Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109006702/ga3117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109006702/ga3117Isup2.hkl |
CCDC reference: 730089
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.
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.
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).
C23H32ClN3O2+·2C8H3Cl2O4−·4H2O | Z = 2 |
Mr = 942.04 | F(000) = 980 |
Triclinic, P1 | Dx = 1.457 Mg m−3 |
Hall symbol: -P 1 | Melting point: 343 K |
a = 10.6392 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.6737 (5) Å | Cell parameters from 5030 reflections |
c = 18.2030 (12) Å | θ = 3.0–32.4° |
α = 77.961 (5)° | µ = 0.41 mm−1 |
β = 89.549 (5)° | T = 200 K |
γ = 76.432 (5)° | Block, yellow |
V = 2147.4 (2) Å3 | 0.20 × 0.20 × 0.15 mm |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 7444 independent reflections |
Radiation source: Enhance (Mo) X-ray tube | 4778 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans | θmax = 25.3°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.909, Tmax = 0.948 | k = −14→14 |
14440 measured reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.078 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.195 | H 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 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C23H32ClN3O2+·2C8H3Cl2O4−·4H2O | γ = 76.432 (5)° |
Mr = 942.04 | V = 2147.4 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.6392 (6) Å | Mo Kα radiation |
b = 11.6737 (5) Å | µ = 0.41 mm−1 |
c = 18.2030 (12) Å | T = 200 K |
α = 77.961 (5)° | 0.20 × 0.20 × 0.15 mm |
β = 89.549 (5)° |
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 = 0.948 | Rint = 0.057 |
14440 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | 0 restraints |
wR(F2) = 0.195 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.70 e Å−3 |
7444 reflections | Δρmin = −0.43 e Å−3 |
593 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl6 | 0.71491 (11) | 0.40203 (10) | 1.12719 (6) | 0.0350 (3) | |
O2 | 0.3581 (3) | 1.0802 (3) | 0.66236 (19) | 0.0427 (11) | |
N10 | 0.4949 (3) | 0.7724 (3) | 0.9367 (2) | 0.0257 (10) | |
N91 | 0.5970 (3) | 0.6337 (3) | 0.7478 (2) | 0.0267 (11) | |
N141 | 0.2206 (3) | 0.4717 (3) | 0.6373 (2) | 0.0305 (11) | |
C1 | 0.4675 (4) | 0.8811 (4) | 0.7315 (2) | 0.0266 (12) | |
C2 | 0.4002 (4) | 0.9979 (4) | 0.7276 (3) | 0.0313 (14) | |
C3 | 0.3671 (4) | 1.0400 (4) | 0.7929 (3) | 0.0320 (13) | |
C4 | 0.3992 (4) | 0.9667 (4) | 0.8615 (3) | 0.0303 (14) | |
C5 | 0.5983 (4) | 0.5935 (4) | 1.0221 (2) | 0.0259 (12) | |
C6 | 0.6786 (4) | 0.4823 (3) | 1.0349 (2) | 0.0257 (12) | |
C7 | 0.7347 (4) | 0.4307 (4) | 0.9758 (2) | 0.0296 (12) | |
C8 | 0.7041 (4) | 0.4909 (4) | 0.9038 (2) | 0.0305 (12) | |
C9 | 0.5752 (4) | 0.6753 (3) | 0.8099 (2) | 0.0222 (11) | |
C11 | 0.5039 (4) | 0.8015 (3) | 0.8023 (2) | 0.0233 (11) | |
C12 | 0.4677 (4) | 0.8444 (3) | 0.8665 (2) | 0.0230 (11) | |
C13 | 0.5693 (4) | 0.6579 (3) | 0.9471 (2) | 0.0234 (11) | |
C14 | 0.6159 (4) | 0.6071 (3) | 0.8856 (2) | 0.0225 (11) | |
C21 | 0.3894 (5) | 1.0430 (5) | 0.5933 (3) | 0.0501 (17) | |
C101 | 0.6492 (4) | 0.5106 (3) | 0.7335 (2) | 0.0282 (11) | |
C102 | 0.7889 (5) | 0.4950 (4) | 0.7128 (3) | 0.0403 (17) | |
C111 | 0.5680 (4) | 0.4900 (4) | 0.6709 (2) | 0.0309 (12) | |
C121 | 0.4255 (4) | 0.5050 (4) | 0.6873 (3) | 0.0305 (12) | |
C131 | 0.3637 (4) | 0.4321 (4) | 0.6440 (3) | 0.0330 (14) | |
C151 | 0.1631 (5) | 0.3906 (5) | 0.5996 (3) | 0.0445 (17) | |
C161 | 0.1905 (6) | 0.4025 (6) | 0.5191 (3) | 0.063 (2) | |
C171 | 0.1556 (5) | 0.4913 (4) | 0.7084 (3) | 0.0362 (14) | |
C181 | 0.1782 (5) | 0.3798 (4) | 0.7707 (3) | 0.0485 (17) | |
Cl3 | −0.06477 (14) | 1.19911 (11) | 0.87634 (7) | 0.0494 (4) | |
Cl4B | 0.10174 (12) | 0.93106 (10) | 0.93854 (6) | 0.0397 (3) | |
O11B | 0.2086 (3) | 0.7601 (3) | 0.70717 (19) | 0.0446 (11) | |
O12B | 0.1318 (4) | 0.8825 (3) | 0.60114 (18) | 0.0495 (13) | |
O21B | 0.0243 (4) | 1.0875 (3) | 0.55335 (17) | 0.0480 (13) | |
O22B | −0.0606 (3) | 1.2507 (3) | 0.59485 (18) | 0.0440 (10) | |
C1B | 0.0929 (4) | 0.9553 (3) | 0.7164 (2) | 0.0237 (11) | |
C2B | 0.0230 (4) | 1.0762 (4) | 0.6876 (2) | 0.0275 (12) | |
C3B | −0.0227 (4) | 1.1465 (4) | 0.7402 (2) | 0.0302 (11) | |
C4B | −0.0026 (4) | 1.1049 (4) | 0.8163 (2) | 0.0304 (14) | |
C5B | 0.0685 (4) | 0.9871 (4) | 0.8438 (2) | 0.0275 (12) | |
C6B | 0.1133 (4) | 0.9155 (4) | 0.7933 (2) | 0.0262 (11) | |
C11B | 0.1491 (4) | 0.8581 (4) | 0.6726 (2) | 0.0293 (12) | |
C21B | −0.0071 (4) | 1.1428 (4) | 0.6067 (2) | 0.0323 (14) | |
Cl4A | 0.11056 (14) | 1.30100 (12) | 1.01560 (8) | 0.0582 (5) | |
Cl5B | 0.05544 (13) | 1.33712 (11) | 1.18081 (10) | 0.0600 (5) | |
O11A | 0.2969 (4) | 0.9431 (4) | 1.3484 (2) | 0.0566 (14) | |
O12A | 0.3872 (4) | 0.8053 (3) | 1.2874 (2) | 0.0671 (16) | |
O21A | 0.4266 (4) | 0.7764 (3) | 1.1637 (3) | 0.0614 (16) | |
O22A | 0.3994 (4) | 0.8845 (4) | 1.0489 (3) | 0.0726 (17) | |
C1A | 0.2771 (4) | 1.0006 (4) | 1.2152 (2) | 0.0279 (12) | |
C2A | 0.3013 (4) | 0.9838 (4) | 1.1416 (3) | 0.0293 (12) | |
C3A | 0.2495 (4) | 1.0790 (4) | 1.0817 (3) | 0.0336 (16) | |
C4A | 0.1743 (4) | 1.1880 (4) | 1.0923 (3) | 0.0339 (14) | |
C5A | 0.1501 (4) | 1.2038 (4) | 1.1642 (3) | 0.0314 (14) | |
C6A | 0.2025 (4) | 1.1123 (4) | 1.2243 (3) | 0.0319 (14) | |
C11A | 0.3226 (5) | 0.9120 (4) | 1.2896 (3) | 0.0386 (17) | |
C21A | 0.3811 (5) | 0.8736 (4) | 1.1154 (3) | 0.0439 (19) | |
O1W | 0.1979 (3) | 0.6864 (3) | 0.53762 (18) | 0.0422 (10) | |
O2W | 0.5917 (4) | 0.7634 (3) | 0.59276 (19) | 0.0519 (13) | |
O3W | 0.4350 (4) | 0.7418 (4) | 0.4753 (2) | 0.0681 (16) | |
O4W | 0.8062 (4) | 0.8662 (4) | 0.5773 (2) | 0.0734 (17) | |
H1 | 0.48950 | 0.85390 | 0.68750 | 0.0320* | |
H3 | 0.32240 | 1.11980 | 0.78930 | 0.0380* | |
H4 | 0.37680 | 0.99570 | 0.90490 | 0.0370* | |
H5 | 0.56290 | 0.62700 | 1.06190 | 0.0310* | |
H7 | 0.79260 | 0.35550 | 0.98600 | 0.0350* | |
H8 | 0.74140 | 0.45570 | 0.86500 | 0.0360* | |
H21 | 0.35410 | 1.10850 | 0.55190 | 0.0600* | |
H22 | 0.35330 | 0.97560 | 0.59110 | 0.0600* | |
H23 | 0.48170 | 1.01970 | 0.59030 | 0.0600* | |
H101 | 0.64420 | 0.45120 | 0.77950 | 0.0340* | |
H102 | 0.83860 | 0.50800 | 0.75280 | 0.0490* | |
H103 | 0.79480 | 0.55220 | 0.66750 | 0.0490* | |
H104 | 0.82200 | 0.41470 | 0.70510 | 0.0490* | |
H111 | 0.57610 | 0.54640 | 0.62470 | 0.0370* | |
H112 | 0.60250 | 0.40920 | 0.66280 | 0.0370* | |
H121 | 0.38120 | 0.58950 | 0.67300 | 0.0370* | |
H122 | 0.41650 | 0.47800 | 0.74080 | 0.0370* | |
H131 | 0.39740 | 0.43900 | 0.59400 | 0.0400* | |
H132 | 0.38830 | 0.34770 | 0.66920 | 0.0400* | |
H151 | 0.19720 | 0.30750 | 0.62540 | 0.0530* | |
H152 | 0.07010 | 0.40960 | 0.60470 | 0.0530* | |
H161 | 0.15190 | 0.34890 | 0.49840 | 0.0750* | |
H162 | 0.28240 | 0.38220 | 0.51360 | 0.0750* | |
H163 | 0.15500 | 0.48410 | 0.49290 | 0.0750* | |
H171 | 0.06320 | 0.52100 | 0.69730 | 0.0440* | |
H172 | 0.18630 | 0.55320 | 0.72600 | 0.0440* | |
H181 | 0.13390 | 0.39920 | 0.81430 | 0.0580* | |
H182 | 0.26930 | 0.35060 | 0.78300 | 0.0580* | |
H183 | 0.14590 | 0.31860 | 0.75440 | 0.0580* | |
H3B | −0.06920 | 1.22550 | 0.72250 | 0.0360* | |
H6B | 0.15950 | 0.83660 | 0.81190 | 0.0310* | |
H3A | 0.26600 | 1.06900 | 1.03290 | 0.0410* | |
H6A | 0.18780 | 1.12500 | 1.27270 | 0.0390* | |
H10 | 0.462 (4) | 0.806 (4) | 0.981 (3) | 0.027 (11)* | |
H91 | 0.574 (5) | 0.680 (5) | 0.705 (3) | 0.047 (16)* | |
H12B | 0.091 (5) | 0.961 (5) | 0.583 (3) | 0.065 (16)* | |
H141 | 0.202 (4) | 0.545 (4) | 0.605 (3) | 0.038 (15)* | |
H21A | 0.404 (5) | 0.788 (5) | 1.211 (3) | 0.075 (17)* | |
H11W | 0.178 (5) | 0.744 (5) | 0.557 (3) | 0.055 (16)* | |
H12W | 0.157 (6) | 0.705 (6) | 0.499 (3) | 0.058 (16)* | |
H21W | 0.560 (4) | 0.757 (5) | 0.550 (3) | 0.066 (15)* | |
H22W | 0.648 (5) | 0.792 (6) | 0.580 (3) | 0.065 (15)* | |
H31W | 0.409 (6) | 0.798 (6) | 0.439 (4) | 0.078 (16)* | |
H32W | 0.366 (5) | 0.726 (5) | 0.493 (4) | 0.080 (15)* | |
H41W | 0.777 (6) | 0.920 (6) | 0.595 (4) | 0.085 (14)* | |
H42W | 0.852 (5) | 0.878 (6) | 0.542 (4) | 0.088 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl6 | 0.0411 (6) | 0.0295 (5) | 0.0297 (5) | −0.0078 (5) | −0.0068 (5) | 0.0038 (4) |
O2 | 0.052 (2) | 0.0246 (16) | 0.043 (2) | −0.0071 (14) | −0.0033 (16) | 0.0094 (15) |
N10 | 0.034 (2) | 0.0157 (16) | 0.0269 (18) | −0.0054 (14) | 0.0027 (15) | −0.0044 (15) |
N91 | 0.037 (2) | 0.0203 (17) | 0.0243 (19) | −0.0100 (15) | 0.0015 (16) | −0.0048 (16) |
N141 | 0.036 (2) | 0.0186 (17) | 0.038 (2) | −0.0107 (15) | −0.0049 (16) | −0.0032 (15) |
C1 | 0.030 (2) | 0.023 (2) | 0.028 (2) | −0.0107 (17) | 0.0025 (18) | −0.0030 (17) |
C2 | 0.030 (2) | 0.020 (2) | 0.040 (3) | −0.0076 (17) | −0.0021 (19) | 0.0041 (19) |
C3 | 0.033 (2) | 0.0128 (18) | 0.048 (3) | −0.0046 (17) | −0.002 (2) | −0.0023 (19) |
C4 | 0.033 (2) | 0.0177 (19) | 0.042 (3) | −0.0058 (17) | 0.000 (2) | −0.0106 (19) |
C5 | 0.025 (2) | 0.025 (2) | 0.028 (2) | −0.0075 (17) | 0.0004 (17) | −0.0047 (18) |
C6 | 0.028 (2) | 0.021 (2) | 0.027 (2) | −0.0094 (17) | −0.0039 (17) | 0.0014 (17) |
C7 | 0.029 (2) | 0.020 (2) | 0.037 (2) | −0.0037 (17) | −0.0056 (19) | −0.0017 (18) |
C8 | 0.034 (2) | 0.023 (2) | 0.034 (2) | −0.0036 (18) | 0.0016 (19) | −0.0087 (18) |
C9 | 0.0188 (19) | 0.0189 (19) | 0.031 (2) | −0.0091 (15) | 0.0037 (16) | −0.0048 (17) |
C11 | 0.022 (2) | 0.0193 (19) | 0.030 (2) | −0.0100 (16) | −0.0008 (17) | −0.0028 (17) |
C12 | 0.023 (2) | 0.0177 (18) | 0.030 (2) | −0.0100 (16) | −0.0012 (17) | −0.0029 (17) |
C13 | 0.020 (2) | 0.0181 (19) | 0.034 (2) | −0.0064 (16) | 0.0028 (17) | −0.0077 (17) |
C14 | 0.0198 (19) | 0.0199 (19) | 0.028 (2) | −0.0052 (16) | −0.0007 (16) | −0.0053 (17) |
C21 | 0.061 (3) | 0.042 (3) | 0.040 (3) | −0.015 (3) | −0.008 (3) | 0.011 (2) |
C101 | 0.032 (2) | 0.0159 (19) | 0.036 (2) | −0.0036 (17) | −0.0010 (19) | −0.0066 (18) |
C102 | 0.045 (3) | 0.035 (3) | 0.043 (3) | −0.011 (2) | 0.000 (2) | −0.011 (2) |
C111 | 0.038 (2) | 0.022 (2) | 0.036 (2) | −0.0105 (18) | 0.0034 (19) | −0.0101 (19) |
C121 | 0.033 (2) | 0.025 (2) | 0.036 (2) | −0.0082 (18) | −0.0005 (19) | −0.0107 (19) |
C131 | 0.037 (2) | 0.024 (2) | 0.041 (3) | −0.0076 (18) | 0.002 (2) | −0.0132 (19) |
C151 | 0.047 (3) | 0.038 (3) | 0.058 (3) | −0.019 (2) | −0.007 (2) | −0.021 (2) |
C161 | 0.072 (4) | 0.061 (4) | 0.071 (4) | −0.024 (3) | 0.001 (3) | −0.040 (3) |
C171 | 0.035 (2) | 0.032 (2) | 0.047 (3) | −0.014 (2) | 0.007 (2) | −0.014 (2) |
C181 | 0.064 (3) | 0.033 (3) | 0.053 (3) | −0.023 (2) | 0.015 (3) | −0.007 (2) |
Cl3 | 0.0824 (10) | 0.0323 (6) | 0.0365 (6) | −0.0115 (6) | 0.0129 (6) | −0.0169 (5) |
Cl4B | 0.0534 (7) | 0.0414 (6) | 0.0234 (5) | −0.0139 (6) | −0.0009 (5) | −0.0021 (5) |
O11B | 0.065 (2) | 0.0228 (16) | 0.0409 (19) | 0.0019 (15) | 0.0026 (17) | −0.0093 (15) |
O12B | 0.079 (3) | 0.0345 (18) | 0.0337 (19) | −0.0041 (17) | −0.0017 (17) | −0.0150 (15) |
O21B | 0.080 (3) | 0.0344 (18) | 0.0255 (17) | −0.0052 (17) | −0.0014 (17) | −0.0070 (15) |
O22B | 0.071 (2) | 0.0221 (16) | 0.0374 (18) | −0.0136 (16) | −0.0088 (17) | −0.0001 (14) |
C1B | 0.026 (2) | 0.0185 (19) | 0.031 (2) | −0.0130 (16) | 0.0017 (17) | −0.0067 (17) |
C2B | 0.032 (2) | 0.026 (2) | 0.029 (2) | −0.0170 (18) | −0.0028 (18) | −0.0045 (18) |
C3B | 0.039 (2) | 0.0169 (19) | 0.035 (2) | −0.0090 (18) | 0.001 (2) | −0.0037 (18) |
C4B | 0.041 (3) | 0.025 (2) | 0.031 (2) | −0.0150 (19) | 0.0054 (19) | −0.0109 (18) |
C5B | 0.030 (2) | 0.029 (2) | 0.025 (2) | −0.0131 (18) | 0.0027 (18) | −0.0024 (18) |
C6B | 0.029 (2) | 0.0197 (19) | 0.030 (2) | −0.0077 (17) | −0.0009 (18) | −0.0036 (17) |
C11B | 0.035 (2) | 0.023 (2) | 0.034 (2) | −0.0124 (19) | 0.0047 (19) | −0.0094 (19) |
C21B | 0.045 (3) | 0.028 (2) | 0.026 (2) | −0.015 (2) | −0.004 (2) | −0.0033 (19) |
Cl4A | 0.0608 (8) | 0.0426 (7) | 0.0643 (9) | −0.0223 (6) | −0.0243 (7) | 0.0165 (7) |
Cl5B | 0.0428 (7) | 0.0329 (6) | 0.1066 (12) | −0.0015 (5) | 0.0068 (7) | −0.0286 (7) |
O11A | 0.079 (3) | 0.061 (2) | 0.034 (2) | −0.033 (2) | −0.0005 (19) | −0.0007 (18) |
O12A | 0.088 (3) | 0.033 (2) | 0.065 (3) | −0.005 (2) | −0.002 (2) | 0.0133 (19) |
O21A | 0.073 (3) | 0.030 (2) | 0.080 (3) | −0.0025 (18) | 0.007 (2) | −0.020 (2) |
O22A | 0.090 (3) | 0.068 (3) | 0.062 (3) | 0.004 (2) | 0.014 (2) | −0.045 (2) |
C1A | 0.031 (2) | 0.024 (2) | 0.033 (2) | −0.0131 (18) | −0.0013 (18) | −0.0081 (18) |
C2A | 0.030 (2) | 0.025 (2) | 0.039 (2) | −0.0140 (18) | 0.0013 (19) | −0.0117 (19) |
C3A | 0.038 (3) | 0.039 (3) | 0.030 (2) | −0.019 (2) | 0.002 (2) | −0.010 (2) |
C4A | 0.029 (2) | 0.028 (2) | 0.045 (3) | −0.0157 (19) | −0.006 (2) | 0.002 (2) |
C5A | 0.024 (2) | 0.022 (2) | 0.053 (3) | −0.0085 (17) | 0.003 (2) | −0.015 (2) |
C6A | 0.031 (2) | 0.039 (3) | 0.036 (2) | −0.018 (2) | 0.006 (2) | −0.020 (2) |
C11A | 0.047 (3) | 0.039 (3) | 0.036 (3) | −0.027 (2) | −0.001 (2) | −0.003 (2) |
C21A | 0.044 (3) | 0.034 (3) | 0.061 (4) | −0.009 (2) | 0.004 (3) | −0.027 (3) |
O1W | 0.063 (2) | 0.0245 (16) | 0.0358 (18) | −0.0068 (15) | −0.0033 (16) | −0.0033 (14) |
O2W | 0.084 (3) | 0.042 (2) | 0.0352 (18) | −0.0302 (19) | 0.0115 (18) | −0.0039 (16) |
O3W | 0.070 (3) | 0.089 (3) | 0.046 (2) | −0.037 (2) | −0.008 (2) | 0.005 (2) |
O4W | 0.084 (3) | 0.099 (3) | 0.058 (3) | −0.054 (3) | 0.014 (2) | −0.027 (2) |
Cl6—C6 | 1.742 (4) | C3—H3 | 0.9300 |
Cl3—C4B | 1.729 (4) | C4—H4 | 0.9300 |
Cl4B—C5B | 1.720 (4) | C5—H5 | 0.9300 |
Cl4A—C4A | 1.725 (5) | C7—H7 | 0.9300 |
Cl5B—C5A | 1.727 (5) | C8—H8 | 0.9300 |
O2—C2 | 1.366 (6) | C111—C121 | 1.519 (6) |
O2—C21 | 1.426 (6) | C21—H22 | 0.9600 |
O11B—C11B | 1.213 (6) | C121—C131 | 1.526 (7) |
O12B—C11B | 1.277 (5) | C21—H21 | 0.9600 |
O21B—C21B | 1.275 (5) | C21—H23 | 0.9600 |
O22B—C21B | 1.229 (6) | C151—C161 | 1.476 (8) |
O12B—H12B | 0.91 (6) | C171—C181 | 1.510 (7) |
O11A—C11A | 1.210 (6) | C101—H101 | 0.9800 |
O12A—C11A | 1.282 (6) | C1B—C6B | 1.382 (5) |
O21A—C21A | 1.276 (7) | C1B—C2B | 1.423 (6) |
O22A—C21A | 1.210 (8) | C1B—C11B | 1.527 (6) |
O21A—H21A | 0.92 (5) | C102—H103 | 0.9600 |
O1W—H11W | 0.81 (6) | C102—H102 | 0.9600 |
O1W—H12W | 0.79 (6) | C102—H104 | 0.9600 |
O2W—H22W | 0.76 (6) | C2B—C21B | 1.513 (5) |
O2W—H21W | 0.88 (5) | C2B—C3B | 1.400 (6) |
N10—C12 | 1.366 (5) | C3B—C4B | 1.370 (5) |
N10—C13 | 1.360 (5) | C4B—C5B | 1.395 (6) |
N91—C101 | 1.490 (5) | C5B—C6B | 1.378 (6) |
N91—C9 | 1.319 (5) | C111—H112 | 0.9700 |
O3W—H31W | 0.83 (7) | C111—H111 | 0.9700 |
O3W—H32W | 0.84 (6) | C121—H122 | 0.9700 |
N10—H10 | 1.00 (5) | C121—H121 | 0.9700 |
N141—C171 | 1.497 (6) | C131—H132 | 0.9700 |
N141—C131 | 1.482 (6) | C131—H131 | 0.9700 |
N141—C151 | 1.514 (7) | C151—H151 | 0.9700 |
N91—H91 | 0.85 (5) | C151—H152 | 0.9700 |
N141—H141 | 0.91 (5) | C161—H162 | 0.9600 |
O4W—H42W | 0.81 (7) | C161—H163 | 0.9600 |
O4W—H41W | 0.77 (7) | C161—H161 | 0.9600 |
C1—C2 | 1.371 (7) | C171—H172 | 0.9700 |
C1—C11 | 1.419 (5) | C171—H171 | 0.9700 |
C2—C3 | 1.391 (7) | C181—H181 | 0.9600 |
C3—C4 | 1.354 (7) | C181—H183 | 0.9600 |
C4—C12 | 1.427 (6) | C181—H182 | 0.9600 |
C5—C13 | 1.412 (5) | C3B—H3B | 0.9300 |
C5—C6 | 1.351 (6) | C6B—H6B | 0.9300 |
C6—C7 | 1.403 (5) | C1A—C6A | 1.400 (7) |
C7—C8 | 1.354 (5) | C1A—C11A | 1.526 (6) |
C8—C14 | 1.432 (6) | C1A—C2A | 1.407 (6) |
C9—C14 | 1.453 (5) | C2A—C21A | 1.530 (7) |
C9—C11 | 1.469 (5) | C2A—C3A | 1.394 (7) |
C11—C12 | 1.383 (5) | C3A—C4A | 1.385 (7) |
C13—C14 | 1.408 (5) | C4A—C5A | 1.374 (7) |
C101—C111 | 1.526 (6) | C5A—C6A | 1.375 (7) |
C101—C102 | 1.509 (7) | C3A—H3A | 0.9300 |
C1—H1 | 0.9300 | C6A—H6A | 0.9300 |
C2—O2—C21 | 117.7 (4) | C101—C102—H103 | 109.00 |
C11B—O12B—H12B | 112 (3) | C3B—C2B—C21B | 114.0 (4) |
C21A—O21A—H21A | 109 (3) | C1B—C2B—C3B | 116.9 (3) |
H11W—O1W—H12W | 106 (6) | C1B—C2B—C21B | 129.1 (4) |
H21W—O2W—H22W | 102 (5) | C2B—C3B—C4B | 123.5 (4) |
C12—N10—C13 | 121.4 (3) | C3B—C4B—C5B | 119.1 (4) |
C9—N91—C101 | 133.0 (3) | Cl3—C4B—C3B | 119.6 (4) |
H31W—O3W—H32W | 103 (6) | Cl3—C4B—C5B | 121.3 (3) |
C12—N10—H10 | 119 (3) | Cl4B—C5B—C4B | 121.4 (3) |
C13—N10—H10 | 120 (3) | Cl4B—C5B—C6B | 120.0 (3) |
C131—N141—C151 | 111.3 (4) | C4B—C5B—C6B | 118.6 (3) |
C131—N141—C171 | 115.3 (4) | C1B—C6B—C5B | 123.2 (4) |
C151—N141—C171 | 112.1 (4) | C101—C111—H112 | 109.00 |
C9—N91—H91 | 121 (4) | C101—C111—H111 | 109.00 |
C101—N91—H91 | 106 (4) | C121—C111—H112 | 109.00 |
C171—N141—H141 | 106 (4) | H111—C111—H112 | 108.00 |
C131—N141—H141 | 106 (4) | C121—C111—H111 | 109.00 |
C151—N141—H141 | 106 (4) | O12B—C11B—C1B | 119.1 (4) |
H41W—O4W—H42W | 117 (7) | O11B—C11B—O12B | 122.3 (4) |
C2—C1—C11 | 120.4 (4) | O11B—C11B—C1B | 118.6 (3) |
O2—C2—C1 | 124.7 (4) | C131—C121—H121 | 110.00 |
O2—C2—C3 | 114.8 (4) | C131—C121—H122 | 109.00 |
C1—C2—C3 | 120.5 (5) | C111—C121—H122 | 110.00 |
C2—C3—C4 | 121.0 (4) | C111—C121—H121 | 110.00 |
C3—C4—C12 | 119.2 (4) | H121—C121—H122 | 108.00 |
C6—C5—C13 | 118.7 (4) | O21B—C21B—O22B | 122.0 (4) |
Cl6—C6—C5 | 119.1 (3) | O22B—C21B—C2B | 117.8 (4) |
C5—C6—C7 | 121.7 (3) | O21B—C21B—C2B | 120.2 (4) |
Cl6—C6—C7 | 119.3 (3) | N141—C131—H132 | 109.00 |
C6—C7—C8 | 119.7 (4) | H131—C131—H132 | 108.00 |
C7—C8—C14 | 122.0 (4) | C121—C131—H132 | 109.00 |
N91—C9—C11 | 117.5 (3) | C121—C131—H131 | 109.00 |
N91—C9—C14 | 125.6 (3) | N141—C131—H131 | 109.00 |
C11—C9—C14 | 116.8 (3) | N141—C151—H151 | 109.00 |
C1—C11—C9 | 122.7 (3) | N141—C151—H152 | 109.00 |
C1—C11—C12 | 118.3 (3) | C161—C151—H151 | 109.00 |
C9—C11—C12 | 119.0 (3) | C161—C151—H152 | 109.00 |
C4—C12—C11 | 120.7 (4) | H151—C151—H152 | 108.00 |
N10—C12—C11 | 121.9 (3) | H161—C161—H163 | 109.00 |
N10—C12—C4 | 117.4 (4) | H161—C161—H162 | 109.00 |
N10—C13—C14 | 121.2 (3) | C151—C161—H162 | 109.00 |
C5—C13—C14 | 121.9 (3) | C151—C161—H163 | 109.00 |
N10—C13—C5 | 116.9 (3) | H162—C161—H163 | 109.00 |
C9—C14—C13 | 119.0 (3) | C151—C161—H161 | 110.00 |
C8—C14—C9 | 125.1 (3) | C181—C171—H172 | 109.00 |
C8—C14—C13 | 115.9 (3) | H171—C171—H172 | 108.00 |
N91—C101—C111 | 109.9 (3) | N141—C171—H171 | 109.00 |
C102—C101—C111 | 110.5 (3) | C181—C171—H171 | 109.00 |
N91—C101—C102 | 110.3 (3) | N141—C171—H172 | 109.00 |
C11—C1—H1 | 120.00 | C171—C181—H182 | 109.00 |
C2—C1—H1 | 120.00 | C171—C181—H183 | 109.00 |
C4—C3—H3 | 120.00 | H181—C181—H182 | 109.00 |
C2—C3—H3 | 119.00 | H181—C181—H183 | 110.00 |
C3—C4—H4 | 120.00 | H182—C181—H183 | 109.00 |
C12—C4—H4 | 120.00 | C171—C181—H181 | 109.00 |
C13—C5—H5 | 121.00 | C4B—C3B—H3B | 118.00 |
C6—C5—H5 | 121.00 | C2B—C3B—H3B | 118.00 |
C8—C7—H7 | 120.00 | C5B—C6B—H6B | 118.00 |
C6—C7—H7 | 120.00 | C1B—C6B—H6B | 118.00 |
C7—C8—H8 | 119.00 | C2A—C1A—C11A | 128.6 (4) |
C14—C8—H8 | 119.00 | C6A—C1A—C11A | 113.2 (4) |
C101—C111—C121 | 113.7 (3) | C2A—C1A—C6A | 118.1 (4) |
O2—C21—H23 | 110.00 | C1A—C2A—C3A | 118.3 (4) |
O2—C21—H21 | 110.00 | C1A—C2A—C21A | 129.3 (4) |
H21—C21—H23 | 109.00 | C3A—C2A—C21A | 112.4 (4) |
H22—C21—H23 | 109.00 | C2A—C3A—C4A | 122.3 (5) |
C111—C121—C131 | 110.6 (4) | C3A—C4A—C5A | 119.2 (5) |
O2—C21—H22 | 109.00 | Cl4A—C4A—C3A | 119.9 (4) |
H21—C21—H22 | 109.00 | Cl4A—C4A—C5A | 120.9 (4) |
N141—C131—C121 | 113.2 (4) | Cl5B—C5A—C4A | 121.2 (4) |
N141—C151—C161 | 113.4 (5) | Cl5B—C5A—C6A | 119.1 (4) |
N141—C171—C181 | 114.2 (4) | C4A—C5A—C6A | 119.6 (4) |
C102—C101—H101 | 109.00 | C1A—C6A—C5A | 122.3 (5) |
C111—C101—H101 | 109.00 | O12A—C11A—C1A | 118.1 (4) |
N91—C101—H101 | 109.00 | O11A—C11A—C1A | 120.0 (4) |
C6B—C1B—C11B | 113.2 (3) | O11A—C11A—O12A | 121.9 (5) |
C2B—C1B—C6B | 118.7 (3) | O21A—C21A—O22A | 123.2 (5) |
C2B—C1B—C11B | 128.1 (3) | O21A—C21A—C2A | 119.5 (5) |
H102—C102—H104 | 109.00 | O22A—C21A—C2A | 117.3 (5) |
H102—C102—H103 | 110.00 | C4A—C3A—H3A | 119.00 |
C101—C102—H104 | 109.00 | C2A—C3A—H3A | 119.00 |
H103—C102—H104 | 110.00 | C1A—C6A—H6A | 119.00 |
C101—C102—H102 | 109.00 | C5A—C6A—H6A | 119.00 |
C21—O2—C2—C1 | −1.8 (6) | C11B—C1B—C2B—C3B | 177.6 (4) |
C21—O2—C2—C3 | 179.7 (4) | C11B—C1B—C2B—C21B | −4.2 (8) |
C13—N10—C12—C4 | −174.3 (4) | C2B—C1B—C6B—C5B | 0.4 (7) |
C13—N10—C12—C11 | 6.1 (6) | C11B—C1B—C6B—C5B | −178.5 (4) |
C12—N10—C13—C5 | 176.2 (4) | C2B—C1B—C11B—O11B | 178.5 (4) |
C12—N10—C13—C14 | −3.2 (6) | C2B—C1B—C11B—O12B | −1.7 (7) |
C101—N91—C9—C11 | −171.0 (4) | C6B—C1B—C11B—O11B | −2.8 (6) |
C101—N91—C9—C14 | 9.2 (7) | C6B—C1B—C11B—O12B | 177.1 (4) |
C9—N91—C101—C102 | −101.7 (5) | C1B—C2B—C3B—C4B | 0.4 (7) |
C9—N91—C101—C111 | 136.3 (4) | C21B—C2B—C3B—C4B | −178.0 (4) |
C11—C1—C2—O2 | −178.3 (4) | C1B—C2B—C21B—O21B | 4.8 (7) |
C11—C1—C2—C3 | 0.2 (7) | C1B—C2B—C21B—O22B | −174.3 (4) |
C2—C1—C11—C9 | 179.6 (4) | C3B—C2B—C21B—O21B | −177.0 (4) |
C2—C1—C11—C12 | 1.1 (6) | C3B—C2B—C21B—O22B | 3.9 (6) |
O2—C2—C3—C4 | 177.9 (4) | C2B—C3B—C4B—Cl3 | −179.4 (4) |
C1—C2—C3—C4 | −0.7 (7) | C2B—C3B—C4B—C5B | 1.0 (7) |
C2—C3—C4—C12 | −0.2 (7) | Cl3—C4B—C5B—Cl4B | −1.9 (6) |
C3—C4—C12—N10 | −178.1 (4) | Cl3—C4B—C5B—C6B | 178.7 (3) |
C3—C4—C12—C11 | 1.6 (7) | C3B—C4B—C5B—Cl4B | 177.8 (3) |
C13—C5—C6—Cl6 | −180.0 (3) | C3B—C4B—C5B—C6B | −1.7 (7) |
C13—C5—C6—C7 | 0.9 (7) | Cl4B—C5B—C6B—C1B | −178.5 (4) |
C6—C5—C13—N10 | −175.9 (4) | C4B—C5B—C6B—C1B | 1.0 (7) |
C6—C5—C13—C14 | 3.5 (7) | C6A—C1A—C2A—C3A | −0.2 (6) |
Cl6—C6—C7—C8 | 178.1 (3) | C6A—C1A—C2A—C21A | 178.5 (5) |
C5—C6—C7—C8 | −2.8 (7) | C11A—C1A—C2A—C3A | −179.7 (4) |
C6—C7—C8—C14 | 0.3 (7) | C11A—C1A—C2A—C21A | −1.0 (8) |
C7—C8—C14—C9 | −177.9 (4) | C2A—C1A—C6A—C5A | 1.7 (7) |
C7—C8—C14—C13 | 3.7 (6) | C11A—C1A—C6A—C5A | −178.7 (4) |
N91—C9—C11—C1 | −5.1 (6) | C2A—C1A—C11A—O11A | 177.1 (5) |
N91—C9—C11—C12 | 173.4 (4) | C2A—C1A—C11A—O12A | −3.3 (8) |
C14—C9—C11—C1 | 174.8 (4) | C6A—C1A—C11A—O11A | −2.5 (7) |
C14—C9—C11—C12 | −6.8 (6) | C6A—C1A—C11A—O12A | 177.2 (5) |
N91—C9—C14—C8 | 11.0 (7) | C1A—C2A—C3A—C4A | −0.8 (7) |
N91—C9—C14—C13 | −170.7 (4) | C21A—C2A—C3A—C4A | −179.7 (4) |
C11—C9—C14—C8 | −168.9 (4) | C1A—C2A—C21A—O21A | 6.4 (8) |
C11—C9—C14—C13 | 9.5 (6) | C1A—C2A—C21A—O22A | −172.5 (5) |
C1—C11—C12—N10 | 177.6 (4) | C3A—C2A—C21A—O21A | −174.9 (5) |
C1—C11—C12—C4 | −2.0 (6) | C3A—C2A—C21A—O22A | 6.3 (7) |
C9—C11—C12—N10 | −0.9 (6) | C2A—C3A—C4A—Cl4A | −178.7 (4) |
C9—C11—C12—C4 | 179.5 (4) | C2A—C3A—C4A—C5A | 0.4 (7) |
N10—C13—C14—C8 | 173.7 (4) | Cl4A—C4A—C5A—Cl5B | −0.1 (6) |
N10—C13—C14—C9 | −4.8 (6) | Cl4A—C4A—C5A—C6A | −179.8 (4) |
C5—C13—C14—C8 | −5.7 (6) | C3A—C4A—C5A—Cl5B | −179.2 (3) |
C5—C13—C14—C9 | 175.9 (4) | C3A—C4A—C5A—C6A | 1.1 (7) |
C6B—C1B—C2B—C3B | −1.1 (6) | Cl5B—C5A—C6A—C1A | 178.2 (4) |
C6B—C1B—C2B—C21B | 177.1 (4) | C4A—C5A—C6A—C1A | −2.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O22A | 1.00 (5) | 1.73 (5) | 2.716 (6) | 172 (5) |
N91—H91···O2W | 0.85 (5) | 2.10 (5) | 2.905 (5) | 158 (5) |
N141—H141···O1W | 0.91 (5) | 1.83 (5) | 2.733 (5) | 169 (4) |
O21A—H21A···O12A | 0.92 (5) | 1.45 (5) | 2.366 (7) | 172 (6) |
O12B—H12B···O21B | 0.91 (6) | 1.47 (6) | 2.378 (5) | 180 (8) |
O1W—H11W···O12B | 0.81 (6) | 1.91 (6) | 2.722 (5) | 179 (9) |
O1W—H12W···O22Bi | 0.79 (6) | 1.91 (6) | 2.702 (5) | 179 (9) |
O2W—H21W···O3W | 0.88 (5) | 1.97 (5) | 2.809 (5) | 160 (4) |
O2W—H22W···O4W | 0.76 (6) | 2.06 (6) | 2.804 (6) | 164 (5) |
O3W—H31W···O11Aii | 0.83 (7) | 2.22 (7) | 3.031 (6) | 168 (6) |
O3W—H32W···O1W | 0.84 (6) | 2.07 (6) | 2.913 (5) | 179 (8) |
O4W—H41W···O11Aiii | 0.76 (7) | 2.08 (7) | 2.842 (6) | 175 (8) |
O4W—H42W···O21Biv | 0.81 (7) | 2.20 (7) | 3.009 (5) | 179 (8) |
C1—H1···O2W | 0.93 | 2.34 | 3.249 (5) | 166 |
C3A—H3A···O22A | 0.93 | 2.25 | 2.628 (7) | 104 |
C3B—H3B···O22B | 0.93 | 2.28 | 2.662 (5) | 104 |
C6A—H6A···O11A | 0.93 | 2.32 | 2.694 (6) | 103 |
C6B—H6B···O11B | 0.93 | 2.28 | 2.660 (5) | 104 |
C6B—H6B···Cl6v | 0.93 | 2.79 | 3.715 (5) | 177 |
C102—H102···Cl5Biii | 0.96 | 2.81 | 3.673 (5) | 150 |
C111—H111···O2W | 0.97 | 2.52 | 3.279 (6) | 135 |
C111—H112···O12Av | 0.97 | 2.46 | 3.291 (6) | 144 |
C121—H121···O11B | 0.97 | 2.55 | 3.397 (6) | 146 |
C151—H152···O22Bvi | 0.97 | 2.60 | 3.198 (7) | 120 |
C171—H172···O11B | 0.97 | 2.44 | 3.311 (6) | 150 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+2; (vi) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C23H32ClN3O2+·2C8H3Cl2O4−·4H2O |
Mr | 942.04 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 2147.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini-S CCD-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.909, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14440, 7444, 4778 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.195, 1.01 |
No. of reflections | 7444 |
No. of parameters | 593 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O22A | 1.00 (5) | 1.73 (5) | 2.716 (6) | 172 (5) |
N91—H91···O2W | 0.85 (5) | 2.10 (5) | 2.905 (5) | 158 (5) |
N141—H141···O1W | 0.91 (5) | 1.83 (5) | 2.733 (5) | 169 (4) |
O21A—H21A···O12A | 0.92 (5) | 1.45 (5) | 2.366 (7) | 172 (6) |
O12B—H12B···O21B | 0.91 (6) | 1.47 (6) | 2.378 (5) | 180 (8) |
O1W—H11W···O12B | 0.81 (6) | 1.91 (6) | 2.722 (5) | 179 (9) |
O1W—H12W···O22Bi | 0.79 (6) | 1.91 (6) | 2.702 (5) | 179 (9) |
O2W—H21W···O3W | 0.88 (5) | 1.97 (5) | 2.809 (5) | 160 (4) |
O2W—H22W···O4W | 0.76 (6) | 2.06 (6) | 2.804 (6) | 164 (5) |
O3W—H31W···O11Aii | 0.83 (7) | 2.22 (7) | 3.031 (6) | 168 (6) |
O3W—H32W···O1W | 0.84 (6) | 2.07 (6) | 2.913 (5) | 179 (8) |
O4W—H41W···O11Aiii | 0.76 (7) | 2.08 (7) | 2.842 (6) | 175 (8) |
O4W—H42W···O21Biv | 0.81 (7) | 2.20 (7) | 3.009 (5) | 179 (8) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y+2, −z+1. |
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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 π–π stacking effects are found in the dichloride but not in the 5-sulfosalicylate. Weak π–π 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 π–π 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 π–π 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.