research communications
The crystal structures of three disordered 2-substituted benzimidazole esters
aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore-574199, India, cInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Strasse 2, D-64287 Darmstadt, Germany, and dSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
*Correspondence e-mail: yathirajan@hotmail.com
The crystal structures of three benzimidazole H-benzimidazole-5-carboxylate, C20H18N2O3, (I), the prop-2-yn-1-oxyphenyl unit is disordered over two sets of atomic sites having effectively equal occupancies, 0.506 (5) and 0.494 (5). The propyl substituent in ethyl 1-propyl-2-(pyren-1-yl)-1H-benzimidazole-5-carboxylate, C29H24N2O2, (II), is disordered over two sets of atomic sites having occupancies 0.601 (8) and 0.399 (8), and the ester unit in ethyl 1-methyl-2-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1H-benzimidazole-5-carboxylate, C21H19ClN4O2 (III), is disordered over two sets of atomic sites having occupancies 0.645 (7) and 0.355 (7). In each of the C—H⋯π(arene) hydrogen bonds in (I), the donor and acceptor form parts of different disorder components, so that no continuous aggregation is possible. The molecules of (II) are linked by a single C—H⋯O hydrogen bond into C(10) chains, which are linked into sheets by a π–π stacking interaction, whereas those of (III) are just linked into C(13) chains, again by a single C—H⋯O hydrogen bond. Comparisons are made with the structures of some related compounds.
containing aryl or heterocyclic substituents at position 2 are reported, and all three exhibit disorder of molecular entities. In ethyl 1-methyl-2-[4-(prop-2-ynoxy)phenyl]-11. Chemical context
The use of compounds containing the benzo[d]imidazole unit as chemotherapeutic agents having antimicrobial, antiparasitic, antitumour and antiviral activity has been comprehensively reviewed (Boiani & Gonzalez, 2005). In particular, 2-substituted benzo[d]imidazoles have recently been evaluated for their antimicrobial and antioxidant activity (Zhou et al., 2013; Bektaş et al., 2020). With these considerations in mind, we have synthesized some new 2-substituted benzo[d]imidazoles and here we report the structures of two new benzimidazole namely ethyl 1-methyl-2-[4-(prop-2-ynoxy)phenyl]-1H-benzimidazole-5-carboxylate (I) (Fig. 1) and ethyl 1-propyl-2-(pyren-1-yl)-1H-benzimidazole-5-carboxylate (II) (Fig. 2) carrying aromatic substituents at position 2 of the heterocyclic ring.
The structure of the related compound ethyl 1-methyl-2-(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1H-benzimidazole-5-carboxylate (III) (Fig. 3) was reported recently (Manju et al., 2018), but the reported was based on a rather unusual disorder model, in which only some of the atoms in the ester function, namely the methylene group and the H atoms of the methyl group, were described as disordered over two sets of atomic sites having occupancies 0.719 (14) and 0.281 (14), but with all other components of this substituent fully ordered. This model leads to some unexpected distances within the ethoxy unit, O—C =1.480 (4) and 1.618 (13) Å and C—C = 1.274 (6) and 1.295 (10) Å, which in turn cast doubt on the correctness of the disorder model. Accordingly, we have taken the opportunity to collect a new, and rather better data set for compound (III) [4250 reflections with Rint = 0.0126 as against 4010 reflections with Rint = 0.0418 (Manju et al., 2018)] and, using a more realistic disorder model, we have refined the structure of (III) to R1 = 0.0395 as against a value of 0.0526 (Manju et al., 2018).
Compounds (I)–(III) were prepared from the commercially available precursor ethyl 4-chloro-3-nitrobenzoate (A) (Fig. 4), which readily undergoes nucleophilic substitution with primary to give the intermediates (B): subsequent reaction of (B) with sodium dithionite in the presence of the appropriate aldehyde leads to the products (I)–(III) in overall yields of 58-68%.
2. Structural commentary
The molecules of compounds (I)–(III) all exhibit disorder. In compound (I) (Fig. 1), the (prop-2-yn-1-oxy)phenyl unit is disordered over two sets of atomic sites having essentially equal occupancies, 0.506 (5) and 0.494 (5), such that the two orientations of the phenyl ring make almost identical dihedral angles with the adjacent imidazole ring, 27.8 (4) and 27.0 (4)° respectively, and with a dihedral angle of 54.7 (3)° between the planes of the two disorder components. The propyl group in compound (II) (Fig. 2) is disordered over two sets of atomic sites having occupancies 0.601 (8) and 0.399 (8), while in compound (III) (Fig. 3), the whole ester unit is disordered over two sets of atomic sites having occupancies 0.645 (7) and 0.355 (7); so, far from there being a single site for the methyl C atom in the ester unit (Manju et al., 2018), there are two such sites in the present disorder model, separated by 0.931 (11) Å.
Despite the fact that atom O51 acts as a hydrogen-bond acceptor in both (II) and (III), although not in (I), the conformation of the ester unit in (II) is different from that in (I) and (III) (Figs. 1–4): the cause of this is unclear. The bond lengths in the pyrene fragment of compound (II) present some interesting features. While the distances in the rings containing atoms C22 and C27 are all typical of those in delocalized aromatic rings, those in the other two rings exhibit significant bond fixation (Glidewell & Lloyd, 1984). Thus the distances C24—C25 and C29—C210, 1.320 (3) and 1.342 (3) Å, are typical of double bonds (Allen et al., 1987), while those for the bonds C23A—C24, C23B—C25B, C25—C25A, C28A—C29 and C210—C20A are all closely grouped in the d range 1.424 (3)–1.436 (3) Å, typical of single bonds carrying alkenyl or aromatic substituents (Allen et al., 1987). Hence there can be no continuous peripheral delocalization in this unit.
3. Supramolecular features
The supramolecular assembly in compounds (II) and (III) is very simple, but that in compound (I) is less straightforward. In compound (II), molecules that are related by the 21 screw axis along (0.5, y, 0.25) are linked by a C—H⋯O hydrogen bond (Table 1) to form a C(10) chain (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) running parallel to the [010] direction (Fig. 5). Two chains of this type, related to one another by inversion, pass through each and these chains are linked by a π–π interaction involving the terminal aromatic ring, containing atom C27 (Fig. 2). The terminal aromatic rings in the molecules at (x, y, z) and (2 − x, 2 − y, 1 − z) are parallel with an interplanar spacing of 3.430 (2) Å: the ring-centroid separation is 3.727 (2) Å and the ring-centroid offset is 1.459 (2) Å. This interaction links the hydrogen-bonded chain around the screw axis along (0.5, y, 0.25) (Fig. 5) with the corresponding chains along (1.5, y, 0.75) and (−0.5, y, −0.25), hence generating a π-stacked sheet of hydrogen-bonded chains lying parallel to (10) (Fig. 6). There is also another short C-H⋯O contact in the structure of (II), involving atom C11 (Table 1), but the C—H⋯O angle is very small, such that the interaction energy here is likely to be negligibly small (Wood et al., 2009). Hence, it is probably better to regard this as an adventitious contact rather than as a structurally significant interaction: in any event, this contact would not influence the dimensionality of the supramolecular assembly.
There is just one C—H⋯O hydrogen bond in the structure of compound (III), and its dimensions for the two disorder components are fairly similar, although the distances in the minor component are rather longer than those for the major form (Table 1); only the major disorder form needs to be considered. The hydrogen bond links molecules that are related by translation to form a C(13) chain running parallel to the [100] direction (Fig. 7).
The structure of compound (I) contains three C—H⋯π(arene) hydrogen bonds, all involving the unfused aryl ring (Table 1), but the alkyne unit acts as neither donor nor acceptor. If all of the donors and acceptors were present with full occupancy, the effect of the hydrogen bonds would be to link the molecules of (I) into a complex ribbon running parallel to the [010] direction (Fig. 8). However, in each of these hydrogen bonds, the donor and the acceptor form parts of different disorder components, so that the ribbon cannot be continuous, but it is punctuated into a succession of short fragments. The punctuated ribbon containing the reference molecule lies along (0.25, y, 0.5) and there are symmetry-related ribbons along (0.25, y, 0), (0.75, y, 0) and (0.75, y, 0.5) (Fig. 9), but with no direction-specific interactions between adjacent ribbons.
4. Database survey
A representative example of a simple 2-substituted benzimidazole is provided by 2-(1-naphthylmethyl)-1H-benzo[d]imidazole (IV) (Ding et al., 2007); here the molecules are linked by a single N—H⋯N hydrogen bond to form C(4) chains, which are themselves linked into sheets by a C—H⋯π(arene) hydrogen bond. Structures have been reported for a number of derived from substituted benzimidazole-5-carboxylic acids, including: ethyl 1-[3-(1H-imidazol-1-yl)propyl]-2-(4-chlorophenyl)-1H-benzo[d]imidazole- 5-caboxylate dehydrate (V) (Yoon et al., 2011), where a combination of O—H⋯O and O—H⋯N hydrogen bonds generates complex sheets, rather than the three-dimensional assembly specified in the original report (Yoon et al., 2011); the two closely related methyl 2-(4-bromophenyl)-1-(5-tert-butyl-1H-pyrazol-3-yl)-1H-benzimidazole-5-carboxylate (VI) (Cortés et al., 2011) and octyl 1-(5-tert-butyl-1H-pyrazol-3-yl)-2-(4-chlorophenyl)1H-benzimidazole-5-carboxylate (VII) (Cortés et al., 2014), where the molecules are linked into chains of edge-fused rings in (VI) by a combination of N—H⋯O and C—H⋯π(arene) hydrogen bonds, but into complex sheets in (VII) generated by a combination of N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds; and ethyl 1-(4-fluorobenzyl)-2-(4-methoxyphenyl)-1H-benzo[d]imidazole-5-carboxylate (VIII) Naveen et al., 2016), in which inversion-related pairs of molecules are linked by C—H⋯O hydrogen bonds to form cyclic, centrosymmetric R22(22) dimers. It is notable that, in marked contrast to the compounds (I)–(III) reported here, none of compounds (IV)–(VIII) exhibits any disorder: we also note the contrasting patterns of supramolecular interactions and assembly in the closely related (VI) and (VII).
5. Synthesis and crystallization
All reagents were obtained commercially, and all were used as received. For the synthesis of the intermediates of type (B) (Fig. 4), ethyl 4-chloro-3-nitrobenzoate (2.29 g, 0.01 mol) was dissolved in tetrahydrofuran (20 ml) and 0.01 mol of the appropriate amine was added [0.80 ml of a 40% aqueous solution of methylamine when R = Me, or 0.059 g of propylamine when R = propyl], and these mixtures were then stirred at ambient temperature for 4 h. The resulting solid intermediates (B) were collected by filtration, dried in air and used without further purification. For the synthesis of the products (I)–(III), sodium dithionite (1.74 g, 0.01 mol) was added to a mixture of (B) (0.01 mol) and the appropriate aldehyde (0.01 mol) [1.61 g of 4-propynyloxybenzaldehyde for (I); 2.30 g of pyrene-1-carboxaldehyde for (II); 2.20 g of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxaldehyde for (III)], in dimethylsulfoxide (30 ml). The reaction mixtures were then subjected to microwave irradiation (600 W) for 5 min for (I), 6.5 min for (II) and 6 min for (III). When the reactions were complete, as judged by thin-later the resulting solid products were collected by filtration and dried in air.
Compound (I). Yield 62%, m.p. 465 K; IR (cm−1) 2218 (C≡C), 1708 (C=O), 1624(C=N); NMR (CDCl3) δ(1H) 1.37 (3H, t, J = 7.1 Hz, ester CH3), 3.48 (1H, t, J = 2.4 Hz, propynyl CH), 3.97 (3H, s, N—CH3), 4.36 (2H, q, J = 7.1 Hz, ester CH2), 4.90 (2H, d, J = 2.4 Hz, propynyl CH2), 7.22 (2H, d, J = 6.9 Hz) and 7.87 (2H, d, J = 6.9 Hz) (–C6H4–), 7.76 (1H, d, J = 8.6 Hz, H-7), 8.01 (1H, dd, J = 8.6 Hz and 1.3 Hz, H-6), 8.29 (1H, d, J = 1.3 Hz, H-4).
Compound (II). Yield 68%, m.p. 553 K; IR (cm−1) 1716 (C=O), 1615 (C=N); NMR (CDCl3) δ(1H) 0.62 (23H, t, J = 7.4 Hz, propyl CH3), 1.45 (3H, t, J = 7.1 Hz, ester CH3), 1.63 (2H, m, central CH2 of propyl), 4.06 (2H, t, J = 7.4 Hz), N—CH2), 4.45 (2H, q, J = 7.1 Hz, ester CH2), 7.53 (1H, d, J = 8.5 Hz, H-7), 7.91 (1H, dd, J = 8.5 Hz and 0.9 Hz, H-6), 8.05–8.32 (9H, m, pyrene), 8.67 (1H, d, J = 0.9 Hz, H-4).
Compound (III). Yield 58%, m.p. 435 K; IR (cm−1) 1703 (C=O), 1614 (C=N); NMR (CDCl3) δ(1H) 1.37 (3H, t, J = 7.0 Hz, ester CH3), 2.33 (3H, s, pyrazole CH3), 3.85 (3H, s, N—CH3), 4.36 (2H, q, J = 7.0 Hz, ester CH2), 7.51–8.30 (8H, m, aromatic).
Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in ethanol-acetonitrile (initial composition 3:1 v/v).
6. Refinement
Crystal data, data collection and structure . Two bad outlier reflections (2 2 9) and (1 1 19) were omitted from the final of compound (I). All H atoms, apart from those in the minor disorder components, were located in difference maps. The H atoms were then all treated as riding atoms in geometrically idealized positions, with C—H distances of 0.93 Å (alkenyl, alkynyl and aromatic), 0.96 Å (CH3) or 0.97 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were allowed to rotate but not to tilt, and 1.2 for all other H atoms. For the disorder components, the corresponding distances between bonding components and the 1,3 distances between non-bonding components were restrained to be equal, subject to s.u. values of 0.01 and 0.02 Å, respectively. In addition, for compound (I), similarity restraints were applied to the atoms of each orientation of the disordered aryl ring, while the anisotropic displacement parameters for corresponding pairs of atoms in the propynyloxy unit were constrained to be the same. Similarity restraints were applied to the displacement parameters of the terminal C atoms of the two disorder components of the propyl group in compound (II), and to those of corresponding pairs of atoms in the disordered ester unit of compound (III). Subject to these conditions, the site occupancies for the disordered fragments refined to 0.506 (5) and 0.494 (5) in (I), 0.601 (8) and 0.399 (8) in (II), and 0.645 (7) and 0.355 (7) in (III).
details are summarized in Table 2
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Supporting information
https://doi.org/10.1107/S2056989021003364/wm5604sup1.cif
contains datablocks global, I, II, III. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021003364/wm5604Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021003364/wm5604IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989021003364/wm5604IIIsup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989021003364/wm5604Isup5.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989021003364/wm5604IIsup6.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989021003364/wm5604IIIsup7.cml
For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell
CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).C20H18N2O3 | F(000) = 1408 |
Mr = 334.36 | Dx = 1.305 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.947 (2) Å | Cell parameters from 3698 reflections |
b = 4.5907 (5) Å | θ = 2.5–27.9° |
c = 41.305 (4) Å | µ = 0.09 mm−1 |
β = 91.016 (8)° | T = 293 K |
V = 3402.6 (6) Å3 | Needle, yellow |
Z = 8 | 0.36 × 0.18 × 0.18 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 3350 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2002 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 26.0°, θmin = 2.5° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −20→22 |
Tmin = 0.956, Tmax = 0.984 | k = −5→5 |
7151 measured reflections | l = −51→50 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.068 | H-atom parameters constrained |
wR(F2) = 0.187 | w = 1/[σ2(Fo2) + (0.0762P)2 + 3.8366P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3350 reflections | Δρmax = 0.24 e Å−3 |
286 parameters | Δρmin = −0.23 e Å−3 |
93 restraints |
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) | |
N1 | 0.43626 (12) | 1.0912 (5) | 0.59851 (6) | 0.0489 (6) | |
C2 | 0.38294 (15) | 0.9896 (6) | 0.57634 (7) | 0.0446 (7) | |
N3 | 0.33476 (13) | 0.8107 (6) | 0.58926 (6) | 0.0512 (7) | |
C3A | 0.35648 (15) | 0.7906 (7) | 0.62171 (7) | 0.0495 (7) | |
C4 | 0.32625 (17) | 0.6286 (8) | 0.64653 (7) | 0.0566 (8) | |
H4 | 0.2840 | 0.5148 | 0.6429 | 0.068* | |
C5 | 0.36027 (17) | 0.6401 (7) | 0.67670 (7) | 0.0544 (8) | |
C6 | 0.42355 (19) | 0.8131 (8) | 0.68213 (8) | 0.0637 (9) | |
H6 | 0.4455 | 0.8170 | 0.7027 | 0.076* | |
C7 | 0.45376 (18) | 0.9757 (8) | 0.65814 (8) | 0.0619 (9) | |
H7 | 0.4957 | 1.0908 | 0.6620 | 0.074* | |
C7A | 0.41952 (16) | 0.9633 (7) | 0.62761 (7) | 0.0482 (7) | |
C11 | 0.4975 (2) | 1.2924 (9) | 0.59433 (9) | 0.0821 (12) | |
H11A | 0.5175 | 1.2689 | 0.5731 | 0.123* | |
H11B | 0.5358 | 1.2531 | 0.6103 | 0.123* | |
H11C | 0.4800 | 1.4885 | 0.5969 | 0.123* | |
C21 | 0.38139 (14) | 1.0664 (6) | 0.54171 (7) | 0.0411 (6) | 0.494 (5) |
C22 | 0.4071 (3) | 1.3274 (12) | 0.52923 (13) | 0.0475 (16) | 0.494 (5) |
H22 | 0.4282 | 1.4637 | 0.5433 | 0.057* | 0.494 (5) |
C23 | 0.4023 (3) | 1.3911 (13) | 0.49670 (13) | 0.0467 (15) | 0.494 (5) |
H23 | 0.4203 | 1.5675 | 0.4890 | 0.056* | 0.494 (5) |
C24 | 0.370 (2) | 1.190 (10) | 0.4754 (3) | 0.043 (4) | 0.494 (5) |
C25 | 0.3444 (3) | 0.9279 (13) | 0.48742 (13) | 0.0438 (15) | 0.494 (5) |
H25 | 0.3234 | 0.7913 | 0.4734 | 0.053* | 0.494 (5) |
C26 | 0.3497 (3) | 0.8692 (12) | 0.52000 (12) | 0.0433 (15) | 0.494 (5) |
H26 | 0.3316 | 0.6930 | 0.5277 | 0.052* | 0.494 (5) |
O24 | 0.374 (4) | 1.250 (18) | 0.4431 (5) | 0.059 (3) | 0.494 (5) |
C27 | 0.3276 (10) | 1.101 (4) | 0.4211 (3) | 0.064 (4) | 0.494 (5) |
H27A | 0.2762 | 1.1196 | 0.4276 | 0.076* | 0.494 (5) |
H27B | 0.3404 | 0.8960 | 0.4209 | 0.076* | 0.494 (5) |
C28 | 0.336 (2) | 1.224 (9) | 0.3893 (4) | 0.066 (7) | 0.494 (5) |
C29 | 0.347 (2) | 1.295 (7) | 0.3629 (5) | 0.087 (6) | 0.494 (5) |
H29 | 0.3550 | 1.3533 | 0.3417 | 0.104* | 0.494 (5) |
C31 | 0.38139 (14) | 1.0664 (6) | 0.54171 (7) | 0.0411 (6) | 0.506 (5) |
C32 | 0.4451 (3) | 1.1350 (13) | 0.52509 (12) | 0.0436 (14) | 0.506 (5) |
H32 | 0.4907 | 1.1427 | 0.5361 | 0.052* | 0.506 (5) |
C33 | 0.4418 (3) | 1.1920 (13) | 0.49242 (12) | 0.0432 (15) | 0.506 (5) |
H33 | 0.4850 | 1.2396 | 0.4815 | 0.052* | 0.506 (5) |
C34 | 0.3741 (18) | 1.179 (9) | 0.4755 (3) | 0.041 (3) | 0.506 (5) |
C35 | 0.3100 (3) | 1.1029 (14) | 0.49176 (12) | 0.0417 (14) | 0.506 (5) |
H35 | 0.2646 | 1.0900 | 0.4806 | 0.050* | 0.506 (5) |
C36 | 0.3141 (3) | 1.0467 (14) | 0.52448 (12) | 0.0451 (15) | 0.506 (5) |
H36 | 0.2711 | 0.9945 | 0.5353 | 0.054* | 0.506 (5) |
O34 | 0.373 (4) | 1.268 (18) | 0.4439 (5) | 0.059 (3) | 0.506 (5) |
C37 | 0.3125 (9) | 1.196 (4) | 0.4235 (3) | 0.064 (4) | 0.506 (5) |
H37A | 0.2675 | 1.2874 | 0.4313 | 0.076* | 0.506 (5) |
H37B | 0.3051 | 0.9866 | 0.4235 | 0.076* | 0.506 (5) |
C38 | 0.328 (2) | 1.296 (9) | 0.3913 (3) | 0.066 (7) | 0.506 (5) |
C39 | 0.331 (2) | 1.388 (6) | 0.3653 (5) | 0.087 (6) | 0.506 (5) |
H39 | 0.3329 | 1.4621 | 0.3443 | 0.104* | 0.506 (5) |
C51 | 0.3279 (2) | 0.4646 (8) | 0.70302 (8) | 0.0633 (9) | |
O51 | 0.26896 (15) | 0.3386 (7) | 0.70080 (5) | 0.0852 (9) | |
O52 | 0.37052 (14) | 0.4589 (6) | 0.72963 (5) | 0.0762 (8) | |
C52 | 0.3433 (2) | 0.2891 (10) | 0.75689 (8) | 0.0840 (12) | |
H52A | 0.2991 | 0.3798 | 0.7655 | 0.101* | |
H52B | 0.3304 | 0.0939 | 0.7498 | 0.101* | |
C53 | 0.4009 (3) | 0.2764 (15) | 0.78145 (10) | 0.125 (2) | |
H53A | 0.3820 | 0.1822 | 0.8004 | 0.187* | |
H53B | 0.4166 | 0.4704 | 0.7869 | 0.187* | |
H53C | 0.4425 | 0.1681 | 0.7735 | 0.187* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0422 (13) | 0.0431 (14) | 0.0613 (16) | −0.0045 (11) | −0.0053 (11) | −0.0034 (12) |
C2 | 0.0377 (14) | 0.0422 (17) | 0.0538 (17) | 0.0026 (13) | −0.0032 (12) | −0.0030 (14) |
N3 | 0.0463 (13) | 0.0586 (16) | 0.0486 (14) | −0.0093 (13) | −0.0047 (11) | −0.0011 (12) |
C3A | 0.0455 (16) | 0.0568 (19) | 0.0459 (16) | 0.0009 (15) | −0.0051 (13) | −0.0032 (15) |
C4 | 0.0532 (17) | 0.065 (2) | 0.0511 (18) | −0.0082 (16) | −0.0030 (14) | −0.0004 (16) |
C5 | 0.0539 (18) | 0.061 (2) | 0.0477 (18) | 0.0026 (16) | −0.0044 (14) | −0.0045 (16) |
C6 | 0.065 (2) | 0.072 (2) | 0.0534 (19) | −0.0010 (18) | −0.0143 (16) | −0.0040 (18) |
C7 | 0.0579 (19) | 0.067 (2) | 0.060 (2) | −0.0075 (17) | −0.0166 (16) | −0.0065 (18) |
C7A | 0.0456 (16) | 0.0505 (18) | 0.0483 (17) | 0.0038 (14) | −0.0041 (13) | −0.0057 (15) |
C11 | 0.077 (2) | 0.087 (3) | 0.081 (3) | −0.040 (2) | −0.018 (2) | 0.005 (2) |
C21 | 0.0351 (13) | 0.0366 (15) | 0.0517 (16) | 0.0024 (12) | −0.0005 (12) | −0.0031 (13) |
C22 | 0.045 (3) | 0.041 (3) | 0.057 (3) | −0.001 (3) | −0.007 (3) | −0.008 (3) |
C23 | 0.041 (3) | 0.039 (3) | 0.060 (3) | −0.006 (3) | −0.003 (3) | 0.004 (3) |
C24 | 0.037 (6) | 0.038 (6) | 0.055 (6) | −0.001 (6) | −0.003 (5) | −0.002 (5) |
C25 | 0.037 (3) | 0.040 (3) | 0.055 (3) | −0.004 (3) | −0.005 (2) | −0.004 (3) |
C26 | 0.034 (3) | 0.038 (3) | 0.058 (3) | −0.003 (3) | −0.001 (2) | 0.002 (3) |
O24 | 0.0579 (19) | 0.069 (7) | 0.0488 (14) | −0.017 (4) | −0.0034 (16) | 0.001 (3) |
C27 | 0.052 (6) | 0.079 (10) | 0.059 (3) | −0.019 (6) | −0.006 (3) | 0.001 (4) |
C28 | 0.062 (8) | 0.078 (17) | 0.057 (2) | −0.015 (10) | −0.004 (3) | −0.010 (5) |
C29 | 0.099 (14) | 0.104 (17) | 0.057 (3) | −0.015 (10) | 0.000 (4) | 0.001 (7) |
C31 | 0.0351 (13) | 0.0366 (15) | 0.0517 (16) | 0.0024 (12) | −0.0005 (12) | −0.0031 (13) |
C32 | 0.033 (3) | 0.042 (3) | 0.056 (3) | 0.002 (2) | −0.005 (2) | −0.007 (3) |
C33 | 0.034 (3) | 0.042 (3) | 0.053 (3) | −0.003 (3) | 0.008 (2) | −0.002 (3) |
C34 | 0.037 (6) | 0.041 (6) | 0.046 (5) | 0.001 (5) | 0.004 (5) | −0.002 (5) |
C35 | 0.035 (3) | 0.042 (3) | 0.048 (3) | 0.000 (3) | −0.006 (2) | 0.002 (3) |
C36 | 0.036 (3) | 0.047 (3) | 0.053 (3) | −0.005 (3) | 0.005 (2) | 0.000 (3) |
O34 | 0.0579 (19) | 0.069 (7) | 0.0488 (14) | −0.017 (4) | −0.0034 (16) | 0.001 (3) |
C37 | 0.052 (6) | 0.079 (10) | 0.059 (3) | −0.019 (6) | −0.006 (3) | 0.001 (4) |
C38 | 0.062 (8) | 0.078 (17) | 0.057 (2) | −0.015 (10) | −0.004 (3) | −0.010 (5) |
C39 | 0.099 (14) | 0.104 (17) | 0.057 (3) | −0.015 (10) | 0.000 (4) | 0.001 (7) |
C51 | 0.066 (2) | 0.075 (2) | 0.0492 (19) | 0.0015 (19) | −0.0055 (16) | −0.0023 (18) |
O51 | 0.0768 (17) | 0.121 (2) | 0.0578 (15) | −0.0251 (17) | −0.0062 (12) | 0.0157 (15) |
O52 | 0.0784 (16) | 0.098 (2) | 0.0520 (13) | −0.0068 (15) | −0.0122 (12) | 0.0099 (13) |
C52 | 0.094 (3) | 0.103 (3) | 0.055 (2) | −0.005 (2) | −0.0054 (19) | 0.017 (2) |
C53 | 0.118 (4) | 0.180 (6) | 0.075 (3) | −0.014 (4) | −0.024 (3) | 0.039 (3) |
N1—C7A | 1.376 (4) | O24—C27 | 1.403 (18) |
N1—C2 | 1.393 (3) | C27—C28 | 1.439 (7) |
N1—C11 | 1.449 (4) | C27—H27A | 0.9700 |
C2—N3 | 1.313 (4) | C27—H27B | 0.9700 |
C2—C21 | 1.473 (4) | C28—C29 | 1.156 (8) |
N3—C3A | 1.392 (4) | C29—H29 | 0.9300 |
C3A—C4 | 1.385 (4) | C32—C33 | 1.375 (6) |
C3A—C7A | 1.399 (4) | C32—H32 | 0.9300 |
C4—C5 | 1.379 (4) | C33—C34 | 1.39 (2) |
C4—H4 | 0.9300 | C33—H33 | 0.9300 |
C5—C6 | 1.401 (5) | C34—O34 | 1.369 (9) |
C5—C51 | 1.480 (5) | C34—C35 | 1.39 (2) |
C6—C7 | 1.361 (5) | C35—C36 | 1.376 (6) |
C6—H6 | 0.9300 | C35—H35 | 0.9300 |
C7—C7A | 1.394 (4) | C36—H36 | 0.9300 |
C7—H7 | 0.9300 | O34—C37 | 1.404 (18) |
C11—H11A | 0.9600 | C37—C38 | 1.440 (7) |
C11—H11B | 0.9600 | C37—H37A | 0.9700 |
C11—H11C | 0.9600 | C37—H37B | 0.9700 |
C21—C22 | 1.386 (6) | C38—C39 | 1.157 (8) |
C21—C26 | 1.389 (5) | C39—H39 | 0.9300 |
C22—C23 | 1.376 (7) | C51—O51 | 1.208 (4) |
C22—H22 | 0.9300 | C51—O52 | 1.328 (4) |
C23—C24 | 1.39 (2) | O52—C52 | 1.460 (4) |
C23—H23 | 0.9300 | C52—C53 | 1.436 (5) |
C24—O24 | 1.368 (9) | C52—H52A | 0.9700 |
C24—C25 | 1.38 (2) | C52—H52B | 0.9700 |
C25—C26 | 1.374 (6) | C53—H53A | 0.9600 |
C25—H25 | 0.9300 | C53—H53B | 0.9600 |
C26—H26 | 0.9300 | C53—H53C | 0.9600 |
C7A—N1—C2 | 105.9 (2) | C25—C26—H26 | 119.2 |
C7A—N1—C11 | 123.7 (3) | C21—C26—H26 | 119.2 |
C2—N1—C11 | 130.5 (3) | C24—O24—C27 | 119.6 (12) |
N3—C2—N1 | 113.1 (2) | O24—C27—C28 | 109.0 (11) |
N3—C2—C21 | 122.9 (2) | O24—C27—H27A | 109.9 |
N1—C2—C21 | 124.0 (3) | C28—C27—H27A | 109.9 |
C2—N3—C3A | 104.9 (2) | O24—C27—H27B | 109.9 |
C4—C3A—N3 | 129.9 (3) | C28—C27—H27B | 109.9 |
C4—C3A—C7A | 120.1 (3) | H27A—C27—H27B | 108.3 |
N3—C3A—C7A | 110.0 (3) | C29—C28—C27 | 173 (5) |
C5—C4—C3A | 118.4 (3) | C28—C29—H29 | 180.0 |
C5—C4—H4 | 120.8 | C33—C32—H32 | 119.7 |
C3A—C4—H4 | 120.8 | C32—C33—C34 | 120.4 (7) |
C4—C5—C6 | 120.8 (3) | C32—C33—H33 | 119.8 |
C4—C5—C51 | 118.0 (3) | C34—C33—H33 | 119.8 |
C6—C5—C51 | 121.2 (3) | O34—C34—C35 | 123 (3) |
C7—C6—C5 | 121.8 (3) | O34—C34—C33 | 117 (2) |
C7—C6—H6 | 119.1 | C35—C34—C33 | 119.6 (5) |
C5—C6—H6 | 119.1 | C36—C35—C34 | 119.4 (7) |
C6—C7—C7A | 117.5 (3) | C36—C35—H35 | 120.3 |
C6—C7—H7 | 121.3 | C34—C35—H35 | 120.3 |
C7A—C7—H7 | 121.3 | C35—C36—H36 | 119.3 |
N1—C7A—C7 | 132.3 (3) | C34—O34—C37 | 119.8 (12) |
N1—C7A—C3A | 106.1 (2) | O34—C37—C38 | 108.8 (10) |
C7—C7A—C3A | 121.5 (3) | O34—C37—H37A | 109.9 |
N1—C11—H11A | 109.5 | C38—C37—H37A | 109.9 |
N1—C11—H11B | 109.5 | O34—C37—H37B | 109.9 |
H11A—C11—H11B | 109.5 | C38—C37—H37B | 109.9 |
N1—C11—H11C | 109.5 | H37A—C37—H37B | 108.3 |
H11A—C11—H11C | 109.5 | C39—C38—C37 | 171 (4) |
H11B—C11—H11C | 109.5 | C38—C39—H39 | 180.0 |
C22—C21—C26 | 117.3 (4) | O51—C51—O52 | 123.0 (3) |
C22—C21—C2 | 124.6 (3) | O51—C51—C5 | 124.0 (3) |
C26—C21—C2 | 118.1 (3) | O52—C51—C5 | 113.0 (3) |
C23—C22—C21 | 122.1 (5) | C51—O52—C52 | 116.9 (3) |
C23—C22—H22 | 119.0 | C53—C52—O52 | 108.7 (3) |
C21—C22—H22 | 119.0 | C53—C52—H52A | 110.0 |
C22—C23—C24 | 119.5 (8) | O52—C52—H52A | 110.0 |
C22—C23—H23 | 120.3 | C53—C52—H52B | 110.0 |
C24—C23—H23 | 120.3 | O52—C52—H52B | 110.0 |
O24—C24—C25 | 123 (3) | H52A—C52—H52B | 108.3 |
O24—C24—C23 | 117 (2) | C52—C53—H53A | 109.5 |
C25—C24—C23 | 119.3 (5) | C52—C53—H53B | 109.5 |
C26—C25—C24 | 120.2 (8) | H53A—C53—H53B | 109.5 |
C26—C25—H25 | 119.9 | C52—C53—H53C | 109.5 |
C24—C25—H25 | 119.9 | H53A—C53—H53C | 109.5 |
C25—C26—C21 | 121.6 (5) | H53B—C53—H53C | 109.5 |
C7A—N1—C2—N3 | 0.1 (3) | N1—C2—C21—C26 | 152.4 (4) |
C11—N1—C2—N3 | −178.9 (3) | C26—C21—C22—C23 | −0.5 (7) |
C7A—N1—C2—C21 | −178.2 (2) | C2—C21—C22—C23 | −178.1 (4) |
C11—N1—C2—C21 | 2.8 (5) | C21—C22—C23—C24 | 0 (3) |
N1—C2—N3—C3A | 0.0 (3) | C22—C23—C24—O24 | −173 (5) |
C21—C2—N3—C3A | 178.4 (3) | C22—C23—C24—C25 | 0 (5) |
C2—N3—C3A—C4 | −178.9 (3) | O24—C24—C25—C26 | 173 (5) |
C2—N3—C3A—C7A | −0.2 (3) | C23—C24—C25—C26 | 1 (5) |
N3—C3A—C4—C5 | 177.9 (3) | C24—C25—C26—C21 | −1 (3) |
C7A—C3A—C4—C5 | −0.7 (5) | C22—C21—C26—C25 | 0.5 (7) |
C3A—C4—C5—C6 | 0.4 (5) | C2—C21—C26—C25 | 178.3 (4) |
C3A—C4—C5—C51 | −179.6 (3) | C25—C24—O24—C27 | 24 (11) |
C4—C5—C6—C7 | 0.1 (5) | C23—C24—O24—C27 | −163 (6) |
C51—C5—C6—C7 | −179.9 (3) | C24—O24—C27—C28 | 174 (7) |
C5—C6—C7—C7A | −0.3 (5) | C32—C33—C34—O34 | 173 (5) |
C2—N1—C7A—C7 | 178.1 (3) | C32—C33—C34—C35 | −1 (5) |
C11—N1—C7A—C7 | −2.8 (5) | O34—C34—C35—C36 | −173 (5) |
C2—N1—C7A—C3A | −0.2 (3) | C33—C34—C35—C36 | 1 (5) |
C11—N1—C7A—C3A | 178.9 (3) | C35—C34—O34—C37 | −21 (11) |
C6—C7—C7A—N1 | −178.2 (3) | C33—C34—O34—C37 | 165 (6) |
C6—C7—C7A—C3A | 0.0 (5) | C34—O34—C37—C38 | −176 (7) |
C4—C3A—C7A—N1 | 179.1 (3) | C4—C5—C51—O51 | −8.8 (5) |
N3—C3A—C7A—N1 | 0.3 (3) | C6—C5—C51—O51 | 171.1 (4) |
C4—C3A—C7A—C7 | 0.5 (5) | C4—C5—C51—O52 | 171.1 (3) |
N3—C3A—C7A—C7 | −178.3 (3) | C6—C5—C51—O52 | −8.9 (5) |
N3—C2—C21—C22 | 151.8 (4) | O51—C51—O52—C52 | 0.3 (5) |
N1—C2—C21—C22 | −30.0 (5) | C5—C51—O52—C52 | −179.6 (3) |
N3—C2—C21—C26 | −25.8 (5) | C51—O52—C52—C53 | 172.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···Cg1i | 0.93 | 2.77 | 3.412 (9) | 127 |
C26—H26···Cg1ii | 0.93 | 2.87 | 3.508 (9) | 127 |
C35—H35···Cg2iii | 0.93 | 2.87 | 3.555 (9) | 131 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1/2, −y+5/2, −z+1. |
C29H24N2O2 | F(000) = 912 |
Mr = 432.50 | Dx = 1.263 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.467 (2) Å | Cell parameters from 4909 reflections |
b = 8.6860 (8) Å | θ = 2.6–27.8° |
c = 14.242 (1) Å | µ = 0.08 mm−1 |
β = 95.359 (7)° | T = 296 K |
V = 2274.5 (4) Å3 | Block, yellow |
Z = 4 | 0.48 × 0.32 × 0.24 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 4691 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2593 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 26.6°, θmin = 2.6° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −18→23 |
Tmin = 0.905, Tmax = 0.981 | k = −10→7 |
9384 measured reflections | l = −14→17 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.147 | w = 1/[σ2(Fo2) + (0.0634P)2 + 0.389P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4691 reflections | Δρmax = 0.15 e Å−3 |
320 parameters | Δρmin = −0.17 e Å−3 |
9 restraints |
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) | |
N1 | 0.65691 (9) | 0.7408 (2) | 0.23708 (12) | 0.0594 (5) | |
C2 | 0.69734 (11) | 0.8183 (3) | 0.30919 (15) | 0.0568 (5) | |
N3 | 0.66307 (9) | 0.8333 (2) | 0.38560 (12) | 0.0614 (5) | |
C3A | 0.59665 (10) | 0.7619 (2) | 0.36420 (15) | 0.0551 (5) | |
C4 | 0.53959 (11) | 0.7415 (2) | 0.41957 (16) | 0.0595 (6) | |
H4 | 0.5418 | 0.7821 | 0.4802 | 0.071* | |
C5 | 0.47943 (11) | 0.6597 (3) | 0.38271 (16) | 0.0608 (6) | |
C6 | 0.47627 (13) | 0.6019 (3) | 0.29037 (18) | 0.0747 (7) | |
H6 | 0.4351 | 0.5478 | 0.2667 | 0.090* | |
C7 | 0.53147 (13) | 0.6219 (3) | 0.23378 (17) | 0.0755 (7) | |
H7 | 0.5285 | 0.5835 | 0.1726 | 0.091* | |
C7A | 0.59237 (11) | 0.7029 (2) | 0.27223 (15) | 0.0581 (6) | |
C21 | 0.77089 (11) | 0.8787 (2) | 0.29866 (14) | 0.0543 (5) | |
C22 | 0.78055 (13) | 0.9853 (3) | 0.22785 (15) | 0.0660 (6) | |
H22 | 0.7404 | 1.0178 | 0.1886 | 0.079* | |
C23 | 0.84795 (13) | 1.0433 (3) | 0.21471 (16) | 0.0686 (6) | |
H23 | 0.8527 | 1.1143 | 0.1669 | 0.082* | |
C23A | 0.90911 (12) | 0.9973 (2) | 0.27184 (15) | 0.0575 (5) | |
C24 | 0.98059 (14) | 1.0554 (3) | 0.26061 (18) | 0.0760 (7) | |
H24 | 0.9867 | 1.1249 | 0.2123 | 0.091* | |
C25 | 1.03788 (14) | 1.0128 (3) | 0.3170 (2) | 0.0791 (7) | |
H25 | 1.0832 | 1.0530 | 0.3070 | 0.095* | |
C25A | 1.03266 (11) | 0.9067 (3) | 0.39295 (16) | 0.0623 (6) | |
C26 | 1.09224 (13) | 0.8616 (3) | 0.4536 (2) | 0.0786 (7) | |
H26 | 1.1379 | 0.9020 | 0.4459 | 0.094* | |
C27 | 1.08436 (14) | 0.7582 (3) | 0.5245 (2) | 0.0823 (8) | |
H27 | 1.1249 | 0.7296 | 0.5644 | 0.099* | |
C28 | 1.01793 (13) | 0.6961 (3) | 0.53772 (17) | 0.0752 (7) | |
H28 | 1.0139 | 0.6253 | 0.5859 | 0.090* | |
C28A | 0.95602 (11) | 0.7384 (3) | 0.47925 (15) | 0.0575 (5) | |
C29 | 0.88535 (12) | 0.6795 (3) | 0.49081 (16) | 0.0672 (6) | |
H29 | 0.8800 | 0.6088 | 0.5387 | 0.081* | |
C210 | 0.82629 (11) | 0.7225 (3) | 0.43487 (15) | 0.0606 (6) | |
H210 | 0.7812 | 0.6814 | 0.4452 | 0.073* | |
C20A | 0.83110 (10) | 0.8306 (2) | 0.35956 (13) | 0.0488 (5) | |
C23B | 0.90095 (10) | 0.8902 (2) | 0.34558 (13) | 0.0492 (5) | |
C25B | 0.96325 (10) | 0.8449 (2) | 0.40574 (14) | 0.0516 (5) | |
C11 | 0.67891 (14) | 0.6952 (3) | 0.14429 (16) | 0.0754 (7) | 0.601 (8) |
H11A | 0.6917 | 0.7873 | 0.1110 | 0.090* | 0.601 (8) |
H11B | 0.6374 | 0.6486 | 0.1082 | 0.090* | 0.601 (8) |
C12 | 0.7423 (3) | 0.5839 (5) | 0.1472 (3) | 0.0673 (16) | 0.601 (8) |
H12A | 0.7850 | 0.6317 | 0.1796 | 0.081* | 0.601 (8) |
H12B | 0.7529 | 0.5605 | 0.0833 | 0.081* | 0.601 (8) |
C13 | 0.7256 (9) | 0.4347 (13) | 0.1976 (10) | 0.118 (5) | 0.601 (8) |
H13A | 0.7673 | 0.3684 | 0.2005 | 0.177* | 0.601 (8) |
H13B | 0.6850 | 0.3842 | 0.1636 | 0.177* | 0.601 (8) |
H13C | 0.7139 | 0.4578 | 0.2604 | 0.177* | 0.601 (8) |
C14 | 0.67891 (14) | 0.6952 (3) | 0.14429 (16) | 0.0754 (7) | 0.399 (8) |
H14A | 0.7242 | 0.7458 | 0.1333 | 0.090* | 0.399 (8) |
H14B | 0.6420 | 0.7269 | 0.0951 | 0.090* | 0.399 (8) |
C15 | 0.6886 (8) | 0.5245 (9) | 0.1412 (6) | 0.125 (5) | 0.399 (8) |
H15A | 0.7010 | 0.4947 | 0.0791 | 0.150* | 0.399 (8) |
H15B | 0.6431 | 0.4746 | 0.1521 | 0.150* | 0.399 (8) |
C16 | 0.7483 (12) | 0.4707 (19) | 0.2155 (15) | 0.114 (6) | 0.399 (8) |
H16A | 0.7573 | 0.3630 | 0.2071 | 0.172* | 0.399 (8) |
H16B | 0.7331 | 0.4878 | 0.2773 | 0.172* | 0.399 (8) |
H16C | 0.7921 | 0.5277 | 0.2087 | 0.172* | 0.399 (8) |
C51 | 0.41793 (12) | 0.6277 (3) | 0.43984 (19) | 0.0696 (6) | |
O51 | 0.36732 (9) | 0.5459 (2) | 0.41475 (14) | 0.1016 (6) | |
O52 | 0.42445 (8) | 0.6961 (2) | 0.52331 (13) | 0.0863 (5) | |
C52 | 0.36844 (13) | 0.6652 (4) | 0.58661 (19) | 0.0901 (8) | |
H52A | 0.3884 | 0.6817 | 0.6513 | 0.108* | |
H52B | 0.3535 | 0.5583 | 0.5803 | 0.108* | |
C53 | 0.30450 (18) | 0.7653 (4) | 0.5657 (2) | 0.1197 (12) | |
H53A | 0.2714 | 0.7513 | 0.6132 | 0.180* | |
H53B | 0.2806 | 0.7389 | 0.5051 | 0.180* | |
H53C | 0.3198 | 0.8709 | 0.5653 | 0.180* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0625 (11) | 0.0609 (11) | 0.0535 (10) | 0.0061 (9) | −0.0013 (8) | −0.0059 (9) |
C2 | 0.0557 (12) | 0.0581 (14) | 0.0559 (13) | 0.0049 (11) | 0.0022 (10) | −0.0014 (10) |
N3 | 0.0505 (10) | 0.0701 (12) | 0.0635 (11) | −0.0064 (9) | 0.0052 (8) | −0.0140 (9) |
C3A | 0.0488 (11) | 0.0558 (13) | 0.0587 (12) | 0.0018 (10) | −0.0052 (9) | −0.0074 (10) |
C4 | 0.0533 (12) | 0.0630 (14) | 0.0607 (13) | −0.0022 (11) | −0.0032 (10) | −0.0086 (11) |
C5 | 0.0504 (12) | 0.0593 (14) | 0.0700 (14) | −0.0004 (10) | −0.0096 (10) | 0.0005 (11) |
C6 | 0.0634 (14) | 0.0779 (17) | 0.0781 (16) | −0.0121 (13) | −0.0175 (13) | −0.0093 (14) |
C7 | 0.0763 (16) | 0.0815 (18) | 0.0650 (14) | −0.0075 (14) | −0.0128 (13) | −0.0140 (13) |
C7A | 0.0575 (13) | 0.0550 (14) | 0.0593 (13) | 0.0059 (11) | −0.0074 (10) | −0.0029 (11) |
C21 | 0.0583 (12) | 0.0519 (13) | 0.0534 (12) | 0.0042 (10) | 0.0086 (9) | −0.0048 (10) |
C22 | 0.0747 (15) | 0.0627 (15) | 0.0605 (14) | 0.0115 (12) | 0.0049 (11) | 0.0077 (12) |
C23 | 0.0854 (17) | 0.0586 (15) | 0.0639 (14) | 0.0042 (13) | 0.0178 (12) | 0.0109 (12) |
C23A | 0.0712 (14) | 0.0465 (12) | 0.0576 (13) | −0.0023 (11) | 0.0214 (11) | −0.0037 (10) |
C24 | 0.0880 (18) | 0.0624 (16) | 0.0828 (17) | −0.0119 (14) | 0.0351 (15) | 0.0031 (13) |
C25 | 0.0704 (16) | 0.0733 (17) | 0.0985 (19) | −0.0165 (14) | 0.0335 (15) | −0.0126 (16) |
C25A | 0.0564 (13) | 0.0593 (14) | 0.0728 (15) | −0.0020 (11) | 0.0152 (11) | −0.0223 (12) |
C26 | 0.0588 (14) | 0.0823 (19) | 0.0951 (19) | −0.0004 (13) | 0.0096 (14) | −0.0338 (16) |
C27 | 0.0648 (16) | 0.093 (2) | 0.0861 (19) | 0.0166 (15) | −0.0078 (13) | −0.0238 (17) |
C28 | 0.0741 (16) | 0.0770 (17) | 0.0732 (16) | 0.0168 (14) | −0.0005 (12) | −0.0047 (13) |
C28A | 0.0603 (13) | 0.0567 (13) | 0.0555 (12) | 0.0068 (11) | 0.0054 (10) | −0.0077 (11) |
C29 | 0.0738 (15) | 0.0660 (15) | 0.0625 (14) | 0.0041 (13) | 0.0100 (12) | 0.0122 (12) |
C210 | 0.0570 (13) | 0.0623 (15) | 0.0635 (13) | −0.0041 (11) | 0.0111 (10) | 0.0076 (11) |
C20A | 0.0569 (12) | 0.0446 (11) | 0.0461 (11) | 0.0002 (10) | 0.0107 (9) | −0.0034 (9) |
C23B | 0.0579 (12) | 0.0415 (11) | 0.0499 (11) | 0.0004 (9) | 0.0141 (9) | −0.0104 (9) |
C25B | 0.0557 (12) | 0.0476 (12) | 0.0526 (12) | 0.0012 (10) | 0.0115 (9) | −0.0142 (10) |
C11 | 0.0969 (18) | 0.0789 (18) | 0.0503 (13) | 0.0105 (15) | 0.0062 (12) | −0.0079 (12) |
C12 | 0.077 (3) | 0.065 (3) | 0.062 (2) | 0.011 (2) | 0.017 (2) | 0.000 (2) |
C13 | 0.175 (13) | 0.073 (6) | 0.113 (6) | 0.030 (7) | 0.053 (6) | 0.014 (6) |
C14 | 0.0969 (18) | 0.0789 (18) | 0.0503 (13) | 0.0105 (15) | 0.0062 (12) | −0.0079 (12) |
C15 | 0.196 (14) | 0.093 (8) | 0.095 (6) | 0.012 (8) | 0.061 (7) | −0.028 (6) |
C16 | 0.118 (10) | 0.066 (8) | 0.170 (12) | 0.022 (8) | 0.069 (9) | −0.016 (8) |
C51 | 0.0540 (13) | 0.0631 (15) | 0.0888 (18) | −0.0051 (12) | −0.0090 (12) | 0.0000 (14) |
O51 | 0.0718 (11) | 0.1071 (15) | 0.1238 (15) | −0.0365 (11) | −0.0019 (10) | −0.0166 (12) |
O52 | 0.0664 (10) | 0.1052 (14) | 0.0885 (12) | −0.0267 (10) | 0.0129 (9) | −0.0138 (11) |
C52 | 0.0686 (16) | 0.111 (2) | 0.0919 (19) | −0.0163 (16) | 0.0125 (14) | 0.0105 (17) |
C53 | 0.129 (3) | 0.100 (2) | 0.138 (3) | 0.023 (2) | 0.051 (2) | 0.017 (2) |
N1—C7A | 1.375 (3) | C28—C28A | 1.399 (3) |
N1—C2 | 1.386 (3) | C28—H28 | 0.9300 |
N1—C11 | 1.472 (3) | C28A—C25B | 1.413 (3) |
C2—N3 | 1.315 (3) | C28A—C29 | 1.426 (3) |
C2—C21 | 1.477 (3) | C29—C210 | 1.342 (3) |
N3—C3A | 1.383 (2) | C29—H29 | 0.9300 |
C3A—C4 | 1.385 (3) | C210—C20A | 1.434 (3) |
C3A—C7A | 1.402 (3) | C210—H210 | 0.9300 |
C4—C5 | 1.381 (3) | C20A—C23B | 1.421 (3) |
C4—H4 | 0.9300 | C23B—C25B | 1.424 (3) |
C5—C6 | 1.404 (3) | C11—C12 | 1.516 (4) |
C5—C51 | 1.484 (3) | C11—H11A | 0.9700 |
C6—C7 | 1.368 (3) | C11—H11B | 0.9700 |
C6—H6 | 0.9300 | C12—C13 | 1.526 (10) |
C7—C7A | 1.394 (3) | C12—H12A | 0.9700 |
C7—H7 | 0.9300 | C12—H12B | 0.9700 |
C21—C22 | 1.392 (3) | C13—H13A | 0.9600 |
C21—C20A | 1.408 (3) | C13—H13B | 0.9600 |
C22—C23 | 1.372 (3) | C13—H13C | 0.9600 |
C22—H22 | 0.9300 | C15—C16 | 1.529 (12) |
C23—C23A | 1.388 (3) | C15—H15A | 0.9700 |
C23—H23 | 0.9300 | C15—H15B | 0.9700 |
C23A—C23B | 1.421 (3) | C16—H16A | 0.9600 |
C23A—C24 | 1.436 (3) | C16—H16B | 0.9600 |
C24—C25 | 1.320 (3) | C16—H16C | 0.9600 |
C24—H24 | 0.9300 | C51—O51 | 1.202 (3) |
C25—C25A | 1.431 (3) | C51—O52 | 1.324 (3) |
C25—H25 | 0.9300 | O52—C52 | 1.459 (3) |
C25A—C26 | 1.390 (3) | C52—C53 | 1.474 (4) |
C25A—C25B | 1.417 (3) | C52—H52A | 0.9700 |
C26—C27 | 1.370 (4) | C52—H52B | 0.9700 |
C26—H26 | 0.9300 | C53—H53A | 0.9600 |
C27—C28 | 1.369 (3) | C53—H53B | 0.9600 |
C27—H27 | 0.9300 | C53—H53C | 0.9600 |
C7A—N1—C2 | 105.76 (17) | C210—C29—C28A | 122.2 (2) |
C7A—N1—C11 | 125.70 (18) | C210—C29—H29 | 118.9 |
C2—N1—C11 | 128.37 (19) | C28A—C29—H29 | 118.9 |
N3—C2—N1 | 113.17 (18) | C29—C210—C20A | 121.5 (2) |
N3—C2—C21 | 124.54 (18) | C29—C210—H210 | 119.2 |
N1—C2—C21 | 122.28 (18) | C20A—C210—H210 | 119.2 |
C2—N3—C3A | 104.99 (17) | C21—C20A—C23B | 118.70 (18) |
N3—C3A—C4 | 129.65 (19) | C21—C20A—C210 | 123.67 (19) |
N3—C3A—C7A | 109.96 (18) | C23B—C20A—C210 | 117.62 (18) |
C4—C3A—C7A | 120.38 (19) | C20A—C23B—C23A | 120.15 (18) |
C5—C4—C3A | 118.5 (2) | C20A—C23B—C25B | 120.52 (18) |
C5—C4—H4 | 120.7 | C23A—C23B—C25B | 119.32 (18) |
C3A—C4—H4 | 120.7 | C28A—C25B—C25A | 119.50 (19) |
C4—C5—C6 | 120.1 (2) | C28A—C25B—C23B | 119.98 (18) |
C4—C5—C51 | 121.2 (2) | C25A—C25B—C23B | 120.5 (2) |
C6—C5—C51 | 118.7 (2) | N1—C11—C12 | 115.1 (2) |
C7—C6—C5 | 122.6 (2) | N1—C11—H11A | 108.5 |
C7—C6—H6 | 118.7 | C12—C11—H11A | 108.5 |
C5—C6—H6 | 118.7 | N1—C11—H11B | 108.5 |
C6—C7—C7A | 116.8 (2) | C12—C11—H11B | 108.5 |
C6—C7—H7 | 121.6 | H11A—C11—H11B | 107.5 |
C7A—C7—H7 | 121.6 | C11—C12—C13 | 111.4 (7) |
N1—C7A—C7 | 132.3 (2) | C11—C12—H12A | 109.3 |
N1—C7A—C3A | 106.11 (17) | C13—C12—H12A | 109.3 |
C7—C7A—C3A | 121.6 (2) | C11—C12—H12B | 109.3 |
C22—C21—C20A | 119.75 (19) | C13—C12—H12B | 109.3 |
C22—C21—C2 | 119.41 (19) | H12A—C12—H12B | 108.0 |
C20A—C21—C2 | 120.84 (19) | C12—C13—H13A | 109.5 |
C23—C22—C21 | 121.5 (2) | C12—C13—H13B | 109.5 |
C23—C22—H22 | 119.3 | H13A—C13—H13B | 109.5 |
C21—C22—H22 | 119.3 | C12—C13—H13C | 109.5 |
C22—C23—C23A | 120.9 (2) | H13A—C13—H13C | 109.5 |
C22—C23—H23 | 119.5 | H13B—C13—H13C | 109.5 |
C23A—C23—H23 | 119.5 | C16—C15—H15A | 109.4 |
C23—C23A—C23B | 119.0 (2) | C16—C15—H15B | 109.4 |
C23—C23A—C24 | 122.7 (2) | H15A—C15—H15B | 108.0 |
C23B—C23A—C24 | 118.3 (2) | C15—C16—H16A | 109.5 |
C25—C24—C23A | 121.8 (2) | C15—C16—H16B | 109.5 |
C25—C24—H24 | 119.1 | H16A—C16—H16B | 109.5 |
C23A—C24—H24 | 119.1 | C15—C16—H16C | 109.5 |
C24—C25—C25A | 122.3 (2) | H16A—C16—H16C | 109.5 |
C24—C25—H25 | 118.9 | H16B—C16—H16C | 109.5 |
C25A—C25—H25 | 118.9 | O51—C51—O52 | 122.4 (2) |
C26—C25A—C25B | 119.1 (2) | O51—C51—C5 | 124.2 (2) |
C26—C25A—C25 | 123.1 (2) | O52—C51—C5 | 113.46 (19) |
C25B—C25A—C25 | 117.8 (2) | C51—O52—C52 | 117.52 (19) |
C27—C26—C25A | 120.7 (2) | O52—C52—C53 | 111.6 (2) |
C27—C26—H26 | 119.7 | O52—C52—H52A | 109.3 |
C25A—C26—H26 | 119.7 | C53—C52—H52A | 109.3 |
C28—C27—C26 | 121.2 (2) | O52—C52—H52B | 109.3 |
C28—C27—H27 | 119.4 | C53—C52—H52B | 109.3 |
C26—C27—H27 | 119.4 | H52A—C52—H52B | 108.0 |
C27—C28—C28A | 120.5 (2) | C52—C53—H53A | 109.5 |
C27—C28—H28 | 119.7 | C52—C53—H53B | 109.5 |
C28A—C28—H28 | 119.7 | H53A—C53—H53B | 109.5 |
C28—C28A—C25B | 119.0 (2) | C52—C53—H53C | 109.5 |
C28—C28A—C29 | 122.9 (2) | H53A—C53—H53C | 109.5 |
C25B—C28A—C29 | 118.15 (19) | H53B—C53—H53C | 109.5 |
C7A—N1—C2—N3 | −0.8 (2) | C26—C27—C28—C28A | −0.7 (4) |
C11—N1—C2—N3 | −176.1 (2) | C27—C28—C28A—C25B | 0.7 (3) |
C7A—N1—C2—C21 | −179.88 (19) | C27—C28—C28A—C29 | −178.9 (2) |
C11—N1—C2—C21 | 4.7 (3) | C28—C28A—C29—C210 | 179.2 (2) |
N1—C2—N3—C3A | 0.3 (2) | C25B—C28A—C29—C210 | −0.4 (3) |
C21—C2—N3—C3A | 179.40 (19) | C28A—C29—C210—C20A | 0.3 (4) |
C2—N3—C3A—C4 | 178.9 (2) | C22—C21—C20A—C23B | −1.4 (3) |
C2—N3—C3A—C7A | 0.3 (2) | C2—C21—C20A—C23B | 179.00 (17) |
N3—C3A—C4—C5 | −177.3 (2) | C22—C21—C20A—C210 | 179.4 (2) |
C7A—C3A—C4—C5 | 1.2 (3) | C2—C21—C20A—C210 | −0.2 (3) |
C3A—C4—C5—C6 | −1.3 (3) | C29—C210—C20A—C21 | 179.6 (2) |
C3A—C4—C5—C51 | 177.2 (2) | C29—C210—C20A—C23B | 0.4 (3) |
C4—C5—C6—C7 | 0.6 (4) | C21—C20A—C23B—C23A | 0.5 (3) |
C51—C5—C6—C7 | −178.0 (2) | C210—C20A—C23B—C23A | 179.80 (18) |
C5—C6—C7—C7A | 0.4 (4) | C21—C20A—C23B—C25B | 179.80 (18) |
C2—N1—C7A—C7 | −178.2 (2) | C210—C20A—C23B—C25B | −0.9 (3) |
C11—N1—C7A—C7 | −2.7 (4) | C23—C23A—C23B—C20A | 0.6 (3) |
C2—N1—C7A—C3A | 0.9 (2) | C24—C23A—C23B—C20A | 179.60 (18) |
C11—N1—C7A—C3A | 176.41 (19) | C23—C23A—C23B—C25B | −178.71 (19) |
C6—C7—C7A—N1 | 178.5 (2) | C24—C23A—C23B—C25B | 0.3 (3) |
C6—C7—C7A—C3A | −0.5 (3) | C28—C28A—C25B—C25A | −0.2 (3) |
N3—C3A—C7A—N1 | −0.7 (2) | C29—C28A—C25B—C25A | 179.43 (18) |
C4—C3A—C7A—N1 | −179.50 (19) | C28—C28A—C25B—C23B | −179.73 (19) |
N3—C3A—C7A—C7 | 178.5 (2) | C29—C28A—C25B—C23B | −0.1 (3) |
C4—C3A—C7A—C7 | −0.3 (3) | C26—C25A—C25B—C28A | −0.3 (3) |
N3—C2—C21—C22 | −120.0 (2) | C25—C25A—C25B—C28A | 179.22 (19) |
N1—C2—C21—C22 | 59.0 (3) | C26—C25A—C25B—C23B | 179.24 (19) |
N3—C2—C21—C20A | 59.6 (3) | C25—C25A—C25B—C23B | −1.2 (3) |
N1—C2—C21—C20A | −121.4 (2) | C20A—C23B—C25B—C28A | 0.8 (3) |
C20A—C21—C22—C23 | 1.1 (3) | C23A—C23B—C25B—C28A | −179.91 (18) |
C2—C21—C22—C23 | −179.3 (2) | C20A—C23B—C25B—C25A | −178.75 (17) |
C21—C22—C23—C23A | 0.0 (3) | C23A—C23B—C25B—C25A | 0.5 (3) |
C22—C23—C23A—C23B | −0.9 (3) | C7A—N1—C11—C12 | −112.6 (3) |
C22—C23—C23A—C24 | −179.9 (2) | C2—N1—C11—C12 | 61.9 (4) |
C23—C23A—C24—C25 | 178.5 (2) | N1—C11—C12—C13 | 59.1 (9) |
C23B—C23A—C24—C25 | −0.5 (3) | C4—C5—C51—O51 | −173.1 (2) |
C23A—C24—C25—C25A | −0.2 (4) | C6—C5—C51—O51 | 5.5 (4) |
C24—C25—C25A—C26 | −179.4 (2) | C4—C5—C51—O52 | 5.7 (3) |
C24—C25—C25A—C25B | 1.1 (3) | C6—C5—C51—O52 | −175.8 (2) |
C25B—C25A—C26—C27 | 0.3 (3) | O51—C51—O52—C52 | 1.8 (4) |
C25—C25A—C26—C27 | −179.2 (2) | C5—C51—O52—C52 | −177.0 (2) |
C25A—C26—C27—C28 | 0.1 (4) | C51—O52—C52—C53 | −83.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···O51i | 0.97 | 2.51 | 3.253 (3) | 133 |
C22—H22···O51i | 0.93 | 2.37 | 3.290 (3) | 168 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
C21H19ClN4O2 | F(000) = 824 |
Mr = 394.85 | Dx = 1.334 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.1095 (4) Å | Cell parameters from 4250 reflections |
b = 9.5126 (4) Å | θ = 2.8–27.8° |
c = 18.6747 (8) Å | µ = 0.22 mm−1 |
β = 95.079 (4)° | T = 296 K |
V = 1965.80 (14) Å3 | Block, yellow |
Z = 4 | 0.48 × 0.40 × 0.40 mm |
Oxford Diffraction Xcalibur with Sapphire CCD diffractometer | 4250 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3323 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
ω scans | θmax = 27.8°, θmin = 2.8° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −14→14 |
Tmin = 0.808, Tmax = 0.916 | k = −12→10 |
8067 measured reflections | l = −20→24 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.5825P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4250 reflections | Δρmax = 0.32 e Å−3 |
294 parameters | Δρmin = −0.29 e Å−3 |
28 restraints |
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) | |
N1 | 0.68249 (11) | 0.22101 (15) | 0.52839 (7) | 0.0373 (3) | |
C2 | 0.67704 (14) | 0.25652 (17) | 0.59966 (8) | 0.0369 (3) | |
N3 | 0.56674 (12) | 0.25655 (16) | 0.61981 (7) | 0.0423 (3) | |
C3A | 0.49392 (14) | 0.22047 (17) | 0.55799 (8) | 0.0367 (3) | |
C4 | 0.36951 (14) | 0.20581 (18) | 0.54660 (9) | 0.0405 (4) | |
H4 | 0.3205 | 0.2204 | 0.5838 | 0.049* | |
C5 | 0.31969 (14) | 0.16872 (18) | 0.47826 (9) | 0.0391 (4) | |
C6 | 0.39284 (15) | 0.14650 (19) | 0.42181 (9) | 0.0429 (4) | |
H6 | 0.3572 | 0.1214 | 0.3767 | 0.051* | |
C7 | 0.51670 (15) | 0.1612 (2) | 0.43215 (8) | 0.0431 (4) | |
H7 | 0.5656 | 0.1467 | 0.3949 | 0.052* | |
C7A | 0.56520 (13) | 0.19862 (17) | 0.50056 (8) | 0.0358 (3) | |
C11 | 0.78783 (15) | 0.1939 (2) | 0.48958 (9) | 0.0458 (4) | |
H11A | 0.8021 | 0.2731 | 0.4596 | 0.069* | |
H11B | 0.7739 | 0.1117 | 0.4602 | 0.069* | |
H11C | 0.8571 | 0.1790 | 0.5233 | 0.069* | |
N21 | 0.95909 (11) | 0.39053 (14) | 0.68756 (7) | 0.0368 (3) | |
N22 | 0.92990 (12) | 0.30048 (15) | 0.74036 (7) | 0.0404 (3) | |
C23 | 0.82543 (14) | 0.24234 (18) | 0.71555 (8) | 0.0388 (4) | |
C24 | 0.78630 (14) | 0.29305 (17) | 0.64600 (8) | 0.0362 (3) | |
C25 | 0.87371 (14) | 0.38756 (17) | 0.63130 (8) | 0.0365 (3) | |
Cl25 | 0.87732 (4) | 0.50148 (5) | 0.56105 (2) | 0.05466 (15) | |
C211 | 1.07114 (14) | 0.46565 (17) | 0.69408 (8) | 0.0380 (4) | |
C212 | 1.15160 (15) | 0.44554 (19) | 0.64275 (9) | 0.0444 (4) | |
H212 | 1.1336 | 0.3831 | 0.6050 | 0.053* | |
C213 | 1.25950 (17) | 0.5195 (2) | 0.64814 (11) | 0.0557 (5) | |
H213 | 1.3144 | 0.5067 | 0.6139 | 0.067* | |
C214 | 1.28538 (19) | 0.6115 (3) | 0.70383 (12) | 0.0660 (6) | |
H214 | 1.3575 | 0.6616 | 0.7072 | 0.079* | |
C215 | 1.2046 (2) | 0.6295 (3) | 0.75463 (12) | 0.0740 (7) | |
H215 | 1.2228 | 0.6918 | 0.7924 | 0.089* | |
C216 | 1.09661 (18) | 0.5567 (2) | 0.75048 (10) | 0.0572 (5) | |
H216 | 1.0423 | 0.5691 | 0.7851 | 0.069* | |
C231 | 0.76612 (18) | 0.1354 (2) | 0.75887 (10) | 0.0566 (5) | |
H31A | 0.7397 | 0.0577 | 0.7286 | 0.085* | |
H31C | 0.6978 | 0.1769 | 0.7788 | 0.085* | |
H31B | 0.8227 | 0.1026 | 0.7971 | 0.085* | |
C51 | 0.18619 (16) | 0.1561 (2) | 0.46711 (10) | 0.0466 (4) | |
O51 | 0.1166 (12) | 0.1806 (17) | 0.5157 (6) | 0.0532 (18) | 0.645 (7) |
O52 | 0.1484 (4) | 0.1283 (5) | 0.4013 (3) | 0.0534 (11) | 0.645 (7) |
C52 | 0.0170 (3) | 0.1216 (6) | 0.3863 (2) | 0.0619 (12) | 0.645 (7) |
H52A | −0.0173 | 0.0617 | 0.4213 | 0.074* | 0.645 (7) |
H52B | −0.0175 | 0.2148 | 0.3895 | 0.074* | 0.645 (7) |
C53 | −0.0108 (4) | 0.0652 (7) | 0.3143 (3) | 0.101 (2) | 0.645 (7) |
H53A | 0.0294 | 0.1201 | 0.2805 | 0.151* | 0.645 (7) |
H53B | −0.0965 | 0.0687 | 0.3021 | 0.151* | 0.645 (7) |
H53C | 0.0163 | −0.0305 | 0.3130 | 0.151* | 0.645 (7) |
O61 | 0.119 (2) | 0.188 (3) | 0.5021 (11) | 0.054 (3) | 0.355 (7) |
O62 | 0.1531 (6) | 0.0711 (9) | 0.4014 (6) | 0.0539 (19) | 0.355 (7) |
C62 | 0.0248 (6) | 0.0360 (9) | 0.3824 (4) | 0.0618 (19) | 0.355 (7) |
H62A | 0.0177 | −0.0526 | 0.3567 | 0.074* | 0.355 (7) |
H62B | −0.0178 | 0.0283 | 0.4254 | 0.074* | 0.355 (7) |
C63 | −0.0251 (7) | 0.1499 (9) | 0.3370 (6) | 0.083 (3) | 0.355 (7) |
H63A | −0.1071 | 0.1282 | 0.3200 | 0.125* | 0.355 (7) |
H63B | 0.0221 | 0.1613 | 0.2968 | 0.125* | 0.355 (7) |
H63C | −0.0233 | 0.2355 | 0.3644 | 0.125* | 0.355 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0295 (6) | 0.0475 (8) | 0.0354 (7) | 0.0004 (6) | 0.0057 (5) | −0.0019 (6) |
C2 | 0.0349 (8) | 0.0412 (9) | 0.0347 (8) | 0.0008 (7) | 0.0040 (6) | 0.0013 (6) |
N3 | 0.0351 (7) | 0.0575 (9) | 0.0348 (7) | −0.0004 (6) | 0.0054 (5) | −0.0028 (6) |
C3A | 0.0343 (8) | 0.0428 (9) | 0.0336 (8) | 0.0017 (7) | 0.0058 (6) | −0.0001 (6) |
C4 | 0.0337 (8) | 0.0505 (10) | 0.0384 (8) | 0.0030 (7) | 0.0093 (6) | 0.0006 (7) |
C5 | 0.0313 (8) | 0.0450 (9) | 0.0409 (8) | 0.0020 (7) | 0.0033 (6) | 0.0042 (7) |
C6 | 0.0388 (8) | 0.0543 (10) | 0.0353 (8) | −0.0015 (8) | 0.0016 (7) | −0.0024 (7) |
C7 | 0.0377 (8) | 0.0589 (11) | 0.0335 (8) | −0.0007 (8) | 0.0080 (6) | −0.0040 (7) |
C7A | 0.0305 (8) | 0.0412 (9) | 0.0361 (8) | 0.0011 (6) | 0.0054 (6) | 0.0013 (6) |
C11 | 0.0346 (8) | 0.0577 (11) | 0.0466 (9) | 0.0007 (8) | 0.0123 (7) | −0.0047 (8) |
N21 | 0.0356 (7) | 0.0413 (7) | 0.0330 (6) | −0.0028 (6) | 0.0005 (5) | 0.0028 (5) |
N22 | 0.0424 (7) | 0.0464 (8) | 0.0324 (7) | −0.0024 (6) | 0.0022 (5) | 0.0051 (6) |
C23 | 0.0376 (8) | 0.0444 (9) | 0.0349 (8) | 0.0002 (7) | 0.0061 (6) | 0.0015 (7) |
C24 | 0.0329 (8) | 0.0412 (9) | 0.0345 (8) | 0.0010 (6) | 0.0034 (6) | −0.0001 (6) |
C25 | 0.0373 (8) | 0.0388 (8) | 0.0331 (8) | 0.0012 (7) | 0.0009 (6) | 0.0028 (6) |
Cl25 | 0.0594 (3) | 0.0554 (3) | 0.0473 (3) | −0.0094 (2) | −0.0065 (2) | 0.0195 (2) |
C211 | 0.0363 (8) | 0.0398 (9) | 0.0372 (8) | −0.0022 (7) | −0.0001 (6) | 0.0010 (6) |
C212 | 0.0433 (9) | 0.0458 (9) | 0.0443 (9) | −0.0010 (8) | 0.0048 (7) | −0.0041 (7) |
C213 | 0.0444 (10) | 0.0655 (13) | 0.0582 (11) | −0.0057 (9) | 0.0104 (8) | 0.0054 (10) |
C214 | 0.0524 (12) | 0.0774 (15) | 0.0665 (13) | −0.0264 (11) | −0.0042 (10) | 0.0033 (11) |
C215 | 0.0748 (15) | 0.0873 (17) | 0.0589 (12) | −0.0327 (13) | −0.0006 (11) | −0.0247 (12) |
C216 | 0.0562 (11) | 0.0709 (13) | 0.0447 (10) | −0.0107 (10) | 0.0064 (8) | −0.0150 (9) |
C231 | 0.0574 (11) | 0.0665 (13) | 0.0461 (10) | −0.0141 (10) | 0.0060 (8) | 0.0122 (9) |
C51 | 0.0349 (9) | 0.0557 (11) | 0.0489 (10) | 0.0006 (8) | 0.0014 (8) | 0.0053 (8) |
O51 | 0.035 (2) | 0.077 (3) | 0.049 (3) | −0.0055 (19) | 0.013 (2) | 0.001 (3) |
O52 | 0.0304 (12) | 0.073 (3) | 0.0555 (15) | −0.0031 (15) | −0.0027 (10) | −0.016 (2) |
C52 | 0.0280 (14) | 0.081 (3) | 0.074 (2) | 0.0052 (18) | −0.0104 (14) | −0.022 (2) |
C53 | 0.056 (2) | 0.126 (5) | 0.113 (4) | 0.014 (3) | −0.029 (2) | −0.062 (3) |
O61 | 0.038 (4) | 0.071 (5) | 0.057 (7) | 0.011 (4) | 0.019 (4) | 0.004 (5) |
O62 | 0.036 (2) | 0.076 (5) | 0.049 (3) | −0.011 (3) | −0.0015 (19) | −0.007 (4) |
C62 | 0.063 (4) | 0.065 (4) | 0.060 (4) | 0.012 (3) | 0.014 (3) | −0.010 (3) |
C63 | 0.072 (5) | 0.080 (6) | 0.096 (7) | 0.005 (4) | 0.000 (5) | −0.003 (5) |
N1—C7A | 1.3761 (19) | C212—H212 | 0.9300 |
N1—C2 | 1.380 (2) | C213—C214 | 1.370 (3) |
N1—C11 | 1.453 (2) | C213—H213 | 0.9300 |
C2—N3 | 1.313 (2) | C214—C215 | 1.373 (3) |
C2—C24 | 1.469 (2) | C214—H214 | 0.9300 |
N3—C3A | 1.393 (2) | C215—C216 | 1.381 (3) |
C3A—C4 | 1.387 (2) | C215—H215 | 0.9300 |
C3A—C7A | 1.404 (2) | C216—H216 | 0.9300 |
C4—C5 | 1.391 (2) | C231—H31A | 0.9600 |
C4—H4 | 0.9300 | C231—H31C | 0.9600 |
C5—C6 | 1.403 (2) | C231—H31B | 0.9600 |
C5—C51 | 1.484 (2) | C51—O61 | 1.080 (19) |
C6—C7 | 1.380 (2) | C51—O51 | 1.265 (10) |
C6—H6 | 0.9300 | C51—O52 | 1.290 (6) |
C7—C7A | 1.388 (2) | C51—O62 | 1.488 (10) |
C7—H7 | 0.9300 | O52—C52 | 1.463 (4) |
C11—H11A | 0.9600 | C52—C53 | 1.455 (5) |
C11—H11B | 0.9600 | C52—H52A | 0.9700 |
C11—H11C | 0.9600 | C52—H52B | 0.9700 |
N21—C25 | 1.3521 (19) | C53—H53A | 0.9600 |
N21—N22 | 1.3666 (18) | C53—H53B | 0.9600 |
N21—C211 | 1.431 (2) | C53—H53C | 0.9600 |
N22—C23 | 1.331 (2) | O62—C62 | 1.477 (7) |
C23—C24 | 1.417 (2) | C62—C63 | 1.455 (7) |
C23—C231 | 1.489 (2) | C62—H62A | 0.9700 |
C24—C25 | 1.369 (2) | C62—H62B | 0.9700 |
C25—Cl25 | 1.7047 (15) | C63—H63A | 0.9600 |
C211—C216 | 1.374 (2) | C63—H63B | 0.9600 |
C211—C212 | 1.381 (2) | C63—H63C | 0.9600 |
C212—C213 | 1.386 (3) | ||
C7A—N1—C2 | 106.34 (12) | C214—C213—C212 | 120.10 (18) |
C7A—N1—C11 | 124.17 (13) | C214—C213—H213 | 120.0 |
C2—N1—C11 | 129.10 (13) | C212—C213—H213 | 120.0 |
N3—C2—N1 | 113.46 (14) | C213—C214—C215 | 119.88 (19) |
N3—C2—C24 | 125.07 (14) | C213—C214—H214 | 120.1 |
N1—C2—C24 | 121.45 (14) | C215—C214—H214 | 120.1 |
C2—N3—C3A | 104.52 (13) | C214—C215—C216 | 121.06 (19) |
C4—C3A—N3 | 130.53 (14) | C214—C215—H215 | 119.5 |
C4—C3A—C7A | 119.33 (14) | C216—C215—H215 | 119.5 |
N3—C3A—C7A | 110.14 (13) | C211—C216—C215 | 118.57 (18) |
C3A—C4—C5 | 118.46 (14) | C211—C216—H216 | 120.7 |
C3A—C4—H4 | 120.8 | C215—C216—H216 | 120.7 |
C5—C4—H4 | 120.8 | C23—C231—H31A | 109.5 |
C4—C5—C6 | 121.19 (14) | C23—C231—H31C | 109.5 |
C4—C5—C51 | 117.43 (15) | H31A—C231—H31C | 109.5 |
C6—C5—C51 | 121.37 (15) | C23—C231—H31B | 109.5 |
C7—C6—C5 | 121.10 (15) | H31A—C231—H31B | 109.5 |
C7—C6—H6 | 119.5 | H31C—C231—H31B | 109.5 |
C5—C6—H6 | 119.5 | O51—C51—O52 | 123.5 (6) |
C6—C7—C7A | 117.12 (14) | O61—C51—C5 | 129.0 (13) |
C6—C7—H7 | 121.4 | O51—C51—C5 | 123.5 (6) |
C7A—C7—H7 | 121.4 | O52—C51—C5 | 112.8 (3) |
N1—C7A—C7 | 131.66 (14) | O61—C51—O62 | 121.3 (13) |
N1—C7A—C3A | 105.54 (13) | C5—C51—O62 | 109.3 (3) |
C7—C7A—C3A | 122.80 (14) | C51—O52—C52 | 115.3 (4) |
N1—C11—H11A | 109.5 | C53—C52—O52 | 108.7 (4) |
N1—C11—H11B | 109.5 | C53—C52—H52A | 110.0 |
H11A—C11—H11B | 109.5 | O52—C52—H52A | 110.0 |
N1—C11—H11C | 109.5 | C53—C52—H52B | 110.0 |
H11A—C11—H11C | 109.5 | O52—C52—H52B | 110.0 |
H11B—C11—H11C | 109.5 | H52A—C52—H52B | 108.3 |
C25—N21—N22 | 110.65 (12) | C52—C53—H53A | 109.5 |
C25—N21—C211 | 128.44 (13) | C52—C53—H53B | 109.5 |
N22—N21—C211 | 120.77 (12) | H53A—C53—H53B | 109.5 |
C23—N22—N21 | 105.33 (12) | C52—C53—H53C | 109.5 |
N22—C23—C24 | 111.40 (14) | H53A—C53—H53C | 109.5 |
N22—C23—C231 | 120.57 (14) | H53B—C53—H53C | 109.5 |
C24—C23—C231 | 128.01 (15) | C62—O62—C51 | 119.0 (7) |
C25—C24—C23 | 104.00 (13) | C63—C62—O62 | 106.4 (6) |
C25—C24—C2 | 126.95 (14) | C63—C62—H62A | 110.5 |
C23—C24—C2 | 129.04 (15) | O62—C62—H62A | 110.5 |
N21—C25—C24 | 108.61 (13) | C63—C62—H62B | 110.5 |
N21—C25—Cl25 | 121.47 (12) | O62—C62—H62B | 110.5 |
C24—C25—Cl25 | 129.59 (12) | H62A—C62—H62B | 108.6 |
C216—C211—C212 | 121.17 (16) | C62—C63—H63A | 109.5 |
C216—C211—N21 | 119.91 (15) | C62—C63—H63B | 109.5 |
C212—C211—N21 | 118.91 (14) | H63A—C63—H63B | 109.5 |
C211—C212—C213 | 119.22 (17) | C62—C63—H63C | 109.5 |
C211—C212—H212 | 120.4 | H63A—C63—H63C | 109.5 |
C213—C212—H212 | 120.4 | H63B—C63—H63C | 109.5 |
C7A—N1—C2—N3 | 0.98 (19) | C211—N21—C25—C24 | 175.07 (15) |
C11—N1—C2—N3 | −171.98 (16) | N22—N21—C25—Cl25 | 173.36 (11) |
C7A—N1—C2—C24 | −177.73 (15) | C211—N21—C25—Cl25 | −10.9 (2) |
C11—N1—C2—C24 | 9.3 (3) | C23—C24—C25—N21 | 0.95 (18) |
N1—C2—N3—C3A | −0.72 (19) | C2—C24—C25—N21 | −179.91 (15) |
C24—C2—N3—C3A | 177.93 (16) | C23—C24—C25—Cl25 | −172.42 (13) |
C2—N3—C3A—C4 | −179.16 (18) | C2—C24—C25—Cl25 | 6.7 (3) |
C2—N3—C3A—C7A | 0.20 (18) | C25—N21—C211—C216 | 124.20 (19) |
N3—C3A—C4—C5 | 179.75 (17) | N22—N21—C211—C216 | −60.5 (2) |
C7A—C3A—C4—C5 | 0.4 (2) | C25—N21—C211—C212 | −55.3 (2) |
C3A—C4—C5—C6 | 0.0 (3) | N22—N21—C211—C212 | 120.02 (17) |
C3A—C4—C5—C51 | −178.95 (16) | C216—C211—C212—C213 | −0.4 (3) |
C4—C5—C6—C7 | −0.2 (3) | N21—C211—C212—C213 | 179.05 (16) |
C51—C5—C6—C7 | 178.64 (17) | C211—C212—C213—C214 | −0.1 (3) |
C5—C6—C7—C7A | 0.1 (3) | C212—C213—C214—C215 | 0.5 (3) |
C2—N1—C7A—C7 | 179.74 (18) | C213—C214—C215—C216 | −0.3 (4) |
C11—N1—C7A—C7 | −6.9 (3) | C212—C211—C216—C215 | 0.6 (3) |
C2—N1—C7A—C3A | −0.77 (17) | N21—C211—C216—C215 | −178.90 (19) |
C11—N1—C7A—C3A | 172.62 (15) | C214—C215—C216—C211 | −0.2 (4) |
C6—C7—C7A—N1 | 179.79 (17) | C4—C5—C51—O61 | 11 (2) |
C6—C7—C7A—C3A | 0.4 (3) | C6—C5—C51—O61 | −167 (2) |
C4—C3A—C7A—N1 | 179.81 (15) | C4—C5—C51—O51 | 1.8 (10) |
N3—C3A—C7A—N1 | 0.38 (18) | C6—C5—C51—O51 | −177.1 (9) |
C4—C3A—C7A—C7 | −0.6 (3) | C4—C5—C51—O52 | 176.7 (3) |
N3—C3A—C7A—C7 | 179.92 (16) | C6—C5—C51—O52 | −2.2 (3) |
C25—N21—N22—C23 | 0.02 (18) | C4—C5—C51—O62 | −160.8 (4) |
C211—N21—N22—C23 | −176.07 (14) | C6—C5—C51—O62 | 20.3 (5) |
N21—N22—C23—C24 | 0.60 (18) | O61—C51—O52—C52 | −9.8 (19) |
N21—N22—C23—C231 | 179.07 (16) | O51—C51—O52—C52 | −2.1 (11) |
N22—C23—C24—C25 | −0.97 (19) | C5—C51—O52—C52 | −177.1 (3) |
C231—C23—C24—C25 | −179.30 (18) | O62—C51—O52—C52 | 98.2 (16) |
N22—C23—C24—C2 | 179.91 (16) | C51—O52—C52—C53 | −169.9 (6) |
C231—C23—C24—C2 | 1.6 (3) | O61—C51—O62—C62 | 3 (2) |
N3—C2—C24—C25 | −128.63 (19) | O51—C51—O62—C62 | 13.4 (13) |
N1—C2—C24—C25 | 49.9 (2) | O52—C51—O62—C62 | −80.8 (13) |
N3—C2—C24—C23 | 50.3 (3) | C5—C51—O62—C62 | 175.7 (5) |
N1—C2—C24—C23 | −131.15 (18) | C51—O62—C62—C63 | 89.5 (11) |
N22—N21—C25—C24 | −0.65 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C212—H212···O51i | 0.93 | 2.54 | 3.460 (14) | 168 |
C212—H212···O61i | 0.93 | 2.67 | 3.59 (2) | 170 |
Symmetry code: (i) x+1, y, z. |
Cg1 and Cg2 represent the centroids of the rings (C31–C36) and (C21–C26), respectively. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C23—H23···Cg1i | 0.93 | 2.77 | 3.412 (9) | 127 |
C26—H26···Cg1ii | 0.93 | 2.87 | 3.508 (9) | 127 | |
C35—H35···Cg2iii | 0.93 | 2.87 | 3.555 (9) | 131 | |
(II) | C11—H11A···O51iv | 0.97 | 2.51 | 3.253 (3) | 133 |
C22—H22···O51iv | 0.93 | 2.37 | 3.290 (3) | 168 | |
(III) | C212—H212···O51v | 0.93 | 2.54 | 3.460 (14) | 168 |
C212—H212···O61v | 0.93 | 2.67 | 3.59 (2) | 170 |
Symmetry codes: (i) x, 1 + y, z; (ii) x, -1 + y, z; (iii) 0.5 - x, 5/2 - y, 1 - z; (iv) 1 - x, 1/2 + y, 1/2 - z; (v) 1 + x, y, z. |
Acknowledgements
CHC thanks the University of Mysore for research facilities.
Funding information
HSY thanks the University Grants Commission, New Delhi, for the award of a BSR Faculty Fellowship for three years.
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