The crystal structure of the triclinic polymorph of 1,4-bis­([2,2′:6′,2′′-terpyridin]-4′-yl)benzene

Sedykh, A.E.; Kurth, D.G.; Müller-Buschbaum, K.

doi:10.1107/S2056989019015810

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 12| December 2019| Pages 1947-1951

https://doi.org/10.1107/S2056989019015810

Open

access

The crystal structure of the triclinic polymorph of 1,4-bis([2,2′:6′,2′′-terpyridin]-4′-yl)benzene

Alexander E. Sedykh,^a,^b Dirk G. Kurth ^c and Klaus Müller-Buschbaum ^a,^b ^*

^aInstitute of Inorganic and Analytical Chemistry, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany, ^bInstitute of Inorganic Chemistry, Julius-Maximilians-University Wüzburg, Am Hubland, 97074 Würzburg, Germany, and ^cLehrstuhl für Chemische Technologie der Materialsynthese, Julius-Maximilians-University Würzburg, Röntgenring 11, 97070 Würzburg, Germany
^*Correspondence e-mail: kmbac@uni-giessen.de

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 28 October 2019; accepted 22 November 2019; online 29 November 2019)

The title triclinic polymorph (Form I) of 1,4-bis([2,2′:6′,2′′-terpyridin]-4′-yl)benzene, C₃₆H₂₄N₆, was formed in the presence of the Lewis acid yttrium trichloride in an attempt to obtain a coordination compound. The crystal structure of the orthorhombic polymorph (Form II), has been described previously [Fernandes et al. (2010 ). Acta Cryst. E66, o3241–o3242]. The asymmetric unit of Form I consists of half a molecule, the whole molecule being generated by inversion symmetry with the central benzene ring being located about a crystallographic centre of symmetry. The side pyridine rings of the 2,2′:6′,2′′-terpyridine (terpy) unit are rotated slightly with respect to the central pyridine ring, with dihedral angles of 8.91 (8) and 10.41 (8)°. Opposite central pyridine rings are coplanar by symmetry, and the angle between them and the central benzene ring is 49.98 (8)°. The N atoms of the pyridine rings inside the terpy entities, N⋯N⋯N, lie in trans–trans positions. In the crystal, molecules are linked by C—H⋯π and offset π–π interactions [intercentroid distances are 3.6421 (16) and 3.7813 (16) Å], forming a three-dimensional structure.

Keywords: crystal structure; terpyridine; C—H⋯π interactions; offset π–π interactions.

CCDC reference: 1967605

1. Chemical context

1,4-Di([2,2′:6′,2′′-terpyridin]-4′-yl)benzene has been used as a ligand in the formation of mononuclear complexes (Santoni et al., 2013 ; Laramée-Milette & Hanan, 2017 ), binuclear complexes (Santoni et al., 2013; Schmittel et al.,2006 ; Maekawa et al., 2004 ), tetranuclear complexes (Schmittel et al., 2005 ), one-dimensional coordination polymers (Koo et al., 2003 ), two-dimensional coordination polymers (Bulut et al., 2015 ; Jones et al. (2010 ), and numerous metallo-supramolecular polymers (without reported crystal structures), see for example: Vaduvescu & Potvin, 2004 ; Nishimori et al., 2007 ; Han et al., 2008 ; Schwarz et al., 2010 ; Ding et al., 2012 ; Muronoi et al., 2013 ; Szczerba et al., 2014 ; Munzert et al., 2016 ; Meded et al., 2017 ; Bera et al., 2018 .

A search of the Cambridge Structural Database (CSD, Version 5.40, update August 2019; Groom et al., 2016 ) for the title compound yielded only nine hits (see supporting information), which included the report on the structure of the orthorhombic polymorph, Form II, by Fernandes et al. (2010).

2. Structural commentary

The molecular structure of the title triclinic polymorph (Form I) is illustrated in Fig. 1. The molecule is located about a crystallographic centre of symmetry in the middle of the central benzene ring (C16–C18/C16′–C18′), hence the molecule has a higher symmetry (point group C_i) than that observed for the orthorhombic polymorph, Form II (Fernandes et al., 2010), which has point group C₁. In Form I the side pyridine rings (N2/C6–C10 and N3/C11–C15) are rotated slightly with respect to the central pyridine ring (N1/C1–C5), with dihedral angles of 8.91 (8) and 10.41 (8)°, respectively. Opposite central pyridine rings (N1/C1–C5 and N1′/C1′–C5′) are coplanar by symmetry, and the angle between them and the central benzene ring (C16–C18/C16′–C18′) is 49.98 (8)° [symmetry code: (') −x, −y, −z]. The nitrogen atoms of the pyridine rings inside the 2,2′:6′,2′′-terpyridine (terpy) entities, N3⋯N1⋯N2, lie in trans–trans positions.

Figure 1
The molecular structure of the title triclinic polymorph (Form I), with atom labelling [symmetry code ('): −x, −y, −z]. Displacement ellipsoids are drawn at the 50% probability level.

In the orthorhombic polymorph, Form II, all the angles between side and central pyridine rings of the terpy units are different (because of the lack of symmetry elements inside the molecule), viz. 24.86 (12) and 5.10 (12)° on one side and 6.30 (11) and 8.21 (12)° on the opposite side. The dihedral angles between the central pyridine rings of the terpy units and the central benzene ring are 34.95 (11) and 36.17 (11)°. A structural overlay of the molecules of the two polymorphs (r.m.s. deviation = 0.0705 Å), illustrating the differences in their conformation, is given in Fig. 2 (Mercury; Macrae et al., 2008 ).

Figure 2
A structural overlay of the title triclinic polymorph (Form I; blue) and the orthorhombic polymorph (Form II; red), drawn using Mercury (Macrae et al., 2008

3. Supramolecular features

In the crystal of the title polymorph, Form I, the molecules stack along the a-, b- and c-axis directions (Fig. 3). They are linked by C—H⋯π interactions (Table 1) and offset π–π interactions, which are summarized in Table 2 for both Form I and Form II. It is interesting to note that the centroid–centroid distances and the offset distances are significantly shorter for Form II. An additional difference between the two polymorphs is the character of stacking: in Form II molecules form several two-dimensional stacks, which are perpendicular to each another, while in Form I the stacking is three-dimensional.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N2/C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯Cg2ⁱ	0.96	2.99	3.682 (2)	131
Symmetry code: (i) x, y-1, z.

Table 2
π–π stacking interactions (Å, °) for Form I and Form II

Form I: Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C5, N2/C6–C10 and N3/C11–C15 rings, respectively. Form II: Cg1 and Cg2 are the centroids of the N1/C1–C5 and N2/C6–C10 rings, respectively (Fernandes et al., 2010).

CgI	CgJ	CgI⋯CgJ	α	β	γ	CgI_Perp	CgJ_Perp	offset
Form I
Cg1	Cg3ⁱⁱ	3.6421 (16)	8.91 (8)	18.6	17.9	3.4648 (6)	3.4525 (8)	1.160
Cg2	Cg3ⁱⁱⁱ	3.7813 (16)	4.43 (8)	26.0	24.8	3.4312 (7)	3.3990 (8)	1.657

Form II
Cg1	Cg2^iv	3.5138 (15)	4.20 (12)	10.9	14.9	3.3963 (12)	3.4501 (9)	0.666
Cg2	Cg1^v	3.5140 (15)	4.20 (12)	14.9	10.9	3.4503 (9)	3.3963 (12)	0.902
Symmetry codes (ii) −x, −y + 1, −z + 1; (iii) −x + 1, −y + 1, −z + 1; (iv) x − $[{1\over 2}]$ , −y, z; (v) x + $[{1\over 2}]$ , −y, z.

Figure 3
The crystal packing of the title triclinic polymorph (Form I) viewed along the a (top), b (middle) and c (bottom) axes.

4. Hirshfeld surfaces and two-dimensional fingerprint plots

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). For an excellent explanation of the use of Hirshfeld surface analysis and other calculations to study molecular packing, see the recent article by Tiekink and collaborators (Tan et al., 2019 ).

The Hirshfeld surfaces are colour-mapped with the normalized contact distance, d_norm, from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii).

The Hirshfeld surface of Forms I and II, mapped over d_norm are given in Fig. 4a and 5a, respectively, where short interatomic contacts are indicated by the faint red spots. The π–π stacking is confirmed by the small blue regions surrounding bright-red spots in the various aromatic rings (Fig. 4b and 5b) on the Hirshfeld surface mapped over the shape-index, and by the flat regions around the aromatic regions in Fig. 4c and 5c, the Hirshfeld surface mapped over the curvedness.

Figure 4
(a) The Hirshfeld surface of Form I, mapped over d_norm, plotted in the range −0.0541 to 1.3209 a.u., (b) the Hirshfeld surface of Form I, mapped over the shape-index and (c) the Hirshfeld surface of Form I, mapped over the curvedness.

Figure 5
(a) The Hirshfeld surface of Form II, mapped over d_norm, plotted in the range −0.1446 to 1.2077 a.u., (b) the Hirshfeld surface of Form II, mapped over the shape-index and (c) the Hirshfeld surface of Form II, mapped over the curvedness.

The fingerprint plots for Forms I and II, are given in Figs. 6 and 7. They reveal that the principal intermolecular contacts in the crystal of Form I are H⋯H at 49.4% (Fig. 6b), C⋯H/H⋯C at 24.7% (Fig. 6c), C⋯C at 9.6% (Fig. 6d), N⋯H/H⋯N at 9.4% (Fig. 6e) and C⋯N at 6.2% (Fig. 6f).

Figure 6
The full two-dimensional fingerprint plot for Form I, and fingerprint plots delineated into H⋯H, C⋯H/H⋯C, C⋯C, N⋯H/H⋯N and C⋯N contacts.

Figure 7
The full two-dimensional fingerprint plot for Form II, and fingerprint plots delineated into H⋯H, C⋯H/H⋯C, N⋯H/H⋯N, C⋯C and C⋯N contacts.

The principal intermolecular contacts in the crystal of Form II are H⋯H at 43.3% (Fig. 7b), C⋯H/H⋯C at 30.6% (Fig. 7c), N⋯H/H⋯N at 13.3% (Fig. 7d), C⋯C at 8.3% (Fig. 7e) and C⋯N at 4.3% (Fig. 7f). Here, the C⋯H/H⋯C and N⋯H/H⋯N contacts at 30.6 and 13.3%, respectively, are more important than those in Form I at 24.7 and 9.4%, respectively.

5. Synthesis and crystallization

1,4-Bis([2,2′:6′,2′′-terpyridin]-4′-yl)benzene was synthesized according to the literature procedure (Winter et al., 2006 ). YCl₃ (99.9%, Strem) was purchased and used as received. Solvents (DMF, toluene) were dried using standard techniques and stored with molecular sieves in flasks with a J. Young valve.

YCl₃ (2 mg, 0.01 mmol), 1,4-bis([2,2′:6′,2′′-terpyridin]-4′-yl)benzene (0.5 mg, 0.001 mmol) and 1 ml DMF were filled together under inert conditions in a self-made Duran^(R) glass ampoule (outer ø 10 mm, wall thickness 1 mm). The ampoule was sealed under vacuum and placed in a resistance heating oven with a thermal control (Eurotherm 2416). The heating program was as follows: heating up to 503 K in 30 min, holding temperature for 8 h, cooling down to RT uncontrollably. The ampoule was then taken out of the oven and a star-like net of needle-shaped single crystals was observed. The ampoule was heated again as previously but up to 523 K and then cooled down to RT uncontrollably. Now only a few plate-shaped single crystals were present. The ampoule was unsealed, the solution removed and the remaining single crystals were washed with toluene (1 ml).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms were included in calculated positions and refined as riding on the parent C atom: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₃₆H₂₄N₆
M_r	540.61
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.312 (2), 8.847 (3), 11.039 (3)
α, β, γ (°)	100.050 (7), 102.247 (6), 104.314 (7)
V (Å³)	656.4 (3)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.53 × 0.30 × 0.23

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
T_min, T_max	0.764, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	10437, 2918, 1953
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.133, 1.09
No. of reflections	2918
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), shelXle (Hübschle et al., 2011 ), Mercury (Macrae et al., 2008), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1967605

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019015810/su5525sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019015810/su5525Isup2.hkl

CSD search. DOI: https://doi.org/10.1107/S2056989019015810/su5525sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989019015810/su5525Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

1,4-Bis([2,2':6',2''-terpyridin]-4'-yl)benzene top

Crystal data top

C₃₆H₂₄N₆	Z = 1
M_r = 540.61	F(000) = 282
Triclinic, P1	D_x = 1.368 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.312 (2) Å	Cell parameters from 3259 reflections
b = 8.847 (3) Å	θ = 2.5–27.1°
c = 11.039 (3) Å	µ = 0.08 mm⁻¹
α = 100.050 (7)°	T = 100 K
β = 102.247 (6)°	Plate, colourless
γ = 104.314 (7)°	0.53 × 0.30 × 0.23 mm
V = 656.4 (3) Å³

Data collection top

Bruker X8 APEXII diffractometer	2918 independent reflections
Radiation source: rotating-anode (Nonius FR-591)	1953 reflections with I > 2σ(I)
Multi-layer mirror monochromator	R_int = 0.049
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.2°, θ_min = 1.9°
φ and ω scans	h = −9→5
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −11→11
T_min = 0.764, T_max = 0.958	l = −14→14
10437 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.09	w = 1/[\s²(F_o²) + (0.0552P)² + 0.1381P] where P = (F_o² + 2F_c²)/3
2918 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.31314 (19)	0.57168 (16)	0.39738 (13)	0.0184 (3)
N2	0.4458 (2)	0.73483 (17)	0.13929 (13)	0.0213 (3)
N3	0.0878 (2)	0.29403 (17)	0.56336 (13)	0.0227 (4)
C1	0.3286 (2)	0.5741 (2)	0.27836 (16)	0.0180 (4)
C2	0.2523 (2)	0.4377 (2)	0.17767 (16)	0.0183 (4)
H2	0.260141	0.444780	0.093931	0.022*
C3	0.1647 (2)	0.2912 (2)	0.20071 (15)	0.0178 (4)
C4	0.1538 (2)	0.2879 (2)	0.32419 (16)	0.0190 (4)
H4	0.098885	0.189236	0.344145	0.023*
C5	0.2242 (2)	0.4309 (2)	0.41872 (15)	0.0170 (4)
C6	0.4396 (2)	0.7297 (2)	0.25945 (15)	0.0177 (4)
C7	0.5401 (2)	0.8601 (2)	0.36334 (16)	0.0223 (4)
H7	0.531212	0.853493	0.446984	0.027*
C8	0.6527 (2)	0.9991 (2)	0.34305 (18)	0.0261 (4)
H8	0.722880	1.089152	0.412386	0.031*
C9	0.6610 (2)	1.0042 (2)	0.22011 (17)	0.0245 (4)
H9	0.737656	1.097586	0.203028	0.029*
C10	0.5551 (2)	0.8702 (2)	0.12213 (17)	0.0236 (4)
H10	0.560586	0.875011	0.037631	0.028*
C11	0.2008 (2)	0.4309 (2)	0.54952 (15)	0.0187 (4)
C12	0.2926 (2)	0.5660 (2)	0.65033 (16)	0.0220 (4)
H12	0.370162	0.661960	0.637260	0.026*
C13	0.2681 (3)	0.5569 (2)	0.77001 (17)	0.0267 (4)
H13	0.330137	0.646686	0.840845	0.032*
C14	0.1533 (3)	0.4169 (2)	0.78556 (17)	0.0270 (4)
H14	0.134352	0.408052	0.866839	0.032*
C15	0.0662 (3)	0.2893 (2)	0.67977 (17)	0.0277 (4)
H15	−0.013662	0.192846	0.690615	0.033*
C16	0.0823 (2)	0.14143 (19)	0.09699 (15)	0.0178 (4)
C17	0.1252 (2)	0.0007 (2)	0.11349 (16)	0.0197 (4)
H17	0.210899	0.000508	0.191289	0.024*
C18	−0.0443 (2)	0.1397 (2)	−0.01748 (15)	0.0200 (4)
H18	−0.075227	0.234999	−0.029841	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0168 (7)	0.0215 (8)	0.0160 (8)	0.0058 (6)	0.0032 (6)	0.0033 (6)
N2	0.0215 (7)	0.0226 (8)	0.0191 (8)	0.0060 (6)	0.0045 (6)	0.0053 (6)
N3	0.0234 (8)	0.0268 (8)	0.0182 (8)	0.0065 (6)	0.0064 (6)	0.0063 (6)
C1	0.0136 (8)	0.0223 (9)	0.0174 (9)	0.0066 (7)	0.0024 (7)	0.0035 (7)
C2	0.0162 (8)	0.0247 (9)	0.0129 (9)	0.0049 (7)	0.0033 (7)	0.0036 (7)
C3	0.0136 (8)	0.0216 (9)	0.0162 (9)	0.0054 (7)	0.0021 (7)	0.0013 (7)
C4	0.0158 (8)	0.0198 (9)	0.0201 (9)	0.0039 (7)	0.0039 (7)	0.0044 (7)
C5	0.0129 (8)	0.0217 (9)	0.0144 (9)	0.0048 (7)	0.0017 (6)	0.0018 (7)
C6	0.0140 (8)	0.0208 (9)	0.0179 (9)	0.0062 (7)	0.0034 (7)	0.0034 (7)
C7	0.0216 (9)	0.0241 (9)	0.0187 (9)	0.0049 (7)	0.0047 (7)	0.0017 (7)
C8	0.0213 (9)	0.0216 (10)	0.0287 (11)	0.0023 (7)	0.0029 (8)	−0.0002 (8)
C9	0.0191 (8)	0.0220 (9)	0.0308 (11)	0.0029 (7)	0.0066 (8)	0.0072 (8)
C10	0.0229 (9)	0.0269 (10)	0.0223 (10)	0.0071 (8)	0.0066 (7)	0.0089 (8)
C11	0.0156 (8)	0.0234 (9)	0.0171 (9)	0.0081 (7)	0.0021 (7)	0.0040 (7)
C12	0.0205 (9)	0.0250 (10)	0.0193 (9)	0.0080 (7)	0.0034 (7)	0.0031 (8)
C13	0.0263 (9)	0.0344 (11)	0.0188 (10)	0.0144 (8)	0.0022 (8)	0.0018 (8)
C14	0.0277 (9)	0.0431 (12)	0.0157 (9)	0.0169 (9)	0.0081 (8)	0.0089 (8)
C15	0.0285 (10)	0.0344 (11)	0.0238 (10)	0.0096 (8)	0.0097 (8)	0.0123 (9)
C16	0.0148 (8)	0.0207 (9)	0.0154 (9)	0.0011 (7)	0.0054 (7)	0.0019 (7)
C17	0.0172 (8)	0.0264 (9)	0.0132 (9)	0.0052 (7)	0.0020 (6)	0.0030 (7)
C18	0.0201 (8)	0.0200 (9)	0.0191 (9)	0.0052 (7)	0.0051 (7)	0.0040 (7)

Geometric parameters (Å, º) top

N1—C5	1.340 (2)	C8—C9	1.379 (3)
N1—C1	1.346 (2)	C8—H8	0.9500
N2—C10	1.334 (2)	C9—C10	1.385 (2)
N2—C6	1.345 (2)	C9—H9	0.9500
N3—C15	1.334 (2)	C10—H10	0.9500
N3—C11	1.340 (2)	C11—C12	1.393 (2)
C1—C2	1.393 (2)	C12—C13	1.384 (2)
C1—C6	1.489 (2)	C12—H12	0.9500
C2—C3	1.389 (2)	C13—C14	1.374 (3)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.387 (2)	C14—C15	1.383 (3)
C3—C16	1.487 (2)	C14—H14	0.9500
C4—C5	1.395 (2)	C15—H15	0.9500
C4—H4	0.9500	C16—C17	1.389 (2)
C5—C11	1.490 (2)	C16—C18	1.394 (2)
C6—C7	1.396 (2)	C17—C18ⁱ	1.388 (2)
C7—C8	1.383 (2)	C17—H17	0.9500
C7—H7	0.9500	C18—H18	0.9500

C5—N1—C1	117.93 (14)	C10—C9—H9	120.7
C10—N2—C6	117.38 (14)	N2—C10—C9	123.93 (17)
C15—N3—C11	117.47 (15)	N2—C10—H10	118.0
N1—C1—C2	122.49 (15)	C9—C10—H10	118.0
N1—C1—C6	116.71 (14)	N3—C11—C12	122.76 (16)
C2—C1—C6	120.75 (15)	N3—C11—C5	115.99 (14)
C3—C2—C1	119.43 (15)	C12—C11—C5	121.25 (15)
C3—C2—H2	120.3	C13—C12—C11	118.34 (17)
C1—C2—H2	120.3	C13—C12—H12	120.8
C4—C3—C2	118.00 (15)	C11—C12—H12	120.8
C4—C3—C16	120.29 (15)	C14—C13—C12	119.44 (17)
C2—C3—C16	121.70 (15)	C14—C13—H13	120.3
C3—C4—C5	119.28 (16)	C12—C13—H13	120.3
C3—C4—H4	120.4	C13—C14—C15	118.26 (17)
C5—C4—H4	120.4	C13—C14—H14	120.9
N1—C5—C4	122.72 (15)	C15—C14—H14	120.9
N1—C5—C11	117.46 (14)	N3—C15—C14	123.72 (18)
C4—C5—C11	119.82 (15)	N3—C15—H15	118.1
N2—C6—C7	122.30 (16)	C14—C15—H15	118.1
N2—C6—C1	116.79 (14)	C17—C16—C18	119.01 (15)
C7—C6—C1	120.83 (15)	C17—C16—C3	120.93 (15)
C8—C7—C6	119.20 (16)	C18—C16—C3	120.04 (15)
C8—C7—H7	120.4	C18ⁱ—C17—C16	120.68 (16)
C6—C7—H7	120.4	C18ⁱ—C17—H17	119.7
C9—C8—C7	118.65 (16)	C16—C17—H17	119.7
C9—C8—H8	120.7	C17ⁱ—C18—C16	120.31 (16)
C7—C8—H8	120.7	C17ⁱ—C18—H18	119.8
C8—C9—C10	118.53 (16)	C16—C18—H18	119.8
C8—C9—H9	120.7

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N2/C6–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Cg2ⁱⁱ	0.96	2.99	3.682 (2)	131

Symmetry code: (ii) x, y−1, z.

π–π stacking interactions (Å,°) for Form I and Form II top

CgI	CgJ	CgI···CgJ	α	β	γ	CgI_Perp	CgJ_Perp	offset
Form I
Cg1	Cg3ⁱⁱ	3.6421 (16)	8.91 (8)	18.6	17.9	3.4648 (6)	3.4525 (8)	1.160
Cg2	Cg3ⁱⁱⁱ	3.7813 (16)	4.43 (8)	26.0	24.8	3.4312 (7)	3.3990 (8)	1.657

Form II
Cg1	Cg2^iv	3.5138 (15)	4.20 (12)	10.9	14.9	3.3963 (12)	3.4501 (9)	0.666
Cg2	Cg1^v	3.5140 (15)	4.20 (12)	14.9	10.9	3.4503 (9)	3.3963 (12)	0.902

Symmetry codes (ii) -x, -y + 1, -z + 1; (iii) -x + 1, -y + 1, -z + 1; (iv) x - 1/2, -y, z; (v) x + 1/2, -y, z.

Funding information

Funding for this research was provided by: Studienstiftung des Deutschen Volkes (scholarship to Alexander E. Sedykh).

References

Bera, M. K., Chakraborty, C., Rana, U. & Higuchi, M. (2018). Macromol. Rapid Commun. 39, 2–7. CrossRef Google Scholar
Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bulut, A., Zorlu, Y., Kirpi, E. E., Çetinkaya, A., Wörle, M., Beckmann, J. & Yücesan, G. (2015). Cryst. Growth Des. 15, 5665–5669. CSD CrossRef CAS Google Scholar
Ding, Y., Yang, Y., Yang, L., Yan, Y., Huang, J. & Cohen Stuart, M. A. (2012). ACS Nano, 6, 1004–1010. CrossRef CAS PubMed Google Scholar
Fernandes, J. A., Almeida Paz, F. A., Lima, P. P., Alves, S. Jr & Carlos, L. D. (2010). Acta Cryst. E66, o3241–o3242. CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Han, F. S., Higuchi, M. & Kurth, D. G. (2008). J. Am. Chem. Soc. 130, 2073–2081. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Jones, S., Liu, H., Ouellette, W., Schmidtke, K., O'Connor, C. J. & Zubieta, J. (2010). Inorg. Chem. Commun. 13, 491–494. Web of Science CSD CrossRef CAS Google Scholar
Koo, B.-K., Bewley, L., Golub, V., Rarig, R. S., Burkholder, E., O'Connor, C. J. & Zubieta, J. (2003). Inorg. Chim. Acta, 351, 167–176. Web of Science CSD CrossRef CAS Google Scholar
Laramée-Milette, B. & Hanan, G. S. (2017). Chem. Commun. 53, 10496–10499. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Maekawa, M., Minematsu, T., Konaka, H., Sugimoto, K., Kuroda-Sowa, T., Suenaga, Y. & Munakata, M. (2004). Inorg. Chim. Acta, 357, 3456–3472. CSD CrossRef CAS Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Meded, V., Knorr, N., Neumann, T., Nelles, G., Wenzel, W. & von Wrochem, F. (2017). Phys. Chem. Chem. Phys. 19, 27952–27959. CrossRef CAS PubMed Google Scholar
Munzert, S. M., Schwarz, G. & Kurth, D. G. (2016). Inorg. Chem. 55, 2565–2573. CrossRef CAS PubMed Google Scholar
Muronoi, Y., Zhang, J., Higuchi, M. & Maki, H. (2013). Chem. Lett. 42, 761–763. CrossRef CAS Google Scholar
Nishimori, Y., Kanaizuka, K., Murata, M. & Nishihara, H. (2007). Chem. Asian J. 2, 367–376. CrossRef PubMed CAS Google Scholar
Santoni, M.-P., Nastasi, F., Campagna, S., Hanan, G. S., Hasenknopf, B. & Ciofini, I. (2013). Dalton Trans. 42, 5281–5291. CSD CrossRef CAS PubMed Google Scholar
Schmittel, M., Kalsani, V., Kishore, R. S. K., Cölfen, H. & Bats, J. W. (2005). J. Am. Chem. Soc. 127, 11544–11545. Web of Science CSD CrossRef PubMed CAS Google Scholar
Schmittel, M., Kalsani, V., Mal, P. & Bats, J. W. (2006). Inorg. Chem. 45, 6370–6377. Web of Science CSD CrossRef PubMed CAS Google Scholar
Schwarz, G., Bodenthin, Y., Geue, T., Koetz, J. & Kurth, D. G. (2010). Macromolecules, 43, 494–500. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szczerba, W., Schott, M., Riesemeier, H., Thünemann, A. F. & Kurth, D. G. (2014). Phys. Chem. Chem. Phys. 16, 19694–19701. CrossRef CAS PubMed Google Scholar
Tan, S. L., Jotani, M. M. & Tiekink, E. R. T. (2019). Acta Cryst. E75, 308–318. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Vaduvescu, S. & Potvin, P. G. (2004). Eur. J. Inorg. Chem. pp. 1763–1769. CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Winter, A., van den Berg, A., Hoogenboom, R., Kickelbick, G. & Schubert, U. S. (2006). Synthesis, pp. 2873–2878. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.