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The asymmetric unit of the title salt [systematic name: bis­(4-(2,3-dichloro­phen­yl)-1-{4-[(2-oxo-1,2,3,4-tetra­hydro­quinolin-7-yl)­oxy]but­yl}piperazin-1-ium) oxalate-oxalic acid (1/1)], 2C23H28Cl2N3O2+·C2O42-·C2H2O4, consists of one protonated aripiprazole unit (HArip+), half an oxalate dianion and half an oxalic acid mol­ecule, the latter two lying on inversion centres. The conformation of the HArip+ cation differs from that in other reported salts and resembles more the conformation of neutral Arip units in reported polymorphs and solvates. The inter­molecular inter­action linking HArip+ cations is also similar to those in reported Arip compounds crystallizing in the space group P\overline{1}, with head-to-head N-H...O hydrogen bonds generating centrosymmetric dimers, which are further organized into planar ribbons parallel to (01\overline{2}). The oxalate anions and oxalic acid mol­ecules form hydrogen-bonded chains running along [010], which `pierce' the planar ribbons, inter­acting with them through a number of stronger N-H...O and weaker C-H...O hydrogen bonds, forming a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113001133/yf3023sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113001133/yf3023Isup2.hkl
Contains datablock I

CCDC reference: 925775

Comment top

Aripiprazole (Arip) is an antipsychotic drug, perhaps the most characteristic representative of a modern family of atypical antipsychotics, with a different therapeutic activity to those of the classical antipsychotic drugs in standard use.

The drug crystallizes in a number of polymorphic forms, some of them described in the literature in a laconic patent form: the structural information therein is far from complete and the main source of structural information on aripiprazole consists of a paper by Tessler & Goldberg (2006), complemented by two excellent works by Braun et al. (2009a,b). In the first of the Braun et al. papers, a number of different polymorphic forms of the Arip molecule are reported, while in the second paper different solvates (ethanol, methanol, 1,2-dichloroethane, water etc.) are studied.

The situation with AripH+ salts is different and even if they have been mentioned in the patent literature, no structures had been reported until very recently when we presented the crystal structures of aripiprazole nitrate, hereafter (II) (Freire et al., 2012a), and aripiprazole perchlorate, hereafter (III) (Freire et al., 2012b). As discussed in these original reports, the protonated state of Arip results in interesting structural properties caused by N—H donor behaviour, which prompted us to proceed with the analysis of other AripH+ salts. We present here the results of our third successful attempt, viz. the structure of bis(aripiprazolium) oxalate–oxalic acid (1/1), 2(AripH+).Oxal2-.H2Oxal, (I) (H2Oxal is oxalic acid).

The asymmetric unit of (I) consists of one protonated aripiprazole unit (HArip+), half an oxalate dianion and half an oxalic acid molecule, the latter two lying on inversion centres (Fig. 1).

The AripH+ cation in (I) is similar to that in (II) and (III) with respect to bond lengths and angles. The conformation of the cation in (I) differs from that of the cation in (II) and (III), mainly in the central region, as shown in Table 1 and Fig. 2a. In fact, the shape of the cation in (I) resembles more those found in the polymorphs and solvates described by Braun et al. (2009a,b) (Fig. 2b).

As usual in this type of structure, the most interesting features are the noncovalent interactions defining the spatial arrangement. In (I), only hydrogen bonds are present (Table 2) and neither ππ nor C—H···π contacts are observed in spite of the presence of many aromatic rings.

The first entry in Table 2 corresponds to an intramolecular C—H···Cl contact, characteristic for the 4-(2,3-dichlorophenyl)piperazin-1-yl group in all reported Arip derivatives.

The next two entries in Table 2 define two well differentiated supramolecular substructures, viz. an anionic chain, comprising toxalate anions and oxalic acid molecules, and a strand of AripH+ cation dimers. The first of these is an (Oxal2-···H2Oxal)n chain parallel to [010] (Fig. 3a), generated by an O—H···O hydrogen bond. The one-dimensional structure intersects the (010) crystallographic plane at x = 1, z = 1/2 and embeds the inversion centres at y = 1/2 and y = 0,1. These chains are well separated from each other by one a, c cell vectors [clarify?].

The elemental building block of the cationic substructure is a head-to-head dimer. Cations in the dimer are linked by an N—H···O hydrogen bond (Table 2, third entry), which is characteristic of many Arip structures (see below). The elongated dimers thus formed [tail-to-tail C···C distance = 37.11 (2) Å] are oriented approximately along [021] and they form strands parallel to (012) by translation along the a axis (Fig. 3b).

The strands are linked into a three-dimensional structure through a number of O—H···O, N—H···O and C—H···O hydrogen bonds (Table 2, entries 4–8) mediated by the anionic chains. The main agent is the N—H···O bond (entry 4 in Table 2) and the way in which it acts is shown in detail in Fig. 4a: the three `objects' shown therein (the anionic chain and two AripH+ cations) appear parallel to the projection plane but at different heights, X being in the plane, while Y and Z lay below/above by approximately half of an a translation. Thus, the AripH+ strands are diagonally `pierced' by the anionic chains, which generates the three-dimensional network shown in Fig. 4b.

The N—H···O hydrogen bond between the amide groups of adjacent AripH+ cations (Table 2, third entry), characteristic of most of the reported Arip variants, is quite interesting. In all the Arip structures where this interaction exists, it produces one of two well defined supramolecular synthons, viz. either a C(4) catemer or a centrosymmetric diamide R22(8) ring (Bernstein et al., 1995). The former synthon (Figa. 5b and 5c) appears in structures crystallizing in space groups with translation symmetry elements (21 axis, glide planes) translating along a short cell dimension, and which serves for the `threading' of the chain. The second (more frequent) synthon generates centrosymmetric dimers (Fig. 5a) and usually occurs in Arip variants crystallizing in the space group P1.

In (II) and (III), the N—H···O hydrogen bond connecting adjacent groups gives rise to two only slightly different synthons, leading to almost identical C(4) substructures differing by the presence, in structure (II) [or its absence in structure (III)], of a secondary C—H···O interaction (Figs. 5b and 5c). The resulting catemers are related by quite different translation symmetry operations, viz. the Pbca a-glide plane in (II) and the P21/c 21-axis in (III). The title salt (I) crystallizes in the space group P1, with no translation elements and presents the usual R22(8) hydrogen-bonded ring (Fig. 5a).

Thus, all three known Arip salts, viz. (I), (II) and (III), adhere to this empirical rule linking symmetry and synthon character. However, the reasons for a given salt `choosing' one or the other are for the moment unclear, and the speculation regarding the possible pre-eminence of the patterns found in (II) and (III), made in some of our previous discussions (Freire et al., 2012b), now seems unsupported. Further work on the subject is in progress.

Related literature top

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

Experimental top

Aripiprazole (1.5 × 10 -4 mol, 67 mg) were dissolved in a boiling mixture of methanol (5 ml) and acetone (0.5 ml). When dissolution was considered complete, an excess of oxalic acid was added and the resulting solution left to cool slowly. Very good quality crystals of (I) in the form of colourless prisms appeared within a few hours and were used as obtained without further recrystallization.

Refinement top

All H atoms were found in a difference map and refined freely [methylene C—H = 0.93 (2)–0.96 (2) Å, aromatic C—H = 0.94 (2)–1.01 (3) Å and N—H = 0.87 (2)–0.95 (2) Å].

Computing details top

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 top
[Figure 1] Fig. 1. A displacement ellipsoid plot of (I), drawn at the 40% probability probability level, showing the asymmetric unit (in full ellipsoids and bonds). The Arip intramolecular hydrogen bond and the O—H···O interaction defining the anionic chain are shown with broken lines. [Symmetry codes: (iii) -x+1, -y+1, -z+1; (v) -x+1, -y+2, -z+1.]
[Figure 2] Fig. 2. A comparison of the stereodisposition of the present structure [(I), bold] with (a) reported Arip salts and (b) different solvates (A and B; Braun et al., 2009a) and polymorphs (C to H; Braun et al., 2009b). Compound codes: (II) is the nitrate salt, (III) is the perchlorate salt, A is an ethanol solvate (CSD refcode MELFEP01), and B, C, D/E, F/G and H are methanol solvates (CSD refcodes MELFOZ01 to MELFIT05).
[Figure 3] Fig. 3. The two different substructures in (I), showing (a) the anionic oxalate chain and (b) an assembly of Arip cationic dimers. [Symmetry code: (i) -x+1, -y-1, -z.]
[Figure 4] Fig. 4. Packing diagram of (I), viewed down a, showing (a) a detailed view of the N—H···O interaction linking both substructures, and (b) the relative orientation of both substructures. The anionic chains (in bold) run in the plane of the figure, while the strand of cationic dimers are shown in projection (one of them in a shadowed background).
[Figure 5] Fig. 5. The three different synthons found for the intermolecular Arip···Arip interactions in (a) (I), (b) (II) and (c) (III).
Bis(4-(2,3-dichlorophenyl)-1-{4-[(2-oxo-1,2,3,4-tetrahydroquinolin-7- yl)oxy]butyl}piperazin-1-ium); oxalate; oxalic acid top
Crystal data top
2C23H28Cl2N3O2+·C2O42·C2H2O4Z = 1
Mr = 1076.82F(000) = 564
Triclinic, P1Dx = 1.388 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9609 (7) ÅCell parameters from 3032 reflections
b = 11.2732 (9) Åθ = 3.8–29.1°
c = 15.8323 (11) ŵ = 0.30 mm1
α = 101.794 (6)°T = 294 K
β = 95.410 (7)°Plate, colourless
γ = 109.767 (8)°0.60 × 0.15 × 0.08 mm
V = 1288.2 (2) Å3
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
6079 independent reflections
Radiation source: fine-focus sealed tube3903 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
ω scans, thick slicesθmax = 29.2°, θmin = 3.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1010
Tmin = 0.95, Tmax = 0.98k = 1515
16111 measured reflectionsl = 021
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0742P)2 + 0.0853P]
where P = (Fo2 + 2Fc2)/3
6079 reflections(Δ/σ)max = 0.001
337 parametersΔρmax = 0.32 e Å3
3 restraintsΔρmin = 0.23 e Å3
Crystal data top
2C23H28Cl2N3O2+·C2O42·C2H2O4γ = 109.767 (8)°
Mr = 1076.82V = 1288.2 (2) Å3
Triclinic, P1Z = 1
a = 7.9609 (7) ÅMo Kα radiation
b = 11.2732 (9) ŵ = 0.30 mm1
c = 15.8323 (11) ÅT = 294 K
α = 101.794 (6)°0.60 × 0.15 × 0.08 mm
β = 95.410 (7)°
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
6079 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
3903 reflections with I > 2σ(I)
Tmin = 0.95, Tmax = 0.98Rint = 0.058
16111 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0573 restraints
wR(F2) = 0.160H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.32 e Å3
6079 reflectionsΔρmin = 0.23 e Å3
337 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl10.24705 (8)0.54881 (6)0.79059 (5)0.0672 (2)
Cl20.30443 (12)0.80669 (8)0.92693 (5)0.0900 (3)
O10.7228 (2)0.50763 (17)0.01832 (12)0.0692 (5)
O20.4837 (2)0.01643 (16)0.21786 (11)0.0608 (5)
N10.6067 (2)0.33562 (15)0.59188 (10)0.0342 (4)
H1N0.687 (2)0.3920 (18)0.5745 (14)0.052 (7)*
N20.5850 (2)0.51519 (16)0.74493 (11)0.0403 (4)
N30.6600 (3)0.35294 (19)0.07242 (13)0.0512 (5)
H3N0.5451 (16)0.390 (3)0.0532 (18)0.082 (9)*
C10.4556 (3)0.3858 (2)0.59495 (13)0.0406 (5)
H1B0.35600.32700.61460.049*
H1C0.41180.38960.53660.049*
C20.5193 (3)0.51949 (19)0.65630 (13)0.0408 (5)
H2A0.61610.57910.63560.049*
H2B0.42010.55110.65750.049*
C30.7385 (3)0.4717 (2)0.74336 (14)0.0485 (5)
H3A0.78360.47000.80200.058*
H3B0.83590.53200.72340.058*
C40.6791 (3)0.3365 (2)0.68233 (14)0.0470 (5)
H4A0.78150.30840.68110.056*
H4B0.58620.27560.70420.056*
C50.6137 (3)0.6317 (2)0.80828 (14)0.0435 (5)
C60.4646 (3)0.6587 (2)0.83523 (14)0.0478 (5)
C70.4896 (4)0.7729 (2)0.89606 (15)0.0570 (6)
C80.6596 (4)0.8628 (3)0.93203 (17)0.0690 (8)
H80.67520.93930.97310.083*
C90.8076 (4)0.8375 (3)0.90613 (18)0.0720 (8)
H90.92390.89780.92990.086*
C100.7856 (3)0.7247 (2)0.84598 (16)0.0586 (6)
H100.88750.70980.82990.070*
C110.5517 (3)0.20455 (18)0.52984 (13)0.0394 (5)
H11A0.44210.14610.54300.047*
H11B0.64640.16980.53820.047*
C120.5183 (3)0.20936 (19)0.43575 (13)0.0441 (5)
H12A0.61250.28460.42680.053*
H12B0.40290.21920.42290.053*
C130.5163 (3)0.0868 (2)0.37300 (14)0.0506 (6)
H13A0.62300.06890.39140.061*
H13B0.41010.01330.37480.061*
C140.5133 (4)0.1022 (2)0.28102 (15)0.0548 (6)
H14A0.41810.13400.26640.066*
H14B0.62790.16690.27790.066*
C150.6264 (3)0.0600 (2)0.20975 (15)0.0501 (5)
C160.5807 (3)0.1784 (2)0.14990 (14)0.0472 (5)
H160.46200.22210.12000.057*
C170.7105 (3)0.2324 (2)0.13404 (14)0.0456 (5)
C180.8883 (3)0.1695 (2)0.17826 (16)0.0543 (6)
C190.9316 (3)0.0503 (3)0.23817 (18)0.0665 (7)
H191.04970.00680.26880.080*
C200.8014 (4)0.0060 (3)0.25359 (17)0.0635 (7)
H200.83320.08680.29290.076*
C210.7780 (3)0.4032 (2)0.03771 (16)0.0545 (6)
C220.9744 (3)0.3217 (3)0.06867 (19)0.0696 (7)
H22A1.01360.26580.02960.083*
H22B1.04290.37870.06480.083*
C231.0195 (3)0.2375 (3)0.1617 (2)0.0714 (8)
H23A1.01630.29140.20250.086*
H23B1.14140.17310.17190.086*
C1A1.0303 (3)0.94180 (19)0.48760 (16)0.0439 (5)
O1A0.9369 (2)0.84251 (14)0.51231 (14)0.0642 (5)
H1A0.976 (4)0.779 (2)0.503 (2)0.099 (11)*
O2A1.1549 (3)0.94871 (19)0.45082 (18)0.0999 (8)
C1B0.9590 (3)0.55404 (18)0.50263 (14)0.0388 (5)
O1B1.0421 (2)0.64998 (13)0.47545 (12)0.0586 (5)
O2B0.8173 (2)0.53727 (14)0.53253 (11)0.0550 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0512 (4)0.0691 (4)0.0832 (5)0.0232 (3)0.0261 (3)0.0152 (3)
Cl20.1043 (6)0.0955 (6)0.0942 (6)0.0634 (5)0.0522 (5)0.0135 (4)
O10.0576 (11)0.0657 (11)0.0818 (12)0.0354 (9)0.0097 (9)0.0075 (9)
O20.0550 (10)0.0633 (10)0.0602 (10)0.0296 (9)0.0138 (8)0.0084 (8)
N10.0358 (9)0.0322 (9)0.0416 (9)0.0179 (8)0.0122 (7)0.0128 (7)
N20.0422 (10)0.0434 (10)0.0400 (9)0.0248 (8)0.0048 (8)0.0063 (7)
N30.0419 (11)0.0493 (11)0.0594 (12)0.0212 (10)0.0059 (10)0.0008 (9)
C10.0396 (11)0.0466 (12)0.0424 (11)0.0262 (10)0.0057 (9)0.0089 (9)
C20.0436 (12)0.0423 (11)0.0446 (11)0.0262 (10)0.0096 (9)0.0096 (9)
C30.0498 (13)0.0559 (14)0.0471 (12)0.0329 (11)0.0016 (10)0.0086 (10)
C40.0556 (13)0.0524 (13)0.0472 (12)0.0353 (11)0.0099 (10)0.0162 (10)
C50.0482 (13)0.0449 (12)0.0422 (11)0.0234 (11)0.0091 (10)0.0099 (9)
C60.0521 (13)0.0490 (13)0.0484 (12)0.0236 (11)0.0133 (10)0.0149 (10)
C70.0760 (18)0.0610 (15)0.0486 (13)0.0404 (14)0.0243 (13)0.0130 (12)
C80.092 (2)0.0558 (16)0.0534 (15)0.0339 (16)0.0063 (15)0.0082 (12)
C90.0643 (18)0.0616 (17)0.0717 (18)0.0186 (14)0.0011 (14)0.0088 (13)
C100.0527 (15)0.0593 (15)0.0577 (15)0.0241 (12)0.0035 (12)0.0012 (11)
C110.0404 (11)0.0310 (10)0.0507 (12)0.0155 (9)0.0151 (9)0.0113 (9)
C120.0519 (13)0.0368 (11)0.0470 (12)0.0198 (10)0.0138 (10)0.0096 (9)
C130.0605 (15)0.0380 (12)0.0556 (14)0.0187 (11)0.0217 (12)0.0100 (10)
C140.0646 (16)0.0531 (14)0.0513 (14)0.0269 (12)0.0189 (12)0.0100 (11)
C150.0442 (13)0.0518 (13)0.0489 (13)0.0145 (11)0.0135 (10)0.0038 (10)
C160.0410 (12)0.0523 (13)0.0453 (12)0.0172 (10)0.0107 (10)0.0044 (10)
C170.0478 (13)0.0458 (12)0.0409 (12)0.0177 (11)0.0064 (10)0.0058 (9)
C180.0421 (13)0.0564 (14)0.0598 (14)0.0154 (11)0.0073 (11)0.0100 (11)
C190.0422 (14)0.0678 (17)0.0682 (17)0.0075 (13)0.0001 (12)0.0023 (13)
C200.0578 (16)0.0569 (15)0.0650 (16)0.0162 (13)0.0170 (13)0.0027 (12)
C210.0509 (14)0.0568 (15)0.0621 (15)0.0294 (12)0.0118 (12)0.0109 (12)
C220.0489 (15)0.0772 (18)0.091 (2)0.0356 (14)0.0186 (14)0.0141 (15)
C230.0435 (14)0.0716 (17)0.098 (2)0.0260 (13)0.0051 (14)0.0135 (16)
C1A0.0302 (10)0.0331 (11)0.0743 (15)0.0154 (9)0.0122 (10)0.0186 (10)
O1A0.0530 (10)0.0318 (8)0.1244 (16)0.0217 (8)0.0391 (10)0.0339 (9)
O2A0.0898 (14)0.0666 (12)0.200 (3)0.0566 (11)0.0992 (16)0.0747 (14)
C1B0.0319 (10)0.0292 (10)0.0599 (13)0.0146 (9)0.0116 (10)0.0137 (9)
O1B0.0490 (9)0.0370 (8)0.1116 (14)0.0253 (7)0.0367 (9)0.0386 (9)
O2B0.0483 (9)0.0413 (8)0.0963 (13)0.0279 (7)0.0361 (9)0.0322 (8)
Geometric parameters (Å, º) top
Cl1—C61.730 (2)C11—C121.504 (3)
Cl2—C71.731 (3)C11—H11A0.9700
O1—C211.231 (3)C11—H11B0.9700
O2—C151.388 (3)C12—C131.522 (3)
O2—C141.428 (3)C12—H12A0.9700
N1—C41.489 (3)C12—H12B0.9700
N1—C111.493 (2)C13—C141.500 (3)
N1—C11.493 (2)C13—H13A0.9700
N1—H1N0.848 (9)C13—H13B0.9700
N2—C51.414 (3)C14—H14A0.9700
N2—C31.464 (2)C14—H14B0.9700
N2—C21.467 (2)C15—C201.372 (3)
N3—C211.354 (3)C15—C161.379 (3)
N3—C171.405 (3)C16—C171.383 (3)
N3—H3N0.862 (10)C16—H160.9300
C1—C21.504 (3)C17—C181.388 (3)
C1—H1B0.9700C18—C191.388 (3)
C1—H1C0.9700C18—C231.503 (3)
C2—H2A0.9700C19—C201.402 (4)
C2—H2B0.9700C19—H190.9300
C3—C41.518 (3)C20—H200.9300
C3—H3A0.9700C21—C221.493 (3)
C3—H3B0.9700C22—C231.516 (4)
C4—H4A0.9700C22—H22A0.9700
C4—H4B0.9700C22—H22B0.9700
C5—C101.395 (3)C23—H23A0.9700
C5—C61.404 (3)C23—H23B0.9700
C6—C71.381 (3)C1A—O2A1.186 (3)
C7—C81.369 (4)C1A—O1A1.277 (2)
C8—C91.381 (4)C1A—C1Ai1.536 (4)
C8—H80.9300O1A—H1A0.858 (10)
C9—C101.370 (3)C1B—O2B1.235 (2)
C9—H90.9300C1B—O1B1.246 (2)
C10—H100.9300C1B—C1Bii1.557 (4)
C15—O2—C14118.99 (18)H11A—C11—H11B107.9
C4—N1—C11112.11 (14)C11—C12—C13111.76 (16)
C4—N1—C1109.18 (15)C11—C12—H12A109.3
C11—N1—C1112.60 (15)C13—C12—H12A109.3
C4—N1—H1N108.5 (15)C11—C12—H12B109.3
C11—N1—H1N110.5 (16)C13—C12—H12B109.3
C1—N1—H1N103.5 (16)H12A—C12—H12B107.9
C5—N2—C3115.85 (16)C14—C13—C12110.97 (17)
C5—N2—C2112.34 (15)C14—C13—H13A109.4
C3—N2—C2109.44 (15)C12—C13—H13A109.4
C21—N3—C17124.7 (2)C14—C13—H13B109.4
C21—N3—H3N121 (2)C12—C13—H13B109.4
C17—N3—H3N114 (2)H13A—C13—H13B108.0
N1—C1—C2110.49 (16)O2—C14—C13112.98 (18)
N1—C1—H1B109.6O2—C14—H14A109.0
C2—C1—H1B109.6C13—C14—H14A109.0
N1—C1—H1C109.6O2—C14—H14B109.0
C2—C1—H1C109.6C13—C14—H14B109.0
H1B—C1—H1C108.1H14A—C14—H14B107.8
N2—C2—C1110.14 (15)C20—C15—C16120.3 (2)
N2—C2—H2A109.6C20—C15—O2125.5 (2)
C1—C2—H2A109.6C16—C15—O2114.16 (19)
N2—C2—H2B109.6C15—C16—C17120.3 (2)
C1—C2—H2B109.6C15—C16—H16119.8
H2A—C2—H2B108.1C17—C16—H16119.8
N2—C3—C4109.74 (17)C16—C17—C18121.0 (2)
N2—C3—H3A109.7C16—C17—N3119.0 (2)
C4—C3—H3A109.7C18—C17—N3120.0 (2)
N2—C3—H3B109.7C19—C18—C17117.8 (2)
C4—C3—H3B109.7C19—C18—C23124.0 (2)
H3A—C3—H3B108.2C17—C18—C23118.1 (2)
N1—C4—C3110.95 (16)C18—C19—C20121.5 (2)
N1—C4—H4A109.4C18—C19—H19119.2
C3—C4—H4A109.4C20—C19—H19119.2
N1—C4—H4B109.4C15—C20—C19119.0 (2)
C3—C4—H4B109.4C15—C20—H20120.5
H4A—C4—H4B108.0C19—C20—H20120.5
C10—C5—C6116.9 (2)O1—C21—N3120.7 (2)
C10—C5—N2123.28 (19)O1—C21—C22123.3 (2)
C6—C5—N2119.78 (19)N3—C21—C22115.9 (2)
C7—C6—C5120.7 (2)C21—C22—C23114.5 (2)
C7—C6—Cl1119.64 (19)C21—C22—H22A108.6
C5—C6—Cl1119.63 (17)C23—C22—H22A108.6
C8—C7—C6121.2 (2)C21—C22—H22B108.6
C8—C7—Cl2118.48 (19)C23—C22—H22B108.6
C6—C7—Cl2120.3 (2)H22A—C22—H22B107.6
C7—C8—C9118.6 (2)C18—C23—C22111.5 (2)
C7—C8—H8120.7C18—C23—H23A109.3
C9—C8—H8120.7C22—C23—H23A109.3
C10—C9—C8121.0 (3)C18—C23—H23B109.3
C10—C9—H9119.5C22—C23—H23B109.3
C8—C9—H9119.5H23A—C23—H23B108.0
C9—C10—C5121.5 (2)O2A—C1A—O1A125.28 (19)
C9—C10—H10119.3O2A—C1A—C1Ai121.3 (2)
C5—C10—H10119.3O1A—C1A—C1Ai113.4 (2)
N1—C11—C12112.24 (14)C1A—O1A—H1A114 (2)
N1—C11—H11A109.2O2B—C1B—O1B125.62 (17)
C12—C11—H11A109.2O2B—C1B—C1Bii117.6 (2)
N1—C11—H11B109.2O1B—C1B—C1Bii116.7 (2)
C12—C11—H11B109.2
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···Cl10.972.623.224 (2)120
O1A—H1A···O1B0.86 (1)1.71 (1)2.561 (2)174 (3)
N3—H3N···O1iii0.86 (1)2.01 (1)2.866 (3)173 (3)
N1—H1N···O2B0.85 (1)1.90 (1)2.730 (2)164 (2)
C1—H1C···O2Biv0.972.493.272 (2)137
C2—H2A···O2B0.972.483.197 (3)131
C11—H11B···O2Aii0.972.413.368 (3)171
C13—H13B···O2Av0.972.433.262 (3)143
Symmetry codes: (ii) x+2, y+1, z+1; (iii) x+1, y1, z; (iv) x+1, y+1, z+1; (v) x1, y1, z.

Experimental details

Crystal data
Chemical formula2C23H28Cl2N3O2+·C2O42·C2H2O4
Mr1076.82
Crystal system, space groupTriclinic, P1
Temperature (K)294
a, b, c (Å)7.9609 (7), 11.2732 (9), 15.8323 (11)
α, β, γ (°)101.794 (6), 95.410 (7), 109.767 (8)
V3)1288.2 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.60 × 0.15 × 0.08
Data collection
DiffractometerOxford Diffraction Gemini CCD S Ultra
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.95, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
16111, 6079, 3903
Rint0.058
(sin θ/λ)max1)0.687
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.160, 1.04
No. of reflections6079
No. of parameters337
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.23

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···Cl10.972.623.224 (2)120.3
O1A—H1A···O1B0.858 (10)1.705 (11)2.561 (2)174 (3)
N3—H3N···O1i0.862 (10)2.009 (11)2.866 (3)173 (3)
N1—H1N···O2B0.848 (9)1.903 (11)2.730 (2)164 (2)
C1—H1C···O2Bii0.972.493.272 (2)137.2
C2—H2A···O2B0.972.483.197 (3)130.8
C11—H11B···O2Aiii0.972.413.368 (3)171.2
C13—H13B···O2Aiv0.972.433.262 (3)143.0
Symmetry codes: (i) x+1, y1, z; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z+1; (iv) x1, y1, z.
Table 1. Comparison of selected torsion angles (°) for (I), (II) and (III) top
Torsion angle(I) (this work)(II) (Freire et al., 2012a)(III) (Freire et al., 2012b)
C2—N2—C5—C674.3 (2)161.37 (17)160.4 (2)
C2—N2—C5—C10-104.9 (2)-15.3 (2)-15.5 (4)
C3—N2—C5—C6-158.83 (19)-67.8 (2)-66.6 (3)
C3—N2—C5—C1021.9 (3)115.59 (17)117.6 (2)
C1—N1—C11—C1269.2 (2)152.38 (14)157.6 (2)
C4—N1—C11—C12-167.23 (19)-84.54 (17)-79.0 (3)
N1—C11—C12—C13163.53 (19)-169.64 (14)-172.7 (2)
C11—C12—C13—C14-170.8 (2)-69.0 (2)-71.0 (3)
C15—O2—C14—C13-77.1 (3)-172.12 (14)-167.47 (19)
 

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