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A simple and effective two-step approach to tricyclic pyrimidine-fused benz­­azepines has been adapted to give the tetracyclic analogues. In (RS)-8-chloro-6-methyl-1,2,6,7-tetra­hydro­pyrimido[5′,4′:6,7]azepino[3,2,1-hi]indole, C15H14ClN3, (I), the five-membered ring adopts an envelope conformation, as does the reduced pyridine ring in (RS)-9-chloro-7-methyl-2,3,7,8-tetra­hydro-1H-pyrimido[5′,4′:6,7]azepino[3,2,1-ij]quinoline, C16H16ClN3, (II). However, the seven-membered rings in (I) and (II) adopt very different conformations, with the result that the methyl substituent occupies a quasi-axial site in (I) but a quasi-equatorial site in (II). The mol­ecules of (I) are linked by C—H...N hydrogen bonds to form C(5) chains and inversion-related pairs of chains are linked by a π–π stacking inter­action. A combination of a C—H...π hydrogen bond and two C—Cl...π inter­actions links the mol­ecules of (II) into complex sheets. Comparisons are made with some similar fused heterocyclic compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615023876/sk3612sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023876/sk3612Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023876/sk3612IIsup3.hkl
Contains datablock II

CCDC references: 1442007; 1442006

Introduction top

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).

Experimental top

Synthesis and crystallization top

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.

Refinement top

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.

Results and discussion top

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 ππ 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.

Structure description top

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 ππ 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.

Synthesis and crystallization top

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.

Refinement details top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the R-enantiomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of the R-enantiomer of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The conformations of the azepine ring in the R-enantiomers of (a) (I) and (b) (II). For the sake of clarity, most of the non-H atoms and all of the H atoms have been omitted.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of a pair of π-stacked hydrogen-bonded C(5) chains running parallel to the [100] direction. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. Hydrogen bonds are shown as dashed lines and the atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (1 + x, y, z), (-1 + x, y, z) and (1 - x, 1 - y, 1 - z), respectively.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of a cyclic hydrogen-bonded dimer. For the sake of clarity, the unit-cell outline and the H atoms not involved in the motif shown have been omitted. Hydrogen bonds are shown as dashed lines and the atoms marked with an asterisk (*) are at the symmetry position (1 - x, -y, -z).
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a sheet parallel to (011) resulting from C—H···π hydrogen bonds, shown as dashed lines, and C—Cl···π interactions, shown as tapered solid lines. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
(I) (RS)-8-chloro-6-methyl-1,2,6,7-tetrahydropyrimido[5',4':6,7]azepino[3,2,1-hi]indole top
Crystal data top
C15H14ClN3F(000) = 568
Mr = 271.74Dx = 1.428 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.6250 (3) ÅCell parameters from 2903 reflections
b = 22.4796 (13) Åθ = 2.6–27.6°
c = 8.6355 (4) ŵ = 0.29 mm1
β = 100.610 (3)°T = 100 K
V = 1264.07 (11) Å3Block, colourless
Z = 40.12 × 0.12 × 0.10 mm
Data collection top
Bruker D8 Venture
diffractometer
2901 independent reflections
Radiation source: high brilliance microfocus sealed tube2329 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.083
φ and ω scansθmax = 27.6°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 88
Tmin = 0.812, Tmax = 0.971k = 2529
16728 measured reflectionsl = 1011
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-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 reflectionsΔρmax = 0.75 e Å3
173 parametersΔρmin = 0.38 e Å3
Crystal data top
C15H14ClN3V = 1264.07 (11) Å3
Mr = 271.74Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.6250 (3) ŵ = 0.29 mm1
b = 22.4796 (13) ÅT = 100 K
c = 8.6355 (4) Å0.12 × 0.12 × 0.10 mm
β = 100.610 (3)°
Data collection top
Bruker D8 Venture
diffractometer
2901 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2329 reflections with I > 2σ(I)
Tmin = 0.812, Tmax = 0.971Rint = 0.083
16728 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.08Δρmax = 0.75 e Å3
2901 reflectionsΔρmin = 0.38 e Å3
173 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6066 (3)0.45800 (9)0.1446 (2)0.0239 (4)
H1A0.58790.50040.17000.029*
H1B0.48120.44370.07400.029*
C20.7956 (3)0.44979 (10)0.0687 (2)0.0291 (5)
H2A0.75620.44530.04700.035*
H2B0.89110.48380.09240.035*
C2a0.8903 (3)0.39374 (10)0.1432 (2)0.0235 (4)
C2b0.8070 (3)0.37952 (9)0.2764 (2)0.0182 (4)
C31.0462 (3)0.36023 (11)0.1012 (2)0.0305 (5)
H31.10010.36980.00970.037*
C41.1228 (3)0.31245 (11)0.1948 (3)0.0327 (5)
H41.23050.28900.16800.039*
C51.0417 (3)0.29879 (10)0.3281 (2)0.0261 (4)
H51.09710.26600.39140.031*
C5a0.8813 (3)0.33159 (9)0.3728 (2)0.0190 (4)
C60.8084 (3)0.31358 (8)0.5213 (2)0.0187 (4)
H60.92820.29450.59120.022*
C70.7471 (3)0.36736 (8)0.6117 (2)0.0179 (4)
H7A0.73930.35460.72010.021*
H7B0.85690.39770.61950.021*
C7a0.5468 (3)0.39584 (8)0.54002 (19)0.0155 (4)
C80.3794 (3)0.40097 (8)0.6144 (2)0.0173 (4)
Cl80.37942 (8)0.36267 (2)0.79091 (6)0.02699 (15)
N90.2123 (2)0.43379 (7)0.56786 (19)0.0191 (3)
C100.2119 (3)0.46273 (8)0.4330 (2)0.0195 (4)
H100.09900.48860.39900.023*
N110.3508 (2)0.45949 (7)0.34097 (18)0.0184 (3)
C11a0.5155 (3)0.42477 (8)0.3914 (2)0.0159 (4)
N120.6516 (3)0.42159 (7)0.29006 (17)0.0184 (3)
C610.6389 (3)0.26674 (9)0.4909 (2)0.0258 (4)
H61A0.68760.23200.43970.039*
H61B0.51790.28350.42220.039*
H61C0.60230.25460.59120.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0356 (12)0.0231 (10)0.0146 (9)0.0019 (9)0.0092 (7)0.0025 (7)
C20.0343 (12)0.0369 (12)0.0193 (9)0.0122 (10)0.0130 (8)0.0012 (8)
C2a0.0230 (10)0.0326 (11)0.0169 (9)0.0103 (8)0.0085 (7)0.0072 (8)
C2b0.0163 (9)0.0244 (10)0.0154 (8)0.0055 (7)0.0070 (7)0.0074 (7)
C30.0232 (11)0.0494 (14)0.0219 (10)0.0118 (10)0.0118 (8)0.0148 (9)
C40.0192 (10)0.0495 (14)0.0312 (11)0.0003 (10)0.0093 (8)0.0164 (10)
C50.0172 (10)0.0338 (11)0.0273 (10)0.0028 (8)0.0041 (7)0.0106 (9)
C5a0.0157 (9)0.0243 (10)0.0177 (9)0.0036 (7)0.0045 (6)0.0081 (7)
C60.0178 (9)0.0216 (9)0.0165 (8)0.0011 (7)0.0028 (6)0.0003 (7)
C70.0175 (9)0.0211 (9)0.0162 (8)0.0015 (7)0.0061 (6)0.0022 (7)
C7a0.0179 (9)0.0150 (8)0.0141 (8)0.0033 (7)0.0044 (6)0.0032 (6)
C80.0193 (9)0.0174 (9)0.0171 (8)0.0042 (7)0.0084 (7)0.0026 (7)
Cl80.0316 (3)0.0308 (3)0.0233 (2)0.0018 (2)0.01737 (19)0.00511 (19)
N90.0164 (8)0.0189 (8)0.0234 (8)0.0017 (6)0.0070 (6)0.0056 (6)
C100.0172 (9)0.0180 (9)0.0229 (9)0.0004 (7)0.0025 (7)0.0048 (7)
N110.0196 (8)0.0169 (8)0.0186 (7)0.0008 (6)0.0034 (6)0.0026 (6)
C11a0.0180 (9)0.0144 (8)0.0163 (8)0.0035 (7)0.0053 (6)0.0028 (7)
N120.0233 (8)0.0196 (8)0.0140 (7)0.0007 (6)0.0081 (6)0.0009 (6)
C610.0280 (11)0.0193 (10)0.0315 (11)0.0010 (8)0.0090 (8)0.0021 (8)
Geometric parameters (Å, º) top
C1—N121.483 (2)C6—C611.527 (3)
C1—C21.528 (3)C6—C71.534 (2)
C1—H1A0.9900C6—H61.0000
C1—H1B0.9900C7—C7a1.501 (3)
C2—C2a1.499 (3)C7—H7A0.9900
C2—H2A0.9900C7—H7B0.9900
C2—H2B0.9900C7a—C81.385 (2)
C2a—C31.380 (3)C7a—C11a1.420 (2)
C2a—C2b1.401 (2)C8—N91.330 (2)
C2b—C5a1.395 (3)C8—Cl81.7506 (18)
C2b—N121.418 (2)N9—C101.334 (2)
C3—C41.383 (3)C10—N111.324 (2)
C3—H30.9500C10—H100.9500
C4—C51.391 (3)N11—C11a1.347 (2)
C4—H40.9500C11a—N121.370 (2)
C5—C5a1.404 (3)C61—H61A0.9800
C5—H50.9500C61—H61B0.9800
C5a—C61.507 (2)C61—H61C0.9800
N12—C1—C2104.12 (17)C5a—C6—H6106.6
N12—C1—H1A110.9C61—C6—H6106.6
C2—C1—H1A110.9C7—C6—H6106.6
N12—C1—H1B110.9C7a—C7—C6115.06 (15)
C2—C1—H1B110.9C7a—C7—H7A108.5
H1A—C1—H1B108.9C6—C7—H7A108.5
C2a—C2—C1103.19 (15)C7a—C7—H7B108.5
C2a—C2—H2A111.1C6—C7—H7B108.5
C1—C2—H2A111.1H7A—C7—H7B107.5
C2a—C2—H2B111.1C8—C7a—C11a112.65 (16)
C1—C2—H2B111.1C8—C7a—C7124.56 (16)
H2A—C2—H2B109.1C11a—C7a—C7122.62 (16)
C3—C2a—C2b121.2 (2)N9—C8—C7a126.82 (17)
C3—C2a—C2128.34 (18)N9—C8—Cl8113.73 (13)
C2b—C2a—C2110.34 (17)C7a—C8—Cl8119.43 (15)
C5a—C2b—C2a121.13 (18)C8—N9—C10113.73 (15)
C5a—C2b—N12130.34 (16)N11—C10—N9127.39 (18)
C2a—C2b—N12108.51 (17)N11—C10—H10116.3
C2a—C3—C4118.83 (19)N9—C10—H10116.3
C2a—C3—H3120.6C10—N11—C11a116.69 (16)
C4—C3—H3120.6N11—C11a—N12114.41 (16)
C3—C4—C5119.9 (2)N11—C11a—C7a122.19 (16)
C3—C4—H4120.0N12—C11a—C7a123.37 (17)
C5—C4—H4120.0C11a—N12—C2b131.40 (16)
C4—C5—C5a122.5 (2)C11a—N12—C1117.32 (16)
C4—C5—H5118.7C2b—N12—C1109.48 (14)
C5a—C5—H5118.7C6—C61—H61A109.5
C2b—C5a—C5116.34 (18)C6—C61—H61B109.5
C2b—C5a—C6125.61 (16)H61A—C61—H61B109.5
C5—C5a—C6118.02 (18)C6—C61—H61C109.5
C5a—C6—C61112.32 (15)H61A—C61—H61C109.5
C5a—C6—C7112.19 (15)H61B—C61—H61C109.5
C61—C6—C7112.08 (15)
N12—C1—C2—C2a20.1 (2)C11a—C7a—C8—N97.1 (3)
C1—C2—C2a—C3169.0 (2)C7—C7a—C8—N9168.26 (17)
C1—C2—C2a—C2b15.0 (2)C11a—C7a—C8—Cl8174.34 (13)
C3—C2a—C2b—C5a1.1 (3)C7—C7a—C8—Cl810.3 (2)
C2—C2a—C2b—C5a175.25 (17)C7a—C8—N9—C101.7 (3)
C3—C2a—C2b—N12179.70 (18)Cl8—C8—N9—C10179.67 (13)
C2—C2a—C2b—N123.3 (2)C8—N9—C10—N113.8 (3)
C2b—C2a—C3—C41.1 (3)N9—C10—N11—C11a2.6 (3)
C2—C2a—C3—C4174.6 (2)C10—N11—C11a—N12178.25 (16)
C2a—C3—C4—C50.3 (3)C10—N11—C11a—C7a3.9 (3)
C3—C4—C5—C5a0.5 (3)C8—C7a—C11a—N118.0 (2)
C2a—C2b—C5a—C50.3 (3)C7—C7a—C11a—N11167.40 (17)
N12—C2b—C5a—C5178.54 (18)C8—C7a—C11a—N12174.27 (17)
C2a—C2b—C5a—C6177.82 (17)C7—C7a—C11a—N1210.3 (3)
N12—C2b—C5a—C60.4 (3)N11—C11a—N12—C2b160.29 (18)
C4—C5—C5a—C2b0.5 (3)C7a—C11a—N12—C2b21.8 (3)
C4—C5—C5a—C6178.78 (18)N11—C11a—N12—C12.6 (2)
C2b—C5a—C6—C6193.1 (2)C7a—C11a—N12—C1175.23 (16)
C5—C5a—C6—C6188.8 (2)C5a—C2b—N12—C11a7.2 (3)
C2b—C5a—C6—C734.2 (2)C2a—C2b—N12—C11a174.44 (19)
C5—C5a—C6—C7143.93 (17)C5a—C2b—N12—C1171.10 (19)
C5a—C6—C7—C7a74.2 (2)C2a—C2b—N12—C110.5 (2)
C61—C6—C7—C7a53.2 (2)C2—C1—N12—C11a174.06 (16)
C6—C7—C7a—C8119.83 (19)C2—C1—N12—C2b19.5 (2)
C6—C7—C7a—C11a65.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···N9i0.992.613.507 (2)151
Symmetry code: (i) x+1, y, z.
(II) (RS)-9-chloro-7-methyl-2,3,7,8-tetrahydro-1H-pyrimido[5',4':6,7]azepino[3,2,1-ij]-quinoline top
Crystal data top
C16H16ClN3Z = 2
Mr = 285.77F(000) = 300
Triclinic, P1Dx = 1.389 Mg m3
a = 8.184 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.5399 (12) ÅCell parameters from 4161 reflections
c = 10.2185 (19) Åθ = 2.2–30.6°
α = 104.471 (7)°µ = 0.27 mm1
β = 101.049 (6)°T = 100 K
γ = 111.324 (5)°Block, colourless
V = 683.40 (18) Å30.14 × 0.14 × 0.12 mm
Data collection top
Bruker D8 Venture
diffractometer
3157 independent reflections
Radiation source: high brilliance microfocus sealed tube2784 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.033
φ and ω scansθmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1010
Tmin = 0.854, Tmax = 0.968k = 1212
15418 measured reflectionsl = 1312
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-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 reflectionsΔρmax = 0.65 e Å3
182 parametersΔρmin = 0.27 e Å3
Crystal data top
C16H16ClN3γ = 111.324 (5)°
Mr = 285.77V = 683.40 (18) Å3
Triclinic, P1Z = 2
a = 8.184 (1) ÅMo Kα radiation
b = 9.5399 (12) ŵ = 0.27 mm1
c = 10.2185 (19) ÅT = 100 K
α = 104.471 (7)°0.14 × 0.14 × 0.12 mm
β = 101.049 (6)°
Data collection top
Bruker D8 Venture
diffractometer
3157 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2784 reflections with I > 2σ(I)
Tmin = 0.854, Tmax = 0.968Rint = 0.033
15418 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.04Δρmax = 0.65 e Å3
3157 reflectionsΔρmin = 0.27 e Å3
182 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8612 (2)0.37892 (17)0.10006 (16)0.0186 (3)
H1A0.99020.39210.12440.022*
H1B0.86320.48520.10830.022*
C20.7536 (2)0.26168 (18)0.05117 (16)0.0194 (3)
H2A0.80460.30690.11950.023*
H2B0.62230.24230.07320.023*
C30.7687 (2)0.10445 (19)0.06408 (16)0.0197 (3)
H3A0.66330.01650.14450.024*
H3B0.88350.11230.08640.024*
C3a0.77022 (18)0.06246 (17)0.06933 (15)0.0153 (3)
C3b0.76949 (18)0.16343 (16)0.19530 (15)0.0139 (3)
C40.7762 (2)0.08192 (18)0.06930 (17)0.0188 (3)
H40.77890.15110.01440.023*
C50.7785 (2)0.12660 (18)0.18774 (18)0.0214 (3)
H50.77940.22670.18450.026*
C60.7794 (2)0.02430 (19)0.31199 (17)0.0204 (3)
H60.78030.05530.39350.025*
C6a0.77892 (19)0.12333 (17)0.31805 (15)0.0165 (3)
C70.7881 (2)0.24291 (19)0.45085 (16)0.0203 (3)
H70.87620.35200.45880.024*
C80.5965 (2)0.24145 (19)0.43391 (16)0.0200 (3)
H8A0.50360.12920.40670.024*
H8B0.59590.30320.52720.024*
C8a0.53912 (19)0.31026 (16)0.32514 (15)0.0153 (3)
C90.39051 (19)0.34871 (17)0.32198 (15)0.0172 (3)
Cl90.24959 (5)0.28487 (5)0.42363 (4)0.02551 (12)
N100.34084 (17)0.43187 (15)0.24867 (14)0.0210 (3)
C110.4540 (2)0.48418 (18)0.17551 (18)0.0223 (3)
H110.43130.55310.12910.027*
N120.59490 (18)0.45071 (15)0.16033 (14)0.0194 (3)
C12a0.63380 (19)0.35715 (16)0.22866 (15)0.0146 (3)
N130.77143 (16)0.31569 (14)0.19881 (13)0.0146 (2)
C710.8549 (3)0.2155 (2)0.58802 (18)0.0308 (4)
H71A0.97390.21110.59520.046*
H71B0.76430.11390.58720.046*
H71C0.86930.30390.66970.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0153 (7)0.0168 (7)0.0255 (8)0.0067 (6)0.0088 (6)0.0087 (6)
C20.0195 (7)0.0232 (7)0.0214 (7)0.0106 (6)0.0107 (6)0.0117 (6)
C30.0196 (7)0.0234 (7)0.0185 (7)0.0124 (6)0.0074 (6)0.0053 (6)
C3a0.0098 (6)0.0169 (7)0.0181 (7)0.0070 (5)0.0028 (5)0.0038 (5)
C3b0.0099 (6)0.0127 (6)0.0175 (7)0.0060 (5)0.0012 (5)0.0032 (5)
C40.0149 (7)0.0167 (7)0.0226 (7)0.0095 (6)0.0031 (5)0.0012 (6)
C50.0166 (7)0.0167 (7)0.0315 (8)0.0102 (6)0.0034 (6)0.0076 (6)
C60.0178 (7)0.0239 (8)0.0235 (8)0.0117 (6)0.0044 (6)0.0122 (6)
C6a0.0131 (6)0.0190 (7)0.0164 (7)0.0083 (5)0.0017 (5)0.0050 (6)
C70.0208 (7)0.0242 (8)0.0154 (7)0.0108 (6)0.0032 (6)0.0062 (6)
C80.0254 (8)0.0238 (7)0.0146 (7)0.0139 (6)0.0082 (6)0.0063 (6)
C8a0.0157 (6)0.0119 (6)0.0149 (7)0.0059 (5)0.0033 (5)0.0007 (5)
C90.0143 (7)0.0145 (7)0.0183 (7)0.0050 (5)0.0047 (5)0.0008 (5)
Cl90.01859 (19)0.0305 (2)0.0277 (2)0.00967 (15)0.01196 (15)0.00840 (16)
N100.0171 (6)0.0183 (6)0.0277 (7)0.0106 (5)0.0058 (5)0.0048 (5)
C110.0227 (8)0.0173 (7)0.0322 (8)0.0132 (6)0.0091 (6)0.0101 (6)
N120.0204 (6)0.0158 (6)0.0268 (7)0.0108 (5)0.0088 (5)0.0094 (5)
C12a0.0129 (6)0.0111 (6)0.0168 (7)0.0053 (5)0.0022 (5)0.0016 (5)
N130.0147 (6)0.0139 (6)0.0170 (6)0.0079 (5)0.0055 (5)0.0056 (5)
C710.0316 (9)0.0436 (10)0.0198 (8)0.0173 (8)0.0066 (7)0.0146 (8)
Geometric parameters (Å, º) top
C1—N131.4790 (18)C6a—C71.508 (2)
C1—C21.521 (2)C7—C711.525 (2)
C1—H1A0.9900C7—C81.539 (2)
C1—H1B0.9900C7—H71.0000
C2—C31.525 (2)C8—C8a1.509 (2)
C2—H2A0.9900C8—H8A0.9900
C2—H2B0.9900C8—H8B0.9900
C3—C3a1.513 (2)C8a—C91.3892 (19)
C3—H3A0.9900C8a—C12a1.426 (2)
C3—H3B0.9900C9—N101.331 (2)
C3a—C41.396 (2)C9—Cl91.7449 (15)
C3a—C3b1.4044 (19)N10—C111.335 (2)
C3b—C6a1.396 (2)C11—N121.3293 (19)
C3b—N131.4382 (17)C11—H110.9500
C4—C51.379 (2)N12—C12a1.3485 (18)
C4—H40.9500C12a—N131.3834 (17)
C5—C61.392 (2)C71—H71A0.9800
C5—H50.9500C71—H71B0.9800
C6—C6a1.396 (2)C71—H71C0.9800
C6—H60.9500
N13—C1—C2108.88 (12)C6a—C7—C71114.46 (13)
N13—C1—H1A109.9C6a—C7—C8108.77 (12)
C2—C1—H1A109.9C71—C7—C8110.18 (13)
N13—C1—H1B109.9C6a—C7—H7107.7
C2—C1—H1B109.9C71—C7—H7107.7
H1A—C1—H1B108.3C8—C7—H7107.7
C1—C2—C3108.63 (12)C8a—C8—C7114.62 (12)
C1—C2—H2A110.0C8a—C8—H8A108.6
C3—C2—H2A110.0C7—C8—H8A108.6
C1—C2—H2B110.0C8a—C8—H8B108.6
C3—C2—H2B110.0C7—C8—H8B108.6
H2A—C2—H2B108.3H8A—C8—H8B107.6
C3a—C3—C2113.32 (12)C9—C8a—C12a113.28 (13)
C3a—C3—H3A108.9C9—C8a—C8119.95 (13)
C2—C3—H3A108.9C12a—C8a—C8126.48 (13)
C3a—C3—H3B108.9N10—C9—C8a127.01 (14)
C2—C3—H3B108.9N10—C9—Cl9114.27 (11)
H3A—C3—H3B107.7C8a—C9—Cl9118.73 (12)
C4—C3a—C3b117.88 (13)C9—N10—C11113.29 (13)
C4—C3a—C3118.93 (13)N12—C11—N10127.31 (14)
C3b—C3a—C3123.18 (13)N12—C11—H11116.3
C6a—C3b—C3a121.39 (13)N10—C11—H11116.3
C6a—C3b—N13120.00 (12)C11—N12—C12a117.62 (13)
C3a—C3b—N13118.47 (12)N12—C12a—N13114.68 (13)
C5—C4—C3a121.63 (14)N12—C12a—C8a120.73 (12)
C5—C4—H4119.2N13—C12a—C8a124.58 (13)
C3a—C4—H4119.2C12a—N13—C3b121.95 (11)
C4—C5—C6119.65 (14)C12a—N13—C1118.05 (12)
C4—C5—H5120.2C3b—N13—C1112.65 (11)
C6—C5—H5120.2C7—C71—H71A109.5
C5—C6—C6a120.63 (14)C7—C71—H71B109.5
C5—C6—H6119.7H71A—C71—H71B109.5
C6a—C6—H6119.7C7—C71—H71C109.5
C6—C6a—C3b118.74 (13)H71A—C71—H71C109.5
C6—C6a—C7123.40 (13)H71B—C71—H71C109.5
C3b—C6a—C7117.86 (13)
N13—C1—C2—C364.95 (14)C7—C8—C8a—C12a7.7 (2)
C1—C2—C3—C3a35.82 (16)C12a—C8a—C9—N105.3 (2)
C2—C3—C3a—C4177.51 (12)C8—C8a—C9—N10168.88 (14)
C2—C3—C3a—C3b3.78 (19)C12a—C8a—C9—Cl9174.96 (10)
C4—C3a—C3b—C6a1.5 (2)C8—C8a—C9—Cl910.83 (18)
C3—C3a—C3b—C6a177.23 (13)C8a—C9—N10—C111.9 (2)
C4—C3a—C3b—N13177.33 (12)Cl9—C9—N10—C11177.85 (11)
C3—C3a—C3b—N131.4 (2)C9—N10—C11—N126.0 (2)
C3b—C3a—C4—C51.0 (2)N10—C11—N12—C12a2.0 (2)
C3—C3a—C4—C5179.80 (13)C11—N12—C12a—N13174.74 (13)
C3a—C4—C5—C61.6 (2)C11—N12—C12a—C8a6.4 (2)
C4—C5—C6—C6a0.3 (2)C9—C8a—C12a—N129.4 (2)
C5—C6—C6a—C3b2.7 (2)C8—C8a—C12a—N12164.32 (14)
C5—C6—C6a—C7177.27 (14)C9—C8a—C12a—N13171.79 (13)
C3a—C3b—C6a—C63.3 (2)C8—C8a—C12a—N1314.5 (2)
N13—C3b—C6a—C6179.11 (12)N12—C12a—N13—C3b146.76 (13)
C3a—C3b—C6a—C7176.66 (13)C8a—C12a—N13—C3b34.4 (2)
N13—C3b—C6a—C70.88 (19)N12—C12a—N13—C11.07 (18)
C6—C6a—C7—C7117.3 (2)C8a—C12a—N13—C1177.77 (13)
C3b—C6a—C7—C71162.65 (14)C6a—C3b—N13—C12a62.33 (18)
C6—C6a—C7—C8106.35 (16)C3a—C3b—N13—C12a121.78 (14)
C3b—C6a—C7—C873.65 (16)C6a—C3b—N13—C1148.28 (13)
C6a—C7—C8—C8a69.36 (16)C3a—C3b—N13—C127.62 (17)
C71—C7—C8—C8a164.43 (13)C2—C1—N13—C12a89.26 (15)
C7—C8—C8a—C9165.69 (13)C2—C1—N13—C3b61.44 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg1i0.952.723.4323 (18)133
Symmetry code: (i) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H14ClN3C16H16ClN3
Mr271.74285.77
Crystal system, space groupMonoclinic, P21/cTriclinic, P1
Temperature (K)100100
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), 90104.471 (7), 101.049 (6), 111.324 (5)
V3)1264.07 (11)683.40 (18)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.290.27
Crystal size (mm)0.12 × 0.12 × 0.100.14 × 0.14 × 0.12
Data collection
DiffractometerBruker D8 VentureBruker D8 Venture
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.812, 0.9710.854, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
16728, 2901, 2329 15418, 3157, 2784
Rint0.0830.033
(sin θ/λ)max1)0.6510.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.114, 1.08 0.038, 0.098, 1.04
No. of reflections29013157
No. of parameters173182
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.75, 0.380.65, 0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Selected geometric parameters (Å, °) top
Ring-puckering parameters(Å, °)
(a) Five-membered ring
(I)(II)Envelope
Q20.202 (2)
φ244.8 (6)36k
(b) Six-membered ring
Q0.5400 (17)
θ126.66 (8)125.3
φ249.1 (2)60k
(c) Seven-membered rings
Q0.612 (2)0.8809 (17)
φ2295.7 (2)41.77 (12)
φ388.7 (3)286.9 (3)
Torsion and dihedral angles
Parameter(I)Parameter(II)
C1-N12-C2b-C5a-171.10 (19)C1-N13_C3b-C6a148.28 (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-C70.88 (19)
C11a-C7a-C7-C6-65.3 (2)C12a-C8a-C8-C77.7 (2)
C2b-C5a-C6-C6193.1 (2)C3b-C6a-C7-C71-162.65 (14)
C7a-C7-C6-C61-53.2 (2)C8a-C8-C7-C71164.43 (13)
Dihedral16.66 (11)Dihedral52.21 (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.
Hydrogen bond parameters (Å, °) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)C7-H7B···N9i0.992.613.507 (2)151
(II)C4-H4···Cg1ii0.952.723.4323 (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.
Geometric parameters (Å, °) for C—Cl···π contacts in (II) top
C—Cl···CgC—ClCl···CgC···CgC—Cl···.Cg
C9—Cl9···Cg1i1.7449 (15)3.5593 (1)4.2210 (17)99.75 (5)
C9—Cl9···Cg2ii1.7449 (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.
 

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