Quinoline derivatives: potential anti­parasitic and anti­viral agents

The crystal structures of closely related quinoline compounds substituted at the 2-position by a vinyl group, either including a Cl atom [2-(1-chloro-2-methyl­prop-1-enyl)-8-nitro­quinoline, C₁₃H₁₁ClN₂O₂, (I)] or not [2-(2-methyl­prop-1-en­yl)-8-nitro­quinoline, C₁₃H₁₂N₂O₂, (II)], show an important deviation of the vinyl group from coplanarity with the quinoline ring system if the Cl atom is present. The nitro group is perpendicular [in (II)] or nearly so [in (I)] to the quinoline ring system. In (II), all non-H atoms except the nitro O atoms are located on a crystallographic mirror plane.

S1. Comment

Recently, some 2-substituted quinoline compounds have been studied for their antiparasitic (Franck et al., 2004) and antiviral (Zouhiri et al., 2005) activities. Aiming at preparing original analogs with pharmacological potential in the quinoline series through a radical reaction approach, we developed a monoelectronic transfer synthesis by reacting nitrated 2-trihalomethylquinolines with 2-nitropropane salts, leading to the corresponding 2-isopropylidene-substituted products, (I) and (II), in high yields (Verhaeghe et al., 2006). Such C-alkylation and elimination reactions present the main advantage of permitting a one-step access to tri- or tetra-substituted vinyl derivatives through mild operating conditions. Different substrates were used for conducting this chemical work. Firstly, 8-nitro-2-trichloromethylquinoline led to the expected vinyl chloride product (I) by reacting with 2-nitroprane and tetrabutylammonium hydroxide, under light irradiation and inert atmosphere. Then 8-nitro-2-tribromomethylquinoline was reacted in the same conditions, and contrary to the previous results obtained, gave the unhalogenated vinyl product (II), previously synthesized by Nishikawa et al. (1980), most probably as a result of an initial in situ reduction of the tribromomethyl substrate into a dibromomethyl one.

The structural study of these two molecules had various objectives. It seemed important to define the relative position of the substituent in the 2-position with respect to the quinoline ring system, evaluating whether the vinyl bond was conjugated with the aromatic cycle or not. We also studied the coplanarity of the nitro group with respect to the quinoline ring system.

Fig. 1 shows views of the asymmetric units of 2-(1-chloro-2-methylpropenyl)-8-nitroquinoline, (I), and 2-(2-methylprop-1-enyl)-8-nitroquinoline, (II). The structures showed that the vinyl group at the 2-position is rigorously coplanar with the quinoline ring system in the nonhalogenated structure (II) [the dihedral angle is exactly 0.0 (s.u.?)°]. In fact, in the crystal structure of (II), all non-H atoms except the nitro group O atom are located on a crystallographic mirror plane, and so the atoms of both groups lie in the same plane. In (I), the vinyl group is strongly deviated from planarity with the quinoline ring system, with a dihedral angle of 51.60 (2)°. The the bond lengths in the vinyl group show that in (I) the first single bond (C2—C9) is longer than the corresponding bond (C2—C9) in (II). The vinyl double bond is shorter in (I) (Table 1). Comparison with reference lengths for single [C—C ≈ 1.53 (2) Å] and double bonds [C═C ≈ 1.3 2(1) Å] (Glusker et al., 1994) indicates that the vinyl bond is conjugated with the aromatic cycle in both structures, but more strongly in (II).

The nitro group is significantly inclined to the quinoline ring system in both structures. The dihedral angle is 90° in (II) and 61.73 (2)° in (I). Usually, nitro groups are found to be coplanar with aromatic rings, but a search among the structures deposited in the Cambridge Structural Database (CSD; Version 5.18; Allen, 2002) indicated that the nitro group attached to the phenyl ring can deviate somewhat from this coplanar arrangement (by as much as 70°; Zinner et al., 1994). The crystal structure of (II) shows that the vinyl group interacts through a weak hydrogen bond with the N atom of the quinoline ring system (Table 4), and so is situated on this side of the molecule. The steric encumbrance thus caused by the vinyl group obviates a coplanar orientation for the nitro fragment. In (I), the vinyl group deviates from coplanarity with the quinoline system, and so it does not introduce the steric hindrance it does in (II). Therefore, the deviation observed for the nitro group in (I) is probably caused by a weak hydrogen bond between one O atom (O2) of the nitro group and the C4/H4 group of the aromatic ring of a neighboring molecule (Table 2).

In (I), the quinoline rings stack in a nearly parallel orientation (with a dihedral angle of 3.06°), forming columns along b. Considering the interaction between the C₆ and C₅N rings, successive pairs along the stack have Cg···Cg distances of 3.5749 (3) Å [from the C₆ ring at (x, y z) to the C₅N ring at (−x, y − 1/2, −z + 1)] and 3.5911 (3) Å [C₆(x, y, z) to C₅N(−x, y + 1/2, −z + 1)] (Fig. 2). Each interaction in the column includes a slight slip in the c-axis direction. Thus, atom C4A is situated approximately facing the center of gravity of the benzene ring at (−x, y − 1/2, −z + 1), and atom C6 lies over the center of gravity of the pyridine ring at (−x, y − 1/2, −z + 1). These columns are related to each other in the a-axis direction through the weak hydrogen bond described above.

In (II), columns are formed in the b direction through stacking interactions with an interplanar distance of b/2 (approximately 3.45 Å; Fig. 3). The rings are rigorously parallel, and as in (I), alternate rings in the column are slipped (here, in the a direction). In this case, atom C4A is situated exactly facing the center of gravity of the benzene ring, and atom C6 faces the center of gravity of the pyridine ring of the neighbouring molecule at (2 − x, y + 1/2, 1 − z).

Related literature

For related literature, see: Franck et al. (2004); Glusker et al. (1994); Nishikawa et al. (1980); Verhaeghe et al. (2006); Zinner et al. (1994); Zouhiri et al. (2005).

S2. Experimental

The compounds were synthesized according to the method of Verhaeghe et al. (2006).

S3. Refinement

All H-atom parameters were refined freely [C—H = 0.85 (2)–1.022 (12) Å in (I) and C—H = 0.965 (14)–1.029 (19) Å in (II)].

Computing details

For both compounds, data collection: APEX2; cell refinement: APEX2; data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Mutually perpendicular views of compounds (I) and (II), with 50% probability displacement ellipsoids and H atoms as circles of arbitrary radius.
	Fig. 2. Stacking interaction and weak hydrogen bonds (dashed lines) in the halogenated compound (I).
	Fig. 3. Stacking interaction in the nonhalogenated compound (II).

(I) 2-(1-chloro-2-methylpropenyl)-8-nitroquinoline

Crystal data

C13H11ClN2O2	F(000) = 272
Mr = 262.69	Dx = 1.444 Mg m^−3
Monoclinic, P21	Melting point: 401 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.6278 (2) Å	Cell parameters from 9787 reflections
b = 6.6525 (2) Å	θ = 3.6–48.8°
c = 11.3284 (3) Å	µ = 0.31 mm^−1
β = 111.658 (1)°	T = 150 K
V = 604.31 (3) Å^3	Prism, translucent colourless
Z = 2	0.59 × 0.34 × 0.23 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	8940 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.023
Graphite monochromator	θmax = 45.5°, θmin = 2.5°
phi and ω scans	h = −16→17
45955 measured reflections	k = −13→13
9975 independent reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	All H-atom parameters refined
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0513P)^2 + 0.0106P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
9975 reflections	Δρmax = 0.55 e Å^−3
207 parameters	Δρmin = −0.44 e Å^−3
1 restraint	Absolute structure: Flack (1983), 4595 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

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	0.02466 (5)	0.63126 (8)	0.72838 (4)	0.01193 (6)
C2	0.18843 (6)	0.63258 (9)	0.78762 (5)	0.01207 (7)
C3	0.30191 (6)	0.63868 (10)	0.72316 (6)	0.01497 (8)
H3	0.4213 (19)	0.642 (3)	0.7703 (15)	0.023 (3)*
C4	0.24060 (7)	0.64404 (10)	0.59322 (6)	0.01547 (8)
H4	0.306 (2)	0.636 (3)	0.5417 (14)	0.024 (3)*
C4A	0.06634 (7)	0.64360 (9)	0.52595 (5)	0.01314 (7)
C5	−0.00734 (8)	0.64532 (10)	0.39136 (5)	0.01646 (9)
H5	0.056 (2)	0.643 (4)	0.3397 (17)	0.036 (4)*
C6	−0.17734 (9)	0.64050 (11)	0.33036 (5)	0.01788 (9)
H6	−0.234 (2)	0.642 (3)	0.2385 (14)	0.023 (3)*
C7	−0.28168 (8)	0.63302 (11)	0.40162 (5)	0.01688 (9)
H7	−0.410 (2)	0.626 (3)	0.3545 (16)	0.028 (4)*
C8	−0.21056 (6)	0.63563 (10)	0.53138 (5)	0.01372 (7)
C8A	−0.03604 (6)	0.63950 (9)	0.59934 (5)	0.01156 (7)
C9	0.25245 (6)	0.62828 (10)	0.92832 (5)	0.01384 (7)
Cl1	0.40550 (2)	0.44320 (4)	0.992777 (17)	0.02599 (5)
C10	0.20757 (7)	0.74991 (10)	1.00440 (5)	0.01551 (8)
C11	0.08555 (11)	0.91861 (13)	0.95364 (7)	0.02266 (12)
H11A	0.049 (2)	0.935 (4)	0.8615 (14)	0.028 (3)*
H11B	0.000 (3)	0.899 (4)	0.980 (2)	0.050 (6)*
H11C	0.139 (3)	1.038 (4)	0.9909 (19)	0.046 (5)*
C12	0.27972 (11)	0.73368 (15)	1.14658 (6)	0.02407 (13)
H12A	0.198 (2)	0.788 (4)	1.1832 (18)	0.039 (5)*
H12B	0.301 (3)	0.610 (4)	1.172 (2)	0.053 (6)*
H12C	0.361 (3)	0.808 (5)	1.176 (2)	0.060 (7)*
N2	−0.32150 (6)	0.62788 (12)	0.60284 (5)	0.01905 (9)
O2	−0.41357 (8)	0.47998 (13)	0.58512 (7)	0.02795 (13)
O1	−0.31845 (8)	0.76646 (16)	0.67379 (7)	0.03291 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.01043 (13)	0.01378 (16)	0.01126 (13)	0.00101 (13)	0.00364 (10)	0.00055 (13)
C2	0.01033 (14)	0.01196 (17)	0.01353 (15)	0.00083 (14)	0.00395 (12)	0.00015 (15)
C3	0.01169 (16)	0.01539 (19)	0.01899 (19)	0.00065 (16)	0.00702 (14)	−0.00012 (18)
C4	0.01519 (18)	0.0153 (2)	0.01937 (19)	0.00050 (16)	0.01044 (15)	0.00014 (18)
C4A	0.01633 (17)	0.01137 (17)	0.01385 (16)	0.00046 (15)	0.00805 (14)	0.00010 (15)
C5	0.0236 (2)	0.0142 (2)	0.01403 (17)	0.00023 (19)	0.00976 (16)	0.00034 (17)
C6	0.0258 (2)	0.0157 (2)	0.01146 (16)	0.0016 (2)	0.00605 (16)	0.00086 (17)
C7	0.01767 (19)	0.0183 (2)	0.01186 (16)	0.00310 (19)	0.00213 (14)	0.00060 (17)
C8	0.01242 (15)	0.01629 (19)	0.01160 (15)	0.00261 (16)	0.00344 (12)	0.00036 (16)
C8A	0.01167 (15)	0.01190 (17)	0.01142 (14)	0.00133 (14)	0.00461 (12)	0.00023 (14)
C9	0.01140 (15)	0.01420 (19)	0.01359 (16)	0.00054 (15)	0.00187 (12)	0.00140 (16)
Cl1	0.02318 (7)	0.02529 (8)	0.02324 (7)	0.01106 (6)	0.00123 (5)	0.00584 (6)
C10	0.01560 (19)	0.0175 (2)	0.01256 (17)	−0.00187 (16)	0.00418 (14)	−0.00001 (16)
C11	0.0284 (3)	0.0223 (3)	0.0192 (2)	0.0075 (2)	0.0110 (2)	−0.0005 (2)
C12	0.0258 (3)	0.0305 (4)	0.01260 (19)	−0.0053 (3)	0.00322 (19)	−0.0006 (2)
N2	0.01086 (15)	0.0311 (3)	0.01429 (16)	0.00479 (18)	0.00354 (12)	0.00092 (19)
O2	0.0186 (2)	0.0375 (4)	0.0297 (3)	−0.0027 (2)	0.01124 (18)	0.0044 (2)
O1	0.0214 (2)	0.0510 (5)	0.0281 (3)	0.0040 (3)	0.0111 (2)	−0.0161 (3)

Geometric parameters (Å, º)

N1—C2	1.3218 (6)	C7—H7	1.039 (17)
N1—C8A	1.3598 (6)	C8—C8A	1.4159 (7)
C2—C3	1.4217 (7)	C8—N2	1.4649 (7)
C2—C9	1.4821 (7)	C9—C10	1.3394 (9)
C3—C4	1.3686 (8)	C9—Cl1	1.7553 (6)
C3—H3	0.970 (16)	C10—C12	1.5011 (9)
C4—C4A	1.4126 (8)	C10—C11	1.5006 (10)
C4—H4	0.951 (15)	C11—H11A	0.979 (15)
C4A—C5	1.4190 (8)	C11—H11B	0.90 (3)
C4A—C8A	1.4193 (7)	C11—H11C	0.94 (3)
C5—C6	1.3718 (10)	C12—H12A	1.00 (2)
C5—H5	0.937 (18)	C12—H12B	0.87 (3)
C6—C7	1.4145 (9)	C12—H12C	0.82 (3)
C6—H6	0.973 (15)	N2—O1	1.2170 (10)
C7—C8	1.3682 (7)	N2—O2	1.2335 (11)
C2—N1—C8A	117.45 (4)	N1—C8A—C8	119.61 (4)
N1—C2—C3	123.31 (5)	N1—C8A—C4A	123.67 (5)
N1—C2—C9	116.76 (4)	C8—C8A—C4A	116.66 (4)
C3—C2—C9	119.93 (4)	C10—C9—C2	126.79 (5)
C4—C3—C2	119.15 (5)	C10—C9—Cl1	120.52 (4)
C4—C3—H3	120.2 (9)	C2—C9—Cl1	112.67 (4)
C2—C3—H3	120.7 (9)	C9—C10—C12	122.90 (6)
C3—C4—C4A	119.48 (5)	C9—C10—C11	122.26 (5)
C3—C4—H4	125.3 (10)	C12—C10—C11	114.80 (6)
C4A—C4—H4	115.0 (10)	C10—C11—H11A	113.4 (13)
C4—C4A—C5	123.04 (5)	C10—C11—H11B	107.8 (18)
C4—C4A—C8A	116.91 (5)	H11A—C11—H11B	113.1 (18)
C5—C4A—C8A	120.04 (5)	C10—C11—H11C	107.5 (14)
C6—C5—C4A	120.85 (5)	H11A—C11—H11C	107.0 (19)
C6—C5—H5	116.5 (11)	H11B—C11—H11C	108 (2)
C4A—C5—H5	122.5 (11)	C10—C12—H12A	109.9 (11)
C5—C6—C7	120.04 (5)	C10—C12—H12B	112.1 (16)
C5—C6—H6	123.9 (9)	H12A—C12—H12B	107 (2)
C7—C6—H6	116.0 (9)	C10—C12—H12C	109.8 (17)
C8—C7—C6	119.03 (6)	H12A—C12—H12C	104 (2)
C8—C7—H7	121.5 (9)	H12B—C12—H12C	113 (3)
C6—C7—H7	119.4 (9)	O1—N2—O2	124.57 (7)
C7—C8—C8A	123.34 (5)	O1—N2—C8	118.62 (7)
C7—C8—N2	117.89 (5)	O2—N2—C8	116.81 (6)
C8A—C8—N2	118.74 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2^i	0.976 (12)	2.482 (13)	3.2098 (7)	131.2 (10)

Symmetry code: (i) x+1, y, z.

(II) 2-(2-methylprop-1-enyl)-8-nitroquinoline

Crystal data

C13H12N2O2	Dx = 1.359 Mg m^−3
Mr = 228.25	Melting point: 363 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9387 reflections
a = 11.5578 (5) Å	θ = 2.3–33.2°
b = 6.8987 (3) Å	µ = 0.09 mm^−1
c = 13.9900 (6) Å	T = 150 K
V = 1115.48 (8) Å^3	Prism, translucent pale orange
Z = 4	0.54 × 0.25 × 0.20 mm
F(000) = 480

Data collection

Bruker APEXII CCD area-detector diffractometer	1973 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.026
Graphite monochromator	θmax = 33.2°, θmin = 2.9°
phi and ω scans	h = −17→17
53490 measured reflections	k = −10→10
2280 independent reflections	l = −21→21

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F^2) = 0.129	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0772P)^2 + 0.2065P] where P = (Fo^2 + 2Fc^2)/3
2280 reflections	(Δ/σ)max = 0.001
132 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.19 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	0.78011 (7)	0.2500	0.47854 (6)	0.01658 (17)
C2	0.74002 (8)	0.2500	0.56744 (6)	0.01613 (17)
C3	0.81541 (8)	0.2500	0.64820 (7)	0.01892 (19)
H3	0.7777 (15)	0.2500	0.7138 (12)	0.024 (4)*
C4	0.93238 (8)	0.2500	0.63549 (7)	0.01976 (19)
H4	0.9854 (16)	0.2500	0.6928 (13)	0.029 (4)*
C4A	0.97806 (8)	0.2500	0.54161 (7)	0.01659 (18)
C5	1.09778 (8)	0.2500	0.52090 (7)	0.01963 (19)
H5	1.1507 (16)	0.2500	0.5747 (13)	0.032 (4)*
C6	1.13621 (8)	0.2500	0.42820 (7)	0.0213 (2)
H6	1.2220 (16)	0.2500	0.4085 (13)	0.030 (4)*
C7	1.05655 (9)	0.2500	0.35169 (7)	0.0209 (2)
H7	1.0837 (15)	0.2500	0.2831 (13)	0.028 (4)*
C8	0.94126 (8)	0.2500	0.37234 (6)	0.01737 (18)
C8A	0.89640 (8)	0.2500	0.46641 (6)	0.01502 (17)
C9	0.61516 (8)	0.2500	0.58622 (7)	0.01895 (19)
H9	0.5940 (15)	0.2500	0.6555 (13)	0.030 (4)*
C10	0.52460 (8)	0.2500	0.52559 (7)	0.01916 (19)
C11	0.53000 (9)	0.2500	0.41864 (8)	0.0235 (2)
H11A	0.4861 (14)	0.137 (3)	0.3953 (11)	0.057 (4)*
H11B	0.6076 (19)	0.2500	0.3924 (15)	0.044 (5)*
C12	0.40412 (9)	0.2500	0.56518 (9)	0.0261 (2)
H12A	0.3640 (12)	0.134 (2)	0.5456 (9)	0.035 (3)*
H12B	0.4061 (18)	0.2500	0.6342 (15)	0.041 (5)*
N2	0.85661 (8)	0.2500	0.29425 (6)	0.0234 (2)
O1	0.82404 (8)	0.09482 (13)	0.26381 (6)	0.0468 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0114 (3)	0.0229 (4)	0.0155 (3)	0.000	−0.0002 (2)	0.000
C2	0.0119 (3)	0.0212 (4)	0.0154 (4)	0.000	−0.0002 (3)	0.000
C3	0.0141 (4)	0.0288 (5)	0.0139 (4)	0.000	−0.0001 (3)	0.000
C4	0.0135 (4)	0.0300 (5)	0.0157 (4)	0.000	−0.0019 (3)	0.000
C4A	0.0120 (3)	0.0214 (4)	0.0164 (4)	0.000	−0.0010 (3)	0.000
C5	0.0117 (4)	0.0282 (5)	0.0191 (4)	0.000	−0.0014 (3)	0.000
C6	0.0126 (4)	0.0303 (5)	0.0210 (4)	0.000	0.0014 (3)	0.000
C7	0.0145 (4)	0.0304 (5)	0.0177 (4)	0.000	0.0023 (3)	0.000
C8	0.0135 (4)	0.0237 (4)	0.0149 (4)	0.000	−0.0007 (3)	0.000
C8A	0.0116 (3)	0.0187 (4)	0.0148 (4)	0.000	−0.0004 (3)	0.000
C9	0.0118 (4)	0.0275 (4)	0.0175 (4)	0.000	0.0009 (3)	0.000
C10	0.0124 (4)	0.0243 (4)	0.0208 (4)	0.000	−0.0006 (3)	0.000
C11	0.0166 (4)	0.0328 (5)	0.0210 (4)	0.000	−0.0048 (3)	0.000
C12	0.0119 (4)	0.0377 (6)	0.0287 (5)	0.000	0.0009 (3)	0.000
N2	0.0159 (4)	0.0396 (5)	0.0147 (4)	0.000	−0.0001 (3)	0.000
O1	0.0513 (5)	0.0502 (5)	0.0390 (4)	−0.0147 (4)	−0.0213 (3)	−0.0059 (3)

Geometric parameters (Å, º)

N1—C2	1.3272 (12)	C7—C8	1.3634 (13)
N1—C8A	1.3547 (11)	C7—H7	1.010 (18)
C2—C3	1.4269 (13)	C8—C8A	1.4145 (12)
C2—C9	1.4668 (13)	C8—N2	1.4666 (12)
C3—C4	1.3635 (13)	C9—C10	1.3472 (13)
C3—H3	1.016 (17)	C9—H9	1.000 (18)
C4—C4A	1.4155 (13)	C10—C11	1.4976 (15)
C4—H4	1.010 (18)	C10—C12	1.4986 (14)
C4A—C8A	1.4135 (13)	C11—H11A	0.988 (17)
C4A—C5	1.4137 (13)	C11—H11B	0.97 (2)
C5—C6	1.3708 (14)	C12—H12A	0.965 (14)
C5—H5	0.970 (19)	C12—H12B	0.97 (2)
C6—C7	1.4119 (14)	N2—O1	1.2120 (9)
C6—H6	1.029 (19)	N2—O1^i	1.2120 (9)
C2—N1—C8A	117.63 (8)	C7—C8—C8A	123.74 (9)
N1—C2—C3	121.93 (8)	C7—C8—N2	119.61 (8)
N1—C2—C9	120.76 (8)	C8A—C8—N2	116.65 (8)
C3—C2—C9	117.32 (8)	N1—C8A—C4A	124.70 (9)
C4—C3—C2	120.15 (9)	N1—C8A—C8	118.70 (8)
C4—C3—H3	122.9 (10)	C4A—C8A—C8	116.60 (8)
C2—C3—H3	117.0 (10)	C10—C9—C2	130.66 (9)
C3—C4—C4A	119.40 (9)	C10—C9—H9	114.8 (10)
C3—C4—H4	119.9 (10)	C2—C9—H9	114.5 (10)
C4A—C4—H4	120.7 (10)	C9—C10—C11	126.63 (9)
C8A—C4A—C5	120.07 (9)	C9—C10—C12	119.29 (9)
C8A—C4A—C4	116.20 (8)	C11—C10—C12	114.08 (9)
C5—C4A—C4	123.73 (9)	C10—C11—H11A	108.0 (9)
C6—C5—C4A	120.73 (9)	C10—C11—H11B	114.6 (12)
C6—C5—H5	122.0 (11)	H11A—C11—H11B	110.5 (11)
C4A—C5—H5	117.3 (11)	C10—C12—H12A	110.0 (8)
C5—C6—C7	120.39 (9)	C10—C12—H12B	110.3 (12)
C5—C6—H6	124.5 (11)	H12A—C12—H12B	107.2 (10)
C7—C6—H6	115.1 (11)	O1—N2—O1^i	124.08 (10)
C8—C7—C6	118.47 (9)	O1—N2—C8	117.96 (5)
C8—C7—H7	120.3 (10)	O1^i—N2—C8	117.96 (5)
C6—C7—H7	121.2 (10)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···N1	0.97 (2)	2.33 (2)	3.0097 (13)	127 (2)