Imino­pyrrole derivatives containing electron-withdrawing substituents: the formation of dimers and supra­molecular arrangements

The crystal structures of two p-substituted phenyl­formimino­pyrrole derivatives, namely 2-[(4-fluoro­phenyl)­imino­meth­yl]­pyrrole, C₁₁H₉FN₂, (1), and 2-[(1H-pyrrol-2-yl­methylidene)­amino]benzonitrile, C₁₂H₉N₃, (2), bear F and C[triple bond]N electron-withdrawing groups, respectively. Both structures feature two independent mol­ecules in the asymmetric unit forming dimers via N—H...N hydrogen bonds. In the case of (1), each dimer inter­acts with two other dimers via C—H...F contacts, thus forming one-dimensional chains in the b direction, whereas in the case of (2), a weak C—H...N inter­action connects the dimers in one-dimensional chains in the (110) direction.

S1. Comment

Pyrrole and its substituted derivatives are well known five-membered heterocyclic compounds, which are involved in a wide range of applications, in areas such as natural products, bioactive molecules, pharmaceuticals, anion-binding systems etc. (Rao & Jothilingam, 2001; Braun et al., 2001; Hewton et al., 2002; Sessler et al., 2005). Moreover, 2-(N-aryl or N-alkyl)iminopyrroles, (I) (Fig. 1), are usually employed as ligand precursors in the preparation of coordination compounds, generally after deprotonation of the pyrrole NH (Mashima & Tsurugi, 2005). The synthethic strategy for the preparation of these iminopyrrole derivatives is very straightforward, consisting of a Vilsmeier–Haack acylation (Garrido et al., 1984), followed by a condensation reaction with a suitable aliphatic or aromatic amine. The resulting complexes are mostly used as precatalysts in polymerization reactions (Mashima & Tsurugi, 2005; Matsugi & Fujita, 2008), but they can also have applications, for example, in luminescence (Wu et al., 2003, 2004).

Recently, we reported the synthesis of new Ni (Bellabarba et al., 2003), Co (Carabineiro et al., 2007, 2008), Na (Gomes et al., 2010) and Zn (Gomes et al., 2009) complexes containing 2-(N-aryl)iminopyrrolyl ligands, where the Ni derivatives were active in the oligomerization of ethylene and the Zn ones showed luminescent properties. In these publications, we also reported the molecular structure of some ligand precursors, namely 2-[N-(mesitylimino)ethyl]pyrrole, 2-[N-(2,6-diisopropylphenylimino)ethyl]pyrrole, two polymorphs of 2-[N-(phenylimino)methyl]pyrrole and 2-[N-(2,6-diisopropylphenylimino)methyl]pyrrole, which can be found in the Cambridge Structural Database (CSD, Version 5.32; Allen, 2002) with refcodes UMUKUI (Bellabarba et al., 2003), LILYUB (Carabineiro et al., 2007), CUKHUM (Gomes et al., 2010), CUKHUM01 (Gomes et al., 2010) and CUKJEY (Gomes et al., 2010), respectively (Fig. 1).

In the present work, we report the crystal structures of 2-[N-(4-fluorophenylimino)methyl]pyrrole, (1), and 2-[N-(4-cyanophenylimino)methyl]pyrrole, (2), in which the para positions of the phenyl rings are substituted by the electron-withdrawing groups F and C≡N (nitrile). The corresponding molecular structures are depicted in Figs. 2 and 3, respectively. In both compounds the asymmetric unit contains two independent molecules, where the pyrrole moieties show planar backbones with similar features. A brief analysis of the bond distances and angles in these derivatives (Table 1) reveals that the longest bond length in the pyrrole ring is C3—C4, with values ranging from 1.390 (3) to 1.397 (2) Å, and that the shortest one is N1—C5. The imine distance varies between 1.2809 (19) and 1.290 (2) Å (Table 1). The torsion angles N2—C6—C2—N1 of -2.6 (3) and -2.4 (3)° [molecules A and B of (1)] and -4.1 (2) and -0.3 (3)° [molecules A and B of (2)] show that the pyrrole ring and the formimino group are nearly coplanar. The C2—C6 distances in the range 1.416 (2)–1.426 (2) Å are slightly shorter than the normal values for typical C—C single bonds, indicating an extension of the pyrrole ring π-electron delocalization towards the formimino substituent. For both compounds (1) and (2), the phenyl substituent of the iminic fragment lies around 45° relative to the pyrrole ring [dihedral angles of 49.08 (9), 45.33 (10), 52.05 (9) and 39.10 (10)° for molecules A and B of (1) and (2), respectively]. In fact, this is also verified [true?] for CUKHUM [46.97 (7) and 45.31 (8)°] and CUKHUM01 [41.96 (12), 8.93 (12), 47.96 (13) and 41.28 (12)°] that do not present any substituents in the phenyl ring, but it differs [is not the case for] from UMUKUI [85.66 (8)°], LILYUB [86.54 (9) and 83.48 (9)°] and CUKJEY [83.84 (10) and 86.17 (9)°], in which the phenyl rings are rotated about the N_imine—C_ipso-phenyl bond, being nearly perpendicular to the formiminopyrrole plane defined by atoms N2—C6—C2—N1, due to the high steric hindrance exerted by the alkyl 2,6-substituting groups (Bellabarba et al., 2003; Carabineiro et al., 2007; Gomes et al., 2010). The value of 8.93 (12)° found in one of the four molecules of polymorph CUKHUM01, which is substantially different from all the others, making the phenyl ring almost coplanar with the iminopyrrole fragment, is due to the supramolecular arrangement.

It is known from the literature (Bellabarba et al., 2003; Munro et al., 2006; Carabineiro et al., 2007; Gomes et al., 2010) that these types of organic derivatives assemble as formiminopyrrole dimers through the formation of two complementary hydrogen bonds between a pyrrole NH and the imine nitrogen belonging to the other molecule of the pair. In agreement with this, both compounds (1) and (2) show dimerization of the iminopyrrole molecules through an R²₂(10) motif as can be seen in Figs. 4 and 5. However, in contrast to what is observed in the more hindered derivatives UMUKUI, LILYUB or CUKJEY, in which the iminopyrrole molecules of the dimer are coplanar, in (1) and (2), and also in CUKHUM, both molecules composing each dimer are not coplanar, the wings of the pyrrole moieties making an angle of 150.55 (10), 138.77 (10) and 151.94 (8)°, in the cases of (1), (2) and CUKHUM, respectively.

In compound (1), the most important observed intermolecular interactions are the two complementary hydrogen bonds N1A—H1A···N2B and N1B—H1B···N2A (Table 2). However, a C—H···F short contact is found with H···F distances and C—H···F angles within the limits reported in the literature for this type of contact (Shimoni & Glusker, 1994; Howard et al., 1996; Dunitz & Taylor, 1997). In fact, these interactions, always involving molecule B, occur between the fluorine atom and the pyrrole NH at position 3 of the neighbouring dimer, forming one-dimensional chains in the b direction (Fig. 4). Conversely, in derivative (2), in addition to the two hydrogen bonds N1A—H1A···N2B and N1B—H1B···N2A, one can also notice the existence of a weak intermolecular hydrogen bond of the type C—H···N, forming chains in the (110) direction, in which a nitrile group interacts weakly with an aromatic meta-hydrogen atom of the neighbouring dimer (Fig. 5), the latter having a more electropositive character than the corresponding hydrogen of derivative (1), due to the proximity of the more powerful electron-withdrawing nitrile group. This is in agreement with the ¹H and ¹³C NMR data for the corresponding meta-proton and meta-carbon nuclei that are clearly more deshielded in compound (2) than in (1) [δ ¹H 7.67–7.63 versus 7.19–7.13 and δ ¹³C 133.4 versus 116.8 p.p.m. for (2) and (1), respectively] (Figs. 4 and 5).

Moreover, comparing these two crystal structures with VIYWUW (Heinze et al., 2008), an iminopyrrole derivative containing a hydroxy substituent in the para position of the phenyl ring (see Fig. 1), it is possible to notice that the phenyl substituent of the iminic fragment also lies around 45° relative to the pyrrole ring [dihedral angle of 49.59 (5)°], and that all the distances within the molecule are in agreement with the ones observed for the derivatives discussed above. On the other hand, the formation of dimers through the establishment of complementary N—H···N hydrogen bonds is disabled in this compound, due to the presence of the para-hydroxy substituent, which is involved in three different interactions: O—H···N, N—H···O and C—H···O. Additionally, similarly to derivative (2), this compound also forms an infinite one-dimensional chain.

Related literature

For related literature, see: Allen (2002); Bellabarba et al. (2003); Braun et al. (2001); Carabineiro et al. (2007, 2008); Dunitz & Taylor (1997); Garrido et al. (1984); Gomes et al. (2009, 2010); Heinze et al. (2008); Hewton et al. (2002); Howard et al. (1996); Mashima & Tsurugi (2005); Matsugi & Fujita (2008); Munro et al. (2006); Rao & Jothilingam (2001); Sessler et al. (2005); Shimoni & Glusker (1994); Wu et al. (2003, 2004).

S2. Experimental

n-Hexane, diethyl ether and absolute ethanol were predried over activated 4 Å molecular sieves and then distilled from sodium and kept under a nitrogen atmosphere. The synthetic procedure followed for the synthesis of 2-(N-aryl)iminopyrroles (1) and (2) was that used previously by our group (Bellabarba et al., 2003; Carabineiro et al., 2007, 2008; Gomes et al., 2010). 2-Formylpyrrole [10.5 mmol in the case of (1) and 14.4 mmol in the case of (2)], aniline (1 equivalent), a catalytic amount of p-toluenesulfonic acid and MgSO₄ (to remove the water formed during the reaction mixture) were suspended in absolute ethanol in a round-bottom flask fitted with a condenser and a CaCl₂ guard tube. The mixture was heated to reflux overnight. After cooling to room temperature, CH₂Cl₂ was added and the suspension filtered through Celite and washed through with more CH₂Cl₂. After removal of all volatiles, the product was dissolved in refluxing n-hexane. In the case of (1), the resulting solution was stored at 253 K, yielding yellow prismatic crystals (yield 54%). However, in the case of (2), the product, which was an oil, was insoluble in n-hexane and partially soluble in diethyl ether. After evaporation of these solvents, the initial oil was transformed into a brown solid, which was purified by sublimation at a temperature of 353 K and a pressure of 10 Pa (yield 49%). Yellow crystals of (2) suitable for X-ray diffraction were obtained by recrystallization in diethyl ether at 253 K.

NMR data for (1): ¹H (300 MHz, CDCl₃): δ_H 9.98 (br s, 1H, NH), 8.25 (s, 1H, CH = N), 7.19–7.13 (m, 2H, m-phenyl), 7.10–7.02 (m, 2H, o-phenyl), 6.86 (br s, 1H, H5), 6.69 (dd, J_HH = 1.38 Hz, 1H, H3), 6.29 (dd, J_HH = 2.49 Hz, 1H, H4). ¹³C{¹H} (75 MHz, CDCl₃): δ_C 160.9 (d, ¹J_CF = 242 Hz, p-phenyl), 149.8 (CH = N), 147.8 (ipso-phenyl), 130.7 (C2), 123.3 (C3), 122.2 (d, ³J_CF = 8 Hz, o-phenyl), 116.8 (C4), 115.9 (d, ²J_CF = 22 Hz, m-phenyl), 110.5 (C5).

NMR data for (2): ¹H (300 MHz, CDCl₃)]: δ_H 9.53 (br s, 1H, NH), 8.21 (s, 1H, CH = N), 7.67–7.63 (m, 2H, m-phenyl), 7.22–7.18 (m, 2H, o-phenyl), 7.03 (d, J_HH = 10.8 Hz, 1H, H5), 6.76 (dd, J_HH = 1.2 Hz, 1H, H3), 6.34 (m, 1H, H4). ¹³C{¹H} (75 MHz, CDCl₃): δ_C 155.7 (ipso-phenyl), 151.1 (CH = N), 133.4 (m-phenyl), 130.4 (C2), 124.2 (C3), 121.7 (o-phenyl), 119.2 (C4), 118.2 (C≡N), 111.1 (p-phenyl), 108.4 (C5).

S3. Refinement

All H atoms, except the pyrrole NH atoms, were inserted in idealized positions and allowed to refine as riding on their parent C atoms, with C—H distances of 0.95 Å for aromatic H atoms, and with U_iso(H) = 1.2U_eq(C). The H atoms of the N_pyrrole were located in the difference Fourier map and allowed to refine freely.

Computing details

For both compounds, data collection: APEX2 (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), Mercury (Macrae et al., 2006); software used to prepare material for publication: enCIFer (Allen et al., 2004), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Figures

Fig. 1. Schematic representation of a general 2-formiminopyrrole, (I), and of some corresponding selected cases reported in the CSD: UMUKUI, LILYUB, CUKHUM, CUKHUM01, CUKJEY and VIYWUW. Fig. 2. ORTEP drawing of 2-(N-(4-fluoro)phenyl)imino-1H-pyrrole, (1). Displacement ellipsoids are drawn at the 50% probability level. Fig. 3. ORTEP drawing of 2-(N-(4-ciano)phenyl)imino-1H-pyrrole, (2). Displacement ellipsoids are drawn at the 50% probability level. Fig. 4. Packing of (1) showing the one-dimensional-chains in the b direction, and the R^22(10) motifs forming the dimers. Donor and acceptor atoms are identified, symmetry code (i) 1 - x, -1/2 + y, 3/2 - z . Dashed lines represent N— H···N and C— H···F interactions (blue and red, respectively, in the electronic version of the paper). Fig. 5. Packing of (2) showing a chain of dimers along the (110) direction, and the R^22(10) motifs forming the dimers. Donor and acceptor atoms are identified, symmetry code (ii) x + 1, y - 1, z . Dashed lines represent N— H···N and C— H···N interactions (blue and red, respectively, in the electronic version of the paper).

(1) 4-fluoro-N-(1H-pyrrol-2-ylmethylidene)aniline

Crystal data

C11H9FN2	F(000) = 1568
Mr = 188.20	Dx = 1.322 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5510 reflections
a = 9.5542 (5) Å	θ = 2.6–24.5°
b = 18.7198 (9) Å	µ = 0.09 mm^−1
c = 21.1509 (12) Å	T = 150 K
V = 3782.9 (3) Å^3	Prism, yellow
Z = 16	0.60 × 0.60 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer	3605 independent reflections
Radiation source: fine-focus sealed tube	2479 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 25.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→8
Tmin = 0.946, Tmax = 0.972	k = −22→22
21637 measured reflections	l = −25→18

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 1.0348P] where P = (Fo^2 + 2Fc^2)/3
3605 reflections	(Δ/σ)max < 0.001
261 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
F1A	1.03248 (12)	0.42197 (6)	0.28313 (6)	0.0557 (3)
N1A	0.56108 (15)	0.72610 (7)	0.48332 (7)	0.0287 (3)
H1A	0.586 (2)	0.6908 (10)	0.5105 (9)	0.049 (6)*
N2A	0.73050 (14)	0.62264 (7)	0.41712 (6)	0.0270 (3)
C2A	0.58678 (17)	0.72689 (8)	0.41955 (8)	0.0272 (4)
C3A	0.51704 (19)	0.78509 (9)	0.39466 (9)	0.0371 (4)
H3A	0.5165	0.7994	0.3516	0.045*
C4A	0.44754 (19)	0.81906 (9)	0.44424 (9)	0.0386 (5)
H4A	0.3912	0.8607	0.4411	0.046*
C5A	0.47535 (18)	0.78145 (8)	0.49797 (9)	0.0337 (4)
H5A	0.4404	0.7922	0.5389	0.040*
C6A	0.66890 (17)	0.67416 (8)	0.38832 (8)	0.0275 (4)
H6A	0.6787	0.6773	0.3437	0.033*
C7A	0.80580 (17)	0.57235 (8)	0.38029 (8)	0.0254 (4)
C8A	0.75076 (19)	0.54081 (9)	0.32625 (8)	0.0313 (4)
H8A	0.6606	0.5544	0.3117	0.038*
C9A	0.8268 (2)	0.48964 (9)	0.29347 (9)	0.0373 (5)
H9A	0.7895	0.4675	0.2567	0.045*
C10A	0.95652 (19)	0.47202 (9)	0.31549 (9)	0.0361 (5)
C11A	1.01431 (19)	0.50139 (9)	0.36859 (9)	0.0367 (5)
H11A	1.1050	0.4877	0.3825	0.044*
C12A	0.93700 (18)	0.55151 (8)	0.40154 (9)	0.0320 (4)
H12A	0.9741	0.5719	0.4391	0.038*
F1B	0.43545 (13)	0.84707 (6)	0.76254 (5)	0.0622 (4)
N1B	0.67720 (15)	0.51369 (7)	0.51762 (7)	0.0300 (4)
H1B	0.688 (2)	0.5555 (10)	0.4948 (9)	0.049 (6)*
N2B	0.59266 (14)	0.63280 (7)	0.59716 (7)	0.0306 (3)
C2B	0.62340 (17)	0.50791 (9)	0.57743 (8)	0.0285 (4)
C3B	0.62831 (18)	0.43651 (9)	0.59385 (9)	0.0361 (5)
H3B	0.5981	0.4165	0.6328	0.043*
C4B	0.68550 (18)	0.39911 (9)	0.54310 (9)	0.0375 (5)
H4B	0.7016	0.3491	0.5411	0.045*
C5B	0.71399 (19)	0.44778 (9)	0.49680 (9)	0.0354 (4)
H5B	0.7532	0.4372	0.4566	0.042*
C6B	0.58091 (17)	0.56759 (9)	0.61470 (8)	0.0306 (4)
H6B	0.5414	0.5584	0.6551	0.037*
C7B	0.54764 (18)	0.68666 (9)	0.64002 (8)	0.0304 (4)
C8B	0.42534 (19)	0.68138 (10)	0.67512 (8)	0.0365 (5)
H8B	0.3669	0.6407	0.6706	0.044*
C9B	0.3882 (2)	0.73533 (11)	0.71683 (9)	0.0447 (5)
H9B	0.3060	0.7314	0.7419	0.054*
C10B	0.4720 (2)	0.79401 (10)	0.72115 (9)	0.0428 (5)
C11B	0.5908 (2)	0.80278 (10)	0.68589 (9)	0.0406 (5)
H11B	0.6458	0.8448	0.6894	0.049*
C12B	0.62817 (19)	0.74816 (10)	0.64481 (9)	0.0364 (4)
H12B	0.7100	0.7529	0.6196	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1A	0.0593 (8)	0.0483 (7)	0.0595 (8)	0.0122 (6)	0.0211 (6)	−0.0166 (6)
N1A	0.0323 (8)	0.0250 (7)	0.0287 (9)	0.0036 (6)	−0.0006 (7)	−0.0012 (7)
N2A	0.0264 (8)	0.0272 (7)	0.0274 (8)	0.0002 (6)	0.0015 (6)	−0.0026 (6)
C2A	0.0277 (9)	0.0265 (8)	0.0273 (10)	−0.0011 (7)	−0.0008 (8)	−0.0009 (7)
C3A	0.0427 (11)	0.0347 (9)	0.0341 (11)	0.0059 (8)	−0.0049 (9)	0.0043 (8)
C4A	0.0387 (11)	0.0318 (9)	0.0454 (12)	0.0104 (8)	−0.0065 (9)	−0.0036 (9)
C5A	0.0342 (10)	0.0292 (9)	0.0378 (11)	0.0061 (8)	0.0009 (8)	−0.0074 (8)
C6A	0.0280 (9)	0.0286 (8)	0.0260 (10)	−0.0031 (7)	0.0025 (8)	0.0000 (8)
C7A	0.0253 (9)	0.0247 (8)	0.0262 (10)	−0.0017 (7)	0.0040 (7)	0.0006 (7)
C8A	0.0283 (10)	0.0374 (9)	0.0281 (10)	−0.0019 (8)	0.0025 (8)	−0.0023 (8)
C9A	0.0410 (11)	0.0390 (10)	0.0318 (11)	−0.0054 (9)	0.0073 (9)	−0.0104 (8)
C10A	0.0380 (11)	0.0293 (9)	0.0411 (12)	0.0020 (8)	0.0163 (9)	−0.0086 (8)
C11A	0.0264 (10)	0.0341 (9)	0.0497 (13)	0.0021 (8)	0.0037 (9)	−0.0010 (9)
C12A	0.0306 (10)	0.0294 (9)	0.0360 (11)	−0.0013 (8)	−0.0012 (8)	−0.0043 (8)
F1B	0.0832 (9)	0.0621 (7)	0.0412 (7)	0.0328 (7)	−0.0037 (6)	−0.0151 (6)
N1B	0.0336 (8)	0.0260 (7)	0.0303 (9)	−0.0022 (6)	−0.0009 (7)	0.0018 (7)
N2B	0.0305 (8)	0.0340 (8)	0.0274 (8)	−0.0013 (6)	0.0010 (6)	0.0003 (7)
C2B	0.0226 (9)	0.0339 (9)	0.0289 (10)	−0.0021 (7)	−0.0026 (8)	0.0056 (8)
C3B	0.0279 (10)	0.0378 (10)	0.0427 (12)	−0.0037 (8)	−0.0032 (8)	0.0130 (9)
C4B	0.0343 (11)	0.0264 (9)	0.0518 (13)	−0.0023 (8)	−0.0061 (9)	0.0040 (9)
C5B	0.0374 (11)	0.0302 (9)	0.0385 (11)	0.0000 (8)	−0.0036 (8)	−0.0045 (8)
C6B	0.0225 (9)	0.0408 (10)	0.0285 (10)	−0.0014 (8)	0.0000 (8)	0.0060 (8)
C7B	0.0336 (10)	0.0359 (9)	0.0216 (9)	0.0052 (8)	−0.0020 (8)	0.0043 (8)
C8B	0.0357 (11)	0.0415 (10)	0.0322 (11)	0.0067 (8)	0.0028 (9)	0.0088 (9)
C9B	0.0479 (12)	0.0541 (12)	0.0322 (12)	0.0197 (10)	0.0085 (9)	0.0093 (10)
C10B	0.0579 (14)	0.0436 (11)	0.0268 (11)	0.0236 (10)	−0.0058 (10)	−0.0025 (9)
C11B	0.0467 (12)	0.0386 (10)	0.0364 (11)	0.0070 (9)	−0.0106 (10)	−0.0026 (9)
C12B	0.0365 (11)	0.0401 (10)	0.0326 (11)	0.0027 (9)	−0.0010 (9)	0.0005 (9)

Geometric parameters (Å, º)

F1A—C10A	1.3685 (19)	F1B—C10B	1.369 (2)
N1A—C5A	1.357 (2)	N1B—C5B	1.356 (2)
N1A—C2A	1.371 (2)	N1B—C2B	1.370 (2)
N1A—H1A	0.91 (2)	N1B—H1B	0.92 (2)
N2A—C6A	1.284 (2)	N2B—C6B	1.281 (2)
N2A—C7A	1.418 (2)	N2B—C7B	1.422 (2)
C2A—C3A	1.381 (2)	C2B—C3B	1.382 (2)
C2A—C6A	1.423 (2)	C2B—C6B	1.426 (2)
C3A—C4A	1.395 (3)	C3B—C4B	1.393 (3)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.363 (3)	C4B—C5B	1.365 (2)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C12A	1.388 (2)	C7B—C8B	1.388 (2)
C7A—C8A	1.390 (2)	C7B—C12B	1.388 (2)
C8A—C9A	1.388 (2)	C8B—C9B	1.387 (3)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.365 (3)	C9B—C10B	1.362 (3)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.367 (3)	C10B—C11B	1.367 (3)
C11A—C12A	1.383 (2)	C11B—C12B	1.389 (3)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—H12A	0.9500	C12B—H12B	0.9500
C5A—N1A—C2A	108.94 (15)	C5B—N1B—C2B	108.98 (15)
C5A—N1A—H1A	124.8 (12)	C5B—N1B—H1B	124.9 (12)
C2A—N1A—H1A	125.7 (12)	C2B—N1B—H1B	126.1 (12)
C6A—N2A—C7A	118.09 (14)	C6B—N2B—C7B	117.68 (15)
N1A—C2A—C3A	107.28 (15)	N1B—C2B—C3B	107.20 (16)
N1A—C2A—C6A	123.21 (15)	N1B—C2B—C6B	123.74 (15)
C3A—C2A—C6A	129.50 (16)	C3B—C2B—C6B	128.93 (17)
C2A—C3A—C4A	107.63 (16)	C2B—C3B—C4B	107.80 (16)
C2A—C3A—H3A	126.2	C2B—C3B—H3B	126.1
C4A—C3A—H3A	126.2	C4B—C3B—H3B	126.1
C5A—C4A—C3A	107.37 (15)	C5B—C4B—C3B	107.19 (16)
C5A—C4A—H4A	126.3	C5B—C4B—H4B	126.4
C3A—C4A—H4A	126.3	C3B—C4B—H4B	126.4
N1A—C5A—C4A	108.77 (16)	N1B—C5B—C4B	108.82 (17)
N1A—C5A—H5A	125.6	N1B—C5B—H5B	125.6
C4A—C5A—H5A	125.6	C4B—C5B—H5B	125.6
N2A—C6A—C2A	123.62 (16)	N2B—C6B—C2B	124.17 (16)
N2A—C6A—H6A	118.2	N2B—C6B—H6B	117.9
C2A—C6A—H6A	118.2	C2B—C6B—H6B	117.9
C12A—C7A—C8A	119.26 (15)	C8B—C7B—C12B	119.12 (16)
C12A—C7A—N2A	117.83 (15)	C8B—C7B—N2B	123.02 (16)
C8A—C7A—N2A	122.81 (15)	C12B—C7B—N2B	117.82 (15)
C9A—C8A—C7A	120.40 (17)	C9B—C8B—C7B	120.24 (18)
C9A—C8A—H8A	119.8	C9B—C8B—H8B	119.9
C7A—C8A—H8A	119.8	C7B—C8B—H8B	119.9
C10A—C9A—C8A	118.16 (17)	C10B—C9B—C8B	118.64 (19)
C10A—C9A—H9A	120.9	C10B—C9B—H9B	120.7
C8A—C9A—H9A	120.9	C8B—C9B—H9B	120.7
C9A—C10A—C11A	123.36 (16)	C9B—C10B—C11B	123.21 (18)
C9A—C10A—F1A	118.46 (17)	C9B—C10B—F1B	118.54 (19)
C11A—C10A—F1A	118.17 (17)	C11B—C10B—F1B	118.25 (19)
C10A—C11A—C12A	118.12 (17)	C10B—C11B—C12B	117.81 (18)
C10A—C11A—H11A	120.9	C10B—C11B—H11B	121.1
C12A—C11A—H11A	120.9	C12B—C11B—H11B	121.1
C11A—C12A—C7A	120.67 (17)	C7B—C12B—C11B	120.90 (18)
C11A—C12A—H12A	119.7	C7B—C12B—H12B	119.5
C7A—C12A—H12A	119.7	C11B—C12B—H12B	119.5
C5A—N1A—C2A—C3A	1.14 (19)	C5B—N1B—C2B—C3B	0.42 (19)
C5A—N1A—C2A—C6A	−177.51 (15)	C5B—N1B—C2B—C6B	176.67 (15)
N1A—C2A—C3A—C4A	−0.6 (2)	N1B—C2B—C3B—C4B	−0.15 (19)
C6A—C2A—C3A—C4A	177.92 (17)	C6B—C2B—C3B—C4B	−176.14 (17)
C2A—C3A—C4A—C5A	−0.1 (2)	C2B—C3B—C4B—C5B	−0.2 (2)
C2A—N1A—C5A—C4A	−1.24 (19)	C2B—N1B—C5B—C4B	−0.5 (2)
C3A—C4A—C5A—N1A	0.8 (2)	C3B—C4B—C5B—N1B	0.4 (2)
C7A—N2A—C6A—C2A	178.13 (14)	C7B—N2B—C6B—C2B	−178.99 (15)
N1A—C2A—C6A—N2A	−2.6 (3)	N1B—C2B—C6B—N2B	−2.4 (3)
C3A—C2A—C6A—N2A	179.06 (17)	C3B—C2B—C6B—N2B	173.03 (17)
C6A—N2A—C7A—C12A	135.80 (16)	C6B—N2B—C7B—C8B	−42.2 (2)
C6A—N2A—C7A—C8A	−47.6 (2)	C6B—N2B—C7B—C12B	140.11 (17)
C12A—C7A—C8A—C9A	−0.7 (2)	C12B—C7B—C8B—C9B	−3.3 (3)
N2A—C7A—C8A—C9A	−177.25 (15)	N2B—C7B—C8B—C9B	179.08 (16)
C7A—C8A—C9A—C10A	−0.6 (3)	C7B—C8B—C9B—C10B	1.8 (3)
C8A—C9A—C10A—C11A	1.0 (3)	C8B—C9B—C10B—C11B	0.6 (3)
C8A—C9A—C10A—F1A	−179.54 (15)	C8B—C9B—C10B—F1B	−179.74 (16)
C9A—C10A—C11A—C12A	0.0 (3)	C9B—C10B—C11B—C12B	−1.4 (3)
F1A—C10A—C11A—C12A	−179.47 (15)	F1B—C10B—C11B—C12B	178.98 (15)
C10A—C11A—C12A—C7A	−1.4 (3)	C8B—C7B—C12B—C11B	2.5 (3)
C8A—C7A—C12A—C11A	1.8 (2)	N2B—C7B—C12B—C11B	−179.73 (16)
N2A—C7A—C12A—C11A	178.46 (15)	C10B—C11B—C12B—C7B	−0.2 (3)

(2) 2-[(1H-pyrrol-2-ylmethylidene)amino]benzonitrile

Crystal data

C12H9N3	F(000) = 816
Mr = 195.22	Dx = 1.251 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2895 reflections
a = 12.5935 (13) Å	θ = 2.4–21.5°
b = 10.1843 (11) Å	µ = 0.08 mm^−1
c = 16.901 (2) Å	T = 150 K
β = 107.035 (5)°	Block, yellow
V = 2072.6 (4) Å^3	0.30 × 0.22 × 0.20 mm
Z = 8

Data collection

Bruker APEXII CCD diffractometer	3944 independent reflections
Radiation source: fine-focus sealed tube	2443 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 25.8°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→15
Tmin = 0.977, Tmax = 0.985	k = −12→12
18378 measured reflections	l = −20→20

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) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0377P)^2 + 0.1668P] where P = (Fo^2 + 2Fc^2)/3
3944 reflections	(Δ/σ)max < 0.001
279 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1A	0.69392 (11)	0.09386 (14)	0.23656 (9)	0.0327 (4)
H1A	0.6968 (14)	0.1219 (17)	0.1884 (11)	0.048 (6)*
N2A	0.51151 (10)	0.27292 (13)	0.17568 (8)	0.0326 (3)
N3A	0.05696 (14)	0.65427 (16)	0.02187 (11)	0.0597 (5)
C2A	0.61564 (13)	0.12078 (15)	0.27548 (10)	0.0320 (4)
C3A	0.64183 (14)	0.04829 (17)	0.34774 (10)	0.0421 (5)
H3A	0.6021	0.0478	0.3876	0.051*
C4A	0.73739 (14)	−0.02412 (17)	0.35139 (11)	0.0418 (5)
H4A	0.7747	−0.0828	0.3942	0.050*
C5A	0.76720 (13)	0.00524 (16)	0.28188 (10)	0.0363 (4)
H5A	0.8289	−0.0305	0.2677	0.044*
C6A	0.52466 (13)	0.20710 (15)	0.24244 (10)	0.0333 (4)
H6A	0.4708	0.2164	0.2714	0.040*
C7A	0.41444 (13)	0.34996 (16)	0.14529 (9)	0.0323 (4)
C8A	0.42516 (14)	0.47557 (17)	0.11705 (10)	0.0410 (5)
H8A	0.4966	0.5081	0.1191	0.049*
C9A	0.33319 (14)	0.55353 (17)	0.08605 (10)	0.0425 (5)
H9A	0.3416	0.6409	0.0690	0.051*
C10A	0.22810 (13)	0.50460 (16)	0.07963 (10)	0.0354 (4)
C11A	0.21600 (14)	0.37768 (17)	0.10469 (10)	0.0407 (4)
H11A	0.1440	0.3434	0.0992	0.049*
C12A	0.30861 (13)	0.30094 (16)	0.13761 (11)	0.0397 (4)
H12A	0.3002	0.2140	0.1552	0.048*
C13A	0.13273 (16)	0.58670 (17)	0.04734 (11)	0.0437 (5)
N1B	0.50641 (12)	0.20324 (14)	0.00486 (10)	0.0375 (4)
H1B	0.5280 (15)	0.2223 (19)	0.0577 (12)	0.060 (6)*
N2B	0.73573 (11)	0.12417 (13)	0.07296 (8)	0.0362 (4)
N3B	1.28103 (15)	−0.03953 (19)	0.20428 (11)	0.0708 (6)
C2B	0.56654 (14)	0.13695 (16)	−0.03764 (10)	0.0358 (4)
C3B	0.50074 (16)	0.12842 (17)	−0.11927 (11)	0.0460 (5)
H3B	0.5208	0.0876	−0.1634	0.055*
C4B	0.40028 (16)	0.19010 (17)	−0.12506 (11)	0.0476 (5)
H4B	0.3393	0.1992	−0.1736	0.057*
C5B	0.40546 (14)	0.23520 (17)	−0.04792 (11)	0.0432 (5)
H5B	0.3482	0.2812	−0.0335	0.052*
C6B	0.67873 (14)	0.09939 (15)	−0.00235 (10)	0.0377 (4)
H6B	0.7143	0.0530	−0.0363	0.045*
C7B	0.84833 (14)	0.08481 (16)	0.09966 (10)	0.0360 (4)
C8B	0.92296 (14)	0.16471 (17)	0.15650 (10)	0.0404 (4)
H8B	0.8968	0.2419	0.1763	0.048*
C9B	1.03396 (14)	0.13356 (18)	0.18437 (11)	0.0434 (5)
H9B	1.0843	0.1894	0.2225	0.052*
C10B	1.07190 (14)	0.01960 (18)	0.15624 (11)	0.0433 (5)
C11B	0.99796 (17)	−0.06265 (18)	0.10161 (12)	0.0502 (5)
H11B	1.0240	−0.1411	0.0832	0.060*
C12B	0.88651 (15)	−0.03099 (17)	0.07388 (11)	0.0436 (5)
H12B	0.8358	−0.0884	0.0371	0.052*
C13B	1.18810 (18)	−0.0132 (2)	0.18392 (12)	0.0541 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0314 (8)	0.0369 (9)	0.0268 (8)	−0.0011 (7)	0.0038 (7)	0.0003 (7)
N2A	0.0301 (8)	0.0340 (8)	0.0316 (8)	−0.0010 (6)	0.0058 (6)	0.0017 (7)
N3A	0.0586 (11)	0.0425 (9)	0.0713 (12)	0.0141 (9)	0.0085 (9)	−0.0037 (9)
C2A	0.0321 (9)	0.0330 (10)	0.0290 (9)	−0.0011 (8)	0.0060 (8)	0.0002 (8)
C3A	0.0449 (11)	0.0473 (11)	0.0335 (10)	−0.0007 (9)	0.0103 (8)	0.0060 (9)
C4A	0.0433 (11)	0.0390 (11)	0.0362 (11)	0.0007 (9)	0.0008 (8)	0.0097 (9)
C5A	0.0295 (9)	0.0359 (10)	0.0363 (10)	0.0017 (8)	−0.0015 (8)	−0.0004 (8)
C6A	0.0351 (10)	0.0328 (10)	0.0317 (10)	−0.0032 (8)	0.0094 (8)	−0.0031 (8)
C7A	0.0351 (10)	0.0336 (10)	0.0269 (9)	0.0001 (8)	0.0071 (7)	−0.0016 (8)
C8A	0.0382 (10)	0.0384 (11)	0.0416 (11)	−0.0078 (9)	0.0039 (8)	0.0047 (9)
C9A	0.0479 (11)	0.0304 (10)	0.0421 (11)	−0.0047 (9)	0.0021 (9)	0.0041 (9)
C10A	0.0410 (10)	0.0333 (10)	0.0298 (9)	0.0038 (8)	0.0072 (8)	−0.0029 (8)
C11A	0.0345 (10)	0.0432 (11)	0.0451 (11)	0.0032 (8)	0.0126 (8)	0.0044 (9)
C12A	0.0389 (10)	0.0329 (10)	0.0490 (11)	−0.0001 (8)	0.0154 (8)	0.0075 (9)
C13A	0.0507 (12)	0.0347 (10)	0.0434 (11)	0.0046 (10)	0.0102 (9)	−0.0051 (9)
N1B	0.0424 (9)	0.0372 (9)	0.0299 (9)	−0.0034 (7)	0.0059 (7)	0.0005 (7)
N2B	0.0424 (9)	0.0335 (8)	0.0336 (9)	−0.0004 (7)	0.0125 (7)	0.0005 (7)
N3B	0.0601 (12)	0.0899 (14)	0.0715 (13)	0.0225 (11)	0.0335 (10)	0.0246 (11)
C2B	0.0487 (11)	0.0262 (9)	0.0313 (10)	−0.0051 (8)	0.0098 (9)	0.0008 (8)
C3B	0.0678 (13)	0.0345 (10)	0.0324 (11)	−0.0089 (10)	0.0097 (9)	−0.0042 (8)
C4B	0.0566 (13)	0.0394 (11)	0.0354 (11)	−0.0083 (9)	−0.0042 (9)	0.0013 (9)
C5B	0.0423 (11)	0.0411 (11)	0.0390 (11)	−0.0036 (9)	0.0005 (9)	0.0040 (9)
C6B	0.0546 (12)	0.0257 (9)	0.0371 (11)	−0.0017 (8)	0.0199 (9)	0.0001 (8)
C7B	0.0471 (11)	0.0331 (10)	0.0333 (10)	0.0031 (8)	0.0202 (8)	0.0054 (8)
C8B	0.0479 (11)	0.0391 (10)	0.0358 (10)	0.0047 (9)	0.0146 (9)	−0.0013 (9)
C9B	0.0468 (11)	0.0468 (11)	0.0387 (11)	0.0022 (9)	0.0159 (9)	0.0047 (9)
C10B	0.0475 (11)	0.0481 (12)	0.0416 (11)	0.0123 (10)	0.0247 (9)	0.0159 (10)
C11B	0.0701 (14)	0.0365 (11)	0.0528 (12)	0.0133 (10)	0.0319 (11)	0.0063 (10)
C12B	0.0557 (12)	0.0352 (11)	0.0431 (11)	0.0040 (9)	0.0194 (9)	0.0017 (9)
C13B	0.0612 (14)	0.0596 (13)	0.0510 (13)	0.0129 (11)	0.0312 (11)	0.0175 (10)

Geometric parameters (Å, º)

N1A—C5A	1.356 (2)	N1B—C5B	1.362 (2)
N1A—C2A	1.364 (2)	N1B—C2B	1.365 (2)
N1A—H1A	0.874 (18)	N1B—H1B	0.875 (18)
N2A—C6A	1.2809 (19)	N2B—C6B	1.290 (2)
N2A—C7A	1.416 (2)	N2B—C7B	1.414 (2)
N3A—C13A	1.153 (2)	N3B—C13B	1.151 (2)
C2A—C3A	1.382 (2)	C2B—C3B	1.388 (2)
C2A—C6A	1.422 (2)	C2B—C6B	1.416 (2)
C3A—C4A	1.397 (2)	C3B—C4B	1.390 (3)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.367 (2)	C4B—C5B	1.366 (2)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.386 (2)	C7B—C12B	1.391 (2)
C7A—C12A	1.393 (2)	C7B—C8B	1.393 (2)
C8A—C9A	1.375 (2)	C8B—C9B	1.375 (2)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.388 (2)	C9B—C10B	1.391 (2)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.383 (2)	C10B—C11B	1.385 (3)
C10A—C13A	1.434 (2)	C10B—C13B	1.439 (3)
C11A—C12A	1.379 (2)	C11B—C12B	1.381 (2)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—H12A	0.9500	C12B—H12B	0.9500
C5A—N1A—C2A	109.27 (15)	C5B—N1B—C2B	109.20 (15)
C5A—N1A—H1A	122.4 (12)	C5B—N1B—H1B	124.5 (12)
C2A—N1A—H1A	128.2 (12)	C2B—N1B—H1B	126.3 (12)
C6A—N2A—C7A	118.97 (14)	C6B—N2B—C7B	118.39 (15)
N1A—C2A—C3A	107.45 (14)	N1B—C2B—C3B	106.99 (16)
N1A—C2A—C6A	123.23 (15)	N1B—C2B—C6B	123.42 (15)
C3A—C2A—C6A	129.31 (16)	C3B—C2B—C6B	129.28 (17)
C2A—C3A—C4A	107.48 (15)	C2B—C3B—C4B	107.91 (17)
C2A—C3A—H3A	126.3	C2B—C3B—H3B	126.0
C4A—C3A—H3A	126.3	C4B—C3B—H3B	126.0
C5A—C4A—C3A	107.24 (15)	C5B—C4B—C3B	107.27 (16)
C5A—C4A—H4A	126.4	C5B—C4B—H4B	126.4
C3A—C4A—H4A	126.4	C3B—C4B—H4B	126.4
N1A—C5A—C4A	108.55 (16)	N1B—C5B—C4B	108.63 (17)
N1A—C5A—H5A	125.7	N1B—C5B—H5B	125.7
C4A—C5A—H5A	125.7	C4B—C5B—H5B	125.7
N2A—C6A—C2A	123.42 (16)	N2B—C6B—C2B	124.13 (16)
N2A—C6A—H6A	118.3	N2B—C6B—H6B	117.9
C2A—C6A—H6A	118.3	C2B—C6B—H6B	117.9
C8A—C7A—C12A	119.06 (15)	C12B—C7B—C8B	119.09 (16)
C8A—C7A—N2A	118.39 (14)	C12B—C7B—N2B	123.13 (16)
C12A—C7A—N2A	122.40 (15)	C8B—C7B—N2B	117.74 (15)
C9A—C8A—C7A	120.54 (16)	C9B—C8B—C7B	120.96 (16)
C9A—C8A—H8A	119.7	C9B—C8B—H8B	119.5
C7A—C8A—H8A	119.7	C7B—C8B—H8B	119.5
C8A—C9A—C10A	119.99 (16)	C8B—C9B—C10B	119.47 (17)
C8A—C9A—H9A	120.0	C8B—C9B—H9B	120.3
C10A—C9A—H9A	120.0	C10B—C9B—H9B	120.3
C11A—C10A—C9A	119.99 (15)	C11B—C10B—C9B	120.10 (17)
C11A—C10A—C13A	120.44 (16)	C11B—C10B—C13B	119.83 (18)
C9A—C10A—C13A	119.57 (16)	C9B—C10B—C13B	120.07 (18)
C12A—C11A—C10A	119.84 (16)	C12B—C11B—C10B	120.20 (17)
C12A—C11A—H11A	120.1	C12B—C11B—H11B	119.9
C10A—C11A—H11A	120.1	C10B—C11B—H11B	119.9
C11A—C12A—C7A	120.51 (16)	C11B—C12B—C7B	120.11 (17)
C11A—C12A—H12A	119.7	C11B—C12B—H12B	119.9
C7A—C12A—H12A	119.7	C7B—C12B—H12B	119.9
N3A—C13A—C10A	179.0 (2)	N3B—C13B—C10B	178.5 (2)
C5A—N1A—C2A—C3A	0.88 (18)	C5B—N1B—C2B—C3B	0.31 (18)
C5A—N1A—C2A—C6A	−177.91 (14)	C5B—N1B—C2B—C6B	174.48 (15)
N1A—C2A—C3A—C4A	−0.49 (18)	N1B—C2B—C3B—C4B	−0.19 (19)
C6A—C2A—C3A—C4A	178.22 (16)	C6B—C2B—C3B—C4B	−173.90 (16)
C2A—C3A—C4A—C5A	−0.08 (19)	C2B—C3B—C4B—C5B	0.0 (2)
C2A—N1A—C5A—C4A	−0.95 (18)	C2B—N1B—C5B—C4B	−0.32 (19)
C3A—C4A—C5A—N1A	0.62 (19)	C3B—C4B—C5B—N1B	0.2 (2)
C7A—N2A—C6A—C2A	176.13 (14)	C7B—N2B—C6B—C2B	−177.96 (15)
N1A—C2A—C6A—N2A	−4.1 (2)	N1B—C2B—C6B—N2B	−0.3 (3)
C3A—C2A—C6A—N2A	177.38 (16)	C3B—C2B—C6B—N2B	172.44 (16)
C6A—N2A—C7A—C8A	136.23 (16)	C6B—N2B—C7B—C12B	−36.6 (2)
C6A—N2A—C7A—C12A	−48.3 (2)	C6B—N2B—C7B—C8B	145.50 (16)
C12A—C7A—C8A—C9A	3.6 (3)	C12B—C7B—C8B—C9B	2.9 (3)
N2A—C7A—C8A—C9A	179.22 (15)	N2B—C7B—C8B—C9B	−179.12 (15)
C7A—C8A—C9A—C10A	−2.7 (3)	C7B—C8B—C9B—C10B	−0.9 (3)
C8A—C9A—C10A—C11A	0.2 (3)	C8B—C9B—C10B—C11B	−1.0 (3)
C8A—C9A—C10A—C13A	179.91 (17)	C8B—C9B—C10B—C13B	179.07 (16)
C9A—C10A—C11A—C12A	1.3 (3)	C9B—C10B—C11B—C12B	0.9 (3)
C13A—C10A—C11A—C12A	−178.33 (16)	C13B—C10B—C11B—C12B	−179.14 (16)
C10A—C11A—C12A—C7A	−0.5 (3)	C10B—C11B—C12B—C7B	1.1 (3)
C8A—C7A—C12A—C11A	−2.0 (2)	C8B—C7B—C12B—C11B	−2.9 (2)
N2A—C7A—C12A—C11A	−177.44 (15)	N2B—C7B—C12B—C11B	179.19 (15)
C11A—C10A—C13A—N3A	147 (13)	C11B—C10B—C13B—N3B	57 (9)
C9A—C10A—C13A—N3A	−32 (13)	C9B—C10B—C13B—N3B	−123 (9)