Four 2-amino-6-aryl-4-meth­oxy-11H-pyrimido[4,5-b][1,4]benzodiazepines: similar mol­ecular structures but different crystal structures

2-Amino-4-meth­oxy-6-phenyl-11H-pyrimido[4,5-b][1,4]benzodiazepine, C₁₈H₁₅N₅O, (I), and its 6-(2-fluoro­phenyl)-, 6-(3-nitro­phenyl)- and 6-(4-methoxy­phenyl)- analogues, viz. C₁₈H₁₄FN₅O, (II), C₁₈H₁₄N₆O₃, (III), and C₁₉H₁₇N₅O₂, (IV), respectively, all adopt mol­ecular conformations which are almost identical, containing boat-shaped seven-membered rings. In each structure, paired N-H...N hydrogen bonds link the mol­ecules into centrosymmetric dimers. In each of (I)-(III), the dimers are further linked, forming a different three-dimensional framework in each case, while in compound (IV) the dimers are linked into sheets. The significance of this study lies in the observation of different crystal structures in four compounds whose mol­ecular structures are very similar.

S1. Comment

Pyrimidine-fused compounds are of considerable interest in medicinal chemistry as they have shown a wide variety of biological properties (Wang et al., 2004; McGuigan et al., 2004; Gangjee et al., 2004). Here, we report the structures of four different 2-amino-4-methoxy-11H-pyrimido[4,5-b][1,4]benzodiazepines, compounds (I)–(IV) (Fig. 1), containing differently substituted 6-aryl groups, all of which have been prepared using a synthetic strategy based on a nitrosation-aminolysis-nitroso reduction sequence followed by a Bischler–Napieralski cyclocondensation (Cobo et al., 2008). The structure of compound (II) has been very briefly reported, as a proof of constitution associated with the synthetic report (Cobo et al., 2008), but without any information on, or discussion of, either the molecular conformation or the hydrogen bonding. In the earlier report, the F-atom site occupancies were fixed at 0.75 and 0.25; these occupancies have now been refined to values of 0.774 (5) and 0.226 (5).

Compounds (I)–(IV) have very similar constitutions, differing only by a single substituent and its location in the pendent aryl ring. The molecules accordingly have very similar conformations (Fig. 1) which lack any internal symmetry, so that the molecules are chiral; the reference molecules were selected so that they all have the same hand. The compounds all crystallize in space group P2₁/n, and their unit-cell dimensions are similar. In addition, the atomic coordinates for corresponding atoms are similar in compounds (I)–(III), whereas the atomic coordinates for compound (IV) are approximately related to those in (I)–(III) by the relationship (1 - x, 1 - y, z), suggesting an approximate relationship equivalent to a twofold rotation around the z axis or, equivalently, a mirror reflection across the [001] plane. However, there are some differences in the patterns of supramolecular aggregation manifested by the intermolecular hydrogen bonds, so that no two of these compounds are strictly isostructural.

The overall molecular conformations are dominated by the seven-membered rings, for which the ring-puckering parameters (Cremer & Pople, 1975) indicate (Table 1) an almost ideal boat form (Evans & Boeyens, 1989) in each compound, with a local pseudo-mirror plane containing atoms N11 and H11 and the mid-point of the bond N5—C6, as demonstrated by the atom-displacements from the mean planes for this ring. The orientation of the pendent phenyl ring, as indicated by the torsion angle N5—C6—C61—C62 (Table 1), is similar in each compound. The nitro and methoxy substituents on the pendent aryl ring and on the fused pyrimidyl ring are both almost coplanar with the rings concerned, as indicated by both the relevant torsion angles and the displacements of the substituent atoms from the ring planes. The conformational similarity between compounds (I)–(IV) in terms of the ring-puckering parameters, the out-of-plane atom displacements and the torsion angles is striking. The bond lengths and angles present no unusual features.

A search of the Cambridge Structural Database (CSD, Version 5.29, January 2008; Allen, 2002) found no examples of pyrimido[4,5-b][1,4]benzodiazepines. However, the structures of several pyrido[2,3-b][1,4]diazepines, (V)–(X), which are very closely related to compounds (I)–(IV), have recently been reported. In each of compounds (V) (CSD refcode INEMOD; Spirlet et al., 2003), (VI) (ZAYPOE; Dupont et al., 1995), (VII) (KOYTIB; Dupont et al., 1992) and (VIII) (IDIMOX; Dupont et al., 2002), the conformation of the seven-membered ring is almost identical to those found in (I)–(IV), as also are those in the N¹¹-substituted compounds (IX) and (X) (SONBOM and SONBIG, respectively; Dupont et al., 1991).

Despite the similarity in the unit-cell dimensions of compounds (I)–(IV) and the close similarity of their molecular structures, these compounds differ in both their crystal structures and in the patterns of the hydrogen bonding. In each compound, paired N—H···N hydrogen bonds, with atom N11 as the donor and pyrimidine atom N1 as the acceptor, generate centrosymmetric R²₂(8) motifs (Bernstein et al., 1995), centred for the sake of convenience at (1/2, 1/2, 1/2) in each case. However, the subsequent linking of the dimeric units is different in each case, leading to the formation of different three-dimensional hydrogen-bonded framework structures in each of (I)–(III), and to a two-dimensional network in (IV).

In each of (I)–(III), a second N—H···N hydrogen bond (Table 2) links the R²₂(8) dimers into a sheet. Amino atom N2 in the molecule at (x, y, z), which forms part of the dimer centred at (1/2, 1/2, 1/2), acts as hydrogen-bond donor to ring atom N5 in the molecule at (1/2 - x, 1/2 + y, 1/2 - z), which forms part of the dimer centred at (0, 1, 0). In this manner, the dimer centred at (1/2, 1/2, 1/2) is directly linked to the four dimers centred at (0, 0, 0), (0, 1, 0), (1, 0, 1) and (1, 1, 1), so forming a sheet parallel to (101) built solely from N—H···N hydrogen bonds and consisting of R²₂(8) rings alternating with R⁶₆(32) rings (Fig. 2).

These sheets are then linked to form a three-dimensional framework by the cooperative action of C—H···N and C—H···π(arene) hydrogen bonds in (I) and by just a single C—H···π(arene) hydrogen bond in (II). In each of (I) and (II) these additional hydrogen bonds form a chain running parallel to [010] in which alternate molecules form parts of adjacent (101) sheets. The final two hydrogen bonds in the structure of (III) link the (101) sheets into a continuous framework structure via two distinct motifs. Aryl atom C8 in the molecule at (x, y, z) acts as donor to nitro atom O632 in the molecule at (2 - x, -y, 1 - z), so forming a centrosymmetric R²₂(20) motif centred at (1, 0, 1/2). This motif links the R²₂(8) dimers into a chain running parallel to [110] and containing R²₂(8) rings centred at (1/2 + n, 1/2 - n, 1/2) (where n represents zero or an integer) alternating with R²₂(20) rings centred at (n, 1 - n, 1/2) (where n represents zero or an integer) (Fig. 3). The combination of a chain along [110] and a sheet parallel to (101) is sufficient to generate a three-dimensional framework structure. Finally, aryl atom C65 at (x, y, z) acts as donor to the ring C6a/C7–C10/C10a in the molecule at (3/2 - x, -1/2 + y, 1/2 - z), so forming a chain running parallel to the [010] direction and consisting of molecules related by the 2₁ screw axis along (3/4, y, 1/4), where successive molecules are components of two different (101) sheets (Fig. 4).

The linking of the R²₂(8) rings in (IV) again generates a sheet parallel to (101), just as in (III), but now the dimers are linked by a C—H···π(arene) hydrogen bond rather than by an N—H···N hydrogen bond (Fig. 5). Indeed, neither of the N—H bonds of the amino group plays any role in the hydrogen bonding, as there are no potential hydrogen-bond acceptors within 2.60 Å of the amino H atoms in (IV). There are no direction-specific interactions of any kind between adjacent sheets, so that the hydrogen-bonded structure of (IV) is strictly two-dimensional. It is striking that in neither compound does pyrimidine atom N3 play any role in the hydrogen bonding.

Thus, although the unit-cell dimensions of compounds (I)–(IV) are similar and their molecular constitutions and conformations are almost identical, unexpectedly the crystal structures, dominated by multiple hydrogen bonds, are somewhat different.

It is of interest briefly to compare the hydrogen-bonded structures of (I)–(IV) with those found in compounds (V)–(VIII). This comparison is of particular interest in view of the non-participation in the hydrogen-bonded structures of (I)–(IV) by atom N3, the sole point of difference in the fused tricyclic systems of (I)–(IV) on the one hand and (V)–(VIII) on the other.

In both (V) and (VI), paired N—H···N hydrogen bonds having the pyridine N atom as acceptor generate centrosymmetric R²₂(8) dimers, exactly as in (I)–(IV). In (V) these dimers are linked into chains of centrosymmetric rings by pairs of symmetry-related C—H···π(arene) hydrogen bonds, but there are no direction-specific interactions between the dimers in (VI). In neither compound do the two N atoms of the pendent piperidine substituent play any part in the hydrogen bonding. By contrast, there are two independent N—H···N hydrogen bonds in (VIII). An intramolecular hydrogen bond is formed by the two N atoms of the dimethylaminopropylamine substituent, and an intermolecular hydrogen bond utilizes the ring N—H as donor and the imine N atom of the diazepine ring as acceptor to form a simple C(5) chain. A single C—H···π(arene) hydrogen bond links these chains into sheets.

Compound (VII) crystallizes from acetone–methanol (50:50 v/v) as a sesquihydrate (Dupont et al., 1992) with two molecules of the organic component and three water molecules in the asymmetric unit. All of the N—H and O—H bonds are involved in the hydrogen bonding, which generates a ribbon or chain of edge-fused rings running parallel to the [111] direction of the triclinic cell, in which there are rings of R²₂(8), R⁴₄(8), R⁴₄(13) and R⁶₆(32) types, the second and fourth of which are centrosymmetric (Fig. 6). Embedded within the ribbon is a homodromic (Saenger & Lindner, 1980) and centrosymmetric ring of four hydrogen-bonded water molecules.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Cobo et al. (2008); Cremer & Pople (1975); Dupont et al. (1991, 1992, 1995, 2002); Evans & Boeyens (1989); Gangjee et al. (2004); McGuigan et al. (2004); Saenger & Lindner (1980); Spirlet et al. (2003); Wang et al. (2004).

S2. Experimental

Samples of compounds (I)–(IV) were prepared as described previously by Cobo et al. (2008). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in methanol.

S3. Refinement

All H atoms were located in difference maps, and then treated as riding atoms with distances C-H 0.95 Å (aromatic)) or 0.98 Å (CH₃) and N-H 0.88 Å, and with U_iso(H) = kU_eq(carrier) where k = 1.5 for the methyl groups and 1.2 for all other H atoms. Compound (I) was handled as a non-merohedral twin, using the HKLF5 option in SHELXL, with a twinning matrix (1,0,0 0,1,0, 0.310,0,1) giving twin fractions of 0.847 (4) and 0.153 (4). In compound (II) the F atom was disordered over two sites, bonded respectively to atoms C62 and C66, with occupancies 0.775 (5) and 0.225 (5); restraints were applied to nsure similarity of the C-F distances and C-C-F angles in the two orientations. For compound (IV) the merging index was 0.179, but this occurred for a weak dataset with only 42.7% of the reflections having I > 2σ(I), despite data collection at 120 K.

Computing details

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structures of (I)–(IV), showing the atom-labelling schemes. (a) Compound (I), (b) (II), (c) (III) and (d) (IV). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The refined occupancies of the F-atom sites in compound (II) are 0.774 (5) and 0.226 (5), respectively.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a sheet of alternating R^22(8) and R^66(36) rings parallel to (101) formed by two independent N—H···N hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted. Entirely analogous sheets can be identified in the structures of (II) and (III).
	Fig. 3. A stereoview of part of the crystal structure of (III), showing the formation of a chain of alternating R^22(8) and R^22(20) rings along [110] formed by N—H···N and C—H···O hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms and not involved in the motif shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (III), showing the formation of a chain along [010] formed by C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms and not involved in the motif shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of (IV), showing the formation of a sheet parallel to (101) using a combination of N—H···N and C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms and not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (V) (CSD refcode KOYTIB; Dupont et al., 1992), showing the formation of a chain containing four types of ring. The original atom coordinates have been used and, for the sake of clarity, H atoms bonded to C atoms have all been omitted.

(I) 2-Amino-4-methoxy-6-phenyl-11H-pyrimido[4,5-b][1,4]benzodiazepine

Crystal data

C18H15N5O	F(000) = 664
Mr = 317.35	Dx = 1.445 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3338 reflections
a = 7.022 (6) Å	θ = 3.0–27.5°
b = 12.855 (9) Å	µ = 0.10 mm^−1
c = 16.199 (8) Å	T = 120 K
β = 93.851 (5)°	Block, colourless
V = 1459.0 (18) Å^3	0.47 × 0.35 × 0.26 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3338 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2768 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→16
Tmin = 0.967, Tmax = 0.976	l = 0→21
3338 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.225	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0493P)^2 + 4.1282P] where P = (Fo^2 + 2Fc^2)/3
3338 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.59 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	0.3932 (4)	0.35940 (19)	0.16820 (13)	0.0235 (6)
N1	0.4481 (4)	0.5128 (2)	0.38514 (16)	0.0224 (6)
N2	0.3360 (5)	0.6578 (2)	0.31532 (17)	0.0254 (7)
H21	0.3453	0.6926	0.3622	0.030*
H22	0.2943	0.6890	0.2693	0.030*
N3	0.3723 (4)	0.5113 (2)	0.23931 (16)	0.0216 (6)
N5	0.4956 (4)	0.2487 (2)	0.30175 (16)	0.0215 (6)
N11	0.5697 (4)	0.3667 (2)	0.45435 (16)	0.0215 (6)
H11	0.5057	0.3652	0.4992	0.026*
C2	0.3853 (5)	0.5575 (3)	0.3141 (2)	0.0211 (7)
C4	0.4114 (5)	0.4125 (3)	0.23912 (19)	0.0214 (7)
C4a	0.4765 (5)	0.3557 (3)	0.30917 (19)	0.0203 (7)
C6	0.6288 (5)	0.1976 (3)	0.34079 (19)	0.0200 (7)
C6a	0.7839 (5)	0.2408 (3)	0.39693 (19)	0.0209 (7)
C7	0.9682 (5)	0.2030 (3)	0.39337 (19)	0.0228 (7)
H7	0.9911	0.1479	0.3562	0.027*
C8	1.1191 (5)	0.2430 (3)	0.4423 (2)	0.0260 (8)
H8	1.2446	0.2168	0.4381	0.031*
C9	1.0852 (6)	0.3218 (3)	0.4975 (2)	0.0268 (8)
H9	1.1871	0.3486	0.5328	0.032*
C10	0.9050 (5)	0.3612 (3)	0.5014 (2)	0.0251 (7)
H10	0.8837	0.4159	0.5391	0.030*
C10a	0.7521 (5)	0.3227 (3)	0.45121 (19)	0.0206 (7)
C11a	0.4976 (5)	0.4133 (3)	0.38066 (19)	0.0198 (7)
C41	0.3365 (6)	0.4167 (3)	0.0952 (2)	0.0265 (8)
H411	0.4354	0.4679	0.0844	0.040*
H412	0.2161	0.4528	0.1029	0.040*
H413	0.3192	0.3689	0.0482	0.040*
C61	0.6320 (5)	0.0853 (3)	0.3227 (2)	0.0218 (7)
C62	0.6699 (5)	0.0121 (3)	0.3845 (2)	0.0260 (8)
H62	0.7038	0.0342	0.4395	0.031*
C63	0.6587 (6)	−0.0922 (3)	0.3665 (2)	0.0303 (8)
H63	0.6842	−0.1420	0.4092	0.036*
C64	0.6104 (6)	−0.1250 (3)	0.2865 (2)	0.0297 (8)
H64	0.6009	−0.1972	0.2742	0.036*
C65	0.5764 (5)	−0.0529 (3)	0.2250 (2)	0.0282 (8)
H65	0.5445	−0.0753	0.1700	0.034*
C66	0.5881 (5)	0.0512 (3)	0.2422 (2)	0.0245 (7)
H66	0.5660	0.1004	0.1989	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0372 (14)	0.0232 (12)	0.0098 (10)	0.0017 (10)	−0.0010 (9)	−0.0015 (9)
N1	0.0331 (16)	0.0209 (14)	0.0127 (13)	0.0023 (12)	−0.0014 (11)	−0.0012 (11)
N2	0.0409 (18)	0.0211 (14)	0.0139 (13)	0.0018 (13)	−0.0009 (12)	−0.0014 (11)
N3	0.0282 (15)	0.0236 (14)	0.0131 (12)	0.0013 (12)	0.0015 (11)	−0.0007 (11)
N5	0.0300 (15)	0.0209 (14)	0.0134 (12)	0.0001 (12)	0.0010 (11)	−0.0017 (11)
N11	0.0313 (15)	0.0251 (14)	0.0080 (11)	0.0033 (12)	0.0008 (10)	0.0008 (11)
C2	0.0245 (16)	0.0242 (16)	0.0145 (14)	−0.0005 (13)	0.0004 (12)	−0.0001 (13)
C4	0.0282 (17)	0.0239 (17)	0.0121 (14)	−0.0008 (14)	0.0017 (12)	−0.0028 (12)
C4a	0.0261 (17)	0.0215 (16)	0.0133 (14)	0.0017 (13)	0.0000 (12)	−0.0012 (12)
C6	0.0262 (17)	0.0222 (16)	0.0119 (13)	−0.0005 (13)	0.0032 (12)	−0.0007 (12)
C6a	0.0295 (17)	0.0212 (16)	0.0118 (14)	−0.0016 (13)	0.0005 (12)	0.0018 (12)
C7	0.0331 (18)	0.0226 (16)	0.0128 (14)	0.0022 (14)	0.0029 (13)	0.0024 (12)
C8	0.0275 (18)	0.0305 (19)	0.0198 (16)	0.0010 (15)	0.0015 (13)	0.0028 (14)
C9	0.0338 (19)	0.0282 (18)	0.0178 (15)	−0.0039 (15)	−0.0032 (14)	0.0010 (14)
C10	0.0360 (19)	0.0247 (17)	0.0140 (15)	−0.0015 (15)	−0.0016 (13)	−0.0011 (13)
C10a	0.0290 (17)	0.0212 (16)	0.0114 (14)	0.0007 (13)	0.0000 (12)	0.0039 (12)
C11a	0.0245 (16)	0.0223 (16)	0.0122 (14)	−0.0005 (13)	−0.0008 (12)	0.0004 (12)
C41	0.041 (2)	0.0260 (18)	0.0116 (14)	0.0012 (15)	−0.0037 (14)	0.0024 (13)
C61	0.0250 (17)	0.0224 (17)	0.0178 (15)	0.0017 (13)	−0.0004 (12)	−0.0024 (13)
C62	0.0338 (19)	0.0263 (18)	0.0174 (15)	0.0009 (15)	−0.0013 (13)	0.0004 (14)
C63	0.040 (2)	0.0240 (18)	0.0270 (18)	−0.0006 (16)	0.0021 (16)	0.0033 (15)
C64	0.035 (2)	0.0230 (18)	0.0313 (19)	0.0018 (15)	0.0045 (16)	−0.0049 (15)
C65	0.0317 (19)	0.0290 (19)	0.0236 (17)	0.0020 (15)	−0.0007 (14)	−0.0080 (15)
C66	0.0321 (18)	0.0244 (17)	0.0170 (15)	0.0032 (14)	0.0007 (13)	−0.0027 (13)

Geometric parameters (Å, º)

O4—C4	1.335 (4)	C7—H7	0.9500
O4—C41	1.427 (4)	C8—C9	1.382 (5)
N1—C11a	1.328 (4)	C8—H8	0.9500
N1—C2	1.335 (4)	C9—C10	1.368 (5)
N2—C2	1.335 (5)	C9—H9	0.9500
N2—H21	0.8800	C10—C10a	1.393 (5)
N2—H22	0.8800	C10—H10	0.9500
N3—C4	1.299 (5)	C41—H411	0.9800
N3—C2	1.347 (4)	C41—H412	0.9800
N5—C6	1.276 (5)	C41—H413	0.9800
N5—C4a	1.388 (4)	C61—C62	1.386 (5)
N11—C11a	1.399 (4)	C61—C66	1.391 (5)
N11—C10a	1.404 (5)	C62—C63	1.373 (5)
N11—H11	0.8800	C62—H62	0.9500
C4—C4a	1.400 (5)	C63—C64	1.384 (5)
C4a—C11a	1.374 (4)	C63—H63	0.9500
C6—C61	1.473 (5)	C64—C65	1.370 (5)
C6—C6a	1.480 (5)	C64—H64	0.9500
C6a—C7	1.387 (5)	C65—C66	1.367 (5)
C6a—C10a	1.399 (5)	C65—H65	0.9500
C7—C8	1.380 (5)	C66—H66	0.9500
C4—O4—C41	117.0 (3)	C9—C10—C10a	121.4 (3)
C11a—N1—C2	116.1 (3)	C9—C10—H10	119.3
C2—N2—H21	120.0	C10a—C10—H10	119.3
C2—N2—H22	120.0	C10—C10a—C6a	119.0 (3)
H21—N2—H22	120.0	C10—C10a—N11	120.3 (3)
C4—N3—C2	115.6 (3)	C6a—C10a—N11	120.7 (3)
C6—N5—C4a	122.6 (3)	N1—C11a—C4a	123.4 (3)
C11a—N11—C10a	114.9 (3)	N1—C11a—N11	116.5 (3)
C11a—N11—H11	122.6	C4a—C11a—N11	120.0 (3)
C10a—N11—H11	122.6	O4—C41—H411	109.5
N1—C2—N2	118.3 (3)	O4—C41—H412	109.5
N1—C2—N3	125.7 (3)	H411—C41—H412	109.5
N2—C2—N3	116.0 (3)	O4—C41—H413	109.5
N3—C4—O4	119.6 (3)	H411—C41—H413	109.5
N3—C4—C4a	124.4 (3)	H412—C41—H413	109.5
O4—C4—C4a	116.0 (3)	C62—C61—C66	118.8 (3)
C11a—C4a—N5	127.0 (3)	C62—C61—C6	121.8 (3)
C11a—C4a—C4	114.4 (3)	C66—C61—C6	119.3 (3)
N5—C4a—C4	118.3 (3)	C63—C62—C61	120.3 (3)
N5—C6—C61	115.3 (3)	C63—C62—H62	119.8
N5—C6—C6a	126.6 (3)	C61—C62—H62	119.8
C61—C6—C6a	118.0 (3)	C62—C63—C64	120.2 (4)
C7—C6a—C10a	118.6 (3)	C62—C63—H63	119.9
C7—C6a—C6	119.5 (3)	C64—C63—H63	119.9
C10a—C6a—C6	121.8 (3)	C65—C64—C63	119.7 (4)
C8—C7—C6a	121.9 (3)	C65—C64—H64	120.2
C8—C7—H7	119.1	C63—C64—H64	120.2
C6a—C7—H7	119.1	C66—C65—C64	120.6 (3)
C7—C8—C9	119.1 (3)	C66—C65—H65	119.7
C7—C8—H8	120.5	C64—C65—H65	119.7
C9—C8—H8	120.5	C65—C66—C61	120.4 (3)
C10—C9—C8	120.1 (3)	C65—C66—H66	119.8
C10—C9—H9	120.0	C61—C66—H66	119.8
C8—C9—H9	120.0
C11a—N1—C2—N2	−179.2 (3)	C7—C6a—C10a—C10	−1.9 (5)
C11a—N1—C2—N3	−1.4 (5)	C6—C6a—C10a—C10	−178.8 (3)
C4—N3—C2—N1	5.5 (5)	C7—C6a—C10a—N11	177.1 (3)
C4—N3—C2—N2	−176.7 (3)	C6—C6a—C10a—N11	0.2 (5)
C2—N3—C4—O4	176.8 (3)	C11a—N11—C10a—C10	116.9 (3)
C2—N3—C4—C4a	−4.5 (5)	C11a—N11—C10a—C6a	−62.1 (4)
C41—O4—C4—N3	2.0 (5)	C2—N1—C11a—C4a	−3.9 (5)
C41—O4—C4—C4a	−176.8 (3)	C2—N1—C11a—N11	177.9 (3)
C6—N5—C4a—C11a	−42.2 (5)	N5—C4a—C11a—N1	−169.0 (3)
C6—N5—C4a—C4	144.5 (3)	C4—C4a—C11a—N1	4.6 (5)
N3—C4—C4a—C11a	−0.2 (5)	N5—C4a—C11a—N11	9.2 (6)
O4—C4—C4a—C11a	178.6 (3)	C4—C4a—C11a—N11	−177.2 (3)
N3—C4—C4a—N5	174.0 (3)	C10a—N11—C11a—N1	−123.3 (3)
O4—C4—C4a—N5	−7.2 (5)	C10a—N11—C11a—C4a	58.4 (4)
C4a—N5—C6—C61	−177.5 (3)	N5—C6—C61—C62	−139.2 (4)
C4a—N5—C6—C6a	−1.7 (5)	C6a—C6—C61—C62	44.7 (5)
N5—C6—C6a—C7	−138.2 (4)	N5—C6—C61—C66	38.1 (5)
C61—C6—C6a—C7	37.4 (4)	C6a—C6—C61—C66	−138.1 (3)
N5—C6—C6a—C10a	38.7 (5)	C66—C61—C62—C63	−1.8 (6)
C61—C6—C6a—C10a	−145.7 (3)	C6—C61—C62—C63	175.4 (4)
C10a—C6a—C7—C8	0.7 (5)	C61—C62—C63—C64	0.3 (6)
C6—C6a—C7—C8	177.7 (3)	C62—C63—C64—C65	0.9 (6)
C6a—C7—C8—C9	1.2 (5)	C63—C64—C65—C66	−0.6 (6)
C7—C8—C9—C10	−2.0 (5)	C64—C65—C66—C61	−0.9 (6)
C8—C9—C10—C10a	0.8 (5)	C62—C61—C66—C65	2.1 (6)
C9—C10—C10a—C6a	1.1 (5)	C6—C61—C66—C65	−175.2 (3)
C9—C10—C10a—N11	−177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···N5^i	0.88	2.40	3.129 (5)	141
N11—H11···N1^ii	0.88	2.45	3.036 (4)	125
C7—H7···N3^iii	0.95	2.57	3.503 (5)	168
C65—H65···Cg^iii	0.95	2.65	3.500 (5)	150

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+1/2.

(II) 2-Amino-4-methoxy-6-(2-fluorophenyl)-11H-pyrimido[4,5- b][1,4]benzodiazepine

Crystal data

C18H14FN5O	F(000) = 696
Mr = 335.34	Dx = 1.517 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3340 reflections
a = 6.9115 (10) Å	θ = 5.1–27.5°
b = 12.8801 (14) Å	µ = 0.11 mm^−1
c = 16.560 (2) Å	T = 120 K
β = 95.11 (1)°	Block, colourless
V = 1468.4 (3) Å^3	0.24 × 0.14 × 0.11 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3340 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2361 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 5.1°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→16
Tmin = 0.976, Tmax = 0.988	l = −21→21
35898 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0798P)^2 + 1.6324P] where P = (Fo^2 + 2Fc^2)/3
3340 reflections	(Δ/σ)max = 0.001
237 parameters	Δρmax = 0.64 e Å^−3
9 restraints	Δρmin = −0.56 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O4	0.3963 (2)	0.36163 (12)	0.17280 (9)	0.0233 (4)
N1	0.4465 (3)	0.51317 (15)	0.38652 (11)	0.0210 (4)
N2	0.3365 (3)	0.65948 (15)	0.31765 (13)	0.0272 (5)
H21	0.3458	0.6935	0.3639	0.033*
H22	0.2956	0.6916	0.2724	0.033*
N3	0.3725 (3)	0.51359 (15)	0.24283 (11)	0.0216 (4)
N5	0.4887 (3)	0.24932 (14)	0.30330 (11)	0.0209 (4)
N11	0.5660 (3)	0.36560 (15)	0.45448 (11)	0.0211 (4)
H11	0.5017	0.3648	0.4980	0.025*
C2	0.3849 (3)	0.55857 (18)	0.31605 (14)	0.0213 (5)
C4	0.4104 (3)	0.41405 (17)	0.24240 (13)	0.0195 (5)
C4A	0.4703 (3)	0.35649 (17)	0.31143 (13)	0.0194 (5)
C6	0.6230 (3)	0.19628 (17)	0.34256 (12)	0.0205 (5)
C6A	0.7800 (3)	0.23756 (18)	0.39958 (13)	0.0212 (5)
C7	0.9656 (3)	0.19729 (18)	0.39802 (14)	0.0233 (5)
H7	0.9873	0.1419	0.3620	0.028*
C8	1.1188 (4)	0.2359 (2)	0.44753 (15)	0.0283 (6)
H8	1.2457	0.2087	0.4445	0.034*
C9	1.0880 (4)	0.3144 (2)	0.50161 (15)	0.0282 (6)
H9	1.1928	0.3396	0.5373	0.034*
C10	0.9050 (4)	0.35620 (18)	0.50378 (14)	0.0237 (5)
H10	0.8842	0.4107	0.5407	0.028*
C10A	0.7505 (3)	0.31901 (18)	0.45218 (14)	0.0211 (5)
C11A	0.4939 (3)	0.41293 (17)	0.38231 (13)	0.0193 (5)
C41	0.3504 (4)	0.41893 (19)	0.09990 (14)	0.0264 (5)
H411	0.2365	0.4627	0.1058	0.040*
H412	0.3222	0.3707	0.0546	0.040*
H413	0.4611	0.4628	0.0892	0.040*
C61	0.6253 (3)	0.08501 (18)	0.31931 (15)	0.0227 (5)
C63	0.6291 (4)	−0.0969 (2)	0.35323 (19)	0.0382 (7)
H63	0.6411	−0.1496	0.3935	0.046*
C64	0.5992 (4)	−0.1223 (2)	0.2725 (2)	0.0380 (7)
H64	0.5886	−0.1931	0.2566	0.046*
C65	0.5847 (4)	−0.04629 (19)	0.21534 (18)	0.0354 (6)
H65	0.5648	−0.0638	0.1595	0.042*
F62	0.6619 (3)	0.02639 (15)	0.45079 (11)	0.0378 (7)	0.775 (5)
C66	0.5991 (4)	0.0561 (2)	0.23870 (15)	0.0294 (6)
H66	0.5908	0.1085	0.1982	0.035*	0.775 (5)
C62	0.6412 (4)	0.0058 (2)	0.37472 (15)	0.0307 (6)
H62	0.6616	0.0228	0.4306	0.037*	0.225 (5)
F66	0.6133 (13)	0.1222 (3)	0.1820 (2)	0.048 (3)	0.225 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0337 (9)	0.0216 (8)	0.0140 (8)	0.0004 (7)	−0.0018 (7)	−0.0018 (6)
N1	0.0254 (10)	0.0190 (10)	0.0182 (10)	0.0020 (8)	−0.0003 (8)	−0.0015 (7)
N2	0.0422 (13)	0.0180 (10)	0.0201 (10)	0.0042 (9)	−0.0043 (9)	−0.0006 (8)
N3	0.0255 (10)	0.0208 (10)	0.0181 (10)	0.0000 (8)	−0.0004 (8)	−0.0012 (8)
N5	0.0277 (11)	0.0168 (9)	0.0179 (9)	−0.0002 (8)	0.0002 (8)	−0.0016 (7)
N11	0.0259 (10)	0.0234 (10)	0.0139 (9)	0.0032 (8)	0.0014 (8)	0.0012 (7)
C2	0.0223 (12)	0.0213 (11)	0.0196 (11)	−0.0007 (9)	−0.0008 (9)	−0.0006 (9)
C4	0.0211 (11)	0.0199 (11)	0.0172 (11)	−0.0025 (9)	0.0003 (9)	−0.0009 (9)
C4A	0.0232 (11)	0.0198 (11)	0.0149 (11)	0.0003 (9)	0.0004 (8)	−0.0004 (8)
C6	0.0251 (12)	0.0202 (11)	0.0161 (11)	−0.0005 (9)	0.0016 (9)	−0.0014 (9)
C6A	0.0271 (12)	0.0203 (11)	0.0162 (11)	0.0010 (9)	0.0020 (9)	0.0008 (9)
C7	0.0284 (12)	0.0219 (12)	0.0196 (11)	0.0021 (9)	0.0023 (9)	−0.0008 (9)
C8	0.0244 (12)	0.0363 (14)	0.0239 (12)	0.0021 (10)	0.0010 (10)	0.0004 (10)
C9	0.0260 (13)	0.0327 (14)	0.0248 (13)	−0.0038 (10)	−0.0031 (10)	−0.0008 (10)
C10	0.0303 (13)	0.0236 (12)	0.0166 (11)	−0.0010 (10)	−0.0012 (9)	−0.0019 (9)
C10A	0.0241 (12)	0.0209 (11)	0.0181 (11)	0.0005 (9)	0.0014 (9)	0.0033 (9)
C11A	0.0214 (11)	0.0204 (11)	0.0160 (11)	−0.0004 (9)	0.0011 (8)	0.0008 (9)
C41	0.0356 (14)	0.0278 (13)	0.0154 (11)	0.0010 (10)	−0.0011 (10)	0.0019 (9)
C61	0.0230 (12)	0.0193 (11)	0.0257 (12)	0.0001 (9)	0.0014 (9)	−0.0022 (9)
C63	0.0339 (15)	0.0217 (13)	0.059 (2)	0.0019 (11)	0.0051 (13)	0.0077 (13)
C64	0.0304 (14)	0.0254 (14)	0.059 (2)	−0.0024 (11)	0.0083 (13)	−0.0143 (13)
C65	0.0320 (14)	0.0337 (15)	0.0411 (16)	−0.0013 (11)	0.0063 (12)	−0.0177 (12)
F62	0.0625 (15)	0.0303 (11)	0.0196 (11)	−0.0037 (9)	−0.0030 (9)	0.0007 (8)
C66	0.0284 (13)	0.0295 (13)	0.0308 (14)	0.0005 (10)	0.0045 (10)	−0.0081 (11)
C62	0.0314 (14)	0.0282 (13)	0.0322 (14)	−0.0001 (10)	0.0010 (11)	0.0012 (11)
F66	0.071 (6)	0.043 (5)	0.031 (4)	0.005 (4)	0.000 (4)	−0.009 (3)

Geometric parameters (Å, º)

O4—C4	1.332 (3)	C8—C9	1.379 (4)
O4—C41	1.426 (3)	C8—H8	0.9500
N1—C11A	1.335 (3)	C9—C10	1.378 (3)
N1—C2	1.340 (3)	C9—H9	0.9500
N2—C2	1.343 (3)	C10—C10A	1.392 (3)
N2—H21	0.8800	C10—H10	0.9500
N2—H22	0.8800	C41—H411	0.9800
N3—C4	1.309 (3)	C41—H412	0.9800
N3—C2	1.340 (3)	C41—H413	0.9800
N5—C6	1.282 (3)	C61—C62	1.370 (3)
N5—C4A	1.394 (3)	C61—C66	1.382 (3)
N11—C11A	1.394 (3)	C63—C64	1.374 (4)
N11—C10A	1.413 (3)	C63—C62	1.370 (4)
N11—H11	0.8800	C63—H63	0.9500
C4—C4A	1.394 (3)	C64—C65	1.359 (4)
C4A—C11A	1.378 (3)	C64—H64	0.9500
C6—C6A	1.473 (3)	C65—C66	1.375 (3)
C6—C61	1.484 (3)	C65—H65	0.9500
C6A—C7	1.386 (3)	F62—C62	1.283 (3)
C6A—C10A	1.390 (3)	C66—F66	1.277 (4)
C7—C8	1.373 (3)	C66—H66	0.9500
C7—H7	0.9500	C62—H62	0.9500
C4—O4—C41	117.64 (18)	C10A—C10—H10	119.8
C11A—N1—C2	115.89 (19)	C6A—C10A—C10	119.8 (2)
C2—N2—H21	120.0	C6A—C10A—N11	121.4 (2)
C2—N2—H22	120.0	C10—C10A—N11	118.8 (2)
H21—N2—H22	120.0	N1—C11A—C4A	122.9 (2)
C4—N3—C2	115.6 (2)	N1—C11A—N11	116.7 (2)
C6—N5—C4A	123.1 (2)	C4A—C11A—N11	120.4 (2)
C11A—N11—C10A	114.66 (18)	O4—C41—H411	109.5
C11A—N11—H11	122.7	O4—C41—H412	109.5
C10A—N11—H11	122.7	H411—C41—H412	109.5
N1—C2—N3	126.1 (2)	O4—C41—H413	109.5
N1—C2—N2	117.7 (2)	H411—C41—H413	109.5
N3—C2—N2	116.1 (2)	H412—C41—H413	109.5
N3—C4—O4	120.1 (2)	C62—C61—C66	116.2 (2)
N3—C4—C4A	124.2 (2)	C62—C61—C6	123.2 (2)
O4—C4—C4A	115.7 (2)	C66—C61—C6	120.5 (2)
C11A—C4A—C4	115.0 (2)	C64—C63—C62	118.9 (3)
C11A—C4A—N5	126.9 (2)	C64—C63—H63	120.6
C4—C4A—N5	118.1 (2)	C62—C63—H63	120.6
N5—C6—C6A	126.3 (2)	C65—C64—C63	120.1 (3)
N5—C6—C61	114.0 (2)	C65—C64—H64	119.9
C6A—C6—C61	119.4 (2)	C63—C64—H64	119.9
C7—C6A—C10A	118.8 (2)	C66—C65—C64	119.7 (3)
C7—C6A—C6	118.9 (2)	C66—C65—H65	120.1
C10A—C6A—C6	122.2 (2)	C64—C65—H65	120.1
C8—C7—C6A	121.2 (2)	F66—C66—C65	116.2 (3)
C8—C7—H7	119.4	F66—C66—C61	121.2 (3)
C6A—C7—H7	119.4	C65—C66—C61	122.0 (2)
C7—C8—C9	119.9 (2)	C65—C66—H66	119.0
C7—C8—H8	120.1	C61—C66—H66	119.0
C9—C8—H8	120.1	F62—C62—C61	119.9 (2)
C10—C9—C8	119.9 (2)	F62—C62—C63	117.0 (2)
C10—C9—H9	120.1	C61—C62—C63	123.1 (2)
C8—C9—H9	120.1	C61—C62—H62	118.5
C9—C10—C10A	120.4 (2)	C63—C62—H62	118.5
C9—C10—H10	119.8
C11A—N1—C2—N3	−2.0 (3)	C9—C10—C10A—N11	−178.3 (2)
C11A—N1—C2—N2	−179.7 (2)	C11A—N11—C10A—C6A	−62.1 (3)
C4—N3—C2—N1	5.6 (3)	C11A—N11—C10A—C10	117.8 (2)
C4—N3—C2—N2	−176.7 (2)	C2—N1—C11A—C4A	−4.1 (3)
C2—N3—C4—O4	178.0 (2)	C2—N1—C11A—N11	177.37 (19)
C2—N3—C4—C4A	−3.3 (3)	C4—C4A—C11A—N1	5.9 (3)
C41—O4—C4—N3	3.6 (3)	N5—C4A—C11A—N1	−170.0 (2)
C41—O4—C4—C4A	−175.2 (2)	C4—C4A—C11A—N11	−175.6 (2)
N3—C4—C4A—C11A	−2.0 (3)	N5—C4A—C11A—N11	8.5 (4)
O4—C4—C4A—C11A	176.77 (19)	C10A—N11—C11A—N1	−123.7 (2)
N3—C4—C4A—N5	174.3 (2)	C10A—N11—C11A—C4A	57.6 (3)
O4—C4—C4A—N5	−7.0 (3)	N5—C6—C61—C62	−133.4 (2)
C6—N5—C4A—C11A	−41.2 (4)	C6A—C6—C61—C62	52.9 (3)
C6—N5—C4A—C4	143.1 (2)	N5—C6—C61—C66	42.6 (3)
C4A—N5—C6—C6A	−1.8 (3)	C6A—C6—C61—C66	−131.1 (2)
C4A—N5—C6—C61	−175.0 (2)	C62—C63—C64—C65	0.9 (4)
N5—C6—C6A—C7	−139.1 (2)	C63—C64—C65—C66	−0.3 (4)
C61—C6—C6A—C7	33.7 (3)	C64—C65—C66—F66	169.9 (5)
N5—C6—C6A—C10A	37.6 (3)	C64—C65—C66—C61	−1.0 (4)
C61—C6—C6A—C10A	−149.5 (2)	C62—C61—C66—F66	−168.8 (5)
C10A—C6A—C7—C8	0.4 (4)	C6—C61—C66—F66	15.0 (6)
C6—C6A—C7—C8	177.3 (2)	C62—C61—C66—C65	1.6 (4)
C6A—C7—C8—C9	1.8 (4)	C6—C61—C66—C65	−174.6 (2)
C7—C8—C9—C10	−2.3 (4)	C66—C61—C62—F62	−178.6 (2)
C8—C9—C10—C10A	0.6 (4)	C6—C61—C62—F62	−2.4 (4)
C7—C6A—C10A—C10	−2.1 (3)	C66—C61—C62—C63	−1.1 (4)
C6—C6A—C10A—C10	−178.8 (2)	C6—C61—C62—C63	175.1 (2)
C7—C6A—C10A—N11	177.8 (2)	C64—C63—C62—F62	177.5 (3)
C6—C6A—C10A—N11	1.0 (3)	C64—C63—C62—C61	−0.1 (4)
C9—C10—C10A—C6A	1.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···N5^i	0.88	2.36	3.099 (3)	142
N11—H11···N1^ii	0.88	2.48	3.069 (3)	125
C65—H65···Cg^iii	0.95	2.75	3.562 (3)	145

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+1/2.

(III) 2-Amino-4-methoxy-6-(3-nitrophenyl)-11H-pyrimido[4,5- b][1,4]benzodiazepine

Crystal data

C18H14N6O3	F(000) = 752
Mr = 362.35	Dx = 1.541 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3467 reflections
a = 7.047 (4) Å	θ = 3.9–27.5°
b = 13.502 (7) Å	µ = 0.11 mm^−1
c = 16.418 (5) Å	T = 120 K
β = 91.22 (5)°	Block, yellow
V = 1561.8 (13) Å^3	0.22 × 0.15 × 0.14 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3467 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1748 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.103
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.9°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −17→17
Tmin = 0.966, Tmax = 0.985	l = −21→21
24447 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.182	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0947P)^2 + 0.1349P] where P = (Fo^2 + 2Fc^2)/3
3467 reflections	(Δ/σ)max < 0.001
245 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	0.4045 (3)	0.38071 (14)	0.16181 (11)	0.0400 (6)
O631	0.6404 (4)	−0.22025 (18)	0.39187 (17)	0.0721 (8)
O632	0.6208 (4)	−0.10514 (18)	0.48169 (16)	0.0683 (8)
N1	0.4366 (3)	0.51877 (17)	0.38096 (13)	0.0323 (6)
N2	0.3292 (3)	0.65975 (17)	0.31631 (15)	0.0384 (6)
N3	0.3713 (3)	0.52251 (17)	0.23714 (14)	0.0346 (6)
N5	0.4876 (3)	0.26868 (17)	0.29115 (13)	0.0335 (6)
N11	0.5450 (3)	0.37620 (17)	0.44527 (14)	0.0331 (6)
N63	0.6281 (4)	−0.1331 (2)	0.41100 (19)	0.0496 (7)
C2	0.3796 (4)	0.5636 (2)	0.31189 (17)	0.0331 (7)
C4	0.4120 (4)	0.4279 (2)	0.23404 (16)	0.0326 (7)
C4a	0.4678 (4)	0.3710 (2)	0.30137 (16)	0.0320 (7)
C6	0.6132 (4)	0.2178 (2)	0.32982 (16)	0.0329 (7)
C6a	0.7611 (4)	0.2551 (2)	0.38748 (17)	0.0322 (7)
C7	0.9451 (4)	0.2166 (2)	0.38355 (17)	0.0372 (7)
C8	1.0884 (4)	0.2522 (2)	0.43258 (18)	0.0402 (8)
C9	1.0517 (4)	0.3256 (2)	0.48826 (18)	0.0397 (7)
C10	0.8720 (4)	0.3653 (2)	0.49338 (17)	0.0372 (7)
C10a	0.7272 (4)	0.3308 (2)	0.44232 (16)	0.0329 (7)
C11a	0.4829 (4)	0.4231 (2)	0.37427 (16)	0.0314 (7)
C41	0.3665 (5)	0.4392 (2)	0.09082 (17)	0.0449 (8)
C61	0.6156 (4)	0.1106 (2)	0.30856 (18)	0.0356 (7)
C62	0.6325 (4)	0.0395 (2)	0.36894 (18)	0.0367 (7)
C63	0.6198 (4)	−0.0593 (2)	0.34643 (19)	0.0391 (7)
C64	0.5915 (4)	−0.0893 (2)	0.2683 (2)	0.0441 (8)
C65	0.5800 (5)	−0.0184 (2)	0.2086 (2)	0.0487 (9)
C66	0.5930 (4)	0.0807 (2)	0.22793 (18)	0.0394 (7)
H21	0.3265	0.6874	0.3648	0.046*
H22	0.2602	0.6855	0.2763	0.046*
H11	0.5411	0.4164	0.4874	0.040*
H7	0.9707	0.1648	0.3462	0.045*
H8	1.2132	0.2264	0.4283	0.048*
H9	1.1507	0.3490	0.5234	0.048*
H10	0.8475	0.4161	0.5318	0.045*
H41A	0.2458	0.4743	0.0968	0.067*
H41B	0.3587	0.3961	0.0429	0.067*
H41C	0.4689	0.4874	0.0841	0.067*
H62	0.6524	0.0579	0.4243	0.044*
H64	0.5800	−0.1577	0.2552	0.053*
H65	0.5630	−0.0378	0.1533	0.058*
H66	0.5864	0.1289	0.1858	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0561 (14)	0.0397 (12)	0.0240 (11)	0.0035 (10)	0.0002 (9)	−0.0008 (9)
O631	0.083 (2)	0.0343 (15)	0.098 (2)	−0.0063 (12)	−0.0270 (16)	0.0027 (14)
O632	0.096 (2)	0.0567 (16)	0.0527 (16)	0.0188 (14)	0.0083 (14)	0.0106 (13)
N1	0.0359 (14)	0.0318 (14)	0.0292 (13)	0.0013 (11)	0.0011 (10)	−0.0013 (10)
N2	0.0484 (16)	0.0324 (14)	0.0342 (14)	−0.0008 (11)	−0.0052 (12)	−0.0001 (11)
N3	0.0361 (14)	0.0361 (14)	0.0318 (14)	−0.0018 (11)	0.0016 (11)	−0.0016 (11)
N5	0.0383 (14)	0.0332 (14)	0.0292 (13)	0.0013 (11)	0.0034 (11)	−0.0010 (11)
N11	0.0376 (14)	0.0358 (14)	0.0258 (12)	0.0060 (11)	0.0003 (10)	−0.0017 (10)
N63	0.0462 (18)	0.0386 (17)	0.064 (2)	0.0038 (13)	−0.0069 (14)	0.0049 (15)
C2	0.0313 (16)	0.0342 (16)	0.0338 (16)	−0.0025 (13)	0.0031 (12)	−0.0010 (13)
C4	0.0311 (16)	0.0383 (17)	0.0284 (15)	−0.0001 (13)	0.0011 (12)	−0.0028 (13)
C4a	0.0334 (16)	0.0322 (16)	0.0304 (15)	0.0004 (12)	0.0011 (12)	0.0000 (12)
C6	0.0382 (17)	0.0358 (16)	0.0249 (15)	−0.0014 (13)	0.0055 (13)	−0.0006 (12)
C6a	0.0380 (17)	0.0303 (15)	0.0282 (15)	0.0017 (13)	0.0007 (13)	0.0045 (12)
C7	0.0430 (19)	0.0383 (17)	0.0305 (16)	0.0057 (14)	0.0056 (14)	0.0049 (13)
C8	0.0355 (18)	0.0448 (18)	0.0405 (18)	0.0014 (14)	0.0012 (14)	0.0060 (15)
C9	0.0376 (18)	0.0465 (18)	0.0347 (17)	−0.0006 (15)	−0.0058 (13)	0.0029 (15)
C10	0.0438 (19)	0.0389 (17)	0.0289 (15)	−0.0017 (14)	0.0011 (13)	0.0003 (13)
C10a	0.0350 (17)	0.0364 (16)	0.0273 (15)	−0.0006 (13)	0.0003 (13)	0.0021 (13)
C11a	0.0305 (16)	0.0360 (16)	0.0277 (15)	0.0005 (13)	0.0011 (12)	0.0029 (13)
C41	0.053 (2)	0.055 (2)	0.0268 (16)	0.0011 (16)	−0.0018 (14)	0.0007 (14)
C61	0.0332 (17)	0.0378 (17)	0.0358 (16)	0.0045 (13)	0.0023 (13)	−0.0036 (14)
C62	0.0364 (18)	0.0360 (17)	0.0377 (17)	0.0040 (13)	0.0020 (13)	−0.0025 (14)
C63	0.0336 (17)	0.0351 (17)	0.0488 (19)	0.0018 (13)	0.0013 (14)	0.0007 (15)
C64	0.0381 (18)	0.0379 (18)	0.056 (2)	0.0074 (15)	−0.0005 (15)	−0.0114 (16)
C65	0.047 (2)	0.052 (2)	0.047 (2)	0.0100 (16)	−0.0034 (15)	−0.0172 (17)
C66	0.0367 (17)	0.0452 (18)	0.0363 (17)	0.0068 (15)	0.0004 (13)	−0.0021 (15)

Geometric parameters (Å, º)

O4—C4	1.346 (3)	C6a—C7	1.400 (4)
O4—C41	1.428 (3)	C7—C8	1.365 (4)
O631—N63	1.221 (3)	C7—H7	0.95
O632—N63	1.223 (4)	C8—C9	1.376 (4)
N1—C11a	1.338 (4)	C8—H8	0.95
N1—C2	1.339 (3)	C9—C10	1.379 (4)
N2—C2	1.349 (4)	C9—H9	0.95
N2—H21	0.88	C10—C10a	1.387 (4)
N2—H22	0.8801	C10—H10	0.95
N3—C4	1.311 (4)	C41—H41A	0.98
N3—C2	1.347 (3)	C41—H41B	0.98
N5—C6	1.278 (3)	C41—H41C	0.98
N5—C4a	1.399 (4)	C61—C62	1.383 (4)
N11—C11a	1.389 (3)	C61—C66	1.390 (4)
N11—C10a	1.424 (4)	C62—C63	1.387 (4)
N11—H11	0.88	C62—H62	0.95
N63—C63	1.455 (4)	C63—C64	1.356 (4)
C4—C4a	1.395 (4)	C64—C65	1.372 (5)
C4a—C11a	1.390 (4)	C64—H64	0.95
C6—C6a	1.481 (4)	C65—C66	1.377 (4)
C6—C61	1.490 (4)	C65—H65	0.95
C6a—C10a	1.387 (4)	C66—H66	0.95
C4—O4—C41	117.4 (2)	C8—C9—H9	119.8
C11a—N1—C2	115.8 (2)	C10—C9—H9	119.8
C2—N2—H21	117.9	C9—C10—C10a	119.8 (3)
C2—N2—H22	118.8	C9—C10—H10	120.1
H21—N2—H22	119.0	C10a—C10—H10	120.1
C4—N3—C2	115.6 (2)	C6a—C10a—C10	120.3 (3)
C6—N5—C4a	122.7 (2)	C6a—C10a—N11	120.5 (3)
C11a—N11—C10a	115.8 (2)	C10—C10a—N11	119.2 (3)
C11a—N11—H11	111.3	N1—C11a—N11	116.4 (2)
C10a—N11—H11	109.6	N1—C11a—C4a	123.0 (2)
O631—N63—O632	123.1 (3)	N11—C11a—C4a	120.6 (2)
O631—N63—C63	118.3 (3)	O4—C41—H41A	109.5
O632—N63—C63	118.6 (3)	O4—C41—H41B	109.5
N1—C2—N3	126.3 (3)	H41A—C41—H41B	109.5
N1—C2—N2	117.6 (3)	O4—C41—H41C	109.5
N3—C2—N2	116.0 (3)	H41A—C41—H41C	109.5
N3—C4—O4	119.4 (2)	H41B—C41—H41C	109.5
N3—C4—C4a	124.3 (3)	C62—C61—C66	119.2 (3)
O4—C4—C4a	116.3 (2)	C62—C61—C6	120.5 (3)
C11a—C4a—C4	114.8 (3)	C66—C61—C6	120.3 (3)
C11a—C4a—N5	126.6 (2)	C61—C62—C63	118.2 (3)
C4—C4a—N5	118.4 (2)	C61—C62—H62	120.9
N5—C6—C6a	127.2 (3)	C63—C62—H62	120.9
N5—C6—C61	114.6 (2)	C64—C63—C62	123.2 (3)
C6a—C6—C61	118.0 (3)	C64—C63—N63	119.2 (3)
C10a—C6a—C7	118.5 (3)	C62—C63—N63	117.6 (3)
C10a—C6a—C6	122.5 (3)	C63—C64—C65	118.2 (3)
C7—C6a—C6	119.0 (3)	C63—C64—H64	120.9
C8—C7—C6a	121.1 (3)	C65—C64—H64	120.9
C8—C7—H7	119.5	C64—C65—C66	120.7 (3)
C6a—C7—H7	119.5	C64—C65—H65	119.6
C7—C8—C9	119.9 (3)	C66—C65—H65	119.6
C7—C8—H8	120.1	C65—C66—C61	120.5 (3)
C9—C8—H8	120.1	C65—C66—H66	119.7
C8—C9—C10	120.4 (3)	C61—C66—H66	119.7
C11a—N1—C2—N3	−2.4 (4)	C9—C10—C10a—N11	−176.7 (3)
C11a—N1—C2—N2	179.1 (2)	C11a—N11—C10a—C6a	−61.2 (4)
C4—N3—C2—N1	4.6 (4)	C11a—N11—C10a—C10	117.0 (3)
C4—N3—C2—N2	−176.9 (2)	C2—N1—C11a—N11	179.0 (2)
C2—N3—C4—O4	179.1 (2)	C2—N1—C11a—C4a	−2.2 (4)
C2—N3—C4—C4a	−2.4 (4)	C10a—N11—C11a—N1	−123.6 (3)
C41—O4—C4—N3	4.8 (4)	C10a—N11—C11a—C4a	57.6 (3)
C41—O4—C4—C4a	−173.8 (3)	C4—C4a—C11a—N1	4.0 (4)
N3—C4—C4a—C11a	−1.6 (4)	N5—C4a—C11a—N1	−170.5 (3)
O4—C4—C4a—C11a	177.0 (2)	C4—C4a—C11a—N11	−177.3 (2)
N3—C4—C4a—N5	173.4 (3)	N5—C4a—C11a—N11	8.3 (4)
O4—C4—C4a—N5	−8.0 (4)	N5—C6—C61—C62	−136.2 (3)
C6—N5—C4a—C11a	−39.9 (4)	C6a—C6—C61—C62	48.0 (4)
C6—N5—C4a—C4	145.8 (3)	N5—C6—C61—C66	41.2 (4)
C4a—N5—C6—C6a	−2.8 (4)	C6a—C6—C61—C66	−134.6 (3)
C4a—N5—C6—C61	−178.1 (2)	C66—C61—C62—C63	−2.1 (4)
N5—C6—C6a—C10a	38.5 (4)	C6—C61—C62—C63	175.3 (3)
C61—C6—C6a—C10a	−146.3 (3)	C61—C62—C63—C64	0.0 (4)
N5—C6—C6a—C7	−137.8 (3)	C61—C62—C63—N63	−176.9 (3)
C61—C6—C6a—C7	37.4 (4)	O631—N63—C63—C64	11.8 (4)
C10a—C6a—C7—C8	0.2 (4)	O632—N63—C63—C64	−167.6 (3)
C6—C6a—C7—C8	176.6 (3)	O631—N63—C63—C62	−171.2 (3)
C6a—C7—C8—C9	1.6 (4)	O632—N63—C63—C62	9.4 (4)
C7—C8—C9—C10	−1.8 (4)	C62—C63—C64—C65	1.8 (5)
C8—C9—C10—C10a	0.3 (4)	N63—C63—C64—C65	178.6 (3)
C7—C6a—C10a—C10	−1.7 (4)	C63—C64—C65—C66	−1.3 (5)
C6—C6a—C10a—C10	−178.0 (3)	C64—C65—C66—C61	−0.8 (5)
C7—C6a—C10a—N11	176.4 (2)	C62—C61—C66—C65	2.6 (4)
C6—C6a—C10a—N11	0.1 (4)	C6—C61—C66—C65	−174.9 (3)
C9—C10—C10a—C6a	1.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···N5^i	0.88	2.34	3.177 (4)	160
N11—H11···N1^ii	0.88	2.33	3.186 (3)	163
C8—H8···O632^iii	0.95	2.48	3.162 (4)	129
C65—H65···Cg^iv	0.95	2.77	3.526 (4)	138

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y, −z+1; (iv) −x+3/2, y−1/2, −z+1/2.

(IV) 2-Amino-4-methoxy-6-(4-methoxyphenyl)-11H-pyrimido[4,5- b][1,4]benzodiazepine

Crystal data

C19H17N5O2	F(000) = 728
Mr = 347.38	Dx = 1.423 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3072 reflections
a = 7.6718 (18) Å	θ = 3.8–26.0°
b = 13.2928 (15) Å	µ = 0.10 mm^−1
c = 15.969 (2) Å	T = 120 K
β = 95.343 (12)°	Lath, yellow
V = 1621.5 (5) Å^3	0.17 × 0.15 × 0.08 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3072 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1312 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.179
Detector resolution: 9.091 pixels mm^-1	θmax = 26.0°, θmin = 3.8°
ϕ and ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→14
Tmin = 0.974, Tmax = 0.992	l = −19→19
22968 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.189	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0939P)^2] where P = (Fo^2 + 2Fc^2)/3
3072 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	0.6006 (3)	0.66252 (18)	0.17304 (15)	0.0334 (7)
O64	0.3677 (4)	1.2297 (2)	0.31953 (17)	0.0427 (8)
N1	0.5693 (4)	0.4980 (2)	0.38468 (19)	0.0304 (8)
N2	0.7098 (4)	0.3710 (2)	0.3202 (2)	0.0365 (9)
N3	0.6431 (4)	0.5125 (2)	0.24295 (19)	0.0298 (8)
N5	0.4992 (4)	0.7610 (2)	0.30853 (18)	0.0296 (8)
N11	0.4328 (4)	0.6288 (2)	0.45010 (19)	0.0309 (8)
C2	0.6382 (5)	0.4642 (3)	0.3164 (2)	0.0289 (10)
C4	0.5892 (5)	0.6078 (3)	0.2429 (2)	0.0271 (9)
C4a	0.5217 (5)	0.6551 (3)	0.3108 (2)	0.0260 (9)
C6	0.3788 (5)	0.8058 (3)	0.3454 (2)	0.0290 (10)
C6a	0.2346 (5)	0.7562 (3)	0.3870 (2)	0.0307 (10)
C7	0.0642 (5)	0.7951 (3)	0.3728 (2)	0.0318 (10)
C8	−0.0743 (5)	0.7494 (3)	0.4068 (2)	0.0348 (10)
C9	−0.0465 (5)	0.6642 (3)	0.4559 (3)	0.0358 (11)
C10	0.1197 (5)	0.6255 (3)	0.4700 (2)	0.0344 (10)
C10a	0.2613 (5)	0.6708 (3)	0.4351 (2)	0.0277 (9)
C11a	0.5067 (5)	0.5930 (3)	0.3794 (2)	0.0305 (10)
C41	0.6586 (6)	0.6116 (3)	0.1016 (2)	0.0399 (11)
C61	0.3751 (5)	0.9178 (3)	0.3404 (2)	0.0288 (9)
C62	0.3221 (5)	0.9755 (3)	0.4052 (2)	0.0323 (10)
C63	0.3166 (5)	1.0795 (3)	0.4006 (2)	0.0330 (10)
C64	0.3658 (5)	1.1267 (3)	0.3305 (2)	0.0299 (10)
C65	0.4222 (5)	1.0708 (3)	0.2646 (2)	0.0354 (10)
C66	0.4278 (5)	0.9680 (3)	0.2703 (2)	0.0287 (10)
C641	0.2923 (6)	1.2875 (3)	0.3773 (3)	0.0386 (11)
H21	0.7000	0.3350	0.3658	0.044*
H22	0.7553	0.3384	0.2795	0.044*
H11	0.4281	0.5876	0.4930	0.037*
H7	0.0441	0.8537	0.3392	0.038*
H8	−0.1889	0.7764	0.3964	0.042*
H9	−0.1415	0.6327	0.4797	0.043*
H10	0.1389	0.5672	0.5040	0.041*
H41A	0.7774	0.5858	0.1156	0.060*
H41B	0.6586	0.6588	0.0544	0.060*
H41C	0.5794	0.5555	0.0858	0.060*
H62	0.2886	0.9430	0.4542	0.039*
H63	0.2790	1.1178	0.4459	0.040*
H65	0.4567	1.1037	0.2159	0.042*
H66	0.4684	0.9301	0.2255	0.034*
H64A	0.1685	1.2692	0.3775	0.058*
H64B	0.3017	1.3587	0.3625	0.058*
H64C	0.3526	1.2759	0.4333	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0461 (19)	0.0330 (16)	0.0218 (14)	0.0040 (13)	0.0067 (12)	0.0018 (13)
O64	0.048 (2)	0.0305 (17)	0.0501 (19)	−0.0001 (14)	0.0097 (15)	0.0035 (14)
N1	0.033 (2)	0.0271 (19)	0.0309 (19)	0.0028 (15)	0.0032 (15)	0.0037 (15)
N2	0.046 (2)	0.030 (2)	0.0334 (19)	0.0069 (17)	0.0065 (17)	0.0010 (15)
N3	0.034 (2)	0.0273 (19)	0.0280 (18)	−0.0008 (15)	0.0017 (15)	0.0004 (15)
N5	0.035 (2)	0.0259 (19)	0.0276 (18)	−0.0002 (15)	−0.0010 (15)	0.0001 (15)
N11	0.036 (2)	0.035 (2)	0.0215 (17)	0.0049 (16)	0.0033 (15)	0.0030 (15)
C2	0.030 (3)	0.032 (2)	0.025 (2)	0.0017 (19)	0.0015 (18)	0.001 (2)
C4	0.028 (2)	0.031 (2)	0.022 (2)	−0.0038 (18)	−0.0004 (17)	0.0012 (19)
C4a	0.026 (2)	0.029 (2)	0.022 (2)	−0.0007 (17)	−0.0005 (17)	0.0012 (18)
C6	0.033 (3)	0.027 (2)	0.026 (2)	0.0018 (19)	0.0004 (19)	−0.0022 (18)
C6a	0.038 (3)	0.029 (2)	0.025 (2)	−0.0025 (19)	0.0036 (19)	−0.0022 (19)
C7	0.038 (3)	0.026 (2)	0.031 (2)	0.003 (2)	0.0020 (19)	−0.0009 (18)
C8	0.034 (3)	0.041 (3)	0.028 (2)	0.001 (2)	−0.0019 (19)	−0.005 (2)
C9	0.032 (3)	0.039 (3)	0.039 (2)	−0.007 (2)	0.013 (2)	−0.005 (2)
C10	0.040 (3)	0.032 (2)	0.032 (2)	−0.002 (2)	0.007 (2)	−0.0008 (19)
C10a	0.033 (3)	0.024 (2)	0.026 (2)	0.0006 (19)	0.0022 (18)	−0.0030 (18)
C11a	0.030 (2)	0.034 (2)	0.027 (2)	−0.0033 (19)	0.0003 (18)	−0.004 (2)
C41	0.046 (3)	0.044 (3)	0.030 (2)	0.003 (2)	0.008 (2)	0.001 (2)
C61	0.027 (2)	0.032 (2)	0.027 (2)	−0.0009 (19)	−0.0010 (18)	0.0025 (19)
C62	0.038 (3)	0.031 (2)	0.028 (2)	−0.005 (2)	0.0037 (18)	0.0038 (19)
C63	0.039 (3)	0.030 (2)	0.031 (2)	−0.0025 (19)	0.0067 (19)	−0.0054 (19)
C64	0.028 (2)	0.029 (2)	0.033 (2)	0.0010 (18)	0.0009 (18)	0.001 (2)
C65	0.038 (3)	0.039 (3)	0.030 (2)	0.002 (2)	0.0059 (19)	0.009 (2)
C66	0.027 (2)	0.030 (2)	0.028 (2)	0.0013 (18)	−0.0006 (17)	0.0024 (19)
C641	0.045 (3)	0.023 (2)	0.045 (3)	−0.006 (2)	−0.009 (2)	0.002 (2)

Geometric parameters (Å, º)

O4—C4	1.341 (4)	C7—H7	0.95
O4—C41	1.433 (4)	C8—C9	1.383 (5)
O64—C641	1.370 (5)	C8—H8	0.95
O64—C64	1.380 (4)	C9—C10	1.373 (6)
N1—C2	1.333 (4)	C9—H9	0.95
N1—C11a	1.351 (5)	C10—C10a	1.402 (5)
N2—C2	1.354 (4)	C10—H10	0.95
N2—H21	0.8799	C41—H41A	0.98
N2—H22	0.8801	C41—H41B	0.98
N3—C4	1.333 (4)	C41—H41C	0.98
N3—C2	1.341 (4)	C61—C62	1.379 (5)
N5—C6	1.286 (4)	C61—C66	1.395 (5)
N5—C4a	1.418 (4)	C62—C63	1.386 (5)
N11—C11a	1.393 (5)	C62—H62	0.95
N11—C10a	1.429 (5)	C63—C64	1.367 (5)
N11—H11	0.8801	C63—H63	0.95
C4—C4a	1.394 (5)	C64—C65	1.391 (5)
C4a—C11a	1.386 (5)	C65—C66	1.370 (5)
C6—C61	1.492 (5)	C65—H65	0.95
C6—C6a	1.495 (5)	C66—H66	0.95
C6a—C10a	1.376 (5)	C641—H64A	0.98
C6a—C7	1.404 (5)	C641—H64B	0.98
C7—C8	1.379 (5)	C641—H64C	0.98
C4—O4—C41	117.1 (3)	C10a—C10—H10	119.5
C641—O64—C64	117.4 (3)	C6a—C10a—C10	119.7 (4)
C2—N1—C11a	115.5 (3)	C6a—C10a—N11	120.2 (3)
C2—N2—H21	117.9	C10—C10a—N11	120.1 (4)
C2—N2—H22	127.2	N1—C11a—C4a	123.4 (3)
H21—N2—H22	114.5	N1—C11a—N11	116.0 (3)
C4—N3—C2	115.0 (3)	C4a—C11a—N11	120.5 (3)
C6—N5—C4a	122.6 (3)	O4—C41—H41A	109.5
C11a—N11—C10a	115.8 (3)	O4—C41—H41B	109.5
C11a—N11—H11	117.8	H41A—C41—H41B	109.5
C10a—N11—H11	105.6	O4—C41—H41C	109.5
N1—C2—N3	126.8 (3)	H41A—C41—H41C	109.5
N1—C2—N2	117.5 (3)	H41B—C41—H41C	109.5
N3—C2—N2	115.7 (3)	C62—C61—C66	117.7 (3)
N3—C4—O4	118.1 (3)	C62—C61—C6	121.3 (3)
N3—C4—C4a	124.5 (3)	C66—C61—C6	121.0 (3)
O4—C4—C4a	117.4 (3)	C61—C62—C63	121.7 (4)
C11a—C4a—C4	114.3 (3)	C61—C62—H62	119.2
C11a—C4a—N5	126.3 (3)	C63—C62—H62	119.2
C4—C4a—N5	118.7 (3)	C64—C63—C62	119.4 (4)
N5—C6—C61	116.7 (3)	C64—C63—H63	120.3
N5—C6—C6a	126.3 (3)	C62—C63—H63	120.3
C61—C6—C6a	116.9 (3)	C63—C64—O64	124.5 (4)
C10a—C6a—C7	118.8 (4)	C63—C64—C65	120.3 (4)
C10a—C6a—C6	122.3 (4)	O64—C64—C65	115.2 (3)
C7—C6a—C6	118.9 (3)	C66—C65—C64	119.5 (4)
C8—C7—C6a	121.0 (4)	C66—C65—H65	120.2
C8—C7—H7	119.5	C64—C65—H65	120.2
C6a—C7—H7	119.5	C65—C66—C61	121.3 (4)
C7—C8—C9	120.0 (4)	C65—C66—H66	119.3
C7—C8—H8	120.0	C61—C66—H66	119.3
C9—C8—H8	120.0	O64—C641—H64A	109.5
C10—C9—C8	119.4 (4)	O64—C641—H64B	109.5
C10—C9—H9	120.3	H64A—C641—H64B	109.5
C8—C9—H9	120.3	O64—C641—H64C	109.5
C9—C10—C10a	121.0 (4)	H64A—C641—H64C	109.5
C9—C10—H10	119.5	H64B—C641—H64C	109.5
C11a—N1—C2—N3	−3.7 (6)	C9—C10—C10a—C6a	1.0 (6)
C11a—N1—C2—N2	177.1 (3)	C9—C10—C10a—N11	−179.5 (3)
C4—N3—C2—N1	7.5 (6)	C11a—N11—C10a—C6a	−64.1 (4)
C4—N3—C2—N2	−173.2 (3)	C11a—N11—C10a—C10	116.4 (4)
C2—N3—C4—O4	176.0 (3)	C2—N1—C11a—C4a	−4.1 (5)
C2—N3—C4—C4a	−3.9 (5)	C2—N1—C11a—N11	179.4 (3)
C41—O4—C4—N3	4.4 (5)	C4—C4a—C11a—N1	7.0 (5)
C41—O4—C4—C4a	−175.8 (3)	N5—C4a—C11a—N1	−163.5 (4)
N3—C4—C4a—C11a	−2.8 (5)	C4—C4a—C11a—N11	−176.7 (3)
O4—C4—C4a—C11a	177.4 (3)	N5—C4a—C11a—N11	12.8 (6)
N3—C4—C4a—N5	168.5 (3)	C10a—N11—C11a—N1	−128.3 (4)
O4—C4—C4a—N5	−11.3 (5)	C10a—N11—C11a—C4a	55.1 (5)
C6—N5—C4a—C11a	−39.8 (6)	N5—C6—C61—C62	−147.2 (4)
C6—N5—C4a—C4	150.0 (4)	C6a—C6—C61—C62	37.3 (5)
C4a—N5—C6—C61	177.8 (3)	N5—C6—C61—C66	31.9 (5)
C4a—N5—C6—C6a	−7.2 (6)	C6a—C6—C61—C66	−143.7 (4)
N5—C6—C6a—C10a	40.5 (6)	C66—C61—C62—C63	1.6 (6)
C61—C6—C6a—C10a	−144.4 (4)	C6—C61—C62—C63	−179.3 (4)
N5—C6—C6a—C7	−136.0 (4)	C61—C62—C63—C64	−0.4 (6)
C61—C6—C6a—C7	39.0 (5)	C62—C63—C64—O64	−179.1 (4)
C10a—C6a—C7—C8	0.5 (5)	C62—C63—C64—C65	−0.5 (6)
C6—C6a—C7—C8	177.2 (3)	C641—O64—C64—C63	−9.6 (6)
C6a—C7—C8—C9	0.2 (6)	C641—O64—C64—C65	171.7 (3)
C7—C8—C9—C10	−0.4 (6)	C63—C64—C65—C66	0.2 (6)
C8—C9—C10—C10a	−0.2 (6)	O64—C64—C65—C66	178.9 (3)
C7—C6a—C10a—C10	−1.1 (5)	C64—C65—C66—C61	1.1 (6)
C6—C6a—C10a—C10	−177.6 (3)	C62—C61—C66—C65	−2.0 (6)
C7—C6a—C10a—N11	179.4 (3)	C6—C61—C66—C65	179.0 (4)
C6—C6a—C10a—N11	2.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N1^i	0.88	2.26	3.132 (4)	171
C65—H65···Cg^ii	0.95	2.61	3.492 (4)	155

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2.