Aripiprazole salts. II. Aripiprazole perchlorate

The mol­ecular structure of aripiprazole perchlorate (systematic name: 4-(2,3-dichloro­phenyl)-1-{4-[(2-oxo-1,2,3,4-tetra­hydro­quinolin-7-yl)­oxy]­butyl}­piperazin-1-ium perchlor­ate), C₂₃H₂₈Cl₂N₃O₂⁺·ClO₄^-, does not differ substantially from the recently published structure of aripiprazole nitrate [Freire, Polla & Baggio (2012). Acta Cryst. C68, o170-o173]. Both compounds have almost identical bond distances, bond angles and torsion angles. The two different counter-ions occupy equivalent places in the two structures, giving rise to very similar first-order `packing motifs'. However, these elemental arrangements inter­act with each other in different ways in the two structures, leading to two-dimensional arrays with quite different organizations.

S1. Comment

Aripiprazole (Arip, 7-{4-[4-(2,3-dichlorophenyl)-1-piperazinyl]butoxy}-3,4-dihydroquinolin-2(1H)-one) is an antipsychotic drug, perhaps the most relevant representative of a modern family of atypical antipsychotics (Travis et al., 2005), with a different therapeutic activity to those of the classical antipsychotic drugs in standard use.

The drug crystallizes in a number of polymorphic and solvatomorphic varieties, described in a large number of patents, but the structural information provided is far from complete, and when their X-ray powder diffraction (XRPD) diagrams are reported they usually fulfill the role of fingerprint identifiers. The main source of structural information on Arip compounds consists of a paper by Tessler & Goldberg (2006), complemented by two excellent works by Braun et al. (2009a,b). In the first of these latter works, Braun and coworkers report a number of different forms of the Arip molecule in its free form, included in the Cambridge Structural Database (CSD; Allen, 2002) with refcodes MELFIT01–05, while in the second of these latter works they present different solvates, viz. MELFEP01 (ethanol solvate), MELFOZ01 (methanol solvate), MELFUF01 (monohydrate) and MOXDAF01 (1,2-dichloroethane solvate)

With Arip salts, the situation is slightly different, and even if some of them have been described in the patent literature, no structure of an Arip salt had been described until recently, namely aripiprazole nitrate, (II) (Freire et al., 2012). The protonated state of the ligand confers interesting properties on the structure, which prompted us to analyse other AripH⁺ salts. We report herein a second AripH⁺ salt, namely aripiprazole perchlorate or HArip⁺.ClO₄^-, (I).

Compound (I) (Fig. 1) consists of an AripH⁺ cation and a ClO₄^- counterion, completing the structure and providing charge balance. The whole AripH⁺–ClO₄^- molecular assembly in (I) is very similar to that in the nitrate counterpart, (II), in terms of bond lengths, bond angles and torsion angles, and reference should be made to the detailed description in Freire et al. (2012). As a measure of these similarities, the least-squares fit of both moieties (counterions excluded) leads to a mean deviation of 0.23° (Fig. 2), and even the (relatively free) counterions, not involved in the fitting, sit in almost exactly the same place, their baricentres lying only 0.52 Å apart.

If the noncovalent interactions defining the spatial arrangement (hydrogen bonds shown in Table 1 and π bonds given in Table 2) are compared with those in the nitrate isologue, (II), it can be seen that all main interactions are present, in particular the hydrogen bonds involving the N—H donors (Table 1, entries 2 and 3). These hydrogen bonds give rise to similar `first-order' packing motifs [point (a) below], which in turn act as building blocks of fairly different structures [point (b) below].

The first entry in Table 1 corresponds to an intramolecular C—H···Cl interaction characteristic for the dichlorophenylpiperazin-1-yl group in all reported Arip variants, being in (I), as it was in (II), rather unexceptional.

(a) The second entry, the strong hydrogen bond between the amide groups of adjacent Arip molecules, is characteristic of most of the reported Arip variants, though leading to different supramolecular synthons, a catemer [graph-set C(4)] or a diamide R₂²(8) dimer [this was discussed in detail in Freire et al. (2012); for graph-set nomenclature, see Bernstein et al. (1995)].

In the cases of (I) and (II), this hydrogen bond leads to almost identical catemers (zones labelled A in Fig. 3), running along the shortest axis in each case [b in (I) and a in (II)]. There is, however, an important structural difference between the two cases, in that the translation symmetry operations relating concatenated moieties in these catemers are the Pbca a-glide plane in (II) but the P2₁/c 2₁ axis in (II), while having very similar translation `steps' of 4.2322 (2) and 4.1552 (3) Å, respectively.

Contrasting with the previous interaction, common to almost all Arip compounds, the second N—H···O bond is instead unique to (I) and (II), as some of the main participants (the nitrate/perchlorate counterions as acceptors, and the extra H1 atom as donor) are present only in these salts. Even though the molecular strips are common constructive blocks in most Arip structures, in the present case this second interaction strengthens their mutual link and enhances their internal cohesion, forming a rather different entity (Fig. 3). In fact, zones B in Fig. 3 show the contribution of both counterions to the stability of the elementary packing units therein depicted. Both include the second strong N—H···O synthon (Table 1, third entry), identical in both structures, and a second, weak, C—H···O hydrogen bond which serves as an effective link between second neighbours in the catemer. However, these are characteristic of each structure, involving C11—H11 in (II) and C14—H14 in (I), a difference which is probably to do with the geometric differences between the anions (planar nitrate versus tetrahedral perchlorate). In spite of these differences, the `first-order' packing motifs shown in Fig. 3 are very similar.

(b) Finally, these motifs further interact laterally, via π–π bonds (shaded C in Fig. 4 [Added text OK?]), but here also there are significant crystallographic differences. In the case of (II), the process is achieved through an (x, y, z + 1) translation of the whole group or, in other words, the interdigitation of aromatic rings in neighbouring cells, adjacent along c (Fig. 4b). These π–π interactions result in the formation of a continuous thread along [100], and the two-dimensional structure generated by juxtaposition of the broad [100] bands ends up being an array parallel to (010).

In contrast, the π–π linkage process in (I) is noticeably more complicated, generated by the P2₁/c c glide (which provides an [001/2] translation) in combination with a further lateral [2,0,0] shift of the resulting image (Fig. 4a and Table 2). These two translational effects combine to give an alternating π–π approach (Fig. 4a) and the consequence is a two-dimensional structure parallel to (401). In summary, the two-dimensional repeat pattern consists of two molecular ribbons parallel to [100] in (II) but of four ribbons parallel to [010] in (I).

There are also differences in the planarity of these two two-dimensional arrays. When viewed in projection, that in (II) appears noticeably undulating (Fig. 5b; largest deviation from the mean plane ~5 Å), consistent with the fact that the linkage operator at A is a plane (shown as a dashed line) and which allows for the `mirror-like' aspect shown therein by the two-dimensional trace. Instead, the 2₁ axis in (I) forces a linear disposition and thus favours a more planar set-up, with a maximum deviation from the mean plane of ~2 Å (Fig. 5b). Regarding packing efficiency, the corrugated scheme in nitrate salt (II) seems to be more efficient than the more planar scheme in perchlorate salt (I), where a significant increase of 6% in molecular weight leads to a mere increase of 2% in density.

The remaining interactions presented in Tables 1 and 2 are noticeably weaker and provide interplanar interactions.

The results presented herein suggest that there are spatial arrangements in AripH⁺ salts (viz. those shown in Fig. 3) which behave as fairly stable motifs. They do not seem to depend on the symmetry or counterion, and can act as well defined building blocks for more complex packing set-ups. This presumed stability should be confirmed through further systematic work on aripiprazole salts, a research line on which we are presently engaged.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Braun et al. (2009a, 2009b); Freire et al. (2012); Tessler & Goldberg (2006); Travis et al. (2005).

S2. Experimental

Aripiprazole (67 mg, 0.15 mmol) was dissolved in a boiling mixture of methanol (5 ml) and acetone (0.5 ml). When dissolution was complete, an excess of concentrated HClO₄ was added dropwise and the resulting solution left to cool slowly. Excellent crystals of AripH⁺.ClO₄^-, (I), in the form of colourless prisms, appeared in a few hours and were used as obtained without further recrystallization.

S3. Refinement

All H atoms were found in a difference map. H atoms attached to N atoms were further refined, giving N—H = 0.81 (3)–0.83 (3) Å and U_iso(H) = 0.037 (7)–0.040 (7) Å^-2. H atoms attached to C atoms were idealized and allowed to ride, with methylene C—H = 0.97 Å and aromatic C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Ring centroids are labelled. Displacement ellipsoids are drawn at the 40% probability level. The dashed line represents the intramolecular C—H···Cl interaction.
	Fig. 2. A comparison of the stereodisposition of (I) (solid lines) and (II) (dashed lines). Note the slight shift between the counterions.
	Fig. 3. Packing diagrams for (a) (I), projected on (401), and (b) (II), projected on (010). Dashed lines indicate hydrogen bonds. The shaded regions A and B correspond to different hydrogen-bonding regimes, as discussed in the text. [Symmetry codes: (i) -x + 2, y + 1/2, -z + 3/2; (ii) x, y - 1, z.]
	Fig. 4. The same views as in Fig. 3, but showing the lateral interactions (dashed lines) between the structures shown therein. The shaded region C is discussed in the text.
	Fig. 5. Packing diagrams for (a) (I) and (b) (II), at right angles to those shown in Fig. 4. The circled areas indicate the symmetry operations giving rise to the packing linkage.

4-(2,3-dichlorophenyl)-1-{4-[(2-oxo-1,2,3,4-tetrahydroquinolin-7- yl)oxy]butyl}piperazin-1-ium perchlorate

Crystal data

C23H28Cl2N3O2^+·ClO4^−	F(000) = 1144
Mr = 548.83	Dx = 1.478 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2995 reflections
a = 14.7348 (5) Å	θ = 3.9–29.0°
b = 8.3103 (3) Å	µ = 0.42 mm^−1
c = 20.1590 (7) Å	T = 291 K
β = 92.557 (3)°	Block, colourless
V = 2466.03 (16) Å^3	0.24 × 0.16 × 0.14 mm
Z = 4

Data collection

Oxford Gemini S Ultra CCD area-detector diffractometer	5590 independent reflections
Radiation source: fine-focus sealed tube	4186 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans, thick slices	θmax = 29.1°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −19→20
Tmin = 0.92, Tmax = 0.94	k = −7→11
11131 measured reflections	l = −22→25

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 1.7253P] where P = (Fo^2 + 2Fc^2)/3
5590 reflections	(Δ/σ)max = 0.001
324 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.02909 (4)	0.08717 (9)	0.89146 (3)	0.04968 (18)
Cl2	−0.16811 (4)	0.13370 (10)	0.93423 (3)	0.0563 (2)
Cl3	0.38233 (4)	0.69866 (7)	0.91332 (3)	0.04517 (17)
O13	0.3472 (2)	0.6025 (3)	0.86097 (13)	0.0967 (9)
O23	0.46611 (18)	0.7626 (4)	0.89993 (18)	0.1181 (11)
O33	0.3917 (2)	0.5974 (3)	0.97086 (12)	0.0894 (8)
O43	0.32302 (17)	0.8266 (3)	0.92687 (15)	0.0938 (9)
O1	1.01383 (12)	−0.5597 (2)	0.75797 (10)	0.0536 (5)
O2	0.68183 (10)	0.0066 (2)	0.82291 (9)	0.0458 (4)
N1	0.36016 (12)	0.2606 (3)	0.94683 (10)	0.0330 (4)
H1	0.3721 (17)	0.358 (3)	0.9514 (12)	0.040 (7)*
N2	0.17244 (12)	0.2462 (3)	0.97990 (8)	0.0352 (4)
N3	0.90059 (13)	−0.3799 (3)	0.76372 (10)	0.0358 (4)
H3	0.9347 (17)	−0.304 (3)	0.7602 (12)	0.037 (7)*
C1	0.33039 (15)	0.1946 (3)	1.01135 (11)	0.0424 (6)
H1A	0.3776	0.2129	1.0456	0.051*
H1B	0.3212	0.0794	1.0072	0.051*
C2	0.24340 (15)	0.2731 (4)	1.03132 (11)	0.0422 (6)
H2A	0.2250	0.2281	1.0730	0.051*
H2B	0.2530	0.3877	1.0375	0.051*
C3	0.19891 (15)	0.3209 (3)	0.91782 (11)	0.0356 (5)
H3A	0.2091	0.4351	0.9247	0.043*
H3B	0.1505	0.3081	0.8840	0.043*
C4	0.28490 (14)	0.2424 (3)	0.89508 (11)	0.0345 (5)
H4A	0.2738	0.1290	0.8866	0.041*
H4B	0.3025	0.2918	0.8540	0.041*
C5	0.08229 (14)	0.2672 (3)	0.99918 (10)	0.0332 (5)
C6	0.00997 (15)	0.1985 (3)	0.96143 (10)	0.0330 (5)
C7	−0.07835 (15)	0.2136 (3)	0.98209 (12)	0.0372 (5)
C8	−0.09673 (16)	0.2897 (3)	1.04034 (13)	0.0441 (6)
H8	−0.1560	0.2962	1.0542	0.053*
C9	−0.02622 (17)	0.3560 (3)	1.07791 (12)	0.0453 (6)
H9	−0.0379	0.4080	1.1175	0.054*
C10	0.06150 (16)	0.3463 (3)	1.05748 (11)	0.0404 (5)
H10	0.1081	0.3938	1.0833	0.049*
C11	0.44789 (15)	0.1838 (3)	0.92796 (12)	0.0399 (5)
H11A	0.4346	0.0800	0.9078	0.048*
H11B	0.4856	0.1654	0.9679	0.048*
C12	0.50047 (16)	0.2839 (3)	0.88035 (13)	0.0418 (6)
H12A	0.5076	0.3922	0.8978	0.050*
H12B	0.4666	0.2905	0.8381	0.050*
C13	0.59399 (16)	0.2117 (3)	0.86974 (13)	0.0434 (6)
H13A	0.6304	0.2901	0.8471	0.052*
H13B	0.6239	0.1904	0.9127	0.052*
C14	0.59062 (15)	0.0591 (3)	0.83015 (13)	0.0443 (6)
H14A	0.5565	−0.0223	0.8529	0.053*
H14B	0.5611	0.0780	0.7869	0.053*
C15	0.69595 (15)	−0.1456 (3)	0.79990 (10)	0.0341 (5)
C16	0.78666 (14)	−0.1845 (3)	0.79061 (10)	0.0340 (5)
H16	0.8319	−0.1073	0.7971	0.041*
C17	0.80845 (14)	−0.3391 (3)	0.77164 (10)	0.0311 (5)
C18	0.74258 (15)	−0.4573 (3)	0.75980 (11)	0.0375 (5)
C19	0.65361 (16)	−0.4142 (3)	0.76851 (13)	0.0439 (6)
H19	0.6083	−0.4906	0.7608	0.053*
C20	0.62917 (15)	−0.2609 (3)	0.78842 (12)	0.0414 (6)
H20	0.5685	−0.2358	0.7940	0.050*
C21	0.93253 (16)	−0.5322 (3)	0.76193 (11)	0.0405 (6)
C22	0.86391 (19)	−0.6623 (3)	0.76817 (16)	0.0566 (7)
H22A	0.8567	−0.6847	0.8149	0.068*
H22B	0.8861	−0.7595	0.7477	0.068*
C23	0.77308 (18)	−0.6196 (3)	0.73637 (15)	0.0537 (7)
H23A	0.7288	−0.7004	0.7475	0.064*
H23B	0.7772	−0.6182	0.6885	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0516 (4)	0.0570 (4)	0.0408 (3)	−0.0040 (3)	0.0065 (3)	−0.0114 (3)
Cl2	0.0366 (3)	0.0708 (5)	0.0609 (4)	−0.0130 (3)	−0.0031 (3)	0.0070 (4)
Cl3	0.0382 (3)	0.0315 (3)	0.0663 (4)	−0.0014 (2)	0.0074 (3)	−0.0003 (3)
O13	0.144 (2)	0.0543 (15)	0.0873 (17)	−0.0009 (16)	−0.0430 (17)	−0.0039 (13)
O23	0.0626 (16)	0.111 (2)	0.185 (3)	−0.0255 (16)	0.0523 (18)	−0.004 (2)
O33	0.155 (3)	0.0460 (13)	0.0661 (14)	−0.0001 (15)	−0.0085 (15)	0.0009 (11)
O43	0.0808 (17)	0.0538 (14)	0.149 (2)	0.0249 (13)	0.0306 (16)	−0.0053 (16)
O1	0.0368 (9)	0.0496 (11)	0.0757 (12)	0.0114 (9)	0.0172 (9)	0.0007 (10)
O2	0.0256 (8)	0.0440 (10)	0.0686 (11)	0.0043 (7)	0.0093 (7)	−0.0153 (9)
N1	0.0271 (9)	0.0292 (10)	0.0433 (10)	0.0018 (8)	0.0074 (8)	−0.0007 (9)
N2	0.0267 (9)	0.0488 (12)	0.0304 (9)	0.0015 (9)	0.0054 (7)	0.0028 (9)
N3	0.0268 (9)	0.0351 (11)	0.0462 (11)	0.0012 (9)	0.0108 (8)	−0.0001 (9)
C1	0.0308 (11)	0.0577 (16)	0.0387 (12)	0.0016 (11)	0.0020 (9)	0.0084 (12)
C2	0.0310 (11)	0.0626 (17)	0.0331 (11)	0.0009 (12)	0.0037 (9)	−0.0011 (11)
C3	0.0299 (11)	0.0399 (13)	0.0375 (11)	0.0030 (10)	0.0063 (9)	0.0042 (10)
C4	0.0326 (11)	0.0366 (12)	0.0347 (11)	0.0013 (10)	0.0068 (9)	−0.0025 (10)
C5	0.0315 (11)	0.0365 (12)	0.0319 (10)	0.0028 (10)	0.0064 (8)	0.0038 (10)
C6	0.0345 (11)	0.0330 (12)	0.0318 (10)	0.0019 (10)	0.0049 (8)	0.0029 (9)
C7	0.0311 (11)	0.0360 (13)	0.0445 (12)	−0.0013 (10)	0.0018 (9)	0.0087 (11)
C8	0.0321 (12)	0.0470 (15)	0.0544 (14)	0.0055 (11)	0.0140 (10)	0.0056 (12)
C9	0.0440 (14)	0.0503 (16)	0.0428 (13)	0.0074 (12)	0.0146 (11)	−0.0062 (12)
C10	0.0347 (12)	0.0464 (14)	0.0404 (12)	0.0018 (11)	0.0046 (9)	−0.0057 (11)
C11	0.0291 (11)	0.0358 (13)	0.0556 (14)	0.0077 (10)	0.0106 (10)	0.0024 (11)
C12	0.0337 (12)	0.0366 (13)	0.0562 (14)	0.0076 (10)	0.0137 (10)	0.0004 (12)
C13	0.0305 (11)	0.0415 (14)	0.0590 (15)	0.0038 (11)	0.0117 (10)	−0.0014 (12)
C14	0.0264 (11)	0.0472 (15)	0.0598 (15)	0.0072 (11)	0.0084 (10)	−0.0037 (13)
C15	0.0303 (11)	0.0384 (13)	0.0339 (11)	0.0049 (10)	0.0054 (9)	−0.0009 (10)
C16	0.0254 (10)	0.0389 (13)	0.0379 (11)	−0.0004 (9)	0.0056 (8)	−0.0023 (10)
C17	0.0282 (10)	0.0372 (12)	0.0283 (10)	0.0024 (9)	0.0053 (8)	0.0025 (9)
C18	0.0331 (11)	0.0375 (13)	0.0422 (12)	−0.0006 (10)	0.0036 (9)	0.0006 (11)
C19	0.0305 (12)	0.0423 (14)	0.0588 (15)	−0.0057 (11)	0.0015 (11)	−0.0004 (12)
C20	0.0239 (10)	0.0479 (15)	0.0526 (14)	0.0015 (10)	0.0055 (10)	0.0004 (12)
C21	0.0394 (13)	0.0424 (14)	0.0406 (12)	0.0070 (11)	0.0120 (10)	0.0030 (11)
C22	0.0492 (15)	0.0390 (15)	0.083 (2)	0.0050 (13)	0.0167 (14)	0.0047 (15)
C23	0.0455 (15)	0.0393 (15)	0.0766 (19)	−0.0028 (12)	0.0063 (13)	−0.0060 (14)

Geometric parameters (Å, º)

Cl1—C6	1.720 (2)	C8—C9	1.374 (4)
Cl2—C7	1.734 (2)	C8—H8	0.9300
Cl3—O23	1.382 (2)	C9—C10	1.376 (3)
Cl3—O13	1.404 (2)	C9—H9	0.9300
Cl3—O43	1.411 (2)	C10—H10	0.9300
Cl3—O33	1.435 (2)	C11—C12	1.510 (3)
O1—C21	1.226 (3)	C11—H11A	0.9700
O2—C15	1.367 (3)	C11—H11B	0.9700
O2—C14	1.427 (3)	C12—C13	1.527 (3)
N1—C1	1.495 (3)	C12—H12A	0.9700
N1—C4	1.496 (3)	C12—H12B	0.9700
N1—C11	1.506 (3)	C13—C14	1.498 (4)
N1—H1	0.83 (3)	C13—H13A	0.9700
N2—C5	1.411 (3)	C13—H13B	0.9700
N2—C2	1.456 (3)	C14—H14A	0.9700
N2—C3	1.465 (3)	C14—H14B	0.9700
N3—C21	1.351 (3)	C15—C20	1.385 (3)
N3—C17	1.415 (3)	C15—C16	1.396 (3)
N3—H3	0.81 (3)	C16—C17	1.382 (3)
C1—C2	1.509 (3)	C16—H16	0.9300
C1—H1A	0.9700	C17—C18	1.394 (3)
C1—H1B	0.9700	C18—C19	1.378 (3)
C2—H2A	0.9700	C18—C23	1.505 (4)
C2—H2B	0.9700	C19—C20	1.387 (4)
C3—C4	1.514 (3)	C19—H19	0.9300
C3—H3A	0.9700	C20—H20	0.9300
C3—H3B	0.9700	C21—C22	1.489 (4)
C4—H4A	0.9700	C22—C23	1.500 (4)
C4—H4B	0.9700	C22—H22A	0.9700
C5—C10	1.393 (3)	C22—H22B	0.9700
C5—C6	1.403 (3)	C23—H23A	0.9700
C6—C7	1.390 (3)	C23—H23B	0.9700
C7—C8	1.371 (3)
O23—Cl3—O13	112.0 (2)	C9—C10—H10	119.2
O23—Cl3—O43	108.34 (18)	C5—C10—H10	119.2
O13—Cl3—O43	111.34 (18)	N1—C11—C12	113.44 (19)
O23—Cl3—O33	109.2 (2)	N1—C11—H11A	108.9
O13—Cl3—O33	107.03 (15)	C12—C11—H11A	108.9
O43—Cl3—O33	108.90 (17)	N1—C11—H11B	108.9
C15—O2—C14	118.45 (19)	C12—C11—H11B	108.9
C1—N1—C4	109.41 (17)	H11A—C11—H11B	107.7
C1—N1—C11	110.65 (18)	C11—C12—C13	111.4 (2)
C4—N1—C11	113.51 (18)	C11—C12—H12A	109.4
C1—N1—H1	109.2 (18)	C13—C12—H12A	109.4
C4—N1—H1	108.8 (18)	C11—C12—H12B	109.4
C11—N1—H1	105.1 (18)	C13—C12—H12B	109.4
C5—N2—C2	116.09 (17)	H12A—C12—H12B	108.0
C5—N2—C3	118.20 (18)	C14—C13—C12	113.5 (2)
C2—N2—C3	109.44 (18)	C14—C13—H13A	108.9
C21—N3—C17	124.4 (2)	C12—C13—H13A	108.9
C21—N3—H3	120.5 (18)	C14—C13—H13B	108.9
C17—N3—H3	115.1 (19)	C12—C13—H13B	108.9
N1—C1—C2	111.0 (2)	H13A—C13—H13B	107.7
N1—C1—H1A	109.4	O2—C14—C13	107.73 (19)
C2—C1—H1A	109.4	O2—C14—H14A	110.2
N1—C1—H1B	109.4	C13—C14—H14A	110.2
C2—C1—H1B	109.4	O2—C14—H14B	110.2
H1A—C1—H1B	108.0	C13—C14—H14B	110.2
N2—C2—C1	109.59 (19)	H14A—C14—H14B	108.5
N2—C2—H2A	109.8	O2—C15—C20	125.4 (2)
C1—C2—H2A	109.8	O2—C15—C16	114.9 (2)
N2—C2—H2B	109.8	C20—C15—C16	119.7 (2)
C1—C2—H2B	109.8	C17—C16—C15	119.2 (2)
H2A—C2—H2B	108.2	C17—C16—H16	120.4
N2—C3—C4	109.51 (18)	C15—C16—H16	120.4
N2—C3—H3A	109.8	C16—C17—C18	122.3 (2)
C4—C3—H3A	109.8	C16—C17—N3	119.3 (2)
N2—C3—H3B	109.8	C18—C17—N3	118.4 (2)
C4—C3—H3B	109.8	C19—C18—C17	117.0 (2)
H3A—C3—H3B	108.2	C19—C18—C23	124.9 (2)
N1—C4—C3	110.45 (18)	C17—C18—C23	118.0 (2)
N1—C4—H4A	109.6	C18—C19—C20	122.4 (2)
C3—C4—H4A	109.6	C18—C19—H19	118.8
N1—C4—H4B	109.6	C20—C19—H19	118.8
C3—C4—H4B	109.6	C15—C20—C19	119.4 (2)
H4A—C4—H4B	108.1	C15—C20—H20	120.3
C10—C5—C6	117.4 (2)	C19—C20—H20	120.3
C10—C5—N2	122.4 (2)	O1—C21—N3	121.3 (2)
C6—C5—N2	120.13 (19)	O1—C21—C22	122.7 (2)
C7—C6—C5	120.0 (2)	N3—C21—C22	116.0 (2)
C7—C6—Cl1	118.95 (18)	C21—C22—C23	112.9 (2)
C5—C6—Cl1	121.02 (16)	C21—C22—H22A	109.0
C8—C7—C6	121.4 (2)	C23—C22—H22A	109.0
C8—C7—Cl2	118.56 (18)	C21—C22—H22B	109.0
C6—C7—Cl2	119.99 (18)	C23—C22—H22B	109.0
C7—C8—C9	118.9 (2)	H22A—C22—H22B	107.8
C7—C8—H8	120.5	C22—C23—C18	110.5 (2)
C9—C8—H8	120.5	C22—C23—H23A	109.5
C8—C9—C10	120.6 (2)	C18—C23—H23A	109.5
C8—C9—H9	119.7	C22—C23—H23B	109.5
C10—C9—H9	119.7	C18—C23—H23B	109.5
C9—C10—C5	121.7 (2)	H23A—C23—H23B	108.1

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C15–C20 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···Cl1	0.97	2.57	3.193 (2)	122
N3—H3···O1^i	0.81 (3)	2.20 (3)	2.985 (3)	162 (2)
N1—H1···O33	0.83 (3)	2.05 (3)	2.875 (3)	174 (3)
C14—H14A···O23^ii	0.97	2.45	3.413 (4)	175
C1—H1A···O23^iii	0.97	2.51	3.441 (4)	160
C4—H4B···Cg2^iii	0.97	2.81	3.541 (2)	133

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