Download citation
Download citation
link to html
For the hydrated proton-transfer compound 6-chloro-9-[(4-diethyl­ammonio-2-methyl­butyl)­amino]-2-methoxy­acridinium 3-carboxyl­ato-4-hydroxy­benzene­sulfonate dihydrate, C23H32ClN3O2+·C7H4O6S2-·2H2O, (I), the conformational features, specifically those of the extended side chain at the 9-position of the acridine parent, have been compared with those of quinacrinium dichloride dihydrate (the drug atabrine or mepacrine). Racemic compound (I) has a three-dimensional hydrogen-bonded framework structure similar to atabrine but also involves the water mol­ecules and both the carboxyl­ate and sulfonate groups of the anion in structure extension. The comparable conformational features found in this uncommon derivative of quinacrine indicate that (I) has potential as a possible pharmaceutical substitute for atabrine.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108020313/dn3093sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108020313/dn3093Isup2.hkl
Contains datablock I

CCDC reference: 700023

Comment top

Quinacrine [N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] was synthesized in 1931 by Bayer [Is a reference or patent available?] and, as the dihydrochloride dehydrate (atabrine, mepacrine), introduced as a drug which was the first alternative to quinine for the treatment of malaria and other parasite-borne diseases (e.g. Chaga's disease, giardiasis). Its use in the treatment of malaria has largely been superceded by chloroquine, which has fewer of the undesirable adverse physiological side effects of quinacrine, e.g. aplastic anaemia and hyperpigmentation (Wilson et al., 1991). However, its more recent experimental and sometimes controversial uses include the possible treatment of Creutzfeldt–Jacob disease, where it has been found to inhibit the accumulation of pathogenic prion protein in cultured neuroblastoma cells (Doh-Ura et al., 2000), and for non-surgical female sterilization (Zipper et al., 1980). The crystal structure of the Trypanosoma cruzi trypanothione reducatase (TR) complex with quinacrine (Jacobi et al., 1996) showed that specific sites on the acridine ring system (the hetero N, C2 methoxy O and C6 chloro substituent groups), as well as the two amino groups of the C9 substituent side chain, are fixed at active sites of the TR enzyme.

The crystal structure of racemic atabrine (quinacrine dihydrochloride dihydrate; Courseille et al., 1973) showed the molecule to be protonated at the hetero N atom of the acridine ring and at the tertiary terminal N atom of the C9 side chain. In addition, the acridine ring systems showed interactive ππ stacking effects. Considering the difficulty in obtaining good crystals of atabrine, we have prepared the salts of this base with the strong aromatic organic acids 3,5-dinitrosalicylic acid (DNSA) and 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) for the purpose of crystallographic examination. This approach has been used previously by us and other research groups with reasonable success since these acids, particularly when used in their anionic forms, are recognized as useful synthons for molecular assembly achieved through hydrogen-bonding interactions involving potentially all interactive substituent functional groups. The method allows the structures of difficult-to-crystallize Lewis base compounds, such as many pharmaceuticals, to be determined.

The crystal structures have been reported of the 1:1 salts of 5-SSA with theophylline (a monohydrate; Madarasz et al., 2002), trimethoprim (a dihydrate; Raj et al., 2003), and pyrimethamine (Hemamalini et al., 2005) and brucine (Smith, Wermuth, Healy & White, 2006) (both anhydrates). With DNSA, the structures of 1:1 anhydrous salts with both brucine (Smith, Wermuth, Healy & White, 2006) and strychnine (Smith et al., 2005) are also known. With the 5-SSA anions formed in the reaction of the acid with Lewis bases, all of the substituent groups provide hydrogen-bonding donor or acceptor atoms with potential for both primary and secondary structure extension. In some examples, particularly those salts with polycyclic heteroaromatic amines (Smith, Wermuth & White, 2004), the structures feature anion–anion or anion–cation ππ interactions. We obtained good crystals of the atabrine salt with 5-SSA from an aqueous ethanol solution but not with the DNSA salt prepared under similar conditions.

The crystal structure of the 5-SSA salt reported here is that of racemic quinacrinium 5-sulfosalicylate dihydrate, C23H32ClN3O2+.C7H4O6S2-.2H2O, (I). The quinacrine molecule is protonated at both the acridine N (N10) and the terminal tertiary diethylamino N atom (N141), while generating a 5-SSA dianion by deprotonation of both the sulfonic acid and carboxylic acid groups. Dianionic 5-SSA anions are not common among the known structures in the crystallographic literature but some are known, e.g. the salts with guanidine (Smith, Wermuth & Healy, 2004), benzylamine (Smith, Wermuth & Healy, 2006), 2-aminopyridine (Yang & Qu, 2006) and piperazine (Su & Li, 2007).

In the asymmetric unit of (I) (Fig. 1), the dication has primary hydrogen-bonding interactions involving the protonated tertiary amine N atom (N141) and one of the water molecules (O1W), as well as the secondary amine N atom (N91) and the second water molecule (O2W), while the H atom of the acridinium N atom is involved in secondary interactions with a carboxyl group of the 5-SSA dianion [cyclic three-centre asymmetric, graph set R21(4) (Etter et al., 1990)] (Table 1). Other secondary inter-species hydrogen bonds generate a three-dimensional framework structure (Fig. 2), which is also found in the structure of quinacrinium chloride dihydrate (Courseille et al., 1973). However, in that structure, the acridinium H atom has a primary interaction with one of the chloride anions, which is in turn associated with the solvent water molecules in structure extension. Conformationally the two structures are similar, with the C91 side chain adopting a comparable perpendicular attitude with respect to the acridine ring (Table 2), which is also the case in the structures of other C9 extended-chain-substituted 6-chloro-2-methoxyacridines, e.g. in the anti-tumour acridine analogues (Berman & Glusker, 1972; Carrell, 1972; Glusker et al., 1972). The only major difference between (I) and the dichloride is found, not unexpectedly, within the terminal diethylamino group. Also in (I) there are no cation–cation or cation–anion aromatic ring ππ interactions, which are present in the structure of the hydrochloride [minimum centroid separation of the inversion-related six-membered rings N10–C13 and C5–C15 = 4.1834 (13) Å].

With the 5-SSA anion species for (I), similar structural and conformational features to those previously observed (Smith, Wermuth & White, 2004) are found. The usual intramolecular Ophenolic—H···Ocarboxyl hydrogen bond is found [series range 2.598 (3)–2.625 (2) Å], giving essentially coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2—C1—C7—O71 = -175.0 (2)°]. In addition, the common aromatic C6A—H6A···O52Asulfonate interaction [2.879 (2) Å] is present. It may be concluded that the chemically stable and structurally similar 5-sulfosalicylate salt of quinacrine, (I), could be considered a possible alternative to atabrine as a drug.

Experimental top

The title compound was synthesized by heating together 1 mmol quantities of quinacrium dichloride dihydrate (atabrine or mepacrine) (O'Neil, 2001) and 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid = 5-SSA) in 50% ethanol–water (50 ml) under reflux for 10 min. After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solution gave yellow blocks of (I) (m.p. 523 K).

Refinement top

H atoms potentially involved in hydrogen-bonding interactions (aminium, carboxylic, phenolic and water) were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinement at calculated positions as riding atoms, with C—H = 0.93 (aromatic) or C—H = 0.96 or 0.97 Å (aliphatic), and with Uiso(I) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular conformation and atom-numbering scheme for the quinacrine dication, the 5-sulfosalicylate dianion and the two solvent water molecules in (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary size. Inter-species hydrogen-bonding associations are shown as dashed lines.
[Figure 2] Fig. 2. Hydrogen-bonding extensions in the structure of (I), shown in a partial view down the approximate c axial direction. [Symmetry codes: (v) x - 1/2, -y + 3/2, z + 1/2; for other symmetry codes, see Table 1.]
6-chloro-9-[(4-diethylammonio-2-methylbutyl)amino]-2-methoxyacridinium 3-carboxylato-4-hydroxybenzenesulfonate dihydrate top
Crystal data top
C23H32ClN3O2+·C7H4O6S2·2H2OF(000) = 1384
Mr = 654.17Dx = 1.356 Mg m3
Monoclinic, P21/nMelting point: 523 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 10.1753 (3) ÅCell parameters from 9373 reflections
b = 30.8461 (7) Åθ = 2.9–28.9°
c = 10.3671 (2) ŵ = 0.24 mm1
β = 99.966 (3)°T = 297 K
V = 3204.81 (14) Å3Block, yellow
Z = 40.20 × 0.20 × 0.15 mm
Data collection top
Oxford Diffraction Gemini-S Ultra CCD detector
diffractometer
5455 independent reflections
Radiation source: Enhance (Mo) X-ray tube3568 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scansθmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1111
Tmin = 0.906, Tmax = 0.960k = 3636
29865 measured reflectionsl = 1212
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0552P)2]
where P = (Fo2 + 2Fc2)/3
5455 reflections(Δ/σ)max = 0.002
433 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C23H32ClN3O2+·C7H4O6S2·2H2OV = 3204.81 (14) Å3
Mr = 654.17Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.1753 (3) ŵ = 0.24 mm1
b = 30.8461 (7) ÅT = 297 K
c = 10.3671 (2) Å0.20 × 0.20 × 0.15 mm
β = 99.966 (3)°
Data collection top
Oxford Diffraction Gemini-S Ultra CCD detector
diffractometer
5455 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3568 reflections with I > 2σ(I)
Tmin = 0.906, Tmax = 0.960Rint = 0.049
29865 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.26 e Å3
5455 reflectionsΔρmin = 0.26 e Å3
433 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å2) top
xyzUiso*/Ueq
Cl60.73514 (8)1.07667 (2)1.02838 (7)0.0788 (3)
O21.37199 (16)0.93866 (5)0.46659 (16)0.0572 (6)
N101.1183 (2)1.02589 (6)0.81378 (18)0.0449 (7)
N910.91323 (18)0.92482 (5)0.61055 (17)0.0361 (6)
N1411.10064 (19)0.78100 (6)0.88969 (17)0.0405 (6)
C11.1711 (2)0.94843 (6)0.5586 (2)0.0406 (8)
C21.3003 (2)0.95817 (7)0.5492 (2)0.0442 (8)
C31.3695 (2)0.99067 (7)0.6276 (2)0.0507 (8)
C41.3091 (2)1.01273 (7)0.7137 (2)0.0488 (9)
C50.9350 (3)1.04771 (6)0.9128 (2)0.0465 (9)
C60.8050 (3)1.04374 (7)0.9227 (2)0.0487 (9)
C70.7218 (3)1.01360 (7)0.8475 (2)0.0516 (9)
C80.7741 (2)0.98673 (6)0.7649 (2)0.0445 (8)
C90.9721 (2)0.95988 (6)0.66931 (18)0.0328 (7)
C111.1046 (2)0.97092 (6)0.64782 (18)0.0345 (7)
C121.1765 (2)1.00352 (6)0.7248 (2)0.0393 (8)
C130.9900 (2)1.02031 (6)0.82663 (19)0.0400 (8)
C140.9107 (2)0.98788 (6)0.75396 (19)0.0356 (7)
C211.3163 (3)0.90073 (8)0.3983 (3)0.0663 (10)
C1010.8054 (2)0.89728 (6)0.64293 (19)0.0368 (7)
C1020.6813 (2)0.90126 (7)0.5384 (2)0.0498 (8)
C1110.8531 (2)0.85013 (6)0.65477 (19)0.0372 (7)
C1210.9708 (2)0.84169 (6)0.7633 (2)0.0415 (8)
C1311.0014 (2)0.79360 (6)0.77116 (19)0.0395 (7)
C1511.0970 (3)0.73304 (7)0.9145 (2)0.0619 (10)
C1611.1456 (4)0.70609 (8)0.8109 (3)0.0925 (13)
C1711.2371 (2)0.79845 (8)0.8845 (2)0.0501 (8)
C1811.3376 (3)0.78939 (10)1.0066 (2)0.0729 (10)
S5A0.68492 (6)0.71943 (2)0.92440 (5)0.0413 (2)
O2A0.53028 (18)0.90192 (5)0.81392 (17)0.0557 (6)
O51A0.73433 (17)0.70207 (5)0.81288 (15)0.0579 (6)
O52A0.55973 (19)0.69969 (5)0.94051 (19)0.0735 (7)
O53A0.7816 (2)0.71921 (5)1.04214 (15)0.0764 (7)
O71A0.82953 (17)0.87392 (5)1.12651 (16)0.0625 (6)
O72A0.69527 (18)0.92267 (5)1.01919 (16)0.0664 (7)
C1A0.6696 (2)0.85020 (6)0.94699 (18)0.0336 (7)
C2A0.5708 (2)0.86055 (6)0.83976 (19)0.0386 (7)
C3A0.5132 (2)0.82784 (7)0.75500 (19)0.0411 (8)
C4A0.5496 (2)0.78537 (6)0.77900 (18)0.0362 (7)
C5A0.6446 (2)0.77423 (6)0.88733 (17)0.0318 (7)
C6A0.7042 (2)0.80682 (6)0.96911 (18)0.0342 (7)
C7A0.7363 (2)0.88417 (7)1.0383 (2)0.0446 (8)
O1W1.0461 (3)0.82390 (8)1.10118 (19)0.0795 (9)
O2W0.9675 (2)0.88264 (6)0.37879 (17)0.0581 (7)
H11.126300.926800.505900.0490*
H31.457200.997100.620400.0610*
H41.355701.034100.766000.0590*
H50.988001.068300.962400.0560*
H70.631801.011900.853800.0620*
H80.718300.967000.714300.0530*
H101.170 (3)1.0455 (8)0.863 (3)0.072 (8)*
H910.947 (2)0.9120 (6)0.546 (2)0.047 (6)*
H1010.783800.906600.727200.0440*
H1020.611600.883400.561600.0750*
H1030.701400.891900.455700.0750*
H1040.652400.930900.532000.0750*
H1110.779300.832000.669400.0450*
H1120.877500.841400.572100.0450*
H1211.048200.857600.745900.0500*
H1220.950000.851700.846200.0500*
H1310.919200.777800.771900.0470*
H1321.035700.785000.693300.0470*
H1411.076 (2)0.7959 (7)0.957 (2)0.064 (8)*
H1511.006100.724700.919300.0740*
H1521.151700.726800.998700.0740*
H1611.132800.675900.827800.1110*
H1621.238800.711600.812700.1110*
H1631.096300.713600.726400.1110*
H1711.230900.829600.870900.0600*
H1721.268800.785800.809900.0600*
H1811.298000.795101.082400.0880*
H1821.364800.759601.006900.0880*
H1831.414000.807701.008000.0880*
H2111.299300.879300.460400.0800*
H2121.378000.889300.346600.0800*
H2131.234200.908200.342000.0800*
H2A0.574 (3)0.9157 (8)0.888 (3)0.086 (10)*
H3A0.449900.834900.682100.0490*
H4A0.510400.763800.722300.0430*
H6A0.769000.799501.040600.0410*
H11W0.985 (3)0.8378 (9)1.107 (3)0.081 (12)*
H12W1.101 (3)0.8184 (10)1.168 (3)0.104 (12)*
H21W0.916 (3)0.8823 (9)0.300 (3)0.105 (11)*
H22W0.999 (3)0.8564 (9)0.394 (3)0.076 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl60.1021 (7)0.0648 (4)0.0759 (5)0.0126 (4)0.0335 (4)0.0225 (3)
O20.0417 (11)0.0654 (10)0.0662 (11)0.0010 (8)0.0138 (8)0.0109 (8)
N100.0482 (15)0.0376 (10)0.0476 (11)0.0108 (10)0.0048 (10)0.0111 (8)
N910.0384 (12)0.0317 (9)0.0384 (10)0.0051 (8)0.0074 (8)0.0066 (8)
N1410.0402 (13)0.0499 (11)0.0320 (9)0.0121 (9)0.0078 (8)0.0050 (8)
C10.0428 (16)0.0341 (11)0.0428 (12)0.0018 (10)0.0014 (10)0.0013 (9)
C20.0411 (17)0.0456 (13)0.0459 (13)0.0015 (12)0.0079 (11)0.0030 (10)
C30.0386 (15)0.0557 (14)0.0574 (15)0.0116 (12)0.0072 (12)0.0034 (12)
C40.0428 (17)0.0448 (13)0.0573 (15)0.0146 (12)0.0041 (12)0.0044 (11)
C50.0611 (19)0.0361 (12)0.0418 (13)0.0022 (11)0.0077 (12)0.0092 (9)
C60.064 (2)0.0366 (12)0.0471 (13)0.0098 (12)0.0145 (12)0.0038 (10)
C70.0555 (17)0.0416 (12)0.0586 (15)0.0078 (12)0.0124 (12)0.0017 (11)
C80.0463 (17)0.0355 (11)0.0505 (13)0.0025 (11)0.0051 (11)0.0066 (10)
C90.0413 (14)0.0250 (10)0.0295 (10)0.0023 (9)0.0008 (9)0.0028 (8)
C110.0376 (14)0.0289 (10)0.0349 (11)0.0023 (9)0.0006 (9)0.0038 (8)
C120.0452 (16)0.0304 (11)0.0402 (12)0.0023 (10)0.0018 (10)0.0013 (9)
C130.0495 (17)0.0309 (11)0.0380 (12)0.0010 (11)0.0032 (10)0.0000 (9)
C140.0410 (15)0.0269 (10)0.0367 (11)0.0016 (9)0.0003 (10)0.0023 (8)
C210.0591 (19)0.0708 (17)0.0708 (18)0.0023 (14)0.0163 (14)0.0199 (14)
C1010.0342 (14)0.0359 (11)0.0394 (11)0.0016 (10)0.0042 (10)0.0030 (9)
C1020.0438 (16)0.0454 (13)0.0556 (14)0.0003 (11)0.0045 (12)0.0053 (10)
C1110.0393 (14)0.0333 (11)0.0368 (11)0.0010 (9)0.0005 (10)0.0001 (8)
C1210.0389 (15)0.0411 (12)0.0418 (12)0.0011 (10)0.0002 (10)0.0014 (9)
C1310.0392 (14)0.0430 (12)0.0347 (11)0.0054 (10)0.0022 (10)0.0032 (9)
C1510.070 (2)0.0565 (15)0.0585 (16)0.0093 (13)0.0094 (14)0.0250 (12)
C1610.141 (3)0.0528 (16)0.080 (2)0.0324 (18)0.009 (2)0.0029 (14)
C1710.0366 (16)0.0707 (15)0.0430 (13)0.0080 (12)0.0070 (11)0.0048 (11)
C1810.0465 (18)0.123 (2)0.0472 (15)0.0158 (16)0.0026 (13)0.0065 (15)
S5A0.0520 (4)0.0364 (3)0.0345 (3)0.0019 (3)0.0051 (2)0.0023 (2)
O2A0.0672 (13)0.0427 (9)0.0524 (10)0.0099 (8)0.0032 (9)0.0021 (8)
O51A0.0681 (12)0.0578 (10)0.0506 (10)0.0141 (9)0.0180 (9)0.0086 (7)
O52A0.0761 (14)0.0456 (9)0.1081 (15)0.0168 (9)0.0418 (12)0.0011 (9)
O53A0.1123 (16)0.0506 (10)0.0505 (10)0.0125 (10)0.0304 (10)0.0000 (8)
O71A0.0579 (12)0.0603 (10)0.0586 (10)0.0028 (9)0.0195 (9)0.0249 (8)
O72A0.0837 (14)0.0377 (9)0.0697 (11)0.0015 (9)0.0094 (10)0.0127 (8)
C1A0.0325 (13)0.0354 (11)0.0325 (11)0.0048 (9)0.0045 (9)0.0032 (8)
C2A0.0390 (14)0.0379 (12)0.0393 (12)0.0004 (10)0.0081 (10)0.0026 (9)
C3A0.0389 (15)0.0504 (13)0.0309 (11)0.0043 (11)0.0024 (10)0.0031 (9)
C4A0.0361 (14)0.0420 (12)0.0294 (10)0.0093 (10)0.0024 (9)0.0060 (9)
C5A0.0314 (13)0.0379 (11)0.0268 (10)0.0068 (9)0.0071 (9)0.0036 (8)
C6A0.0302 (13)0.0427 (12)0.0282 (10)0.0031 (9)0.0012 (9)0.0039 (8)
C7A0.0483 (17)0.0419 (13)0.0433 (13)0.0057 (11)0.0068 (12)0.0095 (10)
O1W0.0739 (17)0.1240 (18)0.0380 (11)0.0435 (15)0.0028 (11)0.0088 (11)
O2W0.0767 (14)0.0510 (11)0.0422 (10)0.0128 (10)0.0021 (9)0.0110 (8)
Geometric parameters (Å, º) top
Cl6—C61.734 (3)C3—H30.9300
S5A—O53A1.4290 (18)C4—H40.9300
S5A—C5A1.7661 (19)C5—H50.9300
S5A—O52A1.447 (2)C7—H70.9300
S5A—O51A1.4413 (17)C8—H80.9300
O2—C21.358 (3)C111—C1211.517 (3)
O2—C211.433 (3)C121—C1311.515 (3)
O2A—C2A1.354 (2)C21—H2130.9600
O71A—C7A1.239 (3)C21—H2120.9600
O72A—C7A1.263 (3)C21—H2110.9600
O2A—H2A0.92 (3)C151—C1611.508 (4)
O1W—H12W0.83 (3)C171—C1811.509 (3)
O1W—H11W0.77 (3)C101—H1010.9800
O2W—H21W0.89 (3)C1A—C2A1.401 (3)
O2W—H22W0.88 (3)C1A—C6A1.393 (3)
N10—C121.366 (3)C1A—C7A1.494 (3)
N10—C131.346 (3)C102—H1020.9600
N91—C91.332 (2)C102—H1030.9600
N91—C1011.472 (3)C102—H1040.9600
N10—H100.90 (3)C2A—C3A1.398 (3)
N141—C1711.499 (3)C3A—C4A1.372 (3)
N141—C1311.500 (3)C4A—C5A1.392 (3)
N141—C1511.503 (3)C5A—C6A1.385 (3)
N91—H910.90 (2)C111—H1120.9700
N141—H1410.91 (2)C111—H1110.9700
C1—C21.368 (3)C121—H1210.9700
C1—C111.418 (3)C121—H1220.9700
C2—C31.401 (3)C131—H1320.9700
C3—C41.352 (3)C131—H1310.9700
C4—C121.403 (3)C151—H1510.9700
C5—C131.414 (3)C151—H1520.9700
C5—C61.350 (4)C161—H1620.9600
C6—C71.400 (3)C161—H1630.9600
C7—C81.364 (3)C161—H1610.9600
C8—C141.414 (3)C171—H1710.9700
C9—C111.445 (3)C171—H1720.9700
C9—C141.448 (3)C181—H1810.9600
C11—C121.408 (3)C181—H1820.9600
C13—C141.417 (3)C181—H1830.9600
C101—C1021.520 (3)C3A—H3A0.9300
C1—H10.9300C4A—H4A0.9300
C101—C1111.531 (3)C6A—H6A0.9300
O52A—S5A—C5A104.58 (10)H211—C21—H212109.00
O53A—S5A—C5A106.86 (9)N141—C131—C121113.62 (16)
O51A—S5A—C5A106.33 (9)N141—C151—C161113.58 (19)
O51A—S5A—O52A111.87 (10)N141—C171—C181113.63 (19)
O51A—S5A—O53A113.53 (11)C102—C101—H101109.00
O52A—S5A—O53A112.89 (11)C111—C101—H101109.00
C2—O2—C21117.64 (19)N91—C101—H101109.00
C2A—O2A—H2A100.6 (16)C2A—C1A—C6A118.43 (17)
H11W—O1W—H12W119 (3)C2A—C1A—C7A121.87 (17)
H21W—O2W—H22W107 (3)C6A—C1A—C7A119.70 (17)
C12—N10—C13122.91 (18)H102—C102—H103109.00
C9—N91—C101131.19 (17)C101—C102—H104109.00
C12—N10—H10116.3 (19)C101—C102—H103109.00
C13—N10—H10120.8 (19)C101—C102—H102109.00
C131—N141—C171111.96 (16)H103—C102—H104110.00
C131—N141—C151111.23 (17)H102—C102—H104109.00
C151—N141—C171114.21 (19)O2A—C2A—C3A118.41 (18)
C9—N91—H91120.0 (13)O2A—C2A—C1A121.62 (17)
C101—N91—H91108.3 (13)C1A—C2A—C3A119.97 (17)
C131—N141—H141105.2 (13)C2A—C3A—C4A120.28 (18)
C171—N141—H141103.1 (13)C3A—C4A—C5A120.65 (18)
C151—N141—H141110.4 (13)S5A—C5A—C4A120.97 (14)
C2—C1—C11120.78 (18)C4A—C5A—C6A118.94 (17)
O2—C2—C1125.11 (19)S5A—C5A—C6A120.05 (14)
O2—C2—C3114.33 (18)C1A—C6A—C5A121.67 (18)
C1—C2—C3120.55 (19)O72A—C7A—C1A117.29 (18)
C2—C3—C4120.19 (19)O71A—C7A—C1A119.63 (19)
C3—C4—C12120.39 (19)O71A—C7A—O72A123.1 (2)
C6—C5—C13119.6 (2)C101—C111—H112109.00
Cl6—C6—C5120.61 (17)C101—C111—H111108.00
Cl6—C6—C7117.8 (2)H111—C111—H112108.00
C5—C6—C7121.6 (2)C121—C111—H112109.00
C6—C7—C8119.3 (3)C121—C111—H111109.00
C7—C8—C14122.0 (2)C131—C121—H122110.00
N91—C9—C14123.69 (19)C111—C121—H122110.00
C11—C9—C14117.71 (17)C111—C121—H121110.00
N91—C9—C11118.61 (17)H121—C121—H122108.00
C9—C11—C12119.23 (17)C131—C121—H121110.00
C1—C11—C12117.35 (18)C121—C131—H132109.00
C1—C11—C9123.27 (17)C121—C131—H131109.00
N10—C12—C11120.01 (19)N141—C131—H132109.00
C4—C12—C11120.73 (19)H131—C131—H132108.00
N10—C12—C4119.24 (18)N141—C131—H131109.00
N10—C13—C5118.87 (19)H151—C151—H152108.00
N10—C13—C14120.69 (18)C161—C151—H151109.00
C5—C13—C14120.4 (2)N141—C151—H151109.00
C8—C14—C9124.53 (18)N141—C151—H152109.00
C8—C14—C13116.87 (17)C161—C151—H152109.00
C9—C14—C13118.52 (18)H161—C161—H162109.00
N91—C101—C111109.15 (16)C151—C161—H162109.00
C102—C101—C111110.28 (16)C151—C161—H161109.00
C11—C1—H1120.00H162—C161—H163109.00
N91—C101—C102110.55 (16)H161—C161—H163110.00
C2—C1—H1120.00C151—C161—H163109.00
C2—C3—H3120.00C181—C171—H172109.00
C4—C3—H3120.00N141—C171—H172109.00
C12—C4—H4120.00H171—C171—H172108.00
C3—C4—H4120.00C181—C171—H171109.00
C6—C5—H5120.00N141—C171—H171109.00
C13—C5—H5120.00C171—C181—H183109.00
C6—C7—H7120.00C171—C181—H181109.00
C8—C7—H7120.00C171—C181—H182109.00
C7—C8—H8119.00H182—C181—H183109.00
C14—C8—H8119.00H181—C181—H183109.00
C101—C111—C121114.90 (16)H181—C181—H182110.00
O2—C21—H212110.00C4A—C3A—H3A120.00
H212—C21—H213109.00C2A—C3A—H3A120.00
C111—C121—C131109.66 (16)C3A—C4A—H4A120.00
H211—C21—H213110.00C5A—C4A—H4A120.00
O2—C21—H211109.00C5A—C6A—H6A119.00
O2—C21—H213109.00C1A—C6A—H6A119.00
O52A—S5A—C5A—C4A58.41 (19)Cl6—C6—C7—C8178.98 (16)
O53A—S5A—C5A—C4A178.33 (17)C6—C7—C8—C140.9 (3)
O51A—S5A—C5A—C6A122.24 (17)C7—C8—C14—C134.0 (3)
O52A—S5A—C5A—C6A119.25 (18)C7—C8—C14—C9179.25 (19)
O53A—S5A—C5A—C6A0.7 (2)C14—C9—C11—C1210.2 (3)
O51A—S5A—C5A—C4A60.10 (19)N91—C9—C11—C15.5 (3)
C21—O2—C2—C3170.4 (2)N91—C9—C11—C12169.92 (18)
C21—O2—C2—C110.0 (3)C14—C9—C11—C1174.41 (18)
C12—N10—C13—C145.0 (3)N91—C9—C14—C812.8 (3)
C13—N10—C12—C4177.11 (19)N91—C9—C14—C13170.54 (18)
C13—N10—C12—C114.4 (3)C11—C9—C14—C8167.09 (18)
C12—N10—C13—C5174.21 (19)C11—C9—C14—C139.6 (3)
C9—N91—C101—C111125.0 (2)C9—C11—C12—C4174.99 (18)
C101—N91—C9—C11157.06 (19)C1—C11—C12—C40.7 (3)
C101—N91—C9—C1423.1 (3)C9—C11—C12—N103.4 (3)
C9—N91—C101—C102113.6 (2)C1—C11—C12—N10179.10 (18)
C9—N91—C101—C111125.0 (2)N10—C13—C14—C8174.69 (18)
N91—C101—C111—C12162.6 (2)C5—C13—C14—C9178.53 (18)
C101—C111—C121—C131175.79 (16)N10—C13—C14—C92.2 (3)
C111—C121—C131—N141170.13 (16)C5—C13—C14—C84.6 (3)
C121—C131—N141—C151163.03 (18)C2A—C1A—C7A—O71A175.0 (2)
C121—C131—N141—C17167.9 (2)C2A—C1A—C7A—O72A3.6 (3)
C131—N141—C151—C16167.4 (3)C6A—C1A—C7A—O71A6.0 (3)
C131—N141—C171—C181175.61 (19)C6A—C1A—C7A—O72A175.40 (19)
C2—C1—C11—C9175.11 (19)C7A—C1A—C2A—O2A0.4 (3)
C11—C1—C2—O2179.66 (19)C7A—C1A—C2A—C3A178.50 (19)
C11—C1—C2—C30.1 (3)C2A—C1A—C6A—C5A0.7 (3)
C2—C1—C11—C120.4 (3)C7A—C1A—C6A—C5A179.74 (19)
C1—C2—C3—C40.1 (3)C6A—C1A—C2A—O2A178.64 (19)
O2—C2—C3—C4179.73 (19)C6A—C1A—C2A—C3A2.5 (3)
C2—C3—C4—C120.4 (3)O2A—C2A—C3A—C4A178.77 (19)
C3—C4—C12—C110.7 (3)C1A—C2A—C3A—C4A2.3 (3)
C3—C4—C12—N10179.16 (19)C2A—C3A—C4A—C5A0.3 (3)
C13—C5—C6—Cl6179.58 (15)C3A—C4A—C5A—C6A1.5 (3)
C6—C5—C13—C142.0 (3)C3A—C4A—C5A—S5A176.24 (16)
C13—C5—C6—C71.3 (3)S5A—C5A—C6A—C1A176.46 (16)
C6—C5—C13—N10177.24 (19)C4A—C5A—C6A—C1A1.3 (3)
C5—C6—C7—C81.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2A···O72A0.92 (3)1.69 (3)2.554 (2)156 (3)
N10—H10···O71Ai0.90 (3)2.49 (2)3.178 (2)134 (2)
N10—H10···O72Ai0.90 (3)1.94 (3)2.825 (3)168 (2)
N91—H91···O2W0.90 (2)2.00 (2)2.869 (2)163.6 (19)
N141—H141···O1W0.91 (2)1.80 (2)2.700 (3)173.3 (19)
O1W—H11W···O71A0.77 (3)1.97 (3)2.740 (3)179 (3)
O1W—H12W···O51Aii0.83 (3)1.95 (3)2.770 (3)172 (3)
O2W—H21W···O71Aiii0.89 (3)1.88 (3)2.759 (2)170 (3)
O2W—H22W···O52Aiv0.88 (3)1.87 (3)2.744 (2)175 (3)
C1—H1···O2W0.932.343.248 (3)166
C6A—H6A···O53A0.932.482.879 (2)106
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1/2, y+3/2, z+1/2; (iii) x, y, z1; (iv) x+1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC23H32ClN3O2+·C7H4O6S2·2H2O
Mr654.17
Crystal system, space groupMonoclinic, P21/n
Temperature (K)297
a, b, c (Å)10.1753 (3), 30.8461 (7), 10.3671 (2)
β (°) 99.966 (3)
V3)3204.81 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.20 × 0.20 × 0.15
Data collection
DiffractometerOxford Diffraction Gemini-S Ultra CCD detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.906, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
29865, 5455, 3568
Rint0.049
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.100, 0.99
No. of reflections5455
No. of parameters433
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.26

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2A···O72A0.92 (3)1.69 (3)2.554 (2)156 (3)
N10—H10···O71Ai0.90 (3)2.49 (2)3.178 (2)134 (2)
N10—H10···O72Ai0.90 (3)1.94 (3)2.825 (3)168 (2)
N91—H91···O2W0.90 (2)2.00 (2)2.869 (2)163.6 (19)
N141—H141···O1W0.91 (2)1.80 (2)2.700 (3)173.3 (19)
O1W—H11W···O71A0.77 (3)1.97 (3)2.740 (3)179 (3)
O1W—H12W···O51Aii0.83 (3)1.95 (3)2.770 (3)172 (3)
O2W—H21W···O71Aiii0.89 (3)1.88 (3)2.759 (2)170 (3)
O2W—H22W···O52Aiv0.88 (3)1.87 (3)2.744 (2)175 (3)
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1/2, y+3/2, z+1/2; (iii) x, y, z1; (iv) x+1/2, y+3/2, z1/2.
Comparison of torsion angles within the C9 side-chain for (I) and quinacrinium dichloride dihydrate (Courseille et al., 1973) top
Torsion angle (°)(I)Quinacrinium dichloride dihydrate
C11–C9–N91–C101157.06 (19)174.4 (5)
C9–N91–C101–C111-125.0 (2)-142.9 (6)
N91–C101–C111–C12162.6 (2)64.4 (5)
C101–C111–C121–C131175.79 (16)172.8 (4)
C111–C121–C131–N141-170.13 (16)-165.3 (4)
C121–C131–N141–C151163.03 (18)64.7 (5)
C121–C131–N141–C171-67.9 (2)-66.1 (6)
C131–N141–C151–C16167.4 (2)55.7 (8)
C131–N141–C171–C181175.61 (19)-147.1 (8)
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds