2-(4-Chloro­phenyl)-1,3-di­cyano-6,7-di­hydro-4-imino-9,10-di­methoxy­benzo­[a]­quinolizine-water (2/5)

Crystals of the title compound, C₂₃H₁₇ClN₄O₂·2.5H₂O, contain channels filled with highly disordered water mol­ecules. The best structure refinement was obtained by removing the solvent contribution from the intensity data and refining against a solvent-free model. The central six-membered ring of the quinolizine mol­ecule has a slightly distorted screw-boat conformation.

S1. Comment

Fused isoquinoline derivatives are of considerable pharmaceutical and agricultural interest (Kleeman & Engel, 1982; Dannhardt & Sommer, 1985; Fülöp et al., 1990). Compounds with a fused five-membered ring at the original isoquinoline C═N bond can be prepared conveniently by 1,3-dipolar cycloadditions with 3,4-dihydroisoquinolines, (I) (Shawali, 1993). For example, [1,2,4]triazolo[3,4-a]isoquinolines of type (II) were obtained in high yield from cycloadditions with nitrile imines (cf. Caramella & Grünanger, 1984), which were generated in situ from the corresponding hydrazonoyl halides by elimination of HX on treatment with a base (Dannhardt & Sommer, 1985; Fülöp et al., 1990; Szabó et al., 1992; Abdelhadi et al., 1996; Elwan et al., 1996; Awad et al., 2002). On the other hand, pyrrolo[2,1-a]isoquinoline derivatives were obtained from 1-(cyanomethyl)-3,4-dihydroisoquinolines and hydrazonoyl halides in refluxing tetrahydrofuran in the presence of Et₃N (Awad et al., 2001). In none of the reactions was a product with a fused six-membered ring formed (cf. Fülöp et al., 1990; Elwan et al., 1996). However, isoquinolines with a fused six-membered ring at the original C═N bond are attractive targets (Fülöp et al., 1997; Fülöp & Bernáth, 1999; Martinek et al., 2000), and several methods for the preparation of benzo[a]quinolizines have been reported (Kametani, 1978; Bhattacharjya, 1983; Maiti & Pakrashi, 1984; Ninomiya et al., 1984; Akhrem & Chernov, 1988).

Recently, we developed a novel and efficient one-pot synthesis for polyfunctional benzo[a]quinolizine derivatives (Awad et al., 2002). The reaction of 1-(cyanomethyl)-6,7-diethoxy-3,4-dihydroisoquinoline [(I), R¹ = CH₂CN] with ethyl β-aryl-α-cyanocinnamates in the presence of piperidine led to 1,3-dicyano-6,7-dihydrobenzo[a]quinolizin-4-ones, (III), in high yield, whereas similar reactions with arylidenemalononitriles gave the corresponding 4-iminoquinolizines, (IV) (Awad et al., 2002). The structures of these products have been established on the basis of their spectroscopic data and elemental analyses. With the aim of proving the structure of the imino compounds of type (IV), the low-temperature crystal structure of the title compound, (IVa) (R = Me, R³ = CN, Ar = 4-ClC₆H₄), has been determined.

Compound (IVa) crystallizes as a hydrate with approximately 2.5 water molecules for every quinolizine molecule. There are two solvent cavities per unit cell so that each cavity contains five water molecules. The water molecules appear to be highly disordered and it was difficult to model their positions and distribution reliably. Therefore, the SQUEEZE function of the program PLATON (van der Sluis & Spek, 1990; Spek, 2001) was used to eliminate the contribution of the electron density in the solvent region from the intensity data and the solvent-free model was employed for the final refinement. Further details are given in the Experimental section. Due to the omission of the water molecules from the model, it was not possible to fully analyse the hydrogen-bonding interactions. Attempts to model the solvent molecules indicated that they are suitably positioned for a series of water–water hydrogen bonds to exist. The packing diagram (Fig. 2) shows that the solvent cavities are aligned into channels through the structure, so that infinite chains of hydrogen-bonded water molecules are conceivable. Fig. 2 also shows that the imine H atom is far from the solvent channels and is therefore unable to form a hydrogen bond with any of the water molecules. Furthermore, the N2—H2 bond is aligned in the plane of the quinolizine molecule and these molecules are stacked parallel to one another. In this position, the imine H atom does not partake in any hydrogen-bonding interactions.

The central six-membered ring of the quinolizine molecule has a slightly distorted screw-boat conformation (Fig. 1), with puckering parameters (Cremer & Pople, 1975) Q = 0.514 (3) Å, θ = 72.7 (2)° and ϕ = 263.3 (3)° for the atom sequence N1—C6—C7—C12—C13—C14. For an ideal screw-boat, the nearest ideal values are θ = 67.5° and ϕ = 270°. Atoms C12 and C13 are 0.409 (4) and 0.887 (4) Å, respectively, from the mean plane defined by atoms N1, C6, C7 and C14, and the r.m.s deviation of these latter four atoms from their plane is 0.035 Å. The r.m.s. deviation of the six atoms of the benzo ring from their mean plane is 0.011 Å, while the cyano-substituted six-membered ring is distorted very slightly from planarity, with an r.m.s. deviation of 0.031 Å; the maximum deviation from this plane is 0.0527 (16) Å for C6. The angle between the mean planes of the benzo and cyano-substituted rings is 29.71 (6)°, while the latter ring makes an angle of 43.25 (6)° with the p-chlorophenyl ring. The bond lengths around the cyano-substituted six-membered ring (Table 1) show that there is significant delocalization of the electron density from the C2═N2, C3═C4 and C5═C6 double bonds towards the N1—C2, N1—C6 and C4—C5 bonds. Similar delocalization involving the N1 atom is observed in the structure of the related compound 11,16,16-trimethyl-8-aza-D-homogona-1,3,5(10),9(11),13,17-hexaen-12-one (Lyakhov et al., 1997).

S2. Experimental

The title compound, (IVa), was obtained in 82% yield by reacting 1-(cyanomethyl)-3,4-dihydro-6,7-dimethoxyisoquinoline [(I), R = Me, R¹ = CH₂CN; 1.15 g, 5 mmol] with (4-chlorophenyl)methylidenemalononitrile (0.94 g, 5 mmol) and piperidine (0.5 ml) in refluxing acetonitrile (40 ml) for 3 h. After evaporation of the solvent in vacuo, the residue was triturated with methanol (10 ml) and crystallized from ethanol (m.p. 494–496 K). Suitable single crystals of (IVa) were obtained by recrystallization from diethyl ether.

S3. Refinement

There are two cavities of 178 ų per unit cell which appear to be filled by rather diffuse water molecules. The symmetry unique cavity is centred at (0.18, 1/4, -0.03). Satisfactory refinement results were obtained when two full-occupancy and one half-occupancy O atom from water molecules were defined in the asymmetric unit. This yields five water molecules per cavity. However, the anisotropic displacement parameters for these O atoms were very large. Several trials at defining additional sites or using lower site-occupation factors for these O atoms yielded inferior results. Therefore, it was assumed that the water molecules are highly disordered within their cavities, which results in smeared-out electron density. As an alternative strategy, the SQUEEZE function of PLATON (van der Sluis & Spek, 1990; Spek, 2001) was used to eliminate the contribution of the electron density in the solvent region from the intensity data. The use of this strategy and the subsequent solvent free model produced slightly better refinement results, and hence more precise geometric parameters, than the attempt to model the solvent atoms. Therefore, the solvent-free model and intensity data were used for the final results reported here. PLATON estimated that each cavity contains approximately 19 electrons, which is almost equivalent to two water molecules. This is contradictory to the results obtained from attempting to model the solvent molecules which suggested that five water molecules, or 50 e, are present in each cavity. However, the electron count produced by the SQUEEZE procedure is very dependent on the low-angle reflections and may be underestimated if some of these are absent from the data set. In the present structure determination, important low-angle reflections such as 100, 200, 020 and 110 are missing because they were obscured by the beam stop, so an underestimated electron count during the SQUEEZE procedure is not surprising.

The methoxy H atoms were constrained to an ideal geometry (C—H = 0.98 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—O bonds. The position of the imine H atom was refined freely along with an isotropic displacement parameter. All other H atoms were placed in geometrically idealized positions (C—H = 0.95–0.99 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).

Figures

	Fig. 1. View of the quinolizine molecule of (IVa) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size. The solvent molecules were not included in the model.
	Fig. 2. Crystal packing of (IVa) viewed down the c axis showing the channels available to the unmodelled water molecules and the stacking of the quinolizine molecules. H atoms bonded to C atoms have been omitted for clarity

2-(4-chlorophenyl)-1,3-dicyano-6,7-dihydro-4-imino- 9,10-dimethoxybenzo[a]quinolizine-water (2/5)

Crystal data

C23H17ClN4O2·2.5H2O	Dx = 1.410 Mg m^−3
Mr = 461.90	Melting point: 495 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 17.4665 (18) Å	Cell parameters from 25 reflections
b = 17.0031 (16) Å	θ = 17.8–19.4°
c = 7.347 (3) Å	µ = 0.22 mm^−1
β = 94.566 (18)°	T = 173 K
V = 2175.1 (9) Å^3	Prism, orange
Z = 4	0.38 × 0.25 × 0.20 mm
F(000) = 964

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.034
Radiation source: Rigaku RU200 rotating-anode generator	θmax = 27.5°, θmin = 2.6°
Graphite monochromator	h = −22→22
ω–2θ scans	k = −22→0
5556 measured reflections	l = 0→9
4982 independent reflections	3 standard reflections every 150 reflections
3141 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.051	Hydrogen site location: geom & difmap
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0795P)^2] where P = (Fo^2 + 2Fc^2)/3
4982 reflections	(Δ/σ)max = 0.001
277 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Solvent used: Crystal mount: glued on a glass fibre ω scan width: (1.42 + 0.35tanθ)° Fixed ω scan speed: 12°/min Up to 4 rescans when I < 10σ(I) and the counts were accumulated. Stationary background counts were recorded on each side of the reflection with a peak / background counting time ratio of 2:1.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 0.2480 (0.0307) x + 2.7903 (0.0178) y + 7.2323 (0.0032) z = 5.1606 (0.0197)

* -0.0452 (0.0014) N1 * 0.0449 (0.0014) C6 * -0.0217 (0.0007) C7 * 0.0220 (0.0007) C14 0.4092 (0.0043) C12 0.8874 (0.0043) C13

Rms deviation of fitted atoms = 0.0354

- 4.5148 (0.0165) x - 6.5318 (0.0156) y + 6.6429 (0.0041) z = 0.4786 (0.0172)

* -0.0032 (0.0016) C16 * 0.0076 (0.0016) C17 * -0.0048 (0.0016) C18 * -0.0023 (0.0017) C19 * 0.0067 (0.0017) C20 * -0.0040 (0.0017) C21

Rms deviation of fitted atoms = 0.0051

0.3067 (0.0154) x + 5.0309 (0.0154) y + 6.9847 (0.0035) z = 5.6372 (0.0115)

Angle to previous plane (with approximate e.s.d.) = 43.25 (0.06)

* 0.0397 (0.0015) N1 * 0.0000 (0.0015) C2 * -0.0256 (0.0016) C3 * 0.0120 (0.0016) C4 * 0.0267 (0.0016) C5 * -0.0527 (0.0016) C6

Rms deviation of fitted atoms = 0.0313

2.8252 (0.0161) x - 3.3333 (0.0161) y + 6.9890 (0.0035) z = 6.6518 (0.0082)

Angle to previous plane (with approximate e.s.d.) = 29.71 (0.06)

* 0.0172 (0.0016) C7 * -0.0124 (0.0016) C8 * -0.0025 (0.0016) C9 * 0.0128 (0.0016) C10 * -0.0080 (0.0016) C11 * -0.0071 (0.0016) C12

Rms deviation of fitted atoms = 0.0111

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl	1.14227 (3)	−0.07018 (4)	0.77710 (9)	0.03323 (18)
O1	0.54027 (9)	−0.16805 (9)	0.6463 (3)	0.0282 (4)
O2	0.41839 (9)	−0.09609 (10)	0.7392 (2)	0.0282 (4)
N1	0.68661 (10)	0.15474 (11)	0.6712 (3)	0.0217 (4)
N2	0.73743 (13)	0.27135 (12)	0.5728 (3)	0.0287 (5)
H2	0.7780 (17)	0.2927 (18)	0.553 (4)	0.033 (8)*
N3	0.93636 (13)	0.24227 (13)	0.5427 (4)	0.0367 (6)
N4	0.77546 (13)	−0.08956 (13)	0.9225 (4)	0.0387 (6)
C2	0.75026 (13)	0.20086 (13)	0.6294 (3)	0.0221 (5)
C3	0.82417 (13)	0.16009 (13)	0.6519 (3)	0.0206 (5)
C4	0.83223 (12)	0.08375 (13)	0.7119 (3)	0.0201 (5)
C5	0.76401 (12)	0.04181 (13)	0.7472 (3)	0.0204 (5)
C6	0.69150 (13)	0.07681 (13)	0.7138 (3)	0.0207 (5)
C7	0.61938 (12)	0.03240 (13)	0.7193 (3)	0.0200 (5)
C8	0.61645 (12)	−0.04838 (13)	0.6777 (3)	0.0214 (5)
H8	0.6611	−0.0746	0.6433	0.026*
C9	0.54894 (13)	−0.08934 (13)	0.6869 (3)	0.0230 (5)
C10	0.48218 (12)	−0.05017 (14)	0.7347 (3)	0.0223 (5)
C11	0.48465 (13)	0.02980 (14)	0.7689 (3)	0.0230 (5)
H11	0.4394	0.0564	0.7978	0.028*
C12	0.55264 (13)	0.07156 (14)	0.7615 (3)	0.0230 (5)
C13	0.55935 (14)	0.15881 (14)	0.7942 (4)	0.0273 (5)
H131	0.5806	0.1687	0.9211	0.033*
H132	0.5078	0.1833	0.7778	0.033*
C14	0.61121 (13)	0.19514 (13)	0.6623 (4)	0.0242 (5)
H141	0.5864	0.1915	0.5366	0.029*
H142	0.6190	0.2515	0.6921	0.029*
C15	0.88814 (14)	0.20438 (14)	0.5941 (3)	0.0255 (5)
C16	0.90869 (12)	0.04449 (13)	0.7329 (3)	0.0208 (5)
C17	0.97199 (13)	0.08429 (13)	0.8167 (3)	0.0230 (5)
H17	0.9657	0.1355	0.8652	0.028*
C18	1.04439 (13)	0.04907 (14)	0.8294 (3)	0.0242 (5)
H18	1.0878	0.0762	0.8841	0.029*
C19	1.05174 (13)	−0.02608 (14)	0.7609 (3)	0.0244 (5)
C20	0.98963 (13)	−0.06739 (14)	0.6794 (3)	0.0262 (5)
H20	0.9959	−0.1192	0.6347	0.031*
C21	0.91809 (13)	−0.03133 (13)	0.6646 (3)	0.0227 (5)
H21	0.8751	−0.0585	0.6075	0.027*
C22	0.77011 (12)	−0.03215 (14)	0.8407 (3)	0.0254 (5)
C23	0.60612 (15)	−0.20684 (15)	0.5826 (4)	0.0382 (7)
H231	0.6237	−0.1779	0.4784	0.057*
H232	0.5922	−0.2606	0.5449	0.057*
H233	0.6474	−0.2085	0.6811	0.057*
C24	0.34736 (13)	−0.05812 (15)	0.7727 (4)	0.0304 (6)
H241	0.3528	−0.0321	0.8920	0.046*
H242	0.3063	−0.0975	0.7718	0.046*
H243	0.3346	−0.0190	0.6772	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0241 (3)	0.0388 (4)	0.0367 (4)	0.0113 (3)	0.0021 (2)	−0.0003 (3)
O1	0.0235 (8)	0.0182 (8)	0.0435 (11)	−0.0026 (7)	0.0067 (7)	−0.0021 (8)
O2	0.0203 (8)	0.0260 (9)	0.0391 (10)	−0.0021 (7)	0.0076 (7)	0.0000 (8)
N1	0.0201 (9)	0.0194 (10)	0.0250 (10)	0.0011 (7)	−0.0005 (8)	0.0005 (8)
N2	0.0281 (11)	0.0200 (10)	0.0378 (13)	−0.0009 (8)	0.0020 (9)	0.0032 (9)
N3	0.0321 (12)	0.0277 (12)	0.0513 (15)	−0.0021 (9)	0.0107 (11)	0.0072 (10)
N4	0.0309 (12)	0.0318 (12)	0.0517 (16)	−0.0042 (9)	−0.0066 (11)	0.0164 (11)
C2	0.0258 (11)	0.0183 (11)	0.0221 (12)	0.0004 (9)	0.0019 (9)	−0.0009 (9)
C3	0.0227 (11)	0.0181 (11)	0.0210 (11)	−0.0019 (9)	0.0020 (9)	−0.0007 (9)
C4	0.0205 (11)	0.0216 (11)	0.0184 (11)	0.0007 (9)	0.0026 (8)	−0.0020 (9)
C5	0.0200 (11)	0.0178 (10)	0.0232 (12)	0.0001 (8)	0.0004 (9)	0.0003 (9)
C6	0.0239 (11)	0.0197 (11)	0.0185 (11)	−0.0005 (9)	0.0013 (9)	−0.0009 (9)
C7	0.0192 (10)	0.0194 (11)	0.0211 (11)	−0.0002 (8)	−0.0005 (8)	0.0012 (9)
C8	0.0174 (10)	0.0222 (11)	0.0238 (12)	0.0020 (8)	−0.0025 (9)	0.0016 (9)
C9	0.0250 (12)	0.0180 (11)	0.0255 (12)	−0.0006 (9)	−0.0011 (10)	0.0001 (9)
C10	0.0185 (11)	0.0267 (12)	0.0215 (11)	−0.0025 (9)	0.0002 (9)	0.0034 (9)
C11	0.0195 (11)	0.0261 (12)	0.0233 (12)	0.0028 (9)	0.0019 (9)	−0.0014 (9)
C12	0.0233 (11)	0.0238 (12)	0.0215 (11)	0.0010 (9)	−0.0013 (9)	0.0000 (9)
C13	0.0258 (12)	0.0235 (12)	0.0327 (14)	0.0038 (10)	0.0026 (10)	−0.0046 (10)
C14	0.0231 (11)	0.0146 (10)	0.0343 (13)	0.0035 (9)	−0.0021 (10)	0.0003 (10)
C15	0.0286 (12)	0.0193 (11)	0.0287 (13)	0.0034 (9)	0.0030 (10)	0.0019 (10)
C16	0.0187 (10)	0.0208 (11)	0.0231 (11)	−0.0001 (8)	0.0021 (9)	0.0015 (9)
C17	0.0246 (11)	0.0214 (12)	0.0232 (12)	0.0012 (9)	0.0024 (9)	0.0002 (9)
C18	0.0203 (11)	0.0269 (12)	0.0255 (12)	−0.0016 (9)	0.0026 (9)	0.0006 (10)
C19	0.0208 (11)	0.0307 (13)	0.0219 (12)	0.0053 (10)	0.0038 (9)	0.0043 (10)
C20	0.0289 (12)	0.0222 (11)	0.0281 (13)	0.0030 (10)	0.0058 (10)	0.0006 (10)
C21	0.0199 (11)	0.0215 (11)	0.0265 (12)	−0.0007 (9)	0.0010 (9)	−0.0007 (9)
C22	0.0171 (11)	0.0270 (13)	0.0318 (13)	−0.0024 (9)	−0.0001 (9)	0.0022 (11)
C23	0.0338 (14)	0.0203 (12)	0.063 (2)	−0.0026 (11)	0.0173 (13)	−0.0068 (12)
C24	0.0204 (11)	0.0332 (14)	0.0382 (15)	0.0009 (10)	0.0068 (10)	0.0029 (11)

Geometric parameters (Å, º)

Cl—C19	1.746 (2)	C10—C11	1.383 (3)
O1—C9	1.377 (3)	C11—C12	1.388 (3)
O1—C23	1.436 (3)	C11—H11	0.95
O2—C10	1.363 (3)	C12—C13	1.506 (3)
O2—C24	1.437 (3)	C13—C14	1.510 (3)
N1—C6	1.363 (3)	C13—H131	0.99
N1—C2	1.414 (3)	C13—H132	0.99
N1—C14	1.482 (3)	C14—H141	0.99
N2—C2	1.283 (3)	C14—H142	0.99
N2—H2	0.82 (3)	C16—C17	1.397 (3)
N3—C15	1.148 (3)	C16—C21	1.398 (3)
N4—C22	1.146 (3)	C17—C18	1.396 (3)
C2—C3	1.463 (3)	C17—H17	0.95
C3—C4	1.374 (3)	C18—C19	1.383 (3)
C3—C15	1.439 (3)	C18—H18	0.95
C4—C5	1.430 (3)	C19—C20	1.388 (3)
C4—C16	1.490 (3)	C20—C21	1.388 (3)
C5—C6	1.403 (3)	C20—H20	0.95
C5—C22	1.433 (3)	C21—H21	0.95
C6—C7	1.472 (3)	C23—H231	0.98
C7—C12	1.399 (3)	C23—H232	0.98
C7—C8	1.407 (3)	C23—H233	0.98
C8—C9	1.376 (3)	C24—H241	0.98
C8—H8	0.95	C24—H242	0.98
C9—C10	1.411 (3)	C24—H243	0.98
C9—O1—C23	116.10 (18)	C12—C13—H132	109.6
C10—O2—C24	117.73 (19)	C14—C13—H132	109.6
C6—N1—C2	123.59 (19)	H131—C13—H132	108.2
C6—N1—C14	119.99 (18)	N1—C14—C13	111.01 (19)
C2—N1—C14	116.40 (18)	N1—C14—H141	109.4
C2—N2—H2	110 (2)	C13—C14—H141	109.4
N2—C2—N1	117.9 (2)	N1—C14—H142	109.4
N2—C2—C3	127.5 (2)	C13—C14—H142	109.4
N1—C2—C3	114.50 (19)	H141—C14—H142	108.0
C4—C3—C15	121.8 (2)	N3—C15—C3	176.3 (3)
C4—C3—C2	123.4 (2)	C17—C16—C21	119.6 (2)
C15—C3—C2	114.68 (19)	C17—C16—C4	120.0 (2)
C3—C4—C5	117.6 (2)	C21—C16—C4	120.4 (2)
C3—C4—C16	121.6 (2)	C18—C17—C16	120.2 (2)
C5—C4—C16	120.7 (2)	C18—C17—H17	119.9
C6—C5—C4	120.7 (2)	C16—C17—H17	119.9
C6—C5—C22	119.2 (2)	C19—C18—C17	118.8 (2)
C4—C5—C22	119.56 (19)	C19—C18—H18	120.6
N1—C6—C5	119.5 (2)	C17—C18—H18	120.6
N1—C6—C7	117.84 (19)	C18—C19—C20	122.2 (2)
C5—C6—C7	122.7 (2)	C18—C19—Cl	118.80 (18)
C12—C7—C8	119.8 (2)	C20—C19—Cl	119.01 (19)
C12—C7—C6	119.5 (2)	C19—C20—C21	118.6 (2)
C8—C7—C6	120.8 (2)	C19—C20—H20	120.7
C9—C8—C7	120.0 (2)	C21—C20—H20	120.7
C9—C8—H8	120.0	C20—C21—C16	120.7 (2)
C7—C8—H8	120.0	C20—C21—H21	119.7
C8—C9—O1	124.1 (2)	C16—C21—H21	119.7
C8—C9—C10	120.1 (2)	N4—C22—C5	177.0 (3)
O1—C9—C10	115.72 (19)	O1—C23—H231	109.5
O2—C10—C11	124.9 (2)	O1—C23—H232	109.5
O2—C10—C9	115.4 (2)	H231—C23—H232	109.5
C11—C10—C9	119.7 (2)	O1—C23—H233	109.5
C10—C11—C12	120.7 (2)	H231—C23—H233	109.5
C10—C11—H11	119.7	H232—C23—H233	109.5
C12—C11—H11	119.7	O2—C24—H241	109.5
C11—C12—C7	119.7 (2)	O2—C24—H242	109.5
C11—C12—C13	123.6 (2)	H241—C24—H242	109.5
C7—C12—C13	116.7 (2)	O2—C24—H243	109.5
C12—C13—C14	110.1 (2)	H241—C24—H243	109.5
C12—C13—H131	109.6	H242—C24—H243	109.5
C14—C13—H131	109.6
C6—N1—C2—N2	172.8 (2)	C24—O2—C10—C11	3.4 (3)
C14—N1—C2—N2	−5.7 (3)	C24—O2—C10—C9	−175.1 (2)
C6—N1—C2—C3	−5.4 (3)	C8—C9—C10—O2	179.8 (2)
C14—N1—C2—C3	176.06 (19)	O1—C9—C10—O2	1.7 (3)
N2—C2—C3—C4	−179.2 (2)	C8—C9—C10—C11	1.2 (3)
N1—C2—C3—C4	−1.2 (3)	O1—C9—C10—C11	−176.8 (2)
N2—C2—C3—C15	−3.3 (4)	O2—C10—C11—C12	179.8 (2)
N1—C2—C3—C15	174.7 (2)	C9—C10—C11—C12	−1.8 (3)
C15—C3—C4—C5	−173.3 (2)	C10—C11—C12—C7	−0.1 (3)
C2—C3—C4—C5	2.4 (3)	C10—C11—C12—C13	179.0 (2)
C15—C3—C4—C16	4.4 (3)	C8—C7—C12—C11	2.5 (3)
C2—C3—C4—C16	−180.0 (2)	C6—C7—C12—C11	−179.2 (2)
C3—C4—C5—C6	2.7 (3)	C8—C7—C12—C13	−176.7 (2)
C16—C4—C5—C6	−175.0 (2)	C6—C7—C12—C13	1.6 (3)
C3—C4—C5—C22	−168.7 (2)	C11—C12—C13—C14	−140.4 (2)
C16—C4—C5—C22	13.6 (3)	C7—C12—C13—C14	38.7 (3)
C2—N1—C6—C5	10.5 (3)	C6—N1—C14—C13	30.8 (3)
C14—N1—C6—C5	−171.0 (2)	C2—N1—C14—C13	−150.6 (2)
C2—N1—C6—C7	−168.4 (2)	C12—C13—C14—N1	−54.0 (3)
C14—N1—C6—C7	10.2 (3)	C3—C4—C16—C17	45.0 (3)
C4—C5—C6—N1	−8.9 (3)	C5—C4—C16—C17	−137.4 (2)
C22—C5—C6—N1	162.5 (2)	C3—C4—C16—C21	−133.2 (2)
C4—C5—C6—C7	169.8 (2)	C5—C4—C16—C21	44.4 (3)
C22—C5—C6—C7	−18.8 (3)	C21—C16—C17—C18	1.1 (3)
N1—C6—C7—C12	−28.0 (3)	C4—C16—C17—C18	−177.2 (2)
C5—C6—C7—C12	153.2 (2)	C16—C17—C18—C19	−1.2 (3)
N1—C6—C7—C8	150.3 (2)	C17—C18—C19—C20	0.3 (4)
C5—C6—C7—C8	−28.5 (3)	C17—C18—C19—Cl	−179.90 (18)
C12—C7—C8—C9	−3.0 (3)	C18—C19—C20—C21	0.8 (4)
C6—C7—C8—C9	178.7 (2)	Cl—C19—C20—C21	−179.02 (18)
C7—C8—C9—O1	179.0 (2)	C19—C20—C21—C16	−1.0 (4)
C7—C8—C9—C10	1.2 (3)	C17—C16—C21—C20	0.0 (4)
C23—O1—C9—C8	−3.0 (3)	C4—C16—C21—C20	178.3 (2)
C23—O1—C9—C10	174.9 (2)