Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615020811/yf3094sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020811/yf3094IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IIsup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IIIsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615020811/yf3094IVsup9.cml |
CCDC references: 1434807; 1434806; 1434805; 1434804
\ 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.
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).
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.
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; π–π 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, π–π 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.
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).
C14H14ClN3 | Z = 2 |
Mr = 259.73 | F(000) = 272 |
Triclinic, P1 | Dx = 1.395 Mg m−3 |
a = 8.6570 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.8622 (17) Å | Cell parameters from 2836 reflections |
c = 9.0321 (11) Å | θ = 2.8–27.5° |
α = 92.649 (13)° | µ = 0.29 mm−1 |
β = 113.635 (9)° | T = 120 K |
γ = 100.632 (12)° | Block, colourless |
V = 618.34 (16) Å3 | 0.37 × 0.21 × 0.17 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 2835 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2068 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.719, Tmax = 0.951 | l = −11→11 |
11681 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-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 reflections | Δρmax = 0.41 e Å−3 |
165 parameters | Δρmin = −0.39 e Å−3 |
C14H14ClN3 | γ = 100.632 (12)° |
Mr = 259.73 | V = 618.34 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6570 (5) Å | Mo Kα radiation |
b = 8.8622 (17) Å | µ = 0.29 mm−1 |
c = 9.0321 (11) Å | T = 120 K |
α = 92.649 (13)° | 0.37 × 0.21 × 0.17 mm |
β = 113.635 (9)° |
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 = 0.951 | Rint = 0.081 |
11681 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
2835 reflections | Δρmin = −0.39 e Å−3 |
165 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5727 (3) | 0.5583 (3) | 0.3561 (3) | 0.0253 (5) | |
C2 | 0.6825 (3) | 0.6548 (3) | 0.4884 (3) | 0.0264 (5) | |
H2 | 0.6647 | 0.7571 | 0.4942 | 0.032* | |
N3 | 0.8157 (3) | 0.6243 (3) | 0.6148 (3) | 0.0256 (5) | |
C4 | 0.8400 (3) | 0.4810 (3) | 0.5945 (3) | 0.0225 (5) | |
Cl4 | 1.02073 (8) | 0.44448 (8) | 0.75489 (8) | 0.02865 (19) | |
C4a | 0.7416 (3) | 0.3672 (3) | 0.4627 (3) | 0.0214 (5) | |
C5 | 0.8010 (3) | 0.2187 (3) | 0.4472 (3) | 0.0238 (5) | |
H5A | 0.7668 | 0.1471 | 0.5152 | 0.029* | |
H5B | 0.9288 | 0.2435 | 0.4922 | 0.029* | |
C6 | 0.7294 (3) | 0.1339 (3) | 0.2725 (3) | 0.0223 (5) | |
H6 | 0.7355 | 0.2127 | 0.1981 | 0.027* | |
C6a | 0.5416 (3) | 0.0566 (3) | 0.2217 (3) | 0.0217 (5) | |
C7 | 0.4827 (3) | −0.1037 (3) | 0.2024 (3) | 0.0247 (5) | |
H7 | 0.5612 | −0.1688 | 0.2123 | 0.030* | |
C8 | 0.3117 (3) | −0.1704 (3) | 0.1688 (3) | 0.0272 (6) | |
H8 | 0.2740 | −0.2798 | 0.1551 | 0.033* | |
C9 | 0.1965 (3) | −0.0765 (3) | 0.1554 (3) | 0.0266 (5) | |
H9 | 0.0801 | −0.1214 | 0.1346 | 0.032* | |
C10 | 0.2512 (3) | 0.0832 (3) | 0.1723 (3) | 0.0231 (5) | |
H10 | 0.1717 | 0.1473 | 0.1619 | 0.028* | |
C10a | 0.4222 (3) | 0.1502 (3) | 0.2044 (3) | 0.0212 (5) | |
N11 | 0.4712 (3) | 0.3151 (2) | 0.2100 (2) | 0.0229 (4) | |
C11a | 0.5954 (3) | 0.4118 (3) | 0.3444 (3) | 0.0209 (5) | |
C61 | 0.8436 (3) | 0.0224 (3) | 0.2668 (3) | 0.0287 (6) | |
H61A | 0.7960 | −0.0349 | 0.1570 | 0.043* | |
H61B | 0.8467 | −0.0507 | 0.3457 | 0.043* | |
H61C | 0.9612 | 0.0815 | 0.2942 | 0.043* | |
C111 | 0.3426 (3) | 0.3854 (3) | 0.0869 (3) | 0.0257 (5) | |
H11A | 0.4012 | 0.4836 | 0.0685 | 0.039* | |
H11B | 0.2567 | 0.4045 | 0.1262 | 0.039* | |
H11C | 0.2847 | 0.3146 | −0.0157 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0267 (11) | 0.0236 (11) | 0.0265 (11) | 0.0056 (9) | 0.0117 (9) | 0.0058 (9) |
C2 | 0.0311 (14) | 0.0215 (13) | 0.0294 (13) | 0.0051 (11) | 0.0154 (11) | 0.0048 (10) |
N3 | 0.0266 (11) | 0.0240 (11) | 0.0248 (11) | 0.0007 (9) | 0.0114 (9) | 0.0021 (9) |
C4 | 0.0199 (12) | 0.0263 (13) | 0.0213 (11) | 0.0021 (10) | 0.0097 (10) | 0.0052 (10) |
Cl4 | 0.0236 (3) | 0.0309 (4) | 0.0249 (3) | 0.0025 (2) | 0.0049 (2) | 0.0049 (2) |
C4a | 0.0194 (11) | 0.0254 (13) | 0.0214 (11) | 0.0032 (10) | 0.0110 (9) | 0.0050 (10) |
C5 | 0.0208 (12) | 0.0259 (13) | 0.0246 (12) | 0.0073 (10) | 0.0084 (10) | 0.0051 (10) |
C6 | 0.0204 (12) | 0.0247 (13) | 0.0245 (12) | 0.0055 (10) | 0.0116 (10) | 0.0051 (10) |
C6a | 0.0240 (12) | 0.0255 (13) | 0.0177 (11) | 0.0065 (10) | 0.0100 (9) | 0.0065 (9) |
C7 | 0.0262 (13) | 0.0241 (13) | 0.0248 (12) | 0.0065 (10) | 0.0110 (10) | 0.0042 (10) |
C8 | 0.0301 (14) | 0.0222 (13) | 0.0292 (13) | 0.0035 (11) | 0.0130 (11) | 0.0049 (10) |
C9 | 0.0223 (12) | 0.0303 (14) | 0.0259 (13) | 0.0016 (11) | 0.0106 (10) | 0.0037 (11) |
C10 | 0.0223 (12) | 0.0257 (13) | 0.0209 (11) | 0.0057 (10) | 0.0084 (10) | 0.0040 (10) |
C10a | 0.0240 (12) | 0.0215 (12) | 0.0163 (11) | 0.0038 (10) | 0.0074 (9) | 0.0015 (9) |
N11 | 0.0225 (10) | 0.0217 (11) | 0.0220 (10) | 0.0052 (9) | 0.0064 (8) | 0.0046 (8) |
C11a | 0.0213 (12) | 0.0224 (12) | 0.0206 (11) | 0.0023 (9) | 0.0111 (9) | 0.0044 (9) |
C61 | 0.0257 (13) | 0.0293 (14) | 0.0328 (14) | 0.0051 (11) | 0.0147 (11) | 0.0011 (11) |
C111 | 0.0266 (13) | 0.0262 (13) | 0.0225 (12) | 0.0082 (11) | 0.0069 (10) | 0.0077 (10) |
N1—C2 | 1.325 (3) | C7—C8 | 1.390 (4) |
N1—C11a | 1.354 (3) | C7—H7 | 0.9500 |
C2—N3 | 1.340 (3) | C8—C9 | 1.386 (4) |
C2—H2 | 0.9500 | C8—H8 | 0.9500 |
N3—C4 | 1.341 (3) | C9—C10 | 1.387 (4) |
C4—C4a | 1.385 (4) | C9—H9 | 0.9500 |
C4—Cl4 | 1.750 (3) | C10—C10a | 1.394 (3) |
C4a—C11a | 1.428 (3) | C10—H10 | 0.9500 |
C4a—C5 | 1.518 (3) | C10a—N11 | 1.437 (3) |
C5—C6 | 1.540 (3) | N11—C11a | 1.372 (3) |
C5—H5A | 0.9900 | N11—C111 | 1.480 (3) |
C5—H5B | 0.9900 | C61—H61A | 0.9800 |
C6—C6a | 1.512 (3) | C61—H61B | 0.9800 |
C6—C61 | 1.534 (3) | C61—H61C | 0.9800 |
C6—H6 | 1.0000 | C111—H11A | 0.9800 |
C6a—C7 | 1.396 (4) | C111—H11B | 0.9800 |
C6a—C10a | 1.407 (3) | C111—H11C | 0.9800 |
C2—N1—C11a | 117.6 (2) | C9—C8—H8 | 120.1 |
N1—C2—N3 | 127.4 (2) | C7—C8—H8 | 120.1 |
N1—C2—H2 | 116.3 | C8—C9—C10 | 120.0 (2) |
N3—C2—H2 | 116.3 | C8—C9—H9 | 120.0 |
C2—N3—C4 | 113.3 (2) | C10—C9—H9 | 120.0 |
N3—C4—C4a | 127.0 (2) | C9—C10—C10a | 120.4 (2) |
N3—C4—Cl4 | 113.32 (19) | C9—C10—H10 | 119.8 |
C4a—C4—Cl4 | 119.63 (19) | C10a—C10—H10 | 119.8 |
C4—C4a—C11a | 113.2 (2) | C10—C10a—C6a | 120.3 (2) |
C4—C4a—C5 | 120.4 (2) | C10—C10a—N11 | 118.7 (2) |
C11a—C4a—C5 | 126.1 (2) | C6a—C10a—N11 | 120.9 (2) |
C4a—C5—C6 | 115.4 (2) | C11a—N11—C10a | 123.9 (2) |
C4a—C5—H5A | 108.4 | C11a—N11—C111 | 117.3 (2) |
C6—C5—H5A | 108.4 | C10a—N11—C111 | 115.6 (2) |
C4a—C5—H5B | 108.4 | N1—C11a—N11 | 114.7 (2) |
C6—C5—H5B | 108.4 | N1—C11a—C4a | 121.1 (2) |
H5A—C5—H5B | 107.5 | N11—C11a—C4a | 124.2 (2) |
C6a—C6—C61 | 114.3 (2) | C6—C61—H61A | 109.5 |
C6a—C6—C5 | 108.37 (19) | C6—C61—H61B | 109.5 |
C61—C6—C5 | 109.1 (2) | H61A—C61—H61B | 109.5 |
C6a—C6—H6 | 108.3 | C6—C61—H61C | 109.5 |
C61—C6—H6 | 108.3 | H61A—C61—H61C | 109.5 |
C5—C6—H6 | 108.3 | H61B—C61—H61C | 109.5 |
C7—C6a—C10a | 118.1 (2) | N11—C111—H11A | 109.5 |
C7—C6a—C6 | 123.0 (2) | N11—C111—H11B | 109.5 |
C10a—C6a—C6 | 118.7 (2) | H11A—C111—H11B | 109.5 |
C8—C7—C6a | 121.5 (2) | N11—C111—H11C | 109.5 |
C8—C7—H7 | 119.3 | H11A—C111—H11C | 109.5 |
C6a—C7—H7 | 119.3 | H11B—C111—H11C | 109.5 |
C9—C8—C7 | 119.7 (2) | ||
C11a—N1—C2—N3 | −0.2 (4) | C9—C10—C10a—C6a | −0.7 (4) |
N1—C2—N3—C4 | 3.8 (4) | C9—C10—C10a—N11 | 175.8 (2) |
C2—N3—C4—C4a | −1.6 (4) | C7—C6a—C10a—C10 | 1.4 (3) |
C2—N3—C4—Cl4 | 176.89 (18) | C6—C6a—C10a—C10 | −174.2 (2) |
N3—C4—C4a—C11a | −3.6 (4) | C7—C6a—C10a—N11 | −175.0 (2) |
Cl4—C4—C4a—C11a | 178.01 (17) | C6—C6a—C10a—N11 | 9.4 (3) |
N3—C4—C4a—C5 | 171.3 (2) | C10—C10a—N11—C11a | 120.1 (3) |
Cl4—C4—C4a—C5 | −7.1 (3) | C6a—C10a—N11—C11a | −63.5 (3) |
C4—C4a—C5—C6 | −156.0 (2) | C10—C10a—N11—C111 | −39.1 (3) |
C11a—C4a—C5—C6 | 18.3 (3) | C6a—C10a—N11—C111 | 137.3 (2) |
C4a—C5—C6—C6a | −74.1 (3) | C2—N1—C11a—N11 | 176.0 (2) |
C4a—C5—C6—C61 | 160.9 (2) | C2—N1—C11a—C4a | −5.7 (3) |
C61—C6—C6a—C7 | 12.0 (3) | C10a—N11—C11a—N1 | −151.8 (2) |
C5—C6—C6a—C7 | −109.9 (3) | C111—N11—C11a—N1 | 7.1 (3) |
C61—C6—C6a—C10a | −172.7 (2) | C10a—N11—C11a—C4a | 29.9 (4) |
C5—C6—C6a—C10a | 65.4 (3) | C111—N11—C11a—C4a | −171.2 (2) |
C10a—C6a—C7—C8 | −0.8 (4) | C4—C4a—C11a—N1 | 7.3 (3) |
C6—C6a—C7—C8 | 174.6 (2) | C5—C4a—C11a—N1 | −167.3 (2) |
C6a—C7—C8—C9 | −0.5 (4) | C4—C4a—C11a—N11 | −174.6 (2) |
C7—C8—C9—C10 | 1.3 (4) | C5—C4a—C11a—N11 | 10.9 (4) |
C8—C9—C10—C10a | −0.7 (4) |
C14H14ClN3O | F(000) = 576 |
Mr = 275.73 | Dx = 1.462 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0251 (7) Å | Cell parameters from 2874 reflections |
b = 21.5510 (17) Å | θ = 3.0–27.5° |
c = 8.0709 (6) Å | µ = 0.30 mm−1 |
β = 116.216 (6)° | T = 120 K |
V = 1252.27 (19) Å3 | Needle, colourless |
Z = 4 | 0.32 × 0.18 × 0.16 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 2870 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2154 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −28→25 |
Tmin = 0.761, Tmax = 0.953 | l = −10→10 |
22327 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H 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 reflections | Δρmax = 0.34 e Å−3 |
177 parameters | Δρmin = −0.28 e Å−3 |
C14H14ClN3O | V = 1252.27 (19) Å3 |
Mr = 275.73 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0251 (7) Å | µ = 0.30 mm−1 |
b = 21.5510 (17) Å | T = 120 K |
c = 8.0709 (6) Å | 0.32 × 0.18 × 0.16 mm |
β = 116.216 (6)° |
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 = 0.953 | Rint = 0.069 |
22327 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.34 e Å−3 |
2870 reflections | Δρmin = −0.28 e Å−3 |
177 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.7799 (2) | 0.54817 (8) | 0.8058 (3) | 0.0204 (4) | |
C2 | 0.7396 (3) | 0.49672 (10) | 0.8689 (3) | 0.0229 (5) | |
H2 | 0.8413 | 0.4707 | 0.9419 | 0.027* | |
N3 | 0.5710 (3) | 0.47716 (8) | 0.8412 (3) | 0.0212 (4) | |
C4 | 0.4323 (3) | 0.51420 (10) | 0.7314 (3) | 0.0191 (4) | |
Cl4 | 0.21309 (7) | 0.48684 (3) | 0.68991 (8) | 0.02518 (15) | |
C4a | 0.4491 (3) | 0.56917 (10) | 0.6523 (3) | 0.0179 (4) | |
C5 | 0.2784 (3) | 0.60396 (10) | 0.5204 (3) | 0.0209 (5) | |
H5A | 0.2355 | 0.6306 | 0.5939 | 0.025* | |
H5B | 0.1790 | 0.5733 | 0.4544 | 0.025* | |
C6 | 0.3015 (3) | 0.64482 (10) | 0.3761 (3) | 0.0190 (5) | |
H6 | 0.3759 | 0.6212 | 0.3253 | 0.023* | |
C6a | 0.4080 (3) | 0.70266 (10) | 0.4681 (3) | 0.0170 (4) | |
C7 | 0.3298 (3) | 0.76142 (10) | 0.4257 (3) | 0.0185 (4) | |
H7 | 0.2058 | 0.7657 | 0.3328 | 0.022* | |
C8 | 0.4274 (3) | 0.81422 (10) | 0.5151 (3) | 0.0190 (5) | |
C9 | 0.6064 (3) | 0.80834 (10) | 0.6554 (3) | 0.0210 (5) | |
H9 | 0.6735 | 0.8439 | 0.7200 | 0.025* | |
C10 | 0.6862 (3) | 0.74989 (10) | 0.7003 (3) | 0.0210 (5) | |
H10 | 0.8083 | 0.7457 | 0.7971 | 0.025* | |
C10a | 0.5907 (3) | 0.69728 (10) | 0.6061 (3) | 0.0178 (4) | |
N11 | 0.6892 (2) | 0.63914 (8) | 0.6432 (3) | 0.0188 (4) | |
C11a | 0.6369 (3) | 0.58616 (10) | 0.7010 (3) | 0.0184 (4) | |
C61 | 0.1098 (3) | 0.65751 (11) | 0.2182 (3) | 0.0226 (5) | |
H61A | 0.0313 | 0.6776 | 0.2671 | 0.034* | |
H61B | 0.0528 | 0.6182 | 0.1590 | 0.034* | |
H61C | 0.1224 | 0.6848 | 0.1273 | 0.034* | |
O81 | 0.3389 (2) | 0.86969 (7) | 0.4575 (2) | 0.0228 (4) | |
H81 | 0.400 (4) | 0.8997 (13) | 0.533 (4) | 0.034* | |
C111 | 0.8832 (3) | 0.64225 (10) | 0.6705 (3) | 0.0218 (5) | |
H11A | 0.9658 | 0.6488 | 0.8017 | 0.033* | |
H11B | 0.8968 | 0.6768 | 0.5983 | 0.033* | |
H11C | 0.9159 | 0.6033 | 0.6295 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0166 (9) | 0.0176 (9) | 0.0234 (10) | 0.0011 (7) | 0.0054 (8) | −0.0008 (8) |
C2 | 0.0194 (11) | 0.0176 (11) | 0.0273 (13) | 0.0034 (8) | 0.0064 (10) | −0.0010 (9) |
N3 | 0.0211 (9) | 0.0160 (9) | 0.0243 (10) | 0.0007 (7) | 0.0081 (8) | −0.0005 (7) |
C4 | 0.0155 (10) | 0.0182 (10) | 0.0217 (11) | −0.0030 (8) | 0.0063 (9) | −0.0047 (9) |
Cl4 | 0.0183 (3) | 0.0244 (3) | 0.0289 (3) | −0.0055 (2) | 0.0068 (2) | 0.0026 (2) |
C4a | 0.0158 (10) | 0.0173 (10) | 0.0186 (11) | 0.0000 (8) | 0.0058 (9) | −0.0027 (8) |
C5 | 0.0131 (10) | 0.0216 (11) | 0.0247 (12) | −0.0003 (8) | 0.0055 (9) | 0.0017 (9) |
C6 | 0.0160 (10) | 0.0183 (11) | 0.0195 (11) | 0.0013 (8) | 0.0049 (9) | −0.0006 (8) |
C6a | 0.0160 (10) | 0.0185 (10) | 0.0165 (11) | −0.0014 (8) | 0.0072 (9) | −0.0017 (8) |
C7 | 0.0150 (10) | 0.0210 (11) | 0.0175 (11) | 0.0001 (8) | 0.0052 (9) | −0.0009 (8) |
C8 | 0.0209 (11) | 0.0174 (11) | 0.0211 (12) | 0.0023 (8) | 0.0116 (9) | 0.0012 (9) |
C9 | 0.0224 (11) | 0.0168 (10) | 0.0224 (12) | −0.0043 (9) | 0.0086 (10) | −0.0035 (9) |
C10 | 0.0149 (10) | 0.0215 (11) | 0.0227 (12) | −0.0006 (8) | 0.0047 (9) | 0.0006 (9) |
C10a | 0.0176 (10) | 0.0161 (10) | 0.0201 (11) | 0.0013 (8) | 0.0087 (9) | 0.0020 (8) |
N11 | 0.0131 (8) | 0.0174 (9) | 0.0231 (10) | 0.0003 (7) | 0.0056 (8) | 0.0012 (7) |
C11a | 0.0157 (10) | 0.0184 (10) | 0.0199 (11) | 0.0009 (8) | 0.0069 (9) | −0.0033 (9) |
C61 | 0.0184 (10) | 0.0215 (11) | 0.0217 (12) | −0.0004 (9) | 0.0031 (9) | −0.0031 (9) |
O81 | 0.0228 (8) | 0.0154 (8) | 0.0248 (9) | 0.0018 (6) | 0.0055 (7) | −0.0006 (7) |
C111 | 0.0142 (10) | 0.0239 (11) | 0.0245 (13) | −0.0011 (9) | 0.0060 (9) | 0.0002 (9) |
N1—C2 | 1.319 (3) | C7—H7 | 0.9500 |
N1—C11a | 1.358 (3) | C8—O81 | 1.363 (3) |
C2—N3 | 1.338 (3) | C8—C9 | 1.387 (3) |
C2—H2 | 0.9500 | C9—C10 | 1.387 (3) |
N3—C4 | 1.338 (3) | C9—H9 | 0.9500 |
C4—C4a | 1.380 (3) | C10—C10a | 1.391 (3) |
C4—Cl4 | 1.742 (2) | C10—H10 | 0.9500 |
C4a—C11a | 1.427 (3) | C10a—N11 | 1.441 (3) |
C4a—C5 | 1.511 (3) | N11—C11a | 1.367 (3) |
C5—C6 | 1.535 (3) | N11—C111 | 1.475 (3) |
C5—H5A | 0.9900 | C61—H61A | 0.9800 |
C5—H5B | 0.9900 | C61—H61B | 0.9800 |
C6—C6a | 1.508 (3) | C61—H61C | 0.9800 |
C6—C61 | 1.528 (3) | O81—H81 | 0.88 (3) |
C6—H6 | 1.0000 | C111—H11A | 0.9800 |
C6a—C7 | 1.387 (3) | C111—H11B | 0.9800 |
C6a—C10a | 1.400 (3) | C111—H11C | 0.9800 |
C7—C8 | 1.389 (3) | ||
C2—N1—C11a | 117.63 (19) | O81—C8—C7 | 116.88 (19) |
N1—C2—N3 | 127.1 (2) | C9—C8—C7 | 119.5 (2) |
N1—C2—H2 | 116.5 | C10—C9—C8 | 119.2 (2) |
N3—C2—H2 | 116.5 | C10—C9—H9 | 120.4 |
C4—N3—C2 | 113.98 (19) | C8—C9—H9 | 120.4 |
N3—C4—C4a | 126.57 (19) | C9—C10—C10a | 121.2 (2) |
N3—C4—Cl4 | 113.55 (16) | C9—C10—H10 | 119.4 |
C4a—C4—Cl4 | 119.88 (16) | C10a—C10—H10 | 119.4 |
C4—C4a—C11a | 113.56 (19) | C10—C10a—C6a | 119.8 (2) |
C4—C4a—C5 | 120.56 (19) | C10—C10a—N11 | 118.42 (19) |
C11a—C4a—C5 | 125.81 (19) | C6a—C10a—N11 | 121.53 (19) |
C4a—C5—C6 | 116.30 (17) | C11a—N11—C10a | 125.08 (17) |
C4a—C5—H5A | 108.2 | C11a—N11—C111 | 116.72 (17) |
C6—C5—H5A | 108.2 | C10a—N11—C111 | 115.95 (17) |
C4a—C5—H5B | 108.2 | N1—C11a—N11 | 114.46 (18) |
C6—C5—H5B | 108.2 | N1—C11a—C4a | 121.0 (2) |
H5A—C5—H5B | 107.4 | N11—C11a—C4a | 124.46 (19) |
C6a—C6—C61 | 113.92 (18) | C6—C61—H61A | 109.5 |
C6a—C6—C5 | 109.41 (18) | C6—C61—H61B | 109.5 |
C61—C6—C5 | 108.70 (18) | H61A—C61—H61B | 109.5 |
C6a—C6—H6 | 108.2 | C6—C61—H61C | 109.5 |
C61—C6—H6 | 108.2 | H61A—C61—H61C | 109.5 |
C5—C6—H6 | 108.2 | H61B—C61—H61C | 109.5 |
C7—C6a—C10a | 118.17 (19) | C8—O81—H81 | 111.2 (18) |
C7—C6a—C6 | 122.49 (19) | N11—C111—H11A | 109.5 |
C10a—C6a—C6 | 119.31 (19) | N11—C111—H11B | 109.5 |
C6a—C7—C8 | 122.01 (19) | H11A—C111—H11B | 109.5 |
C6a—C7—H7 | 119.0 | N11—C111—H11C | 109.5 |
C8—C7—H7 | 119.0 | H11A—C111—H11C | 109.5 |
O81—C8—C9 | 123.7 (2) | H11B—C111—H11C | 109.5 |
C11a—N1—C2—N3 | 0.0 (4) | C8—C9—C10—C10a | 0.6 (3) |
N1—C2—N3—C4 | 2.6 (3) | C9—C10—C10a—C6a | −2.5 (3) |
C2—N3—C4—C4a | −1.7 (3) | C9—C10—C10a—N11 | 172.3 (2) |
C2—N3—C4—Cl4 | 177.86 (16) | C7—C6a—C10a—C10 | 2.0 (3) |
N3—C4—C4a—C11a | −1.4 (3) | C6—C6a—C10a—C10 | −175.9 (2) |
Cl4—C4—C4a—C11a | 179.07 (16) | C7—C6a—C10a—N11 | −172.61 (19) |
N3—C4—C4a—C5 | 175.8 (2) | C6—C6a—C10a—N11 | 9.5 (3) |
Cl4—C4—C4a—C5 | −3.7 (3) | C10—C10a—N11—C11a | 123.6 (2) |
C4—C4a—C5—C6 | −152.9 (2) | C6a—C10a—N11—C11a | −61.7 (3) |
C11a—C4a—C5—C6 | 23.9 (3) | C10—C10a—N11—C111 | −38.7 (3) |
C4a—C5—C6—C6a | −74.6 (2) | C6a—C10a—N11—C111 | 136.0 (2) |
C4a—C5—C6—C61 | 160.39 (19) | C2—N1—C11a—N11 | 178.83 (19) |
C61—C6—C6a—C7 | 6.7 (3) | C2—N1—C11a—C4a | −3.5 (3) |
C5—C6—C6a—C7 | −115.2 (2) | C10a—N11—C11a—N1 | −150.9 (2) |
C61—C6—C6a—C10a | −175.5 (2) | C111—N11—C11a—N1 | 11.3 (3) |
C5—C6—C6a—C10a | 62.6 (2) | C10a—N11—C11a—C4a | 31.5 (3) |
C10a—C6a—C7—C8 | 0.3 (3) | C111—N11—C11a—C4a | −166.2 (2) |
C6—C6a—C7—C8 | 178.1 (2) | C4—C4a—C11a—N1 | 4.1 (3) |
C6a—C7—C8—O81 | 177.69 (19) | C5—C4a—C11a—N1 | −173.0 (2) |
C6a—C7—C8—C9 | −2.2 (3) | C4—C4a—C11a—N11 | −178.5 (2) |
O81—C8—C9—C10 | −178.2 (2) | C5—C4a—C11a—N11 | 4.4 (3) |
C7—C8—C9—C10 | 1.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O81—H81···N3i | 0.88 (3) | 1.91 (3) | 2.737 (2) | 156 (3) |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
C15H16ClN3O | F(000) = 608 |
Mr = 289.76 | Dx = 1.432 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2148 (7) Å | Cell parameters from 3080 reflections |
b = 12.9078 (8) Å | θ = 2.9–27.5° |
c = 15.0778 (6) Å | µ = 0.28 mm−1 |
β = 122.774 (5)° | T = 120 K |
V = 1344.27 (17) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.20 × 0.16 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3076 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1978 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −16→16 |
Tmin = 0.834, Tmax = 0.956 | l = −19→19 |
14823 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-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 reflections | Δρmax = 0.26 e Å−3 |
184 parameters | Δρmin = −0.25 e Å−3 |
C15H16ClN3O | V = 1344.27 (17) Å3 |
Mr = 289.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2148 (7) Å | µ = 0.28 mm−1 |
b = 12.9078 (8) Å | T = 120 K |
c = 15.0778 (6) Å | 0.22 × 0.20 × 0.16 mm |
β = 122.774 (5)° |
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 = 0.956 | Rint = 0.099 |
14823 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.26 e Å−3 |
3076 reflections | Δρmin = −0.25 e Å−3 |
184 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.8430 (3) | 1.20048 (16) | 0.90410 (16) | 0.0275 (5) | |
C2 | 0.8875 (4) | 1.1927 (2) | 1.0028 (2) | 0.0306 (6) | |
H2 | 0.9565 | 1.2495 | 1.0478 | 0.037* | |
N3 | 0.8473 (3) | 1.11524 (18) | 1.04625 (16) | 0.0308 (5) | |
C4 | 0.7654 (4) | 1.0340 (2) | 0.98205 (19) | 0.0257 (6) | |
Cl4 | 0.72336 (11) | 0.92876 (6) | 1.03936 (5) | 0.03398 (19) | |
C4a | 0.7179 (3) | 1.02599 (19) | 0.87877 (18) | 0.0211 (5) | |
C5 | 0.6558 (3) | 0.92301 (19) | 0.82268 (17) | 0.0206 (5) | |
H5A | 0.5184 | 0.9114 | 0.7979 | 0.025* | |
H5B | 0.7328 | 0.8678 | 0.8743 | 0.025* | |
C6 | 0.6772 (3) | 0.91143 (17) | 0.72746 (17) | 0.0188 (5) | |
H6 | 0.8056 | 0.9405 | 0.7474 | 0.023* | |
C6a | 0.5205 (3) | 0.97552 (18) | 0.63861 (18) | 0.0182 (5) | |
C7 | 0.3599 (3) | 0.93194 (18) | 0.54985 (17) | 0.0193 (5) | |
H7 | 0.3542 | 0.8589 | 0.5406 | 0.023* | |
C8 | 0.2072 (3) | 0.99277 (18) | 0.47419 (17) | 0.0193 (5) | |
C9 | 0.2123 (4) | 1.09935 (18) | 0.48690 (18) | 0.0214 (5) | |
H9 | 0.1076 | 1.1414 | 0.4368 | 0.026* | |
C10 | 0.3737 (4) | 1.14320 (18) | 0.57438 (18) | 0.0223 (5) | |
H10 | 0.3793 | 1.2163 | 0.5828 | 0.027* | |
C10a | 0.5269 (3) | 1.08360 (18) | 0.64981 (18) | 0.0197 (5) | |
N11 | 0.6943 (3) | 1.13322 (15) | 0.73691 (15) | 0.0223 (5) | |
C11a | 0.7495 (3) | 1.11875 (19) | 0.83954 (19) | 0.0223 (5) | |
C61 | 0.6732 (4) | 0.79654 (18) | 0.70220 (19) | 0.0231 (5) | |
H61A | 0.6730 | 0.7890 | 0.6375 | 0.035* | |
H61B | 0.5562 | 0.7646 | 0.6923 | 0.035* | |
H61C | 0.7878 | 0.7623 | 0.7606 | 0.035* | |
O81 | 0.0591 (2) | 0.93874 (13) | 0.39116 (12) | 0.0239 (4) | |
C81 | −0.1065 (4) | 0.9973 (2) | 0.31461 (18) | 0.0267 (6) | |
H81A | −0.0685 | 1.0457 | 0.2788 | 0.040* | |
H81B | −0.1581 | 1.0362 | 0.3500 | 0.040* | |
H81C | −0.2061 | 0.9501 | 0.2627 | 0.040* | |
C111 | 0.7676 (4) | 1.22473 (19) | 0.7112 (2) | 0.0302 (6) | |
H11A | 0.9082 | 1.2295 | 0.7605 | 0.045* | |
H11B | 0.7061 | 1.2872 | 0.7170 | 0.045* | |
H11C | 0.7374 | 1.2185 | 0.6391 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0211 (12) | 0.0263 (11) | 0.0302 (12) | 0.0006 (9) | 0.0107 (10) | −0.0086 (9) |
C2 | 0.0202 (14) | 0.0301 (15) | 0.0295 (14) | 0.0056 (11) | 0.0055 (12) | −0.0115 (12) |
N3 | 0.0266 (12) | 0.0350 (13) | 0.0225 (11) | 0.0075 (10) | 0.0078 (10) | −0.0068 (10) |
C4 | 0.0206 (13) | 0.0292 (14) | 0.0251 (13) | 0.0074 (11) | 0.0111 (11) | −0.0008 (11) |
Cl4 | 0.0423 (4) | 0.0393 (4) | 0.0237 (3) | 0.0088 (3) | 0.0201 (3) | 0.0042 (3) |
C4a | 0.0157 (12) | 0.0252 (13) | 0.0200 (11) | 0.0030 (10) | 0.0080 (10) | −0.0011 (10) |
C5 | 0.0176 (12) | 0.0238 (12) | 0.0193 (11) | 0.0003 (10) | 0.0094 (10) | 0.0011 (10) |
C6 | 0.0183 (12) | 0.0203 (12) | 0.0190 (11) | 0.0005 (10) | 0.0108 (10) | −0.0005 (9) |
C6a | 0.0196 (12) | 0.0183 (11) | 0.0217 (11) | 0.0010 (10) | 0.0146 (10) | 0.0001 (9) |
C7 | 0.0228 (12) | 0.0175 (11) | 0.0210 (11) | 0.0009 (10) | 0.0140 (10) | 0.0005 (10) |
C8 | 0.0212 (12) | 0.0225 (12) | 0.0170 (11) | 0.0010 (10) | 0.0123 (10) | 0.0006 (9) |
C9 | 0.0252 (13) | 0.0201 (12) | 0.0210 (12) | 0.0060 (10) | 0.0140 (11) | 0.0051 (9) |
C10 | 0.0303 (14) | 0.0162 (11) | 0.0264 (12) | 0.0015 (10) | 0.0192 (12) | 0.0009 (10) |
C10a | 0.0231 (13) | 0.0201 (12) | 0.0210 (11) | −0.0026 (10) | 0.0153 (10) | −0.0030 (10) |
N11 | 0.0250 (12) | 0.0200 (10) | 0.0239 (10) | −0.0040 (9) | 0.0146 (9) | −0.0032 (8) |
C11a | 0.0182 (13) | 0.0228 (13) | 0.0251 (12) | 0.0012 (10) | 0.0113 (11) | −0.0060 (10) |
C61 | 0.0249 (14) | 0.0212 (12) | 0.0235 (12) | 0.0032 (10) | 0.0133 (11) | −0.0008 (10) |
O81 | 0.0202 (9) | 0.0236 (9) | 0.0194 (8) | 0.0023 (7) | 0.0053 (7) | 0.0017 (7) |
C81 | 0.0218 (13) | 0.0343 (15) | 0.0196 (12) | 0.0047 (12) | 0.0084 (11) | 0.0031 (11) |
C111 | 0.0348 (16) | 0.0194 (13) | 0.0428 (15) | −0.0096 (12) | 0.0252 (13) | −0.0051 (12) |
N1—C2 | 1.330 (3) | C8—O81 | 1.373 (3) |
N1—C11a | 1.357 (3) | C8—C9 | 1.386 (3) |
C2—N3 | 1.332 (4) | C9—C10 | 1.387 (3) |
C2—H2 | 0.9500 | C9—H9 | 0.9500 |
N3—C4 | 1.336 (3) | C10—C10a | 1.385 (3) |
C4—C4a | 1.389 (3) | C10—H10 | 0.9500 |
C4—Cl4 | 1.741 (3) | C10a—N11 | 1.439 (3) |
C4a—C11a | 1.420 (3) | N11—C11a | 1.369 (3) |
C4a—C5 | 1.508 (3) | N11—C111 | 1.470 (3) |
C5—C6 | 1.545 (3) | C61—H61A | 0.9800 |
C5—H5A | 0.9900 | C61—H61B | 0.9800 |
C5—H5B | 0.9900 | C61—H61C | 0.9800 |
C6—C6a | 1.506 (3) | O81—C81 | 1.433 (3) |
C6—C61 | 1.527 (3) | C81—H81A | 0.9800 |
C6—H6 | 1.0000 | C81—H81B | 0.9800 |
C6a—C7 | 1.392 (3) | C81—H81C | 0.9800 |
C6a—C10a | 1.403 (3) | C111—H11A | 0.9800 |
C7—C8 | 1.394 (3) | C111—H11B | 0.9800 |
C7—H7 | 0.9500 | C111—H11C | 0.9800 |
C2—N1—C11a | 116.7 (2) | C8—C9—H9 | 120.7 |
N1—C2—N3 | 128.0 (2) | C10—C9—H9 | 120.7 |
N1—C2—H2 | 116.0 | C10a—C10—C9 | 122.0 (2) |
N3—C2—H2 | 116.0 | C10a—C10—H10 | 119.0 |
C2—N3—C4 | 113.3 (2) | C9—C10—H10 | 119.0 |
N3—C4—C4a | 126.6 (2) | C10—C10a—C6a | 119.7 (2) |
N3—C4—Cl4 | 114.22 (19) | C10—C10a—N11 | 119.8 (2) |
C4a—C4—Cl4 | 119.2 (2) | C6a—C10a—N11 | 120.5 (2) |
C4—C4a—C11a | 113.6 (2) | C11a—N11—C10a | 122.6 (2) |
C4—C4a—C5 | 119.9 (2) | C11a—N11—C111 | 118.4 (2) |
C11a—C4a—C5 | 126.3 (2) | C10a—N11—C111 | 116.3 (2) |
C4a—C5—C6 | 115.6 (2) | N1—C11a—N11 | 114.6 (2) |
C4a—C5—H5A | 108.4 | N1—C11a—C4a | 121.1 (2) |
C6—C5—H5A | 108.4 | N11—C11a—C4a | 124.2 (2) |
C4a—C5—H5B | 108.4 | C6—C61—H61A | 109.5 |
C6—C5—H5B | 108.4 | C6—C61—H61B | 109.5 |
H5A—C5—H5B | 107.4 | H61A—C61—H61B | 109.5 |
C6a—C6—C61 | 114.76 (19) | C6—C61—H61C | 109.5 |
C6a—C6—C5 | 107.52 (19) | H61A—C61—H61C | 109.5 |
C61—C6—C5 | 109.14 (19) | H61B—C61—H61C | 109.5 |
C6a—C6—H6 | 108.4 | C8—O81—C81 | 116.92 (19) |
C61—C6—H6 | 108.4 | O81—C81—H81A | 109.5 |
C5—C6—H6 | 108.4 | O81—C81—H81B | 109.5 |
C7—C6a—C10a | 118.1 (2) | H81A—C81—H81B | 109.5 |
C7—C6a—C6 | 122.8 (2) | O81—C81—H81C | 109.5 |
C10a—C6a—C6 | 118.7 (2) | H81A—C81—H81C | 109.5 |
C6a—C7—C8 | 121.6 (2) | H81B—C81—H81C | 109.5 |
C6a—C7—H7 | 119.2 | N11—C111—H11A | 109.5 |
C8—C7—H7 | 119.2 | N11—C111—H11B | 109.5 |
O81—C8—C9 | 125.2 (2) | H11A—C111—H11B | 109.5 |
O81—C8—C7 | 114.9 (2) | N11—C111—H11C | 109.5 |
C9—C8—C7 | 120.0 (2) | H11A—C111—H11C | 109.5 |
C8—C9—C10 | 118.6 (2) | H11B—C111—H11C | 109.5 |
C11a—N1—C2—N3 | −1.9 (4) | C9—C10—C10a—C6a | −0.2 (3) |
N1—C2—N3—C4 | 5.5 (4) | C9—C10—C10a—N11 | 177.5 (2) |
C2—N3—C4—C4a | −1.6 (4) | C7—C6a—C10a—C10 | 1.2 (3) |
C2—N3—C4—Cl4 | 176.68 (19) | C6—C6a—C10a—C10 | −173.0 (2) |
N3—C4—C4a—C11a | −5.0 (4) | C7—C6a—C10a—N11 | −176.5 (2) |
Cl4—C4—C4a—C11a | 176.78 (18) | C6—C6a—C10a—N11 | 9.3 (3) |
N3—C4—C4a—C5 | 170.2 (2) | C10—C10a—N11—C11a | 117.1 (3) |
Cl4—C4—C4a—C5 | −8.1 (3) | C6a—C10a—N11—C11a | −65.2 (3) |
C4—C4a—C5—C6 | −158.8 (2) | C10—C10a—N11—C111 | −43.7 (3) |
C11a—C4a—C5—C6 | 15.7 (3) | C6a—C10a—N11—C111 | 134.0 (2) |
C4a—C5—C6—C6a | −73.2 (2) | C2—N1—C11a—N11 | 175.5 (2) |
C4a—C5—C6—C61 | 161.8 (2) | C2—N1—C11a—C4a | −5.8 (3) |
C61—C6—C6a—C7 | 13.9 (3) | C10a—N11—C11a—N1 | −150.5 (2) |
C5—C6—C6a—C7 | −107.7 (2) | C111—N11—C11a—N1 | 10.0 (3) |
C61—C6—C6a—C10a | −172.2 (2) | C10a—N11—C11a—C4a | 30.9 (4) |
C5—C6—C6a—C10a | 66.2 (3) | C111—N11—C11a—C4a | −168.6 (2) |
C10a—C6a—C7—C8 | −0.8 (3) | C4—C4a—C11a—N1 | 8.8 (3) |
C6—C6a—C7—C8 | 173.1 (2) | C5—C4a—C11a—N1 | −166.1 (2) |
C6a—C7—C8—O81 | 180.0 (2) | C4—C4a—C11a—N11 | −172.7 (2) |
C6a—C7—C8—C9 | −0.6 (3) | C5—C4a—C11a—N11 | 12.5 (4) |
O81—C8—C9—C10 | −179.0 (2) | C9—C8—O81—C81 | −3.1 (3) |
C7—C8—C9—C10 | 1.6 (3) | C7—C8—O81—C81 | 176.3 (2) |
C8—C9—C10—C10a | −1.2 (3) |
C21H20ClN3O | F(000) = 768 |
Mr = 365.85 | Dx = 1.334 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.9431 (8) Å | Cell parameters from 4178 reflections |
b = 9.2078 (10) Å | θ = 2.8–27.5° |
c = 14.802 (4) Å | µ = 0.23 mm−1 |
β = 106.521 (8)° | T = 120 K |
V = 1821.9 (5) Å3 | Block, colourless |
Z = 4 | 0.28 × 0.22 × 0.16 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 3598 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2321 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.1°, θmin = 2.8° |
φ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.821, Tmax = 0.965 | l = −18→18 |
25675 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H-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 reflections | Δρmax = 0.43 e Å−3 |
238 parameters | Δρmin = −0.40 e Å−3 |
C21H20ClN3O | V = 1821.9 (5) Å3 |
Mr = 365.85 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.9431 (8) Å | µ = 0.23 mm−1 |
b = 9.2078 (10) Å | T = 120 K |
c = 14.802 (4) Å | 0.28 × 0.22 × 0.16 mm |
β = 106.521 (8)° |
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 = 0.965 | Rint = 0.103 |
25675 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.43 e Å−3 |
3598 reflections | Δρmin = −0.40 e Å−3 |
238 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.52465 (17) | 0.1084 (3) | 0.37737 (17) | 0.0203 (6) | |
C2 | 0.6009 (2) | 0.1994 (3) | 0.3850 (2) | 0.0210 (7) | |
N3 | 0.59558 (18) | 0.3446 (3) | 0.38135 (17) | 0.0218 (6) | |
C4 | 0.5053 (2) | 0.3963 (3) | 0.3768 (2) | 0.0211 (6) | |
Cl4 | 0.49862 (6) | 0.58666 (8) | 0.37500 (6) | 0.0284 (2) | |
C4a | 0.4195 (2) | 0.3182 (3) | 0.3747 (2) | 0.0215 (7) | |
C5 | 0.3278 (2) | 0.3918 (3) | 0.3895 (2) | 0.0235 (7) | |
H5A | 0.2909 | 0.4398 | 0.3299 | 0.028* | |
H5B | 0.3502 | 0.4685 | 0.4377 | 0.028* | |
C6 | 0.2555 (2) | 0.2898 (3) | 0.4204 (2) | 0.0252 (7) | |
H6 | 0.2963 | 0.2225 | 0.4696 | 0.030* | |
C6a | 0.2014 (2) | 0.1996 (3) | 0.3356 (2) | 0.0213 (7) | |
C7 | 0.1011 (2) | 0.2229 (3) | 0.2841 (2) | 0.0229 (7) | |
H7 | 0.0625 | 0.2928 | 0.3055 | 0.027* | |
C8 | 0.0579 (2) | 0.1451 (3) | 0.2026 (2) | 0.0221 (7) | |
C9 | 0.1138 (2) | 0.0431 (3) | 0.1701 (2) | 0.0200 (6) | |
H9 | 0.0842 | −0.0098 | 0.1140 | 0.024* | |
C10 | 0.2129 (2) | 0.0189 (3) | 0.2197 (2) | 0.0207 (6) | |
H10 | 0.2513 | −0.0502 | 0.1974 | 0.025* | |
C10a | 0.2563 (2) | 0.0958 (3) | 0.3027 (2) | 0.0201 (6) | |
N11 | 0.35823 (17) | 0.0647 (3) | 0.35510 (17) | 0.0214 (6) | |
C11a | 0.4336 (2) | 0.1660 (3) | 0.3684 (2) | 0.0189 (6) | |
C21 | 0.7002 (2) | 0.1318 (3) | 0.3944 (2) | 0.0212 (7) | |
C22 | 0.7055 (2) | −0.0138 (3) | 0.3685 (2) | 0.0257 (7) | |
H22 | 0.6461 | −0.0698 | 0.3476 | 0.031* | |
C23 | 0.7971 (2) | −0.0763 (4) | 0.3734 (2) | 0.0305 (8) | |
H23 | 0.8003 | −0.1746 | 0.3549 | 0.037* | |
C24 | 0.8845 (2) | 0.0045 (4) | 0.4052 (2) | 0.0314 (8) | |
H24 | 0.9472 | −0.0382 | 0.4075 | 0.038* | |
C25 | 0.8802 (2) | 0.1473 (4) | 0.4336 (2) | 0.0294 (8) | |
H25 | 0.9401 | 0.2015 | 0.4571 | 0.035* | |
C26 | 0.7883 (2) | 0.2112 (3) | 0.4277 (2) | 0.0240 (7) | |
H26 | 0.7855 | 0.3094 | 0.4465 | 0.029* | |
C61 | 0.1875 (2) | 0.3764 (4) | 0.4642 (2) | 0.0314 (8) | |
H61A | 0.1518 | 0.4501 | 0.4194 | 0.047* | |
H61B | 0.2277 | 0.4240 | 0.5217 | 0.047* | |
H61C | 0.1391 | 0.3110 | 0.4798 | 0.047* | |
O81 | −0.03908 (14) | 0.1617 (2) | 0.14707 (15) | 0.0275 (5) | |
C81 | −0.1018 (2) | 0.2587 (4) | 0.1798 (2) | 0.0318 (8) | |
H81A | −0.1036 | 0.2291 | 0.2429 | 0.048* | |
H81B | −0.1696 | 0.2560 | 0.1365 | 0.048* | |
H81C | −0.0752 | 0.3576 | 0.1824 | 0.048* | |
C111 | 0.3866 (2) | −0.0896 (3) | 0.3620 (2) | 0.0260 (7) | |
H11A | 0.4076 | −0.1174 | 0.3066 | 0.039* | |
H11B | 0.3292 | −0.1488 | 0.3649 | 0.039* | |
H11C | 0.4420 | −0.1053 | 0.4191 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0234 (13) | 0.0208 (14) | 0.0161 (13) | 0.0024 (11) | 0.0045 (10) | 0.0000 (11) |
C2 | 0.0237 (15) | 0.0231 (16) | 0.0151 (16) | 0.0021 (14) | 0.0037 (12) | 0.0003 (13) |
N3 | 0.0242 (13) | 0.0202 (13) | 0.0196 (14) | 0.0021 (11) | 0.0039 (11) | −0.0010 (11) |
C4 | 0.0295 (16) | 0.0150 (14) | 0.0169 (15) | 0.0032 (14) | 0.0035 (12) | −0.0028 (13) |
Cl4 | 0.0329 (4) | 0.0174 (4) | 0.0309 (5) | 0.0031 (4) | 0.0026 (3) | −0.0012 (3) |
C4a | 0.0231 (16) | 0.0235 (17) | 0.0160 (16) | 0.0011 (13) | 0.0022 (12) | −0.0032 (13) |
C5 | 0.0254 (16) | 0.0226 (16) | 0.0195 (16) | 0.0036 (13) | 0.0015 (12) | −0.0076 (13) |
C6 | 0.0258 (16) | 0.0279 (17) | 0.0219 (17) | 0.0031 (14) | 0.0069 (13) | −0.0044 (14) |
C6a | 0.0233 (15) | 0.0223 (16) | 0.0202 (16) | 0.0000 (13) | 0.0093 (13) | −0.0012 (13) |
C7 | 0.0250 (16) | 0.0225 (16) | 0.0240 (17) | 0.0007 (13) | 0.0114 (13) | −0.0053 (13) |
C8 | 0.0199 (15) | 0.0210 (15) | 0.0265 (17) | −0.0008 (13) | 0.0084 (13) | 0.0013 (13) |
C9 | 0.0245 (15) | 0.0167 (15) | 0.0189 (16) | −0.0035 (12) | 0.0064 (12) | −0.0042 (12) |
C10 | 0.0264 (16) | 0.0159 (15) | 0.0214 (16) | −0.0003 (13) | 0.0096 (13) | −0.0004 (13) |
C10a | 0.0194 (14) | 0.0200 (15) | 0.0211 (16) | −0.0023 (13) | 0.0063 (12) | 0.0040 (13) |
N11 | 0.0208 (12) | 0.0185 (13) | 0.0234 (14) | 0.0027 (11) | 0.0039 (10) | −0.0005 (11) |
C11a | 0.0213 (15) | 0.0204 (16) | 0.0142 (15) | 0.0020 (13) | 0.0039 (12) | 0.0000 (12) |
C21 | 0.0212 (15) | 0.0247 (17) | 0.0170 (15) | 0.0038 (13) | 0.0045 (12) | 0.0029 (13) |
C22 | 0.0233 (16) | 0.0271 (17) | 0.0246 (17) | 0.0009 (14) | 0.0037 (13) | −0.0034 (14) |
C23 | 0.0329 (18) | 0.0281 (18) | 0.0290 (19) | 0.0076 (16) | 0.0065 (14) | −0.0033 (15) |
C24 | 0.0263 (17) | 0.039 (2) | 0.0272 (18) | 0.0117 (16) | 0.0048 (14) | 0.0036 (16) |
C25 | 0.0230 (17) | 0.0342 (19) | 0.0276 (18) | −0.0009 (15) | 0.0017 (14) | 0.0072 (15) |
C26 | 0.0275 (16) | 0.0197 (16) | 0.0227 (17) | 0.0019 (14) | 0.0037 (13) | 0.0060 (13) |
C61 | 0.0356 (19) | 0.032 (2) | 0.0258 (18) | 0.0076 (15) | 0.0078 (15) | −0.0046 (14) |
O81 | 0.0197 (11) | 0.0300 (12) | 0.0312 (13) | 0.0026 (9) | 0.0050 (9) | −0.0083 (10) |
C81 | 0.0228 (16) | 0.039 (2) | 0.035 (2) | 0.0083 (15) | 0.0103 (14) | −0.0050 (16) |
C111 | 0.0266 (16) | 0.0193 (15) | 0.0315 (18) | 0.0022 (14) | 0.0073 (14) | 0.0047 (14) |
N1—C2 | 1.332 (4) | C10a—N11 | 1.441 (4) |
N1—C11a | 1.348 (4) | N11—C11a | 1.376 (4) |
C2—N3 | 1.340 (4) | N11—C111 | 1.471 (4) |
C2—C21 | 1.488 (4) | C21—C26 | 1.394 (4) |
N3—C4 | 1.330 (4) | C21—C22 | 1.402 (4) |
C4—C4a | 1.388 (4) | C22—C23 | 1.384 (4) |
C4—Cl4 | 1.755 (3) | C22—H22 | 0.9500 |
C4a—C11a | 1.422 (4) | C23—C24 | 1.390 (5) |
C4a—C5 | 1.516 (4) | C23—H23 | 0.9500 |
C5—C6 | 1.540 (4) | C24—C25 | 1.387 (5) |
C5—H5A | 0.9900 | C24—H24 | 0.9500 |
C5—H5B | 0.9900 | C25—C26 | 1.391 (4) |
C6—C6a | 1.516 (4) | C25—H25 | 0.9500 |
C6—C61 | 1.518 (4) | C26—H26 | 0.9500 |
C6—H6 | 1.0000 | C61—H61A | 0.9800 |
C6a—C10a | 1.396 (4) | C61—H61B | 0.9800 |
C6a—C7 | 1.406 (4) | C61—H61C | 0.9800 |
C7—C8 | 1.386 (4) | O81—C81 | 1.427 (4) |
C7—H7 | 0.9500 | C81—H81A | 0.9800 |
C8—O81 | 1.377 (3) | C81—H81B | 0.9800 |
C8—C9 | 1.390 (4) | C81—H81C | 0.9800 |
C9—C10 | 1.386 (4) | C111—H11A | 0.9800 |
C9—H9 | 0.9500 | C111—H11B | 0.9800 |
C10—C10a | 1.397 (4) | C111—H11C | 0.9800 |
C10—H10 | 0.9500 | ||
C2—N1—C11a | 117.9 (3) | C11a—N11—C111 | 117.7 (2) |
N1—C2—N3 | 126.2 (3) | C10a—N11—C111 | 115.7 (2) |
N1—C2—C21 | 116.3 (3) | N1—C11a—N11 | 114.0 (3) |
N3—C2—C21 | 117.4 (3) | N1—C11a—C4a | 121.7 (3) |
C4—N3—C2 | 113.6 (3) | N11—C11a—C4a | 124.3 (3) |
N3—C4—C4a | 127.8 (3) | C26—C21—C22 | 119.3 (3) |
N3—C4—Cl4 | 113.8 (2) | C26—C21—C2 | 121.1 (3) |
C4a—C4—Cl4 | 118.4 (2) | C22—C21—C2 | 119.6 (3) |
C4—C4a—C11a | 112.2 (3) | C23—C22—C21 | 120.2 (3) |
C4—C4a—C5 | 121.4 (3) | C23—C22—H22 | 119.9 |
C11a—C4a—C5 | 126.0 (3) | C21—C22—H22 | 119.9 |
C4a—C5—C6 | 114.8 (3) | C22—C23—C24 | 120.1 (3) |
C4a—C5—H5A | 108.6 | C22—C23—H23 | 119.9 |
C6—C5—H5A | 108.6 | C24—C23—H23 | 119.9 |
C4a—C5—H5B | 108.6 | C25—C24—C23 | 120.1 (3) |
C6—C5—H5B | 108.6 | C25—C24—H24 | 120.0 |
H5A—C5—H5B | 107.5 | C23—C24—H24 | 120.0 |
C6a—C6—C61 | 114.7 (3) | C24—C25—C26 | 120.0 (3) |
C6a—C6—C5 | 107.5 (2) | C24—C25—H25 | 120.0 |
C61—C6—C5 | 110.3 (3) | C26—C25—H25 | 120.0 |
C6a—C6—H6 | 108.0 | C25—C26—C21 | 120.3 (3) |
C61—C6—H6 | 108.0 | C25—C26—H26 | 119.9 |
C5—C6—H6 | 108.0 | C21—C26—H26 | 119.9 |
C10a—C6a—C7 | 118.4 (3) | C6—C61—H61A | 109.5 |
C10a—C6a—C6 | 118.1 (3) | C6—C61—H61B | 109.5 |
C7—C6a—C6 | 123.3 (3) | H61A—C61—H61B | 109.5 |
C8—C7—C6a | 120.8 (3) | C6—C61—H61C | 109.5 |
C8—C7—H7 | 119.6 | H61A—C61—H61C | 109.5 |
C6a—C7—H7 | 119.6 | H61B—C61—H61C | 109.5 |
O81—C8—C7 | 124.9 (3) | C8—O81—C81 | 117.4 (2) |
O81—C8—C9 | 114.9 (3) | O81—C81—H81A | 109.5 |
C7—C8—C9 | 120.2 (3) | O81—C81—H81B | 109.5 |
C10—C9—C8 | 119.8 (3) | H81A—C81—H81B | 109.5 |
C10—C9—H9 | 120.1 | O81—C81—H81C | 109.5 |
C8—C9—H9 | 120.1 | H81A—C81—H81C | 109.5 |
C9—C10—C10a | 120.1 (3) | H81B—C81—H81C | 109.5 |
C9—C10—H10 | 119.9 | N11—C111—H11A | 109.5 |
C10a—C10—H10 | 119.9 | N11—C111—H11B | 109.5 |
C6a—C10a—C10 | 120.6 (3) | H11A—C111—H11B | 109.5 |
C6a—C10a—N11 | 120.2 (3) | N11—C111—H11C | 109.5 |
C10—C10a—N11 | 119.2 (3) | H11A—C111—H11C | 109.5 |
C11a—N11—C10a | 122.6 (2) | H11B—C111—H11C | 109.5 |
C11a—N1—C2—N3 | −2.4 (4) | C9—C10—C10a—N11 | 177.6 (3) |
C11a—N1—C2—C21 | −179.8 (2) | C6a—C10a—N11—C11a | −64.6 (4) |
N1—C2—N3—C4 | 5.3 (4) | C10—C10a—N11—C11a | 116.6 (3) |
C21—C2—N3—C4 | −177.4 (2) | C6a—C10a—N11—C111 | 138.4 (3) |
C2—N3—C4—C4a | −0.6 (4) | C10—C10a—N11—C111 | −40.4 (4) |
C2—N3—C4—Cl4 | 178.5 (2) | C2—N1—C11a—N11 | 176.1 (2) |
N3—C4—C4a—C11a | −5.9 (4) | C2—N1—C11a—C4a | −5.2 (4) |
Cl4—C4—C4a—C11a | 175.0 (2) | C10a—N11—C11a—N1 | −150.4 (3) |
N3—C4—C4a—C5 | 167.4 (3) | C111—N11—C11a—N1 | 6.1 (4) |
Cl4—C4—C4a—C5 | −11.7 (4) | C10a—N11—C11a—C4a | 31.0 (4) |
C4—C4a—C5—C6 | −159.0 (3) | C111—N11—C11a—C4a | −172.5 (3) |
C11a—C4a—C5—C6 | 13.3 (4) | C4—C4a—C11a—N1 | 8.7 (4) |
C4a—C5—C6—C6a | −73.2 (3) | C5—C4a—C11a—N1 | −164.2 (3) |
C4a—C5—C6—C61 | 161.0 (3) | C4—C4a—C11a—N11 | −172.8 (3) |
C61—C6—C6a—C10a | −167.7 (3) | C5—C4a—C11a—N11 | 14.3 (5) |
C5—C6—C6a—C10a | 69.2 (3) | N1—C2—C21—C26 | −162.5 (3) |
C61—C6—C6a—C7 | 17.5 (4) | N3—C2—C21—C26 | 19.8 (4) |
C5—C6—C6a—C7 | −105.6 (3) | N1—C2—C21—C22 | 18.2 (4) |
C10a—C6a—C7—C8 | −0.2 (4) | N3—C2—C21—C22 | −159.5 (3) |
C6—C6a—C7—C8 | 174.6 (3) | C26—C21—C22—C23 | −2.0 (4) |
C6a—C7—C8—O81 | −179.2 (3) | C2—C21—C22—C23 | 177.4 (3) |
C6a—C7—C8—C9 | −0.4 (5) | C21—C22—C23—C24 | 0.9 (5) |
O81—C8—C9—C10 | 179.1 (3) | C22—C23—C24—C25 | 1.0 (5) |
C7—C8—C9—C10 | 0.3 (4) | C23—C24—C25—C26 | −1.9 (5) |
C8—C9—C10—C10a | 0.5 (4) | C24—C25—C26—C21 | 0.8 (5) |
C7—C6a—C10a—C10 | 1.0 (4) | C22—C21—C26—C25 | 1.1 (4) |
C6—C6a—C10a—C10 | −174.1 (3) | C2—C21—C26—C25 | −178.2 (3) |
C7—C6a—C10a—N11 | −177.7 (3) | C7—C8—O81—C81 | −4.8 (4) |
C6—C6a—C10a—N11 | 7.2 (4) | C9—C8—O81—C81 | 176.4 (3) |
C9—C10—C10a—C6a | −1.2 (4) |
Cg2 represents the centroid of the ring C6a/C7–C10/C10a. |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···Cg2i | 0.95 | 2.64 | 3.511 (4) | 153 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C14H14ClN3 | C14H14ClN3O | C15H16ClN3O | C21H20ClN3O |
Mr | 259.73 | 275.73 | 289.76 | 365.85 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 | 120 |
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), 90 | 90, 122.774 (5), 90 | 90, 106.521 (8), 90 |
V (Å3) | 618.34 (16) | 1252.27 (19) | 1344.27 (17) | 1821.9 (5) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.29 | 0.30 | 0.28 | 0.23 |
Crystal size (mm) | 0.37 × 0.21 × 0.17 | 0.32 × 0.18 × 0.16 | 0.22 × 0.20 × 0.16 | 0.28 × 0.22 × 0.16 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.719, 0.951 | 0.761, 0.953 | 0.834, 0.956 | 0.821, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11681, 2835, 2068 | 22327, 2870, 2154 | 14823, 3076, 1978 | 25675, 3598, 2321 |
Rint | 0.081 | 0.069 | 0.099 | 0.103 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.618 |
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 reflections | 2835 | 2870 | 3076 | 3598 |
No. of parameters | 165 | 177 | 184 | 238 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.39 | 0.34, −0.28 | 0.26, −0.25 | 0.43, −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).
Parameter | (I) | (II) | (III) | (IV) | (V) |
(a) | Ring-puckering parameters | ||||
Q | 0.855 (3) | 0.808 (2) | 0.875 (3) | 0.889 (3) | 0.837 (4) |
φ2 | 50.3 (2) | 43.38 (7) | 48.85 (18) | 47.7 (2) | 47.1 (3) |
φ3 | 290.1 (5) | 291.9 (4) | 290.5 (5) | 288.6 (6) | 289.0 (8) |
(b) | Inter-bond, torsion and dihedral angles | ||||
C7—C8—O81 | 116.88 (19) | 114.9 (2) | 124.9 (3) | ||
C9—C8—O81 | 123.7 (2) | 125.2 (2) | 114.9 (3) | ||
C8—O81—H81 | 111.2 (18) | ||||
C8—O81—C81 | 116.92 (19) | 117.4 (2) | |||
C7—C8—O81—H81 | 169 (2) | ||||
C7—C8—O81—C81 | 176.3 (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—C10 | 65.4 (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—C111 | 137.3 (2) | 136.0 (2) | 134.0 (2) | 138.4 (3) | 140.6 (4) |
Dihedral | 50.88 (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)°. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(II) | O81—H81···N3i | 0.88 (3) | 1.91 (3) | 2.737 (2) | 156 (3) |
(IV) | C23—H23···Cg2ii | 0.95 | 2.64 | 3.511 (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. |
Compound | C—Cl···Cg | C—Cl | Cl···Cg | C···Cg | C—Cl···Cg |
(I) | C4—Cl4···Cg1iii | 1.750 (3) | 3.7045 (15) | 4.209 (3) | 94.10 (10) |
(II) | C4—Cl4···Cg1iv | 1.741 (3) | 3.7994 (16) | 3.637 (4) | 71.30 (12) |
(IV) | C4—Cl4···Cg1v | 1.755 (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. |