A versatile synthetic method has been developed for the formation of variously substituted polycyclic pyrimidoazepine derivatives, formed by nucleophilic substitution reactions on the corresponding chloro-substituted compounds; the reactions can be promoted either by conventional heating in basic solutions or by microwave heating in solvent-free systems. Thus, (6RS)-6,11-dimethyl-3,5,6,11-tetrahydro-4H-benzo[b]pyrimido[5,4-f]azepin-4-one, C14H15N3O, (I), was isolated from a solution containing (6RS)-4-chloro-8-hydroxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine and benzene-1,2-diamine; (6RS)-4-butoxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepin-8-ol, C18H23N3O2, (II), was formed by reaction of the corresponding 6-chloro compound with butanol, and (RS)-4-dimethylamino-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepin-8-ol, C16H20N4O, (III), was formed by reaction of the chloro analogue with alkaline dimethylformamide. (6RS)-N-Benzyl-8-methoxy-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepin-4-amine, C22H24N4O, (IV), (6RS)-N-benzyl-6-methyl-1,2,6,7-tetrahydropyrimido[5′,4′:6,7]azepino[3,2,1-hi]indol-8-amine, C22H22N4, (V), and (7RS)-N-benzyl-7-methyl-2,3,7,8-tetrahydro-1H-pyrimido[5′,4′:6,7]azepino[3,2,1-ij]quinolin-9-amine, C23H24N4, (VI), were all formed by reaction of the corresponding chloro compounds with benzylamine under microwave irradiation. In each of compounds (I)–(IV) and (VI), the azepine ring adopts a conformation close to the boat form, with the C-methyl group in a quasi-equatorial site, whereas the corresponding ring in (V) adopts a conformation intermediate between the twist-boat and twist-chair forms, with the C-methyl group in a quasi-axial site. No two of the structures of (I)–(VI) exhibit the same range of intermolecular hydrogen bonds: different types of sheet are formed in each of (I), (II), (V) and (VI), and different types of chain in each of (III) and (IV).
Supporting information
CCDC references: 1469144; 1469143; 1469142; 1469141; 1469140; 1469139
Data collection: COLLECT (Hooft, 1999) for (I); APEX2 (Bruker, 2007) for (II), (III), (IV), (V), (VI). Cell refinement: DIRAX/LSQ (Duisenberg et al., 2000) for (I); SAINT (Bruker, 2007) for (II), (III), (IV), (V), (VI). Data reduction: EVALCCD (Duisenberg et al., 2003) for (I); SAINT (Bruker, 2012) for (II), (III), (IV), (V), (VI). For all compounds, 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).
(I) 6,11-Dimethyl-3,5,6,11-tetrahydro-4
H-benzo[
b]pyrimido[5,4-
f]azepin-4-one
top
Crystal data top
C14H15N3O | F(000) = 512 |
Mr = 241.29 | Dx = 1.369 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.0839 (16) Å | Cell parameters from 2683 reflections |
b = 4.2350 (3) Å | θ = 2.7–27.5° |
c = 16.2258 (18) Å | µ = 0.09 mm−1 |
β = 94.047 (8)° | T = 120 K |
V = 1171.01 (19) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.18 × 0.16 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2681 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1502 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.115 |
φ and ω scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −21→22 |
Tmin = 0.851, Tmax = 0.986 | k = −5→5 |
17222 measured reflections | l = −20→20 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.5675P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2681 reflections | Δρmax = 0.28 e Å−3 |
168 parameters | Δρmin = −0.27 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.08849 (12) | 0.4412 (5) | 0.30295 (13) | 0.0240 (5) | |
C2 | 0.02938 (15) | 0.3079 (7) | 0.33612 (16) | 0.0253 (6) | |
H2 | −0.0189 | 0.2940 | 0.3036 | 0.030* | |
N3 | 0.03210 (12) | 0.1899 (6) | 0.41247 (13) | 0.0230 (5) | |
H3 | −0.0079 (16) | 0.095 (7) | 0.4311 (17) | 0.028* | |
C4 | 0.09824 (14) | 0.2217 (6) | 0.46586 (15) | 0.0212 (6) | |
O4 | 0.09755 (10) | 0.1224 (5) | 0.53850 (11) | 0.0290 (5) | |
C4A | 0.16404 (14) | 0.3752 (6) | 0.43355 (14) | 0.0181 (6) | |
C5 | 0.23085 (13) | 0.4446 (6) | 0.49697 (15) | 0.0198 (6) | |
H5A | 0.2505 | 0.2411 | 0.5202 | 0.024* | |
H5B | 0.2095 | 0.5653 | 0.5426 | 0.024* | |
C6 | 0.30038 (13) | 0.6269 (6) | 0.46742 (14) | 0.0182 (6) | |
H6 | 0.2801 | 0.8337 | 0.4452 | 0.022* | |
C6A | 0.33746 (14) | 0.4584 (6) | 0.39826 (15) | 0.0189 (6) | |
C7 | 0.41255 (14) | 0.3254 (6) | 0.40727 (16) | 0.0220 (6) | |
H7 | 0.4407 | 0.3327 | 0.4598 | 0.026* | |
C8 | 0.44722 (14) | 0.1833 (6) | 0.34197 (16) | 0.0241 (6) | |
H8 | 0.4979 | 0.0912 | 0.3501 | 0.029* | |
C9 | 0.40718 (15) | 0.1773 (6) | 0.26497 (16) | 0.0238 (6) | |
H9 | 0.4307 | 0.0844 | 0.2195 | 0.029* | |
C10 | 0.33256 (14) | 0.3071 (6) | 0.25404 (15) | 0.0214 (6) | |
H10 | 0.3055 | 0.3035 | 0.2008 | 0.026* | |
C10A | 0.29676 (14) | 0.4426 (6) | 0.32008 (15) | 0.0185 (6) | |
N11 | 0.21940 (11) | 0.5721 (5) | 0.30672 (12) | 0.0186 (5) | |
C11A | 0.15830 (14) | 0.4585 (6) | 0.35098 (15) | 0.0192 (6) | |
C61 | 0.35772 (14) | 0.6979 (7) | 0.54163 (15) | 0.0230 (6) | |
H61A | 0.4030 | 0.8138 | 0.5232 | 0.034* | |
H61B | 0.3756 | 0.4993 | 0.5676 | 0.034* | |
H61C | 0.3314 | 0.8262 | 0.5817 | 0.034* | |
C111 | 0.19808 (15) | 0.7032 (7) | 0.22439 (15) | 0.0236 (6) | |
H11A | 0.1582 | 0.8676 | 0.2287 | 0.035* | |
H11B | 0.1771 | 0.5349 | 0.1878 | 0.035* | |
H11C | 0.2447 | 0.7947 | 0.2018 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0169 (11) | 0.0323 (13) | 0.0221 (12) | −0.0030 (10) | −0.0028 (9) | 0.0020 (10) |
C2 | 0.0167 (13) | 0.0376 (16) | 0.0214 (14) | −0.0021 (12) | −0.0007 (11) | 0.0014 (13) |
N3 | 0.0148 (11) | 0.0351 (14) | 0.0193 (12) | −0.0062 (10) | 0.0018 (9) | 0.0048 (10) |
C4 | 0.0164 (13) | 0.0259 (15) | 0.0213 (14) | −0.0003 (11) | 0.0013 (11) | −0.0011 (12) |
O4 | 0.0201 (9) | 0.0470 (14) | 0.0199 (10) | −0.0077 (9) | 0.0023 (7) | 0.0072 (9) |
C4A | 0.0164 (12) | 0.0215 (14) | 0.0166 (13) | 0.0003 (11) | 0.0014 (10) | −0.0006 (11) |
C5 | 0.0183 (12) | 0.0226 (13) | 0.0186 (13) | 0.0002 (11) | 0.0017 (10) | −0.0024 (11) |
C6 | 0.0171 (12) | 0.0217 (14) | 0.0155 (13) | −0.0028 (10) | −0.0004 (10) | 0.0021 (11) |
C6A | 0.0193 (13) | 0.0178 (13) | 0.0199 (13) | −0.0044 (11) | 0.0036 (10) | 0.0016 (11) |
C7 | 0.0196 (13) | 0.0246 (15) | 0.0216 (14) | −0.0044 (11) | 0.0004 (11) | 0.0030 (12) |
C8 | 0.0160 (13) | 0.0268 (14) | 0.0300 (15) | −0.0004 (11) | 0.0051 (11) | 0.0004 (13) |
C9 | 0.0248 (14) | 0.0262 (15) | 0.0214 (14) | −0.0014 (12) | 0.0093 (11) | −0.0028 (12) |
C10 | 0.0240 (14) | 0.0226 (14) | 0.0176 (13) | −0.0058 (12) | 0.0021 (10) | 0.0000 (11) |
C10A | 0.0180 (12) | 0.0178 (13) | 0.0196 (13) | −0.0049 (11) | 0.0015 (10) | 0.0007 (11) |
N11 | 0.0179 (11) | 0.0234 (12) | 0.0145 (10) | −0.0034 (9) | 0.0006 (8) | 0.0028 (9) |
C11A | 0.0180 (13) | 0.0197 (14) | 0.0201 (13) | 0.0005 (11) | 0.0031 (10) | −0.0028 (11) |
C61 | 0.0217 (13) | 0.0275 (15) | 0.0194 (13) | −0.0053 (11) | −0.0009 (10) | −0.0028 (12) |
C111 | 0.0224 (13) | 0.0290 (15) | 0.0191 (13) | −0.0045 (12) | 0.0004 (11) | 0.0074 (12) |
Geometric parameters (Å, º) top
N1—C2 | 1.306 (3) | C7—C8 | 1.387 (4) |
N1—C11A | 1.380 (3) | C7—H7 | 0.9500 |
C2—N3 | 1.334 (3) | C8—C9 | 1.382 (4) |
C2—H2 | 0.9500 | C8—H8 | 0.9500 |
N3—C4 | 1.381 (3) | C9—C10 | 1.388 (4) |
N3—H3 | 0.86 (3) | C9—H9 | 0.9500 |
C4—O4 | 1.252 (3) | C10—C10A | 1.394 (3) |
C4—C4A | 1.430 (3) | C10—H10 | 0.9500 |
C4A—C11A | 1.382 (3) | C10A—N11 | 1.433 (3) |
C4A—C5 | 1.511 (3) | N11—C11A | 1.394 (3) |
C5—C6 | 1.522 (3) | N11—C111 | 1.469 (3) |
C5—H5A | 0.9900 | C61—H61A | 0.9800 |
C5—H5B | 0.9900 | C61—H61B | 0.9800 |
C6—C6A | 1.507 (3) | C61—H61C | 0.9800 |
C6—C61 | 1.528 (3) | C111—H11A | 0.9800 |
C6—H6 | 1.0000 | C111—H11B | 0.9800 |
C6A—C7 | 1.399 (3) | C111—H11C | 0.9800 |
C6A—C10A | 1.405 (3) | | |
| | | |
C2—N1—C11A | 116.9 (2) | C9—C8—C7 | 119.2 (2) |
N1—C2—N3 | 124.6 (2) | C9—C8—H8 | 120.4 |
N1—C2—H2 | 117.7 | C7—C8—H8 | 120.4 |
N3—C2—H2 | 117.7 | C8—C9—C10 | 120.0 (2) |
C2—N3—C4 | 121.3 (2) | C8—C9—H9 | 120.0 |
C2—N3—H3 | 121.5 (18) | C10—C9—H9 | 120.0 |
C4—N3—H3 | 117.2 (18) | C9—C10—C10A | 120.9 (2) |
O4—C4—N3 | 119.7 (2) | C9—C10—H10 | 119.6 |
O4—C4—C4A | 123.9 (2) | C10A—C10—H10 | 119.6 |
N3—C4—C4A | 116.4 (2) | C10—C10A—C6A | 119.9 (2) |
C11A—C4A—C4 | 117.9 (2) | C10—C10A—N11 | 119.4 (2) |
C11A—C4A—C5 | 127.5 (2) | C6A—C10A—N11 | 120.7 (2) |
C4—C4A—C5 | 114.5 (2) | C11A—N11—C10A | 120.4 (2) |
C4A—C5—C6 | 116.9 (2) | C11A—N11—C111 | 116.90 (19) |
C4A—C5—H5A | 108.1 | C10A—N11—C111 | 116.69 (19) |
C6—C5—H5A | 108.1 | N1—C11A—C4A | 122.2 (2) |
C4A—C5—H5B | 108.1 | N1—C11A—N11 | 112.1 (2) |
C6—C5—H5B | 108.1 | C4A—C11A—N11 | 125.7 (2) |
H5A—C5—H5B | 107.3 | C6—C61—H61A | 109.5 |
C6A—C6—C5 | 111.9 (2) | C6—C61—H61B | 109.5 |
C6A—C6—C61 | 113.6 (2) | H61A—C61—H61B | 109.5 |
C5—C6—C61 | 108.84 (19) | C6—C61—H61C | 109.5 |
C6A—C6—H6 | 107.4 | H61A—C61—H61C | 109.5 |
C5—C6—H6 | 107.4 | H61B—C61—H61C | 109.5 |
C61—C6—H6 | 107.4 | N11—C111—H11A | 109.5 |
C7—C6A—C10A | 117.8 (2) | N11—C111—H11B | 109.5 |
C7—C6A—C6 | 122.9 (2) | H11A—C111—H11B | 109.5 |
C10A—C6A—C6 | 119.2 (2) | N11—C111—H11C | 109.5 |
C8—C7—C6A | 122.2 (2) | H11A—C111—H11C | 109.5 |
C8—C7—H7 | 118.9 | H11B—C111—H11C | 109.5 |
C6A—C7—H7 | 118.9 | | |
| | | |
C11A—N1—C2—N3 | 0.2 (4) | C9—C10—C10A—C6A | 2.2 (4) |
N1—C2—N3—C4 | 4.9 (4) | C9—C10—C10A—N11 | −179.5 (2) |
C2—N3—C4—O4 | 176.4 (3) | C7—C6A—C10A—C10 | −2.2 (3) |
C2—N3—C4—C4A | −2.6 (4) | C6—C6A—C10A—C10 | 175.5 (2) |
O4—C4—C4A—C11A | 176.7 (3) | C7—C6A—C10A—N11 | 179.5 (2) |
N3—C4—C4A—C11A | −4.4 (3) | C6—C6A—C10A—N11 | −2.8 (3) |
O4—C4—C4A—C5 | −6.8 (4) | C10—C10A—N11—C11A | 121.3 (3) |
N3—C4—C4A—C5 | 172.1 (2) | C6A—C10A—N11—C11A | −60.4 (3) |
C11A—C4A—C5—C6 | −0.1 (4) | C10—C10A—N11—C111 | −30.6 (3) |
C4—C4A—C5—C6 | −176.1 (2) | C6A—C10A—N11—C111 | 147.7 (2) |
C4A—C5—C6—C6A | −58.6 (3) | C2—N1—C11A—C4A | −7.7 (4) |
C4A—C5—C6—C61 | 175.1 (2) | C2—N1—C11A—N11 | 173.3 (2) |
C5—C6—C6A—C7 | −111.9 (3) | C4—C4A—C11A—N1 | 9.7 (4) |
C61—C6—C6A—C7 | 11.8 (3) | C5—C4A—C11A—N1 | −166.2 (2) |
C5—C6—C6A—C10A | 70.6 (3) | C4—C4A—C11A—N11 | −171.4 (2) |
C61—C6—C6A—C10A | −165.7 (2) | C5—C4A—C11A—N11 | 12.7 (4) |
C10A—C6A—C7—C8 | 0.5 (4) | C10A—N11—C11A—N1 | −141.6 (2) |
C6—C6A—C7—C8 | −177.1 (2) | C111—N11—C11A—N1 | 10.3 (3) |
C6A—C7—C8—C9 | 1.2 (4) | C10A—N11—C11A—C4A | 39.5 (4) |
C7—C8—C9—C10 | −1.2 (4) | C111—N11—C11A—C4A | −168.7 (2) |
C8—C9—C10—C10A | −0.4 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.87 (3) | 1.88 (3) | 2.745 (3) | 175 (3) |
C2—H2···N1ii | 0.95 | 2.52 | 3.304 (3) | 140 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y−1/2, −z+1/2. |
(II) 4-Butoxy-6,11-dimethyl-6,11-dihydro-5
H-benzo[
b]pyrimido[5,4-
f]azepin-8-ol
top
Crystal data top
C18H23N3O2 | F(000) = 672 |
Mr = 313.39 | Dx = 1.211 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 11.4233 (4) Å | Cell parameters from 2981 reflections |
b = 7.3707 (3) Å | θ = 4.3–66.7° |
c = 20.4624 (7) Å | µ = 0.64 mm−1 |
β = 93.561 (2)° | T = 100 K |
V = 1719.56 (11) Å3 | Block, colourless |
Z = 4 | 0.14 × 0.12 × 0.12 mm |
Data collection top
Bruker D8 Venture diffractometer | 2981 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 1931 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.058 |
φ and ω scans | θmax = 66.7°, θmin = 4.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→13 |
Tmin = 0.776, Tmax = 0.926 | k = −8→8 |
15100 measured reflections | l = −23→24 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.7285P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.27 e Å−3 |
2981 reflections | Δρmin = −0.24 e Å−3 |
215 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0056 (5) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.04553 (18) | 0.7842 (3) | 0.52658 (9) | 0.0337 (5) | |
C2 | 0.1058 (2) | 0.8294 (4) | 0.47593 (11) | 0.0360 (6) | |
H2 | 0.0768 | 0.9293 | 0.4504 | 0.043* | |
N3 | 0.20316 (18) | 0.7500 (3) | 0.45668 (9) | 0.0327 (5) | |
C4 | 0.2386 (2) | 0.6061 (3) | 0.49265 (11) | 0.0300 (6) | |
C4A | 0.1849 (2) | 0.5437 (3) | 0.54795 (10) | 0.0289 (6) | |
C5 | 0.2318 (2) | 0.3718 (3) | 0.57956 (11) | 0.0345 (6) | |
H5A | 0.3142 | 0.3937 | 0.5955 | 0.041* | |
H5B | 0.2325 | 0.2769 | 0.5454 | 0.041* | |
C6 | 0.1659 (2) | 0.2967 (3) | 0.63673 (11) | 0.0338 (6) | |
H6 | 0.0831 | 0.2740 | 0.6198 | 0.041* | |
C6A | 0.1618 (2) | 0.4369 (3) | 0.69070 (11) | 0.0285 (6) | |
C7 | 0.2273 (2) | 0.4235 (3) | 0.75010 (11) | 0.0305 (6) | |
H7 | 0.2806 | 0.3254 | 0.7570 | 0.037* | |
C8 | 0.2165 (2) | 0.5504 (3) | 0.79962 (11) | 0.0294 (6) | |
C9 | 0.1374 (2) | 0.6907 (3) | 0.79041 (11) | 0.0306 (6) | |
H9 | 0.1266 | 0.7745 | 0.8248 | 0.037* | |
C10 | 0.0734 (2) | 0.7093 (3) | 0.73068 (10) | 0.0289 (6) | |
H10 | 0.0201 | 0.8075 | 0.7240 | 0.035* | |
C10A | 0.0872 (2) | 0.5848 (3) | 0.68071 (10) | 0.0274 (6) | |
N11 | 0.02281 (17) | 0.6077 (3) | 0.61835 (8) | 0.0296 (5) | |
C11A | 0.0873 (2) | 0.6441 (3) | 0.56392 (10) | 0.0293 (6) | |
O41 | 0.33093 (14) | 0.5083 (2) | 0.47471 (7) | 0.0333 (4) | |
C41 | 0.3787 (2) | 0.5467 (4) | 0.41240 (11) | 0.0348 (6) | |
H41A | 0.4282 | 0.6569 | 0.4157 | 0.042* | |
H41B | 0.3145 | 0.5672 | 0.3784 | 0.042* | |
C42 | 0.4504 (2) | 0.3862 (4) | 0.39495 (11) | 0.0347 (6) | |
H42A | 0.4025 | 0.2748 | 0.3975 | 0.042* | |
H42B | 0.5186 | 0.3746 | 0.4270 | 0.042* | |
C43 | 0.4938 (2) | 0.4031 (4) | 0.32635 (12) | 0.0378 (7) | |
H43A | 0.4254 | 0.4115 | 0.2943 | 0.045* | |
H43B | 0.5396 | 0.5166 | 0.3235 | 0.045* | |
C44 | 0.5694 (3) | 0.2447 (4) | 0.30838 (14) | 0.0533 (8) | |
H44A | 0.6393 | 0.2393 | 0.3386 | 0.080* | |
H44B | 0.5931 | 0.2602 | 0.2635 | 0.080* | |
H44C | 0.5247 | 0.1318 | 0.3114 | 0.080* | |
O81 | 0.28456 (15) | 0.5270 (2) | 0.85678 (7) | 0.0347 (5) | |
H81 | 0.261 (2) | 0.616 (4) | 0.8913 (13) | 0.052* | |
C61 | 0.2172 (3) | 0.1160 (4) | 0.65817 (12) | 0.0439 (7) | |
H61A | 0.3003 | 0.1314 | 0.6719 | 0.066* | |
H61B | 0.2095 | 0.0301 | 0.6216 | 0.066* | |
H61C | 0.1751 | 0.0692 | 0.6949 | 0.066* | |
C111 | −0.0909 (2) | 0.6984 (4) | 0.62020 (12) | 0.0361 (7) | |
H11A | −0.0786 | 0.8283 | 0.6283 | 0.054* | |
H11B | −0.1346 | 0.6461 | 0.6554 | 0.054* | |
H11C | −0.1355 | 0.6816 | 0.5782 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0404 (13) | 0.0364 (12) | 0.0246 (11) | 0.0050 (10) | 0.0055 (9) | 0.0028 (9) |
C2 | 0.0437 (16) | 0.0367 (15) | 0.0279 (13) | 0.0057 (13) | 0.0059 (12) | 0.0038 (11) |
N3 | 0.0377 (13) | 0.0341 (12) | 0.0267 (11) | 0.0030 (10) | 0.0049 (9) | 0.0006 (9) |
C4 | 0.0297 (14) | 0.0351 (15) | 0.0251 (12) | 0.0030 (12) | 0.0018 (11) | −0.0026 (11) |
C4A | 0.0355 (14) | 0.0306 (14) | 0.0206 (12) | 0.0019 (12) | 0.0037 (10) | −0.0003 (10) |
C5 | 0.0460 (16) | 0.0351 (15) | 0.0230 (12) | 0.0052 (13) | 0.0073 (11) | 0.0008 (11) |
C6 | 0.0457 (16) | 0.0320 (14) | 0.0244 (12) | 0.0025 (13) | 0.0073 (11) | 0.0015 (11) |
C6A | 0.0327 (14) | 0.0309 (14) | 0.0228 (12) | −0.0030 (12) | 0.0083 (10) | 0.0026 (10) |
C7 | 0.0342 (14) | 0.0283 (14) | 0.0299 (13) | 0.0024 (12) | 0.0087 (11) | 0.0022 (11) |
C8 | 0.0322 (14) | 0.0341 (14) | 0.0224 (12) | −0.0025 (12) | 0.0050 (10) | 0.0040 (11) |
C9 | 0.0362 (15) | 0.0309 (14) | 0.0252 (12) | −0.0009 (12) | 0.0070 (10) | −0.0019 (10) |
C10 | 0.0325 (14) | 0.0297 (14) | 0.0253 (12) | −0.0002 (11) | 0.0071 (10) | 0.0009 (10) |
C10A | 0.0304 (14) | 0.0308 (14) | 0.0215 (12) | −0.0021 (12) | 0.0043 (10) | 0.0029 (10) |
N11 | 0.0319 (12) | 0.0357 (12) | 0.0217 (10) | 0.0023 (10) | 0.0054 (9) | 0.0001 (9) |
C11A | 0.0346 (15) | 0.0302 (14) | 0.0231 (12) | −0.0005 (12) | 0.0016 (10) | −0.0005 (11) |
O41 | 0.0373 (10) | 0.0414 (10) | 0.0219 (8) | 0.0047 (9) | 0.0067 (7) | 0.0023 (7) |
C41 | 0.0371 (15) | 0.0410 (15) | 0.0273 (13) | 0.0002 (13) | 0.0103 (11) | 0.0025 (11) |
C42 | 0.0335 (14) | 0.0415 (16) | 0.0296 (13) | 0.0001 (13) | 0.0058 (11) | 0.0000 (12) |
C43 | 0.0405 (16) | 0.0408 (16) | 0.0331 (14) | −0.0028 (13) | 0.0099 (12) | −0.0051 (12) |
C44 | 0.0545 (19) | 0.0499 (19) | 0.0581 (19) | −0.0024 (16) | 0.0252 (15) | −0.0107 (16) |
O81 | 0.0404 (11) | 0.0418 (11) | 0.0220 (9) | 0.0035 (9) | 0.0015 (7) | −0.0013 (8) |
C61 | 0.0572 (19) | 0.0395 (17) | 0.0356 (14) | 0.0027 (15) | 0.0064 (13) | −0.0013 (12) |
C111 | 0.0323 (15) | 0.0463 (17) | 0.0305 (13) | 0.0038 (13) | 0.0076 (11) | −0.0020 (12) |
Geometric parameters (Å, º) top
N1—C2 | 1.322 (3) | C10—H10 | 0.9500 |
N1—C11A | 1.354 (3) | C10A—N11 | 1.443 (3) |
C2—N3 | 1.337 (3) | N11—C11A | 1.399 (3) |
C2—H2 | 0.9500 | N11—C111 | 1.463 (3) |
N3—C4 | 1.339 (3) | O41—C41 | 1.445 (3) |
C4—O41 | 1.347 (3) | C41—C42 | 1.495 (3) |
C4—C4A | 1.398 (3) | C41—H41A | 0.9900 |
C4A—C11A | 1.394 (3) | C41—H41B | 0.9900 |
C4A—C5 | 1.506 (3) | C42—C43 | 1.523 (3) |
C5—C6 | 1.533 (3) | C42—H42A | 0.9900 |
C5—H5A | 0.9900 | C42—H42B | 0.9900 |
C5—H5B | 0.9900 | C43—C44 | 1.511 (4) |
C6—C61 | 1.509 (3) | C43—H43A | 0.9900 |
C6—C6A | 1.515 (3) | C43—H43B | 0.9900 |
C6—H6 | 1.0000 | C44—H44A | 0.9800 |
C6A—C7 | 1.391 (3) | C44—H44B | 0.9800 |
C6A—C10A | 1.391 (3) | C44—H44C | 0.9800 |
C7—C8 | 1.391 (3) | O81—H81 | 1.01 (3) |
C7—H7 | 0.9500 | C61—H61A | 0.9800 |
C8—O81 | 1.375 (3) | C61—H61B | 0.9800 |
C8—C9 | 1.378 (3) | C61—H61C | 0.9800 |
C9—C10 | 1.392 (3) | C111—H11A | 0.9800 |
C9—H9 | 0.9500 | C111—H11B | 0.9800 |
C10—C10A | 1.390 (3) | C111—H11C | 0.9800 |
| | | |
C2—N1—C11A | 116.9 (2) | C10A—N11—C111 | 115.79 (18) |
N1—C2—N3 | 127.1 (2) | N1—C11A—C4A | 122.1 (2) |
N1—C2—H2 | 116.4 | N1—C11A—N11 | 114.3 (2) |
N3—C2—H2 | 116.4 | C4A—C11A—N11 | 123.6 (2) |
C2—N3—C4 | 114.4 (2) | C4—O41—C41 | 118.71 (18) |
N3—C4—O41 | 119.3 (2) | O41—C41—C42 | 107.4 (2) |
N3—C4—C4A | 124.9 (2) | O41—C41—H41A | 110.2 |
O41—C4—C4A | 115.8 (2) | C42—C41—H41A | 110.2 |
C11A—C4A—C4 | 114.4 (2) | O41—C41—H41B | 110.2 |
C11A—C4A—C5 | 127.9 (2) | C42—C41—H41B | 110.2 |
C4—C4A—C5 | 117.5 (2) | H41A—C41—H41B | 108.5 |
C4A—C5—C6 | 117.0 (2) | C41—C42—C43 | 111.7 (2) |
C4A—C5—H5A | 108.1 | C41—C42—H42A | 109.3 |
C6—C5—H5A | 108.1 | C43—C42—H42A | 109.3 |
C4A—C5—H5B | 108.1 | C41—C42—H42B | 109.3 |
C6—C5—H5B | 108.1 | C43—C42—H42B | 109.3 |
H5A—C5—H5B | 107.3 | H42A—C42—H42B | 107.9 |
C61—C6—C6A | 114.8 (2) | C44—C43—C42 | 112.6 (2) |
C61—C6—C5 | 109.9 (2) | C44—C43—H43A | 109.1 |
C6A—C6—C5 | 110.4 (2) | C42—C43—H43A | 109.1 |
C61—C6—H6 | 107.2 | C44—C43—H43B | 109.1 |
C6A—C6—H6 | 107.2 | C42—C43—H43B | 109.1 |
C5—C6—H6 | 107.2 | H43A—C43—H43B | 107.8 |
C7—C6A—C10A | 118.4 (2) | C43—C44—H44A | 109.5 |
C7—C6A—C6 | 123.3 (2) | C43—C44—H44B | 109.5 |
C10A—C6A—C6 | 118.3 (2) | H44A—C44—H44B | 109.5 |
C8—C7—C6A | 121.4 (2) | C43—C44—H44C | 109.5 |
C8—C7—H7 | 119.3 | H44A—C44—H44C | 109.5 |
C6A—C7—H7 | 119.3 | H44B—C44—H44C | 109.5 |
O81—C8—C9 | 122.8 (2) | C8—O81—H81 | 110.6 (15) |
O81—C8—C7 | 117.6 (2) | C6—C61—H61A | 109.5 |
C9—C8—C7 | 119.5 (2) | C6—C61—H61B | 109.5 |
C8—C9—C10 | 119.9 (2) | H61A—C61—H61B | 109.5 |
C8—C9—H9 | 120.0 | C6—C61—H61C | 109.5 |
C10—C9—H9 | 120.0 | H61A—C61—H61C | 109.5 |
C10A—C10—C9 | 120.2 (2) | H61B—C61—H61C | 109.5 |
C10A—C10—H10 | 119.9 | N11—C111—H11A | 109.5 |
C9—C10—H10 | 119.9 | N11—C111—H11B | 109.5 |
C10—C10A—C6A | 120.4 (2) | H11A—C111—H11B | 109.5 |
C10—C10A—N11 | 119.9 (2) | N11—C111—H11C | 109.5 |
C6A—C10A—N11 | 119.7 (2) | H11A—C111—H11C | 109.5 |
C11A—N11—C10A | 117.49 (19) | H11B—C111—H11C | 109.5 |
C11A—N11—C111 | 116.42 (19) | | |
| | | |
C11A—N1—C2—N3 | 1.1 (4) | C9—C10—C10A—N11 | −178.4 (2) |
N1—C2—N3—C4 | 2.2 (4) | C7—C6A—C10A—C10 | −4.1 (3) |
C2—N3—C4—O41 | 175.3 (2) | C6—C6A—C10A—C10 | 174.8 (2) |
C2—N3—C4—C4A | −2.9 (3) | C7—C6A—C10A—N11 | 176.8 (2) |
N3—C4—C4A—C11A | 0.4 (4) | C6—C6A—C10A—N11 | −4.4 (3) |
O41—C4—C4A—C11A | −177.9 (2) | C10—C10A—N11—C11A | 114.5 (2) |
N3—C4—C4A—C5 | 175.8 (2) | C6A—C10A—N11—C11A | −66.3 (3) |
O41—C4—C4A—C5 | −2.5 (3) | C10—C10A—N11—C111 | −29.5 (3) |
C11A—C4A—C5—C6 | −0.5 (4) | C6A—C10A—N11—C111 | 149.7 (2) |
C4—C4A—C5—C6 | −175.2 (2) | C2—N1—C11A—C4A | −4.0 (3) |
C4A—C5—C6—C61 | 174.6 (2) | C2—N1—C11A—N11 | 177.3 (2) |
C4A—C5—C6—C6A | −57.8 (3) | C4—C4A—C11A—N1 | 3.2 (3) |
C61—C6—C6A—C7 | 17.1 (3) | C5—C4A—C11A—N1 | −171.6 (2) |
C5—C6—C6A—C7 | −107.7 (3) | C4—C4A—C11A—N11 | −178.2 (2) |
C61—C6—C6A—C10A | −161.7 (2) | C5—C4A—C11A—N11 | 7.0 (4) |
C5—C6—C6A—C10A | 73.5 (3) | C10A—N11—C11A—N1 | −132.0 (2) |
C10A—C6A—C7—C8 | 2.2 (3) | C111—N11—C11A—N1 | 11.8 (3) |
C6—C6A—C7—C8 | −176.7 (2) | C10A—N11—C11A—C4A | 49.3 (3) |
C6A—C7—C8—O81 | −180.0 (2) | C111—N11—C11A—C4A | −166.9 (2) |
C6A—C7—C8—C9 | 1.4 (4) | N3—C4—O41—C41 | −8.4 (3) |
O81—C8—C9—C10 | 178.3 (2) | C4A—C4—O41—C41 | 170.0 (2) |
C7—C8—C9—C10 | −3.2 (3) | C4—O41—C41—C42 | −161.8 (2) |
C8—C9—C10—C10A | 1.3 (4) | O41—C41—C42—C43 | 173.6 (2) |
C9—C10—C10A—C6A | 2.4 (3) | C41—C42—C43—C44 | 178.4 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O81—H81···N3i | 1.01 (3) | 1.82 (3) | 2.825 (2) | 171 (2) |
C2—H2···N1ii | 0.95 | 2.59 | 3.330 (4) | 135 |
C10—H10···Cg1iii | 0.95 | 2.85 | 3.743 (2) | 156 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+2, −z+1; (iii) −x, y+1/2, −z+3/2. |
(III) 4-Dimethylamino-6,11-dimethyl-6,11-dihydro-5
H-benzo[
b]pyrimido[5,4-
f]azepin-8-ol
top
Crystal data top
C16H20N4O | Dx = 1.295 Mg m−3 |
Mr = 284.36 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 3368 reflections |
a = 18.886 (3) Å | θ = 2.1–27.6° |
b = 7.9898 (15) Å | µ = 0.08 mm−1 |
c = 19.335 (3) Å | T = 100 K |
V = 2917.6 (8) Å3 | Block, colourless |
Z = 8 | 0.14 × 0.12 × 0.12 mm |
F(000) = 1216 | |
Data collection top
Bruker D8 Venture diffractometer | 3367 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 2463 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.086 |
φ and ω scans | θmax = 27.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −24→22 |
Tmin = 0.851, Tmax = 0.990 | k = −10→8 |
26680 measured reflections | l = −23→24 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0497P)2 + 2.3537P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3367 reflections | Δρmax = 0.38 e Å−3 |
197 parameters | Δρmin = −0.30 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.04780 (8) | 0.79803 (19) | 0.52021 (7) | 0.0177 (3) | |
C2 | 0.08206 (10) | 0.8796 (2) | 0.56877 (9) | 0.0193 (4) | |
H2 | 0.0555 | 0.9065 | 0.6090 | 0.023* | |
N3 | 0.14911 (8) | 0.92899 (19) | 0.56880 (7) | 0.0166 (3) | |
C4 | 0.18543 (9) | 0.9001 (2) | 0.50950 (9) | 0.0138 (4) | |
C4A | 0.15192 (9) | 0.8382 (2) | 0.44936 (9) | 0.0140 (4) | |
C5 | 0.18613 (10) | 0.8667 (2) | 0.37926 (9) | 0.0173 (4) | |
H5A | 0.2209 | 0.7763 | 0.3710 | 0.021* | |
H5B | 0.2126 | 0.9737 | 0.3808 | 0.021* | |
C6 | 0.13485 (10) | 0.8725 (2) | 0.31767 (9) | 0.0179 (4) | |
H6 | 0.0919 | 0.9373 | 0.3317 | 0.021* | |
C6A | 0.11285 (9) | 0.6941 (2) | 0.30312 (9) | 0.0151 (4) | |
C7 | 0.13781 (10) | 0.6056 (2) | 0.24613 (9) | 0.0172 (4) | |
H7 | 0.1682 | 0.6598 | 0.2140 | 0.021* | |
C8 | 0.11920 (10) | 0.4399 (2) | 0.23524 (9) | 0.0182 (4) | |
C9 | 0.07558 (10) | 0.3592 (2) | 0.28244 (9) | 0.0220 (4) | |
H9 | 0.0619 | 0.2462 | 0.2750 | 0.026* | |
C10 | 0.05222 (10) | 0.4446 (2) | 0.34042 (9) | 0.0194 (4) | |
H10 | 0.0232 | 0.3888 | 0.3732 | 0.023* | |
C10A | 0.07080 (9) | 0.6111 (2) | 0.35119 (9) | 0.0156 (4) | |
N11 | 0.04268 (8) | 0.6971 (2) | 0.41004 (7) | 0.0165 (3) | |
C11A | 0.08264 (9) | 0.7773 (2) | 0.45912 (9) | 0.0141 (4) | |
N4 | 0.25566 (8) | 0.94162 (19) | 0.51069 (7) | 0.0156 (3) | |
C41 | 0.28411 (10) | 1.0212 (2) | 0.57289 (9) | 0.0206 (4) | |
H41A | 0.2848 | 0.9400 | 0.6109 | 0.031* | |
H41B | 0.2542 | 1.1165 | 0.5857 | 0.031* | |
H41C | 0.3324 | 1.0605 | 0.5638 | 0.031* | |
C42 | 0.30805 (10) | 0.8396 (3) | 0.47434 (11) | 0.0248 (5) | |
H42A | 0.2845 | 0.7437 | 0.4527 | 0.037* | |
H42B | 0.3436 | 0.7995 | 0.5073 | 0.037* | |
H42C | 0.3312 | 0.9072 | 0.4386 | 0.037* | |
C61 | 0.16899 (11) | 0.9607 (3) | 0.25648 (10) | 0.0248 (4) | |
H61A | 0.1365 | 0.9586 | 0.2170 | 0.037* | |
H61B | 0.2131 | 0.9033 | 0.2441 | 0.037* | |
H61C | 0.1794 | 1.0770 | 0.2689 | 0.037* | |
O81 | 0.14351 (8) | 0.35198 (17) | 0.17950 (7) | 0.0241 (3) | |
H81 | 0.1532 (12) | 0.422 (3) | 0.1462 (13) | 0.036* | |
C111 | −0.03182 (9) | 0.6633 (3) | 0.42602 (10) | 0.0198 (4) | |
H11A | −0.0527 | 0.7614 | 0.4486 | 0.030* | |
H11B | −0.0350 | 0.5666 | 0.4571 | 0.030* | |
H11C | −0.0575 | 0.6393 | 0.3831 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0180 (7) | 0.0191 (8) | 0.0160 (7) | −0.0002 (6) | 0.0046 (6) | 0.0008 (6) |
C2 | 0.0245 (10) | 0.0178 (9) | 0.0155 (9) | 0.0004 (8) | 0.0062 (8) | −0.0014 (7) |
N3 | 0.0213 (8) | 0.0153 (8) | 0.0133 (7) | −0.0009 (6) | 0.0013 (6) | −0.0005 (6) |
C4 | 0.0190 (8) | 0.0089 (8) | 0.0134 (8) | −0.0006 (7) | 0.0010 (7) | 0.0020 (7) |
C4A | 0.0163 (9) | 0.0129 (9) | 0.0128 (8) | −0.0007 (7) | 0.0014 (7) | 0.0010 (7) |
C5 | 0.0197 (9) | 0.0184 (9) | 0.0140 (8) | −0.0065 (8) | 0.0037 (7) | −0.0023 (7) |
C6 | 0.0220 (9) | 0.0174 (9) | 0.0143 (8) | −0.0031 (8) | 0.0022 (7) | 0.0017 (7) |
C6A | 0.0157 (8) | 0.0169 (9) | 0.0128 (8) | −0.0016 (7) | −0.0041 (7) | 0.0027 (7) |
C7 | 0.0201 (9) | 0.0199 (10) | 0.0115 (8) | −0.0041 (8) | −0.0014 (7) | 0.0031 (7) |
C8 | 0.0246 (10) | 0.0198 (10) | 0.0101 (8) | −0.0003 (8) | −0.0032 (7) | −0.0003 (7) |
C9 | 0.0275 (10) | 0.0175 (10) | 0.0210 (9) | −0.0065 (8) | −0.0035 (8) | 0.0005 (8) |
C10 | 0.0200 (9) | 0.0211 (10) | 0.0172 (9) | −0.0069 (8) | −0.0009 (8) | 0.0033 (8) |
C10A | 0.0136 (8) | 0.0207 (10) | 0.0124 (8) | −0.0017 (7) | −0.0032 (7) | 0.0014 (7) |
N11 | 0.0131 (7) | 0.0217 (8) | 0.0148 (7) | −0.0043 (6) | 0.0011 (6) | 0.0007 (6) |
C11A | 0.0168 (9) | 0.0129 (8) | 0.0127 (8) | 0.0011 (7) | 0.0011 (7) | 0.0021 (7) |
N4 | 0.0162 (7) | 0.0155 (8) | 0.0150 (7) | −0.0018 (6) | −0.0007 (6) | −0.0018 (6) |
C41 | 0.0250 (10) | 0.0201 (10) | 0.0167 (9) | −0.0066 (8) | −0.0040 (8) | −0.0004 (8) |
C42 | 0.0171 (9) | 0.0246 (11) | 0.0327 (11) | −0.0006 (8) | 0.0026 (8) | −0.0049 (9) |
C61 | 0.0317 (11) | 0.0221 (10) | 0.0205 (9) | −0.0034 (9) | 0.0046 (9) | 0.0046 (8) |
O81 | 0.0408 (8) | 0.0179 (7) | 0.0138 (6) | −0.0023 (6) | 0.0016 (6) | −0.0001 (6) |
C111 | 0.0124 (8) | 0.0268 (11) | 0.0204 (9) | −0.0014 (8) | −0.0011 (7) | 0.0029 (8) |
Geometric parameters (Å, º) top
N1—C2 | 1.313 (2) | C9—H9 | 0.9500 |
N1—C11A | 1.362 (2) | C10—C10A | 1.392 (3) |
C2—N3 | 1.326 (2) | C10—H10 | 0.9500 |
C2—H2 | 0.9500 | C10A—N11 | 1.431 (2) |
N3—C4 | 1.356 (2) | N11—C11A | 1.371 (2) |
C4—N4 | 1.367 (2) | N11—C111 | 1.466 (2) |
C4—C4A | 1.413 (2) | N4—C42 | 1.462 (2) |
C4A—C11A | 1.409 (2) | N4—C41 | 1.463 (2) |
C4A—C5 | 1.519 (2) | C41—H41A | 0.9800 |
C5—C6 | 1.536 (2) | C41—H41B | 0.9800 |
C5—H5A | 0.9900 | C41—H41C | 0.9800 |
C5—H5B | 0.9900 | C42—H42A | 0.9800 |
C6—C6A | 1.511 (3) | C42—H42B | 0.9800 |
C6—C61 | 1.520 (2) | C42—H42C | 0.9800 |
C6—H6 | 1.0000 | C61—H61A | 0.9800 |
C6A—C10A | 1.391 (2) | C61—H61B | 0.9800 |
C6A—C7 | 1.392 (2) | C61—H61C | 0.9800 |
C7—C8 | 1.386 (3) | O81—H81 | 0.87 (3) |
C7—H7 | 0.9500 | C111—H11A | 0.9800 |
C8—O81 | 1.366 (2) | C111—H11B | 0.9800 |
C8—C9 | 1.388 (3) | C111—H11C | 0.9800 |
C9—C10 | 1.384 (3) | | |
| | | |
C2—N1—C11A | 116.26 (15) | C6A—C10A—C10 | 119.98 (17) |
N1—C2—N3 | 128.19 (17) | C6A—C10A—N11 | 120.96 (16) |
N1—C2—H2 | 115.9 | C10—C10A—N11 | 118.96 (16) |
N3—C2—H2 | 115.9 | C11A—N11—C10A | 124.76 (14) |
C2—N3—C4 | 115.59 (15) | C11A—N11—C111 | 117.93 (14) |
N3—C4—N4 | 115.79 (15) | C10A—N11—C111 | 115.82 (14) |
N3—C4—C4A | 121.92 (16) | N1—C11A—N11 | 113.03 (15) |
N4—C4—C4A | 122.22 (15) | N1—C11A—C4A | 121.50 (16) |
C11A—C4A—C4 | 115.26 (15) | N11—C11A—C4A | 125.45 (15) |
C11A—C4A—C5 | 124.50 (15) | C4—N4—C42 | 120.86 (15) |
C4—C4A—C5 | 119.44 (15) | C4—N4—C41 | 118.40 (14) |
C4A—C5—C6 | 115.37 (15) | C42—N4—C41 | 112.90 (15) |
C4A—C5—H5A | 108.4 | N4—C41—H41A | 109.5 |
C6—C5—H5A | 108.4 | N4—C41—H41B | 109.5 |
C4A—C5—H5B | 108.4 | H41A—C41—H41B | 109.5 |
C6—C5—H5B | 108.4 | N4—C41—H41C | 109.5 |
H5A—C5—H5B | 107.5 | H41A—C41—H41C | 109.5 |
C6A—C6—C61 | 114.13 (15) | H41B—C41—H41C | 109.5 |
C6A—C6—C5 | 106.83 (15) | N4—C42—H42A | 109.5 |
C61—C6—C5 | 110.48 (15) | N4—C42—H42B | 109.5 |
C6A—C6—H6 | 108.4 | H42A—C42—H42B | 109.5 |
C61—C6—H6 | 108.4 | N4—C42—H42C | 109.5 |
C5—C6—H6 | 108.4 | H42A—C42—H42C | 109.5 |
C10A—C6A—C7 | 118.70 (17) | H42B—C42—H42C | 109.5 |
C10A—C6A—C6 | 118.84 (16) | C6—C61—H61A | 109.5 |
C7—C6A—C6 | 122.26 (16) | C6—C61—H61B | 109.5 |
C8—C7—C6A | 121.33 (17) | H61A—C61—H61B | 109.5 |
C8—C7—H7 | 119.3 | C6—C61—H61C | 109.5 |
C6A—C7—H7 | 119.3 | H61A—C61—H61C | 109.5 |
O81—C8—C7 | 121.72 (17) | H61B—C61—H61C | 109.5 |
O81—C8—C9 | 118.65 (17) | C8—O81—H81 | 108.7 (16) |
C7—C8—C9 | 119.63 (17) | N11—C111—H11A | 109.5 |
C10—C9—C8 | 119.50 (18) | N11—C111—H11B | 109.5 |
C10—C9—H9 | 120.2 | H11A—C111—H11B | 109.5 |
C8—C9—H9 | 120.2 | N11—C111—H11C | 109.5 |
C9—C10—C10A | 120.80 (17) | H11A—C111—H11C | 109.5 |
C9—C10—H10 | 119.6 | H11B—C111—H11C | 109.5 |
C10A—C10—H10 | 119.6 | | |
| | | |
C11A—N1—C2—N3 | −8.0 (3) | C6—C6A—C10A—C10 | −177.35 (16) |
N1—C2—N3—C4 | 4.2 (3) | C7—C6A—C10A—N11 | −178.83 (15) |
C2—N3—C4—N4 | −176.23 (16) | C6—C6A—C10A—N11 | 6.3 (2) |
C2—N3—C4—C4A | 6.6 (2) | C9—C10—C10A—C6A | 0.5 (3) |
N3—C4—C4A—C11A | −12.4 (2) | C9—C10—C10A—N11 | 176.97 (16) |
N4—C4—C4A—C11A | 170.66 (16) | C6A—C10A—N11—C11A | −58.5 (2) |
N3—C4—C4A—C5 | 157.82 (16) | C10—C10A—N11—C11A | 125.05 (19) |
N4—C4—C4A—C5 | −19.2 (3) | C6A—C10A—N11—C111 | 135.75 (17) |
C11A—C4A—C5—C6 | 16.5 (3) | C10—C10A—N11—C111 | −40.7 (2) |
C4—C4A—C5—C6 | −152.75 (17) | C2—N1—C11A—N11 | −177.55 (16) |
C4A—C5—C6—C6A | −75.52 (19) | C2—N1—C11A—C4A | 0.8 (3) |
C4A—C5—C6—C61 | 159.81 (16) | C10A—N11—C11A—N1 | −158.61 (16) |
C61—C6—C6A—C10A | −169.43 (16) | C111—N11—C11A—N1 | 6.8 (2) |
C5—C6—C6A—C10A | 68.1 (2) | C10A—N11—C11A—C4A | 23.1 (3) |
C61—C6—C6A—C7 | 15.9 (2) | C111—N11—C11A—C4A | −171.49 (17) |
C5—C6—C6A—C7 | −106.56 (18) | C4—C4A—C11A—N1 | 8.4 (2) |
C10A—C6A—C7—C8 | 2.7 (3) | C5—C4A—C11A—N1 | −161.18 (17) |
C6—C6A—C7—C8 | 177.38 (17) | C4—C4A—C11A—N11 | −173.38 (17) |
C6A—C7—C8—O81 | −179.92 (16) | C5—C4A—C11A—N11 | 17.0 (3) |
C6A—C7—C8—C9 | −0.9 (3) | N3—C4—N4—C42 | 143.42 (17) |
O81—C8—C9—C10 | 177.96 (16) | C4A—C4—N4—C42 | −39.4 (2) |
C7—C8—C9—C10 | −1.1 (3) | N3—C4—N4—C41 | −3.6 (2) |
C8—C9—C10—C10A | 1.3 (3) | C4A—C4—N4—C41 | 173.59 (16) |
C7—C6A—C10A—C10 | −2.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O81—H81···N3i | 0.87 (2) | 1.91 (2) | 2.767 (2) | 165 (2) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
(IV)
N-Benzyl-8-methoxy-6,11-dimethyl-6,11-dihydro-5
H-
benzo[
b]pyrimido[5,4-
f]azepin-4-amine
top
Crystal data top
C22H24N4O | F(000) = 768 |
Mr = 360.45 | Dx = 1.321 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2994 (8) Å | Cell parameters from 4129 reflections |
b = 9.1501 (5) Å | θ = 2.6–27.5° |
c = 16.1710 (9) Å | µ = 0.08 mm−1 |
β = 95.289 (2)° | T = 120 K |
V = 1812.15 (18) Å3 | Block, colourless |
Z = 4 | 0.12 × 0.10 × 0.10 mm |
Data collection top
Bruker D8 Venture diffractometer | 4129 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 2975 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.054 |
φ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −15→15 |
Tmin = 0.810, Tmax = 0.992 | k = −11→11 |
17697 measured reflections | l = −20→18 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0492P)2 + 0.6796P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4129 reflections | Δρmax = 0.27 e Å−3 |
250 parameters | Δρmin = −0.31 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.75768 (11) | 0.99419 (15) | 0.32499 (8) | 0.0225 (3) | |
C2 | 0.69211 (14) | 1.05234 (18) | 0.26418 (10) | 0.0245 (4) | |
H2 | 0.7254 | 1.1192 | 0.2293 | 0.029* | |
N3 | 0.58567 (11) | 1.02960 (15) | 0.24529 (8) | 0.0234 (3) | |
C4 | 0.53870 (13) | 0.94285 (17) | 0.29928 (9) | 0.0203 (3) | |
C4A | 0.59727 (12) | 0.87925 (16) | 0.36957 (9) | 0.0181 (3) | |
C5 | 0.53193 (12) | 0.80706 (17) | 0.43256 (9) | 0.0203 (3) | |
H5A | 0.5064 | 0.7113 | 0.4099 | 0.024* | |
H5B | 0.4663 | 0.8676 | 0.4383 | 0.024* | |
C6 | 0.58936 (12) | 0.78159 (17) | 0.51958 (9) | 0.0188 (3) | |
H6 | 0.6264 | 0.8745 | 0.5387 | 0.023* | |
C6A | 0.67552 (12) | 0.66548 (17) | 0.51472 (9) | 0.0178 (3) | |
C7 | 0.66718 (12) | 0.52862 (16) | 0.54999 (9) | 0.0185 (3) | |
H7 | 0.6070 | 0.5081 | 0.5810 | 0.022* | |
C8 | 0.74465 (13) | 0.42021 (17) | 0.54131 (9) | 0.0195 (3) | |
C9 | 0.83323 (13) | 0.44871 (18) | 0.49662 (10) | 0.0217 (3) | |
H9 | 0.8866 | 0.3755 | 0.4902 | 0.026* | |
C10 | 0.84261 (13) | 0.58612 (18) | 0.46132 (9) | 0.0215 (3) | |
H10 | 0.9032 | 0.6061 | 0.4306 | 0.026* | |
C10A | 0.76574 (12) | 0.69503 (17) | 0.46976 (9) | 0.0182 (3) | |
N11 | 0.78283 (10) | 0.83762 (14) | 0.43713 (8) | 0.0198 (3) | |
C11A | 0.70991 (13) | 0.90192 (16) | 0.37663 (9) | 0.0191 (3) | |
N41 | 0.42875 (11) | 0.92135 (16) | 0.28584 (8) | 0.0246 (3) | |
H41 | 0.4009 (15) | 0.850 (2) | 0.3140 (12) | 0.030* | |
C47 | 0.35857 (14) | 0.9848 (2) | 0.21697 (11) | 0.0323 (4) | |
H47A | 0.3467 | 0.9124 | 0.1715 | 0.039* | |
H47B | 0.3948 | 1.0714 | 0.1951 | 0.039* | |
C41 | 0.25032 (13) | 1.02897 (19) | 0.24581 (9) | 0.0231 (4) | |
C42 | 0.15889 (14) | 0.93957 (19) | 0.23225 (10) | 0.0267 (4) | |
H42 | 0.1640 | 0.8498 | 0.2034 | 0.032* | |
C43 | 0.06023 (14) | 0.9806 (2) | 0.26057 (11) | 0.0295 (4) | |
H43 | −0.0017 | 0.9189 | 0.2508 | 0.035* | |
C44 | 0.05150 (14) | 1.1104 (2) | 0.30279 (11) | 0.0290 (4) | |
H44 | −0.0161 | 1.1381 | 0.3222 | 0.035* | |
C45 | 0.14194 (15) | 1.20014 (19) | 0.31663 (11) | 0.0287 (4) | |
H45 | 0.1367 | 1.2894 | 0.3460 | 0.034* | |
C46 | 0.24011 (14) | 1.15986 (19) | 0.28766 (10) | 0.0255 (4) | |
H46 | 0.3014 | 1.2229 | 0.2966 | 0.031* | |
C61 | 0.50284 (13) | 0.74562 (18) | 0.57861 (10) | 0.0213 (3) | |
H61A | 0.5385 | 0.7260 | 0.6342 | 0.032* | |
H61B | 0.4616 | 0.6592 | 0.5583 | 0.032* | |
H61C | 0.4530 | 0.8287 | 0.5811 | 0.032* | |
O81 | 0.72694 (9) | 0.28897 (11) | 0.57929 (7) | 0.0228 (3) | |
C81 | 0.78753 (14) | 0.16654 (18) | 0.55387 (11) | 0.0270 (4) | |
H81A | 0.8653 | 0.1810 | 0.5712 | 0.040* | |
H81B | 0.7770 | 0.1570 | 0.4933 | 0.040* | |
H81C | 0.7620 | 0.0775 | 0.5797 | 0.040* | |
C111 | 0.89737 (13) | 0.88409 (18) | 0.43998 (10) | 0.0249 (4) | |
H11A | 0.9009 | 0.9910 | 0.4384 | 0.037* | |
H11B | 0.9305 | 0.8437 | 0.3921 | 0.037* | |
H11C | 0.9372 | 0.8485 | 0.4913 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0265 (7) | 0.0208 (7) | 0.0207 (7) | −0.0032 (6) | 0.0048 (6) | 0.0013 (6) |
C2 | 0.0317 (10) | 0.0227 (9) | 0.0201 (8) | −0.0029 (7) | 0.0068 (7) | 0.0021 (7) |
N3 | 0.0279 (8) | 0.0230 (7) | 0.0200 (7) | −0.0002 (6) | 0.0052 (6) | 0.0011 (6) |
C4 | 0.0257 (8) | 0.0169 (8) | 0.0190 (8) | 0.0007 (6) | 0.0051 (6) | −0.0032 (6) |
C4A | 0.0216 (8) | 0.0152 (7) | 0.0179 (7) | 0.0013 (6) | 0.0034 (6) | −0.0008 (6) |
C5 | 0.0200 (8) | 0.0202 (8) | 0.0211 (8) | 0.0006 (6) | 0.0034 (6) | 0.0025 (6) |
C6 | 0.0204 (8) | 0.0166 (8) | 0.0197 (8) | −0.0014 (6) | 0.0039 (6) | −0.0003 (6) |
C6A | 0.0199 (8) | 0.0193 (8) | 0.0140 (7) | −0.0015 (6) | 0.0002 (6) | −0.0035 (6) |
C7 | 0.0187 (8) | 0.0203 (8) | 0.0166 (7) | −0.0025 (6) | 0.0025 (6) | −0.0018 (6) |
C8 | 0.0232 (8) | 0.0188 (8) | 0.0161 (7) | −0.0007 (6) | −0.0004 (6) | −0.0011 (6) |
C9 | 0.0213 (8) | 0.0227 (8) | 0.0211 (8) | 0.0038 (7) | 0.0023 (6) | −0.0016 (7) |
C10 | 0.0198 (8) | 0.0260 (9) | 0.0189 (8) | −0.0004 (7) | 0.0035 (6) | −0.0011 (7) |
C10A | 0.0206 (8) | 0.0190 (8) | 0.0148 (7) | −0.0018 (6) | 0.0008 (6) | −0.0011 (6) |
N11 | 0.0188 (7) | 0.0196 (7) | 0.0212 (7) | −0.0032 (5) | 0.0034 (5) | 0.0015 (5) |
C11A | 0.0253 (8) | 0.0152 (7) | 0.0172 (7) | 0.0000 (6) | 0.0047 (6) | −0.0031 (6) |
N41 | 0.0225 (7) | 0.0294 (8) | 0.0220 (7) | 0.0020 (6) | 0.0018 (6) | 0.0058 (6) |
C47 | 0.0282 (9) | 0.0492 (12) | 0.0196 (8) | 0.0097 (8) | 0.0028 (7) | 0.0055 (8) |
C41 | 0.0234 (8) | 0.0296 (9) | 0.0160 (8) | 0.0029 (7) | 0.0000 (6) | 0.0066 (7) |
C42 | 0.0341 (10) | 0.0247 (9) | 0.0206 (8) | −0.0002 (7) | −0.0004 (7) | 0.0010 (7) |
C43 | 0.0267 (9) | 0.0329 (10) | 0.0282 (9) | −0.0078 (8) | −0.0004 (7) | 0.0064 (8) |
C44 | 0.0251 (9) | 0.0357 (10) | 0.0264 (9) | 0.0056 (8) | 0.0037 (7) | 0.0075 (8) |
C45 | 0.0367 (10) | 0.0238 (9) | 0.0252 (9) | 0.0056 (8) | −0.0003 (7) | 0.0002 (7) |
C46 | 0.0249 (9) | 0.0272 (9) | 0.0231 (8) | −0.0034 (7) | −0.0047 (7) | 0.0061 (7) |
C61 | 0.0221 (8) | 0.0222 (8) | 0.0201 (8) | −0.0002 (7) | 0.0047 (6) | −0.0025 (7) |
O81 | 0.0271 (6) | 0.0164 (6) | 0.0258 (6) | 0.0020 (5) | 0.0068 (5) | 0.0018 (5) |
C81 | 0.0326 (10) | 0.0201 (9) | 0.0288 (9) | 0.0054 (7) | 0.0059 (7) | 0.0013 (7) |
C111 | 0.0210 (9) | 0.0268 (9) | 0.0269 (9) | −0.0048 (7) | 0.0022 (7) | 0.0019 (7) |
Geometric parameters (Å, º) top
N1—C2 | 1.325 (2) | N11—C111 | 1.4681 (19) |
N1—C11A | 1.3585 (19) | N41—C47 | 1.465 (2) |
C2—N3 | 1.333 (2) | N41—H41 | 0.883 (19) |
C2—H2 | 0.9500 | C47—C41 | 1.506 (2) |
N3—C4 | 1.349 (2) | C47—H47A | 0.9900 |
C4—N41 | 1.364 (2) | C47—H47B | 0.9900 |
C4—C4A | 1.414 (2) | C41—C46 | 1.387 (2) |
C4A—C11A | 1.395 (2) | C41—C42 | 1.392 (2) |
C4A—C5 | 1.507 (2) | C42—C43 | 1.388 (2) |
C5—C6 | 1.533 (2) | C42—H42 | 0.9500 |
C5—H5A | 0.9900 | C43—C44 | 1.379 (3) |
C5—H5B | 0.9900 | C43—H43 | 0.9500 |
C6—C6A | 1.508 (2) | C44—C45 | 1.384 (3) |
C6—C61 | 1.529 (2) | C44—H44 | 0.9500 |
C6—H6 | 1.0000 | C45—C46 | 1.385 (2) |
C6A—C7 | 1.384 (2) | C45—H45 | 0.9500 |
C6A—C10A | 1.408 (2) | C46—H46 | 0.9500 |
C7—C8 | 1.391 (2) | C61—H61A | 0.9800 |
C7—H7 | 0.9500 | C61—H61B | 0.9800 |
C8—O81 | 1.3752 (18) | C61—H61C | 0.9800 |
C8—C9 | 1.386 (2) | O81—C81 | 1.4268 (19) |
C9—C10 | 1.390 (2) | C81—H81A | 0.9800 |
C9—H9 | 0.9500 | C81—H81B | 0.9800 |
C10—C10A | 1.389 (2) | C81—H81C | 0.9800 |
C10—H10 | 0.9500 | C111—H11A | 0.9800 |
C10A—N11 | 1.430 (2) | C111—H11B | 0.9800 |
N11—C11A | 1.395 (2) | C111—H11C | 0.9800 |
| | | |
C2—N1—C11A | 115.96 (14) | C4—N41—C47 | 124.76 (14) |
N1—C2—N3 | 128.71 (15) | C4—N41—H41 | 116.8 (12) |
N1—C2—H2 | 115.6 | C47—N41—H41 | 117.1 (12) |
N3—C2—H2 | 115.6 | N41—C47—C41 | 110.29 (13) |
C2—N3—C4 | 114.44 (14) | N41—C47—H47A | 109.6 |
N3—C4—N41 | 117.34 (14) | C41—C47—H47A | 109.6 |
N3—C4—C4A | 123.08 (14) | N41—C47—H47B | 109.6 |
N41—C4—C4A | 119.54 (14) | C41—C47—H47B | 109.6 |
C11A—C4A—C4 | 115.67 (14) | H47A—C47—H47B | 108.1 |
C11A—C4A—C5 | 126.68 (14) | C46—C41—C42 | 118.44 (15) |
C4—C4A—C5 | 117.38 (13) | C46—C41—C47 | 120.35 (16) |
C4A—C5—C6 | 117.25 (13) | C42—C41—C47 | 121.20 (16) |
C4A—C5—H5A | 108.0 | C43—C42—C41 | 120.50 (16) |
C6—C5—H5A | 108.0 | C43—C42—H42 | 119.8 |
C4A—C5—H5B | 108.0 | C41—C42—H42 | 119.8 |
C6—C5—H5B | 108.0 | C44—C43—C42 | 120.45 (16) |
H5A—C5—H5B | 107.2 | C44—C43—H43 | 119.8 |
C6A—C6—C61 | 114.44 (13) | C42—C43—H43 | 119.8 |
C6A—C6—C5 | 109.02 (12) | C43—C44—C45 | 119.53 (16) |
C61—C6—C5 | 108.51 (12) | C43—C44—H44 | 120.2 |
C6A—C6—H6 | 108.2 | C45—C44—H44 | 120.2 |
C61—C6—H6 | 108.2 | C44—C45—C46 | 120.03 (16) |
C5—C6—H6 | 108.2 | C44—C45—H45 | 120.0 |
C7—C6A—C10A | 118.59 (14) | C46—C45—H45 | 120.0 |
C7—C6A—C6 | 122.48 (13) | C45—C46—C41 | 121.05 (16) |
C10A—C6A—C6 | 118.87 (13) | C45—C46—H46 | 119.5 |
C6A—C7—C8 | 121.74 (14) | C41—C46—H46 | 119.5 |
C6A—C7—H7 | 119.1 | C6—C61—H61A | 109.5 |
C8—C7—H7 | 119.1 | C6—C61—H61B | 109.5 |
O81—C8—C9 | 124.15 (14) | H61A—C61—H61B | 109.5 |
O81—C8—C7 | 116.06 (13) | C6—C61—H61C | 109.5 |
C9—C8—C7 | 119.79 (14) | H61A—C61—H61C | 109.5 |
C8—C9—C10 | 118.89 (15) | H61B—C61—H61C | 109.5 |
C8—C9—H9 | 120.6 | C8—O81—C81 | 116.65 (12) |
C10—C9—H9 | 120.6 | O81—C81—H81A | 109.5 |
C10A—C10—C9 | 121.71 (14) | O81—C81—H81B | 109.5 |
C10A—C10—H10 | 119.1 | H81A—C81—H81B | 109.5 |
C9—C10—H10 | 119.1 | O81—C81—H81C | 109.5 |
C10—C10A—C6A | 119.28 (14) | H81A—C81—H81C | 109.5 |
C10—C10A—N11 | 119.59 (13) | H81B—C81—H81C | 109.5 |
C6A—C10A—N11 | 121.02 (13) | N11—C111—H11A | 109.5 |
C11A—N11—C10A | 122.46 (13) | N11—C111—H11B | 109.5 |
C11A—N11—C111 | 116.92 (13) | H11A—C111—H11B | 109.5 |
C10A—N11—C111 | 115.20 (13) | N11—C111—H11C | 109.5 |
N1—C11A—N11 | 114.00 (13) | H11A—C111—H11C | 109.5 |
N1—C11A—C4A | 121.64 (14) | H11B—C111—H11C | 109.5 |
N11—C11A—C4A | 124.34 (14) | | |
| | | |
C11A—N1—C2—N3 | −2.0 (2) | C10—C10A—N11—C11A | 120.11 (16) |
N1—C2—N3—C4 | 4.7 (2) | C6A—C10A—N11—C11A | −63.8 (2) |
C2—N3—C4—N41 | 176.72 (14) | C10—C10A—N11—C111 | −33.1 (2) |
C2—N3—C4—C4A | −0.9 (2) | C6A—C10A—N11—C111 | 143.05 (15) |
N3—C4—C4A—C11A | −5.0 (2) | C2—N1—C11A—N11 | 176.95 (13) |
N41—C4—C4A—C11A | 177.49 (14) | C2—N1—C11A—C4A | −4.8 (2) |
N3—C4—C4A—C5 | 169.47 (14) | C10A—N11—C11A—N1 | −149.18 (13) |
N41—C4—C4A—C5 | −8.1 (2) | C111—N11—C11A—N1 | 3.57 (19) |
C11A—C4A—C5—C6 | 12.5 (2) | C10A—N11—C11A—C4A | 32.6 (2) |
C4—C4A—C5—C6 | −161.25 (14) | C111—N11—C11A—C4A | −174.61 (14) |
C4A—C5—C6—C6A | −69.32 (17) | C4—C4A—C11A—N1 | 7.9 (2) |
C4A—C5—C6—C61 | 165.45 (13) | C5—C4A—C11A—N1 | −165.94 (14) |
C61—C6—C6A—C7 | 9.9 (2) | C4—C4A—C11A—N11 | −174.03 (14) |
C5—C6—C6A—C7 | −111.75 (16) | C5—C4A—C11A—N11 | 12.1 (2) |
C61—C6—C6A—C10A | −172.72 (14) | N3—C4—N41—C47 | 0.4 (2) |
C5—C6—C6A—C10A | 65.58 (17) | C4A—C4—N41—C47 | 178.04 (15) |
C10A—C6A—C7—C8 | −0.7 (2) | C4—N41—C47—C41 | −141.85 (16) |
C6—C6A—C7—C8 | 176.65 (14) | N41—C47—C41—C46 | 80.7 (2) |
C6A—C7—C8—O81 | −179.95 (13) | N41—C47—C41—C42 | −98.48 (19) |
C6A—C7—C8—C9 | 0.3 (2) | C46—C41—C42—C43 | −0.4 (2) |
O81—C8—C9—C10 | −179.69 (14) | C47—C41—C42—C43 | 178.80 (15) |
C7—C8—C9—C10 | 0.1 (2) | C41—C42—C43—C44 | −0.2 (2) |
C8—C9—C10—C10A | 0.0 (2) | C42—C43—C44—C45 | 0.2 (3) |
C9—C10—C10A—C6A | −0.4 (2) | C43—C44—C45—C46 | 0.5 (3) |
C9—C10—C10A—N11 | 175.77 (14) | C44—C45—C46—C41 | −1.1 (2) |
C7—C6A—C10A—C10 | 0.7 (2) | C42—C41—C46—C45 | 1.1 (2) |
C6—C6A—C10A—C10 | −176.69 (14) | C47—C41—C46—C45 | −178.18 (15) |
C7—C6A—C10A—N11 | −175.40 (14) | C9—C8—O81—C81 | −16.1 (2) |
C6—C6A—C10A—N11 | 7.2 (2) | C7—C8—O81—C81 | 164.17 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O81i | 0.95 | 2.57 | 3.386 (2) | 144 |
C45—H45···Cg1ii | 0.95 | 2.99 | 3.7583 (19) | 139 |
C46—H46···Cg2iii | 0.95 | 2.99 | 3.7583 (19) | 139 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
(V)
N-Benzyl-6-methyl-1,2,6,7-tetrahydropyrimido[5',4':6,7]azepino[3,2,1-
hi]indol-8-amine
top
Crystal data top
C22H22N4 | F(000) = 364 |
Mr = 342.44 | Dx = 1.298 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.7594 (4) Å | Cell parameters from 3037 reflections |
b = 8.5383 (6) Å | θ = 5.8–66.7° |
c = 13.4525 (8) Å | µ = 0.61 mm−1 |
β = 100.483 (3)° | T = 120 K |
V = 876.38 (9) Å3 | Block, colourless |
Z = 2 | 0.14 × 0.12 × 0.09 mm |
Data collection top
Bruker D8 Venture diffractometer | 3037 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 2972 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.023 |
φ and ω scans | θmax = 66.7°, θmin = 5.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.847, Tmax = 0.946 | k = −10→10 |
11308 measured reflections | l = −13→15 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.1235P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.078 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.13 e Å−3 |
3037 reflections | Δρmin = −0.16 e Å−3 |
239 parameters | Absolute structure: Flack x determined using 1344 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
1 restraint | Absolute structure parameter: 0.11 (15) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.9711 (3) | 0.4769 (2) | 0.63564 (15) | 0.0225 (4) | |
H1A | 1.0930 | 0.5088 | 0.6334 | 0.027* | |
H1B | 0.9551 | 0.3662 | 0.6139 | 0.027* | |
C2 | 0.9309 (3) | 0.4984 (3) | 0.74184 (15) | 0.0263 (5) | |
H2A | 0.9319 | 0.3966 | 0.7773 | 0.032* | |
H2B | 1.0167 | 0.5695 | 0.7826 | 0.032* | |
C2A | 0.7500 (3) | 0.5692 (2) | 0.72271 (15) | 0.0215 (4) | |
C2B | 0.7065 (3) | 0.6209 (2) | 0.62191 (15) | 0.0189 (4) | |
C3 | 0.6354 (3) | 0.5884 (2) | 0.78933 (15) | 0.0251 (4) | |
H3 | 0.6653 | 0.5517 | 0.8570 | 0.030* | |
C4 | 0.4750 (3) | 0.6625 (2) | 0.75572 (16) | 0.0260 (5) | |
H4 | 0.3937 | 0.6755 | 0.8000 | 0.031* | |
C5 | 0.4355 (3) | 0.7167 (2) | 0.65737 (15) | 0.0230 (4) | |
H5 | 0.3270 | 0.7691 | 0.6361 | 0.028* | |
C5A | 0.5480 (2) | 0.6983 (2) | 0.58739 (14) | 0.0196 (4) | |
C6 | 0.4924 (2) | 0.7680 (2) | 0.48346 (14) | 0.0191 (4) | |
H6 | 0.4264 | 0.8660 | 0.4926 | 0.023* | |
C7 | 0.6523 (2) | 0.8183 (2) | 0.43823 (14) | 0.0195 (4) | |
H7A | 0.6127 | 0.8913 | 0.3815 | 0.023* | |
H7B | 0.7347 | 0.8760 | 0.4904 | 0.023* | |
C7A | 0.7484 (2) | 0.6849 (2) | 0.40052 (14) | 0.0188 (4) | |
C8 | 0.7593 (2) | 0.6641 (2) | 0.29771 (14) | 0.0206 (4) | |
N9 | 0.8576 (2) | 0.5504 (2) | 0.26604 (12) | 0.0230 (4) | |
C10 | 0.9481 (2) | 0.4622 (2) | 0.33878 (15) | 0.0218 (4) | |
H10 | 1.0217 | 0.3852 | 0.3172 | 0.026* | |
N11 | 0.9494 (2) | 0.46753 (19) | 0.43733 (12) | 0.0209 (4) | |
C11A | 0.8440 (2) | 0.5786 (2) | 0.46714 (14) | 0.0184 (4) | |
N12 | 0.8439 (2) | 0.57966 (19) | 0.57005 (12) | 0.0187 (3) | |
C61 | 0.3671 (2) | 0.6644 (2) | 0.41068 (15) | 0.0233 (4) | |
H61A | 0.4283 | 0.5689 | 0.3963 | 0.035* | |
H61B | 0.3267 | 0.7215 | 0.3475 | 0.035* | |
H61C | 0.2662 | 0.6365 | 0.4415 | 0.035* | |
N81 | 0.6761 (2) | 0.7646 (2) | 0.22618 (13) | 0.0271 (4) | |
H81 | 0.609 (3) | 0.830 (3) | 0.2442 (19) | 0.033* | |
C87 | 0.6467 (3) | 0.7349 (3) | 0.11770 (15) | 0.0290 (5) | |
H87A | 0.7086 | 0.6378 | 0.1045 | 0.035* | |
H87B | 0.6953 | 0.8225 | 0.0833 | 0.035* | |
C81 | 0.4535 (3) | 0.7179 (3) | 0.07542 (15) | 0.0253 (4) | |
C82 | 0.3479 (3) | 0.6203 (3) | 0.12198 (18) | 0.0350 (5) | |
H82 | 0.3987 | 0.5601 | 0.1792 | 0.042* | |
C83 | 0.1696 (4) | 0.6108 (4) | 0.0853 (2) | 0.0481 (7) | |
H83 | 0.0983 | 0.5457 | 0.1184 | 0.058* | |
C84 | 0.0945 (3) | 0.6954 (4) | 0.00074 (18) | 0.0477 (7) | |
H84 | −0.0278 | 0.6876 | −0.0245 | 0.057* | |
C85 | 0.1973 (3) | 0.7908 (3) | −0.04666 (17) | 0.0384 (6) | |
H85 | 0.1464 | 0.8487 | −0.1049 | 0.046* | |
C86 | 0.3760 (3) | 0.8023 (3) | −0.00906 (15) | 0.0285 (5) | |
H86 | 0.4462 | 0.8691 | −0.0418 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0191 (9) | 0.0241 (10) | 0.0234 (10) | 0.0048 (8) | 0.0015 (7) | 0.0020 (8) |
C2 | 0.0244 (10) | 0.0305 (11) | 0.0233 (10) | 0.0015 (8) | 0.0023 (8) | 0.0012 (9) |
C2A | 0.0232 (10) | 0.0200 (9) | 0.0208 (9) | −0.0010 (8) | 0.0032 (7) | −0.0016 (8) |
C2B | 0.0193 (9) | 0.0173 (9) | 0.0212 (10) | −0.0022 (7) | 0.0064 (8) | −0.0039 (7) |
C3 | 0.0299 (11) | 0.0263 (10) | 0.0198 (10) | −0.0025 (8) | 0.0059 (8) | −0.0012 (8) |
C4 | 0.0284 (11) | 0.0265 (11) | 0.0254 (10) | −0.0018 (9) | 0.0112 (8) | −0.0057 (9) |
C5 | 0.0213 (10) | 0.0201 (10) | 0.0287 (11) | 0.0003 (7) | 0.0071 (8) | −0.0027 (8) |
C5A | 0.0205 (10) | 0.0152 (9) | 0.0238 (10) | −0.0016 (7) | 0.0054 (8) | −0.0021 (7) |
C6 | 0.0167 (9) | 0.0157 (9) | 0.0257 (10) | 0.0022 (7) | 0.0054 (7) | 0.0014 (7) |
C7 | 0.0204 (10) | 0.0164 (9) | 0.0217 (9) | −0.0005 (8) | 0.0038 (7) | 0.0012 (8) |
C7A | 0.0150 (9) | 0.0184 (9) | 0.0232 (10) | −0.0021 (7) | 0.0041 (7) | 0.0001 (7) |
C8 | 0.0168 (9) | 0.0222 (10) | 0.0223 (10) | −0.0042 (8) | 0.0022 (7) | 0.0004 (8) |
N9 | 0.0196 (8) | 0.0256 (9) | 0.0246 (8) | −0.0016 (7) | 0.0060 (7) | −0.0031 (7) |
C10 | 0.0172 (9) | 0.0239 (9) | 0.0254 (10) | −0.0004 (8) | 0.0064 (7) | −0.0029 (8) |
N11 | 0.0172 (8) | 0.0214 (8) | 0.0245 (9) | 0.0003 (7) | 0.0051 (6) | −0.0025 (7) |
C11A | 0.0136 (9) | 0.0187 (9) | 0.0229 (10) | −0.0040 (7) | 0.0037 (7) | −0.0014 (8) |
N12 | 0.0163 (8) | 0.0203 (8) | 0.0197 (8) | 0.0018 (6) | 0.0040 (6) | 0.0004 (6) |
C61 | 0.0179 (10) | 0.0229 (10) | 0.0283 (10) | −0.0016 (8) | 0.0025 (8) | 0.0035 (8) |
N81 | 0.0289 (9) | 0.0302 (9) | 0.0217 (9) | 0.0057 (8) | 0.0029 (7) | −0.0003 (7) |
C87 | 0.0286 (11) | 0.0381 (12) | 0.0202 (10) | −0.0003 (9) | 0.0046 (8) | 0.0026 (9) |
C81 | 0.0285 (11) | 0.0292 (11) | 0.0189 (9) | 0.0006 (8) | 0.0060 (8) | −0.0029 (8) |
C82 | 0.0391 (13) | 0.0423 (14) | 0.0244 (11) | −0.0102 (10) | 0.0080 (9) | 0.0002 (9) |
C83 | 0.0420 (14) | 0.070 (2) | 0.0351 (14) | −0.0254 (13) | 0.0154 (11) | −0.0133 (12) |
C84 | 0.0269 (12) | 0.084 (2) | 0.0314 (13) | −0.0058 (13) | 0.0033 (10) | −0.0199 (14) |
C85 | 0.0337 (12) | 0.0554 (16) | 0.0241 (11) | 0.0128 (11) | −0.0003 (9) | −0.0094 (10) |
C86 | 0.0336 (12) | 0.0313 (11) | 0.0204 (10) | 0.0036 (9) | 0.0047 (8) | −0.0038 (8) |
Geometric parameters (Å, º) top
C1—N12 | 1.485 (2) | C8—N9 | 1.351 (3) |
C1—C2 | 1.528 (3) | C8—N81 | 1.361 (3) |
C1—H1A | 0.9900 | N9—C10 | 1.330 (3) |
C1—H1B | 0.9900 | C10—N11 | 1.325 (3) |
C2—C2A | 1.507 (3) | C10—H10 | 0.9500 |
C2—H2A | 0.9900 | N11—C11A | 1.359 (3) |
C2—H2B | 0.9900 | C11A—N12 | 1.385 (2) |
C2A—C3 | 1.383 (3) | C61—H61A | 0.9800 |
C2A—C2B | 1.408 (3) | C61—H61B | 0.9800 |
C2B—C5A | 1.399 (3) | C61—H61C | 0.9800 |
C2B—N12 | 1.421 (2) | N81—C87 | 1.458 (3) |
C3—C4 | 1.396 (3) | N81—H81 | 0.83 (3) |
C3—H3 | 0.9500 | C87—C81 | 1.510 (3) |
C4—C5 | 1.382 (3) | C87—H87A | 0.9900 |
C4—H4 | 0.9500 | C87—H87B | 0.9900 |
C5—C5A | 1.404 (3) | C81—C86 | 1.387 (3) |
C5—H5 | 0.9500 | C81—C82 | 1.394 (3) |
C5A—C6 | 1.509 (3) | C82—C83 | 1.385 (4) |
C6—C61 | 1.529 (3) | C82—H82 | 0.9500 |
C6—C7 | 1.539 (3) | C83—C84 | 1.384 (4) |
C6—H6 | 1.0000 | C83—H83 | 0.9500 |
C7—C7A | 1.500 (3) | C84—C85 | 1.375 (4) |
C7—H7A | 0.9900 | C84—H84 | 0.9500 |
C7—H7B | 0.9900 | C85—C86 | 1.390 (3) |
C7A—C11A | 1.391 (3) | C85—H85 | 0.9500 |
C7A—C8 | 1.412 (3) | C86—H86 | 0.9500 |
| | | |
N12—C1—C2 | 104.94 (16) | N9—C8—C7A | 122.48 (18) |
N12—C1—H1A | 110.8 | N81—C8—C7A | 120.54 (18) |
C2—C1—H1A | 110.8 | C10—N9—C8 | 115.35 (16) |
N12—C1—H1B | 110.8 | N11—C10—N9 | 128.58 (19) |
C2—C1—H1B | 110.8 | N11—C10—H10 | 115.7 |
H1A—C1—H1B | 108.8 | N9—C10—H10 | 115.7 |
C2A—C2—C1 | 103.34 (16) | C10—N11—C11A | 115.09 (17) |
C2A—C2—H2A | 111.1 | N11—C11A—N12 | 114.18 (16) |
C1—C2—H2A | 111.1 | N11—C11A—C7A | 122.95 (17) |
C2A—C2—H2B | 111.1 | N12—C11A—C7A | 122.85 (17) |
C1—C2—H2B | 111.1 | C11A—N12—C2B | 129.03 (16) |
H2A—C2—H2B | 109.1 | C11A—N12—C1 | 117.95 (15) |
C3—C2A—C2B | 121.14 (19) | C2B—N12—C1 | 109.38 (15) |
C3—C2A—C2 | 128.76 (19) | C6—C61—H61A | 109.5 |
C2B—C2A—C2 | 110.10 (17) | C6—C61—H61B | 109.5 |
C5A—C2B—C2A | 120.71 (18) | H61A—C61—H61B | 109.5 |
C5A—C2B—N12 | 130.32 (18) | C6—C61—H61C | 109.5 |
C2A—C2B—N12 | 108.97 (17) | H61A—C61—H61C | 109.5 |
C2A—C3—C4 | 118.99 (19) | H61B—C61—H61C | 109.5 |
C2A—C3—H3 | 120.5 | C8—N81—C87 | 124.44 (19) |
C4—C3—H3 | 120.5 | C8—N81—H81 | 117.4 (18) |
C5—C4—C3 | 119.39 (18) | C87—N81—H81 | 114.6 (18) |
C5—C4—H4 | 120.3 | N81—C87—C81 | 110.95 (17) |
C3—C4—H4 | 120.3 | N81—C87—H87A | 109.4 |
C4—C5—C5A | 123.21 (19) | C81—C87—H87A | 109.4 |
C4—C5—H5 | 118.4 | N81—C87—H87B | 109.4 |
C5A—C5—H5 | 118.4 | C81—C87—H87B | 109.4 |
C2B—C5A—C5 | 116.52 (18) | H87A—C87—H87B | 108.0 |
C2B—C5A—C6 | 125.46 (17) | C86—C81—C82 | 118.4 (2) |
C5—C5A—C6 | 117.98 (17) | C86—C81—C87 | 120.73 (19) |
C5A—C6—C61 | 113.99 (16) | C82—C81—C87 | 120.82 (19) |
C5A—C6—C7 | 111.17 (15) | C83—C82—C81 | 120.4 (2) |
C61—C6—C7 | 111.86 (16) | C83—C82—H82 | 119.8 |
C5A—C6—H6 | 106.4 | C81—C82—H82 | 119.8 |
C61—C6—H6 | 106.4 | C84—C83—C82 | 120.4 (2) |
C7—C6—H6 | 106.4 | C84—C83—H83 | 119.8 |
C7A—C7—C6 | 114.07 (16) | C82—C83—H83 | 119.8 |
C7A—C7—H7A | 108.7 | C85—C84—C83 | 119.8 (2) |
C6—C7—H7A | 108.7 | C85—C84—H84 | 120.1 |
C7A—C7—H7B | 108.7 | C83—C84—H84 | 120.1 |
C6—C7—H7B | 108.7 | C84—C85—C86 | 119.8 (2) |
H7A—C7—H7B | 107.6 | C84—C85—H85 | 120.1 |
C11A—C7A—C8 | 115.41 (17) | C86—C85—H85 | 120.1 |
C11A—C7A—C7 | 121.16 (17) | C81—C86—C85 | 121.1 (2) |
C8—C7A—C7 | 123.28 (17) | C81—C86—H86 | 119.5 |
N9—C8—N81 | 116.91 (18) | C85—C86—H86 | 119.5 |
| | | |
N12—C1—C2—C2A | 17.6 (2) | C8—N9—C10—N11 | 2.8 (3) |
C1—C2—C2A—C3 | 167.5 (2) | N9—C10—N11—C11A | −0.2 (3) |
C1—C2—C2A—C2B | −13.6 (2) | C10—N11—C11A—N12 | 178.51 (16) |
C3—C2A—C2B—C5A | 2.3 (3) | C10—N11—C11A—C7A | −3.3 (3) |
C2—C2A—C2B—C5A | −176.74 (17) | C8—C7A—C11A—N11 | 3.7 (3) |
C3—C2A—C2B—N12 | −177.29 (18) | C7—C7A—C11A—N11 | −171.97 (17) |
C2—C2A—C2B—N12 | 3.7 (2) | C8—C7A—C11A—N12 | −178.21 (17) |
C2B—C2A—C3—C4 | −0.9 (3) | C7—C7A—C11A—N12 | 6.1 (3) |
C2—C2A—C3—C4 | 177.9 (2) | N11—C11A—N12—C2B | −148.68 (18) |
C2A—C3—C4—C5 | −0.9 (3) | C7A—C11A—N12—C2B | 33.1 (3) |
C3—C4—C5—C5A | 1.4 (3) | N11—C11A—N12—C1 | 7.3 (2) |
C2A—C2B—C5A—C5 | −1.7 (3) | C7A—C11A—N12—C1 | −170.90 (16) |
N12—C2B—C5A—C5 | 177.75 (18) | C5A—C2B—N12—C11A | −13.6 (3) |
C2A—C2B—C5A—C6 | 175.82 (17) | C2A—C2B—N12—C11A | 165.95 (18) |
N12—C2B—C5A—C6 | −4.7 (3) | C5A—C2B—N12—C1 | −171.18 (19) |
C4—C5—C5A—C2B | −0.1 (3) | C2A—C2B—N12—C1 | 8.3 (2) |
C4—C5—C5A—C6 | −177.83 (18) | C2—C1—N12—C11A | −176.99 (16) |
C2B—C5A—C6—C61 | 99.4 (2) | C2—C1—N12—C2B | −16.5 (2) |
C5—C5A—C6—C61 | −83.1 (2) | N9—C8—N81—C87 | 17.2 (3) |
C2B—C5A—C6—C7 | −28.2 (3) | C7A—C8—N81—C87 | −165.79 (18) |
C5—C5A—C6—C7 | 149.33 (17) | C8—N81—C87—C81 | 114.1 (2) |
C5A—C6—C7—C7A | 75.8 (2) | N81—C87—C81—C86 | 129.7 (2) |
C61—C6—C7—C7A | −52.9 (2) | N81—C87—C81—C82 | −48.5 (3) |
C6—C7—C7A—C11A | −69.5 (2) | C86—C81—C82—C83 | −1.1 (3) |
C6—C7—C7A—C8 | 115.19 (19) | C87—C81—C82—C83 | 177.1 (2) |
C11A—C7A—C8—N9 | −0.9 (3) | C81—C82—C83—C84 | 1.4 (4) |
C7—C7A—C8—N9 | 174.70 (17) | C82—C83—C84—C85 | −0.6 (4) |
C11A—C7A—C8—N81 | −177.71 (17) | C83—C84—C85—C86 | −0.3 (4) |
C7—C7A—C8—N81 | −2.1 (3) | C82—C81—C86—C85 | 0.2 (3) |
N81—C8—N9—C10 | 174.85 (17) | C87—C81—C86—C85 | −178.1 (2) |
C7A—C8—N9—C10 | −2.1 (3) | C84—C85—C86—C81 | 0.5 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7B···N11i | 0.99 | 2.59 | 3.478 (2) | 150 |
C1—H1B···Cg3ii | 0.99 | 2.94 | 3.758 (2) | 140 |
C5—H5···Cg3iii | 0.95 | 2.90 | 3.712 (2) | 144 |
C7—H7A···Cg4iii | 0.99 | 2.73 | 3.6068 (19) | 147 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) −x+2, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1. |
(VI)
N-Benzyl-7-methyl-2,3,7,8-tetrahydro-1
H-pyrimido[5',4':6,7]azepino[3,2,1-
ij]quinolin-9-amine
top
Crystal data top
C23H24N4 | Dx = 1.284 Mg m−3 |
Mr = 356.46 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 4188 reflections |
a = 15.083 (3) Å | θ = 2.6–27.5° |
b = 27.563 (4) Å | µ = 0.08 mm−1 |
c = 8.8681 (13) Å | T = 120 K |
V = 3686.8 (11) Å3 | Block, colourless |
Z = 8 | 0.12 × 0.12 × 0.10 mm |
F(000) = 1520 | |
Data collection top
Bruker D8 Venture diffractometer | 4188 independent reflections |
Radiation source: high brilliance microfocus sealed tube | 3293 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.056 |
φ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −19→17 |
Tmin = 0.874, Tmax = 0.992 | k = −33→35 |
31735 measured reflections | l = −11→10 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0438P)2 + 1.5761P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4188 reflections | Δρmax = 0.22 e Å−3 |
248 parameters | Δρmin = −0.25 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.47010 (9) | 0.60015 (5) | 0.26984 (16) | 0.0154 (3) | |
H1A | 0.4313 | 0.6207 | 0.3333 | 0.018* | |
H1B | 0.4336 | 0.5736 | 0.2274 | 0.018* | |
C2 | 0.50895 (9) | 0.63038 (5) | 0.14229 (16) | 0.0192 (3) | |
H2A | 0.4608 | 0.6425 | 0.0764 | 0.023* | |
H2B | 0.5494 | 0.6102 | 0.0806 | 0.023* | |
C3 | 0.55978 (9) | 0.67308 (5) | 0.20986 (17) | 0.0196 (3) | |
H3A | 0.6035 | 0.6848 | 0.1350 | 0.024* | |
H3B | 0.5177 | 0.6999 | 0.2301 | 0.024* | |
C3A | 0.60788 (9) | 0.66061 (5) | 0.35447 (16) | 0.0166 (3) | |
C3B | 0.59796 (8) | 0.61583 (4) | 0.42804 (16) | 0.0132 (3) | |
C4 | 0.66180 (9) | 0.69556 (5) | 0.42200 (19) | 0.0221 (3) | |
H4 | 0.6690 | 0.7262 | 0.3747 | 0.026* | |
C5 | 0.70484 (10) | 0.68633 (5) | 0.55619 (19) | 0.0258 (4) | |
H5 | 0.7429 | 0.7102 | 0.5986 | 0.031* | |
C6 | 0.69272 (9) | 0.64231 (5) | 0.62949 (18) | 0.0225 (3) | |
H6 | 0.7221 | 0.6363 | 0.7224 | 0.027* | |
C6A | 0.63786 (8) | 0.60700 (5) | 0.56786 (16) | 0.0149 (3) | |
C7 | 0.61821 (9) | 0.55973 (5) | 0.64707 (15) | 0.0149 (3) | |
H7 | 0.5529 | 0.5539 | 0.6407 | 0.018* | |
C8 | 0.66481 (9) | 0.51785 (4) | 0.56658 (15) | 0.0144 (3) | |
H8A | 0.7293 | 0.5246 | 0.5664 | 0.017* | |
H8B | 0.6554 | 0.4880 | 0.6266 | 0.017* | |
C8A | 0.63663 (8) | 0.50767 (4) | 0.40670 (15) | 0.0122 (3) | |
C9 | 0.66845 (8) | 0.46463 (4) | 0.33830 (15) | 0.0130 (3) | |
N10 | 0.64346 (7) | 0.44984 (4) | 0.19932 (13) | 0.0150 (2) | |
C11 | 0.58159 (9) | 0.47731 (4) | 0.13419 (16) | 0.0150 (3) | |
H11 | 0.5597 | 0.4660 | 0.0400 | 0.018* | |
N12 | 0.54690 (7) | 0.51830 (4) | 0.18438 (13) | 0.0149 (3) | |
C12A | 0.57729 (8) | 0.53462 (4) | 0.31946 (15) | 0.0123 (3) | |
N13 | 0.54186 (7) | 0.57961 (4) | 0.36274 (13) | 0.0131 (2) | |
C71 | 0.64401 (10) | 0.55957 (5) | 0.81365 (16) | 0.0225 (3) | |
H71A | 0.7085 | 0.5627 | 0.8229 | 0.034* | |
H71B | 0.6248 | 0.5291 | 0.8601 | 0.034* | |
H71C | 0.6153 | 0.5869 | 0.8649 | 0.034* | |
N91 | 0.72699 (8) | 0.43561 (4) | 0.41223 (15) | 0.0163 (3) | |
H91 | 0.7449 (11) | 0.4442 (5) | 0.500 (2) | 0.020* | |
C97 | 0.75188 (9) | 0.38722 (4) | 0.36001 (17) | 0.0168 (3) | |
H97A | 0.8106 | 0.3789 | 0.4027 | 0.020* | |
H97B | 0.7579 | 0.3879 | 0.2489 | 0.020* | |
C91 | 0.68631 (9) | 0.34779 (4) | 0.40250 (16) | 0.0160 (3) | |
C92 | 0.70590 (10) | 0.31655 (5) | 0.52123 (17) | 0.0199 (3) | |
H92 | 0.7606 | 0.3199 | 0.5733 | 0.024* | |
C93 | 0.64675 (10) | 0.28055 (5) | 0.56481 (19) | 0.0250 (3) | |
H93 | 0.6607 | 0.2597 | 0.6468 | 0.030* | |
C94 | 0.56714 (10) | 0.27515 (5) | 0.48809 (19) | 0.0250 (4) | |
H94 | 0.5266 | 0.2504 | 0.5168 | 0.030* | |
C95 | 0.54712 (10) | 0.30593 (5) | 0.36942 (19) | 0.0246 (3) | |
H95 | 0.4926 | 0.3023 | 0.3170 | 0.030* | |
C96 | 0.60593 (9) | 0.34196 (5) | 0.32660 (17) | 0.0200 (3) | |
H96 | 0.5915 | 0.3629 | 0.2450 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0115 (6) | 0.0191 (6) | 0.0156 (7) | 0.0028 (5) | −0.0019 (5) | 0.0010 (5) |
C2 | 0.0187 (7) | 0.0229 (7) | 0.0159 (8) | 0.0039 (5) | −0.0010 (6) | 0.0037 (6) |
C3 | 0.0193 (7) | 0.0182 (6) | 0.0213 (8) | 0.0018 (5) | 0.0034 (6) | 0.0056 (6) |
C3A | 0.0128 (6) | 0.0168 (6) | 0.0201 (8) | 0.0031 (5) | 0.0046 (6) | −0.0009 (5) |
C3B | 0.0105 (6) | 0.0135 (6) | 0.0155 (7) | 0.0018 (5) | 0.0019 (5) | −0.0029 (5) |
C4 | 0.0180 (7) | 0.0129 (6) | 0.0352 (9) | 0.0003 (5) | 0.0023 (6) | 0.0006 (6) |
C5 | 0.0206 (7) | 0.0169 (7) | 0.0400 (10) | −0.0023 (6) | −0.0087 (7) | −0.0070 (6) |
C6 | 0.0205 (7) | 0.0207 (7) | 0.0263 (9) | 0.0029 (5) | −0.0090 (6) | −0.0053 (6) |
C6A | 0.0132 (6) | 0.0152 (6) | 0.0163 (8) | 0.0032 (5) | 0.0006 (5) | −0.0043 (5) |
C7 | 0.0143 (6) | 0.0190 (6) | 0.0114 (7) | 0.0001 (5) | −0.0008 (5) | −0.0016 (5) |
C8 | 0.0156 (6) | 0.0145 (6) | 0.0131 (7) | −0.0008 (5) | −0.0018 (5) | 0.0019 (5) |
C8A | 0.0119 (6) | 0.0127 (6) | 0.0120 (7) | −0.0027 (5) | 0.0010 (5) | 0.0006 (5) |
C9 | 0.0120 (6) | 0.0144 (6) | 0.0126 (7) | −0.0037 (5) | 0.0013 (5) | 0.0015 (5) |
N10 | 0.0172 (6) | 0.0156 (5) | 0.0123 (6) | −0.0010 (4) | 0.0000 (5) | −0.0010 (4) |
C11 | 0.0184 (7) | 0.0162 (6) | 0.0104 (7) | −0.0032 (5) | −0.0017 (5) | −0.0008 (5) |
N12 | 0.0163 (6) | 0.0155 (5) | 0.0128 (6) | −0.0008 (4) | −0.0028 (5) | −0.0004 (4) |
C12A | 0.0117 (6) | 0.0137 (6) | 0.0114 (7) | −0.0037 (5) | 0.0015 (5) | 0.0003 (5) |
N13 | 0.0121 (5) | 0.0137 (5) | 0.0134 (6) | 0.0006 (4) | −0.0017 (4) | −0.0001 (4) |
C71 | 0.0247 (8) | 0.0302 (8) | 0.0126 (8) | 0.0027 (6) | −0.0005 (6) | −0.0033 (6) |
N91 | 0.0193 (6) | 0.0136 (5) | 0.0159 (7) | 0.0017 (4) | −0.0056 (5) | −0.0024 (5) |
C97 | 0.0146 (6) | 0.0151 (6) | 0.0208 (8) | 0.0024 (5) | 0.0004 (6) | −0.0014 (5) |
C91 | 0.0167 (7) | 0.0134 (6) | 0.0180 (8) | 0.0030 (5) | 0.0044 (6) | −0.0057 (5) |
C92 | 0.0204 (7) | 0.0168 (6) | 0.0225 (8) | 0.0040 (5) | 0.0006 (6) | −0.0032 (6) |
C93 | 0.0314 (8) | 0.0161 (7) | 0.0276 (9) | 0.0037 (6) | 0.0081 (7) | 0.0018 (6) |
C94 | 0.0253 (8) | 0.0155 (6) | 0.0342 (10) | −0.0037 (6) | 0.0119 (7) | −0.0052 (6) |
C95 | 0.0188 (7) | 0.0235 (7) | 0.0314 (9) | −0.0025 (6) | 0.0017 (6) | −0.0089 (6) |
C96 | 0.0195 (7) | 0.0196 (6) | 0.0210 (8) | 0.0009 (5) | −0.0004 (6) | −0.0023 (6) |
Geometric parameters (Å, º) top
C1—N13 | 1.4734 (16) | C8A—C9 | 1.4162 (18) |
C1—C2 | 1.5221 (19) | C9—N10 | 1.3518 (18) |
C1—H1A | 0.9900 | C9—N91 | 1.3598 (17) |
C1—H1B | 0.9900 | N10—C11 | 1.3331 (17) |
C2—C3 | 1.527 (2) | C11—N12 | 1.3223 (17) |
C2—H2A | 0.9900 | C11—H11 | 0.9500 |
C2—H2B | 0.9900 | N12—C12A | 1.3593 (17) |
C3—C3A | 1.513 (2) | C12A—N13 | 1.4036 (16) |
C3—H3A | 0.9900 | C71—H71A | 0.9800 |
C3—H3B | 0.9900 | C71—H71B | 0.9800 |
C3A—C4 | 1.3958 (19) | C71—H71C | 0.9800 |
C3A—C3B | 1.4042 (18) | N91—C97 | 1.4607 (16) |
C3B—C6A | 1.400 (2) | N91—H91 | 0.855 (17) |
C3B—N13 | 1.4311 (16) | C97—C91 | 1.5171 (18) |
C4—C5 | 1.379 (2) | C97—H97A | 0.9900 |
C4—H4 | 0.9500 | C97—H97B | 0.9900 |
C5—C6 | 1.389 (2) | C91—C92 | 1.392 (2) |
C5—H5 | 0.9500 | C91—C96 | 1.396 (2) |
C6—C6A | 1.3894 (19) | C92—C93 | 1.389 (2) |
C6—H6 | 0.9500 | C92—H92 | 0.9500 |
C6A—C7 | 1.5096 (18) | C93—C94 | 1.388 (2) |
C7—C71 | 1.5277 (19) | C93—H93 | 0.9500 |
C7—C8 | 1.5284 (18) | C94—C95 | 1.385 (2) |
C7—H7 | 1.0000 | C94—H94 | 0.9500 |
C8—C8A | 1.5066 (19) | C95—C96 | 1.385 (2) |
C8—H8A | 0.9900 | C95—H95 | 0.9500 |
C8—H8B | 0.9900 | C96—H96 | 0.9500 |
C8A—C12A | 1.3969 (18) | | |
| | | |
N13—C1—C2 | 110.07 (11) | C12A—C8A—C8 | 127.08 (12) |
N13—C1—H1A | 109.6 | C9—C8A—C8 | 117.61 (11) |
C2—C1—H1A | 109.6 | N10—C9—N91 | 116.32 (12) |
N13—C1—H1B | 109.6 | N10—C9—C8A | 123.27 (12) |
C2—C1—H1B | 109.6 | N91—C9—C8A | 120.42 (12) |
H1A—C1—H1B | 108.2 | C11—N10—C9 | 114.77 (11) |
C1—C2—C3 | 108.87 (12) | N12—C11—N10 | 128.05 (13) |
C1—C2—H2A | 109.9 | N12—C11—H11 | 116.0 |
C3—C2—H2A | 109.9 | N10—C11—H11 | 116.0 |
C1—C2—H2B | 109.9 | C11—N12—C12A | 116.49 (11) |
C3—C2—H2B | 109.9 | N12—C12A—C8A | 121.87 (11) |
H2A—C2—H2B | 108.3 | N12—C12A—N13 | 113.89 (11) |
C3A—C3—C2 | 113.47 (11) | C8A—C12A—N13 | 124.21 (12) |
C3A—C3—H3A | 108.9 | C12A—N13—C3B | 120.12 (10) |
C2—C3—H3A | 108.9 | C12A—N13—C1 | 117.79 (11) |
C3A—C3—H3B | 108.9 | C3B—N13—C1 | 113.11 (10) |
C2—C3—H3B | 108.9 | C7—C71—H71A | 109.5 |
H3A—C3—H3B | 107.7 | C7—C71—H71B | 109.5 |
C4—C3A—C3B | 118.00 (13) | H71A—C71—H71B | 109.5 |
C4—C3A—C3 | 119.10 (12) | C7—C71—H71C | 109.5 |
C3B—C3A—C3 | 122.85 (12) | H71A—C71—H71C | 109.5 |
C6A—C3B—C3A | 121.25 (12) | H71B—C71—H71C | 109.5 |
C6A—C3B—N13 | 119.43 (11) | C9—N91—C97 | 123.44 (12) |
C3A—C3B—N13 | 119.22 (12) | C9—N91—H91 | 118.7 (10) |
C5—C4—C3A | 121.14 (13) | C97—N91—H91 | 117.3 (10) |
C5—C4—H4 | 119.4 | N91—C97—C91 | 114.07 (11) |
C3A—C4—H4 | 119.4 | N91—C97—H97A | 108.7 |
C4—C5—C6 | 120.20 (13) | C91—C97—H97A | 108.7 |
C4—C5—H5 | 119.9 | N91—C97—H97B | 108.7 |
C6—C5—H5 | 119.9 | C91—C97—H97B | 108.7 |
C5—C6—C6A | 120.42 (14) | H97A—C97—H97B | 107.6 |
C5—C6—H6 | 119.8 | C92—C91—C96 | 118.56 (13) |
C6A—C6—H6 | 119.8 | C92—C91—C97 | 119.52 (13) |
C6—C6A—C3B | 118.86 (13) | C96—C91—C97 | 121.93 (13) |
C6—C6A—C7 | 122.57 (13) | C93—C92—C91 | 121.06 (14) |
C3B—C6A—C7 | 118.55 (11) | C93—C92—H92 | 119.5 |
C6A—C7—C71 | 113.73 (11) | C91—C92—H92 | 119.5 |
C6A—C7—C8 | 110.14 (11) | C94—C93—C92 | 119.73 (14) |
C71—C7—C8 | 109.41 (11) | C94—C93—H93 | 120.1 |
C6A—C7—H7 | 107.8 | C92—C93—H93 | 120.1 |
C71—C7—H7 | 107.8 | C95—C94—C93 | 119.68 (13) |
C8—C7—H7 | 107.8 | C95—C94—H94 | 120.2 |
C8A—C8—C7 | 116.77 (11) | C93—C94—H94 | 120.2 |
C8A—C8—H8A | 108.1 | C96—C95—C94 | 120.54 (14) |
C7—C8—H8A | 108.1 | C96—C95—H95 | 119.7 |
C8A—C8—H8B | 108.1 | C94—C95—H95 | 119.7 |
C7—C8—H8B | 108.1 | C95—C96—C91 | 120.44 (14) |
H8A—C8—H8B | 107.3 | C95—C96—H96 | 119.8 |
C12A—C8A—C9 | 115.18 (12) | C91—C96—H96 | 119.8 |
| | | |
N13—C1—C2—C3 | −63.04 (14) | C9—N10—C11—N12 | 4.9 (2) |
C1—C2—C3—C3A | 36.42 (15) | N10—C11—N12—C12A | −0.4 (2) |
C2—C3—C3A—C4 | 175.61 (13) | C11—N12—C12A—C8A | −5.04 (18) |
C2—C3—C3A—C3B | −7.09 (19) | C11—N12—C12A—N13 | 176.53 (11) |
C4—C3A—C3B—C6A | 2.6 (2) | C9—C8A—C12A—N12 | 5.37 (18) |
C3—C3A—C3B—C6A | −174.77 (12) | C8—C8A—C12A—N12 | −170.31 (12) |
C4—C3A—C3B—N13 | 178.94 (12) | C9—C8A—C12A—N13 | −176.37 (11) |
C3—C3A—C3B—N13 | 1.62 (19) | C8—C8A—C12A—N13 | 8.0 (2) |
C3B—C3A—C4—C5 | 0.6 (2) | N12—C12A—N13—C3B | −137.57 (12) |
C3—C3A—C4—C5 | 178.05 (13) | C8A—C12A—N13—C3B | 44.05 (18) |
C3A—C4—C5—C6 | −2.2 (2) | N12—C12A—N13—C1 | 7.39 (16) |
C4—C5—C6—C6A | 0.6 (2) | C8A—C12A—N13—C1 | −170.99 (12) |
C5—C6—C6A—C3B | 2.5 (2) | C6A—C3B—N13—C12A | −64.73 (17) |
C5—C6—C6A—C7 | −176.39 (13) | C3A—C3B—N13—C12A | 118.82 (13) |
C3A—C3B—C6A—C6 | −4.1 (2) | C6A—C3B—N13—C1 | 148.80 (12) |
N13—C3B—C6A—C6 | 179.51 (12) | C3A—C3B—N13—C1 | −27.65 (16) |
C3A—C3B—C6A—C7 | 174.84 (12) | C2—C1—N13—C12A | −88.19 (14) |
N13—C3B—C6A—C7 | −1.54 (18) | C2—C1—N13—C3B | 59.12 (14) |
C6—C6A—C7—C71 | 14.54 (19) | N10—C9—N91—C97 | −9.89 (19) |
C3B—C6A—C7—C71 | −164.37 (12) | C8A—C9—N91—C97 | 169.98 (12) |
C6—C6A—C7—C8 | −108.68 (15) | C9—N91—C97—C91 | −81.94 (17) |
C3B—C6A—C7—C8 | 72.41 (15) | N91—C97—C91—C92 | −102.99 (14) |
C6A—C7—C8—C8A | −63.28 (15) | N91—C97—C91—C96 | 76.50 (17) |
C71—C7—C8—C8A | 171.01 (11) | C96—C91—C92—C93 | −0.6 (2) |
C7—C8—C8A—C12A | 5.31 (19) | C97—C91—C92—C93 | 178.92 (12) |
C7—C8—C8A—C9 | −170.28 (11) | C91—C92—C93—C94 | 0.7 (2) |
C12A—C8A—C9—N10 | −0.53 (18) | C92—C93—C94—C95 | −0.5 (2) |
C8—C8A—C9—N10 | 175.57 (12) | C93—C94—C95—C96 | 0.1 (2) |
C12A—C8A—C9—N91 | 179.60 (11) | C94—C95—C96—C91 | 0.0 (2) |
C8—C8A—C9—N91 | −4.29 (18) | C92—C91—C96—C95 | 0.2 (2) |
N91—C9—N10—C11 | 175.67 (11) | C97—C91—C96—C95 | −179.25 (13) |
C8A—C9—N10—C11 | −4.20 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N91—H91···N10i | 0.857 (17) | 2.446 (17) | 3.2332 (18) | 152.9 (14) |
C11—H11···N12ii | 0.95 | 2.59 | 3.4281 (19) | 147 |
C1—H1A···Cg5iii | 0.99 | 2.85 | 3.8018 (17) | 162 |
C7—H7···Cg6iii | 1.00 | 2.88 | 3.7965 (16) | 153 |
Symmetry codes: (i) −x+3/2, y, z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1. |
Parameters (Å, °) for hydrogen bonds and short intermolecular contacts topCompound | D—H···A | | D—H | H···A | D···A | D—H···A |
(I) | N3—H3···O4i | | 0.87 (3) | 1.88 (3) | 2.745 (3) | 175 (3) |
| C2—H2···N1ii | | 0.95 | 2.52 | 3.304 (3) | 140 |
(II) | O81—H81···N3iii | | 1.01 (3) | 1.82 (3) | 2.825 (2) | 171 (2) |
| C2—H2···N1iv | | 0.95 | 2.59 | 3.330 (4) | 135 |
| C10—H10···Cg1v | | 0.95 | 2.85 | 3.743 (2) | 156 |
(III) | O81—H81···N3vi | | 0.87 (2) | 1.91 (2) | 2.767 (2) | 165 (2) |
(IV) | C2—H2···.O81vi | | 0.95 | 2.57 | 3.386 (2) | 144 |
| C45—H45···Cg1vii | | 0.95 | 2.99 | 3.7583 (19) | 139 |
| C46—H46···Cg2viii | | 0.95 | 2.99 | 3.7583 (19) | 139 |
(V) | C7—H7B···N11ix | | 0.99 | 2.59 | 3.478 (2) | 150 |
| C1—H1B···Cg3x | | 0.99 | 2.94 | 3.758 (2) | 140 |
| C5—H5···Cg3xi | | 0.95 | 2.90 | 3.712 (2) | 144 |
| C7—H7A···Cg4xi | | 0.99 | 2.73 | 3.6068 (19) | 147 |
(VI) | N91—H91···N10xii | | 0.857 (17) | 2.446 (17) | 3.2332 (18) | 152.9 (14) |
| C11—H11···N12xiii | | 0.95 | 2.59 | 3.4281 (19) | 147 |
| C1—H1A···Cg5xiv | | 0.99 | 2.85 | 3.8018 (17) | 162 |
| C7—H7···Cg6xiv | | 1.00 | 2.88 | 3.7965 (16) | 153 |
Cg1–Cg6 represent the centroids of the C6A/C7–C10/C10A,
N1/C2/N3/C4–C6, N9/C8/C7A/C11A/N11/C10, C2A/C2B/C5A/C5/C4/C3,
C91–C96 and N10/C9/C8A/C12A/N12/C11 rings, respectively.
The perpendicular distances of the H atoms from the ring planes in the
C—H···π interactions are (Å): 2.82 for (II),
H45 2.94 and H46 2.95 for (IV);
H1B 2.76, H5 2.68 and H7A 2.69 for (V);
H1A 2.82, H7 2.83 for (VI).
Symmetry codes: (i) -x, -y, -z+1;
(ii) -x, y-1/2, -z+1/2;
(iii) x, -y+3/2, z+1/2;
(iv) -x, -y+2, -z+1;
(v) -x, y+1/2, -z+3/2;
(vi) x, -y+3/2, z-1/2;
(vii) -x+1, -y+2, -z+1;
(viii) -x+1, y+1/2, -z+1/2;
(ix) -x+2, y+1/2, -z+1;
(x) -x+2, y-1/2, -z+1;
(xi) -x+1, y+1/2, -z+1;
(xii) -x+3/2, y, z+1/2;
(xiii) -x+1, -y+1, -z;
(xiv) -x+1, -y+1, -z+1. |
Selected geometric parameters (Å, °) topCompound | (I) | (II) | (III) | (IV) | (V) | (VI) |
Ring-puckering parameters | | | | | | |
(a) | Five-membered ring | | | | | |
Q2 | | | | | 0.176 (2) | |
φ2 | | | | | 47.2 (7) | |
| | | | | | |
(b) | Six-membered ring | | | | | |
Q | | | | | | 0.5135 (14) |
θ | | | | | | 129.17 (16) |
φ | | | | | | 250.8 (2) |
| | | | | | |
(c) | Seven-membered rings | | | | | |
Q | 0.830 (2) | 0.880 (2) | 0.8709 (18) | 0.8444 (16) | 0.6813 (18) | 0.8585 (14) |
φ2 | 34.00 (19) | 29.60 (16) | 51.24 (13) | 45.62 (11) | 302.24 (18) | 35.11 (10) |
φ3 | 290.3 (6) | 295.1 (5) | 283.4 (3) | 291.1 (3) | 85.0 (3) | 292.7 (3) |
| | | | | | |
Dihedral angles | | | | | | |
| 54.37 (12) | 57.43 (11) | 47.49 (8) | 51.02 (7) | 28.05 (8) | 52.90 (6) |
| | | | | | |
Notes: (i) ring-puckering angles are calculated for the following atom
sequences: five-membered ring N12–C1–C2–C2A–C2B;
six-membered ring N13–C1–C2–C3–C3A–C3B;
seven-membered rings N11–C10A–C6A–C6–C5–C4A–C11A for (I)–(IV),
N12–C2B–C5A–C6–C7–C7A–C11A for (V) and
N13–C3B–C6A–C7–C8–C8A–C12A for (VI);
(ii) dihedral denotes the dihedral angle between the mean planes
of the fused phenyl and pyrimidine rings. |
Selected torsion angles in (IV)–(VI) (Å, °) top(IV) | C4A—C4—N41—C47 | 178.04 (15) |
| C4—N41—C47—C41 | -141.85 (16) |
| N41—C47—C41—C42 | -98.48 (19) |
(V) | C7A—C8—N81—C87 | -165.79 (18) |
| C8—N81—C87—C81 | 114.1 (2) |
| N81—C87—C81—C82 | -48.5 (3) |
(VI) | C8A—C9—N91—C97 | 169.98 (12) |
| C9—N91—C97—C91 | -81.94 (17) |
| N91—C97—C91—C92 | -102.99 (14) |
Note: (i) The IUPAC names for compounds (IV)–(VI) lead to different atom
labels for comparable sequences of atoms, but the equivalence of the torsion
angles reported for (IV)–(VI) is shown by Figs. 4–6. |