1,3-Bis(ethyl­amino)-2-nitro­benzene, 1,3-bis­(n-octylamino)-2-nitro­benzene and 4-ethylamino-2-methyl-1H-benz­imid­azole

1,3-Bis(ethyl­amino)-2-nitro­benzene, C₁₀H₁₅N₃O₂, (I), and 1,3-bis­(n-octylamino)-2-nitro­benzene, C₂₂H₃₉N₃O₂, (II), are the first structurally characterized 1,3-bis­(n-alkyl­amino)-2-nitro­benzenes. Both mol­ecules are bis­ected though the nitro N atom and the 2-C and 5-C atoms of the ring by twofold rotation axes. Both display intra­molecular N-H...O hydrogen bonds between the amine and nitro groups, but no inter­molecular hydrogen bonding. The nearly planar mol­ecules pack into flat layers ca 3.4 Å apart that inter­act by hydro­phobic inter­actions involving the n-alkyl groups rather than by [pi]-[pi] inter­actions between the rings. The intra- and inter­molecular inter­actions in these mol­ecules are of inter­est in understanding the physical properties of polymers made from them. Upon heating in the presence of anhydrous potassium carbonate in dimethyl­acetamide, (I) and (II) cyclize with formal loss of hydrogen peroxide to form substituted benzimidazoles. Thus, 4-ethylamino-2-methyl-1H-benzimidazole, C₁₀H₁₃N₃, (III), was obtained from (I) under these reaction conditions. Compound (III) contains two independent mol­ecules with no imposed inter­nal symmetry. The mol­ecules are linked into chains via N-H...N hydrogen bonds involving the imidazole rings, while the ethylamino groups do not participate in any hydrogen bonding. This is the first reported structure of a benzimidazole derivative with 4-amino and 2-alkyl substituents.

S1. Comment

This report is part of our continuing work on polyamines. In our earlier studies (Teng et al., 2006), polyamines were synthesized by the reactions of homologous aliphatic diamines with 1,5-difluoro-2,4-dinitrobenzene. These polymers are only soluble in concentrated mineral acids including sulfuric, nitric and perchloric acids at room temperature. This excellent solvent resistance is believed to be due to the existence of strong inter- and intra-chain hydrogen-bonding interactions, which arise from the presence of secondary amine moieties ortho to an aryl nitro group in the polymer repeat unit. As an extension of this study, we have prepared two more series of polyamines by the reactions of homologous aliphatic diamines with 2,6-difluoronitrobenzene and 2,4-difluoronitrobenzene, respectively, details of which will be published elsewhere. As a precursor to the polymer syntheses, model compounds were synthesized from aliphatic diamines and the isomeric difluorides mentioned above. We report herein the detailed structural characterization of the two title secondary diamines, (I) and (II), derived from 2,6-difluoronitrobenzene. These compounds could be synthesized successfully at a reaction temperature of 393 K in dimethylacetamide (DMAC), in the presence of excess anhydrous potassium carbonate and toluene. These reactions failed to yield the desired compounds when the reaction temperature exceeded 403 K. In order to understand this, the reaction mixture was analyzed periodically by gas chromatography and mass spectroscopy (GC/MS) with increasing reaction temperatures. These studies suggest that the desired diamines, which form quantitatively at or below 403 K, undergo further transformations as the temperature is gradually increased. Compound (III) is obtained from (I) during this process. The benzimidazole derivative (III) is the only product that could be unequivocally identified by GC/MS analyses. However, the presence of a number of other organic products, probably oligomeric in nature, was evident during the purification of (III) using column chromatography. Compound (II) underwent a similar reaction to yield 7-N-octyl-2-heptylbenzimidazole. However, in spite of our repeated attempts, we were unable to obtain crystals of appropriate quality.

Molecules of (I) are bisected by a twofold rotation axis that contains atoms N1, C1, C4 and H4 (Fig. 1). The H atoms on the N atoms of the N-ethylamino groups participate in strong intramolecular hydrogen bonds with the O atoms of the adjacent nitro group (Table 1). This pattern has been observed previously in molecules with primary amine groups on both sides of a nitro group (Ammon et al., 1982). A search of the Cambridge Structural Database (CSD, Version 5.29 plus update of January 2008; Allen, 2002) revealed no prior reports of 1,3-bis(N-alkylamino)-2-nitrobenzene structures, so this would appear to be the first example involving secondary amines. The ethyl groups adopt an anti conformation (C2—N2—C5—C6 torsion angle ca 180°), with the result that the molecules are essentially planar. The molecules pack into flat layers parallel to (103) (Fig. 2). Of note, there are no intermolecular hydrogen bonds involving the amine H atoms. The packing is thus dominated by hydrophobic interactions. Interestingly, although the interlayer spacing (ca 3.4 Å) is short enough for strong π–π interactions, the layers are actually shifted so that the rings are not over one another.

Molecules of (II) are very similar to those of (I), being also bisected through the nitro group and ring by a twofold axis (Fig. 3) and displaying the same intramolecular N—H···O hydrogen bonding (Table 2). The n-octyl groups are in the zigzag anti conformation and the essentially planar molecules pack in flat layers parallel to (301) with no intermolecular N—H···O hydrogen bonding (Fig. 4). Similar to (I), the layers are separated by about 3.4 Å, but the rings are not face-to-face. Rather, the dominant interaction is between the hydrophobic octyl chains. This preference for interactions between long alkyl chains over those between phenyl rings has also been noted in N-(n-decyl)-4-nitroaniline (Yonkey et al., 2008). The absence of intermolecular hydrogen bonding between the amine and nitro groups in the monomers, though understandable given the strong intramolecular interactions, does raise questions about what may be taking place in the polymers. We do note, however, that there are examples of aryl nitro compounds with ortho secondary amines in which the amine participates in simultaneous intra- and intermolecular N—H···O hydrogen bonds (Panunto et al., 1987).

Compound (III) is formed from (I) by an internal cyclization in which a new bond is formed between the α C atom of one of the ethyl groups and the nitro N atom. In the process, the two α H atoms and both nitro O atoms are lost. The presence of a peak of 34 amu in the mass spectrum suggests the possibility of hydrogen peroxide as the decomposition product. Structurally, (III) occurs as two independent molecules that occupy general positions and do not differ significantly in conformation (Fig. 5). The molecules are essentially planar, with a dihedral angle of 57.25 (1)° between them. In both, the amine N atom is most displaced from the least-squares plane of the non-H atoms, by 0.124 (1) Å for atom N12 and 0.057 (1) Å for atom N22. Similar to what is found in benzimidazole itself (Vijayan et al., 2006), the molecules in (III) are linked by N—H···N hydrogen bonds between the protonated and unprotonated N atoms of the imidazole rings of adjacent molecules into chains running parallel to the a axis. The amine groups do not participate in any N—H···N hydrogen bonds. Benzimidazole crystallizes in a non-centrosymmetric space group and is of interest as a potential nonlinear optical material (Vijayan et al., 2006). However, in spite of the similar hydrogen bonding, (III) crystallizes in a centrosymmetric space group. The presence of intermolecular hydrogen bonds in (III) is reflected in the significantly higher melting point compared with (I) and (II). A search of the CSD found no benzimidazole derivatives with N-alkyl groups in the 7-position and an R group in the 2-position, making this the first structurally characterized example.

S2. Experimental

Compounds (I) and (II) were prepared by similar routes. Anhydrous potassium carbonate (1.0943 g, 0.008 mol) and a solution of ethylamine (1.0805 g, 0.0240 mol; 70% in water) or octylamine (0.7284 g, 0.006 mol) in dimethylacetamide (DMAC) (8 ml) were combined in a three-necked 100 ml round-bottomed flask, fitted with a nitrogen inlet, a thermometer, a magnetic stirring bar and a Dean–Stark trap fitted with a condenser. To the stirred solution, 2,6-difluoronitrobenzene (0.4342 g, 0.0027 mol) in DMAC (5 ml) was added. Additional DMAC (8 ml) was used to wash the transfer container and this was added to the reaction mixture, followed by the addition of toluene (20 ml). The color of the reaction mixture turned bright red when the temperature reached 343 K. The temperature of the reaction mixture was raised to 393 K, and the reaction was allowed to continue at this temperature for 3 h. Water, the by-product of the reaction, was removed via azeotropic distillation with toluene. On completion of the reaction, the reaction mixture was allowed to cool to room temperature and diluted with dichloromethane (30 ml). The resulting heterogeneous mixture was then filtered through Celite at reduced pressure, and the solvents from the dark-red filtrate were removed under high vacuum to yield a bright-red solid residue. The crude product was dissolved in hexane (15 ml), transferred to a separating funnel and washed repeatedly with deionized water. The organic layer was collected, dried over anhydrous magnesium sulfate and filtered, and the filtrate was evaporated using a rotary evaporator to yield a bright-red solid. Crystals suitable for X-ray diffraction were obtained by recrystallization from hexane.

Analysis for compound (I): yield 65%; m.p. 336–338 K; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 8.6 (s, 2H), 7.1 (m, 1H), 5.9 (d, 2H), 3.2 (m, 3H), 1.3 (t, 6H); ¹³C NMR (CDCl₃, δ, p.p.m.): 148.51, 137.06, 121.01, 98.01, 38.34, 14.42; IR (KBr, ν > 1400 cm^-1): 3347, 2980, 2860, 1582, 1515, 1472; MS (m/z) (% base peak): 209 (85), 174 (100), 132 (72.5), 147 (55).

Analysis for compound (II): yield 70%; m.p. 343–345 K; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 8.7 (t, 2H), 7.1 (t, 1H), 5.8 (d, 2H), 3.2 (m, 4H), 1.7 (m, 4H), 1.3 (m, 20H), 0.9 (t, 6H); ¹³C NMR (CDCl₃, δ, p.p.m.): 148.69, 136.99, 97.88, 43.76, 32.02, 29.51, 29.42, 28.99, 27.40, 22.86, 14.31; IR (KBr, ν > 1400 cm^-1): 3343, 2957, 2926, 2850, 1583, 1515, 1471; MS (m/z) (% base peak): 377 (63.2), 342 (97.7), 244 (40.3), 232 (43.7), 134 (100).

Compound (III) was synthesized from (I) (prepared as described above) by taking the red solution obtained after azeoptropic removal of the water and heating it to 433 K for 24 h. During this time, the color gradually turned dark brown. The reaction solution was then diluted with dichloromethane (30 ml). The resulting heterogeneous mixture was filtered through Celite at reduced pressure. Solvents were then removed under high vacuum. The crude product was dissolved in dichloromethane (15 ml), transferred to a separating funnel and washed repeatedly with deionized water. The organic layer was collected, dried over anhydrous magnesium sulfate and filtered, and the filtrate was evaporated using a rotary evaporator to yield a dark-brown solid. The crude product was eluted on a neutral alumina column using dichloromethane–ethyl acetate (70:30 v/v) to obtain the desired compound, (III). The bluish–green solid was recrystallized from hexane.

Analysis for compound (III): yield: 15%; m.p. 432–434 K; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 7.1 (m, 1H), 6.7 (m, 1H), 6.3 (m, 1H), 3.3 (q, 2H), 2.6 (s, 3H), 1.3 (t, 3H); ¹³C NMR (CDCl₃, δ, p.p.m.): 148.24, 139.90, 134.53, 131.55, 124.02, 101.55, 99.67, 38.39, 30.00, 15.06; IR (KBr, ν > 1400 cm^-1): 3366, 2961, 1607, 1540, 1422; MS (m/z) (% base peak): 175 (38), 132 (38), 160 (100).

S3. Refinement

All H atoms were located in difference Fourier syntheses and were refined isotropically.

Computing details

For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Version 6.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Version 6.10; Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2006); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008) and local programs.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. The asymmetric unit consists of one-half of the molecule; unlabeled atoms are related to labeled atoms by the symmetry operator (?, ?, ?) [Please complete].
	Fig. 2. A single layer of molecules of (I), viewed along the c axis. Note the absence of intermolecular N—H···O hydrogen bonding.
	Fig. 3. The molecular structure of (II), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. The asymmetric unit consists of one-half of the molecule; unlabeled atoms are related to labeled atoms by the symmetry operator (?, ?, ?) [Please complete].
	Fig. 4. A single layer of molecules of (II), viewed along the a axis. Note the absence of intermolecular N—H···O hydrogen bonding.
	Fig. 5. A packing diagram for (III), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The asymmetric unit consists of two independent molecules. N—H···N hydrogen bonds (dashed lines) involving the imidazole rings link the molecules into chains running parallel to the a axis. There are no hydrogen bonds involving the amine N atoms.

(I) 1,3-bis(n-ethylamino)-2-nitrobenzene

Crystal data

C10H15N3O2	F(000) = 224
Mr = 209.25	Dx = 1.327 Mg m^−3
Monoclinic, P2/n	Melting point: 336 K
Hall symbol: -P 2yac	Mo Kα radiation, λ = 0.71073 Å
a = 5.0425 (6) Å	Cell parameters from 2623 reflections
b = 9.2564 (10) Å	θ = 2.8–33.0°
c = 11.4901 (13) Å	µ = 0.10 mm^−1
β = 102.492 (2)°	T = 140 K
V = 523.61 (10) Å^3	Needle, red
Z = 2	0.40 × 0.06 × 0.03 mm

Data collection

Bruker SMART 6000 CCD area-detector diffractometer	1017 independent reflections
Radiation source: fine-focus sealed tube	919 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→4
Tmin = 0.77, Tmax = 1.00	k = −11→10
3016 measured reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	All H-atom parameters refined
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.1845P] where P = (Fo^2 + 2Fc^2)/3
1017 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.16 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
O1	0.9243 (2)	0.50417 (12)	0.82181 (10)	0.0410 (4)
N1	0.7500	0.43516 (19)	0.7500	0.0281 (4)
N2	1.1793 (2)	0.27164 (15)	0.89937 (10)	0.0268 (4)
C1	0.7500	0.2823 (2)	0.7500	0.0248 (5)
C2	0.9703 (3)	0.20475 (16)	0.82619 (11)	0.0239 (4)
C3	0.9629 (3)	0.05350 (16)	0.82223 (12)	0.0257 (4)
C4	0.7500	−0.0188 (2)	0.7500	0.0271 (5)
C5	1.3992 (3)	0.19564 (16)	0.97807 (12)	0.0262 (4)
C6	1.5899 (3)	0.30237 (19)	1.05306 (15)	0.0340 (4)
H2	1.176 (3)	0.363 (2)	0.9019 (15)	0.034 (5)*
H3	1.106 (3)	0.0036 (17)	0.8670 (15)	0.028 (4)*
H4	0.7500	−0.120 (3)	0.7500	0.019 (5)*
H5A	1.322 (3)	0.1303 (19)	1.0311 (15)	0.033 (4)*
H5B	1.499 (3)	0.1344 (18)	0.9323 (14)	0.030 (4)*
H6C	1.737 (4)	0.254 (2)	1.1045 (17)	0.043 (5)*
H6A	1.665 (4)	0.368 (2)	1.0015 (17)	0.048 (5)*
H6B	1.497 (4)	0.357 (2)	1.1008 (17)	0.045 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0352 (7)	0.0268 (7)	0.0515 (7)	−0.0012 (5)	−0.0113 (5)	−0.0040 (5)
N1	0.0236 (8)	0.0272 (9)	0.0322 (9)	0.000	0.0030 (7)	0.000
N2	0.0258 (7)	0.0246 (7)	0.0296 (7)	0.0017 (5)	0.0053 (5)	0.0004 (5)
C1	0.0255 (10)	0.0252 (11)	0.0264 (10)	0.000	0.0113 (8)	0.000
C2	0.0229 (7)	0.0298 (8)	0.0218 (7)	0.0002 (6)	0.0108 (6)	0.0012 (5)
C3	0.0270 (8)	0.0278 (8)	0.0244 (7)	0.0041 (6)	0.0100 (6)	0.0028 (5)
C4	0.0367 (12)	0.0216 (11)	0.0272 (10)	0.000	0.0162 (9)	0.000
C5	0.0267 (8)	0.0286 (8)	0.0244 (7)	0.0035 (6)	0.0080 (6)	0.0023 (6)
C6	0.0322 (9)	0.0348 (9)	0.0317 (8)	0.0064 (7)	−0.0001 (7)	−0.0009 (7)

Geometric parameters (Å, º)

O1—N1	1.2441 (14)	C3—H3	0.915 (17)
N1—O1^i	1.2441 (14)	C4—C3^i	1.3795 (18)
N1—C1	1.415 (3)	C4—H4	0.93 (2)
N2—C2	1.3483 (18)	C5—C6	1.511 (2)
N2—C5	1.4520 (18)	C5—H5A	0.997 (18)
N2—H2	0.85 (2)	C5—H5B	0.982 (17)
C1—C2	1.4472 (17)	C6—H6C	0.95 (2)
C1—C2^i	1.4472 (18)	C6—H6A	0.98 (2)
C2—C3	1.401 (2)	C6—H6B	0.94 (2)
C3—C4	1.3795 (18)
O1—N1—O1^i	118.21 (17)	C3—C4—C3^i	122.0 (2)
O1—N1—C1	120.90 (9)	C3—C4—H4	119.00 (10)
O1^i—N1—C1	120.90 (9)	C3^i—C4—H4	119.00 (10)
C2—N2—C5	123.68 (14)	N2—C5—C6	110.14 (13)
C2—N2—H2	117.3 (11)	N2—C5—H5A	109.1 (9)
C5—N2—H2	118.9 (11)	C6—C5—H5A	109.5 (9)
N1—C1—C2	119.72 (10)	N2—C5—H5B	110.9 (9)
N1—C1—C2^i	119.72 (10)	C6—C5—H5B	110.3 (9)
C2—C1—C2^i	120.56 (19)	H5A—C5—H5B	106.9 (14)
N2—C2—C3	119.40 (13)	C5—C6—H6C	111.0 (11)
N2—C2—C1	122.95 (15)	C5—C6—H6A	110.1 (11)
C3—C2—C1	117.66 (14)	H6C—C6—H6A	108.4 (16)
C4—C3—C2	121.05 (14)	C5—C6—H6B	110.5 (11)
C4—C3—H3	120.6 (10)	H6C—C6—H6B	108.0 (16)
C2—C3—H3	118.3 (10)	H6A—C6—H6B	108.7 (17)

Symmetry code: (i) −x+3/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.85 (2)	1.91 (2)	2.566 (1)	133 (2)

(II) 1,3-bis(n-octylamino)-2-nitrobenzene

Crystal data

C22H39N3O2	F(000) = 832
Mr = 377.56	Dx = 1.182 Mg m^−3
Monoclinic, C2/c	Melting point: 343 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.5603 (16) Å	Cell parameters from 4172 reflections
b = 9.1066 (7) Å	θ = 2.2–32.5°
c = 12.6778 (10) Å	µ = 0.08 mm^−1
β = 121.560 (2)°	T = 140 K
V = 2121.0 (3) Å^3	Plate, red
Z = 4	0.38 × 0.19 × 0.03 mm

Data collection

Bruker SMART 6000 CCD area-detector diffractometer	2568 independent reflections
Radiation source: fine-focus sealed tube	2012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→28
Tmin = 0.841, Tmax = 1.000	k = −12→12
8645 measured reflections	l = −16→14

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)] = 0.054	Hydrogen site location: difference Fourier map
wR(F^2) = 0.149	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0768P)^2 + 0.9135P] where P = (Fo^2 + 2Fc^2)/3
2568 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.28 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
O1	0.03356 (5)	0.24375 (10)	0.34884 (7)	0.0309 (3)
N1	0.0000	0.31326 (15)	0.2500	0.0183 (3)
N2	0.07516 (5)	0.48067 (12)	0.47798 (8)	0.0192 (3)
H2	0.0744 (9)	0.388 (2)	0.4771 (15)	0.043 (5)*
C1	0.0000	0.46890 (17)	0.2500	0.0168 (4)
C2	0.03837 (6)	0.54746 (13)	0.36629 (10)	0.0162 (3)
C3	0.03701 (6)	0.70176 (13)	0.36179 (10)	0.0193 (3)
C4	0.0000	0.77460 (18)	0.2500	0.0204 (4)
C5	0.11256 (7)	0.56209 (13)	0.59375 (10)	0.0189 (3)
C6	0.15100 (7)	0.45987 (13)	0.70473 (10)	0.0192 (3)
C7	0.19201 (7)	0.54834 (13)	0.82471 (10)	0.0193 (3)
C8	0.23421 (7)	0.45336 (13)	0.94019 (10)	0.0206 (3)
C9	0.27633 (7)	0.54404 (13)	1.05862 (10)	0.0204 (3)
C10	0.31773 (7)	0.44949 (13)	1.17500 (10)	0.0200 (3)
C11	0.36251 (8)	0.53845 (14)	1.29341 (11)	0.0232 (3)
C12	0.39927 (8)	0.44240 (15)	1.40876 (11)	0.0252 (3)
H3	0.0606 (9)	0.7560 (17)	0.4368 (15)	0.038 (4)*
H4	0.0000	0.878 (2)	0.2500	0.022 (5)*
H5A	0.1500 (7)	0.6286 (15)	0.5940 (11)	0.020 (3)*
H5B	0.0762 (7)	0.6235 (15)	0.6010 (12)	0.019 (3)*
H6A	0.1867 (7)	0.3979 (15)	0.6959 (12)	0.021 (3)*
H6B	0.1143 (8)	0.3944 (16)	0.7064 (13)	0.028 (4)*
H7A	0.2281 (8)	0.6181 (16)	0.8201 (12)	0.025 (4)*
H7B	0.1563 (8)	0.6107 (15)	0.8325 (12)	0.023 (3)*
H8A	0.1997 (8)	0.3874 (17)	0.9455 (13)	0.029 (4)*
H8B	0.2701 (8)	0.3910 (16)	0.9317 (13)	0.027 (4)*
H9A	0.2414 (8)	0.6069 (16)	1.0651 (13)	0.027 (4)*
H9B	0.3133 (8)	0.6065 (16)	1.0526 (13)	0.028 (4)*
H10A	0.2827 (8)	0.3886 (17)	1.1826 (13)	0.030 (4)*
H10B	0.3510 (8)	0.3825 (16)	1.1654 (13)	0.028 (4)*
H11A	0.3313 (8)	0.6086 (19)	1.3004 (14)	0.036 (4)*
H11B	0.4004 (8)	0.5952 (17)	1.2868 (13)	0.034 (4)*
H12A	0.3631 (9)	0.3891 (19)	1.4164 (14)	0.043 (5)*
H12B	0.4281 (9)	0.4950 (18)	1.4860 (16)	0.039 (4)*
H12C	0.4332 (8)	0.3747 (18)	1.4050 (14)	0.036 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0443 (6)	0.0206 (5)	0.0118 (4)	0.0014 (4)	0.0036 (4)	0.0029 (3)
N1	0.0202 (7)	0.0196 (7)	0.0125 (6)	0.000	0.0068 (5)	0.000
N2	0.0219 (6)	0.0206 (5)	0.0088 (5)	−0.0012 (4)	0.0035 (4)	−0.0017 (4)
C1	0.0162 (8)	0.0195 (8)	0.0120 (7)	0.000	0.0055 (6)	0.000
C2	0.0136 (6)	0.0216 (6)	0.0122 (6)	−0.0007 (4)	0.0059 (5)	−0.0010 (4)
C3	0.0178 (6)	0.0215 (6)	0.0158 (6)	−0.0023 (4)	0.0068 (5)	−0.0034 (4)
C4	0.0201 (8)	0.0161 (7)	0.0234 (8)	0.000	0.0102 (7)	0.000
C5	0.0197 (6)	0.0223 (6)	0.0108 (5)	−0.0023 (5)	0.0053 (5)	−0.0023 (4)
C6	0.0198 (6)	0.0233 (6)	0.0111 (6)	−0.0006 (5)	0.0058 (5)	−0.0010 (4)
C7	0.0205 (6)	0.0235 (6)	0.0112 (6)	−0.0016 (5)	0.0063 (5)	−0.0014 (4)
C8	0.0222 (7)	0.0233 (6)	0.0121 (6)	−0.0009 (5)	0.0061 (5)	−0.0005 (4)
C9	0.0228 (7)	0.0237 (6)	0.0120 (6)	−0.0001 (5)	0.0073 (5)	−0.0003 (4)
C10	0.0205 (6)	0.0224 (6)	0.0129 (6)	−0.0007 (5)	0.0057 (5)	−0.0012 (4)
C11	0.0258 (7)	0.0235 (6)	0.0131 (6)	−0.0010 (5)	0.0053 (5)	−0.0016 (4)
C12	0.0249 (7)	0.0297 (7)	0.0136 (6)	0.0003 (5)	0.0050 (5)	−0.0014 (5)

Geometric parameters (Å, º)

O1—N1	1.2431 (10)	C7—C8	1.5247 (15)
N1—O1^i	1.2431 (10)	C7—H7A	1.030 (14)
N1—C1	1.417 (2)	C7—H7B	1.002 (14)
N2—C2	1.3522 (14)	C8—C9	1.5276 (16)
N2—C5	1.4544 (14)	C8—H8A	0.986 (15)
N2—H2	0.844 (18)	C8—H8B	1.009 (15)
C1—C2^i	1.4467 (13)	C9—C10	1.5285 (15)
C1—C2	1.4467 (13)	C9—H9A	0.983 (15)
C2—C3	1.4060 (16)	C9—H9B	1.014 (15)
C3—C4	1.3789 (14)	C10—C11	1.5247 (16)
C3—H3	0.949 (16)	C10—H10A	0.981 (15)
C4—C3^i	1.3790 (14)	C10—H10B	0.997 (15)
C4—H4	0.94 (2)	C11—C12	1.5227 (16)
C5—C6	1.5206 (15)	C11—H11A	0.966 (17)
C5—H5A	1.008 (14)	C11—H11B	1.006 (16)
C5—H5B	1.006 (14)	C12—H12A	0.966 (18)
C6—C7	1.5287 (15)	C12—H12B	0.968 (17)
C6—H6A	1.006 (14)	C12—H12C	0.976 (16)
C6—H6B	1.000 (15)
O1^i—N1—O1	118.77 (13)	C8—C7—H7B	109.3 (8)
O1^i—N1—C1	120.61 (7)	C6—C7—H7B	108.8 (8)
O1—N1—C1	120.61 (7)	H7A—C7—H7B	107.4 (12)
C2—N2—C5	122.61 (10)	C7—C8—C9	112.71 (10)
C2—N2—H2	116.1 (11)	C7—C8—H8A	108.6 (9)
C5—N2—H2	121.3 (11)	C9—C8—H8A	110.1 (8)
N1—C1—C2^i	119.64 (7)	C7—C8—H8B	108.8 (8)
N1—C1—C2	119.64 (7)	C9—C8—H8B	108.3 (8)
C2^i—C1—C2	120.73 (14)	H8A—C8—H8B	108.2 (13)
N2—C2—C3	118.71 (10)	C8—C9—C10	112.99 (10)
N2—C2—C1	123.63 (11)	C8—C9—H9A	108.1 (9)
C3—C2—C1	117.66 (11)	C10—C9—H9A	109.4 (8)
C4—C3—C2	120.73 (11)	C8—C9—H9B	108.4 (8)
C4—C3—H3	119.9 (9)	C10—C9—H9B	107.7 (8)
C2—C3—H3	119.4 (9)	H9A—C9—H9B	110.2 (12)
C3—C4—C3^i	122.50 (15)	C11—C10—C9	113.58 (10)
C3—C4—H4	118.75 (8)	C11—C10—H10A	109.1 (8)
C3^i—C4—H4	118.75 (8)	C9—C10—H10A	108.8 (9)
N2—C5—C6	111.56 (10)	C11—C10—H10B	108.7 (8)
N2—C5—H5A	109.3 (7)	C9—C10—H10B	108.7 (8)
C6—C5—H5A	108.5 (7)	H10A—C10—H10B	107.9 (12)
N2—C5—H5B	109.2 (7)	C12—C11—C10	112.55 (11)
C6—C5—H5B	109.2 (7)	C12—C11—H11A	109.2 (9)
H5A—C5—H5B	109.1 (11)	C10—C11—H11A	109.2 (9)
C5—C6—C7	110.45 (10)	C12—C11—H11B	109.8 (9)
C5—C6—H6A	108.6 (7)	C10—C11—H11B	108.3 (9)
C7—C6—H6A	109.2 (8)	H11A—C11—H11B	107.7 (13)
C5—C6—H6B	109.3 (8)	C11—C12—H12A	110.1 (10)
C7—C6—H6B	110.2 (8)	C11—C12—H12B	115.0 (9)
H6A—C6—H6B	109.1 (12)	H12A—C12—H12B	105.7 (13)
C8—C7—C6	113.59 (10)	C11—C12—H12C	110.1 (9)
C8—C7—H7A	108.4 (8)	H12A—C12—H12C	110.6 (14)
C6—C7—H7A	109.2 (8)	H12B—C12—H12C	105.2 (13)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.844 (18)	1.910 (18)	2.570 (1)	134 (2)

(III) 7-n-ethyl-2-methyl-1H-benzimidazole

Crystal data

C10H13N3	F(000) = 752
Mr = 175.23	Dx = 1.234 Mg m^−3
Monoclinic, P21/n	Melting point: 432 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.6166 (3) Å	Cell parameters from 8542 reflections
b = 16.2072 (5) Å	θ = 2.5–33.5°
c = 12.1236 (3) Å	µ = 0.08 mm^−1
β = 93.278 (1)°	T = 140 K
V = 1886.47 (10) Å^3	Pyramidal, blue
Z = 8	0.36 × 0.30 × 0.30 mm

Data collection

Bruker SMART 6000 CCD area-detector diffractometer	4120 independent reflections
Radiation source: fine-focus sealed tube	3759 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.893, Tmax = 1.000	k = −20→20
19605 measured reflections	l = −15→15

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F^2) = 0.118	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 0.7046P] where P = (Fo^2 + 2Fc^2)/3
4120 reflections	(Δ/σ)max < 0.001
339 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.24 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
N11	0.28781 (10)	0.15867 (6)	0.29060 (9)	0.0238 (2)
H11	0.3717 (18)	0.1303 (11)	0.2798 (13)	0.037 (4)*
N12	−0.06234 (11)	0.33365 (7)	0.38748 (10)	0.0281 (3)
H12	−0.1062 (19)	0.3112 (11)	0.3307 (15)	0.042 (5)*
N13	0.05966 (10)	0.18629 (6)	0.28385 (8)	0.0228 (2)
N21	0.78283 (11)	0.11946 (7)	0.28668 (9)	0.0242 (2)
H21	0.8672 (18)	0.1489 (10)	0.2790 (13)	0.036 (4)*
N22	0.43596 (12)	−0.06583 (7)	0.36301 (9)	0.0274 (2)
H22	0.381 (2)	−0.0246 (13)	0.3567 (16)	0.056 (6)*
N23	0.55596 (10)	0.08952 (6)	0.27404 (8)	0.0227 (2)
C10	0.13212 (15)	0.05655 (9)	0.19189 (12)	0.0301 (3)
H10C	0.120 (3)	0.0126 (16)	0.240 (2)	0.087 (8)*
H10B	0.209 (3)	0.0412 (17)	0.153 (2)	0.097 (8)*
H10A	0.051 (3)	0.0598 (17)	0.148 (2)	0.095 (8)*
C12	0.15746 (12)	0.13444 (7)	0.25537 (10)	0.0232 (3)
C14	0.08000 (13)	0.32040 (7)	0.39062 (10)	0.0236 (3)
C15	0.17802 (14)	0.37286 (8)	0.44329 (11)	0.0275 (3)
H15	0.1485 (16)	0.4238 (10)	0.4790 (12)	0.030 (4)*
C16	0.32104 (14)	0.35398 (8)	0.44841 (11)	0.0293 (3)
H16	0.3847 (18)	0.3916 (11)	0.4876 (13)	0.039 (4)*
C17	0.37337 (13)	0.28372 (8)	0.40120 (11)	0.0270 (3)
H17	0.4711 (17)	0.2693 (10)	0.4066 (13)	0.033 (4)*
C18	0.27474 (12)	0.23198 (7)	0.34712 (10)	0.0228 (3)
C19	0.13236 (12)	0.24868 (7)	0.34190 (9)	0.0217 (2)
C20	0.62661 (15)	0.22327 (8)	0.19147 (12)	0.0284 (3)
H20C	0.543 (2)	0.2216 (13)	0.1467 (17)	0.060 (6)*
H20B	0.702 (2)	0.2358 (13)	0.1444 (17)	0.063 (6)*
H20A	0.620 (2)	0.2670 (13)	0.2453 (17)	0.062 (6)*
C22	0.65275 (12)	0.14355 (7)	0.25029 (10)	0.0234 (3)
C24	0.57654 (12)	−0.04809 (7)	0.37341 (10)	0.0233 (3)
C25	0.67585 (14)	−0.10095 (8)	0.42394 (10)	0.0266 (3)
H25	0.6482 (16)	−0.1527 (10)	0.4554 (13)	0.029 (4)*
C26	0.81814 (14)	−0.08090 (8)	0.43200 (11)	0.0284 (3)
H26	0.8834 (17)	−0.1203 (10)	0.4683 (13)	0.035 (4)*
C27	0.86935 (13)	−0.00864 (8)	0.38980 (10)	0.0265 (3)
H27	0.9654 (17)	0.0059 (10)	0.3960 (12)	0.029 (4)*
C28	0.77014 (13)	0.04390 (7)	0.33833 (10)	0.0231 (3)
C29	0.62820 (12)	0.02590 (7)	0.32974 (9)	0.0219 (2)
C32	−0.11810 (14)	0.41224 (8)	0.42203 (11)	0.0278 (3)
H32B	−0.0730 (16)	0.4589 (10)	0.3851 (12)	0.030 (4)*
H32A	−0.0946 (15)	0.4178 (9)	0.5033 (13)	0.030 (4)*
C33	−0.27458 (15)	0.41379 (9)	0.39849 (13)	0.0333 (3)
H33C	−0.3133 (18)	0.4655 (12)	0.4224 (14)	0.045 (5)*
H33B	−0.3159 (18)	0.3691 (11)	0.4380 (14)	0.039 (4)*
H33A	−0.2990 (17)	0.4063 (10)	0.3209 (15)	0.039 (4)*
C42	0.37983 (14)	−0.13834 (8)	0.41501 (11)	0.0274 (3)
H42B	0.4236 (16)	−0.1875 (10)	0.3846 (12)	0.030 (4)*
H42A	0.4069 (16)	−0.1373 (10)	0.4959 (13)	0.031 (4)*
C43	0.22287 (15)	−0.14141 (10)	0.39529 (13)	0.0344 (3)
H43C	0.188 (2)	−0.1904 (13)	0.4301 (16)	0.057 (6)*
H43B	0.1813 (18)	−0.0918 (11)	0.4256 (14)	0.039 (4)*
H43A	0.1961 (17)	−0.1428 (10)	0.3164 (15)	0.040 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0196 (5)	0.0219 (5)	0.0299 (5)	0.0015 (4)	0.0021 (4)	0.0017 (4)
N12	0.0234 (5)	0.0227 (5)	0.0383 (6)	0.0013 (4)	0.0020 (4)	−0.0068 (5)
N13	0.0210 (5)	0.0203 (5)	0.0271 (5)	0.0006 (4)	0.0017 (4)	−0.0001 (4)
N21	0.0199 (5)	0.0221 (5)	0.0305 (5)	−0.0001 (4)	0.0009 (4)	−0.0009 (4)
N22	0.0246 (5)	0.0232 (5)	0.0343 (6)	−0.0010 (4)	0.0009 (4)	0.0032 (4)
N23	0.0209 (5)	0.0197 (5)	0.0275 (5)	0.0019 (4)	0.0011 (4)	0.0005 (4)
C10	0.0295 (7)	0.0257 (7)	0.0351 (7)	0.0021 (5)	0.0024 (6)	−0.0061 (6)
C12	0.0221 (6)	0.0218 (6)	0.0258 (6)	0.0008 (5)	0.0022 (4)	0.0018 (5)
C14	0.0251 (6)	0.0193 (6)	0.0264 (6)	−0.0003 (5)	0.0026 (5)	0.0030 (4)
C15	0.0299 (6)	0.0213 (6)	0.0312 (6)	−0.0021 (5)	0.0007 (5)	−0.0013 (5)
C16	0.0284 (6)	0.0256 (6)	0.0333 (7)	−0.0066 (5)	−0.0040 (5)	0.0007 (5)
C17	0.0211 (6)	0.0255 (6)	0.0339 (7)	−0.0018 (5)	−0.0023 (5)	0.0048 (5)
C18	0.0224 (6)	0.0208 (6)	0.0253 (6)	0.0009 (4)	0.0023 (4)	0.0048 (4)
C19	0.0219 (6)	0.0197 (6)	0.0234 (5)	−0.0016 (4)	0.0014 (4)	0.0031 (4)
C20	0.0284 (6)	0.0221 (6)	0.0347 (7)	0.0017 (5)	0.0039 (5)	0.0030 (5)
C22	0.0220 (6)	0.0212 (6)	0.0272 (6)	0.0018 (5)	0.0024 (4)	−0.0018 (5)
C24	0.0257 (6)	0.0211 (6)	0.0229 (6)	−0.0001 (5)	0.0007 (4)	−0.0025 (4)
C25	0.0311 (7)	0.0212 (6)	0.0272 (6)	0.0018 (5)	−0.0001 (5)	0.0008 (5)
C26	0.0300 (7)	0.0267 (6)	0.0276 (6)	0.0071 (5)	−0.0049 (5)	−0.0012 (5)
C27	0.0217 (6)	0.0278 (6)	0.0294 (6)	0.0035 (5)	−0.0039 (5)	−0.0034 (5)
C28	0.0244 (6)	0.0208 (6)	0.0239 (6)	0.0002 (5)	−0.0001 (4)	−0.0029 (4)
C29	0.0219 (6)	0.0208 (6)	0.0229 (5)	0.0022 (4)	−0.0002 (4)	−0.0022 (4)
C32	0.0300 (7)	0.0222 (6)	0.0312 (7)	0.0035 (5)	0.0022 (5)	−0.0035 (5)
C33	0.0300 (7)	0.0304 (7)	0.0393 (8)	0.0076 (6)	0.0012 (6)	−0.0066 (6)
C42	0.0314 (7)	0.0225 (6)	0.0288 (6)	−0.0026 (5)	0.0052 (5)	−0.0018 (5)
C43	0.0324 (7)	0.0333 (7)	0.0379 (8)	−0.0073 (6)	0.0069 (6)	−0.0045 (6)

Geometric parameters (Å, º)

N11—C12	1.3589 (16)	C17—H17	0.967 (16)
N11—C18	1.3810 (16)	C18—C19	1.3936 (16)
N11—H11	0.945 (17)	C20—C22	1.4902 (17)
N12—C14	1.3839 (16)	C20—H20C	0.94 (2)
N12—C32	1.4529 (16)	C20—H20B	0.97 (2)
N12—H12	0.867 (19)	C20—H20A	0.97 (2)
N13—C12	1.3218 (16)	C24—C25	1.3980 (17)
N13—C19	1.3964 (15)	C24—C29	1.4126 (17)
N21—C22	1.3597 (15)	C25—C26	1.4044 (19)
N21—C28	1.3840 (16)	C25—H25	0.965 (16)
N21—H21	0.950 (17)	C26—C27	1.3801 (19)
N22—C24	1.3807 (16)	C26—H26	0.982 (17)
N22—C42	1.4522 (17)	C27—C28	1.3988 (17)
N22—H22	0.85 (2)	C27—H27	0.952 (16)
N23—C22	1.3216 (16)	C28—C29	1.3938 (17)
N23—C29	1.3957 (15)	C32—C33	1.5158 (19)
C10—C12	1.4912 (18)	C32—H32B	0.992 (16)
C10—H10C	0.94 (3)	C32—H32A	1.003 (15)
C10—H10B	0.94 (3)	C33—H33C	0.968 (19)
C10—H10A	0.92 (3)	C33—H33B	0.966 (18)
C14—C15	1.3965 (18)	C33—H33A	0.964 (17)
C14—C19	1.4099 (17)	C42—C43	1.5155 (19)
C15—C16	1.4069 (19)	C42—H42B	0.982 (16)
C15—H15	0.981 (16)	C42—H42A	1.000 (16)
C16—C17	1.3823 (19)	C43—H43C	0.97 (2)
C16—H16	0.969 (17)	C43—H43B	0.979 (18)
C17—C18	1.4005 (17)	C43—H43A	0.976 (18)
C12—N11—C18	107.22 (10)	H20B—C20—H20A	108.8 (17)
C12—N11—H11	126.5 (10)	N23—C22—N21	112.67 (11)
C18—N11—H11	126.2 (10)	N23—C22—C20	125.25 (11)
C14—N12—C32	120.59 (11)	N21—C22—C20	122.08 (11)
C14—N12—H12	113.1 (12)	N22—C24—C25	123.58 (11)
C32—N12—H12	115.2 (12)	N22—C24—C29	120.40 (11)
C12—N13—C19	104.41 (10)	C25—C24—C29	116.00 (11)
C22—N21—C28	107.31 (10)	C24—C25—C26	121.82 (12)
C22—N21—H21	126.8 (10)	C24—C25—H25	120.6 (9)
C28—N21—H21	125.9 (10)	C26—C25—H25	117.6 (9)
C24—N22—C42	121.01 (11)	C27—C26—C25	122.51 (12)
C24—N22—H22	116.5 (14)	C27—C26—H26	119.1 (10)
C42—N22—H22	115.3 (13)	C25—C26—H26	118.4 (10)
C22—N23—C29	104.93 (10)	C26—C27—C28	115.67 (12)
C12—C10—H10C	110.0 (15)	C26—C27—H27	123.1 (9)
C12—C10—H10B	112.0 (16)	C28—C27—H27	121.2 (9)
H10C—C10—H10B	105 (2)	N21—C28—C29	105.23 (10)
C12—C10—H10A	111.0 (17)	N21—C28—C27	131.68 (12)
H10C—C10—H10A	106 (2)	C29—C28—C27	123.09 (12)
H10B—C10—H10A	113 (2)	C28—C29—N23	109.86 (11)
N13—C12—N11	113.05 (11)	C28—C29—C24	120.90 (11)
N13—C12—C10	125.12 (11)	N23—C29—C24	129.23 (11)
N11—C12—C10	121.83 (11)	N12—C32—C33	109.82 (11)
N12—C14—C15	123.97 (12)	N12—C32—H32B	111.1 (9)
N12—C14—C19	119.52 (11)	C33—C32—H32B	111.0 (9)
C15—C14—C19	116.47 (11)	N12—C32—H32A	107.2 (9)
C14—C15—C16	121.36 (12)	C33—C32—H32A	110.4 (9)
C14—C15—H15	120.6 (9)	H32B—C32—H32A	107.2 (12)
C16—C15—H15	118.0 (9)	C32—C33—H33C	110.6 (11)
C17—C16—C15	122.61 (12)	C32—C33—H33B	109.0 (10)
C17—C16—H16	119.1 (10)	H33C—C33—H33B	109.0 (14)
C15—C16—H16	118.3 (10)	C32—C33—H33A	111.4 (10)
C16—C17—C18	115.74 (11)	H33C—C33—H33A	108.9 (14)
C16—C17—H17	123.1 (10)	H33B—C33—H33A	107.8 (14)
C18—C17—H17	121.1 (10)	N22—C42—C43	110.46 (11)
N11—C18—C19	105.16 (10)	N22—C42—H42B	108.3 (9)
N11—C18—C17	131.99 (11)	C43—C42—H42B	111.0 (9)
C19—C18—C17	122.85 (11)	N22—C42—H42A	109.2 (9)
C18—C19—N13	110.16 (10)	C43—C42—H42A	110.9 (9)
C18—C19—C14	120.96 (11)	H42B—C42—H42A	106.8 (12)
N13—C19—C14	128.88 (11)	C42—C43—H43C	109.2 (12)
C22—C20—H20C	111.4 (13)	C42—C43—H43B	109.7 (10)
C22—C20—H20B	110.6 (12)	H43C—C43—H43B	110.4 (15)
H20C—C20—H20B	107.9 (17)	C42—C43—H43A	111.1 (10)
C22—C20—H20A	109.1 (12)	H43C—C43—H43A	109.1 (15)
H20C—C20—H20A	108.9 (17)	H43B—C43—H43A	107.3 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N23	0.945 (17)	1.896 (18)	2.8293 (14)	169.2 (15)
N21—H21···N13^i	0.950 (17)	1.946 (17)	2.8761 (15)	165.9 (15)

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