(E)-2-Methyl-3-(2-methyl-2-nitro­vinyl)-1H-indole and (E)-3-(2-methyl-2-nitro­vinyl)-2-phenyl-1H-indole

In the title compounds, C₁₂H₁₂N₂O₂, (I), and C₁₇H₁₄N₂O₂, (II), respectively, the indole rings are planar and the vinyl groups lie out of the indole planes, making dihedral angles of 33.48 (5) and 41.31 (8)°, respectively. In (II), the dihedral angle between the phenyl and indole ring planes is 32.06 (6)°. In both mol­ecules, the double bond connecting the methyl­nitro­vinyl group and the indole nucleus adopts an E configuration. Notwithstanding the differences in space group [C2/c for (I) and P2₁2₁2₁ for (II)], the mode of packing of compounds (I) and (II) is determined by similar inter­molecular N—H...O hydrogen-bonding inter­actions, forming chains that run parallel to [101] in (I) and [001] in (II).

S1. Comment

3-(2-Nitrovinyl)indoles are very important synthons for the preparation of tryptamines (Shen et al., 1998) in high yield. They also undergo Michael addition reactions, resulting in the formation of a wide range of indole derivatives (Chakrabarty et al., 2001). Apart from their synthetic utility, 3-(2-nitrovinyl)indoles also exhibit amebicidal (Sharma et al., 1987) and antifungal (Canoira et al., 1989) activity. We have synthesized a series of 3-(2-nitrovinyl)indoles and evaluated them for antitubercular activity (Sonar & Crooks, unpublished work).

The title compounds, (I) and (II), were prepared by condensation of 2-methyl-indole-3-carboxaldehyde and 2-phenyl-indole-3-carboxaldehyde with nitroethane in the presence of ammonium acetate, to afford (E)-2-methyl-3-(2-methyl-2-nitrovinyl)-1H-indole, (I), and (E)-3-(2-methyl-2-nitrovinyl)-2-phenyl-1H-indole, (II), each as a single geometrical isomer. The structures of products (I) and (II) were initially identified by NMR spectroscopy. Generally, condensation reactions of indole-3-carboxaldehydes with nitromethane or nitroethane afford the corresponding E isomer. However, when a nitrovinyl group containing an ester functionality in the 2-position is utilized in these types of reactions, the reaction affords a mixture of Z and E isomers (Bakhmutov et al., 1977). In order to confirm the double-bond geometry of the title compounds, and to obtain more detailed information on the structural conformations of these molecules in the solid state, their X-ray structure determination has been carried out and the results are presented here.

Figs. 1 and 2 illustrate the molecular structures and atom-numbering schemes for (I) and (II), respectively. For ease of comparison, the two compounds are discussed in parallel below. Selected geometric parameters are presented in Tables 1 and 3 for (I) and (II), respectively. For each structure, the indole ring is planar, with bond distances and angles comparable with those reported for other indole derivatives (Mason et al., 2003). Compounds (I) and (II) are E isomers, and the N2—C10 bond is in a trans disposition with respect to the C2—C9 bond. In both compounds, deviations from the ideal bond angle of 120° are observed in the bond angles C2═ C1—C12, C2—C9═C10, C9═C10—C11, C9═C10—N2 and N2—C10—C11. While the N1—C1—C12 and C1═C2—C9 bond angles are close to the ideal value, the C2—C9═C10—N2 torsion angle indicates that the nitrovinyl group is nearly planar [177.96 (11)° in (I) and 178.86 (18)° in (II)], and the plane of the nitrovinyl group is twisted, by 33.48 (5)° for (I) and 41.31 (8)° for (II), with respect to the indole ring plane. However, comparing the C2—C9 bond length [1.4335 (17) Å in (I) and 1.451 (3) Å in (II)] with the standard value for a single bond connecting a C_ar atom to a Csp² atom [1.470 (15) Å; Wilson, 1992] suggests that the indolic system has an extended conjugation through the ethylene double bond and the nitro group. There is further evidence for this in the shortening of the N1—C1 and N2—C10 and lengthening of the C1═C2 and C9═C10 bonds compared with their reported values (Mason et al., 2003; Strauss et al., 2003). [From the Co-Editor: It is not clear what the `reported values' above refer to.] In the case of (II), the phenyl group at the 2-position makes a dihedral angle of 32.06 (6)° with the plane of the indole ring. This extended conjugation suggests that compounds (I) and (II) exist predominantly in resonance forms (Ia) and (IIa), respectively, which explains the highly coloured and crystalline nature of the title compounds. [From the Co-Editor: Please explain how the observed resonance forms enhance crystallinity.] Furthermore, the absence of IR absorption bands at ???? and ???? cm⁻¹ [From the Co-Editor: Please give frequencies of these bands.], which is typical of the nitro group in 3-(2-nitrovinyl)indoles (Bucki & Mark, 1977), the appearance of two new bands between 1300 and 1250 cm⁻¹, and the intense UV absorption near 400 nm confirm the existence of resonance forms (Ia) and (IIa).

The packing of compounds (I) and (II), as viewed along the b and a axes, is illustrated in Figs. 3 and 4, respectively. In each, atom H1 participates in a weak intermolecular N1—H1···O2 interaction [symmetry codes (1/2 + x, 1/2 − y, 1/2 + z) for (I) and (1/2 − x, −y, 1/2 + z) for (II)], linking the title compounds into chains that run parallel to [101] and [001], respectively. [From the Co-Editor: Please check change in direction of chains.]

S2. Experimental

For the preparation of (I), solid ammonium acetate (0.3 g, 3.8 mmol) was added to a suspension of 2-methylindole-3-carboxaldehyde (1.08 g, 6.8 mmol) in nitroethane (3 ml). The mixture was stirred vigorously under reflux at 393–403 K for 2 h. The mixture was then cooled, and the solid which appeared was collected by filtration. Recrystallization from methanol afforded dark-brown crystals of (I) suitable for X-ray analysis. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 2.26 (s, 3H), 2.42 (s, 3H), 7.11 (pd, 2H), 7.37 (dd, 1H), 7.47 (dd, 1H), 8.28 (s, 1H), 11.92 (s, 1H); ¹³C NMR (CDCl₃, δ, p.p.m.): 12.6, 15.8, 105.3, 111.5, 119.4, 120.3, 121.7, 125.6, 129.1, 135.9, 141.5, 145.6. For the preparation of (II), solid ammonium acetate (0.3 g, 3.8 mmol) was added to a suspension of 2-phenyl-indole-3-carboxaldehyde (1.5 g, 6.8 mmol) in nitroethane (3 ml). The mixture was stirred vigorously under reflux at 393–403 K for 2 h. The mixture was then cooled and the solid which appeared was collected by filtration. Recrystallization from methanol afforded orange crystals of (II), which were suitable for X-ray analysis. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 2.22 (s, 3H), 7.20 (m, 2H), 7.58 (m, 7H), 8.17 (s, 1H), 12.28 (s, 1H); ¹³C NMR (CDCl₃, δ, p.p.m.): 15.7, 105.0, 112.1, 120.0, 120.7, 122.7, 125.9, 128.7, 128.9, 129.2, 131.0, 136.5, 141.2, 144.0.

S3. Refinement

[From the Co-Editor: Data collection temperature precision varies between (I) and (II) - is this correct?] The refinement of structure (I) required no particular special treatment. However, for structure (II), which is an all-light atom achiral molecule that happened to crystallize in space group P2₁2₁2₁, the Friedel opposites were not merged and the structure was refined as an inversion twin. Not surprisingly, the Flack parameter (Flack, 1983) in this case, 0.4 (16), was wholly inconclusive, and for this reason the twin fractions were fixed at 50:50 for the final stages of refinement. An alternative treatment involving refinement against a data set where the Friedel pairs had been merged led to some small differences: the largest Fourier difference map features were marginally smaller (0.18 and −0.20 e Å⁻³, versus 0.19 and −0.21 e Å⁻³ for the unmerged data), the value of R₁ was smaller (0.041 versus 0.044), and the s.u. values were larger by a factor of around 1.3, which is approximately the square root of the ratio of the numbers of data present in each set. [From the Co-Editor: R values corrected from 0.41 and 0.44, and minor changes in paragraph above. Please check.] The H atoms in both structures (I) and (II) were found in difference Fourier maps and subsequently refined using riding models, in which the H-atom coordinates were determined geometrically from their attached parent atom. [From the Co-Editor: A riding model is not suitable for methyl groups attached to sp² centres. Please check and correct as necessary.] Bond distances for H atoms were fixed as follows: C_Ar—H = 0.95 Å, C_Me—H = 0.98 Å and N—H = 0.88 Å. Isotropic displacement parameters for the H atoms were defined as 1.2U_eq for C_ArH and NH, and 1.5U_eq for methyl H.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local procedures.

Figures

	Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The crystal structure of (I), viewed along the b axis.
	Fig. 4. The crystal structure of (II), viewed along the a axis.

(I) (E)-2-Methyl-3-(2-methyl-2-nitrovinyl)-1H-indole

Crystal data

C12H12N2O2	F(000) = 912
Mr = 216.24	Dx = 1.380 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2484 reflections
a = 12.1176 (3) Å	θ = 1.0–27.5°
b = 11.3888 (3) Å	µ = 0.10 mm^−1
c = 15.2667 (4) Å	T = 90 K
β = 98.8372 (10)°	Block, orange-brown
V = 2081.87 (9) Å^3	0.40 × 0.35 × 0.30 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	1927 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
Detector resolution: 18 pixels mm^-1	h = −15→15
ω scans at fixed χ = 55°	k = −13→14
4507 measured reflections	l = −19→19
2390 independent reflections

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: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0604P)^2 + 0.7762P] where P = (Fo^2 + 2Fc^2)/3
2390 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.31 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	0.96205 (9)	0.17120 (9)	0.55102 (7)	0.0195 (3)
H1	1.0200	0.2031	0.5844	0.023*
C1	0.90448 (10)	0.22094 (11)	0.47734 (8)	0.0183 (3)
C2	0.82023 (10)	0.14377 (11)	0.43973 (8)	0.0179 (3)
C3	0.82636 (10)	0.04273 (11)	0.49826 (8)	0.0179 (3)
C4	0.76176 (10)	−0.05825 (11)	0.50539 (8)	0.0212 (3)
H4	0.6980	−0.0738	0.4625	0.025*
C5	0.79175 (11)	−0.13491 (12)	0.57545 (9)	0.0244 (3)
H5	0.7481	−0.2033	0.5799	0.029*
C6	0.88487 (11)	−0.11384 (12)	0.63976 (8)	0.0253 (3)
H6	0.9044	−0.1687	0.6865	0.030*
C7	0.94879 (11)	−0.01395 (12)	0.63602 (8)	0.0235 (3)
H7	1.0122	0.0012	0.6794	0.028*
C8	0.91685 (10)	0.06328 (11)	0.56640 (8)	0.0190 (3)
C9	0.74819 (10)	0.17300 (11)	0.35919 (8)	0.0186 (3)
H9	0.7384	0.2546	0.3475	0.022*
C10	0.69223 (10)	0.10059 (11)	0.29748 (8)	0.0194 (3)
C11	0.69933 (12)	−0.02888 (12)	0.28902 (9)	0.0277 (3)
H11A	0.7596	−0.0589	0.3336	0.042*
H11B	0.7148	−0.0489	0.2297	0.042*
H11C	0.6283	−0.0644	0.2982	0.042*
C12	0.93680 (11)	0.33780 (12)	0.44667 (9)	0.0237 (3)
H12A	0.9774	0.3814	0.4969	0.036*
H12B	0.8696	0.3815	0.4218	0.036*
H12C	0.9848	0.3277	0.4011	0.036*
N2	0.62225 (8)	0.15672 (10)	0.22387 (7)	0.0213 (3)
O1	0.56684 (8)	0.09273 (9)	0.16782 (6)	0.0277 (3)
O2	0.61918 (8)	0.26532 (9)	0.21672 (6)	0.0296 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0169 (5)	0.0221 (6)	0.0187 (5)	−0.0023 (4)	0.0000 (4)	−0.0023 (4)
C1	0.0178 (6)	0.0191 (6)	0.0180 (6)	0.0014 (5)	0.0028 (5)	−0.0030 (5)
C2	0.0163 (6)	0.0180 (6)	0.0192 (6)	0.0017 (5)	0.0023 (5)	−0.0026 (5)
C3	0.0174 (6)	0.0197 (6)	0.0170 (6)	0.0021 (5)	0.0039 (5)	−0.0023 (5)
C4	0.0204 (6)	0.0221 (7)	0.0214 (6)	−0.0018 (5)	0.0042 (5)	−0.0042 (5)
C5	0.0285 (7)	0.0211 (7)	0.0253 (7)	−0.0015 (5)	0.0099 (5)	−0.0016 (5)
C6	0.0318 (7)	0.0265 (7)	0.0192 (6)	0.0051 (6)	0.0088 (5)	0.0038 (5)
C7	0.0241 (7)	0.0305 (8)	0.0159 (6)	0.0027 (6)	0.0027 (5)	−0.0015 (5)
C8	0.0186 (6)	0.0215 (6)	0.0171 (6)	0.0007 (5)	0.0035 (5)	−0.0032 (5)
C9	0.0161 (6)	0.0190 (6)	0.0210 (6)	0.0015 (5)	0.0035 (5)	−0.0005 (5)
C10	0.0169 (6)	0.0233 (7)	0.0175 (6)	0.0021 (5)	0.0009 (5)	0.0012 (5)
C11	0.0353 (8)	0.0234 (7)	0.0222 (7)	0.0020 (6)	−0.0030 (6)	−0.0029 (5)
C12	0.0242 (7)	0.0205 (7)	0.0259 (7)	−0.0025 (5)	0.0023 (5)	−0.0014 (5)
N2	0.0168 (5)	0.0275 (6)	0.0191 (5)	0.0007 (4)	0.0011 (4)	0.0013 (4)
O1	0.0233 (5)	0.0375 (6)	0.0200 (5)	−0.0038 (4)	−0.0041 (4)	−0.0040 (4)
O2	0.0304 (6)	0.0251 (6)	0.0303 (5)	0.0025 (4)	−0.0049 (4)	0.0054 (4)

Geometric parameters (Å, º)

N1—C1	1.3534 (16)	C7—C8	1.3881 (18)
N1—C8	1.3803 (16)	C7—H7	0.9500
N1—H1	0.8800	C9—C10	1.3532 (17)
C1—C2	1.4015 (17)	C9—H9	0.9500
C1—C12	1.4833 (18)	C10—N2	1.4484 (15)
C2—C9	1.4335 (17)	C10—C11	1.4838 (18)
C2—C3	1.4517 (17)	C11—H11A	0.9800
C3—C4	1.4048 (17)	C11—H11B	0.9800
C3—C8	1.4102 (17)	C11—H11C	0.9800
C4—C5	1.3853 (18)	C12—H12A	0.9800
C4—H4	0.9500	C12—H12B	0.9800
C5—C6	1.3980 (19)	C12—H12C	0.9800
C5—H5	0.9500	N2—O1	1.2400 (14)
C6—C7	1.3824 (19)	N2—O2	1.2416 (14)
C6—H6	0.9500
C1—N1—C8	110.29 (10)	N1—C8—C7	128.55 (12)
C1—N1—H1	124.9	N1—C8—C3	107.83 (11)
C8—N1—H1	124.9	C7—C8—C3	123.61 (12)
N1—C1—C2	109.15 (11)	C10—C9—C2	129.02 (12)
N1—C1—C12	120.70 (11)	C10—C9—H9	115.5
C2—C1—C12	130.12 (12)	C2—C9—H9	115.5
C1—C2—C9	121.00 (11)	C9—C10—N2	116.25 (12)
C1—C2—C3	106.24 (11)	C9—C10—C11	129.54 (11)
C9—C2—C3	132.75 (11)	N2—C10—C11	113.95 (11)
C4—C3—C8	117.26 (11)	C10—C11—H11A	109.5
C4—C3—C2	136.07 (12)	C10—C11—H11B	109.5
C8—C3—C2	106.44 (11)	H11A—C11—H11B	109.5
C5—C4—C3	119.52 (12)	C10—C11—H11C	109.5
C5—C4—H4	120.2	H11A—C11—H11C	109.5
C3—C4—H4	120.2	H11B—C11—H11C	109.5
C4—C5—C6	121.44 (13)	C1—C12—H12A	109.5
C4—C5—H5	119.3	C1—C12—H12B	109.5
C6—C5—H5	119.3	H12A—C12—H12B	109.5
C7—C6—C5	120.61 (12)	C1—C12—H12C	109.5
C7—C6—H6	119.7	H12A—C12—H12C	109.5
C5—C6—H6	119.7	H12B—C12—H12C	109.5
C6—C7—C8	117.45 (12)	O1—N2—O2	121.27 (11)
C6—C7—H7	121.3	O1—N2—C10	117.80 (11)
C8—C7—H7	121.3	O2—N2—C10	120.92 (11)
C8—N1—C1—C2	−1.96 (13)	C1—N1—C8—C3	0.65 (13)
C8—N1—C1—C12	179.96 (11)	C6—C7—C8—N1	175.65 (12)
N1—C1—C2—C9	−178.22 (10)	C6—C7—C8—C3	−2.67 (18)
C12—C1—C2—C9	−0.4 (2)	C4—C3—C8—N1	−174.48 (10)
N1—C1—C2—C3	2.41 (13)	C2—C3—C8—N1	0.85 (13)
C12—C1—C2—C3	−179.74 (12)	C4—C3—C8—C7	4.14 (18)
C1—C2—C3—C4	172.03 (13)	C2—C3—C8—C7	179.47 (11)
C9—C2—C3—C4	−7.2 (2)	C1—C2—C9—C10	154.03 (13)
C1—C2—C3—C8	−1.97 (13)	C3—C2—C9—C10	−26.8 (2)
C9—C2—C3—C8	178.77 (12)	C2—C9—C10—N2	177.96 (11)
C8—C3—C4—C5	−2.84 (17)	C2—C9—C10—C11	−8.3 (2)
C2—C3—C4—C5	−176.37 (13)	C9—C10—N2—O1	−177.53 (10)
C3—C4—C5—C6	0.31 (19)	C11—C10—N2—O1	7.78 (16)
C4—C5—C6—C7	1.24 (19)	C9—C10—N2—O2	3.40 (16)
C5—C6—C7—C8	−0.10 (18)	C11—C10—N2—O2	−171.28 (11)
C1—N1—C8—C7	−177.88 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.88	2.22	3.0112 (14)	150

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

(II) (E)-3-(2-Methyl-2-nitrovinyl)-2-phenyl-1H-indole

Crystal data

C17H14N2O2	F(000) = 584
Mr = 278.30	Dx = 1.353 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1825 reflections
a = 7.7856 (2) Å	θ = 1.0–27.5°
b = 10.4801 (3) Å	µ = 0.09 mm^−1
c = 16.7489 (5) Å	T = 90 K
V = 1366.61 (7) Å^3	Block, orange-brown
Z = 4	0.25 × 0.22 × 0.22 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2257 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
Detector resolution: 18 pixels mm^-1	h = −10→10
ω scans at fixed χ = 55°	k = −13→13
3128 measured reflections	l = −21→21
3128 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0544P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.19 e Å^−3
3128 reflections	Δρmin = −0.21 e Å^−3
192 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.018 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with how many Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.4 (16)

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.

Achiral molecule in a crystal in space group P 2₁2₁2₁. This was refined as a 50:50 inversion twin because there was no reason to suggest that this would be conformationally 'pure', and of course, no way to tell either.

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

	x	y	z	Uiso*/Ueq
N1	0.2436 (2)	−0.06040 (15)	0.34376 (10)	0.0215 (4)
H1	0.3235	−0.0420	0.3791	0.026*
C1	0.2588 (2)	−0.04445 (19)	0.26283 (11)	0.0197 (4)
C2	0.1085 (2)	−0.08466 (19)	0.22624 (11)	0.0194 (5)
C3	−0.0055 (3)	−0.12754 (18)	0.28902 (12)	0.0192 (5)
C4	−0.1760 (3)	−0.1717 (2)	0.29239 (12)	0.0221 (5)
H4	−0.2414	−0.1815	0.2449	0.027*
C5	−0.2465 (3)	−0.20058 (19)	0.36571 (13)	0.0252 (5)
H5	−0.3607	−0.2321	0.3683	0.030*
C6	−0.1525 (3)	−0.1842 (2)	0.43660 (13)	0.0257 (5)
H6	−0.2041	−0.2060	0.4862	0.031*
C7	0.0125 (3)	−0.13738 (19)	0.43581 (12)	0.0243 (5)
H7	0.0750	−0.1244	0.4838	0.029*
C8	0.0842 (2)	−0.10966 (18)	0.36122 (12)	0.0189 (4)
C9	0.0838 (2)	−0.07431 (18)	0.14065 (12)	0.0200 (5)
H9	0.1330	−0.0012	0.1161	0.024*
C10	0.0006 (3)	−0.15452 (19)	0.09179 (11)	0.0199 (5)
C11	−0.0777 (3)	−0.28083 (19)	0.10955 (13)	0.0288 (5)
H11A	−0.0503	−0.3055	0.1645	0.043*
H11B	−0.0319	−0.3448	0.0726	0.043*
H11C	−0.2027	−0.2754	0.1032	0.043*
C12	0.4197 (2)	0.00079 (19)	0.22721 (12)	0.0194 (5)
C13	0.4729 (2)	−0.04379 (18)	0.15239 (12)	0.0216 (5)
H13	0.4064	−0.1062	0.1252	0.026*
C14	0.6219 (3)	0.00244 (19)	0.11773 (12)	0.0247 (5)
H14	0.6550	−0.0267	0.0663	0.030*
C15	0.7224 (3)	0.09026 (19)	0.15721 (13)	0.0278 (5)
H15	0.8240	0.1223	0.1330	0.033*
C16	0.6739 (3)	0.1317 (2)	0.23284 (14)	0.0270 (5)
H16	0.7442	0.1907	0.2609	0.032*
C17	0.5239 (3)	0.08757 (19)	0.26742 (12)	0.0232 (5)
H17	0.4917	0.1167	0.3190	0.028*
N2	−0.0056 (2)	−0.11723 (16)	0.00823 (10)	0.0251 (4)
O1	−0.0759 (2)	−0.19055 (15)	−0.03904 (9)	0.0428 (5)
O2	0.05761 (18)	−0.01413 (14)	−0.01355 (8)	0.0307 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0200 (9)	0.0222 (9)	0.0221 (9)	0.0001 (8)	−0.0029 (8)	−0.0041 (8)
C1	0.0233 (11)	0.0164 (9)	0.0192 (10)	0.0028 (9)	−0.0001 (9)	−0.0016 (9)
C2	0.0197 (10)	0.0167 (10)	0.0219 (10)	0.0006 (9)	−0.0006 (9)	0.0001 (9)
C3	0.0189 (10)	0.0144 (10)	0.0242 (11)	0.0022 (9)	0.0007 (9)	0.0005 (8)
C4	0.0219 (11)	0.0206 (11)	0.0239 (11)	0.0011 (9)	−0.0017 (9)	−0.0003 (9)
C5	0.0211 (11)	0.0221 (11)	0.0323 (12)	−0.0049 (9)	0.0036 (10)	0.0012 (10)
C6	0.0299 (12)	0.0224 (12)	0.0247 (11)	−0.0014 (10)	0.0078 (10)	0.0011 (10)
C7	0.0298 (13)	0.0216 (11)	0.0214 (11)	0.0022 (10)	−0.0005 (10)	−0.0008 (9)
C8	0.0206 (11)	0.0134 (9)	0.0229 (10)	0.0009 (8)	0.0024 (9)	0.0001 (8)
C9	0.0173 (10)	0.0182 (10)	0.0247 (11)	0.0032 (8)	0.0012 (10)	0.0016 (9)
C10	0.0211 (11)	0.0217 (11)	0.0168 (10)	0.0014 (10)	0.0001 (9)	0.0017 (9)
C11	0.0371 (13)	0.0228 (11)	0.0266 (11)	−0.0062 (10)	−0.0012 (10)	−0.0018 (9)
C12	0.0176 (10)	0.0160 (10)	0.0245 (10)	0.0016 (9)	−0.0015 (9)	0.0015 (9)
C13	0.0209 (10)	0.0177 (10)	0.0263 (11)	0.0007 (9)	0.0005 (10)	0.0006 (9)
C14	0.0216 (11)	0.0252 (12)	0.0273 (11)	0.0058 (10)	0.0003 (10)	0.0038 (10)
C15	0.0211 (11)	0.0220 (11)	0.0404 (13)	0.0016 (9)	0.0056 (11)	0.0071 (11)
C16	0.0208 (11)	0.0175 (11)	0.0428 (14)	−0.0021 (9)	−0.0063 (11)	0.0002 (10)
C17	0.0245 (11)	0.0183 (10)	0.0267 (11)	0.0024 (9)	−0.0035 (10)	−0.0011 (9)
N2	0.0275 (10)	0.0255 (10)	0.0224 (10)	−0.0012 (9)	−0.0003 (9)	−0.0010 (8)
O1	0.0662 (13)	0.0370 (10)	0.0251 (8)	−0.0175 (9)	−0.0085 (8)	−0.0055 (7)
O2	0.0383 (10)	0.0288 (9)	0.0251 (8)	−0.0071 (8)	0.0011 (7)	0.0050 (7)

Geometric parameters (Å, º)

N1—C1	1.371 (2)	C10—N2	1.454 (2)
N1—C8	1.376 (2)	C10—C11	1.488 (3)
N1—H1	0.8800	C11—H11A	0.9800
C1—C2	1.386 (3)	C11—H11B	0.9800
C1—C12	1.466 (3)	C11—H11C	0.9800
C2—C3	1.447 (3)	C12—C17	1.393 (3)
C2—C9	1.451 (3)	C12—C13	1.400 (3)
C3—C4	1.407 (3)	C13—C14	1.385 (3)
C3—C8	1.409 (3)	C13—H13	0.9500
C4—C5	1.379 (3)	C14—C15	1.377 (3)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.405 (3)	C15—C16	1.391 (3)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.376 (3)	C16—C17	1.383 (3)
C6—H6	0.9500	C16—H16	0.9500
C7—C8	1.399 (3)	C17—H17	0.9500
C7—H7	0.9500	N2—O1	1.232 (2)
C9—C10	1.340 (3)	N2—O2	1.242 (2)
C9—H9	0.9500
C1—N1—C8	109.50 (17)	C9—C10—N2	115.80 (18)
C1—N1—H1	125.2	C9—C10—C11	129.37 (18)
C8—N1—H1	125.2	N2—C10—C11	114.72 (17)
N1—C1—C2	109.09 (17)	C10—C11—H11A	109.5
N1—C1—C12	121.03 (17)	C10—C11—H11B	109.5
C2—C1—C12	129.75 (17)	H11A—C11—H11B	109.5
C1—C2—C3	106.89 (17)	C10—C11—H11C	109.5
C1—C2—C9	121.72 (18)	H11A—C11—H11C	109.5
C3—C2—C9	131.32 (18)	H11B—C11—H11C	109.5
C4—C3—C8	118.48 (18)	C17—C12—C13	118.57 (18)
C4—C3—C2	135.2 (2)	C17—C12—C1	120.81 (18)
C8—C3—C2	106.18 (17)	C13—C12—C1	120.62 (18)
C5—C4—C3	118.91 (19)	C14—C13—C12	120.44 (19)
C5—C4—H4	120.5	C14—C13—H13	119.8
C3—C4—H4	120.5	C12—C13—H13	119.8
C4—C5—C6	121.26 (19)	C15—C14—C13	120.6 (2)
C4—C5—H5	119.4	C15—C14—H14	119.7
C6—C5—H5	119.4	C13—C14—H14	119.7
C7—C6—C5	121.4 (2)	C14—C15—C16	119.45 (19)
C7—C6—H6	119.3	C14—C15—H15	120.3
C5—C6—H6	119.3	C16—C15—H15	120.3
C6—C7—C8	117.1 (2)	C17—C16—C15	120.4 (2)
C6—C7—H7	121.5	C17—C16—H16	119.8
C8—C7—H7	121.5	C15—C16—H16	119.8
N1—C8—C7	128.89 (19)	C16—C17—C12	120.5 (2)
N1—C8—C3	108.32 (17)	C16—C17—H17	119.7
C7—C8—C3	122.78 (18)	C12—C17—H17	119.7
C10—C9—C2	128.36 (19)	O1—N2—O2	122.01 (17)
C10—C9—H9	115.8	O1—N2—C10	117.76 (17)
C2—C9—H9	115.8	O2—N2—C10	120.23 (17)
C8—N1—C1—C2	−0.6 (2)	C2—C3—C8—C7	178.19 (18)
C8—N1—C1—C12	−176.88 (16)	C1—C2—C9—C10	144.4 (2)
N1—C1—C2—C3	0.1 (2)	C3—C2—C9—C10	−39.1 (3)
C12—C1—C2—C3	176.04 (19)	C2—C9—C10—N2	178.86 (18)
N1—C1—C2—C9	177.40 (17)	C2—C9—C10—C11	−5.3 (4)
C12—C1—C2—C9	−6.7 (3)	N1—C1—C12—C17	−33.7 (3)
C1—C2—C3—C4	175.8 (2)	C2—C1—C12—C17	150.8 (2)
C9—C2—C3—C4	−1.2 (4)	N1—C1—C12—C13	145.43 (19)
C1—C2—C3—C8	0.3 (2)	C2—C1—C12—C13	−30.1 (3)
C9—C2—C3—C8	−176.6 (2)	C17—C12—C13—C14	−3.1 (3)
C8—C3—C4—C5	−2.5 (3)	C1—C12—C13—C14	177.77 (17)
C2—C3—C4—C5	−177.5 (2)	C12—C13—C14—C15	1.8 (3)
C3—C4—C5—C6	1.3 (3)	C13—C14—C15—C16	0.5 (3)
C4—C5—C6—C7	0.8 (3)	C14—C15—C16—C17	−1.6 (3)
C5—C6—C7—C8	−1.5 (3)	C15—C16—C17—C12	0.2 (3)
C1—N1—C8—C7	−178.00 (19)	C13—C12—C17—C16	2.1 (3)
C1—N1—C8—C3	0.8 (2)	C1—C12—C17—C16	−178.78 (17)
C6—C7—C8—N1	178.77 (19)	C9—C10—N2—O1	177.62 (19)
C6—C7—C8—C3	0.2 (3)	C11—C10—N2—O1	1.2 (3)
C4—C3—C8—N1	−177.00 (17)	C9—C10—N2—O2	−2.9 (3)
C2—C3—C8—N1	−0.7 (2)	C11—C10—N2—O2	−179.29 (17)
C4—C3—C8—C7	1.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.88	2.11	2.953 (2)	161

Symmetry code: (i) −x+1/2, −y, z+1/2.