Crystal structure and Hirshfeld surface analysis of (E)-4-{[2,2-di-chloro-1-(4-meth-oxy-phen-yl)ethen-yl]diazen-yl}benzo-nitrile.

In the title compound, C16H11Cl2N3O, the 4-meth-oxy-substituted benzene ring makes a dihedral angle of 41.86 (9)° with the benzene ring of the benzo-nitrile group. In the crystal, mol-ecules are linked into layers parallel to (020) by C-H⋯O contacts and face-to-face π-π stacking inter-actions [centroid-centroid distances = 3.9116 (14) and 3.9118 (14) Å] between symmetry-related aromatic rings along the a-axis direction. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from Cl⋯H/H⋯Cl (22.8%), H⋯H (21.4%), N⋯H/H⋯N (16.1%), C⋯H/H⋯C (14.7%) and C⋯C (9.1%) inter-actions.

Chemical context

Weak inter­actions, such as hydrogen, aerogen, halogen, chalcogen, pnicogen, tetrel and icosa­gen bonds, as well as n–π*, π–π stacking, π–cation, π–anion and hydro­phobic inter­actions, can control or organize the conformation, aggregation, tertiary and quaternary structure of the mol­ecule, its reactivity, stabilization and other properties (Asadov et al., 2016 ▸; Maharramov et al., 2010 ▸; Mahmudov et al., 2013 ▸, 2014a ▸,b ▸, 2015 ▸, 2017a ▸,b ▸, 2019 ▸; Shixaliyev et al., 2013 ▸, 2014 ▸). The functionalization of azo/hydrazone ligands with non-covalent bond-donor or acceptor sites greatly affects their coordination ability and the catalytic activity of the corresponding coordination compounds (Akbari et al., 2017 ▸; Gurbanov et al., 2018 ▸; Karmakar et al., 2016 ▸; Kopylovich et al., 2011a ▸,b ▸; Ma et al., 2017a ▸,b ▸; Mahmoudi et al., 2016 ▸, 2017a ▸,b ▸,c ▸, 2018a ▸,b ▸,c ▸). In our previous work, we have attached chloro atoms to dye mol­ecules, which lead to halogen bonding (Atioğlu et al., 2019 ▸; Maharramov et al., 2018 ▸; Shixaliyev et al., 2018 ▸, 2019 ▸). In a continuation of this work, we have functionalized a new azo dye, (E)-4-{[2,2-di­chloro-1-(4-meth­oxy­phen­yl)ethen­yl]diazen­yl}benzo­nitrile, which provides weak C—H⋯O inter­molecular hydrogen bonds.

Structural commentary

In the title compound, (Fig. 1 ▸), the dihedral angle between the 4-meth­oxy-substituted benzene ring and the benzene ring of the benzo­nitrile moiety is 41.86 (9)°. The C1—C6—N1—N2, C6—N1—N2—C7, N1—N2—C7—C8, N2—C7—C8—Cl1, N2—C7—C8—Cl2, Cl1—C8—C7—C9 and C8—C7—C9—C14 torsion angles of 24.8 (2), −178.37 (15), −176.77 (17), −2.2 (2), 178.27 (14), −176.26 (14) and −52.1 (3)°, respectively, describe the essentially planar conformation of the di­chloro-vinyl­diazenyl moiety. Bond lengths and angles are within normal ranges and are comparable to those observed in related structures such as (E)-1-[2,2-di­chloro-1-(4-nitro­phen­yl)ethen­yl]-2-(4-fluoro­phen­yl)diazene (Atioğlu et al., 2019 ▸), (2E)-1-(2-hy­droxy-5-methyl­phen­yl)-3-(4-meth­oxy­phen­yl)prop-2-en-1-one (Fun et al., 2011a ▸), (2E)-3-(3-benzyl­oxyphen­yl)-1-(2-hy­droxy-5-methyl­phen­yl)prop-2-en-1-one (Fun et al., 2011b ▸), (2E)-3-[3-(benz­yloxy)phen­yl]-1-(2-hy­droxy­phen­yl)prop-2-en-1-one (Fun et al., 2011c ▸), (2E)-1-(2,5-di­meth­oxy­phen­yl)-3-(3-nitro­phen­yl)prop-2-en-1-one (Fun et al., 2011d ▸) and (2E)-3-(3-nitro­phen­yl)-1-[4-(piperidin-1-yl)phen­yl]prop-2-en-1-one (Fun et al., 2012 ▸).

Figure 1

The mol­ecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features and Hirshfeld surface analysis

In the crystal, the mol­ecules are linked into layers parallel to the (020) plane by C—H⋯O contacts and face-to-face π–π stacking inter­actions [centroid-centroid distances = 3.9116 (14) and 3.9118 (14) Å] along the a-axis between the same aromatic rings (Table 1 ▸; Figs. 2 ▸ and 3 ▸). These mol­ecular layers are held together by weak van der Waals forces.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.95	2.47	3.391 (2)	165
C16—H16C⋯O1ii	0.98	2.59	3.516 (3)	158

Symmetry codes: (i) ; (ii) .

Figure 2

A view of the crystal packing of the title compound. The weak C—H⋯O inter­actions are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3

A packing diagram of the title compound, viewed along the a axis. The C—H⋯O inter­actions are shown as dashed lines.

Hirshfeld surfaces and fingerprint plots were generated for the title compound using CrystalExplorer (McKinnon et al., 2007 ▸) to qu­antify and visualize the inter­molecular inter­actions and to explain the observed crystal packing. The Hirshfeld surface mapped over d norm using a standard surface resolution with a fixed colour scale of −0.1603 (red) to 1.2420 (blue) a.u. is shown in Fig. 4 ▸. The dark-red spots on the d norm surface arise as a result of short inter­atomic contacts (Table 2 ▸), while the other weaker inter­molecular inter­actions appear as light-red spots. The red points, which represent closer contacts and negative d norm values on the surface, correspond to the C—H⋯O inter­actions. The Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ▸) is shown in Fig. 5 ▸. The red regions indicate atoms with the potential to be hydrogen-bond acceptors (negative electrostatic potential), while blue regions indicate atoms with positive electrostatic potential, i.e. hydrogen-bond donors. The shape-index of the Hirshfeld surface is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π inter­actions. Fig. 6 ▸ clearly suggest that there are π–π inter­actions in the title compound.

Figure 4

A view of the three-dimensional Hirshfeld surface of the title compound mapped over d norm showing the C—H⋯O inter­actions (dashed lines).

Table 2

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

Contact	Distance	Symmetry operation
Cl1⋯H5	3.05	1 + x,  − y,  + z
Cl1⋯H10	2.98	x,  − y,  + z
O1⋯H16C	2.59	1 + x, y, z
Cl2⋯N3	3.462	1 − x,  + y,  − z
H16B⋯C13	2.90	2 − x, 2 − y, 1 − z
O1⋯H2	2.47	1 + x,  − y, − + z
H4⋯N3	2.78	−x, 1 − y, 1 − z
H4⋯N3	2.82	1 − x, 1 − y, 1 − z
H13⋯H13	2.52	1 − x, 2 − y, 1 − z

Figure 5

View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms, corresponding to positive and negative potentials, respectively.

Figure 6

Hirshfeld surface of the title compound plotted over shape-index.

The percentage contributions of the various contacts to the total Hirshfeld surface are shown in the two dimensional fingerprint plots in Table 3 ▸. The reciprocal Cl⋯H/H⋯Cl inter­actions appear as two symmetrical broad wings with d e + d i ≃ 2.8 Å and contribute 22.8% to the Hirshfeld surface (Fig. 7 ▸ b). The H⋯H inter­actions appear in the middle of the scattered points in the two dimensional fingerprint plots, with an overall contribution to the Hirshfeld surface of 21.4% (Fig. 7 ▸ c). The N⋯H/H⋯N and C⋯H/H⋯C inter­actions also appear as two symmetrical broad wings with d e + d i ≃ 2.6 and 2.8 Å, respectively, and contribute 16.1 and 14.7%, respectively, to the Hirshfeld surface (Fig. 7 ▸ d,e). The C⋯C inter­actions appear in the middle of the scattered points in the two-dimensional fingerprint plots with an overall contribution to the Hirshfeld surface of 9.1% (Fig. 7 ▸ f). The small percentage contributions from the other different inter­atomic contacts to the Hirshfeld surfaces are listed in Table 3 ▸. The large number of Cl⋯H/H⋯Cl, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C and C⋯C inter­actions suggest that van der Waals inter­actions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ▸).

Table 3

Percentage contributions of inter­atomic contacts to the Hirshfeld surface

Contact	Percentage contribution
Cl⋯H/H⋯Cl	22.8
H⋯H	21.4
N⋯H/H⋯N	16.1
C⋯H/H⋯C	14.7
C⋯C	9.1
O⋯H/H⋯O	5.3
N⋯C/C⋯N	4.2
Cl⋯N/N⋯Cl	2.6
Cl⋯C/C⋯Cl	1.7
Cl⋯Cl	1.6
C⋯O/O⋯C	0.4
N⋯N	0.2

Figure 7

The Hirshfeld surface representations and two-dimensional fingerprint plots of the title compound showing all inter­actions, and the most significant individual types of inter­actions.

Synthesis and crystallization

The title compound was synthesized according to the reported method (Atioğlu et al., 2019 ▸; Maharramov et al., 2018 ▸; Shikhaliyev et al., 2018 ▸, 2019 ▸). A 20 mL screw-neck vial was charged with DMSO (10 mL), (E)-4-[2-(4-meth­oxy­benzyl­idene)hydrazine­yl]benzo­nitrile (251 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 (after TLC analysis showed complete consumption of the corresponding Schiff base), the reaction mixture was poured into an 0.01 M solution of HCl (100 mL, pH = 2–3) and extracted with di­chloro­methane (3x20 mL). The combined organic phase was washed with water (3x50 mL), brine (30 mL), dried over anhydrous Na2SO4 and concentrated in vacuo of the rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di­chloro­methane (3/1–1/1), giving an orange solid (63%); m.p. 471 K. Analysis calculated for C16H11Cl2N3O (M = 332.18): C 57.85, H 3.34, N 12.65; found: C 57.78, H 3.29, N 12.58%. 1H NMR (300 MHz, CDCl3) δ 3.83–3.93 (3H, OCH3), 6.89–7.70 (8H, Ar). 13C NMR (75 MHz, CDCl3) δ 153.89, 133.85, 133.14, 130.54, 130.37, 130.34, 115.49, 115.00, 113.80, 55.51, 29.72, 14.15. ESI–MS: m/z: 333.17 [M + H]+.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. The H atoms of aromatic and methyl groups were placed in calculated positions (C—H = 0.95 and 0.98 Å, respectively) and refined using a riding model with U iso= 1.2U eq(C-aromatic) and 1.5U eq(C-meth­yl).

Table 4

Experimental details

Crystal data
Chemical formula	C16H11Cl2N3O
M r	332.18
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	3.9117 (8), 25.109 (5), 14.968 (3)
β (°)	97.07 (3)
V (Å3)	1459.0 (5)
Z	4
Radiation type	Synchrotron, λ = 0.80246 Å
μ (mm−1)	0.63
Crystal size (mm)	0.25 × 0.05 × 0.03
Data collection
Diffractometer	Rayonix SX165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 ▸)
T min, T max	0.850, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	22750, 3144, 2978
R int	0.068
(sin θ/λ)max (Å−1)	0.639
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.123, 1.07
No. of reflections	3144
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.30, −0.46

Computer programs: Marccd (Doyle, 2011 ▸), iMosflm (Battye et al., 2011 ▸), SHELXLS97 (Sheldrick, 2008 ▸), SHELXL2016 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019009642/lh5909sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009642/lh5909Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019009642/lh5909Isup3.cml

CCDC reference: 1938782

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H11Cl2N3O	F(000) = 680
Mr = 332.18	Dx = 1.512 Mg m−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.80246 Å
a = 3.9117 (8) Å	Cell parameters from 600 reflections
b = 25.109 (5) Å	θ = 1.8–30.0°
c = 14.968 (3) Å	µ = 0.63 mm−1
β = 97.07 (3)°	T = 100 K
V = 1459.0 (5) Å3	Needle, orange
Z = 4	0.25 × 0.05 × 0.03 mm

Rayonix SX165 CCD diffractometer	2978 reflections with I > 2σ(I)
/f scan	Rint = 0.068
Absorption correction: multi-scan (Scala; Evans, 2006)	θmax = 30.9°, θmin = 1.8°
Tmin = 0.850, Tmax = 0.975	h = −4→4
22750 measured reflections	k = −32→32
3144 independent reflections	l = −19→19

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.066P)2 + 0.9448P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.30 e Å−3
3144 reflections	Δρmin = −0.46 e Å−3
201 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.049 (5)

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.

	x	y	z	Uiso*/Ueq
C1	0.4566 (5)	0.66476 (7)	0.67302 (12)	0.0215 (4)
H1	0.463381	0.687885	0.723440	0.026*
C2	0.3294 (5)	0.61359 (7)	0.67752 (13)	0.0221 (4)
H2	0.244963	0.601450	0.730780	0.026*
C3	0.3261 (5)	0.57981 (7)	0.60312 (13)	0.0215 (4)
C4	0.4409 (5)	0.59720 (7)	0.52351 (12)	0.0228 (4)
H4	0.436434	0.574023	0.473208	0.027*
C5	0.5621 (5)	0.64912 (7)	0.51906 (12)	0.0214 (4)
H5	0.636172	0.661965	0.464913	0.026*
C6	0.5748 (5)	0.68213 (7)	0.59378 (12)	0.0197 (4)
C7	0.9517 (5)	0.80678 (7)	0.65882 (12)	0.0199 (4)
C8	1.0851 (5)	0.82299 (7)	0.74254 (13)	0.0218 (4)
C9	0.9344 (5)	0.84019 (7)	0.57700 (12)	0.0199 (4)
C10	1.0545 (5)	0.82125 (7)	0.49838 (13)	0.0210 (4)
H10	1.155098	0.786823	0.498109	0.025*
C11	1.0283 (5)	0.85197 (7)	0.42152 (12)	0.0213 (4)
H11	1.108147	0.838403	0.368576	0.026*
C12	0.8849 (5)	0.90295 (7)	0.42105 (12)	0.0198 (4)
C13	0.7626 (5)	0.92238 (7)	0.49813 (13)	0.0208 (4)
H13	0.662374	0.956840	0.498230	0.025*
C14	0.7886 (5)	0.89082 (7)	0.57518 (13)	0.0210 (4)
H14	0.704725	0.904154	0.627752	0.025*
C15	0.1992 (5)	0.52632 (8)	0.61044 (13)	0.0249 (4)
C16	0.7123 (5)	0.98149 (7)	0.33590 (13)	0.0246 (4)
H16A	0.731494	0.997143	0.276745	0.037*
H16B	0.823240	1.005003	0.383095	0.037*
H16C	0.468596	0.977180	0.343527	0.037*
N1	0.7074 (4)	0.73473 (6)	0.58427 (10)	0.0207 (3)
N2	0.8218 (4)	0.75417 (6)	0.65946 (10)	0.0212 (3)
N3	0.1007 (5)	0.48385 (7)	0.61986 (13)	0.0345 (4)
O1	0.8781 (4)	0.93062 (5)	0.34222 (9)	0.0233 (3)
Cl1	1.07739 (13)	0.78390 (2)	0.83659 (3)	0.02703 (18)
Cl2	1.27416 (13)	0.88356 (2)	0.76669 (3)	0.02496 (18)

	U11	U22	U33	U12	U13	U23
C1	0.0237 (9)	0.0195 (9)	0.0207 (9)	0.0005 (7)	−0.0001 (7)	0.0001 (7)
C2	0.0246 (9)	0.0192 (9)	0.0220 (9)	0.0002 (7)	0.0009 (7)	0.0028 (7)
C3	0.0234 (9)	0.0166 (8)	0.0234 (9)	−0.0005 (7)	−0.0012 (7)	0.0016 (7)
C4	0.0285 (10)	0.0197 (9)	0.0193 (9)	−0.0018 (7)	−0.0009 (7)	−0.0006 (7)
C5	0.0242 (9)	0.0195 (8)	0.0193 (8)	−0.0005 (7)	−0.0021 (7)	0.0024 (7)
C6	0.0207 (9)	0.0154 (8)	0.0218 (9)	0.0007 (7)	−0.0020 (7)	0.0027 (6)
C7	0.0223 (9)	0.0159 (8)	0.0211 (9)	0.0008 (7)	0.0016 (7)	−0.0007 (6)
C8	0.0257 (9)	0.0173 (8)	0.0223 (9)	0.0005 (7)	0.0025 (7)	−0.0010 (7)
C9	0.0215 (9)	0.0167 (8)	0.0207 (9)	−0.0021 (7)	−0.0003 (7)	−0.0006 (6)
C10	0.0244 (9)	0.0159 (8)	0.0221 (9)	0.0002 (7)	0.0000 (7)	−0.0026 (7)
C11	0.0244 (9)	0.0181 (8)	0.0211 (9)	−0.0005 (7)	0.0016 (7)	−0.0021 (7)
C12	0.0221 (9)	0.0186 (8)	0.0179 (8)	−0.0029 (7)	−0.0007 (7)	0.0012 (6)
C13	0.0237 (9)	0.0150 (8)	0.0231 (9)	−0.0004 (7)	0.0006 (7)	−0.0003 (7)
C14	0.0247 (9)	0.0178 (8)	0.0201 (9)	−0.0004 (7)	0.0017 (7)	−0.0018 (6)
C15	0.0294 (10)	0.0231 (10)	0.0217 (9)	−0.0028 (8)	0.0011 (7)	−0.0002 (7)
C16	0.0290 (10)	0.0182 (9)	0.0254 (10)	0.0013 (7)	−0.0015 (7)	0.0030 (7)
N1	0.0225 (8)	0.0161 (7)	0.0227 (8)	0.0004 (6)	−0.0004 (6)	0.0013 (6)
N2	0.0251 (8)	0.0164 (7)	0.0212 (8)	−0.0003 (6)	−0.0007 (6)	−0.0006 (6)
N3	0.0490 (12)	0.0242 (9)	0.0304 (9)	−0.0092 (8)	0.0046 (8)	−0.0008 (7)
O1	0.0307 (7)	0.0186 (6)	0.0203 (7)	0.0020 (5)	0.0018 (5)	0.0023 (5)
Cl1	0.0386 (3)	0.0223 (3)	0.0191 (3)	−0.00365 (18)	−0.00068 (19)	0.00226 (16)
Cl2	0.0343 (3)	0.0185 (3)	0.0213 (3)	−0.00454 (17)	0.00074 (18)	−0.00278 (15)

C1—C2	1.382 (3)	C9—C14	1.392 (2)
C1—C6	1.395 (3)	C9—C10	1.403 (3)
C1—H1	0.9500	C10—C11	1.378 (3)
C2—C3	1.399 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.397 (3)
C3—C4	1.394 (3)	C11—H11	0.9500
C3—C15	1.441 (3)	C12—O1	1.367 (2)
C4—C5	1.392 (3)	C12—C13	1.391 (3)
C4—H4	0.9500	C13—C14	1.393 (3)
C5—C6	1.388 (3)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C6—N1	1.433 (2)	C15—N3	1.149 (3)
C7—C8	1.359 (3)	C16—O1	1.430 (2)
C7—N2	1.416 (2)	C16—H16A	0.9800
C7—C9	1.479 (2)	C16—H16B	0.9800
C8—Cl2	1.7103 (19)	C16—H16C	0.9800
C8—Cl1	1.7196 (19)	N1—N2	1.257 (2)
C2—C1—C6	119.40 (17)	C10—C9—C7	121.08 (16)
C2—C1—H1	120.3	C11—C10—C9	120.81 (17)
C6—C1—H1	120.3	C11—C10—H10	119.6
C1—C2—C3	119.55 (18)	C9—C10—H10	119.6
C1—C2—H2	120.2	C10—C11—C12	120.36 (17)
C3—C2—H2	120.2	C10—C11—H11	119.8
C4—C3—C2	121.20 (17)	C12—C11—H11	119.8
C4—C3—C15	120.48 (17)	O1—C12—C13	124.46 (17)
C2—C3—C15	118.32 (17)	O1—C12—C11	115.79 (16)
C5—C4—C3	118.80 (17)	C13—C12—C11	119.74 (17)
C5—C4—H4	120.6	C12—C13—C14	119.34 (17)
C3—C4—H4	120.6	C12—C13—H13	120.3
C6—C5—C4	119.96 (17)	C14—C13—H13	120.3
C6—C5—H5	120.0	C9—C14—C13	121.59 (17)
C4—C5—H5	120.0	C9—C14—H14	119.2
C5—C6—C1	121.04 (17)	C13—C14—H14	119.2
C5—C6—N1	116.61 (16)	N3—C15—C3	177.3 (2)
C1—C6—N1	122.33 (16)	O1—C16—H16A	109.5
C8—C7—N2	111.75 (16)	O1—C16—H16B	109.5
C8—C7—C9	124.52 (17)	H16A—C16—H16B	109.5
N2—C7—C9	123.71 (15)	O1—C16—H16C	109.5
C7—C8—Cl2	124.62 (15)	H16A—C16—H16C	109.5
C7—C8—Cl1	122.71 (15)	H16B—C16—H16C	109.5
Cl2—C8—Cl1	112.66 (11)	N2—N1—C6	111.24 (15)
C14—C9—C10	118.16 (17)	N1—N2—C7	116.40 (15)
C14—C9—C7	120.73 (17)	C12—O1—C16	118.13 (15)
C6—C1—C2—C3	0.9 (3)	C14—C9—C10—C11	0.0 (3)
C1—C2—C3—C4	−1.6 (3)	C7—C9—C10—C11	178.04 (17)
C1—C2—C3—C15	178.65 (18)	C9—C10—C11—C12	0.8 (3)
C2—C3—C4—C5	0.3 (3)	C10—C11—C12—O1	178.52 (17)
C15—C3—C4—C5	−179.91 (18)	C10—C11—C12—C13	−1.1 (3)
C3—C4—C5—C6	1.5 (3)	O1—C12—C13—C14	−178.90 (17)
C4—C5—C6—C1	−2.2 (3)	C11—C12—C13—C14	0.7 (3)
C4—C5—C6—N1	179.12 (16)	C10—C9—C14—C13	−0.4 (3)
C2—C1—C6—C5	0.9 (3)	C7—C9—C14—C13	−178.47 (17)
C2—C1—C6—N1	179.54 (17)	C12—C13—C14—C9	0.0 (3)
N2—C7—C8—Cl2	178.27 (14)	C5—C6—N1—N2	−156.50 (17)
C9—C7—C8—Cl2	−3.3 (3)	C1—C6—N1—N2	24.8 (2)
N2—C7—C8—Cl1	−2.2 (2)	C6—N1—N2—C7	−178.37 (15)
C9—C7—C8—Cl1	176.26 (14)	C8—C7—N2—N1	−176.77 (17)
C8—C7—C9—C14	−52.1 (3)	C9—C7—N2—N1	4.8 (3)
N2—C7—C9—C14	126.2 (2)	C13—C12—O1—C16	−4.7 (3)
C8—C7—C9—C10	129.9 (2)	C11—C12—O1—C16	175.67 (16)
N2—C7—C9—C10	−51.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.95	2.47	3.391 (2)	165
C16—H16C···O1ii	0.98	2.59	3.516 (3)	158