Six polycyclic pyrimidoazepine derivatives: syntheses, mol­ecular structures and supra­molecular assembly

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).

Computing details

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-4H-benzo[b]pyrimido[5,4-f]azepin-4-one

Crystal data

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) Å^3	Block, colourless
Z = 4	0.25 × 0.18 × 0.16 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 0.5675P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4^i	0.87 (3)	1.88 (3)	2.745 (3)	175 (3)
C2—H2···N1^ii	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-5H-benzo[b]pyrimido[5,4-f]azepin-8-ol

Crystal data

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) Å^3	Block, colourless
Z = 4	0.14 × 0.12 × 0.12 mm

Data collection

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

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0517P)^2 + 0.7285P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0056 (5)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···N3^i	1.01 (3)	1.82 (3)	2.825 (2)	171 (2)
C2—H2···N1^ii	0.95	2.59	3.330 (4)	135
C10—H10···Cg1^iii	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-5H-benzo[b]pyrimido[5,4-f]azepin-8-ol

Crystal data

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) Å^3	Block, colourless
Z = 8	0.14 × 0.12 × 0.12 mm
F(000) = 1216

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 2.3537P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···N3^i	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-5H- benzo[b]pyrimido[5,4-f]azepin-4-amine

Crystal data

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) Å^3	Block, colourless
Z = 4	0.12 × 0.10 × 0.10 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.6796P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O81^i	0.95	2.57	3.386 (2)	144
C45—H45···Cg1^ii	0.95	2.99	3.7583 (19)	139
C46—H46···Cg2^iii	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

Crystal data

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) Å^3	Block, colourless
Z = 2	0.14 × 0.12 × 0.09 mm

Data collection

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

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0471P)^2 + 0.1235P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···N11^i	0.99	2.59	3.478 (2)	150
C1—H1B···Cg3^ii	0.99	2.94	3.758 (2)	140
C5—H5···Cg3^iii	0.95	2.90	3.712 (2)	144
C7—H7A···Cg4^iii	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-1H-pyrimido[5',4':6,7]azepino[3,2,1-ij]quinolin-9-amine

Crystal data

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) Å^3	Block, colourless
Z = 8	0.12 × 0.12 × 0.10 mm
F(000) = 1520

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 1.5761P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N91—H91···N10^i	0.857 (17)	2.446 (17)	3.2332 (18)	152.9 (14)
C11—H11···N12^ii	0.95	2.59	3.4281 (19)	147
C1—H1A···Cg5^iii	0.99	2.85	3.8018 (17)	162
C7—H7···Cg6^iii	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.