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Dibenz[b,f]azepine (DBA) is a privileged 6-7-6 tricyclic ring system of im­portance in both organic and medicinal chemistry. Benzo[b]pyrimido[5,4-f]azepines (BPAs), which also contain a privileged 6-7-6 ring system, are less well investigated, probably because of a lack of straightforward and versatile methods for their synthesis. A simple and versatile synthetic approach to BPAs based on intra­molecular Friedel-Crafts alkyl­ation has been developed. A group of closely-related benzo[b]pyrimido[5,4-f]azepine derivatives, namely (6RS)-4-chloro-6,11-dimethyl-6,11-di­hydro-5H-benzo[b]py­rim­ido[5,4-f]azepine, C14H14ClN3, (I), (6RS)-4-chloro-8-hy­droxy-6,11-dimethyl-6,11-di­hydro-5H-benzo[b]pyrimido[5,4-f]azepine, C14H14ClN3O, (II), (6RS)-4-chloro-8-meth­oxy-6,11-dimethyl-6,11-di­hydro-5H-benzo[b]pyrimido[5,4-f]azepine, C15H16ClN3O, (III), and (6RS)-4-chloro-8-meth­oxy-6,11-dimethyl-2-phenyl-6,11-di­hydro-5H-benzo[b]pyrimido[5,4-f]azepine, C21H20ClN3O, (IV), has been prepared and their structures compared with the recently published structure [Acosta-Quintero et al. (2015). Eur. J. Org. Chem. pp. 5360-5369] of (6RS)-4-chloro-2,6,8,11-tetra­methyl-6,11-di­hydro-5H-benzo[b]pyrimido[5,4-f]azepine, (V). All five com­pounds crystallize as racemic mixtures and they have very similar mol­ecular conformations, with the azepine ring adopting a boat-type conformation in each case, although the orientation of the meth­oxy substituent in each of (III) and (IV) is different. The supra­molecular assemblies in (II) and (IV) depend upon hydrogen bonds of the O-H...N and C-H...[pi](arene) types, respectively, those in (I) and (V) depend upon [pi]-[pi] stacking inter­actions involving pairs of pyrimidine rings, and that in (III) depends upon a [pi]-[pi] stacking inter­action involving pairs of phenyl rings. Short C-Cl...[pi](pyrimidine) contacts are present in (I), (II) and (IV) but not in (III) or (V).

Supporting information

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Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615020811/yf3094sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IVsup5.hkl
Contains datablock IV

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Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094Isup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IIsup7.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IIIsup8.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IVsup9.cml
Supplementary material

CCDC references: 1434807; 1434806; 1434805; 1434804

Introduction top

\ Dibenz[b,f]azepine (DBA) is a privileged (Costantino & Barlocco, 2006) 6-7-6 tricyclic ring system that has long attracted considerable attention due to its importance in both organic and medicinal chemistry (Madsen et al., 1996; Benes et al., 1999; Hohlweg et al., 1999). Anti­depressants such as imipramine [Tofranil; 3-(10,11-di­hydro-5H-dibenzo[b,f]azepin-5-yl)-N,\ N-di­methyl­propan-1-amine], as well as anti-epileptic drugs such as carbamazepine (Tegretol; 5H-dibenzo[b,f]azepine-5-carboxamide) and oxcarbazepine (Trileptal; 10,11-di­hydro-10-oxo-5H-dibenz[b,f]azepine-5-\ carboxamide), all contain this scaffold. By contrast, the 1,3-di­aza analogues, namely benzo[b]pyrimido[5,4-f]azepines (BPAs), which also contain a privileged 6-7-6 ring system, are a less well investigated family of compounds, probably because of a lack of straightforward and versatile methods for their synthesis. The few known BPAs have usually been prepared by approaches involving the construction of: (i) the azepine ring, either through the Pd-catalysed 7-endo-cyclization of 5-bromo-2,6-di­methyl-N-(2-vinyl­phenyl)­pyrimidin-4-amine (Tsvelikhovsky & Buchwald, 2010) or through the cyclization of the 5-(2-amino­phenethyl)­pyrimidin-4-amine phospho­ric acid salt at very high temperature [Reference?]; or (ii) the pyrimidine ring through the cyclo­condensation of suitably functionalized 1-benzazepines with formamide and different 1,3-bis-nucleophiles, such as urea, thio­urea, amidines and guanidines, in the presence of phospho­ryl chloride (Kobayashi, 1973; Bouillon et al., 1994). These atypical and nongeneral methods employ expensive catalysts, harsh reaction conditions and highly functionalized starting materials and therefore they are of reduced scope. Accordingly, we have recently developed (Acosta-Qu­intero et al., 2015) a new synthetic approach (see Scheme 1) based on our previous work on intra­molecular Friedel–Crafts alkyl­ation as the key step in the construction of azepine ring systems containing different nitro­gen-containing heterocycles (Palma et al., 2004, 2010; Yépez et al., 2006). This method involves the reaction, under basic conditions, between a substituted N-methyl­aniline and a di­chloro­pyrimidine, followed by an acid-catalysed intra­molecular alkyl­ation reaction; this procedure has proven to be both simple and versatile (Acosta-Qu­intero et al., 2015) and we report here the molecular and supra­molecular structures of four closely related (6RS)-4-chloro-6,11-di­methyl-6,11-di­hydro-5H-benzo[b]\ pyrimido[5,4-f]azepines, namely the unsubstituted compound, (I), the 8-hy­droxy derivative, (II), the 8-meth­oxy derivative, (III), and the 8-meth­oxy-2-phenyl derivative, (IV), all prepared by this new method, which we compare with (V) (see Scheme 1), whose structure was reported recently (Acosta-Qu­intero et al., 2015) on a proof-of-constitution basis, although with no consideration of any supra­molecular inter­actions.

Experimental top

Synthesis and crystallization top

Compounds (I)–(IV) were all prepared according to the published method of Acosta-Qu­intero et al. (2015). Colourless crystals of each, suitable for single-crystal X-ray diffraction, were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in heptane–ethyl acetate (4:1 v/v).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding 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 C-bound H atoms. For the hy­droxy H atom in (II), the atomic coordinates were refined with Uiso(H) = 1.5Ueq(O), giving an O—H distance of 0.88 (3) Å. A small number of low-angle reflections which had been attenuated by the beam stop were omitted from the final refinements, as follows: (I) 111; (II) 110, 011, 111 and 120; (III) 100, 110, 111 and 021; (IV) 200, 002, 012 and 102. For the refinements of each of (II)–(IV), SHELXL2014 (Sheldrick, 2015) reported large values of K for the very weakest groups of reflections; for (II), a value of K = 3.827 for the group having Fc/Fc(max) in the range 0.000–0.010; for (III), a value K = 4.221 for the group having Fc/Fc(max) in the range 0.000–0.008; and for (IV), a value K = 5.893 for the group having Fc/Fc(max) in the range 0.000–0.007.

Results and discussion top

The constitutions of (I) and (V) differ only in the presence of two methyl groups in (V) which are absent from the structure of (I), but although both crystallize in the space group P1 with moderately similar unit-cell dimensions, a detailed comparison of the two sets of atomic coordinates rules out any possibility that these compounds could be isostructural. Compounds (II) and (III) differ only in the presence of an OH substituent in (II) versus an OMe substituent in (III), but their unit-cell dimensions, both in the space group P21/c, immediately rule out any possibility that these two compounds could be isomorphous.

The molecules of (I)–(V) all contain a stereogenic centre at atom C6 (Figs. 1–4), and for each of (I)–(IV) the reference molecule was selected as one having the R configuration at atom C6. However, the centrosymmetric space groups accommodate equal numbers of the two enanti­omeric forms, confirming that all of these compounds have crystallized as racemic mixtures, as expected, since the synthetic procedure (Acosta-Qu­intero et al., 2015) does not involve any reagent which might lead to enanti­omeric selectivity. The published report (Acosta-Qu­intero et al., 2015) on the structure of (V) utilized as the reference molecule one having the S configuration at atom C6, but all of the geometric comparisons discussed below and summarized in Tables 2 and 3 refer to the R enanti­omer in each compound.

The molecular conformations in (I)–(V) are all very similar, as shown not only by the key torsion and dihedral angles (Table 2), but also by the ring-puckering parameters (Cremer & Pople, 1975; Table 2). The ring-puckering angles show that the dominant contributor to the conformation of the azepine ring in each compound is the cos form 2 or boat conformation (Evans & Boeyens, 1989). Within this boat conformation, atoms C4a, C5, C6a and C10a are very approximately coplanar, forming the keel of the boat, with atom C6 forming the bow and atoms N11 and C11a forming the stern (Fig. 5); there is thus a very approximately noncrystallographic mirror plane through this ring, passing through and C6 [atom label missing?] and through the mid-point of the N11—C11a bond. The approximate symmetry is confirmed by the torsion angles C4a—C5—C6—C6a and C5—C6—C6a—C10a (Table 2) which, for each compound, have similar magnitudes but opposite signs. The overall conformational similarity of the fused tricyclic systems in (I)–(V) is shown by the similar magnitudes for the dihedral angle between the two terminal aromatic rings. The two methyl groups bonded to the azepine ring both adopt quasi-equatorial sites, such that atom C61 is almost coplanar with the C6a/C7–C10/C10a aryl ring (Figs. 1–4). The displacement of atom C61 from the plane of this ring ranges from 0.018 (5) Å in (III) to 0.161 (6) Å in (IV), while atom C111, on the other hand, is significantly displaced from the same plane, with displacements ranging from 0.944 (5) Å in (IV) to 1.116 (4) Å in (II).

The hy­droxy H atom in (II) and the methoxyl C atoms in (III) and (IV) all lie very close to the C6a/C7–C10/C10a plane, having displacements from this plane of 0.08 (3), 0.059 (4) and 0.071 (6) Å, respectively, consistent with the torsion angles C7—C8—O81—H81 and C7—C8—O81—C81 (Table 2), which also confirm the different orientations of the meth­oxy group in (III) and (IV) (cf. Figs. 3 and 4). Consistent with the near coplanarity of atoms H81 or C81 with the adjacent aryl rings, the pairs of exocyclic C—C—O angles in (II)–(IV) all differ by ca 10°, as typically found when alk­oxy and related substituent atoms lie close to the plane of an adjacent aryl ring (Seip et al., 1973; Ferguson et al., 1996). The bond distances in (I)–(IV) show no unusual values; the distances indicate there is strong aromatic delocalization in both the pyrimidine ring and the fused aryl ring.

Despite the very similar molecular structures exhibited by (I)–(V), their crystal structures and, in particular, their supra­molecular assemblies, as determined by the direction-specific inter­molecular inter­actions, are all different. Thus, hydrogen bonds (Table 3) occur only in the structures of (II) and (IV), where they are of the O—H···N and C—H···π(arene) types, respectively; ππ stacking inter­actions occur only in (I), (III) and (V), and these involve pairs of phenyl rings in (III) and pairs of pyrimidine rings in each of (I) and (V), and short C—Cl···π(pyrimidine) contacts (Table 4) occur only in (I), (II) and (IV).

The pyrimidine rings in the molecules of (I) at (x, y, z) and (-x + 1, -y + 1, -z + 1) are strictly parallel, with an inter­planar spacing of 3.2674 (12) Å; the centroid–centroid separation and the ring-centroid offset are 3.7503 (19) and 1.8412 (2) Å, respectively, leading to weak dimer formation (Fig. 6). For the phenyl rings in the molecules of (III) at (x, y, z) and (-x + 1, -y + 2, -z + 1), the corresponding values are 3.4677 (12), 3.7043 (17) and 1.303 (2) Å, respectively, again giving rise to a centrosymmetric dimer (Fig. 7). For the pyrimidine rings in the molecules of (V) at (x, y, z) and (-x + 2, -y + 2, -z + 1), the corresponding parameters are 3.488 (6), 3.4640 (19) and 0.410 (2) Å, respectively, again forming a centrosymmetric dimer (Fig. 8).

The molecules of (II) which are related by the 21 screw axis along (1/2, y, 3/4) are linked by O—H···N hydrogen bonds (Table 3) to form a C(10) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 9). Two chains of this type, related to one another by inversion, pass through each unit cell, and in any given chain all of the molecules have the same configuration. There are no direction-specific inter­actions between adjacent chains. Despite the presence in the molecules of (IV) of three independent aromatic rings, ππ stacking inter­actions are, surprisingly, absent from the structure, and the only significant inter­molecular inter­action is a C—H···π(arene) hydrogen bond (Table 3) involving the fused aryl ring, rather than the pendent aryl ring. Molecules of (IV), which are related by the 21 screw axis along (1/2, y, 1/4), are thus linked to form a chain running parallel to the [010] direction and, like that in (II), containing only a single enanti­omer (Fig. 10). Two chains related to one another by inversion pass through each unit cell but there are no direction-specific inter­actions between adjacent chains.

Short C—Cl···π(pyridine) contacts occur in the structures of (I), (II) and (IV) (Table 4), in each case involving pairs of molecules related by inversion. However, the Cl···Cg distances are somewhat longer than the average for contacts of this type, viz. 3.6 Å (Imai et al., 2008), and it is not clear whether these contacts in (I), (II) and (IV) are best regarded as attractive, repulsive or merely adventitious.

The boat conformation found here for the azepine ring in (I)–(V) has been similarly observed in a series of dibenzo[b,f]azepine derivatives (Yousuf et al., 2012; Abdoh et al., 2013; Manjunath, Vinay Kumar et al., 2013; Manjunath, Kumar et al., 2013), although the azepine conformation in a series of dibenzo[b,e]azepine derivatives was found to be inter­mediate between the boat and twist-boat forms (Sanabría et al., 2014).

Hence, we have shown that while (I)–(V) all exhibit similar molecular structures containing a boat conformation for the azepine ring, all five structures show a different range of direction-specific inter­molecular inter­actions and hence different patterns of supra­molecular assembly.

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); 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 molecular structure of the R enantiomer of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. The molecular structure of the R enantiomer of (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 5] Fig. 5. The conformation of the azepine ring in the R enantiomer of (I). For the sake of clarity, atoms C2, N3, C4, Cl4 and C7–C10 and all of the H atoms have been omitted.
[Figure 6] Fig. 6. Part of the crystal structure of (I), showing the formation of a centrosymmetric π-stacked dimer utilizing inversion-related pyrimidine rings. For the sake of clarity, the unit-cell outline and all of the H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (-x + 1, -y + 1, -z + 1).
[Figure 7] Fig. 7. Part of the crystal structure of (III), showing the formation of a centrosymmetric π-stacked dimer utilizing inversion-related phenyl rings. For the sake of clarity, the unit-cell outline and all of the H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (-x + 1, -y + 2, -z + 1).
[Figure 8] Fig. 8. Part of the crystal structure of (I), showing the formation of a centrosymmetric π-stacked dimer utilizing inversion-related pyrimidine rings. For the sake of clarity, the unit-cell outline and all of the H atoms have been omitted. The original atomic coordinates (Acosta-Quintero et al., 2015) have been inverted so that the reference molecule has the R configuration at atom C6, and slight amendments have been made to the atom labels to match those in (I)–(IV). The atom marked with an asterisk (*) is at the symmetry position (-x + 2, -y + 2, -z + 1).
[Figure 9] Fig. 9. Part of the crystal structure of (II), showing a C(10) chain, built from O—H···N hydrogen bonds and containing only molecules of the R configuration, and running parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have all been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (-x + 1, y + 1/2, -z + 3/2) and (-x + 1, y - 1/2, -z + 3/2) respectively.
[Figure 10] Fig. 10. A stereoview of part of the crystal structure of (IV), showing a chain built from C—H···π(arene) hydrogen bonds,containing only molecules of the R configuration, and running parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have all been omitted.
(I) (6RS)-4-Chloro-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine top
Crystal data top
C14H14ClN3Z = 2
Mr = 259.73F(000) = 272
Triclinic, P1Dx = 1.395 Mg m3
a = 8.6570 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.8622 (17) ÅCell parameters from 2836 reflections
c = 9.0321 (11) Åθ = 2.8–27.5°
α = 92.649 (13)°µ = 0.29 mm1
β = 113.635 (9)°T = 120 K
γ = 100.632 (12)°Block, colourless
V = 618.34 (16) Å30.37 × 0.21 × 0.17 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2835 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2068 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.719, Tmax = 0.951l = 1111
11681 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.136 w = 1/[σ2(Fo2) + (0.0422P)2 + 0.6668P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2835 reflectionsΔρmax = 0.41 e Å3
165 parametersΔρmin = 0.39 e Å3
Crystal data top
C14H14ClN3γ = 100.632 (12)°
Mr = 259.73V = 618.34 (16) Å3
Triclinic, P1Z = 2
a = 8.6570 (5) ÅMo Kα radiation
b = 8.8622 (17) ŵ = 0.29 mm1
c = 9.0321 (11) ÅT = 120 K
α = 92.649 (13)°0.37 × 0.21 × 0.17 mm
β = 113.635 (9)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2835 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2068 reflections with I > 2σ(I)
Tmin = 0.719, Tmax = 0.951Rint = 0.081
11681 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.08Δρmax = 0.41 e Å3
2835 reflectionsΔρmin = 0.39 e Å3
165 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5727 (3)0.5583 (3)0.3561 (3)0.0253 (5)
C20.6825 (3)0.6548 (3)0.4884 (3)0.0264 (5)
H20.66470.75710.49420.032*
N30.8157 (3)0.6243 (3)0.6148 (3)0.0256 (5)
C40.8400 (3)0.4810 (3)0.5945 (3)0.0225 (5)
Cl41.02073 (8)0.44448 (8)0.75489 (8)0.02865 (19)
C4a0.7416 (3)0.3672 (3)0.4627 (3)0.0214 (5)
C50.8010 (3)0.2187 (3)0.4472 (3)0.0238 (5)
H5A0.76680.14710.51520.029*
H5B0.92880.24350.49220.029*
C60.7294 (3)0.1339 (3)0.2725 (3)0.0223 (5)
H60.73550.21270.19810.027*
C6a0.5416 (3)0.0566 (3)0.2217 (3)0.0217 (5)
C70.4827 (3)0.1037 (3)0.2024 (3)0.0247 (5)
H70.56120.16880.21230.030*
C80.3117 (3)0.1704 (3)0.1688 (3)0.0272 (6)
H80.27400.27980.15510.033*
C90.1965 (3)0.0765 (3)0.1554 (3)0.0266 (5)
H90.08010.12140.13460.032*
C100.2512 (3)0.0832 (3)0.1723 (3)0.0231 (5)
H100.17170.14730.16190.028*
C10a0.4222 (3)0.1502 (3)0.2044 (3)0.0212 (5)
N110.4712 (3)0.3151 (2)0.2100 (2)0.0229 (4)
C11a0.5954 (3)0.4118 (3)0.3444 (3)0.0209 (5)
C610.8436 (3)0.0224 (3)0.2668 (3)0.0287 (6)
H61A0.79600.03490.15700.043*
H61B0.84670.05070.34570.043*
H61C0.96120.08150.29420.043*
C1110.3426 (3)0.3854 (3)0.0869 (3)0.0257 (5)
H11A0.40120.48360.06850.039*
H11B0.25670.40450.12620.039*
H11C0.28470.31460.01570.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0267 (11)0.0236 (11)0.0265 (11)0.0056 (9)0.0117 (9)0.0058 (9)
C20.0311 (14)0.0215 (13)0.0294 (13)0.0051 (11)0.0154 (11)0.0048 (10)
N30.0266 (11)0.0240 (11)0.0248 (11)0.0007 (9)0.0114 (9)0.0021 (9)
C40.0199 (12)0.0263 (13)0.0213 (11)0.0021 (10)0.0097 (10)0.0052 (10)
Cl40.0236 (3)0.0309 (4)0.0249 (3)0.0025 (2)0.0049 (2)0.0049 (2)
C4a0.0194 (11)0.0254 (13)0.0214 (11)0.0032 (10)0.0110 (9)0.0050 (10)
C50.0208 (12)0.0259 (13)0.0246 (12)0.0073 (10)0.0084 (10)0.0051 (10)
C60.0204 (12)0.0247 (13)0.0245 (12)0.0055 (10)0.0116 (10)0.0051 (10)
C6a0.0240 (12)0.0255 (13)0.0177 (11)0.0065 (10)0.0100 (9)0.0065 (9)
C70.0262 (13)0.0241 (13)0.0248 (12)0.0065 (10)0.0110 (10)0.0042 (10)
C80.0301 (14)0.0222 (13)0.0292 (13)0.0035 (11)0.0130 (11)0.0049 (10)
C90.0223 (12)0.0303 (14)0.0259 (13)0.0016 (11)0.0106 (10)0.0037 (11)
C100.0223 (12)0.0257 (13)0.0209 (11)0.0057 (10)0.0084 (10)0.0040 (10)
C10a0.0240 (12)0.0215 (12)0.0163 (11)0.0038 (10)0.0074 (9)0.0015 (9)
N110.0225 (10)0.0217 (11)0.0220 (10)0.0052 (9)0.0064 (8)0.0046 (8)
C11a0.0213 (12)0.0224 (12)0.0206 (11)0.0023 (9)0.0111 (9)0.0044 (9)
C610.0257 (13)0.0293 (14)0.0328 (14)0.0051 (11)0.0147 (11)0.0011 (11)
C1110.0266 (13)0.0262 (13)0.0225 (12)0.0082 (11)0.0069 (10)0.0077 (10)
Geometric parameters (Å, º) top
N1—C21.325 (3)C7—C81.390 (4)
N1—C11a1.354 (3)C7—H70.9500
C2—N31.340 (3)C8—C91.386 (4)
C2—H20.9500C8—H80.9500
N3—C41.341 (3)C9—C101.387 (4)
C4—C4a1.385 (4)C9—H90.9500
C4—Cl41.750 (3)C10—C10a1.394 (3)
C4a—C11a1.428 (3)C10—H100.9500
C4a—C51.518 (3)C10a—N111.437 (3)
C5—C61.540 (3)N11—C11a1.372 (3)
C5—H5A0.9900N11—C1111.480 (3)
C5—H5B0.9900C61—H61A0.9800
C6—C6a1.512 (3)C61—H61B0.9800
C6—C611.534 (3)C61—H61C0.9800
C6—H61.0000C111—H11A0.9800
C6a—C71.396 (4)C111—H11B0.9800
C6a—C10a1.407 (3)C111—H11C0.9800
C2—N1—C11a117.6 (2)C9—C8—H8120.1
N1—C2—N3127.4 (2)C7—C8—H8120.1
N1—C2—H2116.3C8—C9—C10120.0 (2)
N3—C2—H2116.3C8—C9—H9120.0
C2—N3—C4113.3 (2)C10—C9—H9120.0
N3—C4—C4a127.0 (2)C9—C10—C10a120.4 (2)
N3—C4—Cl4113.32 (19)C9—C10—H10119.8
C4a—C4—Cl4119.63 (19)C10a—C10—H10119.8
C4—C4a—C11a113.2 (2)C10—C10a—C6a120.3 (2)
C4—C4a—C5120.4 (2)C10—C10a—N11118.7 (2)
C11a—C4a—C5126.1 (2)C6a—C10a—N11120.9 (2)
C4a—C5—C6115.4 (2)C11a—N11—C10a123.9 (2)
C4a—C5—H5A108.4C11a—N11—C111117.3 (2)
C6—C5—H5A108.4C10a—N11—C111115.6 (2)
C4a—C5—H5B108.4N1—C11a—N11114.7 (2)
C6—C5—H5B108.4N1—C11a—C4a121.1 (2)
H5A—C5—H5B107.5N11—C11a—C4a124.2 (2)
C6a—C6—C61114.3 (2)C6—C61—H61A109.5
C6a—C6—C5108.37 (19)C6—C61—H61B109.5
C61—C6—C5109.1 (2)H61A—C61—H61B109.5
C6a—C6—H6108.3C6—C61—H61C109.5
C61—C6—H6108.3H61A—C61—H61C109.5
C5—C6—H6108.3H61B—C61—H61C109.5
C7—C6a—C10a118.1 (2)N11—C111—H11A109.5
C7—C6a—C6123.0 (2)N11—C111—H11B109.5
C10a—C6a—C6118.7 (2)H11A—C111—H11B109.5
C8—C7—C6a121.5 (2)N11—C111—H11C109.5
C8—C7—H7119.3H11A—C111—H11C109.5
C6a—C7—H7119.3H11B—C111—H11C109.5
C9—C8—C7119.7 (2)
C11a—N1—C2—N30.2 (4)C9—C10—C10a—C6a0.7 (4)
N1—C2—N3—C43.8 (4)C9—C10—C10a—N11175.8 (2)
C2—N3—C4—C4a1.6 (4)C7—C6a—C10a—C101.4 (3)
C2—N3—C4—Cl4176.89 (18)C6—C6a—C10a—C10174.2 (2)
N3—C4—C4a—C11a3.6 (4)C7—C6a—C10a—N11175.0 (2)
Cl4—C4—C4a—C11a178.01 (17)C6—C6a—C10a—N119.4 (3)
N3—C4—C4a—C5171.3 (2)C10—C10a—N11—C11a120.1 (3)
Cl4—C4—C4a—C57.1 (3)C6a—C10a—N11—C11a63.5 (3)
C4—C4a—C5—C6156.0 (2)C10—C10a—N11—C11139.1 (3)
C11a—C4a—C5—C618.3 (3)C6a—C10a—N11—C111137.3 (2)
C4a—C5—C6—C6a74.1 (3)C2—N1—C11a—N11176.0 (2)
C4a—C5—C6—C61160.9 (2)C2—N1—C11a—C4a5.7 (3)
C61—C6—C6a—C712.0 (3)C10a—N11—C11a—N1151.8 (2)
C5—C6—C6a—C7109.9 (3)C111—N11—C11a—N17.1 (3)
C61—C6—C6a—C10a172.7 (2)C10a—N11—C11a—C4a29.9 (4)
C5—C6—C6a—C10a65.4 (3)C111—N11—C11a—C4a171.2 (2)
C10a—C6a—C7—C80.8 (4)C4—C4a—C11a—N17.3 (3)
C6—C6a—C7—C8174.6 (2)C5—C4a—C11a—N1167.3 (2)
C6a—C7—C8—C90.5 (4)C4—C4a—C11a—N11174.6 (2)
C7—C8—C9—C101.3 (4)C5—C4a—C11a—N1110.9 (4)
C8—C9—C10—C10a0.7 (4)
(II) (6RS)-4-Chloro-8-hydroxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine top
Crystal data top
C14H14ClN3OF(000) = 576
Mr = 275.73Dx = 1.462 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.0251 (7) ÅCell parameters from 2874 reflections
b = 21.5510 (17) Åθ = 3.0–27.5°
c = 8.0709 (6) ŵ = 0.30 mm1
β = 116.216 (6)°T = 120 K
V = 1252.27 (19) Å3Needle, colourless
Z = 40.32 × 0.18 × 0.16 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2870 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2154 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.4°
φ and ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2825
Tmin = 0.761, Tmax = 0.953l = 1010
22327 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.028P)2 + 1.1981P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
2870 reflectionsΔρmax = 0.34 e Å3
177 parametersΔρmin = 0.28 e Å3
Crystal data top
C14H14ClN3OV = 1252.27 (19) Å3
Mr = 275.73Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0251 (7) ŵ = 0.30 mm1
b = 21.5510 (17) ÅT = 120 K
c = 8.0709 (6) Å0.32 × 0.18 × 0.16 mm
β = 116.216 (6)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2870 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2154 reflections with I > 2σ(I)
Tmin = 0.761, Tmax = 0.953Rint = 0.069
22327 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.34 e Å3
2870 reflectionsΔρmin = 0.28 e Å3
177 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.7799 (2)0.54817 (8)0.8058 (3)0.0204 (4)
C20.7396 (3)0.49672 (10)0.8689 (3)0.0229 (5)
H20.84130.47070.94190.027*
N30.5710 (3)0.47716 (8)0.8412 (3)0.0212 (4)
C40.4323 (3)0.51420 (10)0.7314 (3)0.0191 (4)
Cl40.21309 (7)0.48684 (3)0.68991 (8)0.02518 (15)
C4a0.4491 (3)0.56917 (10)0.6523 (3)0.0179 (4)
C50.2784 (3)0.60396 (10)0.5204 (3)0.0209 (5)
H5A0.23550.63060.59390.025*
H5B0.17900.57330.45440.025*
C60.3015 (3)0.64482 (10)0.3761 (3)0.0190 (5)
H60.37590.62120.32530.023*
C6a0.4080 (3)0.70266 (10)0.4681 (3)0.0170 (4)
C70.3298 (3)0.76142 (10)0.4257 (3)0.0185 (4)
H70.20580.76570.33280.022*
C80.4274 (3)0.81422 (10)0.5151 (3)0.0190 (5)
C90.6064 (3)0.80834 (10)0.6554 (3)0.0210 (5)
H90.67350.84390.72000.025*
C100.6862 (3)0.74989 (10)0.7003 (3)0.0210 (5)
H100.80830.74570.79710.025*
C10a0.5907 (3)0.69728 (10)0.6061 (3)0.0178 (4)
N110.6892 (2)0.63914 (8)0.6432 (3)0.0188 (4)
C11a0.6369 (3)0.58616 (10)0.7010 (3)0.0184 (4)
C610.1098 (3)0.65751 (11)0.2182 (3)0.0226 (5)
H61A0.03130.67760.26710.034*
H61B0.05280.61820.15900.034*
H61C0.12240.68480.12730.034*
O810.3389 (2)0.86969 (7)0.4575 (2)0.0228 (4)
H810.400 (4)0.8997 (13)0.533 (4)0.034*
C1110.8832 (3)0.64225 (10)0.6705 (3)0.0218 (5)
H11A0.96580.64880.80170.033*
H11B0.89680.67680.59830.033*
H11C0.91590.60330.62950.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0166 (9)0.0176 (9)0.0234 (10)0.0011 (7)0.0054 (8)0.0008 (8)
C20.0194 (11)0.0176 (11)0.0273 (13)0.0034 (8)0.0064 (10)0.0010 (9)
N30.0211 (9)0.0160 (9)0.0243 (10)0.0007 (7)0.0081 (8)0.0005 (7)
C40.0155 (10)0.0182 (10)0.0217 (11)0.0030 (8)0.0063 (9)0.0047 (9)
Cl40.0183 (3)0.0244 (3)0.0289 (3)0.0055 (2)0.0068 (2)0.0026 (2)
C4a0.0158 (10)0.0173 (10)0.0186 (11)0.0000 (8)0.0058 (9)0.0027 (8)
C50.0131 (10)0.0216 (11)0.0247 (12)0.0003 (8)0.0055 (9)0.0017 (9)
C60.0160 (10)0.0183 (11)0.0195 (11)0.0013 (8)0.0049 (9)0.0006 (8)
C6a0.0160 (10)0.0185 (10)0.0165 (11)0.0014 (8)0.0072 (9)0.0017 (8)
C70.0150 (10)0.0210 (11)0.0175 (11)0.0001 (8)0.0052 (9)0.0009 (8)
C80.0209 (11)0.0174 (11)0.0211 (12)0.0023 (8)0.0116 (9)0.0012 (9)
C90.0224 (11)0.0168 (10)0.0224 (12)0.0043 (9)0.0086 (10)0.0035 (9)
C100.0149 (10)0.0215 (11)0.0227 (12)0.0006 (8)0.0047 (9)0.0006 (9)
C10a0.0176 (10)0.0161 (10)0.0201 (11)0.0013 (8)0.0087 (9)0.0020 (8)
N110.0131 (8)0.0174 (9)0.0231 (10)0.0003 (7)0.0056 (8)0.0012 (7)
C11a0.0157 (10)0.0184 (10)0.0199 (11)0.0009 (8)0.0069 (9)0.0033 (9)
C610.0184 (10)0.0215 (11)0.0217 (12)0.0004 (9)0.0031 (9)0.0031 (9)
O810.0228 (8)0.0154 (8)0.0248 (9)0.0018 (6)0.0055 (7)0.0006 (7)
C1110.0142 (10)0.0239 (11)0.0245 (13)0.0011 (9)0.0060 (9)0.0002 (9)
Geometric parameters (Å, º) top
N1—C21.319 (3)C7—H70.9500
N1—C11a1.358 (3)C8—O811.363 (3)
C2—N31.338 (3)C8—C91.387 (3)
C2—H20.9500C9—C101.387 (3)
N3—C41.338 (3)C9—H90.9500
C4—C4a1.380 (3)C10—C10a1.391 (3)
C4—Cl41.742 (2)C10—H100.9500
C4a—C11a1.427 (3)C10a—N111.441 (3)
C4a—C51.511 (3)N11—C11a1.367 (3)
C5—C61.535 (3)N11—C1111.475 (3)
C5—H5A0.9900C61—H61A0.9800
C5—H5B0.9900C61—H61B0.9800
C6—C6a1.508 (3)C61—H61C0.9800
C6—C611.528 (3)O81—H810.88 (3)
C6—H61.0000C111—H11A0.9800
C6a—C71.387 (3)C111—H11B0.9800
C6a—C10a1.400 (3)C111—H11C0.9800
C7—C81.389 (3)
C2—N1—C11a117.63 (19)O81—C8—C7116.88 (19)
N1—C2—N3127.1 (2)C9—C8—C7119.5 (2)
N1—C2—H2116.5C10—C9—C8119.2 (2)
N3—C2—H2116.5C10—C9—H9120.4
C4—N3—C2113.98 (19)C8—C9—H9120.4
N3—C4—C4a126.57 (19)C9—C10—C10a121.2 (2)
N3—C4—Cl4113.55 (16)C9—C10—H10119.4
C4a—C4—Cl4119.88 (16)C10a—C10—H10119.4
C4—C4a—C11a113.56 (19)C10—C10a—C6a119.8 (2)
C4—C4a—C5120.56 (19)C10—C10a—N11118.42 (19)
C11a—C4a—C5125.81 (19)C6a—C10a—N11121.53 (19)
C4a—C5—C6116.30 (17)C11a—N11—C10a125.08 (17)
C4a—C5—H5A108.2C11a—N11—C111116.72 (17)
C6—C5—H5A108.2C10a—N11—C111115.95 (17)
C4a—C5—H5B108.2N1—C11a—N11114.46 (18)
C6—C5—H5B108.2N1—C11a—C4a121.0 (2)
H5A—C5—H5B107.4N11—C11a—C4a124.46 (19)
C6a—C6—C61113.92 (18)C6—C61—H61A109.5
C6a—C6—C5109.41 (18)C6—C61—H61B109.5
C61—C6—C5108.70 (18)H61A—C61—H61B109.5
C6a—C6—H6108.2C6—C61—H61C109.5
C61—C6—H6108.2H61A—C61—H61C109.5
C5—C6—H6108.2H61B—C61—H61C109.5
C7—C6a—C10a118.17 (19)C8—O81—H81111.2 (18)
C7—C6a—C6122.49 (19)N11—C111—H11A109.5
C10a—C6a—C6119.31 (19)N11—C111—H11B109.5
C6a—C7—C8122.01 (19)H11A—C111—H11B109.5
C6a—C7—H7119.0N11—C111—H11C109.5
C8—C7—H7119.0H11A—C111—H11C109.5
O81—C8—C9123.7 (2)H11B—C111—H11C109.5
C11a—N1—C2—N30.0 (4)C8—C9—C10—C10a0.6 (3)
N1—C2—N3—C42.6 (3)C9—C10—C10a—C6a2.5 (3)
C2—N3—C4—C4a1.7 (3)C9—C10—C10a—N11172.3 (2)
C2—N3—C4—Cl4177.86 (16)C7—C6a—C10a—C102.0 (3)
N3—C4—C4a—C11a1.4 (3)C6—C6a—C10a—C10175.9 (2)
Cl4—C4—C4a—C11a179.07 (16)C7—C6a—C10a—N11172.61 (19)
N3—C4—C4a—C5175.8 (2)C6—C6a—C10a—N119.5 (3)
Cl4—C4—C4a—C53.7 (3)C10—C10a—N11—C11a123.6 (2)
C4—C4a—C5—C6152.9 (2)C6a—C10a—N11—C11a61.7 (3)
C11a—C4a—C5—C623.9 (3)C10—C10a—N11—C11138.7 (3)
C4a—C5—C6—C6a74.6 (2)C6a—C10a—N11—C111136.0 (2)
C4a—C5—C6—C61160.39 (19)C2—N1—C11a—N11178.83 (19)
C61—C6—C6a—C76.7 (3)C2—N1—C11a—C4a3.5 (3)
C5—C6—C6a—C7115.2 (2)C10a—N11—C11a—N1150.9 (2)
C61—C6—C6a—C10a175.5 (2)C111—N11—C11a—N111.3 (3)
C5—C6—C6a—C10a62.6 (2)C10a—N11—C11a—C4a31.5 (3)
C10a—C6a—C7—C80.3 (3)C111—N11—C11a—C4a166.2 (2)
C6—C6a—C7—C8178.1 (2)C4—C4a—C11a—N14.1 (3)
C6a—C7—C8—O81177.69 (19)C5—C4a—C11a—N1173.0 (2)
C6a—C7—C8—C92.2 (3)C4—C4a—C11a—N11178.5 (2)
O81—C8—C9—C10178.2 (2)C5—C4a—C11a—N114.4 (3)
C7—C8—C9—C101.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O81—H81···N3i0.88 (3)1.91 (3)2.737 (2)156 (3)
Symmetry code: (i) x+1, y+1/2, z+3/2.
(III) (6RS)-4-Chloro-8-methoxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine top
Crystal data top
C15H16ClN3OF(000) = 608
Mr = 289.76Dx = 1.432 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.2148 (7) ÅCell parameters from 3080 reflections
b = 12.9078 (8) Åθ = 2.9–27.5°
c = 15.0778 (6) ŵ = 0.28 mm1
β = 122.774 (5)°T = 120 K
V = 1344.27 (17) Å3Block, colourless
Z = 40.22 × 0.20 × 0.16 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3076 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1978 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.099
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
φ and ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1616
Tmin = 0.834, Tmax = 0.956l = 1919
14823 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0344P)2 + 0.632P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3076 reflectionsΔρmax = 0.26 e Å3
184 parametersΔρmin = 0.25 e Å3
Crystal data top
C15H16ClN3OV = 1344.27 (17) Å3
Mr = 289.76Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.2148 (7) ŵ = 0.28 mm1
b = 12.9078 (8) ÅT = 120 K
c = 15.0778 (6) Å0.22 × 0.20 × 0.16 mm
β = 122.774 (5)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3076 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1978 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.956Rint = 0.099
14823 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.04Δρmax = 0.26 e Å3
3076 reflectionsΔρmin = 0.25 e Å3
184 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.8430 (3)1.20048 (16)0.90410 (16)0.0275 (5)
C20.8875 (4)1.1927 (2)1.0028 (2)0.0306 (6)
H20.95651.24951.04780.037*
N30.8473 (3)1.11524 (18)1.04625 (16)0.0308 (5)
C40.7654 (4)1.0340 (2)0.98205 (19)0.0257 (6)
Cl40.72336 (11)0.92876 (6)1.03936 (5)0.03398 (19)
C4a0.7179 (3)1.02599 (19)0.87877 (18)0.0211 (5)
C50.6558 (3)0.92301 (19)0.82268 (17)0.0206 (5)
H5A0.51840.91140.79790.025*
H5B0.73280.86780.87430.025*
C60.6772 (3)0.91143 (17)0.72746 (17)0.0188 (5)
H60.80560.94050.74740.023*
C6a0.5205 (3)0.97552 (18)0.63861 (18)0.0182 (5)
C70.3599 (3)0.93194 (18)0.54985 (17)0.0193 (5)
H70.35420.85890.54060.023*
C80.2072 (3)0.99277 (18)0.47419 (17)0.0193 (5)
C90.2123 (4)1.09935 (18)0.48690 (18)0.0214 (5)
H90.10761.14140.43680.026*
C100.3737 (4)1.14320 (18)0.57438 (18)0.0223 (5)
H100.37931.21630.58280.027*
C10a0.5269 (3)1.08360 (18)0.64981 (18)0.0197 (5)
N110.6943 (3)1.13322 (15)0.73691 (15)0.0223 (5)
C11a0.7495 (3)1.11875 (19)0.83954 (19)0.0223 (5)
C610.6732 (4)0.79654 (18)0.70220 (19)0.0231 (5)
H61A0.67300.78900.63750.035*
H61B0.55620.76460.69230.035*
H61C0.78780.76230.76060.035*
O810.0591 (2)0.93874 (13)0.39116 (12)0.0239 (4)
C810.1065 (4)0.9973 (2)0.31461 (18)0.0267 (6)
H81A0.06851.04570.27880.040*
H81B0.15811.03620.35000.040*
H81C0.20610.95010.26270.040*
C1110.7676 (4)1.22473 (19)0.7112 (2)0.0302 (6)
H11A0.90821.22950.76050.045*
H11B0.70611.28720.71700.045*
H11C0.73741.21850.63910.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0211 (12)0.0263 (11)0.0302 (12)0.0006 (9)0.0107 (10)0.0086 (9)
C20.0202 (14)0.0301 (15)0.0295 (14)0.0056 (11)0.0055 (12)0.0115 (12)
N30.0266 (12)0.0350 (13)0.0225 (11)0.0075 (10)0.0078 (10)0.0068 (10)
C40.0206 (13)0.0292 (14)0.0251 (13)0.0074 (11)0.0111 (11)0.0008 (11)
Cl40.0423 (4)0.0393 (4)0.0237 (3)0.0088 (3)0.0201 (3)0.0042 (3)
C4a0.0157 (12)0.0252 (13)0.0200 (11)0.0030 (10)0.0080 (10)0.0011 (10)
C50.0176 (12)0.0238 (12)0.0193 (11)0.0003 (10)0.0094 (10)0.0011 (10)
C60.0183 (12)0.0203 (12)0.0190 (11)0.0005 (10)0.0108 (10)0.0005 (9)
C6a0.0196 (12)0.0183 (11)0.0217 (11)0.0010 (10)0.0146 (10)0.0001 (9)
C70.0228 (12)0.0175 (11)0.0210 (11)0.0009 (10)0.0140 (10)0.0005 (10)
C80.0212 (12)0.0225 (12)0.0170 (11)0.0010 (10)0.0123 (10)0.0006 (9)
C90.0252 (13)0.0201 (12)0.0210 (12)0.0060 (10)0.0140 (11)0.0051 (9)
C100.0303 (14)0.0162 (11)0.0264 (12)0.0015 (10)0.0192 (12)0.0009 (10)
C10a0.0231 (13)0.0201 (12)0.0210 (11)0.0026 (10)0.0153 (10)0.0030 (10)
N110.0250 (12)0.0200 (10)0.0239 (10)0.0040 (9)0.0146 (9)0.0032 (8)
C11a0.0182 (13)0.0228 (13)0.0251 (12)0.0012 (10)0.0113 (11)0.0060 (10)
C610.0249 (14)0.0212 (12)0.0235 (12)0.0032 (10)0.0133 (11)0.0008 (10)
O810.0202 (9)0.0236 (9)0.0194 (8)0.0023 (7)0.0053 (7)0.0017 (7)
C810.0218 (13)0.0343 (15)0.0196 (12)0.0047 (12)0.0084 (11)0.0031 (11)
C1110.0348 (16)0.0194 (13)0.0428 (15)0.0096 (12)0.0252 (13)0.0051 (12)
Geometric parameters (Å, º) top
N1—C21.330 (3)C8—O811.373 (3)
N1—C11a1.357 (3)C8—C91.386 (3)
C2—N31.332 (4)C9—C101.387 (3)
C2—H20.9500C9—H90.9500
N3—C41.336 (3)C10—C10a1.385 (3)
C4—C4a1.389 (3)C10—H100.9500
C4—Cl41.741 (3)C10a—N111.439 (3)
C4a—C11a1.420 (3)N11—C11a1.369 (3)
C4a—C51.508 (3)N11—C1111.470 (3)
C5—C61.545 (3)C61—H61A0.9800
C5—H5A0.9900C61—H61B0.9800
C5—H5B0.9900C61—H61C0.9800
C6—C6a1.506 (3)O81—C811.433 (3)
C6—C611.527 (3)C81—H81A0.9800
C6—H61.0000C81—H81B0.9800
C6a—C71.392 (3)C81—H81C0.9800
C6a—C10a1.403 (3)C111—H11A0.9800
C7—C81.394 (3)C111—H11B0.9800
C7—H70.9500C111—H11C0.9800
C2—N1—C11a116.7 (2)C8—C9—H9120.7
N1—C2—N3128.0 (2)C10—C9—H9120.7
N1—C2—H2116.0C10a—C10—C9122.0 (2)
N3—C2—H2116.0C10a—C10—H10119.0
C2—N3—C4113.3 (2)C9—C10—H10119.0
N3—C4—C4a126.6 (2)C10—C10a—C6a119.7 (2)
N3—C4—Cl4114.22 (19)C10—C10a—N11119.8 (2)
C4a—C4—Cl4119.2 (2)C6a—C10a—N11120.5 (2)
C4—C4a—C11a113.6 (2)C11a—N11—C10a122.6 (2)
C4—C4a—C5119.9 (2)C11a—N11—C111118.4 (2)
C11a—C4a—C5126.3 (2)C10a—N11—C111116.3 (2)
C4a—C5—C6115.6 (2)N1—C11a—N11114.6 (2)
C4a—C5—H5A108.4N1—C11a—C4a121.1 (2)
C6—C5—H5A108.4N11—C11a—C4a124.2 (2)
C4a—C5—H5B108.4C6—C61—H61A109.5
C6—C5—H5B108.4C6—C61—H61B109.5
H5A—C5—H5B107.4H61A—C61—H61B109.5
C6a—C6—C61114.76 (19)C6—C61—H61C109.5
C6a—C6—C5107.52 (19)H61A—C61—H61C109.5
C61—C6—C5109.14 (19)H61B—C61—H61C109.5
C6a—C6—H6108.4C8—O81—C81116.92 (19)
C61—C6—H6108.4O81—C81—H81A109.5
C5—C6—H6108.4O81—C81—H81B109.5
C7—C6a—C10a118.1 (2)H81A—C81—H81B109.5
C7—C6a—C6122.8 (2)O81—C81—H81C109.5
C10a—C6a—C6118.7 (2)H81A—C81—H81C109.5
C6a—C7—C8121.6 (2)H81B—C81—H81C109.5
C6a—C7—H7119.2N11—C111—H11A109.5
C8—C7—H7119.2N11—C111—H11B109.5
O81—C8—C9125.2 (2)H11A—C111—H11B109.5
O81—C8—C7114.9 (2)N11—C111—H11C109.5
C9—C8—C7120.0 (2)H11A—C111—H11C109.5
C8—C9—C10118.6 (2)H11B—C111—H11C109.5
C11a—N1—C2—N31.9 (4)C9—C10—C10a—C6a0.2 (3)
N1—C2—N3—C45.5 (4)C9—C10—C10a—N11177.5 (2)
C2—N3—C4—C4a1.6 (4)C7—C6a—C10a—C101.2 (3)
C2—N3—C4—Cl4176.68 (19)C6—C6a—C10a—C10173.0 (2)
N3—C4—C4a—C11a5.0 (4)C7—C6a—C10a—N11176.5 (2)
Cl4—C4—C4a—C11a176.78 (18)C6—C6a—C10a—N119.3 (3)
N3—C4—C4a—C5170.2 (2)C10—C10a—N11—C11a117.1 (3)
Cl4—C4—C4a—C58.1 (3)C6a—C10a—N11—C11a65.2 (3)
C4—C4a—C5—C6158.8 (2)C10—C10a—N11—C11143.7 (3)
C11a—C4a—C5—C615.7 (3)C6a—C10a—N11—C111134.0 (2)
C4a—C5—C6—C6a73.2 (2)C2—N1—C11a—N11175.5 (2)
C4a—C5—C6—C61161.8 (2)C2—N1—C11a—C4a5.8 (3)
C61—C6—C6a—C713.9 (3)C10a—N11—C11a—N1150.5 (2)
C5—C6—C6a—C7107.7 (2)C111—N11—C11a—N110.0 (3)
C61—C6—C6a—C10a172.2 (2)C10a—N11—C11a—C4a30.9 (4)
C5—C6—C6a—C10a66.2 (3)C111—N11—C11a—C4a168.6 (2)
C10a—C6a—C7—C80.8 (3)C4—C4a—C11a—N18.8 (3)
C6—C6a—C7—C8173.1 (2)C5—C4a—C11a—N1166.1 (2)
C6a—C7—C8—O81180.0 (2)C4—C4a—C11a—N11172.7 (2)
C6a—C7—C8—C90.6 (3)C5—C4a—C11a—N1112.5 (4)
O81—C8—C9—C10179.0 (2)C9—C8—O81—C813.1 (3)
C7—C8—C9—C101.6 (3)C7—C8—O81—C81176.3 (2)
C8—C9—C10—C10a1.2 (3)
(IV) (6RS)-4-Chloro-8-methoxy-6,11-dimethyl-2-phenyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine top
Crystal data top
C21H20ClN3OF(000) = 768
Mr = 365.85Dx = 1.334 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.9431 (8) ÅCell parameters from 4178 reflections
b = 9.2078 (10) Åθ = 2.8–27.5°
c = 14.802 (4) ŵ = 0.23 mm1
β = 106.521 (8)°T = 120 K
V = 1821.9 (5) Å3Block, colourless
Z = 40.28 × 0.22 × 0.16 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3598 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2321 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.103
Detector resolution: 9.091 pixels mm-1θmax = 26.1°, θmin = 2.8°
φ and ω scansh = 1717
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.821, Tmax = 0.965l = 1818
25675 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0291P)2 + 2.470P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3598 reflectionsΔρmax = 0.43 e Å3
238 parametersΔρmin = 0.40 e Å3
Crystal data top
C21H20ClN3OV = 1821.9 (5) Å3
Mr = 365.85Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.9431 (8) ŵ = 0.23 mm1
b = 9.2078 (10) ÅT = 120 K
c = 14.802 (4) Å0.28 × 0.22 × 0.16 mm
β = 106.521 (8)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
3598 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2321 reflections with I > 2σ(I)
Tmin = 0.821, Tmax = 0.965Rint = 0.103
25675 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.08Δρmax = 0.43 e Å3
3598 reflectionsΔρmin = 0.40 e Å3
238 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.52465 (17)0.1084 (3)0.37737 (17)0.0203 (6)
C20.6009 (2)0.1994 (3)0.3850 (2)0.0210 (7)
N30.59558 (18)0.3446 (3)0.38135 (17)0.0218 (6)
C40.5053 (2)0.3963 (3)0.3768 (2)0.0211 (6)
Cl40.49862 (6)0.58666 (8)0.37500 (6)0.0284 (2)
C4a0.4195 (2)0.3182 (3)0.3747 (2)0.0215 (7)
C50.3278 (2)0.3918 (3)0.3895 (2)0.0235 (7)
H5A0.29090.43980.32990.028*
H5B0.35020.46850.43770.028*
C60.2555 (2)0.2898 (3)0.4204 (2)0.0252 (7)
H60.29630.22250.46960.030*
C6a0.2014 (2)0.1996 (3)0.3356 (2)0.0213 (7)
C70.1011 (2)0.2229 (3)0.2841 (2)0.0229 (7)
H70.06250.29280.30550.027*
C80.0579 (2)0.1451 (3)0.2026 (2)0.0221 (7)
C90.1138 (2)0.0431 (3)0.1701 (2)0.0200 (6)
H90.08420.00980.11400.024*
C100.2129 (2)0.0189 (3)0.2197 (2)0.0207 (6)
H100.25130.05020.19740.025*
C10a0.2563 (2)0.0958 (3)0.3027 (2)0.0201 (6)
N110.35823 (17)0.0647 (3)0.35510 (17)0.0214 (6)
C11a0.4336 (2)0.1660 (3)0.3684 (2)0.0189 (6)
C210.7002 (2)0.1318 (3)0.3944 (2)0.0212 (7)
C220.7055 (2)0.0138 (3)0.3685 (2)0.0257 (7)
H220.64610.06980.34760.031*
C230.7971 (2)0.0763 (4)0.3734 (2)0.0305 (8)
H230.80030.17460.35490.037*
C240.8845 (2)0.0045 (4)0.4052 (2)0.0314 (8)
H240.94720.03820.40750.038*
C250.8802 (2)0.1473 (4)0.4336 (2)0.0294 (8)
H250.94010.20150.45710.035*
C260.7883 (2)0.2112 (3)0.4277 (2)0.0240 (7)
H260.78550.30940.44650.029*
C610.1875 (2)0.3764 (4)0.4642 (2)0.0314 (8)
H61A0.15180.45010.41940.047*
H61B0.22770.42400.52170.047*
H61C0.13910.31100.47980.047*
O810.03908 (14)0.1617 (2)0.14707 (15)0.0275 (5)
C810.1018 (2)0.2587 (4)0.1798 (2)0.0318 (8)
H81A0.10360.22910.24290.048*
H81B0.16960.25600.13650.048*
H81C0.07520.35760.18240.048*
C1110.3866 (2)0.0896 (3)0.3620 (2)0.0260 (7)
H11A0.40760.11740.30660.039*
H11B0.32920.14880.36490.039*
H11C0.44200.10530.41910.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0234 (13)0.0208 (14)0.0161 (13)0.0024 (11)0.0045 (10)0.0000 (11)
C20.0237 (15)0.0231 (16)0.0151 (16)0.0021 (14)0.0037 (12)0.0003 (13)
N30.0242 (13)0.0202 (13)0.0196 (14)0.0021 (11)0.0039 (11)0.0010 (11)
C40.0295 (16)0.0150 (14)0.0169 (15)0.0032 (14)0.0035 (12)0.0028 (13)
Cl40.0329 (4)0.0174 (4)0.0309 (5)0.0031 (4)0.0026 (3)0.0012 (3)
C4a0.0231 (16)0.0235 (17)0.0160 (16)0.0011 (13)0.0022 (12)0.0032 (13)
C50.0254 (16)0.0226 (16)0.0195 (16)0.0036 (13)0.0015 (12)0.0076 (13)
C60.0258 (16)0.0279 (17)0.0219 (17)0.0031 (14)0.0069 (13)0.0044 (14)
C6a0.0233 (15)0.0223 (16)0.0202 (16)0.0000 (13)0.0093 (13)0.0012 (13)
C70.0250 (16)0.0225 (16)0.0240 (17)0.0007 (13)0.0114 (13)0.0053 (13)
C80.0199 (15)0.0210 (15)0.0265 (17)0.0008 (13)0.0084 (13)0.0013 (13)
C90.0245 (15)0.0167 (15)0.0189 (16)0.0035 (12)0.0064 (12)0.0042 (12)
C100.0264 (16)0.0159 (15)0.0214 (16)0.0003 (13)0.0096 (13)0.0004 (13)
C10a0.0194 (14)0.0200 (15)0.0211 (16)0.0023 (13)0.0063 (12)0.0040 (13)
N110.0208 (12)0.0185 (13)0.0234 (14)0.0027 (11)0.0039 (10)0.0005 (11)
C11a0.0213 (15)0.0204 (16)0.0142 (15)0.0020 (13)0.0039 (12)0.0000 (12)
C210.0212 (15)0.0247 (17)0.0170 (15)0.0038 (13)0.0045 (12)0.0029 (13)
C220.0233 (16)0.0271 (17)0.0246 (17)0.0009 (14)0.0037 (13)0.0034 (14)
C230.0329 (18)0.0281 (18)0.0290 (19)0.0076 (16)0.0065 (14)0.0033 (15)
C240.0263 (17)0.039 (2)0.0272 (18)0.0117 (16)0.0048 (14)0.0036 (16)
C250.0230 (17)0.0342 (19)0.0276 (18)0.0009 (15)0.0017 (14)0.0072 (15)
C260.0275 (16)0.0197 (16)0.0227 (17)0.0019 (14)0.0037 (13)0.0060 (13)
C610.0356 (19)0.032 (2)0.0258 (18)0.0076 (15)0.0078 (15)0.0046 (14)
O810.0197 (11)0.0300 (12)0.0312 (13)0.0026 (9)0.0050 (9)0.0083 (10)
C810.0228 (16)0.039 (2)0.035 (2)0.0083 (15)0.0103 (14)0.0050 (16)
C1110.0266 (16)0.0193 (15)0.0315 (18)0.0022 (14)0.0073 (14)0.0047 (14)
Geometric parameters (Å, º) top
N1—C21.332 (4)C10a—N111.441 (4)
N1—C11a1.348 (4)N11—C11a1.376 (4)
C2—N31.340 (4)N11—C1111.471 (4)
C2—C211.488 (4)C21—C261.394 (4)
N3—C41.330 (4)C21—C221.402 (4)
C4—C4a1.388 (4)C22—C231.384 (4)
C4—Cl41.755 (3)C22—H220.9500
C4a—C11a1.422 (4)C23—C241.390 (5)
C4a—C51.516 (4)C23—H230.9500
C5—C61.540 (4)C24—C251.387 (5)
C5—H5A0.9900C24—H240.9500
C5—H5B0.9900C25—C261.391 (4)
C6—C6a1.516 (4)C25—H250.9500
C6—C611.518 (4)C26—H260.9500
C6—H61.0000C61—H61A0.9800
C6a—C10a1.396 (4)C61—H61B0.9800
C6a—C71.406 (4)C61—H61C0.9800
C7—C81.386 (4)O81—C811.427 (4)
C7—H70.9500C81—H81A0.9800
C8—O811.377 (3)C81—H81B0.9800
C8—C91.390 (4)C81—H81C0.9800
C9—C101.386 (4)C111—H11A0.9800
C9—H90.9500C111—H11B0.9800
C10—C10a1.397 (4)C111—H11C0.9800
C10—H100.9500
C2—N1—C11a117.9 (3)C11a—N11—C111117.7 (2)
N1—C2—N3126.2 (3)C10a—N11—C111115.7 (2)
N1—C2—C21116.3 (3)N1—C11a—N11114.0 (3)
N3—C2—C21117.4 (3)N1—C11a—C4a121.7 (3)
C4—N3—C2113.6 (3)N11—C11a—C4a124.3 (3)
N3—C4—C4a127.8 (3)C26—C21—C22119.3 (3)
N3—C4—Cl4113.8 (2)C26—C21—C2121.1 (3)
C4a—C4—Cl4118.4 (2)C22—C21—C2119.6 (3)
C4—C4a—C11a112.2 (3)C23—C22—C21120.2 (3)
C4—C4a—C5121.4 (3)C23—C22—H22119.9
C11a—C4a—C5126.0 (3)C21—C22—H22119.9
C4a—C5—C6114.8 (3)C22—C23—C24120.1 (3)
C4a—C5—H5A108.6C22—C23—H23119.9
C6—C5—H5A108.6C24—C23—H23119.9
C4a—C5—H5B108.6C25—C24—C23120.1 (3)
C6—C5—H5B108.6C25—C24—H24120.0
H5A—C5—H5B107.5C23—C24—H24120.0
C6a—C6—C61114.7 (3)C24—C25—C26120.0 (3)
C6a—C6—C5107.5 (2)C24—C25—H25120.0
C61—C6—C5110.3 (3)C26—C25—H25120.0
C6a—C6—H6108.0C25—C26—C21120.3 (3)
C61—C6—H6108.0C25—C26—H26119.9
C5—C6—H6108.0C21—C26—H26119.9
C10a—C6a—C7118.4 (3)C6—C61—H61A109.5
C10a—C6a—C6118.1 (3)C6—C61—H61B109.5
C7—C6a—C6123.3 (3)H61A—C61—H61B109.5
C8—C7—C6a120.8 (3)C6—C61—H61C109.5
C8—C7—H7119.6H61A—C61—H61C109.5
C6a—C7—H7119.6H61B—C61—H61C109.5
O81—C8—C7124.9 (3)C8—O81—C81117.4 (2)
O81—C8—C9114.9 (3)O81—C81—H81A109.5
C7—C8—C9120.2 (3)O81—C81—H81B109.5
C10—C9—C8119.8 (3)H81A—C81—H81B109.5
C10—C9—H9120.1O81—C81—H81C109.5
C8—C9—H9120.1H81A—C81—H81C109.5
C9—C10—C10a120.1 (3)H81B—C81—H81C109.5
C9—C10—H10119.9N11—C111—H11A109.5
C10a—C10—H10119.9N11—C111—H11B109.5
C6a—C10a—C10120.6 (3)H11A—C111—H11B109.5
C6a—C10a—N11120.2 (3)N11—C111—H11C109.5
C10—C10a—N11119.2 (3)H11A—C111—H11C109.5
C11a—N11—C10a122.6 (2)H11B—C111—H11C109.5
C11a—N1—C2—N32.4 (4)C9—C10—C10a—N11177.6 (3)
C11a—N1—C2—C21179.8 (2)C6a—C10a—N11—C11a64.6 (4)
N1—C2—N3—C45.3 (4)C10—C10a—N11—C11a116.6 (3)
C21—C2—N3—C4177.4 (2)C6a—C10a—N11—C111138.4 (3)
C2—N3—C4—C4a0.6 (4)C10—C10a—N11—C11140.4 (4)
C2—N3—C4—Cl4178.5 (2)C2—N1—C11a—N11176.1 (2)
N3—C4—C4a—C11a5.9 (4)C2—N1—C11a—C4a5.2 (4)
Cl4—C4—C4a—C11a175.0 (2)C10a—N11—C11a—N1150.4 (3)
N3—C4—C4a—C5167.4 (3)C111—N11—C11a—N16.1 (4)
Cl4—C4—C4a—C511.7 (4)C10a—N11—C11a—C4a31.0 (4)
C4—C4a—C5—C6159.0 (3)C111—N11—C11a—C4a172.5 (3)
C11a—C4a—C5—C613.3 (4)C4—C4a—C11a—N18.7 (4)
C4a—C5—C6—C6a73.2 (3)C5—C4a—C11a—N1164.2 (3)
C4a—C5—C6—C61161.0 (3)C4—C4a—C11a—N11172.8 (3)
C61—C6—C6a—C10a167.7 (3)C5—C4a—C11a—N1114.3 (5)
C5—C6—C6a—C10a69.2 (3)N1—C2—C21—C26162.5 (3)
C61—C6—C6a—C717.5 (4)N3—C2—C21—C2619.8 (4)
C5—C6—C6a—C7105.6 (3)N1—C2—C21—C2218.2 (4)
C10a—C6a—C7—C80.2 (4)N3—C2—C21—C22159.5 (3)
C6—C6a—C7—C8174.6 (3)C26—C21—C22—C232.0 (4)
C6a—C7—C8—O81179.2 (3)C2—C21—C22—C23177.4 (3)
C6a—C7—C8—C90.4 (5)C21—C22—C23—C240.9 (5)
O81—C8—C9—C10179.1 (3)C22—C23—C24—C251.0 (5)
C7—C8—C9—C100.3 (4)C23—C24—C25—C261.9 (5)
C8—C9—C10—C10a0.5 (4)C24—C25—C26—C210.8 (5)
C7—C6a—C10a—C101.0 (4)C22—C21—C26—C251.1 (4)
C6—C6a—C10a—C10174.1 (3)C2—C21—C26—C25178.2 (3)
C7—C6a—C10a—N11177.7 (3)C7—C8—O81—C814.8 (4)
C6—C6a—C10a—N117.2 (4)C9—C8—O81—C81176.4 (3)
C9—C10—C10a—C6a1.2 (4)
Hydrogen-bond geometry (Å, º) top
Cg2 represents the centroid of the ring C6a/C7–C10/C10a.
D—H···AD—HH···AD···AD—H···A
C23—H23···Cg2i0.952.643.511 (4)153
Symmetry code: (i) x+1, y1/2, z+1/2.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC14H14ClN3C14H14ClN3OC15H16ClN3OC21H20ClN3O
Mr259.73275.73289.76365.85
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)120120120120
a, b, c (Å)8.6570 (5), 8.8622 (17), 9.0321 (11)8.0251 (7), 21.5510 (17), 8.0709 (6)8.2148 (7), 12.9078 (8), 15.0778 (6)13.9431 (8), 9.2078 (10), 14.802 (4)
α, β, γ (°)92.649 (13), 113.635 (9), 100.632 (12)90, 116.216 (6), 9090, 122.774 (5), 9090, 106.521 (8), 90
V3)618.34 (16)1252.27 (19)1344.27 (17)1821.9 (5)
Z2444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.290.300.280.23
Crystal size (mm)0.37 × 0.21 × 0.170.32 × 0.18 × 0.160.22 × 0.20 × 0.160.28 × 0.22 × 0.16
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.719, 0.9510.761, 0.9530.834, 0.9560.821, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
11681, 2835, 2068 22327, 2870, 2154 14823, 3076, 1978 25675, 3598, 2321
Rint0.0810.0690.0990.103
(sin θ/λ)max1)0.6500.6500.6500.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.136, 1.08 0.046, 0.104, 1.14 0.052, 0.109, 1.04 0.057, 0.120, 1.08
No. of reflections2835287030763598
No. of parameters165177184238
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.41, 0.390.34, 0.280.26, 0.250.43, 0.40

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Selected geometric parameters (Å, °) for (I)–(V) top
Parameter(I)(II)(III)(IV)(V)
(a)Ring-puckering parameters
Q0.855 (3)0.808 (2)0.875 (3)0.889 (3)0.837 (4)
φ250.3 (2)43.38 (7)48.85 (18)47.7 (2)47.1 (3)
φ3290.1 (5)291.9 (4)290.5 (5)288.6 (6)289.0 (8)
(b)Inter-bond, torsion and dihedral angles
C7—C8—O81116.88 (19)114.9 (2)124.9 (3)
C9—C8—O81123.7 (2)125.2 (2)114.9 (3)
C8—O81—H81111.2 (18)
C8—O81—C81116.92 (19)117.4 (2)
C7—C8—O81—H81169 (2)
C7—C8—O81—C81176.3 (2)-4.8 (4)
C4a—C5—C6—C6a-74.1 (3)-74.6 (2)-73.2 (2)-73.2 (3)-70.6 (4)
C5—C6—C6a—C1065.4 (3)62.6 (2)66.2 (3)69.2 (3)65.9 (4)
C10a—C61A—C6—C61-172.7 (2)-175.5 (2)-172.2 (2)-167.7 (3)-172.3 (3)
C6a—C10a—N11—C111137.3 (2)136.0 (2)134.0 (2)138.4 (3)140.6 (4)
Dihedral50.88 (8)43.38 (7)55.10 (6)55.03 (9)49.48 (19)
Ring-puckering parameters, torsion angles and dihedral angles all refer to the R enantiomers, and the ring-puckering angles are calculated for the atom-sequence N11–C10a–C6a–C6–C5–C4a–C11a in the R enantiomers; thus, for (V), the published structure (Acosta-Quintero et al., 2015) has been inverted to give the same configuration for the reference molecule as in (I)–(IV), and minor amendments have been made to the atom labels. `Dihedral' denotes the dihedral angle between the pyrimidine ring and the fused aryl ring; the dihedral angle between the pyrimidine ring and the pendent aryl ring in (IV) is 18.47 (7)°.
Parameters (Å, °) for hydrogen bonds in (II) and (IV) top
CompoundD—H···AD—HH···AD···AD—H···A
(II)O81—H81···N3i0.88 (3)1.91 (3)2.737 (2)156 (3)
(IV)C23—H23···Cg2ii0.952.643.511 (4)153
Cg2 represents the centroid of the C6a/C7–C10/C10a ring. Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x + 1, y - 1/2, -z + 1/2.
Parameters (Å, °) for C—Cl···Cg contacts in (I), (II) and (IV) top
CompoundC—Cl···CgC—ClCl···CgC···CgC—Cl···Cg
(I)C4—Cl4···Cg1iii1.750 (3)3.7045 (15)4.209 (3)94.10 (10)
(II)C4—Cl4···Cg1iv1.741 (3)3.7994 (16)3.637 (4)71.30 (12)
(IV)C4—Cl4···Cg1v1.755 (3)3.9915 (18)4.913 (3)111.45 (10)
Cg1 represents the centroid of the N1/C2/N3/C4/C4a/C11a ring. Symmetry codes: (iii) -x + 2, -y + 1, -z + 1; (iv) -x + 2, -y + 2, -z + 2; (v) -x + 1, -y + 1, -z + 1.
 

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