658 (12)	−0.0115 (9)	0.0012 (9)	0.0047 (9)
N6	0.0420 (10)	0.0619 (12)	0.0709 (12)	0.0019 (9)	0.0032 (9)	0.0023 (10)
C1	0.0413 (11)	0.0409 (11)	0.0644 (14)	0.0021 (10)	0.0093 (10)	−0.0022 (10)
C2	0.0438 (11)	0.0425 (11)	0.0600 (13)	0.0008 (10)	0.0077 (10)	0.0005 (10)
C3	0.0710 (16)	0.0593 (14)	0.0645 (16)	−0.0153 (13)	0.0033 (12)	−0.0046 (12)
C4	0.110 (2)	0.0819 (19)	0.0580 (16)	−0.0237 (18)	0.0056 (15)	−0.0044 (14)
C5	0.106 (2)	0.0754 (18)	0.0628 (17)	−0.0220 (17)	0.0155 (15)	0.0092 (14)
C6	0.0689 (16)	0.0502 (13)	0.0682 (16)	−0.0122 (12)	0.0097 (12)	0.0038 (12)
C7	0.0445 (12)	0.0385 (11)	0.0603 (14)	0.0037 (9)	0.0061 (10)	0.0010 (10)
C8	0.0345 (10)	0.0446 (11)	0.0613 (13)	−0.0015 (9)	0.0042 (9)	0.0022 (10)
C9	0.0408 (11)	0.0446 (11)	0.0576 (13)	−0.0010 (10)	0.0041 (9)	0.0019 (10)
C10	0.0491 (13)	0.0514 (13)	0.0639 (14)	0.0027 (10)	0.0044 (11)	0.0032 (11)
C11	0.0438 (14)	0.102 (2)	0.104 (2)	−0.0068 (15)	0.0016 (13)	−0.0067 (17)
C12	0.0777 (19)	0.103 (2)	0.110 (2)	0.0393 (18)	−0.0192 (17)	0.0020 (19)
C13	0.0387 (11)	0.0495 (12)	0.0645 (14)	−0.0028 (10)	0.0011 (10)	−0.0013 (11)
C14	0.0614 (15)	0.0550 (14)	0.0714 (16)	−0.0099 (12)	−0.0057 (12)	−0.0020 (12)
C15	0.082 (2)	0.0627 (16)	0.089 (2)	−0.0123 (15)	−0.0093 (16)	−0.0156 (15)
C16	0.0734 (18)	0.087 (2)	0.0711 (18)	−0.0075 (16)	0.0034 (14)	−0.0215 (16)
C17	0.092 (2)	0.0838 (19)	0.0646 (17)	−0.0135 (17)	0.0120 (15)	−0.0045 (15)
C18	0.0849 (19)	0.0615 (15)	0.0653 (16)	−0.0156 (14)	0.0109 (13)	−0.0039 (13)
C19	0.0417 (11)	0.0479 (12)	0.0600 (13)	−0.0059 (10)	0.0034 (10)	0.0004 (11)
C20	0.0448 (12)	0.0485 (12)	0.0648 (14)	−0.0028 (10)	0.0006 (10)	0.0104 (11)
C21	0.0643 (15)	0.0639 (15)	0.0769 (18)	−0.0145 (13)	−0.0126 (13)	0.0119 (13)
C22	0.092 (2)	0.0830 (19)	0.0667 (17)	−0.0213 (17)	−0.0142 (15)	0.0137 (15)
C23	0.091 (2)	0.085 (2)	0.0670 (17)	−0.0198 (17)	0.0016 (15)	0.0234 (15)
C24	0.0685 (16)	0.0655 (16)	0.0743 (17)	−0.0169 (13)	−0.0026 (13)	0.0227 (13)
C25	0.0505 (13)	0.0431 (11)	0.0670 (15)	−0.0024 (10)	0.0001 (11)	0.0091 (11)
C26	0.0404 (11)	0.0474 (12)	0.0619 (14)	−0.0084 (10)	0.0082 (10)	0.0004 (11)
C27	0.0399 (11)	0.0450 (11)	0.0546 (12)	−0.0071 (9)	0.0023 (9)	0.0016 (9)
C28	0.0465 (12)	0.0484 (12)	0.0544 (13)	−0.0078 (10)	0.0034 (10)	0.0024 (10)
C29	0.0438 (13)	0.0841 (18)	0.0881 (18)	−0.0093 (13)	0.0100 (12)	−0.0039 (15)
C30	0.0660 (16)	0.0797 (18)	0.0723 (16)	0.0218 (14)	0.0058 (13)	0.0049 (14)
C31	0.0510 (13)	0.0514 (13)	0.0596 (14)	−0.0110 (10)	0.0118 (10)	−0.0028 (11)
C32	0.092 (2)	0.0630 (16)	0.0647 (16)	−0.0243 (15)	0.0117 (14)	0.0000 (13)
C33	0.142 (3)	0.094 (2)	0.0561 (16)	−0.041 (2)	0.0066 (17)	−0.0020 (15)
C34	0.158 (3)	0.103 (2)	0.0644 (18)	−0.064 (2)	0.0082 (19)	−0.0160 (17)
C35	0.144 (3)	0.0776 (19)	0.080 (2)	−0.058 (2)	0.013 (2)	−0.0136 (16)
C36	0.0922 (19)	0.0621 (15)	0.0684 (16)	−0.0279 (15)	0.0123 (14)	−0.0016 (13)

Geometric parameters (Å, º) top

O1—C1	1.234 (2)	C14—C15	1.372 (3)
O2—C19	1.229 (2)	C14—H14	0.9300
N1—C1	1.362 (3)	C15—C16	1.373 (4)
N1—C2	1.404 (3)	C15—H15	0.9300
N1—HN1	0.8600	C16—C17	1.341 (4)
N2—C8	1.285 (3)	C16—H16	0.9300
N2—C7	1.405 (3)	C17—C18	1.385 (3)
N3—C10	1.346 (3)	C17—H17	0.9300
N3—C11	1.434 (3)	C18—H18	0.9300
N3—C12	1.462 (3)	C19—C27	1.473 (3)
N4—C19	1.369 (3)	C20—C21	1.380 (3)
N4—C20	1.410 (3)	C20—C25	1.404 (3)
N4—HN4	0.8600	C21—C22	1.374 (4)
N5—C26	1.285 (3)	C21—H21	0.9300
N5—C25	1.404 (3)	C22—C23	1.383 (4)
N6—C28	1.343 (3)	C22—H22	0.9300
N6—C29	1.445 (3)	C23—C24	1.375 (3)
N6—C30	1.452 (3)	C23—H23	0.9300
C1—C9	1.475 (3)	C24—C25	1.392 (3)
C2—C3	1.388 (3)	C24—H24	0.9300
C2—C7	1.401 (3)	C26—C27	1.485 (3)
C3—C4	1.365 (3)	C26—C31	1.488 (3)
C3—H3	0.9300	C27—C28	1.358 (3)
C4—C5	1.385 (4)	C28—H28	0.9300
C4—H4	0.9300	C29—H129	0.9600
C5—C6	1.368 (3)	C29—H229	0.9600
C5—H5	0.9300	C29—H329	0.9600
C6—C7	1.387 (3)	C30—H130	0.9600
C6—H6	0.9300	C30—H230	0.9600
C8—C9	1.480 (3)	C30—H330	0.9600
C8—C13	1.490 (3)	C31—C32	1.382 (3)
C9—C10	1.364 (3)	C31—C36	1.390 (3)
C10—H10	0.9300	C32—C33	1.381 (4)
C11—H111	0.9600	C32—H32	0.9300
C11—H211	0.9600	C33—C34	1.364 (4)
C11—H311	0.9600	C33—H33	0.9300
C12—H112	0.9600	C34—C35	1.366 (4)
C12—H212	0.9600	C34—H34	0.9300
C12—H312	0.9600	C35—C36	1.368 (4)
C13—C14	1.381 (3)	C35—H35	0.9300
C13—C18	1.384 (3)	C36—H36	0.9300

C1—N1—C2	125.81 (18)	C15—C16—H16	120.2
C1—N1—HN1	117.1	C16—C17—C18	120.4 (3)
C2—N1—HN1	117.1	C16—C17—H17	119.8
C8—N2—C7	121.94 (18)	C18—C17—H17	119.8
C10—N3—C11	124.4 (2)	C13—C18—C17	121.0 (2)
C10—N3—C12	119.3 (2)	C13—C18—H18	119.5
C11—N3—C12	116.0 (2)	C17—C18—H18	119.5
C19—N4—C20	124.02 (18)	O2—C19—N4	120.08 (19)
C19—N4—HN4	118.0	O2—C19—C27	123.1 (2)
C20—N4—HN4	118.0	N4—C19—C27	116.86 (18)
C26—N5—C25	120.83 (18)	C21—C20—C25	119.4 (2)
C28—N6—C29	123.3 (2)	C21—C20—N4	118.8 (2)
C28—N6—C30	120.1 (2)	C25—C20—N4	121.8 (2)
C29—N6—C30	116.09 (19)	C22—C21—C20	121.2 (2)
O1—C1—N1	119.60 (19)	C22—C21—H21	119.4
O1—C1—C9	123.0 (2)	C20—C21—H21	119.4
N1—C1—C9	117.35 (18)	C21—C22—C23	119.8 (3)
C3—C2—C7	119.6 (2)	C21—C22—H22	120.1
C3—C2—N1	117.26 (19)	C23—C22—H22	120.1
C7—C2—N1	123.1 (2)	C24—C23—C22	119.6 (3)
C4—C3—C2	121.0 (2)	C24—C23—H23	120.2
C4—C3—H3	119.5	C22—C23—H23	120.2
C2—C3—H3	119.5	C23—C24—C25	121.3 (2)
C3—C4—C5	119.7 (2)	C23—C24—H24	119.4
C3—C4—H4	120.2	C25—C24—H24	119.4
C5—C4—H4	120.2	C24—C25—C20	118.6 (2)
C6—C5—C4	119.9 (2)	C24—C25—N5	117.4 (2)
C6—C5—H5	120.0	C20—C25—N5	123.9 (2)
C4—C5—H5	120.0	N5—C26—C27	125.0 (2)
C5—C6—C7	121.5 (2)	N5—C26—C31	116.26 (19)
C5—C6—H6	119.2	C27—C26—C31	118.60 (19)
C7—C6—H6	119.2	C28—C27—C19	113.94 (18)
C6—C7—C2	118.2 (2)	C28—C27—C26	128.89 (19)
C6—C7—N2	117.88 (19)	C19—C27—C26	116.65 (18)
C2—C7—N2	123.59 (19)	N6—C28—C27	131.3 (2)
N2—C8—C9	125.8 (2)	N6—C28—H28	114.4
N2—C8—C13	116.74 (18)	C27—C28—H28	114.4
C9—C8—C13	117.21 (19)	N6—C29—H129	109.5
C10—C9—C1	114.81 (18)	N6—C29—H229	109.5
C10—C9—C8	128.1 (2)	H129—C29—H229	109.5
C1—C9—C8	116.25 (18)	N6—C29—H329	109.5
N3—C10—C9	131.4 (2)	H129—C29—H329	109.5
N3—C10—H10	114.3	H229—C29—H329	109.5
C9—C10—H10	114.3	N6—C30—H130	109.5
N3—C11—H111	109.5	N6—C30—H230	109.5
N3—C11—H211	109.5	H130—C30—H230	109.5
H111—C11—H211	109.5	N6—C30—H330	109.5
N3—C11—H311	109.5	H130—C30—H330	109.5
H111—C11—H311	109.5	H230—C30—H330	109.5
H211—C11—H311	109.5	C32—C31—C36	117.7 (2)
N3—C12—H112	109.5	C32—C31—C26	121.9 (2)
N3—C12—H212	109.5	C36—C31—C26	120.4 (2)
H112—C12—H212	109.5	C33—C32—C31	120.9 (2)
N3—C12—H312	109.5	C33—C32—H32	119.5
H112—C12—H312	109.5	C31—C32—H32	119.5
H212—C12—H312	109.5	C34—C33—C32	120.4 (3)
C14—C13—C18	117.6 (2)	C34—C33—H33	119.8
C14—C13—C8	121.2 (2)	C32—C33—H33	119.8
C18—C13—C8	121.1 (2)	C33—C34—C35	119.3 (3)
C15—C14—C13	120.5 (2)	C33—C34—H34	120.3
C15—C14—H14	119.7	C35—C34—H34	120.3
C13—C14—H14	119.7	C34—C35—C36	121.0 (3)
C14—C15—C16	120.8 (3)	C34—C35—H35	119.5
C14—C15—H15	119.6	C36—C35—H35	119.5
C16—C15—H15	119.6	C35—C36—C31	120.7 (2)
C17—C16—C15	119.6 (3)	C35—C36—H36	119.6
C17—C16—H16	120.2	C31—C36—H36	119.6

C2—N1—C1—O1	155.3 (2)	C20—N4—C19—O2	−152.1 (2)
C2—N1—C1—C9	−25.2 (3)	C20—N4—C19—C27	27.3 (3)
C1—N1—C2—C3	−133.3 (2)	C19—N4—C20—C21	128.2 (2)
C1—N1—C2—C7	49.3 (3)	C19—N4—C20—C25	−53.5 (3)
C7—C2—C3—C4	−2.5 (4)	C25—C20—C21—C22	3.5 (4)
N1—C2—C3—C4	179.9 (2)	N4—C20—C21—C22	−178.2 (2)
C2—C3—C4—C5	0.5 (4)	C20—C21—C22—C23	−1.8 (4)
C3—C4—C5—C6	2.1 (5)	C21—C22—C23—C24	−1.2 (4)
C4—C5—C6—C7	−2.7 (4)	C22—C23—C24—C25	2.6 (4)
C5—C6—C7—C2	0.6 (4)	C23—C24—C25—C20	−0.9 (4)
C5—C6—C7—N2	174.1 (2)	C23—C24—C25—N5	−176.5 (2)
C3—C2—C7—C6	2.0 (3)	C21—C20—C25—C24	−2.1 (3)
N1—C2—C7—C6	179.4 (2)	N4—C20—C25—C24	179.7 (2)
C3—C2—C7—N2	−171.1 (2)	C21—C20—C25—N5	173.2 (2)
N1—C2—C7—N2	6.3 (3)	N4—C20—C25—N5	−5.0 (3)
C8—N2—C7—C6	144.1 (2)	C26—N5—C25—C24	−138.0 (2)
C8—N2—C7—C2	−42.8 (3)	C26—N5—C25—C20	46.6 (3)
C7—N2—C8—C9	−0.2 (3)	C25—N5—C26—C27	−4.4 (3)
C7—N2—C8—C13	174.40 (18)	C25—N5—C26—C31	179.93 (19)
O1—C1—C9—C10	−33.0 (3)	O2—C19—C27—C28	35.1 (3)
N1—C1—C9—C10	147.5 (2)	N4—C19—C27—C28	−144.2 (2)
O1—C1—C9—C8	137.2 (2)	O2—C19—C27—C26	−137.4 (2)
N1—C1—C9—C8	−42.3 (3)	N4—C19—C27—C26	43.3 (3)
N2—C8—C9—C10	−130.9 (2)	N5—C26—C27—C28	129.4 (3)
C13—C8—C9—C10	54.6 (3)	C31—C26—C27—C28	−55.0 (3)
N2—C8—C9—C1	60.4 (3)	N5—C26—C27—C19	−59.4 (3)
C13—C8—C9—C1	−114.2 (2)	C31—C26—C27—C19	116.1 (2)
C11—N3—C10—C9	5.8 (4)	C29—N6—C28—C27	−5.0 (4)
C12—N3—C10—C9	179.3 (3)	C30—N6—C28—C27	−176.9 (2)
C1—C9—C10—N3	−174.9 (2)	C19—C27—C28—N6	173.6 (2)
C8—C9—C10—N3	16.2 (4)	C26—C27—C28—N6	−15.0 (4)
N2—C8—C13—C14	21.1 (3)	N5—C26—C31—C32	165.7 (2)
C9—C8—C13—C14	−163.9 (2)	C27—C26—C31—C32	−10.3 (3)
N2—C8—C13—C18	−155.1 (2)	N5—C26—C31—C36	−15.5 (3)
C9—C8—C13—C18	19.9 (3)	C27—C26—C31—C36	168.6 (2)
C18—C13—C14—C15	0.1 (4)	C36—C31—C32—C33	1.0 (4)
C8—C13—C14—C15	−176.3 (2)	C26—C31—C32—C33	179.9 (3)
C13—C14—C15—C16	−0.8 (4)	C31—C32—C33—C34	−1.2 (5)
C14—C15—C16—C17	1.0 (4)	C32—C33—C34—C35	0.6 (6)
C15—C16—C17—C18	−0.5 (4)	C33—C34—C35—C36	0.3 (6)
C14—C13—C18—C17	0.4 (4)	C34—C35—C36—C31	−0.5 (5)
C8—C13—C18—C17	176.8 (2)	C32—C31—C36—C35	−0.1 (4)
C16—C17—C18—C13	−0.2 (4)	C26—C31—C36—C35	−179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···O2ⁱ	0.86	2.17	2.861 (2)	137
N4—HN4···O1ⁱⁱ	0.86	2.41	2.939 (2)	121

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···O2ⁱ	0.86	2.17	2.861 (2)	137
N4—HN4···O1ⁱⁱ	0.86	2.41	2.939 (2)	121

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

References

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