10-Benzyl-4-oxo-2,3,4,10-tetra­hydro­pyrimido[4,5-b]quinolin-2-iminium chloride sesquihydrate: a polarized electronic structure within a complex hydrogen-bonded sheet structure

In the title compound, C₁₈H₁₅N₄O⁺·Cl⁻·1.5H₂O, one water site is fully ordered with unit occupancy while the other, which lies close to an inversion centre in the space group C2/c, has only 0.5 occupancy. The cation exhibits bond fixation in the fused carbocyclic ring and electronic polarization in the terminal heterocyclic ring. The components are linked into complex sheets by a combination of N—H...O, N—H...Cl, O—H...O, O—H...Cl and C—H...O hydrogen bonds.

S1. Comment

Pyrimido[4,5-b]quinolines have been synthesized by a diverse range of procedures which involve the cyclocondensation of 2-aminoquinoline-3-carboxylic acid derivatives with a variety of reagents such as formamide, acetic anhydride, phenyl isocyanate, phenyl isothiocyanate and diethyl carbonate (Taylor & Kalenda, 1956). The Skraup, Dobner von Miller, Friedländer and Combes syntheses are also well known methods for preparing quinolines (Yang et al., 2007). Despite this, the development of simple, general and efficient procedures for the preparation of these important heterocyclic compounds still proves to be demanding. Here, we report the structure of the title deazaflavine analogue which has been prepared using an intramolecular cyclization of 2-amino-4-(benzyl(phenyl)amino)-6-chloropyrimidine-5-carbaldehyde in acetic acid, mediated by microwave radiation; cyclization of the precursor (A) (see Scheme 1) accompanied by hydrolysis at the 6-position yields as the primary product the salt (B), crystallization of which gave the title compound, (I). We have recently reported the structure of the unsolvated 4-toluenesulfonate salt, (II), of the analogous 10-ethyl cation (Trilleras et al., 2008) prepared in a rather similar way from the precursor (C) (see Scheme 2), but here in the presence of 4-toluenesulfonic acid rather than acetic acid. The molecular and supramolecular structures of compounds (I) and (II) are of interest as they exhibit both similarities and differences. We have not investigated the source of the water which is involved in the formation of compound (I), both in respect of the hydrolysis of the 6-chloro substituent and in the crystallization as a sesquihydrate; however, such hydrolyses appear to be entirely general in syntheses of this type, regardless of the nature of the acid employed (Quiroga et al., 2010), and it seems likely that the acid is the most plausible source of the water component.

The title compound is a hydrated hydrochloride salt containing 1.5 molecules of water per ion pair (Fig. 1). One of the water molecules, that containing atom O1, is fully ordered with unit occupancy, but the other, containing atom O2, has a site occupancy of 0.5 but unfortunately it did not prove possible to make reliable identifications of the corresponding H-atom sites. Atom O2 is located close to a centre of inversion such that the distance between the inversion-related pair of sites occupied by atoms of type O2 is only 1.005 (8) Å; consequently, if at the local level one site in such an inversion-related pair is occupied, the other must necessarily be unoccupied, and conversely [vice versa?].

Despite the presence of four independent entities within the structure it is possible to specify a fairly compact asymmetric unit in which the four components are all linked by hydrogen bonds (Table 2, Fig. 1). In the selected asymmetric unit, the atoms N2 and N3 both act as hydrogen-bond donors to the chloride ion, forming an R¹₂(6) (Bernstein et al., 1995) motif, and atom N2 also acts as hydrogen-bond donor to the full-occupancy water atom O1. The atom O1 in turn acts as hydrogen-bond donor, via atom H11, either to water atom O2 within the selected asymmetric unit or to the inversion-related atom O2 at (1 - x, 1 - y, 1 - z), depending upon which of the two alternative O2 sites is occupied. Thus, with the asymmetric unit specified in this manner, the inversion-related pair of O2 sites lies across (1/2, 1/2, 1/2), but no matter which of these two sites is occupied, the atom O2 which is present in one of them always accepts a hydrogen bond from the adjacent atom O1 at (x, y, z).

Within the fused carbocyclic ring, the C—C distances (Table 1) show evidence of some bond fixation, as the bonds C6—C7 and C8—C9 are significantly shorter than the remaining peripheral bonds, while in the central ring of the fused system, the bond C4A—C5 is very much shorter than the bond C5—C5A, indicative of a double bond between atoms C4A and C5. By contrast, in the ring (C111—C116) the C—C distances all lie within a rather narrow range, 1.368 (4)–1.380 (3) Å. The C—N distances associated with the pyrimidinone ring show some interesting variations: in particular, the exocyclic bond C2—N2 is very short for a single bond [mean value for this type (Allen et al., 1987) 1.355 (20) Å, lower-quartile value 1.340 Å. no s.u. cited], while the bonds C2—N3 and N3—C4 differ only slightly in length. These observations indicate that the predominant canonical form (I) (see Scheme 1) is that having the positive charge localized at atom N2, while the form (Ia) with the charge localized at N3 is less significant. A rather similar pattern of distances was observed in the cation of compound (II), which was described as a protonated iminouracil derivative (Trilleras et al., 2008).

In addition to the four hydrogen bonds within the selected asymmetric unit (Fig. 1), the structure also contains a considerable number of other hydrogen bonds, encompassing O—H···O, O—H···Cl, N—H···O, C—H···O and C—H···Cl types, which link the four-component aggregates defined by the selected asymmetric unit to form complex sheets. However, the analysis of the sheet formation is very much simplified using the sub-structure approach (Ferguson et al., 1998a,b; Gregson et al., 2000), which permits the identification of a one-dimensional sub-structure in the form of a ribbon of edge-fused rings built from the full-occupancy components only, while the linking of adjacent ribbons of this type straightforwardly leads to the formation of a sheet.

The atoms O1 and N2 in the reference aggregate at (x, y, z) act as hydrogen-bond donors, respectively, via atoms H12 and H22, to atoms Cl1 and O4 in the aggregate at (1/2 + x, 1/2 - y, 1/2 + z), so linking aggregates related by the n-glide plane at y = 0.25 into a ribbon running parallel to the [101] direction and built from edge-fused R¹₂(6) and R³₄(10) rings (Fig. 2).

The linking of the ribbons depends upon a combination of O—H···O and C—H···O hydrogen bonds, both having the disordered water atom O2 as the acceptor, and it is convenient to consider, in turn, the two cases where the occupancy of an inversion-related pair of sites involves first the O2 site at (x, y, z) and secondly the O2 site at (1 - x, 1 - y, 1 - z). When the O2 site at (x, y, z) is occupied and that at (1 - x, 1 - y, 1 - z) is vacant, the atom O2 accepts O—H···O hydrogen bonds from the atoms O1 at (x, y, z) and (1 - x, 1 - y, 1 - z), and it accepts a C—H···O hydrogen bond from atom C101 at (1 - x, 1 - y, 1 - z) (Table 2). On the other hand, if the O2 site at (1 - x, 1 - y, 1 - z) is occupied and that at (x, y, z) is vacant, the atom O2 still accepts O—H···O hydrogen bonds from the atoms O1 at (x, y, z) and (1 - x, 1 - y, 1 - z), and it accepts a C—H···O hydrogen bond from the atom C101 at (x, y, z). Consequently, regardless of which of the two inversion-related sites in any such pair is occupied, the atom O2 present accepts hydrogen bonds from the ordered components at (x, y, z) and (1 - x, 1 - y, 1 - z). The ordered components at (x, y, z) form part of that ribbon along [101] which contains the n-glide plane at y = 1/4, while those at (1 - x, 1 - y, 1 - z) lie in the ribbon containing the n-glide plane at y = 3/4, and propagation of these hydrogen bonds by the space-group symmetry operation links the ribbon along [101] into a complex sheet lying parallel to (101). It should be noted here that with the possible exception of the benzyl ring at (x, 1 - y, 1/2 + z), there are no acceptor sites within plausible hydrogen-bonding range of the site O2 other than the two symmetry-related O1 sites: possibly this absence of available acceptor sites leads to positional disorder of the H atoms bonded to O2.

The structure also contains two C—H···Cl contacts, both of which are nearly linear (Table 2). That involving atom C5 lies within the ribbon along [101] and containing the n-glide plane at y = 1/4, while the contact involving atom C101 is between adjacent ribbons within the (101) sheet. Regardless, therefore, of whether these contacts can be regarded as structurally significant (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001), they have no bearing on the overall dimensionality of the hydrogen-bonded structure.

The complex hydrogen-bonded structure of compound (I), dependent on a combination of N—H···O, N—H···Cl, O—H···O, O—H···Cl and C—H···O interactions, may be contrasted with the much simpler supramolecular structure of compound (II) (Trilleras et al., 2008), where three independent N—H···O hydrogen bonds link the ions into centrosymmetric four-ion aggregates, which themselves are linked into sheets by a single, rather strong C—H···O hydrogen bond. The greater complexity in compound (I) is almost certainly a consequence of its crystallization as a hydrate; but why (I) is a hydrate, while (II) is solvent-free cannot readily be explained.

Related literature

For related literature, see: Aakeröy et al. (1999); Allen et al. (1987); Bernstein et al. (1995); Brammer et al. (2001); Ferguson et al. (1998a, 1998b); Gregson et al. (2000); Quiroga et al. (2010); Taylor & Kalenda (1956); Thallapally & Nangia (2001); Trilleras et al. (2008); Yang et al. (2007).

S2. Experimental

A solution of 2-amino-4-(benzyl(phenyl)amino)-6-chloropyrimidine-5-carbaldehyde (1.0 mmol) in glacial acetic acid (1.5 cm³) was subjected to microwave irradiation (maximum power 300 W during 15 min at a controlled temperature of 573 K) using a focused microwave reactor (CEM Discover). The resulting solid product was collected by filtration and washed with hot hexane to give a yellow solid that was recrystallized from hexane to afford crystals suitable for single-crystal X-ray diffraction. Yield 80%, m.p. > 573 K; MS (70 eV) m/z (%) = 303 [(M—Cl—H₂O)⁺, 23], 302 (99), 301 (78), 273 (13), 231 (30), 129 (14), 91 (100).

S3. Refinement

It was apparent from an early stage in the refinement that the atom site designated as O2 (a) had only partial occupancy and (b) was close to an inversion-related analogue. Refinement of the site occupancy for O2, treated anisotropically, gave an occupancy of 0.494 (7): thereafter the site occupancy was fixed at 0.5. Alternative assignments for the site labelled O2 were discounted on the following grounds: chloride and hydroxide were discounted because difference maps provided no evidence of any further protonation elsewhere in the structure, and in any event this site is too close to O1 for it to be occupied by Cl; NH₃ was discounted because refinement of the site occupancy of N gave a value 0.591 (7), which is impossible so close to an inversion centre. Although data were collected to θ = 27.5°, the data were very weak above θ = 25.5° with correspondingly rather high values of R₁ and wR₂: accordingly, in the final refinements θ_max was set to 25.5°. With the exception of the H atoms bonded to O2, all other H atoms were located in difference maps, but there is no evidence for any degree of protonation at atoms N1 or N10. The H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (ring H atoms) or 0.99 Å (CH₂), and with U_iso(H) = 1.2U_eq(C). The H atoms bonded to N atoms were permitted to ride at the positions deduced from the difference maps, with U_iso(H) = 1.2U_eq(N), giving N—H distances in the range 0.86–1.00 Å. The coordinates of the H atoms bonded to water atom O1 were refined, with U_iso(H) = 1.5U_eq(O), with restraints of 0.82 (1) and 1.32 (2) Å, respectively, applied to the O—H and H···H distances, giving final O—H distances of 0.81 (3) and 0.83 (4) Å.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: 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 compound (I) showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit. The water atom O2 has 0.5 occupancy but the associated H atoms could not be located. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. A stereoview of part of the crystal structure of compound (I) showing the formation of a hydrogen-bonded ribbon of R^12(6) and R^34(10) rings running parallel to [101]. For the sake of clarity the H atoms bonded to C atoms and the partial-occupancy water atom O2 have been omitted.

10-Benzyl-4-oxo-2,3,4,10-tetrahydropyrimido[4,5-b]quinolin-2-iminium chloride sesquihydrate

Crystal data

C18H15N4O^+·Cl^−·1.5H2O	F(000) = 1520
Mr = 365.82	Dx = 1.447 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3842 reflections
a = 18.8725 (10) Å	θ = 3.0–27.5°
b = 18.4777 (8) Å	µ = 0.25 mm^−1
c = 13.417 (2) Å	T = 120 K
β = 134.307 (7)°	Block, colourless
V = 3348.2 (7) Å^3	0.41 × 0.25 × 0.22 mm
Z = 8

Data collection

Bruker Nonius KappaCCD diffractometer	3122 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2297 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.0°
ϕ and ω scans	h = −22→22
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −22→22
Tmin = 0.885, Tmax = 0.936	l = −16→16
33176 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) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 5.0661P] where P = (Fo^2 + 2Fc^2)/3
3122 reflections	(Δ/σ)max = 0.001
241 parameters	Δρmax = 0.34 e Å^−3
3 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.28366 (14)	0.40754 (11)	0.6729 (2)	0.0212 (5)
C2	0.28792 (17)	0.33596 (14)	0.6676 (2)	0.0219 (5)
N3	0.20691 (14)	0.29246 (11)	0.5844 (2)	0.0227 (5)
H3	0.2130	0.2384	0.5851	0.027*
C4	0.11264 (17)	0.31881 (13)	0.4844 (2)	0.0230 (5)
C4A	0.10571 (17)	0.39758 (13)	0.4807 (2)	0.0208 (5)
C5	0.01754 (17)	0.43065 (13)	0.3871 (2)	0.0221 (5)
H5	−0.0408	0.4028	0.3199	0.027*
C5A	0.01147 (17)	0.50636 (13)	0.3883 (2)	0.0221 (5)
C6	−0.07907 (18)	0.54281 (14)	0.2909 (3)	0.0256 (6)
H6	−0.1380	0.5161	0.2213	0.031*
C7	−0.08343 (19)	0.61584 (14)	0.2949 (3)	0.0285 (6)
H7	−0.1447	0.6404	0.2267	0.034*
C8	0.00229 (19)	0.65428 (14)	0.3994 (3)	0.0291 (6)
H8	−0.0015	0.7053	0.4035	0.035*
C9	0.09212 (19)	0.62104 (13)	0.4967 (3)	0.0254 (6)
H9	0.1498	0.6487	0.5672	0.031*
C9A	0.09856 (17)	0.54620 (13)	0.4916 (2)	0.0219 (5)
N10	0.18806 (14)	0.51003 (10)	0.58560 (19)	0.0206 (4)
C10A	0.19477 (17)	0.43727 (13)	0.5820 (2)	0.0196 (5)
N2	0.37444 (14)	0.30473 (11)	0.7505 (2)	0.0261 (5)
H21	0.4296	0.3276	0.7958	0.031*
H22	0.3772	0.2569	0.7381	0.031*
O4	0.04242 (13)	0.27879 (9)	0.40847 (19)	0.0350 (5)
C101	0.28004 (17)	0.55194 (13)	0.6920 (2)	0.0230 (5)
H10A	0.3337	0.5185	0.7650	0.028*
H10B	0.2694	0.5869	0.7365	0.028*
C111	0.31152 (17)	0.59210 (13)	0.6315 (2)	0.0207 (5)
C112	0.3348 (2)	0.66459 (14)	0.6589 (3)	0.0311 (6)
H112	0.3304	0.6894	0.7164	0.037*
C113	0.3642 (2)	0.70135 (15)	0.6040 (3)	0.0348 (7)
H113	0.3810	0.7512	0.6247	0.042*
C114	0.3695 (2)	0.66629 (17)	0.5195 (3)	0.0400 (7)
H114	0.3888	0.6918	0.4802	0.048*
C115	0.3469 (2)	0.59412 (17)	0.4921 (3)	0.0438 (8)
H115	0.3508	0.5696	0.4339	0.053*
C116	0.31856 (19)	0.55699 (14)	0.5480 (3)	0.0301 (6)
H116	0.3037	0.5068	0.5291	0.036*
Cl1	0.26888 (4)	0.13346 (3)	0.62419 (6)	0.02335 (17)
O1	0.53555 (13)	0.40476 (11)	0.8831 (2)	0.0353 (5)
H11	0.527 (2)	0.4339 (15)	0.921 (3)	0.053*
H12	0.5928 (15)	0.3928 (17)	0.937 (3)	0.053*
O2	0.5044 (3)	0.4776 (2)	1.0251 (5)	0.0466 (11)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0187 (10)	0.0223 (12)	0.0199 (10)	−0.0026 (8)	0.0125 (10)	−0.0007 (9)
C2	0.0217 (13)	0.0272 (14)	0.0192 (12)	−0.0025 (10)	0.0151 (12)	0.0002 (10)
N3	0.0222 (11)	0.0191 (11)	0.0261 (11)	−0.0014 (8)	0.0166 (10)	−0.0002 (9)
C4	0.0199 (12)	0.0250 (14)	0.0228 (13)	−0.0019 (11)	0.0144 (11)	−0.0022 (11)
C4A	0.0221 (12)	0.0224 (13)	0.0216 (13)	−0.0014 (10)	0.0167 (11)	−0.0008 (10)
C5	0.0234 (13)	0.0265 (14)	0.0196 (12)	−0.0013 (10)	0.0162 (11)	0.0000 (10)
C5A	0.0262 (13)	0.0256 (13)	0.0236 (13)	0.0010 (10)	0.0207 (12)	0.0019 (10)
C6	0.0260 (13)	0.0317 (15)	0.0254 (13)	0.0024 (11)	0.0203 (12)	0.0026 (11)
C7	0.0311 (14)	0.0290 (15)	0.0336 (15)	0.0076 (11)	0.0256 (13)	0.0104 (12)
C8	0.0389 (15)	0.0222 (14)	0.0429 (16)	0.0009 (11)	0.0347 (15)	0.0031 (12)
C9	0.0310 (14)	0.0249 (14)	0.0339 (14)	−0.0029 (11)	0.0276 (13)	−0.0002 (11)
C9A	0.0255 (13)	0.0246 (14)	0.0253 (13)	−0.0010 (10)	0.0212 (12)	0.0018 (10)
N10	0.0233 (10)	0.0205 (11)	0.0213 (10)	−0.0027 (8)	0.0167 (10)	−0.0026 (8)
C10A	0.0239 (13)	0.0232 (13)	0.0184 (12)	−0.0032 (10)	0.0172 (11)	−0.0016 (10)
N2	0.0198 (10)	0.0247 (12)	0.0260 (11)	−0.0006 (9)	0.0132 (10)	−0.0003 (9)
O4	0.0231 (10)	0.0247 (10)	0.0420 (11)	−0.0055 (8)	0.0171 (9)	−0.0075 (9)
C101	0.0254 (13)	0.0225 (13)	0.0217 (12)	−0.0067 (10)	0.0167 (12)	−0.0057 (10)
C111	0.0172 (11)	0.0230 (13)	0.0194 (12)	−0.0011 (10)	0.0119 (11)	−0.0015 (10)
C112	0.0376 (15)	0.0267 (14)	0.0401 (16)	−0.0076 (12)	0.0313 (14)	−0.0098 (12)
C113	0.0405 (16)	0.0283 (15)	0.0446 (17)	−0.0114 (12)	0.0330 (15)	−0.0074 (13)
C114	0.0490 (18)	0.0439 (18)	0.0428 (17)	−0.0197 (14)	0.0379 (16)	−0.0089 (14)
C115	0.062 (2)	0.0455 (19)	0.0514 (19)	−0.0244 (16)	0.0499 (19)	−0.0241 (15)
C116	0.0347 (15)	0.0264 (14)	0.0345 (15)	−0.0088 (12)	0.0262 (13)	−0.0092 (12)
Cl1	0.0217 (3)	0.0243 (3)	0.0228 (3)	0.0001 (3)	0.0151 (3)	0.0014 (3)
O1	0.0230 (10)	0.0315 (11)	0.0369 (11)	0.0013 (8)	0.0156 (9)	−0.0021 (9)
O2	0.032 (2)	0.047 (3)	0.046 (3)	−0.001 (2)	0.022 (2)	−0.003 (2)

Geometric parameters (Å, º)

N1—C2	1.330 (3)	C8—H8	0.9500
C2—N3	1.358 (3)	C9—H9	0.9500
N3—C4	1.367 (3)	N10—C101	1.480 (3)
C4—C4A	1.459 (3)	N2—H21	0.8643
C4A—C5	1.342 (3)	N2—H22	0.9072
C5—C5A	1.405 (3)	C101—C111	1.495 (3)
C5A—C6	1.401 (3)	C101—H10A	0.9900
C6—C7	1.355 (3)	C101—H10B	0.9900
C7—C8	1.385 (4)	C111—C112	1.377 (3)
C8—C9	1.365 (4)	C111—C116	1.380 (3)
C9—C9A	1.394 (3)	C112—C113	1.373 (4)
C9A—N10	1.384 (3)	C112—H112	0.9500
N10—C10A	1.354 (3)	C113—C114	1.368 (4)
C10A—N1	1.321 (3)	C113—H113	0.9500
C4A—C10A	1.421 (3)	C114—C115	1.370 (4)
C5A—C9A	1.408 (3)	C114—H114	0.9500
C2—N2	1.304 (3)	C115—C116	1.370 (4)
C4—O4	1.206 (3)	C115—H115	0.9500
N3—H3	1.0052	C116—H116	0.9500
C5—H5	0.9500	O1—H11	0.83 (4)
C6—H6	0.9500	O1—H12	0.81 (4)
C7—H7	0.9500	O2—O2^i	1.005 (8)
C10A—N1—C2	116.7 (2)	C10A—N10—C9A	122.1 (2)
N2—C2—N1	118.8 (2)	C10A—N10—C101	118.6 (2)
N2—C2—N3	117.3 (2)	C9A—N10—C101	119.3 (2)
N1—C2—N3	123.8 (2)	N1—C10A—N10	118.0 (2)
C2—N3—C4	122.8 (2)	N1—C10A—C4A	124.0 (2)
C2—N3—H3	121.7	N10—C10A—C4A	118.0 (2)
C4—N3—H3	115.2	C2—N2—H21	124.0
O4—C4—N3	121.3 (2)	C2—N2—H22	118.2
O4—C4—C4A	124.3 (2)	H21—N2—H22	114.3
N3—C4—C4A	114.4 (2)	N10—C101—C111	112.30 (19)
C5—C4A—C10A	121.7 (2)	N10—C101—H10A	109.1
C5—C4A—C4	120.6 (2)	C111—C101—H10A	109.1
C10A—C4A—C4	117.7 (2)	N10—C101—H10B	109.1
C4A—C5—C5A	120.0 (2)	C111—C101—H10B	109.1
C4A—C5—H5	120.0	H10A—C101—H10B	107.9
C5A—C5—H5	120.0	C112—C111—C116	118.7 (2)
C6—C5A—C5	121.6 (2)	C112—C111—C101	120.8 (2)
C6—C5A—C9A	119.5 (2)	C116—C111—C101	120.5 (2)
C5—C5A—C9A	118.9 (2)	C113—C112—C111	120.7 (2)
C7—C6—C5A	120.7 (2)	C113—C112—H112	119.6
C7—C6—H6	119.7	C111—C112—H112	119.6
C5A—C6—H6	119.7	C114—C113—C112	120.1 (3)
C6—C7—C8	119.4 (2)	C114—C113—H113	120.0
C6—C7—H7	120.3	C112—C113—H113	120.0
C8—C7—H7	120.3	C113—C114—C115	119.6 (3)
C9—C8—C7	122.0 (2)	C113—C114—H114	120.2
C9—C8—H8	119.0	C115—C114—H114	120.2
C7—C8—H8	119.0	C116—C115—C114	120.6 (3)
C8—C9—C9A	119.5 (2)	C116—C115—H115	119.7
C8—C9—H9	120.3	C114—C115—H115	119.7
C9A—C9—H9	120.3	C115—C116—C111	120.3 (2)
N10—C9A—C9	121.8 (2)	C115—C116—H116	119.8
N10—C9A—C5A	119.2 (2)	C111—C116—H116	119.8
C9—C9A—C5A	119.0 (2)	H11—O1—H12	110 (2)
C10A—N1—C2—N2	176.5 (2)	C5A—C9A—N10—C10A	−0.3 (3)
C10A—N1—C2—N3	−6.3 (3)	C9—C9A—N10—C101	−1.9 (3)
N2—C2—N3—C4	−173.9 (2)	C5A—C9A—N10—C101	178.40 (19)
N1—C2—N3—C4	8.8 (4)	C2—N1—C10A—N10	179.5 (2)
C2—N3—C4—O4	177.1 (2)	C2—N1—C10A—C4A	−0.5 (3)
C2—N3—C4—C4A	−3.9 (3)	C9A—N10—C10A—N1	177.8 (2)
O4—C4—C4A—C5	−1.4 (4)	C101—N10—C10A—N1	−0.9 (3)
N3—C4—C4A—C5	179.7 (2)	C9A—N10—C10A—C4A	−2.2 (3)
O4—C4—C4A—C10A	176.6 (2)	C101—N10—C10A—C4A	179.07 (19)
N3—C4—C4A—C10A	−2.3 (3)	C5—C4A—C10A—N1	−177.3 (2)
C10A—C4A—C5—C5A	−0.5 (3)	C4—C4A—C10A—N1	4.7 (3)
C4—C4A—C5—C5A	177.4 (2)	C5—C4A—C10A—N10	2.7 (3)
C4A—C5—C5A—C6	179.0 (2)	C4—C4A—C10A—N10	−175.3 (2)
C4A—C5—C5A—C9A	−2.1 (3)	C10A—N10—C101—C111	104.9 (2)
C5—C5A—C6—C7	179.2 (2)	C9A—N10—C101—C111	−73.8 (3)
C9A—C5A—C6—C7	0.3 (3)	N10—C101—C111—C112	130.2 (2)
C5A—C6—C7—C8	−2.1 (4)	N10—C101—C111—C116	−50.3 (3)
C6—C7—C8—C9	2.0 (4)	C116—C111—C112—C113	0.1 (4)
C7—C8—C9—C9A	0.0 (4)	C101—C111—C112—C113	179.6 (2)
C8—C9—C9A—N10	178.5 (2)	C111—C112—C113—C114	0.9 (4)
C8—C9—C9A—C5A	−1.8 (3)	C112—C113—C114—C115	−1.1 (5)
C6—C5A—C9A—N10	−178.6 (2)	C113—C114—C115—C116	0.3 (5)
C5—C5A—C9A—N10	2.5 (3)	C114—C115—C116—C111	0.7 (5)
C6—C5A—C9A—C9	1.7 (3)	C112—C111—C116—C115	−0.9 (4)
C5—C5A—C9A—C9	−177.3 (2)	C101—C111—C116—C115	179.6 (3)
C9—C9A—N10—C10A	179.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1	0.86	2.03	2.876 (4)	165
N2—H22···Cl1	0.91	2.71	3.484 (2)	144
N2—H22···O4^ii	0.91	2.33	2.745 (3)	108
N3—H3···Cl1	1.00	2.09	3.068 (2)	163
O1—H11···O2	0.83 (4)	1.90 (4)	2.711 (7)	165 (3)
O1—H11···O2^i	0.83 (4)	2.04 (4)	2.847 (6)	165 (3)
O1—H12···Cl1^ii	0.81 (3)	2.43 (3)	3.233 (3)	172 (3)
C5—H5···Cl1^iii	0.95	2.66	3.570 (3)	161
C101—H10A···O2^i	0.99	2.29	3.112 (6)	139
C101—H10B···Cl1^iv	0.99	2.58	3.519 (3)	159

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