6,6,8-Triméthyl-6,7-dihydro-5H-tétrazolo[1,5-a]azepine

The title compound, C₉H₁₄N₄, crystallizes in the monoclinic system with three molecules in the asymmetric unit. These three molecules have similar conformations and are connected through weak C—H...N interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.097
• wR factor = 0.149
• Data-to-parameter ratio = 13.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.31
         From the CIF: _reflns_number_total               5516
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6006
         Completeness (_total/calc)             91.84%
          Alert C: < 95% complete

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.140


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Les tétrazoles substitués présentent de plus en plus d'intérèt. En effet, ils sont utilisés en médecine, biochimie, agriculture ou comme inhibiteurs de corrosion. Ainsi, le 5-(2-anilinophényl)tétrazole a une activité anti-inflammatoire (Juby et al., 1968), le 5-amino tétrazole est utilisé comme régulateur de la croissance des plantes (Mashtanov, 1970), le 1-alkyl-5-aminotétrazole et le 1-aryl-5-dialkylaminomethyltétrazole ont été identifiés comme stimulants du système nerveux central (Herbst et al., 1952). Dans le but de préparer des systèmes tétrazoliques (Lassaba et al., 1997; Dakir et al., 2001) à base de l'isophorone, nous avons étudié le comportement de ce dernier vis-à-vis de l'acide azothydrique généré in situ à partir de l'azoture de sodium et de l'acide trifluoroacétique. Ainsi, le traitement de l'isophorone par l'azoture de sodium, en présence d'acide trifluoroacétique utilisé comme solvant et catalyseur (Kaye et al., 1995), conduit à deux isomères, avec un rendement de 70%. Ces deux isoméres correspondent à l'insertion de l'atome d'azote d'un côté ou de l'autre du carbonyle. Une analyse cristallographique d'un monocristal du produit majoritaire nous a permis de conclure que ce dernier est un tétrazole résultant de l'insertion de l'atome d'azote du côté du carbone le moins substitué, par la suite de l'identifier au 6,6,8-triméthyl-6,7-dihydro-5H-tétrazolo[1,5-a]azepine. Le deuxième isomère correspond alors au 6,6,8-triméthyl-8,9-dihydro-7H-tétrazolo[1,5-a]azepine, (I). Ce composé cristallize dans le système monoclinique, avec 3 molécules indépendantes dans l'unité asymétrique (Figs. 1 e t 2). Aux erreurs expérimentales près, les distances et angles de liaison sont identiques pour les trois molécules (Tableau 1). La conformation reste la même dans les trois molécules: le plan tétrazolo N1/N2/N3/N4/C10 et le fragment N4/C5/C8/C9/C10 sont coplanaires, l'angle dièdre variant de 1.6 (2) à 3.9 (2)° sur les trois molécules; l'angle de torsion C5–C6–C7–C8 varie de 60.9 (4)° à 64.9 (4)°. Ces molécules sont liées entre elles par de faibles interactions C—H···N (Tableau 2).

S2. Experimental

A une solution de (1 g, 7.2 mmol) d'isophorone dans l'acide trifluoroacétique (25 ml) on ajoute en petites fractions pendant 30 min l'azoture de sodium à une température de 263 K. Après 24 h d'agitation, le mélange réactionnel est neutralisé avec une solution de bicarbonate de sodium (10%) puis extrait avec l'éther (3 × 25 ml). Les phases organiques sont rassemblées, lavées à l'eau et sur sulfate de sodium. Le solvant est évaporé sous pression réduite.

Computing details

Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Dessin ORTEPIII (Burnett & Johnson, 1996) de l'une des molécules. Les ellipsoides de vibration thermiques ont une probabilité de 50%.
	Fig. 2. Vue des interactions C—H···N reliant les trois molécules de l'unité asymétrique. Les ellipsoides de vibration thermiques ont une probabilité de 30%.

(I)

Crystal data

C9H14N4	F(000) = 1152
Mr = 178.24	Dx = 1.201 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 18845 reflections
a = 12.024 (1) Å	θ = 3–26°
b = 13.624 (1) Å	µ = 0.08 mm^−1
c = 18.080 (2) Å	T = 293 K
β = 92.905 (5)°	Prism, colourless
V = 2958.0 (4) Å^3	0.40 × 0.25 × 0.20 mm
Z = 12

Data collection

Nonius KappaCCD diffractometer	3440 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.14
Graphite monochromator	θmax = 26.3°, θmin = 3.1°
ϕ scans	h = −14→14
18845 measured reflections	k = −16→16
5516 independent reflections	l = −22→22

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)] = 0.098	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.011P)^2 + 1.9298P] where P = (Fo^2 + 2Fc^2)/3
4910 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.13 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
N1	0.1612 (3)	0.5499 (2)	−0.01800 (16)	0.0623 (8)
N2	0.2526 (3)	0.5871 (2)	−0.04789 (17)	0.0705 (9)
N3	0.3422 (3)	0.5577 (2)	−0.01115 (17)	0.0608 (8)
N4	0.3076 (2)	0.49988 (19)	0.04372 (15)	0.0506 (7)
N21	0.4018 (2)	0.5333 (2)	0.30194 (15)	0.0557 (8)
N22	0.3093 (3)	0.5781 (2)	0.27291 (16)	0.0637 (8)
N23	0.2247 (2)	0.5616 (2)	0.31326 (16)	0.0577 (8)
N24	0.2638 (2)	0.50424 (18)	0.37043 (14)	0.0482 (7)
N41	0.9036 (3)	0.4504 (2)	0.35568 (17)	0.0665 (9)
N42	0.8128 (3)	0.4094 (2)	0.38442 (17)	0.0708 (9)
N43	0.7236 (3)	0.4309 (2)	0.34407 (17)	0.0623 (8)
N44	0.7568 (2)	0.48686 (19)	0.28775 (15)	0.0491 (7)
C5	0.3883 (3)	0.4555 (2)	0.09782 (18)	0.0529 (9)
H5A	0.3919	0.4953	0.1423	0.064*
H5B	0.4614	0.4566	0.0775	0.064*
C6	0.3608 (3)	0.3502 (2)	0.11882 (17)	0.0477 (8)
C7	0.2611 (3)	0.3459 (2)	0.16748 (18)	0.0515 (9)
H7A	0.2542	0.2784	0.1836	0.062*
H7B	0.2800	0.3845	0.2114	0.062*
C8	0.1477 (3)	0.3783 (2)	0.13899 (18)	0.0475 (8)
C9	0.1229 (3)	0.4413 (2)	0.08425 (18)	0.0515 (9)
H9	0.0474	0.4520	0.0737	0.062*
C10	0.1971 (3)	0.4950 (2)	0.03923 (17)	0.0413 (7)
C11	0.0536 (3)	0.3333 (3)	0.1791 (2)	0.0697 (11)
H11A	−0.0162	0.3555	0.1570	0.105*
H11B	0.0593	0.3526	0.2302	0.105*
H11C	0.0576	0.2631	0.1757	0.105*
C12	0.3418 (3)	0.2864 (3)	0.04976 (19)	0.0671 (11)
H12A	0.3332	0.2191	0.0643	0.101*
H12B	0.4045	0.2921	0.0192	0.101*
H12C	0.2757	0.3078	0.0224	0.101*
C13	0.4627 (3)	0.3120 (3)	0.1648 (2)	0.0755 (12)
H13A	0.4505	0.2449	0.1784	0.113*
H13B	0.4739	0.3512	0.2087	0.113*
H13C	0.5275	0.3161	0.1359	0.113*
C25	0.1892 (3)	0.4740 (3)	0.42799 (19)	0.0578 (9)
H25A	0.1128	0.4802	0.4087	0.069*
H25B	0.1992	0.5182	0.4699	0.069*
C26	0.2086 (3)	0.3689 (2)	0.45484 (18)	0.0523 (9)
C27	0.3169 (3)	0.3594 (3)	0.50148 (18)	0.0596 (10)
H27A	0.3123	0.4045	0.5427	0.071*
H27B	0.3185	0.2937	0.5222	0.071*
C28	0.4270 (3)	0.3762 (2)	0.46899 (18)	0.0525 (9)
C29	0.4482 (3)	0.4302 (2)	0.40976 (18)	0.0514 (9)
H29	0.5221	0.4314	0.3970	0.062*
C30	0.3719 (2)	0.4870 (2)	0.36283 (17)	0.0404 (7)
C31	0.5236 (3)	0.3261 (3)	0.5100 (2)	0.0818 (13)
H31A	0.5915	0.3429	0.4873	0.123*
H31B	0.5131	0.2563	0.5080	0.123*
H31C	0.5276	0.3473	0.5607	0.123*
C32	0.1118 (3)	0.3456 (3)	0.5047 (2)	0.0844 (13)
H32A	0.1215	0.2809	0.5250	0.127*
H32B	0.0426	0.3487	0.4758	0.127*
H32C	0.1110	0.3926	0.5441	0.127*
C33	0.2044 (3)	0.2965 (3)	0.39031 (19)	0.0686 (11)
H33A	0.2108	0.2308	0.4091	0.103*
H33B	0.2648	0.3097	0.3590	0.103*
H33C	0.1349	0.3036	0.3622	0.103*
C45	0.6776 (3)	0.5227 (2)	0.23030 (18)	0.0548 (9)
H45A	0.6028	0.5153	0.2472	0.066*
H45B	0.6834	0.4826	0.1864	0.066*
C46	0.6957 (3)	0.6302 (2)	0.20960 (17)	0.0477 (8)
C47	0.7980 (3)	0.6428 (2)	0.16428 (17)	0.0512 (9)
H47A	0.7844	0.6059	0.1189	0.061*
H47B	0.8011	0.7115	0.1503	0.061*
C48	0.9120 (3)	0.6153 (2)	0.19438 (18)	0.0485 (8)
C49	0.9389 (3)	0.5542 (2)	0.24975 (19)	0.0535 (9)
H49	1.0148	0.5460	0.2606	0.064*
C50	0.8664 (3)	0.4988 (2)	0.29532 (17)	0.0435 (8)
C51	1.0048 (3)	0.6630 (3)	0.1544 (2)	0.0734 (12)
H51A	1.0752	0.6396	0.1746	0.110*
H51B	1.0010	0.7329	0.1603	0.110*
H51C	0.9973	0.6469	0.1027	0.110*
C52	0.7045 (3)	0.6950 (3)	0.27866 (19)	0.0643 (10)
H52A	0.7064	0.7628	0.2641	0.096*
H52B	0.7715	0.6792	0.3073	0.096*
H52C	0.6413	0.6838	0.3079	0.096*
C53	0.5919 (3)	0.6604 (3)	0.1614 (2)	0.0726 (11)
H53A	0.5997	0.7272	0.1455	0.109*
H53B	0.5269	0.6546	0.1898	0.109*
H53C	0.5845	0.6183	0.1189	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.059 (2)	0.061 (2)	0.067 (2)	0.0052 (16)	0.0081 (16)	0.0069 (16)
N2	0.089 (3)	0.058 (2)	0.065 (2)	0.0092 (19)	0.0116 (19)	0.0128 (16)
N3	0.067 (2)	0.0520 (19)	0.065 (2)	−0.0054 (16)	0.0215 (16)	0.0086 (16)
N4	0.057 (2)	0.0411 (17)	0.0546 (18)	−0.0018 (14)	0.0129 (14)	0.0030 (13)
N21	0.0548 (19)	0.0564 (18)	0.0569 (19)	−0.0041 (15)	0.0113 (14)	0.0051 (14)
N22	0.075 (2)	0.0549 (19)	0.062 (2)	−0.0037 (17)	0.0124 (17)	0.0135 (15)
N23	0.063 (2)	0.0518 (18)	0.0584 (19)	0.0038 (15)	0.0029 (15)	0.0156 (15)
N24	0.0521 (19)	0.0434 (16)	0.0493 (17)	−0.0032 (14)	0.0052 (13)	0.0079 (13)
N41	0.066 (2)	0.060 (2)	0.073 (2)	0.0086 (17)	0.0029 (17)	0.0165 (17)
N42	0.083 (3)	0.059 (2)	0.071 (2)	0.0111 (18)	0.0131 (19)	0.0225 (16)
N43	0.067 (2)	0.0512 (19)	0.071 (2)	0.0039 (16)	0.0238 (17)	0.0196 (16)
N44	0.0486 (19)	0.0425 (17)	0.0572 (18)	0.0004 (14)	0.0123 (13)	0.0082 (13)
C5	0.041 (2)	0.060 (2)	0.058 (2)	−0.0078 (17)	0.0075 (16)	0.0011 (17)
C6	0.046 (2)	0.048 (2)	0.050 (2)	0.0020 (16)	0.0048 (15)	0.0018 (15)
C7	0.055 (2)	0.046 (2)	0.054 (2)	−0.0053 (17)	0.0035 (17)	0.0029 (16)
C8	0.050 (2)	0.0432 (19)	0.050 (2)	−0.0115 (17)	0.0143 (16)	−0.0106 (16)
C9	0.040 (2)	0.055 (2)	0.061 (2)	−0.0018 (17)	0.0108 (16)	−0.0052 (18)
C10	0.035 (2)	0.0407 (19)	0.048 (2)	0.0046 (15)	0.0033 (14)	−0.0024 (15)
C11	0.063 (3)	0.066 (3)	0.083 (3)	−0.011 (2)	0.030 (2)	0.000 (2)
C12	0.080 (3)	0.060 (2)	0.062 (2)	0.014 (2)	0.0063 (19)	−0.0128 (19)
C13	0.061 (3)	0.085 (3)	0.079 (3)	0.014 (2)	−0.008 (2)	0.010 (2)
C25	0.051 (2)	0.062 (2)	0.062 (2)	0.0043 (18)	0.0179 (17)	0.0095 (18)
C26	0.057 (2)	0.052 (2)	0.049 (2)	−0.0050 (17)	0.0090 (17)	0.0077 (16)
C27	0.080 (3)	0.051 (2)	0.048 (2)	−0.001 (2)	0.0011 (19)	0.0064 (17)
C28	0.062 (2)	0.045 (2)	0.048 (2)	0.0043 (17)	−0.0147 (17)	−0.0080 (16)
C29	0.040 (2)	0.054 (2)	0.059 (2)	0.0021 (16)	−0.0038 (16)	−0.0091 (18)
C30	0.0335 (19)	0.0401 (18)	0.048 (2)	−0.0057 (15)	0.0085 (14)	−0.0038 (15)
C31	0.090 (3)	0.069 (3)	0.082 (3)	0.014 (2)	−0.036 (2)	0.001 (2)
C32	0.087 (3)	0.086 (3)	0.083 (3)	−0.011 (2)	0.035 (2)	0.023 (2)
C33	0.076 (3)	0.064 (3)	0.065 (3)	−0.022 (2)	0.004 (2)	−0.0015 (19)
C45	0.047 (2)	0.058 (2)	0.060 (2)	−0.0078 (18)	0.0044 (17)	0.0071 (17)
C46	0.050 (2)	0.044 (2)	0.050 (2)	−0.0011 (16)	0.0061 (16)	0.0029 (15)
C47	0.065 (2)	0.0387 (19)	0.050 (2)	−0.0009 (17)	0.0072 (17)	0.0016 (15)
C48	0.051 (2)	0.0395 (19)	0.056 (2)	−0.0032 (16)	0.0151 (17)	−0.0056 (16)
C49	0.044 (2)	0.050 (2)	0.067 (2)	0.0026 (17)	0.0090 (17)	0.0005 (18)
C50	0.042 (2)	0.0363 (19)	0.053 (2)	0.0057 (16)	0.0074 (15)	0.0027 (15)
C51	0.069 (3)	0.066 (3)	0.088 (3)	−0.011 (2)	0.032 (2)	0.010 (2)
C52	0.066 (3)	0.059 (2)	0.068 (3)	0.0169 (19)	0.0140 (19)	−0.0046 (19)
C53	0.059 (3)	0.076 (3)	0.081 (3)	0.003 (2)	−0.011 (2)	0.019 (2)

Geometric parameters (Å, º)

N1—C10	1.331 (4)	C6—C13	1.536 (4)
N1—N2	1.348 (4)	C7—C8	1.499 (4)
N2—N3	1.300 (4)	C8—C9	1.332 (4)
N3—N4	1.349 (3)	C8—C11	1.505 (4)
N4—C10	1.329 (4)	C9—C10	1.437 (4)
N4—C5	1.472 (4)	C25—C26	1.526 (4)
N21—C30	1.334 (4)	C26—C27	1.521 (5)
N21—N22	1.350 (4)	C26—C33	1.526 (5)
N22—N23	1.301 (4)	C26—C32	1.540 (4)
N23—N24	1.360 (3)	C27—C28	1.493 (5)
N24—C30	1.334 (4)	C28—C29	1.334 (4)
N24—C25	1.467 (4)	C28—C31	1.509 (4)
N41—C50	1.333 (4)	C29—C30	1.443 (4)
N41—N42	1.353 (4)	C45—C46	1.530 (4)
N42—N43	1.299 (4)	C46—C47	1.522 (4)
N43—N44	1.348 (3)	C46—C52	1.528 (4)
N44—C50	1.329 (4)	C46—C53	1.541 (4)
N44—C45	1.457 (4)	C47—C48	1.496 (4)
C5—C6	1.524 (4)	C48—C49	1.329 (4)
C6—C7	1.524 (4)	C48—C51	1.508 (4)
C6—C12	1.530 (4)	C49—C50	1.442 (4)
C10—N1—N2	106.5 (3)	N1—C10—C9	122.7 (3)
N3—N2—N1	110.6 (3)	N24—C25—C26	113.6 (3)
N2—N3—N4	106.1 (3)	C27—C26—C25	111.6 (3)
C10—N4—N3	109.2 (3)	C27—C26—C33	111.3 (3)
C10—N4—C5	130.0 (3)	C25—C26—C33	111.4 (3)
N3—N4—C5	120.8 (3)	C27—C26—C32	108.0 (3)
C30—N21—N22	106.4 (3)	C25—C26—C32	105.8 (3)
N23—N22—N21	110.9 (3)	C33—C26—C32	108.5 (3)
N22—N23—N24	106.0 (3)	C28—C27—C26	121.4 (3)
C30—N24—N23	108.9 (2)	C29—C28—C27	127.6 (3)
C30—N24—C25	131.1 (3)	C29—C28—C31	118.0 (3)
N23—N24—C25	120.0 (3)	C27—C28—C31	114.4 (3)
C50—N41—N42	106.0 (3)	C28—C29—C30	128.7 (3)
N43—N42—N41	110.5 (3)	N24—C30—N21	107.8 (3)
N42—N43—N44	106.5 (3)	N24—C30—C29	128.9 (3)
C50—N44—N43	108.8 (3)	N21—C30—C29	123.3 (3)
C50—N44—C45	129.9 (3)	N44—C45—C46	113.6 (3)
N43—N44—C45	121.4 (3)	C47—C46—C52	110.5 (3)
N4—C5—C6	114.1 (3)	C47—C46—C45	111.6 (3)
C5—C6—C7	111.6 (3)	C52—C46—C45	111.0 (3)
C5—C6—C12	110.9 (3)	C47—C46—C53	108.6 (3)
C7—C6—C12	111.1 (3)	C52—C46—C53	109.2 (3)
C5—C6—C13	106.0 (3)	C45—C46—C53	105.8 (3)
C7—C6—C13	107.7 (3)	C48—C47—C46	121.8 (3)
C12—C6—C13	109.3 (3)	C49—C48—C47	127.9 (3)
C8—C7—C6	121.2 (3)	C49—C48—C51	118.2 (3)
C9—C8—C7	127.6 (3)	C47—C48—C51	113.8 (3)
C9—C8—C11	118.4 (3)	C48—C49—C50	128.8 (3)
C7—C8—C11	114.0 (3)	N44—C50—N41	108.2 (3)
C8—C9—C10	128.8 (3)	N44—C50—C49	129.1 (3)
N4—C10—N1	107.7 (3)	N41—C50—C49	122.7 (3)
N4—C10—C9	129.7 (3)
C10—N1—N2—N3	−0.4 (4)	N24—C25—C26—C32	−171.1 (3)
N1—N2—N3—N4	0.2 (4)	C25—C26—C27—C28	−64.9 (4)
N2—N3—N4—C10	0.1 (3)	C33—C26—C27—C28	60.2 (4)
N2—N3—N4—C5	−178.5 (3)	C32—C26—C27—C28	179.2 (3)
C30—N21—N22—N23	0.3 (4)	C26—C27—C28—C29	24.5 (5)
N21—N22—N23—N24	0.1 (4)	C26—C27—C28—C31	−156.3 (3)
N22—N23—N24—C30	−0.4 (3)	C27—C28—C29—C30	1.0 (6)
N22—N23—N24—C25	178.4 (3)	C31—C28—C29—C30	−178.1 (3)
C50—N41—N42—N43	0.1 (4)	N23—N24—C30—N21	0.5 (3)
N41—N42—N43—N44	0.2 (4)	C25—N24—C30—N21	−178.1 (3)
N42—N43—N44—C50	−0.4 (4)	N23—N24—C30—C29	180.0 (3)
N42—N43—N44—C45	178.6 (3)	C25—N24—C30—C29	1.4 (5)
C10—N4—C5—C6	41.5 (5)	N22—N21—C30—N24	−0.5 (3)
N3—N4—C5—C6	−140.2 (3)	N22—N21—C30—C29	−180.0 (3)
N4—C5—C6—C7	−72.0 (4)	C28—C29—C30—N24	5.0 (6)
N4—C5—C6—C12	52.4 (4)	C28—C29—C30—N21	−175.6 (3)
N4—C5—C6—C13	171.0 (3)	C50—N44—C45—C46	−44.6 (5)
C5—C6—C7—C8	64.0 (4)	N43—N44—C45—C46	136.6 (3)
C12—C6—C7—C8	−60.3 (4)	N44—C45—C46—C47	73.5 (4)
C13—C6—C7—C8	180.0 (3)	N44—C45—C46—C52	−50.2 (4)
C6—C7—C8—C9	−24.2 (5)	N44—C45—C46—C53	−168.6 (3)
C6—C7—C8—C11	156.4 (3)	C52—C46—C47—C48	63.0 (4)
C7—C8—C9—C10	−0.8 (6)	C45—C46—C47—C48	−60.9 (4)
C11—C8—C9—C10	178.5 (3)	C53—C46—C47—C48	−177.2 (3)
N3—N4—C10—N1	−0.4 (3)	C46—C47—C48—C49	20.9 (5)
C5—N4—C10—N1	178.0 (3)	C46—C47—C48—C51	−160.3 (3)
N3—N4—C10—C9	178.7 (3)	C47—C48—C49—C50	−0.2 (6)
C5—N4—C10—C9	−2.9 (5)	C51—C48—C49—C50	−178.9 (3)
N2—N1—C10—N4	0.5 (4)	N43—N44—C50—N41	0.4 (4)
N2—N1—C10—C9	−178.7 (3)	C45—N44—C50—N41	−178.5 (3)
C8—C9—C10—N4	−4.6 (6)	N43—N44—C50—C49	−178.7 (3)
C8—C9—C10—N1	174.4 (3)	C45—N44—C50—C49	2.4 (5)
C30—N24—C25—C26	−40.0 (5)	N42—N41—C50—N44	−0.3 (4)
N23—N24—C25—C26	141.6 (3)	N42—N41—C50—C49	178.9 (3)
N24—C25—C26—C27	71.7 (4)	C48—C49—C50—N44	8.5 (6)
N24—C25—C26—C33	−53.4 (4)	C48—C49—C50—N41	−170.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···N22	0.97	2.84	3.744 (5)	155
C7—H7B···N22	0.97	2.88	3.723 (4)	146
C29—H29···N43	0.93	2.65	3.574 (4)	173
C45—H45A···N21	0.97	2.67	3.624 (4)	168