Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615023876/sk3612sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023876/sk3612Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023876/sk3612IIsup3.hkl |
CCDC references: 1442007; 1442006
We have recently described a simple and effective two-step approach to a new series of tricyclic pyrimidine-fused benzazepines, starting with a nucleophilic aminolysis of substituted 5-allyl-4,6-dichloropyrimidines by a substituted aniline, followed by an intramolecular Friedel–Crafts acylation promoted by methanesulfonic acid (Acosta-Quintero et al., 2015). The structures of a number of these compounds have also been reported recently (Acosta et al., 2015) and they exhibit very similar molecular conformations but different supramolecular structures. Compounds of this class, due to their close structural similarity to known bioactive molecules, could serve as promising targets in the development of new central nervous system (CNS) active and anticancer agents (Walker et al., 2011; Ohlmeyer & Kastrinsky, 2014).
If a cyclic amine such as indoline or 1,2,3,4-tetrahydroquinoline is used in our procedure instead of a substituted aniline, then a tetracyclic analogue of the previously reported tricyclic azepine derivatives will result. In a continuation and extension of our earlier study, we now report the molecular and supramolecular structures of two new tetracyclic compounds, namely 8-chloro-6-methyl-1,2,6,7-tetrahydropyrimido[5',4':6,7]azepino[3,2,1-hi]indole, (I) (Fig. 1), and 9-chloro-7-methyl-2,3,7,8-tetrahydro-1H-pyrimido[5',4':6,7]azepino[3,2,1-ij]-quinoline, (II) (Fig. 2). Compounds (I) and (II) were both obtained in good yields through the acid-promoted intramolecular Friedel–Crafts cyclization of the corresponding 1-(5-allyl-6-chloropyrimidin-4-yl)indoline and 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline (see Scheme 1).
Compound (I) was prepared and crystallized as previously described (Acosta-Quintero et al., 2015). For the synthesis of the intermediate 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline, equimolar quantities (5 mmol of each) of 1,2,3,4-tetrahydroquinoline and di(isopropyl)ethylamine were added to a solution of 5-allyl-4,6-dichloropyrimidine (5 mmol) in ethanol (5 ml). The mixture was heated under reflux until the reaction was complete, as judged by thin-layer chromatography. The mixture was then cooled to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified on silica gel using hexane–ethyl acetate (95:5 v/v) as eluent. For the synthesis of (II), methanesulfonic acid (99.5%, 1.0 ml) was added to a solution of 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline in chloroform (1 ml) and the mixture was stirred at 403 K for 25 min. The mixture was then poured onto an excess of crushed ice, and aqueous sodium carbonate solution was added until the pH reached 8.0. The aqueous mixture was then extracted with ethyl acetate (3 × 50 ml), the combined extracts were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude solid product was purified by chromatography on silica gel using hexane–ethyl acetate (12:1 to 8:1 v/v) as eluant. Yield 66%, m.p. 410–411 K; GC–MS (EI, 70 eV) m/z (%) = 285 [M+ (35Cl), 81], 272 (32), 270 (100), 256 (23), 250 (11); HRMS (EI–MS, 70 eV) m/z found 285.1027, C16H16ClN3 requires 285.1033. Colourless crystals [Of both compounds?] suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of a solution in hexane.
Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic C—H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. For (I), the analysis of variance reported a high value of K, 4.869, for the group of 319 very weak reflections having Fc/Fc(max) in the range 0.000 < Fc/Fc(max) < 0.010, while for (II) a value of K = 2.192 was reported for the group of 352 reflections having Fc/Fc(max) in the range 0.000 < Fc/Fc(max) < 0.012.
The constitutions of (I) and (II) differ only in the presence of a fused five-membered ring in (I) as opposed to the corresponding six-membered ring in (II). Because of this difference, the use of atom labels based upon the systematic chemical names leads to differences in the numbers for corresponding atoms in the two compounds (cf. Figs. 1 and 2). Each of (I) and (II) contains a stereogenic centre, at atoms C6 and C7, respectively (Figs. 1 and 2), and in each case the reference molecule was selected as one having the R-configuration at the stereogneic centre. However, the centrosymmetric space groups (P21/c and P1, respectively) confirm that both compounds have crystallized as racemic mixtures.
For the five-membered ring in (I), the ring-puckering parameters (Table 2) (Cremer & Pople, 1975) indicate a conformation close to an envelope form. This ring is folded across the line C2···N12: the four atoms C2, C2a, C2b and N12 are nearly coplanar, with an r.m.s. deviation from their mean plane of only 0.0144 Å, with a maximum deviation of 0.0177 (11) Å for atom C2b, while atom C1 is displaced from this plane by 0.320 (3) Å. Similarly, the six-membered ring which includes atom N13 in (II) also adopts an envelope conformation, now folded across the line C2···N13: the five atoms C2, C3, C3a, C3b and N13 are nearly coplanar, with a maximum deviation from their mean plane of 0.0354 (10) Å for atom C3 and with an r.m.s. deviation of 0.0283 Å. However, the displacement of atom C1 from this plane is 0.727 (2) Å. Hence, the behaviour of these two folded rings in (I) and (II) is rather similar.
In contrast, the behaviour of the seven-membered rings in (I) and (II) shows some substantial differences. The ring-puckering angles (Table 2) for the seven-membered ring in (II) are similar to those (Acosta et al., 2015) for the corresponding rings in compounds (III)–(VII) (see Scheme 2). This ring in (II) has a conformation (Fig. 3b) dominated by the sine form 2 or twist-boat conformation (Evans & Boeyens, 1989). By contrast, the conformation of the seven-membered ring in (I) has significant contributions not only from the twist-boat form but also from the sine form 3 or twist-chair form (Fig. 3a).
As a consequence of the different azepine ring conformations in (I) and (II), the values of the dihedral angle between the two aromatic rings are rather different (Table 2). Although the selected reference molecules both have the R-configuration at the stereogenic C atom, the different conformations of the azepine rings, in particular the sense of the ring fold across the lines C5a···C7 in (I) and C6a···C8 in (II) (Fig. 3), leads to the methyl group occupying a quasi-axial site in (I) and a quasi-equatorial site in (II). Within the series of compounds (I)–(VII), the C-methyl group occupies a quasi-equatorial site in each example apart from (I). It may be significant in this context that (I) is the only example in this group in which one of the C—H bonds of the azepine ring is involved in intermolecular hydrogen bonding, as discussed below, although it is unclear which of these two phenomena, the sense of the ring fold and the intermolecular hydrogen bonding, determines the other.
Molecules of (I) which are related by translation are linked by C—H···N hydrogen bonds (Table 3) to form C(5) (Bernstein et al., 1995) chains running parallel to the [100] direction, with each chain containing only one enantiomorph (Fig. 4). Inversion-related pairs of these chains are linked by a π–π stacking interaction: the pyrimidine rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.2890 (7)°, and the ring-centroid separation is 3.5929 (10) Å, corresponding to an almost ideal ring-centroid offset of 1.4462 (12) Å (Fig. 4).
The only hydrogen bond in the structure of (II) is one of C—H···π type (Table 3) which links inversion-related pairs of molecules into cyclic centrosymmetric dimers (Fig. 5). The structure of (II) also contains two weakly attractive (Imai et al., 2008) C—Cl···π interactions, involving both the phenyl and the pyrimidine rings (Table 4), which link the molecules into a ribbon running parallel to the [100] direction. The combination of this ribbon with the hydrogen-bonded dimers generates a complex sheet lying parallel to (011) (Fig. 6), but there are no direction-specific interactions between adjacent sheets.
In conclusion, although compounds (I) and (II) have closely related molecular constitutions, differing only by the presence of a single additional CH2 unit in one of the rings, both the azepine ring conformations and the supramolecular assemblies in (I) and (II) are very different.
We have recently described a simple and effective two-step approach to a new series of tricyclic pyrimidine-fused benzazepines, starting with a nucleophilic aminolysis of substituted 5-allyl-4,6-dichloropyrimidines by a substituted aniline, followed by an intramolecular Friedel–Crafts acylation promoted by methanesulfonic acid (Acosta-Quintero et al., 2015). The structures of a number of these compounds have also been reported recently (Acosta et al., 2015) and they exhibit very similar molecular conformations but different supramolecular structures. Compounds of this class, due to their close structural similarity to known bioactive molecules, could serve as promising targets in the development of new central nervous system (CNS) active and anticancer agents (Walker et al., 2011; Ohlmeyer & Kastrinsky, 2014).
If a cyclic amine such as indoline or 1,2,3,4-tetrahydroquinoline is used in our procedure instead of a substituted aniline, then a tetracyclic analogue of the previously reported tricyclic azepine derivatives will result. In a continuation and extension of our earlier study, we now report the molecular and supramolecular structures of two new tetracyclic compounds, namely 8-chloro-6-methyl-1,2,6,7-tetrahydropyrimido[5',4':6,7]azepino[3,2,1-hi]indole, (I) (Fig. 1), and 9-chloro-7-methyl-2,3,7,8-tetrahydro-1H-pyrimido[5',4':6,7]azepino[3,2,1-ij]-quinoline, (II) (Fig. 2). Compounds (I) and (II) were both obtained in good yields through the acid-promoted intramolecular Friedel–Crafts cyclization of the corresponding 1-(5-allyl-6-chloropyrimidin-4-yl)indoline and 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline (see Scheme 1).
The constitutions of (I) and (II) differ only in the presence of a fused five-membered ring in (I) as opposed to the corresponding six-membered ring in (II). Because of this difference, the use of atom labels based upon the systematic chemical names leads to differences in the numbers for corresponding atoms in the two compounds (cf. Figs. 1 and 2). Each of (I) and (II) contains a stereogenic centre, at atoms C6 and C7, respectively (Figs. 1 and 2), and in each case the reference molecule was selected as one having the R-configuration at the stereogneic centre. However, the centrosymmetric space groups (P21/c and P1, respectively) confirm that both compounds have crystallized as racemic mixtures.
For the five-membered ring in (I), the ring-puckering parameters (Table 2) (Cremer & Pople, 1975) indicate a conformation close to an envelope form. This ring is folded across the line C2···N12: the four atoms C2, C2a, C2b and N12 are nearly coplanar, with an r.m.s. deviation from their mean plane of only 0.0144 Å, with a maximum deviation of 0.0177 (11) Å for atom C2b, while atom C1 is displaced from this plane by 0.320 (3) Å. Similarly, the six-membered ring which includes atom N13 in (II) also adopts an envelope conformation, now folded across the line C2···N13: the five atoms C2, C3, C3a, C3b and N13 are nearly coplanar, with a maximum deviation from their mean plane of 0.0354 (10) Å for atom C3 and with an r.m.s. deviation of 0.0283 Å. However, the displacement of atom C1 from this plane is 0.727 (2) Å. Hence, the behaviour of these two folded rings in (I) and (II) is rather similar.
In contrast, the behaviour of the seven-membered rings in (I) and (II) shows some substantial differences. The ring-puckering angles (Table 2) for the seven-membered ring in (II) are similar to those (Acosta et al., 2015) for the corresponding rings in compounds (III)–(VII) (see Scheme 2). This ring in (II) has a conformation (Fig. 3b) dominated by the sine form 2 or twist-boat conformation (Evans & Boeyens, 1989). By contrast, the conformation of the seven-membered ring in (I) has significant contributions not only from the twist-boat form but also from the sine form 3 or twist-chair form (Fig. 3a).
As a consequence of the different azepine ring conformations in (I) and (II), the values of the dihedral angle between the two aromatic rings are rather different (Table 2). Although the selected reference molecules both have the R-configuration at the stereogenic C atom, the different conformations of the azepine rings, in particular the sense of the ring fold across the lines C5a···C7 in (I) and C6a···C8 in (II) (Fig. 3), leads to the methyl group occupying a quasi-axial site in (I) and a quasi-equatorial site in (II). Within the series of compounds (I)–(VII), the C-methyl group occupies a quasi-equatorial site in each example apart from (I). It may be significant in this context that (I) is the only example in this group in which one of the C—H bonds of the azepine ring is involved in intermolecular hydrogen bonding, as discussed below, although it is unclear which of these two phenomena, the sense of the ring fold and the intermolecular hydrogen bonding, determines the other.
Molecules of (I) which are related by translation are linked by C—H···N hydrogen bonds (Table 3) to form C(5) (Bernstein et al., 1995) chains running parallel to the [100] direction, with each chain containing only one enantiomorph (Fig. 4). Inversion-related pairs of these chains are linked by a π–π stacking interaction: the pyrimidine rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.2890 (7)°, and the ring-centroid separation is 3.5929 (10) Å, corresponding to an almost ideal ring-centroid offset of 1.4462 (12) Å (Fig. 4).
The only hydrogen bond in the structure of (II) is one of C—H···π type (Table 3) which links inversion-related pairs of molecules into cyclic centrosymmetric dimers (Fig. 5). The structure of (II) also contains two weakly attractive (Imai et al., 2008) C—Cl···π interactions, involving both the phenyl and the pyrimidine rings (Table 4), which link the molecules into a ribbon running parallel to the [100] direction. The combination of this ribbon with the hydrogen-bonded dimers generates a complex sheet lying parallel to (011) (Fig. 6), but there are no direction-specific interactions between adjacent sheets.
In conclusion, although compounds (I) and (II) have closely related molecular constitutions, differing only by the presence of a single additional CH2 unit in one of the rings, both the azepine ring conformations and the supramolecular assemblies in (I) and (II) are very different.
Compound (I) was prepared and crystallized as previously described (Acosta-Quintero et al., 2015). For the synthesis of the intermediate 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline, equimolar quantities (5 mmol of each) of 1,2,3,4-tetrahydroquinoline and di(isopropyl)ethylamine were added to a solution of 5-allyl-4,6-dichloropyrimidine (5 mmol) in ethanol (5 ml). The mixture was heated under reflux until the reaction was complete, as judged by thin-layer chromatography. The mixture was then cooled to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified on silica gel using hexane–ethyl acetate (95:5 v/v) as eluent. For the synthesis of (II), methanesulfonic acid (99.5%, 1.0 ml) was added to a solution of 1-(5-allyl-6-chloropyrimidin-4-yl)-1,2,3,4-tetrahydroquinoline in chloroform (1 ml) and the mixture was stirred at 403 K for 25 min. The mixture was then poured onto an excess of crushed ice, and aqueous sodium carbonate solution was added until the pH reached 8.0. The aqueous mixture was then extracted with ethyl acetate (3 × 50 ml), the combined extracts were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude solid product was purified by chromatography on silica gel using hexane–ethyl acetate (12:1 to 8:1 v/v) as eluant. Yield 66%, m.p. 410–411 K; GC–MS (EI, 70 eV) m/z (%) = 285 [M+ (35Cl), 81], 272 (32), 270 (100), 256 (23), 250 (11); HRMS (EI–MS, 70 eV) m/z found 285.1027, C16H16ClN3 requires 285.1033. Colourless crystals [Of both compounds?] suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of a solution in hexane.
Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic C—H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. For (I), the analysis of variance reported a high value of K, 4.869, for the group of 319 very weak reflections having Fc/Fc(max) in the range 0.000 < Fc/Fc(max) < 0.010, while for (II) a value of K = 2.192 was reported for the group of 352 reflections having Fc/Fc(max) in the range 0.000 < Fc/Fc(max) < 0.012.
For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
C15H14ClN3 | F(000) = 568 |
Mr = 271.74 | Dx = 1.428 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6250 (3) Å | Cell parameters from 2903 reflections |
b = 22.4796 (13) Å | θ = 2.6–27.6° |
c = 8.6355 (4) Å | µ = 0.29 mm−1 |
β = 100.610 (3)° | T = 100 K |
V = 1264.07 (11) Å3 | Block, colourless |
Z = 4 | 0.12 × 0.12 × 0.10 mm |
Bruker D8 Venture diffractometer | 2901 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 2329 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.083 |
φ and ω scans | θmax = 27.6°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→8 |
Tmin = 0.812, Tmax = 0.971 | k = −25→29 |
16728 measured reflections | l = −10→11 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.7689P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2901 reflections | Δρmax = 0.75 e Å−3 |
173 parameters | Δρmin = −0.38 e Å−3 |
C15H14ClN3 | V = 1264.07 (11) Å3 |
Mr = 271.74 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.6250 (3) Å | µ = 0.29 mm−1 |
b = 22.4796 (13) Å | T = 100 K |
c = 8.6355 (4) Å | 0.12 × 0.12 × 0.10 mm |
β = 100.610 (3)° |
Bruker D8 Venture diffractometer | 2901 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2329 reflections with I > 2σ(I) |
Tmin = 0.812, Tmax = 0.971 | Rint = 0.083 |
16728 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.75 e Å−3 |
2901 reflections | Δρmin = −0.38 e Å−3 |
173 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6066 (3) | 0.45800 (9) | 0.1446 (2) | 0.0239 (4) | |
H1A | 0.5879 | 0.5004 | 0.1700 | 0.029* | |
H1B | 0.4812 | 0.4437 | 0.0740 | 0.029* | |
C2 | 0.7956 (3) | 0.44979 (10) | 0.0687 (2) | 0.0291 (5) | |
H2A | 0.7562 | 0.4453 | −0.0470 | 0.035* | |
H2B | 0.8911 | 0.4838 | 0.0924 | 0.035* | |
C2a | 0.8903 (3) | 0.39374 (10) | 0.1432 (2) | 0.0235 (4) | |
C2b | 0.8070 (3) | 0.37952 (9) | 0.2764 (2) | 0.0182 (4) | |
C3 | 1.0462 (3) | 0.36023 (11) | 0.1012 (2) | 0.0305 (5) | |
H3 | 1.1001 | 0.3698 | 0.0097 | 0.037* | |
C4 | 1.1228 (3) | 0.31245 (11) | 0.1948 (3) | 0.0327 (5) | |
H4 | 1.2305 | 0.2890 | 0.1680 | 0.039* | |
C5 | 1.0417 (3) | 0.29879 (10) | 0.3281 (2) | 0.0261 (4) | |
H5 | 1.0971 | 0.2660 | 0.3914 | 0.031* | |
C5a | 0.8813 (3) | 0.33159 (9) | 0.3728 (2) | 0.0190 (4) | |
C6 | 0.8084 (3) | 0.31358 (8) | 0.5213 (2) | 0.0187 (4) | |
H6 | 0.9282 | 0.2945 | 0.5912 | 0.022* | |
C7 | 0.7471 (3) | 0.36736 (8) | 0.6117 (2) | 0.0179 (4) | |
H7A | 0.7393 | 0.3546 | 0.7201 | 0.021* | |
H7B | 0.8569 | 0.3977 | 0.6195 | 0.021* | |
C7a | 0.5468 (3) | 0.39584 (8) | 0.54002 (19) | 0.0155 (4) | |
C8 | 0.3794 (3) | 0.40097 (8) | 0.6144 (2) | 0.0173 (4) | |
Cl8 | 0.37942 (8) | 0.36267 (2) | 0.79091 (6) | 0.02699 (15) | |
N9 | 0.2123 (2) | 0.43379 (7) | 0.56786 (19) | 0.0191 (3) | |
C10 | 0.2119 (3) | 0.46273 (8) | 0.4330 (2) | 0.0195 (4) | |
H10 | 0.0990 | 0.4886 | 0.3990 | 0.023* | |
N11 | 0.3508 (2) | 0.45949 (7) | 0.34097 (18) | 0.0184 (3) | |
C11a | 0.5155 (3) | 0.42477 (8) | 0.3914 (2) | 0.0159 (4) | |
N12 | 0.6516 (3) | 0.42159 (7) | 0.29006 (17) | 0.0184 (3) | |
C61 | 0.6389 (3) | 0.26674 (9) | 0.4909 (2) | 0.0258 (4) | |
H61A | 0.6876 | 0.2320 | 0.4397 | 0.039* | |
H61B | 0.5179 | 0.2835 | 0.4222 | 0.039* | |
H61C | 0.6023 | 0.2546 | 0.5912 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0356 (12) | 0.0231 (10) | 0.0146 (9) | −0.0019 (9) | 0.0092 (7) | 0.0025 (7) |
C2 | 0.0343 (12) | 0.0369 (12) | 0.0193 (9) | −0.0122 (10) | 0.0130 (8) | −0.0012 (8) |
C2a | 0.0230 (10) | 0.0326 (11) | 0.0169 (9) | −0.0103 (8) | 0.0085 (7) | −0.0072 (8) |
C2b | 0.0163 (9) | 0.0244 (10) | 0.0154 (8) | −0.0055 (7) | 0.0070 (7) | −0.0074 (7) |
C3 | 0.0232 (11) | 0.0494 (14) | 0.0219 (10) | −0.0118 (10) | 0.0118 (8) | −0.0148 (9) |
C4 | 0.0192 (10) | 0.0495 (14) | 0.0312 (11) | −0.0003 (10) | 0.0093 (8) | −0.0164 (10) |
C5 | 0.0172 (10) | 0.0338 (11) | 0.0273 (10) | 0.0028 (8) | 0.0041 (7) | −0.0106 (9) |
C5a | 0.0157 (9) | 0.0243 (10) | 0.0177 (9) | −0.0036 (7) | 0.0045 (6) | −0.0081 (7) |
C6 | 0.0178 (9) | 0.0216 (9) | 0.0165 (8) | 0.0011 (7) | 0.0028 (6) | −0.0003 (7) |
C7 | 0.0175 (9) | 0.0211 (9) | 0.0162 (8) | −0.0015 (7) | 0.0061 (6) | −0.0022 (7) |
C7a | 0.0179 (9) | 0.0150 (8) | 0.0141 (8) | −0.0033 (7) | 0.0044 (6) | −0.0032 (6) |
C8 | 0.0193 (9) | 0.0174 (9) | 0.0171 (8) | −0.0042 (7) | 0.0084 (7) | −0.0026 (7) |
Cl8 | 0.0316 (3) | 0.0308 (3) | 0.0233 (2) | 0.0018 (2) | 0.01737 (19) | 0.00511 (19) |
N9 | 0.0164 (8) | 0.0189 (8) | 0.0234 (8) | −0.0017 (6) | 0.0070 (6) | −0.0056 (6) |
C10 | 0.0172 (9) | 0.0180 (9) | 0.0229 (9) | 0.0004 (7) | 0.0025 (7) | −0.0048 (7) |
N11 | 0.0196 (8) | 0.0169 (8) | 0.0186 (7) | −0.0008 (6) | 0.0034 (6) | −0.0026 (6) |
C11a | 0.0180 (9) | 0.0144 (8) | 0.0163 (8) | −0.0035 (7) | 0.0053 (6) | −0.0028 (7) |
N12 | 0.0233 (8) | 0.0196 (8) | 0.0140 (7) | −0.0007 (6) | 0.0081 (6) | 0.0009 (6) |
C61 | 0.0280 (11) | 0.0193 (10) | 0.0315 (11) | −0.0010 (8) | 0.0090 (8) | −0.0021 (8) |
C1—N12 | 1.483 (2) | C6—C61 | 1.527 (3) |
C1—C2 | 1.528 (3) | C6—C7 | 1.534 (2) |
C1—H1A | 0.9900 | C6—H6 | 1.0000 |
C1—H1B | 0.9900 | C7—C7a | 1.501 (3) |
C2—C2a | 1.499 (3) | C7—H7A | 0.9900 |
C2—H2A | 0.9900 | C7—H7B | 0.9900 |
C2—H2B | 0.9900 | C7a—C8 | 1.385 (2) |
C2a—C3 | 1.380 (3) | C7a—C11a | 1.420 (2) |
C2a—C2b | 1.401 (2) | C8—N9 | 1.330 (2) |
C2b—C5a | 1.395 (3) | C8—Cl8 | 1.7506 (18) |
C2b—N12 | 1.418 (2) | N9—C10 | 1.334 (2) |
C3—C4 | 1.383 (3) | C10—N11 | 1.324 (2) |
C3—H3 | 0.9500 | C10—H10 | 0.9500 |
C4—C5 | 1.391 (3) | N11—C11a | 1.347 (2) |
C4—H4 | 0.9500 | C11a—N12 | 1.370 (2) |
C5—C5a | 1.404 (3) | C61—H61A | 0.9800 |
C5—H5 | 0.9500 | C61—H61B | 0.9800 |
C5a—C6 | 1.507 (2) | C61—H61C | 0.9800 |
N12—C1—C2 | 104.12 (17) | C5a—C6—H6 | 106.6 |
N12—C1—H1A | 110.9 | C61—C6—H6 | 106.6 |
C2—C1—H1A | 110.9 | C7—C6—H6 | 106.6 |
N12—C1—H1B | 110.9 | C7a—C7—C6 | 115.06 (15) |
C2—C1—H1B | 110.9 | C7a—C7—H7A | 108.5 |
H1A—C1—H1B | 108.9 | C6—C7—H7A | 108.5 |
C2a—C2—C1 | 103.19 (15) | C7a—C7—H7B | 108.5 |
C2a—C2—H2A | 111.1 | C6—C7—H7B | 108.5 |
C1—C2—H2A | 111.1 | H7A—C7—H7B | 107.5 |
C2a—C2—H2B | 111.1 | C8—C7a—C11a | 112.65 (16) |
C1—C2—H2B | 111.1 | C8—C7a—C7 | 124.56 (16) |
H2A—C2—H2B | 109.1 | C11a—C7a—C7 | 122.62 (16) |
C3—C2a—C2b | 121.2 (2) | N9—C8—C7a | 126.82 (17) |
C3—C2a—C2 | 128.34 (18) | N9—C8—Cl8 | 113.73 (13) |
C2b—C2a—C2 | 110.34 (17) | C7a—C8—Cl8 | 119.43 (15) |
C5a—C2b—C2a | 121.13 (18) | C8—N9—C10 | 113.73 (15) |
C5a—C2b—N12 | 130.34 (16) | N11—C10—N9 | 127.39 (18) |
C2a—C2b—N12 | 108.51 (17) | N11—C10—H10 | 116.3 |
C2a—C3—C4 | 118.83 (19) | N9—C10—H10 | 116.3 |
C2a—C3—H3 | 120.6 | C10—N11—C11a | 116.69 (16) |
C4—C3—H3 | 120.6 | N11—C11a—N12 | 114.41 (16) |
C3—C4—C5 | 119.9 (2) | N11—C11a—C7a | 122.19 (16) |
C3—C4—H4 | 120.0 | N12—C11a—C7a | 123.37 (17) |
C5—C4—H4 | 120.0 | C11a—N12—C2b | 131.40 (16) |
C4—C5—C5a | 122.5 (2) | C11a—N12—C1 | 117.32 (16) |
C4—C5—H5 | 118.7 | C2b—N12—C1 | 109.48 (14) |
C5a—C5—H5 | 118.7 | C6—C61—H61A | 109.5 |
C2b—C5a—C5 | 116.34 (18) | C6—C61—H61B | 109.5 |
C2b—C5a—C6 | 125.61 (16) | H61A—C61—H61B | 109.5 |
C5—C5a—C6 | 118.02 (18) | C6—C61—H61C | 109.5 |
C5a—C6—C61 | 112.32 (15) | H61A—C61—H61C | 109.5 |
C5a—C6—C7 | 112.19 (15) | H61B—C61—H61C | 109.5 |
C61—C6—C7 | 112.08 (15) | ||
N12—C1—C2—C2a | 20.1 (2) | C11a—C7a—C8—N9 | −7.1 (3) |
C1—C2—C2a—C3 | 169.0 (2) | C7—C7a—C8—N9 | 168.26 (17) |
C1—C2—C2a—C2b | −15.0 (2) | C11a—C7a—C8—Cl8 | 174.34 (13) |
C3—C2a—C2b—C5a | 1.1 (3) | C7—C7a—C8—Cl8 | −10.3 (2) |
C2—C2a—C2b—C5a | −175.25 (17) | C7a—C8—N9—C10 | 1.7 (3) |
C3—C2a—C2b—N12 | 179.70 (18) | Cl8—C8—N9—C10 | −179.67 (13) |
C2—C2a—C2b—N12 | 3.3 (2) | C8—N9—C10—N11 | 3.8 (3) |
C2b—C2a—C3—C4 | −1.1 (3) | N9—C10—N11—C11a | −2.6 (3) |
C2—C2a—C3—C4 | 174.6 (2) | C10—N11—C11a—N12 | 178.25 (16) |
C2a—C3—C4—C5 | 0.3 (3) | C10—N11—C11a—C7a | −3.9 (3) |
C3—C4—C5—C5a | 0.5 (3) | C8—C7a—C11a—N11 | 8.0 (2) |
C2a—C2b—C5a—C5 | −0.3 (3) | C7—C7a—C11a—N11 | −167.40 (17) |
N12—C2b—C5a—C5 | −178.54 (18) | C8—C7a—C11a—N12 | −174.27 (17) |
C2a—C2b—C5a—C6 | 177.82 (17) | C7—C7a—C11a—N12 | 10.3 (3) |
N12—C2b—C5a—C6 | −0.4 (3) | N11—C11a—N12—C2b | −160.29 (18) |
C4—C5—C5a—C2b | −0.5 (3) | C7a—C11a—N12—C2b | 21.8 (3) |
C4—C5—C5a—C6 | −178.78 (18) | N11—C11a—N12—C1 | 2.6 (2) |
C2b—C5a—C6—C61 | 93.1 (2) | C7a—C11a—N12—C1 | −175.23 (16) |
C5—C5a—C6—C61 | −88.8 (2) | C5a—C2b—N12—C11a | −7.2 (3) |
C2b—C5a—C6—C7 | −34.2 (2) | C2a—C2b—N12—C11a | 174.44 (19) |
C5—C5a—C6—C7 | 143.93 (17) | C5a—C2b—N12—C1 | −171.10 (19) |
C5a—C6—C7—C7a | 74.2 (2) | C2a—C2b—N12—C1 | 10.5 (2) |
C61—C6—C7—C7a | −53.2 (2) | C2—C1—N12—C11a | 174.06 (16) |
C6—C7—C7a—C8 | 119.83 (19) | C2—C1—N12—C2b | −19.5 (2) |
C6—C7—C7a—C11a | −65.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7B···N9i | 0.99 | 2.61 | 3.507 (2) | 151 |
Symmetry code: (i) x+1, y, z. |
C16H16ClN3 | Z = 2 |
Mr = 285.77 | F(000) = 300 |
Triclinic, P1 | Dx = 1.389 Mg m−3 |
a = 8.184 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.5399 (12) Å | Cell parameters from 4161 reflections |
c = 10.2185 (19) Å | θ = 2.2–30.6° |
α = 104.471 (7)° | µ = 0.27 mm−1 |
β = 101.049 (6)° | T = 100 K |
γ = 111.324 (5)° | Block, colourless |
V = 683.40 (18) Å3 | 0.14 × 0.14 × 0.12 mm |
Bruker D8 Venture diffractometer | 3157 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 2784 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.033 |
φ and ω scans | θmax = 27.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.854, Tmax = 0.968 | k = −12→12 |
15418 measured reflections | l = −13→12 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0445P)2 + 0.4707P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3157 reflections | Δρmax = 0.65 e Å−3 |
182 parameters | Δρmin = −0.27 e Å−3 |
C16H16ClN3 | γ = 111.324 (5)° |
Mr = 285.77 | V = 683.40 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.184 (1) Å | Mo Kα radiation |
b = 9.5399 (12) Å | µ = 0.27 mm−1 |
c = 10.2185 (19) Å | T = 100 K |
α = 104.471 (7)° | 0.14 × 0.14 × 0.12 mm |
β = 101.049 (6)° |
Bruker D8 Venture diffractometer | 3157 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2784 reflections with I > 2σ(I) |
Tmin = 0.854, Tmax = 0.968 | Rint = 0.033 |
15418 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.65 e Å−3 |
3157 reflections | Δρmin = −0.27 e Å−3 |
182 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8612 (2) | 0.37892 (17) | 0.10006 (16) | 0.0186 (3) | |
H1A | 0.9902 | 0.3921 | 0.1244 | 0.022* | |
H1B | 0.8632 | 0.4852 | 0.1083 | 0.022* | |
C2 | 0.7536 (2) | 0.26168 (18) | −0.05117 (16) | 0.0194 (3) | |
H2A | 0.8046 | 0.3069 | −0.1195 | 0.023* | |
H2B | 0.6223 | 0.2423 | −0.0732 | 0.023* | |
C3 | 0.7687 (2) | 0.10445 (19) | −0.06408 (16) | 0.0197 (3) | |
H3A | 0.6633 | 0.0165 | −0.1445 | 0.024* | |
H3B | 0.8835 | 0.1123 | −0.0864 | 0.024* | |
C3a | 0.77022 (18) | 0.06246 (17) | 0.06933 (15) | 0.0153 (3) | |
C3b | 0.76949 (18) | 0.16343 (16) | 0.19530 (15) | 0.0139 (3) | |
C4 | 0.7762 (2) | −0.08192 (18) | 0.06930 (17) | 0.0188 (3) | |
H4 | 0.7789 | −0.1511 | −0.0144 | 0.023* | |
C5 | 0.7785 (2) | −0.12660 (18) | 0.18774 (18) | 0.0214 (3) | |
H5 | 0.7794 | −0.2267 | 0.1845 | 0.026* | |
C6 | 0.7794 (2) | −0.02430 (19) | 0.31199 (17) | 0.0204 (3) | |
H6 | 0.7803 | −0.0553 | 0.3935 | 0.025* | |
C6a | 0.77892 (19) | 0.12333 (17) | 0.31805 (15) | 0.0165 (3) | |
C7 | 0.7881 (2) | 0.24291 (19) | 0.45085 (16) | 0.0203 (3) | |
H7 | 0.8762 | 0.3520 | 0.4588 | 0.024* | |
C8 | 0.5965 (2) | 0.24145 (19) | 0.43391 (16) | 0.0200 (3) | |
H8A | 0.5036 | 0.1292 | 0.4067 | 0.024* | |
H8B | 0.5959 | 0.3032 | 0.5272 | 0.024* | |
C8a | 0.53912 (19) | 0.31026 (16) | 0.32514 (15) | 0.0153 (3) | |
C9 | 0.39051 (19) | 0.34871 (17) | 0.32198 (15) | 0.0172 (3) | |
Cl9 | 0.24959 (5) | 0.28487 (5) | 0.42363 (4) | 0.02551 (12) | |
N10 | 0.34084 (17) | 0.43187 (15) | 0.24867 (14) | 0.0210 (3) | |
C11 | 0.4540 (2) | 0.48418 (18) | 0.17551 (18) | 0.0223 (3) | |
H11 | 0.4313 | 0.5531 | 0.1291 | 0.027* | |
N12 | 0.59490 (18) | 0.45071 (15) | 0.16033 (14) | 0.0194 (3) | |
C12a | 0.63380 (19) | 0.35715 (16) | 0.22866 (15) | 0.0146 (3) | |
N13 | 0.77143 (16) | 0.31569 (14) | 0.19881 (13) | 0.0146 (2) | |
C71 | 0.8549 (3) | 0.2155 (2) | 0.58802 (18) | 0.0308 (4) | |
H71A | 0.9739 | 0.2111 | 0.5952 | 0.046* | |
H71B | 0.7643 | 0.1139 | 0.5872 | 0.046* | |
H71C | 0.8693 | 0.3039 | 0.6697 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0153 (7) | 0.0168 (7) | 0.0255 (8) | 0.0067 (6) | 0.0088 (6) | 0.0087 (6) |
C2 | 0.0195 (7) | 0.0232 (7) | 0.0214 (7) | 0.0106 (6) | 0.0107 (6) | 0.0117 (6) |
C3 | 0.0196 (7) | 0.0234 (7) | 0.0185 (7) | 0.0124 (6) | 0.0074 (6) | 0.0053 (6) |
C3a | 0.0098 (6) | 0.0169 (7) | 0.0181 (7) | 0.0070 (5) | 0.0028 (5) | 0.0038 (5) |
C3b | 0.0099 (6) | 0.0127 (6) | 0.0175 (7) | 0.0060 (5) | 0.0012 (5) | 0.0032 (5) |
C4 | 0.0149 (7) | 0.0167 (7) | 0.0226 (7) | 0.0095 (6) | 0.0031 (5) | 0.0012 (6) |
C5 | 0.0166 (7) | 0.0167 (7) | 0.0315 (8) | 0.0102 (6) | 0.0034 (6) | 0.0076 (6) |
C6 | 0.0178 (7) | 0.0239 (8) | 0.0235 (8) | 0.0117 (6) | 0.0044 (6) | 0.0122 (6) |
C6a | 0.0131 (6) | 0.0190 (7) | 0.0164 (7) | 0.0083 (5) | 0.0017 (5) | 0.0050 (6) |
C7 | 0.0208 (7) | 0.0242 (8) | 0.0154 (7) | 0.0108 (6) | 0.0032 (6) | 0.0062 (6) |
C8 | 0.0254 (8) | 0.0238 (7) | 0.0146 (7) | 0.0139 (6) | 0.0082 (6) | 0.0063 (6) |
C8a | 0.0157 (6) | 0.0119 (6) | 0.0149 (7) | 0.0059 (5) | 0.0033 (5) | 0.0007 (5) |
C9 | 0.0143 (7) | 0.0145 (7) | 0.0183 (7) | 0.0050 (5) | 0.0047 (5) | 0.0008 (5) |
Cl9 | 0.01859 (19) | 0.0305 (2) | 0.0277 (2) | 0.00967 (15) | 0.01196 (15) | 0.00840 (16) |
N10 | 0.0171 (6) | 0.0183 (6) | 0.0277 (7) | 0.0106 (5) | 0.0058 (5) | 0.0048 (5) |
C11 | 0.0227 (8) | 0.0173 (7) | 0.0322 (8) | 0.0132 (6) | 0.0091 (6) | 0.0101 (6) |
N12 | 0.0204 (6) | 0.0158 (6) | 0.0268 (7) | 0.0108 (5) | 0.0088 (5) | 0.0094 (5) |
C12a | 0.0129 (6) | 0.0111 (6) | 0.0168 (7) | 0.0053 (5) | 0.0022 (5) | 0.0016 (5) |
N13 | 0.0147 (6) | 0.0139 (6) | 0.0170 (6) | 0.0079 (5) | 0.0055 (5) | 0.0056 (5) |
C71 | 0.0316 (9) | 0.0436 (10) | 0.0198 (8) | 0.0173 (8) | 0.0066 (7) | 0.0146 (8) |
C1—N13 | 1.4790 (18) | C6a—C7 | 1.508 (2) |
C1—C2 | 1.521 (2) | C7—C71 | 1.525 (2) |
C1—H1A | 0.9900 | C7—C8 | 1.539 (2) |
C1—H1B | 0.9900 | C7—H7 | 1.0000 |
C2—C3 | 1.525 (2) | C8—C8a | 1.509 (2) |
C2—H2A | 0.9900 | C8—H8A | 0.9900 |
C2—H2B | 0.9900 | C8—H8B | 0.9900 |
C3—C3a | 1.513 (2) | C8a—C9 | 1.3892 (19) |
C3—H3A | 0.9900 | C8a—C12a | 1.426 (2) |
C3—H3B | 0.9900 | C9—N10 | 1.331 (2) |
C3a—C4 | 1.396 (2) | C9—Cl9 | 1.7449 (15) |
C3a—C3b | 1.4044 (19) | N10—C11 | 1.335 (2) |
C3b—C6a | 1.396 (2) | C11—N12 | 1.3293 (19) |
C3b—N13 | 1.4382 (17) | C11—H11 | 0.9500 |
C4—C5 | 1.379 (2) | N12—C12a | 1.3485 (18) |
C4—H4 | 0.9500 | C12a—N13 | 1.3834 (17) |
C5—C6 | 1.392 (2) | C71—H71A | 0.9800 |
C5—H5 | 0.9500 | C71—H71B | 0.9800 |
C6—C6a | 1.396 (2) | C71—H71C | 0.9800 |
C6—H6 | 0.9500 | ||
N13—C1—C2 | 108.88 (12) | C6a—C7—C71 | 114.46 (13) |
N13—C1—H1A | 109.9 | C6a—C7—C8 | 108.77 (12) |
C2—C1—H1A | 109.9 | C71—C7—C8 | 110.18 (13) |
N13—C1—H1B | 109.9 | C6a—C7—H7 | 107.7 |
C2—C1—H1B | 109.9 | C71—C7—H7 | 107.7 |
H1A—C1—H1B | 108.3 | C8—C7—H7 | 107.7 |
C1—C2—C3 | 108.63 (12) | C8a—C8—C7 | 114.62 (12) |
C1—C2—H2A | 110.0 | C8a—C8—H8A | 108.6 |
C3—C2—H2A | 110.0 | C7—C8—H8A | 108.6 |
C1—C2—H2B | 110.0 | C8a—C8—H8B | 108.6 |
C3—C2—H2B | 110.0 | C7—C8—H8B | 108.6 |
H2A—C2—H2B | 108.3 | H8A—C8—H8B | 107.6 |
C3a—C3—C2 | 113.32 (12) | C9—C8a—C12a | 113.28 (13) |
C3a—C3—H3A | 108.9 | C9—C8a—C8 | 119.95 (13) |
C2—C3—H3A | 108.9 | C12a—C8a—C8 | 126.48 (13) |
C3a—C3—H3B | 108.9 | N10—C9—C8a | 127.01 (14) |
C2—C3—H3B | 108.9 | N10—C9—Cl9 | 114.27 (11) |
H3A—C3—H3B | 107.7 | C8a—C9—Cl9 | 118.73 (12) |
C4—C3a—C3b | 117.88 (13) | C9—N10—C11 | 113.29 (13) |
C4—C3a—C3 | 118.93 (13) | N12—C11—N10 | 127.31 (14) |
C3b—C3a—C3 | 123.18 (13) | N12—C11—H11 | 116.3 |
C6a—C3b—C3a | 121.39 (13) | N10—C11—H11 | 116.3 |
C6a—C3b—N13 | 120.00 (12) | C11—N12—C12a | 117.62 (13) |
C3a—C3b—N13 | 118.47 (12) | N12—C12a—N13 | 114.68 (13) |
C5—C4—C3a | 121.63 (14) | N12—C12a—C8a | 120.73 (12) |
C5—C4—H4 | 119.2 | N13—C12a—C8a | 124.58 (13) |
C3a—C4—H4 | 119.2 | C12a—N13—C3b | 121.95 (11) |
C4—C5—C6 | 119.65 (14) | C12a—N13—C1 | 118.05 (12) |
C4—C5—H5 | 120.2 | C3b—N13—C1 | 112.65 (11) |
C6—C5—H5 | 120.2 | C7—C71—H71A | 109.5 |
C5—C6—C6a | 120.63 (14) | C7—C71—H71B | 109.5 |
C5—C6—H6 | 119.7 | H71A—C71—H71B | 109.5 |
C6a—C6—H6 | 119.7 | C7—C71—H71C | 109.5 |
C6—C6a—C3b | 118.74 (13) | H71A—C71—H71C | 109.5 |
C6—C6a—C7 | 123.40 (13) | H71B—C71—H71C | 109.5 |
C3b—C6a—C7 | 117.86 (13) | ||
N13—C1—C2—C3 | −64.95 (14) | C7—C8—C8a—C12a | 7.7 (2) |
C1—C2—C3—C3a | 35.82 (16) | C12a—C8a—C9—N10 | −5.3 (2) |
C2—C3—C3a—C4 | 177.51 (12) | C8—C8a—C9—N10 | 168.88 (14) |
C2—C3—C3a—C3b | −3.78 (19) | C12a—C8a—C9—Cl9 | 174.96 (10) |
C4—C3a—C3b—C6a | 1.5 (2) | C8—C8a—C9—Cl9 | −10.83 (18) |
C3—C3a—C3b—C6a | −177.23 (13) | C8a—C9—N10—C11 | −1.9 (2) |
C4—C3a—C3b—N13 | 177.33 (12) | Cl9—C9—N10—C11 | 177.85 (11) |
C3—C3a—C3b—N13 | −1.4 (2) | C9—N10—C11—N12 | 6.0 (2) |
C3b—C3a—C4—C5 | 1.0 (2) | N10—C11—N12—C12a | −2.0 (2) |
C3—C3a—C4—C5 | 179.80 (13) | C11—N12—C12a—N13 | 174.74 (13) |
C3a—C4—C5—C6 | −1.6 (2) | C11—N12—C12a—C8a | −6.4 (2) |
C4—C5—C6—C6a | −0.3 (2) | C9—C8a—C12a—N12 | 9.4 (2) |
C5—C6—C6a—C3b | 2.7 (2) | C8—C8a—C12a—N12 | −164.32 (14) |
C5—C6—C6a—C7 | −177.27 (14) | C9—C8a—C12a—N13 | −171.79 (13) |
C3a—C3b—C6a—C6 | −3.3 (2) | C8—C8a—C12a—N13 | 14.5 (2) |
N13—C3b—C6a—C6 | −179.11 (12) | N12—C12a—N13—C3b | −146.76 (13) |
C3a—C3b—C6a—C7 | 176.66 (13) | C8a—C12a—N13—C3b | 34.4 (2) |
N13—C3b—C6a—C7 | 0.88 (19) | N12—C12a—N13—C1 | 1.07 (18) |
C6—C6a—C7—C71 | 17.3 (2) | C8a—C12a—N13—C1 | −177.77 (13) |
C3b—C6a—C7—C71 | −162.65 (14) | C6a—C3b—N13—C12a | −62.33 (18) |
C6—C6a—C7—C8 | −106.35 (16) | C3a—C3b—N13—C12a | 121.78 (14) |
C3b—C6a—C7—C8 | 73.65 (16) | C6a—C3b—N13—C1 | 148.28 (13) |
C6a—C7—C8—C8a | −69.36 (16) | C3a—C3b—N13—C1 | −27.62 (17) |
C71—C7—C8—C8a | 164.43 (13) | C2—C1—N13—C12a | −89.26 (15) |
C7—C8—C8a—C9 | −165.69 (13) | C2—C1—N13—C3b | 61.44 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg1i | 0.95 | 2.72 | 3.4323 (18) | 133 |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H14ClN3 | C16H16ClN3 |
Mr | 271.74 | 285.77 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 6.6250 (3), 22.4796 (13), 8.6355 (4) | 8.184 (1), 9.5399 (12), 10.2185 (19) |
α, β, γ (°) | 90, 100.610 (3), 90 | 104.471 (7), 101.049 (6), 111.324 (5) |
V (Å3) | 1264.07 (11) | 683.40 (18) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.29 | 0.27 |
Crystal size (mm) | 0.12 × 0.12 × 0.10 | 0.14 × 0.14 × 0.12 |
Data collection | ||
Diffractometer | Bruker D8 Venture | Bruker D8 Venture |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.812, 0.971 | 0.854, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16728, 2901, 2329 | 15418, 3157, 2784 |
Rint | 0.083 | 0.033 |
(sin θ/λ)max (Å−1) | 0.651 | 0.651 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.114, 1.08 | 0.038, 0.098, 1.04 |
No. of reflections | 2901 | 3157 |
No. of parameters | 173 | 182 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −0.38 | 0.65, −0.27 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
Ring-puckering parameters | (Å, °) | ||
(a) Five-membered ring | |||
(I) | (II) | Envelope | |
Q2 | 0.202 (2) | ||
φ2 | 44.8 (6) | 36k | |
(b) Six-membered ring | |||
Q | 0.5400 (17) | ||
θ | 126.66 (8) | 125.3 | |
φ | 249.1 (2) | 60k | |
(c) Seven-membered rings | |||
Q | 0.612 (2) | 0.8809 (17) | |
φ2 | 295.7 (2) | 41.77 (12) | |
φ3 | 88.7 (3) | 286.9 (3) | |
Torsion and dihedral angles | |||
Parameter | (I) | Parameter | (II) |
C1-N12-C2b-C5a | -171.10 (19) | C1-N13_C3b-C6a | 148.28 (13) |
N11-C11a-C7a-C7 | -167.40 (17) | N12-C12a-C8a-C8 | -164.32 (14) |
N12-C2b-C5a-C6 | -0.4 (3) | N13-C3b-C6a-C7 | 0.88 (19) |
C11a-C7a-C7-C6 | -65.3 (2) | C12a-C8a-C8-C7 | 7.7 (2) |
C2b-C5a-C6-C61 | 93.1 (2) | C3b-C6a-C7-C71 | -162.65 (14) |
C7a-C7-C6-C61 | -53.2 (2) | C8a-C8-C7-C71 | 164.43 (13) |
Dihedral | 16.66 (11) | Dihedral | 52.21 (6) |
Ring-puckering angles are calculated for the following atom sequences: five-membered ring N12/C1/C2/C2a/C2b; six-membered ring N12/C1/C2/C3/C3a/C3b; seven-membered rings N12/C2b/C5a/C6/C7/C7a/C11a for (I) and N13/C3b/C6a/C7/C8/C8a/C12a for (II). For the idealised envelope forms of five- and six-membered rings, the index k represents an integer. `Dihedral' denotes the dihedral angle between the mean planes of the phenyl and pyrimidine rings. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C7-H7B···N9i | 0.99 | 2.61 | 3.507 (2) | 151 |
(II) | C4-H4···Cg1ii | 0.95 | 2.72 | 3.4323 (18) | 133 |
Cg1 represents the centroid of the N10/C9/C8a/C12a/N12/C11 ring. Symmetry codes: (i) 1 + x, y, z; (ii) 1 - x, -y, - z. |
C—Cl···Cg | C—Cl | Cl···Cg | C···Cg | C—Cl···.Cg |
C9—Cl9···Cg1i | 1.7449 (15) | 3.5593 (1) | 4.2210 (17) | 99.75 (5) |
C9—Cl9···Cg2ii | 1.7449 (15) | 3.6620 (10) | 4.563 (2) | 109.98 (5) |
Cg1 and Cg2 represent the centroids of the N10/C9/C8a/C12a/N12/C11 and C3a/C3b/C6a/C6/C5/C4 rings, respectively. Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) -1 + x, y, z. |