research communications
The
of the zwitterionic of 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate and 2,4-dichlorophenolaDepartment of Chemistry, University of Johannesburg, PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
*Correspondence e-mail: carderne@uj.ac.za
The title compound, C10H13Cl2NO2·C6H4Cl2O, was formed from the incomplete Mannich condensation reaction of 3-aminopropan-1-ol, formaldehyde and 2,4-dichlorophenol in methanol. This resulted in the formation of a of the zwitterionic Mannich base, 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate and the unreacted 2,4-dichlorophenol. The compound crystallizes in the monoclinic (in Cc) and the contains a molecule each of the 2,4-dichlorophenol and 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate. Examination of the shows that the two components are clearly linked together by hydrogen bonds. The packing patterns are most interesting along the b and the c axes, where the in the packs in a manner that shows alternating aromatic dichlorophenol fragments and polar hydrogen-bonded channels. The 2,4-dichlorophenol rings stack on top of one another, and these are held together by π–π interactions. The crystal studied was refined as an inversion twin.
Keywords: crystal structure; zwitterionic co-crystal; 2,4-dichlorophenol; bifurcated hydrogen bonding; π–π interactions.
CCDC reference: 1952329
1. Chemical context
The Mannich condensation is an important reaction in synthetic organic chemistry. The formation of the C—N bond in the resulting Mannich base is often an important step in the biosynthesis of several natural products, such as et al., 2006). Amino-phenolic ligands have versatile applications in inorganic as well as analytical chemistry. The flexible C—N bond in these ligands offers a tractable three-dimensional structure when coordinated to different metal centres (Riisiö et al., 2012). This provides numerous applications, particularly in enzyme mimicking and catalysis, as well as extraction of trace metals (Maurya et al., 2015; Riisiö et al., 2013; Lee et al., 2010). In the present study, we wanted to prepare a tripodal amino (bis) phenolate Mannich base derived from 3-propanol-1-amine, formaldehyde and 2,4-dichlorophenol. The reaction was performed following conventional bench-top techniques by heating a solution of the reactants in methanol (Sopo et al., 2006). However, probably because of the poor solubility, the dipodal product precipitated out from the incomplete reaction mixture. The dipodal product, 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate is stabilized by extensive intra- as well as intermolecular hydrogen bonding and thus exists as a zwitterion. The zwitterion co-crystallized with the unreacted phenol, resulting in the serendipitous isolation of the title compound.
and flavanoids (Sarhan2. Structural commentary
The title compound crystallizes in the monoclinic Cc. The molecular structure of the title compound is shown in Fig. 1, and the comprises a molecule of both 2,4-dichlorophenol and 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate, held together by hydrogen bonds.
in theA complete geometrical analysis using the Mogul geometry check tool (Bruno et al., 2004) within Mercury (Macrae et al., 2008) did not show any unusual bond lengths or bond angles. The torsion angles of the complete azaniumylphenolate chain (specifically C7–N1–C8–C9–C10–O2) deviate significantly from planarity (Table 1). This can be attributed to the hydrogen bonds in this environment (see below).
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The organic Mannich base exists as a zwitterion with the negative charge of phenolate being stabilized by the positively charged ammonium moiety. This is corroborated by the fact that the phenolic oxygen–carbon bond is slightly shorter [O1—C1 = 1.322 (4) Å] than the corresponding bond in the free 2,4-dichlorophenol [O1B—C1B = 1.355 (4) Å], indicating partial double-bond character and the presence of a phenoxide moiety in the zwitterion fragment. The ammonium nitrogen atom adopts a slightly distorted tetrahedral geometry.
3. Supramolecular features
The ). The zwitterion, 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate, is involved in intra– as well as intermolecular hydrogen bonding. The ammonium hydrogen H1B takes part in a bifurcated intramolecular hydrogen bond, N1—H1B⋯O1 and N1—H1B⋯O2, forcing the propyl chain of the zwitterion to adopt a distorted gauche conformation with an N1—C8—C9—C10 torsion angle of 64.5 (3)°. The other ammonium hydrogen, H1A, is involved in intermolecular hydrogen bonding with the negatively charged O atom of an adjacent zwitterion [d(H1A⋯O1) = 1.76 Å], extending the hydrogen bonding into an infinite network. The two components of the are also bonded together by intermolecular hydrogen bonds between the phenolic proton of 2,4-dichlorophenol and the alcoholic oxygen of the zwitterion [d(H1BA⋯O2) = 1.82 Å]. These hydrogen bonds give rise to interesting graph-set patterns, which are depicted in Fig. 2. The two intramolecular self-motifs of S11(6) are generated as a result of the bifurcation involving H1B, while the zwitterion interacts with a second zwitterion generating a large ring motif with the graph-set R22(16).
structure displays an extensive hydrogen-bonding network (Table 2The packing arrangement of the c-axis direction and also propagate along the a-axis direction, thereby resulting in a ladder-like structure network (Figs. 3 and 4). The presence of the glide plane in the ac plane of the crystal causes the packing to appear like a regular mirror image (Fig. 4). As a result of the nature of the packing arrangement in the it was possible to measure the ring centroid to ring centroid distance between the dichlorophenol rings of the adjacent layers; this distance was found to be in the range 4.045 (17)–4.056 (19) Å (Fig. 5). The layers are stacked in this manner as a result of extensive π–π interactions between the phenyl rings. A detailed list of the relevant π–π interactions is given in Table 3.
involves alternating hydrophobic layers of the aromatic dichlorophenol rings and the hydrogen-bonded polar channels. These layers stack one over the other along the4. Database survey
A search of the Cambridge structural database (Version 5.40, February 2019 updates; Groom et al., 2016) for the zwitterionic Mannich base, 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate gave no hits. Search parameters that included 2,4-dichlorophenol and other relevant starting materials as well as the resulted in only four hits, with one being the of 2,4-dichlorophenol itself (DCPHOM; Bavoux & Perrin, 1979); the second hit was a clathrate containing 2,4-dichlorophenol as a guest molecule within the cavities of zinc tetraphenylporphyrin molecules (JIVNOR; Byrn et al., 1991), and the third and fourth hits were found to be two three–component solvates [EVEYUB (Cai et al., 2016) and ZISJUI (Cai & Jin, 2014)] containing H-atom-bridged 2,4-dichlorophenolate/2,4-dichlorophenol units held together by O—H⋯N and O—H⋯O hydrogen bonds. Of all the hits found in the CSD, none of the structures is reported to have any π–π interactions between the phenyl rings, whereas the title compound has these types of interactions. However, a database search for the alcoholamine fragment, NH2(+)–(CH2)3–OH, gave seven hits. Two of these, GIPHIX (Büttner et al., 2007) and EPANUF (Pestov et al., 2010), also involved intramolecular hydrogen bonding resulting in S11(6) graph sets, as also seen in the title compound.
5. Synthesis and crystallization
The starting materials, comprising of 3-aminopropan-1-ol, formaldehyde and 2,4-dichlorophenol were purchased from Sigma Aldrich and used as received without any purification. To a methanolic solution of 3-amino-1-propanol (5 mmol, 0.38 g) was added a solution of formaldehyde (10 mmol, 0.81 g) in methanol under stirring. A solution of 2,4-dichlorophenol (10 mmol, 1.63 g) in methanol was added to the above mixture to afford a clear solution. The resulting solution was stirred at room temperature for two days to yield an oily solution. The oil was dissolved in diethyl ether and a few drops of methanol were added to the solution. The solution was then cooled in a refrigerator to obtain diffraction-quality single crystals.
6. Refinement
Crystal data, data collection and structure . All carbon-bound H atoms were placed in calculated positions and refined using a riding-model approximation, with C—H = 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C). H atoms bonded to N or O atoms were located from difference-Fourier electron-density maps and were also refined using a riding-model approximation with N—H bond distances of 0.89–0.91 Å and O—H = 0.84 Å with Uiso(H) = 1.5Ueq(N,O). The atom H1A was restrained by DFIX in SHELX to be at a distance of 0.88 (2) Å from N1 and by the SADI command to be equidistant from C7 and C8 (σ = 0.02 Å), so as to inhibit too much movement of this H atom during the The structure was also refined as an but low coverage of Friedel pairs in the data precludes the reliable determination of the All related structure and checks were carried out with PLATON (Spek, 2009).
details are summarized in Table 4
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Supporting information
CCDC reference: 1952329
https://doi.org/10.1107/S2056989019012544/fy2140sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012544/fy2140Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019012544/fy2140Isup3.mol
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C10H13Cl2NO2·C6H4Cl2O | F(000) = 848 |
Mr = 413.10 | Dx = 1.560 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 26.406 (2) Å | Cell parameters from 6679 reflections |
b = 9.5558 (9) Å | θ = 2.3–28.6° |
c = 7.1019 (6) Å | µ = 0.69 mm−1 |
β = 101.076 (2)° | T = 100 K |
V = 1758.6 (3) Å3 | Plank, colourless |
Z = 4 | 0.39 × 0.20 × 0.17 mm |
Bruker APEXII CCD diffractometer | 3842 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.053 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 28.6°, θmin = 1.6° |
Tmin = 0.688, Tmax = 0.746 | h = −34→35 |
15694 measured reflections | k = −12→12 |
4227 independent reflections | l = −9→9 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.092 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.52 e Å−3 |
4227 reflections | Δρmin = −0.25 e Å−3 |
220 parameters | Absolute structure: Refined as an inversion twin |
4 restraints | Absolute structure parameter: 0.03 (8) |
Primary atom site location: dual |
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. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.60636 (12) | 0.3974 (3) | 0.4792 (4) | 0.0142 (6) | |
C2 | 0.63604 (11) | 0.2750 (3) | 0.5205 (4) | 0.0157 (6) | |
C3 | 0.68630 (12) | 0.2726 (3) | 0.6225 (4) | 0.0165 (6) | |
H3 | 0.704950 | 0.187257 | 0.645494 | 0.020* | |
C4 | 0.70848 (12) | 0.3991 (3) | 0.6902 (5) | 0.0168 (6) | |
C5 | 0.68172 (11) | 0.5238 (3) | 0.6521 (4) | 0.0165 (6) | |
H5 | 0.697687 | 0.609545 | 0.698121 | 0.020* | |
C6 | 0.63169 (11) | 0.5240 (3) | 0.5469 (4) | 0.0147 (6) | |
O1 | 0.55807 (8) | 0.3971 (2) | 0.3846 (3) | 0.0155 (5) | |
C7 | 0.60594 (11) | 0.6628 (3) | 0.4870 (4) | 0.0158 (5) | |
H7A | 0.625976 | 0.738673 | 0.561830 | 0.019* | |
H7B | 0.606421 | 0.679235 | 0.349730 | 0.019* | |
N1 | 0.55136 (9) | 0.6690 (2) | 0.5164 (3) | 0.0147 (4) | |
H1A | 0.550581 | 0.642000 | 0.638674 | 0.018* | |
H1B | 0.532185 | 0.606588 | 0.435781 | 0.018* | |
C8 | 0.52697 (11) | 0.8107 (3) | 0.4826 (4) | 0.0175 (5) | |
H8A | 0.550100 | 0.879869 | 0.559396 | 0.021* | |
H8B | 0.494264 | 0.809926 | 0.531229 | 0.021* | |
C9 | 0.51540 (11) | 0.8601 (3) | 0.2744 (4) | 0.0175 (6) | |
H9A | 0.503078 | 0.958053 | 0.271129 | 0.021* | |
H9B | 0.547924 | 0.859396 | 0.224456 | 0.021* | |
C10 | 0.47556 (12) | 0.7729 (3) | 0.1416 (4) | 0.0202 (6) | |
H10A | 0.443328 | 0.769495 | 0.193267 | 0.024* | |
H10B | 0.467599 | 0.817985 | 0.013813 | 0.024* | |
O2 | 0.49333 (8) | 0.6335 (2) | 0.1213 (3) | 0.0184 (4) | |
H2 | 0.513930 | 0.633301 | 0.044658 | 0.028* | |
Cl1 | 0.60850 (3) | 0.11500 (7) | 0.43483 (9) | 0.01842 (17) | |
Cl2 | 0.77111 (3) | 0.39949 (8) | 0.82500 (10) | 0.0250 (2) | |
O1B | 0.44186 (9) | 0.3939 (2) | 0.1038 (4) | 0.0241 (6) | |
H1BA | 0.455585 | 0.473101 | 0.102256 | 0.036* | |
C1B | 0.39283 (14) | 0.3987 (3) | 0.0027 (5) | 0.0199 (7) | |
C2B | 0.36413 (13) | 0.2748 (4) | −0.0255 (5) | 0.0222 (7) | |
C3B | 0.31382 (13) | 0.2721 (4) | −0.1258 (5) | 0.0248 (7) | |
H3B | 0.295037 | 0.186795 | −0.143940 | 0.030* | |
C4B | 0.29142 (13) | 0.3965 (3) | −0.1992 (5) | 0.0218 (7) | |
C5B | 0.31829 (12) | 0.5215 (4) | −0.1709 (4) | 0.0216 (7) | |
H5B | 0.302285 | 0.606604 | −0.219504 | 0.026* | |
C6B | 0.36880 (12) | 0.5211 (3) | −0.0710 (4) | 0.0205 (6) | |
H6B | 0.387375 | 0.606724 | −0.052605 | 0.025* | |
Cl2B | 0.22825 (3) | 0.39666 (9) | −0.32799 (12) | 0.0308 (2) | |
Cl1B | 0.39215 (3) | 0.11872 (9) | 0.07078 (15) | 0.0370 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0169 (16) | 0.0145 (16) | 0.0124 (14) | −0.0011 (11) | 0.0055 (11) | −0.0008 (9) |
C2 | 0.0192 (15) | 0.0122 (15) | 0.0165 (13) | −0.0052 (12) | 0.0057 (11) | −0.0028 (10) |
C3 | 0.0178 (15) | 0.0129 (16) | 0.0189 (13) | 0.0016 (12) | 0.0036 (11) | −0.0006 (10) |
C4 | 0.0110 (15) | 0.0175 (17) | 0.0210 (15) | −0.0005 (11) | 0.0011 (12) | −0.0027 (11) |
C5 | 0.0172 (15) | 0.0150 (16) | 0.0177 (14) | −0.0015 (12) | 0.0048 (11) | −0.0019 (10) |
C6 | 0.0178 (14) | 0.0128 (15) | 0.0151 (13) | 0.0005 (12) | 0.0069 (10) | −0.0004 (10) |
O1 | 0.0145 (12) | 0.0156 (12) | 0.0163 (10) | −0.0013 (8) | 0.0029 (8) | −0.0017 (7) |
C7 | 0.0168 (13) | 0.0120 (14) | 0.0193 (13) | 0.0005 (10) | 0.0049 (10) | 0.0008 (9) |
N1 | 0.0168 (11) | 0.0144 (11) | 0.0130 (11) | −0.0011 (9) | 0.0033 (8) | 0.0003 (8) |
C8 | 0.0223 (14) | 0.0120 (13) | 0.0182 (13) | 0.0004 (10) | 0.0038 (10) | 0.0005 (10) |
C9 | 0.0199 (14) | 0.0154 (14) | 0.0174 (14) | 0.0010 (10) | 0.0037 (11) | 0.0026 (10) |
C10 | 0.0212 (14) | 0.0191 (15) | 0.0197 (14) | 0.0031 (11) | 0.0026 (10) | −0.0015 (11) |
O2 | 0.0193 (10) | 0.0168 (10) | 0.0201 (10) | −0.0005 (8) | 0.0060 (8) | −0.0012 (7) |
Cl1 | 0.0201 (4) | 0.0128 (4) | 0.0216 (3) | −0.0027 (3) | 0.0023 (3) | −0.0022 (3) |
Cl2 | 0.0169 (4) | 0.0194 (4) | 0.0353 (5) | 0.0010 (3) | −0.0038 (3) | −0.0041 (3) |
O1B | 0.0159 (13) | 0.0151 (13) | 0.0403 (15) | −0.0022 (8) | 0.0027 (10) | −0.0003 (9) |
C1B | 0.0152 (16) | 0.0220 (19) | 0.0235 (17) | −0.0002 (12) | 0.0062 (12) | −0.0015 (11) |
C2B | 0.0199 (16) | 0.0120 (17) | 0.0352 (17) | 0.0023 (13) | 0.0068 (13) | 0.0024 (12) |
C3B | 0.0211 (18) | 0.0162 (19) | 0.0373 (18) | −0.0030 (13) | 0.0059 (14) | −0.0017 (13) |
C4B | 0.0184 (18) | 0.0197 (18) | 0.0274 (17) | −0.0020 (12) | 0.0046 (14) | −0.0020 (12) |
C5B | 0.0234 (17) | 0.0164 (17) | 0.0251 (16) | −0.0007 (13) | 0.0045 (12) | 0.0015 (12) |
C6B | 0.0243 (17) | 0.0142 (16) | 0.0242 (16) | −0.0043 (13) | 0.0076 (12) | −0.0022 (11) |
Cl2B | 0.0200 (5) | 0.0207 (5) | 0.0474 (6) | −0.0024 (3) | −0.0038 (4) | 0.0031 (4) |
Cl1B | 0.0209 (5) | 0.0167 (5) | 0.0705 (7) | 0.0004 (3) | 0.0018 (5) | 0.0095 (4) |
C1—C2 | 1.407 (4) | C9—H9A | 0.9900 |
C1—C6 | 1.421 (4) | C9—H9B | 0.9900 |
C1—O1 | 1.322 (4) | C9—C10 | 1.520 (4) |
C2—C3 | 1.385 (4) | C10—H10A | 0.9900 |
C2—Cl1 | 1.751 (3) | C10—H10B | 0.9900 |
C3—H3 | 0.9500 | C10—O2 | 1.429 (3) |
C3—C4 | 1.388 (4) | O2—H2 | 0.8400 |
C4—C5 | 1.386 (4) | O1B—H1BA | 0.8400 |
C4—Cl2 | 1.744 (3) | O1B—C1B | 1.355 (4) |
C5—H5 | 0.9500 | C1B—C2B | 1.400 (5) |
C5—C6 | 1.387 (4) | C1B—C6B | 1.384 (5) |
C6—C7 | 1.514 (4) | C2B—C3B | 1.382 (5) |
C7—H7A | 0.9900 | C2B—Cl1B | 1.745 (3) |
C7—H7B | 0.9900 | C3B—H3B | 0.9500 |
C7—N1 | 1.496 (3) | C3B—C4B | 1.384 (5) |
N1—H1A | 0.9100 | C4B—C5B | 1.385 (4) |
N1—H1B | 0.9100 | C4B—Cl2B | 1.742 (4) |
N1—C8 | 1.499 (3) | C5B—H5B | 0.9500 |
C8—H8A | 0.9900 | C5B—C6B | 1.385 (4) |
C8—H8B | 0.9900 | C6B—H6B | 0.9500 |
C8—C9 | 1.526 (4) | ||
C2—C1—C6 | 115.5 (3) | C9—C8—H8A | 108.3 |
O1—C1—C2 | 123.3 (3) | C9—C8—H8B | 108.3 |
O1—C1—C6 | 121.3 (3) | C8—C9—H9A | 108.6 |
C1—C2—Cl1 | 118.4 (2) | C8—C9—H9B | 108.6 |
C3—C2—C1 | 124.2 (3) | H9A—C9—H9B | 107.6 |
C3—C2—Cl1 | 117.3 (2) | C10—C9—C8 | 114.7 (2) |
C2—C3—H3 | 121.2 | C10—C9—H9A | 108.6 |
C2—C3—C4 | 117.7 (3) | C10—C9—H9B | 108.6 |
C4—C3—H3 | 121.2 | C9—C10—H10A | 109.2 |
C3—C4—Cl2 | 119.0 (2) | C9—C10—H10B | 109.2 |
C5—C4—C3 | 121.1 (3) | H10A—C10—H10B | 107.9 |
C5—C4—Cl2 | 120.0 (2) | O2—C10—C9 | 111.8 (2) |
C4—C5—H5 | 119.9 | O2—C10—H10A | 109.2 |
C4—C5—C6 | 120.2 (3) | O2—C10—H10B | 109.2 |
C6—C5—H5 | 119.9 | C10—O2—H2 | 109.5 |
C1—C6—C7 | 119.6 (3) | C1B—O1B—H1BA | 109.5 |
C5—C6—C1 | 121.3 (3) | O1B—C1B—C2B | 118.9 (3) |
C5—C6—C7 | 118.8 (3) | O1B—C1B—C6B | 123.4 (3) |
C6—C7—H7A | 109.0 | C6B—C1B—C2B | 117.7 (3) |
C6—C7—H7B | 109.0 | C1B—C2B—Cl1B | 119.3 (3) |
H7A—C7—H7B | 107.8 | C3B—C2B—C1B | 122.0 (3) |
N1—C7—C6 | 112.8 (2) | C3B—C2B—Cl1B | 118.6 (3) |
N1—C7—H7A | 109.0 | C2B—C3B—H3B | 120.8 |
N1—C7—H7B | 109.0 | C2B—C3B—C4B | 118.5 (3) |
C7—N1—H1A | 108.7 | C4B—C3B—H3B | 120.8 |
C7—N1—H1B | 108.7 | C3B—C4B—C5B | 121.1 (3) |
C7—N1—C8 | 114.1 (2) | C3B—C4B—Cl2B | 119.7 (3) |
H1A—N1—H1B | 107.6 | C5B—C4B—Cl2B | 119.2 (3) |
C8—N1—H1A | 108.7 | C4B—C5B—H5B | 120.4 |
C8—N1—H1B | 108.7 | C4B—C5B—C6B | 119.2 (3) |
N1—C8—H8A | 108.3 | C6B—C5B—H5B | 120.4 |
N1—C8—H8B | 108.3 | C1B—C6B—C5B | 121.5 (3) |
N1—C8—C9 | 115.8 (2) | C1B—C6B—H6B | 119.3 |
H8A—C8—H8B | 107.4 | C5B—C6B—H6B | 119.3 |
C1—C2—C3—C4 | 0.8 (4) | N1—C8—C9—C10 | 64.5 (3) |
C1—C6—C7—N1 | 50.1 (3) | C8—C9—C10—O2 | −65.1 (3) |
C2—C1—C6—C5 | −2.1 (4) | Cl1—C2—C3—C4 | 179.7 (2) |
C2—C1—C6—C7 | 171.6 (2) | Cl2—C4—C5—C6 | −179.2 (2) |
C2—C3—C4—C5 | −1.8 (5) | O1B—C1B—C2B—C3B | 179.5 (3) |
C2—C3—C4—Cl2 | 178.3 (2) | O1B—C1B—C2B—Cl1B | 0.3 (4) |
C3—C4—C5—C6 | 0.8 (5) | O1B—C1B—C6B—C5B | −179.0 (3) |
C4—C5—C6—C1 | 1.2 (4) | C1B—C2B—C3B—C4B | −0.3 (5) |
C4—C5—C6—C7 | −172.6 (3) | C2B—C1B—C6B—C5B | −0.6 (5) |
C5—C6—C7—N1 | −136.0 (3) | C2B—C3B—C4B—C5B | −0.9 (5) |
C6—C1—C2—C3 | 1.2 (4) | C2B—C3B—C4B—Cl2B | 179.5 (2) |
C6—C1—C2—Cl1 | −177.8 (2) | C3B—C4B—C5B—C6B | 1.4 (5) |
C6—C7—N1—C8 | 172.5 (2) | C4B—C5B—C6B—C1B | −0.6 (5) |
O1—C1—C2—C3 | −178.7 (3) | C6B—C1B—C2B—C3B | 1.1 (5) |
O1—C1—C2—Cl1 | 2.4 (4) | C6B—C1B—C2B—Cl1B | −178.2 (2) |
O1—C1—C6—C5 | 177.7 (3) | Cl2B—C4B—C5B—C6B | −179.0 (2) |
O1—C1—C6—C7 | −8.6 (4) | Cl1B—C2B—C3B—C4B | 178.9 (3) |
C7—N1—C8—C9 | 69.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.91 | 1.76 | 2.663 (3) | 171 |
N1—H1B···O1 | 0.91 | 2.17 | 2.779 (3) | 124 |
N1—H1B···O2 | 0.91 | 2.29 | 2.947 (3) | 129 |
O2—H2···O1ii | 0.84 | 1.80 | 2.634 (3) | 171 |
O1B—H1BA···O2 | 0.84 | 1.82 | 2.653 (3) | 172 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2. |
Cg1 and Cg2 are the centroids of the C1–C6 and C1B–C6B rings, respectively. |
Cg···Cg | Distance | Slippage |
Cg1···Cg1i | 4.0449 (17) | 2.006 |
Cg1···Cg1ii | 4.0448 (17) | 2.583 |
Cg2···Cg2i | 4.0559 (19) | 2.714 |
Cg2···Cg2ii | 4.0559 (19) | 1.849 |
Symmetry codes: (i) x, -y + 1, z + 1/2; (ii) x, -y + 1, z - 1/2. |
Acknowledgements
The authors thank the University of Johannesburg for providing access to the Single Crystal XRD facilities. They also gratefully acknowledge Dr Matthias Zeller, Purdue University, Indiana, USA, for assistance in solving the crystal structure.
Funding information
Funding for this research was provided by: National Research Fund Thuthuka (grant No. 99164 to CA). BU thanks the University of Johannesburg for funding from the UJ–GES post-doctoral fellowship. CA and BU thank the Research Centre for Synthesis and Catalysis for ancillary funding for the project.
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