Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The crystal structure of the hydrated proton-transfer compound of the drug quinacrine [rac-N′-(6-chloro-2-methoxy­acridin-9-yl)-N,N-diethyl­pentane-1,4-diamine] with 4,5-dichloro­phthalic acid, C23H32ClN3O2+·2C8H3Cl2O4·4H2O, has been determined at 200 K. The four labile water mol­ecules of solvation in the structure form discrete ...O—H...O—H... hydrogen-bonded chains parallel to the quin­acrine side chain, the two N—H groups of which act as hydrogen-bond donors for two of the water acceptor mol­ecules. The other water mol­ecules, as well as the acridinium H atom, also form hydrogen bonds with the two anion species and extend the structure into two-dimensional sheets. Between these sheets there are also weak cation–anion and anion–anion π–π aromatic ring inter­actions. This structure represents the third example of a simple quinacrine derivative for which structural data are available but differs from the other two in that it is unstable in the X-ray beam due to efflorescence, probably associated with the destruction of the unusual four-membered water chain structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109006702/ga3117sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109006702/ga3117Isup2.hkl
Contains datablock I

CCDC reference: 730089

Comment top

Quinacrine [rac-N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] is a substituted acridine which, as the dihydrochloride dihydrate, briefly found use as the antimalarial drug atabrine (or mepacrine). More recently, it has been used as an experimental drug for a number of other medical conditions which have been described previously (Smith & Wermuth, 2008). The crystal structures of racemic atabrine (Courseille et al., 1973) and, more recently, racemic quinacrinium 5-sulfosalicylate dihydrate (Smith & Wermuth, 2008), represent the only two simple quinacrine salt structures which have been reported to date. In both of these compounds the quinocrinium dication is protonated at the hetero N atom (N10) of the acridine ring and at the terminal tertiary N atom of the C9 side chain (N141). Hydrogen-bonding interactions involving these centres, the anion species and the solvent water molecules provide three-dimensional structures which form stable crystalline solids with relatively high melting points (ca. 523 K). Interactive aromatic cation–cation ππ stacking effects are found in the dichloride but not in the 5-sulfosalicylate. Weak ππ interactions are also found in the crystal structure of the Trypanosoma cruzi trypanothione reductase (TR) complex with quinacrine (Jacobi et al., 1996). The TR complex shows that specific sites on the acridine ring system (the hetero N, the C2 methoxy O and the C6 chloro substituent groups) and the two amino groups of the substituent side chain at C9 are fixed at the active sites of the TR enzyme.

The halogenated phthalic acid 4,5-dichlorophthalic acid (DCPA) has proved very effective in the stabilization of crystalline aromatic amine salts, particularly as the acid phthalates, and we have determined a number of these structures (Smith et al., 2008a,b, 2009). Using this acid and the same experimental conditions and solvent system (aqueous ethanol) as employed in the preparation of the 5-sulfosalicylate (5-SSA) salt, we obtained apparently good crystals of the title DCPA salt, racemic quinacrinium bis(hydrogen 4,5-dichlorophthalate) tetrahydrate, (I), which were stable in a closed container but which quickly underwent decomposition with efflorescence in the X-ray beam at room temperature. Diffraction data were therefore collected at 200 K from a specimen immersed in an oil drop. These crystal characteristics contrast with the hydrated dichloride and 5-SSA salts, which are chemically stable with relatively high melting points of ca 590 K [523 K in previous paragraph], cf. 343 K for (I), the structure of which we report here.

As expected, the quinacrine molecule of (I) is protonated at both the acridine hetero N atom (N10) and the terminal tertiary diethylamino N atom (N141) (Fig. 1). The four solvent water molecules form discrete ···O—H···O—H··· associated hydrogen-bonded chains, with two of these (O1W and O2W) also acting as acceptors for the two N—H groups of the quinacrine side chain (Table 1). These water chains are parallel to the side chains and also form hydrogen-bonding associations with the carboxyl O-acceptors of the two DCPA anions (Fig. 1). These interactions and an acridinium N—H···Ocarboxyl hydrogen bond result in a two-dimensional layered structure (Fig. 2), which is also found in the structures of quinacrinium dichloride dihydrate (Courseille et al., 1973) and the 5-SSA dihydrate salt (Smith & Wermuth, 2008). In the 5-SSA salt, the two side-chain N—H groups also act as donors for the two discrete water molecules, whereas in the dichloride only one of the water molecules is associated directly with a quinacrine N atom, the other being involved in interactions with the chloride anions. Conformationally all three structures are similar, with the C91 side chains, not unexpectedly, adopting perpendicular attitudes with respect to the acridine ring.

In the structure of (I) there are also weak cation–anion and anion–anion aromatic ring ππ interactions, with minimum centroid separations for the six-membered acridine rings N10/C12/C11/C9/C14/C13 and C1–C4/C12/C11 from the anion ring C1A–C6A of 3.599 (3) and 3.686 (3) Å, respectively, and for anion ring C1A–C6A from anion ring C1B–C6B of 3.693 (3) Å. These ππ associations are present in the structure of the dichloride but are absent in the 5-SSA salt. In addition, there is a short acridine Cl···Ocarboxyl association [Cl6···O11Bv = 3.204 (4) Å; symmetry code (v): -x + 1, -y + 1, -z + 2], similar to the values of 3.2279 (14) and 3.1582 (15) Å observed in the structures of DCPA salts with 3-aminobenzoic acid (Smith et al., 2008b) and nicotinamide (Smith et al., 2009), respectively. However, no intermolecular DCPA Cl···Cl interactions, such as are present in a number of DCPA structures (Smith et al., 2009), are found in (I).

The DCPA anion species in (I) (A and B) are conformationally similar and are essentially planar [torsion angles C2—C1—C11—O11 = 177.1 (5)° for species A and 178.5 (5)° for species B, C1–C2–C21–O22 = -172.5 (5)° for A and -174.2 (4)° for B]. The planarity is maintained by the presence of short intramolecular carboxylic acid O—H···Ocarboxyl hydrogen bonds (Table 1, entries 4 and 5). This planar species, rather than the non-planar one, is typically found in the acid salts of DCPA (Smith et al., 2008a,b, 2009).

From the structure of (I) it may be concluded that the inherent physical instability in the X-ray beam compared with the stable dihydrochloride dihydrate and 5-sulfosalicylate salts may be attributed to the somewhat more fragile tetrahydrate chain structure. This is also reflected in the significantly lower melting point of (I) compared with the other two compounds. However, such properties would not preclude the possibility that compound (I) might be used as an alternative to atabrine as a drug.

Experimental top

The title compound was synthesized by heating together under reflux for 10 min quinacrinium dichloride dihydrate (atabrine or mepacrine; O'Neil, 2001) (1 mmol) and 4,5-dichlorophthalic acid (DCPA) (1 mmol) in 50% ethanol–water (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solution gave pale-yellow prisms of (I) (m.p. 343 K) which, although chemically stable in a closed container, rapidly effloresced in the X-ray beam. This necessitated the use of low-temperature (200 K) collection of X-ray data from the crystal immersed in a silicone oil drop.

Refinement top

H atoms potentially involved in hydrogen-bonding interactions 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 and treated as riding atoms, with C—H = 0.93 Å (aromatic) and 0.96 or 0.97 Å (aliphatic), and with Uiso(H) = 1.2Ueq(C). All collected data were used in the refinement.

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: SHELXS97 (Sheldrick, 2008); 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 two hydrogen 4,5-dichlorophthalate anions (A and B) and the four solvent water molecules of (I). Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen-bonding associations are shown as dashed lines.
[Figure 2] Fig. 2. Hydrogen-bonding extensions in the two-dimensional structure of (I), shown in a perspective view down the approximate a-axis direction of the unit cell. A and B represent the two DCPA anion species. H atoms not involved in the interactions shown have been omitted. For symmetry codes, see Table 1.
[4-(6-chloro-2-methoxyacridin-10-ium-9-ylamino)pentyl]diethylammonium bis(2-carboxy-4,5-dichlorobenzoate) tetrahydrate top
Crystal data top
C23H32ClN3O2+·2C8H3Cl2O4·4H2OZ = 2
Mr = 942.04F(000) = 980
Triclinic, P1Dx = 1.457 Mg m3
Hall symbol: -P 1Melting point: 343 K
a = 10.6392 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.6737 (5) ÅCell parameters from 5030 reflections
c = 18.2030 (12) Åθ = 3.0–32.4°
α = 77.961 (5)°µ = 0.41 mm1
β = 89.549 (5)°T = 200 K
γ = 76.432 (5)°Block, yellow
V = 2147.4 (2) Å30.20 × 0.20 × 0.15 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
7444 independent reflections
Radiation source: Enhance (Mo) X-ray tube4778 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ω scansθmax = 25.3°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.909, Tmax = 0.948k = 1414
14440 measured reflectionsl = 2121
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)] = 0.078Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.195H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.1124P)2]
where P = (Fo2 + 2Fc2)/3
7444 reflections(Δ/σ)max = 0.002
593 parametersΔρmax = 0.70 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C23H32ClN3O2+·2C8H3Cl2O4·4H2Oγ = 76.432 (5)°
Mr = 942.04V = 2147.4 (2) Å3
Triclinic, P1Z = 2
a = 10.6392 (6) ÅMo Kα radiation
b = 11.6737 (5) ŵ = 0.41 mm1
c = 18.2030 (12) ÅT = 200 K
α = 77.961 (5)°0.20 × 0.20 × 0.15 mm
β = 89.549 (5)°
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer
7444 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4778 reflections with I > 2σ(I)
Tmin = 0.909, Tmax = 0.948Rint = 0.057
14440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0780 restraints
wR(F2) = 0.195H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.70 e Å3
7444 reflectionsΔρmin = 0.43 e Å3
593 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 esds 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
Cl60.71491 (11)0.40203 (10)1.12719 (6)0.0350 (3)
O20.3581 (3)1.0802 (3)0.66236 (19)0.0427 (11)
N100.4949 (3)0.7724 (3)0.9367 (2)0.0257 (10)
N910.5970 (3)0.6337 (3)0.7478 (2)0.0267 (11)
N1410.2206 (3)0.4717 (3)0.6373 (2)0.0305 (11)
C10.4675 (4)0.8811 (4)0.7315 (2)0.0266 (12)
C20.4002 (4)0.9979 (4)0.7276 (3)0.0313 (14)
C30.3671 (4)1.0400 (4)0.7929 (3)0.0320 (13)
C40.3992 (4)0.9667 (4)0.8615 (3)0.0303 (14)
C50.5983 (4)0.5935 (4)1.0221 (2)0.0259 (12)
C60.6786 (4)0.4823 (3)1.0349 (2)0.0257 (12)
C70.7347 (4)0.4307 (4)0.9758 (2)0.0296 (12)
C80.7041 (4)0.4909 (4)0.9038 (2)0.0305 (12)
C90.5752 (4)0.6753 (3)0.8099 (2)0.0222 (11)
C110.5039 (4)0.8015 (3)0.8023 (2)0.0233 (11)
C120.4677 (4)0.8444 (3)0.8665 (2)0.0230 (11)
C130.5693 (4)0.6579 (3)0.9471 (2)0.0234 (11)
C140.6159 (4)0.6071 (3)0.8856 (2)0.0225 (11)
C210.3894 (5)1.0430 (5)0.5933 (3)0.0501 (17)
C1010.6492 (4)0.5106 (3)0.7335 (2)0.0282 (11)
C1020.7889 (5)0.4950 (4)0.7128 (3)0.0403 (17)
C1110.5680 (4)0.4900 (4)0.6709 (2)0.0309 (12)
C1210.4255 (4)0.5050 (4)0.6873 (3)0.0305 (12)
C1310.3637 (4)0.4321 (4)0.6440 (3)0.0330 (14)
C1510.1631 (5)0.3906 (5)0.5996 (3)0.0445 (17)
C1610.1905 (6)0.4025 (6)0.5191 (3)0.063 (2)
C1710.1556 (5)0.4913 (4)0.7084 (3)0.0362 (14)
C1810.1782 (5)0.3798 (4)0.7707 (3)0.0485 (17)
Cl30.06477 (14)1.19911 (11)0.87634 (7)0.0494 (4)
Cl4B0.10174 (12)0.93106 (10)0.93854 (6)0.0397 (3)
O11B0.2086 (3)0.7601 (3)0.70717 (19)0.0446 (11)
O12B0.1318 (4)0.8825 (3)0.60114 (18)0.0495 (13)
O21B0.0243 (4)1.0875 (3)0.55335 (17)0.0480 (13)
O22B0.0606 (3)1.2507 (3)0.59485 (18)0.0440 (10)
C1B0.0929 (4)0.9553 (3)0.7164 (2)0.0237 (11)
C2B0.0230 (4)1.0762 (4)0.6876 (2)0.0275 (12)
C3B0.0227 (4)1.1465 (4)0.7402 (2)0.0302 (11)
C4B0.0026 (4)1.1049 (4)0.8163 (2)0.0304 (14)
C5B0.0685 (4)0.9871 (4)0.8438 (2)0.0275 (12)
C6B0.1133 (4)0.9155 (4)0.7933 (2)0.0262 (11)
C11B0.1491 (4)0.8581 (4)0.6726 (2)0.0293 (12)
C21B0.0071 (4)1.1428 (4)0.6067 (2)0.0323 (14)
Cl4A0.11056 (14)1.30100 (12)1.01560 (8)0.0582 (5)
Cl5B0.05544 (13)1.33712 (11)1.18081 (10)0.0600 (5)
O11A0.2969 (4)0.9431 (4)1.3484 (2)0.0566 (14)
O12A0.3872 (4)0.8053 (3)1.2874 (2)0.0671 (16)
O21A0.4266 (4)0.7764 (3)1.1637 (3)0.0614 (16)
O22A0.3994 (4)0.8845 (4)1.0489 (3)0.0726 (17)
C1A0.2771 (4)1.0006 (4)1.2152 (2)0.0279 (12)
C2A0.3013 (4)0.9838 (4)1.1416 (3)0.0293 (12)
C3A0.2495 (4)1.0790 (4)1.0817 (3)0.0336 (16)
C4A0.1743 (4)1.1880 (4)1.0923 (3)0.0339 (14)
C5A0.1501 (4)1.2038 (4)1.1642 (3)0.0314 (14)
C6A0.2025 (4)1.1123 (4)1.2243 (3)0.0319 (14)
C11A0.3226 (5)0.9120 (4)1.2896 (3)0.0386 (17)
C21A0.3811 (5)0.8736 (4)1.1154 (3)0.0439 (19)
O1W0.1979 (3)0.6864 (3)0.53762 (18)0.0422 (10)
O2W0.5917 (4)0.7634 (3)0.59276 (19)0.0519 (13)
O3W0.4350 (4)0.7418 (4)0.4753 (2)0.0681 (16)
O4W0.8062 (4)0.8662 (4)0.5773 (2)0.0734 (17)
H10.489500.853900.687500.0320*
H30.322401.119800.789300.0380*
H40.376800.995700.904900.0370*
H50.562900.627001.061900.0310*
H70.792600.355500.986000.0350*
H80.741400.455700.865000.0360*
H210.354101.108500.551900.0600*
H220.353300.975600.591100.0600*
H230.481701.019700.590300.0600*
H1010.644200.451200.779500.0340*
H1020.838600.508000.752800.0490*
H1030.794800.552200.667500.0490*
H1040.822000.414700.705100.0490*
H1110.576100.546400.624700.0370*
H1120.602500.409200.662800.0370*
H1210.381200.589500.673000.0370*
H1220.416500.478000.740800.0370*
H1310.397400.439000.594000.0400*
H1320.388300.347700.669200.0400*
H1510.197200.307500.625400.0530*
H1520.070100.409600.604700.0530*
H1610.151900.348900.498400.0750*
H1620.282400.382200.513600.0750*
H1630.155000.484100.492900.0750*
H1710.063200.521000.697300.0440*
H1720.186300.553200.726000.0440*
H1810.133900.399200.814300.0580*
H1820.269300.350600.783000.0580*
H1830.145900.318600.754400.0580*
H3B0.069201.225500.722500.0360*
H6B0.159500.836600.811900.0310*
H3A0.266001.069001.032900.0410*
H6A0.187801.125001.272700.0390*
H100.462 (4)0.806 (4)0.981 (3)0.027 (11)*
H910.574 (5)0.680 (5)0.705 (3)0.047 (16)*
H12B0.091 (5)0.961 (5)0.583 (3)0.065 (16)*
H1410.202 (4)0.545 (4)0.605 (3)0.038 (15)*
H21A0.404 (5)0.788 (5)1.211 (3)0.075 (17)*
H11W0.178 (5)0.744 (5)0.557 (3)0.055 (16)*
H12W0.157 (6)0.705 (6)0.499 (3)0.058 (16)*
H21W0.560 (4)0.757 (5)0.550 (3)0.066 (15)*
H22W0.648 (5)0.792 (6)0.580 (3)0.065 (15)*
H31W0.409 (6)0.798 (6)0.439 (4)0.078 (16)*
H32W0.366 (5)0.726 (5)0.493 (4)0.080 (15)*
H41W0.777 (6)0.920 (6)0.595 (4)0.085 (14)*
H42W0.852 (5)0.878 (6)0.542 (4)0.088 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl60.0411 (6)0.0295 (5)0.0297 (5)0.0078 (5)0.0068 (5)0.0038 (4)
O20.052 (2)0.0246 (16)0.043 (2)0.0071 (14)0.0033 (16)0.0094 (15)
N100.034 (2)0.0157 (16)0.0269 (18)0.0054 (14)0.0027 (15)0.0044 (15)
N910.037 (2)0.0203 (17)0.0243 (19)0.0100 (15)0.0015 (16)0.0048 (16)
N1410.036 (2)0.0186 (17)0.038 (2)0.0107 (15)0.0049 (16)0.0032 (15)
C10.030 (2)0.023 (2)0.028 (2)0.0107 (17)0.0025 (18)0.0030 (17)
C20.030 (2)0.020 (2)0.040 (3)0.0076 (17)0.0021 (19)0.0041 (19)
C30.033 (2)0.0128 (18)0.048 (3)0.0046 (17)0.002 (2)0.0023 (19)
C40.033 (2)0.0177 (19)0.042 (3)0.0058 (17)0.000 (2)0.0106 (19)
C50.025 (2)0.025 (2)0.028 (2)0.0075 (17)0.0004 (17)0.0047 (18)
C60.028 (2)0.021 (2)0.027 (2)0.0094 (17)0.0039 (17)0.0014 (17)
C70.029 (2)0.020 (2)0.037 (2)0.0037 (17)0.0056 (19)0.0017 (18)
C80.034 (2)0.023 (2)0.034 (2)0.0036 (18)0.0016 (19)0.0087 (18)
C90.0188 (19)0.0189 (19)0.031 (2)0.0091 (15)0.0037 (16)0.0048 (17)
C110.022 (2)0.0193 (19)0.030 (2)0.0100 (16)0.0008 (17)0.0028 (17)
C120.023 (2)0.0177 (18)0.030 (2)0.0100 (16)0.0012 (17)0.0029 (17)
C130.020 (2)0.0181 (19)0.034 (2)0.0064 (16)0.0028 (17)0.0077 (17)
C140.0198 (19)0.0199 (19)0.028 (2)0.0052 (16)0.0007 (16)0.0053 (17)
C210.061 (3)0.042 (3)0.040 (3)0.015 (3)0.008 (3)0.011 (2)
C1010.032 (2)0.0159 (19)0.036 (2)0.0036 (17)0.0010 (19)0.0066 (18)
C1020.045 (3)0.035 (3)0.043 (3)0.011 (2)0.000 (2)0.011 (2)
C1110.038 (2)0.022 (2)0.036 (2)0.0105 (18)0.0034 (19)0.0101 (19)
C1210.033 (2)0.025 (2)0.036 (2)0.0082 (18)0.0005 (19)0.0107 (19)
C1310.037 (2)0.024 (2)0.041 (3)0.0076 (18)0.002 (2)0.0132 (19)
C1510.047 (3)0.038 (3)0.058 (3)0.019 (2)0.007 (2)0.021 (2)
C1610.072 (4)0.061 (4)0.071 (4)0.024 (3)0.001 (3)0.040 (3)
C1710.035 (2)0.032 (2)0.047 (3)0.014 (2)0.007 (2)0.014 (2)
C1810.064 (3)0.033 (3)0.053 (3)0.023 (2)0.015 (3)0.007 (2)
Cl30.0824 (10)0.0323 (6)0.0365 (6)0.0115 (6)0.0129 (6)0.0169 (5)
Cl4B0.0534 (7)0.0414 (6)0.0234 (5)0.0139 (6)0.0009 (5)0.0021 (5)
O11B0.065 (2)0.0228 (16)0.0409 (19)0.0019 (15)0.0026 (17)0.0093 (15)
O12B0.079 (3)0.0345 (18)0.0337 (19)0.0041 (17)0.0017 (17)0.0150 (15)
O21B0.080 (3)0.0344 (18)0.0255 (17)0.0052 (17)0.0014 (17)0.0070 (15)
O22B0.071 (2)0.0221 (16)0.0374 (18)0.0136 (16)0.0088 (17)0.0001 (14)
C1B0.026 (2)0.0185 (19)0.031 (2)0.0130 (16)0.0017 (17)0.0067 (17)
C2B0.032 (2)0.026 (2)0.029 (2)0.0170 (18)0.0028 (18)0.0045 (18)
C3B0.039 (2)0.0169 (19)0.035 (2)0.0090 (18)0.001 (2)0.0037 (18)
C4B0.041 (3)0.025 (2)0.031 (2)0.0150 (19)0.0054 (19)0.0109 (18)
C5B0.030 (2)0.029 (2)0.025 (2)0.0131 (18)0.0027 (18)0.0024 (18)
C6B0.029 (2)0.0197 (19)0.030 (2)0.0077 (17)0.0009 (18)0.0036 (17)
C11B0.035 (2)0.023 (2)0.034 (2)0.0124 (19)0.0047 (19)0.0094 (19)
C21B0.045 (3)0.028 (2)0.026 (2)0.015 (2)0.004 (2)0.0033 (19)
Cl4A0.0608 (8)0.0426 (7)0.0643 (9)0.0223 (6)0.0243 (7)0.0165 (7)
Cl5B0.0428 (7)0.0329 (6)0.1066 (12)0.0015 (5)0.0068 (7)0.0286 (7)
O11A0.079 (3)0.061 (2)0.034 (2)0.033 (2)0.0005 (19)0.0007 (18)
O12A0.088 (3)0.033 (2)0.065 (3)0.005 (2)0.002 (2)0.0133 (19)
O21A0.073 (3)0.030 (2)0.080 (3)0.0025 (18)0.007 (2)0.020 (2)
O22A0.090 (3)0.068 (3)0.062 (3)0.004 (2)0.014 (2)0.045 (2)
C1A0.031 (2)0.024 (2)0.033 (2)0.0131 (18)0.0013 (18)0.0081 (18)
C2A0.030 (2)0.025 (2)0.039 (2)0.0140 (18)0.0013 (19)0.0117 (19)
C3A0.038 (3)0.039 (3)0.030 (2)0.019 (2)0.002 (2)0.010 (2)
C4A0.029 (2)0.028 (2)0.045 (3)0.0157 (19)0.006 (2)0.002 (2)
C5A0.024 (2)0.022 (2)0.053 (3)0.0085 (17)0.003 (2)0.015 (2)
C6A0.031 (2)0.039 (3)0.036 (2)0.018 (2)0.006 (2)0.020 (2)
C11A0.047 (3)0.039 (3)0.036 (3)0.027 (2)0.001 (2)0.003 (2)
C21A0.044 (3)0.034 (3)0.061 (4)0.009 (2)0.004 (3)0.027 (3)
O1W0.063 (2)0.0245 (16)0.0358 (18)0.0068 (15)0.0033 (16)0.0033 (14)
O2W0.084 (3)0.042 (2)0.0352 (18)0.0302 (19)0.0115 (18)0.0039 (16)
O3W0.070 (3)0.089 (3)0.046 (2)0.037 (2)0.008 (2)0.005 (2)
O4W0.084 (3)0.099 (3)0.058 (3)0.054 (3)0.014 (2)0.027 (2)
Geometric parameters (Å, º) top
Cl6—C61.742 (4)C3—H30.9300
Cl3—C4B1.729 (4)C4—H40.9300
Cl4B—C5B1.720 (4)C5—H50.9300
Cl4A—C4A1.725 (5)C7—H70.9300
Cl5B—C5A1.727 (5)C8—H80.9300
O2—C21.366 (6)C111—C1211.519 (6)
O2—C211.426 (6)C21—H220.9600
O11B—C11B1.213 (6)C121—C1311.526 (7)
O12B—C11B1.277 (5)C21—H210.9600
O21B—C21B1.275 (5)C21—H230.9600
O22B—C21B1.229 (6)C151—C1611.476 (8)
O12B—H12B0.91 (6)C171—C1811.510 (7)
O11A—C11A1.210 (6)C101—H1010.9800
O12A—C11A1.282 (6)C1B—C6B1.382 (5)
O21A—C21A1.276 (7)C1B—C2B1.423 (6)
O22A—C21A1.210 (8)C1B—C11B1.527 (6)
O21A—H21A0.92 (5)C102—H1030.9600
O1W—H11W0.81 (6)C102—H1020.9600
O1W—H12W0.79 (6)C102—H1040.9600
O2W—H22W0.76 (6)C2B—C21B1.513 (5)
O2W—H21W0.88 (5)C2B—C3B1.400 (6)
N10—C121.366 (5)C3B—C4B1.370 (5)
N10—C131.360 (5)C4B—C5B1.395 (6)
N91—C1011.490 (5)C5B—C6B1.378 (6)
N91—C91.319 (5)C111—H1120.9700
O3W—H31W0.83 (7)C111—H1110.9700
O3W—H32W0.84 (6)C121—H1220.9700
N10—H101.00 (5)C121—H1210.9700
N141—C1711.497 (6)C131—H1320.9700
N141—C1311.482 (6)C131—H1310.9700
N141—C1511.514 (7)C151—H1510.9700
N91—H910.85 (5)C151—H1520.9700
N141—H1410.91 (5)C161—H1620.9600
O4W—H42W0.81 (7)C161—H1630.9600
O4W—H41W0.77 (7)C161—H1610.9600
C1—C21.371 (7)C171—H1720.9700
C1—C111.419 (5)C171—H1710.9700
C2—C31.391 (7)C181—H1810.9600
C3—C41.354 (7)C181—H1830.9600
C4—C121.427 (6)C181—H1820.9600
C5—C131.412 (5)C3B—H3B0.9300
C5—C61.351 (6)C6B—H6B0.9300
C6—C71.403 (5)C1A—C6A1.400 (7)
C7—C81.354 (5)C1A—C11A1.526 (6)
C8—C141.432 (6)C1A—C2A1.407 (6)
C9—C141.453 (5)C2A—C21A1.530 (7)
C9—C111.469 (5)C2A—C3A1.394 (7)
C11—C121.383 (5)C3A—C4A1.385 (7)
C13—C141.408 (5)C4A—C5A1.374 (7)
C101—C1111.526 (6)C5A—C6A1.375 (7)
C101—C1021.509 (7)C3A—H3A0.9300
C1—H10.9300C6A—H6A0.9300
C2—O2—C21117.7 (4)C101—C102—H103109.00
C11B—O12B—H12B112 (3)C3B—C2B—C21B114.0 (4)
C21A—O21A—H21A109 (3)C1B—C2B—C3B116.9 (3)
H11W—O1W—H12W106 (6)C1B—C2B—C21B129.1 (4)
H21W—O2W—H22W102 (5)C2B—C3B—C4B123.5 (4)
C12—N10—C13121.4 (3)C3B—C4B—C5B119.1 (4)
C9—N91—C101133.0 (3)Cl3—C4B—C3B119.6 (4)
H31W—O3W—H32W103 (6)Cl3—C4B—C5B121.3 (3)
C12—N10—H10119 (3)Cl4B—C5B—C4B121.4 (3)
C13—N10—H10120 (3)Cl4B—C5B—C6B120.0 (3)
C131—N141—C151111.3 (4)C4B—C5B—C6B118.6 (3)
C131—N141—C171115.3 (4)C1B—C6B—C5B123.2 (4)
C151—N141—C171112.1 (4)C101—C111—H112109.00
C9—N91—H91121 (4)C101—C111—H111109.00
C101—N91—H91106 (4)C121—C111—H112109.00
C171—N141—H141106 (4)H111—C111—H112108.00
C131—N141—H141106 (4)C121—C111—H111109.00
C151—N141—H141106 (4)O12B—C11B—C1B119.1 (4)
H41W—O4W—H42W117 (7)O11B—C11B—O12B122.3 (4)
C2—C1—C11120.4 (4)O11B—C11B—C1B118.6 (3)
O2—C2—C1124.7 (4)C131—C121—H121110.00
O2—C2—C3114.8 (4)C131—C121—H122109.00
C1—C2—C3120.5 (5)C111—C121—H122110.00
C2—C3—C4121.0 (4)C111—C121—H121110.00
C3—C4—C12119.2 (4)H121—C121—H122108.00
C6—C5—C13118.7 (4)O21B—C21B—O22B122.0 (4)
Cl6—C6—C5119.1 (3)O22B—C21B—C2B117.8 (4)
C5—C6—C7121.7 (3)O21B—C21B—C2B120.2 (4)
Cl6—C6—C7119.3 (3)N141—C131—H132109.00
C6—C7—C8119.7 (4)H131—C131—H132108.00
C7—C8—C14122.0 (4)C121—C131—H132109.00
N91—C9—C11117.5 (3)C121—C131—H131109.00
N91—C9—C14125.6 (3)N141—C131—H131109.00
C11—C9—C14116.8 (3)N141—C151—H151109.00
C1—C11—C9122.7 (3)N141—C151—H152109.00
C1—C11—C12118.3 (3)C161—C151—H151109.00
C9—C11—C12119.0 (3)C161—C151—H152109.00
C4—C12—C11120.7 (4)H151—C151—H152108.00
N10—C12—C11121.9 (3)H161—C161—H163109.00
N10—C12—C4117.4 (4)H161—C161—H162109.00
N10—C13—C14121.2 (3)C151—C161—H162109.00
C5—C13—C14121.9 (3)C151—C161—H163109.00
N10—C13—C5116.9 (3)H162—C161—H163109.00
C9—C14—C13119.0 (3)C151—C161—H161110.00
C8—C14—C9125.1 (3)C181—C171—H172109.00
C8—C14—C13115.9 (3)H171—C171—H172108.00
N91—C101—C111109.9 (3)N141—C171—H171109.00
C102—C101—C111110.5 (3)C181—C171—H171109.00
N91—C101—C102110.3 (3)N141—C171—H172109.00
C11—C1—H1120.00C171—C181—H182109.00
C2—C1—H1120.00C171—C181—H183109.00
C4—C3—H3120.00H181—C181—H182109.00
C2—C3—H3119.00H181—C181—H183110.00
C3—C4—H4120.00H182—C181—H183109.00
C12—C4—H4120.00C171—C181—H181109.00
C13—C5—H5121.00C4B—C3B—H3B118.00
C6—C5—H5121.00C2B—C3B—H3B118.00
C8—C7—H7120.00C5B—C6B—H6B118.00
C6—C7—H7120.00C1B—C6B—H6B118.00
C7—C8—H8119.00C2A—C1A—C11A128.6 (4)
C14—C8—H8119.00C6A—C1A—C11A113.2 (4)
C101—C111—C121113.7 (3)C2A—C1A—C6A118.1 (4)
O2—C21—H23110.00C1A—C2A—C3A118.3 (4)
O2—C21—H21110.00C1A—C2A—C21A129.3 (4)
H21—C21—H23109.00C3A—C2A—C21A112.4 (4)
H22—C21—H23109.00C2A—C3A—C4A122.3 (5)
C111—C121—C131110.6 (4)C3A—C4A—C5A119.2 (5)
O2—C21—H22109.00Cl4A—C4A—C3A119.9 (4)
H21—C21—H22109.00Cl4A—C4A—C5A120.9 (4)
N141—C131—C121113.2 (4)Cl5B—C5A—C4A121.2 (4)
N141—C151—C161113.4 (5)Cl5B—C5A—C6A119.1 (4)
N141—C171—C181114.2 (4)C4A—C5A—C6A119.6 (4)
C102—C101—H101109.00C1A—C6A—C5A122.3 (5)
C111—C101—H101109.00O12A—C11A—C1A118.1 (4)
N91—C101—H101109.00O11A—C11A—C1A120.0 (4)
C6B—C1B—C11B113.2 (3)O11A—C11A—O12A121.9 (5)
C2B—C1B—C6B118.7 (3)O21A—C21A—O22A123.2 (5)
C2B—C1B—C11B128.1 (3)O21A—C21A—C2A119.5 (5)
H102—C102—H104109.00O22A—C21A—C2A117.3 (5)
H102—C102—H103110.00C4A—C3A—H3A119.00
C101—C102—H104109.00C2A—C3A—H3A119.00
H103—C102—H104110.00C1A—C6A—H6A119.00
C101—C102—H102109.00C5A—C6A—H6A119.00
C21—O2—C2—C11.8 (6)C11B—C1B—C2B—C3B177.6 (4)
C21—O2—C2—C3179.7 (4)C11B—C1B—C2B—C21B4.2 (8)
C13—N10—C12—C4174.3 (4)C2B—C1B—C6B—C5B0.4 (7)
C13—N10—C12—C116.1 (6)C11B—C1B—C6B—C5B178.5 (4)
C12—N10—C13—C5176.2 (4)C2B—C1B—C11B—O11B178.5 (4)
C12—N10—C13—C143.2 (6)C2B—C1B—C11B—O12B1.7 (7)
C101—N91—C9—C11171.0 (4)C6B—C1B—C11B—O11B2.8 (6)
C101—N91—C9—C149.2 (7)C6B—C1B—C11B—O12B177.1 (4)
C9—N91—C101—C102101.7 (5)C1B—C2B—C3B—C4B0.4 (7)
C9—N91—C101—C111136.3 (4)C21B—C2B—C3B—C4B178.0 (4)
C11—C1—C2—O2178.3 (4)C1B—C2B—C21B—O21B4.8 (7)
C11—C1—C2—C30.2 (7)C1B—C2B—C21B—O22B174.3 (4)
C2—C1—C11—C9179.6 (4)C3B—C2B—C21B—O21B177.0 (4)
C2—C1—C11—C121.1 (6)C3B—C2B—C21B—O22B3.9 (6)
O2—C2—C3—C4177.9 (4)C2B—C3B—C4B—Cl3179.4 (4)
C1—C2—C3—C40.7 (7)C2B—C3B—C4B—C5B1.0 (7)
C2—C3—C4—C120.2 (7)Cl3—C4B—C5B—Cl4B1.9 (6)
C3—C4—C12—N10178.1 (4)Cl3—C4B—C5B—C6B178.7 (3)
C3—C4—C12—C111.6 (7)C3B—C4B—C5B—Cl4B177.8 (3)
C13—C5—C6—Cl6180.0 (3)C3B—C4B—C5B—C6B1.7 (7)
C13—C5—C6—C70.9 (7)Cl4B—C5B—C6B—C1B178.5 (4)
C6—C5—C13—N10175.9 (4)C4B—C5B—C6B—C1B1.0 (7)
C6—C5—C13—C143.5 (7)C6A—C1A—C2A—C3A0.2 (6)
Cl6—C6—C7—C8178.1 (3)C6A—C1A—C2A—C21A178.5 (5)
C5—C6—C7—C82.8 (7)C11A—C1A—C2A—C3A179.7 (4)
C6—C7—C8—C140.3 (7)C11A—C1A—C2A—C21A1.0 (8)
C7—C8—C14—C9177.9 (4)C2A—C1A—C6A—C5A1.7 (7)
C7—C8—C14—C133.7 (6)C11A—C1A—C6A—C5A178.7 (4)
N91—C9—C11—C15.1 (6)C2A—C1A—C11A—O11A177.1 (5)
N91—C9—C11—C12173.4 (4)C2A—C1A—C11A—O12A3.3 (8)
C14—C9—C11—C1174.8 (4)C6A—C1A—C11A—O11A2.5 (7)
C14—C9—C11—C126.8 (6)C6A—C1A—C11A—O12A177.2 (5)
N91—C9—C14—C811.0 (7)C1A—C2A—C3A—C4A0.8 (7)
N91—C9—C14—C13170.7 (4)C21A—C2A—C3A—C4A179.7 (4)
C11—C9—C14—C8168.9 (4)C1A—C2A—C21A—O21A6.4 (8)
C11—C9—C14—C139.5 (6)C1A—C2A—C21A—O22A172.5 (5)
C1—C11—C12—N10177.6 (4)C3A—C2A—C21A—O21A174.9 (5)
C1—C11—C12—C42.0 (6)C3A—C2A—C21A—O22A6.3 (7)
C9—C11—C12—N100.9 (6)C2A—C3A—C4A—Cl4A178.7 (4)
C9—C11—C12—C4179.5 (4)C2A—C3A—C4A—C5A0.4 (7)
N10—C13—C14—C8173.7 (4)Cl4A—C4A—C5A—Cl5B0.1 (6)
N10—C13—C14—C94.8 (6)Cl4A—C4A—C5A—C6A179.8 (4)
C5—C13—C14—C85.7 (6)C3A—C4A—C5A—Cl5B179.2 (3)
C5—C13—C14—C9175.9 (4)C3A—C4A—C5A—C6A1.1 (7)
C6B—C1B—C2B—C3B1.1 (6)Cl5B—C5A—C6A—C1A178.2 (4)
C6B—C1B—C2B—C21B177.1 (4)C4A—C5A—C6A—C1A2.2 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H10···O22A1.00 (5)1.73 (5)2.716 (6)172 (5)
N91—H91···O2W0.85 (5)2.10 (5)2.905 (5)158 (5)
N141—H141···O1W0.91 (5)1.83 (5)2.733 (5)169 (4)
O21A—H21A···O12A0.92 (5)1.45 (5)2.366 (7)172 (6)
O12B—H12B···O21B0.91 (6)1.47 (6)2.378 (5)180 (8)
O1W—H11W···O12B0.81 (6)1.91 (6)2.722 (5)179 (9)
O1W—H12W···O22Bi0.79 (6)1.91 (6)2.702 (5)179 (9)
O2W—H21W···O3W0.88 (5)1.97 (5)2.809 (5)160 (4)
O2W—H22W···O4W0.76 (6)2.06 (6)2.804 (6)164 (5)
O3W—H31W···O11Aii0.83 (7)2.22 (7)3.031 (6)168 (6)
O3W—H32W···O1W0.84 (6)2.07 (6)2.913 (5)179 (8)
O4W—H41W···O11Aiii0.76 (7)2.08 (7)2.842 (6)175 (8)
O4W—H42W···O21Biv0.81 (7)2.20 (7)3.009 (5)179 (8)
C1—H1···O2W0.932.343.249 (5)166
C3A—H3A···O22A0.932.252.628 (7)104
C3B—H3B···O22B0.932.282.662 (5)104
C6A—H6A···O11A0.932.322.694 (6)103
C6B—H6B···O11B0.932.282.660 (5)104
C6B—H6B···Cl6v0.932.793.715 (5)177
C102—H102···Cl5Biii0.962.813.673 (5)150
C111—H111···O2W0.972.523.279 (6)135
C111—H112···O12Av0.972.463.291 (6)144
C121—H121···O11B0.972.553.397 (6)146
C151—H152···O22Bvi0.972.603.198 (7)120
C171—H172···O11B0.972.443.311 (6)150
Symmetry codes: (i) x, y+2, z+1; (ii) x, y, z1; (iii) x+1, y+2, z+2; (iv) x+1, y+2, z+1; (v) x+1, y+1, z+2; (vi) x, y1, z.

Experimental details

Crystal data
Chemical formulaC23H32ClN3O2+·2C8H3Cl2O4·4H2O
Mr942.04
Crystal system, space groupTriclinic, P1
Temperature (K)200
a, b, c (Å)10.6392 (6), 11.6737 (5), 18.2030 (12)
α, β, γ (°)77.961 (5), 89.549 (5), 76.432 (5)
V3)2147.4 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.41
Crystal size (mm)0.20 × 0.20 × 0.15
Data collection
DiffractometerOxford Diffraction Gemini-S CCD-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.909, 0.948
No. of measured, independent and
observed [I > 2σ(I)] reflections
14440, 7444, 4778
Rint0.057
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.078, 0.195, 1.01
No. of reflections7444
No. of parameters593
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.70, 0.43

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H10···O22A1.00 (5)1.73 (5)2.716 (6)172 (5)
N91—H91···O2W0.85 (5)2.10 (5)2.905 (5)158 (5)
N141—H141···O1W0.91 (5)1.83 (5)2.733 (5)169 (4)
O21A—H21A···O12A0.92 (5)1.45 (5)2.366 (7)172 (6)
O12B—H12B···O21B0.91 (6)1.47 (6)2.378 (5)180 (8)
O1W—H11W···O12B0.81 (6)1.91 (6)2.722 (5)179 (9)
O1W—H12W···O22Bi0.79 (6)1.91 (6)2.702 (5)179 (9)
O2W—H21W···O3W0.88 (5)1.97 (5)2.809 (5)160 (4)
O2W—H22W···O4W0.76 (6)2.06 (6)2.804 (6)164 (5)
O3W—H31W···O11Aii0.83 (7)2.22 (7)3.031 (6)168 (6)
O3W—H32W···O1W0.84 (6)2.07 (6)2.913 (5)179 (8)
O4W—H41W···O11Aiii0.76 (7)2.08 (7)2.842 (6)175 (8)
O4W—H42W···O21Biv0.81 (7)2.20 (7)3.009 (5)179 (8)
Symmetry codes: (i) x, y+2, z+1; (ii) x, y, z1; (iii) x+1, y+2, z+2; (iv) x+1, y+2, z+1.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

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