2-Amino-4-(piperidin-1-yl)-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride monohydrate and 2-amino-4-[methyl(2-methyl­phenyl)amino]-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride-benzene-1,2-diamine (1/1): complex sheets generated by multiple hydrogen bonds

In each of 2-amino-4-(piperidin-1-yl)-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride monohydrate, C₁₆H₁₉N₆⁺·Cl^-·H₂O, (I), and 2-amino-4-[methyl(2-methyl­phenyl)amino]-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride-ben­zene-1,2-diamine (1/1), C₁₉H₁₉N₆⁺·Cl^-·C₆H₈N₂, (II), the seven-membered ring in the cation adopts a boat conformation. The pyrimidine ring in (II) adopts a twist-boat conformation, but the corresponding ring in (I) is essentially planar. The amino groups of the benzene-1,2-diamine component of (II) are both pyramidal. The independent components of (I) are linked into complex sheets by a combination of N-H...O, N-H...N, N-H...Cl and O-H...Cl hydrogen bonds. In the crystal structure of (II), one N-H...N hydrogen bond and six independent N-H...Cl hydrogen bonds combine to link the components into complex sheets.

S1. Comment

Pyrimidine-fused compounds belong to the so-called bicyclic privileged structures, which may be useful in the field of medicinal chemistry (Horton et al., 2003), and they have shown a wide variety of biological properties (Gangjee et al., 2004; McGuigan et al., 2004; Wang et al., 2004). We report here the structures of two N⁴-substituted 11H-pyrimido[4,5-b][1,5]benzodiazepine-2,4-diamines, namely 2-amino-4-(piperidin-1-yl)-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride monohydrate, (I) (Fig. 1), and 2-amino-4-[methyl(2-methylphenyl)amino]-11H-pyrimido[4,5-b][1,5]benzodiazepin-6-ium chloride–benzene-1,2-diamine (1/1), (II) (Fig. 2). Compounds (I) and (II) were both prepared rapidly and in satisfactory yield by means of a cyclocondensation reaction between benzene-1,2-diamine and a 2,4-diamino-5-formyl-6-chloropyrimidine, mediated by microwave radiation under solvent-free conditions. The pyrimidine components employed in the syntheses of (I) and (II) differ in the nature of the 4-amino substituent: a piperidine unit in the precursor for (I) and a 2-methyl-(2-methylphenyl)amino unit in the precursor for (II) (see scheme). Both products are fused pyrimidobenzodiapinium [-diazapinium?] chloride salts, with an additional water molecule present in (I) and a molecule of benzene-1,2-diamine present in (II).

The presence of three independent components in each structure provides considerable flexibility in the choice of the asymmetric units. However, for both structures it is possible to specify rather compact asymmetric units in which the independent components are linked by multiple hydrogen bonds (Figs. 1 and 2, Table 2). In compound (I), the three components are linked within the selected asymmetric unit by a combination of N—H···O, O—H···Cl and N—H···Cl hydrogen bonds in a cyclic R²₃(10) motif (Bernstein et al., 1995), while in (II), the components within the selected asymmetric unit are linked by a combination of three independent N—H···Cl hydrogen bonds and one N—H···N hydrogen bond to form edge-fused R¹₂(7) and R²₃(10) rings. It may be noted that the R²₃(10) rings in (I) and (II) differ only in the notional replacement of the water O atom in (I) by an amino N atom in (II).

The pyrimidine ring in (I) is effectively planar, but that in (II) adopts an approximate twist-boat conformation, with a ring-puckering amplitude of 0.129 (2) Å and ring-puckering angles (Cremer & Pople, 1975) of θ = 81.7 (9)° and ϕ = 221.6 (10)°. The idealized ring-puckering angles for a twist-boat form are θ = 90° and ϕ = (60k + 30)°, where k represents an integer. The seven-membered rings adopt very similar boat-type conformations in which the ring atoms C5, N6, N11 and C11a are essentially coplanar, with atoms C4a, C6a and C10a all displaced to the same side of the plane defined by C5/N6/N11/C11a.

The pattern of the bond distances (Table 1) in the fused tricyclic cores are very similar for (I) and (II), and a number of general comments can be made. Firstly, the bond distances in the carbocyclic rings C6a/C7–C10/C10a span only very small ranges, ca 0.015 Å, indicating the occurrence of unperturbed benzenoid delocalization within this ring in both compounds. Secondly, the bond distances in the pyrimidine rings are typical of their types and again are consistent with aromatic-type delocalization in these rings. Thirdly, in the seven-membered rings, there is not even approximate equivalence between the distances in the two halves of the ring (defined by the local pseudo-mirror through atom C4a and the midpoint of the bond C6a—C10a), as expected for a simple benzodiazepinium cation and, in particular, there are some marked differences in the C—N distances. Thus, the C5—N6 bond is markedly shorter than the N6—C6a bond in both compounds, consistent with C5—N6 being a localized double bond. Hence, it may be concluded that there is no electronic delocalization between the fused rings, nor around the periphery, so that the outer rings both behave as closed 6π systems, while the central ring contains a localized double bond.

In the benzene-1,2-diamine component of (II), the N atoms are both markedly pyramidal, with angle sums at N21 and N22 of 340.1 and 336.1°, respectively, and the C—N distances in this component (Table 1) are typical of those in aryl–NH₂ fragments containing pyramidal N atoms (Allen et al., 1987). All of the amino-group H atoms lie on the same side of the aryl ring plane, and the C—C—N—H torsion angles (Table 1) indicate that this component has approximate mirror symmetry, with the mirror normal to the ring plane and passing through the mid-points of the C21—C22 and C24—C25 bonds. By contrast, in pure benzene-1,2-diamine [Cambridge Structural Database (Allen, 2002) refcode BAGFIY; Stalhandske, 1981], where again the amino groups are pyramidal with angle sums at the N atoms of 341 and 335°, the H atoms of the two amino groups lie on opposite sides of the ring plane, so that the molecule has approximate twofold rotation symmetry, with the axis passing through the mid-points of the bonds corresponding to C21—C22 and C24—C25 in (II).

In addition to the three hydrogen bonds within the selected asymmetric unit of (I), the crystal structure of (I) contains three further hydrogen bonds, one each of N—H···N, O—H···Cl and N—H···Cl types, linking the three-component aggregates comprising the asymmetric units to form complex sheets. The formation of the sheets is most simply analysed in terms of two one-dimensional sub-structures. The first sub-structure in (I) is a chain of edge-fused rings running parallel to the [100] direction. Pairs of symmetry-related N—H···N hydrogen bonds link pairs of cations related by inversion, via a centrosymmetric R²₂(8) motif, while O—H···Cl hydrogen bonds link pairs of water molecules and pairs of chloride ions in a centrosymmetric R⁴₄(8) motif. Within the chain of rings, the R²₂(8) rings are centred at (n + 1/2, 1/2, 1/2), where n represents an integer, and the R⁴₄(8) rings are centred at (n, 1/2, 1/2), where n again represents an integer, and these two centrosymmetric motifs are linked by the R²₃(10) ring within the asymmetric unit, giving a continuous chain of edge-fused rings parallel to [100] (Fig. 3). In the second sub-structure in (I), atom N6 in the cation at (x, y, z) acts as hydrogen-bond donor to the chloride ion at (3/2 - x, -1/2 + y, 1/2 - z), so linking the three-component aggregates related by the 2₁ screw axis along (3/4, y, 1/4) into a C²₃(9)C¹₂(10)[R²₃(10)] chain of rings running parallel to the [010] direction (Fig. 4). The combination of [100] and [010] chains of rings generates a sheet of some complexity lying parallel to (001).

In compound (II), there are four N—H bonds exterior to the three-component aggregate comprising the selected asymmetric unit. As in (I), the hydrogen-bonded structure of (II) is two-dimensional and again it is readily analysed in terms of two sub-structures, one involving only the ionic components and the other involving all three components. In the first and simpler of the two sub-structures, the cations and anions are linked by three independent N—H···Cl hydrogen bonds involving atoms N2 and N6 as donors (Table 2) to form a chain of edge-fused centrosymmetric rings running parallel to the [010] direction, in which R²₄(8) rings are centred at (1/2, n, 1/2), alternating with R²₄(20) rings centred at (1/2, n + 1/2, 1/2), where in both cases n represents an integer (Fig. 5). The second, more complex, sub-structure again contains centrosymmetric R²₄(20) rings built from pairs of cations and anions and centred at (n + 1/2, n + 1/2, 1/2), where n represents an integer. These rings alternate with centrosymmetric R²₄(8) rings built from chloride ions and benzene-1,2-diamine molecules which are centred at (n, n, 1/2), where n represents an integer, so forming a chain running parallel to the [110] direction (Fig. 6). The R²₄(8) and R²₄(20) rings in the chain along [110] are spiro-fused, in contrast with the edge-fused R²₄(8) and R²₄(20) rings in the chain along [010]. In addition, the chain along [110] also contains the R¹₂(7) and R²₃(10) rings which lie within the selected asymmetric unit, so that the chain along [110] contains four distinct ring types, as opposed to just two rings types in the chain along [010]. The combination of chains of rings along [010] and [110] generates a complex sheet parallel to (001). Unlike that of (I), the structure of (II) contains a single rather weak C—H···π(arene) hydrogen bond (Table 2) but this lies within the (001) sheet, rather than linking adjacent sheets, so that the hydrogen-bonded structures of (I) and (II) are both strictly two-dimensional.

S2. Experimental

An intimate mixture of benzene-1,2-diamine (0.2 mmol) with the appropriate N⁴-substituted 2,4-diamino-6-chloropyrimidine-5-carbaldehyde (0.2 mmol) [2-amino-6-chloro-4-piperidinopyrimidine-5-carbaldehyde for (I) and 2-amino-6-chloro-4-(2-methylphenylamino)pyrimidine-5-carbaldehyde for (II)] was subjected to microwave irradiation in the absence of solvent (maximum power 300 W during 3 min at a controlled temperature of 378 K) using a focused microwave reactor (CEM Discover). After cooling to ambient temperature, the solid products were washed with ethanol and then with diethyl ether to give red crystals of (I) and (II) suitable for single-crystal X-ray diffraction. For (I), yield 70%, m.p. 524–526 K; MS (70 eV) m/z (%) 294 (M⁺, 100), 293 (34), 251 (19), 237 (17), 169 (11), 84 (16), 36 (15). For (II), yield 70%, m.p. 525–527 K; MS (70 eV) m/z (%) 330 (M⁺, 27), 315 (14), 108 (19), 81 (54), 69 (100), 41 (28).

S3. Refinement

All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic or alkenyl), 0.98 (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. H atoms bonded to N atoms were permitted at the positions located in difference maps, with U_iso(H) = 1.2U_eq(N), giving N—H distances in the range 0.88–0.92 Å. The coordinates of the H atoms of the water molecule in (I) were refined subject to a distance restraint O—H = 0.89 (2) Å, with U_iso(H) = 1.5U_eq(O).

Computing details

For both 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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The independent components of (I), showing the atom-labelling scheme and the hydrogen bonds (dashed lines) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The independent components of (II), showing the atom-labelling scheme and the hydrogen bonds (dashed lines) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain along [100] and containing three types of edge-fused ring. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded C^23(9)C^12(10)[R^23(10)] chain of rings along [010]. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded chain of edge-fused R^24(8) and R^24(20) rings along [010] and containing only the ionic components. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a chain along [110] containing four types of hydrogen-bonded ring. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms have been omitted.

(I) 2-amino-4-(piperidin-1-yl)-11H-pyrimido[4,5-b][1,5]benzodiazepin- 6-ium chloride monohydrate

Crystal data

C16H19N6^+·Cl^−·H2O	F(000) = 736
Mr = 348.84	Dx = 1.464 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3122 reflections
a = 13.7831 (14) Å	θ = 3.4–26.1°
b = 7.5324 (9) Å	µ = 0.26 mm^−1
c = 15.2987 (12) Å	T = 120 K
β = 94.925 (8)°	Plate, red
V = 1582.4 (3) Å^3	0.32 × 0.28 × 0.10 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3122 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2253 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 3.4°
ϕ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.933, Tmax = 0.975	l = −18→18
22943 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 1.364P] where P = (Fo^2 + 2Fc^2)/3
3122 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.26 e Å^−3
2 restraints	Δρmin = −0.32 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.70725 (13)	0.3401 (3)	0.39912 (12)	0.0194 (4)
C2	0.62040 (16)	0.3755 (3)	0.42905 (14)	0.0183 (5)
N3	0.53518 (13)	0.3980 (3)	0.38157 (11)	0.0179 (4)
C4	0.53717 (16)	0.3804 (3)	0.29515 (14)	0.0174 (5)
C4a	0.62321 (16)	0.3304 (3)	0.25553 (14)	0.0172 (5)
C5	0.61503 (17)	0.2528 (3)	0.17284 (14)	0.0195 (5)
H5	0.5510	0.2202	0.1508	0.023*
N6	0.68352 (14)	0.2185 (3)	0.12122 (12)	0.0201 (4)
H6	0.6676	0.1631	0.0714	0.024*
C6a	0.78091 (17)	0.2812 (3)	0.12813 (15)	0.0194 (5)
C7	0.82369 (18)	0.3044 (3)	0.05075 (15)	0.0221 (5)
H7	0.7870	0.2829	−0.0037	0.027*
C8	0.91920 (18)	0.3586 (3)	0.05166 (15)	0.0253 (6)
H8	0.9487	0.3720	−0.0018	0.030*
C9	0.97155 (18)	0.3930 (3)	0.13026 (16)	0.0244 (5)
H9	1.0373	0.4312	0.1312	0.029*
C10	0.92871 (17)	0.3722 (3)	0.20769 (15)	0.0208 (5)
H10	0.9651	0.3980	0.2618	0.025*
C10a	0.83375 (17)	0.3143 (3)	0.20781 (14)	0.0196 (5)
N11	0.79789 (14)	0.2804 (3)	0.28916 (12)	0.0214 (5)
H11	0.8415	0.2735	0.3345	0.026*
C11a	0.70910 (16)	0.3203 (3)	0.31434 (14)	0.0180 (5)
N2	0.62275 (14)	0.3955 (3)	0.51552 (12)	0.0213 (5)
H2A	0.6812	0.4111	0.5420	0.026*
H2B	0.5730	0.4430	0.5394	0.026*
N41	0.45347 (13)	0.4089 (3)	0.24457 (12)	0.0188 (4)
C42	0.36170 (16)	0.4188 (3)	0.28519 (14)	0.0206 (5)
H42A	0.3495	0.5427	0.3028	0.025*
H42B	0.3653	0.3437	0.3385	0.025*
C43	0.27947 (17)	0.3556 (3)	0.22094 (14)	0.0229 (5)
H43A	0.2170	0.3684	0.2479	0.027*
H43B	0.2888	0.2282	0.2083	0.027*
C44	0.27419 (17)	0.4594 (3)	0.13560 (14)	0.0229 (5)
H44A	0.2233	0.4078	0.0935	0.028*
H44B	0.2564	0.5842	0.1466	0.028*
C45	0.37177 (17)	0.4532 (3)	0.09686 (14)	0.0221 (5)
H45A	0.3856	0.3302	0.0787	0.027*
H45B	0.3698	0.5300	0.0442	0.027*
C46	0.45127 (17)	0.5159 (3)	0.16383 (14)	0.0206 (5)
H46A	0.5150	0.5070	0.1388	0.025*
H46B	0.4401	0.6420	0.1781	0.025*
Cl1	0.85239 (4)	0.54851 (8)	0.57634 (4)	0.02468 (17)
O1	0.93790 (13)	0.3149 (3)	0.43028 (11)	0.0327 (5)
H1B	0.9994 (15)	0.353 (4)	0.435 (2)	0.049*
H1A	0.906 (2)	0.363 (4)	0.4719 (16)	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0176 (10)	0.0228 (11)	0.0183 (10)	0.0011 (8)	0.0037 (8)	−0.0005 (8)
C2	0.0217 (12)	0.0153 (12)	0.0181 (11)	−0.0005 (9)	0.0033 (9)	0.0004 (9)
N3	0.0188 (10)	0.0200 (11)	0.0151 (9)	0.0010 (8)	0.0028 (8)	−0.0001 (8)
C4	0.0187 (12)	0.0151 (12)	0.0189 (11)	−0.0018 (9)	0.0036 (9)	0.0002 (9)
C4a	0.0199 (11)	0.0152 (12)	0.0166 (11)	−0.0004 (9)	0.0023 (9)	0.0017 (9)
C5	0.0214 (12)	0.0174 (12)	0.0199 (12)	0.0000 (10)	0.0022 (9)	0.0020 (9)
N6	0.0218 (10)	0.0231 (11)	0.0155 (9)	0.0000 (8)	0.0028 (8)	−0.0048 (8)
C6a	0.0199 (12)	0.0160 (12)	0.0225 (12)	0.0017 (10)	0.0032 (9)	0.0000 (9)
C7	0.0283 (13)	0.0211 (13)	0.0171 (11)	0.0016 (10)	0.0032 (10)	−0.0001 (9)
C8	0.0298 (13)	0.0244 (14)	0.0230 (13)	0.0011 (11)	0.0106 (10)	0.0044 (10)
C9	0.0224 (12)	0.0239 (14)	0.0276 (13)	0.0002 (10)	0.0064 (10)	0.0023 (10)
C10	0.0215 (12)	0.0203 (13)	0.0208 (12)	0.0015 (10)	0.0026 (9)	−0.0011 (10)
C10a	0.0243 (12)	0.0161 (12)	0.0190 (11)	0.0047 (10)	0.0063 (10)	−0.0018 (9)
N11	0.0171 (10)	0.0319 (12)	0.0154 (9)	0.0035 (9)	0.0026 (8)	−0.0010 (8)
C11a	0.0212 (12)	0.0159 (12)	0.0172 (11)	−0.0003 (9)	0.0033 (9)	−0.0008 (9)
N2	0.0177 (10)	0.0304 (12)	0.0162 (9)	0.0016 (8)	0.0033 (8)	−0.0016 (8)
N41	0.0174 (10)	0.0226 (11)	0.0167 (9)	0.0004 (8)	0.0038 (8)	0.0013 (8)
C42	0.0171 (11)	0.0282 (14)	0.0168 (11)	0.0007 (10)	0.0035 (9)	0.0005 (10)
C43	0.0204 (12)	0.0279 (14)	0.0204 (12)	−0.0019 (10)	0.0018 (10)	−0.0009 (10)
C44	0.0247 (13)	0.0249 (13)	0.0186 (11)	−0.0011 (11)	−0.0016 (9)	−0.0023 (10)
C45	0.0266 (13)	0.0234 (13)	0.0164 (11)	−0.0008 (11)	0.0022 (9)	−0.0002 (10)
C46	0.0230 (12)	0.0226 (13)	0.0162 (11)	−0.0008 (10)	0.0027 (9)	0.0042 (9)
Cl1	0.0252 (3)	0.0260 (3)	0.0231 (3)	−0.0016 (3)	0.0040 (2)	−0.0028 (2)
O1	0.0199 (9)	0.0526 (13)	0.0261 (9)	−0.0007 (9)	0.0047 (8)	−0.0118 (9)

Geometric parameters (Å, º)

N1—C11a	1.308 (3)	C10a—N11	1.401 (3)
N1—C2	1.345 (3)	N11—C11a	1.348 (3)
C2—N2	1.329 (3)	N11—H11	0.8794
C2—N3	1.338 (3)	N2—H2A	0.8784
N3—C4	1.331 (3)	N2—H2B	0.8796
C4—N41	1.350 (3)	N41—C42	1.458 (3)
C4—C4a	1.428 (3)	N41—C46	1.473 (3)
C4a—C5	1.389 (3)	C42—C43	1.512 (3)
C4a—C11a	1.426 (3)	C42—H42A	0.9900
C5—N6	1.307 (3)	C42—H42B	0.9900
C5—H5	0.9500	C43—C44	1.518 (3)
N6—C6a	1.418 (3)	C43—H43A	0.9900
N6—H6	0.8796	C43—H43B	0.9900
C6a—C7	1.378 (3)	C44—C45	1.516 (3)
C6a—C10a	1.388 (3)	C44—H44A	0.9900
C7—C8	1.377 (3)	C44—H44B	0.9900
C7—H7	0.9500	C45—C46	1.510 (3)
C8—C9	1.373 (3)	C45—H45A	0.9900
C8—H8	0.9500	C45—H45B	0.9900
C9—C10	1.377 (3)	C46—H46A	0.9900
C9—H9	0.9500	C46—H46B	0.9900
C10—C10a	1.380 (3)	O1—H1B	0.892 (18)
C10—H10	0.9500	O1—H1A	0.885 (18)
C11a—N1—C2	117.00 (19)	N1—C11a—C4a	122.3 (2)
N2—C2—N3	118.1 (2)	N11—C11a—C4a	123.8 (2)
N2—C2—N1	114.5 (2)	C2—N2—H2A	114.6
N3—C2—N1	127.3 (2)	C2—N2—H2B	120.4
C4—N3—C2	115.77 (19)	H2A—N2—H2B	118.1
N3—C4—N41	117.64 (19)	C4—N41—C42	119.58 (18)
N3—C4—C4a	122.4 (2)	C4—N41—C46	121.53 (18)
N41—C4—C4a	119.92 (19)	C42—N41—C46	111.93 (17)
C5—C4a—C11a	123.4 (2)	N41—C42—C43	109.65 (18)
C5—C4a—C4	119.5 (2)	N41—C42—H42A	109.7
C11a—C4a—C4	114.90 (19)	C43—C42—H42A	109.7
N6—C5—C4a	128.8 (2)	N41—C42—H42B	109.7
N6—C5—H5	115.6	C43—C42—H42B	109.7
C4a—C5—H5	115.6	H42A—C42—H42B	108.2
C5—N6—C6a	128.1 (2)	C42—C43—C44	112.1 (2)
C5—N6—H6	118.6	C42—C43—H43A	109.2
C6a—N6—H6	112.7	C44—C43—H43A	109.2
C7—C6a—C10a	120.1 (2)	C42—C43—H43B	109.2
C7—C6a—N6	116.8 (2)	C44—C43—H43B	109.2
C10a—C6a—N6	123.2 (2)	H43A—C43—H43B	107.9
C8—C7—C6a	120.5 (2)	C45—C44—C43	109.98 (19)
C8—C7—H7	119.7	C45—C44—H44A	109.7
C6a—C7—H7	119.7	C43—C44—H44A	109.7
C9—C8—C7	119.7 (2)	C45—C44—H44B	109.7
C9—C8—H8	120.2	C43—C44—H44B	109.7
C7—C8—H8	120.2	H44A—C44—H44B	108.2
C8—C9—C10	120.0 (2)	C46—C45—C44	109.96 (18)
C8—C9—H9	120.0	C46—C45—H45A	109.7
C10—C9—H9	120.0	C44—C45—H45A	109.7
C9—C10—C10a	120.9 (2)	C46—C45—H45B	109.7
C9—C10—H10	119.5	C44—C45—H45B	109.7
C10a—C10—H10	119.5	H45A—C45—H45B	108.2
C10—C10a—C6a	118.8 (2)	N41—C46—C45	111.08 (19)
C10—C10a—N11	117.8 (2)	N41—C46—H46A	109.4
C6a—C10a—N11	123.3 (2)	C45—C46—H46A	109.4
C11a—N11—C10a	127.7 (2)	N41—C46—H46B	109.4
C11a—N11—H11	111.3	C45—C46—H46B	109.4
C10a—N11—H11	116.2	H46A—C46—H46B	108.0
N1—C11a—N11	113.8 (2)	H1B—O1—H1A	110 (3)
C11a—N1—C2—N2	−179.6 (2)	C7—C6a—C10a—N11	−174.8 (2)
C11a—N1—C2—N3	−2.0 (4)	N6—C6a—C10a—N11	3.4 (4)
N2—C2—N3—C4	178.6 (2)	C10—C10a—N11—C11a	139.2 (2)
N1—C2—N3—C4	1.0 (3)	C6a—C10a—N11—C11a	−45.3 (4)
C2—N3—C4—N41	−177.4 (2)	C2—N1—C11a—N11	−178.3 (2)
C2—N3—C4—C4a	3.6 (3)	C2—N1—C11a—C4a	−1.7 (3)
N3—C4—C4a—C5	156.8 (2)	C10a—N11—C11a—N1	−154.1 (2)
N41—C4—C4a—C5	−22.2 (3)	C10a—N11—C11a—C4a	29.3 (4)
N3—C4—C4a—C11a	−6.7 (3)	C5—C4a—C11a—N1	−157.0 (2)
N41—C4—C4a—C11a	174.3 (2)	C4—C4a—C11a—N1	5.7 (3)
C11a—C4a—C5—N6	−27.5 (4)	C5—C4a—C11a—N11	19.2 (4)
C4—C4a—C5—N6	170.5 (2)	C4—C4a—C11a—N11	−178.0 (2)
C4a—C5—N6—C6a	−13.2 (4)	N3—C4—N41—C42	−13.3 (3)
C5—N6—C6a—C7	−148.7 (2)	C4a—C4—N41—C42	165.7 (2)
C5—N6—C6a—C10a	33.1 (4)	N3—C4—N41—C46	135.1 (2)
C10a—C6a—C7—C8	0.7 (4)	C4a—C4—N41—C46	−45.8 (3)
N6—C6a—C7—C8	−177.6 (2)	C4—N41—C42—C43	−150.5 (2)
C6a—C7—C8—C9	−1.3 (4)	C46—N41—C42—C43	58.3 (2)
C7—C8—C9—C10	0.5 (4)	N41—C42—C43—C44	−56.1 (3)
C8—C9—C10—C10a	1.0 (4)	C42—C43—C44—C45	54.6 (3)
C9—C10—C10a—C6a	−1.5 (3)	C43—C44—C45—C46	−54.1 (3)
C9—C10—C10a—N11	174.2 (2)	C4—N41—C46—C45	149.5 (2)
C7—C6a—C10a—C10	0.7 (3)	C42—N41—C46—C45	−59.9 (2)
N6—C6a—C10a—C10	178.9 (2)	C44—C45—C46—N41	56.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.88	2.59	3.422 (2)	159
N11—H11···O1	0.88	1.92	2.782 (3)	167
O1—H1A···Cl1	0.88 (3)	2.29 (3)	3.151 (2)	165 (3)
O1—H1B···Cl1^i	0.89 (2)	2.19 (2)	3.078 (2)	171 (3)
N2—H2B···N3^ii	0.88	2.33	3.198 (3)	169
N6—H6···Cl1^iii	0.88	2.41	3.281 (2)	169

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

(II) 2-amino-4-[methyl(2-methylphenyl)amino]-11H-pyrimido[4,5- b][1,5]benzodiazepin-6-ium chloride–benzene-1,2-diamine (1/1)

Crystal data

C19H19N6^+·Cl^−·C6H8N2	Z = 2
Mr = 475.00	F(000) = 500
Triclinic, P1	Dx = 1.373 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9559 (13) Å	Cell parameters from 4532 reflections
b = 11.2372 (13) Å	θ = 3.1–26.1°
c = 11.432 (2) Å	µ = 0.20 mm^−1
α = 102.894 (12)°	T = 120 K
β = 112.176 (14)°	Plate, red
γ = 107.512 (10)°	0.42 × 0.35 × 0.12 mm
V = 1149.0 (3) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	4532 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3349 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 3.1°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.941, Tmax = 0.977	l = −14→14
30475 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 0.6732P] where P = (Fo^2 + 2Fc^2)/3
4532 reflections	(Δ/σ)max = 0.001
309 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.55239 (17)	0.73823 (16)	0.64680 (16)	0.0209 (4)
C2	0.4417 (2)	0.77397 (19)	0.62447 (19)	0.0212 (4)
N3	0.32250 (18)	0.71468 (17)	0.63410 (17)	0.0240 (4)
C4	0.3064 (2)	0.60181 (19)	0.65521 (19)	0.0214 (4)
C4a	0.4019 (2)	0.53863 (19)	0.65457 (19)	0.0198 (4)
C5	0.3525 (2)	0.39995 (19)	0.61827 (19)	0.0209 (4)
H5	0.2505	0.3512	0.5821	0.025*
N6	0.42532 (18)	0.32711 (16)	0.62647 (17)	0.0229 (4)
H6	0.3705	0.2352	0.5888	0.027*
C6a	0.5774 (2)	0.36777 (19)	0.69327 (19)	0.0209 (4)
C7	0.6241 (2)	0.2770 (2)	0.7359 (2)	0.0282 (5)
H7	0.5545	0.1925	0.7205	0.034*
C8	0.7699 (2)	0.3063 (2)	0.8004 (2)	0.0329 (5)
H8	0.8010	0.2424	0.8282	0.039*
C9	0.8700 (2)	0.4297 (2)	0.8240 (2)	0.0306 (5)
H9	0.9712	0.4515	0.8686	0.037*
C10	0.8240 (2)	0.5208 (2)	0.7832 (2)	0.0257 (4)
H10	0.8941	0.6062	0.8013	0.031*
C10a	0.6780 (2)	0.49138 (19)	0.71653 (19)	0.0200 (4)
N11	0.64165 (17)	0.58687 (16)	0.66964 (17)	0.0221 (4)
H11	0.7177	0.6531	0.6801	0.026*
C11a	0.5317 (2)	0.62148 (19)	0.65989 (19)	0.0199 (4)
N2	0.45923 (18)	0.88352 (17)	0.59617 (17)	0.0256 (4)
H2A	0.5353	0.9169	0.5843	0.031*
H2B	0.3871	0.9074	0.5677	0.031*
N4	0.19417 (18)	0.54615 (17)	0.67809 (18)	0.0252 (4)
C41	0.2007 (2)	0.4658 (2)	0.7605 (2)	0.0230 (4)
C42	0.3089 (2)	0.5232 (2)	0.8951 (2)	0.0276 (5)
C43	0.3129 (3)	0.4422 (2)	0.9700 (2)	0.0330 (5)
H43	0.3887	0.4777	1.0615	0.040*
C44	0.2092 (2)	0.3107 (2)	0.9148 (2)	0.0318 (5)
H44	0.2145	0.2564	0.9679	0.038*
C45	0.0985 (2)	0.2585 (2)	0.7832 (2)	0.0290 (5)
H45	0.0249	0.1691	0.7459	0.035*
C46	0.0942 (2)	0.3359 (2)	0.7054 (2)	0.0268 (5)
H46	0.0180	0.3001	0.6140	0.032*
C47	0.4152 (3)	0.6679 (2)	0.9583 (2)	0.0363 (5)
H47A	0.4768	0.6819	0.9142	0.055*
H47B	0.4764	0.6924	1.0561	0.055*
H47C	0.3624	0.7246	0.9461	0.055*
C48	0.0922 (2)	0.6070 (2)	0.6699 (3)	0.0352 (5)
H48A	0.1278	0.6754	0.7596	0.053*
H48B	−0.0037	0.5370	0.6418	0.053*
H48C	0.0840	0.6494	0.6028	0.053*
C21	1.1188 (2)	0.93489 (19)	0.7734 (2)	0.0242 (4)
C22	1.0316 (2)	0.90222 (19)	0.8347 (2)	0.0224 (4)
C23	1.0953 (2)	0.9155 (2)	0.9691 (2)	0.0265 (5)
H23	1.0352	0.8892	1.0092	0.032*
C24	1.2440 (2)	0.9659 (2)	1.0465 (2)	0.0312 (5)
H24	1.2863	0.9755	1.1394	0.037*
C25	1.3300 (2)	1.0021 (2)	0.9880 (2)	0.0329 (5)
H25	1.4330	1.0389	1.0410	0.039*
C26	1.2679 (2)	0.9856 (2)	0.8524 (2)	0.0312 (5)
H26	1.3289	1.0094	0.8125	0.037*
N21	1.0544 (2)	0.90913 (18)	0.63431 (18)	0.0304 (4)
H21A	0.9772	0.9260	0.6051	0.036*
H21B	1.1175	0.9450	0.6080	0.036*
N22	0.87926 (17)	0.84882 (17)	0.75784 (18)	0.0254 (4)
H22A	0.8501	0.8792	0.6926	0.031*
H22B	0.8393	0.8604	0.8108	0.031*
Cl1	0.75050 (5)	0.97781 (5)	0.52271 (5)	0.02635 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0220 (9)	0.0221 (9)	0.0228 (9)	0.0109 (7)	0.0118 (7)	0.0115 (7)
C2	0.0241 (10)	0.0222 (10)	0.0203 (10)	0.0114 (8)	0.0117 (8)	0.0094 (8)
N3	0.0252 (9)	0.0240 (9)	0.0302 (9)	0.0131 (7)	0.0162 (8)	0.0141 (8)
C4	0.0221 (10)	0.0223 (10)	0.0210 (10)	0.0099 (8)	0.0107 (8)	0.0088 (8)
C4a	0.0227 (10)	0.0208 (10)	0.0200 (10)	0.0104 (8)	0.0126 (8)	0.0088 (8)
C5	0.0247 (10)	0.0222 (10)	0.0213 (10)	0.0112 (8)	0.0146 (8)	0.0096 (8)
N6	0.0258 (9)	0.0181 (8)	0.0265 (9)	0.0098 (7)	0.0141 (7)	0.0079 (7)
C6a	0.0240 (10)	0.0229 (10)	0.0198 (10)	0.0127 (8)	0.0122 (8)	0.0080 (8)
C7	0.0346 (12)	0.0235 (11)	0.0299 (12)	0.0143 (9)	0.0166 (10)	0.0117 (9)
C8	0.0383 (13)	0.0343 (12)	0.0368 (13)	0.0238 (11)	0.0176 (11)	0.0206 (11)
C9	0.0284 (12)	0.0374 (13)	0.0310 (12)	0.0194 (10)	0.0135 (10)	0.0151 (10)
C10	0.0272 (11)	0.0278 (11)	0.0275 (11)	0.0142 (9)	0.0157 (9)	0.0116 (9)
C10a	0.0254 (11)	0.0230 (10)	0.0189 (10)	0.0146 (9)	0.0134 (8)	0.0092 (8)
N11	0.0219 (9)	0.0218 (8)	0.0301 (9)	0.0116 (7)	0.0157 (7)	0.0139 (7)
C11a	0.0245 (10)	0.0221 (10)	0.0169 (10)	0.0115 (8)	0.0117 (8)	0.0086 (8)
N2	0.0266 (9)	0.0268 (9)	0.0353 (10)	0.0157 (8)	0.0183 (8)	0.0200 (8)
N4	0.0256 (9)	0.0249 (9)	0.0382 (10)	0.0150 (7)	0.0212 (8)	0.0177 (8)
C41	0.0270 (11)	0.0223 (10)	0.0308 (11)	0.0139 (9)	0.0203 (9)	0.0128 (9)
C42	0.0341 (12)	0.0223 (10)	0.0292 (12)	0.0089 (9)	0.0216 (10)	0.0073 (9)
C43	0.0410 (13)	0.0319 (12)	0.0238 (11)	0.0105 (10)	0.0180 (10)	0.0092 (10)
C44	0.0419 (13)	0.0281 (11)	0.0354 (13)	0.0138 (10)	0.0258 (11)	0.0172 (10)
C45	0.0299 (12)	0.0209 (10)	0.0403 (13)	0.0088 (9)	0.0218 (10)	0.0126 (10)
C46	0.0216 (11)	0.0268 (11)	0.0329 (12)	0.0098 (9)	0.0142 (9)	0.0116 (9)
C47	0.0399 (14)	0.0271 (12)	0.0318 (13)	0.0053 (10)	0.0175 (11)	0.0060 (10)
C48	0.0336 (13)	0.0348 (13)	0.0565 (15)	0.0223 (11)	0.0296 (12)	0.0253 (12)
C21	0.0274 (11)	0.0176 (10)	0.0309 (12)	0.0110 (8)	0.0152 (9)	0.0106 (9)
C22	0.0205 (10)	0.0170 (10)	0.0286 (11)	0.0083 (8)	0.0107 (9)	0.0083 (8)
C23	0.0269 (11)	0.0255 (11)	0.0301 (12)	0.0128 (9)	0.0147 (9)	0.0118 (9)
C24	0.0281 (12)	0.0288 (12)	0.0305 (12)	0.0140 (10)	0.0083 (10)	0.0084 (10)
C25	0.0214 (11)	0.0257 (11)	0.0429 (14)	0.0100 (9)	0.0093 (10)	0.0093 (10)
C26	0.0256 (11)	0.0265 (11)	0.0442 (14)	0.0113 (9)	0.0195 (10)	0.0126 (10)
N21	0.0327 (10)	0.0346 (10)	0.0340 (10)	0.0170 (8)	0.0209 (9)	0.0180 (9)
N22	0.0212 (9)	0.0273 (9)	0.0282 (9)	0.0098 (7)	0.0116 (7)	0.0125 (8)
Cl1	0.0220 (3)	0.0219 (3)	0.0341 (3)	0.0086 (2)	0.0111 (2)	0.0142 (2)

Geometric parameters (Å, º)

N1—C11a	1.315 (2)	C42—C43	1.381 (3)
N1—C2	1.342 (2)	C42—C47	1.491 (3)
C2—N2	1.319 (2)	C43—C44	1.380 (3)
C2—N3	1.334 (2)	C43—H43	0.9500
N3—C4	1.316 (3)	C44—C45	1.370 (3)
C4—N4	1.350 (2)	C44—H44	0.9500
C4—C4a	1.432 (3)	C45—C46	1.375 (3)
C4a—C5	1.389 (3)	C45—H45	0.9500
C4a—C11a	1.416 (3)	C46—H46	0.9500
C5—N6	1.298 (2)	C47—H47A	0.9800
C5—H5	0.9500	C47—H47B	0.9800
N6—C6a	1.412 (2)	C47—H47C	0.9800
N6—H6	0.9199	C48—H48A	0.9800
C6a—C7	1.374 (3)	C48—H48B	0.9800
C6a—C10a	1.381 (3)	C48—H48C	0.9800
C7—C8	1.374 (3)	C21—C26	1.380 (3)
C7—H7	0.9500	C21—N21	1.391 (3)
C8—C9	1.375 (3)	C21—C22	1.396 (3)
C8—H8	0.9500	C22—C23	1.377 (3)
C9—C10	1.366 (3)	C22—N22	1.404 (2)
C9—H9	0.9500	C23—C24	1.375 (3)
C10—C10a	1.377 (3)	C23—H23	0.9500
C10—H10	0.9500	C24—C25	1.367 (3)
C10a—N11	1.397 (2)	C24—H24	0.9500
N11—C11a	1.347 (2)	C25—C26	1.378 (3)
N11—H11	0.8798	C25—H25	0.9500
N2—H2A	0.8796	C26—H26	0.9500
N2—H2B	0.8799	N21—H21A	0.8802
N4—C41	1.441 (2)	N21—H21B	0.8800
N4—C48	1.461 (3)	N22—H22A	0.8801
C41—C46	1.378 (3)	N22—H22B	0.8800
C41—C42	1.382 (3)
C11a—N1—C2	116.33 (16)	C43—C42—C47	121.2 (2)
N2—C2—N3	118.14 (17)	C41—C42—C47	121.4 (2)
N2—C2—N1	114.70 (17)	C44—C43—C42	121.5 (2)
N3—C2—N1	127.08 (18)	C44—C43—H43	119.3
C4—N3—C2	115.71 (17)	C42—C43—H43	119.3
N3—C4—N4	117.05 (17)	C45—C44—C43	119.9 (2)
N3—C4—C4a	122.62 (17)	C45—C44—H44	120.1
N4—C4—C4a	120.33 (17)	C43—C44—H44	120.1
C5—C4a—C11a	123.46 (17)	C44—C45—C46	119.8 (2)
C5—C4a—C4	120.63 (17)	C44—C45—H45	120.1
C11a—C4a—C4	114.12 (17)	C46—C45—H45	120.1
N6—C5—C4a	129.52 (19)	C45—C46—C41	119.8 (2)
N6—C5—H5	115.2	C45—C46—H46	120.1
C4a—C5—H5	115.2	C41—C46—H46	120.1
C5—N6—C6a	129.59 (17)	C42—C47—H47A	109.5
C5—N6—H6	115.8	C42—C47—H47B	109.5
C6a—N6—H6	114.5	H47A—C47—H47B	109.5
C7—C6a—C10a	119.78 (18)	C42—C47—H47C	109.5
C7—C6a—N6	116.65 (17)	H47A—C47—H47C	109.5
C10a—C6a—N6	123.57 (17)	H47B—C47—H47C	109.5
C6a—C7—C8	121.1 (2)	N4—C48—H48A	109.5
C6a—C7—H7	119.4	N4—C48—H48B	109.5
C8—C7—H7	119.4	H48A—C48—H48B	109.5
C7—C8—C9	119.1 (2)	N4—C48—H48C	109.5
C7—C8—H8	120.5	H48A—C48—H48C	109.5
C9—C8—H8	120.5	H48B—C48—H48C	109.5
C10—C9—C8	120.0 (2)	C26—C21—N21	121.70 (19)
C10—C9—H9	120.0	C26—C21—C22	118.3 (2)
C8—C9—H9	120.0	N21—C21—C22	119.88 (18)
C9—C10—C10a	121.39 (19)	C23—C22—C21	119.52 (18)
C9—C10—H10	119.3	C23—C22—N22	120.12 (18)
C10a—C10—H10	119.3	C21—C22—N22	120.27 (18)
C10—C10a—C6a	118.69 (18)	C24—C23—C22	121.5 (2)
C10—C10a—N11	117.01 (17)	C24—C23—H23	119.3
C6a—C10a—N11	124.19 (17)	C22—C23—H23	119.3
C11a—N11—C10a	129.86 (16)	C25—C24—C23	119.1 (2)
C11a—N11—H11	112.7	C25—C24—H24	120.4
C10a—N11—H11	112.4	C23—C24—H24	120.4
N1—C11a—N11	112.92 (17)	C24—C25—C26	120.2 (2)
N1—C11a—C4a	122.41 (17)	C24—C25—H25	119.9
N11—C11a—C4a	124.54 (18)	C26—C25—H25	119.9
C2—N2—H2A	116.2	C25—C26—C21	121.3 (2)
C2—N2—H2B	120.9	C25—C26—H26	119.4
H2A—N2—H2B	120.6	C21—C26—H26	119.4
C4—N4—C41	121.49 (16)	C21—N21—H21A	113.5
C4—N4—C48	119.71 (17)	C21—N21—H21B	113.0
C41—N4—C48	114.34 (16)	H21A—N21—H21B	113.6
C46—C41—C42	121.54 (19)	C22—N22—H22A	113.3
C46—C41—N4	119.15 (19)	C22—N22—H22B	111.3
C42—C41—N4	119.20 (18)	H22A—N22—H22B	111.5
C43—C42—C41	117.41 (19)
C11a—N1—C2—N2	−172.52 (17)	C4—C4a—C11a—N1	−9.2 (3)
C11a—N1—C2—N3	10.8 (3)	C5—C4a—C11a—N11	−19.9 (3)
N2—C2—N3—C4	176.49 (18)	C4—C4a—C11a—N11	175.30 (18)
N1—C2—N3—C4	−6.9 (3)	N3—C4—N4—C41	−151.10 (18)
C2—N3—C4—N4	174.00 (17)	C4a—C4—N4—C41	28.9 (3)
C2—N3—C4—C4a	−6.0 (3)	N3—C4—N4—C48	3.9 (3)
N3—C4—C4a—C5	−151.95 (19)	C4a—C4—N4—C48	−176.14 (19)
N4—C4—C4a—C5	28.1 (3)	C4—N4—C41—C46	−123.8 (2)
N3—C4—C4a—C11a	13.3 (3)	C48—N4—C41—C46	80.0 (2)
N4—C4—C4a—C11a	−166.66 (18)	C4—N4—C41—C42	59.9 (3)
C11a—C4a—C5—N6	25.0 (3)	C48—N4—C41—C42	−96.3 (2)
C4—C4a—C5—N6	−171.18 (19)	C46—C41—C42—C43	4.8 (3)
C4a—C5—N6—C6a	10.9 (3)	N4—C41—C42—C43	−178.96 (18)
C5—N6—C6a—C7	153.1 (2)	C46—C41—C42—C47	−173.87 (19)
C5—N6—C6a—C10a	−27.1 (3)	N4—C41—C42—C47	2.3 (3)
C10a—C6a—C7—C8	−0.7 (3)	C41—C42—C43—C44	−2.9 (3)
N6—C6a—C7—C8	179.17 (19)	C47—C42—C43—C44	175.8 (2)
C6a—C7—C8—C9	1.0 (3)	C42—C43—C44—C45	−0.6 (3)
C7—C8—C9—C10	−0.1 (3)	C43—C44—C45—C46	2.2 (3)
C8—C9—C10—C10a	−1.0 (3)	C44—C45—C46—C41	−0.4 (3)
C9—C10—C10a—C6a	1.2 (3)	C42—C41—C46—C45	−3.3 (3)
C9—C10—C10a—N11	−175.14 (18)	N4—C41—C46—C45	−179.48 (18)
C7—C6a—C10a—C10	−0.4 (3)	C26—C21—C22—C23	−2.9 (3)
N6—C6a—C10a—C10	179.76 (18)	N21—C21—C22—C23	173.58 (18)
C7—C6a—C10a—N11	175.69 (18)	C26—C21—C22—N22	−179.21 (18)
N6—C6a—C10a—N11	−4.2 (3)	N21—C21—C22—N22	−2.8 (3)
C10—C10a—N11—C11a	−146.2 (2)	C21—C22—C23—C24	2.9 (3)
C6a—C10a—N11—C11a	37.7 (3)	N22—C22—C23—C24	179.23 (18)
C2—N1—C11a—N11	174.35 (16)	C22—C23—C24—C25	−0.8 (3)
C2—N1—C11a—C4a	−1.6 (3)	C23—C24—C25—C26	−1.3 (3)
C10a—N11—C11a—N1	162.65 (18)	C24—C25—C26—C21	1.3 (3)
C10a—N11—C11a—C4a	−21.5 (3)	N21—C21—C26—C25	−175.5 (2)
C5—C4a—C11a—N1	155.61 (19)	C22—C21—C26—C25	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.88	2.65	3.521 (2)	171
N11—H11···N22	0.88	2.09	2.922 (3)	158
N21—H21A···Cl1	0.88	2.60	3.477 (2)	179
N22—H22A···Cl1	0.88	2.51	3.380 (2)	172
N2—H2B···Cl1^i	0.88	2.37	3.209 (2)	161
N6—H6···Cl1^ii	0.92	2.14	3.050 (2)	172
N21—H21B···Cl1^iii	0.88	2.56	3.418 (2)	167
C9—H9···Cg1^iv	0.95	2.96	3.770 (3)	144

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