Crystal structure and Hirshfeld surface analysis of 4-{2,2-di­chloro-1-[(E)-(4-chloro­phen­yl)diazen­yl]ethen­yl}-N,N-di­methyl­aniline

Atioğlu, Z.; Akkurt, M.; Shikhaliyev, N.Q.; Mukhtarova, S.H.; Suleymanova, G.T.; Toze, F.A.A.

doi:10.1107/S2056989020007549

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ISSN: 2056-9890

Volume 76| Part 7| July 2020| Pages 1033-1037

https://doi.org/10.1107/S2056989020007549

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Crystal structure and Hirshfeld surface analysis of 4-{2,2-dichloro-1-[(E)-(4-chlorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline

Zeliha Atioğlu,^a Mehmet Akkurt,^b Namiq Q. Shikhaliyev,^c Sevinc H. Mukhtarova,^c Gulnar T. Suleymanova ^c and Flavien A. A. Toze ^d ^*

^aİlke Education and Health Foundation, Cappadocia University, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, and ^dDepartment of Chemistry, Faculty of Sciences, University of Douala, PO Box 24157, Douala, Republic of , Cameroon
^*Correspondence e-mail: toflavien@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 14 April 2020; accepted 4 June 2020; online 9 June 2020)

The title compound, C₁₆H₁₄Cl₃N₃, comprises three molecules of similar shape in the asymmetric unit. The crystal cohesion is ensured by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds in addition to C—Cl⋯π interactions. Hirshfeld surface analysis and two-dimensional fingerprint plots reveal that Cl⋯H/H⋯Cl (33.6%), H⋯H (27.9%) and C⋯H/H⋯C (17.6%) are the most important contributors towards the crystal packing.

Keywords: crystal structure; non-covalent interactions; azo dye; Hirshfeld surface analysis.

CCDC reference: 2007970

1. Chemical context

Non-covalent interactions, such as hydrogen bonds, halogen–halogen or chalcogen–chalcogen bonds, van der Waals interactions or π–π stacking, π⋯cation and π⋯anion interactions, etc. are much weaker than covalent bonds. Nevertheless, they can control the reactivity of molecules, the crystal packing, tautomerization and other properties (Asadov et al., 2016 ; Mahmudov et al., 2019 ). For example, such kinds of weak interactions can create interesting supramolecular networks in coordination compounds, involving monomeric, oligomeric or polymeric subunits, which affects their catalytic activity (Afkhami et al., 2017 ; Gurbanov et al., 2018 ).

In a previous study we have attached resonance-assisted hydrogen-bonded synthons or chlorine atoms to dye molecules, which leads to intermolecular weak interactions for the resulting products with interesting analytical and solvatochromic properties (Maharramov et al., 2018 ; Mahmudov & Pombeiro, 2016 ). In a continuation of our work in this direction, we now have synthesized a new azo dye, 4-{2,2-dichloro-1-[(E)-(4-chlorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline, which features C—H⋯N, C—H⋯π and C—Cl⋯Cl types of weak intermolecular interactions.

2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) contains three molecules of similar shape, hereafter referred to as Mol-N1 (C1–C16/N1–N3/Cl1–Cl3), Mol-N1A (C1A–C16A/N1A–N3A/Cl1A–Cl3A) and Mol-N1B (C1B–C16B/N1B–N3B/Cl1B–Cl3B). The conformational differences between molecules Mol-N1, Mol-N1A and Mol-N1B are highlighted in an overlay diagram shown in Fig. 2. The dihedral angles between the benzene rings [C1–C6 and C8–C13 (molecule Mol-N1), C1A–C6A and C8A–C13A (molecule Mol-N1A), and C1B–C6B and C8B–C13B (molecule Mol-N1B)] of the 4-chlorophenyl and N,N-dimethylaniline groups are 69.94 (10), 79.68 (12) and 88.08 (13)°, respectively. In molecule Mol-N1, the N1—N2—C7—C14, N2—C7—C14—Cl2, N2—C7—C14—Cl3 and C8—C7—C14—Cl3 torsion angles are −178.7 (2), 3.1 (3), −176.21 (16) and 4.1 (3)°, respectively. The corresponding angles are 178.4 (2), 3.8 (3), −175.1 (2) and 2.5 (3)° for molecule Mol-N1A, and −175.0 (2), 0.3 (3), 179.71 (18) and −0.1 (4) for molecule Mol-N1B.

Figure 1
The molecular structures of the three molecules in the asymmetric unit of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level.

Figure 2
Overlay image of the three molecules in the asymmetric unit of the title compound.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the molecules are connected by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds and C—Cl⋯π interactions, which contribute to the overall packing, forming a three-dimensional network (Table 1; Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg4 are the centroids of the C1–C6 and C8A–C13A rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N3A	0.93	2.68	3.597 (3)	167
C5B—H5BA⋯Cl3ⁱ	0.93	2.95	3.703 (3)	139
C14—Cl3⋯Cg1ⁱⁱ	1.71 (1)	3.55 (1)	4.083 (2)	96 (1)
C14B—Cl3B⋯Cg4ⁱⁱⁱ	1.71 (1)	3.85 (1)	5.300 (3)	142 (1)
Symmetry codes: (i) x, y+1, z-1; (ii) -x+2, -y, -z+2; (iii) -x+1, -y, -z+1.

Figure 3
A partial view of the crystal packing of the title compound. Intermolecular interactions are shown as dashed lines.

Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and intermolecular interactions in the crystal structure. The Hirshfeld surfaces (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) of the title compound were calculated using Crystal Explorer 17.5 (Turner et al., 2017 ). The three-dimensional molecular Hirshfeld surfaces of the three molecules Mol-N1, Mol-N1A and Mol-N1B and the overall surface were generated using a high standard surface resolution colour-mapped over the normalized contact distance. The red, white and blue regions visible on the d_norm surfaces indicate contacts with distances shorter, longer and equal to the van der Waals radii (Fig. 4a). The shape-index of the Hirshfeld surface is a tool to visualize π–π stacking interactions; Fig. 4b clearly suggest that there are no π–π interactions in the title compound. The red spots in Fig. 4a correspond to the relatively strong C—H⋯N hydrogen-bonding interactions in the crystal structure; in Mol-N1A it involves the N3A atoms of the N,N-dimethylaniline group as acceptors with the aromatic H2A donor atom of the chlorobenzene ring in Mol-N1 (C2—H2A⋯N3A).

Figure 4
Hirshfeld surface of the title compound (symmetry-independent molecules Mol-N1, Mol-N1A and Mol-N1B, and overall), with (a) the interaction of neighbouring molecules mapped over d_norm and (b) mapped over shape-index.

Two-dimensional fingerprint plots are presented in Fig. 5. The red points, which represent closer contacts and negative d_norm values on the surface, correspond to C—H⋯Cl interactions. The reciprocal Cl⋯H/H⋯Cl interactions appear as two symmetrical broad wings with d_e + d_i ≃ 2.85 Å and contribute 33.6% to the Hirshfeld surface (Fig. 5b). Another significant reciprocal interaction (H⋯H) with a contribution of 27.9% is present as broad symmetrical spikes at diagonal axes d_e + d_i ≃ 2.2 Å (Fig. 5c). The pair of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C contacts (Tables 2 and 3, Fig. 5d; 17.6% contribution to the Hirshfeld surface), have tips at d_e + d_i ≃ 2.80 Å. The Cl⋯Cl contacts, Fig. 5e (5.7% contribution), have an arrow-shaped distribution of points with the tip at d_e = d_i = 3.50 Å.

Table 2
Summary of short interatomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
(C2) H2A⋯N3A (C11A)	2.68	(x, y, z)
(C4) Cl1⋯Cl1B (C4B)	3.5403 (11)	(2 − x, 2 − y, 1 − z)
(C14) Cl2⋯Cl1 (C4)	3.6580 (11)	(2 − x, 1 − y, 2 − z)
(C13) H13A⋯Cl2 (C14)	3.10	(2 − x, −y, 2 − z)
(C14) Cl3⋯H5BA (C5B)	2.95	(x, −1 + y, 1 + z)
(C9) H9A⋯H15D (C15A)	2.60	(1 − x, −y, 2 − z)
(C15) H15C⋯Cl3 (C14)	3.00	(1 − x, −1 − y, 2 − z)
(C4) C5⋯H12A (C12)	2.95	(x, 1 + y, z)
(C6A) H6AA⋯H12C (C12B)	2.54	(x, y, z)
(C5A) H5AA⋯Cl2A (C14A)	3.10	(1 − x, 1 − y, 1 − z)
(C9A) H9AA⋯N2B (N1B)	2.92	(1 − x, 1 − y, 1 − z)
(C11A) N3A⋯H2A (C2)	2.68	(x, y, z)
(C14A) Cl3A⋯H16E (C16A)	3.09	(x, 1 + y, z)
(C14A) Cl3A⋯Cl1B (C4B)	3.6816 (11)	(2 − x, 2 − y, 1 − z)
(C4A) C5A⋯H15G (C15B)	2.97	(−1 + x, y, z)
(C3A) H3AA⋯H16I (C16B)	2.49	(1 − x, −y, 1 − z)
(C15A) H15D⋯H9A (C9)	2.60	(1 − x, −y, 2 − z)
(C12A) H12B⋯C4B (Cl1B)	2.98	(2 − x, 1 − y, 1 − z)
(C4B) Cl1B⋯Cl1 (C4)	3.5403 (11)	(2 − x, 2 − y, 1 − z)
(C4B) Cl1B⋯Cl3A (C14A)	3.6816 (11)	(2 − x, 2 − y, 1 − z)
(Cl1B) C4B⋯H12B (C12A)	2.98	(2 − x, 1 − y, 1 − z)
(C16B) H16I⋯H3AA (C3A)	2.49	(1 − x, −y, 1 − z)
(N1B) N2B⋯H9AA (C9A)	2.92	(1 − x, 1 − y, 1 − z)
(C8B) C9B⋯H3BA (C3B)	2.92	(x, −1 + y, z)
(C15B) H15G⋯C5A (C4A)	2.97	(1 + x, y, z)
(C15B) H15I⋯H2BA (C2B)	2.37	(2 − x, 1 − y, 1 − z)
(C12B) H12C⋯H6AA (C6A)	2.54	(x, y, z)
(C5B) H5BA⋯Cl3 (C14)	2.95	(x, 1 + y, −1 + z)

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Cl₃N₃
M_r	354.65
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.7515 (5), 9.8203 (5), 26.6696 (16)
α, β, γ (°)	92.338 (2), 91.212 (2), 94.048 (2)
V (Å³)	2544.7 (2)
Z	6
Radiation type	Mo Kα
μ (mm⁻¹)	0.54
Crystal size (mm)	0.24 × 0.15 × 0.09

Data collection
Diffractometer	Bruker APEXII PHOTON 100 detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.894, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	40829, 9634, 6689
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.01
No. of reflections	9634
No. of parameters	601
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30
Computer programs: APEX3 and SAINT (Bruker, 2007 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), OLEX2 (Dolomanov et al., 2009 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Figure 5
Fingerprint plots representative of specific interatomic contacts in the title compound (symmetry-independent molecules Mol-N1, Mol-N1A, Mol-N1B and overall), (a) for all interactions, and delineated into (b) Cl⋯H/H⋯Cl, (c) H⋯H, (d) C⋯H/H⋯C and (e) Cl⋯Cl interactions.

The other weak intermolecular interactions, viz. Cl⋯C/C⋯Cl (5.4%), N⋯H/H⋯N (4.7%), C⋯C (1.7%), Cl⋯N/N⋯Cl (1.6%), N⋯C/C⋯N (1.0%) and N⋯N (0.8%) contacts, show only small contributions and thus have a negligible effect on the packing.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, November 2018; Groom et al., 2016 ) for structures having an (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene skeleton gave 25 hits, of which six closely resemble the title compound, viz. 1-(4-bromophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (CSD refcode HONBOE; Akkurt et al., 2019 ), 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (HONBUK; Akkurt et al., 2019), 1-(4-chlorophenyl)-2-[2,2-dichloro-1-(4-fluorophenyl)ethenyl]diazene (HODQAV; Shixaliyev et al., 2019 ), 1-[2,2-dichloro-1-(4-nitrophenyl)ethenyl]-2-(4-fluorophenyl)diazene (XIZREG; Atioğlu et al., 2019 ), 1,1-[methylenebis(4,1-phenylene)]bis[(2,2-dichloro-1-(4-nitrophenyl)ethenyl]diazene (LEQXIR; Shixaliyev et al., 2018 ), 1,1-[methylenebis(4,1-phenylene)]bis{[2,2-dichloro-1-(4-chlorophenyl) ethenyl]diazene} (LEQXOX; Shixaliyev et al., 2018).

In the crystal structures of HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. Molecules are linked through weak X⋯Cl contacts [X = Br for HONBOE, and Cl for HONBUK], C—H⋯Cl and C—Cl⋯π interactions into sheets parallel to (001). Additional van der Waals interactions consolidate the three-dimensional packing. In the crystal of HODQAV, molecules are stacked in columns along [100] via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further stabilized by short Cl⋯Cl contacts. In XIZREG, molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along [001]. The crystal packing is further stabilized by C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In the crystal of LEQXIR, C—H⋯N and C—H⋯O hydrogen bonds and Cl⋯O contacts were found, and in LEQXOX, C—H⋯N and Cl⋯Cl contacts are observed.

5. Synthesis and crystallization

The title compound was synthesized according to a reported literature protocol (Maharramov et al., 2018). A 20 ml screw-neck vial was charged with DMSO (10 ml), (E)-4-[(2-(4-chlorophenyl)hydrazineylidene]methyl)-N,N-dimethylaniline (274 mg, 1 mmol), tetramethylethylenediamine (TMEDA) (295 mg, 2.5 mmol), CuCl (2 mg, 0.02 mmol) and CCl₄ (20 mmol, 10 equiv). After 1–3 h (until TLC analysis showed complete consumption of the corresponding Schiff base), the reaction mixture was poured into a ∼0.01 M solution of HCl (100 mL, pH = ∼2–3) and extracted with dichloromethane (3 × 20 ml). The combined organic phase was washed with water (3 x 50 ml), brine (30 ml), dried over anhydrous Na₂SO₄ and concentrated in vacuo in a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1) to give an orange solid. Yield: 72%; mp 408 K. Analysis: calculated for C₁₆H₁₄Cl₃N₃: C 54.19, H 3.98, N 11.85; found: C 54.08, H 3.91, N 11.82%. ¹H NMR (300 MHz, CDCl₃) δ 3.05 (6H, NMe₂), 6.79–7.79 (8H, Ar). ¹³C NMR (75 MHz, CDCl₃) δ 152.41, 151.45, 150.29, 137.26, 135.11, 131.08, 129.27, 124.50, 119.11, 111.48, 40.29. ESI–MS: m/z: 355.48 [M + H]⁺.

Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were refined using a riding model with d(C—H) = 0.93 Å, U_i_so(H) = 1.2U_eq(C) for aromatic H atoms, and 0.96 Å, U_iso(H) = 1.5U_eq(C) for methyl H atoms. Owing to poor agreement between observed and calculated intensities, five outliers ( $[\overline{11}]$ 0 4), (4 $[\overline{10}]$ 13), ( $[\overline{5}]$ 8 8), ( $[\overline{7}]$ 2 18) and (1 8 14) were omitted in the final cycles of refinement.

Supporting information

CCDC reference: 2007970

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007549/wm5554sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007549/wm5554Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020007549/wm5554Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: PLATON (Spek, 2020), publCIF (Westrip, 2010).

4-{2,2-Dichloro-1-[(E)-(4-chlorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline top

Crystal data top

C₁₆H₁₄Cl₃N₃	Z = 6
M_r = 354.65	F(000) = 1092
Triclinic, P1	D_x = 1.389 Mg m⁻³
a = 9.7515 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8203 (5) Å	Cell parameters from 9939 reflections
c = 26.6696 (16) Å	θ = 2.3–25.6°
α = 92.338 (2)°	µ = 0.54 mm⁻¹
β = 91.212 (2)°	T = 296 K
γ = 94.048 (2)°	Plate, orange
V = 2544.7 (2) Å³	0.24 × 0.15 × 0.09 mm

Data collection top

Bruker APEXII PHOTON 100 detector diffractometer	6689 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.056
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 25.7°, θ_min = 2.3°
T_min = 0.894, T_max = 0.946	h = −11→11
40829 measured reflections	k = −11→11
9634 independent reflections	l = −32→32

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.050P)² + 0.8216P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
9634 reflections	Δρ_max = 0.29 e Å⁻³
601 parameters	Δρ_min = −0.30 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
C1	0.8482 (2)	0.1999 (2)	0.93028 (8)	0.0452 (5)
C2	0.8218 (2)	0.1942 (2)	0.87896 (8)	0.0546 (6)
H2A	0.774145	0.117448	0.863853	0.066*
C3	0.8656 (3)	0.3016 (2)	0.85007 (9)	0.0572 (6)
H3A	0.848414	0.297623	0.815595	0.069*
C4	0.9351 (2)	0.4144 (2)	0.87313 (9)	0.0524 (5)
C5	0.9607 (2)	0.4232 (2)	0.92419 (9)	0.0539 (6)
H5A	1.006727	0.501099	0.939152	0.065*
C6	0.9173 (2)	0.3156 (2)	0.95289 (8)	0.0511 (5)
H6A	0.934411	0.320453	0.987379	0.061*
C7	0.7902 (2)	−0.0305 (2)	1.02733 (8)	0.0475 (5)
C8	0.7076 (2)	−0.1457 (2)	1.00137 (8)	0.0445 (5)
C9	0.5679 (2)	−0.1675 (2)	1.00872 (9)	0.0534 (6)
H9A	0.526051	−0.111602	1.031902	0.064*
C10	0.4892 (2)	−0.2699 (2)	0.98260 (9)	0.0557 (6)
H10A	0.395461	−0.281093	0.988356	0.067*
C11	0.5471 (2)	−0.3571 (2)	0.94773 (8)	0.0498 (5)
C12	0.6895 (2)	−0.3368 (2)	0.94155 (9)	0.0519 (5)
H12A	0.732733	−0.394639	0.919443	0.062*
C13	0.7660 (2)	−0.2337 (2)	0.96741 (8)	0.0507 (5)
H13A	0.859983	−0.222405	0.962023	0.061*
C14	0.8254 (2)	−0.0283 (2)	1.07589 (8)	0.0509 (5)
C15	0.3225 (3)	−0.4714 (3)	0.92575 (14)	0.0888 (9)
H15A	0.283755	−0.384431	0.924067	0.133*
H15B	0.304255	−0.508699	0.957852	0.133*
H15C	0.281807	−0.532564	0.899690	0.133*
C16	0.5316 (3)	−0.5541 (3)	0.88809 (12)	0.0829 (8)
H16A	0.588830	−0.508824	0.864106	0.124*
H16B	0.461159	−0.612219	0.870729	0.124*
H16C	0.586559	−0.608226	0.908655	0.124*
N1	0.79963 (19)	0.08299 (18)	0.95616 (7)	0.0504 (4)
N2	0.83684 (19)	0.08700 (19)	1.00163 (7)	0.0508 (4)
N3	0.4692 (2)	−0.4541 (2)	0.91918 (9)	0.0725 (6)
Cl1	0.99248 (9)	0.55056 (8)	0.83780 (3)	0.0881 (3)
Cl2	0.91333 (8)	0.10675 (7)	1.10783 (2)	0.0745 (2)
Cl3	0.78721 (7)	−0.16465 (7)	1.11246 (2)	0.06280 (17)
C1A	0.4229 (2)	0.1795 (2)	0.57132 (8)	0.0498 (5)
C2A	0.3627 (3)	0.0499 (3)	0.56121 (9)	0.0640 (6)
H2AA	0.357155	−0.012520	0.586525	0.077*
C3A	0.3104 (3)	0.0118 (3)	0.51352 (11)	0.0718 (7)
H3AA	0.268621	−0.075308	0.506822	0.086*
C4A	0.3211 (3)	0.1042 (3)	0.47640 (9)	0.0646 (7)
C5A	0.3798 (3)	0.2340 (3)	0.48587 (9)	0.0670 (7)
H5AA	0.385665	0.295854	0.460393	0.080*
C6A	0.4299 (2)	0.2718 (3)	0.53333 (9)	0.0593 (6)
H6AA	0.468889	0.360025	0.540009	0.071*
C7A	0.6011 (2)	0.3445 (2)	0.67585 (8)	0.0470 (5)
C8A	0.5983 (2)	0.2358 (2)	0.71298 (8)	0.0454 (5)
C9A	0.4996 (3)	0.2286 (3)	0.74897 (9)	0.0592 (6)
H9AA	0.434165	0.293029	0.749979	0.071*
C10A	0.4954 (3)	0.1287 (3)	0.78346 (9)	0.0607 (6)
H10B	0.426667	0.126346	0.807108	0.073*
C11A	0.5920 (2)	0.0304 (2)	0.78387 (8)	0.0458 (5)
C12A	0.6903 (2)	0.0377 (2)	0.74676 (9)	0.0563 (6)
H12B	0.755564	−0.026818	0.745152	0.068*
C13A	0.6926 (2)	0.1388 (3)	0.71237 (9)	0.0570 (6)
H13B	0.759922	0.141251	0.688154	0.068*
C14A	0.6685 (2)	0.4666 (2)	0.68521 (9)	0.0545 (6)
C15A	0.4881 (4)	−0.0761 (3)	0.85675 (12)	0.0900 (10)
H15D	0.496807	0.005235	0.878115	0.135*
H15E	0.500050	−0.154259	0.876465	0.135*
H15F	0.398498	−0.084793	0.840832	0.135*
C16A	0.6869 (3)	−0.1722 (3)	0.81753 (12)	0.0777 (8)
H16D	0.778592	−0.131172	0.822915	0.117*
H16E	0.680026	−0.219876	0.785322	0.117*
H16F	0.666243	−0.235499	0.843298	0.117*
N1A	0.47860 (19)	0.2058 (2)	0.62087 (7)	0.0521 (5)
N2A	0.53735 (18)	0.3236 (2)	0.62771 (7)	0.0494 (4)
N3A	0.5912 (2)	−0.0680 (2)	0.81912 (7)	0.0600 (5)
Cl1A	0.25859 (11)	0.05792 (10)	0.41636 (3)	0.1059 (3)
Cl2A	0.67447 (7)	0.59912 (7)	0.64516 (3)	0.07071 (19)
Cl3A	0.76185 (9)	0.50455 (7)	0.73961 (3)	0.0824 (2)
C1B	0.8791 (2)	0.7795 (2)	0.30878 (8)	0.0534 (5)
C2B	0.9091 (3)	0.8881 (3)	0.34212 (10)	0.0732 (8)
H2BA	0.907166	0.874525	0.376414	0.088*
C3B	0.9419 (3)	1.0168 (3)	0.32550 (10)	0.0753 (8)
H3BA	0.961150	1.090166	0.348319	0.090*
C4B	0.9458 (3)	1.0357 (3)	0.27501 (9)	0.0580 (6)
C5B	0.9201 (3)	0.9284 (3)	0.24133 (10)	0.0740 (8)
H5BA	0.925262	0.942155	0.207103	0.089*
C6B	0.8865 (3)	0.8002 (3)	0.25782 (9)	0.0710 (7)
H6BA	0.868609	0.727134	0.234787	0.085*
C7B	0.7467 (2)	0.4383 (2)	0.31889 (9)	0.0555 (6)
C8B	0.7881 (2)	0.4045 (2)	0.37050 (9)	0.0496 (5)
C9B	0.9197 (2)	0.3708 (3)	0.38160 (9)	0.0582 (6)
H9BA	0.983240	0.368642	0.356103	0.070*
C10B	0.9597 (2)	0.3403 (3)	0.42917 (10)	0.0609 (6)
H10C	1.048949	0.315983	0.434946	0.073*
C11B	0.8701 (2)	0.3447 (2)	0.46910 (9)	0.0527 (5)
C12B	0.7377 (3)	0.3785 (3)	0.45733 (11)	0.0753 (8)
H12C	0.673596	0.382026	0.482612	0.090*
C13B	0.6991 (3)	0.4069 (3)	0.40940 (11)	0.0752 (8)
H13C	0.609160	0.428491	0.403106	0.090*
C14B	0.6730 (3)	0.3507 (3)	0.28757 (10)	0.0675 (7)
C15B	1.0461 (3)	0.2825 (4)	0.52857 (13)	0.1025 (12)
H15G	1.111103	0.339811	0.510989	0.154*
H15H	1.054616	0.188677	0.518344	0.154*
H15I	1.064191	0.294754	0.564051	0.154*
C16B	0.8219 (3)	0.3376 (3)	0.55890 (11)	0.0845 (9)
H16G	0.785760	0.425916	0.557867	0.127*
H16H	0.873595	0.331524	0.589666	0.127*
H16I	0.747446	0.268088	0.557111	0.127*
N1B	0.8435 (2)	0.6513 (2)	0.32988 (7)	0.0580 (5)
N2B	0.7831 (2)	0.5669 (2)	0.29885 (7)	0.0582 (5)
N3B	0.9100 (2)	0.3187 (3)	0.51715 (8)	0.0759 (7)
Cl1B	0.98597 (9)	1.19767 (8)	0.25356 (3)	0.0849 (2)
Cl2B	0.62580 (10)	0.38856 (10)	0.22766 (3)	0.1031 (3)
Cl3B	0.61794 (9)	0.18941 (8)	0.30326 (3)	0.0901 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0467 (12)	0.0453 (12)	0.0428 (11)	−0.0008 (9)	−0.0046 (9)	0.0019 (9)
C2	0.0661 (15)	0.0469 (13)	0.0481 (13)	−0.0105 (11)	−0.0127 (11)	0.0010 (10)
C3	0.0721 (16)	0.0548 (14)	0.0428 (12)	−0.0086 (11)	−0.0103 (11)	0.0064 (10)
C4	0.0547 (13)	0.0455 (12)	0.0560 (14)	−0.0045 (10)	−0.0061 (11)	0.0098 (10)
C5	0.0580 (14)	0.0462 (13)	0.0553 (14)	−0.0055 (10)	−0.0114 (11)	−0.0032 (10)
C6	0.0567 (14)	0.0524 (13)	0.0424 (12)	−0.0024 (10)	−0.0075 (10)	−0.0024 (10)
C7	0.0461 (12)	0.0515 (13)	0.0446 (12)	−0.0005 (10)	0.0033 (9)	0.0038 (10)
C8	0.0452 (12)	0.0471 (12)	0.0410 (11)	−0.0005 (9)	−0.0003 (9)	0.0058 (9)
C9	0.0513 (13)	0.0570 (14)	0.0520 (13)	0.0034 (11)	0.0091 (10)	−0.0011 (11)
C10	0.0423 (12)	0.0613 (14)	0.0627 (14)	−0.0025 (10)	0.0053 (11)	0.0012 (12)
C11	0.0527 (13)	0.0430 (12)	0.0535 (13)	0.0019 (10)	−0.0043 (10)	0.0066 (10)
C12	0.0535 (14)	0.0487 (13)	0.0541 (13)	0.0097 (10)	0.0019 (10)	−0.0009 (10)
C13	0.0428 (12)	0.0542 (13)	0.0556 (13)	0.0053 (10)	0.0030 (10)	0.0055 (11)
C14	0.0527 (13)	0.0564 (13)	0.0422 (12)	−0.0051 (10)	0.0016 (10)	0.0009 (10)
C15	0.0653 (18)	0.080 (2)	0.116 (3)	−0.0120 (15)	−0.0196 (17)	−0.0149 (18)
C16	0.097 (2)	0.0678 (18)	0.0799 (19)	−0.0049 (16)	−0.0045 (16)	−0.0200 (15)
N1	0.0551 (11)	0.0494 (11)	0.0456 (11)	−0.0032 (8)	−0.0037 (8)	0.0037 (8)
N2	0.0545 (11)	0.0534 (11)	0.0434 (10)	−0.0046 (9)	−0.0012 (8)	0.0041 (8)
N3	0.0592 (13)	0.0619 (13)	0.0931 (17)	−0.0044 (10)	−0.0078 (12)	−0.0172 (12)
Cl1	0.1108 (6)	0.0707 (4)	0.0783 (5)	−0.0343 (4)	−0.0217 (4)	0.0297 (4)
Cl2	0.0924 (5)	0.0755 (4)	0.0505 (3)	−0.0260 (4)	−0.0073 (3)	−0.0010 (3)
Cl3	0.0757 (4)	0.0640 (4)	0.0483 (3)	−0.0032 (3)	0.0018 (3)	0.0122 (3)
C1A	0.0444 (12)	0.0593 (14)	0.0454 (12)	0.0022 (10)	−0.0015 (9)	0.0029 (10)
C2A	0.0755 (17)	0.0601 (15)	0.0561 (15)	0.0021 (13)	−0.0064 (12)	0.0062 (12)
C3A	0.0817 (19)	0.0587 (16)	0.0729 (18)	0.0033 (13)	−0.0159 (14)	−0.0100 (14)
C4A	0.0644 (16)	0.0774 (18)	0.0519 (14)	0.0146 (13)	−0.0122 (12)	−0.0087 (13)
C5A	0.0687 (17)	0.0817 (19)	0.0502 (14)	0.0011 (14)	−0.0101 (12)	0.0115 (13)
C6A	0.0601 (15)	0.0648 (15)	0.0511 (14)	−0.0068 (12)	−0.0070 (11)	0.0054 (11)
C7A	0.0484 (12)	0.0537 (13)	0.0393 (11)	0.0049 (10)	−0.0018 (9)	0.0048 (9)
C8A	0.0477 (12)	0.0499 (12)	0.0381 (11)	0.0014 (10)	−0.0023 (9)	0.0003 (9)
C9A	0.0627 (15)	0.0602 (15)	0.0577 (14)	0.0197 (12)	0.0111 (12)	0.0090 (12)
C10A	0.0650 (15)	0.0648 (15)	0.0552 (14)	0.0146 (12)	0.0180 (12)	0.0106 (12)
C11A	0.0514 (13)	0.0446 (12)	0.0403 (11)	−0.0015 (9)	−0.0049 (9)	−0.0003 (9)
C12A	0.0567 (14)	0.0564 (14)	0.0581 (14)	0.0158 (11)	0.0053 (11)	0.0069 (11)
C13A	0.0566 (14)	0.0644 (15)	0.0521 (13)	0.0110 (12)	0.0118 (11)	0.0103 (11)
C14A	0.0598 (14)	0.0541 (14)	0.0492 (13)	0.0008 (11)	−0.0056 (11)	0.0072 (10)
C15A	0.117 (3)	0.080 (2)	0.0776 (19)	0.0204 (18)	0.0359 (19)	0.0309 (16)
C16A	0.095 (2)	0.0595 (16)	0.0822 (19)	0.0187 (15)	0.0033 (16)	0.0202 (14)
N1A	0.0521 (11)	0.0590 (12)	0.0448 (10)	−0.0002 (9)	−0.0017 (8)	0.0048 (9)
N2A	0.0486 (10)	0.0559 (11)	0.0437 (10)	0.0022 (9)	−0.0021 (8)	0.0050 (8)
N3A	0.0739 (14)	0.0538 (12)	0.0542 (11)	0.0107 (10)	0.0075 (10)	0.0126 (9)
Cl1A	0.1388 (8)	0.1108 (7)	0.0653 (5)	0.0166 (6)	−0.0417 (5)	−0.0205 (4)
Cl2A	0.0811 (4)	0.0591 (4)	0.0719 (4)	−0.0015 (3)	−0.0089 (3)	0.0195 (3)
Cl3A	0.1102 (6)	0.0644 (4)	0.0681 (4)	−0.0145 (4)	−0.0345 (4)	0.0034 (3)
C1B	0.0573 (14)	0.0551 (14)	0.0474 (13)	0.0008 (11)	−0.0043 (10)	0.0054 (10)
C2B	0.117 (2)	0.0571 (16)	0.0454 (13)	0.0029 (15)	−0.0056 (14)	0.0047 (12)
C3B	0.118 (2)	0.0528 (15)	0.0550 (15)	0.0041 (15)	0.0002 (15)	−0.0007 (12)
C4B	0.0583 (14)	0.0583 (14)	0.0585 (15)	0.0047 (11)	0.0070 (11)	0.0125 (12)
C5B	0.093 (2)	0.0810 (19)	0.0453 (14)	−0.0183 (16)	0.0008 (13)	0.0091 (13)
C6B	0.091 (2)	0.0711 (17)	0.0465 (14)	−0.0179 (14)	−0.0012 (13)	−0.0052 (12)
C7B	0.0515 (13)	0.0519 (13)	0.0622 (15)	0.0031 (10)	−0.0065 (11)	−0.0017 (11)
C8B	0.0470 (13)	0.0444 (12)	0.0568 (13)	0.0016 (9)	−0.0025 (10)	0.0011 (10)
C9B	0.0513 (14)	0.0680 (16)	0.0565 (14)	0.0114 (11)	0.0065 (11)	0.0015 (12)
C10B	0.0452 (13)	0.0731 (17)	0.0660 (16)	0.0132 (11)	0.0021 (11)	0.0061 (13)
C11B	0.0482 (13)	0.0515 (13)	0.0590 (14)	0.0045 (10)	0.0043 (11)	0.0063 (11)
C12B	0.0498 (15)	0.111 (2)	0.0682 (17)	0.0185 (15)	0.0148 (13)	0.0153 (16)
C13B	0.0464 (14)	0.105 (2)	0.0774 (19)	0.0201 (14)	0.0014 (13)	0.0136 (16)
C14B	0.0640 (16)	0.0637 (16)	0.0731 (17)	0.0020 (12)	−0.0146 (13)	−0.0041 (13)
C15B	0.083 (2)	0.152 (3)	0.079 (2)	0.037 (2)	−0.0014 (17)	0.037 (2)
C16B	0.095 (2)	0.099 (2)	0.0606 (17)	0.0094 (18)	0.0140 (16)	−0.0004 (16)
N1B	0.0681 (13)	0.0522 (12)	0.0527 (11)	0.0000 (10)	−0.0072 (10)	0.0010 (9)
N2B	0.0605 (12)	0.0570 (12)	0.0560 (12)	0.0011 (9)	−0.0080 (9)	−0.0002 (10)
N3B	0.0611 (13)	0.1092 (19)	0.0611 (13)	0.0214 (13)	0.0082 (11)	0.0188 (13)
Cl1B	0.1076 (6)	0.0658 (4)	0.0832 (5)	0.0017 (4)	0.0239 (4)	0.0219 (4)
Cl2B	0.1230 (7)	0.0965 (6)	0.0848 (5)	−0.0064 (5)	−0.0471 (5)	−0.0079 (4)
Cl3B	0.0889 (5)	0.0609 (4)	0.1158 (6)	−0.0135 (4)	−0.0188 (5)	−0.0088 (4)

Geometric parameters (Å, º) top

C1—C2	1.386 (3)	C10A—C11A	1.395 (3)
C1—C6	1.388 (3)	C10A—H10B	0.9300
C1—N1	1.421 (3)	C11A—N3A	1.376 (3)
C2—C3	1.380 (3)	C11A—C12A	1.393 (3)
C2—H2A	0.9300	C12A—C13A	1.378 (3)
C3—C4	1.373 (3)	C12A—H12B	0.9300
C3—H3A	0.9300	C13A—H13B	0.9300
C4—C5	1.377 (3)	C14A—Cl3A	1.710 (2)
C4—Cl1	1.734 (2)	C14A—Cl2A	1.715 (2)
C5—C6	1.378 (3)	C15A—N3A	1.436 (3)
C5—H5A	0.9300	C15A—H15D	0.9600
C6—H6A	0.9300	C15A—H15E	0.9600
C7—C14	1.332 (3)	C15A—H15F	0.9600
C7—N2	1.418 (3)	C16A—N3A	1.433 (3)
C7—C8	1.481 (3)	C16A—H16D	0.9600
C8—C9	1.383 (3)	C16A—H16E	0.9600
C8—C13	1.385 (3)	C16A—H16F	0.9600
C9—C10	1.377 (3)	N1A—N2A	1.259 (3)
C9—H9A	0.9300	C1B—C2B	1.372 (3)
C10—C11	1.393 (3)	C1B—C6B	1.385 (3)
C10—H10A	0.9300	C1B—N1B	1.423 (3)
C11—N3	1.370 (3)	C2B—C3B	1.375 (4)
C11—C12	1.403 (3)	C2B—H2BA	0.9300
C12—C13	1.368 (3)	C3B—C4B	1.368 (4)
C12—H12A	0.9300	C3B—H3BA	0.9300
C13—H13A	0.9300	C4B—C5B	1.362 (4)
C14—Cl3	1.713 (2)	C4B—Cl1B	1.734 (2)
C14—Cl2	1.714 (2)	C5B—C6B	1.370 (4)
C15—N3	1.445 (4)	C5B—H5BA	0.9300
C15—H15A	0.9600	C6B—H6BA	0.9300
C15—H15B	0.9600	C7B—C14B	1.335 (3)
C15—H15C	0.9600	C7B—N2B	1.417 (3)
C16—N3	1.436 (3)	C7B—C8B	1.483 (3)
C16—H16A	0.9600	C8B—C13B	1.367 (3)
C16—H16B	0.9600	C8B—C9B	1.378 (3)
C16—H16C	0.9600	C9B—C10B	1.370 (3)
N1—N2	1.257 (2)	C9B—H9BA	0.9300
C1A—C2A	1.378 (3)	C10B—C11B	1.393 (3)
C1A—C6A	1.386 (3)	C10B—H10C	0.9300
C1A—N1A	1.425 (3)	C11B—N3B	1.370 (3)
C2A—C3A	1.387 (4)	C11B—C12B	1.389 (3)
C2A—H2AA	0.9300	C12B—C13B	1.370 (4)
C3A—C4A	1.370 (4)	C12B—H12C	0.9300
C3A—H3AA	0.9300	C13B—H13C	0.9300
C4A—C5A	1.371 (4)	C14B—Cl3B	1.707 (3)
C4A—Cl1A	1.733 (3)	C14B—Cl2B	1.716 (3)
C5A—C6A	1.374 (3)	C15B—N3B	1.428 (4)
C5A—H5AA	0.9300	C15B—H15G	0.9600
C6A—H6AA	0.9300	C15B—H15H	0.9600
C7A—C14A	1.338 (3)	C15B—H15I	0.9600
C7A—N2A	1.415 (3)	C16B—N3B	1.435 (3)
C7A—C8A	1.484 (3)	C16B—H16G	0.9600
C8A—C13A	1.370 (3)	C16B—H16H	0.9600
C8A—C9A	1.374 (3)	C16B—H16I	0.9600
C9A—C10A	1.371 (3)	N1B—N2B	1.255 (3)
C9A—H9AA	0.9300

C2—C1—C6	119.6 (2)	N3A—C11A—C12A	121.6 (2)
C2—C1—N1	115.70 (19)	N3A—C11A—C10A	122.0 (2)
C6—C1—N1	124.67 (19)	C12A—C11A—C10A	116.4 (2)
C3—C2—C1	120.6 (2)	C13A—C12A—C11A	121.3 (2)
C3—C2—H2A	119.7	C13A—C12A—H12B	119.4
C1—C2—H2A	119.7	C11A—C12A—H12B	119.4
C4—C3—C2	118.8 (2)	C8A—C13A—C12A	121.6 (2)
C4—C3—H3A	120.6	C8A—C13A—H13B	119.2
C2—C3—H3A	120.6	C12A—C13A—H13B	119.2
C3—C4—C5	121.6 (2)	C7A—C14A—Cl3A	122.02 (18)
C3—C4—Cl1	119.95 (18)	C7A—C14A—Cl2A	125.13 (18)
C5—C4—Cl1	118.43 (18)	Cl3A—C14A—Cl2A	112.84 (14)
C4—C5—C6	119.4 (2)	N3A—C15A—H15D	109.5
C4—C5—H5A	120.3	N3A—C15A—H15E	109.5
C6—C5—H5A	120.3	H15D—C15A—H15E	109.5
C5—C6—C1	120.0 (2)	N3A—C15A—H15F	109.5
C5—C6—H6A	120.0	H15D—C15A—H15F	109.5
C1—C6—H6A	120.0	H15E—C15A—H15F	109.5
C14—C7—N2	115.2 (2)	N3A—C16A—H16D	109.5
C14—C7—C8	123.2 (2)	N3A—C16A—H16E	109.5
N2—C7—C8	121.58 (18)	H16D—C16A—H16E	109.5
C9—C8—C13	117.1 (2)	N3A—C16A—H16F	109.5
C9—C8—C7	121.4 (2)	H16D—C16A—H16F	109.5
C13—C8—C7	121.44 (19)	H16E—C16A—H16F	109.5
C10—C9—C8	121.7 (2)	N2A—N1A—C1A	113.44 (18)
C10—C9—H9A	119.2	N1A—N2A—C7A	112.75 (18)
C8—C9—H9A	119.2	C11A—N3A—C16A	121.3 (2)
C9—C10—C11	121.4 (2)	C11A—N3A—C15A	121.2 (2)
C9—C10—H10A	119.3	C16A—N3A—C15A	117.4 (2)
C11—C10—H10A	119.3	C2B—C1B—C6B	119.0 (2)
N3—C11—C10	122.3 (2)	C2B—C1B—N1B	116.4 (2)
N3—C11—C12	121.2 (2)	C6B—C1B—N1B	124.6 (2)
C10—C11—C12	116.5 (2)	C1B—C2B—C3B	120.9 (2)
C13—C12—C11	121.3 (2)	C1B—C2B—H2BA	119.6
C13—C12—H12A	119.3	C3B—C2B—H2BA	119.6
C11—C12—H12A	119.3	C4B—C3B—C2B	119.2 (3)
C12—C13—C8	121.9 (2)	C4B—C3B—H3BA	120.4
C12—C13—H13A	119.0	C2B—C3B—H3BA	120.4
C8—C13—H13A	119.0	C5B—C4B—C3B	120.8 (2)
C7—C14—Cl3	122.13 (18)	C5B—C4B—Cl1B	119.55 (19)
C7—C14—Cl2	124.47 (18)	C3B—C4B—Cl1B	119.7 (2)
Cl3—C14—Cl2	113.40 (13)	C4B—C5B—C6B	120.1 (2)
N3—C15—H15A	109.5	C4B—C5B—H5BA	120.0
N3—C15—H15B	109.5	C6B—C5B—H5BA	120.0
H15A—C15—H15B	109.5	C5B—C6B—C1B	120.0 (2)
N3—C15—H15C	109.5	C5B—C6B—H6BA	120.0
H15A—C15—H15C	109.5	C1B—C6B—H6BA	120.0
H15B—C15—H15C	109.5	C14B—C7B—N2B	114.6 (2)
N3—C16—H16A	109.5	C14B—C7B—C8B	123.1 (2)
N3—C16—H16B	109.5	N2B—C7B—C8B	122.3 (2)
H16A—C16—H16B	109.5	C13B—C8B—C9B	116.7 (2)
N3—C16—H16C	109.5	C13B—C8B—C7B	122.1 (2)
H16A—C16—H16C	109.5	C9B—C8B—C7B	121.2 (2)
H16B—C16—H16C	109.5	C10B—C9B—C8B	121.8 (2)
N2—N1—C1	113.53 (18)	C10B—C9B—H9BA	119.1
N1—N2—C7	113.61 (18)	C8B—C9B—H9BA	119.1
C11—N3—C16	121.5 (2)	C9B—C10B—C11B	121.7 (2)
C11—N3—C15	120.0 (2)	C9B—C10B—H10C	119.1
C16—N3—C15	117.8 (2)	C11B—C10B—H10C	119.1
C2A—C1A—C6A	119.2 (2)	N3B—C11B—C12B	121.9 (2)
C2A—C1A—N1A	115.7 (2)	N3B—C11B—C10B	122.3 (2)
C6A—C1A—N1A	125.0 (2)	C12B—C11B—C10B	115.8 (2)
C1A—C2A—C3A	120.4 (2)	C13B—C12B—C11B	121.6 (2)
C1A—C2A—H2AA	119.8	C13B—C12B—H12C	119.2
C3A—C2A—H2AA	119.8	C11B—C12B—H12C	119.2
C4A—C3A—C2A	119.2 (3)	C8B—C13B—C12B	122.3 (2)
C4A—C3A—H3AA	120.4	C8B—C13B—H13C	118.8
C2A—C3A—H3AA	120.4	C12B—C13B—H13C	118.8
C3A—C4A—C5A	121.2 (2)	C7B—C14B—Cl3B	123.1 (2)
C3A—C4A—Cl1A	119.9 (2)	C7B—C14B—Cl2B	123.4 (2)
C5A—C4A—Cl1A	118.9 (2)	Cl3B—C14B—Cl2B	113.56 (15)
C4A—C5A—C6A	119.4 (2)	N3B—C15B—H15G	109.5
C4A—C5A—H5AA	120.3	N3B—C15B—H15H	109.5
C6A—C5A—H5AA	120.3	H15G—C15B—H15H	109.5
C5A—C6A—C1A	120.5 (2)	N3B—C15B—H15I	109.5
C5A—C6A—H6AA	119.7	H15G—C15B—H15I	109.5
C1A—C6A—H6AA	119.7	H15H—C15B—H15I	109.5
C14A—C7A—N2A	115.90 (19)	N3B—C16B—H16G	109.5
C14A—C7A—C8A	121.9 (2)	N3B—C16B—H16H	109.5
N2A—C7A—C8A	122.12 (19)	H16G—C16B—H16H	109.5
C13A—C8A—C9A	117.7 (2)	N3B—C16B—H16I	109.5
C13A—C8A—C7A	121.45 (19)	H16G—C16B—H16I	109.5
C9A—C8A—C7A	120.8 (2)	H16H—C16B—H16I	109.5
C10A—C9A—C8A	121.5 (2)	N2B—N1B—C1B	112.63 (19)
C10A—C9A—H9AA	119.2	N1B—N2B—C7B	113.78 (19)
C8A—C9A—H9AA	119.2	C11B—N3B—C15B	121.2 (2)
C9A—C10A—C11A	121.5 (2)	C11B—N3B—C16B	122.0 (2)
C9A—C10A—H10B	119.3	C15B—N3B—C16B	116.6 (2)
C11A—C10A—H10B	119.3

C6—C1—C2—C3	1.1 (4)	N3A—C11A—C12A—C13A	−178.3 (2)
N1—C1—C2—C3	−179.3 (2)	C10A—C11A—C12A—C13A	1.3 (4)
C1—C2—C3—C4	−0.4 (4)	C9A—C8A—C13A—C12A	−0.5 (4)
C2—C3—C4—C5	−0.6 (4)	C7A—C8A—C13A—C12A	−180.0 (2)
C2—C3—C4—Cl1	179.58 (19)	C11A—C12A—C13A—C8A	−0.4 (4)
C3—C4—C5—C6	0.9 (4)	N2A—C7A—C14A—Cl3A	−175.07 (17)
Cl1—C4—C5—C6	−179.27 (18)	C8A—C7A—C14A—Cl3A	2.5 (3)
C4—C5—C6—C1	−0.2 (4)	N2A—C7A—C14A—Cl2A	3.8 (3)
C2—C1—C6—C5	−0.8 (3)	C8A—C7A—C14A—Cl2A	−178.64 (17)
N1—C1—C6—C5	179.7 (2)	C2A—C1A—N1A—N2A	177.3 (2)
C14—C7—C8—C9	74.0 (3)	C6A—C1A—N1A—N2A	−0.3 (3)
N2—C7—C8—C9	−105.6 (2)	C1A—N1A—N2A—C7A	−175.50 (18)
C14—C7—C8—C13	−108.2 (3)	C14A—C7A—N2A—N1A	178.4 (2)
N2—C7—C8—C13	72.2 (3)	C8A—C7A—N2A—N1A	0.8 (3)
C13—C8—C9—C10	−1.6 (3)	C12A—C11A—N3A—C16A	−3.5 (4)
C7—C8—C9—C10	176.3 (2)	C10A—C11A—N3A—C16A	176.9 (3)
C8—C9—C10—C11	0.5 (4)	C12A—C11A—N3A—C15A	−179.0 (3)
C9—C10—C11—N3	−175.9 (2)	C10A—C11A—N3A—C15A	1.4 (4)
C9—C10—C11—C12	1.3 (3)	C6B—C1B—C2B—C3B	2.0 (4)
N3—C11—C12—C13	175.3 (2)	N1B—C1B—C2B—C3B	−178.7 (3)
C10—C11—C12—C13	−2.0 (3)	C1B—C2B—C3B—C4B	−0.7 (5)
C11—C12—C13—C8	1.0 (3)	C2B—C3B—C4B—C5B	−1.1 (4)
C9—C8—C13—C12	0.9 (3)	C2B—C3B—C4B—Cl1B	179.6 (2)
C7—C8—C13—C12	−177.0 (2)	C3B—C4B—C5B—C6B	1.6 (4)
N2—C7—C14—Cl3	−176.21 (16)	Cl1B—C4B—C5B—C6B	−179.1 (2)
C8—C7—C14—Cl3	4.1 (3)	C4B—C5B—C6B—C1B	−0.2 (4)
N2—C7—C14—Cl2	3.1 (3)	C2B—C1B—C6B—C5B	−1.6 (4)
C8—C7—C14—Cl2	−176.55 (17)	N1B—C1B—C6B—C5B	179.2 (3)
C2—C1—N1—N2	173.7 (2)	C14B—C7B—C8B—C13B	−78.7 (3)
C6—C1—N1—N2	−6.7 (3)	N2B—C7B—C8B—C13B	101.5 (3)
C1—N1—N2—C7	−179.12 (18)	C14B—C7B—C8B—C9B	102.2 (3)
C14—C7—N2—N1	−178.7 (2)	N2B—C7B—C8B—C9B	−77.6 (3)
C8—C7—N2—N1	1.0 (3)	C13B—C8B—C9B—C10B	0.4 (4)
C10—C11—N3—C16	−172.1 (2)	C7B—C8B—C9B—C10B	179.5 (2)
C12—C11—N3—C16	10.8 (4)	C8B—C9B—C10B—C11B	−1.4 (4)
C10—C11—N3—C15	−1.9 (4)	C9B—C10B—C11B—N3B	−177.9 (3)
C12—C11—N3—C15	−179.0 (2)	C9B—C10B—C11B—C12B	1.5 (4)
C6A—C1A—C2A—C3A	0.4 (4)	N3B—C11B—C12B—C13B	178.8 (3)
N1A—C1A—C2A—C3A	−177.3 (2)	C10B—C11B—C12B—C13B	−0.6 (4)
C1A—C2A—C3A—C4A	0.9 (4)	C9B—C8B—C13B—C12B	0.6 (4)
C2A—C3A—C4A—C5A	−1.4 (4)	C7B—C8B—C13B—C12B	−178.6 (3)
C2A—C3A—C4A—Cl1A	179.1 (2)	C11B—C12B—C13B—C8B	−0.4 (5)
C3A—C4A—C5A—C6A	0.5 (4)	N2B—C7B—C14B—Cl3B	179.71 (18)
Cl1A—C4A—C5A—C6A	−179.9 (2)	C8B—C7B—C14B—Cl3B	−0.1 (4)
C4A—C5A—C6A—C1A	0.8 (4)	N2B—C7B—C14B—Cl2B	0.3 (3)
C2A—C1A—C6A—C5A	−1.2 (4)	C8B—C7B—C14B—Cl2B	−179.54 (19)
N1A—C1A—C6A—C5A	176.3 (2)	C2B—C1B—N1B—N2B	162.2 (2)
C14A—C7A—C8A—C13A	−92.7 (3)	C6B—C1B—N1B—N2B	−18.5 (3)
N2A—C7A—C8A—C13A	84.7 (3)	C1B—N1B—N2B—C7B	179.93 (19)
C14A—C7A—C8A—C9A	87.8 (3)	C14B—C7B—N2B—N1B	175.0 (2)
N2A—C7A—C8A—C9A	−94.7 (3)	C8B—C7B—N2B—N1B	−5.2 (3)
C13A—C8A—C9A—C10A	0.4 (4)	C12B—C11B—N3B—C15B	179.3 (3)
C7A—C8A—C9A—C10A	179.9 (2)	C10B—C11B—N3B—C15B	−1.3 (4)
C8A—C9A—C10A—C11A	0.6 (4)	C12B—C11B—N3B—C16B	−6.2 (4)
C9A—C10A—C11A—N3A	178.2 (2)	C10B—C11B—N3B—C16B	173.2 (3)
C9A—C10A—C11A—C12A	−1.4 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg4 are the centroids of the C1–C6 and C8A–C13A rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N3A	0.93	2.68	3.597 (3)	167
C5B—H5BA···Cl3ⁱ	0.93	2.95	3.703 (3)	139
C14—Cl3···Cg1ⁱⁱ	1.71 (1)	3.55 (1)	4.083 (2)	96 (1)
C14B—Cl3B···Cg4ⁱⁱⁱ	1.71 (1)	3.85 (1)	5.300 (3)	142 (1)

Symmetry codes: (i) x, y+1, z−1; (ii) −x+2, −y, −z+2; (iii) −x+1, −y, −z+1.

Summary of short interatomic contacts (Å) in the title compound top

Contact	Distance	Symmetry operation
(C2) H2A···N3A (C11A)	2.68	(x, y, z)
(C4) Cl1···Cl1B (C4B)	3.5403 (11)	(2 - x, 2 - y, 1 - z)
(C14) Cl2···Cl1 (C4)	3.6580 (11)	(2 - x, 1 - y, 2 - z)
(C13) H13A···Cl2 (C14)	3.10	(2 - x, -y, 2 - z)
(C14) Cl3···H5BA (C5B)	2.95	(x, -1 + y, 1 + z)
(C9) H9A···H15D (C15A)	2.60	(1 - x, -y, 2 - z)
(C15) H15C···Cl3 (C14)	3.00	(1 - x, -1 - y, 2 - z)
(C4) C5···H12A (C12)	2.95	(x, 1 + y, z)
(C6A) H6AA···H12C (C12B)	2.54	(x, y, z)
(C5A) H5AA···Cl2A (C14A)	3.10	(1 - x, 1 - y, 1 - z)
(C9A) H9AA···N2B (N1B)	2.92	(1 - x, 1 - y, 1 - z)
(C11A) N3A···H2A (C2)	2.68	(x, y, z)
(C14A) Cl3A···H16E (C16A)	3.09	(x, 1 + y, z)
(C14A) Cl3A···Cl1B (C4B)	3.6816 (11)	(2 - x, 2 - y, 1 - z)
(C4A) C5A···H15G (C15B)	2.97	(-1 + x, y, z)
(C3A) H3AA···H16I (C16B)	2.49	(1 - x, -y, 1 - z)
(C15A) H15D···H9A (C9)	2.60	(1 - x, -y, 2 - z)
(C12A) H12B···C4B (Cl1B)	2.98	(2 - x, 1 - y, 1 - z)
(C4B) Cl1B···Cl1 (C4)	3.5403 (11)	(2 - x, 2 - y, 1 - z)
(C4B) Cl1B···Cl3A (C14A)	3.6816 (11)	(2 - x, 2 - y, 1 - z)
(Cl1B) C4B···H12B (C12A)	2.98	(2 - x, 1 - y, 1 - z)
(C16B) H16I···H3AA (C3A)	2.49	(1 - x, -y, 1 - z)
(N1B) N2B···H9AA (C9A)	2.92	(1 - x, 1 - y, 1 - z)
(C8B) C9B···H3BA (C3B)	2.92	(x, -1 + y, z)
(C15B) H15G···C5A (C4A)	2.97	(1 + x, y, z)
(C15B) H15I···H2BA (C2B)	2.37	(2 - x, 1 - y, 1 - z)
(C12B) H12C···H6AA (C6A)	2.54	(x, y, z)
(C5B) H5BA···Cl3 (C14)	2.95	(x, 1 + y, -1 + z)

Funding information

This work was funded by the Science Development Foundation under the President of the Republic of Azerbaijan [grant No. EIF/MQM/Elm-Tehsil-1–2016-1(26)–71/06/4].

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Volume 76| Part 7| July 2020| Pages 1033-1037

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure and Hirshfeld surface analysis of 4-{2,2-di­chloro-1-[(E)-(4-chloro­phen­yl)diazen­yl]ethen­yl}-N,N-di­methyl­aniline

1. Chemical context

2. Structural commentary

3. Supra­molecular features and Hirshfeld surface analysis

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Crystal structure and Hirshfeld surface analysis of 4-{2,2-dichloro-1-[(E)-(4-chlorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline

3. Supramolecular features and Hirshfeld surface analysis