2,2′-(Propane-2,2-di­yl)bis­(1H-pyrrole)

Journot, G.; Neier, R.; Stoeckli-Evans, H.

doi:10.1107/S1600536809054701

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o392

https://doi.org/10.1107/S1600536809054701

Open

access

2,2′-(Propane-2,2-diyl)bis(1H-pyrrole)

Guillaume Journot,^a Reinhard Neier ^a ^* and Helen Stoeckli-Evans ^b

^aInstitute of Chemistry, University of Neuchâtel, rue Emile-Argand 11, 2009 Neuchâtel, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, 2009 Neuchâtel, Switzerland
^*Correspondence e-mail: reinhard.neier@unine.ch

(Received 18 December 2009; accepted 19 December 2009; online 16 January 2010)

The title compound, C₁₁H₁₄N₂, crystallized with two independent molecules (A and B) in the asymmetric unit. The two molecules differ only slightly, with the pyrrole rings being inclined to one another at a dihedral angle of 87.67 (8)° in molecule A and 88.09 (7)° in molecule B. In the crystal, there are no classical hydrogen bonds, but the two pyrrole NH groups of one molecule are involved in N—H⋯π interactions with the pyrrole rings of the other molecule. In this manner, a compact box-like arrangement of the two independent molecules is formed.

Related literature

For substituted calix[4]pyrroles, see: Gale et al. (1998 ); Sessler & Davis (2001 ); Sessler et al. (2003 ). For the synthesis and crystal structure of meso-diethyl-bis(2-pyrrolyl)methane, see: Sobral et al. (2003 ). For intermolecular interactions involving aromatic rings in biological systems, see: Meyer et al. (2003 ). For a spectroscopic analysis of N—H⋯π interactions in pyrroles, see: Dauster et al. (2008 ).

Experimental

Crystal data

C₁₁H₁₄N₂
M_r = 174.24
Triclinic, $[P \overline 1]$
a = 8.4554 (8) Å
b = 9.2001 (8) Å
c = 13.2274 (11) Å
α = 99.802 (7)°
β = 95.321 (7)°
γ = 97.328 (7)°
V = 998.74 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 173 K
0.40 × 0.34 × 0.28 mm

Data collection

Stoe IPDS-2 diffractometer
15270 measured reflections
5385 independent reflections
3816 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.106
S = 1.02
5385 reflections
255 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Geometry of N—H⋯π interactions (Å, °)

D	H	Centroid	N—H	H⋯Cg	D⋯Cg	N—H⋯Cg
N1	H1N	Cg4	0.86 (2)	2.534 (17)	3.2190 (12)	137.4 (14)
N2	H2N	Cg3	0.86 (2)	2.591 (17)	3.2425 (12)	133.7 (13)
N21	H21N	Cg1	0.88 (2)	2.523 (16)	3.1925 (12)	133.9 (12)
N22	H22N	Cg2	0.86 (2)	2.610 (17)	3.2440 (12)	131.3 (13)
Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C4, N2/C5–C8, N21/C21—C24 and N22/C25–C28 rings, respectively.

Data collection: X-AREA (Stoe & Cie, 2009 ); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809054701/is2506sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809054701/is2506Isup2.hkl

checkCIF report

Comment top

The title compound was prepared as a building block for the formation of substituted calix[4]pyrroles. The latter have been shown to form extremely interesting host–guest complexes with various anions (Gale et al., 1998; Sessler & Davis, 2001; Sessler et al., 2003).

The structure of the title compound is shown in Fig. 1, and the geometrical parameters are given in the Supplementary Information and the archived CIF. The compound crystallized in the centrosymmetric triclinic space group P1 with two independent molecules (A and B) in the asymmetric unit. The bond lengths and angles are similar to those observed in the diethyl analogue (Sobral et al., 2003), which also crystallized with two independent molecules, but in the non-centrosymetric monoclinic space group C2.

In the title compound the quateranry centers, C9 in A and C29 in B, impose a twist to the molecules with the pyrrole ring mean-planes being almost perpendicular to one another; 87.67 (8) ° in molecule A and 88.09 (7)° in molecule B. This is similar to the situation in the diethyl analogue where the two dihedral angles are 86.5 (2) and 86.7 (2) °.

N—H···π interactions are extremely important in biological systems and this aspect as been reviewed by (Meyer et al., 2003). The spectroscopic aspects of the N—H···π interactions of the pyrrole dimer have also been studied recently by (Dauster et al., 2008). In the crystal of the title compound the two independent molecules are linked by N—H···π interactions involving the pyrrole NH H-atoms of molecule A with the pyrrole rings of molecule B, and visa-versa (Table 1). This leads to the formation of a compact box-like arrangement of the two molecules, as shown in Fig. 2. Again this arrangement is similar to that observed in the crystal of the diethyl analogue.

Related literature top

For substituted calix[4]pyrroles, see: Gale et al. (1998); Sessler & Davis (2001); Sessler et al. (2003). For the synthesis and crystal structure of meso-diethyl-bis(2-pyrrolyl)methane, see: Sobral et al. (2003). For intermolecular interactions involving aromatic rings in biological systems, see: Meyer et al. (2003). For a spectroscopic analysis of N—H···π interactions in pyrroles, see: Dauster et al. (2008).

Experimental top

A mixture of acetone (4.21 ml, 57.4 mmol) and pyrrole (31.72 ml, 0.459 mol, 8 equiv.) were stirred for 5 min and then trifluoroactetic acid (TFA: 0.44 ml, 2.53 mmol, 0.1 equiv) was added. The mixture stirred for an additional 5 min and then quenched with aqueous NaOH (0.1 N, 30 ml). It was then extracted with CH₂Cl₂ (50 ml × 2) and the organic layer dried (Na₂SO₄). The solvent was removed in vacuo and the remaining oil (82% pure in GC) was purified by flash chromatography on silica (eluent: cyclohexane/ethyl acetate; v:v = 4:1) to give colourless block-like crystals of the title compound (yield 6.8 g, 68%). ¹H NMR (CDCl₃): δ 7.72 (bs, 2H, N—H), 6.62–6.60 (m, 2H, pyrrolic-H1), 6.15–6.13 (m, 2H, pyrrolic-H2), 6.11–6.09 (m, 2H, pyrrolic-H3), 1.59 (s, 6H, –CH₃); ¹³CNMR (CDCl₃): δ 139.24 (C4), 117.19 (C1), 107.91 (C2), 103.87 (C3), 35.52(C5), 29.46 (C6).

Structure description top

For substituted calix[4]pyrroles, see: Gale et al. (1998); Sessler & Davis (2001); Sessler et al. (2003). For the synthesis and crystal structure of meso-diethyl-bis(2-pyrrolyl)methane, see: Sobral et al. (2003). For intermolecular interactions involving aromatic rings in biological systems, see: Meyer et al. (2003). For a spectroscopic analysis of N—H···π interactions in pyrroles, see: Dauster et al. (2008).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the molecular structure of the two independent molecules (A and B) of the title compound, with the displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view, along the a axis, of the crystal packing of the title compound. The N—H···π interactions are shown as dotted black lines for one of the box-like arrangements of the two independent molecules (see Table 1 for details; C-bound H-atoms have been omitted for clarity).

2,2'-(propane-2,2-diyl)bis(1H-pyrrole) top

Crystal data top

C₁₁H₁₄N₂	Z = 4
M_r = 174.24	F(000) = 376
Triclinic, P1	D_x = 1.159 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4554 (8) Å	Cell parameters from 10442 reflections
b = 9.2001 (8) Å	θ = 1.6–29.5°
c = 13.2274 (11) Å	µ = 0.07 mm⁻¹
α = 99.802 (7)°	T = 173 K
β = 95.321 (7)°	Block, colourless
γ = 97.328 (7)°	0.40 × 0.34 × 0.28 mm
V = 998.74 (15) Å³

Data collection top

Stoe IPDS-2 diffractometer	3816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 29.2°, θ_min = 1.6°
φ and ω scans	h = −11→11
15270 measured reflections	k = −12→12
5385 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0549P)² + 0.0012P] where P = (F_o² + 2F_c²)/3
5385 reflections	(Δ/σ)_max < 0.001
255 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₄N₂	γ = 97.328 (7)°
M_r = 174.24	V = 998.74 (15) Å³
Triclinic, P1	Z = 4
a = 8.4554 (8) Å	Mo Kα radiation
b = 9.2001 (8) Å	µ = 0.07 mm⁻¹
c = 13.2274 (11) Å	T = 173 K
α = 99.802 (7)°	0.40 × 0.34 × 0.28 mm
β = 95.321 (7)°

Data collection top

Stoe IPDS-2 diffractometer	3816 reflections with I > 2σ(I)
15270 measured reflections	R_int = 0.046
5385 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.25 e Å⁻³
5385 reflections	Δρ_min = −0.21 e Å⁻³
255 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.12135 (12)	0.25140 (11)	0.31284 (8)	0.0249 (3)
N2	0.40689 (12)	0.01811 (11)	0.24234 (8)	0.0252 (3)
C1	0.13663 (14)	0.38021 (14)	0.38492 (10)	0.0312 (4)
C2	0.17507 (15)	0.34619 (16)	0.47962 (10)	0.0348 (4)
C3	0.18351 (15)	0.19174 (16)	0.46471 (9)	0.0311 (4)
C4	0.14934 (13)	0.13454 (13)	0.36055 (9)	0.0234 (3)
C5	0.24635 (14)	−0.03734 (12)	0.22005 (9)	0.0226 (3)
C6	0.22365 (16)	−0.10944 (14)	0.11865 (9)	0.0305 (4)
C7	0.37369 (18)	−0.09563 (15)	0.07953 (10)	0.0358 (4)
C8	0.48462 (16)	−0.01599 (14)	0.15732 (10)	0.0314 (4)
C9	0.13255 (15)	−0.02364 (14)	0.30167 (9)	0.0277 (3)
C10	−0.04155 (17)	−0.07156 (17)	0.24923 (13)	0.0470 (5)
C11	0.1699 (2)	−0.12827 (17)	0.37732 (13)	0.0479 (5)
N21	0.51399 (12)	0.37264 (11)	0.36601 (7)	0.0232 (3)
N22	0.32603 (13)	0.28069 (11)	0.11006 (7)	0.0253 (3)
C21	0.59997 (14)	0.28840 (14)	0.42014 (9)	0.0264 (3)
C22	0.73108 (15)	0.26137 (15)	0.37047 (10)	0.0308 (4)
C23	0.72320 (14)	0.33192 (14)	0.28313 (9)	0.0281 (4)
C24	0.58798 (13)	0.40056 (13)	0.28184 (8)	0.0225 (3)
C25	0.35755 (14)	0.42785 (13)	0.15697 (8)	0.0229 (3)
C26	0.21946 (16)	0.48825 (14)	0.13876 (9)	0.0298 (4)
C27	0.10133 (16)	0.37382 (15)	0.07998 (10)	0.0340 (4)
C28	0.17016 (15)	0.24721 (14)	0.06366 (9)	0.0307 (3)
C29	0.52308 (14)	0.49773 (13)	0.21071 (9)	0.0251 (3)
C30	0.51173 (19)	0.65164 (14)	0.27414 (11)	0.0381 (4)
C31	0.63878 (17)	0.51784 (17)	0.12898 (10)	0.0381 (4)
H1N	0.1032 (19)	0.2477 (18)	0.2475 (13)	0.040 (4)*
H2N	0.4531 (19)	0.0726 (18)	0.2990 (12)	0.040 (4)*
H1	0.12280	0.47620	0.37120	0.0370*
H2	0.19290	0.41380	0.54380	0.0420*
H3	0.20840	0.13690	0.51730	0.0370*
H6	0.12470	−0.15960	0.08150	0.0370*
H7	0.39370	−0.13470	0.01140	0.0430*
H8	0.59580	0.01080	0.15310	0.0380*
H10A	−0.11590	−0.06340	0.30180	0.0710*
H10B	−0.05400	−0.17510	0.21260	0.0710*
H10C	−0.06530	−0.00660	0.20000	0.0710*
H11A	0.09550	−0.12180	0.43000	0.0720*
H11B	0.28040	−0.09850	0.41070	0.0720*
H11C	0.15750	−0.23100	0.33940	0.0720*
H21N	0.4231 (19)	0.4002 (16)	0.3827 (11)	0.031 (4)*
H22N	0.3894 (19)	0.2146 (18)	0.1123 (11)	0.039 (4)*
H21	0.57330	0.25470	0.48130	0.0320*
H22	0.81210	0.20590	0.39070	0.0370*
H23	0.79840	0.33180	0.23400	0.0340*
H26	0.20540	0.58890	0.16150	0.0360*
H27	−0.00570	0.38380	0.05650	0.0410*
H28	0.11950	0.15250	0.02670	0.0370*
H30A	0.47170	0.71520	0.22810	0.0570*
H30B	0.61830	0.69770	0.30870	0.0570*
H30C	0.43790	0.64010	0.32610	0.0570*
H31A	0.64370	0.42070	0.08640	0.0570*
H31B	0.74620	0.56090	0.16360	0.0570*
H31C	0.60000	0.58470	0.08510	0.0570*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0216 (5)	0.0271 (5)	0.0262 (5)	0.0050 (4)	0.0023 (4)	0.0045 (4)
N2	0.0249 (5)	0.0242 (5)	0.0266 (5)	0.0033 (4)	0.0039 (4)	0.0051 (4)
C1	0.0204 (6)	0.0265 (6)	0.0442 (7)	0.0037 (5)	0.0068 (5)	−0.0019 (5)
C2	0.0263 (6)	0.0400 (7)	0.0321 (6)	−0.0005 (5)	0.0080 (5)	−0.0090 (5)
C3	0.0269 (6)	0.0430 (8)	0.0231 (6)	0.0032 (5)	0.0050 (4)	0.0058 (5)
C4	0.0187 (5)	0.0285 (6)	0.0244 (5)	0.0045 (4)	0.0055 (4)	0.0068 (4)
C5	0.0244 (5)	0.0184 (5)	0.0258 (5)	0.0029 (4)	0.0035 (4)	0.0059 (4)
C6	0.0395 (7)	0.0234 (6)	0.0267 (6)	0.0030 (5)	0.0002 (5)	0.0024 (5)
C7	0.0553 (9)	0.0276 (7)	0.0283 (6)	0.0115 (6)	0.0169 (6)	0.0051 (5)
C8	0.0332 (7)	0.0269 (6)	0.0402 (7)	0.0104 (5)	0.0174 (5)	0.0116 (5)
C9	0.0270 (6)	0.0264 (6)	0.0312 (6)	0.0027 (5)	0.0094 (5)	0.0071 (5)
C10	0.0282 (7)	0.0395 (8)	0.0639 (10)	−0.0074 (6)	0.0111 (6)	−0.0107 (7)
C11	0.0672 (11)	0.0390 (8)	0.0518 (9)	0.0195 (7)	0.0325 (8)	0.0256 (7)
N21	0.0186 (5)	0.0288 (5)	0.0227 (5)	0.0038 (4)	0.0016 (4)	0.0060 (4)
N22	0.0289 (5)	0.0225 (5)	0.0239 (5)	0.0058 (4)	−0.0029 (4)	0.0043 (4)
C21	0.0248 (6)	0.0302 (6)	0.0236 (5)	0.0013 (5)	−0.0040 (4)	0.0087 (5)
C22	0.0238 (6)	0.0332 (7)	0.0360 (7)	0.0079 (5)	−0.0029 (5)	0.0085 (5)
C23	0.0211 (6)	0.0336 (7)	0.0292 (6)	0.0037 (5)	0.0037 (4)	0.0047 (5)
C24	0.0211 (5)	0.0237 (6)	0.0209 (5)	0.0000 (4)	−0.0003 (4)	0.0034 (4)
C25	0.0283 (6)	0.0221 (6)	0.0186 (5)	0.0039 (4)	0.0003 (4)	0.0055 (4)
C26	0.0349 (7)	0.0250 (6)	0.0308 (6)	0.0094 (5)	−0.0012 (5)	0.0074 (5)
C27	0.0289 (6)	0.0382 (7)	0.0347 (7)	0.0056 (5)	−0.0074 (5)	0.0115 (6)
C28	0.0317 (6)	0.0303 (6)	0.0267 (6)	−0.0010 (5)	−0.0080 (5)	0.0063 (5)
C29	0.0275 (6)	0.0242 (6)	0.0223 (5)	0.0002 (4)	−0.0014 (4)	0.0057 (4)
C30	0.0508 (8)	0.0234 (6)	0.0354 (7)	0.0030 (6)	−0.0115 (6)	0.0029 (5)
C31	0.0351 (7)	0.0476 (8)	0.0315 (6)	−0.0054 (6)	0.0023 (5)	0.0163 (6)

Geometric parameters (Å, º) top

N1—C1	1.3724 (17)	C10—H10C	0.9800
N1—C4	1.3705 (16)	C10—H10B	0.9800
N2—C5	1.3739 (16)	C10—H10A	0.9800
N2—C8	1.3655 (17)	C11—H11B	0.9800
N1—H1N	0.858 (17)	C11—H11A	0.9800
N2—H2N	0.856 (16)	C11—H11C	0.9800
N21—C21	1.3704 (16)	C21—C22	1.3683 (18)
N21—C24	1.3720 (14)	C22—C23	1.4186 (18)
N22—C25	1.3712 (15)	C23—C24	1.3750 (17)
N22—C28	1.3750 (17)	C24—C29	1.5170 (16)
N21—H21N	0.875 (16)	C25—C29	1.5192 (17)
N22—H22N	0.863 (16)	C25—C26	1.3744 (18)
C1—C2	1.3626 (19)	C26—C27	1.4211 (19)
C2—C3	1.413 (2)	C27—C28	1.3612 (19)
C3—C4	1.3781 (17)	C29—C31	1.5421 (18)
C4—C9	1.5118 (17)	C29—C30	1.5373 (18)
C5—C6	1.3757 (17)	C21—H21	0.9500
C5—C9	1.5115 (17)	C22—H22	0.9500
C6—C7	1.413 (2)	C23—H23	0.9500
C7—C8	1.3654 (19)	C26—H26	0.9500
C9—C11	1.541 (2)	C27—H27	0.9500
C9—C10	1.544 (2)	C28—H28	0.9500
C1—H1	0.9500	C30—H30A	0.9800
C2—H2	0.9500	C30—H30B	0.9800
C3—H3	0.9500	C30—H30C	0.9800
C6—H6	0.9500	C31—H31A	0.9800
C7—H7	0.9500	C31—H31B	0.9800
C8—H8	0.9500	C31—H31C	0.9800

C1—N1—C4	109.93 (10)	C9—C11—H11C	109.00
C5—N2—C8	110.24 (10)	H11A—C11—H11B	109.00
C1—N1—H1N	123.9 (11)	H11A—C11—H11C	109.00
C4—N1—H1N	126.1 (11)	H11B—C11—H11C	109.00
C5—N2—H2N	126.5 (11)	C9—C11—H11B	109.00
C8—N2—H2N	123.1 (11)	C9—C11—H11A	109.00
C21—N21—C24	110.16 (10)	N21—C21—C22	107.86 (11)
C25—N22—C28	110.04 (10)	C21—C22—C23	107.02 (11)
C21—N21—H21N	123.5 (9)	C22—C23—C24	108.20 (11)
C24—N21—H21N	126.3 (9)	C23—C24—C29	131.63 (10)
C28—N22—H22N	123.0 (11)	N21—C24—C23	106.75 (10)
C25—N22—H22N	126.8 (11)	N21—C24—C29	121.55 (10)
N1—C1—C2	107.93 (12)	N22—C25—C29	121.59 (11)
C1—C2—C3	107.31 (12)	C26—C25—C29	131.53 (11)
C2—C3—C4	108.08 (11)	N22—C25—C26	106.79 (10)
C3—C4—C9	130.99 (12)	C25—C26—C27	108.09 (11)
N1—C4—C9	122.17 (10)	C26—C27—C28	107.19 (12)
N1—C4—C3	106.75 (11)	N22—C28—C27	107.89 (11)
N2—C5—C6	106.70 (11)	C25—C29—C31	109.40 (10)
C6—C5—C9	131.40 (11)	C30—C29—C31	108.82 (11)
N2—C5—C9	121.74 (10)	C25—C29—C30	109.04 (10)
C5—C6—C7	107.85 (11)	C24—C29—C25	110.94 (10)
C6—C7—C8	107.59 (12)	C24—C29—C30	109.35 (10)
N2—C8—C7	107.61 (12)	C24—C29—C31	109.26 (10)
C4—C9—C5	111.44 (10)	N21—C21—H21	126.00
C10—C9—C11	109.12 (12)	C22—C21—H21	126.00
C5—C9—C10	109.09 (10)	C21—C22—H22	126.00
C5—C9—C11	108.66 (11)	C23—C22—H22	127.00
C4—C9—C10	109.10 (11)	C22—C23—H23	126.00
C4—C9—C11	109.41 (10)	C24—C23—H23	126.00
N1—C1—H1	126.00	C25—C26—H26	126.00
C2—C1—H1	126.00	C27—C26—H26	126.00
C3—C2—H2	126.00	C26—C27—H27	126.00
C1—C2—H2	126.00	C28—C27—H27	126.00
C4—C3—H3	126.00	N22—C28—H28	126.00
C2—C3—H3	126.00	C27—C28—H28	126.00
C7—C6—H6	126.00	C29—C30—H30A	109.00
C5—C6—H6	126.00	C29—C30—H30B	109.00
C6—C7—H7	126.00	C29—C30—H30C	109.00
C8—C7—H7	126.00	H30A—C30—H30B	110.00
N2—C8—H8	126.00	H30A—C30—H30C	109.00
C7—C8—H8	126.00	H30B—C30—H30C	109.00
C9—C10—H10A	109.00	C29—C31—H31A	109.00
C9—C10—H10B	109.00	C29—C31—H31B	109.00
C9—C10—H10C	109.00	C29—C31—H31C	109.00
H10B—C10—H10C	110.00	H31A—C31—H31B	109.00
H10A—C10—H10C	109.00	H31A—C31—H31C	110.00
H10A—C10—H10B	109.00	H31B—C31—H31C	109.00

C4—N1—C1—C2	0.14 (14)	N2—C5—C9—C10	170.37 (11)
C1—N1—C4—C3	−0.25 (13)	N2—C5—C9—C11	−70.77 (14)
C1—N1—C4—C9	176.69 (11)	C6—C5—C9—C10	−14.94 (19)
C8—N2—C5—C6	0.67 (14)	C6—C5—C9—C11	103.92 (15)
C8—N2—C5—C9	176.51 (11)	C5—C6—C7—C8	0.07 (16)
C5—N2—C8—C7	−0.63 (14)	C6—C7—C8—N2	0.34 (15)
C21—N21—C24—C29	−177.09 (10)	N21—C21—C22—C23	−0.10 (15)
C24—N21—C21—C22	−0.03 (13)	C21—C22—C23—C24	0.19 (15)
C21—N21—C24—C23	0.15 (13)	C22—C23—C24—N21	−0.21 (14)
C28—N22—C25—C26	−0.63 (13)	C22—C23—C24—C29	176.64 (12)
C28—N22—C25—C29	−177.43 (10)	N21—C24—C29—C25	−63.67 (14)
C25—N22—C28—C27	0.54 (14)	N21—C24—C29—C30	56.63 (15)
N1—C1—C2—C3	0.02 (14)	N21—C24—C29—C31	175.64 (11)
C1—C2—C3—C4	−0.17 (15)	C23—C24—C29—C25	119.88 (14)
C2—C3—C4—C9	−176.31 (12)	C23—C24—C29—C30	−119.82 (14)
C2—C3—C4—N1	0.25 (14)	C23—C24—C29—C31	−0.82 (18)
N1—C4—C9—C5	60.57 (15)	N22—C25—C26—C27	0.48 (13)
N1—C4—C9—C11	−179.26 (11)	C29—C25—C26—C27	176.83 (12)
C3—C4—C9—C5	−123.33 (14)	N22—C25—C29—C24	−47.82 (14)
N1—C4—C9—C10	−59.95 (15)	N22—C25—C29—C30	−168.30 (10)
C3—C4—C9—C11	−3.15 (19)	N22—C25—C29—C31	72.79 (14)
C3—C4—C9—C10	116.16 (15)	C26—C25—C29—C24	136.28 (13)
N2—C5—C9—C4	49.85 (15)	C26—C25—C29—C30	15.80 (17)
C9—C5—C6—C7	−175.73 (12)	C26—C25—C29—C31	−103.11 (15)
N2—C5—C6—C7	−0.44 (14)	C25—C26—C27—C28	−0.16 (14)
C6—C5—C9—C4	−135.46 (13)	C26—C27—C28—N22	−0.23 (14)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂
M_r	174.24
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.4554 (8), 9.2001 (8), 13.2274 (11)
α, β, γ (°)	99.802 (7), 95.321 (7), 97.328 (7)
V (Å³)	998.74 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.40 × 0.34 × 0.28

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15270, 5385, 3816
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.106, 1.02
No. of reflections	5385
No. of parameters	255
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Geometry of N—H···π interactions (Å, °) top

D	H	Centroid	N—H	H···Cg	D···Cg	N—H···Cg
N1	H1N	Cg4	0.86 (2)	2.534 (17)	3.2190 (12)	137.4 (14)
N2	H2N	Cg3	0.86 (2)	2.591 (17)	3.2425 (12)	133.7 (13)
N21	H21N	Cg1	0.88 (2)	2.523 (16)	3.1925 (12)	133.9 (12)
N22	H22N	Cg2	0.86 (2)	2.610 (17)	3.2440 (12)	131.3 (13)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C4, N2/C5–C8, N21/C21-C24 and N22/C25–C28 rings, respectively.

Acknowledgements

HSE is grateful to the XRD Application LAB, Microsystems Technology Division, Swiss Center for Electronics and Microtechnology, Neuchâtel, for access to the X-ray diffraction equipment.

References

Dauster, I., Rice, C. A., Zielke, P. & Suhm, M. A. (2008). Phys. Chem. Chem. Phys. 10, 2827–2835. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gale, P. A., Sessler, J. L. & Král, V. (1998). Chem. Commun. pp. 1–8. Web of Science CrossRef Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Meyer, E. A., Castellano, R. K. & Diederich, F. (2003). Angew. Chem. Int. Ed. 42, 1210–1250. Web of Science CrossRef CAS Google Scholar
Sessler, J. L., Camiolo, S. & Gale, P. A. (2003). Coord. Chem. Rev. 240, 17–55. Web of Science CrossRef CAS Google Scholar
Sessler, J. L. & Davis, J. M. (2001). Acc. Chem. Res. 34, 989–997. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sobral, A. J. F. N., Rebanda, N. G. C. L., da Silva, M., Lampreia, S. H., Silva, M. R., Beja, A. M., Paixão, J. A. & Rocha Gonsalves, A. M. d'A. (2003). Tetrahedron Lett. 44, 3971–3973. Web of Science CSD CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2009). X-AREA and X-RED32. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar