research communications
Whole-molecule disorder of the Schiff base compound 4-chloro-N-(4-nitrobenzylidene)aniline: and Hirshfeld surface analysis
aDepartment of Physics, Ethiraj College for Women, Chennai - 600 008, Tamilnadu, India, bCrystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli - 620 024, India, cPG and Research Department of Physics, Srimad Andavan Arts and Science College, Tiruchirappalli - 620 005, India, dLight and Matter Physics Group, Raman Research Institute, C. V. Raman Avenue, Sadashivanaga, Bangalore - 560 080, India, eDepartment of Bio-Medical Engineering, Aarupadai Veedu Institute of Technology, Vinayaga Mission's Research Foundation, Vinayaga Nagar, Paiyanoor, 603 104, Tamil Nadu, India, and fInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
*Correspondence e-mail: leelabeena@gmail.com, helen.stoeckli-evans@unine.ch
In the crystal of the title Schiff base compound, C13H9ClN2O2, [CNBA; (E)-N-(4-chlorophenyl)-1-(4-nitrophenyl)methanimine], the CNBA molecule shows whole-molecule disorder (occupancy ratio 0.65:0.35), with the disorder components related by a twofold rotation about the shorter axis of the molecule. The aromatic rings are inclined to each other by 39.3 (5)° in the major component and by 35.7 (9)° in the minor component. In the crystal, C—H⋯O hydrogen bonds predominate in linking the major components, while weak C—H⋯Cl interactions predominate in linking the minor components. The result is the formation of corrugated layers lying parallel to the ac plane. The crystal packing was analysed using Hirshfeld surface analysis and compared with related structures.
Keywords: crystal structure; Schiff bases; non-linear optical properties; disorder; hydrogen bonding; Hirshfeld surface analysis.
CCDC reference: 941508
1. Chemical context
A number of benzylideneaniline derivatives crystallize in non-centrosymmetric space groups and are therefore of interest for their non-linear optical properties (Bar & Bernstein, 1977; Batra et al., 2004). In 1970, Bürgi & Dunitz (1970) analysed a number of N-benzylanilines and found that they were twisted about the N=C bond unlike trans-stilbenes (see for example: Behrnd et al., 2010; De Borger et al., 2005) or trans-azobenzenes (see for example: Huang et al., 2002; Bushuyev et al., 2016), which are almost planar.
Benzylideneaniline derivatives are known to exhibit disorder and Bernstein and collaborators (Bar & Bernstein, 1983; Kluge et al., 2003) have defined the different types of orientational disorder of these compounds, where the molecules may be oriented in different ways but in the two or more dispositions each atom is essentially superimposed on another at any one crystallographic site. Static disorder around the C=N bond is also responsible for the apparent shortening of the C=N bond at room temperature (Bar & Bernstein, 1984). This phenomenon has also been studied by Harada et al. (2004a), who, by means of a variable temperature study, concluded that the shortening depends on temperature and is due to a torsional vibration of the C–phenyl and N–phenyl bonds in the crystals.
The crystal structures of a number of disordered benzylideneaniline compounds have been reported on and various forms of the disorder have been analysed (Bar & Bernstein, 1977, 1984; Harada et al., 2004a,b). The disorder appears to fall into three categories (Fig. 1): D1 – twofold rotation about the longer axis of the molecule, D2 – the molecule is located about a crystallographic center of symmetry, and D3 – twofold rotation about the shorter axis of the molecule.
Type D1 disorder has been observed for one of the two independent molecules in the crystal of N-(4-nitrobenzylidene)aniline at 300 and 200 K, but the disorder is not present at 90 K (Harada et al., 2004b). Orientational disorder about a center of symmetry (type D2) was found in N-(p-chlorobenzylidene)-p-chloroaniline (Bar & Bernstein, 1982; Bernstein & Schmidt, 1972). Type D3 disorder has been observed for N-benzylideneaniline (Bernstein & Izak, 1976; Harada et al., 2004a) and for 4-methyl-4′-methoxybenzylideneaniline (Harada et al., 2004a).
Three forms of p-methyl-N-(p-methylbenzylidene)aniline (Bernstein, Bar & Christensen, 1976; Bar & Bernstein, 1982; Bar & Bernstein, 1977) have been shown to exist: Form I (Bar & Bernstein, 1982), crystallizes in P21/c and the C=N bond of the molecule is located about a center of symmetry, hence the molecule has type D2 disorder; form II (Bar & Bernstein, 1977) crystallizes in P21 and the molecule is not disordered; form III (Bar & Bernstein, 1977; Harada et al., 2004b), has a fourfold disorder with the molecule being located about a center of symmetry and has a twofold rotation about the longer axis of the molecule (D1 + D2).
In the past few years some benzylideneaniline compounds have been synthesized using p-nitrobenzaldehyde as one of the reactants; for example, 4-nitro-benzylideneaniline (HNBA; Harada et al., 2004b), 4-fluoro-4′-nitro-benzylideneaniline (FNBA; Subashini et al., 2013b), 4-bromo-4′-nitro-benzylideneaniline (BNBA; Subashini et al., 2013a) and 4-hydroxy-4′-nitro-benzylideneaniline [systematic name: 4-[(E)-(4-nitrobenzylidene)amino]phenol] (HONBA; Atioğlu et al., 2015).
To continue the series of 4-halogen species, we report herein on the et al. (2004), who found that the crystals they obtained showed good second harmonic generation (SHG) of 1.064 micron wavelength radiation. The analysis carried out for CNBA in this work shows that it crystallizes in the centrosymmetric P21/c, and that the molecule has positional disorder (type D3), hence no SHG properties are expected for this particular sample. It is interesting to note that the structure of 4-bromo-4′-nitrobenzylideneaniline (BNBA) crystallizes in a non-centrosymmetric (A2), while the title compound and 4-fluoro-4′-nitrobenzylidene aniline (FNBA; Subashini et al., 2013b) both crystallize in P21/c.
of 4-chloro-4′-nitro-benzylideneaniline (CNBA). It was previously synthesized by Batra2. Structural commentary
The molecular structure of CNBA is shown in Fig. 2. It crystallizes in the centrosymmetric monoclinic P21/c, and is disordered with a twofold rotation about the shorter axis of the molecule – type D3. The twofold axis almost bisects the central C=N bond, so that the two component molecules are superimposed head-to-tail, as shown clearly in a difference-Fourier map (Fig. 3). They have an occupancy ratio that, after initial was fixed at 0.649:0.351. As mentioned above, this type of disorder (D3) has been observed previously for related phases.
The configuration about the C=N bond is E in both components. The dihedral angle between the benzene rings of the major component CNBA_1 (C1–C6 and C8–C13) is 38.6 (2)°, and that between rings C21–C26 and C28–C33 of the minor component (CNBA_2) is 36.5 (4)°. In CNBA_1 the N1=C7 bond length is 1.291 (6) Å, while for CNBA_2 the equivalent N21=C27 bond length is 1.234 (12) Å. The NO2 group, N2/O1/O2, in CNBA_1 is inclined to benzene ring C8–C13 by 2.2 (7)°, and atom Cl1 is displaced by 0.016 (3) Å from benzene ring C1–C6. In component CNBA_2, the NO2 group, N22/O21/O22, is inclined to benzene ring C28–C33 by 9.0 (15)°, while atom Cl2 lies in the plane of the benzene ring C21–C26 [deviation 0.002 (5) Å].
3. Supramolecular features
A view along the a axis of the crystal packing of CNBA is presented in Fig. 4, and details of the hydrogen bonding are given in Table 1. The crystal packing of the individual components, CBNA_1 and CBNA_2, are given in Fig. 5a and 5b, respectively. In Fig. 5a it can be seen that the molecular packing for CNBA_1 is influenced by two C—H⋯O interactions: namely, C5—H5⋯O2 and C13—H13⋯O1. The first of these links the molecules into C(11) chains and the second generates C(6) chains. In Fig. 5b, it can be seen that for CNBA_2 the molecular packing features weak C—H⋯Cl interactions (Table 1). As a result of these interactions, corrugated layers are formed, lying parallel to the ac plane.
4. Database survey
A search of the Cambridge Structural Database (Version 5.41, last update November 2019; Groom et al., 2016) for N,1-diphenylmethanimines gave 73 hits for 63 compounds, while a search for 1-(4-nitrophenyl)-N-phenylmethanimines gave 25 hits for six compounds. In these searches a number of compounds have multiple reports, or have been studied at different temperatures, or concern polymorphs.
The most relevant compounds that concern us here include those reported above in §1 (Chemical context), viz. N-(4-nitrobenzylidene)aniline (CSD refcodes QQQAIY01, QQQAIY02, QQQAIY03: Harada et al., 2004b), the 4-fluoro derivative (MIMDUJ: Subashini et al., 2013b), the 4-bromo derivative (FIBXIZ01: Subashini et al., 2013a), the 4-methyl derivative (NMBYAN: Filipenko et al., 1976; NMBYAN22: Filipenko et al., 1977; NMBYAN01: Cole et al., 2001; NMBYAN25, NMBYAN26: Harada et al., 2004a), the 4-methoxy benzylidene derivative (NMBZYA01, NMBZYA02: Harada et al., 2004a) and the 4-hydroxy derivative (WOTQED: Atioğlu et al., 2015).
For N-(4-nitrobenzylidene)aniline measured at 300 K (QQQAIY01), one of the two independent molecules in the has type D1 disorder. At 200 K (QQQAIY02) a difference-Fourier map indicated only a few weak residual density peaks corresponding to the minor component, while at 90 K (QQQAIY03) no disorder was observed. For the 4-fluoro derivative measured at 173 K (MIMDUJ) no disorder was observed. For the 4-bromo derivative (FIBXIZ01), the crystals were incommensurate and twinned and the structure was refined in A2. A triclinic polymorph of the 4-methyl derivative (NMBYAN) with two independent molecules in the was reported on by Filipenko et al. (1976). A monoclinic polymorph, with one molecule in the was reported on first by Filipenko et al. (1976) for NMBYAN22, and later a neutron diffraction study at 20 K was carried out by Cole et al. (2001) for NMBYAN01. The triclinic polymorph was also studied by Harada et al. (2004a), at 300 K (NMBYAN25) and at 90 K (NMBYAN26) and showed only disorder of the methyl hydrogen atoms at both temperatures. The 4-methoxy benzylidene derivative, measured at 300 K (NMBZYA01) and 90 K (NMBZYA02), showed no disorder at either temperature. Finally, the 4-hydroxy derivative, WOTQED, crystallizes with four independent molecules in the and one of the molecules has type D1 disorder.
The N=C bond lengths vary from as short as ca.1.187 Å, in one of the four independent molecules of WOTQED, to ca 1.281 Å in NMBZYA02. In the title compound, the N1=C7 bond length in the major component is 1.291 (6) Å, while for the minor component the N21=C27 bond length is 1.234 (12) Å. In the above-mentioned compounds, the benzene rings are inclined to each other by dihedral angles varying from ca 2.24° in one of the independent molecules of WOTQED to ca 55.76° in one of the two independent molecules in NMBYAN26; thus the dihedral angles for the disorder components of the title compound fall roughly in the middle of this range.
5. Hirshfeld surface analysis 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) following the protocol of Tiekink and collaborators (Tan et al., 2019).
The Hirshfeld surface of CNBA mapped over dnorm is given in Fig. 6a, where short interatomic contacts are indicated by the red spots. The Hirshfeld surfaces of the individual components, CNBA_1 and CNBA_2, mapped over dnorm are given in Fig. 6b and 6c, respectively.
The full two-dimensional fingerprint plots for CNBA and for the individual components, CNBA_1 and CNBA_2, are given in Fig. 7a, 7b and 7c, respectively. The relative percentage contributions of close contacts to the Hirshfeld surface for CNBA and for the individual components are compared in Table 2. For CNBA the principal intermolecular interactions are delineated into O⋯H/H⋯O at 37.3%, H⋯H at 25.5%, C⋯H/H⋯C and C⋯C both at 10.2%, followed by Cl⋯H/H⋯Cl and N⋯H/H⋯N contacts both at 3.5%. For CNBA_1 and CMBA_2 the order is somewhat different with H⋯H contributions being superior or almost equal to the contributions of the O⋯H/H⋯O contacts, the latter contributions being 22.3 and 24.4%, respectively, compared to 37.3% for CNBA. In contrast, the Cl⋯H/H⋯Cl contacts contribute 14.5% and 14.8% for CNBA_1 and CNBA_2, respectively, compared to only 3.5% for CNBA. This situation reflects the details of the hydrogen bonding in the (see Fig. 5a and 5b, and Table 1).
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6. Synthesis and crystallization
The commercially available organic compounds p-nitrobenzaldehyde and p-chloroaniline were used without further purification and the title compound was synthesized following reported procedures (Batra et al., 2004; Subashini et al., 2013a): the two reactants were taken in equimolar ratio and refluxed in ethanol for 6 h. On cooling, the synthesized compound was deposited at room temperature as a deep-yellow microcrystalline powder. The material was purified by repeated recrystallization using ethanol at room temperature and the purity of the sample was confirmed by thin layer A of CNBA was prepared using mixed solvents of ethanol and ethylacetate (1:1, v:v) and single crystals were obtained as yellow rods by slow evaporation of the solvents at room temperature over a period of 18 days. The 1H NMR spectrum of CNBA recorded in CDCl3 is shown in the supporting information, Fig. 1S, and the FTIR and FT Raman spectra are shown in Fig. 2S.
7. Refinement
Crystal data, data collection and structure . The C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.95 Å with Uiso(H) = 1.2Ueq(C). The molecule is disordered with an occupancy ratio that after was fixed at 0.649: 0.351. The benzene rings in the two components were refined as rigid bodies and the anisotropic displacement parameters of corresponding C atoms were made equal.
details are summarized in Table 3Supporting information
CCDC reference: 941508
https://doi.org/10.1107/S2056989020002212/hb7888sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020002212/hb7888Isup2.hkl
NMR spectra. DOI: https://doi.org/10.1107/S2056989020002212/hb7888sup3.tif
FTIR and FT Raaman spectra. DOI: https://doi.org/10.1107/S2056989020002212/hb7888sup4.tif
Supporting information file. DOI: https://doi.org/10.1107/S2056989020002212/hb7888Isup5.cml
Data collection: X-AREA (Stoe & Cie, 2006); cell
X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).C13H9ClN2O2 | F(000) = 536 |
Mr = 260.67 | Dx = 1.458 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8195 (5) Å | Cell parameters from 3565 reflections |
b = 22.826 (4) Å | θ = 1.7–26.0° |
c = 13.6381 (19) Å | µ = 0.32 mm−1 |
β = 92.829 (11)° | T = 173 K |
V = 1187.6 (3) Å3 | Rod, yellow |
Z = 4 | 0.34 × 0.17 × 0.09 mm |
STOE IPDS-2 diffractometer | 2256 independent reflections |
Radiation source: fine-focus sealed tube | 1498 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
phi & ω scans | θmax = 25.7°, θmin = 1.7° |
Absorption correction: multi-scan (MULABS; Spek, 2020) | h = −4→4 |
Tmin = 0.923, Tmax = 1.000 | k = −27→27 |
9572 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0668P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
2256 reflections | Δρmax = 0.30 e Å−3 |
206 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: (SHELXL2018; Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.036 (4) |
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 | Occ. (<1) | |
Cl1 | 1.0727 (7) | 0.60002 (12) | 0.0780 (3) | 0.0575 (7) | 0.649 |
O1 | 0.0813 (9) | 0.23891 (13) | 0.7308 (2) | 0.0628 (8) | 0.649 |
O2 | 0.212 (2) | 0.1651 (2) | 0.6402 (7) | 0.069 (2) | 0.649 |
N1 | 0.7162 (7) | 0.42998 (14) | 0.3862 (3) | 0.0326 (7) | 0.649 |
N2 | 0.1963 (14) | 0.2188 (2) | 0.6565 (4) | 0.0444 (13) | 0.649 |
C1 | 0.9720 (11) | 0.54801 (15) | 0.16579 (17) | 0.0369 (11) | 0.649 |
C2 | 1.0661 (9) | 0.55941 (11) | 0.26368 (19) | 0.0379 (10) | 0.649 |
H2 | 1.184626 | 0.594746 | 0.281349 | 0.045* | 0.649 |
C3 | 0.9869 (8) | 0.51912 (12) | 0.33572 (13) | 0.0334 (8) | 0.649 |
H3 | 1.051256 | 0.526918 | 0.402629 | 0.040* | 0.649 |
C4 | 0.8136 (8) | 0.46743 (11) | 0.30987 (16) | 0.0297 (8) | 0.649 |
C5 | 0.7194 (11) | 0.45602 (14) | 0.21198 (19) | 0.0353 (10) | 0.649 |
H5 | 0.600963 | 0.420689 | 0.194313 | 0.042* | 0.649 |
C6 | 0.7987 (12) | 0.49631 (18) | 0.13994 (13) | 0.0391 (11) | 0.649 |
H6 | 0.734329 | 0.488517 | 0.073031 | 0.047* | 0.649 |
C7 | 0.7008 (13) | 0.3742 (2) | 0.3713 (5) | 0.0335 (11) | 0.649 |
H7 | 0.774112 | 0.358824 | 0.310888 | 0.040* | 0.649 |
C8 | 0.5727 (10) | 0.33367 (11) | 0.44542 (19) | 0.0305 (10) | 0.649 |
C9 | 0.4512 (9) | 0.35627 (9) | 0.5321 (2) | 0.0346 (9) | 0.649 |
H9 | 0.451447 | 0.397391 | 0.542816 | 0.042* | 0.649 |
C10 | 0.3292 (9) | 0.31870 (11) | 0.60298 (18) | 0.0337 (9) | 0.649 |
H10 | 0.246154 | 0.334147 | 0.662194 | 0.040* | 0.649 |
C11 | 0.3289 (11) | 0.25854 (11) | 0.5872 (2) | 0.0278 (9) | 0.649 |
C12 | 0.4504 (13) | 0.23594 (9) | 0.5006 (3) | 0.0331 (10) | 0.649 |
H12 | 0.450148 | 0.194817 | 0.489855 | 0.040* | 0.649 |
C13 | 0.5724 (12) | 0.27351 (12) | 0.4297 (2) | 0.0333 (10) | 0.649 |
H13 | 0.655443 | 0.258061 | 0.370476 | 0.040* | 0.649 |
Cl2 | 0.1792 (12) | 0.1871 (2) | 0.6481 (4) | 0.0553 (12) | 0.351 |
O21 | 1.1934 (18) | 0.6433 (2) | 0.1833 (4) | 0.0704 (17) | 0.351 |
O22 | 1.091 (5) | 0.5975 (7) | 0.0487 (13) | 0.099 (8) | 0.351 |
N21 | 0.6719 (15) | 0.3947 (3) | 0.4304 (6) | 0.0429 (14) | 0.351 |
N22 | 1.095 (2) | 0.6024 (4) | 0.1364 (8) | 0.053 (2) | 0.351 |
C21 | 0.331 (3) | 0.2457 (2) | 0.5774 (7) | 0.0369 (11) | 0.351 |
C22 | 0.476 (3) | 0.2384 (3) | 0.4867 (7) | 0.0379 (10) | 0.351 |
H22 | 0.496956 | 0.200313 | 0.459614 | 0.045* | 0.351 |
C23 | 0.590 (3) | 0.2869 (4) | 0.4356 (5) | 0.0334 (8) | 0.351 |
H23 | 0.689079 | 0.281974 | 0.373553 | 0.040* | 0.351 |
C24 | 0.559 (2) | 0.3427 (3) | 0.4752 (5) | 0.0297 (8) | 0.351 |
C25 | 0.414 (2) | 0.3500 (2) | 0.5659 (5) | 0.0353 (10) | 0.351 |
H25 | 0.393402 | 0.388076 | 0.592940 | 0.042* | 0.351 |
C26 | 0.300 (2) | 0.3015 (3) | 0.6170 (4) | 0.0391 (11) | 0.351 |
H26 | 0.201277 | 0.306416 | 0.679004 | 0.047* | 0.351 |
C27 | 0.652 (2) | 0.3978 (5) | 0.3399 (7) | 0.039 (2) | 0.351 |
H27 | 0.556380 | 0.365770 | 0.303238 | 0.047* | 0.351 |
C28 | 0.7743 (17) | 0.4503 (2) | 0.2864 (5) | 0.0305 (10) | 0.351 |
C29 | 0.9255 (16) | 0.4963 (3) | 0.3401 (3) | 0.0346 (9) | 0.351 |
H29 | 0.953565 | 0.493632 | 0.409583 | 0.042* | 0.351 |
C30 | 1.0355 (18) | 0.5463 (2) | 0.2922 (5) | 0.0337 (9) | 0.351 |
H30 | 1.138834 | 0.577751 | 0.328889 | 0.040* | 0.351 |
C31 | 0.994 (2) | 0.5502 (3) | 0.1906 (5) | 0.0278 (9) | 0.351 |
C32 | 0.843 (2) | 0.5042 (4) | 0.1369 (3) | 0.0331 (10) | 0.351 |
H32 | 0.815122 | 0.506868 | 0.067426 | 0.040* | 0.351 |
C33 | 0.733 (2) | 0.4542 (3) | 0.1848 (5) | 0.0333 (10) | 0.351 |
H33 | 0.629851 | 0.422748 | 0.148118 | 0.040* | 0.351 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0600 (10) | 0.0436 (10) | 0.070 (2) | 0.0011 (8) | 0.0144 (12) | 0.0180 (13) |
O1 | 0.080 (2) | 0.070 (2) | 0.0402 (16) | −0.0056 (16) | 0.0215 (16) | 0.0067 (15) |
O2 | 0.086 (4) | 0.044 (4) | 0.078 (3) | 0.004 (3) | 0.019 (3) | 0.017 (3) |
N1 | 0.0346 (17) | 0.0294 (16) | 0.0340 (17) | −0.0007 (13) | 0.0049 (13) | 0.0029 (17) |
N2 | 0.039 (2) | 0.048 (3) | 0.046 (2) | 0.005 (3) | −0.0023 (16) | 0.014 (3) |
C1 | 0.038 (2) | 0.0319 (18) | 0.040 (2) | 0.0038 (16) | 0.000 (2) | −0.0006 (18) |
C2 | 0.039 (2) | 0.0315 (18) | 0.044 (3) | 0.0009 (15) | 0.0093 (17) | 0.0016 (15) |
C3 | 0.0362 (19) | 0.0280 (18) | 0.0363 (19) | −0.0026 (14) | 0.0043 (15) | 0.0024 (14) |
C4 | 0.0270 (17) | 0.0295 (18) | 0.0327 (19) | 0.0002 (14) | 0.0011 (15) | −0.0044 (17) |
C5 | 0.0339 (19) | 0.0328 (19) | 0.039 (3) | −0.0006 (14) | 0.0036 (18) | 0.0001 (18) |
C6 | 0.036 (2) | 0.039 (2) | 0.043 (2) | −0.0028 (17) | 0.0006 (16) | 0.0048 (17) |
C7 | 0.029 (2) | 0.037 (3) | 0.034 (3) | 0.005 (2) | 0.0000 (19) | −0.001 (2) |
C8 | 0.0267 (16) | 0.035 (2) | 0.0289 (19) | −0.0004 (14) | −0.0039 (16) | −0.0050 (16) |
C9 | 0.0364 (19) | 0.0323 (17) | 0.035 (2) | −0.0008 (14) | 0.0005 (17) | 0.0035 (15) |
C10 | 0.0367 (19) | 0.0319 (19) | 0.0320 (18) | 0.0049 (16) | −0.0027 (15) | −0.0071 (16) |
C11 | 0.0271 (19) | 0.029 (2) | 0.0267 (17) | 0.0014 (15) | −0.0009 (14) | 0.0031 (16) |
C12 | 0.032 (2) | 0.0383 (19) | 0.030 (2) | 0.0029 (15) | 0.0022 (16) | 0.0033 (15) |
C13 | 0.0344 (19) | 0.033 (2) | 0.0329 (18) | 0.0014 (17) | 0.0026 (15) | 0.0015 (15) |
Cl2 | 0.0509 (15) | 0.057 (4) | 0.058 (2) | 0.007 (3) | 0.0044 (13) | 0.023 (3) |
O21 | 0.101 (5) | 0.041 (3) | 0.069 (4) | −0.019 (3) | 0.007 (3) | −0.008 (3) |
O22 | 0.153 (13) | 0.064 (7) | 0.079 (12) | −0.017 (6) | −0.015 (8) | −0.009 (6) |
N21 | 0.036 (3) | 0.040 (4) | 0.053 (4) | 0.002 (3) | 0.001 (3) | −0.004 (4) |
N22 | 0.045 (4) | 0.052 (5) | 0.063 (6) | −0.014 (3) | 0.010 (5) | −0.018 (5) |
C21 | 0.038 (2) | 0.0319 (18) | 0.040 (2) | 0.0038 (16) | 0.000 (2) | −0.0006 (18) |
C22 | 0.039 (2) | 0.0315 (18) | 0.044 (3) | 0.0009 (15) | 0.0093 (17) | 0.0016 (15) |
C23 | 0.0362 (19) | 0.0280 (18) | 0.0363 (19) | −0.0026 (14) | 0.0043 (15) | 0.0024 (14) |
C24 | 0.0270 (17) | 0.0295 (18) | 0.0327 (19) | 0.0002 (14) | 0.0011 (15) | −0.0044 (17) |
C25 | 0.0339 (19) | 0.0328 (19) | 0.039 (3) | −0.0006 (14) | 0.0036 (18) | 0.0001 (18) |
C26 | 0.036 (2) | 0.039 (2) | 0.043 (2) | −0.0028 (17) | 0.0006 (16) | 0.0048 (17) |
C27 | 0.029 (4) | 0.041 (6) | 0.048 (6) | 0.003 (4) | 0.001 (4) | −0.010 (5) |
C28 | 0.0267 (16) | 0.035 (2) | 0.0289 (19) | −0.0004 (14) | −0.0039 (16) | −0.0050 (16) |
C29 | 0.0364 (19) | 0.0323 (17) | 0.035 (2) | −0.0008 (14) | 0.0005 (17) | 0.0035 (15) |
C30 | 0.0367 (19) | 0.0319 (19) | 0.0320 (18) | 0.0049 (16) | −0.0027 (15) | −0.0071 (16) |
C31 | 0.0271 (19) | 0.029 (2) | 0.0267 (17) | 0.0014 (15) | −0.0009 (14) | 0.0031 (16) |
C32 | 0.032 (2) | 0.0383 (19) | 0.030 (2) | 0.0029 (15) | 0.0022 (16) | 0.0033 (15) |
C33 | 0.0344 (19) | 0.033 (2) | 0.0329 (18) | 0.0014 (17) | 0.0026 (15) | 0.0015 (15) |
Cl1—C1 | 1.743 (4) | Cl2—C21 | 1.763 (7) |
O1—N2 | 1.214 (6) | O21—N22 | 1.182 (9) |
O2—N2 | 1.248 (7) | O22—N22 | 1.20 (2) |
N1—C7 | 1.291 (6) | N21—C27 | 1.234 (12) |
N1—C4 | 1.411 (4) | N21—C24 | 1.412 (9) |
N2—C11 | 1.420 (6) | N22—C31 | 1.462 (11) |
C1—C2 | 1.3900 | C21—C22 | 1.3900 |
C1—C6 | 1.3900 | C21—C26 | 1.3900 |
C2—C3 | 1.3900 | C22—C23 | 1.3900 |
C2—H2 | 0.9500 | C22—H22 | 0.9500 |
C3—C4 | 1.3900 | C23—C24 | 1.3900 |
C3—H3 | 0.9500 | C23—H23 | 0.9500 |
C4—C5 | 1.3900 | C24—C25 | 1.3900 |
C5—C6 | 1.3900 | C25—C26 | 1.3900 |
C5—H5 | 0.9500 | C25—H25 | 0.9500 |
C6—H6 | 0.9500 | C26—H26 | 0.9500 |
C7—C8 | 1.471 (6) | C27—C28 | 1.488 (11) |
C7—H7 | 0.9500 | C27—H27 | 0.9500 |
C8—C9 | 1.3900 | C28—C29 | 1.3900 |
C8—C13 | 1.3900 | C28—C33 | 1.3900 |
C9—C10 | 1.3900 | C29—C30 | 1.3900 |
C9—H9 | 0.9500 | C29—H29 | 0.9500 |
C10—C11 | 1.3900 | C30—C31 | 1.3900 |
C10—H10 | 0.9500 | C30—H30 | 0.9500 |
C11—C12 | 1.3900 | C31—C32 | 1.3900 |
C12—C13 | 1.3900 | C32—C33 | 1.3900 |
C12—H12 | 0.9500 | C32—H32 | 0.9500 |
C13—H13 | 0.9500 | C33—H33 | 0.9500 |
C7—N1—C4 | 119.5 (4) | C27—N21—C24 | 118.5 (9) |
O1—N2—O2 | 122.8 (8) | O21—N22—O22 | 126.8 (14) |
O1—N2—C11 | 117.9 (4) | O21—N22—C31 | 117.0 (9) |
O2—N2—C11 | 119.2 (8) | O22—N22—C31 | 115.9 (12) |
C2—C1—C6 | 120.0 | C22—C21—C26 | 120.0 |
C2—C1—Cl1 | 118.5 (2) | C22—C21—Cl2 | 123.6 (5) |
C6—C1—Cl1 | 121.5 (2) | C26—C21—Cl2 | 116.4 (5) |
C3—C2—C1 | 120.0 | C23—C22—C21 | 120.0 |
C3—C2—H2 | 120.0 | C23—C22—H22 | 120.0 |
C1—C2—H2 | 120.0 | C21—C22—H22 | 120.0 |
C2—C3—C4 | 120.0 | C22—C23—C24 | 120.0 |
C2—C3—H3 | 120.0 | C22—C23—H23 | 120.0 |
C4—C3—H3 | 120.0 | C24—C23—H23 | 120.0 |
C5—C4—C3 | 120.0 | C25—C24—C23 | 120.0 |
C5—C4—N1 | 122.0 (2) | C25—C24—N21 | 115.4 (6) |
C3—C4—N1 | 117.8 (2) | C23—C24—N21 | 124.6 (6) |
C4—C5—C6 | 120.0 | C24—C25—C26 | 120.0 |
C4—C5—H5 | 120.0 | C24—C25—H25 | 120.0 |
C6—C5—H5 | 120.0 | C26—C25—H25 | 120.0 |
C5—C6—C1 | 120.0 | C25—C26—C21 | 120.0 |
C5—C6—H6 | 120.0 | C25—C26—H26 | 120.0 |
C1—C6—H6 | 120.0 | C21—C26—H26 | 120.0 |
N1—C7—C8 | 121.7 (5) | N21—C27—C28 | 122.1 (10) |
N1—C7—H7 | 119.1 | N21—C27—H27 | 118.9 |
C8—C7—H7 | 119.1 | C28—C27—H27 | 118.9 |
C9—C8—C13 | 120.0 | C29—C28—C33 | 120.0 |
C9—C8—C7 | 119.2 (3) | C29—C28—C27 | 118.8 (6) |
C13—C8—C7 | 120.8 (3) | C33—C28—C27 | 121.2 (6) |
C8—C9—C10 | 120.0 | C28—C29—C30 | 120.0 |
C8—C9—H9 | 120.0 | C28—C29—H29 | 120.0 |
C10—C9—H9 | 120.0 | C30—C29—H29 | 120.0 |
C11—C10—C9 | 120.0 | C31—C30—C29 | 120.0 |
C11—C10—H10 | 120.0 | C31—C30—H30 | 120.0 |
C9—C10—H10 | 120.0 | C29—C30—H30 | 120.0 |
C10—C11—C12 | 120.0 | C30—C31—C32 | 120.0 |
C10—C11—N2 | 121.8 (3) | C30—C31—N22 | 122.4 (7) |
C12—C11—N2 | 118.2 (3) | C32—C31—N22 | 117.5 (7) |
C13—C12—C11 | 120.0 | C33—C32—C31 | 120.0 |
C13—C12—H12 | 120.0 | C33—C32—H32 | 120.0 |
C11—C12—H12 | 120.0 | C31—C32—H32 | 120.0 |
C12—C13—C8 | 120.0 | C32—C33—C28 | 120.0 |
C12—C13—H13 | 120.0 | C32—C33—H33 | 120.0 |
C8—C13—H13 | 120.0 | C28—C33—H33 | 120.0 |
C6—C1—C2—C3 | 0.0 | C26—C21—C22—C23 | 0.0 |
Cl1—C1—C2—C3 | 179.4 (3) | Cl2—C21—C22—C23 | −179.9 (8) |
C1—C2—C3—C4 | 0.0 | C21—C22—C23—C24 | 0.0 |
C2—C3—C4—C5 | 0.0 | C22—C23—C24—C25 | 0.0 |
C2—C3—C4—N1 | −175.4 (3) | C22—C23—C24—N21 | 178.9 (8) |
C7—N1—C4—C5 | 34.9 (4) | C27—N21—C24—C25 | −147.7 (7) |
C7—N1—C4—C3 | −149.8 (4) | C27—N21—C24—C23 | 33.4 (10) |
C3—C4—C5—C6 | 0.0 | C23—C24—C25—C26 | 0.0 |
N1—C4—C5—C6 | 175.2 (3) | N21—C24—C25—C26 | −179.0 (7) |
C4—C5—C6—C1 | 0.0 | C24—C25—C26—C21 | 0.0 |
C2—C1—C6—C5 | 0.0 | C22—C21—C26—C25 | 0.0 |
Cl1—C1—C6—C5 | −179.4 (3) | Cl2—C21—C26—C25 | 179.9 (7) |
C4—N1—C7—C8 | −174.8 (3) | C24—N21—C27—C28 | −178.3 (6) |
N1—C7—C8—C9 | 2.8 (6) | N21—C27—C28—C29 | 2.2 (11) |
N1—C7—C8—C13 | −177.2 (4) | N21—C27—C28—C33 | −176.6 (7) |
C13—C8—C9—C10 | 0.0 | C33—C28—C29—C30 | 0.0 |
C7—C8—C9—C10 | −180.0 (4) | C27—C28—C29—C30 | −178.8 (7) |
C8—C9—C10—C11 | 0.0 | C28—C29—C30—C31 | 0.0 |
C9—C10—C11—C12 | 0.0 | C29—C30—C31—C32 | 0.0 |
C9—C10—C11—N2 | −178.0 (4) | C29—C30—C31—N22 | 178.0 (8) |
O1—N2—C11—C10 | 0.1 (6) | O21—N22—C31—C30 | −4.7 (12) |
O2—N2—C11—C10 | −177.9 (7) | O22—N22—C31—C30 | 170.1 (13) |
O1—N2—C11—C12 | −178.0 (4) | O21—N22—C31—C32 | 173.3 (7) |
O2—N2—C11—C12 | 4.1 (9) | O22—N22—C31—C32 | −11.8 (15) |
C10—C11—C12—C13 | 0.0 | C30—C31—C32—C33 | 0.0 |
N2—C11—C12—C13 | 178.1 (4) | N22—C31—C32—C33 | −178.1 (8) |
C11—C12—C13—C8 | 0.0 | C31—C32—C33—C28 | 0.0 |
C9—C8—C13—C12 | 0.0 | C29—C28—C33—C32 | 0.0 |
C7—C8—C13—C12 | 180.0 (4) | C27—C28—C33—C32 | 178.7 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.95 | 2.55 | 3.489 (7) | 172 |
C13—H13···O1ii | 0.95 | 2.57 | 3.426 (5) | 151 |
C27—H27···Cl2i | 0.95 | 2.78 | 3.661 (11) | 155 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, −y+1/2, z−1/2. |
Contact | Percentage contributions | ||
CNBA | CNBA_1 | CNBA_2 | |
H···H | 25.5 | 26.2 | 24.7 |
O···H/H···O | 37.3 | 22.3 | 24.4 |
Cl···H/H···Cl | 3.5 | 14.5 | 14.8 |
C···H/H···C | 10.2 | 12.0 | 12.6 |
C···C | 10.2 | 11.0 | 11.1 |
N···H/H···N | 3.5 | 4.2 | 3.4 |
C···N | 3.2 | 2.4 | 2.4 |
O···O | 2.3 | 0.3 | 0.6 |
C···O | 1.6 | 1.9 | 0.7 |
O···Cl | 0.8 | 2.0 | 1.4 |
C···Cl | 0.4 | 1.0 | 1.9 |
Acknowledgements
HSE is grateful to the University of Neuchâtel and the Swiss National Science Foundation for their support over the years.
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